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Sample records for ferrihydrite phase transformation

  1. Synthesis and phase transformations involving scorodite, ferric arsenate and arsenical ferrihydrite: Implications for arsenic mobility

    NASA Astrophysics Data System (ADS)

    Paktunc, Dogan; Dutrizac, John; Gertsman, Valery

    2008-06-01

    Scorodite, ferric arsenate and arsenical ferrihydrite are important arsenic carriers occurring in a wide range of environments and are also common precipitates used by metallurgical industries to control arsenic in effluents. Solubility and stability of these compounds are controversial because of the complexities in their identification and characterization in heterogeneous media. To provide insights into the formation of scorodite, ferric arsenate and ferrihydrite, series of synthesis experiments were carried out at 70 °C and pH 1, 2, 3 and 4.5 from 0.2 M Fe(SO 4) 1.5 solutions also containing 0.02-0.2 M Na 2HAsO 4. The precipitates were characterized by transmission electron microscopy, X-ray diffraction and X-ray absorption fine structure techniques. Ferric arsenate, characterized by two broad diffuse peaks on the XRD pattern and having the structural formula of FeAsO 4·4-7H 2O, is a precursor to scorodite formation. As defined by As XAFS and Fe XAFS, the local structure of ferric arsenate is profoundly different than that of scorodite. It is postulated that the ferric arsenate structure is made of single chains of corner-sharing Fe(O,OH) 6 octahedra with bridging arsenate tetrahedra alternating along the chains. Scorodite was precipitated from solutions with Fe/As molar ratios of 1 over the pH range of 1-4.5. The pH strongly controls the kinetics of scorodite formation and its transformation from ferric arsenate. The scorodite crystallite size increased from 7 to 33 nm by ripening and aggregation. Precipitates, resulting from continuous synthesis at pH 4.5 from solutions having Fe/As molar ratios ranging from 1 to 4 and resembling the compounds referred to as ferric arsenate, arsenical ferrihydrite and As-rich hydrous ferric oxide in the literature, represent variable mixtures of ferric arsenate and ferrihydrite. When the Fe/As ratio increases, the proportion of ferrihydrite increases at the expense of ferric arsenate. Arsenate adsorption appears to retard

  2. Studies on the controllable transformation of ferrihydrite

    SciTech Connect

    Liu Hui; Ma, Miaorui; Qin, Mei; Yang, Lijuan; Wei, Yu

    2010-09-15

    Ferrihydrite was prepared by two different procedures. Ferrihydrite-1 was prepared by dropping NaOH solution into Fe(III) solution. Ferrihydrite-2 was prepared by adding Fe(III) and NaOH solutions into a certain volume of water simultaneously. Our earlier results obtained at {approx}100 {sup o}C have shown that the structure of ferrihydrite-2 favors its solid state transformation mechanism. Further research reveals that the structure of ferrihydrite-2 favors its dissolution re-crystallization mechanism at a temperature of {<=}60 {sup o}C. Based on the transformation mechanism of ferrihydrite at different temperatures, the controllable transformation from ferrihydrite to various iron (hydr)oxides such as lepidocrocite, goethite, hematite and magnetite can be achieved by adjusting the pH, transformation temperature, transformation time, the amount of Fe(II) as well as the preparation procedures of ferrihydrite. The results in the present paper give a nice example that the transformation of a precursor can be controlled with the help of mechanism. - Graphical abstract: The transformations from ferrihydrite to lepidocrocite, goethite, hematite or magnetite can be controlled with the help of mechanism.

  3. Arsenic Repartitioning during Biogenic Sulfidization and Transformation of Ferrihydrite

    SciTech Connect

    Kocar, B.; Borch, T; Fendorf, S

    2010-01-01

    Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within the zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II){sub (aq)} concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III){sub (s)} depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.

  4. Arsenic repartitioning during biogenic sulfidization and transformation of ferrihydrite

    SciTech Connect

    Kocar, Benjamin D.; Borch, Thomas; Fendorf, Scott

    2012-04-30

    Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within the zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II)(aq) concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III)(s) depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.

  5. Arsenic repartitioning during biogenic sulfidization and transformation of ferrihydrite

    NASA Astrophysics Data System (ADS)

    Kocar, Benjamin D.; Borch, Thomas; Fendorf, Scott

    2010-02-01

    Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within the zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II) (aq) concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III) (s) depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.

  6. Sulfidogenesis Controls on Ferrihydrite Transformation and Repartitioning of Sorbed Arsenic

    NASA Astrophysics Data System (ADS)

    Kocar, B. D.; Fendorf, S.

    2007-12-01

    Iron (hydr)oxides are ubiquitous sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here, we examine diverging pathways of solid phase iron (Fe) transformation during sulfate reduction in the presence of varying As loadings. Columns initially containing As(V)- ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Additionally, abiotic batch reaction experiments were conducted to examine Fe secondary products rapidly formed during sulfidization of As-loaded ferrihydrite. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed within column solids possessing low As(V) surface coverage (10% of the adsorption maximum). Column experiments illustrated that at high As(V) surface coverage (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. The dominant Fe solid-phase transformation products at low As coverage include amorphous FeS within the zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II)aq concentrations exceed 1 mM. Arsenic(V) is reduced to As(III) and displaced from the zone of sulfidogenesis and Fe(III)s depletion. At higher As coverage, green rust carbonate, as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Abiotic batch reactor experiments illustrate that As is readily released from ferrihydrite during sulfidization, and that low As loadings yield initial Fe secondary products of lepidocrocite and FeS, while high loadings inhibit rapid secondary Fe mineral formation. Our observations illustrate that

  7. Effect of solution and solid-phase conditions on the Fe(II)-accelerated transformation of ferrihydrite to lepidocrocite and goethite.

    PubMed

    Boland, Daniel D; Collins, Richard N; Miller, Christopher J; Glover, Chris J; Waite, T David

    2014-05-20

    Aqueous ferrous iron (Fe(II)) accelerates the transformation of ferrihydrite into secondary, more crystalline minerals however the factors controlling the rate and, indeed, the underlying mechanism of this transformation process remain unclear. Here, we present the first detailed study of the kinetics of the Fe(II)-accelerated transformation of ferrihydrite to goethite, via lepidocrocite, for a range of pH and Fe(II) concentrations and, from the results obtained, provide insight into the factors controlling the transformation rate and the processes responsible for transformation. A reaction scheme for the Fe(II)-accelerated secondary mineralization of ferrihydrite is developed in which an Fe(II) atom attaches to the ferrihydrite surface where it is immediately oxidized to Fe(III) with the resultant electron transferred, sequentially, to other iron oxyhydroxide Fe(III) atoms before release to solution as Fe(II). This freshly precipitated Fe(III) forms the nuclei for the formation of secondary minerals and also facilitates the ongoing uptake of Fe(II) from solution by creation of fresh surface sites. The concentration of solid-associated Fe(II) and the rate of transport of Fe(II) to the oxyhydroxide surface appear to determine which particular secondary minerals form and their rates of formation. Lepidocrocite growth is enhanced at lower solid-associated Fe(II) concentrations while conditions leading to more rapid uptake of Fe(II) from solution lead to higher goethite growth rates.

  8. Transformation of ferrihydrite in the presence or absence of trace Fe(II): The effect of preparation procedures of ferrihydrite

    SciTech Connect

    Liu Hui; Li Ping; Lu Bin; Wei Yu; Sun Yuhan

    2009-07-15

    Two-line ferrihydrite was prepared by two different procedures. In procedure 1, which is widely used, ferrihydrite (named as ferrihydrite-1) was prepared by droping NaOH solution into Fe(III) solution. In procedure 2, which is rarely reported, ferrihydrite (named as ferrihydrite-2) was prepared by adding Fe(III) and NaOH solutions into a certain volume of water simultaneously. The results showed that mixing procedures of Fe(III) and alkaline were critical in the sub-microstructures and the conversion mechanisms of ferrihydrites in the presence or absence of trace Fe(II). The sub-microstructure of ferrihydrite-1 favored the mechanism of its dissolution re-crystallization and hematite nanoparticles with rough surface were obtained. The sub-microstructure of ferrihydrite-2 favored the solid state transformation from ferrihydrite to hematite and hematite nanoparticles with smooth surface were formed. These research results will be helpful for us to control the synthesis of hematite nanoparticles with different surface state. - Graphical abstract: Ferrihydrites prepared by mixing Fe{sup 3+} and NaOH solutions according to different procedures can rapidly transform into hematite particles with different surface structures in the presence of trace Fe(II).

  9. Fe(II)-catalyzed Transformation of OM-ferrihydrite Complexes: Impacts on C Dynamics and As Oxidation

    NASA Astrophysics Data System (ADS)

    Chen, C.

    2015-12-01

    Aqueous Fe(II) is known to catalyze the abiotic transformation of ferrihydrite to more stable Fe minerals. While ferrihydrite within most natural environments contains high contents of adsorbed or coprecipitated organic matter (OM), little is known regarding the impact of OM on Fe(II)-catalyzed transformation of ferrihydrite and its consequences for C and metal(oid) dynamics. In this study, we investigated the impacts of adsorbed and coprecipitated OM on the extent and the secondary mineral profiles of Fe(II)-induced ferrihydrite transformation and subsequent C dynamics and As(III) oxidation. The effects of OM types (dissolved organic matter (DOM) vs. polysaccharides) were also compared. Regardless of OM types, both adsorbed and coprecipitated OM resulted in a linear decrease in ferrihydrite transformation with increasing C/Fe ratios. At similar C/Fe ratios, a greater degree of ferrihydrite transformation was observed for the presence of EPS than DOM. Regardless of OM types, the difference in the Fe(II)-catalyzed ferrihydrite was small between adsorbed and coprecipitated OM. DOM impeded goethite and magnetite formation and stimulated lepidocrocite formation, whereas EPS did not alter the secondary Fe minerals formed from transformation of ferrihydrite and goethite was the major secondary Fe minerals in the presence of EPS. Adsorption of As(III) impeded goethite formation and increased the formation of lepidocrcote. The solid-phase C content remained unchanged after reaction, suggesting that OM remains associated with Fe minerals following ferrihydrite transformation to more stable Fe minerals. However, C desorbability by H2PO4- from the resulting Fe minerals following reaction was enhanced implying that Fe(II)-catalyzed transformation of ferrihydrite may decrease the stability of OM in natural environments under moderately reducing conditions. In addition, regardless of DOM or EPS, the presence of OM decreased the degree of As(III) oxidation following Fe

  10. Influence of Coprecipitated Organic Matter on Fe2+(aq) -Catalyzed Transformation of Ferrihydrite: Implications for Carbon Dynamics

    SciTech Connect

    Chen, Chunmei; Kukkadapu, Ravi K.; Sparks, Donald L.

    2015-08-10

    The poorly crystalline Fe(III) hydroxide ferrihydrite is an important sink for organic matter (OM), nutrients and contaminants in soils and sediments. Aqueous Fe(II) is known to catalyze the transformation of ferrihydrite to more crystalline and thus less reactive phases. While coprecipitation of OM with ferrihydrite could be a common process in many environments due to changes in pH, redox potential or ionic strength, little is known about the impacts of coprecipitated OM on Fe(II)-catalyzed ferrihydrite transformation and its consequences for C dynamics. Accordingly, we explored the extent and pathways of Fe(II)-induced transformation of OM-ferrihydrite coprecipitates and subsequent C mobility. Mössbauer spectroscopic results indicated that the coprecipitated OM within ferrihydrite weakened the inter-particle magnetic interactions and decreased average particle size. The coprecipitated OM resulted in diminished Fe(II)-induced ferrihydrite transformation and thus preservation of ferrihydrite. The secondary mineral profiles upon Fe(II) reaction with ferrihydrite were a function of OM content and Fe(II) concentration. At low Fe(II) levels, OM completely inhibited goethite formation and stimulated lepidocrocite formation. At high Fe(II) levels, whereas goethite was formed in the presence of OM, OM reduced the amount of goethite and magnetite formation and increased the formation of lepidocrcocite. The solid-phase C content remained unchanged after reaction, while OM desorpability by H2PO4- was enhanced following reaction of OM-ferrihydrites with aqueous Fe(II). These findings provide insights into the reactivity of natural ferrihydrite containing OM in soils and sediments and the subsequent impact on mineral evolution and C dynamics.

  11. Detailed magnetic monitoring of the enhanced magnetism of ferrihydrite along its progressive transformation into hematite

    NASA Astrophysics Data System (ADS)

    Gutiérrez, L.; Barrón, V.; Andrés-Vergés, M.; Serna, C. J.; Veintemillas-Verdaguer, S.; Morales, M. P.; Lázaro, F. J.

    2016-06-01

    Under certain aging conditions, ferrihydrite evolves into hematite through intermediate products of enhanced magnetism. Although the magnetic properties of the end product, hematite, are to date satisfactorily known, those of ferrihydrite (and especially the products of its progressive aging) are not sufficiently explored. To this end, magnetic experiments, conducted mostly by using alternating magnetic fields, have been performed. The results reveal that two-line ferrihydrite exhibits conspicuous low-temperature spin glass behavior, a new finding that, on the other hand, could be expected given the previous microstructural observations that described this mineral as a very disordered gel. Upon aging, a progressive increase of the effective magnetic moment per iron ion is detected, in agreement with previous observations that ascribed ferrimagnetic character to an intermediate crystalline phase (sometime called ferriferrihydrite) that disappears just before the full transformation into hematite. Transmission electron microscopy observations suggest that this intermediate crystalline phase nucleates at the expense of the primordial gel, remaining physically attached to it until complete transformation into hematite. This microstructural picture appears well supported as, upon aging, the glassy magnetic dynamics found in ferrihydrite persists for the aged products even when dispersed in a nonmagnetic matrix, very likely because part of the so grown ferrimagnetic nanoparticles form aggregates within remains of the nontransformed gel. We propose a coherent model of ferrihydrite aging, based on integrated microstructural and magnetic observations, which is useful for the identification of aging products in geological and biological environments.

  12. Aggregate-scale spatial heterogeneity in reductive transformation of ferrihydrite resulting from coupled biogeochemical and physical processes

    NASA Astrophysics Data System (ADS)

    Pallud, C.; Masue-Slowey, Y.; Fendorf, S.

    2010-05-01

    Iron (hydr)oxides are ubiquitous in soils and sediments and play a dominant role in the geochemistry of surface and subsurface environments. Their fate depends on local environmental conditions, which in structured soils may vary significantly over short distances due to mass-transfer limitations on solute delivery and metabolite removal. In the present study, artificial soil aggregates were used to investigate the coupling of physical and biogeochemical processes affecting the spatial distribution of iron (Fe) phases resulting from reductive transformation of ferrihydrite. Spherical aggregates made of ferrihydrite-coated sand were inoculated with the dissimilatory Fe-reducing bacterium Shewanella putrefaciens strain CN-32, and placed into a flow reactor, the reaction cell simulates a diffusion-dominated soil aggregate surrounded by an advective flow domain. The spatial and temporal evolution of secondary mineralization products resulting from dissimilatory Fe reduction of ferrihydrite were followed within the aggregates in response to a range of flow rates and lactate concentrations. Strong radial variations in the distribution of secondary phases were observed owing to diffusively controlled delivery of lactate and efflux of Fe(II) and bicarbonate. In the aggregate cortex, only limited formation of secondary Fe phases were observed over 30 d of reaction, despite high rates of ferrihydrite reduction. Under all flow conditions tested, ferrihydrite transformation was limited in the cortex (70-85 mol.% Fe remained as ferrihydrite) because metabolites such as Fe(II) and bicarbonate were efficiently removed in outflow solutes. In contrast, within the inner fractions of the aggregate, limited mass-transfer results in metabolite (Fe(II) and bicarbonate) build-up and the consummate transformation of ferrihydrite - only 15-40 mol.% Fe remained as ferrihydrite after 30 d of reaction. Goethite/lepidocrocite, and minor amounts of magnetite, formed in the aggregate mid

  13. Kinetics of Fe(II)-catalyzed transformation of 6-line ferrihydrite under anaerobic flow conditions

    SciTech Connect

    Yang, L.; Steefel, C.I.; Marcus, M.A.; Bargar, J.R.

    2010-04-01

    The readsorption of ferrous ions produced by the abiotic and microbially-mediated reductive dissolution of iron oxy-hydroxides drives a series of transformations of the host minerals. To further understand the mechanisms by which these transformations occur and their kinetics within a microporous flow environment, flow-through experiments were conducted in which capillary tubes packed with ferrihydrite-coated glass spheres were injected with inorganic Fe(II) solutions under circumneutral pH conditions at 25 C. Synchrotron X-ray diffraction was used to identify the secondary phase(s) formed and to provide data for quantitative kinetic analysis. At concentrations at and above 1.8 mM Fe(II) in the injection solution, magnetite was the only secondary phase formed (no intermediates were detected), with complete transformation following a nonlinear rate law requiring 28 hours and 150 hours of reaction at 18 and 1.8 mM Fe(II), respectively. However, when the injection solution consisted of 0.36 mM Fe(II), goethite was the predominant reaction product and formed much more slowly according to a linear rate law, while only minor magnetite was formed. When the rates are normalized based on the time to react half of the ferrihydrite on a reduced time plot, it is apparent that the 1.8 mM and 18 mM input Fe(II) experiments can be described by the same reaction mechanism, while the 0.36 input Fe(II) experiment is distinct. The analysis of the transformation kinetics suggest that the transformations involved an electron transfer reaction between the aqueous as well as sorbed Fe(II) and ferrihydrite acting as a semiconductor, rather than a simple dissolution and recrystallization mechanism. A transformation mechanism involving sorbed inner sphere Fe(II) alone is not supported, since the essentially equal coverage of sorption sites in the 18 mM and 1.8 mM Fe(II) injections cannot explain the difference in the transformation rates observed.

  14. Understanding the biological stabilization of ferrihydrite and its transformation to magnetite

    NASA Astrophysics Data System (ADS)

    Gordon, Lyle; Joester, Derk

    2013-03-01

    The biosynthesis of magnetite in the chiton tooth begins with the formation of ferrihydrite, which is transformed into magnetite. This strategy, which employs crystallization of a precursor into the desired polymorph, is generalized across a range of organisms. However, the specific biological factors that control the transformation are not known. Our results employing atom probe tomography of chiton tooth magnetite revealed the presence of acidic proteins binding sodium and magnesium ions associated with chitin nanofibers. Using a model system we are investigating the influence of organic and inorganic additives on the stabilization of ferrihydrite and the transformation to magnetite. I will discuss the influence of a range of organic and inorganic additives on the formation and transformation of ferrihydrite within the gel. We have found that acidic polymers stabilize ferrihydrite and prevent the formation of the crystalline polymorphs. Transformation of the ferrihydrite to magnetite upon addition of ferrous iron is observed as early as 30 minutes. Taken together, the contribution of these factors to magnetite biomineralization in the presence of an organic matrix will help to elucidate biological mechanisms for nucleation, stabilization, and transformation of iron oxides.

  15. Investigation of solid phase upon γ-irradiation of ferrihydrite-ethanol suspension

    NASA Astrophysics Data System (ADS)

    Jurkin, Tanja; Zadro, Krešo; Gotić, Marijan; Musić, Svetozar

    2011-07-01

    Ferrihydrite (FH) nanoparticles were synthesised and subjected to γ-irradiation in the form of FH-ethanol suspension. The dose rate of γ-radiation was ˜16 kGy/h and the samples were irradiated to doses of up to 2590 kGy. γ-irradiation of FH-ethanol suspensions did not cause the transformation of FH to any of the other iron oxide phases. Likewise, neither the Mössbauer and FT-IR spectroscopy nor the quantitative analysis using Energy Dispersive X-ray Spectroscopy gave any evidence of structural changes of FH upon γ-irradiation. C, H analysis showed that the C concentration in FH gradually increased with dose and was higher in γ-irradiated FH samples than in non-irradiated FH sample. This finding suggested that carbon in FH originated from ethanol degradation. The H concentration in FH gradually increased to the dose of up to 340 kGy and then slightly decreased. Magnetic measurements showed a progressive decrease in magnetisation with an increase in γ-irradiation. The results of magnetic measurements and C, H analysis suggested the carbonisation of FH surface. It was supposed that γ-irradiation of FH-ethanol suspension reductively decomposed ethanol thus generating unsaturated hydrocarbons and acetylides, which in turn formed a conjugate iron complex, thus carbonating the FH surface. The carbonisation of the FH surface prevented FH transformation to other iron oxide phases.

  16. Effect of Humic Substances on the Trapping and Transformations of U(VI) by Ferrihydrite

    NASA Astrophysics Data System (ADS)

    Dublet, G.; Brown, G. E.; Bargar, J.; Fendorf, S. E.; Janot, N.

    2013-12-01

    The Old Rifle DOE site in Colorado was a major site for milling uranium ore. U concentrations up to 1.8 uM persist in the Rifle aquifer, even after 'cleaning' the waste source of contaminations [1]. Understanding the behavior of U(VI) in this anthropogenically perturbed system is crucial for controlling the level of U contamination. Direct investigations of U speciation at this site have shown that U is associated with a wide variety of minerals as well as with natural organic matter (NOM) [2]. NOM has multiple functional groups which can be highly reactive with respect to aqueous metal ions, including actinides. Such interactions result in the formation of organo-mineral-metal (ternary) complexes and catalyze redox transformations; in addition, they can enhance mineral dissolution and metal transport [3,4,5]. In the complex soil/sediment system, aqueous, mineral, and organic phases are intimately mixed and their interactions are difficult to characterize by direct investigation [1]. The nanoparticulate iron hydroxide ferrihydrite (Fh), which is ubiquitous in many natural soils and highly reactive toward metal ions, is expected to significantly influence the fate of U in natural soils and is abundant in the subsurface at the Rifle site. NOM is also abundant at this site; however, little is known about the effect of NOM associated with ferrihydrite on the fate of U in such subsurface environments. To date, simple model systems composed mainly of two components (Fh and NOM) [6], (U and NOM or simple organic molecules) [7], or (Fh and U) [8,9], and more rarely composed of three components [10,11] have been studied in an effort to understand interactions among these components. In order to extend this earlier work to ternary systems, we have carried out batch reactions of U, a humic acid standard - Eliott soil humic acid (ESHA), and Fh under conditions that mimic those in the subsurface at Rifle. We have used U L3- and Fe K-edge XANES and EXAFS spectroscopy coupled

  17. Controlled Growth of Ferrihydrite Branched Nanosheet Arrays and Their Transformation to Hematite Nanosheet Arrays for Photoelectrochemical Water Splitting.

    PubMed

    Ji, Mei; Cai, Jinguang; Ma, Yurong; Qi, Limin

    2016-02-17

    The morphology engineering represents an alternative route toward efficient hematite photoanodes for photoelectrochemical (PEC) water splitting without changing the chemical composition. In this work, a facile and mild solvothermal synthesis of unique ferrihydrite branched nanosheet arrays vertically aligned on FTO substrate was achieved at around 100 °C. The hierarchical branched ferrihydrite nanosheet arrays consisted of tiny branches up to 40 nm in length grown almost vertically on stem nanosheets ∼10 nm in thickness. Moreover, the variation of the morphology of the ferrihydrite nanostructures from bare nanosheet arrays through branched nanosheet arrays to dense branched structures can be readily achieved through the regulation of the reaction time and temperature. The obtained ferrihydrite branched nanosheet arrays can be in situ transformed into α-Fe2O3 nanosheet arrays with small surface protrusions upon annealing at 550 °C. After a simple postgrowth Ti-doping process, the resulting Ti-doped α-Fe2O3 nanosheet arrays showed a good PEC performance for water splitting with a photocurrent density of 1.79 mA/cm(2) at 1.6 V vs RHE under AM 1.5G illumination (100 mW/cm(2)). In contrast, the Ti-doped irregular aggregates of the α-Fe2O3 nanograins transformed from dense ferrihydrite branched structures exhibited a much lower photocurrent density (0.41 mA/cm(2) at 1.6 V vs RHE), demonstrating the important influence of the morphology of α-Fe2O3 photoanodes on the PEC performance. PMID:26517010

  18. Controlled Growth of Ferrihydrite Branched Nanosheet Arrays and Their Transformation to Hematite Nanosheet Arrays for Photoelectrochemical Water Splitting.

    PubMed

    Ji, Mei; Cai, Jinguang; Ma, Yurong; Qi, Limin

    2016-02-17

    The morphology engineering represents an alternative route toward efficient hematite photoanodes for photoelectrochemical (PEC) water splitting without changing the chemical composition. In this work, a facile and mild solvothermal synthesis of unique ferrihydrite branched nanosheet arrays vertically aligned on FTO substrate was achieved at around 100 °C. The hierarchical branched ferrihydrite nanosheet arrays consisted of tiny branches up to 40 nm in length grown almost vertically on stem nanosheets ∼10 nm in thickness. Moreover, the variation of the morphology of the ferrihydrite nanostructures from bare nanosheet arrays through branched nanosheet arrays to dense branched structures can be readily achieved through the regulation of the reaction time and temperature. The obtained ferrihydrite branched nanosheet arrays can be in situ transformed into α-Fe2O3 nanosheet arrays with small surface protrusions upon annealing at 550 °C. After a simple postgrowth Ti-doping process, the resulting Ti-doped α-Fe2O3 nanosheet arrays showed a good PEC performance for water splitting with a photocurrent density of 1.79 mA/cm(2) at 1.6 V vs RHE under AM 1.5G illumination (100 mW/cm(2)). In contrast, the Ti-doped irregular aggregates of the α-Fe2O3 nanograins transformed from dense ferrihydrite branched structures exhibited a much lower photocurrent density (0.41 mA/cm(2) at 1.6 V vs RHE), demonstrating the important influence of the morphology of α-Fe2O3 photoanodes on the PEC performance.

  19. Characterization of the Adsorption of Nucleic Acid Bases onto Ferrihydrite via Fourier Transform Infrared and Surface-Enhanced Raman Spectroscopy and X-ray Diffractometry.

    PubMed

    Canhisares-Filho, José E; Carneiro, Cristine E A; de Santana, Henrique; Urbano, Alexandre; da Costa, Antonio C S; Zaia, Cássia T B V; Zaia, Dimas A M

    2015-09-01

    Minerals could have played an important role in concentration, protection, and polymerization of biomolecules. Although iron is the fourth most abundant element in Earth's crust, there are few works in the literature that describe the use of iron oxide-hydroxide in prebiotic chemistry experiments. In the present work, the interaction of adenine, thymine, and uracil with ferrihydrite was studied under conditions that resemble those of prebiotic Earth. At acidic pH, anions in artificial seawater decreased the pH at the point of zero charge (pHpzc) of ferrihydrite; and at basic pH, cations increased the pHpzc. The adsorption of nucleic acid bases onto ferrihydrite followed the order adenine > uracil > thymine. Adenine adsorption peaked at neutral pH; however, for thymine and uracil, adsorption increased with increasing pH. Electrostatic interactions did not appear to play an important role on the adsorption of nucleic acid bases onto ferrihydrite. Adenine adsorption onto ferrihydrite was higher in distilled water compared to artificial seawater. After ferrihydrite was mixed with artificial seawaters or nucleic acid bases, X-ray diffractograms and Fourier transform infrared spectra did not show any change. Surface-enhanced Raman spectroscopy showed that the interaction of adenine with ferrihydrite was not pH-dependent. In contrast, the interactions of thymine and uracil with ferrihydrite were pH-dependent such that, at basic pH, thymine and uracil lay flat on the surface of ferrihydrite, and at acidic pH, thymine and uracil were perpendicular to the surface. Ferrihydrite adsorbed much more adenine than thymine; thus adenine would have been better protected against degradation by hydrolysis or UV radiation on prebiotic Earth. PMID:26393397

  20. Characterization of the Adsorption of Nucleic Acid Bases onto Ferrihydrite via Fourier Transform Infrared and Surface-Enhanced Raman Spectroscopy and X-ray Diffractometry.

    PubMed

    Canhisares-Filho, José E; Carneiro, Cristine E A; de Santana, Henrique; Urbano, Alexandre; da Costa, Antonio C S; Zaia, Cássia T B V; Zaia, Dimas A M

    2015-09-01

    Minerals could have played an important role in concentration, protection, and polymerization of biomolecules. Although iron is the fourth most abundant element in Earth's crust, there are few works in the literature that describe the use of iron oxide-hydroxide in prebiotic chemistry experiments. In the present work, the interaction of adenine, thymine, and uracil with ferrihydrite was studied under conditions that resemble those of prebiotic Earth. At acidic pH, anions in artificial seawater decreased the pH at the point of zero charge (pHpzc) of ferrihydrite; and at basic pH, cations increased the pHpzc. The adsorption of nucleic acid bases onto ferrihydrite followed the order adenine > uracil > thymine. Adenine adsorption peaked at neutral pH; however, for thymine and uracil, adsorption increased with increasing pH. Electrostatic interactions did not appear to play an important role on the adsorption of nucleic acid bases onto ferrihydrite. Adenine adsorption onto ferrihydrite was higher in distilled water compared to artificial seawater. After ferrihydrite was mixed with artificial seawaters or nucleic acid bases, X-ray diffractograms and Fourier transform infrared spectra did not show any change. Surface-enhanced Raman spectroscopy showed that the interaction of adenine with ferrihydrite was not pH-dependent. In contrast, the interactions of thymine and uracil with ferrihydrite were pH-dependent such that, at basic pH, thymine and uracil lay flat on the surface of ferrihydrite, and at acidic pH, thymine and uracil were perpendicular to the surface. Ferrihydrite adsorbed much more adenine than thymine; thus adenine would have been better protected against degradation by hydrolysis or UV radiation on prebiotic Earth.

  1. The transformation of ferrihydrite in the presence of trace Fe(II): The effect of the ammonia, amine and the coordination ions of Fe(III)

    SciTech Connect

    Liu Hui; Yang Lijuan; Ma Miaorui; Li Ping; Wei Yu

    2010-03-15

    This work examined Fe(II)-induced transformation of ferrihydrite in the presence of ammonia, amine and the coordination ions of Fe(III). Our earlier results showed that ferrihydrite transformed into the mixture of lepidocrocite, goethite and/or hematite in the presence of trace Fe(II) and absence of ammonia and similar species. However, the formation of lepidocrocite was restrained when using ammonia as precipitants. When introducing some amines (e.g. ethanolamine and diethanolamine) and some coordination ions (e.g. F{sup -} and C{sub 2}O{sub 4}{sup 2-} ions) into the reaction system, a similar effect on the transformation of ferrihydrite was found. Probably, the complexes formed between Fe(III) and those additives favor the formation of goethite. At the same time, the introduction of these additives hinders Fe(II) from interacting with ferrihydrite, which makes the catalytic dissolution of ferrihydrite be limited, thus, the formation of lepidocrocite be restrained. - Graphical Abstract: Fe(II)-induced transformation of ferrihydrite in the presence of ammonia, amine and coordination ions of Fe(III) was studied. The introduction of the additives favors the formation of goethite.

  2. Control of Earth-like magnetic fields on the transformation of ferrihydrite to hematite and goethite.

    PubMed

    Jiang, Zhaoxia; Liu, Qingsong; Dekkers, Mark J; Barrón, Vidal; Torrent, José; Roberts, Andrew P

    2016-01-01

    Hematite and goethite are the two most abundant iron oxides in natural environments. Their formation is controlled by multiple environmental factors; therefore, their relative concentration has been used widely to indicate climatic variations. In this study, we aimed to test whether hematite and goethite growth is influenced by ambient magnetic fields of Earth-like values. Ferrihydrite was aged at 95 °C in magnetic fields ranging from ~0 to ~100 μT. Our results indicate a large influence of the applied magnetic field on hematite and goethite growth from ferrihydrite. The synthesized products are a mixture of hematite and goethite for field intensities <~60 μT. Higher fields favour hematite formation by accelerating ferrimagnetic ferrihydrite aggregation. Additionally, hematite particles growing in a controlled magnetic field of ~100 μT appear to be arranged in chains, which may be reduced to magnetite keeping its original configuration, therefore, the presence of magnetic particles in chains in natural sediments cannot be used as an exclusive indicator of biogenic magnetite. Hematite vs. goethite formation in our experiments is influenced by field intensity values within the range of geomagnetic field variability. Thus, geomagnetic field intensity could be a source of variation when using iron (oxyhydr-)oxide concentrations in environmental magnetism. PMID:27458091

  3. Control of Earth-like magnetic fields on the transformation of ferrihydrite to hematite and goethite

    NASA Astrophysics Data System (ADS)

    Jiang, Zhaoxia; Liu, Qingsong; Dekkers, Mark J.; Barrón, Vidal; Torrent, José; Roberts, Andrew P.

    2016-07-01

    Hematite and goethite are the two most abundant iron oxides in natural environments. Their formation is controlled by multiple environmental factors; therefore, their relative concentration has been used widely to indicate climatic variations. In this study, we aimed to test whether hematite and goethite growth is influenced by ambient magnetic fields of Earth-like values. Ferrihydrite was aged at 95 °C in magnetic fields ranging from ~0 to ~100 μT. Our results indicate a large influence of the applied magnetic field on hematite and goethite growth from ferrihydrite. The synthesized products are a mixture of hematite and goethite for field intensities <~60 μT. Higher fields favour hematite formation by accelerating ferrimagnetic ferrihydrite aggregation. Additionally, hematite particles growing in a controlled magnetic field of ~100 μT appear to be arranged in chains, which may be reduced to magnetite keeping its original configuration, therefore, the presence of magnetic particles in chains in natural sediments cannot be used as an exclusive indicator of biogenic magnetite. Hematite vs. goethite formation in our experiments is influenced by field intensity values within the range of geomagnetic field variability. Thus, geomagnetic field intensity could be a source of variation when using iron (oxyhydr-)oxide concentrations in environmental magnetism.

  4. Control of Earth-like magnetic fields on the transformation of ferrihydrite to hematite and goethite

    PubMed Central

    Jiang, Zhaoxia; Liu, Qingsong; Dekkers, Mark J.; Barrón, Vidal; Torrent, José; Roberts, Andrew P.

    2016-01-01

    Hematite and goethite are the two most abundant iron oxides in natural environments. Their formation is controlled by multiple environmental factors; therefore, their relative concentration has been used widely to indicate climatic variations. In this study, we aimed to test whether hematite and goethite growth is influenced by ambient magnetic fields of Earth-like values. Ferrihydrite was aged at 95 °C in magnetic fields ranging from ~0 to ~100 μT. Our results indicate a large influence of the applied magnetic field on hematite and goethite growth from ferrihydrite. The synthesized products are a mixture of hematite and goethite for field intensities <~60 μT. Higher fields favour hematite formation by accelerating ferrimagnetic ferrihydrite aggregation. Additionally, hematite particles growing in a controlled magnetic field of ~100 μT appear to be arranged in chains, which may be reduced to magnetite keeping its original configuration, therefore, the presence of magnetic particles in chains in natural sediments cannot be used as an exclusive indicator of biogenic magnetite. Hematite vs. goethite formation in our experiments is influenced by field intensity values within the range of geomagnetic field variability. Thus, geomagnetic field intensity could be a source of variation when using iron (oxyhydr-)oxide concentrations in environmental magnetism. PMID:27458091

  5. The Mineralogic Transformation of Ferrihydrite Induced by Heterogeneous Reaction with Bioreduced Anthraquinone Disulfonate (AQDS) and the Role of Phosphate

    SciTech Connect

    Zachara, John M.; Kukkadapu, Ravi K.; Peretyazhko, Tetyana; Bowden, Mark E.; Wang, Chong M.; Kennedy, David W.; Moore, Dean A.; Arey, Bruce W.

    2011-10-12

    Anthraquinone-2-6-disulfonate (AQDS) enhances electron donor utilization and mineral product crystallization in studies of Fe(III) oxide reductive mineralization by metal reducing bacteria (MRB) through heterogeneous redox reaction. In spite of the strong effect of AQDS in these systems, little information exits on its direct role in reductive mineralization. To provide such insights, bioreduced AQDS (AH2DS; dihydro-anthraquinone) was reacted with a 2-line, Si-substituted ferrihydrite under anoxic conditions at neutral pH in PIPES buffer. Phosphate (P) and bicarbonate (C); common adsorptive oxyanions and media/buffer components known to effect ferrihydrite mineralization; and Fe(II)aq (as a catalytic mineralization agent) were used in comparative experiments. Heterogeneous AH2DS oxidation coupled with Fe(III) reduction occurred within 0.13-1 day, with mineralogic transformation occurring thereafter. The product suite included lepidocrocite, goethite, and/or magnetite, with proportions varing with reductant:oxidant ratio (r:o) and the presence of P or C. Lepidocrocite was the primary product at low r:o in the absence of P or C, with evidence for multiple formation pathways. P inhibited reductive recrystallization, while C promoted goethite formation. Stoichiometric magnetite was the sole product at higher r:o in the absence and presence of P. Lepidocrocite was the primary mineralization product in the Fe(II)aq system, with magnetite observed at near equal amounts when Fe(II) was high [Fe(II)/Fe(III)]=0.5 and P was absent. P had a greater effect on reductive mineralization in the Fe(II)aq system, while AQDS was more effective than Fe(II)aq in promoting magnetite formation. The direct AH2DS-driven reductive reaction pathway produced mineral products that were different from AH2DS-ferrihydite-MRB systems, particularly in presence of P.

  6. Ordered ferrimagnetic form of ferrihydrite reveals links among structure, composition, and magnetism

    SciTech Connect

    Michel, F. Marc; Barrón, Vidal; Torrent, José; Morales, María P.; Serna, Carlos J.; Boily, Jean-François; Liu, Qingsong; Ambrosini, Andrea; Cismasu, A. Cristina; Brown, Jr., Gordon E.

    2010-11-19

    The natural nanomineral ferrihydrite is an important component of many environmental and soil systems and has been implicated as the inorganic core of ferritin in biological systems. Knowledge of its basic structure, composition, and extent of structural disorder is essential for understanding its reactivity, stability, and magnetic behavior, as well as changes in these properties during aging. Here we investigate compositional, structural, and magnetic changes that occur upon aging of '2-line' ferrihydrite in the presence of adsorbed citrate at elevated temperature. Whereas aging under these conditions ultimately results in the formation of hematite, analysis of the atomic pair distribution function and complementary physicochemical and magnetic data indicate formation of an intermediate ferrihydrite phase of larger particle size with few defects, more structural relaxation and electron spin ordering, and pronounced ferrimagnetism relative to its disordered ferrihydrite precursor. Our results represent an important conceptual advance in understanding the nature of structural disorder in ferrihydrite and its relation to the magnetic structure and also serve to validate a controversial, recently proposed structural model for this phase. In addition, the pathway we identify for forming ferrimagnetic ferrihydrite potentially explains the magnetic enhancement that typically precedes formation of hematite in aerobic soil and weathering environments. Such magnetic enhancement has been attributed to the formation of poorly understood, nano-sized ferrimagnets from a ferrihydrite precursor. Whereas elevated temperatures drive the transformation on timescales feasible for laboratory studies, our results also suggest that ferrimagnetic ferrihydrite could form naturally at ambient temperature given sufficient time.

  7. Photoinduced Oxidation of Arsenite to Arsenate on Ferrihydrite

    SciTech Connect

    N Bhandari; R Reeder; D Strongin

    2011-12-31

    The photochemistry of an aqueous suspension of the iron oxyhydroxide, ferrihydrite, in the presence of arsenite has been investigated using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray absorption near edge structure (XANES), and solution phase analysis. Both ATR-FTIR and XANES show that the exposure of ferrihydrite to arsenite in the dark leads to no change in the As oxidation state, but the exposure of this arsenite-bearing surface, which is in contact with pH 5 water, to light leads to the conversion of the majority of the adsorbed arsenite to the As(V) bearing species, arsenate. Analysis of the solution phase shows that ferrous iron is released into solution during the oxidation of arsenite. The photochemical reaction, however, shows the characteristics of a self-terminating reaction in that there is a significant suppression of this redox chemistry before 10% of the total iron making up the ferrihydrite partitions into solution as ferrous iron. The self-terminating behavior exhibited by this photochemical arsenite/ferrihydrite system is likely due to the passivation of the ferrihydrite surface by the strongly bound arsenate product.

  8. Properties of impurity-bearing ferrihydrite III. Effects of Si on the structure of 2-line ferrihydrite

    NASA Astrophysics Data System (ADS)

    Cismasu, A. Cristina; Michel, F. Marc; Tcaciuc, A. Patricia; Brown, Gordon E.

    2014-05-01

    Siliceous ferrihydrites are abundant nanoparticles in natural environments. Although it is well known that the physical properties of ferrihydrite are affected when formed in the presence of silicate oxoanions (SiO44-), the structure of siliceous ferrihydrites (SiFh), and the speciation of Si within these nanosolids are not well understood. In this study we evaluate the effects of Si (at concentrations ranging from 5 to 40 mol% Si) on synthetic ferrihydrite precipitates using structural data derived from synchrotron-based high energy X-ray scattering and pair distribution function (PDF) analysis, in combination with X-ray absorption near edge structure (XANES) spectroscopy, and transmission electron microscopy (TEM). Silicate oxoanions have a major effect on Fe(O,OH)x polyhedral polymerization and ferrihydrite particle growth, illustrated by the formation of smaller, poorly crystalline, structurally disordered/strained ferrihydrite nanocrystallites. Variation in Fh unit-cell parameters is suggested to arise from substantial particle size-induced structural disorder. As a result of this significant size-dependent structural disorder, it was not possible to identify evidence for Si4+ for Fe3+ substitution in these samples based on unit cell parameter variations or refinement of different structural models. Principal component analyses (PCA) and linear combination fits carried out on the PDFs suggest that iron partitions between several phases (e.g., ferrihydrite and an Fe-bearing amorphous silica phase (Amorph. SiO2 + Fe)) in these co-precipitates. A mechanism of co-precipitation is proposed, in which silicate binds to Fe polymers and Fh particles, thus inhibiting particle growth at low Si content. At higher Si content, SiO44- polymerization traps significant Fe, and we suggest that the occurrence of this second Fe pool limits further the availability of Fe required for ferrihydrite particle development. Such Si-ferrihydrite co-precipitates are expected to be more

  9. Ferrihydrite in soils

    NASA Astrophysics Data System (ADS)

    Vodyanitskii, Yu. N.; Shoba, S. A.

    2016-07-01

    Ferrihydrite—an ephemeral mineral—is the most active Fe-hydroxide in soils. According to modern data, the ferrihydrite structure contains tetrahedral lattice in addition to the main octahedral lattice, with 10-20% of Fe being concentrated in the former. The presence of Fe tetrahedrons influences the surface properties of this mineral. The chemical composition of ferrihydrite samples depends largely on the size of lattice domains ranging from 2 to 6 nm. Chemically pure ferrihydrite rarely occurs in the soil; it usually contains oxyanion (SiO14 4-, PO4 3-) and cation (Al3+) admixtures. Aluminum replace Fe3+ in the structure with a decrease in the mineral particle size. Oxyanions slow down polymerization of Fe3+ aquahydroxomonomers due to the films at the surface of mineral nanoparticles. Si- and Al-ferrihydrites are more resistant to the reductive dissolution than the chemically pure ferrihydrite. In addition, natural ferrihydrite contains organic substance that decreases the grain size of the mineral. External organic ligands favor ferrihydrite dissolution. In the European part of Russia, ferrihydrite is more widespread in the forest soils than in the steppe soils. Poorly crystallized nanoparticles of ferrihydrite adsorb different cations (Zn, Cu) and anions (phosphate, uranyl, arsenate) to immobilize them in soils; therefore, ferrihydrite nanoparticles play a significant role in the biogeochemical cycle of iron and other elements.

  10. Low aggregation state diminishes ferrihydrite reactivity

    NASA Astrophysics Data System (ADS)

    Braunschweig, Juliane; Heister, Katja; Meckenstock, Rainer U.

    2013-04-01

    Ferrihydrite is an abundant iron(oxy)hydroxide in soils and sediments and plays an important role in microbial iron cycling due to its high reactivity. Therefore, it is often synthesized and used in geomicrobiological and mineralogical studies. The reactivities of synthetic ferrihydrites vary between different studies and synthesis protocols. Hence, we synthesized five different ferrihydrites and characterized them with XRD, FTIR, XPS, and BET specific surface area. The reactivity of the ferrihydrite samples towards ascorbic acid was examined and compared with microbial reduction rates by Geobacter sulfurreducens. FTIR and XRD results show the presence of secondary, higher crystalline iron oxide phases like goethite and akaganeite for two samples. Consequently, those samples revealed lower biotic and abiotic reduction rates compared to pure ferrihydrite. Comparison of reduction rates with the specific surface area of all ferrihydrites showed neither correlation with abiotic reductive dissolution nor with microbial reduction. Especially one sample, characterized by a very low aggregation state and presence of secondary minerals, revealed a poor reactivity. We speculate that apart from the occurring secondary minerals also the low aggregation state played an important role. Decreasing aggregation diminishes the amount of kinks and edges on the surfaces, which are produced at contact sites in aggregates. According to dissolution theories, dissolution mainly starts at those surface defects and slows down with decreasing amount of defects. Furthermore, the non-aggregated ferrihydrite is free of micropores, a further stimulant for dissolution. Independent repetitions of experiments and syntheses according to the same protocol but without formation of secondary minerals, confirmed the low reactivity of the non-aggregated ferrihydrite. In summary, our results indicate that a decreasing aggregation state of ferrihydrite to a certain size does increase the reactivity

  11. Iron phase transformations resulting from the respiration of Shewanella putrefaciens on a mixed mineral phase

    NASA Astrophysics Data System (ADS)

    Boyanov, M. I.; O'Loughlin, E. J.; Kemner, K. M.

    2009-11-01

    The initial Fe(III) minerals and the secondary mineralization products of Shewanella putrefaciens CN32 grown in the presence of dissolved phosphate and a commercial Fe(III) oxide, nominally nanoparticulate lepidocrocite, were determined using XRD and XAFS. The starting material was transformed by the bacteria from a reddish brown, rust colour mineral to a dark green phase over 90 days. Acid extraction of the bioreduced solids with 0.75 M HCl recovered 83% of the total iron as Fe(II), leaving a solid, acid-resistant phase. The latter was identified as nanoparticulate hematite by EXAFS. Subsequently, the starting Fe(III) phase was determined to be a mixture of 60% lepidocrocite, 26% ferrihydrite, and 14% hematite, using linear combination EXAFS analysis. For the acid-extractable phase, XANES and EXAFS indicated a predominantly Fe(II) valence state and a spectrum consistent with a mixture of brucite-type minerals(e.g., green rust or ferrous hydroxide) and siderite. The observed transformations suggest that in this mixed-mineral system, lepidocrocite and ferrihydrite are readily reducible to green rust and siderite, whereas hematite is less amenable to bacterial reduction. This study also demonstrates the utility of XAFS spectroscopy in the quantitative characterization of dissimilatory metal transformations, particularly in complex systems such as nanoparticulate minerals in hydrated mineral-bacteria assemblages.

  12. Phase Transformations and Earthquakes

    NASA Astrophysics Data System (ADS)

    Green, H. W.

    2011-12-01

    Phase transformations have been cited as responsible for, or at least involved in, "deep" earthquakes for many decades (although the concept of "deep" has varied). In 1945, PW Bridgman laid out in detail the string of events/conditions that would have to be achieved for a solid/solid transformation to lead to a faulting instability, although he expressed pessimism that the full set of requirements would be simultaneously achieved in nature. Raleigh and Paterson (1965) demonstrated faulting during dehydration of serpentine under stress and suggested dehydration embrittlement as the cause of intermediate depth earthquakes. Griggs and Baker (1969) produced a thermal runaway model of a shear zone under constant stress, culminating in melting, and proposed such a runaway as the origin of deep earthquakes. The discovery of Plate Tectonics in the late 1960s established the conditions (subduction) under which Bridgman's requirements for earthquake runaway in a polymorphic transformation could be possible in nature and Green and Burnley (1989) found that instability during the transformation of metastable olivine to spinel. Recent seismic correlation of intermediate-depth-earthquake hypocenters with predicted conditions of dehydration of antigorite serpentine and discovery of metastable olivine in 4 subduction zones, suggests strongly that dehydration embrittlement and transformation-induced faulting are the underlying mechanisms of intermediate and deep earthquakes, respectively. The results of recent high-speed friction experiments and analysis of natural fault zones suggest that it is likely that similar processes occur commonly during many shallow earthquakes after initiation by frictional failure.

  13. Binary ferrihydrite catalysts

    DOEpatents

    Huffman, Gerald P.; Zhao, Jianmin; Feng, Zhen

    1996-01-01

    A method of preparing a catalyst precursor comprises dissolving an iron salt and a salt of an oxoanion forming agent, in water so that a solution of the iron salt and oxoanion forming agent salt has a ratio of oxoanion/Fe of between 0.0001:1 to 0.5:1. Next is increasing the pH of the solution to 10 by adding a strong base followed by collecting of precipitate having a binary ferrihydrite structure. A binary ferrihydrite catalyst precursor is also prepared by dissolving an iron salt in water. The solution is brought to a pH of substantially 10 to obtain ferrihydrite precipitate. The precipitate is then filtered and washed with distilled water and subsequently admixed with a hydroxy carboxylic acid solution. The admixture is mixed/agitated and the binary ferrihydrite precipitate is then filtered and recovered.

  14. Binary ferrihydrite catalysts

    DOEpatents

    Huffman, G.P.; Zhao, J.; Feng, Z.

    1996-12-03

    A method of preparing a catalyst precursor comprises dissolving an iron salt and a salt of an oxoanion forming agent, in water so that a solution of the iron salt and oxoanion forming agent salt has a ratio of oxoanion/Fe of between 0.0001:1 to 0.5:1. Next is increasing the pH of the solution to 10 by adding a strong base followed by collecting of precipitate having a binary ferrihydrite structure. A binary ferrihydrite catalyst precursor is also prepared by dissolving an iron salt in water. The solution is brought to a pH of substantially 10 to obtain ferrihydrite precipitate. The precipitate is then filtered and washed with distilled water and subsequently admixed with a hydroxy carboxylic acid solution. The admixture is mixed/agitated and the binary ferrihydrite precipitate is then filtered and recovered. 3 figs.

  15. Microbial sulfidogenesis in ferrihydrite-rich environments: Effects on iron mineralogy and arsenic mobility

    NASA Astrophysics Data System (ADS)

    Burton, Edward D.; Johnston, Scott G.; Bush, Richard T.

    2011-06-01

    Microbial sulfidogenesis plays a potentially important role in Fe and As biogeochemistry within wetland soils, sediments and aquifers. This study investigates the specific effects of microbial sulfidogenesis on Fe mineralogy and associated As mobility in mildly acidic (pH 6) and mildly basic (pH 8) advective-flow environments. A series of experiments were conducted using advective-flow columns, with an initial solid-phase comprising As(III)-bearing ferrihydrite-coated quartz sand. Columns for each pH treatment were inoculated with the sulfate-reducing bacteria Desulfovibrio vulgaris, and were compared to additional abiotic control columns. Over a period of 28 days, microbial sulfidogenesis (as coupled to the incomplete oxidation of lactate) caused major changes in Fe mineralogy, including replacement of ferrihydrite by mackinawite and magnetite at the in-flow end of the inoculated columns. At pH 8, the Fe 2+ produced by electron transfer between sulfide and ferrihydrite was mainly retained near its zone of formation. In contrast, at pH 6, much of the produced Fe 2+ was transported with advecting groundwater, facilitating the downstream Fe 2+-catalyzed transformation of ferrihydrite to goethite. At both pH 6 and pH 8, the sulfide-driven reductive dissolution of ferrihydrite and its replacement by mackinawite at the in-flow end of the inoculated columns resulted in substantial mobilization of As into the pore-water. At pH 8, this caused the downstream As concentrations within the inoculated columns to be greater than the corresponding abiotic column. However, the opposite occurred under pH 6 conditions, with the Fe 2+-catalyzed transformation of ferrihydrite to goethite in the inoculated columns causing a decrease in downstream As concentrations compared to the abiotic column. Although thermodynamically favorable at intermediate times and depth intervals within the inoculated columns, solid As sulfide phases were undetectable by As XANES spectroscopy. Our findings

  16. Bioinspired magnetite formation from a disordered ferrihydrite-derived precursor.

    PubMed

    Dey, Archan; Lenders, Jos J M; Sommerdijk, Nico A J M

    2015-01-01

    We show that by reacting ferrihydrite (FeH) with Fe((II)) ions and subsequently increasing the pH, magnetite is formed through a multi-step nucleation process mediated by monodisperse FeH-Fe((II)) primary particles. The interaction of these primary particles with a transient green rust phase leads to the formation of smaller secondary particles which form the feedstock for magnetite formation. Surprisingly, the presence of a polypeptide additive prevents the formation of green rust as an Fe((II))-rich intermediate phase, and leads to the formation of amorphous aggregates of FeH-Fe((II)) particles which subsequently transform into the final magnetite nanocrystals. The observation of multiple transitions and the involvement of disordered precursor phases in this bioinspired crystallization route is important for our understanding of the nucleation of magnetite in geological and biological environments, and may lead to new approaches in the sustainable synthesis of this technologically important mineral.

  17. Phase Transformations in Confined Nanosystems

    SciTech Connect

    Shield, Jeffrey E.; Belashchenko, Kirill

    2014-04-29

    This project discovered that non-equilibrium structures, including chemically ordered structures not observed in bulk systems, form in isolated nanoscale systems. Further, a generalized model was developed that effectively explained the suppression of equilibrium phase transformations. This thermodynamic model considered the free energy decrease associated with the phase transformation was less than the increase in energy associated with the formation of an interphase interface, therefore inhibiting the phase transformation. A critical diameter exists where the system transitions to bulk behavior, and a generalized equation was formulated that successfully predicted this transition in the Fe-Au system. This provided and explains a new route to novel structures not possible in bulk systems. The structural characterization was accomplished using transmission electron microscopy in collaboration with Matthew Kramer of Ames Laboratory. The PI and graduate student visited Ames Laboratory several times a year to conduct the experiments.

  18. Secondary mineralization pathways induced by dissimilatory iron reduction of ferrihydrite under advective flow

    NASA Astrophysics Data System (ADS)

    Hansel, Colleen M.; Benner, Shawn G.; Neiss, Jim; Dohnalkova, Alice; Kukkadapu, Ravi K.; Fendorf, Scott

    2003-08-01

    Iron (hydr)oxides not only serve as potent sorbents and repositories for nutrients and contaminants but also provide a terminal electron acceptor for microbial respiration. The microbial reduction of Fe (hydr)oxides and the subsequent secondary solid-phase transformations will, therefore, have a profound influence on the biogeochemical cycling of Fe as well as associated metals. Here we elucidate the pathways and mechanisms of secondary mineralization during dissimilatory iron reduction by a common iron-reducing bacterium, Shewanella putrefaciens (strain CN32), of 2-line ferrihydrite under advective flow conditions. Secondary mineralization of ferrihydrite occurs via a coupled, biotic-abiotic pathway primarily resulting in the production of magnetite and goethite with minor amounts of green rust. Operating mineralization pathways are driven by competing abiotic reactions of bacterially generated ferrous iron with the ferrihydrite surface. Subsequent to the initial sorption of ferrous iron on ferrihydrite, goethite (via dissolution/reprecipitation) and/or magnetite (via solid-state conversion) precipitation ensues resulting in the spatial coupling of both goethite and magnetite with the ferrihydrite surface. The distribution of goethite and magnetite within the column is dictated, in large part, by flow-induced ferrous Fe profiles. While goethite precipitation occurs over a large Fe(II) concentration range, magnetite accumulation is only observed at concentrations exceeding 0.3 mmol/L (equivalent to 0.5 mmol Fe[II]/g ferrihydrite) following 16 d of reaction. Consequently, transport-regulated ferrous Fe profiles result in a progression of magnetite levels downgradient within the column. Declining microbial reduction over time results in lower Fe(II) concentrations and a subsequent shift in magnetite precipitation mechanisms from nucleation to crystal growth. While the initial precipitation rate of goethite exceeds that of magnetite, continued growth is inhibited by

  19. Ferrous Phosphate Surface Precipitates Resulting from the Reduction of Intragrain 6-line Ferrihydrite by Shewanella oneidensis MR-1

    SciTech Connect

    Peretyazhko, Tetyana; Zachara, John M.; Kennedy, David W.; Fredrickson, Jim K.; Arey, Bruce W.; McKinley, James P.; Wang, Chong M.; Dohnalkova, Alice; Xia, Yuanxian

    2010-07-01

    The reductive biotransformation of 6-line ferrihydrite located within porous silica (intragrain ferrihydrite) by Shewanella oneidensis MR-1 was investigated and compared to the behavior of 6-line ferrihydrite in suspension (free ferrihydrite). The effect of buffer type (PIPES and NaHCO3) and phosphate (P) on the extent of reduction and formation of Fe(II) secondary phases was investigated under anoxic conditions. Electron microscopy and micro X-ray diffraction were applied to evaluate the morphology and mineralogy of the biogenic precipitates and to study the distribution of microorganisms on the surface of porous silica after bioreduction. Kinetic reduction experiments with free and intragrain ferrihydrite revealed contrasting behaviour with respect to the buffer and presence of P. The overall amount of intragrain ferrihydrite reduction was less than that of free ferrihydrite [at 5 mmol L-1 Fe(III)T]. In the intragrain ferrihydrite suspensions, 200-300 µmol L-1 dissolved Fe(III) was released during the initial stages of incubation; no Fe(III)aq was detected in the free ferrihydrite suspensions. Reductive mineralization was not observed in the intragrain ferrihydrite incubations without P, and all biogenic Fe(II) concentrated in the aqueous phase. Distinctive surface precipitates of Fe(II) phosphates with spherical morphology were observed on porous silica when P was present. These precipitates were well colonized by microorganisms and fragments of extracellular materials at the end of incubation.

  20. Biotransformation of two-line silica-ferrihydrite by a dissimilatory Fe(III)-reducing bacterium: formation of carbonate green rust in the presence of phosphate

    NASA Astrophysics Data System (ADS)

    Kukkadapu, Ravi K.; Zachara, John M.; Fredrickson, James K.; Kennedy, David W.

    2004-07-01

    The reductive biotransformation of two Si-ferrihydrite coprecipitates (1 and 5 mole % Si) by Shewanella putrefaciens, strain CN32, was investigated in 1,4-piperazinediethanesulfonic acid-buffered media (pH ˜7) with lactate as the electron donor. Anthraquinone-2,6-disulfonate, an electron shuttle, was present in the media. Experiments were performed without and with PO 43- (P) (1 to 20 mmol/L) in media containing 50 mmol/L Fe. Our objectives were to define the combined effects of SiO 44- (Si) and P on the bioreducibility and biomineralization of ferrihydrites under anoxic conditions. Iron reduction was measured as a function of time, solids were characterized by powder X-ray diffraction and Mössbauer spectroscopy, and aqueous solutions were analyzed for Si, P, Cl - and inorganic carbon. Both of the ferrihydrites were rapidly reduced regardless of the Si and P content. Si concentration had no effect on the reduction rate or mineralization products. Magnetite was formed in the absence of P whereas carbonate green rust GR(CO 32-) ([Fe (6-x)IIFe IIIx(OH) 12] x+(CO 32-) 0.5x · yH 2O) and vivianite [Fe 3(PO 4) 2 · 8H 2O], were formed when P was present. GR(CO 32-) dominated as a mineral product in samples with <4 mmol/L P. The Fe(II)/Fe(III) ratio of GR(CO 32-) varied with P concentration; the ratio was 2 in 1 mmol/L P and approached 1 with 4- and 10 mmol/L P. Green rust appeared to form by solid-state transformation of ferrihydrite. Media P and Si concentration dictated the mechanism of transformation. In the 1 mole % Si coprecipitate with 1 mmol/L P, an intermediate Fe(II)/Fe(III) phase with structural Fe(II) slowly transformed to GR with time. In contrast, when ferrihydrite contained more Si (5 mole %) and/or contained higher P (4 mmol/L), sorbed Fe(II) and residual ferrihydrite together transformed to GR. Despite similar chemistries, P was shown to have a profound effect on extent of ferrihydrite reduction and biotransformations while that of Si was minimal.

  1. Environmental applications of chemically pure natural ferrihydrite.

    PubMed

    Filip, Jan; Zboril, Radek; Schneeweiss, Oldrich; Zeman, Josef; Cernik, Miroslav; Kvapil, Petr; Otyepka, Michal

    2007-06-15

    Fresh precipitates, deposited from seepage waters of complex-ore mine-tailing impoundment at Zlaté Hory, Czech Republic, were characterized by means of X-ray diffraction, transmission electron microscopy, low temperature and in-field Mössbauer spectroscopy, and Brunauer-Emmett-Teller surface area measurements. The prevailing phases (approximately 96 wt %) found in precipitates are poorly crystalline, 2-6 nm sized two-line ferrihydrite, forming globular aggregates of about 150 nm in diameter, rimmed by acicular irregular nanocrystals of goethite. These nanocrystalline ferrihydrite-goethite precipitates are of a relatively high chemical purity (approximately 3% SiO2, Zn approximately 1300 ppm, trace and rare earth elements < 100 ppm) and thus applicable in various nanotechnologies. With a surface area of 270 m2 g(-1), precipitate possesses a high catalytic activity in the decomposition of hydrogen peroxide, which is comparable with that found for commercially accessible FeO(OH) catalyst. Another superior aspect of such natural nanoparticles presents a cheap and suitable precursor for a thermally induced solid-state synthesis of the stable core-shell alpha-Fe-FeO nanoparticles that are well applicable in reductive technologies of groundwater treatment. Just the possibility of using the undesirable waste contaminating the environment in further environmental technologies is the key practical benefit discussed in this paper.

  2. Magnetic and structural properties of ferrihydrite/hematite nanocomposites

    NASA Astrophysics Data System (ADS)

    Pariona, N.; Camacho-Aguilar, K. I.; Ramos-González, R.; Martinez, Arturo I.; Herrera-Trejo, M.; Baggio-Saitovitch, E.

    2016-05-01

    A rich variety of ferrihydrite/hematite nanocomposites (NCs) with specific size, composition and properties were obtained in transformation reactions of 2-line ferrihydrite. Transmission electron microscopy (TEM) observations showed that the NCs consist of clusters of strongly aggregated nanoparticles (NPs) similarly to a "plum pudding", where hematite NPs "raisins" are surrounded by ferrihydrite "pudding". Magnetic measurements of the NCs correlate very well with TEM results; i.e., higher coercive fields correspond to greater hematite crystallite size. First order reversal curve (FORC) measurements were used for the characterization of the magnetic components of the NCs. FORC diagrams revealed that the NCs prepared at short times are composed by single domains with low coercivity, and NCs prepared at times larger than 60 min exhibited elongated distribution along the Hc axis. It suggested that these samples consist of mixtures of different kinds of hematite particles, ones with low coercivity and others with coercivity greater than 600 Oe. For NCs prepared at times larger than 60 min, Mossbauer spectroscopy revealed the presence of two sextets, which one was assigned to fine hematite particles and other to hematite particles with hyperfine parameters near to bulk hematite. The correlation of the structural and magnetic properties of the ferrihydrite/hematite NCs revealed important characteristics of these materials which have not been reported elsewhere.

  3. Biotransformation of Two-Line Silica-Ferrihydrite by a Dissimilatory Fe(III)-Reducing Bacterium: Formation of Carbonate Green Rust in the Presence of Phosphate

    SciTech Connect

    Kukkadapu, Ravi K.; Zachara, John M.; Fredrickson, Jim K.; Kennedy, David W.

    2004-07-01

    The reductive biotransformation of two Si-ferrihydrite (0.01 and 0.05 mole% Si) coprecipiates by Shewanella putrefaciens, strain CN32, was investigated in 1,4-piperazinediethanesulfonic acid-buffered media (pH ~7) with lactate as the electron donor. Anthraquinone-2,6-disulfonate (electron shuttle) that stimulates respiration was present in the media. Experiments were performed without and with PO43- (ranging from 1 to 20 mmol/L in media containing 50 mmol/L Fe). Our objectives were to define the combined effects of SiO44- and PO43- on the bioreducibility and biomineralization of ferrihydrites under anoxic conditions. Iron reduction was measured as a function of time, solids were characterized by powder X-ray diffraction (XRD) and Mossbauer spectroscopy, and aqueous solutions were analyzed for Si, P, Cl- and inorganic carbon. Both of the ferrihydrites were rapidly reduced regardless of the Si content. Si concentration had no effect on the reduction rate or mineralization products. Magnetite was formed in the absence of PO43- whereas carbonate green rust GR(CO32-) ([FeII(6-x)FeIIIx(OH)12]x+(CO32-)0.5x.yH2O) and vivianite [Fe3(PO4)2.8H2O], were formed when PO43- was present. GR(CO32-) dominated as a mineral product in samples with < 4 mmol/L PO43-. The Fe(II)/Fe(III) ratio of GR(CO32-) varied with PO43- concentration; it was 2 in the 1 mmol/L PO43- and approached 1 in the 4- and 10-mmol/L PO43- samples. GR appeared to form by solid-state transformation of ferrihydrite. Medium PO43- concentration dictated the mechanism of transformation. In 1 mmol/L PO43- media, an intermediate Fe(II)/Fe(III) phase with structural Fe(II), which we tentatively assigned to a protomagnetite phase, slowly transformed to GR with time. In contrast, in medium with >4 mmol/L PO43-, a residual ferrihydrite with sorbed Fe2+ phase transformed to GR. Despite similar chemistries, PO43- was shown to have a profound effect on ferrihydrite biotransformations while that of SiO44- was minimal.

  4. Competing Fe (II)-induced mineralization pathways of ferrihydrite.

    PubMed

    Hansel, Colleen M; Benner, Shawn G; Fendorf, Scott

    2005-09-15

    Owing to its high surface area and intrinsic reactivity, ferrihydrite serves as a dominant sink for numerous metals and nutrients in surface environments and is a potentially important terminal electron acceptor for microbial respiration. Introduction of Fe (II), by reductive dissolution of Fe(III) minerals, for example, converts ferrihydrite to Fe phases varying in their retention and reducing capacity. While Fe(II) concentration is the master variable dictating secondary mineralization pathways of ferrihydrite, here we reveal thatthe kinetics of conversion and ultimate mineral assemblage are a function of competing mineralization pathways influenced by pH and stabilizing ligands. Reaction of Fe(II) with ferrihydrite results in the precipitation of goethite, lepidocrocite, and magnetite. The three phases vary in their precipitation extent, rate, and residence time, all of which are primarily a function of Fe(II) concentration and ligand type (Cl, SO4, CO3). While lepidocrocite and goethite precipitate over a large Fe(II) concentration range, magnetite accumulation is only observed at surface loadings greater than 1.0 mmol Fe(II)/g ferrihydrite (in the absence of bicarbonate). Precipitation of magnetite induces the dissolution of lepidocrocite (presence of Cl) or goethite (presence of SO4), allowing for Fe(III)-dependent crystal growth. The rate of magnetite precipitation is a function of the relative proportions of goethite to lepidocrocite; the lower solubility of the former Fe (hydr)oxide slows magnetite precipitation. A one unit pH deviation from 7, however, either impedes (pH 6) or enhances (pH 8) magnetite precipitation. In the absence of magnetite nucleation, lepidocrocite and goethite continue to precipitate at the expense of ferrihydrite with near complete conversion within hours, the relative proportions of the two hydroxides dependent upon the ligand present. Goethite also continues to precipitate at the expense of lepidocrocite in the absence of

  5. Differential arsenic mobilization from As-bearing ferrihydrite by iron-respiring Shewanella strains with different arsenic-reducing activities.

    PubMed

    Jiang, Shenghua; Lee, Ji-Hoon; Kim, Donghun; Kanaly, Robert A; Kim, Min-Gyu; Hur, Hor-Gil

    2013-08-01

    Arsenic immobilization and release in the environment is significantly influenced by bacterial oxidation and reduction of arsenic and arsenic-bearing minerals. In this study, we tested three iron-reducing bacteria, Shewanella oneidensis MR-1, Shewanella sp. HN-41, and Shewanella putrefaciens 200, which have diverse arsenate-reducing activities with regard to reduction of an As-bearing ferrihydrite slurry. In the cultures of S. oneidensis MR-1 and Shewanella sp. HN-41, which are not capable of respiratory reduction of As(V) to As(III), arsenic was maintained predominantly in its pentavalent form, existing in particulate poorly crystalline As-bearing ferrihydrite and formed small quantities of a stable ferrous arsenate [Fe3(AsO4)2] precipitate. However, in the culture of the As(V) reducer, S. putrefaciens 200, As(V) was reduced to As(III) and a small fraction of As-bearing ferrihydrite was transformed into ribbon-shaped siderite that subsequently re-released arsenic into the liquid phase. Our results indicated that release of arsenic and formation of diverse secondary nanoscale Fe-As minerals are specifically closely related to the arsenic-reducing abilities of different bacteria. Therefore, bacterial arsenic reduction appears to significantly influence As mobilization in soils, minerals, and other Fe-rich environments.

  6. Phase Equilibria, Phase Diagrams and Phase Transformations - 2nd Edition

    NASA Astrophysics Data System (ADS)

    Hillert, Mats

    2006-03-01

    Computational tools allow material scientists to model and analyze increasingly complicated systems to appreciate material behavior. Accurate use and interpretation however, requires a strong understanding of the thermodynamic principles that underpin phase equilibrium, transformation and state. This fully revised and updated edition covers the fundamentals of thermodynamics, with a view to modern computer applications. The theoretical basis of chemical equilibria and chemical changes is covered with an emphasis on the properties of phase diagrams. Starting with the basic principles, discussion moves to systems involving multiple phases. New chapters cover irreversible thermodynamics, extremum principles, and the thermodynamics of surfaces and interfaces. Theoretical descriptions of equilibrium conditions, the state of systems at equilibrium and the changes as equilibrium is reached, are all demonstrated graphically. With illustrative examples - many computer calculated - and worked examples, this textbook is an valuable resource for advanced undergraduates and graduate students in materials science and engineering. Fully revised and updated edition covering the fundamentals of thermodynamics with a view to modern computer applications such as Thermo-Calc Emphasis is placed on phase diagrams, the key application of thermodynamics Contains numerous illustrative examples, many computer-calculated and some for real systems, and worked examples to help demonstrate the principles

  7. Composition and reactivity of ferrihydrite-organic matter associations

    NASA Astrophysics Data System (ADS)

    Eusterhues, Karin; Hädrich, Anke; Neidhardt, Julia; Küsel, Kirsten; Totsche, Kai

    2014-05-01

    The formation of organo-mineral associations affects many soil forming processes. On the one hand, it will influence soil organic matter composition and development, because the complex organic matter mixtures usually fractionate during their association with mineral surfaces. Whereas the associated fraction is supposed to be stabilized, the non-associated fraction remains mobile and available to degradation by microorganisms. On the other hand, the organic coating will completely change the interface properties of Fe oxides such as solubility, charge and hydrophobicity. This in turn will strongly influence their reactivity towards nutrients and pollutants, the adsorption of new organic matter, and the availability of ferric Fe towards microorganisms. To better understand such processes we produced ferrihydrite-organic matter associations by adsorption and coprecipitation in laboratory experiments. As a surrogate for dissolved soil organic matter we used the water-extractable fraction of a Podzol forest-floor layer under spruce. Sorptive fractionation of the organic matter was investigated by 13C NMR and FTIR. Relative to the original forest-floor extract, the ferrihydrite-associated OM was enriched in polysaccharides but depleted in aliphatic C and carbonyl C, especially when adsorption took place. Liquid phase incubation experiments were carried out with an inoculum extracted from the podzol forest-floor under oxic conditions at pH 4.8 to quantify the mineralization of the adsorbed and coprecipitated organic matter. These experiments showed that the association with ferrihydrite stabilized the associated organic matter, but that differences in the degradability of adsorbed and coprecipitated organic matter were small. We therefore conclude that coprecipitation does not lead to a significant formation of microbial inaccessible organic matter domains. Microbial reduction experiments were performed using Geobacter bremensis. We observed that increasing amounts of

  8. The Kinetics of Phase Transformation in Welds

    SciTech Connect

    Elmer, J W; Wong, J; Palmer, T

    2002-02-06

    The fundamentals of welding-induced phase transformations in metals and alloys are being investigated using a combination of advanced synchrotron based experimental methods and modem computational science tools. In-situ experimental methods have been developed using a spatially resolved x-ray probe to enable direct observations of phase transformations under the real non- isothermal conditions experienced during welding. These experimental techniques represent a major step forward in the understanding of phase transformations that occur during welding, and are now being used to aid in the development of models to predict microstructural evolution under the severe temperature gradients, high peak temperatures and rapid thermal fluctuations characteristic of welds. Titanium alloys, stainless steels and plain carbon steels are currently under investigation, and the phase transformation data being obtained here cannot be predicted or measured using conventional metallurgical approaches. Two principal synchrotron-based techniques have been developed and refined for in-situ investigations of phase transformation dynamics in the heat-affected zone (HAZ) and fusion zone (FZ) of welds: Spatially Resolved X-Ray Diffraction (SRXRD) and Time Resolved X-Ray Diffraction (TRXRD). Both techniques provide real-time observations of phases that exist during welding, and both have been developed at the Stanford Synchrotron Radiation Laboratory (SSRL) using a high flux wiggler beam line. The SRXRD technique enables direct observations of the phases existing in the HAZ of quasi-stationary moving arc welds, and is used to map the HAZ phases by sequentially jogging the weld with respect to the x-ray beam while taking x-ray diffraction (XRD) patterns at each new location. These spatially resolved XRD patterns are collected in linear traverses perpendicular to the direction of weld travel. The XRD data contained in multiple traverses is later compiled to produce an areal map of the phases

  9. Phase transformation of strontium hexagonal ferrite

    NASA Astrophysics Data System (ADS)

    Bilovol, V.; Martínez-García, R.

    2015-11-01

    The phase transformation of strontium hexagonal ferrite (SrFe12O19) to magnetite (Fe3O4) as main phase and strontium carbonate (SrCO3) as secondary phase is reported here. SrFe12O19 powder was obtained by a heat treatment at 250 °C under controlled oxygen flow. It was observed that the phase transformation occurred when the SrFe12O19 ferrite was heated up to 625 °C in confinement conditions. This transformation took place by a combination of three factors: the presence of stresses in the crystal lattice of SrFe12O19 due to a low synthesis temperature, the reduction of Fe3+ to Fe2+ during the heating up to 625 °C, and the similarity of the coordination spheres of the iron atoms present in the S-block of SrFe12O19 and Fe3O4. X-ray diffraction analysis confirmed the existence of strain and crystal deformation in SrFe12O19 and the absence of them in the material after the phase transformation. Dispersive X-ray absorption spectroscopy and Fe57 Mössbauer spectroscopy provided evidences of the reduction of Fe3+ to Fe2+ in the SrFe12O19 crystal.

  10. Spectral Evolution of Bioreduced Ferrihydrite by Hyperthermophiles

    NASA Astrophysics Data System (ADS)

    Sklute, E. C.; Kashyap, S.; Holden, J. F.; Dyar, M. D.

    2016-05-01

    The hyperthermophile Pyrodictium sp. Su06 reduces ferrihydrite to a black, magnetic, Fe(II)-bearing mineral. Mossbauer spectra for that mineral freeze dried vs. frozen in the original liquid suspension differ. Both represent potential biosignatures.

  11. Characterising microbial reduction of arsenate sorbed to ferrihydrite and its concurrence with iron reduction and the consequent impact on arsenic mobilisation

    NASA Astrophysics Data System (ADS)

    Huang, Jen-How

    2014-05-01

    Mobilisation of solid phase arsenic under reducing conditions involves a combination of microbial arsenate and iron reduction and is affected by secondary reactions of released products. A series of model anoxic incubations were performed to understand the concurrence between arsenate and ferrihydrite reduction by Shewanella putrefaciens strain CN-32 at different concentrations of arsenate, ferrihydrite and lactate, and with given ΔGrxn for arsenate and ferrihydrite reduction in non-growth conditions at pH 7. The reduction kinetics of arsenate sorbed to ferrihydrite is predominately controlled by the availability of dissolved arsenate, which is measured by the integral of dissolved arsenate concentrations against incubation time and shown to correlate with the first order rate constants. Thus, the mobilisation of adsorbed As(V) can be regarded as the rate determining step of microbial reduction of As(V) sorbed to ferrihydrite. High lactate concentrations slightly slowed down the rate of arsenate reduction due to the competition with arsenate for microbial contact. Under all experimental conditions, simultaneous arsenate and ferrihydrite reduction occurred following addition of S. putrefaciens inoculums and suggested no apparent competition between these two enzymatic reductions. Ferrous ions released from iron reduction might retard microbial arsenate reduction at high arsenate and ferrihydrite concentrations due to formation of ferrous arsenate. At high arsenate to ferrihydrite ratios, reductive dissolution of ferrihydrite shifted arsenate from sorption to dissolution and hence accelerated arsenate reduction. Reductive dissolution of ferrihydrite may cause additional releases of adsorbed As(V) into solution, which is especially effective at high As(V) to ferrihydrite ratios. In comparison, formation of Fe(II) secondary minerals during microbial Fe(III) reduction were responsible for trapping solution As(V) in the systems with high ferrihydrite but low As

  12. Phase Transformation in Cast Superaustenitic Stainless Steels

    SciTech Connect

    Lee Phillips, Nathaniel Steven

    2006-01-01

    Superaustenitic stainless steels constitute a group of Fe-based alloys that are compositionally balanced to have a purely austenitic matrix and exhibit favorable pitting and crevice corrosion resistant properties and mechanical strength. However, intermetallic precipitates such as sigma and Laves can form during casting or exposure to high-temperature processing, which degrade the corrosion and mechanical properties of the material. The goal of this study was to accurately characterize the solid-solid phase transformations seen in cast superaustenitic stainless steels. Heat treatments were performed to understand the time and temperature ranges for intermetallic phase formations in alloys CN3MN and CK3MCuN. Microstructures were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy and wavelength dispersive spectroscopy (EDS, WDS). The equilibrium microstructures, composed primarily of sigma and Laves within purely austenitic matrices, showed slow transformation kinetics. Factors that determine the extent of transformation, including diffusion, nucleation, and growth, are discussed.

  13. Phase transformations in binary colloidal monolayers.

    PubMed

    Yang, Ye; Fu, Lin; Marcoux, Catherine; Socolar, Joshua E S; Charbonneau, Patrick; Yellen, Benjamin B

    2015-03-28

    Phase transformations can be difficult to characterize at the microscopic level due to the inability to directly observe individual atomic motions. Model colloidal systems, by contrast, permit the direct observation of individual particle dynamics and of collective rearrangements, which allows for real-space characterization of phase transitions. Here, we study a quasi-two-dimensional, binary colloidal alloy that exhibits liquid-solid and solid-solid phase transitions, focusing on the kinetics of a diffusionless transformation between two crystal phases. Experiments are conducted on a monolayer of magnetic and nonmagnetic spheres suspended in a thin layer of ferrofluid and exposed to a tunable magnetic field. A theoretical model of hard spheres with point dipoles at their centers is used to guide the choice of experimental parameters and characterize the underlying materials physics. When the applied field is normal to the fluid layer, a checkerboard crystal forms; when the angle between the field and the normal is sufficiently large, a striped crystal assembles. As the field is slowly tilted away from the normal, we find that the transformation pathway between the two phases depends strongly on crystal orientation, field strength, and degree of confinement of the monolayer. In some cases, the pathway occurs by smooth magnetostrictive shear, while in others it involves the sudden formation of martensitic plates. PMID:25677504

  14. Decoupling of arsenic and iron release from ferrihydrite suspension under reducing conditions: a biogeochemical model

    PubMed Central

    Burnol, André; Garrido, Francis; Baranger, Philippe; Joulian, Catherine; Dictor, Marie-Christine; Bodénan, Françoise; Morin, Guillaume; Charlet, Laurent

    2007-01-01

    High levels of arsenic in groundwater and drinking water are a major health problem. Although the processes controlling the release of As are still not well known, the reductive dissolution of As-rich Fe oxyhydroxides has so far been a favorite hypothesis. Decoupling between arsenic and iron redox transformations has been experimentally demonstrated, but not quantitatively interpreted. Here, we report on incubation batch experiments run with As(V) sorbed on, or co-precipitated with, 2-line ferrihydrite. The biotic and abiotic processes of As release were investigated by using wet chemistry, X-ray diffraction, X-ray absorption and genomic techniques. The incubation experiments were carried out with a phosphate-rich growth medium and a community of Fe(III)-reducing bacteria under strict anoxic conditions for two months. During the first month, the release of Fe(II) in the aqueous phase amounted to only 3% to 10% of the total initial solid Fe concentration, whilst the total aqueous As remained almost constant after an initial exchange with phosphate ions. During the second month, the aqueous Fe(II) concentration remained constant, or even decreased, whereas the total quantity of As released to the solution accounted for 14% to 45% of the total initial solid As concentration. At the end of the incubation, the aqueous-phase arsenic was present predominately as As(III) whilst X-ray absorption spectroscopy indicated that more than 70% of the solid-phase arsenic was present as As(V). X-ray diffraction revealed vivianite Fe(II)3(PO4)2.8H2O in some of the experiments. A biogeochemical model was then developed to simulate these aqueous- and solid-phase results. The two main conclusions drawn from the model are that (1) As(V) is not reduced during the first incubation month with high Eh values, but rather re-adsorbed onto the ferrihydrite surface, and this state remains until arsenic reduction is energetically more favorable than iron reduction, and (2) the release of As

  15. Effect of ferrihydrite on 2,4,6-trinitrotoluene biotransformation by an aerobic yeast.

    PubMed

    Khilyas, Irina V; Ziganshin, Ayrat M; Pannier, Andy J; Gerlach, Robin

    2013-09-01

    This study investigated the impact of ferrihydrite on the pathway and rate of 2,4,6-trinitrotoluene (TNT) transformation by Yarrowia lipolytica AN-L15. The presence of ferrihydrite in the culture medium decreased the rate of TNT biotransformation but resulted in the accumulation of the same TNT metabolites as in the absence of ferrihydrite, albeit at slightly different concentrations. Transformation products observed included aromatic ring reduction products, such as hydride-Meisenheimer complexes, and nitro group reduction products, such as hydroxylamino- and amino-dinitrotoluenes. Independently of the presence of ferrihydrite the subsequent degradation of the hydride complex(es) resulted in the release of nitrite followed by its conversion to nitrate and nitric oxide at the low pH values observed during yeast cultivation. Nitric oxide generation was ascertained by electron spin resonance spectroscopy. In addition, increased Fe(3+)-reduction was observed in the presence of TNT and Y. lipolytica. This study demonstrates that in the presence of yeast cells, TNT-hydride complexes were formed at approximately the same level as in the presence of ferrihydrite, opening up the possibility of aromatic ring cleavage, instead of promoting the production of potentially toxic nitro group reduction products in the presence of iron minerals.

  16. Non isothermal effects on phase transformation kinetics

    NASA Astrophysics Data System (ADS)

    Sista, Vivekanand

    Cyclic thermal processing has been shown to accelerate the kinetics of several phase transformations, with a significant beneficial impact on productivity and energy consumption of the energy intensive operations like cyclic grain growth kinetics, recrystallization kinetics and austempering. Austempering is an important thermal processing operation, where strong and tough bainitic steel is produced in a single heat treatment. A new process called cyclic austempering was developed where the steel is first austenized and then cooled rapidly to just above the martensite start temperature where the bainitic transformation is carried out in a controlled fluctuating temperature profile, by continuous heating and cooling segments between two temperature limits. Both isothermal and cyclic austempering experiments were performed on 1080 steel. The powerful dilatometry technique was used to measure the diametrical change as a function of transformation time and temperature. The time taken for the complete bainitic transformation in both isothermal and cyclic austempering processes were calculated to see whether the bainitic kinetics are accelerated or not. Asymmetric cyclic austempering was also performed to determine the heating and cooling rate effects on the transformation. Cyclic austempering resulted in accelerating kinetics to about an 80% reduction in time compared to that of conventional isothermal austempering. Incubation times were calculated to propose a possible mechanism for the accelerated kinetics. Microstructure analysis and hardness analysis was used to establish the cyclic transformation kinetics.

  17. Phase Transformations in Cast Duplex Stainless Steels

    SciTech Connect

    Kim, Yoon-Jun

    2004-01-01

    Duplex stainless steels (DSS) constitute both ferrite and austenite as a matrix. Such a microstructure confers a high corrosion resistance with favorable mechanical properties. However, intermetallic phases such as σ and χ can also form during casting or high-temperature processing and can degrade the properties of the DSS. This research was initiated to develop time-temperature-transformation (TTT) and continuous-cooling-transformation (CCT) diagrams of two types of cast duplex stainless steels, CD3MN (Fe-22Cr-5Ni-Mo-N) and CD3MWCuN (Fe-25Cr-7Ni-Mo-W-Cu-N), in order to understand the time and temperature ranges for intermetallic phase formation. The alloys were heat treated isothermally or under controlled cooling conditions and then characterized using conventional metallographic methods that included tint etching, and also using electron microscopy (SEM, TEM) and wavelength dispersive spectroscopy (WDS). The kinetics of intermetallic-phase (σ + χ) formation were analyzed using the Johnson-Mehl-Avrami (MA) equation in the case of isothermal transformations and a modified form of this equation in the case of continuous cooling transformations. The rate of intermetallic-phase formation was found to be much faster in CD3MWCuN than CD3MN due mainly to differences in the major alloying contents such as Cr, Ni and Mo. To examine in more detail the effects of these elements of the phase stabilities; a series of eight steel castings was designed with the Cr, Ni and Mo contents systematically varied with respect to the nominal composition of CD3MN. The effects of varying the contents of alloying additions on the formation of intermetallic phases were also studied computationally using the commercial thermodynamic software package, Thermo-Calc. In general, σ was stabilized with increasing Cr addition and χ by increasing Mo addition. However, a delicate balance among Ni and other minor elements such as N and Si also exists. Phase equilibria in DSS can be affected by

  18. Shock-induced phase transformation in tantalum

    NASA Astrophysics Data System (ADS)

    Hsiung, Luke L.

    2010-09-01

    A TEM study of pure tantalum and tantalum-tungsten alloys explosively shocked at a peak pressure of 30 GPa is presented. While no omega phase was found in shock-recovered pure Ta and Ta-5W which mainly contain a cellular dislocation structure, a shock-induced omega phase was found in Ta-10W which contains evenly distributed dislocations with a density higher than 1 × 1012 cm - 2. The shock-induced \\alpha ~\\mathrm {(bcc)}\\rightarrow \\omega (hexagonal) transition occurs when the dynamic recovery of dislocations becomes largely suppressed in Ta-10W shocked under dynamic-pressure conditions. A dislocation-based mechanism is proposed for the shock-induced phase transformation.

  19. Stability of Ferrihydrite and Organic Matter in Ferrihydrite-Organic Matter Associations

    NASA Astrophysics Data System (ADS)

    Eusterhues, K.; Totsche, K. U.

    2015-12-01

    Iron oxides can bind particularly large amounts of organic matter (OM) and seem to be an important control on OM storage in many soils. To better understand the interactions between Fe oxides and OM, we produced ferrihydrite-OM associations by adsorption and coprecipitation in laboratory experiments. Because ferrihydrites are often formed in OM-rich solutions, we assume that coprecipitation is a common process in nature. In contrast to adsorption on pre-existing ferrihydrite surfaces, coprecipitation involves adsorption, occlusion (physical entrapment of OM), formation of Fe-OM complexes, and poisoning of ferrihydrite growth. The reactivity of coprecipitates may therefore differ from ferriydrites with adsorbed OM. Incubation experiments with an inoculum extracted from a Podzol forest-floor were carried out to quantify the mineralization of the adsorbed and coprecipitated organic matter. These experiments showed that the association with ferrihydrite stabilized the associated organic matter, but that differences in the degradability of adsorbed and coprecipitated organic matter were small. We therefore conclude that coprecipitation does not lead to a significant formation of microbial inaccessible organic matter domains. Microbial reduction experiments were performed using Geobacter bremensis. We observed that increasing amounts of associated OM led to decreasing initial reaction rates and a decreasing degree of dissolution. Reduction of coprecipitated ferrihydrites was faster than reduction of ferrihydrites with adsorbed OM. Our data demonstrate that the association with ferrihydrite can effectively stabilize labile polysaccharides. Vice versa, these polysaccharides may protect ferrihydrite from reduction by Geobacter-like bacteria. However, a challenge for future studies will be to link formation and degradation of mineral-organic associations to natural porous systems, that is, to the complex interplay of mass transport and microbial distribution in the

  20. Modelling Cu(II) adsorption to ferrihydrite and ferrihydrite-bacteria composites: Deviation from additive adsorption in the composite sorption system

    NASA Astrophysics Data System (ADS)

    Moon, Ellen M.; Peacock, Caroline L.

    2013-03-01

    Bacterially associated iron (hydr)oxides are widespread in natural environments and are potent scavengers of dissolved metal ions. However, it is unclear whether metal sorption on these composites adheres to the additivity principle, and thus whether metal concentrations in environments where these composites comprise a significant proportion of the reactive iron phases can be modelled assuming component additivity. Here we address this issue for Cu adsorption on ferrihydrite-Bacillus subtilis composites. We precipitated pure ferrihydrite and ferrihydrite composites with different ferrihydrite:bacteria mass ratios, and measured Cu adsorption as a function of pH, Cu adsorbed concentration and composite mass ratio. We develop a molecular-level surface complexation model for Cu adsorption on pure ferrihydrite. We then combine our end-member models for Cu adsorption on B. subtilis (Moon and Peacock, 2011) and ferrihydrite to model the observed Cu adsorption on the composites, adopting a component linear additivity approach. By comparing observed Cu adsorption to that predicted by our composite model, constrained to the exact best fitting end-member stability constants, we find that Cu adsorption behaviour on ferrihydrite-B. subtilis composites deviates from additivity. Specifically, Cu adsorption on composites composed mainly of ferrihydrite is enhanced across the adsorption pH edge (pH ˜3-6), while on our composite composed mainly of bacteria adsorption is enhanced at mid-high pH (pH ˜5-6) but diminished at mid-low pH (pH ˜5-3), compared to additivity. In current surface complexation modelling constructs, Cu adsorption on composites composed mainly of ferrihydrite can be modelled in a component additivity approach, by optimising the stability constants for Cu adsorption on the ferrihydrite and bacteria fractions to values that are within the uncertainty on the end-member stability constant values. The deviation from additivity of these composites, apparent when

  1. Effect of ferrihydrite biomineralization on methanogenesis in an anaerobic incubation from paddy soil

    NASA Astrophysics Data System (ADS)

    Zhuang, Li; Xu, Jielong; Tang, Jia; Zhou, Shungui

    2015-05-01

    Microbial reduction of Fe(III) can be one of the major factors controlling methane production from anaerobic sedimentary environments, such as paddy soils and wetlands. Although secondary iron mineralization following Fe(III) reduction is a process that occurs naturally over time, it has not yet been considered in methanogenic systems. This study performed a long-term anaerobic incubation of a paddy soil and ferrihydrite-supplemented soil cultures to investigate methanogenesis during ferrihydrite biomineralization. The results revealed that the long-term effect of ferrihydrite on methanogenesis may be enhancement rather than suppression documented in previous studies. During initial microbial ferrihydrite reduction, methanogenesis was suppressed; however, the secondary minerals of magnetite formation was simultaneous with facilitated methanogenesis in terms of average methane production rate and acetate utilization rate. In the phase of magnetite formation, microbial community analysis revealed a strong stimulation of the bacterial Geobacter, Bacillus, and Sedimentibacter and the archaeal Methanosarcina in the ferrihydrite-supplemented cultures. Direct electric syntrophy between Geobacter and Methanosarcina via conductive magnetite is the plausible mechanism for methanogenesis acceleration along with magnetite formation. Our data suggested that a change in iron mineralogy might affect the conversion of anaerobic organic matter to methane and might provide a fresh perspective on the mitigation of methane emissions from paddy soils by ferric iron fertilization.

  2. Phase transformations in xerogels of mullite composition

    NASA Technical Reports Server (NTRS)

    Hyatt, Mark J.; Bansal, Narottam P.

    1988-01-01

    Monophasic and diphasic xerogels have been prepared as precursors for mullite (3Al2O3-2SiO2). Monophasic xerogel was synthesized from tetraethyl orthosilicate and aluminum nitrate nanohydrate and the diphasic xerogel from colloidal suspension of silica and boehmite. The chemical and structural evolutions, as a function of thermal treatment, in these two types of sol-gel derived mullite precursor powders have been characterized by DTA, TGA, X-ray diffraction, SEM and infrared spectroscopy. Monophasic xerogel transforms to an Al-Si spinel from an amorphous structure at approximately 980 C. The spinel then changes into mullite on further heating. Diphasic xerogel forms mullite at approximately 1360 C. The components of the diphasic powder react independently up to the point of mullite formation. The transformation in the monophasic powder occurs rapidly and yields strongly crystalline mullite with no other phases present. The diphasic powder, however, transforms rather slowly and contains remnants of the starting materials (alpha-Al2O3, cristobalite) even after heating at high temperatures for long times (1600 C, 6 hr). The diphasic powder could be sintered to high density but not the monophasic powder in spite of its molecular level homogeneity.

  3. Phase transformation and growth of hygroscopic aerosols

    SciTech Connect

    Tang, I.N.

    1995-09-01

    Ambient aerosols frequently contain large portions of hygroscopic inorganic salts such as chlorides, nitrates, and sulfates in either pure or mixed forms. Such inorganic salt aerosols exhibit the properties of deliquescence and efflorescence in air. The phase transformation from a solid particle to a saline droplet usually occurs spontaneously when the relative humidity of the atmosphere reaches a level specific to the chemical composition of the aerosol particle. Conversely, when the relative humidity decreases and becomes low enough, the saline droplet will evaporate and suddenly crystallize, expelling all its water content. The phase transformation and growth of aerosols play an important role in many atmospheric processes affecting air quality, visibility degradation, and climate changes. In this chapter, an exposition of the underlying thermodynamic principles is given, and recent advances in experimental methods utilizing single-particle levitation are discussed. In addition, pertinent and available thermodynamic data, which are needed for predicting the deliquescence properties of single and multi-component aerosols, are compiled. This chapter is useful to research scientists who are either interested in pursuing further studies of aerosol thermodynamics, or required to model the dynamic behavior of hygroscopic aerosols in a humid environment.

  4. Ferrous phosphate surface precipitates resulting from the reduction of intragrain 6-line ferrihydrite by Shewanella oneidensis MR-1

    SciTech Connect

    Peretyazhko, Tetyana; Zachara, John M.; Kennedy, David W.; Fredrickson, Jim K.; Arey, Bruce W.; McKinley, James P.; Wang, Chong M.; Dohnalkova, Alice; Xia, Yuanxian

    2010-07-01

    The reductive biotransformation of 6-line ferrihydrite located within porous silica (intragrain ferrihydrite) by Shewanella oneidensis MR-1 was investigated and compared to the behavior of 6-line ferrihydrite in suspension (free ferrihydrite). The effect of buffer type (PIPES and NaHCO3), phosphate (P), and an electron shuttle (AQDS) on the extent of reduction and formation of Fe(II) secondary phases was investigated under anoxic conditions. Electron microscopy and micro X-ray diffraction were applied to evaluate the morphology and mineralogy of the biogenic precipitates and to study the distribution of microorganisms on the surface of porous silica after bioreduction. Kinetic reduction experiments with free and intragrain ferrihydrite revealed contrasting behaviour with respect to the buffer and presence of P. The overall amount of intragrain ferrihydrite reduction was less than that of free ferrihydrite [at 5 mmol L-1 Fe(III)T]. Reductive mineralization was not observed in the intragrain ferrihydrite incubations without P, and all biogenic Fe(II) concentrated in the aqueous phase. Irrespective of buffer and AQDS addition, rosettes of Fe(II) phosphate of approximate 20-30 μm size were observed on porous silica when P was present. The rosettes grew not only on the silica surface but also within it, forming a coherent spherical structure. These precipitates were well colonized by microorganisms and contained extracellular materials at the end of incubation. Microbial extracellular polymeric substances may have adsorbed Fe(II) promoting Fe(II) phosphate nucleation with subsequent crystal growth proceeding in different directions from a common center.

  5. Precipitation pathways for ferrihydrite formation in acidic solutions

    DOE PAGESBeta

    Zhu, Mengqiang; Khalid, Syed; Frandsen, Cathrine; Wallace, Adam F.; Legg, Benjamin; Zhang, Hengzhong; Morup, Steen; Banfield, Jillian F.; Waychunas, Glenn A.

    2015-10-03

    In this study, iron oxides and oxyhydroxides form via Fe3+ hydrolysis and polymerization in many aqueous environments, but the pathway from Fe3+ monomers to oligomers and then to solid phase nuclei is unknown. In this work, using combined X-ray, UV–vis, and Mössbauer spectroscopic approaches, we were able to identify and quantify the long-time sought ferric speciation over time during ferric oxyhydroxide formation in partially-neutralized ferric nitrate solutions ([Fe3+] = 0.2 M, 1.8 < pH < 3). Results demonstrate that Fe exists mainly as Fe(H2O)63+, μ-oxo aquo dimers and ferrihydrite, and that with time, the μ-oxo dimer decreases while the othermore » two species increase in their concentrations. No larger Fe oligomers were detected. Given that the structure of the μ-oxo dimer is incompatible with those of all Fe oxides and oxyhydroxides, our results suggest that reconfiguration of the μ-oxo dimer structure occurs prior to further condensation leading up to the nucleation of ferrihydrite. The structural reconfiguration is likely the rate-limiting step involved in the nucleation process.« less

  6. Precipitation pathways for ferrihydrite formation in acidic solutions

    SciTech Connect

    Zhu, Mengqiang; Khalid, Syed; Frandsen, Cathrine; Wallace, Adam F.; Legg, Benjamin; Zhang, Hengzhong; Morup, Steen; Banfield, Jillian F.; Waychunas, Glenn A.

    2015-10-03

    In this study, iron oxides and oxyhydroxides form via Fe3+ hydrolysis and polymerization in many aqueous environments, but the pathway from Fe3+ monomers to oligomers and then to solid phase nuclei is unknown. In this work, using combined X-ray, UV–vis, and Mössbauer spectroscopic approaches, we were able to identify and quantify the long-time sought ferric speciation over time during ferric oxyhydroxide formation in partially-neutralized ferric nitrate solutions ([Fe3+] = 0.2 M, 1.8 < pH < 3). Results demonstrate that Fe exists mainly as Fe(H2O)63+, μ-oxo aquo dimers and ferrihydrite, and that with time, the μ-oxo dimer decreases while the other two species increase in their concentrations. No larger Fe oligomers were detected. Given that the structure of the μ-oxo dimer is incompatible with those of all Fe oxides and oxyhydroxides, our results suggest that reconfiguration of the μ-oxo dimer structure occurs prior to further condensation leading up to the nucleation of ferrihydrite. The structural reconfiguration is likely the rate-limiting step involved in the nucleation process.

  7. Precipitation pathways for ferrihydrite formation in acidic solutions

    NASA Astrophysics Data System (ADS)

    Zhu, Mengqiang; Frandsen, Cathrine; Wallace, Adam F.; Legg, Benjamin; Khalid, Syed; Zhang, Hengzhong; Mørup, Steen; Banfield, Jillian F.; Waychunas, Glenn A.

    2016-01-01

    Iron oxides and oxyhydroxides form via Fe3+ hydrolysis and polymerization in many aqueous environments, but the pathway from Fe3+ monomers to oligomers and then to solid phase nuclei is unknown. In this work, using combined X-ray, UV-vis, and Mössbauer spectroscopic approaches, we were able to identify and quantify the long-time sought ferric speciation over time during ferric oxyhydroxide formation in partially-neutralized ferric nitrate solutions ([Fe3+] = 0.2 M, 1.8 < pH < 3). Results demonstrate that Fe exists mainly as Fe(H2O)63+, μ-oxo aquo dimers and ferrihydrite, and that with time, the μ-oxo dimer decreases while the other two species increase in their concentrations. No larger Fe oligomers were detected. Given that the structure of the μ-oxo dimer is incompatible with those of all Fe oxides and oxyhydroxides, our results suggest that reconfiguration of the μ-oxo dimer structure occurs prior to further condensation leading up to the nucleation of ferrihydrite. The structural reconfiguration is likely the rate-limiting step involved in the nucleation process.

  8. Rate controlling processes in solvent-mediated phase transformations

    NASA Astrophysics Data System (ADS)

    Davey, R. J.; Cardew, P. T.; McEwan, D.; Sadler, D. E.

    1986-12-01

    Transformations between solid phases in contact with a solvent can proceed by a mechanism in which crystals of the stable phase grow and those of the metastable phase dissolve. The kinetics of such a transformation are determined by the relative rates of dissolution and growth of the two phases. Measurement of the concentration profile in solution during a transformation is the best means of quantifying these kinetics. In this paper two solvent-mediated phase transformations, one for a dyestuff, the other for paclobutrazol, a plant growth regulator manufactured by ICI, have been studied. A combination of direct observation of the solid phases and measurement of the solution concentrations with time during the transformations allowed the kinetics to be described in terms of the relative rates of dissolution and growth of the metastable and stable phases.

  9. Crystal Level Continuum Modeling of Phase Transformations: The (alpha) <--> (epsilon) Transformation in Iron

    SciTech Connect

    Barton, N R; Benson, D J; Becker, R; Bykov, Y; Caplan, M

    2004-10-18

    We present a crystal level model for thermo-mechanical deformation with phase transformation capabilities. The model is formulated to allow for large pressures (on the order of the elastic moduli) and makes use of a multiplicative decomposition of the deformation gradient. Elastic and thermal lattice distortions are combined into a single lattice stretch to allow the model to be used in conjunction with general equation of state relationships. Phase transformations change the mass fractions of the material constituents. The driving force for phase transformations includes terms arising from mechanical work, from the temperature dependent chemical free energy change on transformation, and from interaction energy among the constituents. Deformation results from both these phase transformations and elasto-viscoplastic deformation of the constituents themselves. Simulation results are given for the {alpha} to {epsilon} phase transformation in iron. Results include simulations of shock induced transformation in single crystals and of compression of polycrystals. Results are compared to available experimental data.

  10. Ferrihydrite Formation: The Role of Fe13 Keggin Clusters.

    PubMed

    Weatherill, Joshua S; Morris, Katherine; Bots, Pieter; Stawski, Tomasz M; Janssen, Arne; Abrahamsen, Liam; Blackham, Richard; Shaw, Samuel

    2016-09-01

    Ferrihydrite is the most common iron oxyhydroxide found in soil and is a key sequester of contaminants in the environment. Ferrihydrite formation is also a common component of many treatment processes for cleanup of industrial effluents. Here we characterize ferrihydrite formation during the titration of an acidic ferric nitrate solution with NaOH. In situ SAXS measurements supported by ex situ TEM indicate that initially Fe13 Keggin clusters (radius ∼ 0.45 nm) form in solution at pH 0.12-1.5 and are persistent for at least 18 days. The Fe13 clusters begin to aggregate above ∼ pH 1, initially forming highly linear structures. Above pH ∼ 2 densification of the aggregates occurs in conjunction with precipitation of low molecular weight Fe(III) species (e.g., monomers, dimers) to form mass fractal aggregates of ferrihydrite nanoparticles (∼3 nm) in which the Fe13 Keggin motif is preserved. SAXS analysis indicates the ferrihydrite particles have a core-shell structure consisting of a Keggin center surrounded by a Fe-depleted shell, supporting the surface depleted model of ferrihydrite. Overall, we present the first direct evidence for the role of Fe13 clusters in the pathway of ferrihydrite formation during base hydrolysis, showing clear structural continuity from isolated Fe13 Keggins to the ferrihydrite particle structure. The results have direct relevance to the fundamental understanding of ferrihydrite formation in environmental, engineered, and industrial processes. PMID:27480123

  11. Ferrihydrite Formation: The Role of Fe13 Keggin Clusters.

    PubMed

    Weatherill, Joshua S; Morris, Katherine; Bots, Pieter; Stawski, Tomasz M; Janssen, Arne; Abrahamsen, Liam; Blackham, Richard; Shaw, Samuel

    2016-09-01

    Ferrihydrite is the most common iron oxyhydroxide found in soil and is a key sequester of contaminants in the environment. Ferrihydrite formation is also a common component of many treatment processes for cleanup of industrial effluents. Here we characterize ferrihydrite formation during the titration of an acidic ferric nitrate solution with NaOH. In situ SAXS measurements supported by ex situ TEM indicate that initially Fe13 Keggin clusters (radius ∼ 0.45 nm) form in solution at pH 0.12-1.5 and are persistent for at least 18 days. The Fe13 clusters begin to aggregate above ∼ pH 1, initially forming highly linear structures. Above pH ∼ 2 densification of the aggregates occurs in conjunction with precipitation of low molecular weight Fe(III) species (e.g., monomers, dimers) to form mass fractal aggregates of ferrihydrite nanoparticles (∼3 nm) in which the Fe13 Keggin motif is preserved. SAXS analysis indicates the ferrihydrite particles have a core-shell structure consisting of a Keggin center surrounded by a Fe-depleted shell, supporting the surface depleted model of ferrihydrite. Overall, we present the first direct evidence for the role of Fe13 clusters in the pathway of ferrihydrite formation during base hydrolysis, showing clear structural continuity from isolated Fe13 Keggins to the ferrihydrite particle structure. The results have direct relevance to the fundamental understanding of ferrihydrite formation in environmental, engineered, and industrial processes.

  12. Phase transformations in a model mesenchymal tissue

    NASA Astrophysics Data System (ADS)

    Newman, Stuart A.; Forgacs, Gabor; Hinner, Bernhard; Maier, Christian W.; Sackmann, Erich

    2004-06-01

    Connective tissues, the most abundant tissue type of the mature mammalian body, consist of cells suspended in complex microenvironments known as extracellular matrices (ECMs). In the immature connective tissues (mesenchymes) encountered in developmental biology and tissue engineering applications, the ECMs contain varying amounts of randomly arranged fibers, and the physical state of the ECM changes as the fibers secreted by the cells undergo fibril and fiber assembly and organize into networks. In vitro composites consisting of assembling solutions of type I collagen, containing suspended polystyrene latex beads (~6 µm in diameter) with collagen-binding surface properties, provide a simplified model for certain physical aspects of developing mesenchymes. In particular, assembly-dependent topological (i.e., connectivity) transitions within the ECM could change a tissue from one in which cell-sized particles (e.g., latex beads or cells) are mechanically unlinked to one in which the particles are part of a mechanical continuum. Any particle-induced alterations in fiber organization would imply that cells could similarly establish physically distinct microdomains within tissues. Here we show that the presence of beads above a critical number density accelerates the sol-gel transition that takes place during the assembly of collagen into a globally interconnected network of fibers. The presence of this suprathreshold number of beads also dramatically changes the viscoelastic properties of the collagen matrix, but only when the initial concentration of soluble collagen is itself above a critical value. Our studies provide a starting point for the analysis of phase transformations of more complex biomaterials including developing and healing tissues as well as tissue substitutes containing living cells.

  13. Mössbauer studies of ferrihydrite for Fischer-Tropsch catalysts

    NASA Astrophysics Data System (ADS)

    Lim, Jung Tae; Kim, Chul Sung; Chun, Dong Hyun; Park, Ji Chan

    2016-01-01

    The 6-line ferrihydrite sample for Ficher-Tropsch catalysts was prepared by using a combination of a co-precipitation technique and a spraydrying method. The crystallographic and magnetic properties of 6-line ferrihydrite sample were investigated by using x-ray diffractometer (XRD), vibrating sample magnetometer (VSM), and Mössbauer spectrometer. The XRD patterns of the ferrihydrite sample, measured at 295 K, showed 6-lines peak and its structure was found to be a single-phased hexagonal with space group of P3m1 according to JCPDS card. The temperaturedependent magnetization curves were measured under 1000 Oe between 4.2 and 300 K, and showed blocking temperature ( T B ) around 110 K. Also, Mössbauer spectra of the 6-line ferrihydrite sample were taken at various temperatures ranging from 4.2 to 295 K. At temperature below T B , the obtained spectra were analyzed as two-sextets for Fe sites, while At temperature above T B , the obtained spectra showed a doublet due to relaxation, resulting from the spin dynamic effect.

  14. METHODOLOGICAL NOTES: Metastable phases, phase transformations, and phase diagrams in physics and chemistry

    NASA Astrophysics Data System (ADS)

    Brazhkin, Vadim V.

    2006-07-01

    Concepts of a 'phase' and a 'phase transition' are discussed for stable and metastable states of matter. While condensed matter physics primarily considers equilibrium states and treats metastable phases as exceptions, organic chemistry overwhelmingly deals with metastable states. It is emphasized that many simple light-element compounds — including most hydrocarbons; nitrogen oxides, hydrides, and carbides; carbon monoxide CO; alcohols and glycerin — are also metastable at normal pressure in the sense that they do not correspond to a minimum Gibbs free energy for a given chemical composition. At moderate temperatures and pressures, the phase transformations for these metastable phases are reversible with the fulfilment of all laws of equilibrium thermodynamics over the entire range of experimentally accessible times. At sufficiently high pressures (> 1-10 GPa), most of the metastable molecular phases irreversibly transform to lower-energy polymer phases, stable or metastable. These transitions do not correspond to the equality of the Gibbs free energy for the involved phases before and after the transition and so they are not first-order in the 'classical' sense. At normal pressure, the resulting polymer phases can exist at temperatures above the melting point of the original metastable molecular phase, as the examples of polyethylene and polymerized CO dramatically illustrate. As pressure is increased further to 20-50 GPa, the PV contribution to Gibbs free energy gives rise to stable high-density atomic phases. Many of the intermediate-energy polymer phases can likely be synthesized by methods of 'classical' chemistry at normal pressure.

  15. Investigations of pressure induced structural phase transformations in pentaerythritol

    NASA Astrophysics Data System (ADS)

    Garg, Nandini; Sharma, Surinder M.; Sikka, S. K.

    2005-10-01

    We have investigated the pressure induced structural changes in pentaerythritol {2,2-bis-(hydroxymethyl)-1,3-propanediol} with the help of X-ray diffraction studies. Our results show that this compound undergoes transformations to a lower symmetry phase between 5.2-5.9 GPa. It further undergoes phase transformations at ˜8.5 and ˜11 GPa; eventually evolving to a disordered phase beyond 14-15 GPa in agreement with our earlier Raman studies. On release of pressure from 18.5 GPa, the compound transforms back to the initial tetragonal phase.

  16. Molecular- and nm-scale Investigation of the Structure and Compositional Heterogeneity of Naturally Occurring Ferrihydrite

    NASA Astrophysics Data System (ADS)

    Cismasu, C.; Michel, F. M.; Stebbins, J. F.; Tcaciuc, A. P.; Brown, G. E.

    2008-12-01

    Ferrihydrite is a hydrated Fe(III) nano-oxide that forms in vast quantities in contaminated acid mine drainage environments. As a result of its high surface area, ferrihydrite is an important environmental sorbent, and plays an essential role in the geochemical cycling of pollutant metal(loid)s in these settings. Despite its environmental relevance, this nanomineral remains one of the least understood environmental solids in terms of its structure (bulk and surface), compositional variations, and the factors affecting its reactivity. Under natural aqueous conditions, ferrihydrite often precipitates in the presence of several inorganic compounds such as aluminum, silica, arsenic, etc., or in the presence of organic matter. These impurities can affect the molecular-level structure of naturally occurring ferrihydrite, thus modifying fundamental properties that are directly correlated with solid-phase stability and surface reactivity. Currently there exists a significant gap in our understanding of the structure of synthetic vs. natural ferrihydrites, due to the inherent difficulties associated to the investigation of these poorly crystalline nanophases. In this study, we combined synchrotron- and laboratory-based techniques to characterize naturally occurring ferrihydrite from an acid mine drainage system situated at the New Idria mercury mine in California. We used high-energy X-ray total scattering and pair distribution function analysis to elucidate quantitative structural details of these samples. We have additionally used scanning transmission X-ray microscopy high resolution imaging (30 nm) to evaluate the spatial relationship of major elements Si, Al, and C within ferrihydrite. Al, Si and C K-edge near- edge X-ray absorption fine structure spectroscopy and 27Al nuclear magnetic resonance spectroscopy were used to obtain short-range structural information. By combining these techniques we attain the highest level of resolution permitted by current analytical

  17. Phase transformation of boron nitride under hypothermal conditions

    SciTech Connect

    Lian Gang; Zhang Xiao; Zhu Lingling; Cui Deliang; Wang Qilong; Tao Xutang

    2009-06-15

    Phase transformation among different boron nitride (BN) phases in hydrothermal solution was investigated. It was found that hexagonal boron nitride (hBN) firstly formed in the solution at relatively low temperature (i.e., 220 deg. C). After that, a spot of hBN began to transform into wurtzite boron nitride (wBN) and cubic boron nitride (cBN) at 230 deg. C. More and more hBN converted into wBN and cBN with the increase in temperature, and this transformation process completed at 300 deg. C. In this paper, we have explained the mechanism of the above phase transformation by using a reported 'puckering mechanism'. - Graphical abstract: Phase transformations from hBN to wBN and cBN happened with the temperature increasing from 230 to 300 deg. C under hypothermal conditions, and nearly pure cBN has been synthesized at 300 deg. C and 12 MPa.

  18. Phosphate Imposed Limitations on Biological Reduction and Alteration of Ferrihydrite Mineralization

    SciTech Connect

    Borch, Thomas; Masue, Yoko; Kukkadapu, Ravi K.; Fendorf, Scott

    2007-01-01

    Biogeochemical transformation (inclusive of dissolution) of iron (hydr)oxides resulting from dissimilatory reduction has a pronounced impact on the fate and transport of nutrients and contaminants in subsurface environments. Despite the reactivity noted for pristine (unreacted) minerals, iron (hydr)oxides within native environments will likely have a different reactivity owing in part to changes in surface composition. Accordingly, here we explore the impact of surface modifications induced by phosphate adsorption on ferrihydrite reduction by Shewanella putrefaciens under static and advective flow conditions. Alterations in surface reactivity induced by phosphate adsorption change the extent, nearly linearly, and pathway of iron biomineralization. Magnetite is the most appreciable mineralization product while minor amounts of vivianite and green rust-like phases are formed in systems having high aqueous concentrations of phosphate, ferrous iron, and biogenic bicarbonate. Goethite and lepidocrocite, characteristic biomineralization products at low ferrous-iron concentrations, are inhibited in the presence of adsorbed phosphate. Considering deviations in reactivity of iron (hydr)oxides with changes in surface composition is important for deciphering mineralization pathways under native conditions and predicting reactive characteristics.

  19. Phase transformations in ternary monotectic aluminum alloys

    NASA Astrophysics Data System (ADS)

    Gröbner, Joachim; Schmid-Fetzer, Rainer

    2005-09-01

    Monotectic aluminum alloys are of interest for the development of new alloys for technological applications such as self-lubricating bearings. In contrast to the well-known binary phase diagrams, many of the ternary systems are not well established. Moreover, in a ternary monotectic alloy one may encounter the four-phase equilibrium L‧+L″+solid1+solid2, whereas in a binary system only a three-phase equilibrium L‧+L″+solid1 is possible. This opens a window for generating entirely new monotectic microstructures. The basis for such developments is the knowledge of the ternary phase diagrams and the conditions under which such four-phase reactions or different extensions of the binary monotectic reactions may form. This work presents a systematic classification of monotectic ternary aluminum alloys, illustrated by real systems. The study employs thermodynamic calculations of the ternary phase diagrams.

  20. Non-gauge phase transformations in quantum transition amplitudes

    NASA Technical Reports Server (NTRS)

    Reiss, H. R.

    1993-01-01

    The prescription for introducing a gauge transformation into a quantum transition amplitude, nominally well known, contains an ambiguous feature. It is presumed by some authors that an appropriate transformation of the phase of a wave function will generate the associated gauge transformation. It is shown that this is a necessary but not sufficient step. Examples from the literature are cited to show the consequences of the failure of this procedure. One must distinguish between true gauge transformations and unitary transformations within a fixed gauge.

  1. Design of electromagnetic refractor and phase transformer using coordinate transformation theory.

    PubMed

    Lin, Lan; Wang, Wei; Cui, Jianhua; Du, Chunlei; Luo, Xiangang

    2008-05-12

    We designed an electromagnetic refractor and a phase transformer using form-invariant coordinate transformation of Maxwell's equations. The propagation direction of electromagnetic energy in these devices can be modulated as desired. Unlike the conventional dielectric refractor, electromagnetic fields at our refraction boundary do not conform to the Snell's law in isotropic materials and the impedance at this boundary is matched which makes the reflection extremely low; and the transformation of the wave front from cylindrical to plane can be realized in the phase transformer with a slab structure. Two dimensional finite-element simulations were performed to confirm the theoretical results.

  2. Typical Phases of Transformative Learning: A Practice-Based Model

    ERIC Educational Resources Information Center

    Nohl, Arnd-Michael

    2015-01-01

    Empirical models of transformative learning offer important insights into the core characteristics of this concept. Whereas previous analyses were limited to specific social groups or topical terrains, this article empirically typifies the phases of transformative learning on the basis of a comparative analysis of various social groups and topical…

  3. Atomic Structure and Phase Transformations in Pu Alloys

    SciTech Connect

    Schwartz, A J; Cynn, H; Blobaum, K M; Wall, M A; Moore, K T; Evans, W J; Farber, D L; Jeffries, J R; Massalski, T B

    2008-04-28

    Plutonium and plutonium-based alloys containing Al or Ga exhibit numerous phases with crystal structures ranging from simple monoclinic to face-centered cubic. Only recently, however, has there been increased convergence in the actinides community on the details of the equilibrium form of the phase diagrams. Practically speaking, while the phase diagrams that represent the stability of the fcc {delta}-phase field at room temperature are generally applicable, it is also recognized that Pu and its alloys are never truly in thermodynamic equilibrium because of self-irradiation effects, primarily from the alpha decay of Pu isotopes. This article covers past and current research on several properties of Pu and Pu-(Al or Ga) alloys and their connections to the crystal structure and the microstructure. We review the consequences of radioactive decay, the recent advances in understanding the electronic structure, the current research on phase transformations and their relations to phase diagrams and phase stability, the nature of the isothermal martensitic {delta} {yields} {alpha}{prime} transformation, and the pressure-induced transformations in the {delta}-phase alloys. New data are also presented on the structures and phase transformations observed in these materials following the application of pressure, including the formation of transition phases.

  4. Fast microbial reduction of ferrihydrite colloids from a soil effluent

    NASA Astrophysics Data System (ADS)

    Fritzsche, Andreas; Bosch, Julian; Rennert, Thilo; Heister, Katja; Braunschweig, Juliane; Meckenstock, Rainer U.; Totsche, Kai U.

    2012-01-01

    Recent studies on the microbial reduction of synthetic iron oxide colloids showed their superior electron accepting property in comparison to bulk iron oxides. However, natural colloidal iron oxides differ in composition from their synthetic counterparts. Besides a potential effect of colloid size, microbial iron reduction may be accelerated by electron-shuttling dissolved organic matter (DOM) as well as slowed down by inhibitors such as arsenic. We examined the microbial reduction of OM- and arsenic-containing ferrihydrite colloids. Four effluent fractions were collected from a soil column experiment run under water-saturated conditions. Ferrihydrite colloids precipitated from the soil effluent and exhibited stable hydrodynamic diameters ranging from 281 (±146) nm in the effluent fraction that was collected first and 100 (±43) nm in a subsequently obtained effluent fraction. Aliquots of these oxic effluent fractions were added to anoxic low salt medium containing diluted suspensions of Geobacter sulfurreducens. Independent of the initial colloid size, the soil effluent ferrihydrite colloids were quickly and completely reduced. The rates of Fe2+ formation ranged between 1.9 and 3.3 fmol h-1 cell-1, and are in the range of or slightly exceeding previously reported rates of synthetic ferrihydrite colloids (1.3 fmol h-1 cell-1), but greatly exceeding previously known rates of macroaggregate-ferrihydrite reduction (0.07 fmol h-1 cell-1). The inhibition of microbial Fe(III) reduction by arsenic is unlikely or overridden by the concurrent enhancement induced by soil effluent DOM. These organic species may have increased the already high intrinsic reducibility of colloidal ferrihydrite owing to quinone-mediated electron shuttling. Additionally, OM, which is structurally associated with the soil effluent ferrihydrite colloids, may also contribute to the higher reactivity due to increasing solubility and specific surface area of ferrihydrite. In conclusion, ferrihydrite

  5. Phase transformation of Mg-Fe alloys

    SciTech Connect

    Yoneda, Yasuhiro; Abe, Hiroshi; Ohshima, Takeshi; Uchida, Hirohisa

    2010-05-15

    An Mg-Fe alloy system prepared through mechanical alloying (MA) was structurally analyzed. MA can produce single-phase bcc alloys using Mg concentrations up to about 15 mol %. Use of conventional average structure analysis and x-ray pair-distribution function method enabled the long-range and short-range order structures of the Mg-Fe alloys to be bridged. The substituted Mg atoms were randomly arranged in the low-Mg composition but started to have an order structure. The partially ordered Mg-Fe alloy undergoes an austenitic (cubic) to martensitic (orthorhombic) phase change, as increasing Mg composition.

  6. Inhibitory Effects of Ferrihydrite on a Thermophilic Methanogenic Community

    PubMed Central

    Yamada, Chihaya; Kato, Souichiro; Ueno, Yoshiyuki; Ishii, Masaharu; Igarashi, Yasuo

    2014-01-01

    The addition of ferrihydrite to methanogenic microbial communities obtained from a thermophilic anaerobic digester suppressed methanogenesis in a dose-dependent manner. The amount of reducing equivalents consumed by the reduction of iron was significantly smaller than that expected from the decrease in the production of CH4, which suggested that competition between iron-reducing microorganisms and methanogens was not the most significant cause for the suppression of methanogenesis. Microbial community analyses revealed that the presence of ferrihydrite markedly affected the bacterial composition, but not the archaeal composition. These results indicate that the presence of ferrihydrite directly and indirectly suppresses thermophilic methanogenesis. PMID:24859310

  7. TEMPERATURE EFFECTS ON THE SYNTHESIS OF SI-FERRIHYDRITE NANOPARTICLES OF VARIABLE SIZES IDENTIFIED BY MAGNETIC MEASUREMENTS

    EPA Science Inventory

    Ferrihydrite is an antiferromagnetic iron oxyhydroxide formed as an ubiquitous product of natural iron diagenesis, and found in iron-containing water, soil, river sediment and oceanic crust. As such, it is a sensitive indicator or proxy of environmental change. This iron phase ha...

  8. Microstructure and phase transformations in FeSe superconductor

    NASA Astrophysics Data System (ADS)

    Diko, P.; Antal, V.; Kavečansky, V.; Yang, Ch.; Chen, I.

    2012-06-01

    It is shown that a FeSe bulk superconductor prepared by solidification in an inert atmosphere contains an acicular β(Fe1-xSe) phase with a residual δ(Fe1-xSe) high temperature phase. Four different crystal orientations of the β(Fe1-xSe) phase formed from one δ(Fe1-xSe) grain were detected by polarised light microscopy. This behaviour is typical for diffusion-less transformations. The diffusion-less character of δ(Fe1-xSe) to β(Fe1-xSe) transformation was confirmed by thermal analysis.

  9. Kinetics of Propagating Phase Transformation in Compressed Bismuth

    SciTech Connect

    Bastea, M; Bastea, S; Emig, J; Springer, P; Reisman, D

    2004-08-18

    The authors observed dynamically driven phase transitions in isentropically compressed bismuth. By changing the stress loading conditions they explored two distinct cases one in which the experimental signature of the phase transformation corresponds to phase-boundary crossings initiated at both sample interfaces, and another in which the experimental trace is due to a single advancing transformation front in the bulk of the material. They introduce a coupled kinetics-hydrodynamics model that for this second case enables them, under suitable simplifying assumptions, to directly extract characteristic transition times from the experimental measurements.

  10. Phase transformation near the classical limit of stability

    SciTech Connect

    Maibaum, Lutz

    2008-11-06

    Successful theories of phase transformation processes include classical nucleation theory (CNT), which envisions a local equilibrium between coexisting phases, and non--equilibrium kinetic cluster theories. Using computer simulations of the magnetization reversal of the Ising model in three different ensembles we make quantitative connections between these physical pictures. We show that the critical nucleus size of CNT is strongly correlated with a dynamical measure of metastability, and that the metastable phase persists to thermodynamic conditions previously thought of as unstable.

  11. Nanoscale Transforming Mineral Phases in Fresh Nacre.

    PubMed

    DeVol, Ross T; Sun, Chang-Yu; Marcus, Matthew A; Coppersmith, Susan N; Myneni, Satish C B; Gilbert, Pupa U P A

    2015-10-21

    Nacre, or mother-of-pearl, the iridescent inner layer of many mollusk shells, is a biomineral lamellar composite of aragonite (CaCO3) and organic sheets. Biomineralization frequently occurs via transient amorphous precursor phases, crystallizing into the final stable biomineral. In nacre, despite extensive attempts, amorphous calcium carbonate (ACC) precursors have remained elusive. They were inferred from non-nacre-forming larval shells, or from a residue of amorphous material surrounding mature gastropod nacre tablets, and have only once been observed in bivalve nacre. Here we present the first direct observation of ACC precursors to nacre formation, obtained from the growth front of nacre in gastropod shells from red abalone (Haliotis rufescens), using synchrotron spectromicroscopy. Surprisingly, the abalone nacre data show the same ACC phases that are precursors to calcite (CaCO3) formation in sea urchin spicules, and not proto-aragonite or poorly crystalline aragonite (pAra), as expected for aragonitic nacre. In contrast, we find pAra in coral. PMID:26403582

  12. High pressure phase transformation in iron under fast compression

    SciTech Connect

    Bastea, M; Bastea, S; Becker, R

    2009-07-07

    We present experimental results on the solid-solid, {alpha} to {epsilon} phase transformation kinetics of iron under high pressure dynamic compression. We observe kinetic features - velocity loops - similar with the ones recently reported to occur when water is frozen into its ice VII phase under comparable experimental conditions. We analyze this behavior in terms of general ideas coupling the steady sample compression with phase nucleation and growth with a pressure dependent phase interface velocity. The model is used to predict the response of iron when steadily driven across the {alpha} - {epsilon} phase boundary on very short time scales, including those envisioned to be achieved in ultra-fast laser experiments.

  13. Phase Transformation in Tantalum under Extreme Laser Deformation.

    PubMed

    Lu, C-H; Hahn, E N; Remington, B A; Maddox, B R; Bringa, E M; Meyers, M A

    2015-10-19

    The structural and mechanical response of metals is intimately connected to phase transformations. For instance, the product of a phase transformation (martensite) is responsible for the extraordinary range of strength and toughness of steel, making it a versatile and important structural material. Although abundant in metals and alloys, the discovery of new phase transformations is not currently a common event and often requires a mix of experimentation, predictive computations, and luck. High-energy pulsed lasers enable the exploration of extreme pressures and temperatures, where such discoveries may lie. The formation of a hexagonal (omega) phase was observed in recovered monocrystalline body-centered cubic tantalum of four crystallographic orientations subjected to an extreme regime of pressure, temperature, and strain-rate. This was accomplished using high-energy pulsed lasers. The omega phase and twinning were identified by transmission electron microscopy at 70 GPa (determined by a corresponding VISAR experiment). It is proposed that the shear stresses generated by the uniaxial strain state of shock compression play an essential role in the transformation. Molecular dynamics simulations show the transformation of small nodules from body-centered cubic to a hexagonal close-packed structure under the same stress state (pressure and shear).

  14. Phase Transformation in Tantalum under Extreme Laser Deformation

    PubMed Central

    Lu, C.-H.; Hahn, E. N.; Remington, B. A.; Maddox, B. R.; Bringa, E. M.; Meyers, M. A.

    2015-01-01

    The structural and mechanical response of metals is intimately connected to phase transformations. For instance, the product of a phase transformation (martensite) is responsible for the extraordinary range of strength and toughness of steel, making it a versatile and important structural material. Although abundant in metals and alloys, the discovery of new phase transformations is not currently a common event and often requires a mix of experimentation, predictive computations, and luck. High-energy pulsed lasers enable the exploration of extreme pressures and temperatures, where such discoveries may lie. The formation of a hexagonal (omega) phase was observed in recovered monocrystalline body-centered cubic tantalum of four crystallographic orientations subjected to an extreme regime of pressure, temperature, and strain-rate. This was accomplished using high-energy pulsed lasers. The omega phase and twinning were identified by transmission electron microscopy at 70 GPa (determined by a corresponding VISAR experiment). It is proposed that the shear stresses generated by the uniaxial strain state of shock compression play an essential role in the transformation. Molecular dynamics simulations show the transformation of small nodules from body-centered cubic to a hexagonal close-packed structure under the same stress state (pressure and shear). PMID:26478106

  15. Phase Transformation in Tantalum under Extreme Laser Deformation.

    PubMed

    Lu, C-H; Hahn, E N; Remington, B A; Maddox, B R; Bringa, E M; Meyers, M A

    2015-01-01

    The structural and mechanical response of metals is intimately connected to phase transformations. For instance, the product of a phase transformation (martensite) is responsible for the extraordinary range of strength and toughness of steel, making it a versatile and important structural material. Although abundant in metals and alloys, the discovery of new phase transformations is not currently a common event and often requires a mix of experimentation, predictive computations, and luck. High-energy pulsed lasers enable the exploration of extreme pressures and temperatures, where such discoveries may lie. The formation of a hexagonal (omega) phase was observed in recovered monocrystalline body-centered cubic tantalum of four crystallographic orientations subjected to an extreme regime of pressure, temperature, and strain-rate. This was accomplished using high-energy pulsed lasers. The omega phase and twinning were identified by transmission electron microscopy at 70 GPa (determined by a corresponding VISAR experiment). It is proposed that the shear stresses generated by the uniaxial strain state of shock compression play an essential role in the transformation. Molecular dynamics simulations show the transformation of small nodules from body-centered cubic to a hexagonal close-packed structure under the same stress state (pressure and shear). PMID:26478106

  16. Phase transformation in tantalum under extreme laser deformation

    SciTech Connect

    Lu, C. -H.; Hahn, E. N.; Remington, B. A.; Maddox, B. R.; Bringa, E. M.; Meyers, M. A.

    2015-10-19

    The structural and mechanical response of metals is intimately connected to phase transformations. For instance, the product of a phase transformation (martensite) is responsible for the extraordinary range of strength and toughness of steel, making it a versatile and important structural material. Although abundant in metals and alloys, the discovery of new phase transformations is not currently a common event and often requires a mix of experimentation, predictive computations, and luck. High-energy pulsed lasers enable the exploration of extreme pressures and temperatures, where such discoveries may lie. The formation of a hexagonal (omega) phase was observed in recovered monocrystalline body-centered cubic tantalum of four crystallographic orientations subjected to an extreme regime of pressure, temperature, and strain-rate. This was accomplished using high-energy pulsed lasers. The omega phase and twinning were identified by transmission electron microscopy at 70 GPa (determined by a corresponding VISAR experiment). It is proposed that the shear stresses generated by the uniaxial strain state of shock compression play an essential role in the transformation. In conclusion, molecular dynamics simulations show the transformation of small nodules from body-centered cubic to a hexagonal close-packed structure under the same stress state (pressure and shear).

  17. Phase transformation in tantalum under extreme laser deformation

    DOE PAGESBeta

    Lu, C. -H.; Hahn, E. N.; Remington, B. A.; Maddox, B. R.; Bringa, E. M.; Meyers, M. A.

    2015-10-19

    The structural and mechanical response of metals is intimately connected to phase transformations. For instance, the product of a phase transformation (martensite) is responsible for the extraordinary range of strength and toughness of steel, making it a versatile and important structural material. Although abundant in metals and alloys, the discovery of new phase transformations is not currently a common event and often requires a mix of experimentation, predictive computations, and luck. High-energy pulsed lasers enable the exploration of extreme pressures and temperatures, where such discoveries may lie. The formation of a hexagonal (omega) phase was observed in recovered monocrystalline body-centeredmore » cubic tantalum of four crystallographic orientations subjected to an extreme regime of pressure, temperature, and strain-rate. This was accomplished using high-energy pulsed lasers. The omega phase and twinning were identified by transmission electron microscopy at 70 GPa (determined by a corresponding VISAR experiment). It is proposed that the shear stresses generated by the uniaxial strain state of shock compression play an essential role in the transformation. In conclusion, molecular dynamics simulations show the transformation of small nodules from body-centered cubic to a hexagonal close-packed structure under the same stress state (pressure and shear).« less

  18. Partially transformed relaxor ferroelectric single crystals with distributed phase transformation behavior

    NASA Astrophysics Data System (ADS)

    Gallagher, John A.

    2015-11-01

    Relaxor ferroelectric single crystals such as PMN-PT and PIN-PMN-PT undergo field driven phase transformations when electrically or mechanically loaded in crystallographic directions that provide a positive driving force for the transformation. The observed behavior in certain compositions is a phase transformation distributed over a range of fields without a distinct forward or reverse coercive field. This work focuses on the material behavior that is observed when the crystals are loaded sufficiently to drive a partial transformation and then unloaded, as might occur when driving a transducer to achieve high power levels. Distributed transformations have been modeled using a normal distribution of transformation thresholds. A set of experiments was conducted to characterize the hysteresis loops that occur with the partial transformations. In this work the normal distribution model is extended to include the partial transformations that occur when the field is reversed before the transformation is complete. The resulting hysteresis loops produced by the model are in good agreement with the experimental results.

  19. Effect of Phosphate on Surface Properties of Ferrihydrite and its Reactivity towards Aqueous Fe(II)

    NASA Astrophysics Data System (ADS)

    Liao, D.; Schroeder, C.; Haderlein, S.

    2012-12-01

    The iron redox cycle plays a prominent role for the biogeochemical cycling of nutrients and metals as well as transformation of contaminants in soils, sediments and aquifers. The mineral surface acts as a sorption site for Fe(II), which becomes partially oxidized upon sorption [1]. According to Gorski and Scherer [2], the electron is transferred to the bulk mineral, where it may be stored in a conduction band leading to an increased reductive potential of the system. Iron (hydr)oxides also exhibit a high sorption capacity for phosphate which forms strong surface complexes with iron. Phosphate is a common constituent of pore waters as a result of agricultural fertilizers, and is frequently used by microbiologists as buffer in laboratory experiments. We investigated the effect of phosphate on the oxidation of Fe(II) in the presence of ferrihydrite minerals in batch reactors. We synthesized three different ferrihydrites: untreated ferrihydrite (Fh); phosphate-coated ferrihydrite (pc-Fh), where phosphate was added to suspensions of pure ferrihydrite and allowed to sorb to the mineral surface; and phosphate-doped ferrihydrite (pd-Fh), where phosphate co-precipitated with ferrihydrite and was included in the bulk mineral structure. Nitrobenzene was used as model oxidant to study ferrous iron oxidation in anoxic Fh-Fe(II) suspensions. Fe(II) oxidation was much slower in the presence of pc-Fh and pd-Fh compared to untreated Fh. Using Mössbauer spectroscopy, we added dissolved Fe(II) either as pure 57Fe (Mössbauer-active) to analyse for the iron fraction associated with the minerals surface, or as 56Fe (Mössbauer-inactive) to focus on the bulk mineral only. We took Mössbauer spectra for each system before and after Fe(II) oxidation by nitrobenzene. Surface bound Fe(II) was oxidized by two processes: e-transfer to structural Fe(III) in Fh and nitrobenzene reduction. The oxidation product was lepidocrocite which increased with nitrobenzene reduction. Phosphate-doped and

  20. Phase transformation kinetics in finite inhomogeneously nucleated systems

    NASA Technical Reports Server (NTRS)

    Weinberg, Michael; Kapral, Raymond

    1989-01-01

    Phase transformation kinetics that occur by a nucleation and growth process are investigated. A simple discrete space and time model is used for the dynamics and analytical results are obtained for the volume fraction of the material transformed for both finite systems and a special example of an inhomogeneously nucleated system. The theory is developed for two cases, initial nucleation, and continuous nucleation. The results are compared with simulations of the model.

  1. Phase transformations in superconducting and non-superconducting perovskites

    SciTech Connect

    Mitchell, T.E.

    1992-01-01

    Most of the high {Tc} superconductors and other perovskite-related cuprates exhibit some kind of structural instability. For example, tetragonal-to-orthorhombic phase transformations occur in the Y-Ba-Cu-O and La-Sr-Cu-O systems while crystal structures in the Bi-Ca-Sr-Cu-O and Tl-Ba-Ca-Cu-O systems have incommensurate periodicities associated with displacements of the heavy cations. In YBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}}, the transformation is due to the ordering of oxygen vacancies while in La{sub 2-x}Sr{sub x}CuO{sub 4} the transformation is accompanied by tilting of the (CuO{sub 6}) octahedra. Such tilting and distortion of the co-ordination octahedra commonly occur in perovskite-related compounds and transformations between the structures are frequently martensitic. Phase transformations in the superconducting cuprates have been investigated by transmission electron microscopy but none of them appear to be martensitic. The phase transformations are accompanied by twinning and the resulting configurations are used to calculate twin boundary energies.

  2. Phase transformations in superconducting and non-superconducting perovskites

    SciTech Connect

    Mitchell, T.E.

    1992-07-01

    Most of the high {Tc} superconductors and other perovskite-related cuprates exhibit some kind of structural instability. For example, tetragonal-to-orthorhombic phase transformations occur in the Y-Ba-Cu-O and La-Sr-Cu-O systems while crystal structures in the Bi-Ca-Sr-Cu-O and Tl-Ba-Ca-Cu-O systems have incommensurate periodicities associated with displacements of the heavy cations. In YBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}}, the transformation is due to the ordering of oxygen vacancies while in La{sub 2-x}Sr{sub x}CuO{sub 4} the transformation is accompanied by tilting of the [CuO{sub 6}] octahedra. Such tilting and distortion of the co-ordination octahedra commonly occur in perovskite-related compounds and transformations between the structures are frequently martensitic. Phase transformations in the superconducting cuprates have been investigated by transmission electron microscopy but none of them appear to be martensitic. The phase transformations are accompanied by twinning and the resulting configurations are used to calculate twin boundary energies.

  3. Using Neural Networks to Describe Complex Phase Transformation Behavior

    SciTech Connect

    Vitek, J.M.; David, S.A.

    1999-05-24

    Final microstructures can often be the end result of a complex sequence of phase transformations. Fundamental analyses may be used to model various stages of the overall behavior but they are often impractical or cumbersome when considering multicomponent systems covering a wide range of compositions. Neural network analysis may be a useful alternative method of identifying and describing phase transformation beavior. A neural network model for ferrite prediction in stainless steel welds is described. It is shown that the neural network analysis provides valuable information that accounts for alloying element interactions. It is suggested that neural network analysis may be extremely useful for analysis when more fundamental approaches are unavailable or overly burdensome.

  4. Metallurgical Properties and Phase Transformations of Barium-Strontium Modifier

    NASA Astrophysics Data System (ADS)

    Platonov, M. A.; Sulimova, I. S.; Rozhikhina, I. D.; Dmitrienko, V. I.; Horoshun, G. V.

    2016-04-01

    Metallurgical properties and phase transformations of barium-strontium modifier were tested in laboratory conditions resembling steel processing in furnace and ladle. When heating barium-strontium modifier start of melting, kinetics of decomposition, phase and structure transformation were studied. The concentrate under consideration has been revealed to be a complex mineral compound containing barytocalcite, calcite, calciostrontianite, dolomite and siderite. The reaction kinetics of decomposing mineral components of barium-strontium modifier to oxides does not considerably affect slag formation in conditions of out-of-furnace steel processing.

  5. Phase transformations in steels: Processing, microstructure, and performance

    SciTech Connect

    Gibbs, Paul J.

    2014-04-03

    In this study, contemporary steel research is revealing new processing avenues to tailor microstructure and properties that, until recently, were only imaginable. Much of the technological versatility facilitating this development is provided by the understanding and utilization of the complex phase transformation sequences available in ferrous alloys. Today we have the opportunity to explore the diverse phenomena displayed by steels with specialized analytical and experimental tools. Advances in multi-scale characterization techniques provide a fresh perspective into microstructural relationships at the macro- and micro-scale, enabling a fundamental understanding of the role of phase transformations during processing and subsequent deformation.

  6. Mössbauer studies of phase transformations in iron alloys

    NASA Astrophysics Data System (ADS)

    Mercader, R. C.; Desimoni, J.

    1997-09-01

    Procedures related to the preparation of samples for Mössbauer spectroscopy studies of phase transformations in metals research are discussed in examples of works undertaken by the authors; (i) determination of austempering kinetics of compacted graphite cast irons, (ii) CEMS studies aimed at finding suitable polishing treatments that reproduce the bulk phase proportions, (iii) CEMS investigations on samples polished by spark planing, and (iv) the research of surface processes produced by laser melting treatments.

  7. In-situ characterization of transformation plasticity during an isothermal austenite-to-bainite phase transformation

    SciTech Connect

    Holzweissig, M.J.; Canadinc, D.; Maier, H.J.

    2012-03-15

    This paper elucidates the stress-induced variant selection process during the isothermal austenite-to-bainite phase transformation in a tool steel. Specifically, a thorough set of experiments combining electron backscatter diffraction and in-situ digital image correlation (DIC) was carried out to establish the role of superimposed stress level on the evolution of transformation plasticity (TP) strains. The important finding is that TP increases concomitant with the superimposed stress level, and strain localization accompanies phase transformation at all stress levels considered. Furthermore, TP strain distribution within the whole material becomes more homogeneous with increasing stress, such that fewer bainitic variants are selected to grow under higher stresses, yielding a more homogeneous strain distribution. In particular, the bainitic variants oriented along [101] and [201] directions are favored to grow parallel to the loading axis and are associated with large TP strains. Overall, this very first in-situ DIC investigation of the austenite-to-bainite phase transformation in steels evidences the clear relationship between the superimposed stress level, variant selection, and evolution of TP strains. - Highlights: Black-Right-Pointing-Pointer Local variations of strain were observed by DIC throughout the phase transformation. Black-Right-Pointing-Pointer The study clearly established the role of the stress-induced variant selection. Black-Right-Pointing-Pointer Variant selection is a key parameter that governs distortion.

  8. Kinetics of Phase Transformations in CuAu Alloys

    NASA Astrophysics Data System (ADS)

    Malis, O.; Ludwig, K.

    1997-03-01

    We have performed time resolved x-ray scattering studies of the kinetics of phase transformations in CuAu alloys. The equilibrium phase diagram of CuAu presents two first-order ordering transitions which separate the stability range of a high temperature disordered phase and two ordered phases: CuAuI and CuAuII. CuAuII is a modulated phase having a wavelength ten times larger than CuAuI. Our study focused on the competition between CuAuI and CuAuII as well as on the interaction between order and strain as the lattice changes from cubic in the disordered phase to tetragonal in CuAuI. During CuAuI formation from the disordered phase, CuAuII appears and persists even for quenches deep below the coexistence point of CuAuI and CuAuII. We have also found that the formation of CuAuI from CuAuII is considerably slower than the formation of CuAuI from the disordered phase for equal quench temperatures. Langevin simulations based on EMT are in good qualitative agreement with the x-ray results(Elder, Malis, Ludwig, Chakraborty, Goldenfeld in preparation.). With increasing quench depth we also observe a change in kinetics from an incoherent nucleation process to a continuous transformation of the lattice while ordering.

  9. Anomalous compression behavior of germanium during phase transformation

    SciTech Connect

    Yan, Xiaozhi; Tan, Dayong; Ren, Xiangting; Yang, Wenge E-mail: duanweihe@scu.edu.cn; He, Duanwei E-mail: duanweihe@scu.edu.cn; Mao, Ho-Kwang

    2015-04-27

    In this article, we present the abnormal compression and plastic behavior of germanium during the pressure-induced cubic diamond to β-tin structure transition. Between 8.6 GPa and 13.8 GPa, in which pressure range both phases are co-existing, first softening and followed by hardening for both phases were observed via synchrotron x-ray diffraction and Raman spectroscopy. These unusual behaviors can be interpreted as the volume misfit between different phases. Following Eshelby, the strain energy density reaches the maximum in the middle of the transition zone, where the switch happens from softening to hardening. Insight into these mechanical properties during phase transformation is relevant for the understanding of plasticity and compressibility of crystal materials when different phases coexist during a phase transition.

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

    DOE PAGESBeta

    Tan, L.; Yang, Y.

    2015-11-01

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

  11. Simultaneous lead and antimony immobilization in shooting range soil by a combined application of hydroxyapatite and ferrihydrite.

    PubMed

    Ogawa, Shouhei; Katoh, Masahiko; Sato, Takeshi

    2015-01-01

    This study investigated whether a combined application of hydroxyapatite and ferrihydrite could immobilize lead and antimony in shooting range soil in which the level of lead contamination is markedly higher than that of antimony. In addition, we evaluated the stability of lead and antimony immobilized by the combined application with varying soil pH. The levels of water-soluble lead and antimony for the combined application were lower than those of single applications of hydroxyapatite or ferrihydrite, indicating that the combined application could suppress the levels of water-soluble lead and antimony by 99.9% and 95.5%, respectively, as compared with the levels in shooting range soil without immobilization material. The amounts of residual lead and amorphous Fe/Al oxide-bound antimony fractions in sequential extraction increased with a decrease in the exchangeable and carbonate lead fractions as well as in non-specifically bound and specifically bound antimony fractions. The alteration of lead and antimony phases to chemically more stable ones as a result of the combined application would result in the suppression of their mobility. The stability of immobilized lead and antimony in the combined application was equal to that of lead with a single application of hydroxyapatite and that of antimony with a single application of ferrihydrite within neutral to alkaline pH conditions, respectively. Therefore, this study suggests that the combined application of hydroxyapatite and ferrihydrite can simultaneously immobilize lead and antimony in shooting range soil with neutral to alkaline pH.

  12. Aggregate-scale heterogeneity in iron (hydr)oxide reductive transformations

    SciTech Connect

    Tufano, K.J.; Benner, S.G.; Mayer, K.U.; Marcus, M.A.; Nico, P.S.; Fendorf, S.

    2009-06-15

    There is growing awareness of the complexity of potential reaction pathways and the associated solid-phase transformations during the reduction of Fe (hydr)oxides, especially ferrihydrite. An important observation in static and advective-dominated systems is that microbially produced Fe(II) accelerates Ostwald ripening of ferrihydrite, thus promoting the formation of thermodynamically more stable ferric phases (lepidocrocite and goethite) and, at higher Fe(II) surface loadings, the precipitation of magnetite; high Fe(II) levels can also lead to green rust formation, and with high carbonate levels siderite may also be formed. This study expands this emerging conceptual model to a diffusion-dominated system that mimics an idealized micropore of a ferrihydrite-coated soil aggregate undergoing reduction. Using a novel diffusion cell, coupled with micro-x-ray fluorescence and absorption spectroscopies, we determined that diffusion-controlled gradients in Fe{sup 2+}{sub (aq)} result in a complex array of spatially distributed secondary mineral phases. At the diffusive pore entrance, where Fe{sup 2+} concentrations are highest, green rust and magnetite are the dominant secondary Fe (hydr)oxides (30 mol% Fe each). At intermediate distances from the inlet, green rust is not observed and the proportion of magnetite decreases from approximately 30 to <10%. Across this same transect, the proportion of goethite increases from undetectable up to >50%. At greater distances from the advective-diffusive boundary, goethite is the dominant phase, comprising between 40 and 95% of the Fe. In the presence of magnetite, lepidocrocite forms as a transient-intermediate phase during ferrihydrite-to-goethite conversion; in the absence of magnetite, conversion to goethite is more limited. These experimental observations, coupled with results of reactive transport modeling, confirm the conceptual model and illustrate the potential importance of diffusion-generated concentration gradients in

  13. Iterative-Transform Phase Retrieval Using Adaptive Diversity

    NASA Technical Reports Server (NTRS)

    Dean, Bruce H.

    2007-01-01

    A phase-diverse iterative-transform phase-retrieval algorithm enables high spatial-frequency, high-dynamic-range, image-based wavefront sensing. [The terms phase-diverse, phase retrieval, image-based, and wavefront sensing are defined in the first of the two immediately preceding articles, Broadband Phase Retrieval for Image-Based Wavefront Sensing (GSC-14899-1).] As described below, no prior phase-retrieval algorithm has offered both high dynamic range and the capability to recover high spatial-frequency components. Each of the previously developed image-based phase-retrieval techniques can be classified into one of two categories: iterative transform or parametric. Among the modifications of the original iterative-transform approach has been the introduction of a defocus diversity function (also defined in the cited companion article). Modifications of the original parametric approach have included minimizing alternative objective functions as well as implementing a variety of nonlinear optimization methods. The iterative-transform approach offers the advantage of ability to recover low, middle, and high spatial frequencies, but has disadvantage of having a limited dynamic range to one wavelength or less. In contrast, parametric phase retrieval offers the advantage of high dynamic range, but is poorly suited for recovering higher spatial frequency aberrations. The present phase-diverse iterative transform phase-retrieval algorithm offers both the high-spatial-frequency capability of the iterative-transform approach and the high dynamic range of parametric phase-recovery techniques. In implementation, this is a focus-diverse iterative-transform phaseretrieval algorithm that incorporates an adaptive diversity function, which makes it possible to avoid phase unwrapping while preserving high-spatial-frequency recovery. The algorithm includes an inner and an outer loop (see figure). An initial estimate of phase is used to start the algorithm on the inner loop, wherein

  14. Isomorphic phase transformation in shocked cerium using molecular dynamics

    SciTech Connect

    Dupont, Virginie; Germann, Timothy C; Chen, Shao - Ping

    2010-08-12

    Cerium (Ce) undergoes a significant ({approx}16%) volume collapse associated with an isomorphic fcc-fcc phase transformation when subject to compressive loading. We present here a new Embedded Atom Method (EAM) potential for Cerium that models two minima for the two fcc phases. We show results from its use in Molecular Dynamics (MD) simulations of Ce samples subjected to shocks with pressures ranging from 0.5 to 25 GPa. A split wave structure is observed, with an elastic precursor followed by a plastic wave. The plastic wave causes the expected fcc-fcc phase transformation. Comparisons to experiments and MD simulations on Cesium (Cs) indicate that three waves could be observed. The construction of the EAM potential may be the source of the difference.

  15. Nanowire growth by an electron beam induced massive phase transformation

    DOE PAGESBeta

    Sood, Shantanu; Kisslinger, Kim; Gouma, Perena

    2014-11-15

    Tungsten trioxide nanowires of a high aspect ratio have been synthesized in-situ in a TEM under an electron beam of current density 14A/cm² due to a massive polymorphic reaction. Sol-gel processed pseudocubic phase nanocrystals of tungsten trioxide were seen to rapidly transform to one dimensional monoclinic phase configurations, and this reaction was independent of the substrate on which the material was deposited. The mechanism of the self-catalyzed polymorphic transition and accompanying radical shape change is a typical characteristic of metastable to stable phase transformations in nanostructured polymorphic metal oxides. A heuristic model is used to confirm the metastable to stablemore » growth mechanism. The findings are important to the control electron beam deposition of nanowires for functional applications starting from colloidal precursors.« less

  16. Reconstructing solute-induced phase transformations within individual nanocrystals.

    PubMed

    Narayan, Tarun C; Baldi, Andrea; Koh, Ai Leen; Sinclair, Robert; Dionne, Jennifer A

    2016-07-01

    Strain and defects can significantly impact the performance of functional nanomaterials. This effect is well exemplified by energy storage systems, in which structural changes such as volume expansion and defect generation govern the phase transformations associated with charging and discharging. The rational design of next-generation storage materials therefore depends crucially on understanding the correlation between the structure of individual nanoparticles and their solute uptake and release. Here, we experimentally reconstruct the spatial distribution of hydride phases within individual palladium nanocrystals during hydrogen absorption, using a combination of electron spectroscopy, dark-field imaging, and electron diffraction in an environmental transmission electron microscope. We show that single-crystalline cubes and pyramids exhibit a uniform hydrogen distribution at equilibrium, whereas multiply twinned icosahedra exclude hydrogen from regions of high compressive strains. Our technique offers unprecedented insight into nanoscale phase transformations in reactive environments and can be extended to a variety of functional nanomaterials. PMID:27088234

  17. Nanowire growth by an electron beam induced massive phase transformation

    SciTech Connect

    Sood, Shantanu; Kisslinger, Kim; Gouma, Perena

    2014-11-15

    Tungsten trioxide nanowires of a high aspect ratio have been synthesized in-situ in a TEM under an electron beam of current density 14A/cm² due to a massive polymorphic reaction. Sol-gel processed pseudocubic phase nanocrystals of tungsten trioxide were seen to rapidly transform to one dimensional monoclinic phase configurations, and this reaction was independent of the substrate on which the material was deposited. The mechanism of the self-catalyzed polymorphic transition and accompanying radical shape change is a typical characteristic of metastable to stable phase transformations in nanostructured polymorphic metal oxides. A heuristic model is used to confirm the metastable to stable growth mechanism. The findings are important to the control electron beam deposition of nanowires for functional applications starting from colloidal precursors.

  18. Thickness-induced structural phase transformation of layered gallium telluride.

    PubMed

    Zhao, Q; Wang, T; Miao, Y; Ma, F; Xie, Y; Ma, X; Gu, Y; Li, J; He, J; Chen, B; Xi, S; Xu, L; Zhen, H; Yin, Z; Li, J; Ren, J; Jie, W

    2016-07-28

    The thickness-dependent electronic states and physical properties of two-dimensional materials suggest great potential applications in electronic and optoelectronic devices. However, the enhanced surface effect in ultra-thin materials might significantly influence the structural stability, as well as the device reliability. Here, we report a spontaneous phase transformation of gallium telluride (GaTe) that occurred when the bulk was exfoliated to a few layers. Transmission electron microscopy (TEM) results indicate a structural variation from a monoclinic to a hexagonal structure. Raman spectra suggest a critical thickness for the structural transformation. First-principle calculations and thermodynamic analysis show that the surface energy and the interlayer interaction compete to dominate structural stability in the thinning process. A two-stage transformation process from monoclinic (m) to tetragonal (T) and then from tetragonal to hexagonal (h) is proposed to understand the phase transformation. The results demonstrate the crucial role of interlayer interactions in the structural stability, which provides a phase engineering strategy for device applications. PMID:27198938

  19. Thickness-induced structural phase transformation of layered gallium telluride.

    PubMed

    Zhao, Q; Wang, T; Miao, Y; Ma, F; Xie, Y; Ma, X; Gu, Y; Li, J; He, J; Chen, B; Xi, S; Xu, L; Zhen, H; Yin, Z; Li, J; Ren, J; Jie, W

    2016-07-28

    The thickness-dependent electronic states and physical properties of two-dimensional materials suggest great potential applications in electronic and optoelectronic devices. However, the enhanced surface effect in ultra-thin materials might significantly influence the structural stability, as well as the device reliability. Here, we report a spontaneous phase transformation of gallium telluride (GaTe) that occurred when the bulk was exfoliated to a few layers. Transmission electron microscopy (TEM) results indicate a structural variation from a monoclinic to a hexagonal structure. Raman spectra suggest a critical thickness for the structural transformation. First-principle calculations and thermodynamic analysis show that the surface energy and the interlayer interaction compete to dominate structural stability in the thinning process. A two-stage transformation process from monoclinic (m) to tetragonal (T) and then from tetragonal to hexagonal (h) is proposed to understand the phase transformation. The results demonstrate the crucial role of interlayer interactions in the structural stability, which provides a phase engineering strategy for device applications.

  20. Additional losses in three-phase transformer cores

    NASA Astrophysics Data System (ADS)

    Valković, Z.

    1984-02-01

    The influences of T-joint design and of the holes in yoke lamination on the magnetic properties have been investigated on scale models of three-phase three-limbed transformer core. Four variants of V-45° T-joint have been compared, and it has been found that they have virtually equal power losses, while the differences in magnetizing currents amount up to 60%. The variations of losses and magnetizing currents with hole diameter and flux density in the core are given. In distribution transformers of usual dimensions, a 2-4% increase of power losses due to holes in the yoke has been estimated.

  1. The use of Fourier reverse transforms in crystallographic phase refinement

    SciTech Connect

    Ringrose, S.

    1997-10-08

    Often a crystallographer obtains an electron density map which shows only part of the structure. In such cases, the phasing of the trial model is poor enough that the electron density map may show peaks in some of the atomic positions, but other atomic positions are not visible. There may also be extraneous peaks present which are not due to atomic positions. A method for determination of crystal structures that have resisted solution through normal crystallographic methods has been developed. PHASER is a series of FORTRAN programs which aids in the structure solution of poorly phased electron density maps by refining the crystallographic phases. It facilitates the refinement of such poorly phased electron density maps for difficult structures which might otherwise not be solvable. The trial model, which serves as the starting point for the phase refinement, may be acquired by several routes such as direct methods or Patterson methods. Modifications are made to the reverse transform process based on several assumptions. First, the starting electron density map is modified based on the fact that physically the electron density map must be non-negative at all points. In practice a small positive cutoff is used. A reverse Fourier transform is computed based on the modified electron density map. Secondly, the authors assume that a better electron density map will result by using the observed magnitudes of the structure factors combined with the phases calculated in the reverse transform. After convergence has been reached, more atomic positions and less extraneous peaks are observed in the refined electron density map. The starting model need not be very large to achieve success with PHASER; successful phase refinement has been achieved with a starting model that consists of only 5% of the total scattering power of the full molecule. The second part of the thesis discusses three crystal structure determinations.

  2. Surface chemistry of ferrihydrite: Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate

    NASA Astrophysics Data System (ADS)

    Waychunas, G. A.; Rea, B. A.; Fuller, C. C.; Davis, J. A.

    1993-05-01

    EXAFS spectra were collected on both the As and Fe K-edges from samples of two-line ferrihydrite with adsorbed (ADS) and coprecipitated (CPT) arsenate prepared over a range of conditions and arsenate surface coverages. Spectra also were collected for arsenate adsorbed on the surfaces of three FeOOH crystalline polymorphs, α (goethite), β (akaganeite), and γ (lepidocrocite), and as a free ion in aqueous: solution. Analyses of the As EXAFS show clear evidence for inner sphere bidentate (bridging) arsenate complexes on the ferrihydrite surface and on the surfaces of the crystalline FeOOH polymorphs. The bridging arsenate is attached to adjacent apices of edge-sharing Fe oxyhydroxyl octahedra. The arsenic-iron distance at the interface ( 3.28 ±0.01 Å) is close to that expected for this geometry on the FeOOH polymorph surfaces, but is slightly shorter on the ferrihydrite surfaces ( 3.25 ± 0.02 Å). Mono-dentate arsenate linkages ( 3.60 ± 0.03 Å) also occur on the ferrihydrite, but are not generally observed on the crystalline FeOOH polymorphs. The proportion of monodentate bonds appears largest for adsorption samples with the smallest As/Fe molar ratio. In all cases the arsenate tetrahedral complex is relatively undistorted with As-O bonds of 1.66 ± 0.01 Å. Precipitation of arsenate or scorodite-like phases was not observed for any samples, all of which were prepared at a pH value of 8. The Fe EXAFS results confirm that the Fe-Fe correlations in the ferrihydrite are progressively disrupted in the CPT samples as the As/Fe ratio is increased. Coherent crystallite size is probably no more than 10 Å in diameter and no Fe oxyhydroxyl octahedra corner-sharing linkages (as would be present in FeOOH polymorphs) are observed at the largest As/Fe ratios. Comparison of the number and type of Fe-Fe neighbors with the topological constraints imposed by the arsenate saturation limit in the CPT samples (about 0.7 As/Fe) indicates ferrihydrite units consisting mainly of Fe

  3. Surface chemistry of ferrihydrite: Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate

    USGS Publications Warehouse

    Waychunas, G.A.; Rea, B.A.; Fuller, C.C.; Davis, J.A.

    1993-01-01

    EXAFS spectra were collected on both the As and Fe K-edges from samples of two-line ferrihydrite with adsorbed (ADS) and coprecipitated (CPT) arsenate prepared over a range of conditions and arsenate surface coverages. Spectra also were collected for arsenate adsorbed on the surfaces of three FeOOH crystalline polymorphs, ?? (goethite), ?? (akaganeite), and ?? (lepidocrocite), and as a free ion in aqueous: solution. Analyses of the As EXAFS show clear evidence for inner sphere bidentate (bridging) arsenate complexes on the ferrihydrite surface and on the surfaces of the crystalline FeOOH polymorphs. The bridging arsenate is attached to adjacent apices of edge-sharing Fe oxyhydroxyl octahedra. The arsenic-iron distance at the interface (3.28 ??0.01 A ??) is close to that expected for this geometry on the FeOOH polymorph surfaces, but is slightly shorter on the ferrihydrite surfaces (3.25 ?? 0.02 A ??). Mono-dentate arsenate linkages (3.60 ?? 0.03 A ??) also occur on the ferrihydrite, but are not generally observed on the crystalline FeOOH polymorphs. The proportion of monodentate bonds appears largest for adsorption samples with the smallest As Fe molar ratio. In all cases the arsenate tetrahedral complex is relatively undistorted with As-O bonds of 1.66 ?? 0.01 A ??. Precipitation of arsenate or scorodite-like phases was not observed for any samples, all of which were prepared at a pH value of 8. The Fe EXAFS results confirm that the Fe-Fe correlations in the ferrihydrite are progressively disrupted in the CPT samples as the As Fe ratio is increased. Coherent crystallite size is probably no more than 10 A?? in diameter and no Fe oxyhydroxyl octahedra corner-sharing linkages (as would be present in FeOOH polymorphs) are observed at the largest As Fe ratios. Comparison of the number and type of Fe-Fe neighbors with the topological constraints imposed by the arsenate saturation limit in the CPT samples (about 0.7 As Fe) indicates ferrihydrite units consisting mainly

  4. Magnetostructural phase transformations in Tb 1-x Mn 2

    DOE PAGESBeta

    Zou, Junding; Paudyal, Durga; Liu, Jing; Mudryk, Yaroslav; Pecharsky, Vitalij K.; Gschneidner, Karl A.

    2015-01-16

    Magnetism and phase transformations in non-stoichiometric Tb1-xMn2 (x = 0.056, 0.039) have been studied as functions of temperature and magnetic field using magnetization, heat capacity, and X-ray powder diffraction measurements. Lowering the temperature, the compounds sequentially order ferrimagnetically and antiferromagnetically, and finally, exhibit spin reorientation transitions. Moreover, these structural distortions from room temperature cubic to low temperature rhombohedral structures occur at TN, and are accompanied by large volume changes reaching ~-1.27% and -1.42%, respectively. First principles electronic structure calculations confirm the phase transformation from the ferrimagnetic cubic structure to the antiferromagnetic rhombohedral structure in TbMn2.

  5. Application of phase coherent transform to cloud clutter suppression

    SciTech Connect

    Ng, L.C.

    1994-11-15

    This paper describes a tracking algorithm using frame-to-frame correlation with frequency domain clutter suppression. Clutter suppression was mechanized via a `Phase Coherent Transform` (PCT) approach. This approach was applied to explore the feasibility of tracking a post-boost rocket from a low earth orbit satellite with real cloud background data. Simulation results show that the PCT/correlation tracking algorithm can perform satisfactorily at signal-to-clutter ratio (SCR) as low as 5 or 7 dB.

  6. Patterning Oxide Nanopillars at the Atomic Scale by Phase Transformation.

    PubMed

    Chen, Chunlin; Wang, Zhongchang; Lichtenberg, Frank; Ikuhara, Yuichi; Bednorz, Johannes Georg

    2015-10-14

    Phase transformations in crystalline materials are common in nature and often modify dramatically properties of materials. The ability to precisely control them with a high spatial precision represents a significant step forward in realizing new functionalities in confined dimensions. However, such control is extremely challenging particularly at the atomic scale due to the intricacies in governing thermodynamic conditions with a high spatial accuracy. Here, we apply focused electron beam of a scanning transmission electron microscope to irradiate SrNbO3.4 crystals and demonstrate a precise control of a phase transformation from layered SrNbO3.4 to perovskite SrNbO3 at the atomic scale. By purposely squeezing O atoms out of the vertex-sharing NbO6 octahedral slabs, their neighboring slabs zip together, resulting in a patterning of SrNbO3 nanopillars in SrNbO3.4 matrix. Such phase transformations can be spatially manipulated with an atomic precision, opening up a novel avenue for materials design and processing and also for advanced nanodevice fabrication.

  7. Stress and phase transformation phenomena in oxide films

    SciTech Connect

    Exarhos, G.J.; Hess, N.J.

    1992-04-01

    In situ optical methods are reviewed for characterization of phase transformation processes and evaluation of residual stress in solution- deposited metastable oxide films. Such low density films most often are deposited as disordered phases making them prone to crystallization and attendant densification when subjected to increased temperature and/or applied pressure. Inherent stress imparted during film deposition and its evolution during the transformation are evaluated from phonon frequency shifts seen in Raman spectra (TiO{sub 2}) or from changes in the laser-induced fluorescence emission spectra for films containing rare earth (Sm{sup +3}:Y{sub 3}Al{sub 5}O{sub 12}) or transition metal (Cr{sup +3}:Al{sub 2}O{sub 3}) dopants. The data in combination with measured increases in line intensities intrinsic to the evolving phase are used to follow crystallization processes in thin films. In general, film deposition parameters are found to influence the crystallite ingrowth kinetics and the magnitude of stress and stress relaxation in the film during the transformation. The utility of these methods to probe crystallization phenomena in oxide films will be addressed.

  8. Construction of a Fourier-transform phase-modulation fluorometer

    NASA Astrophysics Data System (ADS)

    Iwata, Tetsuo; Shibata, Hironobu; Araki, Tsutomu

    2005-11-01

    We have constructed a Fourier-transform phase-modulation fluorometer (FT-PMF) by which a fluorescence decay waveform can be obtained. In the FT-PMF, the modulation frequency of the excitation light source is swept continuously from a direct current (dc) to a high frequency fmax with a time duration T. The resultant fluorescence signal waveform is Fourier transformed to obtain its amplitude and phase spectra. The ratio of the amplitude spectrum and the difference of the phase spectrum over those of the reference spectra from an excitation waveform are calculated, respectively, and the pair of both spectral data is inverse-Fourier-transformed again to obtain the fluorescence decay waveform. The light source used was an ultraviolet light-emitting diode (UV LED) whose operating condition was fmax = 50-120 MHz and T = 10 µs. To demonstrate the performance of the FT-PMF, we carried out (1) the measurement of a fluorescent decay waveform of YAG materials enclosed in a white LED and (2) determinations of fluorescence lifetimes of 10 ppm quinine sulfate in 0.1 N H2SO4 and 10 ppm rhodamine 6G in ethanol.

  9. Construction of a Fourier-transform phase-modulation fluorometer

    NASA Astrophysics Data System (ADS)

    Shibata, Hironobu; Iwata, Tetsuo

    2005-12-01

    We have constructed a Fourier-transform phase-modulation fluorometer (FT-PMF) by which a fluorescence decay waveform can be obtained. In the FT-PMF, the modulation frequency of the excitation light source is swept continuously from a direct current (dc) to a high frequency f max with a time duration T. The resultant fluorescence signal waveform is Fourier-transformed to obtain its amplitude and phase spectra. The ratio of the amplitude spectrum and the difference of the phase spectrum over those of the reference spectra that are obtained from a non-fluorescent material are calculated, respectively, and the pair of both spectral data is inverse-Fourier-transformed again to obtain the fluorescence decay waveform. The light source used was an ultraviolet light emitting- diode (UV LED) whose typical operating condition was f max = 100 MHz and T = 10 μs. To demonstrate the performance of the FT-PMF, we carried out (1) measurement of a fluorescent decay waveform of YAG materials packed in a white LED, and (2) determination of fluorescence lifetime of 10 ppm quinine sulfate in 0.1N H IISO 4.

  10. Phase transformations in some hafnium-tantalum-titanium-zirconium alloys

    SciTech Connect

    Ohriner, E.K.; Kapoor, D.

    1997-11-01

    Phase transformations in hafnium alloys are of interest as a means of achieving a material which exhibits flow softening and high localized strains during deformation at high strain rates. Hafnium transforms from a body-centered-cubic beta phase to a hexagonal alpha phase upon cooling below 1749{degrees}C. Hafnium-based alloys containing up to 17.5% Ti, up to 17.5% Ta, and up to 7.3% Zr by weight were button-arc melted and, in some cases, hot extruded to obtain a refined grain size. A number of alloys were shown to have beta solvus temperatures in the range of 1100 to 1300{degrees}C and showed evidence of a shear transformation upon water quenching. The Vickers microhardness of the quenched materials are typically above 350 HV as compared to 300 HV or less for materials with an alpha plus beta structure. Quenching dilatometry indicates a martensite start temperature of about 750{degrees}C for the Hf-7.5 Ta-10 Ti-1 Zr alloy and 800{degrees}C or more for the Hf-7.5 Ta-7.5 Ti-1 Zr alloy. Tensile tests at 1 s{sup {minus}1} strain rate show a constant ultimate tensile strength for temperatures up to 600{degrees}C for the above two alloys and a rapid decrease in strength with a further increase in temperature.

  11. Phase field modeling of tetragonal to monoclinic phase transformation in zirconia

    NASA Astrophysics Data System (ADS)

    Mamivand, Mahmood

    Zirconia based ceramics are strong, hard, inert, and smooth, with low thermal conductivity and good biocompatibility. Such properties made zirconia ceramics an ideal material for different applications form thermal barrier coatings (TBCs) to biomedicine applications like femoral implants and dental bridges. However, this unusual versatility of excellent properties would be mediated by the metastable tetragonal (or cubic) transformation to the stable monoclinic phase after a certain exposure at service temperatures. This transformation from tetragonal to monoclinic, known as LTD (low temperature degradation) in biomedical application, proceeds by propagation of martensite, which corresponds to transformation twinning. As such, tetragonal to monoclinic transformation is highly sensitive to mechanical and chemomechanical stresses. It is known in fact that this transformation is the source of the fracture toughening in stabilized zirconia as it occurs at the stress concentration regions ahead of the crack tip. This dissertation is an attempt to provide a kinetic-based model for tetragonal to monoclinic transformation in zirconia. We used the phase field technique to capture the temporal and spatial evolution of monoclinic phase. In addition to morphological patterns, we were able to calculate the developed internal stresses during tetragonal to monoclinic transformation. The model was started form the two dimensional single crystal then was expanded to the two dimensional polycrystalline and finally to the three dimensional single crystal. The model is able to predict the most physical properties associated with tetragonal to monoclinic transformation in zirconia including: morphological patterns, transformation toughening, shape memory effect, pseudoelasticity, surface uplift, and variants impingement. The model was benched marked with several experimental works. The good agreements between simulation results and experimental data, make the model a reliable tool for

  12. Fundamental Mechanisms Driving the Amorphous to Crystalline Phase Transformation

    SciTech Connect

    Reed, B W; Browning, N D; Santala, M K; LaGrange, T; Gilmer, G H; Masiel, D J; Campbell, G H; Raoux, S; Topuria, T; Meister, S; Cui, Y

    2011-01-04

    Phase transformations are ubiquitous, fundamental phenomena that lie at the heart of many structural, optical and electronic properties in condensed matter physics and materials science. Many transformations, especially those occurring under extreme conditions such as rapid changes in the thermodynamic state, are controlled by poorly understood processes involving the nucleation and quenching of metastable phases. Typically these processes occur on time and length scales invisible to most experimental techniques ({micro}s and faster, nm and smaller), so our understanding of the dynamics tends to be very limited and indirect, often relying on simulations combined with experimental study of the ''time infinity'' end state. Experimental techniques that can directly probe phase transformations on their proper time and length scales are therefore key to providing fundamental insights into the whole area of transformation physics and materials science. LLNL possesses a unique dynamic transmission electron microscope (DTEM) capable of taking images and diffraction patterns of laser-driven material processes with resolution measured in nanometers and nanoseconds. The DTEM has previously used time-resolved diffraction patterns to quantitatively study phase transformations that are orders of magnitude too fast for conventional in situ TEM. More recently the microscope has demonstrated the ability to directly image a reaction front moving at {approx}13 nm/ns and the nucleation of a new phase behind that front. Certain compound semiconductor phase change materials, such as Ge{sub 2}Sb{sub 2}Te{sub 5} (GST), Sb{sub 2}Te and GeSb, exhibit a technologically important series of transformations on scales that fall neatly into the performance specifications of the DTEM. If a small portion of such material is heated above its melting point and then rapidly cooled, it quenches into an amorphous state. Heating again with a less intense pulse leads to recrystallization into a vacancy

  13. Properties of impurity-bearing ferrihydrite I. Effects of Al content and precipitation rate on the structure of 2-line ferrihydrite

    SciTech Connect

    Cismasu, A. Cristina; Michel, F. Marc; Stebbins, Jonathan F.; Levard, Clément; Brown, Jr., Gordon E.

    2012-10-11

    The association of Al with ferrihydrite (Fh) may have a considerable effect on the composition, structure, and surface properties of Fh nanoparticles, and thus impact its reactivity and interaction with pollutant species. Aluminous Fh is abundant in natural environments, but the mode of association of Al with this nanomineral is not yet fully understood. Al{sup 3+} speciation may vary from true chemical substitution for Fe{sup 3+}, to adsorption or surface precipitation, and/or to formation of a mixture of two (or more) individual nanoscale phases. The conditions of formation (i.e. slow vs. rapid precipitation) may also affect the nature of Fh nanoparticles in terms of their crystallinity, phase purity, and Al speciation. In this study we used a variety of laboratory (TEM, NMR, ICP-AES) and synchrotron-based techniques (X-ray total scattering and PDF analysis, scanning transmission X-ray microscopy, Al K-edge XANES spectroscopy) to characterize two synthetic Al-bearing Fh series formed at different precipitation rates in the presence of 5-40 mol% Al. We find that Al is dominantly octahedrally coordinated in the synthetic Fh samples and that up to 20-30 mol% Al substitutes for Fe in the Fh structure, regardless of the synthesis method we used. Formation of separate aluminous phases (e.g., gibbsite) was most significant at Al concentrations above 30 mol% Al in slowly precipitated samples. However, small amounts (<6% of total Al) of Al-hydroxide phases were also detected by NMR spectroscopy in samples with lower Al content (as low as 15 mol% Al), particularly in the Fh series that was precipitated slowly. Furthermore, it appears that the amount of Al incorporated in Fh is not affected by the synthesis methods we used and is more likely controlled by the accumulated strain caused by Al substitution in the Fh lattice. Given the prevalence of naturally occurring aluminous ferrihydrite, assumptions about ferrihydrite reactivity in natural environments should consider the

  14. Phase transformation diffusion bonding of titanium alloy with stainless steel

    SciTech Connect

    Qin, B. . E-mail: jjj-jenny@163.com; Sheng, G.M.; Huang, J.W.; Zhou, B.; Qiu, S.Y.; Li, C.

    2006-01-15

    Phase transformation diffusion bonding between a titanium alloy (TA17) and an austenitic stainless steel (0Cr18Ni9Ti) has been carried out in vacuum. Relationships between the bonding parameters and the tensile strength of the joints were investigated, and the optimum bond parameters were obtained: maximum cyclic temperature = 890 deg. C, minimum cyclic temperature = 800 deg. C, number of cycles = 10, bonding pressure = 5 MPa and heating rate = 30 deg. C/s. The maximum tensile strength of the joint was 307 MPa. The reaction products and the interface structure of the joints were investigated by light optical and scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction. The study indicated the existence of {sigma} phase, Fe{sub 2}Ti, Fe-Ti intermetallic and {beta}-Ti in the reaction zone. The presence of the brittle Fe-Ti intermetallic phase lowered both the strength and the ductility of the phase transformation diffusion-bonded joint significantly.

  15. Phase demodulation using adaptive windowed Fourier transform based on Hilbert-Huang transform.

    PubMed

    Wang, Chenxing; Da, Feipeng

    2012-07-30

    The phase demodulation method of adaptive windowed Fourier transform (AWFT) is proposed based on Hilbert-Huang transform (HHT). HHT is analyzed and performed on fringe pattern to obtain instantaneous frequencies firstly. These instantaneous frequencies are further analyzed based on the condition of AWFT to locate local stationary areas where the fundamental spectrum will not be interfered by high-order spectrum. Within each local stationary area, the fundamental spectrum can be extracted accurately and adaptively by using AWFT with the background, which has been determined previously with the presented criterion during HHT, being eliminated to remove the zero-spectrum. This method is adaptive and unconstrained by any precondition for the measured phase. Experiments demonstrate its robustness and effectiveness for measuring the object with discontinuities or complex surface.

  16. Fourier transform infrared phase shift cavity ring down spectrometer

    NASA Astrophysics Data System (ADS)

    Schundler, Elizabeth; Mansur, David J.; Vaillancourt, Robert; Benedict-Gill, Ryan; Newbry, Scott P.; Engel, James R.; Rentz Dupuis, Julia

    2013-05-01

    We report on our current status towards the development of a prototype Fourier transform infrared phase shift cavity ring down spectrometer (FTIR-PS-CRDS) system under a U.S. EPA SBIR contract. Our system uses the inherent wavelength-dependent modulation imposed by the FTIR on a broadband thermal source for the phase shift measurement. This spectrally-dependent phase shift is proportional to the spectrally-dependent ring down time, which is proportional to the losses of the cavity including those due to molecular absorption. Our approach is a broadband and spectral range enhancement to conventional CRDS which is typically done in the near IR at a single wavelength; at the same time our approach is a sensitivity enhancement to traditional FTIR owing to the long effective path of the resonant cavity. In this paper we present a summary of the theory including performance projections and the design details of the prototype FTIR-PS-CRDS system.

  17. A study of geometric phase topology using Fourier transform method

    NASA Astrophysics Data System (ADS)

    Samlan, C. T.; Naik, Dinesh N.; Viswanathan, Nirmal K.

    2016-07-01

    Topological aspect of the geometric phase (GP) due to pure polarization projection is studied using the 2D Fourier transform (2D-FT) method. Projection of orthogonal polarization state results in a phase singularity in the 2D parameter space of ellipticity and orientation of polarization ellipse. Projection of its surrounding states results in an accumulation of GP in different amount that form a spiral structure. A half wave plate-quarter wave plate combination is used to generate different polarization states which are projected using a polarizer. The accumulated phase for each orientation of the wave plate is extracted from 2D-FT of the interferogram, obtained by interfering it with a reference beam in a Mach-Zehnder like interferometer.

  18. Texture evolution during nitinol martensite detwinning and phase transformation

    SciTech Connect

    Cai, S.; Schaffer, J. E.; Ren, Y.

    2013-12-09

    Nitinol has been widely used to make medical devices for years due to its unique shape memory and superelastic properties. However, the texture of the nitinol wires has been largely ignored due to inherent complexity. In this study, in situ synchrotron X-ray diffraction has been carried out during uniaxial tensile testing to investigate the texture evolution of the nitinol wires during martensite detwinning, variant reorientation, and phase transformation. It was found that the thermal martensitic nitinol wire comprised primarily an axial (1{sup ¯}20), (120), and (102)-fiber texture. Detwinning initially converted the (120) and (102) fibers to the (1{sup ¯}20) fiber and progressed to a (1{sup ¯}30)-fiber texture by rigid body rotation. At strains above 10%, the (1{sup ¯}30)-fiber was shifted to the (110) fiber by (21{sup ¯}0) deformation twinning. The austenitic wire exhibited an axial (334)-fiber, which transformed to the near-(1{sup ¯}30) martensite texture after the stress-induced phase transformation.

  19. Nonequilibrium phase transformations in bcc titanium and niobium alloys

    NASA Astrophysics Data System (ADS)

    Doherty, Kevin James

    The major goal throughout this entire study was to find a bulk beta-titanium amorphous system. In this case, the feasibility of bulk amorphization by destabilizing the crystalline phase in bcc titanium alloys is developed. The binary Ti-Cr system was previously reported, by others, to undergo spontaneous vitrification. This work was later proven to be irreproducible by several other groups. With the proper alloying additions to the Ti-Cr system, the resultant bcc matrix is extremely unstable, however, the formation of alpha, o, and intermetallics is inhibited. Powders of the complex system Ti65Cr13Cu 16Mn4Fe2 transform to a fully amorphous structure after just 3 to 4 hours of mechanical milling. In bulk, this system forms nanoscale disordered regions, totaling 20 to 30% of the microstructure, upon annealing of the metastable bcc phase. The phase separation, beta → beta + beta' accompanies this transformation and induces strain into the matrix. Analytical high resolution transmission electron microscopy (TEM) is used to characterize the decomposition behavior by obtaining physical measurements of the microstructure and chemistry, and to determine the mechanism of the phase separation. High resolution and analytical TEM data map the development of successive chromium rich (copper poor) and chromium poor (copper rich) regions formed in <100> directions during heat treatment. This reaction is shown to occur by spinodal decomposition. A known bcc, binary spinodal decomposition system, Nb-Zr, was chosen as a reference system to verify the spinodal mechanism in the 5-component titanium system and to validate the use of analytical TEM to characterize spinodal decomposition. The Ti-Cr system is also investigated for comparison with the complex Ti-Cr-Cu-Mn-Fe system and to resolve some of the issues presented during the earlier spontaneous vitrification studies. Finally, a combination of high resolution TEM and chemical analysis is utilized to differentiate between the

  20. Effect of silicic acid on arsenate and arsenite retention mechanisms on 6-L ferrihydrite: A spectroscopic and batch adsorption approach.

    PubMed

    Gao, Xiaodong; Root, Robert A; Farrell, James; Ela, Wendell; Chorover, Jon

    2013-11-01

    The competitive adsorption of arsenate and arsenite with silicic acid at the ferrihydrite-water interface was investigated over a wide pH range using batch sorption experiments, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) modeling. Batch sorption results indicate that the adsorption of arsenate and arsenite on the 6-L ferrihydrite surface exhibits a strong pH-dependence, and the effect of pH on arsenic sorption differs between arsenate and arsenite. Arsenate adsorption decreases consistently with increasing pH; whereas arsenite adsorption initially increases with pH to a sorption maximum at pH 7-9, where after sorption decreases with further increases in pH. Results indicate that competitive adsorption between silicic acid and arsenate is negligible under the experimental conditions; whereas strong competitive adsorption was observed between silicic acid and arsenite, particularly at low and high pH. In-situ, flow-through ATR-FTIR data reveal that in the absence of silicic acid, arsenate forms inner-sphere, binuclear bidentate, complexes at the ferrihydrite surface across the entire pH range. Silicic acid also forms inner-sphere complexes at ferrihydrite surfaces throughout the entire pH range probed by this study (pH 2.8 - 9.0). The ATR-FTIR data also reveal that silicic acid undergoes polymerization at the ferrihydrite surface under the environmentally-relevant concentrations studied (e.g., 1.0 mM). According to ATR-FTIR data, arsenate complexation mode was not affected by the presence of silicic acid. EXAFS analyses and DFT modeling confirmed that arsenate tetrahedra were bonded to Fe metal centers via binuclear bidentate complexation with average As(V)-Fe bond distance of 3.27 Å. The EXAFS data indicate that arsenite forms both mononuclear bidentate and binuclear bidentate complexes with 6-L ferrihydrite as indicated by two As

  1. The effect of calcium on aqueous uranium(VI) speciation and adsorption to ferrihydrite and quartz

    USGS Publications Warehouse

    Fox, P.M.; Davis, J.A.; Zachara, J.M.

    2006-01-01

    Recent studies of uranium(VI) geochemistry have focused on the potentially important role of the aqueous species, CaUO2 (CO3)32- and Ca2 UO2(CO3)30(aq), on inhibition of microbial reduction and uranium(VI) aqueous speciation in contaminated groundwater. However, to our knowledge, there have been no direct studies of the effects of these species on U(VI) adsorption by mineral phases. The sorption of U(VI) on quartz and ferrihydrite was investigated in NaNO3 solutions equilibrated with either ambient air (430 ppm CO2) or 2% CO2 in the presence of 0, 1.8, or 8.9 mM Ca2+. Under conditions where the Ca2UO2(CO3)30 (aq) species predominates U(VI) aqueous speciation, the presence of Ca in solution lowered U(VI) adsorption on quartz from 77% in the absence of Ca to 42% and 10% at Ca concentrations of 1.8 and 8.9 mM, respectively. U(VI) adsorption to ferrihydrite decreased from 83% in the absence of Ca to 57% in the presence of 1.8 mM Ca. Surface complexation model predictions that included the formation constant for aqueous Ca2UO2(CO3)30(aq) accurately simulated the effect of Ca2+ on U(VI) sorption onto quartz and ferrihydrite within the thermodynamic uncertainty of the stability constant value. This study confirms that Ca2+ can have a significant impact on the aqueous speciation of U(VI), and consequently, on the sorption and mobility of U(VI) in aquifers. ?? 2005 Elsevier Inc. All rights reserved.

  2. Temperature limited heaters using phase transformation of ferromagnetic material

    DOEpatents

    Vitek, John Michael [Oak Ridge, TN; Brady, Michael Patrick [Oak Ridge, TN

    2009-10-06

    Systems, methods, and heaters for treating a subsurface formation are described herein. Systems and methods for making heaters are described herein. At least one heater includes a ferromagnetic conductor and an electrical conductor. The electrical conductor is electrically coupled to the ferromagnetic conductor. The heater provides a first amount of heat at a lower temperature. The heater may provide a second reduced amount of heat when the heater reaches a selected temperature, or enters a selected temperature range, at which the ferromagnetic conductor undergoes a phase transformation.

  3. Two-dimensional phase transformation probed by second harmonic generation: Oscillatory transformation of the K/Al(111) system

    SciTech Connect

    Ying, Z.C.; Plummer, E.W. |

    1995-12-31

    The technique of optical second harmonic generation is used to study phase transformations at two-dimensional surfaces and interfaces. Examples are given to illustrate that changes in surface symmetry, adsorption configuration, and electronic structure can be detected by this nonlinear optical technique. An oscillatory phase transformation of potassium adsorbed atoms on Al(111) probed by second harmonic generation is analyzed in detail.

  4. Target tracking using log-polar transform-based shifted phase-encoded joint transform correlation

    NASA Astrophysics Data System (ADS)

    Islam, Mohammed Nazrul; Bitew, Worku T.

    2014-04-01

    Automatic target detection and tracking requires efficient recognition of the target pattern in variable environmental conditions. Optical joint transform correlation (JTC) method has been proven to be efficient in recognizing a target without requiring complex optical set up. However, the classical JTC suffers from poor correlation performance, which can be improved through the use of different and modified designs. A very successful scheme is developed by employing phase-shifted and phase-encoded fringe-adjusted JTC (SPFJTC), which provides with a high discrimination between a target and non-target objects in a given scene and better utilization of the space-bandwidth resource. Further enhancement of the target detection performance can be achieved by incorporating log-polar transform in the SPFJTC technique. We applied the SPFJTC technique to the log-polar transformation of both the reference image and the input scene that makes the pattern recognition invariant to rotation and scale variations. Peak-to-side lobe ratio is measured and a threshold operation is employed to detect and track a target in an unknown input scene.

  5. Modelling a single phase voltage controlled rectifier using Laplace transforms

    NASA Technical Reports Server (NTRS)

    Kraft, L. Alan; Kankam, M. David

    1992-01-01

    The development of a 20 kHz, AC power system by NASA for large space projects has spurred a need to develop models for the equipment which will be used on these single phase systems. To date, models for the AC source (i.e., inverters) have been developed. It is the intent of this paper to develop a method to model the single phase voltage controlled rectifiers which will be attached to the AC power grid as an interface for connected loads. A modified version of EPRI's HARMFLO program is used as the shell for these models. The results obtained from the model developed in this paper are quite adequate for the analysis of problems such as voltage resonance. The unique technique presented in this paper uses the Laplace transforms to determine the harmonic content of the load current of the rectifier rather than a curve fitting technique. Laplace transforms yield the coefficient of the differential equations which model the line current to the rectifier directly.

  6. On Cyclical Phase Transformations in Driven Alloy Systems

    NASA Astrophysics Data System (ADS)

    Lee, Jong K.

    2008-05-01

    Cyclical phase transformations occurring in driven materials syntheses such as ball milling are described in terms of a free energy minimization process of participant phases. The oscillatory flow behavior of metals with low stacking fault energies during hot working is taken as a prototype in which a ductile crystalline phase sustains undulation in its free energy, due to the alternate succession of work-hardening and work-softening mechanisms. A time-dependent, oscillatory free energy function is then obtained by solving a delay differential equation (DDE), which accounts for a time lag due to diffusion. To understand cyclical transitions on an atomistic scale, work is extended to molecular dynamics simulations. Under shear deformation, a two-dimensional nanocrystal shows cyclical transitions between an equilibrium rhombus and a nonequilibrium square phase. Three-dimensional simulations show crystalline-to-glass transitions at high strain rates, but very high shear strain rates are found to lead to a latticelike network structure in the plane perpendicular to the shear direction, with strings of atoms parallel to the shear direction.

  7. Phase-field-crystal methodology for modeling of structural transformations.

    PubMed

    Greenwood, Michael; Rottler, Jörg; Provatas, Nikolas

    2011-03-01

    We introduce and characterize free-energy functionals for modeling of solids with different crystallographic symmetries within the phase-field-crystal methodology. The excess free energy responsible for the emergence of periodic phases is inspired by classical density-functional theory, but uses only a minimal description for the modes of the direct correlation function to preserve computational efficiency. We provide a detailed prescription for controlling the crystal structure and introduce parameters for changing temperature and surface energies, so that phase transformations between body-centered-cubic (bcc), face-centered-cubic (fcc), hexagonal-close-packed (hcp), and simple-cubic (sc) lattices can be studied. To illustrate the versatility of our free-energy functional, we compute the phase diagram for fcc-bcc-liquid coexistence in the temperature-density plane. We also demonstrate that our model can be extended to include hcp symmetry by dynamically simulating hcp-liquid coexistence from a seeded crystal nucleus. We further quantify the dependence of the elastic constants on the model control parameters in two and three dimensions, showing how the degree of elastic anisotropy can be tuned from the shape of the direct correlation functions. PMID:21517507

  8. Local phase transformation in alloys during charged-particle irradiation

    SciTech Connect

    Lam, N.Q.; Okamoto, P.R.

    1984-10-01

    Among the various mechanisms and processes by which energetic irradiation can alter the phase stability of alloys, radiation-induced segregation is one of the most important phenomena. Radiation-induced segregation in alloys occurs as a consequence of preferential coupling between persistent fluxes of excess defects and solute atoms, leading to local enrichment or depletion of alloying elements. Thus, this phenomenon tends to drive alloy systems away from thermodynamic equilibrium, on a local scale. During charged-particle irradiations, the spatial nonuniformity in the defect production gives rise to a combination of persistent defect fluxes, near the irradiated surface and in the peak-damage region. This defect-flux combination can modify the alloy composition in a complex fashion, i.e., it can destabilize pre-existing phases, causing spatially- and temporally-dependent precipitation of new metastable phases. The effects of radiation-induced segregation on local phase transformations in Ni-based alloys during proton bombardment and high-voltage electron-microscope irradiation at elevated temperatures are discussed.

  9. Synthetic coprecipitates of exopolysaccharides and ferrihydrite. Part I: Characterization

    NASA Astrophysics Data System (ADS)

    Mikutta, Christian; Mikutta, Robert; Bonneville, Steeve; Wagner, Friedrich; Voegelin, Andreas; Christl, Iso; Kretzschmar, Ruben

    2008-02-01

    Iron(III) (hydr)oxides formed at extracellular biosurfaces or in the presence of exopolymeric substances of microbes and plants may significantly differ in their structural and physical properties from their inorganic counterparts. We synthesized ferrihydrite (Fh) in solutions containing acid polysaccharides [polygalacturonic acid (PGA), alginate, xanthan] and compared its properties with that of an abiotic reference by means of X-ray diffraction, transmission electron microscopy, gas adsorption (N 2, CO 2), X-ray absorption spectroscopy, 57Fe Mössbauer spectroscopy, and electrophoretic mobility measurements. The coprecipitates formed contained up to 37 wt% polymer. Two-line Fh was the dominant mineral phase in all precipitates. The efficacy of polymers to precipitate Fh at neutral pH was higher for polymers with more carboxyl C (PGA ˜ alginate > xanthan). Pure Fh had a specific surface area of 300 m 2/g; coprecipitation of Fh with polymers reduced the detectable mineral surface area by up to 87%. Likewise, mineral micro- (<2 nm) and mesoporosity (2-10 nm) decreased by up to 85% with respect to pure Fh, indicative of a strong aggregation of Fh particles by polymers in freeze-dried state. C-1s STXM images showed the embedding of Fh particles in polymer matrices on the micrometer scale. Iron EXAFS spectroscopy revealed no significant changes in the local coordination of Fe(III) between pure Fh and Fh contained in PGA coprecipitates. 57Fe Mössbauer spectra of coprecipitates confirmed Fh as dominant mineral phase with a slightly reduced particle size and crystallinity of coprecipitate-Fh compared to pure Fh and/or a limited magnetic super-exchange between Fh particles in the coprecipitates due to magnetic dilution by the polysaccharides. The pH iep of pure Fh in 0.01 M NaClO 4 was 7.1. In contrast, coprecipitates of PGA and alginate had a pH iep < 2. Considering the differences in specific surface area, porosity, and net charge between the coprecipitates and pure Fh

  10. Diffusion and Phase Transformations of Transition Metals on Silicon Surfaces

    NASA Astrophysics Data System (ADS)

    Lee, Ming-Yi.

    The role of surface diffusion and surface phase reaction kinetics of nickel (Ni) and cobalt (Co) on Si(111) and Si(100) are investigated under Ultra High Vacuum (UHV) conditions using Auger Spectroscopy (AES), Reflection High Electron Energy Diffraction (RHEED) and surface X-ray diffraction. The surface segregation phenomenon and the formation conditions for Si(111)-sqrt{19 } x sqrt{19}- rm R+/-23.4^circ phase (hereafter called sqrt{19}) for Ni/Si(111) are studied by RHEED and AES. Quench cooling induces surface segregation which restores the total accumulated dose of Ni to two surfaces of the wafer. The coverage dependence of phases thus produced follows: 7 x 7 to 1 x 1-RC(0.05Ml) to sqrt{19} (0.16Ml) then to B-type NiSi_2. It is found that there are 3 Ni atoms in the sqrt{19 } unit cell. A "race" of bulk diffusion versus surface diffusion for Ni in/on Si(111) is studied by depositing a laterally confined dot of metal on one side of the double side polished and UHV cleaned Si wafer and then measuring the lateral Auger profile on the reverse side following annealing and quenching. Ni reaches the far side of the wafer at temperatures as low as 500C via bulk diffusion with no measurable contribution from the surface paths, which are short-circuited by numerous, fast bulk paths. Similar results are found for Ni and Co on Si(111) and Si(100). The diffusivity and solid solubility calculated from the experiments are close to the bulk values known from the literature. In addition, the thermal stability, phase transformation and different dissolution mechanisms of sqrt {19} and 1 x 1-RC surface phases of Ni/Si(111) are carefully examined. The activation energies of these processes are compared on an Arrhenius plot. These are discussed in terms of the migration and formation mechanisms involved in these phase transformations. An energy level diagram is used to summarize the atomistic kinetics.

  11. The HCP To BCC Phase Transformation in Ti Characterized by Nanosecond Electron Microscopy

    SciTech Connect

    Campbell, G; LaGrange, T; King, W; Colvin, J; Ziegler, A; Browning, N; Kleinschmidt, H; Bostanjoglo, O

    2005-06-21

    The general class of martensitic phase transformations occurs by a rapid lattice-distortive mechanism, where kinetics and morphology of the transformation are dominated by the strain energy. Since transformation is diffusionless, phase fronts propagate through a crystal with great speed that can approach the speed of sound. We have observed a particular example of this class of phase transformation, the hexagonal close packed (HCP) to body centered cubic (BCC) transformation in titanium that is driven by a rapid increase in temperature. We have used a novel nanosecond electron microscope (the dynamic transmission electron microscope, DTEM) to acquire diffraction and imaging information on the transformation, which is driven in-situ by nanosecond laser irradiation. Using nanosecond exposure times that are possible in the DTEM, data can be collected about the transient events in these fast transformations. We have identified the phase transformation with diffraction patterns and correlated the time of the phase transformation with calculated conditions in the sample.

  12. Multiphase phase field theory for temperature- and stress-induced phase transformations

    NASA Astrophysics Data System (ADS)

    Levitas, Valery I.; Roy, Arunabha M.

    2015-05-01

    Thermodynamic Ginzburg-Landau potential for temperature- and stress-induced phase transformations (PTs) between n phases is developed. It describes each of the PTs with a single order parameter without an explicit constraint equation, which allows one to use an analytical solution to calibrate each interface energy, width, and mobility; reproduces the desired PT criteria via instability conditions; introduces interface stresses; and allows for a controlling presence of the third phase at the interface between the two other phases. A finite-element approach is developed and utilized to solve the problem of nanostructure formation for multivariant martensitic PTs. Results are in a quantitative agreement with the experiment. The developed approach is applicable to various PTs between multiple solid and liquid phases and grain evolution and can be extended for diffusive, electric, and magnetic PTs.

  13. Phase transformations and residual stresses in environmental barrier coatings

    NASA Astrophysics Data System (ADS)

    Harder, Bryan J.

    Silicon-based ceramics (SiC, Si3N4) are promising materials for high-temperature structural applications in turbine engines. However, the silica layer that forms on these materials is susceptible to attack from water vapor present in combustion environments. To protect against this degradation, environmental barrier coatings (EBCs) were developed to protect the underlying substrate. In the case of silicon carbide (SiC), multilayer coating systems consist of a Ba1-xSrxAl2Si 2O8 (BSAS) topcoat, a mullite or mullite + SrAl2Si 2O8 (SAS) interlayer, and a silicon bond coat. In this work, biaxial strains were measured on as-sprayed and heat-treated samples to analyze the stress and phase evolution in the coating system as a function of depth and temperature. Models were used to compare the results with an ideal coating system. In the assprayed state, tensile stresses as high as 175 MPa were measured, and cracking was observed. After thermally cycling the samples, stresses were significantly reduced and cracks in the topcoat had closed. The addition of SAS to the interlayer increased the compressive stress in the BSAS topcoat in thermally-cycled samples, which was desirable for EBC applications. The BSAS topcoat transformed from the as-deposited hexacelsian state to the stable celsian above 1200°C. This phase transformation is accompanied by a CTE reduction. The kinetics of the hexacelsian-to-celsian transformation were quantified for freestanding plasma-sprayed BSAS. Activation energies for bulk bars and crushed powder were determined to be ˜340 kJ/mol and ˜500 kJ/mol, respectively. X-ray diffraction and electron backscatter diffraction were used to establish how microstructural constraints reduce the transformation energy. Barrier coating lifetime and stability are also influenced by exposure to reactive, low-melting point calcium-magnesium-aluminosilicate (CMAS) deposits formed from dust and sand. Multilayer doped aluminosilicate coatings and bulk BSAS material were

  14. Nanoscale heat transfer and phase transformation surrounding intensely heated nanoparticles

    NASA Astrophysics Data System (ADS)

    Sasikumar, Kiran

    Over the last decade there has been significant ongoing research to use nanoparticles for hyperthermia-based destruction of cancer cells. In this regard, the investigation of highly non-equilibrium thermal systems created by ultrafast laser excitation is a particularly challenging and important aspect of nanoscale heat transfer. It has been observed experimentally that noble metal nanoparticles, illuminated by radiation at the plasmon resonance wavelength, can act as localized heat sources at nanometer-length scales. Achieving biological response by delivering heat via nanoscale heat sources has also been demonstrated. However, an understanding of the thermal transport at these scales and associated phase transformations is lacking. A striking observation made in several laser-heating experiments is that embedded metal nanoparticles heated to extreme temperatures may even melt without an associated boiling of the surrounding fluid. This unusual phase stability is not well understood and designing experiments to understand the physics of this phenomenon is a challenging task. In this thesis, we will resort to molecular dynamics (MD) simulations, which offer a powerful tool to investigate this phenomenon, without assumptions underlying continuum-level model formulations. We present the results from a series of steady state and transient non-equilibrium MD simulations performed on an intensely heated nanoparticle immersed in a model liquid. For small nanoparticles (1-10 nm in diameter) we observe a stable liquid phase near the nanoparticle surface, which can be at a temperature well above the boiling point. Furthermore, we report the existence of a critical nanoparticle size (4 nm in diameter) below which we do not observe formation of vapor even when local fluid temperatures exceed the critical temperature. Instead, we report the existence of a stable fluid region with a density much larger than that of the vapor phase. We explain this stability in terms of the

  15. Single beam Fourier transform digital holographic quantitative phase microscopy

    SciTech Connect

    Anand, A. Chhaniwal, V. K.; Mahajan, S.; Trivedi, V.; Faridian, A.; Pedrini, G.; Osten, W.; Dubey, S. K.; Javidi, B.

    2014-03-10

    Quantitative phase contrast microscopy reveals thickness or height information of a biological or technical micro-object under investigation. The information obtained from this process provides a means to study their dynamics. Digital holographic (DH) microscopy is one of the most used, state of the art single-shot quantitative techniques for three dimensional imaging of living cells. Conventional off axis DH microscopy directly provides phase contrast images of the objects. However, this process requires two separate beams and their ratio adjustment for high contrast interference fringes. Also the use of two separate beams may make the system more vulnerable to vibrations. Single beam techniques can overcome these hurdles while remaining compact as well. Here, we describe the development of a single beam DH microscope providing whole field imaging of micro-objects. A hologram of the magnified object projected on to a diffuser co-located with a pinhole is recorded with the use of a commercially available diode laser and an arrayed sensor. A Fourier transform of the recorded hologram directly yields the complex amplitude at the image plane. The method proposed was investigated using various phase objects. It was also used to image the dynamics of human red blood cells in which sub-micrometer level thickness variation were measurable.

  16. Fourier transform infrared phase shift cavity ring down spectrometer

    NASA Astrophysics Data System (ADS)

    Schundler, Elizabeth; Mansur, David J.; Vaillancourt, Robert; Benedict-Gill, Ryan; Newbry, Scott P.; Engel, James R.; Dupuis, Julia Rentz

    2014-05-01

    OPTRA has developed a Fourier transform infrared phase shift cavity ring down spectrometer (FTIR-PS-CRDS) system under a U.S. EPA SBIR contract. This system uses the inherent wavelength-dependent modulation imposed by the FTIR on a broadband thermal source for the phase shift measurement. This spectrally-dependent phase shift is proportional to the spectrally-dependent ring down time. The spectral dependence of both of these values is introduced by the losses of the cavity including those due to the molecular absorption of the sample. OPTRA's approach allows broadband detection of chemicals across the feature-rich fingerprint region of the long-wave infrared. This represents a broadband and spectral range enhancement to conventional CRDS which is typically done at a single wavelength in the near IR; at the same time the approach is a sensitivity enhancement to traditional FTIR, owing to the long effective path of the resonant cavity. In previous papers1,2, OPTRA has presented a breadboard system aimed at demonstrating the feasibility of the approach and a prototype design implementing performance enhancements based on the results of breadboard testing. In this final paper in the series, we will present test results illustrating the realized performance of the fully assembled and integrated breadboard, thereby demonstrating the utility of the approach.

  17. Role of valence electrons in phase transformation kinetics of thallium and its dilute alloys

    NASA Technical Reports Server (NTRS)

    Ahmed, R.; Ahmed, S.

    1991-01-01

    The kinetics of the phase transformation of thallium and its dilute alloys were investigated using XRD and calorimetry. Pure thallium exhibits a beta(bcc) to alpha(hcp) phase transformation on cooling at 508 K. With alloying additions, the crystal structure for each phase does not change, although the size of the unit cell increases. The enthalpy and the temperature of phase transformation of each alloy have been determined. The chemical free energy change associated with the phase transformation of each alloy was calculated. The valence electrons make an outstanding contribution to the chemical free energy change required for the phase change.

  18. Phase-field modeling of the beta to omega phase transformation in Zr–Nb alloys

    DOE PAGESBeta

    Yeddu, Hemantha Kumar; Lookman, Turab

    2015-05-01

    A three-dimensional elastoplastic phase-field model is developed, using the Finite Element Method (FEM), for modeling the athermal beta to omega phase transformation in Zr–Nb alloys by including plastic deformation and strain hardening of the material. The microstructure evolution during athermal transformation as well as under different stress states, e.g. uni-axial tensile and compressive, bi-axial tensile and compressive, shear and tri-axial loadings, is studied. The effects of plasticity, stress states and the stress loading direction on the microstructure evolution as well as on the mechanical properties are studied. The input data corresponding to a Zr – 8 at.% Nb alloy aremore » acquired from experimental studies as well as by using the CALPHAD method. Our simulations show that the four different omega variants grow as ellipsoidal shaped particles. Our results show that due to stress relaxation, the athermal phase transformation occurs slightly more readily in the presence of plasticity compared to that in its absence. The evolution of omega phase is different under different stress states, which leads to the differences in the mechanical properties of the material. The variant selection mechanism, i.e. formation of different variants under different stress loading directions, is also nicely captured by our model.« less

  19. Phase-field modeling of the beta to omega phase transformation in Zr–Nb alloys

    SciTech Connect

    Yeddu, Hemantha Kumar; Lookman, Turab

    2015-05-01

    A three-dimensional elastoplastic phase-field model is developed, using the Finite Element Method (FEM), for modeling the athermal beta to omega phase transformation in Zr–Nb alloys by including plastic deformation and strain hardening of the material. The microstructure evolution during athermal transformation as well as under different stress states, e.g. uni-axial tensile and compressive, bi-axial tensile and compressive, shear and tri-axial loadings, is studied. The effects of plasticity, stress states and the stress loading direction on the microstructure evolution as well as on the mechanical properties are studied. The input data corresponding to a Zr – 8 at.% Nb alloy are acquired from experimental studies as well as by using the CALPHAD method. Our simulations show that the four different omega variants grow as ellipsoidal shaped particles. Our results show that due to stress relaxation, the athermal phase transformation occurs slightly more readily in the presence of plasticity compared to that in its absence. The evolution of omega phase is different under different stress states, which leads to the differences in the mechanical properties of the material. The variant selection mechanism, i.e. formation of different variants under different stress loading directions, is also nicely captured by our model.

  20. Low temperature phase transformations in the metallic phases of iron and stony-iron meteorites

    SciTech Connect

    Reuter, K.B.; Williams, D.B.; Goldstein, J.I. )

    1988-03-01

    Analytical electron microscopy techniques were used to determine the Ni content and structure of kamacite and decomposed taenite (clear taenite 1 (tetrataenite), the cloudy zone, and clear taenite 2) in the metallic phases of meteorites. Clear taenite 1 contains 51.4-45.6 {plus minus} 1.3 wt% Ni and is ordered FeNi with three variants of the L1{sub 0} superstructure. The structure formed by an order/disorder transformation below 320{degree}C. The cloudy zone formed through spinodal decomposition resulting in a two-phase structure consisting of a globular phase and a surrounding honeycomb phase. The globular phase contains 50.9 {plus minus} 1.4 wt% Ni and is ordered FeNi; the honeycomb contains 11.7 {plus minus} 0.5 wt% Ni and is martensite. Clear taenite 2 contains 25.8 to 28.1 wt% Ni and may be ordered Fe{sub 3}Ni with the L1{sub 2} superstructure. Clear taenite 2 was found in all of the iron meteorite groups studied and in the pallasites, but not in the mesosiderites. Using this chemical and structural information, and a newly determined Fe-Ni phase diagram, a better understanding of the low temperature transformations in the metallic regions of meteorites has been obtained.

  1. Magnetic properties of heat treated bacterial ferrihydrite nanoparticles

    NASA Astrophysics Data System (ADS)

    Balaev, D. A.; Krasikov, A. A.; Dubrovskiy, A. A.; Popkov, S. I.; Stolyar, S. V.; Bayukov, O. A.; Iskhakov, R. S.; Ladygina, V. P.; Yaroslavtsev, R. N.

    2016-07-01

    The magnetic properties of ferrihydrite nanoparticles, which are products of vital functions of Klebsiella oxitoca bacteria, have been studied. The initial powder containing the nanoparticles in an organic shell was subjected to low-temperature (T=160 °C) heat treatment for up to 240 h. The bacterial ferrihydrite particles exhibit a superparamagnetic behavior. Their characteristic blocking temperature increases from 26 to 80 K with the heat treatment. Analysis of the magnetization curves with regard to the magnetic moment distribution function and antiferromagnetic contribution shows that the low-temperature heat treatment enhances the average magnetic moment of a particle; i.e., the nanoparticles coarsen, probably due to their partial agglomeration during heat treatment. It was established that the blocking temperature nonlinearly depends on the particle volume. Therefore, a model was proposed that takes into account both the bulk and surface magnetic anisotropy. Using this model, the bulk and surface magnetic anisotropy constants KV≈1.7×105 erg/cm3 and KS≈0.055 erg/cm2 have been determined. The effect of the surface magnetic anisotropy of ferrihydrite nanoparticles on the observed magnetic hysteresis loops is discussed.

  2. Simultaneous lead and antimony immobilization in shooting range soil by a combined application of hydroxyapatite and ferrihydrite.

    PubMed

    Ogawa, Shouhei; Katoh, Masahiko; Sato, Takeshi

    2015-01-01

    This study investigated whether a combined application of hydroxyapatite and ferrihydrite could immobilize lead and antimony in shooting range soil in which the level of lead contamination is markedly higher than that of antimony. In addition, we evaluated the stability of lead and antimony immobilized by the combined application with varying soil pH. The levels of water-soluble lead and antimony for the combined application were lower than those of single applications of hydroxyapatite or ferrihydrite, indicating that the combined application could suppress the levels of water-soluble lead and antimony by 99.9% and 95.5%, respectively, as compared with the levels in shooting range soil without immobilization material. The amounts of residual lead and amorphous Fe/Al oxide-bound antimony fractions in sequential extraction increased with a decrease in the exchangeable and carbonate lead fractions as well as in non-specifically bound and specifically bound antimony fractions. The alteration of lead and antimony phases to chemically more stable ones as a result of the combined application would result in the suppression of their mobility. The stability of immobilized lead and antimony in the combined application was equal to that of lead with a single application of hydroxyapatite and that of antimony with a single application of ferrihydrite within neutral to alkaline pH conditions, respectively. Therefore, this study suggests that the combined application of hydroxyapatite and ferrihydrite can simultaneously immobilize lead and antimony in shooting range soil with neutral to alkaline pH. PMID:25894550

  3. Zig-zag twins and helical phase transformations.

    PubMed

    Ganor, Yaniv; Dumitrică, Traian; Feng, Fan; James, Richard D

    2016-04-28

    We demonstrate the large bending deformation induced by an array of permanent magnets (applied field ∼0.02 T) designed to minimize poles in the bent state of the crystal. Planar cantilevers of NiMnGa (5M modulated martensite) ferromagnetic shape memory alloy deform into an arched shape according to theory, with a zig-zag microstructure that complies with the kinematic and magnetic compatibility between adjacent twin variants. A general theory of bent and twisted states is given, applicable to both twinning and austenite/martensite transformations. Some of these configurations achieve order-of-magnitude amplification of rotation and axial strain. We investigate also atomistic analogues of these bent and twisted configurations with perfect interfaces between phases. These mechanisms of large deformation, induced by small magnetic fields or temperature changes, have potential application to the development of new actuation technologies for micro-robotic systems. PMID:27002072

  4. Zig-zag twins and helical phase transformations.

    PubMed

    Ganor, Yaniv; Dumitrică, Traian; Feng, Fan; James, Richard D

    2016-04-28

    We demonstrate the large bending deformation induced by an array of permanent magnets (applied field ∼0.02 T) designed to minimize poles in the bent state of the crystal. Planar cantilevers of NiMnGa (5M modulated martensite) ferromagnetic shape memory alloy deform into an arched shape according to theory, with a zig-zag microstructure that complies with the kinematic and magnetic compatibility between adjacent twin variants. A general theory of bent and twisted states is given, applicable to both twinning and austenite/martensite transformations. Some of these configurations achieve order-of-magnitude amplification of rotation and axial strain. We investigate also atomistic analogues of these bent and twisted configurations with perfect interfaces between phases. These mechanisms of large deformation, induced by small magnetic fields or temperature changes, have potential application to the development of new actuation technologies for micro-robotic systems.

  5. Phase transformation and thermoelectric properties of bismuth-telluride nanowires.

    PubMed

    Hsin, Cheng-Lun; Wingert, Matthew; Huang, Chun-Wei; Guo, Hua; Shih, Ten-Jen; Suh, Joonki; Wang, Kevin; Wu, Junqiao; Wu, Wen-Wei; Chen, Renkun

    2013-06-01

    Thermoelectric materials have attracted much attention due to the current interest in energy conversion and recent advancements in nano-engineering. A simple approach to synthesize BiTe and Bi2Te3 micro/nanowires was developed by combining solution chemistry reactions and catalyst-free vapor-solid growth. A pathway to transform the as-grown BiTe nanostructures into Bi2Te3 can be identified through the Bi-Te phase diagram. Structural characterization of these products was identified using standard microscopy practices. Meanwhile, thermoelectric properties of individual Bi-Te compound micro/nanowires were determined by the suspended microdevice technique. This approach provides an applicable route to synthesize advanced high performance thermoelectric materials in quantities and can be used for a wide range of low-dimensional structures. PMID:23619552

  6. Phase transformation and thermoelectric properties of bismuth-telluride nanowires

    NASA Astrophysics Data System (ADS)

    Hsin, Cheng-Lun; Wingert, Matthew; Huang, Chun-Wei; Guo, Hua; Shih, Ten-Jen; Suh, Joonki; Wang, Kevin; Wu, Junqiao; Wu, Wen-Wei; Chen, Renkun

    2013-05-01

    Thermoelectric materials have attracted much attention due to the current interest in energy conversion and recent advancements in nano-engineering. A simple approach to synthesize BiTe and Bi2Te3 micro/nanowires was developed by combining solution chemistry reactions and catalyst-free vapor-solid growth. A pathway to transform the as-grown BiTe nanostructures into Bi2Te3 can be identified through the Bi-Te phase diagram. Structural characterization of these products was identified using standard microscopy practices. Meanwhile, thermoelectric properties of individual Bi-Te compound micro/nanowires were determined by the suspended microdevice technique. This approach provides an applicable route to synthesize advanced high performance thermoelectric materials in quantities and can be used for a wide range of low-dimensional structures.Thermoelectric materials have attracted much attention due to the current interest in energy conversion and recent advancements in nano-engineering. A simple approach to synthesize BiTe and Bi2Te3 micro/nanowires was developed by combining solution chemistry reactions and catalyst-free vapor-solid growth. A pathway to transform the as-grown BiTe nanostructures into Bi2Te3 can be identified through the Bi-Te phase diagram. Structural characterization of these products was identified using standard microscopy practices. Meanwhile, thermoelectric properties of individual Bi-Te compound micro/nanowires were determined by the suspended microdevice technique. This approach provides an applicable route to synthesize advanced high performance thermoelectric materials in quantities and can be used for a wide range of low-dimensional structures. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00876b

  7. High-temperature phase transformations. The properties of the phases and their equilibrium under shock loading.

    NASA Astrophysics Data System (ADS)

    Zaretsky, Eugene

    2011-06-01

    Introducing the temperature as a variable parameter in shock wave experiments extends essentially the scope of these investigations. The influence of the temperature variations on either high strain rate elastic-plastic response of solids or parameters of the shock-induces phase transformations are not trivial and are not quite clear yet. The technique of VISAR-monitored planar impact experiments with the samples preheated up to 1400 K was developed and used for the studies of the effect of the preheating on the impact response and on the ``dynamic'' phase diagrams of pure metals (U, Ti, Fe, Co, Ag), and ionic compounds (KCl, KBr). The studies show that the increase of the shear strength of the shock-loaded metal with temperature (first reported by Kanel et al. 1996) is typical for pure FCC (Al, Ag, Cu) and some other (Sn, U) metals, and for the ionic crystals. In the metals with BCC lattice (Mo: Duffy and Ahrens 1994, Fe: Zaretsky 2009) such thermal hardening was not found. The abrupt strength anomalies (either yield or spall or both) were observed in a narrow vicinity of the temperature of any, polymorphic, magnetic, or melting, phase transformation. It was found that when a pure element approaches the phase boundary (the line of either first or second order phase transition) the result is a 50-100-% increase of the shear strength of the low-temperature phase. At the same time the presence of a small (~0.5%) amount of impurities may lead to a five-fold decrease of the strength as it takes place in the vicinity of the Curie point of Ni. The same technique being applied to the study of the shear stress relaxation (elastic precursor decay) near the transformation line may be useful for understanding the mechanisms responsible of these anomalies.

  8. Phase-field modeling of shock-induced α- γ phase transformation of RDX

    NASA Astrophysics Data System (ADS)

    Rahul, -; de, Suvranu

    2015-06-01

    A thermodynamically consistent continuum phase field model has been developed to investigate the role of shock-induced α- γ phase transition in the sensitivity of RDX. Dislocations and phase transformations are distinguished and modeled within a crystal plasticity framework. The Landau potential is derived for the finite elastic deformation analysis. The response of the shock loaded RDX crystal is obtained by solving the continuum momentum equation along with phase evolution equation using a Helmholtz free energy functional, which consists of elastic potential energy and local interfacial energy that follows from the Cahn-Hilliard formalism. We observe that the orientations for which there is a resolved shear stress along the slip direction, the material absorbs large shear strain through plastic deformation, allowing it to be less sensitive as less mechanical work is available for temperature rise. Therefore, plastic slip should be associated with greater shear relaxation and, hence, decreased sensitivity. For elastic orientations, large shear stress arises from steric hindrance that may provides much more mechanical work to increase the temperature and hence more sensitive to detonation. Our simulations suggest that the α- γ phase transformation in RDX may be associated with the increased temperature rise and hence the shock sensitivity. The authors gratefully acknowledge the support of this work through Office of Naval Research (ONR) Grants N000140810462 and N000141210527 with Dr. Clifford Bedford as the cognizant Program Manager.

  9. Spectroscopic and Geochemical Analyses of Ferrihydrite from Hydrothermal Springs in Iceland and Applications to Mars

    NASA Technical Reports Server (NTRS)

    Bishop, Janice; Murad, E.; DeVincenzi, Donald L. (Technical Monitor)

    2001-01-01

    Ferrihydrite samples were collected from a thermal spring and a cold stream in the Landmannalaugar region of Iceland. Chemical and spectroscopic analyses have been performed on the air-dried and fine-grained fractions of these samples. The ferrihydrite from the cold stream is a pure sample, containing small amounts of Ca, P and Si, which do not form minerals detectable with X-ray diffraction (XRD) or reflectance and transmittance spectroscopy. The ferrihydrite from the thermal pool is a less pure sample, containing larger amounts of amorphous Si and P. The XRD and spectral features for this sample are also consistent with a less crystalline structure. Some of the Si is incorporated in the structure of the ferrihydrite. The Ca, P and possibly some of the Si may be biogenic. The spectral character of these Icelandic ferrihydrites is compared with those of synthetic ferrihydrites and other iron oxide/oxyhydroxide minerals. Ferrihydrite is characterized by a broad Fe3+ excitation band near 0.92 microns (approx. 10900/cm) and a strong Fe-O absorption feature near 475/cm (approx. 21 microns) in transmittance spectra. Multiple bands due to H2O and OH are also present for ferrihydrite. Natural ferrihydrites frequently exhibit a band near 950-1050/cm (approx. 10 microns) that is typically not observed for synthetic ferrihydrites and may be due to some Si in the structure. An additional pair of spectral bands near 1400 and 1500/cm (approx. 7 microns) are characteristic of pure ferrihydrites from natural and synthetic sources. Hydrothermal springs may have been present at one time on Mars in association with volcanic activity. Ferrihydrite formation in such an environment may have contributed to the ferric oxide-rich surface material on Mars.

  10. Phase Transformation Hysteresis in a Plutonium Alloy System: Modeling the Resistivity during the Transformation

    SciTech Connect

    Haslam, J J; Wall, M A; Johnson, D L; Mayhall, D J; Schwartz, A J

    2001-11-14

    We have induced, measured, and modeled the {delta}-{alpha}' martensitic transformation in a Pu-Ga alloy by a resistivity technique on a 2.8-mm diameter disk sample. Our measurements of the resistance by a 4-probe technique were consistent with the expected resistance obtained from a finite element analysis of the 4-point measurement of resistivity in our round disk configuration. Analysis by finite element methods of the postulated configuration of {alpha}' particles within model {delta} grains suggests that a considerable anisotropy in the resistivity may be obtained depending on the arrangement of the {alpha}' lens shaped particles within the grains. The resistivity of these grains departs from the series resistance model and can lead to significant errors in the predicted amount of the {alpha}' phase present in the microstructure. An underestimation of the amount of {alpha}' in the sample by 15%, or more, appears to be possible.

  11. Dynamic observation of phase transformation behaviors in indium(III) selenide nanowire based phase change memory.

    PubMed

    Huang, Yu-Ting; Huang, Chun-Wei; Chen, Jui-Yuan; Ting, Yi-Hsin; Lu, Kuo-Chang; Chueh, Yu-Lun; Wu, Wen-Wei

    2014-09-23

    Phase change random access memory (PCRAM) has been extensively investigated for its potential applications in next-generation nonvolatile memory. In this study, indium(III) selenide (In2Se3) was selected due to its high resistivity ratio and lower programming current. Au/In2Se3-nanowire/Au phase change memory devices were fabricated and measured systematically in an in situ transmission electron microscope to perform a RESET/SET process under pulsed and dc voltage swept mode, respectively. During the switching, we observed the dynamic evolution of the phase transformation process. The switching behavior resulted from crystalline/amorphous change and revealed that a long pulse width would induce the amorphous or polycrystalline state by different pulse amplitudes, supporting the improvement of the writing speed, retention, and endurance of PCRAM. PMID:25133955

  12. Three-dimensional phase transformation by impedance-matched dielectric slabs and generation of hollow beams based on transformation optics

    NASA Astrophysics Data System (ADS)

    Wang, Lei; Yang, Shuaisai; Tang, Zhixiang; Shu, Weixing

    2016-10-01

    We propose a three-dimensional (3D) phase transformation method by an impedance-matched dielectric slab and apply it to generating hollow beams. We first employ transformation optics to establish a method for the transformation between two arbitrary 3D wavefronts through a flat dielectric and impedance-matched material. Then the method is used to convert a solid beam into a hollow beam with desired wavefront. By tuning the transformation surface, different hollow beams can be produced. The results are further validated by 3D finite-difference time-domain simulations.

  13. Magnetic-field-induced shape recovery by reverse phase transformation.

    PubMed

    Kainuma, R; Imano, Y; Ito, W; Sutou, Y; Morito, H; Okamoto, S; Kitakami, O; Oikawa, K; Fujita, A; Kanomata, T; Ishida, K

    2006-02-23

    Large magnetic-field-induced strains have been observed in Heusler alloys with a body-centred cubic ordered structure and have been explained by the rearrangement of martensite structural variants due to an external magnetic field. These materials have attracted considerable attention as potential magnetic actuator materials. Here we report the magnetic-field-induced shape recovery of a compressively deformed NiCoMnIn alloy. Stresses of over 100 MPa are generated in the material on the application of a magnetic field of 70 kOe; such stress levels are approximately 50 times larger than that generated in a previous ferromagnetic shape-memory alloy. We observed 3 per cent deformation and almost full recovery of the original shape of the alloy. We attribute this deformation behaviour to a reverse transformation from the antiferromagnetic (or paramagnetic) martensitic to the ferromagnetic parent phase at 298 K in the Ni45Co5Mn36.7In13.3 single crystal.

  14. Role of outer-membrane cytochromes MtrC and OmcA in the biomineralization of ferrihydrite by Shewanella oneidensis MR-1.

    PubMed

    Reardon, C L; Dohnalkova, A C; Nachimuthu, P; Kennedy, D W; Saffarini, D A; Arey, B W; Shi, L; Wang, Z; Moore, D; McLean, J S; Moyles, D; Marshall, M J; Zachara, J M; Fredrickson, J K; Beliaev, A S

    2010-01-01

    In an effort to improve the understanding of electron transfer mechanisms at the microbe-mineral interface, Shewanella oneidensis MR-1 mutants with in-frame deletions of outer-membrane cytochromes (OMCs), MtrC and OmcA, were characterized for the ability to reduce ferrihydrite (FH) using a suite of microscopic, spectroscopic, and biochemical techniques. Analysis of purified recombinant proteins demonstrated that both cytochromes undergo rapid electron exchange with FH in vitro with MtrC displaying faster transfer rates than OmcA. Immunomicroscopy with cytochrome-specific antibodies revealed that MtrC co-localizes with iron solids on the cell surface while OmcA exhibits a more diffuse distribution over the cell surface. After 3-day incubation of MR-1 with FH, pronounced reductive transformation mineral products were visible by electron microscopy. Upon further incubation, the predominant phases identified were ferrous phosphates including vivianite [Fe(3)(PO(4))(2)x8H(2)O] and a switzerite-like phase [Mn(3),Fe(3)(PO(4))(2)x7H(2)O] that were heavily colonized by MR-1 cells with surface-exposed outer-membrane cytochromes. In the absence of both MtrC and OmcA, the cells ability to reduce FH was significantly hindered and no mineral transformation products were detected. Collectively, these results highlight the importance of the outer-membrane cytochromes in the reductive transformation of FH and support a role for direct electron transfer from the OMCs at the cell surface to the mineral.

  15. Interaction between phase transformations and dislocations at the nanoscale. Part 1. General phase field approach

    NASA Astrophysics Data System (ADS)

    Levitas, Valery I.; Javanbakht, Mahdi

    2015-09-01

    Thermodynamically consistent, three-dimensional (3D) phase field approach (PFA) for coupled multivariant martensitic transformations (PTs), including cyclic PTs, variant-variant transformations (i.e., twinning), and dislocation evolution is developed at large strains. One of our key points is in the justification of the multiplicative decomposition of the deformation gradient into elastic, transformational, and plastic parts. The plastic part includes four mechanisms: dislocation motion in martensite along slip systems of martensite and slip systems of austenite inherited during PT and dislocation motion in austenite along slip systems of austenite and slip systems of martensite inherited during reverse PT. The plastic part of the velocity gradient for all these mechanisms is defined in the crystal lattice of the austenite utilizing just slip systems of austenite and inherited slip systems of martensite, and just two corresponding types of order parameters. The explicit expressions for the Helmholtz free energy and the transformation and plastic deformation gradients are presented to satisfy the formulated conditions related to homogeneous thermodynamic equilibrium states of crystal lattice and their instabilities. In particular, they result in a constant (i.e., stress- and temperature-independent) transformation deformation gradient and Burgers vectors. Thermodynamic treatment resulted in the determination of the driving forces for change of the order parameters for PTs and dislocations. It also determined the boundary conditions for the order parameters that include a variation of the surface energy during PT and exit of dislocations. Ginzburg-Landau equations for dislocations include variation of properties during PTs, which in turn produces additional contributions from dislocations to the Ginzburg-Landau equations for PTs. A complete system of coupled PFA and mechanics equations is presented. A similar theory can be developed for PFA to dislocations and other

  16. Shock Condition Forensics and Cryptic Phase Transformations from Crystallographic Orientation Relationships in Zircon

    NASA Astrophysics Data System (ADS)

    Timms, N. E.; Erickson, T. M.; Cavosie, A. J.; Pearce, M. A.; Reddy, S. M.; Zanetti, M.; Tohver, E.; Schmieder, M.; Nemchin, A. A.; Wittmann, A.

    2016-08-01

    We present an approach to constrain pressure and temperature conditions during impact events involving identification of cryptic histories of phase transformations from orientation relationships in shocked zircon, linked to new P-T phase diagrams.

  17. Ferrihydrite dissolution by pyridine-2,6-bis(monothiocarboxylic acid) and hydrolysis products

    NASA Astrophysics Data System (ADS)

    Dhungana, Suraj; Anthony, Charles R.; Hersman, Larry E.

    2007-12-01

    Pyridine-2,6-bis(monothiocarboxylate) (pdtc), a metabolic product of microorganisms, including Pseudomonas putida and Pseudomonas stutzeri was investigated for its ability of dissolve Fe(III)(hydr)oxides at pH 7.5. Concentration dependent dissolution of ferrihydrite under anaerobic environment showed saturation of the dissolution rate at the higher concentration of pdtc. The surface controlled ferrihydrite dissolution rate was determined to be 1.2 × 10 -6 mol m -2 h -1. Anaerobic dissolution of ferrihydrite by pyridine-2,6-dicarboxylic acid or dipicolinic acid (dpa), a hydrolysis product of pdtc, was investigated to study the mechanism(s) involved in the pdtc facilitated ferrihydrite dissolution. These studies suggest that pdtc dissolved ferrihydrite using a reduction step, where dpa chelates the Fe reduced by a second hydrolysis product, H 2S. Dpa facilitated dissolution of ferrihydrite showed very small increase in the Fe dissolution when the concentration of external reductant, ascorbate, was doubled, suggesting the surface dynamics being dominated by the interactions between dpa and ferrihydrite. Greater than stoichiometric amounts of Fe were mobilized during dpa dissolution of ferrihydrite assisted by ascorbate and cysteine. This is attributed to the catalytic dissolution of Fe(III)(hydr)oxides by the in situ generated Fe(II) in the presence of a complex former, dpa.

  18. Incorporation of Uranium into Hematite during Crystallization from Ferrihydrite

    PubMed Central

    2014-01-01

    Ferrihydrite was exposed to U(VI)-containing cement leachate (pH 10.5) and aged to induce crystallization of hematite. A combination of chemical extractions, TEM, and XAS techniques provided the first evidence that adsorbed U(VI) (≈3000 ppm) was incorporated into hematite during ferrihydrite aggregation and the early stages of crystallization, with continued uptake occurring during hematite ripening. Analysis of EXAFS and XANES data indicated that the U(VI) was incorporated into a distorted, octahedrally coordinated site replacing Fe(III). Fitting of the EXAFS showed the uranyl bonds lengthened from 1.81 to 1.87 Å, in contrast to previous studies that have suggested that the uranyl bond is lost altogether upon incorporation into hematite. The results of this study both provide a new mechanistic understanding of uranium incorporation into hematite and define the nature of the bonding environment of uranium within the mineral structure. Immobilization of U(VI) by incorporation into hematite has clear and important implications for limiting uranium migration in natural and engineered environments. PMID:24580024

  19. Incorporation of Uranium into Hematite during crystallization from ferrihydrite.

    PubMed

    Marshall, Timothy A; Morris, Katherine; Law, Gareth T W; Livens, Francis R; Mosselmans, J Frederick W; Bots, Pieter; Shaw, Samuel

    2014-04-01

    Ferrihydrite was exposed to U(VI)-containing cement leachate (pH 10.5) and aged to induce crystallization of hematite. A combination of chemical extractions, TEM, and XAS techniques provided the first evidence that adsorbed U(VI) (≈3000 ppm) was incorporated into hematite during ferrihydrite aggregation and the early stages of crystallization, with continued uptake occurring during hematite ripening. Analysis of EXAFS and XANES data indicated that the U(VI) was incorporated into a distorted, octahedrally coordinated site replacing Fe(III). Fitting of the EXAFS showed the uranyl bonds lengthened from 1.81 to 1.87 Å, in contrast to previous studies that have suggested that the uranyl bond is lost altogether upon incorporation into hematite. The results of this study both provide a new mechanistic understanding of uranium incorporation into hematite and define the nature of the bonding environment of uranium within the mineral structure. Immobilization of U(VI) by incorporation into hematite has clear and important implications for limiting uranium migration in natural and engineered environments.

  20. Near-equilibrium polymorphic phase transformations in Praseodymium under dynamic compression

    SciTech Connect

    Bastea, M; Reisman, D

    2007-02-12

    We report the first experimental observation of sequential, multiple polymorphic phase transformations occurring in Praseodymium dynamically compressed using a ramp wave. The experiments also display the signatures of reverse transformations occuring upon pressure release and reveal the presence of small hysteresys loops. The results are in very good agreement with equilibrium hydrodynamic calculations performed using a thermodynamically consistent, multi-phase equation of state for Praseodymium, suggesting a near-equilibrium transformation behavior.

  1. Phase Stability and Stress-Induced Transformations in Beta Titanium Alloys

    NASA Astrophysics Data System (ADS)

    Kolli, R. Prakash; Joost, William J.; Ankem, Sreeramamurthy

    2015-06-01

    In this article, we provide a brief review of the recent developments related to the relationship between phase stability and stress-induced transformations in metastable body-centered-cubic β-phase titanium alloys. Stress-induced transformations occur during tensile, compressive, and creep loading and influence the mechanical response. These transformations are not fully understood and increased understanding of these mechanisms will permit future development of improved alloys for aerospace, biomedical, and energy applications. In the first part of this article, we review phase stability and discuss a few recent developments. In the second section, we discuss the current status of understanding stress-induced transformations and several areas that require further study. We also provide our perspective on the direction of future research efforts. Additionally, we address the occurrence of the hcp ω-phase and the orthorhombic α″-martensite phase stress-induced transformations.

  2. Low-temperature solid-state phase transformations in 2H silicon carbide.

    NASA Technical Reports Server (NTRS)

    Powell, J. A.; Will, H. A.

    1972-01-01

    Study of the phase transformations taking place in 2H SiC single crystals at temperatures as low as 400 C. Some crystals transformed to a structure with one-dimensional disorder along the crystal c axis. Others transformed to a faulted cubic/6H structure. The transformation is time and temperature dependent, and is greatly enhanced by dislocations. The transformation takes place by means of a slip process perpendicular to the c axis. Cubic SiC crystals were observed to undergo a solid-state transformation above 1400 C.

  3. Low-temperature solid-state phase transformations in 2H silicon carbide

    NASA Technical Reports Server (NTRS)

    Will, H. A.; Powell, J. A.

    1972-01-01

    Single crystals of 2H SiC were observed to undergo phase transformations at temperatures as low as 400 C. Some 2H crystals transformed to a structure with one-dimensional disorder along the crystal c axis. Others transformed to a faulted cubic/6H structure. The transformation is time and temperature dependent and is greatly enhanced by dislocations. Observations indicate that the transformation takes place by means of a slip process perpendicular to the c axis. Cubic SiC crystals were observed to undergo a solid state transformation above 1400 C.

  4. Phase retrieval by using the transport-of-intensity equation with Hilbert transform.

    PubMed

    Li, Wei-Shuo; Chen, Chun-Wei; Lin, Kuo-Feng; Chen, Hou-Ren; Tsai, Chih-Ya; Chen, Chyong-Hua; Hsieh, Wen-Feng

    2016-04-01

    Phase recovery by solving the transport-of-intensity equation (TIE) is a non-iterative and non-interferometric phase retrieval technique. From solving the TIE with conventional, one partial derivative and Hilbert transform methods for both the periodic and aperiodic samples, we demonstrate that the Hilbert transform method can provide the smoother phase images with edge enhancement and fine structures. Furthermore, compared with the images measured by optical and atomic force microscopy, the Hilbert transform method has the ability to quantitatively map out the phase images for both the periodic and aperiodic structures. PMID:27192301

  5. Interplay between diffusive and displacive phase transformations: time-temperature-transformation diagrams and microstructures.

    PubMed

    Bouville, Mathieu; Ahluwalia, Rajeev

    2006-08-01

    Materials which can undergo extremely fast displacive transformations as well as very slow diffusive transformations are studied using a Ginzburg-Landau framework. This simple model captures the essential physics behind microstructure formation and time-temperature-transformation diagrams in alloys such as steels. It also predicts the formation of mixed microstructures by an interplay between diffusive and displacive mechanisms. The intrinsic volume changes associated with the transformations stabilize mixed microstructures such as martensite-retained austenite (responsible for the existence of a martensite finish temperature) and martensite-pearlite.

  6. Deformation-induced {alpha}{sub 2} {yields} {gamma} phase transformation in TiAl alloys

    SciTech Connect

    Chen, C.L.; Lu, W.; Sun Dai; He, L.L.; Ye, H.Q.

    2010-11-15

    Deformation-induced {alpha}{sub 2} {yields} {gamma} phase transformation in high Nb containing TiAl alloys was investigated using high-resolution transmission electron microscopy (HREM) and energy dispersive X-ray spectroscopy (EDS). The dislocations appearing at the tip of deformation-induced {gamma} plate (DI-{gamma}) and the stacking sequence change of the {alpha}{sub 2} matrix were two key evidences for determining the occurrence of the deformation-induced {alpha}{sub 2} {yields} {gamma} phase transformation. Compositional analysis revealed that the product phase of the room-temperature transformation was not standard {gamma} phase; on the contrary, the product phase of the high-temperature transformation was standard {gamma} phase.

  7. Pressure and Temperature effects on the High Pressure Phase Transformation in Zirconium

    SciTech Connect

    Escobedo-Diaz, Juan P.; Cerreta, Ellen K.; Brown, Donald W.; Trujillo, Carl P.; Rigg, Paulo A.; Bronkhorst, Curt A.; Addessio, Francis L.; Lookman, Turab

    2012-06-20

    At high pressure zirconium is known to undergo a phase transformation from the hexagonal close packed (HCP) alpha phase ({alpha}) to the simple hexagonal omega phase ({omega}). Under conditions of shock loading, the high-pressure omega phase is retained upon release. However, the hysteresis in this transformation is not well represented by equilibrium phase diagrams. For this reason, the influence of peak shock pressure and temperature on the retention of omega phase in Zr is explored in this study. In situ VISAR measurements along with post-mortem metallographic and neutron diffraction characterization of soft recovered specimens have been utilized to quantify the volume fraction of retained omega phase, morphology of the shocked alpha and omega phases, and qualitatively understand the kinetics of this transformation. This understanding of the role of peak shock stress will be utilized to address physics to be encoded in our present macro-scale models.

  8. Characterization, Modeling, and Energy Harvesting of Phase Transformations in Ferroelectric Materials

    NASA Astrophysics Data System (ADS)

    Dong, Wenda

    Solid state phase transformations can be induced through mechanical, electrical, and thermal loading in ferroelectric materials that are compositionally close to morphotropic phase boundaries. Large changes in strain, polarization, compliance, permittivity, and coupling properties are typically observed across the phase transformation regions and are phenomena of interest for energy harvesting and transduction applications where increased coupling behavior is desired. This work characterized and modeled solid state phase transformations in ferroelectric materials and assessed the potential of phase transforming materials for energy harvesting applications. Two types of phase transformations were studied. The first type was ferroelectric rhombohedral to ferroelectric orthorhombic observed in lead indium niobate lead magnesium niobate lead titanate (PIN-PMN-PT) and driven by deviatoric stress, temperature, and electric field. The second type of phase transformation is ferroelectric to antiferroelectric observed in lead zirconate titanate (PZT) and driven by pressure, temperature, and electric field. Experimental characterizations of the phase transformations were conducted in both PIN-PMN-PT and PZT in order to understand the thermodynamic characteristics of the phase transformations and map out the phase stability of both materials. The ferroelectric materials were characterized under combinations of stress, electric field, and temperature. Material models of phase transforming materials were developed using a thermodynamic based variant switching technique and thermodynamic observations of the phase transformations. These models replicate the phase transformation behavior of PIN-PMN-PT and PZT under mechanical and electrical loading conditions. The switching model worked in conjunction with linear piezoelectric equations as ferroelectric/ferroelastic constitutive equations within a finite element framework that solved the mechanical and electrical field equations

  9. In Situ TEM Nanoindentation Studies on Stress-Induced Phase Transformations in Metallic Materials

    DOE PAGESBeta

    Liu, Y.; Wang, H.; Zhang, X.

    2015-11-30

    Though abundant phase transformations are in general thermally driven processes, there are many examples wherein stresses can induce phase transformations. We applied numerous in situ techniques, such as in situ x-ray diffraction and neutron diffraction in order to reveal phase transformations. Recently, an in situ nanoindentation technique coupled with transmission electron microscopy demonstrated the capability to directly correlating stresses with phase transformations and microstructural evolutions at a submicron length scale. We briefly review in situ studies on stress-induced diffusional and diffusionless phase transformations in amorphous CuZrAl alloy and NiFeGa shape memory alloy. Moreover, in the amorphous CuZrAl, in situ nanoindentationmore » studies show that the nucleation of nanocrystals (a diffusional process) occurs at ultra-low stresses manifested by a prominent stress drop. In the NiFeGa shape memory alloy, two distinctive types of martensitic (diffusionless) phase transformations accompanied by stress plateaus are observed, including a reversible gradual phase transformation at low stress levels, and an irreversible abrupt phase transition at higher stress levels.« less

  10. In Situ TEM Nanoindentation Studies on Stress-Induced Phase Transformations in Metallic Materials

    SciTech Connect

    Liu, Y.; Wang, H.; Zhang, X.

    2015-11-30

    Though abundant phase transformations are in general thermally driven processes, there are many examples wherein stresses can induce phase transformations. We applied numerous in situ techniques, such as in situ x-ray diffraction and neutron diffraction in order to reveal phase transformations. Recently, an in situ nanoindentation technique coupled with transmission electron microscopy demonstrated the capability to directly correlating stresses with phase transformations and microstructural evolutions at a submicron length scale. We briefly review in situ studies on stress-induced diffusional and diffusionless phase transformations in amorphous CuZrAl alloy and NiFeGa shape memory alloy. Moreover, in the amorphous CuZrAl, in situ nanoindentation studies show that the nucleation of nanocrystals (a diffusional process) occurs at ultra-low stresses manifested by a prominent stress drop. In the NiFeGa shape memory alloy, two distinctive types of martensitic (diffusionless) phase transformations accompanied by stress plateaus are observed, including a reversible gradual phase transformation at low stress levels, and an irreversible abrupt phase transition at higher stress levels.

  11. Metastable phase transformation and hcp-ω transformation pathways in Ti and Zr under high hydrostatic pressures

    NASA Astrophysics Data System (ADS)

    Gao, Lei; Ding, Xiangdong; Lookman, Turab; Sun, Jun; Salje, E. K. H.

    2016-07-01

    The energy landscape of Zr at high hydrostatic pressure suggests that its transformation behavior is strongly pressure dependent. This is in contrast to the known transition mechanism in Ti, which is essentially independent of hydrostatic pressure. Generalized solid-state nudged elastic band calculations at constant pressure shows that α-Zr transforms like Ti only at the lowest pressure inside the stability field of ω-phase. Different pathways apply at higher pressures where the energy landscape contains several high barriers so that metastable states are expected, including the appearance of a transient bcc phase at ca. 23 GPa. The global driving force for the hcp-ω transition increases strongly with increasing pressure and reaches 23.7 meV/atom at 23 GPa. Much of this energy relates to the excess volume of the hcp phase compared with its ω phase.

  12. Investigation of phase transformations in ductile cast iron of differential scanning calorimetry

    NASA Astrophysics Data System (ADS)

    Przeliorz, R.; Piątkowski, J.

    2011-05-01

    The effect of heating rate on phase transformations to austenite range in ductile cast iron of the EN-GJS-450-10 grade was investigated. For studies of phase transformations, the technique of differential scanning calorimetry (DSC) was used. Micro structure was examined by optical microscopy. The calorimetric examinations have proved that on heating three transformations occur in this grade of ductile iron, viz. magnetic transformation at the Curie temperature, pearlite→austenite transformation and ferrite→austenite transformation. An increase in the heating rate shifts the pearlite→austenite and ferrite→austenite transformations to higher temperature range. At the heating rate of 5 and 15 °C min-1, local extrema have been observed to occur: for pearlite→austenite transformation at 784 °C and 795 °C, respectively, and for ferrite+ graphite →austenite transformation at 805 °C and 821 °C, respectively. The Curie temperature of magnetic transformation was extrapolated to a value of 740 °C. Each transformation is related with a specific thermal effect. The highest value of enthalpy is accompanying the ferrite→austenite transformation, the lowest occurs in the case of pearlite→austenite transformation.

  13. Association of organic matter and ferrihydrite: adsorption versus coprecipitation

    NASA Astrophysics Data System (ADS)

    Eusterhues, K.; Rennert, T.; Knicker, H.; Totsche, K. U.

    2009-04-01

    Ferrihydrite (Fh) - even if present at low concentrations - may control the available surface area and therefore, the behaviour of nutrients and pollutants in soils. Its precipitation often takes place in the presence of dissolved organic matter (OM). This involves processes such as adsorption, but also coprecipitation, flocculation/coagulation and poisoning of crystal growth. In this study, we compare coprecipitation of organic matter and ferrihydrite with pure adsorption of OM on ferrihydrite. We therefore prepared an adsorption series and a coprecipitation series using (i) water extractable organic matter from a forest topsoil and (ii) sulfite extractable lignin from paper. Products were investigated by N2-adsorption, XRD and FTIR. In coprecipitation experiments with both types of OM we observed a strong interference of the organic molecules with crystal growth leading to smaller Fh crystals, increased lattice spacings and a lower crystallinity. The highest achieved C loadings were found at approximately 200 mg C per g Fh for the adsorption and coprecipitation of the soil extract as well as for the adsorption of lignin. Coprecipitation of lignin, in contrast, resulted in a much higher maximum loading of 360 mg C per g Fh. The FTIR spectrum of the unreacted soil extract is mainly characterized by carboxyl C and polysaccharide C, with a smaller contribution of phenolic C. Spectra of the adsorbed or coprecipitated soil extract reveal weaker bands and lowered wave numbers indicating removal from solution followed by the formation of chemical bonds between the organic species and Fh by inner-sphere surface complexes. The FTIR spectrum of the lignin material shows a strong contribution of carboxyl C, polysaccharide C, and several aromatic C species. Again, all of these C species seem to form surface complexes after reaction with Fh in adsorption and coprecipitation experiments. Interestingly, at low initial C concentrations in all experiments the sorption of carboxyl

  14. Solution-mediated phase transformation: significance during dissolution and implications for bioavailability.

    PubMed

    Greco, Kristyn; Bogner, Robin

    2012-09-01

    Solubility improvement of poorly soluble drug compounds is a key approach to ensuring the successful development of many new drugs. Methods used to improve the solubility of drug compounds include forming a salt, cocrystal, or amorphous solid. These methods of improving solubility can often lead to a phenomenon called solution-mediated phase transformation, a phase change that is facilitated through exposure to solution. Solution-mediated phase transformation occurs in three steps: dissolution to create a supersaturated solution followed by nucleation of less soluble phase and the growth of that phase. When the growth of the less soluble phase occurs on the surface of the metastable solid, this phenomenon can cause a marked decrease in dissolution rate during in vitro dissolution evaluation, and ultimately in vivo. Therefore, transformation to a less soluble solid during dissolution is an important aspect to consider when evaluating approaches to increase the solubility of a poorly soluble drug. Identification of solution-mediated phase transformation during dissolution is reviewed for powder dissolution, rotating disk method, and channel flow-through apparatus. Types of solution-mediated phase transformation are described in this report, including those involving salts, polymorphs, amorphous solids, and cocrystals. Many experimental examples are provided. Evidence of potential solution-mediated phase transformation in vivo is discussed to better understand the relationship between in vitro dissolution evaluation and in vivo performance.

  15. Nanoindentation-induced phase transformation and structural deformation of monocrystalline germanium: a molecular dynamics simulation investigation

    PubMed Central

    2013-01-01

    Molecular dynamics simulations were conducted to study the nanoindentation of monocrystalline germanium. The path of phase transformation and distribution of transformed region on different crystallographic orientations were investigated. The results indicate the anisotropic behavior of monocrystalline germanium. The nanoindentation-induced phase transformation from diamond cubic structure to β-tin-Ge was found in the subsurface region beneath the tool when indented on the (010) plane, while direct amorphization was observed in the region right under the indenter when the germanium was loaded along the [101] and [111] directions. The transformed phases extend along the < 110 > slip direction of germanium. The depth and shape of the deformed layers after unloading are quite different according to the crystal orientation of the indentation plane. The study results suggest that phase transformation is the dominant mechanism of deformation of monocrystalline germanium film in nanoindentation. PMID:23947487

  16. Comparison between thermochemical and phase stability data for the quartz-coesite-stishovite transformations

    NASA Technical Reports Server (NTRS)

    Weaver, J. S.; Chipman, D. W.; Takahashi, T.

    1979-01-01

    Phase stability and elasticity data have been used to calculate the Gibbs free energy, enthalpy, and entropy changes at 298 K and 1 bar associated with the quartz-coesite and coesite-stishovite transformations in the system SiO2. For the quartz-coesite transformation, these changes disagree by a factor of two or three with those obtained by calorimetric techniques. The phase boundary for this transformation appears to be well determined by experiment; the discrepancy, therefore, suggests that the calorimetric data for coesite are in error. Although the calorimetric and phase stability data for the coesite-stishovite transformation yield the same transition pressure at 298 K, the phase-boundary slopes disagree by a factor of two. At present, it is not possible to determine which of the data are in error. Thus serious inconsistencies exist in the thermodynamic data for the polymorphic transformations of silica.

  17. Co-adsorption of phosphate and zinc(II) on the surface of ferrihydrite.

    PubMed

    Liu, Jing; Zhu, Runliang; Xu, Tianyuan; Xu, Yin; Ge, Fei; Xi, Yunfei; Zhu, Jianxi; He, Hongping

    2016-02-01

    Ferrihydrite (Fh) is of great importance in affecting the migration and transformation of heavy-metal cations and oxyanions. To advance the understanding of co-adsorption reactions on Fh surface, the co-adsorption of phosphate and Zn(II) from aqueous solution to a synthesized Fh was determined. The batch experiments demonstrated a synergistic adsorption of phosphate and Zn(II) on Fh. In the pH range of 3.5-6, the adsorption of the two contaminants showed strong pH dependence in the single solute adsorption systems, but the dependence alleviated in the simultaneous adsorption system. X-ray photoelectron spectroscopy (XPS) revealed that the chemical shifts of Zn 2p1/2 and Zn 2p3/2 binding energies were more significant than that of P 2p in the single and simultaneous adsorption systems. On the other side, in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) observed increased formation of outer- and inner-sphere complexes of phosphate in the simultaneous system. Thus, the synergistic adsorption of the two contaminants could be attributed to the formation of ternary complexes as well as electrostatic interactions, while surface precipitation could not be completely ruled out. On the basis of the results from both the batch adsorption experiments and structural characterization, these two contaminants were likely to form phosphate-bridged ternary complexes (≡Fe-P-Zn) in the simultaneous adsorption system.

  18. Co-adsorption of phosphate and zinc(II) on the surface of ferrihydrite.

    PubMed

    Liu, Jing; Zhu, Runliang; Xu, Tianyuan; Xu, Yin; Ge, Fei; Xi, Yunfei; Zhu, Jianxi; He, Hongping

    2016-02-01

    Ferrihydrite (Fh) is of great importance in affecting the migration and transformation of heavy-metal cations and oxyanions. To advance the understanding of co-adsorption reactions on Fh surface, the co-adsorption of phosphate and Zn(II) from aqueous solution to a synthesized Fh was determined. The batch experiments demonstrated a synergistic adsorption of phosphate and Zn(II) on Fh. In the pH range of 3.5-6, the adsorption of the two contaminants showed strong pH dependence in the single solute adsorption systems, but the dependence alleviated in the simultaneous adsorption system. X-ray photoelectron spectroscopy (XPS) revealed that the chemical shifts of Zn 2p1/2 and Zn 2p3/2 binding energies were more significant than that of P 2p in the single and simultaneous adsorption systems. On the other side, in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) observed increased formation of outer- and inner-sphere complexes of phosphate in the simultaneous system. Thus, the synergistic adsorption of the two contaminants could be attributed to the formation of ternary complexes as well as electrostatic interactions, while surface precipitation could not be completely ruled out. On the basis of the results from both the batch adsorption experiments and structural characterization, these two contaminants were likely to form phosphate-bridged ternary complexes (≡Fe-P-Zn) in the simultaneous adsorption system. PMID:26461439

  19. Investigation on phase transformation mechanism of zeolite NaY under alkaline hydrothermal conditions

    SciTech Connect

    Li, Peng Ding, Tian Liu, Liping Xiong, Guang

    2013-12-15

    The phase transformation mechanism of zeolite NaY under alkaline hydrothermal conditions was investigated by UV Raman spectroscopy, X-ray diffraction, X-ray fluorescence and scanning electron microscopy techniques. The results revealed that the products and transformation rate are dependent on the alkalinities. All of the starting and resulting zeolites are constructed with the 4-ring and 6-ring secondary building units. The products have lower Si/Al ratio, higher framework density and smaller pore size, which are more stable under alkaline hydrothermal condition. During the phase transformation the fragments of faujasite are formed, then the fragments combine to form different zeolites depending on basicity. Zeolite NaY crystals are consumed as the reservoir for the transformation products during the recrystallization process. For the first time, a 4-membered ring intermediate was found at the early stage of the recrystallization process. A cooperative interaction of liquid and solid phases is required for inducing the phase transformation. - Graphical Abstract: Phase transformation of NaY zeolite under alkaline hydrothermal condition is achieved by the cooperative interaction of the liquid and solid phases. A 4-membered ring species is an intermediate for recrystallization process. Highlights: • The products and transformation rate are dependent on the alkalinity. • A 4-membered ring species is an intermediate for recrystallization process. • A cooperative interaction of liquid and solid phases is required.

  20. Fast 3D shape measurement using Fourier transform profilometry without phase unwrapping

    NASA Astrophysics Data System (ADS)

    Song, Kechen; Hu, Shaopeng; Wen, Xin; Yan, Yunhui

    2016-09-01

    This paper presents a novel, simple, yet fast 3D shape measurement method using Fourier transform profilometry. Different from the conventional Fourier transform profilometry, this proposed method introduces the binocular stereo vision and employs two image pairs (i.e., original image pairs and fringe image pairs) to restructure 3D shape. In this proposed method, instead of phase unwrapping algorithm, a coarse disparity map is adopted as a constraint condition to realize phase matching using wrapped phase. Since the local phase matching and sub-pixel disparity refinement are proposed to obtain high measuring accuracy, high-quality phase is not required. The validity of the proposed method is verified by experiments.

  1. In vitro evaluation of ferrihydrite as an enterosorbent for arsenic from contaminated drinking water.

    PubMed

    Taylor, J F; Robinson, A; Johnson, N; Marroquin-Cardona, A; Brattin, B; Taylor, R; Phillips, T D

    2009-07-15

    Arsenic (As) is a toxic trace element found in groundwater due to natural and industrial processes. Exposure has been linked to cancers of the bladder, lungs, skin, kidneys, nasal passages, liver, and the prostate. Arsenic in drinking water is a problem in many countries, notably Bangladesh and Taiwan. The purpose of this research was to utilize binding isotherms, a simulated gastrointestinal (GI) model, and the adult Hydra bioassay to evaluate ferrihydrite's potential to bind As and serve as a potential enterosorbent for As found in drinking water. A variety of clay minerals and synthesized iron oxides including ferrihydrite were screened for their ability to bind As(III), as sodium arsenite, and As(V), as sodium arsenate. After ferrihydrite was demonstrated to be the most effective sorbent for both As species, adsorption isotherms were performed. All isotherm data were fit to the Langmuir equation to determine adsorption capacity (Qmax). Ferrihydrite bound 96% of As(III) and 97% of As(V) in the screening studies and had a Qmax of 1.288 mol/kg for As(III) and 0.744 mol/kg for As(V). Using a simulated GI model, ferrihydrite was found to effectively adsorb As(V) and As(III) in the stomach and intestine. Ferrihydrite (0.25% w/w) protected adult Hydra at levels up to 200 times the minimal effective concentration (MEC) for As(III) and up to 2.5 times the MEC for As(V). These experiments confirm that ferrihydrite is a high capacity sorbent of As and that it is effective at removing As in a simulated GI model. These results suggest that ferrihydrite could be used as a potential enterosorbent for As found in drinking water. Future work will focus on verifying ferrihydrite's safety and efficacy in vivo.

  2. Selective formation of metastable ferrihydrite in the chiton tooth.

    PubMed

    Gordon, Lyle M; Román, Jessica K; Everly, R Michael; Cohen, Michael J; Wilker, Jonathan J; Joester, Derk

    2014-10-20

    Metastable precursors are thought to play a major role in the ability of organisms to create mineralized tissues. Of particular interest are the hard and abrasion-resistant teeth formed by chitons, a class of rock-grazing mollusks. The formation of chiton teeth relies on the precipitation of metastable ferrihydrite (Fh) in an organic scaffold as a precursor to magnetite. In vitro synthesis of Fh under physiological conditions has been challenging. Using a combination of X-ray absorption and electron paramagnetic resonance spectroscopy, we show that, prior to Fh formation in the chiton tooth, iron ions are complexed by the organic matrix. In vitro experiments demonstrate that such complexes facilitate the formation of Fh under physiological conditions. These results indicate that acidic molecules may be integral to controlling Fh formation in the chiton tooth. This biological approach to polymorph selection is not limited to specialized proteins and can be expropriated using simple chemistry.

  3. Selective formation of metastable ferrihydrite in the chiton tooth.

    PubMed

    Gordon, Lyle M; Román, Jessica K; Everly, R Michael; Cohen, Michael J; Wilker, Jonathan J; Joester, Derk

    2014-10-20

    Metastable precursors are thought to play a major role in the ability of organisms to create mineralized tissues. Of particular interest are the hard and abrasion-resistant teeth formed by chitons, a class of rock-grazing mollusks. The formation of chiton teeth relies on the precipitation of metastable ferrihydrite (Fh) in an organic scaffold as a precursor to magnetite. In vitro synthesis of Fh under physiological conditions has been challenging. Using a combination of X-ray absorption and electron paramagnetic resonance spectroscopy, we show that, prior to Fh formation in the chiton tooth, iron ions are complexed by the organic matrix. In vitro experiments demonstrate that such complexes facilitate the formation of Fh under physiological conditions. These results indicate that acidic molecules may be integral to controlling Fh formation in the chiton tooth. This biological approach to polymorph selection is not limited to specialized proteins and can be expropriated using simple chemistry. PMID:25196134

  4. Effects of Forming Induced Phase Transformation on Crushing Behavior of TRIP Steel

    SciTech Connect

    Liu, Wenning N.; Choi, Kyoo Sil; Soulami, Ayoub; Sun, Xin; Khaleel, Mohammad A.

    2010-04-15

    In this paper, results of finite element crash simulation are presented for a TRIP steel side rail with and without considering the phase transformation during forming operations. A homogeneous phase transformation model is adapted to model the mechanical behavior of the austenite-to-martensite phase. The forming process of TRIP steels is simulated with the implementation of the material model. The distribution and volume fraction of the martensite in TRIP steels may be greatly influenced by various factors during forming process and subsequently contribute to the behavior of the formed TRIP steels during the crushing process. The results indicate that, with the forming induced phase transformation, higher energy absorption of the side rail can be achieved. The phase transformation enhances the strength of the side rail

  5. Visualization of anisotropic-isotropic phase transformation dynamics in battery electrode particles

    PubMed Central

    Wang, Jiajun; Karen Chen-Wiegart, Yu-chen; Eng, Christopher; Shen, Qun; Wang, Jun

    2016-01-01

    Anisotropy, or alternatively, isotropy of phase transformations extensively exist in a number of solid-state materials, with performance depending on the three-dimensional transformation features. Fundamental insights into internal chemical phase evolution allow manipulating materials with desired functionalities, and can be developed via real-time multi-dimensional imaging methods. Here, we report a five-dimensional imaging method to track phase transformation as a function of charging time in individual lithium iron phosphate battery cathode particles during delithiation. The electrochemically driven phase transformation is initially anisotropic with a preferred boundary migration direction, but becomes isotropic as delithiation proceeds further. We also observe the expected two-phase coexistence throughout the entire charging process. We expect this five-dimensional imaging method to be broadly applicable to problems in energy, materials, environmental and life sciences. PMID:27516044

  6. Visualization of anisotropic-isotropic phase transformation dynamics in battery electrode particles.

    PubMed

    Wang, Jiajun; Karen Chen-Wiegart, Yu-Chen; Eng, Christopher; Shen, Qun; Wang, Jun

    2016-01-01

    Anisotropy, or alternatively, isotropy of phase transformations extensively exist in a number of solid-state materials, with performance depending on the three-dimensional transformation features. Fundamental insights into internal chemical phase evolution allow manipulating materials with desired functionalities, and can be developed via real-time multi-dimensional imaging methods. Here, we report a five-dimensional imaging method to track phase transformation as a function of charging time in individual lithium iron phosphate battery cathode particles during delithiation. The electrochemically driven phase transformation is initially anisotropic with a preferred boundary migration direction, but becomes isotropic as delithiation proceeds further. We also observe the expected two-phase coexistence throughout the entire charging process. We expect this five-dimensional imaging method to be broadly applicable to problems in energy, materials, environmental and life sciences. PMID:27516044

  7. Phase transformation and deformation behavior of NiTi-Nb eutectic joined NiTi wires.

    PubMed

    Wang, Liqiang; Wang, Cong; Zhang, Lai-Chang; Chen, Liangyu; Lu, Weijie; Zhang, Di

    2016-01-01

    NiTi wires were brazed together via eutectic reaction between NiTi and Nb powder deposited at the wire contact region. Phase transformation and deformation behavior of the NiTi-Nb eutectic microstructure were investigated using transmission electron microscopy (TEM) and cyclic loading-unloading tests. Results show that R phase and B19' martensite transformation are induced by plastic deformation. R phase transformation, which significantly contributes to superelasticity, preferentially occurs at the interfaces between NiTi and eutectic region. Round-shaped Nb-rich phase with rod-like and lamellar-type eutectics are observed in eutectic regions. These phases appear to affect the deformation behavior of the brazed NiTi-Nb region via five distinct stages in stress-strain curves: (I) R phase reorientation, (II) R phase transformation from parent phase, (III) elastic deformation of reoriented martensite accompanied by the plastic deformation of Nb-rich phase and lamellar NiTi-Nb eutectic, (IV) B19' martensitic transformation, and (V) plastic deformation of the specimen. PMID:27049025

  8. Phase transformation and deformation behavior of NiTi-Nb eutectic joined NiTi wires

    PubMed Central

    Wang, Liqiang; Wang, Cong; Zhang, Lai-Chang; Chen, Liangyu; Lu, Weijie; Zhang, Di

    2016-01-01

    NiTi wires were brazed together via eutectic reaction between NiTi and Nb powder deposited at the wire contact region. Phase transformation and deformation behavior of the NiTi-Nb eutectic microstructure were investigated using transmission electron microscopy (TEM) and cyclic loading-unloading tests. Results show that R phase and B19′ martensite transformation are induced by plastic deformation. R phase transformation, which significantly contributes to superelasticity, preferentially occurs at the interfaces between NiTi and eutectic region. Round-shaped Nb-rich phase with rod-like and lamellar-type eutectics are observed in eutectic regions. These phases appear to affect the deformation behavior of the brazed NiTi-Nb region via five distinct stages in stress-strain curves: (I) R phase reorientation, (II) R phase transformation from parent phase, (III) elastic deformation of reoriented martensite accompanied by the plastic deformation of Nb-rich phase and lamellar NiTi-Nb eutectic, (IV) B19′ martensitic transformation, and (V) plastic deformation of the specimen. PMID:27049025

  9. Phase transformation and deformation behavior of NiTi-Nb eutectic joined NiTi wires.

    PubMed

    Wang, Liqiang; Wang, Cong; Zhang, Lai-Chang; Chen, Liangyu; Lu, Weijie; Zhang, Di

    2016-04-06

    NiTi wires were brazed together via eutectic reaction between NiTi and Nb powder deposited at the wire contact region. Phase transformation and deformation behavior of the NiTi-Nb eutectic microstructure were investigated using transmission electron microscopy (TEM) and cyclic loading-unloading tests. Results show that R phase and B19' martensite transformation are induced by plastic deformation. R phase transformation, which significantly contributes to superelasticity, preferentially occurs at the interfaces between NiTi and eutectic region. Round-shaped Nb-rich phase with rod-like and lamellar-type eutectics are observed in eutectic regions. These phases appear to affect the deformation behavior of the brazed NiTi-Nb region via five distinct stages in stress-strain curves: (I) R phase reorientation, (II) R phase transformation from parent phase, (III) elastic deformation of reoriented martensite accompanied by the plastic deformation of Nb-rich phase and lamellar NiTi-Nb eutectic, (IV) B19' martensitic transformation, and (V) plastic deformation of the specimen.

  10. α-Phase transformation kinetics of U - 8 wt% Mo established by in situ neutron diffraction

    NASA Astrophysics Data System (ADS)

    Steiner, M. A.; Calhoun, C. A.; Klein, R. W.; An, K.; Garlea, E.; Agnew, S. R.

    2016-08-01

    The α-phase transformation kinetics of as-cast U - 8 wt% Mo below the eutectoid temperature have been established by in situ neutron diffraction. α-phase weight fraction data acquired through Rietveld refinement at five different isothermal hold temperatures can be modeled accurately utilizing a simple Johnson-Mehl-Avrami-Kolmogorov impingement-based theory, and the results are validated by a corresponding evolution in the γ-phase lattice parameter during transformation that follows Vegard's law. Neutron diffraction data is used to produce a detailed Time-Temperature-Transformation diagram that improves upon inconsistencies in the current literature, exhibiting a minimum transformation start time of 40 min at temperatures between 500 °C and 510 °C. The transformation kinetics of U - 8 wt% Mo can vary significantly from as-cast conditions after extensive heat treatments, due to homogenization of the typical dendritic microstructure which possesses non-negligible solute segregation.

  11. Uncovering the intrinsic size dependence of hydriding phase transformations in nanocrystals

    NASA Astrophysics Data System (ADS)

    Bardhan, Rizia; Hedges, Lester O.; Pint, Cary L.; Javey, Ali; Whitelam, Stephen; Urban, Jeffrey J.

    2013-10-01

    A quantitative understanding of nanocrystal phase transformations would enable more efficient energy conversion and catalysis, but has been hindered by difficulties in directly monitoring well-characterized nanoscale systems in reactive environments. We present a new in situ luminescence-based probe enabling direct quantification of nanocrystal phase transformations, applied here to the hydriding transformation of palladium nanocrystals. Our approach reveals the intrinsic kinetics and thermodynamics of nanocrystal phase transformations, eliminating complications of substrate strain, ligand effects and external signal transducers. Clear size-dependent trends emerge in nanocrystals long accepted to be bulk-like in behaviour. Statistical mechanical simulations show these trends to be a consequence of nanoconfinement of a thermally driven, first-order phase transition: near the phase boundary, critical nuclei of the new phase are comparable in size to the nanocrystal itself. Transformation rates are then unavoidably governed by nanocrystal dimensions. Our results provide a general framework for understanding how nanoconfinement fundamentally impacts broad classes of thermally driven solid-state phase transformations relevant to hydrogen storage, catalysis, batteries and fuel cells.

  12. The correlation of local deformation and stress-assisted local phase transformations in MMC foams

    SciTech Connect

    Berek, H.; Ballaschk, U.; Aneziris, C.G.; Losch, K.; Schladitz, K.

    2015-09-15

    Cellular structures are of growing interest for industry, and are of particular importance for lightweight applications. In this paper, a special case of metal matrix composite foams (MMCs) is investigated. The investigated foams are composed of austenitic steel exhibiting transformation induced plasticity (TRIP) and magnesia partially stabilized zirconia (Mg-PSZ). Both components exhibit martensitic phase transformation during deformation, thus generating the potential for improved mechanical properties such as strength, ductility, and energy absorption capability. The aim of these investigations was to show that stress-assisted phase transformations within the ceramic reinforcement correspond to strong local deformation, and to determine whether they can trigger martensitic phase transformations in the steel matrix. To this end, in situ interrupted compression experiments were performed in an X-ray computed tomography device (XCT). By using a recently developed registration algorithm, local deformation could be calculated and regions of interest could be defined. Corresponding cross sections were prepared and used to analyze the local phase composition by electron backscatter diffraction (EBSD). The results show a strong correlation between local deformation and phase transformation. - Graphical abstract: Display Omitted - Highlights: • In situ compressive deformation on MMC foams was performed in an XCT. • Local deformation fields and their gradient amplitudes were estimated. • Cross sections were manufactured containing defined regions of interest. • Local EBSD phase analysis was performed. • Local deformation and local phase transformation are correlated.

  13. Power Electronic Transformer based Three-Phase PWM AC Drives

    NASA Astrophysics Data System (ADS)

    Basu, Kaushik

    A Transformer is used to provide galvanic isolation and to connect systems at different voltage levels. It is one of the largest and most expensive component in most of the high voltage and high power systems. Its size is inversely proportional to the operating frequency. The central idea behind a power electronic transformer (PET) also known as solid state transformer is to reduce the size of the transformer by increasing the frequency. Power electronic converters are used to change the frequency of operation. Steady reduction in the cost of the semiconductor switches and the advent of advanced magnetic materials with very low loss density and high saturation flux density implies economic viability and feasibility of a design with high power density. Application of PET is in generation of power from renewable energy sources, especially wind and solar. Other important application include grid tied inverters, UPS e.t.c. In this thesis non-resonant, single stage, bi-directional PET is considered. The main objective of this converter is to generate adjustable speed and magnitude pulse width modulated (PWM) ac waveforms from an ac or dc grid with a high frequency ac link. The windings of a high frequency transformer contains leakage inductance. Any switching transition of the power electronic converter connecting the inductive load and the transformer requires commutation of leakage energy. Commutation by passive means results in power loss, decrease in the frequency of operation, distortion in the output voltage waveform, reduction in reliability and power density. In this work a source based partially loss-less commutation of leakage energy has been proposed. This technique also results in partial soft-switching. A series of converters with novel PWM strategies have been proposed to minimize the frequency of leakage inductance commutation. These PETs achieve most of the important features of modern PWM ac drives including 1) Input power factor correction, 2) Common

  14. Phase transformations in the Zn-Al eutectoid alloy after quenching from the high temperature triclinic beta phase

    SciTech Connect

    Sandoval-Jimenez, A.; Torres-Villasenor, G.

    2010-11-15

    Ribbons of the Zn-Al eutectoid alloy obtained by melt-spinning, were heat treated at 350 deg. C during 30 min in a free atmosphere furnace, and then quenched in liquid nitrogen. The temperature correspond to {beta} phase zone, which has a triclinic crystalline structure [1, 2]. Some evidence, obtained by X-ray diffraction, show that the structures present in the just quenched material are both close-packed hexagonal ({eta}-phase) and rhombohedral (R-phase). X-ray diffractograms taken in the same ribbons after annealed 500 h at room temperature, show that the R phase its transform to {alpha} and {eta} phases.

  15. Stress-induced phase transformation in nanocrystalline UO2

    SciTech Connect

    Uberuaga, Blas Pedro; Desai, Tapan

    2009-01-01

    We report a stress-induced phase transfonnation in stoichiometric UO{sub 2} from fluorite to the {alpha}-PbO{sub 2} structure using molecular dynamics (MD) simulations and density functional theory (DFT) calculations. MD simulations, performed on nanocrystalline microstructure under constant-stress tensile loading conditions, reveal a heterogeneous nucleation of the {alpha}-PbO{sub 2} phase at the grain boundaries followed by the growth of this phase towards the interior of the grain. The DFT calculations confinn the existence of the {alpha}-PbO{sub 2} structure, showing that it is energetically favored under tensile loading conditions.

  16. In-Situ Phase Mapping and Direct Observations of Phase Transformations During Arc Welding of 1045 Steel

    SciTech Connect

    Elmer, J; Palmer, T

    2005-09-13

    In-situ Spatially Resolved X-Ray Diffraction (SRXRD) experiments were performed during gas tungsten arc (GTA) welding of AISI 1045 C-Mn steel. Ferrite ({alpha}) and austenite ({gamma}) phases were identified and quantified in the weld heat-affected zone (HAZ) from the real time x-ray diffraction data. The results were compiled along with weld temperatures calculated using a coupled thermal fluids weld model to create a phase map of the HAZ. This map shows the {alpha} {yields} {gamma} transformation taking place during weld heating and the reverse {gamma} {yields} {alpha} transformation taking place during weld cooling. Superheating is required to complete the {alpha} {yields} {gamma} phase transformation, and the amount of superheat above the A3 temperature was shown to vary with distance from the centerline of the weld. Superheat values as high as 250 C above the A3 temperature were observed at heating rates of 80 C/s. The SRXRD experiments also revealed details about the {gamma} phase not observable by conventional techniques, showing that {gamma} is present with two distinct lattice parameters as a result of inhomogeneous distribution of carbon and manganese in the starting pearlitic/ferritic microstructure. During cooling, the reverse {gamma} {yields} {alpha} phase transformation was shown to depend on the HAZ location. In the fine grained region of the HAZ, at distances greater than 2 mm from the fusion line, the {gamma} {yields} {alpha} transformation begins near the A3 temperature and ends near the A1 temperature. In this region of the HAZ where the cooling rates are below 40 C/s, the transformation occurs by nucleation and growth of pearlite. For HAZ locations closer to the fusion line, undercoolings of 200 C or more below the A1 temperature are required to complete the {gamma} {yields} {alpha} transformation. In this region of the HAZ, grain growth coupled with cooling rates in excess of 50 C/s causes the transformation to occur by a bainitic mechanism.

  17. Mechanism of the α -ɛ phase transformation in iron

    NASA Astrophysics Data System (ADS)

    Dewaele, A.; Denoual, C.; Anzellini, S.; Occelli, F.; Mezouar, M.; Cordier, P.; Merkel, S.; Véron, M.; Rausch, E.

    2015-05-01

    The α -Fe↔ɛ -Fe pressure-induced transformation under pure hydrostatic static compression has been characterized with in situ x-ray diffraction using α -Fe single crystals as starting samples. The forward transition starts at 14.9 GPa, and the reverse at 12 GPa, with a width of α -ɛ coexistence domain of the order of 2 GPa. The elastic stress in the sample increases in this domain, and partially relaxes after completion of the transformation. Orientation relations between parent α -Fe and child ɛ -Fe have been determined, which definitely validates the Burgers path for the direct transition. On the reverse transition, an unexpected variant selection is observed. X-ray diffraction data, complemented with ex situ microstructural observations, suggest that this selection is caused by defects and stresses accumulated during the direct transition.

  18. Origins of asymmetric stress-strain response in phase transformations

    SciTech Connect

    Sehitoglu, H.; Gall, K.

    1997-12-31

    It has been determined that the transformation stress-strain behavior of CuZnAl and NiTi shape memory alloys is dependent on the applied stress state. The uniaxial compressive stress necessary to macroscopically trigger the transformation is approximately 34% (CuZnAl) and 26% (NiTi) larger than the required uniaxial tensile stress. For three dimensional stress states, the response of either alloy system is dependent on the directions of the dominant principal stresses along with the hydrostatic stress component of the stress state. The stress state effects are dominated by the favored growth and nucleation of more martensite plates in tension versus compression. The effect of different hydrostatic pressure levels between stress states on martensite plates volume change is considered small.

  19. Texture Evolution and Phase Transformation in Titanium Investigated by In-Situ Neutron Diffraction

    SciTech Connect

    Ma, Dong; Stoica, Alexandru Dan; An, Ke; Yang, Ling; Bei, Hongbin; Mills, Rebecca A; Skorpenske, Harley David; Wang, Xun-Li

    2011-01-01

    We report in-situ neutron diffraction studies of texture evolution and the (hcp) (bcc) phase transformation in commercially pure cold-drawn titanium upon continuous heating and cooling, complemented by differential scanning calorimetry (DSC) measurements. We show that the recrystallization of the phase at elevated temperature enhanced the preexisting fiber texture, which eventually facilitated the nucleation and growth of the phase favored by the Burgers orientation relationship, i.e., {0001} //{110} . More strikingly, upon completion of the transformation, the {110} texture (or preferred orientation) in was eliminated immediately by the rapid grain growth of intergranular allotriomorphs. This resulted in the loss of the original -texture when Ti was transformed back to from to upon subsequent cooling, distinct from the known texture memory effect for rolling textures in titanium. Our present work provides useful experimental results for understanding the mechanisms of texture evolution and phase transformation in titanium and its alloys and, by and large, low-symmetry alloys such as zirconium.

  20. Transformation temperatures of martensite in beta-phase nickel aluminide.

    NASA Technical Reports Server (NTRS)

    Smialek, J. L.; Hehemann, R. F.

    1973-01-01

    Resistivity and thermal arrest measurements determined that the compositional dependence of M sub s temperatures for NiAl martensite was linear between 60 and 69 at. % Ni, with M sub s = (124 Ni - 7410)K. Resistivity and surface relief experiments for selected alloys indicated the presence of thermoelastic martensite. Some aspects of the transformation were studied by hot-stage microscopy and related to the behavior observed for alloys exhibiting the shape-memory effect.

  1. Transformation temperatures of martensite in beta phase nickel aluminide

    NASA Technical Reports Server (NTRS)

    Smialek, J. L.; Hehemann, R. F.

    1972-01-01

    Resistivity and thermal arrest measurements determined that the compositional dependence of Ms (martensite state) temperatures for NiAl martensite was linear between 60 and 69 atomic percent nickel, with Ms = 124 Ni - 7410 K. Resistivity and surface relief experiments indicated the presence of thermoelastic martensite for selected alloys. Some aspects of the transformation were studied by hot stage microscopy and related to the behavior observed for alloys exhibiting the shape-memory effect.

  2. Microstructure and Phase Transformation of a Sinter Bearing Low Ti During Reduction

    NASA Astrophysics Data System (ADS)

    Zhang, Jianliang; Zhang, Yapeng; Li, Kejiang; Wang, Yaozu; Liu, Zhengjian; Wang, Guangwei

    2016-10-01

    To discuss the reduction behaviors and the transformation mechanism of the Fe containing phases and slag phases of low Ti-bearing sinter (LTS), reduction experiments of the LTS were conducted. The reduction of the LTS was divided into four stages based on the reduction rate, deformation quantity of LTS particle column, phase changes, and microstructural changes. The reduction process could be explained with quasi unreacted core model as three stratifications with different phases and microstructures were observed clearly in the medium-temperature reducing stage. For the reduction of Ti-SFCA, a middle phase of the reduction was found and the phase was surrounded by metallic iron. According to the composites of the reduced Ti-SFCA, the middle phase was a solid solution and difficult to be reduced which consisted mainly of brownmillerite-perovskite and monocalcium silicate. The phase transformation and microstructure changes were mutual coupling in the complicated reduction process of the LTS.

  3. Grid-Based Fourier Transform Phase Contrast Imaging

    NASA Astrophysics Data System (ADS)

    Tahir, Sajjad

    Low contrast in x-ray attenuation imaging between different materials of low electron density is a limitation of traditional x-ray radiography. Phase contrast imaging offers the potential to improve the contrast between such materials, but due to the requirements on the spatial coherence of the x-ray beam, practical implementation of such systems with tabletop (i.e. non-synchrotron) sources has been limited. One recently developed phase imaging technique employs multiple fine-pitched gratings. However, the strict manufacturing tolerances and precise alignment requirements have limited the widespread adoption of grating-based techniques. In this work, we have investigated a technique recently demonstrated by Bennett et al. that utilizes a single grid of much coarser pitch. Our system consisted of a low power 100 microm spot Mo source, a CCD with 22 microm pixel pitch, and either a focused mammography linear grid or a stainless steel woven mesh. Phase is extracted from a single image by windowing and comparing data localized about harmonics of the grid in the Fourier domain. A Matlab code was written to perform the image processing. For the first time, the effects on the diffraction phase contrast and scattering amplitude images of varying grid types and periods, and of varying the window function type used to separate the harmonics, and the window widths, were investigated. Using the wire mesh, derivatives of the phase along two orthogonal directions were obtained and new methods investigated to form improved phase contrast images.

  4. A phase-field model for incoherent martensitic transformations including plastic accommodation processes in the austenite

    NASA Astrophysics Data System (ADS)

    Kundin, J.; Raabe, D.; Emmerich, H.

    2011-10-01

    If alloys undergo an incoherent martensitic transformation, then plastic accommodation and relaxation accompany the transformation. To capture these mechanisms we develop an improved 3D microelastic-plastic phase-field model. It is based on the classical concepts of phase-field modeling of microelastic problems (Chen, L.Q., Wang Y., Khachaturyan, A.G., 1992. Philos. Mag. Lett. 65, 15-23). In addition to these it takes into account the incoherent formation of accommodation dislocations in the austenitic matrix, as well as their inheritance into the martensitic plates based on the crystallography of the martensitic transformation. We apply this new phase-field approach to the butterfly-type martensitic transformation in a Fe-30 wt%Ni alloy in direct comparison to recent experimental data (Sato, H., Zaefferer, S., 2009. Acta Mater. 57, 1931-1937). It is shown that the therein proposed mechanisms of plastic accommodation during the transformation can indeed explain the experimentally observed morphology of the martensitic plates as well as the orientation between martensitic plates and the austenitic matrix. The developed phase-field model constitutes a general simulations approach for different kinds of phase transformation phenomena that inherently include dislocation based accommodation processes. The approach does not only predict the final equilibrium topology, misfit, size, crystallography, and aspect ratio of martensite-austenite ensembles resulting from a transformation, but it also resolves the associated dislocation dynamics and the distribution, and the size of the crystals itself.

  5. In-situ Monitoring of Dynamic Phenomena during Solidification and Phase Transformation Processing

    SciTech Connect

    Clarke, Amy J.; Cooley, Jason C.; Morris, Christopher; Merrill, Frank E.; Hollander, Brian J.; Mariam, Fesseha G.; Patterson, Brian M.; Imhoff, Seth D.; Lee, Wah Keat; Fezzaa, Kamel; Deriy, Alex; Tucker, Tim J.; Clarke, Kester D.; Field, Robert D.; Thoma, Dan J.; Teter, David F.; Beard, Timothy V.; Hudson, Richard W.; Freibert, Franz J.; Korzekwa, Deniece R.; Farrow, Adam M.; Cross, Carl E.; Mihaila, Bogdan; Lookman, Turab; Hunter, Abigail; Choudhury, Samrat; Karma, Alain; Ott, Thomas J. Jr.; Barker, Martha R.; O'Neill, Finian; Hill, Joshua; Emigh, Megan G.

    2012-07-30

    The purpose of this project is to: (1) Directly observe phase transformations and microstructure evolution using proton (and synchrotron x-ray) radiography and tomography; (2) Constrain phase-field models for microstructure evolution; (3) Experimentally control microstructure evolution during processing to enable co-design; and (4) Advance toward the MaRIE vision. Understand microstructure evolution and chemical segregation during solidification {yields} solid-state transformations in Pu-Ga.

  6. The investigation of the dynamics of the phase transformation in triolein and oleic acid under pressure

    NASA Astrophysics Data System (ADS)

    Tefelski, D. B.; Siegoczyński, R. M.; Rostocki, A. J.; Kos, A.; Kościesza, R.; Wieja, K.

    2008-07-01

    An aim of our work is the understanding of processes happening during phase transformations under the pressure in triglycerides and unsaturated fatty acids. Particles of investigated liquids possess the double bond between carbon atoms, which causes the bended shape of the particle and makes its free rotation impossible. This property causes low temperatures of melting point and high temperatures of boiling and also investigated by us phase transformations. For study of the dynamics of phase transformation in these liquids we measured light transmission and light scattering at 90 degrees angle, temperature, permittivity and internal pressure versus time. We applied pressure using computer controlled pump with a stepping motor, which makes increase of the pressure steady. The phase transformation in oleic acid lasts several seconds, in triolein it lasts several minutes. We think that the elongated time of phase transformation is caused by a hooked shape of particles of triolein and the dynamics of that process is determined by the tangling of particles. We checked the influence of smaller particles of oleic acid on the phase transformation by investigating the mixture of these liquids.

  7. Nanostructures formation in ferroelectrics in the process of phase transformation

    NASA Astrophysics Data System (ADS)

    Ishchuk, V.; Spiridonov, N.; Sobolev, V.

    2014-11-01

    Inhomogeneous states caused by the coexistence of the ferroelectric (FE) and antiferroelectric (AFE) phases in lead-zirconate-titanate based solid solutions have been investigated. It has been found that the domains of the FE and AFE phases with sizes of the order of 20 nm to 30 nm coexist in the bulk of the samples due to a small difference in the free energies of these phases. The coherent character of the interphase boundaries (IPBs) leads to the concentration of the elastic stresses along these boundaries. These elastic stresses cause the local decomposition of the solid solution and formation of segregates near the IPBS due to the condition that equivalent positions of the crystal lattice are occupied by the ions with different sizes. The sizes of the segregates formed in this way are of the order 8 nm to 15 nm. Some physical effects caused by the presence of these segregate nanostructures are analyzed and discussed.

  8. Amphiphilic phase-transforming catalysts for transesterification of triglycerides

    NASA Astrophysics Data System (ADS)

    Nawaratna, Gayan Ivantha

    Heterogeneous catalytic reactions that involve immiscible liquid-phase reactants are challenging to conduct due to limitations associated with mass transport. Nevertheless, there are numerous reactions such as esterification, transesterification, etherification, and hydrolysis where two immiscible liquid reactants (such as polar and non-polar liquids) need to be brought into contact with a catalyst. With the intention of alleviating mass transport issues associated with such systems but affording the ability to separate the catalyst once the reaction is complete, the overall goal of this study is geared toward developing a catalyst that has emulsification properties as well as the ability to phase-transfer (from liquid-phase to solid-phase) while the reaction is ongoing and evaluating the effectiveness of such a catalytic process in a practical reaction. To elucidate this concept, the transesterification reaction was selected. Metal-alkoxides that possess acidic and basic properties (to catalyze the reaction), amphiphilic properties (to stabilize the alcohol/oil emulsion) and that can undergo condensation polymerization when heated (to separate as a solid subsequent to the completion of the reaction) were used to test the concept. Studies included elucidating the effect of metal sites and alkoxide sites and their concentration effects on transesterification reaction, effect of various metal alkoxide groups on the phase stability of the reactant system, and kinetic effects of the reaction system. The studies revealed that several transition-metal alkoxides, especially, titanium and yttrium based, responded positively to this reaction system. These alkoxides were able to be added to the reaction medium in liquid phase and were able to stabilize the alcohol/oil system. The alkoxides were selective to the transesterification reaction giving a range of ester yields (depending on the catalyst used). It was also observed that transition-metal alkoxides were able to be

  9. Changes in Iron, Sulfur, and Arsenic Speciation Associated with Bacterial Sulfate Reduction in Ferrihydrite-Rich Systems

    SciTech Connect

    Saalfield, S.; Bostick, B

    2009-01-01

    Biologically mediated redox processes have been shown to affect the mobility of iron oxide-bound arsenic in reducing aquifers. This work investigates how dissimilatory sulfate reduction and secondary iron reduction affect sulfur, iron, and arsenic speciation. Incubation experiments were conducted with As(III/V)-bearing ferrihydrite in carbonate-buffered artificial groundwater enriched with lactate (10 mM) and sulfate (0.08-10 mM) and inoculated with Desulfovibrio vulgaris (ATCC 7757, formerly D. desulfuricans), which reduces sulfate but not iron or arsenic. Sulfidization of ferrihydrite led to formation of magnetite, elemental sulfur, and trace iron sulfides. Observed reaction rates imply that the majority of sulfide is recycled to sulfate, promoting microbial sulfate reduction in low-sulfate systems. Despite dramatic changes in Fe and S speciation, and minimal formation of Fe or As sulfides, most As remained in the solid phase. Arsenic was not solubilized in As(V)-loaded incubations, which experienced slow As reduction by sulfide, whereas As(III)-loaded incubations showed limited and transient As release associated with iron remineralization. This suggests that As(III) production is critical to As release under reducing conditions, with sulfate reduction alone unlikely to release As. These data also suggest that bacterial reduction of As(V) is necessary for As sequestration in sulfides, even where sulfate reduction is active.

  10. Transport of ferrihydrite nanoparticles in saturated porous media: role of ionic strength and flow rate.

    PubMed

    Tosco, Tiziana; Bosch, Julian; Meckenstock, Rainer U; Sethi, Rajandrea

    2012-04-01

    The use of nanoscale ferrihydrite particles, which are known to effectively enhance microbial degradation of a wide range of contaminants, represents a promising technology for in situ remediation of contaminated aquifers. Thanks to their small size, ferrihydrite nanoparticles can be dispersed in water and directly injected into the subsurface to create reactive zones where contaminant biodegradation is promoted. Field applications would require a detailed knowledge of ferrihydrite transport mechanisms in the subsurface, but such studies are lacking in the literature. The present study is intended to fill this gap, focusing in particular on the influence of flow rate and ionic strength on particle mobility. Column tests were performed under constant or transient ionic strength, including injection of ferrihydrite colloidal dispersions, followed by flushing with particle-free electrolyte solutions. Particle mobility was greatly affected by the salt concentration, and particle retention was almost irreversible under typical salt content in groundwater. Experimental results indicate that, for usual ionic strength in European aquifers (2 to 5 mM), under natural flow condition ferrihydrite nanoparticles are likely to be transported for 5 to 30 m. For higher ionic strength, corresponding to contaminated aquifers, (e.g., 10 mM) the travel distance decreases to few meters. A simple relationship is proposed for the estimation of travel distance with changing flow rate and ionic strength. For future applications to aquifer remediation, ionic strength and injection rate can be used as tuning parameters to control ferrihydrite mobility in the subsurface and therefore the radius of influence during field injections.

  11. Phase Transformations and Formation of Ultra-Fine Microstructure During Hydrogen Sintering and Phase Transformation (HSPT) Processing of Ti-6Al-4V

    NASA Astrophysics Data System (ADS)

    Sun, Pei; Fang, Zhigang Zak; Koopman, Mark; Xia, Yang; Paramore, James; Ravi Chandran, K. S.; Ren, Yang; Lu, Jun

    2015-12-01

    The hydrogen sintering and phase transformation (HSPT) process is a novel powder metallurgy method for producing Ti alloys, particularly the Ti-6Al-4V alloy, with ultra-fine microstructure in the as-sintered state. The ultra-fine microstructure is obtained as a direct result of the use of H2 gas during sintering. The refinement of the microstructure during HSPT is similar to that of thermal hydrogen processing (THP) of bulk Ti alloys. For both THP and HSPT of Ti-6Al-4V alloy, the mechanisms of the grain refinement depend on the phase equilibria and phase transformations in the presence of hydrogen, which are surprisingly still not well established to date and are still subjected to research and debate. In recent work by the present authors, a pseudo-binary phase diagram of (Ti-6Al-4V)-H has been determined by using in situ synchrotron XRD and TGA/DSC techniques. Aided by this phase diagram, the current paper focuses on the series of phase transformations during sintering and cooling of Ti-6Al-4V in a hydrogen atmosphere and the mechanisms for the formation of the ultra-fine microstructures obtained. Using experimental techniques, including in situ synchrotron XRD, SEM, EBSD, and TEM, the microstructural refinement was found to be the result of (1) the precipitation of ultra-fine α/α2 within coarse β grains during an isothermal hold at intermediate temperatures, and (2) the eutectoid transformation of β → α + δ at approximately 473 K (200 °C).

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

    PubMed

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

    2016-09-14

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

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

    PubMed

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

    2016-09-14

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

  14. Nanoclusters first: a hierarchical phase transformation in a novel Mg alloy

    PubMed Central

    Okuda, Hiroshi; Yamasaki, Michiaki; Kawamura, Yoshihito; Tabuchi, Masao; Kimizuka, Hajime

    2015-01-01

    The Mg-Y-Zn ternary alloy system contains a series of novel structures known as long-period stacking ordered (LPSO) structures. The formation process and its key concept from a viewpoint of phase transition are not yet clear. The current study reveals that the phase transformation process is not a traditional spinodal decomposition or structural transformation but, rather a novel hierarchical phase transformation. In this transformation, clustering occurs first, and the spatial rearrangement of the clusters induce a secondary phase transformation that eventually lead to two-dimensional ordering of the clusters. The formation process was examined using in situ synchrotron radiation small-angle X-ray scattering (SAXS). Rapid quenching from liquid alloy into thin ribbons yielded strongly supersaturated amorphous samples. The samples were heated at a constant rate of 10 K/min. and the scattering patterns were acquired. The SAXS analysis indicated that small clusters grew to sizes of 0.2 nm after they crystallized. The clusters distributed randomly in space grew and eventually transformed into a microstructure with two well-defined cluster-cluster distances, one for the segregation periodicity of LPSO and the other for the in-plane ordering in segregated layer. This transformation into the LPSO structure concomitantly introduces the periodical stacking fault required for the 18R structures. PMID:26387813

  15. Nanoclusters first: a hierarchical phase transformation in a novel Mg alloy.

    PubMed

    Okuda, Hiroshi; Yamasaki, Michiaki; Kawamura, Yoshihito; Tabuchi, Masao; Kimizuka, Hajime

    2015-01-01

    The Mg-Y-Zn ternary alloy system contains a series of novel structures known as long-period stacking ordered (LPSO) structures. The formation process and its key concept from a viewpoint of phase transition are not yet clear. The current study reveals that the phase transformation process is not a traditional spinodal decomposition or structural transformation but, rather a novel hierarchical phase transformation. In this transformation, clustering occurs first, and the spatial rearrangement of the clusters induce a secondary phase transformation that eventually lead to two-dimensional ordering of the clusters. The formation process was examined using in situ synchrotron radiation small-angle X-ray scattering (SAXS). Rapid quenching from liquid alloy into thin ribbons yielded strongly supersaturated amorphous samples. The samples were heated at a constant rate of 10 K/min. and the scattering patterns were acquired. The SAXS analysis indicated that small clusters grew to sizes of 0.2 nm after they crystallized. The clusters distributed randomly in space grew and eventually transformed into a microstructure with two well-defined cluster-cluster distances, one for the segregation periodicity of LPSO and the other for the in-plane ordering in segregated layer. This transformation into the LPSO structure concomitantly introduces the periodical stacking fault required for the 18R structures.

  16. Temperature-induced phase transformation of Fe1-xNix alloys: molecular-dynamics approach

    NASA Astrophysics Data System (ADS)

    Sak-Saracino, Emilia; Urbassek, Herbert M.

    2015-07-01

    Using molecular-dynamics simulation, we study the temperature induced bcc/fcc phase transformation of random Fe1-xNix alloys in the concentration range of x ≤ 40 at%. The Meyer-Entel potential describes faithfully the decrease of the transition temperature with increasing Ni concentration. The austenite transformation proceeds by homogeneous nucleation and results in a fine-grained poly-crystalline structure. The transformation follows the Nishiyama-Wassermann orientation relationship. The martensite phase nucleates at the grain boundaries (heterogeneous nucleation). Even for the largest crystallite studied (2.75 × 105 atoms) the back-transformation results in a single-crystalline grain containing only a small amount of defects. The morphological changes in the transformed material show no significant dependence on Ni content.

  17. Broadband CARS spectral phase retrieval using a time-domain Kramers-Kronig transform.

    PubMed

    Liu, Yuexin; Lee, Young Jong; Cicerone, Marcus T

    2009-05-01

    We describe a closed-form approach for performing a Kramers-Kronig (KK) transform that can be used to rapidly and reliably retrieve the phase, and thus the resonant imaginary component, from a broadband coherent anti-Stokes Raman scattering (CARS) spectrum with a nonflat background. In this approach we transform the frequency-domain data to the time domain, perform an operation that ensures a causality criterion is met, then transform back to the frequency domain. The fact that this method handles causality in the time domain allows us to conveniently account for spectrally varying nonresonant background from CARS as a response function with a finite rise time. A phase error accompanies KK transform of data with finite frequency range. In examples shown here, that phase error leads to small (<1%) errors in the retrieved resonant spectra.

  18. Ab initio molecular dynamics simulation of pressure-induced phase transformation of BeO

    SciTech Connect

    Xiao, H. Y.; Duan, G.; Zu, X. T.; Weber, W. J.

    2011-05-05

    Ab initio molecular dynamics (MD) method has been used to study high pressure-induced phase transformation in BeO based on the local density approximation (LDA) and the generalized gradient approximation (GGA). Both methods show that the wurtzite (WZ) and zinc blende (ZB) BeO transforms to the rocksalt (RS) structure smoothly at high pressure. The transition pressures obtained from the LDA method are about 40 GPa larger than the GGA result for both WZ → RS and ZB → RS phase transformations, and the phase transformation mechanisms revealed by the LDA and GGA methods are different. For WZ → RS phase transformations both mechanisms obtained from the LDA and GGA methods are not comparable to the previous ab initio MD simulations of WZ BeO at 700 GPa based on the GGA method. It is suggested that the phase transformation mechanisms of BeO revealed by the ab initio MD simulations are affected remarkably by the exchange–correlation functional employed and the way of applying pressure.

  19. Study of phase transformation of guanosine 5'-monophosphate in drowning-out crystallization.

    PubMed

    Kang, Jeongki; Tuan, Nguyen Anh; Kim, Jong-Min; Chang, Sang-Mok; Kim, Woo-Sik

    2010-01-01

    The present study used a mechanistic approach to control the phase transformation of guanosine 5'-monophosphate (GMP) via the operating conditions of agitation and feed concentration during drowning-out crystallization. First, Fourier transform infrared and UV/vis spectrophotometry were successfully applied to monitor the mass fraction of GMP polymorphs (amorphous and hydrate crystalline GMPs) and GMP supersaturation, respectively, during the crystallization. The phase transformation of amorphous GMP into hydrate crystals was significantly influenced by the agitation, which promoted the mass transfer of GMP dissolution and growth. Therefore, the phase transformation was quickly finished when increasing the agitation speed. However, a high agitation caused breakage of the hydrate crystals, resulting in a reduced crystal size with a bimodal distribution. The phase transformation was also influenced by the GMP feed concentration, as the crystal growth was promoted and the crystal size increased when increasing the feed concentration up to 61 g/l. However, a further increase in the feed concentration caused secondary nucleation due to the induction of a high supersaturation level during the phase transformation, leading to a small crystal size with a bimodal distribution. In addition, the rectangular-shaped hydrate GMP crystals exhibited a higher growth rate in the b direction rather than the a direction. Therefore, the crystal morphology shifted from a long rectangle to a square when increasing the feed concentration. PMID:19031052

  20. In-situ stabilization of Pb, Zn, Cu, Cd and Ni in the multi-contaminated sediments with ferrihydrite and apatite composite additives.

    PubMed

    Qian, Guangren; Chen, Wei; Lim, Teik Thye; Chui, Pengcheong

    2009-10-30

    Three additives were evaluated for their effectiveness in the attenuation of Pb2+, Zn2+, Cu2+, Cd2+, Ni2+ in contaminated sediments. Apatite, ferrihydrite and their composite were applied to the sediments. For the remediation, BCR, SEM/AVS and TCLP were adopted as the evaluating method and comparison of their results were used for the first time to test in-situ stabilization effect. The results showed that after 5 months composite treatment, more than 70% Pb2+, 40% Zn2+, 90% Cu2+, 50% Cd2+ and 80% Ni2+ was immobilized in oxidizable and residual phases, respectively. Compared to untreated sediment, Pb2+, Zn2+, Cu2+, Cd2+ in residual fraction increased 20%, 10%, 10%, 10% with composite treatment after 5 months, respectively. SigmaSEM/AVS ratio declined from 12.6 to 9.3, in addition, composite treatments reduced the leaching of Pb2+ and Zn2+ from 10.6 mg L(-1) and 42.5 mg L(-1) to 5.4 mg L(-1) and 24.1 mg L(-1) in the sediment by TCLP evaluation. Meanwhile, apatite and ferrihydrite composite additives lowered the bioavailability and toxicity of sediments as well. Ferrihydrite had a positive effect in controlling the bioavailability and toxicity of heavy metals because it effectively retarded the oxidation of AVS in sediment. PMID:19564075

  1. Concurrent ordering and phase transformation in SmCo7 nanograins.

    PubMed

    Seyring, Martin; Song, Xiaoyan; Zhang, Zhexu; Rettenmayr, Markus

    2015-07-28

    Sm-Co alloys with the stabilized SmCo7 phase are most prominent candidates for advanced high temperature permanent magnets, where the stabilization of the SmCo7 phase can be effectuated by nanostructuring. The complex concurrent processes of ordering and phase transformation in a SmCo7 nanograin are characterized on the atomic scale. For the first time early stages of the phase transformation are made visible by highlighting specific superstructures in single nanograins using Fourier reconstruction of high-resolution transmission electron microscopy images. The superstructures are only detectable and can only be distinguished in specific crystallographic orientations. The evolution of the atom arrangement in the crystal structures is demonstrated for the concurrent ordering process and phase transformation. During decomposition of the metastable SmCo7 phase, the hexagonal Sm2Co17 superstructure (2:17H) forms at first as a precursor of the rhombohedral Sm2Co17 superstructure (2:17R) – this can only be detected by analysis of individual grains and has not been described so far. By extensive crystallographic analysis of individual nanograins, a distinct correlation between the fraction of the superstructure phases and the grain size is found, showing directly and unambiguously the grain size dependence of the phase transformation in the nanocrystalline alloy, a phenomenon that so far has only been shown indirectly using volume averaging methods.

  2. Multi phase field model for solid state transformation with elastic strain

    NASA Astrophysics Data System (ADS)

    Steinbach, I.; Apel, M.

    2006-05-01

    A multi phase field model is presented for the investigation of the effect of transformation strain on the transformation kinetics, morphology and thermodynamic stability in multi phase materials. The model conserves homogeneity of stress in the diffuse interface between elastically inhomogeneous phases, in which respect it differs from previous models. The model is formulated consistently with the multi phase field model for diffusional and surface driven phase transitions [I. Steinbach, F. Pezzolla, B. Nestler, M. Seeßelberg, R. Prieler, G.J. Schmitz, J.L.L. Rezende, A phase field concept for multiphase systems, Physica D 94 (1996) 135-147; J. Tiaden, B. Nestler, H.J. Diepers, I. Steinbach, The multiphase-field model with an integrated concept for modeling solute diffusion, Physica D 115 (1998) 73-86; I. Steinbach, F. Pezzolla, A generalized field method for multiphase transformations using interface fields, Physica D 134 (1999) 385] and gives a consistent description of interfacial tension, multi phase thermodynamics and elastic stress balance in multiple junctions between an arbitrary number of grains and phases. Some aspects of the model are demonstrated with respect to numerical accuracy and the relation between transformation strain, external stress and thermodynamic equilibrium.

  3. Double-image self-encoding and hiding based on phase-truncated Fourier transforms and phase retrieval

    NASA Astrophysics Data System (ADS)

    Wang, Xiaogang; Zhao, Daomu

    2011-09-01

    We propose a method to encrypt two covert images into an overt image based on phase-truncated Fourier transforms and phase retrieval. In this method, the two original images are self-encoded in the manner that one of the two images is directly separated into two phase masks (PMs) and used as keys for encryption, and then multiplied by a PM which is generated by using phase retrieval algorithm. At last, the whole encryption process is completed by a Fourier transform operation. In the decryption process, the image without a separation and the two PMs used as keys for encryption are all treated as encoded data. The cryptosystem is asymmetric which means the keys for encryption are different from those for decryption. Numerical simulations are presented to show the viability and good performance of the proposed method.

  4. Crystalline-crystalline phase transformation in two-dimensional In2Se3 thin layers.

    PubMed

    Tao, Xin; Gu, Yi

    2013-08-14

    We report, for the first time, the fabrication of single-crystal In2Se3 thin layers using mechanical exfoliation and studies of crystalline-crystalline (α → β) phase transformations as well as the corresponding changes of the electrical properties in these thin layers. Particularly, using electron microscopy and correlative in situ micro-Raman and electrical measurements, we show that, in contrast to bulk single crystals, the β phase can persist in single-crystal thin layers at room temperature (RT). The single-crystal nature of the layers before and after the phase transition allows for unambiguous determination of changes in the electrical resistivity. Specifically, the β phase has an electrical resistivity about 1-2 orders of magnitude lower than the α phase. Furthermore, we find that the temperature of the α → β phase transformation increases by as much as 130 K with the layer thickness decreasing from ~87 nm to ~4 nm. These single-crystal thin layers are ideal for studying the scaling behavior of the phase transformations and associated changes of the electrical properties. For these In2Se3 thin layers, the accessibility of the β phase at RT, with distinct electrical properties than the α phase, provides the basis for multilevel phase-change memories in a single material system.

  5. Deep-cryogenic-treatment-induced phase transformation in the Al-Zn-Mg-Cu alloy

    NASA Astrophysics Data System (ADS)

    Li, Chun-mei; Cheng, Nan-pu; Chen, Zhi-qian; Guo, Ning; Zeng, Su-min

    2015-01-01

    An aluminum alloy (Al-Zn-Mg-Cu) subjected to deep cryogenic treatment (DCT) was systematically investigated. The results show that a DCT-induced phase transformation varies the microstructures and affects the mechanical properties of the Al alloy. Both Guinier-Preston (GP) zones and a metastable η' phase were observed by high-resolution transmission electron microscopy. The phenomenon of the second precipitation of the GP zones in samples subjected to DCT after being aged was observed. The viability of this phase transformation was also demonstrated by first-principles calculations.

  6. Detection of indentation induced Fe-to-Afe phase transformation in lead zirconate titanate.

    SciTech Connect

    Baddorf, Arthur P.; Shin, Junsoo; Gogotsi, Yury G.; Buchheit, Thomas Edward; Watson, Chad Samuel; Kalinin, Sergei; Juliano, Thomas F.

    2005-08-01

    Instrumented indentation was combined with microscopy and spectroscopy analysis to investigate the local mechanically induced ferroelectric to anti-ferroelectric phase transformation of niobium-modified lead zirconate titanate 95/5. Indentation experiments to a depth of 2 {micro}m were performed using a Berkovich pyramidal three-sided diamond tip. Subsequent Raman spectroscopy and piezoelectric force microscopy revealed that indentation locally induced the ferroelectric to antiferroelectric phase transformation. Piezoelectric force microscopy demonstrated the ability to map the individual phases within and near indented regions on the niobium-modified lead zirconate titanate ceramics.

  7. Phase transformation of oxide film in zirconium alloy in high temperature hydrogenated water

    SciTech Connect

    Kim, Taeho; Kim, Jongjin; Choi, Kyoung Joon; Yoo, Seung Chang; Kim, Seung Hyun; Kim, Ji Hyun

    2015-07-23

    The effect of the variation of the dissolved hydrogen concentration on the oxide phase transformation under high-temperature hydrogenated water conditions was investigated using in situ Raman spectroscopy. The Raman spectrum in 50 cm(3)/kg of dissolved hydrogen concentration indicated the formation of monoclinic and tetragonal zirconium oxide at the water-substrate interface. As the dissolved hydrogen concentration decreased to 30 cm(3)/kg, the Raman peaks corresponding to the zirconium oxide phase changed, indicating an oxide phase transformation. And, the results of SEM and TEM analyses were compared with those of in situ analyses obtained for the oxide structure formed on the zirconium alloy.

  8. Detection of Indentation Induced FE-to-AFE Phase Transformation in Lead Zirconate Titanate

    SciTech Connect

    Baddorf, Arthur P; Kalinin, Sergei V; Shin, Junsoo; Juliano, Thomas F.; Gogotsi, Yury G.; Buchheit, Thomas E.; Watson, Chad S.

    2006-01-01

    Instrumented indentation was combined with microscopy and spectroscopy analysis to investigate the local mechanically induced ferroelectric to anti-ferroelectric phase transformation of niobium-modified lead zirconate titanate 95/5. Indentation experiments to a depth of 2 {micro}m were performed using a Berkovich pyramidal three-sided diamond tip. Subsequent Raman spectroscopy and piezoelectric force microscopy revealed that indentation locally induced the ferroelectric to antiferroelectric phase transformation. Piezoelectric force microscopy demonstrated the ability to map the individual phases within and near indented regions on the niobium-modified lead zirconate titanate ceramics.

  9. Ultra-fast dynamic compression technique to study kinetics of phase transformations in Bismuth

    SciTech Connect

    Smith, R F; Kane, J O; Eggert, J H; Saculla, M D; Jankowski, A F; Bastea, M; Hicks, D G; Collins, G W

    2007-12-28

    Pre-heated Bi was ramp compressed within 30 ns to a peak stress of {approx}11 GPa to explore structural phase transformation kinetics under dynamic loading conditions. Under these ultra-fast compression time-scales the equilibrium Bi I-II phase boundary is overpressurized by {Delta}P {approx} 0.8 GPa. {Delta}P is observed to increase logarithmically with strain rate, {var_epsilon}, above 10{sup 6} s{sup -1}. Estimates from a kinetics model predict that the Bi I phase is fully transformed within 3 ns.

  10. The backward phase flow and FBI-transform-based Eulerian Gaussian beams for the Schroedinger equation

    SciTech Connect

    Leung Shingyu; Qian Jianliang

    2010-11-20

    We propose the backward phase flow method to implement the Fourier-Bros-Iagolnitzer (FBI)-transform-based Eulerian Gaussian beam method for solving the Schroedinger equation in the semi-classical regime. The idea of Eulerian Gaussian beams has been first proposed in . In this paper we aim at two crucial computational issues of the Eulerian Gaussian beam method: how to carry out long-time beam propagation and how to compute beam ingredients rapidly in phase space. By virtue of the FBI transform, we address the first issue by introducing the reinitialization strategy into the Eulerian Gaussian beam framework. Essentially we reinitialize beam propagation by applying the FBI transform to wavefields at intermediate time steps when the beams become too wide. To address the second issue, inspired by the original phase flow method, we propose the backward phase flow method which allows us to compute beam ingredients rapidly. Numerical examples demonstrate the efficiency and accuracy of the proposed algorithms.

  11. Digital carrier superposition by Hilbert-Huang transform for optical phase recovery in speckle shearing interferometry

    NASA Astrophysics Data System (ADS)

    Amar, Said; Bahich, Mustapha; Dalimi, Hanane; Barj, ElMostapha; Afifi, Mohamed

    2015-01-01

    Industrial production constraints often require technical tests and controls. Optical metrology methods allow a non destructive test of wide range of parameters, such as defects and displacements, with very good accuracy. The phase retrieval is an effective way that allows three-dimensional profile reconstruction from intensity shearograms. This research work focuses on the extraction of the phase from one uncarrier shearogram using the Hilbert-Huang transform. An algorithm for the phase calculation based on the bidimensional empirical mode decomposition, Hilbert transform (HT), and Fourier transform (FT) is presented. A spatial digital carrier has been superimposed before the application of the FT or HT which uses two π/2 shifted shearograms, to get access to the phase map via a global analysis of intensity images. An evaluation was made through a numerical simulation to validate and confirm the performance of the proposed algorithm. The main advantage of this technique is its ability to provide a metrological solution for fast dynamic analysis.

  12. Phase equilibria and transformations in the Ti-Al-Nb system

    NASA Astrophysics Data System (ADS)

    Mishurda, Joseph Constantine

    The phase equilibria and transformations in the Nb-Ti-Al system in the vicinity of the Sigma phase field have been examined with respect to the Liquidus Surface (Phase 1), the Phase Equilibria and Equilibrium Transformations (Phase II), and the Phase Transformations, Mechanisms and Kinetics (Phase III). Eight alloy compositions were produced by arc melting. The alloys were characterized by differential thermal analysis, metallography, X-ray diffraction, scanning electron microscopy (BSEI), electron probe microanalysis and transmission electron microscopy. The liquidus examination shed new light on previous microstructural interpretations, opening up new possibilities for microstructural development and control of multiphase alloys. Differential thermal analysis has identified the existence of a beta to sigma + gamma transformation in an alloy where it was not previously thought to exist. The results differed from the calculated diagram by higher titanium solubility in the sigma and delta phases than predicted at lower temperatures and a lower solubility of alpha2 and gamma. The high temperature betao transforms to gamma + sigma in a eutectoid fashion resulting in a desirable lamellar structure of sigma and gamma. The existence of a new body centered tetragonal crystal structure ao = 5.11A and co 28.12A with a point group symmetry of P4/mmm, at 700°C was discovered. A plethel section was found for the sigma + beta two phase alloys. A betao + O + sigma three phase field passes through the alloys between 981 and 1000°C. The plethel section at the transformation has an eutectoid characteristic, however, the nature of the transformation changes to a peritectoid. At temperatures below 970°C, the first transformation to occur is the decomposition of the metastable betao phase to an intermediate metastable phase O'. Reasonable values for Q were obtained, applicable to the diffusion limited region of the TTT-curve. The microstructure evolution of the sigma + beta

  13. Molecular dynamics simulation of the martensitic phase transformation in NiAl alloys.

    PubMed

    Pun, G P Purja; Mishin, Y

    2010-10-01

    Using molecular dynamics simulations with an embedded-atom interatomic potential, we study the effect of chemical composition and uniaxial mechanical stresses on the martensitic phase transformation in Ni-rich NiAl alloys. The martensitic phase has a tetragonal crystal structure and can contain multiple twins arranged in domains and plates. The transformation is reversible and is characterized by a significant temperature hysteresis. The magnitude of the hysteresis depends on the chemical composition and stress. We show that applied compressive and tensile stresses reduce and can even eliminate the hysteresis. Crystalline defects such as free surfaces, dislocations and anti-phase boundaries reduce the martensitic transformation temperature and affect the microstructure of the martensite. Their effect can be explained by heterogeneous nucleation of the new phase in defected regions.

  14. Phase transformation of Mg-calcite to aragonite in active-forming hot spring travertines

    NASA Astrophysics Data System (ADS)

    Greer, Heather F.; Zhou, Wuzong; Guo, Li

    2015-08-01

    A travertine specimen collected from the western part of Yunnan Province of China was subjected to microstructural analysis by powder X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy and energy dispersive X-ray spectroscopy. A new formation mechanism was proposed whereby polycrystalline rhombohedral particles of magnesium-containing calcite underwent a phase transformation into sheaf-like clusters of aragonite microrods. It is proposed that a high concentration of magnesium ions and embedded biological matter poisoned the growth of calcite and therefore instigated the phase transformation of the core of the rhombohedral calcite particles to an aragonite phase with a higher crystallinity. The single crystalline aragonite microrods with a higher density than the Mg-calcite nanocrystallites grew at the expense of the latter to generate sheaf-like clusters. This newly discovered formation mechanism is expected to enhance previous knowledge on this geologically important phase transformation from a morphology point of view.

  15. A Synthetic Quadrature Phase Detector/Demodulator for Fourier Transform Transform Spectrometers

    NASA Technical Reports Server (NTRS)

    Campbell, Joel

    2008-01-01

    A method is developed to demodulate (velocity correct) Fourier transform spectrometer (FTS) data that is taken with an analog to digital converter that digitizes equally spaced in time. This method makes it possible to use simple low cost, high resolution audio digitizers to record high quality data without the need for an event timer or quadrature laser hardware, and makes it possible to use a metrology laser of any wavelength. The reduced parts count and simplicity implementation makes it an attractive alternative in space based applications when compared to previous methods such as the Brault algorithm.

  16. Devil's vortex Fresnel lens phase masks on an asymmetric cryptosystem based on phase-truncation in gyrator wavelet transform domain

    NASA Astrophysics Data System (ADS)

    Singh, Hukum

    2016-06-01

    An asymmetric scheme has been proposed for optical double images encryption in the gyrator wavelet transform (GWT) domain. Grayscale and binary images are encrypted separately using double random phase encoding (DRPE) in the GWT domain. Phase masks based on devil's vortex Fresnel Lens (DVFLs) and random phase masks (RPMs) are jointly used in spatial as well as in the Fourier plane. The images to be encrypted are first gyrator transformed and then single-level discrete wavelet transformed (DWT) to decompose LL , HL , LH and HH matrices of approximation, horizontal, vertical and diagonal coefficients. The resulting coefficients from the DWT are multiplied by other RPMs and the results are applied to inverse discrete wavelet transform (IDWT) for obtaining the encrypted images. The images are recovered from their corresponding encrypted images by using the correct parameters of the GWT, DVFL and its digital implementation has been performed using MATLAB 7.6.0 (R2008a). The mother wavelet family, DVFL and gyrator transform orders associated with the GWT are extra keys that cause difficulty to an attacker. Thus, the scheme is more secure as compared to conventional techniques. The efficacy of the proposed scheme is verified by computing mean-squared-error (MSE) between recovered and the original images. The sensitivity of the proposed scheme is verified with encryption parameters and noise attacks.

  17. Characterization of Solid State Phase Transformation in Continuously Heated and Cooled Ferritic Weld Metal

    SciTech Connect

    Narayana, B; Mills, Michael J.; Specht, Eliot D; Santella, Michael L; Babu, Sudarsanam Suresh

    2010-12-01

    Arc welding processes involve cooling rates that vary over a wide range (1-100 K/s). The final microstructire is thus a product of the heating and cooling cycles experienced by the weld in addition to the weld composition. It has been shown that the first phase to form under weld cooling conditions may not be that predicted by equilibrium calculations. The partitioning of different interstitial/substitutional alloying elements at high temperatures can dramatically affect the subsequent phase transformations. In order to understand the effect of alloying on phase transformation temperatures and final microstructures time-resolved X-ray diffraction technique has been successfully used for characterization. The work by Jacot and Rappaz on pearlitic steels provided insight into austenitization of hypoeutectic steels using a finite volume model. However there is very little work done on the effect of heating and cooling rates on the phase transformation paths in bainitic/martensitic steels and weld metals. Previous work on a weld with higher aluminum content, deposited with a FCAW-S process indicated that even at aluminum levels where the primary phase to solidify from liquid should be delta ferrite, non-equilibrium austenite was observed. The presence of inhomogeneity in composition of the parent microstructure has been attributed to differences in transformation modes, temperatures and microstructures in dual-phase, TRIP steels and ferritic welds. The objectives of the work included the identification of the stability regions of different phases during heating and cooling, differences in the effect of weld heating and cooling rates on the phase transformation temperatures, and the variation in phase fractions of austenite and ferrite in the two phase regions as a function of temperature. The base composition used for the present work is a Fe-1%Al-2%Mn-1%Ni-0.04%C weld metal. A pseudo-binary phase diagram shows the expected solidification path under equilibrium

  18. Phase Transformation in Radially Merged Wurtzite GaAs Nanowires

    PubMed Central

    2015-01-01

    III–V Nanowires (NWs) grown with metal–organic chemical vapor deposition commonly show a polytypic crystal structure, allowing growth of structures not found in the bulk counterpart. In this paper we studied the radial overgrowth of pure wurtzite (WZ) GaAs nanowires and characterized the samples with high resolution X-ray diffraction (XRD) to reveal the crystal structure of the grown material. In particular, we investigated what happens when adjacent WZ NWs radially merge with each other by analyzing the evolution of XRD peaks for different amounts of radial overgrowth and merging. By preparing cross-sectional lamella samples we also analyzed the local crystal structure of partly merged NWs by transmission electron microscopy. Once individual NWs start to merge, the crystal structure of the merged segments is transformed progressively from initial pure WZ to a mixed WZ/ZB structure. The merging process is then modeled using a simple combinatorial approach, which predicts that merging of two or more WZ NWs will result in a mixed crystal structure containing WZ, ZB, and 4H. The existence large and relaxed segments of 4H structure within the merged NWs was confirmed by XRD, allowing us to accurately determine the lattice parameters of GaAs 4H. We compare the measured WZ and 4H unit cells with an ideal tetrahedron and find that both the polytypes are elongated in the c-axis and compressed in the a-axis compared to the geometrically converted cubic ZB unit cell. PMID:26494983

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

    NASA Technical Reports Server (NTRS)

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

    1985-01-01

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

  20. Organizational transformation into the operational phase of the GTC

    NASA Astrophysics Data System (ADS)

    van der Hoeven, Michiel; Rutten, René; Alvarez Martin, Pedro

    2012-09-01

    In this paper we review various organizational issues encountered when GRANTECAN, the Spanish organization responsible for the construction and operation of the GTC telescope, evolved from the construction phase of a large telescope facility into the phase of scientific operation. GRANTECAN now operates and further develops the 10.4m segmented telescope, GTC. The advent of operational pressures to scientifically exploit the telescope enforced a number of organizational changes as priorities shifted towards achieving the best possible level of operational effectiveness. In this paper we will treat the GRANTECAN experience as a case study of the limitations and problems that were encountered throughout this change. We will focus on the processes and strategies applied in order to achieve the necessary changes. We will place our experience in the framework of the McKinsey 7S model, highlight a number of key performance indicators, and will indicate the organizational changes that have taken place, that influenced the way the objectives are achieved. We will present a forward look based on our experience to date.

  1. Finite element analysis of the tetragonal to monoclinic phase transformation during oxidation of zirconium alloys

    NASA Astrophysics Data System (ADS)

    Platt, P.; Frankel, P.; Gass, M.; Howells, R.; Preuss, M.

    2014-11-01

    Corrosion is a key limiting factor in the degradation of zirconium alloys in light water reactors. Developing a mechanistic understanding of the corrosion process offers a route towards improving safety and efficiency as demand increases for higher burn-up of fuel. Oxides formed on zirconium alloys are composed of both monoclinic and meta-stable tetragonal phases, and are subject to a number of potential mechanical degradation mechanisms. The work presented investigates the link between the tetragonal to monoclinic oxide phase transformation and degradation of the protective character of the oxide layer. To achieve this, Abaqus finite element analysis of the oxide phase transformation has been carried out. Study of the change in transformation strain energy shows how relaxation of oxidation induced stress and fast fracture at the metal-oxide interface could destabilise the tetragonal phase. Central to this is the identification of the transformation variant most likely to form, and understanding why twinning of the transformed grain is likely to occur. Development of transformation strain tensors and analysis of the strain components allows some separation of dilatation and shear effects. Maximum principal stress is used as an indication of fracture in the surrounding oxide layer. Study of the stress distributions shows the way oxide fracture is likely to occur and the differing effects of dilatation and shape change. Comparison with literature provides qualitative validation of the finite element simulations.

  2. Phase transformations and phase relations in Ti{sub 50}Pd{sub (50-x)}TM{sub x} alloys

    SciTech Connect

    Schwartz, A.J.; Sluiter, M.H.; Harmon, B.N.; Tanner, L.E.

    1994-07-15

    The effect of transition metal (TM) substitution for Pd in Ti{sub 5O}Pd{sub (50-x}TM{sub x} alloys with x between 5 and 37.5 at.% and TM = V, Cr, Mn and Fe are being characterized by transmission electron microscopy and First-Principles Alloy Theory modeling. The goal is to obtain detailed structural information related to the ternary phase relations and transformations that are necessary for effective shape-memory alloy development. Thus far, the authors have found that the tend to have pseudobinary eutectoid-like configurations with a terminal TiPd and a non-close-packed long period ordered structure type crystal structure) based on the stoichiometry Ti{sub 2}PdTM. The systems exhibit a conventional martensitic transformation, as well as a new type of displacive transformation that shear-modulates B2 to produce a periodically distorted, but non-close-packed metastable product phase.

  3. Understanding strain-induced phase transformations in BiFeO3 thin films

    DOE PAGESBeta

    Dixit, Hemant; Beekman, Christianne; Schlepütz, Christian M.; Siemons, Wolter; Yang, Yongsoo; Senabulya, Nancy; Clarke, Roy; Chi, Miaofang; Christen, Hans M.; Cooper, Valentino R.

    2015-05-01

    Experiments demonstrate that under large epitaxial strain a coexisting striped phase emerges in BiFeO₃ thin films, which comprises a tetragonal-like (T´) and an intermediate S´ polymorph. It exhibits a relatively large piezoelectric response when switching between the coexisting phase and a uniform T´ phase. This strain-induced phase transformation is investigated through a synergistic combination of first-principles theory and experiments. The results show that the S´ phase is energetically very close to the T´ phase, but is structurally similar to the bulk rhombohedral (R) phase. By fully characterizing the intermediate S´ polymorph, it is demonstrated that the flat energy landscape resultingmore » in the absence of an energy barrier between the T´ and S´ phases fosters the above-mentioned reversible phase transformation. This ability to readily transform between the S´ and T´ polymorphs, which have very different octahedral rotation patterns and c/a ratios, is crucial to the enhanced piezoelectricity in strained BiFeO3 films. Additionally, a blueshift in the band gap when moving from R to S´ to T´ is observed. These results emphasize the importance of strain engineering for tuning electromechanical responses or, creating unique energy harvesting photonic structures, in oxide thin film architectures.« less

  4. Understanding strain-induced phase transformations in BiFeO3 thin films

    SciTech Connect

    Dixit, Hemant; Beekman, Christianne; Schlepütz, Christian M.; Siemons, Wolter; Yang, Yongsoo; Senabulya, Nancy; Clarke, Roy; Chi, Miaofang; Christen, Hans M.; Cooper, Valentino R.

    2015-05-01

    Experiments demonstrate that under large epitaxial strain a coexisting striped phase emerges in BiFeO₃ thin films, which comprises a tetragonal-like (T´) and an intermediate S´ polymorph. It exhibits a relatively large piezoelectric response when switching between the coexisting phase and a uniform T´ phase. This strain-induced phase transformation is investigated through a synergistic combination of first-principles theory and experiments. The results show that the S´ phase is energetically very close to the T´ phase, but is structurally similar to the bulk rhombohedral (R) phase. By fully characterizing the intermediate S´ polymorph, it is demonstrated that the flat energy landscape resulting in the absence of an energy barrier between the T´ and S´ phases fosters the above-mentioned reversible phase transformation. This ability to readily transform between the S´ and T´ polymorphs, which have very different octahedral rotation patterns and c/a ratios, is crucial to the enhanced piezoelectricity in strained BiFeO3 films. Additionally, a blueshift in the band gap when moving from R to S´ to T´ is observed. These results emphasize the importance of strain engineering for tuning electromechanical responses or, creating unique energy harvesting photonic structures, in oxide thin film architectures.

  5. Earth physics and phase transformations program: A concept and proposal

    NASA Technical Reports Server (NTRS)

    Bonavito, N. L.; Tanaka, T.

    1971-01-01

    A program to study the geophysical characteristics of the earth is presented as an integration of the different disciplines that constitute the earth sciences, through the foundation of a generalized geodynamic theory of earth physics. A program is considered for defining the physical constants of the earth's material which parametrize the hydrodynamic equation in the microscopic solid state behavior of the crystals of the lithosphere. In addition, in order to lay the foundation for a generalized theory in earth physics, specific research areas are considered, such as the nature of the kinetics of the phase transitions in mineral assemblages, the equilibrium thermodynamic properties of crystals which are major constituents of mineral assemblages, and the transport properties of pure crystals which are major constituents of mineral assemblages.

  6. Thermodynamics and Kinetics of Phase Transformations in Hydrogen Storage Materials

    SciTech Connect

    Ceder, Gerbrand; Marzari, Nicola

    2011-08-31

    The aim of this project is to develop and apply computational materials science tools to determine and predict critical properties of hydrogen storage materials. By better understanding the absorption/desorption mechanisms and characterizing their physical properties it is possible to explore and evaluate new directions for hydrogen storage materials. Particular emphasis is on the determination of the structure and thermodynamics of hydrogen storage materials, the investigation of microscopic mechanisms of hydrogen uptake and release in various materials and the role of catalysts in this process. As a team we have decided to focus on a single material, NaAlH{sub 4}, in order to fully be able to study the many aspects of hydrogen storage. We have focused on phase stability, mass transport and size-dependent reaction mechanisms in this material.

  7. A new phase transformation path from nanodiamond to new-diamond via an intermediate carbon onion.

    PubMed

    Xiao, J; Li, J L; Liu, P; Yang, G W

    2014-12-21

    The investigation of carbon allotropes such as graphite, diamond, fullerenes, nanotubes and carbon onions and mechanisms that underlie their mutual phase transformation is a long-standing problem of great fundamental importance. New diamond (n-diamond) is a novel metastable phase of carbon with a face-centered cubic structure; it is called "new diamond" because many reflections in its electron diffraction pattern are similar to those of diamond. However, producing n-diamond from raw carbon materials has so far been challenging due to n-diamond's higher formation energy than that of diamond. Here, we, for the first time, demonstrate a new phase transformation path from nanodiamond to n-diamond via an intermediate carbon onion in the unique process of laser ablation in water, and establish that water plays a crucial role in the formation of n-diamond. When a laser irradiates colloidal suspensions of nanodiamonds at ambient pressure and room temperature, nanodiamonds are first transformed into carbon onions serving as an intermediate phase, and sequentially carbon onions are transformed into n-diamonds driven by the laser-induced high temperature and high pressure from the carbon onion as a nanoscaled temperature and pressure cell upon the process of laser irradiation in a liquid. This phase transformation not only provides new insight into the physical mechanism involved, but also offers one suitable opportunity for breaking controllable pathways between n-diamond and carbon allotropes such as diamond and carbon onions.

  8. Direct observations of welding-induced solid-state phase transformations

    SciTech Connect

    Elmer, J.W.; Wong, J.; Waide, P.A.

    1994-12-31

    A new diagnostic tool that uses time-resolved x-ray diffraction (TRXRD) for in-situ, spatially resolved, phase identification around a weld is presented for the purpose of mapping the location of phase fields during welding. In this investigation, TRXRD experiments were conducted at the Stanford Sychrotron Radiation Laboratory where a high-intensity tunable synchrotron x-ray `probe` was available. The high spatial resolution of the x-ray probe (1mm) allowed precise mapping of specific phase fields around the weld, while the high intensity of the beam (10{sup 11} photons/s) yielded high signal-to-noise ratio of the diffracted x-rays. These characteristics enabled the crystal structure to be characterized during a 1-s x-ray integration time, thus providing real-time data to be gathered about welding-induced phase transformations. Experiments were performed on unalloyed Grade 4 titanium (Ti, 0.28%Fe, 0.38%O), which has an allotropic phase transition that occurs at 922{degrees}C, where the low temperature hcp phase transforms to the high temperature bcc phase. Welds were made using a semi-automatic tungsten inert gas procedure to establish a quasisteady-state thermal profile on 4.5 in. diameter titanium bar, which was rotated at a speed of 0.5 rpm beneath a 3.5 kW arc. Characteristic hcp, bcc, and liquid diffraction peaks were measured along x-ray probe scans traveling from the base metal through the heat-affected zone and into the weld pool, respectively. The results of this study clearly demonstrate the feasibility of using TRXRD for in-situ investigations of welding-induced phase transformations, thus allowing verification of welding models, the creation of transformation diagrams during rapid thermal cycling of materials, and the ability for real-time investigations of the nucleation and growth behavior of solid-state phase transformations.

  9. In Vitro Evaluation of Ferrihydrite as an Enterosorbent for Arsenic from Contaminated Drinking Water

    PubMed Central

    Taylor, J. F.; Robinson, A.; Johnson, N.; Marroquin-Cardona, A.; Brattin, B.; Taylor, R.; Phillips, T. D.

    2009-01-01

    Arsenic (As) is a toxic trace element found in groundwater due to natural and industrial processes. Exposure has been linked to cancers of the bladder, lungs, skin, kidneys, nasal passages, liver, and the prostate. Arsenic in drinking water is a problem in many countries, notably Bangladesh and Taiwan. The purpose of this research was to utilize binding isotherms, a simulated gastrointestinal (GI) model, and the adult Hydra bioassay to evaluate ferrihydrite’s potential to bind As and serve as a potential enterosorbent for As found in drinking water. A variety of clay minerals and synthesized iron oxides including ferrihydrite were screened for their ability to bind As(III), as sodium arsenite, and As(V), as sodium arsenate. After ferrihydrite was demonstrated to be the most effective sorbent for both As species, adsorption isotherms were performed. All isotherm data were fit to the Langmuir equation to determine adsorption capacity (Qmax). Ferrihydrite bound 96% of As(III) and 97% of As(V) in the screening studies and had a Qmax of 1.288 mol/kg for As(III) and 0.744 mol/kg for As(V). Using a simulated GI model, ferrihydrite was found to effectively adsorb As(V) and As(III) in the stomach and intestine. Ferrihydrite (0.25% w/w) protected adult hydra at levels up to 200 times the minimal effective concentration (MEC) for As(III) and up to 2.5 times the MEC for As(V). These experiments confirm that ferrihydrite is a high capacity sorbent of As, and that it is effective at removing As in a simulated GI model. These results suggest that ferrihydrite could be used as a potential enterosorbent for As found in drinking water. Future work will focus on verifying ferrihydrite’s safety and efficacy in vivo. PMID:19708388

  10. Phase transformations of nano-sized cubic boron nitride to white graphene and white graphite

    SciTech Connect

    Dang, Hongli; Liu, Yingdi; Xue, Wenhua; Anderson, Ryan S.; Sewell, Cody R.; Xue, Sha; Crunkleton, Daniel W.; Shen, Yaogen; Wang, Sanwu

    2014-03-03

    We report quantum-mechanical investigations that predict the formation of white graphene and nano-sized white graphite from the first-order phase transformations of nano-sized boron nitride thin-films. The phase transformations from the nano-sized diamond-like structure, when the thickness d > 1.4 nm, to the energetically more stable nano-sized white graphite involve low activation energies of less than 1.0 eV. On the other hand, the diamond-like structure transforms spontaneously to white graphite when d ≤ 1.4 nm. In particular, the two-dimensional structure with single-layer boron nitride, the so-called white graphene, could be formed as a result of such transformation.

  11. A test of the Johnson-Mehl-Avrami equation. [for phase transformations

    NASA Technical Reports Server (NTRS)

    Weinberg, Michael C.

    1987-01-01

    The accuracy of the Johnson-Mehl-Avrami (JMA) equation is evaluated for the special case of two-dimensional crystallization. The volume fraction transformed is determined directly by computer modeling, and the evaluation of the secondary phase obtained is compared with predictions of the JMA equation. The JMA equation if found to be highly acccurate over virtually the entire range of the transformation process.

  12. Theory of the amplitude-phase retrieval in any linear-transform system and its applications

    NASA Astrophysics Data System (ADS)

    Yang, Guozhen; Gu, Ben-Yuan; Dong, Bi-Zhen

    1992-12-01

    This paper is a summary of the theory of the amplitude-phase retrieval problem in any linear transform system and its applications based on our previous works in the past decade. We describe the general statement on the amplitude-phase retrieval problem in an imaging system and derive a set of equations governing the amplitude-phase distribution in terms of the rigorous mathematical derivation. We then show that, by using these equations and an iterative algorithm, a variety of amplitude-phase problems can be successfully handled. We carry out the systematic investigations and comprehensive numerical calculations to demonstrate the utilization of this new algorithm in various transform systems. For instance, we have achieved the phase retrieval from two intensity measurements in an imaging system with diffraction loss (non-unitary transform), both theoretically and experimentally, and the recovery of model real image from its Hartley-transform modulus only in one and two dimensional cases. We discuss the achievement of the phase retrieval problem from a single intensity only based on the sampling theorem and our algorithm. We also apply this algorithm to provide an optimal design of the phase-adjusted plate for a phase-adjustment focusing laser accelerator and a design approach of single phase-only element for implementing optical interconnect. In order to closely simulate the really measured data, we examine the reconstruction of image from its spectral modulus corrupted by a random noise in detail. The results show that the convergent solution can always be obtained and the quality of the recovered image is satisfactory. We also indicated the relationship and distinction between our algorithm and the original Gerchberg- Saxton algorithm. From these studies, we conclude that our algorithm shows great capability to deal with the comprehensive phase-retrieval problems in the imaging system and the inverse problem in solid state physics. It may open a new way to

  13. The influence of martensite shape, concentration, and phase transformation strain on the deformation behavior of stable dual-phase steels

    NASA Astrophysics Data System (ADS)

    Bhattacharyya, A.; Sakaki, T.; Weng, G. J.

    1993-02-01

    A continuum model is developed to examine the influence of martensite shape, volume fraction, phase transformation strain, and thermal mismatch on the initial plastic state of the ferrite matrix following phase transformation and on the subsequent stress-strain behavior of the dual-phase steels upon loading. The theory is developed based on a relaxed constraint in the ductile matrix and an energy criterion to define its effective stress. In addition, it also assumes the martensite islands to possess a spheroidal shape and to be randomly oriented and homogenously dispersed in the ferrite matrix. It is found that for a typical water-quenched process from an intercritical temperature of 760 °C, the critical martensite volume fraction needed to induce plastic deformation in the ferrite matrix is very low, typically below 1 pct, regardless of the martensite shape. Thus, when the two-phase system is subjected to an external load, plastic deformation commences immediately, resulting in the widely observed “continuous yielding” behavior in dual-phase steels. The subsequent deformation of the dual-phase system is shown to be rather sensitive to the martensite shape, with the disc-shaped morphology giving rise to a superior overall response (over the spherical type). The stress-strain relations are also dependent upon the magnitude of the prior phase transformation strain. The strength coefficient h and the work-hardening exponent n of the smooth, parabolic-type stress-strain curves of the dual-phase system also increase with increasing martensite content for each selected inclusion shape. Comparison with an exact solution and with one set of experimental data indicates that the theory is generally within a reasonable range of accuracy.

  14. Stress-induced phase transformation and optical coupling of silver nanoparticle superlattices into mechanically stable nanowires

    NASA Astrophysics Data System (ADS)

    Li, Binsong; Wen, Xiaodong; Li, Ruipeng; Wang, Zhongwu; Clem, Paul G.; Fan, Hongyou

    2014-06-01

    One-dimensional silver materials display unique optical and electrical properties with promise as functional blocks for a new generation of nanoelectronics. To date, synthetic approaches and property engineering of silver nanowires have primarily focused on chemical methods. Here we report a simple physical method of metal nanowire synthesis, based on stress-induced phase transformation and sintering of spherical Ag nanoparticle superlattices. Two phase transformations of nanoparticles under stress have been observed at distinct length scales. First, the lattice dimensions of silver nanoparticle superlattices may be reversibly manipulated between 0-8 GPa compressive stresses to enable systematic and reversible changes in mesoscale optical coupling between silver nanoparticles. Second, stresses greater than 8 GPa induced an atomic lattice phase transformation, which induced sintering of silver nanoparticles into micron-length scale nanowires. The nanowire synthesis mechanism displays a dependence on both nanoparticle crystal surface orientation and presence of particular grain boundaries to enable nanoparticle consolidation into nanowires.

  15. Neural network calibration of a snapshot birefringent Fourier transform spectrometer with periodic phase errors.

    PubMed

    Luo, David; Kudenov, Michael W

    2016-05-16

    Systematic phase errors in Fourier transform spectroscopy can severely degrade the calculated spectra. Compensation of these errors is typically accomplished using post-processing techniques, such as Fourier deconvolution, linear unmixing, or iterative solvers. This results in increased computational complexity when reconstructing and calibrating many parallel interference patterns. In this paper, we describe a new method of calibrating a Fourier transform spectrometer based on the use of artificial neural networks (ANNs). In this way, it is demonstrated that a simpler and more straightforward reconstruction process can be achieved at the cost of additional calibration equipment. To this end, we provide a theoretical model for general systematic phase errors in a polarization birefringent interferometer. This is followed by a discussion of our experimental setup and a demonstration of our technique, as applied to data with and without phase error. The technique's utility is then supported by comparison to alternative reconstruction techniques using fast Fourier transforms (FFTs) and linear unmixing.

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  17. Neural network calibration of a snapshot birefringent Fourier transform spectrometer with periodic phase errors.

    PubMed

    Luo, David; Kudenov, Michael W

    2016-05-16

    Systematic phase errors in Fourier transform spectroscopy can severely degrade the calculated spectra. Compensation of these errors is typically accomplished using post-processing techniques, such as Fourier deconvolution, linear unmixing, or iterative solvers. This results in increased computational complexity when reconstructing and calibrating many parallel interference patterns. In this paper, we describe a new method of calibrating a Fourier transform spectrometer based on the use of artificial neural networks (ANNs). In this way, it is demonstrated that a simpler and more straightforward reconstruction process can be achieved at the cost of additional calibration equipment. To this end, we provide a theoretical model for general systematic phase errors in a polarization birefringent interferometer. This is followed by a discussion of our experimental setup and a demonstration of our technique, as applied to data with and without phase error. The technique's utility is then supported by comparison to alternative reconstruction techniques using fast Fourier transforms (FFTs) and linear unmixing. PMID:27409947

  18. Influence of Laser Peening on Phase Transformation and Corrosion Resistance of AISI 321 steel

    NASA Astrophysics Data System (ADS)

    Karthik, D.; Swaroop, S.

    2016-07-01

    The objective of this study is to investigate the influence of laser peening without coating (LPwC) on austenitic to martensitic (γ → α') phase transformation and corrosion behavior of austenitic stainless steel AISI 321 in 3.5% NaCl environment. Results indicate that LPwC induces a large compressive residual stresses of nearly -854 MPa and γ → α' phase transformation of about 18% (volume fraction). Microstructures of peened surface confirmed the γ → α' phase transformation and showed no grain refinement. Hardness increased slightly with a case depth of 900 μm. Despite the smaller surface roughness introduced, corrosion resistance improved after peening due to compressive residual stresses.

  19. Phase Field Modeling of Cyclic Austenite-Ferrite Transformations in Fe-C-Mn Alloys

    NASA Astrophysics Data System (ADS)

    Chen, Hao; Zhu, Benqiang; Militzer, Matthias

    2016-08-01

    Three different approaches for considering the effect of Mn on the austenite-ferrite interface migration in an Fe-0.1C-0.5Mn alloy have been coupled with a phase field model (PFM). In the first approach (PFM-I), only long-range C diffusion is considered while Mn is assumed to be immobile during the phase transformations. Both long-range C and Mn diffusions are considered in the second approach (PFM-II). In the third approach (PFM-III), long-range C diffusion is considered in combination with the Gibbs energy dissipation due to Mn diffusion inside the interface instead of solving for long-range diffusion of Mn. The three PFM approaches are first benchmarked with isothermal austenite-to-ferrite transformation at 1058.15 K (785 °C) before considering cyclic phase transformations. It is found that PFM-II can predict the stagnant stage and growth retardation experimentally observed during cycling transformations, whereas PFM-III can only replicate the stagnant stage but not the growth retardation and PFM-I predicts neither the stagnant stage nor the growth retardation. The results of this study suggest a significant role of Mn redistribution near the interface on reducing transformation rates, which should, therefore, be considered in future simulations of austenite-ferrite transformations in steels, particularly at temperatures in the intercritical range and above.

  20. Analysis of Transformation Plasticity in Steel Using a Finite Element Method Coupled with a Phase Field Model

    PubMed Central

    Cho, Yi-Gil; Kim, Jin-You; Cho, Hoon-Hwe; Cha, Pil-Ryung; Suh, Dong-Woo; Lee, Jae Kon; Han, Heung Nam

    2012-01-01

    An implicit finite element model was developed to analyze the deformation behavior of low carbon steel during phase transformation. The finite element model was coupled hierarchically with a phase field model that could simulate the kinetics and micro-structural evolution during the austenite-to-ferrite transformation of low carbon steel. Thermo-elastic-plastic constitutive equations for each phase were adopted to confirm the transformation plasticity due to the weaker phase yielding that was proposed by Greenwood and Johnson. From the simulations under various possible plastic properties of each phase, a more quantitative understanding of the origin of transformation plasticity was attempted by a comparison with the experimental observation. PMID:22558295

  1. Analysis of transformation plasticity in steel using a finite element method coupled with a phase field model.

    PubMed

    Cho, Yi-Gil; Kim, Jin-You; Cho, Hoon-Hwe; Cha, Pil-Ryung; Suh, Dong-Woo; Lee, Jae Kon; Han, Heung Nam

    2012-01-01

    An implicit finite element model was developed to analyze the deformation behavior of low carbon steel during phase transformation. The finite element model was coupled hierarchically with a phase field model that could simulate the kinetics and micro-structural evolution during the austenite-to-ferrite transformation of low carbon steel. Thermo-elastic-plastic constitutive equations for each phase were adopted to confirm the transformation plasticity due to the weaker phase yielding that was proposed by Greenwood and Johnson. From the simulations under various possible plastic properties of each phase, a more quantitative understanding of the origin of transformation plasticity was attempted by a comparison with the experimental observation. PMID:22558295

  2. Linear canonical transformations of coherent and squeezed states in the Wigner phase space

    NASA Technical Reports Server (NTRS)

    Han, D.; Kim, Y. S.; Noz, Marilyn E.

    1988-01-01

    It is shown that classical linear canonical transformations are possible in the Wigner phase space. Coherent and squeezed states are shown to be linear canonical transforms of the ground-state harmonic oscillator. It is therefore possible to evaluate the Wigner functions for coherent and squeezed states from that for the harmonic oscillator. Since the group of linear canonical transformations has a subgroup whose algebraic property is the same as that of the (2+1)-dimensional Lorentz group, it may be possible to test certain properties of the Lorentz group using optical devices. A possible experiment to measure the Wigner rotation angle is discussed.

  3. Neutron Scattering Studies of Pre-Transitional Effects in Solid-Solid Phase Transformations

    SciTech Connect

    Shapiro, S. M.

    1999-06-30

    Neutron scattering studies have played a fundamental role in understanding solid-solid phase transformations, particularly in studying the lattice dynamical behavior associated with precursor effects. A review of the studies performed on solids exhibiting Martensitic transformations is given below. The mode softening and associated elastic diffuse scattering, previously observed in NiAl alloys, will be discussed as well as more recent work on Ni{sub 2}MnGa, a system exhibiting magnetic order as well as a Martensitic transformation. Also, new results on the precursor effects in ordered and disordered FePt alloys will be presented.

  4. Continuous wavelet transform for non-stationary vibration detection with phase-OTDR.

    PubMed

    Qin, Zengguang; Chen, Liang; Bao, Xiaoyi

    2012-08-27

    We propose the continuous wavelet transform for non-stationary vibration measurement by distributed vibration sensor based on phase optical time-domain reflectometry (OTDR). The continuous wavelet transform approach can give simultaneously the frequency and time information of the vibration event. Frequency evolution is obtained by the wavelet ridge detection method from the scalogram of the continuous wavelet transform. In addition, a novel signal processing algorithm based on the global wavelet spectrum is used to determine the location of vibration. Distributed vibration measurements of 500 Hz and 500 Hz to 1 kHz sweep events over 20 cm fiber length are demonstrated using a single mode fiber.

  5. Double image encryption based on phase-amplitude mixed encoding and multistage phase encoding in gyrator transform domains

    NASA Astrophysics Data System (ADS)

    Wang, Qu; Guo, Qing; Lei, Liang

    2013-06-01

    We present a novel method for double image encryption that is based on amplitude-phase mixed encoding and multistage random phase encoding in gyrator transform (GT) domains. In the amplitude-phase mixed encoding operation, a random binary distribution matrix is defined to mixed encode two primitive images to a single complex-valued image, which is then encrypted into a stationary white noise distribution by the multistage phase encoding with GTs. Compared with the earlier methods that uses fully phase encoding, the proposed method reduces the difference between two primitive images in key space and sensitivity to the GT orders. The primitive images can be recovered exactly by applying correct keys with initial conditions of chaotic system, the GT orders and the pixel scrambling operation. Numerical simulations demonstrate that the proposed scheme has considerably high security level and certain robustness against data loss and noise disturbance.

  6. Calcium carbonate phase transformations during the carbonation reaction of calcium heavy alkylbenzene sulfonate overbased nanodetergents preparation.

    PubMed

    Chen, Zhaocong; Xiao, Shan; Chen, Feng; Chen, Dongzhong; Fang, Jianglin; Zhao, Min

    2011-07-01

    The preparation and application of overbased nanodetergents with excess alkaline calcium carbonate is a good example of nanotechnology in practice. The phase transformation of calcium carbonate is of extensive concern since CaCO(3) serves both as an important industrial filling material and as the most abundant biomineral in nature. Industrially valuable overbased nanodetergents have been prepared based on calcium salts of heavy alkylbenzene sulfonate by a one-step process under ambient pressure, the carbonation reaction has been monitored by the instantaneous temperature changes and total base number (TBN). A number of analytical techniques such as TGA, DLS, SLS, TEM, FTIR, and XRD have been utilized to explore the carbonation reaction process and phase transformation mechanism of calcium carbonate. An enhanced understanding on the phase transformation of calcium carbonate involved in calcium sulfonate nanodetergents has been achieved and it has been unambiguously demonstrated that amorphous calcium carbonate (ACC) transforms into the vaterite polymorph rather than calcite, which would be of crucial importance for the preparation and quality control of lubricant additives and greases. Our results also show that a certain amount of residual Ca(OH)(2) prevents the phase transformation from ACC to crystalline polymorphs. Moreover, a vaterite nanodetergent has been prepared for the first time with low viscosity, high base number, and uniform particle size, nevertheless a notable improvement on its thermal stability is required for potential applications.

  7. Titanium α -ω phase transformation pathway and a predicted metastable structure

    NASA Astrophysics Data System (ADS)

    Zarkevich, N. A.; Johnson, D. D.

    2016-01-01

    As titanium is a highly utilized metal for structural lightweighting, its phases, transformation pathways (transition states), and structures have scientific and industrial importance. Using a proper solid-state nudged elastic band method employing two climbing images combined with density functional theory DFT + U methods for accurate energetics, we detail the pressure-induced α (ductile) to ω (brittle) transformation at the coexistence pressure. We find two transition states along the minimal-enthalpy path and discover a metastable body-centered orthorhombic structure, with stable phonons, a lower density than the end-point phases, and decreasing stability with increasing pressure.

  8. Titanium α-ω phase transformation pathway and a predicted metastable structure

    DOE PAGESBeta

    Zarkevich, Nickolai A.; Johnson, Duane D.

    2016-01-15

    A titanium is a highly utilized metal for structural lightweighting and its phases, transformation pathways (transition states), and structures have scientific and industrial importance. Using a proper solid-state nudged elastic band method employing two climbing images combined with density functional theory DFT + U methods for accurate energetics, we detail the pressure-induced α (ductile) to ω (brittle) transformation at the coexistence pressure. We also find two transition states along the minimal-enthalpy path and discover a metastable body-centered orthorhombic structure, with stable phonons, a lower density than the end-point phases, and decreasing stability with increasing pressure.

  9. Critical kinetic control of non-stoichiometric intermediate phase transformation for efficient perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Rong, Yaoguang; Venkatesan, Swaminathan; Guo, Rui; Wang, Yanan; Bao, Jiming; Li, Wenzhi; Fan, Zhiyong; Yao, Yan

    2016-06-01

    Organometal trihalide perovskites (OTP) have attracted significant attention as a low-cost and high-efficiency solar cell material. Due to the strong coordination between lead iodide (PbI2) and dimethyl sulfoxide (DMSO) solvent, a non-stoichiometric intermediate phase of MA2Pb3I8(DMSO)2 (MA = CH3NH3+) usually forms in the one-step deposition method that plays a critical role in attaining high power conversion efficiency. However, the kinetic understanding of how the non-stoichiometric intermediate phase transforms during thermal annealing is currently absent. In this work, we investigated such a phase transformation and provided a clear picture of three phase transition pathways as a function of annealing conditions. The interdiffusion of MAI and DMSO varies strongly with the annealing temperature and time, thus determining the final film composition and morphology. A surprising finding reveals that the best performing cells contain ~18% of the non-stoichiometric intermediate phase, instead of pure phase OTP. The presence of such an intermediate phase enables smooth surface morphology and enhances the charge carrier lifetime. Our results highlight the importance of the intermediate phase growth kinetics that could lead to large-scale production of efficient solution processed perovskite solar cells.Organometal trihalide perovskites (OTP) have attracted significant attention as a low-cost and high-efficiency solar cell material. Due to the strong coordination between lead iodide (PbI2) and dimethyl sulfoxide (DMSO) solvent, a non-stoichiometric intermediate phase of MA2Pb3I8(DMSO)2 (MA = CH3NH3+) usually forms in the one-step deposition method that plays a critical role in attaining high power conversion efficiency. However, the kinetic understanding of how the non-stoichiometric intermediate phase transforms during thermal annealing is currently absent. In this work, we investigated such a phase transformation and provided a clear picture of three phase transition

  10. Phase transformation of Ho[subscript 2]O[subscript 3] at high pressure

    SciTech Connect

    Jiang, Sheng; Liu, Jing; Li, Xiaodong; Bai, Ligang; Xiao, Wansheng; Zhang, Yufeng; Lin, Chuanlong; Li, Yanchun; Tang, Lingyun

    2012-01-20

    The structural stability of cubic Ho{sub 2}O{sub 3} under high pressure has been investigated by angle-dispersive x-ray diffraction (ADXD) in a diamond anvil cell up to 63.0 GPa at room temperature. The diffraction data reveal two structural transformations on compression. The structural transformation from a cubic to a monoclinic structure starts at 8.9 GPa and is complete at 16.3 GPa with an {approx}8.1% volume collapse. A hexagonal phase begins to appear at {approx}14.8 GPa and becomes dominant at 26.4 GPa. This high-pressure hexagonal phase with a small amount of retained monoclinic phase is stable up to the highest pressure of 63.0 GPa in this study. After release of pressure, the hexagonal phase transforms to a monoclinic structure. A third-order Birch-Murnaghan fit yields zero pressure bulk moduli (B{sub 0}) of 206(3), 200(7) and 204(19) GPa and their pressure derivatives (B'{sub 0}) of 4.8(4), 2.1(4), 3.8(5) for the cubic, monoclinic and hexagonal phases, respectively. Comparing with other rare-earth sesquioxides, it is suggested that the transition pressure from cubic to monoclinic phase, as well as the bulk modulus of the cubic phase, increases with the decreasing of the cation radius of rare-earth sesquioxides.

  11. Avalanching strain dynamics during the hydriding phase transformation in individual palladium nanoparticles

    SciTech Connect

    Ulvestad, A.; Welland, M. J.; Collins, S. S. E.; Harder, R.; Maxey, E.; Wingert, J.; Singer, A.; Hy, S.; Mulvaney, P.; Zapol, P.; Shpyrko, O. G.

    2015-12-11

    Phase transitions in reactive environments are crucially important in energy and information storage, catalysis and sensors. Nanostructuring active particles can yield faster charging/ discharging kinetics, increased lifespan and record catalytic activities. However, establishing the causal link between structure and function is challenging for nanoparticles, as ensemble measurements convolve intrinsic single-particle properties with sample diversity. Here we study the hydriding phase transformation in individual palladium nanocubes in situ using coherent X-ray diffractive imaging. The phase transformation dynamics, which involve the nucleation and propagation of a hydrogen-rich region, are dependent on absolute time (aging) and involve intermittent dynamics (avalanching). A hydrogen-rich surface layer dominates the crystal strain in the hydrogen-poor phase, while strain inversion occurs at the cube corners in the hydrogen-rich phase. A three-dimensional phase-field model is used to interpret the experimental results. In conclusion, our experimental and theoretical approach provides a general framework for designing and optimizing phase transformations for single nanocrystals in reactive environments.

  12. Avalanching strain dynamics during the hydriding phase transformation in individual palladium nanoparticles

    DOE PAGESBeta

    Ulvestad, A.; Welland, M. J.; Collins, S. S. E.; Harder, R.; Maxey, E.; Wingert, J.; Singer, A.; Hy, S.; Mulvaney, P.; Zapol, P.; et al

    2015-12-11

    Phase transitions in reactive environments are crucially important in energy and information storage, catalysis and sensors. Nanostructuring active particles can yield faster charging/ discharging kinetics, increased lifespan and record catalytic activities. However, establishing the causal link between structure and function is challenging for nanoparticles, as ensemble measurements convolve intrinsic single-particle properties with sample diversity. Here we study the hydriding phase transformation in individual palladium nanocubes in situ using coherent X-ray diffractive imaging. The phase transformation dynamics, which involve the nucleation and propagation of a hydrogen-rich region, are dependent on absolute time (aging) and involve intermittent dynamics (avalanching). A hydrogen-rich surfacemore » layer dominates the crystal strain in the hydrogen-poor phase, while strain inversion occurs at the cube corners in the hydrogen-rich phase. A three-dimensional phase-field model is used to interpret the experimental results. In conclusion, our experimental and theoretical approach provides a general framework for designing and optimizing phase transformations for single nanocrystals in reactive environments.« less

  13. Avalanching strain dynamics during the hydriding phase transformation in individual palladium nanoparticles

    PubMed Central

    Ulvestad, A.; Welland, M. J.; Collins, S. S. E.; Harder, R.; Maxey, E.; Wingert, J.; Singer, A.; Hy, S.; Mulvaney, P.; Zapol, P.; Shpyrko, O. G.

    2015-01-01

    Phase transitions in reactive environments are crucially important in energy and information storage, catalysis and sensors. Nanostructuring active particles can yield faster charging/discharging kinetics, increased lifespan and record catalytic activities. However, establishing the causal link between structure and function is challenging for nanoparticles, as ensemble measurements convolve intrinsic single-particle properties with sample diversity. Here we study the hydriding phase transformation in individual palladium nanocubes in situ using coherent X-ray diffractive imaging. The phase transformation dynamics, which involve the nucleation and propagation of a hydrogen-rich region, are dependent on absolute time (aging) and involve intermittent dynamics (avalanching). A hydrogen-rich surface layer dominates the crystal strain in the hydrogen-poor phase, while strain inversion occurs at the cube corners in the hydrogen-rich phase. A three-dimensional phase-field model is used to interpret the experimental results. Our experimental and theoretical approach provides a general framework for designing and optimizing phase transformations for single nanocrystals in reactive environments. PMID:26655832

  14. White Layer Formation Due to Phase Transformation to Orthogonal machine of AISI 1045 Annealed Steel

    SciTech Connect

    Han, Sangil; Melkote, Shreyes N; Haluska, Dr. Michael S; Watkins, Thomas R

    2008-01-01

    It is commonly believed that the white layer formed during machining of steels is caused primarily by a thermally induced phase transformation resulting from rapid heating and quenching. As a result, it is often assumed that if the temperature at the tool flank-workpiece interface exceeds the nominal phase transformation temperature for the steel, a white layer forms. However, no attempt has been made to actually measure the temperatures produced at the tool flank-workpiece interface and correlate it with microstructural evidence of phase transformation. This paper aims to address these limitations through suitably designed experiments and analysis. Orthogonal machining tests were performed on AISI 1045 annealed steel at different cutting speeds and tool flank wear. During machining, temperature measurements at the tool flank-workpiece interface were made using an exposed thermocouple technique. Metallographic studies of the machined sub-surface and X-ray diffraction (XRD) measurements were performed to determine the presence and depth of white layer, and the presence of the retained austenite phase in the machined surface layer, respectively. Analysis of the data shows that the white layer can form due to phase transformation at temperatures below the nominal austenitization temperature of the steel. Possible causes of this result are presented.

  15. Study of phase transformations in CMSX-6 and CMSX-8 superalloys

    NASA Astrophysics Data System (ADS)

    Szczotok, Agnieszka; Wierzbicka-Miernik, Anna

    2014-09-01

    Nickel-based superalloys are extensively used mainly in the aircraft and aeronautic industry, particularly in the hottest parts of engines or turbo-reactors. The phase reactions occurring in these heat-resistant materials play a crucial role in many aspects of the processing and service of the highly alloyed materials. Cast Ni-based superalloys are obtained in a complex way and their structure is complicated. Differential scanning calorimetry (DSC) technique was applied for determination of temperature ranges of the phase transformations occurring in the CMSX-6 and CMSX-8 superalloys during heating/cooling processes. Thermophysical properties, including temperatures of the phase transformation, are the critical input parameters in mathematical models of solidification and casting of metallic materials. The literature data concerning phase transformations and performance of the heat treatment for CMSX-6 and CMSX-8 are incomplete and ambiguous. DSC results accompanied by scanning electron microscopy characterization of microstructure of CMSX-6 and CMSX-8 superalloy was applied. The present study will improve the understanding of the fundamental mechanisms of phase transformations of single-crystal nickel-based superalloys.

  16. Phase cycling for optical two-dimensional Fourier-transform spectroscopy

    NASA Astrophysics Data System (ADS)

    Autry, Travis; Moody, Galan; Li, Hebin; Siemens, Mark; Cundiff, Steven

    2011-03-01

    Phase-cycling has been implemented in optical two-dimensional Fourier-transform spectroscopy to extract signals from quantum wells and quantum dots and to eliminate noise such as pump scatter co-propagating with the four-wave mixing signal. Experiments using actively phase-stabilized interferometers to cycle the excitation pulse optical phases suffer from partial noise cancellation because excitation and phase-control laser wavelengths are incommensurate. To obtain full noise elimination, we have incorporated liquid crystal variable retarders capable of imposing a π phase shift for wavelengths 650-950 nm. We present non-rephasing spectra of potassium vapor contained in a ~ 20 μ m transmission cell and show that this phase cycling method removes all noise from pump scatter while drastically reducing the data acquisition time compared to mechanical phase-delay techniques. This work was supported by an NSF-REU grant at the University of Colorado- Boulder.

  17. [A phase error correction method for the new Fourier transforms spectrometer].

    PubMed

    Wang, Ning; Gong, Tian-Cheng; Chen, Jian-Jun; Li, Yang; Yang, Yi-Ning; Zhu, Yong; Zhang, Jie; Chen, Wei-Min

    2014-11-01

    To decrease the distortion of the recovered spectrum, improve the quantity of the recovered spectrum and decrease the influence of the phase error of the new spectrum detection system based on MEMS (micro-electro-mechanical systems) micro-mirrors, a new phase error correction method for this system is proposed in the present paper. The source of phase error of the spectrum detection system based on MEMS micro-mirrors is analyzed firstly. The analyzed result indicated that the phase error of the new spectral Fourier transform detection system is the zero drift of the optical path difference, and the phase error can be corrected by Zero-crossing sampling which is realized by improving the structure of the interferometer system and Mertz product The spectrum detection system is set up and the phase error correction method is verified by this system. The experiment result is show that the quantity of the recovered spectrum of the spectrum detection is improved obviously by using the improved interferometer system and Mertz product, and the recovered spectrum has no negative peaks and the side lobes is suppressed markedly. This correction method can reduce the influence caused by phase error to the system performance well and improve the spectral detection performance effectively. In this paper, the origin of the system phase error based on the new MEMS micromirror Fourier transform spectroscopy detection system is analyzed, and the phase error correction method is proposed. This method can improve the performance of the spectrum detection system.

  18. [A phase error correction method for the new Fourier transforms spectrometer].

    PubMed

    Wang, Ning; Gong, Tian-Cheng; Chen, Jian-Jun; Li, Yang; Yang, Yi-Ning; Zhu, Yong; Zhang, Jie; Chen, Wei-Min

    2014-11-01

    To decrease the distortion of the recovered spectrum, improve the quantity of the recovered spectrum and decrease the influence of the phase error of the new spectrum detection system based on MEMS (micro-electro-mechanical systems) micro-mirrors, a new phase error correction method for this system is proposed in the present paper. The source of phase error of the spectrum detection system based on MEMS micro-mirrors is analyzed firstly. The analyzed result indicated that the phase error of the new spectral Fourier transform detection system is the zero drift of the optical path difference, and the phase error can be corrected by Zero-crossing sampling which is realized by improving the structure of the interferometer system and Mertz product The spectrum detection system is set up and the phase error correction method is verified by this system. The experiment result is show that the quantity of the recovered spectrum of the spectrum detection is improved obviously by using the improved interferometer system and Mertz product, and the recovered spectrum has no negative peaks and the side lobes is suppressed markedly. This correction method can reduce the influence caused by phase error to the system performance well and improve the spectral detection performance effectively. In this paper, the origin of the system phase error based on the new MEMS micromirror Fourier transform spectroscopy detection system is analyzed, and the phase error correction method is proposed. This method can improve the performance of the spectrum detection system. PMID:25752034

  19. Experimental and computational investigation of the effect of phase transformation on fracture parameters of an SMA

    NASA Astrophysics Data System (ADS)

    Haghgouyan, Behrouz; Shafaghi, Nima; Aydıner, C. Can; Anlas, Gunay

    2016-07-01

    A comprehensive, multi-method experimental characterization of fracture is conducted on shape memory alloy NiTi that exhibits superelasticity due to austenite-to-martensite stress induced phase transformation. This characterization includes (i) load-based measurement of critical stress intensity factor (K max) using ASTM standard E399, (ii) measurement of crack tip opening displacement (CTOD) per ASTM standard E1290, (iii) the digital image correlation (DIC) characterization of the transformation zone as well as the displacement-field based measurement of K max from the DIC data. Samples have also been tested at T = 100 °C to suppress the martensitic transformation to investigate transformation toughening. The experimental investigation is complemented with finite element (FE) analysis that uses Auricchio-Taylor-Lubliner constitutive model. A direct observation with DIC revealed a small scale transformation (K-dominance). K max of the transforming material is higher than that of the transformation-suppressed material tested at 100 °C, suggesting transformation toughening. At 100 °C, the material becomes quite brittle with a very small crack-tip plastic zone when the transformation mechanism is blocked. By measures of critical CTOD, the gap widens even more between the superelastic and transformation-suppressed cases, particularly because of the side effect that, in this very interesting material, material modulus increases with temperature. Evaluating the transformation zone from the DIC strains with reference to the uniaxial stress-strain curve, an equivalent strain form is proposed in conjunction with the plane stress FE prediction.

  20. Experimental and computational investigation of the effect of phase transformation on fracture parameters of an SMA

    NASA Astrophysics Data System (ADS)

    Haghgouyan, Behrouz; Shafaghi, Nima; Aydıner, C. Can; Anlas, Gunay

    2016-07-01

    A comprehensive, multi-method experimental characterization of fracture is conducted on shape memory alloy NiTi that exhibits superelasticity due to austenite-to-martensite stress induced phase transformation. This characterization includes (i) load-based measurement of critical stress intensity factor (K max) using ASTM standard E399, (ii) measurement of crack tip opening displacement (CTOD) per ASTM standard E1290, (iii) the digital image correlation (DIC) characterization of the transformation zone as well as the displacement-field based measurement of K max from the DIC data. Samples have also been tested at T = 100 °C to suppress the martensitic transformation to investigate transformation toughening. The experimental investigation is complemented with finite element (FE) analysis that uses Auricchio–Taylor–Lubliner constitutive model. A direct observation with DIC revealed a small scale transformation (K-dominance). K max of the transforming material is higher than that of the transformation-suppressed material tested at 100 °C, suggesting transformation toughening. At 100 °C, the material becomes quite brittle with a very small crack-tip plastic zone when the transformation mechanism is blocked. By measures of critical CTOD, the gap widens even more between the superelastic and transformation-suppressed cases, particularly because of the side effect that, in this very interesting material, material modulus increases with temperature. Evaluating the transformation zone from the DIC strains with reference to the uniaxial stress–strain curve, an equivalent strain form is proposed in conjunction with the plane stress FE prediction.

  1. Self-generated overvoltages due to open-phasing of ungrounded-wye delta transformer banks

    SciTech Connect

    Walling, R.A.; Hartana, R.K.; Ros, W.J.

    1994-12-31

    Disconnecting one phase of an ungrounded-wye delta transformer bank from the source can result in severe overvoltages due to neutral shift and ferroresonance. Neutral shift overvoltages are quantified and their impact on metal-oxide surge arresters are evaluated. Ferroresonance is shown by test data to occur when low-loss banks, 15 kV and higher, are open phased. Design and operating practices to eliminate or mitigate these self-generated overvoltages are discussed.

  2. Self-generated overvoltages due to open-phasing of ungrounded-wye delta transformer banks

    SciTech Connect

    Walling, R.A.; Hartana, R.K.; Ros, W.J.

    1995-01-01

    Disconnecting one phase of an ungrounded-wye delta transformer bank from the source can result In severe overvoltages due to neutral shirt and ferroresonance. Neutral shirt overvoltages are quantified and their Impact on metal-oxide surge arresters are evaluated. Ferroresonance is shown by test data to occur when low-loss banks, 15 kV and higher, are open phased. Design and operating practices to eliminate or mitigate these self-generated overvoltages are discussed.

  3. Manipulating mammalian cell by phase transformed titanium surface fabricated through ultra-short pulsed laser synthesis.

    PubMed

    Chinnakkannu Vijayakumar, Sivaprasad; Venkatakrishnan, Krishnan; Tan, Bo

    2016-01-15

    Developing cell sensitive indicators on interacting substrates that allows specific cell manipulation by a combination of physical, chemical or mechanical cues is a challenge for current biomaterials. Hence, various fabrication approaches have been created on a variety of substrates to mimic or create cell specific cues. However, to achieve cell specific cues a multistep process or a post-chemical treatment is often necessitated. So, a simple approach without any chemical or biological treatment would go a long way in developing bio-functionalized substrates to effectively modulate cell adhesion and interaction. The present investigation is aimed to study the manipulative activity induced by phase transformed titanium surface. An ultra-short laser is used to fabricate the phase transformed titanium surface where a polymorphic titanium oxide phases with titanium monoxide (TiO), tri-titanium oxide (Ti3O) and titanium dioxide (TiO2) have been synthesized on commercially pure titanium. Control over oxide phase transformed area was demonstrated via a combination of laser scanning time (laser pulse interaction time) and laser pulse widths (laser pulse to pulse separation time). The interaction of phase transformed titanium surface with NIH3T3 fibroblasts and MC3T3-E1 osteoblast cells developed a new bio-functionalized platforms on titanium based biomaterials to modulate cell migration and adhesion. The synthesized phase transformed titanium surface on the whole appeared to induce directional cues for cell migration with unique preferential cell adhesion unseen by other fabrication approaches. The precise bio-functionalization controllability exhibited during fabrication offers perceptible edge for developing a variety of smart bio-medical devices, implants and cardiovascular stents where the need in supressing specific cell adhesion and proliferation is of great demand.

  4. Manipulating mammalian cell by phase transformed titanium surface fabricated through ultra-short pulsed laser synthesis.

    PubMed

    Chinnakkannu Vijayakumar, Sivaprasad; Venkatakrishnan, Krishnan; Tan, Bo

    2016-01-15

    Developing cell sensitive indicators on interacting substrates that allows specific cell manipulation by a combination of physical, chemical or mechanical cues is a challenge for current biomaterials. Hence, various fabrication approaches have been created on a variety of substrates to mimic or create cell specific cues. However, to achieve cell specific cues a multistep process or a post-chemical treatment is often necessitated. So, a simple approach without any chemical or biological treatment would go a long way in developing bio-functionalized substrates to effectively modulate cell adhesion and interaction. The present investigation is aimed to study the manipulative activity induced by phase transformed titanium surface. An ultra-short laser is used to fabricate the phase transformed titanium surface where a polymorphic titanium oxide phases with titanium monoxide (TiO), tri-titanium oxide (Ti3O) and titanium dioxide (TiO2) have been synthesized on commercially pure titanium. Control over oxide phase transformed area was demonstrated via a combination of laser scanning time (laser pulse interaction time) and laser pulse widths (laser pulse to pulse separation time). The interaction of phase transformed titanium surface with NIH3T3 fibroblasts and MC3T3-E1 osteoblast cells developed a new bio-functionalized platforms on titanium based biomaterials to modulate cell migration and adhesion. The synthesized phase transformed titanium surface on the whole appeared to induce directional cues for cell migration with unique preferential cell adhesion unseen by other fabrication approaches. The precise bio-functionalization controllability exhibited during fabrication offers perceptible edge for developing a variety of smart bio-medical devices, implants and cardiovascular stents where the need in supressing specific cell adhesion and proliferation is of great demand. PMID:26546983

  5. Evaluation of ferrihydrite as amendment to restore an arsenic-polluted mine soil.

    PubMed

    Abad-Valle, P; Álvarez-Ayuso, E; Murciego, A

    2015-05-01

    The effectiveness of ferrihydrite as amendment to restore the soil habitat functioning of a soil polluted with As by mining activities was evaluated. Its influence on As mobility and phytoavailability was also assessed. Soil treated with increasing amendment doses (0, 1, 2, and 5 %) were analyzed for soil microbiological parameters such as basal soil respiration and dehydrogenase, β-glucosidase, urease, acid and alkaline phosphatase, and arylsulfatase activities. Batch leaching tests and plant growth experiments using ryegrass and alfalfa plants were performed. The treatment with ferrihydrite was effective to reduce As mobility and plant As uptake, translocation, and accumulation. Likewise, the soil microbiological status was generally improved as derived from basal soil respiration and dehydrogenase and acid and alkaline phosphatase activities, which showed increases up to 85, 45, 11, and 47 %, respectively, at a ferrihydrite addition rate of 5 %. PMID:25430010

  6. In-Situ Observations of Phase Transformations in the HAZ of 2205 Duplex Stainless Steel Weldments

    SciTech Connect

    Palmer, T A; Elmer, J W; Wong, J

    2001-08-15

    Ferrite ({delta})/austenite ({gamma}) transformations in the heat affected zone (HAZ) of a gas tungsten arc (GTA) weld in 2205 duplex stainless steel are observed in real-time using spatially resolved X-ray diffraction (SRXRD) with high intensity synchrotron radiation. A map showing the locations of the {delta} and {gamma} phases with respect to the calculated weld pool dimensions has been constructed from a series of SRXRD scans. Regions of liquid, completely transformed {gamma}, a combination of partially transformed {gamma} with untransformed {delta}, and untransformed {delta}+{gamma} are identified. Analysis of each SRXRD pattern provides a semi-quantitative definition of both the {delta}/{gamma} phase balance and the extent of annealing which are mapped for the first time with respect to the calculated weld pool size and shape. A combination of these analyses provides a unique real-time description of the progression of phase transformations in the HAZ. Using these real-time observations, important kinetic information about the transformations occurring in duplex stainless steels during heating and cooling cycles typical of welding can be determined.

  7. Nondestructive inspection of phase transformation in zirconia-containing hip joints by confocal Raman spectroscopy.

    PubMed

    Zhu, Wenliang; Sugano, Nobuhiko; Pezzotti, Giuseppe

    2013-12-01

    Environmental metastability of zirconia (ZrO2) ceramic in the human body [represented by a tetragonal-to-monoclinic (t→m) phase transformation] takes place on the surface of the artificial joint and proceeds with time toward its interior. Its quantitative characterization is mandatory for the safety of joint implants and consists of the assessment of the in-depth monoclinic profile fraction as compared to that of the initially untransformed material. We attempt to fully establish a characterization protocol and present two different nondestructive approaches for resolving highly graded phase-transformation profiles along the hip-joint subsurface by confocal Raman microprobe technique. A series of partially transformed tetragonal zirconia polycrystal and zirconia-toughened alumina ceramics are used as screening samples. Probe biases could be eliminated and the real transformation profiles retrieved through a deconvolution procedure of Raman experimental data collected as a function of pinhole aperture and focal depth, respectively. Confirmation of the confocal assessments was made by a destructive cross-sectional inspection by both laser optical microscope and Raman spectral line scans. This study unveils for the first time the real quantitative amount of surface phase-transformation fractions and the related subsurface profiles in zirconia-based retrieved medical samples. PMID:24297000

  8. Nondestructive inspection of phase transformation in zirconia-containing hip joints by confocal Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhu, Wenliang; Sugano, Nobuhiko; Pezzotti, Giuseppe

    2013-12-01

    Environmental metastability of zirconia (ZrO2) ceramic in the human body [represented by a tetragonal-to-monoclinic (t→m) phase transformation] takes place on the surface of the artificial joint and proceeds with time toward its interior. Its quantitative characterization is mandatory for the safety of joint implants and consists of the assessment of the in-depth monoclinic profile fraction as compared to that of the initially untransformed material. We attempt to fully establish a characterization protocol and present two different nondestructive approaches for resolving highly graded phase-transformation profiles along the hip-joint subsurface by confocal Raman microprobe technique. A series of partially transformed tetragonal zirconia polycrystal and zirconia-toughened alumina ceramics are used as screening samples. Probe biases could be eliminated and the real transformation profiles retrieved through a deconvolution procedure of Raman experimental data collected as a function of pinhole aperture and focal depth, respectively. Confirmation of the confocal assessments was made by a destructive cross-sectional inspection by both laser optical microscope and Raman spectral line scans. This study unveils for the first time the real quantitative amount of surface phase-transformation fractions and the related subsurface profiles in zirconia-based retrieved medical samples.

  9. Nondestructive inspection of phase transformation in zirconia-containing hip joints by confocal Raman spectroscopy.

    PubMed

    Zhu, Wenliang; Sugano, Nobuhiko; Pezzotti, Giuseppe

    2013-12-01

    Environmental metastability of zirconia (ZrO2) ceramic in the human body [represented by a tetragonal-to-monoclinic (t→m) phase transformation] takes place on the surface of the artificial joint and proceeds with time toward its interior. Its quantitative characterization is mandatory for the safety of joint implants and consists of the assessment of the in-depth monoclinic profile fraction as compared to that of the initially untransformed material. We attempt to fully establish a characterization protocol and present two different nondestructive approaches for resolving highly graded phase-transformation profiles along the hip-joint subsurface by confocal Raman microprobe technique. A series of partially transformed tetragonal zirconia polycrystal and zirconia-toughened alumina ceramics are used as screening samples. Probe biases could be eliminated and the real transformation profiles retrieved through a deconvolution procedure of Raman experimental data collected as a function of pinhole aperture and focal depth, respectively. Confirmation of the confocal assessments was made by a destructive cross-sectional inspection by both laser optical microscope and Raman spectral line scans. This study unveils for the first time the real quantitative amount of surface phase-transformation fractions and the related subsurface profiles in zirconia-based retrieved medical samples.

  10. Phase transformation as the single-mode mechanical deformation of silicon

    SciTech Connect

    Wong, Sherman; Haberl, Bianca; Williams, James S.; Bradby, Jodie E.

    2015-06-25

    The mixture of the metastable body-centered cubic (bc8) and rhombohedral (r8) phases of silicon that is formed via nanoindentation of diamond cubic (dc) silicon exhibits properties that are of scientifc and technological interest. This letter demonstrates that large regions of this mixed phase can be formed in crystalline Si via nanoindentation without signifcant damage to the surrounding crystal. Cross-sectional transmission electron microscopy is used to show that volumes 6 μm wide and up to 650 nm deep can be generated in this way using a spherical tip of ~21.5 μm diameter. The phase transformed region is characterised using both Raman microspectroscopy and transmission electron microscopy. It is found that uniform loading using large spherical indenters can favor phase transformation as the sole deformation mechanism as long as the maximum load is below a critical level. We suggest that the sluggish nature of the transformation from the dc-Si phase to the metallic (b-Sn) phase normally results in competing deformation mechanisms such as slip and cracking but these can be suppressed by controlled loading conditions.

  11. Phase transformation as the single-mode mechanical deformation of silicon

    DOE PAGESBeta

    Wong, Sherman; Haberl, Bianca; Williams, James S.; Bradby, Jodie E.

    2015-06-25

    The mixture of the metastable body-centered cubic (bc8) and rhombohedral (r8) phases of silicon that is formed via nanoindentation of diamond cubic (dc) silicon exhibits properties that are of scientifc and technological interest. This letter demonstrates that large regions of this mixed phase can be formed in crystalline Si via nanoindentation without signifcant damage to the surrounding crystal. Cross-sectional transmission electron microscopy is used to show that volumes 6 μm wide and up to 650 nm deep can be generated in this way using a spherical tip of ~21.5 μm diameter. The phase transformed region is characterised using both Ramanmore » microspectroscopy and transmission electron microscopy. It is found that uniform loading using large spherical indenters can favor phase transformation as the sole deformation mechanism as long as the maximum load is below a critical level. We suggest that the sluggish nature of the transformation from the dc-Si phase to the metallic (b-Sn) phase normally results in competing deformation mechanisms such as slip and cracking but these can be suppressed by controlled loading conditions.« less

  12. Natural ferrihydrite as an agent for reducing turbidity caused by suspended clays.

    PubMed

    Rhoton, F E; Bigham, J M

    2009-01-01

    Biologically impaired waters are often caused by the turbidity associated with elevated suspended sediment concentrations. Turbidity can be reduced by the addition of positively charged compounds that coagulate negatively charged particles in suspension, causing them to flocculate. This research was conducted to determine the effectiveness of ferrihydrite, a poorly crystalline Fe oxide, as a flocculating agent for suspended clays similar to those found in high-turbidity waters of the Mississippi delta. Clay concentrations of 100 mg L(-1) from a Dubbs silt loam (fine silty, mixed, active, thermic Typic Hapludalfs), a Forestdale silty clay loam (fine, smectitic, thermic Typic Hapludalfs), and a Sharkey clay (very fine, smectitic, thermic Chromic Epiaquerts) were suspended in 0.0005 mol L(-1) CaCl(2) solutions at pH 5, 6, 7, or 8. Natural ferrihydrite with a zero point of charge at pH 5.8 was acquired from a drinking water treatment facility and mixed with the suspension at concentrations of 0, 10, 25, and 50 mg L(-1). After settling periods of 24 and 48 h, percent transmittance was measured at a wavelength of 420 nm using a 3-mL sample collected at a depth of 2 cm. The greatest reductions in turbidity after 24-h equilibration were recorded for the pH 5 suspensions of the Dubbs (31%) and Forestdale (37%) clays at a ferrihydrite concentration of 10 mg L(-1) and for the Sharkey clay at a ferrihydrite concentration of 25 mg L(-1) (relative to the 0 ferrihydrite treatment). Water clarity for all samples further increased after 48 h. These results indicate that the effectiveness of ferrihydrite, as a means of reducing turbidity associated with suspended clays, is greatest at pH values below its zero point of charge. PMID:19643754

  13. Phase Transformations in CuAu: Morphologies and Kinetics from Quantum Mechanics

    NASA Astrophysics Data System (ADS)

    Elder, Ken; Chakraborty, Bulbul; Goldenfeld, Nigel

    1996-03-01

    The existence of a modulated superlattice at intermediate temperatures in CuAu gives rise to a rich and complex set of phase transformations. For example, quenches from high and low temperatures into the modulated region leads respectively to the nucleation of labyrinth and bullseye patterns. In this alloy even the formation of the ordered superlattice from a disordered phase is dramatically different than that which occurs in standard disorder/order transformations. This transformation is strongly influenced by the presence of small metastable droplets that are the size of the modulated wavelength. A theoretical description(Bulbul Chakraborty, Ken Elder and Nigel Goldenfeld, Physica A, in press (1995)) of these kinetics and morphologies will be presented and compared to experiment. This description is based on a time-dependent Ginzburg-Landau equation that was derived from a quantum mechanical Hamiltonian using the embedded atom method(Bulbul Chakraborty and Zhigang Xi, Phys. Rev. Lett 68), 2039 (1992).

  14. Structural and phase transformation of apatite and quartz in the indentation process single crystals

    SciTech Connect

    Chaikina, Marina

    2014-11-14

    Using the method of scanning and high-resolution electron microscopy, the zones of indentation by scratching for apatite and quartz single crystals were investigated. The textural, structural and phase transformations revealed have been conventionally ascribed to “deformation” and “diffusion” processes of plastic deformation. In zones of indentation by scratching of single crystals there have been two levels of structural transformations revealed, with a sharp boundary between them, at a stress equal to the theoretical ultimate stress limit (σ{sub TSL}). In the top zone of scratches, within the range of stress from the microhardness value H{sub s} up to the σ{sub TSL} value the substance undergoes profound structural and phase transformations. In the bed of scratches at the stress value lower than σ{sub TSL} values, single crystal fragmentation occurs with the formation of blocks and steps.

  15. Phase transformations in SrAl2Si2O8 glass

    NASA Technical Reports Server (NTRS)

    Drummond, Charles H., III; Bansal, Narottam P.

    1992-01-01

    Bulk glass of SrAl2Si2O8 composition crystallized at temperatures below 1000 C into hexacelsian, a hexagonal phase which undergoes a reversible, rapid transformation to an orthorhombic phase at 758 C, and at higher temperatures crystallized as celsian, a monoclinic phase. The glass transition temperature and crystallization onset temperature were determined to be 883 C and 1086 C, respectively, from DSC at a heating rate of 20 C/min. Thermal expansion of the various phases and density and bend strengths of cold isostatically pressed glass powder bars, sintered at various temperatures, were measured. The kinetics of the hexacelsian-to-celsian transformation for SrAl2Si2O8 were studied. Hexacelsian flakes were isothermally heat treated at temperatures from 1025-1200 C for various times. Avrami plots were determined by quantitatively measuring the amount of monoclinic celsian formed at various times using x ray diffraction. The Avrami constant was determined to be 1.1, suggesting a diffusionless, one dimensional transformation mechanism. The activation energy was determined from an Arrhenius plot of 1n k vs. 1/T to be 125 kilocal/mole. This value is consistent with a mechanism which transforms the layered hexacelsian structure to a three dimensional framework celsian structure and involves the breaking of Si-O bonds.

  16. On the thermodynamic criterion for detonability of a phase-transforming substance

    NASA Astrophysics Data System (ADS)

    Fowles, G. Richard

    1990-05-01

    The thermodynamic criterion for detonability of a phase-transforming substance derived by Kuznetsov [Sov. Phys. JETP 22, 1047 (1966)] is shown to be an approximation to the more general criterion for detonability, namely, (∂P/∂λ)E,V>0, where E is internal energy, V is volume, and λ is the reaction coordinate measured positive as the reaction proceeds toward equilibrium.

  17. HIGH CRYSTALLINITY SI-FERRIHYDRITE: AN INSIGHT INTO ITS NÉEL TEMPERATURE AND SIZE DEPENDENCE OF MAGNETIC PROPERTIES

    EPA Science Inventory

    Ferrihydrite, an antiferromagnetic iron oxyhydroxide, is of great importance for the cycling of many trace metals in the environment. Four ferrihydrite samples prepared with 1.3 to 3.5 wt% of Si at different synthesis temperatures (7.5 °C, 22 °C, 50 °C and 75 °C) were studied by ...

  18. A new phase transformation path from nanodiamond to new-diamond via an intermediate carbon onion

    NASA Astrophysics Data System (ADS)

    Xiao, J.; Li, J. L.; Liu, P.; Yang, G. W.

    2014-11-01

    The investigation of carbon allotropes such as graphite, diamond, fullerenes, nanotubes and carbon onions and mechanisms that underlie their mutual phase transformation is a long-standing problem of great fundamental importance. New diamond (n-diamond) is a novel metastable phase of carbon with a face-centered cubic structure; it is called ``new diamond'' because many reflections in its electron diffraction pattern are similar to those of diamond. However, producing n-diamond from raw carbon materials has so far been challenging due to n-diamond's higher formation energy than that of diamond. Here, we, for the first time, demonstrate a new phase transformation path from nanodiamond to n-diamond via an intermediate carbon onion in the unique process of laser ablation in water, and establish that water plays a crucial role in the formation of n-diamond. When a laser irradiates colloidal suspensions of nanodiamonds at ambient pressure and room temperature, nanodiamonds are first transformed into carbon onions serving as an intermediate phase, and sequentially carbon onions are transformed into n-diamonds driven by the laser-induced high temperature and high pressure from the carbon onion as a nanoscaled temperature and pressure cell upon the process of laser irradiation in a liquid. This phase transformation not only provides new insight into the physical mechanism involved, but also offers one suitable opportunity for breaking controllable pathways between n-diamond and carbon allotropes such as diamond and carbon onions.The investigation of carbon allotropes such as graphite, diamond, fullerenes, nanotubes and carbon onions and mechanisms that underlie their mutual phase transformation is a long-standing problem of great fundamental importance. New diamond (n-diamond) is a novel metastable phase of carbon with a face-centered cubic structure; it is called ``new diamond'' because many reflections in its electron diffraction pattern are similar to those of diamond

  19. Kinetic study of phase transformation of n-octane using hydrothermal diamond anvil cell

    NASA Astrophysics Data System (ADS)

    Liu, Chuanjiang; Zheng, Haifei; Wang, Duojun

    2016-02-01

    A kinetic study of phase transformation of n-octane has been performed using a hydrothermal diamond anvil cell. The results show that pressure has a negative effect on the solid-liquid reaction rate. The increase of pressure can accelerate the liquid-solid transformation rate. Upon the liquid-solid transformation, the light transmittance showed a decreased trend with time in the early stage, which was caused by the formation of a large quantity of crystal nuclei. In the later stage, the light transmittance almost remained the same, thus indicating a growth stage of crystal nuclei. The activation volume yields a value of 2.16×10-5 and -1.35×10-5 m3/mol for the solid-liquid and liquid-solid transformations. Based on the obtained activation energy, the solid-liquid transformation is dominated by the interfacial reaction and diffusion, and the liquid-solid transformation is controlled by diffusion. This technique is an effective and powerful tool for the transformation kinetics study of n-octane.

  20. Enhanced reversibility and unusual microstructure of a phase-transforming material.

    PubMed

    Song, Yintao; Chen, Xian; Dabade, Vivekanand; Shield, Thomas W; James, Richard D

    2013-10-01

    Materials undergoing reversible solid-to-solid martensitic phase transformations are desirable for applications in medical sensors and actuators, eco-friendly refrigerators and energy conversion devices. The ability to pass back and forth through the phase transformation many times without degradation of properties (termed 'reversibility') is critical for these applications. Materials tuned to satisfy a certain geometric compatibility condition have been shown to exhibit high reversibility, measured by low hysteresis and small migration of transformation temperature under cycling. Recently, stronger compatibility conditions called the 'cofactor conditions' have been proposed theoretically to achieve even better reversibility. Here we report the enhanced reversibility and unusual microstructure of the first martensitic material, Zn45Au30Cu25, that closely satisfies the cofactor conditions. We observe four striking properties of this material. (1) Despite a transformation strain of 8%, the transformation temperature shifts less than 0.5 °C after more than 16,000 thermal cycles. For comparison, the transformation temperature of the ubiquitous NiTi alloy shifts up to 20 °C in the first 20 cycles. (2) The hysteresis remains approximately 2 °C during this cycling. For comparison, the hysteresis of the NiTi alloy is up to 70 °C (refs 9, 12). (3) The alloy exhibits an unusual riverine microstructure of martensite not seen in other martensites. (4) Unlike that of typical polycrystal martensites, its microstructure changes drastically in consecutive transformation cycles, whereas macroscopic properties such as transformation temperature and latent heat are nearly reproducible. These results promise a concrete strategy for seeking ultra-reliable martensitic materials.

  1. Application of the theory of martensite crystallography to displacive phase transformations in substitutional nonferrous alloys

    NASA Astrophysics Data System (ADS)

    Muddle, B. C.; Nie, J. F.; Hugo, G. R.

    1994-09-01

    It has been demonstrated that the theory of martensite crystallography is capable of accounting successfully for the form and crystallography of a range of plate- or lath-shaped transformation products, even when the formation of the product phase involves significant substitutional diffusion. These transformations include the precipitation of metastable hexagonal γ’ (Ag2Al) plates in disordered face-centered cubic (fcc) solid-solution Al-Ag alloys, the formation of ordered AuCu II plates from disordered fcc solid solution in equiatomic Au-Cu alloys, and the formation of metastable 9R α 1, plates in ordered (B2) Cu-Zn and Ag-Cd alloys. The application of the theory to these transformations is reviewed critically and the features common to them identified. It is confirmed that, in all three transformations, the product phase produces relief at a free surface consistent with an invariant plane-strain shape change and that the transformations are thus properly described as displacive. The agreement between experimental observations and theoretical predictions of the transformation crystallography is in all cases excellent. It is proposed that successful application of the theory implies a growth mechanism in which the coherent or semicoherent, planar interface between parent and product phases maintains its structural identity during migration and that growth proceeds atom by atom in a manner consistent with the maintenance of a correspondence of lattice sites. In the case of the coherent, planar interfaces associated with γ’ precipitate plates in Al-Ag alloys, there is direct experimental evidence that this is accomplished by the motion of transformation dislocations across the coherent broad faces of the precipitate plates; the transformation dislocations define steps that are two atom layers in height normal to the habit plane and have a Burgers vector at least approximately equivalent to an (α/6)(112) Shockley partial dislocation in the parent fcc

  2. Note: An improved calibration system with phase correction for electronic transformers with digital output

    SciTech Connect

    Cheng, Han-miao Li, Hong-bin

    2015-08-15

    The existing electronic transformer calibration systems employing data acquisition cards cannot satisfy some practical applications, because the calibration systems have phase measurement errors when they work in the mode of receiving external synchronization signals. This paper proposes an improved calibration system scheme with phase correction to improve the phase measurement accuracy. We employ NI PCI-4474 to design a calibration system, and the system has the potential to receive external synchronization signals and reach extremely high accuracy classes. Accuracy verification has been carried out in the China Electric Power Research Institute, and results demonstrate that the system surpasses the accuracy class 0.05. Furthermore, this system has been used to test the harmonics measurement accuracy of all-fiber optical current transformers. In the same process, we have used an existing calibration system, and a comparison of the test results is presented. The system after improvement is suitable for the intended applications.

  3. Isothermal Martensitic and Pressure-Induced ? to ?? Phase Transformations in a Pu-Ga Alloy

    SciTech Connect

    Schwartz, A J; Wall, M A; Farber, D L; Moore, K T; Blobaum, K M

    2007-09-10

    A Pu-2 at.% Ga alloy specimen is slowly compressed to {approx}1 GPa in a large volume moissanite anvil cell to induce the face-centered cubic {delta} to simple monoclinic {alpha}{prime} phase transformation. Optical microscopy, x-ray diffraction, and transmission electron microscopy of the specimen recovered to ambient pressure reveal that the vast majority of the microstructure consists of the {alpha}{prime} phase with grain sizes ranging from 10 nm to several hundred nm, with the remainder being {delta} phase dispersed between the {alpha}{prime} grains. This morphology is in contrast to the transformation product of the low-temperature isothermal martensite in which the lath-shaped {alpha}{prime} particles are {approx}20 {micro}m by 2 {micro}m.

  4. ISOTHERMAL PHASE TRANSFORMATION CYCLING IN STEEL BY APPLICATION OF A HIGH MAGNETIC FIELD

    SciTech Connect

    Ludtka, Gerard Michael; Jaramillo, Roger A; Ludtka, Gail Mackiewicz-; Kisner, Roger A; Wilgen, John B

    2007-01-01

    A phase transformation reversal via the application and removal of a large magnetic field was investigated. Because a large magnetic field can alter the phase equilibrium between paramagnetic austenite and ferromagnetic ferrite, volume fractions for each phase constituent can be modified at constant temperature by changing the magnetic field strength. In this research elevated temperature isothermal hold experiments were performed for 5160 steel. During the isothermal hold, the magnetic field was cycled between 0 and 30 Tesla. As companion experiments, temperature cycling and isothermal holds were performed without magnetic fields. The resulting microstructures were examined using optical and SEM metallography. These microstructures indicate that a portion of the microstructure experiences isothermal transformation cycling between austenite and ferrite due to the application and removal of the 30T (Tesla) magnetic field.

  5. High pressure phase transformations in α-AlPO4: an x-ray diffraction investigation

    NASA Astrophysics Data System (ADS)

    Sharma, Surinder M.; Garg, Nandini; Sikka, S. K.

    2000-07-01

    We have re-investigated the high pressure behaviour of berlinite AlPO4 (α-AlPO4) with x-ray diffraction using a powerful synchrotron x-ray source SPring-8. Our results show that it transforms to a crystalline phase beyond ~13 GPa. Our data seem to be consistent with a CrVO4 type of structure in the Cmcm space group, similar to the high pressure phase observed in some isostructural phosphate compounds. The persistence of the diffraction pattern up to 40 GPa establishes that the previously accepted amorphization of AlPO4 around 12-18 GPa is incorrect. Experimental results suggest that the so-called memory glass effect observed earlier may in fact be the reversibility of the α-phase←⇔crystalline phase transformation. Comparisons of our experimental and theoretical results raise serious doubts about the theoretical understanding of the high pressure behaviour of α-AlPO4.

  6. Status on Iterative Transform Phase Retrieval Applied to the GBT Data

    NASA Technical Reports Server (NTRS)

    Dean, Bruce; Aronstein, David; Smith, Scott; Shiri, Ron; Hollis, Jan M.; Lyons, Richard; Prestage, Richard; Hunter, Todd; Ghigo, Frank; Nikolic, Bojan

    2007-01-01

    This slide presentation reviews the use of iterative transform phase retrieval in the analysis of the Green Bank Radio Telescope (GBT) Data. It reviews the NASA projects that have used phase retrieval, and the testbed for the algorithm to be used for the James Webb Space Telescope. It shows the comparison of phase retrieval with an interferometer, and reviews the two approaches used for phase retrieval, iterative transform (ITA) or parametric (non-linear least squares model fitting). The concept of ITA Phase Retrieval is reviewed, and the application to Radio Antennas is reviewed. The presentation also examines the National Radio Astronomy Observatory (NRAO) data from the GBT, and the Fourier model that NRAO uses to analyze the data. The challenge for ITA phase retrieval is reviewed, and the coherent approximation for incoherent data is shown. The validity of the approximation is good for a large tilt. There is a review of the proof of concept of the Phase Review simulation using the input wavefront, and the initial sampling parameters estimate from the focused GBT data.

  7. Probing the Dynamics of the Metallic-to-Semiconducting Structural Phase Transformation in MoS2 Crystals.

    PubMed

    Guo, Yinsheng; Sun, Dezheng; Ouyang, Bin; Raja, Archana; Song, Jun; Heinz, Tony F; Brus, Louis E

    2015-08-12

    We have investigated the phase transformation of bulk MoS2 crystals from the metastable metallic 1T/1T' phase to the thermodynamically stable semiconducting 2H phase. The metastable 1T/1T' material was prepared by Li intercalation and deintercalation. The thermally driven kinetics of the phase transformation were studied with in situ Raman and optical reflection spectroscopies and yield an activation energy of 400 ± 60 meV (38 ± 6 kJ/mol). We calculate the expected minimum energy pathways for these transformations using DFT methods. The experimental activation energy corresponds approximately to the theoretical barrier for a single formula unit, suggesting that nucleation of the phase transformation is quite local. We also report that femtosecond laser writing converts 1T/1T' to 2H in a single laser pass. The mechanisms for the phase transformation are discussed.

  8. Phase coexistence and transformations in field-cooled ternary piezoelectric single crystals near the morphotropic phase boundary

    SciTech Connect

    Luo, Chengtao; Wang, Yaojin Wang, Zhiguang; Ge, Wenwei; Li, Jiefang; Viehland, D.; Luo, Haosu

    2014-12-08

    Structural phase transformations in (100)-oriented Pb(In{sub 1/2}Nb{sub 1/2})O{sub 3}-Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}-PbTiO{sub 3} single crystals have been investigated by X-ray diffraction. A cubic (C) → tetragonal (T) → monoclinic-C (M{sub C}) transformation sequence was observed in the field-cooled condition. Two phase coexistence regions of C + T and T + M{sub C} were found. In addition to an increase in the C → T phase transition temperature and a decrease of the T → M{sub C} one, a broadening of the coexistence regions was also found with increasing field. This broadening can be explained by the presence of polar nano regions within the C, T, and M{sub C} phase regions.

  9. Phase transformation of iron-based catalysts for Fischer-Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Jin, Yaming

    Fischer-Tropsch (F-T) synthesis is used to convert syngas to liquid hydrocarbons using iron-based catalysts. However, the nature of the active phase and phase transformations during F-T synthesis are not well understood. In this work, the phase transformations of Fe catalysts both during F-T synthesis and controlled treatment conditions have been studied using cross-section transmission electron microscopy, x-ray diffraction and Mossbauer spectroscopy. Catalyst samples were obtained from F-T synthesis runs at medium pressure (1.48 MPa) with a H2:CO ratio of 0.7. Samples were analyzed without removal of the wax to preserve the catalyst microstructure intact and prevent oxidation due to air exposure. In all active Fe catalysts, a highly dispersed chi-carbide (Fe5C2) phase with an average particle size <10 nm was seen to be present along with larger sized particles of hexagonal Fe 7C3. On the other hand, the carbide phase whose XRD pattern resembles that obtained by the Barton and Gale was found to be associated with catalysts of low activity. All carbide particles are covered with amorphous carbonaceous layers as seen by electron energy loss spectroscopy (EELS). In a series of separate experiments, phase transformations that occur during catalyst activation at atmospheric pressure were studied. During direct CO carburization of iron oxide at 250°C, multiple nucleation sites lead to formation of smaller Fe carbide particles predominantly of the Barton-Gale carbide. However, starting from metallic Fe we obtain a chi-carbide phase without significant change in particle size. Treatment in syngas (H 2:CO = 0.7) results in less complete carburization and larger particle sizes for both the carbide and the magnetite phases. The presence of trace amounts of water vapor during reduction appears to cause formation of large faceted magnetite crystals, which are difficult to further transform to the active carbide phase. The silica support is effective at keeping the Fe phases

  10. Metastable mantle phase transformations and deep earthquakes in subducting oceanic lithosphere

    NASA Astrophysics Data System (ADS)

    Kirby, Stephen H.; Stein, Seth; Okal, Emile A.; Rubie, David C.

    1996-05-01

    Earth's deepest earthquakes occur as a population in subducting or previously subducted lithosphere at depths ranging from about 325 to 690 km. This depth interval closely brackets the mantle transition zone, characterized by rapid seismic velocity increases resulting from the transformation of upper mantle minerals to higher-pressure phases. Deep earthquakes thus provide the primary direct evidence for subduction of the lithosphere to these depths and allow us to investigate the deep thermal, thermodynamic, and mechanical ferment inside slabs. Numerical simulations of reaction rates show that the olivine → spinel transformation should be kinetically hindered in old, cold slabs descending into the transition zone. Thus wedge-shaped zones of metastable peridotite probably persist to depths of more than 600 km. Laboratory deformation experiments on some metastable minerals display a shear instability called transformational faulting. This instability involves sudden failure by localized superplasticity in thin shear zones where the metastable host mineral transforms to a denser, finer-grained phase. Hence in cold slabs, such faulting is expected for the polymorphic reactions in which olivine transforms to the spinel structure and clinoenstatite transforms to ilmenite. It is thus natural to hypothesize that deep earthquakes result from transformational faulting in metastable peridotite wedges within cold slabs. This consideration of the mineralogical states of slabs augments the traditional largely thermal view of slab processes and explains some previously enigmatic slab features. It explains why deep seismicity occurs only in the approximate depth range of the mantle transition zone, where minerals in downgoing slabs should transform to spinel and ilmenite structures. The onset of deep shocks at about 325 km is consistent with the onset of metastability near the equilibrium phase boundary in the slab. Even if a slab penetrates into the lower mantle, earthquakes

  11. THERMODYNAMICS AND KINETICS OF PHASE TRANSFORMATIONS IN PLUTONIUM ALLOYS - PART I

    SciTech Connect

    Turchi, P A; Kaufman, L; Liu, Z; Zhou, S

    2004-08-18

    In this report we investigate order, stability, and phase transformations for a series of actinide-based alloys. The statics and kinetics of precipitation and ordering in this class of alloys are modeled with a scheme that couples fundamental information on the alloy energetics obtained from experimental and assessed thermo-chemical data to the CALPHAD approach commonly used in industry for designing alloys with engineering specificity with the help of the Thermo-Calc software application. The CALPHAD approach is applied to the study of the equilibrium thermodynamic properties of Pu-based alloys, Pu-X, where X=Al, Fe, Ga. The assessment of the equilibrium phase diagrams in the whole range of alloy composition has been performed with the PARROT module of the Thermo-Calc application software. Predictions are made on the low temperature and Pu-rich side of the phase diagrams of Pu-Ga and Pu-Al for which controversy has been noted in the past. The validity of the assessed thermo-chemical database will be discussed by comparing predicted heats of transformation for pure Pu with measured values from differential scanning calorimetry analysis. An overall picture for the stability properties of Pu-Ga and Pu-Al that reconciles the results of past studies carried out on these alloys is proposed. Results on phase stability in the ternary Fe-Ga-Pu and Al-Fe-Pu alloys are discussed. The information collected in this study is then used to model metastability, long-term stability and aging for this class of alloys by coupling Thermo-Calc with DICTRA, a series of modules that allow the analysis of DIffusion Controlled TRAnsformations. Kinetics information is then summarized in so-called TTT (temperature-time-transformations) diagrams for the most relevant phases of actinide alloys. Specifically, results are presented on kinetics of phase transformations associated with the eutectoid-phase decomposition reaction occurring at low temperature, and with the martensitic transformation

  12. Influence of processing-induced phase transformations on the dissolution of theophylline tablets.

    PubMed

    Debnath, Smita; Suryanarayanan, Raj

    2004-02-12

    The object of this investigation was to evaluate the influence of (1) processing-induced decrease in drug crystallinity and (2) phase transformations during dissolution, on the performance of theophylline tablet formulations. Anhydrous theophylline underwent multiple transformations (anhydrate --> hydrate --> anhydrate) during processing. Although the crystallinity of the anhydrate obtained finally was lower than that of the unprocessed drug, it dissolved at a slower rate. This decrease in dissolution rate was attributed to the accelerated anhydrate to hydrate transformation during the dissolution run. Water vapor sorption studies proved to be a good predictor of powder dissolution behavior. While a decrease in crystallinity was brought about either by milling or by granulation, the effect on tablet dissolution was pronounced only in the latter. Tablet formulations prepared from the granules exhibited higher hardness, longer disintegration time, and slower dissolution than those containing the milled drug. The granules underwent plastic deformation during compression resulting in harder tablets, with delayed disintegration. The high hardness coupled with rapid anhydrate --> hydrate transformation during dissolution resulted in the formation of a hydrate layer on the tablet surface, which further delayed tablet disintegration and, consequently, dissolution. Phase transformations during processing and, more importantly, during dissolution influenced the observed dissolution rates. Product performance was a complex function of the physical state of the active and the processing conditions. PMID:15198529

  13. Kinetics study on phase transformation from titania polymorph brookite to rutile

    NASA Astrophysics Data System (ADS)

    Huberty, Jason; Xu, Huifang

    2008-03-01

    TiO 2 is a polymorphic material of great scientific interest due to its semiconductor properties and uses in heterogeneous photocatalysis. Understanding the stability of the polymorphs is important for designing TiO 2-based photocatalysts and solar cells. Although the phase transformation of anatase→rutile has been well studied, there is only one published work on brookite→rutile to date. The brookite→rutile transformation has been studied in this work using natural material from the Magnet Cove igneous complex mechanically processed to several micrometers in size. The pure phase brookite is annealed from 800 to 900 °C without detection of the anatase polymorph. The transformation kinetics are described by both the standard first-order model, with an activation energy of Ea=411.91 kJ/mol, and the Johnson-Mehl-Avrami-Kolmogorov (JMAK) model, with an activation energy of Ea=492.13 kJ/mol. The rate parameter of the first-order model for the phase transformation is expressed as k=6.85×10 14 exp(-49,451/ T) s -1 for the first-order model and k=4.19×10 18 exp(-59,189/ T) s -1 using the JMAK model. The obtained activation energy is higher than that of brookite nano-crystals. Our results show that the JMAK model fits the kinetics data better than other models.

  14. Unconventional transformation of spin Dirac phase across a topological quantum phase transition

    SciTech Connect

    Xu, Su -Yang; Neupane, Madhab; Belopolski, Ilya; Liu, Chang; Alidoust, Nasser; Bian, Guang; Jia, Shuang; Landolt, Gabriel; Slomski, Batosz; Dil, J. Hugo; Shibayev, Pavel P.; Basak, Susmita; Chang, Tay -Rong; Jeng, Horng -Tay; Cava, Robert J.; Lin, Hsin; Bansil, Arun; Hasan, M. Zahid

    2015-04-17

    The topology of a topological material can be encoded in its surface states. These surface states can only be removed by a bulk topological quantum phase transition into a trivial phase. Here we use photoemission spectroscopy to image the formation of protected surface states in a topological insulator as we chemically tune the system through a topological transition. Surprisingly, we discover an exotic spin-momentum locked, gapped surface state in the trivial phase that shares many important properties with the actual topological surface state in anticipation of the change of topology. Using a spin-resolved measurement, we show that apart from a surface bandgap these states develop spin textures similar to the topological surface states well before the transition. Our results provide a general paradigm for understanding how surface states in topological phases arise from a quantum phase transition and are suggestive for the future realization of Weyl arcs, condensed matter supersymmetry and other fascinating phenomena in the vicinity of a quantum criticality.

  15. Unconventional transformation of spin Dirac phase across a topological quantum phase transition

    DOE PAGESBeta

    Xu, Su -Yang; Neupane, Madhab; Belopolski, Ilya; Liu, Chang; Alidoust, Nasser; Bian, Guang; Jia, Shuang; Landolt, Gabriel; Slomski, Batosz; Dil, J. Hugo; et al

    2015-04-17

    The topology of a topological material can be encoded in its surface states. These surface states can only be removed by a bulk topological quantum phase transition into a trivial phase. Here we use photoemission spectroscopy to image the formation of protected surface states in a topological insulator as we chemically tune the system through a topological transition. Surprisingly, we discover an exotic spin-momentum locked, gapped surface state in the trivial phase that shares many important properties with the actual topological surface state in anticipation of the change of topology. Using a spin-resolved measurement, we show that apart from amore » surface bandgap these states develop spin textures similar to the topological surface states well before the transition. Our results provide a general paradigm for understanding how surface states in topological phases arise from a quantum phase transition and are suggestive for the future realization of Weyl arcs, condensed matter supersymmetry and other fascinating phenomena in the vicinity of a quantum criticality.« less

  16. Unconventional transformation of spin Dirac phase across a topological quantum phase transition

    NASA Astrophysics Data System (ADS)

    Xu, Su-Yang; Neupane, Madhab; Belopolski, Ilya; Liu, Chang; Alidoust, Nasser; Bian, Guang; Jia, Shuang; Landolt, Gabriel; Slomski, Batosz; Dil, J. Hugo; Shibayev, Pavel P.; Basak, Susmita; Chang, Tay-Rong; Jeng, Horng-Tay; Cava, Robert J.; Lin, Hsin; Bansil, Arun; Hasan, M. Zahid

    2015-04-01

    The topology of a topological material can be encoded in its surface states. These surface states can only be removed by a bulk topological quantum phase transition into a trivial phase. Here we use photoemission spectroscopy to image the formation of protected surface states in a topological insulator as we chemically tune the system through a topological transition. Surprisingly, we discover an exotic spin-momentum locked, gapped surface state in the trivial phase that shares many important properties with the actual topological surface state in anticipation of the change of topology. Using a spin-resolved measurement, we show that apart from a surface bandgap these states develop spin textures similar to the topological surface states well before the transition. Our results offer a general paradigm for understanding how surface states in topological phases arise from a quantum phase transition and are suggestive for the future realization of Weyl arcs, condensed matter supersymmetry and other fascinating phenomena in the vicinity of a quantum criticality.

  17. Unconventional transformation of spin Dirac phase across a topological quantum phase transition.

    PubMed

    Xu, Su-Yang; Neupane, Madhab; Belopolski, Ilya; Liu, Chang; Alidoust, Nasser; Bian, Guang; Jia, Shuang; Landolt, Gabriel; Slomski, Batosz; Dil, J Hugo; Shibayev, Pavel P; Basak, Susmita; Chang, Tay-Rong; Jeng, Horng-Tay; Cava, Robert J; Lin, Hsin; Bansil, Arun; Hasan, M Zahid

    2015-04-17

    The topology of a topological material can be encoded in its surface states. These surface states can only be removed by a bulk topological quantum phase transition into a trivial phase. Here we use photoemission spectroscopy to image the formation of protected surface states in a topological insulator as we chemically tune the system through a topological transition. Surprisingly, we discover an exotic spin-momentum locked, gapped surface state in the trivial phase that shares many important properties with the actual topological surface state in anticipation of the change of topology. Using a spin-resolved measurement, we show that apart from a surface bandgap these states develop spin textures similar to the topological surface states well before the transition. Our results offer a general paradigm for understanding how surface states in topological phases arise from a quantum phase transition and are suggestive for the future realization of Weyl arcs, condensed matter supersymmetry and other fascinating phenomena in the vicinity of a quantum criticality.

  18. Phase transformations in multiferroics Bi1- x Ca x Fe1- x Mn x O3

    NASA Astrophysics Data System (ADS)

    Troyanchuk, I. O.; Bushinsky, M. V.; Karpinsky, D. V.; Chobot, A. N.; Tereshko, N. V.; Franz, A.

    2016-09-01

    The crystal structure and the magnetic properties of multiferroics Bi1- x Ca x Fe1- x Mn x O3 ( x ≤ 0.22) have been studied. It has been found that the stoichiometric compositions undergo a crystal-structure transformation from the rhombohedral (space group R3 c) polar phase ( x ≤ 0.18) to the orthorhombic (space group Pnma) nonpolar phase ( x ≥ 0.20) via a two-phase structural state. The polar phase is antiferromagnetic at x < 0.10 and exhibits a metamagnetic behavior. The polar ( x ≥ 0.10) and nonpolar phases are weak ferromagnets at room temperature with a spontaneous magnetization close to 0.07 emu/g ( x = 0.18 and 0.22). A decrease in temperature leads to the transition to a state close to an antiferromagnetic one.

  19. TRANSFORMATION

    SciTech Connect

    LACKS,S.A.

    2003-10-09

    Transformation, which alters the genetic makeup of an individual, is a concept that intrigues the human imagination. In Streptococcus pneumoniae such transformation was first demonstrated. Perhaps our fascination with genetics derived from our ancestors observing their own progeny, with its retention and assortment of parental traits, but such interest must have been accelerated after the dawn of agriculture. It was in pea plants that Gregor Mendel in the late 1800s examined inherited traits and found them to be determined by physical elements, or genes, passed from parents to progeny. In our day, the material basis of these genetic determinants was revealed to be DNA by the lowly bacteria, in particular, the pneumococcus. For this species, transformation by free DNA is a sexual process that enables cells to sport new combinations of genes and traits. Genetic transformation of the type found in S. pneumoniae occurs naturally in many species of bacteria (70), but, initially only a few other transformable species were found, namely, Haemophilus influenzae, Neisseria meningitides, Neisseria gonorrheae, and Bacillus subtilis (96). Natural transformation, which requires a set of genes evolved for the purpose, contrasts with artificial transformation, which is accomplished by shocking cells either electrically, as in electroporation, or by ionic and temperature shifts. Although such artificial treatments can introduce very small amounts of DNA into virtually any type of cell, the amounts introduced by natural transformation are a million-fold greater, and S. pneumoniae can take up as much as 10% of its cellular DNA content (40).

  20. A novel solvethermal method for the preparation of magnetic monodisperse Fe{sub 3}O{sub 4} nanoparticles II: High-surface-activity ferrihydrite used as precursor

    SciTech Connect

    Zhao, Sha; Yang, Caiqin; Yan, Jiawen; Wang, Jing

    2013-10-15

    Graphical abstract: The magnetic monodisperse Fe{sub 3}O{sub 4} nanoparticles (NPs) were prepared by novel solvethemal method at moderate temperature using high surface active ferrihydrit and iron powder as precursors in orgnic solvent. - Highlights: • Facile synthesis of organic ligands-coated monodisperse Fe{sub 3}O{sub 4} nanoparticles at low temperature. • Low-cost high surface active ferrihydrit and reductive iron powder were used as precursors. • N{sub 2}-free reaction environment. • Organic ligands act as reductive. - Abstract: Magnetic monodisperse Fe{sub 3}O{sub 4} nanoparticles (NPs) were prepared from ferrihydrite and iron powder by a novel solvethermal method at moderate temperatures in aqueous and organic solvent media. The effects of temperature and solvent medium on the phase and particle size of Fe{sub 3}O{sub 4} NPs were investigated. The products were characterized by X-ray powder diffraction, infrared spectroscopy, differential scanning calorimetry–thermogravimetric analysis, transmission electron microscopy, and vibrating sample magnetometry. At 120 °C in the organic medium, uniform organic-ligand-coated superparamagnetic Fe{sub 3}O{sub 4} NPs were produced; the particle size increased with the temperature, and the calculated mean particle size was 8.9 nm. At 180 °C in the aqueous medium, pure-phase Fe{sub 3}O{sub 4} was obtained. Thus, the organic solvent did not only serve as a solvent but also participated in the reaction. Fe{sub 3}O{sub 4} production in the aqueous and organic solvent media had different mechanisms.

  1. 77 FR 16559 - Large Power Transformers From Korea: Scheduling of the Final Phase of an Antidumping Investigation

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-03-21

    ... COMMISSION Large Power Transformers From Korea: Scheduling of the Final Phase of an Antidumping Investigation... imports from Korea of large power transformers, provided for in subheading 8504.23.00 of the Harmonized... Commerce has defined the subject merchandise as ``large liquid dielectric power transformers (LPTs)...

  2. Comments on 'Kinetic Study on the Hexacelsian-Celsian Phase Transformation'

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Drummond, Charles H., III

    1992-01-01

    A value of 20.1 +/- 4 kcal/mole for the activation energy (E) for the hexacelsian to celsian phase transformation in BaAl2Si2O8 was reported in an earlier work. In the present work, the earlier experimental data were reanalyzed and a much higher value of E was obtained. This revised E value is consistent with the transformation mechanism of a layered hexacelsian structure into a three-dimensional feldspar structure of celsian which would necessitate the breaking of the Si-O and/or the Al-O bonds.

  3. Metastable mantle phase transformations and deep earthquakes in subducting oceanic lithosphere

    USGS Publications Warehouse

    Kirby, S.H.; Stein, S.; Okal, E.A.; Rubie, David C.

    1996-01-01

    Earth's deepest earthquakes occur as a population in subducting or previously subducted lithosphere at depths ranging from about 325 to 690 km. This depth interval closely brackets the mantle transition zone, characterized by rapid seismic velocity increases resulting from the transformation of upper mantle minerals to higher-pressure phases. Deep earthquakes thus provide the primary direct evidence for subduction of the lithosphere to these depths and allow us to investigate the deep thermal, thermodynamic, and mechanical ferment inside slabs. Numerical simulations of reaction rates show that the olivine ??? spinel transformation should be kinetically hindered in old, cold slabs descending into the transition zone. Thus wedge-shaped zones of metastable peridotite probably persist to depths of more than 600 km. Laboratory deformation experiments on some metastable minerals display a shear instability called transformational faulting. This instability involves sudden failure by localized superplasticity in thin shear zones where the metastable host mineral transforms to a denser, finer-grained phase. Hence in cold slabs, such faulting is expected for the polymorphic reactions in which olivine transforms to the spinel structure and clinoenstatite transforms to ilmenite. It is thus natural to hypothesize that deep earthquakes result from transformational faulting in metastable peridotite wedges within cold slabs. This consideration of the mineralogical states of slabs augments the traditional largely thermal view of slab processes and explains some previously enigmatic slab features. It explains why deep seismicity occurs only in the approximate depth range of the mantle transition zone, where minerals in downgoing slabs should transform to spinel and ilmenite structures. The onset of deep shocks at about 325 km is consistent with the onset of metastability near the equilibrium phase boundary in the slab. Even if a slab penetrates into the lower mantle, earthquakes

  4. Conductor Formation Through Phase Transformation in Ti-Oxide Thin Films

    NASA Astrophysics Data System (ADS)

    Liu, Y. S.; Lin, Y. H.; Wei, Y. S.; Liu, C. Y.

    2012-01-01

    The resistance and transmittance of Ti-oxide thin films sputtered on quartz substrates were studied. The electrical and optical properties can be changed by varying the percentage of O2 introduced during the sputtering. The lowest resistivity for the sputtered Ti-oxide thin film was 2.30 × 10-2 Ω cm for 12.5% O2, which was obtained after annealing at 400°C in ambient oxygen. The results of x-ray photoelectron spectroscopy (XPS) curve-fitting indicate that the Ti-oxide thin film contained both Ti2O3 and TiO2 phases during deposition. The Ti2O3 phase was transformed into the stable TiO2 phase during annealing. The Ti2O3-TiO2 phase transformation initiated the substitution reaction. The substitution of Ti4+ ions in the TiO2 phase for the Ti3+ ions in the Ti2O3 phase created the free electrons. This Ti2O3-TiO2 phase transformation demonstrates the potential mechanism for conduction in the annealed Ti-oxide thin films. The transmittance of the annealed Ti-oxide thin films can be as high as approximately 90% at the 400 nm wavelength with the introduction of 16.5% O2. This result indicates that the annealed Ti-oxide thin films are excellent candidates for use as transparent conducting layers for ultraviolet (UV) or near-UV light-emitting diode (LED) devices.

  5. Phase transformation during mechano-synthesis of nanocrystalline/amorphous Fe–32Mn–6Si alloys

    SciTech Connect

    Amini, Rasool; Shamsipoor, Ali; Ghaffari, Mohammad; Alizadeh, Morteza; Okyay, Ali Kemal

    2013-10-15

    Mechano-synthesis of Fe–32Mn–6Si alloy by mechanical alloying of the elemental powder mixtures was evaluated by running the ball milling process under an inert argon gas atmosphere. In order to characterize the as-milled powders, powder sampling was performed at predetermined intervals from 0.5 to 192 h. X-ray florescence analyzer, X-ray diffraction, scanning electron microscope, and high resolution transmission electron microscope were utilized to investigate the chemical composition, structural evolution, morphological changes, and microstructure of the as-milled powders, respectively. According to the results, the nanocrystalline Fe–Mn–Si alloys were completely synthesized after 48 h of milling. Moreover, the formation of a considerable amount of amorphous phase during the milling process was indicated by quantitative X-ray diffraction analysis as well as high resolution transmission electron microscopy image and its selected area diffraction pattern. It was found that the α-to-γ and subsequently the amorphous-to-crystalline (especially martensite) phase transformation occurred by milling development. - Graphical abstract: Mechano-synthesis of nanocrystalline/amorphous Fe–32Mn–6Si shape memory alloys in the powder form: amorphous phase formation, α-to-γ phase transformation, mechano-crystallization of the amorphous, and martensite phase formation during the process. Highlights: • During MA, the α-to-γ phase transformation and amorphization occurred. • Mechano-crystallization of the amorphous phase occurred at sufficient milling time. • The formation of high amount of ε-martensite was evidenced at high milling times. • The platelet, spherical, and then irregular particle shapes was extended by MA. • By MA, the particles size was increased, then reduced, and afterward re-increased.

  6. Transformers: the changing phases of low-dimensional vanadium oxide bronzes.

    PubMed

    Marley, Peter M; Horrocks, Gregory A; Pelcher, Kate E; Banerjee, Sarbajit

    2015-03-28

    In this feature article, we explore the electronic and structural phase transformations of ternary vanadium oxides with the composition MxV2O5 where M is an intercalated cation. The periodic arrays of intercalated cations ordered along quasi-1D tunnels or layered between 2D sheets of the V2O5 framework induce partial reduction of the framework vanadium atoms giving rise to charge ordering patterns that are specific to the metal M and stoichiometry x. This periodic charge ordering makes these materials remarkably versatile platforms for studying electron correlation and underpins the manifestation of phenomena such as colossal metal-insulator transitions, quantized charge corrals, and superconductivity. We describe current mechanistic understanding of these emergent phenomena with a particular emphasis on the benefits derived from scaling these materials to nanostructured dimensions wherein precise ordering of cations can be obtained and phase relationships can be derived that are entirely inaccessible in the bulk. In particular, structural transformations induced by intercalation are dramatically accelerated due to the shorter diffusion path lengths at nanometer-sized dimensions, which cause a dramatic reduction of kinetic barriers to phase transformations and facilitate interconversion between the different frameworks. We conclude by summarizing numerous technological applications that have become feasible due to recent advances in controlling the structural chemistry and both electronic and structural phase transitions in these versatile frameworks.

  7. In-situ measurement of phase transformation kinetics in austempered ductile iron

    SciTech Connect

    Meier, Leopold; Hofmann, Michael; Saal, Patrick; Volk, Wolfram; Hoffmann, Hartmut

    2013-11-15

    Austempered ductile iron (ADI) alloyed with 0.42% Mn and 0.72% Cu was heat treated in a mirror furnace and the phase transitions were studied in-situ by neutron diffraction. The heat treatment consisted of austenitisation at 920 °C and isothermal austempering at 400 °C, 350 °C and 300 °C, respectively. Due to the growth of ferrite platelets, the austenite content decreases rapidly at all temperatures within the first 15–20 min and reaches a stable plateau after 35 min (400 °C) to 80 min (300 °C). The carbon content of the residual austenite, which was monitored and characterised by the change of the lattice parameter, increases up to 1.6 wt.% caused by redistribution from the newly formed ferrite. While at higher austempering temperatures this takes place almost parallel to the phase transformation, at 300 °C the redistribution of carbon to austenite lags behind considerably. Furthermore the neutron data revealed an austenite peak asymmetry during austempering which is attributed to successive phase transformation. It results temporarily in two fractions of austenite, an initial low-carbon and an enriched high-carbon modification. - Highlights: • The heat treatment of ADI was studied in detail by in-situ neutron diffraction. • The phase fractions were monitored and evaluated quantitatively. • The austenite carbon content increased up to 1.6 wt.% during austempering. • Peak asymmetries indicate two austenite fractions during highest transformation rates.

  8. Phase transformation and optical properties of Cu-doped ZnS nanorods

    SciTech Connect

    Datta, Anuja Panda, Subhendu K.; Chaudhuri, Subhadra

    2008-09-15

    ZnS nanorods doped with 0-15 mol% of Cu have been prepared by simple solvothermal process. With gradual increase in the Cu concentration, phase transformation of the doped ZnS nanorods from wurtzite to cubic was observed. Twins and stacking faults were developed due to atomic rearrangement in the heavily doped ZnS nanorods during phase transformation. UV-vis-NIR absorbance spectroscopy ruled out the presence of any impure Cu-S phase. The doped ZnS nanorods showed luminescence over a wide range from UV to near IR with peaks at 370, 492-498, 565 and 730 nm. The UV region peak is due to the near-band-edge transition, whereas, the green peak can be related to emission from elementary sulfur species on the surfaces of the nanorods. The orange emission at 565 nm may be linked to the recombination of electrons at deep defect levels and the Cu(t{sub 2}) states present near the valence band of ZnS. The near IR emission possibly originated from transitions due to deep-level defects. - Graphical abstract: ZnS nanorods doped with 0-15 mol% of Cu has been prepared by simple solvothermal route. Interestingly, phase transformation of the doped ZnS nanorods from wurtzite to cubic was observed with gradual increase in the Cu concentration. Doped ZnS nanorods showed luminescence over a wide range from UV to near IR, which is also a rare observation.

  9. Solid-gaseous phase transformation of elemental contaminants during the gasification of biomass.

    PubMed

    Jiang, Ying; Ameh, Abiba; Lei, Mei; Duan, Lunbo; Longhurst, Philip

    2016-09-01

    Disposal of plant biomass removed from heavy metal contaminated land via gasification achieves significant volume reduction and can recover energy. However, these biomass often contain high concentrations of heavy metals leading to hot-corrosion of gasification facilities and toxic gaseous emissions. Therefore, it is of significant interest to gain a further understanding of the solid-gas phase transition of metal(loid)s during gasification. Detailed elemental analyses (C, H, O, N and key metal/metalloid elements) were performed on five plant species collected from a contaminated site. Using multi-phase equilibria modelling software (MTDATA), the analytical data allows modelling of the solid/gas transformation of metal(loid)s during gasification. Thermodynamic modelling based on chemical equilibrium calculations was carried out in this study to predict the fate of metal(loid) elements during typical gasification conditions and to show how these are influenced by metal(loid) composition in the biomass and operational conditions. As, Cd, Zn and Pb tend to transform to their gaseous forms at relatively low temperatures (<1000°C). Ni, Cu, Mn and Co converts to gaseous forms within the typical gasification temperature range of 1000-1200°C. Whereas Cr, Al, Fe and Mg remain in solid phase at higher temperatures (>1200°C). Simulation of pressurised gasification conditions shows that higher pressures increase the temperature at which solid-to-gaseous phase transformations takes place. PMID:26603198

  10. Solid-gaseous phase transformation of elemental contaminants during the gasification of biomass.

    PubMed

    Jiang, Ying; Ameh, Abiba; Lei, Mei; Duan, Lunbo; Longhurst, Philip

    2016-09-01

    Disposal of plant biomass removed from heavy metal contaminated land via gasification achieves significant volume reduction and can recover energy. However, these biomass often contain high concentrations of heavy metals leading to hot-corrosion of gasification facilities and toxic gaseous emissions. Therefore, it is of significant interest to gain a further understanding of the solid-gas phase transition of metal(loid)s during gasification. Detailed elemental analyses (C, H, O, N and key metal/metalloid elements) were performed on five plant species collected from a contaminated site. Using multi-phase equilibria modelling software (MTDATA), the analytical data allows modelling of the solid/gas transformation of metal(loid)s during gasification. Thermodynamic modelling based on chemical equilibrium calculations was carried out in this study to predict the fate of metal(loid) elements during typical gasification conditions and to show how these are influenced by metal(loid) composition in the biomass and operational conditions. As, Cd, Zn and Pb tend to transform to their gaseous forms at relatively low temperatures (<1000°C). Ni, Cu, Mn and Co converts to gaseous forms within the typical gasification temperature range of 1000-1200°C. Whereas Cr, Al, Fe and Mg remain in solid phase at higher temperatures (>1200°C). Simulation of pressurised gasification conditions shows that higher pressures increase the temperature at which solid-to-gaseous phase transformations takes place.

  11. Low temperature phase transformations in the metallic phases of iron and stony-iron meteorites

    NASA Astrophysics Data System (ADS)

    Reuter, K. B.; Williams, D. B.; Goldstein, J. I.

    1988-03-01

    The nickel content and the structure of kamacite and decomposed taenite (clear taenite 1, CT-1; the cloudy zone, CZ; and clear taenite 2, CT-2) in the metallic phases of meteorites were determined using X-ray microanalysis techniques in the AEM. The kamacite near the CT-1 interface was found to contain about 4 wt pct Ni. The CT-1 structure contains 51.4-45.6 wt pct Ni; it is ordered FeNi with the L1(0) superstructure. The CZ structure consists of two phases: a globular phase (ordered FeNi containing 50.9 wt pct Ni) and a surrounding honeycomb martensitic phase containing 11.7 wt pct Ni. The CT-2 was found in all of the iron meteorite groups studied and in the pallasites, but not in the mesosiderites. Based on the preliminary evidence, this region is believed to be ordered Fe3Ni. Possible mechanisms for the decomposition of taenite are discussed.

  12. Impact of quasi-dc currents on three-phase distribution transformer installations

    SciTech Connect

    McConnell, B.W.; Barnes, P.R. ); Tesche, F.M. , Dallas, TX ); Schafer, D.A. )

    1992-06-01

    This report summarizes a series of tests designed to determine the response of quasi-dc currents on three-phase power distribution transformers for electric power systems. In general, if the dc injection is limited to the primary side of a step-down transformer, significant harmonic distortion is noted and an increase in the reactive power demand results. For dc injection on the secondary (load) side of the step-down transformer the harmonic content at the secondary side is quite high and saturation occurs with a relatively low level of dc injection; however, the reactive power demand is significantly lower. These tests produced no apparent damage to the transformers. Transformer damage is dependent on the duration of the dc excitation, the level of the excitation, and on thermal characteristics of the transfer. The transformer response time is found to be much shorter than seen in power transformer tests at lower dc injection levels. This shorter response time suggests that the response time is strongly dependent on the injected current levels, and that higher levels of dc injection for shorter durations could produce very high reactive power demands and harmonic distortion within a few tenths of a second. The added reactive power load could result in the blowing of fuses on the primary side of the transformer for even moderate dc injection levels, and neutral currents are quite large under even low-level dc injection. This smoking neutral'' results in high-level harmonic injection into equipment via the neutral and in possible equipment failure.

  13. Natural Ferrihydrite as an Agent for Reducing Turbidity Caused by Suspended Clays

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The turbidity of water can be reduced by the addition of positively charged compounds which coagulate negatively charged clay particles in suspension causing them to flocculate. This research was conducted to determine the effectiveness of the Fe oxide mineral ferrihydrite as a flocculating agent fo...

  14. Bioaccessibility Of Lead Sequestered To Corundum and Ferrihydrite In A Simulated Gastrointestinal System

    EPA Science Inventory

    Lead (Pb) sorption onto oxide surfaces in soils may strongly influence the risk posed from incidental ingestion of Pb-contaminated soil. Lead was sorbed to model oxide minerals of corundum (α-Al2O3) and ferrihydrite (Fe5HO8•4H2

  15. TRANSFORMER

    DOEpatents

    Baker, W.R.

    1959-08-25

    Transformers of a type adapted for use with extreme high power vacuum tubes where current requirements may be of the order of 2,000 to 200,000 amperes are described. The transformer casing has the form of a re-entrant section being extended through an opening in one end of the cylinder to form a coaxial terminal arrangement. A toroidal multi-turn primary winding is disposed within the casing in coaxial relationship therein. In a second embodiment, means are provided for forming the casing as a multi-turn secondary. The transformer is characterized by minimized resistance heating, minimized external magnetic flux, and an economical construction.

  16. A theoretical study of the omega-phase transformation in metals

    NASA Astrophysics Data System (ADS)

    Sanati, Mahdi

    I have studied the formation of o-phase from electronic and mesoscopic (domain wall) points of view. To study the formation of domain walls, I have extended the Landau model of Cook for the o-phase transition by including a spatial gradient (Ginzburg) term of the scalar order parameter. In general, the Landau free energy is an asymmetric double-well potential. From the variational derivative of the total free energy I obtained a static equilibrium condition. By solving this equation for different physical parameters and boundary conditions, I obtained different quasi-one-dimensional soliton-like solutions. These solutions correspond to three different types of domain walls between the o-phase and the beta-matrix. These results are used to model the formation of the o-phase in bcc Ti. Canonical band model and first principles calculations confirmed the instability of the bcc-phase of group III and IV transition metals with respect to the o-phase transformation. I showed that the d-electron density is the controlling parameter for this type of the transformation. Also the possibility of formation of the o-phase for rare earth metals is discussed. First-principles full-potential linear muffin-tin orbital method (FPLMTO) calculations are performed for o-type displacement of the atoms to study the formation of the o-phase in TiAl and Ti 3Al2Nb alloys. The results of my calculations showed an instability in ordered B2 TiAl structure with respect to the o-phase when one third of the Al atoms are replaced by Nb atoms. These phenomena are explained, first by symmetry arguments; then a pair potential model is used to illustrate this instability based on interactions between different pair of atoms derived from the electronic structure. In addition, importance of the atomic arrangements on the structural stability of the Ti3Al2 Nb system is discussed.

  17. Pressure, temperature, and electric field dependence of phase transformations in niobium modified 95/5 lead zirconate titanate

    SciTech Connect

    Dong, Wen D.; Carlos Valadez, J.; Gallagher, John A.; Jo, Hwan R.; Lynch, Christopher S.; Sahul, Raffi; Hackenberger, Wes

    2015-06-28

    Ceramic niobium modified 95/5 lead zirconate-lead titanate (PZT) undergoes a pressure induced ferroelectric to antiferroelectric phase transformation accompanied by an elimination of polarization and a volume reduction. Electric field and temperature drive the reverse transformation from the antiferroelectric to ferroelectric phase. The phase transformation was monitored under pressure, temperature, and electric field loading. Pressures and temperatures were varied in discrete steps from 0 MPa to 500 MPa and 25 °C to 125 °C, respectively. Cyclic bipolar electric fields were applied with peak amplitudes of up to 6 MV m{sup −1} at each pressure and temperature combination. The resulting electric displacement–electric field hysteresis loops were open “D” shaped at low pressure, characteristic of soft ferroelectric PZT. Just below the phase transformation pressure, the hysteresis loops took on an “S” shape, which split into a double hysteresis loop just above the phase transformation pressure. Far above the phase transformation pressure, when the applied electric field is insufficient to drive an antiferroelectric to ferroelectric phase transformation, the hysteresis loops collapse to linear dielectric behavior. Phase stability maps were generated from the experimental data at each of the temperature steps and used to form a three dimensional pressure–temperature–electric field phase diagram.

  18. Dependence of microbial magnetite formation on humic substance and ferrihydrite concentrations

    NASA Astrophysics Data System (ADS)

    Piepenbrock, Annette; Dippon, Urs; Porsch, Katharina; Appel, Erwin; Kappler, Andreas

    2011-11-01

    Iron mineral (trans)formation during microbial Fe(III) reduction is of environmental relevance as it can influence the fate of pollutants such as toxic metal ions or hydrocarbons. Magnetite is an important biomineralization product of microbial iron reduction and influences soil magnetic properties that are used for paleoclimate reconstruction and were suggested to assist in the localization of organic and inorganic pollutants. However, it is not well understood how different concentrations of Fe(III) minerals and humic substances (HS) affect magnetite formation during microbial Fe(III) reduction. We therefore used wet-chemical extractions, magnetic susceptibility measurements and X-ray diffraction analyses to determine systematically how (i) different initial ferrihydrite (FH) concentrations and (ii) different concentrations of HS (i.e. the presence of either only adsorbed HS or adsorbed and dissolved HS) affect magnetite formation during FH reduction by Shewanella oneidensis MR-1. In our experiments magnetite formation did not occur at FH concentrations lower than 5 mM, even though rapid iron reduction took place. At higher FH concentrations a minimum fraction of Fe(II) of 25-30% of the total iron present was necessary to initiate magnetite formation. The Fe(II) fraction at which magnetite formation started decreased with increasing FH concentration, which might be due to aggregation of the FH particles reducing the FH surface area at higher FH concentrations. HS concentrations of 215-393 mg HS/g FH slowed down (at partial FH surface coverage with sorbed HS) or even completely inhibited (at complete FH surface coverage with sorbed HS) magnetite formation due to blocking of surface sites by adsorbed HS. These results indicate the requirement of Fe(II) adsorption to, and subsequent interaction with, the FH surface for the transformation of FH into magnetite. Additionally, we found that the microbially formed magnetite was further reduced by strain MR-1 leading to

  19. Computer simulation and experimental study of transient processes in a single-phase voltage transformer

    NASA Astrophysics Data System (ADS)

    Kruzhaev, A. V.; Elagin, I. A.; Pavleino, M. A.; Dmitriev, V. A.; Chaly, A. M.

    2015-02-01

    We perform simulation and experimental investigation of transient processes emerging in a single-phase transformer when it is connected to the network. The transformer model constructed taking into account the saturation of the steel of the core differs from standard models in detailed accounting for the magnetic flux leakage, which is required, for example, for a correct description of inrush current. Universality of the model for the type of transformers under study is ensured by the allowance for eddy current losses and calculation of the magnetic hysteresis in the steel core. The latter makes it possible to estimate the effect of residual magnetization of the core on the form of a transient process, which is studied in detail. The methods for computing model parameters are described and its experimental verification is carried out.

  20. Effect of Cold Rolling on Phase Transformation Temperatures of NiTi Shape Memory Alloy

    NASA Astrophysics Data System (ADS)

    Pattabi, Manjunatha; Murari, M. S.

    2015-02-01

    The effect of cold rolling and heat treatment on the phase transformation behavior of NiTi shape memory alloy (SMA) heat treated at 660 °C has been investigated. Four sets of samples were cold rolled after heat treatment. The austenite-to-martensite and martensite-to-austenite transformation temperatures for samples without any cold rolling are determined through differential scanning calorimetry (DSC). The austenitic start temperature gets shifted to the higher temperature side with increase in the percentage of the cold rolling up to 12.5%. Austenitic finish temperature could not be detected in cold-rolled samples. Martensitic start temperature increases slightly with increased cold rolling while martensitc finish temperature slightly decreases. Beyond 12.5% cold work, the shape memory effect (SME) is completely lost. The evolution of austenitic phase in SMA subjected to cold rolling was studied through powder x-ray diffraction (XRD) at different temperatures in the range 25 to 160 °C at intervals of 10 °C, during heating and cooling. The XRD results agree with those of DSC. Two sets of cold-rolled samples were again heat treated to 300 and 500 °C and the transformation behavior was studied using DSC. Heat treatment at 300 °C brings back the SME, but with the presence of an intermediate R-Phase due to the additional dislocations present. Even with a heat treatment at 500 °C, the effect of cold work is not completely removed and a single-step transformation is not observed. Another set of samples subjected to cold work were heat treated at 660 °C and the transformation is studied. The effect of cold work even up to 25% is completely removed with this heat treatment as indicated by DSC. The complete regaining of the SME is further confirmed by electrical resistivity measurements also.

  1. Volume and Mass Estimation of Three-Phase High Power Transformers for Space Applications

    NASA Technical Reports Server (NTRS)

    Kimnach, Greg L.

    2004-01-01

    Spacecraft historically have had sub-1kW(sub e), electrical requirements for GN&C, science, and communications: Galileo at 600W(sub e), and Cassini at 900W(sub e), for example. Because most missions have had the same order of magnitude power requirements, the Power Distribution Systems (PDS) use existing, space-qualified technology and are DC. As science payload and mission duration requirements increase, however, the required electrical power increases. Subsequently, this requires a change from a passive energy conversion (solar arrays and batteries) to dynamic (alternator, solar dynamic, etc.), because dynamic conversion has higher thermal and conversion efficiencies, has higher power densities, and scales more readily to higher power levels. Furthermore, increased power requirements and physical distribution lengths are best served with high-voltage, multi-phase AC to maintain distribution efficiency and minimize voltage drops. The generated AC-voltage must be stepped-up (or down) to interface with various subsystems or electrical hardware. Part of the trade-space design for AC distribution systems is volume and mass estimation of high-power transformers. The volume and mass are functions of the power rating, operating frequency, the ambient and allowable temperature rise, the types and amount of heat transfer available, the core material and shape, the required flux density in a core, the maximum current density, etc. McLyman has tabulated the performance of a number of transformers cores and derived a "cookbook" methodology to determine the volume of transformers, whereas Schawrze had derived an empirical method to estimate the mass of single-phase transformers. Based on the work of McLyman and Schwarze, it is the intent herein to derive an empirical solution to the volume and mass estimation of three-phase, laminated EI-core power transformers, having radiated and conducted heat transfer mechanisms available. Estimation of the mounting hardware, connectors

  2. Phase Transformation Surfaces Analysis for SMA Around a Crack Tip with Curvature

    NASA Astrophysics Data System (ADS)

    Laydi, Mohamed Rachid; Lexcellent, Christian

    2015-09-01

    Under loading, for a shape memory alloy, the stress concentration around the crack tip, inside a plate, is a serious fracture problem. The tip shape constitutes an important data. In a recent paper (Lexcellent et al. in Int J Fract 169:1-13, 2011), the determination of phase transformation surfaces around a crack tip without curvature was investigated. For crack with curvature, the approximate stress field solution proposed by Creager and Paris is used (Int J Fract 3:247-252, 1967). The knowledge of phase transformation surfaces dimensions and shapes can help us to define a fracture criterion. The study is focussed on mode I because this opening mode is the most dangerous for the structure. Also, comparisons between experiments and computing can be made. Qualitative agreement was obtained.

  3. Low Scaling Algorithms for the Random Phase Approximation: Imaginary Time and Laplace Transformations.

    PubMed

    Kaltak, Merzuk; Klimeš, Jiří; Kresse, Georg

    2014-06-10

    In this paper, we determine efficient imaginary frequency and imaginary time grids for second-order Møller-Plesset (MP) perturbation theory. The least-squares and Minimax quadratures are compared for periodic systems, finding that the Minimax quadrature performs slightly better for the considered materials. We show that the imaginary frequency grids developed for second order also perform well for the correlation energy in the direct random phase approximation. Furthermore, we show that the polarizabilities on the imaginary time axis can be Fourier-transformed to the imaginary frequency domain, since the time and frequency Minimax grids are dual to each other. The same duality is observed for the least-squares grids. The transformation from imaginary time to imaginary frequency allows one to reduce the time complexity to cubic (in system size), so that random phase approximation (RPA) correlation energies become accessible for large systems.

  4. Optical bandgap widening and phase transformation of nitrogen doped cupric oxide

    NASA Astrophysics Data System (ADS)

    Masudy-Panah, Saeid; Radhakrishnan, K.; Kumar, Avishek; Wong, Ten It; Yi, Ren; Dalapati, Goutam Kumar

    2015-12-01

    The structural and optical properties of sputter deposited nitrogen (N) doped CuO (CuO(N)) thin films are systematically investigated. It is found that the incorporation of N into CuO causes an enlargement of optical bandgap and reduction in resistivity of the CuO(N) films. Furthermore, a gradual phase transformation from CuO to Cu2O is observed with the increase in N concentration. The effects of annealing temperature on the structural properties of CuO (N) and its dependence on N concentration are also investigated. It is observed that the phase transformation process from CuO to Cu2O significantly depends on the N concentration and the annealing temperature. Heterojunction solar cells of p-type CuO(N) on n-type silicon (Si) substrate, p-CuO(N)/n-Si, are fabricated to investigate the impact of N doping on its photovoltaic properties.

  5. Effect of calcination temperature on phase transformation of HfO{sub 2} nanoparticles

    SciTech Connect

    Tripathi, S. K.; Kaur, Charanpreet; Kaur, Ramneek; Kaur, Jagdish

    2015-08-28

    Oxides nanomaterials exhibit unique physical, chemical and structural properties and motivated a big research that focus in the integration of these materials for various optoelectronic device applications. In present work, hafnium oxide (HfO{sub 2}) nanoparticles (NPs) have been synthesized using precipitation method. Hafnium tetrachloride and sodium hydroxide has been used as starting precursors. Prepared oxide material has been characterized by X-Ray Diffraction (XRD), Fourier Transform Infra-Red (FTIR) and UV-Vis spectroscopy. The phase transformation from amorphous to monoclinic is observed with the increase in calcination temperature from 500 °C and 800 °C. In FTIR spectra, the characteristic bands at ν ∼ 758.53 and 509.57 cm{sup −1} reveals the monoclinic phase of prepared HfO{sub 2} NPs. UV-Vis spectroscopy shows an absorption peak at 204 nm and the bandgap calculated is 6.07 eV.

  6. Effect of calcination temperature on phase transformation of HfO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Tripathi, S. K.; Kaur, Charanpreet; Kaur, Ramneek; Kaur, Jagdish

    2015-08-01

    Oxides nanomaterials exhibit unique physical, chemical and structural properties and motivated a big research that focus in the integration of these materials for various optoelectronic device applications. In present work, hafnium oxide (HfO2) nanoparticles (NPs) have been synthesized using precipitation method. Hafnium tetrachloride and sodium hydroxide has been used as starting precursors. Prepared oxide material has been characterized by X-Ray Diffraction (XRD), Fourier Transform Infra-Red (FTIR) and UV-Vis spectroscopy. The phase transformation from amorphous to monoclinic is observed with the increase in calcination temperature from 500 °C and 800 °C. In FTIR spectra, the characteristic bands at ν ˜ 758.53 and 509.57 cm-1 reveals the monoclinic phase of prepared HfO2 NPs. UV-Vis spectroscopy shows an absorption peak at 204 nm and the bandgap calculated is 6.07 eV.

  7. Magnetostructural phase transformations in Tb 1-x Mn 2

    SciTech Connect

    Zou, Junding; Paudyal, Durga; Liu, Jing; Mudryk, Yaroslav; Pecharsky, Vitalij K.; Gschneidner, Karl A.

    2015-01-16

    Magnetism and phase transformations in non-stoichiometric Tb1-xMn2 (x = 0.056, 0.039) have been studied as functions of temperature and magnetic field using magnetization, heat capacity, and X-ray powder diffraction measurements. Lowering the temperature, the compounds sequentially order ferrimagnetically and antiferromagnetically, and finally, exhibit spin reorientation transitions. Moreover, these structural distortions from room temperature cubic to low temperature rhombohedral structures occur at TN, and are accompanied by large volume changes reaching ~-1.27% and -1.42%, respectively. First principles electronic structure calculations confirm the phase transformation from the ferrimagnetic cubic structure to the antiferromagnetic rhombohedral structure in TbMn2.

  8. [Radiation transformation mechanism in a photocatalytic reactor of three-phase internal circulating fluidized bed].

    PubMed

    You, Hong; Luo, Wei-nan; Yao, Jie; Chen, Ping; Cai, Wei-min

    2005-01-01

    A novel three-phase internal circulating fluidized bed photocatalytic reactor was established and the radiation transformation in which was investigated. The experimental results indicate that with the interaction of gas and solid (gas flux > 0.3m3/h), the radiation transformation in the reactor along radial direction conforms to a definite exponential function, which agrees to formula Rose about the rules of light intensity distribution through evenly suspended particles. The value of radiation energy is affected by the initial light intensity, the concentration of photocatalyst and the thickness of liquid layer. The aerated gas amount only influence the state of the fluidized bed and has little effect on the distribution of light intensity along radical direction. Photocatalytic degradation of Rhodamine B indicate that the efficiency of three-phase internal circulating fluidized bed is much higher than slurry bed. The optimal catalyst concentration of this system is 10 - 12g/L.

  9. Thermodynamic properties, nonstoichiometry and phase transformation parameters of oxides in the Eu-O system

    NASA Astrophysics Data System (ADS)

    Sukhushina, I.; Vasiljeva, I.; Balabajeva, R.

    1998-01-01

    The influence of nonstoichiometry on the partial thermodynamic properties of oxygen and the {C to B} transformation parameters of europium sesquioxide within a temperature range from 1200 K to 1400 K using e.m.f., DTA and DSC methods, has been determined. A tentative phase diagram in the {Cto B} transformation region is proposed. L'influence de la nonstoechiométrie sur les propriétés thermodynamiques partielles de l'oxygène et sur les paramètres de la transition {C to B} de Eu2O3 dans l'intervalle de températures de 1200 K à 1400 K a été étudiée par les méthodes EMF, DTA, DSC. Une variante de diagramme de phases dans la région de la transition {Cto B} est présentée.

  10. Transformation toughened ceramics for the heavy duty diesel engine technology program, phase 2

    NASA Technical Reports Server (NTRS)

    Musikant, S.; Samanta, S. C.; Architetto, P.; Feingold, E.

    1985-01-01

    The objective of this program is to develop an insulating structural ceramic for application in a heavy duty adiabatic diesel engine. The approach is to employ transformation toughening (TT) by additions of zirconia-hafnia solid solution (ZHSS). The feasibility of using ZHSS as a toughening agent in mullite and alumina has been demonstrated in Phase 1 of this work. Based on Phase 1 results, a decision was made to concentrate the Phase 2 effort on process optimization of the TT mullite. A strong factor in that decision was the low thermal conductivity and high thermal shock resistance of the mullite. Results of the Phase 2 effort indicate that optimum toughening of mullite by additions of ZHSS is difficult to achieve due to apparent sensitivity to morphology. The 48 ksi room temperature modulus-of-rupture (MOR) achieved in selected specimens is approximately 50% of the original strength target. The MOR deteriorated to 34 ksi at 800 C.

  11. Color image encryption using iterative phase retrieve process in quaternion Fourier transform domain

    NASA Astrophysics Data System (ADS)

    Sui, Liansheng; Duan, Kuaikuai

    2015-02-01

    A single-channel color image encryption method is proposed based on iterative phase iterative process in quaternion Fourier transform domain. First, three components of the plain color image is confused respectively by using cat map. Second, the confused components are combined into a pure quaternion image, which is encode to the phase only function by using an iterative phase retrieval process. Finally, the phase only function is encrypted into the gray scale ciphertext with stationary white noise distribution based on the chaotic diffusion, which has camouflage property to some extent. The corresponding plain color image can be recovered from the ciphertext only with correct keys in the decryption process. Simulation results verify the feasibility and effectiveness of the proposed method.

  12. Indices of ionospheric GPS phase fluctuation derived by using Hilbert-Huang Transform

    NASA Astrophysics Data System (ADS)

    Sun, Y.; Liu, J.

    2008-12-01

    Variations in phase and amplitude of the GPS signal have been used to monitor irregularities of the ionospheric electron density. Based on the Fourier analysis, fluctuations in the total electron content (TEC) recorded by ground-based GPS receivers have been derived the indices of Fp and fp to stand for the hourly and quarterly GPS phase fluctuations. However, it has been well known the ionospheric GPS phase fluctuation to be a non-stationary and nonlinear phenomenon. Therefore, base on the intrinsic and adaptive characters of Hilbert-Huang transform (HHT), we develop a new detrained procedure computing the indices of GPS phase fluctuation. Results confirm that the two indices derived by the HHT yield a better performance.

  13. Direct phase extraction of self-mixing displacement measurement using Hilbert transform

    NASA Astrophysics Data System (ADS)

    Tao, Yufeng; Wang, Ming; Guo, Dongmei; Zhang, Jiahuan

    2016-01-01

    Signals of a self-mixing interferometer established on a semiconductor laser diode are analyzed. Phase is extracted out for decoding measurement which contained in self-mixing fringes. The semiconductor laser diode works as light source and receiver without modulation. By combining Hilbert transform with phase condition of self-mixing interference, micron- displacement is reconstructed by phase information at week or even moderate feedback level. Theoretical analysis and simulation results are presented before verification of experimental measurement. Practical feedback level is estimated by a data fitting technique with a programmable high-resolution PZT. Consistence of the results promises that direct phase extraction on self-mixing interferometer is available for micron-displacement measurement with a nanometer accuracy.

  14. Phase transformation as the single-mode mechanical deformation of silicon

    SciTech Connect

    Wong, S. Williams, J. S.; Bradby, J. E.; Haberl, B.

    2015-06-22

    The metastable body-centered cubic (bc8) and rhombohedral (r8) phases of silicon that are formed after the nanoindentation of diamond cubic silicon exhibit properties that are of both scientific and technological interest. This letter demonstrates that large regions of these phases can be readily formed from crystalline silicon via nanoindentation with minimal damage to the surrounding crystal. Cross-sectional transmission electron microscopy is used to show that volumes of these phases 6 μm wide and up to 650 nm deep can be generated using a symmetrical spherical tip of ∼21.5 μm diameter. This result indicates that the use of large symmetrical spherical tips result in highly hydrostatic conditions that can favor the single phase transformation mode without extensive damage to the surrounding crystalline regions that are observed in previous studies.

  15. Optical cryptosystem of color images using random phase masks in the fractional wavelet transform domain

    NASA Astrophysics Data System (ADS)

    Singh, Hukum

    2016-05-01

    An optical color image encryption in the Fractional Wavelet Transform (FWT) domain is carried out. The original images are segregated into three colors components: R (red), G (green) and B (blue). After that the components are encrypted separately using double random phase encoding (DRPE) in the FWT domain. Random phase masks (RPMs) are used in the input as well as in Fourier plane. The images to be encrypted are transformed with the discrete wavelet transform (DWT), the resulting coefficients from the DWT are multiplied each one by masks different form RPM. Masks are independent each other and the results are applied an inverse discrete Wavelet Transform (IDWT), obtaining the encrypted images. The input images are recovered from their corresponding encrypted images by using the correct parameters of the FWT, and its digital implementation has been performed using MATLAB 7.6.0 (R2008a). The mother wavelet family and fractional orders associated with the FWT are extra keys that access difficulty an attacker; thereby the scheme is more secure as compared to conventional techniques. The sensitivity of proposed scheme is verified with encryption parameters, occlusions, and noise attacks.

  16. Improving the efficiency of molecular replacement by utilizing a new iterative transform phasing algorithm.

    PubMed

    He, Hongxing; Fang, Hengrui; Miller, Mitchell D; Phillips, George N; Su, Wu Pei

    2016-09-01

    An iterative transform method proposed previously for direct phasing of high-solvent-content protein crystals is employed for enhancing the molecular-replacement (MR) algorithm in protein crystallography. Target structures that are resistant to conventional MR due to insufficient similarity between the template and target structures might be tractable with this modified phasing method. Trial calculations involving three different structures are described to test and illustrate the methodology. The relationship of the approach to PHENIX Phaser-MR and MR-Rosetta is discussed. PMID:27580202

  17. Dynamics of Structural Transformations between Lamellar and Inverse Bicontinuous Cubic Lyotropic Phases

    SciTech Connect

    Conn, Charlotte E.; Ces, Oscar; Mulet, Xavier; Seddon, John M.; Templer, Richard H.; Finet, Stephanie; Winter, Roland

    2006-03-17

    The liquid crystalline lamellar (L{sub {alpha}}) to double-diamond inverse bicontinuous cubic (Q{sub II}{sup D}) phase transition for the amphiphile monoelaidin in excess water exhibits a remarkable sequence of structural transformations for pressure or temperature jumps. Our data imply that the transition dynamics depends on a coupling between changes in molecular shape and the geometrical and topological constraints of domain size. We propose a qualitative model for this coupling based on theories of membrane fusion via stalks and existing knowledge of the structure and energetics of bicontinuous cubic phases.

  18. Improving the efficiency of molecular replacement by utilizing a new iterative transform phasing algorithm

    PubMed Central

    He, Hongxing; Fang, Hengrui; Miller, Mitchell D.; Phillips, George N.; Su, Wu-Pei

    2016-01-01

    An iterative transform method proposed previously for direct phasing of high-solvent-content protein crystals is employed for enhancing the molecular-replacement (MR) algorithm in protein crystallography. Target structures that are resistant to conventional MR due to insufficient similarity between the template and target structures might be tractable with this modified phasing method. Trial calculations involving three different structures are described to test and illustrate the methodology. The relationship of the approach to PHENIX Phaser-MR and MR-Rosetta is discussed. PMID:27580202

  19. Phase-recovery improvement using analytic wavelet transform analysis of a noisy interferogram cepstrum.

    PubMed

    Etchepareborda, Pablo; Vadnjal, Ana Laura; Federico, Alejandro; Kaufmann, Guillermo H

    2012-09-15

    We evaluate the extension of the exact nonlinear reconstruction technique developed for digital holography to the phase-recovery problems presented by other optical interferometric methods, which use carrier modulation. It is shown that the introduction of an analytic wavelet analysis in the ridge of the cepstrum transformation corresponding to the analyzed interferogram can be closely related to the well-known wavelet analysis of the interferometric intensity. Subsequently, the phase-recovery process is improved. The advantages and limitations of this framework are analyzed and discussed using numerical simulations in singular scalar light fields and in temporal speckle pattern interferometry. PMID:23041878

  20. Modeling the cure kinetics of crosslinking free radical polymerizations using the Avrami theory of phase transformation

    SciTech Connect

    Finnegan, G.R.; Shine, A.D.

    1995-12-01

    A model, based on Avrami`s theory of phase transformation, has been developed to describe the cure kinetics of crosslinking free radical polymerizations. The model assumes the growing polymer can be treated as a distinct phase and the nucleation rate is proportional to the initiation rate of the polymerization. The Avrami time exponent was verified to be 4.0. This physically-based, two-parameter model fits vinyl ester resin heat flow data as well as the empirical, four-parameter autocatalytic model, and is capable of describing both neat and fiber-containing resin.

  1. Structure, phase transformations, mechanical characteristics, and cold resistance of low-carbon martensitic steels

    NASA Astrophysics Data System (ADS)

    Kozvonin, V. A.; Shatsov, A. A.; Ryaposov, I. V.; Zakirova, M. G.; Generalova, K. N.

    2016-08-01

    Temper-resistant low-carbon Cr-Mn-Ni-Mo-V-Nb steels with concentrations of carbon of 0.15 and 0.27 wt % have been studied. It has been shown that, upon quenching, various morphological types of the α phase can be formed. The structure of the steels is stable in the course of heating below critical temperatures and remains a lath-type structure in the intercritical temperature range. Specific features of structural and phase transformations, as well as the dependence of the mechanical characteristics of the steels, on the tempering temperature have been determined.

  2. Phase transformations in Ti-6.8Mo-4.5Fe-1.5Al

    SciTech Connect

    Azimzadeh, S.; Rack, H.J.

    1998-10-01

    Phase transformations during artificial and isothermal aging of Ti-6.8Mo-4.5Fe-1.5Al have been investigated over the temperature range from 300 C to 750 C utilizing hardness measurements, X-ray diffraction, optical microscopy, and electron microscopy. Artificial aging following solution treatment and water quenching initially involved growth of the athermal {omega} phase. This was followed by formation of the {alpha} phase, either in association with the {omega} phase, through homogeneous precipitation within the matrix, or through heterogeneous grain-boundary nucleation. Similarly, isothermal decomposition of the metastable {beta} phase resulted in the precipitation of {omega} phase exhibiting an ellipsoidal morphology. While precipitation of {omega} was immediate at 345 C, an incubation period was observed upon aging at 390 C. Isothermal aging above this temperature involved direct precipitation of the {alpha} phase, either homogeneously within the {beta} matrix or heterogeneously at {beta} grain boundaries. The extent of homogeneous vs heterogeneous {alpha} nucleation during isothermal aging depended upon aging temperature; low aging temperatures promote homogeneous nucleation and higher aging temperatures promote {alpha} heterogeneous nucleation. Finally, continued aging resulted, independent of aging path, in coarsening and spheroidization of the {alpha} phase.

  3. Infrared small target enhancement via phase spectrum of Quaternion Fourier Transform

    NASA Astrophysics Data System (ADS)

    Qi, Shengxiang; Ma, Jie; Li, Hang; Zhang, Shuiping; Tian, Jinwen

    2014-01-01

    Small target enhancement is one of the crucial stages in infrared small target detection. In this paper, we propose a new method using phase spectrum of Quaternion Fourier Transform to enhance small targets while suppressing backgrounds for infrared images. This is inspired by the property that regularly Gaussian-like shape small targets could be considered as attractively salient signal in infrared images and the location information of such signal is implicitly contained in the phase spectrum from frequency domain. Formally, in the proposed method, we adopt the phase spectrum of Quaternion Fourier Transform instead of using traditional Fourier Transform to enhance the targets since the quaternion provides at most four data channels than only one for the latter, which could be helpful to broad types of background clutters by adding more information. For the construction of the quaternion, we present a second-order directional derivative filter via facet model to compute four second order directional derivative maps from four directions respectively as the four data channels. This filter is used to suppress noises and distinguish the targets and backgrounds into separably different textures so that it would boost the robustness of small target enhancement. In experiments, some typical infrared images with various scenes are tested to validate the effectiveness of the proposed method. The results demonstrate that our method actually has good performance and outperforms several state-of-the-art methods, which can be further used for infrared small target detection and tracking.

  4. Residual stress delaying phase transformation in Y-TZP bio-restorations

    NASA Astrophysics Data System (ADS)

    Allahkarami, Masoud; Hanan, Jay C.

    2012-01-01

    Engineering favorable residual stress for the complex geometry of bi-layer porcelain-zirconia crowns potentially prevents crack initiation and improves the mechanical performance and lifetime of the dental restoration. In addition to external load, the stress field depends on initial residual stress before loading. Residual stress is the result of factors such as the thermal expansion mismatch of layers and compliance anisotropy of zirconia grains in the process of sintering and cooling. Stress induced phase transformation in zirconia extensively relaxes the residual stress and changes the stress state. The objective of this study is to investigate the coupling between tetragonal to monoclinic phase transformations and residual stress. Residual stress, on the surface of the sectioned single load to failure crown, at 23 points starting from the pure tetragonal and ending at a fully monoclinic region were measured using the micro X-ray diffraction sin2 ψ method. An important observation is the significant range in measured residual stress from a compressive stress of -400 MPa up to tensile stress of 400 MPa and up to 100% tetragonal to monoclinic phase transformation.

  5. Temperature-dependent mechanical deformation of silicon at the nanoscale: Phase transformation versus defect propagation

    SciTech Connect

    Kiran, M. S. R. N. Tran, T. T.; Smillie, L. A.; Subianto, D.; Williams, J. S.; Bradby, J. E.; Haberl, B.

    2015-05-28

    This study uses high-temperature nanoindentation coupled with in situ electrical measurements to investigate the temperature dependence (25–200 °C) of the phase transformation behavior of diamond cubic (dc) silicon at the nanoscale. Along with in situ indentation and electrical data, ex situ characterizations, such as Raman and cross-sectional transmission electron microscopy, have been used to reveal the indentation-induced deformation mechanisms. We find that phase transformation and defect propagation within the crystal lattice are not mutually exclusive deformation processes at elevated temperature. Both can occur at temperatures up to 150 °C but to different extents, depending on the temperature and loading conditions. For nanoindentation, we observe that phase transformation is dominant below 100 °C but that deformation by twinning along (111) planes dominates at 150 °C and 200 °C. This work, therefore, provides clear insight into the temperature dependent deformation mechanisms in dc-Si at the nanoscale and helps to clarify previous inconsistencies in the literature.

  6. Precipitation and Phase Transformations in 2101 Lean Duplex Stainless Steel During Isothermal Aging

    NASA Astrophysics Data System (ADS)

    Maetz, Jean-Yves; Cazottes, Sophie; Verdu, Catherine; Kleber, Xavier

    2016-01-01

    The effect of isothermal aging at 963 K (690 °C) on the microstructure of a 2101 lean duplex stainless steel, with the composition Fe-21.5Cr-5Mn-1.6Ni-0.22N-0.3Mo, was investigated using a multi-technique and multi-scale approach. The kinetics of phase transformation and precipitation was followed from a few minutes to thousands of hours using thermoelectric power measurements; based on these results, certain aging states were selected for electron microscopy characterization. Scanning electron microscopy, electron back-scattered diffraction, and transmission electron microscopy were used to quantitatively describe the microstructural evolution through crystallographic analysis, chemical analysis, and volume fraction measurements from the macroscopic scale down to the nanometric scale. During aging, the precipitation of M23C6 carbides, Cr2N nitrides, and σ phase as well as the transformation of ferrite into austenite and austenite into martensite was observed. These complex microstructural changes are controlled by Cr volume diffusion. The precipitation and phase transformation mechanisms are described.

  7. The Effect of Hardenability Variation on Phase Transformation of Spiral Bevel Gear in Quenching Process

    NASA Astrophysics Data System (ADS)

    Zhang, Yingtao; Shi, Wankai; Yang, Lin; Gu, Zhifei; Li, Zhichao

    2016-07-01

    The hardenability of gear steel is dependent on the composition of alloying elements and is one of important criteria to assess process of phase transformation. The variation of hardenability has to be considered in control of the microstructures and distortion during gear quenching. In this paper, the quantitative effect of hardenability has been investigated on phase transformations of spiral bevel gears in die quenching. The hardenability deviation of 22CrMoH steel was assessed by using Jominy test. The dilatometry experiments were conducted to build phase transformation kinetic models for steels with low and high hardenability, respectively. The complete die quenching process of spiral bevel gear was modeled to reveal the significant difference on microstructures and temperature history with variation of hardenability. The final microstructures of the gear are martensite in surface layer after quenching process. There are bainite inside the gear tooth and the mixture of bainite and ferrite inside gear for the gear with low hardenability. The microstructure is bainite inside the gear with high hardenability.

  8. Role of Outer-Membrane Cytochromes MtrC and OmcA in the Biomineralization of Ferrihydrite by Shewanella oneidensis MR-1.

    SciTech Connect

    Reardon, Catherine L.; Dohnalkova, Alice; Nachimuthu, Ponnusamy; Kennedy, David W.; Saffarini, Daad; Arey, Bruce W.; Shi, Liang; Wang, Zheming; Moore, Dean A.; Mclean, Jeffrey S.; Moyles, Dianne M.; Marshall, Matthew J.; Zachara, John M.; Fredrickson, Jim K.; Beliaev, Alex S.

    2010-01-01

    In an effort to improve the understanding of electron transfer mechanisms at the microbe-mineral interface, Shewanella oneidensis MR-1 mutants with in-frame deletions of outer membrane cytochrome genes mtrC, omcA, or both, were characterized for the ability to reduce metal oxides using a suite of microscopic, spectroscopic, and biochemicalr techniques. The results indicate that neither MtrC nor OmcA are essential for the reduction of soluble, complexed Fe(III)-citrate or Fe(III)-NTA; however, at least one of these outer membrane cytochromes is required for the reduction of Fe(III)- and Mn(III/IV)- oxides. In vitro analysis of purified, recombinant protein demonstrated that both cytochromes transfer electrons directly to metal-oxides; however, MtrC transfers electrons at a faster rate than OmcA. Immunolocalization of MtrC and OmcA reveal that both cytochromes are surface-exposed on the cell outer-membrane and co-localize with insoluble iron precipitates when respiring ferrihydrite or cultured aerobically with Fe(III)-citrate. Additionally, during prolonged incubation, wild-type cells promoted biotransformation of ferrihydrite to vivianite [Fe3(PO4)2•8H2O] while the double cytochrome mutant was unable to form any secondary mineral phases. Collectively, our results support a role for direct electron transfer from OMCs to metal oxides by establishing their in vitro electron transfer activities, confirming the requirement of either MtrC or OmcA for in vivo reductive biomineralization of ferrihydrite, and localizing the cytochromes to the cell exterior where they can directly contact mineral substrates.

  9. Phase transformation upon cooling path in Ca2SiO4: Possible geological implication

    NASA Astrophysics Data System (ADS)

    Chang, Yun-Ting; Kung, Jennifer; Hsu, Han

    2016-04-01

    At the contact metamorphism zone two different Ca2SiO4 phases can be found; calcio-olivine (γ phase) and larnite (β phase). In-situ experiments illustrated the existence of five various polymorphs in Ca2SiO4, i.e., α, α'H, α'L, β and γ. The path of phase transformation and the transformation temperatures are shown as follows. γ → α'L(700° C) → α'H(1100° C) → α (1450° C) α'L → β (680° C) → γ (500° C) Experiments showed that the phase transitions at lower temperature is not reversible and seemed to be complicated; β phase is only stable from 500° C to 680° C upon cooling. To understand the possible mechanism of the β phase being metastable at room temperature, atmosphere condition, we were motivated to investigate the route of phase transition in Ca2SiO4 in different thermal process. Powder samples were synthesized by the solid-state reaction. Pure reagent oxides CaCO3 and SiO2 were mixed in 2:1 stoichiometric mole. Two control factors were designated in the experiments; the sintering temperature of starting materials and the cooling path. The sintering temperature was set within the range of stable phase field of α'L phase (˜900° C) and α'H phase (1300° C). The cooling process was designed in three different routes: 1) the quenched procedure from sintering temperature with rate of 900° C/min and 1300° C/min, 2) the furnace cooling procedure, 3) set a slow cooling rate (0.265 ° C/min). The products were examined for the crystal structure by X-ray powder diffraction. First-principle calculation was also applied to investigate the thermodynamic properties of α'H, β and γ phases. A major finding in this study showed that the γ phase presented in the final product when the sintering temperature was set at the stable field of α'H phase; on the other hand, the β phase would present when the sintering temperature was set within the field of α'L phase. It was noted that the existing phase in the product would be modified by the

  10. Liquid-Gas Relative Permeabilities in Fractures: Effects of Flow Structures, Phase Transformation and Surface Roughness

    SciTech Connect

    Chih-Ying Chen

    2005-06-30

    Two-phase flow through fractured media is important in petroleum, geothermal, and environmental applications. However, the actual physics and phenomena that occur inside fractures are poorly understood, and oversimplified relative permeability curves are commonly used in fractured reservoir simulations. In this work, an experimental apparatus equipped with a high-speed data acquisition system, real-time visualization, and automated image processing technology was constructed to study three transparent analog fractures with distinct surface roughnesses: smooth, homogeneously rough, and randomly rough. Air-water relative permeability measurements obtained in this study were compared with models suggested by earlier studies and analyzed by examining the flow structures. A method to evaluate the tortuosities induced by the blocking phase, namely the channel tortuosity, was proposed from observations of the flow structure images. The relationship between the coefficients of channel tortuosity and the relative permeabilities was studied with the aid of laboratory experiments and visualizations. Experimental data from these fractures were used to develop a broad approach for modeling two-phase flow behavior based on the flow structures. Finally, a general model deduced from these data was proposed to describe two-phase relative permeabilities in both smooth and rough fractures. For the theoretical analysis of liquid-vapor relative permeabilities, accounting for phase transformations, the inviscid bubble train models coupled with relative permeability concepts were developed. The phase transformation effects were evaluated by accounting for the molecular transport through liquid-vapor interfaces. For the steam water relative permeabilities, we conducted steam-water flow experiments in the same fractures as used for air-water experiments. We compared the flow behavior and relative permeability differences between two-phase flow with and without phase transformation effects

  11. Instrumental phase-based method for Fourier transform spectrometer measurements processing

    SciTech Connect

    Saggin, Bortolino; Scaccabarozzi, Diego; Tarabini, Marco

    2011-04-20

    Phase correction is a critical procedure for most space-borne Fourier transform spectrometers (FTSs) whose accuracy (owing to often poor signal-to-noise ratio, SNR) can be jeopardized from many uncontrollable environmental conditions. This work considers the phase correction in an FTS working under significant temperature change during the measurement and affected by mechanical disturbances. The implemented method is based on the identification of an instrumental phase that is dependent on the interferometer temperature and on the extraction of a linear phase component through a least-squares approach. The use of an instrumental phase parameterized with the interferometer temperature eases the determination of the linear phase that can be extracted using only a narrow spectral region selected to be immune from disturbances. The procedure, in this way, is made robust against phase errors arising from instrumental effects, a key feature to reduce the disturbances through spectra averaging. The method was specifically developed for the Mars IR Mapper spectrometer, that was designed for operation onboard a rover on the Mars surface; the validation was performed using ground and in-flight measurements of the Fourier transform IR spectrometer planetary Fourier spectrometer, onboard the MarsExpress mission. The symmetrization has been exploited also for the spectra calibration, highlighting the issues deriving from the cases of relevant beamsplitter emission. The applicability of this procedure to other instruments is conditional to the presence in the spectra of at least one spectral region with a large SNR along with a negligible (or known) beamsplitter emission. For the PFS instrument, the processing of data with relevant beamsplitter emission has been performed exploiting the absorption carbon dioxide bands present in Martian spectra.

  12. Instrumental phase-based method for Fourier transform spectrometer measurements processing.

    PubMed

    Saggin, Bortolino; Scaccabarozzi, Diego; Tarabini, Marco

    2011-04-20

    Phase correction is a critical procedure for most space-borne Fourier transform spectrometers (FTSs) whose accuracy (owing to often poor signal-to-noise ratio, SNR) can be jeopardized from many uncontrollable environmental conditions. This work considers the phase correction in an FTS working under significant temperature change during the measurement and affected by mechanical disturbances. The implemented method is based on the identification of an instrumental phase that is dependent on the interferometer temperature and on the extraction of a linear phase component through a least-squares approach. The use of an instrumental phase parameterized with the interferometer temperature eases the determination of the linear phase that can be extracted using only a narrow spectral region selected to be immune from disturbances. The procedure, in this way, is made robust against phase errors arising from instrumental effects, a key feature to reduce the disturbances through spectra averaging. The method was specifically developed for the Mars IR Mapper spectrometer, that was designed for operation onboard a rover on the Mars surface; the validation was performed using ground and in-flight measurements of the Fourier transform IR spectrometer planetary Fourier spectrometer, onboard the MarsExpress mission. The symmetrization has been exploited also for the spectra calibration, highlighting the issues deriving from the cases of relevant beamsplitter emission. The applicability of this procedure to other instruments is conditional to the presence in the spectra of at least one spectral region with a large SNR along with a negligible (or known) beamsplitter emission. For the PFS instrument, the processing of data with relevant beamsplitter emission has been performed exploiting the absorption carbon dioxide bands present in Martian spectra. PMID:21509063

  13. Instrumental phase-based method for Fourier transform spectrometer measurements processing.

    PubMed

    Saggin, Bortolino; Scaccabarozzi, Diego; Tarabini, Marco

    2011-04-20

    Phase correction is a critical procedure for most space-borne Fourier transform spectrometers (FTSs) whose accuracy (owing to often poor signal-to-noise ratio, SNR) can be jeopardized from many uncontrollable environmental conditions. This work considers the phase correction in an FTS working under significant temperature change during the measurement and affected by mechanical disturbances. The implemented method is based on the identification of an instrumental phase that is dependent on the interferometer temperature and on the extraction of a linear phase component through a least-squares approach. The use of an instrumental phase parameterized with the interferometer temperature eases the determination of the linear phase that can be extracted using only a narrow spectral region selected to be immune from disturbances. The procedure, in this way, is made robust against phase errors arising from instrumental effects, a key feature to reduce the disturbances through spectra averaging. The method was specifically developed for the Mars IR Mapper spectrometer, that was designed for operation onboard a rover on the Mars surface; the validation was performed using ground and in-flight measurements of the Fourier transform IR spectrometer planetary Fourier spectrometer, onboard the MarsExpress mission. The symmetrization has been exploited also for the spectra calibration, highlighting the issues deriving from the cases of relevant beamsplitter emission. The applicability of this procedure to other instruments is conditional to the presence in the spectra of at least one spectral region with a large SNR along with a negligible (or known) beamsplitter emission. For the PFS instrument, the processing of data with relevant beamsplitter emission has been performed exploiting the absorption carbon dioxide bands present in Martian spectra.

  14. High pressure phase-transformation induced texture evolution and strengthening in zirconium metal: Experiment and modeling

    DOE PAGESBeta

    Yu, Xiaohui; Zhang, Ruifeng; Weldon, David; Vogel, Sven C.; Zhang, Jianzhong; Brown, Donald W.; Wang, Yanbin; Reiche, Helmut M.; Wang, Shanmin; Du, Shiyu; et al

    2015-07-28

    We studied the phase-transition induced texture changes and strengthening mechanism for zirconium metal under quasi-hydrostatic compression and uni-axial deformation under confined high pressure using the deformation-DIA (D-DIA) apparatus. It is shown that the experimentally obtained texture for ω-phase Zr can be qualitatively described by combining a subset of orientation variants previously proposed in two different models. The determined flow stress for the high-pressure ω-phase is 0.5–1.2 GPa, more than three times higher than that of the α-phase. Using first-principles calculations, we investigated the mechanical and electronic properties of the two Zr polymorphs. We find that the observed strengthening can bemore » attributed to the relatively strong directional bonding in the ω phase, which significantly increases its shear plastic resistance over the α-phase Zr. The present findings provide an alternate route for Zr metal strengthening by high-pressure phase transformation.« less

  15. High pressure phase-transformation induced texture evolution and strengthening in zirconium metal: Experiment and modeling

    SciTech Connect

    Yu, Xiaohui; Zhang, Ruifeng; Weldon, David; Vogel, Sven C.; Zhang, Jianzhong; Brown, Donald W.; Wang, Yanbin; Reiche, Helmut M.; Wang, Shanmin; Du, Shiyu; Jin, Changqing; Zhao, Yusheng

    2015-07-28

    We studied the phase-transition induced texture changes and strengthening mechanism for zirconium metal under quasi-hydrostatic compression and uni-axial deformation under confined high pressure using the deformation-DIA (D-DIA) apparatus. It is shown that the experimentally obtained texture for ω-phase Zr can be qualitatively described by combining a subset of orientation variants previously proposed in two different models. The determined flow stress for the high-pressure ω-phase is 0.5–1.2 GPa, more than three times higher than that of the α-phase. Using first-principles calculations, we investigated the mechanical and electronic properties of the two Zr polymorphs. We find that the observed strengthening can be attributed to the relatively strong directional bonding in the ω phase, which significantly increases its shear plastic resistance over the α-phase Zr. The present findings provide an alternate route for Zr metal strengthening by high-pressure phase transformation.

  16. In-situ characterization of highly reversible phase transformation by synchrotron X-ray Laue microdiffraction

    NASA Astrophysics Data System (ADS)

    Chen, Xian; Tamura, Nobumichi; MacDowell, Alastair; James, Richard D.

    2016-05-01

    The alloy Cu25Au30Zn45 undergoes a huge first-order phase transformation (6% strain) and shows a high reversibility under thermal cycling and an unusual martensitc microstructure in sharp contrast to its nearby compositions. This alloy was discovered by systematically tuning the composition so that its lattice parameters satisfy the cofactor conditions (i.e., the kinematic conditions of compatibility between phases). It was conjectured that satisfaction of these conditions is responsible for the enhanced reversibility as well as the observed unusual fluid-like microstructure during transformation, but so far, there has been no direct evidence confirming that these observed microstructures are those predicted by the cofactor conditions. To verify this hypothesis, we use synchrotron X-ray Laue microdiffraction to measure the orientations and structural parameters of variants and phases near the austenite/martensite interface. The areas consisting of both austenite and multi-variants of martensite are scanned by microLaue diffraction. The cofactor conditions have been examined from the kinematic relation of lattice vectors across the interface. The continuity condition of the interface is precisely verified from the correspondent lattice vectors between two phases.

  17. Nanoalloying and phase transformations during thermal treatment of physical mixtures of Pd and Cu nanoparticles

    NASA Astrophysics Data System (ADS)

    Mukundan, Vineetha; Yin, Jun; Joseph, Pharrah; Luo, Jin; Shan, Shiyao; Zakharov, Dmitri N.; Zhong, Chuan-Jian; Malis, Oana

    2014-04-01

    Nanoscale alloying and phase transformations in physical mixtures of Pd and Cu ultrafine nanoparticles are investigated in real time with in situ synchrotron-based x-ray diffraction complemented by ex situ high-resolution transmission electron microscopy. The combination of metal-support interaction and reactive/non-reactive environment was found to determine the thermal evolution and ultimate structure of this binary system. At 300 °C, the nanoparticles supported on silica and carbon black intermix to form a chemically ordered CsCl-type (B2) alloy phase. The B2 phase transforms into a disordered fcc alloy at higher temperature (> 450 °C). The alloy nanoparticles supported on silica and carbon black are homogeneous in volume, but evidence was found of Pd surface enrichment. In sharp contrast, when supported on alumina, the two metals segregated at 300 °C to produce almost pure fcc Cu and Pd phases. Upon further annealing of the mixture on alumina above 600 °C, the two metals interdiffused, forming two distinct disordered alloys of compositions 30% and 90% Pd. The annealing atmosphere also plays a major role in the structural evolution of these bimetallic nanoparticles. The nanoparticles annealed in forming gas are larger than the nanoparticles annealing in helium due to reduction of the surface oxides that promotes coalescence and sintering.

  18. Geometric phase analysis based on the windowed Fourier transform for the deformation field measurement

    NASA Astrophysics Data System (ADS)

    Dai, Xianglu; Xie, Huimin; Wang, Qinghua

    2014-06-01

    The geometric phase analysis (GPA), an important image-based deformation measurement method, has been used at both micro- and nano-scale. However, when a deformed image has apparent distortion, non-ignorable error in the obtained deformation field could occur by using this method. In this paper, the geometric phase analysis based on the windowed Fourier transform (WFT) is proposed to solve the above-mentioned issue, defined as the WFT-GPA method. In WFT-GPA, instead of the Fourier transform (FT), the WFT is utilized to extract the phase field block by block, and therefore more accurate local phase information can be acquired. The simulation tests, which include detailed discussion of influence factors for measurement accuracy such as window size and image noise, are conducted with digital deformed grids. The results verify that the WFT-GPA method not only keeps all advantages of traditional GPA method, but also owns a better accuracy for deformation measurement. Finally, the WFT-GPA method is applied to measure the machining distortion incurred in soft ultraviolet nanoimprint lithography (UV-NIL) process. The successful measurement shows the feasibility of this method and offers a full-field way for characterizing the replication quality of UV-NIL process.

  19. Evidence for the temperature dependence of phase transformation behavior of silicon at nanoscale

    DOE PAGESBeta

    Mangalampalli S. R. N. Kiran; Tran, Tuan; Smillie, Lachlan; Haberl, Bianca; Subianto, D.; Williams, James S.; Bradby, Jodie E.

    2015-05-27

    This study uses the in-situ high-temperature nanoindentation coupled with electrical measurements to investigate the temperature dependence (25 to 200 C) of the phase transformation behavior of crystalline silicon (dc-Si) at the nanoscale. Along with in-situ indentation and electrical data, ex-situ characterizations such as Raman and cross-sectional transmission electron microscopy (XTEM) have been used to reveal the dominant mode of deformation under the indenter. In contrast to the previous studies, the dominant mode of deformation under the nanoindenter at elevated temperatures is not the dc-Si to metallic phase ( -Sn) transformation. Instead, XTEM images from 150 C indents reveal that themore » dominant mode of deformation is twinning along {111} planes. While the in-situ high-temperature electrical measurements show an increase in the current due to metallic phase formation up to 125 C, it is absent 150 C, revealing that the formation of the metallic phase is negligible in this regime. Thus, this work provides clear insight into the temperature dependent deformation mechanisms in dc-Si at the nanoscale.« less

  20. Deformation and Phase Transformations During Cyclic Oxidation of Ni-Al and Ni-Pt-Al

    SciTech Connect

    Pint, Bruce A; Speakman, Scott A; Rawn, Claudia J; Zhang, Ying

    2006-01-01

    The reversible high-temperature {gamma}' to {beta} phase transformation may be critical to explaining the unusual high-temperature oxidation behavior of (Ni,Pt)Al alloys and coatings. During high-temperature, high-frequency (1 h) cyclic oxidation in dry, flowing O{sub 2}, unprecedented macroscopic deformation was observed in two-phase ({gamma}'+{beta}) cast specimens of Hf-doped Ni-Al at 1,150 C and Hf-doped Ni-Pt-Al at 1,100 and 1,150 C, Outside of this two-phase field or when the cycle frequency was decreased to 100h, no deformation was observed. Using high-temperature x-ray diffraction in an inert environment, the {beta}-to-{gamma}' phase ratio was observed to increase above 1,000 C, causing a 2.5% volume change. The addition of platinum appeared to lower the transformation temperature consistent with the deformation observed in castalloys and rumpling of simple and platinum-modified aluminide coatings.

  1. Evidence for the temperature dependence of phase transformation behavior of silicon at nanoscale

    SciTech Connect

    Mangalampalli S. R. N. Kiran; Tran, Tuan; Smillie, Lachlan; Haberl, Bianca; Subianto, D.; Williams, James S.; Bradby, Jodie E.

    2015-05-27

    This study uses the in-situ high-temperature nanoindentation coupled with electrical measurements to investigate the temperature dependence (25 to 200 C) of the phase transformation behavior of crystalline silicon (dc-Si) at the nanoscale. Along with in-situ indentation and electrical data, ex-situ characterizations such as Raman and cross-sectional transmission electron microscopy (XTEM) have been used to reveal the dominant mode of deformation under the indenter. In contrast to the previous studies, the dominant mode of deformation under the nanoindenter at elevated temperatures is not the dc-Si to metallic phase ( -Sn) transformation. Instead, XTEM images from 150 C indents reveal that the dominant mode of deformation is twinning along {111} planes. While the in-situ high-temperature electrical measurements show an increase in the current due to metallic phase formation up to 125 C, it is absent 150 C, revealing that the formation of the metallic phase is negligible in this regime. Thus, this work provides clear insight into the temperature dependent deformation mechanisms in dc-Si at the nanoscale.

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

    SciTech Connect

    Feng, Kai; Wang, Yibo; Li, Zhuguo; Chu, Paul K.

    2015-08-15

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

  3. Carbonate component reduces o,oEDDHA/Fe sorption on two-line ferrihydrite

    NASA Astrophysics Data System (ADS)

    Yunta, F.; Lucena, J. J.; Smolders, E.

    2012-04-01

    The o,oEDDHA/Fe is the most common and effective iron chelate used as fertilizer in calcareous soils. Several authors have reported that the anionic o,oEDDHA/Fe complex is adsorbed to soil components such as ferrihydrite. The bicarbonate anion may be a competing ion for this sorption, however no studies have yet identified the extent and mechanism of this interaction. The aim of this work was to study the carbonate (bicarbonate + carbonate) effect on EDDHA/Fe adsorption on two-line ferrihydrite. Two-line ferrihydrite was synthetized adding NaOH on a nitrate iron (III) solution up to a final pH to be 8.0 and allowing to age for 22 hours at 20°C. Dialyzed ferrihydrite was characterized by determining specific parameters such as Fe/OH ratio, BET surface, point zero of charge and x-ray diffraction. The sorption was performed at three pH levels (5, 7.5 and 9.5) and three initial carbonate concentrations (from 0 to 2 mM). Initial EDDHA/Fe, ferrihydrite and ionic strength concentrations were adjusted to 0.18 mM, 10 g L-1 and 5 mM respectively. Total dissolved FeEDDHA concentrations were quantified at 480 nm. The o,oEDDHA/Fe isomers (rac-o,oEDDHA/Fe and meso-o,oEDDHA/Fe) were separated and quantified by High Performance Liquid Chromatography (HPLC) fitting a photodiode array detector (PDA). Distribution factor (KD) and sorbed o,oEDDHA/Fe concentration were determined. Actual carbonate concentration was determined using a multi N/C analyzer. Ferrihydrite samples showed a typical XRD pattern of two-line ferrihydrite, two broad peaks at about 35 and 62° respectively. The BET surfaces (two replicates) were 259.2 ± 3.1 m2/g and 256.0 ± 2.5 m2/g. The Point Zero of Salt Effect (PZSE) was 7.9 ± 0.2 as bibliographically supported for all fresh and thus not rigorously de-carbonated ferrihydrite samples. The KD of the o,oEDDHA/Fe increased from 27.4 ± 0.6 to 304 ± 6 l/kg by decreasing pH from 9.5 and 5.0 when no carbonate was added. Increasing equilibrium carbonate

  4. The mechansims by which solute nitrogen affects phase transformations and mechanical properties of automotive dual-phase sheet steel

    NASA Astrophysics Data System (ADS)

    Brown, Tyson W.

    Dual-phase steels have seen increased use in automotive applications in recent years, in order to meet the goals of weight reduction and occupant safety. Variations in nitrogen content that may be encountered in steel sourced from a basic oxygen furnace process compared to an electric arc furnace process require that dual-phase steel producers understand the ways that nitrogen affects processing and properties. In the current work, the distribution of nitrogen was investigated in a dual-phase steel with a base chemistry of 0.1 C, 2.0 Mn, 0.2 Cr, 0.2 Mo (wt pct) across a range of nitrogen contents (30-159 ppm) with Al (0.2 and 0.08 wt pct), and Ti (0.02 wt pct) additions used for precipitation control of nitrogen amounts. The distribution of nitrogen amongst trapping sites, including precipitates, grain boundaries, dislocations, and interstitial sites (away from other types of defects) was determined from a combination of electrolytic dissolution, internal friction, and three-dimensional atom probe tomography experiments. Various mechanisms by which different amounts and locations of nitrogen affect phase transformations and mechanical properties were identified from quantitative metallography, dilatometric measurement of phase transformations, tensile testing, and nanoindentation hardness testing. Results indicate nitrogen that is not precipitated with Ti or Al (free nitrogen) partitions to austenite (and thus martensite) during typical intercritical annealing treatments, and is mostly contained in Cottrell atmospheres in martensite. Due to the austenite stabilizing effect of nitrogen, the presence of free nitrogen during intercritical annealing leads to a higher austenite fraction in certain conditions. Thus, the presence of free nitrogen in a dual-phase microstructure will lead to an increase in tensile and yield strengths from both an increase in martensite fraction, and an increase in martensite hardness due to solid solution strengthening. Despite the presence

  5. Identification of Defect Prone Peritectic Steel Grades by Analyzing High-Temperature Phase Transformations

    NASA Astrophysics Data System (ADS)

    Presoly, Peter; Pierer, Robert; Bernhard, Christian

    2013-12-01

    Continuous casting of peritectic steels is often difficult and critical; bad surface quality, cracks, and even breakouts may occur. The initial solidification of peritectic steels within the mold leads to formation of surface depressions and uneven shell growth. As commercial steels are always multicomponent alloys, the influence also of the alloying elements besides carbon on the peritectic phase transition needs to be taken into account. Information on the solidification sequence and phase diagrams for initial solidification are lacking especially for new steel grades, like high-alloyed TRIP-steels with high Mn, Si, and particularly high Al contents. Based on a comprehensive method development, the current study shows that differential scanning calorimeter measurements allow a clear prediction if an alloy is peritectic ( i.e., critical to cast). In order to confirm these results, thermo-optical analyses with a high-temperature laser-scanning-confocal-microscope are performed to observe the phase transformations in situ up to the melting point.

  6. Novel copyright information hiding method based on random phase matrix of Fresnel diffraction transforms

    NASA Astrophysics Data System (ADS)

    Cao, Chao; Chen, Ru-jun

    2009-10-01

    In this paper, we present a new copyright information hide method for digital images in Moiré fringe formats. The copyright information is embedded into the protected image and the detecting image based on Fresnel phase matrix. Firstly, using Fresnel diffraction transform, the random phase matrix of copyright information is generated. Then, according to Moiré fringe principle, the protected image and the detecting image are modulated respectively based on the random phase matrix, and the copyright information is embedded into them. When the protected image and the detecting image are overlapped, the copyright information can reappear. Experiment results show that our method has good concealment performance, and is a new way for copyright protection.

  7. Fourier transform infrared study of a phase transition in solid chlorodifluoromethane

    NASA Astrophysics Data System (ADS)

    Anderson, A.; Beardsall, A. J.; Fraser, Jim

    1994-01-01

    Infrared spectra of solid chlorodifluoromethane (CHClF2 or Freon 22) at temperatures between 12 K and 105 K have been recorded. Both lattice and internal mode regions have been investigated by utilizing two Fourier transform spectrometers, one for the far-infrared region (20 - 400 cm-1) and the other for the mid-infrared region (400 - 4000 cm-1). Evidence for a solid state phase transition at 55 +/- 5 K is presented. Multiplet structure for the nine internal modes is observed over a wide range of temperature and in most cases is shown to result from crystal field rather than isotopic or other effects. This indicates that both phases are ordered with rather large unit cells, and that the phase transition is therefore of a displacive type.

  8. ISAR Imaging of Maneuvering Targets Based on the Modified Discrete Polynomial-Phase Transform.

    PubMed

    Wang, Yong; Abdelkader, Ali Cherif; Zhao, Bin; Wang, Jinxiang

    2015-01-01

    Inverse synthetic aperture radar (ISAR) imaging of a maneuvering target is a challenging task in the field of radar signal processing. The azimuth echo can be characterized as a multi-component polynomial phase signal (PPS) after the translational compensation, and the high quality ISAR images can be obtained by the parameters estimation of it combined with the Range-Instantaneous-Doppler (RID) technique. In this paper, a novel parameters estimation algorithm of the multi-component PPS with order three (cubic phase signal-CPS) based on the modified discrete polynomial-phase transform (MDPT) is proposed, and the corresponding new ISAR imaging algorithm is presented consequently. This algorithm is efficient and accurate to generate a focused ISAR image, and the results of real data demonstrate the effectiveness of it. PMID:26404299

  9. Small interfering ribonucleic acid induces liquid-to-ripple phase transformation in a phospholipid membrane

    SciTech Connect

    Choubey, Amit; Nomura, Ken-ichi; Kalia, Rajiv K.; Nakano, Aiichiro; Vashishta, Priya

    2014-09-15

    Small interfering ribonucleic acid (siRNA) molecules play a pivotal role in silencing gene expression via the RNA interference mechanism. A key limitation to the widespread implementation of siRNA therapeutics is the difficulty of delivering siRNA-based drugs to cells. Here, we examine changes in the structure and dynamics of a dipalmitoylphosphatidylcholine bilayer in the presence of a siRNA molecule and mechanical barriers to siRNA transfection in the bilayer. Our all-atom molecular dynamics simulation shows that siRNA induces a liquid crystalline-to-ripple phase transformation in the bilayer. The ripple phase consists of a major region of non-interdigitated and a minor region of interdigitated lipid molecules with an intervening kink. In the ripple phase, hydrocarbon chains of lipid molecules have large compressive stresses, which present a considerable barrier to siRNA transfection.

  10. ISAR Imaging of Maneuvering Targets Based on the Modified Discrete Polynomial-Phase Transform

    PubMed Central

    Wang, Yong; Abdelkader, Ali Cherif; Zhao, Bin; Wang, Jinxiang

    2015-01-01

    Inverse synthetic aperture radar (ISAR) imaging of a maneuvering target is a challenging task in the field of radar signal processing. The azimuth echo can be characterized as a multi-component polynomial phase signal (PPS) after the translational compensation, and the high quality ISAR images can be obtained by the parameters estimation of it combined with the Range-Instantaneous-Doppler (RID) technique. In this paper, a novel parameters estimation algorithm of the multi-component PPS with order three (cubic phase signal-CPS) based on the modified discrete polynomial-phase transform (MDPT) is proposed, and the corresponding new ISAR imaging algorithm is presented consequently. This algorithm is efficient and accurate to generate a focused ISAR image, and the results of real data demonstrate the effectiveness of it. PMID:26404299

  11. Phase transformation behavior in a multipurpose dental casting gold alloy during continuous heating.

    PubMed

    Kim, H I; Seol, H J; Hisatsune, K; Htain-Winn; Sakrana, A A; Takuma, Y; Kawasaki, K

    2000-01-01

    Phase transformation in a multipurpose dental casting gold alloy during continuous heating was studied by electrical resistivity measurements, hardness tests, X-ray diffraction and scanning and transmission electron microscopy. The behavior can be explained by the following reaction sequences in the nodule: alpha1(fcc) + alpha2(L1(2)) --> alpha1(fcc) + alpha2(L1(2)) + beta(L1(0)), where fcc is face centred cubic. A discontinuous precipitation with very fine nodules contributed to the hardening and the growth produced the softening. This multipurpose gold alloy is characterized by the introduction of a PtZn ordered phase with L1(0) structure instead of a CuAu I phase.

  12. Fatigue properties of a metastable beta-type titanium alloy with reversible phase transformation.

    PubMed

    Li, S J; Cui, T C; Hao, Y L; Yang, R

    2008-03-01

    Due to recent concern about allergic and toxic effects of Ni ions released from TiNi alloy into human body, much attention has been focused on the development of new Ni-free, metastable beta-type biomedical titanium alloys with a reversible phase transformation between the beta phase and the alpha'' martensite. This study investigates the effect of the stress-induced alpha'' martensite on the mechanical and fatigue properties of Ti-24Nb-4Zr-7.6Sn (wt.%) alloy. The results show that the as-forged alloy has a low dynamic Young's modulus of 55GPa and a recoverable tensile strain of approximately 3%. Compared with Ti-6Al-4V ELI, the studied alloy has quite a high low-cycle fatigue strength because of the effective suppression of microplastic deformation by the reversible martensitic transformation. Due to the low critical stress required to induce the martensitic transformation, it has low fatigue endurance comparable to that of Ti-6Al-4V ELI. Cold rolling produces a beta+alpha'' two-phase microstructure that is characterized by regions of nano-size beta grains interspersed with coarse grains containing alpha'' martensite plates. Cold rolling increases fatigue endurance by approximately 50% while decreasing the Young's modulus to 49GPa along the rolling direction but increasing it to 68GPa along the transverse direction. Due to the effective suppression of the brittle isothermal omega phase, balanced properties of high strength, low Young's modulus and good ductility can be achieved through ageing treatment at intermediate temperature.

  13. Development of a carburizing and quenching simulation tool: A material model for low carbon steels undergoing phase transformations

    SciTech Connect

    Bammann, D.; Prantil, V.; Kumar, A.

    1996-06-24

    An internal state variable formulation for phase transforming alloy steels is presented. We have illustrated how local transformation plasticity can be accommodated by an appropriate choice for the corresponding internal stress field acting between the phases. The state variable framework compares well with a numerical micromechanical calculation providing a discrete dependence of microscopic plasticity on volume fraction and the stress dependence attributable to a softer parent phase. The multiphase model is used to simulate the stress state of a quenched bar and show qualitative trends in the response when the transformation phenomenon is incorporated on the length scale of a global boundary value problem.

  14. Limited reduction of ferrihydrite encrusted by goethite in freshwater sediment.

    PubMed

    Kikuchi, S; Makita, H; Konno, U; Shiraishi, F; Ijiri, A; Takai, K; Maeda, M; Takahashi, Y

    2016-07-01

    Many physical and chemical processes control the extent of Fe(III) oxyhydroxide reduction by dissimilatory Fe(III)-reducing bacteria. The surface precipitation of secondary Fe minerals on Fe(III) oxyhydroxides limits the extent of microbial Fe(III) reduction, but this phenomenon has not yet been observed in nature. This paper reports the observation of secondary Fe-mineral (goethite) encrustation on ferrihydrite surface within freshwater sediment up to 10 cm deep. The sediment surface was characterized by the predominance of ferrihydrites with biogenic stalks and sheaths. An Fe(II)-oxidizing bacterium (Gallionellaceae) was detected by 16S rRNA gene analysis at sediment depths of 1 and 2 cm. Fe(2+) concentration in the sediment pore water was relatively higher at 2-4 cm depths. The 16S rRNA genes affiliated with dissimilatory Fe(III)-reducing bacteria were detected at 1, 2, and 4 cm depths. The results of the Fe K-edge extended X-ray absorption fine structure (EXAFS) analysis suggested the presence of goethite and siderite at depths below 3 cm. However, the change in the Fe-mineral composition was restricted to sediment depths between 3 and 4 cm, despite the presence of abundant ferrihydrite at depths below 4 cm. An increase in CH4 concentration was observed at deeper than 6 cm. Stable isotopic analysis of CH4 in the pore water indicated that acetoclastic CH4 occurred at depths below 7 cm. Transmission electron microscope observations suggested the presence of goethite and siderite on stalks and sheaths at depths below 3 cm. Results from conversion electron yield EXAFS analysis suggested that goethite dominated at 10 cm depth, thereby indicating that ferrihydrite was encrusted by goethite at this depth. Moreover, the incomplete reduction of ferrihydrite below depths of 4 cm was not due to the lack of organic carbon, but was possibly due to the surface encrustation of goethite on ferrihydrite. PMID:27027643

  15. An investigation of phase transformation of titania slag using microwave heating

    NASA Astrophysics Data System (ADS)

    Chen, Guo; Chen, Jin; Peng, Jinhui

    2016-09-01

    The influences of microwave heating on the phase transformation of titania slag were systematically investigated. The thermal stability, surface chemical functional groups and microstructure of the titania slag before and after microwave heating, at a temperature of 950 °C for 60 min, were also analyzed using thermogravimetry and differential thermal analysis (TG-DSC), Fourier transform infrared spectroscopy (FT-IR) spectrum and scanning electron microscope (SEM), respectively. The TG-DSC analysis revealed that the phase transformation of the titania slag from anatase TiO2 to rutile TiO2 occurred between 750 and 1000 °C. The FT-IR rustles demonstrate that the banding form of Ti4+, Ti3+ and Ti2+ ions and the methyl groups on the surface of the titania slag has changed and a new chemical bond Ti-OH was formed. The results of SEM showed that a large number of regulation rutile TiO2 crystals were found on the surface of the microwave-treated samples and the synthetic rutile has been synthesized successfully using microwave heating.

  16. Structural and optical properties of short peptides: nanotubes-to-nanofibers phase transformation.

    PubMed

    Handelman, Amir; Natan, Amir; Rosenman, Gil

    2014-07-01

    Thermally induced phase transformation in bioorganic nanotubes, which self-assembled from two ultrashort dipeptides of different origin, aromatic diphenylalanine (FF) and aliphatic dileucine (LL), is studied. In both FF and LL nanotubes, irreversible phase transformation found at 120-180 °C is governed by linear-to-cyclic dipeptide molecular modification followed by formation of extended β-sheet structure. As a result of this process, native open-end FF and LL nanotubes are transformed into ultrathin nanofibrils. Found deep reconstructions at all levels from macroscopic (morphology) and structural space symmetry to molecular give rise to new optical properties in both aromatic FF and aliphatic LL nanofibrils and generation of blue photoluminescence (PL) emission. It is shown that observed blue PL peak is similar in these supramolecular nanofibrillar structures and is excited by the network of non-covalent hydrogen bonds that link newly thermally induced neighboring cyclic dipeptide strands to final extended β-sheet structure of amyloid-like nanofibrils. The observed blue PL peak in short dipeptide nanofibrils is similar to the blue PL peak that was recently found in amyloid fibrils and can be considered as the optical signature of β-sheet structures. Nanotubular structures were characterized by environmental scanning electron microscope, ToF-secondary ion mass spectroscopy, CD and fluorescence spectroscopy.

  17. In-situ Phase Transformation and Deformation of Iron at High Pressure andTemperature

    SciTech Connect

    Miyagi, Lowell; Kunz, Martin; Knight, Jason; Nasiatka, James; Voltolini, Marco; Wenk, Hans-Rudolf

    2008-07-01

    With a membrane based mechanism to allow for pressure change of a sample in aradial diffraction diamond anvil cell (rDAC) and simultaneous infra-red laser heating, itis now possible to investigate texture changes during deformation and phasetransformations over a wide range of temperature-pressure conditions. The device isused to study bcc (alpha), fcc (gamma) and hcp (epislon) iron. In bcc iron, room temperature compression generates a texture characterized by (100) and (111) poles parallel to the compression direction. During the deformation induced phase transformation to hcp iron, a subset of orientations are favored to transform to the hcp structure first and generate a texture of (01-10) at high angles to the compression direction. Upon further deformation, the remaining grains transform, resulting in a texture that obeys the Burgers relationship of (110)bcc // (0001)hcp. This is in contrast to high temperature results that indicate that texture is developed through dominant pyramidal {2-1-12}<2-1-13> and basal (0001)-{2-1-10} slip based on polycrystal plasticity modeling. We also observe that the high temperature fcc phase develops a 110 texture typical for fcc metals deformed in compression.

  18. Deformation and phase transformation in nano single crystals - when will nano crystals start to behave strangely?

    NASA Astrophysics Data System (ADS)

    Qi, Yue

    2002-03-01

    Single nanocrystals exhibit thermodynamic and mechanical properties that markedly differ from bulk materials due to the large free surface and small size. To highlight some key differences between these materials, we conducted molecular dynamics (MD) studies of a phase transformation process in Ni clusters and high strain rate deformation of Ni, NiCu, and NiAu nanowires. For our phase transformation studies, we examined Ni nanoclusters, ranging from one hundred atoms up to 8007 atoms. We found a transition from nanoscrystalline behavior (where bulk and surface properties are well defined) to molecular behavior between clusters of 750 atoms and 300 atoms. Cooling from the melt led to FCC grains for clusters with N>500, and an icosahedral structure for smaller clusters. For our nanowire deformation studies, we considered pure Ni, NiCu and NiAu alloys under high uniaxial tensile strain rates. We found that deformation proceeds through twinning and coherent slipping mechanisms at lower strain rates, and amorphization at higher strain rates. We also found that the critical strain rate, beyond which the crystal transforms to a glassy state, depends on the glass formability of the alloy. Thus, a new process for forming amorphous metals, which involves the application of rapid strain rates, is proposed.

  19. Kinetics of hexacelsian to celsian phase transformation in SrAl2Si2O8

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Drummond, Charles H., III

    1992-01-01

    The kinetics of hexacelsian to celsian phase transformation in SrAl2Si2O8 have been investigated. Phase pure hexacelsian was prepared by heat treatment of glass flakes at 990 C for 10 h. Bulk hexacelsian was isothermally heat treated at 1026, 1050, 1100, 1152, and 1200 C for various times. The amounts of monoclinic celsian formed were determined using quantitative X-ray diffraction. Values of reaction rate constant, k, at various temperatures were evaluated from the Avrami equation. The Avrami parameter was determined to be 1.1, suggesting a diffusionless, one-dimensional transformation mechanism. From the temperature dependence of k, the activation energy for this reaction was evaluated to be 527 plus or minus 50 kJ/mole (126 plus or minus 12 kcal/mole). This value is consistent with a mechanism involving the transformation of the layered hexacelsian structure to a three-dimensional network celsian structure which necessitates breaking of the strongest bonds, the Si-O bonds.

  20. Identification of material parameters for continuum modeling of phase transformations in multicomponent systems

    NASA Astrophysics Data System (ADS)

    Umantsev, Alex

    2007-01-01

    The continuum (field theoretic) method has become the method of choice for multiscale structure-formation modeling of very different phase transformations in the past decade. One of the challenges in application of the method to transformations in real materials is to obtain the mesoscopic parameters, which characterize the thermodynamic system of interest. Significant progress has been made in the case of pure systems; however, one would like to know what changes need to be made in the case of binary or multicomponent systems. We consider an exactly solvable case of the linear multicomponent system undergoing a phase transformation and derive equations that relate parameters of the continuum method, like barrier height, gradient energy, and relaxation coefficients, to the measurable quantities, like interface energy, interfacial thickness, and kinetic coefficient. We find that the contribution of chemical interactions in the system can be expressed as the renormalization of the barrier-height parameter of the continuum method and replacement of the latent heat with the chemical modulus. Atomic-scale simulations data for a solid/liquid transition in a binary Cu-Ni system were chosen for comparison with the theory and the fitting yields the estimates for the continuum-method parameters. Analysis of the temperature dependence of the interfacial energy allowed us to shed light on the magnitudes of the internal energy and entropy contributions into the solid/liquid interface.

  1. Phase transformations of sputtered ZrV{sub 2} films after annealing and hydrogenation

    SciTech Connect

    Shi, L.Q.; Xu, S.L.

    2006-03-15

    ZrV{sub 2} thin films were prepared using a direct current (dc)-magnetron-sputtering method. The composition and the phase structure after annealing and hydrogenation were investigated by Rutherford backscattering and x-ray-diffraction technologies. The composition of the films deposited at different substrate temperatures are uniformly distributed along the depth of films. The amorphous phase consisting of Zr and V atoms was achieved when the substrate temperature was less than 400 deg. C. But at high temperatures, e.g., 600 deg. C, the multiphase mixture consisted of C14 (MgZn{sub 2}) and C15 (MgCu{sub 2}) Laves phases, Zr{sub 3}V{sub 3}O, {alpha}-Zr, and V forms. The annealing caused the segregation of Zr and V in the film by strain-driven diffusion and leads to nonhomogeneity, which is the main reason why the multiphase coexists there. With increasing annealing temperature, the amount of the stable C15 phase increases, while the amount of the other C14, {alpha}-Zr, and V phases decreases. Hydrogenation could spur phase transformation from the multiphase structure to a stable Laves structure at relatively low temperature.

  2. Structural transformation of Sb-based high-speed phase-change material.

    PubMed

    Matsunaga, Toshiyuki; Kojima, Rie; Yamada, Noboru; Kubota, Yoshiki; Kifune, Kouichi

    2012-12-01

    The crystal structure of a phase-change recording material (the compound Ag(3.4)In(3.7)Sb(76.4)Te(16.5)) enclosed in a vacuum capillary tube was investigated at various temperatures in a heating process using a large Debye-Scherrer camera installed in BL02B2 at SPring-8. The amorphous phase of this material turns into a crystalline phase at around 416 K; this crystalline phase has an A7-type structure with atoms of Ag, In, Sb or Te randomly occupying the 6c site in the space group. This structure was maintained up to around 545 K as a single phase, although thermal expansion of the crystal lattice was observed. However, above this temperature, phase separation into AgInTe(2) and Sb-Te transpired. The first fragment, AgInTe(2), reliably maintained its crystal structure up to the melting temperature. On the other hand, the atomic configuration of the Sb-Te gradually varied with increasing temperature. This gradual structural transformation can be described as a continuous growth of the modulation period γ. PMID:23165592

  3. Characterization of solid phases and study of transformation kinetics in m-chlorofluorobenzene by 35Cl nuclear quadrupole resonance.

    PubMed

    Pérez, Silvina; Wolfenson, Alberto

    2012-02-01

    Polymorphism is of widespread occurrence in the world of molecular crystals. In this work we present experimental results showing the existence of four solid phases in m-chlorofluorobenzene. A glass structure is achieved by quenching the liquid phase at 77 K. This glassy state crystallizes in a disordered phase at T~143 K, which in turn transforms to the high-temperature stable phase (phase I) at T~153 K. Depending on the thermal history of the sample, a different ordered phase (phase III) can be obtained. The disorder is attributed to a molecular orientational disorder. There is no evidence of molecular reorientation in any phase. A study of the disorder-order phase transformation kinetics, using nuclear quadrupole resonance, is presented. The results are analyzed following Cahn's theory. Nucleation seems to take place at grain boundaries. Growth rates for different temperatures have been determined.

  4. Uptake and release of cerium during Fe-oxide formation and transformation in Fe(II) solutions.

    PubMed

    Nedel, S; Dideriksen, K; Christiansen, B C; Bovet, N; Stipp, S L S

    2010-06-15

    Fe-oxides are ubiquitous in soils and sediments and form during Fe(0) corrosion. Depending on redox conditions and solution composition, Fe-oxides such as ferrihydrite, goethite, magnetite, and green rust (GR) may form. These phases typically have high surface area and large affinity for adsorption of trace components. Further, Fe(II)-Fe(III) (hydr)oxides are redox active. Cerium, a member of the lanthanide family, can be used as an analogue for the tri- and tetra-valent actinides found in radioactive waste, expected to be stored in subsurface repositories. In experiments with ferrihydrite, Ce(III) was effectively scavenged from Fe(II)-bearing solutions within 5 min at pH 7. During transformation of ferrihydrite to green rust, however, all Ce(III) was released to solution. By varying initial solution Fe(II):Fe(III) ratio, magnetite and goethite formed together with GR(Na,SO(4)), resulting in decreased Ce(III) release. X-ray photoelectron spectroscopy revealed Ce(III) adsorbed on magnetite. When Fe-oxides were synthesized by air oxidation of Fe(II) solutions at pH 7, GR(Na,SO(4)) played a catalytic role in the oxidation of Ce(III) to Ce(IV) by O(2), removing more than 90% of the dissolved Ce. Transmission electron microscopy revealed that it formed discrete nanocrystals of CeO(2(s)). These results demonstrate that Fe-oxide interaction with radionuclides is likely to depend strongly on the local redox conditions. By analogy with Ce, the trivalent actinides are not expected to be sequestered by preformed GR in anoxic environments. Our results also suggest that trivalent actinides and lanthanides are released when dissimilatory iron reduction of Fe(III)-oxides leads to GR formation However, under oxidizing conditions, GR may influence radionuclide mobility by catalyzing their transformation to a higher oxidation state. PMID:20496931

  5. 1D linear-phase band-pass multiplierless FIR Hilbert transformers and filters

    NASA Astrophysics Data System (ADS)

    Pavlović, Vlastimir D.; Dončov, Nebojša S.; Ćirić, Dejan G.

    2016-06-01

    An original analytical method, based on modified Christoffel-Darboux formula, is used in the paper in order to synthesise a linear-phase band-pass finite impulse response (FIR) filter function that can have an effect of Hilbert transformer. New structure of the band-pass FIR filter in recursive realisation, together with the corresponding difference equation, is presented providing the efficient filter solution without multipliers. Several examples of filter types for different parity of two real free integer parameters, including a particular solution of Hilbert transformer, are considered in terms of required number of adders and values of cut-off frequencies of the pass and stop bands. A comparison of the proposed band-pass filter characteristics with those of a classical filter solution is provided in the paper.

  6. Cost-Optimal Design of a 3-Phase Core Type Transformer by Gradient Search Technique

    NASA Astrophysics Data System (ADS)

    Basak, R.; Das, A.; Sensarma, A. K.; Sanyal, A. N.

    2014-04-01

    3-phase core type transformers are extensively used as power and distribution transformers in power system and their cost is a sizable proportion of the total system cost. Therefore they should be designed cost-optimally. The design methodology for reaching cost-optimality has been discussed in details by authors like Ramamoorty. It has also been discussed in brief in some of the text-books of electrical design. The paper gives a method for optimizing design, in presence of constraints specified by the customer and the regulatory authorities, through gradient search technique. The starting point has been chosen within the allowable parameter space the steepest decent path has been followed for convergence. The step length has been judiciously chosen and the program has been maneuvered to avoid local minimal points. The method appears to be best as its convergence is quickest amongst different optimizing techniques.

  7. Phase transformations and the spectral reflectance of solid sulfur - Can metastable sulfur allotropes exist on Io?

    NASA Technical Reports Server (NTRS)

    Moses, Julianne I.; Nash, Douglas B.

    1991-01-01

    Laboratory investigations have been conducted on the effects of variations in sulfur sample histories on their solid-state transformation rate and the corresponding spectral variation of freshly frozen sulfur. The temporal variations in question may be due to differences in the amount and type of metastable allotropes present in the sulfur after solidification, as well as to the physics of the phase-transformation process itself. The results obtained are pertinent to the physical behavior and spectral variation of such freshly solidified sulfur as may exist on the Jupiter moon Io; this would initially solidify into a glassy solid or monoclinic crystalline lattice, then approach ambient dayside temperatures. Laboratory results imply that the monoclinic or polymeric allotropes can in these circumstances be maintained, and will take years to convert to the stable orthorhombic crystalline form.

  8. Phase Transformation Theory, a Powerful Tool for the Design of Advanced Steels

    SciTech Connect

    Caballero, Francesca G.; Miller, Michael K; Garcia-Mateo, C.; Capdevila, C.; Garcia de Andres, C

    2008-01-01

    An innovative design procedure based on phase transformation theory alone has been successfully applied to design steels with a microstructure consisting of a mixture of bainitic ferrite, retained austenite, and some martensite. An increase in the amount of bainitic ferrite is needed in order to avoid the presence of large regions of untransformed austenite, which under stress decompose to brittle martensite. The design procedure addresses this difficulty by adjusting the T'o curve to greater carbon concentrations with the use of substitutional solutes such as manganese and chromium. The concepts of bainite transformation theory can be exploited even further to design steels with strength in excess of 2.5 GPa and considerable toughness.

  9. Thermodynamic Modelling of Phase Transformation in a Multi-Component System

    SciTech Connect

    Vala, J.

    2007-09-06

    Diffusion in multi-component alloys can be characterized by the vacancy mechanism for substitutional components, by the existence of sources and sinks for vacancies and by the motion of atoms of interstitial components. The description of diffusive and massive phase transformation of a multi-component system is based on the thermodynamic extremal principle by Onsager; the finite thickness of the interface between both phases is respected. The resulting system of partial differential equations of evolution with integral terms for unknown mole fractions (and additional variables in case of non-ideal sources and sinks for vacancies), can be analyzed using the method of lines and the finite difference technique (or, alternatively, the finite element one) together with the semi-analytic and numerical integration formulae and with certain iteration procedure, making use of the spectral properties of linear operators. The original software code for the numerical evaluation of solutions of such systems, written in MATLAB, offers a chance to simulate various real processes of diffusional phase transformation. Some results for the (nearly) steady-state real processes in substitutional alloys have been published yet. The aim of this paper is to demonstrate that the same approach can handle both substitutional and interstitial components even in case of a general system of evolution.

  10. Copper-zirconium tungstate composites exhibiting low and negative thermal expansion influenced by reinforcement phase transformations

    NASA Astrophysics Data System (ADS)

    Balch, Dorian K.; Dunand, David C.

    2004-03-01

    A fully-dense Cu-75 vol pct ZrW2O8 metal matrix composite was fabricated by hot isostatic pressing of Cu-coated ZrW2O8 particles. A small amount of the high-pressure γ-ZrW2O8 phase was created during the cooldown and depressurization following densification; near complete transformation to γ-ZrW2O8 was achieved by subsequent cold isostatic pressing. The thermal expansion behavior of the composite between 25°C and 325°C was altered by the cold isostatic pressing treatment, and also depended on the length of time that had passed between thermal cycles. The measured thermal expansion coefficients within specific temperature ranges varied from -6·10-6 K-1 to far above the thermal expansion coefficient of the copper matrix. The complex temperature-dependent expansion/contraction behavior could be justified by considering the evolution of phase transformations taking place in the ZrW2O8 phase, which were observed by in-situ synchrotron X-ray diffraction measurements.

  11. In situ observation of quasimelting of diamond and reversible graphite-diamond phase transformations.

    PubMed

    Huang, J Y

    2007-08-01

    Because of technique difficulties in achieving the extreme high-pressure and high-temperature (HPHT) simultaneously, direct observation of the structures of carbon at extreme HPHT conditions has not been possible. Banhart and Ajayan discovered remarkably that carbon onions can act as nanoscopic pressure cells to generate high pressures. By heating carbon onions to approximately 700 degrees C and under electron beam irradiation, the graphite-to-diamond transformation was observed in situ by transmission electron microscopy (TEM). However, the highest achievable temperature in a TEM heating holder is less than 1000 degrees C. Here we report that, by using carbon nanotubes as heaters and carbon onions as high-pressure cells, temperatures higher than 2000 degrees C and pressures higher than 40 GPa were achieved simultaneously in carbon onions. At such HPHT conditions and facilitated by electron beam irradiation, the diamond formed in the carbon onion cores frequently changed its shape, size, orientation, and internal structure and moved like a fluid, implying that it was in a quasimelting state. The fluctuation between the solid phase of diamond and the fluid/amorphous phase of diamond-like carbon, and the changes of the shape, size, and orientation of the solid diamond, were attributed to the dynamic crystallization of diamond crystal from the quasimolten state and the dynamic graphite-diamond phase transformations. Our discovery offers unprecedented opportunities to studying the nanostructures of carbon at extreme conditions in situ and at an atomic scale.

  12. Numerical modeling of dielectrics electrocaloric effect near the ferroelectric-paraelectric phase transformation

    NASA Astrophysics Data System (ADS)

    Wang, Yixing; Liu, Liwu; Liu, Yanju; Leng, Jinsong

    2013-08-01

    Dielectrics with great electrocaloric effect (ECE) have great potential to be applied in modern refrigeration industry. Compared with the traditional refrigeration technology, it is environmentally friendly and has a higher efficiency. Researchers have found that compared with ECE occurring in ferroelectric phase, ECE in paraelectric state is giant. This paper is determined on calculating the ECE of several kinds of polar dielectric material so as to find some materials with giant ECE. First, we investigate the theoretical framework of ECE near the Ferroelectric-Paraelectric phase transformation, and we show the formula derivation of ECE near the Ferroelectric-Paraelectric phase transformation in the analytical method of the calculus derivation. Then we deduce the expression of phenomenological study parameters. Finally, we calculate the maximum temperature change, entropy change and the mechanical work of several kinds of dielectrics based on the expression deduced. We successfully find some dielectrics with giant ECE. The paper should offer great help in finding the dielectrics with giant ECE, which is of great value in application.

  13. Liquid-vapor transformations with surfactants. Phase-field model and Isogeometric Analysis

    NASA Astrophysics Data System (ADS)

    Bueno, Jesus; Gomez, Hector

    2016-09-01

    Surfactants are compounds that find energetically favorable to be located at the boundaries between fluids. They are able to modify the properties of those interfaces, for example, reducing surface tension. Here, we propose a new model for liquid-vapor flows with surfactants which captures the dynamics of the surfactant and accounts for phase transformations in the fluid. The aforementioned model is derived from a free energy functional by using a Coleman-Noll approach. The proposed theory emanates from the isothermal Navier-Stokes-Korteweg equations, which describe single-component two-phase flow and naturally allow for phase transformations. We believe that our model has significant potential to study the influence of surfactants in vaporization and condensation processes. From a numerical point of view, the proposed model poses significant challenges to existing discretization methods, including stiffness in space and time, internal and boundary layers as well as higher-order partial differential operators. To overcome these challenges we propose algorithms based on Isogeometric Analysis, which permit an accurate and efficient discretization. Finally, we illustrate the viability of the theoretical framework and the effectiveness of our algorithms by solving several numerical problems in two and three dimensions.

  14. Experimental and Numerical Simulations of Phase Transformations Occurring During Continuous Annealing of DP Steel Strips

    NASA Astrophysics Data System (ADS)

    Wrożyna, Andrzej; Pernach, Monika; Kuziak, Roman; Pietrzyk, Maciej

    2016-04-01

    Due to their exceptional strength properties combined with good workability the Advanced High-Strength Steels (AHSS) are commonly used in automotive industry. Manufacturing of these steels is a complex process which requires precise control of technological parameters during thermo-mechanical treatment. Design of these processes can be significantly improved by the numerical models of phase transformations. Evaluation of predictive capabilities of models, as far as their applicability in simulation of thermal cycles thermal cycles for AHSS is considered, was the objective of the paper. Two models were considered. The former was upgrade of the JMAK equation while the latter was an upgrade of the Leblond model. The models can be applied to any AHSS though the examples quoted in the paper refer to the Dual Phase (DP) steel. Three series of experimental simulations were performed. The first included various thermal cycles going beyond limitations of the continuous annealing lines. The objective was to validate models behavior in more complex cooling conditions. The second set of tests included experimental simulations of the thermal cycle characteristic for the continuous annealing lines. Capability of the models to describe properly phase transformations in this process was evaluated. The third set included data from the industrial continuous annealing line. Validation and verification of models confirmed their good predictive capabilities. Since it does not require application of the additivity rule, the upgrade of the Leblond model was selected as the better one for simulation of industrial processes in AHSS production.

  15. Study of phase transformation and crystal structure for 1D carbon-modified titania ribbons

    SciTech Connect

    Zhou, Lihui Zhang, Fang; Li, Jinxia

    2014-02-15

    One-dimensional hydrogen titanate ribbons were successfully prepared with hydrothermal reaction in a highly basic solution. A series of one-dimensional carbon-modified TiO{sub 2} ribbons were prepared via calcination of the mixture of hydrogen titanate ribbons and sucrose solution under N{sub 2} flow at different temperatures. The phase transformation process of hydrogen titanate ribbons was investigated by in-situ X-ray diffraction at various temperatures. Besides, one-dimensional carbon-modified TiO{sub 2} ribbons calcined at different temperatures were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption isotherms, diffuse reflectance ultraviolet–visible spectroscopy, and so on. Carbon-modified TiO{sub 2} ribbons showed one-dimensional ribbon crystal structure and various crystal phases of TiO{sub 2}. After being modified with carbon, a layer of uniform carbon film was coated on the surface of TiO{sub 2} ribbons, which improved their adsorption capacity for methyl orange as a model organic pollutant. One-dimensional carbon-modified TiO{sub 2} ribbons also exhibited enhanced visible-light absorbance with the increase of calcination temperatures. - Highlights: • The synthesis of 1D carbon-modified TiO{sub 2} ribbons. • The phase transformation of 1D carbon-modified TiO{sub 2} ribbons. • 1D carbon-modified TiO{sub 2} exhibites enhanced visible-light absorbance.

  16. Crystal Plasticity Constitutive Model for Multiphase Advanced High Strength Steels to Account for Phase Transformation and Yield Point Elongation

    NASA Astrophysics Data System (ADS)

    Park, Taejoon; Pourboghrat, Farhang

    2016-08-01

    A constitutive law was developed based on a rate-independent crystal plasticity to account for the mechanical behavior of multiphase advanced high strength steels. Martensitic phase transformation induced by the plastic deformation of the retained austenite was represented by considering the lattice invariant shear deformation and the orientation relationship between parent austenite and transformed martensite. The stress dependent transformation kinetics were represented by adopting the stress state dependent volume fraction evolution law. The plastic deformation of the austenite was determined to have the minimum- energy associated with the work during the phase transformation. In addition to the martensitic phase transformation, yield point elongation and subsequent hardening along with inhomogeneous plastic deformation were also represented by developing a hardening stagnation model induced by the delayed dislocation density evolution.

  17. Numerical estimation of phase transformations in solid state during Yb:YAG laser heating of steel sheets

    SciTech Connect

    Kubiak, Marcin Piekarska, Wiesława; Domański, Tomasz; Saternus, Zbigniew; Stano, Sebastian

    2015-03-10

    This work concerns the numerical modeling of heat transfer and phase transformations in solid state occurring during the Yb:YAG laser beam heating process. The temperature field is obtained by the numerical solution into transient heat transfer equation with convective term. The laser beam heat source model is developed using the Kriging interpolation method with experimental measurements of Yb:YAG laser beam profile taken into account. Phase transformations are calculated on the basis of Johnson - Mehl - Avrami (JMA) and Koistinen - Marburger (KM) kinetics models as well as continuous heating transformation (CHT) and continuous cooling transformation (CCT) diagrams for S355 steel. On the basis of developed numerical algorithms 3D computer simulations are performed in order to predict temperature history and phase transformations in Yb:YAG laser heating process.

  18. Microstructural Evidence for Conditioning-dependent (delta) -> (alpha)' Transformations in Retained (delta)-phase Pu-Ga

    SciTech Connect

    Jeffries, J R; Blobaum, K M; Wall, M A; Schwartz, A J

    2008-06-16

    The retained {delta} phase of a Pu-1.9 at.% Ga alloy is metastable with respect to the martensitic {delta} {yields} {alpha}{prime} transformation that occurs at low temperatures. This transformation has been shown to proceed by means of an isothermal martensitic mode, but the kinetics of the transformation are atypical. The transformation exhibits a 'double-C' in a time-temperature-transformation diagram, wherein there exist two temperatures where a given amount of transformation occurs in a minimum amount of time. The cause of the double-C kinetics remains uncertain, eliciting proposals of multiple mechanisms, multiple paths, or different morphologies as possible origins. Recently, a 'conditioning' treatment was found to affect the {delta} {yields} {alpha}{prime} transformation, but the underlying mechanism by which the conditioning treatment influences the transformation has not yet been resolved. In this study, microstructural characterization as a function of temperature, time, and conditioning has been employed to illuminate the role of conditioning in the {delta} {yields} {alpha}{prime} transformation. Conditioning is found to enhance transformation in the upper-C and to enable transformation in the lower-C. The data garnered from these experiments suggest that conditioning is intimately linked to nucleation processes and of little consequence to the growth and morphology of the {alpha}{prime} product phase.

  19. Reduction of ferrihydrite with adsorbed and coprecipitated organic matter: microbial reduction by Geobacter bremensis vs. abiotic reduction by Na-dithionite

    NASA Astrophysics Data System (ADS)

    Eusterhues, K.; Hädrich, A.; Neidhardt, J.; Küsel, K.; Keller, T. F.; Jandt, K. D.; Totsche, K. U.

    2014-09-01

    Ferrihydrite is a widespread poorly crystalline Fe oxide which becomes easily coated by natural organic matter in the environment. This mineral-bound organic matter entirely changes the mineral surface properties and therefore the reactivity of the original mineral. Here, we investigated 2-line ferrihydrite, ferrihydrite with adsorbed organic matter, and ferrihydrite coprecipitated with organic matter for microbial and abiotic reduction of Fe(III). Ferrihydrite-organic matter associations with different organic matter loadings were reduced either by Geobacter bremensis or abiotically by Na-dithionite. Both types of experiments showed decreasing initial Fe-reduction rates and decreasing degrees of reduction with increasing amounts of mineral-bound organic matter. At similar organic matter loadings, coprecipitated ferrihydrites were more reactive than ferrihydrites with adsorbed organic matter. The difference can be explained by the smaller crystal size and poor crystallinity of such coprecipitates. At small organic matter loadings the poor crystallinity of coprecipitates led to even faster Fe-reduction rates than found for pure ferrihydrite. The amount of mineral-bound organic matter also affected the formation of secondary minerals: goethite was only found after reduction of organic matter-free ferrihydrite and siderite was only detected when ferrihydrites with relatively low amounts of mineral-bound organic matter were reduced. We conclude that direct contact of G. bremensis to the Fe oxide mineral surface was inhibited by attached organic matter. Consequently, mineral-bound organic matter shall be taken into account as a factor in slowing down reductive dissolution.

  20. Phase Transformation and Magnetic Property of Ni-Mn-Ga Powders Prepared by Dry Ball Milling

    NASA Astrophysics Data System (ADS)

    Tian, B.; Chen, F.; Tong, Y. X.; Li, L.; Zheng, Y. F.

    2012-12-01

    This study investigated the phase transformations and magnetic properties of Ni-Mn-Ga alloy powders prepared by dry ball milling in argon atmosphere. The Fe and Cr elements were found to be introduced in the alloy after ball milling, which should result from the severe collision and friction among the particles, balls, and vial. The x-ray diffraction result indicated that the Fe and Cr elements should have alloyed with the Ni-Mn-Ga matrix. The martensitic transformation temperature and Curie temperature of the 800 °C annealed powders decreased by ~33 °C and increased by ~28 °C, respectively, as compared to that of the bulk alloy. The comprehensive effect of the changing of valence electron concentration of the alloy due to the introduction of Fe and Cr and the grain refinement of the alloy caused by ball milling should be responsible for the reduction of martensitic transformation temperature. The saturation magnetization of the 800 °C annealed powders became larger (~5 emu/g) than that of the bulk alloy. The enhancement of magnetic properties, such as the increase of Curie temperature and enhancement of saturation magnetization of the annealed Ni-Mn-Ga powders, should be attributed to the increase of magnetic exchange caused by introduction of Fe in the alloy. The contaminations of Fe and Cr elements emerging from the dry ball milling process changed the phase transformation and magnetic properties of the Ni-Mn-Ga alloy. Therefore, the dry ball milling process is difficult to control the contamination from the milling medium and not suitable to prepare Ni-Mn-Ga powders. On the contrary, the wet ball milling method under liquid medium should be a better method to prevent the contamination and fabricate pure Ni-Mn-Ga ferromagnetic shape memory alloy powders.

  1. Pressure-induced phase transformations during femtosecond-laser doping of silicon

    NASA Astrophysics Data System (ADS)

    Smith, Matthew J.; Lin, Yu-Ting; Sher, Meng-Ju; Winkler, Mark T.; Mazur, Eric; Gradečak, Silvija

    2011-09-01

    Silicon hyperdoped with chalcogens via femtosecond-laser irradiation exhibits unique near-unity sub-bandgap absorptance extending into the infrared region. The intense light-matter interactions that occur during femtosecond-laser doping produce pressure waves sufficient to induce phase transformations in silicon, resulting in the formation of metastable polymorphic phases, but their exact formation mechanism and influence on the doping process are still unknown. We report direct observations of these phases, describe their formation and distribution, and consider their potential impact on sub-bandgap absorptance. Specifically, the transformation from diamond cubic Si-I to pressure-induced polymorphic crystal structures (amorphous Si, Si-XII, and Si-III) during femtosecond-laser irradiation was investigated using scanning electron microscopy, Raman spectroscopy, and transmission electron microscopy. Amorphous Si, Si-XII, and Si-III were found to form in femtosecond-laser doped silicon regardless of the presence of a gaseous or thin-film dopant precursor. The rate of pressure loading and unloading induced by femtosecond-laser irradiation kinetically limits the formation of pressure-induced phases, producing regions of amorphous Si 20 to 200 nm in size and nanocrystals of Si-XII and Si-III. The surface texturing that occurs during femtosecond-laser irradiation produces inhomogeneous pressure distributions across the surface and causes delayed development of high-pressure silicon polymorphs over many laser pulses. Finally, we find that the polymorph phases disappear during annealing more rapidly than the sub-bandgap absorptance decreases, enabling us to decouple these two processes through post-treatment annealing.

  2. Grain size control and phase transformations in nanocrystalline ZrO(2)-Al(2)O(3)

    NASA Astrophysics Data System (ADS)

    Smyser, Bridget Maureen

    1998-12-01

    An effort has been made to develop nanocrystalline ZrOsb2-Alsb2Osb3 powders that exhibit grain size and phase stability during one thermal cycle from room temperature to 1100-1200sp°C for potential use as thermal barrier coating materials. For this use, the tetragonal phase of ZrOsb2 must be maintained. Tetragonal ZrOsb2 can be prevented from transforming to the monoclinic form by maintaining the grain size below a critical value. Alsb2Osb3 was intended to provide this grain size control due to its immiscibility with ZrOsb2. Several sol-gel and precipitation methods of producing the powders were compared, along with two different forms of high energy mixing. The powders were subsequently calcined and heat treated in order to assess their ability to maintain the desired phase distribution during thermal cycling. The powders were characterized by x-ray diffraction and transmission electron microscopy. The method producing the greatest fraction of tetragonal ZrOsb2 with the least amount of added Alsb2Osb3 was that in which a commercial colloidal solution of ZrOsb2 was mixed with an aluminum nitrate solution. The critical grain size of ZrOsb2 in this system was 30 nm. The grain size was controlled not by a pinning mechanism as is often seen in conventional, high Alsb2Osb3,\\ Alsb2Osb3-ZrOsb2 ceramics, but instead by mutual constraint of surrounding grains aided by sluggish grain boundary diffusion. The grain growth kinetics in all the phases tended to be slower than in micron sized materials, and a range of grain growth exponents from n = 1 to n = 30 were determined for the various phases. Transformation kinetics in ZrOsb2 followed classic Avrami behavior. Alsb2Osb3 phase transformation kinetics were not specifically determined, however, gamma-Alsb2Osb3 was identified at temperatures well beyond its usual stability, which is possibly a grain size effect.

  3. Phase transformation and phonon anomalies in Ni{sub 2}MnGa

    SciTech Connect

    Zheludev, A.; Shapiro, S.M.; Wochner, P.; Schwartz, A.; Wall, M.; Tanner, L.E.

    1995-07-01

    Inelastic neutron scattering experiments and transmission electron microscopy have been used to study a single crystal of the Ni{sub 2}MnGa shape memory Hustler alloy in a wide temperature range covering the parent phase (T>T{sub 1}=265 K), a recently discovered pemartensitic (T{sub 1}T>T{sub M}) and martensitic (Tphase regions. A temperature-dependent anomaly in the TA{sub 2} phonon dispersion in the parent phase was observed and related to the phase transformations. The premartensitic phase involves a transverse modulation of the parent cubic structure with a simple periodicity of 1/3 [110]. The approximately tetragonal lattice of the low-temperature martensite is distorted by transverse modulations with incommensurate wave vectors [{zeta}M {zeta}M {sup 0}] and [{sup 2}{zeta}M {sup 2}{zeta}M {sup 0}], {zeta}M {approx}0.43. The observed phenomena are attributed to electron-phonon interactions and anharmonic effects.

  4. Ion beam induced cubic to monoclinic phase transformation of nanocrystalline yttria

    NASA Astrophysics Data System (ADS)

    Shivaramu, N. J.; Lakshminarasappa, B. N.; Nagabhushana, K. R.; Singh, Fouran

    2016-07-01

    Sol gel derived nanocrystalline yttria pellets are irradiated with 120 MeV Ag9+ ions for fluence in the range 1 × 1012-3 × 1013 ions cm-2. Pristine and irradiated samples are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and Raman spectroscopy. XRD pattern of pristine Y2O3 nanocrystal reveal cubic structure. A new XRD peak at 30.36° is observed in pellet irradiated with 1 × 1013 ions cm-2. The peak at 30.36° is corresponding to (4 0 2 bar) plane of monoclinic phase. The diffraction intensity of (4 0 2 bar) plane increases with Ag9+ ion fluence. Raman spectrum of pristine pellet show bands corresponding to cubic phase. And, ion irradiated sample show new peaks at 410, 514 and 641 cm-1 corresponding monoclinic phase. HR-TEM and SAED pattern of ion irradiated sample confirmed the presence of monoclinic phase. Hence, it is confirmed that, 120 MeV Ag9+ ions induce phase transformation in nanocrystalline Y2O3.

  5. LiMO{sub 2} (M=Mn, Fe, and Co): Energetics, polymorphism and phase transformation

    SciTech Connect

    Wang Miaojun; Navrotsky, Alexandra . E-mail: anavrotsky@ucdavis.edu

    2005-04-15

    LiMO{sub 2} materials (M=Mn, Fe, and Co) with different structures were synthesized and their enthalpies of formation from oxides (Li{sub 2}O and M{sub 2}O{sub 3}, M=Mn and Fe), or from oxides (Li{sub 2}O and CoO) plus oxygen at 25{sup o}C were determined by high-temperature oxide melt solution calorimetry. The relative stability of the polymorphs of the compound LiMO{sub 2} was established based on their enthalpies of formation. Phase transformations in LiFeO{sub 2} were investigated by differential scanning calorimetry and high-temperature oxide melt solution calorimetry. The phase transition enthalpies at 25{sup o}C for {beta}->{alpha}, {gamma}->{beta}, and {gamma}->{alpha} are 4.9+/-0.7, 4.3+/-0.8 and 9.2+/-0.9kJ/mol, respectively. Thus the {gamma} phase (ordered cations) is the stable form of LiFeO{sub 2} at room temperature, the {alpha} phase (disordered cations) is stable at high temperature and the {beta} phase may have a stability field at intermediate temperatures.

  6. Experimental evidence of α → β phase transformation in SiC quantum dots and their size-dependent luminescence

    SciTech Connect

    Guo, Xiaoxiao; Dai, Dejian; Fan, Baolu; Fan, Jiyang

    2014-11-10

    Phase transformation can occur among different SiC polytypes under extreme conditions such as high pressure or temperature. It remains unknown whether phase transformation can occur under normal conditions. We demonstrate that the α → β phase transformation can occur at ambient temperature and pressure in nanoscale SiC. The microstructural characterization and light absorption and emission spectroscopy demonstrate the occurrence of this phase transformation. It is found that the quantum-confinement luminescence dominates in larger SiC quantum dots (QDs) and the surface-defect luminescence dominates in ultrasmall SiC QDs. The rare phenomenon of multiple-phonon-assisted light absorption is observed in the SiC QDs.

  7. The evolution of phase transformation in Ni/Ni3Al laminated composite under high temperature treatments

    NASA Astrophysics Data System (ADS)

    Shmorgun, V.; Gurevich, L.; Bogdanov, A.; Trunov, M.

    2016-02-01

    In this study the impact of isothermal annealing on the phase transformation rate in laminated Ni/Ni2Al3 composite was investigated. The method of nickel-aluminide coatings of the required chemical composition fabrication was proposed.

  8. Mechanism of the gamma-beta phase transformation of Mg2SiO4 at high temperature and pressure

    NASA Technical Reports Server (NTRS)

    Rubie, D. C.; Brearley, A. J.

    1990-01-01

    The results of experiments on the phase transformation of Mg2SiO4 olivine at 15 GPa pressure in a multianvil cell are reported. At this pressure and a temperature of 900 C, early formed metastable gamma-spinel transforms partially to the beta-phase. The observed microstructures, which are similar to those in shocked meteorites, show that the gamma-to-beta transformation can occur either by diffusion-controlled growth or by a martensitic mechanism, depending on how far the pressure-temperature conditions deviate from their values at phase equilibrium. The results suggest that the diffusion-controlled mechanism is most likely to operate at the beta/gamma phase boundary in the mantle, but martensitic beta-to-gamma transformation might occur in subduction zones and could reduce the shear strength of the subducting slab.

  9. Gyrator transform based double random phase encoding with sparse representation for information authentication

    NASA Astrophysics Data System (ADS)

    Chen, Jun-xin; Zhu, Zhi-liang; Fu, Chong; Yu, Hai; Zhang, Li-bo

    2015-07-01

    Optical information security systems have drawn long-term concerns. In this paper, an optical information authentication approach using gyrator transform based double random phase encoding with sparse representation is proposed. Different from traditional optical encryption schemes, only sparse version of the ciphertext is preserved, and hence the decrypted result is completely unrecognizable and shows no similarity to the plaintext. However, we demonstrate that the noise-like decipher result can be effectively authenticated by means of optical correlation approach. Simulations prove that the proposed method is feasible and effective, and can provide additional protection for optical security systems.

  10. Universal and special keys based on phase-truncated Fourier transform

    PubMed Central

    Qin, Wan; Peng, Xiang; Meng, Xiangfeng; Gao, Bruce

    2013-01-01

    We propose a novel optical asymmetric cryptosystem based on a phase-truncated Fourier transform. Two decryption keys independent of each other are generated. They are referred to as universal key and special key, respectively. Each of them can be used for decryption independently in absence of the other. The universal key is applicable to decrypt any ciphertext encoded by the same encryption key, but with poor legibility. On the contrary, the special key is adequate for legible decryption, but only valid for one ciphertext corresponding to the specified plaintext. A set of simulation results show the interesting performance of two types of de cryption keys. PMID:25339784

  11. Stress-driven phase transformation and the roughening of solid-solid interfaces.

    PubMed

    Angheluta, L; Jettestuen, E; Mathiesen, J; Renard, F; Jamtveit, B

    2008-03-01

    The application of stress to multiphase solid-liquid systems often results in morphological instabilities. Here we propose a solid-solid phase transformation model for roughening instability in the interface between two porous materials with different porosities under normal compression stresses. This instability is triggered by a finite jump in the free energy density across the interface, and it leads to the formation of fingerlike structures aligned with the principal direction of compaction. The model is proposed as an explanation for the roughening of stylolites-irregular interfaces associated with the compaction of sedimentary rocks that fluctuate about a plane perpendicular to the principal direction of compaction.

  12. A New, More Stable Polymorphic Form of Otilonium Bromide: Solubility, Crystal Structure, and Phase Transformation.

    PubMed

    Vega, Daniel R; Halac, Emilia; Segovia, Luciano; Baggio, Ricardo

    2016-10-01

    A new polymorphic form of otilonium bromide is presented (Form I), and a thorough analysis of its crystal and molecular structure is performed. The compound suffers a temperature-driven first-order phase transition at about 396 K, which transforms it into the polymorph reported by Dapporto P and Sega A (Acta Cryst. 1986;C42:474-478) (Form II). Through thermal analysis and solubility experiments the relative stability of both crystal modifications were determined, confirming that at room temperature this new Form I is the more stable one, Form II existing just in a metastable state. PMID:27444388

  13. A condensed variational model for thermo-mechanically coupled phase transformations in polycrystalline shape memory alloys

    NASA Astrophysics Data System (ADS)

    Junker, Philipp; Hackl, Klaus

    2013-11-01

    We derive an energy-based material model for thermomechanically coupled phase transformations in polycrystalline shape memory alloys. For the variational formulation of the model, we use the principle of the minimum of the dissipation potential for nonisothermal processes for which only a minimal number of constitutive assumptions has to be made. By introducing a condensed formulation for the representative orientation distribution function, the resulting material model is numerically highly efficient. For a first analysis, we present the results of material point calculations, where the evolution of temperature as well as its influence on the mechanical material response is investigated.

  14. Stability of a laser cavity with non-parabolic phase transformation elements.

    PubMed

    Litvin, Igor A

    2013-05-01

    In this paper we present a general approach to determine the stability of a laser cavity which can include non-conventional phase transformation elements. We consider two pertinent examples of the detailed investigation of the stability of a laser cavity firstly with a lens with spherical aberration and thereafter a lens axicon doublet to illustrate the implementation of the given approach. In the particular case of the intra-cavity elements having parabolic surfaces, the approach comes to the well-known stability condition for conventional laser resonators namely 0 ≤ (1-z/R(1))(1-z/R(2)) ≤ 1.

  15. Phase Transformations in Electrically Conductive Ferromagnetic Shape-Memory Alloys, Their Thermodynamics and Analysis

    NASA Astrophysics Data System (ADS)

    Roubíček, Tomáš; Tomassetti, Giuseppe

    2013-10-01

    We derive a thermodynamically consistent general continuum-mechanical model describing mutually coupled martensitic and ferro/paramagnetic phase transformations in electrically-conductive magnetostrictive materials such as NiMnGa. We use small-strain and eddy-current approximations, yet large velocities and electric current injected through the boundary are allowed. Fully nonlinear coupling of magneto-mechanical and thermal effects is considered. The existence of energy-preserving weak solutions is proved by showing convergence of time-discrete approximations constructed by a carefully designed semi-implicit regularized scheme.

  16. Influence of phase transformation on stress evolution during growth of metal thin films on silicon.

    PubMed

    Fillon, A; Abadias, G; Michel, A; Jaouen, C; Villechaise, P

    2010-03-01

    In situ stress measurements during two-dimensional growth of low mobility metal films on amorphous Si were used to demonstrate the impact of interface reactivity and phase transformation on stress evolution. Using Mo1-xSix films as examples, the results show that the tensile stress rise, which develops after the film has become crystalline, is correlated with an increase in lateral grain size. The origin of the tensile stress is attributed to the volume change resulting from the alloy crystallization, which occurs at a concentration-dependent critical thickness. PMID:20366996

  17. A New, More Stable Polymorphic Form of Otilonium Bromide: Solubility, Crystal Structure, and Phase Transformation.

    PubMed

    Vega, Daniel R; Halac, Emilia; Segovia, Luciano; Baggio, Ricardo

    2016-10-01

    A new polymorphic form of otilonium bromide is presented (Form I), and a thorough analysis of its crystal and molecular structure is performed. The compound suffers a temperature-driven first-order phase transition at about 396 K, which transforms it into the polymorph reported by Dapporto P and Sega A (Acta Cryst. 1986;C42:474-478) (Form II). Through thermal analysis and solubility experiments the relative stability of both crystal modifications were determined, confirming that at room temperature this new Form I is the more stable one, Form II existing just in a metastable state.

  18. Iterative Transform Phase Diversity: An Image-Based Object and Wavefront Recovery

    NASA Technical Reports Server (NTRS)

    Smith, Jeffrey

    2012-01-01

    The Iterative Transform Phase Diversity algorithm is designed to solve the problem of recovering the wavefront in the exit pupil of an optical system and the object being imaged. This algorithm builds upon the robust convergence capability of Variable Sampling Mapping (VSM), in combination with the known success of various deconvolution algorithms. VSM is an alternative method for enforcing the amplitude constraints of a Misell-Gerchberg-Saxton (MGS) algorithm. When provided the object and additional optical parameters, VSM can accurately recover the exit pupil wavefront. By combining VSM and deconvolution, one is able to simultaneously recover the wavefront and the object.

  19. High temperature phase transformation studies in magnetite nanoparticles doped with Co2+ ion

    NASA Astrophysics Data System (ADS)

    Pati, S. S.; Gopinath, S.; Panneerselvam, G.; Antony, M. P.; Philip, John

    2012-09-01

    We investigate the effect of Co2+ ion doping in magnetite (Fe3O4) on its crystal structure, magnetic properties, and phase stability during air and vacuum annealing. The nanoparticles are prepared by co-precipitation method and the particles are characterized by XRD, small angle x-ray scattering (SAXS), themogravimetric and differential scanning calorimetry (DSC), and vibrating sample magnetometer. The SAXS analysis on the doped samples show the most probable size, shape, and the polydispersity of particles, synthesized with different fractions (0-0.6) of Co2+ ion doping remains almost the same. On increasing cobalt content ferrimagnetic to the antiferromagnetic hematite (α-Fe2O3) phase transformation temperature is found to increase dramatically. For 0.1 fraction of Co2+ metal ion doping, an enhancement of 100 °C in the γ-Fe2O3 to α-Fe2O3 phase transition temperature is observed in the air annealed samples, whereas magnetic nature remains stable up to 1000 °C in vacuum annealed samples. On increasing the cobalt fractions beyond 0.2, air annealed samples show no change in the phase transition temperature. The observed enhancement in the phase transition temperature is attributed to the increased activation energy for phase transformation in presence of Co2+. Further, the DSC results corroborate the finding of an increase in the maghemite to hematite phase transition temperature with increase in cobalt fraction (x). The decrease in enthalpy from 89.86 to 17.62 J g-1 with an increase in cobalt content indicates that the degree of conversion of maghemite to hematite decreases with the cobalt content, which is in good agreement with the Rietveld analysis. The decrease in the Ms value in air annealed sample is attributed to the re-distribution of cations in the tetrahedral and octahedral sites, as the Fe3+A-Fe3+B super-exchange interaction is different from the Co2+A-Fe3+B interaction. These results suggest that a very small percentage of Co2+ metal ion doping can

  20. Synergistic effect of calcium and bicarbonate in enhancing arsenate release from ferrihydrite

    NASA Astrophysics Data System (ADS)

    Saalfield, Samantha L.; Bostick, Benjamin C.

    2010-09-01

    Many groundwater systems contain anomalously high arsenic concentrations, associated with less than expected retention of As by adsorption to iron (hydr)oxides. Although carbonates are ubiquitous in aquifers, their relationship to arsenate mobilization is not well characterized. This research examines arsenate release from poorly crystalline iron hydroxides in abiotic systems containing calcium and magnesium with bicarbonate under conditions of static and dynamic flow (pH 7.5-8). Aqueous arsenic levels remained low when arsenate-bearing ferrihydrite was equilibrated with artificial groundwater solution containing Ca, Mg, and HCO 3-. In batch titrations in which a solution of Ca and HCO 3- was added repeatedly, the ferrihydrite surface became saturated with adsorbed Ca and HCO 3-, and aqueous As levels increased by 1-2 orders of magnitude. In columns containing Ca or Mg and HCO 3-, As solubility initially mimicked titrations, but then rapidly increased by an additional order of magnitude (reaching 12 μM As). Separately, calcium chloride and other simple salts did not induce As release, although sodium bicarbonate and lactate facilitated minor As release under flow. Results indicate that adsorption of calcium or magnesium with bicarbonate leads to As desorption from ferrihydrite, to a degree greater than expected from competitive effects alone, especially under dynamic flow. This desorption may be an important mechanism of As mobilization in As-impacted, circumneutral aquifers, especially those undergoing rapid mineralization of organic matter, which induces calcite dissolution and the production of dissolved calcium and bicarbonate.

  1. In situ high temperature microscopy study of the surface oxidation and phase transformations in titanium alloys.

    PubMed

    Malinov, S; Sha, W; Voon, C S

    2002-09-01

    Two popular commercial titanium alloys, Ti-6Al-4V and Ti-6Al-2Sn-4Zr-2Mo-0.08Si, were used for in situ high temperature microscopy study. The experiments were performed on an optical microscope equipped with high temperature stage using both normal and florescence lights. Two kinds of experiments were performed, at continuous heating/cooling with different rates and in isothermal conditions at different temperatures. The changes taking place on the sample surface during the experiments were monitored. The morphology of the alpha ==> beta ==> alpha phase transformation was recorded at different heat treatment conditions using the effect of thermal etching. An effect of sample surface oxidation and deoxidation was observed during continuous heating. The appearance and disappearance of ordered titanium oxides Ti3O and Ti2O are discussed based on the phase equilibrium diagram. The kinetics of the surface oxidation was monitored in both isothermal and continuous cooling conditions.

  2. Phase transformations and indications for acoustic mode softening in Tb-Gd orthophosphate

    DOE PAGESBeta

    Tschauner, Oliver; Ushakov, Sergey V.; Navrotsky, Alexandra; Boatner, Lynn A.

    2016-01-06

    At ambient conditions the anhydrous rare-earth orthophosphates assume either the xenotime (zircon) or the monazite structure, with the latter favored for the heavier rare earths. Tb0.5Gd0.5PO4 assumes the xenotime structure at ambient conditions but is at the border between the xenotime and monazite structures. Here we show that, at high pressure, Tb0.5Gd0.5PO4 does not transform directly to monazite but through an intermediate anhydrite-type structure. We show softening of (c1133 + c1313) combined elastic moduli close to the transition from the anhydrite to the monazite structure. Stress response of rare-earth orthophosphate ceramics can be affected by both formation of the anhydrite-typemore » phase and the elastic softening in the vicinity of the monazite-phase. In conclusion, we report the first structural data for an anhydrite-type rare earth orthophosphate.« less

  3. Ultra-thin optical vortex phase plate based on the metasurface and the angular momentum transformation

    NASA Astrophysics Data System (ADS)

    Wang, Wei; Li, Yan; Guo, Zhongyi; Li, Rongzhen; Zhang, Jingran; Zhang, Anjun; Qu, Shiliang

    2015-04-01

    The ultra-thin optical vortex phase plate (VPP) has been designed and investigated based on the metasurface of the metal rectangular split-ring resonators (MRSRRs) array. The circularly polarized incident light can convert into corresponding cross-polarization transmission light, and the phase and the amplitude of cross-polarization transmission light can be simultaneously governed by modulating two arms of the MRSRR. The MRSRR has been arranged in a special order for forming an ultra-thin optical VPP that can covert a plane wave into a vortex beam with a variety of the topological charges, and the transformation between spin angular momentum (SAM) and orbital angular momentum (OAM) has been discussed in detail. The multi-spectral characteristics of the VPP have also been investigated, and the operating bandwidth of the designed VPP is 190 nm (in the range of 710-900 nm), which enable a potential implication for integrated optics and vortex optics.

  4. CEMS study of strain induced phase transformation in manganese Hadfield steel

    NASA Astrophysics Data System (ADS)

    Cabanillas, E. D.; Alvarez, E. P.; Hey, A.; Mercader, R. C.

    1991-11-01

    A Conversion Electron Mössbauer Spectroscopy, (CEMS), study of phase transformations in a Hadfield steel induced by high rate strains is reported. Hadfield steel samples were impact deformed and the ensuing changes in the magnetic properties at the deformed zone and its surroundings have been studied by CEMS. The CEMS results are compared with wear tests and optical microscopy and show a formation of martensite by impact deformation only at the surface. Martensite is not produced by compression or tensile stresses but appears after wear tests in proportions that depend on the load and velocity conditions of test. The understanding of martensite phase formation and its evolution during deformation processes is also addressed.

  5. Phase diagram of the Y–Y{sub 2}Se{sub 3} system, enthalpies of phase transformations

    SciTech Connect

    Andreev, O.V.; Kharitontsev, V.B.; Polkovnikov, A.A.; Elyshev, A.V.; Andreev, P.O.

    2015-10-15

    A phase diagram for the Y–Y{sub 2}Se{sub 3} system has been constructed in which the YSe and Y{sub 2}Se{sub 3} phases melt congruently. The daltonide type YSe phase (ST Y{sub 0,75}Se, a=1.1393 nm, melting point=2380 K, H=2200 MPa) forms a double-sided solid solution from 49–50–53 at% Se. In the 50–53 at% Se range, the unit cell parameter increases to 1.1500 nm, the microhardness increases to 4100 MPa and electrical resistivity increases from 0.018 to 0.114 Ω m. These changes are caused by the dominating influx of newly formed structural cationic vacancies arising from the selenium anions that are surplus for the 1:1 Y:Se stoichiometry. The full-valence Y{sub 2}Se{sub 3} composition exists as a low-temperature modification of ε-Y{sub 2}Se{sub 3} (ST Sc{sub 2}S{sub 3}, a=1.145 nm, b=0.818 nm, c=2.438 nm, melting point=1780 K, ∆fusion enthalpy=4±0.4 J/g) and transforms into a modification of ξ-Y{sub 2}Se{sub 3} that does not undergo fixing by thermo-hardening. The eutectic melting point between the YSe and Y{sub 2}Se{sub 3} phases is 1625±5 K, with a eutectic composition that is assumed to be 57.5 at% Se and have an enthalpy of fusion of 43±4.3 J/g. The eutectic for the Y and YSe phases appears at a temperature of 1600 K and 5 at% Se. - Highlights: • Phase equilibria in the Y–Y{sub 2}Se{sub 3} system from 1000 K to melt were studies. • High-temperature polymorphic transition for Y{sub 2}Se{sub 3} were observed. • Singular points in solid solutions areas for YSe and Y{sub 2}Se{sub 3} were found.

  6. Isomorphism in Fluid Phase Diagrams: Kulinskii Transformations Related to the Acentric Factor

    SciTech Connect

    Wei, Q; Herschbach, DR

    2013-10-31

    For a wide class of molecular fluids, the temperature-density phase diagrams exhibit two prominent generic properties: a nearly linear locus, termed the Zeno line, along which the compressibility factor, Z = P/rho RT = 1 (same as an ideal gas), and the widely arching border of the vapor-liquid coexistence region, termed the binodal curve, with gas and liquid branches meeting at the critical point. The Zeno and binodal loci have been known for more than a century, yet only during the past two decades were striking empirical correlations between them recognized. Recently, Kulinskii introduced a remarkably simple projective transformation, wherein the linearity of the Zeno line and its relation to the binodal curve are geometrical consequences of an approximate isomorphism of the fluid with a venerable theoretical model, the lattice gas (equivalent to the Ising spin model). Here we show the Kulinskii transformation is significantly improved in accuracy and scope by using as input, in place of the lattice gas, the original van der Waals equation or simulation results for the Lennard-Jones potential. Moreover, the key parameters in these transformations can be expressed in terms of the acentric factor, introduced by Pitzer to extend corresponding states.

  7. Modeling the coupling between martensitic phase transformation and plasticity in shape memory alloys

    NASA Astrophysics Data System (ADS)

    Manchiraju, Sivom

    The thermo-mechanical response of NiTi shape memory alloys (SMAs) is predominantly dictated by two inelastic deformation processes---martensitic phase transformation and plastic deformation. This thesis presents a new microstructural finite element (MFE) model that couples these processes and anisotropic elasticity. The coupling occurs via the stress redistribution induced by each mechanism. The approach includes three key improvements to the literature. First, transformation and plasticity are modeled at a crystallographic level and can occur simultaneously. Second, a rigorous large-strain finite element formulation is used, thereby capturing texture development (crystal rotation). Third, the formulation adopts recent first principle calculations of monoclinic martensite stiffness. The model is calibrated to experimental data for polycrystalline NiTi (49.9 at% Ni). Inputs include anisotropic elastic properties, texture, and DSC data as well as a subset of pseudoelastic and load-biased thermal cycling data. This calibration process provides updated material values---namely, larger self-hardening between similar martensite plates. It is then assessed against additional pseudoelastic and load-biased thermal cycling experimental data and neutron diffraction measurements of martensite texture evolution. Several experimental trends are captured---in particular, the transformation strain during thermal cycling monotonically increases with increasing bias stress, reaching a peak and then decreasing due to intervention of plasticity---a trend which existing MFE models are unable to capture. Plasticity is also shown to enhance stress-induced martensite formation during loading and generate retained martensite upon unloading. The simulations even enable a quantitative connection between deformation processing and two-way shape memory effect. Some experimental trends are not captured---in particular, the ratcheting of macrostrain with repeated thermal cycling. This may

  8. Swift heavy ion irradiation induced phase transformation in undoped and niobium doped titanium dioxide composite thin films

    NASA Astrophysics Data System (ADS)

    Gautam, Subodh K.; Chettah, Abdelhak; Singh, R. G.; Ojha, Sunil; Singh, Fouran

    2016-07-01

    Study reports the effect of swift heavy ion (SHI) irradiation induced phase transformation in undoped and Niobium doped anatase TiO2 composite thin films. Investigations were carried out at different densities of electronic excitations (EEs) using 120 MeV Ag and 130 MeV Ni ions irradiations. Films were initially annealed at 900 °C and results revealed that undoped films were highly stable in anatase phase, while the Nb doped films showed the composite nature with the weak presence of Niobium penta-oxide (Nb2O5) phase. The effect at low density of EEs in undoped film show partial anatase to rutile phase transformation; however doped film shows only further growth of Nb2O5 phase beside the anatase to rutile phase transformation. At higher density of EEs induced by Ag ions, registered continuous ion track of ∼3 nm in lattice which leads to nano-crystallization followed by decomposition/amorphization of rutile TiO2 and Nb2O5 phases in undoped and doped films, respectively. However, Ni ions are only induced discontinuous sequence of ion tracks with creation of damage and disorder and do not show amorphization in the lattice. The in-elastic thermal spike calculations were carried out for anatase TiO2 phase to understand the effect of EEs on anatase to rutile phase transformation followed by amorphization in NTO films in terms of continuous and discontinuous track formation by SHI irradiation.

  9. Influence of Temperature on Fatigue-Induced Martensitic Phase Transformation in a Metastable CrMnNi-Steel

    NASA Astrophysics Data System (ADS)

    Biermann, Horst; Glage, Alexander; Droste, Matthias

    2016-01-01

    Metastable austenitic steels can exhibit a fatigue-induced martensitic phase transformation during cyclic loading. It is generally agreed that a certain strain amplitude and a threshold of the cumulated plastic strain must be exceeded to trigger martensitic phase transformation under cyclic loading. With respect to monotonic loading, the martensitic phase transformation takes place up to a critical temperature—the so-called M d temperature. The goal of the present investigation is to determine an M d,c temperature which would be the highest temperature at which a fatigue-induced martensitic phase transformation can take place. For this purpose, fatigue tests controlled by the total strain were performed at different temperatures. The material investigated was a high-alloy metastable austenitic steel X3CrMnNi16.7.7 (16.3Cr-7.2Mn-6.6Ni-0.03C-0.09N-1.0Si) produced using the hot pressing technique. The temperatures were set in the range of 283 K (10 °C) ≤ T ≤ 473 K (200 °C). Depending on the temperature and strain amplitude, the onset of the martensitic phase transformation shifted to different values of the cumulated plastic strain, or was inhibited completely. Moreover, it is known that metastable austenitic CrMnNi steels with higher nickel contents can exhibit the deformation-induced twinning effect. Thus, at higher temperatures and strain amplitudes, a transition from the deformation-induced martensitic transformation to deformation-induced twinning takes place. The fatigue-induced martensitic phase transformation was monitored during cyclic loading using a ferrite sensor. The microstructure after the fatigue tests was examined using the back-scattered electrons, the electron channeling contrast imaging and the electron backscatter diffraction techniques to study the temperature-dependent dislocation structures and phase transformations.

  10. Triple-image encryption based on phase-truncated Fresnel transform and basic vector operation.

    PubMed

    Pan, Xuemei; Meng, Xiangfeng; Yang, Xiulun; Wang, Yurong; Peng, Xiang; He, Wenqi; Dong, Guoyan; Chen, Hongyi

    2015-10-01

    A triple-image encryption method is proposed that is based on phase-truncated Fresnel transform (PTFT), basic vector composition, and XOR operation. In the encryption process, two random phase masks, with one each placed at the input plane and the transform plane, are generated by basic vector resolution operations over the first and the second plaintext images, and then a ciphered image in the input plane is fabricated by XOR encoding for the third plaintext image. When the cryptosystem is illuminated by an on-axis plane, assisted by PTFT, the ciphered image is finally encrypted into an amplitude-only noise-like image in the output plane. During decryption, possessing the correct private key, decryption keys, and the assistant geometrical parameter keys, and placing them at the corresponding correct positions, the original three plaintext images can be successfully decrypted by inverse PTFT, basic vector composition, and XOR decoding. Theoretical analysis and numerical simulations both verify the feasibility of the proposed method. PMID:26479627

  11. Phase Transformations During the Low-Temperature Nitriding of AISI 2205 Duplex Stainless Steel

    NASA Astrophysics Data System (ADS)

    Yan, Jing; Gu, Tan; Qiu, Shaoyu; Wang, Jun; Xiong, Ji; Fan, Hongyuan

    2015-02-01

    Liquid nitriding of type AISI 2205 duplex stainless steel was conducted at 723 K (450 °C), using one type of novel low-temperature liquid chemical thermo-treatment. The transformation of the nitrided surface microstructure was systematically studied. Experimental results revealed that a nitrided layer formed on the sample surface with the thickness ranging from 3 to 28 μm, depending on nitriding time. After the 2205 duplex stainless steel was subjected to liquid nitriding 723 K (450 °C) for less than 8 hours, the pre-existing ferrite region on the surface transformed into the expanded austenite (S phase) by the infusion of nitrogen atoms, most of which stay in the interstitial sites. Generally, the dominant phase of the nitrided layer was the expanded austenite. When the nitriding time prolonged up to 16 hours, some pre-existing ferrite in expanded austenite was decomposed and ɛ-nitride precipitated subsequently. When the treatment time went up to 40 hours, large amount of ɛ-nitride and CrN precipitates were observed in the pre-existing ferritic region in the expanded austenite. Furthermore, many nitrides precipitated from the pre-austenite region. Acicular nitride was identified by transmission electron microscopy. The thickness of the nitrided layer increased with increasing nitriding time. The growth of the nitrided layer is mainly due to nitrogen diffusion in accordance with the expected parabolic rate law. Liquid nitriding effectively increased the surface hardness of 2205 duplex stainless steel by a factor of 3.

  12. Methotrexate intercalated calcium carbonate nanostructures: Synthesis, phase transformation and bioassay study.

    PubMed

    Dai, Chao-Fan; Wang, Wei-Yuan; Wang, Lin; Zhou, Lei; Li, Shu-Ping; Li, Xiao-Dong

    2016-12-01

    The formation and stabilization of amorphous calcium carbonate (ACC) is an active area of research owing to the presence of stable ACC in various biogenic minerals. In this paper, the synthesis of calcium carbonate (CaCO3) under the participation of methotrexate (MTX) via a facile gas diffusion route was reported. The results indicated that the addition of MTX can result in the phase transformation of CaCO3, and then two kinds of hybrids, i.e., MTX-vaterite and stable MTX-ACC came into being. Interestingly, the functional agent MTX served as both the target anticancer drug loaded and effective complexation agents to modify and control the morphology of final samples. The examination of MTX-ACC biodegradation process revealed that the collapse of MTX-ACC nanoparticles was due to the synergistic effect of drug release and the phase transformation. Finally, our study also proved that MTX-ACC exhibited the most excellent suppressing function on the viability of cancer cells, especially after long-time duration.

  13. Calibration of Parameters in Beta-Delta HMX Phase Transformation Kinetics Using Computer Simulations

    SciTech Connect

    Wemhoff, A P; Burnham, A K

    2005-11-17

    The kinetics of the beta-delta solid-solid phase transformation of HMX (nitramine octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) were modeled in ALE2D using four similar equilibrium-inhibited nucleation-growth models: a reversible set of Arrhenius kinetics following a LANL model, and three sets of kinetics derived based on an autocatalytic model using the bidirectional reaction formalism. The parameters for the bidirectional kinetics models were calibrated using simulations of two experimental setup scenarios where experimental data is available: 165 C XRD and SITI. In this calibration, the transition enthalpy and activation energy values were kept constant, while the frequency factors were iterated to achieve results similar to those provided by the experiments. This process yielded six unique sets of kinetic parameters that describe the phase transformation: a pair of sets for each of the three bidirectional kinetics models. The models calibrated using 165 C XRD data showed good agreement with LX-04 STEX experimental results, while the SITI-based models were in good agreement with the LANL model and PBX-9501 STEX experimental data. These bidirectional models were also shown to require less computational effort than the LANL model.

  14. Methotrexate intercalated calcium carbonate nanostructures: Synthesis, phase transformation and bioassay study.

    PubMed

    Dai, Chao-Fan; Wang, Wei-Yuan; Wang, Lin; Zhou, Lei; Li, Shu-Ping; Li, Xiao-Dong

    2016-12-01

    The formation and stabilization of amorphous calcium carbonate (ACC) is an active area of research owing to the presence of stable ACC in various biogenic minerals. In this paper, the synthesis of calcium carbonate (CaCO3) under the participation of methotrexate (MTX) via a facile gas diffusion route was reported. The results indicated that the addition of MTX can result in the phase transformation of CaCO3, and then two kinds of hybrids, i.e., MTX-vaterite and stable MTX-ACC came into being. Interestingly, the functional agent MTX served as both the target anticancer drug loaded and effective complexation agents to modify and control the morphology of final samples. The examination of MTX-ACC biodegradation process revealed that the collapse of MTX-ACC nanoparticles was due to the synergistic effect of drug release and the phase transformation. Finally, our study also proved that MTX-ACC exhibited the most excellent suppressing function on the viability of cancer cells, especially after long-time duration. PMID:27612750

  15. Abnormal correlation between phase transformation and cooling rate for pure metals.

    PubMed

    Han, J J; Wang, C P; Liu, X J; Wang, Y; Liu, Z-K; Zhang, T-Y; Jiang, J Z

    2016-01-01

    This work aims to achieve deep insight into the phenomenon of phase transformation upon rapid cooling in metal systems and reveal the physical meaning of scatter in the time taken to reach crystallization. The total number of pure metals considered in this work accounts for 14. Taking pure copper as an example, the correlation between phase selection of crystal or glass and cooling rate was investigated using molecular dynamic simulations. The obtained results demonstrate that there exists a cooling rate region of 6.3 × 10(11)-16.6 × 10(11) K/s, in which crystalline fractions largely fluctuate along with cooling rates. Glass transformation in this cooling rate region is determined by atomic structure fluctuation, which is controlled by thermodynamic factors. According to the feature of bond-orientation order at different cooling rates, we propose two mechanisms of glass formation: (i) kinetic retardation of atom rearrangement or structural relaxation at a high cooling rate; and (ii) competition of icosahedral order against crystal order near the critical cooling rate. PMID:26939584

  16. Abnormal correlation between phase transformation and cooling rate for pure metals

    PubMed Central

    Han, J. J.; Wang, C. P.; Liu, X. J.; Wang, Y.; Liu, Z.-K.; Zhang, T.-Y.; Jiang, J. Z.

    2016-01-01

    This work aims to achieve deep insight into the phenomenon of phase transformation upon rapid cooling in metal systems and reveal the physical meaning of scatter in the time taken to reach crystallization. The total number of pure metals considered in this work accounts for 14. Taking pure copper as an example, the correlation between phase selection of crystal or glass and cooling rate was investigated using molecular dynamic simulations. The obtained results demonstrate that there exists a cooling rate region of 6.3 × 1011–16.6 × 1011 K/s, in which crystalline fractions largely fluctuate along with cooling rates. Glass transformation in this cooling rate region is determined by atomic structure fluctuation, which is controlled by thermodynamic factors. According to the feature of bond-orientation order at different cooling rates, we propose two mechanisms of glass formation: (i) kinetic retardation of atom rearrangement or structural relaxation at a high cooling rate; and (ii) competition of icosahedral order against crystal order near the critical cooling rate. PMID:26939584

  17. Optical multiple-image encryption based on phase encoding algorithm in the Fresnel transform domain

    NASA Astrophysics Data System (ADS)

    Huang, Jian-Ji; Hwang, Hone-Ene; Chen, Chun-Yuan; Chen, Ching-Mu

    2012-10-01

    A novel method of the optical multiple-image encryption based on the modified Gerchberg-Saxton algorithm (MGSA) is presented. This proposed method with an architecture of two adjacent phase only functions (POFs) in the Fresnel transform (FrT) domain that can extremely increase capacity of system for completely avoiding the crosstalk between the decrypted images. Each encrypted target image is separately encoded into a POF by using the MGSA which is with constraining the encrypted target image. Each created POF is then added to a prescribed fixed POF composed of a proposed MGSA-based phase encoding algorithm. Not only the wavelength and multiple-position parameters in the FrT domain as keys to increase system security, the created POFs are also served mutually as the encryption keys to decrypt target image based on cascading two POFs scheme. Compared with prior methods [23,24], the main advantages of this proposed encryption system is that it does not need any transformative lenses and that makes it very efficient and easy to implement optically. Simulation results show that this proposed encryption system can successfully achieve the multiple-image encryption with multiple-position keys, which is more advantageous in security than previous work [24] for its decryption process with only two POFs keys to accomplish this task.

  18. Nanometric Scale Investigation of Phase Transformations in Advanced Steels for Automotive Application

    NASA Astrophysics Data System (ADS)

    Drillet, Josée; Valle, Nathalie; Iung, Thierry

    2012-12-01

    The current trend toward producing lighter vehicles in the automotive industry is driven by the need to conform to the new exhaust emission control regulations. This objective presents a challenge to steel manufacturers. The difficulty lies in designing new alloys with an optimum strength/formability/cost balance for the various components. Here, the key to success lies in controlling the steel microstructure and especially the phase transformations at the smallest possible scale. Among the different alloying elements, light elements such as carbon and boron are of prime importance due to their major effects on the kinetics of phase transformations. Characterization tools combining high spatial and analytical resolution such as secondary ion mass spectrometry (SIMS) and field emission gun-transmission electron microscopy (TEM) were used. In this article, the examples presented are as follows. (1) Boron segregation and precipitation effects to control hardenability in martensitic steels. (2) Local carbon distribution in advanced high-strength steels, with a specific emphasis on martensite tempering. Links have been established between the boron and carbon distribution and the formability.

  19. A 3-D constitutive model for pressure-dependent phase transformation of porous shape memory alloys.

    PubMed

    Ashrafi, M J; Arghavani, J; Naghdabadi, R; Sohrabpour, S

    2015-02-01

    Porous shape memory alloys (SMAs) exhibit the interesting characteristics of porous metals together with shape memory effect and pseudo-elasticity of SMAs that make them appropriate for biomedical applications. In this paper, a 3-D phenomenological constitutive model for the pseudo-elastic behavior and shape memory effect of porous SMAs is developed within the framework of irreversible thermodynamics. Comparing to micromechanical and computational models, the proposed model is computationally cost effective and predicts the behavior of porous SMAs under proportional and non-proportional multiaxial loadings. Considering the pressure dependency of phase transformation in porous SMAs, proper internal variables, free energy and limit functions are introduced. With the aim of numerical implementation, time discretization and solution algorithm for the proposed model are also presented. Due to lack of enough experimental data on multiaxial loadings of porous SMAs, we employ a computational simulation method (CSM) together with available experimental data to validate the proposed constitutive model. The method is based on a 3-D finite element model of a representative volume element (RVE) with random pores pattern. Good agreement between the numerical predictions of the model and CSM results is observed for elastic and phase transformation behaviors in various thermomechanical loadings.

  20. Thermal stability and phase transformations of martensitic Ti-Nb alloys

    NASA Astrophysics Data System (ADS)

    Bönisch, Matthias; Calin, Mariana; Waitz, Thomas; Panigrahi, Ajit; Zehetbauer, Michael; Gebert, Annett; Skrotzki, Werner; Eckert, Jürgen

    2013-10-01

    Aiming at understanding the governing microstructural phenomena during heat treatments of Ni-free Ti-based shape memory materials for biomedical applications, a series of Ti-Nb alloys with Nb concentrations up to 29 wt% was produced by cold-crucible casting, followed by homogenization treatment and water quenching. Despite the large amount of literature available concerning the thermal stability and ageing behavior of Ti-Nb alloys, only few studies were performed dealing with the isochronal transformation behavior of initially martensitic Ti-Nb alloys. In this work, the formation of martensites (α‧ and α″) and their stability under different thermal processing conditions were investigated by a combination of x-ray diffraction, differential scanning calorimetry, dilatometry and electron microscopy. The effect of Nb additions on the structural competition in correlation with stable and metastable phase diagrams was also studied. Alloys with 24 wt% Nb or less undergo a \\alpha '/\\alpha '' \\to \\alpha + \\beta \\to \\beta transformation sequence on heating from room temperature to 1155 K. In alloys containing >24 wt% Nb α″ martensitically reverts back to β0, which is highly unstable against chemical demixing by formation of isothermal ωiso. During slow cooling from the single phase β domain α precipitates and only very limited amounts of α″ martensite form.

  1. Abnormal correlation between phase transformation and cooling rate for pure metals

    NASA Astrophysics Data System (ADS)

    Han, J. J.; Wang, C. P.; Liu, X. J.; Wang, Y.; Liu, Z.-K.; Zhang, T.-Y.; Jiang, J. Z.

    2016-03-01

    This work aims to achieve deep insight into the phenomenon of phase transformation upon rapid cooling in metal systems and reveal the physical meaning of scatter in the time taken to reach crystallization. The total number of pure metals considered in this work accounts for 14. Taking pure copper as an example, the correlation between phase selection of crystal or glass and cooling rate was investigated using molecular dynamic simulations. The obtained results demonstrate that there exists a cooling rate region of 6.3 × 1011–16.6 × 1011 K/s, in which crystalline fractions largely fluctuate along with cooling rates. Glass transformation in this cooling rate region is determined by atomic structure fluctuation, which is controlled by thermodynamic factors. According to the feature of bond-orientation order at different cooling rates, we propose two mechanisms of glass formation: (i) kinetic retardation of atom rearrangement or structural relaxation at a high cooling rate; and (ii) competition of icosahedral order against crystal order near the critical cooling rate.

  2. Influence of Ni on Martensitic Phase Transformations in NiTi Shape Memory Alloys

    SciTech Connect

    Frenzel, J.; George, Easo P; Dlouhy, A.; Somsen, Ch.; Wagner, M. F.-X; Eggeler, G.

    2010-01-01

    High-precision data on phase transformation temperatures in NiTi, including numerical expressions for the effect of Ni on M{sub S}, M{sub F}, A{sub S}, A{sub F} and T{sub 0}, are obtained, and the reasons for the large experimental scatter observed in previous studies are discussed. Clear experimental evidence is provided confirming the predictions of Tang et al. 1999 regarding deviations from a linear relation between the thermodynamic equilibrium temperature and Ni concentration. In addition to affecting the phase transition temperatures, increasing Ni contents are found to decrease the width of thermal hysteresis and the heat of transformation. These findings are rationalized on the basis of the crystallographic data of Prokoshkin et al. 2004 and the theory of Ball and James. The results show that it is important to document carefully the details of the arc-melting procedure used to make shape memory alloys and that, if the effects of processing are properly accounted for, precise values for the Ni concentration of the NiTi matrix can be obtained.

  3. Carbon deposition and phase transformations in red mud on exposure to methane.

    PubMed

    Sushil, S; Alabdulrahman, A M; Balakrishnan, M; Batra, V S; Blackley, R A; Clapp, J; Hargreaves, J S J; Monaghan, A; Pulford, I D; Rico, J L; Zhou, W

    2010-08-15

    A characterization study detailing the phase transformations and microstructural nature of the carbon deposited during methane decomposition over red mud has been undertaken. In situ XRD was carried out to study the phase transformation sequences of red mud during the reaction. Scanning electron microscopy, high resolution transmission electron microscopy, thermogravimetric analysis, BET surface area determination and CHN analysis were carried out to investigate the properties of the post-reaction samples. Exposure to methane with increasing temperature caused a stepwise reduction of iron oxides in red mud and promoted methane cracking leading to carbon deposition. The presence of carbon nanostructures was confirmed by HRTEM observations. The carbon formed was graphitic in nature and the spent red mud, rich in Fe and Fe(3)C formed as a result of the reduction of the iron oxide, was magnetic in nature. The surface area of the material was enhanced upon reaction. In addition, reactivity comparisons between goethite and red mud were carried out to study the formation of carbon oxides during reaction. PMID:20462696

  4. In situ HVEM studies of phase transformation in Zr alloys and compounds under irradiation

    SciTech Connect

    Motta, A.T.; Faldowski, J.A.; Howe, L.M.; Okamoto, P.R.

    1996-01-01

    The High Voltage Electron Microscope (HVEM)/Tandem facility at Argonne National Laboratory has been used to conduct detailed studies of the phase stability and microstructural evolution in zirconium alloys and compounds under ion and electron irradiation. Detailed kinetic studies of the crystalline-to-amorphous transformation of the intermetallic compounds Zr{sub 3}(Fe{sub 1-x}Ni{sub x}), Zr(Fe{sub 1-x},Cr{sub x}){sub 2}, Zr{sub 3}Fe, and Zr{sub 1.5} Nb{sub 1.5} Fe, both as second phase precipitates and in bulk form, have been performed using the in-situ capabilities of the Argonne facility, under a variety of irradiation conditions (temperature, dose rate). Results include a verification of a dose rate effect on amorphization and the influence of material variables (stoichiometry x, presence of stacking faults, crystal structure) on the critical temperature and on the critical dose for amorphization. Studies were also conducted of the microstructural evolution under irradiation of specially tailored binary and ternary model alloys. The stability of the {omega}-phase in Zr-20%Nb under electron and Ar ion irradiation was investigated as well as the {beta}-phase precipitation in Zr-2.5%Nb under Ar ion irradiation. The ensemble of these results is discussed in terms of theoretical models of amorphization and of irradiation-altered solubility.

  5. Efficient Estimation of Semiparametric Transformation Models for Two-Phase Cohort Studies

    PubMed Central

    ZENG, DONGLIN; LIN, D. Y.

    2013-01-01

    Under two-phase cohort designs, such as case-cohort and nested case-control sampling, information on observed event times, event indicators, and inexpensive covariates is collected in the first phase, and the first-phase information is used to select subjects for measurements of expensive covariates in the second phase; inexpensive covariates are also used in the data analysis to control for confounding and to evaluate interactions. This paper provides efficient estimation of semiparametric transformation models for such designs, accommodating both discrete and continuous covariates and allowing inexpensive and expensive covariates to be correlated. The estimation is based on the maximization of a modified nonparametric likelihood function through a generalization of the expectation-maximization algorithm. The resulting estimators are shown to be consistent, asymptotically normal and asymptotically efficient with easily estimated variances. Simulation studies demonstrate that the asymptotic approximations are accurate in practical situations. Empirical data from Wilms’ tumor studies and the Atherosclerosis Risk in Communities (ARIC) study are presented. PMID:24659837

  6. Phase transformation and fluorescent enhancement of ErF3 at high pressure

    NASA Astrophysics Data System (ADS)

    Li, Wentao; Ren, Xiangting; Huang, Yanwei; Yu, Zhenhai; Mi, Zhongying; Tamura, Nobumichi; Li, Xiaodong; Peng, Fang; Wang, Lin

    2016-09-01

    Pressure-induced phase transformation and fluorescent properties of ErF3 were investigated here using in-situ synchrotron X-ray diffraction and photoluminescence up to 32.1 GPa at room temperature. Results showed that ErF3 underwent a reversible pressure-induced phase transition from the β-YF3-type to the fluocerite LaF3-type at 9.8 GPa. The bulk moduli B0 for low- and high-pressure phases were determined to be 130 and 208 GPa, respectively. Photoluminescencent studies showed that new emission lines belonging to the transition of 2H11/2→4I15/2, 4S3/2→4I15/2, and 4F9/2→4I15/2 appeared during phase transition, suggesting pressure-induced electronic band splitting. Remarkably, significant pressure-induced enhancement of photoluminescence was observed, which was attributed to lattice distortion of the material under high pressure.

  7. Influence of annealing temperature on the phase transformation of Al2O3

    NASA Astrophysics Data System (ADS)

    Mahat, Annie Maria; Mastuli, Mohd Sufri; Kamarulzaman, Norlida

    2016-02-01

    In the present study, Al2O3 powders were prepared via a self-propagating combustion method using citric acid as a combustion agent. Effects of annealing temperature on the phase transformation of the prepared powders were studied on samples annealed at 800 °C and 1000 °C. The Al2O3 samples were characterized using X-Ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and N2 adsorption-desorption measurements. The XRD results showed that pure η-phase and pure α-phase of Al2O3 were obtained at 800 °C and 1000 °C, respectively. Their crystallite sizes are totally different as can be seen clearly from the FESEM micrographs. The η-Al2O3 sample annealed at low temperature has crystallite size smaller than 10 nm compared to the α-Al2O3 sample annealed at higher temperature which has crystallites from few microns to hundreds microns in size. From the BET (Brunauer-Emmett-Teller) method, the specific surface area for both samples are 59.4 m2g-1 and 3.1 m2g-1, respectively. It is proposed that the annealing temperature less pronounced for the morphology, but, it is significant for the phase transitions as well as the size and the specific surface area of the Al2O3 samples.

  8. Swift heavy ion induced phase transformation and thermoluminescence properties of zirconium oxide

    NASA Astrophysics Data System (ADS)

    Lokesha, H. S.; Nagabhushana, K. R.; Singh, Fouran

    2016-07-01

    Zirconium oxide (ZrO2) powder is synthesized by combustion technique. XRD pattern of ZrO2 shows monoclinic phase with average crystallite size 35 nm. Pellets of ZrO2 are irradiated with 100 MeV swift Si7+, Ni7+ and 120 MeV swift Ag9+ ions in the fluence range 3 × 1010-3 × 1013 ions cm-2. XRD pattern show the main diffraction peak correspond to monoclinic and tetragonal phase of ZrO2 in 2θ range 27-33°. Structural phase transformation is observed for Ni7+ and Ag9+ ion irradiated samples at a fluence 1 × 1013 ions cm-2 and 3 × 1012 ions cm-2 respectively, since the deposited electronic energy loss exceeds an effective threshold (>12 keV nm-1). Phase transition induced by Ag9+ ion is nearly 2.9 times faster than Ni7+ ion at 1 × 1013 ions cm-2. Ag9+ ion irradiation leads two ion impact processes. Thermoluminescence (TL) glow curves exhibit two glows, a well resolved peak at ∼424 K and unresolved peak at 550 K for all SHI irradiated samples. TL response is decreased with increase of ion fluence. Beyond 3 × 1012 ions cm-2, samples don't exhibit TL due to annihilation of defects.

  9. Dual phase transformation and resultant magnetic properties in Fe{sub 3}Pt thin films

    SciTech Connect

    Hsiao, S. N.; Lee, H. Y.; Chen, S. K.; Liu, S. H.

    2012-04-01

    Fifty-nm-thick Fe{sub 75}Pt{sub 25} thin films have been made on glass substrates by rf magnetron sputtering at room temperature, and subsequently annealed at 300 -700 deg. C (T{sub a}) for 1 h. The as-deposited Fe{sub 3}Pt film exhibits high magnetization of 1530 emu/cm{sup 3} and a disordered bcc structure, confirmed by high-resolution synchrotron radiation x-ray diffractometry. First-phase transformation from the bcc to disorder fcc structure occurs for samples annealed at 300 deg. C. With increasing of T{sub a} up to 375 deg. C, the film displays a nearly disordered fcc phase with low magnetization of 1083 emu/cm{sup 3}. The fcc phase changes to ordered L1{sub 2} structure for samples with T{sub a} {>=} 400 deg. C. The highly ordered L1{sub 2} phase with magnetization of 1270 emu/cm{sup 3} and coercivity of 66 Oe was obtained in Fe{sub 3}Pt film at 700 deg. C-annealing.

  10. Friction-induced structural transformations of the carbide phase in Hadfield steel

    NASA Astrophysics Data System (ADS)

    Korshunov, L. G.; Sagaradze, V. V.; Chernenko, N. L.; Shabashov, V. A.

    2015-08-01

    Structural transformations of the carbide phase in Hadfield steel (110G13) that occur upon plastic deformation by dry sliding friction have been studied by methods of optical metallography, X-ray diffraction, and transmission electron microscopy. Deformation is shown to lead to the refinement of the particles of the carbide phase (Fe, Mn)3C to a nanosized level. The effect of the deformation-induced dissolution of (Fe, Mn)3C carbides in austenite of 110G13 (Hadfield) steel has been revealed, which manifests in the appearance of new lines belonging to austenite with an unusually large lattice parameter ( a = 0.3660-0.3680 nm) in the X-ray diffraction patterns of steel tempered to obtain a fine-lamellar carbide phase after deformation. This austenite is the result of the deformation-induced dissolution of disperse (Fe, Mn)3C particles, which leads to the local enrichment of austenite with carbon and manganese. The tempering that leads to the formation of carbide particles in 110G13 steel exerts a negative influence on the strain hardening of the steel, despite the increase in the hardness of steel upon tempering and the development of the processes of the deformation-induced dissolution of the carbide phase, which leads to the strengthening of the γ solid solution.

  11. An Exploratory Study of the Viscoelasticity of Phase-Transforming Material

    SciTech Connect

    Li, L.; Wang, L; Vaughan, M

    2009-01-01

    Attenuation and modulus dispersion are typically associated with shear stress and strain. Time-dependent volume changes accompanying pressure variations can give rise to bulk modulus attenuation and dispersion. Phase transformations in a two-phase region are candidates for such phenomena. Here we report laboratory data that are consistent with bulk modulus softening as pressure is cycled in a region of coexisting olivine and spinel. We use Fay70For30 olivine as our sample. Experiments are performed in a multi-anvil high-pressure apparatus (Deformation DIA) using synchrotron (NSLS) X-ray radiation as the probing tool. Pressure is up to 12 GPa and temperature is up to 1450 C. Measurements were carried out within the binary loop where the olivine and spinel phases coexist. We apply a uniaxial oscillation stress onto the sample and Young's modulus and Q{sup -1} are measured at frequencies of 0.1-0.01 Hz. Our results indicate that the sinusoidal force applied to the sample in olivine-ringwoodite region has much lower bulk modulus and higher Q{sup -1} than in the single-phase regions. Our data are consistent with the diffusion controlled model of (Jackson, I., 2007. Physical origins of anelasticity and attenuation in rock, In: Price, G.D. (Ed.) Mineral Physics. Treatise On Geophysics. Elsevier), where the characteristic time decreases with decreasing strain.

  12. An exploratory study of the viscoelasticity of phase-transforming material

    NASA Astrophysics Data System (ADS)

    Li, Li; Wang, Liping; Vaughan, Michael

    2009-05-01

    Attenuation and modulus dispersion are typically associated with shear stress and strain. Time-dependent volume changes accompanying pressure variations can give rise to bulk modulus attenuation and dispersion. Phase transformations in a two-phase region are candidates for such phenomena. Here we report laboratory data that are consistent with bulk modulus softening as pressure is cycled in a region of coexisting olivine and spinel. We use Fay70For30 olivine as our sample. Experiments are performed in a multi-anvil high-pressure apparatus (Deformation DIA) using synchrotron (NSLS) X-ray radiation as the probing tool. Pressure is up to 12 GPa and temperature is up to 1450 °C. Measurements were carried out within the binary loop where the olivine and spinel phases coexist. We apply a uniaxial oscillation stress onto the sample and Young's modulus and Q-1 are measured at frequencies of 0.1-0.01 Hz. Our results indicate that the sinusoidal force applied to the sample in olivine-ringwoodite region has much lower bulk modulus and higher Q-1 than in the single-phase regions. Our data are consistent with the diffusion controlled model of [Jackson, I., 2007. Physical origins of anelasticity and attenuation in rock, In: Price, G.D. (Ed.) Mineral Physics. Treatise On Geophysics. Elsevier], where the characteristic time decreases with decreasing strain.

  13. Phase transformation of PZST-86/14-5-2Nb ceramic under quasi-static loading conditions.