Carbon-coated CoFe–CoFe2O4 composite particles with high and dual-band electromagnetic wave absorbing properties

NASA Astrophysics Data System (ADS)

Guan, Zhen-Jie; Jiang, Jian-Tang; Chen, Na; Gong, Yuan-Xun; Zhen, Liang

2018-07-01

SiO2 and TiO2, as conventional dielectric shells of ferromagnetic/dielectric composite particles, can protect ferromagnetic particles from aggregation and oxidation, but contribute little to electromagnetic loss. In this work, we designed nano-assembled CoFe–CoFe2O4@C composite particles, in which ferrites with high permeability were dielectric elements and carbon was introduced as protective layers, aiming for high-efficiency microwave absorption. These assembled particles with different CoFe contents were prepared through solvothermal methods and subsequent hydrogen-thermal reduction. CoFe nanoparticles were dispersed on a CoFe2O4 matrix via an in situ reduction transformation from CoFe2O4 to CoFe. The microstructure evolution of composite particles and corresponding electromagnetic properties tailoring were investigated. The content and size of CoFe as well as the porosity of composite particles increase gradually as the annealing temperature increases. A maximum reflection loss (RL max) of –71.73 dB is observed at 4.78 GHz in 3.4 mm thick coating using particles annealed at 500 °C as fillers. The coating presents double-band absorbing characteristics, as broad effective absorption bandwidth with RL > 5 (ERL 5) and high RL max are observed in both S-C and X-Ku bands. The tunability as well as the assembled characteristic of the electromagnetic property that endued from the composite structure contributes to the excellent electromagnetic wave absorbing performances.

Carbon-coated CoFe-CoFe2O4 composite particles with high and dual-band electromagnetic wave absorbing properties.

PubMed

Guan, Zhen-Jie; Jiang, Jian-Tang; Chen, Na; Gong, Yuan-Xun; Zhen, Liang

2018-07-27

SiO 2 and TiO 2 , as conventional dielectric shells of ferromagnetic/dielectric composite particles, can protect ferromagnetic particles from aggregation and oxidation, but contribute little to electromagnetic loss. In this work, we designed nano-assembled CoFe-CoFe 2 O 4 @C composite particles, in which ferrites with high permeability were dielectric elements and carbon was introduced as protective layers, aiming for high-efficiency microwave absorption. These assembled particles with different CoFe contents were prepared through solvothermal methods and subsequent hydrogen-thermal reduction. CoFe nanoparticles were dispersed on a CoFe 2 O 4 matrix via an in situ reduction transformation from CoFe 2 O 4 to CoFe. The microstructure evolution of composite particles and corresponding electromagnetic properties tailoring were investigated. The content and size of CoFe as well as the porosity of composite particles increase gradually as the annealing temperature increases. A maximum reflection loss (RL max ) of -71.73 dB is observed at 4.78 GHz in 3.4 mm thick coating using particles annealed at 500 °C as fillers. The coating presents double-band absorbing characteristics, as broad effective absorption bandwidth with RL > 5 (ERL 5 ) and high RL max are observed in both S-C and X-K u bands. The tunability as well as the assembled characteristic of the electromagnetic property that endued from the composite structure contributes to the excellent electromagnetic wave absorbing performances.

Single Crystalline Co3O4 Nanocrystals Exposed with Different Crystal Planes for Li-O2 Batteries

PubMed Central

Su, Dawei; Dou, Shixue; Wang, Guoxiu

2014-01-01

Single crystalline Co3O4 nanocrystals exposed with different crystal planes were synthesised, including cubic Co3O4 nanocrystals enclosed by {100} crystal planes, pseudo octahedral Co3O4 enclosed by {100} and {110} crystal planes, Co3O4 nanosheets exposed by {110} crystal planes, hexagonal Co3O4 nanoplatelets exposed with {111} crystal planes, and Co3O4 nanolaminar exposed with {112} crystal planes. Well single crystalline features of these Co3O4 nanocrystals were confirmed by FESEM and HRTEM analyses. The electrochemical performance for Li-O2 batteries shows that Co3O4 nanocrystals can significantly reduce the discharge-charge over-potential via the effect on the oxygen evolution reaction (OER). From the comparison on their catalytic performances, we found that the essential factor to promote the oxygen evolution reactions is the surface crystal planes of Co3O4 nanocrystals, namely, crystal planes-dependent process. The correlation between different Co3O4 crystal planes and their effect on reducing charge-discharge over-potential was established: {100} < {110} < {112} < {111}. PMID:25169737

Microstructure and inclusion of Ti-6Al-4V fabricated by selective laser melting

NASA Astrophysics Data System (ADS)

Huang, Qianli; Hu, Ningmin; Yang, Xing; Zhang, Ranran; Feng, Qingling

2016-12-01

Selective laser melting (SLM) was used in fabricating the dense part from pre-alloyed Ti-6Al-4V powder. The microstructural evolution and inclusion formation of as-fabricated part were characterized in depth. The microstructure was characterized by features of columnar prior β grains and acicular martensite α'. High density defects such as dislocations and twins can be produced in SLM process. Investigations on the inclusions find out that hard alpha inclusion, amorphous CaO and microcrystalline Al2O3 are three main inclusions formed in SLM. The inclusions formed at some specific sites on melt pool surface. The microstructural evolution and inclusion formation of as-fabricated material are closely related to the SLM process.

Nanocrystallization of LiCoO2 Cathodes for Thin Film Batteries Utilizing Pulse Thermal Processing

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

None

2009-04-01

This factsheet describes a study whose focus is on the nanocrystallization of the LiCoO2 cathode thin films on polyimide substrates and evaluate the microstructural evolution and resistance as a function of PTP processing conditions.

Co@Co3O4 nanoparticle embedded nitrogen-doped carbon architectures as efficient bicatalysts for oxygen reduction and evolution reactions

NASA Astrophysics Data System (ADS)

Qi, Chunling; Zhang, Li; Xu, Guancheng; Sun, Zhipeng; Zhao, Aihua; Jia, Dianzeng

2018-01-01

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) play crucial roles in efficient energy conversion and storage solutions. Here, Co@Co3O4 nanoparticle embedded nitrogen-doped carbon architectures (denoted as Co@Co3O4/NCs) are prepared via a simple two-step and in situ approach by carbonization and subsequent oxidation of Co-MOF containing high contents of carbon and nitrogen. When evaluated as electrocatalyst towards both ORR and OER in a KOH electrolyte solution, the as-fabricated Co@Co3O4/NC-2 exhibits similar ORR catalytic activity to the commercial Pt/C catalyst, but superior stability and good methanol tolerance. Furthermore, the as-fabricated catalysts also show promising catalytic activity for OER. The effective catalytic activities originate from the synergistic effects between well wrapped Co@Co3O4 nanoparticles and nitrogen doped carbon structures.

Synthesis of polycrystalline CoFe2O4 and NiFe2O4 powders by auto-combustion method using a novel amino-based gel

NASA Astrophysics Data System (ADS)

Jiang, Linwen; Yang, Shanshan; Zheng, Mengyao; Wu, Anhua; Chen, Hongbing

2017-12-01

Polycrystalline CoFe2O4/NiFe2O4 powders were prepared by auto-combustion method using a novel amino-based gel. The thermal evolution of gel precursors, as well as the microstructure, morphology and magnetic properties of as-synthesized powders were studied in detail. Energy dispersive x-ray spectroscopy indicated that the ratios of Ni:Fe was close to the theoretical value (Ni:Fe  =  1:2), suggesting high purity of synthesized NiFe2O4 powders. The saturated magnetization (M s) and residual magnetization (M r) of CoFe2O4 were highly dependent upon the annealed temperatures. The M s increased from 77.5 to 84.7 emu g-1, and M r increased from 37.7 emu g-1 to 42.5 emu g-1 by annealing from room temperature to 600 °C. The M s of NiFe2O4 was 38.7 emu g-1, much lower than that of CoFe2O4. The experimental results indicated that this auto-combustion method using amino-based gel was a suitable method for synthesizing high-quality CoFe2O4/NiFe2O4 powders.

Structural evolution of epitaxial SrCoO x films near topotactic phase transition

DOE PAGES

Jeen, Hyoung Jeen; Lee, Ho Nyung

2015-12-18

Control of oxygen stoichiometry in complex oxides via topotactic phase transition is an interesting avenue to not only modifying the physical properties, but utilizing in many energy technologies, such as energy storage and catalysts. However, detailed structural evolution in the close proximity of the topotactic phase transition in multivalent oxides has not been much studied. In this work, we used strontium cobaltites (SrCoO x) epitaxially grown by pulsed laser epitaxy (PLE) as a model system to study the oxidation-driven evolution of the structure, electronic, and magnetic properties. We grew coherently strained SrCoO 2.5thin films and performed post-annealing at various temperaturesmore » for topotactic conversion into the perovskite phase (SrCoO 3-δ). We clearly observed significant changes in electronic transport, magnetism, and microstructure near the critical temperature for the topotactic transformation from the brownmillerite to the perovskite phase. Furthermore, the overall crystallinity was well maintained without much structural degradation, indicating that topotactic phase control can be a useful tool to control the physical properties repeatedly via redox reactions.« less

Effect of Co2+ and Y3+ ions insertion on the microstructure development and magnetic properties of Ni0.5Zn0.5Fe2O4 powders synthesized using Co-precipitation method

NASA Astrophysics Data System (ADS)

Rashad, M. M.; Rayan, D. A.; Turky, A. O.; Hessien, M. M.

2015-01-01

Nanocrystalline Ni0.5Zn0.5-xCoxFe2-zYzO4 powders (x=0-0.3 and z from 0 to 0.3) have been synthesized via a facile co-precipitation technique. X-ray diffraction (XRD), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM) are utilized in order to study the effect of variation of cobalt and yttrium substitutions and its impact on crystalline size, lattice parameter, X-ray density, microstructure and magnetic properties of the formed powders. X-ray diffraction data indicated that, after doping, all samples consisted of the main spinel phase for the formed precursors precipitated at pH 10 annealed at 1000 oC for 2 h. The lattice parameter and the unit cell were decreased linearly with increasing Co content whereas they were increased with increasing the Y incorporation. Additionally, the porosity was increased with increasing Co concentration while it was decreased with increasing the Y insertion. The mean ionic radii and hopping and bond lengths was decreased with the value of Co2+ and they were increased with the value of Y3+ ion as well as both of Y3+ and Co2+ ions. The microstructures of the produced powders were found to be cubic like structure. The addition of Y3+ ion suppressed the grain size whereas addition of Co2+ ion enhanced the grain growth availably. An examination of the magnetic properties revealed an increase in saturation magnetization with increasing Co and Y concentrations incorporation up to x=0.3. Meanwhile, the formed powders exhibited superparamagnetic characteristics. A high saturation magnetization (77.0 emu/g) was achieved for Ni0.5Zn0.2Co0.3Fe2O4 sample annealed at 1000 oC for 2 h.

Preparation and electrochemical properties of NiO-Co3O4 composite as electrode materials for supercapacitors

NASA Astrophysics Data System (ADS)

Wang, X. W.; Zheng, D. L.; Yang, P. Z.; Wang, X. E.; Zhu, Q. Q.; Ma, P. F.; Sun, L. Y.

2017-01-01

The precursor of NiO-Co3O4 composites was synthesized via a simple hydrothermal process. After that, the precursor was calcined at 300 °C for 3 h to obtain the composite powders. The powders calcined at 300 °C showed amorphous, and the powders calcined at 400 °C and 500 °C for comparison showed the composite phase of NiO and Co3O4. The composite products showed a microstructure of micro-spheres. For the samples calcined at 300 °C for 3 h, the specific capacitance reached 801 F g-1 at a current density of 1 A g-1.

Reversible amorphization and the catalytically active state of crystalline Co3O4 during oxygen evolution

PubMed Central

Bergmann, Arno; Martinez-Moreno, Elias; Teschner, Detre; Chernev, Petko; Gliech, Manuel; de Araújo, Jorge Ferreira; Reier, Tobias; Dau, Holger; Strasser, Peter

2015-01-01

Water splitting catalysed by earth-abundant materials is pivotal for global-scale production of non-fossil fuels, yet our understanding of the active catalyst structure and reactivity is still insufficient. Here we report on the structurally reversible evolution of crystalline Co3O4 electrocatalysts during oxygen evolution reaction identified using advanced in situ X-ray techniques. At electrode potentials facilitating oxygen evolution, a sub-nanometre shell of the Co3O4 is transformed into an X-ray amorphous CoOx(OH)y which comprises di-μ-oxo-bridged Co3+/4+ ions. Unlike irreversible amorphizations, here, the formation of the catalytically-active layer is reversed by re-crystallization upon return to non-catalytic electrode conditions. The Co3O4 material thus combines the stability advantages of a controlled, stable crystalline material with high catalytic activity, thanks to the structural flexibility of its active amorphous oxides. We propose that crystalline oxides may be tailored for generating reactive amorphous surface layers at catalytic potentials, just to return to their stable crystalline state under rest conditions. PMID:26456525

Reversible amorphization and the catalytically active state of crystalline Co3O4 during oxygen evolution.

PubMed

Bergmann, Arno; Martinez-Moreno, Elias; Teschner, Detre; Chernev, Petko; Gliech, Manuel; de Araújo, Jorge Ferreira; Reier, Tobias; Dau, Holger; Strasser, Peter

2015-10-12

Water splitting catalysed by earth-abundant materials is pivotal for global-scale production of non-fossil fuels, yet our understanding of the active catalyst structure and reactivity is still insufficient. Here we report on the structurally reversible evolution of crystalline Co3O4 electrocatalysts during oxygen evolution reaction identified using advanced in situ X-ray techniques. At electrode potentials facilitating oxygen evolution, a sub-nanometre shell of the Co3O4 is transformed into an X-ray amorphous CoOx(OH)y which comprises di-μ-oxo-bridged Co(3+/4+) ions. Unlike irreversible amorphizations, here, the formation of the catalytically-active layer is reversed by re-crystallization upon return to non-catalytic electrode conditions. The Co3O4 material thus combines the stability advantages of a controlled, stable crystalline material with high catalytic activity, thanks to the structural flexibility of its active amorphous oxides. We propose that crystalline oxides may be tailored for generating reactive amorphous surface layers at catalytic potentials, just to return to their stable crystalline state under rest conditions.

Crystal Structure, Piezoelectric and Dielectric Properties of (Li, Ce)4+, Nb5+ and Mn2+ Co-doped CaBi4Ti4O15 High-Temperature Ceramics

NASA Astrophysics Data System (ADS)

Xin, Deqiong; Chen, Qiang; Wu, Jiagang; Bao, Shaoming; Zhang, Wen; Xiao, Dingquan; Zhu, Jianguo

2016-07-01

Bismuth-layered structured ceramics Ca0.85(Li,Ce)0.075Bi4Ti4- x Nb x O15-0.01MnCO3 were prepared by the conventional solid-state reaction method. The evolution of microstructure and corresponding electrical properties were studied. All the samples presented a single bismuth layered-structural phase with m = 4, indicating that (Li, Ce)4+, Nb5+ and Mn2+ adequately enter into the pseudo-perovskite structure and form solid solutions. It was found that Ca0.85(Li,Ce)0.075Bi4Ti3.98Nb0.02O15-0.01MnCO3 (CBTLCM-0.02Nb) ceramics possess the optimum electrical properties. The piezoelectric coefficient d 33, dielectric constant ɛ r, loss tan δ, planar electromechanical coupling factor k p and Curie-temperature T C of CBTLCM-0.02Nb ceramics were found to be ˜19.6 pC/N, 160, 0.16%, 8.1% and 767°C, respectively. Furthermore, the thermal depoling behavior demonstrates that the d 33 value of x = 0.02 content remains at 16.8 pC/N after annealing at 500°C. These results suggest that the (Li, Ce)4+-, Nb5+- and Mn2+-doped CBT-based ceramics are promising candidates for high-temperature piezoelectric applications.

In situ TEM study of electron-beam radiation induced boron diffusion and effects on phase and microstructure evolution in nanostructured CoFeB/SiO2 thin film

NASA Astrophysics Data System (ADS)

Liu, B. H.; Teo, H. W.; Mo, Z. H.; Mai, Z. H.; Lam, J.; Xue, J. M.; Zhao, Y. Z.; Tan, P. K.

2017-01-01

Using in situ transmission electron microscopy (TEM), we studied boron diffusion and segregation in CoFeB/SiO2 nanostructured thin film stacks. We also investigated how these phenomena affected the phase and microstructure of CoFeB thin films under electron beam irradiation at 300 kV. A unique phase transformation was observed in CoFeB thin films under high-dose electron irradiation, from a polycrystalline Co3Fe to a unilateral amorphous phase of Co3Fe and nanocrystalline FexCo23-xB6. The unilateral amorphization of the Co3Fe film showed an electron-dose-rate sensitivity with a threshold dose rate. Detailed in situ TEM studies revealed that the unilateral amorphization of the Co3Fe film arose from boron segregation at the bottom of the Co3Fe thin film induced by radiation-enhanced diffusion of boron atoms that were displaced by electron knock-on effects. The radiation-induced nanocrystallization of FexCo23-xB6 was also found to be dose-rate sensitive with a higher electron beam current leading to earlier nucleation and more rapid grain growth. The nanocrystallization of FexCo23-xB6 occurred preferentially at the CoFeB/SiO2 interface. Kinetic studies by in situ TEM revealed the surface crystallization and diffusion-controlled nucleation and grain growth mechanisms. The radiation-enhanced atomic diffusivity and high-concentration of radiation-induced point defects at the Co3Fe/SiO2 interface enhanced the local short-range ordering of Fe, Co, and B atoms, favoring nucleation and grain growth of FexCo23-xB6 at the interface.

Effect of mesoporous g-C3N4 substrate on catalytic oxidation of CO over Co3O4

NASA Astrophysics Data System (ADS)

Yang, Heng; Lv, Kangle; Zhu, Junjiang; Li, Qin; Tang, Dingguo; Ho, Wingkei; Li, Mei; Carabineiro, Sónia A. C.

2017-04-01

Mesoporous graphitic carbon nitride (mpg-CN) was synthesized using Triton X-100, a surfactant containing a hydrophilic polyethylene oxide group and a tert-octyl-phenyl hydrophobic moiety, as a soft template. The obtained mpg-CN was used as a support for Co3O4, and this supported catalyst was used for CO oxidation. The effects of the amount of Triton X-100, weight ratio of Co3O4 to mpg-CN and calcination temperature on the catalytic performances for CO oxidation of Co3O4/mpg-CN composites were systematically studied. It was found that the presence of Triton X-100 not only retarded the polymerization of dicyandiamide, but also affected the microstructure of Co3O4. Bubbles formed because of the hydrophobic group of the surfactant Triton X-100 can be act as a soft template for the synthesis of mesoporous g-C3N4. The enhanced catalytic activity of Co3O4/mpg-CN was attributed to a synergistic effect, enlarged BET surface areas, increased Co3+ and lattice oxygen contents, and the porous structure of mpg-CN support. The high stability of 12.5% Co3O4/mpg-CN(1.0) makes it a promising catalyst for practical applications.

Novel Co3O4 Nanoparticles/Nitrogen-Doped Carbon Composites with Extraordinary Catalytic Activity for Oxygen Evolution Reaction (OER)

NASA Astrophysics Data System (ADS)

Yang, Xiaobing; Chen, Juan; Chen, Yuqing; Feng, Pingjing; Lai, Huixian; Li, Jintang; Luo, Xuetao

2018-03-01

Herein, Co3O4 nanoparticles/nitrogen-doped carbon (Co3O4/NPC) composites with different structures were prepared via a facile method. Structure control was achieved by the rational morphology design of ZIF-67 precursors, which were then pyrolyzed in air to obtain Co3O4/NPC composites. When applied as catalysts for the oxygen evolution reaction (OER), the M-Co3O4/NPC composites derived from the flower-like ZIF-67 showed superior catalytic activities than those derived from the rhombic dodecahedron and hollow spherical ZIF-67. The former M-Co3O4/NPC composite displayed a small over-potential of 0.3 V, low onset potential of 1.41 V, small Tafel slope of 83 mV dec-1, and a desirable stability. (94.7% OER activity was retained after 10 h.) The excellent performance of the flower-like M-Co3O4/NPC composite in the OER was attributed to its favorable structure. [Figure not available: see fulltext.

Effect of ball milling and dynamic compaction on magnetic properties of Al2O3/Co(P) composite particles

NASA Astrophysics Data System (ADS)

Denisova, E. A.; Kuzovnikova, L. A.; Iskhakov, R. S.; Bukaemskiy, A. A.; Eremin, E. V.; Nemtsev, I. V.

2014-05-01

The evolution of the magnetic properties of composite Al2O3/Co(P) particles during ball milling and dynamic compaction is investigated. To prepare starting composite particles, the Al2O3 granules were coated with a Co95P5 shell by electroless plating. The magnetic and structural properties of the composite particles are characterized by scanning electron microscopy, X-ray diffraction, and the use of the Physical Property Measurement System. The use of composite core-shell particles as starting powder for mechanoactivation allows to decrease treatment duration to 1 h and to produce a more homogeneous bulk sample than in the case of the mixture of Co and Al2O3 powders. The magnetic properties of the milled composite particles are correlated with changes in the microstructure. Reduction in grain size of Co during milling leads to an increase of the volume fraction of superparamagnetic particles and to a decrease of the saturation magnetization. The local magnetic anisotropy field depends on the amount of hcp-Co phase in sample. The anisotropy field value decreases from 8.4 kOe to 3.8 kOe with an increase in milling duration up to 75 min. The regimes of dynamic compaction were selected so that the magnetic characteristics—saturation magnetization and coercive field—remained unchanged.

Decoration of mesoporous Co3O4 nanospheres assembled by monocrystal nanodots on g-C3N4 to construct Z-scheme system for improving photocatalytic performance

NASA Astrophysics Data System (ADS)

Wu, Haijun; Li, Chunmei; Che, Huinan; Hu, Hao; Hu, Wei; Liu, Chunbo; Ai, Junzhe; Dong, Hongjun

2018-05-01

The Co3O4/g-C3N4 Z-scheme system is constructed by decoration of mesoporous Co3O4 nanospheres assembled by monocrystal nanodots on the surface of g-C3N4, which dramatically improves the photocatalytic activity for degrading tetracycline hydrochloride (TC) compared with single g-C3N4. The microstructure investigations evidence the mesoporous structure and enlarged specific surface area of Co3O4/g-C3N4 Z-scheme system, which implies the increase of surface active sites and adsorption ability for reactant molecules. Moreover, by virtue of analyzing physical and photoelectrochemical properties, it evidences that the decoration effect of mesoporous Co3O4 nanospheres on the surface of g-C3N4 obviously improves the transfer and separation efficiency of charge carriers between two phase interfaces and broadens light harvest range. These important factors are beneficial to enhancing photocatalytic activity of Co3O4/g-C3N4 Z-scheme system. In addition, the photocatalityc reaction mechanism is also revealed in depth.

Surface chemistry and microstructure of metallic biomaterials for hip and knee endoprostheses

NASA Astrophysics Data System (ADS)

Jenko, Monika; Gorenšek, Matevž; Godec, Matjaž; Hodnik, Maxinne; Batič, Barbara Šetina; Donik, Črtomir; Grant, John T.; Dolinar, Drago

2018-01-01

The surface chemistry and microstructures of titanium alloys (both new and used) and CoCrMo alloys used for hip and knee endoprostheses were determined using SEM (morphology), EBSD (phase analysis), AES and XPS (surface chemistry). Two new and two used endoprostheses were studied. The SEM SE and BE images showed their microstructures, while the EBSD provided the phases of the materials. During the production of the hip and knee endoprostheses, these materials are subject to severe thermomechanical treatments and physicochemical processes that are decisive for CoCrMo alloys. The AES and XPS results showed that thin oxide films on (a) Ti6Al4V are primarily a mixture of TiO2 with a small amount of Al2O3, while the V is depleted, (b) Ti6Al7Nb is primarily a mixture of TiO2 with a small amount of Al2O3 and Nb2O5, and (c) the CoCrMo alloy is primarily a mixture of Cr2O3 with small amounts of Co and Mo oxides. The thin oxide film on the CoCrMo alloy should prevent intergranular corrosion and improve the biocompatibility. The thin oxide films on the Ti alloys prevent further corrosion, improve the biocompatibility, and affect the osseointegration.

Microstructural analysis and thermoelectric properties of Sn-Al co-doped ZnO ceramics

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

Hoemke, Joshua, E-mail: jhoemke@sigma.t.u-tokyo.ac.jp; Tochigi, Eita; Shibata, Naoya

2016-08-26

Sn-Al co-doped polycrystalline ZnO ceramics were prepared by sintering in air. Phase and microstructure analysis was performed by X-ray diffraction and SEM-EDS and thermoelectric properties were measured. XRD analysis showed a ZnO primary phase as well as secondary phase peaks due to the formation of a Zn{sub 2}SnO{sub 4} spinel phase or SnO{sub 2}(ZnO:Sn-Al){sub m} intergrowth phase. SEM analysis revealed a dense microstructure with a small number of nanometric pores, consistent with the measured density of 5.48 g/cm{sup 3}. An activated electrical conductivity characteristic of a semiconducting material was observed as well as a negative Seebeck coefficient with both valuesmore » increasing in absolute value from RT to 730 °C. The power factor had a maximum value of 3.73×10{sup −4} W m{sup −1} K{sup −2} at 730 °C. Thermal conductivity measurements showed a significant reduction over the measured temperature range compared to undoped ZnO. This could be attributed to grain size reduction, the formation of a nanoscale secondary phase or a reduction in crystallinity caused by Sn-Al co-doping. A maximum ZT of 0.06 was obtained at 750 °C for the Sn-Al co-doped ZnO ceramics.« less

Structure Evolution and Multiferroic Properties in Cobalt Doped Bi4NdTi3Fe1-xCoxO15-Bi3NdTi2Fe1-xCoxO12-δ Intergrowth Aurivillius Compounds

PubMed Central

Zhang, D. L.; Huang, W. C.; Chen, Z. W.; Zhao, W. B.; Feng, L.; Li, M.; Yin, Y. W.; Dong, S. N.; Li, X. G.

2017-01-01

Here, we report the structure evolution, magnetic and ferroelectric properties in Co-doped 4- and 3-layered intergrowth Aurivillius compounds Bi4NdTi3Fe1-xCoxO15-Bi3NdTi2Fe1-xCoxO12-δ. The compounds suffer a structure evolution from the parent 4-layered phase (Bi4NdTi3FeO15) to 3-layered phase (Bi3NdTi2CoO12-δ) with increasing cobalt doping level from 0 to 1. Meanwhile the remanent magnetization and polarization show opposite variation tendencies against the doping level, and the sample with x = 0.3 has the largest remanent magnetization and the smallest polarization. It is believed that the Co concentration dependent magnetic properties are related to the population of the Fe3+ -O-Co3+ bonds, while the suppressed ferroelectric polarization is due to the enhanced leakage current caused by the increasing Co concentration. Furthermore, the samples (x = 0.1–0.7) with ferromagnetism show magnetoelectric coupling effects at room temperature. The results indicate that it is an effective method to create new multiferroic materials through modifying natural superlattices. PMID:28272495

Microstructure and microwave magnetic properties of Low-Firing Li0.42Zn0.27Ti0.11Mn0.1Fe2.1O4 ferrite

NASA Astrophysics Data System (ADS)

Xie, Fei; Jia, Lijun; Shen, Qihang; Qiu, Hua; Zhang, Huaiwu

2018-03-01

Low firing temperature and excellent gyromagnetic properties such as high remanence square ratio and narrow ferromagnetic resonance line width are required for the application in nonreciprocal microwave ferrite devices based on low temperature cofired ceramics (LTCC) technology. In this research, Bi2O3-Li2CO3 mixture was introduced as the sintering agent to lower the sintering temperature of Li0.42Zn0.27Ti0.11Mn0.1Fe2.1O4 ferrite. The influence of Bi2O3-Li2CO3 mixture upon the phase composition, composite microstructures and gyromagnetic properties of LiZnTiMn ferrite sintered at low temperature has been investigated for LTCC integration applications. With a proper amount of Bi2O3-Li2CO3 mixture, the sintering temperature of LiZnTiMn ferrite successfully reduced to below 900°C from 1100°C without degradation of magnetic properties, meanwhile, both of saturation flux density and remanence square ratio were increased.

Constructing Highly Uniform Onion-Ring-like Graphitic Carbon Nitride for Efficient Visible-Light-Driven Photocatalytic Hydrogen Evolution.

PubMed

Cui, Lifeng; Song, Jialing; McGuire, Allister F; Kang, Shifei; Fang, Xueyou; Wang, Junjie; Yin, Chaochuang; Li, Xi; Wang, Yangang; Cui, Bianxiao

2018-06-13

The introduction of microstructure to the metal-free graphitic carbon nitride (g-C 3 N 4 ) photocatalyst holds promise in enhancing its catalytic performance. However, producing such microstructured g-C 3 N 4 remains technically challenging due to a complicated synthetic process and high cost. In this study, we develop a facile and in-air chemical vapor deposition (CVD) method that produces onion-ring-like g-C 3 N 4 microstructures in a simple, reliable, and economical manner. This method involves the use of randomly packed 350 nm SiO 2 microspheres as a hard template and melamine as a CVD precursor for the deposition of a thin layer of g-C 3 N 4 in the narrow space between the SiO 2 microspheres. After dissolution of the microsphere template, the resultant g-C 3 N 4 exhibits uniquely uniform onion-ring-like microstructures. Unlike previously reported g-C 3 N 4 powder morphologies that show various degrees of agglomeration and irregularity, the onion-ring-like g-C 3 N 4 is highly dispersed and uniform. The calculated band gap for onion-ring-like g-C 3 N 4 is 2.58 eV, which is significantly narrower than that of bulk g-C 3 N 4 at 2.70 eV. Experimental characterization and testing suggest that, in comparison with bulk g-C 3 N 4 , onion-ring-like g-C 3 N 4 facilitates charge separation, extends the lifetime of photoinduced carriers, exhibits 5-fold higher photocatalytic hydrogen evolution, and shows great potential for photocatalytic applications.

Effects of addition of Bi2Ca2Co2O y on the thermoelectric properties of Ca3Co4O9 polycrystalline ceramics

NASA Astrophysics Data System (ADS)

Feng, Ningbo; Liao, Y. W.; Lu, Y.; He, Y.; Jin, Y. R.; Liu, X. R.

2018-06-01

Thermoelectric properties of Ca3Co4O9 polycrystalline ceramics with sheet grains were optimized by adding Bi2Ca2Co2O y phase. Therefore, the (1 - x) Ca3Co4O9/ x Bi2Ca2Co2O y (0 ≤ x ≤ 1) composites were prepared. The phase constitution and micro-structure of the samples were analyzed by XRD and SEM, respectively. With the addition of Bi2Ca2Co2O y , the apparent density D a and the relative density D r of the samples continuously increases. When x ≤ 0.4, the electrical resistivity of the samples declines, however, when x ≥ 0.4, the electrical resistivity of the samples increases. The Seebeck coefficient of the samples grows with the increase of the x monotonously. The power factor of the 0.6 Ca3Co4O9/0.4 Bi2Ca2Co2O y samples reaches 0.24 mW m-1K-2 at 973 K. Thermal conductivity κ of the 0.6 Ca3Co4O9/0.4 Bi2Ca2Co2O y monotonously decreases with the temperature rising, achieving the minimum about 1.34 W m-1K-1 at 973 K. The ZT of 0.6 Ca3Co4O9/0.4 Bi2Ca2Co2O y composites gets to 0.18, which is comparable to that of most doped Ca3Co4O9 polycrystalline ceramics, implying higher ZT can be realized by combining the strategy of doping and introducing the Bi2Ca2Co2O y .

Effect of Mg and Si co-substitution on microstructure and strength of tricalcium phosphate ceramics.

PubMed

García-Páez, Ismael H; Carrodeguas, Raúl García; De Aza, Antonio H; Baudín, Carmen; Pena, Pilar

2014-02-01

Magnesium and silicon co-doped tricalcium phosphate (TCP) ceramics with compositions corresponding to 0, 5 and 10wt% CaMg(SiO3)2 in the system Ca3(PO4)2-CaMg(SiO3)2 were obtained by conventional sintering of compacted mixtures of Ca3(PO4)2, MgO, SiO2 and CaCO3 powders at temperatures between 1100 and 1450°C. Microstructural analyses were performed by X-ray diffraction and field emission scanning electron microscopy with energy dispersive spectroscopy. Major phases in the obtained ceramics were β- or α+β-tricalcium phosphate containing Mg and Si in solid solution. Certain amounts of liquid were formed during sintering depending on composition and temperature. There were found significant differences in distributions of strength determined by the diametral compression of disc tests (DCDT). Failure strengths were controlled by microstructural defects associated with phase development. Mg and Si additions were found to be effective to improve densification and associated strength of TCP bioceramics due to the enhancement of sintering by the low viscosity liquids formed. The highest density and strength were obtained for the TCP ceramic containing 5wt% CaMg(SiO3)2 sintered at 1300°C. Cracking and porosity increased at higher temperatures due to grain growth and swelling. © 2013 Published by Elsevier Ltd.

Quantitative Analysis of Three-dimensional Microstructure of Li-ion Battery Electrodes

NASA Astrophysics Data System (ADS)

Liu, Zhao

Li-ion batteries (LIBs) have attracted considerable attention in the past two decades due to their widespread applications in portable electronics, and their growing use in electric vehicles and large-scale grid storage. Increasing battery energy density and powder density while maintaining long life, along with battery safety, are the biggest challenges that limit their further development. Various approaches with materials and chemistry have been employed to improve performance. However, one less-studied aspect that also impacts performance is the electrode microstructure. In particular, three-dimensional (3D) electrode microstructural data for LIB electrodes, which were not widely available prior to this thesis, can provide important input for understanding and improving LIB performance. The focus of this thesis is to apply 3D tomographic techniques, together with electrochemical performance data, to obtain LIB microstructure-performance correlations. Two advanced 3D structural analysis techniques, focused ion beam-scanning electron microscopy (FIB-SEM) and transmission X-ray microscopy (TXM) nanotomography, are used to quantify LIB electrode microstructure. 3D characterization of LIB electrode microstructure is used to obtain a deeper understanding of mechanisms that limit LIB performance. Microstructural characterization before and after cycling is used to explore capacity loss mechanisms. It is hoped that the results can guide electrode microstructures design to improve performance and stability. Two types of commercial electrodes, LiCoO2 and LiCoO 2/Li(Ni1/3Mn1/3Co1/3)O2, are studied using FIB-SEM and TXM. Both methods were found to be applicable to quantifying the oxide particle microstructure, including volume fraction, surface area, and particle size distribution, and results agreed well. However, structural inhomogeneity found in these commercial samples, limited the capability to resolve microstructural changes during cycling. In order to also quantify carbonaceous phases in the electrodes, which strongly correlate with LIB transport properties, a three-phase FIB-SEM method was developed where silicone resin was infiltrated into electrode pores, providing good image contrast with the carbon particles. Structural parameters including phase connectivity and tortuosity are quantified for commercial LiCoO 2 and laboratory-made LiFePO4 electrodes to help understand the transport process in these electrodes. For LiCoO2 electrodes, a heterogeneous tortuosity distribution observed in the electrolyte phase may result in inhomogeneous charge/discharge states, and consequently cause battery degradation. For LiFePO4 electrodes, highly percolated and less tortuous carbon found in a templated electrode explain its better high-C-rate performance. Finally, laboratory-made LiMn2O4 electrodes were electrochemically cycled with different operation parameters, including cycle number, temperature, and operating voltage. Quantitative analyses on 3D TXM data sets indicate particle fracture, mainly due to tetragonal to cubic phase transformations induced by the Jahn-Teller effect, resulting in electrode degradation. Moreover, high temperature operation is found to enhance active material dissolution and can also accelerate cell degradation. This ex-situ method, which combines electrochemical cycling and statistical analysis, proved to be an effective approach to provide insight for the interpretation of complex mechanical and electrochemical interactions within the electrodes.

Characterization of 3D interconnected microstructural network in mixed ionic and electronic conducting ceramic composites

NASA Astrophysics Data System (ADS)

Harris, William M.; Brinkman, Kyle S.; Lin, Ye; Su, Dong; Cocco, Alex P.; Nakajo, Arata; Degostin, Matthew B.; Chen-Wiegart, Yu-Chen Karen; Wang, Jun; Chen, Fanglin; Chu, Yong S.; Chiu, Wilson K. S.

2014-04-01

The microstructure and connectivity of the ionic and electronic conductive phases in composite ceramic membranes are directly related to device performance. Transmission electron microscopy (TEM) including chemical mapping combined with X-ray nanotomography (XNT) have been used to characterize the composition and 3-D microstructure of a MIEC composite model system consisting of a Ce0.8Gd0.2O2 (GDC) oxygen ion conductive phase and a CoFe2O4 (CFO) electronic conductive phase. The microstructural data is discussed, including the composition and distribution of an emergent phase which takes the form of isolated and distinct regions. Performance implications are considered with regards to the design of new material systems which evolve under non-equilibrium operating conditions.The microstructure and connectivity of the ionic and electronic conductive phases in composite ceramic membranes are directly related to device performance. Transmission electron microscopy (TEM) including chemical mapping combined with X-ray nanotomography (XNT) have been used to characterize the composition and 3-D microstructure of a MIEC composite model system consisting of a Ce0.8Gd0.2O2 (GDC) oxygen ion conductive phase and a CoFe2O4 (CFO) electronic conductive phase. The microstructural data is discussed, including the composition and distribution of an emergent phase which takes the form of isolated and distinct regions. Performance implications are considered with regards to the design of new material systems which evolve under non-equilibrium operating conditions. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr06684c

Co3O4-x-Carbon@Fe2-yCoyO3 Heterostructural Hollow Polyhedrons for the Oxygen Evolution Reaction.

PubMed

Xu, Wangwang; Xie, Weiwei; Wang, Ying

2017-08-30

Hollow heterostructured nanomaterials have received tremendous interest in new-generation electrocatalyst applications. However, the design and fabrication of such materials remain a significant challenge. In this work, we present Co 3 O 4-x -carbon@Fe 2-y Co y O 3 heterostructural hollow polyhedrons that have been fabricated by facile thermal treatment followed by solution-phase growth for application as efficient oxygen evolution reaction (OER) electrocatalysts. Starting from a single ZIF-67 hollow polyhedron, a novel complex structured composite material constructed from Co 3 O 4-x nanocrystallite-embedded carbon matrix embedded with Fe 2-y Co y O 3 nanowires was successfully prepared. The Co 3 O 4-x nanocrystallite with oxygen vacancies provides both heterogeneous nucleation sites and growth platform for Fe 2-y Co y O 3 nanowires. The resultant heterostructure combines the advantages of Fe 2-y Co y O 3 nanowires with the large surface area and surface defects of Co 3 O 4-x nanocrystallite, resulting in improved electrocatalytic activity and electrical conductivity. As a result, such novel heterostructured OER electrocatalysts exhibit much lower onset potential (1.52 V) and higher current density (70 mA/cm 2 at 1.7 V) than Co 3 O 4-x -carbon hollow polyhedrons (onset 1.55 V, 35 mA/cm 2 at 1.7 V) and pure Co 3 O 4 hollow polyhedrons (onset 1.62 V, 5 mA/cm 2 at 1.7 V). Furthermore, the design and synthesis of metal-organic framework (MOF)-derived nanomaterials in this work offer new opportunities for developing novel and efficient electrocatalysts in electrochemical devices.

A Co3O4-CDots-C3N4 three component electrocatalyst design concept for efficient and tunable CO2 reduction to syngas.

PubMed

Guo, Sijie; Zhao, Siqi; Wu, Xiuqin; Li, Hao; Zhou, Yunjie; Zhu, Cheng; Yang, Nianjun; Jiang, Xin; Gao, Jin; Bai, Liang; Liu, Yang; Lifshitz, Yeshayahu; Lee, Shuit-Tong; Kang, Zhenhui

2017-11-28

Syngas, a CO and H 2 mixture mostly generated from non-renewable fossil fuels, is an essential feedstock for production of liquid fuels. Electrochemical reduction of CO 2 and H + /H 2 O is an alternative renewable route to produce syngas. Here we introduce the concept of coupling a hydrogen evolution reaction (HER) catalyst with a CDots/C 3 N 4 composite (a CO 2 reduction catalyst) to achieve a cheap, stable, selective and efficient route for tunable syngas production. Co 3 O 4 , MoS 2 , Au and Pt serve as the HER component. The Co 3 O 4 -CDots-C 3 N 4 electrocatalyst is found to be the most efficient among the combinations studied. The H 2 /CO ratio of the produced syngas is tunable from 0.07:1 to 4:1 by controlling the potential. This catalyst is highly stable for syngas generation (over 100 h) with no other products besides CO and H 2 . Insight into the mechanisms balancing between CO 2 reduction and H 2 evolution when applying the HER-CDots-C 3 N 4 catalyst concept is provided.

Boosting photocatalytic overall water splitting by Co doping into Mn3O4 nanoparticles as oxygen evolution cocatalysts.

PubMed

Yoshinaga, Taizo; Saruyama, Masaki; Xiong, Anke; Ham, Yeilin; Kuang, Yongbo; Niishiro, Ryo; Akiyama, Seiji; Sakamoto, Masanori; Hisatomi, Takashi; Domen, Kazunari; Teranishi, Toshiharu

2018-06-14

The effect of cobalt doping into a manganese oxide (tetragonal spinel Mn 3 O 4 ) nanoparticle cocatalyst up to Co/(Co + Mn) = 0.4 (mol/mol) on the activity of photocatalytic water oxidation was studied. Monodisperse ∼10 nm Co y Mn 1-y O (0 ≤y≤ 0.4) nanoparticles were uniformly loaded onto photocatalysts and converted to Co x Mn 3-x O 4 nanoparticles through calcination. 40 mol% cobalt-doped Mn 3 O 4 nanoparticle-loaded Rh@Cr 2 O 3 /SrTiO 3 photocatalyst exhibited 1.8 times-higher overall water splitting activity than that with pure Mn 3 O 4 nanoparticles. Investigation on the band structure and electrocatalytic water oxidation activity of Co x Mn 3-x O 4 nanoparticles revealed that the Co doping mainly contributes to the improvement of water oxidation kinetics on the surface of the cocatalyst nanoparticles.

Evolution of the interfacial phases in Al2O3-Kovar® joints brazed using a Ag-Cu-Ti-based alloy

NASA Astrophysics Data System (ADS)

Ali, Majed; Knowles, Kevin M.; Mallinson, Phillip M.; Fernie, John A.

2017-04-01

A systematic investigation of the brazing of Al2O3 to Kovar® (Fe-29Ni-17Co wt.%) using the active braze alloy (ABA) Ag-35.25Cu-1.75Ti wt.% has been undertaken to study the chemical reactions at the interfaces of the joints. The extent to which silica-based secondary phases in the Al2O3 participate in the reactions at the ABA/Al2O3 interface has been clarified. Another aspect of this work has been to determine the influence of various brazing parameters, such as the peak temperature, Tp, and time at Tp, τ, on the resultant microstructure. As a consequence, the microstructural evolution of the joints as a function of Tp and τ is discussed in some detail. The formation of a Fe2Ti layer on the Kovar® and its growth, along with adjacent Ni3Ti particles in the ABA, dominate the microstructural developments at the ABA/Kovar® interface. The presence of Kovar® next to the ABA does not change the intrinsic chemical reactions occurring at the ABA/Al2O3 interface. However, the extent of these reactions is limited if the purity of the Al2O3 is high, and so it is necessary to have some silica-rich secondary phase in the Al2O3 to facilitate the formation of a Ti3Cu3O layer on the Al2O3. Breakdown of the Ti3Cu3O layer, together with fracture of the Fe2Ti layer and separation of this layer from the Kovar®, has been avoided by brazing at temperatures close to the liquidus temperature of the ABA for short periods of time, e.g., for Tp between 820 and 830 °C and τ between 2 and 8 min.

Facile synthesis of ultrafine cobalt oxide nanoparticles for high-performance supercapacitors.

PubMed

Liu, Fangyan; Su, Hai; Jin, Long; Zhang, Haitao; Chu, Xiang; Yang, Weiqing

2017-11-01

The ultrafine Co 3 O 4 nanoparticles are successfully prepared by a novel solvothermal-precipitation approach which exploits the supernatant liquid of Co 3 O 4 nanoflake micropheres synthesized by solvothermal method before. Interestingly, the water is only employed to obtain the ultrafine nanoparticles in supernatant liquid which was usually thrown away before. The microstructure measurement results of the as-grown samples present the homogeneous disperse ultrafine Co 3 O 4 nanoparticles with the size of around 5-10nm. The corresponding synthesis mechanism of the ultrafine Co 3 O 4 nanoparticles is proposed. More importantly, these ultrafine Co 3 O 4 nanoparticles obtained at 250°C show the highest specific capacitance of 523.0Fg -1 at 0.5Ag -1 , 2.6 times that of Co 3 O 4 nanoflake micropheres due to the quantum size effect. Meanwhile, the sample annealed under 350°C possesses the best cycling stability with capacitance retention of 104.9% after 1500 cycles. These results unambiguously demonstrate that this work not only provides a novel, facile, and eco-friendly approach to prepare high-performance Co 3 O 4 nanoparticles electrode materials for supercapacitors but also develops a widely used method for the preparation of other materials on a large scale. Copyright © 2017 Elsevier Inc. All rights reserved.

What determines catalyst functionality in molecular water oxidation? Dependence on ligands and metal nuclearity in cobalt clusters.

PubMed

Smith, Paul F; Kaplan, Christopher; Sheats, John E; Robinson, David M; McCool, Nicholas S; Mezle, Nicholas; Dismukes, G Charles

2014-02-17

The metal-oxo M4O4 "cubane" topology is of special significance to the field of water oxidation as it represents the merging of bioinspired structural principles derived from natural photosynthesis with successful artificial catalysts known to date. Herein, we directly compare the rates of water oxidation/O2 evolution catalyzed by six cobalt-oxo clusters including the Co4O4 cubanes, Co4O4(OAc)4(py)4 and [Co4O4(OAc)2(bpy)4](2+), using the common Ru(bpy)3(2+)/S2O8(2-) photo-oxidant assay. At pH 8, the first-order rate constants for these cubanes differ by 2-fold, 0.030 and 0.015 s(-1), respectively, reflecting the number of labile carboxylate sites that allow substrate water binding in a pre-equilibrium step before O2 release. Kinetic results reveal a deprotonation step occurs on this pathway and that two electrons are removed before O2 evolution occurs. The Co4O4 cubane core is shown to be the smallest catalytic unit for the intramolecular water oxidation pathway, as neither "incomplete cubane" trimers [Co3O(OH)3(OAc)2(bpy)3](2+) and [Co3O(OH)2(OAc)3(py)5](2+) nor "half cubane" dimers [Co2(OH)2(OAc)3(bpy)2](+) and [Co2(OH)2(OAc)3(py)4](+) were found capable of evolving O2, despite having the same ligand sets as their cubane counterparts. Electrochemical studies reveal that oxidation of both cubanes to formally Co4(3III,IV) (0.7 V vs Ag/AgCl) occurs readily, while neither dimers nor trimers are oxidized below 1.5 V, pointing to appreciably greater charge delocalization in the [Co4O4](5+) core. The origin of catalytic activity by Co4O4 cubanes illustrates three key features for water oxidation: (1) four one-electron redox metals, (2) efficient charge delocalization of the first oxidation step across the Co4O4 cluster, allowing for stabilization of higher oxidizing equivalents, and (3) terminal coordination site for substrate aquo/oxo formation.

Heptanuclear CoII5CoIII2 Cluster as Efficient Water Oxidation Catalyst.

PubMed

Xu, Jia-Heng; Guo, Ling-Yu; Su, Hai-Feng; Gao, Xiang; Wu, Xiao-Fan; Wang, Wen-Guang; Tung, Chen-Ho; Sun, Di

2017-02-06

Inspired by the transition-metal-oxo cubical Mn 4 CaO 5 in photosystem II, we herein report a disc-like heptanuclear mixed-valent cobalt cluster, [Co II 5 Co III 2 (mdea) 4 (N 3 ) 2 (CH 3 CN) 6 (OH) 2 (H 2 O) 2 ·4ClO 4 ] (1, H 2 mdea = N-methyldiethanolamine), for photocatalytic oxygen evolution. The topology of the Co 7 core resembles a small piece of cobaltate protected by terminal H 2 O, N 3 - , CH 3 CN, and multidentate N-methyldiethanolamine at the periphery. Under the optimal photocatalytic conditions, 1 exhibits water oxidation activity with a turnover number (TON) of 210 and a turnover frequency (TOF initial ) of 0.23 s -1 . Importantly, electrospray mass spectrometry (ESI-MS) was used to not only identify the possible main active species in the water oxidation reaction but also monitor the evolutions of oxidation states of cobalt during the photocatalytic reactions. These results shed light on the design concept of new water oxidation catalysts and mechanism-related issues such as the key active intermediate and oxidation state evolution in the oxygen evolution process. The magnetic properties of 1 were also discussed in detail.

Fundamental Investigations and Rational Design of Durable High-Performance SOFC Cathodes

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

Chen, Yu; Ding, Dong; Wei, Tao

The main objective of this project is to unravel the degradation mechanism of LSCF cathodes under realistic operating conditions with different types of contaminants, aiming towards the rational design of cathodes with high-performance and enhanced durability by combining a porous backbone (such as LSCF) with a thin catalyst coating. The mechanistic understanding will help us to optimize the composition and morphology of the catalyst layer and microstructure of the LSCF backbone for better performance and durability. More specifically, the technical objectives include: (1) to unravel the degradation mechanism of LSCF cathodes under realistic operating conditions with different types of contaminantsmore » using in situ and ex situ measurements performed on specially-designed cathodes; (2) to examine the microstructural and compositional evolution of LSCF cathodes as well as the cathode/electrolyte interfaces under realistic operating conditions; (3) to correlate the fuel cell performance instability and degradation with the microstructural and morphological evolution and surface chemistry change of the cathode under realistic operating conditions; (4) to explore new catalyst materials and electrode structures to enhance the stability of the LSCF cathode under realistic operating conditions; and (5) to validate the long term stability of the modified LSCF cathode in commercially available cells under realistic operating conditions. We have systematically evaluated LSCF cathodes in symmetrical cells and anode supported cells under realistic conditions with different types of contaminants such as humidity, CO 2, and Cr. Electrochemical models for the design of test cells and understanding of mechanisms have been developed for the exploration of fundamental properties of electrode materials. It is demonstrated that the activity and stability of LSCF cathodes can be degraded by the introduction of contaminants. The microstructural and compositional evolution of LSCF cathodes as well as the cathode/electrolyte interfaces under realistic operating conditions has been studied. It is found that SrO readily segregated/enriched on the LSCF surface. More severe contamination conditions cause more SrO on surface. Novel catalyst coatings through particle depositions (PrOx) or continuous thin films (PNM) were successfully developed to improve the activity and stability of LSCF cathodes. Finally, we have demonstrated enhanced activity and stability of LSCF cathodes over longer periods of time in homemade and commercially available cells by an optimized PNM (dense film and particles) infiltration process, under clean air and realistic operating conditions (3% H 2O, 5% CO 2 and direct Crofer contact). Both performance and durability of single cells with PNM coating has been enhanced compared with those without coating. Raman analysis of cathodes surface indicated that the intensity of SrCrO 4 was significantly decreased.« less

Co/Cr co-doped MgGa{sub 2}O{sub 4} nanoparticles: Microstructure and optical properties

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

Duan, Xiulan, E-mail: xlduan@sdu.edu.cn; Liu, Jian; Yu, Fapeng

2016-01-15

Graphical abstract: The Ga 2p{sub 3/2} spectra consist of two peaks, corresponding to Ga{sup 3+} ions placed at octahedral and tetrahedral sites, respectively. The fraction of tetrahedral Ga{sup 3+} ions (∼1117 eV) increases with increasing doping concentration. - Highlights: • Structural and properties of Co{sup 2+}/Cr{sup 3+}: MgGa{sub 2}O{sub 4} nanoparticles were characterized. • The distribution of cations was studied using XPS. • The inversion degree increased with increasing content of doping ions. • The doping concentration has also effect on absorption and emission properties. • Optical properties of nanoparticles were discussed based on the structural results. - Abstract: MgGa{submore » 2}O{sub 4} nanoparticles co-doped with Co{sup 2+}/Cr{sup 3+} ions were prepared by a citrate sol–gel method. Their microstructure and optical properties were studied using X-ray powder diffraction (XRD), infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), absorption and fluorescence spectroscopy. MgGa{sub 2}O{sub 4} nanoparticles with the size of 10–30 nm were obtained when the precursor was annealed at 800 °C. Results indicated that Ga{sup 3+} and Mg{sup 2+} cations occupied the octahedral sites as well as the tetrahedral sites in samples. The inversion degree of Ga or Mg increased with increasing content of doping ions. Absorption spectra indicated that Co{sup 2+} and Cr{sup 3+} ions entered both the tetrahedral and octahedral sites of spinel structure by substituting Mg{sup 2+} and Ga{sup 3+} ions, respectively. Emission spectra of the co-doped MgGa{sub 2}O{sub 4} showed a broad emission band peaking at 700 and 680 nm, relevant to the emission characteristic of octahedral Cr{sup 3+} and tetrahedral Co{sup 2+} ions.« less

Evolution of microstructural defects of TiO2 nanocrystals by Zr4+ or/and Ge4+ doping lead to high disinfection efficiency for CWAs

NASA Astrophysics Data System (ADS)

Shen, Zhong; Zhong, Jin-Yi; Chai, Na-Na; He, Xin; Zang, Jian-Zheng; Xu, Hui; Han, Xiao-Yuan; Zhang, Peng

2017-06-01

Zr4+, Ge4+ doped and co-doped TiO2 nanoparticles were prepared by a 'one-pot' homogeneous precipitation method. The photocatalytic reaction kinetics of DMMP and the disinfection efficiency of HD, GD and VX on the samples were investigated. By means of a variety of characterization methods, especially the positron annihilation lifetime spectroscopy, the changes in structure and property of TiO2 across doping were studied. The results show that the reasonable engineering design of novel photocatalysts in the field of CWAs decontamination can be realized by adjusting the bulk-to-surface defects ratio, except for crystal structure, specific surface area, pore size distribution and light utilization.

The obtaining and properties of asymmetric ion transport membrane for separating of oxygen from air

NASA Astrophysics Data System (ADS)

Solovieva, A. A.; Kulbakin, I. V.

2018-04-01

The bilayer oxygen-permeable membrane, consisting of a thin-film dense composite based on Co3O4 - 36 wt. % Bi2O3, and of a porous ceramic substrate of Co2SiO4, was synthesized and characterized. The way for obtaining of porous ceramic based on cobalt silicate was found, while the microstructure and the mechanical properties of porous ceramic were studied. Layered casting with post-pressing was used to cover the surface of porous support of Co2SiO4 by the Co3O4 - 36 wt. % Bi2O3 - based film. Transport properties of the asymmetric membrane have been studied, the kinetic features of oxygen transport have been established, and the characteristic thickness of the membrane has been estimated. The methods to prevent the high-temperature creep of ion transport membranes based on solid/molten oxides, which are the promising ones for obtaining of pure oxygen from air, are proposed and discussed.

Electric properties of a textured BiNaKTiO3 ceramic for energy harvesting system

NASA Astrophysics Data System (ADS)

Lim, D. H.; Song, T. K.; Lee, D. S.; Jeong, S. J.; Kim, Min-Soo; Song, Jae-Sung

2012-01-01

Piezoelectric ceramics with microstructural texturing were fabricated and evaluated to investigate their possibility for use in piezoelectric energy harvest devices in response to external mechanical impact. The microstructural evolution and properties of a Bi0.5(Na0.425K0.075) TiO3 (BNKT) ceramic material with platelike Bi4Ti3O12 (BiT) were investigated. The platelike Bi4Ti3O12 (BiT) was used as a template to induce grain growth under a proper heat treatment. The textured BNKTs were fabricated and heated at 1150 °C for 10 h. They exhibited <001>-oriented large grains and improved of ferroelectric properties. The textured microstructure was due to the occurrence of grain growth around the templates. When subjected to a low stress of 0.8 MPa, the textured BNKT had a slightly larger voltage and power than the randomly-oriented BNKT. Meanwhile, when high stresses over 2 MPa were applied, the voltage and the power of the textured specimen were larger than those of the randomly-oriented specimen. The microstructure textured along the <100> direction may contribute to the improved power generation.

Linear magnetic field dependence of the magnetodielectric effect in eutectic BaTiO3-CoFe2O4 multiferroic material fabricated by containerless processing

NASA Astrophysics Data System (ADS)

Fukushima, J.; Ara, K.; Nojima, T.; Iguchi, S.; Hayashi, Y.; Takizawa, H.

2018-05-01

To maximize the formation of an anisotropic interface between the magnetostrictive phase and the electrostrictive phase, a eutectic BaTiO3-CoFe2O4 multiferroic material is fabricated by containerless processing. The composites in this process had a fine eutectic structure, especially at a eutectic composition of BaTiO3:CoFe2O4 = 62:38. TEM observations revealed that the (1 0 0) plane of tetragonal BaTiO3 and the (1 0 0) plane of CoFe2O4 were oriented in parallel. In addition to the largest magnetodielectric effect in the eutectic-composition samples, we confirmed the permittivity is controlled linearly by applying a high magnetic field through forced magnetostriction. So far, the peak of the magnetodielectric effect around 0.25 T has been only found in the sintered CoFe2O4 polycrystalline sample. Thus, the containerless processing provides us a route to produce an ideal microstructure without accompanying 90° domain wall process and rotational magnetization process, which enhances the magnetodielectric effect.

Novel catalysts and photoelectrochemical system for solar fuel production

NASA Astrophysics Data System (ADS)

Zhang, Yan

Solar fuel production from abundant raw chemicals such as CO2 and water is highly desired as a clean renewable energy solution for the future. Developing photoelectrochemical cells is viewed as a promising approach to realize this energy conversion and storage process. Efficient and robust oxygen evolution catalyst made from non-precious materials remains a major challenge for such a system. This thesis basically consists of three parts of work, including studies on enhancing the photocatalytic oxygen evolution activity of cobalt-based spinel nanoparticles by manganese3+ substitution, in situ formation of cobalt oxide nanocubanes as highly active catalyst for photocatalytic oxygen evolution reaction, and development of a photoanode-driven photoelectrochemical cell for CO2 reduction with water. The first part of this thesis work devotes efforts in the development and study on cobalt and other transition metal oxide based oxygen evolution catalyst. Photocatalytic oxygen evolution is a critical step for solar fuel production from abundant sources. It poses a significant challenge because it requires an efficient catalyst to bridge the one-electron photon capture process with the four-electron oxygen reaction. Among all the metal oxides, Co3O4 spinel exhibits a high activity as an oxygen evolution catalyst. The results of this work demonstrate that the photocatalytic oxygen evolution activity of Co3O4 spinel can be further enhanced by substituting Co with Mn in the spinel structure. Using a facile hydrothermal approach, Co3O4 spinel nanoparticles as well as Mn-substituted and Ni-substituted Co3O4 spinel nanoparticles with a typical particle size of 5-7 nm were successfully synthesized. The morphology and crystal structures of the as-synthesized nanoparticle catalysts have been carefully examined using various structural characterization techniques, including powder x-ray diffraction (PXRD), transmission electron microscope (TEM), gas adsorption, and x-ray absorption spectroscopy (XAS). The photocatalytic activities of as-made nanoparticles were investigated using a well-studied visible light driven [Ru(bpy)3]2+-persulfate system. In both Clark electrode and reactor/gas chromatography (GC) systems, Mn-substituted Co3O 4 nanoparticles exhibited the highest turnover frequency (TOF) among all the three kinds of catalysts. The data presented in this paper suggest that the photocatalytic oxygen evolution activity of Co3O 4 spinel catalyst can be further enhanced by Mn3+ substitution at the octahedral sites. The second part of this piece of work was carried out to further investigate cobalt oxide based photocatalytic oxygen evolution catalyst. A new strategy was developed to synthesize nonsupported cobalt oxide nanocubanes through an in situ phase transformation mechanism using a layered Co(OH)(OCH3) precursor. Under sonication, the precursor was exfoliated and transformed into cobalt oxide nanocubanes in the presence of NaHCO 3-Na2SiF6 buffer solution. The resulting cobalt catalyst with an average particle size less than 2 nm exhibited a turnover frequency of 0.0023 per second per cobalt in photocatalytic oxygen evolution reaction. X-ray absorption results suggested that a unique nanocubane structure, where 13 cobalt atoms fully coordinated with oxygen atoms and hydroxide groups in an octahedral arrangement to form 8 Co4O4 cubanes, may be responsible for the exceptionally high oxygen evolution catalysis activity. This thesis work is completed with the development of a photoanode-driven photoelectrochemical cell for CO2 reduction. A NiOx decorated Si photoanode and nanoporous Ag cathode were employed. With an external bias of 2.0 V, a current density at cathode of 10 mA/cm2 and Faradaic efficiency of 70% for CO2 to CO was achieved. Compared to a normal electrochemical cell, the photoelectrochemical cell saves 0.4 V electrical energy by absorbing photo-energy. In addition, post-test photoanodes were carefully characterized by SEM, XAS, and XPS analysis.

3D Microstructural Architectures for Metal and Alloy Components Fabricated by 3D Printing/Additive Manufacturing Technologies

NASA Astrophysics Data System (ADS)

Martinez, E.; Murr, L. E.; Amato, K. N.; Hernandez, J.; Shindo, P. W.; Gaytan, S. M.; Ramirez, D. A.; Medina, F.; Wicker, R. B.

The layer-by-layer building of monolithic, 3D metal components from selectively melted powder layers using laser or electron beams is a novel form of 3D printing or additive manufacturing. Microstructures created in these 3D products can involve novel, directional solidification structures which can include crystallographically oriented grains containing columnar arrays of precipitates characteristic of a microstructural architecture. These microstructural architectures are advantageously rendered in 3D image constructions involving light optical microscopy and scanning and transmission electron microscopy observations. Microstructural evolution can also be effectively examined through 3D image sequences which, along with x-ray diffraction (XRD) analysis in the x-y and x-z planes, can effectively characterize related crystallographic/texture variances. This paper compares 3D microstructural architectures in Co-base and Ni-base superalloys, columnar martensitic grain structures in 17-4 PH alloy, and columnar copper oxides and dislocation arrays in copper.

Synthesis of feather-like CeO2 microstructures and enzymatic electrochemical catalysis for trichloroacetic acid

NASA Astrophysics Data System (ADS)

Xiao, Xin; Zhang, Dong En; Zhang, Fan; Gong, Jun Yan; Zhang, Xiao Bo; Wang, Yi Hui; Ma, Juan Juan; Tong, Zhi Wei

Novel feather-like CeO2 microstructures were achieved by a thermal decomposition approach of Ce(OH)CO3 precursor. The Ce(OH)CO3 was obtained from a solvothermal method employing Ce(NO3)3.6H2O with C6H12N4 and C16H33(CH3)3NBr (CTAB) at 190∘C in a water-PEG-200 mixed solution. The feather-like CeO2 dendrite was obtained by thermal conversion of the feather-like Ce(OH)CO3 at 650∘C in air. A reasonable growth mechanism was proposed with the soft-template effect of PEG-200. The electrochemical behavior and enzyme activity of myoglobin (Mb) immobilized on CeO2-Nafion modified glassy carbon electrode (GCE) are demonstrated by cyclic voltammetric measurements. The results indicate that CeO2 can obviously promote the direct electron transfer between the Mb redox centers and the electrode. The Mb on CeO2-Nafion behaves as an elegant performance on the electrochemical reduction of trichloroacetic acid (TCA) from 0.32μM to 2.28μM. The detection limit is estimated to be 0.08μM.

Surfactant-assisted hydrothermal crystallization of nanostructured lithium metasilicate (Li{sub 2}SiO{sub 3}) hollow spheres: II-Textural analysis and CO{sub 2}-H{sub 2}O sorption evaluation

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

Ortiz-Landeros, Jose; Gomez-Yanez, Carlos; Pfeiffer, Heriberto, E-mail: pfeiffer@iim.unam.mx

In a previous work, the synthesis and structural-microstructural characterization of different nanocrystalline lithium metasilicate (Li{sub 2}SiO{sub 3}) samples were performed. Then, in this work, initially, a textural analysis was performed over the same samples. Li{sub 2}SiO{sub 3} samples prepared with a non-ionic surfactant (TRITON X-114) presented the best textural properties. Therefore, this sample was selected to evaluate its water vapor (H{sub 2}O) and carbon dioxide (CO{sub 2}) sorption properties. Sorption experiments were performed at low temperatures (30-80 deg. C) in presence of water vapor using N{sub 2} or CO{sub 2} as carrier gases. Results clearly evidenced that CO{sub 2} sorptionmore » on these materials is highly improved by H{sub 2}O vapor, and of course, textural properties enhanced the H{sub 2}O-CO{sub 2} sorption efficiency, in comparison with the solid-state reference sample. - Graphical abstract: Li{sub 2}SiO{sub 3} varied significantly its capacity of CO{sub 2} absorption as a function of the microstructural properties and by the water presence. Highlights: > We studied the CO{sub 2} absorption on different Li{sub 2}SiO{sub 3} samples in presence of H{sub 2}O vapor. > It was proved that CO{sub 2} absorption on Li{sub 2}SiO{sub 3} is controlled by different factors. > Li{sub 2}SiO{sub 3} with a porous microstructure produces a higher CO{sub 2} absorption. > H{sub 2}O vapor favors the CO{sub 2} absorption on Li{sub 2}SiO{sub 3} due to a surface hydroxylation.« less

Elastic anomalies and acoustic dissipation associated with spin state transitions in LnCoO3 (Ln=La, Nd, Gd) and Co3O4: analogue behaviour for spin state transitions in minerals

NASA Astrophysics Data System (ADS)

Zhang, Z.; Carpenter, M. A.; Koppensteiner, J.; Schranz, W.

2010-12-01

Iron ions in lower mantle minerals magnesiowüstitue (Mg,Fe)O, perovskite (Mg,Fe)(Si,Al)O3 and post-perovskite phases undergo electronic spin state transitions from high spin (HS) to low spin (LS) or intermediate spin (IS) at high pressures and high temperatures. These spin state transitions give rise to changes in bulk and shear moduli which have significant implications for the physical and chemical properties of the lower mantle. However, the possibility of increased attenuation does not appear to have been considered yet. Co3+ is isoelectronic with Fe2+ and shows analogous HS/LS behaviour at ambient pressure in a temperature range which is easily accessible for in-situ investigations. We have studied spin state transitions in cobalt perovskites LaCoO3, NdCoO3, GdCoO3 and in Co3O4 using resonant ultrasound spectroscopy (RUS) at high frequencies 0.1-1.5 MHz, and dynamic mechanical analysis (DMA) at low frequencies 0.1-50 Hz, in the temperature range 10-1200 K. The specific objectives were to characterize anomalies in the shear moduli and in acoustic attenuation accompanying changes in the spin state of Co3+. Anomalies in shear moduli have been observed at ~110 K and ~590 K for LaCoO3, ~325 K and ~695 K for NdCoO3, ~720 K for GdCoO3, and ~30 K for Co3O4. For LaCoO3, a spin order parameter qspin is expected to couple with volume strain ea as λeaqspin and with shear strain es as λes2qspin. As a consequence of linear/quadratic coupling with es, the shear modulus is expected to vary linearly with qspin. This appears to be approximately the case for LaCoO3. Changes in spin state do not appear to give rise to acoustic attenuation at either DMA frequencies (~1 Hz) or RUS frequencies (~1 MHz), consistent with the expectation that spin/lattice relaxation is rapid in comparison with the time scale of applied stress in each case. On the other hand, for LaCoO3 there is a peak in dissipation near 590 K at low frequencies, which is attributed to freezing of ferroelastic twin walls. At high frequencies, acoustic attenuation increases steeply below ~110 K, and this is attributed to movement of magnetic polarons under stress. Data for thermally activated relaxation processes in LaCoO3 based on different measurements from the literature and our own elasticity data have been combined to give a preliminary anelasticity map. At seismic frequencies, loss mechanisms are likely to be only due to twin wall and magnetic polaron mobility. NdCoO3 and GdCoO3 both have the Pnma structure at room temperature. They also show significant non-linear behaviour in shear modulus as a function of temperature but neither show evidence of significant attenuation which might be attributed to microstructure, spin/lattice coupling or polarons. On the other hand, Co3O4 shows evidence of increasing attenuation above ~800 K and below ~30 K at high frequencies. The origin of the latter is clearly associated with magnetic ordering in this system but the origin of the former is not yet understood, particularly as Co3O4 crystals are not expected to contain any transformation microstructure.

A doping technique that suppresses undesirable H2 evolution derived from overall water splitting in the highly selective photocatalytic conversion of CO2 in and by water.

PubMed

Teramura, Kentaro; Wang, Zheng; Hosokawa, Saburo; Sakata, Yoshihisa; Tanaka, Tsunehiro

2014-08-04

Photocatalytic conversion of CO2 to reduction products, such as CO, HCOOH, HCHO, CH3OH, and CH4, is one of the most attractive propositions for producing green energy by artificial photosynthesis. Herein, we found that Ga2O3 photocatalysts exhibit high conversion of CO2. Doping of Zn species into Ga2O3 suppresses the H2 evolution derived from overall water splitting and, consequently, Zn-doped, Ag-modified Ga2O3 exhibits higher selectivity toward CO evolution than bare, Ag-modified Ga2O3. We observed stoichiometric amounts of evolved O2 together with CO. Mass spectrometry clarified that the carbon source of the evolved CO is not the residual carbon species on the photocatalyst surface, but the CO2 introduced in the gas phase. Doping of the photocatalyst with Zn is expected to ease the adsorption of CO2 on the catalyst surface. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Doping concentration dependence of microstructure and magnetic behaviours in Co-doped TiO2 nanorods

PubMed Central

2014-01-01

Co-doped titanium dioxide (TiO2) nanorods with different doping concentrations were fabricated by a molten salt method. It is found that the morphology of TiO2 changes from nanorods to nanoparticles with increasing doping concentration. The mechanism for the structure and phase evolution is investigated in detail. Undoped TiO2 nanorods show strong ferromagnetism at room temperature, whereas incorporating of Co deteriorates the ferromagnetic ordering. X-ray photoelectron spectroscopy (XPS) and electron spin resonance (ESR) results demonstrate that the ferromagnetism is associated with Ti vacancy. PMID:25593558

Dielectric properties and nonlinear I-V electrical behavior of (Li1+, Al3+) co-doped CaCu3Ti4O12 ceramics

NASA Astrophysics Data System (ADS)

Sun, Li; Ni, Qing; Guo, Jianqin; Cao, Ensi; Hao, Wentao; Zhang, Yongjia; Ju, Lin

2018-06-01

(Li1+, Al3+) co-doped CaCu3Ti4O12 ceramics (CaCu3-2 x Li x Al x Ti4O12, x = 0.05, 0.1, 0.15) were prepared by a sol-gel method and were sintered at 1020-1080 °C for 8 h to improve the geometric microstructure, dielectric and nonlinear I-V electrical properties. Notably, very high dielectric constant of 1 × 105 with good dielectric-frequency as well as dielectric-temperature stability can be achieved in CaCu2.8Li0.1Al0.1Ti4O12 ceramic sintered at 1060 °C. The average grain sizes, resistivity and the non-Ohmic properties are also improved compared to pure CaCu3Ti4O12. These results indicate that (Li1+, Al3+) co-doping at the Cu2+ site can improve the dielectric properties of CaCu3Ti4O12, supporting the internal barrier layer capacitance effect of Schottky barriers at grain boundaries.

Effect of the MgO on microstructure and optical properties of TAG (Tb3Al5O12) transparent ceramics using hot isostatic pressing

NASA Astrophysics Data System (ADS)

Zhang, Shouyi; Liu, Peng; Xu, Xiaodong; Zhang, Jian

2018-06-01

In this work, the TAG transparent ceramics doped with 0.4 wt.% TEOS and different concentration of MgO were fabricated by a reactive sintering process under vacuum sintering combined with hot isostatic pressing (HIP) treatment. The effect of MgO on the microstructure evolution and optical properties of delivered ceramics were investigated. The results showed that the TAG ceramics doped with 0.4 wt.% TEOS and 0.1 wt.% MgO exhibited the optimum optical transmittance, which can reach about 81% in the visible and near-infrared (NIR) regions. The addition of MgO inhibited the grain growth and accelerated the densification of TAG ceramic at the sintering temperature reached about 1600 °C.

Understanding the Oxygen Evolution Reaction Mechanism on CoO x using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy

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

Favaro, Marco; Yang, Jinhui; Nappini, Silvia

Photoelectrochemical water splitting is a promising approach for renewable production of hydrogen from solar energy and requires interfacing advanced water-splitting catalysts with semiconductors. Understanding the mechanism of function of such electrocatalysts at the atomic scale and under realistic working conditions is a challenging, yet important, task for advancing efficient and stable function. This is particularly true for the case of oxygen evolution catalysts and, here, we study a highly active Co 3O 4/Co(OH) 2 biphasic electrocatalyst on Si by means of operando ambient-pressure X-ray photoelectron spectroscopy performed at the solid/liquid electrified interface. Spectral simulation and multiplet fitting reveal that themore » catalyst undergoes chemical-structural transformations as a function of the applied anodic potential, with complete conversion of the Co(OH) 2 and partial conversion of the spinel Co 3O 4 phases to CoO(OH) under precatalytic electrochemical conditions. Furthermore, we observe new spectral features in both Co 2p and O 1s core-level regions to emerge under oxygen evolution reaction conditions on CoO(OH). The operando photoelectron spectra support assignment of these newly observed features to highly active Co 4+ centers under catalytic conditions. Comparison of these results to those from a pure phase spinel Co 3O 4 catalyst supports this interpretation and reveals that the presence of Co(OH) 2 enhances catalytic activity by promoting transformations to CoO(OH). The direct investigation of electrified interfaces presented in this work can be extended to different materials under realistic catalytic conditions, thereby providing a powerful tool for mechanism discovery and an enabling capability for catalyst design.« less

Understanding the Oxygen Evolution Reaction Mechanism on CoO x using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy

DOE PAGES

Favaro, Marco; Yang, Jinhui; Nappini, Silvia; ...

2017-06-09

Photoelectrochemical water splitting is a promising approach for renewable production of hydrogen from solar energy and requires interfacing advanced water-splitting catalysts with semiconductors. Understanding the mechanism of function of such electrocatalysts at the atomic scale and under realistic working conditions is a challenging, yet important, task for advancing efficient and stable function. This is particularly true for the case of oxygen evolution catalysts and, here, we study a highly active Co 3O 4/Co(OH) 2 biphasic electrocatalyst on Si by means of operando ambient-pressure X-ray photoelectron spectroscopy performed at the solid/liquid electrified interface. Spectral simulation and multiplet fitting reveal that themore » catalyst undergoes chemical-structural transformations as a function of the applied anodic potential, with complete conversion of the Co(OH) 2 and partial conversion of the spinel Co 3O 4 phases to CoO(OH) under precatalytic electrochemical conditions. Furthermore, we observe new spectral features in both Co 2p and O 1s core-level regions to emerge under oxygen evolution reaction conditions on CoO(OH). The operando photoelectron spectra support assignment of these newly observed features to highly active Co 4+ centers under catalytic conditions. Comparison of these results to those from a pure phase spinel Co 3O 4 catalyst supports this interpretation and reveals that the presence of Co(OH) 2 enhances catalytic activity by promoting transformations to CoO(OH). The direct investigation of electrified interfaces presented in this work can be extended to different materials under realistic catalytic conditions, thereby providing a powerful tool for mechanism discovery and an enabling capability for catalyst design.« less

Thermodynamic and kinetic analyses of the CO2 chemisorption mechanism on Na2TiO3: Experimental and theoretical evidences

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

Duan, Yuhua

2014-01-01

ABSTRACT: Sodium metatitanate (Na2TiO3) was successfully synthesized via a solid-state reaction. The Na2TiO3 structure and microstructure were characterized using X-ray diffraction, scanning and transmission electron microscopy, and N2 adsorption. Then, the CO2 chemisorption mechanism on Na2TiO3 was systematically analyzed to determine the influence of temperature. The CO2 chemisorption capacity of Na2TiO3 was evaluated both dynamically and isothermally, and the products were reanalyzed to elucidate the Na2TiO3-CO2 reaction mechanism. Different chemical species (Na2CO3, Na2O, and Na4Ti5O12 or Na16Ti10O28) were identified during the CO2 capture process in Na2TiO3. In addition, some CO2 chemisorption kinetic parameters were determined. The ΔH‡ was found tomore » be 140.9 kJ/mol, to the Na2TiO3-CO2 system, between 600 and 780 °C. Results evidenced that CO2 chemisorption on Na2TiO3 highly depends on the reaction temperature. Furthermore, the experiments were theoretically supported by different thermodynamic calculations. The calculated thermodynamic properties of CO2 capture reactions by (Na2TiO3, Na4Ti5O12, and Na16Ti10O28) sodium titanates were fully investigated.« less

Microstructure and dielectric properties of BaTiO{sub 3} ceramic doped with yttrium, magnesium, gallium and silicon for AC capacitor application

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

Wang, Min-Jia; Yang, Hui; Zhejiang California International NanoSystems Institute, Hangzhou 310029

2014-12-15

Graphical abstract: Core–shell structure can be obtained in BaTiO{sub 3} ceramics co-doped with Y–Mg-Ga-Si. Y-Mg-Ga-Si co-dopant can obviously reduce dielectric loss, improve AC breakdown voltage and flatten temperature dependence of capacitance curve. - Highlights: • Y-Mg-Ga-Si co-doped BaTiO{sub 3} ceramics with core-shell structure were prepared. • Y{sup 3+}, Mg{sup 2+}, and Ga{sup 3+} dissolved in the lattice BaTiO{sub 3} replacing Ba{sup 2+} site or Ti{sup 4+} site. • Y{sup 3+} and Ga{sup 3+} tended to remain close to the grain boundaries as a shell maker. • Y-Mg-Ga-Si co-doped BaTiO{sub 3} ceramics show high AC breakdown voltage and low tanδ. -more » Abstract: The microstructures and dielectric properties of Y-Mg-Ga-Si co-doped barium titanate ceramics were investigated. Y{sup 3+} dissolved in the lattice of BaTiO{sub 3} replacing both Ba{sup 2+} site and Ti{sup 4+} site, and Mg{sup 2+} replaced Ti{sup 4+} site. The replacements of Y{sup 3+} and Mg{sup 2+} inhibit the grain growth, cause tetragonal-to-pseudocubic phase transition, reduce the dielectric loss, and flatten the temperature dependence of capacitance curve. The incorporation of Ga{sup 3+} can improve sintering and increase permittivity. Y{sup 3+} and Ga{sup 3+} tended to remain close to the grain boundaries, and play an important role as a shell maker in the formation of the core–shell structure in the co-doped BaTiO{sub 3} ceramics. Excellent dielectric properties: ϵ{sub r} = ∼2487, tanδ = ∼0.7% (at 1 kHz), ΔC/C{sub 25} < ∼6.56% (from −55 °C to 125 °C) and alternating current breakdown voltage E < ∼4.02 kV/mm can be achieved in the BaTiO{sub 3}–0.02Y{sub 2}O{sub 3}–0.03MgO–0.01Ga{sub 2}O{sub 3}–0.005SiO{sub 2} ceramics sintered at 1380 °C. This material has a potential application in alternating current multilayer ceramic capacitor.« less

Assembly of a check-patterned CuSx-TiO2 film with an electron-rich pool and its application for the photoreduction of carbon dioxide to methane

NASA Astrophysics Data System (ADS)

Lee, Homin; Kwak, Byeong Sub; Park, No-Kuk; Baek, Jeom-In; Ryu, Ho-Jung; Kang, Misook

2017-01-01

A new check-patterned CuSx-TiO2 film was designed to improve the photoreduction of CO2 to CH4. The check-patterned CuSx-TiO2 film with a 3D-network microstructure was fabricated by a facile squeeze method. The as-synthesized TiO2 and CuSx powders, as well as the patterned film, were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), UV-visible spectroscopy, cyclic voltammetry (CV), and photoluminescence (PL) spectroscopy, as well as photocurrent density and CO2 temperature-programmed desorption (TPD) measurements. Compared to pure CuSx and TiO2, the check-patterned CuSx-TiO2 film exhibited significantly increased adsorption of CO2 on its networked microstructure, attributed to the enlarged interfaces between the microparticles. The check-patterned CuSx-TiO2 film exhibited superior photocatalytic behavior, with 53.2 μmolgcat-1 L-1 of CH4 produced after 8 h of reaction, whereas 18.1 and 7.3 μmolgcat-1 L-1 of CH4 were produced from pure TiO2 and CuSx films under the same reaction conditions, respectively. A model for enhanced photoactivity over the check-patterned CuSx - TiO2 film was proposed. Results indicated that the check-patterned CuS-TiO2 material is quite promising as a photocatalyst for the reduction of CO2 to CH4.

Internal Stress and Microstructure of Zinc Oxide Films Sputter-Deposited with Carbon Dioxide Gas

NASA Astrophysics Data System (ADS)

Toru Ashida,; Kazuhiro Kato,; Hideo Omoto,; Atsushi Takamatsu,

2010-06-01

The internal stress and microstructure of ZnO films were investigated as a function of carbon dioxide (CO2) gas flow ratio [CO2/(O2+CO2)] during sputter deposition. The internal stress of the ZnO films decreased with increasing CO2 gas flow ratio. The carbon concentration in the films deposited using CO2 gas increased by up to 4.0 at. %. Furthermore, the ZnO films deposited without CO2 gas exhibited a preferred orientation of (002); however, the C-doped ZnO films exhibited random orientations. These findings suggest that the C atoms incorporated in the ZnO crystal lattice induce this random orientation, thereby relaxing the internal stress of C-doped ZnO films.

Facile formation of 2D Co2P@Co3O4 microsheets through in-situ toptactic conversion and surface corrosion: Bifunctional electrocatalysts towards overall water splitting

NASA Astrophysics Data System (ADS)

Yao, Lihua; Zhang, Nan; Wang, Yin; Ni, Yuanman; Yan, Dongpeng; Hu, Changwen

2018-01-01

Exploring efficient non-precious electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is crucial for many renewable energy conversion processes. In this work, we report that 2D Co2P@Co3O4 microsheets can be prepared through an in-situ toptactic conversion from single-crystal β-Co(OH)2 microplatelets, associated with a surface phosphatization and corrosion process. The resultant Co2P@Co3O4 2D hybrid materials can further serve as self-supported bifunctional catalytic electrodes to drive the overall water splitting for HER and OER simultaneously, with low overpotentials and high long-term stability. Furthermore, a water electrolyzer based on Co2P@Co3O4 hybrid as both anode and cathode is fabricated, which achieves 10 mA cm-2 current at only 1.57 V during water splitting process. Therefore, this work provides a facile strategy to obtain 2D Co2P-based micro/nanostructures, which act as low-cost and highly active electrocatalysts towards overall water splitting application.

Preparation, Structural Characterization and Magnetic Properties of La-SUBSTITUTED co Ferrites via a Modified Citrate Precursor Route

NASA Astrophysics Data System (ADS)

Ai, Lunhong; Jiang, Jing

CoLaxFe2-xO4 (x = 0.00, 0.05 and 0.1) nanoparticles were prepared simply by a modified citrate precursor route. Effects of La-substituting level on the their magnetic properties were investigated on the basis of the structural analysis. The thermal evolution of the precursor, as well as the microstructure of as-prepared products were studied by means of a thermogravimetric analyzer (TGA), X-ray diffractometer (XRD) and Fourier transform infrared (FTIR) spectrometer. The magnetic properties of the as-prepared samples were measured using a vibrating sample magnetometer (VSM). It was found that the magnetic properties were dependent on many factors such as La-substituting level, particle size and microstructure. The observed saturation magnetization decreased with increasing La content, whereas coercivity exhibited reverse behavior.

Fe3O4@NiSx/rGO composites with amounts of heterointerfaces and enhanced electrocatalytic properties for oxygen evolution

NASA Astrophysics Data System (ADS)

Zhu, Guoxing; Xie, Xulan; Liu, Yuanjun; Li, Xiaoyun; Xu, Keqiang; Shen, Xiaoping; Yao, Yinjie; Shah, Sayyar Ali

2018-06-01

The sluggish oxygen evolution kinetics involved in water splitting and various metal-air batteries makes the effective and inexpensive electrocatalysts be highly desirable for oxygen evolution reaction (OER). Herein, an effective and facile two-step route is developed to construct Fe3O4@NiSx composite loaded on reduced graphene oxide (rGO). The morphology and microstructure of the composites were characterized by different characterization techniques. The obtained composites show amounts of heterointerfaces. The shift of binding energy in X-ray photoelectron spectrum demonstrates the existence of interfacial charge transfer effect between Fe3O4 and NiSx. The optimized Fe3O4@NiSx/rGO sample exhibits excellent electrocatalytic performance toward OER in alkaline media, showing 10 mA·cm-2 at η = 330 mV, lower Tafel slope (35.5 mV·dec-1), and good durability, demonstrating a great perspective. The excellent OER performance can be ascribed to the synergetic effect between Fe and Ni species. It is believed that the heterointerfaces between Fe3O4 and NiSx perform as active centers for OER.

Microstructure and dielectric properties of (Nb + In) co-doped rutile TiO2 ceramics

NASA Astrophysics Data System (ADS)

Li, Jinglei; Li, Fei; Zhuang, Yongyong; Jin, Li; Wang, Linghang; Wei, Xiaoyong; Xu, Zhuo; Zhang, Shujun

2014-08-01

The (Nb + In) co-doped TiO2 ceramics recently attracted considerable attention due to their colossal dielectric permittivity (CP) (˜100,000) and low dielectric loss (˜0.05). In this research, the 0.5 mol. % In-only, 0.5 mol. % Nb-only, and 0.5-7 mol. % (Nb + In) co-doped TiO2 ceramics were synthesized by standard conventional solid-state reaction method. Microstructure studies showed that all samples were in pure rutile phase. The Nb and In ions were homogeneously distributed in the grain and grain boundary. Impedance spectroscopy and I-V behavior analysis demonstrated that the ceramics may compose of semiconducting grains and insulating grain boundaries. The high conductivity of grain was associated with the reduction of Ti4+ ions to Ti3+ ions, while the migration of oxygen vacancy may account for the conductivity of grain boundary. The effects of annealing treatment and bias filed on electrical properties were investigated for co-doped TiO2 ceramics, where the electric behaviors of samples were found to be susceptible to the annealing treatment and bias field. The internal-barrier-layer-capacitance mechanism was used to explain the CP phenomenon, the effect of annealing treatment and nonlinear I-V behavior for co-doped rutile TiO2 ceramics. Compared with CaCu3Ti4O12 ceramics, the high activation energy of co-doped rutile TiO2 (3.05 eV for grain boundary) was thought to be responsible for the low dielectric loss.

Deposition of Composite LSCF-SDC and SSC-SDC Cathodes by Axial-Injection Plasma Spraying

NASA Astrophysics Data System (ADS)

Harris, Jeffrey; Qureshi, Musab; Kesler, Olivera

2012-06-01

The performance of solid oxide fuel cell cathodes can be improved by increasing the number of electrochemical reaction sites, by controlling microstructures, or by using composite materials that consist of an ionic conductor and a mixed ionic and electronic conductor. LSCF (La0.6Sr0.4Co0.2Fe0.8O3-δ) and SSC (Sm0.5Sr0.5CoO3) cathodes were manufactured by axial-injection atmospheric plasma spraying, and composite cathodes were fabricated by mixing SDC (Ce0.8Sm0.2O1.9) into the feedstock powders. The plasma power was varied by changing the proportion of nitrogen in the plasma gas. The microstructures of cathodes produced with different plasma powers were characterized by scanning electron microscopy and gas permeation measurements. The deposition efficiencies of these cathodes were calculated based on the mass of the sprayed cathode. Particle surface temperatures were measured in-flight to enhance understanding of the relationship between spray parameters, microstructure, and deposition efficiency.

Experimental heat capacities, excess entropies, and magnetic properties of bulk and nano Fe3O4-Co3O4 and Fe3O4-Mn3O4 spinel solid solutions

NASA Astrophysics Data System (ADS)

Schliesser, Jacob M.; Huang, Baiyu; Sahu, Sulata K.; Asplund, Megan; Navrotsky, Alexandra; Woodfield, Brian F.

2018-03-01

We have measured the heat capacities of several well-characterized bulk and nanophase Fe3O4-Co3O4 and Fe3O4-Mn3O4 spinel solid solution samples from which magnetic properties of transitions and third-law entropies have been determined. The magnetic transitions show several features common to effects of particle and magnetic domain sizes. From the standard molar entropies, excess entropies of mixing have been generated for these solid solutions and compared with configurational entropies determined previously by assuming appropriate cation and valence distributions. The vibrational and magnetic excess entropies for bulk materials are comparable in magnitude to the respective configurational entropies indicating that excess entropies of mixing must be included when analyzing entropies of mixing. The excess entropies for nanophase materials are even larger than the configurational entropies. Changes in valence, cation distribution, bonding and microstructure between the mixing ions are the likely sources of the positive excess entropies of mixing.

In Situ Foaming of Porous (La 0.6 Sr 0.4 ) 0.98 (Co 0.2 Fe 0.8 ) O 3-δ (LSCF) Cathodes for Solid Oxide Fuel Cell Applications

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

Gandavarapu, Sodith; Sabolsky, Edward; Sabolsky, Katarzyna

2013-07-18

A binder system containing polyurethane precursors was used to in situ foam (direct foam) a (La{sub 0.6}Sr{sub 0.4}){sub 0.98} (Co{sub 0.2} Fe{sub 0.8}) O{sub 3-{ delta}} (LSCF) composition for solid oxide fuel cell (SOFC) cathode applications. The relation between in situ foaming parameters on the final microstructure and electrochemical properties was characterized by microscopy and electrochemical impedance spectroscopy (EIS), respectively. The optimal porous cathode architecture was formed with a 70 vol% solids loading within a polymer precursor composition with a volume ratio of 8:4:1 (isocyanate: PEG: surfactant) in a terpineol-based ink vehicle. The resultant microstructure displayed a broad pore sizemore » distribution with highly elongated pore structure.« less

Formation of crystalline phase in the glass matrix of Zr-Co-Al glass-matrix composites and its effect on their mechanical properties

NASA Astrophysics Data System (ADS)

Kim, Woo Chul; Kim, Kang Chul; Na, Min Young; Jeong, Seok Hoan; Kim, Won Tae; Kim, Do Hyang

2017-11-01

The microstructural evolution and mechanical properties of Zr-Co-Al alloys, with compositions of (Zr50Co50)x (Zr56Co26Al18)1-x (x = 1/6, 2/6, 3/6, 4/6, 5/6, 1) and Zr54Co35Al11, (referred to as Z1, Z2, Z3, Z4, Z5, Z6, and Z4.5), were investigated. Alloys Z1-Z3 consisted of crystalline phases, while alloys Z4 and Z4.5 consisted of crystalline phase particles ( 3 vol% and 35 vol%, respectively) embedded within the glassy matrix. Alloys Z5 and Z6 consisted of a monolithic glass phase. The crystalline phase of alloys Z1-Z4.5 consisted of primary B2-ZrCo dendrite and an interdendritic B2-ZrCo/Zr6CoAl2 eutectic phase. The B2-ZrCo dendritic phase exhibited a high work-hardening rate, which originated from the deformation-induced B2-to-B33 martensitic transformation. However, when the brittle interdendritic B2-ZrCo/Zr6CoAl2 eutectic phase fraction increased, the work-hardening rate significantly decreased. The ductility of the glass-matrix composites was significantly impaired by the presence of the interdendritic eutectic phase in the crystalline phase. The results indicate that the design of the crystalline particle microstructure is important with regard to enhancing the plasticity of glass-matrix composites.

CoP/WS2 nanoflake heterostructures as efficient electrocatalysts for significant improvement in hydrogen evolution activity

NASA Astrophysics Data System (ADS)

Chen, Yajie; Kang, Chuanhong; Wang, Ruihong; Ren, Zhiyu; Fu, Huiying; Xiao, Yuting; Tian, Guohui

2018-06-01

The CoP/WS2 nanoflake composites were synthesized via the sulfuration and subsequent phosphidation using the pre-prepared WO2.72 nanowires as precursors. Originally, WO2.72 nanowires were prepared and followed by sulfuration to obtain WS2 nanoflakes. The as-prepared WS2 nanoflakes were used as substrates, on which the Co3O4 nanoparticles were uniformly anchored to construct the Co3O4/WS2 nanoflakes. Finally, the Co3O4/WS2 composites were subjected to phosphidation and in-situ converted into CoP/WS2 nanoflakes. Because of the dual functionalities of both CoP and WS2, the abundant interfaces as well as their synergy, the CoP/WS2 nanoflakes exhibited much higher electrocatalytic activity, smaller overpotential (-81 mV), lower Tafel slope (62 mV decade-1), and higher stability toward hydrogen-evolution reaction than those for the single CoP and WS2.

Magnetic properties of Li0.5Fe2.5O4 nanoparticles synthesized by solution combustion method

NASA Astrophysics Data System (ADS)

Naderi, P.; Masoudpanah, S. M.; Alamolhoda, S.

2017-11-01

In this research, lithium ferrite (Li0.5Fe2.5O4) powders were prepared by solution combustion synthesis using glycine and citric acid fuels at various fuel to oxidant molar ratios ( ϕ = 0.5, 1 and 1.5). Phase evolution, microstructure and magnetic properties were characterized by thermal analysis, infrared spectroscopy, X-ray diffraction, electron microscopy and vibration sample magnetometry techniques. Single-phase lithium ferrite was formed using glycine fuel at all fuel to oxidant ratios, while some impurity α-Fe2O3 phase was appeared using citric acid fuel at ϕ ≥ 1. The phase and crystallite size mainly depended on the combustion rate through fuel type. Bulky microstructure observed for citric acid fuel was attributed to its slow combustion, while the fast exhausting of gaseous products led to spongy microstructure for glycine fuel. The highest saturation magnetization of 59.3 emu/g and coercivity of 157 Oe were achieved for the as-combusted powders using glycine fuel.

Synthesis and characterization of mesoporous spinel NiCo2O4 using surfactant-assembled dispersion for asymmetric supercapacitors

NASA Astrophysics Data System (ADS)

Hsu, Chun-Tsung; Hu, Chi-Chang

2013-11-01

A simple and scalable process has been developed for synthesizing spinel NiCo2O4 nanocrystals through a thermal decomposition method. The introduction of hexadecyltrimethylammonium bromide (CTAB, (C16H33)N(CH3)3Br) into precursor solutions significantly enhances the homogeneity and porosity of spinel NiCo2O4. The porosity and high specific surface area of NiCo2O4 preserves the brilliant pseudo-capacitive performances due to providing smooth paths for electrolyte penetration and ion diffusion into inner active sites. Morphologies and microstructures of the active materials are examined by transmission electron microscopic (TEM) and X-ray diffraction (XRD) analyses. Thermogravimetric analysis (TGA) is used to evaluate the thermal properties of precursor solutions. The electrochemical performances of NiCo2O4 are systematically characterized by cyclic voltammetry and charge-discharge tests. Asymmetric supercapacitors are assembled with these brilliant binary oxides as the positive electrode and activated carbon as the negative electrode. The highly porous NiCo2O4 exhibits superior capacitive performances, i.e., high specific capacitance (764 F g-1 at 2 mV s-1) and long cycle life.

Microstructural Evolution of Al2O3-ZrO2 (Y2O3) Composites and its Correlation with Toughness

NASA Astrophysics Data System (ADS)

Kim, Hee Seung; Seo, Mi Young; Kim, Ik Jin

2008-02-01

The microstructure of zirconia (ZrO2) toughened alumina (Al2O3) ceramics was carefully controlled so as to obtain dense and fine-grained ceramics, thereby improving the properties and reliability of the ceramics for capillary applications in semiconductor bonding technology. Al2O3-ZrO2(Y2O3) composite was produced via Ceramic Injection Molding (CIM) technology, followed by Sinter-HIP process. Room temperature strength, hardness, Young's modulus, thermal expansion coefficient and toughness were determined, as well as surface strengthening induced by the fine grained homogenous microstructure and the thermal treatment. The changes in alumina/zirconia grain size, sintering condition and HIP treatment were found to be correlated.

Yb-doped Gd2O2CO3: Structure, microstructure, thermal and magnetic behaviour

NASA Astrophysics Data System (ADS)

Artini, Cristina; Locardi, Federico; Pani, Marcella; Nelli, Ilaria; Caglieris, Federico; Masini, Roberto; Plaisier, Jasper Rikkert; Costa, Giorgio Andrea

2017-04-01

Structural and microstructural features, as well as thermal and magnetic properties of Yb-doped Gd2O2CO3, were investigated with the aim to clarify the location and the oxidation state of Yb within the structure, and its role in driving the extent of the (Gd1-xYbx)2O2CO3 solid solution. Yb is found in the 3+ oxidation state and it enters the structure only at the rare earth atomic site; the solubility limit results to be located in the close vicinity of x=0.25, and thermal analyses reveal a linear decrease of the decomposition temperature with increasing the Yb amount, in agreement with literature data. The structural analysis allows to exclude long-range clusterization of Yb and Gd, since both rare earths randomly distribute over the 4f atomic position, but relying on the results of the microstructural analysis, the presence of compositional inhomogenities at the local scale cannot be excluded. Not all the structural forms are documented for the pure rare earth dioxycarbonates [1]; in particular, while form I exists for each lanthanide ion, form II is stable only for the largest ones (from La to Dy); moreover, even if II-Ho2O2CO3 (rHo3+ CN8=1.015 Å [6]) is not reported to be stable, the existence of II-Y2O2CO3 (rY3+ CN8=1.019 Å [6]) has been claimed [7]. Based on the described evidence, the stability of hexagonal Yb-doped Gd2O2CO3 is not expected along the whole compositional range. As a general remark, not all the rare earth mixed dioxycarbonates exist: (Ce, Gd)2O2CO3, for instance, could not be obtained at any composition [8]; moreover, all the structural forms can be observed only in some mixed systems, such as for example (Gd, Nd)2O2CO3, by varying temperature and tuning the composition [9]. Rare earth dioxycarbonates are studied mainly for their CO2 sensing properties [10,11], and for their emission when properly doped with a luminescent lanthanide ion [12-17]. Recently, a study of this research group [18] revealed in Gd2O2CO3:4% Yb a phenomenon of persistent luminescence, with the emission taking place at 970 nm in correspondence of the Yb3+2F7/2-2F5/2 transition, detectable up to 144 h after the end of irradiation. The origin of persistent luminescence is still substantially unclear, even if it is well known that excitation energy has to be stored in an intrinsic or extrinsic trap to be then slowly released. Extrinsic traps can derive from the presence of an aliovalent ion within the matrix; this should be the case of Yb-doped Gd2O2CO3, due to the valence instability of Yb, that is believed to be induced by irradiation [19,20]. In this respect, the precise knowledge of the dioxycarbonate crystal structure and its compositional extent, as well as the determination of the Yb location and its surroundings within the crystal structure, are of great importance. Also a microstructural approach can provide useful hints about the environment of the doping ion, even if it can not replace an investigation at the local scale. The synthetic route used for the preparation of hexagonal RE dioxycarbonates plays an important role in the obtainment of monophasic samples. The formation of the product via transformation of form I or Ia is documented for light lanthanides up to Sm [1], while thermal decomposition of Gd oxalate at 600 °C in static CO2 was performed to obtain hexagonal Gd2O2CO3[21]. The latter method is useful also for the synthesis of some mixed oxycarbonates, such as the ones containing Gd/Nd [9], but not Gd/Ce [8]. Carbonatation of RE2O3 is also reported as successful for RE≡La [1], Pr [1], Gd [21] and Nd [22]. The duration of the synthetic process is significantly shortened by adding the eutectic mixture Li2CO3-Na2CO3-K2CO3 to oxides, and by heating the whole mixture [7]. Nanostructured Yb- and Er-doped Gd2O2CO3 were also obtained, by coating with SiO2 the corresponding RE(OH)CO3·H2O nanoparticles [23]. In this work we present a structural, microstructural, thermal and magnetic study of a series of Yb-doped Gd2O2CO3 samples, performed by synchrotron x-ray diffraction, differential thermal analysis coupled to thermogravimetry (DTA-TG), and magnetization measurements. Specimens were prepared by a synthetic route that consists in the carbonatation of mixed oxides assisted by the aforementioned eutectic mixture. The structural investigation allowed to identify the solubility limit of Yb within Gd2O2CO3 and to derive its preferential position; moreover, a microstructural effect due to microstrain induced by the introduction of a foreign atom in the 4f site was detected. The extent of the Gd/Yb solid solution, as well as the decomposition temperature, is discussed in terms of dimensional issues of the involved atomic sites. Magnetic measurements allowed to exclude the presence of Yb2+ and to recognize the occurrence of weak antiferromagnetic correlations. From the results obtained in this study a significant aid is expected for the understanding of the mechanisms ruling persistent luminescence in these materials.

High-performance non-enzymatic catalysts based on 3D hierarchical hollow porous Co3O4 nanododecahedras in situ decorated on carbon nanotubes for glucose detection and biofuel cell application.

PubMed

Wang, Shiyue; Zhang, Xiaohua; Huang, Junlin; Chen, Jinhua

2018-03-01

In this work, high-performance non-enzymatic catalysts based on 3D hierarchical hollow porous Co 3 O 4 nanododecahedras in situ decorated on carbon nanotubes (3D Co 3 O 4 -HPND/CNTs) were successfully prepared via direct carbonizing metal-organic framework-67 in situ grown on carbon nanotubes. The morphology, microstructure, and composite of 3D Co 3 O 4 -HPND/CNTs were characterized by scanning electron microscopy, transmission electron microscopy, micropore and chemisorption analyzer, and X-ray diffraction. The electrochemical characterizations indicated that 3D Co 3 O 4 -HPND/CNTs present considerably catalytic activity toward glucose oxidation and could be promising for constructing high-performance electrochemical non-enzymatic glucose sensors and glucose/O 2 biofuel cell. When used for non-enzymatic glucose detection, the 3D Co 3 O 4 -HPND/CNTs modified glassy carbon electrode (3D Co 3 O 4 -HPND/CNTs/GCE) exhibited excellent analytical performance with high sensitivity (22.21 mA mM -1  cm -2 ), low detection limit of 0.35 μM (S/N = 3), fast response (less than 5 s) and good stability. On the other hand, when the 3D Co 3 O 4 -HPND/CNTs/GCE worked as an anode of a biofuel cell, a maximum power density of 210 μW cm -2 at 0.15 V could be obtained, and the open circuit potential was 0.68 V. The attractive 3D hierarchical porous structural features, the large surface area, and the excellent conductivity based on the continuous and effective electron transport network in 3D Co 3 O 4 -HPND/CNTs endow 3D Co 3 O 4 -HPND/CNTs with the enhanced electrochemical performance and promising applications in electrochemical sensing, biofuel cell, and other energy storage and conversion devices such as supercapacitor. Graphical abstract High-performance non-enzymatic catalysts for enzymeless glucose sensing and biofuel cell based on 3D hierarchical hollow porous Co 3 O 4 nanododecahedras anchored on carbon nanotubes were successfully prepared via direct carbonizing metal-organic framework-67 in situ grown on carbon nanotubes.

Crystal phase analysis of SnO{sub 2}-based varistor ceramic using the Rietveld method

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

Moreira, M.L.; Pianaro, S.A.; Andrade, A.V.C.

2006-09-15

A second addition of l mol% of CoO to a pre calcined SnO{sub 2}-based ceramic doped with 1.0 mol% of CoO, 0.05 mol% of Nb{sub 2}O{sub 5} and 0.05 mol% of Cr{sub 2}O{sub 3} promotes the appearance of a secondary phase, Co{sub 2}SnO{sub 4}, besides the SnO{sub 2} cassiterite phase, when the ceramic was sintered at 1350 deg. C/2 h. This was observed using X-ray powder diffraction, scanning electron microscopy and energy dispersive X-ray techniques. Rietveld refinement was carried out to quantify the phases present in the ceramic system. The results of the quantitative analysis were 97 wt.% SnO{sub 2}more » and 3 wt.% Co{sub 2}SnO{sub 4}. The microstructural analysis showed that a certain amount of cobalt ion remains into cassiterite grains.« less

Metal-Organic-Framework-Derived Yolk-Shell-Structured Cobalt-Based Bimetallic Oxide Polyhedron with High Activity for Electrocatalytic Oxygen Evolution.

PubMed

Yu, Zhou; Bai, Yu; Liu, Yuxuan; Zhang, Shimin; Chen, Dandan; Zhang, Naiqing; Sun, Kening

2017-09-20

The development of inexpensive, efficient, and environmentally friendly catalysts for oxygen evolution reaction (OER) is of great significant for green energy utilization. Herein, binary metal oxides (M x Co 3-x O 4 , M = Zn, Ni, and Cu) with yolk-shell polyhedron (YSP) structure were fabricated by facile pyrolysis of bimetallic zeolitic imidazolate frameworks (MCo-ZIFs). Benefiting from the synergistic effects of metal ions and the unique yolk-shell structure, M x Co 3-x O 4 YSP displays good OER catalytic activity in alkaline media. Impressively, Zn x Co 3-x O 4 YSP shows a comparable overpotential of 337 mV at 10 mA cm -2 to commercial RuO 2 and exhibits superior long-term durability. The high activity and good stability reveals its promising application.

Direct Electrophoretic Deposition of Binder-Free Co3O4/Graphene Sandwich-Like Hybrid Electrode as Remarkable Lithium Ion Battery Anode.

PubMed

Yang, Yang; Huang, Jingxin; Zeng, Jing; Xiong, Jian; Zhao, Jinbao

2017-09-27

Co 3 O 4 is emerging as a promising anode candidate for lithium ion batteries (LIBs) with high theoretical capacity (890 mAh g -1 ) but suffers from poor electrochemical cycling stability resulting from the inferior intrinsic electronic conductivity and large volume changes during electrochemical cycling. Here, a new electrophoretic deposition Co 3 O 4 /graphene (EPD Co 3 O 4 /G) hybrid electrode is developed to improve the electrochemical performance. Through EPD, Co 3 O 4 nanocubes can be homogeneously embedded between graphene sheets to form a sandwich-like structure. Owing to the excellent flexibility of graphene and a large number of voids in this sandwich-like structure, the structural integrity and unobstructed conductive network can be maintained during cycling. Moreover, the electrode kinetics has proved to be a fast surface-controlled lithium storage process. As a result, the Co 3 O 4 /G hybrid electrode exhibits high specific capacity and excellent electrochemical cycling performance. The Co 3 O 4 /G hybrid electrode was also further studied by in situ electrochemical XRD to understand the relationship of its structure and performance: (1) The observed Li x Co 3 O 4 indicates an intermediate of possible small volume change in the first discharging. (2) The theoretical capacity achievement of the Co 3 O 4 in hybrid electrode was evidenced. (3) The correlation between the electrochemical performance and the structural evolution of the Co 3 O 4 /G hybrid electrode was discussed detailedly.

The rate of nitrite reduction in leaves as indicated by O2 and CO2 exchange during photosynthesis

PubMed Central

Eichelmann, H.; Oja, V.; Peterson, R.B.; Laisk, A.

2011-01-01

Light response (at 300 ppm CO2 and 10–50 ppm O2 in N2) and CO2 response curves [at absorbed photon fluence rate (PAD) of 550 μmol m−2 s−1] of O2 evolution and CO2 uptake were measured in tobacco (Nicotiana tabacum L.) leaves grown on either NO3− or NH4+ as N source and in potato (Solanum tuberosum L.), sorghum (Sorghum bicolor L. Moench), and amaranth (Amaranthus cruentus L.) leaves grown on NH4NO3. Photosynthetic O2 evolution in excess of CO2 uptake was measured with a stabilized zirconia O2 electrode and an infrared CO2 analyser, respectively, and the difference assumed to represent the rate of electron flow to acceptors alternative to CO2, mainly NO2−, SO42−, and oxaloacetate. In NO3−-grown tobacco, as well as in sorghum, amaranth, and young potato, the photosynthetic O2–CO2 flux difference rapidly increased to about 1 μmol m−2 s−1 at very low PADs and the process was saturated at 50 μmol quanta m−2 s−1. At higher PADs the O2–CO2 flux difference continued to increase proportionally with the photosynthetic rate to a maximum of about 2 μmol m−2 s−1. In NH4+-grown tobacco, as well as in potato during tuber filling, the low-PAD component of surplus O2 evolution was virtually absent. The low-PAD phase was ascribed to photoreduction of NO2− which successfully competes with CO2 reduction and saturates at a rate of about 1 μmol O2 m−2 s−1 (9% of the maximum O2 evolution rate). The high-PAD component of about 1 μmol O2 m−2 s−1, superimposed on NO2− reduction, may represent oxaloacetate reduction. The roles of NO2−, oxaloacetate, and O2 reduction in the regulation of ATP/NADPH balance are discussed. PMID:21239375

Co-regulation of dark and light reactions in three biochemical subtypes of C(4) species.

PubMed

Kiirats, Olavi; Kramer, David M; Edwards, Gerald E

2010-08-01

Regulation of light harvesting in response to changes in light intensity, CO(2) and O(2) concentration was studied in C(4) species representing three different metabolic subtypes: Sorghum bicolor (NADP-malic enzyme), Amaranthus edulis (NAD-malic enzyme), and Panicum texanum (PEP-carboxykinase). Several photosynthetic parameters were measured on the intact leaf level including CO(2) assimilation rates, O(2) evolution, photosystem II activities, thylakoid proton circuit and dissipation of excitation energy. Gross rates of O(2) evolution (J(O)₂'), measured by analysis of chlorophyll fluorescence), net rates of O(2) evolution and CO(2) assimilation responded in parallel to changes in light and CO(2) levels. The C(4) subtypes had similar energy requirements for photosynthesis since there were no significant differences in maximal quantum efficiencies for gross rates of O(2) evolution (average value = 0.072 O(2)/quanta absorbed, approximately 14 quanta per O(2) evolved). At saturating actinic light intensities, when photosynthesis was suppressed by decreasing CO(2), ATP synthase proton conductivity (g (H) (+)) responded strongly to changes in electron flow, decreasing linearly with J(O)₂', which was previously observed in C(3) plants. It is proposed that g (H) (+) is controlled at the substrate level by inorganic phosphate availability. The results suggest development of nonphotochemical quenching in C(4) plants is controlled by a decrease in g (H) (+), which causes an increase in proton motive force by restricting proton efflux from the lumen, rather than by cyclic or pseudocyclic electron flow.

Ceramics with Different Additives

NASA Astrophysics Data System (ADS)

Wang, Juanjuan; Feng, Lajun; Lei, Ali; Zhao, Kang; Yan, Aijun

2014-09-01

Li2CO3, MgCO3, BaCO3, and Bi2O3 dopants were introduced into CaCu3Ti4O12 (CCTO) ceramics in order to improve the dielectric properties. The CCTO ceramics were prepared by conventional solid-state reaction method. The phase structure, microstructure, and dielectric behavior were carefully investigated. The pure structure without any impurity phases can be confirmed by the x-ray diffraction patterns. Scanning Electron Microscopy (SEM) analysis illuminated that the grains of Ca0.90Li0.20Cu3Ti4O12 ceramics were greater than that of pure CCTO. It was important for the properties of the CCTO ceramics to study the additives in complex impedance spectroscopy. It was found that the Ca0.90Li0.20Cu3Ti4O12 ceramics had the higher permittivity (>45000), the lower dielectric loss (<0.025) than those of CCTO at 1 kHz at room temperature and good temperature stability from -30 to 75 °C.

On the role of ultra-thin oxide cathode synthesis on the functionality of micro-solid oxide fuel cells: Structure, stress engineering and in situ observation of fuel cell membranes during operation

NASA Astrophysics Data System (ADS)

Lai, Bo-Kuai; Kerman, Kian; Ramanathan, Shriram

Microstructure and stresses in dense La 0.6Sr 0.4Co 0.8Fe 0.2O 3 (LSCF) ultra-thin films have been investigated to increase the physical thickness of crack-free cathodes and active area of thermo-mechanically robust micro-solid oxide fuel cell (μSOFC) membranes. Processing protocols employ low deposition rates to create a highly granular nanocrystalline microstructure in LSCF thin films and high substrate temperatures to produce linear temperature-dependent stress evolution that is dominated by compressive stresses in μSOFC membranes. Insight and trade-off on the synthesis are revealed by probing microstructure evolution and electrical conductivity in LSCF thin films, in addition to in situ monitoring of membrane deformation while measuring μSOFC performance at varying temperatures. From these studies, we were able to successfully fabricate failure-resistant square μSOFC (LSCF/YSZ/Pt) membranes with width of 250 μm and crack-free cathodes with thickness of ∼70 nm. Peak power density of ∼120 mW cm -2 and open circuit voltage of ∼0.6 V at 560 °C were achieved on a μSOFC array chip containing ten such membranes. Mechanisms affecting fuel cell performance are discussed. Our results provide fundamental insight to pathways of microstructure and stress engineering of ultra-thin, dense oxide cathodes and μSOFC membranes.

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

Effect of annealing on particle size, microstructure and gas sensing properties of Mn substituted CoFe2O4 nanoparticles

NASA Astrophysics Data System (ADS)

Kumar, E. Ranjith; Kamzin, A. S.; Janani, K.

2016-11-01

Microstructure, morphological and gas sensor studies of Mn substituted cobalt ferrite nanoparticles synthesized by a simple evaporation method and auto- combustion method. The influence of heat treatment on phase and particle size of spinel ferrite nanoparticles were determined by X-ray diffraction and Mossbauer spectroscopy. The XRD study reveals that the lattice constant and crystallite size of the samples increases with the increase of annealing temperature. Last one was confirmed by Mossbauer data. The lowest size of particles of MnCoFe2O4 (~3 nm) is obtained by auto combustion method. The spherical shaped nanoparticles are recorded by TEM. Furthermore, conductance response of Mn-Co ferrite nanomaterial was measured by exposing the material to reducing gas like liquefied petroleum gas (LPG) which showed a sensor response of ~0.19 at an optimum operating temperature of 250 °C.

Synthesis of Y1Ba2Cu3O(sub x) superconducting powders by intermediate phase reaction

NASA Technical Reports Server (NTRS)

Moore, C.; Fernandez, J. F.; Recio, P.; Duran, P.

1990-01-01

One of the more striking problems for the synthesis of the Y1Ba2Cu3Ox compound is the high-temperature decomposition of the BaCO3. This compound is present as raw material or as an intermediate compound in chemical processes such as amorphous citrate, coprecipitation oxalate, sol-gel process, acetate pyrolisis, etc. This fact makes difficult the total formation reaction of the Y1Ba2Cu3Ox phase and leads to the presence of undesirable phases such as the BaCuO2 phase, the 'green phase', Y2BaCuO5 and others. Here, a new procedure to overcome this difficulty is studied. The barium cation is previously combined with yttrium and/or copper to form intermediate compounds which can react between them to give Y1Ba2Cu3Ox. BaY2O4 and BaCu2O3 react according to the equation BaY2O4+3BaCu2O3 yields 2Y1Ba2Cu3Ox. BaY2O4 is a stable compound of the Y2O3-BaO system; BaCu2O3 is an intimate mixture of BaCuO2 and uncombined CuO. The reaction kinetics of these phases have been established between 860 and 920 C. The phase evolution has been determined. The crystal structure of the Y1Ba2Cu3Ox obtained powder was studied. According to the results obtained from the kinetics study the Y1Ba2Cu3Ox the synthesis was performed at temperatures of 910 to 920 C for short treatment times (1 to 2 hours). Pure Y1Ba2Cu3Ox was prepared, which develops orthorombic type I structure despite of the cooling cycle. Superconducting transition took place at 91 K. The sintering behavior and the superconducting properties of sintered samples were studied. Density, microstructure and electrical conductivity were measured. Sintering densities higher than 95 percent D(sub th) were attained at temperatures below 940 C. Relatively fine grained microstructure was observed, and little or no-liquid phase was detected.

Comparative study of nano-sized particles CoFe2O4 effects on superconducting properties of Y-123 and Y-358

NASA Astrophysics Data System (ADS)

Slimani, Y.; Hannachi, E.; Ben Salem, M. K.; Hamrita, A.; Varilci, A.; Dachraoui, W.; Ben Salem, M.; Ben Azzouz, F.

2014-10-01

The effects of nano-sized CoFe2O4 particles (10 nm) addition on the structural and the normal state resistivity of YBa2Cu3O7 (noted Y-123) and Y3Ba5Cu8O18 (noted Y-358) polycrystalline were systematically studied. Samples were synthesized in oxygen atmosphere using a standard solid state reaction technique by adding CoFe2O4 up to 2 wt%. Phases, microstructure and superconductivity have been systematically investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrical measurements ρ(T). XRD results reveal that the lattice parameters change for both Y-123 and Y-358 phases. SEM observations reveal that the grain size is reduced with increasing the content of CoFe2O4. The measurements for the resistivity dependence of temperature show that the depression in superconducting temperature is more pronounced for CoFe2O4 addition in Y-358 compound than in Y-123 one. These results may be attributed to the existence of much more disorder due to a greater number of Cu sites to be substituted by Fe and Co in Y-358 compared to Y-123.

Morphological Control of Mesoporosity and Nanoparticles within Co3O4-CuO Electrospun Nanofibers: Quantum Confinement and Visible Light Photocatalysis Performance.

PubMed

Pradhan, Amaresh C; Uyar, Tamer

2017-10-18

The one-dimensional (1D) mesoporous and interconnected nanoparticles (NPs) enriched composite Co 3 O 4 -CuO nanofibers (NFs) in the ratio Co:Cu = 1/4 (Co 3 O 4 -CuO NFs) composite have been synthesized by electrospinning and calcination of mixed polymeric template. Not merely the mesoporous composite Co 3 O 4 -CuO NFs but also single mesoporous Co 3 O 4 NFs and CuO NFs have been produced for comparison. The choice of mixed polymer templates such as polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG) for electrospinning is responsible for the formation of 1D mesoporous NFs. The HR-TEM result showed evolution of interconnected nanoparticles (NPs) and creation of mesoporosity in all electrospun NFs. The quantum confinement is due to NPs within NFs and has been proved by the surface-enhanced Raman scattering (SERS) study and the UV-vis-NRI diffuse reflectance spectra (DRS). The high intense photoluminescence (PL) spectra showing blue shift of all NFs also confirmed the quantum confinement phenomena. The lowering of PL spectrum after mixing of CuO in Co 3 O 4 nanofibers framework (Co 3 O 4 -CuO NFs) proved CuO as an efficient visible light response low cost cocatalyst/charge separator. The red shifting of the band gap in composite Co 3 O 4 -CuO NFs is due to the internal charge transfer between Co 2+ to Co 3+ and Cu 2+ , proved by UV-vis absorption spectroscopy. Creation of oxygen vacancies by mixing of CuO and Co 3 O 4 also prevents the electron-hole recombination and enhances the photocatalytic activity in composite Co 3 O 4 -CuO NFs. The photocurrent density, Mott-Schottky (MS), and electrochemical impedance spectroscopy (EIS) studies of all NFs favor the high photocatalytic performance. The mesoporous composite Co 3 O 4 -CuO NFs exhibits high photocatalytic activity toward phenolic compounds degradation as compared to the other two NFs (Co 3 O 4 NFs and CuO NFs). The kinetic study of phenolic compounds followed first order rate equation. The high photocatalytic activity of composite Co 3 O 4 -CuO NFs is attributed to the formation of mesoporosity and interconnected NPs within NFs framework, quantum confinement, extended light absorption property, internal charge transfer, and effective photogenerated charge separations.

Evolution of Constitution, Structure, and Morphology in FeCo-Based Multicomponent Alloys

NASA Astrophysics Data System (ADS)

Li, R.; Stoica, M.; Liu, G.; Eckert, J.

2010-07-01

Constituent phases, melting behaviors, and microstructure of multicomponent (Fe0.5Co0.5) x (Mo0.1C0.2B0.5Si0.2)100- x alloys ( x = 95, 90, 85, 80, and 70) produced by copper mold casting were evaluated by various analysis techniques, i.e., X-ray diffractometry, scanning electronic microscopy with energy dispersive X-ray spectrometry, and differential scanning calorimetry. Metastable Fe3C- and Cr23C6-type phases were identified in the chill-cast alloys. A schematic illustration was proposed to explain the evolution of constituent phases and microstructure for the alloys with x = 95, 90, and 85 during the solidification process, which could be applicable to controlling microstructural formation of other multicomponent alloys with similar microstructures by artificially adjusting the composition.

Thermoelectric Properties and Microstructure of Ca3 Co 4 O 9 thin films on SrTiO3 and Al2 O 3 Substrates

NASA Astrophysics Data System (ADS)

Paulauskas, T.; Qiao, Q.; Gulec, A.; Klie, R. F.; Ozdemir, M.; Boyraz, C.; Mazumdar, D.; Gupta, A.

2011-03-01

Ca 3 Co 4 O9 (CCO), a misfit layered structure exhibiting large Seebeck coefficient at temperatures up to 1000K has attracted increasing attention as a novel high-temperature thermoelectric material. In this work, we investigate CCO thin films grown on SrTi O3 (001) and Al 2 O3 (0001) using pulsed laser deposition. Quality of the thin films was examined using high-resolution transmission electron microscopy and thermoelectric transport measurements. HRTEM images show incommensurate stacks of Cd I2 -type Co O2 layer alternating with rock-salt-type Ca 2 Co O3 layer along the c-axis. Perovskite buffer layer about 10nm thick was found present between CCO and SrTi O3 accompanied by higher density of stacking faults. The CCO grown on Al 2 O3 exhibited numerous misoriented grains and presence of Ca x Co O2 phase. Seebeck coefficient measurements yield an improvement for both samples compared to the bulk value. We suggest that thermoelectric properties of CCO increase due to additional phonon scattering at the stacking faults as well as at the film surfaces/interfaces. This research was supported by the US Army Research Office (W911NF-10-1-0147) and the Sivananthan Undergraduate Research Fellowship.

Effects of microstructure and CaO addition on the magnetic and mechanical properties of NiCuZn ferrites

NASA Astrophysics Data System (ADS)

Wang, Sea-Fue; Hsu, Yung-Fu; Liu, Yi-Xin; Hsieh, Chung-Kai

2015-11-01

In this study, the effects of grain size and the addition of CaCO3 on the magnetic and mechanical properties of Ni0.5Cu0.3Zn0.2Fe2O4 ceramics were investigated. The bending strength of the ferrites increased from 66 to 84 MPa as the grain size of the sintered ceramics decreased from 10.25 μm to 7.53 μm, while the change in hardness was insignificant. The addition of various amounts of CaCO3 densified the Ni0.5Cu0.3Zn0.2Fe2O4 ceramics at 1075 °C. In the pure Ni0.5Cu0.3Zn0.2Fe2O4 ceramic, second phase CuO was segregated at the grain boundaries. With the CaCO3 content ≥1.5 wt%, a small amount of discrete plate-like second phase Fe2CaO4 was observed, together with the disappearance of the second phase CuO. The grain size of the Ni0.5Cu0.3Zn0.2Fe2O4 ceramic dropped from 7.80 μm to 4.68 μm, and the grain size distribution widened as the CaCO3 content increased from 0 to 5 wt%. Initially rising to 807 after CaCO3 addition up to 2.0 wt%, due to a reduced grain size, the Vickers hardness began to drop as the CaCO3 content increased. The bending strength grew linearly with the CaCO3 content and reached twice the value for the Ni0.5Cu0.3Zn0.2Fe2O4 ceramic with an addition of 5.0 wt% CaCO3. The initial permeability of the Ni0.5Cu0.3Zn0.2Fe2O4 ceramic decreased substantially from 402 to 103 as the addition of CaCO3 in ferrite increased from 0 to 5 wt%, and the quality factor of the Ni0.5Cu0.3Zn0.2Fe2O4 ceramic was maximized at 95 for 1.0 wt% CaCO3 addition.

Hollow Fluffy Co3O4 Cages as Efficient Electroactive Materials for Supercapacitors and Oxygen Evolution Reaction.

PubMed

Zhou, Xuemei; Shen, Xuetao; Xia, Zhaoming; Zhang, Zhiyun; Li, Jing; Ma, Yuanyuan; Qu, Yongquan

2015-09-16

Nano-/micrometer multiscale hierarchical structures not only provide large surface areas for surface redox reactions but also ensure efficient charge conductivity, which is of benefit for utilization in areas of electrochemical energy conversion and storage. Herein, hollow fluffy cages (HFC) of Co3O4, constructed of ultrathin nanosheets, were synthesized by the formation of Co(OH)2 hollow cages and subsequent calcination at 250 °C. The large surface area (245.5 m2 g(-1)) of HFC Co3O4 annealed at 250 °C ensures the efficient interaction between electrolytes and electroactive components and provides more active sites for the surface redox reactions. The hierarchical structures minimize amount of the grain boundaries and facilitate the charge transfer process. Thin thickness of nanosheets (2-3 nm) ensures the highly active sites for the surface redox reactions. As a consequence, HFC Co3O4 as the supercapacitor electrode exhibits a superior rate capability, shows an excellent cycliability of 10,000 cycles at 10 A g(-1), and delivers large specific capacitances of 948.9 and 536.8 F g(-1) at 1 and 40 A g(-1), respectively. Catalytic studies of HFC Co3O4 for oxygen evolution reaction display a much higher turnover frequency of 1.67×10(-2) s(-1) in pH 14.0 KOH electrolyte at 400 mV overpotential and a lower Tafel slope of 70 mV dec(-1). HFC Co3O4 with the efficient electrochemical activity and good stability can remain a promising candidate for the electrochemical energy conversion and storage.

Is [Co4(H2O)2(α-PW9O34)2](10-) a genuine molecular catalyst in photochemical water oxidation? Answers from time-resolved hole scavenging experiments.

PubMed

Natali, Mirco; Berardi, Serena; Sartorel, Andrea; Bonchio, Marcella; Campagna, Sebastiano; Scandola, Franco

2012-09-11

Water oxidation catalysts: evolution of [Co(4)(H(2)O)(2)(α-PW(9)O(34))(2)](10-) to catalytically active species is assessed by laser flash photolysis in sacrificial photocatalytic cycles with Ru(bpy)(3)(2+) as a photosensitizer.

X-ray nanotomography analysis of the microstructural evolution of LiMn 2O 4 electrodes

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

Liu, Zhao; Han, Kai; Chen-Wiegart, Yu-chen Karen

One of the greatest challenges for advancing lithium-ion battery (LIB) technology is to minimize cell degradation during operation for long-term stability. To this end, it is important to understand how cell performance during operation relates to complex LIB microstructures. In this report, transmission X-ray microscopy (TXM) nanotomography is used to gain quantitative three-dimensional (3D) microstructure-performance correlations of LIB cathodes during cycling. The 3D microstructures of LiMn 2O 4 (LMO) electrodes, cycled under different conditions, including cycle number, operating voltage, and temperature, are characterized via TXM and statistically analyzed to investigate the impact of cycling conditions on the electrode microstructural evolutionmore » and cell performance. It is found that the number of cracks formed within LMO particles correlated with capacity fade. For the cell cycled at elevated temperatures, which exhibits the most severe capacity fade among all cells tested, mechanical cracking observed in TXM is not the only dominant contributor to the observed degradation. Mn 2+ dissolution, as verified by detection of Mn on the counter electrode by energy dispersive spectrometry, also contributed. The current work demonstrate 3D TXM nanotomography as a powerful tool to help probe in-depth.« less

X-ray nanotomography analysis of the microstructural evolution of LiMn 2O 4 electrodes

DOE PAGES

Liu, Zhao; Han, Kai; Chen-Wiegart, Yu-chen Karen; ...

2017-06-17

One of the greatest challenges for advancing lithium-ion battery (LIB) technology is to minimize cell degradation during operation for long-term stability. To this end, it is important to understand how cell performance during operation relates to complex LIB microstructures. In this report, transmission X-ray microscopy (TXM) nanotomography is used to gain quantitative three-dimensional (3D) microstructure-performance correlations of LIB cathodes during cycling. The 3D microstructures of LiMn 2O 4 (LMO) electrodes, cycled under different conditions, including cycle number, operating voltage, and temperature, are characterized via TXM and statistically analyzed to investigate the impact of cycling conditions on the electrode microstructural evolutionmore » and cell performance. It is found that the number of cracks formed within LMO particles correlated with capacity fade. For the cell cycled at elevated temperatures, which exhibits the most severe capacity fade among all cells tested, mechanical cracking observed in TXM is not the only dominant contributor to the observed degradation. Mn 2+ dissolution, as verified by detection of Mn on the counter electrode by energy dispersive spectrometry, also contributed. The current work demonstrate 3D TXM nanotomography as a powerful tool to help probe in-depth.« less

Slurry erosion induced surface nanocrystallization of bulk metallic glass

NASA Astrophysics Data System (ADS)

Ji, Xiulin; Wu, Jili; Pi, Jinghong; Cheng, Jiangbo; Shan, Yiping; Zhang, Yingtao

2018-05-01

Microstructure evolution and phase transformation of metallic glasses (MGs) could occur under heating condition or mechanical deformation. The cross-section of as-cast Zr55Cu30Ni5Al10 MG rod was impacted by the solid particles when subjected to erosion in slurry flow. The surface microstructure was observed by XRD before and after slurry erosion. And the stress-driven de-vitrification increases with the increase of erosion time. A microstructure evolution layer with 1-2 μm thickness was formed on the topmost eroded surface. And a short range atomic ordering prevails in the microstructure evolution layer with crystalline size around 2-3 nm embedded in the amorphous matrix. The XPS analysis reveals that most of the metal elements in the MG surface, except for Cu, were oxidized. And a composite layer with ZrO2 and Al2O3 phases were formed in the topmost surface after slurry erosion. The cooling rate during solidification of MG has a strong influence on the slurry erosion induced nanocrystallization. And a lower cooling rate favors the surface nanocrystallization because of lower activation energy and thermo-stability. Finally, the slurry erosion induced surface nanocrystallization and microstructure evolution result in surface hardening and strengthening. Moreover, the microstructure evolution mechanisms were discussed and it is related to the cooling rate of solidification and the impact-induced temperature rise, as well as the combined effects of the impact-induced plastic flow, inter-diffusion and oxidation of the metal elements.

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

Stechel, Ellen Beth; Ambrosini, Andrea; Coker, Eric Nicholas

The Sunshine to Petrol effort at Sandia aims to convert carbon dioxide and water to precursors for liquid hydrocarbon fuels using concentrated solar power. Significant advances have been made in the field of solar thermochemical CO{sub 2}-splitting technologies utilizing yttria-stabilized zirconia (YSZ)-supported ferrite composites. Conceptually, such materials work via the basic redox reactions: Fe{sub 3}O{sub 4} {yields} 3FeO + 0.5O{sub 2} (Thermal reduction, >1350 C) and 3FeO + CO{sub 2} {yields} Fe{sub 3}O{sub 4} + CO (CO{sub 2}-splitting oxidation, <1200 C). There has been limited fundamental characterization of the ferrite-based materials at the high temperatures and conditions present in thesemore » cycles. A systematic study of these composites is underway in an effort to begin to elucidate microstructure, structure-property relationships, and the role of the support on redox behavior under high-temperature reducing and oxidizing environments. In this paper the synthesis, structural characterization (including scanning electron microscopy and room temperature and in-situ x-ray diffraction), and thermogravimetric analysis of YSZ-supported ferrites will be reported.« less

Toward High-Performance and Low-Cost Hydrogen Evolution Reaction Electrocatalysts: Nanostructuring Cobalt Phosphide (CoP) Particles on Carbon Fiber Paper.

PubMed

Yu, Shu Hearn; Chua, Daniel H C

2018-05-02

In this communication, we facily fabricated nanostructured CoP particles (150 to 200 nm) on carbon fiber paper (CFP) for hydrogen evolution reaction (HER) by a simple two-step process via a green route. In the first step, crystalline Co 3 O 4 nanocubes (150-200 nm) were loaded on CFP through a hydrothermal process at low temperature (120 °C). Interestingly, crystalline Co 3 O 4 nanocubes with a size 150-200 nm exhibited different growth mechanisms in contrast to the crystalline Co 3 O 4 nanocubes with a size <100 nm reported earlier. In the second step, these crystalline Co 3 O 4 nanocubes were converted to catalytically active CoP particles through chemical vapor deposition (CVD) phosphorization (denoted as CoP/CFP-H). Remarkably, CoP/CFP-H exhibited a low Tafel slope of 49.7 mV/dec and only required overpotentials of 128.1, 144.4, and 190.8 mV to drive geometric current densities of -10, -20, and -100 mA cm -2 , respectively. Besides, the CoP/CFP-H also demonstrated an excellent durability in an acidic environment under 2000 sweeps at a high scan rate (100 mV s -1 ) and a 24 h chronopotentiometry testing. For comparison, CoP was also fabricated through the electrodeposition method, followed by CVD phosphorization (denoted as CoP/CFP-E). It was found that the latter had exhibited inferior activity compared to CoP/CFP-H. The good performances of CoP/CFP-H are essentially due to the rational designs of electrode: (i) the applications of highly HER active CoP electrocatalyst, (ii) the intimate contact of nanostructured CoP on carbon fibers, and (iii) the large electrochemical surface area at electrocatalyst/electrolyte interface due to the large retaining of particles features after phosphorization. Notably, the intermediate Co 3 O 4 /CFP can serve as a platform to develop other cobalt-based functional materials.

Fabrication and spectroscopic properties of Co:MgAl2O4 transparent ceramics by the HIP post-treatment

NASA Astrophysics Data System (ADS)

Luo, Wei; Ma, Peng; Xie, Tengfei; Dai, Jiawei; Pan, Yubai; Kou, Huamin; Li, Jiang

2017-07-01

Cobalt-doped magnesium aluminate spinel (Co:MgAl2O4) is one of the most important saturable absorbers for the passive Q-switching of solid-state lasers operating at eye-safe wavelength of 1.5 μm. In this work, highly transparent Co:MgAl2O4 ceramics were fabricated by vacuum sintering combined with hot isostatic pressing (HIP) post-treatment, using the mixture of the commercial spinel and the lab-made Co:MgAl2O4 powder as the raw materials. The densification mechanism of Co:MgAl2O4 transparent ceramics was discussed. The microstructure and optical properties of the samples were investigated. The ground state absorption cross section (σGSA) was calculated from the fitted curve of the absorption coefficient spectrum. The results show that Co:MgAl2O4 ceramics fabricated by vacuum sintering at 1500 °C for 5 h and then HIP post-treatment at 1650 °C for 3 h perform good transparency, whose in-line transmittance exceeds 80% at 2500 nm. Moreover, the ground state absorption cross section of 0.02 at.% Co:MgAl2O4 ceramics is calculated to be 3.35 × 10-19 cm2 at the wavelength of 1540 nm, which is promising for the application to the passive Q-switching of solid-state laser operating in the near infrared region (NIR).

Microstructure, Thermal, Mechanical, and Dielectric Properties of BaO-CaO-Al2O3-B2O3-SiO2 Glass-Ceramics

NASA Astrophysics Data System (ADS)

Li, Bo; Bian, Haibo; Fang, Yi

2017-12-01

BaO-CaO-Al2O3-B2O3-SiO2 (BCABS) glass-ceramics were prepared via the method of controlled crystallization. The effect of CaO modification on the microstructure, phase evolution, as well as thermal, mechanical, and dielectric properties was investigated. XRD identified that quartz is the major crystal phase; cristobalite and bazirite are the minor crystal phases. Moreover, the increase of CaO could inhibit the phase transformation from quartz to cristobalite, but excessive CaO would increase the porosity of the ceramics. Additionally, with increasing the amount of CaO, the thermal expansion curve tends to be linear, and subsequently the CTE value decreases gradually, which is attributed to the decrease of cristobalite with high CTE and the formation of CaSiO3 with low CTE. The results indicated that a moderate amount of CaO helps attaining excellent mechanical, thermal, and dielectric properties, that is, the specimen with 9 wt% CaO sintered at 950 °C has a high CTE value (11.5 × 10-6/°C), a high flexural strength (165.7 MPa), and good dielectric properties (ɛr = 6.2, tanδ = 1.8 × 10-4, ρ = 4.6 × 1011 Ω•cm).

Anisotropic electrical and thermal conductivity in Bi2AE2Co2O8+δ [AE = Ca, Sr1-xBax (x = 0.0, 0.25, 0.5, 0.75, 1.0)] single crystals

NASA Astrophysics Data System (ADS)

Dong, Song-Tao; Zhang, Bin-Bin; Xiong, Ye; Lv, Yang-Yang; Yao, Shu-Hua; Chen, Y. B.; Zhou, Jian; Zhang, Shan-Tao; Chen, Yan-Feng

2015-09-01

Bi2AE2Co2O8+δ (AE represents alkaline earth), constructed by stacking of rock-salt Bi2AE2O4 and triangle CoO2 layers alternatively along c-axis, is one of promising thermoelectric oxides. The most impressive feature of Bi2AE2Co2O8+δ, as reported previously, is their electrical conductivity mainly lying along CoO2 plane, adjusting Bi2AE2O4 layer simultaneously manipulates both thermal conductivity and electrical conductivity. It in turn optimizes thermoelectric performance of these materials. In this work, we characterize the anisotropic thermal and electrical conductivity along both ab-plane and c-direction of Bi2AE2Co2O8+δ (AE = Ca, Sr, Ba, Sr1-xBax) single crystals. The results substantiate that isovalence replacement in Bi2AE2Co2O8+δ remarkably modifies their electrical property along ab-plane; while their thermal conductivity along ab-plane only has a slightly difference. At the same time, both the electrical conductivity and thermal conductivity along c-axis of these materials also have dramatic changes. Certainly, the electrical resistance along c-axis is too high to be used as thermoelectric applications. These results suggest that adjusting nano-block Bi2AE2O4 layer in Bi2AE2Co2O8+δ cannot modify the thermal conductivity along high electrical conductivity plane (ab-plane here). The evolution of electrical property is discussed by Anderson localization and electron-electron interaction U. And the modification of thermal conductivity along c-axis is attributed to the microstructure difference. This work sheds more light on the manipulation of the thermal and electrical conductivity in the layered thermoelectric materials.

Spatially-controlled NiCo2O4@MnO2 core–shell nanoarray with hollow NiCo2O4 cores and MnO2 flake shells: an efficient catalyst for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Xue, Hairong; Yu, Hongjie; Li, Yinghao; Deng, Kai; Xu, You; Li, Xiaonian; Wang, Hongjing; Wang, Liang

2018-07-01

Control of structures and components of the nanoarray catalysts is very important for electrochemical energy conversion. Herein, unique NiCo2O4@MnO2 core–shell nanoarray with hollow NiCo2O4 Cores and MnO2 flake shells is in situ fabricated on carbon textile via a two-step hydrothermal treatment followed by a subsequent annealing. The as-made nanoarray is highly active and durable catalyst for oxygen evolution reaction in alkaline media attribute to the synergetic effect derived from spatially separated nanoarray with favorable NiCo2O4 and MnO2 compositions.

Spatially-controlled NiCo2O4@MnO2 core-shell nanoarray with hollow NiCo2O4 cores and MnO2 flake shells: an efficient catalyst for oxygen evolution reaction.

PubMed

Xue, Hairong; Yu, Hongjie; Li, Yinghao; Deng, Kai; Xu, You; Li, Xiaonian; Wang, Hongjing; Wang, Liang

2018-07-13

Control of structures and components of the nanoarray catalysts is very important for electrochemical energy conversion. Herein, unique NiCo 2 O 4 @MnO 2 core-shell nanoarray with hollow NiCo 2 O 4 Cores and MnO 2 flake shells is in situ fabricated on carbon textile via a two-step hydrothermal treatment followed by a subsequent annealing. The as-made nanoarray is highly active and durable catalyst for oxygen evolution reaction in alkaline media attribute to the synergetic effect derived from spatially separated nanoarray with favorable NiCo 2 O 4 and MnO 2 compositions.

Nitrate-Dependent O2 Evolution in Intact Leaves 1

PubMed Central

de la Torre, Angel; Delgado, Begoña; Lara, Catalina

1991-01-01

Evolution of O2 by illuminated intact detached leaves from barley (Hordeum vulgare L. cv Athos) and pea (Pisum sativum L. cv Lincoln) in a CO2-saturating atmosphere was enhanced when KNO3 (1-2.5 millimolar) had been previously supplied through the transpiration stream. The extra O2 evolution observed after feeding KNO3 increased with the light intensity, being maximal at near saturating photon flux densities and resulting in no changes in the initial slope of the O2 versus light-intensity curve. No stimulation of O2 evolution was otherwise observed after feeding KCl or NH4Cl. The data indicate that nitrate assimilation uses photosynthetically generated reductant and stimulates the rate of non-cyclic electron flow by acting as a second electron-accepting assimilatory process in addition to CO2 fixation. PMID:16668272

Facile and cost effective synthesis of mesoporous spinel NiCo2O4 as an anode for high lithium storage capacity

NASA Astrophysics Data System (ADS)

Jadhav, Harsharaj S.; Kalubarme, Ramchandra S.; Park, Choong-Nyeon; Kim, Jaekook; Park, Chan-Jin

2014-08-01

To fulfill the high power and high energy density demands for Li-ion batteries (LIBs) new anode materials need to be explored to replace conventional graphite. Herein, we report the urea assisted facile co-precipitation synthesis of spinel NiCo2O4 and its application as an anode material for LIBs. The synthesized NiCo2O4 exhibited an urchin-like microstructure and polycrystalline and mesoporous nature. In addition, the mesoporous NiCo2O4 electrode exhibited an initial discharge capacity of 1095 mA h g-1 and maintained a reversible capacity of 1000 mA h g-1 for 400 cycles at 0.5 C-rate. The reversible capacity of NiCo2O4 could still be maintained at 718 mA h g-1, even at 10 C. The mesoporous NiCo2O4 exhibits great potential as an anode material for LIBs with the advantages of unique performance and facile preparation.To fulfill the high power and high energy density demands for Li-ion batteries (LIBs) new anode materials need to be explored to replace conventional graphite. Herein, we report the urea assisted facile co-precipitation synthesis of spinel NiCo2O4 and its application as an anode material for LIBs. The synthesized NiCo2O4 exhibited an urchin-like microstructure and polycrystalline and mesoporous nature. In addition, the mesoporous NiCo2O4 electrode exhibited an initial discharge capacity of 1095 mA h g-1 and maintained a reversible capacity of 1000 mA h g-1 for 400 cycles at 0.5 C-rate. The reversible capacity of NiCo2O4 could still be maintained at 718 mA h g-1, even at 10 C. The mesoporous NiCo2O4 exhibits great potential as an anode material for LIBs with the advantages of unique performance and facile preparation. Electronic supplementary information (ESI) available: Experimental details and additional experimental results. See DOI: 10.1039/c4nr02183e

Hydrophilic cobalt sulfide nanosheets as a bifunctional catalyst for oxygen and hydrogen evolution in electrolysis of alkaline aqueous solution.

PubMed

Zhu, Mingchao; Zhang, Zhongyi; Zhang, Hu; Zhang, Hui; Zhang, Xiaodong; Zhang, Lixue; Wang, Shicai

2018-01-01

Hydrophilic medium and precursors were used to synthesize a hydrophilic electro-catalyst for overall water splitting. The cobalt sulfide (Co 3 S 4 ) catalyst exhibits a layered nanosheet structure with a hydrophilic surface, which can facilitate the diffusion of aqueous substrates into the electrode pores and towards the active sites. The Co 3 S 4 catalyst shows excellent bifunctional catalytic activity for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline solution. The assembled water electrolyzer based on Co 3 S 4 exhibits better performance and stability than that of Pt/C-RuO 2 catalyst. Thereforce the hydrophilic Co 3 S 4 is a highly promising bifunctional catalyst for the overall water splitting reaction. Copyright © 2017 Elsevier Inc. All rights reserved.

Effect of microstructure on the thermoelectric performance of La{sub 1−x}Sr{sub x}CoO{sub 3}

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

Viskadourakis, Z.; Department of Mechanical and Manufacturing Engineering, University of Cypruss, 75 Kallipoleos Avenue, P.O. Box 20537, 1678 Nicosia; Athanasopoulos, G.I.

We present a case where the microstructure has a profound effect on the thermoelectric properties of oxide compounds. Specifically, we have investigated the effect of different sintering treatments on La{sub 1−x}Sr{sub x}CoO{sub 3} samples synthesized using the Pechini method. We found that the samples, which are dense and consist of inhomogeneously-mixed grains of different size, exhibit both higher Seebeck coefficient and thermoelectric figure of merit than the samples, which are porous and consist of grains with almost identical size. The enhancement of Seebeck coefficient in the dense samples is attributed to the so-called “energy-filtering” mechanism that is related to themore » energy barrier of the grain boundary. On the other hand, the thermal conductivity for the porous compounds is significantly reduced in comparison to the dense compounds. It is suggested that a fine-manipulation of grain size ratio combined with a fine-tuning of porosity could considerably enhance the thermoelectric performance of oxides. - Graphical abstract: The enhancement of the dimensionless thermoelectric figure ZT of merit is presented for two equally Sr-doped LaCoO3 compounds, possessing different microstructure, indicating the effect of the latter to the thermoelectric performance of the La{sub 1−x}Sr{sub x}CoO{sub 3} solid solution. - Highlights: • Electrical and thermal transport properties are affected by the microstructure in La{sub 1−x}Sr{sub x}CoO{sub 3} polycrystalline materials. • Coarse/fine grain size distribution enhances the Seebeck coefficient. • Porosity reduces the thermal conductivity in La{sub 1−x}Sr{sub x}CoO{sub 3} polycrystalline samples. • The combination of large/small grain ratio distribution with the high porosity may result to the enhancement of the thermoelectric performance of the material.« less

Investigation of microstructure, micro-mechanical and optical properties of HfTiO{sub 4} thin films prepared by magnetron co-sputtering

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

Mazur, Michal, E-mail: michal.mazur@pwr.edu.pl; Wojcieszak, Damian; Domaradzki, Jaroslaw

2015-12-15

Highlights: • HfTiO{sub 4} thin films were deposited by magnetron co-sputtering. • As-prepared and annealed at 800 °C thin films were nanocrystalline. • Optical properties and hardness were investigated in relation to thin films structure. • Hardness was 3-times higher in the case of as-deposited thin films. • HfTiO{sub 4} thin films are suitable for use as optical coatings with protective properties. - Abstract: Titania (TiO{sub 2}) and hafnium oxide (HfO{sub 2}) thin films are in the focus of interest to the microelectronics community from a dozen years. Because of their outstanding properties like, among the others, high stability, highmore » refractive index, high electric permittivity, they found applications in many optical and electronics domains. In this work discussion on the hardness, microstructure and optical properties of as-deposited and annealed HfTiO{sub 4} thin films has been presented. Deposited films were prepared using magnetron co-sputtering method. Performed investigations revealed that as-deposited coatings were nanocrystalline with HfTiO{sub 4} structure. Deposited films were built from crystallites of ca. 4–12 nm in size and after additional annealing an increase in crystallites size up to 16 nm was observed. Micro-mechanical properties, i.e., hardness and elastic modulus were determined using conventional load-controlled nanoindentation testing. the annealed films had 3-times lower hardness as-compared to as-deposited ones (∼9 GPa). Based on optical investigations real and imaginary components of refractive index were calculated, both for as-deposited and annealed thin films. The real refractive index component increased after annealing from 2.03 to 2.16, while extinction coefficient increased by an order from 10{sup −4} to 10{sup −3}. Structure modification was analyzed together with optical energy band-gap, Urbach energy and using Wemple–DiDomenico model.« less

Oxygen Vacancy Engineering of Co3 O4 Nanocrystals through Coupling with Metal Support for Water Oxidation.

PubMed

Zhang, Jun-Jun; Wang, Hong-Hui; Zhao, Tian-Jian; Zhang, Ke-Xin; Wei, Xiao; Jiang, Zhi-Dong; Hirano, Shin-Ichi; Li, Xin-Hao; Chen, Jie-Sheng

2017-07-21

Oxygen vacancies can help to capture oxygen-containing species and act as active centers for oxygen evolution reaction (OER). Unfortunately, effective methods for generating a high amount of oxygen vacancies on the surface of various nanocatalysts are rather limited. Here, we described an effective way to generate oxygen-vacancy-rich surface of transition metal oxides, exemplified with Co 3 O 4 , simply by constructing highly coupled interface of ultrafine Co 3 O 4 nanocrystals and metallic Ti. Impressively, the amounts of oxygen vacancy on the surface of Co 3 O 4 /Ti surpassed the reported values of the Co 3 O 4 modified even under highly critical conditions. The Co 3 O 4 /Ti electrode could provide a current density of 23 mA cm -2 at an OER overpotential of 570 mV, low Tafel slope, and excellent durability in neutral medium. Because of the formation of a large amount of oxygen vacancies as the active centers for OER on the surface, the TOF value of the Co 3 O 4 @Ti electrode was optimized to be 3238 h -1 at an OER overpotential of 570 mV, which is 380 times that of the state-of-the-art non-noble nanocatalysts in the literature. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bias polarization study of steam electrolysis by composite oxygen electrode Ba0.5Sr0.5Co0.8Fe0.2O3-δ/BaCe0.4Zr0.4Y0.2O3-δ

NASA Astrophysics Data System (ADS)

Yang, Tao; Shaula, Aliaksandr; Pukazhselvan, D.; Ramasamy, Devaraj; Deng, Jiguang; da Silva, E. L.; Duarte, Ricardo; Saraiva, Jorge A.

2017-12-01

The polarization behavior of Ba0.5Sr0.5Co0.8Fe0.2O3-δ-BaCe0.4Zr0.4Y0.2O3-δ (BSCF-BCZY) electrode under steam electrolysis conditions was studied in detail. The composite oxygen electrode supported by BCZY electrolyzer has been assessed as a function of temperature (T), water vapor partial pressures (pH2O), and bias polarization voltage for electrodes of comparable microstructure. The Electrochemical impedance spectra show two depressed arcs in general without bias polarization. And the electrode resistance became smaller with the increase of the bias polarization under the same water vapor partial pressures. The total resistance of the electrode was shown to be significantly affected by temperature, with the same level of pH2O and bias polarization voltage. This result highlights BSCF-BCZY as an effective oxygen electrode under moderate polarization and pH2O conditions.

Low-loss Z-type barium hexaferrite composites from nanoscale ZnAl2O4 addition for high-frequency applications

NASA Astrophysics Data System (ADS)

Zheng, Zongliang; Feng, Quanyuan; Harris, Vincent G.

2018-05-01

In this study, nanocrystalline ZnAl2O4 (ZA) were introduced to Z-type barium hexaferrite (Co2Z) and the effects of ZA addition upon the crystal-phase composition, microstructure, permeability and permittivity as well as losses characteristics over a wide frequency range of 10 MHz-1 GHz have been systematically investigated. With increasing ZA content (x) from 0 to 15 wt%, the permeability μ' at low frequencies decreased from 12.0 to 4.3, while the permittivity ɛ' was decreased from 27.4 to 10.7. Correspondingly, the frequency stability of permeability and permittivity were improved and the losses were effectively reduced. When x is in the range of 5-10 wt%, the magnetic loss tan δμ is in the order of 10-2 and the dielectric loss tan δɛ is in the order of 10-3 at 300 MHz, which is lower by one order of magnitude compared with that of undoped Co2Z. The modified magnetic and dielectric properties are closely related to the changing phase composition and microstructure.

Evolution of magnetic properties and microstructure of Hf2Co11B alloys

DOE PAGES

McGuire, Michael A.; Rios, Orlando

2015-02-05

Amorphous Hf 2Co 11B alloys produced by melt-spinning have been crystallized by annealing at 500-800 °C, and the products have been investigated using magnetization measurements, x-ray diffraction, and scanning electron microscopy. The results reveal the evolution of the phase fractions, microstructure, and magnetic properties with both annealing temperature and time. Crystallization of the phase denoted HfCo 7, which is associated with the development of coercivity, occurs slowly at 500 °C. Annealing at intermediate temperatures produces mixed phase samples containing some of the HfCo 7 phase with the highest values of remanent magnetization and coercivity. The equilibrium structure at 800 °Cmore » contains HfCo3B 2, Hf 6Co 23 and Co, and displays soft ferromagnetism. Maximum values for the remanent magnetization, intrinsic coercivity, and magnetic energy product among the samples are approximately 5.2 kG, 2.0 kOe, and 3.1 MGOe, respectively, which indicates that the significantly higher values observed in crystalline, melt-spun Hf 2Co 11B ribbons are a consequence of the non-equilibrium solidification during the melt-spinning process. Application of high magnetic fields during annealing is observed to strongly affect the microstructural evolution, which may provide access to higher performance materials in Zr/Hf-Co hard ferromagnets. The crystal structure of HfCo 7 and the related Zr analogues is unknown, and without knowledge of atomic positions powder diffraction cannot distinguish among proposed unit cells and symmetries found in the literature.« less

Oxidation study of coated Crofer 22 APU steel in dry oxygen

NASA Astrophysics Data System (ADS)

Molin, Sebastian; Chen, Ming; Hendriksen, Peter Vang

2014-04-01

The effect of a dual layer coating composed of a layer of a Co3O4 and a layer of a La0.85Sr0.15MnO3/Co3O4 mixture on the high temperature corrosion of the Crofer 22 APU alloy is reported. Oxidation experiments were performed in dry oxygen at three temperatures: 800 °C, 850 °C and 900 °C for periods up to 1000 h. Additionally at 850 °C a 5000 h long oxidation test was performed to evaluate longer term suitability of the proposed coating. Corrosion kinetics were evaluated by measuring mass gain during oxidation. The corrosion kinetics for the coated samples are analyzed in terms of a parabolic rate law. Microstructural features were investigated by scanning electron microscopy, energy dispersive X-ray analysis and X-ray diffractometry. The coating is effective in reducing the corrosion rate and in ensuring long lifetime of coated alloys. The calculated activation energy for the corrosion process is around 1.8 eV. A complex Co-Mn-Cr spinel is formed caused by diffusion of Cr and Mn from the alloy into the Co3O4 coating and by additional diffusion of Mn from the LSM layer. Adding a layer of LSM/Co3O4, acting as an additional Mn source, on top of the cobalt spinel is beneficial for the improved corrosion resistance.

Effects of Laser Power Level on Microstructural Properties and Phase Composition of Laser-Clad Fluorapatite/Zirconia Composite Coatings on Ti6Al4V Substrates

PubMed Central

Chien, Chi-Sheng; Liu, Cheng-Wei; Kuo, Tsung-Yuan

2016-01-01

Hydroxyapatite (HA) is one of the most commonly used materials for the coating of bioceramic titanium (Ti) alloys. However, HA has poor mechanical properties and a low bonding strength. Accordingly, the present study replaces HA with a composite coating material consisting of fluorapatite (FA) and 20 wt % yttria (3 mol %) stabilized zirconia (ZrO2, 3Y-TZP). The FA/ZrO2 coatings are deposited on Ti6Al4V substrates using a Nd:YAG laser cladding system with laser powers and travel speeds of 400 W/200 mm/min, 800 W/400 mm/min, and 1200 W/600 mm/min, respectively. The experimental results show that a significant inter-diffusion of the alloying elements occurs between the coating layer (CL) and the transition layer (TL). Consequently, a strong metallurgical bond is formed between them. During the cladding process, the ZrO2 is completely decomposed, while the FA is partially decomposed. As a result, the CLs of all the specimens consist mainly of FA, Ca4(PO4)2O (TTCP), CaF2, CaZrO3, CaTiO3 and monoclinic phase ZrO2 (m-ZrO2), together with a small amount of θ-Al2O3. As the laser power is increased, CaO, CaCO3 and trace amounts of tetragonal phase ZrO2 (t-ZrO2) also appear. As the laser power increases from 400 to 800 W, the CL hardness also increases as a result of microstructural refinement and densification. However, at the highest laser power of 1200 W, the CL hardness reduces significantly due to the formation of large amounts of relatively soft CaO and CaCO3 phase. PMID:28773503

Engineering High-Energy Interfacial Structures for High-Performance Oxygen-Involving Electrocatalysis.

PubMed

Guo, Chunxian; Zheng, Yao; Ran, Jingrun; Xie, Fangxi; Jaroniec, Mietek; Qiao, Shi-Zhang

2017-07-10

Engineering high-energy interfacial structures for high-performance electrocatalysis is achieved by chemical coupling of active CoO nanoclusters and high-index facet Mn 3 O 4 nano-octahedrons (hi-Mn 3 O 4 ). A thorough characterization, including synchrotron-based near edge X-ray absorption fine structure, reveals that strong interactions between both components promote the formation of high-energy interfacial Mn-O-Co species and high oxidation state CoO, from which electrons are drawn by Mn III -O present in hi-Mn 3 O 4 . The CoO/hi-Mn 3 O 4 demonstrates an excellent catalytic performance over the conventional metal oxide-based electrocatalysts, which is reflected by 1.2 times higher oxygen evolution reaction (OER) activity than that of Ru/C and a comparable oxygen reduction reaction (ORR) activity to that of Pt/C as well as a better stability than that of Ru/C (95 % vs. 81 % retained OER activity) and Pt/C (92 % vs. 78 % retained ORR activity after 10 h running) in alkaline electrolyte. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthetic control and empirical prediction of redox potentials for Co 4O 4 cubanes over a 1.4 V range: implications for catalyst design and evaluation of high-valent intermediates in water oxidation

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

Nguyen, Andy I.; Wang, Jianing; Levine, Daniel S.

The oxo-cobalt cubane unit [Co 4O 4] is of interest as a homogeneous oxygen-evolution reaction (OER) catalyst, and as a functional mimic of heterogeneous cobalt oxide OER catalysts. The synthesis of several new cubanes allows evaluation of redox potentials for the [Co 4O 4] cluster, which are highly sensitive to the ligand environment and span a remarkable range of 1.42 V. The [Co III 4O 4] 4+/[Co III 3Co IVO 4 ]5+ and [Co III 3Co IVO 4] 5+/[Co III 2Co IV 2O 4] 6+ redox potentials are reliably predicted by the pKas of the ligands. Hydrogen bonding is alsomore » shown to significantly raise the redox potentials, by ~500 mV. The potential-p K a correlation is used to evaluate the feasibility of various proposed OER catalytic intermediates, including high-valent Co-oxo species. The synthetic methods and structure–reactivity relationships developed by these studies should better guide the design of new cubane-based OER catalysts.« less

Synthetic control and empirical prediction of redox potentials for Co 4O 4 cubanes over a 1.4 V range: implications for catalyst design and evaluation of high-valent intermediates in water oxidation

DOE PAGES

Nguyen, Andy I.; Wang, Jianing; Levine, Daniel S.; ...

2017-04-07

The oxo-cobalt cubane unit [Co 4O 4] is of interest as a homogeneous oxygen-evolution reaction (OER) catalyst, and as a functional mimic of heterogeneous cobalt oxide OER catalysts. The synthesis of several new cubanes allows evaluation of redox potentials for the [Co 4O 4] cluster, which are highly sensitive to the ligand environment and span a remarkable range of 1.42 V. The [Co III 4O 4] 4+/[Co III 3Co IVO 4 ]5+ and [Co III 3Co IVO 4] 5+/[Co III 2Co IV 2O 4] 6+ redox potentials are reliably predicted by the pKas of the ligands. Hydrogen bonding is alsomore » shown to significantly raise the redox potentials, by ~500 mV. The potential-p K a correlation is used to evaluate the feasibility of various proposed OER catalytic intermediates, including high-valent Co-oxo species. The synthetic methods and structure–reactivity relationships developed by these studies should better guide the design of new cubane-based OER catalysts.« less

Co-Precipitation Synthesis of Gadolinium Aluminum Gallium Oxide (GAGG) via Different Precipitants

NASA Astrophysics Data System (ADS)

Sun, Yan; Yang, Shenghui; Zhang, Ye; Jiang, Jun; Jiang, Haochuan

2014-02-01

In order to obtain a uniform transparent ceramic scintillator, well-dispersed fine starting powders with high-purity, small grain size, spherical morphology and high sinter-ability are necessary. In this study, Ce3+ doped gadolinium aluminum gallium garnet Gd3Al3Ga2O12 (GAGG) powders were synthesized by the co-precipitation method. NH4OH, NH4HCO3 and the mixed solution of NH4OH and NH4HCO3 were used as precipitants, respectively. The precursor composition, phase formation process, microstructure, morphology, particle size distribution and luminescent properties of obtained GAGG powders were measured. The results show that powders prepared using the mixed precipitant exhibit the best microstructural morphology, good sinter-ability and highest luminescent intensity. Pure GAGG polycrystalline powders could be obtained at about 950°C for 1.5 h and the average size of the particles is about 50 nm. The photoluminescence spectrum shows a strong green-yellow emission near 540 nm.

Microstructure, Mechanical and Tribological Properties of Oxide Dispersion Strengthened High-Entropy Alloys

PubMed Central

Liu, Xinyu; Yin, Hangboce; Xu, Yi

2017-01-01

A novel metal matrix composite CrMnFeCoNi with Y2O3 as reinforcement phase was designed and manufactured by mechanical alloying and spark plasma sintering. After sintering at 900 °C for 5 min, the microstructure consisted of a FCC matrix and Y2O3 nanoparticles. The addition of 0.25 wt % Y2O3 increased the room temperature tensile strength of the CrMnFeCoNi base from 868 MPa to 1001 MPa, while the mechanical properties of the addition of 0.5 wt % Y2O3 composite decreased. In the meantime, the addition of Y2O3 had no significant influence on the coefficient of friction, while the addition of 0.25 wt % Y2O3 composite shows excellent wear-resistance. PMID:29140296

Influence of Lu2O3 on electrical and microstructural properties of CaCu3Ti4O12 ceramics

NASA Astrophysics Data System (ADS)

Xu, Dong; Wang, Biao; Lin, Yuanhua; Jiao, Lei; Yuan, Hongming; Zhao, Guoping; Cheng, Xiaonong

2012-07-01

In this work, the influence of Lu2O3 doped on the dielectric and electrical properties of CaCu3Ti4O12 was reported. Lu2O3-doped CCTO was prepared by a conventional solid state technique using CuO, TiO2, and CaCO3 as starting materials. The samples were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM); dielectric measurements were measured in the 102 Hz-107 Hz frequency range at room temperature; and the nonlinear behavior of all samples was measured. The doping of Lu2O3 resulted in an increase in the dielectric constant of CCTO, but decreased the stability of the frequency dependence. Increasing concentrations of Lu2O3 resulted in decreasing nonlinear coefficients.

Does the conductivity of interconnect coatings matter for solid oxide fuel cell applications?

NASA Astrophysics Data System (ADS)

Goebel, Claudia; Fefekos, Alexander G.; Svensson, Jan-Erik; Froitzheim, Jan

2018-04-01

The present work aims to quantify the influence of typical interconnect coatings used for solid oxide fuel cells (SOFC) on area specific resistance (ASR). To quantify the effect of the coating, the dependency of coating thickness on the ASR is examined on Crofer 22 APU at 600 °C. Three different Co coating thicknesses are investigated, 600 nm, 1500 nm, and 3000 nm. Except for the reference samples, the material is pre-oxidized prior to coating to mitigate the outward diffusion of iron and consequent formation of poorly conducting (Co,Fe)3O4 spinel. Exposures are carried out at 600 °C in stagnant laboratory air for 500 h and subsequent ASR measurements are performed. Additionally the microstructure is investigated with scanning electron microscopy (SEM). On all pre-oxidized samples, a homogenous dense Co3O4 top layer is observed beneath which a thin layer of Cr2O3 is present. As the ASR values range between 7 and 12 mΩcm2 for all pre-oxidized samples, even though different Co3O4 thicknesses are observed, the results strongly suggest that for most applicable cases the impact of the coating on ASR is negligible and the main contributor is Cr2O3.

Structural evolution of the [(CO2)n(H2O)]- cluster anions: quantifying the effect of hydration on the excess charge accommodation motif.

PubMed

Muraoka, Azusa; Inokuchi, Yoshiya; Hammer, Nathan I; Shin, Joong-Won; Johnson, Mark A; Nagata, Takashi

2009-08-06

The [(CO2)n(H2O)]- cluster anions are studied using infrared photodissociation (IPD) spectroscopy in the 2800-3800 cm(-1) range. The observed IPD spectra display a drastic change in the vibrational band features at n = 4, indicating a sharp discontinuity in the structural evolution of the monohydrated cluster anions. The n = 2 and 3 spectra are composed of a series of sharp bands around 3600 cm(-1), which are assignable to the stretching vibrations of H2O bound to C2O4- in a double ionic hydrogen-bonding (DIHB) configuration, as was previously discussed (J. Chem. Phys. 2005, 122, 094303). In the n > or = 4 spectrum, a pair of intense bands additionally appears at approximately 3300 cm(-1). With the aid of ab initio calculations at the MP2/6-31+G* level, the 3300 cm(-1) bands are assigned to the bending overtone and the hydrogen-bonded OH vibration of H2O bound to CO2- via a single O-H...O linkage. Thus, the structures of [(CO2)n(H2O)]- evolve with cluster size such that DIHB to C2O4- is favored in the smaller clusters with n = 2 and 3 whereas CO2- is preferentially stabilized via the formation of a single ionic hydrogen-bonding (SIHB) configuration in the larger clusters with n > or = 4.

Controlled fabrication of photoactive copper oxide-cobalt oxide nanowire heterostructures for efficient phenol photodegradation.

PubMed

Shi, Wenwu; Chopra, Nitin

2012-10-24

Fabrication of oxide nanowire heterostructures with controlled morphology, interface, and phase purity is critical for high-efficiency and low-cost photocatalysis. Here, we have studied the formation of copper oxide-cobalt nanowire heterostructures by sputtering and subsequent air annealing to result in cobalt oxide (Co(3)O(4))-coated CuO nanowires. This approach allowed fabrication of standing nanowire heterostructures with tunable compositions and morphologies. The vertically standing CuO nanowires were synthesized in a thermal growth method. The shell growth kinetics of Co and Co(3)O(4) on CuO nanowires, morphological evolution of the shell, and nanowire self-shadowing effects were found to be strongly dependent on sputtering duration, air-annealing conditions, and alignment of CuO nanowires. Finite element method (FEM) analysis indicated that alignment and stiffness of CuO-Co nanowire heterostructures greatly influenced the nanomechanical aspects such as von Mises equivalent stress distribution and bending of nanowire heterostructures during the Co deposition process. This fundamental knowledge was critical for the morphological control of Co and Co(3)O(4) on CuO nanowires with desired interfaces and a uniform coating. Band gap energies and phenol photodegradation capability of CuO-Co(3)O(4) nanowire heterostructures were studied as a function of Co(3)O(4) morphology. Multiple absorption edges and band gap tailings were observed for these heterostructures, indicating photoactivity from visible to UV range. A polycrystalline Co(3)O(4) shell on CuO nanowires showed the best photodegradation performance (efficiency ~50-90%) in a low-powered UV or visible light illumination with a sacrificial agent (H(2)O(2)). An anomalously high efficiency (~67.5%) observed under visible light without sacrificial agent for CuO nanowires coated with thin (∼5.6 nm) Co(3)O(4) shell and nanoparticles was especially interesting. Such photoactive heterostructures demonstrate unique sacrificial agent-free, robust, and efficient photocatalysts promising for organic decontamination and environmental remediation.

Investigation of Synthesis and Magnetic Properties of Rod-Shaped CoFe2O4 via Precipitation-Topotactic Reaction Employing α-FeOOH and γ-FeOOH As Templates

NASA Astrophysics Data System (ADS)

Cao, Xiaohui; Dong, Hongfei; Tan, Yuzhuo; Meng, Jinhong

2018-03-01

Rod-shaped CoFe2O4 was prepared by chemical precipitation-topotactic reaction method, and in this preparation needle-like γ-FeOOH and α-FeOOH were synthesized to use as template materials. The evolution of phase and morphology in the process of calcination exhibits that α-FeOOH and γ-FeOOH experienced different routes to form the α-Fe2O3 middle phase with different crystallinity and morphology. The synthesis process of CoFe2O4 revealed that the crystallinity, purity and morphology of CoFe2O4 depend on the α-Fe2O3 middle phase. The magnetic measurement showed that the CoFe2O4 prepared from α-FeOOH has higher saturation magnetization and coercivity, and the crystallinity and morphology may play important roles in achieving a better magnetic performance.

Influence of Microstructure and Surface Activation of Dual-Phase Membrane Ce 0.8 Gd 0.2 O 2-δ -FeCo 2 O 4 on Oxygen Permeation

DOE PAGES

Ramasamy, Madhumidha; Baumann, Stefan; Palisaitis, Justinas; ...

2015-09-24

In dual-phase oxygen transport membranes we noticed that there is fast-growing interest in research for oxyfuel combustion process application. One such potential candidate is CGO-FCO (60wt% Ce 0.8Gd 0.2O 2-δ-40wt% FeCo 2O4) identified to provide good oxygen permeation flux with substantial stability in harsh atmosphere. Dense CGO-FCO membranes of 1mm thickness were fabricated by sintering dry pellets pressed from powders synthesized by one-pot method (modified Pechini process) at 1200 degrees C for 10h. Microstructure analysis indicates presence of a third orthorhombic perovskite phase in the sintered composite. We also identified that the spinel phase tends to form an oxygen deficientmore » phase at the grain boundary of spinel and CGO phases. Surface exchange limitation of the membranes was overcome by La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF) porous layer coating over the composite. Moreover, the oxygen permeation flux of the CGO-FCO screen printed with a porous layer of 10mthick LSCF is 0.11mL/cm 2 per minute at 850 degrees C with argon as sweep and air as feed gas at the rates of 50 and 250mL/min.« less

Dielectric and varistor properties of rare-earth-doped ZnO and CaCu3Ti4O12 composite ceramics

NASA Astrophysics Data System (ADS)

Lu, Huafei; Lin, Yuanhua; Yuan, Jiancong; Nan, Cewen; Chen, Kexin

2013-02-01

To investigate the multi-functional ceramics with both high permittivity and large nonlinear coefficient, we have prepared rare-earth Tb-and-Co doped ZnO and TiO2-rich CaCu3Ti4O12 (TCCTO) powders by chemical co-precipitation and sol-gel methods respectively, and then obtained the TCCTO/ZnO composite ceramics, sintered at 1100°C for 3 h in air. Analyzing the composite ceramics of the microstructure and phase composition indicated that the composite ceramics were composed of the main phases of ZnO and CaCu3Ti4O12 (CCTO). Our results revealed that the TCCTO/ZnO composite ceramics showed both high dielectric and good nonlinear electrical behaviors. The composite ceramic of TCCTO: ZnO = 0.3 exhibited a high dielectric constant of 210(1 kHz) with a nonlinear coefficient of 11. The dielectric behavior of TCCTO/ZnO composite could be explained by the mixture rule. With the high dielectric permittivity and tunable varistor behaviors, the composite ceramics has a potential application for the higher voltage transportation devices.

The Influence of Fe Substitution in Lanthanum Calcium Cobalt Oxide on the Oxygen Evolution Reaction in Alkaline Media

DOE PAGES

Abreu-Sepulveda, Maria A.; Dhital, Chetan; Huq, Ashfia; ...

2016-07-30

The effect due to systematic substitution of cobalt by iron in La 0.6Ca 0.4Co 1-xFe xO 3 towards the oxygen evolution reaction(OER) in alkaline media has been investigated. We synthesized these compounds by a facile glycine-nitrate synthesis and the phase formation was confirmed by X-ray diffraction and Neutron Diffraction elemental analysis. The apparent OER activity was evaluated by quasi steady state current measurements in alkaline media using a traditional three-electrode cell. X-ray photoelectron spectroscopy shows iron substitution causes an increase in the surface concentration of various cobalt oxidation states. Tafel slope in the vicinity of 60 mV/decade and electrochemical reactionmore » order towards OH- near unity were achieved for the unsubstituted La 0.6Ca 0.4CoO 3. Moreover, a decrease in the Tafel slope to 49 mV/decade was observed when iron is substituted in high amounts in the perovskite structure. The area specific current density showed dependence on the Fe fraction, however the relationship of specific current density with Fe fraction is not linear. High Fe substitutions, La 0.6Ca 0.4Co 0.2Fe 0.8O 3 and La 0.6Ca 0.4Co 0.1Fe 0.9O 3 showed higher area specific activity towards OER than La 0.6Ca 0.4CoO 3 or La 0.6Ca 0.4FeO 3. Finally, we believe iron inclusion in the cobalt sites of the perovskite helps decrease the electron transfer barrier and facilitates the formation of cobalt-hydroxide at the surface. Possible OER mechanisms based on the observed kinetic parameters will be discussed.« less

Engineering a nanotubular mesoporous cobalt phosphide electrocatalyst by the Kirkendall effect towards highly efficient hydrogen evolution reactions.

PubMed

Miao, Yue-E; Li, Fei; Zhou, Yu; Lai, Feili; Lu, Hengyi; Liu, Tianxi

2017-11-02

Tailoring the size and controlling the morphology of particular nano-architectures are considered as two promising strategies to improve the catalytic performance of metal nanocrystals towards hydrogen evolution reactions (HERs). Herein, mesoporous cobalt phosphide nanotubes (CoP-NTs) with a three-dimensional network structure have been obtained through a facile and efficient electrospinning technique combined with thermal stabilization and phosphorization treatments. The thermal stabilization process has been demonstrated to play a key role in the morphological tailoring of Co 3 O 4 nanotubes (Co 3 O 4 -NTs). As a result, the CoP-NTs show one-dimensional hollow tubular architecture instead of forming a worm-like tubular CoP structure (W-CoP-NTs) or severely aggregated CoP powder (CoP-NPs) which originate from the Co 3 O 4 nanotubes without thermal stabilization treatment and Co 3 O 4 nanoparticles, respectively. Satisfyingly, under an optimized phosphorization degree, the CoP-NT electrode exhibits a low onset overpotential of 53 mV with a low Tafel slope of 50 mV dec -1 during the HER process. Furthermore, the CoP-NT electrode is capable of driving a large cathodic current density of 10 mA cm -2 at an overpotential of 152 mV, which is much lower than those of its contrast samples, i.e. CoP-NPs (211 mV) and W-CoP-NTs (230 mV). Therefore, this work provides a feasible and general strategy for constructing three-dimensionally organized mesoporous non-noble metal phosphide nanotubes as promising alternative high-performance electrocatalysts for the commercial platinum ones.

Polyaniline/Fe3O4-RGO Nanocomposites for Microwave Absorption

NASA Astrophysics Data System (ADS)

Mathew, Jithin; Sathishkumar, M.; Kothurkar, Nikhil K.; Senthilkumar, R.; Sabarish Narayanan, B.

2018-02-01

Fe3O4 nanoparticles were synthesized by co-precipitation of ferric chloride (FeCl3) and ferrous chloride (FeCl2). Reduced graphene oxide (RGO) was prepared by reducing the graphene oxide, which was synthesized by Hummer’s method, using hydrazine hydrate. Three nanocomposites based on sodium dodecyl benzene sulphonate (SDBS)-doped polyaniline were synthesized through in situ polymerization in the presence of the fillers (i) Fe3O4, (ii) reduced graphene oxide (RGO) and (iii) Fe3O4-decorated RGO respectively. The synthesized PANI and the composites were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and transmission electron microscopy. Their microstructures, electrical conductivities, and EMI shielding effectiveness were studied. The nanocomposite containing 10 % RGO showed the maximum electrical conductivity and the one with 10 % RGO and 10 % Fe3O4 showed the maximum EMI shielding effectiveness of 7.5 dB for a 1 mm thick sample.

Facile synthesis and magnetorheological properties of superparamagnetic CoFe2O4/GO nanocomposites

NASA Astrophysics Data System (ADS)

Wang, Guangshuo; Ma, Yingying; Dong, Xufeng; Tong, Yu; Zhang, Lina; Mu, Jingbo; Bai, Yongmei; Hou, Junxian; Che, Hongwei; Zhang, Xiaoliang

2015-12-01

In this study, cobalt ferrite/graphene oxide (CoFe2O4/GO) nanocomposites were synthesized successfully by a facile sonochemical method. The microstructure and physical properties of CoFe2O4/GO nanocomposites were investigated in detail by TEM, XRD and SQUID. It was found that GO nanosheets were fully exfoliated and decorated homogeneously with CoFe2O4 nanoparticles having diameters of 8∼15 nm. The field-dependent magnetization curve indicated superparamagnetic behavior of as-prepared CoFe2O4/GO with saturation magnetization (Ms) of 34.9 emu/g at room temperature. The ferrofluid was prepared by the obtained CoFe2O4/GO with 25 wt% particles and its magnetorheological (MR) properties were tested using a Physica MCR301 rheometer fitted with a magneto-rheological module. The CoFe2O4/GO-based ferrofluid exhibited typical MR effect with increasing viscosity, shear stress and yield stress depending on the applied magnetic field strength.

Could microwave induced catalytic oxidation (MICO) process over CoFe2O4 effectively eliminate brilliant green in aqueous solution?

PubMed

Ju, Yongming; Wang, Xiaoyan; Qiao, Junqin; Li, Guohua; Wu, You; Li, Yuan; Zhang, Xiuyu; Xu, Zhencheng; Qi, Jianying; Fang, Jiande; Dionysiou, Dionysios D

2013-12-15

In this study, we adopted the chemical co-precipitation (CP) method and sol-gel method followed by calcination at temperatures of 100-900°C for 12h to synthesize CoFe2O4 materials, which were further characterized by TEM, XRD and XPS techniques. The properties of CoFe2O4 materials were evaluated in a microwave (MW) induced catalytic oxidation (MICO) process for the elimination of brilliant green (BG). The results showed that: (1) the removal rates of BG gradually decreased over a series of CoFe2O4 materials prepared by CP method and calcinated with 100-700°C (except 900°C) for 12h within three reuse cycles; for comparison, no removal of BG was obtained over CoFe2O4 synthesized by sol-gel method and CoFe2O4-900 (CP); (2) no hydroxyl radicals were captured with salicylic acid used as molecular probe in the MICO process; (3) MW irradiation enhanced the release of residual NaOH within the microstructure of CoFe2O4 and further discolored BG, because BG is sensitive to pH; (4) granular activated carbon (GAC), an excellent MW-absorbing material possessing higher dielectric loss tangent compared to that of a series of CoFe2O4 materials, could not remove BG in suspensions at a higher efficiency, even if the loading amount was 20 g L(-1). Accordingly, MICO process over CoFe2O4 materials and GAC could not effectively eliminate BG in suspensions. Copyright © 2013 Elsevier B.V. All rights reserved.

Facile synthesis of electrospun MFe2O4 (M = Co, Ni, Cu, Mn) spinel nanofibers with excellent electrocatalytic properties for oxygen evolution and hydrogen peroxide reduction.

PubMed

Li, Mian; Xiong, Yueping; Liu, Xiaotian; Bo, Xiangjie; Zhang, Yufan; Han, Ce; Guo, Liping

2015-05-21

Designing and preparing porous transition metal ferrites without using any template, shape-directing agent, and surfactant is a challenge. Herein, heterojunction MFe2O4 (M = Co, Ni, Cu, Mn) nanofiber (NF) based films with three-dimensional configurations were synthesized by electrospinning and the subsequent thermal treatment processes. Characterization results indeed show the 3D net-like textural structures of the electrospun spinel-type MFe2O4 NFs. In particular, the resulting MFe2O4 NFs have lengths up to several dozens of micrometers with an average diameter size of about 150 nm and possess abundant micro/meso/macropores on both the surface and within the films. The hierarchically porous structures and high surface areas of these MFe2O4 NFs (for example, the CoFe2O4 NFs possess a larger BET specific surface area (61.48 m(2) g(-1)) than those of the CoFe2O4 NPs (5.93 m(2) g(-1))) can afford accessible transport channels for effectively decreasing the mass transport resistances, enhancing the electrical conductivity, and increasing the density and reactivity of the exposed catalytic active sites. All these advantages will be responsible for the better electrocatalytic performances of these MFe2O4 NFs compared with their structural isomers (i.e. the MFe2O4 NPs) for the oxygen evolution reaction (OER) and H2O2 reduction in alkaline solution. Meanwhile, both the OER and H2O2 reduction catalytic activities for these MFe2O4 NFs obey the order of CoFe2O4 NFs > CuFe2O4 NFs > NiFe2O4 NFs > MnFe2O4 NFs > Fe2O3 NFs. The CoFe2O4 NFs represent a new class of highly efficient non-noble-metal catalysts for both OER and H2O2 reduction/detection in alkaline media.

Morphology and phase evolution in microwave synthesized Al/FeO4 system.

PubMed

Chuan, Lee Chang; Yoshikawaa, Noboru; Taniguchia, Shoji

2011-01-01

Thermite reaction between Al/Fe3O4 raised by microwave (MW) heating under N2 atmosphere has been investigated, and compared with that by the electric furnace. In addition to the stoichiometric ratio for the production of metallic iron and alumina, mixture with slightly Lower in Al content is also studied. As thermite reaction is highly exothermic, melting of reaction product and destruction of microstructure may occur, which corresponds to the enthalpy and adiabatic temperature of the reaction. Hence, to avoid this problem, reaction coupled with a smaller driving force by controlling the MW ignition condition at low temperature exotherm has been investigated. The phase and microstructure evolution during the reaction were analyzed by differential thermal analysis (DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Thermogram of the DTA analysis, irrespective of their mole ratio, recorded two exothermic peaks, one at - 1310 degrees C and another one at - 1370 degrees C. When heated by microwave at 955 degrees C, the main products were identified as Al, FeO and Fe, minor amount of Fe3O4 and some Fe and alumina were detected. When heating to 1155 degrees C, Al and Fe3O4 peaks disappeared, formation of Fe-Al alloy was observed. For sample heated at 1265 degrees C, a porous body was obtained. Micron sized metal particles with complex morphology, irregular in size and shapes were formed, uniformly distributed within the spinel hercynite and/or alumina matrix. In contrast, conventional heating produced no porous products. Formation of alumina is also observed around the metal particles. Controlling of the reaction progress was possible while heating the sample by MW around the low temperature exotherm region, whereas the combustion wave could not be self-propagated.

Insight into the structure and functional application of the Sr0.95Ce0.05CoO3-δ cathode for solid oxide fuel cells.

PubMed

Yang, Wei; Zhang, Huairuo; Sun, Chunwen; Liu, Lilu; Alonso, J A; Fernández-Díaz, M T; Chen, Liquan

2015-04-06

A new perovskite cathode, Sr0.95Ce0.05CoO3-δ, performs well for oxygen-reduction reactions in solid oxide fuel cells (SOFCs). We gain insight into the crystal structure of Sr1-xCexCoO3-δ (x = 0.05, 0.1) and temperature-dependent structural evolution of Sr0.95Ce0.05CoO3-δ by X-ray diffraction, neutron powder diffraction, and scanning transmission electron microscopy experiments. Sr0.9Ce0.1CoO3-δ shows a perfectly cubic structure (a = a0), with a large oxygen deficiency in a single oxygen site; however, Sr0.95Ce0.05CoO3-δ exhibits a tetragonal perovskite superstructure with a double c axis, defined in the P4/mmm space group, that contains two crystallographically different cobalt positions, with distinct oxygen environments. The structural evolution of Sr0.95Ce0.05CoO3-δ at high temperatures was further studied by in situ temperature-dependent NPD experiments. At 1100 K, the oxygen atoms in Sr0.95Ce0.05CoO3-δ show large and highly anisotropic displacement factors, suggesting a significant ionic mobility. The test cell with a La0.8Sr0.2Ga0.83Mg0.17O3-δ-electrolyte-supported (∼300 μm thickness) configuration yields peak power densities of 0.25 and 0.48 W cm(-2) at temperatures of 1023 and 1073 K, respectively, with pure H2 as the fuel and ambient air as the oxidant. The electrochemical impedance spectra evolution with time of the symmetric cathode fuel cell measured at 1073 K shows that the Sr0.95Ce0.05CoO3-δ cathode possesses superior ORR catalytic activity and long-term stability. Mixed ionic-electronic conduction properties of Sr0.95Ce0.05CoO3-δ account for its good performance as an oxygen-reduction catalyst.

Role of initial heat treatment of the ferrite component on magnetic properties in the composite of ferrimagnetic Co1.75Fe1.25O4 ferrite and non-magnetic BaTiO3 oxide

NASA Astrophysics Data System (ADS)

Bhowmik, R. N.; Kazhugasalamoorthy, S.; Sinha, A. K.

2017-12-01

We have prepared a composite of ferrimagnetic ferrite Co1.75Fe1.25O4 and non-magnetic oxide BaTiO3. The ferrite composition Co1.75Fe1.25O4 has been prepared by chemical co-precipitation and subsequently heated at different temperatures. The heat treated ferrite powder has been mixed with BaTiO3 powder with mass ratio 1:1 and the mixed powder has been finally heated at 1000 °C to form composite material. Structural phase of the composite material has been confirmed by high quality Synchrotron X-ray diffraction pattern and Micro-Raman spectra. The grain surface morphology and elemental composition have been studied by Scanning electron microscope and Energy dispersive X-ray analysis. The distribution of magnetic exchange interactions and blocking behavior of the ferrimagnetic grains in composite samples has been understood by analyzing the temperature and magnetic field dependence of dc magnetization. Finally, information on modified micro-structure and ferrimagnetic parameters in composite samples has been obtained as the variation of annealing temperature of the ferrite component before making composite.

Enhancement of CO Evolution by Modification of Ga2O3 with Rare-Earth Elements for the Photocatalytic Conversion of CO2 by H2O.

PubMed

Tatsumi, Hiroyuki; Teramura, Kentaro; Huang, Zeai; Wang, Zheng; Asakura, Hiroyuki; Hosokawa, Saburo; Tanaka, Tsunehiro

2017-12-12

Modification of the surface of Ga 2 O 3 with rare-earth elements enhanced the evolution of CO as a reduction product in the photocatalytic conversion of CO 2 using H 2 O as an electron donor under UV irradiation in aqueous NaHCO 3 as a pH buffer, with the rare-earth species functioning as a CO 2 capture and storage material. Isotope experiments using 13 CO 2 as a substrate clearly revealed that CO was generated from the introduced gaseous CO 2 . In the presence of the NaHCO 3 additive, the rare-earth (RE) species on the Ga 2 O 3 surface are transformed into carbonate hydrates (RE 2 (CO 3 ) 3 ·nH 2 O) and/or hydroxycarbonates (RE 2 (OH) 2(3-x) (CO 3 ) x ) which are decomposed upon photoirradiation. Consequently, Ag-loaded Yb-modified Ga 2 O 3 exhibits much higher activity (209 μmol h -1 of CO) than the pristine Ag-loaded Ga 2 O 3 . The further modification of the surface of the Yb-modified Ga 2 O 3 with Zn afforded a selectivity toward CO evolution of 80%. Thus, we successfully achieved an efficient Ag-loaded Yb- and Zn-modified Ga 2 O 3 photocatalyst with high activity and controllable selectivity, suitable for use in artificial photosynthesis.

Perovskite solar cells based on nanocolumnar plasma-deposited ZnO thin films.

PubMed

Ramos, F Javier; López-Santos, Maria C; Guillén, Elena; Nazeeruddin, Mohammad Khaja; Grätzel, Michael; Gonzalez-Elipe, Agustin R; Ahmad, Shahzada

2014-04-14

ZnO thin films having a nanocolumnar microstructure are grown by plasma-enhanced chemical vapor deposition at 423 K on pre-treated fluorine-doped tin oxide (FTO) substrates. The films consist of c-axis-oriented wurtzite ZnO nanocolumns with well-defined microstructure and crystallinity. By sensitizing CH3NH3PbI3 on these photoanodes a power conversion of 4.8% is obtained for solid-state solar cells. Poly(triarylamine) is found to be less effective when used as the hole-transport material, compared to 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD), while the higher annealing temperature of the perovskite leads to a better infiltration in the nanocolumnar structure and an enhancement of the cell efficiency. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microstructure of calcite deformed by high-pressure torsion: An X-ray line profile study

NASA Astrophysics Data System (ADS)

Schuster, Roman; Schafler, Erhard; Schell, Norbert; Kunz, Martin; Abart, Rainer

2017-11-01

Calcite aggregates were deformed to high strain using high-pressure torsion and applying confining pressures of 1-6 GPa and temperatures between room temperature and 450 °C. The run products were characterized by X-ray diffraction, and key microstructural parameters were extracted employing X-ray line profile analysis. The dominant slip system was determined as r { 10 1 bar 4 } ⟨ 2 bar 021 ⟩ with edge dislocation character. The resulting dislocation density and the size of the coherently scattering domains (CSD) exhibit a systematic dependence on the P-T conditions of deformation. While high pressure generally impedes recovery through reducing point defect mobility, the picture is complicated by pressure-induced phase transformations in the CaCO3 system. Transition from the calcite stability field to those of the high-pressure polymorphs CaCO3-II, CaCO3-III and CaCO3-IIIb leads to a change of the microstructural evolution with deformation. At 450 °C and pressures within the calcite stability field, dislocation densities and CSD sizes saturate at shear strains exceeding 10 in agreement with earlier studies at lower pressures. In the stability field of CaCO3-II, the dislocation density exhibits a more complex behavior. Furthermore, at a given strain and strain rate, the dislocation density increases and the CSD size decreases with increasing pressure within the stability fields of either calcite or of the high-pressure polymorphs. There is, however, a jump from high dislocation densities and small CSDs in the upper pressure region of the calcite stability field to lower dislocation densities and larger CSDs in the low-pressure region of the CaCO3-II stability field. This jump is more pronounced at higher temperatures and less so at room temperature. The pressure influence on the deformation-induced evolution of dislocation densities implies that pressure variations may change the rheology of carbonate rocks. In particular, a weakening is expected to occur at the transition from the calcite to the CaCO3-II stability field, if aragonite does not form.

Co3O4/MnO2/Hierarchically Porous Carbon as Superior Bifunctional Electrodes for Liquid and All-Solid-State Rechargeable Zinc-Air Batteries.

PubMed

Li, Xuemei; Dong, Fang; Xu, Nengneng; Zhang, Tao; Li, Kaixi; Qiao, Jinli

2018-05-09

The design of efficient, durable, and affordable catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is very indispensable in liquid-type and flexible all-solid-state zinc-air batteries. Herein, we present a high-performance bifunctional catalyst with cobalt and manganese oxides supported on porous carbon (Co 3 O 4 /MnO 2 /PQ-7). The optimized Co 3 O 4 /MnO 2 /PQ-7 exhibited a comparable ORR performance with commercial Pt/C and a more superior OER performance than all of the other prepared catalysts, including commercial Pt/C. When applied to practical aqueous (6.0 M KOH) zinc-air batteries, the Co 3 O 4 /MnO 2 /porous carbon hybrid catalysts exhibited exceptional performance, such as a maximum discharge peak power density as high as 257 mW cm -2 and the most stable charge-discharge durability over 50 h with negligible deactivation to date. More importantly, a series of flexible all-solid-state zinc-air batteries can be fabricated by the Co 3 O 4 /MnO 2 /porous carbon with a layer-by-layer method. The optimal catalyst (Co 3 O 4 /MnO 2 /PQ-7) exhibited an excellent peak power density of 45 mW cm -2 . The discharge potentials almost remained unchanged for 6 h at 5 mA cm -2 and possessed a long cycle life (2.5 h@5 mA cm -2 ). These results make the optimized Co 3 O 4 /MnO 2 /PQ-7 a promising cathode candidate for both liquid-type and flexible all-solid-state zinc-air batteries.

Modification of Ga2O3 by an Ag-Cr core-shell cocatalyst enhances photocatalytic CO evolution for the conversion of CO2 by H2O.

PubMed

Pang, Rui; Teramura, Kentaro; Tatsumi, Hiroyuki; Asakura, Hiroyuki; Hosokawa, Saburo; Tanaka, Tsunehiro

2018-01-25

A core-shell structure of Ag-Cr dual cocatalyst loaded-Ga 2 O 3 was found to significantly enhance the formation rate of CO and selectivity toward CO evolution for the photocatalytic conversion of CO 2 where H 2 O is used as an electron donor.

Microstructure evolution characteristics induced by oxygen vacancy generation in anatase TiO2 based resistive switching devices

NASA Astrophysics Data System (ADS)

Liu, Chen; Gao, Bin; Huang, Peng; Kang, Jinfeng

2017-03-01

In this work, first principle calculations are employed to study the microstructure characteristics of the anatase TiO2 resistive switching material associated with the generation of oxygen vacancy (V o) based nanofilaments during the switching process. The calculations indicate that both the magnéli phase Ti4O7 and V o-defect phase of anatase TiO2 may be formed with the generation of oxygen vacancies during the forming and SET processes. Based on the calculations, a new physical insight is proposed to clarify the microstructure evolution characteristics of the anatase TiO2 resistive switching material and the correlation with resistive switching behaviors. During the forming or SET process, the anatase TiO2 is first excited to a transition state with the generation of oxygen vacancies, then fully relaxes to a stable V o-defect state. This V o-defect state may either recover to the original state with the recombination of the oxygen vacancies, which causes the reversible resistive switching behavior, or further transform to a much more stable state—the magnéli phase Ti4O7, through a phase transition process with the generation of many more oxygen vacancies. The phase transition from V o- defective anatase phase to magnéli phase Ti4O7 causes the failure of the resistive switching due to the significantly reduced possibility of the reversible phase transition from the magnéli phase to the anatase phase, compared with the possibility of the recombination from the V o-defective anatase.

Controllable synthesis and down-conversion properties of flower-like NaY(MoO{sub 4}){sub 2} microcrystals via polyvinylpyrrolidone-mediated

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

Lin, Han; Yan, Xiaohong, E-mail: xhyan@nuaa.edu.cn; College of Electronic Science and Engineering, Nanjing University of Posts and Telecommunications, Nanjing 210046

Double alkaline rare-earth molybdates NaY(MoO{sub 4}){sub 2} with multilayered flower-like architectures have been successfully synthesized via hydrothermal method in polyvinylpyrrolidone (PVP)-modified processes. The crystal structure and morphology of the obtained products were characterized by X-ray diffraction, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that reaction time and the amount of PVP have crucial influences on the morphology of the resulting novel microstructures. Under 450 nm excitation, Ho{sup 3+}/Yb{sup 3+} co-doped NaY(MoO{sub 4}){sub 2} samples exhibit 539 nm green emission and 960–1200 nm broadband near-infrared emission, corresponding to the characteristic lines of Ho{sup 3+} and Yb{supmore » 3+}, respectively. Moreover, increasing Yb{sup 3+} doping enhances the energy transfer efficiency from Ho{sup 3+} to Yb{sup 3+}. - Graphical abstract: Low and high-magnification SEM images demonstrate the perfect flower-like NaY(MoO{sub 4}){sub 2} prepared in the presence of PVP; Detailed TEM and HRTEM images further manifest the single-crystalline feature. Highlights: • NaY(MoO{sub 4}){sub 2} flower-like microstructures were synthesized by hydrothermal method using polyvinylpyrrolidone. • Polyvinylpyrrolidone induces the growth of the NaY(MoO{sub 4}){sub 2} to form multilayered architectures. • Flowerlike NaY(MoO{sub 4}){sub 2}: Ho{sup 3+}, Yb{sup 3+} phosphors were investigated as a downconversion layer candidate.« less

Effect of nanosized Co{sub 0.5}Ni{sub 0.5}Fe{sub 2}O{sub 4} on the transport critical current density of Bi{sub 1.6}Pb{sub 0.4}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10} superconductor

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

Hafiz, M.; Abd-Shukor, R.

2014-09-03

The effects of nano-sized Co{sub 0.5}Ni{sub 0.5}Fe{sub 2}O{sub 4} addition on the superconducting and transport properties of Bi{sub 1.6}Pb{sub 0.4}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10} (Bi-2223) in bulk form has been investigated. Bi-2223 superconductor was fabricated using co-precipitation method and 0.01 – 0.05 wt% of Co{sub 0.5}Ni{sub 0.5}Fe{sub 2}O{sub 4} nanoparticles with average size of 20 nm were added into the samples. The critical temperature (T{sub c}) and critical current density (J{sub c}) of the samples were measured by using the four-point probe method, while the phase formation and microstructure of the samples were examined using x-ray diffraction and SEM respectively.more » It was found that J{sub c} of all samples added with Co{sub 0.5}Ni{sub 0.5}Fe{sub 2}O{sub 4} were higher than non-added sample, with x = 0.01 wt. % sample showing the highest J{sub c}. This study showed that small addition of nano-Co{sub 0.5}Ni{sub 0.5}Fe{sub 2}O{sub 4} can effectively enhance the transport critical current density in Bi-2223 superconductor.« less

Annealing Effects on Microstructure and Mechanical Properties of Ultrafine-Grained Al Composites Reinforced with Nano-Al2O3 by Rotary Swaging

NASA Astrophysics Data System (ADS)

Chen, Cunguang; Wang, Wenwen; Guo, Zhimeng; Sun, Chunbao; Volinsky, Alex A.; Paley, Vladislav

2018-03-01

Microstructure evolution and variations in mechanical properties of Al-Al2O3 nanocomposite produced by powder metallurgy were investigated and compared with commercially pure aluminum (Al-1050) after furnace annealing. Fine gas-atomized Al powder compacts were first sintered in flowing nitrogen, subsequently consolidated into wires by rotary swaging and eventually annealed at 300 and 500 °C for 24 h each. Scanning and transmission electron microscopy with energy-dispersive spectroscopy was utilized to document the microstructure evolution. Rotary swaging was proven to lead to a marked decrease in grain size. After heavy swaging to true deformation degree of φ = 6 and annealing at 500 °C, obvious recrystallization was observed at Al-1050's existing grain boundaries and the crystals began to grow perpendicular to the flow direction. In the Al-Al2O3 nanocomposite, fabricated from d 50 = 6 μm Al powder, recrystallization partially occurred, while grains were still extremely fine. Due to the dual role of fine-grained Al2O3 dispersion strengthening, the nanocomposite showed improved mechanical performance in terms of tensile strength, approximately twice higher than Al-1050 after annealing at 500 °C.

Facile synthesis of electrospun MFe2O4 (M = Co, Ni, Cu, Mn) spinel nanofibers with excellent electrocatalytic properties for oxygen evolution and hydrogen peroxide reduction

NASA Astrophysics Data System (ADS)

Li, Mian; Xiong, Yueping; Liu, Xiaotian; Bo, Xiangjie; Zhang, Yufan; Han, Ce; Guo, Liping

2015-05-01

Designing and preparing porous transition metal ferrites without using any template, shape-directing agent, and surfactant is a challenge. Herein, heterojunction MFe2O4 (M = Co, Ni, Cu, Mn) nanofiber (NF) based films with three-dimensional configurations were synthesized by electrospinning and the subsequent thermal treatment processes. Characterization results indeed show the 3D net-like textural structures of the electrospun spinel-type MFe2O4 NFs. In particular, the resulting MFe2O4 NFs have lengths up to several dozens of micrometers with an average diameter size of about 150 nm and possess abundant micro/meso/macropores on both the surface and within the films. The hierarchically porous structures and high surface areas of these MFe2O4 NFs (for example, the CoFe2O4 NFs possess a larger BET specific surface area (61.48 m2 g-1) than those of the CoFe2O4 NPs (5.93 m2 g-1)) can afford accessible transport channels for effectively decreasing the mass transport resistances, enhancing the electrical conductivity, and increasing the density and reactivity of the exposed catalytic active sites. All these advantages will be responsible for the better electrocatalytic performances of these MFe2O4 NFs compared with their structural isomers (i.e. the MFe2O4 NPs) for the oxygen evolution reaction (OER) and H2O2 reduction in alkaline solution. Meanwhile, both the OER and H2O2 reduction catalytic activities for these MFe2O4 NFs obey the order of CoFe2O4 NFs > CuFe2O4 NFs > NiFe2O4 NFs > MnFe2O4 NFs > Fe2O3 NFs. The CoFe2O4 NFs represent a new class of highly efficient non-noble-metal catalysts for both OER and H2O2 reduction/detection in alkaline media.Designing and preparing porous transition metal ferrites without using any template, shape-directing agent, and surfactant is a challenge. Herein, heterojunction MFe2O4 (M = Co, Ni, Cu, Mn) nanofiber (NF) based films with three-dimensional configurations were synthesized by electrospinning and the subsequent thermal treatment processes. Characterization results indeed show the 3D net-like textural structures of the electrospun spinel-type MFe2O4 NFs. In particular, the resulting MFe2O4 NFs have lengths up to several dozens of micrometers with an average diameter size of about 150 nm and possess abundant micro/meso/macropores on both the surface and within the films. The hierarchically porous structures and high surface areas of these MFe2O4 NFs (for example, the CoFe2O4 NFs possess a larger BET specific surface area (61.48 m2 g-1) than those of the CoFe2O4 NPs (5.93 m2 g-1)) can afford accessible transport channels for effectively decreasing the mass transport resistances, enhancing the electrical conductivity, and increasing the density and reactivity of the exposed catalytic active sites. All these advantages will be responsible for the better electrocatalytic performances of these MFe2O4 NFs compared with their structural isomers (i.e. the MFe2O4 NPs) for the oxygen evolution reaction (OER) and H2O2 reduction in alkaline solution. Meanwhile, both the OER and H2O2 reduction catalytic activities for these MFe2O4 NFs obey the order of CoFe2O4 NFs > CuFe2O4 NFs > NiFe2O4 NFs > MnFe2O4 NFs > Fe2O3 NFs. The CoFe2O4 NFs represent a new class of highly efficient non-noble-metal catalysts for both OER and H2O2 reduction/detection in alkaline media. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr07243j

Electrical properties of samarium cobaltite nanoparticles synthesized using Sol–Gel autocombustion route

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

Sathyamoorthy, B.; Md Gazzali, P.M.; Murugesan, C.

2014-05-01

Highlights: • The structural evolution and its electrical properties of samarium cobaltite nanograins are discussed. • Optimization of SmCoO{sub 3} nanograins is achieved by post sintering as-prepared gel at 800 °C. • The impedance spectra indicate the semiconducting behavior SmCoO{sub 3} nanograins. - Abstract: Nanograins of SmCoO{sub 3} are prepared by citric acid assisted Sol–Gel autocombustion route. The characterizations of crystal structure, surface morphology and electrical properties of SmCoO{sub 3} powder are done using XRD, HRSEM, FTIR and BDS. The structural evolution of SmCoO{sub 3} upon increasing the annealing temperature is followed using XRD and FTIR analyses. The powder samplemore » contains polycrystalline grains with average size equal to 35 nm and orthorhombic perovskite structure with Pbnm space group. The vibrational bands observed in FTIR spectrum at 545 cm{sup −1} and 439 cm{sup −1} correspond to Co-O stretching modes in cobaltite system. HRSEM images of the sample show the formation of hexagonal shaped grains of samarium cobaltite. The AC electrical conductivity of 4.914 × 10{sup −5} S cm{sup −1} at 295 K is measured for SmCoO{sub 3} nanoparticles. The impedance spectra bring out the semiconducting behavior of the material.« less

The impact of NiO on microstructure and electrical property of solid oxide fuel cell anode

PubMed Central

Li, Yan; Luo, Zhong-yang; Yu, Chun-jiang; Luo, Dan; Xu, Zhu-an; Cen, Ke-fa

2005-01-01

Ni-Ce0.8Sm0.2O1.9 (Ni-SDC) cermet was selected as anode material for reduced temperature (800 °C) solid oxide fuel cells in this study. The influence of NiO powder fabrication methods for Ni-SDC cermets on the electrode performance was investigated so that the result obtained can be applied to make high-quality anode. Three kinds of NiO powder were synthesized with a fourth kind being available in the market. Four types of anode precursors were fabricated with these NiO powders and Ce0.8Sm0.2O1.9 (SDC), and then were reduced to anode wafers for sequencing measurement. The electrical conductivity of the anodes was measured and the effect of microstructure was investigated. It was found that the anode electrical conductivity depends strongly on the NiO powder morphologies, microstructure of the cermet anode and particle sizes, which are decided by NiO powder preparation technique. The highest electrical conductivity is obtained for anode cermets with NiO powder synthesized by NiCO3·2Ni(OH)2·4H2O or Ni(NO3)2·6H2O decomposition technique. PMID:16252348

Oxidation behaviour of ferritic stainless steel grade Crofer 22 APU at 700 °C in flowing Ar-75%CO2-12%H2O

NASA Astrophysics Data System (ADS)

Shariff, Nurul Atikah; Othman, Norinsan Kamil; Jalar, Azman

2013-11-01

The oxidation of Ferritic Stainless Steel (FSS) grade Crofer 22 APU has been investigated. FSS alloys were exposed to isothermal conditions in a horizontal tube furnace at a 700 °C in flowing Ar-75%CO2-12%H2O at a pressure of approximately 1 atm. The results showed that the growth of non protective Fe2O3 and spinel was observed after 50 h exposure in the presence of 12% H2O. The weight was increased significantly with time of exposure. The formation of different oxides is presented on the interface of the specimen such as MnCr2O4, Fe3O4 and Fe2O3 were revealed by X-ray diffraction and supported by EDAX analysis. FSS did not form a protective Cr2O3 layer due to water vapour accelerates the kinetics oxidation. Data of microstructure observation is presented and discussed in this paper in term of water vapour effects.

Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen.

PubMed

Mahne, Nika; Renfrew, Sara E; McCloskey, Bryan D; Freunberger, Stefan A

2018-05-04

Solid alkali metal carbonates are universal passivation layer components of intercalation battery materials and common side products in metal-O 2 batteries, and are believed to form and decompose reversibly in metal-O 2 /CO 2 cells. In these cathodes, Li 2 CO 3 decomposes to CO 2 when exposed to potentials above 3.8 V vs. Li/Li + . However, O 2 evolution, as would be expected according to the decomposition reaction 2 Li 2 CO 3 →4 Li + +4 e - +2 CO 2 +O 2 , is not detected. O atoms are thus unaccounted for, which was previously ascribed to unidentified parasitic reactions. Here, we show that highly reactive singlet oxygen ( 1 O 2 ) forms upon oxidizing Li 2 CO 3 in an aprotic electrolyte and therefore does not evolve as O 2 . These results have substantial implications for the long-term cyclability of batteries: they underpin the importance of avoiding 1 O 2 in metal-O 2 batteries, question the possibility of a reversible metal-O 2 /CO 2 battery based on a carbonate discharge product, and help explain the interfacial reactivity of transition-metal cathodes with residual Li 2 CO 3 . © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Nanostructural Tailoring to Induce Flexibility in Thermoelectric Ca3Co4O9 Thin Films

PubMed Central

2017-01-01

Because of their inherent rigidity and brittleness, inorganic materials have seen limited use in flexible thermoelectric applications. On the other hand, for high output power density and stability, the use of inorganic materials is required. Here, we demonstrate a concept of fully inorganic flexible thermoelectric thin films with Ca3Co4O9-on-mica. Ca3Co4O9 is promising not only because of its high Seebeck coefficient and good electrical conductivity but also because of the abundance, low cost, and nontoxicity of its constituent raw materials. We show a promising nanostructural tailoring approach to induce flexibility in inorganic thin-film materials, achieving flexibility in nanostructured Ca3Co4O9 thin films. The films were grown by thermally induced phase transformation from CaO–CoO thin films deposited by reactive rf-magnetron cosputtering from metallic targets of Ca and Co to the final phase of Ca3Co4O9 on a mica substrate. The pattern of nanostructural evolution during the solid-state phase transformation is determined by the surface energy and strain energy contributions, whereas different distributions of CaO and CoO phases in the as-deposited films promote different nanostructuring during the phase transformation. Another interesting fact is that the Ca3Co4O9 film is transferable onto an arbitrary flexible platform from the parent mica substrate by etch-free dry transfer. The highest thermoelectric power factor obtained is above 1 × 10–4 W m–1 K–2 in a wide temperature range, thus showing low-temperature applicability of this class of materials. PMID:28699345

Synthesis of Galaxite, Mn0.9Co0.1Al2O4, and its application as a novel nanocatalyst for electrochemical hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Saeidfirozeh, Homa; Shafiekhani, Azizollah; Beheshti-Marnani, Amirkhosro; Askari, Mohammad Bagher

2018-06-01

A new compound Mn0.9Co0.1Al2O4 nanowires were synthesized by thermal method. The resulting powder samples were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray diffraction (XRD). We found that a set of phase transformation occurred during the process. Eventually, five phases including three spinal phases, the corundum (á-Al2O3) and MnO were formed at 1100 °C.As dominant morphology, the cubic galaxite nanowires were identified by X-ray analysis. Moreover, X-ray analysis showed that Mn3O4 and Co3O4 nanoparticles were formed in tetragonal and cubic symmetry respectively. The SEM image revealed that a dominate morphology of product has cubic nanowires shape with an average diameter in range 38-43 nm. Furthermore, we observed that influence of temperature was very important in the nanowire formation process. Electrochemical hydrogen evolution reaction (HER) of synthetic composite was evaluated and the over potential of HER was calculated about 110 mV with low Tafel slope equal to 42 mV dec-1, which was comparable with amounts reported transition metal dichalcogenides with satisfying durability.

Strain Effects in Epitaxial VO2 Thin Films on Columnar Buffer-Layer TiO2/Al2O3 Virtual Substrates.

PubMed

Breckenfeld, Eric; Kim, Heungsoo; Burgess, Katherine; Charipar, Nicholas; Cheng, Shu-Fan; Stroud, Rhonda; Piqué, Alberto

2017-01-18

Epitaxial VO 2 /TiO 2 thin film heterostructures were grown on (100) (m-cut) Al 2 O 3 substrates via pulsed laser deposition. We have demonstrated the ability to reduce the semiconductor-metal transition (SMT) temperature of VO 2 to ∼44 °C while retaining a 4 order of magnitude SMT using the TiO 2 buffer layer. A combination of electrical transport and X-ray diffraction reciprocal space mapping studies help examine the specific strain states of VO 2 /TiO 2 /Al 2 O 3 heterostructures as a function of TiO 2 film growth temperatures. Atomic force microscopy and transmission electron microscopy analyses show that the columnar microstructure present in TiO 2 buffer films is responsible for the partially strained VO 2 film behavior and subsequently favorable transport characteristics with a lower SMT temperature. Such findings are of crucial importance for both the technological implementation of the VO 2 system, where reduction of its SMT temperature is widely sought, as well as the broader complex oxide community, where greater understanding of the evolution of microstructure, strain, and functional properties is a high priority.

Magnetic properties evolution of the CoxFe3-xO4/SiO2 system due to advanced thermal treatment at 700 °C and 1000 °C

NASA Astrophysics Data System (ADS)

Dippong, Thomas; Levei, Erika Andrea; Tanaselia, Claudiu; Gabor, Mihai; Nasui, Mircea; Barbu Tudoran, Lucian; Borodi, Gheorghe

2016-07-01

The CoxFe3-xO4 (x=0.5-2.5) system embedded in the silica matrix was synthesised by sol-gel method using cobalt nitrate, iron nitrate, 1.4-butanediol and tetraethyl orthosilicate. Five different Co/Fe molar ratios in the presence of diol and one without diol were used for the synthesis. The obtained gels were subjected to thermal treatment at 700 °C and 1000 °C. The oxide species formed in the silica matrix, the optimum temperature for the CoFe2O4 phase formation, the evolution of nanocrystallites size and magnetic properties with the calcination temperature were studied. The formed oxide species were studied using X-ray diffraction, Fourier transformed infrared spectrometry, the Co/Fe molar ratio was confirmed using inductively coupled plasma optical emission spectrometry, the nanocrystallites size, shape and clustering was identified by transmission electron microscopy and scanning electron microscopy, while the formation of magnetic phases was investigated by hysteresis and magnetization derivatives measurements.

Low Temperature Synthesis, Chemical and Electrochemical Characterization of LiNi(x)Co(1-x)O2 (0 less than x less than 1)

NASA Technical Reports Server (NTRS)

Nanjundaswamy, K. S.; Standlee, D.; Kelly, C. O.; Whiteley, R. V., Jr.

1997-01-01

A new method of synthesis for the solid solution cathode materials LiNi(x)Co(1-x)O2 (0 less than x less than 1) involving enhanced reactions at temperatures less than or equal to 700 deg. C, between metal oxy-hydroxide precursors MOOH (M = Ni, Co) and Li-salts (Li2CO3, LiOH, and LiNO3) has been investigated. The effects of synthesis conditions and sources of Li, on phase purity, microstructure, and theoretical electrochemical capacity (total M(3+) content) are characterized by powder X-ray diffraction analysis, scanning electron microscopy, chemical analysis and room temperature magnetic susceptibility. An attempt has been made to correlate the electrochemical properties with the synthesis conditions and microstructure.

Defects in zinc oxide grown by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Ling, Francis C. C.; Wang, Zilan; Ping Ho, Lok; Younas, M.; Anwand, W.; Wagner, A.; Su, S. C.; Shan, C. X.

2016-01-01

ZnO films are grown on c-plane sapphire using the pulsed laser deposition method. Systematic studies on the effects of annealing are performed to understand the thermal evolutions of the defects in the films. Particular attention is paid to the discussions of the ZnO/sapphire interface thermal stability, the Zn-vacancy related defects having different microstructures, the origins of the green luminescence (∼2.4-2.5 eV) and the near band edge (NBE) emission at 3.23 eV.

Doping effect on charge ordering in the spinel compound AlV_2-xCr_xO_4

NASA Astrophysics Data System (ADS)

Horibe, Yoichi; Kurushima, Kosuke; Mori, Shigeo; Shingu, Masao; Katsufuji, Takuro

2004-03-01

It is reported that AlV_2O4 with the spinel-type structure shows the charge-ordering (CO) behavior below 700K.[1] Because the average valence of V is V^2.5+ in this compound, the CO structure is characterized by the unique CO pattern with V^2+:V^4+=3:1. In this talk, we will report doping effect on the CO structure in AlV_2O_4. In particular, we will focus on changes of microstructure related to the CO structure by Cr doping by transmission electron microscopy. Firstly we confirmed that AlV_2O4 has a long-ranged CO structure characterized by a single wave vector q=(1/2)[111]. On the other hand, we found the presence of diffuse scatterings at the (1/2)[111] and (1/2)[1-11]-type positions in AlV_1.875Cr_0.125O4 at room temperature. This means that the CO structure in AlV_1.875Cr_0.125O4 has two wave vectors of q=(1/2)[111] and q=the (1/2)[1-11]. Furthermore, the long-ranged CO structure in AlV_2O4 changes into the short-ranged one by substituting Cr ions into the V ones. The correlation length of CO in x=0.125 can be estimated to be about 5 nm. Our results suggest that the Cr doping destroyed the CO correlation effectively. It is revealed that by substituting Cr ions to V ones, the CO state is suppressed drastically and disappeared with x > 0.125. [1] K. Matsuno et al., J. Phys. Soc. Jpn 70, 1456 (2001)

High Curie temperature and enhanced magnetoelectric properties of the laminated Li0.058(Na0.535K0.48)0.942NbO3/Co0.6 Zn0.4Fe1.7Mn0.3O4 composites

PubMed Central

Yang, Haibo; Zhang, Jintao; Lin, Ying; Wang, Tong

2017-01-01

Laminated magnetoelectric composites of Li0.058(Na0.535K0.48)0.942NbO3 (LKNN)/Co0.6Zn0.4Fe1.7Mn0.3O4 (CZFM) prepared by the conventional solid-state sintering method were investigated for their dielectric, magnetic, and magnetoelectric properties. The microstructure of the laminated composites indicates that the LKNN phase and CZFM phase can coexist in the composites. Compared with the particulate magnetoelectric composites, the laminated composites have better piezoelectric and magnetoelectric properties due to their higher resistances and lower leakage currents. The magnetoelectric behaviors lie on the relative mass ratio of LKNN phase and CZFM phase. The laminated composites possess a high Curie temperature (TC) of 463 °C, and the largest ME coefficient of 285 mV/cm Oe, which is the highest value for the lead-free bulk ceramic magnetoelectric composites so far. PMID:28338006

Carbon supported MnO2-CoFe2O4 with enhanced electrocatalytic activity for oxygen reduction and oxygen evolution

NASA Astrophysics Data System (ADS)

Wang, Ying; Liu, Qing; Hu, Tianjun; Zhang, Limin; Deng, Youquan

2017-05-01

The catalyst MnO2-CoFe2O4/C was firstly synthesized via a two-step process and applied as a bifunctional electrocatalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline media. The composite exhibits better bifunctional activity than CoFe2O4/C and MnO2/C. Moreover, superior durability and high methanol tolerance in alkaline media outperforms the commercial Pt/C electrocatalyst, which signifying its excellent potential for applications in metal-air batteries and alkaline fuel cells.

Molten-salt treatment of waste biomass for preparation of carbon with enhanced capacitive properties and electrocatalytic activity towards oxygen reduction.

PubMed

Lu, Beihu; Zhou, Jing; Song, Yuqiao; Wang, Hailong; Xiao, Wei; Wang, Dihua

2016-08-15

Carbon powders are building blocks for electrochemical energy storage/conversion devices. Green, cost-affordable and facile preparation of carbon with applicable electrochemical properties is therefore essential for effective utilization of fluctuating renewable energy. Herein, the preparation of carbon nanoflakes via impregnation of waste biomass i.e. boiled coffee beans in molten Na2CO3-K2CO3 (with equal mass) at 800 °C and molten CaCl2 at 850 °C is reported. The microstructure and surface chemistry of the obtained carbons are specified. The correlations between synthetic conditions and microstructure/surface chemistry of the obtained carbons are rationalized. The derived carbon nanosheets are tested and compared as active materials for supercapacitors in a configuration of symmetric full cells in 1 M MeEt3NBF4 in acetonitrile and electrocatalysts towards the oxygen reduction reaction (ORR) in O2-saturated 0.1 M aqueous KOH. Despite the lower surface area, the carbon nanosheets derived in molten Na2CO3-K2CO3 exhibit enhanced capacitive properties and electrocatalytic ORR activity. The present study highlights the importance of thermal media on the microstructure, surface chemistry and electrochemistry of carbon from biomass.

Study on photocatalytic activity of nanosized Co0.3Zn0.7Fe2O4 synthesized by hydrothermal method

NASA Astrophysics Data System (ADS)

Mondal, R.; Sarkar, K.; Dey, S.; Bhattacharjee, S.; Ghosh, C. K.; Kumar, S.

2018-04-01

We have reported the photocatalytic activity of nanosized Co0.3Zn0.7Fe2O4 (CZM) synthesized by hydrothermal method. Powder x-ray diffraction (PXRD), field emission and transmission electron microscopic techniques have been employed for structural and microstructural characterization of the sample. The Rietveld refinement of the PXRD pattern of CZM reveals that the sample is a single phase spinel ferrite of F d 3 ¯m symmetry having crystallite size ˜ 20 nm. The average particle size is ˜ 23 nm. The photocatalytic study suggests that CZM can be suitably used as an efficient (rate constant and % degradation are 7.4×10-2 min-1, 95.76 % at 40 min, respectively), magnetically separable, recyclable photocatalyst for removal of Congo Red from its aqueous solution.

Evolution of the Active Phase of CoMo/Al2O3 Catalysts under Industrial Conditions: a High-Pressure MES Study

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

Dugulan, A.I.; Overweg, A.R.; Craje, M.W.J.

2005-04-26

The behavior of CoMo/Al2O3 catalysts sulfided in H2S/H2 gas mixture, under industrial conditions, was investigated using Moessbauer emission spectroscopy (MES). An intermediate Co-Mo phase is formed after increasing the sulfidation pressure to 4 MPa, favoring the Co-Mo-S phase formation. An increase in the quadrupole splitting value of the Co-sulfide species after treatment at 573 K is proposed as a prerequisite for the formation of ideal Co-Mo-S structures.

A hierarchical nanostructure consisting of amorphous MnO 2, Mn 3O 4 nanocrystallites, and single-crystalline MnOOH nanowires for supercapacitors

NASA Astrophysics Data System (ADS)

Hu, Chi-Chang; Hung, Ching-Yun; Chang, Kuo-Hsin; Yang, Yi-Lin

In this communication, a porous hierarchical nanostructure consisting of amorphous MnO 2 (a-MnO 2), Mn 3O 4 nanocrystals, and single-crystalline MnOOH nanowires is designed for the supercapacitor application, which is prepared by a simple two-step electrochemical deposition process. Because of the gradual co-transformation of Mn 3O 4 nanocrystals and a-MnO 2 nanorods into an amorphous manganese oxide, the cycle stability of a-MnO 2 is obviously enhanced by adding Mn 3O 4. This unique ternary oxide nanocomposite with 100-cycle CV activation exhibits excellent capacitive performances, i.e., excellent reversibility, high specific capacitances (470 F g -1 in CaCl 2), high power property, and outstanding cycle stability. The highly porous microstructures of this composite before and after the 10,000-cycle CV test are examined by means of scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

Microstructural Evolution of Dy2O3-TiO2 Powder Mixtures during Ball Milling and Post-Milled Annealing

PubMed Central

Huang, Jinhua; Ran, Guang; Lin, Jianxin; Shen, Qiang; Lei, Penghui; Wang, Xina; Li, Ning

2016-01-01

The microstructural evolution of Dy2O3-TiO2 powder mixtures during ball milling and post-milled annealing was investigated using XRD, SEM, TEM, and DSC. At high ball-milling rotation speeds, the mixtures were fined, homogenized, nanocrystallized, and later completely amorphized, and the transformation of Dy2O3 from the cubic to the monoclinic crystal structure was observed. The amorphous transformation resulted from monoclinic Dy2O3, not from cubic Dy2O3. However, at low ball-milling rotation speeds, the mixtures were only fined and homogenized. An intermediate phase with a similar crystal structure to that of cubic Dy2TiO5 was detected in the amorphous mixtures annealed from 800 to 1000 °C, which was a metastable phase that transformed to orthorhombic Dy2TiO5 when the annealing temperature was above 1050 °C. However, at the same annealing temperatures, pyrochlore Dy2Ti2O7 initially formed and subsequently reacted with the remaining Dy2O3 to form orthorhombic Dy2TiO5 in the homogenous mixtures. The evolutionary mechanism of powder mixtures during ball milling and subsequent annealing was analyzed. PMID:28772375

The co-evolution of microstructure features in self-ion irradiated HT9 at very high damage levels

NASA Astrophysics Data System (ADS)

Getto, E.; Vancoevering, G.; Was, G. S.

2017-02-01

Understanding the void swelling and phase evolution of reactor structural materials at very high damage levels is essential to maintaining safety and longevity of components in Gen IV fast reactors. A combination of ion irradiation and modeling was utilized to understand the microstructure evolution of ferritic-martensitic alloy HT9 at high dpa. Self-ion irradiation experiments were performed on alloy HT9 to determine the co-evolution of voids, dislocations and precipitates up to 650 dpa at 460 °C. Modeling of microstructure evolution was conducted using the modified Radiation Induced Microstructure Evolution (RIME) model, which utilizes a mean field rate theory approach with grouped cluster dynamics. Irradiations were performed with 5 MeV raster-scanned Fe2+ ions on samples pre-implanted with 10 atom parts per million He. The swelling, dislocation and precipitate evolution at very high dpa was determined using Analytical Electron Microscopy in Scanning Transmission Electron Microscopy (STEM) mode. Experimental results were then interpreted using the RIME model. A microstructure consisting only of dislocations and voids is insufficient to account for the swelling evolution observed experimentally at high damage levels in a complicated microstructure such as irradiated alloy HT9. G phase was found to have a minimal effect on either void or dislocation evolution. M2X played two roles; a variable biased sink for defects, and as a vehicle for removal of carbon from solution, thus promoting void growth. When accounting for all microstructure interactions, swelling at high damage levels is a dynamic process that continues to respond to other changes in the microstructure as long as they occur.

The effect of micro-structure on upconversion luminescence of Nd3+/Yb3+ co-doped La2O3-TiO2-ZrO2 glass-ceramics

NASA Astrophysics Data System (ADS)

Zhang, Minghui; Wen, Haiqin; Pan, Xiuhong; Yu, Jianding; Jiang, Meng; Yu, Huimei; Tang, Meibo; Gai, Lijun; Ai, Fei

2018-03-01

Nd3+/Yb3+ co-doped La2O3-TiO2-ZrO2 glasses have been prepared by aerodynamic levitation method. The glasses show high refractive index of 2.28 and Abbe number of 18.3. Glass-ceramics heated at 880 °C for 50 min perform the strongest upconversion luminescence. X-ray diffraction patterns of glass-ceramics with different depths indicate that rare earth ions restrain crystallization. Body crystallization mechanism mixed with surface crystallization is confirmed in the heat treatment. Surface crystals achieve priority to grow, resulting in important effects on upconversion luminescence. The results of atomic force microscope and scanning electron microscope indicate that crystal particles with uniform size distribute densely and homogenously on the surface and large amount of glass matrix exists in the glass ceramics heated at 880 °C for 50 min. Crystals in the glass-ceramics present dense structure and strong boundaries, which can reduce the mutual nonradiative relaxation rate among rare earth ions and then improve upconversion luminescence effectively. Based on micro-structural study, the mechanism that upconversion luminescence can be improved by heat treatment has been revealed. The results of micro-structural analysis agree well with the spectra.

Strength and microstructure of sintered Si3N4 with rare-earth-oxide additions

NASA Technical Reports Server (NTRS)

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

1985-01-01

Room temperature, 700-, 1000-, 1200-, and 1370-C examinations of the effect of 1.7-2.6 mol pct rare earth oxide additions to sintered Si3N4 are conducted. While the room temperature-1000 C bend strengths were higher for this material with Y2O3 additions than with CeO2, La2O3, or Sm2O3, the reverse was true at 1200-1370 C. This phenomenon is explained on the basis of microstructural differences, since quantitative microscopy of SEM replicas showed the Si3N4-Y2O3 composition to contain both a higher percentage of elongated grains and a coarser microstructure than the other three alternatives. The elongated grains appear to increase this composition's low temperature strength irrespective of microstructural coarseness; this coarseness, however, decreases strength relative to the other compositions at higher temperatures.

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

Berto, Tobias F.; Sanwald, Kai E.; Byers, J. Paige

Photocatalytic overall water splitting requires co-catalysts that efficiently promote the generation of H-2 but do not catalyze its reverse oxidation. We demonstrate that CO chemisorbed on metal co-catalysts (Rh, Pt, Pd) suppresses the back reaction while maintaining the rate of H-2 evolution. On Rh/GaN:ZnO, the highest H-2 production rates were obtained with 4-40 mbar of CO, the back reaction remaining suppressed below 7 mbar of O-2. The O-2 and H-2 evolution rates compete with CO oxidation and the back reaction. The rates of all reactions increased with increasing photon absorption. However, due to different dependencies on the rate of chargemore » carrier generation, the selectivities for O-2 and H-2 formation increased in comparison to CO oxidation and the back reaction with increasing photon flux and/or quantum efficiency. Under optimum conditions, the impact of CO to prevent the back reaction is identical to that of a Cr2O3 layer covering the active metal particle.« less

Laboratory studies of cometary ice analogues

NASA Astrophysics Data System (ADS)

Schmitt, B.; Espinasse, S.; Grim, R. J. A.; Greenberg, J. M.; Klinger, J.

1989-12-01

Laboratory studies were performed in order to simulate the physico-chemical processes that are likely to occur in the near surface layers of short and intermediate period comets. Pure H2O ice as well as CO:H2O, CO2:H2O, CH4:H2O, CO:CO2:H2O, and NH3:H2O ice mixtures were studied in the temperature range between 10 and 180 K. The evolution of the composition of ice mixtures, the crystallization of H2O ice as well as the formation and decompostion of clathrate hydrate by different processes were studied as a function of temperature and time. Using the results together with numerical modeling, predictions are made about the survival of amorphous ice, CO, CO2, CH4, and NH3 in the near surface layers of short period comets. The likeliness of finding clathrate and molecular hydrates is discussed. It is proposed that the analytical methods developed here could be fruitfully adapted to the analysis of returned comet samples.

Modulated exchange bias in NiFe/CoO/α-Fe2O3 trilayers and NiFe/CoO bilayers

NASA Astrophysics Data System (ADS)

Li, X.; Lin, K.-W.; Yeh, W.-C.; Desautels, R. D.; van Lierop, J.; Pong, Philip W. T.

2017-02-01

While the exchange bias in ferromagnetic/antiferromagnetic (FM/AF) bilayer and FM1/AF/FM2 trilayer configurations has been widely investigated, the role of an AF2 layer in FM/AF1/AF2 trilayer configurations is still not well understood. In this work, the magnetic properties of NiFe/CoO, NiFe/α-Fe2O3 bilayers, and NiFe/CoO/α-Fe2O3 trilayer were studied comparatively. The microstructure and chemical composition were characterized. Temperature dependent magnetometry reveals increased irreversibility temperature in NiFe/CoO/α-Fe2O3 trilayer compared with NiFe/CoO bilayer. The magnetic hysteresis loops show that the exchange bias (Hex) and coercivity (Hc) depend strongly on the anisotropy of AF layer (CoO, α-Fe2O3 and CoO/α-Fe2O3). Our work shows that the AF1/AF2 interfacial interactions can be used effectively for tuning the exchange bias in FM/AF1/AF2 trilayers.

Microstructural Characteristics and Oxidation Behavior of Low-Pressure Cold-Sprayed CoNiCrAlY Coatings

NASA Astrophysics Data System (ADS)

Zhang, Lin-wei; Lu, Lei; Wang, Lu; Ning, Xian-jin; Wang, Quan-sheng; Wang, Ri-xin

2017-10-01

CoNiCrAlY coatings were deposited by low-pressure cold spraying and subsequently heat-treated at 1050 °C for 4 h in a vacuum environment. The microstructural characteristics and oxidation behavior of CoNiCrAlY coatings were investigated. The as-sprayed coating exhibited low porosity and oxygen content. The high plastic deformation of the sprayed particles led to significant refinement of γ-matrix and dissolution of β-(Ni,Co)Al phase in the as-sprayed coating. After heat treatment, the single phase (γ) in the as-sprayed coating was converted into a γ/β microstructure, and a continuous single α-Al2O3 scale was formed on the coating surface. Vacuum heat treatment can postpone the formation of spinel oxides within 100 h. After being oxidized at 1050 °C for 400 h, the heat-treated coating exhibited better oxidation resistance than the as-sprayed coating. The reduced growth rate of the oxide scale and the suppression of the formation of spinel oxides can be attributed to the vacuum heat treatment, as well as the intrinsic microstructure of the cold-sprayed coating. Finally, the effects of the microstructural changes induced during the cold spraying process on the growth of the thermally grown oxide and the oxidation mechanisms of the CoNiCrAlY coatings were discussed.

CuCo 2O 4 ORR/OER Bi-functional catalyst: Influence of synthetic approach on performance

DOE PAGES

Serov, Alexey; Andersen, Nalin I.; Roy, Aaron J.; ...

2015-02-07

A series of CuCo 2O 4 catalysts were synthesized by pore forming, sol-gel, spray pyrolysis and sacrificial support methods. Catalysts were characterized by XRD, SEM, XPS and BET techniques. The electrochemical activity for the oxygen reduction and oxygen evolution reactions (ORR and OER) was evaluated in alkaline media by RRDE. Density Functional Theory was used to identify two different types of active sites responsible for ORR/OER activity of CuCo 2O 4 and it was found that CuCo 2O 4 can activate the O-O bond by binding molecular oxygen in bridging positions between Co or Co and Cu atoms. It wasmore » found that the sacrificial support method (SSM) catalyst has the highest performance in both ORR and OER and has the highest content of phase-pure CuCo 2O 4. It was shown that the presence of CuO significantly decreases the activity in oxygen reduction and oxygen evolution reactions. As a result, the half-wave potential (E 1/2) of CuCo 2O 4-SSM was found as 0.8 V, making this material a state-of-the-art, unsupported oxide catalyst.« less

Magnetic properties, phase evolution, and microstructure of melt-spun (Sm{sub 1-x}Pr{sub x})Co{sub 7-y}Hf{sub y}C{sub z} (x=0-1; y=0.1-0.3; z=0-0.14) ribbons

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

Chang, H. W.; Chen, I. W.; Chang, C. W.

2008-04-01

Magnetic properties, phase evolution, and microstructure of melt-spun (Sm{sub 1-x}Pr{sub x})Co{sub 7-y}Hf{sub y}C{sub z} ribbons have been investigated. For (Sm{sub 1-x}Pr{sub x})Co{sub 7-y}Hf{sub y} (x=0-1; y=0.1-0.3) ribbons, the magnetization increases, but coercivity decreases, with increasing Pr content. However, the phase constitution and microstructure have not been influenced by modifying Pr content x. The attractive magnetic properties of B{sub r}=6.5 kG, {sub i}H{sub c}=6.1 kOe, and (BH){sub max}=7.2 MG Oe could be obtained for (Sm{sub 0.8}Pr{sub 0.2})Co{sub 6.9}Hf{sub 0.1} ribbons. A slight addition of C in (Sm{sub 0.8}Pr{sub 0.2})Co{sub 6.9}Hf{sub 0.1}C{sub z} (z=0.06-0.14) ribbon not only refines the microstructure, but alsomore » induces nanoscale fcc-Co precipitation in the matrix, leading to the stronger exchange-coupling effect between magnetic grains and the enhancement of remanence and magnetic energy product. As a result, the improved magnetic properties of B{sub r}=7.1 kOe, {sub i}H{sub c}=8.5 kOe, and (BH){sub max}=11.2 MG Oe can be achieved for (Sm{sub 0.8}Pr{sub 0.2})Co{sub 6.9}Hf{sub 0.1}C{sub 0.12} ribbons.« less

Cathodic electrochemical activation of Co3O4 nanoarrays: a smart strategy to significantly boost the hydrogen evolution activity.

PubMed

Yang, Li; Zhou, Huang; Qin, Xin; Guo, Xiaodong; Cui, Guanwei; Asiri, Abdullah M; Sun, Xuping

2018-02-22

Co(hydro)oxides show unsatisfactory catalytic activity for the hydrogen evolution reaction (HER) in alkaline media, and it is thus highly desirable but still remains a challenge to design and develop Co(hydro)oxide derived materials as superb hydrogen-evolving catalysts using a facile, rapid and less energy-intensive method. Here, we propose a cathodic electrochemical activation strategy toward greatly boosted HER activity of a Co 3 O 4 nanoarray via room-temperature cathodic polarization in sodium hypophosphite solution. After activation, the overpotential significantly decreases from 260 to 73 mV to drive a geometrical catalytic current density of 10 mA cm -2 in 1.0 M KOH. Notably, this activated electrode also shows strong long-term electrochemical durability with the retention of its catalytic activity at 100 mA cm -2 for at least 40 h.

Directionally solidified Al2O3/GAP eutectic ceramics by micro-pulling-down method

NASA Astrophysics Data System (ADS)

Cao, Xue; Su, Haijun; Guo, Fengwei; Tan, Xi; Cao, Lamei

2016-11-01

We reported a novel route to prepare directionally solidified (DS) Al2O3/GAP eutectic ceramics by micro-pulling-down (μ-PD) method. The eutectic crystallizations, microstructure characters and evolutions, and their mechanical properties were investigated in detail. The results showed that the Al2O3/GAP eutectic composites can be successfully fabricated through μ-PD method, possessed smooth surface, full density and large crystal size (the maximal size: φ90 mm × 20 mm). At the process of Diameter, the as-solidified Al2O3/GAP eutectic presented a combination of "Chinese script" and elongated colony microstructure with complex regular structure. Inside the colonies, the rod-type or lamellar-type eutectic microstructures with ultra-fine GAP surrounded by the Al2O3 matrix were observed. At an appropriate solidificational rate, the binary eutectic exhibited a typical DS irregular eutectic structure of "chinese script" consisting of interpenetrating network of α-Al2O3 and GAP phases without any other phases. Therefore, the interphase spacing was refined to 1-2 µm and the irregular microstructure led to an outstanding vickers hardness of 17.04 GPa and fracture toughness of 6.3 MPa × m1/2 at room temperature.

CoO-doped MgO-Al2O3-SiO2-colored transparent glass-ceramics with high crystallinity

NASA Astrophysics Data System (ADS)

Tang, Wufu; Zhang, Qian; Luo, Zhiwei; Yu, Jingbo; Gao, Xianglong; Li, Yunxing; Lu, Anxian

2018-02-01

To obtain CoO-doped MgO-Al2O3-SiO2 (MAS)-colored transparent glass-ceramics with high crystallinity, the glass with the composition 21MgO-21Al2O3-54SiO2-4B2O3-0.2CoO (in mol %) was prepared by conventional melt quenching technique and subsequently thermal treated at several temperatures. The crystallization behavior of the glass, the precipitated crystalline phases and crystallinity were analyzed by X-ray diffraction (XRD). The microstructure of the glass-ceramics was characterized by field emission scanning electron microscopy (FSEM). The transmittance of glass-ceramic was measured by UV spectrophotometer. The results show that a large amount of α-cordierite (indianite) with nano-size was precipitated from the glass matrix after treatment at 1020 °C for 3 h. The crystallinity of the transparent glass-ceramic reached up to 97%. Meanwhile, the transmittance of the glass-ceramic was 74% at 400 nm with a complex absorption band from 450 nm to 700 nm. In addition, this colored transparent glass-ceramic possessed lower density (2.469 g/cm3), lower thermal expansion coefficient (1.822 × 10-6 /℃), higher Vickers hardness (9.1 GPa) and higher bending strength (198 MPa) than parent glass.

Electrochemically influenced cation inter-diffusion and Co 3O 4 formation on La 0.6Sr 0.4CoO 3 infiltrated into SOFC cathodes

DOE PAGES

Song, Xueyan; Lee, Shiwoo; Chen, Yun; ...

2015-06-18

Nanosized LSC electrocatalyst was infiltrated into a porous scaffold cathode composed of Sm 2O 3-doped CeO 2 (SDC) and La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF) in a commercial button solid oxide fuel cell (SOFC). To understand the stability of cathodes infiltrated with LSC, the infiltrated composite cells were subjected to both electrochemical operating and thermal aging states at 750 °C for 1500 h. Nanostructure and local chemistry evolution of La 0.6Sr 0.4CoO 3 (LSC) infiltrated cathodes upon operation and aging were investigated by transmission electron microscopy. After operation, the LSC remained a cubic perovskite, and the crystal grains exhibitmore » comparable size to as-infiltrated LSC grains. Inter-diffusion of Fe from the LSCF to a Fe-incorporated LSC layer developed on the LSCF backbone. However, only sharp interfaces were observed between LSC and SDC backbone in the as-infiltrated cathode and such interfaces remain after operation. The infiltrated LSC on the SDC backbone also retains granular particle morphology. Furthermore, newly grown Co 3O 4 nanocrystals were found in the operated cathode. After thermal aging, on the other hand, cation inter-diffusion across the interfaces of the infiltrate particles and the cathode backbones is less than that from the operated cells. Lastly, the following hypothesis is proposed: Co 3O 4 forms on LSC arising from local charge balancing between cobalt and oxygen vacancies.« less

Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts.

PubMed

Cheng, Fangyi; Shen, Jian; Peng, Bo; Pan, Yuede; Tao, Zhanliang; Chen, Jun

2011-01-01

Spinels can serve as alternative low-cost bifunctional electrocatalysts for oxygen reduction/evolution reactions (ORR/OER), which are the key barriers in various electrochemical devices such as metal-air batteries, fuel cells and electrolysers. However, conventional ceramic synthesis of crystalline spinels requires an elevated temperature, complicated procedures and prolonged heating time, and the resulting product exhibits limited electrocatalytic performance. It has been challenging to develop energy-saving, facile and rapid synthetic methodologies for highly active spinels. In this Article, we report the synthesis of nanocrystalline M(x)Mn(3-x)O(4) (M = divalent metals) spinels under ambient conditions and their electrocatalytic application. We show rapid and selective formation of tetragonal or cubic M(x)Mn(3-x)O(4) from the reduction of amorphous MnO(2) in aqueous M(2+) solution. The prepared Co(x)Mn(3-x)O(4) nanoparticles manifest considerable catalytic activity towards the ORR/OER as a result of their high surface areas and abundant defects. The newly discovered phase-dependent electrocatalytic ORR/OER characteristics of Co-Mn-O spinels are also interpreted by experiment and first-principle theoretical studies.

Analysis of the CO 2 Chemisorption in Li 5FeO 4, a New High Temperature CO 2 Captor Material. Effect of the CO 2 and O 2 Partial Pressures

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

Lara-García, Hugo A.; Sanchez-Camacho, Pedro; Duan, Yuhua

Pentalithium ferrite (Li 5FeO 4) was tested in this paper as possible CO 2 captor, both by theoretical calculations and experimental measurements. The pristine Li 5FeO 4 compound with orthorhombic structure was synthesized via solid-state reaction and it was structural and microstructurally characterized. Later, sample was heat-treated at temperatures from room temperature to 900 °C under different CO 2 or CO 2–O 2 atmospheres. Li 5FeO 4 exhibits excellent CO 2 chemisorption abilities with a capture capacity about 12.9 mmol/g, which is outstanding in comparison to other previously reported ceramic captors. This material is able to react with CO 2more » from 200 °C to approximately 715 °C showing a high kinetic of reaction even at CO 2 partial pressure values as low as 0.2. Finally and additionally, results suggest that oxygen addition does enhance the CO 2 chemisorption on Li 5FeO 4 at temperatures below 700 °C, although oxygen addition seems to favor the desorption process at higher temperatures.« less

Analysis of the CO 2 Chemisorption in Li 5FeO 4, a New High Temperature CO 2 Captor Material. Effect of the CO 2 and O 2 Partial Pressures

DOE PAGES

Lara-García, Hugo A.; Sanchez-Camacho, Pedro; Duan, Yuhua; ...

2017-01-23

Pentalithium ferrite (Li 5FeO 4) was tested in this paper as possible CO 2 captor, both by theoretical calculations and experimental measurements. The pristine Li 5FeO 4 compound with orthorhombic structure was synthesized via solid-state reaction and it was structural and microstructurally characterized. Later, sample was heat-treated at temperatures from room temperature to 900 °C under different CO 2 or CO 2–O 2 atmospheres. Li 5FeO 4 exhibits excellent CO 2 chemisorption abilities with a capture capacity about 12.9 mmol/g, which is outstanding in comparison to other previously reported ceramic captors. This material is able to react with CO 2more » from 200 °C to approximately 715 °C showing a high kinetic of reaction even at CO 2 partial pressure values as low as 0.2. Finally and additionally, results suggest that oxygen addition does enhance the CO 2 chemisorption on Li 5FeO 4 at temperatures below 700 °C, although oxygen addition seems to favor the desorption process at higher temperatures.« less

Oxygen potentials and phase equilibria in the system Ca–Co–O and thermodynamic properties of Ca{sub 3}Co{sub 2}O{sub 6} and Ca{sub 3}Co{sub 4}O{sub 9.163}

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

Jacob, K.T., E-mail: katob@materials.iisc.ernet.in; Gupta, Preeti

2015-01-15

Oxygen potentials established by the equilibrium between three condensed phases, CaO{sub ss}+CoO{sub ss}+Ca{sub 3}Co{sub 2}O{sub 6} and CoO{sub ss}+Ca{sub 3}Co{sub 2}O{sub 6}+Ca{sub 3}Co{sub 3.93+α}O{sub 9.36−δ}, are measured as a function of temperature using solid-state electrochemical cells incorporating yttria-stabilized zirconia as the electrolyte and pure oxygen as the reference electrode. Cation non-stoichiometry and oxygen non-stoichiometry in Ca{sub 3}Co{sub 3.93+α}O{sub 9.36−δ} are determined using different techniques under defined conditions. Decomposition temperatures and thermodynamic properties of Ca{sub 3}Co{sub 2}O{sub 6} and Ca{sub 3}Co{sub 4}O{sub 9.163} are calculated from the results. The standard entropy and enthalpy of formation of Ca{sub 3}Co{sub 2}O{sub 6} atmore » 298.15 K are evaluated. Using thermodynamic data from this study and auxiliary information from the literature, phase diagram for the ternary system Ca–Co–O is computed. Isothermal sections at representative temperatures are displayed to demonstrate the evolution of phase relations with temperature. - Graphical abstract: Isothermal section of the phase diagram of the system Ca–Co–O at 1250 K. - Highlights: • Improved definition of cation and oxygen nonstoichiometry of Ca{sub 3}Co{sub 3.93+α}O{sub 9.36−δ}. • Measurement of Δμ{sub O{sub 2}} associated with two 3-phase fields as a function of temperature. • Use of solid-state electrochemical cells for accurate measurement of Δμ{sub O{sub 2}}. • Decomposition temperatures and thermodynamic properties for ternary oxides. • Characterization of ternary phase diagram of the system Ca–Co–O.« less

Hollow structured carbon-supported nickel cobaltite nanoparticles as an efficient bifunctional electrocatalyst for the oxygen reduction and evolution reaction

DOE PAGES

Wang, Jie; Han, Lili; Lin, Ruoqian; ...

2016-01-05

Here, the exploration of efficient electrocatalysts for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is essential for fuel cells and metal-air batteries. In this study, we developed 3D hollow-structured NiCo 2O 4/C nanoparticles with interconnected pores as bifunctional electrocatalysts, which are transformed from solid NiCo 2 alloy nanoparticles through the Kirkendall effect. The unique hollow structure of NiCo 2O 4 nanoparticles increases the number of active sites and improves contact with the electrolyte to result in excellent ORR and OER performances. In addition, the hollow-structured NiCo 2O 4/C nanoparticles exhibit superior long-term stability for both themore » ORR and OER compared to commercial Pt/C. The template- and surfactant-free synthetic strategy could be used for the low-cost and large-scale synthesis of hollow-structured materials, which would facilitate the screening of high-efficiency catalysts for energy conversion.« less

Ultrasonic-assisted in-situ fabrication of BiOBr modified Bi2O2CO3 microstructure with enhanced photocatalytic performance.

PubMed

Cheng, Lijun; Hu, Xumin; Hao, Liang

2018-06-01

Via an ultrasonic-assisted in-situ etching method, BiOBr modified Bi 2 O 2 CO 3 microstructures were fabricated in short time. The samples were characterized by XRD, SEM, TEM, BET, UV-Vis, XPS and PL spectra methods. Rhodamine B (RhB) aqueous solution was applied to evaluate the photocatalytic activities of the as-prepared samples. The results showed that the sample prepared at pH of 2 in which the molar ratio of BiOBr and Bi 2 O 2 CO 3 was 0.69:1 had the largest specific surface area, the best utilization for ultraviolet and visible light and efficient separation efficiency of charge carriers, contributing to its best photocatalytic activity. O 2 - was proved to be main active species in RhB photodegradation process. Last, the photocatalytic mechanism of the composite was discussed in detail. Copyright © 2018 Elsevier B.V. All rights reserved.

Efficient and accurate approach to modeling the microstructure and defect properties of LaCoO3

NASA Astrophysics Data System (ADS)

Buckeridge, J.; Taylor, F. H.; Catlow, C. R. A.

2016-04-01

Complex perovskite oxides are promising materials for cathode layers in solid oxide fuel cells. Such materials have intricate electronic, magnetic, and crystalline structures that prove challenging to model accurately. We analyze a wide range of standard density functional theory approaches to modeling a highly promising system, the perovskite LaCoO3, focusing on optimizing the Hubbard U parameter to treat the self-interaction of the B-site cation's d states, in order to determine the most appropriate method to study defect formation and the effect of spin on local structure. By calculating structural and electronic properties for different magnetic states we determine that U =4 eV for Co in LaCoO3 agrees best with available experiments. We demonstrate that the generalized gradient approximation (PBEsol +U ) is most appropriate for studying structure versus spin state, while the local density approximation (LDA +U ) is most appropriate for determining accurate energetics for defect properties.

Microstructure Evolution During Warm Working of Ti-6Al-4V with a Colony Alpha Microstructure (Preprint)

DTIC Science & Technology

2008-09-01

6 maps such as those shown in Fig. 4 ; typical examples of the cumulative misorientation are given in Figs. 5 and 6 , respectively...misorientation line scans shown in Figs. 5 and 6 . Fig. 5. Typical line scans from EBSD maps in Fig. 4 showing the variation of orientation over a long...e g 0 2 4 6 8 10 12 14 16 (b) Distance, μm 0 20 40 60 80 100 C u m u l a t i v e m i s o r i e n t a t i o n , d e g 0 5 10 15

Effect of Thermochemical Synthetic Conditions on the Structure and Dielectric Properties of Ga1.9Fe0.1O3 Compounds.

PubMed

Roy, Swadipta; Ramana, C V

2018-02-05

We report on the tunable and controlled dielectric properties of iron (Fe)-doped gallium oxide (Ga 2 O 3 ; Ga 1.9 Fe 0.1 O 3 , referred to as GFO) inorganic compounds. The GFO materials were synthesized using a standard high-temperature, solid-state chemical reaction method by varying the thermochemical processing conditions, namely, different calcination and sintering environments. Structural characterization by X-ray diffraction revealed that GFO compounds crystallize in the β-Ga 2 O 3 phase. The Fe doping has induced slight lattice strain in GFO, which is evident in structural analysis. The effect of the sintering temperature (T sint ), which was varied in the range of 900-1200 °C, is significant, as revealed by electron microscopy analysis. T sint influences the grain size and microstructure evolution, which, in turn, influences the dielectric and electrical properties of GFO compounds. The energy-dispersive X-ray spectrometry and mapping data demonstrate the uniform distribution of the elemental composition over the microstructure. The temperature- and frequency-dependent dielectric measurements indicate the characteristic features that are specifically due to Fe doping in Ga 2 O 3 . The spreading factor and relaxation time, calculated using Cole-Cole plots, are in the ranges of 0.65-0.76 and 10 -4 s, respectively. The results demonstrate that densification and control over the microstructure and properties of GFO can be achieved by optimizing T sint .

Long-Term High-Temperature Stability of Directionally Grown [Bi2Ba2O4]p[CoO2] Rods

PubMed Central

Diez, Juan C.; Madre, María A.; Torres, Miguel A.; Rasekh, Shahed; Sotelo, Andrés

2017-01-01

[Bi2Ba2O4]p[CoO2] thermoelectric ceramics have been successfully grown from the melt using the laser floating zone method, followed by a thermal treatment at 700 °C under air between 0 and 1532 h. The microstructural, thermoelectric, and mechanical properties were evaluated as a function of the thermal treatment length. Microstructure has shown that as-grown samples are composed of thermoelectric grains, together with a relatively high amount of secondary phases. Thermal treatment decreased the number and amount of secondary phases, producing nearly single-phase samples after 384 h. Consequently, the thermoelectric properties evaluated through the power factor showed a slight increase with the thermal treatment length, mainly due to the decrease of electrical resistivity, while the Seebeck coefficient was nearly unchanged. On the other hand, flexural strength was practically constant after 24 h thermal treatment. PMID:28772506

Kinetics and mechanism of corrosion of SiC by molten salts

NASA Technical Reports Server (NTRS)

Jacobson, N. S.

1986-01-01

Corrosion of sintered alpha-SiC under thin films of Na2CO3/CO2, Na2SO4/O2, and Na2SO4/SO3 was investigated at 1000 C. Chemical analysis was used to follow silicate and silica evolution as a function of time. This information coupled with morphology observations leads to a detailed corrosion mechanism. In all cases the corrosion reactions occur primarily in the first few hours. In the Na2CO3/CO2 case, rapid oxidation and dissolution lead to a thick layer of silicate melt in about 0.25 h. After this, silica forms a protective layer on the carbide. In the Na2SO4/O2 case, a similar mechanism occurs. In the Na2SO4/SO3 case, a porous nonprotective layer of SiO2 grows directly on the carbide, and a silicate melt forms above this. In addition, SiO2 and regenerated Na2SO4 form at the melt/gas interface due to reaction of silicate with SO3 and SO2 + O2. The reaction slows when the lower silica layer becomes nonporous.

Heterogeneous Electrocatalyst with Molecular Cobalt Ions Serving as the Center of Active Sites.

PubMed

Wang, Jiong; Ge, Xiaoming; Liu, Zhaolin; Thia, Larissa; Yan, Ya; Xiao, Wei; Wang, Xin

2017-02-08

Molecular Co 2+ ions were grafted onto doped graphene in a coordination environment, resulting in the formation of molecularly well-defined, highly active electrocatalytic sites at a heterogeneous interface for the oxygen evolution reaction (OER). The S dopants of graphene are suggested to be one of the binding sites and to be responsible for improving the intrinsic activity of the Co sites. The turnover frequency of such Co sites is greater than that of many Co-based nanostructures and IrO 2 catalysts. Through a series of carefully designed experiments, the pathway for the evolution of the Co cation-based molecular catalyst for the OER was further demonstrated on such a single Co-ion site for the first time. The Co 2+ ions were successively oxidized to Co 3+ and Co 4+ states prior to the OER. The sequential oxidation was coupled with the transfer of different numbers of protons/hydroxides and generated an active Co 4+ ═O fragment. A side-on hydroperoxo ligand of the Co 4+ site is proposed as a key intermediate for the formation of dioxygen.

Characterisations Of Al{sub 2}O{sub 3}-13% Wt TiO{sub 2} Deposition On Mild Steel Via Plasma Spray Method

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

Yusoff, N. H.; Isa, M. C.; Ghazali, M. J.

2011-01-17

To date, plasma sprayed alumina titania have been widely used as wear resistance coatings in textile, machinery and printing industries. Previous studies showed that the coating microstructures and properties were strongly depended on various parameters such as ceramic composition, grain size powders and spray parameters, thus, influencing the melting degree of the alumina titania during the deposition process. The aim of this study focuses on the evolution of the micron sizes of alumina-13%wt titania at different plasma spray power, ranging from 20kW to 40kW. It was noted that the coating porosity of alumina-13%wt titania were decreased from 6.2% to 4%more » by increasing the plasma power from 20 to 40 kW. At lower power value, partially melted powders were deposited, generating over 6% porosity within the microstructures. Percentage of porosity about 5.6% gave the best ratio of bi-modal structures, providing the highest microhardness value. Furthermore, the effect of microstructure and porosity formation on wear resistance was also discussed. Coatings with less porosity exhibited better resistance to wear, in which the wear resistance of coated mild steel possessed only {approx}5 x 10{sup -4} cm{sup 3}/Nm with 4% of porosity.« less

Unique Features of the Photocatalytic Reduction of H2O and CO2 by New Catalysts Based on the Analogues of CdS, Cd4P2X3 (X = Cl, Br, I).

PubMed

Roy, Anand; Chhetri, Manjeet; Prasad, Suchitra; Waghmare, Umesh V; Rao, C N R

2018-01-24

Photochemical reduction of H 2 O and CO 2 has been investigated with a new family of catalysts of the formula Cd 4 P 2 X 3 (X= Cl, Br, I), obtained by the complete aliovalent substitution of the sulfide ions in CdS by P and X (Cl, Br, I). Unlike CdS, the Cd 4 P 2 X 3 compounds exhibit hydrogen evolution and CO 2 reduction from water even in the absence of a sacrificial agent or a cocatalyst. Use of Ni x P y as the cocatalyst, enhances hydrogen evolution, reaching 3870 (apparent quantum yield (AQY) = 4.11) and 9258 (AQY = 9.83) μmol h -1 g -1 , respectively, under artificial and natural (sunlight) irradiation, in the case of Cd 4 P 2 Br 3 /Ni x P y . Electrochemical and spectroscopic studies have been employed to understand the photocatalytic activity of this family of compounds. Unlike most of the semiconductor-based photocatalysts, Cd 4 P 2 X 3 catalysts reduce CO 2 to CO and CH 4 in the absence of sacrificial-agent or cocatalyst using water as the electron source. CO, CH 4 , and H 2 have been obtained with these catalysts under artificial as well as sun-light irradiation. First-principles, calculations have been carried out to understand the electronic structure and catalytic features of these new catalysts.

Preparation and characterization of SnO2 and Carbon Co-coated LiFePO4 cathode materials.

PubMed

Wang, Haibin; Liu, Shuxin; Huang, Yongmao

2014-04-01

The SnO2 and carbon co-coated LiFePO4 cathode materials were successfully synthesized by solid state method. The microstructure and morphology of LiFePO4 composites were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy and transmission electron microscope. The results showed that the SnO2 and carbon co-coated LiFePO4 cathode materials exhibited more uniform particle size distribution. Compared with the uncoated LiFePO4/C, the structure of LiFePO4 with SnO2 and carbon coating had no change. The existence of SnO2 and carbon coating layer effectively enhanced the initial discharge capacity. Among the investigated samples, the one with DBTDL:LiFePO4 molar ratios of 7:100 exhibited the best electrochemical performance.

About properties of ZrO2 thermal protective coatings obtained from spherical powder mixtures

NASA Astrophysics Data System (ADS)

Berdnik, O. B.; Tsareva, I. N.; Tarasenko, Yu P.

2017-05-01

It is developed the technology of high-energy plasma spraying of the zirconium dioxide (ZrO2) thermal protective coating on the basis of ZrO2 tetragonal and cubic phases with the spheroidal grain shape and the columnar substructure, with the total porosity P = 4 %, the hardness HV = 12 GPa, the roughness parameter R a ˜ 6 μm, the thickness 0.3-3 mm. As a sublayer it is used the heat-resistant coating of “Ni-Co-Cr-Al-Y” system with an intermetallic phase composition and the layered microstructure of the grains.

Oxidation behaviour of ferritic stainless steel grade Crofer 22 APU at 700 °C in flowing Ar−75%CO{sub 2}−12%H{sub 2}O

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

Shariff, Nurul Atikah; Othman, Norinsan Kamil; Jalar, Azman

2013-11-27

The oxidation of Ferritic Stainless Steel (FSS) grade Crofer 22 APU has been investigated. FSS alloys were exposed to isothermal conditions in a horizontal tube furnace at a 700 °C in flowing Ar−75%CO{sub 2}−12%H{sub 2}O at a pressure of approximately 1 atm. The results showed that the growth of non protective Fe{sub 2}O{sub 3} and spinel was observed after 50 h exposure in the presence of 12% H{sub 2}O. The weight was increased significantly with time of exposure. The formation of different oxides is presented on the interface of the specimen such as MnCr{sub 2}O{sub 4}, Fe{sub 3}O{sub 4} andmore » Fe{sub 2}O{sub 3} were revealed by X-ray diffraction and supported by EDAX analysis. FSS did not form a protective Cr{sub 2}O{sub 3} layer due to water vapour accelerates the kinetics oxidation. Data of microstructure observation is presented and discussed in this paper in term of water vapour effects.« less

Optical and electrical properties of Mn1.56Co0.96Ni0.48O4 thin films

NASA Astrophysics Data System (ADS)

Gao, Y. Q.; Huang, Z. M.; Hou, Y.; Wu, J.; Chu, J. H.

2013-12-01

Mn1.56Co0.96Ni0.48O4 (MCN) films with different layers have been prepared on Al2O3 substrate by chemical solution deposition method. The microstructures, optical and electrical properties of the films are investigated. X-ray diffraction and microstructure analyses show good crystallization and both the crystalline quality and the grain size are improved with the increasing thickness of the films. Mid-infrared optical properties of MCN films have been investigated using transmission spectra. The results show the red shift of absorption with the increasing film thickness and the energy gap Eg decrease from 0.6422 eV to 0.6354 eV. All the MCN films show an exponential decrease in the resistivity with increasing temperature within the measured range. The temperature dependence resistivity can be described by the small polarons hopping model. Using this model, the characteristic temperature T0 and activation energy E of the MCN films were derived. With the film thickness increase, the T0 and E of the MCN films increase. The calculated room temperature coefficient of resistance (TCR) of MCN film with 100 layers is -3.5% K-1. The MCN films showed appropriate resistance and high value of TCR, these advantages make them very preponderant for thermal sensors.

(S)TEM analysis of functional transition metal oxides

NASA Astrophysics Data System (ADS)

Chi, Miaofang

Perovskite vanadates (AVO3) form an ideal family to study the structure-property relationships in transition metal oxides because their physical properties can easily be tailored by varying the A-site cations. (S)TEM is an ideal tool for this type of study due to its capacity for simultaneous imaging and chemical analysis. Determination of the oxidation state of vanadium in complex oxides have been carried out by electron energy loss spectroscopy. SrVO3/LaAlO3 is then studied both experimentally and theoretically as a prototype system. Extra electrons have been detected on the interface layer, and further proven to originate mainly from a change in the local bonding configuration of V at the La-O terminated substrate surface. Cr-containing stainless steel deposited with a LaCrO3 thin-film layer is a promising interconnect material of Solid Oxide Fuel Cells (SOFC). Our investigation on its microstructural evolution reveals that the LaCrO 3 thin film plays a role in inhibiting the growth of an oxide layer on the metal surface and thus protects the surface of the stainless steel. Ca-doped LaCoO3 is a promising SOFC cathode material. The domain structures and the oxidation state of Co in Ca-doped LaCoO3, which are directly related to its mechanical properties and electronic conductivity, are investigated by in-situ TEM and EELS. The formation of microcracks is observed during thermal cycles. Ca-doping in LaCoO3 is shown to not only improve the electronic conductivity of the material, but is also likely to strengthen the grain boundaries. The realization of its application in SOFCs depends on depressing the ferroelastisity to reduce strain formation during thermal cycles. The application of the (S)TEM techniques used for studying the perovskite systems are further extended to other compounds containing transition metal elements. The refractory minerals from Comet 81 P/Wild-2 are studied to investigate the formation of the early solar system. A relatively high Ti3+/Ti 4+ ratio in fassaite and the presence of osbornite indicate that the Comet refractory minerals formed in the inner solar nebula and were later transported to the outer solar system where the comet formed. This implies a much more dynamic and perhaps more violent solar nebula than was previously suspected.

A polymerized C60 coating enhancing interfacial stability at three-dimensional LiCoO2 in high-potential regime

NASA Astrophysics Data System (ADS)

Hudaya, Chairul; Halim, Martin; Pröll, Johannes; Besser, Heino; Choi, Wonchang; Pfleging, Wilhelm; Seifert, Hans Jürgen; Lee, Joong Kee

2015-12-01

The interfacial instabilities, including side reactions due to electrolyte decompositions and Cobalt (Co) dissolutions, are the main detrimental processes at LiCoO2 cathode when a high-voltage window (>4.2 V) is applied. Nevertheless, cycling the cathode with a voltage above 4.2 V would deliver an increased gravimetric capacity, which is desired for high power battery operation. To address these drawbacks, we demonstrate a synergistic approach by manufacturing the three-dimensional high-temperature LiCoO2 electrodes (3D HT-LCO) using laser-microstructuring, laser-annealing and subsequent coating with polymerized C60 thin films (C60@3D HT-LCO) by plasma-assisted thermal evaporation. The C60@3D HT-LCO cathode delivers higher initial discharge capacity compared to its theoretical value, i.e. 175 mA h g-1 at 0.1 C with cut-off voltage of 3.0-4.5 V. This cathode combines the advantages of the 3D electrode architecture and an advanced C60 coating/passivation concept leading to an improved electrochemical performance, due to an increased active surface area, a decreased charge transfer resistance, a prevented Co dissolution into the electrolyte and a suppressed side reaction and electrolyte decomposition. This work provides a novel solution for other cathode materials having similar concerns in high potential regimes for application in lithium-ion microbatteries.

Flexible and High Performance Supercapacitors Based on NiCo2O4for Wide Temperature Range Applications

NASA Astrophysics Data System (ADS)

Gupta, Ram K.; Candler, John; Palchoudhury, Soubantika; Ramasamy, Karthik; Gupta, Bipin Kumar

2015-10-01

Binder free nanostructured NiCo2O4 were grown using a facile hydrothermal technique. X-ray diffraction patterns confirmed the phase purity of NiCo2O4. The surface morphology and microstructure of the NiCo2O4 analyzed by scanning electron microscopy (SEM) showed flower-like morphology composed of needle-like structures. The potential application of binder free NiCo2O4 as an electrode for supercapacitor devices was investigated using electrochemical methods. The cyclic voltammograms of NiCo2O4 electrode using alkaline aqueous electrolytes showed the presence of redox peaks suggesting pseudocapacitance behavior. Quasi-solid state supercapacitor device fabricated by sandwiching two NiCo2O4 electrodes and separating them by ion transporting layer. The performance of the device was tested using cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy. The device showed excellent flexibility and cyclic stability. The temperature dependent charge storage capacity was measured for their variable temperature applications. Specific capacitance of the device was enhanced by ~150% on raising the temperature from 20 to 60 °C. Hence, the results suggest that NiCo2O4 grown under these conditions could be a suitable material for high performance supercapacitor devices that can be operated at variable temperatures.

Flexible and High Performance Supercapacitors Based on NiCo2O4for Wide Temperature Range Applications.

PubMed

Gupta, Ram K; Candler, John; Palchoudhury, Soubantika; Ramasamy, Karthik; Gupta, Bipin Kumar

2015-10-20

Binder free nanostructured NiCo2O4 were grown using a facile hydrothermal technique. X-ray diffraction patterns confirmed the phase purity of NiCo2O4. The surface morphology and microstructure of the NiCo2O4 analyzed by scanning electron microscopy (SEM) showed flower-like morphology composed of needle-like structures. The potential application of binder free NiCo2O4 as an electrode for supercapacitor devices was investigated using electrochemical methods. The cyclic voltammograms of NiCo2O4 electrode using alkaline aqueous electrolytes showed the presence of redox peaks suggesting pseudocapacitance behavior. Quasi-solid state supercapacitor device fabricated by sandwiching two NiCo2O4 electrodes and separating them by ion transporting layer. The performance of the device was tested using cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy. The device showed excellent flexibility and cyclic stability. The temperature dependent charge storage capacity was measured for their variable temperature applications. Specific capacitance of the device was enhanced by ~150% on raising the temperature from 20 to 60 °C. Hence, the results suggest that NiCo2O4 grown under these conditions could be a suitable material for high performance supercapacitor devices that can be operated at variable temperatures.

Flexible and High Performance Supercapacitors Based on NiCo2O4for Wide Temperature Range Applications

PubMed Central

Gupta, Ram K.; Candler, John; Palchoudhury, Soubantika; Ramasamy, Karthik; Gupta, Bipin Kumar

2015-01-01

Binder free nanostructured NiCo2O4 were grown using a facile hydrothermal technique. X-ray diffraction patterns confirmed the phase purity of NiCo2O4. The surface morphology and microstructure of the NiCo2O4 analyzed by scanning electron microscopy (SEM) showed flower-like morphology composed of needle-like structures. The potential application of binder free NiCo2O4 as an electrode for supercapacitor devices was investigated using electrochemical methods. The cyclic voltammograms of NiCo2O4 electrode using alkaline aqueous electrolytes showed the presence of redox peaks suggesting pseudocapacitance behavior. Quasi-solid state supercapacitor device fabricated by sandwiching two NiCo2O4 electrodes and separating them by ion transporting layer. The performance of the device was tested using cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy. The device showed excellent flexibility and cyclic stability. The temperature dependent charge storage capacity was measured for their variable temperature applications. Specific capacitance of the device was enhanced by ~150% on raising the temperature from 20 to 60 °C. Hence, the results suggest that NiCo2O4 grown under these conditions could be a suitable material for high performance supercapacitor devices that can be operated at variable temperatures. PMID:26482921

Fabrication of Mg-X-O (X = Fe, Co, Ni, Cr, Mn, Ti, V, and Zn) barriers for magnetic tunnel junctions

NASA Astrophysics Data System (ADS)

Yakushiji, K.; Kitagawa, E.; Ochiai, T.; Kubota, H.; Shimomura, N.; Ito, J.; Yoda, H.; Yuasa, S.

2018-05-01

We fabricated magnetic tunnel junctions with a 3d-transition material(X)-doped MgO (Mg-X-O) barrier, and evaluated the effect of the doping on magnetoresistance (MR) and microstructure. Among the variations of X (X = Fe, Co, Ni, Cr, Mn, Ti, V, and Zn), X = Fe and Mn showed a high MR ratio of more than 100%, even at a low resistance-area product of 3 Ωμm2. The microstructure analysis revealed that (001) textured orientation formed for X = Fe and Mn despite substantial doping (about 10 at%). The elemental mappings indicated that Fe atoms in the Mg-Fe-O barrier were segregated at the interfaces, while Mn atoms were evenly involved in the Mg-Mn-O barrier. This suggests that MgO has high adaptability for Fe and Mn dopants in terms of high MR ratio.

Synthesis and study of structural, microstructural and dielectric properties of Ce3+ doped Co-Ni ferrites for automotive applications

NASA Astrophysics Data System (ADS)

Srinivasamurthy, K. M.; Angadi, V. Jagadeesha; Kumar, P. Mohan; Nagaraj, B. S.; Deepthy, P. R.; Pasha, U. Mahaboob; Rudraswamy, B.

2018-05-01

Nano crystalline spinel ferrites of Co0.5Ni0.5CexFe2-xO4 (x=0.01, 0.015, 0.02, 0.025 and 0.03) was prepared by modified solution combustion method using a mixture of fuels for the first time. The influence of rare earth Ce3+ substitution at the Fe3+ site on the structural, microstructural and dielectric properties of Co0.5Ni0.5CexFe2-xO4 was investigated. The X-ray diffraction (XRD) studies confirmed the formation of monophasic nano crystalline samples without any secondary phases. The crystallite size decreases and density increases with the increases of Ce3+ contents. Surface morphology was studied through Scanning Electron Microscopy (SEM). Dielectric properties of these ferrites have been studied at room temperature using impedance analyzer in the frequency range up to 20 MHz. The effect of frequency and composition on dielectric constant (ɛ'), dielectric loss (tanδ) and ac conductivity (σac) have been discussed in terms of hopping of charge carriers (Fe2+↔Fe3+). The decrease in dielectric loss with frequency follows Debye's relaxation phenomena. Both the variation in tan loss and dielectric loss with frequency shows a similar. AC conductivity increases with the increases of frequency which directly proportional to concentration of Ce3+ ions follows Jonscher law. These Cerium doped Cobalt-nickel ferrites are very helpful for automotive applications.

Effects of torsional deformation on the microstructures and mechanical properties of a CoCrFeNiMo0.15 high-entropy alloy

NASA Astrophysics Data System (ADS)

Wu, Wenqian; Guo, Lin; Liu, Bin; Ni, Song; Liu, Yong; Song, Min

2017-12-01

The effects of torsional deformation on the microstructures and mechanical properties of a CoCrFeNiMo0.15 high-entropy alloy have been investigated. The torsional deformation generates a gradient microstructure distribution due to the gradient torsional strain. Both dislocation activity and deformation twinning dominated the torsional deformation process. With increasing the torsional equivalent strain, the microstructural evolution can be described as follows: (1) formation of pile-up dislocations parallel to the trace of {1 1 1}-type slip planes; (2) formation of Taylor lattices; (3) formation of highly dense dislocation walls; (3) formation of microbands and deformation twins. The extremely high deformation strain (strained to fracture) results in the activation of wavy slip. The tensile strength is very sensitive to the torsional deformation, and increases significantly with increasing the torsional angle.

Evaluation of La0.6Sr0.4Co0.2Fe0.8O3-Gd0.1Ce0.9O1.95 composite cathode with three dimensional microstructure reconstruction

NASA Astrophysics Data System (ADS)

Kim, Y. T.; Jiao, Z.; Shikazono, N.

2017-02-01

In the present study, the polarization characteristics of La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) - Gd0.1Ce0.9O1.95 (GDC) composite cathodes with different volume ratios were investigated. Samples with volume ratios of 20:80, 30:70, 50:50, 70:30 and 100:0 vol % were tested. The electrochemical impedance spectroscopy tests and current voltage curve measurements were carried out for the current densities from 0 to 0.2 Acm-2 with an interval of 0.05 Acm-2. The results showed that a volume ratio of LSCF:GDC = 30:70 composite cathode led to the lowest overpotential, and the overpotential increased in the order of 30:70, 50:50, 70:30, 100:0, 20:80 vol %. Three dimensional microstructures of composite cathodes were reconstructed and quantified by dual beam focused ion beam-scanning electron microscope (FIB-SEM). The results showed that neither LSCF surface area nor triple phase boundary (TPB) alone could explain the dependence of polarization characteristics on volume ratios. Current and electrochemical potential distributions were simulated by the Lattice Boltzmann method, in which both surface and TPB reactions were considered. Prediction considering both surface and TPB reactions could predict qualitatively the dependence of overpotentials on LSCF - GDC cathode composition.

Characterization of corrosion resistant on NiCoCr coating layer exposed to 5%NaCl

NASA Astrophysics Data System (ADS)

Sugiarti, E.; Sundawa, R.; Desiati, R. D.; Zaini, K. A.

2018-03-01

Highly corrosion resistant of carbon steel coated NiCoCr was applied in corrosive of marine environtment. Carbon steel coated NiCoCr was prepared by a two step technique of NiCo electro-deposition and Cr pack cementation. The samples were exposed to 5 wt.% NaCl for 48 and 168 hours. The microstructure and corrosion product were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The corrosion resistance of carbon steel coated NiCoCr was found to be better than that of carbon steel substrate without coating. The results showed the microstructure of 48 h corroded sample has duplex layer composed of inner α-(Ni,Co), α-Cr and outer Cr2O3, while a quite thin and continues protective oxide of Cr2O3 was observed in outer layer of 168 h corroded sample. The formation of oxide scale rich in Cr2O3 has contributed for the better corrosion resistance of carbon steel coated NiCoCr, whereas the formation of non protective oxide of iron might caused low corrosion resistance of carbon steel substrate.

Investigation on magnetoelectric behavior of (80Bi0.5Na0.5TiO3-20Bi0.5K0.5TiO3)-CoFe2O4 particulate composites

NASA Astrophysics Data System (ADS)

Liu, Sheng; Yan, Shuoqing; Yao, Lingling; He, Jun; He, Longhui; Hu, Zhaowen; Huang, Shengxiang; Deng, Lianwen

2017-12-01

Particulate magnetoelectric (ME) ceramics constituted by (1-x)(80Bi0.5Na0.5TiO3-20Bi0.5K0.5TiO3)-xCoFe2O4 [(1-x)BNKT-xCFO] (x = 0, 0.1, 0.2, 0.3, 0.4 and 1.0) were synthesized by an powder-in-sol precursor hybrid processing method and their structure, magnetic, ferroelectric, magnetodielectric (MD) and ME properties have been investigated. Results showed that the ceramics consisted of only two chemically separated phases and had homogeneous microstructure. The introduction of CFO into BNKT matrix led to the weakening of ferroelectric and dielectric properties whereas the strengthening magnetic and MD properties. The observation of the MD effect revealed the evidence of the strain-induced ME coupling and the MD value is well scaled with M2. A maximum value of ME output of 25.07 mV/cm·Oe was achieved for the 0.7BNKT-0.3CFO composite. The improved ME response together with the linear MD effect makes the ceramics promise for use in magnetic field controllable devices or magneto-electric transducers.

Chemical and Microstructural Changes in Metallic and Ceramic Materials Exposed to Venusian Surface Conditions

NASA Technical Reports Server (NTRS)

Costa, Gustavo C. C.; Jacobson, Nathan S.; Lukco, Dorothy; Hunter, Gary W.; Nakley, Leah; Radoman-Shaw, Brandon G.; Harvey, Ralph P.

2017-01-01

The chemical and microstructural behavior of steels (304, 310, 316, and 1018), nickel-based alloys (beta-NiAl, G30, and 625), gold, coatings (4YSZ, SilcoNert(TradeMark) 1040 (SilcoTek Co.), Dursan(TradeMark)? (SilcoTek Co.), and porcelain), and bulk ceramics (alpha-Al2O3, fused quartz, beta-SiC, and alpha-Si3N4) were probed after exposure to supercritical fluid with temperature, pressure, and composition mimicking the Venus lower atmosphere. Exposures were carried out in the Glenn Extreme Environments Rig (GEER) chamber with the Venusian gas mixture (96.5% CO2, 3.5% N2, 30 ppm H2O, 150 ppm SO2, 28 ppm CO, 15 ppm OCS, 3 ppm H2S, 0.5 ppm HCl, and 5 ppb HF) at 92 bar (1330 psi) and 467 C (873 F) for durations of 10 and 42 days. An additional 21-day exposure was done to stainless steel uncoated and coated with SilcoNert(TradeMark) and Dursan(TradeMark). Samples were characterized before and after the experiment by gravimetric analysis, X-ray diffraction, X-ray photoelectron and Auger electron spectroscopies, and cross section electron microscopy analysis. All steels exposed for 10 and 42 days formed double-layered scales consisting mainly of metal (Cr, Fe, Ni) oxides and sulfides showing different chemistry, microstructure, and crystalline phases. The alloys G30 and 625 formed double-layered scales consisting mainly of nickel sulfides. After 10 days, the beta-NiAl exhibited no detectable scale, suggesting only a very thin film was formed. The 304 and 316 stainless steels coated with 4YSZ that were exposed for 10 and 42 days exhibited no significant oxidation. Steel 1018 coated with 4YSZ exhibited a corrosion scale of iron and/or chromium oxide formed at the base of the alloy. The 304 steel coated with porcelain did not exhibit corrosion, although the coating exhibited recession. SilcoNert(TradeMark) exposed for 10 and 42 days exhibited recession, although no oxidation was found to occur at the base of the alloy. Stainless steel 316 coated with Dursan(TradeMark) ? exhibited corrosion at the base of the alloy. All ceramics tested showed no clear evidence of reaction. The weight-gain-per-area performance of the materials exposed in the GEER for 10 and 42 days are reported from the lowest to the highest weight gain per area as follows: gold did not exhibit any weight change; nickel-based alloys: beta- NiAl < G30 < 625; steels: 304 < 310 < 316 < 1018; ceramics: considering the experimental uncertainties, no weight change was observed for all ceramics of this work (alpha-Al2O3, Si3N4, SiC, and amorphous SiO2).

Phase Separation Kinetics in Isopycnic Mixtures of H2O/CO2/Ethoxylated Alcohol Surfactants

NASA Technical Reports Server (NTRS)

Lesemann, Markus; Paulaitis, Michael E.; Kaler, Eric W.

1999-01-01

Ternary mixtures of H2O and CO2 with ethoxylated alcohol (C(sub i)E(sub j)) surfactants form three coexisting liquid phases at conditions where two of the phases have equal densities (isopycnic phases). Isopycnic phase behavior has been observed for mixtures containing C8E5, C10E6, and C12E6 surfactants, but not for those mixtures containing either C4E1 or C8E3 surfactants. Pressure-temperature (PT) projections for this three-phase equilibrium were determined for H2O/CO2/C8E5 and H2O/CO2/C10E6 mixtures at temperatures from approximately 25 to 33 C and pressures between 90 and 350 bar. Measurements of the microstructure in H2O/CO2/C12E6 mixtures as a function of temperature (25-31 C), pressure (63.1-90.7 bar), and CO2 composition (0-3.9 wt%) have also been carried out to show that while micellar structure remains essentially un-changed, critical concentration fluctuations increase as the phase boundary and plait point are approached. In this report, we present our first measurements of the kinetics of isopycnic phase separation for ternary mixtures of H2O/CO2/C8E5.

A novel ruthenium(II)-cobaloxime supramolecular complex for photocatalytic H2 evolution: Synthesis, characterisation, and mechanistic studies

PubMed Central

Cropek, Donald M.; Metz, Anja; Müller, Astrid M.; Gray, Harry B.; Horne, Toyketa; Horton, Dorothy C.; Poluektov, Oleg; Tiede, David M.; Weber, Ralph T.; Jarrett, William L.; Phillips, Joshua D.

2012-01-01

We report the synthesis and characterization of novel mixed-metal binuclear ruthenium(II)-cobalt(II) photocatalysts for hydrogen evolution in acidic acetonitrile. First, 2-(2′-pyridyl)benzothiazole (pbt), 1, was reacted with RuCl3·xH2O to produce [Ru(pbt)2Cl2] ·0.25CH3COCH3, 2, which was then reacted with 1,10-phenanthroline-5,6-dione (phendione), 3 in order to produce [Ru(pbt)2(phendione)](PF6)2·4H2O, 4. Compound 4 was then reacted with 4-pyridinecarboxaldehyde in order to produce [Ru(pbt)2(L-pyr)](PF6)2·9.5H2O, 5 (where L-pyr = (4-pyridine)oxazolo[4,5-f]phenanthroline). Compound 5 was then reacted with [Co(dmgBF2)2(H2O)2] (where dmgBF2 = difluorboryldimethylglyoximate) in order to produce the mixed-metal binuclear complex, [Ru(pbt)2(L-pyr)Co(dmgBF2)2(H2O)](PF6)2·11H2O·1.5CH3COCH3, 6. [Ru(Me2bpy)2(L-pyr)Co(dmgBF2)2(OH2)](PF6)2, 7 (where Me2bpy = 1,10-phenanthroline, 4,4′-dimethyl-2,2′-bipyridine) and [Ru(phen)2(L-pyr)Co(dmgBF2)2(OH2)](PF6)2, 8 were also synthesised. All complexes were characterized by elemental analysis, UV-visible absorption, 11B, 19F, and 59Co NMR, ESR spectroscopy, and cyclic voltammetry, where appropriate. Photocatalytic studies carried out in acidified acetonitrile demonstrated constant hydrogen generation longer than a 42 hour period as detected by gas chromatography. Time resolved spectroscopic measurements were performed on compound 6, which proved an intramolecular electron transfer from an excited Ru(II) metal centre to the Co(II) metal centre via the bridging L-pyr ligand. This resulted in the formation of a cobalt(I)-containing species that is essential for the production of H2 gas in the presence of H+ ions. A proposed mechanism for the generation of hydrogen is presented. PMID:23001132

High-temperature chemical and microstructural transformations of an organic-inorganic nanohybrid captopril intercalated Mg-Al layered double hydroxide

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

Zhang Hui; Guo Shaohuan; Zou Kang

The thermal evolution of a crystalline organic-inorganic nanohybrid captopril intercalated Mg-Al layered double hydroxide (LDH) [Mg{sub 0.68}Al{sub 0.32}(OH){sub 2}] (C{sub 9}H{sub 13}NO{sub 3}S){sub 0.130}(CO{sub 3}){sub 0.030}.0.53H{sub 2}O obtained by coprecipitation method is studied based upon in situ high-temperature X-ray diffraction, in situ infrared and thermogravimetric analysis coupled with mass spectroscopy analysis. The results reveal that a metastable quasi-interstratified layered nanohybrid involving carbonate-LDH and reoriented less ordered captopril-LDH was firstly observed as captopril-LDH heat-treated between 140 and 230 deg. C. The major decomposition/combustion of interlayer organics occur between 270 and 550 deg. C. A schematic model on chemical and microstructural evolutionmore » of this particular drug-inorganic nanohybrid upon heating in air atmosphere is proposed.« less

Investigation of the laser engineered net shaping process for nanostructured cermets

NASA Astrophysics Data System (ADS)

Xiong, Yuhong

Laser Engineered Net Shaping (LENSRTM) is a solid freeform fabrication (SFF) technology that combines high power laser deposition and powder metallurgy technologies. The LENSRTM technology has been used to fabricate a number of metallic alloys with improved physical and mechanical material properties. The successful application provides a motivation to also apply this method to fabricate non-metallic alloys, such as tungsten carbide-cobalt (WC-Co) cermets in a timely and easy way. However, reports on this topic are very limited. In this work, the LENSRTM technology was used to investigate its application to nanostructured WC-Co cermets, including processing conditions, microstructural evolution, thermal behavior, mechanical properties, and environmental and economic benefits. Details of the approaches are described as follows. A comprehensive analysis of the relationships between process parameters, microstructural evolution and mechanical properties was conducted through various analytical techniques. Effects of process parameters on sample profiles and microstructures were analyzed. Dissolution, shape change and coarsening of WC particles were investigated to study the mechanisms of microstructural evolution. The thermal features were correlated with the microstructure and mechanical properties. The special thermal behavior during this process and its relevant effects on the microstructure have been experimentally studied and numerically simulated. A high-speed digital camera was applied to study the temperature profile, temperature gradient and cooling rate in and near the molten pool. Numerical modeling was employed for 3D samples using finite element method with ADINA software for the first time. The validated modeling results were used to interpret microstructural evolution and thermal history. In order to fully evaluate the capability of the LENSRTM technology for the fabrication of cermets, material properties of WC-Co cermets produced by different powder metallurgy technologies were compared. In addition, another cermet system, nanostructured titanium/tungsten carbide-nickel ((Ti,W)C-Ni) powder, prepared using high-energy ball milling process, was also deposited by the LENSRTM technology. Because of the near net shape feature of the LENSRTM process, special emphasis was also placed on its potential environmental and economic benefits by applying life cycle assessment (LCA) and technical cost modeling (TCM). Comparisons were conducted between the conventional powder metallurgy processes and the LENSRTM process.

Tandem assays of protein and glucose with functionalized core/shell particles based on magnetic separation and surface-enhanced Raman scattering.

PubMed

Kong, Xianming; Yu, Qian; Lv, Zhongpeng; Du, Xuezhong

2013-10-11

Tandem assays of protein and glucose in combination with mannose-functionalized Fe3 O4 @SiO2 and Ag@SiO2 tag particles have promising potential in effective magnetic separation and highly sensitive and selective SERS assays of biomaterials. It is for the first time that tandem assay of glucose is developed using SERS based on the Con A-sandwiched microstructures between the functionalized magnetic and tag particles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

FAST TRACK COMMUNICATION: Mechanical, electrical and micro-structural properties of La0.6Sr0.4Co0.2Fe0.8O3 perovskite-based ceramic foams

NASA Astrophysics Data System (ADS)

Gupta, Ravindra K.; Kim, Eun Yi; Noh, Ho Sung; Whang, Chin Myung

2008-02-01

Mechanical, electrical and micro-structural properties of new electronic conducting ceramic foams are reported. Ceramic foams are prepared using the slurry of La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) by the polymeric sponge method, which is followed by spray coating for increasing the number of coatings-sinterings on polyurethane foams of 30, 45 and 60 ppi (pores per linear inch). An increase in the number of coatings-sinterings and ppi improved the compressive strength, density and electrical conductivity by decreasing the porosity to ~76%, as also observed by the SEM study. The three-times coated-sintered ceramic foams (60 ppi) exhibited optimum values of compressive strength of ~1.79 MPa and relative density of ~0.24 at 25 °C and electrical conductivity of ~22 S cm-1 at 600 °C with an activation energy of ~0.22 eV indicating its suitability as a solid oxide fuel cell current collector. The experimental results are discussed in terms of the Gibson and Ashby theoretical model.

Stratospheric ozone depletion due to nitrous oxide: influences of other gases

PubMed Central

Portmann, R. W.; Daniel, J. S.; Ravishankara, A. R.

2012-01-01

The effects of anthropogenic emissions of nitrous oxide (N2O), carbon dioxide (CO2), methane (CH4) and the halocarbons on stratospheric ozone (O3) over the twentieth and twenty-first centuries are isolated using a chemical model of the stratosphere. The future evolution of ozone will depend on each of these gases, with N2O and CO2 probably playing the dominant roles as halocarbons return towards pre-industrial levels. There are nonlinear interactions between these gases that preclude unambiguously separating their effect on ozone. For example, the CH4 increase during the twentieth century reduced the ozone losses owing to halocarbon increases, and the N2O chemical destruction of O3 is buffered by CO2 thermal effects in the middle stratosphere (by approx. 20% for the IPCC A1B/WMO A1 scenario over the time period 1900–2100). Nonetheless, N2O is expected to continue to be the largest anthropogenic emission of an O3-destroying compound in the foreseeable future. Reductions in anthropogenic N2O emissions provide a larger opportunity for reduction in future O3 depletion than any of the remaining uncontrolled halocarbon emissions. It is also shown that 1980 levels of O3 were affected by halocarbons, N2O, CO2 and CH4, and thus may not be a good choice of a benchmark of O3 recovery. PMID:22451111

The effects of CuO particle size on microstructure evolution of AgCuO compo-sites in plastic deformation process: finite element simulation and experimental study

NASA Astrophysics Data System (ADS)

Li, Zhiguo; Cao, Hanxing; Zhou, Xiaolong; Zhou, Zhaobo; Cao, Jianchun

2018-04-01

The effects of CuO with different particle sizes on the microstructure evolution of AgCuO composite material during plastic deformation process were investigated by finite element (FE) analysis and experiment. The results are as follows: with the decrease of CuO particle size, the degree of radial compression and axial elongation of CuO particle cluster increase gradually, as well as the dispersion of CuO also increase. Meanwhile, the shape of CuO particles is constantly transformed from polygonal to fibrous, which makes the number of linear fibrous CuO increase continuously while bent fibrous CuO reduce gradually. By comparing the simulation and experiment results we find that there are four different typical microstructure regions, which caused by the interaction between monoclinic and cubic CuO during the extrusion process.

Anisotropic electrical and thermal conductivity in Bi{sub 2}AE{sub 2}Co{sub 2}O{sub 8+δ} [AE = Ca, Sr{sub 1−x}Ba{sub x} (x = 0.0, 0.25, 0.5, 0.75, 1.0)] single crystals

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

Dong, Song-Tao; Institute of Material Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003; Zhang, Bin-Bin

Bi{sub 2}AE{sub 2}Co{sub 2}O{sub 8+δ} (AE represents alkaline earth), constructed by stacking of rock-salt Bi{sub 2}AE{sub 2}O{sub 4} and triangle CoO{sub 2} layers alternatively along c-axis, is one of promising thermoelectric oxides. The most impressive feature of Bi{sub 2}AE{sub 2}Co{sub 2}O{sub 8+δ}, as reported previously, is their electrical conductivity mainly lying along CoO{sub 2} plane, adjusting Bi{sub 2}AE{sub 2}O{sub 4} layer simultaneously manipulates both thermal conductivity and electrical conductivity. It in turn optimizes thermoelectric performance of these materials. In this work, we characterize the anisotropic thermal and electrical conductivity along both ab-plane and c-direction of Bi{sub 2}AE{sub 2}Co{sub 2}O{sub 8+δ}more » (AE = Ca, Sr, Ba, Sr{sub 1−x}Ba{sub x}) single crystals. The results substantiate that isovalence replacement in Bi{sub 2}AE{sub 2}Co{sub 2}O{sub 8+δ} remarkably modifies their electrical property along ab-plane; while their thermal conductivity along ab-plane only has a slightly difference. At the same time, both the electrical conductivity and thermal conductivity along c-axis of these materials also have dramatic changes. Certainly, the electrical resistance along c-axis is too high to be used as thermoelectric applications. These results suggest that adjusting nano-block Bi{sub 2}AE{sub 2}O{sub 4} layer in Bi{sub 2}AE{sub 2}Co{sub 2}O{sub 8+δ} cannot modify the thermal conductivity along high electrical conductivity plane (ab-plane here). The evolution of electrical property is discussed by Anderson localization and electron-electron interaction U. And the modification of thermal conductivity along c-axis is attributed to the microstructure difference. This work sheds more light on the manipulation of the thermal and electrical conductivity in the layered thermoelectric materials.« less

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

Sharma, Richa; Tandon, R. P., E-mail: ram-tandon@hotmail.com

In the present work, (1-x)Ba{sub 0.95}Sr{sub 0.05}TiO{sub 3}-(x)CoFe{sub 1.8}Mn{sub 0.2}O{sub 4} composites are prepared by standard solid state reaction method. The X-ray diffraction measurement of the composites shows that both the phases coexist in the composite, individually. The morphology of the composites were examined by field emission scanning electron microscopy and reveals homogeneous microstructure with two types of grains, smaller grains of the Ba{sub 0.95}Sr{sub 0.05}TiO{sub 3} (BST) and bigger grains of the CoFe{sub 1.8}Mn{sub 0.2}O{sub 4} (CFM). The dielectric studies show that all the composites exhibit dispersion in the lower frequency region attributable to the interfacial polarization. In addition,more » at lower frequencies, the dielectric constant (ε´) is found to increase with increase in CFM content in the composites. The ferromagnetic properties of the composites improve with the increase in the CFM content.« less

Comparative investigations on ferrite nanocomposites for magnetic hyperthermia applications

NASA Astrophysics Data System (ADS)

El-Dek, S. I.; Ali, Maha A.; El-Zanaty, Sara M.; Ahmed, Shehab E.

2018-07-01

Superparamagnetic iron oxide nanoparticles (SPION) Fe3O4 nanoparticles were prepared using different approaches: co-precipitation and sonochemical methods. This article is a comparative study on how different synthesis techniques greatly affect the magnetic properties and heating efficiency of such nanomaterial. Another important issue addressed here is the correlation between microstructure, colloidal stability, magnetization and specific absorption rate (SAR) of the nanoparticles. The results reveal that the sonochemical method for polyethylene glycol (PEGylated) Fe3O4 with size 5 nm leads to pseudo single domain with smallest loop area. Additionally, large SAR values are obtained within 10-15 min using low magnetic field.

Cations in Octahedral Sites: A Descriptor for Oxygen Electrocatalysis on Transition-Metal Spinels

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

Wei, Chao; Feng, Zhenxing; Scherer, Günther G.

2017-04-10

Exploring efficient and low-cost electrocatalysts for the oxygen-reduction reaction (ORR) and oxygen-evolution reaction (OER) is critical for developing renewable energy technologies such as fuel cells, metal–air batteries, and water electrolyzers. A rational design of a catalyst can be guided by identifying descriptors that determine its activity. Here, a descriptor study on the ORR/OER of spinel oxides is presented. With a series of MnCo2O4, the Mn in octahedral sites is identified as an active site. This finding is then applied to successfully explain the ORR/OER activities of other transition-metal spinels, including MnxCo3-xO4 (x = 2, 2.5, 3), LixMn2O4 (x = 0.7,more » 1), XCo2O4 (X = Co, Ni, Zn), and XFe2O4 (X = Mn, Co, Ni). A general principle is concluded that the eg occupancy of the active cation in the octahedral site is the activity descriptor for the ORR/OER of spinels, consolidating the role of electron orbital filling in metal oxide catalysis.« less

Yb:Y2O3 transparent ceramics processed with hot isostatic pressing

NASA Astrophysics Data System (ADS)

Wang, Jun; Ma, Jie; Zhang, Jian; Liu, Peng; Luo, Dewei; Yin, Danlei; Tang, Dingyuan; Kong, Ling Bing

2017-09-01

Highly transparent 5 at.% Yb:Y2O3 ceramics were fabricated by using a combination method of vacuum sintering and hot isostatic pressing (HIP). Co-precipitated Yb:Y2O3 powders, with 1 at.% ZrO2 as the sintering aid, were used as the starting material. The Yb:Y2O3 ceramics, vacuum sintered at 1700 °C for 2 h and HIPed at 1775 °C for 4 h, exhibited small grain size of 1.9 μm and highly dense microstructure. In-line optical transmittance of the ceramics reached 83.4% and 78.9% at 2000 and 600 nm, respectively. As the ceramic slab was pumped by a fiber-coupled laser diode at about 940 nm, a maximum output power of 0.77 W at 1076 nm was achieved, with a corresponding slope efficiency of 10.6%.

Effect of electrochemical corrosion on the subsurface microstructure evolution of a CoCrMo alloy in albumin containing environment

NASA Astrophysics Data System (ADS)

Wang, Zhongwei; Yan, Yu; Su, Yanjing; Qiao, Lijie

2017-06-01

The subsurface microstructures of metallic implants play a key role in bio-tribocorrosion. Due to wear or change of local environment, the implant surface can have inhomogeneous electrochemical corrosion properties. In this work, the effect of electrochemical corrosion conditions on the subsurface microstructure evolution of CoCrMo alloys for artificial joints was investigated. Transmission electron microscope (TEM) was employed to observe the subsurface microstructures of worn areas at different applied potentials in a simulated physiological solution. The results showed that applied potentials could affect the severity of the subsurface deformation not only by changing the surface passivation but also affecting the adsorption of protein on the alloy surface.

Effect of anode firing on the performance of lanthanum and nickel co-doped SrTiO3 (La0.2Sr0.8Ti0.9Ni0.1O3-δ) anode of solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Park, Byung Hyun; Choi, Gyeong Man

2015-10-01

Perovskite oxides have potential for use as alternative anode materials in solid oxide fuel cells (SOFCs) due to stability in anode atmosphere; donor-doped SrTiO3 (e.g., La0.2Sr0.8TiO3-δ) is a good candidate for this purpose. Electro-catalytic nanoparticles can be produced in oxide anodes by the ex-solution method, e.g., by incorporating Ni into a perovskite oxide in air, then reducing the oxide in H2 atmosphere. In this study, we varied the temperature (1100, 1250 °C) and atmosphere (air, H2) of La0.2Sr0.8Ti0.9Ni0.1O3-δ (LSTN) anode firing to control the degree of Ni ex-solution and microstructure. LSTN fired at 1250 °C in H2 showed the best anodic performance for scandia-stabilized zirconia (ScSZ) electrolyte-supported cells in H2 and CH4 fuels due to the favorable microstructure and Ni ex-solution.

The Effect of Preheat Temperature and Inter-Pass Reheating on Microstructure and Texture Evolution During Hot Rolling of Ti-6Al-4V (Preprint)

DTIC Science & Technology

2008-02-01

three broad types of microstructures can be developed in alpha/beta titanium alloys by TMP [2- 4 ], namely, fully lamellar, fully equiaxed, and...32-45. 4 . M. Peters, G. Luetjering, in: Titanium 80: Science and Technology, ed. H. Kimura and O. Izumi, Kyoto, Japan, 1980, pp. 925-938. 5. G...Lutjering, J.C. Williams, in: Titanium , Springer-Verlag, Berlin, Germany, 2003, pp.220- 224. 6 . A.A. Salem, M.G. Glavicic, S.L. Semiatin, Materials

Composite anode La0.8Sr0.2MnO3 impregnated with cobalt oxide for steam electrolysis

NASA Astrophysics Data System (ADS)

Li, Shisong; Cheng, Jigui; Xie, Kui; Li, Peipei; Wu, Yucheng

2013-12-01

Oxygen-ion conducting solid oxide electrolyzer (SOE) has attracted a great deal of interest because it converts electrical energy into chemical energy directly. The oxygen evolution reaction (OER) is occurred at the anode of solid oxide electrolyzer as the O2- being oxidized and form O2 gas, which is considered as one of the major cause of overpotentials in steam electrolyzers. This paper investigates the electrolysis of steam based on cobalt oxide impregnated La0.8Sr0.2MnO3 (LSM) composite anode in an oxide-ion-conducting solid oxide electrolyzer. The conductivity of LSM is studied versus temperature and oxygen partial pressure and correlated to the electrochemical properties of the composite electrodes in symmetric cells at 800 °C. Different contents of Co3O4 (wt.1%, 2%, 4%, 6%, 8%, 10%) were impregnated into LSM electrode and it was found that the polarization resistance (Rp) of symmetric cells gradually improved from 1.16 Ω•cm2 (LSM) to 0.24 Ω•cm2 (wt.10%Co3O4-LSM). Steam electrolysis based on LSM and wt.6%Co3O4-LSM anode electrolyzers are tested at 800°C and the AC impedance spectroscopy results indicated that the Rp of high frequency process significantly decreased from1.1 Ω•cm2 (LSM) to 0.5 Ω•cm2 (wt.6%Co3O4-LSM) under 1.8V electrolysis voltage and the Rp of low frequency process decreased from 14.9 Ω•cm2 to 5.7 Ω•cm2. Electrochemical catalyst Co3O4 can efficiently improve the electrode and enhance the performance of high temperature solid oxide electrolyzer.

Magnetic properties of Sr 3 NiIrO 6 and Sr 3 CoIrO 6 : Magnetic hysteresis with coercive fields of up to 55 T

DOE PAGES

Singleton, John; Kim, Jae Wook; Topping, Craig V.; ...

2016-12-08

Here, we report extraordinarily large magnetic hysteresis loops in the iridates Sr 3NiIrO 5 and Sr 3CoIrO 6. We find coercive magnetic fields of up to 55 T with switched magnetic moments ≈1μ B per formula unit in Sr 3NiIrO 6 and coercive fields of up to 52 T with switched moments ≈3μ B per formula unit in Sr 3CoIrO 6. We propose that the magnetic hysteresis involves the field-induced evolution of quasi-one-dimensional chains in a frustrated triangular configuration. In conclusion, the striking magnetic behavior is likely to be linked to the unusual spin-orbit-entangled local state of the Ir 4+more » ion and its potential for anisotropic exchange interactions.« less

Structural, dielectric and gas sensing behavior of Mn substituted spinel MFe2O4 (M=Zn, Cu, Ni, and Co) ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Ranjith Kumar, E.; Siva Prasada Reddy, P.; Sarala Devi, G.; Sathiyaraj, S.

2016-01-01

Spinel ferrite (MnZnFe2O4, MnCuFe2O4, MnNiFe2O4 and MnCoFe2O4) nanoparticles have been prepared by evaporation method. The annealing temperature plays an important role on changing particle size of the spinel ferrite nanoparticles was found out by X-ray diffraction and transmission electron microscopy. The role of manganese substitution in the spinel ferrite nanoparticles were also analyzed for different annealing temperature. The substitution of Mn also creates a vital change in dielectric properties have been measured in the frequency range of 100 kHz to 5 MHz. These spinel ferrites are decomposed to α-Fe2O3 after annealing above 550 °C in air. Through the characterization of the prepared powder, the effect of annealing temperature, chemical composition and preparation technique on the microstructure, particle size and dielectric properties of the Mn substituted spinel ferrite nanoparticles are discussed. Furthermore, Conductance response of Mn substituted MFe2O4 ferrite nanoparticles were measured by exposing the materials to reducing gas like liquefied petroleum gas (LPG).

Structural and magnetic properties of pure and Ca-doped LaCoO3 nanopowders obtained by a sol-gel route.

PubMed

Armelao, Lidia; Barreca, Davide; Bottaro, Gregorio; Maragno, Cinzia; Tondello, Eugenio; Caneschi, Andrea; Sangregorio, Claudio; Gialanella, Stefano

2006-04-01

Pure and Ca-doped LaCoO3 nanopowders were prepared by a non-alkoxidic sol-gel route using cobalt(II) acetate, lanthanum(III) nitrate and calcium(II) acetate as oxide precursors. The structural evolution and magnetic properties of the samples were studied as a function of thermal treatments in air up to 1273 K. In particular, the microstructure and composition of the systems were analyzed by X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM), and X-ray Photoelectron Spectroscopy (XPS). Both pure and calcium-doped samples annealing at 973 K resulted in the formation of cubic LaCoO3 (average crystallite size <30 nm). This phase was fully retained in the calcium-doped materials even after annealing at higher temperatures, whereas a transition to the rhomboedral polymorph was detected in the pure samples at 1073 K. The magnetic behavior of the nanopowders was investigated as a function of temperature and applied field using both dynamic and static susceptibility measurements. Pure lanthanum cobaltite samples underwent a transition to an ordered state at 88 K, and their magnetic properties changed as a function of thermal treatments. As concerns calcium-doped samples, they ordered ferromagnetically at 171 and 185 K depending on the annealing temperature and displayed open hysteresis loops with coercive fields as large as 1.75 T at low temperatures.

Nano-crystalline phase evolution and structural modification in Co/V substituted Li2O-Bi2O3-B2O3 glasses

NASA Astrophysics Data System (ADS)

Yadav, Arti; Dahiya, M. S.; Hooda, A.; Agarwal, A.; Khasa, S.

2018-05-01

Co/V substituted Li2O-Bi2O3-B2O3 glasses having composition 7CoO•23Li2O•20Bi2O3•50B2O3(CLBB) and xCoO•(30-x)Li2O•20Bi2O3•50B2O3(x = 0.0, 2.0, 5.0, 7.0 and 10.0 mol%, CVLBB1-5 respectively) developed via melt- quench route. The effect of annealing on structural properties of prepared samples was investigated by using XRD patterns and FTIR spectroscopy. Glasses annealed at 400˚C remained amorphous whereas glasses annealed at 500˚C changes from glasses to glass ceramics. The different crystalline phases i.e. Bi2(V0.9Co0.1)O5.25, LiCoVO4, V2O5 & Bi2(VO5) evolve on annealing at 500°C for 6 hours confirmed from the corresponding XRD patterns. The crystallite size of prepared samples were found to vary as 38-60nm This indicated that CoO and V2O5 introduced in matrix act as crystallizing agents and cause structural modification as studied by the FTIR spectra for all heat treated compositions.

Base-Metal Electrode-Multilayer Ceramic Capacitors: Past, Present and Future Perspectives

NASA Astrophysics Data System (ADS)

Kishi, Hiroshi; Mizuno, Youichi; Chazono, Hirokazu

2003-01-01

Multilayer ceramic capacitor (MLCC) production and sales figures are the highest among fine-ceramic products developed in the past 30 years. The total worldwide production and sales reached 550 billion pieces and 6 billion dollars, respectively in 2000. In the course of progress, the development of base-metal electrode (BME) technology played an important role in expanding the application area. In this review, the recent progress in MLCCs with BME nickel (Ni) electrodes is reviewed from the viewpoint of nonreducible dielectric materials. Using intermediate-ionic-size rare-earth ion (Dy2O3, Ho2O3, Er2O3, Y2O3) doped BaTiO3 (ABO3)-based dielectrics, highly reliable Ni-MLCCs with a very thin layer below 2 μm in thickness have been developed. The effect of site occupancy of rare-earth ions in BaTiO3 on the electrical properties and microstructure of nonreducible dielectrics is studied systematically. It appears that intermediate-ionic-size rare-earth ions occupy both A- and B-sites in the BaTiO3 lattice and effectively control the donor/acceptor dopant ratio and microstructural evolution. The relationship between the electrical properties and the microstructure of Ni-MLCCs is also presented.

Radiation-induced changes in electrical conductivity and structure of BaPbO3 after γ-irradiation

NASA Astrophysics Data System (ADS)

Shan, Qing; Cai, Pingkun; Zhang, Xinlei; Li, Jiatong; Chu, Shengnan; Jia, Wenbao

2015-11-01

Several barium plumbate (BaPbO3) solid samples, made from PbO and BaCO3 powder by chemistry liquid-phase coprecipitation, were investigated before and after γ-irradiation. The solid samples were irradiated by a 60Co γ-irradiation source whose dose rate is about 0.7 kGy per hour. The irradiation times were 0, 72, 144, 216, 288 and 360 h. Then, the four-probe method, X-ray diffraction (XRD), scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS) were used to indicate the changes in electrical conductivity and microstructure of BaPbO3 after γ-irradiation. The XRD results indicated that the content of PbO was reduced as the irradiation dose was increased and eventually vanished from the surface of samples. However, there was no new obvious substance phase found from the XRD atlas. It seems that the PbO transformed into nearly amorphous Pb5O8. The conjecture could be proved by the results of annealing experiment and SEM. The XPS results seem to show that the microstructure of BaPbO3 was slightly changed.

Mechanical and electrochemical response of a LiCoO 2 cathode using reconstructed microstructures

DOE PAGES

Mendoza, Hector; Roberts, Scott Alan; Brunini, Victor; ...

2016-01-01

As LiCoO 2 cathodes are charged, delithiation of the LiCoO 2 active material leads to an increase in the lattice spacing, causing swelling of the particles. When these particles are packed into a bicontinuous, percolated network, as is the case in a battery electrode, this swelling leads to the generation of significant mechanical stress. In this study we performed coupled electrochemical-mechanical simulations of the charging of a LiCoO 2 cathode in order to elucidate the mechanisms of stress generation and the effect of charge rate and microstructure on these stresses. Energy dispersive spectroscopy combined with scanning electron microscopy imaging wasmore » used to create 3D reconstructions of a LiCoO 2 cathode, and the Conformal Decomposition Finite Element Method is used to automatically generate computational meshes on this reconstructed microstructure. Replacement of the ideal solution Fickian diffusion model, typically used in battery simulations, with a more general non-ideal solution model shows substantially smaller gradients of lithium within particles than is typically observed in the literature. Using this more general model, lithium gradients only appear at states of charge where the open-circuit voltage is relatively constant. While lithium gradients do affect the mechanical stress state in the particles, the maximum stresses are always found in the fully-charged state and are strongly affected by the local details of the microstructure and particle-to-particle contacts. These coupled electrochemical-mechanical simulations begin to yield insight into the partitioning of volume change between reducing pore space and macroscopically swelling the electrode. Lastly, preliminary studies that include the presence of the polymeric binder suggest that it can greatly impact stress generation and that it is an important area for future research.« less

Controllable fabrication of urchin-like Co3O4 hollow spheres for high-performance supercapacitors and lithium-ion batteries.

PubMed

Chen, Fashen; Liu, Xiaohe; Zhang, Zhian; Zhang, Ning; Pan, Anqiang; Liang, Shuquan; Ma, Renzhi

2016-09-27

Urchin-like cobalt oxide (Co 3 O 4 ) hollow spheres can be successfully prepared by thermal decomposition of cobalt carbonate hydroxide hydrate (Co(CO 3 ) 0.5 (OH)·0.11H 2 O) obtained by template-assisted hydrothermal synthesis. The morphology, crystal structure evolution and thermal decomposition behaviors of the as-prepared products have been carefully investigated. A plausible formation mechanism of the urchin-like Co 3 O 4 hollow spheres in the presence of hexadecyl trimethyl ammonium bromide (CTAB) as the surfactant template is proposed. The urchin-like Co 3 O 4 hollow spheres are further constructed as electrode materials for high-performance supercapacitors with a high specific capacitance of 460 F g -1 at a current density of 4 A g -1 and excellent cycling stability. Furthermore, as anode materials for lithium-ion batteries (LIBs), superior lithium storage performance of 1342.2 mA h g -1 (0.1 C) and 1122.7 mA h g -1 (0.2 C) can also be achieved. The excellent performances can be ascribed to the unique hierarchical urchin-like hollow structure of the electrode materials, which offers a large specific surface area, short electron and ion diffusion paths and high permeability while being directly in contact with the electrolyte. Moreover, the hollow structure with sufficient internal void spaces can self-accommodate volume change during electrochemical reactions, which improves the structural stability and integrity.

Interpenetrating Triphase Cobalt-Based Nanocomposites as Efficient Bifunctional Oxygen Electrocatalysts for Long-Lasting Rechargeable Zn–Air Batteries

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

Jiang, Yi; Deng, Ya-Ping; Fu, Jing

Rational construction of atomic-scale interfaces in multiphase nanocomposites is an intriguing and challenging approach to developing advanced catalysts for both oxygen reduction (ORR) and evolution reactions (OER). In this paper, a hybrid of interpenetrating metallic Co and spinel Co 3O 4 “Janus” nanoparticles stitched in porous graphitized shells (Co/Co 3O 4@PGS) is synthesized via ionic exchange and redox between Co 2+ and 2D metal–organic-framework nanosheets. This strategy is proven to effectively establish highways for the transfer of electrons and reactants within the hybrid through interfacial engineering. Specifically, the phase interpenetration of mixed Co species and encapsulating porous graphitized shells providesmore » an optimal charge/mass transport environment. Furthermore, the defect-rich interfaces act as atomic-traps to achieve exceptional adsorption capability for oxygen reactants. Finally, robust coupling between Co and N through intimate covalent bonds prohibits the detachment of nanoparticles. As a result, Co/Co 3O 4@PGS outperforms state-of-the-art noble-metal catalysts with a positive half-wave potential of 0.89 V for ORR and a low potential of 1.58 V at 10 mA cm -2 for OER. Finally, in a practical demonstration, ultrastable cyclability with a record lifetime of over 800 h at 10 mA cm -2 is achieved by Zn–air batteries with Co/Co 3O 4@PGS within the rechargeable air electrode.« less

Interpenetrating Triphase Cobalt-Based Nanocomposites as Efficient Bifunctional Oxygen Electrocatalysts for Long-Lasting Rechargeable Zn–Air Batteries

DOE PAGES

Jiang, Yi; Deng, Ya-Ping; Fu, Jing; ...

2018-01-31

Rational construction of atomic-scale interfaces in multiphase nanocomposites is an intriguing and challenging approach to developing advanced catalysts for both oxygen reduction (ORR) and evolution reactions (OER). In this paper, a hybrid of interpenetrating metallic Co and spinel Co 3O 4 “Janus” nanoparticles stitched in porous graphitized shells (Co/Co 3O 4@PGS) is synthesized via ionic exchange and redox between Co 2+ and 2D metal–organic-framework nanosheets. This strategy is proven to effectively establish highways for the transfer of electrons and reactants within the hybrid through interfacial engineering. Specifically, the phase interpenetration of mixed Co species and encapsulating porous graphitized shells providesmore » an optimal charge/mass transport environment. Furthermore, the defect-rich interfaces act as atomic-traps to achieve exceptional adsorption capability for oxygen reactants. Finally, robust coupling between Co and N through intimate covalent bonds prohibits the detachment of nanoparticles. As a result, Co/Co 3O 4@PGS outperforms state-of-the-art noble-metal catalysts with a positive half-wave potential of 0.89 V for ORR and a low potential of 1.58 V at 10 mA cm -2 for OER. Finally, in a practical demonstration, ultrastable cyclability with a record lifetime of over 800 h at 10 mA cm -2 is achieved by Zn–air batteries with Co/Co 3O 4@PGS within the rechargeable air electrode.« less

Phase composition and microstructure of WC-Co alloys obtained by selective laser melting

NASA Astrophysics Data System (ADS)

Khmyrov, Roman S.; Shevchukov, Alexandr P.; Gusarov, Andrey V.; Tarasova, Tatyana V.

2018-03-01

Phase composition and microstructure of initial WC, BK8 (powder alloy 92 wt.% WC-8 wt.% Co), Co powders, ball-milled powders with four different compositions (1) 25 wt.% WC-75 wt.% Co, (2) 30 wt.% BK8-70 wt.% Co, (3) 50 wt.% WC-50 wt.% Co, (4) 94 wt.% WC-6 wt.% Co, and bulk alloys obtained by selective laser melting (SLM) from as-milled powders in as-melted state and after heat treatment were investigated by scanning electron microscopy and X-ray diffraction analysis. Initial and ball-milled powders consist of WC, hexagonal α-Co and face-centered cubic β-Co. The SLM leads to the formation of major new phases W3Co3C, W4Co2C and face-centered cubic β-Co-based solid solution. During the heat treatment, there occurs partial decomposition of the face-centered cubic β-Co-based solid solution with the formation of W2C and hexagonal α-Co solid solution. The microstructure of obtained bulk samples, in general, corresponds to the observed phase composition.

Isothermal reduction kinetics and mineral phase of chromium-bearing vanadium-titanium sinter reduced with CO gas at 873-1273 K

NASA Astrophysics Data System (ADS)

Yang, Song-tao; Zhou, Mi; Jiang, Tao; Xue, Xiang-xin

2018-02-01

Reduction of chromium-bearing vanadium-titanium sinter (CVTS) was studied under simulated conditions of a blast furnace, and thermodynamics and kinetics were theoretically analyzed. Reduction kinetics of CVTS at different temperatures was evaluated using a shrinking unreacted core model. The microstructure, mineral phase, and variation of the sinter during reduction were observed by X-ray diffraction, scanning electron microscopy, and metallographic microscopy. Results indicate that porosity of CVTS increased with temperature. Meanwhile, the reduction degree of the sinter improved with the reduction rate. Reduction of the sinter was controlled by a chemical reaction at the initial stage and inner diffusion at the final stage. Activation energies measured 29.22-99.69 kJ/mol. Phase transformations in CVTS reduction are as follows: Fe2O3→Fe3O4→FeO→Fe; Fe2TiO5→Fe2TiO4→FeTiO3; FeO·V2O3→V2O3; FeO·Cr2O3→Cr2O3.

Effect of Spray Distance on Microstructure and Tribological Performance of Suspension Plasma-Sprayed Hydroxyapatite-Titania Composite Coatings

NASA Astrophysics Data System (ADS)

Zhang, Chao; Xu, Haifeng; Geng, Xin; Wang, Jingjing; Xiao, Jinkun; Zhu, Peizhi

2016-10-01

Hydroxyapatite (HA)-titania (TiO2) composite coatings prepared on Ti6Al4V alloy surface can combine the excellent mechanical property of the alloy substrate and the good biocompatibility of the coating material. In this paper, HA-TiO2 composite coatings were deposited on Ti6Al4V substrates using suspension plasma spray (SPS). X-ray diffraction, scanning electron microscopy, Fourier infrared absorption spectrometry and friction tests were used to analyze the microstructure and tribological properties of the obtained coatings. The results showed that the spray distance had an important influence on coating microstructure and tribological performance. The amount of decomposition phases decreased as the spray distance increased. The increase in spray distance from 80 to 110 mm improved the crystalline HA content and decreased the wear performance of the SPS coatings. In addition, the spray distance had a big effect on the coating morphology due to different substrate temperature resulting from different spray distance. Furthermore, a significant presence of OH- and CO3 2- was observed, which was favorable for the biomedical applications.

Isopycnic Phases and Structures in H2O/CO2/Ethoxylated Alcohol Surfactant Mixtures

NASA Technical Reports Server (NTRS)

Paulaitis, Michael E.; Zielinski, Richard G.; Kaler, Eric W.

1996-01-01

Ternary mixtures of H2O and CO2 with ethoxylated alcohol (C(i)E(j)) surfactants can form three coexisting liquid phases at conditions where two of the phases have the same density (isopycnic phases). Isopycnic phase behavior has been observed for mixtures containing the surfactants C8E5, C10E6, and C12E6, but not for those mixtures containing either C4E1 or CgE3. Pressure-temperature (PT) projections for this isopycnic three-phase equilibrium were determined for H2O/CO2/C8E5 and H2O/CO2/C10E6 mixtures at temperatures from approximately 25 to 33 C and pressures between 90 and 350 bar. As a preliminary to measuring the microstructure in isopycnic three component mixtures, phase behavior and small angle neutron scattering (SANS) experiments were performed on mixtures of D2O/CO2/ n-hexaethyleneglycol monododecyl ether (C12E6) as a function of temperature (25-31 C), pressure (63.1-90.7 bar), and CO2 composition (0-3.9 wt%). Parameters extracted from model fits of the SANS spectra indicate that, while micellar structure remains essentially unchanged, critical concentration fluctuations increase as the phase boundary and plait point are approached.

Carbonate mineral solubility at low temperatures in the Na-K-Mg-Ca-H-Cl-SO 4-OH-HCO 3-CO 3-CO 2-H 2O system

NASA Astrophysics Data System (ADS)

Marion, Giles M.

2001-06-01

Carbonate minerals have played an important role in the geochemical evolution of Earth, and may have also played an important role in the geochemical evolution of Mars and Europa. Several models have been published in recent years that describe chloride and sulfate mineral solubilities in concentrated brines using the Pitzer equations. Few of these models are parameterized for subzero temperatures, and those that are do not include carbonate chemistry. The objectives of this work are to estimate Pitzer-equation bicarbonate-carbonate parameters and carbonate mineral solubility products and to incorporate them into the FREZCHEM model to predict carbonate mineral solubilities in the Na-K-Mg-Ca-H-Cl-SO 4-OH-HCO 3-CO 3-CO 2-H 2O system at low temperatures (≤25°C) with a special focus on subzero temperatures. Most of the Pitzer-equation parameters and equilibrium constants are taken from the literature and extrapolated into the subzero temperature range. Solubility products for 14 sodium, potassium, magnesium, and calcium bicarbonate and carbonate minerals are included in the model. Most of the experimental data are at temperatures ≥ -8°C; only for the NaHCO 3-NaCl-H 2O and Na 2CO 3-NaCl-H 2O systems are there bicarbonate and carbonate data to temperatures as low as -21.6°C. In general, the fit of the model to the experimental data is good. For example, calculated eutectic temperatures and compositions for NaHCO 3, Na 2CO 3, and their mixtures with NaCl and Na 2SO 4 salts are in good agreement with experimental data to temperatures as low as -21.6°C. Application of the model to eight saline, alkaline carbonate waters give predicted pHs ranging from 9.2 to 10.2, in comparison with measured pHs that range from 8.7 to 10.2. The model suggests that the CaCO 3 mineral that precipitates during seawater freezing is probably calcite and not ikaite. The model demonstrates that a proposed salt assemblage for the icy surface of Europa consisting of highly hydrated MgSO 4 salts and natron (Na 2CO 3 · 10H 2O) is an incompatible salt assemblage.

Exchange bias mediated by interfacial nanoparticles (invited)

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

Berkowitz, A. E., E-mail: aberk@ucsd.edu; Center for Magnetic Recording Research, University of California, California 92093; Sinha, S. K.

2015-05-07

The objective of this study on the iconic exchange-bias bilayer Permalloy/CoO has been to identify those elements of the interfacial microstructure and accompanying magnetic properties that are responsible for the exchange-bias and hysteretic properties of this bilayer. Both epitaxial and polycrystalline samples were examined. X-ray and neutron reflectometry established that there existed an interfacial region, of width ∼1 nm, whose magnetic properties differed from those of Py or CoO. A model was developed for the interfacial microstructure that predicts all the relevant properties of this system; namely; the temperature and Permalloy thickness dependence of the exchange-bias, H{sub EX}, and coercivity, H{submore » C}; the much smaller measured values of H{sub EX} from what was nominally expected; the different behavior of H{sub EX} and H{sub C} in epitaxial and polycrystalline bilayers. A surprising result is that the exchange-bias does not involve direct exchange-coupling between Permalloy and CoO, but rather is mediated by CoFe{sub 2}O{sub 4} nanoparticles in the interfacial region.« less

Agricultural Fires in the Southeastern U.S. During SEAC4RS: Emissions of Trace Gases and Particles and Evolution of Ozone, Reactive Nitrogen, and Organic Aerosol

NASA Technical Reports Server (NTRS)

Liu, X.; Zhang, Y.; Huey, L. G.; Yokelson, R. J.; Wang, Y.; Jimenez, J. L.; Campuzano-Jost, P.; Beyersdorf, A. J.; Blake, D. R.; Choi, Y.;

Raman evidence of the formation of LT-LiCoO 2 thin layers on NiO in molten carbonate at 650°C

NASA Astrophysics Data System (ADS)

Mendoza, L.; Baddour-Hadjean, R.; Cassir, M.; Pereira-Ramos, J. P.

2004-03-01

The structural evolution of thin layers of Co 3O 4 elaborated on nickel-based substrates in the Li 2CO 3-Na 2CO 3 carbonate eutectic at 650 °C as a function of time immersion is reported. Raman microspectrometry has been applied in order to provide more information on the nature of the protective cobalt oxide layers. The typical Raman fingerprint of the LT-LiCoO 2 compound has been obtained, with four well defined bands at 449, 484, 590 and 605 cm -1, while XRD data are unable to distinguish the layered phase (HT) from the spinel one (LT). The mechanical stability of such films does not exceed 10 h in direct contact with the molten carbonate bulk at 650 °C; nevertheless, these conditions are much more corrosive than in a molten carbonate fuel cell (MCFC).

Evolution of C-O-H-N volatile species in the magma ocean during core formation.

NASA Astrophysics Data System (ADS)

Dalou, C.; Le Losq, C.; Hirschmann, M. M.; Jacobsen, S. D.; Fueri, E.

2017-12-01

The composition of the Hadean atmosphere affected how life began on Earth. Magma ocean degassing of C, O, H, and N was a key influence on the composition of the Hadean atmosphere. To identify the nature of degassed C-O-H-N species, we determined their speciation in reduced basaltic glasses (in equilibrium with Fe-C-N metal alloy, synthetized at 1400 and 1600 ºC and 1.2-3 GPa) via Raman spectroscopy. We addressed the effect of oxygen fugacity (fO2) on C-O-H-N speciation between IW-2.3 and IW-0.4, representing the evolution of the shallow upper mantle fO2 during the Hadean. We observe H2, NH2, NH3, CH3, CH4, CO, N2, and OH species in all glasses. With increasing ƒO2, our results support the formation of OH groups at the expense of N-H and C-H bonds in the melt, implying the equilibria at IW-2: (1) 2OH- (melt) + ½ N2 (melt) ↔ NH2 (melt) + 2 O2- (melt) , (2) 2OH- (melt) + ½ N2 (melt) + ½ H2 (melt) ↔ NH3 (melt) + 2 O2- (melt) . With increasing fO2, eqs. (1) and (2) shift to the left. From IW-2 to IW, we also observe an increase in the intensity of the NH2 peak relative to NH3. Carbon is present as CH3, CH4, and CO in all our glasses. While CO is likely the main carbon specie under reduced conditions (e.g., Armstrong et al. 2015), CH species should remain stable from moderately (IW-0.4) to very reduced (IW-3; Ardia et al. 2014; Kadik et al. 2015, 2017) conditions in hydrous silicate glasses following the equilibria: (3) 3OH- (melt) + C (graphite) ↔ CH3 (melt) + 3O2- (melt) , (4) 4OH- (melt) + C (graphite) ↔ CH4 (melt) + 4O2- (melt) . With increasing fO2, eqs. (3) and (4) shift to the left. As metal segregation and core formation drove the ƒO2 of the magma ocean from IW-4 to IW during the Hadean (Rubie et al. 2011), the nature of species degassed by the magma ocean should have evolved during that time. The C-O-H-N species we observe dissolved in our reduced glasses may not directly correspond to those degassed (Schaeffer and Fegley, 2007), but a better understanding of species abundances and gas phase equilibria should constrain the contribution of magma ocean degassing to the Hadean atmosphere. As reactions involving CO, N2, and OH are sufficient to form amino acids, and NH2, NH3, CH3, and CH4 are amino acid components, the availability of such reduced molecules for outgassing from the magma ocean suggest a central role in the formation of the first organic molecules.

Dealloyed Pt3Co nanoparticles with higher geometric strain for superior hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Saquib, Mohammad; Halder, Aditi

2018-06-01

In the present work, the effect of surface strain in the carbon supported Pt3Co dealloy catalyst towards hydrogen evolution reaction (HER) has been reported. Dealloying process is adopted to generate the geometric strain in Pt3Co/C alloy by preferential dissolution of non-noble metal (Co) from the alloy. The developed geometric strain has been estimated by different microstructural characterization techniques. Electrochemical studies showed that the highest current density for HER was obtained for Pt3Co/C dealloy catalyst and it was nearly 2 and 5 times higher than Pt3Co/C alloy and Pt/C respectively. Tafel slope for HER was improved from 49 (Pt/C) to 34 mV dec-1 (Pt3Co/C dealloy), indicating that the surface strain plays important role in the improvement of the catalytic activity of Pt3Co catalyst. The chronoamperometry data, LSV curves and ECSA values before and after chronoamperometry confirmed that Pt3Co/C dealloy catalyst was a stable as well as a durable electrocatalyst for HER.

Co@Co3O4 Encapsulated in Carbon Nanotube-Grafted Nitrogen-Doped Carbon Polyhedra as an Advanced Bifunctional Oxygen Electrode.

PubMed

Aijaz, Arshad; Masa, Justus; Rösler, Christoph; Xia, Wei; Weide, Philipp; Botz, Alexander J R; Fischer, Roland A; Schuhmann, Wolfgang; Muhler, Martin

2016-03-14

Efficient reversible oxygen electrodes for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are vitally important for various energy conversion devices, such as regenerative fuel cells and metal-air batteries. However, realization of such electrodes is impeded by insufficient activity and instability of electrocatalysts for both water splitting and oxygen reduction. We report highly active bifunctional electrocatalysts for oxygen electrodes comprising core-shell Co@Co3O4 nanoparticles embedded in CNT-grafted N-doped carbon-polyhedra obtained by the pyrolysis of cobalt metal-organic framework (ZIF-67) in a reductive H2 atmosphere and subsequent controlled oxidative calcination. The catalysts afford 0.85 V reversible overvoltage in 0.1 m KOH, surpassing Pt/C, IrO2 , and RuO2 and thus ranking them among one of the best non-precious-metal electrocatalysts for reversible oxygen electrodes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microstructural evolutions and stress studies of titania films derived by "spin-deposition" methods

NASA Astrophysics Data System (ADS)

Eun, Tai Hee

Titania (TiO2) films were fabricated by a "spin-deposition" process. Titanium alkoxides react with moisture in the air, leading to the formation of metal hydroxides which subsequently form an oxide network during deposition. The microstructure of film is easily controlled by the selection of titanium alkoxides and solvents. Films from titanium n-butoxide (Ti(OC 4H9n)4) in toluene exhibited a dense microstructure devoid of cracks. In contrast, films produced from titanium isopropoxide (Ti(OC3H7i)4) in the toluene regularly contained micro-cracks. Titanium isopropoxide in either isopropanol or n-propanol produces highly porous films. After annealing at 300°C, the film derived from titanium n-butoxide in toluene possessed 2˜3 nm nanocrystallites of titanium monoxide (TiO, cubic) in amorphous matrices. TEM and FTIR investigations indicate that the intermediates formed from the oligomers of titanium n-butoxide lead to the formation of the TiO. By annealing at 400°C, the TiO nanoparticles transformed to the TiO2 (anatase). At annealing higher than 450°C, the film was completely crystallized into a polycrystalline of ˜5 nm anatase. In water-rich environments, all amorphous titania films crystallized within 24 hours at 100°C. The crystallization of films is confirmed by XRD and FTIR studies. Amorphous titania films have remnant bridging and terminal hydroxy groups. Removal of these hydroxy groups is promoted by water vapor, which induces the crystallization of amorphous titania to anatase. The mechanism of crystallization in a water-rich environment was proposed based on the FTIR study. Stress evolution in titania films spin-deposited on silicon with solutions of titanium n-butoxide in toluene was investigated by an in-situ wafer curvature method. Tensile stresses were induced due to the densification by removal of water molecules attached to Ti-O-Ti linkages from 200°C to 300°C. The effect of crystallization on stress in the film was studied by comparing results of oxygen and nitrogen anneals. Compositional stress in anatase (a non-stoichiometric oxide) was measured by cyclic reduction-oxidation experiments performed at 700°C. The state of stress observed under reduction conditions was tensile in nature while compressive stresses evolved under oxidizing conditions. The measured value of the compositional stress of the film is 29.6 MPa.

Hybrids of NiCo2O4 nanorods and nanobundles with graphene as promising electrode materials for supercapacitors.

PubMed

Wang, Zhuo; Zhang, Xin; Zhang, Zhongshen; Qiao, Nanli; Li, Yang; Hao, Zhengping

2015-12-15

High dispersion of NiCo2O4 nanorods and porous NiCo2O4 nanobundles decorated on RGO have been synthesized by a facile hydrothermal method, followed by calcination in one step. By adjusting the starting metal sources to realize the synthesis of different morphologies of NiCo2O4. The morphology and the microstructure of the as-prepared composites were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and transmission electron microscope (TEM) techniques. Among them, the porous RGO/NiCo2O4 nanobundles gives a higher specific capacitance of 1278F/g at 1A/g and 719F/g at 20A/g, showing a remarkable rate capability. The excellent electrochemical performances could ascribed to the unique structural feature with higher surface area. It could be anticipated that the synthesized electrode material will gain promising applications in supercapacitors and other devices because of their outstanding characteristics of controllable capacitance and facilely synthesized. Copyright © 2015 Elsevier Inc. All rights reserved.

X-ray spectroscopic characterization of Co(IV) and metal–metal interactions in Co 4O 4: Electronic structure contributions to the formation of high-valent states relevant to the oxygen evolution reaction

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

Hadt, Ryan G.; Hayes, Dugan; Brodsky, Casey N.

2016-08-12

In this paper, the formation of high-valent states is a key factor in making highly active transition metal-based catalysts of the oxygen-evolving reaction (OER). These high oxidation states will be strongly influenced by the local geometric and electronic structures of the metal ion, which is difficult to study due to spectroscopically active and complex backgrounds, short lifetimes, and limited concentrations. Here, we use a wide range of complementary X-ray spectroscopies coupled to DFT calculations to study Co 4O 4 cubanes, which provide insight into the high-valent Co(IV) centers responsible for the activity of molecular and heterogeneous OER catalysts. The combinationmore » of X-ray absorption and 1s3p resonant inelastic X-ray scattering (Kβ RIXS) allow Co(IV) to be isolated and studied against a spectroscopically active Co(III) background. Co K- and L-edge X-ray absorption data allow for a detailed characterization of the 3d-manifold of effectively localized Co(IV) centers and provide a direct handle on the ligand field environment and covalency of the t 2g-based redox active molecular orbital. Kβ RIXS is also shown to provide a powerful probe of Co(IV), and specific spectral features are sensitive to the degree of oxo-mediated metal-metal coupling across Co 4O 4. Guided by the data, calculations show electron-hole delocalization can actually oppose Co(IV) formation. Computational extension of Co 4O 4 to CoM 3O 4 structures (M = redox-inactive metal) defines electronic structure contri-butions to Co(IV) formation. Redox activity is shown to be linearly related to covalency, and M(III) oxo inductive effects on Co(IV) oxo bonding can tune the covalency of high-valent sites over a large range and thereby tune E 0 over hundreds of mVs.« less

Three cobalt(II)-linked {P8W48} network assemblies: syntheses, structures, and magnetic and photocatalysis properties.

PubMed

Jiao, Yan-Qing; Qin, Chao; Wang, Xin-Long; Wang, Chun-Gang; Sun, Chun-Yi; Wang, Hai-Ning; Shao, Kui-Zhan; Su, Zhong-Min

2014-02-01

Three cobalt(II)-containing tungstophosphate compounds, Na8Li8Co5[Co5.5(H2O)19P8W48.5O184]⋅60 H2O (1), K2Na4Li11Co5[Co7(H2O)28P8W48O184]Cl⋅ 59 H2O (2), and K2Na4LiCo11[Co8(H2O)32P8W48O184](CH3COO)4Cl⋅47 H2O (3), have been synthesized and characterized by IR spectroscopy, thermogravimetric analysis, elemental analyses, and magnetic measurements. The pH value impacts the formation of distinct cobalt-linked frameworks. The cyclic cavity of the polyanion accommodates 5.5, 7, and 8 cobalt ions in 1, 2, and 3, respectively. In compounds 1 and 2, each {Co5.5P8W48} and {Co7P8W48} fragment links to four others through multiple {Co-O-W} coordination bonds to generate a two-dimensional network. Compound 3 can be considered as a 3D network based on the {Co-O-W} coordination bonds and the {Co3(CH3COO)2(H2O)10} linkers between the {P8W48} fragments. Interestingly, acetate ligands have been employed to form the {Co3(CH3COO)2(H2O)10} unit, thereby inducing the construction of a 12-connected framework. To the best of our knowledge, compound 3 contains the largest-ever number of cobalt ions in a {P8W48}-based polyoxometalate when counterions are taken into account and the {P8W48} unit shows the highest number of connections thanks to the carboxyl bridges. The UV/Vis diffuse reflectance spectra of these powder samples indicate that the corresponding well-defined optical absorption associated with Eg can be assessed at 2.58, 2.48, and 2.73 eV and reveal the presence of an optical band gap. The photocatalytic H2 evolution activities of these {P8W48}-based compounds are evaluated. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microstructure and Mechanical Properties Evolution of the Al, C-Containing CoCrFeNiMn-Type High-Entropy Alloy during Cold Rolling.

PubMed

Klimova, Margarita; Stepanov, Nikita; Shaysultanov, Dmitry; Chernichenko, Ruslan; Yurchenko, Nikita; Sanin, Vladimir; Zherebtsov, Sergey

2017-12-29

The effect of cold rolling on the microstructure and mechanical properties of an Al- and C-containing CoCrFeNiMn-type high-entropy alloy was reported. The alloy with a chemical composition (at %) of (20-23) Co, Cr, Fe, and Ni; 8.82 Mn; 3.37 Al; and 0.69 C was produced by self-propagating high-temperature synthesis with subsequent induction. In the initial as-cast condition the alloy had an face centered cubic single-phase coarse-grained structure. Microstructure evolution was mostly associated with either planar dislocation glide at relatively low deformation during rolling (up to 20%) or deformation twinning and shear banding at higher strain. After 80% reduction, a heavily deformed twinned/subgrained structure was observed. A comparison with the equiatomic CoCrFeNiMn alloy revealed higher dislocation density at all stages of cold rolling and later onset of deformation twinning that was attributed to a stacking fault energy increase in the program alloy; this assumption was confirmed by calculations. In the initial as-cast condition the alloy had low yield strength of 210 MPa with yet very high uniform elongation of 74%. After 80% rolling, yield strength approached 1310 MPa while uniform elongation decreased to 1.3%. Substructure strengthening was found to be dominated at low rolling reductions (<40%), while grain (twin) boundary strengthening prevailed at higher strains.

Strain-sensitive spin-state ordering in thin films of perovskite LaCoO3

NASA Astrophysics Data System (ADS)

Fujioka, J.; Yamasaki, Y.; Doi, A.; Nakao, H.; Kumai, R.; Murakami, Y.; Nakamura, M.; Kawasaki, M.; Arima, T.; Tokura, Y.

2015-11-01

We have investigated the lattice distortion coupled to the Co 3 d -spin-state ordering in thin films of perovskite LaCoO3 with various epitaxial strains by measurements of the magnetization, x-ray diffraction, and optical spectra. In the system with tensile strain about 0.5%, a lattice distortion characterized by the modulation vector q =(1 /6 ,1 /6 ,1 /6 ) emerges at 40 K, followed by a ferromagnetic ordering at 24 K. Alternatively, in systems with tensile strain exceeding 1%, the lattice distortion characterized by q =(1 /4 ,1 /4 ,1 /4 ) emerges at 120 K or higher, and subsequently the ferromagnetic or ferrimagnetic ordering occurs around 90 K. The evolution of infrared phonon spectra and resonant x-ray scattering at the Co K edge suggests that the population change in the Co 3 d spin state causes the strain-induced switching of spin-state ordering as well as of magnetic ordering in this canonical spin-state crossover system.

Atomic layer deposited cobalt oxide: An efficient catalyst for NaBH{sub 4} hydrolysis

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

Nandi, Dip K.; Manna, Joydev; Dhara, Arpan

2016-01-15

Thin films of cobalt oxide are deposited by atomic layer deposition using dicobalt octacarbonyl [Co{sub 2}(CO){sub 8}] and ozone (O{sub 3}) at 50 °C on microscope glass substrates and polished Si(111) wafers. Self-saturated growth mechanism is verified by x-ray reflectivity measurements. As-deposited films consist of both the crystalline phases; CoO and Co{sub 3}O{sub 4} that gets converted to pure cubic-Co{sub 3}O{sub 4} phase upon annealing at 500 °C under ambient condition. Elemental composition and uniformity of the films is examined by x-ray photoelectron spectroscopy and secondary ion-mass spectroscopy. Both as-deposited and the annealed films have been successfully tested as a catalyst formore » hydrogen evolution from sodium borohydride hydrolysis. The activation energy of the hydrolysis reaction in the presence of the as-grown catalyst is found to be ca. 38 kJ mol{sup −1}. Further implementation of multiwalled carbon nanotube, as a scaffold layer, improves the hydrogen generation rate by providing higher surface area of the deposited catalyst.« less

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

Ben Smida, Youssef; Marzouki, Riadh; Georges, Samuel

A new sodium cobalt (II) arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} has been synthesized by a solid-state reaction and its crystal structure determined from single crystal X-ray diffraction data. It crystallizes in the monoclinic system, space group C2/m, with a=10.7098(9) Å, b=14.7837(9) Å, c=6.6845(7) Å, and β=105.545(9)°. The structure is described as a three-dimensional framework built up of corner-edge sharing CoO{sub 6}, CoO{sub 4} and AsO{sub 4} polyhedra, with interconnecting channels along [100] in which the Na{sup +} cations are located. The densest ceramics with relative density of 94% was obtained by ball milling and optimization of sintering temperature, andmore » its microstructure characterized by scanning electron microscopy. The electrical properties of the ceramics were studied over a temperature interval from 280 °C to 560 °C using the complex impedance spectroscopy over the range of 13 MHz–5 Hz. The ionic bulk conductivity value of the sample at 360 °C is 2.51 10{sup −5} S cm{sup −1} and the measured activation energy is Ea=1 eV. The sodium migration pathways in the crystal structure were investigated computationally using the bond valence site energy (BVSE) model and classical molecular dynamics (MD) simulations. - Graphical abstract: Correlation between crystal structure, microstructure and ionic conductivity . Display Omitted - Highlights: • A new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} was prepared by solid state reaction. • Its crystal structure was determined by powder X-ray diffraction. • Na{sup +} ionic conductivity was probed by complex impedance spectroscopy. • Na{sup +} conduction pathways were modeled by bond-valence method and molecular dynamics.« less

Microstructure and Property Evolution in Advanced Cladding and Duct Materials Under Long-Term and Elevated Temperature Irradiation: Modeling and Experimental Investigation

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

Wirth, Brian; Morgan, Dane; Kaoumi, Djamel

2013-12-01

The in-service degradation of reactor core materials is related to underlying changes in the irradiated microstructure. During reactor operation, structural components and cladding experience displacement of atoms by collisions with neutrons at temperatures at which the radiation-induced defects are mobile, leading to microstructure evolution under irradiation that can degrade material properties. At the doses and temperatures relevant to fast reactor operation, the microstructure evolves by dislocation loop formation and growth, microchemistry changes due to radiation-induced segregation, radiation-induced precipitation, destabilization of the existing precipitate structure, and in some cases, void formation and growth. These processes do not occur independently; rather, theirmore » evolution is highly interlinked. Radiationinduced segregation of Cr and existing chromium carbide coverage in irradiated alloy T91 track each other closely. The radiation-induced precipitation of Ni-Si precipitates and RIS of Ni and Si in alloys T91 and HCM12A are likely related. Neither the evolution of these processes nor their coupling is understood under the conditions required for materials performance in fast reactors (temperature range 300-600°C and doses beyond 200 dpa). Further, predictive modeling is not yet possible as models for microstructure evolution must be developed along with experiments to characterize these key processes and provide tools for extrapolation. To extend the range of operation of nuclear fuel cladding and structural materials in advanced nuclear energy and transmutation systems to that required for the fast reactor, the irradiation-induced evolution of the microstructure, microchemistry, and the associated mechanical properties at relevant temperatures and doses must be understood. Predictive modeling relies on an understanding of the physical processes and also on the development of microstructure and microchemical models to describe their evolution under irradiation. This project will focus on modeling microstructural and microchemical evolution of irradiated alloys by performing detailed modeling of such microstructure evolution processes coupled with well-designed in situ experiments that can provide validation and benchmarking to the computer codes. The broad scientific and technical objectives of this proposal are to evaluate the microstructure and microchemical evolution in advanced ferritic/martensitic and oxide dispersion strengthened (ODS) alloys for cladding and duct reactor materials under long-term and elevated temperature irradiation, leading to improved ability to model structural materials performance and lifetime. Specifically, we propose four research thrusts, namely Thrust 1: Identify the formation mechanism and evolution for dislocation loops with Burgers vector of a<100> and determine whether the defect microstructure (predominately dislocation loop/dislocation density) saturates at high dose. Thrust 2: Identify whether a threshold irradiation temperature or dose exists for the nucleation of growing voids that mark the beginning of irradiation-induced swelling, and begin to probe the limits of thermal stability of the tempered Martensitic structure under irradiation. Thrust 3: Evaluate the stability of nanometer sized Y- Ti-O based oxide dispersion strengthened (ODS) particles at high fluence/temperature. Thrust 4: Evaluate the extent to which precipitates form and/or dissolve as a function of irradiation temperature and dose, and how these changes are driven by radiation induced segregation and microchemical evolutions and determined by the initial microstructure.« less

Thermal treatment and ammoniacal leaching for the recovery of valuable metals from spent lithium-ion batteries.

PubMed

Chen, Yongming; Liu, Nannan; Hu, Fang; Ye, Longgang; Xi, Yan; Yang, Shenghai

2018-05-01

The recycling of spent commercial lithium-ion batteries (LIBs) generates numerous environmental and economic benefits. In this research, a thermal treatment-ammoniacal leaching process is proposed to recover valuable metals from cathode active powder. Based on the thermal behavior by TG-DSC analysis, the cathode active powder is calcined at 300 °C and 550 °C in air atmosphere, and the crystalline phase characterization indicates that a new phase of Co 3 O 4 appears in the cathode active powder calcined at 550 °C, which signifies that the layer structure of LiCoO 2 collapses. The valence of manganese increases to form Li 4 Mn 5 O 12 in spinel structure of LiMn 2 O 4 . Using calcined cathode powder as feed material, ammoniacal leaching is carried out in (NH 4 ) 2 SO 4 -(NH 4 ) 2 SO 3 solution. Under the optimum conditions, Ni, Co, Mn and Li can be completely leached out with efficiencies of 98%, 81%, 92% and 98%, respectively. However, with the increase of ammonia concentration, the leaching efficiency of Mn decreases dramatically to 4% due to the formation of double salts. It is found that Co and Mn can be precipitated into residues in the form of (NH 4 ) 2 Co(SO 4 ) 2 ·H 2 O, (NH 4 ) 2 Mn(SO 3 ) 2 ·H 2 O and (NH 4 ) 2 Mn(SO 4 ) 2 ·6H 2 O under different leaching parameters. Based on the corresponding relationship between the leaching efficiency and phase evolution of object element, selective leaching can be achieved by controlling the formation of double salts. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effect of CeO2 and Y2O3 on microstructure, bioactivity and degradability of laser cladding CaO-SiO2 coating on titanium alloy.

PubMed

Li, H C; Wang, D G; Chen, C Z; Weng, F

2015-03-01

To solve the lack of strength of bulk biomaterials for load-bearing applications and improve the bioactivity of titanium alloy (Ti-6Al-4V), CaO-SiO2 coatings on titanium alloy were fabricated by laser cladding technique. The effect of CeO2 and Y2O3 on microstructure and properties of laser cladding coating was analyzed. The cross-section microstructure of ceramic layer from top to bottom gradually changes from cellular-dendrite structure to compact cellular crystal. The addition of CeO2 or Y2O3 refines the microstructure of the ceramic layer in the upper and middle regions. The refining effect on the grain is related to the kinds of additives and their content. The coating is mainly composed of CaTiO3, CaO, α-Ca2(SiO4), SiO2 and TiO2. Y2O3 inhibits the formation of CaO. After soaking in simulated body fluid (SBF), the calcium phosphate layer is formed on the coating surface, indicating the coating has bioactivity. After soaking in Tris-HCl solution, the samples doped with CeO2 or Y2O3 present a lower weight loss, indicating the addition of CeO2 or Y2O3 improves the degradability of laser cladding sample. Copyright © 2015 Elsevier B.V. All rights reserved.

Pressureless sintered beta prime-Si3N4 solid solution: Fabrication, microstructure, and strength

NASA Technical Reports Server (NTRS)

Dutta, S.

1977-01-01

Si3N4, AlN, and Al2O3 were used as basic constituents in a study of the pressureless sintering of beta prime-Si3N4 solid solution as a function of temperature. Y2O3-SiO2 additions were used to promote liquid-phase sintering. The sintered specimens were characterized with respect to density, microstructure, strength, oxidation, and thermal shock resistance. Density greater than 98 percent of theoretical was achieved by pressureless sintering at 1750 C. The microstructure consisted essentially of fine-grained beta prime-Si3N4 solid solution as the major phase. Modulus of rupture strengths up to 483 MPa were achieved at moderate temperature (1000 C), but decreased to 228 MPa at 1380 C. This substantial strength loss was attributed to a glassy grain boundary phase formed during cooling from the sintering temperature. The best oxidation resistance was exhibited by a composition containing 3 mol % Y2O3-SiO2 additives. Water quench thermal shock resistance was equivalent to that of reaction sintered silicon nitride but lower than hot-pressed silicon nitride.

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

NASA Astrophysics Data System (ADS)

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

2014-02-01

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

Synergetic effect of MoS{sub 2} and g-C{sub 3}N{sub 4} as cocatalysts for enhanced photocatalytic H{sub 2} production activity of TiO{sub 2}

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

Yang, Xixian; Huang, Hongyu, E-mail: huanghy@ms.giec.ac.cn; Kubota, Mitsuhiro

Highlights: • A hydrogen evolution reaction of g-C{sub 3}N{sub 4}/MoS{sub 2}/TiO{sub 2} photocatalyst was synthesized. • g-C{sub 3}N{sub 4}/MoS{sub 2}/TiO{sub 2} presents highly efficient H{sub 2} evolution without noble metals. • The effect of g-C{sub 3}N{sub 4} and MoS{sub 2} co-catalyst content in the composites was studied. • The mechanism of g-C{sub 3}N{sub 4}/MoS{sub 2}/TiO{sub 2} photocatalyst under UV–vis light was discussed. - Abstract: In this paper, we report a new g-C{sub 3}N{sub 4}/MoS{sub 2}/TiO{sub 2} composite material as a high-performance photocatalyst for H{sub 2} evolution. Without a noble-metal cocatalyst, the g-C{sub 3}N{sub 4}/MoS{sub 2}/TiO{sub 2} composite reaches a highmore » H{sub 2} production rate of 125 μmol h{sup −1} when the content of the g-C{sub 3}N{sub 4}/MoS{sub 2} cocatalyst is 1.0 wt.% and the content of g-C{sub 3}N{sub 4} in this cocatalyst is 10 wt.%. This unusual photocatalytic activity is attributed to the positive synergetic effect between the MoS{sub 2} and g-C{sub 3}N{sub 4} components in this cocatalyst, which serve as an electron collector and a source of active adsorption sites, respectively.« less

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

Singleton, John; Kim, Jae Wook; Topping, Craig V.

Here, we report extraordinarily large magnetic hysteresis loops in the iridates Sr 3NiIrO 5 and Sr 3CoIrO 6. We find coercive magnetic fields of up to 55 T with switched magnetic moments ≈1μ B per formula unit in Sr 3NiIrO 6 and coercive fields of up to 52 T with switched moments ≈3μ B per formula unit in Sr 3CoIrO 6. We propose that the magnetic hysteresis involves the field-induced evolution of quasi-one-dimensional chains in a frustrated triangular configuration. In conclusion, the striking magnetic behavior is likely to be linked to the unusual spin-orbit-entangled local state of the Ir 4+more » ion and its potential for anisotropic exchange interactions.« less

Syntheses of near-net-shaped monolithic hydroxyapatite and hydroxyapatite-ASTM F75 composites by the oxidation of solid metal-bearing precursors

NASA Astrophysics Data System (ADS)

Saw, Eaden

A novel powder-metallurgical route was used to fabricate near net-shaped hydroxyapatite, Ca10(PO4)6(OH)2 (HA) and HA+Co-C-Mo composite bodies. Ca and beta-Ca2P 2O7 with Ca/P ˜ 1.67 was intimately mixed by high-energy mechanical alloying, formed into desired shapes by pressing and machining, and then converted into HA with a series of heat treatments: a 600°C annealing in dry O2 completely oxidized calcium within 3 h, and a subsequent annealing at ≤1150°C in moist O2 yielded phase-pure HA. The reduction in solid volume associated with the oxidation of calcium (Vm[CaO] < Vm[Ca]) was offset by the increase in solid volume associated with the conversion of CaO and Ca2P2O7 into HA. Thus, the overall dimensional changes upon transformation of Ca+beta-Ca2P 2O7 precursors into HA can be relatively small. A mixture of Co-Cr-Mo powder with the precursor prepared from Ca and beta-Ca 2P2O7, targeted to yield a 75 to 25 volume ratio of Co-Cr-Mo to stoichiometric HA were prepared with the same method but different annealing cycles: annealing at 1150°C in de-oxygenized, flowing Ar resulted in partial densification of the composite bodies, and subsequent annealing at 850°C in a moist O2 atmosphere yielded a composite of Co-Cr-Mo alloy with phase-pure HA. The overall dimensional changes upon transformation of Ca+beta-Ca2P2O7+CO-Cr-Mo precursors into HA/Co-Cr-Mo composite were relatively small. In this thesis, the phase and microstructural evolution at various stages of transformation to monolithic HA and to HA/Co-Cr-Mo alloy composites are discussed. Planar reaction couples and powder compacts of CaO-TCP were prepared to study the kinetics for HA formation from CaO+TCP. Pt strips were used in the planar reaction couples as inert markers. These reaction couples were heated at 1150°C for various times in moist O2. The results of powder compact analyses fits Carter's model, which indicated that the rate of HA conversion from CaO and TCP is limited by solid state diffusion of Ca 2+ and/or OH- through the HA layer.

Formation of interstellar methanol ice prior to the heavy CO freeze-out stage

NASA Astrophysics Data System (ADS)

Qasim, D.; Chuang, K.-J.; Fedoseev, G.; Ioppolo, S.; Boogert, A. C. A.; Linnartz, H.

2018-04-01

Context. The formation of methanol (CH3OH) on icy grain mantles during the star formation cycle is mainly associated with the CO freeze-out stage. Yet there are reasons to believe that CH3OH also can form at an earlier period of interstellar ice evolution in CO-poor and H2O-rich ices. Aims: This work focuses on CH3OH formation in a H2O-rich interstellar ice environment following the OH-mediated H-abstraction in the reaction, CH4 + OH. Experimental conditions are systematically varied to constrain the CH3OH formation yield at astronomically relevant temperatures. Methods: CH4, O2, and hydrogen atoms are co-deposited in an ultrahigh vacuum chamber at 10-20 K. OH radicals are generated by the H + O2 surface reaction. Temperature programmed desorption - quadrupole mass spectrometry (TPD-QMS) is used to characterize CH3OH formation, and is complemented with reflection absorption infrared spectroscopy (RAIRS) for CH3OH characterization and quantitation. Results: CH3OH formation is shown to be possible by the sequential surface reaction chain, CH4 + OH → CH3 + H2O and CH3 + OH → CH3OH at 10-20 K. This reaction is enhanced by tunneling, as noted in a recent theoretical investigation Lamberts et al. (2017, A&A, 599, A132). The CH3OH formation yield via the CH4 + OH route versus the CO + H route is approximately 20 times smaller for the laboratory settings studied. The astronomical relevance of the new formation channel investigated here is discussed.

Evolution of the phonon density of states of LaCoO3 over the spin state transition

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

Golosova, N. O.; Kozlenko, D. P.; Kolesnikov, Alexander I

2011-01-01

The phonon spectra of LaCoO3 were studied by inelastic neutron scattering in the temperature range of 4 120 K. The DFT calculations of the lattice dynamics have been made for interpretation of the experimental data. The observed and calculated phonon frequencies were found to be in a reasonable agreement. The evolution of the phonon density of states over the spin state transition was analyzed. In the low-temperature range (T < 50 K), an increase in the energy of resolved breathing, stretching, and bending phonon modes was found, followed by their softening and broadening at higher temperatures due to the spinmore » state transition and relevant orbital-phonon coupling.« less

ZT 0.1 Electron-Carrying Polymer Thermoelectric Composites with In Situ SnCl 2 Microstructure Growth (Open Access)

DTIC Science & Technology

2015-05-08

derivatives as potential dopants , [ 21 ] achieving elec- trical conductivities of nearly 0.01 S cm −1 and PF of 0.6 W m −1 K −2 . Segalman and co-workers...Weinheim cobalt (III) acetylacetonate (Co(acac) 3 )) to show more broadly that weakly doping microstructured inclusions can act synergis- tically with...P3 ) and PBTTT-C14 ( P4 ). The weak dopant Co(acac) 3 will form large crystals readily in p-type polymers such as P3 and P4 . S > 2000 µV K

Effect of microstructure on the high temperature mechanical properties of (CeO{sub 2}){sub 0.8}(GdO{sub 1.5}){sub 0.2} electrolytes

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

Sammes, N.M.; Zhang, Y.

CeO{sub 2}-based oxides have recently been shown to have great potential as electrolytes in medium temperature solid oxide fuel cell applications, primarily due to their high ionic conductivity. Steele et al., for example, have examined a cell of the type: O{sub 2}, La{sub 0.6}Sr{sub 0.4}Fe{sub 0.8}Co{sub 0.2}O{sub 3}{vert_bar}Ce{sub 0.9}Gd{sub 0.1}O{sub 1.95}{vert_bar}Ni-ZrO{sub 2}, H{sub 2}/H{sub 2}O at 715{degrees}C. Gd{sub 2}O{sub 3} doped CeO{sub 2} has been reported as having one of the highest oxygen ion conductivities of the ceria-based materials. An ionic conductivity of 8.3 x 10{sup -2} s/cm has been reported for (CeO{sub 2}){sub 0.8}(GdO{sub 1.5}){sub 0.2} at 800{degrees}C, whichmore » is approximately four times that of Y{sub 2}O{sub 3}-doped ZrO{sub 2}, at the same temperature. Although the electrical properties of the material have been examined in detail, very little work has considered the microstructural/property relationships, particularly in relation to the mechanical properties. It is well know that CeO{sub 2}-based materials are difficult to density and attempts have been performed to examine this. Preliminary studies have also been undertaken to examine the effect of sintering on the mechanical properties of the material. In this paper we examine the effect of microstructure on the high temperature mechanical properties of (CeO{sub 2}){sub 0.8}(GdO{sub 1.5}){sub 0.2}.« less

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

Abreu-Sepulveda, Maria A.; Dhital, Chetan; Huq, Ashfia

The effect due to systematic substitution of cobalt by iron in La 0.6Ca 0.4Co 1-xFe xO 3 towards the oxygen evolution reaction(OER) in alkaline media has been investigated. We synthesized these compounds by a facile glycine-nitrate synthesis and the phase formation was confirmed by X-ray diffraction and Neutron Diffraction elemental analysis. The apparent OER activity was evaluated by quasi steady state current measurements in alkaline media using a traditional three-electrode cell. X-ray photoelectron spectroscopy shows iron substitution causes an increase in the surface concentration of various cobalt oxidation states. Tafel slope in the vicinity of 60 mV/decade and electrochemical reactionmore » order towards OH- near unity were achieved for the unsubstituted La 0.6Ca 0.4CoO 3. Moreover, a decrease in the Tafel slope to 49 mV/decade was observed when iron is substituted in high amounts in the perovskite structure. The area specific current density showed dependence on the Fe fraction, however the relationship of specific current density with Fe fraction is not linear. High Fe substitutions, La 0.6Ca 0.4Co 0.2Fe 0.8O 3 and La 0.6Ca 0.4Co 0.1Fe 0.9O 3 showed higher area specific activity towards OER than La 0.6Ca 0.4CoO 3 or La 0.6Ca 0.4FeO 3. Finally, we believe iron inclusion in the cobalt sites of the perovskite helps decrease the electron transfer barrier and facilitates the formation of cobalt-hydroxide at the surface. Possible OER mechanisms based on the observed kinetic parameters will be discussed.« less

Amorphous cobalt potassium phosphate microclusters as efficient photoelectrochemical water oxidation catalyst

NASA Astrophysics Data System (ADS)

Zhang, Ye; Zhao, Chunsong; Dai, Xuezeng; Lin, Hong; Cui, Bai; Li, Jianbao

2013-12-01

A novel amorphous cobalt potassium phosphate hydrate compound (KCoPO4·H2O) is identified to be active photocatalyst for oxygen evolution reaction (OER) to facilitate hydrogen generation from water photolysis. It has been synthesized through a facile and cost-effective solution-based precipitation method using earth-abundant materials. Its highly porous structure and large surface areas are found to be responsible for the excellent electrochemical performance featuring a low OER onset at ∼550 mVSCE and high current density in alkaline condition. Unlike traditional cobalt-based spinel oxides (Co3O4, NiCo2O4) and phosphate (Co-Pi, Co(PO3)2) electrocatalysts, with proper energy band alignment for light-assisted water oxidation, cobalt potassium phosphate hydrate also exhibits robust visible-light response, generating a photocurrent density of ∼200 μA cm-2 at 0.7 VSCE. This catalyst could thus be considered as a promising candidate to perform photoelectrochemical water splitting.

Evolution of the magnetic and structural properties of Fe 1 - x Co x V 2 O 4

DOE PAGES

Sinclair, R.; Ma, Jie; Cao, H. B.; ...

2015-10-12

The magnetic and structural properties of single-crystal Fe 1-xCo xV 2O 4 samples have been investigated by performing specific heat, susceptibility, neutron diffraction, and x-ray diffraction measurements. As the orbital-active Fe 2+ ions with larger ionic size are gradually substituted by the orbital-inactive Co 2+ ions with smaller ionic size, the system approaches the itinerant electron limit with decreasing V-V distance. Then, various factors such as the Jahn-Teller distortion and the spin-orbital coupling of the Fe 2+ ions on the A sites and the orbital ordering and electronic itinerancy of the V 3+ ions on the B sites compete withmore » each other to produce a complex magnetic and structural phase diagram. Finally, this phase diagram is compared to those of Fe 1-xMn xV 2O 4 and Mn 1-xCo xV 2O 4 to emphasize several distinct features.« less

Effect of microstructural evolution on mechanical and tribological properties of Ti-doped DLC films: How was an ultralow friction obtained?

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

Zhao, Fei; Li, Hongxuan; Ji, Li

2016-05-15

This paper examined the evolution of microstructure and its effect on the mechanical and tribological properties of ultralow friction Ti-doped diamondlike carbon (DLC) films, by adjusting the CH{sub 4}/Ar ratio under constant radio frequency discharge power and bias. The Raman, high resolution transmission electron microscopy, atomic force microscope and nanoindentation measurements consistently reveal or indicate the formation of curved graphene sheets or fullerenelike nanostructures with increasing CH{sub 4}/Ar ratio. The superior frictional performance (0.008–0.01) of Ti-DLC films can be attributed to the special microstructure related to the development of embedded fullerenelike nanostructures as a result of incorporation of TiO{sub 2}more » clusters. The contributing factors include high hardness and cohesion, excellent toughness, high load-bearing capacity, as well as the ultralow shear resistance transform layer and the excellent antioxidation stability brought by the doped Ti.« less

Surface-engineered core-shell nano-size ferrites and their antimicrobial activity

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

Baraliya, Jagdish D., E-mail: jdbaraliya@yahoo.co.in; Joshi, Hiren H., E-mail: jdbaraliya@yahoo.co.in

We report the results of biological study on core-shell structured MFe{sub 2}O{sub 4} (where M = Co, Mn, Ni) nanoparticles and influence of silica- DEG dual coating on their antimicrobial activity. Spherical MFe{sub 2}O{sub 4} nanoparticles were prepared via a Co-precipitation method. The microstructures and morphologies of these nanoparticles were studied by x-ray diffraction and FTIR. The antimicrobial activity study carried out in nutrient agar medium with addition of antimicrobial synthesis compound which is tested for its activity against different types of bacteria.

Surface-engineered core-shell nano-size ferrites and their antimicrobial activity

NASA Astrophysics Data System (ADS)

Baraliya, Jagdish D.; Joshi, Hiren H.

2014-04-01

We report the results of biological study on core-shell structured MFe2O4 (where M = Co, Mn, Ni) nanoparticles and influence of silica- DEG dual coating on their antimicrobial activity. Spherical MFe2O4 nanoparticles were prepared via a Co-precipitation method. The microstructures and morphologies of these nanoparticles were studied by x-ray diffraction and FTIR. The antimicrobial activity study carried out in nutrient agar medium with addition of antimicrobial synthesis compound which is tested for its activity against different types of bacteria.

Microstructure and wear resistance of Ti-Cu-N composite coating prepared via laser cladding/laser nitriding technology on Ti-6Al-4V alloy

NASA Astrophysics Data System (ADS)

Yang, Yuling; Cao, Shiyin; Zhang, Shuai; Xu, Chuan; Qin, Gaowu

2017-07-01

Ti-Cu-N coatings with three different Cu contents on Ti-6Al-4V alloy (TC4) were obtained via laser cladding together with laser nitriding (LC/LN) technology. Phase constituents, microstructure, microhardness, and wear resistance of the coatings were investigated. The evolution of the coefficients of friction for the three coatings was measured under dry sliding conditions as a function of the revolutions until the coating failure. The results show that the coatings are mainly composed of TiN, CuTi3 and some TiO6 phases dispersed in the matrix. A good metallurgical bonding between the coating and substrate has been successfully obtained. The prepared Ti-Cu-N composite coatings almost doubly enhance the microhardness of the TC4 alloy and reduce the friction down to 1/4-1/2 of the TC4 alloy, and thus significantly improve the wear resistance. The coefficient of friction depends on the Cu content in the coating.

Evolution of frozen magnetic state in co-precipitated ZnδCo1-δFe2O4 (0 ≤ δ ≤ 1) ferrite nanopowders

NASA Astrophysics Data System (ADS)

Kubisztal, M.; Kubisztal, J.; Karolus, M.; Prusik, K.; Haneczok, G.

2018-05-01

The evolution of frozen magnetic state of ZnδCo1-δFe2O4 (0 ≤ δ ≤ 1) ferrite nanoparticles was studied by applying vibrating sample magnetometer measurements in temperature range 5-350 K and magnetic fields up to 7 T. It was shown that gradual conversion from the inverse spinel (δ = 0) to the normal one (δ = 1.0) is correlated with a drop of freezing temperature Tf (corresponding to blocking of mean magnetic moment of the system) from 238 K (δ = 0) to 9 K (δ = 1.0) and with a decrease of magnetic anisotropy constant K1 from about 8 · 105 J/m3 to about 3 · 105 J/m3. The percolation threshold predicted for bulk ferrites at 1 - δ ≈ 0.33 was observed as a significant weakness of ferrimagnetic coupling. In this case magnetization curves, determined according to the zero field cooling protocol, reveal two distinct maxima indicating that the system splits into two assemblies with specific ions distribution between A and B sites.

On-line estimation of O2 production, CO2 uptake, and growth kinetics of microalgal cultures in a gas-tight photobioreactor

PubMed Central

Riisgård, Frederik Kier; Gunther, William Stuart; Lønsmann Iversen, Jens Jørgen

2006-01-01

Growth of the green algae Chlamydomonas reinhardtii and Chlorella sp. in batch cultures was investigated in a novel gas-tight photobioreactor, in which CO2, H2, and N2 were titrated into the gas phase to control medium pH, dissolved oxygen partial pressure, and headspace pressure, respectively. The exit gas from the reactor was circulated through a loop of tubing and re-introduced into the culture. CO2 uptake was estimated from the addition of CO2 as acidic titrant and O2 evolution was estimated from titration by H2, which was used to reduce O2 over a Pd catalyst. The photosynthetic quotient, PQ, was estimated as the ratio between O2 evolution and CO2 up-take rates. NH4+, NO2−, or NO3− was the final cell density limiting nutrient. Cultures of both algae were, in general, characterised by a nitrogen sufficient growth phase followed by a nitrogen depleted phase in which starch was the major product. The estimated PQ values were dependent on the level of oxidation of the nitrogen source. The PQ was 1 with NH4+ as the nitrogen source and 1.3 when NO3− was the nitrogen source. In cultures grown on all nitrogen sources, the PQ value approached 1 when the nitrogen source was depleted and starch synthesis became dominant, to further increase towards 1.3 over a period of 3–4 days. This latter increase in PQ, which was indicative of production of reduced compounds like lipids, correlated with a simultaneous increase in the degree of reduction of the biomass. When using the titrations of CO2 and H2 into the reactor headspace to estimate the up-take of CO2, the production of O2, and the PQ, the rate of biomass production could be followed, the stoichiometrical composition of the produced algal biomass could be estimated, and different growth phases could be identified. PMID:19396354

Quality of Metal Deposited Flux Cored Wire With the System Fe-C-Si-Mn-Cr-Mo-Ni-V-Co

NASA Astrophysics Data System (ADS)

Gusev, Aleksander I.; Kozyrev, Nikolay A.; Osetkovskiy, Ivan V.; Kryukov, Roman E.; Kozyreva, Olga A.

2017-10-01

Studied the effect of the introduction of vanadium and cobalt into the charge powder fused wire system Fe-C-Si-Mn-Cr-Ni-Mo-V, used in cladding assemblies and equipment parts and mechanisms operating under abrasive and abrasive shock loads. the cored wires samples were manufactured in the laboratory conditions and using appropriate powder materials and as a carbonfluoride contained material were used the dust from gas purification of aluminum production, with the following components composition, %: Al2O3 = 21-46.23; F = 18-27; Na2O = 8-15; K2O = 0.4-6; CaO = 0.7-2.3; Si2O = 0.5-2.48; Fe2O3 = 2.1-3.27; C = 12.5-30.2; MnO = 0.07-0.9; MgO = 0.06-0.9; S = 0.09-0.19; P = 0.1-0.18. Surfacing was produced on the St3 metal plates in 6 layers under the AN-26C flux by welding truck ASAW-1250. Cutting and preparation of samples for research had been implemented. The chemical composition and the hydrogen content of the weld metal were determined by modern methods. The hardness and abrasion rate of weld metal had been measured. Conducted metallographic studies of weld metal: estimated microstructure, grain size, contamination of oxide non-metallic inclusions. Metallographic studies showed that the microstructure of the surfaced layer by cored wire system Fe-C-Si-Mn-Cr-Mo-Ni-V-Co is uniform, thin dendrite branches are observed. The microstructure consists of martensite, which is formed inside the borders of the former austenite grain retained austenite present in small amounts in the form of separate islands, and thin layers of δ-ferrite, which is located on the borders of the former austenite grains. Carried out an assessment the effect of the chemical composition of the deposited metal on the hardness and wear and hydrogen content. In consequence of multivariate correlation analysis, it was determined dependence to the hardness of the deposited layer and the wear resistance of the mass fraction of the elements included in the flux-cored wires of the system Fe-C-Si-Mn-Cr-Mo-Ni-V-Co. The calculated value of the average approximation error suggests that the dependence is adequate and can be used to determine the resulting indicators. These dependencies can be used to predict the hardness of the deposited layer and its wear resistance while changing the chemical composition of the weld metal.

The Viking gas exchange experiment results from Chryse and Utopia surface samples

NASA Technical Reports Server (NTRS)

Oyama, V. I.; Berdahl, B. J.

1977-01-01

Immediate gas changes occurred when untreated Martian surface samples were humidified and/or wet by an aqueous nutrient medium in the Viking lander gas exchange experiment. The evolutions of N2, CO2, and Ar are mainly associated with soil surface desorption caused by water vapor, while O2 evolution is primarily associated with decomposition of superoxides inferred to be present on Mars. On recharges with fresh nutrient and test gas, only CO2 was given off, and its rate of evolution decreased with each recharge. This CO2 evolution is thought to come from the oxidation of organics present in the nutrient by gamma Fe2O3 in the surface samples. Atmospheric analyses were also performed at both sites. The mean atmospheric composition from four analyses is N2, 2.3%; O2, not greater than 0.15%; Ar, 1.5% and CO2, 96.2%.

Rose-like monodisperse bismuth subcarbonate hierarchical hollow microspheres: one-pot template-free fabrication and excellent visible light photocatalytic activity and photochemical stability for NO removal in indoor air.

PubMed

Dong, Fan; Lee, S C; Wu, Zhongbiao; Huang, Yu; Fu, Min; Ho, Wing-Kei; Zou, Shichun; Wang, Bo

2011-11-15

Rose-like monodisperse hierarchical (BiO)(2)CO(3) hollow microspheres are fabricated by a one-pot template-free method for the first time based on hydrothermal treatment of ammonia bismuth citrate and urea in water. The microstructure and band structure of the as-prepared (BiO)(2)CO(3) superstructure are characterized in detail by X-ray diffraction, Raman spectroscopy, Fourier transform-infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, N(2) adsorption-desorption isotherms, X-ray photoelectron spectroscopy and UV-vis diffuse reflectance spectroscopy. The monodisperse hierarchical (BiO)(2)CO(3) microspheres are constructed by the self-assembly of single-crystalline nanosheets. The aggregation of nanosheets result in the formation of three dimensional hierarchical framework containing mesopores and macropores, which is favorable for efficient transport of reaction molecules and harvesting of photo-energy. The result reveals the existence of special two-band-gap structure (3.25 and 2.0 eV) for (BiO)(2)CO(3). The band gap of 3.25 eV is intrinsic and the formation of smaller band gap of 2.0 eV can be ascribed to the in situ doped nitrogen in lattice. The performance of hierarchical (BiO)(2)CO(3) microspheres as efficient photocatalyst are further demonstrated in the removal of NO in indoor air under both visible light and UV irradiation. It is found that the hierarchical (BiO)(2)CO(3) microspheres not only exhibit excellent photocatalytic activity but also high photochemical stability during long term photocatalytic reaction. The special microstructure, the high charge separation efficiency due to the inductive effect, and two-band-gap structure in all contribute to the outstanding photocatalytic activities. The discovery of monodisperse hierarchical nitrogen doped (BiO)(2)CO(3) hollow structure is significant because of its potential applications in environmental pollution control, solar energy conversion, catalysis and other related areas. Copyright © 2011 Elsevier B.V. All rights reserved.

Effect of A-Site Cation Ordering on Chemical Stability, Oxygen Stoichiometry and Electrical Conductivity in Layered LaBaCo2O5+δ Double Perovskite

PubMed Central

Bernuy-Lopez, Carlos; Høydalsvik, Kristin; Einarsrud, Mari-Ann; Grande, Tor

2016-01-01

The effect of the A-site cation ordering on the chemical stability, oxygen stoichiometry and electrical conductivity in layered LaBaCo2O5+δ double perovskite was studied as a function of temperature and partial pressure of oxygen. Tetragonal A-site cation ordered layered LaBaCo2O5+δ double perovskite was obtained by annealing cubic A-site cation disordered La0.5Ba0.5CoO3-δ perovskite at 1100 °C in N2. High temperature X-ray diffraction between room temperature (RT) and 800 °C revealed that LaBaCo2O5+δ remains tetragonal during heating in oxidizing atmosphere, but goes through two phase transitions in N2 and between 450 °C and 675 °C from tetragonal P4/mmm to orthorhombic Pmmm and back to P4/mmm due to oxygen vacancy ordering followed by disordering of the oxygen vacancies. An anisotropic chemical and thermal expansion of LaBaCo2O5+δ was demonstrated. La0.5Ba0.5CoO3-δ remained cubic at the studied temperature irrespective of partial pressure of oxygen. LaBaCo2O5+δ is metastable with respect to La0.5Ba0.5CoO3-δ at oxidizing conditions inferred from the thermal evolution of the oxygen deficiency and oxidation state of Co in the two materials. The oxidation state of Co is higher in La0.5Ba0.5CoO3-δ resulting in a higher electrical conductivity relative to LaBaCo2O5+δ. The conductivity in both materials was reduced with decreasing partial pressure of oxygen pointing to a p-type semiconducting behavior. PMID:28773279

Oxygen electrode bifunctional electrocatalyst NiCo2O4 spinel

NASA Technical Reports Server (NTRS)

Fielder, William L.; Singer, Joseph

1988-01-01

A significant increase in energy density may be possible if a two-unit alkaline regenerative H2-O2 fuel cell is replaced with a single-unit system that uses passive means for H2O transfer and thermal control. For this single-unit system, new electrocatalysts for the O2 electrode will be required which are not only bifunctionally active but also chemically and electrochemically stable between the voltage range of about 0.7 and 1.5 V. NiCo2O4 spinel is reported to have certain characteristics that make it useful for a study of electrode fabrication techniques. High surface area NiCo2O4 powder was fabricated into unsupported, bifunctional, PTFE-bonded, porous gas fuel cell electrodes by commercial sources using varying PTFE contents and sintering temperatures. The object of this study is to measure the bifunctional activities of these electrodes and to observe what performance differences might result from different commercial electrode fabricators. O2 evolution and O2 reduction data were obtained at 80 C (31 percent KOH). An irreversible reaction (i.e., aging) occurred during O2 evolution at potentials greater than about 1.5 V. Anodic Tafel slopes of 0.06 and 0.12 V/decade were obtained for the aged electrodes. Within the range of 15 to 25 percent, the PTFE content was not a critical parameter for optimizing the electrode for O2 evolution activity. Sintering temperatures between 300 and 340 C may be adequate but heating at 275 C may not be sufficient to properly sinter the PTFE-NiCo2O4 mixture. Electrode disintegration was observed during O2 reduction. Transport of O2 to the NiCo2O4 surface became prohibitive at greater than about -0.02 A/sq cm. Cathodic Tafel slopes of -0.6 and -0.12 V/decade were assumed for the O2 reduction process. A PTFE content of 25 percent (or greater) appears to be preferable for sintering the PTFE-NiCo2O4 mixture.

Microstructural, dielectric and magnetic properties of multiferroic composite system barium strontium titanate – nickel cobalt ferrite

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

Pahuja, Poonam, E-mail: poonampahuja123@gmail.com; Tandon, R. P., E-mail: ram-tandon@hotmail.com

2015-05-15

Multiferroic composites (1-x) Ba{sub 0.95}Sr{sub 0.05}TiO{sub 3} + (x) Ni{sub 0.8}Co{sub 0.2}Fe{sub 2}O{sub 4} (where x = 0.1, 0.2, 0.3, 0.4) has been prepared by solid state reaction method. X-ray diffraction analysis of the composite samples confirmed the presence of both barium strontium titanate (BST) and nickel cobalt ferrite (NCF) phases. FESEM images indicated the well dispersion of NCF grains among BST grains. Dielectric constant and loss of the composite samples decreases with increase in frequency following Maxwell-Wagner relaxation mechanism. Composite sample with highest ferrite content possesses highest values of remanent and saturation magnetization.

Evolution of crystal structure during the initial stages of ZnO atomic layer deposition

DOE PAGES

Boichot, R.; Tian, L.; Richard, M. -I.; ...

2016-01-05

In this study, a complementary suite of in situ synchrotron X-ray techniques is used to investigate both structural and chemical evolution during ZnO growth by atomic layer deposition. Focusing on the first 10 cycles of growth, we observe that the structure formed during the coalescence stage largely determines the overall microstructure of the film. Furthermore, by comparing ZnO growth on silicon with a native oxide with that on Al 2O 3(001), we find that even with lattice-mismatched substrates and low deposition temperatures, the crystalline texture of the films depend strongly on the nature of the interfacial bonds.

Effects of elevated pCO2 on physiological performance of marine microalgae Dunaliella salina (Chlorophyta, Chlorophyceae

NASA Astrophysics Data System (ADS)

Hu, Shunxin; Wang, You; Wang, Ying; Zhao, Yan; Zhang, Xinxin; Zhang, Yongsheng; Jiang, Ming; Tang, Xuexi

2018-03-01

The present study was conducted to determine the effects of elevated pCO2 on growth, photosynthesis, dark respiration and inorganic carbon acquisition in the marine microalga Dunaliella salina. To accomplish this, D. salina was incubated in semi-continuous cultures under present-day CO2 levels (390 μatm, pHNBS: 8.10), predicted year 2100 CO2 levels (1 000 μatm, pHNBS: 7.78) and predicted year 2300 CO2 levels (2 000 μatm, pHNBS: 7.49). Elevated pCO2 significantly enhanced photosynthesis (in terms of gross photosynthetic O2 evolution, effective quantum yield (Δ F/ F' m ), photosynthetic efficiency ( α), maximum relative electron transport rate (rETRmax) and ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) activity) and dark respiration of D. salina, but had insignificant effects on growth. The photosynthetic O2 evolution of D. salina was significantly inhibited by the inhibitors acetazolamide (AZ), ethoxyzolamide (EZ) and 4,4'-diisothiocyanostilbene-2,2'-disulfonate (DIDS), indicating that D. salina is capable of acquiring HCOˉ 3 via extracellular carbonic anhydrase and anion-exchange proteins. Furthermore, the lower inhibition of the photosynthetic O2 evolution at high pCO2 levels by AZ, EZ and DIDS and the decreased carbonic anhydrase showed that carbon concentrating mechanisms were down-regulated at high pCO2. In conclusion, our results show that photosynthesis, dark respiration and CCMs will be affected by the increased pCO2/low pH conditions predicted for the future, but that the responses of D. salina to high pCO2/low pH might be modulated by other environmental factors such as light, nutrients and temperature. Therefore, further studies are needed to determine the interactive effects of pCO2, temperature, light and nutrients on marine microalgae.

Effects of elevated pCO2 on physiological performance of marine microalgae Dunaliella salina (Chlorophyta, Chlorophyceae)

NASA Astrophysics Data System (ADS)

Hu, Shunxin; Wang, You; Wang, Ying; Zhao, Yan; Zhang, Xinxin; Zhang, Yongsheng; Jiang, Ming; Tang, Xuexi

2017-06-01

The present study was conducted to determine the effects of elevated pCO2 on growth, photosynthesis, dark respiration and inorganic carbon acquisition in the marine microalga Dunaliella salina. To accomplish this, D. salina was incubated in semi-continuous cultures under present-day CO2 levels (390 μatm, pHNBS: 8.10), predicted year 2100 CO2 levels (1 000 μatm, pHNBS: 7.78) and predicted year 2300 CO2 levels (2 000 μatm, pHNBS: 7.49). Elevated pCO2 significantly enhanced photosynthesis (in terms of gross photosynthetic O2 evolution, effective quantum yield (ΔF/F' m ), photosynthetic efficiency (α), maximum relative electron transport rate (rETRmax) and ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) activity) and dark respiration of D. salina, but had insignificant effects on growth. The photosynthetic O2 evolution of D. salina was significantly inhibited by the inhibitors acetazolamide (AZ), ethoxyzolamide (EZ) and 4,4'-diisothiocyanostilbene-2,2'-disulfonate (DIDS), indicating that D. salina is capable of acquiring HCO3 - via extracellular carbonic anhydrase and anion-exchange proteins. Furthermore, the lower inhibition of the photosynthetic O2 evolution at high pCO2 levels by AZ, EZ and DIDS and the decreased carbonic anhydrase showed that carbon concentrating mechanisms were down-regulated at high pCO2. In conclusion, our results show that photosynthesis, dark respiration and CCMs will be affected by the increased pCO2/low pH conditions predicted for the future, but that the responses of D. salina to high pCO2/low pH might be modulated by other environmental factors such as light, nutrients and temperature. Therefore, further studies are needed to determine the interactive effects of pCO2, temperature, light and nutrients on marine microalgae.

Atomic structures of Ruddlesden-Popper faults in LaCoO3/SrRuO3 multilayer thin films induced by epitaxial strain

NASA Astrophysics Data System (ADS)

Wang, Wei; Zhang, Hui; Shen, Xi; Guan, Xiangxiang; Yao, Yuan; Wang, Yanguo; Sun, Jirong; Yu, Richeng

2018-05-01

In this paper, scanning transmission electron microscopy is used to study the microstructures of the defects in LaCoO3/SrRuO3 multilayer films grown on the SrTiO3 substrates, and these films have different thickness of SrRuO3 (SRO) layers. Several types of Ruddlesden-Popper (R.P.) faults at an atomic level are found, and these chemical composition fluctuations in the growth process are induced by strain fields originating from the film-film and film-substrate lattice mismatches. Furthermore, we propose four types of structural models based on the atomic arrangements of the R.P. planar faults, which severely affect the functional properties of the films.

Tunable Bifunctional Activity of Mnx Co3-x O4 Nanocrystals Decorated on Carbon Nanotubes for Oxygen Electrocatalysis.

PubMed

Zhao, Tingting; Gadipelli, Srinivas; He, Guanjie; Ward, Matthew J; Do, David; Zhang, Peng; Guo, Zhengxiao

2018-04-25

Noble-metal-free electrocatalysts are attractive for cathodic oxygen catalysis in alkaline membrane fuel cells, metal-air batteries, and electrolyzers. However, much of the structure-activity relationship is poorly understood. Herein, the comprehensive development of manganese cobalt oxide/nitrogen-doped multiwalled carbon nanotube hybrids (Mn x Co 3-x O 4 @NCNTs) is reported for highly reversible oxygen reduction and evolution reactions (ORR and OER, respectively). The hybrid structures are rationally designed by fine control of surface chemistry and synthesis conditions, including tuning of functional groups at surfaces, congruent growth of nanocrystals with controllable phases and particle sizes, and ensuring strong coupling across catalyst-support interfaces. Electrochemical tests reveal distinctly different oxygen catalytic activities among the hybrids, Mn x Co 3-x O 4 @NCNTs. Nanocrystalline MnCo 2 O 4 @NCNTs (MCO@NCNTs) hybrids show superior ORR activity, with a favorable potential to reach 3 mA cm -2 and a high current density response, equivalent to that of the commercial Pt/C standard. Moreover, the hybrid structure exhibits tunable and durable catalytic activities for both ORR and OER, with a lowest overall potential of 0.93 V. It is clear that the long-term electrochemical activities can be ensured by rational design of hybrid structures from the nanoscale. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Evolution of Interstellar Ices

NASA Astrophysics Data System (ADS)

Allamandola, Louis J.; Bernstein, Max P.; Sandford, Scott A.; Walker, Robert L.

1999-10-01

Infrared observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the building blocks of comets. Ices in molecular clouds are dominated by the very simple molecules H2O, CH3OH, NH3, CO, CO2, and probably H2CO and H2. More complex species including nitriles, ketones, and esters are also present, but at lower concentrations. The evidence for these, as well as the abundant, carbon-rich, interstellar, polycyclic aromatic hydrocarbons (PAHs) is reviewed. Other possible contributors to the interstellar/pre-cometary ice composition include accretion of gas-phase molecules and in situ photochemical processing. By virtue of their low abundance, accretion of simple gas-phase species is shown to be the least important of the processes considered in determining ice composition. On the other hand, photochemical processing does play an important role in driving dust evolution and the composition of minor species. Ultraviolet photolysis of realistic laboratory analogs readily produces H2, H2CO, CO2, CO, CH4, HCO, and the moderately complex organic molecules: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), R-CN (nitriles), and hexamethylenetetramine (HMT, C6H12N4), as well as more complex species including amides, ketones, and polyoxymethylenes (POMs). Inclusion of PAHs in the ices produces many species similar to those found in meteorites including aromatic alcohols, quinones and ethers. Photon assisted PAH-ice deuterium exchange also occurs. All of these species are readily formed and are therefore likely cometary constituents.

Binary cobalt ferrite nanomesh arrays as the advanced binder-free electrode for applications in oxygen evolution reaction and supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Li; Zhang, Huijuan; Mu, Yanping; Bai, Yuanjuan; Wang, Yu

2016-09-01

The porous CoFe2O4nanomesh arrays are successfully synthesized on nickel foam substrate through a high temperature and pressure hydrothermal method, following by the thermal post-treatment in air. The CoFe2O4 nanomesh arrays own numerous pores and large specific surface area, which is in favor of exposing more active sites. In consideration of the structural preponderances and versatility of the materials, the CoFe2O4 nanomesh arrays have been researched as the binder-free electrode materials for electrocatalysis and supercapacitors. When the CoFe2O4nanomesh arrays on nickel foam (CoFe2O4 NM-As/Ni) directly act as the free-binder catalyst toward catalyzing the oxygen evolution reaction (OER) of electrochemical water splitting, CoFe2O4 NM-As/Ni exhibits an admirable OER property with a low onset potential of 1.47 V(corresponding to the onset overpotential of 240 mV), a minimal overpotential (η10 = 253 mV), a small Tafel slope (44 mV dec-1), large anodic currents and long-term durability for 35 h in alkaline media. In addition, as an electrode of supercapacitors, CoFe2O4 NM-As/Ni obtains a desired specific capacitance (1426 F/g at the current density of 1 A/g), remarkable rate capability (1024 F/g at the current density of 20 A/g) and eminent capacitance retention (92.6% after 3000 cycles). The above results demonstrate the CoFe2O4 NM-As/Ni possesses great potential application in electrocatalysis and supercapacitors.

Discontinuous Precipitation Reactions in Co-10Al-4C (At. Pct)

NASA Astrophysics Data System (ADS)

Kamali, H.; Hossein Nedjad, S.; Kaufman, M. J.; Field, R. D.; Clarke, A. J.

2018-05-01

The evolution of microstructure and microhardness of a Co-10Al-4C (at. pct) alloy during isothermal aging at 800 and 900 °C is reported. Fine κ-Co3AlC0.5 intermetallic precipitates form in an FCC α-Co matrix after aging at both temperatures. Lamellar discontinuous precipitation also occurred at grain boundaries and the lamellar transformation product consumed the fine κ-Co3AlC0.5 precipitates in the matrix during aging. The microhardness of the alloy decreased dramatically upon formation of the lamellar product. Transmission electron microscopy revealed that the lamellar product consists of α-Co, κ-Co3AlC0.5, and B2-CoAl phases at 800 °C. The orientation relationship between α-Co and κ-Co3AlC0.5 phases, and between α-Co and B2-CoAl phases were identified as cube-on-cube and Kurdjumov-Sachs, respectively. The discontinuous product at 900 °C was composed of alternating α-Co and κ-Co3AlC0.5 lamellae, without the B2-CoAl phase that formed at 800 °C. Additional continuous coarsening of κ-Co3AlC0.5 phase was observed in the lamellar aggregate during prolonged aging at 900 °C. The main driving force for the discontinuous reaction appears to be the reduction in both interfacial energy and elastic strain energy where the latter is attributed to the relatively high lattice mismatch between the κ-Co3AlC0.5 precipitates and the α-Co matrix.

Processing, microstructure evolution and properties of nanoscale aluminum alloys

NASA Astrophysics Data System (ADS)

Han, Jixiong

In this project, phase transformations and precipitation behavior in age-hardenable nanoscale materials systems, using Al-Cu alloys as model materials, were first studied. The Al-Cu nanoparticles were synthesized by a Plasma Ablation process and found to contain a 2˜5 nm thick adherent aluminum oxide scale, which prevented further oxidation. On aging of the particles, a precipitation sequence consisting of, nearly pure Cu precipitates to the metastable theta' to equilibrium theta was observed, with all three forming along the oxide-particle interface. The structure of theta' and its interface with the Al matrix has been characterized in detail. Ultrafine Al-Cu nanoparticles (5˜25 nm) were also synthesized by inert gas condensation (IGC) and their aging behavior was studied. These particles were found to be quite stable against precipitation. Secondly, pure Al nanoparticles were prepared by the Exploding Wire process and their sintering and consolidation behavior were studied. It was found that nanopowders of Al could be processed to bulk structures with high hardness and density. Sintering temperature was found to have a dominant effect on density, hardness and microstructure. Sintering at temperatures >600°C led to breakup of the oxide scale, leading to an interesting nanocomposite composed of 100˜200 nm Al oxide dispersed in a bimodal nanometer-micrometer size Al matrix grains. Although there was some grain growth, the randomly dispersed oxide fragments were quite effective in pinning the Al grain boundaries, preventing excessive grain growth and retaining high hardness. Cold rolling and hot rolling were effective methods for attaining full densification and high hardness. Thirdly, the microstructure evolution and mechanical behavior of Al-Al 2O3 nanocomposites were studied. The composites can retain high strength at elevated temperature and thermal soaking has practically no detrimental effect on strength. Although the ductility of the composite remains quite low, there was substantial evidence for high localized plasticity. The strengthening mechanisms of the composite include: Orowan strengthening, grain size strengthening and Forest strengthening. Finally, the microstructure evolution and mechanical behavior of 2024Al-Al 2O3 nanocomposites were studied. This 2024Al-Al2O 3 composite exhibits similar thermal stability and high strength at elevated temperature as Al-Al2O3. On aging, the matrix of 2024Al-Al2O3 composites revealed a precipitation sequence of: alphaAl → GP/GPB → theta'/S' → theta/S. The strengthening mechanisms of the 2024Al-Al2O3 composites include precipitation strengthening, Orowan strengthening, grain size strengthening and Forest strengthening.

Low temperature processed MnCo2O4 and MnCo1.8Fe0.2O4 as effective protective coatings for solid oxide fuel cell interconnects at 750 °C

NASA Astrophysics Data System (ADS)

Molin, S.; Jasinski, P.; Mikkelsen, L.; Zhang, W.; Chen, M.; Hendriksen, P. V.

2016-12-01

In this study two materials, MnCo2O4 and MnCo1.8Fe0.2O4 are studied as potential protective coatings for Solid Oxide Fuel Cell interconnects working at 750 °C. First powder fabrication by a modified Pechini method is described followed by a description of the coating procedure. The protective action of the coating applied on Crofer 22 APU is evaluated by following the area specific resistance (ASR) of the scale/coating for 5500 h including several thermal cycles. The coating is prepared by brush painting and has a porous structure after deposition. Post mortem microstructural characterization performed on the coated samples shows good protection against chromium diffusion from the chromia scale ensured by a formation of a dense reaction layer. This study shows, that even without high temperature sintering and/or reactive sintering it is possible to fabricate protective coatings based on MnCo spinels.

Decorating unoxidized-carbon nanotubes with homogeneous Ni-Co spinel nanocrystals show superior performance for oxygen evolution/reduction reactions

NASA Astrophysics Data System (ADS)

Yang, Jun; Fujigaya, Tsuyohiko; Nakashima, Naotoshi

2017-03-01

We present a new concept for homogeneous spinel nanocrystal-coating on high crystalline pristine-carbon nanotubes (CNTs) for efficient and durable oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Oxidized CNTs have widely been used to functionalize with metal or metal oxides since the defect sites act as anchoring for metal oxide binding. However, such defects on the tubes cause the decrease in electrical conductivity and stability, leading to lower catalyst performance. In the present study, at first, pristine multi-walled carbon nanotubes (MWNTs) were wrapped by pyridine-based polybenzimidazole (PyPBI) to which uniform NixCo3-xO4 nanocrystals were homogeneously deposited by the solvothermal method without damaging the MWNTs, in which PyPBI acted as efficient anchoring sites for the deposition of spinel oxide nanocrystals with ~5 nm size. The obtained catalyst (MWNT-PyPBI-NixCo3-xO4) outperformed most state-of-the-art non-precious metal-based bifunctional catalysts; namely, for OER, the potential at 10 mA cm-2 and Tafel slope in 1 M KOH solution were 1.54 V vs. RHE and 42 mV dec-1, respectively. For ORR, the onset and half-wave potentials are 0.918 V and 0.811 V vs. RHE, respectively. Moreover, the MWNT-PyPBI-NixCo3-xO4 demonstrates an excellent durability for both ORR and OER.

Co and Fe doping effect on negative temperature coefficient characteristics of nano-grained NiMn2O4 thick films fabricated by aerosol-deposition.

PubMed

Ryu, Jungho; Han, Guifang; Lee, Jong-Pil; Lim, Dong-Soo; Park, Yun-Soo; Jeong, Dae-Yong

2013-05-01

Spinel structured highly dense NiMn2O4-based (NMO) negative temperature coefficient (NTC) thermistor thick films were fabricated by aerosol-deposition at room temperature. To enhance the thermistor B constant, which represents the temperature sensitivity of the NMO thermistor material, Co and Co-Fe doping was applied. In the case of single element doping of Co, 5 mol% doped NMO showed a high B constant of over 5000 K, while undoped NMO showed -4000 K. By doping Fe to the 5 mol% Co doped NMO, the B constant was more enhanced at over 5600 K. The aging effect on the NTC characteristics of Co doped and Fe-Co co-doped NMO thick film showed very stable resistivity-time characteristics because of the highly dense microstructure.

Thermal response, catalytic activity, and color change of the first hybrid vanadate containing Bpe guest molecules.

PubMed

Fernández de Luis, Roberto; Urtiaga, M Karmele; Mesa, José L; Larrea, Edurne S; Iglesias, Marta; Rojo, Teófilo; Arriortua, María I

2013-03-04

Four isomorphic compounds with formula [{Co2(H2O)2(Bpe)2}(V4O12)]·4H2O·Bpe, CoBpe 1; [{CoNi(H2O)2(Bpe)2}(V4O12)]·4H2O·Bpe, CoNiBpe 2; [{Co0.6Ni1.4(H2O)2(Bpe)2}(V4O12)]·4H2O·Bpe, NiCoBpe 3; and [{Ni2(H2O)2(Bpe)2}(V4O12)]·4H2O·Bpe, NiBpe 4, have been obtained by hydrothermal synthesis. The crystal structures of CoBpe 1 and NiBpe 4 were determined by single-crystal X-ray diffraction (XRD). The Rietveld refinement of CoNiBpe 2 and NiCoBpe 3 XRD patterns confirms that those are isomorphic. The compounds crystallize in the P1̅ space group, exhibiting a crystal structure constructed from inorganic layers pillared by Bpe ligands. The crystal structure contains intralayer and interlayer channels, in which the crystallization water molecules and Bpe guest molecules, respectively, are located. The solvent molecules establish a hydrogen bonding network with the coordinated water molecules. Thermodiffractometric and thermogravimetric studies showed that the loss of crystallization and coordinated water molecules takes place at different temperatures, giving rise to crystal structure transformations that involve important reduction of the interlayer distance, and strong reduction of crystallinity. The IR, Raman, and UV-vis spectra of the as-synthesized and heated compounds confirm that the structural building blocks and octahedral coordination environment of the metal centers are maintained after the structural transformations. The color change and reversibility of the water molecules uptake/removal were tested showing that the initial color is not completely recovered when the compounds are heated at temperatures higher than 200 °C. The thermal evolution of the magnetic susceptibility indicates one-dimensional antiferromagnetic coupling of the metal centers at high temperatures. For NiCoBpe 3 and NiBpe 4 compounds magnetic ordering is established at low temperatures, as can be judged by the maxima observed in the magnetic susceptibilities. CoNiBpe 2 was proved as catalyst being active for cyanosilylation reactions of aldehydes.

Preparation and characterization of coating sodium trisilicate (Na2O.nSiO2) at calcium carbonate (CaCO3) for blowing agent in Mg alloy foam

NASA Astrophysics Data System (ADS)

Erryani, Aprilia; Lestari, Franciska Pramuji; Annur, Dhyah; Kartika, Ika

2018-05-01

The role of blowing agent in the manufacture of porous metal alloys is very important to produce the desired pore. The thermal stability and speed of foam formation have an effect on the resulting pore structure. In porous metal alloys, uniformity of size and pore deployment are the main determinants of the resulting alloys. The coating process of calcium carbonate (CaCO3) has been done using Sodium trisilicate solution by sol-gel method. Foaming agent was pretreated by coating SiO2 passive layer on the surface of CaCO3. This coating aims to produce a more stable blowing agent so that the foaming process can produce a more uniform pore size. The microstructure of the SiO2 passive was observed using Scanning Electron Microscope (SEM) equipped by Energy Dispersive X-Ray Spectrometer (EDS) mapping. The results showed coating CaCO3 using sodium trisilicate was successfully done creating a passive layer of SiO2 on the surface of CaCO3. By the coating process, the thermal stability of coated CaCO3 increased compared to uncoated CaCO3.

Physical, mechanical and electrochemical characterization of all-perovskite intermediate temperature solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Mohammadi, Alidad

Strontium- and magnesium-doped lanthanum gallate (LSGM) has been considered as a promising electrolyte for solid oxide fuel cell (SOFC) systems in recent years due to its high ionic conductivity and chemical stability over a wide range of oxygen partial pressures and temperatures. This research describes synthesis, physical and mechanical behavior, electrochemical properties, phase evolution, and microstructure of components of an all-perovskite anode-supported intermediate temperature solid oxide fuel cell (ITSOFC), based on porous La 0.75Sr0.25Cr0.5Mn0.5O3 (LSCM) anode, La0.8Sr0.2Ga0.8Mg0.2O 2.8 (LSGM) electrolyte, and porous La0.6Sr0.4Fe 0.8Co0.2O3 (LSCF) cathode. The phase evolution of synthesized LSGM and LSCM powders has been investigated, and it has been confirmed that there is no reaction between LSGM and LSCM at sintering temperature. Using different amounts of poreformers and binders as well as controlling firing temperature, porosity of the anode was optimized while still retaining good mechanical integrity. The effect of cell operation conditions under dry hydrogen fuel on the SOFC open circuit voltage (OCV) and cell performance were also investigated. Characterization study of the synthesized LSGM indicates that sintering at 1500°C obtains higher electrical conductivity compared to the currently published results, while conductivity of pellets sintered at 1400°C and 1450°C would be slightly lower. The effect of sintering temperature on bulk and grain boundary resistivities was also discussed. The mechanical properties, such as hardness, Young's modulus, fracture toughness and modulus of rupture of the electrolyte were determined and correlated with scanning electron microscopy (SEM) morphological characterization. Linear thermal expansion and thermal expansion coefficient of LSGM were also measured.

NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires with surface rich high valence state metal oxide as an efficient electrocatalyst for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Yang, Liting; Chen, Lin; Yang, Dawen; Yu, Xu; Xue, Huaiguo; Feng, Ligang

2018-07-01

High valence transition metal oxide is significant for anode catalyst of proton membrane water electrolysis technique. Herein, we demonstrate NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires hierarchical nanocomposite catalyst with surface rich high valence metal oxide as an efficient catalyst for oxygen evolution reaction. A low overpotential of 310 mV is needed to drive a 10 mA cm-2 with a Tafel slope of 99 mV dec-1, and a remarkable stability during 8 h is demonstrated in a chronoamperometry test. Theoretical calculation displays the change in the rate-determining step on the nanocomposite electrode in comparison to NiCo2O4 nanowires alone. It is found high valence Ni and Mn oxide in the catalyst system can efficiently facilitate the charge transport across the electrode/electrolyte interface. The enhanced electrical conductivity, more accessible active sites and synergistic effects between NiMn layered double hydroxide nanosheets and NiCo2O4 nanowires can account for the excellent oxygen evolution reaction. The catalytic performance is comparable to most of the best non-noble catalysts and IrO2 noble catalyst, indicating the promising applications in water-splitting technology. It is an important step in the development of hierarchical nanocomposites by surface valence state tuning as an alternative to noble metals for oxygen evolution reaction.

Microstructures and magnetic properties of Co-Al-O granular thin films

NASA Astrophysics Data System (ADS)

Ohnuma, M.; Hono, K.; Onodera, H.; Ohnuma, S.; Fujimori, H.; Pedersen, J. S.

2000-01-01

The microstructures of Co-Al-O thin films of wide varieties of compositions are studied by transmission electron microscopy and small angle x-ray scattering (SAXS). In the superparamagnetic specimens, high resolution electron microscope images reveal that isolated spherical Co particles are surrounded by an amorphous aluminum oxide matrix. However, in the soft ferromagnetic films, the shape of the Co particles is prolate ellipsoidal. SAXS intensities from the soft magnetic specimens decrease inversely with the wave vector, q, in a low wave-vector region, while an interparticle interference peak is observed for the superparamagnetic specimens. The scattering profiles of the soft magnetic films imply that the Co particles have a cylindrical shape and are randomly oriented. The correlation between the magnetic properties and the microstructures is discussed.

Effect of the addition of B{sub 2}O{sub 3} and BaO-B{sub 2}O{sub 3}-SiO{sub 2} glasses on the microstructure and dielectric properties of giant dielectric constant material CaCu{sub 3}Ti{sub 4}O{sub 12}

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

Shri Prakash, B.; Varma, K.B.R.

2007-06-15

The effect of the addition of glassy phases on the microstructure and dielectric properties of CaCu{sub 3}Ti{sub 4}O{sub 12} (CCTO) ceramics was investigated. Both single-component (B{sub 2}O{sub 3}) and multi-component (30 wt% BaO-60 wt% B{sub 2}O{sub 3}-10 wt% SiO{sub 2} (BBS)) glass systems were chosen to study their effect on the density, microstructure and dielectric properties of CCTO. Addition of an optimum amount of B{sub 2}O{sub 3} glass facilitated grain growth and an increase in dielectric constant. However, further increase in the B{sub 2}O{sub 3} content resulted in its segregation at the grain boundaries associated with a reduction in themore » grain size. In contrast, BBS glass addition resulted in well-faceted grains and increase in the dielectric constant and decrease in the dielectric loss. An internal barrier layer capacitance (IBLC) model was invoked to correlate the dielectric constant with the grain size in these samples. - Graphical abstract: Scanning electron micrograph of 30 wt% BaO-60 wt% B{sub 2}O{sub 3}-10 wt% SiO{sub 2} (BBS) glass-added CaCu{sub 3}Ti{sub 4}O{sub 12} ceramic on sintering.« less

Rational Design of Hierarchically Core-Shell Structured Ni3 S2 @NiMoO4 Nanowires for Electrochemical Energy Storage.

PubMed

Chen, Fangshuai; Ji, Shan; Liu, Quanbing; Wang, Hui; Liu, Hao; Brett, Dan J L; Wang, Guoxiu; Wang, Rongfang

2018-05-30

Rational design and controllable synthesis of nanostructured materials with unique microstructure and excellent electrochemical performance for energy storage are crucially desired. In this paper, a facile method is reported for general synthesis of hierarchically core-shell structured Ni 3 S 2 @NiMoO 4 nanowires (NWs) as a binder-free electrode for asymmetric supercapacitors. Due to the intimate contact between Ni 3 S 2 and NiMoO 4 , the hierarchical structured electrodes provide a promising unique structure for asymmetric supercapacitors. The as-prepared binder-free Ni 3 S 2 @NiMoO 4 electrode can significantly improve the electrical conductivity between Ni 3 S 2 and NiMoO 4 , and effectively avoid the aggregation of NiMoO 4 nanosheets, which provide more active space for storing charge. The Ni 3 S 2 @NiMoO 4 electrode presents a high areal capacity of 1327.3 µAh cm -2 and 67.8% retention of its initial capacity when current density increases from 2 to 40 mA cm -2 . In a two-electrode Ni 3 S 2 @NiMoO 4 //active carbon cell, the active materials deliver a high energy density of 121.5 Wh kg -1 at a power density of 2.285 kW kg -1 with excellent cycling stability. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microstructure and magnetic properties of MFe2O4 (M = Co, Ni, and Mn) ferrite nanocrystals prepared using colloid mill and hydrothermal method

NASA Astrophysics Data System (ADS)

Wang, Wei; Ding, Zui; Zhao, Xiruo; Wu, Sizhu; Li, Feng; Yue, Ming; Liu, J. Ping

2015-05-01

Three kinds of spinel ferrite nanocrystals, MFe2O4 (M = Co, Ni, and Mn), are synthesized using colloid mill and hydrothermal method. During the synthesis process, a rapid mixing and reduction of cations with sodium borohydride (NaBH4) take place in a colloid mill then through a hydrothermal reaction, a slow oxidation and structural transformation of the spinel ferrite nanocrystals occur. The phase purity and crystal lattice parameters are estimated by X-ray diffraction studies. Scanning electron microscopy and transmission electron microscopy images show the morphology and particle size of the as-synthesized ferrite nanocrystals. Raman spectrum reveals active phonon modes at room temperature, and a shifting of the modes implies cation redistribution in the tetrahedral and octahedral sites. Magnetic measurements show that all the obtained samples exhibit higher saturation magnetization (Ms). Meanwhile, experiments demonstrate that the hydrothermal reaction time has significant effects on microstructure, morphologies, and magnetic properties of the as-synthesized ferrite nanocrystals.

Mechanistic Investigations of Water Oxidation by a Molecular Cobalt Oxide Analogue: Evidence for a Highly Oxidized Intermediate and Exclusive Terminal Oxo Participation.

PubMed

Nguyen, Andy I; Ziegler, Micah S; Oña-Burgos, Pascual; Sturzbecher-Hohne, Manuel; Kim, Wooyul; Bellone, Donatela E; Tilley, T Don

2015-10-14

Artificial photosynthesis (AP) promises to replace society's dependence on fossil energy resources via conversion of sunlight into sustainable, carbon-neutral fuels. However, large-scale AP implementation remains impeded by a dearth of cheap, efficient catalysts for the oxygen evolution reaction (OER). Cobalt oxide materials can catalyze the OER and are potentially scalable due to the abundance of cobalt in the Earth's crust; unfortunately, the activity of these materials is insufficient for practical AP implementation. Attempts to improve cobalt oxide's activity have been stymied by limited mechanistic understanding that stems from the inherent difficulty of characterizing structure and reactivity at surfaces of heterogeneous materials. While previous studies on cobalt oxide revealed the intermediacy of the unusual Co(IV) oxidation state, much remains unknown, including whether bridging or terminal oxo ligands form O2 and what the relevant oxidation states are. We have addressed these issues by employing a homogeneous model for cobalt oxide, the [Co(III)4] cubane (Co4O4(OAc)4py4, py = pyridine, OAc = acetate), that can be oxidized to the [Co(IV)Co(III)3] state. Upon addition of 1 equiv of sodium hydroxide, the [Co(III)4] cubane is regenerated with stoichiometric formation of O2. Oxygen isotopic labeling experiments demonstrate that the cubane core remains intact during this stoichiometric OER, implying that terminal oxo ligands are responsible for forming O2. The OER is also examined with stopped-flow UV-visible spectroscopy, and its kinetic behavior is modeled, to surprisingly reveal that O2 formation requires disproportionation of the [Co(IV)Co(III)3] state to generate an even higher oxidation state, formally [Co(V)Co(III)3] or [Co(IV)2Co(III)2]. The mechanistic understanding provided by these results should accelerate the development of OER catalysts leading to increasingly efficient AP systems.

Effect of Rare Earth Cerium Addition on Microstructures and Mechanical Properties of Low Carbon High Manganese Steels

NASA Astrophysics Data System (ADS)

Jiang, M. Z.; Yu, Y. C.; Li, H.; Ren, X.; Wang, S. B.

2017-02-01

Low carbon high manganese steels with different Ce contents were melted in medium frequency vacuum induction furnace. The microstructures and mechanical properties of steels were studied by OM, SEM, EDS and mechanical property testing. The results showed that the microstructures of experimental steels were refined remarkably, inclusions distributed more finely and uniformly, the tensile strength and impact toughness of tested steels both improved greatly after the addition of Ce. Thermodynamic calculation results demonstrated that Ce contained inclusions were Ce2O3 and Ce3S4, which agreed well with the results observed by SEM and EDS. By analysis of two-dimensional lattice disregistry, it was shown that the lattice misfit parameter between δ-Fe and Ce2O3, Ce3S4 are less than 6 %, which indicated that Ce2O3 and Ce3S4 could effectively act as the heterogeneous nuclei of initial δ-Fe. Therefore, the microstructures were refined significantly and the mechanical properties were improved correspondingly in Ce-added low carbon high manganese steels.

Forging property, processing map, and mesoscale microstructural evolution modeling of a Ti-17 alloy with a lamellar (α+β) starting microstructure

NASA Astrophysics Data System (ADS)

Matsumoto, Hiroaki; Naito, Daiki; Miyoshi, Kento; Yamanaka, Kenta; Chiba, Akihiko; Yamabe-Mitarai, Yoko

2017-12-01

This work identifies microstructural conversion mechanisms during hot deformation (at temperatures ranging from 750 °C to 1050 °C and strain rates ranging from 10-3 s-1 to 1 s-1) of a Ti-5Al-2Sn-2Zr-4Mo-4Cr (Ti-17) alloy with a lamellar starting microstructure and establishes constitutive formulae for predicting the microstructural evolution using finite-element analysis. In the α phase, lamellae kinking is the dominant mode in the higher strain rate region and dynamic globularization frequently occurs at higher temperatures. In the β phase, continuous dynamic recrystallization is the dominant mode below the transition temperature, Tβ (880 890 °C). Dynamic recovery tends to be more active at conditions of lower strain rates and higher temperatures. At temperatures above Tβ, continuous dynamic recrystallization of the β phase frequently occurs, especially in the lower strain rate region. A set of constitutive equations modeling the microstructural evolution and processing map characteristic are established by optimizing the experimental data and were later implemented in the DEFORM-3D software package. There is a satisfactory agreement between the experimental and simulated results, indicating that the established series of constitutive models can be used to reliably predict the properties of a Ti-17 alloy after forging in the (α+β) region.

Forging property, processing map, and mesoscale microstructural evolution modeling of a Ti-17 alloy with a lamellar (α+β) starting microstructure

PubMed Central

Matsumoto, Hiroaki; Naito, Daiki; Miyoshi, Kento; Yamanaka, Kenta; Chiba, Akihiko; Yamabe-Mitarai, Yoko

2017-01-01

Abstract This work identifies microstructural conversion mechanisms during hot deformation (at temperatures ranging from 750 °C to 1050 °C and strain rates ranging from 10−3 s−1 to 1 s−1) of a Ti-5Al-2Sn-2Zr-4Mo-4Cr (Ti-17) alloy with a lamellar starting microstructure and establishes constitutive formulae for predicting the microstructural evolution using finite-element analysis. In the α phase, lamellae kinking is the dominant mode in the higher strain rate region and dynamic globularization frequently occurs at higher temperatures. In the β phase, continuous dynamic recrystallization is the dominant mode below the transition temperature, T β (880~890 °C). Dynamic recovery tends to be more active at conditions of lower strain rates and higher temperatures. At temperatures above T β, continuous dynamic recrystallization of the β phase frequently occurs, especially in the lower strain rate region. A set of constitutive equations modeling the microstructural evolution and processing map characteristic are established by optimizing the experimental data and were later implemented in the DEFORM-3D software package. There is a satisfactory agreement between the experimental and simulated results, indicating that the established series of constitutive models can be used to reliably predict the properties of a Ti-17 alloy after forging in the (α+β) region. PMID:29152021

Forging property, processing map, and mesoscale microstructural evolution modeling of a Ti-17 alloy with a lamellar (α+β) starting microstructure.

PubMed

Matsumoto, Hiroaki; Naito, Daiki; Miyoshi, Kento; Yamanaka, Kenta; Chiba, Akihiko; Yamabe-Mitarai, Yoko

2017-01-01

This work identifies microstructural conversion mechanisms during hot deformation (at temperatures ranging from 750 °C to 1050 °C and strain rates ranging from 10 -3  s -1 to 1 s -1 ) of a Ti-5Al-2Sn-2Zr-4Mo-4Cr (Ti-17) alloy with a lamellar starting microstructure and establishes constitutive formulae for predicting the microstructural evolution using finite-element analysis. In the α phase, lamellae kinking is the dominant mode in the higher strain rate region and dynamic globularization frequently occurs at higher temperatures. In the β phase, continuous dynamic recrystallization is the dominant mode below the transition temperature, T β (880~890 °C). Dynamic recovery tends to be more active at conditions of lower strain rates and higher temperatures. At temperatures above T β , continuous dynamic recrystallization of the β phase frequently occurs, especially in the lower strain rate region. A set of constitutive equations modeling the microstructural evolution and processing map characteristic are established by optimizing the experimental data and were later implemented in the DEFORM-3D software package. There is a satisfactory agreement between the experimental and simulated results, indicating that the established series of constitutive models can be used to reliably predict the properties of a Ti-17 alloy after forging in the (α+ β ) region.

Sulfur evolution in chemical looping combustion of coal with MnFe2O4 oxygen carrier.

PubMed

Wang, Baowen; Gao, Chuchang; Wang, Weishu; Zhao, Haibo; Zheng, Chuguang

2014-05-01

Chemical looping combustion (CLC) of coal has gained increasing attention as a novel combustion technology for its advantages in CO2 capture. Sulfur evolution from coal causes great harm from either the CLC operational or environmental perspective. In this research, a combined MnFe2O4 oxygen carrier (OC) was synthesized and its reaction with a typical Chinese high sulfur coal, Liuzhi (LZ) bituminous coal, was performed in a thermogravimetric analyzer (TGA)-Fourier transform infrared (FT-IR) spectrometer. Evolution of sulfur species during reaction of LZ coal with MnFe2O4 OC was systematically investigated through experimental means combined with thermodynamic simulation. TGA-FTIR analysis of the LZ reaction with MnFe2O4 indicated MnFe2O4 exhibited the desired superior reactivity compared to the single reference oxides Mn3O4 or Fe2O3, and SO2 produced was mainly related to oxidization of H2S by MnFe2O4. Experimental analysis of the LZ coal reaction with MnFe2O4, including X-ray diffraction and X-ray photoelectron spectroscopy analysis, verified that the main reduced counterparts of MnFe2O4 were Fe3O4 and MnO, in good agreement with the related thermodynamic simulation. The obtained MnO was beneficial to stabilize the reduced MnFe2O4 and avoid serious sintering, although the oxygen in MnO was not fully utilized. Meanwhile, most sulfur present in LZ coal was converted to solid MnS during LZ reaction with MnFe2O4, which was further oxidized to MnSO4. Finally, the formation of both MnS and such manganese silicates as Mn2SiO4 and MnSiO3 should be addressed to ensure the full regeneration of the reduced MnFe2O4. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Disintegration of Meatball Electrodes for LiNi x Mn y Co z O 2 Cathode Materials

DOE PAGES

Xu, R.; de Vasconcelos, L. S.; Shi, J.; ...

2017-05-12

Mechanical degradation of Li-ion batteries caused by the repetitive swelling and shrinking of electrodes upon electrochemical cycles is now well recognized. Structural disintegration of the state-of-art cathode materials of a hierarchical structure is relatively less studied. In this paper, we track the microstructural evolution of different marked regimes in LiNi x Mn y Co z O 2 (NMC) electrodes after lithiation cycles. Decohesion of primary particles constitutes the major mechanical degradation in the NMC materials, which results in the loss of connectivity of the conductive network and impedance increase. We find that the structural disintegration is largely dependent on themore » charging rate – slow charging causes more damage, and is relatively insensitive to the cyclic voltage window. We use finite element modeling to study the evolution of Li concentration and stresses in a NMC secondary particle and employ the cohesive zone model to simulate the interfacial fracture between primary particles. Finally, we reveal that microcracks accumulate and propagate during the cyclic lithiation and delithiation at a slow charging rate.« less

Effect of microstructure on the zinc phosphate conversion coatings on magnesium alloy AZ91

NASA Astrophysics Data System (ADS)

Van Phuong, Nguyen; Moon, Sungmo; Chang, Doyon; Lee, Kyu Hwan

2013-01-01

The effect of the microstructure, particularly of β-Mg17Al12 phase, on the formation and growth of zinc phosphate conversion coatings on magnesium alloy AZ91 (AZ91) was studied. The zinc phosphate coatings were formed on AZ91 with different microstructures produced by heat treatment. The effect of the microstructure on the zinc phosphate coatings were examined using optical microscope (OM), X-ray diffraction (XRD), coatings weight and etching weight balances, scanning electron microscopy (SEM) and salt immersion test. Results showed that as-cast AZ91 contained a high volume fraction of the β-Mg17Al12 phase and it was dissolved into α-Mg phase during heat treatment at 400 °C. The β-phase became center for hydrogen evolution during phosphating reaction (cathodic sites). The decreased volume fraction of the β-phase caused decreasing both coatings weight and etching weight of the phosphating process. However, it increased the crystal size of the coatings and improved corrosion resistance of AZ91 by immersing in 0.5 M NaCl solution. Results also showed that the structure of the zinc phosphate conversion on AZ91 consisted of two layers: an outer crystal Zn3(PO4)2·4H2O (hopeite) and an inner which was mainly composed of MgZn2(PO4)2 and Mg3(PO4)2. A mechanism for the formation of two layers of the coatings was also proposed in this study.

Enhanced magneto-optical and photo-catalytic properties of transition metal cobalt (Co2+ ions) doped spinel MgFe2O4 ferrite nanocomposites

NASA Astrophysics Data System (ADS)

Abraham, A. Godlyn; Manikandan, A.; Manikandan, E.; Vadivel, S.; Jaganathan, S. K.; Baykal, A.; Renganathan, P. Sri

2018-04-01

In this study, spinel magnesium cobalt ferrite (CoxMg1-xFe2O4: x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) nanocomposites were synthesized successfully by modified sol-gel combustion method. Magnesium nitrate, cobalt nitrate and iron nitrate were used as the source of divalent (Mg2+ and Co2+) and trivalent (Fe3+) cations, respectively and urea were used as the reducing (fuel) agent. The effects of cobalt ions on morphology, structural, optical, magnetic and photo-catalytic properties of spinel CoxMg1-xFe2O4 nanocomposites were investigated. Various characterization methods, including X-ray powder diffraction (XRD), high resolution scanning electron microscope (HR-SEM), transmission electron microscopy (HR-TEM), energy-dispersive X-ray spectroscopy (EDX), Fourier transforms infrared (FT-IR) spectroscopy, vibrating sample magnetometer (VSM) and photo-catalytic degradation (PCD) activity were used to study the phase purity, microstructure, particle size, elemental composition, functional group determination, band gap calculation, magnetic properties and degradation efficiency of nanoparticles, respectively. The observed results showed that the final products consists cubic spinel phase with sphere-like nanoparticles morphologies. Furthermore, spinel Co0.6Mg0.4Fe2O4 nanocomposite showed highest PCD efficiency (98.55%) than other composition of ferrite nanoparticles.

Structure Evolution of BaTiO3 on Co Doping: X-ray diffraction and Raman study

NASA Astrophysics Data System (ADS)

Mansuri, Amantulla; Mishra, Ashutosh

2016-10-01

In the present study, we have synthesize polycrystalline samples of BaTi1-xCoxO3 (x = 0, 0.05 and 0.1) with standard solid state reaction technique. The obtained samples are characterized by X-ray diffraction (XRD) and Raman spectroscopy. The detail structural analysis has been performed by Rietveld refinement using Fullprof program. The structural analysis reveal the samples are chemical pure and crystallize in tetragonal phase with space group Pm3m. We observe an increase in lattice parameters which results due to substitution of Co2+ with large ionic radii (0.9) for smaller ionic radii (0.6) Ti4+. Moreover peak at 45.5° shift to 45° on Co doping, which is due to structure phase transition from tetragonal to cubic. Raman study infers that the intensity of characteristic peaks decreases and linewidth increases with Co doping. The bands linked with the tetragonal structure (307 cm1) decreased due to the tetragonal-towards-cubic phase transition with Co doping. Our structural study reveals the expansion of BTO unit cell and tetragonal-to-cubic phase transformation takes place, results from different characterization techniques are conclusive and show structural evolution with Co doping.

In-situ electrochemical-AFM study of localized corrosion of AlxCoCrFeNi high-entropy alloys in chloride solution

NASA Astrophysics Data System (ADS)

Shi, Yunzhu; Collins, Liam; Balke, Nina; Liaw, Peter K.; Yang, Bin

2018-05-01

In-situ electrochemical (EC)-AFM is employed to investigate the localized corrosion of the AlxCoCrFeNi high-entropy alloys (HEAs). Surface topography changes on the micro/sub-micro scale are monitored at different applied anodizing potentials in a 3.5 wt% NaCl solution. The microstructural evolutions with the increased Al content in the alloys are characterized by SEM, TEM, EDS and EBSD. The results show that by increasing the Al content, the microstructure changes from single solid-solution to multi-phases, leading to the segregations of elements. Due to the microstructural variations in the AlxCoCrFeNi HEAs, localized corrosion processes in different ways after the breakdown of the passive film, which changes from pitting to phase boundary corrosion. The XPS results indicate that an increased Al content in the alloys/phases corresponds to a decreased corrosion resistance of the surface passive film.

Suppressed Sr segregation and performance of directly assembled La0.6Sr0.4Co0.2Fe0.8O3-δ oxygen electrode on Y2O3-ZrO2 electrolyte of solid oxide electrolysis cells

NASA Astrophysics Data System (ADS)

Ai, Na; He, Shuai; Li, Na; Zhang, Qi; Rickard, William D. A.; Chen, Kongfa; Zhang, Teng; Jiang, San Ping

2018-04-01

Active and stable oxygen electrode is probably the most important in the development of solid oxide electrolysis cells (SOECs) technologies. Herein, we report the successful development of mixed ionic and electronic conducting (MIEC) La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) perovskite oxides directly assembled on barrier-layer-free yttria-stabilized zirconia (YSZ) electrolyte as highly active and stable oxygen electrodes of SOECs. Electrolysis polarization effectively induces the formation of electrode/electrolyte interface, similar to that observed under solid oxide fuel cell (SOFC) operation conditions. However, in contrast to the significant performance decay under SOFC operation conditions, the cell with directly assembled LSCF oxygen electrodes shows excellent stability, tested for 300 h at 0.5 A cm-2 and 750 °C under SOEC operation conditions. Detailed microstructure and phase analysis reveal that Sr segregation is inevitable for LSCF electrode, but anodic polarization substantially suppresses Sr segregation and migration to the electrode/electrolyte interface, leading to the formation of stable and efficient electrode/electrolyte interface for water and CO2 electrolysis under SOECs operation conditions. The present study demonstrates the feasibility of using directly assembled MIEC cobaltite based oxygen electrodes on barrier-layer-free YSZ electrolyte of SOECs.

Studies on magnetocapacitance, dielectric, ferroelectric, and magnetic properties of microwave sintered (1-x) (Ba0.8Sr0.2TiO3) - x (Co0.9Ni0.1Fe2O4) multiferroic composite

NASA Astrophysics Data System (ADS)

Mane, Sagar M.; Tirmali, Pravin M.; Ranjit, Bhakti; Khan, Madiha; Khan, Nargis; Tarale, Arjun N.; Kulkarni, Shrinivas B.

2018-07-01

Present paper reports the synthesis of multiferroic composite (1-x) [Ba0.8Sr0.2Ti)O3]-x[Co0.9Ni0.1Fe2O4] were x = 0.1, 0.2, 0.3 and 0.4. Both phases of the composite i.e. ferroelectric (BST) and ferrite (CNFO) are synthesized via hydroxide co-precipitation method followed by microwave sintering technique at 1100 °C. These composites were characterized for their structural, microstructural, dielectric analysis, magnetodielectric (MD) effect and ferroelectric properties. Presence of both the phases ferroelectric (BST) and ferromagnetic (CNFO) are confirmed by the x-ray diffraction and scanning electron microscopic analysis. Maxwell-Wagner type dielectric dispersion is observed in frequency dependent dielectric measurement. Temperature-dependent dielectric properties were measured from 25 °C to 500 °C at various applied frequencies. Ferroelectric behavior in the composites was confirmed by the polarization vs. Electric field analysis. The magnetodielectric effect was studied in the presence of applied magnetic field from 0 to 1 Tesla. Magnetocapacitance (%) increases with increase in the ferrite concentration in the ferroelectric phase. The maximum percentage of magnetocapacitance is observed in 60BST-40CNFO composite which is MC = 30% at the frequency 1 KHz with the applied magnetic field is 1-Tesla. Room temperature magnetic hysteresis loops show an increase in saturation magnetization (Ms) with an increase in ferrite concentration.

Single-Crystalline Ultrathin Co 3O 4 Nanosheets with Massive Vacancy Defects for Enhanced Electrocatalysis

DOE PAGES

Cai, Zhao; Bi, Yongmin; Hu, Enyuan; ...

2017-09-18

The role of vacancy defects is demonstrated to be positive in various energy-related processes. However, introducing vacancy defects into single-crystalline nanostructures with given facets and studying their defect effect on electrocatalytic properties remains a great challenge. Here this paper deliberately introduces oxygen defects into single-crystalline ultrathin Co 3O 4 nanosheets with O-terminated {111} facets by mild solvothermal reduction using ethylene glycol under alkaline condition. As-prepared defect-rich Co 3O 4 nanosheets show a low overpotential of 220 mV with a small Tafel slope of 49.1 mV dec -1 for the oxygen evolution reaction (OER), which is among the best Co-based OERmore » catalysts to date and even more active than the state-of-the-art IrO 2 catalyst. Such vacancy defects are formed by balancing with reducing environments under solvothermal conditions, but are surprisingly stable even after 1000 cycles of scanning under OER working conditions. Density functional theory plus U calculation attributes the enhanced performance to the oxygen vacancies and consequently exposed second-layered Co metal sites, which leads to the lowered OER activation energy of 2.26 eV and improved electrical conductivity. Finally, this mild solvothermal reduction concept opens a new door for the understanding and future designing of advanced defect-based electrocatalysts.« less

Single-Crystalline Ultrathin Co 3O 4 Nanosheets with Massive Vacancy Defects for Enhanced Electrocatalysis

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

Cai, Zhao; Bi, Yongmin; Hu, Enyuan

The role of vacancy defects is demonstrated to be positive in various energy-related processes. However, introducing vacancy defects into single-crystalline nanostructures with given facets and studying their defect effect on electrocatalytic properties remains a great challenge. Here this paper deliberately introduces oxygen defects into single-crystalline ultrathin Co 3O 4 nanosheets with O-terminated {111} facets by mild solvothermal reduction using ethylene glycol under alkaline condition. As-prepared defect-rich Co 3O 4 nanosheets show a low overpotential of 220 mV with a small Tafel slope of 49.1 mV dec -1 for the oxygen evolution reaction (OER), which is among the best Co-based OERmore » catalysts to date and even more active than the state-of-the-art IrO 2 catalyst. Such vacancy defects are formed by balancing with reducing environments under solvothermal conditions, but are surprisingly stable even after 1000 cycles of scanning under OER working conditions. Density functional theory plus U calculation attributes the enhanced performance to the oxygen vacancies and consequently exposed second-layered Co metal sites, which leads to the lowered OER activation energy of 2.26 eV and improved electrical conductivity. Finally, this mild solvothermal reduction concept opens a new door for the understanding and future designing of advanced defect-based electrocatalysts.« less

From Mixed-Metal MOFs to Carbon-Coated Core-Shell Metal Alloy@Metal Oxide Solid Solutions: Transformation of Co/Ni-MOF-74 to CoxNi1-x@CoyNi1-yO@C for the Oxygen Evolution Reaction.

PubMed

Sun, Dengrong; Ye, Lin; Sun, Fangxiang; García, Hermenegildo; Li, Zhaohui

2017-05-01

Calcination of the mixed-metal species Co/Ni-MOF-74 leads to the formation of carbon-coated Co x Ni 1-x @Co y Ni 1-y O with a metal core diameter of ∼3.2 nm and a metal oxide shell thickness of ∼2.4 nm embedded uniformly in the ligand-derived carbon matrix. The close proximity of Co and Ni in the mixed-metal Co/Ni-MOF-74 promotes the metal alloying and the formation of a solid solution of metal oxide during the calcination process. The presence of the tightly coated carbon shell prohibits particle agglomeration and stabilizes the Co x Ni 1-x @Co y Ni 1-y O nanoparticles in small size. The Co x Ni 1-x @Co y Ni 1-y O@C derived from Co/Ni-MOF-74 nanocomposites show superior performance for the oxygen evolution reaction (OER). The use of mixed-metal MOFs as precursors represents a powerful strategy for the fabrication of metal alloy@metal oxide solid solution nanoparticles in small size. This method also holds great promise in the development of multifunctional carbon-coated complex core-shell metal/metal oxides owing to the diversified MOF structures and their flexible chemistry.

Bifunctional bamboo-like CoSe2 arrays for high-performance asymmetric supercapacitor and electrocatalytic oxygen evolution.

PubMed

Chen, Tian; Li, Songzhan; Gui, Pengbin; Wen, Jian; Fu, Xuemei; Fang, Guojia

2018-05-18

Bifunctional bamboo-like CoSe 2 arrays are synthesized by thermal annealing of Co(CO 3 ) 0.5 OH grown on carbon cloth in Se atmosphere. The CoSe 2 arrays obtained have excellent electrical conductivity, larger electrochemical active surface areas, and can directly serve as a binder-free electrode for supercapacitors and the oxygen evolution reaction (OER). When tested as a supercapacitor electrode, the CoSe 2 delivers a higher specific capacitance (544.6 F g -1 at current density of 1 mA cm -2 ) compared with CoO (308.2 F g -1 ) or Co 3 O 4 (201.4 F g -1 ). In addition, the CoSe 2 electrode possesses excellent cycling stability. An asymmetric supercapacitor (ASC) is also assembled based on bamboo-like CoSe 2 as a positive electrode and active carbon as a negative electrode in a 3.0 M KOH aqueous electrolyte. Owing to the unique stucture and good electrochemical performance of bamboo-like CoSe 2 , the as-assembled ACS can achieve a maximum operating voltage window of 1.7 V, a high energy density of 20.2 Wh kg -1 at a power density of 144.1 W kg -1 , and an outstanding cyclic stability. As the catalyst for the OER, the CoSe 2 exhibits a lower potential of 1.55 V (versus RHE) at current density of 10 mA cm -2 , a smaller Tafel slope of 62.5 mV dec -1 and an also outstanding stability.

Bifunctional bamboo-like CoSe2 arrays for high-performance asymmetric supercapacitor and electrocatalytic oxygen evolution

NASA Astrophysics Data System (ADS)

Chen, Tian; Li, Songzhan; Gui, Pengbin; Wen, Jian; Fu, Xuemei; Fang, Guojia

2018-05-01

Bifunctional bamboo-like CoSe2 arrays are synthesized by thermal annealing of Co(CO3)0.5OH grown on carbon cloth in Se atmosphere. The CoSe2 arrays obtained have excellent electrical conductivity, larger electrochemical active surface areas, and can directly serve as a binder-free electrode for supercapacitors and the oxygen evolution reaction (OER). When tested as a supercapacitor electrode, the CoSe2 delivers a higher specific capacitance (544.6 F g‑1 at current density of 1 mA cm‑2) compared with CoO (308.2 F g‑1) or Co3O4 (201.4 F g‑1). In addition, the CoSe2 electrode possesses excellent cycling stability. An asymmetric supercapacitor (ASC) is also assembled based on bamboo-like CoSe2 as a positive electrode and active carbon as a negative electrode in a 3.0 M KOH aqueous electrolyte. Owing to the unique stucture and good electrochemical performance of bamboo-like CoSe2, the as-assembled ACS can achieve a maximum operating voltage window of 1.7 V, a high energy density of 20.2 Wh kg‑1 at a power density of 144.1 W kg‑1, and an outstanding cyclic stability. As the catalyst for the OER, the CoSe2 exhibits a lower potential of 1.55 V (versus RHE) at current density of 10 mA cm‑2, a smaller Tafel slope of 62.5 mV dec‑1 and an also outstanding stability.

Morphology Control of Carbon-Free Spinel NiCo 2 O 4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media

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

Devaguptapu, Surya V.; Hwang, Sooyeon; Karakalos, Stavros

Spinel NiCo 2O 4 is considered a promising precious metal-free catalyst that is also carbon-free for oxygen electrocatalysis. Current efforts mainly focus on optimal chemical doping and substituent to tune its electronic structures for enhanced activity. Here, we study its morphology control and elucidate the morphology-dependent catalyst performance for bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Three types of NiCo 2O 4 catalysts with significantly distinct morphologies were prepared using temple-free, Pluronic-123 (P-123) soft, and SiO 2 hard templates, respectively, via hydrothermal methods following by a calcination. While the hard-template yields sphere-like dense structures, soft-template assists themore » formation of a unique nano-needle cluster assembly containing abundant meso- and macro pores. Furthermore, the effect of morphology of NiCo 2O 4 on their corresponding bifunctional catalytic performance was systematically investigated. The flower-like nano-needle assembly NiCo 2O 4 catalyst via the soft template method exhibited the highest catalytic activity and stability for both ORR and OER. In particular, it exhibited an onset and half-wave potentials of 0.94 and 0.82 V vs. RHE, respectively, for the ORR in alkaline media. Although it is still inferior to Pt, the NiCo 2O 4 represents one of the best ORR catalyst compared to other reported carbon-free oxides. Meanwhile, remarkable OER activity and stability were achieved with an onset potential of 1.48 V and a current density of 15 mA/cm 2 at 1.6 V, showing no activity loss after 20,000 potential cycles (0 to 1.9 V). The demonstrated stability is even superior to Ir for the OER. The morphology-controlled approach provides an effective solution to create a robust 3D architecture with increased surface areas and enhanced mass transfer. More importantly, the soft template can yield high degree of spinel crystallinity with ideal stoichiometric ratios between Ni and Co, thus promoting structural integrity with enhanced electrical conductivity and catalytic properties.« less

Morphology Control of Carbon-Free Spinel NiCo 2 O 4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media

DOE PAGES

Devaguptapu, Surya V.; Hwang, Sooyeon; Karakalos, Stavros; ...

2017-12-06

Spinel NiCo 2O 4 is considered a promising precious metal-free catalyst that is also carbon-free for oxygen electrocatalysis. Current efforts mainly focus on optimal chemical doping and substituent to tune its electronic structures for enhanced activity. Here, we study its morphology control and elucidate the morphology-dependent catalyst performance for bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Three types of NiCo 2O 4 catalysts with significantly distinct morphologies were prepared using temple-free, Pluronic-123 (P-123) soft, and SiO 2 hard templates, respectively, via hydrothermal methods following by a calcination. While the hard-template yields sphere-like dense structures, soft-template assists themore » formation of a unique nano-needle cluster assembly containing abundant meso- and macro pores. Furthermore, the effect of morphology of NiCo 2O 4 on their corresponding bifunctional catalytic performance was systematically investigated. The flower-like nano-needle assembly NiCo 2O 4 catalyst via the soft template method exhibited the highest catalytic activity and stability for both ORR and OER. In particular, it exhibited an onset and half-wave potentials of 0.94 and 0.82 V vs. RHE, respectively, for the ORR in alkaline media. Although it is still inferior to Pt, the NiCo 2O 4 represents one of the best ORR catalyst compared to other reported carbon-free oxides. Meanwhile, remarkable OER activity and stability were achieved with an onset potential of 1.48 V and a current density of 15 mA/cm 2 at 1.6 V, showing no activity loss after 20,000 potential cycles (0 to 1.9 V). The demonstrated stability is even superior to Ir for the OER. The morphology-controlled approach provides an effective solution to create a robust 3D architecture with increased surface areas and enhanced mass transfer. More importantly, the soft template can yield high degree of spinel crystallinity with ideal stoichiometric ratios between Ni and Co, thus promoting structural integrity with enhanced electrical conductivity and catalytic properties.« less

Effects of pH and Oxygen on Photosynthetic Reactions of Intact Chloroplasts 1

PubMed Central

Heber, Ulrich; Andrews, T. John; Boardman, N. Keith

1976-01-01

Oxygen inhibition of photosynthesis was studied with intact spinach (Spinacia oleracea L.) chloroplasts which exhibited very high rates of photosynthetic CO2 reduction and were insensitive to additions of photosynthetic intermediates when CO2 was available at saturating concentrations. Photosynthetic rates were measured polarographically as O2 evolution, and the extent of the reduction of substrate was estimated from the amount of O2 evolved. With CO2 as substrate, inhibition of photosynthesis by O2 was dependent on pH. At pH values above 8, rates of O2 evolution were strongly inhibited by O2 and only a fraction of the added bicarbonate was reduced before O2 evolution ceased. The extent of O2 evolution declined with increasing O2 concentration and decreasing initial bicarbonate concentration. At pH 7.2, the initial photosynthetic rate was inhibited about 30% at high O2 levels, but the extent of O2 evolution was unaffected and most of the added bicarbonate was reduced. Photosynthetic O2 evolution with 3-phosphoglycerate as substrate was similarly dependent on pH and O2 concentration. In contrast, there was little effect of O2 and pH on oxaloacetate-dependent oxygen evolution. Acid-base shift experiments with osmotically shocked chloroplasts showed that ATP formation was not affected by O2. The results are discussed in terms of a balance between photosynthetic O2 evolution and O2 consumption by the ribulose diphosphate oxygenase reaction. PMID:16659466

Reversible adapting layer produces robust single-crystal electrocatalyst for oxygen evolution.

PubMed

Tung, Ching-Wei; Hsu, Ying-Ya; Shen, Yen-Ping; Zheng, Yixin; Chan, Ting-Shan; Sheu, Hwo-Shuenn; Cheng, Yuan-Chung; Chen, Hao Ming

2015-08-28

Electrochemically converting water into oxygen/hydrogen gas is ideal for high-density renewable energy storage in which robust electrocatalysts for efficient oxygen evolution play crucial roles. To date, however, electrocatalysts with long-term stability have remained elusive. Here we report that single-crystal Co3O4 nanocube underlay with a thin CoO layer results in a high-performance and high-stability electrocatalyst in oxygen evolution reaction. An in situ X-ray diffraction method is developed to observe a strong correlation between the initialization of the oxygen evolution and the formation of active metal oxyhydroxide phase. The lattice of skin layer adapts to the structure of the active phase, which enables a reversible facile structural change that facilitates the chemical reactions without breaking the scaffold of the electrocatalysts. The single-crystal nanocube electrode exhibits stable, continuous oxygen evolution for >1,000 h. This robust stability is attributed to the complementary nature of defect-free single-crystal electrocatalyst and the reversible adapting layer.

Analyses of microstructural and elastic properties of porous SOFC cathodes based on focused ion beam tomography

NASA Astrophysics Data System (ADS)

Chen, Zhangwei; Wang, Xin; Giuliani, Finn; Atkinson, Alan

2015-01-01

Mechanical properties of porous SOFC electrodes are largely determined by their microstructures. Measurements of the elastic properties and microstructural parameters can be achieved by modelling of the digitally reconstructed 3D volumes based on the real electrode microstructures. However, the reliability of such measurements is greatly dependent on the processing of raw images acquired for reconstruction. In this work, the actual microstructures of La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathodes sintered at an elevated temperature were reconstructed based on dual-beam FIB/SEM tomography. Key microstructural and elastic parameters were estimated and correlated. Analyses of their sensitivity to the grayscale threshold value applied in the image segmentation were performed. The important microstructural parameters included porosity, tortuosity, specific surface area, particle and pore size distributions, and inter-particle neck size distribution, which may have varying extent of effect on the elastic properties simulated from the microstructures using FEM. Results showed that different threshold value range would result in different degree of sensitivity for a specific parameter. The estimated porosity and tortuosity were more sensitive than surface area to volume ratio. Pore and neck size were found to be less sensitive than particle size. Results also showed that the modulus was essentially sensitive to the porosity which was largely controlled by the threshold value.

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

Wang, Dan; Yang, Ping, E-mail: mse_yangp@ujn.edu.cn; Huang, Baibiao

Graphical abstract: The iron alkoxide precursors are calcined into α-Fe{sub 2}O{sub 3}, Fe{sub 3}O{sub 4} microstructures with different morphologies by changing calcination atmosphere, reaction time of precursors and calcination temperature simply. The Fe{sub 2}O{sub 3}/Ag hybrid composites prepared through aqueous synthesis and light irradiation. - Highlights: • α-Fe{sub 2}O{sub 3} and Fe{sub 3}O{sub 4} microstructures with different morphologies were created. • Solvents play an important role for the solvothermal treatment of precursors. • The α-Fe{sub 2}O{sub 3} microstructures show excellent adsorption properties. • Fe{sub 2}O{sub 3}/Ag hybrid composites were prepared to improve their properties. - Abstract: The flower-like precursors ofmore » Fe alkoxide constructed by the self-assembly of nanoflakes were prepared. Time-dependent experiments confirmed the formation mechanism of flower-like precursors. After calcination, α-Fe{sub 2}O{sub 3} and Fe{sub 3}O{sub 4} nanostructures with different morphologies were created. Fe{sub 3}O{sub 4} nanostructures containing blocks with a truncated octahedron structure were obtained under N{sub 2} protection. α-Fe{sub 2}O{sub 3} nanostructures were prepared in an air atmosphere. The values of maximum adsorption capacity of α-Fe{sub 2}O{sub 3} nanostructures for Cr{sup 6+} ions were much higher than that of commercial bulk α-Fe{sub 2}O{sub 3}. Ag NPs were deposited on α-Fe{sub 2}O{sub 3} nanostructures through an aqueous synthesis and light irradiation using L-cysteine as a linker. Such procedure is utilizable for the preparation of the composites of noble metals and magnetic materials.« less

Study on Tribological Properties of CoCrMo Alloys against Metals and Ceramics as Bearing Materials for Artificial Cervical Disc

NASA Astrophysics Data System (ADS)

Xiang, Dingding; Song, Jian; Wang, Song; Liao, Zhenhua; Liu, Yuhong; Tyagi, Rajnesh; Liu, Weiqiang

2018-02-01

CoCrMo alloys are believed to be a kind of potential material for artificial cervical disc. However, the tribological properties of CoCrMo alloys against different metals and ceramics are not systematically studied. In this study, the tribological behaviors of CoCrMo alloys against metals (316L, Ti6Al4V) and ceramics (Si3N4, ZrO2) were focused under dry friction and 25 wt.% newborn calf serum (NCS)-lubricated conditions using a ball-on-disc apparatus under reciprocating motion. The microstructure, composition and hardness of CoCrMo alloys were characterized using x-ray diffraction, scanning electron microscopy (SEM) and hardness testers, respectively. The contact angles of the CoCrMo alloys with deionized water and 25 wt.% NCS were measured by the OCA contact angle measuring instrument. The maximum wear width, wear depth and wear volume were measured by three-dimensional white light interference. The morphology and the EDX analysis of the wear marks on CoCrMo alloys were examined by SEM to determine the basic mechanism of friction and wear. The dominant wear mechanism in dry friction for CoCrMo alloys against all pairings was severe abrasive wear, accompanied with a lot of material transfer. Under 25 wt.% NCS-lubricated condition, the wear mechanism for CoCrMo alloys against ceramics (Si3N4, ZrO2) was also mainly severe abrasive wear. However, severe abrasive wear and electrochemical corrosion occurred for the CoCrMo-316L pairing under lubrication. Severe abrasive wear, adhesive wear and electrochemical corrosion occurred for the CoCrMo-Ti6Al4V pairing under lubrication. According to the results, the tribological properties of CoCrMo alloys against ceramics were better than those against metals. The CoCrMo-ZrO2 pairing displayed the best tribological behaviors and could be taken as a potential candidate bearing material for artificial cervical disc.

YBa_2Cu_3O_{7-δ} : in pursuit of the ideal microstructure

NASA Astrophysics Data System (ADS)

Smith, D. S.; Suasmoro, S.; Lejeune, M.; Rabier, J.; Denanot, M. F.; Heintz, J. M.; Magro, C.; Bonnet, J. P.

1992-02-01

This paper examines the role of different factors in the microstructure of ceramic YBa2Cu3O{7-δ} with emphasis on its electrical response. In particular we discuss : 1. the effect of microstructural variations on j_c and ρ_{300}, 2. measurement of j_c, 3. the presence of minor phases and carbonates, 4. oxygen uptake and microcracks, 5. plastic deformation and related structural defects. Dans cet article, nous examinons d'une part la réponse électrique de céramiques supraconductrices massives de type YBa2Cu3O{7-δ} et d'autre part sa relation avec la microstructure. Nous présenterons successivement : 1. L'incidence de modifications microstructurales sur les valeurs de j_c et ρ_{300}, 2. les mesures expérimentales de j_c, 3. la présence de phases minoritaires et de carbonates, 4. la reprise d'oxygène et la microfissuration, 5. la déformation plastique et les défauts structuraux associés.

Ferromagnetism enhanced by structural relaxation of biaxially compressed LaCoO3 films

NASA Astrophysics Data System (ADS)

Mehta, Virat; Suzuki, Yuri

2011-04-01

Epitaxial LaCoO3 films were synthesized on LaAlO3 substrates to explore the role of epitaxial strain and structure on the ferromagnetism observed in these biaxially compressed films. Coherent strain and tetragonal structure were only achieved in thin film samples grown using higher energy densities. The strain relaxed with increasing thickness and was accompanied by increasing mosaic spread. Higher magnetization values were consistently seen in fully relaxed films grown using lower laser energy density. These results suggest that epitaxial strain is not the only factor determining the ferromagnetism and that the microstructure and defects may play a significant role.

Monitoring the growth of polyoxomolybdate nanoparticles in suspension by flow field-flow fractionation.

PubMed

Chen, Bailin; Jiang, Huijian; Zhu, Yan; Cammers, Arthur; Selegue, John P

2005-03-30

We follow the evolution of polyoxomolybdate nanoparticles in suspensions derived from the keplerate (NH4)42[MoVI72MoV60O372(CH3CO2)30(H2O)72].ca..300H2O.ca..10CH3CO2NH4 ({Mo132}) by flow field-flow fractionation (FlFFF) to monitor the particle-size distribution in situ, atomic force and high-resolution transmission electron microscopy (AFM, SEM, and HRTEM) to confirm particle sizes, inductively coupled plasma-optical emission spectrometry (ICP-OES) to determine the Mo content of the FlFFF-separated fractions, and UV/visible spectroscopy to confirm the identity of the species in suspension. We observe the formation of 3-75-nm polyoxomolybdate particles in suspension and the dynamic growth of {Mo132} crystals.

Oxygen ion conductivity of La0.8Sr0.2Ga0.83Mg0.17-xCoxO3-δ synthesized by laser rapid solidification

NASA Astrophysics Data System (ADS)

Zhang, Jie; Yuan, Chao; Wang, Jun-Qiao; Liang, Er-Jun; Chao, Ming-Ju

2013-08-01

Materials La0.8Sr0.2Ga0.83Mg0.17-xCoxO3-δ with x = 0, 0.05, 0.085, 0.10, and 0.15 are synthesized by laser rapid solidification. It is shown that the samples prepared by laser rapid solidification give rise to unique spear-like or leaf-like microstructures which are orderly arranged and densely packed. Their electrical properties each show a general dependence of the Co content and the total conductivities of La0.8Sr0.2Ga0.83Mg0.085Co0.085O3-δ prepared by laser rapid solidification are measured to be 0.067, 0.124, and 0.202 S·cm-1 at 600, 700, and 800 °C, respectively, which are much higher than by conventional solid state reactions. Moreover, the electrical conductivities each as a function of the oxygen partial pressure are also measured. It is shown that the samples with the Co content values <= 8.5 mol% each exhibit basically ionic conduction while those for Co content values >= 10 mol % each show ionic mixed electronic conduction under oxygen partial pressures from 10-16 atm (1 atm = 1.01325 × 105 Pa) to 0.98 atm. The improved ionic conductivity of La0.8Sr0.2Ga0.83Mg0.085Co0.085O3-δ prepared by laser rapid solidification compared with by solid state reactions is attributed to the unique microstructure of the sample generated during laser rapid solidification.

Evaluation of Microstructure and Mechanical Properties of Nano-Y2O3-Dispersed Ferritic Alloy Synthesized by Mechanical Alloying and Consolidated by High-Pressure Sintering

NASA Astrophysics Data System (ADS)

Karak, Swapan Kumar; Dutta Majumdar, J.; Witczak, Zbigniew; Lojkowski, Witold; Ciupiński, Łukasz; Kurzydłowski, K. J.; Manna, Indranil

2013-06-01

In this study, an attempt has been made to synthesize 1.0 wt pct nano-Y2O3-dispersed ferritic alloys with nominal compositions: 83.0 Fe-13.5 Cr-2.0 Al-0.5 Ti (alloy A), 79.0 Fe-17.5 Cr-2.0 Al-0.5 Ti (alloy B), 75.0 Fe-21.5 Cr-2.0 Al-0.5 Ti (alloy C), and 71.0 Fe-25.5 Cr-2.0 Al-0.5 Ti (alloy D) steels (all in wt pct) by solid-state mechanical alloying route and consolidation the milled powder by high-pressure sintering at 873 K, 1073 K, and 1273 K (600°C, 800°C, and 1000°C) using 8 GPa uniaxial pressure for 3 minutes. Subsequently, an extensive effort has been undertaken to characterize the microstructural and phase evolution by X-ray diffraction, scanning and transmission electron microscopy, and energy dispersive spectroscopy. Mechanical properties including hardness, compressive strength, Young's modulus, and fracture toughness were determined using micro/nano-indentation unit and universal testing machine. The present ferritic alloys record extraordinary levels of compressive strength (from 1150 to 2550 MPa), Young's modulus (from 200 to 240 GPa), indentation fracture toughness (from 3.6 to 15.4 MPa√m), and hardness (from13.5 to 18.5 GPa) and measure up to 1.5 through 2 times greater strength but with a lower density (~7.4 Mg/m3) than other oxide dispersion-strengthened ferritic steels (<1200 MPa) or tungsten-based alloys (<2200 MPa). Besides superior mechanical strength, the novelty of these alloys lies in the unique microstructure comprising uniform distribution of either nanometric (~10 nm) oxide (Y2Ti2O7/Y2TiO5 or un-reacted Y2O3) or intermetallic (Fe11TiY and Al9.22Cr2.78Y) particles' ferritic matrix useful for grain boundary pinning and creep resistance.

Subsurface damage and microstructure development in precision microground hard ceramics using magnetorheological finishing spots.

PubMed

Shafrir, Shai N; Lambropoulos, John C; Jacobs, Stephen D

2007-08-01

We demonstrate the use of spots taken with magnetorheological finishing (MRF) for estimating subsurface damage (SSD) depth from deterministic microgrinding for three hard ceramics: aluminum oxynitride (Al(23)O(27)N(5)/ALON), polycrystalline alumina (Al(2)O(3)/PCA), and chemical vapor deposited (CVD) silicon carbide (Si(4)C/SiC). Using various microscopy techniques to characterize the surfaces, we find that the evolution of surface microroughness with the amount of material removed shows two stages. In the first, the damaged layer and SSD induced by microgrinding are removed, and the surface microroughness reaches a low value. Peak-to-valley (p-v) surface microroughness induced from grinding gives a measure of the SSD depth in the first stage. With the removal of additional material, a second stage develops, wherein the interaction of MRF and the material's microstructure is revealed. We study the development of this texture for these hard ceramics with the use of power spectral density to characterize surface features.

Subsurface Damage and Microstructure Development in Precision Microground Hard Ceramics Using Magnetorheological Finishing Spots

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

Shafrir, S.N.; Lambropoulos, J.C.; Jacobs, S.D.

2007-08-01

We demonstrate the use of spots taken with magnetorheological finishing (MRF) for estimating subsurface damage (SSD) depth from deterministic microgrinding for three hard ceramics: aluminum oxynitride (Al23O27N5/ALON), polycrystalline alumina (AL2O3/PCA), and chemical vapor deposited (CVD) silicon carbide (Si4C/SiC). Using various microscopy techniques to characterize the surfaces, we find that the evolution of surface microroughness with the amount of material removed shows two stages. In the first, the damaged layer and SSD induced by microgrinding are removed, and the surface roughness reaches a low value. Peak-to-valley (p-v) surface microroughness induced from grinding gives a measure of the SSD depth in themore » first stage. With the removal of additional material, a second stage develops, wherein the interaction of MRF and the material's microstructure is revealed. We study the development of this texture for these har ceramics with the use of power spectral density to characterize surface features.« less

Preparation of γ-Al2O3 films by laser chemical vapor deposition

NASA Astrophysics Data System (ADS)

Gao, Ming; Ito, Akihiko; Goto, Takashi

2015-06-01

γ- and α-Al2O3 films were prepared by chemical vapor deposition using CO2, Nd:YAG, and InGaAs lasers to investigate the effects of varying the laser wavelength and deposition conditions on the phase composition and microstructure. The CO2 laser was found to mostly produce α-Al2O3 films, whereas the Nd:YAG and InGaAs lasers produced γ-Al2O3 films when used at a high total pressure. γ-Al2O3 films had a cauliflower-like structure, while the α-Al2O3 films had a dense and columnar structure. Of the three lasers, it was the Nd:YAG laser that interacted most with intermediate gas species. This promoted γ-Al2O3 nucleation in the gas phase at high total pressure, which explains the cauliflower-like structure of nanoparticles observed.

Microwave-Assisted Synthesis, Microstructure, and Magnetic Properties of Rare-Earth Cobaltites.

PubMed

Gutiérrez Seijas, Julia; Prado-Gonjal, Jesús; Ávila Brande, David; Terry, Ian; Morán, Emilio; Schmidt, Rainer

2017-01-03

The series of perovskite rare-earth (RE) doped cobaltites (RE)CoO 3 (RE = La-Dy) was prepared by microwave-assisted synthesis. The crystal structure undergoes a change of symmetry depending on the size of the RE cation. LaCoO 3 is rhombohedral, S.G. R3̅c (No. 167), while, for the rest of the RE series (Pr-Dy), the symmetry is orthorhombic, S.G. Pnma (No. 62). The crystal structure obtained by X-ray diffraction was confirmed by high-resolution transmission electron microscopy, which yielded a good match between experimental and simulated images. It is further shown that the well-known magnetism in LaCoO 3 , which involves a thermally induced Co 3+ (d 6 ) low spin to intermediate or high spin state transition, is strongly modified by the RE cation, and a rich variety of magnetic order has been detected across the series.

Effects of pore formers on microstructure and performance of cathode membranes for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Nie, Lifang; Liu, Juncheng; Zhang, Yujun; Liu, Meilin

La 0.6Sr 0.4Co 0.2Fe 0.8O 3- δ (LSCF) is the most widely used cathode material for intermediate temperature solid oxide fuel cells. In the present communication, porous LSCF cathodes are fabricated by tape casting, a low-cost and reproducible fabrication process. The effects of four different pore formers, namely, graphite, carbon black, rice starch, and corn starch, on the microstructure and electrochemical performance of the LSCF cathode are investigated. Examination of the microstructures reveals that the shape of the pores, the pore size, and the pore distribution in the final ceramic are related to the type of pore formers. Impedance analysis and cell testing show that the best performance is obtained from the cathode using graphite as the pore former. The microstructure indicates that graphite results in a porous LSCF cathode with a large surface area and high porosity, which can offer a considerably long triple phase boundary for catalytic reactions as well as channels for gas phase transport.

Model for origin and evolution of water at volcanoes in São Miguel, Azores (Portugal), based on geochemical and isotopic data set

NASA Astrophysics Data System (ADS)

Woitischek, Julia; Dietzel, Martin; Virgílio Cruz, J.; Inguaggiato, Salvatore; Leis, Albrecht; Böttcher, Michael E.

2016-04-01

A conceptual model is presented to better constrain the origin and evolution of discharges at Sete Cidades, Fogo and Furnas Volcano, using geochemical and isotopic analyses of rock and water as well as recalculated gas composition. The evolution of thermal water clearly reveals that Na-HCO3 and Na-SO4 type of springs have their origin in meteoric water as isotope data are close to the local meteoric water line (δ 18OH2O =-3 ± 1 ‰ V-SMOW; δ DH2O= -13 ± 7 ‰ V-SMOW) with exception of a Na-Cl spring named Ferraria, Sete Cidades area (δ 18OH2O = 0.45 ‰ V-SMOW ; δ DH2O= 4.18 ‰ V-SMOW). Analysed solutions are chemical evolved by evaporation, uptake of volcanic gas, leaching of local basaltic rocks, precipitation of solids, partly admixture of sea water and/or biological activity. Following the individual concentrations supports this model e.g.: HCO3 concentration and the recalculated isotopic composition of gaseous CO2 (δ 13CCO_2 = -4 ± 2.5 ‰ V-PDB) reflect evolved magmatic CO2 uptake and the subsequent leaching progress; High SO42- concentration of up to 16.5 mmol L-1 with δ 34SSO4 = 0.35 ± 0.3 ‰ (V-CDT) reflects magmatic origin which mainly control water chemistry of boiling pools of both Fogo and Furnas lake; δ 18OSO4 = 10.5 ‰ (V-SMOW) suggests organic origin and fits together with the observation of stromatolitic structures in the related precipitates; Molar Mg/Caratio (≈ 0.77) of all thermal discharges reflects leaching of analysed local basalt (Mg/Ca≈ 0.78). Furthermore, shallow and evolved outgassing effects can be distinguished. Equilibrium temperatures for various minerals given in SI vs. T plots and further geothermometers (e.g. Na-K, Na-K-Ca geothermometers) were discussed to estimate temperatures of reservoirs.

Microstructure Hierarchical Model of Competitive e+-Ps Trapping in Nanostructurized Substances: from Nanoparticle-Uniform to Nanoparticle-Biased Systems.

PubMed

Shpotyuk, Oleh; Ingram, Adam; Bujňáková, Zdenka; Baláž, Peter

2017-12-01

Microstructure hierarchical model considering the free-volume elements at the level of interacting crystallites (non-spherical approximation) and the agglomerates of these crystallites (spherical approximation) was developed to describe free-volume evolution in mechanochemically milled As 4 S 4 /ZnS composites employing positron annihilation spectroscopy in a lifetime measuring mode. Positron lifetime spectra were reconstructed from unconstrained three-term decomposition procedure and further subjected to parameterization using x3-x2-coupling decomposition algorithm. Intrinsic inhomogeneities due to coarse-grained As 4 S 4 and fine-grained ZnS nanoparticles were adequately described in terms of substitution trapping in positron and positronium (Ps) (bound positron-electron) states due to interfacial triple junctions between contacting particles and own free-volume defects in boundary compounds. Compositionally dependent nanostructurization in As 4 S 4 /ZnS nanocomposite system was imagined as conversion from o-Ps trapping sites to positron traps. The calculated trapping parameters that were shown could be useful to characterize adequately the nanospace filling in As 4 S 4 /ZnS composites.

A Novel Hybrid Axial-Radial Atmospheric Plasma Spraying Technique for the Fabrication of Solid Oxide Fuel Cell Anodes Containing Cu, Co, Ni, and Samaria-Doped Ceria

NASA Astrophysics Data System (ADS)

Cuglietta, Mark; Kuhn, Joel; Kesler, Olivera

2013-06-01

Composite coatings containing Cu, Co, Ni, and samaria-doped ceria (SDC) have been fabricated using a novel hybrid atmospheric plasma spraying technique, in which a multi-component aqueous suspension of CuO, Co3O4, and NiO was injected axially simultaneously with SDC injected radially in a dry powder form. Coatings were characterized for their microstructure, permeability, porosity, and composition over a range of plasma spray conditions. Deposition efficiency of the metal oxides and SDC was also estimated. Depending on the conditions, coatings displayed either layering or high levels of mixing between the SDC and metal phases. The deposition efficiencies of both feedstock types were strongly dependent on the nozzle diameter. Plasma-sprayed metal-supported solid oxide fuel cells utilizing anodes fabricated with this technique demonstrated power densities at 0.7 V as high as 366 and 113 mW/cm2 in humidified hydrogen and methane, respectively, at 800 °C.

Formation and Stability of Radiation Products in Europa's Icy Shell

NASA Technical Reports Server (NTRS)

Moore, M. H.; Hudson, R. L.; Carlson, R. W.; Ferrante, R. F.

2004-01-01

Spectra of Europa reveal a surface dominated by water-ice along with hydrated materials and minor amounts of SO2, CO2, and H2O2. Jovian magnetospheric ions (protons, sulfur, and oxygen) and electrons produce significant chemical modifications of the surface on time scales of a few years at micrometer depths. Our laboratory studies examine the formation and stability of radiation products in H2O-rich ices relevant to Europa. Infrared (IR) spectra of ices before and after irradiation reveal the radiation destruction of molecules and the formation of products at 86 - 132 K. In addition, spectra of ices during warming track thermal evolution due to chemical changes and sublimation processes. IR-identified radiation products in 86 - 132 K irradiated H2O + SO2 ices are the bisulfate ion, HSO4(-), sulfate ion, SO4(2-) and the hydronium ion, H3O(+). Warming results in the formation of a residual spectrum similar to liquid sulfuric acid, H2SO4, for H2O:SO2 ratios of 30:1, whereas hydrated sulfuric acid, H2SO4 4 H2O, forms for ratios of 30:1. Radiation products identified for irradiated H2O + H2S ices at 86 K are H2S2 and SO2. When irradiated at 110 and 132 K, ices with H2O:H2S ratios if either 3:1 or 30:1 show the formation of H2SO4 4 H2O on warming to 175 K. We have also examined the radiation stability of H2SO4. Addition of CO2 to H2O + SO2 ices results in the formation of CO3 at 2046 cm (sup -1) (4.89 m). This is the strongest band from a carbon-containing product in the mid-IR spectral region, and it is also seen when either pure CO2 or H2O + CO2 ice is irradiated. Experiments with CH4 added to H2O + SO2 + CO2 ices addressed the question of methane's use as a marker of methanogens in an irradiated ice environment. New results on the near-IR spectrum of pure H2O2 will be included in this presentation. Interpretations of near-IR water bands, with H2O2 present, will be discussed. Irradiations of H2O2 and H2O + H2O2 mixtures, to examine the possibility of O2 and O3 formation, are currently under investigation and new results will be discussed.

Coexisting nanoscale inverse spinel and rock salt crystallographic phases in NiCo2O4 epitaxial thin films grown by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Sharona, H.; Loukya, B.; Bhat, U.; Sahu, R.; Vishal, B.; Silwal, P.; Gupta, A.; Datta, R.

2017-12-01

The origin of alternating wavy dark-bright stripe-like contrast in strain contrast transmission electron microscopy images of NiCo2O4 (NCO) epitaxial thin films grown by pulsed laser deposition has been investigated. The nanoscale stripe-like pattern is determined to be associated with coexisting rock salt (RS) and inverse spinel crystal phases. The presence of two different phases, not addressed in previous reports, is experimentally confirmed by both electron diffraction and high resolution transmission electron microscopy imaging. First principles based calculations, together with compressive strain present in the films, support the formation of such coexisting crystallographic phases in NCO. Similar microstructural patterns and RS structure are not observed in epitaxial films of two other oxides of the spinel family, namely, NiFe2O4 and CoFe2O4. A correlation between the coexisting structures and the macroscopic physical properties of NCO is discussed.

Effect of aging temperature on phase decomposition and mechanical properties in cast duplex stainless steels

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

Mburu, Sarah; Kolli, R. Prakash; Perea, Daniel E.

The microstructure and mechanical properties in unaged and thermally aged (at 280 oC, 320 oC, 360 oC, and 400 oC to 4300 h) CF–3 and CF–8 cast duplex stainless steels (CDSS) are investigated. The unaged CF–8 steel has Cr-rich M23C6 carbides located at the δ–ferrite/γ– austenite heterophase interfaces that were not observed in the CF–3 steel and this corresponds to a difference in mechanical properties. Both unaged steels exhibit incipient spinodal decomposition into Fe-rich α–domains and Cr-rich α’–domains. During aging, spinodal decomposition progresses and the mean wavelength (MW) and mean amplitude (MA) of the compositional fluctuations increase as a functionmore » of aging temperature. Additionally, G–phase precipitates form between the spinodal decomposition domains in CF–3 at 360 oC and 400 oC and in CF–8 at 400 oC. The microstructural evolution is correlated to changes in mechanical properties.« less

CONDENSED MATTER: ELECTRONIC STRUCTURE, ELECTRICAL, MAGNETIC, AND OPTICAL PROPERTIES: Influence of Ytterbia Content on Residual Stress and Microstructure of Y2O3-ZrO2 Thin Films Prepared by EB-PVD*

NASA Astrophysics Data System (ADS)

Xiao, Qi-Ling; Shao, Sriu-Ying; He, Hong-Bo; Shao, Jian-Da; Fan, Zheng-Xiu

2008-09-01

Y2O3 stabilized ZrO2 (YSZ) thin films with different Y2O3 molar contents (0, 3, 7, and 12mol%) are deposited on BK7 substrates by electron-beam evaporation technique. The effects of different Y2O3 contents on residual stresses and structures of YSZ thin films are studied. Residual stresses are investigated by means of two different techniques: the curvature measurement and x-ray diffraction method. It is found that the evolution of residual stresses of YSZ thin films by the two different methods is consistent. Residual stresses of films transform from compressive stress into tensile stress and the tensile stress incre ases monotonically with the increase of Y2O3 content. At the same time, the structures of these films change from the mixture of amorphous and monoclinic phases into high temperature cubic phase. The variations of residual stress correspond to the evolution of structures induced by adding of Y2O3 content.

Ho3+/Yb3+ co-doped TeO2-BaF2-Y2O3 glasses for ∼1.2 μm laser applications

NASA Astrophysics Data System (ADS)

Wang, Shunbin; Li, Chengzhi; Yao, Chuanfei; Jia, Shijie; Jia, Zhixu; Qin, Guanshi; Qin, Weiping

2017-02-01

Intense ∼1.2 μm fluorescence is observed in Ho3+/Yb3+ co-doped TeO2-BaF2-Y2O3 glasses under 915 nm laser diode excitation. The 1.2 μm emission can be ascribed to the transition 5I6→5I8 of Ho3+. With the introducing of BaF2, the content of OH in the glasses drops markedly, and the 1.2 μm emission intensity increases gradually as increasing the concentration percentage of BaF2. Furthermore, microstructured fibers based on the TeO2-BaF2-Y2O3 glasses are fabricated by using a rod-in-tube method, and a relative positive gain of ∼9.42 dB at 1175.3 nm is obtained in a 5 cm long fiber.

Co₃O₄ nanocrystal ink printed on carbon fiber paper as a large-area electrode for electrochemical water splitting.

PubMed

Du, Shichao; Ren, Zhiyu; Zhang, Jun; Wu, Jun; Xi, Wang; Zhu, Jiaqing; Fu, Honggang

2015-05-11

A large-area, self-supported Co3O4 nanocrystal/carbon fiber electrode for oxygen and hydrogen evolution reaction was fabricated via thermal decomposition of the [Co(NH3)n](2+)-oleic acid complex and subsequent spray deposition. Due to the exposed active sites and good electrical conductivity, its operate voltage for overall water splitting is nearly the same as commercial Pt/C.

Deformation mechanisms to ameliorate the mechanical properties of novel TRIP/TWIP Co-Cr-Mo-(Cu) ultrafine eutectic alloys

PubMed Central

Kim, J. T.; Hong, S. H.; Park, H. J.; Kim, Y. S.; Suh, J. Y.; Lee, J. K.; Park, J. M.; Maity, T.; Eckert, J.; Kim, K. B.

2017-01-01

In the present study, the microstructural evolution and the modulation of the mechanical properties have been investigated for a Co-Cr-Mo (CCM) ternary eutectic alloy by addition of a small amount of copper (0.5 and 1 at.%). The microstructural observations reveal a distinct dissimilarity in the eutectic structure such as a broken lamellar structure and a well-aligned lamellar structure and an increasing volume fraction of Co lamellae as increasing amount of copper addition. This microstructural evolution leads to improved plasticity from 1% to 10% without the typical tradeoff between the overall strength and compressive plasticity. Moreover, investigation of the fractured samples indicates that the CCMCu alloy exhibits higher plastic deformability and combinatorial mechanisms for improved plastic behavior. The improved plasticity of CCMCu alloys originates from several deformation mechanisms; i) slip, ii) deformation twinning, iii) strain-induced transformation and iv) shear banding. These results reveal that the mechanical properties of eutectic alloys in the Co-Cr-Mo system can be ameliorated by micro-alloying such as Cu addition. PMID:28067248

Modeling aqueous ferrous iron chemistry at low temperatures with application to Mars

USGS Publications Warehouse

Marion, G.M.; Catling, D.C.; Kargel, J.S.

2003-01-01

Major uncertainties exist with respect to the aqueous geochemical evolution of the Martian surface. Considering the prevailing cryogenic climates and the abundance of salts and iron minerals on Mars, any attempt at comprehensive modeling of Martian aqueous chemistry should include iron chemistry and be valid at low temperatures and high solution concentrations. The objectives of this paper were to (1) estimate ferrous iron Pitzer-equation parameters and iron mineral solubility products at low temperatures (from < 0 ??C to 25 ??C), (2) incorporate these parameters and solubility products into the FREZCHEM model, and (3) use the model to simulate the surficial aqueous geochemical evolution of Mars. Ferrous iron Pitzer-equation parameters were derived in this work or taken from the literature. Six new iron minerals [FeCl2??4H2O, FeCl2??6H2O, FeSO4??H2O, FeSO4??7H2O, FeCO3, and Fe(OH)3] were added to the FREZCHEM model bringing the total solid phases to 56. Agreement between model predictions and experimental data are fair to excellent for the ferrous systems: Fe-Cl, Fe-SO4, Fe-HCO3, H-Fe-Cl, and H-Fe-SO4. We quantified a conceptual model for the aqueous geochemical evolution of the Martian surface. The five stages of the conceptual model are: (1) carbonic acid weathering of primary ferromagnesian minerals to form an initial magnesium-iron-bicarbonate-rich solution; (2) evaporation and precipitation of carbonates, including siderite (FeCO3), with evolution of the brine to a concentrated NaCl solution; (3) ferrous/ferric iron oxidation; (4) either evaporation or freezing of the brine to dryness; and (5) surface acidification. What began as a dilute Mg-Fe-HCO3 dominated leachate representing ferromagnesian weathering evolved into an Earth-like seawater composition dominated by NaCl, and finally into a hypersaline Mg-Na-SO4-Cl brine. Weathering appears to have taken place initially under conditions that allowed solution of ferrous iron [low O2(g)], but later caused oxidation of iron [high O2(g)]. Surface acidification and/or sediment burial can account for the minor amounts of Martian surface carbonates. This model rests on a large number of assumptions and is therefore speculative. Nevertheless, the model is consistent with current understanding concerning surficial salts and minerals based on Martian meteorites, Mars lander data, and remotely-sensed spectral analyses. ?? 2003 Elsevier Ltd.

An experimental study of perovskite-structured mixed ionic- electronic conducting oxides and membranes

NASA Astrophysics Data System (ADS)

Zeng, Pingying

In recent decades, ceramic membranes based on mixed ionic and electronic conducting (MIEC) perovskite-structured oxides have received many attentions for their applications for air separation, or as a membrane reactor for methane oxidation. While numerous perovskite oxide materials have been explored over the past two decades; there are hardly any materials with sufficient practical economic value and performance for large scale applications, which justifies continuing the search for new materials. The main purposes of this thesis study are: (1) develop several novel SrCoO3-delta based MIEC oxides, SrCoCo1-xMxO3-delta, based on which membranes exhibit excellent oxygen permeability; (2) investigate the significant effects of the species and concentration of the dopants M (metal ions with fixed valences) on the various properties of these membranes; (3) investigate the significant effects of sintering temperature on the microstructures and performance of oxygen permeation membranes; and (4) study the performance of oxygen permeation membranes as a membrane reactor for methane combustion. To stabilize the cubic phase structure of the SrCoO3-delta oxide, various amounts of scandium was doped into the B-site of SrCoO 3-delta to form a series of new perovskite oxides, SrScxCoCo 1-xO3-delta (SSCx, x = 0-0.7). The significant effects of scandium-doping concentration on the phase structure, electrical conductivity, sintering performance, thermal and structural stability, cathode performance, and oxygen permeation performance of the SSCx membranes, were systematically studied. Also for a more in-depth understanding, the rate determination steps for the oxygen transport process through the membranes were clarified by theoretical and experimental investigation. It was found that only a minor amount of scandium (5 mol%) doping into the B-site of SrCoO3-delta can effectively stabilize the cubic phase structure, and thus significantly improve the electrical conductivity and oxygen permeability of the SrCoO3-delta membrane. Among all the disk-shaped SSCx (x = 0-0.7) membranes with a thickness of 0.91 mm, both SSC0.05 and SSC0.1 exhibit the highest oxygen permeation rate of about 3.2 mL.cm-2.min-1 (STP) at 900 °C, SSC0.1 also shows excellent cathode performance for a solid oxide fuel cell. Therefore SSC0.1 is of special interest, and thus investigated regarding the performance as a membrane reactor for methane combustion. The performance was evaluated based on the results of methane conversion rates and CO 2 selectivity. Inspired by the above findings, a series of mixed-conducting perovskite oxides SrCo0.95M0.05O3-delta (SCM, M = Bi5+, Zr4+, Ce4+, Sc3+ , La3+, Y3+, Al3+, Zn 2+) were prepared to study the effects of different dopants M on the performance of SrCo0.95M0.05O3-delta. It was found that the M cations significantly affect the crystal phase structure, grain growth, membrane porosity, electrical conductivity, and the oxygen permeability of the SCM membranes. Specifically, it is postulated in this study that the formation of the cubic perovskite structure is dependent on the electron configuration in the outer orbits of M cations, which may provide theoretical guidance for future development of high oxygen permeation ceramic membranes based on the perovskite materials. To study the significant effects of grain sizes on the oxygen permeation behaviors of La0.6Sr0.4Co0.2Fe0.8O3-delta (LSCF) and SrSc0.1Co0.9O 3-delta (SSC0.1) membranes, the LSCF and SSC0.1 membranes were sintered at various temperatures to form different microstructures. Properties of these membranes with varied grain sizes were compared. Results showed that the oxygen permeation rate of the LSCF membrane increases with increasing the grain size, however, it is interesting that the oxygen permeation rate of the SSC0.1 membrane decreases with increasing the grain size. This implies that oxygen transport occurs more, however, less rapidly along grain boundaries than through the bulks in the LSCF and SSC0.1 membranes, respectively. A LSCF hollow fiber membrane and a SSC0.1 planar membrane were applied as membrane reactors for methane combustion. To improve their performances, LSCF powder and SSC0.1 powder were dip-coated and spray-coated on the permeation sides of LSCF hollow fiber membranes and SSC0.1 planar membranes, respectively. The exhaust gas components were analyzed by Gas Chromatography (GC). The performance was evaluated based on the results of methane conversion rates and CO 2 selectivity. The highest CO2 selectivity of the LSCF hollow fiber membrane and the SSC0.1 planar membrane is about 88 and 85 %, respectively. This indicates that the application of an oxygen permeation membrane as methane combustion reactor is feasible.

New insights into microstructural evolution of epitaxial Ni-Mn-Ga films on MgO (1 0 0) substrate by high-resolution X-ray diffraction and orientation imaging investigations

NASA Astrophysics Data System (ADS)

Sharma, Amit; Mohan, Sangeneni; Suwas, Satyam

2018-04-01

In this work, a detailed investigation has been performed on hetero-epitaxial growth and microstructural evolution in highly oriented Ni-Mn-Ga (1 0 0) films grown on MgO (1 0 0) substrate using high-resolution X-ray diffraction and orientation imaging microscopy. Mosaicity of the films has been analysed in terms of tilt angle, twist angle, lateral and vertical coherence length and threading dislocation densities by performing rocking curve measurements and reciprocal space mapping. Density of edge dislocations is found to be an order of magnitude higher than the density of screw dislocations, irrespective of film thickness. X-ray pole figure measurements have revealed an orientation relationship of ? || (1 0 0)MgO; ? || [0 0 1]MgO between the film and substrate. Microstructure predicted by X-ray diffraction is in agreement with that obtained from electron microscopy and atomic force microscopy. The evolution of microstructure in the film with increasing thickness has been explained vis-à-vis dislocation generation and growth mechanisms. Orientation imaging microscopy observations indicate evolutionary growth of film by overgrowth mechanism. Decrease in coercivity with film thickness has been explained as an interplay between stress field developed due to crystal defects and magnetic domain pinning due to surface roughness.

Topotactic phase transformation of the brownmillerite SrCoO2.5 to the perovskite SrCoO3- δ.

PubMed

Jeen, H; Choi, W S; Freeland, J W; Ohta, H; Jung, C U; Lee, H N

2013-07-19

Pulsed laser epitaxy of brownmillerite SrCoO2.5 thin films and their phase transformation to the perovskite SrCoO3-δ are investigated. While the direct growth of the fully oxidized perovskite films is found to be an arduous task, filling some of oxygen vacancies into SrCoO2.5 by topotactic oxidation accompanies systematic evolution of electronic, magnetic, and thermoelectric properties, useful for many information and energy technologies. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Advanced Nanofiber-Based Lithium-Ion Battery Cathodes

NASA Astrophysics Data System (ADS)

Toprakci, Ozan

Among various energy storage technologies, rechargeable lithium-ion batteries have been considered as effective solution to the increasing need for high-energy density electrochemical power sources. Rechargeable lithium-ion batteries offer energy densities 2 - 3 times and power densities 5 - 6 times higher than conventional Ni-Cd and Ni-MH batteries, and as a result, they weigh less and take less space for a given energy delivery. However, the use of lithium-ion batteries in many large applications such as electric vehicles and storage devices for future power grids is hindered by the poor thermal stability, relatively high toxicity, and high cost of lithium cobalt oxide (LiCoO2) powders, which are currently used as the cathode material in commercial lithium-ion batteries. Recently, lithium iron phosphate (LiFePO 4) powders have become a favorable cathode material for lithium-ion batteries because of their low cost, high discharge potential (around 3.4 V versus Li/Li+), large specific capacity (170 mAh g -1), good thermal stability, and high abundance with the environmentally benign and safe nature. As a result, there is a huge demand for the production of high-performance LiFePO4. However, LiFePO4 also has its own limitation such as low conductivity (˜10-9 S cm -1), which results in poor rate capability. To address this problem, various approaches can be used such as decreasing particle size of LiFePO 4, doping LiFePO4 with metal ions or coating LiFePO 4 surface with carboneous materials. Formation of conductive layer on LiFePO4 and decreasing particle size are promising approaches due to their superior contribution to electrical conductivity and electrochemical performance of LiFePO4. Although different approaches can be used for surface coating and particle size decrement, electrospinning can be potentially considered as an efficient, simple and inexpensive way. In this study, LiFePO 4/carbon and carbon nanotube- and graphene-loaded electrospun LiFePO 4/carbon composite nanofibers were synthesized by using a combination of sol-gel and electrospinning. During the material preparation, polyacrylonitrile (PAN) was used as an electrospinning media and a carbon source. LiFePO 4 precursor materials and/or conductive materials (carbon nanotubes and graphene) and PAN were dissolved in N,N-dimethylformamide separately and they were mixed before electrospinning. LiFePO4 precursor/PAN fibers were heat treated, during which LiFePO4 precursor transformed to energy-storage LiFePO4 material and PAN was converted to carbon. The surface morphology, microstructure and electrochemical performance of the materials were analyzed. Compared with conventional powder based positive electrodes, the novel LiFePO4/C composite nanofiber cathodes possess better electrochemical performance. Furthermore, the newly developed LiFePO 4/C composite nanofibers are easy to fabricate, highly controllable, and can be used in practical Lithium-ion battery applications. In addition to LiFePO4, more recent efforts have been directed to mixed form of layered lithiummetal oxides (Li-Ni-Mn-Co). Nickel and manganese are of importance because of their lower cost, safety and higher abundance in nature. These new cathodes offer noticeable improvement in the capacity and cycling behavior. In these cathodes, LiNi1/3Co1/3Mn 1/3O2 attracted significant interest because of its good electrochemical properties such as high capacity, prolonged cycling life, and so on. On the other hand, it has some disadvantages such as instability at high voltages and high current densities. To overcome these problems, synthesis of layered Li-rich composite materials such as xLi2MnO3˙(1-x)LiCo 1/3Ni1/3Mn1/3O2 can be a promising approach. In this study, various xLi2MnO3˙(1-x)LiCo 1/3Ni1/3Mn1/3O2 (x=0.1, 0.2, 0.3, 0.4, 0.5) composite cathode materials were prepared by a one-step sol-gel route. Morphology, microstructure and electrochemical behavior of these cathode materials were evaluated. The resultant cathode material shows good electrochemical performance. Relatively low cost and simple preparation route make new xLi2MnO3˙(1-x)LiMn1/3Ni 1/3Co1/3O2 composite materials possible to use as potential cathode candidate for lithium-ion batteries.

(Ba1- x Bi0.33 x Sr0.67 x )(Ti1- x Bi0.67 x V0.33 x )O3 and (Ba1- x Bi0.5 x Sr0.5 x )(Ti1- x Bi0.5 x Ti0.5 x )O3 solid solutions: phase evolution, microstructure, dielectric properties and impedance analysis

NASA Astrophysics Data System (ADS)

Chen, Xiuli; Li, Xiaoxia; Yan, Xiao; Liu, Gaofeng; Zhou, Huanfu

2018-06-01

Perovskite solid solution ceramics of (Ba1- x Bi0.33 x Sr0.67 x )(Ti1- x Bi0.67 x V0.33 x )O3 and (Ba1- x Bi0.5 x Sr0.5 x )(Ti1- x Bi0.5 x Ti0.5 x )O3 (BBSTBV, BBSTBT, 0.02 ≤ x ≤ 0.2) were prepared by the traditional solid state reaction technique. The phase evolution, microstructure and dielectric properties of BBSTBV and BBSTBT ceramics were researched. X-Ray diffraction results illustrated that both BBSTBV and BBSTBT could form a homogenous solid solution which has a similar structure with BaTiO3. The optimized properties of (Ba0.8Bi0.1Sr0.1)(Ti0.8Bi0.1Ti0.1)O3 ceramics with stable ɛ r ( 1769-2293), small Δ ɛ/ ɛ 25 °C values (± 15%) over a broad temperature range from - 58 to 151 °C and low tan δ ≤ 0.03 from - 11 to 131 °C were obtained. In the high-temperature region, the relaxation and conduction process are attributed to the thermal activation and the oxygen vacancies may be the ionic charge carriers in perovskite ferroelectrics.

Cobalt-Doped Perovskite-Type Oxide LaMnO3 as Bifunctional Oxygen Catalysts for Hybrid Lithium-Oxygen Batteries.

PubMed

Liu, Xiao; Gong, Hao; Wang, Tao; Guo, Hu; Song, Li; Xia, Wei; Gao, Bin; Jiang, Zhongyi; Feng, Linfei; He, Jianping

2018-03-02

Perovskite-type oxides based on rare-earth metals containing lanthanum manganate are promising catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolyte. Perovskite-type LaMnO 3 shows excellent ORR performance, but poor OER activity. To improve the OER performance of LaMnO 3 , the element cobalt is doped into perovskite-type LaMnO 3 through a sol-gel method followed by a calcination process. To assess electrocatalytic activities for the ORR and OER, a series of LaMn 1-x Co x O 3 (x=0, 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5) perovskite oxides were synthesized. The results indicate that the amount of doped cobalt has a significant effect on the catalytic performance of LaMn 1-x Co x O 3 . If x=0.3, LaMn 0.7 Co 0.3 O 3 not only shows a tolerable electrocatalytic activity for the ORR, but also exhibits a great improvement (>200 mV) on the catalytic activity for the OER; this indicates that the doping of cobalt is an effective approach to improve the OER performance of LaMnO 3 . Furthermore, the results demonstrate that LaMn 0.7 Co 0.3 O 3 is a promising cost-effective bifunctional catalyst with high performance in the ORR and OER for application in hybrid Li-O 2 batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

BiVO4 microstructures with various morphologies: Synthesis and characterization

NASA Astrophysics Data System (ADS)

Wu, Min; Jing, Qifeng; Feng, Xinyan; Chen, Limiao

2018-01-01

Bismuth vanadate (BiVO4) microstructures with dumbbell, rod, ellipsoid, sphere, and cake-like morphologies have been successfully fabricated by using a surfactant-free hydrothermal method, in which the morphology of the BiVO4 microstructures can be tuned by simply varying the molar ratio of Bi(NO)3·5H2O to NaVO3 in the starting materials. Based on a series of contrast experiments, the probable formation mechanism of the BiVO4 microstructures with multiple shapes have been proposed. The photocatalytic performances of the as-prepared BiVO4 microstructures have been evaluated by studying the degradation of Rhodamine B solutions under visible light irradiation. The results reveal that the cake-like BiVO4 microstructures exhibit the higher photocatalytic activity than other BiVO4 microstructures due to its high surface area and unique morphology.

Microstructure optimization for high-performance PrBa0.5Sr0.5Co1.5Fe0.5O5+δ-La2NiO4+δ core-shell cathode of solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Li, Jin; Qiu, Peng; Xia, Meng; Jia, Lichao; Chi, Bo; Pu, Jian; Li, Jian

2018-03-01

Four PrBa0.5Sr0.5Co1.5Fe0.5O5+δ (PBSCF)-La2NiO4+δ (LN) core-shell cathodes, designated as PL-0, PL-1, PL-3 and PL-5, are prepared by infiltrating LN solution into PBSCF scaffold, and they are investigated in terms of the effect of LN thickness on their electrochemical performance. PL-3 with a continuous LN coating of a moderate average thickness (∼9 nm) demonstrates the lowest initial polarization resistance (0.51 Ω cm2) and highest power density (0.71 W cm-2) among all the cathodes. Polarized at 400 mA cm-2 and 700 °C for up to 40 h, the polarization resistance of all the prepared cathodes increases to approach a stable level after early stage decrease due to current activation, and PL-3 exhibits a slower average rate of performance degradation (25%). The electrochemical performance improvement is mainly attributed to that LN has a relatively high oxygen surface exchange coefficient and continuous LN coating depresses Sr segregation at PBSCF/LN interface.

An Investigation on the Wear and Corrosion Behavior of HVOF-Sprayed WC-12Co-Al2O3 Cermet Coating

NASA Astrophysics Data System (ADS)

Chakradhar, R. P. S.; Prasad, G.; Venkateswarlu, K.; Srivastava, Meenu

2018-03-01

The aim of the present study is to develop thermally sprayable WC-12Co and WC-12Co- xAl2O3 ( x = 10 and 15 wt.%) cermet coatings on steel substrate (SS 304) by high-velocity oxy fuel (HVOF) method. Influence of Al2O3 addition on the wear and corrosion behavior of WC-12Co coating has been studied. The microstructure and chemical composition of the coatings were analyzed using field emission scanning electron microscope (FESEM), and phase identification was carried out using x-ray diffraction (XRD) studies. The morphology of the coating appears as coarse granular structure. The XRD studies revealed the presence of hexagonal WC phase along with η-Co6W6C phase. It has been observed from the microhardness measurements, that the values gradually increase from 950 to 1300 HK with the addition of Al2O3 from 0 to 15 wt.%. The wear rate of WC-12Co-15Al2O3 (3.19 × 10-6 mm3/Nm) and WC-12Co-10Al2O3 (5.26 × 10-6 mm3/Nm) coatings was seen to be one order of magnitude lower than that of WC-12Co (2.9 × 10-5 mm3/Nm) coating. The polarization studies revealed that WC-12Co-15Al2O3 cermet coating showed superior corrosion protection than that of WC-12Co-10Al2O3 and WC-12Co coatings. This has been attributed to the gradual decrease in the porosity levels with an increase in Al2O3 content which is supported by morphology studies. The microhardness and wear behavior of WC-12Co-Al2O3 coatings are equivalent to those of hard chrome suggesting the possibility of its replacement.

Heavy ion irradiation-induced microstructural evolution in pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} at room temperature and 723 K

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

Xie, Q.R.; Zhang, J., E-mail: zhangjian@xmu.edu.cn; Dong, X.N.

Polycrystalline pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated with 600 keV Kr{sup 3+} at room temperature and 723 K to a fluence of 4×10{sup 15} ions/cm{sup 2}, corresponding to an average ballistic damage dose of 10 displacements per atom in the peak damage region. Irradiation-induced microstructural evolution was examined by grazing incidence X-ray diffraction, and cross-sectional transmission electron microscopy. Incomplete amorphization was observed in the sample irradiated at room temperature due to the formation of nano-crystal which has the identical structure of pyrochlore, and the formation of nano-crystal is attributed to the mechanism of epitaxial recrystallization. However, an orderedmore » pyrochlore phase to a swelling disordered fluorite phase transformation is occurred for the Lu{sub 2}Ti{sub 2}O{sub 7} sample irradiated at 723 K, which is due to the disordering of metal cations and anion vacancies. - Graphical Abstract: Polycrystalline pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated with 600 keV Kr{sup 3+} to a fluence of 4×10{sup 15} ions/cm{sup 2} at room temperature and 723 K, Incomplete amorphization was observed in the sample irradiated at room temperature due to the formation of nano-crystal. However, an ordered pyrochlore phase to a swelling disordered fluorite phase transformation is occurred for the Lu{sub 2}Ti{sub 2}O{sub 7} sample irradiated at 723 K, which is due to the disordering of metal cations and anion vacancies. - Highlights: Pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated by heavy ions at RT and 723 K. At RT irradiation, ~75% of amorphization was achieved. The nano-crystals were formed in the damage layer at RT irradiation. The formed nano-crystals enhanced the radiation tolerance of Lu{sub 2}Ti{sub 2}O{sub 7}. A pyrochlore to fluorite phase transformation was observed at 723 K irradiation.« less

In-situ Raman spectroscopic investigation of LiMn1.45Ni0.45M0.1O4 (M = Cr, Co) 5 V cathode materials

NASA Astrophysics Data System (ADS)

Zhu, W.; Liu, D.; Trottier, J.; Gagnon, C.; Howe, J.; Mauger, A.; Julien, C. M.; Zaghib, K.

2015-12-01

In-situ Raman spectroscopy is employed to investigate the valence state variations of nickel and manganese, as well as the local structure change of LiMn1.45Ni0.45M0.1O4 (M = Cr, Co) cathodes (LMN) during galvanostatic charge-discharge. Raman spectra are collected between 3.5 and 4.9 V in the wave number range of 100-800 cm-1. The Raman observations showed that the pristine cathodes of Cr- and Co-doped LMN have essentially the same spectra, and they also have similar evolution patterns during cycling showing their reversible behaviour in the de-lithiation and lithiation processes. The Raman spectra of the pristine cathodes have eleven bands, located at 162, 220, 378, 408, 486, 498, 528, 593, 613, 639 and 672 cm-1. The bands with wave number <300 cm-1 are attributed to the translation mode of molecular vibration; the 486, 593 and 639 cm-1 bands are assigned to the stretching mode of Mn-O bond; and the vibration modes at 408, 498, 528 and 613 cm-1 originated from the Ni-O bond; The band at 672 cm-1 is attributed to A1g mode of Cr3+-O/Co3+-O. During cycling, several new bands are detected near the end of charge, among which the T2g(T) band at 170 cm-1 is attributed to the translation mode of lattice vibration in which the lithium concentration is low, and the T2g band at 538 cm-1 is due to the presence of Ni4+-O bond in the crystal structure. The T2g(T) and T2g(Ni4+-O) bands are clearly evident at V ≥ 4.78 (x ∼ 0.32) and V ≥ 4.82 (x ∼ 0.28) for Cr- and Co-doped LMN, respectively.

Fractionation of Zr and Hf during the differentiation of peralkaline magmatic system (Lovozero rare metal deposit, Kola Peninsula)

NASA Astrophysics Data System (ADS)

Kogarko, Liya

2016-04-01

Zirconium and hafnium are valuable strategic metals. We assessed principal features of the distribution of these elements in peralkaline rocks, ores and rock-forming and accessory minerals of Lovozero complex. The accumulation of these elements during the evolution of alkaline magma of Lovozero deposit up to extremely high concentrations in eudialyte ores (5-8% ZrO2 and 1200-1800 ppm Hf) has been established. These ores represent valuable complex raw material not only for Zr and Hf, but for REE as well. We evaluated partition coefficients of these elements in alkaline pyroxenes (aegirines) from porphyry-like agpaitic lujavrites of Lovozero massif which are 0.40 for zirconium and 0.58 for hafnium. We assessed variations of Zr/Hf ratio for all the rocks of Lovozero alkaline massif. The growth of this ratio in the course of the evolution of alkaline magma has been observed from 38 in the earliest magmatic phase, to 44 in the second phase and to 51-53 in the latest manifestation of alkaline magmatsm. On the basis of the obtained data and equations of equilibrium and fractional crystallization the model of the fractionation of zirconium and hafnium during the evolution of Lovozero intrusion has been constructed. We have demonstrated that the source of strongly enriched magmatic systems similar to Lovozero rare metal deposit is short-lived enriched reservoir - metasomatized and carbonatized mantle substrate. We investigated the fractionation of zirconium and hafnium in carbonatized mantle xenoliths from East Antarctica. The elevated Zr/Hf ratios (up to 125) in metasomatized xenoliths by comparison with the chondritic value have been found. The main reactions of carbonate metasomatism lead to the replacement of primary orthopyroxene by clinopyroxene 2Mg2Si2O6 + CaMg(CO3)2 = 2Mg2SiO4 + CaMgSi2O6 + 2CO2 3CaMg(CO3)2 + CaMgSi2O6 = 4CaCO3 + 2Mg2SiO4 + 2CO2 The substantial expansion of the clinopyroxene crystallization field results in increase of Zr/Hf ratio in equilibrium melt due to the higher value of Hf partition coefficient by comparison with Zr. The migration of active carbonate and carbonate-silicate melts equilibrated with the metasomatic wehrlites leads to the increase in Zr/Hf ratio in carbonatized mantle substrate. This work has been financially supported by the grant 15-17-30019 of the Russian Science Foundation.

Porous nanocubic Mn3O4-Co3O4 composites and their application as electrochemical supercapacitors.

PubMed

Pang, Huan; Deng, Jiawei; Du, Jimin; Li, Sujuan; Li, Juan; Ma, Yahui; Zhang, Jiangshan; Chen, Jing

2012-09-14

A simple approach has been developed to fabricate ideal supercapacitors based on porous Mn(3)O(4)-Co(3)O(4) nanocubic composite electrodes. We can easily obtain porous corner-truncated nanocubic Mn(3)O(4)-Co(3)O(4) composite nanomaterials without any subsequent complicated workup procedure for the removal of a hard template, seed or by using a soft template. In such a composite, the porous Mn(3)O(4)-Co(3)O(4) enables a fast and reversible redox reaction to improve the specific capacitance. The porous nanocubic Mn(3)O(4)-Co(3)O(4) composite electrode can effectively transport electrolytes and shorten the ion diffusion path, which offers excellent electrochemical performance. These results suggest that such porous Mn(3)O(4)-Co(3)O(4) composite nanocubes are very promising for next generation high-performance supercapacitors.

Enhanced hydrogen release by catalyzed hydrolysis of sodium borohydride-ammonia borane mixtures: a solution-state 11B NMR study.

PubMed

Hannauer, J; Demirci, U B; Geantet, C; Herrmann, J M; Miele, P

2011-03-07

Hydrolysis of mixtures consisting of sodium borohydride NaBH(4) (SB) and ammonia borane NH(3)BH(3) (AB) was studied in the absence/presence of a Co catalyst. The kinetics of the H(2) evolutions was measured. The reactions were followed in situ by solution-state (11)B NMR and the hydrolysis by-products characterized by NMR, XRD and IR. It is demonstrated that the combination of the two compounds gives a synergetic effect. SB rapidly reduces the Co catalyst precursor and the NH(4)(+) ions from AB contribute in the dispersion of the in situ formed Co nanoparticles. As a result, the kinetics of H(2) evolution is greatly improved. For instance, a hydrogen generation rate of 29.6 L min(-1) g(-1)(Co) was found for a mixture consisting of 81 wt% NH(3)BH(3), 9 wt% NaBH(4) and 10 wt% CoCl(2). By (11)B NMR, it was showed that the reaction mechanisms are quite trivial. As soon as the Co catalyst forms in situ, SB, rather than AB, hydrolyzes until it is totally converted. Then, the overall hydrolysis continues with that of AB. Both reactions follow a bimolecular Langmuir-Hinshelwood mechanism; no reaction intermediates were observed during the process. In fact, SB and AB convert directly into B(OH)(4)(-), which comes in equilibrium with a polyborate compound identified as B(3)O(3)(OH)(4)(-). All of these results are discussed herein.

Light in the darkening on Naica gypsum crystals

NASA Astrophysics Data System (ADS)

Castillo-Sandoval, I.; Fuentes-Cobas, L. E.; Fuentes-Montero, M. E.; Esparza-Ponce, H. E.; Carreno-Márquez, J.; Reyes-Cortes, M.; Montero-Cabrera, M. E.

2015-07-01

Naica mine is located in a semi-desertic region at the central-south of Chihuahua State. The Cave of Swords was discovered in 1910 and the Cave of Crystals 90 years later at Naica mines. It is expected that during the last century the human presence has changed the microclimatic conditions inside the cave, resulting in the deterioration of the crystals and the deposition of impurities on gypsum surfaces. As a contribution to the clarification of the mentioned issues, the present work refers to the use of synchrotron radiation for the identification of phases on these surfaces. All the experiments were performed at the Stanford Synchrotron Radiation Lightsource. Grazing incidence X-ray diffraction (GIXRD) and radiography-aided X-ray diffraction (RAXRD) experiments were performed at beamline 11-3. X-Ray micro-fluorescence (μ-SXRF) and micro-X-ray absorption (μ-XANES) were measured at beamline 2-3. Representative results obtained may be summarized as follows: a) Gypsum, galena, sphalerite, hematite and cuprite at the surface of the gypsum crystals were determined. b) The samples micro-structure is affected by impurities. c) The elemental distributions and correlations (0.6-0.9) of Cu, K, Fe, Mn, Pb, Zn, Ca and S were identified by μ-SXRF. The correlations among elemental contents confirmed the phase identification, with the exception of manganese and potassium due to the amorphous nature of some impurity compounds in these samples. The compounds hematite (Fe2O3), β-MnO2, Mn2O3, MnO and/or MnCO3, PbS, PbCO3 and/or PbSO4, ZnO4, ZnS and/or smithsonite (ZnCO3), CuS + Cu Oxide were identified by XANES. Plausibly, these latter compounds do not form crystalline phases.

Effect of starting powder characteristics on density, microstructure and low temperature oxidation behavior of a Si3N48w/o Y2O3 ceramic

NASA Technical Reports Server (NTRS)

Schuon, S.; Dutta, S.

1980-01-01

The densification and oxidation behavior of Si3N4 - 8w/oY2O3 prepared from three commercial starting powders were studied. Bars of SN 402, SN 502, and CP 85/15 were sintered for 3 to 4.5 hours at 1750 C. A second set was hot pressed for 2 hours at 1750 C. The microstructures were studied by transmission electron microscopy and scanning electron microscopy, densities were determined, and the phase compositions were determined by X-ray diffraction. Densification and microstructure were greatly influenced by the starting powder morphology and impurity content. Although SN 402 exhibited the maximum weight lose, the highest sintered and hot pressed densities were obtained with this powder. All powders had both equiaxed and elongated grains. Sintered bars were composed of beta silicon nitride and n-melelite. In contrast, hot pressed bars contained beta silicon nitride, H-phase, and J-phase, but no melelite. Yttria distribution in sintered bars was related to the presence of cation impurities such as Ca, Fe, and Mg. A limited oxidation study at 750 C in air showed no instability in these Si3N4 - 8 w/oY2O3 specimens, regardless of startin powder.

Microstructural examination of V-(3-6%)Cr-(3-5%)Ti irradiated in the ATR-A1 experiment

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

Gelles, D.S.

Microstructural examination results are reported for four heats of V-(3-6%)Cr-(3-5%)Ti irradiated in the ATR-A1 experiment to {approximately}4 dpa at {approximately}200 and 300 C to provide an understanding of the microstructural evolution that may be associated with degradation of mechanical properties. Fine precipitates were observed in high density intermixed with small defect clusters for all conditions examined following the irradiation. The irradiation-induced precipitation does not appear to be affected by preirradiation heat treatment or composition.

Superparamagnetic iron oxide-reduced graphene oxide nanohybrid-a vehicle for targeted drug delivery and hyperthermia treatment of cancer

NASA Astrophysics Data System (ADS)

Gupta, Jagriti; Prakash, Anand; Jaiswal, Manish K.; Agarrwal, Atanuu; Bahadur, D.

2018-02-01

In this work, an efficient superparamagnetic iron oxide-reduced graphene oxide (Fe3O4-RGO) nanohybrid has been synthesized following one-step co-precipitation method. The phase identification, microstructure and magnetic behavior of nanohybrid were characterized by X-ray diffraction, transmission electron microscopy (TEM), raman spectroscopy and vibrating sample magnetometer (VSM), respectively. TEM micrograph confirms the presence of well-segregated Fe3O4 nanoparticles in RGO layers. The layered RGO minimizes the agglomeration in Fe3O4 nanoparticles with slight reduction in magnetic behavior. Doxorubicin (DOX) has been used as a model drug to investigate the loading efficiency of nanohybrid and chemo-thermo therapeutic effect on human cervical cancer (HeLa cells). The DOX loaded nanohybrid (DOX-Fe3O4-RGO) shows maximum inhibition of human cervical cancer cell lines during magnetic field assisted hyperthermia treatment. The synergistic effect of nanohybrid demonstrated the potential for cancer cell proliferation prevention up to 90% when treated at the concentration of 2 mg mL-1 for one million cells and exposed to AC field of 335 Oe at a fixed frequency of 265 kHz for 35 min.

Intrinsic stress evolution during amorphous oxide film growth on Al surfaces

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

Flötotto, D., E-mail: d.floetotto@is.mpg.de; Wang, Z. M.; Jeurgens, L. P. H.

2014-03-03

The intrinsic stress evolution during formation of ultrathin amorphous oxide films on Al(111) and Al(100) surfaces by thermal oxidation at room temperature was investigated in real-time by in-situ substrate curvature measurements and detailed atomic-scale microstructural analyses. During thickening of the oxide a considerable amount of growth stresses is generated in, remarkably even amorphous, ultrathin Al{sub 2}O{sub 3} films. The surface orientation-dependent stress evolutions during O adsorption on the bare Al surfaces and during subsequent oxide-film growth can be interpreted as a result of (i) adsorption-induced surface stress changes and (ii) competing processes of free volume generation and structural relaxation, respectively.

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

Cao, J., E-mail: cao_jian@hit.edu.cn; State Key Laboratory of Advanced Welding and Joining, Harbin Institute of Technology, Harbin 150001; Song, X.G., E-mail: song_xiaoguohit@yahoo.com.cn

Reliable brazing of ZrO{sub 2} ceramic and Ti–6Al–4V alloy was achieved using NiCrSiB amorphous filler foil. The interfacial microstructure of ZrO{sub 2}/Ti–6Al–4V joints was characterized by scanning electron microscope, energy dispersive spectrometer and micro-focused X-ray diffractometer. The effects of brazing temperature on the interfacial microstructure and joining properties of brazed joints were investigated in detail. Active Ti of Ti–6Al–4V alloy dissolved into molten filler metal and reacted with ZrO{sub 2} ceramic to form a continuous TiO reaction layer, which played an important role in brazing. Various reaction phases including Ti{sub 2}Ni, Ti{sub 5}Si{sub 3} and β-Ti were formed in brazedmore » joints. With an increasing of brazing temperature, the TiO layer thickened gradually while the Ti{sub 2}Ni amount reduced. Shear test indicated that brazed joints tend to fracture at the interface between ZrO{sub 2} ceramic and brazing seam or Ti{sub 2}Ni intermetallic layer. The maximum average shear strength reached 284.6 MPa when brazed at 1025 °C for 10 min. - Graphical Abstract: Interfacial microstructure of ZrO{sub 2}/TC4 joint brazed using NiCrSiB amorphous filler foil was: ZrO{sub 2}/TiO/Ti{sub 2}Ni + β-Ti + Ti{sub 5}Si{sub 3}/β-Ti/Widmanstätten structure/TC4. - Highlights: • Brazing of ZrO{sub 2} ceramic and Ti-6Al-4V alloy was achieved. • Interfacial microstructure was TiO/Ti{sub 2}Ni + β + Ti{sub 5}Si{sub 3}/β/Widmanstätten structure. • The formation of TiO produced the darkening effect of ZrO{sub 2} ceramic. • The highest joining strength of 284.6MPa was obtained.« less

Ab initio molecular dynamics simulations reveal localization and time evolution dynamics of an excess electron in heterogeneous CO2-H2O systems.

PubMed

Liu, Ping; Zhao, Jing; Liu, Jinxiang; Zhang, Meng; Bu, Yuxiang

2014-01-28

In view of the important implications of excess electrons (EEs) interacting with CO2-H2O clusters in many fields, using ab initio molecular dynamics simulation technique, we reveal the structures and dynamics of an EE associated with its localization and subsequent time evolution in heterogeneous CO2-H2O mixed media. Our results indicate that although hydration can increase the electron-binding ability of a CO2 molecule, it only plays an assisting role. Instead, it is the bending vibrations that play the major role in localizing the EE. Due to enhanced attraction of CO2, an EE can stably reside in the empty, low-lying π(*) orbital of a CO2 molecule via a localization process arising from its initial binding state. The localization is completed within a few tens of femtoseconds. After EE trapping, the ∠OCO angle of the core CO2 (-) oscillates in the range of 127°∼142°, with an oscillation period of about 48 fs. The corresponding vertical detachment energy of the EE is about 4.0 eV, which indicates extreme stability of such a CO2-bound solvated EE in [CO2(H2O)n](-) systems. Interestingly, hydration occurs not only on the O atoms of the core CO2 (-) through formation of O⋯H-O H-bond(s), but also on the C atom, through formation of a C⋯H-O H-bond. In the latter binding mode, the EE cloud exhibits considerable penetration to the solvent water molecules, and its IR characteristic peak is relatively red-shifted compared with the former. Hydration on the C site can increase the EE distribution at the C atom and thus reduce the C⋯H distance in the C⋯H-O H-bonds, and vice versa. The number of water molecules associated with the CO2 (-) anion in the first hydration shell is about 4∼7. No dimer-core (C2O4 (-)) and core-switching were observed in the double CO2 aqueous media. This work provides molecular dynamics insights into the localization and time evolution dynamics of an EE in heterogeneous CO2-H2O media.

Efficient Removal of Methane over Cobalt-Monoxide-Doped AuPd Nanocatalysts.

PubMed

Xie, Shaohua; Liu, Yuxi; Deng, Jiguang; Zang, Simiao; Zhang, Zhenhua; Arandiyan, Hamidreza; Dai, Hongxing

2017-02-21

To overcome deactivation of Pd-based catalysts at high temperatures, we herein design a novel pathway by introducing a certain amount of CoO to the supported Au-Pd alloy nanoparticles (NPs) to generate high-performance Au-Pd-xCoO/three-dimensionally ordered macroporous (3DOM) Co 3 O 4 (x is the Co/Pd molar ratio) catalysts. The doping of CoO induced the formation of PdO-CoO active sites, which was beneficial for the improvement in adsorption and activation of CH 4 and catalytic performance. The Au-Pd-0.40CoO/3DOM Co 3 O 4 sample performed the best (T 90% = 341 °C at a space velocity of 20 000 mL g -1 h -1 ). Deactivation of the 3DOM Co 3 O 4 -supported Au-Pd, Pd-CoO, and Au-Pd-xCoO nanocatalysts resulting from water vapor addition was due to the formation and accumulation of hydroxyl on the catalyst surface, whereas deactivation of the Pd-CoO/3DOM Co 3 O 4 catalyst at high temperatures (680-800 °C) might be due to decomposition of the PdO y active phase into aggregated Pd 0 NPs. The Au-Pd-xCoO/3DOM Co 3 O 4 nanocatalysts exhibited better thermal stability and water tolerance ability compared to the 3DOM Co 3 O 4 -supported Au-Pd and Pd-CoO nanocatalysts. We believe that the supported Au-Pd-xCoO nanomaterials are promising catalysts in practical applications for organic combustion.

X-ray and optical crystallographic parameters investigations of high frequency induction melted Al-(alpha-Al(2)O(3)) alloys.

PubMed

Bourbia, A; Draissia, M; Bedboudi, H; Boulkhessaim, S; Debili, M Y

2010-01-01

This article deals with the microstructural strengthening mechanisms of aluminium by means of hard alpha-Al(2)O(3) alumina fine particles. A broad of understanding views covering materials preparations, elaboration process, characterization techniques and associated microstructural characteristic parameters measurements is given. In order to investigate the microstructural characteristic parameters and the mechanical strengthening mechanisms of pure aluminium by hard fine particles, a set of Al-(alpha-Al(2)O(3)) alloys samples were made under vacuum by high fusion temperature melting, the high frequency (HF) process, and rapidly solidified under ambient temperature from a mixture of cold-compacted high-pure fine Al and alpha-Al(2)O(3) powders. The as-solidified Al-(alpha-Al(2)O(3)) alloys were characterized by means of X-ray diffraction (XRD) analyses, optical microscopy observations and Vickers microhardness tests in both brut and heat-treated states. It was found that the as-solidified HF Al-(alpha-Al(2)O(3)) alloys with compositions below 4 wt.% (alpha-Al(2)O(3)) are single-phase microstructures of the solid solution FCC Al phase and over two-phase microstructures of the solid solution FCC Al and the Rhombohedral alpha-Al(2)O(3) phases. The optical micrographs reveal the presence of a grain size refinement in these alloys. Vickers microhardness of the as-solidified Al-(alpha-Al(2)O(3)) is increased by means of pure fine alpha-Al(2)O(3) alumina particles. These combined effects of strengthening and grain size refinement observed in the as-solidified Al-(alpha-Al(2)O(3)) alloys are essentially due to a strengthening of Al by the alpha-Al(2)O(3) alumina particles insertion in the (HF) melted and rapidly solidified alloys.

Influence of nanogold additives on phase formation, microstructure and dielectric properties of perovskite BaTiO3 ceramics

NASA Astrophysics Data System (ADS)

Nonkumwong, Jeeranan; Ananta, Supon; Srisombat, Laongnuan

2015-06-01

The formation of perovskite phase, microstructure and dielectric properties of nanogold-modified barium titanate (BaTiO3) ceramics was examined as a function of gold nanoparticle contents by employing a combination of X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray, Archimedes principle and dielectric measurement techniques. These ceramics were fabricated from a simple mixed-oxide method. The amount of gold nanoparticles was found to be one of the key factors controlling densification, grain growth and dielectric response in BaTiO3 ceramics. It was found that under suitable amount of nanogold addition (4 mol%), highly dense perovskite BaTiO3 ceramics with homogeneous microstructures of refined grains (~0.5-3.1 μm) and excellence dielectric properties can be produced.

A new coating method for alleviating surface degradation of LiNi0.6Co0.2Mn0.2O2 cathode material: nanoscale surface treatment of primary particles.

PubMed

Kim, Hyejung; Kim, Min Gyu; Jeong, Hu Young; Nam, Haisol; Cho, Jaephil

2015-03-11

Structural degradation of Ni-rich cathode materials (LiNi(x)M(1-x)O2; M = Mn, Co, and Al; x > 0.5) during cycling at both high voltage (>4.3 V) and high temperature (>50 °C) led to the continuous generation of microcracks in a secondary particle that consisted of aggregated micrometer-sized primary particles. These microcracks caused deterioration of the electrochemical properties by disconnecting the electrical pathway between the primary particles and creating thermal instability owing to oxygen evolution during phase transformation. Here, we report a new concept to overcome those problems of the Ni-rich cathode material via nanoscale surface treatment of the primary particles. The resultant primary particles' surfaces had a higher cobalt content and a cation-mixing phase (Fm3̅m) with nanoscale thickness in the LiNi0.6Co0.2Mn0.2O2 cathode, leading to mitigation of the microcracks by suppressing the structural change from a layered to rock-salt phase. Furthermore, the higher oxidation state of Mn(4+) at the surface minimized the oxygen evolution at high temperatures. This approach resulted in improved structural and thermal stability in the severe cycling-test environment at 60 °C between 3.0 and 4.45 V and at elevated temperatures, showing a rate capability that was comparable to that of the pristine sample.

Effect of cyanato, azido, carboxylato, and carbonato ligands on the formation of cobalt(II) polyoxometalates: characterization, magnetic, and electrochemical studies of multinuclear cobalt clusters.

PubMed

Lisnard, Laurent; Mialane, Pierre; Dolbecq, Anne; Marrot, Jérôme; Clemente-Juan, Juan Modesto; Coronado, Eugenio; Keita, Bineta; de Oliveira, Pedro; Nadjo, Louis; Sécheresse, Francis

2007-01-01

Five Co(II) silicotungstate complexes are reported. The centrosymmetric heptanuclear compound K(20)[{(B-beta-SiW(9)O(33)(OH))(beta-SiW(8)O(29)(OH)(2))Co(3)(H(2)O)}(2)Co(H(2)O)(2)]47 H(2)O (1) consists of two {(B-beta-SiW(9)O(33)(OH))(beta-SiW(8)O(29)(OH)(2))Co(3)(H(2)O)} units connected by a {CoO(4)(H(2)O)(2)} group. In the chiral species K(7)[Co(1.5)(H(2)O)(7))][(gamma-SiW(10)O(36))(beta-SiW(8)O(30)(OH))Co(4)(OH)(H(2)O)(7)]36 H(2)O (2), a {gamma-SiW(10)O(36)} and a {beta-SiW(8)O(30)(OH)} unit enclose a mononuclear {CoO(4)(H(2)O)(2)} group and a {Co(3)O(7)(OH)(H(2)O)(5)} fragment. The two trinuclear Co(II) clusters present in 1 enclose a mu(4)-O atom, while in 2 a mu(3)-OH bridging group connects the three paramagnetic centers of the trinuclear unit, inducing significantly larger Co-L-Co (L=mu(4)-O (1), mu(3)-OH (2)) bridging angles in 2 (theta(av(Co-L-Co))=99.1 degrees ) than in 1 (theta(av(Co-L-Co))=92.8 degrees ). Weaker ferromagnetic interactions were found in 2 than in 1, in agreement with larger Co-L-Co angles in 2. The electrochemistry of 1 was studied in detail. The two chemically reversible redox couples observed in the positive potential domain were attributed to the redox processes of Co(II) centers, and indicated that two types of Co(II) centers in the structure were oxidized in separate waves. Redox activity of the seventh Co(II) center was not detected. Preliminary experiments indicated that 1 catalyzes the reduction of nitrite and NO. Remarkably, a reversible interaction exists with NO or related species. The hybrid tetranuclear complexes K(5)Na(3)[(A-alpha-SiW(9)O(34))Co(4)(OH)(3)(CH(3)COO)(3)]18 H(2)O (3) and K(5)Na(3)[(A-alpha-SiW(9)O(34))Co(4)(OH)(N(3))(2)(CH(3)COO)(3)]18 H(2)O (4) were characterized: in both, a tetrahedral {Co(4)(L(1))(L(2))(2)(CH(3)COO)(3)} (3: L(1)=L(2)=OH; 4: L(1)=OH, L(2)=N(3)) unit capped the [A-alpha-SiW(9)O(34)](10-) trivacant polyanion. The octanuclear complex K(8)Na(8)[(A-alpha-SiW(9)O(34))(2)Co(8)(OH)(6)(H(2)O)(2)(CO(3))(3)]52 H(2)O (5), containing two {Co(4)O(9)(OH)(3)(H(2)O)} units, was also obtained. Compounds 2, 3, 4, and 5 were less stable than 1, but their partial electrochemical characterization was possible; the electronic effect expected for 3 and 4 was observed.

Ternary mixed metal Fe-doped NiCo2O4 nanowires as efficient electrocatalysts for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Yan, Kai-Li; Shang, Xiao; Li, Zhen; Dong, Bin; Li, Xiao; Gao, Wen-Kun; Chi, Jing-Qi; Chai, Yong-Ming; Liu, Chen-Guang

2017-09-01

Designing mixed metal oxides with unique nanostructures as efficient electrocatalysts for water electrolysis has been an attractive approach for the storage of renewable energies. The ternary mixed metal spinel oxides FexNi1-xCo2O4 (x = 0, 0.1, 0.25, 0.5, 0.75, 0.9, 1) have been synthesized by a facile hydrothermal approach and calcination treatment using nickel foam as substrate. Fe/Ni ratios have been proved to affect the nanostructures of FexNi1-xCo2O, which imply different intrinsic activity for oxygen evolution reaction (OER). SEM images show that Fe0.5Ni0.5Co2O4 has the uniform nanowires morphology with about 30 nm of the diameter and 200-300 nm of the length. The OER measurements show that Fe0.5Ni0.5Co2O4 exhibits the better electrocatalytic performances with lower overpotential of 350 mV at J = 10 mA cm-2. In addition, the smaller Tafel slope of 27 mV dec-1 than other samples with different Fe/Ni ratios for Fe0.5Ni0.5Co2O4 is obtained. The improved OER activity of Fe0.5Ni0.5Co2O4 may be attributed to the synergistic effects from ternary mixed metals especially Fe-doping and the uniform nanowires supported on NF. Therefore, synthesizing Fe-doped multi-metal oxides with novel nanostructures may be a promising strategy for excellent OER electrocatalysts and it also provides a facile way for the fabrication of high-activity ternary mixed metal oxides electrocatalysts.

Low-Temperature Sintering Li3Mg1.8Ca0.2NbO6 Microwave Dielectric Ceramics with LMZBS Glass

NASA Astrophysics Data System (ADS)

Wang, Gang; Zhang, Huaiwu; Liu, Cheng; Su, Hua; Jia, Lijun; Li, Jie; Huang, Xin; Gan, Gongwen

2018-05-01

Li3Mg1.8Ca0.2NbO6 ceramics doped with Li2O-MgO-ZnO-B2O3-SiO2 glass (LMZBS) were prepared via a solid-state route. The LMZBS glass effectively reduced the sintering temperature of Li3Mg1.8Ca0.2NbO6 ceramics to 950°C. The effects of the LMZBS glass on the sintering behavior, microstructures and microwave dielectric properties of Li3Mg1.8Ca0.2NbO6 ceramics are discussed in detail. Among all the LMZBS doped Li3Mg1.8Ca0.2NbO6 ceramics, the sample with 1 wt.% of LMZBS glass sintered at 950°C for 4 h exhibited good dielectric properties: ɛ r = 16.7, Q × f = 31,000 GHz (9.92 GHz), τ f = - 1.3 ppm/°C. The Li3Mg1.8Ca0.2NbO6 ceramics possessed excellent chemical compatibility with Ag electrodes, and could be applied in low temperature co-fired ceramics (LTCC) applications.

Densification, Microstructural Evolution, Mechanical Properties and Oxidation Study of CrB2 + EuB6 Composite

NASA Astrophysics Data System (ADS)

Raju, K.; Sonber, J. K.; Murthy, T. S. R. Ch.; Sairam, K.; Majumdar, S.; Kain, V.; Nageswar Rao, G. V. S.

2018-05-01

This paper reports the results of investigation on densification, microstructural evolution, mechanical properties and oxidation study of CrB2 + EuB6 composite. CrB2 + EuB6 (10 and 20 wt.%) composites have been fabricated by hot pressing at a temperature of 1700 °C and 35 MPa pressure. The hardness and flexural strength were measured in the range of 21.25-24.48 GPa and 171-199 MPa, respectively. The fracture toughness increased from 3.3 to 4.01 MPa m1/2 by the addition of 20% EuB6. Microstructural evolution revealed the uniform distribution of EuB6 and absence of any reaction product. Fracture surface analysis confirmed the presence of transgranular mode of fracture. Oxidation study at 1200 °C revealed that the developed composites have good oxidation resistance and followed the parabolic rate of oxidation.

Microanalysis of an oxidized cobalt oxide: Zirconia eutectic

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

Bentley, J.; McKernan, S.; Carter, C.B.

The compositions of CoO, Co{sub 3}O{sub 4}, and Ca-stabilized cubic ZrO{sub 2} in an oxidized directionally solidified CoO-ZrO{sub 2} eutectic were determined by PEELS and EDS. An oxygen gradient exists across the Co{sub 3}O{sub 4} with highest levels near the ZrO{sub 2} interface. Oxygen ELNES for CoO and Co{sub 3}O{sub 4} are quite different; published oxygen ELNES have been incorrectly attributed to CoO. Normalized Co-L{sub 23} white line intensity (WLI) ratios for CoO and Co{sub 3}O{sub 4} are similar (0.53 {plus_minus} 0.02) but L{sub 3}/L{sub 2} WLI ratios are 3.88 and 2.58, respectively. ELCE data suggest Co{sub 3}O{sub 4} hasmore » the inverse spinel structure.« less

Porous ZnO-Coated Co3O4 Nanorod as a High-Energy-Density Supercapacitor Material.

PubMed

Gao, Miao; Wang, Wei-Kang; Rong, Qing; Jiang, Jun; Zhang, Ying-Jie; Yu, Han-Qing

2018-06-27

Co 3 O 4 with a high theoretical capacitance has been widely recognized as a promising electrode material for supercapacitor, but its poor electrical conductivity and stability limit its practical applications. Here, we developed an effective synthetic route to synthesize one-dimensional (1D) porous ZnO/Co 3 O 4 heterojunction composites. Benefiting from the heterostructure to promote the charge transfer and protect Co 3 O 4 from corrosion and the 1D porous structure to improve ion diffusion and prevent structural collapse in charge and discharge process, the as-prepared ZnO/Co 3 O 4 composites exhibited an excellent capacitive performance and good cycling stability. The specific capacitance of the ZnO/Co 3 O 4 -450 (1135 F g -1 at 1 A g -1 ) was 1.4 times higher than that of Co 3 O 4 (814 F g -1 ), and the high-rate performance for ZnO/Co 3 O 4 -450 was 4.9 times better than that of Co 3 O 4 . Also, approximately 83% of its specific capacitance was retained after 5000 cycles at 10 A g -1 . Most importantly, the as-fabricated asymmetric supercapacitor, with a ZnO/Co 3 O 4 -450 positive electrode and an activated carbon negative electrode, delivered a prominent energy density of 47.7 W h kg -1 and a high power density of 7500 W kg -1 . Thus, the ZnO/Co 3 O 4 composites could serve as a high-activity material for supercapacitor and the preparation method also offers an attractive strategy to enhance the capacitive performance of Co 3 O 4 .

Effect of Fluoride on the Morphology and Electrochemical Property of Co3O4 Nanostructures for Hydrazine Detection

PubMed Central

Gao, Wanlin; Wang, Qiang; Umar, Ahmad

2018-01-01

In this paper, we systematically investigated the influence of fluoride on the morphology and electrochemical property of Co3O4 nanostructures for hydrazine detection. The results showed that with the introduction of NH4F during the synthesis process of Co3O4, both Co(CO3)0.5(OH)·0.11H2O and Co(OH)F precursors would be generated. To understand the influence of F on the morphology and electrochemical property of Co3O4, three Co3O4 nanostructures that were respectively obtained from bare Co(CO3)0.5(OH)·0.11H2O, Co(OH)F and Co(CO3)0.5(OH)·0.11H2O mixtures and bare Co(OH)F were successfully synthesized. The electrochemical tests revealed the sensing performance of prepared Co3O4 nanostructures decreased with the increase in the fluoride contents of precursors. The more that dosages of NH4F were used, the higher crystallinity and smaller specific surface area of Co3O4 was gained. Among these three Co3O4 nanostructures, the Co3O4 that was obtained from bare Co(CO3)0.5(OH)·0.11H2O-based hydrazine sensor displayed the best performances, which exhibited a great sensitivity (32.42 μA·mM−1), a low detection limit (9.7 μΜ), and a wide linear range (0.010–2.380 mM), together with good selectivity, great reproducibility and longtime stability. To the best of our knowledge, it was revealed for the first time that the sensing performance of prepared Co3O4 nanostructures decreased with the increase in fluoride contents of precursors. PMID:29382161

Holmium-doped fluorotellurite microstructured fibers for 2.1 μm lasing.

PubMed

Yao, Chuanfei; He, Chunfeng; Jia, Zhixu; Wang, Shunbin; Qin, Guanshi; Ohishi, Yasutake; Qin, Weiping

2015-10-15

Holmium (Ho3+)-doped fluorotellurite microstructured fibers based on TeO2-BaF2-Y2O3 glasses are fabricated by using a rod-in-tube method. By using a 1.992 μm fiber laser as the pump source, lasing at 2.077 μm is obtained from a 27 cm long Ho3+-doped fluorotellurite microstructured fiber. The maximum unsaturated power is about 161 mW and the corresponding slope efficiency is up to 67.4%. The influence of fiber length on lasing at 2.1 μm is also investigated. Our results show that Ho3+-doped fluorotellurite microstructured fibers are promising gain media for 2.1 μm laser applications.

Noteworthy performance of La(1-x)Ca(x)MnO3 perovskites in generating H2 and CO by the thermochemical splitting of H2O and CO2.

PubMed

Dey, Sunita; Naidu, B S; Govindaraj, A; Rao, C N R

2015-01-07

Perovskite oxides of the composition La1-xCaxMnO3 (LCM) have been investigated for the thermochemical splitting of H2O and CO2 to produce H2 and CO, respectively. The study was carried out in comparison with La1-xSrxMnO3, CeO2 and other oxides. The LCM system exhibits superior characteristics in high-temperature evolution of oxygen, and in reducing CO2 to CO and H2O to H2. The best results were obtained with La0.5Ca0.5MnO3 whose performance is noteworthy compared to that of other oxides including ceria. The orthorhombic structure of LCM seems to be a crucial factor.

3D Nitrogen, Sulfur-Codoped Carbon Nanomaterial-Supported Cobalt Oxides with Polyhedron-Like Particles Grafted onto Graphene Layers as Highly Active Bicatalysts for Oxygen-Evolving Reactions.

PubMed

Huang, Xiaobo; Wang, Jianqiang; Bao, Hongliang; Zhang, Xiangkun; Huang, Yongmin

2018-02-28

The extensive research and developments of highly efficient oxygen electrode electrocatalysts to get rid of the kinetic barriers for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are very important in energy conversion and storage devices. Especially, exploring nonprecious metal alternatives to replace traditional noble metal catalysts with high cost and poor durability is the paramount mission. In this paper, we utilize property-flexible ZIF-67 and sulfur-functionalized graphene oxide to obtain a cobalt, nitrogen, and sulfur codoped nanomaterial with 3D hierarchical porous structures, owing to their rich dopant species and good conductivity. The crosslinked structures of polyhedron particles throughout the whole carbon framework speeds up the mass transportation and charge-delivery processes during oxygen-evolving reactions. Also, by exploring the location and coordination type of sulfur dopants, we emphasize the effects of sulfone and sulfide functional groups anchored into the graphitic structure on enhancing the catalytic abilities for ORR and OER. To note, compared to the noble metal electrocatalysts, the best-performing CoO@Co 3 O 4 /NSG-650 (0.79 V) is 40 mV less active than the commercial Pt/C catalyst (0.83 V) for ORR and merely 10 mV behind IrO 2 (1.68 V) for OER. Besides, the metric between ORR and OER difference for CoO@Co 3 O 4 /NSG-650 to evaluate its overall electrocatalytic activity is 0.90 V, surpassing 290 and 430 mV over Pt/C (1.19 V) and IrO 2 (1.33 V). Comprehensively, the as-prepared CoO@Co 3 O 4 /NSG-650 indicates excellent bifunctional catalytic activities for ORR and OER, which shows great potential for replacing noble metal catalysts in the application of fuel cells and metal-air batteries.

Design and Synthesis of Spherical Multicomponent Aggregates Composed of Core-Shell, Yolk-Shell, and Hollow Nanospheres and Their Lithium-Ion Storage Performances.

PubMed

Park, Gi Dae; Kang, Yun Chan

2018-03-01

Micrometer-sized spherical aggregates of Sn and Co components containing core-shell, yolk-shell, hollow nanospheres are synthesized by applying nanoscale Kirkendall diffusion in the large-scale spray drying process. The Sn 2 Co 3 -Co 3 SnC 0.7 -C composite microspheres uniformly dispersed with Sn 2 Co 3 -Co 3 SnC 0.7 mixed nanocrystals are formed by the first-step reduction of spray-dried precursor powders at 900 °C. The second-step oxidation process transforms the Sn 2 Co 3 -Co 3 SnC 0.7 -C composite into the porous microsphere composed of Sn-Sn 2 Co 3 @CoSnO 3 -Co 3 O 4 core-shell, Sn-Sn 2 Co 3 @CoSnO 3 -Co 3 O 4 yolk-shell, and CoSnO 3 -Co 3 O 4 hollow nanospheres at 300, 400, and 500 °C, respectively. The discharge capacity of the microspheres with Sn-Sn 2 Co 3 @CoSnO 3 -Co 3 O 4 core-shell, Sn-Sn 2 Co 3 @CoSnO 3 -Co 3 O 4 yolk-shell, and CoSnO 3 -Co 3 O 4 hollow nanospheres for the 200 th cycle at a current density of 1 A g -1 is 1265, 987, and 569 mA h g -1 , respectively. The ultrafine primary nanoparticles with a core-shell structure improve the structural stability of the porous-structured microspheres during repeated lithium insertion and desertion processes. The porous Sn-Sn 2 Co 3 @CoSnO 3 -Co 3 O 4 microspheres with core-shell primary nanoparticles show excellent cycling and rate performances as anode materials for lithium-ion batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shape-controlled synthesis of NiCo2S4 and their charge storage characteristics in supercapacitors.

PubMed

Zhang, Yufei; Ma, Mingze; Yang, Jun; Sun, Chencheng; Su, Haiquan; Huang, Wei; Dong, Xiaochen

2014-08-21

In this work, a facile hydrothermal approach for the shape-controlled synthesis of NiCo2S4 architectures is reported. Four different morphologies, urchin-, tube-, flower-, and cubic-like NiCo2S4 microstructures, have been successfully synthesized by employing various solvents. The obtained precursors and products have been characterized by X-ray diffraction, field-emission scanning electron microscopy and transmission electron microscopy. It is revealed that the supersaturation of nucleation and crystal growth is determined by the solvent polarity and solubility, which can precisely control the morphology of NiCo2S4 microstructures. The detailed electrochemical performances of the various NiCo2S4 microstructures are investigated by cyclic voltammetry and galvanostatic charge-discharge measurements. The results indicate that the tube-like NiCo2S4 exhibits promising capacitive properties with high capacitance and excellent retention. Its specific capacitance can reach 1048 F g(-1) at the current density of 3.0 A g(-1) and 75.9% of its initial capacitance is maintained at the current density of 10.0 A g(-1) after 5000 charge-discharge cycles.

Shape-controlled synthesis of NiCo2S4 and their charge storage characteristics in supercapacitors

NASA Astrophysics Data System (ADS)

Zhang, Yufei; Ma, Mingze; Yang, Jun; Sun, Chencheng; Su, Haiquan; Huang, Wei; Dong, Xiaochen

2014-07-01

In this work, a facile hydrothermal approach for the shape-controlled synthesis of NiCo2S4 architectures is reported. Four different morphologies, urchin-, tube-, flower-, and cubic-like NiCo2S4 microstructures, have been successfully synthesized by employing various solvents. The obtained precursors and products have been characterized by X-ray diffraction, field-emission scanning electron microscopy and transmission electron microscopy. It is revealed that the supersaturation of nucleation and crystal growth is determined by the solvent polarity and solubility, which can precisely control the morphology of NiCo2S4 microstructures. The detailed electrochemical performances of the various NiCo2S4 microstructures are investigated by cyclic voltammetry and galvanostatic charge-discharge measurements. The results indicate that the tube-like NiCo2S4 exhibits promising capacitive properties with high capacitance and excellent retention. Its specific capacitance can reach 1048 F g-1 at the current density of 3.0 A g-1 and 75.9% of its initial capacitance is maintained at the current density of 10.0 A g-1 after 5000 charge-discharge cycles.

Effect of BiFeO3 doping on the structural, dielectric and electrical properties of CaCu3Ti4O12 ceramics

NASA Astrophysics Data System (ADS)

Dai, Haiyang; Liu, Dewei; Chen, Jing; Xue, Renzhong; Li, Tao; Xiang, Huiwen; Chen, Zhenping; Liu, Haizeng

2015-04-01

(1 - x)CaCu3Ti4O12- xBiFeO3 ( x = 0, 0.003, 0.006, 0.010 and 0.015) ceramics have been fabricated by the solid-state reaction method. The effects of BiFeO3 (BFO) doping on the microstructure, dielectric and electrical properties of CaCu3Ti4O12 (CCTO) ceramics were investigated. It is found that BFO doping can affect the microstructure of the CCTO ceramics, and some properties of CCTO ceramics can hence be improved by BFO doping. The XRD and Raman results show that no phase transition has occurred in the doping content range, but BFO doping induces the crystal structure distortion. Analysis of microstructure indicates that the grain morphology varies significantly with increasing BFO content, and an appropriate amount of BFO can promote the grain growth. Impedance spectroscopy results show that the dielectric constant and loss of the BFO-doped CCTO samples are stable with frequency. The dielectric constant and nonohmic properties can be enhanced markedly in an appropriate doping content. The dielectric loss of all BFO-doped samples was lower than that of undoped CCTO sample in low frequencies. The related mechanism is also discussed in the paper.

Composite Magnetite and Protein Containing CaCO3 Crystals. External Manipulation and Vaterite → Calcite Recrystallization-Mediated Release Performance.

PubMed

Sergeeva, Alena; Sergeev, Roman; Lengert, Ekaterina; Zakharevich, Andrey; Parakhonskiy, Bogdan; Gorin, Dmitry; Sergeev, Sergey; Volodkin, Dmitry

2015-09-30

Biocompatibility and high loading capacity of mesoporous CaCO3 vaterite crystals give an option to utilize the polycrystals for a wide range of (bio)applications. Formation and transformations of calcium carbonate polymorphs have been studied for decades, aimed at both basic and applied research interests. Here, composite multilayer-coated calcium carbonate polycrystals containing Fe3O4 magnetite nanoparticles and model protein lysozyme are fabricated. The structure of the composite polycrystals and vaterite → calcite recrystallization kinetics are studied. The recrystallization results in release of both loaded protein and Fe3O4 nanoparticles (magnetic manipulation is thus lost). Fe3O4 nanoparticles enhance the recrystallization that can be induced by reduction of the local pH with citric acid and reduction of the polycrystal crystallinity. Oppositely, the layer-by-layer assembled poly(allylamine hydrochloride)/poly(sodium styrenesulfonate) polyelectrolyte coating significantly inhibits the vaterite → calcite recrystallization (from hours to days) most likely due to suppression of the ion exchange giving an option to easily tune the release kinetics for a wide time scale, for example, for prolonged release. Moreover, the recrystallization of the coated crystals results in formulation of multilayer capsules keeping the feature of external manipulation. This study can help to design multifunctional microstructures with tailor-made characteristics for loading and controlled release as well as for external manipulation.

Enhanced activity of gold-supported cobalt oxide for the electrochemical evolution of oxygen.

PubMed

Yeo, Boon Siang; Bell, Alexis T

2011-04-13

Scanning electron microscopy, linear sweep voltammetry, chronoamperometry, and in situ surface-enhanced Raman spectroscopy were used to investigate the electrochemical oxygen evolution reaction (OER) occurring on cobalt oxide films deposited on Au and other metal substrates. All experiments were carried out in 0.1 M KOH. A remarkable finding is that the turnover frequency for the OER exhibited by ∼0.4 ML of cobalt oxide deposited on Au is 40 times higher than that of bulk cobalt oxide. The activity of small amounts of cobalt oxide deposited on Pt, Pd, Cu, and Co decreased monotonically in the order Au > Pt > Pd > Cu > Co, paralleling the decreasing electronegativity of the substrate metal. Another notable finding is that the OER turnover frequency for ∼0.4 ML of cobalt oxide deposited on Au is nearly three times higher than that for bulk Ir. Raman spectroscopy revealed that the as-deposited cobalt oxide is present as Co(3)O(4) but undergoes progressive oxidation to CoO(OH) with increasing anodic potential. The higher OER activity of cobalt oxide deposited on Au is attributed to an increase in fraction of the Co sites present as Co(IV) cations, a state of cobalt believed to be essential for OER to occur. A hypothesis for how Co(IV) cations contribute to OER is proposed and discussed. © 2011 American Chemical Society

Microstructure and high-temperature oxidation resistance of TiN/Ti3Al intermetallic matrix composite coatings on Ti6Al4V alloy surface by laser cladding

NASA Astrophysics Data System (ADS)

Zhang, Xiaowei; Liu, Hongxi; Wang, Chuanqi; Zeng, Weihua; Jiang, Yehua

2010-11-01

A high-temperature oxidation resistant TiN embedded in Ti3Al intermetallic matrix composite coating was fabricated on titanium alloy Ti6Al4V surface by 6kW transverse-flow CO2 laser apparatus. The composition, morphology and microstructure of the laser clad TiN/Ti3Al intermetallic matrix composite coating were characterized by optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive spectrometer (EDS). In order to evaluate the high-temperature oxidation resistance of the composite coatings and the titanium alloy substrate, isothermal oxidation test was performed in a conventional high-temperature resistance furnace at 600°C and 800°C respectively. The result shows that the laser clad intermetallic composite coating has a rapidly solidified fine microstructure consisting of TiN primary phase (granular-like, flake-like, and dendrites), and uniformly distributed in the Ti3Al matrix. It indicates that a physical and chemical reaction between the Ti powder and AlN powder occurred completely under the laser irradiation. In addition, the microhardness of the TiN/Ti3Al intermetallic matrix composite coating is 844HV0.2, 3.4 times higher than that of the titanium alloy substrate. The high-temperature oxidation resistance test reveals that TiN/Ti3Al intermetallic matrix composite coating results in the better modification of high-temperature oxidation behavior than the titanium substrate. The excellent high-temperature oxidation resistance of the laser cladding layer is attributed to the formation of the reinforced phase TiN and Al2O3, TiO2 hybrid oxide. Therefore, the laser cladding TiN/Ti3Al intermetallic matrix composite coating is anticipated to be a promising oxidation resistance surface modification technique for Ti6Al4V alloy.

Microstructure and magnetic properties of MFe{sub 2}O{sub 4} (M = Co, Ni, and Mn) ferrite nanocrystals prepared using colloid mill and hydrothermal method

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

Wang, Wei, E-mail: wangwei@mail.buct.edu.cn; Ding, Zui; Zhao, Xiruo

2015-05-07

Three kinds of spinel ferrite nanocrystals, MFe{sub 2}O{sub 4} (M = Co, Ni, and Mn), are synthesized using colloid mill and hydrothermal method. During the synthesis process, a rapid mixing and reduction of cations with sodium borohydride (NaBH{sub 4}) take place in a colloid mill then through a hydrothermal reaction, a slow oxidation and structural transformation of the spinel ferrite nanocrystals occur. The phase purity and crystal lattice parameters are estimated by X-ray diffraction studies. Scanning electron microscopy and transmission electron microscopy images show the morphology and particle size of the as-synthesized ferrite nanocrystals. Raman spectrum reveals active phonon modesmore » at room temperature, and a shifting of the modes implies cation redistribution in the tetrahedral and octahedral sites. Magnetic measurements show that all the obtained samples exhibit higher saturation magnetization (M{sub s}). Meanwhile, experiments demonstrate that the hydrothermal reaction time has significant effects on microstructure, morphologies, and magnetic properties of the as-synthesized ferrite nanocrystals.« less

Microstructure and texture evolution in cold-rolled and annealed alloy MA-956

NASA Astrophysics Data System (ADS)

Hosoda, Takashi

The microstructural and texture development with thermomechanical processing, performed through a combination of cold-rolling and annealing, in MA-956 plate consisting of a layered and inhomogeneous microstructure was systematically assessed. The alloy contained in mass percent, 20 Cr, 4.8 Al, 0.4 Ti, 0.4 Y2O3, and the balance iron. The starting material was as-hot-rolled plate, 9.7 mm thick. The as-hot-rolled plate was subjected to 40%, 60%, and 80% cold-rolling reduction and subsequently annealed at 1000, 1200, or 1380. Assessment of microstructural and texture developments before and after cold-rolling and annealing was performed using light optical microscopy (LOM), Vickers hardness testing, and electron backscatter diffraction (EBSD). Locally introduced misorientations by cold-rolling in each region were evaluated by Kernel Average Misorientation (KAM) maps. The as-hot-rolled condition contained a layered and inhomogeneous microstructure consisting of thin and coarse elongated grains, and aggregated regions which consisted of fine grains and sub-grains with {100} texture parallel to the longitudinal direction. The microstructure of the 40% cold-rolled condition contained deformation bands, and the 60% and 80% cold-rolled conditions also contained highly deformed regions where the deformation bands were intricately tangled. A predominant orientation of (001) parallel to the rolling direction was developed during cold-rolling, becoming more prominent with increasing reduction. The magnitudes of KAM angles varied through the thickness depending on the initial microstructures. Recrystallization occurred in regions where high KAM angles were dense after annealing and nucleation sites were the aggregation regions, deformation bands, and highly deformed regions. The shape and size of the recrystallized grains varied depending on the nucleation sites.

Preparation and Scintillating Properties of Sol-Gel Eu3+, Tb3+ Co-Doped Lu2O3 Nanopowders

PubMed Central

de Jesús Morales Ramírez, Ángel; Murillo, Antonieta García; de Jesús Carrillo Romo, Felipe; Hernández, Margarita García; Palmerin, Joel Moreno; Guerrero, Rosario Ruiz

2011-01-01

Nanocrystalline Eu3+, Tb3+ co-doped Lu2O3 powders with a maximum size of 25.5 nm were prepared by the sol-gel process, using lutetium, europium and terbium nitrates as precursors, and ethanol as a solvent. Differential thermal analysis (DTA) and infrared spectroscopy (IR) were used to study the chemical changes during the xerogel annealing. After the sol evaporation at 100 °C, the formed gel was annealed from 300 to 900 °C for 30 min under a rich O2 atmosphere, and the yielded product was analyzed by X-ray diffraction (XRD) to characterize the microstructural behavior and confirm the crystalline structure. The results showed that Lu2O3 nanopowders start to crystallize at 400 °C and that the crystallite size increases along with the annealing temperature. A transmission electron microscopy (TEM) study of samples annealed at 700 and 900 °C was carried out in order to analyze the microstructure, as well as the size, of crystallites. Finally, in regard to scintillating properties, Eu3+ dopant (5 mol%), Tb3+ codoped Lu2O3 exhibited a typical red emission at 611 nm (D°→7F2), furthermore, the effect of Tb3+ molar content (0.01, 0.015 and 0.02% mol) on the Eu3+ radioluminiscence was analyzed and it was found that the higher emission intensity corresponds to the lower Tb3+ content. PMID:22016655

Al2O3/ZrO2/Y3Al5O12 Composites: A High-Temperature Mechanical Characterization

PubMed Central

Palmero, Paola; Pulci, Giovanni; Marra, Francesco; Valente, Teodoro; Montanaro, Laura

2015-01-01

An Al2O3/5 vol%·ZrO2/5 vol%·Y3Al5O12 (YAG) tri-phase composite was manufactured by surface modification of an alumina powder with inorganic precursors of the second phases. The bulk materials were produced by die-pressing and pressureless sintering at 1500 °C, obtaining fully dense, homogenous samples, with ultra-fine ZrO2 and YAG grains dispersed in a sub-micronic alumina matrix. The high temperature mechanical properties were investigated by four-point bending tests up to 1500 °C, and the grain size stability was assessed by observing the microstructural evolution of the samples heat treated up to 1700 °C. Dynamic indentation measures were performed on as-sintered and heat-treated Al2O3/ZrO2/YAG samples in order to evaluate the micro-hardness and elastic modulus as a function of re-heating temperature. The high temperature bending tests highlighted a transition from brittle to plastic behavior comprised between 1350 and 1400 °C and a considerable flexural strength reduction at temperatures higher than 1400 °C; moreover, the microstructural investigations carried out on the re-heated samples showed a very limited grain growth up to 1650 °C. PMID:28787961

From Layered Structures to Cubic Frameworks. Expanding the Structural Diversity of Uranyl Carboxyphosphonates via the Incorporation of Cobalt

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

Alsobrook, Andrea N.; Hauser, Brad G.; Hupp, Joseph T.

2011-02-08

Five heterobimetallic U(VI)/Co(II) carboxyphosphonates have been synthesized under mild hydrothermal conditions by reacting UO 3, Co(CH 3CO 2) 2·4H 2O, and triethyl phosphonoacetate. These compounds, Co(H 2O) 4[(UO 2) 2(PO 3CH 2CO 2) 2(H 2O) 2] (CoUPAA-1), [Co(H 2O) 6][UO 2(PO 3CH 2CO 2)] 2·8H 2O (CoUPAA-2), Co(H 2O) 4[UO 2(PO 3CH 2CO 2)] 2·4H 2O (CoUPAA-3), Co(H 2O) 4[(UO 2) 62CH 2CO 2) 2O 2(OH) 3(H 2O) 3] 2·3H 2O (CoUPAA-4), and Co 2(UO 2) 6(PO 3CH 2CO 2) 3O 3(OH)(H 2O) 2·16H 2O (CoUPAA-5), range from two- to three-dimensional structures. CoUPAA-1 to CoUPAA-3 all possess uranyl carboxyphosphonate layersmore » that are separated by the Co(II) cation with varying degrees of hydration. CoUPAA-4 contains both UO 7 pentagonal bipyramids and UO 8 hexagonal bipyramids within the uranyl carboxyphosphonate plane. Unlike the first four low-symmetry compounds, CoUPAA-5 is a cubic, three-dimensional network with large cavities approximately 16 Å in diameter that are filled with cocrystallized water molecules. Differential gas absorption measurements performed on CoUPAA-5 displayed a surface area uptake for CO 2 of 40 m 2 g -1 at 273 K, and no uptake for N 2 at 77 K.« less

Fabrication of lead-free piezoelectric Li2CO3-added (Ba,Ca)(Ti,Sn)O3 ceramics under controlled low oxygen partial pressure and their properties

NASA Astrophysics Data System (ADS)

Noritake, Kouta; Sakamoto, Wataru; Yuitoo, Isamu; Takeuchi, Teruaki; Hayashi, Koichiro; Yogo, Toshinobu

2018-02-01

Reduction-resistant lead-free (Ba,Ca)(Ti,Sn)O3 piezoceramics with high piezoelectric constants were fabricated by optimizing the amount of Li2CO3 added. Oxygen partial pressure was controlled during the sintering of (Ba,Ca)(Ti,Sn)O3 ceramics in a reducing atmosphere using H2-CO2 gas. Enhanced grain growth and a high-polarization state after poling treatment were achieved by adding Li2CO3. Optimizing the amount of Li2CO3 added to (Ba0.95Ca0.05)(Ti0.95Sn0.05)O3 ceramics sintered under a low oxygen partial pressure resulted in improved piezoelectric properties while maintaining the high sintered density. The prepared Li2CO3-added ceramic samples had homogeneous microstructures with a uniform dispersion of each major constituent element. However, the residual Li content in the 3 mol % Li2CO3-added (Ba0.95Ca0.05)(Ti0.95Sn0.05)O3 ceramics after sintering was less than 0.3 mol %. Sintered bodies of this ceramic prepared in a CO2 (1.5%)-H2 (0.3%)/Ar reducing atmosphere (PO2 = 10-8 atm at 1350 °C), exhibited sufficient electrical resistivity and a piezoelectric constant (d 33) exceeding 500 pC/N. The piezoelectric properties of this nonreducible ceramic were comparable or superior to those of the same ceramic sintered in air.

Re-creation of single phase, and improvement of magnetic property of CoFe2O4 nanoparticles versus heat treatment

NASA Astrophysics Data System (ADS)

Tran, N.; Kim, D. H.; Phan, T. L.; Dang, N. T.; Bach, T. N.; Manh, D. H.; Lee, B. W.

2018-03-01

Our studies on the crystal characterization and magnetic property of CoFe2O4 nanoparticles (NPs) point out their instability in a specific temperature range. While as-prepared NPs exhibit single phase in a cubic spinel structure, annealing at temperatures T=673-1273 K leads to the development of an impurity phase of Fe2O3. Interestingly, annealing at higher temperatures re-creates the single phase of NPs. This strongly influences their magnetic property. The magnetic inhomogeneity and/or multiple phase exist in as-prepared NPs and in those annealed below 1273 K, better magnetic property is found in the samples with annealing temperature (Tan) higher than 1273 K. Ferromagnetic-paramagnetic phase transition temperatures of these samples are located around 815-850 K, and are less dependent on Tan. At room temperature, their saturation magnetization is located in the range of 41-55 emu/g, while the coercivity can be changed from 600 to 3200 Oe. These results are related to microstructures, structural phases, and exchange interactions between Fe and Co ions situated in the A and B sites of the spinel structure, which are modified by heat treatment.

High-temperature heat capacity of Co3O4 spinel: thermally induced spin unpairing transition

USGS Publications Warehouse

Mocala, K.; Navrotsky, A.; Sherman, David M.

1992-01-01

A strong anomaly was found in the heat capacity of Co3O4 between 1000 K and the decomposition temperature. This anomaly is not related to the decomposition of Co3O4 to CoO. The measured entropy of transition, ??S=46??4 J mol-1 K-1 of Co3O4, supports the interpretation that this anomaly reflects a spin unpairing transition in octahedrally coordinated Co3+ cations. Experimental values of heat capacity, heat content and entropy of Co3O4 in the high temperature region are provided. The enthalpy of the spin unpairing transition is 53??4 kJ mol-1 of Co3O4. ?? 1992 Springer-Verlag.

Metal-Matrix Composites and Porous Materials: Constitute Models, Microstructure Evolution and Applications

DTIC Science & Technology

2000-02-23

eonomical to rotate the stress and the c strain once rather than having to rotate 4th order tensors like c Amat, Bmat , MHS etc. whose...nu2,sigyO real*8 deps(3,3),eps_plastic,dep_plas,dumd(6,6) real*8 det,kll,dphidf,phil,phi2,ftest real*8 el212,e2323,el313,pil212,pi2323,pil313, bmat ...pi2323-f*pi2323 el313=pil313-f*pil313 spath=.true. call Btensor(a,b,c,ad,bd,cd,f,mul,kl,mu2,k2, Bmat ) do 41 i=l,3 do 42 j=l,6 Bmat (i,j)=0.0 42

Large-scale one-dimensional Bi x O y I z nanostructures: synthesis, characterization, and photocatalytic applications

NASA Astrophysics Data System (ADS)

Liu, Chaohong; Zhang, Dun

2015-03-01

The performances of Bi x O y I z photofunctional materials are very sensitive to their composition and microstructures; however, the morphology evolution and crystallization process of one-dimensional Bi x O y I z nanostructures, the roles of experimental factors, and related reaction mechanisms remain poorly understood. In this work, large-scale one-dimensional Bi x O y I z nanostructures were fabricated using simple inorganic iodine source. By combing the results of X-ray diffraction and scanning electron microscope, the effect of volume ratios of water and ethanol, concentration of NaOH, and reaction time on the morphologies and crystal phases of Bi x O y I z were elaborated. On the basis of characterizations, a possible process for the growth of Bi5O7I nanobelts was proposed. The optical performances of Bi x O y I z nanostructures were evaluated by ultraviolet-visible-near infrared diffuse reflectance spectra as well as photocatalytic degradation of organic dye and corrosive bacteria. The as-prepared Bi5O7I/Bi2O2CO3/BiOI composite showed excellent photocatalytic activity over malachite green under visible light irradiation, which was deduced closely related to its heterojunction structures.

Transition-metal redox evolution in LiNi0.5Mn0.3Co0.2O2 electrodes at high potentials

NASA Astrophysics Data System (ADS)

Qiao, Ruimin; Liu, Jun; Kourtakis, Kostantinos; Roelofs, Mark G.; Peterson, Darin L.; Duff, James P.; Deibler, Dean T.; Wray, L. Andrew; Yang, Wanli

2017-08-01

The mixed transition-metal layered compound, LiNi0.5Mn0.3Co0.2O2 (NMC532), is a promising high-energy cathode material. However, the required high-voltage (>4.3 V) cycling is accompanied by a rapid capacity fade associated with a complex redox mechanism that has not been clarified. Here we report soft x-ray absorption spectroscopy of NMC532 electrodes, both pristine and those charged to 4.2, 4.35, or 4.5 V in graphite/NMC532 cells. A quantitative sXAS analysis shows that about 20% of the nickel exists as Ni4+ in the as-synthesized NMC532. The Ni redox reaction contributes only to the experimental capacity obtained below 4.2 V, while Co redox reactions take place throughout the entire electrochemical cycling up to 4.5 V. In contrast to the changing ratio of the well-defined Ni2+, Ni3+ and Ni4+ ions, Co always displays ill-defined intermediate valence states in the charged NMC532 electrodes. This indicates an itinerant electron system in NMC electrodes related to the improved rate performance through Co doping. Additionally, about 20% of Ni2+ is found on the electrode surface at the high potential, which suggests that the electrode surface has either gone through surface reconstruction or reacted with the electrolyte at high voltage.

Synthesis of scaly Sn3O4/TiO2 nanobelt heterostructures for enhanced UV-visible light photocatalytic activity

NASA Astrophysics Data System (ADS)

Chen, Guohui; Ji, Shaozheng; Sang, Yuanhua; Chang, Sujie; Wang, Yana; Hao, Pin; Claverie, Jerome; Liu, Hong; Yu, Guangwei

2015-02-01

A novel scaly Sn3O4/TiO2 nanobelt heterostructured photocatalyst was fabricated via a facile hydrothermal route. The scaly Sn3O4 nanoflakes can be synthesized in situ and assembled on surface coarsened TiO2 nanobelts through a hydrothermal process. The morphology and distribution of Sn3O4 nanoflakes can be well-controlled by simply tuning the Sn/Ti molar ratio of the reactants. Compared with single phase nanostructures of Sn3O4 and TiO2, the scaly hybrid nanobelts exhibited markedly enhanced photoelectrochemical (PEC) response, which caused higher photocatalytic hydrogen evolution even without the assistance of Pt as a co-catalyst, and enhanced the degradation ability of organic pollutants under both UV and visible light irradiation. In addition to the increased exposure of active facets and broad light absorption, the outstanding performance is ascribed to the matching energy band structure between Sn3O4 and TiO2 at the two sides of the heterostructure, which efficiently reduces the recombination of photo-excited electron-hole pairs and prolongs the lifetime of charge carriers. Both photocatalytic assessment and PEC tests revealed that Sn3O4/TiO2 heterostructures with a molar ratio of Sn/Ti of 2/1 exhibited the highest photocatalytic activity. This study provides a facile and low-cost method for the large scale production of Sn3O4 based materials in various applications.A novel scaly Sn3O4/TiO2 nanobelt heterostructured photocatalyst was fabricated via a facile hydrothermal route. The scaly Sn3O4 nanoflakes can be synthesized in situ and assembled on surface coarsened TiO2 nanobelts through a hydrothermal process. The morphology and distribution of Sn3O4 nanoflakes can be well-controlled by simply tuning the Sn/Ti molar ratio of the reactants. Compared with single phase nanostructures of Sn3O4 and TiO2, the scaly hybrid nanobelts exhibited markedly enhanced photoelectrochemical (PEC) response, which caused higher photocatalytic hydrogen evolution even without the assistance of Pt as a co-catalyst, and enhanced the degradation ability of organic pollutants under both UV and visible light irradiation. In addition to the increased exposure of active facets and broad light absorption, the outstanding performance is ascribed to the matching energy band structure between Sn3O4 and TiO2 at the two sides of the heterostructure, which efficiently reduces the recombination of photo-excited electron-hole pairs and prolongs the lifetime of charge carriers. Both photocatalytic assessment and PEC tests revealed that Sn3O4/TiO2 heterostructures with a molar ratio of Sn/Ti of 2/1 exhibited the highest photocatalytic activity. This study provides a facile and low-cost method for the large scale production of Sn3O4 based materials in various applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr05749j

Superior Cycle Stability Performance of Quasi-Cuboidal CoV2O6 Microstructures as Electrode Material for Supercapacitors.

PubMed

Wang, Yucheng; Chai, Hui; Dong, Hong; Xu, Jiayu; Jia, Dianzeng; Zhou, Wanyong

2016-10-12

In this study, a rapid, facile, and environment-friendly microwave-assisted method followed by annealing for synthesizing the quasi-cuboidal CoV 2 O 6 is developed. The as-prepared samples manifest high supercapacitor properties with a specific capacitance of 223 F g -1 , good rate capability, and superior cycle stability, retaining 123.3% capacitance when the number of cycles reaches 15,000 after determined by electrochemical tests. More importantly, the quasi-cuboidal CoV 2 O 6 for the first time is introduced into the supercapacitor as a kind of electrode material. The superior electrochemical performance of the quasi-cuboidal CoV 2 O 6 will render the metal vanadium oxides as new and attractive active material for promising application in supercapacitors.

FTIR study of CO2 and H2O/CO2 nanoparticles and their temporal evolution at 80 K.

PubMed

Taraschewski, M; Cammenga, H K; Tuckermann, R; Bauerecker, S

2005-04-21

Fourier transform infrared (FTIR) spectroscopy combined with a long-path collisional cooling cell was used to investigate the temporal evolution of CO2 nanoparticles and binary H2O/CO2 nanocomposites in the aerosol phase at 80 K. The experimental conditions for the formation of different CO2 particle shapes as slab, shell, sphere, cube, and needle have been studied by comparison with calculated data from the literature. The H2O/CO2 nanoparticles were generated with a newly developed multiple-pulse injection technique and with the simpler flow-in technique. The carbon dioxide nu3-vibration band at 2360 cm(-1) and the water ice OH-dangling band at 3700 cm(-1) were used to study the evolution of structure, shape, and contact area of the nanocomposites over 150 s. Different stages of binary nanocomposites with primary water ice cores were identified dependent on the injected CO2 portion: (a) disordered (amorphous) CO2 slabs on water particle surfaces, (b) globular crystalline CO2 humps sticking on the water cores, and (c) water cores being completely enclosed in bigger predominantly crystalline CO2 nanoparticles. However, regular CO2 shell structures on primary water particles showing both longitudinal (LO) and transverse (TO) optical mode features of the nu3-vibration band could not be observed. Experiments with reversed nucleation order indicate that H2O/CO2 composite particles with different initial structures evolve toward similar molecular nanocomposites with separated CO2 and H2O regions.

Hydrothermal fabrication of N-doped (BiO)2CO3: Structural and morphological influence on the visible light photocatalytic activity

NASA Astrophysics Data System (ADS)

Dong, Fan; Wang, Rui; Li, Xinwei; Ho, Wing-Kei

2014-11-01

Various 3D N-doped (BiO)2CO3 (N-BOC) hierarchical superstructures self-assembled with 2D nanosheets were fabricated by one-step hydrothermal treatment of bismuth citrate and urea. The as-obtained samples were characterized by XRD, XPS, FT-IR, SEM, N2 adsorption-desorption isotherms and UV-vis DRS. The hydrothermal temperature plays a crucial role in tuning the crystal and morphological structure of the samples. Adjusting the reaction temperature to 150, 180 and 210 °C, we obtained N-doped (BiO)2CO3 samples with corresponding attractive persimmon-like, flower-like and nanoflakes nano/microstructures. The photocatalytic activities of the samples were evaluated by removal of NO under visible and solar light irradiation. The results revealed that the N-doped (BiO)2CO3 hierarchical superstructures showed enhanced visible light photocatalytic activity compared to pure (BiO)2CO3 and TiO2-based visible light photocatalysts. The outstanding photocatalytic performance of N-BOC samples can be ascribed to the doped nitrogen and the special hierarchical structure. The present work could provide new perspectives in controlling the morphological structure and photocatalytic activity of photocatalyst for better environmental pollution control.

Density functional theory study on the structures, electronic and magnetic properties of the MFe3n‑1O4n (n = 1–3) (M=Mn, Co and Ni) clusters

NASA Astrophysics Data System (ADS)

Li, Zhi; Zhao, Zhen; Wang, Qi; Yin, Xi-tao

2018-04-01

The structures, electronic and magnetic properties of the MFe3n‑1O4n (n = 1–3) (M=Mn, Co and Ni) clusters are obtained by using the GGA-PBE functional. The results found that the CoFe3n‑1O4n (n = 1–3) clusters are more stable than the corresponding NiFe3n‑1O4n and MnFe3n‑1O4n clusters. The NiFe2O4, MnFe5O8 and CoFe5O8 clusters have higher kinetic stability than their neighbors. The average magnetic moments of MFe3n‑1O4n (n = 1–3) (M=Mn, Co and Ni) clusters are successively: NiFe3n‑1O4n > CoFe3n‑1O4n > MnFe3n‑1O4n. For NiFe3n‑1O4n and CoFe3n‑1O4n clusters, the average magnetic moments are decreased with the cluster size increasing while for MnFe3n‑1O4n, the opposite situation is occur. The difference of 3d orbital electrons of M (M=Mn, Co and Ni) atoms influence the magnetic properties of MFe3n‑1O4n clusters.

Synthesis and photocatalytic activity of p–n junction CeO2/Co3O4 photocatalyst for the removal of various dyes from wastewater

NASA Astrophysics Data System (ADS)

Tang, Yuanzheng; Zhang, Meng; Wu, Zhengying; Chen, Zhigang; Liu, Chengbao; Lin, Yun; Chen, Feng

2018-04-01

CeO2, Co3O4, and Co3O4/CeO2 composites are successfully synthesized by a simple coprecipitation method. X-ray powder diffraction (XRD) and Fourier transform infrared (FTIR) results indicate that the CeO2, Co3O4, and Co3O4/CeO2 precursors sintered at 500 °C has good crystallization. The cerium nitrate introduced into cobalt nitrate precursor solution improved the surface morphology and photocatalytic activity of Co3O4 significantly. The photo-degradation of methylene blue (MB), xylenol orange (XO), methyl orange (MO), and methyl red (MR) catalyzed by prepared nanocomposites were studied under visible light irradiation. Photocatalytic experiment results indicate that the photocatalytic activity of Co3O4/CeO2 composites for degradation of various dyes highly depend on pH value. The optimum conditions for the photocatalytic experiments of Co3O4/CeO2 composites were determined to be as follows: dye concentration, 50 mg L‑1, and catalyst concentration, 50 mg L‑1. The excellent photocatalytic activity of the p–n junction Co3O4/CeO2 composites can be ascribed to the ·O2‑ radicals and h+.

Recycling of cobalt from spent Li-ion batteries as β-Co(OH)2 and the application of Co3O4 as a pseudocapacitor

NASA Astrophysics Data System (ADS)

Barbieri, E. M. S.; Lima, E. P. C.; Lelis, M. F. F.; Freitas, M. B. J. G.

2014-12-01

This work has investigated recycling cobalt from the cathodes of spent Li-ion batteries as β-Co(OH)2, obtaining Co3O4. β-Co(OH)2 with a hexagonal structure by using chemical precipitation (CP) or electrochemical precipitation (EP). In addition, the study has investigated whether the charge density applied directly affects the β-Co(OH)2 morphology. Co3O4 is formed by heat-treating β-Co(OH)2 at 450 °C for 3 h (h) in an air atmosphere. After calcining, the Co3O4 shows a cubic structure and satisfactory purity grade, regardless of the route used for preparation via which it was obtained. Cyclic voltammetry (CV) is then used for electrochemical characterization of the Co3O4 composite electrodes. In the cathodic process, CoO2 undergoes reduction to CoOOH, which undergoes further reduction to Co3O4. In the anodic process, Co3O4 undergoes oxidation to CoOOH, which simultaneously undergoes further oxidation to CoO2. The composite electrodes containing Co3O4, carbon black, and epoxy resin show great reversibility, charge efficiency, and a specific capacitance of 13.0 F g-1 (1.0 mV s-1). The synthesis method of Co(OH)2 influences the charge efficiency of Co3O4 composite electrodes at a scan rate of 10.0 mV s-1. Therefore, in addition to presenting an alternative use for exhausted batteries, Co3O4 composites exhibit favorable characteristics for use as pseudocapacitors.

Co3O4 nanorod-supported Pt with enhanced performance for catalytic HCHO oxidation at room temperature

NASA Astrophysics Data System (ADS)

Yan, Zhaoxiong; Xu, Zhihua; Cheng, Bei; Jiang, Chuanjia

2017-05-01

Formaldehyde (HCHO) removal from air at room (ambient) temperature by effective catalysts is of significance for improving indoor air quality, and catalysts with high efficiency and good recyclability are highly desirable. In this study, platinum (Pt) supported on nanorod-shaped Co3O4 (Pt/Co3O4) was prepared by calcination of microwave-assisted synthesized Co3O4 precursor followed by NaBH4-reduction of Pt precursor. The as-prepared Co3O4 exhibited a morphology of nanorods with lengths of 400-700 nm and diameters of approximately 40-50 nm, which were self-assembled by nanoparticles. The Pt/Co3O4 catalyst exhibited a superior catalytic performance for HCHO oxidation at room temperature compared to Pt supported on commercial Co3O4 (Pt/Co3O4-c) and Pt supported on commercial TiO2 (Pt/TiO2), which is mainly due to the high oxygen mobility resulting from its distinct nanorod morphology, strong metal-support interaction between Pt and Co3O4, and the intrinsic redox nature of the Co3O4 support. This study provides new insights into the fabrication of high-performance catalysts for indoor air purification.

Microstructural Evolution of AlCoCrFeNiSi High-Entropy Alloy Powder during Mechanical Alloying and Its Coating Performance

PubMed Central

Fu, Ming; Xiong, Wei

2018-01-01

High-entropy alloys (HEAs) are promising structural materials due to their excellent comprehensive performances. The use of mechanically alloyed powders to deposit HEA coatings through atmospheric plasma spraying (APS) is an effective approach that can broaden the application areas of the HEAs. In this paper, a ductility–brittleness AlCoCrFeNiSi system was chosen as an object of study, and the detailed evolution of the surface morphology, particle size distribution, and microstructure of the powder during mechanical alloying was investigated. An AlCoCrFeNiSi HEA coating was deposited using powder milled for 10 h, which can be used as an ideal feedstock for APS. The surface morphology, microstructure, microhardness, and wear behavior of the coating at room temperature were investigated. The results showed that as the milling time increased, the particle size first increased, and then decreased. At the milling time of 10 h, simple body-centered cubic (BCC) and face-centered cubic (FCC) solid solution phases were formed. After spraying, the lamellar structure inside a single particle disappeared. An ordered BCC phase was detected, and the diffraction peaks of the Si element also disappeared, which indicates that phase transformation occurred during plasma spraying. A transmission electron microscopy analysis showed that nanometer crystalline grains with a grain size of about 30 nm existed in the APS coating. For the coating, an average microhardness of 612 ± 41 HV was obtained. Adhesive wear, tribo-oxidation wear, and slight abrasion wear took place during the wear test. The coating showed good wear resistance, with a volume wear rate of 0.38 ± 0.08 × 10−4 mm3·N−1·m−1, which makes it a promising coating for use in abrasive environments. PMID:29473872

THE IMPRINT OF EXOPLANET FORMATION HISTORY ON OBSERVABLE PRESENT-DAY SPECTRA OF HOT JUPITERS

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

Mordasini, C.; Van Boekel, R.; Mollière, P.

The composition of a planet’s atmosphere is determined by its formation, evolution, and present-day insolation. A planet’s spectrum therefore may hold clues on its origins. We present a “chain” of models, linking the formation of a planet to its observable present-day spectrum. The chain links include (1) the planet’s formation and migration, (2) its long-term thermodynamic evolution, (3) a variety of disk chemistry models, (4) a non-gray atmospheric model, and (5) a radiometric model to obtain simulated spectroscopic observations with James Webb Space Telescope and ARIEL. In our standard chemistry model the inner disk is depleted in refractory carbon asmore » in the Solar System and in white dwarfs polluted by extrasolar planetesimals. Our main findings are: (1) envelope enrichment by planetesimal impacts during formation dominates the final planetary atmospheric composition of hot Jupiters. We investigate two, under this finding, prototypical formation pathways: a formation inside or outside the water iceline, called “dry” and “wet” planets, respectively. (2) Both the “dry” and “wet” planets are oxygen-rich (C/O < 1) due to the oxygen-rich nature of the solid building blocks. The “dry” planet’s C/O ratio is <0.2 for standard carbon depletion, while the “wet” planet has typical C/O values between 0.1 and 0.5 depending mainly on the clathrate formation efficiency. Only non-standard disk chemistries without carbon depletion lead to carbon-rich C/O ratios >1 for the “dry” planet. (3) While we consistently find C/O ratios <1, they still vary significantly. To link a formation history to a specific C/O, a better understanding of the disk chemistry is thus needed.« less

Evolution of Interstellar Grains

NASA Technical Reports Server (NTRS)

Allamandola, Lou J.; DeVincenzi, Donald L. (Technical Monitor)

1998-01-01

During the past two decades observations combined with laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the raw materials from which planets, comets and stars form. Most interstellar material is concentrated in large molecular clouds where simple molecules are formed by dust-grain and gas-phase reactions. Gaseous species striking the cold (10K) dust stick, forming an icy grain mantle. This accretion, coupled with UV photolysis, produces a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. Ices in molecular clouds contain the very simple molecules H2O, CH3OH, CO, CO2, H2, and perhaps some NH3 and H2CO, as well as more complex species. The evidence for these compounds, as well as carbon-rich materials, will be reviewed and the possible connections with comets and meteorites will be presented in the first part of the talk . The second part of the presentation will focus on interstellar/precometary ice photochemical evolution and the species likely to be found in comets. The chemical composition and photochemical evolution of realistic interstellar/pre-cometary ice analogs will be discussed. Ultraviolet photolysis of these ices produces H2, H2CO, CO2, CO, CH4, HCO, and more complex molecules. When ices representative of interstellar grains and comets are exposed to UV radiation at low temperature a series of moderately complex organic molecules are formed in the ice including: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), and R-C=N (nitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. After warming to room temperature an organic residue remains. This is composed primarily of hexamethylenetetramine (HMT, C6H12N4), with lesser amounts of polyoxymethylene-related species (POMs), amides, and ketones. This is in sharp contrast to the organic residues produced by irradiating unrealistic interstellar ice analogs or thermally promoted polymerization-type reactions in unirradiated realistic ice mixtures.

Investigating microstructural evolution during the electroreduction of UO2 to U in LiCl-KCl eutectic using focused ion beam tomography

NASA Astrophysics Data System (ADS)

Brown, L. D.; Abdulaziz, R.; Tjaden, B.; Inman, D.; Brett, D. J. L.; Shearing, P. R.

2016-11-01

Reprocessing of spent nuclear fuels using molten salt media is an attractive alternative to liquid-liquid extraction techniques. Pyroelectrochemical processing utilizes direct, selective, electrochemical reduction of uranium dioxide, followed by selective electroplating of a uranium metal. Thermodynamic prediction of the electrochemical reduction of UO2 to U in LiCl-KCl eutectic has shown to be a function of the oxide ion activity. The pO2- of the salt may be affected by the microstructure of the UO2 electrode. A uranium dioxide filled "micro-bucket" electrode has been partially electroreduced to uranium metal in molten lithium chloride-potassium chloride eutectic. This partial electroreduction resulted in two distinct microstructures: a dense UO2 and a porous U metal structure were characterised by energy dispersive X-ray spectroscopy. Focused ion beam tomography was performed on five regions of this electrode which revealed an overall porosity ranging from 17.36% at the outer edge to 3.91% towards the centre, commensurate with the expected extent of reaction in each location. The pore connectivity was also seen to reduce from 88.32% to 17.86% in the same regions and the tortuosity through the sample was modelled along the axis of propagation of the electroreduction, which was seen to increase from a value of 4.42 to a value of infinity (disconnected pores). These microstructural characteristics could impede the transport of O2- ions resulting in a change in the local pO2- which could result in the inability to perform the electroreduction.

Epitaxial growth of cobalt oxide phases on Ru(0001) for spintronic device applications

NASA Astrophysics Data System (ADS)

Olanipekun, Opeyemi; Ladewig, Chad; Kelber, Jeffry A.; Randle, Michael D.; Nathawat, Jubin; Kwan, Chun-Pui; Bird, Jonathan P.; Chakraborti, Priyanka; Dowben, Peter A.; Cheng, Tao; Goddard, W. A., III

2017-09-01

Cobalt oxide films are of technological interest as magnetic substrates that may support the direct growth of graphene, for use in various spintronic applications. In this work, we demonstrate the controlled growth of both Co3O4(111) and CoO(111) on Ru(0001) substrates. The growth is performed by Co molecular beam epitaxy, at a temperature of 500 K and in an O2 partial pressure of 10-4 Torr for Co3O4(111), and 7.5 × 10-7 Torr for CoO(111). The films are distinguished by their dissimilar Co 2p x-ray photoemission (XPS) spectra, while XPS-derived O/Co stoichiometric ratios are 1.33 for Co3O4(111) and 1.1 for CoO(111). Electron energy loss (EELS) spectra for Co3O4(111) indicate interband transitions at ˜2.1 and 3.0 eV, while only a single interband transition near 2.0 eV is observed for CoO(111). Low energy electron diffraction (LEED) data for Co3O4(111) indicate twinning during growth, in contrast to the LEED data for CoO(111). For Co3O4(111) films of less than 20 Å average thickness, however, XPS, LEED and EELS data are similar to those of CoO(111). XPS data indicate that both Co oxide phases are hydroxylated at all thicknesses. The two phases are moreover found to be thermally stable to at least 900 K in UHV, while ex situ atomic force microscopy measurements of Co3O4(111)/Ru(0001) indicate an average surface roughness below 1 nm. Electrical measurements indicate that Co3O4(111)/Ru(0001) films exhibit dielectric breakdown at threshold voltages of ˜1 MV cm-1. Collectively, these data show that the growth procedures yield Co3O4(111) films with topographical and electrical characteristics that are suitable for a variety of advanced device applications.

Nonprotective Alumina Growth in Sulfur-Doped NiAl(Zr)

NASA Technical Reports Server (NTRS)

Smialek, James L.

2000-01-01

The 1200 C oxidation behavior of NiAl was examined at various levels of sulfur and zirconium dopants to test the possibility of a critical S/Zr ratio required for adhesion. Cyclic furnace testing for 200 1 -hr cycles and interrupted testing for 500 hr were used as screening tests. Pure NiAl and NiAl(Zr) with 0. 14 at.% Zr were chosen as model base compositions; they exhibited normal, slow-growing scales (3 Mg/sq cm) with excellent adhesion for the Zr-doped alloys. NiAl with about 120 ppma S exhibited a substantial weight loss (-20 Mg/sq cm) in cyclic tests and a very large weight gain (+60 Mg/sq cm) in interrupted tests. The major surface phase remained as alpha -Al2O3. Sulfur doping the NiAl(Zr) alloy caused massive weight gains of 80 - 100 Mg/sq cm, swelling, cracking, and nearly complete conversion into NiAl2O4, and alpha- Al2O3. The initial objective of determining critical S/Zr ratios for adhesion was therefore unattainable. Initiation of the catastrophic attack was examined after a 10 hr exposure, revealing a few sites of broad, raised, and cracked ridges. In cross-section, the ridges appeared as modular intrusions, with a complex, fractal, oxide-metal interface. They were primarily alumina (with occasional entrapped islands of NiAl2O4 or pure Ni metal). They possessed a unique microstructure consisting of 0.3 microns lamellae, separated by 0.1 microns open channels. This allowed for rapid growth controlled by gaseous diffusion. The microstructure is discussed in terms of SO2 evolution and a sulfur-driven de-passivation process.

Microstructural evolution and precipitation behavior in heat affected zone of Inconel 625 and AISI 904L dissimilar welds

NASA Astrophysics Data System (ADS)

Senthur Prabu, S.; Devendranath Ramkumar, K.; Arivazhagan, N.

2017-11-01

In the present investigation an attempt has been made to join the dissimilar combination of Inconel 625 super alloy and super austenitic stainless steel (AISI 904L) using manual multi-pass continuous current gas tungsten arc (CCGTA) welding processes. Two different filler wires such as ERNiCrMo-4 and ERNiCrCoMo-1 have been used to compare the metallurgical properties of these welded joints. Both optical microscopy and scanning electron microscopy techniques were adopted to disseminate the microstructure traits of these weldments. Formation of secondary phases at the HAZ and weld interface of AISI 904L was witnessed while using the ERNiCrCoMo-1 filler, along with Solidification Grain Boundary (SGB) and Migrated Grain Boundary (MGB) were also observed at the weld zone.

Patterned solid state growth of barium titanate crystals

NASA Astrophysics Data System (ADS)

Ugorek, Michael Stephen

An understanding of microstructure evolution in ceramic materials, including single crystal development and abnormal/enhanced grain growth should enable more controlled final ceramic element structures. In this study, two different approaches were used to control single crystal development in a patterned array. These two methods are: (1) patterned solid state growth in BaTiO 3 ceramics, and (2) metal-mediated single crystal growth in BaTiO 3. With the patterned solid state growth technique, optical photolithography was used to pattern dopants as well as [001] and [110] BaTiO3 single crystal template arrays with a 1000 microm line pattern array with 1000 microm spacings. These patterns were subsequently used to control the matrix grain growth evolution and single crystal development in BaTiO3. It was shown that the growth kinetics can be controlled by a small initial grain size, atmosphere conditions, and the introduction of a dopant at selective areas/interfaces. By using a PO2 of 1x10-5 atm during high temperature heat treatment, the matrix coarsening has been limited (to roughly 2 times the initial grain size), while retaining single crystal boundary motion up to 0.5 mm during growth for dwell times up to 9 h at 1300°C. The longitudinal and lateral growth rates were optimized at 10--15 microm/h at 1300°C in a PO2 of 1x10 -5 atm for single crystal growth with limited matrix coarsening. Using these conditions, a patterned microstructure in BaTiO3 was obtained. With the metal-mediated single crystal growth technique, a novel approach for fabricating 2-2 single crystal/polymer composites with a kerf < 5 microns was demonstrated. Surface templated grain growth was used to propagate a single crystal interface into a polycrystalline BaTiO3 or Ba(Zr0.05 Ti0.95)O3 matrix with lamellar nickel layers. The grain growth evolution and texture development were studied using both [001] and [110] BaTiO3 single crystals templates. By using a PO 2 of 1x10-11 atm during high temperature heat treatment, matrix coarsening was limited while enabling single crystal boundary motion up to 0.35 mm during growth between 1250°C and 1300°C with growth rates ˜ 3--4 microm/h for both single crystal orientations. By removing the inner electrodes, 2-2 single crystal (or ceramic) composites were prepared. The piezoelectric and dielectric properties of the composites of the two compositions were measured. The d33 and d31 of the composites were similar to the polycrystalline ceramic of the same composition.

The facile synthesis of hierarchical NiCoO2 nanotubes comprised ultrathin nanosheets for supercapacitors

NASA Astrophysics Data System (ADS)

Xu, Xin; Zhou, Han; Ding, Shujiang; Li, Jun; Li, Beibei; Yu, Demei

2014-12-01

Hierarchical NiCoO2 nanosheets nanotubes are successfully prepared by a mild solution method based on the template of polymeric nanotubes (PNT) followed by a thermal annealing treatment. The microstructure and chemical composition of NiCoO2 nanosheets nanotubes are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) analyzer, X-ray diffraction (XRD) and Thermogravimetric analysis (TGA). When evaluated as an electrode material for supercapacitors, the results of electrochemical test show that the unique NiCoO2 nanosheets nanotubes exhibit relatively high specific capacitance of 1468, 1352, 1233, 1178, 1020 and 672 F g-1 at the discharge current densities of 2, 4, 8, 10, 20 and 40 A g-1, respectively. They also reveal an excellent cycling stability of 99.2% retention after 3000 cycles at 10 A g-1. The smart nanostructures of the NiCoO2 nanosheets nanotubes make a prominent contribution to the excellent electrochemical performance.

Synthesis of Co3O4 nanoparticles with block and sphere morphology, and investigation into the influence of morphology on biological toxicity

PubMed Central

RAMAN, VENKATARAMANAN; SURESH, SHRUTHI; SAVARIMUTHU, PHILIP ANTHONY; RAMAN, THIAGARAJAN; TSATSAKIS, ARISTIDES MICHAEL; GOLOKHVAST, KIRIL SERGEEVICH; VADIVEL, VINOD KUMAR

2016-01-01

In the present study, cobalt oxide (Co3O4) magnetic nanoparticles with block and sphere morphologies were synthesized using various surfactants, and the toxicity of the particles was analyzed by monitoring biomarkers of nanoparticle toxicity in zebrafish. The use of tartarate as a surfactant produced highly crystalline blocks of Co3O4 nanoparticles with pores on the sides, whereas citrate lead to the formation of nanoparticles with a spherical morphology. Co3O4 structure, crystallinity, size and morphology were studied using X-ray diffractogram and field emission scanning electron microscopy. Following an increase in nanoparticle concentration from 1 to 200 ppm, there was a corresponding increase in nitric oxide (NO) generation, induced by both types of nanoparticles [Co3O4-NP-B (block), r=0.953; Co3O4-NP-S (sphere), r=1.140]. Comparative analyses indicated that both types of nanoparticle produced significant stimulation at ≥5 ppm (P<0.05) compared with a control. Upon analyzing the effect of nanoparticle morphology on NO generation, it was observed that Co3O4-NP-S was more effective compared with Co3O4-NP-B (5 and 100 ppm, P<0.05; 200 ppm, P<0.01). Exposure to both types of nanoparticles produced reduction in liver glutathione (GSH) activity with corresponding increase in dose (Co3O4-NP-B, r=−0.359; Co3O4-NP-S, r=−0.429). However, subsequent analyses indicated that Co3O4-NP-B was more potent in inhibiting liver GSH activity compared with Co3O4-NP-S. Co3O4-NP-B proved to be toxic at 5 ppm (P<0.05) and GSH activity was almost completely inhibited at 200 ppm. A similar toxicity was observed with both types of Co3O4-NPs against brain levels of acetylcholinesterase (AChE; Co3O4-NP-B, r=−0.180; Co3O4-NP-S, r=−0.230), indicating the ability of synthesized Co3O4-NPs to cross the blood-brain barrier and produce neuronal toxicity. Co3O4-NP-B showed increased inhibition of brain AChE activity compared with Co3O4-NP-S (1,5, and 10 ppm, P<0.05; 50, 100 and 200 ppm, P<0.01). These results suggested that the morphology of nanoparticle and surface area contribute to toxicity, which may have implications for their biological application. PMID:26893646

Micro-CT in situ study of carbonate rock microstructural evolution for geologic CO2 storage

NASA Astrophysics Data System (ADS)

Zheng, Y.; Yang, Y.; Rogowska, M.; Gundlach, C.

2017-09-01

To achieve the 2°C target made in the 2016 Paris Agreement, it is essential to reduce the emission of CO2 into the atmosphere. Carbon Capture and Storage (CCS) has been given increasing importance over the last decade. One of the suggested methods for CCS is to inject CO2 into geologic settings such as the carbonate reservoirs in the North Sea. The final aim of our project is to find out how to control the evolution of petrophysical parameters during CO2 injection using an optimal combination of flow rate, injection pressure and chemical composition of the influent. The first step to achieve this is to find a suitable condition to create a stable 3D space in carbonate rock by injecting liquid to prepare space for the later CO2 injection. Micro-CT imaging is a non-destructive 3D method that can be used to study the property changes of carbonate rocks during and after CO2 injection. The advance in lab source based micro-CT has made it capable of in situ experiments. We used a commercial bench top micro-CT (Zeiss Versa XRM410) to study the microstructure changes of chalk during liquid injection. Flexible temporal CT resolution is essential in this study because that the time scales of coupled physical and chemical processes can be very different. The results validated the feasibility of using a bench top CT system with a pressure cell to monitor the mesoscale multiphase interactions in chalk.

Exchange-coupled Fe3O4/CoFe2O4 nanoparticles for advanced magnetic hyperthermia

NASA Astrophysics Data System (ADS)

Glassell, M.; Robles, J.; Das, R.; Phan, M. H.; Srikanth, H.

Iron oxide nanoparticles especially Fe3O4, γ-Fe2O3 have been extensively studied for magnetic hyperthermia because of their tunable magnetic properties and stable suspension in superparamagnetic regime. However, their relatively low heating capacity hindered practical application. Recently, a large improvement in heating efficiency has been reported in exchange-coupled nanoparticles with exchange coupling between soft and hard magnetic phases. Here, we systematically studied the effect of core and shell size on the heating efficiency of the Fe3O4/CoFe2O4 core/shell nanoparticles. The nanoparticles were synthesized using thermal decomposition of organometallic precursors. Transmission electron microscopy (TEM) showed formation of spherical shaped Fe3O4 and Fe3O-/CoFe2O4 nanoparticles. Magnetic measurements showed high magnetization (≅70 emu/g) and superparamagnetic behavior for the nanoparticles at room temperature. Magnetic hyperthermia results showed a large increase in specific absorption rate (SAR) for 8nm Fe3O4/CoFe2O4 compared to Fe3O4 nanoparticles of the same size. The heating efficiency of the Fe3O4/CoFe2O4 with 1 nm CoFe2O4 (shell) increased from 207 to 220 W/g (for 800 Oe) with increase in core size from 6 to 8 nm. The heating efficiency of the Fe3O4/CoFe2O4 with 2 nm CoFe2O4 (shell) and core size of 8 nm increased from 220 to 460 W/g (for 800 Oe). These exchange-coupled Fe3O4/CoFe2O4 core/shell nanoparticles can be a good candidate for advanced hyperthermia application.

High coercivity microcrystalline Nd-rich Nd-Fe-Co-Al-B bulk magnets prepared by direct copper mold casting

NASA Astrophysics Data System (ADS)

Zhao, L. Z.; Hong, Y.; Fang, X. G.; Qiu, Z. G.; Zhong, X. C.; Gao, X. S.; Liu, Z. W.

2016-06-01

High coercivity Nd25Fe40Co20Al15-xBx (x=7-15) hard magnets were prepared by a simple process of injection casting. Different from many previous investigations on nanocomposite compositions, the magnets in this work contain hard magnetic Nd2(FeCoAl)14B, Nd-rich, and Nd1+ε(FeCo)4B4 phases. The magnetic properties, phase evolution, and microstructure of the as-cast and annealed magnets were investigated. As the boron content increased from 7 to 11 at%, the intrinsic coercivity Hcj of the as-cast magnet increased from 816 to 1140 kA/m. The magnets annealed at 750 °C have shown more regular and smaller grains than the as-cast alloys, especially for the x=11 alloy. The high intrinsic coercivities for the annealed alloys with x=8~11 result from the presence of small-sized grains in the microstructure. The highest Hcj of 1427 kA/m was obtained for the heat treated alloy with x=10. This work provides an alternative approach for preparing fully dense Nd-rich bulk hard magnets with relatively good properties.

Synthesis of magnetic Bi2O2CO3/ZnFe2O4 composite with improved photocatalytic activity and easy recyclability

NASA Astrophysics Data System (ADS)

Liu, Yumin; Ren, Hao; Lv, Hua; Guang, Jing; Cao, Yafei

2018-03-01

Magnetic Bi2O2CO3/ZnFe2O4 heterojunction photocatalysts with varying content of ZnFe2O4 were constructed by modifying Bi2O2CO3 nanosheets with mesoporous ZnFe2O4 nanoparticles. The photoactivity of the products was investigated by decomposing RhodamineB (RhB) and it was found that the photoactivity of Bi2O2CO3/ZnFe2O4 composite was closely related to the loading amount of ZnFe2O4. Under simulant sunlight irradiation, the optimum photoactivity of Bi2O2CO3/ZnFe2O4 composite was almost 2.3 and 2.1 times higher than that by bare ZnFe2O4 and Bi2O2CO3, respectively. The improved photoactivity resulted from the synergistic effect of Bi2O2CO3 and ZnFe2O4, which not only extended the photoabsorption region but also significantly facilitated the interfacial charge transfer. Besides the high photocatalytic performance, Bi2O2CO3/ZnFe2O4 composite also exhibited excellent stable and recycling properties, which enabled it have great potential in a long-term practical use.

On the thermal behavior of model Li-Li xCoO 2 systems containing ionic liquids in standard electrolyte solutions

NASA Astrophysics Data System (ADS)

Larush, L.; Borgel, V.; Markevich, E.; Haik, O.; Zinigrad, E.; Aurbach, D.; Semrau, G.; Schmidt, M.

We report herein on the possibility of using ionic liquids (ILs) as additives to conventional electrolyte solutions, based on alkyl carbonates and LiPF 6 for attenuating thermal reactions in Li battery systems. As a model, a Li-Li 0.5CoO 2 system was used. The ionic liquids chosen included cations based on derivatives of pyrrolidinium and imidazolium, and the anions bioxalato borate (C 4O 8B -, BOB), (CH 3SO 2) 2N - (TFSI), and PF 3(C 2S 5) 3 - (FAP). The thermal behavior of solutions alone, solutions with Li metal, Li 0.5CoO 2 and Li metal + Li 0.5CoO 2 was studied. It was found that the presence of 10% of ILs, with derivatives of pyrrolidinium cations and FAP or TFSI anions in standard EC-DMC/LiPF 6 solutions, improves considerably the thermal stability of Li 0.5CoO 2 in electrolyte solutions. The onset temperatures of the thermal reactions of Li 0.5CoO 2 with solution species are higher and their heat evolution is considerably lower, when they contain these ionic liquids as additives. This finding opens the door for further studies and optimization of the use of selected ILs as additives that may improve the safety features of Li-ion batteries.

Porous LaCo1-xNixO3-δ Nanostructures as an Efficient Electrocatalyst for Water Oxidation and for a Zinc-Air Battery.

PubMed

Vignesh, Ahilan; Prabu, Moni; Shanmugam, Sangaraju

2016-03-09

Perovskites have emerged as promising earth-abundant alternatives to precious metals for catalyzing the oxygen evolution reaction (OER). Herein, we report the synthesis of a series of porous perovskite nanostructures, LaCo0.97O3-δ, with systematic Ni substitution in Co octahedral sites. Their electrocatalytic activity during the water oxidation reaction was studied in alkaline electrolytes. The electrocatalytic OER activity and stability of the perovskite nanostructure was evaluated using the rotating disk electrode technique. We show that the progressive replacement of Co by Ni in the LaCo0.97O3-δ perovskite structure greatly altered the electrocatalytic activity and that the La(Co0.71Ni0.25)0.96O3-δ composition exhibited the lowest OER overpotential of 324 and 265 mV at 10 mA cm(-2) in 0.1 M KOH and 1 M KOH, respectively. This value was much lower than that of the noble metal catalysts, IrO2, Ru/C, and Pt/C. Furthermore, the La(Co0.71Ni0.25)0.96O3-δ nanostructure showed outstanding electrode stability, with no observable decrease in performance up to 114th cycle in the auxiliary linear sweep voltammetry that lasted for 10 h in chronoamperometry studies. The excellent oxygen evolution activity of the La(Co0.71Ni0.25)0.96O3-δ perovskite nanostructure can be attributed to its intrinsic structure, interconnected particle arrangement, and unique redox characteristics. The enhanced intrinsic electrocatalytic activity of the La(Co0.71Ni0.25)0.96O3-δ catalyst was correlated with several parameters, such as the electrochemical surface area, the roughness factor, and the turnover frequency, with respect to variation in the transition metals of the perovskite structure. Subsequently, La(Co0.71Ni0.25)0.96O3-δ was utilized as the air cathode in a zinc-air battery application.

Ceramics reinforced metal base composite coatings produced by CO II laser cladding

NASA Astrophysics Data System (ADS)

Yang, Xichen; Wang, Yu; Yang, Nan

2008-03-01

Due to the excellent performance in high strength, anti-temperature and anti-wear, ceramics reinforced metal base composite material was used in some important fields of aircraft, aerospace, automobile and defense. The traditional bulk metal base composite materials are the expensive cost, which is limited in its industrial application. Development of laser coating of ceramics reinforced metal base composite is very interesting in economy. This paper is focused on three laser cladding ceramics coatings of SiC particle /Al matrix , Al IIO 3 powder/ Al matrix and WC + Co/mild steel matrix. Powder particle sizes are of 10-60μm. Chemical contents of aluminum matrix are of 3.8-4.0% Cu, 1.2-1.8% Mg, 0.3-0.99% Mn and balance Al. 5KW CO II laser, 5 axes CNC table, JKF-6 type powder feeder and co-axis feeder nozzle are used in laser cladding. Microstructure and performance of laser composite coatings have been respectively examined with OM,SEM and X-ray diffraction. Its results are as follows : Microstructures of 3C-,6H- and 5H- SiC particles + Al + Al 4SiC 4 + Si in SiC/Al composite, hexagonal α-Al IIO 3 + cubic γ-Al IIO 3 + f.c.c Al in Al IIO 3 powder/ Al composite and original WC particles + separated WC particles + eutectic WC + γ-Co solid solution + W IIC particles in WC + Co/steel coatings are respectively recognized. New microstructures of 5H-SiC in SiC/Al composite, cubic γ-Al IIO 3 in Al IIO 3 composite and W IIC in WC + Co/ steel composite by laser cladding have been respectively observed.

Magnetic and magnetocaloric properties of Ba and Ti co-doped SrRuO{sub 3}

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

Sarkar, Babusona; Dalal, Biswajit; Dev Ashok, Vishal

2014-12-28

Temperature evolution of magnetic properties in Ba and Ti doped SrRuO{sub 3} has been investigated to observe the effects of larger ionic radius Ba at Sr site and isovalent nonmagnetic impurity Ti at Ru site. Ionic radius mismatch and different electronic configuration in comparison with Ru modify Sr(Ba)-O and Ru(Ti)-O bond lengths and Ru-O-Ru bond angle. The apical and basal Ru-O-Ru bond angles vary significantly with Ti doping. Ferromagnetic Curie temperature decreases from 161 K to 149 K monotonically with Ba (10%) and Ti (10%) substitutions at Sr and Ru sites. The zero field cooled (ZFC) magnetization reveals a prominent peak whichmore » shifts towards lower temperature with application of magnetic field. The substitution of tetravalent Ti with localized 3d{sup 0} orbitals for Ru with more delocalized 4d{sup 4} orbitals leads to a broad peak in ZFC magnetization. A spontaneous ZFC magnetization becomes negative below 160 K for all the compositions. The occurrence of both normal and inverse magnetocaloric effects in Ba and Ti co-doped SrRuO{sub 3} makes the system more interesting.« less

Liquid-feed flame spray pyrolysis synthesis of oxide nanopowders for the processing of ceramic composites

NASA Astrophysics Data System (ADS)

Taylor, Nathan John

In the liquid-feed flame spray pyrolysis (LF-FSP) process, alcohol solutions of metalloorganic precursors are aerosolized by O2 and combusted. The metal oxide combustion products are rapidly quenched (< 10 ms) from flame temperatures of 1500°C to temperatures < 400° C, limiting particle growth. The resulting nanopowders are typically agglomerated but unaggregated. Here, we demonstrate two processing approaches to dense materials: nanopowders with the exact composition, and mixed single metal oxide nanopowders. The effect of the initial degree of phase separation on the final microstructures was determined by sintering studies. Our first studies included the production of yttrium aluminum garnet, Y3Al5O12 (YAG), tubes which we extruded from a thermoplastic/ceramic blend. At equivalent final densities, we found finer grain sizes in the from the mixed Y2O3 and Al2 O3 nanopowders, which was attributed to densification occurring before full transformation to the YAG phase. The enhanced densification in production of pure YAG from the reactive sintering process led us to produce composites in the YAG/alpha-Al 2O3 system. Finally, a third Y2O3 stabilized ZrO2 (YSZ) phase was added to further refine grain sizes using the same two processing approaches. In a separate study, single-phase metastable Al2O3 rich spinels with the composition MO•3Al 2O3 where M = Mg, Ni, and Co were sintered to produce dense MAl2O4/alpha-Al2O3 composites. All of these studies provide a test of the bottom-up approach; that is, how the initial length scale of mixing affects the final composite microstructure. Overall, the length scale of mixing is highly dependent upon the specific oxide composites studied. This work provides a processing framework to be adopted by other researchers to further refine microstructural size. LF-FSP flame temperatures were mapped using different alcohols with different heats of combustion: methanol, ethanol, 1-propanol, and n-butanol. The effect of different alcohols on particle size and phase was determined through studies on Al2O3, Y2O3 and TiO2 nanopowders. The final studies describe the morphology of composite nanopowders produced in the WO3-TiO2 and CuO-TiO2 systems. The composite nanopowders have novel morphology, and may offer novel electronic, optical, or catalytic properties.

Nature-Inspired 2D-Mosaic 3D-Gradient Mesoporous Framework: Bimetal Oxide Dual-Composite Strategy toward Ultrastable and High-Capacity Lithium Storage.

PubMed

Yu, Jia; Wang, Yanlei; Mou, Lihui; Fang, Daliang; Chen, Shimou; Zhang, Suojiang

2018-02-27

In allusion to traditional transition-metal oxide (TMO) anodes for lithium-ion batteries, which face severe volume variation and poor conductivity, herein a bimetal oxide dual-composite strategy based on two-dimensional (2D)-mosaic three-dimensional (3D)-gradient design is proposed. Inspired by natural mosaic dominance phenomena, Zn 1-x Co x O/ZnCo 2 O 4 2D-mosaic-hybrid mesoporous ultrathin nanosheets serve as building blocks to assemble into a 3D Zn-Co hierarchical framework. Moreover, a series of derivative frameworks with high evolution are controllably synthesized, based on which a facile one-pot synthesis process can be developed. From a component-composite perspective, both Zn 1-x Co x O and ZnCo 2 O 4 provide superior conductivity due to bimetal doping effect, which is verified by density functional theory calculations. From a structure-composite perspective, 2D-mosaic-hybrid mode gives rise to ladder-type buffering and electrochemical synergistic effect, thus realizing mutual stabilization and activation between the mosaic pair, especially for Zn 1-x Co x O with higher capacity yet higher expansion. Moreover, the inside-out Zn-Co concentration gradient in 3D framework and rich oxygen vacancies further greatly enhance Li storage capability and stability. As a result, a high reversible capacity (1010 mA h g -1 ) and areal capacity (1.48 mA h cm -2 ) are attained, while ultrastable cyclability is obtained during high-rate and long-term cycles, rending great potential of our 2D-mosaic 3D-gradient design together with facile synthesis.

Nanoscale PdO Catalyst Functionalized Co3O4 Hollow Nanocages Using MOF Templates for Selective Detection of Acetone Molecules in Exhaled Breath.

PubMed

Koo, Won-Tae; Yu, Sunmoon; Choi, Seon-Jin; Jang, Ji-Soo; Cheong, Jun Young; Kim, Il-Doo

2017-03-08

The increase of surface area and the functionalization of catalyst are crucial to development of high-performance semiconductor metal oxide (SMO) based chemiresistive gas sensors. Herein, nanoscale catalyst loaded Co 3 O 4 hollow nanocages (HNCs) by using metal-organic framework (MOF) templates have been developed as a new sensing platform. Nanoscale Pd nanoparticles (NPs) were easily loaded on the cavity of Co based zeolite imidazole framework (ZIF-67). The porous structure of ZIF-67 can restrict the size of Pd NPs (2-3 nm) and separate Pd NPs from each other. Subsequently, the calcination of Pd loaded ZIF-67 produced the catalytic PdO NPs functionalized Co 3 O 4 HNCs (PdO-Co 3 O 4 HNCs). The ultrasmall PdO NPs (3-4 nm) are well-distributed in the wall of Co 3 O 4 HNCs, the unique structure of which can provide high surface area and high catalytic activity. As a result, the PdO-Co 3 O 4 HNCs exhibited improved acetone sensing response (R gas /R air = 2.51-5 ppm) compared to PdO-Co 3 O 4 powders (R gas /R air = 1.98), Co 3 O 4 HNCs (R gas /R air = 1.96), and Co 3 O 4 powders (R gas /R air = 1.45). In addition, the PdO-Co 3 O 4 HNCs showed high acetone selectivity against other interfering gases. Moreover, the sensor array clearly distinguished simulated exhaled breath of diabetics from healthy people's breath. These results confirmed the novel synthesis of MOF templated nanoscale catalyst loaded SMO HNCs for high performance gas sensors.

In situ TEM of radiation effects in complex ceramics.

PubMed

Lian, Jie; Wang, L M; Sun, Kai; Ewing, Rodney C

2009-03-01

In situ transmission electron microscopy (TEM) has been extensively applied to study radiation effects in a wide variety of materials, such as metals, ceramics and semiconductors and is an indispensable tool in obtaining a fundamental understanding of energetic beam-matter interactions, damage events, and materials' behavior under intense radiation environments. In this article, in situ TEM observations of radiation effects in complex ceramics (e.g., oxides, silicates, and phosphates) subjected to energetic ion and electron irradiations have been summarized with a focus on irradiation-induced microstructural evolution, changes in microchemistry, and the formation of nanostructures. New results for in situ TEM observation of radiation effects in pyrochlore, A(2)B(2)O(7), and zircon, ZrSiO(4), subjected to multiple beam irradiations are presented, and the effects of simultaneous irradiations of alpha-decay and beta-decay on the microstructural evolution of potential nuclear waste forms are discussed. Furthermore, in situ TEM results of radiation effects in a sodium borosilicate glass subjected to electron-beam exposure are introduced to highlight the important applications of advanced analytical TEM techniques, including Z-contrast imaging, energy filtered TEM (EFTEM), and electron energy loss spectroscopy (EELS), in studying radiation effects in materials microstructural evolution and microchemical changes. By combining ex situ TEM and advanced analytical TEM techniques with in situ TEM observations under energetic beam irradiations, one can obtain invaluable information on the phase stability and response behaviors of materials under a wide range of irradiation conditions. (c) 2009 Wiley-Liss, Inc.

Spark plasma sintering of bulk SrAl2O4-Sr3Al2O6 eutectic glass with wide-band optical window.

PubMed

Liu, Jiaxi; Lu, Nan; He, Gang; Li, Xiaoyu; Li, Jianqiang; Li, Jiangtao

2018-06-15

SrAl 2 O 4 -Sr 3 Al 2 O 6 eutectic glass was prepared by using an aerodynamic levitator equipped with a CO 2 laser device. A bulk transparent amorphous sample was obtained by the spark plasma sintering (SPS) of the prepared eutectic glass. XRD, a UV-vis-NIR spectrophotometer and FT-IR were employed to characterize the phase evolution and optical properties. The results show that the bulk SrAl 2 O 4 -Sr 3 Al 2 O 6 samples fabricated by the containerless process and SPS between 852 °C-857 °C were fully amorphous. The amorphous sample has a wide transparent window between 270 nm and 6.2 μm. The average refractive index in the visible light region is 1.680 and the Abbe number is 27.4. The prepared bulk SrAl 2 O 4 -Sr 3 Al 2 O 6 eutectic glass with the wide-band optical window may be a promising candidate for optical applications.

Spark plasma sintering of bulk SrAl2O4-Sr3Al2O6 eutectic glass with wide-band optical window

NASA Astrophysics Data System (ADS)

Liu, Jiaxi; Lu, Nan; He, Gang; Li, Xiaoyu; Li, Jianqiang; Li, Jiangtao

2018-06-01

SrAl2O4-Sr3Al2O6 eutectic glass was prepared by using an aerodynamic levitator equipped with a CO2 laser device. A bulk transparent amorphous sample was obtained by the spark plasma sintering (SPS) of the prepared eutectic glass. XRD, a UV–vis-NIR spectrophotometer and FT-IR were employed to characterize the phase evolution and optical properties. The results show that the bulk SrAl2O4-Sr3Al2O6 samples fabricated by the containerless process and SPS between 852 °C–857 °C were fully amorphous. The amorphous sample has a wide transparent window between 270 nm and 6.2 μm. The average refractive index in the visible light region is 1.680 and the Abbe number is 27.4. The prepared bulk SrAl2O4-Sr3Al2O6 eutectic glass with the wide-band optical window may be a promising candidate for optical applications.

Study of xCo0.8Ni0.2Fe2O4+(1-x) Pb0.99625 La0.0025Zr0.55Ti0.45O3 magnetoelectric composites

NASA Astrophysics Data System (ADS)

Dipti; Singh, Sangeeta; Juneja, J. K.; Raina, K. K.; Kotnala, R. K.; Prakash, Chandra

2016-06-01

We are reporting here, the studies of the structural, dielectric, ferroelectric and magnetic properties of magnetoelectric composites of La modified lead zirconate titanate (PLZT) and Ni modified cobalt ferrite (CNFO) with compositional formula xCo0.8Ni0.2Fe2O4+(1-x) Pb0.99625La0.0025Zr0.55Ti0.45O3 (x=0.00, 0.05, 0.10, 0.15 and 1.00 by weight) prepared by the solid state reaction method. Coexistence of both the phases in composites was confirmed by X-Ray diffraction technique. The microstructure and average grain size were determined from Scanning Electron Micrograph (SEM) in backscattered mode. Both the phases could be observed clearly. The variations of dielectric properties with frequency and temperature were also studied. P-E and M-H hysteresis measurements were carried. Magnetoelectric coupling (ME) coefficient for samples with x=0.05 and 0.10 were measured as a function of DC magnetic field. Maximum value of ME coefficient (1.2 mV/cm Oe) and piezoelectric coefficient (96 pC/N) for x=0.05 were observed.

Mo and P co-doped Ba5Ta4O15 for hydrogen evolution under solar light

NASA Astrophysics Data System (ADS)

Li, Songjie; Cao, Wenbo; Wang, Chengduo; Du, Xueshan; Lu, Shufen

2018-07-01

Based on density functional calculations, Mo and P co-doped Ba5Ta4O15 compared with their mono-doping was studied for splitting water. The results showed that Mo-P co-doping significantly reduced the energy gap of Ba5Ta4O15 from 4.05 eV to 2.15 eV, being almost the optimum value for utilizing solar energy as much as possible. The top of valence band and the bottom of conduction band are both compatible with the oxidation-reduction potentials of water. More importantly, Mo-P co-doping prevents the filled spin-down states of Mo and the empty spin-down states of P from arising due to the charge compensation of Mo-P pairs. We propose that Mo-P co-doped Ba5Ta4O15 is one of the most promising photocatalyst candidates for solar water splitting.

The effect of doping (Mn,B)3O4 materials as protective layers in different metallic interconnects for Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Miguel-Pérez, Verónica; Martínez-Amesti, Ana; Nó, María Luisa; Larrañaga, Aitor; Arriortua, María Isabel

2013-12-01

Spinel oxides with the general formula of (Mn,B)3O4 (B = Co, Fe) were used as barrier materials between the cathode and the metallic interconnect to reduce the rate of cathode degradation by Cr poisoning. The effect of doping at the B position was investigated terms of microstructure and electrical conductivity to determine its behaviour and effectiveness as a protective layer in contact with three metallic materials (Crofer 22 APU, SS430 and Conicro 4023 W 188). The analysis showed that the use of these materials considerably decreased the reactivity and diffusion of Cr between the cathode and the metallic interconnects. The protective layer doped with Fe at the B position exhibited the least amount of reactivity with the interconnector and cathode materials. The worst results were observed for SS430 cells coated with a protective layer perhaps due to their low Cr content. The Crofer 22 APU and Conicro 4023 W 188 samples exhibited very similar conductivity results in the presence of the MnCo1.9Fe0.1O4 protective coating. As a result, these two material combinations are a promising option for use as bipolar plates in SOFC.

CoMoS2/rGO/C3N4 ternary heterojunctions catalysts with high photocatalytic activity and stability for hydrogen evolution under visible light irradiation

NASA Astrophysics Data System (ADS)

Xu, Xuejun; Si, Zhichun; Liu, Liping; Wang, Zehao; Chen, Ze; Ran, Rui; He, Yonghong; Weng, Duan

2018-03-01

Noble metal free MoS2/g-C3N4 catalyst has attracted intense attentions for visible light photocatalytic hydrogen evolution as a result of its earth abundance, low cost and unique heterojunctions stacked with two dimensional sheets. However, the low charge separation efficiency resulted from the poor conductivity of g-C3N4 and MoS2, and lack of abundant active sites from coordinative unsaturated atoms in MoS2, restricts the photocatalytic hydrogen evolution activity and stability enhancement of MoS2/C3N4 composite catalysts. Herein, CoMoS2/rGO/g-C3N4 catalysts with ternary heterojunctions are prepared by facile solvothermal method, which exhibit high visible light photocatalytic activity and stability for hydrogen evolution. The optimal hydrogen evolution rate of CoMoS2/rGO/g-C3N4 catalysts is 684 μmol g-1 h-1 when the content of CoMoS2 is 2% and the content of rGO is 0.5%. The stability of CoMoS2/rGO/C3N4 catalysts just decrease about 3% after 4 cycling runs for 16 h. The good catalytic performances of catalysts are attributed to the synergistic effect among the g-C3N4 nanosheets, rGO nanosheets and CoMoS2 nanosheets. The high conductivity of rGO nanosheets enhances the electron-hole separation and charge transfer, and Co doping increases the active sites for hydrogen evolution due to the increase of unsaturated atoms in CoMoS2 nanosheets.

Compressibility and reversible amorphization of thaumasite Ca3Si(OH)6(CO3)(SO4)·12H2O pressurized in methanol-ethanol-H2O up to 5 GPa

NASA Astrophysics Data System (ADS)

Likhacheva, A. Yu.; Dementiev, S. N.; Goryainov, S. V.

2017-08-01

The elastic and structure behavior of natural thaumasite compressed in methanol-ethanol-H2O up to 5 GPa was studied by synchrotron powder diffraction with a diamond anvil cell. In the pressure range between 0.0001 and 4.5 GPa, the compression is regular and slightly anisotropic, with a more rigid ab-plane coinciding with the orientation of hydrogen bonds and S-O, C-O bonds in anion groups. The corresponding bulk moduli derived from the third-order Birch-Murnaghan EoS fit are K a = 43(2), K c = 35(2), K T = 39(2) GPa. Rietveld refinements reveal some general features of the structure evolution of thaumasite, which are consistent with the observed elastic anisotropy. The compression within the ab-plane proceeds mainly at the expense of shortening of hydrogen bonds and much lesser decrease of C-O and S-O bonds. In the range of 0.0001-3 GPa the Ca-O polyhedra contract more rapidly along the c-axis as compared to the ab-plane. At about 5 GPa, thaumasite undergoes a reversible transformation to an amorphous phase. The observed behavior differs drastically with that studied previously using helium as the pressure medium, which suggests the effect of He penetration increasing the structure stiffness. Without helium support, the thaumasite structure is preserved only up to 4.5 GPa.

The effect of calcination temperature on the performance of Co3O4-Bi2O3 as a heterogeneous catalyst of peroxymonosulfate

NASA Astrophysics Data System (ADS)

Zhang, Guangshan; Hu, Limin; Wang, Peng; Yuan, Yixing

2017-11-01

In this work, a time-saving microwave-assisted method for synthesis of Co3O4-Bi2O3 was reported. The synthesized Co3O4-Bi2O3 samples were characterized with different techniques to probe their crystalline structures and morphologies. The catalytic performances of synthesized Co3O4-Bi2O3 as peroxymonosulfate activator were evaluated by the degradation of bisphenol A. The effect of calcination temperature on Co3O4-Bi2O3 products was explored and the result showed that the sample calcined at 400 °C possessing superior catalytic activity.

A microstructural study of the degradation and calcium release from hydroxyapatite-calcium oxide ceramics made by infiltration.

PubMed

Zhang, Qinghao; Schmelzer, Eva; Gerlach, Jörg C; Nettleship, Ian

2017-04-01

Hydroxyapatite pellets, partially densified in a low-temperature heat treatment, were infiltrated with calcium nitrate solution followed by in-situ precipitation of Ca(OH) 2 and CaCO 3 . The infiltrated bodies were then densified to high relative density and the calcium carbonate transformed to calcium oxide during sintering and resulted in biphasic hydroxyapatite-CaO ceramics. This work investigated the influence of the infiltration on surface morphology, weight change, and microstructural-level degradation caused by exposure to saline at pH=7.4 and a temperature of 20°C. The CaO rendered the materials more susceptible to degradation, and released calcium into the saline faster than single phase, calcium deficient hydroxyapatite (HA) that were used as a control. In consequence, these ceramics could be used to release calcium into the culture microenvironments of bone tissue or bone marrow cells next to a scaffold surface. Copyright © 2016 Elsevier B.V. All rights reserved.

Dynamic Response of CoSb2O6 Trirutile-Type Oxides in a CO2 Atmosphere at Low-Temperatures

PubMed Central

Guillén-Bonilla, Alex; Rodríguez-Betancourtt, Verónica-María; Flores-Martínez, Martín; Blanco-Alonso, Oscar; Reyes-Gómez, Juan; Gildo-Ortiz, Lorenzo; Guillén-Bonilla, Héctor

2014-01-01

Experimental work on the synthesis of the CoSb2O6 oxide and its CO2 sensing properties is presented here. The oxide was synthesized by a microwave-assisted colloidal method in presence of ethylenediamine after calcination at 600 °C. This CoSb2O6 oxide crystallized in a tetragonal structure with cell parameters a = 4.6495 and c = 9.2763 Å, and space group P42/mnm. To prove its physical, chemical and sensing properties, the oxide was subjected to a series of tests: Raman spectroscopy, Scanning Electron Microscopy (SEM) and impedance (Z) measurements. Microstructures, like columns, bars and hollow hemispheres, were observed. For the CO2 sensing test, a thick film of CoSb2O6 was used, measuring the impedance variations on the presence of air/CO2 flows (0.100 sccm/0.100 sccm) using AC (alternating current) signals in the frequency-range 0.1–100 kHz and low relative temperatures (250 and 300 °C). The CO2 sensing results were quite good. PMID:25162232

Advanced Materials and Processing 2010

NASA Astrophysics Data System (ADS)

Zhang, Yunfeng; Su, Chun Wei; Xia, Hui; Xiao, Pengfei

2011-06-01

Strain sensors made from MWNT/polymer nanocomposites / Gang Yin, Ning Hu and Yuan Li -- Shear band evolution and nanostructure formation in titanium by cold rolling / Dengke Yang, Peter D. Hodgson and Cuie Wen -- Biodegradable Mg-Zr-Ca alloys for bone implant materials / Yuncang Li ... [et al.] -- Hydroxyapatite synthesized from nanosized calcium carbonate via hydrothermal method / Yu-Shiang Wu, Wen-Ku Chang and Min Jou -- Modeling of the magnetization process and orthogonal fluxgate sensitivity of ferromagnetic micro-wire arrays / Fan Jie ... [et al.] -- Fabrication of silicon oxide nanowires on Ni coated silicon substrate by simple heating process / Bo Peng and Kwon-Koo Cho -- Deposition of TiOxNy thin films with various nitrogen flow rate: growth behavior and structural properties / S.-J. Cho ... [et al.] -- Observation on photoluminescence evolution in 300 KeV self-ion implanted and annealed silicon / Yu Yang ... [et al.] -- Facile synthesis of lithium niobate from a novel precursor H[symbol] / Meinan Liu ... [et al.] -- Effects of the buffer layers on the adhesion and antimicrobial properties of the amorphous ZrAlNiCuSi films / Pai-Tsung Chiang ... [et al.] -- Fabrication of ZnO nanorods by electrochemical deposition process and its photovoltaic properties / Jin-Hwa Kim ... [et al.] -- Cryogenic resistivities of NbTiAlVTaLax, CoCrFeNiCu and CoCrFeNiAl high entropy alloys / Xiao Yang and Yong Zhang -- Modeling of centrifugal force field and the effect on filling and solidification in centrifugal casting / Wenbin Sheng, Chunxue Ma and Wanli Gu -- Electrochemical properties of TiO[symbol] nanotube arrays film prepared by anodic oxidation / Young-Jin Choi ... [et al.] -- Effect of Ce additions on high temperature properties of Mg-5Sn-3Al-1Zn alloy / Byoung Soo Kang ... [et al.] -- Sono-electroless plating of Ni-Mo-P film / Atsushi Chiba, Masato Kanou and Wen-Chang Wu -- Diameter dependence of giant magneto-impedance effect in co-based melt extracted amorphous wires / Shuling Zhang, Dawei Xing and Jianfei Sun -- Effect of Yb addition on the microstructure and tensile properties of Mg-5Al alloy / Su Mi Jo ... [et al.] -- Finite element analysis of the warm deep-drawing process of magnesium matrix composite reinforced with CNTs / Li Weixue and Zhang Hujun -- Effect of ultrasonic shot peening on the microstructural evolution and mechanical properties of SUS304 / Deokgi Ahn ... [et al.] -- Microstructure of Fe-Cr surface infiltrated composite layer on gray iron substrate / Gui-Rong Yang ... [et al.] -- Effect of carbon contents and Ti addition on the microstructure of ultra-low carbon steel / Yinsheng He ... [et al.].Microstructure and mechanical property of laser direct manufacturing metal thin wall cylinder / X. D. Zhang ... [et al.] -- Evolution of morphology and composition of the carbides in Cr-Mo-V steel after service exposure / Jiling Dong ... [et al.] -- Thermal annealing treatment to achieve switchable and reversible wettability on ZnO nanowires surface / Changsong Liu ... [et al.] -- Physical and electrochemical properties of nanostructured nickel sulfide as a cathode material for lithium ion batteries / Seong-Ju Sim ... [et al.] -- Effect of heat treatment on fatigue behavior of biomedical Ni-Ti alloy wires under ultrasonic conditions / Zhou Huimin ... [et al.] -- The electrochemical behavior of Mg-Ce-Zn system / Kyung Chul Park ... [et al.] -- Fabrication of highly-oleophobic and superhydrophobic surfaces on microtextured Al substrates / Changsong Liu ... [et al.] -- Effect of cooling rate on microstructure and properties of Fe3Al intermetallics / Li Ya-Min, Liu Hong-Jun and Hao Yuan -- Calculation of laser transformation hardening with a circle beam / Binggong Yan and Jichang Liu -- The application of the unified homogeneous periodical boundary conditions to the prediction of effective elastic stiffness in a widespread field / Dong Yu, Hong Yang and Dong-Mei Luo -- Cyclic visco-plastic behavior of API X80 line-pipe steel and its finite element simulation / Kyong-Ho Chang and Gab-Chul Jang -- Residual stress distribution of 600MPa grade high tensile strength steel pipe using welding FE simulation / Kyong-Ho Chang and Gab-Chul Jang -- In-situ preparation and magnetic properties of Fe[symbol]O[symbol]/wood composite / Honglin Gao ... [et al.] -- The application of the cohesive zone model on the analysis of mechanical properties of carbon nano-tube composites with debonding interface / Wen-Liang Zhu and Dong-Mei Luo -- Microstructures and mechanical properties of As-Cast Mg-Zr-Ca alloys for biomedical applications / Ying-Long Zhou ... [et al.] -- Effect of polyurethane/nano-SiO[symbol] composites coating on thermo-mechanical properties of polyethylene film / Ching Yern Chee and Iskandar Idris Yaacob -- Effects evaluation for different rare earth elements in magnesium-lithium alloy / Bin Jiang ... [et al.] -- Effect of sintering temperature on the structure and bioactivity of HAp-5.0wt.%SO[symbol] bioceramic composites / Xiao-Wu Li ... [et al.] -- Study on the high cycle fatigue property of Ti-600 alloy at ambient temperature / Liying Zeng ... [et al.] -- Study on deformation-induced ferrite transformation of steel 2.25Cr1MoNb / Li Qing-Fen, Zhou Hui-Min and Chen Hong-Bin -- Effect of Fe addition on the cycle performance of FeS2 cathode for Li/FeS[symbol] battery / Young-Jin Choi ... [et al.] -- Effect of annealing process on recrystallization microstructure and texture of low carbon steel strip / Haiyan Wang ... [et al.].Grain-boundary segregation and co-segregation behavior of three elements in steel 2.25Gr1Mo / Wang Jun ... [et al.] -- Effect of partial crystallization on the mechanical properties of [symbol] bulk metallic glass / P. H. Tsai ... [et al.] -- Influence of plastic deformation on the evolution of defect structures, microhardness and electrical conductivity of copper / Jingmei Tao ... [et al.] -- Microstructure and room temperature mechanical properties of the Ni[symbol]Si-based alloy with titanium addition / S. K. Wang ... [et al.] -- Improvement of magnetic properties and size of directly casted Nd-Fe-B bulk magnets by Ti/Zr cosubstitutions / H. W. Chang ... [et al.] -- Wear behavior of the ceramic coatings on the Al6061 alloy prepared by plasma electrolytic oxidation / Jin Long Bian ... [et al.] -- Hydrogels with rapid thermal-responsibility by using liquid crystallite as template / Qingsong Zhang ... [et al.] -- The effects of TiO[symbol] buffer layer in carbon nanotubes growth on Ti substrate by thermal chemical vapor deposition and their electrochemical properties / Yong-Hwan Gwon ... [et al.] -- Phase transfer catalytic synthesis of 4-Benzyloxyl-3-Methoxylbenzaldehyde-Copolystyrene resin / Qiang Huang and Baozhong Zheng -- Compressive behaviour of nanocrystallilne Mg-5%Al alloys / H. Diao ... [et al.] -- Predicting the formation enthalpies of Al-Ga-In, Al-Ga-Sn, Cd-Ga-Sn and Ga-Sn-Zn liquid alloys by molecular interaction volume model / Hongwei Yang, Dongping Tao and Qingmei Yuan -- Low-temperature preparation and properties of high activity anatase TiO[symbol] aqueous sols / Qingju Liu ... [et al.] -- Effects of Ge mole fraction on electrical characteristics of strained SiGe channel p-MOSFET / Zhou Yang ... [et al.] -- Evaluation of oxidation and mechanical properties of the nano-sized WC-10%Nicrobraz composites consolidated by high frequency induction heated sintering / Duck-Soo Kang ... [et al.] -- Effect of ECAP on the high-temperature compressive deformation behavior of LY12 aluminum alloys / Qing-Wei Jiang ... [et al.] -- Surface energy effect on polymers adhesive bonding at room temperature / Yingxia Jin ... [et al.] -- Annealing effects on selfassembled Ge/Si (100) islands prepared by ion beam sputtering / Jie Yang ... [et al.] -- Effect of Gd on the microstructures and corrosion behaviors of magnesium alloy Mg-8.0Al-1.0Zn / Li Lei, Xie Shuisheng and Huang Guojie -- Synthesis, characterization and sensing properties of Perovskite EuFe[symbol] materials / Huen Kan ... [et al.] -- Synthesis and characterization of Ni(OH)[symbol] nanosheets by a simple route at low temperature / Qian Li ... [et al.] -- The prediction of laser clad parameters based on neural network / Jichang Liu and Libin Ni -- The effects of Y[symbol] doping on the phase structure and photoluminescence properties of (Gd[symbol]) red phosphors / Qi Zhu ... [et al.] -- Design of an in situ detection system for laser hardened width / Caixia Yang and Jichang Liu -- Numerical simulation microstructure morphology evolution and solute microsegregation of Al-Si-Cu ternary alloys during solidification process / Shuisheng Xie ... [et al.].A shear-lag model for carbon nonotube-reinforced magnesium matrix composites / Wei-Xue Li ... [et al.] -- Corrosion behavior of the Alumina Coated Al6061 Alloy by Plasma electrolytic oxidation / Kai Wang ... [et al.] -- A simple route for synthesis of tin dioxide nanorods based on improved solid-state reactions / Yuehua Li ... [et al.] -- Comparative study on microstructure and magnetic properties of amorphous wires with different diameters / Jing-Shun Liu ... [et al.] -- Chemical-Vapor-Depositing (CVD) aluminium film on steel surface with the disproportionation reaction of Al[symbol]S / Wu Guoyuan and Dai Yongnian -- The microstructure and properties of super martensitic stainless steel microalloyed with tungsten and copper / Dong Ye ... [et al.] -- Design of low elastic modulus Ti-Nb-Zr alloys for implant materials / Xiping Song ... [et al.] -- In situ monitoring molten pool parameters for detecting visible defects in laser cladding / Liusha Yang ... [et al.].

Biomimetic Oxygen-Evolving Photobacteria Based on Amino Acid and Porphyrin Hierarchical Self-Organization.

PubMed

Liu, Kai; Zhang, Han; Xing, Ruirui; Zou, Qianli; Yan, Xuehai

2017-12-26

Biomimetic organization provides a promising strategy to develop functional materials and understand biological processes. However, how to mimic complex biological systems using simple biomolecular units remains a great challenge. Herein, we design and fabricate a biomimetic cyanobacteria model based on self-integration of small bioinspired molecules, including amphiphilic amino acid, 3,4-dihydroxyphenylalanine (DOPA), and metalloporphyrin and cobalt oxide nanoparticles (Co 3 O 4 NPs), with the assistance of chemical conjugation and molecular self-assembly. The assembled amino acid fiber can be modified by DOPA to form covalently bound DOPA melanin containing hydroxyl and quinone species via Schiff base reaction. The adhering template can further tune the self-assembly of metalloporphyrin and Co 3 O 4 NPs into J-aggregation and dispersive distribution, respectively, mainly via coordination binding. Metalloporphyrin molecules in the resulting hybrid fibers capture light; quinone species accept the excited electrons, and Co 3 O 4 NPs catalyze water oxidation. Thus, the essential components of the photosystem-II protein complex in cyanobacteria are simplified and engineered into a simple framework, still retaining a similar photosynthetic mechanism. In addition, this architecture leads to efficient coupling of antenna, quinone-type reaction center, and photocatalyst, which increases the flux of light energy from antenna to reaction center for charge separation, resulting in enhanced oxygen evolution rate with excellent sustainability.

Effect of wheel speed and annealing temperature on microstructure and texture evolution of Ni{sub 45}Mn{sub 36.6}In{sub 13.4}Co{sub 5} ribbon

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

Feng, Yan, E-mail: yanfeng@nwpu.edu.cn

Ni{sub 45}Mn{sub 36.6}In{sub 13.4}Co{sub 5} magnetic shape memory alloy was successfully produced as preferentially textured ribbon by melting spinning with different wheel speed. X-ray diffraction (XRD) and electron back scatter diffraction (EBSD) were used to study structure and texture evolution of these melt-spun ribbons. The thickness of melt-spun ribbon is 42 μm, 65 μm and 30 μm depending on wheel speed of 1 0 m/s, 15 m/s and 20 m/s, respectively. Density of α fiber texture (〈100〉//ND) vary with wheel speed changes, and is most intensive in the ribbon with wheel speed of 15 m/s. Grains of the ribbons growmore » after being annealed at 873 K, 973 K, 1073 K and 1173 K, recrystallization was not observed in ribbons after being annealed at 873 K but occurred in ribbons after being annealed at higher temperatures. The α fiber texture becomes weaker to some extent after annealing at different temperatures, due to new recrystallization texture formed at the process of annealing. - Highlights: •Sectional part of shape memory ribbon is firstly investigated by EBSD method. •Thickness and texture of ribbons vary with wheel speed. •Annealing temperature affect texture and microstructure evolution greatly. •Recrystallization textures were observed in ribbons after being annealed.« less

Production of carbon molecular sieves from Illinois coal

USGS Publications Warehouse

Lizzio, A.A.; Rostam-Abadi, M.

1993-01-01

Carbon molecular sieves (CMS) have become an increasingly important class of adsorbents for application in the separation of gas molecules that vary in size and shape. A study is in progress at the Illinois State Geological Survey to determine whether Illinois basin coals are suitable feedstocks for the production of CMS and to evaluate their potential application in gas separation processes of commercial importance. Chars were prepared from Illinois coal in a fixed-bed reactor under a wide range of heat treatment and activation conditions. The effects of various coal/char pretreatments, including coal demineralization, preoxidation, char activation, and carbon deposition, on the molecular sieve properties of the chars were also investigated. Chars with commercially significant BET surface areas of 1500 m2/g were produced by chemical activation using potassium hydroxide as the activant. These high-surface-area (HSA) chars had more than twice the adsorption capacity of commercial carbon and zeolite molecular sieves. The kinetics of adsorption of various gases, e.g., N2, O2, CO2, CH4, CO and H2, on these chars at 25??C was measured. The O2/N2 molecular sieve properties of one char prepared without chemical activation were similar to those of a commercial CMS. On the other hand, the O2/N2 selectivity of the HSA char was comparable to that of a commercial activated carbon, i.e., essentially unity. Carbon deposition, using methane as the cracking gas, increased the O2/N2 selectivity of the HSA char, but significantly decreased its adsorption capacity. Several chars showed good potential for efficient CO2/CH4 separation; both a relatively high CO2 adsorption capacity and CO2/CH4 selectivity were achieved. The micropore size distribution of selected chars was estimated by equilibrium adsorption of carbon dioxide, n-butane and iso-butane at O??C. The extent of adsorption of each gas corresponded to the effective surface area contained in pores with diameters greater than 3.3, 4.3 and 5.0 A??, respectively. Kinetic and equilibrium adsorption data provided complementary information on the molecular sieving capabilities and microstructure of the prepared chars. ?? 1993.

Characterization of Microstructure and Wear Resistance of PEO Coatings Containing Various Microparticles on Ti6Al4V Alloy

NASA Astrophysics Data System (ADS)

Li, Xinyi; Dong, Chaofang; Zhao, Qing; Pang, Yu; Cheng, Fasong; Wang, Shuaixing

2018-02-01

Titania-based composite coatings were prepared by plasma electrolytic oxidation (PEO) treatment of Ti6Al4V alloy in electrolyte with α-Al2O3, Cr2O3 or h-BN microparticles in suspension. The microstructure, composition of PEO composite coatings were analyzed by SEM, EDS and XRD. The wear resistance of composite ceramic coatings was studied by ball-on-disk wear test at ambient temperature and 300 °C. The results showed that the addition of microparticles accelerated the growth rate of PEO coating and changed the microstructure and composition of PEO coating. PEO coating was porous and mainly composed of rutile-TiO2, anatase-TiO2 and Al2TiO5. PEO/α-Al2O3 (Cr2O3 or h-BN) composite coating only had small micropores and appeared some α-Al2O3 (Cr2O3 or h-BN) phase. Besides, the addition of α-Al2O3 (Cr2O3 or h-BN) microparticles greatly improved the wear resistance of PEO coating. At ambient temperature, abrasive wear dominated the wear behavior of PEO coating, but abrasive wear and adhesive peel simultaneously happened at 300 °C. Whether at ambient temperature or 300 °C, PEO composite coating had better wear resistance than PEO coating. Besides, PEO/h-BN composite coating outperformed other composite coatings regardless of the temperature.

Microstructural and strength improvements through the use of Na{sub 2}CO{sub 3} in a cementless Ca(OH){sub 2}-activated Class F fly ash system

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

Jeon, Dongho; Jun, Yubin; Jeong, Yeonung

2015-01-15

This study explores the beneficial effects of Na{sub 2}CO{sub 3} as an additive for microstructural and strength improvements in a Ca(OH){sub 2}-activated fly ash system. NaOH-activated fly ash samples were also tested to compare the effect of Na{sub 2}CO{sub 3}. Compressive strength testing, XRD, SEM/BSE/EDS, {sup 29}Si/{sup 27}Al MAS-NMR, MIP and TGA were performed. The testing results indicate that the use of Na{sub 2}CO{sub 3} for Ca(OH){sub 2}-activation led to a noticeable improvement in strength and microstructure, primarily due to (1) more dissolution of raw fly ash at an early age, (2) more formation of C–S–H [or C–S–H(I)], (3) porositymore » reduction, and (4) pore-size refinement. We also found that (1) an early high alkalinity from the NaOH formation was not a major cause of strength, (2) geopolymer was not formed despite the early NaOH formation, and (3) no visible pore-filling action of CaCO{sub 3} was observed. However, Na{sub 2}CO{sub 3} did not produce any improvement in strength for NaOH-activated fly ash. -- Highlights: •The use of Na{sub 2}CO{sub 3} significantly improved strength and microstructure. •The use of Na{sub 2}CO{sub 3} induced more dissolution of raw fly ash at early ages. •The use of Na{sub 2}CO{sub 3} promoted more C–S–H [or C–S–H(I)] formation. •The use of Na{sub 2}CO{sub 3} reduced total porosity and refined pore-size distribution. •The use of Na{sub 2}CO{sub 3} produced neither geopolymer formations nor pore-filling actions from CaCO{sub 3}.« less

Catalysis of nickel ferrite for photocatalytic water oxidation using [Ru(bpy)3]2+ and S2O8(2-).

PubMed

Hong, Dachao; Yamada, Yusuke; Nagatomi, Takaharu; Takai, Yoshizo; Fukuzumi, Shunichi

2012-12-05

Single or mixed oxides of iron and nickel have been examined as catalysts in photocatalytic water oxidation using [Ru(bpy)(3)](2+) as a photosensitizer and S(2)O(8)(2-) as a sacrificial oxidant. The catalytic activity of nickel ferrite (NiFe(2)O(4)) is comparable to that of a catalyst containing Ir, Ru, or Co in terms of O(2) yield and O(2) evolution rate under ambient reaction conditions. NiFe(2)O(4) also possesses robustness and ferromagnetic properties, which are beneficial for easy recovery from the solution after reaction. Water oxidation catalysis achieved by a composite of earth-abundant elements will contribute to a new approach to the design of catalysts for artificial photosynthesis.

Microstructure, electronic structure and optical properties of combustion synthesized Co doped ZnO nanoparticles

NASA Astrophysics Data System (ADS)

Srinatha, N.; Nair, K. G. M.; Angadi, Basavaraj

2015-10-01

We report on the microstructure, electronic structure and optical properties of nanocrystalline Zn1-xCoxO (x=0, 0.01, 0.03, 0.05 and 0.07) particles prepared by solution combustion technique using L-Valine as fuel. The detailed structural and micro-structural studies were carried out by XRD, HRTEM and TEM-SAED respectively, which confirms the formation of single phased, nano-sized particles. The electronic structure was determined through NEXAFS and atomic multiplet calculations/simulations performed for various symmetries and valence states of 'Co' to determine the valance state, symmetry and crystal field splitting. The correlations between the experimental NEXAFS spectra and atomic multiplet simulations, confirms that, 'Co' present is in the 2+ valence state and substituted at the 'Zn' site in tetrahedral symmetry with crystal field splitting, 10Dq =-0.6 eV. The optical properties and 'Co' induced defect formation of as-synthesized materials were examined by using diffuse reflectance and Photoluminescence spectroscopy, respectively. Red-shift of band gap energy (Eg) was observed in Zn1-xCoxO samples due to Co (0.58 Å) substitution at Zn (0.60 Å) site of the host ZnO. Also, in PL spectra, a prominent pre-edge peak corresponds to ultraviolet (UV) emission around 360-370 nm was observed with Co concentration along with near band edge emission (NBE) of the wide band gap ZnO and all samples show emission in the blue region.

Dendrite-like Co3O4 nanostructure and its applications in sensors, supercapacitors and catalysis.

PubMed

Pang, Huan; Gao, Feng; Chen, Qun; Liu, Rongmei; Lu, Qingyi

2012-05-21

Dendrite-like Co(3)O(4) nanostructure, made up of many nanorods with diameters of 15-20 nm and lengths of 2-3 μm, has been successfully prepared by calcining the corresponding nanostructured Co-8-hydroxyquinoline coordination precursor in air. The Co(3)O(4) nanostructure was evaluated as an electrochemical sensor for H(2)O(2) detection and the results reveal that it has good linear dependence and high sensitivity to H(2)O(2) concentration changes. As an electrode material of a supercapacitor, it was found that the nanostructured Co(3)O(4) electrode exhibits high specific capacitance and long cycle life. The Co(3)O(4) nanostructure also has good catalytic properties and is steadily active for CO oxidation, giving 100% CO conversion at low temperatures. The multifunctional Co(3)O(4) nanostructure would be a promising functional nanomaterial applied in multi industrialized fields.

Influence of Li3BO3 additives on the Li+ conductivity and stability of Ca/Ta-substituted Li6.55(La2.95Ca0.05)(Zr1.5Ta0.5)O12 electrolytes

NASA Astrophysics Data System (ADS)

Zhang, L. C.; Yang, J. F.; Gao, Y. X.; Wang, X. P.; Fang, Q. F.; Chen, C. H.

2017-07-01

The cubic Ca/Ta-substituted Li6.55(La2.95Ca0.05)(Zr1.5Ta0.5)O12 (LLCZTO) electrolytes were synthesized at 800 °C with Li3BO3 as additives. The optimal amount of Li3BO3 and its influences on the microstructure, crystal structures, Li+ conductivity and the stability of the Li6.55(La2.95Ca0.05)(Zr1.5Ta0.5)O12 were studied by SEM, XRD and EIS. Among all the samples, when the molar ratio of Li3BO3 to the Li6.55(La2.95Ca0.05)(Zr1.5Ta0.5)O12 is 4:5, the highest Li+ conductivity of 1.33 × 10-4 S cm-1 at 30 °C is obtained. When the LLCZTO samples are exposed in air, the Li+ conductivity is deteriorated possibly owing to the side reactions between the LLCZTO and the H2O or CO2 in the air. The Li3BO3 addition can alleviate such deterioration of the Li+ conductivity.

Effects of cation contaminants in conductive TiO2 ceramics

NASA Astrophysics Data System (ADS)

Yan, M. F.; Rhodes, W. W.

1982-12-01

Ten cation contaminants, namely Al, Ga, Co, Fe, Mg, Zn, Zr, Ca, Sr, and Ba were investigated for their effects on the electrical properties, microstructures, and discoloration of conductive TiO2 ceramics. It was found that Al, Ga, Co, Fe, and Mg cause discoloration and increase the electrical resistivity by a factor of 104 to 106 in Nb-doped TiO2 ceramics. The other dopants do not introduce such changes in TiO2. The electrical properties, microstructures, and discoloration were measured in specimens of AlxNb0.007Ti0.993-xO2 with 0≤x≤0.01. When the Al content exceeds a critical value, ranging from 0.48% at 1400 °C to 0.25% at 1200 °C, the electrical resistivities and grain size increase rapidly, and the specimen is discolored from the original black to an ivory white color. Color boundary migration induced by Al diffusion in Nb-doped TiO2 was quantitatively measured. From the kinetics of the boundary migration, the Al diffusivity (D) was calculated to be D=2.67 exp(-53.3 kcal/mole/RT) cm2/s in the temperature range of 1200 to 1400 °C. The rapid diffusion of the small cations, namely Al, Ga, Co, Fe, and Mg, results from an interstitial diffusion mechanism. However, other cations, having a radius larger than the interstitial channel (˜0.77 Å radius), cannot diffuse by this mechanism. Defect reactions are proposed to explain the increase in the electrical resistivity and microstructural changes due to Al diffusion. These defect reactions also show that the problem of acceptor contamination cannot be avoided by adding an excess quantity of donor dopant if the solubility of the donor is much less than that of the acceptor contaminant.

Microstructure development and photoluminescence of annealed nanosized Ce:YAG/Al2O3 and Ce:YAG/Cr:Al2O3 powder composites

NASA Astrophysics Data System (ADS)

Peter, Samuel; Kuyanov, Paul; Isik Goktas, Nebile; LaPierre, Ray; Kitai, Adrian

2018-03-01

In an effort to control aggregation and sintering of phosphor nanoparticles at elevated annealing temperatures, glycothermally synthesized cerium-doped yttrium aluminum garnet (Ce:YAG) nanoparticles were annealed in a matrix of aluminum oxide between 1000 °C and 1200 °C. Scanning electron microscopy images showed that glycothermal synthesis yields ∼100 nm particles, and that the alumina matrix was able to control grain growth of Ce:YAG at annealing temperatures up to 1200 °C. Analysis by x-ray diffraction and Fourier transform infrared spectroscopy showed an increase in the degree of crystallinity at increasing temperatures as well as the evolution of alumina phases. Photoluminescence of the composite product showed the expected broad Ce:YAG spectrum, with characteristic chromium R lines present due to the formation of corundum at 1200 °C with trace chromium content. The same procedure was performed to synthesize a Ce:YAG/Cr:Al2O3 nanocomposite, yielding photoluminescence of both the expected Ce:YAG and Cr:Al2O3 peaks as well as clear evidence of energy transfer between Ce and Cr centers in YAG. The luminescence of these composites was used to determine their CIE colour co-ordinates. It was found that the colour profile of the resulting emission may be tuned by adjusting the Cr content and annealing conditions of the composite materials.

Controllable Fabrication and Tuned Electrochemical Performance of Potassium Co-Ni Phosphate Microplates as Electrodes in Supercapacitors.

PubMed

Liang, Bo; Chen, Yule; He, Jiangyu; Chen, Chen; Liu, Wenwen; He, Yuanqing; Liu, Xiaohe; Zhang, Ning; Roy, Vellaisamy A L

2018-01-31

Most reported pristine phosphates, such as NH 4 MPO 4 ·H 2 O (M = Co, Ni), are not very stable as supercapacitor electrodes because of their chemical properties. In this work, KCo x Ni 1-x PO 4 ·H 2 O microplates were fabricated by a facile hydrothermal method at low temperature and used as electrodes in supercapacitors. The Co and Ni content could be adjusted, and optimal electrochemical performance was found in KCo 0.33 Ni 0.67 PO 4 ·H 2 O, which also possessed superior specific capacitance, rate performance, and long-term chemical stability compared with NH 4 Co 0.33 Ni 0.67 PO 4 ·H 2 O because of its unique chemical composition and microstructure. Asymmetric supercapacitor cells based on KCo 0.33 Ni 0.67 PO 4 ·H 2 O and active carbon were assembled, which produce specific capacitance of 34.7 mA h g -1 (227 F g -1 ) under current density of 1.5 A g -1 and retain 82% as initial specific capacitance after charging and discharging approximately 5000 times. The assembled asymmetric supercapacitor cells (ASCs) exhibited much higher power and energy density than most previously reported transition metal phosphate ASCs. The KCo x Ni 1-x PO 4 ·H 2 O electrodes fabricated in this work are efficient, inexpensive, and composed of naturally abundant materials, rendering them promising for energy storage device applications.

Thermoelectric transport properties of Ca3Co4- x Ni x O9+ δ oxide materials

NASA Astrophysics Data System (ADS)

Park, K.; Cha, J. S.; Nam, S. W.; Choi, S.-M.; Seo, W.-S.; Lee, S.; Lim, Y. S.

2016-01-01

Nano-sized Ca3Co4- x Ni x O9+ δ (0 ≤ x ≤ 0.3) thermoelectric powders are synthesized by using the solution combustion method, with aspartic acid as a combustion fuel. The synthesized Ca3Co4- x Ni x O9+ δ nano-sized powders exhibit a spherical-like shape and a smooth surface. Higher Ni content results in a smaller grain size and a higher porosity, resulting in a decrease in the electrical conductivity. However, the Seebeck coefficient of Ni-added Ca3Co4O9 is much higher than that of Ca3Co4O9. The highest power factor (1.4 × 10-4 Wm-1K-2), which is more than nine times larger than that of Ca3Co4O9, is attained for Ca3Co0.38Ni0.2O9+ δ at 800 °C. The addition of a small amount of Ni is highly effective in improving the thermoelectric properties of Ca3Co4O9. We believe that Ca3Co4- x Ni x O9+ δ is a potential p-type thermoelectric material for renewable energy conversion.

High-temperature deformation and microstructural analysis for Si3N4-Sc2O3

NASA Technical Reports Server (NTRS)

Cheong, Deock-Soo; Sanders, William A.

1990-01-01

It was indicated that Si3N4 doped with Sc2O3 may exhibit high temperature mechanical properties superior to Si3N4 systems with various other oxide sintered additives. High temperature deformation of samples was studied by characterizing the microstructures before and after deformation. It was found that elements of the additive, such as Sc and O, exist in small amounts at very thin grain boundary layers and most of them stay in secondary phases at triple and multiple grain boundary junctions. These secondary phases are devitrified as crystalline Sc2Si2O7. Deformation of the samples was dominated by cavitational processes rather than movements of dislocations. Thus the excellent deformation resistance of the samples at high temperature can be attributed to the very small thickness of the grain boundary layers and the crystalline secondary phase.

2011 Summer Student Research

DTIC Science & Technology

2012-08-29

material using solid reaction method for SOFC application. The start materials are Sr2CO3, Ga2O3 ,V2O5 and Sc2O3. The powders were mixed proportionally...according to the chemical reaction equation (1) and (2) as below: 4SrCO3+ V2O5+ Ga2O3 = 2 Sr2GaVO6+4CO2 (1) 4SrCO3+ V2O5+ Sc2O3 = 2 Sr2ScVO6+4CO2...the XRD patterns of the compound in air and H2 reduction atmosphere using Sr2CO3, Ga2O3 and V2O5 as starting materials, respectively. The main

Iron-Induced Activation of Ordered Mesoporous Nickel Cobalt Oxide Electrocatalyst for the Oxygen Evolution Reaction.

PubMed

Deng, Xiaohui; Öztürk, Secil; Weidenthaler, Claudia; Tüysüz, Harun

2017-06-28

Herein, ordered mesoporous nickel cobalt oxides prepared by the nanocasting route are reported as highly active oxygen evolution reaction (OER) catalysts. By using the ordered mesoporous structure as a model system and afterward elevating the optimal catalysts composition, it is shown that, with a simple electrochemical activation step, the performance of nickel cobalt oxide can be significantly enhanced. The electrochemical impedance spectroscopy results indicated that charge transfer resistance increases for Co 3 O 4 spinel after an activation process, while this value drops for NiO and especially for CoNi mixed oxide significantly, which confirms the improvement of oxygen evolution kinetics. The catalyst with the optimal composition (Co/Ni 4/1) reaches a current density of 10 mA/cm 2 with an overpotential of a mere 336 mV and a Tafel slope of 36 mV/dec, outperforming benchmarked and other reported Ni/Co-based OER electrocatalysts. The catalyst also demonstrates outstanding durability for 14 h and maintained the ordered mesoporous structure. The cyclic voltammograms along with the electrochemical measurements in Fe-free KOH electrolyte suggest that the activity boost is attributed to the generation of surface Ni(OH) 2 species that incorporate Fe impurities from the electrolyte. The incorporation of Fe into the structure is also confirmed by inductively coupled plasma optical emission spectrometry.

Morphology-controlled synthesis of Co{sub 3}O{sub 4} by one step template-free hydrothermal method

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

Zhou, Keqing; Liu, Jiajia; Wen, Panyue

2015-07-15

Highlights: • Co{sub 3}O{sub 4} crystals had been synthesized by one step template-free hydrothermal method. • The H{sub 2}O{sub 2} plays a crucial role in morphological control of Co{sub 3}O{sub 4} nanostructures. • The morphology has significant effect on the optical property of Co{sub 3}O{sub 4}. - Abstract: We had developed a facile synthetic route of Co{sub 3}O{sub 4} crystals with different morphologies via one step template-free hydrothermal method. The phase and composition of the Co{sub 3}O{sub 4} were investigated by X-ray powder diffraction and Raman spectrum. The morphology and structure of the synthesized samples were characterized by scanning electronmore » microscopy and transmission electron microscopy. The H{sub 2}O{sub 2} played a crucial role in morphological control of Co{sub 3}O{sub 4} nanostructures. It only obtained Co-based precursor in the absence of H{sub 2}O{sub 2}. On the contrary, the Co{sub 3}O{sub 4} with different morphologies including nanoparticles, nano-discs and well-defined octahedral nanostructures were synthesized in the presence of H{sub 2}O{sub 2}. In addition, the optical property of the obtained Co{sub 3}O{sub 4} samples was investigated by UV–vis spectra.« less

Low Temperature Superplasticity of Ti-6Al-4V Processed by Warm Multidirectional Forging (Preprint)

DTIC Science & Technology

2012-07-01

microstructure in the two-phase titanium alloy Ti- 6Al - 4V . A microstructure with a grain size of 135 nm was attained, enabling low-temperature...the / titanium alloy Ti- 6Al - 4V [3]. The great interest in microstructure refinement is associated with significantly reduced superplastic (SP...consisted of the / titanium alloy Ti- 6Al - 4V with a nominal composition (in weight pct.) of 6.3 Al, 4.1 V, 0.18 Fe, 0.03 Si, 0.02 Zr, 0.01 C, 0.18 O, 0.01 N

Catalytic properties of Co3O4 nanoparticles for rechargeable Li/air batteries.

PubMed

Kim, Kwan Su; Park, Yong Joon

2012-01-05

Three types of Co3O4 nanoparticles are synthesized and characterized as a catalyst for the air electrode of a Li/air battery. The shape and size of the nanoparticles are observed using scanning electron microscopy and transmission electron microscopy analyses. The formation of the Co3O4 phase is confirmed by X-ray diffraction. The electrochemical property of the air electrodes containing Co3O4 nanoparticles is significantly associated with the shape and size of the nanoparticles. It appears that the capacity of electrodes containing villiform-type Co3O4 nanoparticles is superior to that of electrodes containing cube- and flower-type Co3O4 nanoparticles. This is probably due to the sufficient pore spaces of the villiform-type Co3O4 nanoparticles.

Effect of annealing temperature on microstructural evolution and electrical properties of sol-gel processed ZrO2/Si films

NASA Astrophysics Data System (ADS)

Hwang, Soo Min; Lee, Seung Muk; Park, Kyung; Lee, Myung Soo; Joo, Jinho; Lim, Jun Hyung; Kim, Hyoungsub; Yoon, Jae Jin; Kim, Young Dong

2011-01-01

High-permittivity (k) ZrO2/Si(100) films were fabricated by a sol-gel technique and the microstructural evolution with the annealing temperature (Ta) was correlated with the variation of their electrical performance. With increasing Ta, the ZrO2 films crystallized into a tetragonal (t) phase which was maintained until 700 °C at nanoscale thicknesses. Although the formation of the t-ZrO2 phase obviously enhanced the k value of the ZrO2 dielectric layer, the maximum capacitance in accumulation was decreased by the growth of a low-k interfacial layer (IL) between ZrO2 and Si with increasing Ta. On the other hand, the gate leakage current was remarkably depressed with increasing Ta probably due to the combined effects of the increased IL thickness, optical band gap of ZrO2, and density of ZrO2 and decreased remnant organic components.

Brownmillerite-type Ca2 FeCoO5 as a Practicable Oxygen Evolution Reaction Catalyst.

PubMed

Tsuji, Etsushi; Motohashi, Teruki; Noda, Hiroyuki; Kowalski, Damian; Aoki, Yoshitaka; Tanida, Hajime; Niikura, Junji; Koyama, Yukinori; Mori, Masahiro; Arai, Hajime; Ioroi, Tsutomu; Fujiwara, Naoko; Uchimoto, Yoshiharu; Ogumi, Zempachi; Habazaki, Hiroki

2017-07-21

Here, we report remarkable oxygen evolution reaction (OER) catalytic activity of brownmillerite (BM)-type Ca 2 FeCoO 5 . The OER activity of this oxide is comparable to or beyond those of the state-of-the-art perovskite (PV)-catalyst Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ (BSCF) and a precious-metal catalyst RuO 2 , emphasizing the importance of the characteristic BM structure with multiple coordination environments of transition metal (TM) species. Also, Ca 2 FeCoO 5 is clearly advantageous in terms of expense/laboriousness of the material synthesis. These facts make this oxide a promising OER catalyst used in many energy conversion technologies such as metal-air secondary batteries and hydrogen production from electrochemical/photocatalytic water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Process for producing hydrogen from water using cobalt and barium compounds

DOEpatents

Bamberger, Carlos E.; Richardson, deceased, Donald M.

1979-01-01

A thermochemical process for producing hydrogen comprises the step of reacting CoO with BaO or Ba(OH).sub.2 in the presence of steam to produce H.sub.2 and novel double oxides of Ba and Co having the empirical formulas BaCoO.sub.2.33 and Ba.sub.2 CoO.sub.3.33. The double oxide can be reacted with H.sub.2 O to form Co.sub.3 O.sub.4 and Ba(OH).sub.2 which can be recycled to the original reaction. The Co.sub.3 O.sub.4 is converted to CoO by either of two procedures. In one embodiment Co.sub.3 O.sub.4 is heated, preferably in steam, to form CoO. In another embodiment Co.sub.3 O.sub.4 is reacted with aqueous HCl solution to produce CoCl.sub.2 and Cl.sub.2. The CoCl.sub.2 is reacted with H.sub.2 O to form CoO and HCl and the CoO is recycled to the initial reaction step. The Cl.sub.2 can be reacted with H.sub.2 O to produce HCl. HCl can be recycled for reaction with Co.sub.3 O.sub.4.

All-in-one: a versatile gas sensor based on fiber enhanced Raman spectroscopy for monitoring postharvest fruit conservation and ripening.

PubMed

Jochum, Tobias; Rahal, Leila; Suckert, Renè J; Popp, Jürgen; Frosch, Torsten

2016-03-21

In today's fruit conservation rooms the ripening of harvested fruit is delayed by precise management of the interior oxygen (O2) and carbon dioxide (CO2) levels. Ethylene (C2H4), a natural plant hormone, is commonly used to trigger fruit ripening shortly before entering the market. Monitoring of these critical process gases, also of the increasingly favored cooling agent ammonia (NH3), is a crucial task in modern postharvest fruit management. The goal of this work was to develop and characterize a gas sensor setup based on fiber enhanced Raman spectroscopy for fast (time resolution of a few minutes) and non-destructive process gas monitoring throughout the complete postharvest production chain encompassing storage and transport in fruit conservation chambers as well as commercial fruit ripening in industrial ripening rooms. Exploiting a micro-structured hollow-core photonic crystal fiber for analyte gas confinement and sensitivity enhancement, the sensor features simultaneous quantification of O2, CO2, NH3 and C2H4 without cross-sensitivity in just one single measurement. Laboratory measurements of typical fruit conservation gas mixtures showed that the sensor is capable of quantifying O2 and CO2 concentration levels with accuracy of 3% or less with respect to reference concentrations. The sensor detected ammonia concentrations, relevant for chemical alarm purposes. Due to the high spectral resolution of the gas sensor, ethylene could be quantified simultaneously with O2 and CO2 in a multi-component mixture. These results indicate that fiber enhanced Raman sensors have a potential to become universally usable on-site gas sensors for controlled atmosphere applications in postharvest fruit management.

Persistent luminescence in powdered and ceramic polycrystalline Gd3Al2Ga3O12:Ce

NASA Astrophysics Data System (ADS)

Dosovitskiy, G.; Fedorov, A.; Mechinsky, V.; Borisevich, A.; Dosovitskiy, A.; Tret'jak, E.; Korjik, M.

2017-02-01

This paper studies powders of Gd3Ga3Al2O12:Ce, a promising scintillator composition, as a possible object for express pre-characterization of scintillation kinetics and level of persistent luminescence. Garnet phase powders with uniform microstructure, consisting of 1-2 μm grains, were obtained by co-precipitation approach. It was shown, that both scintillation decay time and presence of persistent luminescence are influenced by both powder thermal treatment temperature and strong Ga deficit.

Solution Combustion Synthesis of Ni/NiO/ZnO Nanocomposites for Photodegradation of Methylene Blue Under Ultraviolet Irradiation

NASA Astrophysics Data System (ADS)

Biglari, Z.; Masoudpanah, S. M.; Alamolhoda, S.

2018-02-01

In this work, Ni/NiO/ZnO nanocomposites were synthesized by the one-pot solution combustion synthesis method. Phase evolution investigated by the x-ray diffraction method showed that the ZnO and NiO contents can be tuned by addition of a zinc precursor. The microstructure characterized by electron microscopy exhibited granular morphology with a particle size of 1.1 μm decreasing to 90 nm as a function of the amounts of ZnO and NiO phases. Specific surface area determined by N2 adsorption-desorption isotherms increased from 1.4 m2/g to 25.6 m2/g with the increase of oxide phases. However, the saturation magnetization decreased from 51.3 emu/g to 25.9 emu/g in the presence of antiferromagnetic NiO and nonmagnetic ZnO phases. Photodegradation of methylene blue under ultraviolet light exhibited the maximum efficiency in the sample containing 16.25 wt.% of ZnO and 21.25 wt.% of NiO, and may be due to the synergic effect between ZnO and NiO.

Surface damage mitigation of TC4 alloy via micro arc oxidation for oil and gas exploitation application: Characterizations of microstructure and evaluations on surface performance

NASA Astrophysics Data System (ADS)

Xie, Ruizhen; Lin, Naiming; Zhou, Peng; Zou, Jiaojuan; Han, Pengju; Wang, Zhihua; Tang, Bin

2018-04-01

Because of its excellent corrosion resistance, high specific strength and high tensile strength, TC4 titanium alloys used as petroleum tubes have received wide interest from material engineers after many technical investigations and estimations. However, because of its low surface hardness values, high coefficient of friction and poor wear resistance, the TC4 alloy is seldom adopted in tribological-related engineering components. In this work, micro-arc oxidation (MAO) coatings were fabricated on TC4 alloys in NaAlO2 and (NaPO3)6 electrolytes with and without ultrasonic assistance. The microstructural characterizations of the produced MAO coatings were investigated. Comparative estimations of electrochemical corrosion in CO2-saturated simulated oilfield brine and tribological behaviours on MAO coatings and TC4 alloys were conducted. The results showed that the introduction of ultrasound increased the thickness of the MAO coatings. The thickness increased by 34% and 15% in the NaAlO2 and (NaPO3)6 electrolytes, respectively. There was no significant discrepancy in phase constitutions when the MAO processes were conducted with and without ultrasonic assistance. Both MAO coatings obtained with and without ultrasonic assistance were found to improve the corrosion and wear resistance of the TC4 alloy. MAO treatments made it possible to ensure the working surface of a TC4 alloy with an enhanced surface performance for oil and gas exploitation applications.

A comprehensive overview on the structure and comparison of magnetic properties of nanocrystalline synthesized by a thermal treatment method

NASA Astrophysics Data System (ADS)

Naseri, Mahmoud Goodarz; Halimah, M. K.; Dehzangi, Arash; Kamalianfar, Ahmad; Saion, Elias B.; Majlis, Burhanuddin Y.

2014-03-01

This study reports the simple synthesis of MFe2O4 (where M=Zn, Mn and Co) nanostructures by a thermal treatment method, followed by calcination at various temperatures from 723 to 873 K. Poly(vinyl pyrrolidon) (PVP) was used as a capping agent to stabilize the particles and prevent them from agglomeration. The pyrolytic behaviors of the polymeric precursor were analyzed by use of simultaneous thermo-gravimetry analyses (TGA) and derivative thermo-gravimetry (DTG) analyses. The characterization studies were conducted by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Fourier transform infrared spectroscopy (FT-IR) confirmed the presence of metal oxide bands for all the calcined samples. Magnetic properties were demonstrated by a vibrating sample magnetometer (VSM), which displayed that the calcined samples exhibited different types of magnetic behavior. The present study also substantiated that magnetic properties of ferrite nanoparticles prepared by the thermal treatment method, from viewing microstructures of them, can be explained as the results of the two important factors: cation distribution and impurity phase of α-Fe2O3. These two factors are subcategory of the preparation method which is related to macrostructure of ferrite. Electron paramagnetic resonance (EPR) spectroscopy showed the existence of unpaired electrons ZnFe2O4 and MnFe2O4 nanoparticles while it did not exhibit resonance signal for CoFe2O4 nanoparticles.

Cathodic Electrodeposition of Ni-Mo on Semiconducting NiFe2 O4 for Photoelectrochemical Hydrogen Evolution in Alkaline Media.

PubMed

Wijten, Jochem H J; Jong, Ronald P H; Mul, Guido; Weckhuysen, Bert M

2018-04-25

Photocathodes for hydrogen evolution from water were made by electrodeposition of Ni-Mo layers on NiFe 2 O 4 substrates, deposited by spin coating on F:SnO 2 -glass. Analysis confirmed the formation of two separate layers, without significant reduction of NiFe 2 O 4 . Bare NiFe 2 O 4 was found to be unstable under alkaline conditions during (photo)electrochemistry. To improve the stability significantly, the deposition of a bifunctional Ni-Mo layer through a facile electrodeposition process was performed and the composite electrodes showed stable operation for at least 1 h. Moreover, photocurrents up to -2.1 mA cm -2 at -0.3 V vs. RHE were obtained for Ni-Mo/NiFe 2 O 4 under ambient conditions, showing that the new combination functions as both a stabilizing and catalytic layer for the photoelectrochemical evolution of hydrogen. The photoelectrochemical response of these composite electrodes decreased with increasing NiFe 2 O 4 layer thickness. Transient absorption spectroscopy showed that the lifetime of excited states is short and on the ns timescale. An increase in lifetime was observed for NiFe 2 O 4 of large layer thickness, likely explained by decreasing the defect density in the primary layer(s), as a result of repetitive annealing at elevated temperature. The photoelectrochemical and transient absorption spectroscopy results indicated that a short charge carrier lifetime limits the performance of Ni-Mo/NiFe 2 O 4 photocathodes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

PREPARATION OF FLOWER-LIKE Co3O4/Fe3O4 MAGNETIC MICROSPHERES FOR PHOTODEGRADATION OF RhB UNDER UV LIGHT

NASA Astrophysics Data System (ADS)

Zhang, Baoliang; Zhang, Hepeng; Zhou, Lunwei; Ali, Nisar; Geng, Wangchang; Zhang, Qiuyu

2013-07-01

Flower-like Co3O4/Fe3O4 magnetic microspheres were prepared by coprecipitation of Fe2+ and Fe3+ in presence of flower-like Co3O4 microspheres as template. The preparation process included three steps: preparation of flower-like Co3O4 microspheres by hydrothermal method; immersion of Fe2+ and Fe3+ ions; coprecipitation in the presence of OH-. Rhodamine B (RhB) was chosen as model pollutants to investigate the photodegradation capacities of Co3O4/Fe3O4 magnetic microspheres. The results showed that the microspheres exhibited excellent degradation property and can be recycled to use again. After four times use the degradation efficiency was still above 90%.

Structural and thermal stabilities of layered Li(Ni 1/3Co 1/3Mn 1/3)O 2 materials in 18650 high power batteries

NASA Astrophysics Data System (ADS)

He, Yan-Bing; Ning, Feng; Yang, Quan-Hong; Song, Quan-Sheng; Li, Baohua; Su, Fangyuan; Du, Hongda; Tang, Zhi-Yuan; Kang, Feiyu

The structural and thermal stabilities of the layered Li(Ni 1/3Co 1/3Mn 1/3)O 2 cathode materials under high rate cycling and abusive conditions are investigated using the commercial 18650 Li(Ni 1/3Co 1/3Mn 1/3)O 2/graphite high power batteries. The Li(Ni 1/3Co 1/3Mn 1/3)O 2 materials maintain their layered structure even when the power batteries are subjected to 200 cycles with 10 C discharge rate at temperatures of 25 and 50 °C, whereas their microstructure undergoes obvious distortion, which leads to the relatively poor cycling performance of power batteries at high charge/discharge rates and working temperature. Under abusive conditions, the increase in the battery temperature during overcharge is attributed to both the reactions of electrolyte solvents with overcharged graphite anode and Li(Ni 1/3Co 1/3Mn 1/3)O 2 cathode and the Joule heat that results from the great increase in the total resistance (R cell) of batteries. The reactions of fully charged Li(Ni 1/3Co 1/3Mn 1/3)O 2 cathodes and graphite anodes with electrolyte cannot be activated during short current test in the fully charged batteries. However, these reactions occur at around 140 °C in the fully charged batteries during oven test, which is much lower than the temperature of about 240 °C required for the reactions outside batteries.

Observations of CO2 in Comets C/2012 S1 ISON and C/2012 K1 PANSTARRS

NASA Astrophysics Data System (ADS)

McKay, Adam; Kelley, Michael; DiSanti, Michael; Cochran, Anita; Dello Russo, Neil; Lisse, Carey; Chanover, Nancy

2013-10-01

Comets have undergone very little thermal evolution in their lifetimes, resulting in a primitive composition. This primitive composition makes observations of comets very important tools for understanding the origin of the Solar System. The ices H2O, CO2, and CO are the primary ices present in cometary nuclei, and constraining their abundances has tremendous implications for the formation and evolutionary history of comets. Of these ices, H2O and CO can be observed from the ground, while CO2 cannot. A potentially effective tracer for CO2 in comets that is accessible from the ground is atomic oxygen. However, the relationship between these ices and atomic oxygen is only understood at a qualitative level. We propose to use Spitzer observations in IRAC's 4.5 micron band pass to observe the CO2 v3 band at 4.26 microns in comets C/2012 S1 ISON and C/2012 K1 PANSTARRS. These observations will be coordinated with observations of atomic oxygen obtained at Apache Point Observatory and McDonald Observatory and observations of H2O and CO at Keck and IRTF. These observations of H2O, CO2, and atomic oxygen in a cometary coma will increase our understanding of the link between these primary ices and atomic oxygen. With a complete understanding of the relationship between atomic oxygen and the primary ices on the nucleus, observations of atomic oxygen can serve as a powerful proxy for the production of CO2. In addition, ISON is the target of an extensive observing campaign led by NASA, and the proposed Spitzer observations fill a vital niche as the only observatory that can observe CO2 during both the near-perihelion time frame and significantly (months) after perihelion. Understanding the evolution of the CO2 abundance over the apparition is a key piece to understanding how the volatile compostion of the comet changes over the apparition.

Microstructural and magnetic property evolution with different heat-treatment conditions in an alnico alloy

DOE PAGES

Zhou, Lin; Tang, Wei; Ke, Liqin; ...

2017-05-08

Further property enhancement of alnico, an attractive near-term, non-rare-earth permanent magnet alloy system, primarily composed of Al, Ni, Co, and Fe, relies on improved morphology control and size refinement of its complex spinodally decomposed nanostructure that forms during heat-treatment. Using a combination of transmission electron microscopy and atom probe tomography techniques, this study evaluates the magnetic properties and microstructures of an isotropic 32.4Fe-38.1Co-12.9Ni-7.3Al-6.4Ti-3.0Cu (wt.%) alloy in terms of processing parameters such as annealing temperature, annealing time, application of an external magnetic field, as well as low-temperature “draw” annealing. Optimal spinodal morphology and spacing is formed within a narrow temperature andmore » time range (~840 °C and 10 min) during thermal-magnetic annealing (MA). The ideal morphology is a mosaic structure consisting of periodically arrayed ~40 nm diameter (Fe-Co)-rich rods (α 1 phase) embedded in an (Al-Ni)-rich (α 2 phase) matrix. A Cu-enriched phase with a size of ~3–5 nm is located at the corners of two adjacent {110} facets of the α 1 phase. The MA process significantly increased remanence (B r) (~40–70%) of the alloy due to biased elongation of the α 1 phase along the <100> crystallographic direction, which is closest in orientation to the applied magnetic field. As a result, the optimum magnetic properties of the alloy with an intrinsic coercivity (H cj) of 1845 Oe and a maximum energy product (BH max) of 5.9 MGOe were attributed to the uniformity of the mosaic structure.« less

Novel Co- or Ni-Mn binary oxide catalysts with hydroxyl groups for NH3-SCR of NOx at low temperature

NASA Astrophysics Data System (ADS)

Gao, Fengyu; Tang, Xiaolong; Yi, Honghong; Zhao, Shunzheng; Wang, Jiangen; Shi, Yiran; Meng, Xiaomi

2018-06-01

Novel hydroxyl-containing Me-Mn binary oxides (Me = Co, Ni) were prepared for the selective catalytic reduction of NOx with NH3 by a combined complexation-esterification method. The binary oxides of Co-MnOx and Ni-MnOx with mixed crystal phases of Mn3O4 and Co3O4, Mn2O3 and NiMnO3 were obtained at 550 °C. SCR activity decreased in the order of Mn3O4-Co3O4-OH > Mn2O3-NiMnO3-OH > Mn2O3-OH > Mn3O4-OH, benefiting from the high concentration of chemisorbed oxygen and effective electron transformation of cations. Mn2O3-containing catalysts had better selectivity to N2 than those containing Mn3O4. Higher selectivity to N2O over Mn3O4-containing catalysts was attributed to the depth dehydrogenation of coordinated NH3 by the active oxygen species with lower Mnsbnd O band energy. The typical Eley-Rideal mechanism over Mn3O4-OH and Mn3O4-Co3O4-OH, and the additional formation pathway of NH4NO3 species over Mn2O3-OH and Mn2O3-NiMnO3-OH catalysts were proposed via the in-situ DRIFTS experiments. Although the Co and Ni elements had a good role in delaying the poisoning of SO2, these catalysts were eventually sulfated by SO2 over the postponement, which might due to the metal sulfate and ammonia hydrogensulfite species.

Color tone and interfacial microstructure of white oxide layer on commercially pure Ti and Ti-Nb-Ta-Zr alloys

NASA Astrophysics Data System (ADS)

Miura-Fujiwara, Eri; Mizushima, Keisuke; Watanabe, Yoshimi; Kasuga, Toshihiro; Niinomi, Mitsuo

2014-11-01

In this study, the relationships among oxidation condition, color tone, and the cross-sectional microstructure of the oxide layer on commercially pure (CP) Ti and Ti-36Nb-2Ta-3Zr-0.3O were investigated. “White metals” are ideal metallic materials having a white color with sufficient strength and ductility like a metal. Such materials have long been sought for in dentistry. We have found that the specific biomedical Ti alloys, such as CP Ti, Ti-36Nb-2Ta-3Zr-0.3O, and Ti-29Nb-13Ta-4.6Zr, form a bright yellowish-white oxide layer after a particular oxidation heat treatment. The brightness L* and yellowness +b* of the oxide layer on CP Ti and Ti-36Nb-2Ta-3Zr-0.3O increased with heating time and temperature. Microstructural observations indicated that the oxide layer on Ti-29Nb-13Ta-4.6Zr and Ti-36Nb-2Ta-3Zr-0.3O was dense and firm, whereas a piecrust-like layer was formed on CP Ti. The results obtained in this study suggest that oxide layer coating on Ti-36Nb-2Ta-3Zr-0.3O is an excellent technique for dental applications.

Water Splitting via Decoupled Photocatalytic Water Oxidation and Electrochemical Proton Reduction Mediated by Electron-Coupled-Proton Buffer.

PubMed

Li, Fei; Yu, Fengshou; Du, Jian; Wang, Yong; Zhu, Yong; Li, Xiaona; Sun, Licheng

2017-10-18

Water splitting mediated by electron-coupled-proton buffer (ECPB) provides an efficient way to avoid gas mixing by separating oxygen evolution from hydrogen evolution in space and time. Though electrochemical and photoelectrochemcial water oxidation have been incorporated in such a two-step water splitting system, alternative ways to reduce the cost and energy input for decoupling two half-reactions are desired. Herein, we show the feasibility of photocatalytic oxygen evolution in a powder system with BiVO 4 as a photocatalyst and polyoxometalate H 3 PMo 12 O 40 as an electron and proton acceptor. The resulting reaction mixture was allowed to be directly used for the subsequent hydrogen evolution with the reduced H 3 PMo 12 O 40 as electron and proton donors. Our system exhibits excellent stability in repeated oxygen and hydrogen evolution, which brings considerable convenience to decoupled water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heavy-ion irradiation effects on U3O8 incorporated Gd2Zr2O7 waste forms.

PubMed

Lu, Xirui; Shu, Xiaoyan; Chen, Shunzhang; Zhang, Kuibao; Chi, Fangtin; Zhang, Haibin; Shao, Dadong; Mao, Xueli

2018-06-12

In this research, the heavy-ion irradiation effects of U-bearing Gd 2 Zr 2 O 7 ceramics were explored for nuclear waste immobilization. U 3 O 8 was designed to be incorporated into Gd 2 Zr 2 O 7 from two different routes in the form of (Gd 1-4 x U 2 x ) 2 (Zr 1- x U x ) 2 O 7 (x = 0.1, 0.14). The self-irradiation of actinide nuclides was simulated by Xe 20+ heavy-ion radiation under different fluences. Grazing incidence X-ray diffraction (GIXRD) analysis reveals the relationship between radiation dose, damage and depth. The radiation tolerance is promoted with the increment of U 3 O 8 content in the discussed range. Raman spectroscopy testifies the enhancement of radiation tolerance and microscopically existed phase evolution from the chemical bond vibrations. In addition, the microstructure and elemental distribution of the irradiated samples were analyzed as well. The amorphization degree of the sample surface declines as the U content was elevated from x = 0.1 to x = 0.14. Copyright © 2018 Elsevier B.V. All rights reserved.

Reduction of Hematite to Magnetite in CO/CO2 Gas Mixtures Under Carbon Looping Combustion Conditions

NASA Astrophysics Data System (ADS)

Simmonds, Tegan; Hayes, Peter C.

2017-12-01

Iron oxides have been identified as promising materials for use as oxygen carriers in chemical looping combustion technologies as there are abundant resources available in the form of ore and in industrial wastes. The isothermal reduction of hematite (Fe2O3) in the fuel reactor and the subsequent oxidation of magnetite (Fe3O4) in air are the principal reactions of interest for these applications. Experimental investigations have been carried out to characterize the microstructural changes taking place as a result of the reduction reactions for a range of CO/CO2 gas compositions at temperatures between 1073 K and 1373 K (800 °C and 1100 °C). It has been shown that magnetite spinel is formed directly from hematite under these conditions and that porous magnetite or dense platelet or "lath" type morphologies can be formed depending on gas composition and reaction temperature. The conditions for the lath/pore transition are established. Dendritic gas pores are formed during the creation of the porous magnetite. This morphology allows continuous contact between the gas reactant and reaction interface and results in high reduction reaction rates.

Synthesis of cationic iridium(I) complexes of water-soluble phosphine ligands, [Ir(CO)(TPPMS){sub 3}]CF{sub 3}SO{sub 3}, [Ir(CO)(H{sub 2}O)(TPPTS){sub 2}]CF{sub 3}SO{sub 3}, and [Ir(CO){sub 2}(TPPMS){sub 3}]ClO{sub 4} (TPPMS = PPh{sub 2}(m-C{sub 6}H{sub 4}SO{sub 3}K), TPPTS = P(m-C{sub 6}H{sub 4}SO{sub 3}Na){sub 3})

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

Paterniti, D.P.; Francisco, L.W.; Atwood, J.D.

Several new water-soluble iridium(I) complexes were synthesized and their reactivities with small molecules (H{sub 2} or CO) in polar solvents (DMSO or H{sub 2}O) examined. Reaction of H{sub 2} with [Ir(CO)(TPPMS){sub 3}]CF{sub 3}SO{sub 3} (TPPMS = P(C{sub 6}H{sub 5}){sub 2}(m-C{sub 6}H{sub 4}SO{sub 3}K)) in DMSO or H{sub 2}O produces [cis,mer-Ir(CO)(H){sub 2}(TPPMS){sub 3}]CF{sub 3}SO{sub 3}, while the reaction of CO with [Ir(CO)(TPPMS){sub 3}]-CF{sub 3}SO{sub 3} in water yields [Ir(CO){sub 2}(TPPMS){sub 3}]CF{sub 3}SO{sub 3}. Carbonylation of [Ir(CO){sub 2}(TPPMS){sub 3}]ClO{sub 4} in DMSO produces [Ir(CO){sub 3}(TPPMS){sub 2}]ClO{sub 4} and TPPMS; no reaction is observed in H{sub 2}O. Hydrogenation of [Ir(CO){sub 2}(TPPMS){sub 3}]ClO{sub 4}more » in DMSO or H{sub 2}O yields [cis,mer-Ir(CO)(H){sub 2}(TPPMS){sub 3}]ClO{sub 4}, while reaction of H{sub 2} with an aqueous solution of [Ir(CO)(H{sub 2}O)(TPPTS){sub 2}]CF{sub 3}SO{sub 3} produces [Ir(CO)(H{sub 2}O)(H){sub 2}(TPPTS){sub 2}]CF{sub 3}SO{sub 3}. Reaction of trans-Ir(CO)ClL{sub 2} (L = TPPMS or TPPTS) with excess L in H{sub 2}O produces [Ir(CO)L{sub 3}]Cl, while no reaction occurs in DMSO, [Ir(CO){sub 3}(TPPMS){sub 2}]Cl reacts irreversibly with TPPMS in H{sub 2}O to produce [Ir(CO){sub 2}-(TPPMS){sub 3}]Cl.« less

Evolution of the atmosphere of Venus

NASA Technical Reports Server (NTRS)

Yung, Y. L.

1981-01-01

The photochemistry of the stratosphere of Venus was modeled using an updated and expanded chemical scheme, and the results of recent laboratory studies. The model satisfactorily accounts for the observations of CO, O2, (1) and SO2 in the stratosphere. Oxygen, derived from CO2 photolysis, is primarily consumed by CO2 recombination and oxidation of SO2 to H2SO4. Photolysis of HCl in the upper stratosphere provides a major source of odd hydrogen radicals essential for the catalytic oxidation of CO. Oxidation of SO2 by O occurs in the lower stratosphere, with the O-O bond broken by S + O2 and SO + HO2. The sensitivity of stratospheric chemistry to ambient H2 abundance was studied and the model prefers the high value (1 10 ppm) recently inferred from the Pioneer Venus ionospheric measurements. The importance of the photochemical production of S2O, (SO)2, S2, H2S2O2 and H2S2O3 is speculated. A number of previously unsuspected similarities between the chemistry of the stratospheres of Venus and the Earth, presented and discussed.

A comparative study of the properties of five-layered Aurivillius oxides A2Bi4Ti5O18 (A = Ba, Pb, and Sr) synthesized by different wet chemical routes

NASA Astrophysics Data System (ADS)

Dubey, Shivangi; Subohi, Oroosa; Kurchania, Rajnish

2018-07-01

This paper reports the detailed study of the effect of different wet chemical synthesis routes (solution combustion, co-precipitation, and sol-gel route) on the microstructure, phase formation, dielectric, electrical, and ferroelectric properties of five-layered Aurivillius oxides: A2Bi4Ti5O18 (A = Ba, Pb, and Sr). Different synthesis parameters like the precursors used, synthesis temperature, and reaction time affects the morphology of the ceramics. Microstructure in turn influences the dielectric and ferroelectric properties. It was observed that the sol-gel-synthesized ceramics possess higher dielectric constant and remanent polarization, low dielectric loss due to lower conductivity in these samples as a result of higher density in these compounds as compared to those synthesized by other wet chemical synthesis routes such as solution combustion route and co-precipitation technique. The XRD data are used for phase analysis and surface morphology is studied using SEM images. Dielectric and electrical properties are investigated as a function of frequency and temperature.

Bimetallic-organic framework derived porous Co3O4/Fe3O4/C-loaded g-C3N4 nanocomposites as non-enzymic electrocatalysis oxidization toward ascorbic acid, dopamine acid, and uric acid

NASA Astrophysics Data System (ADS)

Hu, Bin; Liu, Yongkang; Wang, Zhuo-Wei; Song, Yingpan; Wang, Minghua; Zhang, Zhihong; Liu, Chun-Sen

2018-05-01

We report on the synthesis of Co- and Fe-based bimetallic nanocatalysts embedded in mesoporous carbon and g-C3N4 nanosheets (denoted as Co3O4/Fe3O4/mC@g-C3N4) for selectively simultaneous determination of ascorbic acid (AA), dopamine acid (DA), and uric acid (UA). These electrocatalysts consisting of bimetallic Co-Fe alloy nanoparticles encapsulated in N-doped carbon matrix were prepared via pyrolysis of Co/Fe-MOFs after grinding with high amounts of melamine. Chemical/crystal structures suggest high contents of mesoporous carbon in calcinated Co3O4/Fe3O4/mC nanocomposites, which exhibited enhanced electrocatalytic activity toward small biomolecules. The intrinsic performances of Co/Fe-MOFs with large specific surface area and regular nodes in the two-dimensional nanostructured g-C3N4 nanosheets endowed the as-prepared series of Co3O4/Fe3O4/mC@g-C3N4 nanocomposites with remarkable electrocatalytic activities and high adsorption ability toward oxidation of AA, DA, and UA. The developed biosensors also showed long-term stability and high selectivity for targeted analytes, with satisfactory results on actual samples in human urine. The results indicate that the as-synthesized Co3O4/Fe3O4/mC@g-C3N4 nanostructure exhibits good electrocatalytic activity and potential applications in clinical diagnosis and biosensing.

One-step engineered self-assembly Co3O4 nanoparticles to nanocubes for supercapacitors

NASA Astrophysics Data System (ADS)

Nagajyothi, P. C.; Pandurangan, M.; Sreekanth, T. V. M.; Shim, Jaesool

2018-02-01

Tricobalt tetraoxide or cobalt oxide (Co3O4) nanocubes (NCs) were synthesized from the self-assemblies of Co3O4 nanoparticles (NPs) via a simple one-step hydrothermal method. X-ray diffraction analysis confirmed the cubic crystal structure of Co3O4 NCs. The surface properties were investigated by x-ray photoelectron spectroscopy, which suggests the co-existence of Co in +2 and +3 states. The self-assemblies of aggregation of NPs to NCs were inspected using scanning electron microscopy, which is supported by transmission electron microscopy. The electrochemical properties of Co3O4 NCs were carried out by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) curves and impedance analysis. The areal capacitance of 3.04 mF cm-2 was obtained at current density of 10 μA cm-2. The Co3O4 NCs electrode exhibits good long-cyclic stability with 92.1% capacitance retention over 3000 cycles. The CV, GCD and impedance curves of Co3O4 NCs were recorded after cyclic test, which are similar to the curves recorded before the test. Therefore, the Co3O4 NCs serves good candidate as positive electrode materials for asymmetric supercapacitors.

Transition-metal redox evolution in LiNi 0.5Mn 0.3Co 0.2O 2 electrodes at high potentials

DOE PAGES

Qiao, Ruimin; Liu, Jun; Kourtakis, Kostantinos; ...

2017-06-12

The mixed transition-metal layered compound, LiNi 0.5Mn 0.3Co 0.2O 2 (NMC532), is a promising high-energy cathode material. However, the required high-voltage (>4.3 V) cycling is accompanied by a rapid capacity fade associated with a complex redox mechanism that has not been clarified. Here in this paper, we report soft x-ray absorption spectroscopy of NMC532 electrodes, both pristine and those charged to 4.2, 4.35, or 4.5 V in graphite/NMC532 cells. A quantitative sXAS analysis shows that about 20% of the nickel exists as Ni 4+ in the as-synthesized NMC532. The Ni redox reaction contributes only to the experimental capacity obtained belowmore » 4.2 V, while Co redox reactions take place throughout the entire electrochemical cycling up to 4.5 V. In contrast to the changing ratio of the well-defined Ni 2+, Ni 3+ and Ni 4+ ions, Co always displays ill-defined intermediate valence states in the charged NMC532 electrodes. This indicates an itinerant electron system in NMC electrodes related to the improved rate performance through Co doping. Furthermore, about 20% of Ni 2+ is found on the electrode surface at the high potential, which suggests that the electrode surface has either gone through surface reconstruction or reacted with the electrolyte at high voltage.« less

Recycling of spent ion-lithium batteries as cobalt hydroxide, and cobalt oxide films formed under a conductive glass substrate, and their electrochemical properties

NASA Astrophysics Data System (ADS)

Barbieri, E. M. S.; Lima, E. P. C.; Cantarino, S. J.; Lelis, M. F. F.; Freitas, M. B. J. G.

2014-12-01

In this work, Co(OH)2 and Co3O4 films have been obtained using a solution to leach the cathodes of spent Li-ion batteries. The Co(OH)2 is electrodeposited onto conductive glass by the application of -0.85 V, with a charge density of 20 C cm-2, and its efficiency is found to be 66.67%. The Co3O4 film is obtained by heat treatment of the Co(OH)2 film at 450 °C for 3 h, in an air atmosphere, with a conversion efficiency of 64.29%. The cyclic voltammetry of Co(OH)2, in KOH 1.0 mol L-1 shows: three anodic peaks in the first cycle associated with the oxidation of Co(OH)2 to Co3O4, the conversion of Co3O4 into CoOOH, and the formation of CoOOH to CoO2 and the oxidation of water. The absence of cathodic peaks shows that oxidation from Co(OH)2 to CoO2 is an irreversible process. For the Co3O4 electrode, this verifies the existence of a redox pair associated with reversible oxidation of the Co3O4 to CoO2. The Co3O4 obtains a charge efficiency of 77% for the first 10 cycles (1.0 mV s-1) and a specific capacitance of 31.2 F g-1 (1.0 mV s-1) and 10.5 F g-1 (10 mV s-1). Co3O4 films have promising applications as pseudocapacitors.

Synergetic Effect of Dy2O3 and Ca Co-Dopants towards Enhanced Coercivity of Rare Earth Abundant RE-Fe-B Magnets.

PubMed

Li, Yingfei; Tian, Na; Fan, Xiaodong; You, Caiyin; Pei, Wenli; Cheng, Zhenxiang

2017-12-13

Low coercivity is the main disadvantage of RE-Fe-B permanent magnets containing highly abundant rare earths (RE: La, Ce) from the application point of view, even though they exhibit many cost and resource advantages. In this work, an industrial mixed rare earth alloy (RE 100  = La 30.6 Ce 50.2 Pr 6.4 Nd 12.8 ) with a high amount of the more abundant elements was adopted to fabricate RE-Fe-B permanent magnets by means of mechanical alloying accompanied by post-annealing. A synergetic effect towards enhancing the coercivity was observed after co-doping with Dy 2 O 3 and Ca, with the coercivity increasing from 2.44 kOe to 11.43 kOe for co-dopant percentages of 7 wt.% Dy 2 O 3  + 2.3 wt.% Ca. Through analysis of the phase constituents and microstructure, it was determined that part of the Dy atoms entered the matrix of RE 2 Fe 14 B phase to enhance the magnetocrystalline anisotropy; due to the reductive effect of Ca on Dy 2 O 3 , nanocrystals of Dy-rich RE 2 Fe 14 B were present throughout the matrix, which could increase the resistance to domain wall movement. These are the dominant factors behind the improvement of the coercivity of the RE-Fe-B magnets with highly abundant RE elements.

Architecture, microstructure and Jc anisotropy of highly oriented biaxially textured Co-doped BaFe2As2 on Fe/IBAD-MgO-buffered metal tapes

NASA Astrophysics Data System (ADS)

Trommler, S.; Hänisch, J.; Matias, V.; Hühne, R.; Reich, E.; Iida, K.; Haindl, S.; Schultz, L.; Holzapfel, B.

2012-08-01

Optimized, biaxially textured BaFe1.8Co0.2As2 thin films with an in-plane alignment of 1.7° have been realized on high-quality IBAD-textured MgO-coated technical substrates utilizing additional Fe buffer layers. High critical current densities (Jc) were achieved, comparable to films on single crystalline MgO (Jc ≥ 1 MA cm-2 at 4 K, self-field). Transmission electron microscopy investigations reveal a small number of c-axis correlated defects introduced by the MgO template. The effect of these defects on the Jc anisotropy was determined in angular-dependent electronic transport measurements.

A Co3O4-embedded porous ZnO rhombic dodecahedron prepared using zeolitic imidazolate frameworks as precursors for CO2 photoreduction

NASA Astrophysics Data System (ADS)

Wang, Tao; Shi, Li; Tang, Jing; Malgras, Victor; Asahina, Shunsuke; Liu, Guigao; Zhang, Huabin; Meng, Xianguang; Chang, Kun; He, Jianping; Terasaki, Osamu; Yamauchi, Yusuke; Ye, Jinhua

2016-03-01

Metal-organic frameworks (MOFs) are attracting considerable attention for their use as both the precursor and the template to prepare metal oxides or carbon-based materials. For the first time in this paper, the core-shell ZIF-8@ZIF-67 crystals are thermally converted into porous ZnO@Co3O4 composites by combining a seed-mediated growth process with a two-step calcination. The designed porous ZnO@Co3O4 composites exhibited the highest photocatalytic activity with an excellent stability for the reduction of CO2 among the commonly reported composite photocatalysts. Their superior photocatalytic performance is demonstrated to be resulting from the unique porous structure of ZnO@Co3O4 and the co-catalytic function of Co3O4 which can effectively suppress the photocorrosion of ZnO.Metal-organic frameworks (MOFs) are attracting considerable attention for their use as both the precursor and the template to prepare metal oxides or carbon-based materials. For the first time in this paper, the core-shell ZIF-8@ZIF-67 crystals are thermally converted into porous ZnO@Co3O4 composites by combining a seed-mediated growth process with a two-step calcination. The designed porous ZnO@Co3O4 composites exhibited the highest photocatalytic activity with an excellent stability for the reduction of CO2 among the commonly reported composite photocatalysts. Their superior photocatalytic performance is demonstrated to be resulting from the unique porous structure of ZnO@Co3O4 and the co-catalytic function of Co3O4 which can effectively suppress the photocorrosion of ZnO. Electronic supplementary information (ESI) available: Additional TG and DTA curves, XRD patterns, SEM images, TEM images, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy and GC-MS spectra of the samples. See DOI: 10.1039/c5nr08747c

Three-dimensional Co3O4@MWNTs nanocomposite with enhanced electrochemical performance for nonenzymatic glucose biosensors and biofuel cells

NASA Astrophysics Data System (ADS)

Jiao, Kailong; Jiang, Yu; Kang, Zepeng; Peng, Ruiyun; Jiao, Shuqiang; Hu, Zongqian

2017-12-01

Three-dimensional nanoarchitectures of Co3O4@multi-walled carbon nanotubes (Co3O4@MWNTs) were synthesized via a one-step process with hydrothermal growth of Co3O4 nanoparticles onto MWNTs. The structure and morphology of the Co3O4@MWNTs were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller, scanning electron microscopy and transmission electron microscopy. The electrocatalytic mechanism of the Co3O4@MWNTs was studied by X-ray photoelectron spectroscopy and cyclic voltammetry. Co3O4@MWNTs exhibited high electrocatalytic activity towards glucose oxidation in alkaline medium and could be used in nonenzymatic electrochemical devices for glucose oxidation. The open circuit voltage of the nonenzymatic glucose/O2 fuel cell was 0.68 V, with a maximum power density of 0.22 mW cm-2 at 0.30 V. The excellent electrochemical properties, low cost, and facile preparation of Co3O4@MWNTs demonstrate the potential of strongly coupled oxide/nanocarbon hybrid as effective electrocatalyst in glucose fuel cells and biosensors.