Rhodium enalcarbenoids: direct synthesis of indoles by rhodium(II)-catalyzed [4+2] benzannulation of pyrroles.

Science.gov (United States)

Dawande, Sudam Ganpat; Kanchupalli, Vinaykumar; Kalepu, Jagadeesh; Chennamsetti, Haribabu; Lad, Bapurao Sudam; Katukojvala, Sreenivas

2014-04-14

Disclosed herein is the design of an unprecedented electrophilic rhodium enalcarbenoid which results from rhodium(II)-catalyzed decomposition of a new class of enaldiazo compounds. The synthetic utility of these enalcarbenoids has been successfully demonstrated in the first transition-metal-catalyzed [4+2] benzannulation of pyrroles, thus leading to substituted indoles. The new benzannulation has been applied to the efficient synthesis of the natural product leiocarpone as well as a potent adipocyte fatty-acid binding protein inhibitor. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effects of primary beam filters on the analysis of rhodium and cadmium using a rhodium target x-ray tube

International Nuclear Information System (INIS)

Anzelmo, J.A.; Boyer, B.W.

1986-01-01

Since its introduction in 1964, the thin end-window rhodium target x-ray tube has been considered to be an excellent general purpose source of excitation. Heavy elements are efficiently excited by high Bremsstrahlung and the K lines of rhodium while the light elements are excited by the L lines of rhodium. The ability to efficiently excite both heavy and light elements is essential to special applications such as auto catalysts, which are composed of precious metals in a clay-like matrix. Close control of the light elements, including sodium, phosphorous, aluminum and silicon, and the heavy element precious metals, such as rhodium, are necessary to keep operating characteristics and manufacturing expense at desired levels. A quick survey of typical x-ray tube targets shows that some targets are more efficient for light elements while others are more efficient for heavy elements. The few general purpose x-ray tubes that are available have characteristic lines which overlap on elements to be determined. The rhodium target, which is a good excitation source for most of the elements mentioned, contains line overlaps on cadmium (RHKB) and rhodium (RHKA). When using a sequential wavelength dispersive XRF spectrometer, the characteristic lines of the tube scattered from the sample can be removed by a programmable primary beam filter having an absorption edge just higher in wavelength than the wavelengths to be removed. The thickness and composition of the filter, as well as the choice of KV and MA, will determine the operating parameter necessary to achieve the optimum precision and lowest limits of detection. For this study, synthetic samples are made up using Kaolin as the matrix

Electronic and magnetic properties of ultrathin rhodium nanowires

CERN Document Server

Wang Bao Lin; Ren-Yun; Sun Hou Qian; Chen Xiao Shuang; Zhao Ji Jun

2003-01-01

The structures of ultrathin rhodium nanowires are studied using empirical molecular dynamics simulations with a genetic algorithm. Helical multishell cylindrical and pentagonal packing structures are found. The electronic and magnetic properties of the rhodium nanowires are calculated using an spd tight-binding Hamiltonian in the unrestricted Hartree-Fock approximation. The average magnetic moment and electronic density of states are obtained. Our results indicate that the electronic and magnetic properties of the rhodium nanowires depend not only on the size of the wire but also on the atomic structure. In particular, centred pentagonal and hexagonal structures can be unusually ferromagnetic.

Rhodium Catalyzed Decarbonylation

DEFF Research Database (Denmark)

Garcia Suárez, Eduardo José; Kahr, Klara; Riisager, Anders

2017-01-01

Rhodium catalyzed decarbonylation has developed significantly over the last 50 years and resulted in a wide range of reported catalyst systems and reaction protocols. Besides experimental data, literature also includes mechanistic studies incorporating Hammett methods, analysis of kinetic isotope...

Hydroformylation of methyl oleate catalyzed by rhodium complexes

International Nuclear Information System (INIS)

Mendes, Ana Nery Furlan; Rosa, Ricardo Gomes da; Gregorio, Jose Ribeiro

2012-01-01

In this work, we describe the hydroformylation of methyl oleate catalyzed by several rhodium complexes. Parameters including total pressure, phosphorous/rhodium and CO/H 2 ratio, temperature and phosphorous ligands were scanned. Total conversion of the starting double bonds was achieved while maintaining excellent selectivity in aldehydes. (author)

Quantification of Rhodium in a Series of Inorganic and ...

African Journals Online (AJOL)

NICO

... such as rhodium hydridocarbonyl tristriphenylphosphine, [HRh(CO)(PPh3)3], .... The selection of the most suitable wavelengths for rhodium, yttrium and cobalt ... chloride ions were removed from the CRM samples as chlorine gas with the ...

An Extended X-ray Absorption Fine Structure Study of Rhodium-Oxygen Bonds in a Highly Dispersed Rhodium/Aluminum Oxide Catalyst

NARCIS (Netherlands)

Koningsberger, D.C.; Zon, J.B.A.D. van; Blik, H.F.J. van 't; Visser, G.J.; Prins, R.; Mansour, A.N.; Sayers, D.E.; Short, D.R.

1985-01-01

Analysis of in situ EXAFS measurements on a 2.4 wt % Rh/A120, catalyst, reduced at 473 K after calcination at 623 K, shows the presence of two different rhodium-oxygen bonds (viz. 2.05 and 2.68 A). The oxygen neighbors of rhodium at a distance of 2.05 A disappear after reduction at 673 K. The

First-principles study of hydrogen diffusion in transition metal Rhodium

International Nuclear Information System (INIS)

Bao, Wulijibilige; Cui, Xin; Wang, Zhi-Ping

2015-01-01

In this study, the diffuse pattern and path of hydrogen in transition metal rhodium are investigated by the first-principles calculations. Density functional theory is used to calculate the system energies of hydrogen atom occupying different positions in rhodium crystal lattice. The results indicate that the most stable position of hydrogen atom in rhodium crystal lattice locates at the octahedral interstice, and the tetrahedral interstice is the second stable site. The activation barrier energy for the diffusion of atomic hydrogen in transition metal rhodium is quantified by determining the most favorable path, i.e., the minimum-energy pathway for diffusion, that is the indirect octahedral-tetrahedral-octahedral (O-T-O) pathway, and the activation energy is 0.8345eV

Chemical Posttranslational Modification with Designed Rhodium(II) Catalysts.

Science.gov (United States)

Martin, S C; Minus, M B; Ball, Z T

2016-01-01

Natural enzymes use molecular recognition to perform exquisitely selective transformations on nucleic acids, proteins, and natural products. Rhodium(II) catalysts mimic this selectivity, using molecular recognition to allow selective modification of proteins with a variety of functionalized diazo reagents. The rhodium catalysts and the diazo reactivity have been successfully applied to a variety of protein folds, the chemistry succeeds in complex environments such as cell lysate, and a simple protein blot method accurately assesses modification efficiency. The studies with rhodium catalysts provide a new tool to study and probe protein-binding events, as well as a new synthetic approach to protein conjugates for medical, biochemical, or materials applications. © 2016 Elsevier Inc. All rights reserved.

Kalman filtering for rhodium self-powered neutron detectors

International Nuclear Information System (INIS)

Kantrowitz, M.L.

1988-01-01

Rhodium self-powered neutron detectors are utilized in many pressurized water reactors to determine the neutronic behavior within the core. In order to compensate for the inherent time delay associated with the response of these detectors, a dynamic compensation algorithm is currently used in Combustion Engineering plants to reconstruct the dynamic flux signal which is being sensed by the rhodium detectors. This paper describes a new dynamic compensation algorithm, based on Kalman filtering, which improves on the noise gain and response time characteristics of the algorithm currently used, and offers the possibility of utilizing the proven rhodium detector based fixed in-core detector system as an integral part of advanced core control and/or protection systems

Block copolymer lithography of rhodium nanoparticles for high temperature electrocatalysis.

Science.gov (United States)

Boyd, David A; Hao, Yong; Li, Changyi; Goodwin, David G; Haile, Sossina M

2013-06-25

We present a method for forming ordered rhodium nanostructures on a solid support. The approach makes use of a block copolymer to create and assemble rhodium chloride nanoparticles from solution onto a surface; subsequent plasma and thermal processing are employed to remove the polymer and fully convert the nanostructures to metallic rhodium. Films cast from a solution of the triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) dissolved in toluene with rhodium(III) chloride hydrate were capable of producing a monolayer of rhodium nanoparticles of uniform size and interparticle spacing. The nanostructures were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. The electrocatalytic performance of the nanoparticles was investigated with AC impedance spectroscopy. We observed that the addition of the particles to a model solid oxide fuel cell anode provided up to a 14-fold improvement in the anode activity as evidenced by a decrease in the AC impedance resistance. Examination of the anode after electrochemical measurement revealed that the basic morphology and distribution of the particles were preserved.

Dinuclear ditertiary phosphite derivatives of rhodium

International Nuclear Information System (INIS)

Meintjies, E.

1981-08-01

The overall objective of the research described in this thesis was the design, synthesis, characterization and chemistry of dinuclear complexes of rhodium in which the metal atoms are held in close proximity to each other. Complexes of this nature are of considerable interest owing, in part, to their potential as models for multicentred metal catalysts, as well as to the highly novel and unusual chemistry already discovered for a number of them. A survey of dinuclear complexes of rhodium containing carbonyl and group V donor ligands has been presented as a background introduction to the research reported in this thesis. The coordination behaviour of the diphosphazane ligands, (RO) 2 PN(R')P(OR) 2 (R=Ph or Me, R' = Et; R = Et or Pr/i, R' = Me), and the ditertiary phosphite ligand, (EtO) 2 POP(OEt) 2 , towards certain rhodium precursors has been investigated. A number of highly unusual neutral dinuclear complexes of rhodium, in which these ligands bridge-bond the two rhodium atoms, have been synthesized. Two types of monocarbonyl decarbonylation products are observed for compounds of the type, [Rh 2 Cl 2 (CO) 2 (μ-diphosphazane) 2 ]. 1 H and 31 P[ 1 H] n.m.r. spectral studies have been carried out with the object of establishing the nature of the bridging halogen ligands in the tricarbonyl species. Asymetric zerovalent dinuclear species of the type, [Rh 2 (CO) 3 -[μ-(RO) 2 PN(R')P(OR) 2 ] 2 ] (R = Ph or Me, R' = Et; R = Pr/i, R' = Me), are obtained. A single crystal X-ray analysis has been carried out. Homoleptic cationic species are obtained by reaction of the alkoxydiphosphazane ligands with [Rh(C 8 H 12 )(solvent)(n)] + under the appropriate reaction conditions. The solution and solid-state infrared spectra and the 31 P[ 1 H] n.m.r. spectra of all new compounds synthesized in this study are discussed in terms of possible structures for these compounds. Where appropriate, the n.m.r. spectral data are also discussed in terms of fluxional behaviour

Industrial tests of rhodium self-powered detectors: the Golfech 2 experimentation

International Nuclear Information System (INIS)

Mourlevat, J.L.; Janvier, D.; Warren, H.D.

2000-01-01

In co-operation with Electricite de France (EDF), FRAMATOME has been testing two in-core strings which are equipped with rhodium self-powered detectors (SPDs) in the Golfech Unit 2 reactor (1300 MW, 4L plant) since August 1997. The rhodium SPDs and the strings which support them were designed and built by the US FRAMATOME subsidiary FRAMATOME-COGEMA-FUEL (FCF). The rhodium signals and some other plant parameters are acquired through the use of a specific device designed by the CEA (Commissariat a l'Energie Atomique) and are processed off-line by FRAMATOME. This demonstration test is planned to last until mid-2000. The following presentation is focused on the results obtained during the first demonstration cycle (from 08/97 to 12/98). The tests that have been conducted consist of checking the rhodium depletion and of comparing the rhodium signals to the movable probes. In order to compensate for the delay in the rhodium signals, a deconvolution algorithm has also been tested. Up to now, the results are very satisfactory and a future large scale industrial application is being discussed with the EDF. The main objective of the next experimentation phase is to test - under industrial conditions - a prototype of an on-line monitoring unit known as the Partial In-Core Monitoring System (PIMS). This system will include 16 rhodium in-core strings and will use an on-line 3-D core model. (authors)

Low gravity containerless processing of immiscible gold rhodium alloys

Science.gov (United States)

Andrews, J. Barry

1986-01-01

Under normal one-g conditions immiscible alloys segregate extensively during solidification due to sedementation of the more dense of the immiscible liquid phases. However, under low-g conditions it should be possible to form a dispersion of the two immiscible liquids and maintain this dispersed structure during solidification. Immiscible (hypermonotectic) gold-rhodium alloys were processed in the Marshall Space Flight Center 105 meter drop tube in order to investigate the influence of low gravity, containerless solidification on their microstructure. Hypermonotectic alloys composed of 65 atomic % rhodium exhibited a tendency for the gold rich liquid to wet the outer surface of the containerless processed samples. This tendency led to extensive segregation in several cases. However, well dispersed microstructures consisting of 2 to 3 micron diameter rhodium-rich spheres in a gold-rich matrix were produced in 23.4 atomic % rhodium alloys. This is one of the best dispersions obtained in research on immiscible alloy-systems to data.

Free Rhodium (II) citrate and rhodium (II) citrate magnetic carriers as potential strategies for breast cancer therapy

Science.gov (United States)

2011-01-01

Background Rhodium (II) citrate (Rh2(H2cit)4) has significant antitumor, cytotoxic, and cytostatic activity on Ehrlich ascite tumor. Although toxic to normal cells, its lower toxicity when compared to carboxylate analogues of rhodium (II) indicates Rh2(H2cit)4 as a promising agent for chemotherapy. Nevertheless, few studies have been performed to explore this potential. Superparamagnetic particles of iron oxide (SPIOs) represent an attractive platform as carriers in drug delivery systems (DDS) because they can present greater specificity to tumor cells than normal cells. Thus, the association between Rh2(H2cit)4 and SPIOs can represent a strategy to enhance the former's therapeutic action. In this work, we report the cytotoxicity of free rhodium (II) citrate (Rh2(H2cit)4) and rhodium (II) citrate-loaded maghemite nanoparticles or magnetoliposomes, used as drug delivery systems, on both normal and carcinoma breast cell cultures. Results Treatment with free Rh2(H2cit)4 induced cytotoxicity that was dependent on dose, time, and cell line. The IC50 values showed that this effect was more intense on breast normal cells (MCF-10A) than on breast carcinoma cells (MCF-7 and 4T1). However, the treatment with 50 μM Rh2(H2cit)4-loaded maghemite nanoparticles (Magh-Rh2(H2cit)4) and Rh2(H2cit)4-loaded magnetoliposomes (Lip-Magh-Rh2(H2cit)4) induced a higher cytotoxicity on MCF-7 and 4T1 than on MCF-10A (p rhodium (II) citrate-loaded maghemite nanoparticles and magnetoliposomes induced more specific cytotoxicity on breast carcinoma cells than on breast normal cells, which is the opposite of the results observed with free Rh2(H2cit)4 treatment. Thus, magnetic nanoparticles represent an attractive platform as carriers in Rh2(H2cit)4 delivery systems, since they can act preferentially in tumor cells. Therefore, these nanopaticulate systems may be explored as a potential tool for chemotherapy drug development. PMID:21443799

Local Electric Field Effects on Rhodium-Porphyrin and NHC-Gold Catalysts

Science.gov (United States)

2015-01-05

AFRL-OSR-VA-TR-2015-0023 (NII) - Local Electric Field Effects on Rhodium -Porphyrin and NHC-Gold Catalysts MATTHEW KANAN LELAND STANFORD JUNIOR UNIV...Effects on Rhodium -Porphyrin and NHC-Gold Catalysts Principal Investigator: Matthew W. Kanan Project Publications: 1. “An Electric Field–Induced Change...Stanford University Grant/Contract Title The full title of the funded effort. (NII)-Local Electric Field Effects on Rhodium -Porphyrin and NHC-Gold

Electronic and magnetic properties of small rhodium clusters

Energy Technology Data Exchange (ETDEWEB)

Soon, Yee Yeen; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

2015-04-24

We report a theoretical study of the electronic and magnetic properties of rhodium-atomic clusters. The lowest energy structures at the semi-empirical level of rhodium clusters are first obtained from a novel global-minimum search algorithm, known as PTMBHGA, where Gupta potential is used to describe the atomic interaction among the rhodium atoms. The structures are then re-optimized at the density functional theory (DFT) level with exchange-correlation energy approximated by Perdew-Burke-Ernzerhof generalized gradient approximation. For the purpose of calculating the magnetic moment of a given cluster, we calculate the optimized structure as a function of the spin multiplicity within the DFT framework. The resultant magnetic moments with the lowest energies so obtained allow us to work out the magnetic moment as a function of cluster size. Rhodium atomic clusters are found to display a unique variation in the magnetic moment as the cluster size varies. However, Rh{sub 4} and Rh{sub 6} are found to be nonmagnetic. Electronic structures of the magnetic ground-state structures are also investigated within the DFT framework. The results are compared against those based on different theoretical approaches available in the literature.

Electrochemical behavior of rhodium(III) in 1-butyl-3-methylimidazolium chloride ionic liquid

Energy Technology Data Exchange (ETDEWEB)

Jayakumar, M.; Venkatesan, K.A. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Srinivasan, T.G. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)], E-mail: tgs@igcar.gov.in

2008-02-15

Electrochemical behavior of rhodium(III) chloride in 1-butyl-3-methylimidazolium chloride was investigated by various electrochemical transient techniques at glassy carbon working electrode at different temperatures (343-373 K). Cyclic voltammogram of rhodium(III) in bmimCl consisted of a surge in reduction current occurring at a potential of -0.48 V (vs. Pd) is due to the reduction of Rh(III) to metallic rhodium and a very small oxidation wave occurring at -0.1 V. Increase of scan rate increases the peak current and remarkably shifts the cathodic peak potential (E{sub p}{sup c1}) in negative direction indicating the irreversibility of electroreduction of rhodium(III). The diffusion coefficient of rhodium(III) in bmimCl ({approx}10{sup -9} cm{sup 2}/s) was determined and the energy of activation ({approx}25 kJ/mol) was deduced from cyclic voltammograms at various temperatures. The cathodic ({tau}{sub r}) and anodic ({tau}{sub o}) transition times were measured from chronopotential transients and the ratio {tau}{sub o}/{tau}{sub r} was found to be 1:7. Electrowinning of rhodium from bmimCl medium results in a deposition of metallic rhodium with lower (20-25%) Faradaic efficiency. A separation factor of rhodium from co-existing noble metal fission product palladium in bmimCl was determined during electrodeposition.

Rhodium trichloride as a homogeneous catalyst for isotopic hydrogen exchange. Comparison with heterogeneous rhodium in the deuteriation of aromatic compounds and alkanes

Energy Technology Data Exchange (ETDEWEB)

Blake, M R; Garnett, J L; Gregor, I K; Hannan, W; Hoa, K; Long, M A [New South Wales Univ., Kensington (Australia)

1975-12-03

The use of rhodium trichloride as a homogeneous catalyst for the exchange of aromatic compounds and alkanes is described; comparison of the results with corresponding data from heterogeneous rhodium metal and other homogeneous systems, e.g., platinum and iridium, supports the proposal that specific type of ..pi..-complex mechanisms are common to all such exchange systems.

Rhodium self-powered neutron detector's lifetime for korean standard nuclear power plants

International Nuclear Information System (INIS)

Yoo, Choon Sung; Kim, Byoung Chul; Park, Jong Ho; Fero, Arnold H.; Anderson, S. L.

2005-01-01

A method to estimate the relative sensitivity of a self-powered rhodium detector for an upcoming cycle is developed by combining the rhodium depletion data from a nuclear design with the site measurement data. This method can be used both by nuclear power plant designers and by site staffs of Korean standard nuclear power plants for determining which rhodium detectors should be replaced during overhauls

About the extraction recovery of fission rhodium from radioactive wastes

International Nuclear Information System (INIS)

Khaperskaya, A.V.; Renard, E.V.; Koltunov, V.S.

2000-01-01

The report will cover a radically new approach to the problem of rhodium recovery from HLLW after the transformation of kinetically inert poly-aqua cation of trivalent rhodium (which is not recoverable by the majority known extractants) to Rh (IV) form by chemical methods. Presented are the research results of Rh (IV) extraction from nitric acid solutions by several extractants that are of considerable current use in noble metals and radiochemical industries (tri-n-butyl phosphate, di-octyl-sulphide, tri-n-octylamine, quaternary ammonium bases). High level of rhodium extraction has been found for the above extractants: for several systems, for example, tri-n-octylamine - diethyl-benzene, rhodium distribution coefficient achieves high values (10-plus), as well as the sufficient extraction kinetics. Rhodium extraction increases with a decrease of the acidity, a rise in phase mixing time and in the following series: tri-n-butyl phosphate → di-octyl-sulphide → quaternary ammonium bases → tri-n-octylamine. Rh (IV) can be easily reduced to non-extractable Rh (III) by such reductants as Fe (II), HCOOH, C 6 H 8 O 6 , NH 2 OH, N 2 H 4 et al, that may be applied for the re-extraction process. (authors)

"On-water" rhodium-catalysed hydroformylation for the production of linear alcohols

NARCIS (Netherlands)

Diebolt, O.H.; Müller, Christian; Vogt, D.

2012-01-01

Optimisation of the reaction conditions for the rhodium-catalysed aldehyde hydrogenation under hydroformylation conditions showed that water used as co-solvent enhances both rate and selectivity towards primary alcohols. One-pot hydroformylation–hydrogenation using rhodium as the only transition

Antagonizing STAT3 dimerization with a rhodium(III) complex.

Science.gov (United States)

Ma, Dik-Lung; Liu, Li-Juan; Leung, Ka-Ho; Chen, Yen-Ting; Zhong, Hai-Jing; Chan, Daniel Shiu-Hin; Wang, Hui-Min David; Leung, Chung-Hang

2014-08-25

Kinetically inert metal complexes have arisen as promising alternatives to existing platinum and ruthenium chemotherapeutics. Reported herein, to our knowledge, is the first example of a substitutionally inert, Group 9 organometallic compound as a direct inhibitor of signal transducer and activator of transcription 3 (STAT3) dimerization. From a series of cyclometalated rhodium(III) and iridium(III) complexes, a rhodium(III) complex emerged as a potent inhibitor of STAT3 that targeted the SH2 domain and inhibited STAT3 phosphorylation and dimerization. Significantly, the complex exhibited potent anti-tumor activities in an in vivo mouse xenograft model of melanoma. This study demonstrates that rhodium complexes may be developed as effective STAT3 inhibitors with potent anti-tumor activity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rhodium and Hafnium Influence on the Microstructure, Phase Composition, and Oxidation Resistance of Aluminide Coatings

OpenAIRE

Maryana Zagula-Yavorska; Małgorzata Wierzbińska; Jan Sieniawski

2017-01-01

A 0.5 μm thick layer of rhodium was deposited on the CMSX 4 superalloy by the electroplating method. The rhodium-coated superalloy was hafnized and aluminized or only aluminized using the Chemical vapour deposition method. A comparison was made of the microstructure, phase composition, and oxidation resistance of three aluminide coatings: nonmodified (a), rhodium-modified (b), and rhodium- and hafnium-modified (c). All three coatings consisted of two layers: the additive layer and the interdi...

Rhodium-Catalyzed Linear Codimerization and Cycloaddition of Ketenes with Alkynes

Directory of Open Access Journals (Sweden)

Teruyuki Kondo

2010-06-01

Full Text Available A novel rhodium-catalyzed linear codimerization of alkyl phenyl ketenes with internal alkynes to dienones and a novel synthesis of furans by an unusual cycloaddition of diaryl ketenes with internal alkynes have been developed. These reactions proceed smoothly with the same rhodium catalyst, RhCl(PPh33, and are highly dependent on the structure and reactivity of the starting ketenes.

Rhodium(III)-Catalyzed Amidation of Unactivated C(sp(3) )-H Bonds.

Science.gov (United States)

Wang, He; Tang, Guodong; Li, Xingwei

2015-10-26

Nitrogenation by direct functionalization of C-H bonds represents an important strategy for constructing C-N bonds. Rhodium(III)-catalyzed direct amidation of unactivated C(sp(3) )-H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp(3) )-H bonds are amidated under rhodium catalysis in high efficiency using 3-substituted 1,4,2-dioxazol-5-ones as the amide source. The protocol broadens the scope of rhodium(III)-catalyzed C(sp(3) )-H activation chemistry, and is applicable to the late-stage functionalization of natural products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In vitro permeation of platinum and rhodium through Caucasian skin.

Science.gov (United States)

Franken, A; Eloff, F C; Du Plessis, J; Badenhorst, C J; Jordaan, A; Du Plessis, J L

2014-12-01

During platinum group metals (PGMs) refining the possibility exists for dermal exposure to PGM salts. The dermal route has been questioned as an alternative route of exposure that could contribute to employee sensitisation, even though literature has been focused on respiratory exposure. This study aimed to investigate the in vitro permeation of platinum and rhodium through intact Caucasian skin. A donor solution of 0.3mg/ml of metal, K2PtCl4 and RhCl3 respectively, was applied to the vertical Franz diffusion cells with full thickness abdominal skin. The receptor solution was removed at various intervals during the 24h experiment, and analysed with high resolution ICP-MS. Skin was digested and analysed by ICP-OES. Results indicated cumulative permeation with prolonged exposure, with a significantly higher mass of platinum permeating after 24h when compared to rhodium. The mass of platinum retained inside the skin and the flux of platinum across the skin was significantly higher than that of rhodium. Permeated and skin retained platinum and rhodium may therefore contribute to sensitisation and indicates a health risk associated with dermal exposure in the workplace. Copyright © 2014 Elsevier Ltd. All rights reserved.

Rhodium-Catalyzed Decarbonylation of Aldoses

DEFF Research Database (Denmark)

Monrad, Rune; Madsen, Robert

2007-01-01

A catalytic procedure is described for decarbonylation of unprotected aldoses to afford alditols with one less carbon atom. The reaction is performed with the rhodium complex Rh(dppp)2Cl in a refluxing diglyme - DMA solution. A slightly improved catalyst turnover is observed when a catalytic amount...

Rhodium-catalyzed regioselective olefination directed by a carboxylic group.

Science.gov (United States)

Mochida, Satoshi; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro

2011-05-06

The ortho-olefination of benzoic acids can be achieved effectively through rhodium-catalyzed oxidative coupling with alkenes. The carboxylic group is readily removable to allow ortho-olefination/decarboxylation in one pot. α,β-Unsaturated carboxylic acids such as methacrylic acid also undergo the olefination at the β-position. Under the rhodium catalysis, the cine-olefination of heteroarene carboxylic acids such as thiophene-2-carboxylic acid proceeds smoothly accompanied by decarboxylation to selectively produce the corresponding vinylheteroarene derivatives. © 2011 American Chemical Society

Relationship between electronic structure and electric conductivity of double rhodium oxides from X-ray spectral data

International Nuclear Information System (INIS)

Firsov, M.N.; Nefedov, V.I.; Shaplygin, I.S.

1983-01-01

Quantum yield spectra of X-ray photoemission of O K - and Rh M 3 -bands of double rhodium oxides with Be, Mg, Ca, Sr, Ba, Cd, V, Nb, Ta, Mo, W are obtained. Quantum yield spectra are analogous to absorption spectra and reflect vacant states in a crystal, in particular, the quantum yield spectrum of O K-band is associated with oxygen vacant states of p-symmetry while Rh M 3 -band spectrum with rhomium vacant states of d-symmetry. In all rhodium compounds investigated the first vacant band is formed by the rhodium 4d-states. The forbidden zone between the last occupied and first free states of rhodiUm has a small width (eV fractions), which explains the semiconductor character of electric conductivity of the investigated compounds. Electric resistance variation in investigated series of rhodium compounds is in agreement with peculiarities of their electronic structure and entirely depends on variation in the electron density on rhodium atoms

Superconductivity in zirconium-rhodium alloys

Science.gov (United States)

Zegler, S. T.

1969-01-01

Metallographic studies and transition temperature measurements were made with isothermally annealed and water-quenched zirconium-rhodium alloys. The results clarify both the solid-state phase relations at the Zr-rich end of the Zr-Rh alloy system and the influence upon the superconducting transition temperature of structure and composition.

A study on the sensitivity depletion laws for rhodium self-powered neutron detectors

International Nuclear Information System (INIS)

Kim, Gil Gon

1999-02-01

The rhodium self-powered neutron detectors (SPND) in a reactor core provide the operator with the on-line 3-dimensional nuclear power distribution. The signal produced by rhodium SPND is interpreted into the local neutron flux by using a sensitivity depletion law and the local neutron flux is interpreted into the local power by using a power conversion factor. This work on the sensitivity depletion laws for rhodium self-powered neutron detectors (SPND) is performed to improve the uncertainty of the sensitivity depletion law used in ABB-CE reactors employing a rhodium SPND and to develop a calculational tool for providing the sensitivity depletion laws to interpret the signal of the newly designed rhodium SPND into the local neutron flux. The calculational tools for a time dependent neutron flux distribution in the rhodium emitter during depletion and for a time dependent beta escape probability that a beta generated in the emitter is escaped into the collector were developed. Due to the cost, the exposure to the radiation, and the longer fuel cycle, there is a strong incentive that the loading density of an in-core instrumentation is reduced and the lifetime of the detector is lengthened. These objectives can be achieved by reducing the uncertainty which is amplified as it depletes. The calculational tools above provide the sensitivity depletion law and show the reduction of the uncertainty to about 1 % in interpreting the signal into the local neutron flux compared to the method employed by ABB-CE. The reduction in the uncertainty of 1 % in interpreting the signal into the local neutron flux is equivalent to the reduction in the uncertainty of 1 % or more in interpreting the signal into the local power and to the extension of the lifetime of rhodium SPND to about 10 % as reported by ABB-CE

Rhodium Phosphine-π-Arene Intermediates in the Hydroamination of Alkenes

Science.gov (United States)

Liu, Zhijian; Yamamichi, Hideaki; Madrahimov, Sherzod T.; Hartwig, John F.

2011-01-01

A detailed mechanistic study of the intramolecular hydroamination of alkenes with amines catalyzed by rhodium complexes of a biaryldialkylphosphine are reported. The active catalyst is shown to contain the phosphine ligand bound in a κ1, η6 form in which the arene is π-bound to rhodium. Addition of deuterated amine to an internal olefin showed that the reaction occurs by trans addition of the N-H bond across the C=C bond, and this stereochemistry implies that the reaction occurs by nucleophilic attack of the amine on a coordinated alkene. Indeed, the cationic rhodium fragment binds the alkene over the secondary amine, and the olefin complex was shown to be the catalyst resting state. The reaction was zero-order in substrate, when the concentration of olefin was high, and a primary isotope effect was observed. The primary isotope effect, in combination with the observation of the alkene complex as the resting state, implies that nucleophilic attack of the amine on the alkene is reversible and is followed by turnover-limiting protonation. This mechanism constitutes an unusual pathway for rhodium-catalyzed additions to alkenes and is more closely related to the mechanism for palladium-catalyzed addition of amide N-H bonds to alkenes. PMID:21309512

Electrochemical properties of lanthanum nitride with calcium nitride additions

International Nuclear Information System (INIS)

Lesunova, R.P.; Fishman, L.S.

1986-01-01

This paper reports on the electrochemical properties of lanthanum nitride with calcium nitride added. The lanthanum nitride was obtained by nitriding metallic lanthanum at 870 K in an ammonia stream. The product contained Cl, Pr, Nd, Sm, Fe, Ca, Cu, Mo, Mg, Al, Si, and Be. The calcium nitride was obtained by nitriding metallic calcium in a nitrogen stream. The conductivity on the LaN/C 3 N 2 system components are shown as a function of temperature. A table shows the solid solutions to be virtually electronic conductors and the lanthanum nitride a mixed conductor

Atmosphere-Controlled Chemoselectivity: Rhodium-Catalyzed Alkylation and Olefination of Alkylnitriles with Alcohols.

Science.gov (United States)

Li, Junjun; Liu, Yuxuan; Tang, Weijun; Xue, Dong; Li, Chaoqun; Xiao, Jianliang; Wang, Chao

2017-10-17

The chemoselective alkylation and olefination of alkylnitriles with alcohols have been developed by simply controlling the reaction atmosphere. A binuclear rhodium complex catalyzes the alkylation reaction under argon through a hydrogen-borrowing pathway and the olefination reaction under oxygen through aerobic dehydrogenation. Broad substrate scope is demonstrated, permitting the synthesis of some important organic building blocks. Mechanistic studies suggest that the alkylation product may be formed through conjugate reduction of an alkene intermediate by a rhodium hydride, whereas the formation of olefin product may be due to the oxidation of the rhodium hydride complex with molecular oxygen. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure of Rhodium in an Ultradispersed Rhodium/Alumina Catalyst as Studied by EXAFS and Other Technique

NARCIS (Netherlands)

Koningsberger, D.C.; Blik, H.F.J. van 't; Zon, J.B.A.D. van; Huizinga, T.; Vis, J.C.; Prins, R.

1985-01-01

The structure of rhodium in an ultradispersed 0.57 wt % Rh/y-Al,O, catalyst before and after CO adsorption was studied with extended X-ray absorption fine structure (EXAFS), X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR), temperature programmed reduction (TPR), CO infrared

Rhodium-catalyzed C-H alkynylation of arenes at room temperature.

Science.gov (United States)

Feng, Chao; Loh, Teck-Peng

2014-03-03

The rhodium(III)-catalyzed ortho C-H alkynylation of non-electronically activated arenes is disclosed. This process features a straightforward and highly effective protocol for the synthesis of functionalized alkynes and represents the first example of merging a hypervalent iodine reagent with rhodium(III) catalysis. Notably, this reaction proceeds at room temperature, tolerates a variety of functional groups, and more importantly, exhibits high selectivity for monoalkynylation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Superconducting structure with layers of niobium nitride and aluminum nitride

International Nuclear Information System (INIS)

Murduck, J.M.; Lepetre, Y.J.; Schuller, I.K.; Ketterson, J.B.

1989-01-01

A superconducting structure is formed by depositing alternate layers of aluminum nitride and niobium nitride on a substrate. Deposition methods include dc magnetron reactive sputtering, rf magnetron reactive sputtering, thin-film diffusion, chemical vapor deposition, and ion-beam deposition. Structures have been built with layers of niobium nitride and aluminum nitride having thicknesses in a range of 20 to 350 Angstroms. Best results have been achieved with films of niobium nitride deposited to a thickness of approximately 70 Angstroms and aluminum nitride deposited to a thickness of approximately 20 Angstroms. Such films of niobium nitride separated by a single layer of aluminum nitride are useful in forming Josephson junctions. Structures of 30 or more alternating layers of niobium nitride and aluminum nitride are useful when deposited on fixed substrates or flexible strips to form bulk superconductors for carrying electric current. They are also adaptable as voltage-controlled microwave energy sources. 8 figs

Scalar Relativistic Study of the Structure of Rhodium Acetate

Directory of Open Access Journals (Sweden)

Emily E. Edwards

2004-01-01

Full Text Available Abstract: Rhodium acetate, related rhodium carboxylates, and rhodium amide complexes are powerful catalysts for carbene chemistry. They readily promote the decomposition of diazo compounds and transfer the resulting carbene to a variety of substrates. There have been several quantum chemistry studies of these compounds, particularly of the acetate. These have all used non-relativistic methods, and all have shown optimized Rh-Rh bond lengths significantly longer than the experimental value. In this study we have surveyed several scalar relativistic DFT methods using Gaussian, Slater, and numerical basis functions (in DGAUSS, ADF, and DMOL3. Several combinations of exchange-correlation functionals with relativistic and non-relativistic effective core potentials (ECP were investigated, as were non-relativistic and all electron scalar relativistic methods. The combination of the PW91 exchange and PW91 correlation functional with the Christiansen-Ermler ECP gave the best results: 2.3918 Å compared to the experimental value of 2.3855±0.0005 Å.

Crystal structures of fac-tri?chlorido?tris?(tri?methyl?phosphane-?P)rhodium(III) monohydrate and fac-tri?chlorido?tris?(tri?methyl?phosphane-?P)rhodium(III) methanol hemisolvate: rhodium structures that are isotypic with their iridium analogs

OpenAIRE

Merola, Joseph S.; Franks, Marion A.

2015-01-01

The crystal structures of two solvates of fac-tri-chlorido-tris-(tri-methyl-phosphane-κP)rhodium(III) are reported, i.e. one with water in the crystal lattice, fac-[RhCl3(Me3P)3]·H2O, and one with methanol in the crystal lattice, fac-[RhCl3(Me3P)3]·0.5CH3OH. These rhodium compounds exhibit distorted octahedral coordination spheres at the metal and are isotypic with the analogous iridium compounds previously reported by us [Merola et al. (2013 ▶). Polyhedron, 54, 67-73]. Comparison is made bet...

Olefins hydro-formylation catalysed by rhodium complexes using ionic liquids; Hydroformylation des olefines par les complexes du rhodium dans les liquides ioniques

Energy Technology Data Exchange (ETDEWEB)

Favre, F.

2000-10-26

Biphasic long chain olefins hydro-formylation catalysed by rhodium complexes using ionic liquids allows a selective reaction and an easy separation of the products from the catalyst. This study reports the synthesis of ionic liquids that were used as the catalyst's solvent. Their physical and chemical properties (melting point, solubility of organic substrates) can be varied with the structure of the organic cation (imidazolium, pyridinium, pyrrolydinium) and with its substituents (nature, length, number). It depends also on the nature of the inorganic anion (hexa-fluoro-phosphate, tetrafluoroborate, tri-fluoro-acetate, triflate, bistriflylamidure...). The use of phosphorus ligands bearing ionic functions proved to be efficient to maintain the onerous rhodium catalyst in the ionic liquid phase. Phosphines, phosphites and phosphinites including anionic (sulfonate, carboxylate) or cationic (imidazolium, pyridinium, guanidinium, phosphonium) groups have been synthesised. Finally, the influences of the ligand and of the ionic liquid on the catalytic system performances are described. Selectivities in aldehydes and reaction rates proved to be highly dependent on the nature of the ligand and of the ionic liquid. The different possibilities of recycling the ionic phase containing the rhodium catalyst have been also studied. (author)

Spectrophotometric determination of ruthenium(III) and rhodium(III) after extraction of their cyclohexylthioglycolate complexes into chloroform

International Nuclear Information System (INIS)

Rao, A.L.J.; Gupta, Usha; Puri, B.K.

1986-01-01

Cyclohexylthioglycolate has been used as a reagent for the spectrophotometric determination of ruthenium(III) and rhodium(III) after the extraction of their complexes into chloroform. Various parameters involved in the extraction have been studied and the composition of the extracted complex has been established in each instance. Ruthenium and rhodium complexes are extracted into chloroform in the pH ranges 5.0-9.0 and 9.0-12.5, respectively. The ruthenium complex absorbs strongly at 365 nm, whereas the rhodium complex shows a maximum absorption at 345 nm. Beer's law is obeyed over the concentration range 6-96 μg for ruthenium and 2-41 μg for rhodium in 10 ml of the chloroform solution. The molar absorptivities are 5.02 x 10 3 l mol -1 cm -1 for ruthenium and 1.60 x 10 4 l mol -1 cm -1 for rhodium. Ten replicate determinations on a sample solution containing 60.3 μg of ruthenium or 20.6 μg of rhodium gave mean absorbances of 0.300 and 0.320 with standard deviations of 0.0021 and 0.0025 and relative standard deviations of 0.70% and 0.78%, respectively. The interference of various ions has been studied and the method has been applied to the determination of the metals in various synthetic samples. Conditions have also been developed for the simultaneous determination of ruthenium and rhodium. (author)

Rhodium-Catalyzed Dehydrogenative Borylation of Cyclic Alkenes

Science.gov (United States)

Kondoh, Azusa; Jamison, Timothy F.

2010-01-01

A rhodium-catalyzed dehydrogenative borylation of cyclic alkenes is described. This reaction provides direct access to cyclic 1-alkenylboronic acid pinacol esters, useful intermediates in organic synthesis. Suzuki-Miyaura cross-coupling applications are also presented. PMID:20107646

Snapshot analysis for rhodium fixed incore detector using BEACON methodology

International Nuclear Information System (INIS)

Cha, Kyoon Ho; Choi, Yu Sun; Lee, Eun Ki; Park, Moon Ghu; Morita, Toshio; Heibel, Michael D.

2004-01-01

The purpose of this report is to process the rhodium detector data of the Yonggwang nuclear unit 4 cycle 5 core for the measured power distribution by using the BEACON methodology. Rhodium snapshots of the YGN 4 cycle 5 have been analyzed by both BEACON/SPINOVA and CECOR to compare the results of both codes. By analyzing a large number of snapshots obtained during normal plant operation. Reviewing the results of this analysis, the BEACON/SPNOVA can be used for the snapshot analysis of Korean Standard Nuclear Power (KSNP) plants

Spectrophotometric determination of ruthenium (III) and rhodium (III) with 9,10-phenanthrenequinone monoxime after extraction into molten naphthalene

International Nuclear Information System (INIS)

Wasey, A.; Bansal, R.K.; Puri, B.K.; Satake, Masatada.

1983-01-01

9,10-Phenanthrenequinone monoxime has been used as a reagent for the spectrophotometric determination of ruthenium(III) and rhodium(III) after extraction into molten naphthalene. The extracted mixture of the metal complex and naphthalene was dissolved in chloroform and ruthenium and rhodium were determined spectrophotometrically. Beer's law holds in the concentration range of 0.2-4.1 μg/cm 3 for ruthenium and 0.3-5.3 μg/cm 3 for rhodium in 10 cm 3 of the final solution. The molar absorptivities and Sandell sensitivities are calculated to be 9.70 x 10 3 l mol -1 cm -1 and 0.01 μg/cmsup(2 ) (660 nm) for ruthenium and 1.13 x 10 4 l mol -1 cm -1 and 0.009 μg/cm 2 (410 nm) for rhodium respectively. Aliquots containing 2.0 μg of ruthenium and 4.1 μg of rhodium give mean absorbances of 0.192 and 0.451 with standard deviations of 0.0017 and 0.0039, respectively. Interference of various ions has been studied and the method has been applied to the determination of ruthenium and rhodium in various synthetic mixtures. This procedure is also applied to the simultaneous determination of ruthenium and rhodium present together in a solution. (author)

Interaction between water-soluble rhodium complex RhCl(CO)(TPPTS)₂ and surfactants probed by spectroscopic methods.

Science.gov (United States)

Zhou, Li-Mei; Guo, Cai-Hong; Fu, Hai-Yan; Jiang, Xiao-Hui; Chen, Hua; Li, Rui-Xiang; Li, Xian-Jun

2012-07-01

The interactions of rhodium complex RhCl(CO)(TPPTS)(2) [TPPTS=P(m-C(6)H(4)SO(3)Na)(3)] with cationic, nonionic, and anionic surfactants have been investigated by UV-vis, fluorescence and (1)H NMR measurements. The presence of four different species of RhCl(CO)(TPPTS)(2) in cationic cetyltrimethylammonium (CTAB) solution has been demonstrated: free rhodium complex, rhodium complex bound to CTAB monomer, rhodium complex bound to CTAB premicelles, rhodium complex bound to CTAB micelles. The spectroscopy data show that RhCl(CO)(TPPTS)(2) can adsorb on the interface of cationic CTAB micelles by strong electrostatic attraction, weakly bind to the nonionic polyoxyethylene (20) sorbitan monolaurate (Tween 20) micelles by hydrophobic interaction, and does not interact with anion sodium dodecyl sulfate (SDS) micelles due to the strong electrostatic repulsion. Copyright © 2012 Elsevier B.V. All rights reserved.

The influence of pH on the in vitro permeation of rhodium through human skin.

Science.gov (United States)

Jansen Van Rensburg, Sané; Franken, Anja; Du Plessis, Jeanetta; Du Plessis, Johannes Lodewykus

2017-06-01

Workers in precious metals refineries are at risk of exposure to salt compounds of the platinum group metals through inhalation, as well as through the skin. Rhodium salt permeation through the skin has previously been proven using rhodium trichloride (RhCl 3 ) dissolved in synthetic sweat at a pH of 6.5. However, the skin surface pH of refinery workers may be lower than 6.5. The aim of this study was to investigate the influence of pH 6.5 and 4.5 on the in vitro permeation of rhodium through intact Caucasian skin using Franz diffusion cells. A concentration of 0.3 mg mL -1 rhodium was used and analyses were performed using inductively coupled plasma mass spectrometry and inductively coupled plasma optical emission spectrometry. Results indicated a cumulative increase in permeation over 24 h. Rhodium permeation after 12 h was significantly greater at pH 4.5 (1.56 ± 0.24 ng cm -2 ) than at 6.5 (0.85 ± 0.13 ng cm -2 ; p = 0.02). At both pH levels, there was a highly significant difference ( p rhodium remaining in the skin (1428.68 ± 224.67 ng cm -2 at pH 4.5 and 1029.90 ± 115.96 ng cm -2 at pH 6.5) and the mass that diffused through (0.88 ± 0.17 ng cm -2 at pH 4.5 and 0.62 ± 0.10 ng cm -2 at pH 6.5). From these findings, it is evident that an acidic working environment or low skin surface pH may enhance permeation of rhodium salts, contributing to sensitization and adverse health effects.

Modifiers in rhodium catalysts for carbon monoxide hydrogenation: Structure-activity relationships

Energy Technology Data Exchange (ETDEWEB)

Bhore, N. A.

1989-05-01

This report is aimed at identifying interesting modified rhodium systems and elucidating structure-activity relationships in these systems with the overall goal of understanding the scientific issues in the catalytic conversion of syngas to oxygenates. Specific additives (sodium and molybdenum) are selected based on the scoping experiments. The effect of the additives on supported rhodium catalysts is then investigated. Throughout the investigation, experiments and analysis were performed on real systems instead of ideal systems. 374 refs., 82 figs., 57 tabs.

Inhibiting prolyl isomerase activity by hybrid organic-inorganic molecules containing rhodium(II) fragments.

Science.gov (United States)

Coughlin, Jane M; Kundu, Rituparna; Cooper, Julian C; Ball, Zachary T

2014-11-15

A small molecule containing a rhodium(II) tetracarboxylate fragment is shown to be a potent inhibitor of the prolyl isomerase FKBP12. The use of small molecules conjugates of rhodium(II) is presented as a general strategy for developing new protein inhibitors based on distinct structural and sequence features of the enzyme active site. Copyright © 2014 Elsevier Ltd. All rights reserved.

Tandem rhodium catalysis: exploiting sulfoxides for asymmetric transition-metal catalysis.

Science.gov (United States)

Kou, K G M; Dong, V M

2015-06-07

Sulfoxides are uncommon substrates for transition-metal catalysis due to their propensity to inhibit catalyst turnover. In a collaborative effort with Ken Houk, we developed the first dynamic kinetic resolution (DKR) of allylic sulfoxides using asymmetric rhodium-catalyzed hydrogenation. A detailed mechanistic analysis of this transformation using both experimental and theoretical methods revealed rhodium to be a tandem catalyst that promoted both hydrogenation of the alkene and racemization of the allylic sulfoxide. Using a combination of deuterium labelling and DFT studies, a novel mode of allylic sulfoxide racemization via a Rh(III)-π-allyl intermediate was identified.

Energetic driving force of H spillover between rhodium and titania surfaces : a DFT view

NARCIS (Netherlands)

Conradie, J.; Gracia, J.; Niemantsverdriet, J.W.

2012-01-01

Hydrogen spillover from a rhodium particle, over the most stable (111) surface, to a TiO2 rutile support occurs at low hydrogen coverage because the adsorption energy of H atoms at low hydrogen coverage on rutile is larger than that on rhodium. H diffuses over the support with an activation barrier

DNA Mismatch Binding and Antiproliferative Activity of Rhodium Metalloinsertors

Science.gov (United States)

Ernst, Russell J.; Song, Hang; Barton, Jacqueline K.

2009-01-01

Deficiencies in mismatch repair (MMR) are associated with carcinogenesis. Rhodium metalloinsertors bind to DNA base mismatches with high specificity and inhibit cellular proliferation preferentially in MMR-deficient cells versus MMR-proficient cells. A family of chrysenequinone diimine complexes of rhodium with varying ancillary ligands that serve as DNA metalloinsertors has been synthesized, and both DNA mismatch binding affinities and antiproliferative activities against the human colorectal carcinoma cell lines HCT116N and HCT116O, an isogenic model system for MMR deficiency, have been determined. DNA photocleavage experiments reveal that all complexes bind to the mismatch sites with high specificities; DNA binding affinities to oligonucleotides containing single base CA and CC mismatches, obtained through photocleavage titration or competition, vary from 104 to 108 M−1 for the series of complexes. Significantly, binding affinities are found to be inversely related to ancillary ligand size and directly related to differential inhibition of the HCT116 cell lines. The observed trend in binding affinity is consistent with the metalloinsertion mode where the complex binds from the minor groove with ejection of mismatched base pairs. The correlation between binding affinity and targeting of the MMR-deficient cell line suggests that rhodium metalloinsertors exert their selective biological effects on MMR-deficient cells through mismatch binding in vivo. PMID:19175313

Nitride alloy layer formation of duplex stainless steel using nitriding process

Science.gov (United States)

Maleque, M. A.; Lailatul, P. H.; Fathaen, A. A.; Norinsan, K.; Haider, J.

2018-01-01

Duplex stainless steel (DSS) shows a good corrosion resistance as well as the mechanical properties. However, DSS performance decrease as it works under aggressive environment and at high temperature. At the mentioned environment, the DSS become susceptible to wear failure. Surface modification is the favourable technique to widen the application of duplex stainless steel and improve the wear resistance and its hardness properties. Therefore, the main aim of this work is to nitride alloy layer on the surface of duplex stainless steel by the nitriding process temperature of 400°C and 450°C at different time and ammonia composition using a horizontal tube furnace. The scanning electron microscopy and x-ray diffraction analyzer are used to analyse the morphology, composition and the nitrided alloy layer for treated DSS. The micro hardnesss Vickers tester was used to measure hardness on cross-sectional area of nitrided DSS. After nitriding, it was observed that the hardness performance increased until 1100 Hv0.5kgf compared to substrate material of 250 Hv0.5kgf. The thickness layer of nitride alloy also increased from 5μm until 100μm due to diffusion of nitrogen on the surface of DSS. The x-ray diffraction results showed that the nitride layer consists of iron nitride, expanded austenite and chromium nitride. It can be concluded that nitride alloy layer can be produced via nitriding process using tube furnace with significant improvement of microstructural and hardness properties.

The isomerization of allylrhodium intermediates in the rhodium-catalyzed nucleophilic allylation of cyclic imines.

Science.gov (United States)

Hepburn, Hamish B; Lam, Hon Wai

2014-10-20

Allylrhodium species generated from potassium allyltrifluoroborates can undergo isomerization by 1,4-rhodium(I) migration to give more complex isomers, which then react with cyclic imines to provide products with up to three new stereochemical elements. High enantioselectivities are obtained using chiral diene-rhodium complexes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Separation of carrier-free rhodium isotopes from ruthenium cyclotron targets by the extraction of nitrosylruthenium from hydrochloric acid solution

International Nuclear Information System (INIS)

Haasbroek, F.J.; Strelow, F.W.E.; Van der Walt, T.N.

1981-01-01

A method is presented for the separation of rhodium isotopes from ruthenium cyclotron targets. After bombardment with deuterons and dissolution of the target material, the ruthenium is converted into a nitrosyl complex by treatment with hydroxylammonium chloride. Aluminium and other elements which have been introduced in the dissolution step, are separated by cation exchange. Ruthenium is then separated by extraction with a mixture of tri-n-butyl phosphate and hexane (4:1), leaving the rhodium in the aqueous phase. No ruthenium is found in the rhodium fraction and the recovery of rhodium is better than 90 per cent [af

Activation of heterogenised rhodium carbonylation catalyst infrared spectroscopic study

Energy Technology Data Exchange (ETDEWEB)

Scurrell, M S

1977-01-01

In a study related to heterogeneous versions of homogeneous catalysts active in carbonylation of methanol to acetic acid, the catalyst consisted of 1Vertical Bar3< rhodium as rhodium trichloride supported on 13X zeolite and evacuated at 437/sup 0/K. Contacting the catalyst with carbon monoxide caused two bands, at 2025 and 2095 cm/sup -1/, to appear. Contact with a mixture of carbon monoxide and methyl iodide (the usual promoter) caused bands at 2085, 1710, 1440, and 1370 cm/sup -1/ to appear; the first two correspond to the bands at 2062 and 1711 cm/sup -1/ in homogeneous catalysts attributed to the formation of Rh(CH/sup 3/CO)(CO)X/sup 2/I/sup -/. Spectra.

The extraction of rhodium from aqueous nitric acid by dinonylnaphthalene sulphonic acid

International Nuclear Information System (INIS)

Patel, N.M.; Miles, J.H.; Thornback, J.R.

1987-01-01

The extraction of rhodium from aqueous nitric acid using dinonylnaphthalene sulphonic acid has been investigated. The extraction occurs readily from 0.1 M to 1.0 M nitric acid and, since the rhodium is extracted as {Rh(H 2 O) 6 } 3+ into the inverted micelles of the organic solution, equilibration times are less than 5 minutes. Extraction is enhanced by addition of nitrite ion to form {Rh(H 2 O) 5 NO 2 } 2+ as the extracted species. (author)

Mechanism of intermolecular hydroacylation of vinylsilanes catalyzed by a rhodium(I) olefin complex: a DFT study.

Science.gov (United States)

Meng, Qingxi; Shen, Wei; Li, Ming

2012-03-01

Density functional theory (DFT) was used to investigate the Rh(I)-catalyzed intermolecular hydroacylation of vinylsilane with benzaldehyde. All intermediates and transition states were optimized completely at the B3LYP/6-31G(d,p) level (LANL2DZ(f) for Rh). Calculations indicated that Rh(I)-catalyzed intermolecular hydroacylation is exergonic, and the total free energy released is -110 kJ mol(-1). Rh(I)-catalyzed intermolecular hydroacylation mainly involves the active catalyst CA2, rhodium-alkene-benzaldehyde complex M1, rhodium-alkene-hydrogen-acyl complex M2, rhodium-alkyl-acyl complex M3, rhodium-alkyl-carbonyl-phenyl complex M4, rhodium-acyl-phenyl complex M5, and rhodium-ketone complex M6. The reaction pathway CA2 + R2 → M1b → T1b → M2b → T2b1 → M3b1 → T4b → M4b → T5b → M5b → T6b → M6b → P2 is the most favorable among all reaction channels of Rh(I)-catalyzed intermolecular hydroacylation. The reductive elimination reaction is the rate-determining step for this pathway, and the dominant product predicted theoretically is the linear ketone, which is consistent with Brookhart's experiments. Solvation has a significant effect, and it greatly decreases the free energies of all species. The use of the ligand Cp' (Cp' = C(5)Me(4)CF(3)) decreased the free energies in general, and in this case the rate-determining step was again the reductive elimination reaction.

Co-deposition of rhodium and tungsten films for the first-mirror on ITER

International Nuclear Information System (INIS)

Marot, Laurent; Steiner, Roland; Gantenbein, Markus; Mathys, Daniel; Meyer, Ernst

2011-01-01

The detailed characterizations of rhodium/tungsten films prepared by co-deposition using a dual magnetron sputtering have been carried out on silicon substrates at room temperature. Effects of the tungsten incorporated in the film on the chemical bonding state, optical reflectivity and crystallinity were investigated using X-ray photoelectron spectroscopy (XPS), reflectivity measurements, X-rays diffraction (XRD) and scanning electron microscopy (SEM). The incorporation of tungsten changes the films crystalline structure i.e. leading to Rh 3 W formation. The reflectivity of the films decreases linearly with the decrease of rhodium concentration. XPS and ultraviolet photoemission spectroscopy (UPS) measurements show a positive shift of the core level binding energy of rhodium which is coupled to a shift of the Rh d-band ΔE d away from the Fermi level. Opposite shifts are observed for tungsten.

Structural properties of small rhodium clusters

Energy Technology Data Exchange (ETDEWEB)

Soon, Yee Yeen; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

2015-04-24

We report a systematic study of the structural properties of rhodium clusters at the atomistic level. A novel global-minimum search algorithm, known as parallel tempering multicanonical basin hopping plus genetic algorithm (PTMBHGA), is used to obtain the geometrical structures with lowest minima at the semi-empirical level where Gupta potential is used to describe the atomic interaction among the rhodium atoms. These structures are then re-optimized at the density functional theory (DFT) level with exchange-correlation energy approximated by Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA). The structures are optimized for different spin multiplicities. The ones with lowest energies will be taken as ground-state structures. In most cases, we observe only minor changes in the geometry and bond length of the clusters as a result of DFT-level re-optimization. Only in some limited cases, the initial geometries obtained from the PTMBHGA are modified by the re-optimization. The variation of structural properties, such as ground-state geometry, symmetry and binding energy, with respect to the cluster size is studied and agreed well with other results available in the literature.

Light-induced reduction of rhodium(III) and palladium(II) on titanium dioxide dispersions and the selective photochemical separation and recovery of gold(III), platinum(IV), and rhodium(III) in chloride media

Energy Technology Data Exchange (ETDEWEB)

Borgarello, E.; Serpone, N.; Emo, G.; Harris, R.; Pelizzetti, E.; Minero, C.

1986-12-03

Irradiation of aqueous TiO/sub 2/ dispersions containing palladium(II) or rhodium(III) chloride salts with AM1 simulated sunlight leads to the photoreduction of these metals, which are deposited on the semiconductor particle surface. Oxygen is detrimental to the photoreduction of rhodium(III) but not the photoreduction of palladium(II). However, in both cases the reduction process is most efficient if the solution contains CH/sub 3/OH, which acts to scavenge valence band holes of the illuminated TiO/sub 2/ semiconductor. The selective photoreduction and recovery of precious metals from a dilute solution (as might be found in industrial wastes) have been investigated for a mixture of gold(III), platinum(IV), and rhodium(III) chloride salts as a function of various parameters (pH, presence or absence of O/sub 2/, presence or absence of a hole scavenger, and the concentration of the semiconductor). At pH 0, gold is easily separated from platinum and rhodium. The rate of photoreduction of gold(III) on TiO/sub 2/ is nearly independent of the concentration of the semiconductor, under the experimental conditions employed; the limiting rate is 2.7 x 10/sup -7/ M s/sup -1/. The potential utility of this selective photochemical technique is discussed.

Rhodium SPND's Error Reduction using Extended Kalman Filter combined with Time Dependent Neutron Diffusion Equation

International Nuclear Information System (INIS)

Lee, Jeong Hun; Park, Tong Kyu; Jeon, Seong Su

2014-01-01

The Rhodium SPND is accurate in steady-state conditions but responds slowly to changes in neutron flux. The slow response time of Rhodium SPND precludes its direct use for control and protection purposes specially when nuclear power plant is used for load following. To shorten the response time of Rhodium SPND, there were some acceleration methods but they could not reflect neutron flux distribution in reactor core. On the other hands, some methods for core power distribution monitoring could not consider the slow response time of Rhodium SPND and noise effect. In this paper, time dependent neutron diffusion equation is directly used to estimate reactor power distribution and extended Kalman filter method is used to correct neutron flux with Rhodium SPND's and to shorten the response time of them. Extended Kalman filter is effective tool to reduce measurement error of Rhodium SPND's and even simple FDM to solve time dependent neutron diffusion equation can be an effective measure. This method reduces random errors of detectors and can follow reactor power level without cross-section change. It means monitoring system may not calculate cross-section at every time steps and computing time will be shorten. To minimize delay of Rhodium SPND's conversion function h should be evaluated in next study. Neutron and Rh-103 reaction has several decay chains and half-lives over 40 seconds causing delay of detection. Time dependent neutron diffusion equation will be combined with decay chains. Power level and distribution change corresponding movement of control rod will be tested with more complicated reference code as well as xenon effect. With these efforts, final result is expected to be used as a powerful monitoring tool of nuclear reactor core

Rhodium SPND's Error Reduction using Extended Kalman Filter combined with Time Dependent Neutron Diffusion Equation

Energy Technology Data Exchange (ETDEWEB)

Lee, Jeong Hun; Park, Tong Kyu; Jeon, Seong Su [FNC Technology Co., Ltd., Yongin (Korea, Republic of)

2014-05-15

The Rhodium SPND is accurate in steady-state conditions but responds slowly to changes in neutron flux. The slow response time of Rhodium SPND precludes its direct use for control and protection purposes specially when nuclear power plant is used for load following. To shorten the response time of Rhodium SPND, there were some acceleration methods but they could not reflect neutron flux distribution in reactor core. On the other hands, some methods for core power distribution monitoring could not consider the slow response time of Rhodium SPND and noise effect. In this paper, time dependent neutron diffusion equation is directly used to estimate reactor power distribution and extended Kalman filter method is used to correct neutron flux with Rhodium SPND's and to shorten the response time of them. Extended Kalman filter is effective tool to reduce measurement error of Rhodium SPND's and even simple FDM to solve time dependent neutron diffusion equation can be an effective measure. This method reduces random errors of detectors and can follow reactor power level without cross-section change. It means monitoring system may not calculate cross-section at every time steps and computing time will be shorten. To minimize delay of Rhodium SPND's conversion function h should be evaluated in next study. Neutron and Rh-103 reaction has several decay chains and half-lives over 40 seconds causing delay of detection. Time dependent neutron diffusion equation will be combined with decay chains. Power level and distribution change corresponding movement of control rod will be tested with more complicated reference code as well as xenon effect. With these efforts, final result is expected to be used as a powerful monitoring tool of nuclear reactor core.

Transient-response study of CO insertion into CHx surface intermediates on a vanadium-promoted rhodium catalyst

NARCIS (Netherlands)

Koerts, T.; Santen, van R.A.

1992-01-01

The rate of CO insertion into surface CHx species was investigated on silica-supported rhodium and rhodium-vanadium catalysts. Isotopically labelled 13CO was used in a transient kinetic experiment under steady-state conditions. A main conclusion is that vanadium promotion does not affect the rate of

Rhodium coated mirrors deposited by magnetron sputtering for fusion applications

International Nuclear Information System (INIS)

Marot, L.; De Temmerman, G.; Oelhafen, P.; Covarel, G.; Litnovsky, A.

2007-01-01

Metallic mirrors will be essential components of all optical spectroscopy and imaging systems for ITER plasma diagnostics. Any change in the mirror performance, in particular, its reflectivity, due to erosion of the surface by charge exchange neutrals or deposition of impurities will influence the quality and reliability of the detected signals. Due to its high reflectivity in the visible wavelength range and its low sputtering yield, rhodium appears as an attractive material for first mirrors in ITER. However, the very high price of the raw material calls for using it in the form of a film deposited onto metallic substrates. The development of a reliable technique for the preparation of high reflectivity rhodium films is therefore of the highest importance. Rhodium layers with thicknesses of up to 2 μm were produced on different substrates of interest (Mo, stainless steel, Cu) by magnetron sputtering. Produced films exhibit a low roughness and crystallite size of about 10 nm with a dense columnar structure. No impurities were detected on the surface after deposition. Scratch tests demonstrate that adhesion properties increase with substrate hardness. Detailed optical characterizations of Rh-coated mirrors as well as results of erosion tests performed both under laboratory conditions and in the TEXTOR tokamak are presented in this paper

Rhodium-coated mirrors deposited by magnetron sputtering for fusion applications

International Nuclear Information System (INIS)

Marot, L.; Temmermann, G. de; Oelhafen, P.; Mathys, D.; Covarel, G.; Litnovsky, A.

2007-01-01

Metallic mirrors will be essential components of all optical spectroscopy and imaging systems for plasma diagnostics that will be used in ITER. Any change in the mirror performance, in particular its reflectivity, will influence the quality and reliability of detected signals. Due to its high reflectivity in the visible wavelength range and its low sputtering yield, rhodium may be a good candidate material for first mirrors in ITER. However, the very high price of the raw material calls for using it in the form of a film deposited onto metallic substrates. The development of a reliable technique for the preparation of high reflectivity rhodium films is therefore of the highest importance. Rhodium layers with thicknesses of up to 2 μm were produced on different relevant substrates (Mo, Stainless Steel, Cu) by magnetron sputtering. Produced films exhibit a low roughness, crystallite size of about 10 nm with a dense columnar structure. No impurities were detected on the surface after deposition. Scratch test results demonstrate that adhesion properties increase with the substrate hardness. The detailed optical characterizations of Rh coated mirrors as well as the results of erosion tests performed both under laboratory conditions and in TEXTOR will be presented in this paper. (orig.)

Plasma nitriding of steels

CERN Document Server

Aghajani, Hossein

2017-01-01

This book focuses on the effect of plasma nitriding on the properties of steels. Parameters of different grades of steels are considered, such as structural and constructional steels, stainless steels and tools steels. The reader will find within the text an introduction to nitriding treatment, the basis of plasma and its roll in nitriding. The authors also address the advantages and disadvantages of plasma nitriding in comparison with other nitriding methods. .

Chemo- and regioselective homogeneous rhodium-catalyzed hydroamidomethylation of terminal alkenes to N-alkylamides.

Science.gov (United States)

Raoufmoghaddam, Saeed; Drent, Eite; Bouwman, Elisabeth

2013-09-01

A rhodium/xantphos homogeneous catalyst system has been developed for direct chemo- and regioselective mono-N-alkylation of primary amides with 1-alkenes and syngas through catalytic hydroamidomethylation with 1-pentene and acetamide as model substrates. For appropriate catalyst performance, it appears to be essential that catalytic amounts of a strong acid promoter, such as p-toluenesulfonic acid (HOTs), as well as larger amounts of a weakly acidic protic promoter, particularly hexafluoroisopropyl alcohol (HOR(F) ) are applied. Apart from the product N-1-hexylacetamide, the isomeric unsaturated intermediates, hexanol and higher mass byproducts, as well as the corresponding isomeric branched products, can be formed. Under optimized conditions, almost full alkene conversion can be achieved with more than 80% selectivity to the product N-1-hexylamide. Interestingly, in the presence of a relatively high concentration of HOR(F) , the same catalyst system shows a remarkably high selectivity for the formation of hexanol from 1-pentene with syngas, thus presenting a unique example of a selective rhodium-catalyzed hydroformylation-hydrogenation tandem reaction under mild conditions. Time-dependent product formation during hydroamidomethylation batch experiments provides evidence for aldehyde and unsaturated intermediates; this clearly indicates the three-step hydroformylation/condensation/hydrogenation reaction sequence that takes place in hydroamidomethylation. One likely role of the weakly acidic protic promoter, HOR(F) , in combination with the strong acid HOTs, is to establish a dual-functionality rhodium catalyst system comprised of a neutral rhodium(I) hydroformylation catalyst species and a cationic rhodium(III) complex capable of selectively reducing the imide and/or ene-amide intermediates that are in a dynamic, acid-catalyzed condensation equilibrium with the aldehyde and amide in a syngas environment. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diphosphinoazine Rhodium(I) and Iridium(I) Complexes

Czech Academy of Sciences Publication Activity Database

Pošta, Martin; Čermák, Jan; Vojtíšek, P.; Císařová, I.

2006-01-01

Roč. 71, č. 2 (2006), s. 197-206 ISSN 0010-0765 R&D Projects: GA ČR(CZ) GA203/01/0554; GA ČR(CZ) GA203/99/M037 Institutional research plan: CEZ:AV0Z40720504 Keywords : diphosphinoazines * rhodium complexes * iridium complexes Subject RIV: CC - Organic Chemistry Impact factor: 0.881, year: 2006

Determination of rhodium in metallic alloy and water samples using cloud point extraction coupled with spectrophotometric technique

Science.gov (United States)

Kassem, Mohammed A.; Amin, Alaa S.

2015-02-01

A new method to estimate rhodium in different samples at trace levels had been developed. Rhodium was complexed with 5-(4‧-nitro-2‧,6‧-dichlorophenylazo)-6-hydroxypyrimidine-2,4-dione (NDPHPD) as a complexing agent in an aqueous medium and concentrated by using Triton X-114 as a surfactant. The investigated rhodium complex was preconcentrated with cloud point extraction process using the nonionic surfactant Triton X-114 to extract rhodium complex from aqueous solutions at pH 4.75. After the phase separation at 50 °C, the surfactant-rich phase was heated again at 100 °C to remove water after decantation and the remaining phase was dissolved using 0.5 mL of acetonitrile. Under optimum conditions, the calibration curve was linear for the concentration range of 0.5-75 ng mL-1 and the detection limit was 0.15 ng mL-1 of the original solution. The enhancement factor of 500 was achieved for 250 mL samples containing the analyte and relative standard deviations were ⩽1.50%. The method was found to be highly selective, fairly sensitive, simple, rapid and economical and safely applied for rhodium determination in different complex materials such as synthetic mixture of alloys and environmental water samples.

Rhodium(iii)-catalyzed ortho-olefination of aryl phosphonates.

Science.gov (United States)

Chary, Bathoju Chandra; Kim, Sunggak

2013-09-25

Rhodium(iii)-catalyzed C-H olefination of aryl phosphonic esters is reported for the first time. In this mild and efficient process, the phosphonic ester group is utilized successfully as a new directing group. In addition, mono-olefination for aryl phosphonates is observed using a phosphonic diamide directing group.

Sorption properties study of nitron fibre S-3 relative to rhodium (III)

International Nuclear Information System (INIS)

Rustamov, S.; Khusainov, A.D.; Shadieva, S.F.

2001-01-01

The purpose of present work is studying of sorption properties of nitron fibre S-3 relative to rhodium (III) from chloride solutions. Nitron sorbent S-3 was synthesised by reprocessing of wastes of production of nitron fibre by sulfited compound Na 2 Sn:NH 4 SCN=50:50 during 3 hours at temperature 90 d ig C . The sulfur containing in the sorbent was about 9%. During investigation by authors was determined that fibre nitron-S has good kinetic characteristics relative to rhodium (III), limitative stage of sorption process is diffusion and kinetics of sorption has mixed-diffusion character

Ion nitriding of aluminium

International Nuclear Information System (INIS)

Fitz, T.

2002-09-01

The present study is devoted to the investigation of the mechanism of aluminium nitriding by a technique that employs implantation of low-energy nitrogen ions and diffusional transport of atoms. The nitriding of aluminium is investigated, because this is a method for surface modification of aluminium and has a potential for application in a broad spectrum of fields such as automobile, marine, aviation, space technologies, etc. However, at present nitriding of aluminium does not find any large scale industrial application, due to problems in the formation of stoichiometric aluminium nitride layers with a sufficient thickness and good quality. For the purposes of this study, ion nitriding is chosen, as an ion beam method with the advantage of good and independent control over the process parameters, which thus can be related uniquely to the physical properties of the resulting layers. Moreover, ion nitriding has a close similarity to plasma nitriding and plasma immersion ion implantation, which are methods with a potential for industrial application. (orig.)

Cell-Selective Biological Activity of Rhodium Metalloinsertors Correlates with Subcellular Localization

Science.gov (United States)

Komor, Alexis C.; Schneider, Curtis J.; Weidmann, Alyson G.; Barton, Jacqueline K.

2013-01-01

Deficiencies in the mismatch repair (MMR) pathway are associated with several types of cancers, as well as resistance to commonly used chemotherapeutics. Rhodium metalloinsertors have been found to bind DNA mismatches with high affinity and specificity in vitro, and also exhibit cell-selective cytotoxicity, targeting MMR-deficient cells over MMR-proficient cells. Ten distinct metalloinsertors with varying lipophilicities have been synthesized and their mismatch binding affinities and biological activities determined. Although DNA photocleavage experiments demonstrate that their binding affinities are quite similar, their cell-selective antiproliferative and cytotoxic activities vary significantly. Inductively coupled plasma mass spectrometry (ICP-MS) experiments have uncovered a relationship between the subcellular distribution of these metalloinsertors and their biological activities. Specifically, we find that all of our metalloinsertors localize in the nucleus at sufficient concentrations for binding to DNA mismatches. However, the metalloinsertors with high rhodium localization in the mitochondria show toxicity that is not selective for MMR-deficient cells, whereas metalloinsertors with less mitochondrial rhodium show activity that is highly selective for MMR-deficient versus proficient cells. This work supports the notion that specific targeting of the metalloinsertors to nuclear DNA gives rise to their cell-selective cytotoxic and antiproliferative activities. The selectivity in cellular targeting depends upon binding to mismatches in genomic DNA. PMID:23137296

Selectivity of a heterogeneous rhodium catalyst for the carbonylation of monohydric alcohols

Energy Technology Data Exchange (ETDEWEB)

Christensen, B; Scurrell, M S

1977-01-01

Selectivity of a heterogeneous rhodium catalyst for the carbonylation of monohydric alcohols with carbon monoxide in the presence of the corresponding alkyl iodides as promotors was studied in a glass reactor at approx. 0.05:1 alcohol/carbon monoxide ratio. The 1% by wt rhodium-zeolite catalyst was prepared by immersing a Linde molecular sieve zeolite Type 13X in rhodium trichloride at 80/sup 0/C for 15 hr. Methanol was converted to methyl acetate at 433/sup 0/-513/sup 0/K with selectivites > 90% even at the highest temperatures, and dimethyl ether was by-produced. In the absence of methyl iodide, the carbonylation rate decreased drastically but the dehydration was virtually unaffected. The selectivity for ethanol carbonylation decreased from 99% at 383/sup 0/K to 6% at 523/sup 0/K due to the formation of ethylene (predominant at > 470/sup 0/K) and diethyl ether. The only product of the reaction with propan-2-ol studied at 433/sup 0/ or 473/sup 0/K was propene with 100% conversion at 473/sup 0/K. These results are consistent with the relative ease of reactant dehydration on polar catalysts. Table and 13 references.

Enantioselective rhodium/ruthenium photoredox catalysis en route to chiral 1,2-aminoalcohols.

Science.gov (United States)

Ma, Jiajia; Harms, Klaus; Meggers, Eric

2016-08-09

A rhodium-based chiral Lewis acid catalyst combined with [Ru(bpy)3](PF6)2 as a photoredox sensitizer allows for the visible-light-activated redox coupling of α-silylamines with 2-acyl imidazoles to afford, after desilylation, 1,2-amino-alcohols in yields of 69-88% and with high enantioselectivity (54-99% ee). The reaction is proposed to proceed via an electron exchange between the α-silylamine (electron donor) and the rhodium-chelated 2-acyl imidazole (electron acceptor), followed by a stereocontrolled radical-radical reaction. Substrate scope and control experiments reveal that the trimethylsilyl group plays a crucial role in this reductive umpolung of the carbonyl group.

A multi-target caffeine derived rhodium(i) N-heterocyclic carbene complex: evaluation of the mechanism of action.

Science.gov (United States)

Zhang, Jing-Jing; Muenzner, Julienne K; Abu El Maaty, Mohamed A; Karge, Bianka; Schobert, Rainer; Wölfl, Stefan; Ott, Ingo

2016-08-16

A rhodium(i) and a ruthenium(ii) complex with a caffeine derived N-heterocyclic carbene (NHC) ligand were biologically investigated as organometallic conjugates consisting of a metal center and a naturally occurring moiety. While the ruthenium(ii) complex was largely inactive, the rhodium(i) NHC complex displayed selective cytotoxicity and significant anti-metastatic and in vivo anti-vascular activities and acted as both a mammalian and an E. coli thioredoxin reductase inhibitor. In HCT-116 cells it increased the reactive oxygen species level, leading to DNA damage, and it induced cell cycle arrest, decreased the mitochondrial membrane potential, and triggered apoptosis. This rhodium(i) NHC derivative thus represents a multi-target compound with promising anti-cancer potential.

Nitride stabilized core/shell nanoparticles

Science.gov (United States)

Kuttiyiel, Kurian Abraham; Sasaki, Kotaro; Adzic, Radoslav R.

2018-01-30

Nitride stabilized metal nanoparticles and methods for their manufacture are disclosed. In one embodiment the metal nanoparticles have a continuous and nonporous noble metal shell with a nitride-stabilized non-noble metal core. The nitride-stabilized core provides a stabilizing effect under high oxidizing conditions suppressing the noble metal dissolution during potential cycling. The nitride stabilized nanoparticles may be fabricated by a process in which a core is coated with a shell layer that encapsulates the entire core. Introduction of nitrogen into the core by annealing produces metal nitride(s) that are less susceptible to dissolution during potential cycling under high oxidizing conditions.

Hydroformylation of methyl oleate catalyzed by rhodium complexes; Hidroformilacao do oleato de metila catalisada por complexos de rodio

Energy Technology Data Exchange (ETDEWEB)

Mendes, Ana Nery Furlan [Universidade Federal do Espirito Santo (UFES), Sao Mateus, ES (Brazil). Centro Universitario Norte do Espirito Santo. Dept. de Ciencias Naturais; Rosa, Ricardo Gomes da; Gregorio, Jose Ribeiro, E-mail: jrg@iq.ufrgs.br [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica

2012-07-01

In this work, we describe the hydroformylation of methyl oleate catalyzed by several rhodium complexes. Parameters including total pressure, phosphorous/rhodium and CO/H{sub 2} ratio, temperature and phosphorous ligands were scanned. Total conversion of the starting double bonds was achieved while maintaining excellent selectivity in aldehydes. (author)

A rhodium(III)-based inhibitor of autotaxin with antiproliferative activity.

Science.gov (United States)

Kang, Tian-Shu; Wang, Wanhe; Zhong, Hai-Jing; Liang, Jia-Xin; Ko, Chung-Nga; Lu, Jin-Jian; Chen, Xiu-Ping; Ma, Dik-Lung; Leung, Chung-Hang

2017-02-01

Cancer of the skin is by far the most common of all cancers. Melanoma accounts for only about 1% of skin cancers but causes a large majority of skin cancer deaths. Autotaxin (ATX), also known as ectonucleotide pyrophosphatase/phosphodiesterase 2 (ENPP2), regulates physiological and pathological functions of lysophosphatidic acid (LPA), and is thus an important therapeutic target. We synthesized ten metal-based complexes and a novel cyclometalated rhodium(III) complex 1 was identified as an ATX enzymatic inhibitor using multiple methods, including ATX enzymatic assay, thermal shift assay, western immunoblotting and so on. Protein thermal shift assays showed that 1 increased the melting temperature (T m ) of ATX by 3.5°C. 1 also reduced ATX-LPA mediated downstream survival signal pathway proteins such as ERK and AKT, and inhibited the activation of the transcription factor nuclear factor κB (NF-κB) and signal transducer and activator of transcription 3 (STAT3). 1 also exhibited strong anti-proliferative activity against A2058 melanoma cells (IC 50 =0.58μM). Structure-activity relationship indicated that both the rhodium(III) center and the auxiliary ligands of complex 1 are important for bioactivity. 1 represents a promising scaffold for the development of small-molecule ATX inhibitors for anti-tumor applications. To our knowledge, complex 1 is the first metal-based ATX inhibitor reported to date. Rhodium complexes will have the increased attention in therapeutic and bioanalytical applications. Copyright © 2016 Elsevier B.V. All rights reserved.

A Concise Synthesis of the Erythrina Alkaloid 3–Demethoxyerythratidinone via Combined Rhodium Catalysis

Science.gov (United States)

Joo, Jung Min; David, Ramoncito A.; Yuan, Yu; Lee, Chulbom

2010-01-01

The total synthesis of the erythrina alkaloid 3–demethoxyerythratidinone has been achieved via a strategy based on combined rhodium catalysis. The catalytic tandem cyclization effected by the interplay of alkynyl and vinylidene rhodium species allows for efficient access to the A and B rings of the tetracyclic erythrinane skeleton in a single step. The synthesis also features rapid preparation of the requisite precursor for the double ring closure and thus has been completed in only 7 total steps in 41% overall yield. PMID:21090648

Fabrication of vanadium nitride by carbothermal nitridation reaction

International Nuclear Information System (INIS)

Wang Xitang; Wang Zhuofu; Zhang Baoguo; Deng Chengji

2005-01-01

Vanadium nitride is produced from V 2 O 5 by carbon-thermal reduction and nitridation. When the sintered temperature is above 1273 K, VN can be formed, and the nitrogen content of the products increased with the firing temperature raised, and then is the largest when the sintered temperature is 1573 K. The C/V 2 O 5 mass ratio of the green samples is the other key factor affecting on the nitrogen contents of the products. The nitrogen content of the products reaches the most when the C/V 2 O 5 mass ratio is 0.33, which is the theoretical ratio of the carbothermal nitridation of V 2 O 5 . (orig.)

Adducts of nitrogenous ligands with rhodium(II) tetracarboxylates and tetraformamidinate: NMR spectroscopy and density functional theory calculations.

Science.gov (United States)

Cmoch, Piotr; Głaszczka, Rafał; Jaźwiński, Jarosław; Kamieński, Bohdan; Senkara, Elżbieta

2014-03-01

Complexation of tetrakis(μ2-N,N'-diphenylformamidinato-N,N')-di-rhodium(II) with ligands containing nitrile, isonitrile, amine, hydroxyl, sulfhydryl, isocyanate, and isothiocyanate functional groups has been studied in liquid and solid phases using (1)H, (13)C and (15)N NMR, (13)C and (15)N cross polarisation-magic angle spinning NMR, and absorption spectroscopy in the visible range. The complexation was monitored using various NMR physicochemical parameters, such as chemical shifts, longitudinal relaxation times T1 , and NOE enhancements. Rhodium(II) tetraformamidinate selectively bonded only unbranched amine (propan-1-amine), pentanenitrile, and (1-isocyanoethyl)benzene. No complexation occurred in the case of ligands having hydroxyl, sulfhydryl, isocyanate, and isothiocyanate functional groups, and more expanded amine molecules such as butan-2-amine and 1-azabicyclo[2.2.2]octane. Such features were opposite to those observed in rhodium(II) tetracarboxylates, forming adducts with all kind of ligands. Special attention was focused on the analysis of Δδ parameters, defined as a chemical shift difference between signal in adduct and corresponding signal in free ligand. In the case of (1)H NMR, Δδ values were either negative in adducts of rhodium(II) tetraformamidinate or positive in adducts of rhodium(II) tetracarboxylates. Experimental findings were supported by density functional theory molecular modelling and gauge independent atomic orbitals chemical shift calculations. The calculation of chemical shifts combined with scaling procedure allowed to reproduce qualitatively Δδ parameters. Copyright © 2013 John Wiley & Sons, Ltd.

Asymmetric Synthesis of Hydrocarbazoles Catalyzed by an Octahedral Chiral-at-Rhodium Lewis Acid.

Science.gov (United States)

Huang, Yong; Song, Liangliang; Gong, Lei; Meggers, Eric

2015-12-01

A bis-cyclometalated chiral-at-metal rhodium complex catalyzes the Diels-Alder reaction between N-Boc-protected 3-vinylindoles (Boc = tert-butyloxycarbonyl) and β-carboxylic ester-substituted α,β-unsaturated 2-acyl imidazoles with good-to-excellent regioselectivity (up to 99:1) and excellent diastereoselectivity (>50:1 d.r.) as well as enantioselectivity (92-99% ee) under optimized conditions. The rhodium catalyst serves as a chiral Lewis acid to activate the 2-acyl imidazole dienophile by two-point binding and overrules the preferred regioselectivity of the uncatalyzed reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method for producing polycrystalline boron nitride

International Nuclear Information System (INIS)

Alexeevskii, V.P.; Bochko, A.V.; Dzhamarov, S.S.; Karpinos, D.M.; Karyuk, G.G.; Kolomiets, I.P.; Kurdyumov, A.V.; Pivovarov, M.S.; Frantsevich, I.N.; Yarosh, V.V.

1975-01-01

A mixture containing less than 50 percent of graphite-like boron nitride treated by a shock wave and highly defective wurtzite-like boron nitride obtained by a shock-wave method is compressed and heated at pressure and temperature values corresponding to the region of the phase diagram for boron nitride defined by the graphite-like compact modifications of boron nitride equilibrium line and the cubic wurtzite-like boron nitride equilibrium line. The resulting crystals of boron nitride exhibit a structure of wurtzite-like boron nitride or of both wurtzite-like and cubic boron nitride. The resulting material exhibits higher plasticity as compared with polycrystalline cubic boron nitride. Tools made of this compact polycrystalline material have a longer service life under impact loads in machining hardened steel and chilled iron. (U.S.)

Functionalized cyclopentadienyl rhodium(III) bipyridine complexes: synthesis, characterization, and catalytic application in hydrogenation of ketones.

Science.gov (United States)

Wang, Wan-Hui; Suna, Yuki; Himeda, Yuichiro; Muckerman, James T; Fujita, Etsuko

2013-07-14

A series of highly functionalized cyclopentadienyl rhodium(III) complexes, [Cp'Rh(bpy)Br](ClO4) (Cp' = substituted cyclopentadienyl), was synthesized from various multi-substituted cyclopentadienes (Cp'H). [Rh(cod)Cl]2 and Cp'H were firstly converted to [Cp'Rh(cod)] complexes, which were then treated with Br2 to give the rhodium(III) dibromides [Cp'RhBr2]2. The novel complexes [Cp'Rh(bpy)Br](ClO4) were obtained readily by the reaction of 2,2'-bipyridine with [Cp'RhBr2]2. These rhodium complexes [Cp'Rh(bpy)Br](ClO4) were fully characterized and utilized in the hydrogenation of cyclohexanone and acetophenone with generally high yields, but they did not exhibit the same reactivity trends for the two substrate ketones. The different activity of these complexes for the different substrates may be due to the influence of the substituents on the Cp' rings.

Exposure of the German general population to platinum and rhodium - Urinary levels and determining factors.

Science.gov (United States)

Munker, Sven; Kilo, Sonja; Röß, Christoph; Jeitner, Peter; Schierl, Rudolf; Göen, Thomas; Drexler, Hans

2016-11-01

In this study the exposure of the general population in Germany to platinum and rhodium and its determinants was investigated in 259 participants (subdivided in three groups) by urine analyses and assessment of the dental status. Complementary, an interview including questions characterising possible exposure to traffic exhaust was conducted. The median excretion was 2.42ng platinum/g creatinine and 7.27ng rhodium/g creatinine. The detailed analysis of the collected data showed significant higher platinum excretion values with increasing number of surfaces covered with restorations containing precious metals (R=0.389; prhodium excretion values (median=7.27ng/g; 95th percentile=13.5 ng/g). In summary, the study showed that exhaust emissions have an influence on platinum and rhodium excretion, but for platinum this influence is rather low compared to the influence of precious metals containing restorations. Copyright © 2016 Elsevier GmbH. All rights reserved.

Dihydropyranone Formation by Ipso C–H Activation in a Glucal 3-Carbamate-Derived Rhodium Acyl Nitrenoid

Science.gov (United States)

Hurlocker, Brisa; Abascal, Nadia C.; Repka, Lindsay M.; Santizo-Deleon, Elsy; Smenton, Abigail L.; Baranov, Victoria; Gupta, Ritu; Bernard, Sarah E.; Chowdhury, Shenjuti; Rojas, Christian M.

2011-01-01

By using (N-tosyloxy)-3-O-carbamoyl-D-glucal 10, which removes the need for a hypervalent iodine(III) oxidant, we provide evidence for rhodium nitrenoid-mediated ipso C–H activation as the origin of a C3-oxidized dihydropyranone product 3. This system may be especially susceptible to such a pathway due to the ease of forming a cation upon hydride transfer to the rhodium-complexed acyl nitrene. PMID:21381715

Electrodeposition of carrier-free 57Co on rhodium as an approach to the preparation of Moessbauer sources

International Nuclear Information System (INIS)

Cieszykowska, Izabela; ZoLtowska, MaLgorzata; Mielcarski, MieczysLaw

2011-01-01

Electrodeposition of carrier-free 57 Co on a rhodium matrix as the first step of preparing Moessbauer sources was studied. To optimize the plating parameters, the influences of current density, volume and pH of the electrolyte solution, shape, thickness, and surface area of the rhodium cathode, mode of cathode pretreatment, concentration of 57 Co and duration of electrolysis were investigated.

Excess Substrate is a Spectator Ligand in a Rhodium-Catalyzed Asymmetric [2+2+2] Cycloaddition of Alkenyl Isocyanates with Tolanes

Science.gov (United States)

Oinen, Mark Emil; Yu, Robert T.; Rovis, Tomislav

2009-01-01

Excess substrate has been identified as an unintended spectator ligand affecting enantioselectivity in the [2+2+2] cycloaddition of alkenyl isocyanates with tolanes. Replacement of excess substrate with an exogenous additive affords products with consistent and higher ee’s. The increase in enantioselectivity is the result of a change in composition of a proposed rhodium(III) intermediate on the catalytic cycle. The net result is a rational probe of a short-lived rhodium(III) intermediate, and gives insight that may have applications in many rhodium catalyzed reactions. PMID:19803471

Extraction of ruthenium thiocyanate and its separation from rhodium by polyurethane foam

International Nuclear Information System (INIS)

Al-Bazi, S.J.; Chow, A.

1984-01-01

Conditions for the formation and extraction of the thiocyanate complex of ruthenium are reported. Distribution coefficients of more than 10 4 and a capacity of about 0.24 mole per kg of foam were obtained. The effect of the chloride salts of various univalent cations on the extraction of Ru(SCN) 6 3- indicated that the efficiency of ruthenium extraction depends on how well the cation fits into the polyether segment of the polyurethane foam, which agrees with the 'cation-chelation' mechanism. The separation of ruthenium and rhodium indicated that more than 95% of the rhodium remained in the aqueous phase and about 95% of the ruthenium was retained by the polyurethane foam and could be easily recovered. (author)

Antitumor effect of free rhodium (II) citrate and rhodium (II) citrate-loaded maghemite nanoparticles on mice bearing breast cancer: a systemic toxicity assay.

Science.gov (United States)

Peixoto, Raphael Cândido Apolinário; Miranda-Vilela, Ana Luisa; de Souza Filho, José; Carneiro, Marcella Lemos' Brettas; Oliveira, Ricardo G S; da Silva, Matheus Oliveira; de Souza, Aparecido R; Báo, Sônia Nair

2015-05-01

Breast cancer is one of the most prevalent cancer types among women. The use of magnetic fluids for specific delivery of drugs represents an attractive platform for chemotherapy. In our previous studies, it was demonstrated that maghemite nanoparticles coated with rhodium (II) citrate (Magh-Rh2Cit) induced in vitro cytotoxicity and in vivo antitumor activity, followed by intratumoral administration in breast carcinoma cells. In this study, our aim was to follow intravenous treatment to evaluate the systemic antitumor activity and toxicity induced by these formulations in Balb/c mice bearing orthotopic 4T1 breast carcinoma. Female Balb/c mice were evaluated with regard to toxicity of intravenous treatments through analyses of hemogram, serum levels of alanine aminotransferase, iron, and creatinine and liver, kidney, and lung histology. The antitumor activity of rhodium (II) citrate (Rh2Cit), Magh-Rh2Cit, and maghemite nanoparticles coated with citrate (Magh-Cit), used as control, was evaluated by tumor volume reduction, histology, and morphometric analysis. Magh-Rh2Cit and Magh-Cit promoted a significant decrease in tumor area, and no experimental groups presented hematotoxic effects or increased levels of serum ALT and creatinine. This observation was corroborated by the histopathological examination of the liver and kidney of mice. Furthermore, the presence of nanoparticles was verified in lung tissue with no morphological changes, supporting the idea that our nanoformulations did not induce toxicity effects. No studies about the systemic action of rhodium (II) citrate-loaded maghemite nanoparticles have been carried out, making this report a suitable starting point for exploring the therapeutic potential of these compounds in treating breast cancer.

Preparation of uranium nitride

International Nuclear Information System (INIS)

Potter, R.A.; Tennery, V.J.

1976-01-01

A process is described for preparing actinide-nitrides from massive actinide metal which is suitable for sintering into low density fuel shapes by partially hydriding the massive metal and simultaneously dehydriding and nitriding the dehydrided portion. The process is repeated until all of the massive metal is converted to a nitride

Rhodium-catalyzed C-H functionalization with N-acylsaccharins.

Science.gov (United States)

Wu, Hongxiang; Liu, Tingting; Cui, Ming; Li, Yue; Jian, Junsheng; Wang, Hui; Zeng, Zhuo

2017-01-18

A rhodium-catalyzed C-H functionalization with activated amides by decarbonylation has been developed. Notably, this is the first C-H arylation employing N-acylsaccharins as coupling partners to give biaryls in good to excellent yields. The highlight of the work is the high tolerance of functional groups such as formyl, ester, and vinyl and the use of a removable directing group.

Rhodium(II)-Catalyzed Asymmetric Sulfur(VI) Reduction of Diazo Sulfonylamidines

OpenAIRE

Selander, Nicklas; Fokin, Valery V.

2012-01-01

Diazo sulfonylamidines readily undergo enantioselective oxygen transfer from sulfur to carbon atom in the presence of chiral rhodium(II) carboxylates resulting in chiral sulfinylamidines. This unusual asymmetric atom transfer “reduction” occurs rapidly under mild conditions, and sulfinylamidines are obtained in excellent yield.

The liquid-liquid extraction of chloro-(trichlorostannato)-rhodium(I/III) and -ruthenium (II) complexes from dilute hydrochloric acid into 4-methylpentan-2-one

International Nuclear Information System (INIS)

Wyrley-Birch, J.M.

1984-10-01

The effect of stannous chloride on the liquid-liquid extraction of rhodium and ruthenium from hydrochloric acid solutions into 4-methyl-pentan-2-one (MIBK)/hexane mixtures was studied in detail. Stannous chloride concentrations were found to considerably increase the efficiency of the extraction of rhodium and ruthenium into the organic phase. Chloro-(trichlorostannato)-rhodium (I/III) complexes were formed at room temperature. The rate of chloro-(trichlorostannato)-ruthenium (II) complex formation was extremely slow at room temperature, but increased on heating of the aqueous solutions. The amount of rhodium and ruthenium extracted into the organic phase depend on the Sn(II):M molar ratio, the HCl, H sup(+) and Cl sup(-) concentrations, as well as the equilibration time. A 119 Sn NMR study of the MIBK extracts, showed that the stoichiometry of the chloro-(trichlorostannato)-rhodium (I/III) complexes extracted into the organic phase was dependent on the Sn(II):Rh(III) molar ratio as well as the HCl, H sup(+) and Cl sup(-) concentrations in the aqueous phase. The predominant species observed in the organic phase from HCl solutions containing Sn(II):Rh(III) ratios >= 5:1, was shown to be an hydrido complex having the form [RhH(SnCl 3 ) 4 Cl] 3 sup(-) or [RhH(SnCl 3 ) 4 ]2 sup(-). An essentially quantitative separation of rhodium and ruthenium was achieved utilising the variation in the rates of rhodium-tin and ruthenium-tin complex formation

Selective Cytotoxicity of Rhodium Metalloinsertors in Mismatch Repair-Deficient Cells†

Science.gov (United States)

Ernst, Russell J.; Komor, Alexis C.; Barton, Jacqueline K.

2011-01-01

Mismatches in DNA occur naturally during replication and as a result of endogenous DNA damaging agents, but the mismatch repair (MMR) pathway acts to correct mismatches before subsequent rounds of replication. Rhodium metalloinsertors bind to DNA mismatches with high affinity and specificity and represent a promising strategy to target mismatches in cells. Here we examine the biological fate of rhodium metalloinsertors bearing dipyridylamine ancillary ligands in cells deficient in MMR versus those that are MMR-proficient. These complexes are shown to exhibit accelerated cellular uptake which permits the observation of various cellular responses, including disruption of the cell cycle, monitored by flow cytometry assays, and induction of necrosis, monitored by dye exclusion and caspase inhibition assays, that occur preferentially in the MMR-deficient cell line. These cellular responses provide insight into the mechanisms underlying the selective activity of this novel class of targeted anti-cancer agents. PMID:22103240

Process for the production of metal nitride sintered bodies and resultant silicon nitride and aluminum nitride sintered bodies

Science.gov (United States)

Yajima, S.; Omori, M.; Hayashi, J.; Kayano, H.; Hamano, M.

1983-01-01

A process for the manufacture of metal nitride sintered bodies, in particular, a process in which a mixture of metal nitrite powders is shaped and heated together with a binding agent is described. Of the metal nitrides Si3N4 and AIN were used especially frequently because of their excellent properties at high temperatures. The goal is to produce a process for metal nitride sintered bodies with high strength, high corrosion resistance, thermal shock resistance, thermal shock resistance, and avoidance of previously known faults.

Plasmonic Titanium Nitride Nanostructures via Nitridation of Nanopatterned Titanium Dioxide

DEFF Research Database (Denmark)

Guler, Urcan; Zemlyanov, Dmitry; Kim, Jongbum

2017-01-01

Plasmonic titanium nitride nanostructures are obtained via nitridation of titanium dioxide. Nanoparticles acquired a cubic shape with sharper edges following the rock-salt crystalline structure of TiN. Lattice constant of the resulting TiN nanoparticles matched well with the tabulated data. Energy...

Surface characterization of nickel titanium orthodontic arch wires

Science.gov (United States)

Krishnan, Manu; Seema, Saraswathy; Tiwari, Brijesh; Sharma, Himanshu S.; Londhe, Sanjay; Arora, Vimal

2015-01-01

Background Surface roughness of nickel titanium orthodontic arch wires poses several clinical challenges. Surface modification with aesthetic/metallic/non metallic materials is therefore a recent innovation, with clinical efficacy yet to be comprehensively evaluated. Methods One conventional and five types of surface modified nickel titanium arch wires were surface characterized with scanning electron microscopy, energy dispersive analysis, Raman spectroscopy, Atomic force microscopy and 3D profilometry. Root mean square roughness values were analyzed by one way analysis of variance and post hoc Duncan's multiple range tests. Results Study groups demonstrated considerable reduction in roughness values from conventional in a material specific pattern: Group I; conventional (578.56 nm) > Group V; Teflon (365.33 nm) > Group III; nitride (301.51 nm) > Group VI (i); rhodium (290.64 nm) > Group VI (ii); silver (252.22 nm) > Group IV; titanium (229.51 nm) > Group II; resin (158.60 nm). It also showed the defects with aesthetic (resin/Teflon) and nitride surfaces and smooth topography achieved with metals; titanium/silver/rhodium. Conclusions Resin, Teflon, titanium, silver, rhodium and nitrides were effective in decreasing surface roughness of nickel titanium arch wires albeit; certain flaws. Findings have clinical implications, considering their potential in lessening biofilm adhesion, reducing friction, improving corrosion resistance and preventing nickel leach and allergic reactions. PMID:26843749

Rhodium. Suppl. Vol. B1

International Nuclear Information System (INIS)

Griffith, W.P.; Jehn, H.; McCleverty, J.A.; Raub, C.J.; Robinson, S.D.

1982-01-01

The present rhodium vol. B1 is concerned largely with linary compounds and coordination complexes of this important metal, which is used either alone or in alloy form for fabrication of other materials or for heterogeneous catalysis. In first two chapters are devoted for hydrides, oxides, ternary and quaternary oxorhodates. Third chapter is on different type of complexes with nitrogen. From chapter four to seven is on halogen complexes with this metal. Next chapters are on sulphides, sulphoxide and sulphito complexes, sulphates and sulphato complexes, selenides and tellurides, borides, borane complexes, carbides, carbonato, cyno, fulminato and thiocyanato complexes. Finally, silicide, phosphides, phosphito and arsenides are treated over here. (AB)

Electrooxidative Rhodium-Catalyzed C-H/C-H Activation: Electricity as Oxidant for Cross-Dehydrogenative Alkenylation.

Science.gov (United States)

Qiu, Youai; Kong, Wei-Jun; Struwe, Julia; Sauermann, Nicolas; Rogge, Torben; Scheremetjew, Alexej; Ackermann, Lutz

2018-04-06

Rhodium(III) catalysis has enabled a plethora of oxidative C-H functionalizations, which predominantly employ stoichiometric amounts of toxic and/or expensive metal oxidants. In contrast, we describe the first electrochemical C-H activation by rhodium catalysis that avoids hazardous chemical oxidants. Thus, environmentally-benign twofold C-H/C-H functionalizations were accomplished with weakly-coordinating benzoic acids and benzamides, employing electricity as the terminal oxidant with H2 as the sole byproduct. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hot pressing of uranium nitride and mixed uranium plutonium nitride

International Nuclear Information System (INIS)

Chang, J.Y.

1975-01-01

The hot pressing characteristics of uranium nitride and mixed uranium plutonium nitride were studied. The utilization of computer programs together with the experimental technique developed in the present study may serve as a useful purpose of prediction and fabrication of advanced reactor fuel and other high temperature ceramic materials for the future. The densification of nitrides follow closely with a plastic flow theory expressed as: d rho/ dt = A/T(t) (1-rho) [1/1-(1-rho)/sup 2/3/ + B1n (1-rho)] The coefficients, A and B, were obtained from experiment and computer curve fitting. (8 figures) (U.S.)

Ring Expansion and Rearrangements of Rhodium(II) Azavinyl Carbenes

Science.gov (United States)

Selander, Nicklas; Worrell, Brady T.

2013-01-01

An efficient, regioselective and convergent method for the ring expansion and rearrangement of 1-sulfonyl-1,2,3-triazoles under rhodium(II)-catalyzed conditions is described. These denitrogenative reactions form substituted enaminone and olefin-based products, which in the former case can be further functionalized to unique products rendering the sulfonyl triazole traceless. PMID:23161725

Rhodium(II)-catalyzed enantioselective synthesis of troponoids.

Science.gov (United States)

Murarka, Sandip; Jia, Zhi-Jun; Merten, Christian; Daniliuc, Constantin-G; Antonchick, Andrey P; Waldmann, Herbert

2015-06-22

We report a rhodium(II)-catalyzed highly enantioselective 1,3-dipolar cycloaddition reaction between the carbonyl moiety of tropone and carbonyl ylides to afford troponoids in good to high yields with excellent enantioselectivity. We demonstrate that α-diazoketone-derived carbonyl ylides, in contrast to carbonyl ylides derived from diazodiketoesters, undergo [6+3] cycloaddition reactions with tropone to yield the corresponding bridged heterocycles with excellent stereoselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rhodium-catalyzed Chemo- and Regioselective Cross-dimerization of Two Terminal Alkynes

Science.gov (United States)

Xu, Hua-Dong; Zhang, Ren-Wei; Li, Xiaoxun; Huang, Suyu; Tang, Weiping; Hu, Wen-Hao

2013-01-01

Cross-dimerization of terminal arylacetylenes and terminal propargylic alcohols/amides has been achieved in the effect of a rhodium catalyst. This method features high chemo- and regioselectivities rendering convenient and atom economical access to functionalized enynes. PMID:23356993

Metal Nitrides for Plasmonic Applications

DEFF Research Database (Denmark)

Naik, Gururaj V.; Schroeder, Jeremy; Guler, Urcan

2012-01-01

Metal nitrides as alternatives to metals such as gold could offer many advantages when used as plasmonic material. We show that transition metal nitrides can replace metals providing equally good optical performance for many plasmonic applications.......Metal nitrides as alternatives to metals such as gold could offer many advantages when used as plasmonic material. We show that transition metal nitrides can replace metals providing equally good optical performance for many plasmonic applications....

Rhodium target preparation from homemade chloride plating baths used for the industrial cyclotron production of palladium-L03

International Nuclear Information System (INIS)

Sadeghi, M.; Van den Winkel, P.; Afarideh, H.; Haji-Saeid, M.; Syrafi Nafis, H.

2004-01-01

Purpose: To avoid acquisition problems of commercially available western rhodium plating solutions in developing countries, a new plating/recovery cycle for Rh-103 electroplated target material (1 g Rh per target) used for the industrial cyclotron production of Pd-103 was developed. Rhodium chloride plating solutions can be prepared by dissolution of the analytical grade compound or from rhodium recovery solutions obtained after electrosolubilisation of irradiated targets and extraction of palladium. Methods: The technology involves the selective removal of the copper target backing of an irradiated target in concentrated nitric acid using a homemade flow-through stripper. The resulting rhodium fragments are dissolved in a constant-volume (40 ml), homemade graphite centrifugal ac-electrodissolution mini-reactor operating at 90 degree C, 2 A.cm-2 and 1000-rpm rotation speed. The system allows time-controlled 99 % solubilisation of up to 3g rhodium (as fragments, powder or small pieces of wire) in less than 3 hours when 12 N hydrochloric acid is applied. Upon solvent-solvent extraction of the non-carrier added Pd-103 from the resulting HCI solution; the following procedure can be used for the simultaneous preparation of 4 targets showing a surface area of 11.69 cm 2 and a physical thickness of 48 Um. Dissolve an amount of hydrated RhC13 containing 2.8 g of rhodium in 400 ml of water. Alternatively, the filtered (0.45 μm filter) combined recovery solutions containing the same weight of rhodium can be evaporated to near dryness (350 degree C at the start, 150 degree C near the end) and residue taken up (gentle stirring, 50 degree C) in 400 ml of distilled water, After filtration, a stress reducing agent (sulfamic acid) is added and the pH sodium hydroxide. Upon make up to volume (450 ml) adjusted to the optimum value (pH = 2) with and preheating to 40 degree C, the resulting solution is introduced in a cylindrical home-made constant-volume, 4- target plating vessel

Liquid-liquid extraction/separation of platinum(IV) and rhodium(III) from acidic chloride solutions using tri-iso-octylamine

Energy Technology Data Exchange (ETDEWEB)

Lee, Jin-Young, E-mail: jinlee@kigam.re.kr [Metals Recovery Department, Minerals Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), 92 Gahangno, Yuesong-gu, Daejeon 305-350 (Korea, Republic of); Rajesh Kumar, J., E-mail: rajeshkumarphd@rediffmail.com [Metals Recovery Department, Minerals Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), 92 Gahangno, Yuesong-gu, Daejeon 305-350 (Korea, Republic of); Kim, Joon-Soo; Park, Hyung-Kyu; Yoon, Ho-Sung [Metals Recovery Department, Minerals Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), 92 Gahangno, Yuesong-gu, Daejeon 305-350 (Korea, Republic of)

2009-08-30

Liquid-liquid extraction/separation of platinum(IV) and rhodium(III) from acidic chloride solutions was carried out using tri-iso-octylamine (Alamine 308) as an extractant diluted in kerosene. The percentage extraction of platinum(IV) and rhodium(III) increased with increase in acid concentration up to 8 mol L{sup -1}. However, at 10 mol L{sup -1} HCl concentration, the extraction behavior was reversed, indicating the solvation type mechanism during extraction. The quantitative extraction of {approx}98% platinum(IV) and 36% rhodium(III) was achieved with 0.01 mol L{sup -1} Alamine 308. The highest separation factor (S.F. = 184.7) of platinum(IV) and rhodium(III) was achieved with 0.01 mol L{sup -1} Alamine 308 at 1.0 mol L{sup -1} of hydrochloric acid concentration. Alkaline metal salts like sodium chloride, sodium nitrate, sodium thiocyanate, lithium chloride, lithium nitrate, potassium chloride and potassium thiocyanate used for the salting-out effect. LiCl proved as best salt for the extraction of platinum(IV). Temperature effect demonstrates that the extraction process is exothermic. Hydrochloric acid and thiourea mixture proved to be better stripping reagents when compared with other mineral acids and bases.

Characteristics of Au/PZT/TiO2/Nitride/Si structure capacitors with ICP nitride treatments

International Nuclear Information System (INIS)

Min, Hyung Seob; Kim, Tae Ho; Jeon, Chang Bae; Lee, Jae Gab; Kim, Ji Young

2002-01-01

In this study, the characteristics of PZT/TiO 2 ferroelectric gate stack capacitors with Inductively Coupled Plasma (ICP) nitridation were investigated for field effect transistor (FET)-type Ferroelectric Random Access Memory (FeRAM) applications. If a high accumulation capacitance is to be had, the ICP nitridation time needs to be optimized. While a short ICP treatment time results in thermal oxide growth due to lack of nitrogen, a long nitridation time causes a nitride layer which is too thick. Au/PZT(200 nm)/TiO 2 (40 nm)/Nitride/Si (MeFINS) structure capacitors show a memory window (ΔV) of 1.6 V under ±3-V operation while Au/PZT(200 nm)/TiO 2 (40 nm)/Si (MeFIS) capacitors without nitride treatment exhibit a small memory window of 0.6 V. At the same time, the capacitance of the MeFINS device is almost twice that of the MeFIS capacitor. This result implies that the ICP nitride treatment suppresses the formation of a low dielectric constant interfacial SiO x layer and alleviates the series capacitance problem

Stereoselective hydrogenation of olefins using rhodium-substituted carbonic anhydrase--a new reductase.

Science.gov (United States)

Jing, Qing; Okrasa, Krzysztof; Kazlauskas, Romas J

2009-01-01

One useful synthetic reaction missing from nature's toolbox is the direct hydrogenation of substrates using hydrogen. Instead nature uses cofactors like NADH to reduce organic substrates, which adds complexity and cost to these reductions. To create an enzyme that can directly reduce organic substrates with hydrogen, researchers have combined metal hydrogenation catalysts with proteins. One approach is an indirect link where a ligand is linked to a protein and the metal binds to the ligand. Another approach is direct linking of the metal to protein, but nonspecific binding of the metal limits this approach. Herein, we report a direct hydrogenation of olefins catalyzed by rhodium(I) bound to carbonic anhydrase (CA-[Rh]). We minimized nonspecific binding of rhodium by replacing histidine residues on the protein surface using site-directed mutagenesis or by chemically modifying the histidine residues. Hydrogenation catalyzed by CA-[Rh] is slightly slower than for uncomplexed rhodium(I), but the protein environment induces stereoselectivity favoring cis- over trans-stilbene by about 20:1. This enzyme is the first cofactor-independent reductase that reduces organic molecules using hydrogen. This catalyst is a good starting point to create variants with tailored reactivity and selectivity. This strategy to insert transition metals in the active site of metalloenzymes opens opportunities to a wider range of enzyme-catalyzed reactions.

Spatial and temporal distribution of platinum, palladium and rhodium in Zagreb air.

Science.gov (United States)

Rinkovec, Jasmina; Pehnec, Gordana; Godec, Ranka; Davila, Silvije; Bešlić, Ivan

2018-09-15

Platinum (Pt), palladium (Pd) and rhodium (Rh) are most widely used in the production of automotive catalytic converters that serve to reduce toxic emissions from motor vehicles. The aim of this study was to quantitatively determine the levels of platinum, palladium and rhodium in the PM 10 and PM 2.5 fraction of airborne particle matter and find their spatial and temporal distribution at different polluted areas of the city of Zagreb, Croatia. The method used in this paper included weekly sampling of airborne particle matter on quartz filters, microwave digestion in acid under high pressure and temperature, and analysis by inductively coupled plasma mass spectrometry (ICP MS). The results have shown that the highest mean values at all three sampling stations (North, Center, South) were obtained for palladium (3.856 pg m -3 , 5.396 pg m -3 , 5.600 pg m -3 ) and the lowest for rhodium (0.444 pg m -3 , 0.643 pg m -3 , 0.750 pg m -3 ). The average mass concentrations of platinum group elements (PGE) in PM 10 increased for all three elements in the direction North Zagreb are the first results of their kind for this area and will provide insights into the contribution of catalytic converters to the presence of these elements in the environment. Copyright © 2018 Elsevier B.V. All rights reserved.

Properties of minor actinide nitrides

International Nuclear Information System (INIS)

Takano, Masahide; Itoh, Akinori; Akabori, Mitsuo; Arai, Yasuo; Minato, Kazuo

2004-01-01

The present status of the research on properties of minor actinide nitrides for the development of an advanced nuclear fuel cycle based on nitride fuel and pyrochemical reprocessing is described. Some thermal stabilities of Am-based nitrides such as AmN and (Am, Zr)N were mainly investigated. Stabilization effect of ZrN was cleary confirmed for the vaporization and hydrolytic behaviors. New experimental equipments for measuring thermal properties of minor actinide nitrides were also introduced. (author)

Photocatalytic carbon dioxide reduction with rhodium-based catalysts in solution and heterogenized within metal-organic frameworks.

Science.gov (United States)

Chambers, Matthew B; Wang, Xia; Elgrishi, Noémie; Hendon, Christopher H; Walsh, Aron; Bonnefoy, Jonathan; Canivet, Jérôme; Quadrelli, Elsje Alessandra; Farrusseng, David; Mellot-Draznieks, Caroline; Fontecave, Marc

2015-02-01

The first photosensitization of a rhodium-based catalytic system for CO2 reduction is reported, with formate as the sole carbon-containing product. Formate has wide industrial applications and is seen as valuable within fuel cell technologies as well as an interesting H2 -storage compound. Heterogenization of molecular rhodium catalysts is accomplished via the synthesis, post-synthetic linker exchange, and characterization of a new metal-organic framework (MOF) Cp*Rh@UiO-67. While the catalytic activities of the homogeneous and heterogeneous systems are found to be comparable, the MOF-based system is more stable and selective. Furthermore it can be recycled without loss of activity. For formate production, an optimal catalyst loading of ∼10 % molar Rh incorporation is determined. Increased incorporation of rhodium catalyst favors thermal decomposition of formate into H2 . There is no precedent for a MOF catalyzing the latter reaction so far. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

Science.gov (United States)

Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

2011-07-12

A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

Thermodynamic assessment of the rhodium-ruthenium-oxygen (Rh-Ru-O) system

Science.gov (United States)

Gossé, S.; Bordier, S.; Guéneau, C.; Brackx, E.; Domenger, R.; Rogez, J.

2018-03-01

Ruthenium (Ru) and rhodium (Rh) are abundant platinum-group metals formed during burn-up of nuclear fuels. Under normal operating conditions, Rh and Ru accumulate and predominantly form metallic precipitates with other fission products like Mo, Pd and Tc. In the framework of vitrification of high-level nuclear waste, these fission products are poorly soluble in molten glasses. They precipitate as metallic particles and oxide phases. Moreover, these Ru and Rh rich phases strongly depend on temperature and the oxygen fugacity of the glass melt. In case of severe accidental conditions with air ingress, oxidation of the Ru and Rh is possible. At low temperatures (T 1422 K for rhodium sesquioxide and T > 1815 K for ruthenium dioxide), they may decompose into (Rh)-FCC or (Ru)-HCP metallic phases and radiotoxic volatile gaseous species. A thermodynamic assessment of the Rh-Ru-O system will enable the prediction of: (1) the metallic and oxide phases that form during the vitrification of high-level nuclear wastes and (2) the release of volatile gaseous species during a severe accident. The Calphad method developed herein employs a thermodynamic approach in the investigation of the thermochemistry of rhodium and ruthenium at high temperatures. Current literature on the thermodynamic properties and phase diagram data enables preliminary thermodynamic assessments of the Rh-O and Ru-O systems. Additionally, select compositions in the ternary Rh-Ru-O system underwent experimental tests to complement data found in literature and to establish the phase equilibria in the ternary system.

Rhodium-Catalyzed Enantioselective Cyclopropanation of Olefins with N-Sulfonyl 1,2,3-Triazoles

Science.gov (United States)

Chuprakov, Stepan; Kwok, Sen Wai; Zhang, Li; Lercher, Lukas; Fokin, Valery V.

2009-01-01

N-Sulfonyl 1,2,3-triazoles readily form rhodium(II) azavinyl carbenes, which react with olefins to produce cyclopropanes with excellent diastereo- and enantioselectivity and in high yield. PMID:19928917

STABLE SILICA-GRAFTED POLYMER-BOUND BULKY-PHOSPHITE MODIFIED RHODIUM HYDROFORMYLATION CATALYSTS

NARCIS (Netherlands)

JONGSMA, T; VANAERT, H; FOSSEN, M; CHALLA, G; VANLEEUWEN, PWNM

1993-01-01

The present study demonstrates that silica-grafted polymer-bound phosphite modified rhodium complexes can be used in continuous flow reactors. The hydroformylation of styrene was carried out at moderate pressure (p(CO/H-2) = 30 bar) and temperature (T = 100-degrees-C), yielding constant conversions

Rhodium-103m generator

International Nuclear Information System (INIS)

Mamadaliev, N.; Levin, V.I.; Malinin, A.B.

1978-01-01

103 Pd separated from metal rhodium irradiated with deuterons has been used without a carrier for sup( 03m)Rh generator The generator of sup(103m)Rh is a column 6mm in diameter filled with an anionite in Cl - form (Dowex-2,8,200-400 mesh) with an adsorbed parent isotope of 103 Pd. As a result of its decay, a 103 Rh daughter isotope is accumulated, which can be washed out from the generator from time to time with a corresponding solution. To prepare the generator, 0.5g of the resin with an adsorbed 103 Pd is charged into the column containing 1g of the same resin. Washing out with 2N HCl yields more than 90% of sup(103m)Rh with a radionuclide purity of more than 99.99%

Controlled Oxygen Chemisorption on an Alumina Supported Rhodium Catalyst. The Formation of a New Metal-Metal Oxide Interface Determined with EXAFS.

NARCIS (Netherlands)

Koningsberger, D.C.; Martens, J.H.A.; Prins, R.

1989-01-01

An alumina-supported rhodium catalyst has been studied with EXAFS. After reduction and evacuation, oxygen was admitted at 100 and 300 K. EXAFS spectra of the catalyst after oxygen admission at 100 K indicated the beginning of oxidation. At 300 K only a small part of the rhodium particles remained

Correlation between the Stereochemistry and Bioactivity in Octahedral Rhodium Prolinato Complexes.

Science.gov (United States)

Rajaratnam, Rajathees; Martin, Elisabeth K; Dörr, Markus; Harms, Klaus; Casini, Angela; Meggers, Eric

2015-08-17

Controlling the relative and absolute configuration of octahedral metal complexes constitutes a key challenge that needs to be overcome in order to fully exploit the structural properties of octahedral metal complexes for applications in the fields of catalysis, materials sciences, and life sciences. Herein, we describe the application of a proline-based chiral tridentate ligand to decisively control the coordination mode of an octahedral rhodium(III) complex. We demonstrate the mirror-like relationship of synthesized enantiomers and differences between diastereomers. Further, we demonstrate, using the established pyridocarbazole pharmacophore ligand as part of the organometallic complexes, the importance of the relative and absolute stereochemistry at the metal toward chiral environments like protein kinases. Protein kinase profiling and inhibition data confirm that the proline-based enantiopure rhodium(III) complexes, despite having all of the same constitution, differ strongly in their selectivity properties despite their unmistakably mutual origin. Moreover, two exemplary compounds have been shown to induce different toxic effects in an ex vivo rat liver model.

Adhesion of rhodium films on metallic substrates

International Nuclear Information System (INIS)

Marot, L.; Covarel, G.; Tuilier, M.-H.; Steiner, R.; Oelhafen, P.

2008-01-01

Rhodium coated metallic films were prepared by magnetron sputtering on metallic substrates. All films were elaborated in same conditions on copper, molybdenum and stainless steel. Adhesion strength tests were carried out by scratch test. The results reveal that the adhesion strength between the film and the substrate is influenced by the hardness of the substrate. Increase of deposition temperature improves the adhesion of the coating. In addition, pre-treatment of substrates by a filtered cathodic vacuum arc and the layer thickness have has some effects on the final adhesion strength

Adhesion of rhodium films on metallic substrates

Energy Technology Data Exchange (ETDEWEB)

Marot, L. [Department of Physics, University of Basel, Klingelbergstrasse 82, CH-4056 Basel (Switzerland)], E-mail: laurent.marot@unibas.ch; Covarel, G.; Tuilier, M.-H. [Laboratoire Mecanique, Materiaux et Procedes de Fabrication, Pole STIC-SPI-Math 61 rue Albert Camus, Universite de Haute-Alsace, F-68093 - Mulhouse Cedex (France); Steiner, R.; Oelhafen, P. [Department of Physics, University of Basel, Klingelbergstrasse 82, CH-4056 Basel (Switzerland)

2008-09-01

Rhodium coated metallic films were prepared by magnetron sputtering on metallic substrates. All films were elaborated in same conditions on copper, molybdenum and stainless steel. Adhesion strength tests were carried out by scratch test. The results reveal that the adhesion strength between the film and the substrate is influenced by the hardness of the substrate. Increase of deposition temperature improves the adhesion of the coating. In addition, pre-treatment of substrates by a filtered cathodic vacuum arc and the layer thickness have has some effects on the final adhesion strength.

Relaxation of polarized nuclei in superconducting rhodium

DEFF Research Database (Denmark)

Knuuttila, T.A.; Tuoriniemi, J.T.; Lefmann, K.

2000-01-01

Nuclear spin lattice relaxation rates were measured in normal and superconducting (sc) rhodium with nuclear polarizations up to p = 0.55. This was sufficient to influence the sc state of Rh, whose T, and B-c, are exceptionally low. Because B-c ... is unchanged, the nuclear spin entropy was fully sustained across the sc transition. The relaxation in the sc state was slower at all temperatures without the coherence enhancement close to T-c. Nonzero nuclear polarization strongly reduced the difference between the relaxation rates in the sc and normal...

Treatment of ammonia by catalytic wet oxidation process over platinum-rhodium bimetallic catalyst in a trickle-bed reactor: effect of pH.

Science.gov (United States)

Hung, Chang-Mao; Lin, Wei-Bang; Ho, Ching-Lin; Shen, Yun-Hwei; Hsia, Shao-Yi

2010-08-01

This work adopted aqueous solutions of ammonia for use in catalytic liquid-phase reduction in a trickle-bed reactor with a platinum-rhodium bimetallic catalyst, prepared by the co-precipitation of chloroplatinic acid (H2PtCl6) and rhodium nitrate [Rh(NO3)3]. The experimental results demonstrated that a minimal amount of ammonia was removed from the solution by wet oxidation in the absence of any catalyst, while approximately 97.0% of the ammonia was removed by wet oxidation over the platinum-rhodium bimetallic catalyst at 230 degrees C with an oxygen partial pressure of 2.0 MPa. The oxidation of ammonia has been studied as a function of pH, and the main reaction products were determined. A synergistic effect is manifest in the platinum-rhodium bimetallic structure, in which the material has the greatest capacity to reduce ammonia. The reaction pathway linked the oxidizing ammonia to nitric oxide, nitrogen, and water.

Catalytic wet oxidation of ammonia solution: Activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst

International Nuclear Information System (INIS)

Hung, C.-M.

2009-01-01

Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H 2 PtCl 6 , Pd(NO 3 ) 3 and Rh(NO 3 ) 3 . Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h -1 in the wet catalytic processes

Catalytic wet oxidation of ammonia solution: Activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst

Energy Technology Data Exchange (ETDEWEB)

Hung, C.-M. [Department of Industry Engineering and Management, Yung-Ta Institute of Technology and Commerce, 316 Chung-shan Road, Linlo, Pingtung 909, Taiwan (China)], E-mail: hungcm1031@gmail.com

2009-04-15

Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H{sub 2}PtCl{sub 6}, Pd(NO{sub 3}){sub 3} and Rh(NO{sub 3}){sub 3}. Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h{sup -1} in the wet catalytic processes.

Catalytic wet oxidation of ammonia solution: activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst.

Science.gov (United States)

Hung, Chang-Mao

2009-04-15

Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H(2)PtCl(6), Pd(NO(3))(3) and Rh(NO(3))(3). Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes.

Column preconcentration and electrothermal atomic absorption spectrometric determination of rhodium in some food and standard samples.

Science.gov (United States)

Taher, Mohammad Ali; Pourmohammad, Fatemeh; Fazelirad, Hamid

2015-12-01

In the present work, an electrothermal atomic absorption spectrometric method has been developed for the determination of ultra-trace amounts of rhodium after adsorption of its 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol/tetraphenylborate ion associated complex at the surface of alumina. Several factors affecting the extraction efficiency such as the pH, type of eluent, sample and eluent flow rates, sorption capacity of alumina and sample volume were investigated and optimized. The relative standard deviation for eight measurements of 0.1 ng/mL of rhodium was ±6.3%. In this method, the detection limit was 0.003 ng/mL in the original solution. The sorption capacity of alumina and the linear range for Rh(III) were evaluated as 0.8 mg/g and 0.015-0.45 ng/mL in the original solution, respectively. The proposed method was successfully applied for the extraction and determination of rhodium content in some food and standard samples with high recovery values. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extraction of fission product rhodium from nitric acid solutions. 1

International Nuclear Information System (INIS)

Gorski, B.; Beer, M.; Russ, L.

1988-01-01

The extraction of noble metals from nitric acid solutions represents one problem of separating valueable substances from nuclear wastes in nuclear fuel reprocessing. Results of distribution experiments demonstrate the possibility of solvent extraction of rhodium using tertiary amines in presence of nitrite. Even short mixing times realize high distribution coefficients allowing quantitative separation from aqueous solutions. (author)

Komplexe zouten van trans-1-2-diaminocyclohexaan met driewaardig rhodium en kobalt

NARCIS (Netherlands)

Bijkerk, Lucas

1937-01-01

Some complex salts of trans-I-2-díominocyclohexane with trivalent cobaltum and rhodium were prepared and their properties described in detail. Diaminocyclohexanwe as obtained by the following series of reactions: cyclohexanone --> cyclohexanone-I-oxalylicester --> cyclohexonone-I-carboxylicester-2

Surface modification of 17-4PH stainless steel by DC plasma nitriding and titanium nitride film duplex treatment

International Nuclear Information System (INIS)

Qi, F.; Leng, Y.X.; Huang, N.; Bai, B.; Zhang, P.Ch.

2007-01-01

17-4PH stainless steel was modified by direct current (DC) plasma nitriding and titanium nitride film duplex treatment in this study. The microstructure, wear resistance and corrosion resistance were characterized by X-ray diffraction (XRD), pin-on-disk tribological test and polarization experiment. The results revealed that the DC plasma nitriding pretreatment was in favor of improving properties of titanium nitride film. The corrosion resistance and wear resistance of duplex treatment specimen was more superior to that of only coated titanium nitride film

A NEW TYPE OF HIGHLY-ACTIVE POLYMER-BOUND RHODIUM HYDROFORMYLATION CATALYST

NARCIS (Netherlands)

JONGSMA, T; KIMKES, P; CHALLA, G; VANLEEUWEN, PWNM

1992-01-01

A new route of attaching phosphites to a (co)polymer chain is described. These copolymers are used for the preparation of a rhodium phosphite hydroformylation catalyst. The catalytic activity of this polymer-bound system is identical to that of the low molecular weight analogue. The catalysts show a

A Mixed-Ligand Chiral Rhodium(II) Catalyst Enables the Enantioselective Total Synthesis of Piperarborenine B.

Science.gov (United States)

Panish, Robert A; Chintala, Srinivasa R; Fox, Joseph M

2016-04-11

A novel, mixed-ligand chiral rhodium(II) catalyst, Rh2(S-NTTL)3(dCPA), has enabled the first enantioselective total synthesis of the natural product piperarborenine B. A crystal structure of Rh2(S-NTTL)3(dCPA) reveals a "chiral crown" conformation with a bulky dicyclohexylphenyl acetate ligand and three N-naphthalimido groups oriented on the same face of the catalyst. The natural product was prepared on large scale using rhodium-catalyzed bicyclobutanation/ copper-catalyzed homoconjugate addition chemistry in the key step. The route proceeds in ten steps with an 8% overall yield and 92% ee. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of human serun albumin in some biological properties of rhodium(II complexes

Directory of Open Access Journals (Sweden)

Espósito Breno P.

2000-01-01

Full Text Available The affinities for human albumin (HSA of five rhodium(II complexes of general formula [Rh2(bridge4] (bridge = acetate, propionate, butyrate, trifluoroacetate and trifluoroacetamidate were determined by spectrophotometry. In the case of the alkylcarboxylates, an inverse correlation of affinity with their liposolubilities was observed. Diffusion of the free or protein-bound complexes into Ehrlich cells in vitro seems to be primarily governed by the hydrophobic character of the complex. The complex [Rh2(tfc4] exhibited affinity towards the protein (K = 214.1 as well as cell partition both in the absence (32.1% and presence (48.6% of HSA. The compound HSA: [Rh2(tfc4] has had its antitumoral action in tumor-bearing Balb-c mice investigated, showing that HSA can be a drug reservoir for the rhodium complex.

Nitriding of high speed steel

International Nuclear Information System (INIS)

Doyle, E.D.; Pagon, A.M.; Hubbard, P.; Dowey, S.J.; Pilkington, A.; McCulloch, D.G.; Latham, K.; DuPlessis, J.

2010-01-01

Current practice when nitriding HSS cutting tools is to avoid embrittlement of the cutting edge by limiting the depth of the diffusion zone. This is accomplished by reducing the nitriding time and temperature and eliminating any compound layer formation. However, in many applications there is an argument for generating a compound layer with beneficial tribological properties. In this investigation results are presented of a metallographic, XRD and XPS analysis of nitrided surface layers generated using active screen plasma nitriding and reactive vapour deposition using cathodic arc. These results are discussed in the context of built up edge formation observed while machining inside a scanning electron microscope. (author)

Arylation of Rhodium(II) Azavinyl Carbenes with Boronic Acids

Science.gov (United States)

Selander, Nicklas; Worrell, Brady T.; Chuprakov, Stepan; Velaparthi, Subash; Fokin, Valery V.

2013-01-01

A highly efficient and stereoselective arylation of in situ generated azavinyl carbenes affording 2,2-diaryl enamines at ambient temperatures has been developed. These transition metal carbenes are directly produced from readily available and stable 1-sulfonyl-1,2,3-triazoles in the presence of a rhodium carboxylate catalyst. In several cases, the enamines generated in this reaction can be cyclized into substituted indoles employing copper catalysts. PMID:22913576

Inter-diffusion study of rhodium and tantalum by RBS

International Nuclear Information System (INIS)

Nuttens, V.E.; Hubert, R.L.; Bodart, F.; Lucas, S.

2005-01-01

The inter-diffusion of rhodium and tantalum has been studied with the goal of synthesizing an alloy acting as a diffusion barrier for high temperature applications. Rh/Ta sandwiched samples were annealed in vacuum at temperature ranging from 800 to 900 deg. C and from 1000 to 1075 deg. C. The diffusion profiles were obtained by RBS. They suggest the formation of two clearly different phases in each temperature range considered

Solvothermal synthesis: a new route for preparing nitrides

CERN Document Server

Demazeau, G; Denis, A; Largeteau, A

2002-01-01

Solvothermal synthesis appears to be an interesting route for preparing nitrides such as gallium nitride and aluminium nitride, using ammonia as solvent. A nitriding additive is used to perform the reaction and, in the case of gallium nitride, is encapsulated by melt gallium. The syntheses are performed in the temperature range 400-800 deg. C and in the pressure range 100-200 MPa. The synthesized powders are characterized by x-ray diffraction and scanning electron microscopy. Finely divided gallium nitride GaN and aluminium nitride AlN, both with wurtzite-type structure, can be obtained by this route.

Bimetallic poly- and oligo-nuclear complexes based on a rhodium(III) metalloligand

Science.gov (United States)

Vasilchenko, Danila B.; Venediktov, Anatoliy B.; Korenev, Sergey V.; Filatov, Evgeniy Yu.; Baidina, Iraida A.; Nadolinnyi, Vladimir A.

2012-10-01

Interaction of trans-[Rh(i-Nic)4Cl2]3- anions (i-Nic- - isonicotinate anion) with Cuaq2+ and Coaq2+ cations in water has afforded complex salts Co3[Rh(i-Nic)4Cl2]2·17H2O (1) and Cu3[Rh(i-Nic)4Cl2]2·14H2O (2). Oligonuclear character of 1 and 2 has been established. A coordination polymer Cu5[Rh(i-Nic)4Cl2]2(i-Nic)2(OH)2·2H2O (3) has been crystallized by hydrothermal treatment of 2 at 160 °C, and its structure was determined by X-ray structural analysis. EPR data for the complexes has been collected and interpreted. Thermal decomposition of the salts was studied by c-DTA. Bimetallic alloys rhodium-copper and rhodium-cobalt have been obtained as final products of thermal decomposition.

Preparation of aluminum nitride-silicon carbide nanocomposite powder by the nitridation of aluminum silicon carbide

NARCIS (Netherlands)

Itatani, K.; Tsukamoto, R.; Delsing, A.C.A.; Hintzen, H.T.J.M.; Okada, I.

2002-01-01

Aluminum nitride (AlN)-silicon carbide (SiC) nanocomposite powders were prepared by the nitridation of aluminum-silicon carbide (Al4SiC4) with the specific surface area of 15.5 m2·g-1. The powders nitrided at and above 1400°C for 3 h contained the 2H-phases which consisted of AlN-rich and SiC-rich

Microstructural characterization of an AISI-SAE 4140 steel without nitridation and nitrided

International Nuclear Information System (INIS)

Medina F, A.; Naquid G, C.

2000-01-01

It was micro structurally characterized an AISI-SAE 4140 steel before and after of nitridation through the nitridation process by plasma post-unloading microwaves through Optical microscopy (OM), Scanning electron microscopy (SEM) by means of secondary electrons and retrodispersed, X-ray diffraction (XRD), Energy dispersion spectra (EDS) and mapping of elements. (Author)

Precipitation of metal nitrides from chloride melts

International Nuclear Information System (INIS)

Slater, S.A.; Miller, W.E.; Willit, J.L.

1996-01-01

Precipitation of actinides, lanthanides, and fission products as nitrides from molten chloride melts is being investigated for use as a final cleanup step in treating radioactive salt wastes generated by electrometallurgical processing of spent nuclear fuel. The radioactive components (eg, fission products) need to be removed to reduce the volume of high-level waste that requires disposal. To extract the fission products from the salt, a nitride precipitation process is being developed. The salt waste is first contacted with a molten metal; after equilibrium is reached, a nitride is added to the metal phase. The insoluble nitrides can be recovered and converted to a borosilicate glass after air oxidation. For a bench-scale experimental setup, a crucible was designed to contact the salt and metal phases. Solubility tests were performed with candidate nitrides and metal nitrides for which there are no solubility data. Experiments were performed to assess feasibility of precipitation of metal nitrides from chloride melts

Intramolecular Hydroamination of Unbiased and Functionalized Primary Aminoalkenes Catalyzed by a Rhodium Aminophosphine Complex

Science.gov (United States)

Julian, Lisa D.; Hartwig, John F.

2010-01-01

We report a rhodium catalyst that exhibits high reactivity for the hydroamination of primary aminoalkenes that are unbiased toward cyclization and that possess functional groups that would not be tolerated in hydroaminations catalyzed by more electrophilic systems. This catalyst contains an unusual diaminophosphine ligand that binds to rhodium in a κ3-P,O,P mode. The reactions catalyzed by this complex typically proceed at mild temperatures (room temperature to 70 °C), occur with primary aminoalkenes lacking substituents on the alkyl chain that bias the system toward cyclization, occur with primary aminoalkenes containing chloride, ester, ether, enolizable ketone, nitrile, and unprotected alcohol functionality, and occur with primary aminoalkenes containing internal olefins. Mechanistic data imply that these reactions occur with a turnover-limiting step that is different from that of reactions catalyzed by late transition metal complexes of Pd, Pt, and Ir. This change in the turnover-limiting step and resulting high activity of the catalyst stem from favorable relative rates for protonolysis of the M-C bond to release the hydroamination product vs reversion of the aminoalkyl intermediate to regenerate the acyclic precursor. Probes for the origin of the reactivity of the rhodium complex of L1 imply that the aminophosphine groups lead to these favorable rates by effects beyond steric demands and simple electron donation to the metal center. PMID:20839807

Hydrogen adsorption on skeletal rhodium-tantalum electrodes-catalysts

International Nuclear Information System (INIS)

Tsinstevich, V.M.; Krejnina, N.M.

1975-01-01

Skeleton rhodium-tantalic catalyst electrodes with a tantalum mass percentage of 0 to 100 have been obtained by the methodology of Crupp and others. The hydrogen adsorption is studied through the method of removing the galvano-static and potentiodynamic curves of charging in sulfuric acid and potassium hydroxide. It has been discovered that the maximum adsorption ability relatively to the hydrogen can be observed in an alloy with a 5% tantalum contents. The energetic characteristics of the alloys are higher in alkali than in acid

Molecular recognition in protein modification with rhodium metallopeptides

Science.gov (United States)

Ball, Zachary T.

2015-01-01

Chemical manipulation of natural, unengineered proteins is a daunting challenge which tests the limits of reaction design. By combining transition-metal or other catalysts with molecular recognition ideas, it is possible to achieve site-selective protein reactivity without the need for engineered recognition sequences or reactive sites. Some recent examples in this area have used ruthenium photocatalysis, pyridine organocatalysis, and rhodium(II) metallocarbene catalysis, indicating that the fundamental ideas provide opportunities for using diverse reactivity on complex protein substrates and in complex cell-like environments. PMID:25588960

Examining Rhodium Catalyst complexes for Use with Conducting Polymers Designed for Fuel Cells in Preparing Biosensors

Energy Technology Data Exchange (ETDEWEB)

Carpio, M.M.; Kerr, J.B.

2005-01-01

Biosensing devices are important because they can detect, record, and transmit information regarding the presence of, or physiological changes in, different chemical or biological materials in the environment. The goal of this research is to prepare a biosensing device that is effective, quick, and low cost. This is done by examining which chemicals will work best when placed in a biosensor. The first study involved experimenting on a rhodium catalyst complexed with ligands such as bipyridine and imidazole. The rhodium catalyst is important because it is reduced from RhIII to RhI, forms a hydride by reaction with water and releases the hydride to react with nicotinamide adenine dinucleotide (NAD+) to selectively produce 1,4-NADH, the reduced form of NAD+. The second study looked at different types of ketones and enzymes for the enzyme-substrate reaction converting a ketone into an alcohol. Preliminary results showed that the rhodium complexed with bipyridine was able to carry out all the reactions, while the rhodium complexed with imidazole was not able to produce and release hydrides. In addition, the most effective ketone to use is benzylacetone with the enzyme alcohol dehydrogenase from baker’s yeast. Future work includes experimenting with bis-imidazole, which mimics the structure of bipyridine to see if it has the capability to reduce and if the reduction rate is comparable to the bipyridine complex. Once all testing is completed, the fastest catalysts will be combined with polymer membranes designed for fuel cells to prepare biosensing devices that can be used in a variety of applications including ones in the medical and environmental fields.

The reaction mechanism of the partial oxidation of methane to synthesis gas: a transient kinetic study over rhodium and a comparison with platinum

NARCIS (Netherlands)

Mallens, E.P.J.; Hoebink, J.H.B.J.; Marin, G.B.M.M.

1997-01-01

The partial oxidation of methane to synthesis gas over rhodium sponge has been investigated by admitting pulses of pure methane and pure oxygen as well as mixtures of methane and oxygen to rhodium sponge at temperatures from 873 to 1023 K. Moreover, pulses of oxygen followed by methane and vice

Effective Duration of Gas Nitriding Process on AISI 316L for the Formation of a Desired Thickness of Surface Nitrided Layer

Directory of Open Access Journals (Sweden)

Mahmoud Hassan R. S.

2014-07-01

Full Text Available High temperature gas nitriding performed on AISI 316L at the temperature of 1200°C. The microstructure of treated AISI 316L samples were observed to identify the formation of the microstructure of nitrided surface layer. The grain size of austenite tends to be enlarged when the nitriding time increases, but the austenite single phase structure is maintained even after the long-time solution nitriding. Using microhardness testing, the hardness values drop to the center of the samples. The increase in surface hardness is due to the high nitrogen concentration at or near the surface. At 245HV, the graph of the effective duration of nitriding process was plotted to achieve the maximum depth of nitrogen diffuse under the surface. Using Sigma Plot software best fit lines of the experimental result found and plotted to find out effective duration of nitriding equation as Y=1.9491(1-0.7947x, where Y is the thickness of nitrided layer below the surface and X is duration of nitriding process. Based on this equation, the duration of gas nitriding process can be estimated to produce desired thickness of nitrided layer.

Separation of zirconium--hafnium by nitride precipitation

International Nuclear Information System (INIS)

Anderson, R.N.; Parlee, N.A.

1977-01-01

A method is described for the separation of a light reactive metal (e.g., zirconium) from a heavy reactive metal (e.g., hafnium) by forming insoluble nitrides of the metals in a molten metal solvent (e.g., copper) inert to nitrogen and having a suitable density for the light metal nitride to form a separate phase in the upper portion of the solvent and for the heavy metal nitride to form a separate phase in the lower portion of the solvent. Nitriding is performed by maintaining a nitrogen-containing atmosphere over the bath. The light and heavy metals may be an oxide mixture and carbothermically reduced to metal form in the same bath used for nitriding. The nitrides are then separately removed and decomposed to form the desired separate metals. 16 claims, 1 figure

Nitride fuels irradiation performance data base

International Nuclear Information System (INIS)

Brozak, D.E.; Thomas, J.K.; Peddicord, K.L.

1987-01-01

An irradiation performance data base for nitride fuels has been developed from an extensive literature search and review that emphasized uranium nitride, but also included performance data for mixed nitrides [(U,Pu)N] and carbonitrides [(U,Pu)C,N] to increase the quantity and depth of pin data available. This work represents a very extensive effort to systematically collect and organize irradiation data for nitride-based fuels. The data base has many potential applications. First, it can facilitate parametric studies of nitride-based fuels to be performed using a wide range of pin designs and operating conditions. This should aid in the identification of important parameters and design requirements for multimegawatt and SP-100 fuel systems. Secondly, the data base can be used to evaluate fuel performance models. For detailed studies, it can serve as a guide to selecting a small group of pin specimens for extensive characterization. Finally, the data base will serve as an easily accessible and expandable source of irradiation performance information for nitride fuels

Simple process to fabricate nitride alloy powders

International Nuclear Information System (INIS)

Yang, Jae Ho; Kim, Dong-Joo; Kim, Keon Sik; Rhee, Young Woo; Oh, Jang-Soo; Kim, Jong Hun; Koo, Yang Hyun

2013-01-01

Uranium mono-nitride (UN) is considered as a fuel material [1] for accident-tolerant fuel to compensate for the loss of fissile fuel material caused by adopting a thickened cladding such as SiC composites. Uranium nitride powders can be fabricated by a carbothermic reduction of the oxide powders, or the nitriding of metal uranium. Among them, a direct nitriding process of metal is more attractive because it has advantages in the mass production of high-purity powders and the reusing of expensive 15 N 2 gas. However, since metal uranium is usually fabricated in the form of bulk ingots, it has a drawback in the fabrication of fine powders. The Korea Atomic Energy Research Institute (KAERI) has a centrifugal atomisation technique to fabricate uranium and uranium alloy powders. In this study, a simple reaction method was tested to fabricate nitride fuel powders directly from uranium metal alloy powders. Spherical powder and flake of uranium metal alloys were fabricated using a centrifugal atomisation method. The nitride powders were obtained by thermal treating the metal particles under nitrogen containing gas. The phase and morphology evolutions of powders were investigated during the nitriding process. A phase analysis of nitride powders was also part of the present work. KAERI has developed the centrifugal rotating disk atomisation process to fabricate spherical uranium metal alloy powders which are used as advanced fuel materials for research reactors. The rotating disk atomisation system involves the tasks of melting, atomising, and collecting. A nozzle in the bottom of melting crucible introduces melt at the center of a spinning disk. The centrifugal force carries the melt to the edge of the disk and throws the melt off the edge. Size and shape of droplets can be controlled by changing the nozzle size, the disk diameter and disk speed independently or simultaneously. By adjusting the processing parameters of the centrifugal atomiser, a spherical and flake shape

Microhardness and microplasticity of zirconium nitride

International Nuclear Information System (INIS)

Neshpor, V.S.; Eron'yan, M.A.; Petrov, A.N.; Kravchik, A.E.

1978-01-01

To experimentally check the concentration dependence of microhardness of 4 group nitrides, microhardness of zirconium nitride compact samples was measured. The samples were obtained either by bulk saturation of zirconium iodide plates or by chemical precipitation from gas. As nitrogen content decreased within the limits of homogeneity of zirconium nitride samples where the concentration of admixed oxygen was low, the microhardness grew from 1500+-100 kg/mm 2 for ZrNsub(1.0) to 27000+-100 kg/mm 2 for ZrNsub(0.78). Microplasticity of zirconium nitride (resistance to fracture) decreased, as the concentration of nitrogen vacancies was growing

Surface analysis in steel nitrides by using Moessbauer spectroscopy

International Nuclear Information System (INIS)

Figueiredo, R.S. de.

1991-07-01

The formation of iron nitride layer at low temperatures, 600-700 K, by Moessbauer spectroscopy is studied. These layers were obtained basically through two different processes: ion nitriding and ammonia gas nitriding. A preliminary study about post-discharge nitriding was made using discharge in hollow cathode as well as microwave excitation. The assembly of these chambers is also described. The analysis of the nitrided samples was done by CEMS and CXMS, aided by optical microscopy, and the CEMS and CXMS detectors were constructed by ourselves. We also made a brief study about these detectors, testing as acetone as the mixture 80% He+10% C H 4 as detection gases for the use of CEMS. The surface analysis of the samples showed that in the ammonia gas process nitriding the nitrided layer starts by the superficial formation of an iron nitride rich nitrogen. By thermal evolution this nitride promotes the diffusion of nitrogen and the formation of other more stable nitrides. (author)

Permeation of platinum and rhodium nanoparticles through intact and damaged human skin

International Nuclear Information System (INIS)

Mauro, Marcella; Crosera, Matteo; Bianco, Carlotta; Adami, Gianpiero; Montini, Tiziano; Fornasiero, Paolo; Jaganjac, Morana; Bovenzi, Massimo; Filon, Francesca Larese

2015-01-01

The aim of the study was to evaluate percutaneous penetration of platinum and rhodium nanoparticles (PtNPs: 5.8 ± 0.9 nm, RhNPs: 5.3 ± 1.9 nm) through human skin. Salts compounds of these metals are sensitizers and some also carcinogenic agents. In vitro permeation experiments were performed using Franz diffusion cells with intact and damaged skin. PtNPs and RhNPs, stabilized with polyvinylpyrrolidone, were synthesized by reduction of Na 2 PtC l6 and RhCl 3 ·3H 2 O respectively. Suspensions with a concentration of 2.0 g/L of PtNPs and RhNPs were dispersed separately in synthetic sweat at pH 4.5 and applied as donor phases to the outer surface of the skin for 24 h. Measurements of the content of the metals in the receiving solution and in the skin were performed subsequently. Rhodium skin permeation was demonstrated through damaged skin, with a permeation flux of 0.04 ± 0.04 μg cm −2  h −1 and a lag time of 7.9 ± 1.1 h, while no traces of platinum were found in receiving solutions. Platinum and rhodium skin-analysis showed significantly higher concentrations of the metals in damaged skin. Rh and Pt applied as NPs can penetrate the skin barrier and Rh can be found in receiving solutions. These experiments pointed out the need for skin contamination prevention, since even a minor injury to the skin barrier can significantly increase penetration

Permeation of platinum and rhodium nanoparticles through intact and damaged human skin

Energy Technology Data Exchange (ETDEWEB)

Mauro, Marcella [University of Trieste, Clinical Unit of Occupational Medicine, Department of Medical Sciences (Italy); Crosera, Matteo; Bianco, Carlotta; Adami, Gianpiero; Montini, Tiziano; Fornasiero, Paolo [University of Trieste, Department of Chemical and Pharmaceutical Sciences (Italy); Jaganjac, Morana [Rudjer Boskovic Institute, Laboratory for Oxidative Stress, Department of Molecular Medicine (Croatia); Bovenzi, Massimo; Filon, Francesca Larese, E-mail: larese@units.it [University of Trieste, Clinical Unit of Occupational Medicine, Department of Medical Sciences (Italy)

2015-06-15

The aim of the study was to evaluate percutaneous penetration of platinum and rhodium nanoparticles (PtNPs: 5.8 ± 0.9 nm, RhNPs: 5.3 ± 1.9 nm) through human skin. Salts compounds of these metals are sensitizers and some also carcinogenic agents. In vitro permeation experiments were performed using Franz diffusion cells with intact and damaged skin. PtNPs and RhNPs, stabilized with polyvinylpyrrolidone, were synthesized by reduction of Na{sub 2}PtC{sub l6} and RhCl{sub 3}·3H{sub 2}O respectively. Suspensions with a concentration of 2.0 g/L of PtNPs and RhNPs were dispersed separately in synthetic sweat at pH 4.5 and applied as donor phases to the outer surface of the skin for 24 h. Measurements of the content of the metals in the receiving solution and in the skin were performed subsequently. Rhodium skin permeation was demonstrated through damaged skin, with a permeation flux of 0.04 ± 0.04 μg cm{sup −2} h{sup −1} and a lag time of 7.9 ± 1.1 h, while no traces of platinum were found in receiving solutions. Platinum and rhodium skin-analysis showed significantly higher concentrations of the metals in damaged skin. Rh and Pt applied as NPs can penetrate the skin barrier and Rh can be found in receiving solutions. These experiments pointed out the need for skin contamination prevention, since even a minor injury to the skin barrier can significantly increase penetration.

Bioenvironmental aspects of europium and rhodium: a selected bibliography

International Nuclear Information System (INIS)

Fore, C.S.; Carrier, R.F.; Talmage, S.S.; Fielden, J.M.; Daniel, E.W.

1983-09-01

This bibliography of 428 abstracted references represents a summary of the domestic and foreign literature relevant to the biological and environmental aspects of europium and rhodium. The collected data are organized by current NAEG interests - research highlighting inventory and distribution of the radionulcides, ecological studies covering terrestrial and aquatic systems, and biological studies in both man and animals. Studies that focus directly on research conducted at specific sites (e.g., the Nevada Test Site) are emphasized throughout the bibliography

Rhodium-catalyzed redox-neutral coupling of phenidones with alkynes.

Science.gov (United States)

Fan, Zhoulong; Lu, Heng; Li, Wei; Geng, Kaijun; Zhang, Ao

2017-07-21

A switchable synthesis of N-substituted indole derivatives from phenidones via rhodium-catalyzed redox-neutral C-H activation has been achieved. In this protocol, we firstly disclosed that the reactivity of Rh(iii) catalysis could be enhanced through employing palladium acetate as an additive. Some representative features include external oxidant-free, applicable to terminal alkynes, short reaction time and operational simplicity. The utility of this method is further showcased by the economical synthesis of potent anticancer PARP-1 inhibitors.

Leachability of nitrided ilmenite in hydrochloric acid

OpenAIRE

Swanepoel, J.J.; van Vuuren, D.S.; Heydenrych, M.

2011-01-01

Titanium nitride in upgraded nitrided ilmenite (bulk of iron removed) can selectively be chlorinated to produce titanium tetrachloride. Except for iron, most other components present during this low temperature (ca. 200°C) chlorination reaction will not react with chlorine. It is therefore necessary to remove as much iron as possible from the nitrided ilmenite. Hydrochloric acid leaching is a possible process route to remove metallic iron from nitrided ilmenite without excessive dissolution o...

Double-spin-flip resonance of rhodium nuclei at positive and negative spin temperatures

DEFF Research Database (Denmark)

Tuoriniemi, J.T.; Knuuttila, T.A.; Lefmann, K.

2000-01-01

Sensitive SQUID-NMR measurements were used to study the mutual interactions in the highly polarized nuclear-spin system of rhodium metal. The dipolar coupling gives rise to a weak double-spin-flip resonance. The observed frequency shifts allow deducing separately the dipolarlike contribution...

Nitriding behavior of Ni and Ni-based binary alloys

Energy Technology Data Exchange (ETDEWEB)

Fonovic, Matej

2015-01-15

Gaseous nitriding is a prominent thermochemical surface treatment process which can improve various properties of metallic materials such as mechanical, tribological and/or corrosion properties. This process is predominantly performed by applying NH{sub 3}+H{sub 2} containing gas atmospheres serving as the nitrogen donating medium at temperatures between 673 K and 873 K (400 C and 600 C). NH{sub 3} decomposes at the surface of the metallic specimen and nitrogen diffuses into the surface adjacent region of the specimen whereas hydrogen remains in the gas atmosphere. One of the most important parameters characterizing a gaseous nitriding process is the so-called nitriding potential (r{sub N}) which determines the chemical potential of nitrogen provided by the gas phase. The nitriding potential is defined as r{sub N} = p{sub NH{sub 3}}/p{sub H{sub 2}{sup 3/2}} where p{sub NH{sub 3}} and p{sub H{sub 2}} are the partial pressures of the NH{sub 3} and H{sub 2} in the nitriding atmosphere. In contrast with nitriding of α-Fe where the nitriding potential is usually in the range between 0.01 and 1 atm{sup -1/2}, nitriding of Ni and Ni-based alloys requires employing nitriding potentials higher than 100 atm{sup -1/2} and even up to ∞ (nitriding in pure NH{sub 3} atmosphere). This behavior is compatible with decreased thermodynamic stability of the 3d-metal nitrides with increasing atomic number. Depending on the nitriding conditions (temperature, nitriding potential and treatment time), different phases are formed at the surface of the Ni-based alloys. By applying very high nitriding potential, formation of hexagonal Ni{sub 3}N at the surface of the specimen (known as external nitriding) leads to the development of a compound layer, which may improve tribological properties. Underneath the Ni{sub 3}N compound layer, two possibilities exist: (i) alloying element precipitation within the nitrided zone (known as internal nitriding) and/or (ii) development of metastable and

Divergent Reactivity of Rhodium(I) Carbenes Derived from Indole Annulations.

Science.gov (United States)

Li, Xiaoxun; Li, Hui; Song, Wangze; Tseng, Po-Sen; Liu, Lingyan; Guzei, Ilia A; Tang, Weiping

2015-10-26

Rhodium(I) carbenes were generated from propargylic alcohol derivatives as the result of a dehydrative indole annulation. Depending on the choice of the electron-withdrawing group on the aniline nitrogen nucleophile, either a cyclopropanation product or dimerization product was obtained chemoselectively. Intramolecular hydroamidation occurred for the same type of propargylic alcohol derivatives when other transition-metal catalysts were employed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interfacial bonding stabilizes rhodium and rhodium oxide nanoparticles on layered Nb oxide and Ta oxide supports.

Science.gov (United States)

Strayer, Megan E; Binz, Jason M; Tanase, Mihaela; Shahri, Seyed Mehdi Kamali; Sharma, Renu; Rioux, Robert M; Mallouk, Thomas E

2014-04-16

Metal nanoparticles are commonly supported on metal oxides, but their utility as catalysts is limited by coarsening at high temperatures. Rhodium oxide and rhodium metal nanoparticles on niobate and tantalate supports are anomalously stable. To understand this, the nanoparticle-support interaction was studied by isothermal titration calorimetry (ITC), environmental transmission electron microscopy (ETEM), and synchrotron X-ray absorption and scattering techniques. Nanosheets derived from the layered oxides KCa2Nb3O10, K4Nb6O17, and RbTaO3 were compared as supports to nanosheets of Na-TSM, a synthetic fluoromica (Na0.66Mg2.68(Si3.98Al0.02)O10.02F1.96), and α-Zr(HPO4)2·H2O. High surface area SiO2 and γ-Al2O3 supports were also used for comparison in the ITC experiments. A Born-Haber cycle analysis of ITC data revealed an exothermic interaction between Rh(OH)3 nanoparticles and the layered niobate and tantalate supports, with ΔH values in the range -32 kJ·mol(-1) Rh to -37 kJ·mol(-1) Rh. In contrast, the interaction enthalpy was positive with SiO2 and γ-Al2O3 supports. The strong interfacial bonding in the former case led to "reverse" ripening of micrometer-size Rh(OH)3, which dispersed as 0.5 to 2 nm particles on the niobate and tantalate supports. In contrast, particles grown on Na-TSM and α-Zr(HPO4)2·H2O nanosheets were larger and had a broad size distribution. ETEM, X-ray absorption spectroscopy, and pair distribution function analyses were used to study the growth of supported nanoparticles under oxidizing and reducing conditions, as well as the transformation from Rh(OH)3 to Rh nanoparticles. Interfacial covalent bonding, possibly strengthened by d-electron acid/base interactions, appear to stabilize Rh(OH)3, Rh2O3, and Rh nanoparticles on niobate and tantalate supports.

Alloy Effects on the Gas Nitriding Process

Science.gov (United States)

Yang, M.; Sisson, R. D.

2014-12-01

Alloy elements, such as Al, Cr, V, and Mo, have been used to improve the nitriding performance of steels. In the present work, plain carbon steel AISI 1045 and alloy steel AISI 4140 were selected to compare the nitriding effects of the alloying elements in AISI 4140. Fundamental analysis is carried out by using the "Lehrer-like" diagrams (alloy specific Lehrer diagram and nitriding potential versus nitrogen concentration diagram) and the compound layer growth model to simulate the gas nitriding process. With this method, the fundamental understanding for the alloy effect based on the thermodynamics and kinetics becomes possible. This new method paves the way for the development of new alloy for nitriding.

Ion nitridation - physical and technological aspects

International Nuclear Information System (INIS)

Elbern, A.W.

1980-01-01

Ion nitridation, is a technique which allows the formation of a controlled thickness of nitrides in the surface of the material, using this material as the cathode in a low pressure glow discharge, which presents many advantages over the conventional method. A brief review of the ion nitriding technique, the physical fenomena involved, and we discuss technological aspects of this method, are presented. (Author) [pt

Silicon nitride-fabrication, forming and properties

International Nuclear Information System (INIS)

Yehezkel, O.

1983-01-01

This article, which is a literature survey of the recent years, includes description of several methods for the formation of silicone nitride, and five methods of forming: Reaction-bonded silicon nitride, sintering, hot pressing, hot isostatic pressing and chemical vapour deposition. Herein are also included data about mechanical and physical properties of silicon nitride and the relationship between the forming method and the properties. (author)

Synthesis of reduced carbon nitride at the reduction by hydroquinone of water-soluble carbon nitride oxide (g-C{sub 3}N{sub 4})O

Energy Technology Data Exchange (ETDEWEB)

Kharlamov, Alexey [Frantsevich Institute for Problems of Materials Science of NASU, Krzhyzhanovsky St. 3, 03680 Kiev (Ukraine); Bondarenko, Marina, E-mail: mebondarenko@ukr.net [Frantsevich Institute for Problems of Materials Science of NASU, Krzhyzhanovsky St. 3, 03680 Kiev (Ukraine); Kharlamova, Ganna [Taras Shevchenko National University of Kiev, Volodymyrs' ka St. 64, 01601 Kiev (Ukraine); Fomenko, Veniamin [Frantsevich Institute for Problems of Materials Science of NASU, Krzhyzhanovsky St. 3, 03680 Kiev (Ukraine)

2016-09-15

For the first time at the reduction by hydroquinone of water-soluble carbon nitride oxide (g-C{sub 3}N{sub 4})O reduced carbon nitride (or reduced multi-layer azagraphene) is obtained. It is differed from usually synthesized carbon nitride by a significantly large (on 0.09 nm) interplanar distance is. At the same time, the chemical bonds between atoms in a heteroatomic plane of reduced carbon nitride correspond to the bonds in a synthesized g-C{sub 3}N{sub 4}. The samples of water-soluble carbon nitride oxide were synthesized under the special reactionary conditions of a pyrolysis of melamine and urea. We believe that reduced carbon nitride consists of weakly connected carbon-nitrogen monosheets (azagraphene sheets) as well as reduced (from graphene oxide) graphene contains weakly connected graphene sheets. - Graphical abstract: XRD pattern and schematic atomic model of one layer of reduced carbon nitride, carbon nitride oxide and synthesized carbon nitride. For the first time at the reduction by hydroquinone of the water-soluble carbon nitride oxide (g-C{sub 3}N{sub 4})O is obtained the reduced carbon nitride (or reduced multi-layer azagraphene). Display Omitted - Highlights: • First the reduced carbon nitride (RCN) at the reduction of the carbon nitride oxide was obtained. • Water-soluble carbon nitride oxide was reduced by hydroquinone. • The chemical bonds in a heteroatomic plane of RCN correspond to the bonds in a synthesized g-C{sub 3}N{sub 4}. • Reduced carbon nitride consists of poorly connected heteroatomic azagraphene layers.

A Recyclable Nanoparticle-Supported Rhodium Catalyst for Hydrogenation Reactions

Directory of Open Access Journals (Sweden)

Maria Michela Dell’Anna

2010-05-01

Full Text Available Catalytic hydrogenation under mild conditions of olefins, unsaturated aldeydes and ketones, nitriles and nitroarenes was investigated, using a supported rhodium complex obtained by copolymerization of Rh(cod(aaema [cod: 1,5-cyclooctadiene, aaema–: deprotonated form of 2-(acetoacetoxyethyl methacrylate] with acrylamides. In particular, the hydrogenation reaction of halonitroarenes was carried out under 20 bar hydrogen pressure with ethanol as solvent at room temperature, in order to minimize hydro-dehalogenation. The yields in haloanilines ranged from 85% (bromoaniline to 98% (chloroaniline.

The determination, by atomic-absorption spectrophotometry using electrothermal atomization, of platinum, palladium, rhodium, ruthenium, and iridium

International Nuclear Information System (INIS)

Haines, J.; Robert, R.V.D.

1982-01-01

A method that involves measurement by atomic-absorption spectrophotometry using electrothermal atomization has been developed for the determination of trace quantities of platinum, palladium, rhodium, ruthenium, and iridium in mineralogical samples. The elements are separated and concentrated by fusion, nickel sulphide being used as the collector, and the analyte elements are measured in the resulting acid solution. An organic extraction procedure was found to offer no advantages over the proposed method. Mutual interferences between the five platinum-group metals examined, as well as interferences from gold, silver, and nickel were determined. The accuracy of the measurement was established by the analysis of a platinum-ore reference material. The lower limits of determination of each of the analyte elements in a sample material are as follows: platinum 1,6μg/l, palladium 0,2μg/1, rhodium 0,5μg/l, ruthenium 3μg/l, and iridium 2,5μg/l. The relative standard deviations range from 0,05 for rhodium to 0.08 for iridium. The method, which is described in detail in the Appendix, is applicable to the determination of these elements in ores, tailings, and geological materials in which the total concentration of the noble metals is less than 1g/t

Complexation of rhodium(II) tetracarboxylates with aliphatic diamines in solution: 1H and 13C NMR and DFT investigations.

Science.gov (United States)

Jaźwiński, Jarosław; Sadlej, Agnieszka

2013-10-01

The complexation of rhodium(II) tetraacetate, tetrakistrifluoroaceate and tetrakisoctanoate with a set of diamines (ethane-1,diamine, propane-1,3-diamine and nonane-1,9-diamine) and their N,N'-dimethyl and N,N,N',N'-tetramethyl derivatives in chloroform solution has been investigated by (1) H and (13) C NMR spectroscopy and density functional theory (DFT) modelling. A combination of two bifunctional reagents, diamines and rhodium(II) tetracarboxylates, yielded insoluble coordination polymers as main products of complexation and various adducts in the solution, being in equilibrium with insoluble material. All diamines initially formed the 2 : 1 (blue), (1 : 1)n oligomeric (red) and 1 : 2 (red) axial adducts in solution, depending on the reagents' molar ratio. Adducts of primary and secondary diamines decomposed in the presence of ligand excess, the former via unstable equatorial complexes. The complexation of secondary diamines slowed down the inversion at nitrogen atoms in NH(CH3 ) functional groups and resulted in the formation of nitrogenous stereogenic centres, detectable by NMR. Axial adducts of tertiary diamines appeared to be relatively stable. The presence of long aliphatic chains in molecules (adducts of nonane-1,9-diamines or rhodium(II) tetrakisoctanoate) increased adduct solubility. Hypothetical structures of the equatorial adduct of rhodium(II) tetraacetate with ethane-1,2-diamine and their NMR parameters were explored by means of DFT calculations. Copyright © 2013 John Wiley & Sons, Ltd.

Topotactic synthesis of vanadium nitride solid foams

International Nuclear Information System (INIS)

Oyama, S.T.; Kapoor, R.; Oyama, H.T.; Hofmann, D.J.; Matijevic, E.

1993-01-01

Vanadium nitride has been synthesized with a surface area of 120 m 2 g -1 by temperature programmed nitridation of a foam-like vanadium oxide (35 m 2 g -1 ), precipitated from vanadate solutions. The nitridation reaction was established to be topotactic and pseudomorphous by x-ray powder diffraction and scanning electron microscopy. The crystallographic relationship between the nitride and oxide was {200}//{001}. The effect of precursor geometry on the product size and shape was investigated by employing vanadium oxide solids of different morphologies

Microstructure and mechanical properties of silicon nitride structural ceramics of silicon nitride

International Nuclear Information System (INIS)

Strohaecker, T.R.; Nobrega, M.C.S.

1989-01-01

The utilization of direct evaluation technic of tenacity for fracturing by hardness impact in silicon nitride ceramics is described. The microstructure were analysied, by Scanning Electron Microscopy, equiped with a microanalysis acessory by X ray energy dispersion. The difference between the values of K IC measure for two silicon nitride ceramics is discussed, in function of the microstructures and the fracture surfaces of the samples studied. (C.G.C.) [pt

Anti corrosion layer for stainless steel in molten carbonate fuel cell - comprises phase vapour deposition of titanium nitride, aluminium nitride or chromium nitride layer then oxidising layer in molten carbonate electrolyte

DEFF Research Database (Denmark)

2000-01-01

Forming an anticorrosion protective layer on a stainless steel surface used in a molten carbonate fuel cell (MCFC) - comprises the phase vapour deposition (PVD) of a layer comprising at least one of titanium nitride, aluminium nitride or chromium nitride and then forming a protective layer in situ...

PipPhos and MorfPhos : Privileged monodentate phosphoramidite ligands for rhodium-catalyzed asymmetric hydrogenation

NARCIS (Netherlands)

Bernsmann, Heiko; van den Berg, M; Hoen, Robert; Minnaard, AJ; Mehler, G; Reetz, MT; De Vries, JG; Feringa, BL

2005-01-01

A library of 20 monodentate phosphoramidite ligands has been prepared and applied in rhodium-catalyzed asymmetric hydrogenation. This resulted in the identification of two ligands, PipPhos and MorfPhos, that afford excellent and in several cases unprecedented enantioselectivities in the

The prospect of uranium nitride (UN) and mixed nitride fuel (UN-PuN) for pressurized water reactor

International Nuclear Information System (INIS)

Syarifah, Ratna Dewi; Suud, Zaki

2015-01-01

Design study of small Pressurized Water Reactors (PWRs) core loaded with uranium nitride fuel (UN) and mixed nitride fuel (UN-PuN), Pa-231 as burnable poison, and Americium has been performed. Pa-231 known as actinide material, have large capture cross section and can be converted into fissile material that can be utilized to reduce excess reactivity. Americium is one of minor actinides with long half life. The objective of adding americium is to decrease nuclear spent fuel in the world. The neutronic analysis results show that mixed nitride fuel have k-inf greater than uranium nitride fuel. It is caused by the addition of Pu-239 in mixed nitride fuel. In fuel fraction analysis, for uranium nitride fuel, the optimum volume fractions are 45% fuel fraction, 10% cladding and 45% moderator. In case of UN-PuN fuel, the optimum volume fractions are 30% fuel fraction, 10% cladding and 60% coolant/ moderator. The addition of Pa-231 as burnable poison for UN fuel, enrichment U-235 5%, with Pa-231 1.6% has k-inf more than one and excess reactivity of 14.45%. And for mixed nitride fuel, the lowest value of reactivity swing is when enrichment (U-235+Pu) 8% with Pa-231 0.4%, the excess reactivity value 13,76%. The fuel pin analyze for the addition of Americium, the excess reactivity value is lower than before, because Americium absorb the neutron. For UN fuel, enrichment U-235 8%, Pa-231 1.6% and Am 0.5%, the excess reactivity is 4.86%. And for mixed nitride fuel, when enrichment (U-235+Pu) 13%, Pa-231 0.4% and Am 0.1%, the excess reactivity is 11.94%. For core configuration, it is better to use heterogeneous than homogeneous core configuration, because the radial power distribution is better

The prospect of uranium nitride (UN) and mixed nitride fuel (UN-PuN) for pressurized water reactor

Science.gov (United States)

Syarifah, Ratna Dewi; Suud, Zaki

2015-09-01

Design study of small Pressurized Water Reactors (PWRs) core loaded with uranium nitride fuel (UN) and mixed nitride fuel (UN-PuN), Pa-231 as burnable poison, and Americium has been performed. Pa-231 known as actinide material, have large capture cross section and can be converted into fissile material that can be utilized to reduce excess reactivity. Americium is one of minor actinides with long half life. The objective of adding americium is to decrease nuclear spent fuel in the world. The neutronic analysis results show that mixed nitride fuel have k-inf greater than uranium nitride fuel. It is caused by the addition of Pu-239 in mixed nitride fuel. In fuel fraction analysis, for uranium nitride fuel, the optimum volume fractions are 45% fuel fraction, 10% cladding and 45% moderator. In case of UN-PuN fuel, the optimum volume fractions are 30% fuel fraction, 10% cladding and 60% coolant/ moderator. The addition of Pa-231 as burnable poison for UN fuel, enrichment U-235 5%, with Pa-231 1.6% has k-inf more than one and excess reactivity of 14.45%. And for mixed nitride fuel, the lowest value of reactivity swing is when enrichment (U-235+Pu) 8% with Pa-231 0.4%, the excess reactivity value 13,76%. The fuel pin analyze for the addition of Americium, the excess reactivity value is lower than before, because Americium absorb the neutron. For UN fuel, enrichment U-235 8%, Pa-231 1.6% and Am 0.5%, the excess reactivity is 4.86%. And for mixed nitride fuel, when enrichment (U-235+Pu) 13%, Pa-231 0.4% and Am 0.1%, the excess reactivity is 11.94%. For core configuration, it is better to use heterogeneous than homogeneous core configuration, because the radial power distribution is better.

Bifunctional Rhodium Intercalator Conjugates as Mismatch-Directing DNA Alkylating Agents

OpenAIRE

Schatzschneider, Ulrich; Barton, Jacqueline K.

2004-01-01

A conjugate of a DNA mismatch-specific rhodium intercalator, containing the bulky chrysenediimine ligand, and an aniline mustard has been prepared, and targeting of mismatches in DNA by this conjugate has been examined. The preferential alkylation of mismatched over fully matched DNA is found by a mobility shift assay at concentrations where untethered organic mustards show little reaction. The binding site of the Rh intercalator was determined by DNA photocleavage, and the position of covale...

Humidity-dependent stability of amorphous germanium nitrides fabricated by plasma nitridation

International Nuclear Information System (INIS)

Kutsuki, Katsuhiro; Okamoto, Gaku; Hosoi, Takuji; Shimura, Takayoshi; Watanabe, Heiji

2007-01-01

We have investigated the stability of amorphous germanium nitride (Ge 3 N 4 ) layers formed by plasma nitridation of Ge(100) surfaces using x-ray photoelectron spectroscopy and atomic force microscopy. We have found that humidity in the air accelerates the degradation of Ge 3 N 4 layers and that under 80% humidity condition, most of the Ge-N bonds convert to Ge-O bonds, producing a uniform GeO 2 layer, within 12 h even at room temperature. After this conversion of nitrides to oxides, the surface roughness drastically increased by forming GeO 2 islands on the surfaces. These findings indicate that although Ge 3 N 4 layers have superior thermal stability compared to the GeO 2 layers, Ge 3 N 4 reacts readily with hydroxyl groups and it is therefore essential to take the best care of the moisture in the fabrication of Ge-based devices with Ge 3 N 4 insulator or passivation layers

Optical characterization of gallium nitride

NARCIS (Netherlands)

Kirilyuk, Victoria

2002-01-01

Group III-nitrides have been considered a promising system for semiconductor devices since a few decades, first for blue- and UV-light emitting diodes, later also for high-frequency/high-power applications. Due to the lack of native substrates, heteroepitaxially grown III-nitride layers are usually

Rhodium-catalyzed chemo- and regioselective decarboxylative addition of β-ketoacids to alkynes.

Science.gov (United States)

Li, Changkun; Grugel, Christian P; Breit, Bernhard

2016-04-30

A highly efficient rhodium-catalyzed chemo- and regioselective addition of β-ketoacids to alkynes is reported. Applying a Rh(i)/(S,S)-DIOP catalyst system, γ,δ-unsaturated ketones were prepared with exclusively branched selectivity under mild conditions. This demonstrates that readily available alkynes can be an alternative entry to allyl electrophiles in transition-metal catalyzed allylic alkylation reactions.

Rhodium Catalyzed Annulation of N-Benzoylsulfonamide with Isocyanide via C-H Activation

Science.gov (United States)

Zhu, Chen; Xie, Weiqing; Falck, John R.

2012-01-01

Isocyanide insertion: the first rhodium-catalyzed annulation of N-benzoylsulfonamide incorporating with isocyanide via C-H activation is described. The transformation is broadly compatible with N-benzoylsulfonamides bearing various electron-properties as well as isocyanides. From practical point of view, this methodology provides the most straightforward approach to a series of 3-(imino)isoindolinones. PMID:21972033

Synthesis and structural study of the transition metal doped rhodium perovskites

International Nuclear Information System (INIS)

Ting, J.; Kennedy, B.; Zhang, Z.

2009-01-01

Full text: One of the most common structures encountered in solid state chemistry is the perovskite structure. With a general formula of AB0 3, the A-type cations are 12-coordinate within a cubo-octahedral environment, while the B-type cations are 6-coordinate, forming an interconnecting three-dimensional octahedral network with neighbouring oxygen anions. While the ideal perovskite structure is cubic in Pm 3 m, many perovskites exhibit symmetry lowering tilting of the corner-sharing B0 6o ctahedral units as a result of A- and B-type cation size disparity. This is also evident in substituted perovskites, where two cations occupy the smaller octahedral site, AB 1- xB' x0 3' Electronic effects can also lower the symmetry. The two most commonly observed effects are the polarisation of the B-cation with a d 0 electronic configuration and Jahn-Teller distortion where the B-cation has a d 4 or d 9 electronic configuration, such as Mn 3+ or Cu 2+ respectively. Manganese containing perovskites have been shown in some compounds to exhibit long-range orbital ordering, giving rise to interesting properties. Heavier transition metals such as ruthenium and iridium have been previously incorporated into these perovskites as an avenue to regulate the properties of these materials. Two orthorhombic rhodium perovskite structures are presented, LaMn 0 . 5 Rh 0 . 5 O 3 and LaCu 05 Rh 0 . 5 O 3 ' A combination of synchrotron x-ray and neutron powder diffraction has been used to elucidate their structures, and have shown both B- and B'-type cations to be disordered across the same crystallographic site for both compounds. x-ray absorption spectroscopy measurements have been used to provide an insight into the valence states of the cations, which show a valency of +3.5 for rhodium due to an extensive charge delocalisation between copper and rhodium.

Immobilization of rhodium complexes at thiolate monolayers on gold surfaces : Catalytic and structural studies

NARCIS (Netherlands)

Belser, T; Stöhr, Meike; Pfaltz, A

2005-01-01

Chiral rhodium-diphosphine complexes have been incorporated into self-assembled thiolate monolayers (SAMS) on gold colloids. Catalysts of this type are of interest because they combine properties of homogeneous and heterogeneous systems. In addition, it should be possible to influence the catalytic

A MECHANISTIC STUDY OF RHODIUM TRI(ORTHO-TERT-BUTYLPHENYL)PHOSPHITE COMPLEXES AS HYDROFORMYLATION CATALYSTS

NARCIS (Netherlands)

JONGSMA, T; CHALLA, G; VANLEEUWEN, PWNM

1991-01-01

A mechanistic study of the hydroformylation cycle with a rhodium tri(o-t-butylphenyl)phosphite complex as catalyst is presented. Spectroscopic experiments prove that under hydroformylation conditions this complex is coordinated by only one phosphite. The complex has a high activity in the

Hydrogen diffusion between plasma-deposited silicon nitride-polyimide polymer interfaces

International Nuclear Information System (INIS)

Nguyen, S.V.; Kerbaugh, M.

1988-01-01

This paper reports a nuclear reaction analysis (NRA) for hydrogen technique used to analyze the hydrogen concentration near plasma enhanced chemical vapor deposition (PECVD) silicon nitride-polyimide interfaces at various nitride-deposition and polyimide-polymer-curing temperatures. The CF 4 + O 2 (8% O 2 ) plasma-etch-rate variation of PECVD silicon nitride films deposited on polyimide appeared to correlate well with the variation of hydrogen-depth profiles in the nitride films. The NRA data indicate that hydrogen-depth-profile fluctuation in the nitride films is due to hydrogen diffusion between the nitride-polyimide interfaces during deposition. Annealing treatment of polyimide films in a hydrogen atmosphere prior to the nitride film deposition tends to enhance the hydrogen-depth-profile uniformity in the nitride films, and thus substantially reduces or eliminates variation in the nitride plasma-etch rate

Nucleation of iron nitrides during gaseous nitriding of iron; the effect of a preoxidation treatment

DEFF Research Database (Denmark)

Friehling, Peter B.; Poulsen, Finn Willy; Somers, Marcel A.J.

2001-01-01

grains. On prolonged nitriding, immediate nucleation at the surface of iron grains becomes possible. Calculated incubation times for the nucleation of gamma'-Fe4N1-x during nitriding are generally longer than those observed experimentally in the present work. The incubation time is reduced dramatically...

RF plasma nitriding of severely deformed iron-based alloys

International Nuclear Information System (INIS)

Ferkel, H.; Glatzer, M.; Estrin, Y.; Valiev, R.Z.; Blawert, C.; Mordike, B.L.

2003-01-01

The effect of severe plastic deformation by cold high pressure torsion (HPT) on radio frequency (RF) plasma nitriding of pure iron, as well as St2K50 and X5CrNi1810 steels was investigated. Nitriding was carried out for 3 h in a nitrogen atmosphere at a pressure of 10 -5 bar and temperatures of 350 and 400 deg. C. Nitrided specimens were analysed by scanning electron microscopy (SEM), X-ray diffraction and micro hardness measurements. It was found that HPT enhances the effect of nitriding leading almost to doubling of the thickness of the nitrided layer for pure iron and the high alloyed steel. The largest increase in hardness was observed when HPT was combined with RF plasma nitriding at 350 deg. C. In the case of pure iron, the X-ray diffraction spectra showed the formation of ε and γ' nitrides in the compound layer, with a preferential formation of γ' at the expense of the α-phase at the higher nitriding temperature. The corresponding surface hardness was up to 950 HV0.01. While the HPT-processed St2K50 exhibits both nitride phases after nitriding at 350 deg. C, only the γ'-phase was observed after nitriding at 400 deg. C. A surface hardness of up to 1050 HV0.01 was measured for this steel. The high alloyed steel X5CrNi1810 exhibited the highest increase in surface hardness when HPT was combined with nitriding at 350 deg. C. The surface hardness of this steel was greater than 1400 HV0.025. The XRD analyses indicate the formation of the expanded austenite (S-phase) in the surface layer as a result of RF plasma nitriding. Furthermore, after HPT X5CrNi1810 was transformed completely into deformation martensite which did not transform back to austenite under thermochemical treatment. However, in the case of nitriding of the HPT-processed high alloyed steel at 400 deg. C, the formation of the S-phase was less pronounced. In view of the observed XRD peak broadening, the formation of nitrides, such as e.g. CrN, cannot be ruled out

Development of pseudocapacitive molybdenum oxide–nitride for electrochemical capacitors

Energy Technology Data Exchange (ETDEWEB)

Ting, Yen-Jui Bernie [Department of Electrical and Computer Engineering, University of Toronto, Toronto, Ontario M5S 3E4 (Canada); Wu, Haoran [Department of Materials Science and Engineering, University of Toronto, Toronto, Ontario M5S 3E4 (Canada); Kherani, Nazir P. [Department of Electrical and Computer Engineering, University of Toronto, Toronto, Ontario M5S 3E4 (Canada); Department of Materials Science and Engineering, University of Toronto, Toronto, Ontario M5S 3E4 (Canada); Lian, Keryn, E-mail: keryn.lian@utoronto.ca [Department of Materials Science and Engineering, University of Toronto, Toronto, Ontario M5S 3E4 (Canada)

2015-03-15

A thin film Mo oxide–nitride pseudocapacitive electrode was synthesized by electrodeposition of Mo oxide on Ti and a subsequent low-temperature (400 °C) thermal nitridation. Two nitridation environments, N{sub 2} and NH{sub 3}, were used and the results were compared. Surface analyses of these nitrided films showed partial conversion of Mo oxide to nitrides, with a lower conversion percentage being the film produced in N{sub 2}. However, the electrochemical analyses showed that the surface of the N{sub 2}-treated film had better pseudocapacitive behaviors and outperformed that nitrided in NH{sub 3}. Cycle life of the resultant N{sub 2}-treated Mo oxide–nitride was also much improved over Mo oxide. A two-electrode cell using Mo oxide–nitride electrodes was demonstrated and showed high rate performance. - Highlights: • Mo(O,N){sub x} was developed by electrodeposition and nitridation in N{sub 2} or NH{sub 3}. • N{sub 2} treated Mo(O,N){sub x} showed a capacitive performance superior to that treated by NH{sub 3}. • The promising electrochemical performance was due to the formation of γ-Mo{sub 2}N.

Direct C-H alkylation and indole formation of anilines with diazo compounds under rhodium catalysis.

Science.gov (United States)

Mishra, Neeraj Kumar; Choi, Miji; Jo, Hyeim; Oh, Yongguk; Sharma, Satyasheel; Han, Sang Hoon; Jeong, Taejoo; Han, Sangil; Lee, Seok-Yong; Kim, In Su

2015-12-18

The rhodium(III)-catalyzed direct functionalization of aniline C-H bonds with α-diazo compounds is described. These transformations provide a facile construction of ortho-alkylated anilines with diazo malonates or highly substituted indoles with diazo acetoacetates.

In Situ Structure-Function Studies of Oxide Supported Rhodium Catalysts by Combined Energy Dispersive XAFS and DRIFTS Spectroscopies

International Nuclear Information System (INIS)

Evans, John; Dent, Andrew J.; Diaz-Moreno, Sofia; Fiddy, Steven G.; Jyoti, Bhrat; Tromp, Moniek; Newton, Mark A.

2007-01-01

The techniques of energy dispersive EXAFS (EDE), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) and mass spectrometry (MS) have been combined to study the structure and function of an oxide supported metal catalyst, namely 5 wt% Rh/Al2O3. Using a FreLoN camera as the EDE detector and a rapid-scanning IR spectrometer, experiments could be performed with a repetition rate of 50 ms. The results show that the nature of the rhodium centers is a function of the partial pressures of the reacting gases (CO and NO) and also temperature. This combination of gases oxidizes metallic rhodium particles to Rh(CO)2 at room temperature. The proportion of the rhodium adopting this site increases as the temperature is raised (up to 450 K). Above that temperature the dicarbonyl decomposes and the metal reclusters. Once this condition is met, catalysis ensues. Gas switching techniques show that at 573 K with NO in excess, the clusters can be oxidized rapidly to afford a linear nitrosyl complex; re-exposure to CO also promotes reclustering and the CO adopts terminal (atop) and bridging (2-fold) sites

New Routes to Lanthanide and Actinide Nitrides

Energy Technology Data Exchange (ETDEWEB)

Butt, D.P.; Jaques, B.J.; Osterberg, D.D. [Boise State University, 1910 University Dr., Boise, Idaho 83725-2075 (United States); Marx, B.M. [Concurrent Technologies Corporation, Johnstown, PA (United States); Callahan, P.G. [Carnegie Mellon University, Pittsburgh, PA (United States); Hamdy, A.S. [Central Metallurgical R and D Institute, Helwan, Cairo (Egypt)

2009-06-15

The future of nuclear energy in the U.S. and its expansion worldwide depends greatly on our ability to reduce the levels of high level waste to minimal levels, while maintaining proliferation resistance. Implicit in the so-called advanced fuel cycle is the need for higher levels of fuel burn-up and consequential use of complex nuclear fuels comprised of fissile materials such as Pu, Am, Np, and Cm. Advanced nitride fuels comprised ternary and quaternary mixtures of uranium and these actinides have been considered for applications in advanced power plants, but there remain many processing challenges as well as necessary qualification testing. In this presentation, the advantages and disadvantages of nitride fuels are discussed. Methods of synthesizing the raw materials and sintering of fuels are described including a discussion of novel, low cost routes to nitrides that have the potential for reducing the cost and footprint of a fuel processing plant. Phase pure nitrides were synthesized via four primary methods; reactive milling metal flakes in nitrogen at room temperature, directly nitriding metal flakes in a pure nitrogen atmosphere, hydriding metal flakes prior to nitridation, and carbo-thermically reducing the metal oxide and carbon mixture prior to nitridation. In the present study, the sintering of UN, DyN, and their solid solutions (U{sub x}, Dy{sub 1-x}) (x = 1 to 0.7) were also studied. (authors)

Rhodium self-powered detector for monitoring neutron fluence, energy production, and isotopic composition of fuel

International Nuclear Information System (INIS)

Sokolov, A.P.; Pochivalin, G.P.; Shipovskikh, Yu.M.; Garusov, Yu.V.; Chernikov, O.G.; Shevchenko, V.G.

1993-01-01

The use of self-powered detectors (SPDs) with a rhodium emitter customarily involves monitoring of neutron fields in the core of a nuclear reactor. Since current in an SPD is generated primarily because of the neutron flux, which is responsible for the dynamics of particular nuclear transformations, including fission reactions of heavy isotopes, the detector signal can be attributed unambiguously to energy release at the location of the detector. Computation modeling performed with the KOMDPS package of programs of the current formation in a rhodium SPD along with the neutron-physical processes that occur in the reactor core makes it possible to take account of the effect of the principal factors characterizing the operating conditions and the design features of the fuel channel and the detector, reveal quantitative relations between the generated signal and individual physical parameters, and determine the metrological parameters of the detector. The formation and transport of changed particles in the sensitive part of the SPC is calculated by the Monte Carlo method. The emitter activation, neutron transport, and dynamics of the isotopic composition in the fuel channel containing the SPD are determined by solving the kinetic equation in the multigroup representation of the neutron spectrum, using the discrete ordinate method. In this work the authors consider the operation of a rhodium SPD in a bundle of 49 fuel channels of the RBMK-1000 reactor with a fuel enrichment of 2.4% from the time it is inserted into a fresh channel

Moessbauer spectroscopic characterisation of catalysts obtained by interaction between tetra-n-butyl-tin and silica or silica supported rhodium

International Nuclear Information System (INIS)

Millet, J.M.M.; Toyir, J.; Didillon, B.; Candy, J.P.; Nedez, C.; Basset, J.M.

1997-01-01

Moessbauer spectroscopy at 78 K was used to study the interaction between tetra-n-butyl-tin and the surfaces of silica or silica supported rhodium. At room temperature, the tetra-n-butyl-tin was physically adsorbed on the surfaces. After reaction under hydrogen at 373 K, the formation of grafted organometallic fragments on the Rh surface was confirmed whereas with pure silica, ≡SiO-Sn(n-C 4 H 9 ) 3 moieties were observed. After treatment at 523 K, the rhodium grafted organometallic species was completely decomposed and there was formation of a defined bimetallic RhSn compound

Plasma nitriding - an eco friendly surface hardening process

International Nuclear Information System (INIS)

Mukherjee, S.

2015-01-01

Surface hardening is a process of heating the metal such that the surface gets only hardened. This process is adopted for many components like gears, cams, and crankshafts, which desire high hardness on the outer surface with a softer core to withstand the shocks. So, to attain such properties processes like carburising, nitriding, flame hardening and induction hardening are employed. Amongst these processes nitriding is the most commonly used process by many industries. In nitriding process the steel material is heated to a temperature of around 550 C and then exposed to atomic nitrogen. This atomic nitrogen reacts with iron and other alloying elements and forms nitrides, which are very hard in nature. By this process both wear resistance and hardness of the product can be increased. The atomic nitrogen required for this process can be obtained using ammonia gas (gas nitriding), cyanide based salt bath (liquid nitriding) and plasma medium (plasma nitriding). However, plasma nitriding has recently received considerable industrial interest owing to its characteristic of faster nitrogen penetration, short treatment time, low process temperature, minimal distortion, low energy use and easier control of layer formation compared with conventional techniques such as gas and liquid nitriding. This process can be used for all ferrous materials including stainless steels. Plasma nitriding is carried out using a gas mixture of nitrogen and hydrogen gas at sub atmospheric pressures hence, making it eco-friendly in nature. Plasma nitriding allows modification of the surface layers and hardness profiles by changing the gas mixture and temperature. The wide applicable temperature range enables a multitude of applications, beyond the possibilities of gas or salt bath processes. This has led to numerous applications of this process in industries such as the manufacture of machine parts for plastics and food processing, packaging and tooling as well as pumps and hydraulic, machine

Advancing liquid metal reactor technology with nitride fuels

International Nuclear Information System (INIS)

Lyon, W.F.; Baker, R.B.; Leggett, R.D.; Matthews, R.B.

1991-08-01

A review of the use of nitride fuels in liquid metal fast reactors is presented. Past studies indicate that both uranium nitride and uranium/plutonium nitride possess characteristics that may offer enhanced performance, particularly in the area of passive safety. To further quantify these effects, the analysis of a mixed-nitride fuel system utilizing the geometry and power level of the US Advanced Liquid Metal Reactor as a reference is described. 18 refs., 2 figs., 2 tabs

Complexes of technetium, rhenium, and rhodium with sexidentate Schiff-base ligands

International Nuclear Information System (INIS)

Hunter, G.; Kilcullen, N.

1989-01-01

The monocationic technetium (IV) and rhenium (IV) complexes with the sexidentate Schiff-base ligands tris[2-(2'-hydroxybenzylideneethyl)]amine and its substituted derivatives have been prepared and their electrochemical properties studied. The variable-temperature 90.6 MHz 13 C-{ 1 H} n.m.r. spectrum of the rhodium (III) complex of tris[2-(2-hydroxy-5'-isopropylbenzylideneethyl)-amine] has been observed, indicating fluxionality at temperatures above 218 K. (author)

Exploring electrolyte preference of vanadium nitride supercapacitor electrodes

Energy Technology Data Exchange (ETDEWEB)

Wang, Bo; Chen, Zhaohui; Lu, Gang [Department of Electrical Engineering and Automation, Luoyang Institute of Science and Technology, Luoyang 471023 (China); Wang, Tianhu [School of Electrical Information and Engineering, Jiangsu University of Technology, Changzhou 213001 (China); Ge, Yunwang, E-mail: ywgelit@126.com [Department of Electrical Engineering and Automation, Luoyang Institute of Science and Technology, Luoyang 471023 (China)

2016-04-15

Highlights: • Hierarchical VN nanostructures were prepared on graphite foam. • Electrolyte preference of VN supercapacitor electrodes was explored. • VN showed better capacitive property in organic and alkaline electrolytes than LiCl. - Abstract: Vanadium nitride hierarchical nanostructures were prepared through an ammonia annealing procedure utilizing vanadium pentoxide nanostructures grown on graphite foam. The electrochemical properties of hierarchical vanadium nitride was tested in aqueous and organic electrolytes. As a result, the vanadium nitride showed better capacitive energy storage property in organic and alkaline electrolytes. This work provides insight into the charge storage process of vanadium nitride and our findings can shed light on other transition metal nitride-based electrochemical energy storage systems.

Modeling the Gas Nitriding Process of Low Alloy Steels

Science.gov (United States)

Yang, M.; Zimmerman, C.; Donahue, D.; Sisson, R. D.

2013-07-01

The effort to simulate the nitriding process has been ongoing for the last 20 years. Most of the work has been done to simulate the nitriding process of pure iron. In the present work a series of experiments have been done to understand the effects of the nitriding process parameters such as the nitriding potential, temperature, and time as well as surface condition on the gas nitriding process for the steels. The compound layer growth model has been developed to simulate the nitriding process of AISI 4140 steel. In this paper the fundamentals of the model are presented and discussed including the kinetics of compound layer growth and the determination of the nitrogen diffusivity in the diffusion zone. The excellent agreements have been achieved for both as-washed and pre-oxided nitrided AISI 4140 between the experimental data and simulation results. The nitrogen diffusivity in the diffusion zone is determined to be constant and only depends on the nitriding temperature, which is ~5 × 10-9 cm2/s at 548 °C. It proves the concept of utilizing the compound layer growth model in other steels. The nitriding process of various steels can thus be modeled and predicted in the future.

Synthesis of Uranium nitride powders using metal uranium powders

International Nuclear Information System (INIS)

Yang, Jae Ho; Kim, Dong Joo; Oh, Jang Soo; Rhee, Young Woo; Kim, Jong Hun; Kim, Keon Sik

2012-01-01

Uranium nitride (UN) is a potential fuel material for advanced nuclear reactors because of their high fuel density, high thermal conductivity, high melting temperature, and considerable breeding capability in LWRs. Uranium nitride powders can be fabricated by a carbothermic reduction of the oxide powders, or the nitriding of metal uranium. The carbothermic reduction has an advantage in the production of fine powders. However it has many drawbacks such as an inevitable engagement of impurities, process burden, and difficulties in reusing of expensive N 15 gas. Manufacturing concerns issued in the carbothermic reduction process can be solved by changing the starting materials from oxide powder to metals. However, in nitriding process of metal, it is difficult to obtain fine nitride powders because metal uranium is usually fabricated in the form of bulk ingots. In this study, a simple reaction method was tested to fabricate uranium nitride powders directly from uranium metal powders. We fabricated uranium metal spherical powder and flake using a centrifugal atomization method. The nitride powders were obtained by thermal treating those metal particles under nitrogen containing gas. We investigated the phase and morphology evolutions of powders during the nitriding process. A phase analysis of nitride powders was also a part of the present work

Rhodium-catalyzed triarylphosphine synthesis via cross-coupling of aryl iodides and acylphosphines

Directory of Open Access Journals (Sweden)

Jiefang Yang

2018-01-01

Full Text Available Rhodium(I-catalyzed C–P cross-coupling reaction with aryl iodides and acylphosphines was disclosed for a straight forward synthesis of triarylphosphines. The acylphosphines were successfully employed as both the phosphorus source and the ligand to the Rh(I catalyst. The triarylphosphines could be afforded in a yield up to 98% with good toleration of wide functional groups.

The oxidation of titanium nitride- and silicon nitride-coated stainless steel in carbon dioxide environments

International Nuclear Information System (INIS)

Mitchell, D.R.G.; Stott, F.H.

1992-01-01

A study has been undertaken into the effects of thin titanium nitride and silicon nitride coatings, deposited by physical vapour deposition and chemical vapour deposition processes, on the oxidation resistance of 321 stainless steel in a simulated advanced gas-cooled reactor carbon dioxide environment for long periods at 550 o C and 700 o C under thermal-cycling conditions. The uncoated steel contains sufficient chromium to develop a slow-growing chromium-rich oxide layer at these temperatures, particularly if the surfaces have been machine-abraded. Failure of this layer in service allows formation of less protective iron oxide-rich scales. The presence of a thin (3-4 μm) titanium nitride coating is not very effective in increasing the oxidation resistance since the ensuing titanium oxide scale is not a good barrier to diffusion. Even at 550 o C, iron oxide-rich nodules are able to develop following relatively rapid oxidation and breakdown of the coating. At 700 o C, the coated specimens oxidize at relatively similar rates to the uncoated steel. A thin silicon nitride coating gives improved oxidation resistance, with both the coating and its slow-growing oxide being relatively electrically insulating. The particular silicon nitride coating studied here was susceptible to spallation on thermal cycling, due to an inherently weak coating/substrate interface. (Author)

Surface modification of titanium by plasma nitriding

Directory of Open Access Journals (Sweden)

Kapczinski Myriam Pereira

2003-01-01

Full Text Available A systematic investigation was undertaken on commercially pure titanium submitted to plasma nitriding. Thirteen different sets of operational parameters (nitriding time, sample temperature and plasma atmosphere were used. Surface analyses were performed using X-ray diffraction, nuclear reaction and scanning electron microscopy. Wear tests were done with stainless steel Gracey scaler, sonic apparatus and pin-on-disc machine. The obtained results indicate that the tribological performance can be improved for samples treated with the following conditions: nitriding time of 3 h; plasma atmosphere consisting of 80%N2+20%H2 or 20%N2+80%H2; sample temperature during nitriding of 600 or 800 degreesC.

Rhodium, iridium and nickel complexes with a 1,3,5-triphenylbenzene tris-MIC ligand. Study of the electronic properties and catalytic activities

Directory of Open Access Journals (Sweden)

Carmen Mejuto

2015-12-01

Full Text Available The coordination versatility of a 1,3,5-triphenylbenzene-tris-mesoionic carbene ligand is illustrated by the preparation of complexes with three different metals: rhodium, iridium and nickel. The rhodium and iridium complexes contained the [MCl(COD] fragments, while the nickel compound contained [NiCpCl]. The preparation of the tris-MIC (MIC = mesoionic carbene complex with three [IrCl(CO2] fragments, allowed the estimation of the Tolman electronic parameter (TEP for the ligand, which was compared with the TEP value for a related 1,3,5-triphenylbenzene-tris-NHC ligand. The electronic properties of the tris-MIC ligand were studied by cyclic voltammetry measurements. In all cases, the tris-MIC ligand showed a stronger electron-donating character than the corresponding NHC-based ligands. The catalytic activity of the tri-rhodium complex was tested in the addition reaction of arylboronic acids to α,β-unsaturated ketones.

Electrochemical Solution Growth of Magnetic Nitrides

Energy Technology Data Exchange (ETDEWEB)

Monson, Todd C. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Pearce, Charles [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2014-10-01

Magnetic nitrides, if manufactured in bulk form, would provide designers of transformers and inductors with a new class of better performing and affordable soft magnetic materials. According to experimental results from thin films and/or theoretical calculations, magnetic nitrides would have magnetic moments well in excess of current state of the art soft magnets. Furthermore, magnetic nitrides would have higher resistivities than current transformer core materials and therefore not require the use of laminates of inactive material to limit eddy current losses. However, almost all of the magnetic nitrides have been elusive except in difficult to reproduce thin films or as inclusions in another material. Now, through its ability to reduce atmospheric nitrogen, the electrochemical solution growth (ESG) technique can bring highly sought after (and previously inaccessible) new magnetic nitrides into existence in bulk form. This method utilizes a molten salt as a solvent to solubilize metal cations and nitrogen ions produced electrochemically and form nitrogen compounds. Unlike other growth methods, the scalable ESG process can sustain high growth rates (~mm/hr) even under reasonable operating conditions (atmospheric pressure and 500 °C). Ultimately, this translates into a high throughput, low cost, manufacturing process. The ESG process has already been used successfully to grow high quality GaN. Below, the experimental results of an exploratory express LDRD project to access the viability of the ESG technique to grow magnetic nitrides will be presented.

Simulation of the Nitriding Process

Science.gov (United States)

Krukovich, M. G.

2004-01-01

Simulation of the nitriding process makes it possible to solve many practical problems of process control, prediction of results, and development of new treatment modes and treated materials. The presented classification systematizes nitriding processes and processes based on nitriding, enables consideration of the theory and practice of an individual process in interrelation with other phenomena, outlines ways for intensification of various process variants, and gives grounds for development of recommendations for controlling the structure and properties of the obtained layers. The general rules for conducting the process and formation of phases in the layer and properties of the treated surfaces are used to create a prediction computational model based on analytical, numerical, and empirical approaches.

Simultaneous determination of palladium, platinum and rhodium by on-line column enrichment and HPLC with 2,4-dihydroxybenzylidenethiorhodanine as pre-column derivatization reagent

Directory of Open Access Journals (Sweden)

Dong Xuechang

2006-01-01

Full Text Available A new method for the simultaneous determination of palladium, platinum and rhodium ions as metal-DHBTR chelates was developed. The palladium, platinum and rhodium ions were pre-column derivatized with 2,4-dihydroxybenzylidenethiorhodanine (DHBTR to form colored chelates. The Pd-DHBTR, Pt-DHBTR and Rh-DHBTR chelates can be absorbed onto the front of the enrichment column when they were injected into the injector and sent to the enrichment column with a 0.05 mol L-1 sodium acetate-acetic acid buffer solution (pH 3.5 as mobile phase. After the enrichment had finished, by switching the six ports switching valve, the retained chelates were back-flushed by mobile phase and traveling towards the analytical column. These chelates separation on the analytical column was satisfactory with 62% (v/v acetonitrile (containing 0.05 mol L-1 of pH 3.5 sodium acetate-acetic acid buffer salt and 0.1% (m/v of tritonX-100 as mobile phase. The Limits of detection of palladium, platinum and rhodium are 3.6 ng L-1, 3.2 ng L-1 and 4.5 ng L-1, respectively. This method was applied to the determination of palladium, platinum and rhodium in water, urine and soil samples with good results.

Ion flotation of rhodium(III) and palladium(II) with anionic surfactants.

Science.gov (United States)

He, X C

1991-03-01

The ion flotation of rhodium(III) and palladium(II) with some anionic surfactants has been investigated. Two flotation procedures are proposed for the separation of some platinum metals, based on differences in the kinetic properties of the chloro-complexes of rhodium(III), palladium(II) and platinum(IV). The first involves the selective flotation of Rh(H(2)O)(3+)(6) from PdCl(2-)(4) and PtCl(2-)(6) in dilute hydrochloric acid with sodium dodecylbenzenesulfonate (SDBS). After precipitation of the hydroxide and redissolution in dilute acid, the Rh(III) is converted into Rh(H(2)O)(3+)(6), Pd(II) and Pt(IV) remaining as PdCl(2-)(4) and PtCl(2-)(6) respectively, and separation is achieved by floating the Rh(H(2)O)(3+)(6) with SDBS. The second is for separation of Pd(II). Prior to flotation, the solution of PdCl(2-)(4) and PtCl(2-)(6) is heated with ammonium acetate to convert PdCl(2-)(4) into Pd(NH(3))(2+)(4). The chloro-complex of Pt(IV) is unaffected. The complex cation, Pd(NH(3))(2+)(4), is then selectively floated with SDBS. The procedures are fast, simple and do not require expensive reagents and apparatus.

Rhodium-catalysed syn-carboamination of alkenes via a transient directing group.

Science.gov (United States)

Piou, Tiffany; Rovis, Tomislav

2015-11-05

Alkenes are the most ubiquitous prochiral functional groups--those that can be converted from achiral to chiral in a single step--that are accessible to synthetic chemists. For this reason, difunctionalization reactions of alkenes (whereby two functional groups are added to the same double bond) are particularly important, as they can be used to produce highly complex molecular architectures. Stereoselective oxidation reactions, including dihydroxylation, aminohydroxylation and halogenation, are well established methods for functionalizing alkenes. However, the intermolecular incorporation of both carbon- and nitrogen-based functionalities stereoselectively across an alkene has not been reported. Here we describe the rhodium-catalysed carboamination of alkenes at the same (syn) face of a double bond, initiated by a carbon-hydrogen activation event that uses enoxyphthalimides as the source of both the carbon and the nitrogen functionalities. The reaction methodology allows for the intermolecular, stereospecific formation of one carbon-carbon and one carbon-nitrogen bond across an alkene, which is, to our knowledge, unprecedented. The reaction design involves the in situ generation of a bidentate directing group and the use of a new cyclopentadienyl ligand to control the reactivity of rhodium. The results provide a new way of synthesizing functionalized alkenes, and should lead to the convergent and stereoselective assembly of amine-containing acyclic molecules.

Characterization of plasma nitrided layers produced on sintered iron

Directory of Open Access Journals (Sweden)

Marcos Alves Fontes

2014-07-01

Full Text Available Plasma nitriding is a thermo-physical-chemical treatment process, which promotes surface hardening, caused by interstitial diffusion of atomic nitrogen into metallic alloys. In this work, this process was employed in the surface modification of a sintered ferrous alloy. Scanning electron microscopy (SEM, X-ray diffraction (XRD analyses, and wear and microhardness tests were performed on the samples submitted to ferrox treatment and plasma nitriding carried out under different conditions of time and temperature. The results showed that the nitride layer thickness is higher for all nitrided samples than for ferrox treated samples, and this layer thickness increases with nitriding time and temperature, and temperature is a more significant variable. The XRD analysis showed that the nitrided layer, for all samples, near the surface consists in a mixture of γ′-Fe4N and ɛ-Fe3N phases. Both wear resistance and microhardness increase with nitriding time and temperature, and temperature influences both the characteristics the most.

Innovative boron nitride-doped propellants

Directory of Open Access Journals (Sweden)

Thelma Manning

2016-04-01

Full Text Available The U.S. military has a need for more powerful propellants with balanced/stoichiometric amounts of fuel and oxidants. However, balanced and more powerful propellants lead to accelerated gun barrel erosion and markedly shortened useful barrel life. Boron nitride (BN is an interesting potential additive for propellants that could reduce gun wear effects in advanced propellants (US patent pending 2015-026P. Hexagonal boron nitride is a good lubricant that can provide wear resistance and lower flame temperatures for gun barrels. Further, boron can dope steel, which drastically improves its strength and wear resistance, and can block the formation of softer carbides. A scalable synthesis method for producing boron nitride nano-particles that can be readily dispersed into propellants has been developed. Even dispersion of the nano-particles in a double-base propellant has been demonstrated using a solvent-based processing approach. Stability of a composite propellant with the BN additive was verified. In this paper, results from propellant testing of boron nitride nano-composite propellants are presented, including closed bomb and wear and erosion testing. Detailed characterization of the erosion tester substrates before and after firing was obtained by electron microscopy, inductively coupled plasma and x-ray photoelectron spectroscopy. This promising boron nitride additive shows the ability to improve gun wear and erosion resistance without any destabilizing effects to the propellant. Potential applications could include less erosive propellants in propellant ammunition for large, medium and small diameter fire arms.

Regioselective syntheses of 1,2-benzothiazines by rhodium-catalyzed annulation reactions.

Science.gov (United States)

Cheng, Ying; Bolm, Carsten

2015-10-12

Rhodium-catalyzed directed carbene insertions into aromatic CH bonds of S-aryl sulfoximines lead to intermediates, which upon dehydration provide 1,2-benzothiazines in excellent yields. The domino-type process is regioselective and shows a high functional-group tolerance. It is scalable, and the only by-products are dinitrogen and water. Three illustrative transformations underscore the synthetic value of the products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Generation and Characteristics of IV-VI transition Metal Nitride and Carbide Nanoparticles using a Reactive Mesoporous Carbon Nitride

KAUST Repository

Alhajri, Nawal Saad

2016-02-22

Interstitial nitrides and carbides of early transition metals in groups IV–VI exhibit platinum-like electronic structures, which make them promising candidates to replace noble metals in various catalytic reactions. Herein, we present the preparation and characterization of nano-sized transition metal nitries and carbides of groups IV–VI (Ti, V, Nb, Ta, Cr, Mo, and W) using mesoporous graphitic carbon nitride (mpg-C3N4), which not only provides confined spaces for restricting primary particle size but also acts as a chemical source of nitrogen and carbon. We studied the reactivity of the metals with the template under N2 flow at 1023 K while keeping the weight ratio of metal to template constant at unity. The produced nanoparticles were characterized by powder X-ray diffraction, CHN elemental analysis, nitrogen sorption, X-ray photoelectron spectroscopy, and transmission electron microscopy. The results show that Ti, V, Nb, Ta, and Cr form nitride phases with face centered cubic structure, whereas Mo and W forme carbides with hexagonal structures. The tendency to form nitride or carbide obeys the free formation energy of the transition metal nitrides and carbides. This method offers the potential to prepare the desired size, shape and phase of transition metal nitrides and carbides that are suitable for a specific reaction, which is the chief objective of materials chemistry.

Preparation and study of the nitrides and mixed carbide-nitrides of uranium and of plutonium

International Nuclear Information System (INIS)

Anselin, F.

1966-06-01

A detailed description is given of a simple method for preparing uranium and plutonium nitrides by the direct action of nitrogen under pressure at moderate temperatures (about 400 C) on the partially hydrogenated bulk metal. It is shown that there is complete miscibility between the UN and PuN phases. The variations in the reticular parameters of the samples as a function of temperature and in the presence of oxide have been used to detect and evaluate the solubility of oxygen in the different phases. A study has been made of the sintering of these nitrides as a function of the preparation conditions with or without sintering additives. A favorable but non-reproducible, effect has been found for traces of oxide. The best results were obtained for pure UN at 1600 C (96 per cent theoretical density) on condition that a well defined powder, was used. The criterion used is the integral width of the X-ray diffraction lines. The compounds UN and PuN are completely miscible with the corresponding carbides. This makes it possible to prepare carbide-nitrides of the general formula (U,Pu) (C,N) by solid-phase diffusion, at around 1400 C. The sintering of these carbide-nitrides is similar to that of the carbides if the nitrogen content is low; in particular, nickel is an efficient sintering agent. For high contents, the sintering is similar to that of pure nitrides. (author) [fr

Oxidative Olefination of Anilides with Unactivated Alkenes Catalyzed by an (Electron-Deficient η(5) -Cyclopentadienyl)Rhodium(III) Complex Under Ambient Conditions.

Science.gov (United States)

Takahama, Yuji; Shibata, Yu; Tanaka, Ken

2015-06-15

The oxidative olefination of sp(2) C-H bonds of anilides with both activated and unactivated alkenes using an (electron-deficient η(5) -cyclopentadienyl)rhodium(III) complex is reported. In contrast to reactions using this electron-deficient rhodium(III) catalyst, [Cp*RhCl2 ]2 showed no activity against olefination with unactivated alkenes. In addition, the deuterium kinetic isotope effect (DKIE) study revealed that the C-H bond cleavage step is thought to be the turnover-limiting step. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes with substituted allenes: stereoselective construction of tri- and tetrasubstituted exocyclic olefins.

Science.gov (United States)

Evans, P Andrew; Negru, Daniela E; Shang, Deju

2015-04-13

The development of the stereoselective rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes (ACPs) with substituted allenes is described. This work demonstrates that activated and unactivated allenes preferentially undergo carbometalation at the distal terminus to generate tri- and tetrasubstituted exocyclic olefins with a neutral rhodium catalyst. In addition, this method provides a strategy for the total synthesis of the guaiane family of sesquiterpenes, which are not directly accessible using alkynes as exogenous π-components. Finally, the preparation of the bicyclo[5.4.0]undecane ring system using a homologated ACP tether serves to further illustrate the versatility of this approach. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation and characteristics of various rare earth nitrides

International Nuclear Information System (INIS)

Imamura, H.; Imahashi, T.; Zaimi, M.; Sakata, Y.

2008-01-01

Active nanocrystalline nitrides of EuN and YbN with high surface areas were successfully prepared by the thermal decomposition of the rare earth amides (Eu(NH 2 ) 2 , Yb(NH 2 ) 2 and Yb(NH 2 ) 3 ). For the preparation of CeN, PrN and NdN, the direct reaction of the rare earth metals with ammonia was extensively studied to determine optimal conditions. In the reaction of rare earth metals with ammonia, hydrides besides the nitrides were competitively formed. The reaction conditions such as temperatures and ratios of ammonia to rare earth metal were crucial in preferential formation of nitride. The nanocrystalline YbN and EuN readily absorbed large amounts of ammonia even at room temperature upon contact with ammonia (13.3 kPa). The absorbed ammonia existed in at least two forms on/in the nitride; the one was surface-adsorbed ammonia and the other ammonia absorbed in the nitride in a decomposed state. The properties of ammonia absorbed by the nitride were further evaluated by temperature-programmed desorption (TPD), FT-IR and XRD techniques

Activity of iridium-ruthenium and iridium-rhodium adsorption catalysts in decomposition of hydrogen peroxide

Energy Technology Data Exchange (ETDEWEB)

Zubovich, I A; Mikhaylov, V A; Migulina, N N [Yaroslavskij Politekhnicheskij Inst. (USSR)

1976-06-01

Experimental data for the activities of iridium-ruthenium and iridium-rhodium adsorption catalysts in the decomposition of hydrogen peroxide are considered and the results of magnetic susceptibility measurements are presented. It is concluded that surface structures (complexes) may be formed and that micro-electronic feaures play a role in heterogeneous catalysis.

Sensitivity change of rhodium self -powered detectors with burn-up

International Nuclear Information System (INIS)

Girgis, R.; Akimov, I.S.; Hamouda, I.

1976-01-01

The scope of the present paper is to obtain the calculation formulae to evaluate the rate of sensitivity change of the neutron self-powered detectors with burn-up. A code written in FORTRAN 4 was developed to be operational on the IBM-1130 computer. It has been established in the case of rhodium detectors that neglecting the β-particle absorption in the calculations leads to the underestimation of the detector sensitivity decrease up to 40%. The derived formulae can be used for other self-powered detectors. (author)

Enhancement of ethanol oxidation at Pt and PtRu nanoparticles dispersed over hybrid zirconia-rhodium supports

Science.gov (United States)

Rutkowska, Iwona A.; Koster, Margaretta D.; Blanchard, Gary J.; Kulesza, Pawel J.

2014-12-01

A catalytic material for electrooxidation of ethanol that utilizes PtRu nanoparticles dispersed over thin films of rhodium-free and rhodium-containing zirconia (ZrO2) supports is described here. The enhancement of electrocatalytic activity (particularly in the potential range as low as 0.25-0.5 V vs. RHE), that has been achieved by dispersing PtRu nanoparticles (loading, 100 μg cm-2) over the hybrid Rh-ZrO2 support composed of nanostructured zirconia and metallic rhodium particles, is clearly evident from comparison of the respective voltammetric and chronoamperometric current densities recorded at room temperature (22 °C) in 0.5 mol dm-3 H2SO4 containing 0.5 mol dm-3 ethanol. Porous ZrO2 nanostructures, that provide a large population of hydroxyl groups in acidic medium in the vicinity of PtRu sites, are expected to facilitate the ruthenium-induced removal of passivating CO adsorbates from platinum, as is apparent from the diagnostic experiments with a small organic molecule such as methanol. Although Rh itself does not show directly any activity toward ethanol oxidation, the metal is expected to facilitate C-C bond splitting in C2H5OH. It has also been found during parallel voltammetric and chronoamperometric measurements that the hybrid Rh-ZrO2 support increases activity of the platinum component itself toward ethanol oxidation in the low potential range.

Rhodium (II) cycle alkanecarboxylate: synthesis, spectroscopic and thermo analytic studies and evaluation of the antitumor potential

International Nuclear Information System (INIS)

Souza, Aparecido Ribeiro de

1995-01-01

Four new rhodium(II) carboxylates (cyclopropane, cyclobutane, cyclopentane, and cyclohexanecarboxylate), and other already known rhodium (II) carboxylates (acetate, propionate, butyrate, metoxyacetate, dichloroacetate, and trifluoroacetate), have been prepared for study in this work. The compounds were characterized by elementary and thermogravimetric analysis, magnetic susceptibility, and electronic, Raman, and infrared spectroscopy. The reaction of Rh CL 3 .aq with the sodium carboxylates was studied aiming to improve the understanding of the redox process involved. Spectroscopy studies (Raman and electronic) were made to examine the transition involved in the Rh-Rh and Rh-O bonds. The results have shown a direct relation between the force of the carboxylic acid and the Rh-O force, but show a inverse relation with the Rh-Rh bond force. Thermal analysis studies were undertaken and the obtained date show a resemblance of the TG/DTG curves with that found in literature. In the other hand, the DSC curves show a different results: in open crucible, the peaks associated with the cage breakdown are exothermic and, in closed crucible this peaks are endothermic. The thermodecomposition products were analyzed. The evolved gases were identified by GC?MS and 1 H and 13 C NMR spectra. The residues were analyzed by X-ray diffraction. Antitumor activity of rhodium cyclopropanecarboxylate was evaluated in vitro (cell cultures K562 and Ehrlich) and in vivo (Balb-c mice with ascite Ehrlich tumor), indicating an increased life span (87.5%) of the treated animals. (author)

Stereoselective 1,3-Insertions of Rhodium(II) Azavinyl Carbenes

Science.gov (United States)

Chuprakov, Stepan; Worrell, Brady T.; Selander, Nicklas; Sit, Rakesh K.; Fokin, Valery V.

2014-01-01

Rhodium(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild and convergent formal 1,3-insertion into N–H and O–H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bis-functionalized Z-olefins with perfect regio- and stereoselectively. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition metal carbene complexes, including α-allenyl ketones and amino-substituted heterocycles. PMID:24295389

Burnup Estimation of Rhodium Self-Powered Neutron Detector Emitter in VVER Reactor Core Using Monte Carlo Simulations

OpenAIRE

Khrutchinsky, А. А.; Kuten, S. A.; Babichev, L. F.

2011-01-01

Estimation of burn-up in a rhodium-103 emitter of self-powered neutron detector in VVER-1000 reactor core has been performed using Monte Carlo simulations within approximation of a constant neutron flux.

Method of preparation of uranium nitride

Science.gov (United States)

Kiplinger, Jaqueline Loetsch; Thomson, Robert Kenneth James

2013-07-09

Method for producing terminal uranium nitride complexes comprising providing a suitable starting material comprising uranium; oxidizing the starting material with a suitable oxidant to produce one or more uranium(IV)-azide complexes; and, sufficiently irradiating the uranium(IV)-azide complexes to produce the terminal uranium nitride complexes.

Microstructural Characterization of Low Temperature Gas Nitrided Martensitic Stainless Steel

DEFF Research Database (Denmark)

Fernandes, Frederico Augusto Pires; Christiansen, Thomas Lundin; Somers, Marcel A. J.

2015-01-01

The present work presents microstructural investigations of the surface zone of low temperature gas nitrided precipitation hardening martensitic stainless steel AISI 630. Grazing incidence X-ray diffraction was applied to investigate the present phases after successive removal of very thin sections...... of the sample surface. The development of epsilon nitride, expanded austenite and expanded martensite resulted from the low temperature nitriding treatments. The microstructural features, hardness and phase composition are discussed with emphasis on the influence of nitriding duration and nitriding potential....

Pyrochemical reprocessing of nitride fuel

International Nuclear Information System (INIS)

Nakazono, Yoshihisa; Iwai, Takashi; Arai, Yasuo

2004-01-01

Electrochemical behavior of actinide nitrides in LiCl-KCl eutectic melt was investigated in order to apply pyrochemical process to nitride fuel cycle. The electrode reaction of UN and (U, Nd)N was examined by cyclic voltammetry. The observed rest potential of (U, Nd)N depended on the equilibrium of U 3+ /UN and was not affected by the addition of NdN of 8 wt.%. (author)

Ammonia synthesis in the presence of rhodium-ruthenium-iridium carbonyl clusters

International Nuclear Information System (INIS)

Fedoseev, I.V.; Solov'ev, N.V.

2007-01-01

Researches in the field of platinum metal coordination compounds, where nitrogen enters as a ligand in coordination sphere of metal, are discussed. Results of experiments on the ammonia synthesis during the CO+N 2 mixture passing through alkali solution containing mixture of carbonyl clusters of rhodium, ruthenium and iridium at atmospheric pressure are given. Technique of the experiment and steps of assumed reactions of nitrogen fixation by Rh, Ir and Ru carbonyl clusters are demonstrated [ru

Fusion bonding of silicon nitride surfaces

DEFF Research Database (Denmark)

Reck, Kasper; Østergaard, Christian; Thomsen, Erik Vilain

2011-01-01

While silicon nitride surfaces are widely used in many micro electrical mechanical system devices, e.g. for chemical passivation, electrical isolation or environmental protection, studies on fusion bonding of two silicon nitride surfaces (Si3N4–Si3N4 bonding) are very few and highly application...

EDITORIAL: Non-polar and semipolar nitride semiconductors Non-polar and semipolar nitride semiconductors

Science.gov (United States)

Han, Jung; Kneissl, Michael

2012-02-01

Throughout the history of group-III-nitride materials and devices, scientific breakthroughs and technological advances have gone hand-in-hand. In the late 1980s and early 1990s, the discovery of the nucleation of smooth (0001) GaN films on c-plane sapphire and the activation of p-dopants in GaN led very quickly to the realization of high-brightness blue and green LEDs, followed by the first demonstration of GaN-based violet laser diodes in the mid 1990s. Today, blue InGaN LEDs boast record external quantum efficiencies exceeding 80% and the emission wavelength of the InGaN-based laser diode has been pushed into the green spectral range. Although these tremenduous advances have already spurred multi-billion dollar industries, there are still a number of scientific questions and technological issues that are unanswered. One key challenge is related to the polar nature of the III-nitride wurtzite crystal. Until a decade ago all research activities had almost exclusively concentrated on (0001)-oriented polar GaN layers and heterostructures. Although the device characteristics seem excellent, the strong polarization fields at GaN heterointerfaces can lead to a significant deterioration of the device performance. Triggered by the first demonstration non-polar GaN quantum wells grown on LiAlO2 by Waltereit and colleagues in 2000, impressive advances in the area of non-polar and semipolar nitride semiconductors and devices have been achieved. Today, a large variety of heterostructures free of polarization fields and exhibiting exceptional electronic and optical properties have been demonstrated, and the fundamental understanding of polar, semipolar and non-polar nitrides has made significant leaps forward. The contributions in this Semiconductor Science and Technology special issue on non-polar and semipolar nitride semiconductors provide an impressive and up-to-date cross-section of all areas of research and device physics in this field. The articles cover a wide range of

Plasma nitridation optimization for sub-15 A gate dielectrics

NARCIS (Netherlands)

Cubaynes, F.N; Schmitz, Jurriaan; van der Marel, C.; Snijders, J.H.M.; Veloso, A.; Rothschild, A.; Olsen, C.; Date, L.

The work investigates the impact of plasma nitridation process parameters upon the physical properties and upon the electrical performance of sub-15 A plasma nitrided gate dielectrics. The nitrogen distribution and chemical bonding of ultra-thin plasma nitrided films have been investigated using

Diagnostic of corrosion–erosion evolution for [Hf-Nitrides/V-Nitrides]n structures

Energy Technology Data Exchange (ETDEWEB)

Escobar, C.; Villarreal, M. [Thin Film Group, Universidad del Valle, A.A. 25360, Cali (Colombia); Caicedo, J.C., E-mail: jcaicedoangulo1@gmail.com [Powder Metallurgy and Processing of Solid Recycled Research Group, Universidad del Valle, Cali (Colombia); Aperador, W. [Ingeniería Mecatrónica, Universidad Militar Nueva Granada, Bogotá (Colombia); Caicedo, H.H. [Department of Bioengineering, University of Illinois at Chicago, IL 60612 (United States); Department of Anatomy and Cell Biology, University of Illinois at Chicago, IL 60612 (United States); Prieto, P. [Thin Film Group, Universidad del Valle, A.A. 25360, Cali (Colombia); Center of Excellence for Novel Materials, CENM, Cali (Colombia)

2013-10-31

HfN/VN multilayered systems were grown on 4140 steel substrates with the aim to improve their electrochemical behavior. The multilayered coatings were grown via reactive r.f. magnetron sputtering technique by systematically varying the bilayer period (Λ) and the bilayer number (n) while maintaining constant the total coating thickness (∼ 1.2 μm). The coatings were characterized by X-ray diffraction (XRD), and electron microscopy. The electrochemical properties were studied by Electrochemical Impedance Spectroscopy and Tafel curves. XRD results showed preferential growth in the face-centered cubic (111) crystal structure for [HfN/VN]{sub n} multilayered coatings. The maximum corrosion resistance was obtained for coatings with (Λ) equal to 15 nm, corresponding to bilayer n = 80. Polarization resistance and corrosion rate was around 112.19 kΩ cm{sup 2} and 0.094*10{sup −3} mmy respectively; moreover, these multilayered system showed a decrease of 80% on mass loss due to the corrosive–erosive process, in relation to multilayered systems with n = 1 and Λ = 1200. HfN/VN multilayers have been designed and deposited on Si (100) and AISI 4140 steel substrates with bilayer periods (Λ) in a broad range, from nanometers to hundreds of nanometers to study the microstructural evolution and electrochemical progress with decreasing bilayer thickness. - Highlights: • Enhancements on surface electrochemical properties and response to surface corrosion attack. • Superficial phenomenon that occurs in corrosion surface of [Hf-Nitrides/V-Nitrides]n • Corrosion–erosion evolution for [Hf-Nitrides/V-Nitrides]n structures.

Diagnostic of corrosion–erosion evolution for [Hf-Nitrides/V-Nitrides]n structures

International Nuclear Information System (INIS)

Escobar, C.; Villarreal, M.; Caicedo, J.C.; Aperador, W.; Caicedo, H.H.; Prieto, P.

2013-01-01

HfN/VN multilayered systems were grown on 4140 steel substrates with the aim to improve their electrochemical behavior. The multilayered coatings were grown via reactive r.f. magnetron sputtering technique by systematically varying the bilayer period (Λ) and the bilayer number (n) while maintaining constant the total coating thickness (∼ 1.2 μm). The coatings were characterized by X-ray diffraction (XRD), and electron microscopy. The electrochemical properties were studied by Electrochemical Impedance Spectroscopy and Tafel curves. XRD results showed preferential growth in the face-centered cubic (111) crystal structure for [HfN/VN] n multilayered coatings. The maximum corrosion resistance was obtained for coatings with (Λ) equal to 15 nm, corresponding to bilayer n = 80. Polarization resistance and corrosion rate was around 112.19 kΩ cm 2 and 0.094*10 −3 mmy respectively; moreover, these multilayered system showed a decrease of 80% on mass loss due to the corrosive–erosive process, in relation to multilayered systems with n = 1 and Λ = 1200. HfN/VN multilayers have been designed and deposited on Si (100) and AISI 4140 steel substrates with bilayer periods (Λ) in a broad range, from nanometers to hundreds of nanometers to study the microstructural evolution and electrochemical progress with decreasing bilayer thickness. - Highlights: • Enhancements on surface electrochemical properties and response to surface corrosion attack. • Superficial phenomenon that occurs in corrosion surface of [Hf-Nitrides/V-Nitrides]n • Corrosion–erosion evolution for [Hf-Nitrides/V-Nitrides]n structures

Solvent extraction of no-carrier-added 103Pd from irradiated rhodium target with α-furyldioxime

International Nuclear Information System (INIS)

Mahdi Sadeghi; Behrouz Shirazi; Nami Shadanpour

2006-01-01

Solvent extraction of no-carrier-added 103 Pd was investigated from irradiated rhodium target with a-furyldioxime in chloroform from diluted hydrochloric acid. Extraction yield was 85.3% for a single extraction from 0.37M HCl and 103 Pd purity was better than 99%. (author)

Identification of short-lived neutron-rich ruthenium and rhodium isotopes in fission

International Nuclear Information System (INIS)

Franz, G.; Herrmann, G.

1975-01-01

Short-lived ruthenium and rhodium isotopes ( 107 Ru, 108 Ru, 108 Rh, 109 Ru, 109 Rh, 110 Ru, 110 Rh, 111 Ru, 111 Rh, 112 Ru, 112 Rh, 113 Ru) have been separated from fission products by a rapid chemical procedure and identified by means of γ-ray spectroscopy. Nuclides with half-lives down to 3 sec were accessible. Ruthenium isotopes up to mass number 113 have been identified. (author)

1,3-dialkyl- and 1,3-diaryl-3,4,5,6-tetrahydropyrimidin-2-ylidene rhodium(i) and palladium(II) complexes: synthesis, structure, and reactivity.

Science.gov (United States)

Mayr, Monika; Wurst, Klaus; Ongania, Karl-Hans; Buchmeiser, Michael R

2004-03-05

The synthesis of novel 1,3-diaryl- and 1,3-dialkylpyrimidin-2-ylidene-based N-heterocyclic carbenes (NHCs) and their rhodium(i) and palladium(II) complexes is described. The rhodium compounds bromo(cod)[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (7), bromo(cod)(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (8) (cod=eta(4)-1,5-cyclooctadiene, mesityl=2,4,6-trimethylphenyl), chloro(cod)(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (9), and chloro(cod)[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (10) were prepared by reaction of [[Rh(cod)Cl](2)] with lithium tert-butoxide followed by addition of 1,3-dimesityl-3,4,5,6-tetrahydropyrimidinium bromide (3), 1,3-dimesityl-3,4,5,6-tetrahydropyrimidinium tetrafluoroborate (4), 1,3-di-2-propyl-3,4,5,6-tetrahydropyrimidinium bromide (6), and 1,3-di-2-propyl-3,4,5,6-tetrahydropyrimidinium tetrafluoroborate, respectively. Complex 7 crystallizes in the monoclinic space group P2(1)/n, and 8 in the monoclinic space group P2(1). Complexes 9 and 10 were used for the synthesis of the corresponding dicarbonyl complexes dicarbonylchloro(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (11), and dicarbonylchloro[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (12). The wavenumbers nu(CO I)/nu(CO II) for 11 and 12 were used as a quantitative measure for the basicity of the NHC ligand. The values of 2062/1976 and 2063/1982 cm(-1), respectively, indicate that the new NHCs are among the most basic cyclic ligands reported so far. Compounds 3 and 6 were additionally converted to the corresponding cationic silver(i) bis-NHC complexes [Ag(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)(2)]AgBr(2) (13) and [Ag[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene](2)]AgBr(2) (14), which were subsequently used in transmetalation reactions for the synthesis of the corresponding palladium(II) complexes Pd(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2

Rhodium(III)-Catalyzed [3+2]/[5+2] Annulation of 4-Aryl 1,2,3-Triazoles with Internal Alkynes through Dual C(sp2)-H Functionalization.

Science.gov (United States)

Yang, Yuan; Zhou, Ming-Bo; Ouyang, Xuan-Hui; Pi, Rui; Song, Ren-Jie; Li, Jin-Heng

2015-05-26

A rhodium(III)-catalyzed [3+2]/[5+2] annulation of 4-aryl 1-tosyl-1,2,3-triazoles with internal alkynes is presented. This transformation provides straightforward access to indeno[1,7-cd]azepine architectures through a sequence involving the formation of a rhodium(III) azavinyl carbene, dual C(sp(2))-H functionalization, and [3+2]/[5+2] annulation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A rhodium(III) complex inhibits LPS-induced nitric oxide production and angiogenic activity in cellulo.

Science.gov (United States)

Liu, Li-Juan; Lin, Sheng; Chan, Daniel Shiu-Hin; Vong, Chi Teng; Hoi, Pui Man; Wong, Chun-Yuen; Ma, Dik-Lung; Leung, Chung-Hang

2014-11-01

Metal-containing complexes have arisen as viable alternatives to organic molecules as therapeutic agents. Metal complexes possess a number of advantages compared to conventional carbon-based compounds, such as distinct geometries, interesting electronic properties, variable oxidation states and the ability to arrange different ligands around the metal centre in a precise fashion. Meanwhile, nitric oxide (NO) plays key roles in the regulation of angiogenesis, vascular permeability and inflammation. We herein report a novel cyclometalated rhodium(III) complex as an inhibitor of lipopolysaccharides (LPS)-induced NO production in RAW264.7 macrophages. Experiments suggested that the inhibition of NO production in cells by complex 1 was mediated through the down-regulation of nuclear factor-κB (NF-κB) activity. Furthermore, complex 1 inhibited angiogenesis in human umbilical vein endothelial cells (HUVECs) as revealed by an endothelial tube formation assay. This study demonstrates that kinetically inert rhodium(III) complexes may be potentially developed as effective anti-angiogenic agents. Copyright © 2014 Elsevier Inc. All rights reserved.

Complexation of diphenyl(phenylacetenyl)phosphine to rhodium(III) tetraphenyl porphyrins

DEFF Research Database (Denmark)

Stulz, Eugen; Scott, Sonya M; Bond, Andrew D

2003-01-01

). The methylide on rhodium in 3 is not displaced, leading selectively to the mono-phosphine complex (DPAP)(Me)Rh(TPP) (5). The first and second association constants, as determined by isothermal titration calorimetry and UV-vis titrations, are in the range 10(4)-10(7) M(-1) (in CH(2)Cl(2)). Using LDI-TOF mass....... The largest values of DeltaG degrees are found for 6. The thermodynamic and UV-vis data reveal that the methylide and the phosphine ligand have an almost identical electronic trans-influence on the sixth ligand....

Nano-particulate Aluminium Nitride/Al: An Efficient and Versatile Heterogeneous Catalyst for the Synthesis of Biginelli Scaffolds

Science.gov (United States)

Tekale, S. U.; Tekale, A. B.; Kanhe, N. S.; Bhoraskar, S. V.; Pawar, R. P.

2011-12-01

Nano-particulate aluminium nitride/Al (7:1) is reported as a new heterogeneous solid acid catalyst for the synthesis of 3, 4-dihydroxypyrimidi-2-(1H)-ones and their sulphur analogues using the Biginelli reaction. This method involves short reaction time, easy separation, high yields and purity of products.

Mesoporous coaxial titanium nitride-vanadium nitride fibers of core-shell structures for high-performance supercapacitors.

Science.gov (United States)

Zhou, Xinhong; Shang, Chaoqun; Gu, Lin; Dong, Shanmu; Chen, Xiao; Han, Pengxian; Li, Lanfeng; Yao, Jianhua; Liu, Zhihong; Xu, Hongxia; Zhu, Yuwei; Cui, Guanglei

2011-08-01

In this study, titanium nitride-vanadium nitride fibers of core-shell structures were prepared by the coaxial electrospinning, and subsequently annealed in the ammonia for supercapacitor applications. These core-shell (TiN-VN) fibers incorporated mesoporous structure into high electronic conducting transition nitride hybrids, which combined higher specific capacitance of VN and better rate capability of TiN. These hybrids exhibited higher specific capacitance (2 mV s(-1), 247.5 F g(-1)) and better rate capability (50 mV s(-1), 160.8 F g(-1)), which promise a good candidate for high-performance supercapacitors. It was also revealed by electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS) characterization that the minor capacitance fade originated from the surface oxidation of VN and TiN.

Additive Manufacturing of Dense Hexagonal Boron Nitride Objects

Energy Technology Data Exchange (ETDEWEB)

Marquez Rossy, Andres E [ORNL; Armstrong, Beth L [ORNL; Elliott, Amy M [ORNL; Lara-Curzio, Edgar [ORNL

2017-05-12

The feasibility of manufacturing hexagonal boron nitride objects via additive manufacturing techniques was investigated. It was demonstrated that it is possible to hot-extrude thermoplastic filaments containing uniformly distributed boron nitride particles with a volume concentration as high as 60% and that these thermoplastic filaments can be used as feedstock for 3D-printing objects using a fused deposition system. Objects 3D-printed by fused deposition were subsequently sintered at high temperature to obtain dense ceramic products. In a parallel study the behavior of hexagonal boron nitride in aqueous solutions was investigated. It was shown that the addition of a cationic dispersant to an azeotrope enabled the formulation of slurries with a volume concentration of boron nitride as high as 33%. Although these slurries exhibited complex rheological behavior, the results from this study are encouraging and provide a pathway for manufacturing hexagonal boron nitride objects via robocasting.

Rhodium(I)-catalyzed cyclization of allenynes with a carbonyl group through unusual insertion of a C-O bond into a rhodacycle intermediate.

Science.gov (United States)

Oonishi, Yoshihiro; Yokoe, Takayuki; Hosotani, Akihito; Sato, Yoshihiro

2014-01-20

Rhodium(I)-catalyzed cyclization of allenynes with a tethered carbonyl group was investigated. An unusual insertion of a CO bond into the C(sp(2) )-rhodium bond of a rhodacycle intermediate occurs via a highly strained transition state. Direct reductive elimination from the obtained rhodacyle intermediate proceeds to give a tricyclic product containing an 8-oxabicyclo[3.2.1]octane skeleton, while β-hydride elimination from the same intermediate gives products that contain fused five- and seven-membered rings in high yields. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aluminum nitride insulating films for MOSFET devices

Science.gov (United States)

Lewicki, G. W.; Maserjian, J.

1972-01-01

Application of aluminum nitrides as electrical insulator for electric capacitors is discussed. Electrical properties of aluminum nitrides are analyzed and specific use with field effect transistors is defined. Operational limits of field effect transistors are developed.

Capacitive performance of molybdenum nitride/titanium nitride nanotube array for supercapacitor

Energy Technology Data Exchange (ETDEWEB)

Xie, Yibing, E-mail: ybxie@seu.edu.cn; Tian, Fang

2017-01-15

Highlights: • MoN{sub x}/TiN NTA is fully converted from MoO{sub 2}/TiO{sub 2} NTA by one-step nitridation process. • MoN{sub x}/TiN NTA is used as feasible electrode material of high-performance supercapacitor. • MoN{sub x}/TiN NTA shows high capacitance, rate capability and cycling stability. - Abstract: Molybdenum nitride (MoN{sub x}) depositing on titanium nitride nanotube array (TiN NTA) was designed as MoN{sub x}/TiN NTA for supercapacitor electrode material. MoN{sub x}/TiN NTA was fabricated by electrodepositing molybdenum oxide onto titanium dioxide NTA and one-step nitridation treatment in ammonia. MoN{sub x}/TiN NTA involved top-surface layer of MoN{sub x} nanoparticles and underlying layer of TiN NTA, which contributed to electric double layer capacitance in aqueous lithium-ion electrolyte solution. The specific capacitance was increased from 69.05 mF cm{sup −2} for TiN NTA to 121.50 mF cm{sup −2} for MoN{sub x}/TiN NTA at 0.3 mA cm{sup −2}, presenting the improved capacitance performance. MoN{sub x} exhibited the capacitance of 174.83 F g{sup −1} at 1.5 A g{sup −1} and slightly declined to 109.13 F g{sup −1} at 30 A g{sup −1}, presenting high rate capability. MoN{sub x}/TiN NTA exhibited the capacitance retention ratio of 93.8% at 3.0 mA cm{sup −2} after 1000 cycles, presenting high cycling stability. MoN{sub x}/TiN NTA could act as a promising electrode material of supercapacitor.

Nitride coating enhances endothelialization on biomedical NiTi shape memory alloy

Energy Technology Data Exchange (ETDEWEB)

Ion, Raluca [University of Bucharest, Department of Biochemistry and Molecular Biology, 91-95 Spl. Independentei, 050095 Bucharest (Romania); Luculescu, Catalin [National Institute for Laser, Plasma and Radiation Physics, 409 Atomistilor, P.O. Box MG-36, 077125 Magurele-Bucharest (Romania); Cimpean, Anisoara, E-mail: anisoara.cimpean@bio.unibuc.ro [University of Bucharest, Department of Biochemistry and Molecular Biology, 91-95 Spl. Independentei, 050095 Bucharest (Romania); Marx, Philippe [AMF Company, Route de Quincy, 18120 Lury-sur-Arnon (France); Gordin, Doina-Margareta; Gloriant, Thierry [INSA Rennes, UMR CNRS 6226 ISCR, 20 Avenue des Buttes de Coësmes, 35708 Rennes Cedex 7 (France)

2016-05-01

Surface nitriding was demonstrated to be an effective process for improving the biocompatibility of implantable devices. In this study, we investigated the benefits of nitriding the NiTi shape memory alloy for vascular stent applications. Results from cell experiments indicated that, compared to untreated NiTi, a superficial gas nitriding treatment enhanced the adhesion of human umbilical vein endothelial cells (HUVECs), cell spreading and proliferation. This investigation provides data to demonstrate the possibility of improving the rate of endothelialization on NiTi by means of nitride coating. - Highlights: • Gas nitriding process of NiTi is competent to promote cell spreading. • Surface nitriding of NiTi is able to stimulate focal adhesion formation and cell proliferation. • Similar expression pattern of vWf and eNOS was exhibited by bare and nitrided NiTi. • Gas nitriding treatment of NiTi shows promise for better in vivo endothelialization.

Electrochemical behavior of rare earth metals and their nitrides

International Nuclear Information System (INIS)

Ito, Yasuhiko; Goto, Takuya

2004-01-01

Pyrometallurgical recycle process using molten salts is considered to be a high potential in pyro-reprocess technologies for spent nitride fuels, and it is important to understand chemical and electro-chemical behavior of nitrides and metals in molten salts. In this study, cadmium nitrates deposited on the anode Cd plate in motlen salt (LiCl-KCl) with addition of Li 3 N are examined. The cadmium nitrates deposited have various compositions corresponding to polarization potentials and then, the relationship between the deposition potential of nitride Cd and their composition is cleared. Their standard chemical potential of CdN is estimated from electrochemical measurement. And then, potential-pH 3- diagram is drawn by voltametry examination of nitride resolution behavior with using thermochemical data of nitrides. (A. Hishinuma)

Leachability of nitrided ilmenite in hydrochloric acid

CSIR Research Space (South Africa)

Swanepoel, JJ

2010-10-01

Full Text Available Titanium nitride in upgraded nitrided ilmenite (bulk of iron removed) can selectively be chlorinated to produce titanium tetrachloride. Except for iron, most other components present during this low temperature (ca. 200 °C) chlorination reaction...

Thermodynamics, kinetics and process control of nitriding

DEFF Research Database (Denmark)

Mittemeijer, Eric J.; Somers, Marcel A. J.

1999-01-01

As a prerequisite for predictability of properties obtained by a nitriding treatment of iron-based workpieces, the relation between the process parameters and the composition and structure of the surface layer produced must be known. At present (even) the description of thermodynamic equilibrium...... of pure iron-nitrogen phases has not been achieved fully. It has been shown that taking into account ordering of nitrogen in the epsilon and gamma' iron-nitride phases, leads to an improved understanding of the Fe-N phase diagram. Although thermodynamics indicate the state the system strives for......, the nitriding result is determined largely by the kinetics of the process. The nitriding kinetics have been shown to be characterised by the occurring local near-equilibria and stationary states at surfaces and interfaces, and the diffusion coefficient of nitrogen in the various phases, for which new data have...

Residual Stress Induced by Nitriding and Nitrocarburizing

DEFF Research Database (Denmark)

Somers, Marcel A.J.

2005-01-01

The present chapter is devoted to the various mechanisms involved in the buildup and relief of residual stress in nitrided and nitrocarburized cases. The work presented is an overview of model studies on iron and iron-based alloys. Subdivision is made between the compound (or white) layer......, developing at the surfce and consisting of iron-based (carbo)nitrides, and the diffusion zone underneath, consisting of iron and alloying element nitrides dispersed in af ferritic matrix. Microstructural features are related directly to the origins of stress buildup and stres relief....

Substrate-induced antiferromagnetism of ultrathin iron overlayers on the iridium and rhodium (001) surfaces

Czech Academy of Sciences Publication Activity Database

Máca, František; Kudrnovský, Josef; Drchal, Václav; Turek, Ilja; Bengone, O.; Redinger, J.

2009-01-01

Roč. 11, - (2009), s. 38-40 ISSN 1642-6037 R&D Projects: GA ČR GA202/07/0456; GA MŠk OC09028 Institutional research plan: CEZ:AV0Z10100520; CEZ:AV0Z20410507 Keywords : iridium * rhodium * iron * magnetismus in thin layers * density functional calculations Subject RIV: BM - Solid Matter Physics ; Magnetism

Rhodium-Catalyzed Regioselective C7-Olefination of Indazoles Using an N-Amide Directing Group.

Science.gov (United States)

Guo, Lei; Chen, Yanyu; Zhang, Rong; Peng, Qiujun; Xu, Lanting; Pan, Xianhua

2017-02-01

A rhodium-catalyzed regioselective C-H olefination of indazole is described. This protocol relies on the use of an efficient and removable N,N-diisopropylcarbamoyl directing group, which offers facile access to C7-olefinated indazoles with high regioselectivity, ample substrate scope and broad functional group tolerance. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical Sensor Based on Rh(III) Ion-Imprinted Polymer as a New Modifying Agent for Rhodium Determination.

Science.gov (United States)

Bai, Huiping; Xiong, Caiyun; Wang, Chunqiong; Liu, Peng; Dong, Su; Cao, Qiue

2018-05-01

A rhodium (III) ion carbon paste electrode (CPE) based on an ion imprinted polymer (IIP) as a new modifying agent has been prepared and studied. Rh(III) ion imprinted polymer was synthesized by copolymerization of acrylamide-Rh(III) complex and ethylene glycol dimethacrylate according to the precipitation polymerization. Acrylamide acted as both functional monomer and complexing agent to create selective coordination sites in a cross-linked polymer. The ion imprinted carbon paste electrode (IIP-CPE) was prepared by mixing rhodium IIP-nanoparticles and graphite powder in n-eicosane as an adhesive and then embedding them in a Teflon tube. Amperometric i-t curve method was applied as the determination technique. Several parameters, including the functional monomer, molar ratio of template, monomer and cross-linking agent, the amounts of IIP, the applied potential, the buffer solution and pH have been studied. According to the results, IIP-CPE showed a considerably higher response in comparison with the electrode embedded with non-imprinted polymer (NIP), indicating the formation of suitable recognition sites in the IIP structure during the polymerization stage. The introduced electrode showed a linear range of 1.00×10-8~3.0×10-5 mol·L-1 and detection limit of 6.0 nmol L-1 (S/N = 3). The IIP-CPE was successfully applied for the trace rhodium determination in catalyst and plant samples with RSD of less than 3.3% (n = 5) and recoveries in the range of 95.5~102.5%.

Rhodium-catalyzed asymmetric hydrogenation of unprotected NH imines assisted by a thiourea.

Science.gov (United States)

Zhao, Qingyang; Wen, Jialin; Tan, Renchang; Huang, Kexuan; Metola, Pedro; Wang, Rui; Anslyn, Eric V; Zhang, Xumu

2014-08-04

Asymmetric hydrogenation of unprotected NH imines catalyzed by rhodium/bis(phosphine)-thiourea provided chiral amines with up to 97% yield and 95% ee. (1)H NMR studies, coupled with control experiments, implied that catalytic chloride-bound intermediates were involved in the mechanism through a dual hydrogen-bonding interaction. Deuteration experiments proved that the hydrogenation proceeded through a pathway consistent with an imine. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamical model of computation of the rhodium self-powered neutron detector current

International Nuclear Information System (INIS)

Erben, O.; Slovacek, M.; Zerola, L.

1992-01-01

A model is presented for the calculation of the rhodium self-powered neutron detector current in dependence on the neutron flux density during reactor core transients. The total signal consists of a beta emission, prompt, and gamma component and a background signal. The model has been verified by means of experimental data obtained during measurements on the LVR-15 research reactor and at the Dukovany nuclear power plant. (author) 9 figs., 21 refs

Methane Steam Reforming Kinetics for a Rhodium-Based Catalyst

DEFF Research Database (Denmark)

Jakobsen, Jon Geest; Jakobsen, M.; Chorkendorff, Ib

2010-01-01

Methane steam reforming is the key reaction to produce synthesis gas and hydrogen at the industrial scale. Here the kinetics of methane steam reforming over a rhodium-based catalyst is investigated in the temperature range 500-800 A degrees C and as a function of CH4, H2O and H-2 partial pressures....... The methane steam reforming reaction cannot be modeled without taking CO and H coverages into account. This is especially important at low temperatures and higher partial pressures of CO and H-2. For methane CO2 reforming experiments, it is also necessary to consider the repulsive interaction of CO...

Rhodium-catalyzed asymmetric hydroboration of γ,δ-unsaturated amide derivatives: δ-borylated amides.

Science.gov (United States)

Hoang, G L; Zhang, S; Takacs, J M

2018-05-08

γ,δ-Unsaturated amides in which the alkene moiety bears an aryl or heteroaryl substituent undergo regioselective rhodium-catalyzed δ-borylation by pinacolborane to afford chiral secondary benzylic boronic esters. The results contrast the γ-borylation of γ,δ-unsaturated amides in which the disubstituted alkene moiety bears only alkyl substituents; the reversal in regiochemistry is coupled with a reversal in the sense of π-facial selectivity.

Rhodium mediated bond activation: from synthesis to catalysis

Energy Technology Data Exchange (ETDEWEB)

Ho, Hung-An [Iowa State Univ., Ames, IA (United States)

2012-01-01

Recently, our lab has developed monoanionic tridentate ligand, To^R, showing the corresponding coordination chemistry and catalyst reactivity of magnesium, zirconium, zinc and iridium complexes. This thesis details synthetic chemistry, structural study and catalytic reactivity of the To^R-supported rhodium compounds. Tl[To^R] has been proved to be a superior ligand transfer agent for synthesizing rhodium complexes. The salt metathesis route of Tl[To^M] with [Rh(μ-Cl)(CO)]₂ and [Rh(μ- Cl)(COE)]₂ gives To^MRh(CO)₂ (2.2) and To^MRhH(β³-C₈H₁₃) (3.1) respectively while Tl[To^M] with [Rh(μ-Cl)(CO)]₂ affords To^PRh(CO)₂ (2.3). 2.2 reacts with both strong and weak electrophiles, resulting in the oxazoline N-attacked and the metal center-attacked compounds correspondingly. Using one of the metal center-attacked electrophiles, 2.3 was demonstrated to give high diastereoselectivity. Parallel to COE allylic C-H activation complex 3.1, the propene and allylbenzene allylic C-H activation products have also been synthesized. The subsequent functionalization attempts have been examined by treating with Brønsted acids, Lewis acids, electrophiles, nucleophiles, 1,3-dipolar reagents and reagents containing multiple bonds able to be inserted. Various related complexes have been obtained under these conditions, in which one of the azide insertion compounds reductively eliminates to give an allylic functionalization product stoichiometrically. 3.1 reacts with various primary alcohols to give the decarbonylation dihydride complex To^MRh(H)₂CO (4.1). 4.1 shows catalytic reactivity for primary alcohol decarbonylation under a photolytic condition. Meanwhile, 2.2 has been found to be more reactive than 4.1 for catalytic alcohol decarbonylation under the same condition. Various complexes and primary

Enantioselective Rhodium Enolate Protonations. A New Methodology for the Synthesis of β2-Amino Acids

Science.gov (United States)

Sibi, Mukund P.; Tatamidani, Hiroto; Patil, Kalyani

2008-01-01

Rhodium catalyzed conjugate addition of an aryl boronic acid to α-methylamino acrylates followed by enantioselective protonation of the oxa-π-allylrhodium intermediate provides access to aryl substituted β2-amino acids. The impact of the different variables of the reaction on the levels of enantioselectivity has been assessed. PMID:15957893

3D-atom probe analysis of Cr and Cu added nitriding steels

International Nuclear Information System (INIS)

Takahashi, J.; Kawakami, K.; Sugiyama, M.; Kawasaki, K.

2004-01-01

Full text: Nitriding treatment is a very effective method for hardening the surface of steels and realizing improvement in wear-resistance. Although this technology has been performed for many years, the precipitation and hardening mechanisms are not completely clear. It was not easy to observe very fine precipitates which may be generated in nitriding steels. We performed a three-dimensional atom probe analysis of the nitriding steel plate in which two kinds of precipitates were generated. Hot-rolled steel plates, which mainly contained Cr 1.0wt.% and Cu 1.3wt.%, were nitrided by annealing (550-6000 o ) in a mainly NH 3 atmosphere. The material before the nitriding had a hardness of about 100 Hv. By the nitriding, the surface hardness increased to more than 700 Hv, and the inside hardness also increased to 200 Hv. The specimens were taken from 0.15 mm, 0.3 mm and 0.8 mm depth from the surface, which mostly correspond to the peak, the half and the inside hardness, respectively. In the specimen of 0.8 mm depth, prolate spheroidal Cu precipitates of more than 8 nm in diameter were observed. In the specimen of 0.3 mm depth, plate-shape nitride precipitates of 6-10 nm in diameter were observed in addition to the Cu precipitates. Each Cu precipitate made a pair with the nitride precipitate. In the 0.15 mm depth specimen, Cr nitride precipitates of high volume density in addition to the pairs consisting of a Cu precipitate and a Cr nitride precipitate were observed. The size of the nitride precipitate forming the pair was slightly larger than that of the single Cr nitride precipitates. Furthermore, the denuded zone where the nitride precipitate does not exist was observed around the pairs. From these results, it was concluded that three stages of precipitation arose as follows: By the heat treatment of nitriding processing, Cu precipitates were generated first. Then, Cr nitride nucleated at the surface of the Cu precipitates inhomogeneously, and surrounding solute Cr was

Intermolecular rhodium-catalyzed [2 + 2 + 2] carbocyclization reactions of 1,6-enynes with symmetrical and unsymmetrical alkynes†

Science.gov (United States)

Andrew Evans, P.; Sawyer, James R.; Lai, Kwong Wah; Huffman, John C.

2006-01-01

The crossed intermolecular rhodium-catalyzed [2 + 2 + 2] carbocyclization of carbon and heteroatom tethered 1,6-enynes can be accomplished with symmetrical and unsymmetrical alkynes, to afford the corresponding bicyclohexadienes in an efficient and highly selective manner. PMID:16075089

The Advanced Aluminum Nitride Synthesis Methods and Its Applications: Patent Review.

Science.gov (United States)

Shishkin, Roman A; Elagin, Andrey A; Mayorova, Ekaterina S; Beketov, Askold R

2016-01-01

High purity nanosized aluminum nitride synthesis is a current issue for both industry and science. However, there is no up-to-date review considering the major issues and the technical solutions for different methods. This review aims to investigate the advanced methods of aluminum nitride synthesis and its development tendencies. Also the aluminum nitride application patents and prospects for development of the branch have been considered. The patent search on "aluminum nitride synthesis" has been carried out. The research activity has been analyzed. Special attention has been paid to the patenting geography and the leading researchers in aluminum nitride synthesis. Aluminum nitride synthesis methods have been divided into 6 main groups, the most studied approaches are carbothermal reduction (88 patents) and direct nitridation (107 patents). The current issues for each group have been analyzed; the main trends are purification of the final product and nanopowder synthesis. The leading researchers in aluminum nitride synthesis have represented 5 countries, namely: Japan, China, Russia, South Korea and USA. The main aluminum nitride application spheres are electronics (59,1 percent of applications) and new materials manufacturing (30,9 percent). The review deals with the state of the art data in nanosized aluminum nitride synthesis, the major issues and the technical solutions for different synthesis methods. It gives a full understanding of the development tendencies and of the current leaders in the sphere.

Fabrication of Aluminum Gallium Nitride/Gallium Nitride MESFET And It's Applications in Biosensing

Science.gov (United States)

Alur, Siddharth

Gallium Nitride has been researched extensively for the past three decades for its application in Light Emitting Diodes (LED's), power devices and UV photodetectors. With the recent developments in crystal growth technology and the ability to control the doping there has been an increased interest in heterostructures formed between Gallium nitride and it's alloy Aluminium Gallium Nitride. These heterostructures due to the combined effect of spontaneous and piezoelectric effect can form a high density and a high mobility electron gas channel without any intentional doping. This high density electron gas makes these heterostructures ideal to be used as sensors. Gallium Nitride is also chemically very stable. Detection of biomolecules in a fast and reliable manner is very important in the areas of food safety and medical research. For biomolecular detection it is paramount to have a robust binding of the probes on the sensor surface. Therefore, in this dissertation, the fabrication and application of the AlGaN/GaN heterostructures as biological sensors for the detection of DNA and Organophosphate hydrolase enzyme is discussed. In order to use these AlGaN/GaN heterostructures as biological sensors capable of working in a liquid environment photodefinable polydimethyl-siloxane is used as an encapsulant. The immobilization conditions for a robust binding of thiolated DNA and the catalytic receptor enzyme organophosphate hydrolase on gold surfaces is developed with the help of X-ray photoelectron spectroscopy. DNA and OPH are detected by measuring the change in the drain current of the device as a function of time.

Trans-Selective Rhodium Catalysed Conjugate Addition of Organoboron Reagents to Dihydropyranones

Directory of Open Access Journals (Sweden)

Hannah J. Edwards

2015-04-01

Full Text Available The selective synthesis of 2,6-trans-tetrahydropyran derivatives employing the rhodium catalysed addition of organoboron reagents to dihydropyranone templates, derived from a zinc-catalysed hetero-Diels-Alder reaction, is reported. The addition of both arylboronic acids and potassium alkenyltrifluoroborates have been accomplished in high yields using commercially-available [Rh(cod(OH]2 catalyst. The selective formation of the 2,6-trans-tetrahydropyran stereoisomer is consistent with a mechanism involving alkene association and carbometalation on the less hindered face of the dihydropyranone.

Enantioselective rhodium enolate protonations. A new methodology for the synthesis of beta2-amino acids.

Science.gov (United States)

Sibi, Mukund P; Tatamidani, Hiroto; Patil, Kalyani

2005-06-23

[reaction: see text] Rhodium-catalyzed conjugate addition of an aryl boronic acid to alpha-methylamino acrylates followed by enantioselective protonation of the oxa-pi-allylrhodium intermediate provides access to aryl-substituted beta(2)-amino acids. The impact of the different variables of the reaction on the levels of enantioselectivity has been assessed.

The divergent synthesis of nitrogen heterocycles by rhodium(II)-catalyzed cycloadditions of 1-sulfonyl 1,2,3-triazoles with 1,3-dienes.

Science.gov (United States)

Shang, Hai; Wang, Yuanhao; Tian, Yu; Feng, Juan; Tang, Yefeng

2014-05-26

The first rhodium(II)-catalyzed aza-[4+3] cycloadditions of 1-sulfonyl 1,2,3-triazoles with 1,3-dienes have been developed, and enable the efficient synthesis of highly functionalized 2,5-dihydroazepines from readily available precursors. In some cases, the reaction pathway could divert to formal aza-[3+2] cycloadditions, thus leading to 2,3-dihydropyrroles. In this context, the titled reaction represents a capable tool for the divergent synthesis of two types of synthetically valuable aza-heterocycles from common rhodium(II) iminocarbene intermediates. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

One-pot synthesis of 2,5-dihydropyrroles from terminal alkynes, azides, and propargylic alcohols by relay actions of copper, rhodium, and gold.

Science.gov (United States)

Miura, Tomoya; Tanaka, Takamasa; Matsumoto, Kohei; Murakami, Masahiro

2014-12-01

Relay actions of copper, rhodium, and gold formulate a one-pot multistep pathway, which directly gives 2,5-dihydropyrroles starting from terminal alkynes, sulfonyl azides, and propargylic alcohols. Initially, copper-catalyzed 1,3-dipolar cycloaddition of terminal alkynes with sulfonyl azides affords 1-sulfonyl-1,2,3-triazoles, which then react with propargylic alcohols under the catalysis of rhodium. The resulting alkenyl propargyl ethers subsequently undergo the thermal Claisen rearrangement to give α-allenyl-α-amino ketones. Finally, a gold catalyst prompts 5-endo cyclization to produce 2,5-dihydropyrroles. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Plasma nitriding of CA-6NM steel: effect of H2 + N2 gas mixtures in nitride layer formation for low N2 contents at 500 ºC

Directory of Open Access Journals (Sweden)

Angela Nardelli Allenstein

2010-12-01

Full Text Available This work aims to characterize the phases, thickness, hardness and hardness profiles of the nitride layers formed on the CA-6NM martensitic stainless steel which was plasma nitrided in gas mixtures containing different nitrogen amounts. Nitriding was performed at 500 ºC temperature, and 532 Pa (4 Torr pressure, for gas mixtures of 5% N2 + 95% H2, 10% N2 + 90% H2, and 20% N2 + 80% H2, and 2 hours nitriding time. A 6 hours nitriding time condition for gas mixture of 5% N2 + 95% H2 was also studied. Nitrided samples results were compared with non-nitrided condition. Thickness and microstructure of the nitrided layers were characterized by optical microscopy (OM, using Villela and Nital etchants, and the phases were identified by X-ray diffraction. Hardness profiles and hardness measured on surface steel were determined using Vickers hardness and nanoindentation tester, respectively. It was verified that nitrided layer produced in CA-6NM martensitc stainless steel is constituted of compound layer, being that formation of the diffusion zone was not observed for the studied conditions. The higher the nitrogen amounts in gas mixture the higher is the thickness of the nitrided layer and the probability to form different nitride phases, in the case γ'-Fe4N, ε-Fe2-3N and CrN phases. Intrinsic hardness of the nitrided layers produced in the CA-6NM stainless steel is about 12-14 GPa (~1200-1400 HV.

Ion nitriding in 316=L stainless steel

International Nuclear Information System (INIS)

Rojas-Calderon, E.L.

1989-01-01

Ion nitriding is a glow discharge process that is used to induce surface modification in metals. It has been applied to 316-L austenitic stainless steel looking for similar benefits already obtained in other steels. An austenitic stainless steel was selected because is not hardenable by heat treatment and is not easy to nitride by gas nitriding. The samples were plastically deformed to 10, 20, 40, 50 AND 70% of their original thickness in order to obtain bulk hardening and to observe nitrogen penetration dependence on it. The results were: an increase of one to two rockwell hardness number (except in 70% deformed sample because of its thickness); an increase of even several hundreds per cent in microhardness knoop number in nitrided surface. The later surely modifies waste resistance which would be worth to quantify in further studies. Microhardness measured in an internal transversal face to nitrided surface had a gradual diminish in its value with depth. Auger microanalysis showed a higher relative concentration rate C N /C F e near the surface giving evidence of nitrogen presence till 250 microns deep. The color metallography etchant used, produced faster corrosion in nitrited regions. Therefore, corrosion studies have to be done before using ion nitrited 316-L under these chemicals. (Author)

UN2−x layer formed on uranium metal by glow plasma nitriding

International Nuclear Information System (INIS)

Long, Zhong; Hu, Yin; Chen, Lin; Luo, Lizhu; Liu, Kezhao; Lai, Xinchun

2015-01-01

Highlights: • We used a very simple method to prepare nitride layer on uranium metal surface. • This modified layer is nitrogen-rich nitride, which should be written as UN 2−x . • TEM images show the nitride layer is composed of nano-sized grains. • XPS analysis indicates there is uranium with abnormal low valence in the nitride. - Abstract: Glow plasma nitriding is a simple and economical surface treatment method, and this technology was used to prepare nitride layer on the surface of uranium metal with thickness of several microns. The composition and structure of the nitride layer were analyzed by AES and XRD, indicating that this modified layer is nitrogen-rich uranium nitride, which should be written as UN 2−x . TEM images show the nitride layer is composed of nano-sized grains, with compact structure. And XPS analysis indicates there is uranium with abnormal low valence existing in the nitride. After the treated uranium storage in air for a long time, oxygen just entered the surface several nanometers, showing the nitride layer has excellent oxidation resistance. The mechanism of nitride layer formation and low valence uranium appearance is discussed

Problems and possibilities of development of boron nitride ceramics

International Nuclear Information System (INIS)

Rusanova, L.N.; Romashin, A.G.; Kulikova, G.I.; Golubeva, O.P.

1988-01-01

The modern state of developments in the field of technology of ceramics produced from boron nitride is analyzed. Substantial difficulties in production of pure ceramics from hexagonal and wurtzite-like boron nitride are stated as related to the structure peculiarities and inhomogeneity of chemical bonds in elementary crystal cells of various modifications. Advantages and disadvantages of familiar technological procedures in production of boron nitride ceramics are compared. A new technology is suggested, which is based on the use of electroorganic compounds for hardening and protection of porous high-purity boron-nitride die from oxidation, and as high-efficient sintered elements for treatment of powders of various structures and further pyrolisis. The method is called thermal molecular lacing (TML). Properties of ceramics produced by the TML method are compared with characteristics of well-known brands of boron nitride ceramics

Development of nitride fuel and pyrochemical process for transmutation of minor actinides

International Nuclear Information System (INIS)

Arai, Yasuo; Akabori, Mitsuo; Minato, Kazuo; Uno, Masayoshi

2010-01-01

Nitride fuel cycle for transmutation of minor actinides has been investigated under the double-strata fuel cycle concept. Mononitride solid solutions containing minor actinides have been prepared and characterised. Thermo-physical properties, such as thermal expansion, heat capacity and thermal diffusivity, have been measured by use of minor actinide nitride and burn-up simulated nitride samples. Irradiation behaviour of nitride fuel has been examined by irradiation tests. Pyrochemical process for treatment of spent nitride fuel has been investigated mainly by electrochemical measurements and nitride formation behaviour in pyrochemical process has been studied for recycled fuel fabrication. Recent results of experimental study on nitride fuel and pyrochemical process are summarised in the paper. (authors)

Corrosion fatigue behaviour of ion nitrided AISI 4140 steel

Energy Technology Data Exchange (ETDEWEB)

Genel, K. [Sakarya Univ., Adapazari (Turkey). Mech. Eng. Dept.; Demirkol, M.; Guelmez, T. [Faculty of Mechanical Engineering, Istanbul Technical University, Guemuessuyu, 80191, Istanbul (Turkey)

2000-08-31

Machine components suffer from corrosion degradation of fatigue characteristics and improvement can be attained by the application of a nitriding treatment, particularly to low alloy steels. In the present study, the effect of ion nitriding on corrosion fatigue performance of AISI 4140 steel has been investigated by conducting a series of rotary bending corrosion fatigue tests at 95 Hz, in 3% NaCl aqueous solution. Hourglass shaped, 4 mm diameter fatigue specimens were ion nitrided at 748 K for 1, 3, 8 and 16 h prior to the tests. It was observed that distinct fatigue limit behaviour of ion nitrided steel in air completely disappeared in corrosive environment besides severe degradation in fatigue characteristics. An improvement reaching to 60% in corrosion fatigue strength can be attained by successive ion nitriding practice based on a fatigue life of 10{sup 7} cycles. An attempt was made to establish an empirical relationship between corrosion fatigue strength and relative case depth, which considers the size of the ion nitrided specimen. It was also determined that a power relationship holds between corrosion fatigue strength and fatigue life of ion nitrided steel. The presence of white layer has resulted in additional improvement in corrosion fatigue resistance, and it was observed that corrosion fatigue cracks were initiated dominantly under the white layer by pit formation mechanism. (orig.)

Corrosion fatigue behaviour of ion nitrided AISI 4140 steel

International Nuclear Information System (INIS)

Genel, K.

2000-01-01

Machine components suffer from corrosion degradation of fatigue characteristics and improvement can be attained by the application of a nitriding treatment, particularly to low alloy steels. In the present study, the effect of ion nitriding on corrosion fatigue performance of AISI 4140 steel has been investigated by conducting a series of rotary bending corrosion fatigue tests at 95 Hz, in 3% NaCl aqueous solution. Hourglass shaped, 4 mm diameter fatigue specimens were ion nitrided at 748 K for 1, 3, 8 and 16 h prior to the tests. It was observed that distinct fatigue limit behaviour of ion nitrided steel in air completely disappeared in corrosive environment besides severe degradation in fatigue characteristics. An improvement reaching to 60% in corrosion fatigue strength can be attained by successive ion nitriding practice based on a fatigue life of 10 7 cycles. An attempt was made to establish an empirical relationship between corrosion fatigue strength and relative case depth, which considers the size of the ion nitrided specimen. It was also determined that a power relationship holds between corrosion fatigue strength and fatigue life of ion nitrided steel. The presence of white layer has resulted in additional improvement in corrosion fatigue resistance, and it was observed that corrosion fatigue cracks were initiated dominantly under the white layer by pit formation mechanism. (orig.)

Radiofrequency cold plasma nitrided carbon steel: Microstructural and micromechanical characterizations

International Nuclear Information System (INIS)

Bouanis, F.Z.; Bentiss, F.; Bellayer, S.; Vogt, J.B.; Jama, C.

2011-01-01

Highlights: → C38 carbon steel samples were plasma nitrided using a radiofrequency (rf) nitrogen plasma discharge. → RF plasma treatment enables nitriding for non-heated substrates. → The morphological and chemical analyses show the formation of a uniform thickness on the surface of the nitrided C38 steel. → Nitrogen plasma active species diffuse into the samples and lead to the formation of Fe x N. → The increase in microhardness values for nitrided samples with plasma processing time is interpreted by the formation of a thicker nitrided layer on the steel surface. - Abstract: In this work, C38 carbon steel was plasma nitrided using a radiofrequency (rf) nitrogen plasma discharge on non-heated substrates. General characterizations were performed to compare the chemical compositions, the microstructures and hardness of the untreated and plasma treated surfaces. The plasma nitriding was carried out on non-heated substrates at a pressure of 16.8 Pa, using N 2 gas. Surface characterizations before and after N 2 plasma treatment were performed by means of the electron probe microanalysis (EPMA), X-ray photoelectron spectroscopy (XPS) and Vickers microhardness measurements. The morphological and chemical analysis showed the formation of a uniform structure on the surface of the nitrided sample with enrichment in nitrogen when compared to untreated sample. The thickness of the nitride layer formed depends on the treatment time duration and is approximately 14 μm for 10 h of plasma treatment. XPS was employed to obtain chemical-state information of the plasma nitrided steel surfaces. The micromechanical results show that the surface microhardness increases as the plasma-processing time increases to reach, 1487 HV 0.005 at a plasma processing time of 8 h.

Radiofrequency cold plasma nitrided carbon steel: Microstructural and micromechanical characterizations

Energy Technology Data Exchange (ETDEWEB)

Bouanis, F.Z. [Universite Lille Nord de France, F-59000 Lille (France); Unite Materiaux et Transformations (UMET), Ingenierie des Systemes Polymeres, CNRS UMR 8207, ENSCL, BP 90108, F-59652 Villeneuve d' Ascq Cedex (France); Bentiss, F. [Laboratoire de Chimie de Coordination et d' Analytique, Faculte des Sciences, Universite Chouaib Doukkali, B.P. 20, M-24000 El Jadida (Morocco); Bellayer, S.; Vogt, J.B. [Universite Lille Nord de France, F-59000 Lille (France); Unite Materiaux et Transformations (UMET), Ingenierie des Systemes Polymeres, CNRS UMR 8207, ENSCL, BP 90108, F-59652 Villeneuve d' Ascq Cedex (France); Jama, C., E-mail: charafeddine.jama@ensc-lille.fr [Universite Lille Nord de France, F-59000 Lille (France); Unite Materiaux et Transformations (UMET), Ingenierie des Systemes Polymeres, CNRS UMR 8207, ENSCL, BP 90108, F-59652 Villeneuve d' Ascq Cedex (France)

2011-05-16

Highlights: {yields} C38 carbon steel samples were plasma nitrided using a radiofrequency (rf) nitrogen plasma discharge. {yields} RF plasma treatment enables nitriding for non-heated substrates. {yields} The morphological and chemical analyses show the formation of a uniform thickness on the surface of the nitrided C38 steel. {yields} Nitrogen plasma active species diffuse into the samples and lead to the formation of Fe{sub x}N. {yields} The increase in microhardness values for nitrided samples with plasma processing time is interpreted by the formation of a thicker nitrided layer on the steel surface. - Abstract: In this work, C38 carbon steel was plasma nitrided using a radiofrequency (rf) nitrogen plasma discharge on non-heated substrates. General characterizations were performed to compare the chemical compositions, the microstructures and hardness of the untreated and plasma treated surfaces. The plasma nitriding was carried out on non-heated substrates at a pressure of 16.8 Pa, using N{sub 2} gas. Surface characterizations before and after N{sub 2} plasma treatment were performed by means of the electron probe microanalysis (EPMA), X-ray photoelectron spectroscopy (XPS) and Vickers microhardness measurements. The morphological and chemical analysis showed the formation of a uniform structure on the surface of the nitrided sample with enrichment in nitrogen when compared to untreated sample. The thickness of the nitride layer formed depends on the treatment time duration and is approximately 14 {mu}m for 10 h of plasma treatment. XPS was employed to obtain chemical-state information of the plasma nitrided steel surfaces. The micromechanical results show that the surface microhardness increases as the plasma-processing time increases to reach, 1487 HV{sub 0.005} at a plasma processing time of 8 h.

Rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes.

Science.gov (United States)

Li, Changkun; Kähny, Matthias; Breit, Bernhard

2014-12-08

A rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes to give branched N-allyl 2-pyridones is reported. Preliminary mechanistic studies support the hypothesis that the reaction was initiated from the more acidic 2-hydroxypyridine form, and the initial kinetic O-allylation product was finally converted into the thermodynamically more stable N-allyl 2-pyridones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intrinsic ferromagnetism in hexagonal boron nitride nanosheets

Energy Technology Data Exchange (ETDEWEB)

Si, M. S.; Gao, Daqiang, E-mail: gaodq@lzu.edu.cn, E-mail: xueds@lzu.edu.cn; Yang, Dezheng; Peng, Yong; Zhang, Z. Y.; Xue, Desheng, E-mail: gaodq@lzu.edu.cn, E-mail: xueds@lzu.edu.cn [Key Laboratory for Magnetism and Magnetic Materials of the Ministry of Education, Lanzhou University, Lanzhou 730000 (China); Liu, Yushen [Jiangsu Laboratory of Advanced Functional Materials and College of Physics and Engineering, Changshu Institute of Technology, Changshu 215500 (China); Deng, Xiaohui [Department of Physics and Electronic Information Science, Hengyang Normal University, Hengyang 421008 (China); Zhang, G. P. [Department of Physics, Indiana State University, Terre Haute, Indiana 47809 (United States)

2014-05-28

Understanding the mechanism of ferromagnetism in hexagonal boron nitride nanosheets, which possess only s and p electrons in comparison with normal ferromagnets based on localized d or f electrons, is a current challenge. In this work, we report an experimental finding that the ferromagnetic coupling is an intrinsic property of hexagonal boron nitride nanosheets, which has never been reported before. Moreover, we further confirm it from ab initio calculations. We show that the measured ferromagnetism should be attributed to the localized π states at edges, where the electron-electron interaction plays the role in this ferromagnetic ordering. More importantly, we demonstrate such edge-induced ferromagnetism causes a high Curie temperature well above room temperature. Our systematical work, including experimental measurements and theoretical confirmation, proves that such unusual room temperature ferromagnetism in hexagonal boron nitride nanosheets is edge-dependent, similar to widely reported graphene-based materials. It is believed that this work will open new perspectives for hexagonal boron nitride spintronic devices.

16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

Science.gov (United States)

2010-01-01

... 16 Commercial Practices 1 2010-01-01 2010-01-01 false Misuse of the words âplatinum,â âiridium,â... § 23.7 Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.” (a) It is unfair or deceptive to use the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium...

Structure and electrochemical properties of plasma-nitrided low alloy steel

Energy Technology Data Exchange (ETDEWEB)

Chyou, S.D.; Shih, H.C. (Dept. of Materials Science and Engineering, National Tsing Hua Univ., Hsinchu (Taiwan))

1990-10-01

Plasma-nitrided SAE 4140 steel has been widely applied industrially because of its superior resistance to wear and fatigue. However, its corrosion behaviour in aqueous environments has not been completely explored. The effects of nitriding on corrosion were investigated by performing electrochemical tests on both nitrided and untreated SAE 4140. It was found that, by plasma nitriding, the corrosion resistance improved significantly in HNO{sub 3} and Na{sub 2}SO{sub 4} aqueous environments. A reaction model is proposed to explain the beneficial effect of nitride on corrosion resistance. It is concluded that nitrogen and chromium (an alloying element) act synergistically to form a dense protective layer which is responsible for the corrosion resistance. Characterization of the surface layers by Auger electron spectroscopy and X-ray photoelectron spectroscopy reveals that the protective layer is composed of (Fe, Cr){sub 4}N, (Fe, Cr){sub 2-3}N and CrN in the inner layer, Fe{sub 2}O{sub 3}, Cr{sub 2}O{sub 3} together with nitrides in the middle layer, and nitrides, {gamma}'-FeOOH, and Cr(OH){sub 3}.H{sub 2}O in the outermost layer. (orig.).

Initial Stages in the Rhodium(III)-Catalyzed C-H Bond Activation of Primary Alcohols in Aqueous Solution

DEFF Research Database (Denmark)

Eriksen, J.; Monsted, L.; Monsted, O.

2010-01-01

The mechanism of the catalytic HID exchange in primary alcohol substrates derived from aldopentoses, promoted by a macrocyclic rhodium(III) complex, has been shown to occur by a reversible redox reaction that gives aldehyde and a rhodium hydride complex. Hydride exchange in the latter complex...... promotes the introduction of solvent hydrogen in the primary alcohol formed by the reverse reaction. The hydride complex has been crystallographically characterized as a trifluoromethanesulfonate salt that contains the trans-[Rh(cycb)(H)(OH2)](2+) (cycb = rac-5,5,7,12,12,14-hexamethyl-1......,4,8,11-tetraazacyclotetradecane) cation. The hydride complex is stable for extended periods of time in acidic solution in the absence of oxidants. In basic solutions a series of base-catalyzed reactions take place to yield ultimately the same mixture of [Rh(cycb)(OH)(2)](+) isomers as produced by base hydrolysis of the trans...

A chemical-biological evaluation of rhodium(I) N-heterocyclic carbene complexes as prospective anticancer drugs.

Science.gov (United States)

Oehninger, Luciano; Küster, Laura Nadine; Schmidt, Claudia; Muñoz-Castro, Alvaro; Prokop, Aram; Ott, Ingo

2013-12-23

Rhodium(I) complexes bearing N-heterocyclic carbene (NHC) ligands have been widely used in catalytic chemistry, but there are very few reports of biological properties of these organometallics. A series of Rh(I)-NHC derivatives with 1,5-cyclooctadiene and CO as secondary ligands were synthesized, characterized, and biologically investigated as prospective antitumor drug candidates. Pronounced antiproliferative effects were noted for all complexes, along with moderate inhibitory activity of thioredoxin reductase (TrxR) and efficient binding to biomolecules (DNA, albumin). Biodistribution studies showed that the presence of albumin lowered the cellular uptake and confirmed the transport of rhodium into the nuclei. Changes in the mitochondrial membrane potential (MMP) were observed as well as DNA fragmentation in wild-type and daunorubicin- or vincristine-resistant Nalm-6 leukemia cells. Overall, these studies indicated that Rh(I)-NHC fragments could be used as partial structures of new antitumor agents, in particular in those drugs designed to address resistant malignant tissues. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomic Resolution Microscopy of Nitrides in Steel

DEFF Research Database (Denmark)

Danielsen, Hilmar Kjartansson

2014-01-01

MN and CrMN type nitride precipitates in 12%Cr steels have been investigated using atomic resolution microscopy. The MN type nitrides were observed to transform into CrMN both by composition and crystallography as Cr diffuses from the matrix into the MN precipitates. Thus a change from one...

Defects in dilute nitrides

International Nuclear Information System (INIS)

Chen, W.M.; Buyanova, I.A.; Tu, C.W.; Yonezu, H.

2005-01-01

We provide a brief review our recent results from optically detected magnetic resonance studies of grown-in non-radiative defects in dilute nitrides, i.e. Ga(In)NAs and Ga(Al,In)NP. Defect complexes involving intrinsic defects such as As Ga antisites and Ga i self interstitials were positively identified.Effects of growth conditions, chemical compositions and post-growth treatments on formation of the defects are closely examined. These grown-in defects are shown to play an important role in non-radiative carrier recombination and thus in degrading optical quality of the alloys, harmful to performance of potential optoelectronic and photonic devices based on these dilute nitrides. (author)

Hydrolysis of Letrozole catalyzed by macrocyclic Rhodium (I) Schiff-base complexes.

Science.gov (United States)

Reddy, P Muralidhar; Shanker, K; Srinivas, V; Krishna, E Ravi; Rohini, R; Srikanth, G; Hu, Anren; Ravinder, V

2015-03-15

Ten mononuclear Rhodium (I) complexes were synthesized by macrocyclic ligands having N4 and N2O2 donor sites. Square planar geometry is assigned based on the analytical and spectral properties for all complexes. Rh(I) complexes were investigated as catalysts in hydrolysis of Nitrile group containing pharmaceutical drug Letrozole. A comparative study showed that all the complexes are efficient in the catalysis. The percent yields of all the catalytic reaction products viz. drug impurities were determined by spectrophotometric procedures and characterized by spectral studies. Copyright © 2014 Elsevier B.V. All rights reserved.

Low temperature anodic bonding to silicon nitride

DEFF Research Database (Denmark)

Weichel, Steen; Reus, Roger De; Bouaidat, Salim

2000-01-01

Low-temperature anodic bonding to stoichiometric silicon nitride surfaces has been performed in the temperature range from 3508C to 4008C. It is shown that the bonding is improved considerably if the nitride surfaces are either oxidized or exposed to an oxygen plasma prior to the bonding. Both bu...

Review of actinide nitride properties with focus on safety aspects

Energy Technology Data Exchange (ETDEWEB)

Albiol, Thierry [CEA Cadarache, St Paul Lez Durance Cedex (France); Arai, Yasuo [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

2001-12-01

This report provides a review of the potential advantages of using actinide nitrides as fuels and/or targets for nuclear waste transmutation. Then a summary of available properties of actinide nitrides is given. Results from irradiation experiments are reviewed and safety relevant aspects of nitride fuels are discussed, including design basis accidents (transients) and severe (core disruptive) accidents. Anyway, as rather few safety studies are currently available and as many basic physical data are still missing for some actinide nitrides, complementary studies are proposed. (author)

Colloidal Plasmonic Titanium Nitride Nanoparticles: Properties and Applications

DEFF Research Database (Denmark)

Guler, Urcan; Suslov, Sergey; Kildishev, Alexander V.

2015-01-01

Optical properties of colloidal plasmonic titanium nitride nanoparticles are examined with an eye on their photothermal and photocatalytic applications via transmission electron microscopy and optical transmittance measurements. Single crystal titanium nitride cubic nanoparticles with an average ...

Microstructure and Hardness of High Temperature Gas Nitrided AISI 420 Martensitic Stainless Steel

Directory of Open Access Journals (Sweden)

Ibrahim Nor Nurulhuda Md.

2014-07-01

Full Text Available This study examined the microstructure and hardness of as-received and nitrided AISI 420 martensitic stainless steels. High temperature gas nitriding was employed to treat the steels at 1200°C for one hour and four hours using nitrogen gas, followed by furnace cooled. Chromium nitride and iron nitride were formed and concentrated at the outmost surface area of the steels since this region contained the highest concentration of nitrogen. The grain size enlarged at the interior region of the nitrided steels due to nitriding at temperature above the recrystallization temperature of the steel and followed by slow cooling. The nitrided steels produced higher surface hardness compared to as-received steel due to the presence of nitrogen and the precipitation of nitrides. Harder steel was produced when nitriding at four hours compared to one hour since more nitrogen permeated into the steel.

Influence of plastic deformation on nitriding of a molybdenum-hafnium alloy

International Nuclear Information System (INIS)

Lakhtin, Yu.M.; Kogan, Ya.D.; Shashkov, D.P.; Likhacheva, T.E.

1982-01-01

The influence of a preliminary plastic strain on the structure and properties of molybdenum alloy with 0.2 wt.% Hf upon nitriding in the ammonia medium at 900-1200 deg C during 1-6 h is investigated. The study of microhardness distribution across the nitrided layer thickness has shown that with increase of the degree of preliminary plastic strain up to 50 % the nitrided layer hardness decreases and with further reduction growth up to 90 % - increases. Nitriding sharply (hundred times) increases wear resistance of molybdenum alloy with hafnium addition. At the reduction degree 25 % the wear resistance is less than at other values of percentage reduction in area owing to the minimum thickness of the nitride zone. The alloy strained before nitriding by 25 % has shown the best results during heat resistance testing

Efficient Synthesis of Spirobarbiturates and Spirothiobarbiturates Bearing Cyclopropane Rings by Rhodium(II)-Catalyzed Reactions of Cyclic Diazo Compounds

International Nuclear Information System (INIS)

Wang, Xue; Lee, Yong Rok

2013-01-01

Rhodium(II)-catalyzed reactions of cyclic diazo compounds derived from barbituric acid and thiobarbituric acid with a variety of styrene moieties were examined. These reactions provide rapid synthetic routes to the preparations of spirobarbiturates and spirothiobarbiturates bearing cyclopropane rings

Efficient Synthesis of Spirobarbiturates and Spirothiobarbiturates Bearing Cyclopropane Rings by Rhodium(II)-Catalyzed Reactions of Cyclic Diazo Compounds

Energy Technology Data Exchange (ETDEWEB)

Wang, Xue; Lee, Yong Rok [Yeungnam Univ., Gyeongsan (Korea, Republic of)

2013-06-15

Rhodium(II)-catalyzed reactions of cyclic diazo compounds derived from barbituric acid and thiobarbituric acid with a variety of styrene moieties were examined. These reactions provide rapid synthetic routes to the preparations of spirobarbiturates and spirothiobarbiturates bearing cyclopropane rings.

Structure and properties of nitrided surface layer produced on NiTi shape memory alloy by low temperature plasma nitriding

International Nuclear Information System (INIS)

Czarnowska, Elżbieta; Borowski, Tomasz; Sowińska, Agnieszka; Lelątko, Józef; Oleksiak, Justyna; Kamiński, Janusz; Tarnowski, Michał; Wierzchoń, Tadeusz

2015-01-01

Highlights: • Low temperature plasma nitriding process of NiTi shape memory alloy is presented. • The possibility of treatment details of sophisticated shape. • TiN surface layer has diffusive character. • TiN surface layer increases corrosion resistance of NiTi alloy. • Produced TiN layer modify the biological properties of NiTi alloy. - Abstract: NiTi shape memory alloys are used for bone and cardiological implants. However, on account of the metallosis effect, i.e. the release of the alloy elements into surrounding tissues, they are subjected to various surface treatment processes in order to improve their corrosion resistance and biocompatibility without influencing the required shape memory properties. In this paper, the microstructure, topography and morphology of TiN surface layer on NiTi alloy, and corrosion resistance, both before and after nitriding in low-temperature plasma at 290 °C, are presented. Examinations with the use of the potentiodynamic and electrochemical impedance spectroscopy methods were carried out and show an increase of corrosion resistance in Ringer's solution after glow-discharge nitriding. This surface titanium nitride layer also improved the adhesion of platelets and the proliferation of osteoblasts, which was investigated in in vitro experiments with human cells. Experimental data revealed that nitriding NiTi shape memory alloy under low-temperature plasma improves its properties for bone implant applications

Structure and properties of nitrided surface layer produced on NiTi shape memory alloy by low temperature plasma nitriding

Energy Technology Data Exchange (ETDEWEB)

Czarnowska, Elżbieta [Children' s Memorial Health Institute, Pathology Department, Al. Dzieci Polskich 20, 04-730 Warsaw (Poland); Borowski, Tomasz [Warsaw University of Technology, Faculty of Materials Science and Engineering, Wołoska 141, 02-507 Warsaw (Poland); Sowińska, Agnieszka [Children' s Memorial Health Institute, Pathology Department, Al. Dzieci Polskich 20, 04-730 Warsaw (Poland); Lelątko, Józef [Silesia University, Faculty of Computer Science and Materials Science, 75 Pułku Piechoty 1A, 41-500 Chorzów (Poland); Oleksiak, Justyna; Kamiński, Janusz; Tarnowski, Michał [Warsaw University of Technology, Faculty of Materials Science and Engineering, Wołoska 141, 02-507 Warsaw (Poland); Wierzchoń, Tadeusz, E-mail: twierz@inmat.pw.edu.pl [Warsaw University of Technology, Faculty of Materials Science and Engineering, Wołoska 141, 02-507 Warsaw (Poland)

2015-04-15

Highlights: • Low temperature plasma nitriding process of NiTi shape memory alloy is presented. • The possibility of treatment details of sophisticated shape. • TiN surface layer has diffusive character. • TiN surface layer increases corrosion resistance of NiTi alloy. • Produced TiN layer modify the biological properties of NiTi alloy. - Abstract: NiTi shape memory alloys are used for bone and cardiological implants. However, on account of the metallosis effect, i.e. the release of the alloy elements into surrounding tissues, they are subjected to various surface treatment processes in order to improve their corrosion resistance and biocompatibility without influencing the required shape memory properties. In this paper, the microstructure, topography and morphology of TiN surface layer on NiTi alloy, and corrosion resistance, both before and after nitriding in low-temperature plasma at 290 °C, are presented. Examinations with the use of the potentiodynamic and electrochemical impedance spectroscopy methods were carried out and show an increase of corrosion resistance in Ringer's solution after glow-discharge nitriding. This surface titanium nitride layer also improved the adhesion of platelets and the proliferation of osteoblasts, which was investigated in in vitro experiments with human cells. Experimental data revealed that nitriding NiTi shape memory alloy under low-temperature plasma improves its properties for bone implant applications.

Method of production of hollow silicon nitride articles

International Nuclear Information System (INIS)

Parr, N.L.; Brown, R.L.

1971-01-01

The hollow articles prepared according to the invention have a high density, exhibit no internal stresses and correspond to high demands of tolerance and surface quality. One obtains these by flame spraying silicon powder on a pre-heated form designed with separating agent - e.g. NaCl. After removing the form, the silicon is nitridated to silicon nitride by heating in N 2 or in an atmosphere of ammonia. This process can be interrupted if the article is also to be mechanically processed, and then the nitridation can be completed. (Hoe/LH) [de

Ion beam induces nitridation of silicon

International Nuclear Information System (INIS)

Petravic, M.; Williams, J.S.; Conway, M.

1998-01-01

High dose ion bombardment of silicon with reactive species, such as oxygen and nitrogen, has attracted considerable interest due to possible applications of beam-induced chemical compounds with silicon. For example, high energy oxygen bombardment of Si is now routinely used to form buried oxide layers for device purposes, the so called SIMOX structures. On the other hand, Si nitrides, formed by low energy ( 100 keV) nitrogen beam bombardment of Si, are attractive as oxidation barriers or gate insulators, primarily due to the low diffusivity of many species in Si nitrides. However, little data exists on silicon nitride formation during bombardment and its angle dependence, in particular for N 2 + bombardment in the 10 keV range, which is of interest for analytical techniques such as SIMS. In SIMS, low energy oxygen ions are more commonly used as bombarding species, as oxygen provides stable ion yields and enhances the positive secondary ion yield. Therefore, a large body of data can be found in the literature on oxide formation during low energy oxygen bombardment. Nitrogen bombardment of Si may cause similar effects to oxygen bombardment, as nitrogen and oxygen have similar masses and ranges in Si, show similar sputtering effects and both have the ability to form chemical compounds with Si. In this work we explore this possibility in some detail. We compare oxide and nitride formation during oxygen and nitrogen ion bombardment of Si under similar conditions. Despite the expected similar behaviour, some large differences in compound formation were found. These differences are explained in terms of different atomic diffusivities in oxides and nitrides, film structural differences and thermodynamic properties. (author)

Reversible switching of the sol- gel transition with ultrasound in rhodium(I) and iridium(I) coordination networks

NARCIS (Netherlands)

Paulusse, J.M.J.; Beek, van D.J.M.; Sijbesma, R.P.

2007-01-01

Reversible coordination networks were prepared by combining diphenylphosphinite telechelic polytetrahydrofuran (2) with [RhCl(COD)]2 or [IrCl(COD)]2 in chloroform. Both systems resulted in stable gels at concentrations above 50 and 30 g/L for the rhodium(I) and iridium(I) networks, respectively. The

Plasmonic spectral tunability of conductive ternary nitrides

Energy Technology Data Exchange (ETDEWEB)

Kassavetis, S.; Patsalas, P., E-mail: ppats@physics.auth.gr [Department of Physics, Aristotle University of Thessaloniki, GR-54124 Thessaloniki (Greece); Bellas, D. V.; Lidorikis, E. [Department of Materials Science and Engineering, University of Ioannina, GR-45110 Ioannina (Greece); Abadias, G. [Institut Pprime, Département Physique et Mécanique des Matériaux, Université de Poitiers-CNRS-ENSMA, 86962 Chasseneuil-Futuroscope (France)

2016-06-27

Conductive binary transition metal nitrides, such as TiN and ZrN, have emerged as a category of promising alternative plasmonic materials. In this work, we show that ternary transition metal nitrides such as Ti{sub x}Ta{sub 1−x}N, Ti{sub x}Zr{sub 1−x}N, Ti{sub x}Al{sub 1−x}N, and Zr{sub x}Ta{sub 1−x}N share the important plasmonic features with their binary counterparts, while having the additional asset of the exceptional spectral tunability in the entire visible (400–700 nm) and UVA (315–400 nm) spectral ranges depending on their net valence electrons. In particular, we demonstrate that such ternary nitrides can exhibit maximum field enhancement factors comparable with gold in the aforementioned broadband range. We also critically evaluate the structural features that affect the quality factor of the plasmon resonance and we provide rules of thumb for the selection and growth of materials for nitride plasmonics.

UN{sub 2−x} layer formed on uranium metal by glow plasma nitriding

Energy Technology Data Exchange (ETDEWEB)

Long, Zhong [China Academy of Engineering Physics, P.O. Box 919-71, Mianyang 621907 (China); Hu, Yin [Science and Technology on Surface Physics and Chemistry Laboratory, P.O. Box 718-35, Mianyang 621907 (China); Chen, Lin [China Academy of Engineering Physics, P.O. Box 919-71, Mianyang 621907 (China); Luo, Lizhu [Science and Technology on Surface Physics and Chemistry Laboratory, P.O. Box 718-35, Mianyang 621907 (China); Liu, Kezhao, E-mail: liukz@hotmail.com [Science and Technology on Surface Physics and Chemistry Laboratory, P.O. Box 718-35, Mianyang 621907 (China); Lai, Xinchun, E-mail: lai319@yahoo.com [Science and Technology on Surface Physics and Chemistry Laboratory, P.O. Box 718-35, Mianyang 621907 (China)

2015-01-25

Highlights: • We used a very simple method to prepare nitride layer on uranium metal surface. • This modified layer is nitrogen-rich nitride, which should be written as UN{sub 2−x}. • TEM images show the nitride layer is composed of nano-sized grains. • XPS analysis indicates there is uranium with abnormal low valence in the nitride. - Abstract: Glow plasma nitriding is a simple and economical surface treatment method, and this technology was used to prepare nitride layer on the surface of uranium metal with thickness of several microns. The composition and structure of the nitride layer were analyzed by AES and XRD, indicating that this modified layer is nitrogen-rich uranium nitride, which should be written as UN{sub 2−x}. TEM images show the nitride layer is composed of nano-sized grains, with compact structure. And XPS analysis indicates there is uranium with abnormal low valence existing in the nitride. After the treated uranium storage in air for a long time, oxygen just entered the surface several nanometers, showing the nitride layer has excellent oxidation resistance. The mechanism of nitride layer formation and low valence uranium appearance is discussed.

Nitridation of porous GaAs by an ECR ammonia plasma

International Nuclear Information System (INIS)

Naddaf, M; Hullavarad, S S; Ganesan, V; Bhoraskar, S V

2006-01-01

The effect of surface porosity of GaAs on the nature of growth of GaN, by use of plasma nitridation of GaAs, has been investigated. Porous GaAs samples were prepared by anodic etching of n-type (110) GaAs wafers in HCl solution. Nitridation of porous GaAs samples were carried out by using an electron-cyclotron resonance-induced ammonia plasma. The formation of mixed phases of GaN was investigated using the grazing angle x-ray diffraction method. A remarkable improvement in the intensity of photoluminescence (PL) compared with that of GaN synthesized by direct nitriding of GaAs surface has been observed. The PL intensity of nitrided porous GaAs at the temperature of 380 deg. C was found to be about two orders of magnitude higher as compared with the directly nitrided GaAs at the temperature of 500 deg. C. The changes in the morphology of nitrided porous GaAs have been investigated using both scanning electron microscopy and atomic force microscopy

Nitridation of porous GaAs by an ECR ammonia plasma

Energy Technology Data Exchange (ETDEWEB)

Naddaf, M [Center for Advanced Studies in Material Science and Solid State Physics, University of Pune, Pune 411 007 (India); Department of Physics, Atomic Energy Commission of Syria, PO Box 6091, Damascus (Syrian Arab Republic); Hullavarad, S S [Center for Superconductivity Research, Department of Physics, University of Maryland, College Park, MD 20742 (United States); Ganesan, V [Inter University Consortium, Indore (India); Bhoraskar, S V [Center for Advanced Studies in Material Science and Solid State Physics, University of Pune, Pune 411 007 (India)

2006-02-15

The effect of surface porosity of GaAs on the nature of growth of GaN, by use of plasma nitridation of GaAs, has been investigated. Porous GaAs samples were prepared by anodic etching of n-type (110) GaAs wafers in HCl solution. Nitridation of porous GaAs samples were carried out by using an electron-cyclotron resonance-induced ammonia plasma. The formation of mixed phases of GaN was investigated using the grazing angle x-ray diffraction method. A remarkable improvement in the intensity of photoluminescence (PL) compared with that of GaN synthesized by direct nitriding of GaAs surface has been observed. The PL intensity of nitrided porous GaAs at the temperature of 380 deg. C was found to be about two orders of magnitude higher as compared with the directly nitrided GaAs at the temperature of 500 deg. C. The changes in the morphology of nitrided porous GaAs have been investigated using both scanning electron microscopy and atomic force microscopy.

Nitridation of porous GaAs by an ECR ammonia plasma

Science.gov (United States)

Naddaf, M.; Hullavarad, S. S.; Ganesan, V.; Bhoraskar, S. V.

2006-02-01

The effect of surface porosity of GaAs on the nature of growth of GaN, by use of plasma nitridation of GaAs, has been investigated. Porous GaAs samples were prepared by anodic etching of n-type (110) GaAs wafers in HCl solution. Nitridation of porous GaAs samples were carried out by using an electron-cyclotron resonance-induced ammonia plasma. The formation of mixed phases of GaN was investigated using the grazing angle x-ray diffraction method. A remarkable improvement in the intensity of photoluminescence (PL) compared with that of GaN synthesized by direct nitriding of GaAs surface has been observed. The PL intensity of nitrided porous GaAs at the temperature of 380 °C was found to be about two orders of magnitude higher as compared with the directly nitrided GaAs at the temperature of 500 °C. The changes in the morphology of nitrided porous GaAs have been investigated using both scanning electron microscopy and atomic force microscopy.

Rhodium in car exhaust tips by total automatic activation analysis

International Nuclear Information System (INIS)

Grass, F.; Westphal, G.P.; Lemmel, H.; Sterba, J.

2007-01-01

Exhaust systems of modern cars contain catalysts for the reduction of CO, NO x and hydrocarbons. These catalysts are made of ceramic materials with a large surface on which platinum metals catalyse the oxidation. The catalysts contain approximately 2 g of platinum and 0.4 g of rhodium. Recently platinum is being replaced by palladium. During driving the platinum-group elements (PGEs) are expelled from the tip in fine particles and are deposited in the environment. For a projected study of emissions from cars driven on streets and highways it is important to know which elements can be measured by short time activation analysis without any chemical procedure. (author)

Analysis of mechanical properties of steel 1045 plasma nitriding: with and without tempering

International Nuclear Information System (INIS)

Machado, N.T.B.; Passos, M.L.M. dos; Riani, J.C.; Recco, A.A.C.

2014-01-01

The purpose of this study was to evaluate the possibility of tempering during the nitriding of AISI 1045 steel. The objective was to evaluate the possibility of eliminating this phase, with the nitriding properties remaining unaltered. For this, three parameter samples were compared: quenched, tempered and nitrided for 2h; quenching and nitrided for 2h and quenching and nitrided for 4h. The analysis techniques used for characterizing the samples before and after nitriding were optical microscopy, hardness Rockwell C (HRC), scanning electron microscopy (SEM), X-ray diffraction (XRD). Results showed that phase γ is the most favorable of all parameters tested. The hardness assays showed that samples with different initial hardness (with and without tempering) and even nitriding time showed similar mechanical properties. This fact suggests that the tempering process occurred parallel to the nitriding process. (author)

Surface Area, and Oxidation Effects on Nitridation Kinetics of Silicon Powder Compacts

Science.gov (United States)

Bhatt, R. T.; Palczer, A. R.

1998-01-01

Commercially available silicon powders were wet-attrition-milled from 2 to 48 hr to achieve surface areas (SA's) ranging from 1.3 to 70 sq m/g. The surface area effects on the nitridation kinetics of silicon powder compacts were determined at 1250 or 1350 C for 4 hr. In addition, the influence of nitridation environment, and preoxidation on nitridation kinetics of a silicon powder of high surface area (approximately equals 63 sq m/g) was investigated. As the surface area increased, so did the percentage nitridation after 4 hr in N2 at 1250 or 1350 C. Silicon powders of high surface area (greater than 40 sq m/g) can be nitrided to greater than 70% at 1250 C in 4 hr. The nitridation kinetics of the high-surface-area powder compacts were significantly delayed by preoxidation treatment. Conversely, the nitridation environment had no significant influence on the nitridation kinetics of the same powder. Impurities present in the starting powder, and those accumulated during attrition milling, appeared to react with the silica layer on the surface of silicon particles to form a molten silicate layer, which provided a path for rapid diffusion of nitrogen and enhanced the nitridation kinetics of high surface area silicon powder.

Synthesis and characterization of group V metal carbide and nitride catalysts

Science.gov (United States)

Kwon, Heock-Hoi

1998-11-01

Group V transition metal carbides and nitrides were prepared via the temperature programmed reaction (TPR) of corresponding oxides with NHsb3 or a CHsb4/Hsb2 mixture. Except for the tantalum compounds, phase-pure carbides and nitrides were prepared. The vanadium carbides and nitrides were the most active and selective catalysts. Therefore the principal focus of the research was the preparation, characterization, and evaluation of high surface area vanadium nitride catalysts. A series of vanadium nitrides with surface areas up to 60 msp2/g was prepared. Thermal gravimetric analysis coupled with x-ray diffraction and scanning electron microscopy indicated that the solid-state reaction proceeded by the sequential reduction of Vsb2Osb5 to VOsb{0.9} and concluded with the topotactic substitution of nitrogen for oxygen in VOsb{0.9}. The transformation of Vsb2Osb5 to VN was pseudomorphic. An experimental design was executed to determine effects of the heating rates and space velocities on the VN microstructures. The heating rates had minor effects on the surface areas and pore size distributions; however, increasing the space velocity significantly increased the surface area. The materials were mostly mesoporous. Oxygen chemisorption on the vanadium nitrides scaled linearly with the surface area. The corresponding O/Vsbsurface ratio was ≈0.6. The vanadium nitrides were active for butane activation and pyridine hydrodenitrogenation. During butane activation, their selectivities towards dehydrogenation products were as high as 98%. The major product in pyridine hydrodenitrogenation was pentane. The reaction rates increased almost linearly with the surface area suggesting that these reactions were structure insensitive. The vanadium nitrides were not active for crotonaldehyde hydrogenation; however, they catalyzed an interesting ring formation reaction that produced methylbenzaldehyde and xylene from crotonaldehyde. A new method was demonstrated for the production of very

Surface enrichment with chrome and nitriding of IF steel under an abnormal glow discharge

International Nuclear Information System (INIS)

Meira, S.R.; Borges, P.C.; Bernardelli, E.A.

2014-01-01

The objective of this work is to evaluate the influence of surface enrichment of IF steel with chrome, and nitriding, the formation of the nitrided layer. Thus, IF steel samples were subjected to surface enrichment process, using 409 stainless steel as a target for sputtering, followed by plasma nitriding, both under a dc abnormal glow discharge. The enrichment treatment was operated at 1200 ° C for 3h. The nitriding treatment was operated at 510 ° C for 2 h. The influence of the treatments on the layers formed was studied through optical microscopy (OM), scan electron microscopy (SEM), X-ray diffraction (XRD) and Vickers microindentation. The results show that the enrichment is effective to enrich the IF surface, furthermore, improves the characteristics of nitriding, comparing nitriding samples to nitriding and enriched, was observed needles of nitrides, as well as a higher hardness, which is associated with the nitrides of chrome, on the nitriding and enriched samples. (author)

Continuum modelling for carbon and boron nitride nanostructures

International Nuclear Information System (INIS)

Thamwattana, Ngamta; Hill, James M

2007-01-01

Continuum based models are presented here for certain boron nitride and carbon nanostructures. In particular, certain fullerene interactions, C 60 -C 60 , B 36 N 36 -B 36 N 36 and C 60 -B 36 N 36 , and fullerene-nanotube oscillator interactions, C 60 -boron nitride nanotube, C 60 -carbon nanotube, B 36 N 36 -boron nitride nanotube and B 36 N 36 -carbon nanotube, are studied using the Lennard-Jones potential and the continuum approach, which assumes a uniform distribution of atoms on the surface of each molecule. Issues regarding the encapsulation of a fullerene into a nanotube are also addressed, including acceptance and suction energies of the fullerenes, preferred position of the fullerenes inside the nanotube and the gigahertz frequency oscillation of the inner molecule inside the outer nanotube. Our primary purpose here is to extend a number of established results for carbon to the boron nitride nanostructures

Comparative study involving the uranium determination through catalytic reduction of nitrates and nitrides by using decoupled plasma nitridation (DPN)

International Nuclear Information System (INIS)

Aguiar, Marco Antonio Souza; Gutz, Ivano G. Rolf

1999-01-01

This paper reports a comparative study on the determination of uranium through the catalytic reduction of nitrate and nitride using the decoupled plasma nitridation. The uranyl ions are a good catalyst for the reduction of NO - 3 and NO - 2 ions on the surface of a hanging drop mercury electrode (HDME). The presence of NO - in a solution with p H = 3 presented a catalytic signal more intense than the signal obtained with NO - 3 (concentration ten times higher). A detection limit of 1x10 9 M was obtained using the technique of decoupled plasma nitridation (DPN), suggesting the development of a sensitive way for the determination of uranium in different matrixes

Synthesis of graphitic carbon nitride by reaction of melamine and uric acid

International Nuclear Information System (INIS)

Dante, Roberto C.; Martin-Ramos, Pablo; Correa-Guimaraes, Adriana; Martin-Gil, Jesus

2011-01-01

Highlights: → Graphitic carbon nitrides by CVD of melamine and uric acid on alumina. → The building blocks of carbon nitrides are heptazine nuclei. → Composite particles with alumina core and carbon nitride coating. - Abstract: Graphitic carbon nitrides were synthesized starting from melamine and uric acid. Uric acid was chosen because it thermally decomposes, and reacts with melamine by condensation at temperatures in the range of 400-600 deg. C. The reagents were mixed with alumina and subsequently the samples were treated in an oven under nitrogen flux. Alumina favored the deposition of the graphitic carbon nitrides layers on the exposed surface. This method can be assimilated to an in situ chemical vapor deposition (CVD). Infrared (IR) spectra, as well as X-ray diffraction (XRD) patterns, are in accordance with the formation of a graphitic carbon nitride with a structure based on heptazine blocks. These carbon nitrides exhibit poor crystallinity and a nanometric texture, as shown by transmission electron microscopy (TEM) analysis. The thermal degradation of the graphitic carbon nitride occurs through cyano group formation, and involves the bridging tertiary nitrogen and the bonded carbon, which belongs to the heptazine ring, causing the ring opening and the consequent network destruction as inferred by connecting the IR and X-ray photoelectron spectroscopy (XPS) results. This seems to be an easy and promising route to synthesize graphitic carbon nitrides. Our final material is a composite made of an alumina core covered by carbon nitride layers.

Study of heat transfer parameters on rhodium target for 103Pd production

International Nuclear Information System (INIS)

Sadeghi, M.; Tenreiro, C.; Van den Winkel, P.

2009-01-01

The efficiency of cooling and the particle beam characteristics are important when high beam current irradiations are intended for production of radionuclides. The efficiency of cooling is determined by both the target carrier geometry and the flow rate of coolant, while the beam characteristics deal with the current density distribution on the irradiated surface area. Heat transfer on rhodium target to produce 103 Pd via the 103 Rh(p,n) 103 Pd reaction was investigated and the beam current was obtained more than 500 μA. (authors)

Some new aspects of microstructural development during sintering of silicon nitride

International Nuclear Information System (INIS)

Feuer, H.; Woetting, G.; Gugel, E.

1994-01-01

The mechanical properties of silicon nitride ceramics strongly depend on their microstructure. However, there is still a lively discussion about the parameters controlling the microstructural development. The current research was stimulated by the observation that a bimodal grain-size distribution in dense silicon nitride has a very beneficial effect on the mechanical properties, especially on the fracture toughness. This paper is focused on the relationship between the α-β-transformation and the densification of silicon nitride powders with different characteristics and sintering additives. Effects of β-grains originally present in the silicon nitride powder, of added β-silicon nitride seeds and of β-crystals formed by the α/β-transformation on the resulting microstructure and on the properties are discussed. The results are summarised in a model describing prerequisites and processing conditions, which are necessary to achieve a bimodal microstructure, i. e. a self-reinforced silicon nitride ceramic. (orig.)

Hot carrier dynamics in plasmonic transition metal nitrides

Science.gov (United States)

Habib, Adela; Florio, Fred; Sundararaman, Ravishankar

2018-06-01

Extraction of non-equilibrium hot carriers generated by plasmon decay in metallic nano-structures is an increasingly exciting prospect for utilizing plasmonic losses, but the search for optimum plasmonic materials with long-lived carriers is ongoing. Transition metal nitrides are an exciting class of new plasmonic materials with superior thermal and mechanical properties compared to conventional noble metals, but their suitability for plasmonic hot carrier applications remains unknown. Here, we present fully first principles calculations of the plasmonic response, hot carrier generation and subsequent thermalization of all group IV, V and VI transition metal nitrides, fully accounting for direct and phonon-assisted transitions as well as electron–electron and electron–phonon scattering. We find the largest frequency ranges for plasmonic response in ZrN, HfN and WN, between those of gold and silver, while we predict strongest absorption in the visible spectrum for the VN, NbN and TaN. Hot carrier generation is dominated by direct transitions for most of the relevant energy range in all these nitrides, while phonon-assisted processes dominate only below 1 eV plasmon energies primarily for the group IV nitrides. Finally, we predict the maximum hot carrier lifetimes to be around 10 fs for group IV and VI nitrides, a factor of 3–4 smaller than noble metals, due to strong electron–phonon scattering. However, we find longer carrier lifetimes for group V nitrides, comparable to silver for NbN and TaN, while exceeding 100 fs (twice that of silver) for VN, making them promising candidates for efficient hot carrier extraction.

Iron Carbides and Nitrides: Ancient Materials with Novel Prospects.

Science.gov (United States)

Ye, Zhantong; Zhang, Peng; Lei, Xiang; Wang, Xiaobai; Zhao, Nan; Yang, Hua

2018-02-07

Iron carbides and nitrides have aroused great interest in researchers, due to their excellent magnetic properties, good machinability and the particular catalytic activity. Based on these advantages, iron carbides and nitrides can be applied in various areas such as magnetic materials, biomedical, photo- and electrocatalysis. In contrast to their simple elemental composition, the synthesis of iron carbides and nitrides still has great challenges, particularly at the nanoscale, but it is usually beneficial to improve performance in corresponding applications. In this review, we introduce the investigations about iron carbides and nitrides, concerning their structure, synthesis strategy and various applications from magnetism to the catalysis. Furthermore, the future prospects are also discussed briefly. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Role of the Element Rhodium in the Hyperbolic Law of the Periodic Table of Elements

Directory of Open Access Journals (Sweden)

Albert Khazan

2008-07-01

Full Text Available The role of the element rhodium as an independent affirmation of calculations by the Hyperbolic Law and validity of all its relations is shown herein. The deviation in calculation by this method of the atomic mass of heaviest element is 0.0024%, and its coefficient of scaling 0.001-0.005%.

Tribological properties of plasma and pulse plasma nitrided AISI 4140 steel

Energy Technology Data Exchange (ETDEWEB)

Podgornik, B.; Vizintin, J. [Ljubljana Univ. (Slovenia). Center of Tribology and Tech. Diagnostics; Leskovsek, V. [Inst. of Metals and Technologies, Ljubljana (Slovenia)

1998-10-10

Plasma nitriding is usually used for ferrous materials to improve their surface properties. Knowledge of the properties of thin surface layers is essential for designing engineering components with optimal wear performance. In our study, we investigated the microstructural, mechanical and tribological properties of plasma- and pulse plasma-nitrided AISI 4140 steel in comparison to hardened steel. The influence of nitriding case depth as well as the presence of a compound layer on its tribological behaviour was also examined. Plasma and pulse plasma nitriding were carried out using commercial nitriding processes. Nitrided samples were fully characterised, using metallographic, SEM microscopic, microhardness and profilometric techniques, before and after wear testing. Wear tests were performed on a pin-on-disc wear testing machine in which nitrided pins were mated to hardened ball bearing steel discs. The wear tests were carried out under dry conditions where hardened samples were used as a reference. The resulting wear loss as well as the coefficient of friction was monitored as a function of load and test time. Several microscopic techniques were used to analyse the worn surfaces and wear debris in order to determine the dominant friction and wear characteristics. Results showed improved tribological properties of AISI 4140 steel after plasma and pulse plasma nitriding compared to hardening. However, the compound layer should be removed from the surface by mechanical means or by decreasing the amount of nitrogen in the nitriding atmosphere, to avoid impairment of the tribological properties by fracture of the hard and brittle compound layer followed by the formation of hard abrasive particles. (orig.) 10 refs.

Microstructure and antibacterial properties of microwave plasma nitrided layers on biomedical stainless steels

International Nuclear Information System (INIS)

Lin, Li-Hsiang; Chen, Shih-Chung; Wu, Ching-Zong; Hung, Jing-Ming; Ou, Keng-Liang

2011-01-01

Nitriding of AISI 303 austenitic stainless steel using microwave plasma system at various temperatures was conducted in the present study. The nitrided layers were characterized via scanning electron microscopy, glancing angle X-ray diffraction, transmission electron microscopy and Vickers microhardness tester. The antibacterial properties of this nitrided layer were evaluated. During nitriding treatment between 350 deg. C and 550 deg. C, the phase transformation sequence on the nitrided layers of the alloys was found to be γ → (γ + γ N ) → (γ + α + CrN). The analytical results revealed that the surface hardness of AISI 303 stainless steel could be enhanced with the formation of γ N phase in nitriding process. Antibacterial test also demonstrated the nitrided layer processed the excellent antibacterial properties. The enhanced surface hardness and antibacterial properties make the nitrided AISI 303 austenitic stainless steel to be one of the essential materials in the biomedical applications.

Electronic structure and mechanical properties of plasma nitrided ferrous alloys

Energy Technology Data Exchange (ETDEWEB)

Portolan, E. [Centro de Ciencias Exatas e Tecnologia, Universidade de Caxias do Sul, 95070-560 Caxias do Sul-RS (Brazil); Baumvol, I.J.R. [Centro de Ciencias Exatas e Tecnologia, Universidade de Caxias do Sul, 95070-560 Caxias do Sul-RS (Brazil); Instituto de Fisica, Universidade Federal do Rio Grande do Sul, Porto Alegre 91509-970 (Brazil); Figueroa, C.A., E-mail: cafiguer@ucs.br [Centro de Ciencias Exatas e Tecnologia, Universidade de Caxias do Sul, 95070-560 Caxias do Sul-RS (Brazil)

2009-04-15

The electronic structures of the near-surface regions of two different nitrided steels (AISI 316 and 4140) were investigated using X-ray photoelectron spectroscopy. Photoelectron groups from all main chemical elements involved were addressed for steel samples with implanted-N concentrations in the range 16-32 at.%. As the implanted-N concentrations were increased, rather contrasting behaviors were observed for the two kinds of steel. The N1s photoelectrons had spectral shifts toward lower (nitrided AISI 316) or higher (nitrided AISI 4140) binding energies, whereas the Fe2p{sub 3/2} photoelectron spectrum remains at a constant binding energy (nitrided AISI 316) or shifts toward higher binding energies (AISI 4140). These trends are discussed in terms of the metallic nitride formation and the overlapping of atomic orbitals. For nitrided AISI 316, a semi-classical approach of charge transfer between Cr and N is used to explain the experimental facts (formation of CrN), while for nitrided AISI 4140 we propose that the interaction between orbitals 4s from Fe and 2p from N promotes electrons to the conduction band increasing the electrical attraction of the N1s and Fe2p electrons in core shells (formation of FeN{sub x}). The increase in hardness of the steel upon N implantation is attributed to the localization of electrons in specific bonds, which diminishes the metallic bond character.

Electronic structure and mechanical properties of plasma nitrided ferrous alloys

Science.gov (United States)

Portolan, E.; Baumvol, I. J. R.; Figueroa, C. A.

2009-04-01

The electronic structures of the near-surface regions of two different nitrided steels (AISI 316 and 4140) were investigated using X-ray photoelectron spectroscopy. Photoelectron groups from all main chemical elements involved were addressed for steel samples with implanted-N concentrations in the range 16-32 at.%. As the implanted-N concentrations were increased, rather contrasting behaviors were observed for the two kinds of steel. The N1s photoelectrons had spectral shifts toward lower (nitrided AISI 316) or higher (nitrided AISI 4140) binding energies, whereas the Fe2p 3/2 photoelectron spectrum remains at a constant binding energy (nitrided AISI 316) or shifts toward higher binding energies (AISI 4140). These trends are discussed in terms of the metallic nitride formation and the overlapping of atomic orbitals. For nitrided AISI 316, a semi-classical approach of charge transfer between Cr and N is used to explain the experimental facts (formation of CrN), while for nitrided AISI 4140 we propose that the interaction between orbitals 4s from Fe and 2p from N promotes electrons to the conduction band increasing the electrical attraction of the N1s and Fe2p electrons in core shells (formation of FeN x). The increase in hardness of the steel upon N implantation is attributed to the localization of electrons in specific bonds, which diminishes the metallic bond character.

Electronic structure and mechanical properties of plasma nitrided ferrous alloys

International Nuclear Information System (INIS)

Portolan, E.; Baumvol, I.J.R.; Figueroa, C.A.

2009-01-01

The electronic structures of the near-surface regions of two different nitrided steels (AISI 316 and 4140) were investigated using X-ray photoelectron spectroscopy. Photoelectron groups from all main chemical elements involved were addressed for steel samples with implanted-N concentrations in the range 16-32 at.%. As the implanted-N concentrations were increased, rather contrasting behaviors were observed for the two kinds of steel. The N1s photoelectrons had spectral shifts toward lower (nitrided AISI 316) or higher (nitrided AISI 4140) binding energies, whereas the Fe2p 3/2 photoelectron spectrum remains at a constant binding energy (nitrided AISI 316) or shifts toward higher binding energies (AISI 4140). These trends are discussed in terms of the metallic nitride formation and the overlapping of atomic orbitals. For nitrided AISI 316, a semi-classical approach of charge transfer between Cr and N is used to explain the experimental facts (formation of CrN), while for nitrided AISI 4140 we propose that the interaction between orbitals 4s from Fe and 2p from N promotes electrons to the conduction band increasing the electrical attraction of the N1s and Fe2p electrons in core shells (formation of FeN x ). The increase in hardness of the steel upon N implantation is attributed to the localization of electrons in specific bonds, which diminishes the metallic bond character.

Study of activation cross-sections of deuteron induced reactions on rhodium up to 40 MeV

International Nuclear Information System (INIS)

Ditroi, F.; Tarkanyi, F.; Takacs, S.; Hermanne, A.; Yamazaki, H.; Baba, M.; Mohammadi, A.; Ignatyuk, A.V.

2011-01-01

Highlights: → Excitation function measurement of deuteron induced reactions on rhodium up to 40 MeV. → Model code calculations with EMPIRE, ALICE and TALYS. → Integral production yield calculation. → Thin layer activation (TLA) with the produced isotopes. - Abstract: In the frame of a systematic study of the activation cross-sections of deuteron induced nuclear reactions, excitation functions of the 103 Rh(d,x) 100,101,103 Pd, 100g,101m,101g,102m,102g Rh and 103g Ru reactions were determined up to 40 MeV. Cross-sections were measured with the activation method using a stacked foil irradiation technique. Excitation functions of the contributing reactions were calculated using the ALICE-IPPE, EMPIRE-II and TALYS codes. From the measured cross-section data integral production yields were calculated and compared with experimental integral yield data reported in the literature. From the measured cross-sections and previous data, activation curves were deduced to support thin layer activation (TLA) on rhodium and Rh containing alloys.

Fabrication of carbide and nitride pellets and the nitride irradiations Niloc 1 and Niloc 2

International Nuclear Information System (INIS)

Blank, H.

1991-01-01

Besides the relatively well-known advanced LMFBR mixed carbide fuel an advanced mixed nitride is also an attractive candidate for the optimised fuel cycle of the European Fast Reactor, but the present knowledge about the nitride is still insufficient and should be raised to the level of the carbide. For such an optimised fuel cycle the following general conditions have been set up for the fuel: (i) the burnup of the optimised MN and MC should be at least 15 a/o or even beyond, at moderate linear ratings of less than 75 kW/m (ii) the fuel will be used in a He-bonding pin concept and (iii) as far as available an advanced economic pellet fabrication method should be employed. (iv) The fuel structure must contain 15 - 20% porosity in order to accomodate the fission product swelling at high burnup. This report gives a comprehensive description of fuel and pellet fabrication and characterization, irradiation, and post-irradiation examination. From the results important conclusions can be drawn about future work on nitrides

Magnetic properties of Nd3(Fe,Mo)29 compound and its nitride

International Nuclear Information System (INIS)

Pan Hongge

1998-01-01

The iron-rich ternary intermetallic compound Nd 3 (Fe,Mo) 29 with the Nd 3 (Fe,Ti) 29 -type monoclinic structure and its nitride were prepared. After nitrogenation, the nitride retains the structure of the parent compound, but the unit-cell volume of the nitride is 5.9% greater than that of the parent compound. The Curie temperature of Nd 3 (Fe,Mo) 29 nitride is 70.9% higher than that of the parent compound and the saturation magnetization of the nitride is about 6.6% (at 4.2 K) and 23.7% (at 300 K) higher than that of the parent compound. The anisotropy of the nitride is similar to that of parent compound, which exhibits plane anisotropy. (orig.)

Local heating with titanium nitride nanoparticles

DEFF Research Database (Denmark)

Guler, Urcan; Ndukaife, Justus C.; Naik, Gururaj V.

2013-01-01

We investigate the feasibility of titanium nitride (TiN) nanoparticles as local heat sources in the near infrared region, focusing on biological window. Experiments and simulations provide promising results for TiN, which is known to be bio-compatible.......We investigate the feasibility of titanium nitride (TiN) nanoparticles as local heat sources in the near infrared region, focusing on biological window. Experiments and simulations provide promising results for TiN, which is known to be bio-compatible....

Precipitation of Chromium Nitrides in the Super Duplex Stainless Steel 2507

Science.gov (United States)

Pettersson, Niklas; Pettersson, Rachel F. A.; Wessman, Sten

2015-03-01

Precipitation of chromium nitrides during cooling from temperatures in the range 1373 K to 1523 K (1100 °C to 1250 °C) has been studied for the super duplex stainless steel 2507 (UNS S32750). Characterization with optical, scanning and transmission electron microscopy was combined to quantify the precipitation process. Primarily Cr2N nitrides were found to precipitate with a high density in the interior of ferrite grains. An increased cooling rate and/or an increased austenite spacing clearly promoted nitride formation, resulting in precipitation within a higher fraction of the ferrite grains, and lager nitride particles. Furthermore, formation of the meta-stable CrN was induced by higher cooling rates. The toughness seemed unaffected by nitrides. A slight decrease in pitting resistance was, however, noticed for quenched samples with large amounts of precipitates. The limited adverse effect on pitting resistance is attributed to the small size (~200 nm) of most nitrides. Slower cooling of duplex stainless steels to allow nitrogen partitioning is suggested in order to avoid large nitrides, and thereby produce a size distribution with a smaller detrimental effect on pitting resistance.

Gravimetric preparation and characterization of primary reference solutions of molybdenum and rhodium.

Science.gov (United States)

Kaltenbach, Angela; Noordmann, Janine; Görlitz, Volker; Pape, Carola; Richter, Silke; Kipphardt, Heinrich; Kopp, Gernot; Jährling, Reinhard; Rienitz, Olaf; Güttler, Bernd

2015-04-01

Gravimetrically prepared mono-elemental reference solutions having a well-known mass fraction of approximately 1 g/kg (or a mass concentration of 1 g/L) define the very basis of virtually all measurements in inorganic analysis. Serving as the starting materials of all standard/calibration solutions, they link virtually all measurements of inorganic analytes (regardless of the method applied) to the purity of the solid materials (high-purity metals or salts) they were prepared from. In case these solid materials are characterized comprehensively with respect to their purity, this link also establishes direct metrological traceability to The International System of Units (SI). This, in turn, ensures the comparability of all results on the highest level achievable. Several national metrology institutes (NMIs) and designated institutes (DIs) have been working for nearly two decades in close cooperation with commercial producers on making an increasing number of traceable reference solutions available. Besides the comprehensive characterization of the solid starting materials, dissolving them both loss-free and completely under strict gravimetric control is a challenging problem in the case of several elements like molybdenum and rhodium. Within the framework of the European Metrology Research Programme (EMRP), in the Joint Research Project (JRP) called SIB09 Primary standards for challenging elements, reference solutions of molybdenum and rhodium were prepared directly from the respective metals with a relative expanded uncertainty associated with the mass fraction of U rel(w) methods required to assist with the preparation and as dissemination tools.

Anomalous piezoelectricity in two-dimensional graphene nitride nanosheets.

Science.gov (United States)

Zelisko, Matthew; Hanlumyuang, Yuranan; Yang, Shubin; Liu, Yuanming; Lei, Chihou; Li, Jiangyu; Ajayan, Pulickel M; Sharma, Pradeep

2014-06-27

Piezoelectricity is a unique property of materials that permits the conversion of mechanical stimuli into electrical and vice versa. On the basis of crystal symmetry considerations, pristine carbon nitride (C3N4) in its various forms is non-piezoelectric. Here we find clear evidence via piezoresponse force microscopy and quantum mechanical calculations that both atomically thin and layered graphitic carbon nitride, or graphene nitride, nanosheets exhibit anomalous piezoelectricity. Insights from ab inito calculations indicate that the emergence of piezoelectricity in this material is due to the fact that a stable phase of graphene nitride nanosheet is riddled with regularly spaced triangular holes. These non-centrosymmetric pores, and the universal presence of flexoelectricity in all dielectrics, lead to the manifestation of the apparent and experimentally verified piezoelectric response. Quantitatively, an e11 piezoelectric coefficient of 0.758 C m(-2) is predicted for C3N4 superlattice, significantly larger than that of the commonly compared α-quartz.

Alkaline fuel cell with nitride membrane

Science.gov (United States)

Sun, Shen-Huei; Pilaski, Moritz; Wartmann, Jens; Letzkus, Florian; Funke, Benedikt; Dura, Georg; Heinzel, Angelika

2017-06-01

The aim of this work is to fabricate patterned nitride membranes with Si-MEMS-technology as a platform to build up new membrane-electrode-assemblies (MEA) for alkaline fuel cell applications. Two 6-inch wafer processes based on chemical vapor deposition (CVD) were developed for the fabrication of separated nitride membranes with a nitride thickness up to 1 μm. The mechanical stability of the perforated nitride membrane has been adjusted in both processes either by embedding of subsequent ion implantation step or by optimizing the deposition process parameters. A nearly 100% yield of separated membranes of each deposition process was achieved with layer thickness from 150 nm to 1 μm and micro-channel pattern width of 1μm at a pitch of 3 μm. The process for membrane coating with electrolyte materials could be verified to build up MEA. Uniform membrane coating with channel filling was achieved after the optimization of speed controlled dip-coating method and the selection of dimethylsulfoxide (DMSO) as electrolyte solvent. Finally, silver as conductive material was defined for printing a conductive layer onto the MEA by Ink-Technology. With the established IR-thermography setup, characterizations of MEAs in terms of catalytic conversion were performed successfully. The results of this work show promise for build up a platform on wafer-level for high throughput experiments.

Research and development of nitride fuel cycle technology in Japan

International Nuclear Information System (INIS)

Minato, Kazuo; Arai, Yasuo; Akabori, Mitsuo; Tamaki, Yoshihisa; Itoh, Kunihiro

2004-01-01

The research on the nitride fuel was started for an advanced fuel, (U, Pn)N, for fast reactors, and the research activities have been expanded to minor actinide bearing nitride fuels. The fuel fabrication, property measurements, irradiation tests and pyrochemical process experiments have been made. In 2002 a five-year-program named PROMINENT was started for the development of nitride fuel cycle technology within the framework of the Development of Innovative Nuclear Technologies by the Ministry of Education, Culture, Sports, Science and Technology of Japan. In the research program PROMINENT, property measurements, pyrochemical process and irradiation experiments needed for nitride fuel cycle technology are being made. (author)

The preparation of high-adsorption, spherical, hexagonal boron nitride by template method

Energy Technology Data Exchange (ETDEWEB)

Zhang, Ning, E-mail: zhangning5832@163.com; Liu, Huan; Kan, Hongmin; Wang, Xiaoyang; Long, Haibo; Zhou, Yonghui

2014-11-15

Highlights: • The high-adsorption, spherical, hexagonal boron nitride powders were prepared. • The influence mechanism of template content on the micro-morphology and adsorption was explored. • At appropriate synthesis temperature, higher adsorption mesoporous spheres h-BN began to form. - Abstract: This research used low-cost boric acid and borax as a source of boron, urea as a nitrogen source, dodecyl-trimethyl ammonium chloride (DTAC) as a template, and thus prepared different micro-morphology hexagonal boron nitride powders under a flowing ammonia atmosphere at different nitriding temperatures. The effects of the template content and nitriding temperature on the micro-morphology of hexagonal boron nitride were studied and the formation mechanism analysed. The influences of the template content and nitriding temperature on adsorption performance were also explored. The results showed that at a nitriding temperature of 675 °C, the micro-morphologies of h-BN powder were orderly, inhomogeneous spherical, uniform spherical, beam, and pie-like with increasing template content. The micro-morphology was inhomogeneous spherical at a DTAC dose of 7.5%. The micro-morphology was uniform spherical at a DTAC dose of 10%. At a DTAC dose of 12%, the micro-morphology was a mixture of beam and pie-like shapes. At a certain template content (DTAC at 10%) and at lower nitriding temperatures (625 °C and 650 °C), spherical shell structures with surface subsidence began to form. The porous spheres would appear at a nitriding temperature of 675 °C, and the ball diameter thus formed was approximately 500–600 nm. The ball diameter was about 600–700 nm when the nitriding temperature was 700 °C. At a nitriding temperature of 725 °C, the ball diameter was between 800 and 1000 nm and sintering necking started to form. When the relative pressure was higher, previously closed pores opened and connected with the outside world: the adsorption then increased significantly. The

White light-emitting diodes (LEDs) using (oxy)nitride phosphors

International Nuclear Information System (INIS)

Xie, R-J; Hirosaki, N; Sakuma, K; Kimura, N

2008-01-01

(Oxy)nitride phosphors have attracted great attention recently because they are promising luminescent materials for phosphor-converted white light-emitting diodes (LEDs). This paper reports the luminescent properties of (oxy)nitride phosphors in the system of M-Si-Al-O-N (M = Li, Ca or Sr), and optical properties of white LEDs using a GaN-based blue LED and (oxy)nitride phosphors. The phosphors show high conversion efficiency of blue light, suitable emission colours and small thermal quenching. The bichromatic white LEDs exhibit high luminous efficacy (∼55 lm W -1 ) and the multi-phosphor converted white LEDs show high colour rendering index (Ra 82-95). The results indicate that (oxy)nitride phosphors demonstrate their superior suitability to use as down-conversion luminescent materials in white LEDs

Corrosion stability of cermets on the base of titanium nitride

International Nuclear Information System (INIS)

Kajdash, O.N.; Marinich, M.A.; Kuzenkova, M.A.; Manzheleev, I.V.

1991-01-01

Corrosion resistance of titanium nitride and its cermets in 5% of HCl, 7% of HNO 3 , 10% of H 2 SO 4 is studied. It is established that alloys TiN-Ni-Mo alloyed with chromium (from 10 to 15%) possess the highest corrosion resistance. Cermet TiN-Cr has the higher stability than titanium nitride due to formation of binary nitride (Ti, Cr)N

Microstructural characterization of pulsed plasma nitrided 316L stainless steel

International Nuclear Information System (INIS)

Asgari, M.; Barnoush, A.; Johnsen, R.; Hoel, R.

2011-01-01

Highlights: → The low temperature pulsed plasma nitrided layer of 316 SS was studied. → The plastic deformation induced in the austenite due to nitriding is characterized by EBSD at different depths (i.e., nitrogen concentration). → Nanomechanical properties of the nitride layer was investigated by nanoindentation at different depths (i.e., nitrogen concentration). → High hardness, high nitrogen concentration and high dislocation density is detected in the nitride layer. → The hardness and nitrogen concentration decreased sharply beyond the nitride layer. - Abstract: Pulsed plasma nitriding (PPN) treatment is one of the new processes to improve the surface hardness and tribology behavior of austenitic stainless steels. Through low temperature treatment (<440 deg. C), it is possible to obtain unique combinations of wear and corrosion properties. Such a combination is achieved through the formation of a so-called 'extended austenite phase'. These surface layers are often also referred to as S-phase, m-phase or γ-phase. In this work, nitrided layers on austenitic stainless steels AISI 316L (SS316L) were examined by means of a nanoindentation method at different loads. Additionally, the mechanical properties of the S-phase at different depths were studied. Electron back-scatter diffraction (EBSD) examination of the layer showed a high amount of plasticity induced in the layer during its formation. XRD results confirmed the formation of the S-phase, and no deleterious CrN phase was detected.

Rhodium(III)-catalyzed three-component reaction of imines, alkynes, and aldehydes through C-H activation.

Science.gov (United States)

Huang, Ji-Rong; Song, Qiang; Zhu, Yu-Qin; Qin, Liu; Qian, Zhi-Yong; Dong, Lin

2014-12-15

An efficient rhodium(III)-catalyzed tandem three-component reaction of imines, alkynes and aldehydes through CH activation has been developed. High stereo- and regioselectivity, as well as good yields were obtained in most cases. The simple and atom-economical approach offers a broad scope of substrates, providing polycyclic skeletons with potential biological properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface modification of austenitic steel by various glow-discharge nitriding methods

Directory of Open Access Journals (Sweden)

Tomasz Borowski

2015-09-01

Full Text Available Recent years have seen intensive research on modifying glow-discharge nitriding processes. One of the most commonly used glow-discharge methods includes cathodic potential nitriding (conventional method, and active screen plasma nitriding. Each of these methods has a number of advantages. One very important, common feature of these techniques is full control of the microstructure, chemical and phase composition, thickness and the surface topography of the layers formed. Another advantage includes the possibility of nitriding such materials as: austenitic steels or nickel alloys, i.e. metallic materials which do not diffuse nitrogen as effectively as ferritic or martensitic steels. However, these methods have some disadvantages as well. In the case of conventional plasma nitriding, engineers have to deal with the edge effect, which makes it difficult to use this method for complexly shaped components. In turn, in the case of active screen plasma nitriding, the problem disappears. A uniform, smooth layer forms, but is thinner, softer and is not as resistant to friction compared to layers formed using the conventional method. Research is also underway to combine these methods, i.e. use an active screen in conventional plasma nitriding at cathodic potential. However, there is a lack of comprehensive data presenting a comparison between these three nitriding processes and the impact of pulsating current on the formation of the microstructure and functional properties of austenitic steel surfaces. The article presents a characterisation of nitrided layers produced on austenitic X2CrNiMo17-12-2 (AISI 316L stainless steel in the course of glow-discharge nitriding at cathodic potential, at plasma potential and at cathodic potential incorporating an active screen. All processes were carried out at 440 °C under DC glow-discharge conditions and in 100 kHz frequency pulsating current. The layers were examined in terms of their microstructure, phase and

Two-Dimensional Modeling of Aluminum Gallium Nitride/Gallium Nitride High Electron Mobility Transistor

National Research Council Canada - National Science Library

Holmes, Kenneth

2002-01-01

Gallium Nitride (GaN) High Electron Mobility Transistors (HEMT's) are microwave power devices that have the performance characteristics to improve the capabilities of current and future Navy radar and communication systems...

Gold film with gold nitride - A conductor but harder than gold

International Nuclear Information System (INIS)

Siller, L.; Peltekis, N.; Krishnamurthy, S.; Chao, Y.; Bull, S.J.; Hunt, M.R.C.

2005-01-01

The formation of surface nitrides on gold films is a particularly attractive proposition, addressing the need to produce harder, but still conductive, gold coatings which reduce wear but avoid the pollution associated with conventional additives. Here we report production of large area gold nitride films on silicon substrates, using reactive ion sputtering and plasma etching, without the need for ultrahigh vacuum. Nanoindentation data show that gold nitride films have a hardness ∼50% greater than that of pure gold. These results are important for large-scale applications of gold nitride in coatings and electronics

The Effect of Polymer Char on Nitridation Kinetics of Silicon

Science.gov (United States)

Chan, Rickmond C.; Bhatt, Ramakrishna T.

1994-01-01

Effects of polymer char on nitridation kinetics of attrition milled silicon powder have been investigated from 1200 to 1350 C. Results indicate that at and above 1250 C, the silicon compacts containing 3.5 wt percent polymer char were fully converted to Si3N4 after 24 hr exposure in nitrogen. In contrast, the silicon compacts without polymer char could not be fully converted to Si3N4 at 1350 C under similar exposure conditions. At 1250 and 1350 C, the silicon compacts with polymer char showed faster nitridation kinetics than those without the polymer char. As the polymer char content is increased, the amount of SiC in the nitrided material is also increased. By adding small amounts (approx. 2.5 wt percent) of NiO, the silicon compacts containing polymer char can be completely nitrided at 1200 C. The probable mechanism for the accelerated nitridation of silicon containing polymer char is discussed.

Isolation and characterization of a uranium(VI)-nitride triple bond

Science.gov (United States)

King, David M.; Tuna, Floriana; McInnes, Eric J. L.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.

2013-06-01

The nature and extent of covalency in uranium bonding is still unclear compared with that of transition metals, and there is great interest in studying uranium-ligand multiple bonds. Although U=O and U=NR double bonds (where R is an alkyl group) are well-known analogues to transition-metal oxo and imido complexes, the uranium(VI)-nitride triple bond has long remained a synthetic target in actinide chemistry. Here, we report the preparation of a uranium(VI)-nitride triple bond. We highlight the importance of (1) ancillary ligand design, (2) employing mild redox reactions instead of harsh photochemical methods that decompose transiently formed uranium(VI) nitrides, (3) an electrostatically stabilizing sodium ion during nitride installation, (4) selecting the right sodium sequestering reagent, (5) inner versus outer sphere oxidation and (6) stability with respect to the uranium oxidation state. Computational analyses suggest covalent contributions to U≡N triple bonds that are surprisingly comparable to those of their group 6 transition-metal nitride counterparts.

Preparation and chemical stability of iron-nitride-coated iron microparticles

International Nuclear Information System (INIS)

Luo Xin; Liu Shixiong

2007-01-01

Iron-nitride-coated iron microparticles were prepared by nitridation of the surface of iron microparticles with ammonia gas at a temperature of 510 deg. C. The phases, composition, morphology, magnetic properties, and chemical stability of the particles were studied. The phases were α-Fe, ε-Fe 3 N, and γ-Fe 4 N. The composition varied from the core to the surface, with 99.8 wt% Fe in the core, and 93.8 wt% Fe and 6 wt% N in the iron-nitride coating. The thickness of the iron-nitride coating was about 0.28 μm. The chemical stability of the microparticles was greatly improved, especially the corrosion resistance in corrosive aqueous media. The saturation magnetization and the coercive force were 17.1x10 3 and 68 kA/m, respectively. It can be concluded that iron-nitride-coated iron microparticles will be very useful in many fields, such as water-based magnetorheological fluids and polishing fluids

An assessment of the thermodynamic properties of uranium nitride, plutonium nitride and uranium-plutonium mixed nitride

International Nuclear Information System (INIS)

Matsui, T.; Ohse, R.W.

1986-01-01

Thermodynamic properties such as vapour pressures, heat capacities and enthalpies of formation for UN(s), PuN(s) and (U, Pu)N(s) are critically evaluated. The equations of the vapour pressures and the heat capacities for the three nitrides are assessed. Thermal functions, and thermodynamic functions for the formation of UN(s), PuN(s) and (U, Pu)N(s), are calculated

Low-temperature direct synthesis of mesoporous vanadium nitrides for electrochemical capacitors

Energy Technology Data Exchange (ETDEWEB)

Lee, Hae-Min [Institute of NT-IT Fusion Technology, Ajou University, 206 Worldcup-ro, Yeongtong-gu, Suwon 16499 (Korea, Republic of); Jeong, Gyoung Hwa [Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Banyeon 100, Ulsan 44919 (Korea, Republic of); Kim, Sang-Wook [Department of Molecular Science and Technology, Ajou University, 206 Worldcup-ro, Yeongtong-gu, Suwon 16499 (Korea, Republic of); Kim, Chang-Koo, E-mail: changkoo@ajou.ac.kr [Department of Chemical Engineering and Department of Energy Systems Research, Ajou University, 206 Worldcup-ro, Yeongtong-gu, Suwon 16499 (Korea, Republic of)

2017-04-01

Highlights: • Vanadium nitrides were directly synthesized by a one-step chemical precipitation method. • This method was carried out at a low temperature of 70 °C. • Vanadium nitrides had a specific capacitance of 598 F/g. • The equivalent series resistance of the vanadium nitride electrode was 1.42 Ω after 5000 cycles. - Abstract: Mesoporous vanadium nitrides are directly synthesized by a one-step chemical precipitation method at a low temperature (70 °C). Structural and morphological analyses reveal that vanadium nitride consist of long and slender nanowhiskers, and mesopores with diameters of 2–5 nm. Compositional analysis confirms the presence of vanadium in the VN structure, along with oxidized vanadium. The cyclic voltammetry and charge-discharge tests indicate that the obtained material stores charges via a combination of electric double-layer capacitance and pseudocapacitance mechanisms. The vanadium nitride electrode exhibits a specific capacitance of 598 F/g at a current density of 4 A/g. After 5000 charge-discharge cycles, the electrode has an equivalent series resistance of 1.42 Ω and retains 83% of its initial specific capacitance. This direct low-temperature synthesis of mesoporous vanadium nitrides is a simple and promising method to achieve high specific capacitance and low equivalent series resistance for electrochemical capacitor applications.

Turbostratic boron nitride coated on high-surface area metal oxide templates

DEFF Research Database (Denmark)

Klitgaard, Søren Kegnæs; Egeblad, Kresten; Brorson, M.

2007-01-01

Boron nitride coatings on high-surface area MgAl2O4 and Al2O3 have been synthesized and characterized by transmission electron microscopy and by X-ray powder diffraction. The metal oxide templates were coated with boron nitride using a simple nitridation in a flow of ammonia starting from ammonium...

Intragranular Chromium Nitride Precipitates in Duplex and Superduplex Stainless Steel

OpenAIRE

Iversen, Torunn Hjulstad

2012-01-01

Intragranular chromium nitrides is a phenomenon with detrimental effects on material properties in superduplex stainless steels which have not received much attention. Precipitation of nitrides occurs when the ferritic phase becomes supersaturated with nitrogen and there is insufficient time during cooling for diffusion of nitrogen into austenite. Heat treatment was carried out at between 1060◦C and 1160◦C to study the materials susceptibility to nitride precipitation with...

Electronic Biosensors Based on III-Nitride Semiconductors.

Science.gov (United States)

Kirste, Ronny; Rohrbaugh, Nathaniel; Bryan, Isaac; Bryan, Zachary; Collazo, Ramon; Ivanisevic, Albena

2015-01-01

We review recent advances of AlGaN/GaN high-electron-mobility transistor (HEMT)-based electronic biosensors. We discuss properties and fabrication of III-nitride-based biosensors. Because of their superior biocompatibility and aqueous stability, GaN-based devices are ready to be implemented as next-generation biosensors. We review surface properties, cleaning, and passivation as well as different pathways toward functionalization, and critically analyze III-nitride-based biosensors demonstrated in the literature, including those detecting DNA, bacteria, cancer antibodies, and toxins. We also discuss the high potential of these biosensors for monitoring living cardiac, fibroblast, and nerve cells. Finally, we report on current developments of covalent chemical functionalization of III-nitride devices. Our review concludes with a short outlook on future challenges and projected implementation directions of GaN-based HEMT biosensors.

Bifunctional rhodium intercalator conjugates as mismatch-directing DNA alkylating agents.

Science.gov (United States)

Schatzschneider, Ulrich; Barton, Jacqueline K

2004-07-21

A conjugate of a DNA mismatch-specific rhodium intercalator, containing the bulky chrysenediimine ligand, and an aniline mustard has been prepared, and targeting of mismatches in DNA by this conjugate has been examined. The preferential alkylation of mismatched over fully matched DNA is found by a mobility shift assay at concentrations where untethered organic mustards show little reaction. The binding site of the Rh intercalator was determined by DNA photocleavage, and the position of covalent modification was established on the basis of the enhanced depurination associated with N-alkylation. The site-selective alkylation at mismatched DNA renders these conjugates useful tools for the covalent tagging of DNA base pair mismatches and new chemotherapeutic design.

First principles calculations of interstitial and lamellar rhenium nitrides

Energy Technology Data Exchange (ETDEWEB)

Soto, G., E-mail: gerardo@cnyn.unam.mx [Universidad Nacional Autonoma de Mexico, Centro de Nanociencias y Nanotecnologia, Km 107 Carretera Tijuana-Ensenada, Ensenada Baja California (Mexico); Tiznado, H.; Reyes, A.; Cruz, W. de la [Universidad Nacional Autonoma de Mexico, Centro de Nanociencias y Nanotecnologia, Km 107 Carretera Tijuana-Ensenada, Ensenada Baja California (Mexico)

2012-02-15

Highlights: Black-Right-Pointing-Pointer The possible structures of rhenium nitride as a function of composition are analyzed. Black-Right-Pointing-Pointer The alloying energy is favorable for rhenium nitride in lamellar arrangements. Black-Right-Pointing-Pointer The structures produced by magnetron sputtering are metastable variations. Black-Right-Pointing-Pointer The structures produced by high-pressure high-temperature are stable configurations. Black-Right-Pointing-Pointer The lamellar structures are a new category of interstitial dissolutions. - Abstract: We report here a systematic first principles study of two classes of variable-composition rhenium nitride: i, interstitial rhenium nitride as a solid solution and ii, rhenium nitride in lamellar structures. The compounds in class i are cubic and hexagonal close-packed rhenium phases, with nitrogen in the octahedral and tetrahedral interstices of the metal, and they are formed without changes to the structure, except for slight distortions of the unit cells. In the compounds in class ii, by contrast, the nitrogen inclusion provokes stacking faults in the parent metal structure. These faults create trigonal-prismatic sites where the nitrogen residence is energetically favored. This second class of compounds produces lamellar structures, where the nitrogen lamellas are inserted among multiple rhenium layers. The Re{sub 3}N and Re{sub 2}N phases produced recently by high-temperature and high-pressure synthesis belong to this class. The ratio of the nitrogen layers to the rhenium layers is given by the composition. While the first principle calculations point to higher stability for the lamellar structures as opposed to the interstitial phases, the experimental evidence presented here demonstrates that the interstitial classes are synthesizable by plasma methods. We conclude that rhenium nitrides possess polymorphism and that the two-dimensional lamellar structures might represent an emerging class of materials

First principles calculations of interstitial and lamellar rhenium nitrides

International Nuclear Information System (INIS)

Soto, G.; Tiznado, H.; Reyes, A.; Cruz, W. de la

2012-01-01

Highlights: ► The possible structures of rhenium nitride as a function of composition are analyzed. ► The alloying energy is favorable for rhenium nitride in lamellar arrangements. ► The structures produced by magnetron sputtering are metastable variations. ► The structures produced by high-pressure high-temperature are stable configurations. ► The lamellar structures are a new category of interstitial dissolutions. - Abstract: We report here a systematic first principles study of two classes of variable-composition rhenium nitride: i, interstitial rhenium nitride as a solid solution and ii, rhenium nitride in lamellar structures. The compounds in class i are cubic and hexagonal close-packed rhenium phases, with nitrogen in the octahedral and tetrahedral interstices of the metal, and they are formed without changes to the structure, except for slight distortions of the unit cells. In the compounds in class ii, by contrast, the nitrogen inclusion provokes stacking faults in the parent metal structure. These faults create trigonal-prismatic sites where the nitrogen residence is energetically favored. This second class of compounds produces lamellar structures, where the nitrogen lamellas are inserted among multiple rhenium layers. The Re 3 N and Re 2 N phases produced recently by high-temperature and high-pressure synthesis belong to this class. The ratio of the nitrogen layers to the rhenium layers is given by the composition. While the first principle calculations point to higher stability for the lamellar structures as opposed to the interstitial phases, the experimental evidence presented here demonstrates that the interstitial classes are synthesizable by plasma methods. We conclude that rhenium nitrides possess polymorphism and that the two-dimensional lamellar structures might represent an emerging class of materials within binary nitride chemistry.

On the effect of pre-oxidation on the nitriding kinetics

DEFF Research Database (Denmark)

Friehling, Peter Bernhard; Somers, Marcel A. J.

2000-01-01

The oxidation of ferritic surfaces prior to gaseous nitriding has been reported to lead to improved uniformity of the compound layer thickness and enhanced nitriding kinetics. The present work considers the nucleation and growth of a model compound layer on pure iron and, using previous...... experimental and theoretical work reported in the literature, puts forward two hypotheses to explain the effects of pre-oxidation on compound layer formation. It is proposed that the nucleation of iron nitrides is enhanced by the presence of an iron-oxide layer and that the growth of an iron-nitride layer...... proceeds faster after pre-oxidation, due to a higher nitrogen content in the part of the compound layer closest to the surface....

REGIOSELECTIVE OXIDATIONS OF EQUILENIN DERIVATIVES CATALYZED BY A RHODIUM (III) PORPHYRIN COMPLEX-CONTRAST WITH THE MANGANESE (III) PORPHYRIN. (R826653)

Science.gov (United States)

AbstractEquilenin acetate and dihydroequilenin acetate were oxidized with iodosobenzene and a rhodium(III) porphyrin catalyst. The selectivity of the reactions differs from that with the corresponding Mn(III) catalyst, or from that of free radical chain oxidation.

Plasma nitriding monitoring reactor: A model reactor for studying plasma nitriding processes using an active screen

Science.gov (United States)

Hamann, S.; Börner, K.; Burlacov, I.; Spies, H.-J.; Strämke, M.; Strämke, S.; Röpcke, J.

2015-12-01

A laboratory scale plasma nitriding monitoring reactor (PLANIMOR) has been designed to study the basics of active screen plasma nitriding (ASPN) processes. PLANIMOR consists of a tube reactor vessel, made of borosilicate glass, enabling optical emission spectroscopy (OES) and infrared absorption spectroscopy. The linear setup of the electrode system of the reactor has the advantages to apply the diagnostic approaches on each part of the plasma process, separately. Furthermore, possible changes of the electrical field and of the heat generation, as they could appear in down-scaled cylindrical ASPN reactors, are avoided. PLANIMOR has been used for the nitriding of steel samples, achieving similar results as in an industrial scale ASPN reactor. A compact spectrometer using an external cavity quantum cascade laser combined with an optical multi-pass cell has been applied for the detection of molecular reaction products. This allowed the determination of the concentrations of four stable molecular species (CH4, C2H2, HCN, and NH3). With the help of OES, the rotational temperature of the screen plasma could be determined.

Plasma nitriding monitoring reactor: A model reactor for studying plasma nitriding processes using an active screen

International Nuclear Information System (INIS)

Hamann, S.; Röpcke, J.; Börner, K.; Burlacov, I.; Spies, H.-J.; Strämke, M.; Strämke, S.

2015-01-01

A laboratory scale plasma nitriding monitoring reactor (PLANIMOR) has been designed to study the basics of active screen plasma nitriding (ASPN) processes. PLANIMOR consists of a tube reactor vessel, made of borosilicate glass, enabling optical emission spectroscopy (OES) and infrared absorption spectroscopy. The linear setup of the electrode system of the reactor has the advantages to apply the diagnostic approaches on each part of the plasma process, separately. Furthermore, possible changes of the electrical field and of the heat generation, as they could appear in down-scaled cylindrical ASPN reactors, are avoided. PLANIMOR has been used for the nitriding of steel samples, achieving similar results as in an industrial scale ASPN reactor. A compact spectrometer using an external cavity quantum cascade laser combined with an optical multi-pass cell has been applied for the detection of molecular reaction products. This allowed the determination of the concentrations of four stable molecular species (CH 4 , C 2 H 2 , HCN, and NH 3 ). With the help of OES, the rotational temperature of the screen plasma could be determined

Plasma nitriding monitoring reactor: A model reactor for studying plasma nitriding processes using an active screen

Energy Technology Data Exchange (ETDEWEB)

Hamann, S., E-mail: hamann@inp-greifswald.de; Röpcke, J. [INP-Greifswald, Felix-Hausdorff-Str. 2, 17489 Greifswald (Germany); Börner, K.; Burlacov, I.; Spies, H.-J. [TU Bergakademie Freiberg, Institute of Materials Engineering, Gustav-Zeuner-Str. 5, 09599 Freiberg (Germany); Strämke, M.; Strämke, S. [ELTRO GmbH, Arnold-Sommerfeld-Ring 3, 52499 Baesweiler (Germany)

2015-12-15

A laboratory scale plasma nitriding monitoring reactor (PLANIMOR) has been designed to study the basics of active screen plasma nitriding (ASPN) processes. PLANIMOR consists of a tube reactor vessel, made of borosilicate glass, enabling optical emission spectroscopy (OES) and infrared absorption spectroscopy. The linear setup of the electrode system of the reactor has the advantages to apply the diagnostic approaches on each part of the plasma process, separately. Furthermore, possible changes of the electrical field and of the heat generation, as they could appear in down-scaled cylindrical ASPN reactors, are avoided. PLANIMOR has been used for the nitriding of steel samples, achieving similar results as in an industrial scale ASPN reactor. A compact spectrometer using an external cavity quantum cascade laser combined with an optical multi-pass cell has been applied for the detection of molecular reaction products. This allowed the determination of the concentrations of four stable molecular species (CH{sub 4}, C{sub 2}H{sub 2}, HCN, and NH{sub 3}). With the help of OES, the rotational temperature of the screen plasma could be determined.

The wear and corrosion resistance of shot peened-nitrided 316L austenitic stainless steel

International Nuclear Information System (INIS)

Hashemi, B.; Rezaee Yazdi, M.; Azar, V.

2011-01-01

Research highlights: → Shot peening-nitriding increased the wear resistance and surface hardness of samples. → This treatment improved the surface mechanical properties. → Shot peening alleviates the adverse effects of nitriding on the corrosion behavior. -- Abstract: 316L austenitic stainless steel was gas nitrided at 570 o C with pre-shot peening. Shot peening and nitriding are surface treatments that enhance the mechanical properties of surface layers by inducing compressive residual stresses and formation of hard phases, respectively. The structural phases, micro-hardness, wear behavior and corrosion resistance of specimens were investigated by X-ray diffraction, Vickers micro-hardness, wear testing, scanning electron microscopy and cyclic polarization tests. The effects of shot peening on the nitride layer formation and corrosion resistance of specimens were studied. The results showed that shot peening enhanced the nitride layer formation. The shot peened-nitrided specimens had higher wear resistance and hardness than other specimens. On the other hand, although nitriding deteriorated the corrosion resistance of the specimens, cyclic polarization tests showed that shot peening before the nitriding treatment could alleviate this adverse effect.

Enantioselective Construction of 3-Hydroxypiperidine Scaffolds by Sequential Action of Light and Rhodium upon N-Allylglyoxylamides.

Science.gov (United States)

Ishida, Naoki; Nečas, David; Masuda, Yusuke; Murakami, Masahiro

2015-06-15

3-Hydroxypiperidine scaffolds were enantioselectively constructed in an atom-economical way by sequential action of light and rhodium upon N-allylglyoxylamides. In a formal sense, the allylic C-H bond was selectively cleaved and enantioselectively added across the ketonic carbonyl group with migration of the double bond (carbonyl-ene-type reaction). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Martensitic Stainless Steels Low-temperature Nitriding: Dependence of Substrate Composition

OpenAIRE

Ferreira, Lauro Mariano; Brunatto, Silvio Francisco; Cardoso, Rodrigo Perito

2015-01-01

Low-temperature plasma assisted nitriding is a very promising technique to improve surface mechanical properties of stainless steels, keeping unaltered or even improving their surface corrosion resistance. During treatment, nitrogen diffuses into the steel surface, increasing its hardness and wear resistance. In the present work the nitriding process of different martensitic stainless steels was studied. As-quenched AISI 410, 410NiMo, 416 and 420 stainless steel samples were plasma nitrided a...

Carbonyl complexes of rhodium with N-donor ligands: factors determining the formation of terminal versus bridging carbonyls

NARCIS (Netherlands)

Dzik, W.I.; Creusen, C.; de Gelder, R.; Peters, T.P.J.; Smits, J.M.M.; de Bruin, B.

2010-01-01

Cationic rhodium carbonyl complexes supported by a series of different N-3- and N-4-donor ligands were prepared, and their ability to form carbonyl-bridged species was evaluated. Complex [Rh(K3-bpa)(cod)r (1(+)) (bpa = bis(2-picolyBamine, cod = cis,cis-1,5-cyclooctadiene) reacts with I bar of CO to

Dissolution performance of plutonium nitride based fuel materials

Energy Technology Data Exchange (ETDEWEB)

Aneheim, E.; Hedberg, M. [Nuclear Chemistry, Chemistry and Chemical Engineering, Chalmers University of Technology, Kemivaegen 4, Gothenburg, SE41296 (Sweden)

2016-07-01

Nitride fuels have been regarded as one viable fuel option for Generation IV reactors due to their positive features compared to oxides. To be able to close the fuel cycle and follow the Generation IV concept, nitrides must, however, demonstrate their ability to be reprocessed. This means that the dissolution performance of actinide based nitrides has to be thoroughly investigated and assessed. As the zirconium stabilized nitrides show even better potential as fuel material than does the pure actinide containing nitrides, investigations on the dissolution behavior of both PuN and (Pu,Zr)N has been undertaken. If possible it is desirable to perform the fuel dissolutions using nitric acid. This, as most reprocessing strategies using solvent-solvent extraction are based on a nitride containing aqueous matrix. (Pu,Zr)N/C microspheres were produced using internal gelation. The spheres dissolution performance was investigated using nitric acid with and without additions of HF and Ag(II). In addition PuN fuel pellets were produced from powder and their dissolution performance were also assessed in a nitric acid based setting. It appears that both PuN and (Pu,Zr)N/C fuel material can be completely dissolved in nitric acid of high concentration with the use of catalytic amounts of HF. The amount of HF added strongly affects dissolution kinetics of (Pu, Zr)N and the presence of HF affects the 2 solutes differently, possibly due to inhomogeneity o the initial material. Large additions of Ag(II) can also be used to facilitate the dissolution of (Pu,Zr)N in nitric acid. PuN can be dissolved by pure nitric acid of high concentration at room temperature while (Pu, Zr)N is unaffected under similar conditions. At elevated temperature (reflux), (Pu,Zr)N can, however, also be dissolved by concentrated pure nitric acid.

Plasma nitriding of a precipitation hardening stainless steel to improve erosion and corrosion resistance

International Nuclear Information System (INIS)

Cabo, Amado; Bruhl, Sonia P.; Vaca, Laura S.; Charadia, Raul Charadia

2010-01-01

Precipitation hardening stainless steels are used as structural materials in the aircraft and the chemical industry because of their good combination of mechanical and corrosion properties. The aim of this work is to analyze the structural changes produced by plasma nitriding in the near surface of Thyroplast PH X Supra®, a PH stainless steel from ThyssenKrupp, and to study the effect of nitriding parameters in wear and corrosion resistance. Samples were first aged and then nitriding was carried out in an industrial facility at two temperatures, with two different nitrogen partial pressures in the gas mixture. After nitriding, samples were cut, polished, mounted in resin and etched with Vilella reagent to reveal the nitrided case. Nitrided structure was also analyzed with XRD. Erosion/Corrosion was tested against sea water and sand flux, and corrosion in a salt spray fog (ASTM B117). All nitrided samples presented high hardness. Samples nitrided at 390 deg C with different nitrogen partial pressure showed similar erosion resistance against water and sand flux. The erosion resistance of the nitrided samples at 500 deg C was the highest and XRD revealed nitrides. Corrosion resistance, on the contrary, was diminished; the samples suffered of general corrosion during the salt spray fog test. (author)

Molecular dynamics studies of actinide nitrides

International Nuclear Information System (INIS)

Kurosaki, Ken; Uno, Masayoshi; Yamanaka, Shinsuke; Minato, Kazuo

2004-01-01

The molecular dynamics (MD) calculation was performed for actinide nitrides (UN, NpN, and PuN) in the temperature range from 300 to 2800 K to evaluate the physical properties viz., the lattice parameter, thermal expansion coefficient, compressibility, and heat capacity. The Morse-type potential function added to the Busing-Ida type potential was employed for the ionic interactions. The interatomic potential parameters were determined by fitting to the experimental data of the lattice parameter. The usefulness and applicability of the MD method to evaluate the physical properties of actinide nitrides were studied. (author)

Performance analysis of nitride alternative plasmonic materials for localized surface plasmon applications

DEFF Research Database (Denmark)

Guler, U.; Naik, G. V.; Boltasseva, Alexandra

2012-01-01

. Titanium nitride and zirconium nitride, which were recently suggested as alternative plasmonic materials in the visible and near-infrared ranges, are compared to the performance of gold. In contrast to the results from quasistatic methods, both nitride materials are very good alternatives to the usual...

Modification of Low-Alloy Steel Surface by High-Temperature Gas Nitriding Plus Tempering

Science.gov (United States)

Jiao, Dongling; Li, Minsong; Ding, Hongzhen; Qiu, Wanqi; Luo, Chengping

2018-02-01

The low-alloy steel was nitrided in a pure NH3 gas atmosphere at 640 660 °C for 2 h, i.e., high-temperature gas nitriding (HTGN), followed by tempering at 225 °C, which can produce a high property surface coating without brittle compound (white) layer. The steel was also plasma nitriding for comparison. The composition, microstructure and microhardness of the nitrided and tempered specimens were examined, and their tribological behavior investigated. The results showed that the as-gas-nitrided layer consisted of a white layer composed of FeN0.095 phase (nitrided austenite) and a diffusional zone underneath the white layer. After tempering, the white layer was decomposed to a nano-sized (α-Fe + γ'-Fe4N + retained austenite) bainitic microstructure with a high hardness of 1150HV/25 g. Wear test results showed that the wear resistance and wear coefficient yielded by the complex HTGN plus tempering were considerably higher and lower, respectively, than those produced by the conventional plasma nitriding.

CTAB micelles and the hydroformylation of octene with rhodium/TPPTS catalysts - Evidence for the interaction of TPPTS with micelle surfaces

DEFF Research Database (Denmark)

Riisager, Anders; Hanson, Brian E.

2002-01-01

The addition of cetyltrimethylammonium bromide (CTAB) to TPPTS/rhodium hydroformylation catalysts has a complicated effect on reaction activity and selectivity. In water alone as the solvent, high CTAB concentration leads to the formation of emulsions and reaction selectivity drops. In aqueous...

The Rôle of the Element Rhodium in the Hyperbolic Law of the Periodic Table of Elements

Directory of Open Access Journals (Sweden)

Khazan A.

2008-07-01

Full Text Available The role of the element rhodium as an independent affirmation of calculations by the Hyperbolic Law and validity of all its relations is shown herein. The deviation in cal- culation by this method of the atomic mass of heaviest element is 0.0024%, and its coefficient of scaling 0.001–0.005%

Suspended HfO2 photonic crystal slab on III-nitride/Si platform

International Nuclear Information System (INIS)

Wang, Yongjin; Feng, Jiao; Cao, Ziping; Zhu, Hongbo

2014-01-01

We present here the fabrication of suspended hafnium oxide (HfO 2 ) photonic crystal slab on a III-nitride/Si platform. The calculations are performed to model the suspended HfO 2 photonic crystal slab. Aluminum nitride (AlN) film is employed as the sacrificial layer to form air gap. Photonic crystal patterns are defined by electron beam lithography and transferred into HfO 2 film, and suspended HfO 2 photonic crystal slab is achieved on a III-nitride/Si platform through wet-etching of AlN layer in the alkaline solution. The method is promising for the fabrication of suspended HfO 2 nanostructures incorporating into a III-nitride/Si platform, or acting as the template for epitaxial growth of III-nitride materials. (orig.)

Nitride surface passivation of GaAs nanowires: impact on surface state density.

Science.gov (United States)

Alekseev, Prokhor A; Dunaevskiy, Mikhail S; Ulin, Vladimir P; Lvova, Tatiana V; Filatov, Dmitriy O; Nezhdanov, Alexey V; Mashin, Aleksander I; Berkovits, Vladimir L

2015-01-14

Surface nitridation by hydrazine-sulfide solution, which is known to produce surface passivation of GaAs crystals, was applied to GaAs nanowires (NWs). We studied the effect of nitridation on conductivity and microphotoluminescence (μ-PL) of individual GaAs NWs using conductive atomic force microscopy (CAFM) and confocal luminescent microscopy (CLM), respectively. Nitridation is found to produce an essential increase in the NW conductivity and the μ-PL intensity as well evidence of surface passivation. Estimations show that the nitride passivation reduces the surface state density by a factor of 6, which is of the same order as that found for GaAs/AlGaAs nanowires. The effects of the nitride passivation are also stable under atmospheric ambient conditions for six months.

Ion-nitriding of austenitic stainless steels

International Nuclear Information System (INIS)

Pacheco, O.; Hertz, D.; Lebrun, J.P.; Michel, H.

1995-01-01

Although ion-nitriding is an extensively industrialized process enabling steel surfaces to be hardened by nitrogen diffusion, with a resulting increase in wear, seizure and fatigue resistance, its direct application to stainless steels, while enhancing their mechanical properties, also causes a marked degradation in their oxidation resistance. However, by adaption of the nitriding process, it is possible to maintain the improved wear resistant properties while retaining the oxidation resistance of the stainless steel. The controlled diffusion permits the growth of a nitrogen supersaturated austenite layer on parts made of stainless steel (AISI 304L and 316L) without chromium nitride precipitation. The diffusion layer remains stable during post heat treatments up to 650 F for 5,000 hrs and maintains a hardness of 900 HV. A very low and stable friction coefficient is achieved which provides good wear resistance against stainless steels under diverse conditions. Electrochemical and chemical tests in various media confirm the preservation of the stainless steel characteristics. An example of the application of this process is the treatment of Reactor Control Rod Cluster Assemblies (RCCAs) for Pressurized Water Nuclear Reactors

Redox-Neutral Rhodium-Catalyzed [4+1] Annulation through Formal Dehydrogenative Vinylidene Insertion.

Science.gov (United States)

Liu, Huan; Song, Shengjin; Wang, Cheng-Qiang; Feng, Chao; Loh, Teck-Peng

2017-01-10

A synthetic protocol for the expedient construction of 5-methylene-1H-pyrrol-2(5H)-one derivatives through rhodium-catalyzed [4+1] annulation with gem-difluoroacrylate as the C 1 component was reported. By taking advantage of the twofold C-F bond cleavage occurring during the annulation, this reaction not only allows the synthesis of these heterocyclic compounds under overall oxidant-free conditions but also renders the transformation stereospecific. The very mild reaction conditions employed ensure compatibility with a wide variety of synthetically useful functional groups. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reaction-bonded silicon nitride

International Nuclear Information System (INIS)

Porz, F.

1982-10-01

Reaction-bonded silicon nitride (RBSN) has been characterized. The oxidation behaviour in air up to 1500 0 C and 3000 h and the effects of static and cyclic oxidation on room-temperature strength have been studied. (orig./IHOE) [de

Low Temperature Gaseous Nitriding of a Stainless Steel Containing Strong Nitride Formers

DEFF Research Database (Denmark)

Fernandes, Frederico Augusto Pires; Christiansen, Thomas Lundin; Somers, Marcel A. J.

Low temperature thermochemical surface hardening of the precipitation hardening austenitic stainless steel A286 in solution treated state was investigated. A286 contains, besides high amounts of Cr, also substantial amounts of strong nitride formers as Ti, Al and V. It is shown that simultaneous...

Fabrication of functional structures on thin silicon nitride membranes

NARCIS (Netherlands)

Ekkels, P.; Tjerkstra, R.W.; Krijnen, Gijsbertus J.M.; Berenschot, Johan W.; Brugger, J.P.; Elwenspoek, Michael Curt

A process to fabricate functional polysilicon structures above large (4×4 mm2) thin (200 nm), very flat LPCVD silicon rich nitride membranes was developed. Key features of this fabrication process are the use of low-stress LPCVD silicon nitride, sacrificial layer etching, and minimization of

Mono and dinuclear iridium, rhodium and ruthenium complexes containing chelating carboxylato pyrazine ligands: Synthesis, molecular structure and electrochemistry

Czech Academy of Sciences Publication Activity Database

Govindaswamy, P.; Therrien, B.; Süss-Fink, G.; Štěpnička, P.; Ludvík, Jiří

2007-01-01

Roč. 692, č. 8 (2007), s. 1661-1671 ISSN 0022-328X R&D Projects: GA MŠk LC510; GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40400503 Keywords : dinuclear complexes * iridium * rhodium * ruthenium * electrochemistry Subject RIV: CG - Electrochemistry Impact factor: 2.168, year: 2007

Compositional analysis of silicon oxide/silicon nitride thin films

Directory of Open Access Journals (Sweden)

Meziani Samir

2016-06-01

Full Text Available Hydrogen, amorphous silicon nitride (SiNx:H abbreviated SiNx films were grown on multicrystalline silicon (mc-Si substrate by plasma enhanced chemical vapour deposition (PECVD in parallel configuration using NH3/SiH4 gas mixtures. The mc-Si wafers were taken from the same column of Si cast ingot. After the deposition process, the layers were oxidized (thermal oxidation in dry oxygen ambient environment at 950 °C to get oxide/nitride (ON structure. Secondary ion mass spectroscopy (SIMS, Rutherford backscattering spectroscopy (RBS, Auger electron spectroscopy (AES and energy dispersive X-ray analysis (EDX were employed for analyzing quantitatively the chemical composition and stoichiometry in the oxide-nitride stacked films. The effect of annealing temperature on the chemical composition of ON structure has been investigated. Some species, O, N, Si were redistributed in this structure during the thermal oxidation of SiNx. Indeed, oxygen diffused to the nitride layer into Si2O2N during dry oxidation.

Estimation of tribological anticorrosion properties of impregnated nitriding layers

International Nuclear Information System (INIS)

Iwanow, J.; Senatorski, J.; Tacikowski, J.

1999-01-01

In this paper is described aim, experimental and test result of tribological anticorrosion properties of thin nitriding layer (12.5 μm) obtained on 45 steel grade in controlled gas-nitriding process (570 o C, 4 h) impregnated with oil-based formulations, containing corrosion inhibitor BS-43, modified with tribological additives based on ashen organometallic compounds as well as ash-free organic compounds. It was stated, that tribological additives does not influence, in fact, on behaviour of corrosion resistance of nitriding layers impregnated with oil-base formulations mainly connected with inhibitor BS-43. Synergy of tribological additive and corrosion inhibitor is however more visible in modelling of wear resistance of nitriding layer. The influence nature of tribological additives in combination with corrosion inhibitor BS-43 is dependent on their kind and as result improves or worsens the wear resistance by friction. Hence in choice of impregnated formulation, which is enable to accomplish of tribological anticorrosion requirements, determined, above all, tribological additive. (author)

Thermodynamics, kinetics and process control of nitriding

DEFF Research Database (Denmark)

Mittemeijer, Eric J.; Somers, Marcel A. J.

1997-01-01

As a prerequisite for the predictability of properties obtained by a nitriding treatment of iron based workpieces, the relation between the process parameters and the composition and structure of the surface layer produced must be known. At present, even the description of thermodynamic equilibrium...... of pure Fe-N phases has not been fully achieved. It is shown that taking into account the ordering of nitrogen in the epsilon and gamma' iron nitride phases leads to an improved understanding of the Fe-N phase diagram. Although consideration of thermodynamics indicates the state the system strives for...... for process control of gaseous nitriding by monitoring the partial pressure of oxygen in the furnace using a solid state electrolyte is provided. At the time the work was carried out the authors were in the Laboratory of Materials Science, Delft University of Technology, Rotterdamseweg 137, 2628 AL Delft...

Preparing microspheres of actinide nitrides from carbon containing oxide sols

International Nuclear Information System (INIS)

Triggiani, L.V.

1975-01-01

A process is given for preparing uranium nitride, uranium oxynitride, and uranium carboxynitride microspheres and the microspheres as compositions of matter. The microspheres are prepared from carbide sols by reduction and nitriding steps. (Official Gazette)

Duplex surface treatment of AISI 1045 steel via plasma nitriding of chromized layer

International Nuclear Information System (INIS)

Hakami, F.; Sohi, M. Heydarzadeh; Ghani, J. Rasizadeh

2011-01-01

In this work AISI 1045 steel were duplex treated via plasma nitriding of chromized layer. Samples were pack chromized by using a powder mixture consisting of ferrochromium, ammonium chloride and alumina at 1273 K for 5 h. The samples were then plasma-nitrided for 5 h at 803 K and 823 K, in a gas mixture of 75%N 2 + 25%H 2 . The treated specimens were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis and Vickers micro-hardness test. The thickness of chromized layer before nitriding was about 8 μm and it was increased after plasma nitriding. According to XRD analysis, the chromized layer was composed of chromium and iron carbides. Plasma nitriding of chromized layer resulted in the formation of chromium and iron nitrides and carbides. The hardness of the duplex layers was significantly higher than the hardness of the base material or chromized layer. The main cause of the large improvement in surface hardness was due to the formation of Cr x N and Fe x N phases in the duplex treated layers. Increasing of nitriding temperature from 803 to 823 K enhanced the formation of CrN in the duplex treated layer and increased the thickness of the nitrided layer.

Mechanical properties of molybdenum-titanium alloys micro-structurally controlled by multi-step internal nitriding

International Nuclear Information System (INIS)

Nagae, M.; Yoshio, T.; Takemoto, Y.; Takada, J.; Hiraoka, Y.

2001-01-01

Internally nitrided dilute Mo-Ti alloys having a heavily deformed microstructure near the specimen surface were prepared by a novel two-step nitriding process at 1173 to 1773 K in N 2 gas. For the nitrided specimens three-point bend tests were performed at temperatures from 77 to 298 K in order to investigate the effect of microstructure control by internal nitriding on the ductile-to-brittle transition temperature (DBTT) of the alloy Yield strength obtained at 243 K of the specimen maintaining the deformed microstructure by the two-step nitriding was about 1.7 times as much as recrystallized specimen. The specimen subjected to the two-step nitriding was bent more than 90 degree at 243 K, whereas recrystallized specimen was fractured after showing a slight ductility at 243 K. DBTT of the specimen subjected to the two-step nitriding and recrystallized specimen was about 153 K and 203 K, respectively. These results indicate that multi-step internal nitriding is very effective to the improvement in the embrittlement by the recrystallization of molybdenum alloys. (author)

Vertical integration of high-Q silicon nitride microresonators into silicon-on-insulator platform.

Science.gov (United States)

Li, Qing; Eftekhar, Ali A; Sodagar, Majid; Xia, Zhixuan; Atabaki, Amir H; Adibi, Ali

2013-07-29

We demonstrate a vertical integration of high-Q silicon nitride microresonators into the silicon-on-insulator platform for applications at the telecommunication wavelengths. Low-loss silicon nitride films with a thickness of 400 nm are successfully grown, enabling compact silicon nitride microresonators with ultra-high intrinsic Qs (~ 6 × 10(6) for 60 μm radius and ~ 2 × 10(7) for 240 μm radius). The coupling between the silicon nitride microresonator and the underneath silicon waveguide is based on evanescent coupling with silicon dioxide as buffer. Selective coupling to a desired radial mode of the silicon nitride microresonator is also achievable using a pulley coupling scheme. In this work, a 60-μm-radius silicon nitride microresonator has been successfully integrated into the silicon-on-insulator platform, showing a single-mode operation with an intrinsic Q of 2 × 10(6).

Titanium Matrix Composite Ti/TiN Produced by Diode Laser Gas Nitriding

Directory of Open Access Journals (Sweden)

Aleksander Lisiecki

2015-01-01

Full Text Available A high power direct diode laser, emitting in the range of near infrared radiation at wavelength 808–940 nm, was applied to produce a titanium matrix composite on a surface layer of titanium alloy Ti6Al4V by laser surface gas nitriding. The nitrided surface layers were produced as single stringer beads at different heat inputs, different scanning speeds, and different powers of laser beam. The influence of laser nitriding parameters on the quality, shape, and morphology of the surface layers was investigated. It was found that the nitrided surface layers consist of titanium nitride precipitations mainly in the form of dendrites embedded in the titanium alloy matrix. The titanium nitrides are produced as a result of the reaction between molten Ti and gaseous nitrogen. Solidification and subsequent growth of the TiN dendrites takes place to a large extent at the interface of the molten Ti and the nitrogen gas atmosphere. The direction of TiN dendrites growth is perpendicular to the surface of molten Ti. The roughness of the surface layers depends strongly on the heat input of laser nitriding and can be precisely controlled. In spite of high microhardness up to 2400 HV0.2, the surface layers are crack free.

Kinetic parameters of nitridation of molybdenum and niobium alloys with various structure states

International Nuclear Information System (INIS)

Solodkin, G.A.; Bulgach, A.A.; Likhacheva, T.E.

1985-01-01

Effect of preliminary plastic strain under rolling on kinetic parameters of nitridation of VN-2AEh, VN-3 niobium alloys and molybdenum alloy with hafnium is investigated. Extreme character of dependence of kinetic parameters of nitridation on the degree of reduction under rolling is determined. Preliminary plastic strain at negligible reduction is shown to accelerate growth of the zone of internal nitridation and decelerates growth of the nitride zone. Nitrogen atom removal from the surface to the centre is retarded at the increase of the degree of reduction up to 50% and higher. The degree of deformations is the higher the lower nitridation temperature is

Preparation and characterization of morph-genetic aluminum nitride/carbon composites from filter paper

International Nuclear Information System (INIS)

Wang Wei; Xue Tao; Jin Zhihao; Qiao Guanjun

2008-01-01

Morph-genetic aluminum nitride/carbon composites with cablelike structure were prepared from filter paper template through the surface sol-gel process and carbothermal nitridation reaction. The resulting materials have a hierarchical structure originating from the morphology of cellulose paper. The aluminum nitride/carbon composites have the core-shell microstructure, the core is graphitic carbon, and the shell is aluminum nitride nanocoating formed by carbothermal nitridation reduction of alumina with the interfacial carbon in nitrogen atmosphere. Scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, and transmission electron microscope were employed to characterize the structural morphology and phase compositions of the final products

Partitioning of rhodium and ruthenium between Pd–Rh–Ru and (Ru,Rh)O{sub 2} solid solutions in high-level radioactive waste glass

Energy Technology Data Exchange (ETDEWEB)

Sugawara, Toru, E-mail: toru@gipc.akita-u.ac.jp [Center for Engineering Science, Akita University, 1-1, Tegatagakuenmachi, Akita City, Akita 010-8502 (Japan); Ohira, Toshiaki [Center for Engineering Science, Akita University, 1-1, Tegatagakuenmachi, Akita City, Akita 010-8502 (Japan); Komamine, Satoshi; Ochi, Eiji [Research and Development Department, Reprocessing Business Division, Japan Nuclear Fuel Limited, 4-108, Okitsuke, Obuchi, Rokkasho-mura, Aomori 039-3212 (Japan)

2015-10-15

The partitioning of rhodium and ruthenium between Pd–Rh–Ru alloy with a face-centered cubic (FCC) structure and (Ru,Rh)O{sub 2} solid solution has been investigated between 1273 and 1573 K at atmospheric oxygen fugacity. The rhodium and ruthenium contents in FCC increase, while the RhO{sub 2} content in (Ru,Rh)O{sub 2} decreases with increasing temperature due to progressive reduction of the system. Based on the experimental results and previously reported thermodynamic data, the thermodynamic mixing properties of FCC phase and (Ru,Rh)O{sub 2} have been calibrated in an internally consistent manner. Phase equilibrium of platinum grope metals in an HLW glass was calculated by using the obtained thermodynamic parameters.

Facile CO cleavage by a multimetallic CsU2 nitride complex

International Nuclear Information System (INIS)

Falcone, Marta; Scopelliti, Rosario; Mazzanti, Marinella; Kefalidis, Christos E.; Maron, Laurent

2016-01-01

Uranium nitrides are important materials with potential for application as fuels for nuclear power generation, and as highly active catalysts. Molecular nitride compounds could provide important insight into the nature of the uranium-nitride bond, but currently little is known about their reactivity. In this study, we found that a complex containing a nitride bridging two uranium centers and a cesium cation readily cleaved the C≡O bond (one of the strongest bonds in nature) under ambient conditions. The product formed has a [CsU 2 (μ-CN)(μ-O)] core, thus indicating that the three cations cooperate to cleave CO. Moreover, the addition of MeOTf to the nitride complex led to an exceptional valence disproportionation of the CsU IV -N-U IV core to yield CsU III (OTf) and [MeN=U V ] fragments. The important role of multimetallic cooperativity in both reactions is illustrated by the computed reaction mechanisms.

Facile CO Cleavage by a Multimetallic CsU2 Nitride Complex.

Science.gov (United States)

Falcone, Marta; Kefalidis, Christos E; Scopelliti, Rosario; Maron, Laurent; Mazzanti, Marinella

2016-09-26

Uranium nitrides are important materials with potential for application as fuels for nuclear power generation, and as highly active catalysts. Molecular nitride compounds could provide important insight into the nature of the uranium-nitride bond, but currently little is known about their reactivity. In this study, we found that a complex containing a nitride bridging two uranium centers and a cesium cation readily cleaved the C≡O bond (one of the strongest bonds in nature) under ambient conditions. The product formed has a [CsU2 (μ-CN)(μ-O)] core, thus indicating that the three cations cooperate to cleave CO. Moreover, the addition of MeOTf to the nitride complex led to an exceptional valence disproportionation of the CsU(IV) -N-U(IV) core to yield CsU(III) (OTf) and [MeN=U(V) ] fragments. The important role of multimetallic cooperativity in both reactions is illustrated by the computed reaction mechanisms. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrotreatment activities of supported molybdenum nitrides and carbides

Energy Technology Data Exchange (ETDEWEB)

Dolce, G.M.; Savage, P.E.; Thompson, L.T. [University of Michigan, Ann Arbor, MI (United States). Dept. of Chemical Engineering

1997-05-01

The growing need for alternative sources of transportation fuels encourages the development of new hydrotreatment catalysts. These catalysts must be active and more hydrogen efficient than the current commercial hydrotreatment catalysts. Molybdenum nitrides and carbides are attractive candidate materials possessing properties that are comparable or superior to those of commercial sulfide catalysts. This research investigated the catalytic properties of {gamma}-Al{sub 2}O{sub 3}-supported molybdenum nitrides and carbides. These catalysts were synthesized via temperature-programmed reaction of supported molybdenum oxides with ammonia or methane/hydrogen mixtures. Phase constituents and compositions were determined by X-ray diffraction, elemental analysis, and neutral activation analysis. Oxygen chemisorption was used to probe the surface properties of the catalysts. Specific activities of the molybdenum nitrides and carbides were competitive with those of a commercial sulfide catalyst for hydrodenitrogenation (HDN), hydrodesulfurization (HDS), and hydrodeoxygenation (HDO). For HDN and HDS, the catalytic activity on a molybdenum basis was a strong inverse function of the molybdenum loading. Product distributions of the HDN, HDO and HDS of a variety of heteroatom compounds indicated that several of the nitrides and carbides were more hydrogen efficient than the sulfide catalyst. 35 refs., 8 figs., 7 tabs.

Critical fields of niobium nitride films of various granularity

International Nuclear Information System (INIS)

Antonova, E.A.; Sukhov, V.A.

1983-01-01

The behaviour of lattice parameter, specific electrical resistivity, critical temperature, and temperature dependence of upper critical field near Tsub(cr) of sputtered niobium nitride films is investigated versus the substrate temperature and gas mixture composition in the process of reactive cathode sputtering. The relation between extrapolated value of the upper critical field and granularity of niobium nitride films, close as to composition to the stoichiometric one, has been found. Values of the kappa parameter of the Ginsburg-Landau theory and of the coherence length for niobium nitride films of various granularity are estimated in an approximation of uniform distribution of impurities in a sample

Conclusive evidence on the mechanism of the rhodium-mediated decyanative borylation.

Science.gov (United States)

Esteruelas, Miguel A; Oliván, Montserrat; Vélez, Andrea

2015-09-30

The stoichiometric reactions proposed in the mechanism of the rhodium-mediated decyanative borylation have been performed and all relevant intermediates isolated and characterized including their X-ray structures. Complex RhCl{xant(P(i)Pr2)2} (1, xant(P(i)Pr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) reacts with bis(pinacolato)diboron (B2pin2), in benzene, to give the rhodium(III) derivative RhHCl(Bpin){xant(P(i)Pr2)2} (4) and PhBpin. The reaction involves the oxidative addition of B2pin2 to 1 to give RhCl(Bpin)2{xant(P(i)Pr2)2}, which eliminates ClBpin generating Rh(Bpin){xant(P(i)Pr2)2} (2). The reaction of the latter with the solvent yields PhBpin and the monohydride RhH{xant(P(i)Pr2)2} (6), which adds the eliminated ClBpin. Complex 4 and its catecholboryl counterpart RhHCl(Bcat){xant(P(i)Pr2)2} (7) have also been obtained by oxidative addition of HBR2 to 1. Complex 2 is the promoter of the decyanative borylation. Thus, benzonitrile and 4-(trifluoromethyl)benzonitrile insert into the Rh-B bond of 2 to form Rh{C(R-C6H4)═NBpin}{xant(P(i)Pr2)2} (R = H (8), p-CF3 (9)), which evolve into the aryl derivatives RhPh{xant(P(i)Pr2)2} (3) and Rh(p-CF3-C6H4){xant(P(i)Pr2)2} (10), as a result of the extrusion of CNBpin. The reactions of 3 and 10 with B2pin2 yield the arylBpin products and regenerate 2.

77 FR 51825 - Ferrovanadium and Nitrided Vanadium From Russia

Science.gov (United States)

2012-08-27

... Nitrided Vanadium From Russia Determination On the basis of the record \\1\\ developed in the subject five... order on ferrovanadium and nitrided vanadium from Russia would not be likely to lead to continuation or recurrence of material injury to an industry in the United States within a reasonably foreseeable time. \\1...

Direct Synthesis of 5-Aryl Barbituric Acids by Rhodium(II)-Catalyzed Reactions of Arenes with Diazo Compounds**

Science.gov (United States)

Best, Daniel; Burns, David J; Lam, Hon Wai

2015-01-01

A commercially available rhodium(II) complex catalyzes the direct arylation of 5-diazobarbituric acids with arenes, allowing straightforward access to 5-aryl barbituric acids. Free N—H groups are tolerated on the barbituric acid, with no complications arising from N—H insertion processes. This method was applied to the concise synthesis of a potent matrix metalloproteinase (MMP) inhibitor. PMID:25959544

Low temperature gaseous nitriding of Ni based superalloys

DEFF Research Database (Denmark)

Eliasen, K. M.; Christiansen, Thomas Lundin; Somers, Marcel A. J.

2010-01-01

In the present work the nitriding response of selected Ni based superalloys at low temperatures is addressed. The alloys investigated are nimonic series nos. 80, 90, 95 and 100 and nichrome (Ni/Cr......In the present work the nitriding response of selected Ni based superalloys at low temperatures is addressed. The alloys investigated are nimonic series nos. 80, 90, 95 and 100 and nichrome (Ni/Cr...

Analytical and Experimental Evaluation of Joining Silicon Carbide to Silicon Carbide and Silicon Nitride to Silicon Nitride for Advanced Heat Engine Applications Phase II

Energy Technology Data Exchange (ETDEWEB)

Sundberg, G.J.

1994-01-01

Techniques were developed to produce reliable silicon nitride to silicon nitride (NCX-5101) curved joins which were used to manufacture spin test specimens as a proof of concept to simulate parts such as a simple rotor. Specimens were machined from the curved joins to measure the following properties of the join interlayer: tensile strength, shear strength, 22 C flexure strength and 1370 C flexure strength. In parallel, extensive silicon nitride tensile creep evaluation of planar butt joins provided a sufficient data base to develop models with accurate predictive capability for different geometries. Analytical models applied satisfactorily to the silicon nitride joins were Norton's Law for creep strain, a modified Norton's Law internal variable model and the Monkman-Grant relationship for failure modeling. The Theta Projection method was less successful. Attempts were also made to develop planar butt joins of siliconized silicon carbide (NT230).

High temperature mechanical performance of a hot isostatically pressed silicon nitride

Energy Technology Data Exchange (ETDEWEB)

Wereszczak, A.A.; Ferber, M.K.; Jenkins, M.G.; Lin, C.K.J. [and others

1996-01-01

Silicon nitride ceramics are an attractive material of choice for designers and manufacturers of advanced gas turbine engine components for many reasons. These materials typically have potentially high temperatures of usefulness (up to 1400{degrees}C), are chemically inert, have a relatively low specific gravity (important for inertial effects), and are good thermal conductors (i.e., resistant to thermal shock). In order for manufacturers to take advantage of these inherent properties of silicon nitride, the high-temperature mechanical performance of the material must first be characterized. The mechanical response of silicon nitride to static, dynamic, and cyclic conditions at elevated temperatures, along with reliable and representative data, is critical information that gas turbine engine designers and manufacturers require for the confident insertion of silicon nitride components into gas turbine engines. This final report describes the high-temperature mechanical characterization and analyses that were conducted on a candidate structural silicon nitride ceramic. The high-temperature strength, static fatigue (creep rupture), and dynamic and cyclic fatigue performance were characterized. The efforts put forth were part of Work Breakdown Structure Subelement 3.2.1, {open_quotes}Rotor Data Base Generation.{close_quotes} PY6 is comparable to other hot isostatically pressed (HIPed) silicon nitrides currently being considered for advanced gas turbine engine applications.

Rolling Contact Fatigue Failure Mechanisms of Plasma-Nitrided Ductile Cast Iron

Science.gov (United States)

Wollmann, D.; Soares, G. P. P. P.; Grabarski, M. I.; Weigert, N. B.; Escobar, J. A.; Pintaude, G.; Neves, J. C. K.

2017-05-01

Rolling contact fatigue (RCF) of a nitrided ductile cast iron was investigated. Flat washers machined from a pearlitic ductile cast iron bar were quenched and tempered to maximum hardness, ground, polished and divided into four groups: (1) specimens tested as quenched and tempered; (2) specimens plasma-nitrided for 8 h at 400 °C; (3) specimens plasma-nitrided and submitted to a diffusion process for 16 h at 400 °C; and (4) specimens submitted to a second tempering for 24 h at 400 °C. Hardness profiles, phase analyses and residual stress measurements by x-ray diffraction, surface roughness and scanning electron microscopy were applied to characterize the surfaces at each step of this work. Ball-on-flat washer tests were conducted with a maximum contact pressure of 3.6 GPa, under flood lubrication with a SAE 90 API GL-5 oil at 50 °C. Test ending criterion was the occurrence of a spalling. Weibull analysis was used to characterize RCF's lifetime data. Plasma-nitrided specimens exhibited a shorter RCF lifetime than those just quenched and tempered. The effects of nitriding on the mechanical properties and microstructure of the ductile cast iron are discussed in order to explain the shorter endurance of nitrided samples.

Technical assistance for development of thermally conductive nitride filler for epoxy molding compounds

Energy Technology Data Exchange (ETDEWEB)

Ryu, Ho Jin; Song, Kee Chan; Jung, In Ha

2005-07-15

Technical assistance was carried out to develop nitride filler for thermally conductive epoxy molding compounds. Carbothermal reduction method was used to fabricate silicon nitride powder from mixtures of silica and graphite powders. Microstructure and crystal structure were observed by using scanning electron microscopy and x-ray diffraction technique. Thermal properties of epoxy molding compounds containing silicon nitride were measured by using laser flash method. Fabrication process of silicon nitride nanowire was developed and was applied to a patent.

Plasma-nitriding assisted micro-texturing into stainless steel molds

Directory of Open Access Journals (Sweden)

Aizawa Tatsuhiko

2015-01-01

Full Text Available Micro-texturing has grown up to be one of the most promising procedures. This related application required for large-area, fine micro-texturing onto the stainless steel mold materials. A new method other than laser-machining, micro-milling or micro-EDM was awaited for further advancement of this micro-texturing. In the present paper, a plasma nitriding assisted micro-texturing was developed to make various kinds of micro-patterns onto the martensitic stainless steels. First, original patterns were printed onto the surface of substrate by using the ink-jet printer. Then, the masked substrate was subjected to high density plasma nitriding; the un-masked surfaces were nitrided to have higher hardness. This nitrided substrate was further treated by sand-blasting to selectively dig the soft, masked surfaces. Finally, the micro-patterned martensitic stainless steel substrate was fabricated as a mold to duplicate these micro-patterns onto the work materials. The spatial resolution and depth profile controllability of this plasma nitriding assisted micro-texturing was investigated for variety of initial micro-patterns. The original size and dimension of initial micro-patterns were precisely compared with the three dimensional geometry of micro-textures after blasting treatment. The plastic cover case for smart cellular phones was employed to demonstrate how useful this processing is in practice.

Performance analysis of a mixed nitride fuel system for an advanced liquid metal reactor

International Nuclear Information System (INIS)

Lyon, W.F.; Baker, R.B.; Leggett, R.D.

1991-01-01

In this paper, the conceptual development and analysis of a proposed mixed nitride driver and blanket fuel system for a prototypic advanced liquid metal reactor design is performed. As a first step, an intensive literature survey is completed on the development and testing of nitride fuel systems. Based on the results of this survey, prototypic mixed nitride fuel and blanket pins is designed and analyzed using the SIEX computer code. The analysis predicts that the nitride fuel consistently operated at peak temperatures and cladding strain levels that compared quite favorably with competing fuel designs. These results, along with data available in the literature on nitride fuel performance, indicate that a nitride fuel system should offer enhanced capabilities for advanced liquid metal reactors

Performance analysis of a mixed nitride fuel system for an advanced liquid metal reactor

International Nuclear Information System (INIS)

Lyon, W.F.; Baker, R.B.; Leggett, R.D.

1990-11-01

The conceptual development and analysis of a proposed mixed nitride driver and blanket fuel system for a prototypic advanced liquid metal reactor design has been performed. As a first step, an intensive literature survey was completed on the development and testing of nitride fuel systems. Based on the results of this survey, prototypic mixed nitride fuel and blanket pins were designed and analyzed using the SIEX computer code. The analysis predicted that the nitride fuel consistently operated at peak temperatures and cladding strain levels that compared quite favorably with competing fuel designs. These results, along with data available in the literature on nitride fuel performance, indicate that a nitride fuel system should offer enhanced capabilities for advanced liquid metal reactors. 13 refs., 10 figs., 2 tabs

Colloidal characterization of ultrafine silicon carbide and silicon nitride powders

Science.gov (United States)

Whitman, Pamela K.; Feke, Donald L.

1986-01-01

The effects of various powder treatment strategies on the colloid chemistry of aqueous dispersions of silicon carbide and silicon nitride are examined using a surface titration methodology. Pretreatments are used to differentiate between the true surface chemistry of the powders and artifacts resulting from exposure history. Silicon nitride powders require more extensive pretreatment to reveal consistent surface chemistry than do silicon carbide powders. As measured by titration, the degree of proton adsorption from the suspending fluid by pretreated silicon nitride and silicon carbide powders can both be made similar to that of silica.

Conductive and robust nitride buffer layers on biaxially textured substrates

Science.gov (United States)

Sankar, Sambasivan [Chicago, IL; Goyal, Amit [Knoxville, TN; Barnett, Scott A [Evanston, IL; Kim, Ilwon [Skokie, IL; Kroeger, Donald M [Knoxville, TN

2009-03-31

The present invention relates to epitaxial, electrically conducting and mechanically robust, cubic nitride buffer layers deposited epitaxially on biaxially textured substrates such as metals and alloys. The invention comprises of a biaxially textured substrate with epitaxial layers of nitrides. The invention also discloses a method to form such epitaxial layers using a high rate deposition method as well as without the use of forming gases. The invention further comprises epitaxial layers of oxides on the biaxially textured nitride layer. In some embodiments the article further comprises electromagnetic devices which may have superconducting properties.

Effects of Ion-Nitriding on the Pitting Behavior of Austenitic Stainless Steels Containing Mo

International Nuclear Information System (INIS)

Cho, Yong Seok; Choe, Han Cheol; Kim, Kwan Hyu

1994-01-01

Austenitic stainless steels(ASS) containing 1-4wt% Mo were ion-nitrided at 550 .deg. C for 20hrs and 30hrs, and their pitting behavior was examined by the electrochemical measurements. The formation of multiphase surface layers composed of the ε-{(Fe, Cr) 2- 3N} and the γ'-{(Fe, Cr) 4 N} phases was observed after ion-nitriding. The compound layers were approximately 50 μm thick after nitriding for 20hrs and 70 μm thick after 30hrs. Anodic polarization curves indicated that passive current density(I p ) and critical current density(I c ) increased, and corrosion potential(E corr ) decreased as a results of ion-nitriding. As the Mo content in the ion-nitrided ASS increased, passivation breakdown potential(E b ) and repassivation potential(E r ) increased, whereas I c and I p decreased. The pit nucleation time of the ASS nitrided for 20hrs was 10 minutes, while that of the 30hr nitrided samples was 3 minutes. The nucleation and growth of pits were significantly increased with the decreasing of Mo content as well as the increasing of ion-nitriding time

Iron-based alloy and nitridation treatment for PEM fuel cell bipolar plates

Science.gov (United States)

Brady, Michael P [Oak Ridge, TN; Yang, Bing [Oak Ridge, TN; Maziasz, Philip J [Oak Ridge, TN

2010-11-09

A corrosion resistant electrically conductive component that can be used as a bipolar plate in a PEM fuel cell application is composed of an alloy substrate which has 10-30 wt. % Cr, 0.5 to 7 wt. % V, and base metal being Fe, and a continuous surface layer of chromium nitride and vanadium nitride essentially free of base metal. A oxide layer of chromium vanadium oxide can be disposed between the alloy substrate and the continuous surface nitride layer. A method to prepare the corrosion resistant electrically conductive component involves a two-step nitridization sequence by exposing the alloy to a oxygen containing gas at an elevated temperature, and subsequently exposing the alloy to an oxygen free nitrogen containing gas at an elevated temperature to yield a component where a continuous chromium nitride layer free of iron has formed at the surface.

Enantioselective synthesis of chiral 3-aryl-1-indanones through rhodium-catalyzed asymmetric intramolecular 1,4-addition.

Science.gov (United States)

Yu, Yue-Na; Xu, Ming-Hua

2013-03-15

Enantioselective synthesis of potentially useful chiral 3-aryl-1-indanones was achieved through a rhodium-catalyzed asymmetric intramolecular 1,4-addition of pinacolborane chalcone derivatives using extraordinary simple MonoPhos as chiral ligand under relatively mild conditions. This novel protocol offers an easy access to a wide variety of enantioenriched 3-aryl-1-indanone derivatives in high yields (up to 95%) with excellent enantioselectivities (up to 95% ee).

Metallurgical response of an AISI 4140 steel to different plasma nitriding gas mixtures

Directory of Open Access Journals (Sweden)

Adão Felipe Oliveira Skonieski

2013-01-01

Full Text Available Plasma nitriding is a surface modification process that uses glow discharge to diffuse nitrogen atoms into the metallic matrix of different materials. Among the many possible parameters of the process, the gas mixture composition plays an important role, as it impacts directly the formed layer's microstructure. In this work an AISI 4140 steel was plasma nitrided under five different gas compositions. The plasma nitriding samples were characterized using optical and scanning electron microscopy, microhardness test, X-ray diffraction and GDOES. The results showed that there are significant microstructural and morphological differences on the formed layers depending on the quantity of nitrogen and methane added to the plasma nitriding atmosphere. Thicknesses of 10, 5 and 2.5 µm were obtained when the nitrogen content of the gas mixtures were varied. The possibility to obtain a compound layer formed mainly by γ'-Fe4N nitrides was also shown. For all studied plasma nitriding conditions, the presence of a compound layer was recognized as being the responsible to hinder the decarburization on the steel surface. The highest value of surface hardness - 1277HV - were measured in the sample which were nitrided with 3vol.% of CH4.

Platinum, palladium, and rhodium analyses of ultramafic and mafic rocks from the Stillwater Complex, Montana

Science.gov (United States)

Page, Norman J; Riley, Leonard Benjamin; Haffty, Joseph

1969-01-01

Analyses by a combination fire- assay-solution-optical-emission spectrographic method of 137 rocks from the Stillwater Complex, Mont., indicate that platinum, palladium, and rhodium are preferentially concentrated in chromitite zones. The A chromitite zone (21 samples) has an average of 988.9 ppb (pans per billion, 10-9) Pt, 2290.2 ppb Pd, and 245.9 ppb Rh and reaches a maximum (to date) of 8,000 ppb Pt, 11,000 ppb Pd, and 1,700 ppb Rh.

Determination of Rhodium(III Ions by Flame Atomic Absorption Spectrometry after Preconcentration with Modified Magnetic Activated Carbon

Directory of Open Access Journals (Sweden)

Maryam Fayazi

2016-06-01

Full Text Available A new method for analysis of trace amount of Rh(III ions by magnetic activated carbon modified with 2,3,5,6-tetra(2-pyridylpyrazine (MAC/TPPZ as the magnetic sorbent has been proposed. The proposed adsorbent was found to be advantageous over conventional solid phase extraction (SPE in terms of operational simplicity and low time-consuming. The experimental parameters affecting the extraction/preconcentration and determination of the analyte were systematically examined. In order to investigate the selectivity of this magnetic sorbent, the effect of a variety of ions on preconcentration and recovery of Rh(III ions were also investigated. Under optimum conditions, the calibration graph was linear for the concentration range of 0.8-650 µg l-1. The limit of detection (LOD, 3Sb/m and the relative standard deviation (RSD, n = 8, c = 50 µg l-1 were 0.1 µg l-1 and 3.6%, respectively. The maximum sorption capacity of the adsorbent for rhodium was found to be 21.6 mg g-1. The presented procedure was applied to monitoring rhodium in water and synthetic samples.

An operando FTIR spectroscopic and kinetic study of carbon monoxide pressure influence on rhodium-catalyzed olefin hydroformylation.

Science.gov (United States)

Kubis, Christoph; Sawall, Mathias; Block, Axel; Neymeyr, Klaus; Ludwig, Ralf; Börner, Armin; Selent, Detlef

2014-09-08

The influence of carbon monoxide concentration on the kinetics of the hydroformylation of 3,3-dimethyl-1-butene with a phosphite-modified rhodium catalyst has been studied for the pressure range p(CO)=0.20-3.83 MPa. Highly resolved time-dependent concentration profiles of the organometallic intermediates were derived from IR spectroscopic data collected in situ for the entire olefin-conversion range. The dynamics of the catalyst and organic components are described by enzyme-type kinetics with competitive and uncompetitive inhibition reactions involving carbon monoxide taken into account. Saturation of the alkyl-rhodium intermediates with carbon monoxide as a cosubstrate occurs between 1.5 and 2 MPa of carbon monoxide pressure, which brings about a convergence of aldehyde regioselectivity. Hydrogenolysis of the acyl intermediate is fast at 30 °C and low pressure of p(CO)=0.2 MPa, but is of minus first order with respect to the solution concentration of carbon monoxide. Resting 18-electron hydrido and acyl complexes that correspond to early and late rate-determining states, respectively, coexist as long as the conversion of the substrate is not complete. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transferrable monolithic III-nitride photonic circuit for multifunctional optoelectronics

Science.gov (United States)

Shi, Zheng; Gao, Xumin; Yuan, Jialei; Zhang, Shuai; Jiang, Yan; Zhang, Fenghua; Jiang, Yuan; Zhu, Hongbo; Wang, Yongjin

2017-12-01

A monolithic III-nitride photonic circuit with integrated functionalities was implemented by integrating multiple components with different functions into a single chip. In particular, the III-nitride-on-silicon platform is used as it integrates a transmitter, a waveguide, and a receiver into a suspended III-nitride membrane via a wafer-level procedure. Here, a 0.8-mm-diameter suspended device architecture is directly transferred from silicon to a foreign substrate by mechanically breaking the support beams. The transferred InGaN/GaN multiple-quantum-well diode (MQW-diode) exhibits a turn-on voltage of 2.8 V with a dominant electroluminescence peak at 453 nm. The transmitter and receiver share an identical InGaN/GaN MQW structure, and the integrated photonic circuit inherently works for on-chip power monitoring and in-plane visible light communication. The wire-bonded monolithic photonic circuit on glass experimentally demonstrates in-plane data transmission at 120 Mb/s, paving the way for diverse applications in intelligent displays, in-plane light communication, flexible optical sensors, and wearable III-nitride optoelectronics.

Synthesis of hexagonal boron nitride graphene-like few layers

Science.gov (United States)

Yuan, S.; Toury, B.; Journet, C.; Brioude, A.

2014-06-01

Self-standing highly crystallized hexagonal boron nitride (h-BN) mono-, bi- and few-layers have been obtained for the first time via the Polymer Derived Ceramics (PDCs) route by adding lithium nitride (Li3N) micropowders to liquid-state polyborazylene (PBN). Incorporation of Li3N as a crystallization promoter allows the onset of crystallization of h-BN at a lower temperature (1200 °C) than under classical conditions (1800 °C). The hexagonal structure was confirmed by both electron and X-ray diffraction.Self-standing highly crystallized hexagonal boron nitride (h-BN) mono-, bi- and few-layers have been obtained for the first time via the Polymer Derived Ceramics (PDCs) route by adding lithium nitride (Li3N) micropowders to liquid-state polyborazylene (PBN). Incorporation of Li3N as a crystallization promoter allows the onset of crystallization of h-BN at a lower temperature (1200 °C) than under classical conditions (1800 °C). The hexagonal structure was confirmed by both electron and X-ray diffraction. Electronic supplementary information (ESI) available: See DOI: 10.1039/c4nr01017e

Semipolar III-nitride laser diodes with zinc oxide cladding.

Science.gov (United States)

Myzaferi, Anisa; Reading, Arthur H; Farrell, Robert M; Cohen, Daniel A; Nakamura, Shuji; DenBaars, Steven P

2017-07-24

Incorporating transparent conducting oxide (TCO) top cladding layers into III-nitride laser diodes (LDs) improves device design by reducing the growth time and temperature of the p-type layers. We investigate using ZnO instead of ITO as the top cladding TCO of a semipolar (202¯1) III-nitride LD. Numerical modeling indicates that replacing ITO with ZnO reduces the internal loss in a TCO clad LD due to the lower optical absorption in ZnO. Lasing was achieved at 453 nm with a threshold current density of 8.6 kA/cm 2 and a threshold voltage of 10.3 V in a semipolar (202¯1) III-nitride LD with ZnO top cladding.

Effect of gas pressure on active screen plasma nitriding response

International Nuclear Information System (INIS)

Nishimoto, Akio; Nagatsuka, Kimiaki; Narita, Ryota; Nii, Hiroaki; Akamatsu, Katsuya

2010-01-01

An austenitic stainless steel AISI 304 was active screen plasma nitrided using a 304 steel screen to investigate the effect of the gas pressure on the ASPN response. The sample was treated for 18 ks at 723 K in 25% N2 + 75% H2 gases. The gas pressure was changed to 100, 600 and 1200 Pa. The distance between screen and sample was also changed to 10, 30 and 50 mm. The nitrided samples were characterized by appearance observation, surface roughness, optical microscopy, X-ray diffraction, and microhardness testing. After nitriding, polygonal particles with a normal distribution were observed at the center and edges of all the ASPN-treated sample surfaces. Particles on the sample surfaces were finer with an increase in the gas pressure. The nitrided layer with a greater and homogeneous thickness was obtained at a low gas pressure of 100 Pa. (author)

Rhodium deposition onto a 4-mercaptopyridine SAM on Au(1 1 1)

Energy Technology Data Exchange (ETDEWEB)

Manolova, M. [Institute of Electrochemistry, University of Ulm, 89069 Ulm (Germany); Kayser, M. [Institute of Electrochemistry, University of Ulm, 89069 Ulm (Germany); Kolb, D.M. [Institute of Electrochemistry, University of Ulm, 89069 Ulm (Germany)]. E-mail: dieter.kolb@uni-ulm.de; Boyen, H.-G. [Institute of Solid State Physics, University of Ulm, 89069 Ulm (Germany); Ziemann, P. [Institute of Solid State Physics, University of Ulm, 89069 Ulm (Germany); Mayer, D. [BASF Electronic Materials GmbH, 67056 Ludwigshafen (Germany); Wirth, A. [BASF Electronic Materials GmbH, 67056 Ludwigshafen (Germany)

2007-02-10

The application of a recently developed method for the deposition of Pd and Pt on top of a SAM, has been successfully extended to Rh, thus proving the versatility of the new concept. Experimental evidence from cyclic voltammetry, in situ STM and ex situ X-ray photoemission spectroscopy is presented for the deposition of monoatomic high rhodium islands onto a 4-mercaptopyridine self-assembled monolayer on a Au(1 1 1) electrode. By repetitive complexation of the Rh ions to the ring-nitrogen and reduction in a Rh-ion free solution, an almost completely covered SAM is obtained. The consequences of making contacts for molecular electronics are briefly discussed.

(η2,η2-Cycloocta-1,5-diene[2-(diphenylphosphanylmethylpyridine-κ2N,P]rhodium(I tetrafluoridoborate 1,2-dichloroethane monosolvate

Directory of Open Access Journals (Sweden)

Siping Wei

2016-08-01

Full Text Available The title compound, [Rh(C8H12(C18H16NP]BF4 has been prepared as a precatalyst for applications in rhodium-catalysed additions of carbocyclic acids to terminal alkynes leading to anti-Markovnikov Z-enol esters. Here the triclinic pseudopolymorph of the title compound is presented. In contrast to the earlier reported pseudopolymorph (orthorhombic space group [Wei et al. (2013. Chem. Eur. J. 19, 12067–12076], the triclinic polymorph contains half a molecule of dichloromethane as solvent in the asymmetric unit. The rhodium(I atom exhibits a square-planar coordination. The estimated diffraction contribution of the disordered solvent (a half molecule of dichloroethane per asymmetric unit was subtracted from the observed diffraction data using the SQUEEZE [Spek (2015. Acta Cryst. C71, 9–16] routine in PLATON. The given chemical formula and other crystal data do not take the solvent into account.

Friction and Wear of Unlubricated NiTiHf with Nitriding Surface Treatments

Science.gov (United States)

Stanford, Malcolm K.

2018-01-01

The unlubricated friction and wear properties of the superelastic materials NiTi and NiTiHf, treated by either gas nitriding or plasma nitriding, have been investigated. Pin on disk testing of the studied materials was performed at sliding speeds from 0.01 to 1m/s at normal loads of 1, 5 or 10N. For all of the studied friction pairs (NiTiHf pins vs. NiTi and NiTiHf disks) over the given parameters, the steady-state coefficients of friction varied from 0.22 to 1.6. Pin wear factors ranged from approximately 1E-6 against the NiTiHf and plasma nitrided disks to approximately 1E-4 for the gas nitrided disks. The plasma nitrided disks provided wear protection in several cases and tended to wear by adhesion. The gas nitrided treatment generated the most pin wear but had essentially no disk wear except at the most severe of the studied conditions (1N load and 1m/s sliding speed). The results of this study are expected to provide guidance for design of components such as gears and fasteners.

Second-harmonic generation in substoichiometric silicon nitride layers

Science.gov (United States)

Pecora, Emanuele; Capretti, Antonio; Miano, Giovanni; Dal Negro, Luca

2013-03-01

Harmonic generation in optical circuits offers the possibility to integrate wavelength converters, light amplifiers, lasers, and multiple optical signal processing devices with electronic components. Bulk silicon has a negligible second-order nonlinear optical susceptibility owing to its crystal centrosymmetry. Silicon nitride has its place in the microelectronic industry as an insulator and chemical barrier. In this work, we propose to take advantage of silicon excess in silicon nitride to increase the Second Harmonic Generation (SHG) efficiency. Thin films have been grown by reactive magnetron sputtering and their nonlinear optical properties have been studied by femtosecond pumping over a wide range of excitation wavelengths, silicon nitride stoichiometry and thermal processes. We demonstrate SHG in the visible range (375 - 450 nm) using a tunable 150 fs Ti:sapphire laser, and we optimize the SH emission at a silicon excess of 46 at.% demonstrating a maximum SHG efficiency of 4x10-6 in optimized films. Polarization properties, generation efficiency, and the second order nonlinear optical susceptibility are measured for all the investigated samples and discussed in terms of an effective theoretical model. Our findings show that the large nonlinear optical response demonstrated in optimized Si-rich silicon nitride materials can be utilized for the engineering of nonlinear optical functions and devices on a Si chip.

Molecular coatings of nitride semiconductors for optoelectronics, electronics, and solar energy harvesting

KAUST Repository

Ng, Tien Khee; Zhao, Chao; Priante, Davide; Ooi, Boon S.; Hussein, Mohamed Ebaid Abdrabou

2018-01-01

Gallium nitride based semiconductors are provided having one or more passivated surfaces. The surfaces can have a plurality of thiol compounds attached thereto for enhancement of optoelectronic properties and/or solar water splitting properties. The surfaces can also include wherein the surface has been treated with chemical solution for native oxide removal and / or wherein the surface has attached thereto a plurality of nitrides, oxides, insulating compounds, thiol compounds, or a combination thereof to create a treated surface for enhancement of optoelectronic properties and / or solar water splitting properties. Methods of making the gallium nitride based semiconductors are also provided. Methods can include cleaning a native surface of a gallium nitride semiconductor to produce a cleaned surface, etching the cleaned surface to remove oxide layers on the surface, and applying single or multiple coatings of nitrides, oxides, insulating compounds, thiol compounds, or a combination thereof attached to the surface.

Molecular coatings of nitride semiconductors for optoelectronics, electronics, and solar energy harvesting

KAUST Repository

Ng, Tien Khee

2018-02-01

Gallium nitride based semiconductors are provided having one or more passivated surfaces. The surfaces can have a plurality of thiol compounds attached thereto for enhancement of optoelectronic properties and/or solar water splitting properties. The surfaces can also include wherein the surface has been treated with chemical solution for native oxide removal and / or wherein the surface has attached thereto a plurality of nitrides, oxides, insulating compounds, thiol compounds, or a combination thereof to create a treated surface for enhancement of optoelectronic properties and / or solar water splitting properties. Methods of making the gallium nitride based semiconductors are also provided. Methods can include cleaning a native surface of a gallium nitride semiconductor to produce a cleaned surface, etching the cleaned surface to remove oxide layers on the surface, and applying single or multiple coatings of nitrides, oxides, insulating compounds, thiol compounds, or a combination thereof attached to the surface.

Preparation of high-pressure phase boron nitride films by physical vapor deposition

CERN Document Server

Zhu, P W; Zhao, Y N; Li, D M; Liu, H W; Zou Guang Tian

2002-01-01

The high-pressure phases boron nitride films together with cubic, wurtzic, and explosive high-pressure phases, were successfully deposited on the metal alloy substrates by tuned substrate radio frequency magnetron sputtering. The percentage of cubic boron nitride phase in the film was about 50% as calculated by Fourier transform infrared measurements. Infrared peak position of cubic boron nitride at 1006.3 cm sup - sup 1 , which is close to the stressless state, indicates that the film has very low internal stress. Transition electron microscope micrograph shows that pure cubic boron nitride phase exits on the surface of the film. The growth mechanism of the BN films was also discussed.

Nitride passivation of the interface between high-k dielectrics and SiGe

Energy Technology Data Exchange (ETDEWEB)

Sardashti, Kasra [Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093-0358 (United States); Materials Science and Engineering Program, University of California, San Diego, La Jolla, California 92093-0411 (United States); Hu, Kai-Ting [Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093-0358 (United States); Department of Mechanical and Aerospace Engineering, University of California, San Diego, La Jolla, California 92093-0411 (United States); Tang, Kechao; McIntyre, Paul [Department of Materials Science and Engineering, Stanford University, Stanford, California 94305 (United States); Madisetti, Shailesh; Oktyabrsky, Serge [Colleges of Nanoscale Science and Engineering, SUNY Polytechnic Institute, Albany, New York 12222 (United States); Siddiqui, Shariq; Sahu, Bhagawan [TD Research, GLOBALFOUNDRIES US, Inc., Albany, New York 12203 (United States); Yoshida, Naomi; Kachian, Jessica; Dong, Lin [Applied Materials, Inc., Santa Clara, California 95054 (United States); Fruhberger, Bernd [California Institute for Telecommunications and Information Technology, University of California San Diego, La Jolla, California 92093-0436 (United States); Kummel, Andrew C., E-mail: akummel@ucsd.edu [Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093-0358 (United States)

2016-01-04

In-situ direct ammonia (NH{sub 3}) plasma nitridation has been used to passivate the Al{sub 2}O{sub 3}/SiGe interfaces with Si nitride and oxynitride. X-ray photoelectron spectroscopy of the buried Al{sub 2}O{sub 3}/SiGe interface shows that NH{sub 3} plasma pre-treatment should be performed at high temperatures (300 °C) to fully prevent Ge nitride and oxynitride formation at the interface and Ge out-diffusion into the oxide. C-V and I-V spectroscopy results show a lower density of interface traps and smaller gate leakage for samples with plasma nitridation at 300 °C.

Tribological and microstructural characteristics of ion-nitrided steels

Science.gov (United States)

Spalvins, T.

1983-01-01

Three steels AISI 4140, AISI 4340 and AISI 304 stainless steel were ion nitrided in a plasma consisting of a 75:25 mixture of H2:N2, sometimes with a trace of CH4. Their surface topography was characterized by SEM and two distinct compound phases were identified: the gamma and the epsilon. The core-case hardness profiles were also established. The low Cr alloy steels have an extended diffusion zone in contrast to the 3034 stainless steels which have a sharp interface. The depth of ion-nitriding is increased as the Cr content is decreased. Friction tests reveal that the gamma surface phase has a lower coefficient of friction than the epsilon phase. The lowest coefficient of friction is achieved when both the rider and the specimen surface are ion nitrided. Previously announced in STAR as N83-24635

Cavitation contributes substantially to tensile creep in silicon nitride

International Nuclear Information System (INIS)

Luecke, W.E.; Wiederhorn, S.M.; Hockey, B.J.; Krause, R.F. Jr.; Long, G.G.

1995-01-01

During tensile creep of a hot isostatically pressed (HIPed) silicon nitride, the volume fraction of cavities increases linearly with strain; these cavities produce nearly all of the measured strain. In contrast, compressive creep in the same stress and temperature range produces very little cavitation. A stress exponent that increases with stress (var-epsilon ∝ σ n , 2 < n < 7) characterizes the tensile creep response, while the compressive creep response exhibits a stress dependence of unity. Furthermore, under the same stress and temperature, the material creeps nearly 100 times faster in tension than in compression. Transmission electron microscopy (TEM) indicates that the cavities formed during tensile creep occur in pockets of residual crystalline silicate phase located at silicon nitride multigrain junctions. Small-angle X-ray scattering (SAXS) from crept material quantifies the size distribution of cavities observed in TEM and demonstrates that cavity addition, rather than cavity growth, dominates the cavitation process. These observations are in accord with a model for creep based on the deformation of granular materials in which the microstructure must dilate for individual grains t slide past one another. During tensile creep the silicon nitride grains remain rigid; cavitation in the multigrain junctions allows the silicate to flow from cavities to surrounding silicate pockets, allowing the dilation of the microstructure and deformation of the material. Silicon nitride grain boundary sliding accommodates this expansion and leads to extension of the specimen. In compression, where cavitation is suppressed, deformation occurs by solution-reprecipitation of silicon nitride

Rhodium on tungsten carbide - a new catalyst for reforming CH{sub 4} with CO{sub 2}; Rhodium auf Wolframcarbid - ein neuer Katalysator zum Reformieren von CH{sub 4} mit CO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Voelter, J. [Inst. fuer Angewandte Chemie e.V., Berlin (Germany); Berndt, H. [Inst. fuer Angewandte Chemie e.V., Berlin (Germany); Lietz, G. [Inst. fuer Angewandte Chemie e.V., Berlin (Germany); Preiss, H. [TU Bergakademie Freiberg (Germany). Inst. fuer Energieverfahrenstechnik; Tamme, R. [Deutsche Forschungsanstalt fuer Luft- und Raumfahrt e.V., Stuttgart (Germany). Inst. fuer Technische Thermodynamik

1997-02-01

bei 600 bis 700 C wieder als Waerme gewonnen werden. Die vorliegende Arbeit betrifft Katalysatoren zum Reformieren im Solarreceiverreaktor. Bisher wurde eine mit dispersem Rhodium geschwaerzte, makroporoese Schaumkeramik sowohl zur Absorption von Solarenergie wie auch zur Aktivierung der Reformierreaktion benutzt. Dabei ist die Menge Rhodium, die fuer eine effektive Absorption der Strahlung eingesetzt werden muss, viel groesser als die Rh-Menge, die fuer die katalytische Reaktion erforderlich ist. Um hochdisperses Rhodium zu erzeugen, wird die Schaumkeramik aus {alpha}-Al{sub 2}O{sub 3} mit einem Washcoat ({gamma}-Al{sub 2}O{sub 3}) beschichtet. Ziel unserer Untersuchungen war es, Rh nur noch als Katalysator einzusetzen und fuer die Strahlungsabsorption ein anderes geeignetes Material zu verwenden. Es sollte untersucht werden, ob das die Strahlung reflektierende {gamma}-Al{sub 2}O{sub 3} durch einen schwarzen poroesen Katalysatortraeger ersetzt werden kann. Als Material, das auch der thermischen Belastung standhalten kann, kam Wolframcarbid (WC) in Frage. WC ist bisher in der Literatur noch nicht als Traeger fuer einen Metallkatalysator beschrieben worden. Fuer die spezielle Anwendung im Receiverreaktor musste untersucht werden, ob es als ein Traeger zur Dispergierung von Rhodium geeignet ist und wie es sich als Washcoat zur Beschichtung der Schaumkeramik verhaelt. (orig./SR)

Four-Wave Mixing in Silicon-Rich Nitride Waveguides

DEFF Research Database (Denmark)

Mitrovic, Miranda; Guan, Xiaowei; Ji, Hua

2015-01-01

We demonstrate four-wave mixing wavelength conversion in silicon-rich nitride waveguides which are a promising alternative to silicon for nonlinear applications. The obtained conversion efficiency reaches -13.6 dB while showing no significant nonlinear loss.......We demonstrate four-wave mixing wavelength conversion in silicon-rich nitride waveguides which are a promising alternative to silicon for nonlinear applications. The obtained conversion efficiency reaches -13.6 dB while showing no significant nonlinear loss....

Nitrogen Atom Transfer From High Valent Iron Nitrides

Energy Technology Data Exchange (ETDEWEB)

Johnson, Michael D. [New Mexico State Univ., Las Cruces, NM (United States); Smith, Jeremy M. [Indiana Univ., Bloomington, IN (United States)

2015-10-14

This report describes the synthesis and reactions of high valent iron nitrides. Organonitrogen compounds such as aziridines are useful species for organic synthesis, but there are few efficient methods for their synthesis. Using iron nitrides to catalytically access these species may allow for their synthesis in an energy-and atom-efficient manner. We have developed a new ligand framework to achieve these goals as well as providing a method for inducing previously unknown reactivity.

Enantioselective Access to Spirocyclic Sultams by Chiral Cp(x) -Rhodium(III)-Catalyzed Annulations.

Science.gov (United States)

Pham, Manh V; Cramer, Nicolai

2016-02-12

Chiral spirocyclic sultams are a valuable compound class in organic and medicinal chemistry. A rapid entry to this structural motif involves a [3+2] annulation of an N-sulfonyl ketimine and an alkyne. Although the directing-group properties of the imino group for C-H activation have been exploited, the developments of related asymmetric variants have remained very challenging. The use of rhodium(III) complexes equipped with a suitable atropchiral cyclopentadienyl ligand, in conjunction with a carboxylic acid additive, enables an enantioselective and high yielding access to such spirocyclic sultams. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rhodium(III) as a potentiator of the effects of X-rays on cells

Energy Technology Data Exchange (ETDEWEB)

Richmond, R C; Centilli, M A; Cross, M H; Powers, E L

1986-08-01

A rhodium compound, Rh(NH/sub 3/)/sub 3/Cl/sub 3/, does not sensitize the spores of Bacillus megaterium to X-rays. However, it is a very effective sensitizer of vegetative cells of Staphylococcus aureus, raising the sensitivity four times in O/sub 2/ and over 100 times in anoxia. The inhibition by oxygen of the sensitizing action of Rh(III), which operates over a wide range of (O/sub 2/), is noteworthy. These experiments were performed in saline-phosphate buffer using 50 kVp X-rays. The results are discussed in terms of the known radiation chemistry of this compound.

Nitrogen ion induced nitridation of Si(111) surface: Energy and fluence dependence

Energy Technology Data Exchange (ETDEWEB)

Kumar, Praveen [Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore 560064 (India); ISOM, Universidad Politecnia de Madrid, 28040 (Spain); Kumar, Mahesh [Physics and Energy Harvesting Group, National Physical Laboratory, New Delhi 110012 (India); Nötzel, R. [ISOM, Universidad Politecnia de Madrid, 28040 (Spain); Shivaprasad, S.M., E-mail: smsprasad@jncasr.ac.in [Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore 560064 (India)

2014-06-01

We present the surface modification of Si(111) into silicon nitride by exposure to energetic N{sub 2}{sup +} ions. In-situ UHV experiments have been performed to optimize the energy and fluence of the N{sub 2}{sup +} ions to form silicon nitride at room temperature (RT) and characterized in-situ by X-ray photoelectron spectroscopy. We have used N{sub 2}{sup +} ion beams in the energy range of 0.2–5.0 keV of different fluence to induce surface reactions, which lead to the formation of Si{sub x}N{sub y} on the Si(111) surface. The XPS core level spectra of Si(2p) and N(1s) have been deconvoluted into different oxidation states to extract qualitative information, while survey scans have been used for quantifying of the silicon nitride formation, valence band spectra show that as the N{sub 2}{sup +} ion fluence increases, there is an increase in the band gap. The secondary electron emission spectra region of photoemission is used to evaluate the change in the work function during the nitridation process. The results show that surface nitridation initially increases rapidly with ion fluence and then saturates. - Highlights: • A systematic study for the formation of silicon nitride on Si(111). • Investigation of optimal energy and fluence for energetic N{sub 2}{sup +} ions. • Silicon nitride formation at room temperature on Si(111)

First-principle study of silicon cluster doped with rhodium: Rh{sub 2}Si{sub n} (n = 1–11) clusters

Energy Technology Data Exchange (ETDEWEB)

Zhang, Shuai; Luo, Chang Geng; Li, Hua Yang [Department of Physics, Nanyang Normal University, Nanyang 473061 (China); Lu, Cheng, E-mail: lucheng@calypso.cn [Department of Physics, Nanyang Normal University, Nanyang 473061 (China); State Key Laboratory of Superhard Materials, Jilin University, Changchun 130012 (China); Li, Gen Quan; Lu, Zhi Wen [Department of Physics, Nanyang Normal University, Nanyang 473061 (China)

2015-06-15

The geometries, stabilities and electronic properties of rhodium-doped silicon clusters Rh{sub 2}Si{sub n} (n = 1–11) have been systematically studied by using density functional calculations at the B3LYP/GENECP level. The optimized results show that the lowest-energy isomers of Rh{sub 2}Si{sub n} clusters favor three-dimensional structures for n = 2–11. Based on the averaged binding energy, fragmentation energy, second-order energy difference and HOMO-LUMO energy gap, the stabilities of Rh{sub 2}Si{sub n} (n = 1–11) clusters have been analyzed. The calculated results suggest that the Rh{sub 2}Si{sub 6} cluster has the strongest relative stability and the doping with rhodium atoms can reduce the chemical stabilities of Si{sub n} clusters. The natural population and natural electron configuration analysis indicate that there is charge transfer from the Si atoms and 5s orbital of the Rh atoms to the 4d and 5p orbitals of Rh atoms. The analysis of electron localization function reveal that the Si–Si bonds are mainly covalent bonds and the Si–Rh bonds are almost ionic bonds. Moreover, the vertical ionization potential, vertical electron affinity, chemical hardness, chemical potential, vibrational spectrum and polarizability are also discussed. - Highlights: • The geometric structures of Rh{sub 2}Si{sub n} (n = 1–11) clusters are determined. • The stabilities and electronic properties of Rh{sub 2}Si{sub n} clusters are discussed. • The Rh{sub 2}Si{sub 6} cluster has the higher stability than other clusters. • The doped rhodium atoms can reduce the chemical stabilities of Si{sub n} clusters.

Pentamethylcyclopentadienyl-rhodium and iridium complexes containing (N^N and N^O) bound chloroquine analogue ligands: synthesis, characterization and antimalarial properties.

Science.gov (United States)

Ekengard, Erik; Kumar, Kamlesh; Fogeron, Thibault; de Kock, Carmen; Smith, Peter J; Haukka, Matti; Monari, Magda; Nordlander, Ebbe

2016-03-07

The synthesis and characterization of twenty new pentamethylcyclopentadienyl-rhodium and iridium complexes containing N^N and N^O-chelating chloroquine analogue ligands are described. The in vitro antimalarial activity of the new ligands as well as the complexes was evaluated against the chloroquine sensitive (CQS) NF54 and the chloroquine resistant (CQR) Dd2 strains of Plasmodium falciparum. The antimalarial activity was found to be good to moderate; although all complexes are less active than artesunate, some of the ligands and complexes showed better activity than chloroquine (CQ). In particular, rhodium complexes were found to be considerably more active than iridium complexes against the CQS NF54 strain. Salicylaldimine Schiff base ligands having electron-withdrawing groups (F, Cl, Br, I and NO2) in para position of the salicyl moiety and their rhodium complexes showed good antiplasmodial activity against both the CQS-NF54 and the CQR-Dd2 strains. The crystal structures of (η(5)-pentamethylcyclopentadienyl){N(1)-(7-chloroquinolin-4-yl)-N(2)-(pyridin-2-ylmethyl)ethane-1,2-diamine)} chlororhodium(III) chloride and (η(5)-pentamethylcyclopentadienyl){(4-chloro-2-(((2-((7-chloroquinolin-4-yl)amino)ethyl)imino)methyl)phenolate)}chlororhodium(III) chloride are reported. The crystallization of the amino-pyridyl complex (η(5)-pentamethylcyclopentadienyl){(N(1)-(7-chloroquinolin-4-yl)-N(2)-(pyridin-2-ylmethyl)ethane-1,2-diamine)}chloroiridium(III) chloride in acetone resulted in the formation of the imino-pyridyl derivative (η(5)-pentamethylcyclopentadienyl){(N1-(7-chloroquinolin-4-yl)-N2-(pyridin-2-ylmethylene)ethane-1,2-diamine)}chloroiridium(III) chloride, the crystal structure of which is also reported.

Metal surface nitriding by laser induced plasma

Science.gov (United States)

Thomann, A. L.; Boulmer-Leborgne, C.; Andreazza-Vignolle, C.; Andreazza, P.; Hermann, J.; Blondiaux, G.

1996-10-01

We study a nitriding technique of metals by means of laser induced plasma. The synthesized layers are composed of a nitrogen concentration gradient over several μm depth, and are expected to be useful for tribological applications with no adhesion problem. The nitriding method is tested on the synthesis of titanium nitride which is a well-known compound, obtained at present by many deposition and diffusion techniques. In the method of interest, a laser beam is focused on a titanium target in a nitrogen atmosphere, leading to the creation of a plasma over the metal surface. In order to understand the layer formation, it is necessary to characterize the plasma as well as the surface that it has been in contact with. Progressive nitrogen incorporation in the titanium lattice and TiN synthesis are studied by characterizing samples prepared with increasing laser shot number (100-4000). The role of the laser wavelength is also inspected by comparing layers obtained with two kinds of pulsed lasers: a transversal-excited-atmospheric-pressure-CO2 laser (λ=10.6 μm) and a XeCl excimer laser (λ=308 nm). Simulations of the target temperature rise under laser irradiation are performed, which evidence differences in the initial laser/material interaction (material heated thickness, heating time duration, etc.) depending on the laser features (wavelength and pulse time duration). Results from plasma characterization also point out that the plasma composition and propagation mode depend on the laser wavelength. Correlation of these results with those obtained from layer analyses shows at first the important role played by the plasma in the nitrogen incorporation. Its presence is necessary and allows N2 dissociation and a better energy coupling with the target. Second, it appears that the nitrogen diffusion governs the nitriding process. The study of the metal nitriding efficiency, depending on the laser used, allows us to explain the differences observed in the layer features

Effect of component's geometry on the plasma nitriding behavior of AISI 4340 steel

International Nuclear Information System (INIS)

Asadi, Z. Soltani; Mahboubi, F.

2012-01-01

Highlights: → The thickness of the compound layer increases with increasing in temperature and groove width. → Surface layer at the remote regions from the edge is thinner than that of closer regions. → The hardness and the case depth of the nitrided layer increase with increasing the width of the groove. → Intensity of ε phase increases with increasing the width of the groove in both methods. → The ASPN specimens are covered by hexagonal particles and for the CPN by cauliflower shape nitrides. -- Abstract: The main aim of this work was to investigate the effect of the sample geometry on properties of the conventional plasma nitrided (CPN) and active screen plasma nitrided (ASPN) steel. Sample assemblies consisting of rectangular grooved steel blocks with different groove dimensions of 2, 4, 6, 8 and 10 (W) x 40 (H) x 20 (L) mm 3 and AISI 4340 steel plates (substrates) with dimensions of 10 x 40 x 60 mm 3 , to serve as groove cover, were prepared. The sample assemblies were conventional and active screen plasma nitrided under the gas mixture of 75%N 2 + 25%H 2 , at temperatures of 500 o C and 540 o C, pressure of 4 torr, for 5 h. Properties of the nitrided substrates were investigated by evaluating compound layer thickness, case depth, phase composition and hardness profile. Results of the experiments showed that the thickness of the compound layer, hardness and nitrided case depth increased with increasing the width of the groove for both methods. Also, in each sample, nitrogen atoms penetrated more deeply in the regions of the groove closer to the edge. Hallow cathode effect occurred at the sample with 2 mm width groove, in the CPN method, leading to the overheating of the sample. In ASPN, the hardness and the nitrided case depth are lower in comparison with CPN. The surface morphology of the CPN treated samples consists of cauliflower shape surface nitrides while the surface of the AS plasma nitrided samples are covered by the hexagonal particles with

Sequential rhodium/palladium catalysis: enantioselective formation of dihydroquinolinones in the presence of achiral and chiral ligands.

Science.gov (United States)

Zhang, Lei; Qureshi, Zafar; Sonaglia, Lorenzo; Lautens, Mark

2014-12-08

Compatible combinations of achiral and chiral ligands can be used in rhodium/palladium catalysis to achieve highly enantioselective domino reactions. The difference in rates of catalysis and minimal effects of ligand interference confer control in the domino sequence. The "all-in-one" 1,4-conjugate arylation and C-N cross-coupling through sequential Rh/Pd catalysis provides access to enantioenriched dihydroquinolinone building blocks. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Construction of axial chirality by rhodium-catalyzed asymmetric dehydrogenative Heck coupling of biaryl compounds with alkenes.

Science.gov (United States)

Zheng, Jun; You, Shu-Li

2014-11-24

Enantioselective construction of axially chiral biaryls by direct C-H bond functionalization reactions has been realized. Novel axially chiral biaryls were synthesized by the direct C-H bond olefination of biaryl compounds, using a chiral [Cp*Rh(III)] catalyst, in good to excellent yields and enantioselectivities. The obtained axially chiral biaryls were found as suitable ligands for rhodium-catalyzed asymmetric conjugate additions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methods for improved growth of group III nitride buffer layers

Science.gov (United States)

Melnik, Yurity; Chen, Lu; Kojiri, Hidehiro

2014-07-15

Methods are disclosed for growing high crystal quality group III-nitride epitaxial layers with advanced multiple buffer layer techniques. In an embodiment, a method includes forming group III-nitride buffer layers that contain aluminum on suitable substrate in a processing chamber of a hydride vapor phase epitaxy processing system. A hydrogen halide or halogen gas is flowing into the growth zone during deposition of buffer layers to suppress homogeneous particle formation. Some combinations of low temperature buffers that contain aluminum (e.g., AlN, AlGaN) and high temperature buffers that contain aluminum (e.g., AlN, AlGaN) may be used to improve crystal quality and morphology of subsequently grown group III-nitride epitaxial layers. The buffer may be deposited on the substrate, or on the surface of another buffer. The additional buffer layers may be added as interlayers in group III-nitride layers (e.g., GaN, AlGaN, AlN).

Development of accurate mass spectrometric routine and reference methods for the determination of trace amounts of iridium and rhodium in photographic emulsionsf

NARCIS (Netherlands)

Krystek, Petra; Heumann, Klaus G.

1999-01-01

For the determination of trace amounts of iridium and rhodium in photographic emulsions different sample treatment procedures were coupled with inductively coupled plasma mass spectrometry (ICP-MS) and, for iridium, also with negative thermal ionisation isotope dilution mass spectrometry (NTI-IDMS)

Tribo-electrochemical characterization of hafnium multilayer systems deposited on nitride/vanadium nitride AISI 4140 steel

Science.gov (United States)

Mora, M.; Vera, E.; Aperador, W.

2016-02-01

In this work is presented the synergistic behaviour among corrosion/wear (tribocorrosion) of the multilayer coatings hafnium nitride/vanadium nitride [HfN/VN]n. The multilayers were deposited on AISI 4140 steel using the technique of physical vapor deposition PVD magnetron sputtering, the tests were performed using a pin-on-disk tribometer, which has an adapted potentiostat galvanostat with three-electrode electrochemical cell. Tribocorrosive parameters such as: Friction coefficient between the coating and the counter body (100 Cr6 steel ball); Polarization resistance by means of electrochemical impedance spectroscopy technique and corrosion rate by polarization curves were determined. It was observed an increase in the polarization resistance, a decrease in the corrosion rate and a low coefficient of friction in comparison with the substrate, due to an increase on the number of bilayers.

Tribo-electrochemical characterization of hafnium multilayer systems deposited on nitride/vanadium nitride AISI 4140 steel

International Nuclear Information System (INIS)

Mora, M; Vera, E; Aperador, W

2016-01-01

In this work is presented the synergistic behaviour among corrosion/wear (tribocorrosion) of the multilayer coatings hafnium nitride/vanadium nitride [HfN/VN]n. The multilayers were deposited on AISI 4140 steel using the technique of physical vapor deposition PVD magnetron sputtering, the tests were performed using a pin-on-disk tribometer, which has an adapted potentiostat galvanostat with three-electrode electrochemical cell. Tribocorrosive parameters such as: Friction coefficient between the coating and the counter body (100 Cr6 steel ball); Polarization resistance by means of electrochemical impedance spectroscopy technique and corrosion rate by polarization curves were determined. It was observed an increase in the polarization resistance, a decrease in the corrosion rate and a low coefficient of friction in comparison with the substrate, due to an increase on the number of bilayers. (paper)

Oligomeric complexes of some heteroaromatic ligands and aromatic diamines with rhodium and molybdenum tetracarboxylates: 13C and 15N CPMAS NMR and density functional theory studies.

Science.gov (United States)

Leniak, Arkadiusz; Kamieński, Bohdan; Jaźwiński, Jarosław

2015-05-01

Seven new oligomeric complexes of 4,4'-bipyridine; 3,3'-bipyridine; benzene-1,4-diamine; benzene-1,3-diamine; benzene-1,2-diamine; and benzidine with rhodium tetraacetate, as well as 4,4'-bipyridine with molybdenum tetraacetate, have been obtained and investigated by elemental analysis and solid-state nuclear magnetic resonance spectroscopy, (13)C and (15)N CPMAS NMR. The known complexes of pyrazine with rhodium tetrabenzoate, benzoquinone with rhodium tetrapivalate, 4,4'-bipyridine with molybdenum tetrakistrifluoroacetate and the 1 : 1 complex of 2,2'-bipyridine with rhodium tetraacetate exhibiting axial-equatorial ligation mode have been obtained as well for comparison purposes. Elemental analysis revealed 1 : 1 complex stoichiometry of all complexes. The (15)N CPMAS NMR spectra of all new complexes consist of one narrow signal, indicating regular uniform structures. Benzidine forms a heterogeneous material, probably containing linear oligomers and products of further reactions. The complexes were characterized by the parameter complexation shift Δδ (Δδ = δcomplex  - δligand). This parameter ranged from around -40 to -90 ppm in the case of heteroaromatic ligands, from around -12 to -22 ppm for diamines and from -16 to -31 ppm for the complexes of molybdenum tetracarboxylates with 4,4'-bipyridine. The experimental results have been supported by a density functional theory computation of (15)N NMR chemical shifts and complexation shifts at the non-relativistic Becke, three-parameter, Perdew-Wang 91/[6-311++G(2d,p), Stuttgart] and GGA-PBE/QZ4P levels of theory and at the relativistic scalar and spin-orbit zeroth order regular approximation/GGA-PBE/QZ4P level of theory. Nucleus-independent chemical shifts have been calculated for the selected compounds. Copyright © 2015 John Wiley & Sons, Ltd.

Rhodium-catalyzed annulation of arenes with alkynes through weak chelation-assisted C-H activation.

Science.gov (United States)

Yang, Yudong; Li, Kaizhi; Cheng, Yangyang; Wan, Danyang; Li, Mingliang; You, Jingsong

2016-02-18

The purpose of this article is to give a brief review of weak chelation-assistance as a powerful means for the rhodium-catalyzed annulation of arenes with alkynes. The use of commonly occurring functional groups (e.g., ketones, aldehydes, carboxylic acids and alcohols) as the directing groups enriches the versatility of auxiliary ligands and extends the scope of products. This short article offers an overview on emerging procedures, highlights their advantages and limitations, and covers the latest progress in the rapid synthesis of organic functional materials and natural products.

Facile CO cleavage by a multimetallic CsU{sub 2} nitride complex

Energy Technology Data Exchange (ETDEWEB)

Falcone, Marta; Scopelliti, Rosario; Mazzanti, Marinella [Ecole Polytechnique de Federale de Lausanne (EPFL) (Switzerland). Inst. des Sciences et Ingenierie Chimiques; Kefalidis, Christos E.; Maron, Laurent [Toulouse Univ. (France). LPCNO, CNRS et INSA, UPS

2016-09-26

Uranium nitrides are important materials with potential for application as fuels for nuclear power generation, and as highly active catalysts. Molecular nitride compounds could provide important insight into the nature of the uranium-nitride bond, but currently little is known about their reactivity. In this study, we found that a complex containing a nitride bridging two uranium centers and a cesium cation readily cleaved the C≡O bond (one of the strongest bonds in nature) under ambient conditions. The product formed has a [CsU{sub 2}(μ-CN)(μ-O)] core, thus indicating that the three cations cooperate to cleave CO. Moreover, the addition of MeOTf to the nitride complex led to an exceptional valence disproportionation of the CsU{sup IV}-N-U{sup IV} core to yield CsU{sup III}(OTf) and [MeN=U{sup V}] fragments. The important role of multimetallic cooperativity in both reactions is illustrated by the computed reaction mechanisms.

Rhodium-Catalyzed Insertion Reaction of PhP Group of Pentaphenylcyclopentaphosphine with Acyclic and Cyclic Disulfides.

Science.gov (United States)

Arisawa, Mieko; Sawahata, Kyosuke; Yamada, Tomoki; Sarkar, Debayan; Yamaguchi, Masahiko

2018-02-16

Organophosphorus compounds with a phosphorus atom attached to a phenyl group and two organothio/organoseleno groups were synthesized using the rhodium-catalyzed insertion reaction of the PhP group of pentaphenylcyclopentaphosphine (PhP) 5 with acyclic disulfides and diselenides. The method was applied to the synthesis of heterocyclic compounds containing the S-P-S group by the reaction of (PhP) 5 and cyclic disulfides such as 1,2-dithietes, 1,2-dithiocane, 1,4,5-dithiopane, and 1,2-dithiolanes.

Regio- and enantioselective synthesis of N-substituted pyrazoles by rhodium-catalyzed asymmetric addition to allenes.

Science.gov (United States)

Haydl, Alexander M; Xu, Kun; Breit, Bernhard

2015-06-08

The rhodium-catalyzed asymmetric N-selective coupling of pyrazole derivatives with terminal allenes gives access to enantioenriched secondary and tertiary allylic pyrazoles, which can be employed for the synthesis of medicinally important targets. The reaction tolerates a large variety of functional groups and labelling experiments gave insights into the reaction mechanism. This new methodology was further applied in a highly efficient synthesis of JAK 1/2 inhibitor (R)-ruxolitinib. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dispersive oxidation of rhodium clusters in Na-Y by the combined action of zeolite protons and carbon monoxide

International Nuclear Information System (INIS)

Wong, T.T.T.; Sachtler, W.M.H.; Stakheev, A.Yu.

1992-01-01

This paper uses x-ray photoelectron spectroscopy, fourier transform infrared spectroscopy and temperature programmed mass-spectrometric analysis to study the interaction of Na-Y supported rhodium with hydrogen, carbon monoxide, and zeolite protons. This report attempts to clarify the mechanism of dispersive oxidation of reduced Rh particles in the presence of CO, leading to the formation of Rh + (CO) 2 cations

Optimization of time–temperature schedule for nitridation of silicon ...

Indian Academy of Sciences (India)

pact was optimized by kinetic study of the reaction, 3Si + 2N2 = Si3N4 at four different temperatures (1250°C,. 1300°C, 1350°C and 1400°C). ... Reaction sintered silicon nitride; nitridation; reaction kinetics. 1. Introduction. Formation of ..... cation of silica layer resulted in active oxidation of silicon at high temperature to ...

Microstructural characterization of an AISI-SAE 4140 steel without nitridation and nitrided; Caracterizacion microestructural de un acero AISI-SAE 4140 sin nitrurar y nitrurado

Energy Technology Data Exchange (ETDEWEB)

Medina F, A.; Naquid G, C. [Gerencia de Ciencia de Materiales, Depto. de Sintesis y Caracterizacion de Materiales, A.P. 18-1027, 11801 Mexico D.F. (Mexico)

2000-07-01

It was micro structurally characterized an AISI-SAE 4140 steel before and after of nitridation through the nitridation process by plasma post-unloading microwaves through Optical microscopy (OM), Scanning electron microscopy (SEM) by means of secondary electrons and retrodispersed, X-ray diffraction (XRD), Energy dispersion spectra (EDS) and mapping of elements. (Author)

Discovery of earth-abundant nitride semiconductors by computational screening and high-pressure synthesis

Science.gov (United States)

Hinuma, Yoyo; Hatakeyama, Taisuke; Kumagai, Yu; Burton, Lee A.; Sato, Hikaru; Muraba, Yoshinori; Iimura, Soshi; Hiramatsu, Hidenori; Tanaka, Isao; Hosono, Hideo; Oba, Fumiyasu

2016-01-01

Nitride semiconductors are attractive because they can be environmentally benign, comprised of abundant elements and possess favourable electronic properties. However, those currently commercialized are mostly limited to gallium nitride and its alloys, despite the rich composition space of nitrides. Here we report the screening of ternary zinc nitride semiconductors using first-principles calculations of electronic structure, stability and dopability. This approach identifies as-yet-unreported CaZn2N2 that has earth-abundant components, smaller carrier effective masses than gallium nitride and a tunable direct bandgap suited for light emission and harvesting. High-pressure synthesis realizes this phase, verifying the predicted crystal structure and band-edge red photoluminescence. In total, we propose 21 promising systems, including Ca2ZnN2, Ba2ZnN2 and Zn2PN3, which have not been reported as semiconductors previously. Given the variety in bandgaps of the identified compounds, the present study expands the potential suitability of nitride semiconductors for a broader range of electronic, optoelectronic and photovoltaic applications. PMID:27325228

Wear behaviour of nitrogen-implanted and nitrided Ti-6Al-4V alloy

International Nuclear Information System (INIS)

Martinella, R.; Giovanardi, S.; Chevallard, G.; Villani, M.; Molinari, A.; Tosello, C.

1985-01-01

The comparison between the wear behaviour of nitrogen-implanted Ti-6Al-4V alloy and that of nitrided Ti-6Al-4V alloy is reported. Both treatments were carried out at temperatures from 573 to 973 K on lapped surfaces; in order to compare roughness effects, nitriding was also carried out on rougher samples. An improvement in wear resistance for lapped surfaces was noted after implantation at 573 K or higher temperatures and after nitriding at temperatures over 773 K only; however, at 873 K, nitriding was more effective than implantation. Rough nitrided surfaces showed better wear resistance than lapped nitrided surfaces or lapped implanted surfaces. Most probably the improvement in wear resistance on implanted samples is due to a reduction in friction induced by chemical modification of the surface as a result of oxide and TiN. Scanning electron microscopy observations which show subsurface voids and coalescence are in good agreement with a wear model previously reported. As implantation preserves the surface finish, a possible application is suggested. (Auth.)

Crystallo-chemistry of actinide nitrides (U1-yPuy)N and effect of impurities

International Nuclear Information System (INIS)

Beauvy, M.; Coulon-Picard, E.; Pelletier, M.

2004-01-01

Investigations on actinide nitrides has been done in our Laboratories for Fast Breeder Reactors since the seventies and some properties are reported to show the interest for these fuels. Today, the actinide nitrides are reconsidered as possible fuels for the future fission reactors (GFR and LMFR selected by the international forum Generation IV). The results of new investigations on crystal structure of mixed mono-nitrides (U,Pu)N, and the effects of oxygen and carbon contaminations on this structure are presented. The cubic 'NaCl-fcc' type structure of actinide nitrides AnN with space group O5/h-Fm3m does not respect the 'Vegard law' model for the mixed nitrides (U 1-y Pu y )N. These nitrides are usually considered with strong metallic character associated with partial ionic bonding, but the ionic contribution in the An-N bonding determined in this work is very important and near 41.6% for UN and PuN. From results published on resistivity of mixed nitrides, the data on bonding must be also modified for partial covalence. This is in good agreement with the experimental lattice parameters which are not compatible with dominant metallic bonding. The numbers of bonding electrons in the nitrides (U 1-y Pu y )N are reevaluated and the low values proposed comparatively with those previously published confirm the strong ionic character with high concentration of An 3+ ions. The solubility of oxygen and carbon in actinide nitrides (U 1-y Pu y )N are discussed from measurements on volume concentration of actinide oxide phase, total oxygen and carbon contents, and lattice parameter of nitrides. The oxygen solubility limit in UN is near 1000 ppm, with a lightly higher value of 1200 ppm for the mixed nitride (U 0.8 Pu 0.2 )N. The effects of oxygen or carbon atoms in the lattice of (U 1-y Pu y )N are analysed

Process for producing ceramic nitrides anc carbonitrides and their precursors

Science.gov (United States)

Brown, G.M.; Maya, L.

1987-02-25

A process for preparing ceramic nitrides and carbon nitrides in the form of very pure, fine particulate powder. Appropriate precursors is prepared by reaching a transition metal alkylamide with ammonia to produce a mixture of metal amide and metal imide in the form of an easily pyrolyzable precipitate.

III-nitride semiconductors and their modern devices

CERN Document Server

2013-01-01

This book is dedicated to GaN and its alloys AlGaInN (III-V nitrides), semiconductors with intrinsic properties well suited for visible and UV light emission and electronic devices working at high temperature, high frequency, and harsh environments. There has been a rapid growth in the industrial activity relating to GaN, with GaN now ranking at the second position (after Si) among all semiconductors. This is mainly thanks to LEDs, but also to the emergence of lasers and high power and high frequency electronics. GaN-related research activities are also diversifying, ranging from advanced optical sources and single electron devices to physical, chemical, and biological sensors, optical detectors, and energy converters. All recent developments of nitrides and of their technology are gathered here in a single volume, with chapters written by world leaders in the field. This third book of the series edited by B. Gil is complementary to the preceding two, and is expected to offer a modern vision of nitrides and...

Silicon nitride nanosieve membrane

NARCIS (Netherlands)

Tong, D.H.; Jansen, Henricus V.; Gadgil, V.J.; Bostan, C.G.; Berenschot, Johan W.; van Rijn, C.J.M.; Elwenspoek, Michael Curt

2004-01-01

An array of very uniform cylindrical nanopores with a pore diameter as small as 25 nm has been fabricated in an ultrathin micromachined silicon nitride membrane using focused ion beam (FIB) etching. The pore size of this nanosieve membrane was further reduced to below 10 nm by coating it with

Defect reduction in seeded aluminum nitride crystal growth

Science.gov (United States)

Bondokov, Robert T.; Schowalter, Leo J.; Morgan, Kenneth; Slack, Glen A; Rao, Shailaja P.; Gibb, Shawn Robert

2017-09-26

Bulk single crystal of aluminum nitride (AlN) having an areal planar defect density.ltoreq.100 cm.sup.-2. Methods for growing single crystal aluminum nitride include melting an aluminum foil to uniformly wet a foundation with a layer of aluminum, the foundation forming a portion of an AlN seed holder, for an AlN seed to be used for the AlN growth. The holder may consist essentially of a substantially impervious backing plate.

Synthesis of nitrided MoO{sub 2} and its application as anode materials for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Yoon, Sukeun, E-mail: skyoon@kier.re.kr [New and Renewable Energy Research Division, Korea Institute of Energy Research, Daejeon 305-343 (Korea, Republic of); Jung, Kyu-Nam; Jin, Chang Soo; Shin, Kyung-Hee [New and Renewable Energy Research Division, Korea Institute of Energy Research, Daejeon 305-343 (Korea, Republic of)

2012-09-25

Highlights: Black-Right-Pointing-Pointer Synthesis of nitrided molybdenum oxide by nitridation. Black-Right-Pointing-Pointer Superior cyclability for nitrided molybdenum oxide anodes. Black-Right-Pointing-Pointer Electrochemical reaction behavior of nitrided molybdenum oxide with lithium. - Abstract: Nitrided MoO{sub 2} has been synthesized by hydrothermal processing followed by post-nitridation with NH{sub 3} and investigated as alternative anode materials for rechargeable lithium batteries. Characterization data reveal the presence of molybdenum nitride ({gamma}-Mo{sub 2}N and {delta}-MoN) and molybdenum oxynitride (MoO{sub x}N{sub y}). The nitrided MoO{sub 2} exhibits a capacity of >420 mAh/g after 100 cycles and good rate capability. The improved electrochemical performance of the nitrided MoO{sub 2} compared to that of molybdenum oxide (MoO{sub 2}) is attributed to high electrical conductivity provided by nitrogen doping/or substitution in the oxygen octahedral site of MoO{sub 2} structure.

Ionic nitriding of high chromium martensitic stainless steels

International Nuclear Information System (INIS)

Bruhl, S.P; Charadia, R; Vaca, L.S; Cimetta, J

2008-01-01

Martensitic stainless steels are used in industrial applications where resistance to corrosion and mechanical resistance are needed simultaneously. These steels are normally used in tempering and annealing condition which gives them hardnesses of 500 and 600 HV (about 54 HRC). Ionic nitriding is an assisted diffusion technique that has recently been successfully applied to harden austenitic stainless steels without reducing their resistance to corrosion. The application with AISI 420 martensitic steels has not given good results yet, because in most cases, it affects their corrosion resistance. This work presents the results of the pulsed nitriding of martensitic steels with a higher chrome content, such as the M340 and M333 Boehler steels and they are compared with the same materials after tempering and annealing, without nitriding. The influence of the variations in the parameters of the process, such as the percentage of active time in the pulsed wave, partial nitrogen pressure, current density and effective tension in the microstructure, hardness and wear and corrosion resistance was studied. The microstructure was studied with an optic microscope; the wear resistance with abrasion tests following ASTM G-65 and corrosion with 100 hour long saline haze tests, in a device built according to ASTM B117. Hardness was found to rise to values of 1000 to 1350 HV in all the steels after ionic nitriding, the modified layers oscillated from 3 to 15 microns. As a result, wear resistance also increased, with differences depending on the microstructure and the thickness of the modified layer. However, corrosion resistance was not good, except in the case of the M333 steel test piece with less hardness and a less thick nitrided layer without a noticeable interphase (au)

Erosion-corrosion resistance properties of 316L austenitic stainless steels after low-temperature liquid nitriding

Science.gov (United States)

Zhang, Xiangfeng; Wang, Jun; Fan, Hongyuan; Pan, Dong

2018-05-01

The low-temperature liquid nitriding of stainless steels can result in the formation of a surface zone of so-called expanded austenite (S-phase) by the dissolution of large amounts of nitrogen in the solid solution and formation of a precipitate-free layer supersaturated with high hardness. Erosion-corrosion measurements were performed on low-temperature nitrided and non-nitrided 316L stainless steels. The total erosion-corrosion, erosion-only, and corrosion-only wastages were measured directly. As expected, it was shown that low-temperature nitriding dramatically reduces the degree of erosion-corrosion in stainless steels, caused by the impingement of particles in a corrosive medium. The nitrided 316L stainless steels exhibited an improvement of almost 84% in the erosion-corrosion resistance compared to their non-nitrided counterparts. The erosion-only rates and synergistic levels showed a general decline after low-temperature nitriding. Low-temperature liquid nitriding can not only reduce the weight loss due to erosion but also significantly reduce the weight loss rate of interactions, so that the total loss of material decreased evidently. Therefore, 316L stainless steels displayed excellent erosion-corrosion behaviors as a consequence of their highly favorable corrosion resistances and superior wear properties.

Low-temperature plasma nitriding of sintered PIM 316L austenitic stainless steel

Energy Technology Data Exchange (ETDEWEB)

Mendes, Aecio Fernando; Scheuer, Cristiano Jose; Joanidis, Ioanis Labhardt; Cardoso, Rodrigo Perito; Mafra, Marcio; Klein, Aloisio Nelmo; Brunatto, Silvio Francisco, E-mail: brunatto@ufpr.br [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Dept. de Engenharia Mecanica. Grupo de Tecnologia de Fabricacao Assistida pro Plasma e Metalurgia do Po

2014-08-15

This work reports experimental results on sintered PIM 316L stainless steel low-temperature plasma nitriding. The effect of treatment temperature and time on process kinetics, microstructure and surface characteristics of the nitrided samples were investigated. Nitriding was carried out at temperatures of 350, 380, 410 and 440 °C , and times of 4, 8 and 16 h, using a gas mixture composed by 60% N2 + 20% H2 + 20% Ar, at a gas flow rate of 5.00 X 10{sup 6} Nm{sup 3-1}, and a pressure of 800 Pa. The treated samples were characterized by scanning electron microscopy, X-ray diffractometry and microhardness measurements. Results indicate that low-temperature plasma nitriding is a diffusion controlled process. The calculated activation energy for nitrided layer growth was 111.4 kJmol{sup -1}. Apparently precipitation-free layers were produced in this study. It was also observed that the higher the treatment temperature and time the higher is the obtained surface hardness. Hardness up to 1343 HV{sub 0.025} was verified for samples nitrided at 440 °C. Finally, the characterization of the treated surface indicates the formation of cracks, which were observed in regions adjacent to the original pores after the treatment. (author)

Influence of epoxy, polytetrafluoroethylene (PTFE) and rhodium surface coatings on surface roughness, nano-mechanical properties and biofilm adhesion of nickel titanium (Ni-Ti) archwires

Science.gov (United States)

Asiry, Moshabab A.; AlShahrani, Ibrahim; Almoammar, Salem; Durgesh, Bangalore H.; Kheraif, Abdulaziz A. Al; Hashem, Mohamed I.

2018-02-01

Aim. To investigate the effect of epoxy, polytetrafluoroethylene (PTFE) and rhodium surface coatings on surface roughness, nano-mechanical properties and biofilm adhesion of nickel titanium (Ni-Ti) archwires Methods. Three different coated (Epoxy, polytetrafluoroethylene (PTFE) and rhodium) and one uncoated Ni-Ti archwires were evaluated in the present study. Surface roughness (Ra) was assessed using a non-contact surface profilometer. The mechanical properties (nano-hardness and elastic modulus) were measured using a nanoindenter. Bacterial adhesion assays were performed using Streptococcus mutans (MS) and streptococcus sobrinus (SS) in an in-vitro set up. The data obtained were analyzed using analyses of variance, Tukey’s post hoc test and Pearson’s correlation coefficient test. Result. The highest Ra values (1.29 ± 0.49) were obtained for epoxy coated wires and lowest Ra values (0.29 ± 0.16) were obtained for the uncoated wires. No significant differences in the Ra values were observed between the rhodium coated and uncoated archwires (P > 0.05). The highest nano-hardness (3.72 ± 0.24) and elastic modulus values (61.15 ± 2.59) were obtained for uncoated archwires and the lowest nano-hardness (0.18 ± 0.10) and elastic modulus values (4.84 ± 0.65) were observed for epoxy coated archwires. No significant differences in nano-hardness and elastic modulus values were observed between the coated archwires (P > 0.05). The adhesion of Streptococcus mutans (MS) to the wires was significantly greater than that of streptococcus sobrinus (SS). The epoxy coated wires demonstrated an increased adhesion of MS and SS and the uncoated wires demonstrated decreased biofilm adhesion. The Spearman correlation test showed that MS and SS adhesion was positively correlated with the surface roughness of the wires. Conclusion. The different surface coatings significantly influence the roughness, nano-mechanical properties and biofilm adhesion parameters of the archwires. The

On the buckling of hexagonal boron nitride nanoribbons via structural mechanics

Science.gov (United States)

Giannopoulos, Georgios I.

2018-03-01

Monolayer hexagonal boron nitride nanoribbons have similar crystal structure as graphene nanoribbons, have excellent mechanical, thermal insulating and dielectric properties and additionally present chemical stability. These allotropes of boron nitride can be used in novel applications, in which graphene is not compatible, to achieve remarkable performance. The purpose of the present work is to provide theoretical estimations regarding the buckling response of hexagonal boron nitride monolayer under compressive axial loadings. For this reason, a structural mechanics method is formulated which employs the exact equilibrium atomistic structure of the specific two-dimensional nanomaterial. In order to represent the interatomic interactions appearing between boron and nitrogen atoms, the Dreiding potential model is adopted which is realized by the use of three-dimensional, two-noded, spring-like finite elements of appropriate stiffness matrices. The critical compressive loads that cause the buckling of hexagonal boron nitride nanoribbons are computed with respect to their size and chirality while some indicative buckled shapes of them are illustrated. Important conclusions arise regarding the effect of the size and chirality on the structural stability of the hexagonal boron nitride monolayers. An analytical buckling formula, which provides good fitting of the numerical outcome, is proposed.

Waste conversion into high-value ceramics: Carbothermal nitridation synthesis of titanium nitride nanoparticles using automotive shredder waste.

Science.gov (United States)

Mayyas, Mohannad; Pahlevani, Farshid; Maroufi, Samane; Liu, Zhao; Sahajwalla, Veena

2017-03-01

Environmental concern about automotive shredder residue (ASR) has increased in recent years due to its harmful content of heavy metals. Although several approaches of ASR management have been suggested, these approaches remain commercially unproven. This study presents an alternative approach for ASR management where advanced materials can be generated as a by-product. In this approach, titanium nitride (TiN) has been thermally synthesized by nitriding pressed mixture of automotive shredder residue (ASR) and titanium oxide (TiO 2 ). Interactions between TiO 2 and ASR at non-isothermal conditions were primarily investigated using thermogravimetric analysis (TGA) and differential scanning calorimetry. Results indicated that TiO 2 influences and catalyses degradation reactions of ASR, and the temperature, at which reduction starts, was determined around 980 °C. The interaction between TiO 2 and ASR at isothermal conditions in the temperature range between 1200 and 1550 °C was also studied. The pressed mixture of both materials resulted in titanium nitride (TiN) ceramic at all given temperatures. Formation kinetics were extracted using several models for product layer diffusion-controlled solid-solid and solid-fluid reactions. The effect of reactants ratio and temperature on the degree of conversion and morphology was investigated. The effect of reactants ratio was found to have considerable effect on the morphology of the resulting material, while temperature had a lesser impact. Several unique structures of TiN (porous nanostructured, polycrystalline, micro-spherical and nano-sized structures) were obtained by simply tuning the ratio of TiO 2 to ASR, and a product with appreciable TiN content of around 85% was achieved after only one hour nitridation at 1550 °C. Copyright © 2016 Elsevier Ltd. All rights reserved.

Enantioselective Synthesis of Aminodiols by Sequential Rhodium-Catalysed Oxyamination/Kinetic Resolution: Expanding the Substrate Scope of Amidine-Based Catalysis.

Science.gov (United States)

Guasch, Joan; Giménez-Nueno, Irene; Funes-Ardoiz, Ignacio; Bernús, Miguel; Matheu, M Isabel; Maseras, Feliu; Castillón, Sergio; Díaz, Yolanda

2018-03-26

Regio- and stereoselective oxyamination of dienes through a tandem rhodium-catalysed aziridination-nucleophilic opening affords racemic oxazolidinone derivatives, which undergo a kinetic resolution acylation process with amidine-based catalysts (ABCs) to achieve s values of up to 117. This protocol was applied to the enantioselective synthesis of sphingosine. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extraction of carrier-free 103Pd from thin rhodium wire irradiated with a proton beam in U-150 cyclotron

International Nuclear Information System (INIS)

Yuldashev, B.S.; Khudajbergenov, U.; Gulamov, I.R.; Mirzarva, M.A.; Rylov, A.A.

2003-01-01

A procedure for preparation of 103 Pd isotope of 99.9 % purity from a thin rhodium wire irradiated by 21 MeV proton beam in a cyclotron was developed. The desired product was prepared by electrolytic dissolution of the irradiated target in 6 M HCl with subsequent extraction of 103 Pd isotope without carrier by dimethylglyoxime in chloroform [ru

Surface Texturing-Plasma Nitriding Duplex Treatment for Improving Tribological Performance of AISI 316 Stainless Steel

Directory of Open Access Journals (Sweden)

Naiming Lin

2016-10-01

Full Text Available Surface texturing-plasma nitriding duplex treatment was conducted on AISI 316 stainless steel to improve its tribological performance. Tribological behaviors of ground 316 substrates, plasma-nitrided 316 (PN-316, surface-textured 316 (ST-316, and duplex-treated 316 (DT-316 in air and under grease lubrication were investigated using a pin-on-disc rotary tribometer against counterparts of high carbon chromium bearing steel GCr15 and silicon nitride Si3N4 balls. The variations in friction coefficient, mass loss, and worn trace morphology of the tested samples were systemically investigated and analyzed. The results showed that a textured surface was formed on 316 after electrochemical processing in a 15 wt % NaCl solution. Grooves and dimples were found on the textured surface. As plasma nitriding was conducted on a 316 substrate and ST-316, continuous and uniform nitriding layers were successfully fabricated on the surfaces of the 316 substrate and ST-316. Both of the obtained nitriding layers presented thickness values of more than 30 μm. The nitriding layers were composed of iron nitrides and chromium nitride. The 316 substrate and ST-316 received improved surface hardness after plasma nitriding. When the tribological tests were carried out under dry sliding and grease lubrication conditions, the tested samples showed different tribological behaviors. As expected, the DT-316 samples revealed the most promising tribological properties, reflected by the lowest mass loss and worn morphologies. The DT-316 received the slightest damage, and its excellent tribological performance was attributed to the following aspects: firstly, the nitriding layer had high surface hardness; secondly, the surface texture was able to capture wear debris, store up grease, and then provide continuous lubrication.

Ionic liquid ultrasound assisted dispersive liquid-liquid microextraction method for preconcentration of trace amounts of rhodium prior to flame atomic absorption spectrometry determination

Energy Technology Data Exchange (ETDEWEB)

Molaakbari, Elaheh [Chemistry Department, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of); Young Research Society, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of); Mostafavi, Ali, E-mail: mostafavi.ali@gmail.com [Chemistry Department, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of); Afzali, Daryoush [Environment and Nanochemistry Department, Research Institute of Environmental Science, International Center for Science, High Technology and Environmental Science, Kerman (Iran, Islamic Republic of); Mineral Industries Research Center, Shahid Bahonar University of Kerman, Kerman (Iran, Islamic Republic of)

2011-01-30

In this article, we consider ionic liquid based ultrasound-assisted dispersive liquid-liquid microextraction of trace amounts of rhodium from aqueous samples and show that this is a fast and reliable sample pre-treatment for the determination of rhodium ions by flame atomic absorption spectrometry. The Rh(III) was transferred into its complex with 2-(5-bromo-2-pyridylazo)-5-diethylamino phenol as a chelating agent, and an ultrasonic bath with the ionic liquid, 1-octyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide at room temperature was used to extract the analyte. The centrifuged rhodium complex was then enriched in the form of ionic liquid droplets and prior to its analysis by flame atomic absorption spectrometry, 300 {mu}L ethanol was added to the ionic liquid-rich phase. Finally, the influence of various parameters on the recovery of Rh(III) was optimized. Under optimum conditions, the calibration graph was linear in the range of 4.0-500.0 ng mL{sup -1}, the detection limit was 0.37 ng mL{sup -1} (3S{sub b}/m, n = 7) and the relative standard deviation was {+-}1.63% (n = 7, C = 200 ng mL{sup -1}). The results show that ionic liquid based ultrasound assisted dispersive liquid-liquid microextraction, combined with flame atomic absorption spectrometry, is a rapid, simple, sensitive and efficient analytical method for the separation and determination of trace amounts of Rh(III) ions with minimum organic solvent consumption.

Bonding silicon nitride using glass-ceramic

International Nuclear Information System (INIS)

Dobedoe, R.S.

1995-01-01

Silicon nitride has been successfully bonded to itself using magnesium-aluminosilicate glass and glass-ceramic. For some samples, bonding was achieved using a diffusion bonder, but in other instances, following an initial degassing hold, higher temperatures were used in a nitrogen atmosphere with no applied load. For diffusion bonding, a small applied pressure at a temperature below which crystallisation occurs resulted in intimate contact. At slightly higher temperatures, the extent of the reaction at the interface and the microstructure of the glass-ceramic joint was highly sensitive to the bonding temperature. Bonding in a nitrogen atmosphere resulted in a solution-reprecipitation reaction. A thin layer of glass produced a ''dry'', glass-free joint, whilst a thicker layer resulted in a continuous glassy join across the interface. The chromium silicide impurities within the silicon nitride react with the nucleating agent in the glass ceramic, which may lead to difficulty in producing a fine glass-ceramic microstructure. Slightly lower temperatures in nitrogen resulted in a polycrystalline join but the interfacial contact was poor. It is hoped that one of the bonds produced may be developed to eventually form part of a graded joint between silicon nitride and a high temperature nickel alloy. (orig.)

Heterostructures for Increased Quantum Efficiency in Nitride LEDs

Energy Technology Data Exchange (ETDEWEB)

Davis, Robert F. [Carnegie Mellon Univ., Pittsburgh, PA (United States)

2010-09-30

Task 1. Development of an advanced LED simulator useful for the design of efficient nitride-based devices. Simulator will contain graphical interface software that can be used to specify the device structure, the material parameters, the operating conditions and the desired output results. Task 2. Theoretical and experimental investigations regarding the influence on the microstructure, defect concentration, mechanical stress and strain and IQE of controlled changes in the chemistry and process route of deposition of the buffer layer underlying the active region of nitride-based blue- and greenemitting LEDs. Task 3. Theoretical and experimental investigations regarding the influence on the physical properties including polarization and IQE of controlled changes in the geometry, chemistry, defect density, and microstructure of components in the active region of nitride-based blue- and green-emitting LEDs. Task 4. Theoretical and experimental investigations regarding the influence on IQE of novel heterostructure designs to funnel carriers into the active region for enhanced recombination efficiency and elimination of diffusion beyond this region. Task 5. Theoretical and experimental investigations regarding the influence of enhanced p-type doping on the chemical, electrical, and microstructural characteristics of the acceptor-doped layers, the hole injection levels at Ohmic contacts, the specific contact resistivity and the IQE of nitride-based blue- and green-emitting LEDs. Development and optical and electrical characterization of reflective Ohmic contacts to n- and p-type GaN films.

The UV Plasmonic Behavior of Distorted Rhodium Nanocubes

Directory of Open Access Journals (Sweden)

Yael Gutiérrez

2017-12-01

Full Text Available For applications of surface-enhanced spectroscopy and photocatalysis, the ultraviolet (UV plasmonic behavior and charge distribution within rhodium nanocubes is explored by a detailed numerical analysis. The strongest plasmonic hot-spots and charge concentrations are located at the corners and edges of the nanocubes, exactly where they are the most spectroscopically and catalytically active. Because intense catalytic activity at corners and edges will reshape these nanoparticles, distortions of the cubical shape, including surface concavity, surface convexity, and rounded corners and edges, are also explored to quantify how significantly these distortions deteriorate their plasmonic and photocatalytic properties. The fact that the highest fields and highest carrier concentrations occur in the corners and edges of Rh nanocubes (NCs confirms their tremendous potential for plasmon-enhanced spectroscopy and catalysis. It is shown that this opportunity is fortuitously enhanced by the fact that even higher field and charge concentrations reside at the interface between the metal nanoparticle and a dielectric or semiconductor support, precisely where the most chemically active sites are located.

Preparation of phosphorus targets using the compound phosphorus nitride

International Nuclear Information System (INIS)

Maier-Komor, P.

1987-01-01

Commercially available phosphorus nitride (P 3 N 5 ) shows a high oxygen content. Nevertheless, this material is attractive for use as phosphorus targets in experiments where red phosphorus would disappear due to its high vapor pressure and where a metal partner in the phosphide must be excluded due to its high atomic number. Methods are described to produce phosphorus nitride targets by vacuum evaporation condensation. (orig.)

Remarkable promoting effect of rhodium on the catalytic performance of Ag/Al2O3 for the selective reduction of NO with decane

International Nuclear Information System (INIS)

Sato, Kazuhito; Yoshinari, Tomohiro; Kintaichi, Yoshiaki; Haneda, Masaaki; Hamada, Hideaki

2003-01-01

The addition of small amounts of rhodium enhanced the activity of Ag/Al 2 O 3 catalyst for the selective reduction of NO with decane at low temperatures. The Rh-promoted Ag/Al 2 O 3 showed its high performance even in the presence of low concentrations of SO 2 . Based on the catalytic activity for elementary reactions, it was suggested that the role of added rhodium is to enhance the reaction between NO x and decane-derived species, leading to NO reduction. Catalyst characterization by UV-Vis spectroscopy indicated that the major silver species on Rh-promoted Ag/Al 2 O 3 is Ag nn δ+ clusters, which would be responsible for the high activity. FT-IR measurements revealed that the formation rate of isocyanate species, which is a major reaction intermediate, is higher on Rh-promoted Ag/Al 2 O 3

Determination of Ultra-trace Rhodium in Water Samples by Graphite Furnace Atomic Absorption Spectrometry after Cloud Point Extraction Using 2-(5-Iodo-2-Pyridylazo)-5-Dimethylaminoaniline as a Chelating Agent.

Science.gov (United States)

Han, Quan; Huo, Yanyan; Wu, Jiangyan; He, Yaping; Yang, Xiaohui; Yang, Longhu

2017-03-24

A highly sensitive method based on cloud point extraction (CPE) separation/preconcentration and graphite furnace atomic absorption spectrometry (GFAAS) detection has been developed for the determination of ultra-trace amounts of rhodium in water samples. A new reagent, 2-(5-iodo-2-pyridylazo)-5-dimethylaminoaniline (5-I-PADMA), was used as the chelating agent and the nonionic surfactant TritonX-114 was chosen as extractant. In a HAc-NaAc buffer solution at pH 5.5, Rh(III) reacts with 5-I-PADMA to form a stable chelate by heating in a boiling water bath for 10 min. Subsequently, the chelate is extracted into the surfactant phase and separated from bulk water. The factors affecting CPE were investigated. Under the optimized conditions, the calibration graph was linear in the range of 0.1-6.0 ng/mL, the detection limit was 0.023 ng/mL for rhodium and relative standard deviation was 3.67% ( c = 1.0 ng/mL, n = 11)．The method has been applied to the determination of trace rhodium in water samples with satisfactory results.

Production of 15N for nitride type nuclear fuel

International Nuclear Information System (INIS)

Axente, Damian

2005-01-01

Full text: Nitride nuclear fuel is the choice for advanced nuclear reactors and ADS, considering its favorable properties as: melting point, excellent thermal conductivity, high fissile density, lower fission gas release and good radiation tolerance. The application of nitride fuels in different nuclear reactors requires use of 15 N enriched nitrogen to suppress 14 C production due to (n,p) reaction on 14 N. Nitride fuel is a promising candidate for transmutation in ADSs of radioactive minor actinides, which are converted into nitrides with 15 N for that purpose. Taking into account that at present the world wide 15 N market is about 20 - 40 Kg 15 N/y, the supply of that isotope for nitride type nuclear fuel, would demand an increase in production capacity by a factor of 1000. For an industrial plant producing 100 t/y 15 N at 99 at. % 15 N concentration, using present technology of 15 N/ 14 N isotopic exchange in Nitrox system, the first separation stage of the cascade would be fed with 10M HNO 3 solution at a 600 m 3 /h flow-rate. If conversion of HNO 3 into NO, NO 2 , at the enriching end of the columns, would be done with gaseous SO 2 , for an industrial plant of 100 t/y 15 N a consumption of 4 million t SO 2 /y and a production of 70 % H 2 SO 4 waste solution of 4.5 million m 3 /y are estimated. The reconversion of H 2 SO 4 into SO 2 in order to recycle SO 2 is a problem to be solved to compensate the cost of sulfur dioxide and to diminish the amount of sulfuric acid waste solution. It should be taken into consideration an important price reduction of 15 N in order to make possible its utilization for industrial production of nitride type nuclear fuel. (authors)

Preparation of uranium-plutonium mixed nitride pellets with high purity

International Nuclear Information System (INIS)

Arai, Yasuo; Shiozawa, Ken-ichi; Ohmichi, Toshihiko

1992-01-01

Uranium-plutonium mixed nitride pellets have been prepared in the gloveboxes with high purity Ar gas atmosphere. Carbothermic reduction of the oxides in N 2 -H 2 mixed gas stream was adopted for synthesizing mixed nitride. Sintering was carried out in various conditions and the effect on the pellet characteristics was investigated. (author)

Device for neutron flux monitoring in IEA-R1 reactor using rhodium self powered neutron detector; Dispositivo de mapeamento de fluxo de neutron atraves do SPN/Rodio no IEA-R1

Energy Technology Data Exchange (ETDEWEB)

Ricci Filho, Walter; Fernando, Alberto de Jesus; Jerez, Rogerio; Tondin, Julio B.M.; Pasqualetto, Hertz [Instituto de Pesquisas Energeticas e Nucleares (IPEN), Sao Paulo, SP (Brazil)

2000-07-01

The IEA-R1 reactor has undergone a modernization tio increase its operating power to 5 MW, in order to allow a more efficient production of radioisotopes. The objective of this work is to provide the reactor with flux monitoring device using a rhodium self powered neutron detector. Self powered detectors are rugged miniature devices with are increasingly being used for fixed in core reactor monitoring both for safety purposes and flux mapping. The work presents the results obtained with Rhodium-SPND in several irradiation position inside the reactor core. (author)

Nitriding and Nitrocarburizing; Current Status and Future Challenges

DEFF Research Database (Denmark)

Somers, Marcel A. J.

, aspects of low temperature surface hardening of stainless steels in a gaseous environment will be addressed. Here, the developed case consists of expanded austenite and/or expanded martensite, which essentially is a super saturated solid solution of nitrogen/carbon in austenite/martensite. The current......This contribution addresses the current understanding of gaseous nitriding and nitrocarburizing. Aspects of thermodynamics, kinetics and microstructure development in iron and heat treatable steel will be explained. In these materials the nitrided/ nitrocarburized case can be subdivided...

trans-Carbonylchloridobis[dicyclohexyl(4-isopropylphenylphosphane]rhodium(I acetone monosolvate

Directory of Open Access Journals (Sweden)

Sizwe Makhoba

2011-09-01

Full Text Available The title rhodium Vaska-type complex, trans-[RhCl{P(C6H112(C6H4-4-C3H72}2(CO], crystallizes with an accompanying acetone solvent molecule. The metal atom shows a distorted square-planar coordination environment with selected important geometrical parameters of Rh—P = 2.3237 (6 and 2.3253 (6 Å, Rh—Cl = 2.3724 (6 Å, Rh—C = 1.802 (2 Å, P—Rh—P = 173.42 (2° and Cl—Rh—C = 179.13 (7°. Effective cone angles for the two P atoms are 165 and 161°, respectively. Both isopropyl groups and the acetone molecule are disordered with occupancy values of 0.523 (5:0.477 (5, 0.554 (8:0.446 (8 and 0.735 (4:0.265 (4, respectively. The crystal packing is stabilized by weak C—H...O and C—H...Cl contacts.

Kinetic modelling of chlorination of nitrided ilmenite using MATLAB

Energy Technology Data Exchange (ETDEWEB)

Ramakrishnan, Sivakumar, E-mail: srsivakumar@usm.my; Kwok, Teong Chen, E-mail: ctck@live.com; Hamid, Sheikh Abdul Rezan Sheikh Abdul, E-mail: rezanshk@gmail.com [School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, 14300, Nibong Tebal, Penang (Malaysia)

2016-07-19

In the present study, chlorination of nitride ilmenite using 2{sup k} factorial design was investigated. The reduction experiments were carried out in a temperature range of 400°C to 500°C, chlorination duration from 1 hour to 3 hours and using different type of carbon reactant. Phases of raw materials and reduced samples were analyzed by X-ray diffraction (XRD). Ilmenite was reduced to TiO{sub x}C{sub y}N{sub z} through carbothermal and nitridation for further chlorination into titanium tetrachloride. The Design of Experiment analysis suggested that the types of carbon reactant contribute most influence to the extent of chlorination of nitride ilmenite. The extent of chlorination was highest at 500°C with 3 hours chlorination time and carbon nanotube as carbon reactant.

Crystal structures of fac-trichloridotris(trimethylphosphane-κPrhodium(III monohydrate and fac-trichloridotris(trimethylphosphane-κPrhodium(III methanol hemisolvate: rhodium structures that are isotypic with their iridium analogs

Directory of Open Access Journals (Sweden)

Joseph S. Merola

2015-02-01

Full Text Available The crystal structures of two solvates of fac-trichloridotris(trimethylphosphane-κPrhodium(III are reported, i.e. one with water in the crystal lattice, fac-[RhCl3(Me3P3]·H2O, and one with methanol in the crystal lattice, fac-[RhCl3(Me3P3]·0.5CH3OH. These rhodium compounds exhibit distorted octahedral coordination spheres at the metal and are isotypic with the analogous iridium compounds previously reported by us [Merola et al. (2013. Polyhedron, 54, 67–73]. Comparison is made between the rhodium and iridium compounds, highlighting their isostructural relationships.

The influence of nitride thickness variations on the switching speed of MNOS memory transistors

DEFF Research Database (Denmark)

Bruun, Erik

1978-01-01

The influence of nitride thickness variations on the switching speed of MNOS memory transistors is examined. The switching time constant is calculated as a function of the nitride thickness using a model of modified Fowler-Nordheim injection. The calculated characteristics compare well with measu......The influence of nitride thickness variations on the switching speed of MNOS memory transistors is examined. The switching time constant is calculated as a function of the nitride thickness using a model of modified Fowler-Nordheim injection. The calculated characteristics compare well...

Comprehensive perspective on the mechanism of preferred orientation in reactive-sputter-deposited nitrides

International Nuclear Information System (INIS)

Kajikawa, Yuya; Noda, Suguru; Komiyama, Hiroshi

2003-01-01

Texture control of sputter-deposited nitride films has provoked a great deal of interest due to its technological importance. Despite extensive research, however, the reported results are scattered and discussions about the origin of preferred orientation (PO) are sometimes conflicting, and therefore controversial. The aim of this study is to acquire a clear perspective in order to discuss the origin of PO of sputter-deposited nitrides. Among nitrides, we focus on titanium nitride (TiN), aluminum nitride (AlN), and tantalum nitride (TaN), which are three commonly used nitrides. First, we collected reported experimental results about the relation between operating conditions and PO, because PO is considered to be determined by film formation processes, such as surface diffusion or grain growth, which is affected by operating conditions. We also collected reported results about such PO-determining processes. Then, we categorized the PO-determining processes into an initial stage and a growth stage of film deposition, and further categorized each stage into a vapor-solid interface and a solid-solid interface. Then, we related each stage and interface to film morphology and to PO-determining processes. Finally, based on existing results, previous models, and proposed schema, we discuss the origin of PO. Based on previous experimental results on film morphology, PO of nitride films occurred in the growth stage at the vapor-solid interface, where the sticking process of the precursor and the surface diffusion process determine PO, rather than in the initial stage and in the growth stage at the solid-solid interface. TiN (002) PO, however, seems to be caused in the initial stage at the solid-solid interface

Colloidal characterization of silicon nitride and silicon carbide

Science.gov (United States)

Feke, Donald L.

1986-01-01

The colloidal behavior of aqueous ceramic slips strongly affects the forming and sintering behavior and the ultimate mechanical strength of the final ceramic product. The colloidal behavior of these materials, which is dominated by electrical interactions between the particles, is complex due to the strong interaction of the solids with the processing fluids. A surface titration methodology, modified to account for this interaction, was developed and used to provide fundamental insights into the interfacial chemistry of these systems. Various powder pretreatment strategies were explored to differentiate between true surface chemistry and artifacts due to exposure history. The colloidal behavior of both silicon nitride and carbide is dominated by silanol groups on the powder surfaces. However, the colloid chemistry of silicon nitride is apparently influenced by an additional amine group. With the proper powder treatments, silicon nitride and carbide powder can be made to appear colloidally equivalent. The impact of these results on processing control will be discussed.

Electron trapping during irradiation in reoxidized nitrided oxide

International Nuclear Information System (INIS)

Mallik, A.; Vasi, J.; Chandorkar, A.N.

1993-01-01

Isochronal detrapping experiments have been performed following irradiation under different gate biases in reoxidized nitrided oxide (RNO) MOS capacitors. These show electron trapping by the nitridation-induced electron traps at low oxide fields during irradiation. A difference in the detrapping behavior of trapped holes and electrons is observed, with trapped holes being detrapped at relatively lower temperatures compared to trapped electrons. Electron trapping shows a strong dependence on tile magnitude of the applied gate bias during irradiation but is independent of its polarity. Conventional oxide devices, as expected, do not show any electron trapping during irradiation by the native electron traps. Finally, a comparison of the isochronal detrapping behavior following irradiation and following avalanche injection of electrons has been made to estimate the extent of electron trapping. The results show that electron trapping by the nitridation-induced electron traps does not play the dominant role in improving radiation performance of RNO, though its contribution cannot be completely neglected for low oxide field irradiations

Reduction of Defects on Microstructure Aluminium Nitride Using High Temperature Annealing Heat Treatment

Science.gov (United States)

Tanasta, Z.; Muhamad, P.; Kuwano, N.; Norfazrina, H. M. Y.; Unuh, M. H.

2018-03-01

Aluminium Nitride (AlN) is a ceramic 111-nitride material that is used widely as components in functional devices. Besides good thermal conductivity, it also has a high band gap in emitting light which is 6 eV. AlN thin film is grown on the sapphire substrate (0001). However, lattice mismatch between both materials has caused defects to exist along the microstructure of AlN thin films. The defects have affected the properties of Aluminium Nitride. Annealing heat treatment has been proved by the previous researcher to be the best method to improve the microstructure of Aluminium Nitride thin films. Hence, this method is applied at four different temperatures for two hour. The changes of Aluminium Nitride microstructures before and after annealing is observed using Transmission Electron Microscope. It is observed that inversion domains start to occur at temperature of 1500 °C. Convergent Beam Electron Diffraction pattern simulation has confirmed the defects as inversion domain. Therefore, this paper is about to extract the matters occurred during the process of producing high quality Aluminium Nitride thin films and the ways to overcome this problem.

Study on the nitride fuel fabrication for FBR cycle (1)

International Nuclear Information System (INIS)

Shinkai, Yasuo; Ono, Kiyoshi; Tanaka, Kenya

2002-07-01

In the phase-II of JNC's 'Feasibility Study on Commercialized Fuel Reactor Cycle System (the F/S)', the nitride fuels are selected as candidate for fuels for heavy metal cooled reactor, gas cooled reactor, and small scale reactor. In particular, the coated fuel particles are a promising concept for gas cooled reactor. In addition, it is necessary to study in detail the application possibility of pellet nitride fuel and vibration compaction nitride fuel for heavy metal cooled reactor and small scale reactor in the phase-II. In 2001, we studied more about additional equipments for the nitride fuel fabrication in processes from gelation to carbothermic reduction in the vibration compaction method. The result of reevaluation of off-gas mass flow around carbothermic reduction equipment in the palletizing method, showed that quantity of off-gas flow reduced and its reduction led the operation cost to decrease. We studied the possibility of fabrication of large size particles in the coated fuel particles for helium gas cooled reactor and we made basic technical issues clear. (author)