Reaction mechanisms at 4H-SiC/SiO2 interface during wet SiC oxidation

Science.gov (United States)

Akiyama, Toru; Hori, Shinsuke; Nakamura, Kohji; Ito, Tomonori; Kageshima, Hiroyuki; Uematsu, Masashi; Shiraishi, Kenji

2018-04-01

The reaction processes at the interface between SiC with 4H structure (4H-SiC) and SiO2 during wet oxidation are investigated by electronic structure calculations within the density functional theory. Our calculations for 4H-SiC/SiO2 interfaces with various orientations demonstrate characteristic features of the reaction depending on the crystal orientation of SiC: On the Si-face, the H2O molecule is stable in SiO2 and hardly reacts with the SiC substrate, while the O atom of H2O can form Si-O bonds at the C-face interface. Two OH groups are found to be at least necessary for forming new Si-O bonds at the Si-face interface, indicating that the oxidation rate on the Si-face is very low compared with that on the C-face. On the other hand, both the H2O molecule and the OH group are incorporated into the C-face interface, and the energy barrier for OH is similar to that for H2O. By comparing the calculated energy barriers for these reactants with the activation energies of oxide growth rate, we suggest the orientation-dependent rate-limiting processes during wet SiC oxidation.

Electronic and optical properties of Y-doped Si{sub 3}N{sub 4} by density functional theory

Energy Technology Data Exchange (ETDEWEB)

Huang, Zhifeng [State Key Lab of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China); Chen, Fei, E-mail: chenfei027@gmail.com [State Key Lab of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China); Key Laboratory of Advanced Technology for Specially Functional Materials, Ministry of Education, Wuhan University of Technology, Wuhan 430070 (China); Su, Rui; Wang, Zhihao; Li, Junyang; Shen, Qiang [State Key Lab of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China); Zhang, Lianmeng [State Key Lab of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China); Key Laboratory of Advanced Technology for Specially Functional Materials, Ministry of Education, Wuhan University of Technology, Wuhan 430070 (China)

2015-07-15

Highlights: • Y-doped α-Si{sub 3}N{sub 4} and β-Si{sub 3}N{sub 4} are systematically investigated by DFT. • Impacts of local structure and bond character on electronic property are studied. • Static dielectric constants and optical absorption properties are investigated. - Abstract: Geometry structures, formation energies, electronic and optical properties of Y-doped α-Si{sub 3}N{sub 4} and β-Si{sub 3}N{sub 4} are investigated based on the density functional theory (DFT). The low values of formation energies indicate both Y-doped Si{sub 3}N{sub 4} models can be easily synthesized. Besides, the negative formation energies of α-Y{sub i}-Si{sub 3}N{sub 4} demonstrate that interstitial Y-doped α-Si{sub 3}N{sub 4} has an excellent stability. The energies of impurity levels are different resulting from the different chemical environment around Y atoms. The impurity levels localized in the band gap reduces the maximum energy gaps, which enhances the optical properties of Si{sub 3}N{sub 4}. The static dielectric constants become larger and the optical absorption spectra show the red-shift phenomena for all Y-doped Si{sub 3}N{sub 4} models.

The Au/Si eutectic bonding compatibility with KOH etching for 3D devices fabrication

Science.gov (United States)

Liang, Hengmao; Liu, Mifeng; Liu, Song; Xu, Dehui; Xiong, Bin

2018-01-01

KOH etching and Au/Si eutectic bonding are cost-efficient technologies for 3D device fabrication. Aimed at investigating the process compatibility of KOH etching and Au/Si bonding, KOH etching tests have been carried out for Au/bulk Si and Au/amorphous Si (a-Si) bonding wafers in this paper. For the Au/bulk Si bonding wafer, a serious underetch phenomenon occurring on the damage layer in KOH etching definitely results in packaging failure. In the microstructure analysis, it is found that the formation of the damage layer between the bonded layer and bulk Si is attributed to the destruction of crystal Si lattices in Au/bulk Si eutectic reaction. Considering the occurrence of underetch for Au/Si bonding must meet two requirements: the superfluous Si and the defective layer near the bonded layer, the Au/a-Si bonding by regulating the a-Si/Au thickness ratio is presented in this study. Only when the a-Si/Au thickness ratio is relatively low are there not underetch phenomena, of which the reason is the full reaction of the a-Si layer avoiding the formation of the damage layer for easy underetch. Obviously, the Au/a-Si bonding via choosing a moderate a-Si/Au thickness ratio (⩽1.5:1 is suggested) could be reliably compatible with KOH etching, which provides an available and low-cost approach for 3D device fabrication. More importantly, the theory of the damage layer proposed in this study can be naturally applied to relevant analyses on the eutectic reaction of other metals and single crystal materials.

Nanostructures based in boro nitride thin films deposited by PLD onto Si/Si3N4/DLC substrate

International Nuclear Information System (INIS)

Roman, W S; Riascos, H; Caicedo, J C; Ospina, R; Tirado-MejIa, L

2009-01-01

Diamond-like carbon and boron nitride were deposited like nanostructered bilayer on Si/Si 3 N 4 substrate, both with (100) crystallographic orientation, these films were deposited through pulsed laser technique (Nd: YAG: 8 Jcm -2 , 9ns). Graphite (99.99%) and boron nitride (99.99%) targets used to growth the films in argon atmosphere. The thicknesses of bilayer were determined with a perfilometer, active vibration modes were analyzed using infrared spectroscopy (FTIR), finding bands associated around 1400 cm -1 for B - N bonding and bands around 1700 cm -1 associated with C=C stretching vibrations of non-conjugated alkenes and azometinic groups, respectively. The crystallites of thin films were analyzed using X-ray diffraction (XRD) and determinated the h-BN (0002), α-Si 3 N 4 (101) phases. The aim of this study is to relate the dependence on physical and chemical characteristics of the system Si/Si 3 N 4 /DLC/BN with gas pressure adjusted at the 1.33, 2.67 and 5.33 Pa values.

LiCa{sub 4}Si{sub 4}N{sub 8}F and LiSr{sub 4}Si{sub 4}N{sub 8}F. Nitridosilicate fluorides with a BCT-zeolite-type network structure

Energy Technology Data Exchange (ETDEWEB)

Horky, Katrin; Schnick, Wolfgang [Department of Chemistry, Inorganic Solid-State, Chemistry, University of Munich (LMU), Butenandtstrasse 5-13, 81377, Munich (Germany)

2017-02-17

LiCa{sub 4}Si{sub 4}N{sub 8}F and LiSr{sub 4}Si{sub 4}N{sub 8}F were synthesized from Si{sub 3}N{sub 4}, LiNH{sub 2}, CaH{sub 2}/SrH{sub 2}, and LiF through a metathesis reaction in a radiofrequency furnace. The crystal structures of both compounds were solved and refined on the basis of single-crystal X-ray diffraction data [LiCa{sub 4}Si{sub 4}N{sub 8}F: P2{sub 1}/c (no. 14), a = 10.5108(3), b = 9.0217(3), c = 10.3574(3) Aa, β = 117.0152(10) , R{sub 1} = 0.0422, wR{sub 2} = 0.0724, Z = 4; LiSr{sub 4}Si{sub 4}N{sub 8}F: P4nc (no. 104), a = 9.3118(4), b = 9.3118(4), c = 5.5216(2) Aa, R{sub 1} = 0.0160, wR{sub 2} = 0.0388, Z = 2]. The silicate substructure of both compounds is built up of vertex-sharing SiN{sub 4} tetrahedra, thereby forming a structure analogous to the BCT zeolite with Ca{sup 2+}/Sr{sup 2+}, Li{sup +}, and F{sup -} ions filling the voids. The crystal structure of LiSr{sub 4}Si{sub 4}N{sub 8}F is homeotypic with that of Li{sub 2}Sr{sub 4}Si{sub 4}N{sub 8}O as it exhibits the same zeolite-type [SiN{sub 2}]{sup 2-} framework, but incorporates LiF instead of Li{sub 2}O. In contrast to the respective Sr compound, LiCa{sub 4}Si{sub 4}N{sub 8}F shows a distortion of the BCT-zeolite-type network as well as an additional site for F. Both F sites in LiCa{sub 4}Si{sub 4}N{sub 8}F exhibit different coordination spheres to LiSr{sub 4}Si{sub 4}N{sub 8}F. The title compounds are the first reported lithium alkaline-earth nitridosilicates containing fluorine. The crystal structures were confirmed by lattice-energy calculations (MAPLE), energy-dispersive X-ray spectroscopy (EDX) measurements, and powder X-ray diffraction. IR spectra confirmed the absence of N-H bonds. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Sintering behaviour and phase relationships of Si[sub 3]N[sub 4] ceramics in the Si[sub 3]N[sub 4]-SiO[sub 2]-MgO-Y[sub 2]O[sub 3] system. Sinterverhalten und Phasenbeziehungen von Si[sub 3]N[sub 4]-Keramiken im System Si[sub 3]N[sub 4]-SiO[sub 2]-MgO-Y[sub 2]O[sub 3

Energy Technology Data Exchange (ETDEWEB)

Mahoney, F.M.

1992-10-12

The aim of this work is the investigation of the sintering or crystallisation behaviour of Si[sub 3]N[sub 4] ceramics depending on the additive composition in the Si[sub 3]N[sub 4]-SiO[sub 2]-MgO-Y[sub 2]O[sub 3] system. With regard to the complicated manufacturing process of sintered and heat-treated Si[sub 3]N[sub 4] ceramics, one should first determine which additive compositions make complete compression possible. The effect of the composition on the volume and the viscosity of the melting phase should be cleared up, where determining the Si[sub 3]N[sub 4] solubility relative to the additive composition is of special importance. The phase relationships between Si[sub 3]N[sub 4] and the possible crystalline secondary phases should be determined for the crystallisation behaviour. Due to the very fine distribution of only a 5-15% proportion of additive in conventional Si[sub 3]N[sub 4] samples, a characterisation of the secondary phases is difficult to carry out with X-ray or REM/EDX analysis. Therefore, experiments with oxy-nitridic model samples were carried out in this work, which have the same phase relationships as conventional Si[sub 3]N[sub 4] compositions, but with an appreciably higher proportion of additive. The possibility of transferring the results of the model samples were tested on examples of three Si[sub 3]N[sub 4] ceramics. (orig.)

Oxidation Protection of Porous Reaction-Bonded Silicon Nitride

Science.gov (United States)

Fox, D. S.

1994-01-01

Oxidation kinetics of both as-fabricated and coated reaction-bonded silicon nitride (RBSN) were studied at 900 and 1000 C with thermogravimetry. Uncoated RBSN exhibited internal oxidation and parabolic kinetics. An amorphous Si-C-O coating provided the greatest degree of protection to oxygen, with a small linear weight loss observed. Linear weight gains were measured on samples with an amorphous Si-N-C coating. Chemically vapor deposited (CVD) Si3N4 coated RBSN exhibited parabolic kinetics, and the coating cracked severely. A continuous-SiC-fiber-reinforced RBSN composite was also coated with the Si-C-O material, but no substantial oxidation protection was observed.

Improvement of photoluminescence intensity of Ce-doped Y{sub 3}Al{sub 5}O{sub 12} phosphor by Si{sub 3}N{sub 4} addition

Energy Technology Data Exchange (ETDEWEB)

Shyu, Jiin-Jyh, E-mail: jjshyu@ttu.edu.tw; Yang, Chia-Wei

2017-06-01

Yttrium aluminum garnet (Y{sub 3}Al{sub 5}O{sub 12}, YAG) has been widely used as a host for luminescent ions. The present paper describes the effects of Si{sub 3}N{sub 4} addition on the formation and photoluminescence properties of the Ce-doped YAG yellow phosphors. Phosphor powders with the nominal compositions of Y{sub 2.95}Ce{sub 0.05}Al{sub 5-m}Si{sub m}O{sub 12-m}N{sub m} (m = 0–0.6) were prepared by calcining the mixed raw materials at 1500 °C in nitrogen atmosphere. X-ray diffraction, x-ray photoelectron spectroscopy, scanning electron microscope, and transmission electron microscopy equipped with an energy dispersive x-ray spectrometer were used to characterize the structure of the calcined powders. The photoluminescence properties were measured with fluorescence spectrophotometry. It was found that in the range of m = 0–0.27, single phase YAG solid solution (s.s.) in which the Y, Al, and O sites are partially occupied by Ce, Si, and N ions, respectively. The nitrogen ions do not distribute homogeneously over the YAG lattice. The tendency to bond with nitrogen ion for the cations is (Y, Ce) > Si > Al. With the increase in the Si{sub 3}N{sub 4} content, the increase in both the Ce{sup 3+}/(Ce{sup 3+} + Ce{sup 4+}) ratio and the Ce-N bonds improve the intensity of the photoluminescent emission. At m = 0.27, the emission intensity reaches a maximum which is about 2.5 and 1.6 times of that for the Si{sub 3}N{sub 4}-free composition (m = 0) calcined in air and nitrogen, respectively. When the Si{sub 3}N{sub 4} content (m) is higher than 0.27, the emission intensity decreases due to the existence of residual Si{sub 3}N{sub 4} phase. - Highlights: • Addition of Si{sub 3}N{sub 4} can increase the emission intensity of YAG:Ce up to 2.5 times. • Increase in the Ce{sup 3+}/Ce{sup 4+} ratio and the number of Ce-N bonds improve the emission. • The tendency to bond with nitrogen ion for cations in YAG:Ce is (Y, Ce) > Si > Al. • The incomplete dissolution

Effect of Pressurizing during Compaction and Sintering on the Formation of Reaction-Bonded SiC–Ti{sub 3}SiC{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Kim, Sun-Han; Jung, Yang-Il; Rhee, Young-Woo; Park, Dong-Jun; Park, Jung-Hwan; Park, Jeong-Yong; Kim, Hyun-Gil; Koo, Yang-Hyun [LWR Fuel Technology Division, KAERI, Daejeon (Korea, Republic of)

2016-05-15

A reaction-bonded SiC-Ti{sub 3}SiC{sub 2} ceramic composite was produced for use in a ceramic-metal composite cladding tube. The diffusion reaction between TiC and Si was investigated with respect to process pressure. The mole-fraction of TiC and Si was controlled to be 3:2 to obtain a Ti{sub 3}SiC{sub 2} phase in the ceramic composite. Sintering was conducted at 1450 °C where TiC particles could react with melted Si. SiC ceramic composites consisting of Ti{sub 3}SiC{sub 2} and TiSi{sub 2} matrix phases were obtained. The formation of the constituent phases was strongly related to the processing pressure. The number of second phases in the SiC-Ti{sub 3}SiC{sub 2} composite was controlled by adjusting the processing pressure. When the powder compacts were not pressurized, no Ti{sub 3}SiC{sub 2} phase was formed. However, the Ti{sub 3}SiC{sub 2} phase was formed under pressurizing during compaction and/or sintering. The higher the pressure the higher the purity of SiC-Ti{sub 3}SiC{sub 2}. The dual-phased SiC-Ti{sub 3}SiC{sub 2} composite, however, revealed the decreased resistance to high-temperature oxidation. It is suggested that the incorporation of TiSi{sub 2} in the composite increases the oxidation resistance as well as mechanical property.

Fluorocarbon based atomic layer etching of Si{sub 3}N{sub 4} and etching selectivity of SiO{sub 2} over Si{sub 3}N{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Li, Chen [Department of Physics, and Institute for Research in Electronics and Applied Physics, University of Maryland, College Park, Maryland 20742 (United States); Metzler, Dominik; Oehrlein, Gottlieb S., E-mail: oehrlein@umd.edu [Department of Materials Science and Engineering, and Institute for Research in Electronics and Applied Physics, University of Maryland, College Park, Maryland 20742 (United States); Lai, Chiukin Steven; Hudson, Eric A. [Lam Research Corporation, 4400 Cushing Parkway, Fremont, California 94538 (United States)

2016-07-15

Angstrom-level plasma etching precision is required for semiconductor manufacturing of sub-10 nm critical dimension features. Atomic layer etching (ALE), achieved by a series of self-limited cycles, can precisely control etching depths by limiting the amount of chemical reactant available at the surface. Recently, SiO{sub 2} ALE has been achieved by deposition of a thin (several Angstroms) reactive fluorocarbon (FC) layer on the material surface using controlled FC precursor flow and subsequent low energy Ar{sup +} ion bombardment in a cyclic fashion. Low energy ion bombardment is used to remove the FC layer along with a limited amount of SiO{sub 2} from the surface. In the present article, the authors describe controlled etching of Si{sub 3}N{sub 4} and SiO{sub 2} layers of one to several Angstroms using this cyclic ALE approach. Si{sub 3}N{sub 4} etching and etching selectivity of SiO{sub 2} over Si{sub 3}N{sub 4} were studied and evaluated with regard to the dependence on maximum ion energy, etching step length (ESL), FC surface coverage, and precursor selection. Surface chemistries of Si{sub 3}N{sub 4} were investigated by x-ray photoelectron spectroscopy (XPS) after vacuum transfer at each stage of the ALE process. Since Si{sub 3}N{sub 4} has a lower physical sputtering energy threshold than SiO{sub 2}, Si{sub 3}N{sub 4} physical sputtering can take place after removal of chemical etchant at the end of each cycle for relatively high ion energies. Si{sub 3}N{sub 4} to SiO{sub 2} ALE etching selectivity was observed for these FC depleted conditions. By optimization of the ALE process parameters, e.g., low ion energies, short ESLs, and/or high FC film deposition per cycle, highly selective SiO{sub 2} to Si{sub 3}N{sub 4} etching can be achieved for FC accumulation conditions, where FC can be selectively accumulated on Si{sub 3}N{sub 4} surfaces. This highly selective etching is explained by a lower carbon consumption of Si{sub 3}N{sub 4} as compared to Si

Thermal effects on the mechanical properties of SiC fiber reinforced reaction bonded silicon nitride matrix (SiC/RBSN) composites

Science.gov (United States)

Bhatt, R. T.; Phillips, R. E.

1988-01-01

The elevated temperature four-point flexural strength and the room temperature tensile and flexural strength properties after thermal shock were measured for ceramic composites consisting of 30 vol pct uniaxially aligned 142 micron diameter SiC fibers in a reaction bonded Si3N4 matrix. The elevated temperature strengths were measured after 15 min of exposure in air at temperatures to 1400 C. Thermal shock treatment was accomplished by heating the composite in air for 15 min at temperatures to 1200 C and then quenching in water at 25 C. The results indicate no significant loss in strength properties either at temperature or after thermal shock when compared with the strength data for composites in the as-fabricated condition.

Friction and wear study of NR/SBR blends with Si3N4Filler

Science.gov (United States)

GaneshKumar, A.; Balaganesan, G.; Sivakumar, M. S.

2018-04-01

The aim of this paper is to investigate mechanical and frictional properties of natural rubber/styrene butadiene rubber (NR/SBR) blends with and without silicon nitride (Si3N4) filler. The rubber is surface modified by silane coupling agent (Si-69) for enhancing hydrophobic property. The Si3N4of percentage 0 1, 3, 5 and 7, is incorporated into NR/SBR rubber compounds with 20% precipitated silica. The specimens with and without fillers are prepared as per standard for tensile and friction testing. Fourier transform infrared (FTIR) spectroscopy test is conducted and it is inferred that the coupling agent is covalently bonded on the surface of Si3N4 particles and an organic coating layer is formed. The co-efficient of friction and specific wear rate of NR/SBR blends are examined using an in-house built friction tester in a disc-on-plate (DOP) configuration. The specimens are tested to find coefficient of friction (COF) against steel grip antiskid plate under dry, mud, wet and oil environmental conditions. It is found that the increase in tensile strength and modulus at low percentage of Si3N4 dispersion. It is also observed that increase in sliding friction co-efficient and decrease in wear rate for 1% of Si3N4 dispersion in NR/SBR blends. The friction tested surfaces are inspected using Scanning Electron Microscope (SEM) and 3D non contact surface profiler.

Early-transition-metal ketenimine complexes. Synthesis, reactivity, and structural characterization of complexes with. eta. sup 2 (C,N)-ketenimine groups bound to the halogenobis((trimethylsilyl)cyclopentadienyl)niobium unit. X-ray structure of Nb(. eta. sup 5 -C sub 5 H sub 4 SiMe sub 3 ) sub 2 Cl(. eta. sup 2 (C,N)-PhN double bond C double bond CPh sub 2 )

Energy Technology Data Exchange (ETDEWEB)

Antinolo, A.; Fajardo, M.; Lopez Mardomingo, C.; Otero, A. (Univ. de Alcala de Henares (Spain)); Mourad, Y.; Mugnier, Y. (Centre National de la Recherche Scientifique, Dijon (France)); Sanz-Aparicio, J.; Fonseca, I.; Florencio, F. (CSIC, Madrid (Spain))

1990-11-01

The reaction of Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}X (X = Cl, Br) with 1 equiv of various ketenimines, R{sup 1}N{double bond}C{double bond}CR{sup 2}R{sup 3}, leads to the niobium derivatives Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}X({eta}{sup 2}(C,N)-R{sup 1}N{double bond}C{double bond}CR{sup 2}R{sup 3}) (1, X = Cl, R{sup 1} = R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 2, X = Cl, R{sup 1} = p-CH{sub 3}-C{sub 6}H{sub 4}, R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 3, X = Br, R{sup 1} = R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 4, X = Br, R{sup 1} = p-CH{sub 3}-C{sub 6}H{sub 4}, R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 5, X = Cl, R{sup 1} = R{sup 2} = C{sub 6}H{sub 5}, R{sup 3} = CH{sub 3}; 6, X = Br, R{sup 1} = R{sup 2} = C{sub 6}H{sub 5}, R{sup 3} = CH{sub 3}) with the expected ketenimine C{double bond}N bonding mode. Reduction of 1 with 1 equiv of Na/Hg gives the complex Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}({eta}{sup 2}(C,N)-PhN{double bond}C{double bond}CPh{sub 2}) (9) as a paramagnetic compound. The reduction of 9 with 1 equiv of Na/Hg and the subsequent addition of a proton source (ethanol) leads to the iminoacyl compound Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}(CRNR{sup 1}) (10, R = CH(Ph{sub 2}), R{sup 1} = Ph). The one- and two-electron reductions of 1 have been studied by cyclic voltammetry experiments. The structure of 1 was determined by single-crystal X-ray diffractometry: a = 24.4904 (14) {angstrom}, b = 11.0435 (04) {angstrom}, c = 26.6130 (15) {angstrom}, {beta} = 109.890 (5){degree}, monoclinic, space group C2/c, Z = 8, V = 6,768.4 (5) {angstrom}{sup 3}, {rho}{sub calcd} = 1.3194 g/mL, R = 0.048, R{sub w} = 0.060 based on 4,806 observed reflections. The structure contains a niobium atom bonded to two cyclopentadienyl rings in a {eta}{sup 5} fashion; the coordination of the metal is completed by a Cl atom and a {eta}{sup 2}(C,N)-bonded ketenimine ligand.

Reactions of 4-nitro-1,2,3-triazole with alkylating agents and compounds with activated multiple bonds

Energy Technology Data Exchange (ETDEWEB)

Vereshchagin, L.I.; Kuznetsova, N.I.; Kirillova, L.P.; Shcherbakov, V.V.; Sukhanov, G.T.; Gareev, G.A.

1987-01-01

When 4-nitro-1,2,3-triazole is alkylated, a mixture of N1- and N2-isomers is formed, with the latter usually predominating. The same behavior is also observed in addition reactions of 4-nitrotriazole to activated multiple bonds.

Effects of surface passivation on α-Si_3N_4 nanobelts: A first-principles study

International Nuclear Information System (INIS)

Xiong, Li; Dai, Jianhong; Song, Yan; Wen, Guangwu; Qin, Chunlin

2016-01-01

Highlights: • The stability and electronic properties of α-Si_3N_4 nanobelts are theoretically studied. • The surface of α-Si_3N_4 nanobelts are passivated with H, OH, F and Cl atoms. • The structural stability of nanobelts decreases in the order of OH, F, Cl, and H passivations. • The surface passivation greatly changes the electronic structures of α-Si_3N_4 nanobelts. - Abstract: The energetic stability and electronic structures of H, OH, F, or Cl passivated α-Si_3N_4 nanobelts orientating along various directions are systematically investigated via first-principles calculations. The results show that the stability of nanobelts is more sensitive to the surface passivation than growth direction. It decreases in the order of (100% OH), (50% H, 50% OH), (50% H, 50% F), (100% F), (50% H, 50% Cl), (100% Cl), (100% H), and unpassivation. H atoms prefer to bond with surface N atoms of nanobelts, while OH, F and Cl prefer to bond with Si atoms of nanobelts. In addition, the surface passivation greatly changes the electronic structures of nanobelts. The OH and F passivations result in the larger band gaps than the Cl passivation. While the coverage of OH, F or Cl increases to 100%, their band gaps decrease significantly, indicating an improvement of electrical properties, which is good agreement with the experimental findings. The 100% Cl-passivated nanobelt orientating along the [011] direction possesses the smallest band gap of 1.038 eV. The band gaps are found to be affected by a competition between quantum confinement effect and the role of the surface passivated groups or atoms at the band-gap edges.

Nanostructures based in boro nitride thin films deposited by PLD onto Si/Si{sub 3}N{sub 4}/DLC substrate

Energy Technology Data Exchange (ETDEWEB)

Roman, W S; Riascos, H [Grupo Plasma, Laser y Aplicaciones, Universidad Tecnologica de Pereira (Colombia); Caicedo, J C [Grupo de PelIculas Delgadas, Universidad del Valle, Cali (Colombia); Ospina, R [Laboratorio de Plasma, Universidad Nacional de Colombia, sede Manizales (Colombia); Tirado-MejIa, L, E-mail: hriascos@utp.edu.c [Laboratorio de Optoelectronica, Universidad del Quindio (Colombia)

2009-05-01

Diamond-like carbon and boron nitride were deposited like nanostructered bilayer on Si/Si{sub 3}N{sub 4} substrate, both with (100) crystallographic orientation, these films were deposited through pulsed laser technique (Nd: YAG: 8 Jcm{sup -2}, 9ns). Graphite (99.99%) and boron nitride (99.99%) targets used to growth the films in argon atmosphere. The thicknesses of bilayer were determined with a perfilometer, active vibration modes were analyzed using infrared spectroscopy (FTIR), finding bands associated around 1400 cm{sup -1} for B - N bonding and bands around 1700 cm{sup -1} associated with C=C stretching vibrations of non-conjugated alkenes and azometinic groups, respectively. The crystallites of thin films were analyzed using X-ray diffraction (XRD) and determinated the h-BN (0002), alpha-Si{sub 3}N{sub 4} (101) phases. The aim of this study is to relate the dependence on physical and chemical characteristics of the system Si/Si{sub 3}N{sub 4}/DLC/BN with gas pressure adjusted at the 1.33, 2.67 and 5.33 Pa values.

Characterization of Si3N4-Al interface after corrosion tests Caracterização da interface Si3N4-Al após testes de corrosão

Directory of Open Access Journals (Sweden)

C. dos Santos

2003-12-01

Full Text Available Silicon nitride is a covalent ceramic material of high corrosion resistance and mechanical stability at elevated temperatures. Due to these properties, its use in metallurgical processes, such as the casting of alloys, is increasing. Therefore, the characterization of the interface between Si3N4 and the casted metal is of great importance to investigate possible interactions, which might deteriorate the ceramic mould or contaminate the metal. In this work, the use of Si3N4 as crucible material for Al-casting has been studied, by investigating the corrosion attack of liquid Al at a temperature of 1150 ºC during 30 days in air. The interface was characterized by X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. It has been found that due to superficial oxidation two oxide layers form - SiO2 on Si3N4 and Al2O3 on Al - which effectively hinder further reactions under the conditions studied, confering high corrosion resistance to the Si3N4 crucible.Nitreto de silício (Si3N4 é um material cerâmico covalente de elevada resistência à corrosão e estabilidade mecânica em temperaturas elevadas. Devido a essas propriedades, sua utilização em processos metalúrgicos, tais como em fundição de ligas metálicas, é crescente. Desta forma, a caracterização da interface entre Si3N4 e metais fundidos é de grande interesse para investigar possíveis interações as quais poderão deteriorar o material cerâmico e/ou contaminar o metal. Nesse trabalho o uso de Si3N4 como material base de cadinhos para fundição de alumínio foi estudado, pela investigação do ataque corrosivo de Al líquido a 1150 ºC durante 30 dias, ao ar. A interface foi caracterizada por difração de raios X, microscopia eletrônica de varredura e espectroscopia de energia dispersiva. É encontrado que devido à oxidação superficial dois óxidos se formam - SiO2 no Si3N4 e Al2O3 no Al - os quais evitam possíveis reações sob as condi

Adsorption and surface reaction of bis-diethylaminosilane as a Si precursor on an OH-terminated Si (0 0 1) surface

International Nuclear Information System (INIS)

Baek, Seung-Bin; Kim, Dae-Hee; Kim, Yeong-Cheol

2012-01-01

The adsorption and the surface reaction of bis-diethylaminosilane (SiH 2 [N(C 2 H 5 ) 2 ] 2 , BDEAS) as a Si precursor on an OH-terminated Si (0 0 1) surface were investigated to understand the initial reaction mechanism of the atomic layer deposition (ALD) process using density functional theory. The bond dissociation energies between two atoms in BDEAS increased in the order of Si-H, Si-N, and the rest of the bonds. Therefore, the relatively weak Si-H and Si-N bonds were considered for bond breaking during the surface reaction. Optimum locations of BDEAS for the Si-H and Si-N bond breaking were determined on the surface, and adsorption energies of 0.43 and 0.60 eV, respectively, were obtained. The Si-H bond dissociation energy of the adsorbed BDEAS on the surface did not decrease, so that a high reaction energy barrier of 1.60 eV was required. On the other hand, the Si-N bond dissociation energy did decrease, so that a relatively low reaction energy barrier of 0.52 eV was required. When the surface reaction energy barrier was higher than the adsorption energy, BDEAS would be desorbed from the surface instead of being reacted. Therefore, the Si-N bond breaking would be dominantly involved during the surface reaction, and the result is in good agreement with the experimental data in the literature.

Insertion reactions into Pd[bond]O and Pd[bond]N bonds: preparation of alkoxycarbonyl, carbonato, carbamato, thiocarbamate, and thioureide complexes of palladium(II).

Science.gov (United States)

Ruiz, José; Martínez, M Teresa; Florenciano, Félix; Rodríguez, Venancio; López, Gregorio; Pérez, José; Chaloner, Penny A; Hitchcock, Peter B

2003-06-02

Mononuclear palladium hydroxo complexes of the type [Pd(N[bond]N)(C(6)F(5))(OH)] [(N[bond]N = 2,2'-bipyridine (bipy), 4,4'-dimethyl-2,2'-bipyridine (Me(2)bipy), 1,10-phenanthroline (phen), or N,N,N',N'-tetramethylethylenediamine (tmeda)] have been prepared by reaction of [Pd(N[bond]N)(C(6)F(5))(acetone)]ClO(4) with KOH in methanol. These hydroxo complexes react, in methanol, with CO (1 atm, room temperature) to yield the corresponding methoxycarbonyl complexes [Pd(N[bond]N)(C(6)F(5))(CO(2)Me)]. Similar alkoxycarbonyl complexes [Pd(N[bond]N)(C(6)F(5))(CO(2)R)] (N[bond]N = bis(3,5-dimethylpyrazol-1-yl)methane); R = Me, Et, or (i)Pr) are obtained when [Pd(N[bond]N)(C(6)F(5))Cl] is treated with KOH in the corresponding alcohol ROH and CO is bubbled through the solution. The reactions of [Pd(N[bond]N)(C(6)F(5))(OH)] (N[bond]N = bipy or Me(2)bipy) with CO(2), in tetrahydrofuran, lead to the formation of the binuclear carbonate complexes [(N[bond]N)(C(6)F(5))Pd(mu-eta(2)-CO(3))Pd(C(6)F(5))(N[bond]N)]. Complexes [Pd(N[bond]N)(C(6)F(5))(OH)] react in alcohol with PhNCS to yield the corresponding N-phenyl-O-alkylthiocarbamate complexes [Pd(N[bond]N)(C(6)F(5))[SC(OR)NPh

Highly selective SiO2 etching over Si3N4 using a cyclic process with BCl3 and fluorocarbon gas chemistries

Science.gov (United States)

Matsui, Miyako; Kuwahara, Kenichi

2018-06-01

A cyclic process for highly selective SiO2 etching with atomic-scale precision over Si3N4 was developed by using BCl3 and fluorocarbon gas chemistries. This process consists of two alternately performed steps: a deposition step using BCl3 mixed-gas plasma and an etching step using CF4/Ar mixed-gas plasma. The mechanism of the cyclic process was investigated by analyzing the surface chemistry at each step. BCl x layers formed on both SiO2 and Si3N4 surfaces in the deposition step. Early in the etching step, the deposited BCl x layers reacted with CF x radicals by forming CCl x and BF x . Then, fluorocarbon films were deposited on both surfaces in the etching step. We found that the BCl x layers formed in the deposition step enhanced the formation of the fluorocarbon films in the CF4 plasma etching step. In addition, because F radicals that radiated from the CF4 plasma reacted with B atoms while passing through the BCl x layers, the BCl x layers protected the Si3N4 surface from F-radical etching. The deposited layers, which contained the BCl x , CCl x , and CF x components, became thinner on SiO2 than on Si3N4, which promoted the ion-assisted etching of SiO2. This is because the BCl x component had a high reactivity with SiO2, and the CF x component was consumed by the etching reaction with SiO2.

Reaction of (carbonylimido)sulfur(IV) derivatives with TAS-fluoride, (Me2N)3S+Me3SiF2-.

Science.gov (United States)

Lork, E; Viets, D; Mews, R; Oberhammer, H

2000-10-16

In the reaction of TAS-fluoride, (Me2N)3S+Me3SiF2-, with carbonyl sulfur difluoride imides RC(O)NSF2 (R = F, CF3), C-N bond, cleavage is observed, and TAS+RC(O)F2- and NSF are the final products. From TASF and RC(O)NS(CF3)F, the salts TAS+RC(O)NS(CF3)F2- (R = F (14), CF3 (15)), with psi-pentacoordinate sulfur centers in the anions, are formed. An X-ray structure investigation of 14 shows that the fluorine atoms occupy axial positions and CF3, NC(O)F, and the sulfur lone pair occupy equatorial positions of the trigonal bipyramid. The -C(O)F group lies in the equatorial plane with the CO bond synperiplanar to the SN bond. According to B3LYP calculations, this structure corresponds to a global minimum and the expected axial orientation of the -C(O)F group represents a transition state. Calculations for the unstable FC(O)NSF3- anion show a different geometry. The -C(O)F group deviates 40 degrees from axial orientation, and the equatorially bonded fluorine is, in contrast to the -CF3 group in 14, syn positioned.

LiCa{sub 3}Si{sub 2}N{sub 5} - A Lithium nitridosilicate with a [Si{sub 2}N{sub 5}]{sup 7-} double-chain

Energy Technology Data Exchange (ETDEWEB)

Lupart, Saskia; Schnick, Wolfgang [Department Chemie, Lehrstuhl fuer Anorganische Festkoerperchemie, Ludwig-Maximilians-Universitaet Muenchen (Germany)

2012-10-15

The lithium nitridosilicate LiCa{sub 3}Si{sub 2}N{sub 5} was synthesized by the reaction of calcium with Si(NH){sub 2} and Li{sub 3}N in weld shut tantalum ampoules at 900 C. The structure of LiCa{sub 3}Si{sub 2}N{sub 5} [space group C2/c, no. 15, a = 5.1454(10), b = 20.380(4), c = 10.357(2) Aa, β = 91.24(3) , wR{sub 2} = 0.1084, 863 data, 102 parameters] consists of [Si{sub 2}N{sub 5}]{sup 7-} double-chains including edge-sharing tetrahedra. The lithium atoms in the crystal structure are situated in strands along the crystallographic b axis. Lattice energy calculations (MAPLE) and EDX measurements confirmed the electrostatic bonding interactions and the chemical composition. The {sup 29}Si and {sup 7}Li solid-state MAS NMR spectroscopic investigations are reported. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Thermal effects on the mechanical properties of SiC fibre reinforced reaction-bonded silicon nitride matrix composites

Science.gov (United States)

Bhatt, R. T.; Phillips, R. E.

1990-01-01

The elevated temperature four-point flexural strength and the room temperature tensile and flexural strength properties after thermal shock were measured for ceramic composites consisting of 30 vol pct uniaxially aligned 142 micron diameter SiC fibers in a reaction bonded Si3N4 matrix. The elevated temperature strengths were measured after 15 min of exposure in air at temperatures to 1400 C. Thermal shock treatment was accomplished by heating the composite in air for 15 min at temperatures to 1200 C and then quenching in water at 25 C. The results indicate no significant loss in strength properties either at temperature or after thermal shock when compared with the strength data for composites in the as-fabricated condition.

Pressure-assisted reaction bonding between W and Si80Ge20 alloy with Ni as the interlayer

International Nuclear Information System (INIS)

Xu, Y.; Laabs, F.C.; Beaudry, B.J.; Gschneidner, K.A. Jr.

1991-01-01

The conditions and reaction mechanism of W/Ni/Si 80 Ge 20 hot-press bonding have been studied. It was found that a Ni/Si 80 Ge 20 bond can be formed using low pressure, 19.6 MPa, in the temperature range between 780 and 900 degree C in a short time. The kinetics follows a parabolic pattern, suggesting it is a diffusion-controlled process. The activation energy is 2.7 eV and the parabolic rate constant is given by K P = 4.0 x 10 14 exp(-3.2x10 4 /T) (μm 2 /min). The bonding interface has a multilayered structure. A phenomenological mechanism of the bonding formation has been proposed based on scanning electron microscopy observations and energy dispersive spectroscopy. The cracking problem due to thermal stress is discussed based on Oxx's equation. It was found that bonds free from cracks in the Si 80 Ge 20 alloy are formed when the Ni consumption (as measured by the thickness of the nickel layer) is sufficiently small ( 4 . As an interlayer, nickel can join the tungsten sheet and the Si 80 Ge 20 together. It has been also demonstrated that a thin nickel layer formed by vapor deposition on a tungsten sheet may be used as the interlayer in place of nickel sheet

Enhancement of photoluminescence properties and modification of crystal structures of Si3N4 doping Li2Sr0.995SiO4:0.005Eu2+ phosphors

International Nuclear Information System (INIS)

Song, Kaixin; Zhang, Fangfang; Chen, Daqin; Wu, Song; Zheng, Peng; Huang, Qingming; Jiang, Jun; Xu, Junming; Qin, Huibin

2015-01-01

Highlights: • Si 3 N 4 modified Li 2 Sr 0.995 SiO 4 :0.005Eu 2+ phosphors were prepared. • The luminescence intensity of Li 2 Sr 0.995 SiO 4 :Eu 2+ was enhanced by doping Si 3 N 4 . • The fluorescence decay times and thermal stability were enhanced by doping Si 3 N 4 . - Abstract: Si 3 N 4 modified Li 2 Sr 0.995 SiO 4 :0.005Eu 2+ (Li 2 Sr 0.995 SiO 4−3x/2 N x :0.005Eu 2+ ) phosphors were synthesized with the conventional solid-state reaction in the reduced atmosphere. The crystal structure and vibrational modes were analyzed by X-ray diffraction, Raman scattering spectroscopy and Rietveld crystal structure refinement. Photoluminescence (PL) and photoluminescence excitation (PLE) spectra showed that Li 2 Sr 0.995 SiO 4−3x/2 N x :0.005Eu 2+ powder exhibited a broad yellow emission band centered at 560 nm under the excitation of 460 nm visible light, due to the 4f 6 5d 1 → 4f 7 transition of Eu 2+ . The partial nitridation of Li 2 Sr 0.995 SiO 4−3x/2 N x :0.005Eu 2+ (x = 0.01) phosphors led to a large enhancement in the luminescence intensity, as much as 190%. At the same time, the fluorescence decay behavior curves further showed that the photoluminescence efficiencies of Li 2 Sr 0.995 SiO 4−3x/2 N x :0.005Eu 2+ phosphors were enhanced by addition of Si 3 N 4 . The temperature quenching characteristics confirmed that the oxynitride based Li 2 Sr 0.995 SiO 4−3x/2 N x :0.005Eu 2+ showed slightly higher stability. It is implied that Li 2 Sr 0.995 SiO 4−3x/2 N x :0.005Eu 2+ phosphors had a possible potential application on white LEDs to match blue light chips

Non-condensed (oxo)nitridosilicates: La{sub 3}-[SiN{sub 4}]F and the polymorph o-La{sub 3}-[SiN{sub 3}O]O

Energy Technology Data Exchange (ETDEWEB)

Durach, Dajana; Schnick, Wolfgang [Department of Chemistry, Chair in Inorganic Solid-State Chemistry, University of Munich (LMU) (Germany)

2015-08-15

The isotypic compounds La{sub 3}[SiN{sub 4}]F and La{sub 3}[SiN{sub 3}O]O were synthesized in a radio-frequency furnace at 1600 C. The crystal structures [Pnma (no. 62), Z = 4; La{sub 3}(SiN{sub 4})F: a = 9.970(3), b = 7.697(2), c = 6.897(2) Aa, V = 529.3(3) Aa{sup 3}; La{sub 3}(SiON{sub 3})O: a = 9.950(2), b = 7.6160(15), c = 6.9080(14) Aa, V = 523.48(18) Aa{sup 3}] were elucidated from single-crystal X-ray diffraction data and corroborated by Rietveld refinement, lattice-energy calculations (Madelung part of lattice energy, MAPLE) and Raman/FTIR spectroscopy. Both compounds are homeotypic with Na{sub 2}Pr[GeO{sub 4}]OH forming a network of vertex-sharing FLa{sub 6}/OLa{sub 6} octahedra, whose voids are filled with non-condensed SiN{sub 4}/SiN{sub 3}O tetrahedra. o-La{sub 3}[SiON{sub 3}]O is the orthorhombic polymorph of this compound, which probably represents the high-temperature modification, whereas the tetragonal polymorph t-La{sub 3}[SiON{sub 3}]O represents the low-temperature modification. While the space group of the t-polymorph [I4/mcm (no. 140)] differs from the new La{sub 3}[SiN{sub 4}]F and o-La{sub 3}[SiN{sub 3}O]O, the crystal structure contains the same linking pattern. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Ultrathin silicon oxynitride layer on GaN for dangling-bond-free GaN/insulator interface.

Science.gov (United States)

Nishio, Kengo; Yayama, Tomoe; Miyazaki, Takehide; Taoka, Noriyuki; Shimizu, Mitsuaki

2018-01-23

Despite the scientific and technological importance of removing interface dangling bonds, even an ideal model of a dangling-bond-free interface between GaN and an insulator has not been known. The formation of an atomically thin ordered buffer layer between crystalline GaN and amorphous SiO 2 would be a key to synthesize a dangling-bond-free GaN/SiO 2 interface. Here, we predict that a silicon oxynitride (Si 4 O 5 N 3 ) layer can epitaxially grow on a GaN(0001) surface without creating dangling bonds at the interface. Our ab initio calculations show that the GaN/Si 4 O 5 N 3 structure is more stable than silicon-oxide-terminated GaN(0001) surfaces. The electronic properties of the GaN/Si 4 O 5 N 3 structure can be tuned by modifying the chemical components near the interface. We also propose a possible approach to experimentally synthesize the GaN/Si 4 O 5 N 3 structure.

Angular dependence of Si3N4 etch rates and the etch selectivity of SiO2 to Si3N4 at different bias voltages in a high-density C4F8 plasma

International Nuclear Information System (INIS)

Lee, Jin-Kwan; Lee, Gyeo-Re; Min, Jae-Ho; Moon, Sang Heup

2007-01-01

The dependence of Si 3 N 4 etch rates and the etch selectivity of SiO 2 to Si 3 N 4 on ion-incident angles was studied for different bias voltages in a high-density C 4 F 8 plasma. A Faraday cage and specially designed substrate holders were used to accurately control the angles of incident ions on the substrate surface. The normalized etch yield (NEY), defined as the etch yield obtained at a given ion-incident angle normalized to that obtained on a horizontal surface, was unaffected by the bias voltage in Si 3 N 4 etching, but it increased with the bias voltage in SiO 2 etching in the range of -100 to -300 V. The NEY changed showing a maximum with an increase in the ion-incident angle in the etching of both substrates. In the Si 3 N 4 etching, a maximum NEY of 1.7 was obtained at 70 deg. in the above bias voltage range. However, an increase in the NEY at high ion-incident angles was smaller for SiO 2 than for Si 3 N 4 and, consequently, the etch selectivity of SiO 2 to Si 3 N 4 decreased with an increase in the ion-incident angle. The etch selectivity decreased to a smaller extent at high bias voltage because the NEY of SiO 2 had increased. The characteristic changes in the NEY for different substrates could be correlated with the thickness of a steady-state fluorocarbon (CF x ) film formed on the substrates

Effect of strain on bond-specific reaction kinetics during the oxidation of H-terminated (111) Si

International Nuclear Information System (INIS)

Gokce, Bilal; Aspnes, David E.; Gundogdu, Kenan

2011-01-01

Although strain is used in semiconductor technology for manipulating optical, electronic, and chemical properties of semiconductors, the understanding of the microscopic phenomena that are affected or influenced by strain is still incomplete. Second-harmonic generation data obtained during the air oxidation of H-terminated (111) Si reveal the effect of compressive strain on this chemical reaction. Even small amounts of strain manipulate the reaction kinetics of surface bonds significantly, with tensile strain enhancing oxidation and compressive strain retarding it. This dramatic change suggests a strain-driven charge transfer mechanism between Si-H up bonds and Si-Si back bonds in the outer layer of Si atoms.

Air-stable n-type doping of graphene from overlying Si3N4 film

International Nuclear Information System (INIS)

Wang, Zegao; Li, Pingjian; Chen, Yuanfu; Liu, Jingbo; Qi, Fei; Tian, Hongjun; Zheng, Binjie; Zhou, Jinhao

2014-01-01

In this study, we report a facile method to obtain air-stable n-type graphene by plasma-enhanced chemical vapor depositing Si 3 N 4 film on the surface of graphene. We have demonstrated that the overlying Si 3 N 4 film can not only act as the penetration-barrier against H 2 O and O 2 adsorbed on the graphene surface, but also cause an effective n-type doping due to the amine groups at the interface of graphene/Si 3 N 4 . Furthermore, the studies reveal that the Dirac point of graphene can be modulated by the thickness of Si 3 N 4 film, which is due to competing effects of Si 3 N 4 -induced doping (n-type) and penetrating H 2 O (O 2 )-induced doping (p-type). We expect this method to be used for obtaining stable n-type graphene field-effect transistors in air, which will be widely used in graphene electronic devices.

Microstructure, mechanical and tribological performance of hybrid A359/(SiC  +  Si3N4) composites for automotive applications

Science.gov (United States)

Shalaby, Essam A. M.; Churyumov, Alexander Yu

2017-11-01

In this study, microstructure analysis, yield strength at high temperatures and wear rate of hybrid A359/(SiC  +  Si3N4) composites were investigated. Different weight percent of (SiC  +  Si3N4) particles were introduced to synthesis the composites using stir/squeeze process. XRD, SEM, TEM and EDS were utilized to investigate the distribution of particles throughout the matrix, and the interfacial reaction at matrix/particle interface. It confirmed the existence of MgAl2O4 which enhances the wettability between the particles and the matrix, and the absence of particle agglomeration. The (SiC  +  Si3N4) addition not only enhances the hardness measurements but also leads to a reduction in the dendritic arm spacing (DAS). Moreover, it develops the wear performance and the yield strength at high temperatures. The developed composites provide a promising material suitable for automotive industries.

Thermal expansion of spinel-type Si3N4

DEFF Research Database (Denmark)

Paszkowics, W.; Minkikayev, R.; Piszora, P.

2004-01-01

The lattice parameter and thermal expansion coefficient (TEC) for the spinel-type Si3N4 phase prepared under high-pressure and high-temperature conditions are determined for 14 K......The lattice parameter and thermal expansion coefficient (TEC) for the spinel-type Si3N4 phase prepared under high-pressure and high-temperature conditions are determined for 14 K...

Efecto de la microestructura en el comportamiento tribológico de materiales monolíticos de Si3N4 y de compuestos Si3N4–SiC

Directory of Open Access Journals (Sweden)

Silva, R. F.

2000-06-01

Full Text Available The tribological behaviour of various Si3N4 based materials, including Si3N4/SiC composites, has been analysed from room temperature up to 700ºC, and for sliding speeds between 0.5 and 2 m/s. Materials have been prepared by hot pressing at 1750ºC in nitrogen atmosphere, varying α-Si3N4 phase content, microstructure coarseness and shape and size of the SiC particles. Wear tests were performed in self-mated pairs using a pin on disc tribometer, without lubrication and at a fixed load of 5 N. Pin and disc worn surfaces were observed by scanning electron microscopy (SEM-EDS. Debris generated during tests was analysed by SEM-EDS and X-ray diffraction (XRD. Results showed friction, f, and wear coefficients, K, above 0.3 y 10-6 mm3N-1m-1, respectively. Wear mechanism depended on the microstructure and the mechanical properties of the materials.Se ha analizado el comportamiento tribológico de materiales de Si3N4 y de compuestos Si3N4/SiC, desde temperatura ambiente hasta 700ºC y en el rango de velocidades 0.5-2 m/s. Los materiales se han preparado mediante prensado en caliente a 1750ºC en atmósfera de nitrógeno, variando el contenido en fase α-Si3N4, el tamaño medio de grano, y la morfología de las partículas de SiC adicionadas. Los ensayos se han realizado en pares homólogos utilizando un tribómetro del tipo punta sobre disco, sin lubricación y a una carga constante de 5 N. Las superficies de desgaste de las puntas y los discos se observaron en un microscopio electrónico de barrido con capacidad analítica (MEB-EDX. Los residuos generados durante los ensayos se analizaron mediante MEB-EDX y difracción de rayos X (DRX. Los resultados obtenidos en los ensayos daban valores de coeficiente de fricción, f, y de desgaste, K, superiores a 0.3 y 10-6 mm3N-1m-1, respectivamente. El mecanismo de desgaste predominante dependía de la microestructura y de las propiedades mecánicas del material ensayado.

Prediction of novel hard phases of Si{sub 3}N{sub 4}: First-principles calculations

Energy Technology Data Exchange (ETDEWEB)

Cui, Lin; Hu, Meng; Wang, Qianqian; Xu, Bo; Yu, Dongli; Liu, Zhongyuan; He, Julong, E-mail: hjl@ysu.edu.cn

2015-08-15

Exploration of novel hard metastable phases of silicon nitride was performed using a recently developed particle-swarm optimization method within the CALYPSO software package. Three potential hard metastable phases of t-Si{sub 3}N{sub 4}, m-Si{sub 3}N{sub 4}, and o-Si{sub 3}N{sub 4} were predicted. These phases are mechanically and dynamically stable at ambient pressure based on their elastic constants and phonon dispersions. t-Si{sub 3}N{sub 4} and m-Si{sub 3}N{sub 4} exhibit lower energies than γ-Si{sub 3}N{sub 4} at pressures below 2.5 GPa and 2.9 GPa, respectively, which promise that the formers could be obtained by quenching from γ-Si{sub 3}N{sub 4}. o-Si{sub 3}N{sub 4} is a better high-pressure metastable phase than CaTi{sub 2}O{sub 4}-type Si{sub 3}N{sub 4} proposed by Tatsumi et al. and it can come from the transition of γ-Si{sub 3}N{sub 4} under 198 GPa. The theoretical band gaps of t-Si{sub 3}N{sub 4}, m-Si{sub 3}N{sub 4}, and o-Si{sub 3}N{sub 4} at ambient pressure were 3.15 eV, 3.90 eV, and 3.36 eV, respectively. At ambient pressure, the Vickers hardness values of t-Si{sub 3}N{sub 4} (32.6 GPa), m-Si{sub 3}N{sub 4} (31.5 GPa), and o-Si{sub 3}N{sub 4} (36.1 GPa) are comparable to β-Si{sub 3}N{sub 4} and γ-Si{sub 3}N{sub 4}. With the pressure increasing, t-Si{sub 3}N{sub 4}, m-Si{sub 3}N{sub 4}, and o-Si{sub 3}N{sub 4} will change from the brittle to ductile state at about 15.7 GPa, 7.3 GPa and 28.9 GPa, respectively. - Graphical abstract: This figure shows the crystal structures of three Si{sub 3}N{sub 4} predicted in this manuscript, and left to right: t-Si{sub 3}N{sub 4}, m-Si{sub 3}N{sub 4} and o-Si{sub 3}N{sub 4}. - Highlights: • We explored three metastable phases of Si{sub 3}N{sub 4} — t-Si{sub 3}N{sub 4}, m-Si{sub 3}N{sub 4}, and o-Si{sub 3}N{sub 4}. • The enthalpies of t and m- are much lower than that of γ at ambient pressure. • ois one further high pressure phase than γ. • o-Si{sub 3}N{sub 4} is the most hardest phase in Si

Protein surface labeling reactivity of N-hydroxysuccinimide esters conjugated to Fe{sub 3}O{sub 4}@SiO{sub 2} magnetic nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Pirani, Parisa; Patil, Ujwal S.; Apsunde, Tushar Dattu; Trudell, Mark L.; Cai, Yang, E-mail: ycai@chnola-research.org; Tarr, Matthew A., E-mail: mtarr@uno.edu [University of New Orleans, Department of Chemistry (United States)

2015-09-15

The N-hydroxysuccinimide (NHS) ester moiety is one of the most widely used amine reactive groups for covalent conjugation of proteins/peptides to other functional targets. In this study, a cleave-analyze approach was developed to quantify NHS ester groups conjugated to silica-coated iron oxide magnetic nanoparticles (Fe{sub 3}O{sub 4}@SiO{sub 2} MNPs). The fluorophore dansylcadaverine was attached to Fe{sub 3}O{sub 4}@SiO{sub 2} magnetic nanoparticles (MNPs) via reaction with NHS ester groups, and then released from the MNPs by cleavage of the disulfide bond in the linker between the fluorophore and the MNPs moiety. The fluorophore released from Fe{sub 3}O{sub 4}@SiO{sub 2} MNPs was fluorometrically measured, and the amount of fluorophore should be equivalent to the quantity of the NHS ester groups on the surface of Fe{sub 3}O{sub 4}@SiO{sub 2} MNPs that participated in the fluorophore conjugation reaction. Another sensitive and semiquantitative fluorescence microscopic test was also developed to confirm the presence of NHS ester groups on the surface of Fe{sub 3}O{sub 4}@SiO{sub 2} MNPs. Surface-conjugated NHS ester group measurements were primarily performed on Fe{sub 3}O{sub 4}@SiO{sub 2} MNPs of 100–150 nm in diameter and also on 20-nm nanoparticles of the same type but prepared by a different method. The efficiency of labeling native proteins by NHS ester-coated Fe{sub 3}O{sub 4}@SiO{sub 2} MNPs was explored in terms of maximizing the number of MNPs conjugated per BSA molecule or maximizing the number of BSA molecules conjugated per each nanoparticle. Maintaining the amount of fresh NHS ester moieties in the labeling reaction system was essential especially when maximizing the number of MNPs conjugated per protein molecule. The methodology demonstrated in this study can serve as a guide in labeling the exposed portions of proteins by bulky multivalent labeling reagents.

Are Nonadiabatic Reaction Dynamics the Key to Novel Organosilicon Molecules? The Silicon (Si(3P))-Dimethylacetylene (C4H6(X1A1g)) System as a Case Study.

Science.gov (United States)

Thomas, Aaron M; Dangi, Beni B; Yang, Tao; Kaiser, Ralf I; Lin, Lin; Chou, Tzu-Jung; Chang, Agnes H H

2018-06-06

The bimolecular gas phase reaction of ground-state silicon (Si; 3 P) with dimethylacetylene (C 4 H 6 ; X 1 A 1g ) was investigated under single collision conditions in a crossed molecular beams machine. Merged with electronic structure calculations, the data propose nonadiabatic reaction dynamics leading to the formation of singlet SiC 4 H 4 isomer(s) and molecular hydrogen (H 2 ) via indirect scattering dynamics along with intersystem crossing (ISC) from the triplet to the singlet surface. The reaction may lead to distinct energetically accessible singlet SiC 4 H 4 isomers ( 1 p8- 1 p24) in overall exoergic reaction(s) (-107 -20 +12 kJ mol -1 ). All feasible reaction products are either cyclic, carry carbene analogous silylene moieties, or carry C-Si-H or C-Si-C bonds that would require extensive isomerization from the initial collision complex(es) to the fragmenting singlet intermediate(s). The present study demonstrates the first successful crossed beams study of an exoergic reaction channel arising from bimolecular collisions of silicon, Si( 3 P), with a hydrocarbon molecule.

Ionic ASi{sub 2}N{sub 3} (A=Li, Na, K and Rb) stabilized by the covalent Si–N bonding: First-principles calculations

Energy Technology Data Exchange (ETDEWEB)

Zhang, Huijun [College of Information Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Ren, Jiadong, E-mail: jdren@ysu.edu.cn [College of Information Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Wu, Lailei [Key Laboratory of Metastable Materials Science and Technology, College of Material Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Zhang, Jingwu, E-mail: zjw@ysu.edu.cn [Key Laboratory of Metastable Materials Science and Technology, College of Material Science and Engineering, Yanshan University, Qinhuangdao 066004 (China)

2017-01-15

The structural, elastic and electronic properties of LiSi{sub 2}N{sub 3} and its substitutions by Na, K and Rb were investigated through first-principles computations. The expansion of lattice parameters of ASi{sub 2}N{sub 3} from Li, Na, K to Rb is found to be determined by the bond angle of Si–N1–Si, which suggests a possible way to improve the lithium ionic conductivity by substitutions. ASi{sub 2}N{sub 3} (A=Li, Na, K and Rb) shows the similar elastic behaviors, while the electronic band gap gradually decreases from 5.1 to 3.4 eV from LiSi{sub 2}N{sub 3} to RbSi{sub 2}N{sub 3}. Interestingly, the analysis of electronic structure, crystal orbital Hamiltonian populations and Bader charges shows that the covalence of Si–N bonding is critical for the stability of ASi{sub 2}N{sub 3} phase. Among ASi{sub 2}N{sub 3} phases, there is a relatively high ionicity in NaSi{sub 2}N{sub 3}; the Si–N bond strength in [Si{sub 2}N{sub 3}]{sup −} net for KSi{sub 2}N{sub 3} and RbSi{sub 2}N{sub 3} is comparable to LiSi{sub 2}N{sub 3}, but stronger than NaSi{sub 2}N{sub 3}. - Graphic abstract: Universal trend of structural and electronic properties in alkaline metal silicon nitrides, ASi{sub 2}N{sub 3}, A=Li, Na, K and Rb. - Highlights: • Trend in structure, electronic and mechanical properties of ASi{sub 2}N{sub 3} (A=Li-Rb) were predicted. • Lattice expansion of ASi{sub 2}N{sub 3} induced by the bond angle of Si–N1–Si was found. • Calculated band gap decreases from 5.1 to 3.4 eV from LiSi{sub 2}N{sub 3} to RbSi{sub 2}N{sub 3}. • Covalent Si–N bonding is critical for the stability of ASi{sub 2}N{sub 3}.

Cross sections and reaction rates for 23Na(p,n) 23Mg, 27Al(p,n) 27Si, 27Al(α,n) 30P, 29Si(α,n) 32S, and 30Si(α,n) 33S

International Nuclear Information System (INIS)

Flynn, D.S.; Sekharan, K.K.; Hiller, B.A.; Laumer, H.; Weil, J.L.; Gabbard, F.

1978-01-01

The total neutron production cross sections for the 23 Na(p,n) 23 Mg, 27 Al(p,n) 27 Si, 27 Al(α,n) 30 P, 29 Si(α,n) 32 S, and 30 Si(α,n) 33 S reactions have been measured for bombarding energies from threshold to 6.3 MeV. The neutron detector was a 60-cm diameter sphere of polyethylene with eight 10 BF 3 counters and was insensitive to the angle and energy of the emitted neutrons. Cross sections for inverse reactions have been obtained using the principle of detailed balance. The data have been used to determine parameters for statistical model calculations to facilitate extrapolation of cross sections to higher bombarding energies. These reactions are relevant to problems of nucleosynthesis and stellar evolution and to studies of radiation damage. Nucleosynthesis reaction rates, N/sub A/(sigmav), were determined for the reactions studied and are tabulated for temperatures ranging from 0.4 x 10 9 to 10.0 x 10 9 K

Plastic Deformation Induced by Nanoindentation Test Applied on ZrN/Si3N4 Multilayer Coatings

Directory of Open Access Journals (Sweden)

Zhengtao Wu

2017-12-01

Full Text Available ZrN/Si3N4 multilayer coating that alternates with either nanocrystalline ZrN or amorphous Si3N4 interlayers was fabricated by reactively magnetron sputtering in an Ar-N2 mixture atmosphere. The thicknesses of the nanocrystalline ZrN and the amorphous Si3N4 interlayers are ~12.5 and 2.5 nm, respectively. The ZrN/Si3N4 coating exhibits a promoted hardness of 28.6 ± 1.2 GPa when compared to the binary ZrN. Microstructure evolution just underneath the nanoindentation impression of the ZrN/Si3N4 multilayer coating has been investigated. The result indicates that both ZrN nanograin rotations and plastic flow of the Si3N4 interlayers contribute to the permanent deformation of the multilayer coating induced by the nanoindentation. In addition, the introduction of the a-Si3N4 interlayers hinders both the initiation and propagation of microcracks when the multilayer coating was applied to the scratch test. The propagation deflection of the microcracks was observed attributed to the heterogenous interface, which produces the hardness promotion of the multilayer coating eventually.

Atomic structure and potential energy of β-Si3N4/diamond interface in the process of detachment: A first-principles study

Science.gov (United States)

Chen, Naichao; Chen, Yingchao; Ai, Jun; Li, Cheng; He, Ping; Ren, Jianxing; Zhu, Quanjun

2018-03-01

Peeling is regarded as a main technique barrier for the application of coating. Many factors affects the peeling of coating. Among them, the interfacial properties between coating and substrate plays a vital role. In this work, the β-Si3N4/diamond interface is conducted as the sample to study the changes in atomic structure and potential energy in the process of detachment by the first-principles calculations. The β-Si3N4/diamond (2 × 2) crystal unit is used as the calculated model. The detachment is simulated by moving up β-Si3N4 far from diamond by the 0.1 Å of each step. The results show that in the beginning of detachment, the bonds in the interface keep a constant length, rather than extension like spring. When the distance between β-Si3N4 and diamond reaches a certain distance, the interfacial bonds would suddenly break, and the elongated β-Si3N4 resumes its original statues indicating that the interface between two surfaces may exist a threshold value to control the peeling. When the external force is less than this threshold value, the peeling of coating would not occur. However, once the external force is greater than this one, the peeling would immediately present. The interface presents the brittle failure in the process of detachment, which is in good agreement with the experimental observation. Meanwhile, the different physical properties between van der Waals and quantum effects lead to the transient status in the process of detachment, where although the interfacial bonds are broken, the adhesive strength is still strong due to its low negative adsorption energy.

Si{sub 3}N{sub 4} materials and applications; Si{sub 3}N{sub 4}-Werkstoffe und deren Anwendung

Energy Technology Data Exchange (ETDEWEB)

Woetting, G.; Leimer, G.; Gugel, E. [Cremer Forschungsinstitut GmbH und Co. KG, Roedental (Germany)

2000-07-01

Silicon nitrides, or silicon nitride-based materials, offer a very wide range of high-duty applications due to their high mechanical strength and good resistance to thermal, corrosive, and/or abrasive wear. Variation and optimization of their properties in response to intended applications is described in detail, also referring to potential new applications. (orig./CB) [German] Siliciumnitrid(Si3N4)- bzw. SN-Werkstoffe finden aufgrund ihrer hohen mechanischen Festigkeit sowie guten thermischen, korrosiven und/oder abrasiven Bestaendigkeit bereits vielfaeltige Anwendungen als hochbelastete Bauteile. Um fuer die jeweiligen Einsatzbedingungen optimale Werkstoffe einzusetzen, sind spezifische Modifizierungen moeglich und sinnvoll. Diesbezueglich kommerziell verfuegbare Si3N4-Werkstoffqualitaeten werden vorgestellt und derzeitige sowie potentielle Anwendungen ausgefuehrt. Die haeufig als Hemmnis fuer einen breiten Einsatz angefuehrten Bauteilkosten werden diskutiert. (orig.)

Characterization of rare-earth doped Si 3 N4 /SiC micro/nanocomposites

Directory of Open Access Journals (Sweden)

Peter Tatarko

2010-03-01

Full Text Available Influence of various rare-earth oxide additives (La2O3, Nd2O3, Sm2O3, Y2O3, Yb2O3 and Lu2O3 on the mechanical properties of hot-pressed silicon nitride and silicon nitride/silicon carbide micro/nano-composites has been investigated. The bimodal character of microstructures was observed in all studied materials where elongated β-Si3N4 grains were embedded in the matrix of much finer Si3N4 grains. The fracture toughness values increased with decreasing ionic radius of rare-earth elements. The fracture toughness of composites was always lower than that of monoliths due to their finer Si3N4/SiC microstructures. Similarly, the hardness and bending strength values increased with decreasing ionic radius of rare-earth elements either in monoliths or composites. On the other hand, the positive influence of finer microstructure of the composites on strength was not observed due to the present defects in the form of SiC clusters and non-reacted carbon zones. Wear resistance at room temperature also increased with decreasing ionic radius of rare-earth element. Significantly improved creep resistance was observed in case either of composite materials or materials with smaller radius of RE3+.

Effects of Si content on microstructure and mechanical properties of TiAlN/Si3N4-Cu nanocomposite coatings

Science.gov (United States)

Feng, Changjie; Hu, Shuilian; Jiang, Yuanfei; Wu, Namei; Li, Mingsheng; Xin, Li; Zhu, Shenglong; Wang, Fuhui

2014-11-01

TiAlN/Si3N4-Cu nanocomposite coatings of various Si content (0-5.09 at.%) were deposited on AISI-304 stainless steel by DC reactive magnetron sputtering technique. The chemical composition, microstructure, mechanical and tribological properties of these coatings were systematically investigated by means of X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), nanoindentation tester, a home-made indentation system, a scratch tester and a wear tester. Results indicated that with increasing Si content in these coatings, a reduction of grain size and surface roughness, a transformation of the (1 1 1) preferred orientation was detected by XRD and FESEM. Furthermore the hardness of these coatings increase from 9.672 GPa to 18.628 GPa, and the elastic modulus reveal the rising trend that increase from 224.654 GPa to 251.933 GPa. However, the elastic modulus of TiAlN/Si3N4-Cu coating containing 3.39 at.% Si content dropped rapidly and changed to about 180.775 GPa. The H3/E2 ratio is proportional to the film resistance to plastic deformation. The H3/E2 ratio of the TiAlN/Si3N4-Cu coating containing 3.39 at.% Si content possess of the maximum of 0.11 GPa, and the indentation test indicate that few and fine cracks were observed from its indentation morphologies. The growth pattern of cracks is mainly bending growing. The present results show that the best toughness is obtained for TiAlN/Si3N4-Cu nanocomposite coating containing 3.39 at.% Si content. In addition, the TiAlN/Si3N4-Cu coating containing 3.39 at.% Si content also has good adhesion property and superior wear resistance, and the wear mechanism is mainly adhesion wear.

Theoretical study of the elasticity, mechanical behavior, electronic structure, interatomic bonding, and dielectric function of an intergranular glassy film model in prismatic β-Si3N4

International Nuclear Information System (INIS)

Ching, W. Y.; Rulis, Paul; Aryal, Sitaram; Ouyang, Lizhi; Misra, Anil

2010-01-01

Microstructures such as intergranular glassy films (IGFs) are ubiquitous in many structural ceramics. They control many of the important physical properties of polycrystalline ceramics and can be influenced during processing to modify the performance of devices that contain them. In recent years, there has been intense research, both experimentally and computationally, on the structure and properties of IGFs. Unlike grain boundaries or dislocations with well-defined crystalline planes, the atomic scale structure of IGFs, their fundamental electronic interactions, and their bonding characteristics are far more complicated and not well known. In this paper, we present the results of theoretical simulations using ab initio methods on an IGF model in β-Si 3 N 4 with prismatic crystalline planes. The 907-atom model has a dimension of 14.533 A x 15.225 A x 47.420 A . The IGF layer is perpendicular to the z axis, 16.4 A wide, and contains 72 Si, 32 N, and 124 O atoms. Based on this model, the mechanical and elastic properties, the electronic structure, the interatomic bonding, the localization of defective states, the distribution of electrostatic potential, and the optical dielectric function are evaluated and compared with crystalline β-Si 3 N 4 . We have also performed a theoretical tensile experiment on this model by incrementally extending the structure in the direction perpendicular to the IGF plane until the model fully separated. It is shown that fracture occurs at a strain of 9.42% with a maximum stress of 13.9 GPa. The fractured segments show plastic behavior and the formation of surfacial films on the β-Si 3 N 4 . These results are very different from those of a previously studied basal plane model [J. Chen et al., Phys. Rev. Lett. 95, 256103 (2005)] and add insights to the structure and behavior of IGFs in polycrystalline ceramics. The implications of these results and the need for further investigations are discussed.

Electronic structure and bonding in the ternary silicide YNiSi3

International Nuclear Information System (INIS)

Sung, Gi Hong; Kang, Dae Bok

2003-01-01

An analysis of the electronic structure and bonding in the ternary silicide YNiSi 3 is made, using extended Hueckel tight-binding calculations. The YNiSi 3 structure consists of Ni-capped Si 2 dimer layers and Si zigzag chains. Significant bonding interactions are present between the silicon atoms in the structure. The oxidation state formalism of (Y 3+ )(Ni 0 )(Si 3 ) 3- for YNiSi 3 constitutes a good starting point to describe its electronic structure. Si atoms receive electrons form the most electropositive Y in YNiSi 3 , and Ni 3d and Si 3p states dominate below the Fermi level. There is an interesting electron balance between the two Si and Ni sublattices. Since the π orbitals in the Si chain and the Ni d and s block levels are almost completely occupied, the charge balance for YNiSi 3 can be rewritten as (Y 3+ )(Ni 2- )(Si 2- )(Si-Si) + , making the Si 2 layers oxidized. These results suggest that the Si zigzag chain contains single bonds and the Si 2 double layer possesses single bonds within a dimer with a partial double bond character. Stronger Si-Si and Ni-Si bonding interactions are important for giving stability to the structure, while essentially no metal-metal bonding exists at all. The 2D metallic behavior of this compound is due to the Si-Si interaction leading to dispersion of the several Si 2 π bands crossing the Fermi level in the plane perpendicular to the crystallographic b axis

Residual stresses and mechanical properties of Si3N4/SiC multilayered composites with different SiC layers; Las tensiones residuales y las propiedades mecánicas de compuestos multicapa de Si3N4/SiC con diferentes capas de SiC

Energy Technology Data Exchange (ETDEWEB)

Liua, S.; Lia, Y.; Chena, P.; Lia, W.; Gaoa, S.; Zhang, B.; Yeb, F.

2017-11-01

The effect of residual stresses on the strength, toughness and work of fracture of Si3N4/SiC multilayered composites with different SiC layers has been investigated. It may be an effective way to design and optimize the mechanical properties of Si3N4/SiC multilayered composites by controlling the properties of SiC layers. Si3N4/SiC multilayered composites with different SiC layers were fabricated by aqueous tape casting and pressureless sintering. Residual stresses were calculated by using ANSYS simulation, the maximum values of tensile and compressive stresses were 553.2MPa and −552.1MPa, respectively. Step-like fracture was observed from the fracture surfaces. Fraction of delamination layers increased with the residual stress, which can improve the reliability of the materials. Tensile residual stress was benefit to improving toughness and work of fracture, but the strength of the composites decreased. [Spanish] Se ha investigado el efecto de las tensiones residuales en la resistencia, dureza y trabajo de fractura de los compuestos multicapa de Si3N4/SiC con diferentes capas de SiC. Puede ser una manera eficaz de diseñar y optimizar las propiedades mecánicas de los compuestos multicapa de Si3N4/SiC mediante el control de las propiedades de las capas de SiC. Los compuestos multicapa de Si3N4/SiC con diferentes capas de SiC se fabricaron por medio de colado en cinta en medio acuoso y sinterización sin presión. Las tensiones residuales se calcularon mediante el uso de la simulación ANSYS, los valores máximos de las fuerzas de tracción y compresión fueron 553,2 MPa y −552,1 MPa, respectivamente. Se observó una fractura escalonada a partir de las superficies de fractura. La fracción de capas de deslaminación aumenta con la tensión residual, lo que puede mejorar la fiabilidad de los materiales. La fuerza de tracción residual era beneficiosa para la mejora de la dureza y el trabajo de fractura, pero la resistencia de los compuestos disminuyó.

Interfacial study of NiTi–Ti{sub 3}SiC{sub 2} solid state diffusion bonded joints

Energy Technology Data Exchange (ETDEWEB)

Kothalkar, A. [Department of Materials Science and Engineering, Texas A and M University, College Station, TX 77843 (United States); Cerit, A. [Department of Industrial Design Engineering, Erciyes University, Kayseri (Turkey); Proust, G. [School of Civil Engineering, University of Sydney, Sydney, NSW 2006 (Australia); Basu, S. [Agilent Technologies, Chandler, AZ (United States); Radovic, M., E-mail: mradovic@tamu.edu [Department of Materials Science and Engineering, Texas A and M University, College Station, TX 77843 (United States); Karaman, I., E-mail: ikaraman@tamu.edu [Department of Materials Science and Engineering, Texas A and M University, College Station, TX 77843 (United States)

2015-01-12

The interfaces between the stress-assisted diffusion bonded Ti{sub 3}SiC{sub 2} and equiatomic NiTi, two distinct material systems that show pseudoelasticity were studied. The interfaces were formed in the 800–1000 °C temperature range, for 1, 5 and 10 h under flowing argon. Bonding was observed in all the cases considered, except at 800 °C after 1 h. Morphology and reaction phases in the interface were characterized using scanning electron microscopy, elemental micro probe analysis and electron backscatter diffraction analysis. The interfacial structure formed between NiTi and Ti{sub 3}SiC{sub 2} layers consists of NiTi/Ti{sub 2}Ni/Ti{sub 5}Si{sub 3}/NiTiSi/Ti{sub 3}SiC{sub 2}. Diffusion of Si into NiTi from Ti{sub 3}SiC{sub 2}, and Ni from NiTi into reaction zone was found to be responsible for the formation of reaction layers in the interface and thus for bonding at these conditions. The overall reaction layer thickness grows following the parabolic kinetic law. Nano-indentation and Vickers micro hardness tests were carried out to investigate the mechanical properties of the interface. Nano-indentation showed that the elastic moduli of the phases in the interface are close to that of Ti{sub 3}SiC{sub 2} while their hardness is higher than that of both Ti{sub 3}SiC{sub 2} and NiTi. Artificially formed cracks through microindents were observed to be branched and propagated into Ti{sub 3}SiC{sub 2} phase indicating good resistance against delamination.

U(SMes*)n, (n = 3, 4) and Ln(SMes*)3 (Ln = La, Ce, Pr, Nd): lanthanide(III)/actinide(III) differentiation in agostic interactions and an unprecedented eta3 ligation mode of the arylthiolate ligand, from X-ray diffraction and DFT analysis.

Science.gov (United States)

Roger, Mathieu; Barros, Noémi; Arliguie, Thérèse; Thuéry, Pierre; Maron, Laurent; Ephritikhine, Michel

2006-07-12

Reaction of U(NEt(2))(4) with HS-2,4,6-(t)Bu(3)C(6)H(2) (HSMes) gave U(SMes)(3)(NEt(2))(py) (1), whereas similar treatment of U[N(SiMe(3))SiMe(2)CH(2)][N(SiMe(3))(2)](2) afforded U(SMes)[N(SiMe(3))(2)](3) (2) and U(SMes)(3)[N(SiMe(3))(2)]. The first neutral homoleptic uranium(IV) thiolate to have been crystallographically characterized, U(SMes)(4) (4), was isolated from the reaction of U(BH(4))(4) and KSMes. The first homoleptic thiolate complex of uranium(III), U(SMes)(3) (5), was synthesized by protonolysis of U[N(SiMe(3))(2)](3) with HSMes in cyclohexane. The crystal structure of 5 exhibits the novel eta(3) ligation mode for the arylthiolate ligand. Comparison of the crystal structure of 5 with those of the isomorphous lanthanide congeners Ln(SMes)(3) (Ln = La, Ce, Pr, and Nd) indicates that the U-S, U-C(ipso)(), and U-C(ortho)() bond lengths are shorter than the corresponding ones in the 4f-element analogues, when taking into account the variation in the ionic radii of the metals. The distance between the uranium and the carbon atoms involved in the U...H-C epsilon agostic interaction of each thiolate ligand is shorter, by approximately 0.05 A, than that expected from a purely ionic bonding model. The lanthanide(III)/actinide(III) differentiation was analyzed by density functional theory (DFT). The nature of the M-S bond is shown to be ionic strongly polarized at the sulfur for M = U and iono-covalent (i.e. strongly ionic with low orbital interaction), for M = Ln. The strength of the U...H-C epsilon agostic interaction is proposed to be controlled by the maximization of the interaction between U(+) and S(-) under steric constraints. The eta(3) ligation mode of the arylthiolate ligand is also obtained from DFT.

Germanium growth on electron beam lithography patterned Si3N4/Si(001) substrate using molecular beam epitaxy

Science.gov (United States)

Sarkar, Subhendu Sinha; Katiyar, Ajit K.; Sarkar, Arijit; Dhar, Achintya; Rudra, Arun; Khatri, Ravinder K.; Ray, Samit Kumar

2018-04-01

It is important to investigate the growth dynamics of Ge adatoms under different surface stress regimes of the patterned dielectric to control the selective growth of self-assembled Ge nanostructures on silicon. In the present work, we have studied the growth of Ge by molecular beam epitaxy on nanometer scale patterned Si3N4/Si(001) substrates generated using electron beam lithography. The pitch of the patterns has been varied to investigate its effect on the growth of Ge in comparison to un-patterned Si3N4. For the patterned Si3N4 film, Ge did not desorbed completely from the Si3N4 film and hence no site selective growth pattern is observed. Instead, depending upon the pitch, Ge growth has occurred in different growth modes around the openings in the Si3N4. For the un-patterned substrate, the morphology exhibits the occurrence of uniform 3D clustering of Ge adatoms on Si3N4 film. This variation in the growth modes of Ge is attributed to the variation of residual stress in the Si3N4 film for different pitch of holes, which has been confirmed theoretically through Comsol Multiphysics simulation. The variation in stress for different pitches resulted in modulation of surface energy of the Si3N4 film leading to the different growth modes of Ge.

U(SMes*)n, (n=3, 4) and Ln(SMes*)3 (Ln = La, Ce, Pr, Nd): Lanthanide(III)/actinide(III) differentiation in agostic interactions and an unprecedented eta(3) Ligation mode of the aryl-thiolate ligand, from X-ray diffraction and DFT analysis

International Nuclear Information System (INIS)

Roger, Mathieu; Barros, Noemi; Arliguie, Therese; Thuery, Pierre; Maron, Laurent; Ephritikhine, Michel

2006-01-01

Reaction of U(NEt 2 ) 4 with HS-2,4,6- t Bu 3 C 6 H 2 (HSMes*) gave U(SMes*) 3 (NEt 2 )(py) (1), whereas similar treatment of U[N(SiMe 3 )SiMe 2 CH 2 ][N(SiMe 3 ) 2 ] 2 afforded U(SMes*)[N(SiMe 3 ) 2 ] 3 (2) and U(SMes*) 3 [N(SiMe 3 ) 2 ]. The first neutral homoleptic uranium(IV) thiolate to have been crystallographically characterized, U(SMes*) 4 (4), was isolated from the reaction of U(BH 4 ) 4 and KSMes*. The first homoleptic thiolate complex of uranium(III), U(SMes*) 3 (5), was synthesized by proton-lysis of U[N(SiMe 3 ) 2 ] 3 with HSMes* in cyclohexane. The crystal structure of 5 exhibits the novel η 3 ligation mode for the aryl-thiolate ligand. Comparison of the crystal structure of 5 with those of the isomorphous lanthanide congeners Ln(SMes*) 3 (Ln) La, Ce, Pr, and Nd) indicates that the U-S, U-C ipso , and U-C ortho bond lengths are shorter than the corresponding ones in the 4f-element analogues, when taking into account the variation in the ionic radii of the metals. The distance between the uranium and the carbon atoms involved in the U center dot center dot center dot H-C ε agostic interaction of each thiolate ligand is shorter, by ∼ 0.05 angstrom, than that expected from a purely ionic bonding model. The lanthanide( III)/actinide(III) differentiation was analyzed by density functional theory (DFT). The nature of the M-S bond is shown to be ionic strongly polarized at the sulfur for M) U and ion-covalent (i.e. strongly ionic with low orbital interaction), for M) Ln. The strength of the U center dot center dot center dot H-C ε agostic interaction is proposed to be controlled by the maximization of the interaction between U + and S - under steric constraints. The η 3 ligation mode of the aryl-thiolate ligand is also obtained from DFT. (authors)

A comparative study on microstructure and tribological properties of Si3N4 and TiN thin films produced by IBED method

International Nuclear Information System (INIS)

Zhuang Daming; Liu Jiajun; Zhu Baoliang; Li Wenzhi; Zhang Xushou; Yang Shengrong

1995-01-01

In this paper, the tribological properties of Si 3 N 4 and TiN thin films produced by ion beam enhanced deposition (IBED) method were compared on an SRV friction and wear testing machine. In order to understand the reasons of their excellent properties the microstructure, microhardness and bonding strength with the substrate were analysed by SEM, X-ray diffraction, Knoop hardness test and scratching test methods separately. The results show that the TiN(1) films exhibits the best tribological properties, which are closely related with its higher hardness and bonding strength. (author)

Enhanced visible light photocatalytic H{sub 2} evolution of metal-free g-C{sub 3}N{sub 4}/SiC heterostructured photocatalysts

Energy Technology Data Exchange (ETDEWEB)

Wang, Biao, E-mail: wangbiao@fjirsm.ac.cn [Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); University of the Chinese Academy of Sciences, Beijing 100049 (China); Zhang, Jingtao, E-mail: zhangjtao@mail.sysu.edu.cn [State Key Laboratory of Optoelectronic Materials and Technologies, School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou 510006 (China); Huang, Feng, E-mail: huangfeng@mail.sysu.edu.cn [Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); State Key Laboratory of Optoelectronic Materials and Technologies, School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou 510006 (China)

2017-01-01

Highlights: • Novel g-C{sub 3}N{sub 4}/SiC composite was prepared by synthesizing g-C{sub 3}N{sub 4} on the surface of SiC. • g-C{sub 3}N{sub 4}/SiC composites exhibit much higher H{sub 2} production activity than pure g-C{sub 3}N{sub 4}. • The g-C{sub 3}N{sub 4}/SiC heterojunction mainly accounts for improved photocatalytic activity. - Abstract: g-C{sub 3}N{sub 4} has been attracting much attention for application in visible light photocatalytic water splitting due to its suitable band structure, and high thermal and chemical stability. However, the rapid recombination of photogenerated carriers has inhibited its wide use. For this reason, novel g-C{sub 3}N{sub 4}/SiC composites were prepared via in situ synthesis of g-C{sub 3}N{sub 4} on the surface of SiC, with which g-C{sub 3}N{sub 4} shows tight interaction (chemical bonding). The g-C{sub 3}N{sub 4}/SiC composites exhibit high stability in H{sub 2} production under irradiation with visible light (λ ≥ 420 nm), demonstrating a maximum of 182 μmol g{sup −1} h{sup −1}, being 3.4 times higher than that of pure g-C{sub 3}N{sub 4}. The enhanced photocatalytic H{sub 2} production ability for g-C{sub 3}N{sub 4}/SiC photocatalysts is primarily ascribed to the combined effects of enhanced separation of photogenerated carriers through efficient migration of electron and enlarged surface areas, in addition to the possible contributions of increased hydrophilicity of SiC and polymerization degree of g-C{sub 3}N{sub 4}. This study may provide new insights into the development of g-C{sub 3}N{sub 4}-based composites as stable and efficient photocatalysts for H{sub 2} production from water splitting.

P-type sp3-bonded BN/n-type Si heterodiode solar cell fabricated by laser-plasma synchronous CVD method

International Nuclear Information System (INIS)

Komatsu, Shojiro; Nagata, Takahiro; Chikyo, Toyohiro; Sato, Yuhei; Watanabe, Takayuki; Hirano, Daisuke; Takizawa, Takeo; Nakamura, Katsumitsu; Hashimoto, Takuya; Nakamura, Takuya; Koga, Kazunori; Shiratani, Masaharu; Yamamoto, Atsushi

2009-01-01

A heterojunction of p-type sp 3 -bonded boron nitride (BN) and n-type Si fabricated by laser-plasma synchronous chemical vapour deposition (CVD) showed excellent rectifying properties and proved to work as a solar cell with photovoltaic conversion efficiency of 1.76%. The BN film was deposited on an n-type Si (1 0 0) substrate by plasma CVD from B 2 H 6 + NH 3 + Ar while doping of Si into the BN film was induced by the simultaneous irradiation of an intense excimer laser with a pulse power of 490 mJ cm -2 , at a wavelength of 193 nm and at a repetition rate of 20 Hz. The source of dopant Si was supposed to be the Si substrate ablated at the initial stage of the film growth. The laser enhanced the doping (and/or diffusion) of Si into BN as well as the growth of sp 3 -bonded BN simultaneously in this method. P-type conduction of BN films was determined by the hot (thermoelectric) probe method. The BN/Si heterodiode with an essentially transparent p-type BN as a front layer is supposed to efficiently absorb light reaching the active region so as to potentially result in high efficiency.

Residual stresses and mechanical properties of Si3N4/SiC multilayered composites with different SiC layers

International Nuclear Information System (INIS)

Liua, S.; Lia, Y.; Chena, P.; Lia, W.; Gaoa, S.; Zhang, B.; Yeb, F.

2017-01-01

The effect of residual stresses on the strength, toughness and work of fracture of Si3N4/SiC multilayered composites with different SiC layers has been investigated. It may be an effective way to design and optimize the mechanical properties of Si3N4/SiC multilayered composites by controlling the properties of SiC layers. Si3N4/SiC multilayered composites with different SiC layers were fabricated by aqueous tape casting and pressureless sintering. Residual stresses were calculated by using ANSYS simulation, the maximum values of tensile and compressive stresses were 553.2MPa and −552.1MPa, respectively. Step-like fracture was observed from the fracture surfaces. Fraction of delamination layers increased with the residual stress, which can improve the reliability of the materials. Tensile residual stress was benefit to improving toughness and work of fracture, but the strength of the composites decreased. [es

B-H Bond Activation by an Amidinate-Stabilized Amidosilylene: Non-Innocent Amidinate Ligand.

Science.gov (United States)

Khoo, Sabrina; Shan, Yu-Liang; Yang, Ming-Chung; Li, Yongxin; Su, Ming-Der; So, Cheuk-Wai

2018-05-21

The activation of B-H and B-Cl bonds in boranes by base-stabilized low-valent silicon compounds is described. The reaction of the amidinato amidosilylene-borane adduct [L{Ar(Me 3 Si)N}SiBH 3 ] [1; L = PhC(N tBu) 2 , and Ar = 2,6- iPr 2 C 6 H 3 ] with MeOTf in toluene at room temperature formed [L{Ar(Me 3 Si)N}SiBH 2 OTf] (2). [LSiN(SiMe 3 )Ar] in compound 2 then underwent a B-H bond activation with BH 2 OTf in refluxing toluene to afford the B-H bond activation product [LB(H)Si(H)(OTf){N(SiMe 3 )Ar}] (3). On the other hand, when compound 2 was reacted with 4-dimethylaminopyridine in refluxing toluene, another B-H bond activation product [(μ-κ1:κ1-L)B(H)(DMAP)Si(H){N(Ar)SiMe 3 }]OTf (4) was afforded. Mechanistic studies show that "(μ-κ1:κ1-L)B(H)(OTf)Si(H){N(Ar)SiMe 3 }" (2A) is the key intermediate in the reactions mentioned above. The formation of 2A is further evidenced by the activation of the B-Cl bond in PhBCl 2 by the amidinato silicon(I) dimer [LSi:] 2 to form the B-Cl bond activation product [(μ-κ1:κ1-L)B(Cl)(Ph)Si(Cl)] 2 (6). Compounds 2-4 and 6 were characterized by nuclear magnetic resonance spectroscopy and X-ray crystallography.

Infrared Spectra and Structures of SiH{sub 2}-(CH{sub 2}){sub 2} and CH{sub 2}=CH-SiH{sub 3} Intermediates Prepared in Reactions of Laser-ablated Silicon Atoms with Ethane

Energy Technology Data Exchange (ETDEWEB)

Cho, Han-Gook [Incheon National University, Incheon (Korea, Republic of); Andrews, Lester [University of Virginia, Charlottesville (United States)

2016-03-15

SiH{sub 2}-(CH{sub 2}){sub 2} and CH{sub 2}=CH-SiH{sub 3} were observed in the matrix IR spectra following reactions of laser-ablated Si atoms with ethane on the basis of correlation with computed frequencies. Evidently photon energy is required for the formation of the cyclic Si compound. These Si complexes are similar to the primary products in the previous studies of group 4 metals, in line with the previous results that s{sup 2}p{sup 2} and s{sup 2}d{sup 2} electronic configurations yield similar products. The relatively long C–C bond in the cyclic Si product reflects the structural strain, and the short C-Si and C-C bonds of CH{sub 3}CH=SiH{sub 2} and CH{sub 2}=CH-SiH{sub 3} show that they are true double bonds in line with the natural bond orders. Reactions of transition-metal atoms with small alkanes and halomethanes have been studied in a series of recent investigations. High oxidation-state products (methylidenes and methylidynes) along with insertion complexes were identified in the matrix spectra. It is interesting whether or not Si, a group 14 metalloid, undergoes similar reactions with larger hydrocarbons to provide higher oxidation-state compounds.

Geometric structure of thin SiO xN y films on Si(100)

Science.gov (United States)

Behrens, K.-M.; Klinkenberg, E.-D.; Finster, J.; Meiwes-Broer, K.-H.

1998-05-01

Thin films of amorphous stoichometric SiO xN y are deposited on radiation-heated Si(100) by rapid thermal low-pressure chemical vapour deposition. We studied the whole range of possible compositions. In order to determine the geometric structure, we used EXAFS and photoelectron spectroscopy. Tetrahedrons constitute the short-range units with a central Si atom connected to N and O. The distribution of the possible tetrahedrons can be described by a mixture of the Random Bonding Model and the Random Mixture Model. For low oxygen contents x/( x+ y)≤0.3, the geometric structure of the film is almost the structure of a-Si 3N 4, with the oxygen preferably on top of Si-N 3 triangles. Higher oxygen contents induce changes in the bond lengths, bond angles and coordination numbers.

Bond-specific reaction kinetics during the oxidation of (111) Si: Effect of n-type doping

International Nuclear Information System (INIS)

Gokce, B.; Aspnes, D. E.; Lucovsky, G.; Gundogdu, K.

2011-01-01

It is known that a higher concentration of free carriers leads to a higher oxide growth rate in the thermal oxidation of silicon. However, the role of electrons and holes in oxidation chemistry is not clear. Here, we report real-time second-harmonic-generation data on the oxidation of H-terminated (111)Si that reveal that high concentrations of electrons increase the chemical reactivity of the outer-layer Si-Si back bonds relative to the Si-H up bonds. However, the thicknesses of the natural oxides of all samples stabilize near 1 nm at room temperature, regardless of the chemical kinetics of the different bonds.

Improvement of photoluminescence from Ge layer with patterned Si3N4 stressors

International Nuclear Information System (INIS)

Oda, Katsuya; Okumura, Tadashi; Tani, Kazuki; Saito, Shin-ichi; Ido, Tatemi

2014-01-01

Lattice strain applied by patterned Si 3 N 4 stressors in order to improve the optical properties of Ge layers directly grown on a Si substrate was investigated. Patterned Si 3 N 4 stressors were fabricated by various methods and their effects on the strain and photoluminescence were studied. Although we found that when the stressor was fabricated by thermal chemical vapor deposition (CVD), the Ge waveguide was tensilely and compressively strained in the edge and center positions, respectively, and photoluminescence (PL) could be improved by decreasing the width of the waveguide, the crystallinity of the Ge waveguide was degraded by the thermal impact of the deposition process. Low-temperature methods were therefore used to make the patterned stressors. The tensile strain of the Ge layer increased from 0.14% to 0.2% when the stressor was grown by plasma enhanced CVD at 350 °C, but the effects of the increased tensile strain could not be confirmed because the Si 3 N 4 layer was unstable when irradiated with the excitation light used in photoluminescence measurements. Si 3 N 4 stressors grown by inductively coupled plasma CVD at room temperature increased the tensile strain of the Ge layer up to 0.4%, thus red-shifting the PL peak and obviously increasing the PL intensity. These results indicate that the Si 3 N 4 stressors fabricated by the room-temperature process efficiently improve the performance of Ge light-emitting devices. - Highlights: • Ge layers were directly grown on a Si substrate by low-temperature epitaxial growth. • Si 3 N 4 stressors were fabricated on the Ge layers by various methods. • Tensile strain of the Ge layers was improved by the Si 3 N 4 stressors. • Photoluminescence (PL) intensity was increased with the Si 3 N 4 stressors. • Red-shift of the PL spectra was observed from the tensile strained Ge layers

Synthesis of magnetically recyclable ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts and their catalytic performance for Knoevenagel reaction

Energy Technology Data Exchange (ETDEWEB)

Li, Qingyuan; Jiang, Sai; Ji, Shengfu, E-mail: jisf@mail.buct.edu.cn; Ammar, Muhammad; Zhang, Qingmin; Yan, Junlei

2015-03-15

Novel magnetic ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts were synthesized by encapsulating magnetic SiO{sub 2}@Fe{sub 3}O{sub 4} nanoparticles into ZIF-8 through in situ method. The structures of the catalysts were characterized by TEM, SEM, XRD, FT-IR, VSM, N{sub 2} adsorption/desorption and CO{sub 2}-TPD technology. The catalytic activity and recovery properties of the catalysts for the Knoevenagel reaction of p-chlorobenzaldehyde with malononitrile were evaluated. The results showed that the magnetic ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts had the larger surface areas, the suitable superparamagnetism, and good catalytic activity for Knoevenagel reaction. The conversion of p-chlorobenzaldehyde can reach ~98% and the selectivity of the production can reach ~99% over35.8%ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} (MZC-5) catalyst under the reaction condition of 25 °C and 4 h. The magnetic ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts also had good substrates adaptation. After reaction, the catalyst can be easily separated from the reaction mixture by an external magnet. The recovery catalyst can be reused five times and the conversion of p-chlorobenzaldehyde can be kept over 90%. - Graphical abstract: Novel magnetically recyclable ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts were synthesized by encapsulating magnetic SiO{sub 2}@Fe{sub 3}O{sub 4} nanoparticles into ZIF-8 and the as-synthesized catalysts exhibited a good catalytic activity for the Knoevenagel reaction. - Highlights: • A series of novel magnetic ZIF-8@SiO{sub 2}@Fe{sub 3}O{sub 4} catalysts were synthesized. • The catalysts had the larger surface areas and the suitable superparamagnetism. • The catalysts exhibited good catalytic activity for the Knoevenagel reaction. • After reaction the catalyst can be easily separated by an external magnet. • The recovery catalyst can be reused five times and can keep its catalytic activity.

Total Ionizing Dose Effects of Si Vertical Diffused MOSFET with SiO2 and Si3N4/SiO2 Gate Dielectrics

Directory of Open Access Journals (Sweden)

Jiongjiong Mo

2017-01-01

Full Text Available The total ionizing dose irradiation effects are investigated in Si vertical diffused MOSFETs (VDMOSs with different gate dielectrics including single SiO2 layer and double Si3N4/SiO2 layer. Radiation-induced holes trapping is greater for single SiO2 layer than for double Si3N4/SiO2 layer. Dielectric oxidation temperature dependent TID effects are also studied. Holes trapping induced negative threshold voltage shift is smaller for SiO2 at lower oxidation temperature. Gate bias during irradiation leads to different VTH shift for different gate dielectrics. Single SiO2 layer shows the worst negative VTH at VG=0 V, while double Si3N4/SiO2 shows negative VTH shift at VG=-5 V, positive VTH shift at VG=10 V, and negligible VTH shift at VG=0 V.

Tribological characteristics of Si3N4-based composites in unlubricated sliding against steel ball

International Nuclear Information System (INIS)

Liu, C.-C.; Huang, J.-L.

2004-01-01

The dry-sliding wear mechanism of Si 3 N 4 -based composites against AISI-52100 steel ball was studied using a ball-on-disc mode in a reciprocation motion. The addition of TiN particles can increase the fracture toughness of Si 3 N 4 -based composites. The fracture toughness of Si 3 N 4 -based composites played an important role for wear behavior. The Si 3 N 4 -based composites exhibits a small friction and wear coefficient compared to monolithic Si 3 N 4 . Atomic force microscopy (AFM) studies displayed fine wear grooves along the sliding traces. The subsurface deformation shows that the microcrack propagation extends along the TiN/Si 3 N 4 grain interface. The wear mechanisms were determined with scanning electron microscopy, transmission electron microscopy, X-ray diffraction and atomic force microscopy

Tribological Behavior of Si3N4/Ti3SiC2 Contacts Lubricated by Lithium-Based Ionic Liquids

Directory of Open Access Journals (Sweden)

Haizhong Wang

2014-01-01

Full Text Available The tribological performance of Si3N4 ball sliding against Ti3SiC2 disc lubricated by lithium-based ionic liquids (ILs was investigated using an Optimol SRV-IV oscillating reciprocating friction and wear tester at room temperature (RT and elevated temperature (100°C. Glycerol and the conventional imidazolium-based IL 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonylimide (L-F106 were used as references under the same experimental conditions. The results show that the lithium-based ILs had higher thermal stabilities than glycerol and lower costs associated with IL preparation than L-F106. The tribotest results show that the lithium-based ILs were effective in reducing the friction and wear of Si3N4/Ti3SiC2 contacts. [Li(urea]TFSI even produced better tribological properties than glycerol and L-F106 both at RT and 100°C. The SEM/EDS and XPS results reveal that the excellent tribological endurance of Si3N4/Ti3SiC2 contacts lubricated by lithium-based ILs was mainly attributed to the formation of surface protective films composed of various tribochemical products.

The Co-III-C bond in (1-thia-4,7-diazacyclodecyl-kappa N-3(4),N-7,C-10)(1,4,7-triazacyclononane-kappa N-3(1),N-4,N-7)-cobalt(III) dithionate hydrate

DEFF Research Database (Denmark)

Harris, Pernille; Kofod, P.; Song, Y.S.

2003-01-01

In the title compound, [Co(C6H15N3)(C7H15N2S)]S2O6.H2O, the Co-C bond distance is 1.9930 (13) Angstrom, which is shorter than for related compounds with the linear 1,6-diamino-3-thiahexan-4-ide anion in place of the macrocyclic 1-thia-4,7-diazacyclodecan-8-ide anion. The coordinated carbanion pro...... produces an elongation of 0.102 (7) Angstrom of the Co-N bond to the 1,4,7-triazacyclononane N atom in the trans position. This relatively small trans influence is presumably a result of the triamine ligand forming strong bonds to the Co-III atom....

Uptake properties of Ni2+ by nCaO.Al2O3.2SiO2 (n=1-4) prepared from solid-state reaction of kaolinite and calcite.

Science.gov (United States)

Jha, Vinay Kumar; Kameshima, Yoshikazu; Nakajima, Akira; Okada, Kiyoshi; MacKenzie, Kenneth J D

2005-08-31

A series of nCaO.Al2O3.2SiO2 samples (n=1-4) were prepared by solid-state reaction of mechanochemically treated mixtures of kaolinite and calcite fired at 600-1000 degrees C for 24 h. All the samples were X-ray amorphous after firing at 600-800 degrees C but had crystallized by 900 degrees C. The main crystalline phases were anorthite (n=1), gehlenite (n=2 and 3) and larnite (n=4). The uptake of Ni2+ by nCaO.Al2O3.2SiO2 samples fired at 800 and 900 degrees C was investigated at room temperature using solutions with initial Ni2+ concentrations of 0.1-50 mmol/l. Amorphous samples (fired at 800 degrees C) showed a higher Ni2+ uptake capacity than crystalline samples (fired at 900 degrees C). Ni2+ uptake was found to increase with increasing of CaO content. Amorphous 4CaO.Al2O3.2SiO2 showed the highest Ni2+ uptake capacity (about 9 mmol/g). The Ni2+ uptake abilities of the present samples are higher than those of other materials reported in the literature. Since the sorbed Ni2+/released Ca2+ ratios of these samples are close to unity, ion replacement of Ni2+ for Ca2+ is thought to be the principal mechanism of Ni2+ uptake by the present samples.

Process control & monitoring for laser micromaching of Si3N4 ceramics

CSIR Research Space (South Africa)

Tshabalala, L

2012-09-01

Full Text Available Laser machining which is a non-contact process that offers the advantage of machining advanced ceramics. In laser machining Si3N4, surface temperature is increased and controlled to evaporate the YSiAlON glassy phase of the Si3N4. However...

Structural, bonding, anisotropic mechanical and thermal properties of Al4SiC4 and Al4Si2C5 by first-principles investigations

Directory of Open Access Journals (Sweden)

Liang Sun

2016-09-01

Full Text Available The structural, bonding, electronic, mechanical and thermal properties of ternary aluminum silicon carbides Al4SiC4 and Al4Si2C5 are investigated by first-principles calculations combined with the Debye quasi-harmonic approximation. All the calculated mechanical constants like bulk, shear and Young's modulus are in good agreement with experimental values. Both compounds show distinct anisotropic elastic properties along different crystalline directions, and the intrinsic brittleness of both compounds is also confirmed. The elastic anisotropy of both aluminum silicon carbides originates from their bonding structures. The calculated band gap is obtained as 1.12 and 1.04 eV for Al4SiC4 and Al4Si2C5 respectively. From the total electron density distribution map, the obvious covalent bonds exist between Al and C atoms. A distinct electron density deficiency sits between AlC bond along c axis among Al4SiC4, which leads to its limited tensile strength. Meanwhile, the anisotropy of acoustic velocities for both compounds is also calculated and discussed.

The temperature dependence of the Young's modulus of MgSiN2, AlN and Si3N4

NARCIS (Netherlands)

Bruls, R.J.; Hintzen, H.T.J.M.; With, de G.; Metselaar, R.

2001-01-01

The temperature dependence of the Young's modulus of MgSiN2 and AlN was measured between 293 and 973 K using the impulse excitation method and compared with literature data reported for Si3N4. The data could be fitted with . The values of the fitting parameters E0 and T0 are related to the Debye

Preparation of rod-like β-Si3N4 single crystal particles

International Nuclear Information System (INIS)

Hirao, K.; Tsuge, A.; Brito, M.E.; Kanzaki, S.

1994-01-01

The use of β-Si 3 N 4 particles as a seed material has been demonstrated to be effective for development of a self-reinforcing microstructure in sintered silicon nitride ceramics. We have confirmed the seeding effect and arrived at a concept that seed particles should consist of rod-like single crystals free from defects and with a large diameter. The present work describes our attempts to produce such particles with a controlled morphology and in high amount. β-Si 3 N 4 particles with a diameter of 1μm and length of 5μm were obtained by heating a mixture of α-Si 3 N 4 , SiO 2 and Y 2 O 3 , followed by acid rinse treatments to remove residual glassy phase. (orig.)

Large resistive-switching phenomena observed in Ag/Si3N4/Al memory cells

International Nuclear Information System (INIS)

Kim, Hee-Dong; An, Ho-Myoung; Kim, Kyoung Chan; Seo, Yujeong; Kim, Tae Geun; Nam, Ki-Hyun; Chung, Hong-Bay; Lee, Eui Bok

2010-01-01

An effective resistive-switching effect has been observed in silicon nitride (Si 3 N 4 ) dielectrics in Ag/Si 3 N 4 /Al memory cells. The ratio of the low resistance to high resistance state was larger than 10 7 at ±1.2 V for a 10 nm thick Si 3 N 4 layer. This switching behavior is attributed to a change in the conductivity of the Si 3 N 4 dielectrics, depending on whether nitride-related traps are filled with electrons under positive biases or unfilled under negative biases. This assertion is experimentally confirmed from the relationship between the amount of charges trapped in the Si 3 N 4 layer and the corresponding changes in its resistance with respect to bias voltages. In addition, the formation or dissolution of the conductive path is confirmed by conductive atomic force microscopy current images

Grinding Si3N4 Powder In Si3N4 Equipment

Science.gov (United States)

Herbell, Thomas P.; Freedman, Marc R.; Kiser, James D.

1989-01-01

Three methods of grinding compared. Report based on study of grinding silicon nitride powder in preparation for sintering into solid ceramic material. Attrition, vibratory, and ball mills lined with reaction-bonded silicon nitride tested. Rates of reduction of particle sizes and changes in chemical compositions of powders measured so grinding efficiences and increases in impurity contents from wear of mills and media evaluated for each technique.

Low-temperature Au/a-Si wafer bonding

International Nuclear Information System (INIS)

Jing, Errong; Xiong, Bin; Wang, Yuelin

2011-01-01

The Si/SiO 2 /Ti/Au–Au/Ti/a-Si/SiO 2 /Si bonding structure, which can also be used for the bonding of non-silicon material, was investigated for the first time in this paper. The bond quality test showed that the bond yield, bond repeatability and average shear strength are higher for this bonding structure. The interfacial microstructure analysis indicated that the Au-induced crystallization of the amorphous silicon process leads to big Si grains extending across the bond interface and Au filling the other regions of the bond interface, which result into a strong and void-free bond interface. In addition, the Au-induced crystallization reaction leads to a change in the IR images of the bond interface. Therefore, the IR microscope can be used to evaluate and compare the different bond strengths qualitatively. Furthermore, in order to verify the superiority of the bonding structure, the Si/SiO 2 /Ti/Au–a-Si/SiO 2 /Si (i.e. no Ti/Au layer on the a-Si surface) and Si/SiO 2 /Ti/Au–Au/Ti/SiO 2 /Si bonding structures (i.e. Au thermocompression bonding) were also investigated. For the Si/SiO 2 /Ti/Au–a-Si/SiO 2 /Si bonding structure, the poor bond quality is due to the native oxide layer on the a-Si surface, and for the Si/SiO 2 /Ti/Au–Au/Ti/SiO 2 /Si bonding structure, the poor bond quality is caused by the wafer surface roughness which prevents intimate contact and limits the interdiffusion at the bond interface.

DSC法研究MMA／纳米Si3N4体系的聚合过程%STUDY ON POLYMERIZATION PROCESS OF MMA/NANO-SI3N4 BY DSC

Institute of Scientific and Technical Information of China (English)

王小东

2011-01-01

Polymerization process of MMA/nano-Si3N4 was studied by DSC. Effects of polymerization temperature, nano-Si3N4 amount and initator concentration of AIBN on polymerization rate were investigated in this article. The results showed that with the polymerization temperature rising,the rate of polymerization increased;the initiatior concentration could effectually improve the polymerization rate; but with the increasing of nano-Si3N4 amount, the polymerization rate was decreased.%利用差示扫描量热仪（DSC）对MMA／纳米Si3N4体系的聚合过程进行研究，着重考察了聚合温度，纳米Si2N4粉体加入量及引发剂AIBN用量对体系聚合速率的影响．结果表明：升高聚合反应温度，增大引发剂用量，均可使体系的凝胶效应提前出现，聚合速率增大；而纳米Si3N4粉体的加入对体系的聚合起到延缓的作用，且随着加入量的增加，聚合速率逐渐降低．

Magnetic behavior of Si-Ge bond in SixGe4-x nano-clusters

Science.gov (United States)

Nahali, Masoud; Mehri, Ali

2018-06-01

The structure of SixGe4-x nano-clusters were optimized by MPW1B95 level of theory using MG3S and SDB-aug-cc-PVTZ basis set. The agreement of the calculated ionization and dissociation energies with experimental values validates the reported structures of nano-clusters and justifies the use of hybrid meta density functional method. Since the Si-Si bond is stronger than Si-Ge and Ge-Ge bonds, the Si-Si, Si-Ge, and Ge-Ge diagonal bonds determine the precedence of the stability in these nano-clusters. The hybrid meta density functional calculations were carried out to investigate the adsorption of CO on all possible SixGe4-x nano-clusters. It was found that the silicon atom generally makes a stronger bond with CO than germanium and thereby preferentially affects the shape of structures having higher multiplicity. In Si-Ge structures with higher spin more than 95% of spins accumulate on positions with less bonds to other atoms of the cluster. Through CO adsorption on these clusters bridge structures are made that behave as spin bridge which conduct the spin from the nano-cluster surface to the adsorbate atoms. A better understanding of bridged structures was achieved upon introducing the 'spin bridge' concept. Based on exhaustive spin density analysis, it was found that the reason for the extra negative charge on oxygen in the bridged structures is the relocation of spin from the surface through the bridge.

Processing, Microstructure, and Mechanical Properties of Si3N4/SiC Nanocomposites from Precursor Derived Ceramics

Science.gov (United States)

Strong, Kevin Thomas, Jr.

Polymer-derived ceramics (PDCs) provides a unique processing route to create Si3N4/SiC composites. Silazane precursor polyureasilazane (Ceraset PURS20) produce's an amorphous SiCN ceramic at temperatures of ~800 -- 1200 °C and crystallizes to a Si3N4/SiC nanocomposite at temperatures >1500 °C. A novel processing technique was developed where crosslinked polymers were heat-treated in a reactive NH3 atmosphere to control the stoichiometry of the pyrolyzed SiCN ceramic. Using this technique processing parameters were established to produce SiCN powders that resulted in nanocomposites with approximately 0, 5, 10, 20 and 30 vol. % SiC. Lu2O3 was added to these powders as a sintering aid and were densified using Hot Pressing and Field Assisted Sintering. The sintered nanocomposites resulted in microstructures with multiple-length scales. These length-scales included Si3N4 (0.1 -- 5 microm), SiC (10 -- 100 nm) and the intergranular grain boundary phase (<1 nm). Using a combination of SEM and TEM it was possible to quantify some of these microstructural features such as the size and location of the SiC. Hardness and fracture toughness testing was conducted to compared the room temperature mechanical properties of these resultant microstructures. This research was intended to develop robust processing approaches that can be used to control the nanostructures of Si3N4/SiC composites with significant structural features at multiple length scales. The control of their features and the investigation of their affect on the properties of composites can be used to simulate the affect of the structure on properties. These models can then be used to design optimal microstructures for specific applications.

Enhancement of photoluminescence properties and modification of crystal structures of Si{sub 3}N{sub 4} doping Li{sub 2}Sr{sub 0.995}SiO{sub 4}:0.005Eu{sup 2+} phosphors

Energy Technology Data Exchange (ETDEWEB)

Song, Kaixin, E-mail: kxsong@hdu.edu.cn [College of Electronic Information and Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China); Zhang, Fangfang [College of Electronic Information and Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China); Chen, Daqin [College of Materials Sciences and Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China); Wu, Song; Zheng, Peng [College of Electronic Information and Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China); Huang, Qingming [Instrument Analysis and Testing Center, Fuzhou University, Fuzhou 350002 (China); Jiang, Jun [Ningbo Institute of Materials Technologies and Engineering, Chinese Academy of Sciences, Ningbo 315201 (China); Xu, Junming; Qin, Huibin [College of Electronic Information and Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China)

2015-10-15

Highlights: • Si{sub 3}N{sub 4} modified Li{sub 2}Sr{sub 0.995}SiO{sub 4}:0.005Eu{sup 2+} phosphors were prepared. • The luminescence intensity of Li{sub 2}Sr{sub 0.995}SiO{sub 4}:Eu{sup 2+} was enhanced by doping Si{sub 3}N{sub 4}. • The fluorescence decay times and thermal stability were enhanced by doping Si{sub 3}N{sub 4}. - Abstract: Si{sub 3}N{sub 4} modified Li{sub 2}Sr{sub 0.995}SiO{sub 4}:0.005Eu{sup 2+} (Li{sub 2}Sr{sub 0.995}SiO{sub 4−3x/2}N{sub x}:0.005Eu{sup 2+}) phosphors were synthesized with the conventional solid-state reaction in the reduced atmosphere. The crystal structure and vibrational modes were analyzed by X-ray diffraction, Raman scattering spectroscopy and Rietveld crystal structure refinement. Photoluminescence (PL) and photoluminescence excitation (PLE) spectra showed that Li{sub 2}Sr{sub 0.995}SiO{sub 4−3x/2}N{sub x}:0.005Eu{sup 2+} powder exhibited a broad yellow emission band centered at 560 nm under the excitation of 460 nm visible light, due to the 4f{sup 6}5d{sup 1} → 4f{sup 7} transition of Eu{sup 2+}. The partial nitridation of Li{sub 2}Sr{sub 0.995}SiO{sub 4−3x/2}N{sub x}:0.005Eu{sup 2+} (x = 0.01) phosphors led to a large enhancement in the luminescence intensity, as much as 190%. At the same time, the fluorescence decay behavior curves further showed that the photoluminescence efficiencies of Li{sub 2}Sr{sub 0.995}SiO{sub 4−3x/2}N{sub x}:0.005Eu{sup 2+} phosphors were enhanced by addition of Si{sub 3}N{sub 4}. The temperature quenching characteristics confirmed that the oxynitride based Li{sub 2}Sr{sub 0.995}SiO{sub 4−3x/2}N{sub x}:0.005Eu{sup 2+} showed slightly higher stability. It is implied that Li{sub 2}Sr{sub 0.995}SiO{sub 4−3x/2}N{sub x}:0.005Eu{sup 2+} phosphors had a possible potential application on white LEDs to match blue light chips.

Lattice dynamics of a- Si3N4

International Nuclear Information System (INIS)

Schulz, P.A.B.; Silva, C.E.T.G. da

1984-01-01

We introduce a model for the lattice dynamics of SI 3 N 4 in its amorphous phase. This model is based on a Born hamiltonian, solved in the Bethe lattice approximation. We included the local vicinity until third nearest neighbours, building up the central cluster. (M.W.O.) [pt

C=C bond cleavage on neutral VO3(V2O5)n clusters.

Science.gov (United States)

Dong, Feng; Heinbuch, Scott; Xie, Yan; Bernstein, Elliot R; Rocca, Jorge J; Wang, Zhe-Chen; Ding, Xun-Lei; He, Sheng-Gui

2009-01-28

The reactions of neutral vanadium oxide clusters with alkenes (ethylene, propylene, 1-butene, and 1,3-butadiene) are investigated by experiments and density function theory (DFT) calculations. Single photon ionization through extreme ultraviolet radiation (EUV, 46.9 nm, 26.5 eV) is used to detect neutral cluster distributions and reaction products. In the experiments, we observe products (V(2)O(5))(n)VO(2)CH(2), (V(2)O(5))(n)VO(2)C(2)H(4), (V(2)O(5))(n)VO(2)C(3)H(4), and (V(2)O(5))(n)VO(2)C(3)H(6), for neural V(m)O(n) clusters in reactions with C(2)H(4), C(3)H(6), C(4)H(6), and C(4)H(8), respectively. The observation of these products indicates that the C=C bonds of alkenes can be broken on neutral oxygen rich vanadium oxide clusters with the general structure VO(3)(V(2)O(5))(n=0,1,2...). DFT calculations demonstrate that the reaction VO(3) + C(3)H(6) --> VO(2)C(2)H(4) + H(2)CO is thermodynamically favorable and overall barrierless at room temperature. They also provide a mechanistic explanation for the general reaction in which the C=C double bond of alkenes is broken on VO(3)(V(2)O(5))(n=0,1,2...) clusters. A catalytic cycle for alkene oxidation on vanadium oxide is suggested based on our experimental and theoretical investigations. The reactions of V(m)O(n) with C(6)H(6) and C(2)F(4) are also investigated by experiments. The products VO(2)(V(2)O(5))(n)C(6)H(4) are observed for dehydration reactions between V(m)O(n) clusters and C(6)H(6). No product is detected for V(m)O(n) clusters reacting with C(2)F(4). The mechanisms of the reactions between VO(3) and C(2)F(4)/C(6)H(6) are also investigated by calculations at the B3LYP/TZVP level.

On a two-layer Si_3N_4/SiO_2 dielectric mask for low-resistance ohmic contacts to AlGaN/GaN HEMTs

International Nuclear Information System (INIS)

Arutyunyan, S. S.; Pavlov, A. Yu.; Pavlov, B. Yu.; Tomosh, K. N.; Fedorov, Yu. V.

2016-01-01

The fabrication of a two-layer Si_3N_4/SiO_2 dielectric mask and features of its application in the technology of non-fired epitaxially grown ohmic contacts for high-power HEMTs on AlGaN/GaN heterostructures are described. The proposed Si_3N_4/SiO_2 mask allows the selective epitaxial growth of heavily doped ohmic contacts by nitride molecular-beam epitaxy and the fabrication of non-fired ohmic contacts with a resistance of 0.15–0.2 Ω mm and a smooth surface and edge morphology.

Preparation of Si3N4 Form Diatomite via a Carbothermal Reduction-Nitridation Process

Science.gov (United States)

Ma, Bin; Huang, Zhaohui; Mei, Lefu; Fang, Minghao; Liu, Yangai; Wu, Xiaowen; Hu, Xiaozhi

2016-05-01

Si3N4 was produced using diatomite and sucrose as silicon and carbon sources, respectively. The effect of the C/SiO2 molar ratio, heating temperature and soaking time on the morphology and phase compositions of the final products was investigated by scanning electron microscopy, x-ray diffraction analysis and energy dispersive spectroscopy. The phase equilibrium relationships of the system at different heating temperatures were also investigated based on the thermodynamic analysis. The results indicate that the phase compositions depended on the C/SiO2 molar ratio, heating temperature and soaking time. Fabrication of Si3N4 from the precursor via carbothermal reduction nitridation was achieved at 1550°C for 1-8 h using a C/SiO2 molar ratio of 3.0. The as-prepared Si3N4 contained a low amount of Fe3Si (<1 wt.%).

Formation of doubly and triply bonded unsaturated compounds HCN, HNC, and CH2NH via N + CH4 low-temperature solid state reaction: from molecular clouds to solar system objects

Science.gov (United States)

Mencos, Alejandro; Krim, Lahouari

2018-06-01

We show in the current study carried out in solid phase at cryogenic temperatures that methane (CH4) ice exposed to nitrogen atoms is a source of two acids HCN, HNC, and their corresponding hydrogenated unsaturated species CH2NH, in addition to CH3, C2H6, CN-, and three nitrogen hydrides NH, NH2, and NH3. The solid state N + CH4 reaction taken in the ground state seems to be strongly temperature dependent. While at temperatures lower than 10 K only CH3, NH, NH2, and NH3 species formation is promoted due to CH bond dissociation and NH bond formation, stable compounds with CN bonds are formed at temperatures ranged between 10 and 40 K. Many of these reaction products, resulting from CH4 + N reaction, have already been observed in N2-rich regions such as the atmospheres of Titan, Kuiper belt objects, and molecular clouds of the interstellar medium. Our results show the power of the solid state N-atom chemistry in the transformation of simple astrochemical relevant species, such as CH4 molecules and N atoms into complex organic molecules which are also potentially prebiotic species.

Sequence of phase transitions in (NH4)3SiF7.

Science.gov (United States)

Mel'nikova, S V; Molokeev, M S; Laptash, N M; Pogoreltsev, E I; Misyul, S V; Flerov, I N

2017-02-21

Single crystals of silicon double salt (NH 4 ) 3 SiF 7 = (NH 4 ) 2 SiF 6 ·NH 4 F = (NH 4 ) 3 [SiF 6 ]F were grown and studied by the methods of polarization optics, X-ray diffraction and calorimetry. A sequence of symmetry transformations with the temperature change was established: P4/mbm (Z = 2) (G 1 ) ↔ Pbam (Z = 4) (G 2 ) ↔ P2 1 /c (Z = 4) (G 3 ) ↔ P1[combining macron] (Z = 4) (G 4 ) ↔ P2 1 /c (Z = 8) (G 5 ). Crystal structures of different phases were determined. The experimental data were also interpreted by a group-theoretical analysis of the complete condensate of order parameters taking into account critical and noncritical atomic displacements. Strengthening of the N-HF hydrogen bonds can be a driving force of the observed phase transitions.

Improvement of photoluminescence from Ge layer with patterned Si{sub 3}N{sub 4} stressors

Energy Technology Data Exchange (ETDEWEB)

Oda, Katsuya, E-mail: Katsuya.Oda.cb@hitachi.com; Okumura, Tadashi; Tani, Kazuki; Saito, Shin-ichi; Ido, Tatemi

2014-04-30

Lattice strain applied by patterned Si{sub 3}N{sub 4} stressors in order to improve the optical properties of Ge layers directly grown on a Si substrate was investigated. Patterned Si{sub 3}N{sub 4} stressors were fabricated by various methods and their effects on the strain and photoluminescence were studied. Although we found that when the stressor was fabricated by thermal chemical vapor deposition (CVD), the Ge waveguide was tensilely and compressively strained in the edge and center positions, respectively, and photoluminescence (PL) could be improved by decreasing the width of the waveguide, the crystallinity of the Ge waveguide was degraded by the thermal impact of the deposition process. Low-temperature methods were therefore used to make the patterned stressors. The tensile strain of the Ge layer increased from 0.14% to 0.2% when the stressor was grown by plasma enhanced CVD at 350 °C, but the effects of the increased tensile strain could not be confirmed because the Si{sub 3}N{sub 4} layer was unstable when irradiated with the excitation light used in photoluminescence measurements. Si{sub 3}N{sub 4} stressors grown by inductively coupled plasma CVD at room temperature increased the tensile strain of the Ge layer up to 0.4%, thus red-shifting the PL peak and obviously increasing the PL intensity. These results indicate that the Si{sub 3}N{sub 4} stressors fabricated by the room-temperature process efficiently improve the performance of Ge light-emitting devices. - Highlights: • Ge layers were directly grown on a Si substrate by low-temperature epitaxial growth. • Si{sub 3}N{sub 4} stressors were fabricated on the Ge layers by various methods. • Tensile strain of the Ge layers was improved by the Si{sub 3}N{sub 4} stressors. • Photoluminescence (PL) intensity was increased with the Si{sub 3}N{sub 4} stressors. • Red-shift of the PL spectra was observed from the tensile strained Ge layers.

Colloidal processing and rapid prototyping of Si{sub 3}N{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Liwu Wang

1998-12-01

Some progresses have been made in the wet shaping of Si{sub 3}N{sub 4} based on a better understanding of the colloidal behavior of suspensions and by improved pressure casting with porous polystyrene (PS) molds. This work illustrated that the combination of proper colloidal processing and rapid prototyping is an effective way to fabricate high-performance ceramics with complex shapes. In colloidal processing the packing density and microstructure of green bodies can be controlled if the interaction between ceramic particles in suspensions and the conditions under which the suspensions are consolidated are understood. Therefore, detailed studies on the surface chemistry of the Si{sub 3}N{sub 4} powder, the dispersing behavior of Si{sub 3}N{sub 4} suspensions, the influence of dispersants and the mechanism during powder consolidation into complex-shaped green bodies are performed. (orig.)

4,6-Dibromo-N-{3-[(4,6-dibromo-2,3-dimethylphenylimino]butan-2-ylidene}-2,3-dimethylaniline

Directory of Open Access Journals (Sweden)

Lina Huang

2013-10-01

Full Text Available The title compound, C20H20Br4N2, is a product of the condensation reaction of 4,6-dibromo-2,3-dimethylaniline and butane-2,3-dione. The molecule has a center of symmetry at the mid-point of the central C—C bond. The dihedral angle between the benzene ring and the 1,4-diazabutadiene plane is 78.3 (2°. Niether hydrogen bonding nor aromatic stacking is observed in the crystal structure.

Fatigue strength of Al2O3 and Si3N4 ceramics

International Nuclear Information System (INIS)

Sonsino, C.M.

1992-01-01

Various Al 2 O 3 ceramics and random samples of two Si 3 N 4 ceramics were examined, with all specimens differing in terms of material and manufacturing parameters. Of the Al 2 O 3 ceramics, randomly selected specimens were tested for their banding strength at room temperature, and three specifically selected specimens were tested for their compressive strength at room temperature, at 800 C and at 1200 C. A number of specimen variants were examined by cyclic fatigue tests at room temperature and 800 C, and at 1200 C in one case, the specimens used being slightly notched specimens (α n = 1,02 and 1,08), or more heavily notched speciments (α n = 1.77, 1.90 and 2.24), with bending loads being either cyclic or growing. The Si 3 N 4 specimens were randomly chosen for bending tests and cyclic fatigue tests, at room temperature. (orig./MM) [de

A Three-Step Atomic Layer Deposition Process for SiN x Using Si2Cl6, CH3NH2, and N2 Plasma.

Science.gov (United States)

Ovanesyan, Rafaiel A; Hausmann, Dennis M; Agarwal, Sumit

2018-06-06

We report a novel three-step SiN x atomic layer deposition (ALD) process using Si 2 Cl 6 , CH 3 NH 2 , and N 2 plasma. In a two-step process, nonhydrogenated chlorosilanes such as Si 2 Cl 6 with N 2 plasmas lead to poor-quality SiN x films that oxidize rapidly. The intermediate CH 3 NH 2 step was therefore introduced in the ALD cycle to replace the NH 3 plasma step with a N 2 plasma, while using Si 2 Cl 6 as the Si precursor. This three-step process lowers the atomic H content and improves the film conformality on high-aspect-ratio nanostructures as Si-N-Si bonds are formed during a thermal CH 3 NH 2 step in addition to the N 2 plasma step. During ALD, the reactive surface sites were monitored using in situ surface infrared spectroscopy. Our infrared spectra show that, on the post-N 2 plasma-treated SiN x surface, Si 2 Cl 6 reacts primarily with the surface -NH 2 species to form surface -SiCl x ( x = 1, 2, or 3) bonds, which are the reactive sites during the CH 3 NH 2 cycle. In the N 2 plasma step, reactive -NH 2 surface species are created because of the surface H available from the -CH 3 groups. At 400 °C, the SiN x films have a growth per cycle of ∼0.9 Å with ∼12 atomic percent H. The films grown on high-aspect-ratio nanostructures have a conformality of ∼90%.

Interaction of silicene with β-Si3N4(0001)/Si(111) substrate; energetics and electronic properties

International Nuclear Information System (INIS)

Filippone, Francesco

2014-01-01

The free-standing, quasi-2D layer of Si is known as silicene, in analogy with graphene. Much effort is devoted in the study of silicene, since, similarly to graphene, it shows a very high electron mobility. The interaction of silicene with a hybrid substrate, β-Si 3 N 4 (0001)/Si(111), exposing the β-Si 3 N 4 (0001) surface, has been studied by means of Density Functional calculations, with van der Waals interactions included. Once deepened the most important structural and electronic features of the hybrid substrate, we demonstrated that an electron transfer occurs from the substrate to the silicene layer. In turn, such an electron transfer can be modulated by the doping of the substrate. The β-Si 3 N 4 /silicene interaction appears to be strong enough to ensure adequate adsorption stability. It is also shown that electronic states of substrate and adsorbate still remain decoupled, paving the way for the exploitation of the peculiar electron mobility properties of the silicene layer. A detailed analysis in both direct and reciprocal space is reported. (paper)

Investigation of the fabrication processes of AlGaN/AlN/GaN HEMTs with in situ Si3N4 passivation

International Nuclear Information System (INIS)

Tomosh, K. N.; Pavlov, A. Yu.; Pavlov, V. Yu.; Khabibullin, R. A.; Arutyunyan, S. S.; Maltsev, P. P.

2016-01-01

The optimum mode of the in situ plasma-chemical etching of a Si 3 N 4 passivating layer in C 3 F 8 /O 2 medium is chosen for the case of fabricating AlGaN/AlN/GaN HEMTs. It is found that a bias of 40–50 V at a high-frequency electrode provides anisotropic etching of the insulator through a resist mask and introduces no appreciable radiation-induced defects upon overetching of the insulator films in the region of gate-metallization formation. To estimate the effect of in situ Si 3 N 4 growth together with the heterostructure in one process on the AlGaN/AlN/GaN HEMT characteristics, transistors with gates without the insulator and with gates through Si 3 N 4 slits are fabricated. The highest drain current of the AlGaN/AlN/GaN HEMT at 0 V at the gate is shown to be 1.5 times higher in the presence of Si 3 N 4 than without it.

The formal combination of three singlet biradicaloid entities to a singlet hexaradicaloid metalloid Ge14[Si(SiMe3)3]5[Li(THF)2]3 cluster.

Science.gov (United States)

Schenk, Christian; Kracke, Andreas; Fink, Karin; Kubas, Adam; Klopper, Wim; Neumaier, Marco; Schnöckel, Hansgeorg; Schnepf, Andreas

2011-03-02

The reaction of GeBr with LiSi(SiMe(3))(3) leads to the metalloid cluster compound [(THF)(2)Li](3)Ge(14)[Si(SiMe(3))(3)](5) (1). After the introduction of a first cluster of this type, in which 14 germanium atoms form an empty polyhedron, [(THF)(2)Li](3)Ge(14)[Ge(SiMe(3))(3)](5) (2), we present here further investigations on 1 to obtain preliminary insight into its chemical and bonding properties. The molecular structure of 1 is determined via X-ray crystal structure solution using synchrotron radiation. The electronic structure of the Ge(14) polyhedron is further examined by quantum chemical calculations, which indicate that three singlet biradicaloid entities formally combine to yield the singlet hexaradicaloid character of 1. Moreover, the initial reactions of 1 after elimination of the [Li(THF)(2)](+) groups by chelating ligands (e.g., TMEDA or 12-crown-4) are presented. Collision induced dissociation experiments in the gas phase, employing FT-ICR mass spectrometry, lead to the elimination of the singlet biradicaloid Ge(5)H(2)[Si(SiMe(3))(3)](2) cluster. The unique multiradicaloid bonding character of the metalloid cluster 1 might be used as a model for reactions and properties in the field of surface science and nanotechnology.

N-[3-(tert-Butyldimethylsiloxymethyl-5-nitrophenyl]acetamide

Directory of Open Access Journals (Sweden)

David Barker

2008-10-01

Full Text Available The title compound, C15H24N2O4Si, was prepared by the reaction of (3-acetamido-5-nitrobenzylmethanol with tert-butyldimethylsilyl chloride and is a key intermediate in the synthesis of novel nonsymmetrical DNA minor groove-binding agents. There are two independent molecules in the structure, which differ primarily in the rotation about the C—O bond next to the Si atom. Two strong N—H...O hydrogen bonds align the molecules into a wide ribbon extending approximately parallel to the b axis.

Corrosion resistant coatings for SiC and Si{sub 3}N{sub 4} ceramics

Energy Technology Data Exchange (ETDEWEB)

Nguyen Thierry; Shaokai Yang; J.J. Brown

1998-09-01

It is the goal of this program to (1) develop coatings for SiC and Si{sub 3}N{sub 4} that will enhance their performance as heat exchangers under coal combustion conditions and (2) to conduct an in-depth evaluation of the cause and severity of ceramic heat exchanger deterioration and failure under coal combustion conditions.

Ba{sub 1.63}La{sub 7.39}Si{sub 11}N{sub 23}Cl{sub 0.42}:Ce{sup 3+} - a nitridosilicate chloride with a zeolite-like structure

Energy Technology Data Exchange (ETDEWEB)

Schultz, Peter; Oeckler, Oliver [Institute of Mineralogy, Crystallography and Materials Science, Faculty of Chemistry and Mineralogy, Leipzig University, Scharnhorststrasse 20, 04275 Leipzig (Germany); Durach, Dajana; Schnick, Wolfgang [Department of Chemistry, University of Munich (LMU), Butenandtstrasse 5-13, 81377 Munich (Germany)

2016-05-15

The nitridosilicate chloride Ba{sub 1.63}La{sub 7.39}Si{sub 11}N{sub 23}Cl{sub 0.42}:Ce{sup 3+} was synthesized by metathesis reaction starting from LaCl{sub 3}, BaH{sub 2}, CeF{sub 3} and the product of the ammonolysis of Si{sub 2}Cl{sub 6}. The title compound is stable towards air and moisture. Diffraction data of a microcrystal were recorded using microfocused synchrotron radiation. X-ray spectroscopy confirms the chemical composition of the crystal. IR spectra corroborate absence of N-H bonds. The compound is homeotypic to Ba{sub 2}Nd{sub 7}Si{sub 11}N{sub 23} and crystallizes in space group Cmmm with a = 11.009(3), b = 23.243(8), c = 9.706(4) Aa and Z = 4, R{sub 1}(all) = 0.0174. According to bond valence sum calculations, some crystallographic positions show complete occupancy by Ba or La whereas others contain significant amounts of both elements. In contrast to the structure prototype Ba{sub 2}Nd{sub 7}Si{sub 11}N{sub 23}, Ba{sub 1.63}La{sub 7.39}Si{sub 11}N{sub 23}Cl{sub 0.42}:Ce{sup 3+} contains chloride ions in channels of the SiN{sub 4} tetrahedra network, hinting at various substitution possibilities of the complex zeolite-like structure. (Copyright copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Reaction of ReH sub 7 (PPh sub 3 ) sub 2 with silanes: Preparation and characterization of the first silyl polyhydride complexes, ReH sub 6 (SiR sub 3 )(PPh sub 3 ) sub 2 (SiR sub 3 = SiPh sub 3 , SiEt sub 3 , SiHEt sub 2 )

Energy Technology Data Exchange (ETDEWEB)

Luo, Xiaoliang; Baudry, D.; Boydell, P.; Charpin, P.; Nierlich, M.; Ephritikhine, M.; Crabtree, R.H. (Yale Univ., New Haven, CT (USA) CEA-CEN Saclay, Gif-sur-Yvette (France))

1990-04-18

Reaction of silanes with ReH{sub 7}(PPh{sub 3}){sub 2} (1) gives the novel rhenium silyl hexahydride complexes ReH{sub 6}(SiR{sub 3})(PPh{sub 3}){sub 2} (SiR{sub 3} = SiPh{sub 3} (2a), SiEt{sub 3} (2b), SiHEt{sub 2} (2c)), which have been fully characterized by IR and {sup 1}H, {sup 31}P, and {sup 13}C NMR spectroscopy and, in the case of 2a, by single-crystal x-ray crystallography. The spectroscopic and x-ray diffraction data suggest that 2a-c probably have a classical nine-coordinate tricapped trigonal-prismatic structure with the two phosphine ligands and the silyl group occupying the three equatorial sites and the six hydride ligands occupying the six axial positions. 2a has been obtained in two crystalline forms, one solvated (CH{sub 2}Cl{sub 2}) and the other unsolvated, and structures were determined on both. The crystal structures of crystals of unsolvated 2a and 2a {times} CH{sub 2} Cl{sub 2} are reported. The Re-Si bond lengths, 2.474 (4) {angstrom} (2a) and 2.475 (4) {angstrom} (2a {times} CH{sub 2}Cl{sub 2}), are shorter than the sum of the covalent radii of the Re and Si atoms (2.65 {angstrom}), which is unusual for a transition-metal silyl complex with a formal d{sup 0} configuration. 35 refs., 2 figs., 4 tabs.

Characterization of a n+3C/n−4H SiC heterojunction diode

Energy Technology Data Exchange (ETDEWEB)

Minamisawa, R. A.; Mihaila, A. [Department of Power Electronics, ABB Corporate Research Center, CH-5405 Baden-Dättwil (Switzerland); Farkas, I.; Hsu, C.-W.; Janzén, E. [Semiconductor Materials, IFM, Linköping University, SE-58183 Linköping (Sweden); Teodorescu, V. S. [National Institute of Material Physics, R-077125 Bucharest-Măgurele (Romania); Afanas' ev, V. V. [Semiconductor Physics Laboratory, KU Leuven, 3001 Leuven (Belgium); Rahimo, M. [ABB Semiconductors, Fabrikstrasse 3, CH-5600 Lenzburg (Switzerland)

2016-04-04

We report on the fabrication of n + 3C/n-4H SiC heterojunction diodes (HJDs) potentially promising the ultimate thermal stability of the junction. The diodes were systematically analyzed by TEM, X-ray diffraction, AFM, and secondary ion mass spectroscopy, indicating the formation of epitaxial 3C-SiC crystal on top of 4H-SiC substrate with continuous interface, low surface roughness, and up to ∼7 × 10{sup 17 }cm{sup −3} dopant impurity concentration. The conduction band off-set is about 1 V as extracted from CV measurements, while the valence bands of both SiC polytypes are aligned. The HJDs feature opening voltage of 1.65 V, consistent with the barrier height of about 1.5 eV extracted from CV measurement. We finally compare the electrical results of the n + 3C/n-4H SiC heterojunction diodes with those featuring Si and Ge doped anodes in order to evaluate current challenges involved in the fabrication of such devices.

Nanowires and nanotubes of BN, GaN and Si3N4

International Nuclear Information System (INIS)

Deepak, F.L.; Gundiah, G.; Govindaraj, A.; Rao, C.N.

2002-01-01

Simple methods of synthesizing nanotubes and nanowires of boron nitride, gallium nitride and silicon nitride have been investigated. The nanotubes and nanowires have been examined by electron microscopy and other techniques. In the case of BN, activated carbon or multi-walled carbon nanotubes (MWNTs) was heated with boric acid in the presence of NH 3 . With activated carbon, BN nanowires constitute the primary products, but good yields of BN nanotubes are obtained with MWNTs. Aligned BN nanotubes are obtained when aligned MWNTs are employed as the starting material suggesting templating role of carbon nanotubes. Single crystal gallium nitride nanowires have been obtained by heating carbon nanotubes coated with gallium acetylacetonate in NH 3 vapor at 910 o C. Single walled carbon nanotubes were used as templated to reduce the diameter of the GaN nanowires. The growth direction of the GaN nanowires is nearly perpendicular to the [100] planes and the nanowires exhibit satisfactory photoluminescence spectra. Si 3 N 4 nanowires have been synthesized by heating multi-walled carbon nanotubes with silica gel at 1360 o C in an atmosphere of NH 3 . Si 3 N 4 nanotubes are found occasionally when aligned multi-walled nanotubes are employed as templates. (author)

Electrical properties of MBE grown Si{sub 3}N{sub 4}-cubic GaN MIS structures

Energy Technology Data Exchange (ETDEWEB)

Zado, A.; Lischka, K.; As, D.J. [University of Paderborn, Faculty of Science, Department of Physics, Warburger Str. 100, 33098 Paderborn (Germany)

2012-03-15

In this work we report on the electrical characterization of non-polar cubic GaN metal-insulator-semiconductor (MIS) structures. Si{sub 3}N{sub 4} layers were deposited in-situ on top of cubic GaN grown on 3C-SiC (001) substrates. The electric characteristics of the MIS structures are measured by capacitance and admittance spectroscopy techniques. From the hysteresis in the capacitance-voltage curves and the peak height of the conductance G{sub p} -{omega} frequency curves the interface state densities are calculated. We find interface traps about 0.3 eV below the conduction band. The density of these traps is D{sub it} = 2.5x10{sup 11} cm{sup -2}eV{sup -1}. This is one order of magnitude lower than in MIS structures with a Si{sub 3}N{sub 4} insulator produced by plasma enhanced vapour deposition and two orders of magnitude lower than in MIS structures on c-GaN with SiO{sub 2} as insulator (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Large scale synthesis of α-Si3N4 nanowires through a kinetically favored chemical vapour deposition process

Science.gov (United States)

Liu, Haitao; Huang, Zhaohui; Zhang, Xiaoguang; Fang, Minghao; Liu, Yan-gai; Wu, Xiaowen; Min, Xin

2018-01-01

Understanding the kinetic barrier and driving force for crystal nucleation and growth is decisive for the synthesis of nanowires with controllable yield and morphology. In this research, we developed an effective reaction system to synthesize very large scale α-Si3N4 nanowires (hundreds of milligrams) and carried out a comparative study to characterize the kinetic influence of gas precursor supersaturation and liquid metal catalyst. The phase composition, morphology, microstructure and photoluminescence properties of the as-synthesized products were characterized by X-ray diffraction, fourier-transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy and room temperature photoluminescence measurement. The yield of the products not only relates to the reaction temperature (thermodynamic condition) but also to the distribution of gas precursors (kinetic condition). As revealed in this research, by controlling the gas diffusion process, the yield of the nanowire products could be greatly improved. The experimental results indicate that the supersaturation is the dominant factor in the as-designed system rather than the catalyst. With excellent non-flammability and high thermal stability, the large scale α-Si3N4 products would have potential applications to the improvement of strength of high temperature ceramic composites. The photoluminescence spectrum of the α-Si3N4 shows a blue shift which could be valued for future applications in blue-green emitting devices. There is no doubt that the large scale products are the base of these applications.

Interfacial reaction in SiC_f/Ti-6Al-4V composite by using transmission electron microscopy

International Nuclear Information System (INIS)

Huang, Bin; Li, Maohua; Chen, Yanxia; Luo, Xian; Yang, Yanqing

2015-01-01

The interfacial reactions of continuous SiC fiber reinforced Ti-6Al-4V matrix composite (SiC_f/Ti-6Al-4V composite) and continuous SiC fiber coated by C reinforced Ti-6Al-4V matrix composite (SiC_f/C/Ti-6Al-4V composite) were investigated by using micro-beam electron diffraction (MBED) and energy disperse spectroscopy (EDS) on transmission electron microscopy (TEM). The sequence of the interfacial reactions in the as-processed and exposed at 900°C for 50h SiC_f/Ti-6Al-4V composites can be described as SiC||TiC||Ti_5Si_3 + TiC||Ti-6Al-4V and SiC||TiC||Ti_5Si_3||TiC||Ti_5Si_3||TiC||Ti_5Si_3||Ti-6Al-4V, respectively. Additionally, both in as-processed and exposed composites, Ti_3SiC_2 and Ti_3Si are absent at the interfaces. For the SiC_f/C/Ti-6Al-4V composite exposed at 900 °C for 50 h, the sequence of the interfacial reaction can be described as SiC||C||TiC_F||TiC_C||Ti-6Al-4V before C coating is completely consumed by interfacial reaction. When interfacial reaction consumes C coating completely, the sequence of the interfacial reaction can be described as SiC||TiC||Ti_5Si_3||TiC||Ti-6Al-4V. Furthermore, in SiC_f/C/Ti-6Al-4V composite, C coating can absolutely prevent Si diffusion from SiC fiber to matrix. Basing on these results, the model of formation process of the interfacial reaction products in the composites was proposed. - Highlights: • We obtained the sequence of the interfacial reactions in the as-processed and exposed at 900 °C for 50 h SiC_f/Ti-6Al-4 V composites as well as in the SiC_f/C/Ti-6Al-4 V composite exposed at 900 °C for 50 h. • We verified that both in as-processed and exposed SiC_f/Ti-6Al-4 V composites, Ti_3SiC_2 and Ti_3Si are absent at the interfaces. • Carbon coating can absolutely prevent silicon diffusion from SiC fiber to matrix. • Basing on these results, the model of formation process of the interfacial reaction products in the composites was proposed.

High-temperature elastic properties of in situ-reinforced Si3N4

International Nuclear Information System (INIS)

Swift, Geoffrey A.; Uestuendag, Ersan; Clausen, Bjoern; Bourke, Mark A.M.; Lin, H.-T.

2003-01-01

A high-temperature tensile stress study of a monolithic silicon nitride (Si 3 N 4 ) was performed with time-of-flight neutron diffraction. A dedicated engineering diffractometer was employed at temperatures reaching 1375 deg. C. Rietveld refinements of diffraction spectra allowed the determination of (1) the coefficient of thermal expansion tensor during heating and (2) lattice strains during loading. The stress-strain response of individual lattice reflections was used to calculate the single-crystal elastic stiffness tensor of Si 3 N 4 at 1375 deg. C via a self-consistent model

Incorporating Si3 N4 into PEEK to Produce Antibacterial, Osteocondutive, and Radiolucent Spinal Implants.

Science.gov (United States)

Pezzotti, Giuseppe; Marin, Elia; Adachi, Tetsuya; Lerussi, Federica; Rondinella, Alfredo; Boschetto, Francesco; Zhu, Wenliang; Kitajima, Takashi; Inada, Kosuke; McEntire, Bryan J; Bock, Ryan M; Bal, B Sonny; Mazda, Osam

2018-04-24

Polyetheretherketone (PEEK) is a popular polymeric biomaterial which is primarily used as an intervertebral spacer in spinal fusion surgery; but it is developed for trauma, prosthodontics, maxillofacial, and cranial implants. It has the purported advantages of an elastic modulus which is similar to native bone and it can be easily formed into custom 3D shapes. Nevertheless, PEEK's disadvantages include its poor antibacterial resistance, lack of bioactivity, and radiographic transparency. This study presents a simple approach to correcting these three shortcomings while preserving the base polymer's biocompatibility, chemical stability, and elastic modulus. The proposed strategy consists of preparing a PEEK composite by dispersing a minor fraction (i.e., 15 vol%) of a silicon nitride (Si 3 N 4 ) powder within its matrix. In vitro tests of PEEK composites with three Si 3 N 4 variants-β-Si 3 N 4 , α-Si 3 N 4 , and β-SiYAlON-demonstrate significant improvements in the polymer's osteoconductive versus SaOS-2 cells and bacteriostatic properties versus gram-positive Staphylococcus epidermidis bacteria. These properties are clearly a consequence of adding the bioceramic dispersoids, according to chemistry similar to that previously demonstrated for bulk Si 3 N 4 ceramics in terms of osteogenic behavior (vs both osteosarcoma and mesenchymal progenitor cells) and antibacterial properties (vs both gram-positive and gram-negative bacteria). © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

N{sub 2}O + SO{sub 2} reaction over Si- and C-doped boron nitride nanotubes: A comparative DFT study

Energy Technology Data Exchange (ETDEWEB)

Esrafili, Mehdi D., E-mail: esrafili@maragheh.ac.ir; Saeidi, Nasibeh

2017-05-01

Highlights: • The mechanisms of N{sub 2}O + SO{sub 2} reaction are investigated over Si- and C-doped BNNTs. • Both Si- and C-doped BNNTs can be used as an efficient catalyst for the N{sub 2}O + SO{sub 2} reaction. • The 2N{sub 2}O → O{sub 2} + N{sub 2} reaction needs a large activation energy over both surfaces. - Abstract: Density functional theory calculations are performed to investigate the mechanisms of N{sub 2}O reduction by SO{sub 2} over Si- and C-doped (6,0) boron nitride nanotubes (BNNTs). According to our results, the Si or C adatom can be strongly stabilized over the vacancy defect of the BNNT. The adsorption energy of Si and C atoms over defective BNNT is calculated to be −297.3 and −333.7 kcal/mol, respectively, indicating a strong interaction between these dopant atoms and the tube surface. The N{sub 2}O reduction reaction includes the decomposition of N{sub 2}O (i.e. N{sub 2}O → N{sub 2} + O*), followed by the reduction of O* by SO{sub 2} molecule (i.e. SO{sub 2} + O* → SO{sub 3}). The calculated energy barrier of the SO{sub 2} + O* → SO{sub 3} reaction on Si- and C-doped BNNTs is 2.4 and 5.4 kcal/mol, respectively. Moreover, the effects of tube diameter and length on the N{sub 2}O reduction are studied in detail. The disproportionation of N{sub 2}O molecules (2N{sub 2}O → 2N{sub 2} + O{sub 2}) over both surfaces needs a quite large activation energy, which indicates the impossibility of this reaction at ambient condition. The results show that both Si- and C-doped BNNTs can be viewed as an effective green catalyst for the reduction of N{sub 2}O.

Effect of Si3N4 Addition on Oxidation Resistance of ZrB2-SiC Composites

Directory of Open Access Journals (Sweden)

Manab Mallik

2017-06-01

Full Text Available The oxidation behavior of ZrB2-20 vol % SiC and ZrB2-20 vol % SiC-5 vol % Si3N4 composites prepared by hot-pressing and subjected to isothermal exposure at 1200 or 1300 °C for durations of 24 or 100 h in air, as well as cyclic exposure at 1300 °C for 24 h, have been investigated. The oxidation resistance of the ZrB2-20 vol % SiC composite has been found to improve by around 20%–25% with addition of 5 vol % Si3N4 during isothermal or cyclic exposures at 1200 or 1300 °C. This improvement in oxidation resistance has been attributed to the formation of higher amounts of SiO2 and Si2N2O, as well as a greater amount of continuity in the oxide scale, because these phases assist in closing the pores and lower the severity of cracking by exhibiting self-healing type behavior. For both the composites, the mass changes are found to be higher during cyclic exposure at 1300 °C by about 2 times compared to that under isothermal conditions.

Preparation and luminescence properties of Ce3+ and Ce3+/Tb(3+)-activated Y4Si2O7N2 phosphors.

Science.gov (United States)

Xia, Zhiguo; Wu, Weiwei

2013-09-28

Ce(3+) and Ce(3+)/Tb(3+)-activated Y4Si2O7N2 phosphors are synthesized by the solid-state method, which can be efficiently excited by near ultraviolet (UV) light emitting diode (LED) chips. The PL spectrum of Y4Si2O7N2:Ce(3+) shows a broad hump between 380 and 650 nm, assigned to the electron transition from the 4f energy level to different 5d sub levels of the Ce(3+) ions at different Y(3+) sites. The color of the Y4Si2O7N2:Ce(3+) phosphor can shift from blue to green by introducing Tb(3+). In addition, the energy transfer process from Ce(3+) to Tb(3+) in the Y4Si2O7N2 host was investigated and discussed in terms of both the luminescence spectra and decay curves. The energy transfer critical distance has been calculated and evaluated by the concentration quenching method. Therefore, the Ce(3+) and Ce(3+)/Tb(3+)-activated Y4Si2O7N2 phosphors can serve as key materials for phosphor-converted white-light UV-LEDs.

Improvement of photoluminescence properties and thermal stability of Y2.9Ce0.1Al5−xSixO12 phosphors with Si3N4 addition

International Nuclear Information System (INIS)

Zhang, Fangfang; Song, Kaixin; Jiang, Jun; Wu, Song; Zheng, Peng; Huang, Qingming; Xu, Junming; Qin, Huibin

2014-01-01

Highlights: • Y 2.9 Ce 0.1 Al 5−x Si x O 12 phosphors were prepared by solid-state reaction in reduced air ambience. • Si 4+ could be incorporated into the host lattice of Y 3 Al 5 O 12 through partial occupation of the Al 3+ sites. • Si 3 N 4 addition can improve photoluminescence efficiency and thermal stability of Y 3 Al 5 O 12 :Ce. - Abstract: A series of Si 3 N 4 doping Y 2.9 Ce 0.1 Al 5−x Si x O 12−3x/2 N 4x/3 phosphors were prepared by solid-state reaction in 95%N 2 –5%H 2 reduced air ambience. The XRD characteristics plus Rietveld refinement results shows that the as-sintered powders are unique crystal phase with the same crystal structure of Y 3 Al 5 O 12 (PDF No. 79-1891). The N element was not detected by the analysis of X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectrum (EDS). The photoluminescence spectra (PL and PLE) tests show that the exciting and emitting intensity of PLE and PL gradually increase due to the increase of Si 3 N 4 concentration. Meanwhile, the phosphorescence decay times are prolonged from 45 ns (x = 0) to 78 ns (x = 0.3), under the monitor of 530 nm wavelength. The thermoluminescence tests (TL) confirm the thermal stability of as-phosphors with Si 3 N 4 addition is much better than that of the pristine Y 2.9 Ce 0.1 Al 5 O 12 phosphors

Spectroscopic characterization of a single dangling bond on a bare Si(100)- c ( 4 × 2 ) surface for n - and p -type doping

KAUST Repository

Mantega, M.

2012-07-19

We investigate the charging state of an isolated single dangling bond formed on an unpassivated Si(100) surface with c(4×2) reconstruction, by comparing scanning tunneling microscopy and spectroscopy analysis with density functional theory calculations. The dangling bond is created by placing a single hydrogen atom on the bare surface with the tip of a scanning tunneling microscope. The H atom passivates one of the dimer dangling bonds responsible for the surface one-dimensional electronic structure. This leaves a second dangling at the reacted surface dimer which breaks the surface periodicity. We consider two possible H adsorption configurations for both the neutral and the doped situation (n- and p-type). In the case of n-doping we find that the single dangling bond state is doubly occupied and the most stable configuration is that with H bonded to the bottom Si atom of the surface dimer. In the case of p-doping the dangling bond is instead empty and the configuration with the H attached to the top atom of the dimer is the most stable. Importantly the two configurations have different scattering properties and phase shift fingerprints. This might open up interesting perspectives for fabricating a switching device by tuning the doping level or by locally charging the single dangling bond state. © 2012 American Physical Society.

Spectroscopic characterization of a single dangling bond on a bare Si(100)- c ( 4 × 2 ) surface for n - and p -type doping

KAUST Repository

Mantega, M.; Rungger, I.; Naydenov, B.; Boland, J. J.; Sanvito, S.

2012-01-01

We investigate the charging state of an isolated single dangling bond formed on an unpassivated Si(100) surface with c(4×2) reconstruction, by comparing scanning tunneling microscopy and spectroscopy analysis with density functional theory calculations. The dangling bond is created by placing a single hydrogen atom on the bare surface with the tip of a scanning tunneling microscope. The H atom passivates one of the dimer dangling bonds responsible for the surface one-dimensional electronic structure. This leaves a second dangling at the reacted surface dimer which breaks the surface periodicity. We consider two possible H adsorption configurations for both the neutral and the doped situation (n- and p-type). In the case of n-doping we find that the single dangling bond state is doubly occupied and the most stable configuration is that with H bonded to the bottom Si atom of the surface dimer. In the case of p-doping the dangling bond is instead empty and the configuration with the H attached to the top atom of the dimer is the most stable. Importantly the two configurations have different scattering properties and phase shift fingerprints. This might open up interesting perspectives for fabricating a switching device by tuning the doping level or by locally charging the single dangling bond state. © 2012 American Physical Society.

Synthesis and reactivity of bis(tetramethylcyclopentadienyl) yttrium metallocenes including the reduction of Me(3)SiN(3) to [(Me(3)Si)(2)N](-) with [(C(5)Me(4)H)(2)Y(THF)](2)(mu-eta(2):eta(2)-N(2)).

Science.gov (United States)

Lorenz, Sara E; Schmiege, Benjamin M; Lee, David S; Ziller, Joseph W; Evans, William J

2010-07-19

The metallocene precursors needed to provide the tetramethylcyclopentadienyl yttrium complexes (C(5)Me(4)H)(3)Y, [(C(5)Me(4)H)(2)Y(THF)](2)(mu-eta(2):eta(2)-N(2)), and [(C(5)Me(4)H)(2)Y(mu-H)](2) for reactivity studies have been synthesized and fully characterized, and their reaction chemistry has led to an unexpected conversion of an azide to an amide. (C(5)Me(4)H)(2)Y(mu-Cl)(2)K(THF)(x), 1, synthesized from YCl(3) and KC(5)Me(4)H reacts with allylmagnesium chloride to make (C(5)Me(4)H)(2)Y(eta(3)-C(3)H(5)), 2, which is converted to [(C(5)Me(4)H)(2)Y][(mu-Ph)(2)BPh(2)], 3, with [Et(3)NH][BPh(4)]. Complex 3 reacts with KC(5)Me(4)H to form (C(5)Me(4)H)(3)Y, 4. The reduced dinitrogen complex, [(C(5)Me(4)H)(2)Y(THF)](2)(mu-eta(2):eta(2)-N(2)), 5, can be synthesized from either [(C(5)Me(4)H)(2)Y](2)[(mu-Ph)(2)BPh(2)], 3, or (C(5)Me(4)H)(3)Y, 4, with potassium graphite under a dinitrogen atmosphere. The (15)N labeled analogue, [(C(5)Me(4)H)(2)Y(THF)](2)(mu-eta(2):eta(2)-(15)N(2)), 5-(15)N, has also been prepared, and the (15)N NMR data have been compared to previously characterized reduced dinitrogen complexes. Complex 2 reacts with H(2) to form the corresponding hydride, [(C(5)Me(4)H)(2)Y(mu-H)](2), 6. Complex 5 displays similar reactivity to that of the analogous [(C(5)Me(4)H)(2)Ln(THF)](2)(mu-eta(2):eta(2)-N(2)) complexes (Ln = La, Lu), with substrates such as phenazine, anthracene, and CO(2). In addition, 5 reduces Me(3)SiN(3) to form (C(5)Me(4)H)(2)Y[N(SiMe(3))(2)], 7.

Improvement of photoluminescence properties and thermal stability of Y{sub 2.9}Ce{sub 0.1}Al{sub 5−x}Si{sub x}O{sub 12} phosphors with Si{sub 3}N{sub 4} addition

Energy Technology Data Exchange (ETDEWEB)

Zhang, Fangfang [College of Electronic Information and Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China); Song, Kaixin, E-mail: kxsong@hdu.edu.cn [College of Electronic Information and Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China); Jiang, Jun [Ningbo Institute of Materials Technologies and Engineering, Chinese Academy of Sciences, Ningbo 315201 (China); Wu, Song; Zheng, Peng [College of Electronic Information and Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China); Huang, Qingming [Instrument Analysis and Testing Center, Fuzhou University, Fuzhou 350002 (China); Xu, Junming; Qin, Huibin [College of Electronic Information and Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China)

2014-12-05

Highlights: • Y{sub 2.9}Ce{sub 0.1}Al{sub 5−x}Si{sub x}O{sub 12} phosphors were prepared by solid-state reaction in reduced air ambience. • Si{sup 4+} could be incorporated into the host lattice of Y{sub 3}Al{sub 5}O{sub 12} through partial occupation of the Al{sup 3+} sites. • Si{sub 3}N{sub 4} addition can improve photoluminescence efficiency and thermal stability of Y{sub 3}Al{sub 5}O{sub 12}:Ce. - Abstract: A series of Si{sub 3}N{sub 4} doping Y{sub 2.9}Ce{sub 0.1}Al{sub 5−x}Si{sub x}O{sub 12−3x/2}N{sub 4x/3} phosphors were prepared by solid-state reaction in 95%N{sub 2}–5%H{sub 2} reduced air ambience. The XRD characteristics plus Rietveld refinement results shows that the as-sintered powders are unique crystal phase with the same crystal structure of Y{sub 3}Al{sub 5}O{sub 12} (PDF No. 79-1891). The N element was not detected by the analysis of X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectrum (EDS). The photoluminescence spectra (PL and PLE) tests show that the exciting and emitting intensity of PLE and PL gradually increase due to the increase of Si{sub 3}N{sub 4} concentration. Meanwhile, the phosphorescence decay times are prolonged from 45 ns (x = 0) to 78 ns (x = 0.3), under the monitor of 530 nm wavelength. The thermoluminescence tests (TL) confirm the thermal stability of as-phosphors with Si{sub 3}N{sub 4} addition is much better than that of the pristine Y{sub 2.9}Ce{sub 0.1}Al{sub 5}O{sub 12} phosphors.

On a two-layer Si{sub 3}N{sub 4}/SiO{sub 2} dielectric mask for low-resistance ohmic contacts to AlGaN/GaN HEMTs

Energy Technology Data Exchange (ETDEWEB)

Arutyunyan, S. S., E-mail: spartakmain@gmail.com; Pavlov, A. Yu.; Pavlov, B. Yu.; Tomosh, K. N.; Fedorov, Yu. V. [Russian Academy of Sciences, Institute of Ultrahigh Frequency Semiconductor Electronics (Russian Federation)

2016-08-15

The fabrication of a two-layer Si{sub 3}N{sub 4}/SiO{sub 2} dielectric mask and features of its application in the technology of non-fired epitaxially grown ohmic contacts for high-power HEMTs on AlGaN/GaN heterostructures are described. The proposed Si{sub 3}N{sub 4}/SiO{sub 2} mask allows the selective epitaxial growth of heavily doped ohmic contacts by nitride molecular-beam epitaxy and the fabrication of non-fired ohmic contacts with a resistance of 0.15–0.2 Ω mm and a smooth surface and edge morphology.

Low-temperature conducting channel switching in hybrid Fe{sub 3}O{sub 4}/SiO{sub 2}/n-Si structures

Energy Technology Data Exchange (ETDEWEB)

Vikulov, V.A., E-mail: vikulov@iacp.dvo.ru [Institute of Automation and Control Processes, FEB RAS, 5 Radio Street, 690041 Vladivostok (Russian Federation); Dimitriev, A.A.; Balashev, V.V.; Pisarenko, T.A.; Korobtsov, V.V. [Institute of Automation and Control Processes, FEB RAS, 5 Radio Street, 690041 Vladivostok (Russian Federation); School of Natural Sciences, Far Eastern Federal University, 690950 Vladivostok (Russian Federation)

2016-09-15

Highlights: • Conducting channel switching between the polycrystalline Fe{sub 3}O{sub 4} film and the n-Si substrate takes place in the Fe{sub 3}O{sub 4}/SiO{sub 2}/n-Si structure at temperature below 125 K. • This effect occurs via the field-assisted tunneling through the composite insulating layer that consists of the highly resistive Fe{sub 3}O{sub 4} and the tunnel SiO{sub 2}. • The switching is attended by a change in the shape of the current-voltage characteristics from the linear at 300 K to the S-type at 80 K. - Abstract: The carrier transport properties of the polycrystalline magnetite (Fe{sub 3}O{sub 4}) films grown on an n-type Si substrate with 5 nm-thick SiO{sub 2} have been investigated between 80 and 300 K in current-in-plane geometry. It was established that at temperature decrease to about 120 K, the resistivity of thin Fe{sub 3}O{sub 4} films increases up to a peak value and then abruptly drops. This process is attended by a change in the shape of the current-voltage characteristics from the linear at 300 K to the S-type at 80 K. The observed peculiarities are explained by conducting channel switching from the Fe{sub 3}O{sub 4} film to the Si substrate via the field-assisted tunneling of carriers through the composite insulating layer consisting of highly resistive Fe{sub 3}O{sub 4} and tunnel SiO{sub 2}.

Pressure bonding molybdenum alloy (TZM) to reaction-bonded silicon nitride

International Nuclear Information System (INIS)

Huffsmith, S.A.; Landingham, R.L.

1978-01-01

Topping cycles could boost the energy efficiencies of a variety of systems by using what is now waste heat. One such topping cycle uses a ceramic helical expander and would require that a reaction-bonded silicon nitride (RBSN) rotor be bonded to a shaft of TZM (Mo-0.5 wt % Ti-0.08 wt % Zr). Coupon studies show that TZM can be bonded to RBSN at 1300 0 C and 69 MPa if there is an interlayer of MoSi 2 . A layer of finely ground (10 μm) MoSi 2 facilitates bond formation and provides a thicker bond interface. The hardness and grain structure of the TZM and RBSN were not affected by the temperature and pressure required to bond the coupons

Silicon-incorporated diamond-like coatings for Si3N4 mechanical seals

International Nuclear Information System (INIS)

Camargo, S.S.; Gomes, J.R.; Carrapichano, J.M.; Silva, R.F.; Achete, C.A.

2005-01-01

Amorphous silicon carbide (a-SiC) and silicon-incorporated diamond-like carbon films (DLC-Si) were evaluated as protective and friction reduction coatings onto Si 3 N 4 rings. Unlubricated tribological tests were performed with a pin-on-disk apparatus against stainless steel pins with loads ranging from 3 to 55 N and sliding velocities from 0.2 to 1.0 m/s under ambient air and 50-60% relative humidity. At the lowest loads, a-SiC coatings present a considerable improvement with respect to the behavior of uncoated disks since the friction coefficient is reduced to about 0.2 and the system is able to run stably for thousands of meters. At higher loads, however, a-SiC coatings fail. DLC-Si-coated rings, on the other hand, presented for loads up to 10 N a steady-state friction coefficient below 0.1 and very low wear rates. The lowest steady-state mean friction coefficient value of only 0.055 was obtained with a sliding velocity of 0.5 m/s. For higher loads in the range of 20 N, the friction coefficient drops to values around 0.1 but no steady state is reached. For the highest loads of over 50 N, a catastrophic behavior is observed. Typically, wear rates below 5x10 -6 and 2x10 -7 mm 3 /N m were obtained for the ceramic rings and pins, respectively, with a load of 10 N and a sliding velocity of 0.5 m/s. Analysis of the steel pin contact surface by scanning electron microscopy (SEM)-energy dispersive X-ray spectrometry (EDS) and Auger spectroscopy revealed the formation of an adherent tribo-layer mainly composed by Si, C and O. The unique structure of DLC-Si films is thought to be responsible for the formation of the tribo-layer

Plasma spray formed near-net-shape MoSi2-Si3N4 bulk nanocomposites-structure property evaluation

International Nuclear Information System (INIS)

Hong, S.J.; Viswanathan, V.; Rea, K.; Patil, S.; Deshpande, S.; Georgieva, P.; McKechnie, T.; Seal, S.

2005-01-01

This article, for the first time, presents the challenges toward the successful consolidation of near-net-shape bulk MoSi 2 -Si 3 N 4 -SiC nanocomposite using plasma spray forming. A detailed characterization of the spray formed bulk nanocomponent has been performed using optical microscopy (OM), scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), and Vickers hardness testing. Vickers hardness (900 Hv) and fracture toughness (∼>5 MPa m 1/2 ) of the nanocomposite showed a little deviation from the expected, which might be due to the difference in the particle (Si 3 N 4 ) size and their distribution in the MoSi 2 matrix as a function of component thickness. Relatively higher hardness is attributed to the retention of the nanostructure in the composite. In addition, the as fabricated bulk nanocomposite showed enhanced oxidation resistance

Investigation of the fabrication processes of AlGaN/AlN/GaN HEMTs with in situ Si{sub 3}N{sub 4} passivation

Energy Technology Data Exchange (ETDEWEB)

Tomosh, K. N., E-mail: sky77781@mail.ru; Pavlov, A. Yu.; Pavlov, V. Yu.; Khabibullin, R. A.; Arutyunyan, S. S.; Maltsev, P. P. [Russian Academy of Sciences, Institute of Ultra-High-Frequency Semiconductor Electronics (Russian Federation)

2016-10-15

The optimum mode of the in situ plasma-chemical etching of a Si{sub 3}N{sub 4} passivating layer in C{sub 3}F{sub 8}/O{sub 2} medium is chosen for the case of fabricating AlGaN/AlN/GaN HEMTs. It is found that a bias of 40–50 V at a high-frequency electrode provides anisotropic etching of the insulator through a resist mask and introduces no appreciable radiation-induced defects upon overetching of the insulator films in the region of gate-metallization formation. To estimate the effect of in situ Si{sub 3}N{sub 4} growth together with the heterostructure in one process on the AlGaN/AlN/GaN HEMT characteristics, transistors with gates without the insulator and with gates through Si{sub 3}N{sub 4} slits are fabricated. The highest drain current of the AlGaN/AlN/GaN HEMT at 0 V at the gate is shown to be 1.5 times higher in the presence of Si{sub 3}N{sub 4} than without it.

Crystal structure of 2-bromo-3-dimethylamino-N,N,N′,N′,4-pentamethyl-4-(trimethylsilyloxypent-2-eneamidinium bromide

Directory of Open Access Journals (Sweden)

Ioannis Tiritiris

2015-12-01

Full Text Available The reaction of the orthoamide 1,1,1-tris(dimethylamino-4-methyl-4-(trimethylsilyloxypent-2-yne with bromine in benzene, yields the title salt, C15H33BrN3OSi+·Br−. The C—N bond lengths in the amidinium unit are 1.319 (6 and 1.333 (6 Å, indicating double-bond character, pointing towards charge delocalization within the NCN plane. The C—Br bond length of 1.926 (5 Å is characteristic for a C—Br single bond. Additionally, there is a bromine–bromine interaction [3.229 (3 Å] present involving the anion and cation. In the crystal, weak C—H...Br interactions between the methyl H atoms of the cation and the bromide ions are present.

Corrosion behavior of nanostructured Ni-Si{sub 3}N{sub 4} composite films: A study of electrochemical impedance spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Li, J.M.; Cai, C.; Xue, M.Z.; Liu, Y.G. [School of Chemistry and Chemical Technology, Shanghai Jiao Tong University, Shanghai (China); Yin, J.Y.; Zhang, Z. [Department of Chemistry, Zhejiang University, Hangzhou (China); Key Laboratory for Light Alloy Materials Technology, JiaXing (China); Li, J.F. [School of Materials Science and Engineering, Central South University, Changsha (China); Yang, J.F. [State Key Laboratory for Mechanical Behavior of Materials, Xi' an Jiaotong University (China)

2012-07-15

Ni-Si{sub 3}N{sub 4} nanocomposite films with both the consecutive Ni crystallites and dispersed Si{sub 3}N{sub 4} particles in the nanometer range have been fabricated using DC electroplating technique, and characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM), and X-ray diffraction (XRD). The corrosion resistance of the Ni-Si{sub 3}N{sub 4} nanocomposite film has been compared to that of pure Ni coating through polarization. Meanwhile, the corrosion process of Ni-Si{sub 3}N{sub 4} nanocomposite film in neutral 3.5% NaCl solution has been investigated using electrochemical impedance spectroscopy (EIS). The results show that the Ni-Si{sub 3}N{sub 4} nanocomposite film is more resistant to corrosion than the pure Ni coating. The corrosion of Ni-Si{sub 3}N{sub 4} nanocomposite film is controlled by electrochemical step, and the whole corrosion process is divided into two sequential stages. The main corrosion type of Ni-Si{sub 3}N{sub 4} nanocomposite films in neutral 3.5% NaCl solution is pitting. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Fabrication of Si3N4 thin films on phynox alloy substrates for electronic applications

Science.gov (United States)

Shankernath, V.; Naidu, K. Lakshun; Krishna, M. Ghanashyam; Padmanabhan, K. A.

2018-04-01

Thin films of Si3N4 are deposited on Phynox alloy substrates using radio frequency magnetron sputtering. The thickness of the films was varied between 80-150 nm by increasing the duration of deposition from 1 to 3 h at a fixed power density and working pressure. X-ray diffraction patterns reveal that the Si3N4 films had crystallized inspite of the substrates not being heated during deposition. This was confirmed using selected area electron diffraction and high resolution transmission electron microscopy also. It is postulated that a low lattice misfit between Si3N4 and Phynox provides energetically favourable conditions for ambient temperature crystallization. The hardness of the films is of the order of 6 to 9 GPa.

Decreased bacteria activity on Si3N4 surfaces compared with PEEK or titanium

Directory of Open Access Journals (Sweden)

Puckett S

2012-09-01

Full Text Available Deborah Gorth,1 Sabrina Puckett,1 Batur Ercan,1 Thomas J Webster,1 Mohamed Rahaman,2 B Sonny Bal31School of Engineering and Department of Orthopaedics, Brown University, Providence, RI, 2Department of Materials Science and Engineering, Missouri University of Science and Technology, Rolla, MO, 3Department of Orthopaedic Surgery, School of Medicine, University of Missouri, Columbia, MO, USAAbstract: A significant need exists for orthopedic implants that can intrinsically resist bacterial colonization. In this study, three biomaterials that are used in spinal implants – titanium (Ti, poly-ether-ether-ketone (PEEK, and silicon nitride (Si3N4 – were tested to understand their respective susceptibility to bacterial infection with Staphylococcus epidermidis, Staphlococcus aureus, Pseudomonas aeruginosa, Escherichia coli and Enterococcus. Specifically, the surface chemistry, wettability, and nanostructured topography of respective biomaterials, and the effects on bacterial biofilm formation, colonization, and growth were investigated. Ti and PEEK were received with as-machined surfaces; both materials are hydrophobic, with net negative surface charges. Two surface finishes of Si3N4 were examined: as-fired and polished. In contrast to Ti and PEEK, the surface of Si3N4 is hydrophilic, with a net positive charge. A decreased biofilm formation was found, as well as fewer live bacteria on both the as-fired and polished Si3N4. These differences may reflect differential surface chemistry and surface nanostructure properties between the biomaterials tested. Because protein adsorption on material surfaces affects bacterial adhesion, the adsorption of fibronectin, vitronectin, and laminin on Ti, PEEK, and Si3N4 were also examined. Significantly greater amounts of these proteins adhered to Si3N4 than to Ti or PEEK. The findings of this study suggest that surface properties of biomaterials lead to differential adsorption of physiologic proteins, and that this

Centrosymmetric [N(CH3)4]2TiF6 vs. noncentrosymmetric polar [C(NH2)3]2TiF6: A hydrogen-bonding effect on the out-of-center distortion of TiF6 octahedra

International Nuclear Information System (INIS)

Kim, Eun-ah; Lee, Dong Woo; Ok, Kang Min

2012-01-01

The syntheses, structures, and characterization of organically templated zero-dimensional titanium fluoride materials, A 2 TiF 6 (A=[N(CH 3 ) 4 ] or [C(NH 2 ) 3 ]), are reported. Phase pure samples of A 2 TiF 6 were synthesized by either solvothermal reaction method or a simple mixing method. While [N(CH 3 ) 4 ] 2 TiF 6 crystallizes in a centrosymmetric space group, R-3, [C(NH 2 ) 3 ] 2 TiF 6 crystallizes in a noncentrosymmetric polar space group, Cm. The asymmetric out-of-center distortion of TiF 6 octahedra in polar [C(NH 2 ) 3 ] 2 TiF 6 are attributable to the hydrogen-bonding interactions between the fluorine atoms in TiF 6 octahedra and the nitrogen atoms in the [C(NH 2 ) 3 ] + cation. Powder second-harmonic generation (SHG) measurements on the [C(NH 2 ) 3 ] 2 TiF 6 , using 1064 nm radiation, indicate the material has SHG efficiency of 25× that of α-SiO 2 , which indicates an average nonlinear optical susceptibility, 〈d eff 〉 exp of 2.8 pm/V. Additional SHG measurements reveal that the material is not phase-matchable (Type 1). The magnitudes of out-of-center distortions and dipole moment calculations for TiF 6 octahedra will be also reported. - Graphical abstract: The out-of-center distortion of TiF 6 octahedron in the polar noncentrosymmetric [C(NH 2 ) 3 ] 2 TiF 6 is attributable to the hydrogen-bonding interactions between the F in TiF 6 octahedron and the H–N in the [C(NH 2 ) 3 ] + . Highlights: ► Two titanium fluorides materials have been synthesized in high yields. ► Hydrogen-bonds are crucial for the out-of-center distortion of TiF 6 octahedra. ► [C(NH 2 ) 3 ] 2 TiF 6 has a SHG efficiency of 25× that of α-SiO 2 .

Interface reactions in the Al-Si-SiC and Mg-Al-Al{sub 2}O{sub 3} composite systems

Energy Technology Data Exchange (ETDEWEB)

Johnson, P.K. [Commission of the European Communities, Petten (Netherlands). Inst. for Advanced Materials; Fazal-Ur-Rehman [Imperial Coll. of Science, Technology and Medicine, London (United Kingdom). Dept. of Materials; Fox, S. [Imperial Coll. of Science, Technology and Medicine, London (United Kingdom). Dept. of Materials; Flower, H.M. [Imperial Coll. of Science, Technology and Medicine, London (United Kingdom). Dept. of Materials; West, D.R.F.

1995-12-31

Structural and compositional observations are reported on the influence of the interfaces on the mechanisms and kinetics of liquid metal-ceramic reactions in Al-SiC, Al-Si-SiC, Mg-Al{sub 2}O{sub 3} and Mg-Al-Al{sub 2}O{sub 3} composites. The aluminium based materials contained up to 20 vol% SiC in particulate form, and were produced by a spray casting process; subsequently the interface reactions were studied in samples heated to temperatures up to 1100 C. The reaction product was Al{sub 4}C{sub 3} in both Al-SiC and Al-Si-SiC composites. The influence of the crystallography and topology of the SiC particle surfaces on the nucleation of the Al{sub 4}C{sub 3} has been demonstrated; surface asperities play an important role. Growth of nuclei proceeds to form continuous reaction product layers which control the subsequent kinetics. The magnesium based composites contained 5 vol% Al{sub 2}O{sub 3} fibres (3 {mu}m in diameter), and were produced by a liquid infiltration process. SD Safimax fibres with relatively low and high porosity, and also RF Saffil fibres, with a silica binder, were investigated. Fibre porosity plays a major role in accelerating the penetration of Mg into the fibres with reaction to form MgO. Silica binder on the fibre surface transforms to MgO. The reaction rate was reduced by the presence of aluminium in the matrix. The factors controlling the reactions in the aluminium and magnesium based composites are compared. (orig.)

Microstructure and properties of thick nanocomposite TiN/Si{sub 3}N{sub 4} coatings on Vanadis 23 HS steel

Energy Technology Data Exchange (ETDEWEB)

Moskalewicz, Tomasz; Czyrska-Filemonowicz, Aleksandra [AGH Univ. of Science and Technology, Faculty of Metals Engineering and Industrial Computer Science, Krakow (Poland); Zimowski, Slawomir [AGH Univ. of Science and Technology, Faculty of Mechanical Engineering and Robotics, Krakow (Poland); Wendler, Bogdan; Progalskiy, Ivan [Lodz Univ. of Technology (Poland). Inst. of Materials Science and Engineering

2015-07-15

The microstructure and selected micro-mechanical properties of a 13.4 μm thick nanocomposite TiN/Si{sub 3}N{sub 4} coating deposited onto Vanadis 23 HS steel by a new gas pulsed magnetron sputtering technique were investigated. Scanning and transmission electron microscopy were employed to investigate the detailed microstructure of the coating. It was found that the coating exhibited a fully nanocrystalline structure and was composed of two zones: the outer zone with columnar structure and the inner one with equiaxed, fine columnar structure. Both zones consisted mainly of the δ-TiN nanocrystallites with a small amount of α-Si{sub 3}N{sub 4} and β-Si{sub 3}N{sub 4}. In order to increase coating adhesion to the substrate, a graded intermediate layer consisting of three different phases (pure Cr, CrN and Cr2N) was applied. The hardness of the as-deposited TiN/Si{sub 3}N{sub 4} coating was equal to 48 GPa, whereas it was equal to 40 GPa after annealing. The coatings exhibited very good adhesion to the underlying steel substrate.

Simple Lanthanide Amides [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3 as Highly Efficient Catalysts for the Nitroaldol Reaction

Institute of Scientific and Technical Information of China (English)

LIU,Yu-yu; WANG,Shao-Wu; ZHANG,Li-Jun; WU,Yun-Jun; LI,Qing-Hai; YANG,Gao-Sheng; XIE,Mei-Hua

2008-01-01

This contribution is to report the application of simple lanthanide amides [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3 exhib-iting a high activity toward catalyzing Henry reaction of aromatic aldehydes with nitroalkanes to give β-nitroalcohols or β-nitroolefins with a very good chemoselectivity by controlling the reaction temperatures and by selecting aromatic aldehydes. It was found that this catalytic system was compatible with a wide range of substrates of aldehydes.

Luminescent Properties of Sr4Si3O8Cl4:Eu2+, Bi3+ Phosphors for Near UV InGaN-Based Light-Emitting-Diodes

Directory of Open Access Journals (Sweden)

Wangqing Shen

2015-12-01

Full Text Available Sr4Si3O8Cl4 co-doped with Eu2+, Bi3+ were prepared by the high temperature reaction. The structure and luminescent properties of Sr4Si3O8Cl4:Eu2+, Bi3+ were investigated. With the introduction of Bi3+, luminescent properties of these phosphors have been optimized. Compared with Sr3.90Si3O8Cl4:0.10Eu2+, the blue-green phosphor Sr3.50Si3O8Cl4:0.10Eu2+, 0.40Bi3+ shows stronger blue-green emission with broader excitation in near-UV range. Bright blue-green light from the LED means this phosphor can be observed by the naked eye. Hence, it may have an application in near UV LED chips.

Mechanical Properties and Thermal Shock Resistance Analysis of BNNT/Si3N4 Composites

Science.gov (United States)

Wang, Shouren; Wang, Gaoqi; Wen, Daosheng; Yang, Xuefeng; Yang, Liying; Guo, Peiquan

2018-04-01

BNNT/Si3N4 ceramic composites with different weight amount of BNNT fabricated by hot isostatic pressing were introduced. The mechanical properties and thermal shock resistance of the composites were investigated. The results showed that BNNT-added ceramic composites have a finer and more uniform microstructure than that of BNNT-free Si3N4 ceramic because of the retarding effect of BNNT on Si3N4 grain growth. The addition of 1.5 wt.% BNNT results in simultaneous increase in flexural strength, fracture toughness, and thermal shock resistance. The analysis of the results indicates that BNNT brings many thermal transport channels in the microstructure, increasing the efficiency of thermal transport, therefore results in increase of thermal shock resistance. In addition, BNNT improves the residual flexural strength of composites by crack deflection, bridging, branching and pinning, which increase the crack propagation resistance.

Gibbs free energy of reactions involving SiC, Si3N4, H2, and H2O as a function of temperature and pressure

Science.gov (United States)

Isham, M. A.

1992-01-01

Silicon carbide and silicon nitride are considered for application as structural materials and coating in advanced propulsion systems including nuclear thermal. Three-dimensional Gibbs free energy were constructed for reactions involving these materials in H2 and H2/H2O. Free energy plots are functions of temperature and pressure. Calculations used the definition of Gibbs free energy where the spontaneity of reactions is calculated as a function of temperature and pressure. Silicon carbide decomposes to Si and CH4 in pure H2 and forms a SiO2 scale in a wet atmosphere. Silicon nitride remains stable under all conditions. There was no apparent difference in reaction thermodynamics between ideal and Van der Waals treatment of gaseous species.

Influence of Si ion implantation on structure and morphology of g-C{sub 3}N{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Varalakshmi, B.; Sreenivasulu, K.V. [School of Engineering Sciences and Technology (SEST), University of Hyderabad, Hyderabad 500046 (India); Asokan, K. [Inter University Accelerator Centre (IUAC), Aruna Asaf Ali Marg, Near Vasant Kunj, New Delhi 110067 (India); Srikanth, V.V.S.S., E-mail: vvsssse@uohyd.ernet.in [School of Engineering Sciences and Technology (SEST), University of Hyderabad, Hyderabad 500046 (India)

2016-07-15

Effect of Si ion implantation on structural and morphological features of graphite-like carbon nitride (g-C{sub 3}N{sub 4}) was investigated. g-C{sub 3}N{sub 4} was prepared by using a simple atmospheric thermal decomposition process. The g-C{sub 3}N{sub 4} pellets were irradiated with a Si ion beam of energy 200 keV with different fluencies. Structural, morphological and elemental, and phase analysis of the implanted samples in comparison with the pristine samples was carried out by using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) with energy dispersive spectroscopy (EDS) and Fourier transform infrared spectroscopy (FTIR) techniques, respectively. The observations revealed that Si ion implantation results in a negligible change in the crystallite size and alteration of the network-like to the sheet-like morphology of g-C{sub 3}N{sub 4} and Si ions in the g-C{sub 3}N{sub 4} network.

Gold-coated iron nanoparticles in transparent Si3N4 matrix thin films

Science.gov (United States)

Sánchez-Marcos, J.; Céspedes, E.; Jiménez-Villacorta, F.; Muñoz-Martín, A.; Prieto, C.

2013-06-01

A new method to prepare thin films containing gold-coated iron nanoparticles is presented. The ternary Fe-Au-Si3N4 system prepared by sequential sputtering has revealed a progressive variation of microstructures from Au/Fe/Au/Si3N4 multilayers to iron nanoparticles. Microstructural characterization by transmission electron microscopy, analysis of the magnetic properties and probing of the iron short-range order by X-ray absorption spectroscopy confirm the existence of a gold-coated iron nanoparticles of 1-2 nm typical size for a specific range of iron and gold contents per layer in the transparent silicon nitride ceramic matrix.

Investigation based on nano-electromechanical system double Si3N4 resonant beam pressure sensor.

Science.gov (United States)

Yang, Chuan; Guo, Can; Yuan, Xiaowei

2011-12-01

This paper presents a type of NEMS (Nano-Electromechanical System) double Si3N4 resonant beams pressure sensor. The mathematical models are established in allusion to the Si3N4 resonant beams and pressure sensitive diaphragm. The distribution state of stress has been analyzed theoretically based on the mathematical model of pressure sensitive diaphragm; from the analysis result, the position of the Si3N4 resonant beams above the pressure sensitive diaphragm was optimized and then the dominance observed after the double resonant beams are adopted is illustrated. From the analysis result, the position of the Si3N4 resonant beams above the pressure sensitive diaphragm is optimized, illustrating advantages in the adoption of double resonant beams. The capability of the optimized sensor was generally analyzed using the ANSYS software of finite element analysis. The range of measured pressure is 0-400 Kpa, the coefficient of linearity correlation is 0.99346, and the sensitivity of the sensor is 498.24 Hz/Kpa, higher than the traditional sensors. Finally the processing techniques of the sensor chip have been designed with sample being successfully processed.

Magnetic SiO2/Fe3O4 colloidal crystals

International Nuclear Information System (INIS)

Huang, C-K; Hou, C-H; Chen, C-C; Tsai, Y-L; Chang, L-M; Wei, H-S; Hsieh, K-H; Chan, C-H

2008-01-01

We proposed a novel technique to fabricate colloidal crystals by using monodisperse SiO 2 coated magnetic Fe 3 O 4 (SiO 2 /Fe 3 O 4 ) microspheres. The magnetic SiO 2 /Fe 3 O 4 microspheres with a diameter of 700 nm were synthesized in the basic condition with ferric sulfate, ferrous sulfate, tartaric acid and tetraethyl orthosilicate (TEOS) in the reaction system. Monodisperse SiO 2 /Fe 3 O 4 superparamagnetic microspheres have been successfully used to fabricate colloidal crystals under the existing magnetic field

Experimental investigation of the reactions 25Mg(α,n)28Si, 26Mg(α,n)29Si, 18O(α,n)21Ne and their impact on stellar nucleosynthesis

International Nuclear Information System (INIS)

Falahat, Sascha

2010-01-01

In the present dissertation, the nuclear reactions 25 Mg(α,n) 28 Si, 26 Mg(α,n) 29 Si, 18 O(α,n) 21 Ne are investigated in the astrophysically interesting energy region from E α =1000 keV to E α =2450 keV. The experiments were performed at the Nuclear Structure Laboratory of the University of Notre Dame (USA) with the Van-de-Graaff accelerator KN. Solid state targets with evaporated magnesium or anodized oxygen were bombarded with α-particles and the released neutrons detected. For the detection of the released neutrons, computational simulations were used to construct a neutron detector based on 3 He counters. Because of the strong occurrence of background reactions, different methods of data analysis were employed. Finally, the impact of the reactions 25 Mg(α,n) 28 Si, 26 Mg(α,n) 29 Si, 18 O(α,n) 21 Ne on stellar nucleosynthesis is investigated by means of network calculations. (orig.)

Electronic Structure and Chemical Bond of Ti3SiC2 and Adding Al Element

Institute of Scientific and Technical Information of China (English)

MIN Xinmin; LU Ning; MEI Bingchu

2006-01-01

The relation among electronic structure, chemical bond and property of Ti3SiC2 and Al-doped was studied by density function and discrete variation (DFT-DVM) method. When Al element is added into Ti3SiC2, there is a less difference of ionic bond, which does not play a leading role to influent the properties. After adding Al, the covalent bond of Al and the near Ti becomes somewhat weaker, but the covalent bond of Al and the Si in the same layer is obviously stronger than that of Si and Si before adding. Therefore, in preparation of Ti3SiC2, adding a proper quantity of Al can promote the formation of Ti3SiC2. The density of state shows that there is a mixed conductor character in both of Ti3SiC2 and adding Al element. Ti3SiC2 is with more tendencies to form a semiconductor. The total density of state near Fermi lever after adding Al is larger than that before adding, so the electric conductivity may increase after adding Al.

N2O + CO reaction over Si- and Se-doped graphenes: An ab initio DFT study

International Nuclear Information System (INIS)

Gholizadeh, Reza; Yu, Yang-Xin

2015-01-01

Graphical abstract: Si-doped graphene can be one of efficient green catalysts for conversion of the airborne pollutants. - Highlights: • N 2 O can be efficiently reduced by CO over Si-doped graphenes. • Enough charge transferred from Si to N 2 O makes the N 2 –O bond break easily. • Si-doped graphene is efficient green catalysts for conversion of the airborne pollutants. • vdW interaction and ZPE energy significantly influence the predictions of activation energies. - Abstract: Catalytic conversion of non-CO 2 green house gases and other harmful gases is a promising way to protect the atmospheric environment. Non-metal atom-doped graphene is attractive for use as a catalyst in the conversion due to its unique electronic properties, relatively low price and leaving no burden to the environment. To make an attempt on the development of green catalysts for the conversion, ab initio density functional theory is used to investigate the mechanisms of N 2 O reduction by CO on Si- and Se-doped graphenes. We have calculated the geometries and adsorption energies of reaction species (N 2 O, CO, N 2 and CO 2 ) as well as energy profiles along the reaction pathways. The activation energies of N 2 O decomposition and CO oxidation on both Si- and Se-doped graphenes have been obtained. Our calculated results indicate that the catalytic activity of Si-doped graphene is better than the Fe + in gas phase and comparable to the single Fe atom embedded on graphene. In the calculations, we found that van der Waals interactions and zero-point energy are two non-negligible factors for the predictions of the activation energies. Further discussion shows that Si-doped graphene can be one of efficient green catalysts for conversion of the airborne pollutants and Se-doped graphene can be a candidate for oxidizing CO by atomic oxygen.

Thermal stability and chemical bonding states of AlOxNy/Si gate stacks revealed by synchrotron radiation photoemission spectroscopy

International Nuclear Information System (INIS)

He, G.; Toyoda, S.; Shimogaki, Y.; Oshima, M.

2010-01-01

Annealing-temperature dependence of the thermal stability and chemical bonding states of AlO x N y /SiO 2 /Si gate stacks grown by metalorganic chemical vapor deposition (MOCVD) using new chemistry was investigated by synchrotron radiation photoemission spectroscopy (SRPES). Results have confirmed the formation of the AlN and AlNO compounds in the as-deposited samples. Annealing the AlO x N y samples in N 2 ambient in 600-800 deg. C promotes the formation of SiO 2 component. Meanwhile, there is no formation of Al-O-Si and Al-Si binding states, suggesting no interdiffusion of Al with the Si substrate. A thermally induced reaction between Si and AlO x N y to form volatile SiO and Al 2 O is suggested to be responsible for the full disappearance of the Al component that accompanies annealing at annealing temperature of 1000 deg. C. The released N due to the breakage of the Al-N bonding will react with the SiO 2 interfacial layer and lead to the formation of the Si 3 -N-O/Si 2 -N-O components at the top of Si substrate. These results indicate high temperature processing induced evolution of the interfacial chemistry and application range of AlO x N y /Si gate stacks in future CMOS devices.

In situ synthesis and properties of self-reinforced Si3N4–SiO2 ...

Indian Academy of Sciences (India)

reinforced glass–ceramic composites were obtained without any β -Si 3 N 4 seed crystal. These composites with different compositions were prepared in a nitrogenatmosphere for comparison of phase transformation and mechanical properties.

Al-Si/B{sub 4}C composite coatings on Al-Si substrate by plasma spray technique

Energy Technology Data Exchange (ETDEWEB)

Sarikaya, Ozkan [Sakarya University, Faculty of Engineering, Department of Mechanical Engineering, Esentepe Campus, Sakarya 54187 (Turkey); Anik, Selahaddin [Sakarya University, Faculty of Engineering, Department of Mechanical Engineering, Esentepe Campus, Sakarya 54187 (Turkey); Aslanlar, Salim [Sakarya University, Faculty of Technical Education, Department of Mechanical Engineering, Esentepe Campus, Sakarya 54187 (Turkey); Cem Okumus, S. [Sakarya University, Faculty of Engineering, Department of Metallurgical and Materials Engineering, Esentepe Campus, Sakarya 54187 (Turkey); Celik, Erdal [Dokuz Eylul University, Engineering Faculty, Department of Metallurgical and Materials Engineering, Buca, Izmir 35160 (Turkey)]. E-mail: erdal.celik@deu.edu.tr

2007-07-01

Plasma-sprayed coatings of Al-Si/B{sub 4}C have been prepared on Al-Si piston alloys for diesel engine motors. The Al-Si/B{sub 4}C composite powders including 5-25 wt% B{sub 4}C were prepared by mixing and ball-milling processes. These powders were deposited on Al-Si substrate using an atmospheric plasma spray technique. The coatings have been characterised with respect to phase composition, microstructure, microhardness, bond strength and thermal expansion. It was found that Al, Si, B{sub 4}C and Al{sub 2}O{sub 3} phases were determined in the coatings with approximately 600 {mu}m thick by using X-ray diffraction analysis. Scanning electron microscope observation revealed that boron carbide particles were uniformly distributed in composite coatings and B{sub 4}C particles were fully wetted by Al-Si alloy. Also, no reaction products were observed in Al-Si/B{sub 4}C composite coatings. It was found that surface roughness, porosity, bond strength and thermal expansion coefficient of composite coatings decreased with increasing fraction of the boron carbide particle. It was demonstrated that the higher the B{sub 4}C content, the higher the hardness of coatings because the hardness of B{sub 4}C is higher than that of Al-Si.

Synthesis of the (N2)3- radical from Y2+ and its protonolysis reactivity to form (N2H2)2- via the Y[N(SiMe3)2]3/KC8 reduction system.

Science.gov (United States)

Fang, Ming; Lee, David S; Ziller, Joseph W; Doedens, Robert J; Bates, Jefferson E; Furche, Filipp; Evans, William J

2011-03-23

Examination of the Y[N(SiMe(3))(2)](3)/KC(8) reduction system that allowed isolation of the (N(2))(3-) radical has led to the first evidence of Y(2+) in solution. The deep-blue solutions obtained from Y[N(SiMe(3))(2)](3) and KC(8) in THF at -35 °C under argon have EPR spectra containing a doublet at g(iso) = 1.976 with a 110 G hyperfine coupling constant. The solutions react with N(2) to generate (N(2))(2-) and (N(2))(3-) complexes {[(Me(3)Si)(2)N](2)(THF)Y}(2)(μ-η(2):η(2)-N(2)) (1) and {[(Me(3)Si)(2)N](2)(THF)Y}(2)(μ-η(2):η(2)-N(2))[K(THF)(6)] (2), respectively, and demonstrate that the Y[N(SiMe(3))(2)](3)/KC(8) reaction can proceed through an Y(2+) intermediate. The reactivity of (N(2))(3-) radical with proton sources was probed for the first time for comparison with the (N(2))(2-) and (N(2))(4-) chemistry. Complex 2 reacts with [Et(3)NH][BPh(4)] to form {[(Me(3)Si)(2)N](2)(THF)Y}(2)(μ-N(2)H(2)), the first lanthanide (N(2)H(2))(2-) complex derived from dinitrogen, as well as 1 as a byproduct, consistent with radical disproportionation reactivity.

Surface texturing of Si3N4–SiC ceramic tool components by pulsed laser machining

CSIR Research Space (South Africa)

Tshabalala, LC

2016-03-01

Full Text Available texturing of Si(sub3)N(sub4)–SiC composites in the fabrication of machining tool inserts for various tribological applications. The samples were machined at varied laser energy (0.1–0.6 mJ) and lateral pulse overlap (50–88%) in order to generate a sequence...

Development and characterisation of Ni-Si3N4 nanocomposites

International Nuclear Information System (INIS)

R, Mohan Reddy; M, Praveen B.; M, Praveen C.; V, Venkatesha T.; Kumar N B, Rithin

2015-01-01

Nickel–Si 3 N 4 composites were generated by means of pulse-reverse (PR) electrodeposition technique. The corrosion rate was calculated for the composites by electrochemical methods such as polarisation and impedance methods. Composites were characterised by scanning electron microscope (SEM) and X-ray diffractometer (XRD) to evaluate their microstructures. Coatings obtained by PR method shows more corrosion resistance than DC generated coatings

Influence of H on the composition and atomic concentrations of 'N-rich' plasma deposited SiOxNyHz films

International Nuclear Information System (INIS)

Prado, A. del; San Andres, E.; Martil, I.; Gonzalez-Diaz, G.; Bohne, W.; Roehrich, J.; Selle, B.

2004-01-01

The influence of H on the composition and atomic concentrations of Si, O, and N of plasma deposited SiO x N y H z films was investigated. The bonding scheme of H was analyzed by Fourier-transform infrared spectroscopy. The composition and absolute concentrations of all the species present in the SiO x N y H z , including H, was measured by heavy-ion elastic recoil detection analysis (HI-ERDA). Samples were deposited from SiH 4 , O 2 , and N 2 gas mixtures, with different gas flow ratios in order to obtain compositions ranging from SiN y H z to SiO 2 . Those samples deposited at higher SiH 4 partial pressures show both Si-H and N-H bonds, while those deposited at lower SiH 4 partial pressures show N-H bonds only. The Si-H and N-H bond concentrations were found to be proportional to the N concentration. The concentration of H was evaluated from the Si-H and N-H stretching absorption bands and compared to the HI-ERDA results, finding good agreement between both measurements. The deviation from H-free stoichiometric SiO x N y composition due to the presence of N-H bonds results in an effective coordination number of N to produce Si-N bonds lower than 3. By fitting the experimental composition data to a theoretical model taking into account the influence of N-H bonds, the actual concentration of N-H bonds was obtained, making evident the presence of nonbonded H. The presence of Si-H and Si-Si bonds was found to partially compensate the effect of N-H bonds, from the point of view of the relative N and Si contents. Finally, the presence of N-H bonds results in a lower Si atom concentration with respect to the stoichiometric film, due to a replacement of Si atoms by H atoms. This decrease of the Si concentration is lower in those films containing Si-H and Si-Si bonds. A model was developed to calculate the Si, O, and N atom concentrations taking into account the influence of N-H, Si-H, and Si-Si bonds, and was found to be in perfect agreement with the experimental data

Temperature-Dependent Electrical Characteristics of Au/Si3N4/4H n-SiC MIS Diode

Science.gov (United States)

Yigiterol, F.; Güllü, H. H.; Bayraklı, Ö.; Yıldız, D. E.

2018-03-01

Electrical characteristics of the Au/Si3N4/4H n-SiC metal-insulator-semiconductor (MIS) diode were investigated under the temperature, T , interval of 160-400 K using current-voltage (I-V), capacitance-voltage ( C {-} V ) and conductance-voltage ( G/ω {-} V ) measurements. Firstly, the Schottky diode parameters as zero-bias barrier height ( Φ_{B0} ) and ideality factor ( n ) were calculated according to the thermionic emission (TE) from forward bias I-V analysis in the whole working T . Experimental results showed that the values of Φ_{B0} were in increasing behavior with increasing T while n values decreased with inverse proportionality in n versus Φ_{{{{B}}0}} plot. Therefore, the non-ideal I-V behavior with inhomogeneous barrier height (BH) formation has been discussed under the assumption of Gaussian distribution (GD). From the GD of BHs, the mean BH was found to be about 1.40 eV with 0.1697 standard deviation and the modified Richardson constant A^{*} of this diode was obtained as 141.65 A/cm2 K2 in good agreement with the literature (the theoretical value of A^{*} is 137.21 A/cm2 K2). The relationship between Φ_{B0} and n showed an abnormal I-V behavior depending on T , and it was modeled by TE theory with GD of BH due to the effect in inhomogeneous BH at the interface. Secondly, according to Cheung's model, series resistance, R_{{S}} values were calculated in the T range of 160-400 K and these values were found to decrease with increasing T . Finally, the density of interface states, D_{{it}} was calculated and the T dependence of energy distribution of D_{{it}} profiles determined the forward I {-} V measurements by taking into account the bias dependence of the effective BH, Φ_{{e}} and n . D_{{it}} were also calculated according to the Hill-Coleman method from C {-} V and G/ω {-} V analysis. Furthermore, the variation of D_{{it}} as a function of frequency, f and T were determined.

Development and characterization of Si3N4 coated AlCrN ceramic cutting tool

International Nuclear Information System (INIS)

Souza, J.V.C.; Nono, M.C.A.; Martins, G.V.; Machado, J.P.B.; Silva, O.M.M.

2009-01-01

Nowadays, silicon nitride based cutting tools are used to machine cast iron from the automotive industry and nickel superalloys from the aero industries. Advances in manufacturing technologies (increased cutting speeds, dry machining, etc.) induced the fast commercial growth of physical vapor deposition (PVD) coatings for cutting tools, in order to increase their life time. In this work, a new composition of the Si 3 N 4 ceramic cutting tool was developed, characterized and subsequently coated, using a PVD process, with aluminum chromium nitride (AlCrN). The Si 3 N 4 substrate properties were analyzed by XRD, AFM, hardness and fracture toughness. The AlCrN coating was analyzed by AFM, grazing incidence X-ray diffraction (GIXRD) and hardness. The results showed that this PVD coating could be formed homogeneously, without cracks and promoted a higher surface hardness to the insert and consequently it can produce a better wear resistance during its application on high speed machining. (author)

Ge nanocrystals embedded in ultrathin Si3N4 multilayers with SiO2 barriers

Science.gov (United States)

Bahariqushchi, R.; Gundogdu, Sinan; Aydinli, A.

2017-04-01

Multilayers of germanium nanocrystals (NCs) embedded in thin films of silicon nitride matrix separated with SiO2 barriers have been fabricated using plasma enhanced chemical vapor deposition (PECVD). SiGeN/SiO2 alternating bilayers have been grown on quartz and Si substrates followed by post annealing in Ar ambient from 600 to 900 °C. High resolution transmission electron microscopy (HRTEM) as well as Raman spectroscopy show good crystallinity of Ge confined to SiGeN layers in samples annealed at 900 °C. Strong compressive stress for SiGeN/SiO2 structures were observed through Raman spectroscopy. Size, as well as NC-NC distance were controlled along the growth direction for multilayer samples by varying the thickness of bilayers. Visible photoluminescence (PL) at 2.3 and 3.1 eV with NC size dependent intensity is observed and possible origin of PL is discussed.

Synthesis of 1,2,4-Triazoles via Oxidative Heterocyclization: Selective C-N Bond Over C-S Bond Formation.

Science.gov (United States)

Gogoi, Anupal; Guin, Srimanta; Rajamanickam, Suresh; Rout, Saroj Kumar; Patel, Bhisma K

2015-09-18

The higher propensity of C-N over C-S bond forming ability was demonstrated, through formal C-H functionalization during the construction of 4,5-disubstituted 1,2,4-triazole-3-thiones from arylidenearylthiosemicarbazides catalyzed by Cu(II). However, steric factors imparted by the o-disubstituted substrates tend to change the reaction path giving thiodiazole as the major or an exclusive product. Upon prolonging the reaction time, the in situ generated thiones are transformed to 4,5-disubstituted 1,2,4-triazoles via a desulfurization process. Two classes of heterocycles viz. 4,5-disubstituted 1,2,4-triazole-3-thiones and 4,5-disubstituted 1,2,4-triazoles can be synthesized from arylidenearylthiosemicarbazides by simply adjusting the reaction time. Desulfurization of 1,2,4-triazole-3-thiones is assisted by thiophilic Cu to provide 1,2,4-triazoles with concomitant formation of CuS and polynuclear sulfur anions as confirmed from scanning electron microscope and energy dispersive X-ray spectroscopy measurements. A one-pot synthesis of an antimicrobial compound has been successfully achieved following this strategy.

First-principles quantum molecular calculations of structural and mechanical properties of TiN/SiN{sub x} heterostructures, and the achievable hardness of the nc-TiN/SiN{sub x} nanocomposites

Energy Technology Data Exchange (ETDEWEB)

Ivashchenko, V.I., E-mail: ivash@ipms.kiev.ua [Institute of Problems of Material Science, National Academy of Science of Ukraine, Krzhyzhanosky Str. 3, 03142 Kyiv (Ukraine); Veprek, S., E-mail: stan.veprek@lrz.tum.de [Department of Chemistry, Technical University Munich, Lichtenbergstrasse 4, D-85747 Garching (Germany); Argon, A.S. [Department of Mechanical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139 (United States); Turchi, P.E.A. [Lawrence Livermore National Laboratory (L-352), P.O. Box 808, Livermore, CA 94551 (United States); Gorb, L. [Badger Technical Services, LLC, Vicksburg, MS 39180 (United States); U.S. Army ERDC, Vicksburg, MS 39180 (United States); Hill, F. [U.S. Army ERDC, Vicksburg, MS 39180 (United States); Leszczynski, J. [Department of Chemistry and Biochemistry, Interdisciplinary Center for Nanotoxicity, Jackson State University, Jackson, MS 39217 (United States)

2015-03-02

TiN/SiN{sub x} heterostructures with one monolayer of the interfacial SiN{sub x} have been investigated in the framework of first-principles molecular dynamics calculations in the temperature range of 0 to 1400 K with subsequent static relaxation. The atomic configurations, thermal stability and stress–strain relations have been calculated. Among the heterostructures studied, only the TiN(111)/SiN/TiN(111) and TiN(111)/Si{sub 2}N{sub 3}/TiN(111) ones are thermally stable. Upon tensile load, decohesion occurs between the Ti−N bonds adjacent to the SiN{sub x} interfacial layer for TiN(001)/SiN/TiN(001) and TiN(111)/Si{sub 2}N{sub 3}/TiN(111) heterostructures, and inside the TiN slab for TiN(001)/Si{sub 3}N{sub 4}/TiN(001) and TiN(110)/SiN/TiN(110) ones. Upon shear, failure occurs in TiN near the interfaces in all the heterostructures, except for the TiN(001)/Si{sub 3}N{sub 4}/TiN(001) one, for which the plastic flow occurs inside the TiN slab. Based on these results we estimate the maximum achievable hardness of nc-TiN/Si{sub 3}N{sub 4} nanocomposites free of impurities to be about 170 GPa. - Highlights: • Interface stability in TiN/SiN{sub x} heterostructures at T ≤ 1400 K is studied by quantum molecular dynamics. • Ideal decohesion and shear strengths of the heterostructures have been calculated. • Achievable hardness of nc-TiN/Si{sub 3}N{sub 4}-like nanocomposites of about 170 GPa is calculated. • Experimentally achieved lower hardness is limited by flaws, such as oxygen impurities.

Exploring the Nature of Silicon-Noble Gas Bonds in H3SiNgNSi and HSiNgNSi Compounds (Ng = Xe, Rn

Directory of Open Access Journals (Sweden)

Sudip Pan

2015-03-01

Full Text Available Ab initio and density functional theory-based computations are performed to investigate the structure and stability of H3SiNgNSi and HSiNgNSi compounds (Ng = Xe, Rn. They are thermochemically unstable with respect to the dissociation channel producing Ng and H3SiNSi or HSiNSi. However, they are kinetically stable with respect to this dissociation channel having activation free energy barriers of 19.3 and 23.3 kcal/mol for H3SiXeNSi and H3SiRnNSi, respectively, and 9.2 and 12.8 kcal/mol for HSiXeNSi and HSiRnNSi, respectively. The rest of the possible dissociation channels are endergonic in nature at room temperature for Rn analogues. However, one three-body dissociation channel for H3SiXeNSi and one two-body and one three-body dissociation channels for HSiXeNSi are slightly exergonic in nature at room temperature. They become endergonic at slightly lower temperature. The nature of bonding between Ng and Si/N is analyzed by natural bond order, electron density and energy decomposition analyses. Natural population analysis indicates that they could be best represented as (H3SiNg+(NSi− and (HSiNg+(NSi−. Energy decomposition analysis further reveals that the contribution from the orbital term (ΔEorb is dominant (ca. 67%–75% towards the total attraction energy associated with the Si-Ng bond, whereas the electrostatic term (ΔEelstat contributes the maximum (ca. 66%–68% for the same in the Ng–N bond, implying the covalent nature of the former bond and the ionic nature of the latter.

Rare-earth element doped Si3N4/SiC micro/nano-composites-RT and HT mechanical properties

Czech Academy of Sciences Publication Activity Database

Lojanová, Š.; Tatarko, P.; Chlup, Zdeněk; Hnatko, M.; Dusza, J.; Lenčéš, Z.; Šajgalík, P.

2010-01-01

Roč. 30, č. 9 (2010), s. 1931-1944 ISSN 0955-2219 Institutional research plan: CEZ:AV0Z20410507 Keywords : Si3N4 * SiC * Nano-composites * Fracture toughness * Hardness * Strength * Creep Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass Impact factor: 2.574, year: 2010

C and Si delta doping in Ge by CH_3SiH_3 using reduced pressure chemical vapor deposition

International Nuclear Information System (INIS)

Yamamoto, Yuji; Ueno, Naofumi; Sakuraba, Masao; Murota, Junichi; Mai, Andreas; Tillack, Bernd

2016-01-01

C and Si delta doping in Ge are investigated using a reduced pressure chemical vapor deposition system to establish atomic-order controlled processes. CH_3SiH_3 is exposed at 250 °C to 500 °C to a Ge on Si (100) substrate using H_2 or N_2 carrier gas followed by a Ge cap layer deposition. At 350 °C, C and Si are uniformly adsorbed on the Ge surface and the incorporated C and Si form steep delta profiles below detection limit of SIMS measurement. By using N_2 as carrier gas, the incorporated C and Si doses in Ge are saturated at one mono-layer below 350 °C. At this temperature range, the incorporated C and Si doses are nearly the same, indicating CH_3SiH_3 is adsorbed on the Ge surface without decomposing the C−Si bond. On the other hand, by using H_2 as carrier gas, lower incorporated C is observed in comparison to Si. CH_3SiH_3 injected with H_2 carrier gas is adsorbed on Ge without decomposing the C−Si bond and the adsorbed C is reduced by dissociation of the C−Si bond during temperature ramp up to 550 °C. The adsorbed C is maintained on the Ge surface in N_2 at 550 °C. - Highlights: • C and Si delta doping in Ge is investigated using RPCVD system by CH_3SiH_3 exposure. • Atomically flat C and Si delta layers are fabricated at 350 °C. • Incorporated C and Si doses are saturated at one mono-layer below 350 °C. • CH_3SiH_3 adsorption occurred without decomposing C−Si bond. • Adsorbed C is desorbed due to dissociation by hydrogen during postannealing at 550 °C.

Intergranular phase of the Si3 N4 hot pressed with Mg O/Y2 O3

International Nuclear Information System (INIS)

Costa, Celio A.; Todd, Judith A.

1997-01-01

Monolithic and composite Si 3 N 4 hot-pressed with 3% Mgo or 6% Y 2 O 3 were analyzed with X-ray diffraction and transmission electron microscopy. The results showed materials to be composed of β-Si 3 N 4 grains and an intergranular phase which was partially crystalline and partially amorphous. For the materials sintered with Mg O, the identification of the intergranular phase was not conclusive. For the materials sintered with Y 2 O 3 . It was observed that the amount of intergranular crystalline phase decreased as whiskers were added to the material and the intergranular crystalline part had a crystallographic structure similar to yttrium-silicon-oxide-nitride family. (author)

Influence of carbon on structure stability, mechanical and tribological properties of β-Si3(Cx,N1‑x)4 silicon carbonitride

Science.gov (United States)

Zhong, Jing; Hua, Guomin; Chen, Linbo; Li, Changsheng; Yang, Jianhong; Cheng, Xiaonong

2018-05-01

In this study, β-Si3(Cx,N1‑x)4 Silicon Carbonitride was prepared by Self-Propagation High-Temperature Synthesis (SHS). And the influence of carbon on structure stability, mechanical and tribological properties of β-Si3(Cx,N1‑x)4 were investigated. The results showed that the solubility of carbon in β-Si3(Cx,N1‑x)4 was about 10 wt%, beyond which cubic-SiC segregated out of β-Si3(Cx,N1‑x)4 to form β-Si3N4/cubic-SiC composite. Regarding influences of carbon concentration on mechanical properties, the hardness of β-Si3(Cx,N1‑x)4 decreased from 1400 Hv to 1200 Hv with the increase of carbon concentration. Whereas, the fracture toughness of β-Si3(Cx,N1‑x)4 increased from 6.5 MPa · m0.5 to 7.6 MPa · m0.5 with the increase of carbon concentration. The tribological property studies revealed the anti-wear performance of β-Si3(Cx,N1‑x)4 was enhanced by the increase of carbon concentration. The dominated wear mechanism could be attributed to the abrasive wear by fracture.

Formation of InN atomic-size wires by simple N adsorption on the In/Si(111)–(4 × 1) surface

International Nuclear Information System (INIS)

Guerrero-Sánchez, J.; Takeuchi, Noboru

2016-01-01

Highlights: • N atoms on the surface form bonds with two In atoms and one Si atom. • Surface formation energy calculations show two stable structures with formation of InN atomic-size wires. • Projected density of states shows a tendency to form In−N and Si−N bonds on the surface. • Charge density corroborates the covalent character of the In−N bonds. - Abstract: We have carried out first principles total energy calculations to study the formation of InN atomic-size wires on the In/Si(111)–(4 × 1) surface. In its most favorable adsorption site, a single N atom forms InN arrangements. The deposit of 0.25 monolayers (MLs) of N atoms, result in the breaking of one of the original In chains and the formation of an InN atomic size wire. Increasing the coverage up to 0.5 ML of N atoms results in the formation of two of those wires. Calculated surface formation energies show that for N-poor conditions the most stable configuration is the original In/Si(111)–(4 × 1) surface with no N atoms. Increasing the N content, and in a reduced range of chemical potential, the formation of an InN wire is energetically favorable. Instead, from intermediate to N-rich conditions, two InN atomic wires are more stable. Projected density of states calculations have shown a trend to form covalent bonds between the In−p and N−p orbitals in these stable models.

Light coupling and distribution for Si3N4/SiO2 integrated multichannel single-mode sensing system

Science.gov (United States)

Kaźmierczak, Andrzej; Dortu, Fabian; Schrevens, Olivier; Giannone, Domenico; Bouville, David; Cassan, Eric; Gylfason, Kristinn B.; Sohlström, Hans; Sanchez, Benito; Griol, Amadeu; Hill, Daniel

2009-01-01

We present an efficient and highly alignment-tolerant light coupling and distribution system for a multichannel Si3N4/SiO2 single-mode photonics sensing chip. The design of the input and output couplers and the distribution splitters is discussed. Examples of multichannel data obtained with the system are given.

Modified Wagner model for the active-to-passive transition in the oxidation of Si3N4

International Nuclear Information System (INIS)

Wang Junjie; Zhang Litong; Zeng Qingfeng; Cheng Laifei; Xu Yongdong

2008-01-01

Si 3 N 4 is used as the coating material of space shuttle structures which receive very high thermal fluxes during the atmospheric re-entry phase. Two main regimes govern the oxidation of Si 3 N 4 : the passive oxidation, with the formation of a protective silica layer leading generally to a mass gain, and the active oxidation, with vaporization of SiO leading to a mass loss of the sample. To ensure that silicon nitride will efficiently protect a material in given oxidizing environments, its own oxidation behaviour must be previously known. Therefore, the active-to-passive transition of Si 3 N 4 oxidation is a problem of deep scientific importance and of wide technological relevance. In this paper, a modified Wager model for the active-to-passive transition in the oxidation of Si 3 N 4 is presented, which includes the non-equilibrium effects caused by the mass transfer. The present theoretical calculations satisfactorily explained the reported experimental and theoretical data. The influence of flow rate on the active-to-passive transition boundary has been explained using our model. The rate controlling mechanism of the oxidation at the active-to-passive transition point is proposed

Functionalization of Fe3O4/SiO2 with N-(2-Aminoethyl-3-aminopropyl for Sorption of [AuCl4]-

Directory of Open Access Journals (Sweden)

Nuryono Nuryono

2016-08-01

Full Text Available Synthesis of Fe3O4/SiO2 modified with N-(2-aminoethyl-3-aminopropyl group (Fe3O4/SiO2/ED via coating method and its application for adsorption-desorption of anionic gold in aqueous solution have been conducted. The synthesized product was characterized with an X-ray diffractometer (XRD, a Fourier transform infrared (FT-IR spectrophotometer and a transmission electron microscopy (TEM. Adsorption of Au(III was conducted in a batch system and the variables included pH, contact time, and initial concentration were investigated. Results showed that magnetite/silica has been successfully functionalized with N-(2-aminoethyl-3-aminopropyl in a homogeneous system. Kinetics study showed that adsorption of Au(III followed the pseudo-second order model with rate constant of 0.710 g mmol L-1min-1. Furthermore, the experimental data fitted well with the Langmuir isotherm model with the maximum adsorption capacity for Au(III of 142.9 mg g-1 and the energy of 25.0 kJ mol-1. Gold loaded on the Fe3O4/SiO2/ED could be easily desorbed with 0.2 mol L-1 HCl containing 2 wt.% of thiourea with recovery of 99.8%. Fe3O4/SiO2/ED was reusable and stable in 5 cycles of adsorption-desorption with recovery more than 90%. Fe3O4/SiO2/ED showed high selectivity towards Au(III in the multimetal system Au(III/Cu(II/Cr(VI with the coefficient selectivity for αAu-Cu of 227.5and for αAu-Cr of 12.3.

Varying the Lewis base coordination of the Y2N2 core in the reduced dinitrogen complexes {[(Me3Si)2N]2(L)Y}2(μ-η2:η2-N2) (L = benzonitrile, pyridines, triphenylphosphine oxide, and trimethylamine N-oxide).

Science.gov (United States)

Corbey, Jordan F; Farnaby, Joy H; Bates, Jefferson E; Ziller, Joseph W; Furche, Filipp; Evans, William J

2012-07-16

The effect of the neutral donor ligand, L, on the Ln(2)N(2) core in the (N═N)(2-) complexes, [A(2)(L)Ln](2)(μ-η(2):η(2)-N(2)) (Ln = Sc, Y, lanthanide; A = monoanion; L = neutral ligand), is unknown since all of the crystallographically characterized examples were obtained with L = tetrahydrofuran (THF). To explore variation in L, displacement reactions between {[(Me(3)Si)(2)N](2)(THF)Y}(2)(μ-η(2):η(2)-N(2)), 1, and benzonitrile, pyridine (py), 4-dimethylaminopyridine (DMAP), triphenylphosphine oxide, and trimethylamine N-oxide were investigated. THF is displaced by all of these ligands to form {[(Me(3)Si)(2)N](2)(L)Y}(2)(μ-η(2):η(2)-N(2)) complexes (L = PhCN, 2; py, 3; DMAP, 4; Ph(3)PO, 5; Me(3)NO, 6) that were fully characterized by analytical, spectroscopic, density functional theory, and X-ray crystallographic methods. The crystal structures of the Y(2)N(2) cores in 2-5 are similar to that in 1 with N-N bond distances between 1.255(3) Å and 1.274(3) Å, but X-ray analysis of the N-N distance in 6 shows it to be shorter: 1.198(3) Å.

A novel yellow-emitting SrAlSi4N7:Ce3+ phosphor for solid state lighting: Synthesis, electronic structure and photoluminescence properties

Science.gov (United States)

Ruan, Jian; Xie, Rong-Jun; Funahashi, Shiro; Tanaka, Yoshinori; Takeda, Takashi; Suehiro, Takayuki; Hirosaki, Naoto; Li, Yuan-Qiang

2013-12-01

Ce3+-doped and Ce3+/Li+-codoped SrAlSi4N7 phosphors were synthesized by gas pressure sintering of powder mixtures of Sr3N2, AlN, α-Si3N4, CeN and Li3N. The phase purity, electronic crystal structure, photoluminescence properties of SrAlSi4N7:Ce3+(Ce3+/Li+) were investigated in this work. The band structure calculated by the DMol3 code shows that SrAlSi4N7 has a direct band gap of 3.87 eV. The single crystal analysis of Ce3+-doped SrAlSi4N7 indicates a disordered Si/Al distribution and nitrogen vacnacy defects. SrAlSi4N7 was identified as a major phase of the fired powders, and Sr5Al5Si21N35O2 and AlN as minor phases. Both Ce3+ and Ce3+/Li+ doped SrAlSi4N7 phosphors can be efficiently excited by near-UV or blue light and show a broadband yellow emission peaking around 565 nm. A highest external quantum efficiency of 38.3% under the 450 nm excitation was observed for the Ce3+/Li+-doped SrAlSi4N7 (5 mol%). A white light LED lamp with color temperature of 6300 K and color rendering index of Ra=78 was achieved by combining Sr0.97Al1.03Si3.997N\\94\\maccounttest14=t0005_18193 7:Ce3+0.03 with a commercial blue InGaN chip. It indicates that SrAlSi4N7:Ce3+ is a promising yellow emitting down-conversion phosphor for white LEDs.

The uranium(VI) oxoazides [UO{sub 2}(N{sub 3}){sub 2}.CH{sub 3}CN], [(bipy){sub 2}(UO{sub 2}){sub 2}(N{sub 3}){sub 4}], [(bipy)UO{sub 2}(N{sub 3}){sub 3}]{sup -}, [UO{sub 2}(N{sub 3}){sub 4}]{sup 2-}, and [(UO{sub 2}){sub 2}(N{sub 3}){sub 8}]{sup 4-}

Energy Technology Data Exchange (ETDEWEB)

Haiges, Ralf; Christe, Karl O. [Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, Los Angeles, CA (United States); Vasiliu, Monica; Dixon, David A. [Department of Chemistry, The University of Alabama, Tuscaloosa, AL (United States)

2017-01-12

The reaction between [UO{sub 2}F{sub 2}] and an excess of Me{sub 3}SiN{sub 3} in acetonitrile solution results in fluoride-azide exchange and the uranium(VI) dioxodiazide adduct [UO{sub 2}(N{sub 3}){sub 2}.CH{sub 3}CN] was isolated in quantitative yield. The subsequent reaction of [UO{sub 2}(N{sub 3}){sub 2}.CH{sub 3}CN] with 2,2{sup '}-bipyridine (bipy) resulted in the formation of the azido-bridged binuclear complex [(bipy){sub 2}(UO{sub 2}){sub 2}(N{sub 3}){sub 4}]. The triazido anion [(bipy)UO{sub 2}(N{sub 3}){sub 3}]{sup -} was obtained by the reaction of [UO{sub 2}(N{sub 3}){sub 2}.CH{sub 3}CN] with stoichiometric amounts of bipy and the ionic azide [PPh{sub 4}][N{sub 3}]. The reaction of [UO{sub 2}(N{sub 3}){sub 2}] with two equivalents of the [PPh{sub 4}][N{sub 3}] resulted in the formation of the mononuclear tetraazido anion [UO{sub 2}(N{sub 3}){sub 4}]{sup 2-} as well as the azido-bridged binuclear anion [(UO{sub 2}){sub 2}(N{sub 3}){sub 8}]{sup 4-}. The novel uranium oxoazides were characterized by their vibrational spectra and in the case of [(bipy){sub 2}(UO{sub 2}){sub 2}(N{sub 3}){sub 4}].CH{sub 3}CN, [PPh{sub 4}][(bipy)UO{sub 2}(N{sub 3}){sub 3}], [PPh{sub 4}]{sub 2}[UO{sub 2}(N{sub 3}){sub 4}], [PPh{sub 4}]{sub 2}[UO{sub 2}(N{sub 3}){sub 4}].2CH{sub 3}CN, and [PPh{sub 4}]{sub 4}[(UO{sub 2}){sub 2}(N{sub 3}){sub 8}].4CH{sub 3}CN by their X-ray crystal structures. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Mechanistic aspects of hydrosilylation catalyzed by (ArN=)Mo(H)(Cl)(PMe3)3.

Science.gov (United States)

Khalimon, Andrey Y; Shirobokov, Oleg G; Peterson, Erik; Simionescu, Razvan; Kuzmina, Lyudmila G; Howard, Judith A K; Nikonov, Georgii I

2012-04-02

The reaction of (ArN=)MoCl(2)(PMe(3))(3) (Ar = 2,6-diisopropylphenyl) with L-Selectride gives the hydrido-chloride complex (ArN=)Mo(H)(Cl)(PMe(3))(3) (2). Complex 2 was found to catalyze the hydrosilylation of carbonyls and nitriles as well as the dehydrogenative silylation of alcohols and water. Compound 2 does not show any productive reaction with PhSiH(3); however, a slow H/D exchange and formation of (ArN=)Mo(D)(Cl)(PMe(3))(3) (2(D)) was observed upon addition of PhSiD(3). Reactivity of 2 toward organic substrates was studied. Stoichiometric reactions of 2 with benzaldehyde and cyclohexanone start with dissociation of the trans-to-hydride PMe(3) ligand followed by coordination and insertion of carbonyls into the Mo-H bond to form alkoxy derivatives (ArN=)Mo(Cl)(OR)(PMe(2))L(2) (3: R = OCH(2)Ph, L(2) = 2 PMe(3); 5: R = OCH(2)Ph, L(2) = η(2)-PhC(O)H; 6: R = OCy, L(2) = 2 PMe(3)). The latter species reacts with PhSiH(3) to furnish the corresponding silyl ethers and to recover the hydride 2. An analogous mechanism was suggested for the dehydrogenative ethanolysis with PhSiH(3), with the key intermediate being the ethoxy complex (ArN=)Mo(Cl)(OEt)(PMe(3))(3) (7). In the case of hydrosilylation of acetophenone, a D-labeling experiment, i.e., a reaction of 2 with acetophenone and PhSiD(3) in the 1:1:1 ratio, suggests an alternative mechanism that does not involve the intermediacy of an alkoxy complex. In this particular case, the reaction presumably proceeds via Lewis acid catalysis. Similar to the case of benzaldehyde, treatment of 2 with styrene gives trans-(ArN=)Mo(H)(η(2)-CH(2)═CHPh)(PMe(3))(2) (8). Complex 8 slowly decomposes via the release of ethylbenzene, indicating only a slow insertion of styrene ligand into the Mo-H bond of 8.

Moisture distribution measurements in adhesive-bonded composites using the D (3He,p)4 He reaction

International Nuclear Information System (INIS)

Schulte, R.L.; Deiasi, R.J.

1981-01-01

Adhesive bonding of composite materials for many aircraft components offers a distinct advantage in weight and cost reduction compared to similar structures that have been joined by riveting. However, the long term performance of adhesive-bonded components depends on the degree and rate of moisture absorption by the adhesive in the service environment. To investigate the rate and the mechanism of water transport in adhesive-bonded composite materials, a nuclear reaction analysis method based on the D( 3 He,p) 4 He reaction is used to measure the moisture distributions. Samples of graphite/epoxy composite materials were bonded with an epoxy adhesive and isothermally conditioned in a controlled D 2 O environment at 70% relative humidity and 77 0 C for various exposure times. The moisture profiles were measured along the adhesive (adhesive scan) as well as through the thickness of the bonded joint (transverse scan). The dimensions of the probing beam were 125 μm x 125 μm for the adhesive scan and 25 μ x 200 μm for the transverse scan. Absolute deuterium concentrations were determined by comparison of the proton yield from the composite/adhesive to that from reference standards. Calculations from diffusion models of water transport based on parameters determined from bulk measurement techniques are compared to the measured profile and the agreement indicates that classical Fickian diffusion describes the transport of moisture in these materials

3Y-TZP/Si2N2O composite obtained by pressureless sintering

International Nuclear Information System (INIS)

Santos, Carlos Augusto Xavier

2006-01-01

Zirconia 3YTZP presents excellent properties at room temperature. These properties decrease as the temperature increases because high temperature acts negatively over the stress induced transformation toughening in the matrix. The addition of Si 3 N 4 and SiC in a Y-TZP matrix is very interesting because leads to formation of silicon oxynitride and it increases the mechanical properties like toughness and hardness. Certainly the mechanical properties increment is limited by several difficulties which have appeared during processing and heating of these materials. This paper studies the Y-TZP/Si 2 N 2 0 pressureless sintered composite, under different temperatures, showing the behavior of 20 vol %Si 3 N 4 -SiC when added in YTZP matrix and heated under no pressure system. Al 2 O 3 and Y 2 O 3 were used as sintering aids. The mixture was milled and molded by cold isostatic pressure. Samples were heated at 1500 deg, 1600 deg and 17000 deg C x 2h without pressure under atmospheric conditions using Si 3 N 4 bed-powder. Samples were characterized by XRD and density, hardness, toughness, bending strength were measured. The structure of the material was observed in SEMITEM/EPMA to verify the distribution and composition of the materials in the composite and the contact between filler surface and the matrix. The formation of SiON 2 was observed in the sintered material due to reaction between both nitride and carbide with Y - TZP matrix. Furthermore the material showed an increment of both hardness and toughness as temperature increases. The samples presented considerable resistance to oxidation below 1000 deg C. (author)

A computational study on the adsorption configurations and reactions of SiHx(x = 1-4) on clean and H-covered Si(100) surfaces

Science.gov (United States)

Le, Thong N.-M.; Raghunath, P.; Huynh, Lam K.; Lin, M. C.

2016-11-01

Possible adsorption configurations of H and SiHx (x = 1 - 4) on clean and H-covered Si(100) surfaces are determined by using spin-polarized DFT calculations. The results show that, on the clean surface, the gas-phase hydrogen atom and SiH3 radicals effectively adsorb on the top sites, while SiH and SiH2 prefer the bridge sites of the first layer. Another possibility for SiH is to reside on the hollow sites with a triple-bond configuration. For a partially H-coverd Si(100) surface, the mechanism is similar but with higher adsorption energies in most cases. This suggests that the surface species become more stable in the presence of surface hydrogens. The minimum energy paths for the adsorption/migration and reactions of H/SiHx species on the surfaces are explored using the climbing image-nudged elastic band method. The competitive surface processes for Si thin-film formation from SiHx precursors are also predicted. The study reveals that the migration of hydrogen adatom is unimportant with respect to leaving open surface sites because of its high barriers (>29.0 kcal/mol). Alternatively, the abstraction of hydrogen adatoms by H/SiHx radicals is more favorable. Moreover, the removal of hydrogen atoms from adsorbed SiHx, an essential step for forming Si layers, is dominated by abstraction rather than the decomposition processes.

A novel yellow-emitting SrAlSi4N7:Ce3+ phosphor for solid state lighting: Synthesis, electronic structure and photoluminescence properties

International Nuclear Information System (INIS)

Ruan, Jian; Xie, Rong-Jun; Funahashi, Shiro; Tanaka, Yoshinori; Takeda, Takashi; Suehiro, Takayuki; Hirosaki, Naoto; Li, Yuan-Qiang

2013-01-01

Ce 3+ -doped and Ce 3+ /Li + -codoped SrAlSi 4 N 7 phosphors were synthesized by gas pressure sintering of powder mixtures of Sr 3 N 2 , AlN, α-Si 3 N 4 , CeN and Li 3 N. The phase purity, electronic crystal structure, photoluminescence properties of SrAlSi 4 N 7 :Ce 3+ (Ce 3+ /Li + ) were investigated in this work. The band structure calculated by the DMol 3 code shows that SrAlSi 4 N 7 has a direct band gap of 3.87 eV. The single crystal analysis of Ce 3+ -doped SrAlSi 4 N 7 indicates a disordered Si/Al distribution and nitrogen vacnacy defects. SrAlSi 4 N 7 was identified as a major phase of the fired powders, and Sr 5 Al 5 Si 21 N 35 O 2 and AlN as minor phases. Both Ce 3+ and Ce 3+ /Li + doped SrAlSi 4 N 7 phosphors can be efficiently excited by near-UV or blue light and show a broadband yellow emission peaking around 565 nm. A highest external quantum efficiency of 38.3% under the 450 nm excitation was observed for the Ce 3+ /Li + -doped SrAlSi 4 N 7 (5 mol%). A white light LED lamp with color temperature of 6300 K and color rendering index of Ra=78 was achieved by combining Sr 0.97 Al 1.03 Si 3.997 N/94/maccounttest14=t0005 1 8193 7 :Ce 3+ 0.03 with a commercial blue InGaN chip. It indicates that SrAlSi 4 N 7 :Ce 3+ is a promising yellow emitting down-conversion phosphor for white LEDs. - Graphical abstract: One-phosphor converted white light-emitting diode (LED) was fabricated by combining a blue LED chip and a yellow-emitting SrAlSi4N7:Ce 3+ phosphor (see inset), which has the color rendering index of 78 and color temperature of 6300 K. - Highlights: • We reported a new yellow nitride phosphor suitable for solid state lighting. • We solved the crystal structure and evidenced a disordered Si/Al distribution. • We fabricated a high color rendering white LEDs by using a single SrAlSi4N7:Ce

Analysis of reaction between c+a and -c+a dislocations in GaN layer grown on 4-inch Si(111) substrate with AlGaN/AlN strained layer superlattice by transmission electron microscopy

Energy Technology Data Exchange (ETDEWEB)

Sugawara, Yoshihiro; Ishikawa, Yukari, E-mail: yukari@jfcc.or.jp [Japan Fine Ceramics Center, Atsuta, Nagoya, 456-8587 (Japan); Watanabe, Arata [Research Center for Nano Devices and Advanced Materials, Nagoya Institute of Technology, Nagoya, 466-8555 (Japan); Miyoshi, Makoto; Egawa, Takashi [Research Center for Nano Devices and Advanced Materials, Nagoya Institute of Technology, Nagoya, 466-8555 (Japan); Innovation Center for Multi-Business of Nitride Semiconductors, Nagoya Institute of Technoloy, Nagoya, 466-8555 (Japan)

2016-04-15

The behavior of dislocations in a GaN layer grown on a 4-inch Si(111) substrate with an AlGaN/AlN strained layer superlattice using horizontal metal-organic chemical vapor deposition was observed by transmission electron microscopy. Cross-sectional observation indicated that a drastic decrease in the dislocation density occurred in the GaN layer. The reaction of a dislocation (b=1/3[-211-3]) and anothor dislocation (b =1/3[-2113]) to form one dislocation (b =2/3[-2110]) in the GaN layer was clarified by plan-view observation using weak-beam dark-field and large-angle convergent-beam diffraction methods.

Lu{sub 3}(Al,Si){sub 5}(O,N){sub 12}:Ce{sup 3+} phosphors with broad emission band and high thermal stability for white LEDs

Energy Technology Data Exchange (ETDEWEB)

Liu, Jiaqing; Wang, Xiaojun; Xuan, Tongtong; Wang, Chunbo; Li, Huili, E-mail: hlli@phy.ecnu.edu.cn; Sun, Zhuo

2015-02-15

A yellow-orange emitting Lu{sub 3}Al{sub 5−x}Si{sub x}O{sub 12−x}N{sub x}:Ce{sup 3+} phosphor with excellent color rendering, high luminescent efficiency and high thermal stability was reported in this paper. It was synthesized by a conventional solid-state reaction method. The effect of Si{sup 4+}–N{sup 3−} incorporation on the optical properties of Lu{sub 3}Al{sub 5}O{sub 12}:Ce{sup 3+} phosphor was investigated and compared to YAG:Ce{sup 3+} with the same compositions. Similarly, the addition of α-Si{sub 3}N{sub 4} leads to a distinct redshift and broadening of photoluminescent spectrum, which is assigned to the increased covalency and crystal field strength caused by N{sup 3−}. Nevertheless, an excellent thermal stability and a higher integrated intensity presented by α-Si{sub 3}N{sub 4}-doped LuAG:Ce{sup 3+} are distinctive. Further, the emission intensity can be greatly enhanced by adding NaF flux. Finally, the white LED flat lamp with a CRI as high as 83 and a luminous efficiency of 85 lm/W is successfully realized by using a single LuAG-based oxynitride phosphor combined with a blue LED chip, which is completely feasible for general indoor illuminations to replace the traditional fluorescent or incandescent lamps. - Highlights: • Si{sub 3}N{sub 4}-doped LuAG:Ce{sup 3+} oxynitride phosphors were synthesized by a solid-state reaction. • The effect of Si{sup 4+}–N{sup 3−} incorporation on the optical properties was investigated. • The addition of Si{sub 3}N{sub 4} leads to an obvious redshift of the emission spectra. • Lu{sub 3}Al{sub 5−x}Si{sub x}O{sub 12−x}N{sub x}:Ce{sup 3+} shows an excellent thermal stability and a higher intensity. • A warm white LED with CRI=83 is achieved by a single oxynitride phosphor.

Effects of Surface Treatment Processes of SiC Ceramic on Interfacial Bonding Property of SiC-AFRP

Directory of Open Access Journals (Sweden)

WEI Ru-bin

2016-12-01

Full Text Available To improve the interfacial bonding properties of SiC-aramid fiber reinforced polymer matrix composites (SiC-AFRP, the influences of etching process of SiC ceramic, coupling treatment process, and the adhesives types on the interfacial peel strength of SiC-AFRP were studied. The results show that the surface etching process and coupling treatment process of silicon carbide ceramic can effectively enhance interfacial bonding property of the SiC-AFRP. After soaked the ceramic in K3Fe(CN6 and KOH mixed etching solution for 2 hours, and coupled with vinyl triethoxy silane coupling agent, the interfacial peel strength of the SiC-AFRP significantly increases from 0.45kN/m to 2.20kN/m. EVA hot melt film with mass fraction of 15%VA is ideal for interface adhesive.

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...

Surface texturing of Si3N4–SiC ceramic tool components by pulsed laser machining

CSIR Research Space (South Africa)

Tshabalala, LC

2016-03-01

Full Text Available Traditional abrasive techniques such as grinding and lapping have long been used in the surface conditioning of engineering materials. However, in the processing of hard and brittle materials like silicon nitride (Si(sub3)N(sub4)), machining...

First-principles quantum molecular calculations of structural and mechanical properties of TiN/SiNx heterostructures, and the achievable hardness of the nc-TiN/SiNx nanocomposites

International Nuclear Information System (INIS)

Ivashchenko, V.I.; Veprek, S.; Argon, A.S.; Turchi, P.E.A.; Gorb, L.; Hill, F.; Leszczynski, J.

2015-01-01

TiN/SiN x heterostructures with one monolayer of the interfacial SiN x have been investigated in the framework of first-principles molecular dynamics calculations in the temperature range of 0 to 1400 K with subsequent static relaxation. The atomic configurations, thermal stability and stress–strain relations have been calculated. Among the heterostructures studied, only the TiN(111)/SiN/TiN(111) and TiN(111)/Si 2 N 3 /TiN(111) ones are thermally stable. Upon tensile load, decohesion occurs between the Ti−N bonds adjacent to the SiN x interfacial layer for TiN(001)/SiN/TiN(001) and TiN(111)/Si 2 N 3 /TiN(111) heterostructures, and inside the TiN slab for TiN(001)/Si 3 N 4 /TiN(001) and TiN(110)/SiN/TiN(110) ones. Upon shear, failure occurs in TiN near the interfaces in all the heterostructures, except for the TiN(001)/Si 3 N 4 /TiN(001) one, for which the plastic flow occurs inside the TiN slab. Based on these results we estimate the maximum achievable hardness of nc-TiN/Si 3 N 4 nanocomposites free of impurities to be about 170 GPa. - Highlights: • Interface stability in TiN/SiN x heterostructures at T ≤ 1400 K is studied by quantum molecular dynamics. • Ideal decohesion and shear strengths of the heterostructures have been calculated. • Achievable hardness of nc-TiN/Si 3 N 4 -like nanocomposites of about 170 GPa is calculated. • Experimentally achieved lower hardness is limited by flaws, such as oxygen impurities

Computer Aided Multi-scale Design of SiC-Si3N4 Nanoceramic Composites for High-Temperature Structural Applications

Energy Technology Data Exchange (ETDEWEB)

Vikas Tomer; John Renaud

2010-08-31

It is estimated that by using better and improved high temperature structural materials, the power generation efficiency of the power plants can be increased by 15% resulting in significant cost savings. One such promising material system for future high-temperature structural applications in power plants is Silicon Carbide-Silicon Nitride (SiC-Si{sub 3}N{sub 4}) nanoceramic matrix composites. The described research work focuses on multiscale simulation-based design of these SiC-Si{sub 3}N{sub 4} nanoceramic matrix composites. There were two primary objectives of the research: (1) Development of a multiscale simulation tool and corresponding multiscale analyses of the high-temperature creep and fracture resistance properties of the SiC-Si{sub 3}N{sub 4} nanocomposites at nano-, meso- and continuum length- and timescales; and (2) Development of a simulation-based robust design optimization methodology for application to the multiscale simulations to predict the range of the most suitable phase morphologies for the desired high-temperature properties of the SiC-Si{sub 3}N{sub 4} nanocomposites. The multiscale simulation tool is based on a combination of molecular dynamics (MD), cohesive finite element method (CFEM), and continuum level modeling for characterizing time-dependent material deformation behavior. The material simulation tool is incorporated in a variable fidelity model management based design optimization framework. Material modeling includes development of an experimental verification framework. Using material models based on multiscaling, it was found using molecular simulations that clustering of the SiC particles near Si{sub 3}N{sub 4} grain boundaries leads to significant nanocomposite strengthening and significant rise in fracture resistance. It was found that a control of grain boundary thicknesses by dispersing non-stoichiometric carbide or nitride phases can lead to reduction in strength however significant rise in fracture strength. The

N{sub 2}O + CO reaction over Si- and Se-doped graphenes: An ab initio DFT study

Energy Technology Data Exchange (ETDEWEB)

Gholizadeh, Reza [Laboratory of Chemical Engineering Thermodynamics, Department of Chemical Engineering, Tsinghua University, Beijing 100084 (China); Yu, Yang-Xin, E-mail: yangxyu@mail.tsinghua.edu.cn [Laboratory of Chemical Engineering Thermodynamics, Department of Chemical Engineering, Tsinghua University, Beijing 100084 (China); State Key Laboratory of Chemical Engineering, Tsinghua University, Beijing 100084 (China)

2015-12-01

Graphical abstract: Si-doped graphene can be one of efficient green catalysts for conversion of the airborne pollutants. - Highlights: • N{sub 2}O can be efficiently reduced by CO over Si-doped graphenes. • Enough charge transferred from Si to N{sub 2}O makes the N{sub 2}–O bond break easily. • Si-doped graphene is efficient green catalysts for conversion of the airborne pollutants. • vdW interaction and ZPE energy significantly influence the predictions of activation energies. - Abstract: Catalytic conversion of non-CO{sub 2} green house gases and other harmful gases is a promising way to protect the atmospheric environment. Non-metal atom-doped graphene is attractive for use as a catalyst in the conversion due to its unique electronic properties, relatively low price and leaving no burden to the environment. To make an attempt on the development of green catalysts for the conversion, ab initio density functional theory is used to investigate the mechanisms of N{sub 2}O reduction by CO on Si- and Se-doped graphenes. We have calculated the geometries and adsorption energies of reaction species (N{sub 2}O, CO, N{sub 2} and CO{sub 2}) as well as energy profiles along the reaction pathways. The activation energies of N{sub 2}O decomposition and CO oxidation on both Si- and Se-doped graphenes have been obtained. Our calculated results indicate that the catalytic activity of Si-doped graphene is better than the Fe{sup +} in gas phase and comparable to the single Fe atom embedded on graphene. In the calculations, we found that van der Waals interactions and zero-point energy are two non-negligible factors for the predictions of the activation energies. Further discussion shows that Si-doped graphene can be one of efficient green catalysts for conversion of the airborne pollutants and Se-doped graphene can be a candidate for oxidizing CO by atomic oxygen.

Cross-Dehydrogenative Coupling Reactions Between P(O)-H and X-H (X = S, N, O, P) Bonds.

Science.gov (United States)

Hosseinian, Akram; Farshbaf, Sepideh; Fekri, Leila Zare; Nikpassand, Mohammad; Vessally, Esmail

2018-05-26

P(O)-X (X = S, N, O, P) bond-containing compounds have extensive application in medicinal chemistry, agrochemistry, and material chemistry. These useful organophosphorus compounds also have many applications in organic synthesis. In light of the importance of titled compounds, there is continuing interest in the development of synthetic methods for P(O)-X bonds construction. In the last 4 years, the direct coupling reaction of P(O)-H compounds with thiols, alcohols, and amines/amides has received much attention because of the atom-economic character. This review aims to give an overview of new developments in cross-dehydrogenative coupling reactions between P(O)-H and X-H (X = S, N, O, P) bonds, with special emphasis on the mechanistic aspects of the reactions.

Evaluation of cross sections for 197Au(n,3n) and 197Au(n,4n) reactions from threshold to 50 MeV

International Nuclear Information System (INIS)

Yu Baosheng; Shen Qingbiao; Cai Dunjiu

1994-01-01

The measured data of cross sections for 197 Au(n,3n) and 197 Au(n,4n) reactions were collected and analysed. The theoretical calculations of above mentioned reactions were carried out to predict the data in higher energy region. The sets of cross sections for 197 Au(n,3n) and 197 Au(n,4n) reactions from threshold to 50 MeV were recommended on the basis of the experimental and calculated data. (2 figs)

Wear Characteristics According of Heat Treatment of Si3N4 with Different Amounts of SiO2 Nano-Colloid

International Nuclear Information System (INIS)

Ahn, Seok Hwan; Nam, Ki Woo

2014-01-01

This study sintered Si 3 N 4 with different amounts of SiO 2 nano-colloid. The surface of a mirror-polished specimen was coated with SiO 2 nano-colloid, and cracks were healed when the specimen was treated at a temperature of 1273 K for 1 h in air. Wear specimen experiments were conducted after heat treatments for 10 min at 1073, 1273, and 1573 K. The heat-treated surface that was coated with the SiO 2 nano-colloid was slightly rougher than the noncoated surface. The oxidation state of the surface according to the heat treatment temperature showed no correlation with the surface roughness. Moreover, the friction coefficient, wear loss, and bending strength were not related to the surface roughness. Si 3 N 4 exhibited an abrasive wear behavior when SKD11 was used as an opponent material. The friction coefficient was proportional to the wear loss, and the bending strength was inversely proportional to the friction coefficient and wear loss. The friction coefficient and wear loss increased with increasing amounts of the SiO 2 nanocolloid. In addition, the friction coefficient was slightly increased by increasing the heat treatment temperature

Synthesis and mechanical characterization of PZT/Sr based composite ceramics with addition of Si{sub 3}N{sub 4}; Sintese e caracterizacao mecanica de ceramicas compositas a base de PZT/Sr com adicoes de Si{sub 3}N{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Santos, M.A.P.; Santos, R.C.P.; Santos, M.C.C.; Rocha, C.D.G.; Silva, M., E-mail: cida@ipqm.mar.mil.b [Instituto de Pesquisas da Marinha (IPqM), Ilha do Governador, RJ (Brazil). Grupo de Materiais

2010-07-01

In the Underwater Acoustics field, piezoelectric ceramics are the most usually employed materials for the conversion of mechanical energy (acoustic signal) into electric energy (electric signal) and vice-versa, in sensors (hydrophones) or hydroacoustic projectors. In the development of new compositions for these applications, piezoelectric performance is generally prioritized, to the expense of its mechanical properties. With this in mind, the object of this work was to study the effects of the addition of Si{sub 3}N{sub 4} in the mechanical properties of PZT-Sr based electronic ceramics. Thus, a novel piezoelectric ceramic with the addition of small percentages in weight (0;0.1;1;3 and 5) of the structural ceramic Si{sub 3}N{sub 4} was successfully processed by the oxide mixing route ; the compounds were sintered in a conventional at 1200 deg C for 2h. The densities of the compounds thus obtained for the different percentages of Si{sub 3}N{sub 4} ranged from 55 to 97% and decreased with the increase of the content of Si{sub 3}N{sub 4}. Presence of equiaxial grains with normal growth was observed in all samples. MEV/EDS analysis of the micro-structures of the compositions detected the presence of a second phase rich in Zr, confirmed by DRX, which is a result of large quantities of volatilized PbO; the sintered pieces had their mechanical properties investigated by ultra-sonic inspection. It was observed that, among the sintered compositions, the PZT-Sr ceramic with 0.1% Si{sub 3}N{sub 4} presented the smallest value for Young's Modulus E and Shear Modulus G, 75 Gpa and 28 Gpa, respectively. The Poisson's Coefficients {nu} tended to decrease with the increase of Si{sub 3}N{sub 4} added to the PZT-Sr ceramic, indicating, thus, that the added compound may be used to adjust the mechanical properties of the material. (author)

C-N Bond Activation and Ring Opening of a Saturated N-Heterocyclic Carbene by Lateral Alkali-Metal-Mediated Metalation.

Science.gov (United States)

Hernán-Gómez, Alberto; Kennedy, Alan R; Hevia, Eva

2017-06-01

Combining alkali-metal-mediated metalation (AMMM) and N-heterocyclic carbene (NHC) chemistry, a novel C-N bond activation and ring-opening process is described for these increasingly important NHC molecules, which are generally considered robust ancillary ligands. Here, mechanistic investigations on reactions of saturated NHC SIMes (SIMes=[:C{N(2,4,6-Me 3 C 6 H 2 )CH 2 } 2 ]) with Group 1 alkyl bases suggest this destructive process is triggered by lateral metalation of the carbene. Exploiting co-complexation and trans-metal-trapping strategies with lower polarity organometallic reagents (Mg(CH 2 SiMe 3 ) 2 and Al(TMP)iBu 2 ), key intermediates in this process have been isolated and structurally defined. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stress in ion-implanted CVD Si3N4 films

International Nuclear Information System (INIS)

EerNisse, E.P.

1977-01-01

The compressive stress buildup caused in chemical-vapor-deposited (CVD) Si 3 N 4 films by ion implantation is shown to be caused entirely by atomic collision effects, ionization effects being unimportant. The stress introduction rate is shown to be independent of CVD processing variables and O content of the film. The maximum attainable compressive stress change is 3.5 x 10 10 dyn/cm 2 , resulting in a maximum net compressive stress of 2 x 10 10 dyn/cm 2 for films on Si where the as-deposited films inherently have 1.5 x 10 10 dyn/cm 2 tensile stress before ion implantation. Results are presented which show that O in the films inhibits thermal annealing of the ion-implantation-induced compressive stress. Results for introduction rate and annealing effects are presented in normalized form so that workers can use the effects for intentional stress level adjustment in the films to reduce probability of cracking and detachment

Investigation of the flatband voltage (V(FB)) shift of Al2O3 on N2 plasma treated Si substrate.

Science.gov (United States)

Kim, Hyungchul; Lee, Jaesang; Jeon, Heeyoung; Park, Jingyu; Jeon, Hyeongtag

2013-09-01

The relationships between the physical and electrical characteristics of films treated with N2 plasma followed by forming gas annealing (FGA) were investigated. The Si substrates were treated with various radio frequency (RF) power levels under a N2 ambient. Al2O3 films were then deposited on Si substrates via remote plasma atomic-layer deposition. The plasma characteristics, such as the radical and ion density, were investigated using optical emission spectroscopy. Through X-ray photoelectron spectroscopy, the chemical-bonding configurations of the samples treated with N2 plasma and FGA were examined. The quantity of Si-N bonds increased as the RF power was increased, and Si--O--N bonds were generated after FGA. The flatband voltage (VFB) was shifted in the negative direction with increasing RF power, but the VFB values of the samples after FGA shifted in the positive direction due to the formation of Si--O--N bonds. N2 plasma treatment with various RF power levels slightly increased the leakage current due to the generation of defect sites.

Bond breaking and bond making in tetraoxygen: analysis of the O2(X3Sigma(g)-) + O2(X3Sigma(g)-) O4 reaction using the electron pair localization function.

Science.gov (United States)

Scemama, Anthony; Caffarel, Michel; Ramírez-Solís, Alejandro

2009-08-06

We study the nature of the electron pairing at the most important critical points of the singlet potential energy surface of the 2O2 O4 reaction and its evolution along the reaction coordinate using the electron pair localization function (EPLF) [Scemama, A.; Chaquin, P.; Caffarel, M. J. Chem. Phys. 2004, 121, 1725]. To do that, the 3D topology of the EPLF calculated with quantum Monte Carlo (at both variational and fixed-node-diffusion Monte Carlo levels) using Hartree-Fock, multiconfigurational CASSCF, and explicitly correlated trial wave functions is analyzed. At the O4 equilibrium geometry the EPLF analysis reveals four equivalent covalent bonds and two lone pairs on each oxygen atom. Along the reaction path toward dissociation it is found that the two oxygen-oxygen bonds are not broken simultaneously but sequentially, and then the lone pairs are rearranged. In a more general perspective, the usefulness of the EPLF as a unique tool to analyze the topology of electron pairing in nontrivial chemical bonding situations as well as to visualize the major steps involved in chemical reactivity is emphasized. In contrast with most standard schemes to reveal electron localization (atoms in molecules, electron localization function, natural bond orbital, etc.), the newly introduced EPLF function gives a direct access to electron pairings in molecules.

Si{sub 3}N{sub 4} optomechanical crystals in the resolved-sideband regime

Energy Technology Data Exchange (ETDEWEB)

Davanço, M., E-mail: mdavanco@nist.gov [Center for Nanoscale Science and Technology, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); Department of Applied Physics, California Institute of Technology, Pasadena, California 91125 (United States); Ates, S.; Liu, Y. [Center for Nanoscale Science and Technology, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); Maryland NanoCenter, University of Maryland, College Park, Maryland 20742 (United States); Srinivasan, K. [Center for Nanoscale Science and Technology, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States)

2014-01-27

We demonstrate sideband-resolved Si{sub 3}N{sub 4} optomechanical crystals supporting 10{sup 5} quality factor optical modes at 980 nm, coupled to ≈4 GHz frequency mechanical modes with quality factors of ≈3000. Optomechanical electromagnetically induced transparency and absorption are observed at room temperature and in atmosphere with intracavity photon numbers in excess of 10{sup 4}.

Gold-coated iron nanoparticles in transparent Si{sub 3}N{sub 4} matrix thin films

Energy Technology Data Exchange (ETDEWEB)

Sanchez-Marcos, J. [Consejo Superior de Investigaciones Cientificas, Instituto de Ciencia de Materiales de Madrid (Spain); Cespedes, E. [Keele University, Institute for Science and Technology in Medicine, Guy Hilton Research Centre (United Kingdom); Jimenez-Villacorta, F. [Northeastern University, Department of Chemical Engineering (United States); Munoz-Martin, A. [Universidad Autonoma de Madrid, Centro de Microanalisis de Materiales (Spain); Prieto, C., E-mail: cprieto@icmm.csic.es [Consejo Superior de Investigaciones Cientificas, Instituto de Ciencia de Materiales de Madrid (Spain)

2013-06-15

A new method to prepare thin films containing gold-coated iron nanoparticles is presented. The ternary Fe-Au-Si{sub 3}N{sub 4} system prepared by sequential sputtering has revealed a progressive variation of microstructures from Au/Fe/Au/Si{sub 3}N{sub 4} multilayers to iron nanoparticles. Microstructural characterization by transmission electron microscopy, analysis of the magnetic properties and probing of the iron short-range order by X-ray absorption spectroscopy confirm the existence of a gold-coated iron nanoparticles of 1-2 nm typical size for a specific range of iron and gold contents per layer in the transparent silicon nitride ceramic matrix.

C and Si delta doping in Ge by CH{sub 3}SiH{sub 3} using reduced pressure chemical vapor deposition

Energy Technology Data Exchange (ETDEWEB)

Yamamoto, Yuji, E-mail: yamamoto@ihp-microelectronics.com [IHP, Im Technologiepark 25, 15236 Frankfurt (Oder) (Germany); Ueno, Naofumi; Sakuraba, Masao [Laboratory for Nanoelectronics and Spintronics, Research Institute of Electrical Communication, Tohoku University, 2-1-1, Katahira, Aoba-Ku, Sendai 980-8577 (Japan); Murota, Junichi [Micro System Integration Center, Tohoku University, 519-1176, Aramaki aza Aoba, Aoba-ku, Sendai 980-0845 (Japan); Mai, Andreas [IHP, Im Technologiepark 25, 15236 Frankfurt (Oder) (Germany); Tillack, Bernd [IHP, Im Technologiepark 25, 15236 Frankfurt (Oder) (Germany); Technische Universität Berlin, HFT4, Einsteinufer 25, 10587 Berlin (Germany)

2016-03-01

C and Si delta doping in Ge are investigated using a reduced pressure chemical vapor deposition system to establish atomic-order controlled processes. CH{sub 3}SiH{sub 3} is exposed at 250 °C to 500 °C to a Ge on Si (100) substrate using H{sub 2} or N{sub 2} carrier gas followed by a Ge cap layer deposition. At 350 °C, C and Si are uniformly adsorbed on the Ge surface and the incorporated C and Si form steep delta profiles below detection limit of SIMS measurement. By using N{sub 2} as carrier gas, the incorporated C and Si doses in Ge are saturated at one mono-layer below 350 °C. At this temperature range, the incorporated C and Si doses are nearly the same, indicating CH{sub 3}SiH{sub 3} is adsorbed on the Ge surface without decomposing the C−Si bond. On the other hand, by using H{sub 2} as carrier gas, lower incorporated C is observed in comparison to Si. CH{sub 3}SiH{sub 3} injected with H{sub 2} carrier gas is adsorbed on Ge without decomposing the C−Si bond and the adsorbed C is reduced by dissociation of the C−Si bond during temperature ramp up to 550 °C. The adsorbed C is maintained on the Ge surface in N{sub 2} at 550 °C. - Highlights: • C and Si delta doping in Ge is investigated using RPCVD system by CH{sub 3}SiH{sub 3} exposure. • Atomically flat C and Si delta layers are fabricated at 350 °C. • Incorporated C and Si doses are saturated at one mono-layer below 350 °C. • CH{sub 3}SiH{sub 3} adsorption occurred without decomposing C−Si bond. • Adsorbed C is desorbed due to dissociation by hydrogen during postannealing at 550 °C.

Preparation and characterization of hybrid A359/(SiC+Si{sub 3}N{sub 4}) composites synthesized by stir/squeeze casting techniques

Energy Technology Data Exchange (ETDEWEB)

Shalaby, Essam A.M.; Churyumov, Alexander Yu., E-mail: churyumov@misis.ru; Solonin, Alexey N.; Lotfy, A.

2016-09-30

Stir followed by squeeze casting techniques were used to produce A359 composites containing different weight percentage of (SiC+Si{sub 3}N{sub 4}) particles. Microstructures of the composites showed a homogeneous and even distribution of hybrid reinforcements within the matrix. Moreover, particles agglomerations, residual porosity, and other casting problems were not noticed. Interfacial reactions between the particles and the matrix were investigated using X-ray diffraction and energy dispersive X-ray analyses. The presence of particles in squeezed composites did not only increase the peak hardness of the composites, but also accelerated the aging kinetics. As compared with the A359 matrix alloy, a compression test of the hybrid composites exhibited a significant increase in the yield and the ultimate compressive strengths with a relative reduction in the failure strain. Finite element modeling of the composite compression showed that strain concentration near large SiC particles is the main reason for low ductility of the composite. The development of those lightweight hybrid composites with high mechanical properties has a high potential to be used for automotive and aerospace applications.

Reactions of N,3-diarylpropiolamides with arenes under superelectrophilic activation: synthesis of 4,4-diaryl-3,4-dihydroquinolin-2(1H-ones and their derivatives

Directory of Open Access Journals (Sweden)

Larisa Yu. Gurskaya

2016-05-01

Full Text Available The reaction of 3-aryl-N-(arylpropiolamides with arenes in TfOH at room temperature for 0.5 h led to 4,4-diaryl-3,4-dihydroquinolin-2-(1H-ones in yields of 44–98%. The obtained dihydroquinolinones were further transformed into the corresponding N-acyl or N-formyl derivatives. For the latter, the superelectrophilic activation of the N-formyl group by TfOH in the reaction with benzene resulted in the formation of N-(diphenylmethyl-substituted dihydroquinolinones.

Electrochemical behavior of low phosphorus electroless Ni-P-Si3N4 composite coatings

International Nuclear Information System (INIS)

Balaraju, J.N.; Ezhil Selvi, V.; Rajam, K.S.

2010-01-01

In the present investigation the electroless Ni-P-Si 3 N 4 composite coatings were prepared by using a low phosphorus bath containing submicron size silicon nitride particles. Plain Ni-P deposits were also prepared for comparison. The phosphorus contents present in electroless plain Ni-P and Ni-P-Si 3 N 4 coatings are 3.7 and 3.4 wt.%, respectively. Scanning electron microscope (SEM) images obtained for composite coatings (cross-sections) showed that the second phase particles are uniformly distributed throughout the thickness of the deposits. It was found that nodularity increased with particle codeposition in Ni-P matrix. To find out the electrochemical behavior of plain Ni-P and composite coatings, potentiodynamic polarization and electrochemical impedance (EIS) studies were carried out in 3.5 wt.% sodium chloride solution in non-deaerated condition. Second phase particle incorporation in Ni-P matrix indicated a marginal decrease in corrosion current density compared to the plain Ni-P deposits. This was further confirmed by EIS studies and SEM analysis of the corroded samples.

Impact of SiO2 on Al–Al thermocompression wafer bonding

International Nuclear Information System (INIS)

Malik, Nishant; Finstad, Terje G; Schjølberg-Henriksen, Kari; Poppe, Erik U; Taklo, Maaike M V

2015-01-01

Al–Al thermocompression bonding suitable for wafer level sealing of MEMS devices has been investigated. This paper presents a comparison of thermocompression bonding of Al films deposited on Si with and without a thermal oxide (SiO 2 film). Laminates of diameter 150 mm containing device sealing frames of width 200 µm were realized. The wafers were bonded by applying a bond force of 36 or 60 kN at bonding temperatures ranging from 300–550 °C for bonding times of 15, 30 or 60 min. The effects of these process variations on the quality of the bonded laminates have been studied. The bond quality was estimated by measurements of dicing yield, tensile strength, amount of cohesive fracture in Si and interfacial characterization. The mean bond strength of the tested structures ranged from 18–61 MPa. The laminates with an SiO 2 film had higher dicing yield and bond strength than the laminates without SiO 2 for a 400 °C bonding temperature. The bond strength increased with increasing bonding temperature and bond force. The laminates bonded for 30 and 60 min at 400 °C and 60 kN had similar bond strength and amount of cohesive fracture in the bulk silicon, while the laminates bonded for 15 min had significantly lower bond strength and amount of cohesive fracture in the bulk silicon. (paper)

Reactions of R(2)P-P(SiMe(3))Li with [(R'(3)P)(2)PtCl(2)]. A general and efficient entry to phosphanylphosphinidene complexes of platinum. Syntheses and structures of [(eta(2)-P=(i)Pr(2))Pt(p-Tol(3)P)(2)], [(eta(2)-P=(t)Bu(2))Pt(p-Tol(3)P)(2)], [{eta(2)-P=(N(i)Pr(2))(2)}Pt(p-Tol(3)P)(2)] and [{(Et(2)PhP)(2)Pt}(2)P(2)].

Science.gov (United States)

Domańska-Babul, Wioleta; Chojnacki, Jaroslaw; Matern, Eberhard; Pikies, Jerzy

2009-01-07

The reactions of lithium derivatives of diphosphanes R(2)P-P(SiMe(3))Li (R = (t)Bu, (i)Pr, Et(2)N and (i)Pr(2)N) with [(R'(3)P)(2)PtCl(2)] (R'(3)P = Et(3)P, Et(2)PhP, EtPh(2)P and p-Tol(3)P) proceed in a facile manner to afford side-on bonded phosphanylphosphinidene complexes of platinum [(eta(2)-P=R(2))Pt(PR'(3))(2)]. The related reactions of Ph(2)P-P(SiMe(3))Li with [(R'(3)P)(2)PtCl(2)] did not yield [(eta(2)-P=PPh(2))Pt(PR'(3))(2)] and resulted mainly in the formation of [{(R'(3)P)(2)Pt}(2)P(2)], Ph(2)P-PLi-PPh(2), (Me(3)Si)(2)PLi and (Me(3)Si)(3)P. Crystallographic data are reported for the compounds [(eta(2)-P=R(2))Pt(p-Tol(3)P)(2)] (R = (t)Bu, (i)Pr, ((i)Pr(2)N)(2)P) and for [{(Et(2)PhP)(2)Pt}(2)P(2)].

One-Step Preparation of Blue-Emitting (La,Ca)Si3(O,N)5:Ce3+ Phosphors for High-Color Rendering White Light-Emitting Diodes

Science.gov (United States)

Yaguchi, Atsuro; Suehiro, Takayuki; Sato, Tsugio; Hirosaki, Naoto

2011-02-01

Highly phase-pure (La,Ca)Si3(O,N)5:Ce3+ blue-emitting phosphors were successfully synthesized via the one-step solid-state reaction from the system La2O3-CaO-CeO2-Si3N4. The synthesized (La,Ca)Si3(O,N)5:Ce3+ exhibits tunable blue broadband emission with the dominant wavelength of 466-479 nm and the external quantum efficiency up to ˜45% under 380 nm near-UV (NUV) excitation. Spectral simulations of the trichromatic white light-emitting diodes (LEDs) using (La,Ca)Si3(O,N)5:Ce3+ demonstrated markedly higher color rendering index Ra values of 93-95, compared to 76-90 attained by the systems using a conventional BAM:Eu2+ phosphor or InGaN blue LED. The present achievement indicates the promising applicability of (La,Ca)Si3(O,N)5:Ce3+ as a blue luminescent source for NUV-converting high-color rendering white LEDs.

Computational Study of Pincer Iridium Catalytic Systems: C-H, N-H, and C-C Bond Activation and C-C Coupling Reactions

Science.gov (United States)

Zhou, Tian

Computational chemistry has achieved vast progress in the last decades in the field, which was considered to be only experimental before. DFT (density functional theory) calculations have been proven to be able to be applied to large systems, while maintaining high accuracy. One of the most important achievements of DFT calculations is in exploring the mechanism of bond activation reactions catalyzed by organometallic complexes. In this dissertation, we discuss DFT studies of several catalytic systems explored in the lab of Professor Alan S. Goldman. Headlines in the work are: (1) (R4PCP)Ir alkane dehydrogenation catalysts are highly selective and different from ( R4POCOP)Ir catalysts, predicting different rate-/selectivity-determining steps; (2) The study of the mechanism for double C-H addition/cyclometalation of phenanthrene or biphenyl by (tBu4PCP)Ir(I) and ( iPr4PCP)Ir illustrates that neutral Ir(III) C-H addition products can undergo a very facile second C-H addition, particularly in the case of sterically less-crowded Ir(I) complexes; (3) (iPr4PCP)Ir pure solid phase catalyst is highly effective in producing high yields of alpha-olefin products, since the activation enthalpy for dehydrogenation is higher than that for isomerization via an allyl pathway; higher temperatures favor the dehydrogenation/isomerization ratio; (4) (PCP)Ir(H)2(N2H4) complex follows a hydrogen transfer mechanism to undergo both dehydrogenation to form N 2 and H2, as well as hydrogen transfer followed by N-N bond cleavage to form NH3, N2, and H2; (5) The key for the catalytic effect of solvent molecule in CO insertion reaction for RMn(CO)5 is hydrogen bond assisted interaction. The basicity of the solvent determines the strength of the hydrogen bond interaction during the catalytic path and determines the catalytic power of the solvent; and (6) Dehydrogenative coupling of unactivated C-H bonds (intermolecular vinyl-vinyl, intramolecular vinyl-benzyl) is catalyzed by precursors of the