Synthesis, second-harmonic generation (SHG), and photoluminescence (PL) properties of noncentrosymmetric bismuth selenite solid solutions, Bi2-xLnxSeO5 (Ln = La and Eu; x = 0-0.3)

NASA Astrophysics Data System (ADS)

Qi, Hai-Xin; Jo, Hongil; Oh, Seung-Jin; Ok, Kang Min

2018-02-01

A series of La3+ or Eu3+-doped noncentrosymmetric (NCS) bismuth selenite solid solutions, Bi2-xLnxSeO5 (x = 0.1, 0.2, and 0.3), have been successfully synthesized via standard solid-state reactions under vacuum with Bi2O3, La2O3 (or Eu2O3), and SeO2 as starting materials. Crystal structures and phase purities of the resultant materials were thoroughly characterized by powder X-ray diffraction using the Rietveld method. The results clearly show that the reported materials crystallize in the orthorhombic space group, Abm2 (No. 39), and exhibit pseudo-three-dimensional frameworks consisting of BiO3, BiO5, and SeO3 polyhedra that share edges and corners. Detailed diffraction studies indicate that the cell volume of Bi2-xLnxSeO5 decreases with an increasing amount of Ln3+ on the Bi3+ sites. However, no ordering between Ln3+ and Bi3+ was observed in the Bi2-xLnxSeO5 solid solutions. Powder second-harmonic generation (SHG) measurements, using 1064 nm radiation, reveal that SHG efficiencies of Bi2-xLnxSeO5 solid solutions continuously decrease as more Ln3+ cations are added to the sites of polarizable Bi3+ cations. Photoluminescence (PL) measurements on Bi2-xEuxSeO5 exhibit three specific emission peaks at 592, 613, and 702 nm (5D0 → 7F1, 2, 4) owing to the 4f-4f intrashell transitions of Eu3+ ions.

Zinc-aluminum oxide solid solution nanosheets obtained by pyrolysis of layered double hydroxide as the photoanodes for dye-sensitized solar cells.

PubMed

Xu, Zhiyuan; Shi, Jingjing; Haroone, Muhammad Sohail; Chen, Wenpeng; Zheng, Shufang; Lu, Jun

2018-04-01

Due to the superiority of metal-doped ZnO compared to TiO 2 , the Zn-M (M = Al 3+ , Ga 3+ , Cr 3+ , Ti 4+ , Ce 4+ ) mixed metal oxide solid solutions have been extensively studied for photocatalytic and photovoltaic applications. In this work, a systematic research has proceeded for the preparation of a zinc-aluminum oxide semiconductor as a photoanode for the dye-sensitized solar cells (DSSCs) by a simple pyrolysis route with the Zn-Al layered double hydroxide (LDH) as a precursor. The Zn-Al oxide solid solution has been applied for DSSCs as an electron acceptor, which is used to study the influence of different Al content and sintering temperature on the device efficiency. Finally, the Zn-Al oxide solid solution with calcination temperature 600 °C and Al 27 at.% content exhibits the best performance. The photoelectric efficiency improved 100 times when the Al 3+ content decreased from 44 to 27 at.%. The Zn x Al y O solid solution show a reasonable efficiency as photoanode materials in DSSCs, with the best preliminary performance reported so far, and shows its potential application for the photovoltaic devices. Copyright © 2018 Elsevier Inc. All rights reserved.

Dynamics of Re(2,2'-bipyridine)(CO)3Cl MLCT formation and decay after picosecond pulsed X-ray excitation and femtosecond UV excitation.

PubMed

Zhao, Liyan; Odaka, Hideho; Ono, Hiroshi; Kajimoto, Shinji; Hatanaka, Koji; Hobley, Jonathan; Fukumura, Hiroshi

2005-01-01

The dynamics of Re(2,2'-bipyridine)(CO)3Cl MLCT state formation and decay were determined after femtosecond UV laser excitation and picosecond pulsed X-ray excitation, in an N,N-dimethylformamide (DMF) solution as well as in its solid form. At room temperature, after UV excitation, this MLCT excited state emits both in DMF solution and in the solid form. Transient absorption spectra were measured in solution at various delay times following excitation by a 160 fs, 390 nm laser pulse. There was a prompt absorption increase at around 460 nm occurring within the pump probe convolution (<1 ps), which was assigned to the formation of the 3MLCT state. This transient absorbance was constant over 100 ps. In contrast to the solution state, in the solid state, the emission maximum slightly red-shifts with increasing time after laser excitation. In both solid and solution the emission rises within the system response time. The solid sample exhibited a 1.4 ns emission decay that was not observed for the solution sample. The emission rise from a solid sample after 20 ps pulsed X-ray excitation was significantly slower than the system's time resolution. It is proposed that kinetically energetic electrons are ejected following X-ray induced ionisation, creating ionised tracks in which energetic cations and electrons take time to recombine yielding delayed 3MLCT states that emit.

Solid Solution Photocatalyst with Spontaneous Polarization Exhibiting Low Recombination Toward Efficient CO2 Photoreduction.

PubMed

Zhou, Peng; Wang, Xin; Yan, Shicheng; Zou, Zhigang

2016-08-23

Decreasing the recombination of photogenerated carriers is a major challenge for efficiently converting solar energy into chemical energy by photocatalysis. Here, we have demonstrated that growth of a polar GaN:ZnO solid solution single crystal along its polarization axis is beneficial to efficient separation of photogenerated carriers, owing to the periodic potential barriers and wells generated from the periodically positive and negative atom arrangements in crystal structure. Local charge imbalance caused by replacing Ga(3+) with Zn(2+) leads to a polarization vector in the {0 0 0 1} planes of GaN:ZnO solid solution, thus forming a 1 D electron transport path along [2 1‾  1‾  0] in the {0 0 0 1} planes of GaN:ZnO solid solution to decrease recombination. Shorting the hole-transport distance by synthesizing porous nanoplates can further decrease recombination under the polarization field and improve the performance of polar photocatalyst in photoreduction of CO2 into CH4 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid-State Nanopore.

PubMed

Yuan, Zhishan; Wang, Chengyong; Yi, Xin; Ni, Zhonghua; Chen, Yunfei; Li, Tie

2018-02-20

Solid-state nanopore has captured the attention of many researchers due to its characteristic of nanoscale. Now, different fabrication methods have been reported, which can be summarized into two broad categories: "top-down" etching technology and "bottom-up" shrinkage technology. Ion track etching method, mask etching method chemical solution etching method, and high-energy particle etching and shrinkage method are exhibited in this report. Besides, we also discussed applications of solid-state nanopore fabrication technology in DNA sequencing, protein detection, and energy conversion.

Solid-State Nanopore

NASA Astrophysics Data System (ADS)

Yuan, Zhishan; Wang, Chengyong; Yi, Xin; Ni, Zhonghua; Chen, Yunfei; Li, Tie

2018-02-01

Solid-state nanopore has captured the attention of many researchers due to its characteristic of nanoscale. Now, different fabrication methods have been reported, which can be summarized into two broad categories: "top-down" etching technology and "bottom-up" shrinkage technology. Ion track etching method, mask etching method chemical solution etching method, and high-energy particle etching and shrinkage method are exhibited in this report. Besides, we also discussed applications of solid-state nanopore fabrication technology in DNA sequencing, protein detection, and energy conversion.

Molten-salt synthesis and composition-dependent luminescent properties of barium tungsto-molybdate-based solid solution phosphors

NASA Astrophysics Data System (ADS)

Xiang-Hong, He; Zhao-Lian, Ye; Ming-Yun, Guan; Ning, Lian; Jian-Hua, Sun

2016-02-01

Pr3+-activated barium tungsto-molybdate solid solution phosphor Ba(Mo1-zWz)O4:Pr3+ is successfully fabricated via a facile molten-salt approach. The as-synthesized microcrystal is of truncated octahedron and exhibits deep-red-emitting upon blue light excitation. Powder x-ray diffraction and Raman spectroscopy techniques are utilized to investigate the formation of solid solution phosphor. The luminescence behaviors depend on the resulting composition of the microcrystals with fixed Pr3+-doping concentration, while the host lattices remain in a scheelite structure. The forming solid solution via the substitution of [WO4] for [MoO4] can significantly enhance its luminescence, which may be due to the fact that Ba(Mo1-zWz)O4:Pr3+ owns well-defined facets and uniform morphologies. Owing to its properties of high phase purity, well-defined facets, highly uniform morphologies, exceptional chemical and thermal stabilities, and stronger emission intensity, the resulting solid solution phosphor is expected to find potential applications in phosphor-converted white light-emitting diodes (LEDs). Project supported by the Construction Fund for Science and Technology Innovation Group from Jiangsu University of Technology, China, the Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, China (Grant No. KHK1409), the Priority Academic Program Development of Jiangsu Higher Education Institutions, China, and the National Natural Science Foundation of China (Grant No. 21373103).

Calibration-free quantification of interior properties of porous media with x-ray computed tomography.

PubMed

Hussein, Esam M A; Agbogun, H M D; Al, Tom A

2015-03-01

A method is presented for interpreting the values of x-ray attenuation coefficients reconstructed in computed tomography of porous media, while overcoming the ambiguity caused by the multichromatic nature of x-rays, dilution by void, and material heterogeneity. The method enables determination of porosity without relying on calibration or image segmentation or thresholding to discriminate pores from solid material. It distinguishes between solution-accessible and inaccessible pores, and provides the spatial and frequency distributions of solid-matrix material in a heterogeneous medium. This is accomplished by matching an image of a sample saturated with a contrast solution with that saturated with a transparent solution. Voxels occupied with solid-material and inaccessible pores are identified by the fact that they maintain the same location and image attributes in both images, with voxels containing inaccessible pores appearing empty in both images. Fully porous and accessible voxels exhibit the maximum contrast, while the rest are porous voxels containing mixtures of pore solutions and solid. This matching process is performed with an image registration computer code, and image processing software that requires only simple subtraction and multiplication (scaling) processes. The process is demonstrated in dolomite (non-uniform void distribution, homogeneous solid matrix) and sandstone (nearly uniform void distribution, heterogeneous solid matrix) samples, and its overall performance is shown to compare favorably with a method based on calibration and thresholding. Copyright © 2014 Elsevier Ltd. All rights reserved.

Efficient encapsulation of chloroform with cryptophane-M and the formation of exciplex studied by fluorescence spectroscopy.

PubMed

Shi, Yanqi; Li, Xueming; Yang, Jianchun; Gao, Fang; Tao, Chuanyi

2011-03-01

Efficient encapsulation of small molecules with supermolecules is one of significantly important subjects due to strong application potentials. This article presents the interaction between cryptophane-M and chloroform by fluorescence spectroscopy. The sonicated cryptophane-M solution exhibits light green color in chloroform, and the solid obtained from the evaporation of chloroform also has different color from that of cryptophane-M. In contrast, the sonicated cryptophane-M solutions in other solvents are colorless, and the solid obtained from the evaporation of these solvents has the same color as that of cryptophane-M. Furthermore, the freshly prepared cryptophane-M solution in different solvents is almost colorless, and the solid obtained from the evaporation of these solvents displays the same color as that of cryptophane-M. Although the sonicated cryptophane-M solutions in different solvents have very similar absorption spectra, they exhibit quite different emission spectra in chloroform. In contrast, the freshly-prepared cryptophane-M solutions show similar absorption and emission spectroscopy in various solvents. The variation of the fluorescence spectroscopy in binary solvents with the increasing chloroform ratio suggests that cryptophane-M and chloroform form a 1:1 exciplex, and the binding constant is estimated to be 292.95 M(-1). Although all solvents are able to enter into the cavity of cryptophane-M, only chloroform can stay in the cavity of cryptophane-M for a while, which is mostly due to the strong intermolecular interaction between cryptophane-M and chloroform, and this results in the formation of the exciplex between them. © Springer Science+Business Media, LLC 2010

Dendritic copper phthalocyanine with aggregation induced blue emission and solid-state fluorescence

NASA Astrophysics Data System (ADS)

Wang, Jiayi; Pan, Lin; Zhou, Xuefei; Jia, Kun; Liu, Xiaobo

2016-09-01

In this work, dendritic copper phthalocyanine (CuPc) showing obvious aggregation induced emission (AIE) and strong solid-state fluorescence was synthesized. It was found that synthesized CuPc can be easily solubilized in polar aprotic solvent, where no fluorescence signal was detected. Interestingly, both the CuPc aggregates in solution and solid-state powder exhibited strong fluorescence emission around 480 nm, which should be attributed to the restriction of intramolecular rotation as rationalized in aggregation induced emission framework. Meanwhile the obvious crystalline enhanced solid-state fluorescent emission is observed for CuPc powder.

Composition design for Laves phase-related body-centered cubic-V solid solution alloys with large hydrogen storage capacities.

PubMed

Wang, H B; Wang, Q; Dong, C; Yuan, L; Xu, F; Sun, L X

2008-03-19

This paper analyzes the characteristics of alloy compositions with large hydrogen storage capacities in Laves phase-related body-centered cubic (bcc) solid solution alloy systems using the cluster line approach. Since a dense-packed icosahedral cluster A(6)B(7) characterizes the local structure of AB(2) Laves phases, in an A-B-C ternary system, such as Ti-Cr (Mn, Fe)-V, where A-B forms AB(2) Laves phases while A-C and B-C tend to form solid solutions, a cluster line A(6)B(7)-C is constructed by linking A(6)B(7) to C. The alloy compositions with large hydrogen storage capacities are generally located near this line and are approximately expressed with the cluster-plus-glue-atom model. The cluster line alloys (Ti(6)Cr(7))(100-x)V(x) (x = 2.5-70 at.%) exhibit different structures and hence different hydrogen storage capacities with increasing V content. The alloys (Ti(6)Cr(7))(95)V(5) and Ti(30)Cr(40)V(30) with bcc solid solution structure satisfy the cluster-plus-glue-atom model.

Thermoelectric SnS and SnS-SnSe solid solutions prepared by mechanical alloying and spark plasma sintering: Anisotropic thermoelectric properties

PubMed Central

Asfandiyar; Wei, Tian-Ran; Li, Zhiliang; Sun, Fu-Hua; Pan, Yu; Wu, Chao-Feng; Farooq, Muhammad Umer; Tang, Huaichao; Li, Fu; Li, Bo; Li, Jing-Feng

2017-01-01

P–type SnS compound and SnS1−xSex solid solutions were prepared by mechanical alloying followed by spark plasma sintering (SPS) and their thermoelectric properties were then studied in different compositions (x = 0.0, 0.2, 0.5, 0.8) along the directions parallel (//) and perpendicular (⊥) to the SPS–pressurizing direction in the temperature range 323–823 Κ. SnS compound and SnS1−xSex solid solutions exhibited anisotropic thermoelectric performance and showed higher power factor and thermal conductivity along the direction ⊥ than the // one. The thermal conductivity decreased with increasing contents of Se and fell to 0.36 W m−1 K−1 at 823 K for the composition SnS0.5Se0.5. With increasing selenium content (x) the formation of solid solutions substantially improved the electrical conductivity due to the increased carrier concentration. Hence, the optimized power factor and reduced thermal conductivity resulted in a maximum ZT value of 0.64 at 823 K for SnS0.2Se0.8 along the parallel direction. PMID:28240324

Thermoelectric SnS and SnS-SnSe solid solutions prepared by mechanical alloying and spark plasma sintering: Anisotropic thermoelectric properties.

PubMed

Asfandiyar; Wei, Tian-Ran; Li, Zhiliang; Sun, Fu-Hua; Pan, Yu; Wu, Chao-Feng; Farooq, Muhammad Umer; Tang, Huaichao; Li, Fu; Li, Bo; Li, Jing-Feng

2017-02-27

P-type SnS compound and SnS 1-x Se x solid solutions were prepared by mechanical alloying followed by spark plasma sintering (SPS) and their thermoelectric properties were then studied in different compositions (x = 0.0, 0.2, 0.5, 0.8) along the directions parallel (//) and perpendicular (⊥) to the SPS-pressurizing direction in the temperature range 323-823 Κ. SnS compound and SnS 1-x Se x solid solutions exhibited anisotropic thermoelectric performance and showed higher power factor and thermal conductivity along the direction ⊥ than the // one. The thermal conductivity decreased with increasing contents of Se and fell to 0.36 W m -1  K -1 at 823 K for the composition SnS 0.5 Se 0.5 . With increasing selenium content (x) the formation of solid solutions substantially improved the electrical conductivity due to the increased carrier concentration. Hence, the optimized power factor and reduced thermal conductivity resulted in a maximum ZT value of 0.64 at 823 K for SnS 0.2 Se 0.8 along the parallel direction.

Fabrication of Heterogeneous-Phase Solid-Solution Promoting Band Structure and Charge Separation for Enhancing Photocatalytic CO2 Reduction: A Case of ZnXCa1-XIn2S4.

PubMed

Zeng, Chao; Huang, Hongwei; Zhang, Tierui; Dong, Fan; Zhang, Yihe; Hu, Yingmo

2017-08-23

Photocatalytic CO 2 reduction into solar fuels illustrates huge charm for simultaneously settling energy and environmental issues. The photoreduction ability of a semiconductor is closely correlated to its conduction band (CB) position. A homogeneous-phase solid-solution with the same crystal system always has a monotonously changed CB position, and the high CB level has to be sacrificed to achieve a benign photoabsorption. Herein, we report the fabrication of heterogeneous-phase solid-solution Zn X Ca 1-X In 2 S 4 between trigonal ZnIn 2 S 4 and cubic CaIn 2 S 4 . The Zn X Ca 1-X In 2 S 4 solid solutions with orderly tuned photoresponsive range from 540 to 640 nm present a more negative CB level and highly enhanced charge-separation efficiency. Profiting from these merits, all of these Zn X Ca 1-X In 2 S 4 solid solutions exhibit remarkably strengthened photocatalytic CO 2 reduction performance under visible light (λ > 420 nm) irradiation. Zn 0.4 Ca 0.6 In 2 S 4 , bearing the most negative CB position and highest charge-separation efficiency, casts the optimal photocatalytic CH 4 and CO evolution rates, which reach 16.7 and 6.8 times higher than that of ZnIn 2 S 4 and 7.2 and 3.9 times higher than that of CaIn 2 S 4 , respectively. To verify the crucial role of the heterogeneous-phase solid solution in promoting the band structure and photocatalytic performance, another heterogeneous-phase solid-solution Zn X Cd 1-X In 2 S 4 has been synthesized. It also displays an upshifted CB level and promoted charge separation. This work may provide a new perspective into the development of an efficient visible-light driven photocatalyst for CO 2 reduction and other photoreduction reactions.

A Study of the Structure-Activity Relationship of GABAA-Benzodiazepine Receptor Bivalent Ligands by Conformational Analysis with Low Temperature NMR and X-ray Analysis

PubMed Central

Han, Dongmei; Försterling, F. Holger; Li, Xiaoyan; Deschamps, Jeffrey R.; Parrish, Damon; Cao, Hui; Rallapalli, Sundari; Clayton, Terry; Teng, Yun; Majumder, Samarpan; Sankar, Subramaniam; Roth, Bryan L.; Sieghart, Werner; Furtmuller, Roman; Rowlett, James; Weed, Mike R.; Cook, James M.

2013-01-01

The stable conformations of GABAA-benzodiazepine receptor bivalent ligands were determined by low temperature NMR spectroscopy and confirmed by single crystal X-ray analysis. The stable conformations in solution correlated well with those in the solid state. The linear conformation was important for these dimers to access the binding site and exhibit potent in vitro affinity and was illustrated for α5 subtype selective ligands. Bivalent ligands with an oxygen-containing linker folded back upon themselves both in solution and the solid state. Dimers which are folded do not bind to Bz receptors. PMID:18790643

The polymorphic and mesomorphic behavior of four esters of cholesterol.

NASA Technical Reports Server (NTRS)

Merritt, W. G.; Cole, G. D.; Walker, W. W.

1971-01-01

The techniques of differential scanning calorimetry, X-ray powder diffractometry, and positron annihilation have been used to study the polymorphic and mesomorphic behavior of the following esters of cholesterol: cholesteryl formate, cholesteryl butyrate, cholesteryl benzoate, and cholesteryl cinnamate. Each of these compounds exhibits a single mesophase of the cholesteric type. The solid phase formed from the melt for each ester was observed to be structurally different from the solid phase obtained from solution. Solvents from which the solution-grown samples were crystallized were as follows: cholesteryl formate and cholesteryl butyrate from acetone, cholesteryl benzoate from benzene, and cholesteryl cinnamate from 2-butanone.

Raman spectroscopic investigation of thorium dioxide-uranium dioxide (ThO₂-UO₂) fuel materials.

PubMed

Rao, Rekha; Bhagat, R K; Salke, Nilesh P; Kumar, Arun

2014-01-01

Raman spectroscopic investigations were carried out on proposed nuclear fuel thorium dioxide-uranium dioxide (ThO2-UO2) solid solutions and simulated fuels based on ThO2-UO2. Raman spectra of ThO2-UO2 solid solutions exhibited two-mode behavior in the entire composition range. Variations in mode frequencies and relative intensities of Raman modes enabled estimation of composition, defects, and oxygen stoichiometry in these compounds that are essential for their application. The present study shows that Raman spectroscopy is a simple, promising analytical tool for nondestructive characterization of this important class of nuclear fuel materials.

Synthesis and photocatalytic degradation study of methylene blue dye under visible light irradiation by Fe1-xBixVO4 solid solutions (0 ≤ x ≤ 1.0)

NASA Astrophysics Data System (ADS)

Bera, Ganesh; Reddy, V. R.; Mal, Priyanath; Das, Pradip; Turpu, G. R.

2018-05-01

The novel hetero-structures Fe1-xBixVO4 solid solutions (0 ≤ x ≤ 1.0) with the two dissimilar end member of FeVO4 - BiVO4, were successfully synthesized by the standard solid state reaction method. The structural and chemical properties of as prepared photo-catalyst samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR) and UV-visible absorption spectroscopy techniques. It is confirmed from the results of XRD, Raman and FT-IR that FeVO4 and BiVO4 are in triclinic (space group P-1 (2)) and monoclinic (space group I2/b (15)) phases respectively. The Bi incorporation into Fe site of FeVO4 emerges as hetero-structures of both the end members of the solid solutions. In addition, the photocatalytic activity in the degradation of methylene blue (MB) dye under visible light irradiation was carried out through UV-visible spectroscopy measurement of photo-catalysts FeVO4, BiVO4 and mixed phases of both photo-catalyst. The results indicate that under visible light irradiation the photocatalytic activity of mixed phases were very effective and higher than the both single phases of the solid solutions. The composition x= 0.25 exhibits an excellent photocatalytic property for the degradation of MB solution under visible light irradiation rather than other.

Enhancement of dissolution rate through eutectic mixture and solid solution of posaconazole and benznidazole.

PubMed

Figueirêdo, Camila Bezerra Melo; Nadvorny, Daniela; de Medeiros Vieira, Amanda Carla Quintas; Soares Sobrinho, José Lamartine; Rolim Neto, Pedro José; Lee, Ping I; de La Roca Soares, Monica Felts

2017-06-15

Benznidazole (BNZ), the only commercialized antichagasic drug, and the antifungal compound posaconazole (PCZ) have shown synergistic action in the therapy of Chagas disease, however both active pharmaceutical ingredients (APIs) exhibit low aqueous solubility potentially limiting their bioavailability and therapeutic efficacy. In this paper, we report for the first time the formation of a eutectic mixture as well as an amorphous solid solution of PCZ and BNZ (at the same characteristic ratio of 80:20wt%), which provided enhanced solubility and dissolution rate for both APIs. This eutectic system was characterized by DSC and the melting points obtained were used for the construction of a phase diagram. The preservation of the characteristic PXRD patterns and the IR spectra of the parent APIs, and the visualization of a characteristic eutectic lamellar crystalline microstructure using Confocal Raman Microscopy confirm this system as a true eutectic mixture. The PXRD result also confirms the amorphous nature of the prepared solid solution. Theoretical chemical analyses indicate the predominance of π-stacking interactions in the amorphous solid solution, whereas an electrostatic interaction between the APIs is responsible for maintaining the alternating lamellar crystalline microstructure in the eutectic mixture. Both the eutectic mixture and the amorphous solid solution happen to have a characteristic PCZ to BNZ ratio similar to that of their pharmacological doses for treating Chagas disease, thus providing a unique therapeutic combination dose with enhanced apparent solubility and dissolution rate. Copyright © 2017 Elsevier B.V. All rights reserved.

Detection of X-ray photons by solution-processed organic-inorganic perovskites

PubMed Central

Yakunin, Sergii; Sytnyk, Mykhailo; Kriegner, Dominik; Shrestha, Shreetu; Richter, Moses; Matt, Gebhard J.; Azimi, Hamed; Brabec, Christoph J.; Stangl, Julian; Kovalenko, Maksym V.; Heiss, Wolfgang

2017-01-01

The evolution of real-time medical diagnostic tools such as angiography and computer tomography from radiography based on photographic plates was enabled by the development of integrated solid-state X-ray photon detectors, based on conventional solid-state semiconductors. Recently, for optoelectronic devices operating in the visible and near infrared spectral regions, solution-processed organic and inorganic semiconductors have also attracted immense attention. Here we demonstrate a possibility to use such inexpensive semiconductors for sensitive detection of X-ray photons by direct photon-to-current conversion. In particular, methylammonium lead iodide perovskite (CH3NH3PbI3) offers a compelling combination of fast photoresponse and a high absorption cross-section for X-rays, owing to the heavy Pb and I atoms. Solution processed photodiodes as well as photoconductors are presented, exhibiting high values of X-ray sensitivity (up to 25 µC mGyair-1 cm-3) and responsivity (1.9×104 carriers/photon), which are commensurate with those obtained by the current solid-state technology. PMID:28553368

Formation of soft magnetic high entropy amorphous alloys composites containing in situ solid solution phase

NASA Astrophysics Data System (ADS)

Wei, Ran; Sun, Huan; Chen, Chen; Tao, Juan; Li, Fushan

2018-03-01

Fe-Co-Ni-Si-B high entropy amorphous alloys composites (HEAACs), which containing high entropy solid solution phase in amorphous matrix, show good soft magnetic properties and bending ductility even in optimal annealed state, were successfully developed by melt spinning method. The crystallization phase of the HEAACs is solid solution phase with body centered cubic (BCC) structure instead of brittle intermetallic phase. In addition, the BCC phase can transformed into face centered cubic (FCC) phase with temperature rise. Accordingly, Fe-Co-Ni-Si-B high entropy alloys (HEAs) with FCC structure and a small amount of BCC phase was prepared by copper mold casting method. The HEAs exhibit high yield strength (about 1200 MPa) and good plastic strain (about 18%). Meanwhile, soft magnetic characteristics of the HEAs are largely reserved from HEAACs. This work provides a new strategy to overcome the annealing induced brittleness of amorphous alloys and design new advanced materials with excellent comprehensive properties.

Atomic-scale dynamics of edge dislocations in Ni and concentrated solid solution NiFe alloys

DOE PAGES

Zhao, Shijun; Osetsky, Yuri N.; Zhang, Yanwen; ...

2017-01-19

Single-phase concentrated solid solution alloys (CSAs), including high entropy alloys, exhibit excellent mechanical properties compared to conventional dilute alloys. However, the origin of this observation is not clear yet because the dislocation properties in CSAs are poorly understood. In this work, the mobility of a <110>{111} edge dislocation in pure Ni and equiatomic solid solution Ni 0.5Fe 0.5 (NiFe) is studied using molecular dynamics simulations with different empirical potentials. The threshold stress to initiate dislocation movement in NiFe is found to be much higher compared to pure Ni. The drag coefficient of the dislocation motion calculated from the linear regimemore » of dislocation velocities versus applied stress suggests that the movement of dislocations in NiFe is strongly damped compared to that in Ni. The present results indicate that the mobility of edge dislocations in fcc CSAs are controlled by the fluctuations in local stacking fault energy caused by the local variation of alloy composition.« less

Bi2MoxW1-xO6 solid solutions with tunable band structure and enhanced visible-light photocatalytic activities

NASA Astrophysics Data System (ADS)

Li, Wenqi; Ding, Xingeng; Wu, Huating; Yang, Hui

2018-07-01

Semiconductor photocatalysis is an effective green way to combat water pollution. For the first time, this study reports a novel method to develop Bi2MoxW1-xO6 solid solution with microsphere structure through anion-exchange method. All Bi2MoxW1-xO6 samples exhibit an Aurivillius-type crystal structure without any secondary phase, confirming that in complete solid solutions as the value of x increases, the band gap energy of Bi2MoxW1-xO6 solid solutions decreases, while the optical absorption edge moves to longer wavelength. The Raman spectra research shows an increase in orthorhombic distortion with progressive replacement of W sites in Bi2WO6 with Mo6+ ions. Compared to Bi2MoO6 and Bi2WO6 samples, Bi2Mo0.4W0.6O6 sample displayed best photocatalytic activity and cycling stability for degradation of RhB dye. The enhanced photocatalytic activity of Bi2Mo0.4W0.6O6 sample can be synergetically linked to hierarchical hollow structure, enhanced light absorbance, and high carrier-separation efficiency. Additionally, the hollow Bi2MoxW1-xO6 microspheres formation can be attributed to the Kirkendall effect.

High-throughput 96-well solvent mediated sonic blending synthesis and on-plate solid/solution stability characterization of pharmaceutical cocrystals.

PubMed

Luu, Van; Jona, Janan; Stanton, Mary K; Peterson, Matthew L; Morrison, Henry G; Nagapudi, Karthik; Tan, Helming

2013-01-30

A 96-well high-throughput cocrystal screening workflow has been developed consisting of solvent-mediated sonic blending synthesis and on-plate solid/solution stability characterization by XRPD. A strategy of cocrystallization screening in selected blend solvents including water mixtures is proposed to not only manipulate solubility of the cocrystal components but also differentiate physical stability of the cocrystal products. Caffeine-oxalic acid and theophylline-oxalic acid cocrystals were prepared and evaluated in relation to saturation levels of the cocrystal components and stability of the cocrystal products in anhydrous and hydrous solvents. AMG 517 was screened with a number of coformers, and solid/solution stability of the resulting cocrystals on the 96-well plate was investigated. A stability trend was observed and confirmed that cocrystals comprised of lower aqueous solubility coformers tended to be more stable in water. Furthermore, cocrystals which could be isolated under hydrous solvent blending condition exhibited superior physical stability to those which could only be obtained under anhydrous condition. This integrated HTS workflow provides an efficient route in an API-sparing approach to screen and identify cocrystal candidates with proper solubility and solid/solution stability properties. Copyright © 2012 Elsevier B.V. All rights reserved.

Recycling: You are the solution

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

Not Available

Americans produce nearly 150 million tons of residential and commercial solid waste each year, or slightly less than 1,400 lb for each one of us. This document contains various items related to public education: exhibit text, vocabulary, collection sites, classroom and individual activities, puzzles, classroom simulations.

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

PubMed

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

2012-11-05

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

Catalytic method for synthesizing hydrocarbons

DOEpatents

Sapienza, R.S.; Sansone, M.J.; Slegeir, W.A.R.

A method for synthesizing hydrocarbons from carbon monoxide and hydrogen by contacting said gases with a slurry of a catalyst composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants.

Catalytic method for synthesizing hydrocarbons

DOEpatents

Sapienza, Richard S.; Sansone, Michael J.; Slegeir, William A. R.

1984-01-01

A method for synthesizing hydrocarbons from carbon monoxide and hydrogen by contacting said gases with a slurry of a catalyst composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants.

An Investigation of the Effects of Self-Assembled Monolayers on Protein Crystallisation

PubMed Central

Zhang, Chen-Yan; Shen, He-Fang; Wang, Qian-Jin; Guo, Yun-Zhu; He, Jin; Cao, Hui-Ling; Liu, Yong-Ming; Shang, Peng; Yin, Da-Chuan

2013-01-01

Most protein crystallisation begins from heterogeneous nucleation; in practice, crystallisation typically occurs in the presence of a solid surface in the solution. The solid surface provides a nucleation site such that the energy barrier for nucleation is lower on the surface than in the bulk solution. Different types of solid surfaces exhibit different surface energies, and the nucleation barriers depend on the characteristics of the solid surfaces. Therefore, treatment of the solid surface may alter the surface properties to increase the chance to obtain protein crystals. In this paper, we propose a method to modify the glass cover slip using a self-assembled monolayer (SAM) of functional groups (methyl, sulfydryl and amino), and we investigated the effect of each SAM on protein crystallisation. The results indicated that both crystallisation success rate in a reproducibility study, and crystallisation hits in a crystallisation screening study, were increased using the SAMs, among which, the methyl-modified SAM demonstrated the most significant improvement. These results illustrated that directly modifying the crystallisation plates or glass cover slips to create surfaces that favour heterogeneous nucleation can be potentially useful in practical protein crystallisation, and the utilisation of a SAM containing a functional group can be considered a promising technique for the treatment of the surfaces that will directly contact the crystallisation solution. PMID:23749116

High-Performance Thermoelectric Semiconductors

NASA Technical Reports Server (NTRS)

Fleurial, Jean-Pierre; Caillat, Thierry; Borshchevsky, Alexander

1994-01-01

Figures of merit almost double current state-of-art thermoelectric materials. IrSb3 is semiconductor found to exhibit exceptional thermoelectric properties. CoSb3 and RhSb3 have same skutterudite crystallographic structure as IrSb3, and exhibit exceptional transport properties expected to contribute to high thermoelectric performance. These three compounds form solid solutions. Combination of properties offers potential for development of new high-performance thermoelectric materials for more efficient thermoelectric power generators, coolers, and detectors.

Recycling: You are the solution. Final report

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

Not Available

Americans produce nearly 150 million tons of residential and commercial solid waste each year, or slightly less than 1,400 lb for each one of us. This document contains various items related to public education: exhibit text, vocabulary, collection sites, classroom and individual activities, puzzles, classroom simulations.

Development of SiAlON materials

NASA Technical Reports Server (NTRS)

Layden, G. K.

1977-01-01

Cold pressing and sintering techniques were used to produce ceramic bodies in which the major phase was beta prime Si3-Al-O-N4 solid solution. A variety of foreign oxides were used to promote liquid phase sintering, and this resulted in the incorporation of additional solid phases in the ceramic bodies which controlled elevated temperature properties. None of the bodies studied to date exhibited both adequate high temperature mechanical properties and oxidation resistance. Criteria are suggested to guide the formulation of bodies with improved high temperature properties.

Humic acid facilitates the transport of ARS-labeled hydroxyapatite nanoparticles in iron oxyhydroxide-coated sand

USDA-ARS?s Scientific Manuscript database

Hydroxyapatite nanoparticles (nHAP) have been widely used to remediate soil and wastewater contaminated with metals and radionuclides. However, our understanding of nHAP transport and fate is limited in natural environments that exhibit significant variability in solid and solution chemistry. The tr...

Temperature Dependence of the Mechanical Properties of Equiatomic Solid Solution Alloys with FCC Crystal Structures

DOE PAGES

Wu, Zhenggang; Bei, Hongbin; Pharr, George M.; ...

2014-10-03

We found that compared to decades-old theories of strengthening in dilute solid solutions, the mechanical behavior of concentrated solid solutions is relatively poorly understood. A special subset of these materials includes alloys in which the constituent elements are present in equal atomic proportions, including the high-entropy alloys of recent interest. A unique characteristic of equiatomic alloys is the absence of “solvent” and “solute” atoms, resulting in a breakdown of the textbook picture of dislocations moving through a solvent lattice and encountering discrete solute obstacles. Likewise, to clarify the mechanical behavior of this interesting new class of materials, we investigate heremore » a family of equiatomic binary, ternary and quaternary alloys based on the elements Fe, Ni, Co, Cr and Mn that were previously shown to be single-phase face-centered cubic (fcc) solid solutions. The alloys were arc-melted, drop-cast, homogenized, cold-rolled and recrystallized to produce equiaxed microstructures with comparable grain sizes. Tensile tests were performed at an engineering strain rate of 10 -3 s -1 at temperatures in the range 77–673 K. Unalloyed fcc Ni was processed similarly and tested for comparison. The flow stresses depend to varying degrees on temperature, with some (e.g. NiCoCr, NiCoCrMn and FeNiCoCr) exhibiting yield and ultimate strengths that increase strongly with decreasing temperature, while others (e.g. NiCo and Ni) exhibit very weak temperature dependencies. Moreover, to better understand this behavior, the temperature dependencies of the yield strength and strain hardening were analyzed separately. Lattice friction appears to be the predominant component of the temperature-dependent yield stress, possibly because the Peierls barrier height decreases with increasing temperature due to a thermally induced increase of dislocation width. In the early stages of plastic flow (5–13% strain, depending on material), the temperature dependence of strain hardening is due mainly to the temperature dependence of the shear modulus. In all the equiatomic alloys, ductility and strength increase with decreasing temperature down to 77 K. Keywords« less

Microhardness and In Vitro Corrosion of Heat-Treated Mg–Y–Ag Biodegradable Alloy

PubMed Central

Vlček, Marián; Lukáč, František; Kudrnová, Hana; Smola, Bohumil; Stulíková, Ivana; Luczak, Monika; Szakács, Gábor; Hort, Norbert; Willumeit-Römer, Regine

2017-01-01

Magnesium alloys are promising candidates for biodegradable medical implants which reduce the necessity of second surgery to remove the implants. Yttrium in solid solution is an attractive alloying element because it improves mechanical properties and exhibits suitable corrosion properties. Silver was shown to have an antibacterial effect and can also enhance the mechanical properties of magnesium alloys. Measurements of microhardness and electrical resistivity were used to study the response of Mg–4Y and Mg–4Y–1Ag alloys to isochronal or isothermal heat treatments. Hardening response and electrical resistivity annealing curves in these alloys were compared in order to investigate the effect of silver addition. Procedures for solid solution annealing and artificial aging of the Mg–4Y–1Ag alloy were developed. The corrosion rate of the as-cast and heat-treated Mg–4Y–1Ag alloy was measured by the mass loss method. It was found out that solid solution heat treatment, as well artificial aging to peak hardness, lead to substantial improvement in the corrosion properties of the Mg–4Y–1Ag alloy. PMID:28772414

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.

Influence of compositional complexity on interdiffusion in Ni-containing concentrated solid-solution alloys

DOE PAGES

Jin, Ke; Zhang, Chuan; Zhang, Fan; ...

2018-03-07

To investigate the compositional effects on thermal-diffusion kinetics in concentrated solid-solution alloys, interdiffusion in seven diffusion couples with alloys from binary to quinary is systematically studied. The alloys with higher compositional complexity exhibit in general lower diffusion coefficients against homologous temperature, however, an exception is found that diffusion in NiCoFeCrPd is faster than in NiCoFeCr and NiCoCr. While the derived diffusion parameters suggest that diffusion in medium and high entropy alloys is overall more retarded than in pure metals and binary alloys, they strongly depend on specific constituents. The comparative features are captured by computational thermodynamics approaches using a self-consistentmore » database.« less

Raman effect in multiferroic Bi5Fe1+xTi3-xO15 solid solutions: A temperature study

NASA Astrophysics Data System (ADS)

Rodríguez Aranda, Ma. Del Carmen; Rodríguez-Vázquez, Ángel G.; Salazar-Kuri, Ulises; Mendoza, María Eugenia; Navarro-Contreras, Hugo R.

2018-02-01

In this work, a Raman study of powder samples of multiferroic Bi5Fe1+xTi3-xO15 solid solutions and Bi6Fe2Ti3O18 as a function of temperature from 27 °C (room temperature) to 850 °C is presented. The values of x (i.e., the Fe composition) for the solid solutions were 1.0, 1.1, 1.3, and 1.4. The temperature coefficients of eight phonon frequencies were determined for all the samples. The large observed phonon broadenings with increasing temperature precluded the observation of several of the phonon bands above defined temperatures in the range of 200-700 °C depending on the sample. These phonon broadenings were explained on the basis of the Klemens model, which considers that the broadenings are due to the thermal expansion of the lattice with a major contribution in terms of magnitude from anharmonic phonon-phonon interactions. However, some evidence for the presence of several of the phonons persisted up to 800-850 °C. These solid solutions are expected to exhibit a ferroelectric-paraelectric phase transition at 742 to 750 °C and a ferromagnetic-antiferromagnetic transition at 426 °C. We also observed changes in the slopes of the temperature dependence of the phonon frequencies for the lines at 228 cm-1 for Bi5FeTi3O15 and 330 cm-1 for Bi6Fe2Ti3O18 at temperatures of 247 °C and 347 °C, respectively. No similar temperature-frequency slope changes indicative of possible phase transitions were observed for any of the phonon lines of the other three Bi5Fe1+xTi3-xO15 solid solutions examined.

Linear adsorption of nonionic organic compounds from water onto hydrophilic minerals: Silica and alumina

USGS Publications Warehouse

Su, Y.-H.; Zhu, Y.-G.; Sheng, G.; Chiou, C.T.

2006-01-01

To characterize the linear adsorption phenomena in aqueous nonionic organic solute-mineral systems, the adsorption isotherms of some low-molecular- weightnonpolar nonionic solutes (1,2,3-trichlorobenzene, lindane, phenanthrene, and pyrene) and polar nonionic solutes (1,3-dinitrobenzene and 2,4-dinitrotoluene) from single-and binary-solute solutions on hydrophilic silica and alumina were established. Toward this objective, the influences of temperature, ionic strength, and pH on adsorption were also determined. It is found that linear adsorption exhibits low exothermic heats and practically no adsorptive competition. The solute-solid configuration and the adsorptive force consistent with these effects were hypothesized. For nonpolar solutes, the adsorption occurs presumably by London (dispersion) forces onto a water film above the mineral surface. For polar solutes, the adsorption is also assisted by polar-group interactions. The reduced adsorptive forces of solutes with hydrophilic minerals due to physical separation by the water film and the low fractions of the water-film surface covered by solutes offer a theoretical basis for linear solute adsorption, low exothermic heats, and no adsorptive competition. The postulated adsorptive forces are supported by observations that ionic strength or pH poses no effect on the adsorption of nonpolar solutes while it exhibits a significant effect on the uptake of polar solutes. ?? 2006 American Chemical Society.

Room-temperature synthesis of Zn(0.80)Cd(0.20)S solid solution with a high visible-light photocatalytic activity for hydrogen evolution.

PubMed

Wang, Dong-Hong; Wang, Lei; Xu, An-Wu

2012-03-21

Visible light photocatalytic H(2) production from water splitting is of great significance for its potential applications in converting solar energy into chemical energy. In this study, a series of Zn(1-x)Cd(x)S solid solutions with a nanoporous structure were successfully synthesized via a facile template-free method at room temperature. The obtained solid solutions were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), ultraviolet-visible (UV-vis) diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS) and N(2) adsorption-desorption analysis. The solid solutions show efficient photocatalytic activity for H(2) evolution from aqueous solutions containing sacrificial reagents S(2-) and SO(3)(2-) under visible-light irradiation without a Pt cocatalyst, and loading of the Pt cocatalyst further improves the visible-light photocatalytic activity. The optimal photocatalyst with x = 0.20 prepared at pH = 7.3 displays the highest activity for H(2) evolution. The bare and 0.25 wt% Pt loaded Zn(0.80)Cd(0.20)S nanoparticles exhibit a high H(2) evolution rate of 193 μmol h(-1) and 458 μmol h(-1) under visible-light irradiation (λ ≥ 420 nm), respectively. In addition, the bare and 0.25 wt% Pt loaded Zn(0.80)Cd(0.20)S catalysts show a high H(2) evolution rate of 252 and 640 μmol h(-1) under simulated solar light irradiation, respectively. Moreover, the Zn(0.80)Cd(0.20)S catalyst displays a high photocatalytic stability for H(2) evolution under long-term light irradiation. The incorporation of Cd in the solid solution leads to the visible light absorption, and the high content of Zn in the solid solution results in a relatively negative conduction band, a modulated band gap and a rather wide valence bandwidth, which are responsible for the excellent photocatalytic performance of H(2) production and for the high photostability. This journal is © The Royal Society of Chemistry 2012

Dispersoid reinforced alloy powder and method of making

DOEpatents

Anderson, Iver E [Ames, IA; Terpstra, Robert L [Ames, IA

2012-06-12

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomized particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.

Dispersoid reinforced alloy powder and method of making

DOEpatents

Anderson, Iver E.; Terpstra, Robert L.

2010-04-20

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomized particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.

Determinants of the efficiency of photon upconversion by triplet-triplet annihilation in the solid state: zinc porphyrin derivatives in PVA.

PubMed

Rautela, Ranjana; Joshi, Neeraj K; Novakovic, Sacha; Wong, Wallace W H; White, Jonathan M; Ghiggino, Kenneth P; Paige, Matthew F; Steer, Ronald P

2017-08-30

Spectroscopic, photophysical and computational studies designed to expose and explain the differences in the efficiencies of non-coherent photon upconversion (NCPU) by triplet-triplet annihilation (TTA) have been carried out for a new series of alkyl-substituted diphenyl and tetraphenyl zinc porphyrins, both in fluid solution and in solid films. Systematic variations in the alkyl-substitution of the phenyl groups in both the di- and tetraphenyl porphyrins introduces small, but well-understood changes in their spectroscopic and photophysical properties and in their TTA efficiencies. In degassed toluene solution TTA occurs for all derivatives and produces the fluorescent S 2 product states in all cases. In PVA matrices, however, none of the di-phenylporphyrins exhibit measurable NCPU whereas all the tetraphenyl-substituted compounds remain upconversion-active. In PVA the NCPU efficiencies of the zinc tetraphenylporphyrins vary significantly with their steric characteristics; the most sterically crowded tetraphenyl derivative exhibits the greatest efficiency. DFT-D computations have been undertaken and help reveal the sources of these differences.

A Synthetic Pseudo-Rh: NOx Reduction Activity and Electronic Structure of Pd-Ru Solid-solution Alloy Nanoparticles

NASA Astrophysics Data System (ADS)

Sato, Katsutoshi; Tomonaga, Hiroyuki; Yamamoto, Tomokazu; Matsumura, Syo; Zulkifli, Nor Diana Binti; Ishimoto, Takayoshi; Koyama, Michihisa; Kusada, Kohei; Kobayashi, Hirokazu; Kitagawa, Hiroshi; Nagaoka, Katsutoshi

2016-06-01

Rh is one of the most important noble metals for industrial applications. A major fraction of Rh is used as a catalyst for emission control in automotive catalytic converters because of its unparalleled activity toward NOx reduction. However, Rh is a rare and extremely expensive element; thus, the development of Rh alternative composed of abundant elements is desirable. Pd and Ru are located at the right and left of Rh in the periodic table, respectively, nevertheless this combination of elements is immiscible in the bulk state. Here, we report a Pd-Ru solid-solution-alloy nanoparticle (PdxRu1-x NP) catalyst exhibiting better NOx reduction activity than Rh. Theoretical calculations show that the electronic structure of Pd0.5Ru0.5 is similar to that of Rh, indicating that Pd0.5Ru0.5 can be regarded as a pseudo-Rh. Pd0.5Ru0.5 exhibits better activity than natural Rh, which implies promising applications not only for exhaust-gas cleaning but also for various chemical reactions.

Experimental measurements of U60 nanocluster stability in aqueous solution

NASA Astrophysics Data System (ADS)

Flynn, Shannon L.; Szymanowski, Jennifer E. S.; Gao, Yunyi; Liu, Tianbo; Burns, Peter C.; Fein, Jeremy B.

2015-05-01

In this study, the aqueous behavior of isolated U60 nanoclusters (K16Li25[UO2(O2)OH]60)-19 was studied under several pH conditions and nanocluster concentrations to determine if the nanoclusters exhibit solid phase buffering behavior or if they exhibit behavior more like aqueous complexes. U60 is a cage cluster consisting of 60 (UO2)(O2)2(OH)2 uranyl polyhedral which share OH and O2 groups with their neighboring uranyl polyhedral, resulting in negatively charged cage clusters whose charge is at least partially offset by K+ and Li+ in the aqueous phase. Batch experiments to monitor nanocluster stability were conducted for 16 days at pH 7.5, 8.0 and 8.5 at nanocluster suspension concentrations of 1.4, 2.8 and 6.0 g/L. The aqueous concentrations of U, Li, and K, determined after 10 kDa molecular weight filtration, achieved steady-state with the nanoclusters within 24 h. The steady-state aqueous U, Li, and K concentrations were independent of solution pH, however they increased with increasing nanocluster concentration, indicating that the nanoclusters do not buffer the aqueous activities as a bulk solid phase would, but exhibit behavior that is more characteristic of dissolved aqueous complexes. The ion activity product (I.A.P.) value was calculated using two approaches: (1) treating the nanoclusters as a solid phase with an activity of one, and (2) treating the nanoclusters as aqueous complexes with a non-unit activity equal to their concentration in solution. The I.A.P. values that were calculated with non-unit activity for the nanoclusters exhibited significantly less variation as a function of nanocluster concentration compared to the I.A.P. values calculated with a nanocluster activity of one. The results yield a calculated log dissociation constant for the U60 nanoclusters of 9.2 + 0.2/-0.3 (1σ). Our findings provide a better understanding of the thermodynamic stability and behavior of U60 nanoclusters in aqueous systems, and can be used to estimate the dissociation behavior of nanoclusters under a range of aqueous conditions.

Hydrocarbon synthesis catalyst and method of preparation

DOEpatents

Sapienza, R.S.; Sansone, M.J.; Slegeir, W.A.R.

1983-08-02

A catalyst for the synthesis of hydrocarbons from carbon monoxide and hydrogen composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants. The catalyst is preferably used in dilute slurry form, which is desirable from a heat transfer standpoint. 9 figs.

Hydrocarbon synthesis catalyst and method of preparation

DOEpatents

Sapienza, Richard S.; Sansone, Michael J.; Slegeir, William A. R.

1983-08-02

A catalyst for the synthesis of hydrocarbons from carbon monoxide and hydrogen composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants. The catalyst is preferably used in dilute slurry form, which is desirable from a heat transfer standpoint.

A Saturn-Like Complex Composed of Macrocyclic Oligothiophene and C60 Fullerene: Structure, Stability, and Photophysical Properties in Solution and the Solid State.

PubMed

Shimizu, Hideyuki; Park, Kyu Hyung; Otani, Hiroyuki; Aoyagi, Shinobu; Nishinaga, Tohru; Aso, Yoshio; Kim, Dongho; Iyoda, Masahiko

2018-03-12

A Saturn-like 1:1 complex composed of macrocyclic oligothiophene E-8T7A and C 60 fullerene (C 60 ) was synthesized to investigate the interaction between macrocyclic oligothiophenes and C 60 in solution and the solid state. Because the Saturn-like 1:1 complex E-8T7A⋅C 60 is mainly stabilized by van der Waals interactions between C 60 and the sulfur atoms of the E-8T7A macrocycle, C 60 is rather weakly incorporated inside the macro-ring in solution. However, in the solid state the Saturn-like 1:1 complex preferentially formed single crystals or nanostructured polymorphs. Interestingly, X-ray analysis and theoretical calculations exhibited hindered rotation of C 60 in the Saturn-like complex due to interactions between C 60 and the sulfur atoms. Furthermore, the photoinduced charge transfer (CT) interaction between E-8T7A and C 60 in solution was investigated by using femtosecond transient absorption (TA) spectroscopy. The ultrafast TA spectral changes in the photoinduced absorption bands were attributed to the CT process in the Saturn-like structure. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coupling between magnetic and optical properties of stable Au-Fe solid solution nanoparticles

NASA Astrophysics Data System (ADS)

de Julián Fernández, C.; Mattei, G.; Paz, E.; Novak, R. L.; Cavigli, L.; Bogani, L.; Palomares, F. J.; Mazzoldi, P.; Caneschi, A.

2010-04-01

Au-Fe nanoparticles constitute one of the simplest prototypes of a multifunctional nanomaterial that can exhibit both magnetic and optical (plasmonic) properties. This solid solution, not feasible in the bulk phase diagram in thermal equilibrium, can be formed as a nanostructure by out-of-equilibrium processes. Here, the novel magnetic, optical and magneto-optical properties of ion-implanted Au-Fe solid solution nanoparticles dispersed in a SiO2 matrix are investigated and correlated. The surface plasmon resonance of the Au-Fe nanoparticles with almost equicomposition is strongly damped when compared to pure Au and to Au-rich Au-Fe nanoparticles. In all cases, the Au atoms are magnetically polarized, as measured by x-ray magnetic circular dichroism, and ferromagnetically coupled with Fe atoms. Although the chemical stability of Au-Fe nanoparticles is larger than that of Fe nanoparticles, both the magnetic moment per Fe atom and the order temperature are smaller. These results suggest that electronic and magnetic properties are more influenced by the hybridization of the electronic bands in the Au-Fe solid solution than by size effects. On the other hand, the magneto-optical transitions allowed in the vis-nIR spectral regions are very similar. In addition, we also observe, after studying the properties of thermally treated samples, that the Au-Fe alloy is stabilized, not by surface effects, but by the combination of the out-of-equilibrium nature of the ion implantation technique and by changes in the properties due to size effects.

Coupling between magnetic and optical properties of stable Au-Fe solid solution nanoparticles.

PubMed

de Julián Fernández, C; Mattei, G; Paz, E; Novak, R L; Cavigli, L; Bogani, L; Palomares, F J; Mazzoldi, P; Caneschi, A

2010-04-23

Au-Fe nanoparticles constitute one of the simplest prototypes of a multifunctional nanomaterial that can exhibit both magnetic and optical (plasmonic) properties. This solid solution, not feasible in the bulk phase diagram in thermal equilibrium, can be formed as a nanostructure by out-of-equilibrium processes. Here, the novel magnetic, optical and magneto-optical properties of ion-implanted Au-Fe solid solution nanoparticles dispersed in a SiO(2) matrix are investigated and correlated. The surface plasmon resonance of the Au-Fe nanoparticles with almost equicomposition is strongly damped when compared to pure Au and to Au-rich Au-Fe nanoparticles. In all cases, the Au atoms are magnetically polarized, as measured by x-ray magnetic circular dichroism, and ferromagnetically coupled with Fe atoms. Although the chemical stability of Au-Fe nanoparticles is larger than that of Fe nanoparticles, both the magnetic moment per Fe atom and the order temperature are smaller. These results suggest that electronic and magnetic properties are more influenced by the hybridization of the electronic bands in the Au-Fe solid solution than by size effects. On the other hand, the magneto-optical transitions allowed in the vis-nIR spectral regions are very similar. In addition, we also observe, after studying the properties of thermally treated samples, that the Au-Fe alloy is stabilized, not by surface effects, but by the combination of the out-of-equilibrium nature of the ion implantation technique and by changes in the properties due to size effects.

Rh-Catalyzed annulations of N-methoxybenzamides with ketenimines: synthesis of 3-aminoisoindolinones and 3-diarylmethyleneisoindolinones with strong aggregation induced emission properties.

PubMed

Zhou, Xiaorong; Peng, Zhixing; Zhao, Hongyang; Zhang, Zhiyin; Lu, Ping; Wang, Yanguang

2016-08-23

Rhodium-catalyzed C-H activation/annulation reactions of ketenimines with N-methoxybenzamides furnished 3-aminoisoindolin-1-ones and 3-(diarylmethylene)isoindolin-1-ones. The synthesized 3-(diarylmethylene)isoindolin-1-ones exhibited aggregation induced emissions in aqueous tetrahydrofuran solution and strong green-yellow emissions in solids.

Study of liquid?liquid demixing from drug solution

NASA Astrophysics Data System (ADS)

Lafferrère, Laurent; Hoff, Christian; Veesler, Stéphane

2004-09-01

In pharmaceutical industry, a deep understanding of the phase diagram is required in design of crystallization processes. We have investigated the phase diagram of a pharmaceutical compound (C 35H 41Cl 2N 3O 2) in a mixture of ethanol/water. This phase diagram exhibits a solid-solid (polymorphism) and a liquid-liquid-phase separation (LLPS) as a function of temperature and drug substance concentration. This study focuses on the LLPS which is metastable with respect to the crystallization of the two polymorphs FI and FII of C 35H 41Cl 2N 3O 2 in an ethanol/water mixture. The LLPS is metastable towards the solubility curve on the whole solvent-solute concentrations and temperature range studied. The LLPS occurred within the metastable zone for crystallization. In our experiments the liquid-liquid-phase transition prevented the drug from crystallizing, while it changed the medium and the conditions of crystallization, which consequently affected the process. The coexistence curves for the liquid phases, also named TL-L boundary, and the spinodal line were measured for a ternary mixture of water-drug-ethanol at atmospheric pressure over a temperature range of 10-50°C. This temperature range corresponds to that used in the crystallization process. Static Light Scattering, HPLC measurements and Karl-Fischer titration were applied to investigate the drug-phase diagram. The isoplethe section of the phase diagram exhibits four regions: one homogeneous (one liquid) and three two-phases (two regions with one liquid+one solid and one region with two liquids), the two solids phases being two polymorphs.

The effect of carbon distribution on deformation and cracking of Ni-16Cr-9Fe-C alloys

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

Hertzberg, J.L.; Was, G.S.

1995-12-31

Constant extension rate tensile (CERT) tests and constant load tensile (CLT) tests were conducted on controlled purity Ni-16Cr-9Fe-C alloys. The amount and form of carbon were varied in order to investigate the roles of carbon in solution and as intergranular (IG) carbides in the deformation and IG cracking behavior in 360 C argon and primary water environments. Results show that the strength, ductility and creep resistance of these alloys are increased with carbon present in solid solution, while IG cracking on the fracture surface is suppressed. Alloys containing carbon in the form of IG carbides, however, exhibit reduced strength andmore » ductility relative to carbon in solution, while maintaining high IG cracking resistance with respect to carbon-free alloys. CERT results of commercial alloy 600 and controlled purity, carbon containing alloys yield comparable failure strains and IG cracking amounts. CLT comparisons with creep tests of alloy 600 suggest that alloys containing IG carbides are more susceptible to creep than those containing all carbon in solid solution.« less

Multilayer heterostructures and their manufacture

DOEpatents

Hammond, Scott R; Reese, Matthew; Rupert, Benjamin; Miedaner, Alexander; Curtis, Clavin; Olson, Dana; Ginley, David S

2015-11-04

A method of synthesizing multilayer heterostructures including an inorganic oxide layer residing on a solid substrate is described. Exemplary embodiments include producing an inorganic oxide layer on a solid substrate by a liquid coating process under relatively mild conditions. The relatively mild conditions include temperatures below 225.degree. C. and pressures above 9.4 mb. In an exemplary embodiment, a solution of diethyl aluminum ethoxide in anhydrous diglyme is applied to a flexible solid substrate by slot-die coating at ambient atmospheric pressure, and the diglyme removed by evaporation. An AlO.sub.x layer is formed by subjecting material remaining on the solid substrate to a relatively mild oven temperature of approximately 150.degree. C. The resulting AlO.sub.x layer exhibits relatively high light transmittance and relatively low vapor transmission rates for water. An exemplary embodiment of a flexible solid substrate is polyethylene napthalate (PEN). The PEN is not substantially adversely affected by exposure to 150.degree. C

Laser-induced fluorescence spectrometer based on tunable color center laser for low-impurity-solution diagnostic and analysis

NASA Astrophysics Data System (ADS)

Basiev, Tasoltan T.; Fedorov, Vladimir V.; Karasik, Alexander Y.; Lin'kov, S. I.; Orlovskii, Yurii V.; Osiko, Vyacheslav V.; Panov, Vitaly A.; Prokhorov, Alexander M.; Vorob'ev, Ivan N.; Zverev, Peter G.

1996-11-01

Solid state (SS) tunable LiF:F2 color center laser with second and fourth harmonic generation for visible and ultra violet spectral ranges was developed for the laser induced fluorescence spectroscopy (LIFS). The construction and properties of excitation, registration and flame atomization systems for water solution diagnostic are discussed. The testing experiment with low iron concentrated water sample exhibits ultrahigh sensitivity which was estimated to be 0.05 ppb in our set-up. The SS LIFS spectrometer developed is usable to measure more than 42 metal elements in solution on the ppm, ppb level for various medical and biological applications.

Hydrothermal Synthesis of Nanostructured Vanadium Oxides

PubMed Central

Livage, Jacques

2010-01-01

A wide range of vanadium oxides have been obtained via the hydrothermal treatment of aqueous V(V) solutions. They exhibit a large variety of nanostructures ranging from molecular clusters to 1D and 2D layered compounds. Nanotubes are obtained via a self-rolling process while amazing morphologies such as nano-spheres, nano-flowers and even nano-urchins are formed via the self-assembling of nano-particles. This paper provides some correlation between the molecular structure of precursors in the solution and the nanostructure of the solid phases obtained by hydrothermal treatment. PMID:28883325

Compression behavior of quaternary and higher order solid-solution L1(2) trialuminides

NASA Technical Reports Server (NTRS)

Kumar, K. S.; Brown, S. A.

1992-01-01

Results from preliminary studies undertaken to evaluate the existence of single-phase L1(2) solid solutions between pairs of ternary L1(2) trialuminides are presented. Two-kilogram ingots of selected quaternary compositions were cast, homogenized and forged into pancakes; compression specimens were machined from the forgings and tested as a function of temperature. The results are compared against existing data for the ternary alloys. The ternary L1(2) trialuminides Al66Ti25Mn9, Al67Ti25Cr8, and Al22Ti8Fe3 were found to exhibit continuous solubility in one another. The quaternary Cr-Mn composition does not indicate any strength advantage over its ternary counterparts. The continuous replacement of Mn with Fe enhances the strength of the quaternary compound over the ternary Al66Ti25 Mn9.

Enhancements and limits in drug membrane transport using supersaturated solutions of poorly water soluble drugs.

PubMed

Raina, Shweta A; Zhang, Geoff G Z; Alonzo, David E; Wu, Jianwei; Zhu, Donghua; Catron, Nathaniel D; Gao, Yi; Taylor, Lynne S

2014-09-01

Amorphous solid dispersions (ASDs) give rise to supersaturated solutions (solution concentration greater than equilibrium crystalline solubility). We have recently found that supersaturating dosage forms can exhibit the phenomenon of liquid-liquid phase separation (LLPS). Thus, the high supersaturation generated by dissolving ASDs can lead to a two-phase system wherein one phase is an initially nanodimensioned and drug-rich phase and the other is a drug-lean continuous aqueous phase. Herein, the membrane transport of supersaturated solutions, at concentrations above and below the LLPS concentration has been evaluated using a side-by-side diffusion cell. Measurements of solution concentration with time in the receiver cell yield the flux, which reflects the solute thermodynamic activity in the donor cell. As the nominal concentration of solute in the donor cell increases, a linear increase in flux was observed up to the concentration where LLPS occurred. Thereafter, the flux remained essentially constant. Both nifedipine and felodipine solutions exhibit such behavior as long as crystallization is absent. This suggests that there is an upper limit in passive membrane transport that is dictated by the LLPS concentration. These results have several important implications for drug delivery, especially for poorly soluble compounds requiring enabling formulation technologies. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association.

Wafer-scale development and experimental verification of 0.36 mm2 228 mV open-circuit-voltage solid-state CMOS-compatible glucose fuel cell

NASA Astrophysics Data System (ADS)

Arata, Shigeki; Hayashi, Kenya; Nishio, Yuya; Kobayashi, Atsuki; Nakazato, Kazuo; Niitsu, Kiichi

2018-04-01

The world’s smallest (0.36 mm2) solid-state CMOS-compatible glucose fuel cell, which exhibits an open-circuit voltage (OCV) of 228 mV and a power generation density of 1.32 µW/cm2 with a 30 mM glucose solution, is reported in this paper. Compared with conventional wet etching, dry etching (reactive ion etching) for patterning minimizes damage to the anode and cathode, resulting in a cell with a small size and a high OCV, sufficient for CMOS circuit operation.

Effect of d electrons on defect properties in equiatomic NiCoCr and NiCoFeCr concentrated solid solution alloys

DOE PAGES

Zhao, Shijun; Egami, Takeshi; Stocks, G. Malcolm; ...

2018-01-01

Here, the role of d electrons in determining distributions of formation and migration energies for point defects in equiatomic NiCoCr and NiCoFeCr concentrated solid solution alloys (CSAs) are studied regarding electron density deformation flexibility based on first-principles calculations. The disordered state is taken into account by constructing special quasirandom structures. The migration barriers are determined by directly optimizing the saddle point. It is found that the formation energies of interstitials in CSAs are lower than those in pure Ni, whereas the formation energies of vacancies are higher. In both NiCoCr and NiCoFeCr, Co-related dumbbell interstitials exhibit lower formation energies. Notably,more » the distributions of migration energies for Cr interstitials and vacancies exhibit a remarkable overlap region. A detailed analysis of electronic properties reveals that the electronic charge deformation flexibility regarding e g to t 2g transition has a dominant effect on defect energetics for different elements in CSAs. Thus the electron deformation ability is suggested as a key factor in understanding the peculiar defect behavior in CSAs.« less

Effect of d electrons on defect properties in equiatomic NiCoCr and NiCoFeCr concentrated solid solution alloys

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

Zhao, Shijun; Egami, Takeshi; Stocks, G. Malcolm

Here, the role of d electrons in determining distributions of formation and migration energies for point defects in equiatomic NiCoCr and NiCoFeCr concentrated solid solution alloys (CSAs) are studied regarding electron density deformation flexibility based on first-principles calculations. The disordered state is taken into account by constructing special quasirandom structures. The migration barriers are determined by directly optimizing the saddle point. It is found that the formation energies of interstitials in CSAs are lower than those in pure Ni, whereas the formation energies of vacancies are higher. In both NiCoCr and NiCoFeCr, Co-related dumbbell interstitials exhibit lower formation energies. Notably,more » the distributions of migration energies for Cr interstitials and vacancies exhibit a remarkable overlap region. A detailed analysis of electronic properties reveals that the electronic charge deformation flexibility regarding e g to t 2g transition has a dominant effect on defect energetics for different elements in CSAs. Thus the electron deformation ability is suggested as a key factor in understanding the peculiar defect behavior in CSAs.« less

Flipping the Switch: Fast Photoisomerization in a Confined Environment.

PubMed

Williams, Derek E; Martin, Corey R; Dolgopolova, Ekaterina A; Swifton, Anton; Godfrey, Danielle C; Ejegbavwo, Otega A; Pellechia, Perry J; Smith, Mark D; Shustova, Natalia B

2018-05-28

Stimuli-responsive materials are vital for addressing emerging demands in the advanced technology sector as well as current industrial challenges. Here, we report for the first time that coordinative integration of photoresponsive building blocks possessing photochromic spiropyran and diarylethene moieties within a rigid scaffold of metal-organic frameworks (MOFs) could control photophysics; in particular, cycloreversion kinetics with the level of control, which is not accessible in the solid state or solution. On the series of photoactive materials, we demonstrated for the first time that photoisomerization rates of photochromic compounds could be tuned within almost two orders of magnitude. Moreover, cycloreversion rates of photoresponsive derivatives could be modulated as a function of the framework structure. Furthermore, through MOF engineering we were able to achieve complete isomerization for coordinatively immobilized spiropyran derivatives, typically exhibiting limited photoswitching behavior in the solid state. For instance, spectroscopic analysis revealed that the novel monosubstituted spiropyran derivative grafted to the backbone of the MOF pillar exhibits a remarkable photoisomerization rate of 0.16 s-1, typical for cycloreversion in solution. We also applied the acquired fundamental principles towards mapping of changes in material properties, which could provide a pathway for monitoring material aging or structural deterioration.

Dispersoid reinforced alloy powder and method of making

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

Anderson, Iver E.; Terpstra, Robert L.

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomizedmore » particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.« less

Automated electrochemical synthesis and photoelectrochemical characterization of Zn1-xCo(x)O thin films for solar hydrogen production.

PubMed

Jaramillo, Thomas F; Baeck, Sung-Hyeon; Kleiman-Shwarsctein, Alan; Choi, Kyoung-Shin; Stucky, Galen D; McFarland, Eric W

2005-01-01

High-throughput electrochemical methods have been developed for the investigation of Zn1-xCo(x)O films for photoelectrochemical hydrogen production from water. A library of 120 samples containing 27 different compositions (0

Dispersoid reinforced alloy powder and method of making

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

Anderson, Iver E.; Terpstra, Robert L.

2017-10-10

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomizedmore » particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.« less

Aluminum-doped ceria-zirconia solid solutions with enhanced thermal stability and high oxygen storage capacity.

PubMed

Dong, Qiang; Yin, Shu; Guo, Chongshen; Sato, Tsugio

2012-10-01

A facile solvothermal method to synthesize aluminum-doped ceria-zirconia (Ce0.5Zr0.5-xAlxO2-x/2, x = 0.1 to 0.4) solid solutions was carried out using Ce(NH4)2(NO3)6, Zr(NO3)3·2H2O Al(NO3)3·9H2O, and NH4OH as the starting materials at 200°C for 24 h. The obtained solid solutions from the solvothermal reaction were calcined at 1,000°C for 20 h in air atmosphere to evaluate the thermal stability. The synthesized Ce0.5Zr0.3Al0.2O1.9 particle was characterized for the oxygen storage capacity (OSC) in automotive catalysis. For the characterization, X-ray diffraction, transmission electron microscopy, and the Brunauer-Emmet-Teller (BET) technique were employed. The OSC values of all samples were measured at 600°C using thermogravimetric-differential thermal analysis. Ce0.5Zr0.3Al0.2O1.9 solid solutions calcined at 1,000°C for 20 h with a BET surface area of 18 m2 g-1 exhibited a considerably high OSC of 427 μmol-O g-1 and good OSC performance stability. The same synthesis route was employed for the preparation of the CeO2 and Ce0.5Zr0.5O2. The incorporation of aluminum ion in the lattice of ceria-based catalyst greatly enhanced the thermal stability and OSC.

Dynamic fields near a crack tip growing in an elastic-perfectly-plastic solid

NASA Technical Reports Server (NTRS)

Nemat-Nasser, S.; Gao, Y. C.

1983-01-01

A full asymptotic solution is presented for the fields in the neighborhood of the tip of a steadily advancing crack in an incompressible elastic-perfectly-plastic solid. There are four findings for mode I crack growth in the plane strain condition. The first is that the entire crack tip in steady crack growth is surrounded by a plastic region and that no elastic unloading is predicted by the complete dynamic asymptotic solution. The second is that, in contrast to the quasi-static solution, the dynamic solution yields strain fields with a logarithmic singularity everywhere near the crack tip. The third is that whereas the stress field varies throughout the entire crack tip neighborhood, it does not exhibit behavior that can be approximated by a constant field followed by an essentially centered-fan field and then by another constant field, especially for small crack growth speeds. The fourth finding is that there are two shock fronts emanating from the crack tip across which certain stress and strain components undergo jump discontinuities. After reviewing the mode III steady-state crack growth, it is concluded that ductile fracture criteria for nonstationary cracks must be based on solutions that include the inertia effects and that for this purpose quasi-static solutions may be inadequate.

Physicochemical characterization and water vapor sorption of organic solution advanced spray-dried inhalable trehalose microparticles and nanoparticles for targeted dry powder pulmonary inhalation delivery.

PubMed

Li, Xiaojian; Mansour, Heidi M

2011-12-01

Novel advanced spray-dried inhalable trehalose microparticulate/nanoparticulate powders with low water content were successfully produced by organic solution advanced spray drying from dilute solution under various spray-drying conditions. Laser diffraction was used to determine the volumetric particle size and size distribution. Particle morphology and surface morphology was imaged and examined by scanning electron microscopy. Hot-stage microscopy was used to visualize the presence/absence of birefringency before and following particle engineering design pharmaceutical processing, as well as phase transition behavior upon heating. Water content in the solid state was quantified by Karl Fisher (KF) coulometric titration. Solid-state phase transitions and degree of molecular order were examined by differential scanning calorimetry (DSC) and powder X-ray diffraction, respectively. Scanning electron microscopy showed a correlation between particle morphology, surface morphology, and spray drying pump rate. All advanced spray-dried microparticulate/nanoparticulate trehalose powders were in the respirable size range and exhibited a unimodal distribution. All spray-dried powders had very low water content, as quantified by KF. The absence of crystallinity in spray-dried particles was reflected in the powder X-ray diffractograms and confirmed by thermal analysis. DSC thermal analysis indicated that the novel advanced spray-dried inhalable trehalose microparticles and nanoparticles exhibited a clear glass transition (T(g)). This is consistent with the formation of the amorphous glassy state. Spray-dried amorphous glassy trehalose inhalable microparticles and nanoparticles exhibited vapor-induced (lyotropic) phase transitions with varying levels of relative humidity as measured by gravimetric vapor sorption at 25°C and 37°C.

Programmable Payload Release from Transient Polymer Microcapsules Triggered by a Specific Ion Coactivation Effect.

PubMed

Tang, Shijia; Tang, Liuyan; Lu, Xiaocun; Liu, Huiying; Moore, Jeffrey S

2018-01-10

Stimuli-responsive materials activated by a pair of molecular or ionic species are of interest in the design of chemical logic gates and signal amplification schemes. There are relatively few materials whose coactivated response has been well-characterized. Here, we demonstrate a specific ion coactivation (SICA) effect at the interfaces of transient polymer solids and liquid solutions. We found that depolymerization of the transient polymer, cyclic poly(phthalaldehyde) (cPPA), exhibited a SICA effect when the cPPA core-shell microcapsules were suspended in ion-containing acidic methanol solutions. Significant acceleration in cPPA depolymerization rate is triggered by the combination of acid and ion coactivators. Intriguingly, the SICA effect is related to the Hofmeister behavior. The SICA effect is primarily determined by anions, and cations exhibit a secondary effect that modulates the coactivation strength. Based on these observations, we developed cPPA programmable microcapsules whose payload release rates depend on the composition and concentration of the salt/acidic-methanol solutions.

Solid-Solution Anion-Enhanced Electrochemical Performances of Metal Sulfides/Selenides for Sodium-Ion Capacitors: The Case of FeS2- xSe x.

PubMed

Long, Yaqiong; Yang, Jing; Gao, Xin; Xu, Xuena; Fan, Weiliu; Yang, Jian; Hou, Shifeng; Qian, Yitai

2018-04-04

Transition-metal sulfides/selenides are explored as advanced electrode materials for nonaqueous sodium-ion capacitors, using FeS 2- x Se x as an example. A solid solution of S/Se in FeS 2- x Se x allows it to combine the high capacity of FeS 2 and the good diffusion kinetics of FeSe 2 together, thereby exhibiting excellent cycle stability (∼220 mA h g -1 after 6000 cycles at 2 A g -1 ) and superior rate capability (∼210 mA h g -1 at 40 A g -1 ) within 0.8-3.0 V. These results are much better than those of FeS 2 and FeSe 2 , confirming the advantages of S/Se solid solution, as supported by EIS spectra, DFT calculations, and electronic conductivity. As FeS 2- x Se x is paired with the activated carbon (AC) as Na-ion capacitors, this device is also better than sodium-ion batteries of FeS 2- x Se x //Na 3 V 2 (PO 4 ) 3 and sodium-ion capacitors of metal oxides//AC, particularly at high rates. These results open a new door for the applications of sulfides/selenides in another device of electrochemical energy storage.

Disappearance of superconductivity in the solid solution between (Ca4Al2O6)(Fe2As2) and (Ca4Al2O6)(Fe2P2) superconductors.

PubMed

Shirage, Parasharam M; Kihou, Kunihiro; Lee, Chul-Ho; Takeshita, Nao; Eisaki, Hiroshi; Iyo, Akira

2012-09-19

The effect of alloying the two perovskite-type iron-based superconductors (Ca(4)Al(2)O(6))(Fe(2)As(2)) and (Ca(4)Al(2)O(6))(Fe(2)P(2)) was examined. While the two stoichiometric compounds possess relatively high T(c)'s of 28 and 17 K, respectively, their solid solutions of the form (Ca(4)Al(2)O(6))(Fe(2)(As(1-x)P(x))(2)) do not show superconductivity over a wide range from x = 0.50 to 0.95. The resultant phase diagram is thus completely different from those of other typical iron-based superconductors such as BaFe(2)(As,P)(2) and LaFe(As,P)O, in which superconductivity shows up when P is substituted for As in the non-superconducting "parent" compounds. Notably, the solid solutions in the non-superconducting range exhibit resistivity anomalies at temperatures of 50-100 K. The behavior is reminiscent of the resistivity kink commonly observed in various non-superconducting parent compounds that signals the onset of antiferromagnetic/orthorhombic long-range order. The similarity suggests that the suppression of the superconductivity in the present case also has a magnetic and/or structural origin.

Preparation of poly(N-vinylpyrrolidone)-stabilized ZnO colloid nanoparticles

PubMed Central

Gutul, Tatyana; Condur, Nadejda; Ursaki, Veaceslav; Goncearenco, Evgenii; Vlazan, Paulina

2014-01-01

Summary We propose a method for the synthesis of a colloidal ZnO solution with poly(N-vinylpyrrolidone) (PVP) as stabilizer. Stable colloidal solutions with good luminescence properties are obtained by using PVP as stabilizer in the synthesis of ZnO nanoparticles by a sol–gel method assisted by ultrasound. Nanoparticles with sizes of 30–40 nm in a PVP matrix are produced as a solid product. The colloidal ZnO/PVP/methanol solution, apart from the most intense PL band at 356 nm coming from the PVP, exhibits a strong PL band at 376 nm (3.30 eV) which corresponds to the emission of the free exciton recombination in ZnO nanoparticles. PMID:24778966

Synthesis and fluorescence properties of some difluoroboron β-diketonate complexes and composite containing PMMA

NASA Astrophysics Data System (ADS)

Xing, Dongye; Hou, Yanjun; Niu, Haijun

2018-03-01

A series of difluoroboron β-diketonate complexes, containing the indon-β-diketonate ligand carrying methyl or methoxyl substituents was synthesized. The crystal structures of the complexes were confirmed by single crystal X-ray diffraction studies. The fluorescence properties of compounds were studied in solution state, solid state and on PMMA polymer matrix. The photophysical data of compounds 2a-2d exhibited strong fluorescence and photostability under the ultraviolet light (Hg lamp). The complex 2b showed higher fluorescence intensity in solution state as compared to other complexes of the series. The complexes 2c and 2d showed higher fluorescence intensity in the solid state, which are ascribed to the stronger π-π interactions between ligands in the solid state. The introduction of methoxyl or methyl groups on the benzene rings enhanced the absorption intensity, emission intensity, quantum yields and fluorescence lifetimes due to their electron-donating nature. Furthermore, the complex 2b was doped into the PMMA to produce hybrid materials, where the PMMA matrix acted as sensitizer for the central boron ion to enhance the fluorescence emission intensity and quantum yields.

Effect of hydrogen on fatigue crack propagation in vanadium

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

Chung, D.W.; Stoloff, N.S.

The influence of hydrogen on fatigue crack propagation in unalloyed vanadium and several hydrogen-charged vanadium alloys has been investigated. The Paris--Erdogan equation, da/dN = C(..delta..K)/sup m/, was approximately obeyed for all alloys. Crack growth rates were lowest in vanadium and dilute vanadium-hydrogen alloys, and were not very sensitive to volume fraction of hydrides in more concentrated alloys. The crack growth exponent, m, is inversely proportional to the cyclic strain hardening rate, n', and the rate constant C is inversely proportional to the square of the ultimate tensile stress, sigma/sub UTS/: metallographic examination showed hydride reorientation and growth in the originallymore » hydrided alloys. No stress-induced hydrides were observed in V-H solid-solution alloys. Fractures in hydrided materials exhibited cleavage-like features, while striations were noted in unalloyed vanadium and dilute solid-solution alloys.« less

Effect of hydrogen on fatigue crack propagation in vanadium

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

Chung, D.W.; Stoloff, N.S.

The influence of hydrogen on fatigue crack propagation in unalloyed vanadium and several hydrogen-charged vanadium alloys has been investigated. The Paris--Erdogan equation, da/dN = C(..delta..K)/sup m/, was approximately obeyed for all alloys. Crack growth rates were lowest in vanadium and dilute vanadium--hydrogen alloys, and were not very sensitive to volume fraction of hydrides in more concentrated alloys. The crack growth exponent, m, is inversely proportional to the cyclic strain hardening rate, n', and the rate constant C is inversely proportional to the square of the ultimate tensile stress, sigma/sub UTS/: metallographic examination showed hydride reorientation and growth in the originallymore » hydrided alloys. No stress-induced hydrides were observed in V--H solid-solution alloys. Fractures in hydrided materials exhibited cleavage-like features, while striations were noted in unalloyed vanadium and dilute solid-solution alloys.« less

Electronic structure and optical properties of CdSxSe1-x solid solution nanostructures from X-ray absorption near edge structure, X-ray excited optical luminescence, and density functional theory investigations

NASA Astrophysics Data System (ADS)

Murphy, M. W.; Yiu, Y. M.; Ward, M. J.; Liu, L.; Hu, Y.; Zapien, J. A.; Liu, Yingkai; Sham, T. K.

2014-11-01

The electronic structure and optical properties of a series of iso-electronic and iso-structural CdSxSe1-x solid solution nanostructures have been investigated using X-ray absorption near edge structure, extended X-ray absorption fine structure, and X-ray excited optical luminescence at various absorption edges of Cd, S, and Se. It is found that the system exhibits compositions, with variable local structure in-between that of CdS and CdSe accompanied by tunable optical band gap between that of CdS and CdSe. Theoretical calculation using density functional theory has been carried out to elucidate the observations. It is also found that luminescence induced by X-ray excitation shows new optical channels not observed previously with laser excitation. The implications of these observations are discussed.

Magnetic properties of quadruple perovskite solid solutions Ca{sub 1–x}Y{sub x}Cu{sub 3}Fe{sub 4}O{sub 12} and Y{sub 1–y}Ce{sub x}Cu{sub 3}Fe{sub 4}O{sub 12}

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

Murakami, Makoto; Mori, Shigeo; Yamada, Ikuya, E-mail: i-yamada@21c.osakafu-u.ac.jp

Magnetic properties of the quadruple perovskite solid solutions Ca{sub 1–x}Y{sub x}Cu{sub 3}Fe{sub 4}O{sub 12} and Y{sub 1–y}Ce{sub y}Cu{sub 3}Fe{sub 4}O{sub 12} are investigated. Ca{sub 1–x}Y{sub x}Cu{sub 3}Fe{sub 4}O{sub 12} shows continuous increase in the ferromagnetic transition temperature as x increases. Y{sub 1–y}Ce{sub y}Cu{sub 3}Fe{sub 4}O{sub 12} exhibits a ferromagnetic-antiferromagnetic transition in the vicinity of y = 0.5. These observations demonstrate the electron doping effect on magnetic properties of charge-disproportionated ACu{sub 3}Fe{sub 4}O{sub 12} phases.

MoNbTaV Medium-Entropy Alloy

DOE PAGES

Yao, Hongwei; Qiao, Jun -Wei; Gao, Michael; ...

2016-05-19

Guided by CALPHAD (Calculation of Phase Diagrams) modeling, the refractory medium-entropy alloy MoNbTaV was synthesized by vacuum arc melting under a high-purity argon atmosphere. A body-centered cubic solid solution phase was experimentally confirmed in the as-cast ingot using X-ray diffraction and scanning electron microscopy. The measured lattice parameter of the alloy (3.208 Å) obeys the rule of mixtures (ROM), but the Vickers microhardness (4.95 GPa) and the yield strength (1.5 GPa) are about 4.5 and 4.6 times those estimated from the ROM, respectively. Using a simple model on solid solution strengthening predicts a yield strength of approximately 1.5 GPa. Inmore » conclusion, thermodynamic analysis shows that the total entropy of the alloy is more than three times the configurational entropy at room temperature, and the entropy of mixing exhibits a small negative departure from ideal mixing.« less

Preparation of the polyelectrolyte complex hydrogel of biopolymers via a semi-dissolution acidification sol-gel transition method and its application in solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Zhao, Jian; Chen, Yu; Yao, Ying; Tong, Zong-Rui; Li, Pu-Wang; Yang, Zi-Ming; Jin, Shao-Hua

2018-02-01

Hydrogels have drawn many attentions as the solid-state electrolytes in flexible solid-state supercapacitors (SCs) recently. Among them, the polyelectrolyte complex hydrogel (PECH) electrolytes of natural polymers are more competitive because of their environmentally friendly property and low cost. However, while mixing two biopolymer solutions with opposite charges, the strong electrostatic interactions between the cationic and anionic biopolymers may result in precipitates instead of hydrogels. Here we report a novel method, semi-dissolution acidification sol-gel transition (SD-A-SGT), for the preparation of the PECH of chitosan (CTS) and sodium alginate (SA), with the controllable sol-gel transition and uniform composition and successfully apply it as the hydrogel electrolyte of solid-state supercapacitors (SCs). The CTS-SA PECH exhibits an extremely high ionic conductivity of 0.051 S·cm-1 and reasonable mechanical properties with a tensile strength of 0.29 MPa and elongation at break of 109.5%. The solid-state SC fabricated with the CTS-SA PECH and conventional polyaniline (PANI) nanowire electrodes provided a high specific capacitance of 234.6 F·g-1 at 5 mV·s-1 and exhibited excellent cycling stability with 95.3% capacitance retention after 1000 cycles. Our work may pave a novel avenue to the preparation of biodegradable PECHs of full natural polymers, and promote the development of environmentally friendly electronic devices.

Surface modification of solid lipid nanoparticles for oral delivery of curcumin: Improvement of bioavailability through enhanced cellular uptake, and lymphatic uptake.

PubMed

Baek, Jong-Suep; Cho, Cheong-Weon

2017-08-01

Curcumin has been reported to exhibit potent anticancer effects. However, poor solubility, bioavailability and stability of curcumin limit its in vivo efficacy for the cancer treatment. Solid lipid nanoparticles (SLN) are a promising delivery system for the enhancement of bioavailability of hydrophobic drugs. However, burst release of drug from SLN in acidic environment limits its usage as oral delivery system. Hence, we prepared N-carboxymethyl chitosan (NCC) coated curcumin-loaded SLN (NCC-SLN) to inhibit the rapid release of curcumin in acidic environment and enhance the bioavailability. The NCC-SLN exhibited suppressed burst release in simulated gastric fluid while sustained release was observed in simulated intestinal fluid. Furthermore, NCC-SLN exhibited increased cytotoxicity and cellular uptake on MCF-7 cells. The lymphatic uptake and oral bioavailability of NCC-SLN were found to be 6.3-fold and 9.5-fold higher than that of curcumin solution, respectively. These results suggest that NCC-SLN could be an efficient oral delivery system for curcumin. Copyright © 2017 Elsevier B.V. All rights reserved.

A facile method to prepare "green" nano-phosphors with a large Stokes-shift and solid-state enhanced photophysical properties based on surface-modified gold nanoclusters.

PubMed

Cheng, C H; Huang, H Y; Talite, M J; Chou, W C; Yeh, J M; Yuan, C T

2017-12-15

Colloidal nano-materials, such as quantum dots (QDs) have been applied to light-conversion nano-phosphors due to their unique tunable emission. However, most of the QDs involve toxic elements and are synthesized in a hazardous solvent. In addition, conventional QD nano-phosphors with a small Stokes shift suffered from reabsorption losses and aggregation-induced quenching in the solid state. Here, we demonstrate a facile, matrix-free method to prepare eco-friendly nano-phosphors with a large Stokes shift based on aqueous thiolate-stabilized gold nanoclusters (GSH-AuNCs) with simple surface modifications. Our method is just to drop GSH-AuNCs solution on the aluminum foil and then surface-modified AuNCs (Al-GSH-AuNCs) can be spontaneously precipitated out of the aqueous solution. Compared with pristine GSH-AuNCs in solution, the Al-GSH-AuNCs exhibit enhanced solid-state PL quantum yields, lengthened PL lifetime, and spectral blue shift, which can be attributed to the aggregation-induced emission enhancement facilitated by surface modifications. Such surface-treatment induced aggregation of AuNCs can restrict the surface-ligand motion, leading to the enhancement of PL properties in the solid state. In addition, the Al-GSH-AuNCs nano-phosphors with a large Stokes shift can mitigate the aggregation-induced PL quenching and reabsorption losses, which would be potential candidates for "green" nano-phosphors. Copyright © 2017 Elsevier Inc. All rights reserved.

Alloy softening in binary iron solid solutions

NASA Technical Reports Server (NTRS)

Stephens, J. R.; Witzke, W. R.

1976-01-01

An investigation was conducted to determine softening and hardening behavior in 19 binary iron-alloy systems. Microhardness tests were conducted at four temperatures in the range 77 to 411 K. Alloy softening was exhibited by 17 of the 19 alloy systems. Alloy softening observed in 15 of the alloy systems was attributed to an intrinsic mechanism, believed to be lowering of the Peierls (lattice friction) stress. Softening and hardening rates could be correlated with the atomic radius ratio of solute to iron. Softening observed in two other systems was attributed to an extrinsic mechanism, believed to be associated with scavenging of interstitial impurities.

Method of preparing graphene-sulfur nanocomposites for rechargeable lithium-sulfur battery electrodes

DOEpatents

Liu, Jun; Lemmon, John P; Yang, Zhenguo; Cao, Yuliang; Li, Xiaolin

2015-04-07

A method of preparing a graphene-sulfur nanocomposite for a cathode in a rechargeable lithium-sulfur battery comprising thermally expanding graphite oxide to yield graphene layers, mixing the graphene layers with a first solution comprising sulfur and carbon disulfide, evaporating the carbon disulfide to yield a solid nanocomposite, and grinding the solid nanocomposite to yield the graphene-sulfur nanocomposite. Rechargeable-lithium-sulfur batteries having a cathode that includes a graphene-sulfur nanocomposite can exhibit improved characteristics. The graphene-sulfur nanocomposite can be characterized by graphene sheets with particles of sulfur adsorbed to the graphene sheets. The sulfur particles have an average diameter of less than 50 nm.

Phase relations in the system NaCl-KCl-H2O: V. Thermodynamic-PTX analysis of solid-liquid equilibria at high temperatures and pressures

USGS Publications Warehouse

Sterner, S.M.; Chou, I.-Ming; Downs, R.T.; Pitzer, Kenneth S.

1992-01-01

The Gibbs energies of mixing for NaCl-KCl binary solids and liquids and solid-saturated NaCl-KCl-H2O ternary liquids were modeled using asymmetric Margules treatments. The coefficients of the expressions were calibrated using an extensive array of binary solvus and solidus data, and both binary and ternary liquidus data. Over the PTX range considered, the system exhibits complete liquid miscibility among all three components and extensive solid solution along the anhydrous binary. Solid-liquid and solid-solid phase equilibria were calculated by using the resulting equations and invoking the equality of chemical potentials of NaCl and KCl between appropriate phases at equilibrium. The equations reproduce the ternary liquidus and predict activity coefficients for NaCl and KCl components in the aqueous liquid under solid-saturation conditions between 673 and 1200 K from vapor saturation up to 5 kbar. In the NaCl-KCl anhydrous binary system, the equations describe phase equilibria and predict activity coefficients of the salt components for all stable compositions of solid and liquid phases between room temperature and 1200 K and from 1 bar to 5 kbar. ?? 1992.

Synthesis, electronic and ESR spectral studies on copper(II) nitrate complexes with some acylhydrazines and hydrazones.

PubMed

Singh, Vinod P

2008-11-01

This paper describes the preparation of [Cu(bh)2(H2O)2](NO3)2], [Cu(ibh)2(NO3)2], [Cu(ibh)2(H2O)2](NO3)2 and [Cu(iinh)2(NO3)2] (bh = benzoyl hydrazine (C6H5CONHNH2); ibh = isonicotinoyl hydrazine (NC5H4CONHNH2); ibh = isopropanone benzoyl hydrazone (C6H5CONHN=C(CH3)2; iinh = isopropanone isonicotinoyl hydrazone (NC5H4CONHN=C(CH3)2). These copper(II) complexes are characterized by elemental analyses, molar conductances, dehydration studies, ESR, IR and electronic spectral studies. The electronic and ESR spectra indicate that each complex exhibits a six-coordinate tetragonally distorted octahedral geometry in the solid state and in DMSO solution. The ESR spectra of most of the complexes are typically isotropic type at room temperature (300 K) in solid state as well as in DMSO solution. However, all the complexes exhibit invariably axial signals at 77 K in DMSO solution. The trend g(||) > g(perpendicular) > g(e,) observed in all the complexes suggests the presence of an unpaired electron in the d x2-y2 orbital of the Cu(II). The bh and inh ligands bond to Cu(II) through the >C=O and -NH2 groups whereas, ibh and iinh bond through >C=O and >C=N- groups. The IR spectra of bh and ibh complexes also show H-O-H stretching and bending modes of coordinated water.

End-Member Formulation of Solid Solutions and Reactive Transport

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

Lichtner, Peter C.

2015-09-01

A model for incorporating solid solutions into reactive transport equations is presented based on an end-member representation. Reactive transport equations are solved directly for the composition and bulk concentration of the solid solution. Reactions of a solid solution with an aqueous solution are formulated in terms of an overall stoichiometric reaction corresponding to a time-varying composition and exchange reactions, equivalent to reaction end-members. Reaction rates are treated kinetically using a transition state rate law for the overall reaction and a pseudo-kinetic rate law for exchange reactions. The composition of the solid solution at the onset of precipitation is assumed tomore » correspond to the least soluble composition, equivalent to the composition at equilibrium. The stoichiometric saturation determines if the solid solution is super-saturated with respect to the aqueous solution. The method is implemented for a simple prototype batch reactor using Mathematica for a binary solid solution. Finally, the sensitivity of the results on the kinetic rate constant for a binary solid solution is investigated for reaction of an initially stoichiometric solid phase with an undersaturated aqueous solution.« less

Summary Report of Laboratory Testing to Establish the Effectiveness of Proposed Treatment Methods for Unremediated and Remediated Nitrate Salt Waste Streams

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

Anast, Kurt Roy; Funk, David John

The inadvertent creation of transuranic waste carrying hazardous waste codes D001 and D002 requires the treatment of the material to eliminate the hazardous characteristics and allow its eventual shipment and disposal at the Waste Isolation Pilot Plant (WIPP). This report documents the effectiveness of two treatment methods proposed to stabilize both the unremediated and remediated nitrate salt waste streams (UNS and RNS, respectively). The two technologies include the addition of zeolite (with and without the addition of water as a processing aid) and cementation. Surrogates were developed to evaluate both the solid and liquid fractions expected from parent waste containers,more » and both the solid and liquid fractions were tested. Both technologies are shown to be effective at eliminating the characteristic of ignitability (D001), and the addition of zeolite was determined to be effective at eliminating corrosivity (D002), with the preferred option1 of zeolite addition currently planned for implementation at the Waste Characterization, Reduction, and Repackaging Facility. During the course of this work, we established the need to evaluate and demonstrate the effectiveness of the proposed remedy for debris material, if required. The evaluation determined that Wypalls absorbed with saturated nitrate salt solutions exhibit the ignitability characteristic (all other expected debris is not classified as ignitable). Follow-on studies will be developed to demonstrate the effectiveness of stabilization for ignitable Wypall debris. Finally, liquid surrogates containing saturated nitrate salts did not exhibit the characteristic of ignitability in their pure form (those neutralized with Kolorsafe and mixed with sWheat did exhibit D001). As a result, additional nitrate salt solutions (those exhibiting the oxidizer characteristic) will be tested to demonstrate the effectiveness of the remedy.« less

Effect of cyclophosphamide on the solid form of mannitol during lyophilization.

PubMed

Patel, Krupaliben; Munjal, Bhushan; Bansal, Arvind K

2017-04-01

Mannitol is a commonly used bulking agent in lyophilized formulations. It can crystallize into multiple solid forms during lyophilization thereby exhibiting phase heterogeneity and variability in product performance. In this manuscript, we studied the effect of cyclophosphamide (CPA), an anticancer drug, on the solid form of mannitol during lyophilization from aqueous solutions. Freeze-concentration studies were performed in the DSC while lyophilization was performed in a lab scale freeze dryer. DSC experiments revealed two-stage crystallization of mannitol (1.5% w/v) during freeze-concentration, evident as two distinct exothermic events (at -18.2°C and -30°C) in the cooling curve. This was complemented by two eutectic melting endotherms in the subsequent heating curve. Addition of CPA (4.0% w/v) completely inhibited the exotherm at -18.2°C, but enhanced the enthalpy of exotherm at -30°C by five folds. Likewise, only one eutectic melting endotherm was observed in the subsequent heating curve. Lyophilization of the solution containing only mannitol, yielded a mixture of β- (major) and δ- (minor) polymorphs of mannitol. However, in the presence of CPA, only δ-polymorph was observed in the lyophilized sample. This selective favoring of the metastable δ-polymorph over the stable β-polymorph, was explained by altered freezing kinetics of the solution in presence of CPA. The study provides mechanistic insights into solute crystallization behaviour during lyophilization of multi-component systems. Copyright © 2017. Published by Elsevier B.V.

Brooker's merocyanine: Comparison of single crystal structures

NASA Astrophysics Data System (ADS)

Hayes, Kathleen L.; Lasher, Emily M.; Choczynski, Jack M.; Crisci, Ralph R.; Wong, Calvin Y.; Dragonette, Joseph; Deschner, Joshua; Cardenas, Allan Jay P.

2018-06-01

Brooker's merocyanine and its derivatives are well-studied molecules due to their very interesting optical properties. Merocyanine dyes exhibit different colors in solution depending on the solvent's polarity, pH, aggregation and intermolecular interactions. The synthesis of 1-methyl-4-[(oxocyclohexadienylidene)ethylidene]-1,4-dihydropyridine (MOED) dye yielded a particularly interesting solid state structure where in one crystal lattice, MOED and its protonated form are bound by hydrogen bonding interactions.

The Stokes-Einstein relationship and the levitation effect: size-dependent diffusion maximum in dense fluids and close-packed disordered solids.

PubMed

Ghorai, Pradip Kr; Yashonath, S

2005-03-31

We report a molecular dynamics study of a binary mixture consisting of a large (host) particle and a smaller (guest) particle whose radius is varied over a range. These simulations investigate the possible existence of a diffusion anomaly or levitation effect in dense fluids, previously seen for guest molecules diffusing within porous solids. The voids in the larger component have been characterized in terms of void and neck distributions by means of Voronoi polyhedral analysis. Four different mixtures with differing ratios of guest to host diffusivities (D) have been studied. The results suggest that the diffusion anomaly is seen in both close-packed solids with disorder and dense fluids. In the latter, the void network is constantly and dynamically changing and possesses a considerable degree of disorder. The two regimes, viz., the linear regime (LR) and the anomalous regime (AR), found for porous solids are shown to exist for a dense medium as well. The linear regime is characterized by D(g) proportional to 1/sigma(gg)(2), where sigma(gg) is the diameter of the guest. The anomalous regime exhibits a maximum in D up to rather high temperatures (T = 1.663), even though in porous solids the maximum disappears at higher temperatures. In agreement with previous studies on porous solids, a particle in the AR is associated with lower activation energy, lower friction, and less backscattering in the velocity autocorrelation function when compared to a particle in the LR. Wavevector dependent self-diffusivity, Delta, and decay of the intermediate scattering function, F(s)(k, t), exhibit contrasting behaviors for the LR and AR. For LR, Delta exhibits a minimum at values of k at which there are spatial correlations in S(k) while a smooth decrease with k is seen for AR. For LR, F(s)(k, t) shows a biexponential decay corresponding to two different time scales of motion. Probably, the fast decay is associated with motion within the first shell of solvent neighbors and the slow decay with motion past these shells. For AR, a single-exponential decay is seen. The results indicate a breakdown of the Stokes-Einstein (SE) relationship. The relevant quantity that determines the validity of the SE relationship is the levitation parameter which is indirectly related to the solute/solvent radius ratio and not either the size of the solute or the solvent alone.

Skutterudite Compounds For Power Semiconductor Devices

NASA Technical Reports Server (NTRS)

Fleurial, Jean-Pierre; Caillat, Thierry; Borshchevsky, Alexander; Vandersande, Jan

1996-01-01

New semiconducting materials with p-type carrier mobility values much higher than state-of-art semiconductors discovered. Nine compounds, antimonides CoSb(sub3), RhSb(sub3), IrSb(sub3), arsenides CoAs(sub3), RhAs(sub3), IrAs(sub3), and phosphides CoP(sub3), RhP(sub3) and IrP(sub3), exhibit same skutterudite crystallographic structure and form solid solutions of general composition Co(1-x-y)RH(x)Ir(y)P(1-w-z)As(w)Sb(z). Materials exhibit high hole mobilities, high doping levels, and high electronic figures of merit. Some compositions show great potential for application to thermoelectric devices.

Three-Phase Melting Curves in the Binary System of Carbon Dioxide and Water

NASA Astrophysics Data System (ADS)

Abramson, E. H.

2017-10-01

Invariant, three-phase melting curves, of ice VI in equilibrium with solid CO2, of ice VII in equilibrium with solid CO2, and of solid CO2 in simultaneous equilibrium with a majority aqueous and a majority CO2 fluid, were explored in the binary system of carbon dioxide and water. Diamond-anvil cells were used to develop pressures of 5 GPa. Water exhibits a large melting temperature depression (73°C less than its pure melting temperature of 253°C at 5 GPa) indicative of large concentrations of CO2 in the aqueous solution. The melting point of water-saturated CO2 does not show a measureable departure from that of the pure system at temperatures lower than ∼200°C and only 10°C at 5 GPa (from 327°C).

Synthesis and the luminescent properties of the Nd3+ ions doped three kinds of fluoride nanocrystals in organic solvents

NASA Astrophysics Data System (ADS)

Chen, Zhuo; Tian, Changyong; Bo, Shuhui; Liu, Xinhou; Zhen, Zhen

2015-10-01

Oleic acid (OA)-modified LaF3:Nd, NaYF4:Nd and CaF2:Nd nanocrystals (NCs) with the different Nd3+ ion concentration (2% and 5%) have been prepared. The structure and morphology of NCs were identified by XRD, TEM, FT-IR and TGA. The size of OA-modified NC is a mean diameter of 5-10 nm and can be dispersed in common organic solvents to form a transparent solution. The optical loss of NCs in organic solvent is the first time to discuss in this work. The luminescence properties of NCs were also characterized and studied by fluorescence spectrometer. The nanoparticles in solid and in the solution all exhibited the strong emission at the 1060 nm when the materials were excited around 800 nm. Compared with the LaF3 and CaF2 matrix, NaYF4 as the host can protect the Nd3+ ions more efficiently away from the nonradiative transitions. The longest luminescent lifetime of the solid NaYF4:2%Nd NCs was up to 136 μs, and the little difference of the fluorescence lifetime existed between the NCs in solid state and in solution. The low optical loss in organic solvent indicated that the Nd3+ ions-doped fluoride NCs are promising materials for optical amplification fields.

Properties of Poly- and Oligopentacenes Synthesized from Modular Building Blocks

DOE PAGES

Kumarasamy, Elango; Sanders, Samuel N.; Pun, Andrew B.; ...

2016-02-09

Here, we describe a facile route to well-defined, solution-processable pentacene oligomers (2 to 7) and homopolymer using Suzuki–Miyaura cross-coupling reactions. This synthetic strategy leads to regioisomers, regiopure syn- and anti-trimers were also synthesized, revealing minimal changes in solution properties but significant changes in the solid state arising from differing levels of crystallinity. The materials were characterized by steady state absorption spectroscopy and cyclic voltammetry to study their electronic structure. The steady state absorption spectra exhibit a new high-energy transition in the oligomers, which intensifies as a function of oligomer length, thus increasing the range of absorption to include the entiremore » visible spectrum. Density functional theory calculations indicate that the new peak results directly from the oligomerization. Solid state UV–vis suggests that while the monomer is amorphous, bricklayer packing in the higher oligomers significantly alters the solid state absorption relative to solution. The effect of oligomerization on packing was corroborated by GIWAXS analysis, which revealed crystalline domains in the oligomers. These domains, which are most evident in anti-trimer, become more pronounced upon thermal annealing. Photodegradation studies revealed considerable stability enhancement of oligomers toward oxygen and cycloaddition reactions relative to monomer. The synthesis and characterization of the first higher oligomers and homopolymer of pentacene should pave the way to applications in singlet fission, organic field-effect transistors, and organic photovoltaics.« less

Effects of chemical alternation on damage accumulation in concentrated solid-solution alloys

DOE PAGES

Ullah, Mohammad W.; Xue, Haizhou; Velisa, Gihan; ...

2017-06-23

Single-phase concentrated solid-solution alloys (SP-CSAs) have recently gained unprecedented attention due to their promising properties. To understand effects of alloying elements on irradiation-induced defect production, recombination and evolution, an integrated study of ion irradiation, ion beam analysis and atomistic simulations are carried out on a unique set of model crystals with increasing chemical complexity, from pure Ni to Ni 80Fe 20, Ni 50Fe 50, and Ni 80Cr 20 binaries, and to a more complex Ni 40Fe 40Cr 20 alloy. Both experimental and simulation results suggest that the binary and ternary alloys exhibit higher radiation resistance than elemental Ni. The modelingmore » work predicts that Ni 40Fe 40Cr 20 has the best radiation tolerance, with the number of surviving Frenkel pairs being factors of 2.0 and 1.4 lower than pure Ni and the 80:20 binary alloys, respectively. While the reduced defect mobility in SP-CSAs is identified as a general mechanism leading to slower growth of large defect clusters, the effect of specific alloying elements on suppression of damage accumulation is clearly demonstrated. This work suggests that concentrated solid-solution provides an effective way to enhance radiation tolerance by creating elemental alternation at the atomic level. The demonstrated chemical effects on defect dynamics may inspire new design principles of radiation-tolerant structural alloys for advanced energy systems.« less

Fluorine substituted (Mn,Ir)O 2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis

DOE PAGES

Ghadge, Shrinath Dattatray; Patel, Prasad Prakash; Datta, Moni Kanchan; ...

2017-03-20

Identification and development of high performance with reduced overpotential (i.e. reduced operating electricity cost) oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane (PEM) based water electrolysis with ultra-low noble metal content (i.e. reduced materials cost) is of significant interest for economic hydrogen production, thus increasing the commercialization potential of PEM water electrolysis. Accordingly, a novel electrocatalyst should exhibit low overpotential, excellent electrochemical activity and durability superior to state of the art noble metal based electro-catalysts (e.g. Pt, IrO 2, RuO 2). Here in this paper, for the very first time to the best of our knowledge, exploiting first-principles theoreticalmore » calculations of the total energies and electronic structures, we have identified a reduced noble metal content fluorine doped solid solution of MnO 2 and IrO 2, denoted as (Mn 1-xIr x)O 2:F (x = 0.2, 0.3, 0.4), OER electrocatalyst system exhibiting lower overpotential and higher current density than the state of the art IrO 2 and other previously reported systems for PEM water electrolysis. The doped solid solution displays an excellent electrochemical performance with a lowest reported onset potential to date of ~1.35 V (vs. RHE), ~80 mV lower than that of IrO 2 (~1.43 V vs. RHE) and ~15 fold (x = 0.3 and 0.4) higher electrochemical activity compared to pure IrO 2. In addition, the system displays excellent long term electrochemical durability, similar to that of IrO 2 in harsh acidic OER operating conditions. Our study therefore demonstrates remarkable, ~60–80% reduction in noble metal content along with lower overpotential and excellent electrochemical performance clearly demonstrating the potential of the (Mn 1-xIr x)O 2:F system as an OER electro-catalyst for PEM water electrolysis.« less

Room-temperature ferromagnetic transitions and the temperature dependence of magnetic behaviors in FeCoNiCr-based high-entropy alloys

NASA Astrophysics Data System (ADS)

Na, Suok-Min; Yoo, Jin-Hyeong; Lambert, Paul K.; Jones, Nicholas J.

2018-05-01

High-entropy alloys (HEAs) containing multiple principle alloying elements exhibit unique properties so they are currently receiving great attention for developing innovative alloy designs. In FeCoNi-based HEAs, magnetic behaviors strongly depend on the addition of alloying elements, usually accompanied by structural changes. In this work, the effect of non-magnetic components on the ferromagnetic transition and magnetic behaviors in equiatomic FeCoNiCrX (X=Al, Ga, Mn and Sn) HEAs was investigated. Alloy ingots of nominal compositions of HEAs were prepared by arc melting and the button ingots were cut into discs for magnetic measurements as functions of magnetic field and temperature. The HEAs of FeCoNiCrMn and FeCoNiCrSn show typical paramagnetic behaviors, composed of solid solution FCC matrix, while the additions of Ga and Al in FeCoNiCr exhibit ferromagnetic behaviors, along with the coexistence of FCC and BCC phases due to spinodal decomposition. The partial phase transition in both HEAs with the additions of Ga and Al would enhance ferromagnetic properties due to the addition of the BCC phase. The saturation magnetization for the base alloy FeCoNiCr is 0.5 emu/g at the applied field of 20 kOe (TC = 104 K). For the HEAs of FeCoNiCrGa and FeCoNiCrAl, the saturation magnetization significantly increased to 38 emu/g (TC = 703 K) and 25 emu/g (TC = 277 K), respectively. To evaluate the possibility of solid solution FCC and BCC phases in FeCoNiCr-type HEAs, we introduced a parameter of valence electron concentration (VEC). The proposed rule for solid solution formation by the VEC was matched with FeCoNiCr-type HEAs.

Fluorine substituted (Mn,Ir)O 2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis

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

Ghadge, Shrinath Dattatray; Patel, Prasad Prakash; Datta, Moni Kanchan

Identification and development of high performance with reduced overpotential (i.e. reduced operating electricity cost) oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane (PEM) based water electrolysis with ultra-low noble metal content (i.e. reduced materials cost) is of significant interest for economic hydrogen production, thus increasing the commercialization potential of PEM water electrolysis. Accordingly, a novel electrocatalyst should exhibit low overpotential, excellent electrochemical activity and durability superior to state of the art noble metal based electro-catalysts (e.g. Pt, IrO 2, RuO 2). Here in this paper, for the very first time to the best of our knowledge, exploiting first-principles theoreticalmore » calculations of the total energies and electronic structures, we have identified a reduced noble metal content fluorine doped solid solution of MnO 2 and IrO 2, denoted as (Mn 1-xIr x)O 2:F (x = 0.2, 0.3, 0.4), OER electrocatalyst system exhibiting lower overpotential and higher current density than the state of the art IrO 2 and other previously reported systems for PEM water electrolysis. The doped solid solution displays an excellent electrochemical performance with a lowest reported onset potential to date of ~1.35 V (vs. RHE), ~80 mV lower than that of IrO 2 (~1.43 V vs. RHE) and ~15 fold (x = 0.3 and 0.4) higher electrochemical activity compared to pure IrO 2. In addition, the system displays excellent long term electrochemical durability, similar to that of IrO 2 in harsh acidic OER operating conditions. Our study therefore demonstrates remarkable, ~60–80% reduction in noble metal content along with lower overpotential and excellent electrochemical performance clearly demonstrating the potential of the (Mn 1-xIr x)O 2:F system as an OER electro-catalyst for PEM water electrolysis.« less

Using Environment-Sensitive Fluorescent Probes to Characterize Liquid-Liquid Phase Separation in Supersaturated Solutions of Poorly Water Soluble Compounds.

PubMed

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

2015-11-01

Highly supersaturated aqueous solutions of poorly soluble compounds can undergo liquid-liquid phase separation (LLPS) when the concentration exceeds the "amorphous solubility". This phenomenon has been widely observed during high throughput screening of new molecular entities as well as during the dissolution of amorphous solid dispersions. In this study, we have evaluated the use of environment-sensitive fluorescence probes to investigate the formation and properties of the non-crystalline drug-rich aggregates formed in aqueous solutions as a result of LLPS. Six different environment-sensitive fluorophores were employed to study LLPS in highly supersaturated solutions of several model compounds, all dihydropyridine derivatives. Each fluoroprobe exhibited a large hypsochromic shift with decreasing environment polarity. Upon drug aggregate formation, the probes partitioned into the drug-rich phase and exhibited changes in emission wavelength and intensity consistent with sensing a lower polarity environment. The LLPS onset concentrations determined using the fluorescence measurements were in good agreement with light scattering measurements as well as theoretically estimated amorphous solubility values. Environment-sensitive fluorescence probes are useful to help understand the phase behavior of highly supersaturated aqueous solutions, which in turn is important in the context of developing enabling formulations for poorly soluble compounds.

Smart Core-Shell Nanowire Architectures for Multifunctional Nanoscale Devices

DTIC Science & Technology

2014-02-16

Andrew R. Akbashev, Peter K. Davies, Jonathan E. Spanier, Andrew M. Rappe. Perovskite oxides for visible- light -absorbing ferroelectric and...without loss of polar character. Shown for a single phase solid solution ferroelectric oxide perovskite (K,Ba),(Ni,Nb)O_(3-delta), this material...exhibits a compositionally tunable and direct band gap in the range of 1.1 – 3.8 eV, with potential for novel nonlinear light -matter applications in addition

The influence of incorporating MgO into Ni-based cermets by plasma spraying on anode microstructural and chemical stability in dry methane

NASA Astrophysics Data System (ADS)

Lay, E.; Metcalfe, C.; Kesler, O.

2012-11-01

The Solution Precursor Plasma Spray (SPPS) process was successfully used to deposit cermet coatings that exhibit fine microstructures with high surface area. MgO addition in Ni-YSZ and Ni-SDC cermets results in (Ni,Mg)O solid solution formation, and nickel particles after reduction are finer than in coatings without magnesia. The influence of MgO on the chemical stability of cermets in anodic operating conditions is discussed. It was found that a sufficient amount of magnesia addition (Ni0.9(MgO)0.1) helps to reduce carbon deposition in dry methane.

Bio-inspired surfactant assisted nano-catalyst impregnation of Solid-Oxide Fuel Cell (SOFC) electrodes

DOE PAGES

Ozmen, Ozcan; Zondlo, John W.; Lee, Shiwoo; ...

2015-11-02

A bio-inspired surfactant was utilized to assist in the efficient impregnation of a nano-CeO₂ catalyst throughout both porous Solid Oxide Fuel Cells (SOFC’s) electrodes simultaneously. The process included the initial modification of electrode pore walls with a polydopamine film. The cell was then submersed into a cerium salt solution. The amount of nano-CeO₂ deposited per impregnation step increased by 3.5 times by utilizing this two-step protocol in comparison to a conventional drip impregnation method. The impregnated cells exhibited a 20% higher power density than a baseline cell without the nano-catalyst at 750°C (using humid H₂ fuel).

Chain Conformation of Phosphorycholine-based Zwitterionic Polymer Brushes in Aqueous Solutions

NASA Astrophysics Data System (ADS)

Mao, Jun; Yu, Jing; Lee, Sungsik; Yuan, Guangcui; Satija, Sushil; Chen, Wei; Tirrell, Matthew

Polyzwitterionic brushes are resistant to nonspecific accumulation of proteins and microorganisms, making them excellent candidates for antifouling applications. It is well-known that polyzwitterions exhibit the so-called antipolyelectrolyte effect: Polyzwitterionic brushes would adopt a collapsed conformation at a low ionic strength due to the electrostatic inter/intra-chain association; whereas at a high ionic strength, they would exhibit an extended conformation because the electrostatic inter/intra-chain dipole-dipole interaction is weakened. However, poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) is a unique member in polyzwitterionic families. Its ultrahigh affinity to water leads to no detectable shrinks in aqueous solutions even at low ionic strengths. In this study, we synthesized highly dense PMPC brushes via surface initiated radical polymerization and systematically investigate their conformational behaviors at solid-liquid interfaces in the presence of multivalent counterions, combining X-ray and neutron scattering and force measurements. We have demonstrated that despite no obvious changes of the entire lengths of extended PMPC brushes in aqueous solutions, the chain conformations including, but not limited to, polyzwitterion distribution and charge correlation, varied, dependent on salt types, ionic strengths and ion valences.

Ionic liquid supported on an electrodeposited polycarbazole film for the headspace solid-phase microextraction and gas chromatography determination of aromatic esters.

PubMed

Feng, Yuanyuan; Zhao, Faqiong; Zeng, Baizhao

2015-05-01

A polycarbazole film was electrodeposited on a stainless-steel wire from a solution of N,N-dimethylformamide/propylene carbonate (1:9 v/v) containing 0.10 M carbazole and 0.10 M tetrabutylammonium perchlorate. The obtained polycarbazole fiber was immersed into an ionic liquid (1-hydroxyethyl-3-methyl imidazolium bis[(trifluoromethyl)sulfonyl]imide) solution (in dimethylsulfoxide) for 30 min, followed by drying under an infrared lamp. The resulting polycarbazole/ionic liquid fiber was applied to the headspace solid-phase microextraction and determination of aromatic esters by coupling with gas chromatography and flame ionization detection. Under the optimized conditions, the limits of detection were below 61 ng/L (S/N = 3) and the linear ranges were 0.061-500 μg/L with correlation coefficients above 0.9876. The relative standard deviations were below 4.8% (n = 5) for a single fiber, and below 9.9% for multi-fiber (n = 4). This fiber also exhibited good stability. It could be used for more than 160 times of headspace solid-phase microextraction and could withstand a high temperature up to 350°C. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Near-saturated red emitters: four-coordinate copper(i) halide complexes containing 8-(diphenylphosphino)quinoline and 1-(diphenylphosphino)naphthalene ligands.

PubMed

Liu, Li-Ping; Li, Qian; Xiang, Song-Po; Liu, Li; Zhong, Xin-Xin; Liang, Chen; Li, Guang Hua; Hayat, Tasawar; Alharbi, Njud S; Li, Fa-Bao; Zhu, Nian-Yong; Wong, Wai-Yeung; Qin, Hai-Mei; Wang, Lei

2018-06-07

Recently, highly emissive neutral copper halide complexes have received much attention. Here, a series of four-coordinate mononuclear Cu(i) halide complexes, [CuX(dpqu)(dpna)] (dpqu = 8-(diphenylphosphino)quinoline, dpna = 1-(diphenylphosphino)naphthalene, X = I (1), Br (2) and Cl (3)), were synthesized, and their molecular structures and photophysical properties were investigated. These complexes exhibit near-saturated red emission in the solid state at room temperature and have peak emission wavelengths at 669-691 nm with microsecond lifetimes (τ = 0.46-1.80 μs). Small S1-T1 energy gaps in the solid state indicate that the emission occurs from a thermally activated excited singlet state at ambient temperature. The emission of the complexes 1-3 mainly originates from MLCT transition. The solution-processed devices of complex 1 exhibit stable red emission with a CIE(x, y) of (0.62, 0.38) for a doped device and (0.63, 0.37) for a non-doped device.

Ferroelectric and optical properties of `Ba-doped' new double perovskites

NASA Astrophysics Data System (ADS)

Parida, B. N.; Panda, Niranjan; Padhee, R.; Parida, R. K.

2018-06-01

Solid solution of Pb1.5Ba0.5BiNbO6 ceramic is explored here to obtain its ferroelectric and optical properties. The polycrystalline sample was prepared by a standard solid state reaction route. Room temperature XRD and FTIR spectra of the compound exhibit an appreciable change in its crystal structure of Pb2BiNbO6 on addition of 'Ba' in A site. The surface morphology of the gold-plated sintered pellet sample recorded by SEM exhibits a uniform distribution of small grains with well-defined grain boundaries. Detailed studies on the nature of polarization and variation of dielectric constant, tangent loss with temperature as well as frequency indicate the existence of Ferro-electricity in the sample. Using UV-Vis spectroscopy, the optical band gap of the studied sample has been estimated as 2.1 eV, which is useful for photo catalytic devices. Photoluminescence analysis of the powder sample shows a strong red photoluminescence with blue excitation, which is basically useful for LED.

Changes in Wetting Hysteresis During Bioremediation: Changes in fluid flow behavior monitored with low-frequency seismic attenuation

NASA Astrophysics Data System (ADS)

Wempe, W.; Spetzler, H.; Kittleson, C.; Pursley, J.

2003-12-01

We observed significant reduction in wetting hysteresis with time while a diesel-contaminated quartz crystal was dipped in and out of an oil-reducing bacteria solution. This wetting hysteresis is significantly greater than the wetting hysteresis when the diesel-contaminated quartz crystal is dipped in and out of (1) water, (2) diesel and (3) the bacterial food solution that does not contain bacteria. The reduction in wetting hysteresis of the bacteria solution on the quartz surface results from a reduction in the advancing contact angle formed at the air-liquid-quartz contact with time; the receding contact angle remains the same with time. Our results suggest that the bacteria solution moves across the quartz surface with less resistance after bioremediation has begun. These results imply that bioremediation may influence fluid flow behavior with time. For many fluid-solid systems there is a difference between the contact angle while a contact line advances and recedes across a solid surface; this difference is known as wetting hysteresis. Changes in wetting hysteresis can occur from changes in surface tension or the surface topography. Low contact angle values indicate that the liquid spreads or wets well, while high values indicate poor wetting or non-wetting. Contact angles are estimated in the lab by measuring the weight of the meniscus formed at the air-liquid-quartz interface and by knowing the fluid surface tension. In the lab, we have been able to use low-frequency seismic attenuation data to detect changes in the wetting characteristics of glass plates and of Berea sandstone. The accepted seismic attenuation mechanism is related to the loss of seismic energy due to the hysteresis of meniscus movement (wetting hysteresis) when a pore containing two fluids is stressed at very low frequencies (< 10 Hz). When fluid-fluid-solid systems that exhibit wettability hysteresis are stressed at low frequencies, we observe seismic attenuation, whereas in a system that does not exhibit wettability hysteresis we do not. From our wettability hysteresis results, we conclude that we may be able to monitor bioremediation progress using seismic attenuation data. We are measuring low-frequency seismic attenuation in the lab while flowing bacteria solution through Berea sandstone and we are testing this application in the field.

Effects of drug-carrier interactions on drug dissolution from binary and ternary matrices

NASA Astrophysics Data System (ADS)

Iqbal, Zafar

For nearly five decades, pharmaceutical researchers have studied solid solutions of drugs in polymers as a potential means to enhance the dissolution of drugs with poor aqueous solubility. This has become of greater importance in recent years because most new potential drug compounds (new chemical entities) exhibit poor water solubility and present great challenges to scientists who must design dosage forms from which the drugs are bioavailable. During the formulation of a solid solution, the drug undergoes physical but not chemical alterations that increase its chemical potential in the formulation relative to that of the pure drug in its stable form. This increased chemical potential is responsible for enhanced dissolution as well as physical instabilities, such as amorphous to crystalline conversions and precipitation within the solid state. The chemical potential is derived from the Gibbs free energy, so it is reasonable to explain the behavior of solid solution systems in terms of thermodynamics. Solid solutions and dispersions have been extensively studied by pharmaceutical scientists, both with regard to manufacturing aspects and the proposal of various models in attempts to explain the physical bases for how these systems work. Recently, Dave and Bellantone proposed a model based on the thermodynamic changes resulting from the formulation of binary solid solutions of a drug in the polymer PVP. Their model introduced a modification of the F-H theory, which was used to quantify the drug-polymer interaction energies and calculate the entropy of mixing of the drug and polymer. In this work, the model of Dave and Bellantone was extended to include three-component systems, consisting of one drug mixed in a carrier matrix consisting of mixture of two polymers or a polymer and a surfactant. For this research, solid solutions were formed using various drug weight fractions in the formulations. The study focused on the following points: (1) Prepare solid solution formulations and perform appropriate physical characterizations. (2) Characterize the increase in drug dissolution rates resulting from solid solution formulations. (3) Relate the initial dissolution rates to the drug solubility. (4) Explain the solubility enhancement from solid solution dosage in terms of the drug polymer interactions using the extended thermodynamic model. Two poorly water soluble drugs, levonorgestrel (LEVO) and ethinyl estradiol (EE) were formulated in seven solid solution preparations comprised of four carrier systems. Materials used as carriers included various combinations of the polymers PVP K-30, Copovidone (COP), Poloxamer 182, and the surfactant TweenRTM 20. Additionally, ibuprofen (IBU) was used in three formulations consisting of various combinations of PVP K-30, Copovidone and TweenRTM 20. Formulations with various drug weight fractions (0.5%--30%) were prepared using the solvent evaporation technique. Each formulation was tested for dissolution using intrinsic dissolution apparatus (USP). The solid solutions were compressed into tablets into the sample die that maintained a constant surface area during the dissolution process. DSC, XRD and NIRS scans identified that the crystalline peaks of the drug disappeared with the addition of the polymer for all ratios of EE, indicating the formation of solid solutions (to within the limits of detection of the equipment). This was also observed for the LEVO dispersions up to 10% drug loading. At higher drug loading, solutions were formed but some small degree crystallinity was also present. For each experiment, the initial dissolution rates were obtained from the slope of the mass dissolved vs. time plots taken at early times, and volume normalized initial dissolution rates RV were calculated by dividing the initial dissolution rate by the volume fraction of the drug in the formulation. Comparison of the RV values for the various formulations with a reference RV (typically that of the pure drug or of the formulation with the highest polymer content) allowed calculation of relative volume normalized dissolution rates (RNV). The various RNV were used in the thermodynamic model for data analyses and to determine the interactions between the drug and carrier molecules. It was generally seen that RNV increased with decreased drug fraction, and was adequately modeled by the equations derived from the extended thermodynamic model. It was concluded that the model proposed for the binary and ternary systems successfully represented the mechanism of drug-polymer interaction and the energy changes taken place within the dispersion systems. The dissolution data analysis and subsequent understanding of physical modifications in the dispersion systems characterized by XRD, NIRS and DSC further substantiated the findings. The understanding of the fundamental physical might help scientists to predict the effects of mixing various drugs and polymers, and the effects of varying ratios.

Processing of solid solution, mixed uranium/refractory metal carbides for advanced space nuclear power and propulsion systems

NASA Astrophysics Data System (ADS)

Knight, Travis Warren

Nuclear thermal propulsion (NTP) and space nuclear power are two enabling technologies for the manned exploration of space and the development of research outposts in space and on other planets such as Mars. Advanced carbide nuclear fuels have been proposed for application in space nuclear power and propulsion systems. This study examined the processing technologies and optimal parameters necessary to fabricate samples of single phase, solid solution, mixed uranium/refractory metal carbides. In particular, the pseudo-ternary carbide, UC-ZrC-NbC, system was examined with uranium metal mole fractions of 5% and 10% and corresponding uranium densities of 0.8 to 1.8 gU/cc. Efforts were directed to those methods that could produce simple geometry fuel elements or wafers such as those used to fabricate a Square Lattice Honeycomb (SLHC) fuel element and reactor core. Methods of cold uniaxial pressing, sintering by induction heating, and hot pressing by self-resistance heating were investigated. Solid solution, high density (low porosity) samples greater than 95% TD were processed by cold pressing at 150 MPa and sintering above 2600 K for times longer than 90 min. Some impurity oxide phases were noted in some samples attributed to residual gases in the furnace during processing. Also, some samples noted secondary phases of carbon and UC2 due to some hyperstoichiometric powder mixtures having carbon-to-metal ratios greater than one. In all, 33 mixed carbide samples were processed and analyzed with half bearing uranium as ternary carbides of UC-ZrC-NbC. Scanning electron microscopy, x-ray diffraction, and density measurements were used to characterize samples. Samples were processed from powders of the refractory mono-carbides and UC/UC 2 or from powders of uranium hydride (UH3), graphite, and refractory metal carbides to produce hypostoichiometric mixed carbides. Samples processed from the constituent carbide powders and sintered at temperatures above the melting point of UC showed signs of liquid phase sintering and were shown to be largely solid solutions. Pre-compaction of mixed carbide powders prior to sintering was shown to be necessary to achieve high densities. Hypostoichiometric, samples processed at 2500 K exhibited only the initial stage of sintering and solid solution formation. Based on these findings, a suggested processing methodology is proposed for producing high density, solid solution, mixed carbide fuels. Pseudo-binary, refractory carbide samples hot pressed at 3100 K and 6 MPa showed comparable densities (approximately 85% of the theoretical value) to samples processed by cold pressing and sintering at temperatures of 2800 K.

Negative differential electrolyte resistance in a solid-state nanopore resulting from electroosmotic flow bistability.

PubMed

Luo, Long; Holden, Deric A; White, Henry S

2014-03-25

A solid-state nanopore separating two aqueous solutions containing different concentrations of KCl is demonstrated to exhibit negative differential resistance (NDR) when a constant pressure is applied across the nanopore. NDR refers to a decrease in electrical current when the voltage applied across the nanopore is increased. NDR results from the interdependence of solution flow (electroosmotic and pressure-engendered) with the distributions of K+ and Cl- within the nanopore. A switch from a high-conductivity state to a low-conductivity state occurs over a very narrow voltage window (<2 mV) that depends on the nanopore geometry, electrolyte concentration, and nanopore surface charge density. Finite element simulations based on a simultaneous solution of the Navier-Stokes, Poisson, and Nernst-Planck equations demonstrate that NDR results from a positive feedback mechanism between the ion distributions and electroosmotic flow, yielding a true bistability in fluid flow and electrical current at a critical applied voltage, i.e., the NDR "switching potential". Solution pH and Ca2+ were separately employed as chemical stimuli to investigate the dependence of the NDR on the surface charge density. The NDR switching potential is remarkably sensitive to the surface charge density, and thus to pH and the presence of Ca2+, suggesting possible applications in chemical sensing.

Eco-friendly luminescent solar concentrators with low reabsorption losses and resistance to concentration quenching based on aqueous-solution-processed thiolate-gold nanoclusters

NASA Astrophysics Data System (ADS)

Huang, H. Y.; Cai, K. B.; Chang, L. Y.; Chen, P. W.; Lin, T. N.; Lin, C. A. J.; Shen, J. L.; Talite, M. J.; Chou, W. C.; Yuan, C. T.

2017-09-01

Heavy-metal-containing quantum dots (QDs) with engineered electronic states have been served as luminophores in luminescent solar concentrators (LSCs) with impressive optical efficiency. Unfortunately, those QDs involve toxic elements and need to be synthesized in a hazardous solvent. Recently, biocompatible, eco-friendly gold nanoclusters (AuNCs), which can be directly synthesized in an aqueous solution, have gained much attention for promising applications in ‘green photonics’. Here, we explored the solid-state photophysical properties of aqueous-solution-processed, glutathione-stabilized gold nanoclusters (GSH-AuNCs) with a ligand-to-metal charge-transfer (LMCT) state for developing ‘green’ LSCs. We found that such GSH-AuNCs exhibit a large Stokes shift with almost no spectral overlap between the optical absorption and PL emission due to the LMCT states, thus, suppressing reabsorption losses. Compared with GSH-AuNCs in solution, the photoluminescence quantum yields (PL-QYs) of the LSCs can be enhanced, accompanied with a lengthened PL lifetime owing to the suppression of non-radiative recombination rates. In addition, the LSCs do not suffer from severe concentration-induced PL quenching, which is a common weakness for conventional luminophores. As a result, a common trade-off between light-harvesting efficiency and solid-state PL-QYs can be bypassed due to nearly-zero spectral overlap integral between the optical absorption and PL emission. We expect that GSH-AuNCs hold great promise for serving as luminophores for ‘green’ LSCs by further enhancing solid-state PL-QYs.

Eco-friendly luminescent solar concentrators with low reabsorption losses and resistance to concentration quenching based on aqueous-solution-processed thiolate-gold nanoclusters.

PubMed

Huang, H Y; Cai, K B; Chang, L Y; Chen, P W; Lin, T N; Lin, C A J; Shen, J L; Talite, M J; Chou, W C; Yuan, C T

2017-09-15

Heavy-metal-containing quantum dots (QDs) with engineered electronic states have been served as luminophores in luminescent solar concentrators (LSCs) with impressive optical efficiency. Unfortunately, those QDs involve toxic elements and need to be synthesized in a hazardous solvent. Recently, biocompatible, eco-friendly gold nanoclusters (AuNCs), which can be directly synthesized in an aqueous solution, have gained much attention for promising applications in 'green photonics'. Here, we explored the solid-state photophysical properties of aqueous-solution-processed, glutathione-stabilized gold nanoclusters (GSH-AuNCs) with a ligand-to-metal charge-transfer (LMCT) state for developing 'green' LSCs. We found that such GSH-AuNCs exhibit a large Stokes shift with almost no spectral overlap between the optical absorption and PL emission due to the LMCT states, thus, suppressing reabsorption losses. Compared with GSH-AuNCs in solution, the photoluminescence quantum yields (PL-QYs) of the LSCs can be enhanced, accompanied with a lengthened PL lifetime owing to the suppression of non-radiative recombination rates. In addition, the LSCs do not suffer from severe concentration-induced PL quenching, which is a common weakness for conventional luminophores. As a result, a common trade-off between light-harvesting efficiency and solid-state PL-QYs can be bypassed due to nearly-zero spectral overlap integral between the optical absorption and PL emission. We expect that GSH-AuNCs hold great promise for serving as luminophores for 'green' LSCs by further enhancing solid-state PL-QYs.

Improving the dissolution rate of poorly water soluble drug by solid dispersion and solid solution: pros and cons.

PubMed

Chokshi, Rina J; Zia, Hossein; Sandhu, Harpreet K; Shah, Navnit H; Malick, Waseem A

2007-01-01

The solid dispersions with poloxamer 188 (P188) and solid solutions with polyvinylpyrrolidone K30 (PVPK30) were evaluated and compared in an effort to improve aqueous solubility and bioavailability of a model hydrophobic drug. All preparations were characterized by differential scanning calorimetry, powder X-ray diffraction, intrinsic dissolution rates, and contact angle measurements. Accelerated stability studies also were conducted to determine the effects of aging on the stability of various formulations. The selected solid dispersion and solid solution formulations were further evaluated in beagle dogs for in vivo testing. Solid dispersions were characterized to show that the drug retains its crystallinity and forms a two-phase system. Solid solutions were characterized to be an amorphous monophasic system with transition of crystalline drug to amorphous state. The evaluation of the intrinsic dissolution rates of various preparations indicated that the solid solutions have higher initial dissolution rates compared with solid dispersions. However, after storage at accelerated conditions, the dissolution rates of solid solutions were lower due to partial reversion to crystalline form. The drug in solid dispersion showed better bioavailability in comparison to solid solution. Therefore, considering physical stability and in vivo study results, the solid dispersion was the most suitable choice to improve dissolution rates and hence the bioavailability of the poorly water soluble drug.

Preferential diffusion in concentrated solid solution alloys: NiFe, NiCo and NiCoCr

DOE PAGES

Zhao, Shijun; Osetsky, Yuri; Zhang, Yanwen

2017-02-13

In single-phase concentrated solid-solution alloys (CSAs), including high entropy alloys (HEAs), remarkable mechanical properties are exhibited, as well as extraordinary corrosion and radiation resistance compared to pure metals and dilute alloys. But, the mechanisms responsible for these properties are unknown in many cases. In this work, we employ ab initio molecular dynamics based on density functional theory to study the diffusion of interstitial atoms in Ni and Ni-based face-centered cubic CSAs including NiFe, NiCo and NiCoCr. We model the defect trajectories over >100 ps and estimate tracer diffusion coefficients, correlation factors and activation energies. Furthermore, we found that the diffusionmore » mass transport in CSAs is not only slower than that in pure components, i.e. sluggish diffusion, but also chemically non-homogeneous. The results obtained here can be used in understanding and predicting the atomic segregation and phase separation in CSAs under irradiation conditions.« less

Using the Semiconductors Materials of InSb-ZnTe System in Sensors for Gas Control

NASA Astrophysics Data System (ADS)

Shubenkova, E. G.

2017-04-01

The samples of thin film semiconductor compounds InSb, ZnTe and solid solutions based on them were obtained by vapor deposition of components on a dielectric substrate in a vacuum, followed by annealing and their surface properties in CO, O2 and NH3 gas atmospheres were investigated. Identification of the samples was carried out by X-ray diffraction techniques. In the temperature range 253 ÷ 403 K and a pressure range of 1÷12 Pa the gas adsorption was measured by piezoelectric microbalance technique. In order to establish the basic regularities of processes flowing on samples surface in addition to the electrophisical were used Infrared and Raman spectroscopic measurements. The resulting addiction “surface property - composition” is extreme and have allowed to determine solid solution InSb0,95-ZnTe0,05 as the most sensitive to the presence of ammonia, selective and this sample exhibits a negligible oxidation of surface.

Hybrid organic-inorganic inks flatten the energy landscape in colloidal quantum dot solids

NASA Astrophysics Data System (ADS)

Liu, Mengxia; Voznyy, Oleksandr; Sabatini, Randy; García de Arquer, F. Pelayo; Munir, Rahim; Balawi, Ahmed Hesham; Lan, Xinzheng; Fan, Fengjia; Walters, Grant; Kirmani, Ahmad R.; Hoogland, Sjoerd; Laquai, Frédéric; Amassian, Aram; Sargent, Edward H.

2017-02-01

Bandtail states in disordered semiconductor materials result in losses in open-circuit voltage (Voc) and inhibit carrier transport in photovoltaics. For colloidal quantum dot (CQD) films that promise low-cost, large-area, air-stable photovoltaics, bandtails are determined by CQD synthetic polydispersity and inhomogeneous aggregation during the ligand-exchange process. Here we introduce a new method for the synthesis of solution-phase ligand-exchanged CQD inks that enable a flat energy landscape and an advantageously high packing density. In the solid state, these materials exhibit a sharper bandtail and reduced energy funnelling compared with the previous best CQD thin films for photovoltaics. Consequently, we demonstrate solar cells with higher Voc and more efficient charge injection into the electron acceptor, allowing the use of a closer-to-optimum bandgap to absorb more light. These enable the fabrication of CQD solar cells made via a solution-phase ligand exchange, with a certified power conversion efficiency of 11.28%. The devices are stable when stored in air, unencapsulated, for over 1,000 h.

Electrodeposition mechanism and characterization of Ni-Cu alloy coatings from a eutectic-based ionic liquid

NASA Astrophysics Data System (ADS)

Wang, Shaohua; Guo, Xingwu; Yang, Haiyan; Dai, JiChun; Zhu, Rongyu; Gong, Jia; Peng, Liming; Ding, Wenjiang

2014-01-01

The electrodeposition mechanism, microstructures and corrosion resistances of Ni-Cu alloy coatings on Cu substrate were investigated in a choline chloride-urea (1:2 molar ratio) eutectic-based ionic liquid (1:2 ChCl-urea IL) containing nickel and copper chlorides. Cyclic voltammetry showed that the onset reduction potentials for Cu (∼-0.32 V) and for Ni (∼-0.47 V) were close to each other, indicating that Ni-Cu co-deposition could be easily achieved in the absence of complexing agent which was indispensable in aqueous plating electrolyte. Chronoamperometric investigations revealed that Ni-Cu deposits followed the three-dimensional instantaneous nucleation/growth mechanism, thus producing a solid solution. The compositions, microstructures and corrosion resistances of Ni-Cu alloy coatings were significantly dependent on the deposition current densities. Ni-Cu alloy coatings were α-Ni(Cu) solid solutions, and the coating containing ∼17.6 at.% Cu exhibited the best corrosion resistance because of its dense and crack-free structure.

Synthesis, structures, and photophysical properties of π-expanded oligothiophene 8-mers and their Saturn-like C₆₀ complexes.

PubMed

Shimizu, Hideyuki; Cojal González, José D; Hasegawa, Masashi; Nishinaga, Tohru; Haque, Tahmina; Takase, Masayoshi; Otani, Hiroyuki; Rabe, Jürgen P; Iyoda, Masahiko

2015-03-25

Two isomers of a multifunctional π-expanded macrocyclic oligothiophene 8-mer, E,E-1 and Z,Z-1, were synthesized using a McMurry coupling of a dialdehyde composed of four 2,5-thienylene and three ethynylene units under high dilution conditions. On the other hand, cyclo[8](2,5-thienylene-ethynylene) 2 was synthesized by intramolecular Sonogashira cyclization of ethynyl bromide 5. From STM measurements, both E,E-1 and Z,Z-1 formed self-assembled monolayers at the solid-liquid interface to produce porous networks, and from X-ray analyses of E,E-1 and 2, both compounds had a round shape with a honeycomb stacked structure. E,E-1 formed various fibrous polymorphs due to nanophase separation of the macrorings. E,E-1 and Z,Z-1 in solution exhibited photochromism upon irradiation with visible and UV light, respectively, and this photoisomerization was confirmed by using STM. Furthermore, amorphous films of Z,Z-1 and E,E-1 showed photoisomerization, although single crystals, fibers, and square tubes of E,E-1 remained unchanged under similar conditions. E,E-1 with a 12.5-14.7 Å inner cavity incorporated fullerene C60 in the cavity in solution and the solid state to produce a Saturn-like complex, whose structure was determined by X-ray analysis. 2 also formed a Saturn-like complex with C60 in the solid state. These Saturn-like complexes are stabilized by van der Waals interactions between the sulfur atoms of 8-mer and C60. The complexes exhibited charge-transfer interactions in the solid state. Like E,E-1, Saturn-like complex E,E-1⊃C60 formed small cube and fiber structures depending on the solvent used, whereas those of Saturn-like complex 2⊃C60 were limited due to the rigidity of the macroring of 2.

Thermodynamic modeling of solid solutions between monosulfate and monochromate 3CaO Bullet Al{sub 2}O{sub 3} Bullet Ca[(CrO{sub 4}){sub x}(SO{sub 4}){sub 1-x}] Bullet nH{sub 2}O

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

Leisinger, Sabine M., E-mail: sabine.leisinger@eawag.ch; Institute of Biogeochemistry and Pollutant Dynamics, ETH, CH-8092 Zurich; Lothenbach, Barbara

2012-01-15

In hydrated cement paste AFm-phases are regarded to play an important role in the binding of the toxic contaminant chromate through isomorphic substitution with sulfate. Solid solutions formation can lower the solubility of the solids, thus reducing chromate leaching concentrations. Solid solutions between monosulfate and monochromate were synthesized and characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX) and inductive coupled plasma optical emission spectroscopy (ICP-OES). Based on the measured ion concentrations in solution total solubility products of the solid solution series were determined. For pure monochromate a logK = - 28.4more » {+-} 0.7 was determined. Results from solid and solution analysis showed that limited solid solutions exist. Based on XRD diffractograms a solid solution with a miscibility gap 0.15 < Crx < 0.85 with a dimensionless Guggenheim parameter of 2.43 was proposed.« less

Computational design of microscopic swimmers and capsules: From directed motion to collective behavior

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

Nikolov, Svetoslav V.; Shum, Henry; Balazs, Anna C.

Systems of motile microscopic particles can exhibit behaviors that resemble those of living microorganisms, including cooperative motion, self-organization, and adaptability to changing environments. Using mesoscale computational modeling, we design synthetic microswimmers and microcapsules that undergo controllable, self-propelled motion in solution. Stimuli-responsive hydrogels are used to actuate the microswimmers and to enable their navigation and chemotaxing behavior. The self-propelled motion of microcapsules on solid surfaces is achieved by the release of encapsulated solutes that alter the surface adhesiveness. These signaling solutes also enable interactions among multiple microcapsules that lead to complex, cooperative behavior. Our findings provide guidelines for creating microscopic devicesmore » and machines able to autonomously move and mimic the communication and chemotaxis of biological microorganisms.« less

Structural, Electronic, and Optical Properties of BiOX1-xYx (X, Y = F, Cl, Br, and I) Solid Solutions from DFT Calculations.

PubMed

Zhao, Zong-Yan; Liu, Qing-Lu; Dai, Wen-Wu

2016-08-23

Six BiOX1-xYx (X, Y = F, Cl, Br, and I) solid solutions have been systematically investigated by density functional theory calculations. BiOCl1-xBrx, BiOBr1-xIx, and BiOCl1-xIx solid solutions have very small bowing parameters; as such, some of their properties increase almost linearly with increasing x. For BiOF1-xYx solid solutions, the bowing parameters are very large and it is extremely difficult to fit the related calculated data by a single equation. Consequently, BiOX1-xYx (X, Y = Cl, Br, and I) solid solutions are highly miscible, while BiOF1-xYx (Y = Cl, Br, and I) solid solutions are partially miscible. In other words, BiOF1-xYx solid solutions have miscibility gaps or high miscibility temperature, resulting in phase separation and F/Y inhomogeneity. Comparison and analysis of the calculated results and the related physical-chemical properties with different halogen compositions indicates that the parameters of BiOX1-xYx solid solutions are determined by the differences of the physical-chemical properties of the two halogen compositions. In this way, the large deviation of some BiOX1-xYx solid solutions from Vegard's law observed in experiments can be explained. Moreover, the composition ratio of BiOX1-xYx solid solutions can be measured or monitored using optical measurements.

Evaluation of the flow properties of xanthan gum solution

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

Duda, J.L.; Klaus, E.E.; Leung, W.C.

1981-02-01

In this study, the solution properties of two forms of xanthan gum, a powder and a broth, which are commercially available were evaluated. As previous studies have shown, the solutions prepared from the broth do exhibit better injectivity properties. However, this investigation also shows that other properties of these solutions are not equivalent. In its natural state, xanthane gum exists as a multistranded helix. This ordered confirmation can be destroyed and in a denatured state, the xanthan gum exhibits a more random configuration and consequently higher viscosity. One of the major conclusions of this study is that the xanthan powdermore » is partially denatured when compared to the xanthan molecules which exist in the broth. This denaturing may occur during the drying process in which the xanthan solids are removed from the broth. Solutions prepared from the broth in the absence of the added salt show a transition in the viscosity-temperature relationship at approximately 40 to 50/sup 0/C. This is consistent with the behavior of native xanthan gum solutions. At approximately 50/sup 0/C, the molecules in solution go into a more random state and consequently, an abrupt rise in the viscosity is observed. However, solutions prepared from the polymer powder do not show any evidence of such a transition. The solutions prepared from the broth can be thermally denatured, and this denaturing results in viscosities which are equivalent to the viscosities realized with the powdered polymer. Before denaturing, the broth solution showed a lower viscosity. Further, intrinsic viscosity measurements indicate that the hydrodynamic volume of the polymer solutions prepared from the borth are smaller than the hydrodynamic volumes of solutions prepared from the powder.« less

Green Perylene Bisimide Dyes: Synthesis, Photophysical and Electrochemical Properties

PubMed Central

Chang, Che-Wei; Tsai, Hsing-Yang; Chen, Kew-Yu

2014-01-01

Three asymmetric amino-substituted perylene bisimide dyes with different n-alkyl chain lengths (n = 6, 12, or 18), 1-(N,N-dialkylamino)perylene bisimides (1a–1c), were synthesized under mild condition in high yields and were characterized by 1H NMR, 13C NMR (nuclear magnetic resonance), HRMS (High Resolution Mass Spectrometer), UV-Vis and fluorescence spectra, as well as cyclic voltammetry (CV). These molecules show intense green color in both solution and solid state and are highly soluble in dichloromethane and even in nonpolar solvents, such as hexane. The shapes of the absorption spectra of 1a–1c in solid state and in solution were found to be virtually the same, indicating that the long alkyl chains could efficiently prevent aggregation. They exhibit a unique charge transfer emission in the near-infrared region, of which the peak wavelengths show strong solvatochromism. The dipole moments of the compounds have been estimated using the Lippert-Mataga equation, and upon excitation, they show larger dipole moment changes than that of 1-aminoperylene bisimide (2). Furthermore, all of the compounds exhibit two quasi-reversible one-electron oxidations and two quasi-reversible one-electron reductions in dichloromethane at modest potentials. Complementary density functional theory (DFT) calculations performed on these dyes are reported in order to rationalize their molecular structures and electronic properties. PMID:28788140

1,7-Bis-(N,N-dialkylamino)perylene Bisimides: Facile Synthesis and Characterization as Near-Infrared Fluorescent Dyes

PubMed Central

Chen, Kew-Yu; Chang, Che-Wei

2014-01-01

Three symmetric alkylamino-substituted perylene bisimides with different n-alkyl chain lengths (n = 6, 12, or 18), 1,7-bis-(N,N-dialkylamino)perylene bisimides (1a–1c), were synthesized under mild condition and were characterized by 1H NMR, 13C NMR and high resolution mass spectroscopy. Their optical and electrochemical properties were measured using UV-Vis and emission spectroscopic techniques as well as cyclic voltammetry (CV). These compounds show deep green color in both solution and solid state, and are highly soluble in dichloromethane and even in nonpolar solvents such as hexane. The shapes of the absorption spectra of 1a–1c in the solution and solid state were found to be almost the same, indicating that the long alkyl chains could efficiently prevent intermolecular contact and aggregation. They show a unique charge transfer emission in the near-infrared region, of which the peak wavelengths exhibit strong solvatochromism. The dipole moments of the molecules have been estimated using the Lippert–Mataga equation, and upon excitation, they show larger dipole moment changes than that of 1,7-diaminoperylene bisimide (2). Moreover, all the dyes exhibit two irreversible one-electron oxidations and two quasi-reversible one-electron reductions in dichloromethane at modest potentials. Complementary density functional theory calculations performed on these chromophores are reported in order to rationalize their electronic structure and optical properties. PMID:28788262

Thermal and sonochemical synthesis of porous (Ce,Zr)O2 mixed oxides from metal β-diketonate precursors and their catalytic activity in wet air oxidation process of formic acid.

PubMed

Cau, Camille; Guari, Yannick; Chave, Tony; Larionova, Joulia; Nikitenko, Sergey I

2014-07-01

Porous (Ce0.5Zr0.5)O2 solid solutions were prepared by thermolysis (T=285 °C) or sonolysis (20 kHz, I=32 W cm(-2), Pac=0.46 W mL(-1), T=200 °C) of Ce(III) and Zr(IV) acetylacetonates in oleylamine or hexadecylamine under argon followed by heat treatment of the precipitates obtained in air at 450 °C. Transmission Electron Microscopy images of the samples show nanoparticles of ca. 4-6 nm for the two synthetic approaches. The powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray and μ-Raman spectroscopy of solids obtained after heat treatment indicate the formation of (Ce0.5Zr0.5)O2 solid solutions with a metastable tetragonal crystal structure for the two synthetic routes. The specific surface area of the samples varies between 78 and 149 m(2) g(-1) depending on synthesis conditions. The use of Barrett-Joyner-Halenda and t-plot methods reveal the formation of mixed oxides with a hybrid morphology that combines mesoporosity and microporosity regardless of the method of preparation. Platinum nanoparticles were deposited on the surface of the mixed oxides by sonochemical reduction of Pt(IV). It was found that the materials prepared by sonochemistry exhibit better resistance to dissolution during the deposition process of platinum. X-ray photoelectron spectroscopy analysis shows the presence of Pt(0) and Pt(II) on the surface of mixed oxides. Porous (Ce0.5Zr0.5)O2 mixed oxides loaded with 1.5%wt. platinum exhibit high activity in catalytic wet air oxidation of formic acid at 40 °C. Copyright © 2014 Elsevier B.V. All rights reserved.

Ultrahigh-efficiency solution-processed simplified small-molecule organic light-emitting diodes using universal host materials

PubMed Central

Han, Tae-Hee; Choi, Mi-Ri; Jeon, Chan-Woo; Kim, Yun-Hi; Kwon, Soon-Ki; Lee, Tae-Woo

2016-01-01

Although solution processing of small-molecule organic light-emitting diodes (OLEDs) has been considered as a promising alternative to standard vacuum deposition requiring high material and processing cost, the devices have suffered from low luminous efficiency and difficulty of multilayer solution processing. Therefore, high efficiency should be achieved in simple-structured small-molecule OLEDs fabricated using a solution process. We report very efficient solution-processed simple-structured small-molecule OLEDs that use novel universal electron-transporting host materials based on tetraphenylsilane with pyridine moieties. These materials have wide band gaps, high triplet energy levels, and good solution processabilities; they provide balanced charge transport in a mixed-host emitting layer. Orange-red (~97.5 cd/A, ~35.5% photons per electron), green (~101.5 cd/A, ~29.0% photons per electron), and white (~74.2 cd/A, ~28.5% photons per electron) phosphorescent OLEDs exhibited the highest recorded electroluminescent efficiencies of solution-processed OLEDs reported to date. We also demonstrate a solution-processed flexible solid-state lighting device as a potential application of our devices. PMID:27819053

Quantitative Characterization of Magnetic Mobility of Nanoparticle in Solution-Based Condition.

PubMed

Rodoplu, Didem; Boyaci, Ismail H; Bozkurt, Akif G; Eksi, Haslet; Zengin, Adem; Tamer, Ugur; Aydogan, Nihal; Ozcan, Sadan; Tugcu-Demiröz, Fatmanur

2015-01-01

Magnetic nanoparticles are considered as the ideal substrate to selectively isolate target molecules or organisms from sample solutions in a wide variety of applications including bioassays, bioimaging and environmental chemistry. The broad array of these applications in fields requires the accurate magnetic characterization of nanoparticles for a variety of solution based-conditions. Because the freshly synthesized magnetic nanoparticles demonstrated a perfect magnetization value in solid form, they exhibited a different magnetic behavior in solution. Here, we present simple quantitative method for the measurement of magnetic mobility of nanoparticles in solution-based condition. Magnetic mobility of the nanoparticles was quantified with initial mobility of the particles using UV-vis absorbance spectroscopy in water, ethanol and MES buffer. We demonstrated the efficacy of this method through a systematic characterization of four different core-shell structures magnetic nanoparticles over three different surface modifications. The solid nanoparticles were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD) and saturation magnetization (Ms). The surfaces of the nanoparticles were functionalized with 11-mercaptoundecanoic acid and bovine serum albumin BSA was selected as biomaterial. The effect of the surface modification and solution media on the stability of the nanoparticles was monitored by zeta potentials and hydrodynamic diameters of the nanoparticles. Results obtained from the mobility experiments indicate that the initial mobility was altered with solution media, surface functionalization, size and shape of the magnetic nanoparticle. The proposed method easily determines the interactions between the magnetic nanoparticles and their surrounding biological media, the magnetophoretic responsiveness of nanoparticles and the initial mobilities of the nanoparticles.

Superior lithium adsorption and required magnetic separation behavior of iron-doped lithium ion-sieves

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

Wang, Shulei; Zheng, Shili; Wang, Zheming

The recent research on adsorption-based lithium recovery from lithium-containing solutions has been centred on adsorption capacity and separation of lithium ion-sieves powder from solutions. Herein, an effective iron-doped lithium titanium oxide (Fe-doped Li 2TiO 3) was synthesized by Fe-doping via solid state reactions followed by acid treatment to form iron-doped lithium ion-sieves (Fe/Ti-x(H)). The resulting solid powder displays both superior adsorption capacity of lithium and high separation efficiency of the adsorbent from the solutions. SEM imaging and BET surface area measurement results showed that at Fe doping levels x ≤ 0.15, Fe-doping led to grain shrinkage as compared to Limore » 2TiO 3 and at the same time the BET surface area increased. The Fe/Ti-0.15(H) exhibited saturated magnetization values of 13.76 emu g -1, allowing effective separation of the material from solid suspensions through the use of a magnet. Consecutive magnetic separation results suggested that the Fe/Ti-0.15(H) powders could be applied at large-scale and continuously removed from LiOH solutions with separation efficiency of 96% or better. Lithium adsorption studies indicated that the equilibrium adsorption capacity of Fe/Ti-0.15(H) in LiOH solutions (1.8 g L -1 Li, pH 12) reached 53.3 mg g -1 within 24 h, which was higher than that of pristine Li 2TiO 3 (50.5 mg g-1) without Fe doping. Competitive adsorption and regeneration results indicated that the Fe/Ti-0.15(H) possessed a high selectivity for Li with facile regeneration. Therefore, it could be expected that the iron-doped lithium ion-sieves have practical applicability potential for large scale lithium extraction and recovery from lithium-bearing solutions.« less

Superior lithium adsorption and required magnetic separation behavior of iron-doped lithium ion-sieves

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

Wang, Shulei; Zheng, Shili; Wang, Zheming

The recent research on adsorption-based lithium recovery from lithium-containing solutions has been centred on adsorption capacity and separation of lithium ion-sieves powder from solutions. Herein, an effective iron-doped lithium titanium oxide (Fe-doped Li2TiO3) was synthesized by Fe-doping via solid state reactions followed by acid treatment to form iron-doped lithium ion-sieves (Fe/Ti-x(H)). The resulting solid powder displays both superior adsorption capacity of lithium and high separation efficiency of the adsorbent from the solutions. SEM imaging and BET surface area measurement results showed that at Fe doping levels x0.15, Fe-doping led to grain shrinkage as compared to Li2TiO3 and at the samemore » time the BET surface area increased. The Fe/Ti-0.15(H) exhibited saturated magnetization values of 13.76 emu g-1, allowing effective separation of the material from solid suspensions through the use of a magnet. Consecutive magnetic separation results suggested that the Fe/Ti-0.15(H) powders could be applied at large-scale and continuously removed from LiOH solutions with separation efficiency of 96% or better. Lithium adsorption studies indicated that the equilibrium adsorption capacity of Fe/Ti-0.15(H) in LiOH 2 solutions (1.8 g L-1 Li, pH 12) reached 53.3 mg g-1 within 24 h, which was higher than that of pristine Li2TiO3 (50.5 mg g-1) without Fe doping. Competitive adsorption and regeneration results indicated that the Fe/Ti-0.15(H) possessed a high selectivity for Li with facile regeneration. Therefore, it could be expected that the iron-doped lithium ion-sieves have practical applicability potential for large scale lithium extraction and recovery from lithium-bearing solutions.« less

Superior lithium adsorption and required magnetic separation behavior of iron-doped lithium ion-sieves

DOE PAGES

Wang, Shulei; Zheng, Shili; Wang, Zheming; ...

2018-09-09

The recent research on adsorption-based lithium recovery from lithium-containing solutions has been centred on adsorption capacity and separation of lithium ion-sieves powder from solutions. Herein, an effective iron-doped lithium titanium oxide (Fe-doped Li 2TiO 3) was synthesized by Fe-doping via solid state reactions followed by acid treatment to form iron-doped lithium ion-sieves (Fe/Ti-x(H)). The resulting solid powder displays both superior adsorption capacity of lithium and high separation efficiency of the adsorbent from the solutions. SEM imaging and BET surface area measurement results showed that at Fe doping levels x ≤ 0.15, Fe-doping led to grain shrinkage as compared to Limore » 2TiO 3 and at the same time the BET surface area increased. The Fe/Ti-0.15(H) exhibited saturated magnetization values of 13.76 emu g -1, allowing effective separation of the material from solid suspensions through the use of a magnet. Consecutive magnetic separation results suggested that the Fe/Ti-0.15(H) powders could be applied at large-scale and continuously removed from LiOH solutions with separation efficiency of 96% or better. Lithium adsorption studies indicated that the equilibrium adsorption capacity of Fe/Ti-0.15(H) in LiOH solutions (1.8 g L -1 Li, pH 12) reached 53.3 mg g -1 within 24 h, which was higher than that of pristine Li 2TiO 3 (50.5 mg g-1) without Fe doping. Competitive adsorption and regeneration results indicated that the Fe/Ti-0.15(H) possessed a high selectivity for Li with facile regeneration. Therefore, it could be expected that the iron-doped lithium ion-sieves have practical applicability potential for large scale lithium extraction and recovery from lithium-bearing solutions.« less

Single crystal structure analyses of scheelite-powellite CaW1-xMoxO4 solidsolutions and unique occurrence in Jisyakuyama skarn deposits

NASA Astrophysics Data System (ADS)

Yamashita, K.; Yoshiasa, A.; Miyazaki, H.; Tokuda, M.; Tobase, T.; Isobe, H.; Nishiyama, T.; Sugiyama, K.; Miyawaki, R.

2017-12-01

Jisyakuyama skarn deposit, Fukuchi, Fukuoka, Japan, shows a simple occurrenceformed by penetration of hot water into limestone cracks. A unique occurrence of scheelite-powellite CaW1-xMoxO4 minerals is observed in the skarn deposit. Many syntheticexperiments for scheelite-powellite solid solutions have been reported as research onfluorescent materials. In this system it is known that a complete continuous solid solution isformed even at room temperature. In this study, we have carried out the chemical analyses,crystal structural refinements and detail description of occurrence on scheelite-powelliteminerals. We have also attempted synthesis of single crystal of solid solution in a widecomposition range. The chemical compositions were determined by JEOL scanningelectron microscope and EDS, INCA system. We have performed the crystal structurerefinements of the scheelite-powellite CaW1-xMoxO4 solid solutions (x=0.0-1.0) byRIGAKU single-crystal structure analysis system RAPID. The R and S values are around0.0s and 1.03. As the result of structural refinements of natural products and many solidsolutions, we confirm that most large natural single crystals have compositions at bothendmembers, and large solid solution crystals are rare. The lattice constants, interatomicdistances and other crystallographic parameters for the solid solution change uniquely withcomposition and it was confirmed as a continuous solid solution. Single crystals of scheeliteendmember + powellite endmember + solid solution with various compositions form anaggregate in the deposit (Figure 1). Crystal shapes of powellite and scheelite arehypidiomorphic and allotriomorphic, respectively. Many solid solution crystals areaccompanied by scheelite endmember and a compositional gap is observed betweenpowellite and solid-solution crystals. The presence of several penetration solutions withsignificantly different W and Mo contents may be assumed. This research can be expectedto lead to giving restrictive conditions to elucidate the mineralization process. Figure1. Scheelite + Powellite + solid solution aggregate

Self-assembled nanostructures of linear arylacetylenes and their aza-substituted analogues

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

Xu, Jia-Ju; Department of Physics and Materials Science and Centre of Super Diamond and Advanced Films; Yang, Xiong-Bo

2016-06-15

A series of linear phenylene ethynylene molecules have been synthesized, and aza-substitution has been used as a strategy to fine-tune the properties of the molecules. All the compounds exhibited pure blue emission both in solution and solid state, and fluorescence quantum yields as high as 0.66, 0.63 and 0.82 were found in chloroform solutions. The well-defined nanostructures such as quasi-cubes, cubes and rods were fabricated by self-assembly method from these compounds. The photophysical properties and aggregation behavior of self-assembled structures were analyzed in detail. The morphology as well as photophysical properties of these nanostructures have been tuned with selective requirements.

Solid-Solution Sulfides Derived from Tunable Layered Double Hydroxide Precursors/Graphene Aerogel for Pseudocapacitors and Sodium-Ion Batteries.

PubMed

Song, Yajie; Li, Hui; Yang, Lan; Bai, Daxun; Zhang, Fazhi; Xu, Sailong

2017-12-13

Transition-metal sulfides (TMSs) are suggested as promising electrode materials for electrochemical pseudocapacitors and lithium- and sodium-ion batteries; however, they typically involve mixed composites or conventionally stoichiometric TMSs (such as NiCo 2 S 4 and Ni 2 CoS 4 ). Herein we demonstrate a preparation of solid-solution sulfide (Ni 0.7 Co 0.3 )S 2 supported on three-dimensional graphene aerogel (3DGA) via a sulfuration of NiCo-layered double hydroxide (NiCo-LDH) precursor/3DGA. The electrochemical tests show that the (Ni 0.7 Co 0.3 )S 2 /3DGA electrode exhibits a capacitance of 2165 F g -1 at 1 A g -1 , 2055 F g -1 at 2 A g -1 , and 1478 F g -1 at 10 A g -1 ; preserves 78.5% capacitance retention upon 1000 cycles for pseudocapacitors; and in particular, possesses a relatively high charge capacity of 388.7 mA h g -1 after 50 cycles at 100 mA g -1 as anode nanomaterials for sodium-ion batteries. Furthermore, the electrochemical performances are readily tuned by varying the cationic type of the tunable LDH precursors to prepare different solid-solution sulfides, such as (Ni 0.7 Fe 0.3 )S 2 /3DGA and (Co 0.7 Fe 0.3 )S 2 /3DGA. Our results show that engineering LDH precursors can offer an alternative for preparing diverse transition-metal sulfides for energy storage.

Microwave-assisted solid-phase synthesis of highly fluorescent carbon nanoparticles and its application in intracellular pH sensing.

PubMed

Yang, Shenghong; Chen, Xiao; Liu, Shuqin; Wang, Fuxin; Ouyang, Gangfeng

2018-08-15

Fluorescent carbon nanoparticles (FCNPs) have been deeply researched and widely applied in recent years due to their good optics performance, chemical stability and biocompatibility. Herein, a green and rapid microwave-assisted solid-phase synthesis (solvent-free) approach was proposed for the fabrication of highly FCNPs in a very short period of time, 4 min. The as-prepared FCNPs can emit a blue emission with quantum yield of up to 63.2% in water solution and show yellow fluorescence in the solid state. The FCNPs also exhibit special solvent effect that the fluorescence emission can be adjusted by controlling the solvent ratio of ethanol and water. Most importantly, the FCNPs possess a narrow-range pH response. The probe responds linearly and rapidly to minor pH fluctuations within the range of 3.47-5.10 and the correlation coefficient is above 0.99. The proposed FCNPs also exhibit high photostability and reusability. As expected, the cell imaging and intracellular pH monitoring was achieved successfully in living SMMC 7721 hepatoma cells by this probe. The FCNPs is promising as a convenient and general fluorescent pH sensor for bioimaging applications. Copyright © 2018. Published by Elsevier B.V.

The effect of Si and Al concentrations on the removal of U(VI) in the alkaline conditions created by NH3 gas

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

Katsenovich, Yelena P.; Cardona, Claudia; Lapierre, Robert

2016-10-01

Remediation of uranium in the deep unsaturated zone is a challenging task, especially in the presence of oxygenated, high-carbonate alkalinity soil and pore water composition typical for arid and semi-arid environments of the western regions of the U.S. This study evaluates the effect of various pore water constituencies on changes of uranium concentrations in alkaline conditions, created in the presence of reactive gases such as NH3 to effectively mitigate uranium contamination in the vadose zone sediments. This contaminant is a potential source for groundwater pollution through slow infiltration of soluble and highly mobile uranium species towards the water table. Themore » objective of this research was to evaluate uranium sequestration efficiencies in the alkaline synthetic pore water solutions prepared in a broad range of Si, Al, and bicarbonate concentrations typically present in field systems of the western U.S. regions and identify solid uranium-bearing phases that result from ammonia gas treatment. In previous studies (Szecsody et al. 2012; Zhong et al. 2015), although uranium mobility was greatly decreased, solid phases could not be identified at the low uranium concentrations in field-contaminated sediments. The chemical composition of the synthetic pore water used in the experiments varied for silica (5–250 mM), Al3+ (2.8 or 5 mM), HCO3- (0–100 mM) and U(VI) (0.0021–0.0084 mM) in the solution mixture. Experiment results suggested that solutions with Si concentrations higher than 50 mM exhibited greater removal efficiencies of U(VI). Solutions with higher concentrations of bicarbonate also exhibited greater removal efficiencies for Si, Al, and U(VI). Overall, the silica polymerization reaction leading to the formation of Si gel correlated with the removal of U(VI), Si, and Al from the solution. If no Si polymerization was observed, there was no U removal from the supernatant solution. Speciation modeling indicated that the dominant uranium species in the presence of bicarbonate were anionic uranyl carbonate complexes (UO2(CO3)2-2 and UO2(CO3)3-4) and in the absence of bicarbonate in the solution, U(VI) major species appeared as uranyl-hydroxide (UO2(OH)3- and UO2(OH)4-2) species. The model also predicted the formation of uranium solid phases. Uranyl carbonates as rutherfordine [UO2CO3], cejkaite [Na4(UO2)(CO3)3] and hydrated uranyl silicate phases as Na-boltwoodite [Na(UO2)(SiO4)·1.5H2O] were anticipated for most of the synthetic pore water compositions amended from medium (2.9 mM) to high (100 mM) bicarbonate concentrations.« less

Casting of Halide and Fluoride Alloys for Laser Windows

DTIC Science & Technology

1974-07-15

mechanism leads to an inverse square root dependence of fracture strength on grain size. Since CaF2, SrFp and BaFp all exhibit at least microplastic ...flaws or microplasticity is the strength limiting factor is not known. 4.2.2 Solid-solution strengthening 4.2.2. 1 General If fracture in these...Temperature Microplasticity in SrF2 Single Crystals, " J. Appl. Phys. 41_(4) 1871 (1970). 12. T.S. Liu and C.H. Li, " Plasticity of Barium Fluoride

Stirring-controlled solidified floating solid-liquid drop microextraction as a new solid phase-enhanced liquid-phase microextraction method by exploiting magnetic carbon nanotube-nickel hybrid.

PubMed

Ghazaghi, Mehri; Mousavi, Hassan Zavvar; Shirkhanloo, Hamid; Rashidi, Alimorad

2017-01-25

A specific technique is introduced to overcome limitations of classical solidification of floating organic drop microextraction, such as tedious and time-consuming centrifuge step and using disperser solvent, by facile and efficient participation of solid and liquid phases. In this proposed method of stirring-controlled solidified floating solid-liquid drop microextraction (SC-SF-SLDME), magnetic carbon nanotube-nickel hybrid (MNi-CNT) as a solid part of the extractors are dispersed ultrasonically in sample solution, and the procedure followed by dispersion of liquid phase (1-undecanol) through high-rate stirring and easily recollection of MNi-CNT in organic solvent droplets through hydrophobic force. With the reduction in speed of stirring, one solid-liquid drop is formed on top of the solution. MNi-CNT acts as both extractor and the coalescence helper between organic droplets for a facile recollection. MNi-CNT was prepared by spray pyrolysis of nickel oleate/toluene mixture at 1000 °C. Four tyrosine kinase inhibitors were selected as model analytes and the effecting parameters were investigated. The results confirmed that magnetic nanoadsorbent has an important role in the procedure and complete collection of dispersed solvent is not achieved in the absence of the solid phase. Also, short extraction time exhibited success of the proposed method and effect of dispersed solid/liquid phases. The limits of quantification (LOQs) for imatinib, sunitinib, erlotinib, and nilotinib were determined to be as low as 0.7, 1.7, 0.6, and 1.0 μg L -1 , respectively. The intra-day precisions (RSDs) were lower than 4.5%. Method performance was investigated by determination of mentioned tyrosine kinase inhibitors (TKIs) in human serum and cerebrospinal fluid samples with good recoveries in the range of 93-98%. Copyright © 2016 Elsevier B.V. All rights reserved.

Enabling Surgical Placement of Hydrogels through Achieving Paste-Like Rheological Behavior in Hydrogel Precursor Solutions

PubMed Central

Beck, Emily C.; Lohman, Brooke L.; Tabakh, Daniel B.; Kieweg, Sarah L.; Gehrke, Stevin H.; Berkland, Cory J.; Detamore, Michael S.

2015-01-01

Hydrogels are a promising class of materials for tissue regeneration, but they lack the ability to be molded into a defect site by a surgeon because hydrogel precursors are liquid solutions that are prone to leaking during placement. Therefore, although the main focus of hydrogel technology and developments are on hydrogels in their crosslinked form, our primary focus is on improving the fluid behavior of hydrogel precursor solutions. In this work, we introduce a method to achieve paste-like hydrogel precursor solutions by combining hyaluronic acid nanoparticles with traditional crosslinked hyaluronic acid hydrogels. Prior to crosslinking, the samples underwent rheological testing to assess yield stress and recovery using linear hyaluronic acid as a control. The experimental groups containing nanoparticles were the only solutions that exhibited a yield stress, demonstrating that the nanoparticulate rather than the linear form of hyaluronic acid was necessary to achieve paste-like behavior. The gels were also photocrosslinked and further characterized as solids, where it was demonstrated that the inclusion of nanoparticles did not adversely affect the compressive modulus and that encapsulated bone marrow-derived mesenchymal stem cells remained viable. Overall, this nanoparticle-based approach provides a platform hydrogel system that exhibits a yield stress prior to crosslinking, and can then be crosslinked into a hydrogel that is capable of encapsulating cells that remain viable. This behavior may hold significant impact for hydrogel applications where a paste-like behavior is desired in the hydrogel precursor solution. PMID:25691398

Electronic structure-sunlight driven water splitting activity correlation of (Zn1-yGay)(O1-zNz).

PubMed

RajaAmbal, Sivaraman; Yadav, A K; Jha, S N; Bhattacharyya, D; Gopinath, Chinnnakonda S

2014-11-21

(Zn1-yGay)(O1-zNz) (y≤ 0.10; z≤ 0.15) solid solutions have been investigated for their electronic structure and visible light photocatalytic activity, and a correlation was found between them. (Zn1-yGay)(O1-zNz) with ZnO as the major component have been synthesized by a solution combustion method in 10 minutes using simple raw materials. The local structures of Zn K edge and Ga K edge, and changes in the chemical environment with the incorporation of Ga and N in ZnO were determined by EXAFS study. EXAFS and XRD results suggested the dissolution of GaN in the ZnO lattice. The homogeneity of the solid solution was demonstrated from HRTEM studies. Photoluminescence studies revealed the creation of a new band at the top of the ZnO valence band (VB), and thus the broadening of the VB of (Zn1-yGay)(O1-zNz) or a decrease in the band gap was attributed to the origin of visible light absorption. UV-Vis spectral studies showed light absorption up to 550 nm, which directly supports the VB broadening. Predominant oxygen vacancies and high photocorrosion observed for ZnO were fully suppressed for (Zn1-yGay)(O1-zNz), indicating the minimization of defects, and thus more sustainability under irradiation conditions. The bare solid solution exhibited reasonable and promising activity for solar hydrogen evolution and photoelectrochemical current generation at 0 V. The present work explained factors such as the preparation method, single phase structure with the stabilization of integral parts, homogeneity in the structure, compensation of oxygen vacancies, and suppression of the density of recombination centres that play a pivotal role in realizing solar energy harvesting.

Partition characteristics of polycyclic aromatic hydrocarbons on soils and sediments

USGS Publications Warehouse

Chiou, C.T.; Mcgroddy, S.E.; Kile, D.E.

1998-01-01

The partition behavior was determined for three polycyclic aromatic hydrocarbons (PAHs), i.e., naphthalene, phenanthrene, and pyrene, from water to a range of soil and sediment samples. The measured partition coefficients of the individual PAHs between soil/sediment organic matter (SOM) and water (i.e., K(oc) values) are relatively invariant either for the 'clean' (uncontaminated) soils or for the clean sediments; however, the mean K(oc) values on the sediments are about twice the values on the soils. This disparity is similar to the earlier observation for other nonpolar solutes and reflects the compositional differences between soil and sediment organic matters. No significant differences in K(oc) are observed between a clean coastal marine sediment and freshwater sediments. The coastal sediments that are significantly impacted by organic contaminants exhibit higher K(oc) values. At given K(ow) values (octanol-water), the PAHs exhibit much higher K(oc) values than other relatively nonpolar solutes (e.g., chlorinated hydrocarbons). This effect is shown to result from the enhanced partition of PAHs to SOM rather than from lower K(ow) values of PAHs at given supercooled liquid solute solubilities in water. The enhanced partition of PAHs over other nonpolar solutes in SOM provides an account of the markedly different correlations between log K(oc) and log K(ow) for PAHs and for other nonpolar solutes. The improved partition of PAHs in SOM stems apparently from the enhanced compatibility of their cohesive energy densities with those of the aromatic components in SOM. The approximate aromatic fraction in soil/sediment organic matter has been assessed by solid-state 13C-NMR spectroscopy.The partition behavior was determined for three polycyclic aromatic hydrocarbons (PAHs), i.e., naphthalene, phenanthrene, and pyrene, from water to a range of soil and sediment samples. The measured partition coefficients of the individual PAHs between soil/sediment organic matter (SOM) and water (i.e., Koc values) are relatively invariant either for the `clean' (uncontaminated) soils or for the clean sediments; however, the mean Koc values on the sediments are about twice the values on the soils. This disparity is similar to the earlier observation for other nonpolar solutes and reflects the compositional differences between soil and sediment organic matters. No significant differences in Koc are observed between a clean coastal marine sediment and freshwater sediments. The coastal sediments that are significantly impacted by organic contaminants exhibit higher Koc values. At given Kow values (octanol-water), the PAHs exhibit much higher Koc values than other relatively nonpolar solutes (e.g., chlorinated hydrocarbons). This effect is shown to result from the enhanced partition of PAHs to SOM rather than from lower Kow values of PAHs at given supercooled liquid solute solubilities in water. The enhanced partition of PAHs over other nonpolar solutes in SOM provides an account of the markedly different correlations between log Koc and log Kow for PAHs and for other nonpolar solutes. The improved partition of PAHs in SOM stems apparently from the enhanced compatibility of their cohesive energy densities with those of the aromatic components in SOM. The approximate aromatic fraction in soil/sediment organic matter has been assessed by solid-state 13C-NMR spectroscopy.

Structural and low temperature dielectric studies on Pb0.8Bi0.2Fe0.6Nb0.4O3 multiferroic solid solution

NASA Astrophysics Data System (ADS)

Dadami, Sunanda T.; Matteppanvar, Shidaling; Shivaraja, I.; Rayaprol, Sudhindra; Deshapande, S. K.; Angadi, Basavaraj

2018-05-01

In this paper the structural and low temperature dielectric properties of Pb0.8Bi0.2Fe0.6Nb0.4O3 (PBFNO) multiferroic solid solution were reported. PBFNO multiferroic was synthesized by single step solid state reaction method. Calcination was carried out at 700 °/2hr with different sintering temperature (800 °C, 850 °C, 900 °C, 950 °C, 1000 °C and 1050 °C for 1 hr) and time duration (800 °C for 1 to 5 hr). Single phase was confirmed through room temperature (RT) X-ray Diffraction (XRD). It was found that sintering carried out at 800°C/3 hr gives single phase. Rietveld refined lattice parameters using monoclinic structure are: a = 5.6663(1) Å, b = 5.6694(1) Å, c = 4.0112(1) Å and β = 90.038(1)° with the average grain size as 2.987 µm. The dielectric properties studied over a wide range of frequency (100 Hz - 5 MHz) and temperature (133 K - 293 K). Dielectric constant and loss tangent exhibits frequency dispersion nature at low frequency region. AC conductivity increases with increase in temperature corresponds to negative temperature coefficient of resistance (NTCR) behaviour.

Research update: Prediction of high figure of merit plateau in SnS and solid solution of (Pb,Sn)S

DOE PAGES

Hao, Shiqiang; Dravid, Vinayak P.; Kanatzidis, Mercouri G.; ...

2016-10-17

Direct conversion between thermal and electrical energy can be achieved by thermoelectric materials, which provide a viable route for power generation and solid state refrigeration. Here, we use a combination of energetic, electronic, and vibrational first-principles based results to predict the figure of merit performance in hole doped single crystals of SnS and (Pb,Sn)S. We find high ZT values for both materials, specifically for (Pb,Sn)S along the b-axis. Both SnS and (Pb,Sn)S have excellent power factors when doped, due to a combination of increased electrical conductivity (due to doping) and a significantly enhanced Seebeck coefficient obtained by a doping-induced multibandmore » effect. Anharmonic phonon calculations combined with a Debye-Calloway model show that the lattice thermal conductivity of both compounds is low, due to intrinsic anharmonicity, and is lowered further by the random, solid solution nature of the cation sublattice of (Pb,Sn)S. (Pb,Sn)S exhibits a high ZT plateau ranging from 1.3 at 300 K to 1.9 at 800 K. Finally, the overall ZT of the hole doped (Pb,Sn)S crystals is predicted to outperform most of the current state-of-the-art thermoelectric sulfide materials.« less

Research update: Prediction of high figure of merit plateau in SnS and solid solution of (Pb,Sn)S

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

Hao, Shiqiang; Dravid, Vinayak P.; Kanatzidis, Mercouri G.

Direct conversion between thermal and electrical energy can be achieved by thermoelectric materials, which provide a viable route for power generation and solid state refrigeration. Here, we use a combination of energetic, electronic, and vibrational first-principles based results to predict the figure of merit performance in hole doped single crystals of SnS and (Pb,Sn)S. We find high ZT values for both materials, specifically for (Pb,Sn)S along the b-axis. Both SnS and (Pb,Sn)S have excellent power factors when doped, due to a combination of increased electrical conductivity (due to doping) and a significantly enhanced Seebeck coefficient obtained by a doping-induced multibandmore » effect. Anharmonic phonon calculations combined with a Debye-Calloway model show that the lattice thermal conductivity of both compounds is low, due to intrinsic anharmonicity, and is lowered further by the random, solid solution nature of the cation sublattice of (Pb,Sn)S. (Pb,Sn)S exhibits a high ZT plateau ranging from 1.3 at 300 K to 1.9 at 800 K. Finally, the overall ZT of the hole doped (Pb,Sn)S crystals is predicted to outperform most of the current state-of-the-art thermoelectric sulfide materials.« less

Nanostructural hierarchy increases the strength of aluminium alloys.

PubMed

Liddicoat, Peter V; Liao, Xiao-Zhou; Zhao, Yonghao; Zhu, Yuntian; Murashkin, Maxim Y; Lavernia, Enrique J; Valiev, Ruslan Z; Ringer, Simon P

2010-09-07

Increasing the strength of metallic alloys while maintaining formability is an interesting challenge for enabling new generations of lightweight structures and technologies. In this paper, we engineer aluminium alloys to contain a hierarchy of nanostructures and possess mechanical properties that expand known performance boundaries-an aerospace-grade 7075 alloy exhibits a yield strength and uniform elongation approaching 1 GPa and 5%, respectively. The nanostructural architecture was observed using novel high-resolution microscopy techniques and comprises a solid solution, free of precipitation, featuring (i) a high density of dislocations, (ii) subnanometre intragranular solute clusters, (iii) two geometries of nanometre-scale intergranular solute structures and (iv) grain sizes tens of nanometres in diameter. Our results demonstrate that this novel architecture offers a design pathway towards a new generation of super-strong materials with new regimes of property-performance space.

Summary Report of Comprehensive Laboratory Testing to Establish the Effectiveness of Proposed Treatment Methods for Unremediated and Remediated Nitrate Salt Waste Streams

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

Anast, Kurt Roy; Funk, David John; Hargis, Kenneth Marshall

The inadvertent creation of transuranic waste carrying hazardous waste codes D001 and D002 requires the treatment of the material to eliminate the hazardous characteristics and allow its eventual shipment and disposal at the Waste Isolation Pilot Plant (WIPP). This report documents the effectiveness of two treatment methods proposed to stabilize both the unremediated and remediated nitrate salt waste streams (UNS and RNS, respectively) at Los Alamos National Laboratory (LANL). The two technologies include the addition of zeolite (with and without the addition of water as a processing aid) and cementation. Surrogates were developed to evaluate both the solid and liquidmore » fractions expected from parent waste containers, and both the solid and liquid fractions were tested. Both technologies are shown to be effective at eliminating the characteristic of ignitability (D001), and the addition of zeolite was determined to be effective at eliminating corrosivity (D002), with the preferred option1 of adding zeolite currently planned for implementation at LANL’s Waste Characterization, Reduction, and Repackaging Facility (WCRRF). The course of this work verified the need to evaluate and demonstrate the effectiveness of the proposed remedy for debris material, if required. The evaluation determined that WypAlls, cheesecloth, and Celotex absorbed with saturated nitrate salt solutions exhibit the ignitability characteristic (all other expected debris is not classified as ignitable). Finally, liquid surrogates containing saturated nitrate salts did not exhibit the characteristic of ignitability in their pure form (those neutralized with Kolorsafe and mixed with sWheat did exhibit D001). Sensitivity testing and an analysis were conducted to evaluate the waste form for reactivity. Tests included subjecting surrogate material to mechanical impact, friction, electrostatic discharge and thermal insults. The testing confirmed that the waste does not exhibit the characteristic of reactivity (D003). Follow-on testing was conducted to demonstrate the effectiveness of zeolite stabilization for ignitable WypAll and cheesecloth debris and additional nitrate salt solutions (those exhibiting the oxidizer characteristic) to demonstrate the effectiveness of the remedy. Follow-on testing also included testing of surrogate materials containing Waste Lock 770, which is present in four of the RNS containers, and potential items of debris such as plywood and Celotex material. Testing to evaluate the effectiveness of the remedy was performed using the specific remediation processes that are planned for use at the WCRRF. Finally, testing was also performed to evaluate the holding capacity of zeolite using a highly acidic surrogate solution and to characterize the composition of gases generated during mixing of zeolite with surrogate solutions. All these tests demonstrated the effectiveness of adding zeolite as the planned remedy.« less

Production of thermostable invertases by Aspergillus caespitosus under submerged or solid state fermentation using agroindustrial residues as carbon source

PubMed Central

Alegre, Ana Cláudia Paiva; de Lourdes Teixeira de Moraes Polizeli, Maria; Terenzi, Héctor Francisco; Jorge, João Atílio; Guimarães, Luis Henrique Souza

2009-01-01

The filamentous fungus Aspergillus caespitosus was a good producer of intracellular and extracellular invertases under submerged (SbmF) or solid-state fermentation (SSF), using agroindustrial residues, such as wheat bran, as carbon source. The production of extracellular enzyme under SSF at 30°C, for 72h, was enhanced using SR salt solution (1:1, w/v) to humidify the substrate. The extracellular activity under SSF using wheat bran was around 5.5-fold higher than that obtained in SbmF (Khanna medium) with the same carbon source. However, the production of enzyme with wheat bran plus oat meal was 2.2-fold higher than wheat bran isolated. The enzymatic production was affected by supplementation with nitrogen and phosphate sources. The addition of glucose in SbmF and SSF promoted the decreasing of extracellular activity, but the intracellular form obtained in SbmF was enhanced 3-5-fold. The invertase produced in SSF exhibited optimum temperature at 50°C while the extra- and intracellular enzymes produced in SbmF exhibited maximal activities at 60°C. All enzymatic forms exhibited maximal activities at pH 4.0-6.0 and were stable up to 1 hour at 50°C. PMID:24031406

White/blue-emitting, water-dispersible CdSe quantum dots prepared by counter ion-induced polymer collapse

NASA Astrophysics Data System (ADS)

Wang, Jing; Goh, Jane Betty; Goh, M. Cynthia; Giri, Neeraj Kumar; Paige, Matthew F.

2015-09-01

The synthesis and characterization of water-dispersible, luminescent CdSe/ZnS semiconductor quantum dots that exhibit nominal "white" fluorescence emission and have potential applications in solid-state lighting is described. The nanomaterials, prepared through counter ion-induced collapse and UV cross-linking of high-molecular weight polyacrylic acid in the presence of appropriate aqueous inorganic ions, were of ∼2-3 nm diameter and could be prepared in gram quantities. The quantum dots exhibited strong luminescence emission in two bands, the first in the blue-region (band edge) of the optical spectrum and the second, a broad emission in the red-region (attributed to deep trap states) of the optical spectrum. Because of the relative strength of emission of the band edge and deep trap state luminescence, it was possible to achieve visible white luminescence from the quantum dots in aqueous solution and in dried, solid films. The optical spectroscopic properties of the nanomaterials, including ensemble and single-molecule spectroscopy, was performed, with results compared to other white-emitting quantum dot systems described previously in the literature.

Structural, thermodynamic, and mechanical properties of WCu solid solutions

NASA Astrophysics Data System (ADS)

Liang, C. P.; Wu, C. Y.; Fan, J. L.; Gong, H. R.

2017-11-01

Various properties of Wsbnd Cu solid solutions are systematically investigated through a combined use of first-principles calculation, cluster expansion, special quasirandom structures (SQS), and lattice dynamics. It is shown that SQS are effective to unravel the intrinsic nature of solid solutions, and that BCC and FCC W100-xCux solid solutions are energetically more stable when 0 ≤ x ≤ 70 and 70 < x ≤ 100, respectively. Calculations also reveal that the Debye model should be appropriate to derive thermodynamic properties of Wsbnd Cu, and that the coefficients of thermal expansion of W100-xCux solid solutions are much lower than those of corresponding mechanical mixtures. In addition, the G/B values of W100-xCux solid solutions reach a minimum at x = 50, which is fundamentally due to the softening of phonons as well as strong chemical bonding between W and Cu with a mainly metallic feature.

Conversion of depleted uranium hexafluoride to a solid uranium compound

DOEpatents

Rothman, Alan B.; Graczyk, Donald G.; Essling, Alice M.; Horwitz, E. Philip

2001-01-01

A process for converting UF.sub.6 to a solid uranium compound such as UO.sub.2 and CaF. The UF.sub.6 vapor form is contacted with an aqueous solution of NH.sub.4 OH at a pH greater than 7 to precipitate at least some solid uranium values as a solid leaving an aqueous solution containing NH.sub.4 OH and NH.sub.4 F and remaining uranium values. The solid uranium values are separated from the aqueous solution of NH.sub.4 OH and NH.sub.4 F and remaining uranium values which is then diluted with additional water precipitating more uranium values as a solid leaving trace quantities of uranium in a dilute aqueous solution. The dilute aqueous solution is contacted with an ion-exchange resin to remove substantially all the uranium values from the dilute aqueous solution. The dilute solution being contacted with Ca(OH).sub.2 to precipitate CaF.sub.2 leaving dilute NH.sub.4 OH.

Shape-Controlled Fabrication of the Polymer-Based Micromotor Based on the Polydimethylsiloxane Template.

PubMed

Su, Miaoda; Liu, Mei; Liu, Limei; Sun, Yunyu; Li, Mingtong; Wang, Dalei; Zhang, Hui; Dong, Bin

2015-11-03

We report the utilization of the polydimethylsiloxane template to construct polymer-based autonomous micromotors with various structures. Solid or hollow micromotors, which consist of polycaprolactone and platinum nanoparticles, can be obtained with controllable sizes and shapes. The resulting micromotor can not only be self-propelled in solution based on the bubble propulsion mechanism in the presence of the hydrogen peroxide fuel, but also exhibit structure-dependent motion behavior. In addition, the micromotors can exhibit various functions, ranging from fluorescence, magnetic control to cargo transportation. Since the current method can be extended to a variety of organic and inorganic materials, we thus believe it may have great potential in the fabrication of different functional micromotors for diverse applications.

Synthesis of nano-scale fast ion conducting cubic Li7La3Zr2O12.

PubMed

Sakamoto, Jeff; Rangasamy, Ezhiylmurugan; Kim, Hyunjoung; Kim, Yunsung; Wolfenstine, Jeff

2013-10-25

A solution-based process was investigated for synthesizing cubic Li7La3Zr2O12 (LLZO), which is known to exhibit the unprecedented combination of fast ionic conductivity, and stability in air and against Li. Sol-gel chemistry was developed to prepare solid metal-oxide networks consisting of 10 nm cross-links that formed the cubic LLZO phase at 600 ° C. Sol-gel LLZO powders were sintered into 96% dense pellets using an induction hot press that applied pressure while heating. After sintering, the average LLZO grain size was 260 nm, which is 13 times smaller compared to LLZO prepared using a solid-state technique. The total ionic conductivity was 0.4 mS cm(-1) at 298 K, which is the same as solid-state synthesized LLZO. Interestingly, despite the same room temperature conductivity, the sol-gel LLZO total activation energy is 0.41 eV, which 1.6 times higher than that observed in solid-state LLZO (0.26 eV). We believe the nano-scale grain boundaries give rise to unique transport phenomena that are more sensitive to temperature when compared to the conventional solid-state LLZO.

The Synthesis of LiMnxFe1−xPO4/C Cathode Material through Solvothermal Jointed with Solid-State Reaction

PubMed Central

He, Xiangming; Wang, Jixian; Dai, Zhongjia; Wang, Li; Tian, Guangyu

2016-01-01

LiMnxFe1−xPO4/C material has been synthesized through a facile solid-state reaction under the condition of carbon coating, using solvothermal-prepared LiMnPO4 and LiFePO4 as precursors and sucrose as a carbon resource. XRD and element distribution analysis reveal completed solid-state reaction of precursors. LiMnxFe1−xPO4/C composites inherit the morphology of precursors after heat treatment without obvious agglomeration and size increase. LiMnxFe1−xPO4 solid solution forms at low temperature around 350 °C, and Mn2+/Fe2+ diffuse completely within 1 h at 650 °C. The LiMnxFe1−xPO4/C (x < 0.8) composite exhibits a high-discharge capacity of over 120 mAh·g−1 (500 Wh·kg−1) at low C-rates. This paves a way to synthesize the crystal-optimized LiMnxFe1−xPO4/C materials for high performance Li-ion batteries. PMID:28773887

Microstructure and Shear Strength in Brazing Joint of Mo-Cu Composite with 304 Stainless Steel by Ni-Cr-P Filler Metal

NASA Astrophysics Data System (ADS)

Wang, Juan; Wang, Jiteng; Li, Yajiang; Zheng, Deshuang

2015-07-01

The brazing of Mo-Cu composite and 304 stainless steel was carried out in vacuum with Ni-Cr-P filler metal at 980 °C for 20 min. Microstructure in Mo-Cu/304 stainless steel joint was investigated by field-emission scanning electron microscope (FE-SEM) with energy dispersive spectrometer (EDS) and shear strength was measured by shearing test. The results indicate that shear strength of the Mo-Cu/304 stainless steel joint is about 155 MPa. There forms eutectic structure of γ-Ni solid solution with Ni3P in the braze seam. Ni-Cu(Mo) and Ni-Fe solid solution are at the interface beside Mo-Cu composite and 304 stainless steel, respectively. Shear fracture exhibits mixed ductile-brittle fracture feature with trans-granular fracture, ductile dimples and tearing edges. Fracture originates from the interface between brazing seam and Mo-Cu composite and it propagates to the braze seam due to the formation of brittle Ni5P2 and Cr3P precipitation.

Synthesis, vapor growth, polymerization, and characterization of thin films of novel diacetylene derivatives of pyrrole. The use of computer modeling to predict chemical and optical properties of these diacetylenes and poly(diacetylenes)

NASA Technical Reports Server (NTRS)

Paley, M. S.; Frazier, D. O.; Abeledeyem, H.; Mcmanus, S. P.; Zutaut, S. E.

1992-01-01

In the present work two diacetylene derivatives of pyrrole which are predicted by semiempirical AM1 calculations to have very different properties, are synthesized; the polymerizability of these diacetylenes in the solid state is determined, and the results are compared to the computer predictions. Diacetylene 1 is novel in that the monomer is a liquid at room temperature; this may allow for the possibility of polymerization in the liquid state as well as the solid state. Thin poly(diacetylene) films are obtained from compound 1 by growing films of the monomer using vapor deposition and polymerizing with UV light; these films are then characterized. Interestingly, while the poly(diacetylene) from 1 does not possess good nonlinear optical properties, the monomer exhibits very good third-order effects (phase conjugation) in solution. Dilute acetone solutions of the monomer 1 give intensity-dependent refractive indices on the order of 10 exp -6 esu; these are 10 exp 6 times better than for CS2.

Hybrid organic-inorganic inks flatten the energy landscape in colloidal quantum dot solids.

PubMed

Liu, Mengxia; Voznyy, Oleksandr; Sabatini, Randy; García de Arquer, F Pelayo; Munir, Rahim; Balawi, Ahmed Hesham; Lan, Xinzheng; Fan, Fengjia; Walters, Grant; Kirmani, Ahmad R; Hoogland, Sjoerd; Laquai, Frédéric; Amassian, Aram; Sargent, Edward H

2017-02-01

Bandtail states in disordered semiconductor materials result in losses in open-circuit voltage (V oc ) and inhibit carrier transport in photovoltaics. For colloidal quantum dot (CQD) films that promise low-cost, large-area, air-stable photovoltaics, bandtails are determined by CQD synthetic polydispersity and inhomogeneous aggregation during the ligand-exchange process. Here we introduce a new method for the synthesis of solution-phase ligand-exchanged CQD inks that enable a flat energy landscape and an advantageously high packing density. In the solid state, these materials exhibit a sharper bandtail and reduced energy funnelling compared with the previous best CQD thin films for photovoltaics. Consequently, we demonstrate solar cells with higher V oc and more efficient charge injection into the electron acceptor, allowing the use of a closer-to-optimum bandgap to absorb more light. These enable the fabrication of CQD solar cells made via a solution-phase ligand exchange, with a certified power conversion efficiency of 11.28%. The devices are stable when stored in air, unencapsulated, for over 1,000 h.

Electromechanical properties of Na0.5Bi0.5TiO3-SrTiO3-PbTiO3 solid solutions

NASA Astrophysics Data System (ADS)

Svirskas, Šarūnas; Dunce, Marija; Birks, Eriks; Sternberg, Andris; Banys, Jūras

2018-03-01

Thorough studies of electric field-induced strain are presented in 0.4Na1/2Bi1/2TiO3-(0.6-x)SrTiO3-xPbTiO3 (NBT-ST-PT) ternary solid solutions. The increase of concentration of lead x induces crossover from relaxor to ferroelectric. Strain in a relaxor state can be described by electrostrictive behavior. The electrostrictive coefficients correspond to other well-known relaxor ferroelectrics. The concentration region with a stable ferroelectric phase revealed that the polarization dependence of strain does not exhibit nonlinearity, although they are inherent to the electric field dependence of strain. In this case, electric field dependence of strain is described in terms of the Rayleigh law and the role of domain wall contribution is extracted. Finally, the character of strain at the electric field-induced phase transition between the nonpolar and the ferroelectric states is studied. The data shows that in the vicinity of the electric field induced phase transition the strain vs. electric field displays electrostrictive character.

Ionic liquids for metal extraction from chalcopyrite: solid, liquid and gas phase studies.

PubMed

Kuzmina, O; Symianakis, E; Godfrey, D; Albrecht, T; Welton, T

2017-08-16

We studied leaching of Cu and Fe from naturally occurring chalcopyrite ore using aqueous solutions of ionic liquids (ILs) based on imidazolium and ethylammonium cations and hydrogensulfate, nitrate, acetate or dicyanamide anions. Liquid, solid and gas phases of the leaching systems were characterised. We have shown that nonoxidative leaching is greatly dependant not only on temperature and pH, but on the anion species of the IL. Solutions of 1-butylimidazolium hydrogen sulfate exhibited the best leaching performance among hydrogen sulphate ILs. We have suggested that the formation of an oxide layer in some ILs may be responsible for a reduced leaching ability. The analysis of the gas phase showed the production of CO 2 and CS 2 in all leached samples. Our results suggested that the CS 2 produced upon leaching could be responsible for decreasing the sulfur, but not oxide, layer on the surface of chalcopyrite samples and therefore more efficient leaching. This is the first study, to our knowledge, to provide a systematic comparison of the leaching performance of ILs composed of different anions and cations and without added oxidants.

Synthesis, fluorescence, TGA and crystal structure of thiazolyl-pyrazolines derived from chalcones

NASA Astrophysics Data System (ADS)

Suwunwong, T.; Chantrapromma, S.; Fun, H.-K.

2015-04-01

Thiazolyl-pyrazolines 3a-3d were synthesized in a three step procedure using chalcones as starting materials and characterized by FT-IR, UV-Vis, and 1H NMR techniques. The crystal structure of compound 3a was also determined by X-ray diffraction analysis. Compound 3a crystallized out in the orthorhombic P212121 space group with the unit cell dimensions: a = 5.2106(2) Å, b = 12.4341(5) Å, c = 33.3254(13) Å, α = β = γ = 90°, V = 2159.12(15) Å3, Z = 4, D cald = 1.372 M gm-3 and F(000) = 928. Fluorescence of 3a-3d were studied in solid state and acetonitrile solution. It was found that, these compounds exhibit the green fluorescence light (506-508 nm) in both solid and solution states. The pH stability on fluorescence property and the thermal gravimetric analysis of compound 3a were specifically carried out. It was revealed that 3a shows high thermal stability up to around 250°C and presenting high stability in various pH ranges in the acetonitrilewater matrix.

Microstructure and properties of Ti-Fe-Y alloy fabricated by laser-aided direct metal deposition

NASA Astrophysics Data System (ADS)

Wang, Cunshan; Han, Liying

2018-04-01

Ti-Fe-Y alloys were designed using a "cluster-plus-glue-atom" model and then were prepared by laser-aided direct metal deposition (LDMD) on a pure titanium substrate. The influence of the Y addition on the microstructure and properties of the alloys were investigated. The results show that the alloys are composed of β-Ti solid solution and FeTi compound. The addition of Y not only suppresses the formation of Ti4Fe2O oxide but also increases the supercooling degree of the melt, leading to the grain refinement and the increase in the solid solution of the β-Ti. Meanwhile, the microstructure changes sequentially from eutectic to hypereutectic to hypoeutectic with the increasing of the Y addition. The strengest Ti-Fe-Y alloy has a dispersed eutectic structure and exhibits a good combination of mechanical, tribological, and forming properties, which is superior to that obtained for the binary Ti70.6Fe29.4 eutectic alloy. This makes the alloy a promising candidate as a LDMD material.

First-principles study of the solid solution of hydrogen in lanthanum

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

Schoellhammer, Gunther; Herzig, Peter; Wolf, Walter

2011-09-01

Results from first-principles investigations of the energetical, structural, electronic, and vibrational properties of model structures probing the metal-rich region of the lanthanum-hydrogen system, i.e., the region of the solid solution of hydrogen in lanthanum, are presented. We have studied the site preference and the ordering tendency of hydrogen atoms interstitially bonded in close-packed lanthanum. Spatially separated hydrogen atoms have turned out to exhibit an energetical preference for the occupation of octahedral interstitial sites at low temperature. Indications for a reversal of the site preference in favor of the occupation of tetrahedral interstitial sites at elevated temperature have been found. Linearmore » arrangements consisting of pairs of octahedrally and/or tetrahedrally coordinated hydrogen atoms collinearly bonded to a central lanthanum atom have turned out to be energetically favorable structure elements. Further stabilization is achieved if such hydrogen pairs are in turn linked together so that extended chains of La-H bonds are formed. Pair formation and chain linking counteract the energetical preference for octahedral coordination observed for separated hydrogen atoms.« less

Tribological properties and surface structures of ion implanted 9Cr18Mo stainless steels

NASA Astrophysics Data System (ADS)

Fengbin, Liu; Guohao, Fu; Yan, Cui; Qiguo, Sun; Min, Qu; Yi, Sun

2013-07-01

The polished quenched-and-tempered 9Cr18Mo steels were implanted with N ions and Ti ions respectively at a fluence of 2 × 1017 ions/cm2. The mechanical properties of the samples were investigated by using nanoindenter and tribometer. The results showed that the ion implantations would improve the nanohardness and tribological property, especially N ion implantation. The surface analysis of the implanted samples was carried out by using XRD, XPS and AES. It indicated that the surface exhibits graded layers after ion implantation. For N ion implantation, the surface about 20 nm thickness is mainly composed of supersaturated interstitial N solid solution, oxynitrides, CrxCy phase and metal nitrides. In the subsurface region, the metal nitrides dominate and the other phases disappear. For Ti ion implantation, the surface of about 20 nm thickness is mainly composed of titanium oxides and carbon amorphous phase, the interstitial solid solution of Ti in Fe is abundant in the subsurface region. The surface components and structures have significant contributions to the improved mechanical properties.

Lanthanide Contraction as a Design Factor for High-Performance Half-Heusler Thermoelectric Materials.

PubMed

Liu, Yintu; Fu, Chenguang; Xia, Kaiyang; Yu, Junjie; Zhao, Xinbing; Pan, Hongge; Felser, Claudia; Zhu, Tiejun

2018-06-25

Forming solid solutions, as an effective strategy to improve thermoelectric performance, has a dilemma that alloy scattering will reduce both the thermal conductivity and carrier mobility. Here, an intuitive way is proposed to decouple the opposite effects, that is, using lanthanide contraction as a design factor to select alloying atoms with large mass fluctuation but small radius difference from the host atoms. Typical half-Heusler alloys, n-type (Zr,Hf)NiSn and p-type (Nb,Ta)FeSb solid solutions, are taken as paradigms to attest the validity of this design strategy, which exhibit greatly suppressed lattice thermal conductivity and maintained carrier mobility. Furthermore, by considering lanthanide contraction, n-type (Zr,Hf)CoSb-based alloys with high zT of ≈1.0 are developed. These results highlight the significance of lanthanide contraction as a design factor in enhancing the thermoelectric performance and reveal the practical potential of (Zr,Hf)CoSb-based half-Heusler compounds due to the matched n-type and p-type thermoelectric performance. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Closantel nano-encapsulated polyvinyl alcohol (PVA) solutions.

PubMed

Vega, Abraham Faustino; Medina-Torres, Luis; Calderas, Fausto; Gracia-Mora, Jesus; Bernad-Bernad, MaJosefa

2016-08-01

The influence of closantel on the rheological and physicochemical properties (particle size and by UV-Vis absorption spectroscopy) of PVA aqueous solutions is studied here. About 1% PVA aqueous solutions were prepared by varying the closantel content. The increase of closantel content led to a reduction in the particle size of final solutions. All the solutions were buffered at pH 7.4 and exhibited shear-thinning behavior. Furthermore, in oscillatory flow, a "solid-like" type behavior was observed for the sample containing 30 μg/mL closantel. Indicating a strong interaction between the dispersed and continuous phases and evidencing an interconnected network between the nanoparticle and PVA, this sample also showed the highest shear viscosity and higher shear thinning slope, indicating a more intrincate structure disrupted by shear. In conclusion, PVA interacts with closantel in aqueous solution and the critical concentration for closantel encapsulation by PVA was about 30 μg/mL; above this concentration, the average particle size decreased notoriously which was associated to closantel interacting with the surface of the PVA aggregates and thus avoiding to some extent direct polymer-polymer interaction.

Wash Solution Bath Life Extension for the Space Shuttle Rocket Motor Aqueous Cleaning System

NASA Technical Reports Server (NTRS)

Saunders, Chad; Evans, Kurt; Sagers, Neil

1999-01-01

A spray-in-air aqueous cleaning system, which replaced 1,1,1 trichloroethane (TCA) vapor degreasing, is used for critical cleaning of Space Shuttle Redesigned Solid Rocket Motor (RSRM) metal parts. Small-scale testing demonstrated that the alkaline-based wash solution possesses adequate soil loading and cleaning properties. However, full-scale testing exhibited unexpected depletion of some primary components of the wash solution. Specifically, there was a significant decrease in the concentration of sodium metasilicate which forced change-out of the wash solution after eight days. Extension of wash solution bath life was necessary to ease the burden of frequent change-out on manufacturing. A laboratory study supports a depletion mechanism that is initiated by the hydrolysis of sodium tripolyphosphate (STPP) lowering the pH of the solution. The decrease in pH causes polymerization and subsequent precipitation of sodium metasilicate (SM). Further investigation showed that maintaining the pH was the key to preventing the precipitation of the sodium metasilicate. Implementation to the full scale operation demonstrated that periodic additions of potassium hydroxide (KOH) extended the useful bath life to more than four months.

Thermodynamics of magnesian calcite solid-solutions at 25°C and 1 atm total pressure

USGS Publications Warehouse

Busenberg, Eurybiades; Plummer, Niel

1989-01-01

The stability of magnesian calcites was reexamined, and new results are presented for 28 natural inorganic, 12 biogenic, and 32 synthetic magnesian calcites. The magnesian calcite solid-solutions were separated into two groups on the basis of differences in stoichiometric solubility and other physical and chemical properties. Group I consists of solids of mainly metamorphic and hydrothermal origin, synthetic calcites prepared at high temperatures and pressures, and synthetic solids prepared at low temperature and very low calcite supersaturations () from artificial sea water or NaClMgCl2CaCl2solutions. Group I solids are essentially binary s of CaCO2 and MgCO2, and are thought to be relatively free of structural defects. Group II solid-solutions are of either biogenic origin or are synthetic magnesian calcites and protodolomites (0–20 and ∼ 45 mole percent MgCO3) prepared at high calcite supersaturations () from NaClNa2SO4MgCl2CaCl2 or NaClMgCl2CaCl2 solutions. Group II solid-solutions are treated as massively defective solids. The defects include substitution foreign ions (Na+ and SO42−) in the magnesian calcite lattice (point defects) and dislocations (~2 · 109 cm−2). Within each group, the excess free energy of mixing, GE, is described by the mixing model , where x is the mole fraction of the end-member Ca0.5Mg0.5CO3 in the solid-solution. The values of A0and A1 for Group I and II solids were evaluated at 25°C. The equilibrium constants of all the solids are closely described by the equation ln , where KC and KD are the equilibrium constants of calcite and Ca0.5Mg0.5CO3. Group I magnesian calcites were modeled as sub-regular solid-solutions between calcite and dolomite, and between calcite and “disordered dolomite”. Both models yield almost identical equilibrium constants for these magnesian calcites. The Group II magnesian calcites were modeled as sub-regular solid-solutions between defective calcite and protodolomite. Group I and II solid-solutions differ significantly in stability. The rate of crystal growth and the chemical composition of the aqueous solutions from which the solids were formed are the main factors controlling stoichiometric solubility of the magnesian calcites and the density of crystal defects. The literature on the occurrence and behavior of magnesian calcites in sea water and other aqueous solutions is also examined.

Effect of Gold on the Corrosion Behavior of an Electroless Nickel/Immersion Gold Surface Finish

NASA Astrophysics Data System (ADS)

Bui, Q. V.; Nam, N. D.; Yoon, J. W.; Choi, D. H.; Kar, A.; Kim, J. G.; Jung, S. B.

2011-09-01

The performance of surface finishes as a function of the pH of the utilized plating solution was evaluated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests in 3.5 wt.% NaCl solution. In addition, the surface finishes were examined by x-ray diffraction (XRD), and the contact angle of the liquid/solid interface was recorded. NiP films on copper substrates with gold coatings exhibited their highest coating performance at pH 5. This was attributed to the films having the highest protective efficiency and charge transfer resistance, lowest porosity value, and highest contact angle among those examined as a result of the strongly preferred Au(111) orientation and the improved surface wettability.

Evaluation of epirubicin in thermogelling and bioadhesive liquid and solid suppository formulations for rectal administration.

PubMed

Lo, Yu-Li; Lin, Yijun; Lin, Hong-Ru

2013-12-31

Temperature sensitive Pluronic (Plu) and pH-sensitive polyacrylic acid (PAA) were successfully mixed in different ratios to form in situ gelling formulations for colon cancer therapy. The major formulations were prepared as the liquid and solid suppository dosage forms. Epirubicin (Epi) was chosen as a model anticancer drug. In vitro characterization and in vivo pharmacokinetics and therapeutic efficacy of Epi in six Plu/PAA formulations were evaluated. Our in vitro data indicate that Epi in Plu 14%/PAA 0.75% of both solid and liquid suppositories possess significant cytotoxicity, strong bioadhesive force, long-term appropriate suppository base, sustained release, and high accumulation of Epi in rat rectums. These solid and liquid suppositories were retained in the upper rectum of Sprague-Dawley (SD) rats for at least 12 h. An in vivo pharmacokinetic study using SD rats showed that after rectal administration of solid and liquid suppositories, Epi had greater area under the curve and higher relative bioavailability than in a rectal solution. These solid and liquid suppositories exhibited remarkable inhibition on the tumor growth of CT26 bearing Balb/c mice in vivo. Our findings suggest that in situ thermogelling and mucoadhesive suppositories demonstrate a great potential as colon anticancer delivery systems for protracted release of chemotherapeutic agents.

Evaluation of Epirubicin in Thermogelling and Bioadhesive Liquid and Solid Suppository Formulations for Rectal Administration

PubMed Central

Lo, Yu-Li; Lin, Yijun; Lin, Hong-Ru

2014-01-01

Temperature sensitive Pluronic (Plu) and pH-sensitive polyacrylic acid (PAA) were successfully mixed in different ratios to form in situ gelling formulations for colon cancer therapy. The major formulations were prepared as the liquid and solid suppository dosage forms. Epirubicin (Epi) was chosen as a model anticancer drug. In vitro characterization and in vivo pharmacokinetics and therapeutic efficacy of Epi in six Plu/PAA formulations were evaluated. Our in vitro data indicate that Epi in Plu 14%/PAA 0.75% of both solid and liquid suppositories possess significant cytotoxicity, strong bioadhesive force, long-term appropriate suppository base, sustained release, and high accumulation of Epi in rat rectums. These solid and liquid suppositories were retained in the upper rectum of Sprague-Dawley (SD) rats for at least 12 h. An in vivo pharmacokinetic study using SD rats showed that after rectal administration of solid and liquid suppositories, Epi had greater area under the curve and higher relative bioavailability than in a rectal solution. These solid and liquid suppositories exhibited remarkable inhibition on the tumor growth of CT26 bearing Balb/c mice in vivo. Our findings suggest that in situ thermogelling and mucoadhesive suppositories demonstrate a great potential as colon anticancer delivery systems for protracted release of chemotherapeutic agents. PMID:24384838

Structural Studies of Perfluoroaryldiselenadiazolyl Radicals: Insights into Dithiadiazolyl Chemistry.

PubMed

Melen, Rebecca L; Less, Robert J; Pask, Christopher M; Rawson, Jeremy M

2016-11-21

The synthesis and structural characterization of a series of perfluoroaryldiselenadiazolyls [DSeDA; p-XC 6 F 4 CNSeSeN (X = F, Cl, Br, CF 3 , NO 2 , and CN for 2a-2f, respectively)] are described. Concentration-dependent solution UV/vis measurements on 2a follow the Beer-Lambert law and the transitions assigned through time-dependent density functional theory (TD-DFT) studies, indicating little propensity for dimerization in solution (10 -3 -10 -4 M). Solution electron paramagnetic resonance (EPR) spectra reveal that these radicals exhibit a broad featureless singlet around g = 2.04 but form well-resolved anisotropic EPR spectra in frozen solution, from which spin densities were determined and found to reflect an increase in the spin density at the chalcogen in relation to the corresponding dithiadiazolyl (DTDA) radicals, p-XC 6 F 4 CNSSN. The solid-state structures of 2a and 2d-2f all adopt spin-paired cis-cofacial dimers in which the dimers are held together via multicenter π*-π* "pancake bonding" interactions. Conversely, 2b and 2c exhibit an orthogonal mode of association, which is unique to DSeDA chemistry but which also affords a singlet ground state evidenced by SQUID magnetometry. The more sterically demanding diselenadiazolyl radical 2f was also prepared and exhibits a trans-antarafacial dimerization mode. DFT studies [UPBE0-D3 ccPVTZ-PP(-F)++] on the model radical HCNSeSeN confirm that each dimer is a stable energy minimum on the potential energy surface, reproducing well the experimental geometric parameters with relative stability in the order cis-cofacial > orthogonal > trans-antarafacial. Computational studies reflect stronger dimerization for DSeDA radicals in relation to their sulfur analogues, consistent with the experimental observation: While 2a and 2d are isomorphous with their corresponding DTDA radicals, 2b, 2c, and 2e-2g are all dimeric, in contrast to their DTDA analogues, which are monomeric in the solid-state. A study on 2f reveals that significant geometric strain accumulates in order to support the propensity for both cis dimerization and intermolecular CN···Se interactions. Conversely, p-NCC 6 F 4 CNSSN likely forfeits dimerization in the analogous packing motif in order to release strain but retains the favorable intermolecular CN···S interactions.

Single crystals of metal solid solutions

NASA Technical Reports Server (NTRS)

Miller, J. F.; Austin, A. E.; Richard, N.; Griesenauer, N. M.; Moak, D. P.; Mehrabian, M. R.; Gelles, S. H.

1974-01-01

The following definitions were sought in the research on single crystals of metal solid solutions: (1) the influence of convection and/or gravity present during crystallization on the substructure of a metal solid solution; (2) the influence of a magnetic field applied during crystallization on the substructure of a metal solid solution; and (3) requirements for a space flight experiment to verify the results. Growth conditions for the selected silver-zinc alloy system are described, along with pertinent technical and experimental details of the project.

Solid-state and solution /sup 13/C NMR in the conformational analysis of methadone-hydrochloride and related narcotic analgesics

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

Sumner, S.C.J.

1986-01-01

Solid state and solution /sup 13/C NMR have been used to study the conformations of the racemic mixtures and single enantiomers of methadone hydrochloride, alpha and beta methadol hydrochloride, and alpha and beta acetylmethadol hydrochloride. The NMR spectra acquired for the compounds as solids, and in polar and nonpolar solvents are compared, in order to determine the conformation of the molecules in solution. To determine the reliability of assigning solution conformations by comparing solution and solid state chemical shift data, three bond coupling constants measured in solution are compared with those calculated from X-ray data. The conformations of the racemicmore » mixture and plus enantiomer of methadone hydrochloride have been shown to be very similar in the solid state, where minor differences in conformation can be seen by comparing NMR spectra obtained for the solids. Also shown is that the molecules of methadone hydrochloride have conformations in polar and in nonpolar solvents which are very similar to the conformation of the molecules in the solid state.« less

Evolution of Microstructure in Brazed Joints of Austenitic-Martensitic Stainless Steel with Pure Silver Obtained with Ag-27Cu-5Sn Brazing Filler Material

NASA Astrophysics Data System (ADS)

Gangadharan, S.; Sivakumar, D.; Venkateswaran, T.; Kulkarni, Kaustubh

2016-12-01

Brazing of an austenitic-martensitic stainless steel (AMSS) with pure silver was carried out at 1053 K, 1073 K, and 1093 K (780 °C, 800 °C, and 820 °C) with Ag-27Cu-5Sn (wt pct) as brazing filler material (BFM). Wettability of the liquid BFM over base AMSS surface was found to be poor. Application of nickel coating to the steel was observed to enhance the wettability and to enable the formation of a good bond between BFM and the steel. The mechanism responsible for enhanced metallurgical bonding of the BFM with AMSS in the presence of nickel coating was explained based on diffusional interactions and uphill diffusion of iron, chromium and nickel observed in the brazed microstructure. Good diffusion-assisted zone was observed to form on silver side at all three temperatures. Four phases were encountered within the joint including silver solid solution, copper solid solution, Cu3Sn intermetallic and Ni-Fe solid solution. The Cu3Sn intermetallic was present in small amounts in the joints brazed at 1053 K and 1073 K (780 °C and 800 °C). The joint formed at 1093 K (820 °C) exhibited the absence of Cu3Sn, fewer defects and larger diffusion-assisted zone. Hardness of base AMSS was found to reduce during brazing due to austenite reversion and post-brazing sub-zero treatment for 2.5 hours was found suitable to recover the hardness.

Dy3TaO7, A stoichiometric spin glass and the effect of disorder via chemical substitution in the Dy3-xYxTaO7 (0 ≤ x ≤ 3) solid solution

NASA Astrophysics Data System (ADS)

Gómez-García, J. Francisco; Bucio, Lauro; Tavizon, Gustavo

2018-01-01

In this work, we present both structural and magnetic (DC magnetization and AC susceptibility) studies of the Dy3-xYxTaO7 solid solution. The structural characterization of samples was performed by Rietveld refinements of the X-ray diffraction data. All compounds crystallized in a weberite-related structure in the orthorhombic C2221 space group (No. 20); the variations of the lattice parameters obey the Vegard´s law in the whole range of composition. DC magnetic measurements of the Dy3-xYxTaO7 system showed a Curie-Weiss paramagnetic behaviour, with antiferromagnetic interactions at T>150 K. Below 3 K a spin glass behaviour in the 0 ≤ x ≤ 1 range of the solid solution was observed. The stoichiometric Dy3TaO7 compound showed spin glass behaviour although there is no evidence of structural disorder. For some Y3+ doped compounds (x = 0.33, 0.66 and 1.0), chemical disorder reduced the freezing temperature (Tg) values with a ×1/3 dependence. Cole-Cole analysis of the AC magnetic field response showed similar phenomenological parameters for the stoichiometric (x = 0) and the Y3+ doped compounds with spin glassiness, suggesting an analogous mechanism for these compounds. For the Dy3-xYxTaO7 system, in which the spin glass behaviour seems to exhibit a critical concentration, a magnetic phase diagram is proposed.

Purification of uranothorite solid solutions from polyphase systems

NASA Astrophysics Data System (ADS)

Clavier, Nicolas; Szenknect, Stéphanie; Costin, Dan Tiberiu; Mesbah, Adel; Ravaux, Johann; Poinssot, Christophe; Dacheux, Nicolas

2013-10-01

The mineral coffinite, nominally USiO4, and associated Th1-xUxSiO4 uranothorite solid solutions are of great interest from a geochemical point of view and in the case of the direct storage of spent nuclear fuels. Nevertheless, they clearly exhibit a lack in the evaluation of their thermodynamic data, mainly because of the difficulties linked with their preparation as pure phases. This paper thus presents physical and chemical methods aiming to separate uranothorite solid solutions from oxide additional phases such as amorphous SiO2 and nanometric crystallized Th1-yUyO2. The repetition of centrifugation steps envisaged in first place was rapidly dropped due to poor recovery yields, to the benefit of successive washings in acid then basic media. Under both static and dynamic flow rates (i.e. low or high rate of leachate renewal), ICP-AES (Inductively Coupled Plasma - Atomic Emission Spectroscopy) analyses revealed the systematic elimination of Th1-yUyO2 in acid media and of SiO2 in basic media. Nevertheless, two successive steps were always needed to reach pure samples. On this basis, a first cycle performed in static conditions was chosen to eliminate the major part of the accessory phases while a second one, in dynamic conditions, allowed the elimination of the residual impurities. The complete purification of the samples was finally evidenced through the characterization of the samples by the means of PXRD (Powder X-Ray Diffraction), SEM (Scanning Electron Microscopy) observations and X-EDS (X-Ray Energy Dispersive Spectroscopy) analyses.

Klucel™ EF and ELF polymers for immediate-release oral dosage forms prepared by melt extrusion technology.

PubMed

Mohammed, Noorullah Naqvi; Majumdar, Soumyajit; Singh, Abhilasha; Deng, Weibin; Murthy, Narasimha S; Pinto, Elanor; Tewari, Divya; Durig, Thomas; Repka, Michael A

2012-12-01

The objective of this research work was to evaluate Klucel™ hydroxypropylcellulose (HPC) EF and ELF polymers, for solubility enhancement as well as to address some of the disadvantages associated with solid dispersions. Ketoprofen (KPR), a Biopharmaceutics Classification System class II drug with poor solubility, was utilized as a model compound. Preliminary thermal studies were performed to confirm formation of a solid solution/dispersion of KPR in HPC matrix and also to establish processing conditions for hot-melt extrusion. Extrudates pelletized and filled into capsules exhibited a carrier-dependent release with ELF polymer exhibiting a faster release. Tablets compressed from milled extrudates exhibited rapid release owing to the increased surface area of the milled extrudate. Addition of mannitol (MNT) further enhanced the release by forming micro-pores and increasing the porosity of the extrudates. An optimized tablet formulation constituting KPR, MNT, and ELF in a 1:1:1 ratio exhibited 90% release in 15 min similar to a commercial capsule formulation. HPC polymers are non-ionic hydrophilic polymers that undergo polymer-chain-length-dependent solubilization and can be used to enhance solubility or dissolution rate of poorly soluble drugs. Dissolution/release rate could be tailored for rapid-release applications by selecting a suitable HPC polymer and altering the final dosage form. The release obtained from pellets was carrier-dependent and not drug-dependent, and hence, such a system can be effectively utilized to address solubility or precipitation issues with poorly soluble drugs in the gastrointestinal environment.

All-Solid-State Sodium-Selective Electrode with a Solid Contact of Chitosan/Prussian Blue Nanocomposite

PubMed Central

Ghosh, Tanushree; Rieger, Jana

2017-01-01

Conventional ion-selective electrodes with a liquid junction have the disadvantage of potential drift. All-solid-state ion-selective electrodes with solid contact in between the metal electrode and the ion-selective membrane offer high capacitance or conductance to enhance potential stability. Solution-casted chitosan/Prussian blue nanocomposite (ChPBN) was employed as the solid contact layer for an all-solid-state sodium ion-selective electrode in a potentiometric sodium ion sensor. Morphological and chemical analyses confirmed that the ChPBN is a macroporous network of chitosan that contains abundant Prussian blue nanoparticles. Situated between a screen-printed carbon electrode and a sodium-ionophore-filled polyvinylchloride ion-selective membrane, the ChPBN layer exhibited high redox capacitance and fast charge transfer capability, which significantly enhanced the performance of the sodium ion-selective electrode. A good Nernstian response with a slope of 52.4 mV/decade in the linear range from 10−4–1 M of NaCl was observed. The stability of the electrical potential of the new solid contact was tested by chronopotentiometry, and the capacitance of the electrode was 154 ± 4 µF. The response stability in terms of potential drift was excellent (1.3 µV/h) for 20 h of continuous measurement. The ChPBN proved to be an efficient solid contact to enhance the potential stability of the all-solid-state ion-selective electrode. PMID:29099804

LiGa(OTf)(sub 4) as an Electrolyte Salt for Li-Ion Cells

NASA Technical Reports Server (NTRS)

Reddy, V. Prakash; Prakash, G. K. Syria; Hu, Jinbo; Yan, Ping; Smart, Marshall; Bugga, ratnakumar; Chin, Keith; Surampudi, Subarao

2008-01-01

Lithium tetrakis(trifluoromethane sulfo - nato)gallate [abbreviated "LiGa(OTf)4" (wherein "OTf" signifies trifluoro - methanesulfonate)] has been found to be promising as an electrolyte salt for incorporation into both liquid and polymer electrolytes in both rechargeable and non-rechargeable lithium-ion electrochemical cells. This and other ingredients have been investigated in continuing research oriented toward im proving the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. As described in more detail in those articles, lithiumion cells most commonly contain nonaqueous electrolyte solutions consisting of lithium hexafluorophosphate (LiPF6) dissolved in mixtures of cyclic and linear alkyl carbonates, including ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). Although such LiPF6-based electrolyte solutions are generally highly ionically conductive and electrochemically stable, as needed for good cell performance, there is interest in identifying alternate lithium electrolyte salts that, relative to LiPF6, are more resilient at high temperature and are less expensive. Experiments have been performed on LiGa(OTf)4 as well as on several other candidate lithium salts in pursuit of this interest. As part of these experiments, LiGa(OTf)4 was synthesized by the reaction of Ga(OTf)3 with an equimolar portion of LiOTf in a solvent consisting of anhydrous acetonitrile. Evaporation of the solvent yielded LiGa(OTf)4 as a colorless crystalline solid. The LiGa(OTf)4 and the other salts were incorporated into solutions with PC and DMC. The resulting electrolyte solutions exhibited reasonably high ionic conductivities over a relatively wide temperature range down to 40 C (see figure). In cyclic voltammetry measurements, LiGa(OTf)4 and the other salts exhibited acceptably high electrochemical stability over the relatively wide potential window of 0 to 5 V versus Li+/Li. 13C nuclear-magneticresonance measurements yielded results that suggested that in comparison with the other candidate salts, LiGa(OTf)4 exhibits less ion pairing. Planned further development will include optimization of the salt and solvent contents of such electrolyte solutions and incorporation of LiGa(OTf)4 into gel and solid-state polymer electrolytes. Of the salts, LiGa(OTf)4 is expected to be especially desirable for incorporation into lithium polymer electrolytes, wherein decreased ion pairing is advantageous and the large delocalized anions can exert a plasticizing effect.

Two tautomeric forms of 2-amino-5,6-dimethylpyrimidin-4-one.

PubMed

Hall, Victoria M; Bertke, Jeffery A; Swift, Jennifer A

2016-06-01

Derivatives of 4-hydroxypyrimidine are an important class of biomolecules. These compounds can undergo keto-enol tautomerization in solution, though a search of the Cambridge Structural Database shows a strong bias toward the 3H-keto tautomer in the solid state. Recrystallization of 2-amino-5,6-dimethyl-4-hydroxypyrimidine, C6H9N3O, from aqueous solution yielded triclinic crystals of the 1H-keto tautomer, denoted form (I). Though not apparent in the X-ray data, the IR spectrum suggests that small amounts of the 4-hydroxy tautomer are also present in the crystal. Monoclinic crystals of form (II), comprised of a 1:1 ratio of both the 1H-keto and the 3H-keto tautomers, were obtained from aqueous solutions containing uric acid. Forms (I) and (II) exhibit one-dimensional and three-dimensional hydrogen-bonding motifs, respectively.

Heterometallic molecular precursors for a lithium-iron oxide material: synthesis, solid state structure, solution and gas-phase behaviour, and thermal decomposition.

PubMed

Han, Haixiang; Wei, Zheng; Barry, Matthew C; Filatov, Alexander S; Dikarev, Evgeny V

2017-05-02

Three heterometallic single-source precursors with a Li : Fe = 1 : 1 ratio for a LiFeO 2 oxide material are reported. Heterometallic compounds LiFeL 3 (L = tbaoac (1), ptac (2), and acac(3)) have been obtained on a large scale, in nearly quantitative yields by one-step reactions that employ readily available reagents. The heterometallic precursor LiFe(acac) 3 (3) with small, symmetric substituents on the ligand (acac = pentane-2,4-dionate), maintains a 1D polymeric structure in the solid state that limits its volatility and prevents solubility in non-coordinating solvents. The application of the unsymmetrical ligands, tbaoac (tert-butyl acetoacetate) and ptac (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate), that exhibit different bridging properties at the two ends of the ligand, allowed us to change the connectivity pattern within the heterometallic assembly. The latter was demonstrated by structural characterization of heterometallic complexes LiFe(tbaoac) 3 (1) and LiFe(ptac) 3 (2) that consist of discrete heterocyclic tetranuclear molecules Li 2 Fe 2 L 6 . The compounds are highly volatile and exhibit a congruent sublimation character. DART mass spectrometric investigation revealed the presence of heterometallic molecules in the gas phase. The positive mode spectra are dominated by the presence of [M - L] + peaks (M = Li 2 Fe 2 L 6 ). In accord with their discrete molecular structure, complexes 1 and 2 are highly soluble in nearly all common solvents. In order to test the retention of the heterometallic structure in solution, the diamagnetic analog of 1, LiMg(tbaoac) 3 (4), has been isolated. Its tetranuclear molecular structure was found to be isomorphous to that of the iron counterpart. 1 H and 7 Li NMR spectroscopy unambiguously confirmed the presence of heterometallic molecules in solutions of non-coordinating solvents. The heterometallic precursor 1 was shown to exhibit clean thermal decomposition in air that results in phase-pure α-modification of layered oxide LiFeO 2 , the prospective cathode material for lithium ion batteries.

Improvement of Physico-mechanical Properties of Partially Amorphous Acetaminophen Developed from Hydroalcoholic Solution Using Spray Drying Technique

PubMed Central

Sadeghi, Fatemeh; Torab, Mansour; Khattab, Mostafa; Homayouni, Alireza; Afrasiabi Garekani, Hadi

2013-01-01

Objective(s): This study was performed aiming to investigate the effect of particle engineering via spray drying of hydroalcoholic solution on solid states and physico-mechanical properties of acetaminophen. Materials and Methods: Spray drying of hydroalcoholic solution (25% v/v ethanol/water) of acetaminophen (5% w/v) in the presence of small amounts of polyninylpyrrolidone K30 (PVP) (0, 1.25, 2.5 and 5% w/w based on acetaminophen weight) was carried out. The properties of spray dried particles namely morphology, surface characteristics, particle size, crystallinity, dissolution rate and compactibility were evaluated. Results: Spray drying process significantly changed the morphology of acetaminophen crystals from acicular (rod shape) to spherical microparticle. Differential scanning calorimetery (DSC) and x-ray powder diffraction (XRPD) studies ruled out any polymorphism in spray dried samples, however, a major reduction in crystallinity up to 65%, especially for those containing 5% w/w PVP was observed. Spray dried acetaminophen particles especially those obtained in the presence of PVP exhibited an obvious improvement of the dissolution and compaction properties. Tablets produced from spray dried samples exhibited excellent crushing strengths and no tendency to cap. Conclusions: The findings of this study revealed that spray drying of acetaminophen from hydroalcoholic solution in the presence of small amount of PVP produced partially amorphous particles with improved dissolution and excellent compaction properties. PMID:24379968

Multistimuli-responsive benzothiadiazole-cored phenylene vinylene derivative with nanoassembly properties.

PubMed

Dou, Chuandong; Chen, Dong; Iqbal, Javed; Yuan, Yang; Zhang, Hongyu; Wang, Yue

2011-05-17

A trifluoromethyl-substituted benzothiadiazole-cored phenylene vinylene fluorophore (1) was synthesized and displayed piezo- and vapochromism and thermo-induced fluorescence variation in solid phase. Grinding could disrupt the crystalline compound 1 with orange emission into amorphous compound 1 with green emission, and heating treatment could change the amorphous compound 1 into crystalline compound 1. Ultraviolet-visible (UV-vis) absorption spectra, (13)C nuclear magnetic resonance (NMR), and powder X-ray diffraction (PXRD) characterizations demonstrated that crystalline and amorphous compound 1 possess different molecular packing. A differential scanning calorimetry (DSC) measurement revealed that the emission switching was due to the exchange between the thermodynamic-stable crystalline and metastable amorphous states. The ground sample exhibited vapochromic fluorescence property. Furthermore, compound 1 showed interesting supramolecular assembly characteristics in solution. Slowly cooling the hot N,N-dimethylformamide (DMF) solution of compound 1 resulted in the formation of orange fluorescent fibers, whereas sonication treatment of the cooling solution led to the generation of organic molecular gel. The field emission scanning electronic microscope (FESEM) and fluorescent microscopy images revealed smooth nano- or microfiber and network morphology properties. The PXRD spectra confirmed that these nano- or microstructures had a similar molecular-packing model with the crystalline state of compound 1. Slow evaporation of the toluene solution of compound 1 could produce green emissive microrods, which exhibited interesting thermo-induced fluorescence variation.

Addressing the Interface Issues in All-Solid-State Bulk-Type Lithium Ion Battery via an All-Composite Approach.

PubMed

Chen, Ru-Jun; Zhang, Yi-Bo; Liu, Ting; Xu, Bing-Qing; Lin, Yuan-Hua; Nan, Ce-Wen; Shen, Yang

2017-03-22

All-solid-state bulk-type lithium ion batteries (LIBs) are considered ultimate solutions to the safety issues associated with conventional LIBs using flammable liquid electrolyte. The development of bulk-type all-solid-state LIBs has been hindered by the low loading of active cathode materials, hence low specific surface capacity, and by the high interface resistance, which results in low rate and cyclic performance. In this contribution, we propose and demonstrate a synergistic all-composite approach to fabricating flexible all-solid-state LIBs. PEO-based composite cathode layers (filled with LiFePO 4 particles) of ∼300 μm in thickness and composite electrolyte layers (filled with Al-LLZTO particles) are stacked layer-by-layer with lithium foils as negative layer and hot-pressed into a monolithic all-solid-state LIB. The flexible LIB delivers a high specific discharge capacity of 155 mAh/g, which corresponds to an ultrahigh surface capacity of 10.8 mAh/cm 2 , exhibits excellent capacity retention up to at least 10 cycles and could work properly under harsh operating conditions such as bending or being sectioned into pieces. The all-composite approach is favorable for improving both mesoscopic and microscopic interfaces inside the all-solid-state LIB and may provide a new toolbox for design and fabrication of all-solid-state LIBs.

Thermodynamic Study of Solid-Liquid Equilibrium in NaCl-NaBr-H2O System at 288.15 K

NASA Astrophysics Data System (ADS)

Li, Dan; Meng, Ling-zong; Deng, Tian-long; Guo, Ya-fei; Fu, Qing-Tao

2018-06-01

The solubility data, composition of the solid solution and refractive indices of the NaCl-NaBr-H2O system at 288.15 K were studied with the isothermal equilibrium dissolution method. The solubility diagram and refractive index diagram of this system were plotted at 288.15 K. The solubility diagram consists of two crystallization zones for solid solution Na(Cl,Br) · 2H2O and Na(Cl,Br), one invariant points cosaturated with two solid solution and two univariant solubility isothermal curves. On the basis of Pitzer and Harvie-Weare (HW) chemical models, the composition equations and solubility equilibrium constant equations of the solid solutions at 288.15 K were acquired using the solubility data, the composition of solid solutions, and binary Pitzer parameters. The solubilities calculated using the new method combining the equations are in good agreement with the experimental data.

Synthesis of GaN:ZnO solid solution by solution combustion method and characterization for photocatalytic application

NASA Astrophysics Data System (ADS)

Menon, Sumithra Sivadas; Anitha, R.; Gupta, Bhavana; Baskar, K.; Singh, Shubra

2016-05-01

GaN-ZnO solid solution has emerged as a successful and reproducible photocatalyst for overall water splitting by one-step photoexcitation, with a bandgap in visible region. When the solid solution is formed, some of the Zn and O ions are replaced by Ga and N ions respectively and there is a narrowing of bandgap which is hypothesized as due to Zn3d-N2p repulsion. The traditional method of synthesis of GaN-ZnO solid solution is by nitridation of the starting oxides under constant ammonia flow. Here we report a solution combustion technique for the synthesis of the solid solution at a temperature about 500 ° C in a muffle furnace with metal nitrates as precursors and urea as the fuel. The as prepared samples showed change in color with the increased concentration of ZnO in the solution. The structural, microstructural, morphological and optical properties of the samples were realized by Powder X ray diffraction, Scanning electron microscopy, Energy dispersive X ray analysis, Transmission electron microscopy and Photoluminescence. Finally the hydrogen production efficiency of the GaN-ZnO nanopowders by water splitting was found, using methanol as a scavenger. The apparent quantum yield (AQY) of 0.048% is obtained for GaN-ZnO solid solution.

Ion mobility and conductivity in the M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (M=K, Rb) solid solutions with fluorite structure

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

Kavun, V. Ya., E-mail: kavun@ich.dvo.ru; Uvarov, N.F.; Slobodyuk, A.B.

Ionic mobility and conductivity in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} and Rb{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (x=0.05, 0.09) solid solutions with the fluorite structure have been investigated using the methods of {sup 19}F NMR, X-ray diffraction and impedance spectroscopy. Types of ionic motions in the fluoride sublattice of solid solutions have been established and temperature ranges of their realization have been determined (150–450 K). Diffusion of fluoride ions is a dominating type of ionic motions in the fluoride sublattice of solid solutions under study above 350 K. Due to high ionic conductivity, above 10{sup –3} S/cm at 450 K,more » these solid solutions can be used as solid electrolytes in various electrochemical devices and systems. - Graphical abstract: Temperature dependence of the concentration of mobile (2, 4) and immobile (1, 3) F ions in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions. - Highlights: • Studied the ion mobility, conductivity in M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions (M=K, Rb). • An analysis of {sup 19}F NMR spectra made it possible to identify types of ion mobility. • The main type of ion motion above 300 K in solid solutions is a diffusion of ions F{sup –}. • The ionic conductivity of the solid solutions studied more than 10{sup –3} S/cm at 450 K.« less

An added-mass partition algorithm for fluid–structure interactions of compressible fluids and nonlinear solids

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

Banks, J.W., E-mail: banksj3@rpi.edu; Henshaw, W.D., E-mail: henshw@rpi.edu; Kapila, A.K., E-mail: kapila@rpi.edu

We describe an added-mass partitioned (AMP) algorithm for solving fluid–structure interaction (FSI) problems involving inviscid compressible fluids interacting with nonlinear solids that undergo large rotations and displacements. The computational approach is a mixed Eulerian–Lagrangian scheme that makes use of deforming composite grids (DCG) to treat large changes in the geometry in an accurate, flexible, and robust manner. The current work extends the AMP algorithm developed in Banks et al. [1] for linearly elasticity to the case of nonlinear solids. To ensure stability for the case of light solids, the new AMP algorithm embeds an approximate solution of a nonlinear fluid–solidmore » Riemann (FSR) problem into the interface treatment. The solution to the FSR problem is derived and shown to be of a similar form to that derived for linear solids: the state on the interface being fundamentally an impedance-weighted average of the fluid and solid states. Numerical simulations demonstrate that the AMP algorithm is stable even for light solids when added-mass effects are large. The accuracy and stability of the AMP scheme is verified by comparison to an exact solution using the method of analytical solutions and to a semi-analytical solution that is obtained for a rotating solid disk immersed in a fluid. The scheme is applied to the simulation of a planar shock impacting a light elliptical-shaped solid, and comparisons are made between solutions of the FSI problem for a neo-Hookean solid, a linearly elastic solid, and a rigid solid. The ability of the approach to handle large deformations is demonstrated for a problem of a high-speed flow past a light, thin, and flexible solid beam.« less

WS2 nanopores for molecule analysis

NASA Astrophysics Data System (ADS)

Danda, Gopinath; Masih Das, Paul; Chou, Yung-Chien; Mlack, Jerome; Naylor, Carl; Perea-Lopez, Nestor; Lin, Zhong; Fulton, Laura Beth; Terrones, Mauricio; Johnson, A. T. Charlie; Drndic, Marija

Atomically thin 2D materials like graphene and transition metal dichalcogenides (TMDs) are interesting as membranes in solid state nanopore sensors for DNA analysis as they may facilitate single base resolution sequencing. These materials also exhibit unique optical and electronic properties which may be exploited to enhance the functionality of nanopore sensors. Here, we report WS2 nanopores, fabricated using a focused TEM beam. We also report their controlled laser-induced expansion in ionic solution. This study demonstrates the possibility of dynamic control of nanopore characteristics optically. NIH Grant R21HG007856, NSF EFRI-1542707.

Investigation of compositional segregation during unidirectional solidification of solid solution semiconducting alloys

NASA Technical Reports Server (NTRS)

Wang, J. C.

1982-01-01

Compositional segregation of solid solution semiconducting alloys in the radial direction during unidirectional solidification was investigated by calculating the effect of a curved solid liquid interface on solute concentration at the interface on the solid. The formulation is similar to that given by Coriell, Boisvert, Rehm, and Sekerka except that a more realistic cylindrical coordinate system which is moving with the interface is used. Analytical results were obtained for very small and very large values of beta with beta = VR/D, where V is the velocity of solidification, R the radius of the specimen, and D the diffusivity of solute in the liquid. For both very small and very large beta, the solute concentration at the interface in the solid C(si) approaches C(o) (original solute concentration) i.e., the deviation is minimal. The maximum deviation of C(si) from C(o) occurs for some intermediate value of beta.

Process for recovering chaotropic anions from an aqueous solution also containing other ions

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1999-01-01

A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

Process for recovering chaotropic anions from an aqueous solution also containing other ions

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1999-03-30

A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 19 figs.

Role of lattice distortion on diffuse phase transition temperatures in Bi0.5Na0.5TiO3-BaTiO3 [BNBTO] solid solutions

NASA Astrophysics Data System (ADS)

Pradhan, Lagen Kumar; Pandey, Rabichandra; Kumar, Sunil; Supriya, Sweety; Kar, Manoranjan

2018-04-01

Effect of lattice distortion on diffuse phase transition in BNBTO solid solutions near Morphotropic phase boundary (MPB) has been investigated. Solid solutions of (Bi0.5Na0.5)1-xBaxTiO3 (with mole % of x= 0.04, 0.05, 0.06, 0.07 and 0.08) were prepared by the planetary ball mill method in ethanol medium. Rietveld refinement technique with rhombohedral (R3c) and tetragonal (P4bm) crystal symmetry has been employed for structural as well as phase analysis of the solid solutions. Both rhombohedral and tetragonal lattice distortion (c/a) tends toward the pseudo-cubic crystal symmetry with the increase of mole fraction of Ba2+ near MPB (x= 6 mole %). Also, the average crystallite size and grain size decrease with increase of mole fraction of Ba2+ in BNT ceramic are due to larger ionic radius of Ba2+ and grain boundary pinning process in the solid solutions respectively. Additionally, depolarization temperature (Td) and maximum temperature (Tm) reduces due to the lattice distortion of both the phases in BNBTO solid solutions, which is explained extensively. Significant increase of dielectric constant has been observed near MPB composition (x=6%) in BNBTO solid solutions.

Dynamic transverse shear modulus for a heterogeneous fluid-filled porous solid containing cylindrical inclusions

NASA Astrophysics Data System (ADS)

Song, Yongjia; Hu, Hengshan; Rudnicki, John W.; Duan, Yunda

2016-09-01

An exact analytical solution is presented for the effective dynamic transverse shear modulus in a heterogeneous fluid-filled porous solid containing cylindrical inclusions. The complex and frequency-dependent properties of the dynamic shear modulus are caused by the physical mechanism of mesoscopic-scale wave-induced fluid flow whose scale is smaller than wavelength but larger than the size of pores. Our model consists of three phases: a long cylindrical inclusion, a cylindrical shell of poroelastic matrix material with different mechanical and/or hydraulic properties than the inclusion and an outer region of effective homogeneous medium of laterally infinite extent. The behavior of both the inclusion and the matrix is described by Biot's consolidation equations, whereas the surrounding effective medium which is used to describe the effective transverse shear properties of the inner poroelastic composite is assumed to be a viscoelastic solid whose complex transverse shear modulus needs to be determined. The determined effective transverse shear modulus is used to quantify the S-wave attenuation and velocity dispersion in heterogeneous fluid-filled poroelastic rocks. The calculation shows the relaxation frequency and relative position of various fluid saturation dispersion curves predicted by this study exhibit very good agreement with those of a previous 2-D finite-element simulation. For the double-porosity model (inclusions having a different solid frame than the matrix but the same pore fluid as the matrix) the effective shear modulus also exhibits a size-dependent characteristic that the relaxation frequency moves to lower frequencies by two orders of magnitude if the radius of the cylindrical poroelastic composite increases by one order of magnitude. For the patchy-saturation model (inclusions having the same solid frame as the matrix but with a different pore fluid from the matrix), the heterogeneity in pore fluid cannot cause any attenuation in the transverse shear modulus at all. A comparison with the case of spherical inclusions illustrates that the transverse shear modulus for the cylindrical inclusion exhibits more S-wave attenuation than spherical inclusions.

Preparation of Sic/AIN Solid Solutions Using Organometallic Precursors

DTIC Science & Technology

1989-02-15

pyrolysis of organoaluminum and organosilicon compounds was investigated as a potential source of SiC /AUI solid solutions. Using two different co... pyrolysis methods, homogeneous mixtures of organoaluminum amides and both a vinylic polysilane and a poly- carbosilane were convertec to a preceramic ...solid that transformed to crystalline SiC /AiN solid solutions at 򒸀 C. Moreover, the liquid, polymeric , form of these precursor mixtures provides a

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

Brgoch, Jakoah; Klob, Simon D.; Denault, Kristin A.

The preparation of Eu 2+-substituted barium aluminum silicates is achieved using a rapid microwave-assisted preparation. The phase evolution of two BaAl 2Si 2O 8:Eu 2+ polymorphs, the higher temperature hexagonal phase (hexacelsian), and the lower temperature monoclinic phase (celsian), is explored by varying the ramp time and soak time. This preparation method significantly reduces the reaction time needed to form these phases compared to conventional solid state routes. The luminescent properties of the two phases are identified under UV excitation with the hexagonal phase emitting in the UV region (λ em = 372 nm) and the monoclinic phase emitting inmore » the blue region (λ em = 438 nm). The differences in optical properties of the two polymorphs are correlated to the coordination number and arrangement of the alkali earth site. The optical properties of the monoclinic phase can be further tuned through the substitution of Sr 2+, forming the solid solution (Ba 1–xSr x)Al 2Si 2O 8:Eu 2+. Changes in the crystal structure due to Sr 2+ substitution produce a surprising blue-shift in the emission spectrum, which is explained by a greater dispersion of bond lengths in the (Ba/Sr)–O polyhedra. The entire monoclinic solid solution exhibits excellent quantum yields of nearly 90 %, owing to the structural rigidity provided by the highly connected tetrahedral network.« less

The Positively Charged Hyperbranched Polymers with Tunable Fluorescence and the Cell Imaging Application.

PubMed

Ma, Hengchang; Qin, Yanfang; Yang, Zenming; Yang, Manyi; Ma, Yucheng; Yin, Pei; Yang, Yuan; Wang, Tao; Lei, Ziqiang; Yao, Xiaoqiang

2018-04-25

Fluorescence-tunable materials are becoming increasingly attractive for their potential application in optics, electronics, and biomedical technology. Herein, a multi-color molecular pixel system is realized using simple copolymerization method. Bleeding both of complementary colors from blue and yellow fluorescence segments, reproduced a serious multicolor fluorescence materials. Interestingly, the emission colors of the polymers can be fine-tuned in solid state, solution phase, and in hydrogel state. More importantly, the positive fluorescent polymers exhibited cell-membrane permeable ability, and were found to accumulate on the cell nucleus, exhibiting remarkable selectivity to give bright fluorescence. The DNA/RNA selectivity experiments in vitro and in vivo verified that [tris(4-(pyridin-4-yl)phenyl)amine]-[1,8-dibromooctane] (TPPA-DBO) has prominent selectivity to DNA over RNA inside cells.

A high performance flexible all solid state supercapacitor based on the MnO2 sphere coated macro/mesoporous Ni/C electrode and ionic conducting electrolyte

NASA Astrophysics Data System (ADS)

Zhi, Jian; Reiser, Oliver; Wang, Youfu; Hu, Aiguo

2016-06-01

A high contact resistance between the active materials and the current collector, a low ionic conductivity of the gel electrolyte, and an impenetrable electrode structure are the three major barriers which greatly limit the capacitance of MnO2 in solid state supercapacitors. As a potential solution to these problems, in this work we report a novel electrode for solid state supercapacitors, based on a ternary system composed of hierarchical MnO2 spheres as the active material, macroporous Ni foam as gel penetrable skeletons and an ordered mesoporous carbon (OMC) membrane as the charge-transport accelerating layer. By employing butyl-3-methylimidazolium chloride (BMIMCl) modified gels as the ionic conducting electrolyte, the utilization efficiency of MnO2 on the specific capacitance was enhanced up to 88% of the theoretical value, delivering a volumetric capacitance of 81 F cm-3, which is the highest value among MnO2 based solid state supercapacitors. Moreover, such a flexible device exhibits exceptional volumetric energy and power density (6.6 Wh L-1 and 549 W L-1, based on the whole device volume) combined with a small capacity loss of 8.5% after 6000 cycles under twisting. These encouraging findings unambiguously overcome the energy bottleneck of MnO2 in solid state supercapacitors, and open up a new application of macro/mesoporous materials in flexible devices.A high contact resistance between the active materials and the current collector, a low ionic conductivity of the gel electrolyte, and an impenetrable electrode structure are the three major barriers which greatly limit the capacitance of MnO2 in solid state supercapacitors. As a potential solution to these problems, in this work we report a novel electrode for solid state supercapacitors, based on a ternary system composed of hierarchical MnO2 spheres as the active material, macroporous Ni foam as gel penetrable skeletons and an ordered mesoporous carbon (OMC) membrane as the charge-transport accelerating layer. By employing butyl-3-methylimidazolium chloride (BMIMCl) modified gels as the ionic conducting electrolyte, the utilization efficiency of MnO2 on the specific capacitance was enhanced up to 88% of the theoretical value, delivering a volumetric capacitance of 81 F cm-3, which is the highest value among MnO2 based solid state supercapacitors. Moreover, such a flexible device exhibits exceptional volumetric energy and power density (6.6 Wh L-1 and 549 W L-1, based on the whole device volume) combined with a small capacity loss of 8.5% after 6000 cycles under twisting. These encouraging findings unambiguously overcome the energy bottleneck of MnO2 in solid state supercapacitors, and open up a new application of macro/mesoporous materials in flexible devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr02215d

A green-yellow emitting oxyfluoride solid solution phosphor Sr[subscript 2]Ba(AlO[subscript 4]F)[subscript 1;#8722;x](SiO[subscript 5])x:Ce[superscript 3+] for thermally stable, high color rendition solid state white lighting

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

Denault, Kristin A.; George, Nathan C.; Paden, Sara R.

2012-10-23

A near-UV excited, oxyfluoride phosphor solid solution Sr{sub 1.975}Ce{sub 0.025}Ba(AlO{sub 4}F){sub 1-x}(SiO{sub 5}){sub x} has been developed for solid state white lighting applications. An examination of the host lattice, and the local structure around the Ce{sup 3+} activator ions through a combination of density functional theory, synchrotron X-ray and neutron powder diffraction and total scattering, and electron paramagnetic resonance, points to how chemical substitutions play a crucial role in tuning the optical properties of the phosphor. The maximum emission wavelength can be tuned from green ({lambda}{sub em} = 523 nm) to yellow ({lambda}{sub em} = 552 nm) by tuning themore » composition, x. Photoluminescent quantum yield is determined to be 70 {+-} 5% for some of the examples in the series. Excellent thermal properties were found for the x = 0.5 sample, with the photoluminescence intensity at 160 C only decreased to 82% of its room temperature value. Phosphor-converted LED devices fabricated using an InGaN LED ({lambda}{sub max} = 400 nm) exhibit high color rendering white light with R{sub a} = 70 and a correlated color temperature near 7000 K. The value of R{sub a} could be raised to 90 by the addition of a red component, and the correlated color temperature lowered to near 4000 K.« less

Highly planar diarylamine-fused porphyrins and their remarkably stable radical cations† †Electronic supplementary information (ESI) available. CCDC 1469154–1469160. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc02721k Click here for additional data file. Click here for additional data file.

PubMed Central

Fukui, Norihito; Cha, Wonhee; Shimizu, Daiki; Oh, Juwon

2017-01-01

Oxidative fusion reactions of meso-phenoxazino Ni(ii) porphyrin were found to be temperature dependent, giving rise to either a doubly phenylene-fused product at room temperature or a singly phenoxazine-fused product at 70 °C. The latter was further oxidized to a doubly phenoxazine-fused Ni(ii) porphyrin, which was subsequently converted to the corresponding free base porphyrin and Zn(ii) porphyrin. Compared to previously reported diphenylamine-fused porphyrins that displayed a molecular twist, doubly phenoxazine-fused porphyrins exhibited distinctly different properties owing to their highly planar structures, such as larger fluorescence quantum yields, formation of an offset face-to-face dimer both in solution and the solid state, and the generation of a mixed-valence π-radical cation dimer upon electrochemical oxidation. One-electron oxidation of the phenoxazine-fused Ni(ii) porphyrin with Magic Blue gave the corresponding radical cation, which was certainly stable and could be isolated by separation over a silica gel column but slowly chlorinated at the reactive β-positions in the solid state. This finding led to us to examine β,β′-dichlorinated phenoxazine-fused and diphenylamine-fused Ni(ii) porphyrins, which, upon treatment with Magic Blue, provided remarkably stable radical cations to an unprecedented level. It is actually possible to purify these radical cations by silica gel chromatography, and they can be stored for over 6 months without any sign of deterioration. Moreover, they exhibited no degradation even after the CH2Cl2 solution was washed with water. However, subtle structural differences (planar versus partly twisted) led to different crystal packing structures and solid-state magnetic properties. PMID:28451165

Investigation of phase segregation using Rietveld refinement in Mg doped BaTiO3 solid solutions and their ferroelectric properties

NASA Astrophysics Data System (ADS)

Aanchal, Kaur, Kiranpreet; Singh, Anupinder; Singh, Mandeep

2018-05-01

Ba(1-x) Mgx Ti O3 (BMT) samples were synthesised using solid state reaction route with `x' varying from 0.025 to 0.10. The structural and ferroelectric properties of the bulk samples were investigated. The XRD analysis shows the presence of two phases, the first phase being magnesium doped BT (space group P4mm) and the second phase being Ba2TiO4 (space group Pna21). The tetragonal phase was found to be the major phase in the samples. The double phase Rietveld refinement was done and the weight percentage of orthorhombic phase was found to vary from 3.43% to 6.96% for x varying from 0.025≤x≤0.10. The P - E measurements reveal that all the samples exhibit lossy behaviour.

Mosaic-shaped cathode for highly durable solid oxide fuel cell under thermal stress

NASA Astrophysics Data System (ADS)

Joo, Jong Hoon; Jeong, Jaewon; Kim, Se Young; Yoo, Chung-Yul; Jung, Doh Won; Park, Hee Jung; Kwak, Chan; Yu, Ji Haeng

2014-02-01

In this study, we propose a novel "mosaic structure" for a SOFC (solid oxide fuel cell) cathode with high thermal expansion to improve the stability against thermal stress. Self-organizing mosaic-shaped cathode has been successfully achieved by controlling the amount of binder in the dip-coating solution. The anode-supported cell with mosaic-shaped cathode shows itself to be highly durable performance for rapid thermal cycles, however, the performance of the cell with a non-mosaic cathode exhibits severe deterioration originated from the delamination at the cathode/electrolyte interface after 7 thermal cycles. The thermal stability of an SOFC cathode can be evidently improved by controlling the surface morphology. In view of the importance of the thermal expansion properties of the cathode, the effects of cathode morphology on the thermal stress stability are discussed.

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

Rai, R.N., E-mail: rn_rai@yahoo.co.in; Kant, Shiva; Reddi, R.S.B.

Urea is an attractive material for frequency conversion of high power lasers to UV (for wavelength down to 190 nm), but its usage is hindered due to its hygroscopic nature, though there is no alternative organic NLO crystal which could be transparent up to 190 nm. The hygroscopic character of urea has been modified by making the solid solution (UCNB) of urea (U) and p-chloronitrobenzene (CNB). The formation of the solid solution of CNB in U is explained on the basis of phase diagram, powder XRD, FTIR, elemental analysis and single crystal XRD studies. The solubility of U, CNB andmore » UCNB in ethanol solution is evaluated at different temperatures. Transparent single crystals of UCNB are grown from its saturated solution in ethanol. Optical properties e.g., second harmonic generation (SHG), refractive index and the band gap for UCNB crystal were measured and their values were compared with the parent compounds. Besides modification in hygroscopic nature, UCNB has also shown the higher SHG signal and mechanical hardness in comparison to urea crystal. - Highlights: • The hygroscopic character of urea was modified by making the solid solution • Solid solution formation is support by elemental, powder- and single crystal XRD • Crystal of solid solution has higher SHG signal and mechanical stability. • Refractive index and band gap of solid solution crystal have determined.« less

Dissolution of aragonite-strontianite solid solutions in nonstoichiometric Sr (HCO3)2-Ca (HCO3)2-CO2-H2O solutions

USGS Publications Warehouse

Plummer, Niel; Busenberg, E.; Glynn, P.D.; Blum, A.E.

1992-01-01

Synthetic strontianite-aragonite solid-solution minerals were dissolved in CO2-saturated non-stoichiometric solutions of Sr(HCO3)2 and Ca(HCO3)2 at 25??C. The results show that none of the dissolution reactions reach thermodynamic equilibrium. Congruent dissolution in Ca(HCO3)2 solutions either attains or closely approaches stoichiometric saturation with respect to the dissolving solid. In Sr(HCO3)2 solutions the reactions usually become incongruent, precipitating a Sr-rich phase before reaching stoichiometric saturation. Dissolution of mechanical mixtures of solids approaches stoichiometric saturation with respect to the least stable solid in the mixture. Surface uptake from subsaturated bulk solutions was observed in the initial minutes of dissolution. This surficial phase is 0-10 atomic layers thick in Sr(HCO3)2 solutions and 0-4 layers thick in Ca(HCO3)2 solutions, and subsequently dissolves and/or recrystallizes, usually within 6 min of reaction. The initial transient surface precipitation (recrystallization) process is followed by congruent dissolution of the original solid which proceeds to stoichiometric saturation, or until the precipitation of a more stable Sr-rich solid. The compositions of secondary precipitates do not correspond to thermodynamic equilibrium or stoichiometric saturation states. X-ray photoelectron spectroscopy (XPS) measurements indicate the formation of solid solutions on surfaces of aragonite and strontianite single crystals immersed in Sr(HCO3)2 and Ca(HCO3)2 solutions, respectively. In Sr(HCO3)2 solutions, the XPS signal from the outer ~ 60 A?? on aragonite indicates a composition of 16 mol% SrCO3 after only 2 min of contact, and 14-18 mol% SrCO3 after 3 weeks of contact. The strontianite surface averages approximately 22 mol% CaCO3 after 2 min of contact with Ca(HCO3)2 solution, and is 34-39 mol% CaCO3 after 3 weeks of contact. XPS analysis suggests the surface composition is zoned with somewhat greater enrichment in the outer ~25 A?? (as much as 26 mol% SrCO3 on aragonite and 44 mol% CaCO3 on strontianite). The results indicate rapid formation of a solid-solution surface phase from subsaturated aqueous solutions. The surface phase continually adjusts in composition in response to changes in composition of the bulk fluid as net dissolution proceeds. Dissolution rates of the endmembers are greatly reduced in nonstoichiometric solutions relative to dissolution rates observed in stoichiometric solutions. All solids dissolve more slowly in solutions spiked with the least soluble component ((Sr(HCO3)2)) than in solutions spiked with the more soluble component (Ca(HCO3)2), an effect that becomes increasingly significant as stoichiometric saturation is approached. It is proposed that the formation of a non-stoichiometric surface reactive zone significantly decreases dissolution rates. ?? 1992.

Precipitation in Al–Mg solid solution prepared by solidification under high pressure

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

Jie, J.C., E-mail: jiejc@dlut.edu.cn; School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001; Wang, H.W.

2014-01-15

The precipitation in Al–Mg solid solution containing 21.6 at.% Mg prepared by solidification under 2 GPa was investigated. The results show that the γ-Al{sub 12}Mg{sub 17} phase is formed and the β′ phase cannot be observed in the solid solution during ageing process. The precipitation of γ and β phases takes place in a non-uniform manner during heating process, i.e. the γ and β phases are first formed in the interdendritic region, which is caused by the inhomogeneous distribution of Mg atoms in the solid solution solidified under high pressure. Peak splitting of X-ray diffraction patterns of Al(Mg) solid solutionmore » appears, and then disappears when the samples are aged at 423 K for different times, due to the non-uniform precipitation in Al–Mg solid solution. The direct transformation from the γ to β phase is observed after ageing at 423 K for 24 h. It is considered that the β phase is formed through a peritectoid reaction of α + γ → β which needs the diffusion of Mg atoms across the interface of α/γ phases. - Highlights: • The γ phase is formed and the β′ phase is be observed in Al(Mg) solid solution. • Peak splitting of XRD pattern of Al(Mg) solid solution appears during aged at 150 °C. • The β phase is formed through a peritectoid reaction of α + γ → β.« less

Supramolecular structures and assembly and luminescent properties of quinacridone derivatives.

PubMed

Ye, Kaiqi; Wang, Jia; Sun, Hui; Liu, Yu; Mu, Zhongcheng; Li, Fei; Jiang, Shimei; Zhang, Jingying; Zhang, Hongxing; Wang, Yue; Che, Chi-Ming

2005-04-28

The synthesis and single-crystal X-ray structures of two quinacridone derivatives, N,N'-di(n-butyl)quinacridone (1) and N,N'-di(n-butyl)-1,3,8,10-tetramethylquinacridone (2), are reported, and the 1H NMR, absorption, photoluminescent (PL), and electroluminescent (EL) characteristics are presented. Both these crystal structures are characterized by intermolecular pi...pi and hydrogen bonding interactions. The intermolecular pi...pi interactions lead to the formation of molecular columns in the solids of 1 and 2, and the interplanar contact distances between two adjacent molecules are 3.48 and 3.55 angstroms, respectively. Crystals of 1 display shorter intermolecular pi...pi contacts and higher density than 2. These results suggest that tighter intermolecular interactions exist in 1. The 1H NMR, absorption, and PL spectra of 1 and 2 in solutions exhibit concentration-dependent properties. The PL quantum yields of 1 in solutions decrease more quickly with the increase of concentration compared to that of 2 in solutions. For solid thin films of Alq3:1 (Alq3 = tris(8-hydroxyquinolinato)aluminum), emission intensities dramatically decrease and obvious red shifts are observed when the dopant concentration is above 4.2%, while for films of Alq3:2, a similar phenomenon occurs when the concentration is above 6.7%. EL devices with Alq3:1 as emitting layer only show high efficiencies (20.3-14.5 cd/A) within the narrow dopant concentration range of 0.5-1.0%. In contrast, high efficiencies (21.5-12.0 cd/A) are achieved for a wider dopant concentration range of 0.5-5.0% when Alq3:2 films are employed as emitting layer. The different PL and EL concentration-dependent properties of the solid thin films Alq3:1 and Alq3:2 are attributed to their different molecular packing characteristics in the solid state.

Synthesis of GaN:ZnO solid solution by solution combustion method and characterization for photocatalytic application

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

Menon, Sumithra Sivadas; Anitha, R.; Baskar, K.

2016-05-23

GaN-ZnO solid solution has emerged as a successful and reproducible photocatalyst for overall water splitting by one-step photoexcitation, with a bandgap in visible region. When the solid solution is formed, some of the Zn and O ions are replaced by Ga and N ions respectively and there is a narrowing of bandgap which is hypothesized as due to Zn3d-N2p repulsion. The traditional method of synthesis of GaN-ZnO solid solution is by nitridation of the starting oxides under constant ammonia flow. Here we report a solution combustion technique for the synthesis of the solid solution at a temperature about 500 °more » C in a muffle furnace with metal nitrates as precursors and urea as the fuel. The as prepared samples showed change in color with the increased concentration of ZnO in the solution. The structural, microstructural, morphological and optical properties of the samples were realized by Powder X ray diffraction, Scanning electron microscopy, Energy dispersive X ray analysis, Transmission electron microscopy and Photoluminescence. Finally the hydrogen production efficiency of the GaN-ZnO nanopowders by water splitting was found, using methanol as a scavenger. The apparent quantum yield (AQY) of 0.048% is obtained for GaN-ZnO solid solution.« less

Molecular determinants for drug-receptors Part 11. The preferred conformation of N-(p-anisoyl)pyrrolidin-2-one (``Aniracetam'') in the solid and solution states as indicated by X-ray crystal structure analysis, dipole moment and theoretical calculations

NASA Astrophysics Data System (ADS)

Bandoli, Giuliano; Nicolini, Marino; Lumbroso, Henri; Grassi, Antonio; Pappalardo, Giuseppe C.

1987-09-01

N-( p-anisoyl)pyrrolidin-2-one in the crystalline state exhibites a cis— rans conrotatory conformation with NCO and COC ar rotational angles of 33.5° and 38.5° respectively, and the p-methoxy group situated cis to the central carbonyl bond, as shown by X-ray structure analysis. As suggested by dipole moment analysis and MMP2 molecular mechanics calculations, in solution similar conrotatory models hold for both c- and t-subconformers having the p-methoxy group cis or trans to the central carbonyl bond. INDO calculations were also carried out, indicating that both subconformers are equally stable.

The boundary element method applied to 3D magneto-electro-elastic dynamic problems

NASA Astrophysics Data System (ADS)

Igumnov, L. A.; Markov, I. P.; Kuznetsov, Iu A.

2017-11-01

Due to the coupling properties, the magneto-electro-elastic materials possess a wide number of applications. They exhibit general anisotropic behaviour. Three-dimensional transient analyses of magneto-electro-elastic solids can hardly be found in the literature. 3D direct boundary element formulation based on the weakly-singular boundary integral equations in Laplace domain is presented in this work for solving dynamic linear magneto-electro-elastic problems. Integral expressions of the three-dimensional fundamental solutions are employed. Spatial discretization is based on a collocation method with mixed boundary elements. Convolution quadrature method is used as a numerical inverse Laplace transform scheme to obtain time domain solutions. Numerical examples are provided to illustrate the capability of the proposed approach to treat highly dynamic problems.

Zwitterionic Hydrogel-Biopolymer Assembly towards Biomimetic Superlubricants

NASA Astrophysics Data System (ADS)

Seekell, Raymond; Zhu, Elaine

2014-03-01

One superlubricant in nature is the synovial fluid (SF), comprising of a high molecular weight polysaccharide, hyaluronic acid (HA), and a globule protein, lubricin. In this bio-inspired materials research, we have explored hydrogel particles to mimic lubricin as a ``ball-bearing'' and control their interaction with the viscoelastic HA matrix. Biocompatible poly(N-[2-(Methacyloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide) (PMSA) hydrogel particles are synthesized to examine the electrostatic induced assembly of PMSA-HA supramolecular complexes in aqueous solutions. Fluorescence microscopy and rheology experiments have characterized the tunable network structure and viscoelastic properties of PMSA-HA aggregates by HA concentration and ionic conditions in aqueous solution. When being grafted to a solid surface, the PMSA-HA composite thin film exhibits superior low biofouling and friction performance, suggesting great promises as artificial superlubricants.

CH4 Hydrate Formation between Silica and Graphite Surfaces: Insights from Microsecond Molecular Dynamics Simulations.

PubMed

He, Zhongjin; Linga, Praveen; Jiang, Jianwen

2017-10-31

Microsecond simulations have been performed to investigate CH 4 hydrate formation from gas/water two-phase systems between silica and graphite surfaces, respectively. The hydrophilic silica and hydrophobic graphite surfaces exhibit substantially different effects on CH 4 hydrate formation. The graphite surface adsorbs CH 4 molecules to form a nanobubble with a flat or negative curvature, resulting in a low aqueous CH 4 concentration, and hydrate nucleation does not occur during 2.5 μs simulation. Moreover, an ordered interfacial water bilayer forms between the nanobubble and graphite surface thus preventing their direct contact. In contrast, the hydroxylated-silica surface prefers to be hydrated by water, with a cylindrical nanobubble formed in the solution, leading to a high aqueous CH 4 concentration and hydrate nucleation in the bulk region; during hydrate growth, the nanobubble is gradually covered by hydrate solid and separated from the water phase, hence slowing growth. The silanol groups on the silica surface can form strong hydrogen bonds with water, and hydrate cages need to match the arrangements of silanols to form more hydrogen bonds. At the end of the simulation, the hydrate solid is separated from the silica surface by liquid water, with only several cages forming hydrogen bonds with the silica surface, mainly due to the low CH 4 aqueous concentrations near the surface. To further explore hydrate formation between graphite surfaces, CH 4 /water homogeneous solution systems are also simulated. CH 4 molecules in the solution are adsorbed onto graphite and hydrate nucleation occurs in the bulk region. During hydrate growth, the adsorbed CH 4 molecules are gradually converted into hydrate solid. It is found that the hydrate-like ordering of interfacial water induced by graphite promotes the contact between hydrate solid and graphite. We reveal that the ability of silanol groups on silica to form strong hydrogen bonds to stabilize incipient hydrate solid, as well as the ability of graphite to adsorb CH 4 molecules and induce hydrate-like ordering of the interfacial water, are the key factors to affect CH 4 hydrate formation between silica and graphite surfaces.

Exploring hardness enhancement in superhard tungsten tetraboride-based solid solutions using radial X-ray diffraction

DOE PAGES

Xie, Miao; Mohammadi, Reza; Turner, Christopher L.; ...

2015-07-29

In this paper, we explore the hardening mechanisms in WB4-based solid solutions upon addition of Ta, Mn, and Cr using in situ radial X-ray diffraction techniques under nonhydrostatic pressure. By examining the lattice-supported differential strain, we provide insights into the mechanism for hardness increase in binary solid solutions at low dopant concentrations. Speculations on the combined effects of electronic structure and atomic size in ternary WB 4 solid solutions containing Ta with Mn or Cr are also included to understand the extremely high hardness of these materials.

Ion mobility and transport properties of bismuth fluoride-containing solid solutions with tysonite-type structure

NASA Astrophysics Data System (ADS)

Kavun, V. Ya.; Uvarov, N. F.; Slobodyuk, A. B.; Merkulov, E. B.; Polyantsev, M. M.

2018-07-01

The ion mobility and conductivity of solid solutions with tysonite-type structure obtained by doping bismuth trifluoride with lead (II) fluoride, and zirconium and bismuth oxides have been studied using 19F NMR, X-ray diffraction analysis, and impedance spectroscopy. The types of ionic motions in the fluoride sublattice of the synthesized solid solutions in the temperature range 150-450 K have been determined and the energy of their activation has been estimated. Due to high ionic conductivity, above 10-2 S/cm at 570 K, these solid solutions can be considered as superionic conductors.

Solid-solution CrCoCuFeNi high-entropy alloy thin films synthesized by sputter deposition

DOE PAGES

An, Zhinan; Jia, Haoling; Wu, Yueying; ...

2015-05-04

The concept of high configurational entropy requires that the high-entropy alloys (HEAs) yield single-phase solid solutions. However, phase separations are quite common in bulk HEAs. A five-element alloy, CrCoCuFeNi, was deposited via radio frequency magnetron sputtering and confirmed to be a single-phase solid solution through the high-energy synchrotron X-ray diffraction, energy-dispersive spectroscopy, wavelength-dispersive spectroscopy, and transmission electron microscopy. The formation of the solid-solution phase is presumed to be due to the high cooling rate of the sputter-deposition process.

Enhanced Physical Stability of Amorphous Drug Formulations via Dry Polymer Coating.

PubMed

Capece, Maxx; Davé, Rajesh

2015-06-01

Although amorphous solid drug formulations may be advantageous for enhancing the bioavailability of poorly soluble active pharmaceutical ingredients, they exhibit poor physical stability and undergo recrystallization. To address this limitation, this study investigates stability issues associated with amorphous solids through analysis of the crystallization behavior for acetaminophen (APAP), known as a fast crystallizer, using a modified form of the Avrami equation that kinetically models both surface and bulk crystallization. It is found that surface-enhanced crystallization, occurring faster at the free surface than in the bulk, is the major impediment to the stability of amorphous APAP. It is hypothesized that a novel use of a dry-polymer-coating process referred to as mechanical-dry-polymer-coating may be used to inhibit surface crystallization and enhance stability. The proposed process, which is examined, simultaneously mills and coats amorphous solids with polymer, while avoiding solvents or solutions, which may otherwise cause stability or crystallization issues during coating. It is shown that solid dispersions of APAP (64% loading) with a small particle size (28 μm) could be prepared and coated with the polymer, carnauba wax, in a vibratory ball mill. The resulting amorphous solid was found to have excellent stability as a result of inhibition of surface crystallization. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Modelling solid solutions with cluster expansion, special quasirandom structures, and thermodynamic approaches

NASA Astrophysics Data System (ADS)

Saltas, V.; Horlait, D.; Sgourou, E. N.; Vallianatos, F.; Chroneos, A.

2017-12-01

Modelling solid solutions is fundamental in understanding the properties of numerous materials which are important for a range of applications in various fields including nanoelectronics and energy materials such as fuel cells, nuclear materials, and batteries, as the systematic understanding throughout the composition range of solid solutions for a range of conditions can be challenging from an experimental viewpoint. The main motivation of this review is to contribute to the discussion in the community of the applicability of methods that constitute the investigation of solid solutions computationally tractable. This is important as computational modelling is required to calculate numerous defect properties and to act synergistically with experiment to understand these materials. This review will examine in detail two examples: silicon germanium alloys and MAX phase solid solutions. Silicon germanium alloys are technologically important in nanoelectronic devices and are also relevant considering the recent advances in ternary and quaternary groups IV and III-V semiconductor alloys. MAX phase solid solutions display a palette of ceramic and metallic properties and it is anticipated that via their tuning they can have applications ranging from nuclear to aerospace industries as well as being precursors for particular MXenes. In the final part, a brief summary assesses the limitations and possibilities of the methodologies discussed, whereas there is discussion on the future directions and examples of solid solution systems that should prove fruitful to consider.

Room temperature structural and dielectric studies of Pb(Fe0.585Nb0.25W0.165)O3 solid solution

NASA Astrophysics Data System (ADS)

Nagaraja, T.; Dadami, Sunanda T.; Angadi, Basavaraj

2018-05-01

The perovskite A(B'B''B''')O3 structure Pb(Fe0.585Nb0.25W0.165)O3 (PFNW) multiferroic material was synthesized by single step solid state reaction method. The single phase was achieved at low temperature with optimized synthesis parameters as calcination (700°C/2hr) and sintering (800 °C /3hr). Single phase was confirmed by room temperature (RT) X-ray diffraction (XRD). The scanning electron microscopy (SEM) shows the uniform distribution of grains throughout the surface of PFNW and the energy dispersive X-ray spectroscopy (EDX) confirms the exact elemental composition as that of the experimental. Fourier transform infrared spectroscopy (FTIR) exhibits two absorption bands at 602 cm-1 and 1385 cm-1 corresponds to the bending and stretching vibrations of metal oxides. RT dielectric studies (dielectric constant, tanδ, AC conductivity) exhibits maximum values at lower frequency region and decreases as the frequency increases. Thesingle semicircular arc in RT impedance spectra (Nyquist plot)indicatesthe contribution to the conductivity is from grains only. Hence PFNW is a potential candidate for near room temperature applications.

Single phase Pb0.7Bi0.3Fe0.65Nb0.35O3 multiferroic: Neutron diffraction, impedance and modulus studies

NASA Astrophysics Data System (ADS)

Dadami, Sunanda T.; Matteppanvar, Shidaling; Shivaraja, I.; Rayaprol, Sudhindra; Deshpande, S. K.; Angadi, Basavaraj

2018-04-01

The Pb0.7Bi0.3Fe0.65Nb0.35O3 (PBFNO) multiferroic solid solution was synthesized by using single step solid state reaction method. Single phase formation was confirmed through room temperature (RT) X Ray Diffraction (XRD) and Neutron Diffraction (ND). Rietveld refinement was used to perform the structural analysis using FullProf Suite program. RT XRD and ND patterns well fitted with monoclinic structure (Cm space group) and cell parameters from the ND data are found to be a = 5.6474(4) Å, b = 5.6415(3) Å, c = 3.9992(3) Å and β = 89.95(2)°. ND data at RT exhibits G-type antiferromagnetic structure. The electrical properties (impedance and modulus) of PBFNO were studied as a function of frequency (100 Hz - 5 MHz) and temperature (133 K - 293 K) by Impedance spectroscopy technique. Impedance and modulus spectroscopy studies confirm the contribution to the conductivity is from grains only and the relaxation is of non-Debye type. The PBFNO sample exhibits negative temperature coefficient of resistance (NTCR) behaviour. PBFNO is found be a potential candidate for RT applications.

Easy solid-phase synthesis of pH-insensitive heterogeneous CNTs/FeS Fenton-like catalyst for the removal of antibiotics from aqueous solution.

PubMed

Ma, Jie; Yang, Mingxuan; Yu, Fei; Chen, Junhong

2015-04-15

We report a facile solid method to synthesize efficient carbon-based Fenton-like catalyst (CNTs/FeS) using as-prepared carbon nanotubes (APCNTs), which makes full use of the iron nanoparticles in APCNTs without needless purification. Furthermore, the CNTs/FeS was characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric (TG) and other analysis techniques, and then the CNTs/FeS was used as a Fenton-like catalyst for removing ciprofloxacin from aqueous solution. Response Surface Methodology (RSM) was applied to find the effect of the reaction parameter and the optimum operating condition. Results shows the catalytic reaction had better suitability than previous studies in a wide range of pH values (pH 3-8) and the Fenton-like catalyst CNTs/FeS exhibits good catalytic activity for removing of antibiotic, which be attributed to the synergistic effect of adsorption-advanced oxidation and significantly improves efficiency of advanced oxidation. More importantly, the CNTs/FeS catalyst exhibit good regeneration performance and retains a high catalytic capacity (>75%) even after four reaction cycles. The catalytic mechanism were also studied further, the removal mechanism of ciprofloxacin by a CNTs/FeS heterogeneous Fenton-like process primarily involves three removal pathways occurring simultaneously: (a) adsorption removal by CNTs, (b) Fenton-like degradation catalyzed by FeS, (c) catalytic degradation by CNTs catalyst. And these actions also have synergistic effects for ciprofloxacin removal. Copyright © 2014 Elsevier Inc. All rights reserved.

Quench-age method for the fabrication of niobium-aluminum superconductors

DOEpatents

Pickus, Milton R.; Ciardella, Robert L.

1978-01-01

A flexible Nb.sub.3 Al superconducting wire is fabricated from a niobium-aluminum composite wire by heating to form a solid solution which is retained at room temperature as a metastable solid solution by quenching. The metastable solid solution is then transformed to the stable superconducting A-15 phase by low temperature aging. The transformation induced by aging can be controlled to yield either a multifilamentary or a solid A-15 core surrounded by ductile niobium.

Solid-state, ambient-operation thermally activated delayed fluorescence from flexible, non-toxic gold-nanocluster thin films: towards the development of biocompatible light-emitting devices

NASA Astrophysics Data System (ADS)

Talite, M. J. A.; Lin, H. T.; Jiang, Z. C.; Lin, T. N.; Huang, H. Y.; Heredia, E.; Flores, A.; Chao, Y. C.; Shen, J. L.; Lin, C. A. J.; Yuan, C. T.

2016-08-01

Luminescent gold nanoclusters (AuNCs) with good biocompatibility have gained much attention in bio-photonics. In addition, they also exhibit a unique photo-physical property, namely thermally activated delayed fluorescence (TADF), by which both singlet and triplet excitons can be harvested. The combination of their non-toxic material property and unique TADF behavior makes AuNCs biocompatible nano-emitters for bio-related light-emitting devices. Unfortunately, the TADF emission is quenched when colloidal AuNCs are transferred to solid states under ambient environment. Here, a facile, low-cost and effective method was used to generate efficient and stable TADF emissions from solid AuNCs under ambient environment using polyvinyl alcohol as a solid matrix. To unravel the underlying mechanism, temperature-dependent static and transient photoluminescence measurements were performed and we found that two factors are crucial for solid TADF emission: small energy splitting between singlet and triplet states and the stabilization of the triplet states. Solid TADF films were also deposited on the flexible plastic substrate with patterned structures, thus mitigating the waveguide-mode losses. In addition, we also demonstrated that warm white light can be generated based on a co-doped single emissive layer, consisting of non-toxic, solution-processed TADF AuNCs and fluorescent carbon dots under UV excitation.

Correlation of Solid State and Solution Coordination Numbers with Infrared Spectroscopy in Five-, Six-, and Eight-Coordinate Transition Metal Complexes of DOTAM.

PubMed

Nagata, Maika K C T; Brauchle, Paul S; Wang, Sen; Briggs, Sarah K; Hong, Young Soo; Laorenza, Daniel W; Lee, Andrea G; Westmoreland, T David

2016-08-16

Three new DOTAM (1,4,7,10-tetrakis(acetamido)-1,4,7,10-tetraazacyclododecane) complexes have been synthesized and characterized by X-ray crystallography: [Co(DOTAM)]Cl 2 •3H 2 O, [Ni(DOTAM)]Cl 2 •4H 2 O, and [Cu(DOTAM)](ClO 4 ) 2 •H 2 O. Solid state and solution IR spectroscopic features for a series of [M(DOTAM)] 2+ complexes (M=Mn, Co, Cu, Ni, Ca, Zn) correlate with solid state and solution coordination numbers. [Co(DOTAM)] 2+ , [Ni(DOTAM)] 2+ , and [Zn(DOTAM)] 2+ are demonstrated to be six-coordinate in both the solid state and in solution, while [Mn(DOTAM)] 2+ and [Ca(DOTAM)] 2+ are eight-coordinate in the solid state and remain so in solution. [Cu(DOTAM)] 2+ , which is five-coordinate by X-ray crystallography, is shown to increase its coordination number in solution to six-coordinate.

Defect energetics of concentrated solid-solution alloys from ab initio calculations: Ni 0.5Co 0.5, Ni 0.5Fe 0.5, Ni 0.8Fe 0.2 and Ni 0.8Cr 0.2

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

Zhao, Shijun; Stocks, George Malcolm; Zhang, Yanwen

2016-08-03

It has been shown that concentrated solid solution alloys possess unusual electronic, magnetic, transport, mechanical and radiation-resistant properties that are directly related to underlying chemical complexity. Because every atom experiences a different local atomic environment, the formation and migration energies of vacancies and interstitials in these alloys exhibit a distribution, rather than a single value as in a pure metal or dilute alloy. In this study, using ab initio calculations based on density functional theory and special quasirandom structure, we have characterized the distribution of defect formation energy and migration barrier in four Ni-based solid-solution alloys: Ni 0.5Co 0.5, Nimore » 0.5Fe 0.5, Ni 0.8Fe 0.2 and Ni 0.8Cr 0.2. As defect formation energies in finite-size models depend sensitively on the elemental chemical potential, we have developed a computationally efficient method for determining it which takes into account the global composition and the local short-range order. In addition we have compared the results of our ab initio calculations to those obtained from available embedded atom method (EAM) potentials. Our results indicate that the defect formation and migration energies are closely related to the specific atomic size in the structure, which further determines the elemental diffusion properties. In conclusion, different EAM potentials yield different features of defect energetics in concentrated alloys, pointing to the need for additional potential development efforts in order to allow spatial and temporal scale-up of defect and simulations, beyond those accessible to ab initio methods.« less

Defect energetics of concentrated solid-solution alloys from ab initio calculations: Ni0.5Co0.5, Ni0.5Fe0.5, Ni0.8Fe0.2 and Ni0.8Cr0.2.

PubMed

Zhao, Shijun; Stocks, G Malcolm; Zhang, Yanwen

2016-09-14

It has been shown that concentrated solid solution alloys possess unusual electronic, magnetic, transport, mechanical and radiation-resistant properties that are directly related to underlying chemical complexity. Because every atom experiences a different local atomic environment, the formation and migration energies of vacancies and interstitials in these alloys exhibit a distribution, rather than a single value as in a pure metal or dilute alloy. Using ab initio calculations based on density functional theory and special quasirandom structures, we have characterized the distribution of defect formation energy and migration barrier in four Ni-based solid-solution alloys: Ni0.5Co0.5, Ni0.5Fe0.5, Ni0.8Fe0.2, and Ni0.8Cr0.2. As defect formation energies in finite-size models depend sensitively on the elemental chemical potential, we have developed a computationally efficient method for determining it which takes into account the global composition and the local short-range order. In addition we have compared the results of our ab initio calculations to those obtained from available embedded atom method (EAM) potentials. Our results indicate that the defect formation and migration energies are closely related to the specific atoms in the structure, which further determines the elemental diffusion properties. Different EAM potentials yield different features of defect energetics in concentrated alloys, pointing to the need for additional potential development efforts in order to allow spatial and temporal scale-up of defect and simulations, beyond those accessible to ab initio methods.

Solid/liquid interfacial free energies in binary systems

NASA Technical Reports Server (NTRS)

Nason, D.; Tiller, W. A.

1973-01-01

Description of a semiquantitative technique for predicting the segregation characteristics of smooth interfaces between binary solid and liquid solutions in terms of readily available thermodynamic parameters of the bulk solutions. A lattice-liquid interfacial model and a pair-bonded regular solution model are employed in the treatment with an accommodation for liquid interfacial entropy. The method is used to calculate the interfacial segregation and the free energy of segregation for solid-liquid interfaces between binary solutions for the (111) boundary of fcc crystals. The zone of compositional transition across the interface is shown to be on the order of a few atomic layers in width, being moderately narrower for ideal solutions. The free energy of the segregated interface depends primarily upon the solid composition and the heats of fusion of the component atoms, the composition difference of the solutions, and the difference of the heats of mixing of the solutions.

77 FR 16679 - Emergency Planning and Notification; Emergency Planning and List of Extremely Hazardous...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-03-22

...The U.S. Environmental Protection Agency (EPA or the Agency) is taking final action to revise the manner for applying the threshold planning quantities (TPQs) for those extremely hazardous substances (EHSs) that are non-reactive solid chemicals in solution. This revision allows facilities subject to the Emergency Planning requirements that have a non-reactive solid EHS in solution, to first multiply the amount of the solid chemical in solution on-site by 0.2 before determining if this quantity equals or exceeds the lower published TPQ. This change is based on data that shows less potential for non-reactive solid chemicals in solution to remain airborne and dispersed beyond a facility's fence line in the event of an accidental release. Previously, EPA assumed that 100% of non-reactive solid chemicals in solution could become airborne and dispersed beyond the fenceline in the event of an accidental release.

Gold nanoparticle incorporated polymer/bioactive glass composite for controlled drug delivery application.

PubMed

Jayalekshmi, A C; Sharma, Chandra P

2015-02-01

The present study discusses the development of a biodegradable polymer encapsulated-nanogold incorporated-bioactive glass composite (AuPBG) by a low-temperature method. The composite was analyzed by atomic force microscopy (AFM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, thermogravimetry (TG), fluorescence and dissolution analysis. The composite exhibited aggregation behaviour in solid and solution states and exhibited negative zeta potential (-13.3 ± 1.4 mV). The composite exhibited fast degradation starting from the 5(th) day onwards in phosphate buffered saline (PBS) for a period of 14 days. The composite showed fluorescence quenching effect at pH 7 and the fluorescence recovered at pH 5. The composite has been found to be suitable for the release of doxorubicin at high rates at acidic pH (∼ 5) which is the intracellular pH of tumour cells. The drug loading ratio is also high and it exhibited a controlled release for a period of 8 days in PBS. The system serves as a promising material for targeted drug delivery applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Controlling mechanisms of metals release form cement-based waste form in acetic acid solution

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

Cheng, Kuang Ye.

1991-01-01

The purpose of this dissertation is to identify the individual leaching mechanisms of metals by knowing the pH profile within the leached specimen and the physical and chemical properties of the leached material. Leaching of cement-based waste form in acetic acid solutions with different acidic strengths has been investigated in this work. The pH profile along the acid penetration route in the cement-based waste form was identified by various pH color indicators. The pH in the surface altered layer varies from 5.0 to 6.0, which is very close to the pH in the bulk leachate. A reacting zone, where themore » pH abruptly changes from 6 to 12, sharply divides the altered surface layer from the remaining unleached waste form or kernel. Leaching of metals is controlled by the acidity available in the leachant. Dissolution of alkaline materials leaves a silica-rich layer on the surface of the cement-based waste form. This surface layer exhibits different properties than those of the unleached material. The surface layer has a higher water content, is lighter weight, and is soft and friable. Furthermore, the abundant silicate content on the solid surface detains portion of the leached metals, while they are moving through the leached layer into bulk solution. The leaching of metals is a consequence of acid penetration. The distance from the solid/solution interface to the front of the leaching boundary can be regarded as the depth of leaching zone, where the metals dissolve and diffuse out of the waste form. The metal ions diffuse through the leached layer may be retarded on the solid surface by the pH-dependent adsorption reactions. It is found that the leaching process through the leached layer is diffusion-controlled for calcium and cadmium, whereas diffusion and adsorption occur simultaneously in the leached layer for lead and arsenic.« less

System and process for dissolution of solids

DOEpatents

Liezers, Martin; Farmer, III, Orville T.

2017-10-10

A system and process are disclosed for dissolution of solids and "difficult-to-dissolve" solids. A solid sample may be ablated in an ablation device to generate nanoscale particles. Nanoparticles may then swept into a coupled plasma device operating at atmospheric pressure where the solid nanoparticles are atomized. The plasma exhaust may be delivered directly into an aqueous fluid to form a solution containing the atomized and dissolved solids. The composition of the resulting solution reflects the composition of the original solid sample.

Probing Interfacial Friction and Dissipation in Granular Gold­ Nickel Alloys with a Quartz Crystal Oscillator in an External Magnetic Field

NASA Astrophysics Data System (ADS)

Stevens, K. M.; Krim, J.

2015-03-01

We present here a quartz crystal microbalance study of two-phase gold nickel alloys whose internal granular properties are probed by exposure to a fluctuating external magnetic field. The work is motivated by prior studies demonstrating that granular two-phase materials exhibited lower friction and wear than solid solution alloys with identical compositions. In particular, we report a ``flexing'' effect which appears when an external magnetic field is applied, and is manifested as a decrease in the magnitude of oscillation amplitude that is synchronized with the applied field; the effect is not seen on the complimentary solid solution samples. The effect is consistent with internal interfacial friction between nickel and gold grains, indicating a degree of freedom which may decrease friction even in the absence of an external magnetic field. This is supported through analysis of energy dissipation in the system, using the Butterworth­-Van Dyke equivalent circuit model. Data and interpretation are also presented that rule out alternate explanations such as giant magnetoresistance and/or other resistive phenomenon within the film. Funding provided by NSF DMR0805204. Thanks to L. Pan for sample preparation.

Effect of Halide Composition on the Photochemical Stability of Perovskite Photovoltaic Materials.

PubMed

Misra, Ravi K; Ciammaruchi, Laura; Aharon, Sigalit; Mogilyansky, Dmitry; Etgar, Lioz; Visoly-Fisher, Iris; Katz, Eugene A

2016-09-22

The photochemical stability of encapsulated films of mixed halide perovskites with a range of MAPb(I 1-x Br x ) 3 (MA=methylammonium) compositions (solid solutions) was investigated under accelerated stressing using concentrated sunlight. The relevance of accelerated testing to standard operational conditions of solar cells was confirmed by comparison to degradation experiments under outdoor sunlight exposure. We found that MAPbBr 3 films exhibited no degradation, while MAPbI 3 and mixed halide MAPb(I 1-x Br x ) 3 films decomposed yielding crystallization of inorganic PbI 2 accompanied by degradation of the perovskite solar light absorption, with faster absorption degradation in mixed halide films. The crystal coherence length was found to correlate with the stability of the films. We postulate that the introduction of Br into the mixed halide solid solution stressed its structure and induced more structural defects and/or grain boundaries compared to pure halide perovskites, which might be responsible for the accelerated degradation. Hence, the cause for accelerated degradation may be the increased defect density rather than the chemical composition of the perovskite materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic liquid polymer functionalized carbon nanotubes-doped poly(3,4-ethylenedioxythiophene) for highly-efficient solid-phase microextraction of carbamate pesticides.

PubMed

Wu, Mian; Wang, Liying; Zeng, Baizhao; Zhao, Faqiong

2016-04-29

A poly(3,4-ethylenedioxythiophene)-ionic liquid polymer functionalized multiwalled carbon nanotubes (PEDOT-PIL/MWCNTs) composite solid-phase microextraction (SPME) coating was fabricated by electrodeposition. After being dipped in Nafion solution, a Nafion-modified coating was obtained. The outer layer Nafion played a crucial role in enhancing the durability and stability of the coating, thus it was robust enough for replicated extraction for at least 150 times without decrease of extraction performance. The Nafion-modified coating exhibited much higher sensitivity than commercial coatings for the direct extraction of carbamate pesticides in aqueous solutions, due to its strong hydrophobic effect and π-π affinity based enrichment. When it was used for the determination of carbamate pesticides in combination with gas chromatography-flame ionization detection, good linearity (correlation coefficients higher than 0.9981), low limits of detection (15.2-27.2 ng/L) and satisfactory precision (relative standard deviation <8.2%, n=5) were achieved. The developed method was applied to the analysis of four carbamate pesticides in apple and lettuce samples, and acceptable recoveries (i.e. 87.5-106.5%) were obtained for the standard addition. Copyright © 2016 Elsevier B.V. All rights reserved.

FAST TRACK COMMUNICATION: A closer look at arrested spinodal decomposition in protein solutions

NASA Astrophysics Data System (ADS)

Gibaud, Thomas; Schurtenberger, Peter

2009-08-01

Concentrated aqueous solutions of the protein lysozyme undergo a liquid-solid transition upon a temperature quench into the unstable spinodal region below a characteristic arrest temperature of Tf = 15 °C. We use video microscopy and ultra-small angle light scattering in order to investigate the arrested structures as a function of initial concentration, quench temperature and rate of the temperature quench. We find that the solid-like samples show all the features of a bicontinuous network that is formed through an arrested spinodal decomposition process. We determine the correlation length ξ and demonstrate that ξ exhibits a temperature dependence that closely follows the critical scaling expected for density fluctuations during the early stages of spinodal decomposition. These findings are in agreement with an arrest scenario based on a state diagram where the arrest or gel line extends far into the unstable region below the spinodal line. Arrest then occurs when during the early stage of spinodal decomposition the volume fraction phi2 of the dense phase intersects the dynamical arrest threshold phi2,Glass, upon which phase separation gets pinned into a space-spanning gel network with a characteristic length ξ.

Spectroscopic and Structural Studies of a Surface Active Porphyrin in Solution and in Langmuir-Blodgett Films.

PubMed

Ponce, Concepcion P; Araghi, Hessamaddin Younesi; Joshi, Neeraj K; Steer, Ronald P; Paige, Matthew F

2015-12-22

Controlling aggregation of the dual sensitizer-emitter (S-E) zinc tetraphenylporphyrin (ZnTPP) is an important consideration in solid state noncoherent photon upconversion (NCPU) applications. The Langmuir-Blodgett (LB) technique is a facile means of preparing ordered assemblies in thin films to study distance-dependent energy transfer processes in S-E systems and was used in this report to control the aggregation of a functionalized ZnTPP on solid substrates. This was achieved by synthetic addition of a short polar tail to one of the pendant phenyl rings in ZnTPP in order to make it surface active. The surface active ZnTPP derivative formed rigid films at the air-water interface and exhibited mean molecular areas consistent with approximately vertically oriented molecules under appropriate film compression. A red shift in the UV-vis spectra as well as unquenched fluorescence emission of the LB films indicated formation of well-ordered aggregates. However, NCPU, present in the solution phase, was not observed in the LB films, suggesting that NCPU from ZnTPP as a dual S-E required not just a controlled aggregation but a specific orientation of the molecules with respect to each other.

Analytical solution for the transient wave propagation of a buried cylindrical P-wave line source in a semi-infinite elastic medium with a fluid surface layer

NASA Astrophysics Data System (ADS)

Shan, Zhendong; Ling, Daosheng

2018-02-01

This article develops an analytical solution for the transient wave propagation of a cylindrical P-wave line source in a semi-infinite elastic solid with a fluid layer. The analytical solution is presented in a simple closed form in which each term represents a transient physical wave. The Scholte equation is derived, through which the Scholte wave velocity can be determined. The Scholte wave is the wave that propagates along the interface between the fluid and solid. To develop the analytical solution, the wave fields in the fluid and solid are defined, their analytical solutions in the Laplace domain are derived using the boundary and interface conditions, and the solutions are then decomposed into series form according to the power series expansion method. Each item of the series solution has a clear physical meaning and represents a transient wave path. Finally, by applying Cagniard's method and the convolution theorem, the analytical solutions are transformed into the time domain. Numerical examples are provided to illustrate some interesting features in the fluid layer, the interface and the semi-infinite solid. When the P-wave velocity in the fluid is higher than that in the solid, two head waves in the solid, one head wave in the fluid and a Scholte wave at the interface are observed for the cylindrical P-wave line source.

Solid lipid nanoparticles suspension versus commercial solutions for dermal delivery of minoxidil.

PubMed

Padois, Karine; Cantiéni, Céline; Bertholle, Valérie; Bardel, Claire; Pirot, Fabrice; Falson, Françoise

2011-09-15

Solid lipid nanoparticles have been reported as possible carrier for skin drug delivery. Solid lipid nanoparticles are produced from biocompatible and biodegradable lipids. Solid lipid nanoparticles made of semi-synthetic triglycerides stabilized with a mixture of polysorbate and sorbitan oleate were loaded with 5% of minoxidil. The prepared systems were characterized for particle size, pH and drug content. Ex vivo skin penetration studies were performed using Franz-type glass diffusion cells and pig ear skin. Ex vivo skin corrosion studies were realized with a method derived from the Corrositex(®) test. Solid lipid nanoparticles suspensions were compared to commercial solutions in terms of skin penetration and skin corrosion. Solid lipid nanoparticles suspensions have been shown as efficient as commercial solutions for skin penetration; and were non-corrosive while commercial solutions presented a corrosive potential. Solid lipid nanoparticles suspensions would constitute a promising formulation for hair loss treatment. Copyright © 2011 Elsevier B.V. All rights reserved.

Ceo2 Based Catalysts for the Treatment of Propylene in Motorcycle’s Exhaust Gases

PubMed Central

Pham, Phuong Thi Mai; Le Minh, Thang; Nguyen, Tien The; Van Driessche, Isabel

2014-01-01

In this work, the catalytic activities of several single metallic oxides were studied for the treatment of propylene, a component in motorcycles’ exhaust gases, under oxygen deficient conditions. Amongst them, CeO2 is one of the materials that exhibit the highest activity for the oxidation of C3H6. Therefore, several mixtures of CeO2 with other oxides (SnO2, ZrO2, Co3O4) were tested to investigate the changes in catalytic activity (both propylene conversion and CO2 selectivity). Ce0.9Zr0.1O2, Ce0.8Zr0.2O2 solid solutions and the mixtures of CeO2 and Co3O4 was shown to exhibit the highest propylene conversion and CO2 selectivity. They also exhibited good activities when tested under oxygen sufficient and excess conditions and with the presence of co-existing gases (CO, H2O). PMID:28788253

Phase Behaviour and Miscibility Studies of Collagen/Silk Fibroin Macromolecular System in Dilute Solutions and Solid State.

PubMed

Ghaeli, Ima; de Moraes, Mariana A; Beppu, Marisa M; Lewandowska, Katarzyna; Sionkowska, Alina; Ferreira-da-Silva, Frederico; Ferraz, Maria P; Monteiro, Fernando J

2017-08-18

Miscibility is an important issue in biopolymer blends for analysis of the behavior of polymer pairs through the detection of phase separation and improvement of the mechanical and physical properties of the blend. This study presents the formulation of a stable and one-phase mixture of collagen and regenerated silk fibroin (RSF), with the highest miscibility ratio between these two macromolecules, through inducing electrostatic interactions, using salt ions. For this aim, a ternary phase diagram was experimentally built for the mixtures, based on observations of phase behavior of blend solutions with various ratios. The miscibility behavior of the blend solutions in the miscible zones of the phase diagram was confirmed quantitatively by viscosimetric measurements. Assessing the effects of biopolymer mixing ratio and salt ions, before and after dialysis of blend solutions, revealed the importance of ion-specific interactions in the formation of coacervate-based materials containing collagen and RSF blends that can be used in pharmaceutical, drug delivery, and biomedical applications. Moreover, the conformational change of silk fibroin from random coil to beta sheet, in solution and in the final solid films, was detected by circular dichroism (CD) and Fourier transform infrared spectroscopy (FTIR), respectively. Scanning electron microscopy (SEM) exhibited alterations of surface morphology for the biocomposite films with different ratios. Surface contact angle measurement illustrated different hydrophobic properties for the blended film surfaces. Differential scanning calorimetry (DSC) showed that the formation of the beta sheet structure of silk fibroin enhances the thermal stability of the final blend films. Therefore, the novel method presented in this study resulted in the formation of biocomposite films whose physico-chemical properties can be tuned by silk fibroin conformational changes by applying different component mixing ratios.

Surface acidity and solid-state compatibility of excipients with an acid-sensitive API: case study of atorvastatin calcium.

PubMed

Govindarajan, Ramprakash; Landis, Margaret; Hancock, Bruno; Gatlin, Larry A; Suryanarayanan, Raj; Shalaev, Evgenyi Y

2015-04-01

The objectives of this study were to measure the apparent surface acidity of common excipients and to correlate the acidity with the chemical stability of an acid-sensitive active pharmaceutical ingredient (API) in binary API-excipient powder mixtures. The acidity of 26 solid excipients was determined by two methods, (i) by measuring the pH of their suspensions or solutions and (ii) the pH equivalent (pHeq) measured via ionization of probe molecules deposited on the surface of the excipients. The chemical stability of an API, atorvastatin calcium (AC), in mixtures with the excipients was evaluated by monitoring the appearance of an acid-induced degradant, atorvastatin lactone, under accelerated storage conditions. The extent of lactone formation in AC-excipient mixtures was presented as a function of either solution/suspension pH or pHeq. No lactone formation was observed in mixtures with excipients having pHeq > 6, while the lactone levels were pronounced (> 0.6% after 6 weeks at 50°C/20% RH) with excipients exhibiting pHeq < 3. The three pHeq regions (> 6, 3-6, and < 3) were consistent with the reported solution pH-stability profile of AC. In contrast to the pHeq scale, lactone formation did not show any clear trend when plotted as a function of the suspension/solution pH. Two mechanisms to explain the discrepancy between the suspension/solution pH and the chemical stability data were discussed. Acidic excipients, which are expected to be incompatible with an acid-sensitive API, were identified based on pHeq measurements. The incompatibility prediction was confirmed in the chemical stability tests using AC as an example of an acid-sensitive API.

Manipulating the alkali metal charge compensation and tungsten oxide to continuously enhance the red fluorescence in (Li,Na,K)Ca(Mo,W)O4:Eu3+ solid solution compounds

NASA Astrophysics Data System (ADS)

Xie, Wei; Li, Jiaxin; Tian, Canxin; Wang, Zesong; Xie, Mubiao; Zou, Changwei; Sun, Guohuan; Kang, Fengwen

2018-02-01

When compared to other phosphors typically the blue and green phosphors, red phosphors, which can be used for white light-emitting diodes (wLEDs), always suffer from various problems such as higher cost, lower luminescence efficiency and bad thermal stability. And thus, great interests have been paid to how to enhance the red fluorescence intensity in the recent years. Here we report on a red-emitting solid solutions, (Li,Na,K)Ca(Mo,W)O4:Eu3+, which enable exhibiting continuous Eu3+ emission enhancement through manipulating the alkali metal ions and the relative content ratios between tungsten and molybdenum oxides. X-ray powder diffraction (XRD) has been employed to check the phase purity, and results show that all samples crystallize in a scheelite structure with space group of I41/a (No.88). A regular blue-shifting of XRD peaks, which indicates the increase of crystal plane spacing, appears as the alkali cationic radius increases from 0.92 Å (for Li), 1.18 Å (for Na) and to 1.38 Å (for K). Replacing Mo ion (0.41 Å) by W ion (0.42 Å) enables not only forming the solid solution compounds (Li,Na,K)Ca(Mo,W)O4:Eu3+, but also blue-shifting the XRD position. Similar to the XRD position shifting, our samples also exhibit the regular change in the photoluminescence (PL) spectra, in which the charge transfer (CT) band position as the alkali cationic radii increase from Li, Na and to K and further from Mo to W shows a continuous red-shifting behavior. As for the CT and Eu3+ intensity, our experimental results show that the alkali ion that corresponds to the maximum intensity is Li, and this intensity can be further enhanced by adding W. In coincidence with the change in the excitation spectral intensity, the continuous enhanced Eu3+ emission intensity can be observed up excitation at the CT band and Eu3+ lines. We have discussed the above CT band shifting and Eu3+ fluorescence enhancement and give a feasible mechanism profile that base on the energy transfer from CT band to Eu3+ dopant.

FeRh ground state and martensitic transformation

DOE PAGES

Zarkevich, Nikolai A.; Johnson, Duane D.

2018-01-09

Cubic B2 FeRh exhibits a metamagnetic transition [(111) antiferromagnet (AFM) to ferromagnet (FM)] around 353 K and remains structurally stable at higher temperatures. However, the calculated zero-Kelvin phonons of AFM FeRh exhibit imaginary modes at M points in the Brillouin zone, indicating a premartensitic instability, which is a precursor to a martensitic transformation at low temperatures. Combining electronic-structure calculations with ab initio molecular dynamics, conjugate gradient relaxation, and the solid-state nudged-elastic band methods, we predict that AFM B2 FeRh becomes unstable at ambient pressure and transforms without a barrier to an AFM(111) orthorhombic (martensitic) ground state below 90±10K. In conclusion,more » we also consider competing structures, in particular, a tetragonal AFM(100) phase that is not the global ground state, as proposed, but a constrained solution.« less

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

Levin, I.; Laws, W. J.; Wang, D.

A crystal-chemical framework has been proposed for the design of pseudocubic perovskites with nanoscale ferroelectric order, and its applicability has been demonstrated using a series of representative solid solutions that combined ferroelectric (K0.5Bi0.5TiO3, BaTiO3, and PbTiO3) and antiferroelectric (Nd-substituted BiFeO3) end members. The pseudocubic structures obtained in these systems exhibited distortions that were coherent on a scale ranging from sub-nanometer to tens of nanometers, but, in all cases, the macroscopic distortion remained unresolvable even if using high-resolution X-ray powder diffraction. Different coherence lengths for the local atomic displacements account for the distinctly different dielectric, ferroelectric, and electromechanical properties exhibited bymore » the samples. The guidelines identified provide a rationale for chemically tuning the coherence length to obtain the desired functional response.« less

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

Zarkevich, Nikolai A.; Johnson, Duane D.

Cubic B2 FeRh exhibits a metamagnetic transition [(111) antiferromagnet (AFM) to ferromagnet (FM)] around 353 K and remains structurally stable at higher temperatures. However, the calculated zero-Kelvin phonons of AFM FeRh exhibit imaginary modes at M points in the Brillouin zone, indicating a premartensitic instability, which is a precursor to a martensitic transformation at low temperatures. Combining electronic-structure calculations with ab initio molecular dynamics, conjugate gradient relaxation, and the solid-state nudged-elastic band methods, we predict that AFM B2 FeRh becomes unstable at ambient pressure and transforms without a barrier to an AFM(111) orthorhombic (martensitic) ground state below 90±10K. In conclusion,more » we also consider competing structures, in particular, a tetragonal AFM(100) phase that is not the global ground state, as proposed, but a constrained solution.« less

A New Star-shaped Carbazole Derivative with Polyhedral Oligomeric Silsesquioxane Core: Crystal Structure and Unique Photoluminescence Property.

PubMed

Xu, Zixuan; Yu, Tianzhi; Zhao, Yuling; Zhang, Hui; Zhao, Guoyun; Li, Jianfeng; Chai, Lanqin

2016-01-01

A new inorganic–organic hybrid material based on polyhedral oligomeric silsesquioxane (POSS) capped with carbazolyl substituents, octakis[3-(carbazol-9-yl)propyldimethylsiloxy]-silsesquioxane (POSS-8Cz), was successfully synthesized and characterized. The X-ray crystal structure of POSS-8Cz were described. The photophysical properties of POSS-8Cz were investigated by using UV–vis,photoluminescence spectroscopic analysis. The hybrid material exhibits blue emission in the solution and the solid film.The morphology and thermal stablity properties were measured by X-ray diffraction (XRD) and TG-DTA analysis.

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

Ozmen, Ozcan; Zondlo, John W.; Lee, Shiwoo

A bio-inspired surfactant was utilized to assist in the efficient impregnation of a nano-CeO₂ catalyst throughout both porous Solid Oxide Fuel Cells (SOFC’s) electrodes simultaneously. The process included the initial modification of electrode pore walls with a polydopamine film. The cell was then submersed into a cerium salt solution. The amount of nano-CeO₂ deposited per impregnation step increased by 3.5 times by utilizing this two-step protocol in comparison to a conventional drip impregnation method. The impregnated cells exhibited a 20% higher power density than a baseline cell without the nano-catalyst at 750°C (using humid H₂ fuel).

Growth of Tungsten Bronze Family Crystals

DTIC Science & Technology

1989-03-01

BaTiO, exhibits several plane.’ s A wide range of solid solutions can be obtained structural transitions, and it has a room-temperature tetrag- by...hiro117Ccrystals are as tbilbis Tu ngst en Hri nze (’’mpi s itiotis 71ungst en Hirwnze Ci injw site ’i ( It The\\~ are molticompi nent and siilid -siilut in svs...cttntrol temperature instabilitY because of poor .0OD-10.1i :NG t-St. G-0 IoCA, LSA.( .. Is...asSO* Ihermal (otnduc(ti\\ it ,. -"o~ s . .. O"oA’’ Ci(o~ ’ing

Mixed conductivity, structural and microstructural characterization of titania-doped yttria tetragonal zirconia polycrystalline/titania-doped yttria stabilized zirconia composite anode matrices

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

Colomer, M.T., E-mail: tcolomer@icv.csic.e; Maczka, M.

2011-02-15

Taking advantage of the fact that TiO{sub 2} additions to 8YSZ cause not only the formation of a titania-doped YSZ solid solution but also a titania-doped YTZP solid solution, composite materials based on both solutions were prepared by solid state reaction. In particular, additions of 15 mol% of TiO{sub 2} give rise to composite materials constituted by 0.51 mol fraction titania-doped yttria tetragonal zirconia polycrystalline and 0.49 mol fraction titania-doped yttria stabilized zirconia (0.51TiYTZP/0.49TiYSZ). Furthermore, Y{sub 2}(Ti{sub 1-y}Zr{sub y}){sub 2}O{sub 7} pyrochlore is present as an impurity phase with y close to 1, according to FT-Raman results. Lower and highermore » additions of titania than that of 15 mol%, i.e., x=0, 5, 10, 20, 25 and 30 mol% were considered to study the evolution of 8YSZ phase as a function of the TiO{sub 2} content. Furthermore, zirconium titanate phase (ZrTiO{sub 4}) is detected when the titania content is equal or higher than 20 mol% and this phase admits Y{sub 2}O{sub 3} in solid solution according to FE-SEM-EDX. The 0.51TiYTZP/0.49TiYSZ duplex material was selected in this study to establish the mechanism of its electronic conduction under low oxygen partial pressures. In the pO{sub 2} range from 0.21 to 10{sup -7.5} atm. the conductivity is predominantly ionic and constant over the range and its value is 0.01 S/cm. The ionic plus electronic conductivity is 0.02 S/cm at 1000 {sup o}C and 10{sup -12.3} atm. Furthermore, the onset of electronic conductivity under reducing conditions exhibits a -1/4 pO{sub 2} dependence. Therefore, it is concluded that the n-type electronic conduction in the duplex material can be due to a small polaron-hopping between Ti{sup 3+} and Ti{sup 4+}. -- Graphical abstract: FE-SEM micrograph of a polished and thermal etched surface of a Ti-doped YTZP/Ti-doped YSZ composite material. Display Omitted Research highlights: {yields} Ti-doped YTZP/Ti-doped YSZ composite materials are mixed conductors under low partial pressures. {yields} From 5 mol% of TiO{sub 2}, Y{sub 2}(Ti{sub 1-y},Zr{sub y}){sub 2}O{sub 7} pyrochlore is present as a minor phase, being y close to 1 according to FT-Raman studies. {yields} The onset of the electronic conductivity under reducing conditions exhibit a -1/4 pO{sub 2} dependence. The n-type electronic conduction is due to a small polaron-hopping between Ti{sup 3+} and Ti{sup 4+}.« less

Eutectics as improved pharmaceutical materials: design, properties and characterization.

PubMed

Cherukuvada, Suryanarayan; Nangia, Ashwini

2014-01-28

Eutectics are a long known class of multi-component solids with important and useful applications in daily life. In comparison to other multi-component crystalline solids, such as salts, solid solutions, molecular complexes and cocrystals, eutectics are less studied in terms of molecular structure organization and bonding interactions. Classically, a eutectic is defined based on its low melting point compared to the individual components. In this article, we attempt to define eutectics not just based on thermal methods but from a structural organization view point, and discuss their microstructures and properties as organic materials vis-a-vis solid solutions and cocrystals. The X-ray crystal structure of a cocrystal is different from that of the individual components whereas the unit cell of a solid solution is similar to that of one of the components. Eutectics are closer to the latter species in that their crystalline arrangement is similar to the parent components but they are different with respect to the structural integrity. A solid solution possesses structural homogeneity throughout the structure (single phase) but a eutectic is a heterogeneous ensemble of individual components whose crystal structures are like discontinuous solid solutions (phase separated). Thus, a eutectic may be better defined as a conglomerate of solid solutions. A structural analysis of cocrystals, solid solutions and eutectics has led to an understanding that materials with strong adhesive (hetero) interactions between the unlike components will lead to cocrystals whereas those having stronger cohesive (homo/self) interactions will more often give rise to solid solutions (for similar structures of components) and eutectics (for different structures of components). We demonstrate that the same crystal engineering principles which have been profitably utilized for cocrystal design in the past decade can now be applied to make eutectics as novel composite materials, illustrated by stable eutectics of the hygroscopic salt of the anti-tuberculosis drug ethambutol as a case study. A current gap in the characterization of eutectic microstructure may be fulfilled through pair distribution function (PDF) analysis of X-ray diffraction data, which could be a rapid signature technique to differentiate eutectics from their components.

Solid and solution NMR studies of the complexation of Ag + with the trans isomer of captopril: Biological activities of this high blood pressure drug along with its Ag + complex

NASA Astrophysics Data System (ADS)

Isab, Anvarhusein A.; Wazeer, Mohamed I. M.

2006-09-01

Complexation of Ag + with captopril, 1-[(2 S)-3-mercapto-2-methylpropionyl]- L-proline, has been studied by 1H and 13C-NMR spectroscopy. The equilibrium constants for the trans to cis isomers of captopril bound to Ag + were measured by 1H NMR spectroscopy. It is observed that the trans isomer of the drug binds more strongly to Ag + between pH 5 and 8, as shown by the broadening of the trans isomer's resonances in 13C NMR spectra on complexation. A monodentate complexation of the trans captopril with Ag + via the thiol site is proposed based on the solid-state NMR and IR data. A superior antimicrobial activity is exhibited by the Cap-Ag(I) complex compared to captopril ligand itself against Heterotrotropic Plate Counts (HPC), Pseudomonas aeruginosa and Fecal streptococcus bacteria.

Unsupervised Calculation of Free Energy Barriers in Large Crystalline Systems

NASA Astrophysics Data System (ADS)

Swinburne, Thomas D.; Marinica, Mihai-Cosmin

2018-03-01

The calculation of free energy differences for thermally activated mechanisms in the solid state are routinely hindered by the inability to define a set of collective variable functions that accurately describe the mechanism under study. Even when possible, the requirement of descriptors for each mechanism under study prevents implementation of free energy calculations in the growing range of automated material simulation schemes. We provide a solution, deriving a path-based, exact expression for free energy differences in the solid state which does not require a converged reaction pathway, collective variable functions, Gram matrix evaluations, or probability flux-based estimators. The generality and efficiency of our method is demonstrated on a complex transformation of C 15 interstitial defects in iron and double kink nucleation on a screw dislocation in tungsten, the latter system consisting of more than 120 000 atoms. Both cases exhibit significant anharmonicity under experimentally relevant temperatures.

Determination of trace quaternary ammonium surfactants in water by combining solid-phase extraction with surface-assisted laser desorption/ionization mass spectrometry.

PubMed

Chen, Y C; Sun, M C

2001-01-01

This study demonstrates the feasibility of combining solid-phase extraction (SPE) with surface-assisted laser desorption/ionization (SALDI) mass spectrometry to determine trace quaternary ammonium surfactants in water. The trace surfactants in water were directly concentrated on the surface of activated carbon sorbent in SPE. The activated carbon sorbent was then mixed with the SALDI liquid for SALDI analysis. No SPE elution procedure was necessary. Experimental results indicate that the surfactants with longer chain alkyl groups exhibit higher sensitivities than those with shorter chain alkyl groups in SPE-SALDI analysis. The detection limit for hexadecyltrimethylammonium bromide is around 10 ppt in SPE-SALDI analysis by sampling 100 mL of aqueous solution, while that of tetradecyltrimethylammonium bromide is about 100 ppt. The detection limit for decyltrimethylammonium bromide and dodecyltrimethylammonium bromide is in the low-ppb range. Copyright 2001 John Wiley & Sons, Ltd.

2D all-solid state fabric supercapacitor fabricated via an all solution process for use in smart textiles

NASA Astrophysics Data System (ADS)

Jang, Yunseok; Jo, Jeongdai; Woo, Kyoohee; Lee, Seung-Hyun; Kwon, Sin; Kim, Kwang-Young; Kang, Dongwoo

2017-05-01

We propose a method to fabricate a supercapacitor for smart textiles using silver (Ag) nanoparticle (NP) ink, simple spray patterning systems, and intense pulsed light (IPL) sintering systems. The Ag NP current collectors provided as high conductivity as the metal current collectors. The spray patterning technique is useful for fabricating supercapacitors because it is simple, fast, and cheap. IPL systems reduced the sintering temperature of Ag NPs and prevented thermal damage to the textiles during the Ag NP sintering process. The two-dimensional (2D) all-solid state fabric supercapacitor with an interdigitated configuration, developed here, exhibited a specific capacitance of 25.7 F/g and an energy density of 1.5 Wh/kg at a power density of 64.3 W/kg. These results support the utility of our proposed method in the development of energy textiles.

Solution and solid trinitrotoluene (TNT) photochemistry: persistence of TNT-like ultraviolet (UV) resonance Raman bands.

PubMed

Gares, Katie L; Bykov, Sergei V; Godugu, Bhaskar; Asher, Sanford A

2014-01-01

We examined the 229 nm deep-ultraviolet resonance Raman (DUVRR) spectra of solution and solid-state trinitrotoluene (TNT) and its solution and solid-state photochemistry. Although TNT photodegrades with a solution quantum yield of ϕ ∼ 0.015, the initial photoproducts show DUVRR spectra extraordinarily similar to pure TNT, due to the similar photoproduct enhancement of the -NO2 stretching vibrations. This results in TNT-like DUVRR spectra even after complete TNT photolysis. These ultraviolet resonance Raman spectral bands enable DUVRR of trace as well as DUVRR standoff TNT detection. We determined the structure of various initial TNT photoproducts by using liquid chromatography-mass spectrometry and tandem mass spectrometry. Similar TNT DUVRR spectra and photoproducts are observed in the solution and solid states.

NEUTRALIZATIONS OF HIGH ALUMINUM LOW URANIUM USED NUCLEAR FUEL SOLUTIONS CONTAINING GADOLINIUM AS A NEUTRON POISON

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

Taylor-Pashow, K.

2011-06-08

H-Canyon will begin dissolving High Aluminum - Low Uranium (High Al/Low U) Used Nuclear Fuel (UNF) following approval by DOE which is anticipated in CY2011. High Al/Low U is an aluminum/enriched uranium UNF with small quantities of uranium relative to aluminum. The maximum enrichment level expected is 93% {sup 235}U. The High Al/Low U UNF will be dissolved in H-Canyon in a nitric acid/mercury/gadolinium solution. The resulting solution will be neutralized and transferred to Tank 39H in the Tank Farm. To confirm that the solution generated could be poisoned with Gd, neutralized, and discarded to the Savannah River Site (SRS)more » high level waste (HLW) system without undue nuclear safety concerns the caustic precipitation of simulant solutions was examined. Experiments were performed with three simulant solutions representative of the H-Canyon estimated concentrations in the final solutions after dissolution. The maximum U, Gd, and Al concentration were selected for testing from the range of solution compositions provided. Simulants were prepared in three different nitric acid concentrations, ranging from 0.5 to 1.5 M. The simulant solutions were neutralized to four different endpoints: (1) just before a solid phase was formed (pH 3.5-4), (2) the point where a solid phase was obtained, (3) 0.8 M free hydroxide, and (4) 1.2 M free hydroxide, using 50 wt % sodium hydroxide (NaOH). The settling behavior of the neutralized solutions was found to be slower compared to previous studies, with settling continuing over a one week period. Due to the high concentration of Al in these solutions, precipitation of solids was observed immediately upon addition of NaOH. Precipitation continued as additional NaOH was added, reaching a point where the mixture becomes almost completely solid due to the large amount of precipitate. As additional NaOH was added, some of the precipitate began to redissolve, and the solutions neutralized to the final two endpoints mixed easily and had expected densities of typical neutralized waste. Based on particle size and scanning electron microscopy analyses, the neutralized solids were found to be homogeneous and less than 20 microns in size. The majority of solids were less than 4 microns in size. Compared to previous studies, a larger percentage of the Gd was found to precipitate in the partially neutralized solutions (at pH 3.5-4). In addition the Gd:U mass ratio was found to be at least 1.0 in all of the solids obtained after partial or full neutralization. The hydrogen to U (H:U) molar ratios for two accident scenarios were also determined. The first was for transient neutralization and agitator failure. Experimentally this scenario was determined by measuring the H:U ratio of the settled solids. The minimum H:U molar ratio for solids from fully neutralized solutions was 388:1. The second accident scenario is for the solids drying out in an unagitiated pump box. Experimentally, this scenario was determined by measuring the H:U molar ratio in centrifuged solids. The minimum H:U atom ratios for centrifuged precipitated solids was 250:1. It was determined previously that a 30:1 H:Pu atom ratio was sufficient for a 1:1 Gd:Pu mass ratio. Assuming a 1:1 equivalence with {sup 239}Pu, the results of these experiments show Gd is a viable poison for neutralizing U/Gd solutions with the tested compositions.« less

Molecularly imprinted solid-phase extraction for the determination of ten macrolide drugs residues in animal muscles by liquid chromatography-tandem mass spectrometry.

PubMed

Song, Xuqin; Zhou, Tong; Liu, Qingying; Zhang, Meiyu; Meng, Chenying; Li, Jiufeng; He, Limin

2016-10-01

A simple and sensitive method based on molecularly imprinted solid-phase extraction coupled with liquid chromatography-tandem mass spectrometry was developed for the determination of the residues of ten macrolide drugs in swine, cattle and chicken muscles samples. The molecularly imprinted polymers (MIPs) were synthesized using tylosin as a template and methacrylic acid as a functional monomer. Samples were extracted with sodium borate buffer solution and ethyl acetate, and purified by the MIP cartridge. The results showed that the cartridge exhibited good recognition performance for macrolides, and better purification effect than the traditional solid-phase extraction cartridges. Recoveries of analytes at three spiking levels 1, 5 and 20μgkg(-1) ranged from 60.7% to 100.3% with the relative standard deviations less than 14%. The limits of detection of the method were between 0.1 and 0.4μgkg(-1). The method is useful for the routine monitoring of the residues of macrolide drugs in animal muscles. Copyright © 2016 Elsevier Ltd. All rights reserved.

Process for recovering pertechnetate ions from an aqueous solution also containing other ions

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1997-01-01

A solid/liquid process for the separation and recovery of TcO.sub.4.sup.-1 ions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups; whereas the aqueous solution from which the TcO.sub.4.sup.-1 ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO.sub.4.sup.-1 ions in such an aqueous solution that is free from MoO.sub.4.sup.-2 ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

Solid state stability and solubility of triethylenetetramine dihydrochloride.

PubMed

Henriet, Théo; Gana, Inès; Ghaddar, Carine; Barrio, Maria; Cartigny, Yohann; Yagoubi, Najet; Do, Bernard; Tamarit, Josep-Lluis; Rietveld, Ivo B

2016-09-10

The API triethylenetetramine dihydrochloride used as an alternative treatment of Wilson's disease is sensitive to water and it exhibits polymorphism. As this may become an issue for the drug formulation, the physical stability has been studied by differential scanning calorimetry, high-pressure thermal analysis, dynamic vapor sorption, and X-ray diffraction as a function of temperature. In addition, high-pressure liquid chromatography and mass spectrometry have been used to study the purity and chemical stability of the API. A pressure-temperature phase diagram of the pure compound has been constructed and it can be concluded that form II is monotropic in relation to form I, which is the only stable solid. The solubilities of the different solid forms have been determined with the help of a temperature - composition phase diagram. The API is very soluble, at 20° C about 10% of the saturated solution with respect to the dihydrate consists of API and the solubility of the pure form I is twice as high. Moreover, it has been shown that at 20°C, a relative humidity above 40% induces the formation of the dihydrate and at 70% a saturated solution appears. At higher temperatures, the formation of the dihydrate appears at lower relative humidity values. A clear link has been established between the API's chemical stability, its physical stability and the relative humidity in the air. Humidity levels above 40% are detrimental to the quality of the API. Copyright © 2016 Elsevier B.V. All rights reserved.

Natural convection in melt crystal growth - The influence of flow pattern on solute segregation

NASA Technical Reports Server (NTRS)

Brown, R. A.; Yamaguchi, Y.; Chang, C. J.

1982-01-01

The results of two lines of research aimed at calculating the structure of the flows driven by buoyancy in small-scale crystal growth systems and at understanding the coupling between these flows, the shape of the solidification interface, and dopant segregation in the crystal are reviewed. First, finite-element methods are combined with computer-aided methods for detecting multiple steady solutions to analyze the structure of the buoyancy-driven axisymmetric flows in a vertical cylinder heated from below. This system exhibits onset of convection, multiple steady flows, and loss of the primary stable flow beyond a critical value of the Rayleigh number. Second, results are presented for calculations of convection, melt/solid interface shape, and dopant segregation within a vertical ampoule with thermal boundary conditions that represent a prototype of the vertical Bridgman growth system.

Thermomechanical deformation behavior of a dynamic strain aging alloy, Hastelloy X

NASA Technical Reports Server (NTRS)

Castelli, Michael G.; Miner, Robert V.; Robinson, David N.

1992-01-01

An experimental study was performed to identify the effects of dynamic strain aging (solute drag) and metallurgical instabilities under thermomechanical loading conditions. The study involved a series of closely controlled thermomechanical deformation tests on the solid-solution-strenghened nickel-base superalloy, Hastelloy X. This alloy exhibits a strong isothermal strain aging peak at approximately 600 C, promoted by the effects of solute drag and precipitation hardening. Macroscopic thermomechanical hardening trends are correlated with microstructural characteristics through the use of transmission electron microscopy. These observations are compared and contrasted with isothermal conditions. Thermomechanical behavior unique to the isothermal database is identified and discussed. The microstructural characteristics were shown to be dominated by effects associated with the highest temperature of the thermomechanical cycle. Results indicate that the deformation behavior of Hastelloy X is thermomechanically path dependent. In addition, guidance is given pertaining to deformation modeling in the context of macroscopic unified theory. An internal state variable is formulated to qualitatively reflect the isotropic hardening trends identified in the TMD experiments.

AMOchar: Amorphous manganese oxide coating of biochar improves its efficiency at removing metal(loid)s from aqueous solutions.

PubMed

Trakal, Lukáš; Michálková, Zuzana; Beesley, Luke; Vítková, Martina; Ouředníček, Petr; Barceló, Andreu Piqueras; Ettler, Vojtěch; Číhalová, Sylva; Komárek, Michael

2018-06-01

A novel sorbent made from biochar modified with an amorphous Mn oxide (AMOchar) was compared with pure biochar, pure AMO, AMO+biochar mixtures and biochar+birnessite composite for the removal of various metal(loid)s from aqueous solutions using adsorption and solid-state analyses. In comparison with the pristine biochar, both Mn oxide-biochar composites were able to remove significantly greater quantities of various metal(loid)s from the aqueous solutions, especially at a ratio 2:1 (AMO:biochar). The AMOchar proved most efficient, removing almost 99, 91 and 51% of Pb, As and Cd, respectively. Additionally, AMOchar and AMO+biochar mixture exhibited reduced Mn leaching, compared to pure AMO. Therefore, it is concluded that the synthesis of AMO and biochar is able to produce a double acting sorbent ('dorbent') of enhanced efficiency, compared with the individual deployment of their component materials. Copyright © 2017 Elsevier B.V. All rights reserved.

LEACHING OF TITANIUM FROM MONOSODIUM TITANATE AND MODIFIED MST

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

Taylor-Pashow, K.; Fondeur, F.; Fink, S.

2012-08-01

Analysis of a fouled coalescer and pre-filters from Actinide Removal Process/Modular Caustic Side Solvent Extraction Unit (ARP/MCU) operations showed evidence of Ti containing solids. Based on these results a series of tests were planned to examine the extent of Ti leaching from monosodium titanate (MST) and modified monosodium titanate (mMST) in various solutions. The solutions tested included a series of salt solutions with varying free hydroxide concentrations, two sodium hydroxide concentrations, 9 wt % and 15 wt %, nitric and oxalic acid solutions. Overall, the amount of Ti leached from the MST and mMST was much greater in the acidmore » solutions compared to the sodium hydroxide or salt solutions, which is consistent with the expected trend. The leaching data also showed that increasing hydroxide concentration, whether pure NaOH solution used for filter cleaning in ARP or the waste salt solution, increased the amount of Ti leached from both the MST and mMST. For the respective nominal contact times with the MST solids - for filter cleaning or the normal filter operation, the dissolved Ti concentrations are comparable suggesting either cause may contribute to the increased Ti fouling on the MCU coalescers. Tests showed that Ti containing solids could be precipitated from solution after the addition of scrub acid and a decrease in temperature similar to expected in MCU operations. FTIR analysis of these solids showed some similarity to the solids observed on the fouled coalescer and pre-filters. Although only a cursory study, this information suggests that the practice of increasing free hydroxide in feed solutions to MCU as a mitigation to aluminosilicate formation may be offset by the impact of formation of Ti solids in the overall process. Additional consideration of this finding from MCU and SWPF operation is warranted.« less

Solid lithium ion conducting electrolytes and methods of preparation

DOEpatents

Narula, Chaitanya K; Daniel, Claus

2013-05-28

A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

Solid lithium ion conducting electrolytes and methods of preparation

DOEpatents

Narula, Chaitanya K.; Daniel, Claus

2015-11-19

A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

INTERNATIONAL CONFERENCE ON SEMICONDUCTOR INJECTION LASERS SELCO-87: Simple formula for the thermal conductivity of a quaternary solid solution

NASA Astrophysics Data System (ADS)

Nakwaski, W.

1988-11-01

An analysis is made of the thermal conductivity of quaternary solid solutions (alloys) allowing for their disordered structure on the basis of a phenomenological analysis proposed by Abeles. This method is applied to a quaternary solid solution In1 - xGaxAsyP1 - y. A simple analytic expression is derived for the thermal conductivity of this material.

Lattice Parameter Behavior with Different Nd and O Concentrations in (U 1-yNd y)O 2±x Solid Solution

DOE PAGES

Lee, Seung Min; Knight, Travis W.; Voit, Stwart L.; ...

2016-02-02

The solid solution of (U1-yFPy)O- 2±x, has the same fluorite structure as UO 2±x lambda, and the lattice parameter is affected by dissolved fission product and oxygen concentrations. We investigated the relation between the lattice parameter and the concentrations of neodymium and oxygen in the fluorite structure of (U 1-yNd y)O 2±x using X-ray diffraction. Moreover, the lattice parameter behavior in the (U 1-yNd y)O 2±x, solid solution shows a linear change as a function of the oxygen-to-metal ratio and solubility of neodymium. The lattice parameter depends on the radii of ions forming the fluorite structure and also can bemore » expressed by a particular rule (modified Vegard's law). Furthermore, the numerical analyses of the lattice parameters for the stoichiometric and nonstoichionietric solid solutions were conducted, and the lattice parameter model for the (U1-yNdy)O 2±x, solid solution was assessed. There is a very linear relationship between the lattice parameter and the Nd and O concentration for the stoichiometry and nonstoichiometry of the (U 1-yNd y)O 2±x solid solution was verified.« less

Revisiting HgCl 2: A solution- and solid-state 199Hg NMR and ZORA-DFT computational study

NASA Astrophysics Data System (ADS)

Taylor, R. E.; Carver, Colin T.; Larsen, Ross E.; Dmitrenko, Olga; Bai, Shi; Dybowski, C.

2009-07-01

The 199Hg chemical-shift tensor of solid HgCl 2 was determined from spectra of polycrystalline materials, using static and magic-angle spinning (MAS) techniques at multiple spinning frequencies and field strengths. The chemical-shift tensor of solid HgCl 2 is axially symmetric ( η = 0) within experimental error. The 199Hg chemical-shift anisotropy (CSA) of HgCl 2 in a frozen solution in dimethylsulfoxide (DMSO) is significantly smaller than that of the solid, implying that the local electronic structure in the solid is different from that of the material in solution. The experimental chemical-shift results (solution and solid state) are compared with those predicted by density functional theory (DFT) calculations using the zeroth-order regular approximation (ZORA) to account for relativistic effects. 199Hg spin-lattice relaxation of HgCl 2 dissolved in DMSO is dominated by a CSA mechanism, but a second contribution to relaxation arises from ligand exchange. Relaxation in the solid state is independent of temperature, suggesting relaxation by paramagnetic impurities or defects.

Structural and thermo-rheological analysis of solutions and gels of a β-lactoglobulin fraction isolated from bovine whey.

PubMed

Estévez, Natalia; Fuciños, Pablo; Bargiela, Verónica; Pastrana, Lorenzo; Tovar, Clara Asunción; Luisa Rúa, M

2016-05-01

A β-Lactoglobulin fraction (r-βLg) was isolated from milk whey hydrolysates produced with cardosins from Cynara cardunculus. The impact of the technological process on the r-βLg structure and how in turn this determined its heat-induced gelation was investigated. Results were analysed taking pure β-Lg (p-βLg) as control sample. The process induced changes in the r-βLg native conformation causing exposure of hydrophobic groups, lower thermal stability and also, shorter thermal treatments needed to give rise to non-native and aggregated species. At pH 3.2, r-βLg and p-βLg solutions exhibited two gelation steps, with the advantage that r-βLg protein may form stable gels at lower temperature than p-βLg. At pH 7.2, a specific thermo-viscoelastic stability to 73 °C was found, which corresponded to the gel point in both protein solutions. The difference was that while for p-βLg solution in sol state δ<45° (solid-like), however for r-βLg solution δ>45° (fluid-like). Copyright © 2015 Elsevier Ltd. All rights reserved.

Facile Co-Electrodeposition Method for High-Performance Supercapacitor Based on Reduced Graphene Oxide/Polypyrrole Composite Film.

PubMed

Chen, Junchen; Wang, Yaming; Cao, Jianyun; Liu, Yan; Zhou, Yu; Ouyang, Jia-Hu; Jia, Dechang

2017-06-14

A facile co-electrodeposition method has been developed to fabricate reduced graphene oxide/polypyrrole (rGO/PPy) composite films, with sodium dodecyl benzene sulfonate as both a surfactant and supporting electrolyte in the precursor solution. The introduction of rGO into the PPy films forms porous structure and enhances the conductivity across the film, leading to superior electrochemical performance. By controlling the deposition time and rGO concentration, the highest area capacitance can reach 411 mF/cm 2 (0.2 mA/cm 2 ) for rGO/PPy films, whereas optimized specific capacitance is as high as 361 F/g (0.2 mA/cm 2 ). All of the composite films exhibit excellent rate capability (at least 175 F/g at the current density of 12 mA/cm 2 ) compared with pure PPy film (only 12 F/g at the current density of 12 mA/cm 2 ). The rGO/PPy composite exhibits excellent cycling stability that maintains 104% of its initial capacitance after cycling for 2000 cycles and 80% for 5000 cycles. The two-electrode solid-state supercapacitor (SC) based on rGO/PPy composite electrodes demonstrates good rate performance, excellent cycling stability, as well as a high area capacitance of 222 mF/cm 2 . The solid-state planar SC based on the rGO/PPy composite exhibits an area capacitance of 9.4 mF/cm 2 , demonstrating great potential for fabrication of microsupercapacitors.

Effects of synthesis techniques on chemical composition, microstructure and dielectric properties of Mg-doped calcium titanate

NASA Astrophysics Data System (ADS)

Jongprateep, Oratai; Sato, Nicha

2018-04-01

Calcium titanate (CaTiO3) has been recognized as a material for fabrication of dielectric components, owing to its moderate dielectric constant and excellent microwave response. Enhancement of dielectric properties of the material can be achieved through doping, compositional and microstructural control. This study, therefore, aimed at investigating effects of powder synthesis techniques on compositions, microstructure, and dielectric properties of Mg-doped CaTiO3. Solution combustion and solid-state reaction were powder synthesis techniques employed in preparation of undoped CaTiO3 and CaTiO3 doped with 5-20 at% Mg. Compositional analysis revealed that powder synthesis techniques did not exhibit a significant effect on formation of secondary phases. When Mg concentration did not exceed 5 at%, the powders prepared by both techniques contained only a single phase. An increase of MgO secondary phase was observed as Mg concentrations increased from 10 to 20 at%. Experimental results, on the contrary, revealed that powder synthesis techniques contributed to significant differences in microstructure. Solution combustion technique produced powders with finer particle sizes, which consequently led to finer grain sizes and density enhancement. High-density specimens with fine microstructure generally exhibit improved dielectric properties. Dielectric measurements revealed that dielectric constants of all samples ranged between 231 and 327 at 1 MHz, and that superior dielectric constants were observed in samples prepared by the solution combustion technique.

Magnetism and Solid Solution Effects in NiAI (40% AI) Alloys

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

Liu, Chain T; Fu, Chong Long; Chisholm, Matthew F

2007-01-01

The solid solution effects of ternary additions of transition elements in intermetallic Ni-40% Al were investigated by both experimental studies and theoretical calculations. Co solute atoms when sitting at Ni sublattice sites do not affect the lattice parameter and hardening behavior of Ni-40Al. On the other hand, Fe, Mn, and Cr solutes, which are mainly on Al sublattice sites, substantially expand the lattice parameter and produce an unusual solid solution softening effect. First-principles calculations predict that these solute atoms with large unfilled d-band electrons develop large magnetic moments and effectively expand the lattice parameter when occupying Al sublattice sites. Themore » theoretical predictions were verified by both electron loss-energy spectroscopy (EELS) analyses and magnetic susceptibility measurements. The observed softening behavior can be explained quantitatively by the replacement of Ni anti-site defects (potent hardeners) by Fe, Mn, and Cr anti-site defects with smaller atom size mismatch between solute and Al atoms. This study has led to the identification of magnetic interaction as an important physical parameter affecting the solid solution hardening in intermetallic alloys containing transition elements.« less

Research on the synergistic doped effects and the catalysis properties of Cu2+ and Zn2+ co-doped CeO2 solid solutions

NASA Astrophysics Data System (ADS)

Zhang, Guofang; Li, Yiming; Hou, Zhonghui; Xv, Jianyi; Wang, Qingchun; Zhang, Yanghuan

2018-08-01

The Cu2+ and Zn2+ co-doped CeO2-based solid solutions were synthesized via hydrothermal method. The microstructure and the spectra features of the solid solutions were characterized systematically. The XRD results showed that the dopants were incorporated into the CeO2 lattice to form Ce1-xCu0.5xZn0.5xO2 solid solutions when x was lower than 0.14. The cell parameters and the crystalline size decreased linearly, and the lattice strain gradually increased with increasing the doping level. The TEM patterns showed that the particle size in the solid solution was lower than 10 nm which is in accordance with the XRD results. The ICP analysis indicated that the real doped content in the solid solution was close to the nominal proportion. XPS proved that the Ce3+ component was increased by doping. The Raman and PL spectra indicated that the lattice distortion and the oxygen vacancies also increased following the same trend. At the same time, the synergistic effects of two ions co-doped solid solutions were studied by comparing them with that of single ions doped samples. The catalysis effects of Cu2+ and Zn2+ co-doped CeO2-based solid solutions on the hydrogen storage electrochemical and kinetic properties of Mg2Ni alloys were detected. The electrochemistry properties of the Mg2Ni-Ni-5 wt% Ce1-xCu0.5xZn0.5xO2 composites indicated that the doped catalysts could provide better optimizations to improve the maximum discharge capacities and the discharge potentials. On the other hand, the charge transfer abilities on the surface and diffusion rate of H atoms in the bulk of alloys also got improved. The DSC measurements showed that the hydrogen desorption activation of the hydrogenated composites with Ce0.88Cu0.06Zn0.06O2 solid solutions decreased to 77.03 kJ mol-1, while that of the composites with pure CeO2 was 97.62 kJ mol-1. The catalysis effect was enhanced by the doped content increase that means that the catalysis mechanism had close links to the oxygen vacancy concentration and the lattice defects in the solid solutions. On the other hand, the doped Cu2+ and Zn2+ ions could also play an important role in the catalytic process.

Systematic Introduction of Aromatic Rings to Diphosphine Ligands for Emission Color Tuning of Dinuclear Copper(I) Iodide Complexes.

PubMed

Okano, Yuka; Ohara, Hiroki; Kobayashi, Atsushi; Yoshida, Masaki; Kato, Masako

2016-06-06

We have newly synthesized two solution-stable luminescent dinuclear copper(I) complexes, [Cu2(μ-I)2(dpppy)2] (Cu-py) and [Cu2(μ-I)2(dpppyz)2] (Cu-pyz), where dpppy = 2,3-bis(diphenylphosphino)pyridine and dpppyz = 2,3-bis(diphenylphosphino)pyrazine, using chelating diphosphine ligands composed of N-heteroaromatic rings. X-ray analysis clearly indicates that the molecular structures of Cu-py and Cu-pyz are almost identical with that of the parent complex, [Cu2(μ-I)2(dppb)2] [Cu-bz; dppb = 2,3-bis(diphenylphosphino)benzene]. Complexes Cu-py and Cu-pyz exhibit luminescence [emission quantum yield (Φem) = 0.48 and 0.02, respectively] in the solid state at 298 K. A wide emission color tuning, from 497 to 638 nm (energy = 0.55 eV, with an emission color ranging from green to reddish-orange), was achieved in the solid state by the introduction of pyridinic N atoms into the bridging phenyl group between the two diphenylphosphine groups. Density functional theory calculations suggest that the emission could originate from the effective combination of the metal-to-ligand charge-transfer excited state with the halide-to-ligand charge-transfer excited state. Thus, the emission color change is due to stabilization of the π* levels of the central aryl group in the diphosphine ligand. Furthermore, these copper(I) complexes exhibit thermally activated delayed fluorescence at 298 K because of the small singlet-triplet energy difference (ΔE = 523 and 564 cm(-1) for Cu-py and Cu-pyz, respectively). The stability of these complexes in chloroform, due to the rigid bonds between the diphosphine ligands and the Cu(I) ions, enables the preparation of emissive poly(methyl methacrylate) films by the solution-doping technique.

Disproportionation of a crystalline citrate salt of a developmental pharmaceutical compound: characterization of the kinetics using pH monitoring and online Raman spectroscopy plus quantitation of the crystalline free base form in binary physical mixtures using FT-Raman, XRPD and DSC.

PubMed

Skrdla, Peter J; Zhang, Dan

2014-03-01

The crystalline citrate salt (CS) of a developmental pharmaceutical compound, MK-Q, was investigated in this work from two different, but related, perspectives. In the first part of the paper, the apparent disproportionation kinetics were surveyed using two different slurry systems, one containing water and the other a pH 6.9 phosphate buffer, using time-dependent measurements of the solution pH or by acquiring online Raman spectra of the solids. While the CS is generally stable when stored as a solid under ambient conditions of temperature and humidity, its low pHmax (<3) facilitates rapid disproportionation in aqueous solution, particularly at higher pH values. The rate of disappearance of the CS was found to obey first-order (Noyes-Whitney/dissolution rate-limited) kinetics, however, the formation of the crystalline product form in the slurry system was observed to exhibit kinetics consistent with a heterogeneous nucleation-and-growth mechanism. In the second part of this paper, more sensitive offline measurements made using XRPD, DSC and FT-Raman spectroscopy were applied to the characterization of binary physical mixtures of the CS and free base (FB) crystalline forms of MK-Q to obtain a calibration curve for each technique. It was found that all calibration plots exhibited good linearity of response, with the limit of detection (LOD) for each technique estimated to be ≤7 wt% FB. While additional calibration curves would need to be constructed to allow for accurate quantitation in various slurry systems, the general feasibility of these techniques is demonstrated for detecting low levels of CS disproportionation. Copyright © 2013 Elsevier B.V. All rights reserved.

Effect of Isovalent Substitution on the Electronic Structure and Thermoelectric Properties of the Solid Solution α-As2Te3-xSex (0 ≤ x ≤ 1.5).

PubMed

Vaney, Jean-Baptiste; Delaizir, Gaëlle; Wiendlocha, Bartlomiej; Tobola, Janusz; Alleno, Eric; Piarristeguy, Andrea; Gonçalves, Antonio Pereira; Gendarme, Christine; Malaman, Bernard; Dauscher, Anne; Candolfi, Christophe; Lenoir, Bertrand

2017-02-20

We report on the influence of Se substitution on the electronic band structure and thermoelectric properties (5-523 K) of the solid solution α-As 2 Te 3-x Se x (0 ≤ x ≤ 1.5). All of the polycrystalline compounds α-As 2 Te 3-x Se x crystallize isostructurally in the monoclinic space group C2/m (No. 12, Z = 4). Regardless of the Se content, chemical analyses performed by scanning electron microscopy and electron probe microanalysis indicate a good chemical homogeneity, with only minute amounts of secondary phases for some compositions. In agreement with electronic band structure calculations, neutron powder diffraction suggests that Se does not randomly substitute for Te but exhibits a site preference. These theoretical calculations further predict a monotonic increase in the band gap energy with the Se content, which is confirmed experimentally by absorption spectroscopy measurements. Increasing x up to x = 1.5 leaves unchanged both the p-type character and semiconducting nature of α-As 2 Te 3 . The electrical resistivity and thermopower gradually increase with x as a result of the progressive increase in the band gap energy. Despite the fact that α-As 2 Te 3 exhibits very low lattice thermal conductivity κ L , the substitution of Se for Te further lowers κ L to 0.35 W m -1 K -1 at 300 K. The compositional dependence of the lattice thermal conductivity closely follows classical models of phonon alloy scattering, indicating that this decrease is due to enhanced point-defect scattering.

Process for recovering pertechnetate ions from an aqueous solution also containing other ions

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1997-02-18

A solid/liquid process for the separation and recovery of TcO{sub 4}{sup {minus}1} ions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups; whereas the aqueous solution from which the TcO{sub 4}{sup {minus}1} ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO{sub 4}{sup {minus}1} ions in such an aqueous solution that is free from MoO{sub 4}{sup {minus}2} ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 15 figs.

Influence of carbonate ion in the crystallization medium on the formation and chemical composition of CaHA-SrHA solid solutions

NASA Astrophysics Data System (ADS)

Nikolaev, Anton; Kuz'mina, Maria; Frank-Kamenetskaya, Olga; Zorina, Maina

2015-06-01

The study of the influence of carbonate ions in a solution to Sr-distribution in system «solution-crystal» and to ion substitutions and the non-stoichiometry of formed CaHA-SrHA solid solutions was carried out. The CaHA-SrHA solid solutions were synthesized by precipitation from aqueous solutions with the atomic C/P ratio equal to 0, 0.05 and 0.1 at T = 90 °C. Resulting precipitates were studied using various methods including X-ray powder diffraction, infrared spectroscopy and different chemical analyses. The results of the study have shown that in the range of values of (Ca + Sr)/P in the water solution from 40% to 85%, the presence of carbonate ions (C/P = 0.05-0.1) promotes the incorporation of strontium in the apatite. Crystalline apatite solid solutions formed from water solutions of such composition are more defective compared to apatites that are mainly calcium or strontium. They are characterized by a smaller size coherence scattering domain length along [0 0 1] direction and a greater number of carbonate ions, water molecules and vacancies at the Ca-sites.

ZrB 2-HfB 2 solid solutions as electrode materials for hydrogen reaction in acidic and basic solutions

DOE PAGES

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

2016-11-09

Spark plasma sintered transition metal diborides such as HfB 2, ZrB 2 and their solid solutions were investigated as electrode materials for electrochemical hydrogen evolutions reactions (HER) in 1 M H 2SO 4 and 1 M NaOH electrolytes. HfB 2 and ZrB 2 formed complete solid solutions when mixed in 1:1, 1:4, and 4:1 ratios and they were stable in both electrolytes. The HER kinetics of the diborides were slower in the basic solution than in the acidic solutions. The Tafel slopes in 1 M H 2SO 4 were in the range of 0.15 - 0.18 V/decade except for puremore » HfB 2 which showed a Tafel slope of 0.38 V/decade. In 1 M NaOH the Tafel slopes were in the range of 0.12 - 0.27 V/decade. The composition of Hf xZr 1-xB 2 solid solutions with x = 0.2 - 0.8, influenced the exchange current densities, overpotentials and Tafel slopes of the HER. As a result, the EIS data were fitted with a porous film equivalent circuit model in order to better understand the HER behavior. In addition, modeling calculations, using density functional theory approach, were carried out to estimate the density of states and band structure of the boride solid solutions.« less

Synthesis of phthalocyanine doped sol-gel materials

NASA Technical Reports Server (NTRS)

Dunn, Bruce

1993-01-01

The synthesis of sol-gel silica materials doped with three different types of metallophthalocyanines has been studied. Homogeneous materials of good optical quality were prepared and the first optical limiting measurements of dyes in sol-gel hosts were carried out. The properties of these solid state limiters are similar to limiters based on phthalocyanine (Pc) in solution. Sol-gel silica materials containing copper, tin and germanium phthalocyanines were investigated. The initial step in all cases was to prepare silica sols by the sonogel method using tetramethoxy silane (TMOS), HCl and distilled water. Thereafter, the synthesis depended upon the specific Pc and its solubility characteristics. Copper phthalocyanine tetrasulfonic acid tetra sodium salt (CuPc4S) is soluble in water and various doping levels (1 x 10 (exp -4) M to 1 x 10 (exp -5) M) were added to the sol. The group IV Pc's, SnPc(OSi(n-hexyl)3)2 and GePc(OSi(n-hexyl)3)2, are insoluble in water and the process was changed accordingly. In these cases, the compounds were dissolved in THF and then added to the sol. The Pc concentration in the sol was 2 x 10(exp -5)M. The samples were then aged and dried in the standard method of making xerogel monoliths. Comparative nanosecond optical limiting experiments were performed on silica xerogels that were doped with the different metallophthalocyanines. The ratio of the net excited state absorption cross section (sigma(sub e)) to the ground state cross section (sigma(sub g)) is an important figure of merit that is used to characterize these materials. By this standard the SnPc sample exhibits the best limiting for the Pc doped sol-gel materials. Its cross section ratio of 19 compares favorably with the value of 22 that was measured in toluene. The GePc materials appear to not be as useful as those containing SnPc. The GePc doped solids exhibit a higher onset energy (2.5 mj and lower cross section ratio, 7. The CuPc4S sol-gel material has a still lower cross section ratio, 4, however, the tetrasulfonate groups make the dye soluble in water which greatly facilitates its incorporation into the sol-gel matrix. The nonlinear transmission of CuPc4S in a pH 2 buffer solution and in a silica xerogel were compared. It is evident that the CuPc4S preserves its optical limiting behavior in the sol-gel matrix, indicating that the fundamental excited state absorption process is essentially the same for a molecule in solution or in the solid state. Although the spectroscopic details of energy level lifetimes are unknown, the significance is that passive optical limiting has been achieved in the solid state via incorporation of a dye into an inorganic host. The only compromise occurs at the extremely high energy regime where photobleaching is observed. This is a result of the limited mobility of the dye molecules in the solid silica host relative to a liquid host. The effects of photodegradation in the xerogel are additive, whereas the solution provides a supply of fresh molecules that are free to enter the active volume between pulses.

Ultrasonic transient bounded-beam propagation in a solid cylinder waveguide embedded in a solid medium.

PubMed

Laguerre, Laurent; Grimault, Anne; Deschamps, Marc

2007-04-01

A semianalytical solution alternative and complementary to modal technique is presented to predict and interpret the ultrasonic pulsed-bounded-beam propagation in a solid cylinder embedded in a solid matrix. The spectral response to an inside axisymmetric velocity source of longitudinal and transversal cylindrical waves is derived from Debye series expansion of the embedded cylinder generalized cylindrical reflection/transmission coefficients. So, the transient guided wave response, synthesized by inverse double Fourier-Bessel transform, is expressed as a combination of the infinite medium contribution, longitudinal, transversal, and coupled longitudinal and transversal waveguide sidewall interactions. Simulated (f, 1/lambdaz) diagrams show the influence of the number of waveguide sidewall interactions to progressively recover dispersion curves. Besides, they show the embedding material filters specific signal portions by concentrating the propagating signal in regions where phase velocity is closer to phase velocity in steel. Then, simulated time waveforms using broadband high-frequency excitation show that signal leading portions exhibit a similar periodical pattern, for both free and embedded waveguides. Debye series-based interpretation shows that double longitudinal/transversal and transversal/longitudinal conversions govern the time waveform leading portion as well as the radiation attenuation in the surrounding cement grout. Finally, a methodology is deduced to minimize the radiation attenuation for the long-range inspection of embedded cylinders.

Surface active stabilizer Tyloxapol in colloidal dispersions exerts cytostatic effects and apoptotic dismissal of cells

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

Kristl, Julijana; Teskac, Karmen; Milek, Miha

Solid lipid nanoparticles (SLN) have been praised for their advantageous drug delivery properties such as biocompatibility, controlled release and passive drug targeting. However, the cytotoxicity of SLN and their ingredients, especially over a longer time period, has not been investigated in detail. We examined the critical issues regarding the use of a surface active stabilizer Tyloxapol (Tyl) for the preparation of solid lipid particles (SLP) and their effects on cellular functions and viability. SLP composed of behenate, phospholipids and a stabilizer, Tyloxapol or Lutrol (Lut), were prepared by the lipid melt method, labeled with a fluorescent dye and tested onmore » Jurkat or HEK293 cells. The nano-sized particles were rapidly internalized and exhibited cytoplasmic localization. Incubation of cells with SLP-Tyl resulted in a dose- and time-dependent cytostatic effect, and also caused moderate and delayed cytotoxicity. Tyloxapol solution or SLP-Tyl dispersion caused the detachment of HEK293 cells, a decrease in cell proliferation and alterations in cellular morphology. Cell cycle analysis revealed that, while the unfavourable effects of SLP-Tyl and Tyloxapol solution are similar initially, longer incubation results in partial recovery of cells incubated with the dispersion of SLP-Tyl, whereas the presence of Tyloxapol solution induces apoptotic cell death. These findings indicate that Tyloxapol is an unfavourable stabilizer of SLP used for intracellular delivery and reinforce the role of stabilizers in a design of SLP with minimal cytotoxic properties.« less

Thermal processing of a poorly water-soluble drug substance exhibiting a high melting point: the utility of KinetiSol® Dispersing.

PubMed

Hughey, Justin R; Keen, Justin M; Brough, Chris; Saeger, Sophie; McGinity, James W

2011-10-31

Poorly water-soluble drug substances that exhibit high melting points are often difficult to successfully process by fusion-based techniques. The purpose of this study was to identify a suitable polymer system for meloxicam (MLX), a high melting point class II BCS compound, and investigate thermal processing techniques for the preparation of chemically stable single phase solid dispersions. Thermal and solution based screening techniques were utilized to screen hydrophilic polymers suitable for immediate release formulations. Results of the screening studies demonstrated that Soluplus(®)(SOL) provided the highest degree of miscibility and solubility enhancement. A hot-melt extrusion feasibility study demonstrated that high temperatures and extended residence times were required in order to render compositions amorphous, causing significant degradation of MLX. A design of experiments (DOE) was conducted on the KinetiSol(®) Dispersing (KSD) process to evaluate the effect of processing conditions on the chemical stability and amorphous character of MLX. The study demonstrated that ejection temperature significantly impacted MLX stability. All samples prepared by KSD were substantially amorphous. Dissolution analysis of the KSD processed solid dispersions showed increased dissolution rates and extent of supersaturation over the marketed generic MLX tablets. Copyright © 2011 Elsevier B.V. All rights reserved.

Solution based synthesis of mixed-phase materials in the Li2TiO3-Li4SiO4 system

NASA Astrophysics Data System (ADS)

Hanaor, Dorian A. H.; Kolb, Matthias H. H.; Gan, Yixiang; Kamlah, Marc; Knitter, Regina

2015-01-01

As candidate tritium breeder materials for use in the ITER helium cooled pebble bed, ceramic multiphasic compounds lying in the region of the quasi-binary lithium metatitanate-lithium orthosilicate system may exhibit mechanical and physical advantages relative to single phase materials. Here we present an organometallic solution-based synthesis procedure for the low-temperature fabrication of compounds in the Li2TiO3-Li4SiO4 region and investigate phase stability and transformations through temperature varied X-ray diffraction and scanning calorimetry. Results demonstrate that the metatitanate and metasilicate phases Li2TiO3 and Li2SiO3 readily crystallise in nanocrystalline form at temperatures below 180 °C. Lithium deficiency in the region of 5% results from Li sublimation from Li4SiO4 and/or from excess Li incorporation in the metatitanate phase and brings about a stoichiometry shift, with product compounds exhibiting mixed lithium orthosilicate/metasilicate content towards the Si rich region and predominantly Li2TiO3 content towards the Ti rich region. Above 1150 °C the transformation of monoclinic to cubic γ-Li2TiO3 disordered solid-solution occurs while the melting of silicate phases indicates a likely monotectic type system with a solidus line in the region 1050-1100 °C. Synthesis procedures involving a lithium chloride precursor are not likely to be a viable option for breeder pebble synthesis as this route was found to yield materials with a more significant Li-deficiency exhibiting the crystallisation of the Li2TiSiO5 phase at intermediate compositions.

Calculation of open and closed system elastic coefficients for multicomponent solids

NASA Astrophysics Data System (ADS)

Mishin, Y.

2015-06-01

Thermodynamic equilibrium in multicomponent solids subject to mechanical stresses is a complex nonlinear problem whose exact solution requires extensive computations. A few decades ago, Larché and Cahn proposed a linearized solution of the mechanochemical equilibrium problem by introducing the concept of open system elastic coefficients [Acta Metall. 21, 1051 (1973), 10.1016/0001-6160(73)90021-7]. Using the Ni-Al solid solution as a model system, we demonstrate that open system elastic coefficients can be readily computed by semigrand canonical Monte Carlo simulations in conjunction with the shape fluctuation approach. Such coefficients can be derived from a single simulation run, together with other thermodynamic properties needed for prediction of compositional fields in solid solutions containing defects. The proposed calculation approach enables streamlined solutions of mechanochemical equilibrium problems in complex alloys. Second order corrections to the linear theory are extended to multicomponent systems.

Dispersoid reinforced alloy powder and method of making

DOEpatents

Anderson, Iver E; Terpstra, Robert L

2014-10-21

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomized particles to a depth below the surface of said atomized particles. Bodies made from the dispersion strengthened solidified particles exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures.

Synthesis, Luminescent Properties of aza-Boron-Diquinomethene Difluoride Complexes and Their Application for Fluorescent Security Inks.

PubMed

Gu, Long; Liu, Rui; Shi, Hong; Wang, Qiang; Song, Guangliang; Zhu, Xiaolin; Yuan, Shidong; Zhu, Hongjun

2016-03-01

Two aza-boron-diquinomethene (aza-BODIQU) complexes bearing phenyl and carbazyl substituents were synthesized and characterized. Their photophysical properties were investigated systematically via spectroscopic and theoretical methods. Both complexes exhibit strong (1)π-π* transition absorptions (λ(abs) = 400-540 nm) and intense fluorescent emissions (λ(em) = 440-600 nm, Φ(PL) = 0.93 and 0.78) in CH2Cl2 solution and in solid state at room temperature. Compared to the complex with phenyl groups, the complex bearing carbazyl groups shows significant bathochromic shift in both absorption and emission. This could be attributed to the larger π-electron conjugation of the carbazole unit and intramolecular charge transfer feature from carbazole to aza-BODIQU component. In addition, the complexes exhibit intense photoluminescence and good stability on antacid, anti-alkali and stability in printing ink samples, which makes them potential dopants for the application of fluorescent security inks.

FeRh ground state and martensitic transformation

NASA Astrophysics Data System (ADS)

Zarkevich, Nikolai A.; Johnson, Duane D.

2018-01-01

Cubic B 2 FeRh exhibits a metamagnetic transition [(111) antiferromagnet (AFM) to ferromagnet (FM)] around 353 K and remains structurally stable at higher temperatures. However, the calculated zero-Kelvin phonons of AFM FeRh exhibit imaginary modes at M points in the Brillouin zone, indicating a premartensitic instability, which is a precursor to a martensitic transformation at low temperatures. Combining electronic-structure calculations with ab initio molecular dynamics, conjugate gradient relaxation, and the solid-state nudged-elastic band methods, we predict that AFM B 2 FeRh becomes unstable at ambient pressure and transforms without a barrier to an AFM(111) orthorhombic (martensitic) ground state below 90 ±10 K . We also consider competing structures, in particular, a tetragonal AFM(100) phase that is not the global ground state, as proposed [Phys. Rev. B 94, 180407(R) (2016), 10.1103/PhysRevB.94.180407], but a constrained solution.

Formation of Multi-Layer Structures in Bi3Pb7 Intermetallic Compounds under an Ultra-High Gravitational Field

NASA Astrophysics Data System (ADS)

Mashimo, T.; Iguchi, Y.; Bagum, R.; Sano, T.; Sakata, O.; Ono, M.; Okayasu, S.

2008-02-01

Ultra-high gravitational field (Mega-gravity field) can promote sedimentation of atoms (diffusion) even in solids, and is expected to form a compositionally-graded structure and/or nonequilibrium phase in multi-component condensed matter. We had achieved sedimentation of substitutional solute atoms in miscible systems (Bi-Sb, In-Pb, etc.). In this study, a mega-gravity experiment at high temperature was performed on a thin-plate sample (0.7 mm in thickness) of the intermetallic compound Bi3Pb7. A visible four-layer structure was produced, which exhibited different microscopic structures. In the lowest-gravity region layer, Bi phase appeared. In the mid layers, a compositionally-graded structure was formed, with differences observed in the powder X-ray diffraction patterns. Such a multi-layer structure is expected to exhibit unique physical properties such as superconductivity.

Stabilized antiferroelectricity in xBiScO3-(1-x)NaNbO3 lead-free ceramics with established double hysteresis loops

NASA Astrophysics Data System (ADS)

Gao, Lisheng; Guo, Hanzheng; Zhang, Shujun; Randall, Clive A.

2018-02-01

We previously reported various solid solution systems that demonstrated the stabilized antiferroelectric (P) phases in NaNbO3 through lowering the tolerance factor. However, all those reported modifications were achieved by adding A2+B4+O3 type solid solutions. A lead-free antiferroelectric (AFE) solid solution xBiScO3-(1-x)NaNbO3 was rationalized by adopting the tolerance factor design rule. Specifically, adding BiScO3 was found to effectively stabilize the AFE phase without changing the crystal symmetry of NaNbO3. Microstructure and electron zone axis diffraction patterns from transmission electron microscopy revealed the stabilized AFE (P) phase in this solid solution. Besides, the electric-field-induced polarization with a double-hysteresis loop was observed. The present results pointed out that the strategy could also be applied while adding A3+B3+O3 type solid solutions. In addition, it expanded the compositional design that can be applied to antiferroelectric materials.

Lithium-Based High Energy Density Flow Batteries

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar V. (Inventor); West, William C. (Inventor); Kindler, Andrew (Inventor); Smart, Marshall C. (Inventor)

2014-01-01

Systems and methods in accordance with embodiments of the invention implement a lithium-based high energy density flow battery. In one embodiment, a lithium-based high energy density flow battery includes a first anodic conductive solution that includes a lithium polyaromatic hydrocarbon complex dissolved in a solvent, a second cathodic conductive solution that includes a cathodic complex dissolved in a solvent, a solid lithium ion conductor disposed so as to separate the first solution from the second solution, such that the first conductive solution, the second conductive solution, and the solid lithium ionic conductor define a circuit, where when the circuit is closed, lithium from the lithium polyaromatic hydrocarbon complex in the first conductive solution dissociates from the lithium polyaromatic hydrocarbon complex, migrates through the solid lithium ionic conductor, and associates with the cathodic complex of the second conductive solution, and a current is generated.

Electrolyte for batteries with regenerative solid electrolyte interface

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

Xiao, Jie; Lu, Dongping; Shao, Yuyan

2017-08-01

An energy storage device comprising: an anode; and a solute-containing electrolyte composition wherein the solute concentration in the electrolyte composition is sufficiently high to form a regenerative solid electrolyte interface layer on a surface of the anode only during charging of the energy storage device, wherein the regenerative layer comprises at least one solute or solvated solute from the electrolyte composition.

Design principles for radiation-resistant solid solutions

NASA Astrophysics Data System (ADS)

Schuler, Thomas; Trinkle, Dallas R.; Bellon, Pascal; Averback, Robert

2017-05-01

We develop a multiscale approach to quantify the increase in the recombined fraction of point defects under irradiation resulting from dilute solute additions to a solid solution. This methodology provides design principles for radiation-resistant materials. Using an existing database of solute diffusivities, we identify Sb as one of the most efficient solutes for this purpose in a Cu matrix. We perform density-functional-theory calculations to obtain binding and migration energies of Sb atoms, vacancies, and self-interstitial atoms in various configurations. The computed data informs the self-consistent mean-field formalism to calculate transport coefficients, allowing us to make quantitative predictions of the recombined fraction of point defects as a function of temperature and irradiation rate using homogeneous rate equations. We identify two different mechanisms according to which solutes lead to an increase in the recombined fraction of point defects; at low temperature, solutes slow down vacancies (kinetic effect), while at high temperature, solutes stabilize vacancies in the solid solution (thermodynamic effect). Extension to other metallic matrices and solutes are discussed.

Adsorption of surfactants and polymers at interfaces

NASA Astrophysics Data System (ADS)

Rojas, Orlando Jose

Surface tension and high-resolution laser light scattering experiments were used to investigate the adsorption of isomeric sugar-based surfactants at the air/liquid interface in terms of surfactant surface packing and rheology. Soluble monolayers of submicellar surfactant solutions exhibited a relatively viscous behavior. It was also proved that light scattering of high-frequency thermally-induced capillary waves can be utilized to study surfactant exchange between the surface and the bulk solution. Such analysis revealed the existence of a diffusional relaxation mechanism. A procedure based on XPS was developed for quantification, on an absolute basis, of polymer adsorption on mica and Langmuir-Blodgett cellulose films. The adsorption of cationic polyelectrolytes on negatively-charged solid surfaces was highly dependent on the polymer ionicity. It was found that the adsorption process is driven by electrostatic mechanisms. Charge overcompensation (or charge reversal) of mica occurred after adsorption of polyelectrolytes of ca. 50% charge density, or higher. It was demonstrated that low-charge-density polyelectrolytes adsorb on solid surfaces with an extended configuration dominated by loops and tails. In this case the extent of adsorption is limited by steric constraints. The conformation of the polyelectrolyte in the adsorbed layer is dramatically affected by the presence of salts or surfactants in aqueous solution. The phenomena which occur upon increasing the ionic strength are consistent with the screening of the electrostatic attraction between polyelectrolyte segments and solid surface. This situation leads to polyelectrolyte desorption accompanied by both an increase in the layer thickness and the range of the steric force. Adsorbed polyelectrolytes and oppositely charged surfactants readily associate at the solid/liquid interface. Such association induces polyelectrolyte desorption at a surfactant concentration which depends on the polyelectrolyte charge density. In practical systems the adsorption phenomena were found to be far more complex. Electrostatic and hydrogen bonding interactions play a major role in the adsorption of cationic polyelectrolytes on cellulosic substrates. Cationic and underivatized guar gum macromolecules form complexes with fines and dissolved and colloidal carbohydrates which are then retained on the cellulose fibers. The extent of the adsorption and association depends on the charge and nature of all the components present in pulp suspensions.

Studies on solid solutions based on layered honeycomb-ordered phases P2-Na{sub 2}M{sub 2}TeO{sub 6} (M=Co, Ni, Zn)

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

Berthelot, Romain; Schmidt, Whitney; Sleight, A.W.

2012-12-15

Three complete solid solutions between the layered phases P2-Na{sub 2}M{sub 2}TeO{sub 6} (M=Co, Ni, Zn) have been prepared by conventional solid state method and investigated through X-ray diffraction, magnetism and optical measurements. All compositions are characterized by a M{sup 2+}/X{sup 6+} honeycomb ordering within the slabs and crystallize in a hexagonal unit cell. However, a structural transition based on a different stacking is observed as nickel (space group P6{sub 3}/mcm) is substituted by zinc or cobalt (space group P6{sub 3}22). All compositions exhibit a paramagnetic Curie-Weiss behavior at high temperatures; and the magnetic moment values confirm the presence of Ni{supmore » 2+} and/or Co{sup 2+} cations. The low-temperature antiferromagnetic order of Na{sub 2}Ni{sub 2}TeO{sub 6} and Na{sub 2}Co{sub 2}TeO{sub 6} is suppressed by zinc substitution. The color of the obtained compositions varies from pink, to light green and white when M=Co, Ni, Zn, respectively. - Graphical abstract: The comparison between the structure of Na{sub 2}Ni{sub 2}TeO{sub 6} (left) and Na{sub 2}M{sub 2}TeO{sub 6} (M=Co, Zn) (right) evidences the stacking difference with distinct atom sequences along the hexagonal c-axis. Highlights: Black-Right-Pointing-Pointer Solid solutions between lamellar phases Na{sub 2}M{sub 2}TeO{sub 6} (M=Co, Ni, Zn) are investigated. Black-Right-Pointing-Pointer A M{sup 2+}/X{sup 6+} honeycomb ordering characterized all the compositions. Black-Right-Pointing-Pointer A structural transition is shown when Ni is replaced by Co or Zn. Black-Right-Pointing-Pointer The low-temperature AFM ordering of Na{sub 2}Ni{sub 2}TeO{sub 6} and Na{sub 2}Co{sub 2}TeO{sub 6} is suppressed by zinc substitution. Black-Right-Pointing-Pointer Color changes from pink to light green and white when M=Co, Ni, Zn, respectively.« less

First-principles investigation of competing magnetic interactions in (Mn ,Fe )Ru2Sn Heusler solid solutions

NASA Astrophysics Data System (ADS)

Decolvenaere, Elizabeth; Gordon, Michael; Seshadri, Ram; Van der Ven, Anton

2017-10-01

Many Heusler compounds possess magnetic properties well suited for applications as spintronic materials. The pseudobinary Mn0.5Fe0.5Ru2Sn , formed as a solid solution of two full Heuslers, has recently been shown to exhibit exchange hardening suggestive of two magnetic phases, despite existing as a single chemical phase. We have performed a first-principles study of the chemical and magnetic degrees of freedom in the Mn1 -xFexRu2Sn pseudobinary to determine the origin of the unique magnetic behavior responsible for exchange hardening within a single phase. We find a transition from antiferromagnetic (AFM) to ferromagnetic (FM) behavior upon replacement of Mn with Fe, consistent with experimental results. The lowest energy orderings in Mn1 -xFexRu2Sn consist of chemically and magnetically uniform (111) planes, with Fe-rich regions preferring FM ordering and Mn-rich regions preferring AFM ordering, independent of the overall composition. Analysis of the electronic structure suggests that the magnetic behavior of this alloy arises from a competition between AFM-favoring Sn-mediated superexchange and FM-favoring RKKY exchange mediated by spin-polarized conduction electrons. Changes in valency upon replacement of Mn with Fe shifts the balance from superexchange-dominated interactions to RKKY-dominated interactions.

Mononuclear nickel (II) and copper (II) coordination complexes supported by bispicen ligand derivatives: Experimental and computational studies

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

Singh, Nirupama; Niklas, Jens; Poluektov, Oleg

2017-01-01

The synthesis, characterization and density functional theory calculations of mononuclear Ni and Cu complexes supported by the N,N’-Dimethyl-N,N’-bis-(pyridine-2-ylmethyl)-1,2-diaminoethane ligand and its derivatives are reported. The complexes were characterized by X-ray crystallography as well as by UV-visible absorption spectroscopy and EPR spectroscopy. The solid state structure of these coordination complexes revealed that the geometry of the complex depended on the identity of the metal center. Solution phase characterization data are in accord with the solid phase structure, indicating minimal structural changes in solution. Optical spectroscopy revealed that all of the complexes exhibit color owing to d-d transition bands in the visiblemore » region. Magnetic parameters obtained from EPR spectroscopy with other structural data suggest that the Ni(II) complexes are in pseudo-octahedral geometry and Cu(II) complexes are in a distorted square pyramidal geometry. In order to understand in detail how ligand sterics and electronics affect complex topology detailed computational studies were performed. The series of complexes reported in this article will add significant value in the field of coordination chemistry as Ni(II) and Cu(II) complexes supported by tetradentate pyridyl based ligands are rather scarce.« less

Fe1-xZnxS ternary solid solution as an efficient Fenton-like catalyst for ultrafast degradation of phenol.

PubMed

Gao, Jing; Liu, Yutang; Xia, Xinnian; Wang, Longlu; Dong, Wanyue

2018-07-05

Heterogeneous Fenton-like system has been proved to be an promising alternative to Fenton system due to its easy separation. However, it's a challenge to design heterogeneous Fenton-like catalysts with high activity and great durability. Here, ternary solid solution Fe 1-x Zn x S were prepared via hydrothermal synthesis as heterogeneous Fenton-like catalysts. The Fe 0.7 Zn 0.3 S sample exhibited state of the art activity for yielding OH by H 2 O 2 decomposition, and the ultrafast degradation of phenol was achieved in 4 min at initial acidic condition under room temperature. The phenol degradation rate constant of Fe 0.7 Zn 0.3 S was 99 and 70 times of ZnS and FeS, respectively. Further, we show that the unique structural configuration of iron atoms, the formation of FeS 2 -pyrite with (200) plane, are responsible for the excellent activity. The intermediate products were identified by LC-MS and a possible pathway was accordingly proposed to elucidate the mechanism of phenol degradation by OH. Overall, this work provides an idea for the rational design of the relevant heterogeneous Fenton-like catalysts. Copyright © 2018 Elsevier B.V. All rights reserved.

Mechanical Alloying of W-Mo-V-Cr-Ta High Entropy Alloys

NASA Astrophysics Data System (ADS)

Das, Sujit; Robi, P. S.

2018-04-01

Recent years have seen the emergence of high-entropy alloys (HEAs) consisting of five or more elements in equi-atomic or near equi-atomic ratios. These alloys in single phase solid solution exhibit exceptional mechanical properties viz., high strength at room and elevated temperatures, reasonable ductility and stable microstructure over a wide range of temperatures making it suitable for high temperature structural materials. In spite of the attractive properties, processing of these materials remains a challenge. Reports regarding fabrication and characterisation of a few refractory HEA systems are available. The processing of these alloys have been carried out by arc melting of small button sized materials. The present paper discusses the development of a novel refractory W-Mo-V-Cr-Ta HEA powder based on a new alloy design concept. The powder mixture was milled for time periods up to 64 hours. Single phase alloy powder having body centred cubic structure was processed by mechanical alloying. The milling characteristics and extent of alloying during the ball milling were characterized using X-ray diffractiometre (XRD), field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM). A single phase solid solution alloy powder having body-centred cubic (BCC) structure with a lattice parameter of 3.15486 Å was obtained after milling for 32 hours.

Structural and magnetic characterization of the complete delafossite solid solution (CuAlO2)1-x(CuCrO2)x

NASA Astrophysics Data System (ADS)

Barton, Phillip; Seshadri, Ram; Knöller, Andrea; Rosseinsky, Matthew

2012-02-01

We have prepared the complete delafossite solid solution between diamagnetic CuAlO2 and the t2g^3 frustrated antiferromagnet CuCrO2. The crystal structure and magnetism were studied with powder x-ray diffraction and magnetometry. The unit cell parameters follow the V'egard law and μeff is equal to the Cr^3+ spin-only S = 3/2 value. θCW is negative and its magnitude increases with Cr substitution. For dilute Cr compositions, JBB was estimated by mean-field theory to be 3.0,eV. Despite the sizable θCW, long-range antiferromagnetic order does not develop until x is almost 1, and is preceeded by glassy behavior. For all samples, the 5,isothermal magnetization is sub-Brillouin and does not saturate in fields up to 5,. A scaled inverse susceptibility plot reveals that significant short-range antiferromagnetic interactions occur in CuCrO2 above its N'eel temperature. Additionally, the Al-substituted samples exhibit uncompensated short-range behavior and x = 0.75 shows glassy characteristics. It is suggested that reduction in magnetic frustration due to the presence of non-magnetic Al does not have as dominant an effect on magnetism as do chemical disorder and dilution of magnetic exchange.

Production of a water-soluble fertilizer containing amino acids by solid-state fermentation of soybean meal and evaluation of its efficacy on the rapeseed growth.

PubMed

Wang, Jianlei; Liu, Zhemin; Wang, Yue; Cheng, Wen; Mou, Haijin

2014-10-10

Soybean meal is a by-product of soybean oil extraction and contains approximately 44% protein. We performed solid-state fermentation by using Bacillus subtilis strain N-2 to produce a water-soluble fertilizer containing amino acids. Strain N-2 produced a high yield of protease, which transformed the proteins in soybean meal into peptide and free amino acids that were dissolved in the fermentation products. Based on the Plackett-Burman design, the initial pH of the fermentation substrate, number of days of fermentation, and the ratio of liquid to soybean meal exhibited significant effects on the recovery of proteins in the resulting water-soluble solution. According to the predicted results of the central composite design, the highest recovery of soluble proteins (99.072%) was achieved at the optimum conditions. Under these conditions, the resulting solution contained 50.42% small peptides and 7.9% poly-γ-glutamic acid (γ-PGA). The water-soluble fertilizer robustly increased the activity of the rapeseed root system, chlorophyll content, leaf area, shoot dry weight, root length, and root weight at a concentration of 0.25% (w/v). This methodology offers a value-added use of soybean meal. Copyright © 2014 Elsevier B.V. All rights reserved.

Lipid immiscibility and biophysical properties: Molecular order within and among unit cell volumes

USDA-ARS?s Scientific Manuscript database

Saturated and unsaturated fatty acids clearly have a discrete chemical structure in the solid state. In a saturated solution, the solid state and solution state are in chemical equilibrium. The lipid stearic acid packs in unit cell volumes in the liquid state as well as in the solid state. Normal...

Paper-based solid-phase nucleic acid hybridization assay using immobilized quantum dots as donors in fluorescence resonance energy transfer.

PubMed

Noor, M Omair; Shahmuradyan, Anna; Krull, Ulrich J

2013-02-05

A paper-based solid-phase assay is presented for transduction of nucleic acid hybridization using immobilized quantum dots (QDs) as donors in fluorescence resonance energy transfer (FRET). The surface of paper was modified with imidazole groups to immobilize QD-probe oligonucleotide conjugates that were assembled in solution. Green-emitting QDs (gQDs) were FRET-paired with Cy3 acceptor. Hybridization of Cy3-labeled oligonucleotide targets provided the proximity required for FRET-sensitized emission from Cy3, which served as an analytical signal. The assay exhibited rapid transduction of nucleic acid hybridization within minutes. Without any amplification steps, the limit of detection of the assay was found to be 300 fmol with the upper limit of the dynamic range at 5 pmol. The implementation of glutathione-coated QDs for the development of nucleic acid hybridization assay integrated on a paper-based platform exhibited excellent resistance to nonspecific adsorption of oligonucleotides and showed no reduction in the performance of the assay in the presence of large quantities of noncomplementary DNA. The selectivity of nucleic acid hybridization was demonstrated by single-nucleotide polymorphism (SNP) detection at a contrast ratio of 19 to 1. The reuse of paper over multiple cycles of hybridization and dehybridization was possible, with less than 20% reduction in the performance of the assay in five cycles. This work provides an important framework for the development of paper-based solid-phase QD-FRET nucleic acid hybridization assays that make use of a ratiometric approach for detection and analysis.

Elements of an improved model of debris‐flow motion

USGS Publications Warehouse

Iverson, Richard M.

2009-01-01

A new depth‐averaged model of debris‐flow motion describes simultaneous evolution of flow velocity and depth, solid and fluid volume fractions, and pore‐fluid pressure. Non‐hydrostatic pore‐fluid pressure is produced by dilatancy, a state‐dependent property that links the depth‐averaged shear rate and volumetric strain rate of the granular phase. Pore‐pressure changes caused by shearing allow the model to exhibit rate‐dependent flow resistance, despite the fact that the basal shear traction involves only rate‐independent Coulomb friction. An analytical solution of simplified model equations shows that the onset of downslope motion can be accelerated or retarded by pore‐pressure change, contingent on whether dilatancy is positive or negative. A different analytical solution shows that such effects will likely be muted if downslope motion continues long enough, because dilatancy then evolves toward zero, and volume fractions and pore pressure concurrently evolve toward steady states.

Elements of an improved model of debris-flow motion

USGS Publications Warehouse

Iverson, R.M.

2009-01-01

A new depth-averaged model of debris-flow motion describes simultaneous evolution of flow velocity and depth, solid and fluid volume fractions, and pore-fluid pressure. Non-hydrostatic pore-fluid pressure is produced by dilatancy, a state-dependent property that links the depth-averaged shear rate and volumetric strain rate of the granular phase. Pore-pressure changes caused by shearing allow the model to exhibit rate-dependent flow resistance, despite the fact that the basal shear traction involves only rate-independent Coulomb friction. An analytical solution of simplified model equations shows that the onset of downslope motion can be accelerated or retarded by pore-pressure change, contingent on whether dilatancy is positive or negative. A different analytical solution shows that such effects will likely be muted if downslope motion continues long enough, because dilatancy then evolves toward zero, and volume fractions and pore pressure concurrently evolve toward steady states. ?? 2009 American Institute of Physics.

Friction stir weld tools having fine grain structure

DOEpatents

Grant, Glenn J.; Frye, John G.; Kim, Jin Yong; Lavender, Curt A.; Weil, Kenneth Scott

2016-03-15

Tools for friction stir welding can be made with fewer process steps, lower cost techniques, and/or lower cost ingredients than other state-of-the-art processes by utilizing improved compositions and processes of fabrication. Furthermore, the tools resulting from the improved compositions and processes of fabrication can exhibit better distribution and homogeneity of chemical constituents, greater strength, and/or increased durability. In one example, a friction stir weld tool includes tungsten and rhenium and is characterized by carbide and oxide dispersoids, by carbide particulates, and by grains that comprise a solid solution of the tungsten and rhenium. The grains do not exceed 10 micrometers in diameter.

Method for fabricating wrought components for high-temperature gas-cooled reactors and product

DOEpatents

Thompson, Larry D.; Johnson, Jr., William R.

1985-01-01

A method and alloys for fabricating wrought components of a high-temperature gas-cooled reactor are disclosed. These wrought, nickel-based alloys, which exhibit strength and excellent resistance to carburization at elevated temperatures, include aluminum and titanium in amounts and ratios to promote the growth of carburization resistant films while preserving the wrought character of the alloys. These alloys also include substantial amounts of molybdenum and/or tungsten as solid-solution strengtheners. Chromium may be included in concentrations less than 10% to assist in fabrication. Minor amounts of carbon and one or more carbide-forming metals also contribute to high-temperature strength.

Study of low-temperature active rare-earth oxide catalysts for automotive exhaust clean-up.

DOT National Transportation Integrated Search

2014-02-01

We report a facile onepot synthesis of CexZr1-xO2 (0x1) solid solution nanocrystals using hydrothermal reactions. A direct formation of oxide solid solutions in aqueous solution under pressure at low temperatures was clearly revealed by X-ra...

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

Xie, Miao; Mohammadi, Reza; Turner, Christopher L.

In this paper, we explore the hardening mechanisms in WB4-based solid solutions upon addition of Ta, Mn, and Cr using in situ radial X-ray diffraction techniques under nonhydrostatic pressure. By examining the lattice-supported differential strain, we provide insights into the mechanism for hardness increase in binary solid solutions at low dopant concentrations. Speculations on the combined effects of electronic structure and atomic size in ternary WB 4 solid solutions containing Ta with Mn or Cr are also included to understand the extremely high hardness of these materials.

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

Xie, Miao; Turner, Christopher L.; Mohammadi, Reza

In this work, we explore the hardening mechanisms in WB{sub 4}-based solid solutions upon addition of Ta, Mn, and Cr using in situ radial X-ray diffraction techniques under non-hydrostatic pressure. By examining the lattice-supported differential strain, we provide insights into the mechanism for hardness increase in binary solid solutions at low dopant concentrations. Speculations on the combined effects of electronic structure and atomic size in ternary WB{sub 4} solid solutions containing Ta with Mn or Cr are also included to understand the extremely high hardness of these materials.

Solid-solution thermodynamics in Al-Li alloys

NASA Astrophysics Data System (ADS)

Alekseev, A. A.; Lukina, E. A.

2016-05-01

The relative equilibrium concentrations of lithium atoms distributed over different electron-structural states has been estimated. The possibility of the existence of various nonequilibrium electron-structural states of Li atoms in the solid solution in Al has been substantiated thermodynamically. Upon the decomposition of the supersaturated solid solution, the supersaturation on three electron-structural states of Li atoms that arises upon the quenching of the alloy can lead to the formation of lithium-containing phases in which the lithium atoms enter in one electron-structural state.

Concentration Dependent Physical Properties of Ge1-xSnx Solid Solution

NASA Astrophysics Data System (ADS)

Jivani, A. R.; Jani, A. R.

2011-12-01

Our own proposed potential is used to investigate few physical properties like total energy, bulk modulus, pressure derivative of bulk modulus, elastic constants, pressure derivative of elastic constants, Poisson's ratio and Young's modulus of Ge1-xSnx solid solution with x is atomic concentration of α-Sn. The potential combines linear plus quadratic types of electron-ion interaction. First time screening function proposed by Sarkar et al is used to investigate the properties of the Ge-Sn solid solution system.

New anatase-type Til-2xNbxAlxO2 solid solution nanoparticles: direct formation, phase stability, and photocatalytic performance.

PubMed

Hirano, Masanori; Ito, Takaharu

2006-12-01

New anatase-type titania solid solutions co-doped with niobium and aluminum (Til-2xNbxAIlxO2 (X = 0 -0.20)) were synthesized as nanoparticles from precursor solutions of TiOSO4, NbCl5, and Al(NO3)3 under mild hydrothermal conditions at 180 degrees C for 5 h using the hydrolysis of urea. The lattice parameters a0 and c0 of anatase slightly and gradually increased, when the content of niobium and aluminum increased from X = 0 to 0.20. The crystallite size of anatase increased from 12 to 28 nm with increasing the value of X from 0 to 0.20. Their photocatalytic activity and adsorptivity were evaluated separately by the measurement of the concentration of methylene blue (MB) remained in the solution in the dark or under UV-light irradiation. The adsorptivity of TiO2 was improved by the formation of anatase-type Til-2xNbxAlxO2 solid solutions. The photocatalytic activity of anatase-type Til-2xNbxAlxO2 solid solutions was superior to that of commercially available anatase-type pure TiO2 (ST-01) and anatase-type pure TiO2 hydrothermally prepared. The new anatase phase of Til-2xNbxAlxO2 (X = 0-0.20) solid solutions existed stably up to 850 0C during heat treatment in air. In comparison with hydrothermal pure TiO2, the starting temperature of anatase-to-rutile phase transformation was delayed by the formation of Ti1-2xNbxAlxO, (X = 0-0.20) solid solutions, although its completing temperature was accelerated.

Ground-fire effects on the composition of dissolved and total organic matter in forest floor and soil solutions from Scots pine forests in Germany: new insights from solid state 13C NMR analysis

NASA Astrophysics Data System (ADS)

Näthe, Kerstin; Michalzik, Beate; Levia, Delphis; Steffens, Markus

2016-04-01

Fires represent an ecosystem disturbance and are recognized to seriously pertubate the nutrient budgets of forested ecosystems. While the effects of fires on chemical, biological, and physical soil properties have been intensively studied, especially in Mediterranean areas and North America, few investigations examined the effects of fire-induced alterations in the water-bound fluxes and the chemical composition of dissolved and particulate organic carbon and nitrogen (DOC, POC, DN, PN). The exclusion of the particulate organic matter fraction (0.45 μm < POM < 500 μm) potentially results in misleading inferences and budgeting gaps when studying the effects of fires on nutrient and energy fluxes. To our best knowledge, this is the first known study to present fire-induced changes on the composition of dissolved and total organic matter (DOM, TOM) in forest floor (FF) and soil solutions (A, B horizon) from Scots pine forests in Germany. In relation to control sites, we test the effects of low-severity fires on: (1) the composition of DOM and TOM in forest floor and soil solutions; and (2) the translocated amount of particulate in relation to DOC and DN into the subsoil. The project aims to uncover the mechanisms of water-bound organic matter transport along an ecosystem profile and its compositional changes following a fire disturbance. Forest floor and soil solutions were fortnightly sampled from March to December 2014 on fire-manipulated and control plots in a Scots pine forest in Central Germany. Shortly after the experimental duff fire in April 2014 pooled solutions samples were taken for solid-state 13C NMR spectroscopy to characterize DOM (filtered solution < 0.8μm pore size) and TOM in unfiltered solutions. Independent from fire manipulation, the composition of TOM was generally less aromatic (aromaticity index [%] according to Hatcher et al., 1981) with values between 18 (FF) - 25% (B horizon) than the DOM fraction with 23 (FF) - 27% (B horizon). For DOM in FF solution, fire manipulation caused an increase in aromaticity from 23 to 27% compared to the control, due to an increase of the aryl-C and a decrease of the O-alkyl-C and alkyl-C signal. Fire effects were leveled out in the mineral soil. For TOM, fire effects became notable only in the A horizon, exhibiting a decrease in aromaticity from 22 to 18% compared to the control, due to increased O-alkyl-C and diminished aryl-C proportions. Compared to the control, fire only caused minor DOC release rates (< 10%) in the FF and mineral soil, while DN in the FF was significantly mobilized (+ 40%) by fire exhibiting annual values of 33 at the control sites compared to 46 kg DN ha-1 at the fire treated sites. Compared to the control, fire events did not significantly enhance the proportion of POC and PN in the total C and N amounts exhibiting values between 10 and 20%. To fully understand the quality and amount of translocated organic C and N compounds within soils under both ambient as well as fire environments, dissolved and particulate size fractions need to be considered.

Major- and minor-metal composition of three distinct solid material fractions associated with Juan de Fuca hydrothermal fluids (northeast Pacific), and calculation of dilution fluid samples

USGS Publications Warehouse

Hinkley, T.K.; Seeley, J.L.; Tatsumoto, M.

1988-01-01

Three distinct types of solid material are associated with each sample of the hydrothermal fluid that was collected from the vents of the Southern Juan de Fuca Ridge. The solid materials appear to be representative of deposits on ocean floors near mid-ocean ridges, and interpretation of the chemistry of the hydrothermal solutions requires understanding of them. Sr isotopic evidence indicates that at least two and probably all three of these solid materials were removed from the solution with which they are associated, by precipitation or adsorption. This occurred after the "pure" hydrothermal fluid was diluted and thoroughly mixed with ambient seawater. The three types of solid materials, are, respectively, a coarse Zn- and Fe-rich material with small amounts of Na and Ca; a finer material also rich in Zn and Fe, but with alkali and alkaline-earth metals; and a scum composed of Ba or Zn, with either considerable Fe or Si, and Sr. Mineral identification is uncertain because of uncertain anion composition. Only in the cases of Ba and Zn were metal masses greater in solid materials than in the associated fluids. For all other metals measured, masses in fluids dwarf those in solids. The fluids themselves contain greater concentrations of all metals measured, except Mg, than seawater. We discuss in detail the relative merits of two methods of determining the mixing proportions of "pure" hydrothermal solution and seawater in the fluids, one based on Sr isotopes, and another previously used method based on Mg concentrations. Comparison of solute concentrations in the several samples shows that degree of dilution of "pure" hydrothermal solutions by seawater, and amounts of original solutes that were removed from it as solid materials, are not related. There is no clear evidence that appreciable amounts of solid materials were not conserved (lost) either during or prior to sample collection. ?? 1988.

Effect of varying Ga content in ZnO:GaN solid solution synthesized by solution combustion technique for photocatalytic applications

NASA Astrophysics Data System (ADS)

Menon, Sumithra Sivadas; Janani, R.; Baskar, K.; Gupta, Bhavana; Singh, Shubra

2017-05-01

ZnO:GaN (oxy)nitride solid solution has been established as the most efficient non-oxide photocatalyst for water splitting under visible irradiation with one step photoexcitation and also boasts a band gap tunability from 2.8 eV to 2.5 eV[1]. The solid solution of GaN in ZnO is formed by the intersubstitution of few of Zn/O ions by Ga/N ions, and this results in the introduction of new defect levels above the valence band which narrows the effective band gap enabling activity under visible region of spectra. In this work, we report the synthesis of ZnO:GaN solid solution by a solution combustion technique where metal nitrates and urea are used as precursors. The Zn/Ga ratio was varied from 16 to 1 in the precursors. The as synthesized samples were characterized as phase pure by X-ray diffraction, where the wurtzite structure was retained up to Zn/Ga ratio of 5. The Diffuse reflectance spectroscopy studies revealed that as the Ga content in the solid solution increases there is a reduction in band gap, from 2.9 eV to 2.4 eV. The reduced band gap of the samples facilitates its photocatalytic activity under visible region of the spectra as evaluated by photoelectrochemical measurements.

Method of fabricating lipid bilayer membranes on solid supports

NASA Technical Reports Server (NTRS)

Cho, Nam-Joon (Inventor); Frank, Curtis W. (Inventor); Glenn, Jeffrey S. (Inventor); Cheong, Kwang Ho (Inventor)

2012-01-01

The present invention provides a method of producing a planar lipid bilayer on a solid support. With this method, a solution of lipid vesicles is first deposited on the solid support. Next, the lipid vesicles are destabilized by adding an amphipathic peptide solution to the lipid vesicle solution. This destabilization leads to production of a planar lipid bilayer on the solid support. The present invention also provides a supported planar lipid bilayer, where the planar lipid bilayer is made of naturally occurring lipids and the solid support is made of unmodified gold or titanium oxide. Preferably, the supported planar lipid bilayer is continuous. The planar lipid bilayer may be made of any naturally occurring lipid or mixture of lipids, including, but not limited to phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylinsitol, cardiolipin, cholesterol, and sphingomyelin.

Conformation-Based Design and Synthesis of Apratoxin A Mimetics Modified at the α,β-Unsaturated Thiazoline Moiety.

PubMed

Onda, Yuichi; Masuda, Yuichi; Yoshida, Masahito; Doi, Takayuki

2017-08-10

We have demonstrated design, synthesis, and biological evaluation of apratoxin A mimetics. In the first generation, the moCys moiety was replaced with seven simple amino acids as their 3D structures can be similar to that of apratoxin A. Apratoxins M1-M7 were synthesized using solid-phase peptide synthesis and solution-phase macrolactamization. Apratoxin M7, which contains a piperidinecarboxylic acid moiety, exhibited potent cytotoxicity against HCT-116 cells. In the second generation, substitution of each amino acid residue in the tripeptide Tyr(Me)-MeAla-MeIle moiety in apratoxin M7 led to the development of the highly potent apratoxin M16 possessing biphenylalanine (Bph) instead of Tyr(Me), which exhibited an IC 50 value of 1.1 nM against HCT-116 cells. Moreover, compared to apratoxin A, apratoxin M16 exhibited a similarly high level of growth inhibitory activity against various cancer cell lines. The results indicate that apratoxin M16 could be a potential candidate as an anticancer agent.

Planet Patrol. An Educational Unit on Solid Waste Solutions for Grades 4-6.

ERIC Educational Resources Information Center

Shively, Patti J.; And Others

This educational unit on solid waste solutions is intended to convey to students an understanding of the four methods of solid waste handling, in priority order, as recommended by the Environmental Protection Agency: (1) reduction in the volume of waste produced; (2) recycling and composting; (3) waste combustion, i.e., incineration of waste; and…

Polarization-sensitive nanowire photodetectors based on solution-synthesized CdSe quantum-wire solids.

PubMed

Singh, Amol; Li, Xiangyang; Protasenko, Vladimir; Galantai, Gabor; Kuno, Masaru; Xing, Huili Grace; Jena, Debdeep

2007-10-01

Polarization-sensitive photodetectors are demonstrated using solution-synthesized CdSe nanowire (NW) solids. Photocurrent action spectra taken with a tunable white light source match the solution linear absorption spectra of the NWs, showing that the NW network is responsible for the device photoconductivity. Temperature-dependent transport measurements reveal that carriers responsible for the dark current through the nanowire solids are thermally excited across CdSe band gap. The NWs are aligned using dielectrophoresis between prepatterned electrodes using conventional optical photolithography. The photocurrent through the NW solid is found to be polarization-sensitive, consistent with complementary absorption (emission) measurements of both single wires and their ensembles. The range of solution-processed semiconducting NW materials, their facile synthesis, ease of device fabrication, and compatibility with a variety of substrates make them attractive for potential nanoscale polarization-sensitive photodetectors.

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

Ab initio calculation of excess properties of La{sub 1−x}(Ln,An){sub x}PO{sub 4} solid solutions

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

Li, Yan; JARA High-Performance Computing, Schinkelstrasse 2, 52062 Aachen; Kowalski, Piotr M., E-mail: p.kowalski@fz-juelich.de

2014-12-15

We used ab initio computational approach to predict the excess enthalpy of mixing and the corresponding regular/subregular model parameters for La{sub 1−x}Ln{sub x}PO{sub 4} (Ln=Ce,…, Tb) and La{sub 1−x}An{sub x}PO{sub 4} (An=Pu, Am and Cm) monazite-type solid solutions. We found that the regular model interaction parameter W computed for La{sub 1−x}Ln{sub x}PO{sub 4} solid solutions matches the few existing experimental data. Within the lanthanide series W increases quadratically with the volume mismatch between LaPO{sub 4} and LnPO{sub 4} endmembers (ΔV=V{sub LaPO{sub 4}}−V{sub LnPO{sub 4}}), so that W(kJ/mol)=0.618(ΔV(cm{sup 3}/mol)){sup 2}. We demonstrate that this relationship also fits the interaction parameters computedmore » for La{sub 1−x}An{sub x}PO{sub 4} solid solutions. This shows that lanthanides can be used as surrogates for investigation of the thermodynamic mixing properties of actinide-bearing solid solutions. - Highlights: • The excess enthalpies of mixing for monazite-type solid solutions are computed. • The excess enthalpies increase with the endmembers volume mismatch. • The relationship derived for lanthanides is transferable to La{sub 1−x}An{sub x}PO{sub 4} systems.« less

X-ray absorption investigation of local structural disorder in Ni 1-xFe x (x=0.10, 0.20, 0.35, and 0.50) alloys

DOE PAGES

Zhang, Fuxiang X.; Jin, Ke; Zhao, Shijun; ...

2017-04-27

Defect energetics in structural materials has long been recognized to be affected by specific alloy compositions. Significantly enhanced radiation resistance has recently been observed in concentrated solid-solution alloys. However, the link between local structural disorder and modified defect dynamics in solid solutions remains unclear. To reveal the atomic-level lattice distortion, the local structures of Ni and Fe in Ni 1-xFe x (x=0.1, 0.2, 0.35 and 0.5) solid solution alloys were measured with extended X-ray absorption fine structure (EXAFS) technique. The lattice constant and the first-neighbor distances increase with the increase of Fe content in the solid solutions. EXAFS measurements havemore » revealed that the bond length of Fe with surrounding atoms is 0.01-0.03 larger than that of Ni in the alloy systems. Debye-Waller factor of the Fe-Fe bonds in all the systems is also slightly larger than that of the Ni-Ni bond. EXAFS fitting suggests that the local structural disorder is enhanced with the addition of Fe elements in the solid solution. The local bonding environments from ab initio calculation are in good agreement with the experimental results, which suggest that the Fe has a larger first-neighbor bonding distance than that of Ni, and thus Ni atom inside the Ni-Fe solid solution alloys undergoes compressive strain.« less

X-ray absorption investigation of local structural disorder in Ni 1-xFe x (x=0.10, 0.20, 0.35, and 0.50) alloys

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

Zhang, Fuxiang X.; Jin, Ke; Zhao, Shijun

Defect energetics in structural materials has long been recognized to be affected by specific alloy compositions. Significantly enhanced radiation resistance has recently been observed in concentrated solid-solution alloys. However, the link between local structural disorder and modified defect dynamics in solid solutions remains unclear. To reveal the atomic-level lattice distortion, the local structures of Ni and Fe in Ni 1-xFe x (x=0.1, 0.2, 0.35 and 0.5) solid solution alloys were measured with extended X-ray absorption fine structure (EXAFS) technique. The lattice constant and the first-neighbor distances increase with the increase of Fe content in the solid solutions. EXAFS measurements havemore » revealed that the bond length of Fe with surrounding atoms is 0.01-0.03 larger than that of Ni in the alloy systems. Debye-Waller factor of the Fe-Fe bonds in all the systems is also slightly larger than that of the Ni-Ni bond. EXAFS fitting suggests that the local structural disorder is enhanced with the addition of Fe elements in the solid solution. The local bonding environments from ab initio calculation are in good agreement with the experimental results, which suggest that the Fe has a larger first-neighbor bonding distance than that of Ni, and thus Ni atom inside the Ni-Fe solid solution alloys undergoes compressive strain.« less

K2 Mn4 O8 /Reduced Graphene Oxide Nanocomposites for Excellent Lithium Storage and Adsorption of Lead Ions.

PubMed

Hao, Shu-Meng; Qu, Jin; Yang, Jing; Gui, Chen-Xi; Wang, Qian-Qian; Li, Qian-Jie; Li, Xiaofeng; Yu, Zhong-Zhen

2016-03-01

Ion diffusion efficiency at the solid-liquid interface is an important factor for energy storage and adsorption from aqueous solution. Although K 2 Mn 4 O 8 (KMO) exhibits efficient ion diffusion and ion-exchange capacities, due to its high interlayer space of 0.70 nm, how to enhance its mass transfer performance is still an issue. Herein, novel layered KMO/reduced graphene oxide (RGO) nanocomposites are fabricated through the anchoring of KMO nanoplates on RGO with a mild solution process. The face-to-face structure facilitates fast transfer of lithium and lead ions; thus leading to excellent lithium storage and lead ion adsorption. The anchoring of KMO on RGO not only increases electrical conductivity of the layered nanocomposites, but also effectively prevents aggregation of KMO nanoplates. The KMO/RGO nanocomposite with an optimal RGO content exhibits a first cycle charge capacity of 739 mA h g -1 , which is much higher than that of KMO (326 mA h g -1 ). After 100 charge-discharge cycles, it still retains a charge capacity of 664 mA h g -1 . For the adsorption of lead ions, the KMO/RGO nanocomposite exhibits a capacity of 341 mg g -1 , which is higher than those of KMO (305 mg g -1 ) and RGO (63 mg g -1 ) alone. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid-water detoxifying reagents for chemical and biological agents

DOEpatents

Hoffman, Dennis M [Livermore, CA; Chiu, Ing Lap [Castro Valley, CA

2006-04-18

Formation of solid-water detoxifying reagents for chemical and biological agents. Solutions of detoxifying reagent for chemical and biological agents are coated using small quantities of hydrophobic nanoparticles by vigorous agitation or by aerosolization of the solution in the presence of the hydrophobic nanoparticles to form a solid powder. For example, when hydrophobic fumed silica particles are shaken in the presence of IN oxone solution in approximately a 95:5-weight ratio, a dry powder results. The hydrophobic silica forms a porous coating of insoluble fine particles around the solution. Since the chemical or biological agent tends to be hydrophobic on contact with the weakly encapsulated detoxifying solution, the porous coating breaks down and the detoxifying reagent is delivered directly to the chemical or biological agent for maximum concentration at the point of need. The solid-water (coated) detoxifying solutions can be blown into contaminated ventilation ducting or other difficult to reach sites for detoxification of pools of chemical or biological agent. Once the agent has been detoxified, it can be removed by flushing the area with air or other techniques.

Influence of isotopic disorder on solid state amorphization and polyamorphism in solid H2O -D2O solutions

NASA Astrophysics Data System (ADS)

Gromnitskaya, E. L.; Danilov, I. V.; Lyapin, A. G.; Brazhkin, V. V.

2015-10-01

We present a low-temperature and high-pressure ultrasonic study of elastic properties of isotopic H2O-D2O solid solutions, comparing their properties with those of the isotopically pure H2O and D2O ices. Measurements were carried out for solid state amorphization (SSA) from 1h to high-density amorphous (HDA) ice upon compression up to 1.8 GPa at 77 K and for the temperature-induced (77 -190 K ) u-HDA (unrelaxed HDA) → e-HDA (expanded HDA) → low-density amorphous (LDA )→1 c cascade of ice transformations near room pressure. There are many similarities in the elasticity behaviour of H2O ,D2O , and H2O-D2O solid solutions, including the softening of the shear elastic modulus as a precursor of SSA and the HDA →LDA transition. We have found significant isotopic effects during H/D substitution, including elastic softening of H2O -D2O solid solutions with respect to the isotopically pure ices in the case of the bulk moduli of ices 1c and 1h and for both bulk and shear elastic moduli of HDA ice at high pressures (>1 GPa ) . This softening is related to the configurational isotopic disorder in the solid solutions. At low pressures, the isotope concentration dependence of the elastic moduli of u-HDA ice changes remarkably and becomes monotonic with pronounced change of the bulk modulus (≈20 %) .

Effect of epoxidation level on thermal properties and ionic conductivity of epoxidized natural rubber solid polymer nanocomposite electrolytes

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

Harun, Fatin; Chan, Chin Han; Winie, Tan

Effect of epoxide content on the thermal and conductivity properties of epoxidized natural rubber (ENR) solid polymer nanocomposite electrolytes was investigated. Commercial available epoxidized natural rubber having 25 (ENR25) and 50 mole% (ENR50) epoxide, respectively were incorporated with lithium perchlorate (LiClO{sub 4}) salt and titanium dioxide (TiO{sub 2}) nanofiller via solution casting method. The solid polymer nanocomposite electrolytes were characterized by differential scanning calorimetry (DSC) and impedance spectroscopy (IS) for their thermal properties and conductivity, respectively. It was evident that introduction of LiClO{sub 4} causes a greater increase in glass transition temperature (T{sub g}) and ionic conductivity of ENR50 asmore » compared to ENR25. Upon addition of TiO{sub 2} in ENR/LiClO{sub 4} system, a remarkable T{sub g} elevation was observed for both ENRs where ENR50 reveals a more pronounced changes. It is interesting to note that they exhibit different phenomenon in ionic conductivity with TiO{sub 2} loading where ENR25 shows enhancement of conductivity while ENR50 shows declination.« less

Effect of softening precipitate composition and surface characteristics on natural organic matter adsorption.

PubMed

Russell, Caroline G; Lawler, Desmond F; Speitel, Gerald E; Katz, Lynn E

2009-10-15

Natural organic matter (NOM) removal during water softening is thought to occur through adsorption onto or coprecipitation with calcium and magnesium solids. However, details of precipitate composition and surface chemistry and subsequent interactions with NOM are relatively unknown. In this study, zeta potentiometry analyses of precipitates formed from inorganic solutions under varying conditions (e.g., Ca-only, Mg-only, Ca + Mg, increasing lime or NaOH dose) indicated that both CaCO3 and Mg(OH)2 were positively charged at higher lime (Ca(OH)2) and NaOH doses (associated with pH values above 11.5), potentially yielding a greater affinity for adsorbing negatively charged organic molecules. Environmental scanning electron microscopy (ESEM) images of CaCO3 solids illustrated the rhombohedral shape characteristic of calcite. In the presence of increasing concentrations of magnesium, the CaCO3 rhombs shifted to more elongated crystals. The CaCO3 solids also exhibited increasingly positive surface charge from Mg incorporation into the crystal lattice, potentially creating more favorable conditions for adsorption of organic matter. NOM adsorption experiments using humic substances extracted from Lake Austin and Missouri River water elucidated the role of surface charge and surface area on adsorption.

Solid-state voltammetry-based electrochemical immunosensor for Escherichia coli using graphene oxide-Ag nanoparticle composites as labels.

PubMed

Jiang, Xiaochun; Chen, Kun; Wang, Jing; Shao, Kang; Fu, Tao; Shao, Feng; Lu, Donglian; Liang, Jiangong; Foda, M Frahat; Han, Heyou

2013-06-21

A new electrochemical immunosensor based on solid-state voltammetry was fabricated for the detection of Escherichia coli (E. coli) by using graphene oxide-Ag nanoparticle composites (P-GO-Ag) as labels. To construct the platform, Au nanoparticles (AuNPs) were first self-assembled on an Au electrode surface through cysteamine and served as an effective matrix for antibody (Ab) attachment. Under a sandwich-type immunoassay format, the analyte and the probe (P-GO-Ag-Ab) were successively captured onto the immunosensor. Finally, the bonded AgNPs were detected through a solid-state redox process in 0.2 M of KCl solution. Combining the advantages of the high-loading capability of graphene oxide with promoted electron-transfer rate of AuNPs, this immunosensor produced a 26.92-fold signal enhancement compared with the unamplified protocol. Under the optimal conditions, the immunosensor exhibited a wide linear dependence on the logarithm of the concentration of E. coli ranging from 50 to 1.0 × 10(6) cfu mL(-1) with a detection limit of 10 cfu mL(-1). Moreover, as a practical application, the proposed immunosensor was used to monitor E. coli in lake water with satisfactory results.

Coatable Li4 SnS4 Solid Electrolytes Prepared from Aqueous Solutions for All-Solid-State Lithium-Ion Batteries.

PubMed

Choi, Young Eun; Park, Kern Ho; Kim, Dong Hyeon; Oh, Dae Yang; Kwak, Hi Ram; Lee, Young-Gi; Jung, Yoon Seok

2017-06-22

Bulk-type all-solid-state lithium-ion batteries (ASLBs) for large-scale energy-storage applications have emerged as a promising alternative to conventional lithium-ion batteries (LIBs) owing to their superior safety. However, the electrochemical performance of bulk-type ASLBs is critically limited by the low ionic conductivity of solid electrolytes (SEs) and poor ionic contact between the active materials and SEs. Herein, highly conductive (0.14 mS cm -1 ) and dry-air-stable SEs (Li 4 SnS 4 ) are reported, which are prepared using a scalable aqueous-solution process. An active material (LiCoO 2 ) coated by solidified Li 4 SnS 4 from aqueous solutions results in a significant improvement in the electrochemical performance of ASLBs. Side-effects of the exposure of LiCoO 2 to aqueous solutions are minimized by using predissolved Li 4 SnS 4 solution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Creep Properties of the As-Cast Al-A319 Alloy: T4 and T7 Heat Treatment Effects

NASA Astrophysics Data System (ADS)

Erfanian-Naziftoosi, Hamid R.; Rincón, Ernesto J.; López, Hugo F.

2016-08-01

In this work, the creep behavior of a commercial Al-A319 alloy was investigated in the temperature range of 413 K to 533 K (140 °C to 260 °C). Tensile creep specimens in the as-cast condition and after heat treating by solid solution (T4) and by aging (T7) were tested in a stress range varying from 60 to 170 MPa. It was found that steady-state creep strain rate was significantly low in the T7 condition when compared with either the T4 or as-cast alloy conditions. As a result, the time to failure behavior considerably increased. The experimentally determined creep exponents measured from the stress-strain curves were 4 for the as-cast alloy, 7.5 in the solid solution, and 9.5 after aging. In particular, after solid solution a grain substructure was found to develop which indicated that creep in a constant subgrain structure was active, thus accounting for the n exponent of 7.5. In the aged condition, a stress threshold is considered to account for the power law creep exponent n of 9.5. Moreover, It was found that the creep activation energy values were rather similar for the alloys in the as-cast (134 kJ/mol) and T4 (146 kJ/mol) conditions. These values are close to the one corresponding to pure Al self-diffusion (143 kJ/mol). In the aged alloy, the apparent creep activation energy (202 kJ/mol) exceeded that corresponding to Al self-diffusion. This deviation in activation energy is attributed to the effect of temperature on the alloy elastic modulus. Microstructural observations using transmission electron microscopy provided further support for the various dislocation-microstructure interactions exhibited by the alloy under the investigated creep conditions and implemented heat treatments.

New catalysts and adsorbents on the basis of the InSb-CdTe semiconducting system

NASA Astrophysics Data System (ADS)

Kirovskaya, I. A.

2007-04-01

The acid-base properties of solid solutions and binary components of the InSb-CdTe system were studied by IR spectroscopy, pH isoelectric point measurements, and conductometric titration; adsorption properties with respect to CO, O2, NO2, NH3, CO + O2, and NO2 + NH3, by piezoquartz microweighing; and catalytic properties in the oxidation of carbon(II) oxide and reduction of nitrogen(IV) oxide with ammonia, by the pulsed and circulation flow methods. The nature, strength, and concentration of acid centers were determined. Changes in the concentration of acid centers under the action of gases (NO2 and NH3), gamma irradiation, and composition variations were estimated. The experimental dependences, thermodynamic and kinetic adsorption characteristics, the electrophysical, acid-base, and other physicochemical characteristics of the adsorbents, and adsorption characteristic-composition phase diagrams were analyzed taking into account the electronic nature of adsorbate molecules to determine the mechanism and characteristics of adsorption processes depending on the conditions of adsorption and the composition of the system. The results of adsorption studies were used to preliminarily determine the temperature regions of the occurrence and the mechanism of the reactions studied. A shock mechanism was suggested. Separate components (predominantly, solid solutions) of the InSb-CdTe system showed high catalytic activity at comparatively low temperatures. Along with behavior common to the system and its binary compounds (InSb and CdTe), solid solutions exhibited features characteristic of multi-component systems. These were the presence of extrema in the pHiso-composition, adsorption characteristic-composition, and catalytic activity-composition diagrams. The use of these diagrams allowed us to discover system components most active with respect to the gases and reactions studied and create high-sensitivity and selective sensors and high-activity and selective catalysts on the basis of these components.

Phonon scattering mechanisms dictating the thermal conductivity of lead zirconate titanate (PbZr 1- xTi xO 3) thin films across the compositional phase diagram

DOE PAGES

Foley, Brian M.; Paisley, Elizabeth A.; DiAntonio, Christopher; ...

2017-05-23

This paper represents a thorough investigation of the thermal conductivity (κ) in both thin film and bulk PbZr 1–xTi xO 3 (PZT) across the compositional phase diagram. Given the technological importance of PZT as a superb piezoelectric and ferroelectric material in devices and systems impacting a wide array of industries, this research serves to fill the gap in knowledge regarding the thermal properties. The thermal conductivities of both thin film and bulk PZT are found to vary by a considerable margin as a function of composition x. Additionally, we observe a discontinuity in κ in the vicinity of the morphotropicmore » phase boundary (MPB, x = 0.48) where there is a 20%–25% decrease in κ in our thin film data, similar to that found in literature data for bulk PZT. The comparison between bulk and thin film materials highlights the sensitivity of κ to size effects such as film thickness and grain size even in disordered alloy/solid-solution materials. A model for the thermal conductivity of PZT as a function of composition (κ(x)) is presented, which enables the application of the virtual crystal approximation for alloy-type material systems with very different crystals structures, resulting in differing temperature trends for κ. We show that in the case of crystalline solid-solutions where the thermal conductivity of one of the parent materials exhibits glass-like temperature trends the compositional dependence of thermal conductivity is relatively constant for most values of x. Finally, this is in stark contrast with the typical trends of thermal conductivity with x in alloys, where the thermal conductivity increases dramatically as the composition of the alloy or solid-solution approaches that of a pure parent materials (i.e., as x = 0 or 1).« less

Phonon scattering mechanisms dictating the thermal conductivity of lead zirconate titanate (PbZr 1- xTi xO 3) thin films across the compositional phase diagram

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

Foley, Brian M.; Paisley, Elizabeth A.; DiAntonio, Christopher

This paper represents a thorough investigation of the thermal conductivity (κ) in both thin film and bulk PbZr 1–xTi xO 3 (PZT) across the compositional phase diagram. Given the technological importance of PZT as a superb piezoelectric and ferroelectric material in devices and systems impacting a wide array of industries, this research serves to fill the gap in knowledge regarding the thermal properties. The thermal conductivities of both thin film and bulk PZT are found to vary by a considerable margin as a function of composition x. Additionally, we observe a discontinuity in κ in the vicinity of the morphotropicmore » phase boundary (MPB, x = 0.48) where there is a 20%–25% decrease in κ in our thin film data, similar to that found in literature data for bulk PZT. The comparison between bulk and thin film materials highlights the sensitivity of κ to size effects such as film thickness and grain size even in disordered alloy/solid-solution materials. A model for the thermal conductivity of PZT as a function of composition (κ(x)) is presented, which enables the application of the virtual crystal approximation for alloy-type material systems with very different crystals structures, resulting in differing temperature trends for κ. We show that in the case of crystalline solid-solutions where the thermal conductivity of one of the parent materials exhibits glass-like temperature trends the compositional dependence of thermal conductivity is relatively constant for most values of x. Finally, this is in stark contrast with the typical trends of thermal conductivity with x in alloys, where the thermal conductivity increases dramatically as the composition of the alloy or solid-solution approaches that of a pure parent materials (i.e., as x = 0 or 1).« less

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

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

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

2012-08-15

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

Fluidized bed gasification of extracted coal

DOEpatents

Aquino, Dolores C.; DaPrato, Philip L.; Gouker, Toby R.; Knoer, Peter

1986-01-01

Coal or similar carbonaceous solids are extracted by contacting the solids in an extraction zone (12) with an aqueous solution having a pH above 12.0 at a temperature between 65.degree. C. and 110.degree. C. for a period of time sufficient to remove bitumens from the coal into said aqueous solution and the extracted solids are then gasified at an elevated pressure and temperature in a fluidized bed gasification zone (60) wherein the density of the fluidized bed is maintained at a value above 160 kg/m.sup.3. In a preferred embodiment of the invention, water is removed from the aqueous solution in order to redeposit the extracted bitumens onto the solids prior to the gasification step.

76 FR 21299 - Emergency Planning and Notification; Emergency Planning and List of Extremely Hazardous...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-04-15

...EPA is proposing to revise the manner by which the regulated community would apply the threshold planning quantities (TPQs) for those extremely hazardous substances (EHSs) that are non-reactive solid chemicals in solution form. Specifically, facilities with a solid EHS in solution would be subject to the Emergency Planning requirements if the amount of the solid chemical on-site, when multiplied by 0.2, equaled or exceeded the lower published TPQ, based on data that shows less potential for the solid chemical in solution to remain airborne in the event of an accidental release. Previously, EPA assumed that 100% of the chemical could become airborne in the event of an accidental release.

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

Lee, Seung Min; Knight, Travis W.; Voit, Stwart L.

The solid solution of (U1-yFPy)O- 2±x, has the same fluorite structure as UO 2±x lambda, and the lattice parameter is affected by dissolved fission product and oxygen concentrations. We investigated the relation between the lattice parameter and the concentrations of neodymium and oxygen in the fluorite structure of (U 1-yNd y)O 2±x using X-ray diffraction. Moreover, the lattice parameter behavior in the (U 1-yNd y)O 2±x, solid solution shows a linear change as a function of the oxygen-to-metal ratio and solubility of neodymium. The lattice parameter depends on the radii of ions forming the fluorite structure and also can bemore » expressed by a particular rule (modified Vegard's law). Furthermore, the numerical analyses of the lattice parameters for the stoichiometric and nonstoichionietric solid solutions were conducted, and the lattice parameter model for the (U1-yNdy)O 2±x, solid solution was assessed. There is a very linear relationship between the lattice parameter and the Nd and O concentration for the stoichiometry and nonstoichiometry of the (U 1-yNd y)O 2±x solid solution was verified.« less

Ca and Fe modified biochars as adsorbents of arsenic and chromium in aqueous solutions.

PubMed

Agrafioti, Evita; Kalderis, Dimitrios; Diamadopoulos, Evan

2014-12-15

This work investigated the production of Ca and Fe modified biochars in order to use them for the removal of arsenic As(V) and chromium Cr(VI) from aqueous solutions. Rice husk was impregnated with CaO at an impregnation ratio 0.114, while both rice husk and the organic fraction of municipal solid wastes were impregnated with Fe(0) and Fe(3+) at impregnation ratios 0.114 and 0.23. The modified biochars exhibited high As(V) removal capacity (>95%), except for the case of rice husk impregnated with Fe(0), whose removal capacity reached only 58%. All modified biochars exhibited much better As(V) removal capacity compared to the non-impregnated biochars. However, the Cr(VI) removal rates were not as high as the As(V) ones. The maximum Cr(VI) removal was observed in the case of rice husk biochar impregnated with 2.3% w/w Fe(3+), whereas the majority of impregnation agents examined did not manage to enhance the biochars' Cr(VI) removal ability. The equilibrium study showed that the Freundlich model can adequately describe the sorption process for the majority of samples examined. Analysis of the amount of Fe present in the equilibrium solutions suggested that the main mechanisms of As(V) and Cr(VI) removal were possibly metal precipitation and electrostatic interactions between the modified biochars and the adsorbate. Copyright © 2014 Elsevier Ltd. All rights reserved.

Photophysical and antibacterial properties of complex systems based on smectite, a cationic surfactant and methylene blue.

PubMed

Donauerová, Alena; Bujdák, Juraj; Smolinská, Miroslava; Bujdáková, Helena

2015-10-01

Solid or colloidal materials with embedded photosensitizers are promising agents from the medical or environmental perspective, where the direct use of photoactive solutions appears to be problematic. Colloids based on layered silicates of the saponite (Sap) and montmorillonite (Mon) type, including those modified with dodecylammonium cations (C12) and photosensitizer--methylene blue (MB) were studied. Two representatives of bacteria, namely Enterobacter cloacae and Escherichia coli, were selected for this work. A spectral study showed that MB solutions and also colloids with Sap including C12 exhibited the highest photoactivities. The antimicrobial properties of the smectite colloids were not directly linked to the photoactivity of the adsorbed MB cations. They were also influenced by other parameters, such as light vs. dark conditions, the spectrum, power and duration of the light used for the irradiation; growth phases, and the pre-treatment of microorganisms. Both the photoactivity and antimicrobial properties of the colloids were improved upon pre-modification with C12. Significantly higher antimicrobial properties were observed for the colloids based on Mon with MB in the form of molecular aggregates without significant photoactivities. The MB/Mon colloids, both modified and non-modified with C12 cations, exhibited higher antimicrobial effects than pure MB solution. Besides the direct effect of photosensitization, the surface properties of the silicate particles likely played a crucial role in the interactions with microorganisms. Copyright © 2015 Elsevier B.V. All rights reserved.

Capillary-Channeled Polymer (C-CP) Fibers as a Stationary Phase for Sample Clean-Up of Protein Solutions for Matrix-Assisted Laser/Desorption Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Manard, Benjamin T.; Marcus, R. Kenneth

2012-08-01

Capillary-channeled polymer (C-CP) fibers are employed in a micropipette tip format to affect a stationary phase for the solid phase extraction (SPE) of proteins from buffer solutions prior to MALDI-MS analysis. Proteins readily adsorb to the polypropylene (PP) C-CP fibers while buffer species are easily washed off the tips using DI-H2O. Elution of the solutes is achieved with an aliquot of 50:50 ACN:H2O, which is compatible with the subsequent spotting on the MALDI target with the matrix solution. Lysozyme and cytochrome c are used as test species, with a primary buffer composition of 100 mM Tris-HCl. In this case, direct MALDI-MS produces no discernible protein signals. SPE on the C-CP fibers yields high fidelity mass spectra for 1 μL sample volumes. Limits of detection for cytochrome c in 100 mM Tris-HCl are on the order of 40 nM. Extraction of cytochrome c from buffer concentrations of up to 1 M Tris-HCl, provides signal recoveries that are suppressed by only ~50 % versus neat protein solutions. Finally, extraction of 3.1 μM cytochrome c from a synthetic urine matrix exhibits excellent recovery.

Solid-state one-way photoisomerisation of Z,E,Z-1,6-(4,4'-diphenyl)hexa-1,3,5-triene dicarboxylate examined using higher-order derivative spectra and powder XRD patterns.

PubMed

Sonoda, Yoriko; Goto, Midori; Ichimura, Kunihiro

2018-03-14

Higher order derivative spectra were applied at first to one-way ZEZ-to-EEE photoisomerisation of dimethyl ester (ZEZ-DPH1) of the titled compound in a methylcyclohexane solution. Many common crossing points emerged in UV-induced derivative-spectral changes to reveal the direct ZEZ-to-EEE photoisomerisation without the transient formation of an intermediate to suggest the bicycle-pedal mechanism. The solid-state photoisomerisation was subsequently monitored by tracing changes in the fourth-order derivatives of absorption spectra of a thin crystalline layer of ZEZ-DPH1 prepared by the drop-casting method, because the distortion of absorption spectra due to light scattering is cancelled. It was suggested that the solid-state photochemical event consists of three steps: fast ZEZ-to-EEE photoisomerisation, a subsequent slow ZEZ-to-EEE photoisomerisation and very slow disappearance of the EEE-isomer. Studies on powder XRD were also carried out for a drop-cast solid layer of ZEZ-DPH1 to disclose the coexistence of a crystal form other than the original one, and the former exhibited faster ZEZ-to-EEE photoisomerisation when compared with the original crystal form. The results revealed by XRD analysis are in line with those obtained by higher-order derivative spectra, confirming the solid-state one-way photoisomerisation to take place through the bicycle-pedal process.

A high performance flexible all solid state supercapacitor based on the MnO2 sphere coated macro/mesoporous Ni/C electrode and ionic conducting electrolyte.

PubMed

Zhi, Jian; Reiser, Oliver; Wang, Youfu; Hu, Aiguo

2016-06-09

A high contact resistance between the active materials and the current collector, a low ionic conductivity of the gel electrolyte, and an impenetrable electrode structure are the three major barriers which greatly limit the capacitance of MnO2 in solid state supercapacitors. As a potential solution to these problems, in this work we report a novel electrode for solid state supercapacitors, based on a ternary system composed of hierarchical MnO2 spheres as the active material, macroporous Ni foam as gel penetrable skeletons and an ordered mesoporous carbon (OMC) membrane as the charge-transport accelerating layer. By employing butyl-3-methylimidazolium chloride (BMIMCl) modified gels as the ionic conducting electrolyte, the utilization efficiency of MnO2 on the specific capacitance was enhanced up to 88% of the theoretical value, delivering a volumetric capacitance of 81 F cm(-3), which is the highest value among MnO2 based solid state supercapacitors. Moreover, such a flexible device exhibits exceptional volumetric energy and power density (6.6 Wh L(-1) and 549 W L(-1), based on the whole device volume) combined with a small capacity loss of 8.5% after 6000 cycles under twisting. These encouraging findings unambiguously overcome the energy bottleneck of MnO2 in solid state supercapacitors, and open up a new application of macro/mesoporous materials in flexible devices.

Semi-interpenetrating solid polymer electrolyte based on thiol-ene cross-linker for all-solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Suk, Jungdon; Lee, Yu Hwa; Kim, Do Youb; Kim, Dong Wook; Cho, Song Yun; Kim, Ji Man; Kang, Yongku

2016-12-01

We developed highly promising solid polymer electrolytes (SPEs) based on a novel cross-linker containing star-shaped phosphazene with poly(ethylene oxide) (PEO) branches with very high ionic conductivity (7.6 × 10-4 S cm-1), improved mechanical stability, and good electrochemical stability for all-solid-state lithium batteries. In particular, allyl groups were introduced at the ends of the cross-linker in order to overcome the easy self-polymerization of existing cross-linking acrylate end groups. A novel semi-interpenetrating network (semi-IPN) SPE was prepared by in-situ radical polymerization of a precursor solution containing lithium salt, poly(ethylene glycol) dimethyl ether as a plasticizer, and a mixture of pentaerythritol tetrakis(3-mercaptopropionate) and a synthesized hexakis(allyloxy)cyclotriphosphazene (thiol-ene PAL) as the cross-linker. Batteries employing LiFePO4 as the cathode, lithium foil as the anode, and the SPE thin film as the electrolyte were assembled and tested. At ambient temperature, the initial discharge capacity was 147 mAh/g at 0.1 °C and 132 mAh/g at 0.5 °C, and 97% of the capacity was retained at the 100th cycle. All-solid-state pouch-package lithium cells assembled with the SPEs exhibited stable electrochemical performance, even under a severely wrinkled state. These outstanding properties of SPEs based on thiol-ene PAL demonstrate feasibility for practical battery applications with improved reliability and safety.

Computer simulation of concentrated solid solution strengthening

NASA Technical Reports Server (NTRS)

Kuo, C. T. K.; Arsenault, R. J.

1976-01-01

The interaction forces between a straight edge dislocation moving through a three-dimensional block containing a random array of solute atoms were determined. The yield stress at 0 K was obtained by determining the average maximum solute-dislocation interaction force that is encountered by edge dislocation, and an expression relating the yield stress to the length of the dislocation and the solute concentration is provided. The magnitude of the solid solution strengthening due to solute atoms can be determined directly from the numerical results, provided the dislocation line length that moves as a unit is specified.

Enhancement of in-vitro drug dissolution of ketoconazole for its optimal in-vivo absorption using Nanoparticles and Solid Dispersion forms of the drug

NASA Astrophysics Data System (ADS)

Syed, Mohammed Irfan

Ketoconazole is one of the most widely prescribed oral antifungal drugs for the systemic treatment of various fungal infections. However, due its hydrophobic nature and poor solubility profiles in the gastro-intestinal fluids, variations in its bioavailability have been documented. Therefore, to enhance its dissolution in the biological fluids, this study was initiated to develop and evaluate Nanoparticles and Solid Dispersion forms of the drug. Nanoparticles of ketoconazole were developed by Wet Bead Milling technique using PVP-10k as the stabilizing material at a weight ratio of (2:1). Solid dispersion powder was prepared by Hot Melt method using PEG-8000 at a weight ratio of (1:2). A commercial product containing 200mg of ketoconazole tablet and pure drug powder were used as the control for comparison purposes. The dissolution studies were carried out in SGF, SIF, USP; and SIF with 0.2% sodium lauryl sulfate using the USP-II method for a 2 hours period. Physical characterizations were carried out using SEM, DSC, XRD and FTIR studies. Wet Bead Milling method yielded nanoparticles in the particles size range of (100-300nm.). First all samples were evaluated for their in-vitro dissolution in SGF at pH=1.2. After 15 minutes, the amounts of drug dissolved were observed to be 27% from both the pure powder and commercial tablet (control), 29% from solid dispersion and 100% from the Nanoparticles dosage form. This supports the fact that Nanoparticles had a strong influence on the dissolution rate of the drug and exhibited much faster dissolution of ketoconazole. When the same formulations were studied in the SIF, USP medium, the control formulation gave 3%, solid dispersion 8% and Nanoparticles 8% drug dissolution after 2 hours period. This could be because the weakly basic ketoconazole drug remained un-dissociated in the alkaline medium. Since this medium was unable to clearly distinguish the dissolution profiles from different formulation of the drug, the SIF solution was modified to include 0.02%, 0.05% and 0.1% sodium lauryl sulfate. Here, after 2 hours, the amount of drug dissolved was calculated to be 10% from controls, 21% from solid dispersion and 36% from nanoparticles in SIF with 0.02% SLS. Drug release was 20% from controls, 41% from solid dispersion and 52% from nanoparticle formulation in SIF with 0.05% SLS. Whereas amount of drug released in SIF with 0.1% SLS showed 21% from the control, 62% from solid dispersion and 85% from Nanoparticles respectively. This data supports that the ketoconazole Nanoparticles and its solid-dispersion exhibit many fold increase in dissolution of the drug, which could lead to a less variable and enhanced in-vivo drug absorption profiles. In addition, the data from the Physical Characterization (DSC, XRD and FTIR) supports that there were no interaction within the ingredients occurred in Nanoparticles and solid-dispersion formulations of the drug sample. Wet Bead Milling and Hot Melt methods proved useful in developing the Nanoparticles and solid dispersion form of ketoconazole. Results from particle size analysis were in correlation with data obtained from Scanning electron Microscopy and size of the nanoparticles was below 100nm. The dissolution studies with the modified simulated intestinal fluid (SIF) exhibited several fold increase in the dissolution of the drug compared to the pure drug powder and the commercial products used as the control. Also, the results from the physical characterization studies clearly support the stability of ketoconazole in both of these formulations.

Supercritical fluid molecular spray film deposition and powder formation

DOEpatents

Smith, Richard D.

1986-01-01

Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercritical fluid solution at an elevated pressure and then rapidly expanding the solution through a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. Upon expansion and supersonic interaction with background gases in the low pressure region, any clusters of solvent are broken up and the solvent is vaporized and pumped away. Solute concentration in the solution is varied primarily by varying solution pressure to determine, together with flow rate, the rate of deposition and to control in part whether a film or powder is produced and the granularity of each. Solvent clustering and solute nucleation are controlled by manipulating the rate of expansion of the solution and the pressure of the lower pressure region. Solution and low pressure region temperatures are also controlled.

A solid solution series of atacamite type Ni{sub 2x}Mg{sub 2−2x}Cl(OH){sub 3}

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

Bette, Sebastian; Dinnebier, Robert E.; Röder, Christian

2015-08-15

For the first time a complete solid solution series Ni{sub 2x}Mg{sub 2−2x}Cl(OH){sub 3} of an atacamite type alkaline main group metal chloride, Mg{sub 2}Cl(OH){sub 3}, and a transition group metal chloride, Ni{sub 2}Cl(OH){sub 3}, was prepared and characterized by chemical and thermal analysis as well as by Raman and IR spectroscopy, and high resolution laboratory X-ray powder diffraction. All members of the solid solution series crystallize in space group Pnam (62). The main building units of these crystal structures are distorted, edge-linked Ni/MgO{sub 4}Cl{sub 2} and Ni/MgO{sub 5}Cl octahedra. The distribution of Ni{sup 2+}- and Mg{sup 2+}-ions among these twomore » metal-sites within the solid solution series is discussed in detail. The crystallization of the solid solution phases occurs via an intermediate solid solution series, (Ni/Mg)Cl{sub 2x}(OH){sub 2−2x}, with variable Cl: OH ratio up to the 1:3 ratio according to the formula Ni{sub 2x}Mg{sub 2−2x} Cl(OH){sub 3}. For one isolated intermediate solid solution member, Ni{sub 0.70}Mg{sub 0.30}Cl{sub 0.58}(OH){sub 1.42}, the formation and crystal structure is presented as well. - Graphical abstract: For the first time a complete solid solution series, Ni{sub 2x}Mg{sub 2−2x} Cl(OH){sub 3}, was synthesized and characterized. Structure solution by revealed that Ni{sup 2+} prefers to occupy the Jahn–Teller-like distorted hole, out of two available cation sites. Substitution of Ni{sup 2+} by Mg{sup 2+} in atacamite type Ni{sub 2}Cl(OH){sub 3} results in systematic band shifts in Raman and IR spectra as well as in systematic changes in thermal properties. The α-polymorphs M{sub 2}Cl(OH){sub 3} with M=Mg{sup 2+}, Ni{sup 2+} and other divalent transition metal ions, as described in literature, were identified as separate compounds. - Highlights: • First synthesis of solid solution series between main and transition metal chloride. • Ni{sup 2+} prefers to occupy Jahn–Teller-like distorted octahedral holes. • Substitution of Ni{sup 2+} by Mg{sup 2+} results in systematic Raman and IR band shifts. • α-Polymorphs M{sub 2}Cl(OH){sub 3} with M=Mg{sup 2+}, Ni{sup 2+}, … as described in literature do not exist.« less

SOLIDS PRECIPITATION EVENT IN MCU CAUSAL ANALYSIS AND RECOMMENDATIONS FROM SOLIDS RECOVERY TEAM

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

Garrison, A.; Aponte, C.

A process upset occurred in the Modular Caustic-Side Solvent Extraction Unit (MCU) facility on April 6th, 2014. During recovery efforts, a significant amount of solids were found in the Salt Solution Feed Tank (SSFT), Salt Solution Receipt Tanks (SSRTs), two extraction contactors, and scrub contactors. The solids were identified by Savannah River National Laboratory (SRNL) as primarily sodium oxalate and sodium alumina silicate (NAS) with the presence of some aluminum hydroxide. NAS solids have been present in the SSFT since simulant runs during cold chemical startup of MCU in 2007, and have not hindered operations since that time. During themore » process upset in April 2014, the oxalate solids partially blocked the aqueous outlet of the extraction contactors, causing salt solution to exit through the contactor organic outlet to the scrub contactors with the organic phase. This salt solution overwhelmed the scrub contactors and passed with the organic phase to the strip section of MCU. The partially reversed flow of salt solution resulted in a Strip Effluent (SE) stream that was high in Isopar™ L, pH and sodium. The primary cause of the excessive solids accumulation in the SSRTs and SSFT at MCU is attributed to an increase in the frequency of oxalic acid cleaning of the 512-S primary filter. Agitation in the SSRTs at MCU in response to cold weather likely provided the primary mechanism to transfer the solids to the contactors. Sources of the sodium oxalate solids are attributed to the oxalic acid cleaning solution used to clean the primary filter at the Actinide Removal Process (ARP) filtration at 512-S, as well as precipitation from the salt batch feed, which is at or near oxalate saturation. The Solids Recovery Team was formed to determine the cause of the solids formation and develop recommendations to prevent or mitigate this event in the future. A total of 53 recommendations were generated. These recommendations were organized into 4 focus areas: • Improve understanding of oxalate equilibrium and kinetics in salt solutions • Reduction/elimination of oxalic acid cleaning in 512-S • Flowsheet optimization • Improving diagnostic capability The recommendations implemented prior to resumption of MCU operations provide a risk mitigation or detection function through additional sampling and observation. The longer term recommendations provide a framework to increase the basic process knowledge of both oxalate chemistry and filtration behavior and then facilitate decisions that improve the salt flowsheet as a system.« less

Finite element analysis of the effect of a non-planar solid-liquid interface on the lateral solute segregation during unidirectional solidification

NASA Technical Reports Server (NTRS)

Carlson, F. M.; Chin, L.-Y.; Fripp, A. L.; Crouch, R. K.

1982-01-01

The effect of solid-liquid interface shape on lateral solute segregation during steady-state unidirectional solidification of a binary mixture is calculated under the assumption of no convection in the liquid. A finite element technique is employed to compute the concentration field in the liquid and the lateral segregation in the solid with a curved boundary between the liquid and solid phases. The computational model is constructed assuming knowledge of the solid-liquid interface shape; no attempt is made to relate this shape to the thermal field. The influence of interface curvature on the lateral compositional variation is investigated over a range of system parameters including diffusivity, growth speed, distribution coefficient, and geometric factors of the system. In the limiting case of a slightly nonplanar interface, numerical results from the finite element technique are in good agreement with the analytical solutions of Coriell and Sekerka obtained by using linear theory. For the general case of highly non-planar interface shapes, the linear theory fails and the concentration field in the liquid as well as the lateral solute segregation in the solid can be calculated by using the finite element method.

Dielectric properties of A- and B-site doped BaTiO 3: Effect of La and Ga

NASA Astrophysics Data System (ADS)

Gulwade, Devidas; Gopalan, Prakash

2009-06-01

Extremely small amounts of La and Ga doping on the A- and B-site of BaTiO 3, respectively, resulting in a solid solution of the type Ba 1-3xLa 2xTi 1-3yGa 4yO 3 have been investigated. The present work dwells on the influence of the individual dopants, namely La and Ga, on the dielectric properties of BaTiO 3. The compositions have been prepared by solid-state reaction. X-ray diffraction (XRD) reveals the presence of tetragonal (P4/mmm) phase. The XRD data has been analyzed using FULLPROF, a Rietveld refinement package. The microstructure have been studied by orientation imaging microscopy (OIM). The compositions have been characterized by dielectric spectroscopy between room temperature and 250 °C. Further, the nature of phase transition has been studied using high temperature XRD. The resulting compounds exhibit high dielectric constant, enhanced diffuseness and low temperature coefficient of capacitance.

Hybrid solid polymer electrolyte from diapers as separator for electrochemical double layer capacitor (EDLC)

NASA Astrophysics Data System (ADS)

Hashim, Mohd Azman; Yatim, Nadhrah Md.; Mahmud, Nor Azura Che; Sazali, Nur Ezniera Shafieza; Hamdan, Ellisah; Yahya, Mohd Adib; Ngah, Che Wan Zanariah Che Wan; Suhaimi, Syahida

2018-06-01

EDLC was fabricated using hybrid solid polymer electrolyte from PVA-diapers and an activated carbon powder as electrode by using solution casting method. For comparison, four types of EDLC cells were constructed and tested. It was found that an EDLC with a PVA-diapers (60:40) polymer electrolyte exhibited much higher capacitance and longer cycle-life. The electrocapacitive properties of the supercapacitor (P50HD50, P60HD40, P70HD30 and P80HD20) were done using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and galvanostatic charge discharge (GCD). Results from these analysis showed that P60HD40 cell had recorded excellent rate capability and highest Csp value of 179 F g-1 (EIS), 50 F g-1 (CV), 328 F g-1 (GCD) respectively. Futher, results from ESR (GCD) analysis showed that P60HD40 composition of PVA/H3PO4 liquid electroyte gave a lower value of 88.05 Ω in the supercapacitor cell compared with another cells.

CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

NASA Astrophysics Data System (ADS)

Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

2014-07-01

An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system.

Band-gap tailoring and visible-light-driven photocatalytic performance of porous (GaN)1-x(ZnO)x solid solution.

PubMed

Wu, Aimin; Li, Jing; Liu, Baodan; Yang, Wenjin; Jiang, Yanan; Liu, Lusheng; Zhang, Xinglai; Xiong, Changmin; Jiang, Xin

2017-02-21

(GaN) 1-x (ZnO) x solid solution has attracted extensive attention due to its feasible band-gap tunability and excellent photocatalytic performance in overall water splitting. However, its potential application in the photodegradation of organic pollutants and environmental processing has rarely been reported. In this study, we developed a rapid synthesis process to fabricate porous (GaN) 1-x (ZnO) x solid solution with a tunable band gap in the range of 2.38-2.76 eV for phenol photodegradation. Under visible-light irradiation, (GaN) 0.75 (ZnO) 0.25 solid solution achieved the highest photocatalytic performance compared to other (GaN) 1-x (ZnO) x solid solutions with x = 0.45, 0.65 and 0.85 due to its higher redox capability and lower lattice deformation. Slight Ag decoration with a content of 1 wt% on the surface of the (GaN) 0.75 (ZnO) 0.25 solid solution leads to a significant enhancement in phenol degradation, with a reaction rate eight times faster than that of pristine (GaN) 0.75 (ZnO) 0.25 . Interestingly, phenol in aqueous solution (10 mg L -1 ) can also be completely degraded within 60 min, even under the direct exposure of sunlight irradiation. The photocurrent response indicates that the enhanced photocatalytic activity of (GaN) 0.75 (ZnO) 0.25 /Ag is directly induced by the improved transfer efficiency of the photogenerated electrons at the interface. The excellent phenol degradation performance of (GaN) 1-x (ZnO) x /Ag further broadens their promising photocatalytic utilization in environmental processing, besides in overall water splitting for hydrogen production.

Polypyrrole-polyoxometalate/reduced graphene oxide ternary nanohybrids for flexible, all-solid-state supercapacitors.

PubMed

Chen, Yuyun; Han, Min; Tang, Yujia; Bao, Jianchun; Li, Shunli; Lan, Yaqian; Dai, Zhihui

2015-08-11

Novel polypyrrole-polyoxometalate/reduced graphene oxide ternary nanohybrids (TNHs) are synthesized via a one-pot redox relay strategy. The TNHs exhibit high areal specific capacitance (2.61 mF cm(-2)), and the fabricated solid device also exhibits good rate capability, excellent flexibility and mechanical stability.

The exchange interactions and the state of manganese atoms in the solid solutions in Bi{sub 3}NbO{sub 7} of cubic and tetragonal modifications

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

Chezhina, N.V., E-mail: chezhina@nc2490.spb.edu; Zhuk, N.A.; Korolev, D.A.

2016-01-15

The comparative analysis of magnetic behavior of manganese-containing solid solutions Bi{sub 3}Nb{sub 1−x}Mn{sub x}O{sub 7−δ} (x=0.01−0.10) of cubic and tetragonal modifications was performed. Based on the results of magnetic susceptibility studies paramagnetic manganese atoms in solid solutions of cubic and tetragonal modifications were found to be in the form of Mn(III), Mn(IV) monomers and exchange-coupled dimers of Mn(III)–O–Mn(III), Mn(IV)–O–Mn(IV), Mn(III)–O–Mn(IV). The exchange parameters and the distribution of monomers and dimers in solid solutions as a function of the content of paramagnetic atoms were calculated. - Graphical abstract: Structural transition of cubic to tetragonal Bi{sub 3}NbO{sub 7−δ}.

Isotope Labeling for Solution and Solid-State NMR Spectroscopy of Membrane Proteins

PubMed Central

Verardi, Raffaello; Traaseth, Nathaniel J.; Masterson, Larry R.; Vostrikov, Vitaly V.; Veglia, Gianluigi

2013-01-01

In this chapter, we summarize the isotopic labeling strategies used to obtain high-quality solution and solid-state NMR spectra of biological samples, with emphasis on integral membrane proteins (IMPs). While solution NMR is used to study IMPs under fast tumbling conditions, such as in the presence of detergent micelles or isotropic bicelles, solid-state NMR is used to study the structure and orientation of IMPs in lipid vesicles and bilayers. In spite of the tremendous progress in biomolecular NMR spectroscopy, the homogeneity and overall quality of the sample is still a substantial obstacle to overcome. Isotopic labeling is a major avenue to simplify overlapped spectra by either diluting the NMR active nuclei or allowing the resonances to be separated in multiple dimensions. In the following we will discuss isotopic labeling approaches that have been successfully used in the study of IMPs by solution and solid-state NMR spectroscopy. PMID:23076578

Efficacy of pectin solution for preventing gastro-esophageal reflux events in patients with percutaneous endoscopic gastrostomy.

PubMed

Adachi, Kyoichi; Furuta, Kenji; Aimi, Masahito; Fukazawa, Kousuke; Shimura, Shino; Ohara, Shunji; Nakata, Shuji; Inoue, Yukiko; Ryuko, Kanji; Ishine, Junichi; Katoh, Kyoko; Hirata, Toshiaki; Ohhata, Shuzo; Katoh, Setsushi; Moriyama, Mika; Sumikawa, Masuko; Sanpei, Mari; Kinoshita, Yoshikazu

2012-05-01

The aim of this study was to determine the efficacy of pectin solution, which increases the viscosity of liquid nutrient, for prevention of gastro-esophageal reflux in comparison with half-solid nutrient. The subjects were 10 elderly patients undergoing percutaneous endoscopic gastrostomy feeding. Twenty-four-hour esophageal multichannel intraluminal impedance and pH testing was performed during intake of half-solid nutrient and a combination of pectin solution and liquid nutrient. During 4 h after delivery, there was no significant difference in the total number of gastro-esophageal reflux events between the feeding of the half-solid nutrient and the combination of pectin solution and liquid nutrient (5.7 ± 1.2 vs 5.3 ± 1.0/4 h). Acidic reflux after delivery of the half-solid nutrient was significantly more frequent than that after delivery of the combination of pectin solution and liquid nutrient (80.7% vs 60.4%, p = 0.018). The incidence of gastro-esophageal reflux reaching the upper portion of the esophagus tended to be higher during delivery of the half-solid nutrient than during delivery of the combination of pectin solution and liquid nutrient (47.4% vs 34.0%, p = 0.153). In conclusion, the usage of pectin solution combined with liquid nutrient is effective for preventing acidic gastro-esophageal reflux and gastro-esophageal reflux reaching the upper portion of the esophagus.

Asymmetrically Substituted and π-Conjugated 2,2'-Bipyridine Derivatives: Synthesis, Spectroscopy, Computation, and Crystallography.

PubMed

Bodapati, Ramakrishna; Sarma, Monima; Kanakati, Arunkumar; Das, Samar K

2015-12-18

A new series of monosubstituted styryl- and bistyryl-2,2'-bipyridine luminophores (compounds 16-23) have been synthesized via Horner-Wadsworth-Emmons reaction involving a monophosphonate and donor aromatic aldehydes. In the title chromophores, the amino donors are varied between acyclic and cyclic while the alkoxy donors are varied in terms of their number and position. The absorption maxima of these chromophores shift predominantly due to intramolecular charge transfer (ICT) between different donor and acceptor moieties. The title donor-acceptor molecules exhibit intense fluorescence in solution at room temperature, and their emissive behavior has been found to be highly sensitive to solvent polarity. The fluorescence spectra and quantum yields of all the chromophores were recorded in four different solvent media, and the chromophores 16, 17, 19, and 21 exhibit fluorescence in the solid state too. The influence of the nature and position of the donor functionalities in the conjugated backbone of the bipyridine moiety on the electronic absorption properties of the title chromophores (16-23) has been demonstrated, which has further been corroborated by DFT and TD-DFT computation both in gas phase and in solution phase. The crystal structure of compound 18 has been described as a representative member of the family (16-23).

Ion-Specific Modulation of Interfacial Interaction Potentials between Solid Substrates and Cell-Sized Particles Mediated via Zwitterionic, Super-Hydrophilic Poly(sulfobetaine) Brushes.

PubMed

Higaki, Yuji; Fröhlich, Benjamin; Yamamoto, Akihisa; Murakami, Ryo; Kaneko, Makoto; Takahara, Atsushi; Tanaka, Motomu

2017-02-16

Zwitterionic polymer brushes draw increasing attention not only because of their superhydrophilic, self-cleaning capability but also due to their excellent antifouling capacity. We investigated the ion-specific modulation of the interfacial interaction potential via densely packed, uniform poly(sulfobetaine) brushes. The vertical Brownian motion of a cell-sized latex particle was monitored by microinterferometry, yielding the effective interfacial interaction potentials V(Δh) and the autocorrelation function of height fluctuation. The potential curvature V″(Δh) exhibited a monotonic increase according to the increase in monovalent salt concentrations, implying the sharpening of the potential confinement. An opposite tendency was observed in CaCl 2 solutions, suggesting that the ion specific modulation cannot be explained by the classical Hofmeister series. When the particle fluctuation was monitored in the presence of free sulfobetaine molecules, the increase in [sulfobetaine] resulted in a distinct increase in hydrodynamic friction. This was never observed in all the other salt solutions, suggesting the interference of zwitterionic pairing of sulfobetaine side chains by the intercalation of sulfobetaine molecules into the brush layer. Furthermore, poly(sulfobetaine) brushes exhibited a very low V″(Δh) and hydrodynamic friction to human erythrocytes, which seems to explain the excellent blood repellency of zwitterionic polymer materials.

Comparative Study of the Structure of Hydroproducts Derived from Loblolly Pine and Straw Grass

DOE PAGES

Wu, Qiong; Huang, Lang; Yu, Shitao; ...

2017-05-26

We investigated the structural characteristics of products derived from the hydrothermal carbonization (HTC) of loblolly pine (LP) and straw grass (SG) via solid-state cross-polarization/magic angle spinning nuclear magnetic resonance (CP/MAS 13C NMR), heteronuclear single-quantum correlation nuclear magnetic resonance (HSQC-NMR), and solution 13C NMR and 31P NMR techniques. Our results revealed that after HTC, hydrochars from both LP and SG mainly consisted of a combination of lignin, furfural, and condensed polyaromatic structures with a high level of fixed carbon content and higher heating value (HHV). Hydrochar from LP exhibited a higher aryl to furan ratio, and those from SG contained moremore » aliphatic functional groups. Solution 13C NMR and HSQC revealed that both liquid chemicals were condensed polyphenolic structures with aliphatic groups that exist mainly in the form of side chains. Although the LP products exhibited a higher proportion of aromatic structures, the types of polyphenol and aliphatic C–H were more diverse in the SG products. Results also indicated that reactions such as chain scission and condensation occurred during hydrothermal carbonization processes. Overall, HTC was found to be an effective refinery treatment for converting different waste biomass into valuable energy materials and chemicals.« less

Comparative Study of the Structure of Hydroproducts Derived from Loblolly Pine and Straw Grass

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

Wu, Qiong; Huang, Lang; Yu, Shitao

We investigated the structural characteristics of products derived from the hydrothermal carbonization (HTC) of loblolly pine (LP) and straw grass (SG) via solid-state cross-polarization/magic angle spinning nuclear magnetic resonance (CP/MAS 13C NMR), heteronuclear single-quantum correlation nuclear magnetic resonance (HSQC-NMR), and solution 13C NMR and 31P NMR techniques. Our results revealed that after HTC, hydrochars from both LP and SG mainly consisted of a combination of lignin, furfural, and condensed polyaromatic structures with a high level of fixed carbon content and higher heating value (HHV). Hydrochar from LP exhibited a higher aryl to furan ratio, and those from SG contained moremore » aliphatic functional groups. Solution 13C NMR and HSQC revealed that both liquid chemicals were condensed polyphenolic structures with aliphatic groups that exist mainly in the form of side chains. Although the LP products exhibited a higher proportion of aromatic structures, the types of polyphenol and aliphatic C–H were more diverse in the SG products. Results also indicated that reactions such as chain scission and condensation occurred during hydrothermal carbonization processes. Overall, HTC was found to be an effective refinery treatment for converting different waste biomass into valuable energy materials and chemicals.« less

Inorganic chemistry of water and bed sediment in selected tributaries of the south Umpqua River, Oregon, 1998

USGS Publications Warehouse

Hinkle, Stephen R.

1999-01-01

Ten sites on small South Umpqua River tributaries were sampled for inorganic constituents in water and streambed sediment. In aqueous samples, high concentrations (concentrations exceeding U.S. Environmental Protection Agency criterion continuous concentration for the protection of aquatic life) of zinc, copper, and cadmium were detected in Middle Creek at Silver Butte, and the concentration of zinc was high at Middle Creek near Riddle. Similar patterns of trace-element occurrence were observed in streambed-sediment samples.The dissolved aqueous load of zinc carried by Middle Creek along the stretch between the upper site (Middle Creek at Silver Butte) and the lower site (Middle Creek near Riddle) decreased by about 0.3 pounds per day. Removal of zinc from solution between the upper and lower sites on Middle Creek evidently was occurring at the time of sampling. However, zinc that leaves the aqueous phase is not necessarily permanently lost from solution. For example, zinc solubility is pH-dependent, and a shift between solid and aqueous phases towards release of zinc to solution in Middle Creek could occur with a perturbation in stream-water pH. Thus, at least two potentially significant sources of zinc may exist in Middle Creek: (1) the upstream source(s) producing the observed high aqueous zinc concentrations and (2) the streambed sediment itself (zinc-bearing solid phases and/or adsorbed zinc). Similar behavior may be exhibited by copper and cadmium because these trace elements also were present at high concentrations in streambed sediment in the Middle Creek Basin.

Structural and electrochemical characterization and surface modification of layered solid solution oxide cathodes of lithium ion batteries

NASA Astrophysics Data System (ADS)

Wu, Yan

Lithium ion batteries are widely used to power portable electronic devices such as cell phones and laptop computers due to their high energy density. However, the currently used layered LiCoO2 cathode could deliver only 50 % of its theoretical capacity in practical lithium ion cells (140 mAh/g) due to the chemical and structural instabilities at deep charge with (1-x) < 0.5 in Li1-xCoO2. Also, cobalt is relatively expensive and toxic. These difficulties have generated enormous interest in alternative cathode hosts. In this regard, solid solutions between layered Li[Li1/3Mn2/3]O2 (commonly designated as Li2MnO3) and LiMO2 (M = Mn, Ni, Co)) have become appealing as some of them exhibit much higher capacity (˜ 250 mAh/g on charging to 4.8 V) with lower cost and better safety compared to LiCoO 2. This dissertation investigates the (1-z) Li[Li1/3Mn 2/3]O2 - (z) Li[Mn0.5-yNi0.5-yCo 2y]O2 (y = 1/12, 1/6 and 1/3 and 0.25 = z = 0.75) layered oxide cathodes, which belong to a solid solution series between layered Li[Li 1/3Mn2/3]O2 and Li[Mn0.5-yNi0.5-y Co2y]O2, with an aim to develop a better understanding of the charge-discharge mechanisms and optimize the electrochemical performance of these materials. To accomplish this, the structural and electrochemical characterization of the (1- z) Li[Li1/3Mn2/3]O2 - (z) Li[Mn 0.5-yNi0.5-yCo2y]O2 cathodes is carried out. It is found that the amount of oxygen loss is related to the lithium content in the transition metal layer, and the Co and Mn4+ contents play a role in influencing the electrochemical behavior. In addition, the chemically delithiated samples are found to transform to O1 or P3 structure with a vanishing of the superlattice reflections arising from cationic ordering in the transition metal layer due to the incorporation of protons from the chemical delithiation medium, while the electrochemically charged samples retain the initial O3 structure. These layered solid solution oxides exhibit high irreversible capacity (IRC) loss (difference between first charge and discharge capacity) values (up to 100 mAh/g), which have been reduced significantly by modifying the cathode surface with other materials like Al2O3, AlPO 4, and F-. For example, compared to an IRC of 75 mAh/g and a first discharge capacity of 253 mAh/g for the pristine Li[Li0.2 Mn0.54Ni0.13Co0.13]O2 (y = 1/6 and z = 0.4), the 3 wt. % Al2O3 modified sample exhibits a lower IRC of 41 mAh/g and a higher first discharge capacity of 285 mAh/g, which is two times higher than that achieved with the LiCoO 2 cathode. A careful and systematic analysis of the experimentally observed capacity and IRC values suggest that part of the oxide ion vacancies created during first charge is retained in the layered lattice in contrast to the idealized model (elimination of all oxide ion vacancies) proposed in the literature. The surface modification helps to retain even more number of oxide ion vacancies in the lattice, which leads to a lower IRC and higher discharge capacity values. Additionally, bulk cationic and anionic substitutions of Al3+ and F- in Li[Li0.17Mn0.58Ni0.25 ]O2 (y = 0 and z = 0.5) are found to sensitively decrease the amount of oxygen loss from the lattice.

Formulation design and photochemical studies on nanocrystal solid dispersion of curcumin with improved oral bioavailability.

PubMed

Onoue, Satomi; Takahashi, Haruki; Kawabata, Yohei; Seto, Yoshiki; Hatanaka, Junya; Timmermann, Barbara; Yamada, Shizuo

2010-04-01

Considerable interest has been focused on curcumin due to its use to treat a wide variety of disorders, however, the therapeutic potential of curcumin could often be limited by its poor solubility, bioavailability, and photostability. To overcome these drawbacks, efficacious formulations of curcumin, including nanocrystal solid dispersion (CSD-Cur), amorphous solid dispersion (ASD-Cur), and nanoemulsion (NE-Cur), were designed with the aim of improving physicochemical and pharmacokinetic properties. Physicochemical properties of the prepared formulations were characterized by scanning/transmission electron microscope for morphological analysis, laser diffraction, and dynamic light scattering for particle size analysis, and polarized light microscope, powder X-ray diffraction and differential scanning calorimetry for crystallinity assessment. In dissolution tests, all curcumin formulations exhibited marked improvement in the dissolution behavior when compared with crystalline curcumin. Significant improvement in pharmacokinetic behavior was observed in the newly developed formulations, as evidenced by 12- (ASD-Cur), 16- (CSD-Cur), and 9-fold (NE-Cur) increase of oral bioavailability. Upon photochemical characterization, curcumin was found to be photoreactive and photodegradable in the solution state, possibly via type 2 photochemical reaction, whereas high photochemical stability was seen in the solid formulations, especially CSD-Cur. On the basis of these observations, taken together with dissolution and pharmacokinetic behaviors, CSD strategy would be efficacious to enhance bioavailability of curcumin with high photochemical stability. 2009 Wiley-Liss, Inc. and the American Pharmacists Association

Amplified solid-state electrochemiluminescence detection of cholesterol in near-infrared range based on CdTe quantum dots decorated multiwalled carbon nanotubes@reduced graphene oxide nanoribbons.

PubMed

Huan, Juan; Liu, Qian; Fei, Airong; Qian, Jing; Dong, Xiaoya; Qiu, Baijing; Mao, Hanping; Wang, Kun

2015-11-15

An amplified solid-state electrochemiluminescence (ECL) biosensor for detection of cholesterol in near-infrared (NIR) range was constructed based on CdTe quantum dots (QDs) decorated multiwalled carbon nanotubes@reduced graphene nanoribbons (CdTe-MWCNTs@rGONRs), which were prepared by electrostatic interactions. The CdTe QDs decorated on the MWCNTs@rGONRs resulted in the amplified ECL intensity by ~4.5 fold and decreased onset potential by ~100 mV. By immobilization of the cholesterol oxidase (ChOx) and NIR CdTe-MWCNTs@rGONRs on the electrode surface, a solid-state ECL biosensor for cholesterol detection was constructed. When cholesterol was added to the detection solution, the immobilized ChOx catalyzed the oxidation of cholesterol to generate H2O2, which could be used as the co-reactant in the ECL system of CdTe-MWCNTs@rGONRs. The as-prepared biosensor exhibited good performance for cholesterol detection including good reproducibility, selectivity, and acceptable linear range from 1 μM to 1mM with a relative low detection limit of 0.33 μM (S/N=3). The biosensor was successfully applied to the determination of cholesterol in biological fluid and food sample, which would open a new possibility for development of solid-state ECL biosensors with NIR emitters. Copyright © 2015 Elsevier B.V. All rights reserved.

All-solid-state flexible microsupercapacitors based on reduced graphene oxide/multi-walled carbon nanotube composite electrodes

NASA Astrophysics Data System (ADS)

Mao, Xiling; Xu, Jianhua; He, Xin; Yang, Wenyao; Yang, Yajie; Xu, Lu; Zhao, Yuetao; Zhou, Yujiu

2018-03-01

All-solid-state flexible microsupercapacitors have been intensely investigated in order to meet the rapidly growing demands for portable microelectronic devices. Herein, we demonstrate a facile, readily scalable and cost-effective laser induction process for preparing reduced graphene oxide/multi-walled carbon nanotube composite, which can be used as the interdigital electrodes in microsupercapacitors. The obtained composite exhibits high volumetric capacitance about 49.35 F cm-3, which is nearly 5 times higher than that of the pristine reduced graphene oxide film in aqueous 1.0 M H2SO4 solution (measured at a current density of 5 A cm-3 in a three-electrode testing). Additionally, an all-solid-state flexible microsupercapacitor employing these composite electrodes with PVA/H3PO4 gel electrolyte delivers high volumetric energy density of 6.47 mWh cm-3 at 10 mW cm-3 under the current density of 20 mA cm-3 as well as achieve excellent cycling stability retaining 88.6% of its initial value and outstanding coulombic efficiency after 10,000 cycles. Furthermore, the microsupercapacitors array connected in series/parallel can be easily adjusted to achieve the demands in practical applications. Therefore, this work brings a promising new candidate of prepare technologies for all-solid-state flexible microsupercapacitors as miniaturized power sources used in the portable and wearable electronics.

Fluidized bed gasification of extracted coal

DOEpatents

Aquino, D.C.; DaPrato, P.L.; Gouker, T.R.; Knoer, P.

1984-07-06

Coal or similar carbonaceous solids are extracted by contacting the solids in an extraction zone with an aqueous solution having a pH above 12.0 at a temperature between 65/sup 0/C and 110/sup 0/C for a period of time sufficient to remove bitumens from the coal into said aqueous solution, and the extracted solids are then gasified at an elevated pressure and temperature in a fluidized bed gasification zone (60) wherein the density of the fluidized bed is maintained at a value above 160 kg/m/sup 3/. In a preferred embodiment of the invention, water is removed from the aqueous solution in order to redeposit the extracted bitumens onto the solids prior to the gasification step. 2 figs., 1 tab.

Suppression of vacancy cluster growth in concentrated solid solution alloys

DOE PAGES

Zhao, Shijun; Velisa, Gihan; Xue, Haizhou; ...

2016-12-13

Large vacancy clusters, such as stacking-fault tetrahedra, are detrimental vacancy-type defects in ion-irradiated structural alloys. Suppression of vacancy cluster formation and growth is highly desirable to improve the irradiation tolerance of these materials. In this paper, we demonstrate that vacancy cluster growth can be inhibited in concentrated solid solution alloys by modifying cluster migration pathways and diffusion kinetics. The alloying effects of Fe and Cr on the migration of vacancy clusters in Ni concentrated alloys are investigated by molecular dynamics simulations and ion irradiation experiment. While the diffusion coefficients of small vacancy clusters in Ni-based binary and ternary solid solutionmore » alloys are higher than in pure Ni, they become lower for large clusters. This observation suggests that large clusters can easily migrate and grow to very large sizes in pure Ni. In contrast, cluster growth is suppressed in solid solution alloys owing to the limited mobility of large vacancy clusters. Finally, the differences in cluster sizes and mobilities in Ni and in solid solution alloys are consistent with the results from ion irradiation experiments.« less

Carbon nanotube enhanced label-free detection of microRNAs based on hairpin probe triggered solid-phase rolling-circle amplification

NASA Astrophysics Data System (ADS)

Tian, Qianqian; Wang, Ying; Deng, Ruijie; Lin, Lei; Liu, Yang; Li, Jinghong

2014-12-01

The detection of microRNAs (miRNAs) is imperative for gaining a better understanding of the functions of these biomarkers and has great potential for the early diagnosis of human disease. High sensitivity and selectivity for miRNA detection brings new challenges. Herein, an ultrasensitive protocol for electrochemical detection of miRNA is designed through carbon nanotube (CNT) enhanced label-free detection based on hairpin probe triggered solid-phase rolling-circle amplification (RCA). Traditionally, RCA, widely applied for signal enhancement in the construction of a variety of biosensors, has an intrinsic limitation of ultrasensitive detection, as it is difficult to separate the enzymes, templates, and padlock DNAs from the RCA products in the homogeneous solution. We purposely designed a solid-phase RCA strategy, using CNTs as the solid substrate, integrated with a hairpin structured probe to recognize target miRNA. In the presence of miRNA the stem-loop structure will be unfolded, triggering the CNT based RCA process. Due to the efficient blocking effect originating from the polymeric RCA products, the label-free assay of miRNA exhibits an ultrasensitive detection limit of 1.2 fM. Furthermore, the protocol possesses excellent specificity for resolving lung cancer-related let-7 family members which have only one-nucleotide variations. The high sensitivity and selectivity give the method great potential for applications in online diagnostics and in situ detection in long-term development.The detection of microRNAs (miRNAs) is imperative for gaining a better understanding of the functions of these biomarkers and has great potential for the early diagnosis of human disease. High sensitivity and selectivity for miRNA detection brings new challenges. Herein, an ultrasensitive protocol for electrochemical detection of miRNA is designed through carbon nanotube (CNT) enhanced label-free detection based on hairpin probe triggered solid-phase rolling-circle amplification (RCA). Traditionally, RCA, widely applied for signal enhancement in the construction of a variety of biosensors, has an intrinsic limitation of ultrasensitive detection, as it is difficult to separate the enzymes, templates, and padlock DNAs from the RCA products in the homogeneous solution. We purposely designed a solid-phase RCA strategy, using CNTs as the solid substrate, integrated with a hairpin structured probe to recognize target miRNA. In the presence of miRNA the stem-loop structure will be unfolded, triggering the CNT based RCA process. Due to the efficient blocking effect originating from the polymeric RCA products, the label-free assay of miRNA exhibits an ultrasensitive detection limit of 1.2 fM. Furthermore, the protocol possesses excellent specificity for resolving lung cancer-related let-7 family members which have only one-nucleotide variations. The high sensitivity and selectivity give the method great potential for applications in online diagnostics and in situ detection in long-term development. Electronic supplementary information (ESI) available: Preparation of the chemically modified multi-walled carbon nanotubes (CNTs), characterization of the CNTs and modified CNTs, preparation of the circular probe, gel electrophoresis of the RCA products, and DNA probes as noted in the text. See DOI: 10.1039/c4nr05243a

Seasonal multiphase equilibria in the atmospheres of Titan and Pluto

NASA Astrophysics Data System (ADS)

Tan, S. P.; Kargel, J. S.

2017-12-01

At the extremely low temperatures in Titan's upper troposphere and on Pluto's surface, the atmospheres as a whole are subject to freeze into solid solutions, not pure ices. The presence of the solid phases introduces conditions with rich phase equilibria upon seasonal changes, even if the temperature undergoes only small changes. For the first time, the profile of atmospheric methane in Titan's troposphere will be reproduced complete with the solid solutions. This means that the freezing point, i.e. the altitude where the first solid phase appears, is determined. The seasonal change will also be evaluated both at the equator and the northern polar region. For Pluto, also for the first time, the seasonal solid-vapor equilibria will be evaluated. The fate of the two solid phases, the methane-rich and carbon-monoxide-rich solid solutions, will be analyzed upon temperature and pressure changes. Such investigations are enabled by the development of a molecular-based thermodynamic model for cryogenic chemical systems, referred to as CRYOCHEM, which includes solid solutions in its phase-equilibria calculations. The atmospheres of Titan and Pluto are modeled as ternary gas mixtures: nitrogen-methane-ethane and nitrogen-methane-carbon monoxide, respectively. Calculations using CRYOCHEM can provide us with compositions not only in two-phase equilibria, but also that in three-phase equilibria. Densities of all phases involved will also be calculated. For Titan, density inversion between liquid and solid phases will be identified and presented. In the inversion, the density of solid phase is less than that in the liquid phase. The method and results of this work will be useful for further investigations and modeling on the atmospheres of Titan, Pluto, and other bodies with similar conditions in the Solar System and beyond.

Scattering of focused ultrasonic beams by cavities in a solid half-space.

PubMed

Rahni, Ehsan Kabiri; Hajzargarbashi, Talieh; Kundu, Tribikram

2012-08-01

The ultrasonic field generated by a point focused acoustic lens placed in a fluid medium adjacent to a solid half-space, containing one or more spherical cavities, is modeled. The semi-analytical distributed point source method (DPSM) is followed for the modeling. This technique properly takes into account the interaction effect between the cavities placed in the focused ultrasonic field, fluid-solid interface and the lens surface. The approximate analytical solution that is available in the literature for the single cavity geometry is very restrictive and cannot handle multiple cavity problems. Finite element solutions for such problems are also prohibitively time consuming at high frequencies. Solution of this problem is necessary to predict when two cavities placed in close proximity inside a solid can be distinguished by an acoustic lens placed outside the solid medium and when such distinction is not possible.

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

PubMed

Purohit, Hitesh S; Taylor, Lynne S

2017-12-01

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

Characterization of molecular disorder in vapor-deposited thin films of aluminum tris(quinoline-8-olate) by one-dimensional 27Al NMR under magic angle spinning.

PubMed

Utz, Marcel; Nandagopal, Magesh; Mathai, Mathew; Papadimitrakopoulos, Fotios

2006-01-21

Aluminum tris (quinoline-8-olate) (Alq3) is used as an electron-transport layer in organic light-emitting diodes. The material can be obtained in a wide range of different solid phases, both crystalline and amorphous, by deposition from the vapor phase or from solution under controlled conditions. While the structure of the crystalline polymorphs of Alq3 has been investigated thoroughly by x-ray diffraction as well as solid-state NMR, very little information is currently available on the amount of structural disorder in the amorphous forms of Alq3. In the present contribution, we report the use of 27Al NMR spectroscopy in the solid state under magic angle spinning to extract such information from amorphous vapor deposits of Alq3. The NMR spectra obtained from these samples exhibit different degrees of broadening, reflecting distributions of the electric-field gradient tensor at the site of the aluminum ion. These distributions can be obtained from the NMR spectra by solving the corresponding inverse problem. From these results, the magnitude of structural disorder in terms of molecular geometry has been estimated by density-functional theory calculations. It was found that the electric-field gradient anisotropy delta follows a bimodal distribution. Its majority component is centered around delta values comparable to the meridianal alpha crystal polymorph and has a width of about 10%, corresponding to distortions of the molecular geometry of a few degrees in the orientation of the ligands. Alq3 samples obtained at higher deposition rates exhibit higher degrees of disorder. The minor component, present at about 7%, has a much smaller anisotropy, suggesting that it may be due to the facial isomer of Alq3.

Polymorphous Supercapacitors Constructed from Flexible Three-Dimensional Carbon Network/Polyaniline/MnO2 Composite Textiles.

PubMed

Wang, Jinjie; Dong, Liubing; Xu, Chengjun; Ren, Danyang; Ma, Xinpei; Kang, Feiyu

2018-04-04

Polymorphous supercapacitors were constructed from flexible three-dimensional carbon network/polyaniline (PANI)/MnO 2 composite textile electrodes. The flexible textile electrodes were fabricated through a layer-by-layer construction strategy: PANI, carbon nanotubes (CNTs), and MnO 2 were deposited on activated carbon fiber cloth (ACFC) in turn through an electropolymerization process, "dipping and drying" method, and in situ chemical reaction, respectively. In the fabricated ACFC/PANI/CNTs/MnO 2 textile electrodes, the ACFC/CNT hybrid framework serves as a porous and electrically conductive 3D network for the rapid transmission of electrons and electrolyte ions, where ACFC, PANI, and MnO 2 are high-performance supercapacitor electrode materials. In the electrolyte of H 2 SO 4 solution, the textile electrode-based symmetric supercapacitor delivers superior areal capacitance, energy density, and power density of 4615 mF cm -2 (for single electrode), 157 μW h cm -2 , and 10372 μW cm -2 , respectively, whereas asymmetric supercapacitor assembled with the prepared composite textile as the positive electrode and ACFC as the negative electrode exhibits an improved energy density of 413 μW h cm -2 and a power density of 16120 μW cm -2 . On the basis of the ACFC/PANI/CNTs/MnO 2 textile electrodes, symmetric and asymmetric solid-state textile supercapacitors with a PVA/H 2 SO 4 gel electrolyte were also produced. These solid-state textile supercapacitors exhibit good electrochemical performance and high flexibility. Furthermore, flexible solid-state fiber-like supercapacitors were prepared with fiber bundle electrodes dismantled from the above composite textiles. Overall, this work makes a meaningful exploration of the versatile applications of textile electrodes to produce polymorphous supercapacitors.

Self-mixing of fly larvae during feeding

NASA Astrophysics Data System (ADS)

Shishkov, Olga; Johnson, Christopher; Zhang, Bryan; Hu, David

2016-11-01

How do we sustainably feed a growing world population? One solution of increasing interest is the use of black solider fly larvae, pea-sized grubs envisioned to transform hundreds of tons of food waste into a sustainable protein source. Although startups across the world are raising these larvae, a physical understanding of how they should be raised and fed remains missing. In this study, we present experiments measuring their feeding rate as a function of number of larvae. We show that larger groups of larvae have greater mixing which entrains hungry larvae around the food, increasing feeding rate. Feeding of larvae thus differs from feeding of cattle or other livestock which exhibit less self-mixing.

Self mixing of fly larvae during feeding

NASA Astrophysics Data System (ADS)

Shishkov, Olga; Johnson, Christopher; Hu, David

How do we sustainably feed a growing world population? One solution of increasing interest is the use of black solider fly larvae, pea-sized grubs envisioned to transform hundreds of tons of food waste into a sustainable protein source. Although startups across the world are raising these larvae, a physical understanding of how they should be raised and fed remains missing. In this study, we present experiments measuring their feeding rate as a function of number of larvae. We show that larger groups of larvae have greater mixing which entrains hungry larvae around the food, increasing feeding rate. Feeding of larvae thus differs from feeding of cattle or other livestock which exhibit less self-mixing.

Enhanced damage resistance and novel defect structure of CrFeCoNi under in situ electron irradiation

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

He, Mo -Rigen; Wang, Shuai; Jin, Ke

Defect production and growth in CrFeCoNi, a single-phase concentrated solid solution alloy, is characterized using in situ electron irradiation inside a transmission electron microscope operated at 400–1250 kV and 400 °C. All observed defects are interstitial-type, either elliptical Frank loops or polygonal (mostly rhombus) perfect loops. Both forms of loops in CrFeCoNi exhibit a sublinear power law of growth that is > 40 times slower than the linear defect growth in pure Ni. Lastly, this result shows how compositional complexity impacts the production of Frenkel pairs and the agglomeration of interstitials into loops, and, thus, enhances the radiation tolerance.

Enhanced damage resistance and novel defect structure of CrFeCoNi under in situ electron irradiation

DOE PAGES

He, Mo -Rigen; Wang, Shuai; Jin, Ke; ...

2016-07-25

Defect production and growth in CrFeCoNi, a single-phase concentrated solid solution alloy, is characterized using in situ electron irradiation inside a transmission electron microscope operated at 400–1250 kV and 400 °C. All observed defects are interstitial-type, either elliptical Frank loops or polygonal (mostly rhombus) perfect loops. Both forms of loops in CrFeCoNi exhibit a sublinear power law of growth that is > 40 times slower than the linear defect growth in pure Ni. Lastly, this result shows how compositional complexity impacts the production of Frenkel pairs and the agglomeration of interstitials into loops, and, thus, enhances the radiation tolerance.

Assessment of empirical potential for MOX nuclear fuels and thermomechanical properties

NASA Astrophysics Data System (ADS)

Balboa, Hector; Van Brutzel, Laurent; Chartier, Alain; Le Bouar, Yann

2017-11-01

We assess five empirical interatomic potentials in the approximation of rigid ions and pair interactions for the (U1-y,Puy)O solid solution. The assessment compares available experimental data and Fink's recommendation with simulations on: the structural, thermodynamics, and mechanical properties over the full range of plutonium composition, from pure UO2 to pure PuO2 and for temperatures ranging from 300 K to the melting point. The best results are obtained by potentials referred as Cooper and Potashnikov potentials. The first one reproduces more accurately recommendations for the thermodynamics and mechanical properties exhibiting ductile-like behaviour during crack propagation, while the second one gives brittle behaviour at low temperature.

Solid-state properties and crystallization behavior of PHA-739521 polymorphs.

PubMed

Sun, Changquan Calvin

2006-08-17

PHA-739521 is an experimental compound that exhibits polymorphism. The two anhydrous crystal forms, I and II, are characterized using powder X-ray diffractometry, thermal analyses, moisture sorption gravimetry. Both Forms I and II are non-hygroscopic and are stable to compaction pressure. The melting temperature is about 152 degrees C for Form I and 168 degrees C for Form II. Forms I and II are enantiotropically related where Form I is more stable below a transition temperature of approximately 70 degrees C. Crystallization behavior of this compound from solutions and during heating is also studied. Information obtained is used to design an appropriate crystallization process to successfully manufacture desired polymorph at large scale.

High temperature coercive field behavior of Fe-Zr powder

NASA Astrophysics Data System (ADS)

Mishra, Debabrata; Perumal, A.; Srinivasan, A.

2009-04-01

We report the investigation of high temperature coercive field behavior of Fe80Zr20 nanocrystalline alloy powder having two-phase microstructure prepared by mechanical alloying process. Thermomagnetization measurement shows the presence of two different magnetic phase transitions corresponding to the amorphous matrix and nonequilibrium Fe(Zr) solid solution. Temperature dependent coercivity exhibits a sharp increase in its value close to the Curie temperature of the amorphous matrix. This feature is attributed to the loss of intergranular ferromagnetic exchange coupling between the nanocrystallites due to the paramagnetic nature of the amorphous matrix. The temperature dependent coercive field behavior is ascribed to the variations in both the effective anisotropy and the exchange stiffness constant with temperature.

Garnet: featured mineral group at the 1993 Tucson Show

USGS Publications Warehouse

Modreski, P.J.

1993-01-01

The garnets are a common but complex group of minerals. They are perhaps the mineral kingdom's best example of solid solution: a relationship in which minerals have chemical compositions that are intermediate between two or more ideal end-member species. In garnet, we deal with a complex group of solid-solution series between as many as 14 end-member minerals. The varying intergradations of solid solution between these different end-members help to explain the garnet group's variety of color, environment of occurrence, gem use, and variation in such physical properties as specific gravity, refractive index, and hardness. -from Author

Atomic-level simulation of ferroelectricity in perovskite solid solutions

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

Sepliarsky, M.; Instituto de Fisica Rosario, CONICET-UNR, Rosario,; Phillpot, S. R.

2000-06-26

Building on the insights gained from electronic-structure calculations and from experience obtained with an earlier atomic-level method, we developed an atomic-level simulation approach based on the traditional Buckingham potential with shell model which correctly reproduces the ferroelectric phase behavior and dielectric and piezoelectric properties of KNbO{sub 3}. This approach now enables the simulation of solid solutions and defected systems; we illustrate this capability by elucidating the ferroelectric properties of a KTa{sub 0.5}Nb{sub 0.5}O{sub 3} random solid solution. (c) 2000 American Institute of Physics.

[Experimental investigation of the straw pre-treatment to enhance its high solid anaerobic digestion].

PubMed

Jiang, Jian-Guo; Zhao, Zhen-Zhen; Du, Xue-Juan; Sui, Ji-Chao; Wu, Shi-Yao

2007-04-01

The straw contains a high content of lignin, which cannot be well utilized by anaerobic bacteria in high solid anaerobic digestion process. This paper presents the experimental investigation of the straw pre-treatment, which aims to destroy the complex structure of the lignin to enhance its high solid anaerobic digestion. The straw is pre-treated in different solutions including NaOH, ammonia, H2SO4, and carbamide. The pre-treating effects are expressed by COD concentration dissolved in the solutions and the 14-day biogas generation in the enhanced aerogenic experiment. Different affecting factors, such as the concentration of the chemical solution, the species of the straw, the pre-treatment reaction time, the reaction temperature and the size of the straw, are investigated. The results show that NaOH solution is the most effective pre-treatment chemical among the four different solutions. The experimental results still indicate that the accumulative biogas production can be 1 500 mL (10 g straw) in 14 days after pre-treatment in 4 mg/L NaOH solution and the dissolved COD in the solution reaches 39 000 mg/L after 24 hours. In addition, the experiment shows that the lignin content in the straw is reduced from 28% to 19% after pre-treatment in 1.5% (in weight) NaOH solution, and it can improve the straw treatment efficiency using high solid anaerobic digestion process.

Quinary wurtzite Zn-Ga-Ge-N-O solid solutions and their photocatalytic properties under visible light irradiation

PubMed Central

Xie, Yinghao; Wu, Fangfang; Sun, Xiaoqin; Chen, Hongmei; Lv, Meilin; Ni, Shuang; Liu, Gang; Xu, Xiaoxiang

2016-01-01

Wurtzite solid solutions between GaN and ZnO highlight an intriguing paradigm for water splitting into hydrogen and oxygen using solar energy. However, large composition discrepancy often occurs inside the compound owing to the volatile nature of Zn, thereby prescribing rigorous terms on synthetic conditions. Here we demonstrate the merits of constituting quinary Zn-Ga-Ge-N-O solid solutions by introducing Ge into the wurtzite framework. The presence of Ge not only mitigates the vaporization of Zn but also strongly promotes particle crystallization. Synthetic details for these quinary compounds were systematically explored and their photocatalytic properties were thoroughly investigated. Proper starting molar ratios of Zn/Ga/Ge are of primary importance for single phase formation, high particle crystallinity and good photocatalytic performance. Efficient photocatalytic hydrogen and oxygen production from water were achieved for these quinary solid solutions which is strongly correlated with Ge content in the structure. Apparent quantum efficiency for optimized sample approaches 1.01% for hydrogen production and 1.14% for oxygen production. Theoretical calculation reveals the critical role of Zn for the band gap reduction in these solid solutions and their superior photocatalytic acitivity can be understood by the preservation of Zn in the structure as well as a good crystallinity after introducing Ge. PMID:26755070

Quinary wurtzite Zn-Ga-Ge-N-O solid solutions and their photocatalytic properties under visible light irradiation.

PubMed

Xie, Yinghao; Wu, Fangfang; Sun, Xiaoqin; Chen, Hongmei; Lv, Meilin; Ni, Shuang; Liu, Gang; Xu, Xiaoxiang

2016-01-12

Wurtzite solid solutions between GaN and ZnO highlight an intriguing paradigm for water splitting into hydrogen and oxygen using solar energy. However, large composition discrepancy often occurs inside the compound owing to the volatile nature of Zn, thereby prescribing rigorous terms on synthetic conditions. Here we demonstrate the merits of constituting quinary Zn-Ga-Ge-N-O solid solutions by introducing Ge into the wurtzite framework. The presence of Ge not only mitigates the vaporization of Zn but also strongly promotes particle crystallization. Synthetic details for these quinary compounds were systematically explored and their photocatalytic properties were thoroughly investigated. Proper starting molar ratios of Zn/Ga/Ge are of primary importance for single phase formation, high particle crystallinity and good photocatalytic performance. Efficient photocatalytic hydrogen and oxygen production from water were achieved for these quinary solid solutions which is strongly correlated with Ge content in the structure. Apparent quantum efficiency for optimized sample approaches 1.01% for hydrogen production and 1.14% for oxygen production. Theoretical calculation reveals the critical role of Zn for the band gap reduction in these solid solutions and their superior photocatalytic acitivity can be understood by the preservation of Zn in the structure as well as a good crystallinity after introducing Ge.

Contribution of Lattice Distortion to Solid Solution Strengthening in a Series of Refractory High Entropy Alloys

NASA Astrophysics Data System (ADS)

Chen, H.; Kauffmann, A.; Laube, S.; Choi, I.-C.; Schwaiger, R.; Huang, Y.; Lichtenberg, K.; Müller, F.; Gorr, B.; Christ, H.-J.; Heilmaier, M.

2018-03-01

We present an experimental approach for revealing the impact of lattice distortion on solid solution strengthening in a series of body-centered-cubic (bcc) Al-containing, refractory high entropy alloys (HEAs) from the Nb-Mo-Cr-Ti-Al system. By systematically varying the Nb and Cr content, a wide range of atomic size difference as a common measure for the lattice distortion was obtained. Single-phase, bcc solid solutions were achieved by arc melting and homogenization as well as verified by means of scanning electron microscopy and X-ray diffraction. The atomic radii of the alloying elements for determination of atomic size difference were recalculated on the basis of the mean atomic radii in and the chemical compositions of the solid solutions. Microhardness (μH) at room temperature correlates well with the deduced atomic size difference. Nevertheless, the mechanisms of microscopic slip lead to pronounced temperature dependence of mechanical strength. In order to account for this particular feature, we present a combined approach, using μH, nanoindentation, and compression tests. The athermal proportion to the yield stress of the investigated equimolar alloys is revealed. These parameters support the universality of this aforementioned correlation. Hence, the pertinence of lattice distortion for solid solution strengthening in bcc HEAs is proven.

Quinary wurtzite Zn-Ga-Ge-N-O solid solutions and their photocatalytic properties under visible light irradiation

NASA Astrophysics Data System (ADS)

Xie, Yinghao; Wu, Fangfang; Sun, Xiaoqin; Chen, Hongmei; Lv, Meilin; Ni, Shuang; Liu, Gang; Xu, Xiaoxiang

2016-01-01

Wurtzite solid solutions between GaN and ZnO highlight an intriguing paradigm for water splitting into hydrogen and oxygen using solar energy. However, large composition discrepancy often occurs inside the compound owing to the volatile nature of Zn, thereby prescribing rigorous terms on synthetic conditions. Here we demonstrate the merits of constituting quinary Zn-Ga-Ge-N-O solid solutions by introducing Ge into the wurtzite framework. The presence of Ge not only mitigates the vaporization of Zn but also strongly promotes particle crystallization. Synthetic details for these quinary compounds were systematically explored and their photocatalytic properties were thoroughly investigated. Proper starting molar ratios of Zn/Ga/Ge are of primary importance for single phase formation, high particle crystallinity and good photocatalytic performance. Efficient photocatalytic hydrogen and oxygen production from water were achieved for these quinary solid solutions which is strongly correlated with Ge content in the structure. Apparent quantum efficiency for optimized sample approaches 1.01% for hydrogen production and 1.14% for oxygen production. Theoretical calculation reveals the critical role of Zn for the band gap reduction in these solid solutions and their superior photocatalytic acitivity can be understood by the preservation of Zn in the structure as well as a good crystallinity after introducing Ge.

Superhard Rhenium/Tungsten Diboride Solid Solutions.

PubMed

Lech, Andrew T; Turner, Christopher L; Lei, Jialin; Mohammadi, Reza; Tolbert, Sarah H; Kaner, Richard B

2016-11-02

Rhenium diboride (ReB 2 ), containing corrugated layers of covalently bonded boron, is a superhard metallic compound with a microhardness reaching as high as 40.5 GPa (under an applied load of 0.49 N). Tungsten diboride (WB 2 ), which takes a structural hybrid between that of ReB 2 and AlB 2 , where half of the boron layers are planar (as in AlB 2 ) and half are corrugated (as in ReB 2 ), has been shown not to be superhard. Here, we demonstrate that the ReB 2 -type structure can be maintained for solid solutions of tungsten in ReB 2 with tungsten content up to a surprisingly large limit of nearly 50 atom %. The lattice parameters for the solid solutions linearly increase along both the a- and c-axes with increasing tungsten content, as evaluated by powder X-ray and neutron diffraction. From micro- and nanoindentation hardness testing, all of the compositions within the range of 0-48 atom % W are superhard, and the bulk modulus of the 48 atom % solid solution is nearly identical to that of pure ReB 2 . These results further indicate that ReB 2 -structured compounds are superhard, as has been predicted from first-principles calculations, and may warrant further studies into additional solid solutions or ternary compounds taking this structure type.

Diffuse interface immersed boundary method for multi-fluid flows with arbitrarily moving rigid bodies

NASA Astrophysics Data System (ADS)

Patel, Jitendra Kumar; Natarajan, Ganesh

2018-05-01

We present an interpolation-free diffuse interface immersed boundary method for multiphase flows with moving bodies. A single fluid formalism using the volume-of-fluid approach is adopted to handle multiple immiscible fluids which are distinguished using the volume fractions, while the rigid bodies are tracked using an analogous volume-of-solid approach that solves for the solid fractions. The solution to the fluid flow equations are carried out using a finite volume-immersed boundary method, with the latter based on a diffuse interface philosophy. In the present work, we assume that the solids are filled with a "virtual" fluid with density and viscosity equal to the largest among all fluids in the domain. The solids are assumed to be rigid and their motion is solved using Newton's second law of motion. The immersed boundary methodology constructs a modified momentum equation that reduces to the Navier-Stokes equations in the fully fluid region and recovers the no-slip boundary condition inside the solids. An implicit incremental fractional-step methodology in conjunction with a novel hybrid staggered/non-staggered approach is employed, wherein a single equation for normal momentum at the cell faces is solved everywhere in the domain, independent of the number of spatial dimensions. The scalars are all solved for at the cell centres, with the transport equations for solid and fluid volume fractions solved using a high-resolution scheme. The pressure is determined everywhere in the domain (including inside the solids) using a variable coefficient Poisson equation. The solution to momentum, pressure, solid and fluid volume fraction equations everywhere in the domain circumvents the issue of pressure and velocity interpolation, which is a source of spurious oscillations in sharp interface immersed boundary methods. A well-balanced algorithm with consistent mass/momentum transport ensures robust simulations of high density ratio flows with strong body forces. The proposed diffuse interface immersed boundary method is shown to be discretely mass-preserving while being temporally second-order accurate and exhibits nominal second-order accuracy in space. We examine the efficacy of the proposed approach through extensive numerical experiments involving one or more fluids and solids, that include two-particle sedimentation in homogeneous and stratified environment. The results from the numerical simulations show that the proposed methodology results in reduced spurious force oscillations in case of moving bodies while accurately resolving complex flow phenomena in multiphase flows with moving solids. These studies demonstrate that the proposed diffuse interface immersed boundary method, which could be related to a class of penalisation approaches, is a robust and promising alternative to computationally expensive conformal moving mesh algorithms as well as the class of sharp interface immersed boundary methods for multibody problems in multi-phase flows.

Effect of Antifoam Agent on Oxidative Leaching of Hanford Tank Sludge Simulants

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

Rapko, Brian M.; Jones, Susan A.; Lumetta, Gregg J.

2010-02-26

Oxidative leaching of simulant tank waste containing an antifoam agent (AFA) to reduce the chromium content of the sludge was tested using permanganate as the oxidant in 0.25 M NaOH solutions. AFA is added to the waste treatment process to prevent foaming. The AFA, Dow Corning Q2-3183A, is a surface-active polymer that consists of polypropylene glycol, polydimethylsiloxane, octylphenoxy polyethoxy ethanol, treated silica, and polyether polyol. Some of the Hanford Tank Waste Treatment and Immobilization Plant (WTP) waste slurries contain high concentrations of undissolved solids that would exhibit undesirable behavior without AFA addition. These tests were conducted to determine the effectmore » of the AFA on oxidative leaching of Cr(III) in waste by permanganate. It has not previously been determined what effect AFA has on the permanganate reaction. This study was conducted to determine the effect AFA has on the oxidation of the chromium, plus plutonium and other criticality-related elements, specifically Fe, Ni and Mn. During the oxidative leaching process, Mn is added as liquid permanganate solution and is converted to an insoluble solid that precipitates as MnO2 and becomes part of the solid waste. Caustic leaching was performed followed by an oxidative leach at either 25°C or 45°C. Samples of the leachate and solids were collected at each step of the process. Initially, Battelle-Pacific Northwest Division (PNWD) was contracted by Bechtel National, Inc. to perform these further scoping studies on oxidative alkaline leaching. The data obtained from the testing will be used by the WTP operations to develop procedures for permanganate dosing of Hanford tank sludge solids during oxidative leaching. Work was initially conducted under contract number 24590-101-TSA-W000-00004. In February 2007, the contract mechanism was switched to Pacific Northwest National Laboratory (PNNL) operating Contract DE-AC05-76RL01830. In summary, this report describes work focused on determining the effect of AFA on chromium oxidation by permanganate with Hanford sludge simulant.« less

Method of making supercritical fluid molecular spray films, powder and fibers

DOEpatents

Smith, Richard D.

1988-01-01

Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercritical fluid solution at an elevated pressure and then rapidly expanding the solution through a heated nozzle having a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. In another embodiment, the temperature of the solution and nozzle is elevated above the melting point of the solute, which is preferably a polymer, and the solution is maintained at a pressure such that, during expansion, the solute precipitates out of solution within the nozzle in a liquid state. Alternatively, a secondary solvent mutually soluble with the solute and primary solvent and having a higher critical temperature than that of primary solvent is used in a low concentration (<20%) to maintain the solute in a transient liquid state. The solute is discharged in the form of long, thin fibers. The fibers are collected at sufficient distance from the orifice to allow them to solidify in the low pressure/temperature region.

Using solid 13C NMR coupled with solution 31P NMR spectroscopy to investigate molecular species and lability of organic carbon and phosphorus from aquatic plants in Tai Lake, China

USDA-ARS?s Scientific Manuscript database

Aquatic plants are involved in the storage and release capacity for organic matter and nutrients. In this study, solid 13C and solution 31P nuclear magnetic resonance (NMR) spectroscopy were used to characterize the biomass samples of six aquatic plants. Solid 13C NMR spectroscopy revealed the domin...

Understanding the role of A-site and B-site cations on piezoelectric instability in lead--free (1-x) BaTiO3 -- xA(Cu1/3Nb2/3)O3 (A = Sr, Ca, Ba) solid solutions

NASA Astrophysics Data System (ADS)

Maurya, Deepam; Zhou, Yuan; Priya, Shashank

2013-03-01

This study provides fundamental understanding of the enhanced piezoelectric instability in lead-free piezoelectric (1-x) BaTiO3-xA(Cu1/3Nb2/3) O3(A: Sr, Ba and Ca and x = 0.0-0.03) solid solutions. These compositions were found to exhibit large longitudinal piezoelectric constant (d33) of ~330 pC/N and electromechanical planar coupling constant (kp) ~ 46% at room temperature. The X-ray diffraction coupled with atomic pair distribution functions (PDF)s indicated increase in local polarization. Raman scattering and electron paramagnetic resonance (EPR) analysis revealed that substitutions on A and B-site both substantially perturbed the local octahedral dynamics and resulted in localized nano polar regions with lower symmetry. The presence of nano domains and local structural distortions smears the Curie peak resulting in diffuse order-disorder type phase transitions. The effect of these distortions on the variations in physical property was modeled and analyzed within the context of nanodomains and phase transitions. *spriya@vt.edu The financial support from National Science Foundation and Office of Basic Energy Science, Department of Energy (Microscopy analysis) is gratefully acknowledged. The authors would also like to acknowledge the support from KIMS (new piezoelectric)

Imaging secondary structure of individual amyloid fibrils of a β2-microglobulin fragment using near-field infrared spectroscopy.

PubMed

Paulite, Melissa; Fakhraai, Zahra; Li, Isaac T S; Gunari, Nikhil; Tanur, Adrienne E; Walker, Gilbert C

2011-05-18

Amyloid fibril diseases are characterized by the abnormal production of aggregated proteins and are associated with many types of neuro- and physically degenerative diseases. X-ray diffraction techniques, solid-state magic-angle spinning NMR spectroscopy, circular dichroism (CD) spectroscopy, and transmission electron microscopy studies have been utilized to detect and examine the chemical, electronic, material, and structural properties of amyloid fibrils at up to angstrom spatial resolution. However, X-ray diffraction studies require crystals of the fibril to be analyzed, while other techniques can only probe the bulk solution or solid samples. In the work reported here, apertureless near-field scanning infrared microscopy (ANSIM) was used to probe the secondary structure of individual amyloid fibrils made from an in vitro solution. Simultaneous topographic and infrared images of individual amyloid fibrils synthesized from the #21-31 peptide fragment of β(2)-microglobulin were acquired. Using this technique, IR spectra of the amyloid fibrils were obtained with a spatial resolution of less than 30 nm. It is observed that the experimental scattered field spectrum correlates strongly with that calculated using the far-field absorption spectrum. The near-field images of the amyloid fibrils exhibit much lower scattering of the IR radiation at approximately 1630 cm(-1). In addition, the near-field images also indicate that composition and/or structural variations among individual amyloid fibrils were present. © 2011 American Chemical Society

Eggshell membrane-based biotemplating of mixed hemimicelle/admicelle as a solid-phase extraction adsorbent for carcinogenic polycyclic aromatic hydrocarbons.

PubMed

Wang, Weidong; Chen, Bo; Huang, Yuming

2014-08-13

A new solid-phase extraction (SPE) format was demonstrated, based on eggshell membrane (ESM) templating of the mixed hemimicelle/admicelle of linear alkylbenzenesulfonates (LAS) as an adsorbent for the enrichment of carcinogenic polycyclic aromatic hydrocarbons (PAHs) in environmental aqueous samples. The LAS mixed hemimicelle/admicelle formation and SPE of the target PAHs were conducted simultaneously by adding the organic target and LAS through a column filled with 500 mg of ESM. The effect of various factors, including LAS concentration, solution pH, ionic strength, and humic acid concentration on the recoveries of PAHs were investigated and optimized. The results showed that LAS concentration and solution pH had obvious effect on extraction of PAHs, and the recoveries of PAHs compounds decreased in the presence of salt and humic acid. Under the optimized analytical conditions, the present method could respond down to 0.1-8.6 ng/L PAHs with a linear calibration ranging from 0.02 to 10 μg/L, showing a good PAHs enrichment ability with high sensitivity. The developed method was used satisfactorily for the detection of PAHs in environmental water samples. The mixed hemimicelle/admicelle adsorbent exhibited high extraction efficiency to PAHs and good selectivity with respect to natural organic matter and was advantageous over commercial C₁₈ adsorbent, for example, high extraction yield, high breakthrough volume, and easy regeneration.

The microbial transglutaminase immobilization on carboxylated poly(N-isopropylacrylamide) for thermo-responsivity.

PubMed

Zhou, Jian Qin; He, Ting; Wang, Jian Wen

2016-06-01

Microbial transglutaminase (mTG) is widely utilized in the PEGylation of pharmaceutical proteins. mTG immobilization can be achieved via covalent bonding on solid supports. However, the catalytic efficiency of mTG immobilized on solid supports was significantly reduced by mass transfer limitation. To overcome this limitation, mTG was covalently immobilized on the thermo-responsive carboxylated poly(N-isopropylacrylamide) (pNIPAM). The pNIPAM-mTG conjugate exhibited reversibly solubility in aqueous solution with a low critical solution temperature (LCST) at 39°C, i.e., it was insoluble above 39°C and soluble below 39°C. The pH dependence of the pNIPAM-mTG conjugate was similar with that of the native mTG. Upon conjugation to pNIPAM, the optimal temperature of mTG shifted down from 50-55°C to 40-45°C, and the thermal stability of the conjugate was elevated. The easy separation of the pNIPAM-mTG conjugate with its substrate and the catalytic efficiency of the pNIPAM-mTG conjugate were demonstrated by employing the pNIPAM-mTG conjugate to cross-link bovine serum albumin (BSA) and catalyze PEGylation of therapeutic protein, cytochrome c (Cyt C), respectively. The thermo-responsive mTG is suitable to modify proteins in food processing and biomedical engineering. Copyright © 2016 Elsevier Inc. All rights reserved.

The development of Ce3+-activated (Gd,Lu)3Al5O12 garnet solid solutions as efficient yellow-emitting phosphors

NASA Astrophysics Data System (ADS)

Li, Jinkai; Li, Ji-Guang; Liu, Shaohong; Li, Xiaodong; Sun, Xudong; Sakka, Yoshio

2013-10-01

Ce3+-activated Gd3Al5O12 garnet, effectively stabilized by Lu3+ doping, has been developed for new yellow-emitting phosphors. The powder processing of [(Gd1-xLux)1-yCey]3Al5O12 solid solutions was achieved through precursor synthesis via carbonate precipitation, followed by annealing. The resultant (Gd,Lu)AG:Ce3+ phosphor particles exhibit typical yellow emission at ˜570 nm (5d-4f transition of Ce3+) upon blue-light excitation at ˜457 nm (the 2F5/2-5d transition of Ce3+). The quenching concentration of Ce3+ was determined to be ˜1.0 at% (y = 0.01) and the quenching mechanism was suggested to be driven by exchange interactions. The best luminescent [(Gd0.9Lu0.1)0.99Ce0.01]AG phosphor is comparative to the well-known YAG:Ce3+ in emission intensity but has a substantially red-shifted emission band that is desired for warm-white lighting. The effects of processing temperature (1000-1500 °C) on the spectroscopic properties of the phosphors, especially those of Lu3+/Ce3+, were thoroughly investigated and discussed from the centroid position and crystal field splitting of the Ce3+ 5d energy levels.

Simulation of radial solute segregation in vertical Bridgman growth of pyridine-doped benzene, a surrogate for binary organic nonlinear optical materials

NASA Astrophysics Data System (ADS)

Lee, Hanjie; Pearlstein, Arne J.

2000-09-01

We present steady axisymmetric computations of solute distributions and radial segregation for vertical Bridgman growth of pyridine-doped benzene, a binary aromatic system with anisotropic solid-phase thermal conductivity, that serves as a model of solute transport in crystal growth of organic nonlinear optical materials. The radial variation of solid-phase mass fraction ( Cs) of pyridine, which is rejected at the growing interface, depends strongly on growth conditions. High growth velocities tend to increase Cs near the centerline, the ampoule wall, or both, and low growth velocities give more nearly uniform radial distributions. The maximum ampoule-wall temperature gradient also affects radial segregation, with convex-to-the-liquid interfaces at small temperature gradients being associated with radially monotonic Cs distributions, and ridged interfaces at higher gradients being associated with nonmonotonic distributions having maxima at the centerline and ampoule wall. Nonuniformity is strongly determined by both interface shape and the nature of the flow near the interface. Solute is transported down to the interface by a large toroidal vortex, and swept radially inward to the centerline by a second, flattened toroidal cell. When the interface is depressed at its junction with the ampoule wall, rejected solute accumulates in the overlying liquid, where convection is relatively weak, resulting in local solute enrichment of the solid. Computations at normal and zero gravity show that for two very similar interface shapes, a maximum in the radial solid-phase solute distribution at the ampoule wall is associated with the interface shape, while the maximum on the centerline is associated with sweeping of solute to the centerline by a vortical flow on the interface. We also show that radial solute segregation depends significantly on whether account is taken of the anisotropy of the solid-phase thermal conductivity. Finally, the computations provide guidance as to the minimum ampoule length required to produce an axially uniform solute distribution over at least part of the length of a boule.

Impact of fluid-rock chemical interactions on tracer transport in fractured rocks.

PubMed

Mukhopadhyay, Sumit; Liu, H-H; Spycher, N; Kennedy, B M

2013-11-01

In this paper, we investigate the impact of chemical interactions, in the form of mineral precipitation and dissolution reactions, on tracer transport in fractured rocks. When a tracer is introduced in fractured rocks, it moves through the fracture primarily by advection and it also enters the stagnant water of the surrounding rock matrix through diffusion. Inside the porous rock matrix, the tracer chemically interacts with the solid materials of the rock, where it can precipitate depending on the local equilibrium conditions. Alternatively, it can be dissolved from the solid phase of the rock matrix into the matrix pore water, diffuse into the flowing fluids of the fracture and is advected out of it. We show that such chemical interactions between the fluid and solid phases have significant impact on tracer transport in fractured rocks. We invoke the dual-porosity conceptualization to represent the fractured rocks and develop a semi-analytical solution to describe the transient transport of tracers in interacting fluid-rock systems. To test the accuracy and stability of the semi-analytical solution, we compare it with simulation results obtained with the TOUGHREACT simulator. We observe that, in a chemically interacting system, the tracer breakthrough curve exhibits a pseudo-steady state, where the tracer concentration remains more or less constant over a finite period of time. Such a pseudo-steady condition is not observed in a non-reactive fluid-rock system. We show that the duration of the pseudo-state depends on the physical and chemical parameters of the system, and can be exploited to extract information about the fractured rock system, such as the fracture spacing and fracture-matrix interface area. © 2013.

Free energies of formation of WC and WzC and the thermodynamic properties of carbon in solid tungsten

NASA Technical Reports Server (NTRS)

Gupta, D. K.; Seigle, L. L.

1974-01-01

The activity of carbon in the two-phase regions - W + WC and W + W2C was obtained from the carbon content of iron rods equilibrated with mixtures of metal plus carbide powders. From this activity data the standard free energies of formation of WC and W2C were calculated. The temperature of the invariant reaction W2C = W + WC was fixed at 1570 + or - 5K. Using available solubility data for C in solid W, the partial molar free energy of C in the dilute solid solution was also calculated. The heat of solution of C in W, and the excess entropy for the interstitial solid solution, were computed, assuming that the carbon atoms reside in the octahedral interstices of bcc W.

New interpretation of data of the Earth's solid core

NASA Astrophysics Data System (ADS)

Guliyev, H. H.

2017-06-01

The commonly accepted scientific opinions on the inner core as the deformable solid globe are based on the solution of the problem on the distribution of elastic parameters in the inner structures of the Earth. The given solution is obtained within the necessary integral conditions on its self-weight, moment of inertia concerning the axes of rotation and periods of free oscillations of the Earth. It is shown that this solution does not satisfy the mechanics of the deformable solid body with sufficient local conditions following from basic principles concerning the strength, stability and actuality of velocities of propagation of elastic waves. The violation of local conditions shows that the inner core cannot exist in the form of the deformable solid body within the commonly accepted elastic parameters.

Optical and Piezoelectric Study of KNN Solid Solutions Co-Doped with La-Mn and Eu-Fe.

PubMed

Peña-Jiménez, Jesús-Alejandro; González, Federico; López-Juárez, Rigoberto; Hernández-Alcántara, José-Manuel; Camarillo, Enrique; Murrieta-Sánchez, Héctor; Pardo, Lorena; Villafuerte-Castrejón, María-Elena

2016-09-28

The solid-state method was used to synthesize single phase potassium-sodium niobate (KNN) co-doped with the La 3+ -Mn 4+ and Eu 3+ -Fe 3+ ion pairs. Structural determination of all studied solid solutions was accomplished by XRD and Rietveld refinement method. Electron paramagnetic resonance (EPR) studies were performed to determine the oxidation state of paramagnetic centers. Optical spectroscopy measurements, excitation, emission and decay lifetime were carried out for each solid solution. The present study reveals that doping KNN with La 3+ -Mn 4+ and Eu 3+ -Fe 3+ at concentrations of 0.5 mol % and 1 mol %, respectively, improves the ferroelectric and piezoelectric behavior and induce the generation of optical properties in the material for potential applications.

Optical and Piezoelectric Study of KNN Solid Solutions Co-Doped with La-Mn and Eu-Fe

PubMed Central

Peña-Jiménez, Jesús-Alejandro; González, Federico; López-Juárez, Rigoberto; Hernández-Alcántara, José-Manuel; Camarillo, Enrique; Murrieta-Sánchez, Héctor; Pardo, Lorena; Villafuerte-Castrejón, María-Elena

2016-01-01

The solid-state method was used to synthesize single phase potassium-sodium niobate (KNN) co-doped with the La3+–Mn4+ and Eu3+–Fe3+ ion pairs. Structural determination of all studied solid solutions was accomplished by XRD and Rietveld refinement method. Electron paramagnetic resonance (EPR) studies were performed to determine the oxidation state of paramagnetic centers. Optical spectroscopy measurements, excitation, emission and decay lifetime were carried out for each solid solution. The present study reveals that doping KNN with La3+–Mn4+ and Eu3+–Fe3+ at concentrations of 0.5 mol % and 1 mol %, respectively, improves the ferroelectric and piezoelectric behavior and induce the generation of optical properties in the material for potential applications. PMID:28773925

Trace element abundances in single presolar silicon carbide grains by synchrotron X-ray fluorescence

NASA Astrophysics Data System (ADS)

Kashiv, Yoav

2004-12-01

Synchrotron x-ray fluorescence (SXRF) was applied to the study of presolar grains for the first time in this study. 41 single SiC grains of the KJF size fraction (mass-weighted median size of 1.86 μm) from the Murchison (CM2) Meteorite were analyzed. The absolute abundances of the following elements were determined (not every element in every grain): S, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Sr, Y, Zr, Nb, Mo, Ru, Os, Ir and Pt (underlined elements were detected here for the first time in single grains). There is good agreement between the heavier trace element abundances in the grains and s-process nucleosynthesis calculations. It suggests that smaller 13C pocket sizes are needed in the parent stars, a free parameter in the stellar models, than is deduced from isotopic analyses of s-, and s-mainly, elements, such as Zr and Mo. In addition, the data confirms the radiogenic nature of the Nb in the grains, due to the in situ decay of 93Zr (t 1/2 = 1.5 × 106 year). The data suggest that the trace elements condensed into the host SiC grains by a combination of condensation in solid solution and incorporation of subgrains. It seems that many of the trace elements reside mainly in subgrains of two solid solution: (1)a TiC based solid solution, and (2)a Mo-Ru carbide based solid solution. The presence of subgrains of an Fe-Ni alloy solid solution is suggested as well. Subgrains of all 3 solid solutions were observed previously in presolar graphite grains.* *This dissertation is a compound document (contains both a paper copy and a CD as part of the dissertation). The CD requires the following system requirements: Adobe Acrobat.

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

Chezhina, N.V., E-mail: chezhina@nc2490.spb.edu; Korolev, D.A.; Zhuk, N.A.

On the basis of the results of magnetic susceptibility and ESR studies of the Bi{sub 3}Nb{sub 1−x}Fe{sub x}O{sub 7−δ} solid solutions iron atoms in the solid solutions of cubic modification of bismuth niobate were found to exist as Fe(III) monomers and exchange bound Fe(III)-O-Fe(III) dimers with antiferro- and ferromagnetic type of superexchange. The exchange parameters and the distribution of monomers and dimers in the solid solutions were calculated as a function of paramagnetic atom content. - Graphical abstract: The study of the Bi{sub 3}Nb{sub 1−x}Fe{sub x}O{sub 7−δ} solid solutions showed that the introduction of iron atoms into the structure ofmore » Bi{sub 3}NbO{sub 7} stabilizes the cubic structure of bismuth niobate making the phase transition tetragonal ↔ cubic structure irreversible. In the Bi{sub 3}Nb{sub 1−x}Fe{sub x}O{sub 7−δ} solid solutions we observe the formation of dimers with antiferro- and ferromagnetic exchange. Such clusters are partially retained even at the infinite dilution of the solid solution, which testifies for their rigidity. A sufficiently high parameter of ferromagnetic exchange in a dimer (+53 cm{sup −1}) seems to result from iron atoms being located in the vicinity of oxygen vacancy. - Highlights: • The reversible transition cubic – tetragonal modifications in Bi{sub 3}NbO{sub 7} becomes irreversible. • Only cubic modification of Bi{sub 3}Nb{sub 1-x}Fe{sub x}O{sub 7-δ} is stable due to clusters of Fe atoms. • These clusters are sufficiently strong and retained even at the infinite dilution. • The calculations of magnetic susceptibility give the distribution of the clusters and single atoms.« less

Using colloidal silica as isolator, diverter and blocking agent for subsurface geological applications

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

Bourcier, William L.; Roberts, Sarah K.; Roberts, Jeffery J.

A system for blocking fast flow paths in geological formations includes preparing a solution of colloidal silica having a nonviscous phase and a solid gel phase. The solution of colloidal silica is injected into the geological formations while the solution of colloidal silica is in the nonviscous phase. The solution of colloidal silica is directed into the fast flow paths and reaches the solid gel phase in the fast flow paths thereby blocking flow of fluid in the fast paths.

Containerless synthesis of amorphous and nanophase organic materials

DOEpatents

Benmore, Chris J.; Weber, Johann R.

2016-05-03

The invention provides a method for producing a mixture of amorphous compounds, the method comprising supplying a solution containing the compounds; and allowing at least a portion of the solvent of the solution to evaporate while preventing the solute of the solution from contacting a nucleation point. Also provided is a method for transforming solids to amorphous material, the method comprising heating the solids in an environment to form a melt, wherein the environment contains no nucleation points; and cooling the melt in the environment.

Solid composite electrolytes for lithium batteries

DOEpatents

Kumar, Binod; Scanlon, Jr., Lawrence G.

2000-01-01

Solid composite electrolytes are provided for use in lithium batteries which exhibit moderate to high ionic conductivity at ambient temperatures and low activation energies. In one embodiment, a ceramic-ceramic composite electrolyte is provided containing lithium nitride and lithium phosphate. The ceramic-ceramic composite is also preferably annealed and exhibits an activation energy of about 0.1 eV.

Unexpected opioid activity profiles of analogues of the novel peptide kappa opioid receptor ligand CJ-15,208.

PubMed

Aldrich, Jane V; Kulkarni, Santosh S; Senadheera, Sanjeewa N; Ross, Nicolette C; Reilley, Kate J; Eans, Shainnel O; Ganno, Michelle L; Murray, Thomas F; McLaughlin, Jay P

2011-09-05

An alanine scan was performed on the novel κ opioid receptor (KOR) peptide ligand CJ-15,208 to determine which residues contribute to the potent in vivo agonist activity observed for the parent peptide. These cyclic tetrapeptides were synthesized by a combination of solid-phase peptide synthesis of the linear precursors, followed by cyclization in solution. Like the parent peptide, each of the analogues exhibited agonist activity and KOR antagonist activity in an antinociceptive assay in vivo. Unlike the parent peptide, the agonist activity of the potent analogues was mediated predominantly, if not exclusively, by μ opioid receptors (MOR). Thus analogues 2 and 4, in which one of the phenylalanine residues was replaced by alanine, exhibited both potent MOR agonist activity and KOR antagonist activity in vivo. These peptides represent novel lead compounds for the development of peptide-based opioid analgesics. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of a novel cationic hydrogel base on salecan-g-PMAPTAC.

PubMed

Wei, Wei; Qi, Xiaoliang; Li, Junjian; Zhong, Yin; Zuo, Gancheng; Pan, Xihao; Su, Ting; Zhang, Jianfa; Dong, Wei

2017-08-01

Salecan is a biological macromolecular and biocompatible polysaccharide that has been investigated for recent years. Herein, we report a novel cationic hydrogel fabricated by graft-polymerizing 3-(methacryloylamino)propyl-trimethylammonium chloride (MAPTAC) onto salecan chains. The obtained hydrogels were transparent, solid-elastic, macro-porous, ion-sensitive, and non-cytotoxic. The swelling ratios increased with salecan content, while mechanical strength does the opposite. Moreover, drug delivery test was studied as a potential application. Diclofenac sodium (DS) and insulin were selected as model drugs. Interestingly, in drug loading process, DS molecules exhibited highly affinity to these cationic hydrogels. Almost all the DS molecules in loading solution were absorbed and spread into the hydrogel. For drug release profiles, insulin-loaded hydrogel showed an initial rapid release and a sustained release. As a comparison, DS-loaded hydrogel exhibited a more sustained release profile. Results suggested salecan-g-PMAPTAC hydrogel could be a good candidate for anionic drug loading and delivery. Copyright © 2017 Elsevier B.V. All rights reserved.

Dispersoid reinforced alloy powder and method of making

DOEpatents

Anderson, Iver E; Rieken, Joel

2013-12-10

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with an introduced reactive species than does the alloying element and wherein one or more atomizing parameters is/are modified to controllably reduce the amount of the reactive species, such as oxygen, introduced into the atomized particles so as to reduce anneal times and improve reaction (conversion) to the desired strengthening dispersoids in the matrix. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies are made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.

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

Lingenfelter, A. C., LLNL

Materials for gas turbine engines are required to meet a wide range of temperature and stress application requirements. These alloys exhibit a combination of creep resistance, creep rupture strength, yield and tensile strength over a wide temperature range, resistance to environmental attack (including oxidation, nitridation, sulphidation and carburization), fatigue and thermal fatigue resistance, metallurgical stability and useful thermal expansion characteristics. These properties are exhibited by a series of solid-solution-strengthened and precipitation-hardened nickel, iron and cobalt alloys. The properties needed to meet the turbine engine requirements have been achieved by specific alloy additions, by heat treatment and by thermal mechanical processing.more » A thorough understanding of the metallurgy and metallurgical processing of these materials is imperative in order to successfully fusion weld them. This same basic understanding is required for repair of a component with the added dimension of the potential effects of thermal cycling and environmental exposure the component will have endured in service. This article will explore the potential problems in joining and repair welding these materials.« less

Water-Soluble Polymers with Strong Photoluminescence through an Eco-Friendly and Low-Cost Route.

PubMed

Guo, Zhaoyan; Ru, Yue; Song, Wenbo; Liu, Zhenjie; Zhang, Xiaohong; Qiao, Jinliang

2017-07-01

Photoluminescence (PL) of nonconjugated polymers brings a favorable opportunity for low-cost and nontoxic luminescent materials, while most of them still exhibit relatively weak emission. Strong PL from poly[(maleic anhydride)-alt-(vinyl acetate)] (PMV) from low-cost monomer has been found in organic solvents, yet the necessity of noxious solvents would hinder its practical applications. Herein, through a novel, eco-friendly, and one-step route, PMV-derived PL polymers can be fabricated with the highest quantum yield of 87% among water-soluble nonconjugated PL polymers ever reported. These PMV-derived polymers emit strong blue emission in both solutions and solids, and can be transformed into red-emission agents easily. These PL polymers exhibit application potentials in light-conversion agricultural films. It is assumed that this work not only puts forward a convenient preparation routine for nonconjugated polymers with high PL, but also provides an industrial application possibility for them. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

First-principles study of band gap engineering via oxygen vacancy doping in perovskite ABB'O₃ solid solutions

DOE PAGES

Qi, Tingting; Curnan, Matthew T.; Kim, Seungchul; ...

2011-12-15

Oxygen vacancies in perovskite oxide solid solutions are fundamentally interesting and technologically important. However, experimental characterization of the vacancy locations and their impact on electronic structure is challenging. We have carried out first-principles calculations on two Zr-modified solid solutions, Pb(Zn 1/3Nb 2/3)O₃ and Pb(Mg 1/3Nb 2/3)O₃, in which vacancies are present. We find that the vacancies are more likely to reside between low-valent cation-cation pairs than high-valent cation-cation pairs. Based on the analysis of our results, we formulate guidelines that can be used to predict the location of oxygen vacancies in perovskite solid solutions. Our results show that vacancies canmore » have a significant impact on both the conduction and valence band energies, in some cases lowering the band gap by ≈0.5 eV. The effects of vacancies on the electronic band structure can be understood within the framework of crystal field theory.« less

Solid solutions of platinum(II) and palladium(II) oxalato-complex salt as precursors of nanoalloys

NASA Astrophysics Data System (ADS)

Zadesenets, A. V.; Asanova, T. I.; Vikulova, E. S.; Filatov, E. Yu.; Plyusnin, P. E.; Baidina, I. A.; Asanov, I. P.; Korenev, S. V.

2013-03-01

A solid solution of platinum (II) and palladium (II) oxalato-complex salt, (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O, has been synthesized and studied as a precursor for preparing bimetallic PtPd nanoparticles through its thermal decomposition. The smallest homogenous bimetallic PtPd nanoparticles were found to form in hydrogen and helium atmospheres. The annealing temperature and time have low effect on the bimetallic particles size. Comparative analysis of structural and thermal properties of the solid solution and individual Pt, Pd oxalato-complex salts was performed to investigate a mechanism of thermal decomposition of (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O. Based on in situ X-ray photoemission spectroscopy investigation it was proposed a mechanism of formation of bimetallic PtPd nanoparticles from the solid-solution oxalato-complex salt during thermal decomposition.

Design of high-strength refractory complex solid-solution alloys

DOE PAGES

Singh, Prashant; Sharma, Aayush; Smirnov, A. V.; ...

2018-03-28

Nickel-based superalloys and near-equiatomic high-entropy alloys containing molybdenum are known for higher temperature strength and corrosion resistance. Yet, complex solid-solution alloys offer a huge design space to tune for optimal properties at slightly reduced entropy. For refractory Mo-W-Ta-Ti-Zr, we showcase KKR electronic structure methods via the coherent-potential approximation to identify alloys over five-dimensional design space with improved mechanical properties and necessary global (formation enthalpy) and local (short-range order) stability. Deformation is modeled with classical molecular dynamic simulations, validated from our first-principle data. We predict complex solid-solution alloys of improved stability with greatly enhanced modulus of elasticity (3× at 300 K)more » over near-equiatomic cases, as validated experimentally, and with higher moduli above 500 K over commercial alloys (2.3× at 2000 K). We also show that optimal complex solid-solution alloys are not described well by classical potentials due to critical electronic effects.« less

Atomistic simulation of mineral-melt trace-element partitioning

NASA Astrophysics Data System (ADS)

Allan, Neil L.; Du, Zhimei; Lavrentiev, Mikhail Yu.; Blundy, Jon D.; Purton, John A.; van Westrenen, Wim

2003-09-01

We discuss recent advances in computational approaches to trace-element incorporation in minerals and melts. It is crucial to take explicit account of the local structural environment of each ion in the solid and the change in this environment following the introduction of a foreign atom or atoms. Particular attention is paid to models using relaxation (strain) energies and solution energies, and the use of these different models for isovalent and heterovalent substitution in diopside and forsterite. Solution energies are also evaluated for pyrope and grossular garnets, and pyrope-grossular solid solutions. Unfavourable interactions between dodecahedral sites containing ions of the same size and connected by an intervening tetrahedron lead to larger solubilities of trace elements in the garnet solid solution than in either end member compound and to the failure of Goldschmidt's first rule. Our final two examples are the partitioning behaviour of noble gases, which behave as 'ions of zero charge' and the direct calculation of high-temperature partition coefficients between CaO solid and melt via Monte Carlo simulations.

Design of high-strength refractory complex solid-solution alloys

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

Singh, Prashant; Sharma, Aayush; Smirnov, A. V.

Nickel-based superalloys and near-equiatomic high-entropy alloys containing molybdenum are known for higher temperature strength and corrosion resistance. Yet, complex solid-solution alloys offer a huge design space to tune for optimal properties at slightly reduced entropy. For refractory Mo-W-Ta-Ti-Zr, we showcase KKR electronic structure methods via the coherent-potential approximation to identify alloys over five-dimensional design space with improved mechanical properties and necessary global (formation enthalpy) and local (short-range order) stability. Deformation is modeled with classical molecular dynamic simulations, validated from our first-principle data. We predict complex solid-solution alloys of improved stability with greatly enhanced modulus of elasticity (3× at 300 K)more » over near-equiatomic cases, as validated experimentally, and with higher moduli above 500 K over commercial alloys (2.3× at 2000 K). We also show that optimal complex solid-solution alloys are not described well by classical potentials due to critical electronic effects.« less

Hydrothermal synthesis of pollucite, analcime and their solid solutions and analysis of their properties

NASA Astrophysics Data System (ADS)

Jing, Zhenzi; Cai, Kunchuan; Li, Yan; Fan, Junjie; Zhang, Yi; Miao, Jiajun; Chen, Yuqian; Jin, Fangming

2017-05-01

Pollucite, as a perfect long-term potential host for radioactive Cs immobilization, barely exists in pure form naturally but in an isomorphism form between pollucite and analcime due to coexistence of Cs and Na. Pollucite could be hydrothermally synthesized with Cs-polluted soil or clay minerals which contain Cs and Na, and it is necessary to study the properties of the synthesis if Cs and Na contained. Pure pollucite, analcime and their solid solutions were hydrothermally synthesized with chemicals, and it was found that the most formed pollucite analcime solid solutions with Cs/(Cs + Na) ratios of 2/6-5/6 had very similar properties in mineral composition, morphology and size, structural water (Cs cations) and coordination environment to pollucite. This also suggests that even coexistence of Cs and Na in nature, pollucite favors to form due to site preference for Cs over Na, which leads to the property and the structure of the most solid solutions similar to that of pollucite.

Elastic constants and pressure derivative of elastic constants of Si1-xGex solid solution

NASA Astrophysics Data System (ADS)

Jivani, A. R.; Baria, J. K.; Vyas, P. S.; Jani, A. R.

2013-02-01

Elastic properties of Si1-xGex solid solution with arbitrary (atomic) concentration (x) are studied using the pseudo-alloy atom model based on the pseudopotential theory and on the higher-order perturbation scheme with the application of our own proposed model potential. We have used local-field correction function proposed by Sarkar et al to study Si-Ge system. The Elastic constants and pressure derivatives of elastic constants of the solid solution is investigated with different concentration x of Ge. It is found in the present study that the calculated numerical values of the aforesaid physical properties of Si-Ge system are function of x. The elastic constants (C11, C12 and C44) decrease linearly with increase in concentration x and pressure derivative of elastic constants (C11, C12 and C44) increase with the concentration x of Ge. This study provides better set of theoretical results for such solid solution for further comparison either with theoretical or experimental results.

Flow of variably fluidized granular masses across three-dimensional terrain I. Coulomb mixture theory

USGS Publications Warehouse

Iverson, R.M.; Denlinger, R.P.

2001-01-01

Rock avalanches, debris flows, and related phenomena consist of grain-fluid mixtures that move across three-dimensional terrain. In all these phenomena the same basic forces, govern motion, but differing mixture compositions, initial conditions, and boundary conditions yield varied dynamics and deposits. To predict motion of diverse grain-fluid masses from initiation to deposition, we develop a depth-averaged, threedimensional mathematical model that accounts explicitly for solid- and fluid-phase forces and interactions. Model input consists of initial conditions, path topography, basal and internal friction angles of solid grains, viscosity of pore fluid, mixture density, and a mixture diffusivity that controls pore pressure dissipation. Because these properties are constrained by independent measurements, the model requires little or no calibration and yields readily testable predictions. In the limit of vanishing Coulomb friction due to persistent high fluid pressure the model equations describe motion of viscous floods, and in the limit of vanishing fluid stress they describe one-phase granular avalanches. Analysis of intermediate phenomena such as debris flows and pyroclastic flows requires use of the full mixture equations, which can simulate interaction of high-friction surge fronts with more-fluid debris that follows. Special numerical methods (described in the companion paper) are necessary to solve the full equations, but exact analytical solutions of simplified equations provide critical insight. An analytical solution for translational motion of a Coulomb mixture accelerating from rest and descending a uniform slope demonstrates that steady flow can occur only asymptotically. A solution for the asymptotic limit of steady flow in a rectangular channel explains why shear may be concentrated in narrow marginal bands that border a plug of translating debris. Solutions for static equilibrium of source areas describe conditions of incipient slope instability, and other static solutions show that nonuniform distributions of pore fluid pressure produce bluntly tapered vertical profiles at the margins of deposits. Simplified equations and solutions may apply in additional situations identified by a scaling analysis. Assessment of dimensionless scaling parameters also reveals that miniature laboratory experiments poorly simulate the dynamics of full-scale flows in which fluid effects are significant. Therefore large geophysical flows can exhibit dynamics not evident at laboratory scales.

Flow of variably fluidized granular masses across three-dimensional terrain: 1. Coulomb mixture theory

NASA Astrophysics Data System (ADS)

Iverson, Richard M.; Denlinger, Roger P.

2001-01-01

Rock avalanches, debris flows, and related phenomena consist of grain-fluid mixtures that move across three-dimensional terrain. In all these phenomena the same basic forces govern motion, but differing mixture compositions, initial conditions, and boundary conditions yield varied dynamics and deposits. To predict motion of diverse grain-fluid masses from initiation to deposition, we develop a depth-averaged, three-dimensional mathematical model that accounts explicitly for solid- and fluid-phase forces and interactions. Model input consists of initial conditions, path topography, basal and internal friction angles of solid grains, viscosity of pore fluid, mixture density, and a mixture diffusivity that controls pore pressure dissipation. Because these properties are constrained by independent measurements, the model requires little or no calibration and yields readily testable predictions. In the limit of vanishing Coulomb friction due to persistent high fluid pressure the model equations describe motion of viscous floods, and in the limit of vanishing fluid stress they describe one-phase granular avalanches. Analysis of intermediate phenomena such as debris flows and pyroclastic flows requires use of the full mixture equations, which can simulate interaction of high-friction surge fronts with more-fluid debris that follows. Special numerical methods (described in the companion paper) are necessary to solve the full equations, but exact analytical solutions of simplified equations provide critical insight. An analytical solution for translational motion of a Coulomb mixture accelerating from rest and descending a uniform slope demonstrates that steady flow can occur only asymptotically. A solution for the asymptotic limit of steady flow in a rectangular channel explains why shear may be concentrated in narrow marginal bands that border a plug of translating debris. Solutions for static equilibrium of source areas describe conditions of incipient slope instability, and other static solutions show that nonuniform distributions of pore fluid pressure produce bluntly tapered vertical profiles at the margins of deposits. Simplified equations and solutions may apply in additional situations identified by a scaling analysis. Assessment of dimensionless scaling parameters also reveals that miniature laboratory experiments poorly simulate the dynamics of full-scale flows in which fluid effects are significant. Therefore large geophysical flows can exhibit dynamics not evident at laboratory scales.

Both solubility and chemical stability of curcumin are enhanced by solid dispersion in cellulose derivative matrices.

PubMed

Li, Bin; Konecke, Stephanie; Wegiel, Lindsay A; Taylor, Lynne S; Edgar, Kevin J

2013-10-15

Amorphous solid dispersions (ASD) of curcumin (Cur) in cellulose derivative matrices, hydroxypropylmethylcellulose acetate succinate (HPMCAS), carboxymethylcellulose acetate butyrate (CMCAB), and cellulose acetate adipate propionate (CAAdP) were prepared in order to investigate the structure-property relationship and identify polymer properties necessary to effectively increase Cur aqueous solution concentration. XRD results indicated that all investigated solid dispersions were amorphous, even at a 9:1 Cur:polymer ratio. Both stability against crystallization and Cur solution concentration from these ASDs were significantly higher than those from physical mixtures and crystalline Cur. Remarkably, curcumin was also stabilized against chemical degradation in solution. Chemical stabilization was polymer-dependent, with stabilization in CAAdP>CMCAB>HPMCAS>PVP, while matrices enhanced solution concentration as PVP>HPMCAS>CMCAB≈CAAdP. HPMCAS/Cur dispersions have useful combinations of pH-triggered release profile, chemical stabilization, and strong enhancement of Cur solution concentration. Copyright © 2013 Elsevier Ltd. All rights reserved.

Energetics of a uranothorite (Th 1–xU xSiO 4) solid solution

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

Guo, Xiaofeng; Szenknect, Stephanie; Mesbah, Adel

High-temperature oxide melt solution calorimetric measurements were completed to determine the enthalpies of formation of the uranothorite, (USiO 4) x–(ThSiO 4) 1–x, solid solution. Phase-pure samples with x values of 0, 0.11, 0.21, 0.35, 0.71, and 0.84 were prepared, purified, and characterized by powder X-ray diffraction, electron probe microanalysis, thermogravimetric analysis and differential scanning calorimetry coupled with in situ mass spectrometry, and high-temperature oxide melt solution calorimetry. This work confirms the energetic metastability of coffinite, USiO 4, and U-rich intermediate silicate phases with respect to a mixture of binary oxides. Furthermore, variations in unit cell parameters and negative excess volumesmore » of mixing, coupled with strongly exothermic enthalpies of mixing in the solid solution, suggest short-range cation ordering that can stabilize intermediate compositions, especially near x = 0.5.« less

Energetics of a uranothorite (Th 1–xU xSiO 4) solid solution

DOE PAGES

Guo, Xiaofeng; Szenknect, Stephanie; Mesbah, Adel; ...

2016-10-11

High-temperature oxide melt solution calorimetric measurements were completed to determine the enthalpies of formation of the uranothorite, (USiO 4) x–(ThSiO 4) 1–x, solid solution. Phase-pure samples with x values of 0, 0.11, 0.21, 0.35, 0.71, and 0.84 were prepared, purified, and characterized by powder X-ray diffraction, electron probe microanalysis, thermogravimetric analysis and differential scanning calorimetry coupled with in situ mass spectrometry, and high-temperature oxide melt solution calorimetry. This work confirms the energetic metastability of coffinite, USiO 4, and U-rich intermediate silicate phases with respect to a mixture of binary oxides. Furthermore, variations in unit cell parameters and negative excess volumesmore » of mixing, coupled with strongly exothermic enthalpies of mixing in the solid solution, suggest short-range cation ordering that can stabilize intermediate compositions, especially near x = 0.5.« less

Corrosion behaviour of Al-Fe-Ti-V medium entropy alloy

NASA Astrophysics Data System (ADS)

Bodunrin, M. O.; Obadele, B. A.; Chown, L. H.; Olubambi, P. A.

2017-12-01

Alloys containing up to four multi-principal elements in equiatomic ratios are referred to as medium entropy alloys (MEA). These alloys have attracted the interest of many researchers due to the superior mechanical properties it offers over the traditional alloys. The design approach of MEA often results to simple solid solution with either body centered cubic; face centered cubic structures or both. As the consideration for introducing the alloys into several engineering application increases, there have been efforts to study the corrosion behaviour of these alloys. Previous reports have shown that some of these alloys are more susceptible to corrosion when compared with traditional alloys due to lack of protective passive film. In this research, we have developed AlFeTiV medium entropy alloys containing two elements (Ti and Al) that readily passivate when exposed to corrosive solutions. The alloys were produced in vacuum arc furnace purged with high purity argon. Open circuit potential and potentiodynamic polarisation tests were used to evaluate the corrosion behaviour of the as-cast AlFeTiV alloy in 3.5 wt% NaCl and 1 M H2SO4. The corrosion performance of the alloy was compared with Ti-6Al-4V alloy tested under similar conditions. The results show that unlike in Ti-6Al-4V alloy, the open circuit potential of the AlFeTiV alloy move towards the negative values in both 3.5 wt% NaCl and 1 M H2SO4 solutions indicating that self-activation occurred rapidly on immersion. Anodic polarisation of the alloys showed that AlFeTiV alloy exhibited a narrow range of passivity in both solutions. In addition, the alloys exhibited lower Ecorr and higher Icorr when compared with traditional Ti-6Al-4V alloy. The traditional Ti-6Al-4V alloy showed superior corrosion resistant to the AlFeTiV alloy in both 3.5 wt.% NaCl and 1 M H2SO4 solutions.

A facile synthesis of Zn(x)Cd(1-x)S/CNTs nanocomposite photocatalyst for H2 production.

PubMed

Wang, Lei; Yao, Zhongping; Jia, Fangzhou; Chen, Bin; Jiang, Zhaohua

2013-07-21

The sulfide solid solution has become a promising and important visible-light-responsive photocatalyst for hydrogen production nowadays. Zn(x)Cd(1-x)S/CNT nanocomposites were synthesized to improve the dispersion, adjust the energy band gap, and enhance the separation of the photogenerated electrons and holes. The as-prepared photocatalysts were characterized by scanning electron-microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV-visible diffuse reflectance spectra (UV-visible), respectively. And the effects of CNTs on structure, composition and optical absorption property of the sulfide solid solutions were investigated along with their inherent relationships. For Zn0.83Cd0.17S/CNTs, sulfide solid solution is assembled along the CNTs orderly, with a diameter of 100 nm or so. XPS analysis shows that there is bonding effect between the solid solutions and the CNTs due to the strong adsorption of Zn(2+) and Cd(2+) on the surface of CNTs. There are two obvious absorption edges for Zn0.83Cd0.17S/CNTs, corresponding to two kinds of sulfide solid solutions with different molar ratios of Zn/Cd. The hybridization of solid solutions with CNTs makes the absorption spectrum red shift. The photocatalytic property was evaluated by splitting Na2S + Na2SO3 solution into H2, and the highest rate of H2 evolution of 6.03 mmol h(-1) g(-1) was achieved over Zn0.83Cd0.17S/CNTs. The high activity of photocatalytic H2 production is attributed to the following factors: (1) the optimum band gap and a moderate position of the conduction band (which needs to match the irradiation spectrum of the Xe lamp best), (2) the efficient separation of photogenerated electrons and holes by hybridization, and (3) the improvement of the dispersion of nanocomposites by assembling along the CNTs as well.

Non-uniform lithium-ion migration on micrometre scale for garnet- and NASICON-type solid electrolytes studied by 7Li PGSE-NMR diffusion spectroscopy.

PubMed

Hayamizu, Kikuko; Seki, Shiro; Haishi, Tomoyuki

2018-06-21

The migration behaviours of Li+ in three garnet- and one NASICON-type solid oxide electrolytes were studied on the micrometre scale by pulsed-gradient spin-echo (PGSE) 7Li NMR diffusion spectroscopy to clarify common and specific characteristics of each electrolyte. In these solid electrolytes, clear evidences of grain boundary effects in the diffusion of Li+ were not observed. The Li+ diffusion constants were dependent on parameters such as observation time (Δ) and pulsed field gradient (PFG) strength (g) for all the studied inorganic solid electrolytes. For low Δ values, Li+ ions underwent collisions and diffractions with diffraction distance Rdiffraction [μm]. The apparent Li+ diffusion constants (Dapparent [m2 s-1]) exhibited distributions in a wide range. In this paper, we introduced the apparent diffusion radius, rradius [μm], and compared it with Rdiffraction and mean square displacement (MSD) [μm]; the lengths of these distances were of the micrometre order (10-6 m). The relations between the values of rradius, Rdiffraction and MSD suggested that the migration behaviours of Li+ on the micrometre scale were complicated. Using high Δ and high g values, we obtained an equilibrated value of DLi. The temperature dependences of the number of carrier ions were estimated from the DLi values and ionic conductivities in the four solid oxide electrolytes. For simple comparison and reference, the data of DLi and ionic conductivity of LiPF6 in 1 M solution of propylene carbonate were added.

Enhanced intestinal permeability and oral bioavailability of enalapril maleate upon complexation with the cationic polymethacrylate Eudragit E100.

PubMed

Ramírez-Rigo, María V; Olivera, María E; Rubio, Modesto; Manzo, Ruben H

2014-05-13

The low bioavailability of enalapril maleate associated to its instability in solid state motivated the development of a polyelectrolyte-drug complex between enalapril maleate and the cationic polymethacrylate Eudragit E100. The solid complexes were characterized by DSC-TG, FT-IR and X-ray diffraction. Their aqueous dispersions were evaluated for drug delivery in bicompartimental Franz cells and electrokinetic potentials. Stability in solid state was also evaluated using an HPLC-UV stability indicating method. Absorption of enalapril maleate was assessed thorough the rat everted gut sac model. In addition, urinary recovery after oral administration in rats was used as an indicator of systemic exposition. The solid materials are stable amorphous solids in which both moieties of enalapril maleate are ionically bonded to the polymer. Their aqueous dispersions exhibited controlled release over more than 7h in physiologic saline solution, being ionic exchange the fundamental mechanism that modified the extent and rate of drug release. Intestinal permeation of enalapril maleate was 1.7 times higher in the presence of the cationic polymer. This increase can be related with the capacity to adhere the mucosa due to the positive zeta potential of the complexes. As a consequence bioavailability was significantly improved (1.39 times) after oral administration of the complexes. In addition, no signs of chemical decomposition were observed after a 14months period. The results indicated that the products are new chemical entities that improve unfavorable properties of a useful drug. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis, structural and semiconducting properties of Ba(Cu1/3 Sb2/3)O3-PbTiO3 solid solutions

NASA Astrophysics Data System (ADS)

Singh, Chandra Bhal; Kumar, Dinesh; Prashant, Verma, Narendra Kumar; Singh, Akhilesh Kumar

2018-05-01

We report the synthesis and properties of a new solid solution 0.05Ba(Cu1/3Sb2/3)O3-0.95PbTiO3 (BCS-PT) which shows the semiconducting properties. In this study, we have designed new perovskite-type (ABO3) solid solution of BCS-PT that have tunable optical band gap. BCS-PT compounds were prepared by conventional solid-state reaction method and their structural, micro-structural and optical properties were analyzed. The calcination temperature for BCS-PT solid solutions has been optimized to obtain a phase pure system. The Reitveld analysis of X-ray data show that all samples crystallize in tetragonal crystal structure with space group P4mm. X-ray investigation revealed that increase in calcination temperature led to increase of lattice parameter `a' while `c' parameter value lowered. The band gap of PbTiO3 is reduced from 3.2 eV to 2.8 eV with BCS doping and with increasing calcination temperature it further reduces to 2.56 eV. The reduced band gap indicated that the compounds are semiconducting and can be used for photovoltaic device applications.

Role of Precursor-Conversion Chemistry in the Crystal-Phase Control of Catalytically Grown Colloidal Semiconductor Quantum Wires.

PubMed

Wang, Fudong; Buhro, William E

2017-12-26

Crystal-phase control is one of the most challenging problems in nanowire growth. We demonstrate that, in the solution-phase catalyzed growth of colloidal cadmium telluride (CdTe) quantum wires (QWs), the crystal phase can be controlled by manipulating the reaction chemistry of the Cd precursors and tri-n-octylphosphine telluride (TOPTe) to favor the production of either a CdTe solute or Te, which consequently determines the composition and (liquid or solid) state of the Bi x Cd y Te z catalyst nanoparticles. Growth of single-phase (e.g., wurtzite) QWs is achieved only from solid catalysts (y ≪ z) that enable the solution-solid-solid growth of the QWs, whereas the liquid catalysts (y ≈ z) fulfill the solution-liquid-solid growth of the polytypic QWs. Factors that affect the precursor-conversion chemistry are systematically accounted for, which are correlated with a kinetic study of the composition and state of the catalyst nanoparticles to understand the mechanism. This work reveals the role of the precursor-reaction chemistry in the crystal-phase control of catalytically grown colloidal QWs, opening the possibility of growing phase-pure QWs of other compositions.

Compositional dependence of elastic moduli for transition-metal oxide spinels

NASA Astrophysics Data System (ADS)

Reichmann, H. J.; Jacobsen, S. D.; Boffa Ballaran, T.

2012-12-01

Spinel phases (AB2O4) are common non-silicate oxides in the Earth's crust and upper mantle. A characteristic of this mineral group is the ability to host a wide range of transition metals. Here we summarize the influence of transition metals (Fe, Zn, and Mn) on the pressure dependence of elastic moduli of related spinels (magnetite, gahnite, and franklinite) using GHz-ultrasonic interferometry. Measurements were carried out up to 10 GPa in diamond-anvil cells using hydrostatic pressure media. Transition metals with unfilled 3d orbitals strongly influence the elastic properties of spinels. Franklinite (Zn,Mn)Fe2O4 and magnetite Fe3O4 with transition metals on both A and B cation sites exhibit pressure-induced mode softening of C44, whereas C44 of gahnite(ZnAl2O4) and spinel (MgAl2O4) exhibit positive pressure derivatives of the shear moduli. Spinels with two transition elements tend to undergo phase changes at a lower pressure than those with none or only one transition metal. Along the Mn-Zn solid solution, the variation of moduli with composition is non-linear, and a mid-range franklinite composition studied here shows a minimum in C44 compared with either end-member: MnFe2O 4 or ZnFe2O4. In general, the linear variation of sound velocity with density (Birch's Law) is followed by spinels, however spinels containing only one or no transition metals follow a distinct slope from those containing transition metals on both A and B sites. The Cauchy relation, 0.5(C12 - C44) = P is fulfilled by spinels with only one or no transition metals, suggesting that that Coulomb interactions dominate. Spinels with two transition metals fail to meet the Cauchy relation, indicating strong directional dependence and covalent character of bonding. The bonding character of transition metals is crucial to understanding the elastic behavior of natural and synthetic spinel solid solutions containing transition metals.

High temperature resistant cermet and ceramic compositions

NASA Technical Reports Server (NTRS)

Phillips, W. M. (Inventor)

1978-01-01

Cermet compositions having high temperature oxidation resistance, high hardness and high abrasion and wear resistance, and particularly adapted for production of high temperature resistant cermet insulator bodies are presented. The compositions are comprised of a sintered body of particles of a high temperature resistant metal or metal alloy, preferably molybdenum or tungsten particles, dispersed in and bonded to a solid solution formed of aluminum oxide and silicon nitride, and particularly a ternary solid solution formed of a mixture of aluminum oxide, silicon nitride and aluminum nitride. Also disclosed are novel ceramic compositions comprising a sintered solid solution of aluminum oxide, silicon nitride and aluminum nitride.

Chemically and compositionally modified solid solution disordered multiphase nickel hydroxide positive electrode for alkaline rechargeable electrochemical cells

DOEpatents

Ovshinsky, Stanford R.; Corrigan, Dennis; Venkatesan, Srini; Young, Rosa; Fierro, Christian; Fetcenko, Michael A.

1994-01-01

A high capacity, long cycle life positive electrode for use in an alkaline rechargeable electrochemical cell comprising: a solid solution nickel hydroxide material having a multiphase structure that comprises at least one polycrystalline .gamma.-phase including a polycrystalline .gamma.-phase unit cell comprising spacedly disposed plates with at least one chemical modifier incorporated around the plates, the plates having a range of stable intersheet distances corresponding to a 2.sup.+ oxidation state and a 3.5.sup.+, or greater, oxidation state; and at least one compositional modifier incorporated into the solid solution nickel hydroxide material to promote the multiphase structure.

Hydrogen generation from water/methanol under visible light using aerogel prepared strontium titanate (SrTiO3) nanomaterials doped with ruthenium and rhodium metals

NASA Astrophysics Data System (ADS)

Kuo, Yenting; Klabunde, Kenneth J.

2012-07-01

Nanostructured strontium titanate visible-light-driven photocatalysts containing rhodium and ruthenium were synthesized by a modified aerogel synthesis using ruthenium chloride and rhodium nitrate as dopant precursors, and titanium isopropoxide and strontium metal as the metal sources. The well-defined crystalline SrTiO3 structure was confirmed by means of x-ray diffraction. After calcination at 500 °C, diffuse reflectance spectroscopy shows an increase in light absorption at 370 nm due to the presence of Rh3 + ; however an increase of the calcination temperature to 600 °C led to a decrease in intensity, probably due to a loss of surface area. An increase in the rhodium doping level also led to an increase in absorption at 370 nm however, the higher amounts of dopant lowered the photocatalytic activity. The modified aerogel synthesis allows greatly enhanced H2 production performance from an aqueous methanol solution under visible light irradiation compared with lower surface area conventional materials. We believe that this enhanced activity is due to the higher surface areas while high quality nanocrystalline materials are still obtained. Furthermore, the surface properties of these nanocrystalline aerogel materials are different, as exhibited by the higher activities in alkaline solutions, while conventional materials (obtained via high temperature solid-state synthesis methods) only exhibit reasonable hydrogen production in acidic solutions. Moreover, an aerogel synthesis approach gives the possibility of thin-film formation and ease of incorporation into practical solar devices.

Enterocin A Mutants Identified by Saturation Mutagenesis Enhance Potency Towards Vancomycin-Resistant Enterococci

PubMed Central

McClintock, Maria K.; Kaznessis, Yiannis N.; Hackel, Benjamin J.

2016-01-01

Vancomycin-resistant Enterococci infections are a significant clinical problem. One proposed solution is to use probiotics, such as lactic acid bacteria, to produce antimicrobial peptides at the site of infection. Enterocin A, a class 2a bacteriocin, exhibits inhibitory activity against E. faecium and E. faecalis, which account for 86% of vancomycin-resistant Enterococci infections. In this study, we aimed to engineer enterocin A mutants with enhanced potency within a lactic acid bacterial production system. Peptide mutants resulting from saturation mutagenesis at sites A24 and T27 were efficiently screened in a 96-well plate assay for inhibition of pathogen growth. Several mutants exhibit increased potency relative to wild-type enterocin A in both liquid- and solid-medium growth assays. In particular, A24P and T27G exhibit enhanced inhibition of multiple strains of E. faecium and E. faecalis, including clinically isolated vancomycin-resistant strains. A24P and T27G enhance killing of E. faecium 8 by 13±3- and 18±4-fold, respectively. The engineered enterocin A/lactic acid bacteria systems offer significant potential to combat antibiotic-resistant infections. PMID:26191783

Enterocin A mutants identified by saturation mutagenesis enhance potency towards vancomycin-resistant Enterococci.

PubMed

McClintock, Maria K; Kaznessis, Yiannis N; Hackel, Benjamin J

2016-02-01

Vancomycin-resistant Enterococci infections are a significant clinical problem. One proposed solution is to use probiotics, such as lactic acid bacteria, to produce antimicrobial peptides at the site of infection. Enterocin A, a class 2a bacteriocin, exhibits inhibitory activity against E. faecium and E. faecalis, which account for 86% of vancomycin-resistant Enterococci infections. In this study, we aimed to engineer enterocin A mutants with enhanced potency within a lactic acid bacterial production system. Peptide mutants resulting from saturation mutagenesis at sites A24 and T27 were efficiently screened in a 96-well plate assay for inhibition of pathogen growth. Several mutants exhibit increased potency relative to wild-type enterocin A in both liquid- and solid-medium growth assays. In particular, A24P and T27G exhibit enhanced inhibition of multiple strains of E. faecium and E. faecalis, including clinically isolated vancomycin-resistant strains. A24P and T27G enhance killing of E. faecium 8 by 13 ± 3- and 18 ± 4-fold, respectively. The engineered enterocin A/lactic acid bacteria systems offer significant potential to combat antibiotic-resistant infections. © 2015 Wiley Periodicals, Inc.

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

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

Spark plasma sintered transition metal diborides such as HfB 2, ZrB 2 and their solid solutions were investigated as electrode materials for electrochemical hydrogen evolutions reactions (HER) in 1 M H 2SO 4 and 1 M NaOH electrolytes. HfB 2 and ZrB 2 formed complete solid solutions when mixed in 1:1, 1:4, and 4:1 ratios and they were stable in both electrolytes. The HER kinetics of the diborides were slower in the basic solution than in the acidic solutions. The Tafel slopes in 1 M H 2SO 4 were in the range of 0.15 - 0.18 V/decade except for puremore » HfB 2 which showed a Tafel slope of 0.38 V/decade. In 1 M NaOH the Tafel slopes were in the range of 0.12 - 0.27 V/decade. The composition of Hf xZr 1-xB 2 solid solutions with x = 0.2 - 0.8, influenced the exchange current densities, overpotentials and Tafel slopes of the HER. As a result, the EIS data were fitted with a porous film equivalent circuit model in order to better understand the HER behavior. In addition, modeling calculations, using density functional theory approach, were carried out to estimate the density of states and band structure of the boride solid solutions.« less

Electrical resistivity of the UAs 1- xSex solid solutions

NASA Astrophysics Data System (ADS)

Breandon, C.; Bartholin, H.; Tchapoutian, R.; Therond, P. G.; Schoenes, J.; Vogt, O.

1987-01-01

The electrical resistivity ϱ of UAs 1- xSex solid solutions has been measured between 13 K and room temperature. The magnetic phase diagram has been deduced. Effects of uniaxial stress on ϱ allow to understand some results and to reveal anisotropy of ϱ.

Production and properties of electrosprayed sericin nanopowder

NASA Astrophysics Data System (ADS)

Hazeri, Najmeh; Tavanai, Hossein; Moradi, Ali Reza

2012-06-01

Sericin is a proteinous substrate that envelops fibroin (silk) fiber, and its recovery provides significant economical and social benefits. Sericin is an antibacterial agent that resists oxidation and absorbs moisture and UV light. In powder form, sericin has a wide range of applications in food, cosmetics and drug delivery. Asides from other techniques of producing powder, such as precipitation and spray drying, electrospraying can yield solid nanoparticles, particularly in the submicron range. Here, we report the production of sericin nanopowder by electrospraying. Sericin sponge was recovered from Bombyx mori cocoons through a high-temperature, high-pressure process, followed by centrifugation and freeze drying of the sericin solution. The electrospraying solution was prepared by dissolving the sericin sponge in dimethyl sulfoxide. We demonstrate that electrospraying is capable of producing sericin nanopowder with an average particle size of 25 nm, which is by far smaller than the particles produced by other techniques. The electrosprayed sericin nanopowder consists of small crystallites and exhibits a high moisture absorbance.

Synthesis, characterization, crystal structure and solution studies of a novel proton transfer (charge transfer) complex of 2,2‧-dipyridylamine with 2,6-pyridine dicarboxylic acid

NASA Astrophysics Data System (ADS)

Ghasemi, Khaled; Rezvani, Ali Reza; Shokrollahi, Ardeshir; Zarghampour, Fereshteh; Moghimi, Abolghasem; García-Granda, Santiago; Mendoza-Meroño, Rafael

2015-06-01

Reaction between 2,2‧-dipyridylamine (DPA) and 2,6-pyridine dicarboxylic acid (dipicolinic acid, dipicH2), in water results in the formation of a proton transfer or charge transfer (CT) complex, (DPAH)+(dipicH)-·H2O, 1. The characterization was performed using 1H NMR and FTIR spectroscopy, elemental analysis and X-ray crystallography. The crystal system is triclinic with space group P1. The structural investigations exhibit that the hydrogen bonds and π-π stacking interactions stabilize the crystal structure of proton transfer complex. The protonation constants of 2,6-pyridine dicarboxylic acid, 2,2‧-dipyridylamine and the equilibrium constants for dipic-DPA (1:1) proton transfer system were calculated by potentiometric pH titration method using Hyperquad2008 program. The stoichiometries of the proton transfer species in solution was in agreement with the solid state result.

Structural, thermal and optical characterization of a Schiff base as a new organic material for nonlinear optical crystals and films with reversible noncentrosymmetry.

PubMed

Rodríguez, Mario; Ramos-Ortíz, Gabriel; Maldonado, José Luis; Herrera-Ambriz, Víctor M; Domínguez, Oscar; Santillan, Rosa; Farfán, Norberto; Nakatani, Keitaro

2011-09-01

Macroscopic single crystals of (E)-5-(diethylamino)-2-((3,5-dinitrophenylimino)methyl)phenol (DNP) were obtained from slow cooling of chloroform or dichlorometane saturated solutions at controlled temperature. X-ray diffraction analysis showed that this compound crystallizes in a noncentrosymmetric space group (P2(1)2(1)2(1)). Thermal analysis was performed and indicated that the crystals are stable until 260 °C. Second-order nonlinear optical properties of DNP were experimentally investigated in solution through EFISH technique and in solid state through the Kurtz-Perry powder technique. Crystals of compound DNP exhibited a second-harmonic signals 39 times larger than of the technologically useful potassium dihydrogenphosphate (KDP) under excitation at infrared wavelengths. In addition, the second-order nonlinear optical properties of DNP were also studied at visible wavelengths through the photorefractive effect and applied to demonstrate dynamic holographic reconstruction. Copyright © 2011 Elsevier B.V. All rights reserved.

Multi-functional bis(alkynyl)gold(iii) N⁁C complexes with distinct mechanochromic luminescence and electroluminescence properties† †Electronic supplementary information (ESI) available: CCDC 1552808. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc02410j

PubMed Central

Wong, Ben Yiu-Wing; Wong, Hok-Lai; Wong, Yi-Chun; Au, Vonika Ka-Man

2017-01-01

A new class of donor–acceptor type luminescent bis(alkynyl)gold(iii) N⁁C complexes has been synthesized and characterized. These gold(iii) complexes not only exhibit high photoluminescence quantum yields of up to 0.81, but also interesting mechanochromic luminescence behaviors that are reversible. Upon grinding, a dramatic luminescence color change from green to red can be observed in solid samples of the gold(iii) complexes, and the mechanochromic luminescence can be readily tuned via a judicious selection of substituents on the pyridine ring. In addition, solution-processable OLEDs based on this class of complexes with EQE values of up to 4.0% have been realized, representing the first demonstration of bis(alkynyl)gold(iii) N⁁C complexes as emissive materials in solution-processable OLEDs. PMID:29147519

Masked PDAMNA Film On Glass

NASA Technical Reports Server (NTRS)

1996-01-01

Polydiacetylenes are a unique class of highly conjugated organic polymers that are of interest for both electronic and photonic applications. Photodeposition from solutions is a novel process superior to those grown by conventional techniques. Evidence of this is seen when the films are viewed under a microscope; they exhibit small particles of solid polymer which form in the bulk solution, get transported by convection to the surface of the growing film, and become embedded. Also convection tends to cause the film thickness to be less uniform, and may even affect the molecular orientation of the films. The thrust of the research is to investigate in detail, both in 1-g and low-g, the effects of convection (and lack thereof) on this novel and interesting reaction. In this example, a portion of the substrate was blocked from exposure to the UV light by the mask, which was placed on the opposite side of the glass disk as the film, clearly demonstrating that photodeposition occurs only where the substrate is irradiated directly.

Microgravity

NASA Image and Video Library

1996-08-01

Polydiacetylenes are a unique class of highly conjugated organic polymers that are of interest for both electronic and photonic applications. Photodeposition from solutions is a novel process superior to those grown by conventional techniques. Evidence of this is seen when the films are viewed under a microscope; they exhibit small particles of solid polymer which form in the bulk solution, get transported by convection to the surface of the growing film, and become embedded. Also convection tends to cause the film thickness to be less uniform, and may even affect the molecular orientation of the films. The thrust of the research is to investigate in detail, both in 1-g and low-g, the effects of convection (and lack thereof) on this novel and interesting reaction. In this example, a portion of the substrate was blocked from exposure to the UV light by the mask, which was placed on the opposite side of the glass disk as the film, clearly demonstrating that photodeposition occurs only where the substrate is irradiated directly.

Inhibition of the solid state transformation of carbamazepine in aqueous solution: impact of polymeric properties.

PubMed

Gift, Alan D; Hettenbaugh, Jacob A; Quandahl, Rachel A; Mapes, Madison

2017-11-06

The effects of polymers on the anhydrate-to-hydrate transformation of carbamazepine (CBZ) was investigated. The three types of polymers studied were polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and substituted celluloses which included hydroxypropyl methylcellulose (HPMC) and methylcellulose (MC). Anhydrous CBZ was added to dilute aqueous polymer solutions and Raman spectroscopy measurements were collected to monitor the kinetics of the solution-mediated transformation to CBZ dihydrate. Polymers exhibiting the greatest inhibition were able to reduce the growth phase of the solution-mediated transformation and change the habit of the hydrate crystal indicating polymer adsorption to the hydrate crystal surface as the mechanism of inhibition. The results of the various polymers showed that short chain substituted celluloses (HPMC and MC) inhibited the CBZ transformation to a much greater extent than longer chains. The same trend was observed for PVP and PVA, but to a lesser extent. These chain length effects were attributed to changes in polymer confirmation when adsorbed on the crystal surface. Additionally, decreasing the percentage of hydroxyl groups on the PVA polymer backbone reduced the ability of the polymer to inhibit the transformation and changing the degree of substitutions of methyl and hydroxypropyl groups on the cellulosic polymer backbone had no effect on the transformation.

Evidence of dithionite contribution to the low-frequency resonance Raman spectrum of reduced and mixed-valence cytochrome c oxidase.

PubMed

Centeno, J A

1992-02-01

The resonance Raman spectra of deoxygenated solutions of mixed-valence cyanide-bound and fully reduced cytochrome oxidase derivatives that have been reduced in the presence of aqueous or solid sodium dithionite exhibit two new low-frequency lines centered at 474 and 590 cm-1. These lines were not observed when the reductant system was changed to a solution containing ascorbate and N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD). Under enzyme turnover conditions, the addition of dithionite to the reoxidized protein (the 428-nm or "oxygenated" form) increases the intensity of these lines, while reoxidation and rereduction of the enzyme in the presence of ascorbate/TMPD resulted in the absence of both lines. Our data suggest that both lines must have contributions from species formed from aqueous dithionite, presumably the SO2 species, since these two lines are also observed in the Raman spectrum of a solution of aqueous dithionite, but not in the spectrum of an ascorbate/TMPD solution. Since heme metal-ligand stretch vibrations are expected to appear in the low-frequency region from 215 to 670 cm-1, our results indicate that special care should be exercised during the interpretation of the cytochrome a3 resonance Raman spectrum.

TANK 26F SUPERNATANT AND 2F EVAPORATOR EDUCTOR PUMP SAMPLE CHARACTERIZATION RESULTS

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

King, W.; Hay, M.; Coleman, C.

2011-08-23

In an effort to understand the reasons for system plugging problems in the SRS 2F evaporator, supernatant samples were retrieved from the evaporator feed tank (Tank 26F) and solids were collected from the evaporator eductor feed pump for characterization. The variable depth supernatant samples were retrieved from Tank 26F in early December of 2010 and samples were provided to SRNL and the F/H Area laboratories for analysis. Inspection and analysis of the samples at SRNL was initiated in early March of 2011. During the interim period, samples were frequently exposed to temperatures as low as 12 C with daily temperaturemore » fluctuations as high as 10 C. The temperature at the time of sample collection from the waste tank was 51 C. Upon opening the supernatant bottles at SRNL, many brown solids were observed in both of the Tank 26F supernatant samples. In contrast, no solids were observed in the supernatant samples sent to the F/H Area laboratories, where the analysis was completed within a few days after receipt. Based on these results, it is believed that the original Tank 26F supernatant samples did not contain solids, but solids formed during the interim period while samples were stored at ambient temperature in the SRNL shielded cells without direct climate control. Many insoluble solids (>11 wt. % for one sample) were observed in the Tank 26F supernatant samples after three months of storage at SRNL which would not dissolve in the supernatant solution in two days at 51 C. Characterization of these solids along with the eductor pump solids revealed the presence of sodium oxalate and clarkeite (uranyl oxyhydroxide) as major crystalline phases. Sodium nitrate was the dominant crystalline phase present in the unwashed Eductor Pump solids. Crystalline sodium nitrate may have formed during the drying of the solids after filtration or may have been formed in the Tank 26F supernatant during storage since the solution was found to be very concentrated (9-12 M Na{sup +}). Concentrated mineral acids and elevated temperature were required to dissolve all of these solids. The refractory nature of some of the solids is consistent with the presence of metal oxides such as aluminosilicates (observed as a minor phase by XRD). Characterization of the water wash solutions and the digested solids confirmed the presence of oxalate salts in both solid samples. Sulfate enrichment was also observed in the Tank 26F solids wash solution, indicating the presence of sulfate precipitates such as burkeite. OLI modeling of the Tank 26F filtered supernatant composition revealed that sodium oxalate has a very low solubility in this solution. The model predicts that the sodium oxalate solubility in the Tank 26F supernatant is only 0.0011 M at 50 C. The results indicate that the highly concentrated nature of the evaporator feed solution and the addition of oxalate anion to the waste stream each contribute to the formation of insoluble solids in the 2F evaporator system.« less

Calorimetric determination of energetics of solid solutions of UO 2+ x with CaO and Y 2O 3

NASA Astrophysics Data System (ADS)

Mazeina, Lena; Navrotsky, Alexandra; Greenblatt, Martha

2008-02-01

Quantitative study of thermodynamic properties of solid solutions of UO 2+ x with divalent and trivalent oxides is important for predicting the behavior of oxide fuel. Although early literature work measured vapor pressure in some of these solid solutions, direct calorimetric measurements of enthalpies of formation have been hampered by the refractory nature of such oxides. First measurements of the enthalpies of formation in the systems UO 2+ x-CaO and UO 2+ x-YO 1.5, obtained by high-temperature oxide melt solution calorimetry, are reported. Both systems show significantly negative (exothermic) heats of formation from binary oxides (UO 2, plus O 2 and CaO or YO 1.5, as well as from UO 2 plus UO 3 and CaO or YO 1.5), consistent with reported free energy measurements in the urania-yttria system. The energetic contributions of oxygen content (oxidation of U 4+) and of charge balanced ionic substitution as well as defect clustering are discussed. Behavior of urania-yttria is compared to that of corresponding systems in which the tetravalent ion is Ce, Zr, or Hf. The substantial additional stability in the solid solutions compared to pure UO 2+ x may retard, in both thermodynamic and kinetic sense, the oxidation and leaching of spent fuel to form aqueous U 6+ and solid uranyl phases.

Incorporation of Cadmium and Nickel into Ferrite Spinel Solid Solution: X-ray Diffraction and X-ray Absorption Fine Structure Analyses.

PubMed

Su, Minhua; Liao, Changzhong; Chan, Tingshan; Shih, Kaimin; Xiao, Tangfu; Chen, Diyun; Kong, Lingjun; Song, Gang

2018-01-16

The feasibility of incorporating Cd and Ni in hematite was studied by investigating the interaction mechanism for the formation of Cd x Ni 1-x Fe 2 O 4 solid solutions (CNFs) from CdO, NiO, and α-Fe 2 O 3 . X-ray diffraction results showed that the CNFs crystallized into spinel structures with increasing lattice parameters as the Cd content in the precursors was increased. Cd 2+ ions were found to occupy the tetrahedral sites, as evidenced by Rietveld refinement and extended X-ray absorption fine structure analyses. The incorporation of Cd and Ni into ferrite spinel solid solution strongly relied on the processing parameters. The incorporation of Cd and Ni into the CNFs was greater at high x values (0.7 < x ≤ 1.0) than at low x values (0.0 ≤ x ≤ 0.7). A feasible treatment technique based on the investigated mechanism of CNF formation was developed, involving thermal treatment of waste sludge containing Cd and Ni. Both of these metals in the waste sludge were successfully incorporated into a ferrite spinel solid solution, and the concentrations of leached Cd and Ni from this solid solution were substantially reduced, stabilizing at low levels. This research offers a highly promising approach for treating the Cd and Ni content frequently encountered in electronic waste and its treatment residues.

Quantum junction solar cells.

PubMed

Tang, Jiang; Liu, Huan; Zhitomirsky, David; Hoogland, Sjoerd; Wang, Xihua; Furukawa, Melissa; Levina, Larissa; Sargent, Edward H

2012-09-12

Colloidal quantum dot solids combine convenient solution-processing with quantum size effect tuning, offering avenues to high-efficiency multijunction cells based on a single materials synthesis and processing platform. The highest-performing colloidal quantum dot rectifying devices reported to date have relied on a junction between a quantum-tuned absorber and a bulk material (e.g., TiO(2)); however, quantum tuning of the absorber then requires complete redesign of the bulk acceptor, compromising the benefits of facile quantum tuning. Here we report rectifying junctions constructed entirely using inherently band-aligned quantum-tuned materials. Realizing these quantum junction diodes relied upon the creation of an n-type quantum dot solid having a clean bandgap. We combine stable, chemically compatible, high-performance n-type and p-type materials to create the first quantum junction solar cells. We present a family of photovoltaic devices having widely tuned bandgaps of 0.6-1.6 eV that excel where conventional quantum-to-bulk devices fail to perform. Devices having optimal single-junction bandgaps exhibit certified AM1.5 solar power conversion efficiencies of 5.4%. Control over doping in quantum solids, and the successful integration of these materials to form stable quantum junctions, offers a powerful new degree of freedom to colloidal quantum dot optoelectronics.

Effect of Te substitution on crystal structure and transport properties of AgBiSe2 thermoelectric material.

PubMed

Goto, Y; Nishida, A; Nishiate, H; Murata, M; Lee, C H; Miura, A; Moriyoshi, C; Kuroiwa, Y; Mizuguchi, Y

2018-02-20

Silver bismuth diselenide (AgBiSe 2 ) has attracted much attention as an efficient thermoelectric material, owing to its intrinsically low lattice thermal conductivity. While samples synthesized using a solid-state reaction showed n-type conductivity and their dimensionless figure of merit (ZT) reached ∼1 by electron doping, theoretical calculations predicted that a remarkably high thermoelectric performance can be achieved in p-type AgBiSe 2 . In this paper, we present the effect of Te substitution on the crystal structure and thermoelectric properties of AgBiSe 2 , expecting p-type conductivity due to the shallowing of the energy potential of the valence band. We found that all AgBiSe 2-x Te x (x = 0-0.8) prepared using a solid-state reaction exhibits n-type conductivity from 300 to 750 K. The room-temperature lattice thermal conductivity decreased to as low as 0.3 W m -1 K -1 by Te substitution, which was qualitatively described using the point defect scattering model for the solid solution. We show that ZT reaches ∼0.6 for x = 0.8 at a broad range of temperatures, from 550 to 750 K, due to the increased power factor, although the carrier concentration has not been optimized yet.

PEGylation of magnetic multi-walled carbon nanotubes for enhanced selectivity of dispersive solid phase extraction.

PubMed

Zeng, Qiong; Liu, Yi-Ming; Jia, Yan-Wei; Wan, Li-Hong; Liao, Xun

2017-02-01

Carbon nanotubes (CNTs) possess large potential as extraction absorbents in solid phase extraction. They have been widely applied in biomedicine research, while very rare application in natural product chemistry has been reported. In this work, methoxypolyethylene glycol amine (mPEG-NH 2 ) is covalently coupled to CNTs-magnetic nanoparticles (CNTs-MNP) to prepare a novel magnetic nanocomposite (PEG-CNTs-MNP) for use as dispersive solid-phase extraction (DSPE) absorbent. The average particle size was 86nm, and the saturation magnetization was 52.30emu/g. This nanocomposite exhibits excellent dispersibility in aqueous systems, high selectivity and fast binding kinetics when used for extraction of Z-ligustilide, the characteristic bioactive compound from two popular Asian herbal plants, R. chuanxiong and R. ligusticum. HPLC quantification of Z-ligustilide extracted from the standard sample solution showed a high recovery of 98.9%, and the extraction rate from the extracts of the above two herbs are both around 70.0%. To our knowledge, this is the first report on using PEG-CNTs-MNP as DSPE nanosorbents for selective extraction of natural products. This nano-material has promising application in isolation and enrichment of targeted components from complex matrices. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Du Hongliang; Zhou Wancheng; Luo Fa

The (1-x)(K{sub 0.5}Na{sub 0.5})NbO{sub 3}-x(Ba{sub 0.5}Sr{sub 0.5})TiO{sub 3} (KNN-BST) solid solution has been synthesized by conventional solid-state sintering in order to search for the new lead-free relaxor ferroelectrics for high temperature applications. The phase structure, dielectric properties, and relaxor behavior of the (1-x)KNN-xBST solid solution are systematically investigated. The phase structure of the (1-x)KNN-xBST solid solution gradually changes from pure perovskite phase with an orthorhombic symmetry to the tetragonal symmetry, then to the pseudocubic phase, and to the cubic phase with increasing addition of BST. The 0.90KNN-0.10BST solid solution shows a broad dielectric peak with permittivity maximum near 2500 andmore » low dielectric loss (<4%) in the temperature range of 100-250 deg. C. The result indicates that this material may have great potential for a variety of high temperature applications. The diffuse phase transition and the temperature of the maximum dielectric permittivity shifting toward higher temperature with increasing frequency, which are two typical characteristics for relaxor ferroelectrics, are observed in the (1-x)KNN-xBST solid solution. The dielectric relaxor behavior obeys a modified Curie-Weiss law and a Vogel-Fulcher relationship. The relaxor nature is attributed to the appearance of polar nanoregions owing to the formation of randon fields including local electric fields and elastic fields. These results confirm that the KNN-based relaxor ferroelectrics can be regarded as an alternative direction for the development of high temperature lead-free relaxor ferroelectrics.« less

Mixing Acid Salts and Layered Double Hydroxides in Nanoscale under Solid Condition

PubMed Central

Nakayama, Hirokazu; Hayashi, Aki

2014-01-01

The immobilization of potassium sorbate, potassium aspartate and sorbic acid in layered double hydroxide under solid condition was examined. By simply mixing two solids, immobilization of sorbate and aspartate in the interlayer space of nitrate-type layered double hydroxide, so called intercalation reaction, was achieved, and the uptakes, that is, the amount of immobilized salts and the interlayer distances of intercalation compounds were almost the same as those obtained in aqueous solution. However, no intercalation was achieved for sorbic acid. Although intercalation of sorbate and aspartate into chloride-type layered double hydroxide was possible, the uptakes for these intercalation compounds were lower than those obtained using nitrate-type layered double hydroxide. The intercalation under solid condition could be achieved to the same extent as for ion-exchange reaction in aqueous solution, and the reactivity was similar to that observed in aqueous solution. This method will enable the encapsulation of acidic drug in layered double hydroxide as nano level simply by mixing both solids. PMID:25080007

Mixing Acid Salts and Layered Double Hydroxides in Nanoscale under Solid Condition.

PubMed

Nakayama, Hirokazu; Hayashi, Aki

2014-07-30

The immobilization of potassium sorbate, potassium aspartate and sorbic acid in layered double hydroxide under solid condition was examined. By simply mixing two solids, immobilization of sorbate and aspartate in the interlayer space of nitrate-type layered double hydroxide, so called intercalation reaction, was achieved, and the uptakes, that is, the amount of immobilized salts and the interlayer distances of intercalation compounds were almost the same as those obtained in aqueous solution. However, no intercalation was achieved for sorbic acid. Although intercalation of sorbate and aspartate into chloride-type layered double hydroxide was possible, the uptakes for these intercalation compounds were lower than those obtained using nitrate-type layered double hydroxide. The intercalation under solid condition could be achieved to the same extent as for ion-exchange reaction in aqueous solution, and the reactivity was similar to that observed in aqueous solution. This method will enable the encapsulation of acidic drug in layered double hydroxide as nano level simply by mixing both solids.

The mechanical problems on additive manufacturing of viscoelastic solids with integral conditions on a surface increasing in the growth process

NASA Astrophysics Data System (ADS)

Parshin, D. A.; Manzhirov, A. V.

2018-04-01

Quasistatic mechanical problems on additive manufacturing aging viscoelastic solids are investigated. The processes of piecewise-continuous accretion of such solids are considered. The consideration is carried out in the framework of linear mechanics of growing solids. A theorem about commutativity of the integration over an arbitrary surface increasing in the solid growing process and the time-derived integral operator of viscoelasticity with a limit depending on the solid point is proved. This theorem provides an efficient way to construct on the basis of Saint-Venant principle solutions of nonclassical boundary-value problems for describing the mechanical behaviour of additively formed solids with integral satisfaction of boundary conditions on the surfaces expanding due to the additional material influx to the formed solid. The constructed solutions will retrace the evolution of the stress-strain state of the solids under consideration during and after the processes of their additive formation. An example of applying the proved theorem is given.

Characterization, dissolution and solubility of the hydroxypyromorphite-hydroxyapatite solid solution [(PbxCa1-x)5(PO4)3OH] at 25 °C and pH 2-9.

PubMed

Zhu, Yinian; Huang, Bin; Zhu, Zongqiang; Liu, Huili; Huang, Yanhua; Zhao, Xin; Liang, Meina

2016-01-01

The interaction between Ca-HAP and Pb(2+) solution can result in the formation of a hydroxyapatite-hydroxypyromorphite solid solution [(PbxCa1-x)5(PO4)3(OH)], which can greatly affect the transport and distribution of toxic Pb in water, rock and soil. Therefore, it's necessary to know the physicochemical properties of (PbxCa1-x)5(PO4)3(OH), predominantly its thermodynamic solubility and stability in aqueous solution. Nevertheless, no experiment on the dissolution and related thermodynamic data has been reported. Dissolution of the hydroxypyromorphite-hydroxyapatite solid solution [(PbxCa1-x)5(PO4)3(OH)] in aqueous solution at 25 °C was experimentally studied. The aqueous concentrations were greatly affected by the Pb/(Pb + Ca) molar ratios (XPb) of the solids. For the solids with high XPb [(Pb0.89Ca0.11)5(PO4)3OH], the aqueous Pb(2+) concentrations increased rapidly with time and reached a peak value after 240-720 h dissolution, and then decreased gradually and reached a stable state after 5040 h dissolution. For the solids with low XPb (0.00-0.80), the aqueous Pb(2+) concentrations increased quickly with time and reached a peak value after 1-12 h dissolution, and then decreased gradually and attained a stable state after 720-2160 h dissolution. The dissolution process of the solids with high XPb (0.89-1.00) was different from that of the solids with low XPb (0.00-0.80). The average K sp values were estimated to be 10(-80.77±0.20) (10(-80.57)-10(-80.96)) for hydroxypyromorphite [Pb5(PO4)3OH] and 10(-58.38±0.07) (10(-58.31)-10(-58.46)) for calcium hydroxyapatite [Ca5(PO4)3OH]. The Gibbs free energies of formation (ΔG f (o) ) were determined to be -3796.71 and -6314.63 kJ/mol, respectively. The solubility decreased with the increasing Pb/(Pb + Ca) molar ratios (XPb) of (PbxCa1‒x)5(PO4)3(OH). For the dissolution at 25 °C with an initial pH of 2.00, the experimental data plotted on the Lippmann diagram showed that the solid solution (PbxCa1-x)5(PO4)3(OH) dissolved stoichiometrically at the early stage of dissolution and moved gradually up to the Lippmann solutus curve and the saturation curve for Pb5(PO4)3OH, and then the data points moved along the Lippmann solutus curve from right to left. The Pb-rich (PbxCa1-x)5(PO4)3(OH) was in equilibrium with the Ca-rich aqueous solution. Graphical abstractLippmann diagrams for dissolution of the hydroxypyromorphite-hydroxyapatite solid solution [(PbxCa1-x)5(PO4)3OH] at 25 ˚C and an initial pH of 2.00.

Compositional effects on the chemorheological properties and forming behavior of aqueous alumina-poly(vinyl alcohol) gelcasting suspensions

NASA Astrophysics Data System (ADS)

Morissette, Sherry L.

A new gelcasting system based on aqueous, alumina-poly(vinyl alcohol) (PVA) suspensions cross-linked by an organotitanate coupling agent has been developed. Both the chemorheological properties and forming behavior of this system exhibited a strong compositional dependence. A sol- gel phase diagram was established, which yielded the critical titanium concentration [Ti] c required for gelation at a given PVA volume fraction, as well as the minimum PVA volume fraction ( fminPVA = 0.0245) and titanium PVA concentration ([Ti]min = 9.984 x 10--4 g Ti/ml) below which gelation was not observed irrespective of solution composition. The gelation time of suspensions of constant PVA volume fraction ( fsolnPVA ) decreased with increasing cross-linking agent concentration, PVA temperature, and solids volume fraction. The steady-state viscosity and elastic modulus of polymer solutions ( fsolnPVA = 0.05) of varying [Ti] were well described by the PVA percolation model, giving scaling exponents of 0.84 and 1.79, respectively. The steady-state elastic modulus of gel casting suspensions, which provides a measure of their handling strength in the as-gelled state, increased with increasing solids volume fraction. Gelcasting suspensions were used as feedstock for solid free-form fabrication (SFF) of ceramic components. The influence of processing conditions (e.g., tip diameter, mixing rate, table speed, etc.) and suspension rheology on deposition behavior was investigated. Continuous printablity was achieved for tip diameters ranging from dt = 0.254 -- 1.370 mm for all mixing rates (Rmix 5 -- 300 rpm) and suspension compositions (i.e., fAl2O3 = 0.45, φPVA = 0.275, [Ti] 0 -- 6.30 x 10--3 g Ti/ml) probed, where the minimum tip diameter for continuous printing was 0.203 mm. Printed lines were uniform with good edge definition. Line dimensions were independent of mixing rate for the given process conditions. The as-cast alumina volume fraction ( fAl2O3 ) depended on casting conditions and cross-linking agent concentration, where fAl2O3 decreased with increasing tip diameter and increased with increasing cross-linking agent concentration. Free-fomied Al2O3 components exhibited uniform particle packing and had minimal macro-defects (e.g., slumping or stair casing) and no detectable micro-defects (e.g., bubbles or cracking).

Kinetic precipitation of solution-phase polyoxomolybdate followed by transmission electron microscopy: a window to solution-phase nanostructure.

PubMed

Zhu, Yan; Cammers-Goodwin, Arthur; Zhao, Bin; Dozier, Alan; Dickey, Elizabeth C

2004-05-17

This study aimed to elucidate the structural nature of the polydisperse, nanoscopic components in the solution and the solid states of partially reduced polyoxomolybdate derived from the [Mo132] keplerate, [(Mo)Mo5]12-[Mo2 acetate]30. Designer tripodal hexamine-tris-crown ethers and nanoscopic molybdate coprecipitated from aqueous solution. These microcrystalline solids distributed particle radii between 2-30 nm as assayed by transmission electron microscopy (TEM). The solid materials and their particle size distributions were snap shots of the solution phase. The mother liquor of the preparation of the [Mo132] keplerate after three days revealed large species (r=20-30 nm) in the coprecipitate, whereas [Mo132] keplerate redissolved in water revealed small species (3-7 nm) in the coprecipitate. Nanoparticles of coprecipitate were more stable than solids derived solely from partially reduced molybdate. The TEM features of all material analyzed lacked facets on the nanometer length scale; however, the structures diffracted electrons and appeared to be defect-free as evidenced by Moiré patterns in the TEM images. Moiré patterns and size-invariant optical densities of the features in the micrographs suggested that the molybdate nanoparticles were vesicular.

Solute redistribution in dendritic solidification with diffusion in the solid

NASA Technical Reports Server (NTRS)

Ganesan, S.; Poirier, D. R.

1989-01-01

An investigation of solute redistribution during dendritic solidification with diffusion in the solid has been performed using numerical techniques. The extent of diffusion is characterized by the instantaneous and average diffusion parameters. These parameters are functions of the diffusion Fourier number, the partition ratio and the fraction solid. Numerical results are presented as an approximate model, which is used to predict the average diffusion parameter and calculate the composition of the interdendritic liquid during solidification.

Assessing the Selectivity of Extractant Solutions for Recovering Labile Arsenic Associated with Iron (Hydr)oxides and Sulfides in Sediments

EPA Science Inventory

Sequential extractions can provide analytical constraints on the identification of mineral phases that control arsenic speciation in sediments. Model solids were used in this study to evaluate different solutions designed to extract arsenic from relatively labile solid phases. ...

Thermodynamics of aragonite-strontianite solid solutions: Results from stoichiometric solubility at 25 and 76°C

USGS Publications Warehouse

Plummer, Niel; Busenberg, E.

1987-01-01

Neither equilibrium nor stoichiometric saturation is observed at 76°C during laboratory recrystallization of strontianite-aragonite solid solutions even after apparent 100 percent conversion to a narrow secondary composition and demonstration of a nearly constant composition system for periods of 300 hours.

A fluorescent chemosensor for Zn(II). Exciplex formation in solution and the solid state.

PubMed

Bencini, Andrea; Berni, Emanuela; Bianchi, Antonio; Fornasari, Patrizia; Giorgi, Claudia; Lima, Joao C; Lodeiro, Carlos; Melo, Maria J; de Melo, J Seixas; Parola, Antonio Jorge; Pina, Fernando; Pina, Joao; Valtancoli, Barbara

2004-07-21

The macrocyclic phenanthrolinophane 2,9-[2,5,8-triaza-5-(N-anthracene-9-methylamino)ethyl]-[9]-1,10-phenanthrolinophane (L) bearing a pendant arm containing a coordinating amine and an anthracene group forms stable complexes with Zn(II), Cd(II) and Hg(II) in solution. Stability constants of these complexes were determined in 0.10 mol dm(-3) NMe(4)Cl H(2)O-MeCN (1:1, v/v) solution at 298.1 +/- 0.1 K by means of potentiometric (pH metric) titration. The fluorescence emission properties of these complexes were studied in this solvent. For the Zn(II) complex, steady-state and time-resolved fluorescence studies were performed in ethanol solution and in the solid state. In solution, intramolecular pi-stacking interaction between phenanthroline and anthracene in the ground state and exciplex emission in the excited state were observed. From the temperature dependence of the photostationary ratio (I(Exc)/I(M)), the activation energy for the exciplex formation (E(a)) and the binding energy of the exciplex (-DeltaH) were determined. The crystal structure of the [ZnLBr](ClO(4)).H(2)O compound was resolved, showing that in the solid state both intra- and inter-molecular pi-stacking interactions are present. Such interactions were also evidenced by UV-vis absorption and emission spectra in the solid state. The absorption spectrum of a thin film of the solid complex is red-shifted compared with the solution spectra, whereas its emission spectrum reveals the unique featureless exciplex band, blue shifted compared with the solution. In conjunction with X-ray data the solid-state data was interpreted as being due to a new exciplex where no pi-stacking (full overlap of the pi-electron cloud of the two chromophores - anthracene and phenanthroline) is observed. L is a fluorescent chemosensor able to signal Zn(II) in presence of Cd(II) and Hg(II), since the last two metal ions do not give rise either to the formation of pi-stacking complexes or to exciplex emission in solution.

Liquid-like cationic sub-lattice in copper selenide clusters

NASA Astrophysics Data System (ADS)

White, Sarah L.; Banerjee, Progna; Jain, Prashant K.

2017-02-01

Super-ionic solids, which exhibit ion mobilities as high as those in liquids or molten salts, have been employed as solid-state electrolytes in batteries, improved thermoelectrics and fast-ion conductors in super-capacitors and fuel cells. Fast-ion transport in many of these solids is supported by a disordered, `liquid-like' sub-lattice of cations mobile within a rigid anionic sub-lattice, often achieved at high temperatures or pressures via a phase transition. Here we show that ultrasmall clusters of copper selenide exhibit a disordered cationic sub-lattice under ambient conditions unlike larger nanocrystals, where Cu+ ions and vacancies form an ordered super-structure similar to the bulk solid. The clusters exhibit an unusual cationic sub-lattice arrangement wherein octahedral sites, which serve as bridges for cation migration, are stabilized by compressive strain. The room-temperature liquid-like nature of the Cu+ sub-lattice combined with the actively tunable plasmonic properties of the Cu2Se clusters make them suitable as fast electro-optic switches.

Determination of the Fracture Parameters in a Stiffened Composite Panel

NASA Technical Reports Server (NTRS)

Lin, Chung-Yi

2000-01-01

A modified J-integral, namely the equivalent domain integral, is derived for a three-dimensional anisotropic cracked solid to evaluate the stress intensity factor along the crack front using the finite element method. Based on the equivalent domain integral method with auxiliary fields, an interaction integral is also derived to extract the second fracture parameter, the T-stress, from the finite element results. The auxiliary fields are the two-dimensional plane strain solutions of monoclinic materials with the plane of symmetry at x(sub 3) = 0 under point loads applied at the crack tip. These solutions are expressed in a compact form based on the Stroh formalism. Both integrals can be implemented into a single numerical procedure to determine the distributions of stress intensity factor and T-stress components, T11, T13, and thus T33, along a three-dimensional crack front. The effects of plate thickness and crack length on the variation of the stress intensity factor and T-stresses through the thickness are investigated in detail for through-thickness center-cracked plates (isotropic and orthotropic) and orthotropic stiffened panels under pure mode-I loading conditions. For all the cases studied, T11 remains negative. For plates with the same dimensions, a larger size of crack yields larger magnitude of the normalized stress intensity factor and normalized T-stresses. The results in orthotropic stiffened panels exhibit an opposite trend in general. As expected, for the thicker panels, the fracture parameters evaluated through the thickness, except the region near the free surfaces, approach two-dimensional plane strain solutions. In summary, the numerical methods presented in this research demonstrate their high computational effectiveness and good numerical accuracy in extracting these fracture parameters from the finite element results in three-dimensional cracked solids.

High-Solids Polyimide Precursor Solutions

NASA Technical Reports Server (NTRS)

Chuang, Chun-Hua (Inventor)

2004-01-01

The invention is a highly concentrated stable solution of polymide precursors (monometers) having a solids content ranging from about 80 to 98 percent by weight in lower aliphatic alcohols i.e. methyl and/or ethylalcohol. the concentrated polyimide precursos solution comparisons effective amounts of at least one aromatic diamine, at least one aromatic dianhydride, and a monofunctional endcap including monoamines, monoanhydrides and lower alkyl esters of said monoanhydrides. These concentrated polyimide precursor solutions are particularly useful for the preparation of fibrous prepregs and composites for use in structural materials for military and civil applications.

PROCESS OF MAKING A NEUTRONIC REACTOR FUEL ELEMENT COMPOSITION

DOEpatents

Alter, H.W.; Davidson, J.K.; Miller, R.S.; Mewherter, J.L.

1959-01-13

A process is presented for making a ceramic-like material suitable for use as a nuclear fuel. The material consists of a solid solution of plutonium dioxide in uranium dioxide and is produced from a uranyl nitrate -plutonium nitrate solution containing uraniunm and plutonium in the desired ratio. The uranium and plutonium are first precipitated from the solution by addition of NH/ sub 4/OH and the dried precipitate is then calcined at 600 C in a hydrogen atmosphere to yield the desired solid solution of PuO/sub 2/ in UO/sub 2/.

Emergency deployable core catcher

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

Rosewell, M.P.

An emergency melt down core catcher apparatus for a nuclear reactor having a retrofitable eutectic solute holding vessel connected to a core containment vessel with particle transferring fluid and particles or granules of solid eutectic solute materials contained therein and transferable by automatically operated valve means to transport and position the solid eutectic solute material in a position below the core to catch and react with any partial or complete melt down of the fuel core.

Organic-inorganic hybrid polymer electrolytes based on polyether diamine, alkoxysilane, and trichlorotriazine: Synthesis, characterization, and electrochemical applications

NASA Astrophysics Data System (ADS)

Saikia, Diganta; Wu, Cheng-Gang; Fang, Jason; Tsai, Li-Duan; Kao, Hsien-Ming

2014-12-01

A new type of highly conductive organic-inorganic hybrid polymer electrolytes has been synthesized by the reaction of poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether), 2,4,6-trichloro-1,3,5-triazine and alkoxysilane precursor 3-(glycidyloxypropyl)trimethoxysilane, followed by doping of LiClO4. The 13C and 29Si solid-sate NMR results confirm the successful synthesis of the organic-inorganic hybrid structure. The solid hybrid electrolyte thus obtained exhibits a maximum ionic conductivity of 1.6 × 10-4 S cm-1 at 30 °C, which is the highest among the organic-inorganic hybrid electrolytes. The hybrid electrolytes are electrochemically stable up to 4.2 V. The prototype electrochromic device with such a solid hybrid electrolyte demonstrates a good coloration efficiency value of 183 cm2 C-1 with a cycle life over 200 cycles. For the lithium-ion battery test, the salt free solid hybrid membrane is swelled with a LiPF6-containing electrolyte solution to reach an acceptable ionic conductivity value of 6.5 × 10-3 S cm-1 at 30 °C. The battery cell carries an initial discharge capacity of 100 mAh g-1 at 0.2C-rate and a coulombic efficiency of about 95% up to 30 cycles without the sign of cell failure. The present organic-inorganic hybrid electrolytes hold promise for applications in electrochromic devices and lithium ion batteries.

Low-temperature solid-state preparation of ternary CdS/g-C3N4/CuS nanocomposites for enhanced visible-light photocatalytic H2-production activity

NASA Astrophysics Data System (ADS)

Cheng, Feiyue; Yin, Hui; Xiang, Quanjun

2017-01-01

Low-temperature solid-state method were gradually demonstrated as a high efficiency, energy saving and environmental protection strategy to fabricate composite semiconductor materials. CdS-based multiple composite photocatalytic materials have attracted increasing concern owning to the heterostructure constituents with tunable band gaps. In this study, the ternary CdS/g-C3N4/CuS composite photocatalysts were prepared by a facile and novel low-temperature solid-state strategy. The optimal ternary CdS/g-C3N4/CuS composite exhibits a high visible-light photocatalytic H2-production rate of 57.56 μmol h-1 with the corresponding apparent quantum efficiency reaches 16.5% at 420 nm with Na2S/Na2SO3 mixed aqueous solution as sacrificial agent. The ternary CdS/g-C3N4/CuS composites show the enhanced visible-light photocatalytic H2-evolution activity comparing with the binary CdS-based composites or simplex CdS. The enhanced photocatalytic activity is ascribed to the heterojunctions and the synergistic effect of CuS and g-C3N4 in promotion of the charge separation and charge mobility. This work shows that the low-temperature solid-state method is efficient and environmentally benign for the preparation of CdS-based multiple composite photocatalytic materials with enhanced visible-light photocatalytic H2-production activity.

Temporal variability and annual budget of inorganic dissolved matter in Andean Pacific Rivers located along a climate gradient from northern Ecuador to southern Peru

NASA Astrophysics Data System (ADS)

Moquet, Jean-Sébastien; Guyot, Jean-Loup; Morera, Sergio; Crave, Alain; Rau, Pedro; Vauchel, Philippe; Lagane, Christelle; Sondag, Francis; Lavado, Casimiro Waldo; Pombosa, Rodrigo; Martinez, Jean-Michel

2018-01-01

In Ecuador and Peru, geochemical information from Pacific coastal rivers is limited and scarce. Here, we present an unedited database of major element concentrations from five HYBAM observatory stations monitored monthly between 4 and 10 years, and the discrete sampling of 23 Andean rivers distributed along the climate gradient of the Ecuadorian and Peruvian Pacific coasts. Concentration (C) vs. discharge (Q) relationships of the five monitored basins exhibit a clear dilution behavior for evaporites and/or pyrite solutes, while the solute concentrations delivered by other endmembers are less variable. Spatially, the annual specific fluxes for total dissolved solids (TDS), Ca2+, HCO3-, K+, Mg2+, and SiO2 are controlled on the first order by runoff variability, while Cl-, Na+ and SO42- are controlled by the occurrence of evaporites and/or pyrite. The entire Pacific basin in Ecuador and Peru exported 30 Mt TDS·yr-1, according to a specific flux of ∼70 t·km-2·yr-1. This show that, even under low rainfall conditions, this orogenic context is more active, in terms of solute production, than the global average.

Effect of heat treatment on interfacial and mechanical properties of A6022/A7075/A6022 roll-bonded multi-layer Al alloy sheets

NASA Astrophysics Data System (ADS)

Cha, Joon-Hyeon; Kim, Su-Hyeon; Lee, Yun-Soo; Kim, Hyoung-Wook; Choi, Yoon Suk

2016-09-01

Multi-layered Al alloy sheets can exhibit unique properties by the combination of properties of component materials. A poor corrosion resistance of high strength Al alloys can be complemented by having a protective surface with corrosion resistant Al alloys. Here, a special care should be taken regarding the heat treatment of multi-layered Al alloy sheets because dissimilar Al alloys may exhibit unexpected interfacial reactions upon heat treatment. In the present study, A6022/A7075/A6022 sheets were fabricated by a cold roll-bonding process, and the effect of the heat treatment on the microstructure and mechanical properties was examined. The solution treatment gave rise to the diffusion of Zn, Mg, Cu and Si elements across the core/clad interface. In particular, the pronounced diffusion of Zn, which is a major alloying element (for solid-solution strengthening) of the A7075 core, resulted in a gradual hardness change across the core/clad interface. Mg2Si precipitates and the precipitate free zone were also formed near the interface after the heat treatment. The heat-treated sheet showed high strengths and reasonable elongation without apparent deformation misfit or interfacial delamination during the tensile deformation. The high strength of the sheet was mainly due to the T4 and T6 heat treatment of the A7075 core.

Atom probe tomographic studies of precipitation in Al-0.1Zr-0.1Ti (at.%) alloys.

PubMed

Knipling, Keith E; Dunand, David C; Seidman, David N

2007-12-01

Atom probe tomography was utilized to measure directly the chemical compositions of Al(3)(Zr(1)-(x)Ti(x)) precipitates with a metastable L1(2) structure formed in Al-0.1Zr-0.1Ti (at.%) alloys upon aging at 375 degrees C or 425 degrees C. The alloys exhibit an inhomogeneous distribution of Al(3)(Zr(1)-(x)Ti(x)) precipitates, as a result of a nonuniform dendritic distribution of solute atoms after casting. At these aging temperatures, the Zr:Ti atomic ratio in the precipitates is about 10 and 5, respectively, indicating that Ti remains mainly in solid solution rather than partitioning to the Al(3)(Zr(1)-(x)Ti(x)) precipitates. This is interpreted as being due to the very small diffusivity of Ti in alpha-Al, consistent with prior studies on Al-Sc-Ti and Al-Sc-Zr alloys, where the slower diffusing Zr and Ti atoms make up a small fraction of the Al(3)(Zr(1)-(x)Ti(x)) precipitates. Unlike those alloys, however, the present Al-Zr-Ti alloys exhibit no interfacial segregation of Ti at the matrix/precipitate heterophase interface, a result that may be affected by a significant disparity in the evaporation fields of the alpha-Al matrix and Al(3)(Zr(1)-(x)Ti(x)) precipitates and/or a lack of local thermodynamic equilibrium at the interface.

MBSSAS: A code for the computation of margules parameters and equilibrium relations in binary solid-solution aqueous-solution systems

USGS Publications Warehouse

Glynn, P.D.

1991-01-01

The computer code MBSSAS uses two-parameter Margules-type excess-free-energy of mixing equations to calculate thermodynamic equilibrium, pure-phase saturation, and stoichiometric saturation states in binary solid-solution aqueous-solution (SSAS) systems. Lippmann phase diagrams, Roozeboom diagrams, and distribution-coefficient diagrams can be constructed from the output data files, and also can be displayed by MBSSAS (on IBM-PC compatible computers). MBSSAS also will calculate accessory information, such as the location of miscibility gaps, spinodal gaps, critical-mixing points, alyotropic extrema, Henry's law solid-phase activity coefficients, and limiting distribution coefficients. Alternatively, MBSSAS can use such information (instead of the Margules, Guggenheim, or Thompson and Waldbaum excess-free-energy parameters) to calculate the appropriate excess-free-energy of mixing equation for any given SSAS system. ?? 1991.

The structure investigations of dehydroacetic acid and 1,8-diaminonaphthalene condensation product by NMR, MS, and X-ray measurements

NASA Astrophysics Data System (ADS)

Kołodziej, B.; Morawiak, M.; Kamieński, B.; Schilf, W.

2016-05-01

A new unexpected product of condensation reaction of 1,8-diaminonaphthalene (DAN) and carbonyl compound (here: dehydroacetic acid (dha)) was synthesized. Discussion about the molecular structure of possible products of this reaction was done on the base of NMR studies. The structure of the titled product in both DMSO solution and in the solid state was resolved by analysis of its spectral data (X-ray structure analysis, multinuclear NMR in solution and solid state spectra) and MS measurements. The presented studies provided clear evidence that the titled product exists in diluted DMSO solution as the mixture of two kinetic free ionic species whereas in concentrated DMSO solution as well as in the solid state this system forms associated ionic pairs bonded together by hydrogen bonds.

Local Bonding Influence on the Band Edge and Band Gap Formation in Quaternary Chalcopyrites.

PubMed

Miglio, Anna; Heinrich, Christophe P; Tremel, Wolfgang; Hautier, Geoffroy; Zeier, Wolfgang G

2017-09-01

Quaternary chalcopyrites have shown to exhibit tunable band gaps with changing anion composition. Inspired by these observations, the underlying structural and electronic considerations are investigated using a combination of experimentally obtained structural data, molecular orbital considerations, and density functional theory. Within the solid solution Cu 2 ZnGeS 4- x Se x , the anion bond alteration parameter changes, showing larger bond lengths for metal-selenium than for metal-sulfur bonds. The changing bonding interaction directly influences the valence and conduction band edges, which result from antibonding Cu-anion and Ge-anion interactions, respectively. The knowledge of the underlying bonding interactions at the band edges can help design properties of these quaternary chalcopyrites for photovoltaic and thermoelectric applications.

Using light transmission to watch hydrogen diffuse

PubMed Central

Pálsson, Gunnar K.; Bliersbach, Andreas; Wolff, Max; Zamani, Atieh; Hjörvarsson, Björgvin

2012-01-01

Because of its light weight and small size, hydrogen exhibits one of the fastest diffusion rates in solid materials, comparable to the diffusion rate of liquid water molecules at room temperature. The diffusion rate is determined by an intricate combination of quantum effects and dynamic interplay with the displacement of host atoms that is still only partially understood. Here we present direct observations of the spatial and temporal changes in the diffusion-induced concentration profiles in a vanadium single crystal and we show that the results represent the experimental counterpart of the full time and spatial solution of Fick's diffusion equation. We validate the approach by determining the diffusion rate of hydrogen in a single crystal vanadium (001) film, with net diffusion in the [110] direction. PMID:22692535

Using light transmission to watch hydrogen diffuse

NASA Astrophysics Data System (ADS)

Pálsson, Gunnar K.; Bliersbach, Andreas; Wolff, Max; Zamani, Atieh; Hjörvarsson, Björgvin

2012-06-01

Because of its light weight and small size, hydrogen exhibits one of the fastest diffusion rates in solid materials, comparable to the diffusion rate of liquid water molecules at room temperature. The diffusion rate is determined by an intricate combination of quantum effects and dynamic interplay with the displacement of host atoms that is still only partially understood. Here we present direct observations of the spatial and temporal changes in the diffusion-induced concentration profiles in a vanadium single crystal and we show that the results represent the experimental counterpart of the full time and spatial solution of Fick's diffusion equation. We validate the approach by determining the diffusion rate of hydrogen in a single crystal vanadium (001) film, with net diffusion in the [110] direction.

High temperature resistant cermet and ceramic compositions. [for thermal resistant insulators and refractory coatings

NASA Technical Reports Server (NTRS)

Phillips, W. M. (Inventor)

1978-01-01

High temperature oxidation resistance, high hardness and high abrasion and wear resistance are properties of cermet compositions particularly to provide high temperature resistant refractory coatings on metal substrates, for use as electrical insulation seals for thermionic converters. The compositions comprise a sintered body of particles of a high temperature resistant metal or metal alloy, preferably molybdenum or tungsten particles, dispersed in and bonded to a solid solution formed of aluminum oxide and silicon nitride, and particularly a ternary solid solution formed of a mixture of aluminum oxide, silicon nitride and aluminum nitride. Ceramic compositions comprising a sintered solid solution of aluminum oxide, silicon nitride and aluminum nitride are also described.

Influence of Dy in solid solution on the degradation behavior of binary Mg-Dy alloys in cell culture medium.

PubMed

Yang, Lei; Ma, Liangong; Huang, Yuanding; Feyerabend, Frank; Blawert, Carsten; Höche, Daniel; Willumeit-Römer, Regine; Zhang, Erlin; Kainer, Karl Ulrich; Hort, Norbert

2017-06-01

Rare earth element Dy is one of the promising alloying elements for magnesium alloy as biodegradable implants. To understand the effect of Dy in solid solution on the degradation of Mg-Dy alloys in simulated physiological conditions, the present work studied the microstructure and degradation behavior of Mg-Dy alloys in cell culture medium. It is found the corrosion resistance enhances with the increase of Dy content in solid solution in Mg. This can be attributed to the formation of a relatively more corrosion resistant Dy-enriched film which decreases the anodic dissolution of Mg. Copyright © 2017 Elsevier B.V. All rights reserved.