Compositional and surface characterization of HULIS by UV-Vis, FTIR, NMR and XPS: Wintertime study in Northern India

NASA Astrophysics Data System (ADS)

Kumar, Varun; Goel, Anubha; Rajput, Prashant

2017-09-01

This study (first attempt) characterizes HULIS (Humic Like Substances) in wintertime aerosols (n = 12 during day and nighttime each) from Indo-Gangetic Plain (IGP, at Kanpur) by using various state-of-the art techniques such as UV-VIS, FTIR, 1H NMR and XPS. Based on UV-Vis analysis the absorption coefficient at 365 nm (babs-365) of HULIS was found to average at 13.6 and 28.8 Mm-1 during day and nighttime, respectively. Relatively high babs-365 of HULIS during the nighttime is attributed to influence of fog-processing. However, the power fit of UV-Vis spectrum provided near similar AAE (absorption Angstrom exponent) value of HULIS centering at 4.9 ± 1.4 and 5.1 ± 1.3 during daytime and nighttime, respectively. FTIR spectra and its double derivative revealed the presence of various functional groups viz. alcohols, ketones aldehydes, carboxylic acids as well as unsaturated and saturated carbon bonds. 1H NMR spectroscopy was applied to quantify relative percentage of various types of hydrogen atoms contained in HULIS, whereas XPS technique provided information on surface composition and oxidation states of various elements present. A significantly high abundance of H‒C‒O group has been observed in HULIS (based on 1H NMR); 41.4± 2.7% and 30.9± 2.4% in day and nighttime, respectively. However, aromatic protons (Ar-H) were higher in nighttime samples (19.3± 1.8%) as compared to that in daytime samples (7.5 ± 1.9). XPS studies revealed presence of various species on the surface of HULIS samples. Carbon existed in 7 different chemical states while total nitrogen and sulfur exhibited 3 and 2 different oxidation states (respectively) on the surface of HULIS. This study reports structural information and absorption properties of HULIS which has implications to their role as cloud condensation nuclei and atmospheric direct radiative forcing.

A Study of Ziegler–Natta Propylene Polymerization Catalysts by Spectroscopic Methods

PubMed Central

Tkachenko, Olga P.; Kucherov, Alexey V.; Kustov, Leonid M.; Virkkunen, Ville; Leinonen, Timo; Denifl, Peter

2017-01-01

Ziegler–Natta polymerization catalysts were characterized by a complex of surface- and bulk-sensitive methods (DRIFTS, XPS, ESR, and XAS = XANES + EXAFS). A diffuse-reflectance Fourier-transform IR spectroscopy (DRIFTS) study showed the presence of strong Lewis acid sites in different concentrations and absence of strong basic sites in the polymerization catalysts. X-ray photoelectron spectroscopy (XPS), electron-spin resonance (ESR), and (X-ray absorption near-edge structure (XANES) analysis revealed the presence of Ti4+, Ti3+, Ti2+, and Ti1+ species in the surface layers and in the bulk of catalysts. The samples under study differ drastically in terms of the number of ESR-visible paramagnetic sites. The EXAFS study shows the presence of a Cl atom as a nearest neighbor of the absorbing Ti atom. PMID:28772850

The effect of Cr substitution on the structural, electronic and magnetic properties of pulsed laser deposited NiFe2O4 thin films

NASA Astrophysics Data System (ADS)

Panwar, Kalpana; Tiwari, Shailja; Bapna, Komal; Heda, N. L.; Choudhary, R. J.; Phase, D. M.; Ahuja, B. L.

2017-01-01

We have studied the structural, electronic and magnetic properties of pulsed laser deposited thin films of Ni1-xCrxFe2O4 (x=0.02 and 0.05) on Si (111) and Si (100) substrates. The films reveal single phase, polycrystalline structure with larger grain size on Si (111) substrate than that on Si (100) substrate. Contrary to the expected inverse spinel structure, x-ray photoemission (XPS) studies reveal the mixed spinel structure. XPS results suggest that Ni and Fe ions exist in 2+ and 3+ states, respectively, and they exist in tetrahedral as well as octahedral sites. The deviation from the inverse spinel leads to modified magnetic properties. It is observed that saturation magnetization drastically drops compared to the expected saturation value for inverse spinel structure. Strain in the films and lattice distortion produced by the Cr doping also appear to influence the magnetic properties.

Application of surface analysis to solve problems of wear

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1981-01-01

Results are presented for the use of surface analytical tools including field ion microscopy, Auger emission spectroscopy analysis (AES), cylindrical mirror Auger analysis and X-ray photoelectron spectroscopy (XPS). Data from the field ion microscope reveal adhesive transfer (wear) at the atomic level with the formation of surface compounds not found in the bulk, and AES reveals that this transfer will occur even in the presence of surface oxides. Both AES and XPS reveal that in abrasive wear with silicon carbide and diamond contacting the transition metals, the surface and the abrasive undergo a chemical or structural change which effects wear. With silicon carbide, silicon volatilizes leaving behind a pseudo-graphitic surface and the surface of diamond is observed to graphitize.

Surface modification of EPDM rubber by plasma treatment.

PubMed

Grythe, Kai Frode; Hansen, Finn Knut

2006-07-04

The effect of argon, oxygen, and nitrogen plasma treatment of solvent cast EPDM rubber films has been investigated by means of atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and surface energy measurements. Plasma treatment leads to changes in the surface energy from 25 to 70 mN/m. Treatment conditions influenced both the changes in surface energy and the stability, and it became more difficult to obtain good contact angle measurements after longer (> ca. 4 min) treatment times, probably because of an increasingly uneven surface structure. XPS analyses revealed that up to 20 at. % oxygen can be easily incorporated and that variations of approximately 5% can be controlled by the plasma conditions. Oxygen was mainly found in hydroxyl groups, but also as carbonyl and carboxyl. XPS analyses showed more stable surfaces than expected from contact angles, probably because XPS analysis is less surface sensitive than contact angle measurements. AFM measurements revealed different surface structures with the three gases. The surface roughness increased generally with treatment time, and dramatic changes could be observed at longer times. At short times, surface energy changes were much faster than the changes in surface structure, showing that plasma treatment conditions can be utilized to tailor both surface energies and surface structure of EPDM rubber.

Transcription analysis of pilS and xpsEL genes from Xylella fastidiosa.

PubMed

Coltri, Patricia P; Rosato, Yoko B

2005-04-01

Xylella fastidiosa is a xylem-limited phytopathogen responsible for diseases in several plants such as citrus and coffee. Analysis of the bacterial genome revealed some putative pathogenicity-related genes that could help to elucidate the molecular mechanisms of plant-pathogen interactions. In the present work, the transcription of three genes of the bacterium, grown in defined and rich media and also in media containing host plant extracts (sweet orange, 'ponkan' and coffee) was analyzed by RT-PCR. The pilS gene, which encodes a sensor histidine kinase responsible for the biosynthesis of fimbriae, was transcribed when the bacterium was grown in more complex media such as PW and in medium containing plant extracts. The xps genes (xpsL and xpsE) which are related to the type II secretion system were also detected when the bacterium was grown in rich media and media with 'ponkan' and coffee extracts. It was thus observed that pilS and xpsEL genes of X. fastidiosa can be modulated by environmental factors and their expression is dependent on the nutritional status of the growth medium.

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

Unuigbe, David M.; Harting, Margit; Jonah, Emmanuel O.

The presence of native oxide on the surface of silicon nanoparticles is known to inhibit charge transport on the surfaces. Scanning electron microscopy (SEM) studies reveal that the particles in the printed silicon network have a wide range of sizes and shapes. High-resolution transmission electron microscopy reveals that the particle surfaces have mainly the (111)- and (100)-oriented planes which stabilizes against further oxidation of the particles. X-ray absorption spectroscopy (XANES) and X-ray photoelectron spectroscopy (XPS) measurements at the O 1s-edge have been utilized to study the oxidation and local atomic structure of printed layers of silicon nanoparticles which were milledmore » for different times. XANES results reveal the presence of the +4 (SiO 2) oxidation state which tends towards the +2 (SiO) state for higher milling times. Si 2pXPS results indicate that the surfaces of the silicon nanoparticles in the printed layers are only partially oxidized and that all three sub-oxide, +1 (Si 2O), +2 (SiO) and +3 (Si 2O 3), states are present. The analysis of the change in the sub-oxide peaks of the silicon nanoparticles shows the dominance of the +4 state only for lower milling times.« less

Impression of plasma voltage on growth of α-V2O5 nanostructured thin films

NASA Astrophysics Data System (ADS)

Sharma, Rabindar Kumar; Kumar, Prabhat; Reddy, G. B.

2015-06-01

In this communication, we synthesized vanadium pentoxide (α-V2O5) nanostructured thin films (NSTs) accompanied with nanoflakes/ nanoplates on the Ni-coated glass substrates employing plasma assisted sublimation process (PASP) as a function of plasma voltage (Vp). The effect of plasma voltage on structural, morphological, compositional, and vibrational properties have been studied systematically. The structural analysis divulged that all films deposited at different Vp have pure orthorhombic phase, no impurity phase is detected under resolution limit of XRD and XPS. The morphological studies of samples is carried out by SEM, revealed that features as well as alignment of V2O5 NSTs is greatly monitored by Vp and the film possessing the best features is obtained at 2500volt. In addition, XPS results reveal that V5+ oxidation state is the most prominent state in sample V2, which represents better stoichiometric nature of film. The vibrational study of all samples is performed by FTIR and strongly support the XRD observations. All the results are in consonance with each other.

In Situ X-Ray Photoelectron Spectroscopy of Model Catalysts: At the Edge of the Gap

NASA Astrophysics Data System (ADS)

Blomberg, S.; Hoffmann, M. J.; Gustafson, J.; Martin, N. M.; Fernandes, V. R.; Borg, A.; Liu, Z.; Chang, R.; Matera, S.; Reuter, K.; Lundgren, E.

2013-03-01

We present high-pressure x-ray photoelectron spectroscopy (HP-XPS) and first-principles kinetic Monte Carlo study addressing the nature of the active surface in CO oxidation over Pd(100). Simultaneously measuring the chemical composition at the surface and in the near-surface gas phase, we reveal both O-covered pristine Pd(100) and a surface oxide as stable, highly active phases in the near-ambient regime accessible to HP-XPS. Surprisingly, no adsorbed CO can be detected during high CO2 production rates, which can be explained by a combination of a remarkably short residence time of the CO molecule on the surface and mass-transfer limitations in the present setup.

Reference binding energies of transition metal carbides by core-level x-ray photoelectron spectroscopy free from Ar+ etching artefacts

NASA Astrophysics Data System (ADS)

Greczynski, G.; Primetzhofer, D.; Hultman, L.

2018-04-01

We report x-ray photoelectron spectroscopy (XPS) core level binding energies (BE's) for the widely-applicable groups IVb-VIb transition metal carbides (TMCs) TiC, VC, CrC, ZrC, NbC, MoC, HfC, TaC, and WC. Thin film samples are grown in the same deposition system, by dc magnetron co-sputtering from graphite and respective elemental metal targets in Ar atmosphere. To remove surface contaminations resulting from exposure to air during sample transfer from the growth chamber into the XPS system, layers are either (i) Ar+ ion-etched or (ii) UHV-annealed in situ prior to XPS analyses. High resolution XPS spectra reveal that even gentle etching affects the shape of core level signals, as well as BE values, which are systematically offset by 0.2-0.5 eV towards lower BE. These destructive effects of Ar+ ion etch become more pronounced with increasing the metal atom mass due to an increasing carbon-to-metal sputter yield ratio. Systematic analysis reveals that for each row in the periodic table (3d, 4d, and 5d) C 1s BE increases from left to right indicative of a decreased charge transfer from TM to C atoms, hence bond weakening. Moreover, C 1s BE decreases linearly with increasing carbide/metal melting point ratio. Spectra reported here, acquired from a consistent set of samples in the same instrument, should serve as a reference for true deconvolution of complex XPS cases, including multinary carbides, nitrides, and carbonitrides.

UV irradiation study of a tripeptide isolated in an argon matrix: A tautomerism process evidenced by infrared and X-ray photoemission spectroscopies

NASA Astrophysics Data System (ADS)

Mateo-Marti, E.; Pradier, C. M.

2013-05-01

Matrix isolation is a powerful tool for studying photochemical processes occurring in isolated molecules. In this way, we characterized the chemical modifications occurring within a tri peptide molecule, IGF, when exposed to the influence of Ultraviolet (UV) irradiation. This paper first describes the successful formation of the tripeptide (IGF) argon matrix under vacuum conditions, followed by the in situ UV irradiation and characterization of the molecular matrix reactivity after UV-irradiation. These studies have been performed by combining two complementary spectroscopic techniques, Fourier-Transform Reflexion Absorption Spectroscopy (FT-IRRAS) and X-ray Photoelectron Spectroscopy (XPS). The IR spectra of the isolated peptide-matrix, before and after UV irradiation, revealed significant differences that could be associated either to a partial deprotonation of the molecule or to a tautomeric conversion of some amide bonds to imide ones on some peptide molecules. XPS analyses undoubtedly confirmed the second hypothesis; the combination of IRRAS and XPS results provide evidence that UV irradiation of peptides induces a chemical reaction, namely a shift of the double bond, meaning partial conversion from amide tautomer into an imidic acid tautomer.

Morphology and Chemical Composition of soot particles emitted by Wood-burning Cook-Stoves: a HRTEM, XPS and Elastic backscattering Studies.

NASA Astrophysics Data System (ADS)

Carabali-Sandoval, G. A., Sr.; Castro, T.; Peralta, O.; De la Cruz, W.; Días, J.; Amelines, O.; Rivera-Hernández, M.; Varela, A.; Muñoz-Muñoz, F.; Policroniades, R.; Murillo, G.; Moreno, E.

2014-12-01

The morphology, microstructure and the chemical composition on surface of soot particles were studied by using high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and elastic backscattering spectrometry. In order to obtain freshly soot particles emitted by home-made wood-burning cook stoves, copper grids for Transmission Electron Microscope (TEM) were placed on the last two of an 8-stages MOUDI cascade impactor. The analysis of HRTEM micrographs revealed the nanostructure and the particle size of soot particles. The XPS survey spectra show a large carbon peak around 285 eV and the oxygen signal at 533 eV. Some differences observed in the carbon/oxygen (C/O) ratio of the particles probably depend on the combustion process efficiency of each cook-stove analyzed. The C-1s XPS spectra show an asymmetric broad peak and other with low intensity that corresponds to sp2 and sp3hybridization, which were fitted with a convolution using Gaussian functions. Elastic backscattering technique allows a chemical elemental analysis of samples and confirms the presence of C, O and Si observed by XPS. Additionally, the morphological properties of soot aggregates were analyzed calculating the border-based fractal dimension (Df). Particles exhibit complex shapes with high values of Df. Also, real-time absorption (σabs) and scattering (σsct) coefficients of fine (with aerodynamic diameter < 2.5 µm) soot particles were measured. The trend in σabs and σsct indicate that the cooking process has two important combustion stages which varied in its flaming strength, being vigorous in the first stage and soft in the second one.

Electronic structure and fine structural features of the air-grown UNxOy on nitrogen-rich uranium nitride

NASA Astrophysics Data System (ADS)

Long, Zhong; Zeng, Rongguang; Hu, Yin; Liu, Jing; Wang, Wenyuan; Zhao, Yawen; Luo, Zhipeng; Bai, Bin; Wang, Xiaofang; Liu, Kezhao

2018-06-01

Oxide formation on surface of nitrogen-rich uranium nitride film/particles was investigated using X-ray photoelectron spectroscopy (XPS), auger electron spectroscopy (AES), aberration-corrected transmission electron microscopy (TEM), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) coupled with electron energy-loss spectroscopy (EELS). XPS and AES studies indicated that the oxidized layer on UN2-x film is ternary compound uranium oxynitride (UNxOy) in 5-10 nm thickness. TEM/HAADF-STEM and EELS studies revealed the UNxOy crystallizes in the FCC CaF2-type structure with the lattice parameter close to the CaF2-type UN2-x matrix. The work can provide further information to the oxidation mechanism of uranium nitride.

Auger electron diffraction study of the growth of Fe(001) films on ZnSe(001)

NASA Astrophysics Data System (ADS)

Jonker, B. T.; Prinz, G. A.

1991-03-01

The growth of Fe films on ZnSe(001) epilayers and bulk GaAs(001) substrates has been studied to determine the mode of film growth, the formation of the interface, and the structure of the overlayer at the 1-10 monolayer level. Auger electron diffraction (AED), x-ray photoelectron spectroscopy (XPS), and reflection high-energy electron diffraction data are obtained for incremental deposition of the Fe(001) overlayer. The coverage dependence of the AED forward scattering peaks reveals a predominantly layer-by-layer mode of film growth at 175 °C on ZnSe, while a more three-dimensional growth mode occurs on the oxide-desorbed GaAs(001) substrate. XPS studies of the semiconductor 3d levels indicate that the Fe/ZnSe interface is less reactive than the Fe/GaAs interface.

Investigation of nanoparticulate silicon as printed layers using scanning electron microscopy, transmission electron microscopy, X-ray absorption spectroscopy and X-ray photoelectron spectroscopy

DOE PAGES

Unuigbe, David M.; Harting, Margit; Jonah, Emmanuel O.; ...

2017-08-21

The presence of native oxide on the surface of silicon nanoparticles is known to inhibit charge transport on the surfaces. Scanning electron microscopy (SEM) studies reveal that the particles in the printed silicon network have a wide range of sizes and shapes. High-resolution transmission electron microscopy reveals that the particle surfaces have mainly the (111)- and (100)-oriented planes which stabilizes against further oxidation of the particles. X-ray absorption spectroscopy (XANES) and X-ray photoelectron spectroscopy (XPS) measurements at the O 1s-edge have been utilized to study the oxidation and local atomic structure of printed layers of silicon nanoparticles which were milledmore » for different times. XANES results reveal the presence of the +4 (SiO 2) oxidation state which tends towards the +2 (SiO) state for higher milling times. Si 2pXPS results indicate that the surfaces of the silicon nanoparticles in the printed layers are only partially oxidized and that all three sub-oxide, +1 (Si 2O), +2 (SiO) and +3 (Si 2O 3), states are present. The analysis of the change in the sub-oxide peaks of the silicon nanoparticles shows the dominance of the +4 state only for lower milling times.« less

Structural Studies of the Initial Stages of Fluoride Epitaxy on Silicon and GERMANIUM(111)

NASA Astrophysics Data System (ADS)

Denlinger, Jonathan David

The epitaxial growth of ionic insulators on semiconductor substrates is of interest due to fundamental issues of interface bonding and structure as well as to potential technological applications. The initial stages of Group IIa fluoride insulator growth on (111) Si and Ge substrates by molecular beam epitaxy are studied with the in situ combination of X-ray Photoelectron Spectroscopy (XPS) and Diffraction (XPD). While XPS probes the electronic structure, XPD reveals atomic structure. In addition, low energy electron diffraction (LEED) is used to probe surface order and a separate study using X-ray standing wave (XSW) fluorescence reveals interface cation bonding sites. Following the formation of a chemically-reacted interface layer in CaF_2 epitaxy on Si(111), the morphology of the subsequent bulk layers is found to be dependent on substrate temperature and incident flux rate. At temperatures >=600 ^circC a transition from three -dimensional island formation at low flux to laminar growth at higher flux is observed with bulk- and interface-resolved XPD. At lower substrate temperatures, laminar growth is observed at all fluxes, but with different bulk nucleation behavior due to changes in the stoichiometry of the interface layer. This new observation of kinetic effects on the initial nucleation in CaF_2 epitaxy has important ramifications for the formation of thicker heterostructures for scientific or device applications. XPS and XPD are also used to identify for the first time, surface core-level species of Ca and F, and a secondary interface-shifted F Auger component arising from a second-layer site directly above interface-layer Ca atoms. The effects of lattice mismatch (from -3% to 8%) are investigated with various growths of Ca_{rm x}Sr _{rm 1-x}F_2 on Si and Ge (111) substrates. Triangulation of (111) and (220) XSW indicates a predominance of 3-fold hollow Sr bonding sites coexisting with 4-fold top sites for monolayers of SrF_2 on Si. XSW and LEED reveal a lateral discommensuration of the overlayer for lattice mismatches of >5% relative to the substrate. XPD also reveals a transition from single - to mixed-domains of overlayer crystallographic orientation for mismatches >=3.5%.

Impression of plasma voltage on growth of α-V{sub 2}O{sub 5} nanostructured thin films

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

Sharma, Rabindar Kumar, E-mail: rkrksharma6@gmail.com; Kumar, Prabhat; Reddy, G. B.

2015-06-24

In this communication, we synthesized vanadium pentoxide (α-V{sub 2}O{sub 5}) nanostructured thin films (NST{sub s}) accompanied with nanoflakes/ nanoplates on the Ni-coated glass substrates employing plasma assisted sublimation process (PASP) as a function of plasma voltage (V{sub p}). The effect of plasma voltage on structural, morphological, compositional, and vibrational properties have been studied systematically. The structural analysis divulged that all films deposited at different V{sub p} have pure orthorhombic phase, no impurity phase is detected under resolution limit of XRD and XPS. The morphological studies of samples is carried out by SEM, revealed that features as well as alignment ofmore » V{sub 2}O{sub 5} NST{sub s} is greatly monitored by V{sub p} and the film possessing the best features is obtained at 2500volt. In addition, XPS results reveal that V{sup 5+} oxidation state is the most prominent state in sample V{sub 2}, which represents better stoichiometric nature of film. The vibrational study of all samples is performed by FTIR and strongly support the XRD observations. All the results are in consonance with each other.« less

Effects of rare earth doping on multi-core iron oxide nanoparticles properties

NASA Astrophysics Data System (ADS)

Petran, Anca; Radu, Teodora; Borodi, Gheorghe; Nan, Alexandrina; Suciu, Maria; Turcu, Rodica

2018-01-01

New multi-core iron oxide magnetic nanoparticles doped with rare earth metals (Gd, Eu) were obtained by a one step synthesis procedure using a solvothermal method for potential biomedical applications. The obtained clusters were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray microanalysis (EDX), X-ray photoelectron spectroscopy (XPS) and magnetization measurements. They possess high colloidal stability, a saturation magnetization of up to 52 emu/g, and nearly spherical shape. The presence of rare earth ions in the obtained samples was confirmed by EDX and XPS. XRD analysis proved the homogeneous distribution of the trivalent rare earth ions in the inverse-spinel structure of magnetite and the increase of crystal strain upon doping the samples. XPS study reveals the valence state and the cation distribution on the octahedral and tetrahedral sites of the analysed samples. The observed shift of the XPS valence band spectra maximum in the direction of higher binding energies after rare earth doping, as well as theoretical valence band calculations prove the presence of Gd and Eu ions in octahedral sites. The blood protein adsorption ability of the obtained samples surface, the most important factor of the interaction between biomaterials and body fluids, was assessed by interaction with bovine serum albumin (BSA). The rare earth doped clusters surface show higher afinity for binding BSA. In vitro cytotoxicity test results for the studied samples showed no cytotoxicity in low and medium doses, establishing a potential perspective for rare earth doped MNC to facilitate multiple therapies in a single formulation for cancer theranostics.

Study of the kinetics and mechanism of the thermal nitridation of SiO2

NASA Technical Reports Server (NTRS)

Vasquez, R. P.; Madhukar, A.; Grunthaner, F. J.; Naiman, M. L.

1985-01-01

X-ray photoelectron spectroscopy (XPS) has been used to study the nitridation time and temperature dependence of the nitrogen distribution in thermally nitrided SiO2 films. The XPS data show that the maximum nitrogen concentration near the (SiO(x)N(y)/Si interface is initially at the interface, but moves 20-25 A away from the interface with increasing nitridation time. Computer modeling of the kinetic processes involved is carried out and reveals a mechanism in which diffusing species, initially consisting primarily of nitrogen, react with the substrate, followed by formation of the oxygen-rich oxynitride due to reaction of the diffusing oxygen displaced by the slower nitridation of the SiO2. The data are consistent with this mechanism provided the influence of the interfacial strain on the nitridation and oxidation kinetics is explicitly accounted for.

XPS and 31P NMR inquiry of Eu3+-induced structural modification in SnO-containing phosphate glass

NASA Astrophysics Data System (ADS)

Jiménez, José A.; Fachini, Esteban Rosim; Zhao, Chunqing

2018-07-01

The influence of Eu3+ doping on the structural properties of SnO-containing phosphate glass has been investigated by X-ray photoelectron spectroscopy (XPS) and 31P nuclear magnetic resonance (NMR) spectroscopy. Oxygen 1s XPS data indicates that the Eu3+ doping results in a higher concentration of non-bridging oxygens in the glass matrix, whereas 31P NMR shows an increase in the terminal phosphate chain tetrahedral units, i.e. the amount of Q1 sites with only one bridging oxygen. Accordingly, both techniques agree with a depolymerization effect induced by the Eu3+ ions. Further, XPS reveals that together with the Eu3+ doping, the presence of Sn4+ is supported while the presence of Eu2+ is also indicated. The structural changes are then indicated to be a consequence of redox chemistry between Sn2+ and Eu3+ promoting a transition of tin from Sn2+ with a role as network former to Sn4+ acting as network modifier in the glass system.

The effect of simulated low earth orbit radiation on polyimides (UV degradation study)

NASA Technical Reports Server (NTRS)

Forsythe, John S.; George, Graeme A.; Hill, David J. T.; Odonnell, James H.; Pomery, Peter J.; Rasoul, Firas A.

1995-01-01

UV degradation of polyimide films in air and vacuum were studied using UV-visible, ESR, FTIR, and XPS spectroscopies. The UV-visible spectra of polyimide films showed a blue shift in the absorption compared to Kapton. This behavior was attributed to the presence of bulky groups and kinks along the polymer chains which disrupt the formation of a charge transfer complex. The UV-visible spectra showed also that UV irradiation of polyimides result extensively in surface degradation, leaving the bulk of the polymer intact. ESR spectra of polyimides irradiated in vacuum revealed the formation of stable carbon-centered radicals which give a singlet ESR spectrum, while polyimides irradiated in air produced an asymmetric signal shifted to a lower magnetic field, with a higher g value and line width. This signal was attributed to oxygen-cenetered radicals of peroxy and/or alkoxy type. The rate of radical formation in air was two fold higher than for vacuum irradiation, and reached a plateau after a short time. This suggests a continuous depletion of radicals on the surface via an ablative degradation process. FTIR, XPS, and weight loss studies supported this postulate. An XPS study of the surface indicated a substantial increase in the surface oxidation after irradiation in air. The sharp increase in the C-O binding energy peak relative to the C-C peak was believed to be associated with an aromatic ring opening reaction.

Preparation of γ-LiV2O5 from polyoxovanadate cluster Li7[V15O36(CO3)] as a high-performance cathode material and its reaction mechanism revealed by operando XAFS

NASA Astrophysics Data System (ADS)

Wang, Heng; Isobe, Jin; Shimizu, Takeshi; Matsumura, Daiju; Ina, Toshiaki; Yoshikawa, Hirofumi

2017-08-01

γ-phase LiV2O5, which shows superior electrochemical performance as cathode material in Li-ion batteries, was prepared by annealing the polyoxovanadate cluster Li7 [V15O36(CO3)]. The reaction mechanism was studied using operando X-ray absorption fine structure (XAFS), powder X-ray diffraction (PXRD), and X-ray photoelectron spectroscopy (XPS) analyses. The X-ray absorption near edge structure (XANES) and XPS results reveal that γ-LiV2O5 undergoes two-electron redox reaction per V2O5 pyramid unit, resulting in a large reversible capacity of 260 Ah/kg. The extended X-ray absorption fine structure (EXAFS) and PXRD analyses also suggest that the V-V distance slightly increases, due to the reduction of V5+ to V4+ during Li ion intercalation as the material structure is maintained. As a result, γ-LixV2O5 shows highly reversible electrochemical reaction with x = 0.1-1.9.

Influence of heat treatment temperature on the morphological and structural aspects of reticulated vitreous carbon used in polyaniline electrosynthesis

NASA Astrophysics Data System (ADS)

Gonçalves, E. S.; Dalmolin, C.; Biaggio, S. R.; Nascente, P. A. P.; Rezende, M. C.; Ferreira, N. G.

2007-08-01

Reticulated vitreous carbon (RVC) was obtained from different heat treatment temperature (HTT), in the range from 700 up to 2000 °C, and used as a substrate for polyaniline growth from electrosynthesis. The influence of HTT on RVC chemical surface was studied by X-ray photoelectron spectroscopy (XPS) and correlated to electrochemical parameters used in the electrosynthesis. XPS analyses have shown that RVC heteroatoms decrease as HTT increases. The results reveal the migration of chemical bonds from oxidized carbon forms towards carbon atoms as the unique final product. Cyclic voltammetry, electrochemical impedance spectroscopy, and stability test of polyaniline films were performed from oxidized and non-oxidized RVC substrates. Cyclic voltammetry in 0.5 mol L -1 H 2SO 4 revealed higher capacitance for the RVC treated at 1000 °C and oxidized in a hot H 2SO 4 solution. The charge accumulation after RVC chemical treatment has increased around ten times. The lowest electric resistivities and impedances were obtained for the RVC treated at 2000 °C, which also showed the highest polyaniline stability.

Cyclic fatigue resistance of XP-endo Shaper compared with different nickel-titanium alloy instruments.

PubMed

Elnaghy, Amr; Elsaka, Shaymaa

2018-04-01

The aims of this study were to assess and compare the resistance to cyclic fatigue of XP-endo Shaper (XPS; FKG Dentaire, La Chaux-de-Fonds, Switzerland) instruments with TRUShape (TRS; Dentsply Tulsa Dental Specialties, Tulsa, OK, USA), HyFlex CM (HCM; Coltene, Cuyahoga Falls, OH, USA), Vortex Blue (VB; Dentsply Tulsa Dental Specialties), and iRace (iR; FKG Dentaire) nickel-titanium rotary instruments at body temperature. Size 30, 0.01 taper of XPS, size 30, 0.04 taper of HCM, VB, iR, and size 30, 0.06 taper of TRS instruments were immersed in saline at 37 ± 1 °C during cyclic fatigue testing. The instruments were tested with 60° angle of curvature and a 3-mm radius of curvature. The number of cycles to failure (NCF) was calculated and the length of the fractured segment was measured. Fractographic examination of the fractured surface was performed using a scanning electron microscope. The data were analyzed statistically using Kruskal-Wallis H test and Mann-Whitney U tests. Statistical significance was set at P < 0.05. XPS had a significantly greater NCF compared with the other instruments (P < 0.001). The topographic appearance of the fracture surfaces of tested instruments revealed ductile fracture of cyclic fatigue failure. XPS instruments exhibited greater cyclic fatigue resistance compared with the other tested instruments. XP-endo Shaper instruments could be used more safely in curved canals due to their higher fatigue resistance.

Effects of Mn Ion Implantation on XPS Spectroscopy of GaN Thin Films

NASA Astrophysics Data System (ADS)

Majid, Abdul; Ahmad, Naeem; Rizwan, Muhammad; Khan, Salah Ud-Din; Ali, Fekri Abdulraqeb Ahmed; Zhu, Jianjun

2018-02-01

Gallium nitride (GaN) thin film was deposited onto a sapphire substrate and then implanted with 250 keV Mn ions at two different doses of 2 × 1016 ions/cm2 and 5 × 1016 ions/cm2. The as-grown and post-implantation-thermally-annealed samples were studied in detail using x-ray photoelectron spectroscopy (XPS). The XPS peaks of Ga 3 d, Ga 2 p, N 1 s, Mn 2 p and C 1 s were recorded in addition to a full survey of the samples. The doublet peaks of Ga 2 p for pure GaN were observed blue-shifted when compared with elemental Ga, and appeared further shifted to higher energies for the implanted samples. These observations point to changes in the bonds and the chemical environment of the host as a result of ion implantation. The results revealed broadening of the N 1 s peak after implantation, which is interpreted in terms of the presence of N-Mn bonds in addition to N-Ga bonds. The XPS spectra of Mn 2 p recorded for ion-implanted samples indicated splitting of Mn 2 p 1/2 and Mn 2 p 3/2 peaks higher than that for metallic Mn, which helps rule out the possibility of clustering and points to substitutional doping of Mn. These observations provide a framework that sheds light on the local environment of the material for understanding the mechanism of magnetic exchange interactions in Mn:GaN based diluted magnetic semiconductors.

Evolution of Eu valence and superconductivity in layered Eu0.5La0.5FBiS2 -xSex system

NASA Astrophysics Data System (ADS)

Mizuguchi, Y.; Paris, E.; Wakita, T.; Jinno, G.; Puri, A.; Terashima, K.; Joseph, B.; Miura, O.; Yokoya, T.; Saini, N. L.

2017-02-01

We have studied the effect of Se substitution on Eu valence in a layered Eu0.5La0.5FBiS2 -xSex superconductor using a combined analysis of x-ray absorption near-edge structure (XANES) and x-ray photoelectron spectroscopy (XPS) measurements. Eu L3-edge XANES spectra reveal that Eu is in the mixed valence state with coexisting Eu2 + and Eu3 +. The average Eu valence decreases sharply from ˜2.3 for x =0.0 to ˜2.1 for x =0.4 . Consistently, Eu 3 d XPS shows a clear decrease in the average valence by Se substitution. Bi 4 f XPS indicates that effective charge carriers in the BiCh2 (Ch = S, Se) layers are slightly increased by Se substitution. On the basis of the present results it has been discussed that the metallic character induced by Se substitution in Eu0.5La0.5FBiS2 -xSex is likely to be due to increased in-plane orbital overlap driven by reduced in-plane disorder that affects the carrier mobility.

Elucidating the resistance to failure under tribological tests of various boron-based films by XPS and ToF-SIMS

NASA Astrophysics Data System (ADS)

Spadaro, F.; Rossi, A.; Lainé, E.; Woodward, P.; Spencer, N. D.

2017-12-01

Tribotests performed on boron-based thermal films have revealed higher mechanical durability and lower wear coefficients compared to results from tests performed on boron-free thermal films. In the current study, in order to follow and identify the tribochemical reactions taking place in the contact regions, post-characterization has been carried out on the steel ball and on the steel disc. The techniques adopted to achieve this goal were small-area X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary-ion mass spectroscopy (ToF-SIMS). The contact areas have been investigated before and after failure of the thermal films, revealing thermal-film removal inside the wear track on the disc and the presence of a transfer film in the contact area on the steel ball following tribotesting. Furthermore, borate contributions in the deeper layers within the tribo-stressed area on the disc were revealed at the end of the tribotest. These procedures shed light on the tribomechanical and tribochemical reactions taking place in the contact region, on the ability of boron species to sustain tribological stress and provide mechanical stability, and on the mechanical-mixing processes occurring within the sliding contacts. The mass spectra collected before tribotesting on all thermal films suggest the presence of phosphate- and borate-containing structures.

Nanopatterning of metal-coated silicon surfaces via ion beam irradiation: Real time x-ray studies reveal the effect of silicide bonding

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

El-Atwani, Osman; Birck Nanotechnology Center, Purdue University, West Lafayette, Indiana 47907; Gonderman, Sean

We investigated the effect of silicide formation on ion-induced nanopatterning of silicon with various ultrathin metal coatings. Silicon substrates coated with 10 nm Ni, Fe, and Cu were irradiated with 200 eV argon ions at normal incidence. Real time grazing incidence small angle x-ray scattering (GISAXS) and x-ray fluorescence (XRF) were performed during the irradiation process and real time measurements revealed threshold conditions for nanopatterning of silicon at normal incidence irradiation. Three main stages of the nanopatterning process were identified. The real time GISAXS intensity of the correlated peaks in conjunction with XRF revealed that the nanostructures remain for amore » time period after the removal of the all the metal atoms from the sample depending on the binding energy of the metal silicides formed. Ex-situ XPS confirmed the removal of all metal impurities. In-situ XPS during the irradiation of Ni, Fe, and Cu coated silicon substrates at normal incidence demonstrated phase separation and the formation of different silicide phases that occur upon metal-silicon mixing. Silicide formation leads to nanostructure formation due the preferential erosion of the non-silicide regions and the weakening of the ion induced mass redistribution.« less

Application of surface analytical methods in thin film analysis

NASA Astrophysics Data System (ADS)

Wen, Xingu

Self-assembly and the sol-gel process are two promising methods for the preparation of novel materials and thin films. In this research, these two methods were utilized to prepare two types of thin films: self-assembled monolayers of peptides on gold and SiO2 sol-gel thin films modified with Ru(II) complexes. The properties of the resulting thin films were investigated by several analytical techniques in order to explore their potential applications in biomaterials, chemical sensors, nonlinear optics and catalysis. Among the analytical techniques employed in the study, surface analytical techniques, such as X-ray photoelectron spectroscopy (XPS) and grazing angle reflection absorption Fourier transform infrared spectroscopy (RA-FTIR), are particularly useful in providing information regarding the compositions and structures of the thin films. In the preparation of peptide thin films, monodisperse peptides were self-assembled on gold substrate via the N-terminus-coupled lipoic acid. The film compositions were investigated by XPS and agreed well with the theoretical values. XPS results also revealed that the surface coverage of the self-assembled films was significantly larger than that of the physisorbed films and that the chemisorption between the peptides and gold surface was stable in solvent. Studies by angle dependent XPS (ADXPS) and grazing angle RA-FTIR indicated that the peptides were on average oriented at a small angle from the surface normal. By using a model of orientation distribution function, both the peptide tilt angle and film thickness can be well calculated. Ru(II) complex doped SiO2 sol-gel thin films were prepared by low temperature sol-gel process. The ability of XPS coupled with Ar + ion sputtering to provide both chemical and compositional depth profile information of these sol-gel films was evaluated. This technique, together with UV-VIS and electrochemical measurements, was used to investigate the stability of Ru complexes in the composite films. The stability of Ru complexes with respect to dopant leaching was dependent on the film microstructures. Three methods aiming to improve the dopant stability were also explored. In addition, the ion exchange properties of the composite films, upon exposure to various ions in aqueous solutions, were investigated by XPS, and the ion exchange mechanism was elucidated.

Confirmation of Incorporation of Cu and Se Ions in Applied p- and n-Type-Doped Sb2S3 by Photoemission Spectroscopy

NASA Astrophysics Data System (ADS)

Validžić, Ivana Lj; Popović, Maja; Lojpur, Vesna; Bundaleski, Nenad; Rakočević, Zlatko

2018-04-01

The effect of incorporating copper (Cu) and selenium (Se) ions into stibnite (Sb2S3) lattice was investigated using x-ray photoelectron spectroscopy (XPS). The incorporation of Cu and Se ions was verified by comparing the XPS spectra of the undoped (amorphous Sb2S3), doped ( p and n-doped) and pure Se and Cu-acetate powders. The main photoelectron Cu 2p1/2 (951.8 eV) and Cu 2p3/2 (932.1 eV) lines derived from the Cu-doped and Cu-acetate powder samples were clearly observed, whereas in the undoped sample, none of the characteristic lines of Cu were detected. The Se Auger line (138.6 eV), the only line of Se which does not coincide with the lines of Sb and S, was successfully detected in an Se-doped XPS sample and the spectrum of pure Se, while Se in the undoped sample was not found. Further, the XPS measurements revealed the relative amounts of Cu and Se in antimony sulfide, as well as the oxidation state of copper incorporated into the matrix.

Incorporation of low energy activated nitrogen onto HOPG surface: Chemical states and thermal stability studies by in-situ XPS and Raman spectroscopy

NASA Astrophysics Data System (ADS)

Chandran, Maneesh; Shasha, Michal; Michaelson, Shaul; Hoffman, Alon

2016-09-01

In this paper we report the chemical states analysis of activated nitrogen incorporated highly oriented pyrolytic graphite (HOPG) surface under well-controlled conditions. Nitrogen incorporation is carried out by two different processes: an indirect RF nitrogen plasma and low energy (1 keV) N2+ implantation. Bonding configuration, concentration and thermal stability of the incorporated nitrogen species by aforesaid processes are systematically compared by in-situ X-ray photoelectron spectroscopy (XPS). Relatively large concentration of nitrogen is incorporated onto RF nitride HOPG surface (16.2 at.%), compared to N2+ implanted HOPG surface (7.7 at.%). The evolution of N 1s components (N1, N2, N3) with annealing temperature is comprehensively discussed, which indicates that the formation and reorganization of local chemical bonding states are determined by the process of nitridation and not by the prior chemical conditioning (i.e., amorphization or hydrogenation) of the HOPG surface. A combined XPS and Raman spectroscopy studies revealed that N2+ implantation process resulted in a high level of defects to the HOPG surface, which cannot be annealed-out by heat treatment up to 1000 °C. On the other hand, the RF nitrogen plasma process did not produce a high level of surface defects, while incorporating nearly the same amount of stable nitrogen species.

Scanning electron and atomic force microscopy, and raman and x-ray photoelectron spectroscopy characterization of near-isogenic soft and hard wheat kernels and corresponding flours

USDA-ARS?s Scientific Manuscript database

Atomic force microscopy (AFM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) are used to investigate vitreous (hard) and non-vitreous (soft) wheat kernels and their corresponding wheat flours. AFM data reveal two different microstructures. The vitreous kernel reveals a granular text...

Characterization of BN rich layer on ammonia treated Nextel{trademark}312 fibers

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

Khasgiwale, N.R.; Butler, E.P.; Tsakalakos, L.

A BN rich layer grown on Nextel{trademark}312 fibers by appropriate ammonia treatments was evaluated using various complimentary techniques including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM)/Parallel Electron Energy Loss Spectroscopy (PEELS in TEM). Three different ammonia treatments were studied. Ammonia treatment resulted in crystallization of the Nextel{trademark}312 fiber. The BN rich surface layer formed due to ammonia treatment was clearly detected in XPS and PEELS both before and after oxidation. The layer thickness was estimated to be between 5--10 nm. The layer was stable after oxidation treatment at 600 C formore » 100 hours. High resolution TEM observations of the fiber surface revealed a variable BN rich layer thickness. Patches of turbostratic BN were observed under certain conditions, however mostly the layer appeared to be amorphous.« less

Metallization of ultra-thin, non-thiol SAMs with flat-lying molecular units: Pd on 1, 4-dicyanobenzene.

PubMed

Eberle, Felix; Metzler, Martin; Kolb, Dieter M; Saitner, Marc; Wagner, Patrick; Boyen, Hans-Gerd

2010-09-10

Self-assembled monolayers of 1,4-dicyanobenzene on Au(111) electrodes are studied by cyclic voltammetry, in-situ STM and ex-situ XPS. High-resolution STM images reveal a long-range order of propeller-like assemblies each of which consists of three molecules, all lying flat on the gold substrate with the cyano groups oriented parallel to the metal surface. It is demonstrated that both functional groups can act as complexation sites for metal ions from solution. Surprisingly, such arrangements still allow the metal to be deposited on top of the molecules by electrochemical reduction despite the close vicinity to the Au surface. The latter is demonstrated by angle-resolved XPS which unequivocally shows that the metal indeed resides on top of the organic layer rather than underneath, despite the flat arrangement of the molecules.

Surface Modification of Polyimide for Improving Adhesion Strength by Inductively Coupled Plasma

NASA Astrophysics Data System (ADS)

Byun, Tae Joon; Kim, Sung Il; Kim, Youn Joon; Choi, Yoon Suk; Choi, In Sik; Setsuhara, Yuichi; Geon Han, Jeon

2009-08-01

This study examined the effect of an inductively coupled plasma (ICP) treatment using an argon and helium gas mixture on the adhesion between polyimide and a copper film. Optical emission spectroscopy (OES) of the ICP revealed the emission intensity of helium and argon at various intensities with the helium mixing ratio. The treated polyimide surface was analyzed using a contact angle analyzer, Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The contact angle and RMS roughness ranged from 66 to 31° and 2.3 to 4.1 nm, respectively. XPS showed an increase in C-O bonding. The highest peel strength was 0.43 kgf/cm at a 40% of helium mixing ratio, which contained the highest level of activate species. Overall, an ICP treatment of a polyimide surface with a 40% helium gas mixture improves the adhesion strength between copper and polyimide significantly.

Thickness Influence on In Vitro Biocompatibility of Titanium Nitride Thin Films Synthesized by Pulsed Laser Deposition

PubMed Central

Duta, Liviu; Stan, George E.; Popa, Adrian C.; Husanu, Marius A.; Moga, Sorin; Socol, Marcela; Zgura, Irina; Miculescu, Florin; Urzica, Iuliana; Popescu, Andrei C.; Mihailescu, Ion N.

2016-01-01

We report a study on the biocompatibility vs. thickness in the case of titanium nitride (TiN) films synthesized on 410 medical grade stainless steel substrates by pulsed laser deposition. The films were grown in a nitrogen atmosphere, and their in vitro cytotoxicity was assessed according to ISO 10993-5 [1]. Extensive physical-chemical analyses have been carried out on the deposited structures with various thicknesses in order to explain the differences in biological behavior: profilometry, scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction and surface energy measurements. XPS revealed the presence of titanium oxynitride beside TiN in amounts that vary with the film thickness. The cytocompatibility of films seems to be influenced by their TiN surface content. The thinner films seem to be more suitable for medical applications, due to the combined high values of bonding strength and superior cytocompatibility. PMID:28787846

Unraveling the Molecular Weight Dependence of Interfacial Interactions in Poly(2-vinylpyridine)/Silica Nanocomposites

DOE PAGES

Voylov, Dmitry N.; Holt, Adam P.; Doughty, Benjamin; ...

2017-01-10

In this paper, the structure and polymer–nanoparticle interactions among physically adsorbed poly(2-vinylpyridine) chains on the surface of silica nanoparticles (NPs) were systematically studied as a function of molecular weight (MW) by sum frequency generation (SFG) and X-ray photoelectron (XPS) spectroscopies. Analysis of XPS data identified hydrogen bonds between the polymer and NPs, while SFG evaluated the change in the number of free OH sites on the NP’s surface. Our data revealed that the hydrogen bonds and amount of the free ¯OH sites have a significant dependence on the polymer’s MW. Finally, these results provide clear experimental evidence that the interactionmore » of physically adsorbed chains with nanoparticles is strongly MW dependent and aids in unraveling the microscopic mechanism responsible for the strong MW dependence of dynamics of the interfacial layer in polymer nanocomposites.« less

Unraveling the Molecular Weight Dependence of Interfacial Interactions in Poly(2-vinylpyridine)/Silica Nanocomposites

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

Voylov, Dmitry N.; Holt, Adam P.; Doughty, Benjamin

In this paper, the structure and polymer–nanoparticle interactions among physically adsorbed poly(2-vinylpyridine) chains on the surface of silica nanoparticles (NPs) were systematically studied as a function of molecular weight (MW) by sum frequency generation (SFG) and X-ray photoelectron (XPS) spectroscopies. Analysis of XPS data identified hydrogen bonds between the polymer and NPs, while SFG evaluated the change in the number of free OH sites on the NP’s surface. Our data revealed that the hydrogen bonds and amount of the free ¯OH sites have a significant dependence on the polymer’s MW. Finally, these results provide clear experimental evidence that the interactionmore » of physically adsorbed chains with nanoparticles is strongly MW dependent and aids in unraveling the microscopic mechanism responsible for the strong MW dependence of dynamics of the interfacial layer in polymer nanocomposites.« less

Surface characterization of LDEF materials

NASA Astrophysics Data System (ADS)

Wightman, J. P.; Grammer, Holly Little

1993-10-01

The NASA Long Duration Exposure Facility (LDEF), a passive experimental satellite, was placed into low-Earth orbit by the Shuttle Challenger in Apr. 1984. The LDEF spent an unprecedented 69 months in space. The flight and recovery of the LDEF provided a wealth of information on the longterm space environmental effects of a variety of materials exposed to the low-Earth orbit environment. Surface characterization of LDEF materials included polymers, composites, thermal control paints, and aluminum. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), scanning electron microscopy (SEM), and contact angle analysis were used to document changes in both the surface composition and surface chemistry of these materials. Detailed XPS analysis of the polymer systems, such as Kapton, polyimide polysiloxane copolymers, and fluorinated ethylene propylene thermal blankets on the backside of the LDEF revealed significant changes in both the surface composition and surface chemistry as a result of exposure to the low-Earth orbit environment. Polymer systems such as Kapton, polyimide polysiloxane copolymers, and polysulfone showed a common trend of decreasing carbon content and increasing oxygen content with respect to the control sample. Carbon 1s curve fit XPS analysis of the composite samples, in conjunction with SEM photomicrographs, revealed significant ablation of the polymer matrix resin to expose the carbon fibers of the composite during exposure to the space environment. Surface characterization of anodized aluminum tray clamps, which were located at regular intervals over the entire LDEF frame, provided the first results to evaluate the extent of contamination with respect to position on the LDEF. The XPS results clearly showed that the amount and state of both silicon and fluorine contamination were directly dependent upon the position of the tray clamp on the LDEF.

Surface characterization of LDEF materials

NASA Technical Reports Server (NTRS)

Wightman, J. P.; Grammer, Holly Little

1993-01-01

The NASA Long Duration Exposure Facility (LDEF), a passive experimental satellite, was placed into low-Earth orbit by the Shuttle Challenger in Apr. 1984. The LDEF spent an unprecedented 69 months in space. The flight and recovery of the LDEF provided a wealth of information on the longterm space environmental effects of a variety of materials exposed to the low-Earth orbit environment. Surface characterization of LDEF materials included polymers, composites, thermal control paints, and aluminum. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), scanning electron microscopy (SEM), and contact angle analysis were used to document changes in both the surface composition and surface chemistry of these materials. Detailed XPS analysis of the polymer systems, such as Kapton, polyimide polysiloxane copolymers, and fluorinated ethylene propylene thermal blankets on the backside of the LDEF revealed significant changes in both the surface composition and surface chemistry as a result of exposure to the low-Earth orbit environment. Polymer systems such as Kapton, polyimide polysiloxane copolymers, and polysulfone showed a common trend of decreasing carbon content and increasing oxygen content with respect to the control sample. Carbon 1s curve fit XPS analysis of the composite samples, in conjunction with SEM photomicrographs, revealed significant ablation of the polymer matrix resin to expose the carbon fibers of the composite during exposure to the space environment. Surface characterization of anodized aluminum tray clamps, which were located at regular intervals over the entire LDEF frame, provided the first results to evaluate the extent of contamination with respect to position on the LDEF. The XPS results clearly showed that the amount and state of both silicon and fluorine contamination were directly dependent upon the position of the tray clamp on the LDEF.

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

Sarkar, S.; Mondal, A.; Dey, K.

Highlights: • Reduced graphene oxides (RGO) are prepared by two chemical routes. • Defects in RGO are characterized by Raman, FTIR and XPS studies. • Defects tailor colossal dielectricity in RGO. - Abstract: Reduced graphene oxide (RGO) is prepared in two different chemical routes where reduction of graphene oxide is performed by hydrazine hydrate and through high pressure in hydrothermal reactor. Samples are characterized by X-ray powdered diffraction (XRD), thermo gravimetric analysis (TGA), field emission scanning electron microscopy (FESEM) and tunneling electron microscopy (TEM). Types of defects are probed by Raman, FTIR spectroscopy and X-ray photoelectron spectroscopy (XPS). UV–vis absorptionmore » reveals different optical band gaps of the two RGOs. Conductivity mechanism is studied through I–V measurements displaying different characteristic features which are addressed due to the presence of defects appeared in different synthesis. Significantly high value (∼10{sup 4}) of dielectric permittivity at 10 MHz is attractive for technological application which could be tuned by the defects present in RGO.« less

Hydrothermal-reduction synthesis of manganese oxide nanomaterials for electrochemical supercapacitors.

PubMed

Zhang, Xiong; Chen, Yao; Yu, Peng; Ma, Yanwei

2010-11-01

In the present work, amorphous manganese oxide nanomaterials have been synthesized by a common hydrothermal method based on the redox reaction between MnO4(-) and Fe(2+) under an acidic condition. The synthesized MnO2 samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and electrochemical studies. XRD results showed that amorphous manganese oxide phase was obtained. XPS quantitative analysis revealed that the atomic ratio of Mn to Fe was 3.5 in the MnO2 samples. TEM images showed the porous structure of the samples. Electrochemical properties of the MnO2 electrodes were studied using cyclic voltammetry and galvanostatic charge-discharge cycling in 1 M Na2SO4 aqueous electrolyte, which showed excellent pseudocapacitance properties. A specific capacitance of 192 Fg(-1) at a current density of 0.5 Ag(-1) was obtained at the potential window from -0.1 to 0.9 V (vs. SCE).

Synthesis and characterization of an effective organic/inorganic hybrid green corrosion inhibitive complex based on zinc acetate/Urtica Dioica

NASA Astrophysics Data System (ADS)

Salehi, E.; Naderi, Reza; Ramezanzadeh, B.

2017-02-01

This study aims at synthesis and characterization of an effective corrosion inhibitive complex based on zinc acetate/Urtica Dioica (ZnA-U.D) for corrosion protection of mild steel in chloride solution. The chemical structure and morphology of the complex were characterized by Fourier transform infrared spectroscopy (FT-IR), UV-vis, thermal gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The corrosion protection performance of the mild steel samples dipped in 3.5 wt.% NaCl solutions with and without ZnA-U.D extract was investigated by visual observations, open circuit potential (OCP) measurements, electrochemical impedance spectroscopy (EIS) and polarization test. Results revealed that the ZnA successfully chelated with organic inhibitive compounds (i.e Quercetin, Quinic acid, Caffeic acid, Hystamine and Serotonin) present in the U.D extract. The electrochemical measurements revealed the effective inhibition action of ZnA-U.D complex in the sodium chloride solution on the mild steel. The synergistic effect between Zn2+ and organic compounds present in the U.D extract resulted in protective film deposition on the steel surface, which was proved by SEM and XPS analyses.

Effects of argon addition on a-CNx film deposition by hot carbon filament chemical vapor deposition

NASA Astrophysics Data System (ADS)

Watanabe, Yoshihisa; Aono, Masami; Yamazaki, Ayumi; Kitazawa, Nobuaki; Nakamura, Yoshikazu

2002-07-01

Using a carbon filament which supplies carbon and heat, amorphous carbon nitride (a-CNx) films were prepared on Si (100) substrates by hot filament chemical vapor deposition. Deposition was performed in a low-pressure atmosphere of pure nitrogen and a gas mixture of nitrogen and argon. Effects of argon additions to the nitrogen atmosphere on the film microstructure and interface composition between the film and substrate were studied by field-emission scanning electron microscopy (FESEM) and x-ray photoelectron spectroscopy (XPS). FESEM observations reveal that the film prepared in a pure nitrogen atmosphere has uniform nucleation and a densely packed columnar pieces structure. The film prepared in the nitrogen and argon gas mixture exhibits preferential nucleation and a tapered structure with macroscopic voids. Depth analyses using XPS reveal that the film prepared in pure nitrogen possesses a broad interface, which includes silicon carbide as well as a-CNx, whereas a sharp interface is discerned in the film prepared in the mixed nitrogen and argon gas. We observed that silicon carbide formation is suppressed by an argon addition to the nitrogen atmosphere during deposition. copyright 2002 American Vacuum Society.

The polymeric nanofilm of triazinedithiolsilane fabricated by self-assembled technique on copper surface. Part 2: Characterization of composition and morphology

NASA Astrophysics Data System (ADS)

Wang, Yabin; Liu, Zhong; Huang, Yudong; Qi, Yutai

2015-11-01

In the first part, a novel design route for metal protection against corrosion was proposed, and a class of triazinedithiolsilane compounds was conceived as protector for copper. The protective capability of the polymeric nanofilm, fabricated by self-assembling one representative (abbreviated as TESPA) of triazinedithiolsilane compounds onto copper surface, has been investigated and evaluated by electrochemical tests. The results show that the polymeric nanofilm significantly inhibits copper corrosion. This study, on the one hand, concentrates on the chemical composition of the TESPA polymeric nanofilm by means of X-ray photoelectron spectroscopy (XPS). The XPS results reveal that the chemical bonds between copper and TESPA monomers, three dimensional disulfide units and siloxane networks are responsible for the satisfactory protection of TESPA polymeric nanofilm against copper corrosion. On the other hand, scanning electron microscope (SEM) and energy-dispersive spectroscopy (EDS) are utilized to reveal the morphology and the uniformity of the TESPA polymeric nanofilm. The SEM-EDS results demonstrate that the copper surfaces are uniformly covered with TESPA self-assembled monolayer and the polymeric nanofilm. The TESPA-covered copper surfaces turn out to be smoother than that of the bare copper surface.

Selective depression mechanism of ferric chromium lignin sulfonate for chalcopyrite-galena flotation separation

NASA Astrophysics Data System (ADS)

Yu, Jin-sheng; Liu, Run-qing; Wang, Li; Sun, Wei; Peng, Hong; Hu, Yue-hua

2018-05-01

Selective recovery of chalcopyrite-galena ore by flotation remains a challenging issue. The development of highly efficient, low-cost, and environmentally friendly depressants for this flotation is necessary because most of available reagents (e.g., K2Cr2O4) are expensive and adversely affect the environment. In this study, ferric chromium lignin sulfonate (FCLS), which is a waste-product from the paper and pulp industry, was introduced as a selective depressant for galena with butyl xanthate (BX) as a collector. Results show that the residue recovery of Pb in Cu concentrate was substantially reduced to 4.73% using FCLS compared with 10.71% using the common depressant K2Cr2O4. The underlying mechanisms were revealed using zeta-potential measurements and X-ray photoelectron spectroscopy (XPS). Zeta-potential measurements revealed that FCLS was more efficiently absorbed onto galena than onto chalcopyrite. XPS measurements further suggested that FCLS enhanced the surface oxidation of galena but prevented that of chalcopyrite. Thus, FCLS could be a potential candidate as a depressant for chalcopyrite-galena flotation because of its low cost and its lack of detrimental effects on the environment.

A Multicenter Randomized Noninferiority Trial Comparing GreenLight-XPS Laser Vaporization of the Prostate and Transurethral Resection of the Prostate for the Treatment of Benign Prostatic Obstruction: Two-yr Outcomes of the GOLIATH Study.

PubMed

Thomas, James A; Tubaro, Andrea; Barber, Neil; d'Ancona, Frank; Muir, Gordon; Witzsch, Ulrich; Grimm, Marc-Oliver; Benejam, Joan; Stolzenburg, Jens-Uwe; Riddick, Antony; Pahernik, Sascha; Roelink, Herman; Ameye, Filip; Saussine, Christian; Bruyère, Franck; Loidl, Wolfgang; Larner, Tim; Gogoi, Nirjan-Kumar; Hindley, Richard; Muschter, Rolf; Thorpe, Andrew; Shrotri, Nitin; Graham, Stuart; Hamann, Moritz; Miller, Kurt; Schostak, Martin; Capitán, Carlos; Knispel, Helmut; Bachmann, Alexander

2016-01-01

The GOLIATH study is a 2-yr trial comparing transurethral resection of prostate (TURP) to photoselective vaporization with the GreenLight XPS Laser System (GL-XPS) for the treatment of benign prostatic obstruction (BPO). Noninferiority of GL-XPS to TURP was demonstrated based on a 6-mo follow-up from the study. To determine whether treatment effects observed at 6 mo between GL-XPS and TURP was maintained at the 2-yr follow-up. Prospective randomized controlled trial at 29 centers in nine European countries involving 281 patients with BPO. Photoselective vaporization using the 180-W GreenLight GL-XPS or conventional (monopolar or bipolar) TURP. The primary outcome was the International Prostate Symptom Score for which a margin of three was used to evaluate the noninferiority of GL-XPS. Secondary outcomes included Qmax, prostate volume, prostate specific antigen, Overactive Bladder Questionnaire Short Form, International Consultation on Incontinence Questionnaire Short Form, occurrence of surgical retreatment, and freedom from complications. One hundred and thirty-six patients were treated using GL-XPS and 133 using TURP. Noninferiority of GL-XPS on International Prostate Symptom Score, Qmax, and freedom from complications was demonstrated at 6-mo and was sustained at 2-yr. The proportion of patients complication-free through 24-mo was 83.6% GL-XPS versus 78.9% TURP. Reductions in prostate volume and prostate specific antigen were similar in both arms and sustained over the course of the trial. Compared with the 1(st) yr of the study, very few adverse events or retreatments were reported in either arm. Treatment differences in the Overactive Bladder Questionnaire Short Form observed at 12-mo were not statistically significant at 24-mo. A limitation was that patients and treating physicians were not blinded to the therapy. Twenty-four-mo follow-up data demonstrated that GL-XPS provides a durable surgical option for the treatment of BPO that exhibits efficacy and safety outcomes similar to TURP. The long-term effectiveness and safety of GLP-XLS was similar to conventional TURP for the treatment of prostate enlargement. Copyright © 2015 European Association of Urology. Published by Elsevier B.V. All rights reserved.

Energy level alignment at the methylammonium lead iodide/copper phthalocyanine interface

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

Chen, Shi; Goh, Teck Wee; Sum, Tze Chien, E-mail: Alfred@ntu.edu.sg, E-mail: Tzechien@ntu.edu.sg

2014-08-01

The energy level alignment at the CH{sub 3}NH{sub 3}PbI{sub 3}/copper phthalocyanine (CuPc) interface is investigated by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). XPS reveal a 0.3 eV downward band bending in the CuPc film. UPS validate this finding and further reveal negligible interfacial dipole formation – verifying the viability of vacuum level alignment. The highest occupied molecular orbital of CuPc is found to be closer to the Fermi level than the valance band maximum of CH{sub 3}NH{sub 3}PbI{sub 3}, facilitating hole transfer from CH{sub 3}NH{sub 3}PbI{sub 3} to CuPc. However, subsequent hole extraction from CuPc may bemore » impeded by the downward band bending in the CuPc layer.« less

X-ray photoelectron spectroscopic and morphologic studies of Ru nanoparticles deposited onto highly oriented pyrolytic graphite

NASA Astrophysics Data System (ADS)

Bavand, R.; Yelon, A.; Sacher, E.

2015-11-01

Ruthenium nanoparticles (Ru NPs) function as effective catalysts in specific reactions, such as methanation and Fischer-Tropsch syntheses. It is our purpose to physicochemically characterize their surfaces, at which catalysis occurs, by surface-sensitive X-ray photoelectron spectroscopy (XPS), using the symmetric peak component anaylsis technique developed in our laboratory to reveal previously hidden components. Ru NPs were deposited by evaporation (0.25-1.5 nm nominal deposition range) onto highly oriented pyrolytic graphite (HOPG). In addition to their surfaces being characterized by XPS, an indication of morphology was obtained from transmission electron microscopy (TEM). Our use of symmetric peak component XPS analysis has revealed detailed information on a previously unidentified surface oxide initially formed, as well as on the valence electronic structure and its variation with NP size, information that is of potential importance in the use of these NPs in catalysis. Each of the several Ru core XPS spectra characterized (3d, 3p and 3s) was found to be composed of three symmetric components. Together with two metal oxide O1s components, these give evidence of a rather complex, previously unidentified oxide that is initially formed. The Ru valence band (4d and 5s) spectra clearly demonstrate a loss of metallicity, a simultaneous increase of the Kubo gap, and an abrupt transfer in valence electron density from the 4d to the 5s orbitals (known as electron spill-over), as the NP size decreases below 0.5 nm. TEM photomicrographs, as a function of deposition rate, show that, at a rate that gives insufficient time for the NP condensation energy to dissipate, the initially well-separated NPs are capable of diffusing laterally and aggregating. This indicates weak NP bonding to the HOPG substrate. Carbide is formed, at both high and low deposition rates, at Ru deposition thicknesses greater than 0.25 nm, its formation explained by Ru NPs reacting with residual hydrocarbon vapor, under the influence of the heat of condensation released on Ru deposition, and not by Ru reacting with the HOPG substrate.

New insights into micro/nanoscale combined probes (nanoAuger, μXPS) to characterize Ag/Au@SiO2 core-shell assemblies.

PubMed

Ledeuil, J B; Uhart, A; Soulé, S; Allouche, J; Dupin, J C; Martinez, H

2014-10-07

This work has examined the elemental distribution and local morphology at the nanoscale of core@shell Ag/Au@SiO2 particles. The characterization of such complex metal/insulator materials becomes more efficient when using an initial cross-section method of preparation of the core@shell nanoparticles (ion milling cross polisher). The originality of this route of preparation allows one to obtain undamaged, well-defined and planar layers of cross-cut nano-objects. Once combined with high-resolution techniques of characterization (XPS, Auger and SEM), the process appears as a powerful way to minimize charging effects and enhance the outcoming electron signal (potentially affected by the topography of the material) during analysis. SEM experiments have unambiguously revealed the hollow-morphology of the metal core, while Auger spectroscopy observations showed chemical heterogeneity within the particles (as silver and gold are randomly found in the core ring). To our knowledge, this is the first time that Auger nano probe spectroscopy has been used and successfully optimized for the study of some complex metal/inorganic interfaces at such a high degree of resolution (≈12 nm). Complementarily, XPS Au 4f and Ag 3d peaks were finally detected attesting the possibility of access to the whole chemistry of such nanostructured assemblies.

New insights into micro/nanoscale combined probes (nanoAuger, μXPS) to characterize Ag/Au@SiO2 core-shell assemblies

NASA Astrophysics Data System (ADS)

Ledeuil, J. B.; Uhart, A.; Soulé, S.; Allouche, J.; Dupin, J. C.; Martinez, H.

2014-09-01

This work has examined the elemental distribution and local morphology at the nanoscale of core@shell Ag/Au@SiO2 particles. The characterization of such complex metal/insulator materials becomes more efficient when using an initial cross-section method of preparation of the core@shell nanoparticles (ion milling cross polisher). The originality of this route of preparation allows one to obtain undamaged, well-defined and planar layers of cross-cut nano-objects. Once combined with high-resolution techniques of characterization (XPS, Auger and SEM), the process appears as a powerful way to minimize charging effects and enhance the outcoming electron signal (potentially affected by the topography of the material) during analysis. SEM experiments have unambiguously revealed the hollow-morphology of the metal core, while Auger spectroscopy observations showed chemical heterogeneity within the particles (as silver and gold are randomly found in the core ring). To our knowledge, this is the first time that Auger nano probe spectroscopy has been used and successfully optimized for the study of some complex metal/inorganic interfaces at such a high degree of resolution (~12 nm). Complementarily, XPS Au 4f and Ag 3d peaks were finally detected attesting the possibility of access to the whole chemistry of such nanostructured assemblies.This work has examined the elemental distribution and local morphology at the nanoscale of core@shell Ag/Au@SiO2 particles. The characterization of such complex metal/insulator materials becomes more efficient when using an initial cross-section method of preparation of the core@shell nanoparticles (ion milling cross polisher). The originality of this route of preparation allows one to obtain undamaged, well-defined and planar layers of cross-cut nano-objects. Once combined with high-resolution techniques of characterization (XPS, Auger and SEM), the process appears as a powerful way to minimize charging effects and enhance the outcoming electron signal (potentially affected by the topography of the material) during analysis. SEM experiments have unambiguously revealed the hollow-morphology of the metal core, while Auger spectroscopy observations showed chemical heterogeneity within the particles (as silver and gold are randomly found in the core ring). To our knowledge, this is the first time that Auger nano probe spectroscopy has been used and successfully optimized for the study of some complex metal/inorganic interfaces at such a high degree of resolution (~12 nm). Complementarily, XPS Au 4f and Ag 3d peaks were finally detected attesting the possibility of access to the whole chemistry of such nanostructured assemblies. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03211j

Study of the interaction of inorganic and organic compounds of cell culture medium with a Ti surface.

PubMed

Burgos-Asperilla, L; García-Alonso, M C; Escudero, M L; Alonso, C

2010-02-01

The interaction between Ti and each component of Dulbecco's modified Eagle's medium was studied in depth using different techniques, such as the measurement of the corrosion potential, electrochemical impedance spectroscopy and polarization curves. The characterization of metal surfaces was carried out by scanning electron microscopy and X-ray photoelectron spectroscopy (XPS). The adsorption process of each component was studied using the quartz crystal balance (QCM). The QCM and XPS results reveal that the adsorption kinetics for phosphate and calcium ions is slow. However, the bovine serum albumin (BSA) totally covers the Ti surface rapidly. Because the passive film (titanium oxide) has acidic hydroxyl groups, the calcium ions would have a bridging effect on the electrostatic adsorption of phosphate ions as well as that of BSA. The polarization curves reveal that the adsorbed glucose permits the ionic diffusion of the oxygen to the electrode, while the BSA and fetal bovine serum (FBS) adsorbed after 7 days of immersion act as a diffusive barrier. The impedance measurement and data fitting to the electrical equivalent circuit model show that the resistance of the proteins/TiO(2) interface, for Ti immersed in FBS, is higher than those obtained for BSA, due to the proteins present in the solution as well as the fact that the adsorbed proteins on the surface are greater.

Modification of Wetting Properties of PMMA by Immersion Plasma Ion Implantation

NASA Astrophysics Data System (ADS)

Mireault, N.; Ross, G. G.

Advancing and receding contact angles below 5° have been obtained on PMMA surfaces with the implantation of argon and oxygen ions. The ion implantations were performed by means of the Immersion Plasma Ion Implantation (IPII) technique, a hybrid between ion beams and immersion plasmas. Characterization of treated PMMA surfaces by means of XPS and its combination with chemical derivatization (CD-XPS) have revealed the depletion of oxygen and the creation of dangling bonds, together with the formation of new chemical functions such as -OOH, -COOH and C=C. These observations provide a good explanation for the strong increase of the wetting properties of the PMMA surfaces.

The (001) 3C SiC surface termination and band structure after common wet chemical etching procedures, stated by XPS, LEED, and HREELS

NASA Astrophysics Data System (ADS)

Tengeler, Sven; Kaiser, Bernhard; Ferro, Gabriel; Chaussende, Didier; Jaegermann, Wolfram

2018-01-01

The (001) surface of cubic silicon carbide (3C SiC) after cleaning, Ar sputtering and three different wet chemical etching procedures was thoroughly investigated via (angle resolved) XPS, HREELS, and LEED. While Ar sputtering was found to be unsuitable for surface preparation, all three employed wet chemical etching procedures (piranha/NH4F, piranha/HF, and RCA) provide a clean surface. HF as oxide removal agent tends to result in fluorine traces on the sample surface, despite thorough rinsing. All procedures yield a 1 × 1 Si-OH/C-H terminated surface. However, the XPS spectra reveal some differences in the resulting surface states. NH4F for oxide removal produces a flat band situation, whereas the other two procedures result in a slight downward (HF) or upward (RCA) band bending. Because the band bending is small, it can be concluded that the number of unsaturated surface defects is low.

Adsorption differences between low coverage enantiomers of alanine on the chiral Cu{421}R surface.

PubMed

Gladys, Michael J; Han, Jeong Woo; Pedersen, Therese S; Tadich, Anton; O'Donnell, Kane M; Thomsen, Lars

2017-05-31

Chiral separation using heterogeneous methods has long been sought after. Chiral metal surfaces have the potential to make it possible to model these systems using small amino acids, the building blocks for proteins. A comparison of submonolayer concentrations of alanine enantiomers adsorbed onto Cu{421} R has revealed a large geometrical differences between the two molecules as compared to the saturated coverage. Large differences were observed in HR-XPS and NEXAFS and complemented by theoretical DFT calculations. At approximately one third of a monolayer a comparison of the C1s XPS signal showed a shift in the methyl group of more than 300 meV indicating that the two enantiomers are in different chemical environments. NEXAFS spectroscopy confirmed the XPS variations and showed large differences in the orientation of the adsorbed molecules. Our DFT results show that the l-enantiomer is energetically the most stable in the {311} microfacet configuration. In contrast to the full monolayer coverage, these lower coverages showed enhanced selectivity.

XPS Protocol for the Characterization of Pristine and Functionalized Single Wall Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Sosa, E. D.; Allada, R.; Huffman, C. B.; Arepalli, S.

2009-01-01

Recent interest in developing new applications for carbon nanotubes (CNT) has fueled the need to use accurate macroscopic and nanoscopic techniques to characterize and understand their chemistry. X-ray photoelectron spectroscopy (XPS) has proved to be a useful analytical tool for nanoscale surface characterization of materials including carbon nanotubes. Recent nanotechnology research at NASA Johnson Space Center (NASA-JSC) helped to establish a characterization protocol for quality assessment for single wall carbon nanotubes (SWCNTs). Here, a review of some of the major factors of the XPS technique that can influence the quality of analytical data, suggestions for methods to maximize the quality of data obtained by XPS, and the development of a protocol for XPS characterization as a complementary technique for analyzing the purity and surface characteristics of SWCNTs is presented. The XPS protocol is then applied to a number of experiments including impurity analysis and the study of chemical modifications for SWCNTs.

Effect of substrate surface treatment on electrochemically assisted photocatalytic activity of N-S co-doped TiO2 films

NASA Astrophysics Data System (ADS)

Parada-Gamboa, N. J.; Pedraza-Avella, J. A.; Meléndez, A. M.

2017-01-01

To investigate whether different metal surface treatments, performed on meshes of stainless steel 304 and titanium, affect the photocatalytic activity (PCA) of supported modified anodic TiO2 films, metallic substrates were coated with titanium isopropoxide sol-gel precursor modified with thiourea. Substrates were pretreated by some of the following techniques: a) sandblasting, b) pickling, c) hydroxylation and d) passivation. The as-prepared electrode materials were characterized by X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), and voltammetry in the dark and under light UVA irradiation. PCA of modified N-S-TiO2 electrodes was evaluated by electrochemically assisted photocatalytic degradation of methyl orange. The results of XPS revealed that N and S were incorporated into the lattice of TiO2. FESEM showed that surface roughness and thickness of films varies depending on surface treatment. Voltammetric and XPS characterization of N-S co-doped TiO2 films supported on stainless steel revealed that their surface contains alpha-Fe2O3/FeOOH. Accordingly, iron contamination of the films coming from stainless steel was detrimental to the degradation of methyl orange. Prior to sol-gel coating process, sandblasting followed by nitric acid passivation for stainless steel or hydrofluoric acid pickling process in the case of titanium improved the PCA of N-S co-doped TiO2 films.

In situ NAP-XPS spectroscopy during methane dry reforming on ZrO2/Pt(1 1 1) inverse model catalyst

NASA Astrophysics Data System (ADS)

Rameshan, C.; Li, H.; Anic, K.; Roiaz, M.; Pramhaas, V.; Rameshan, R.; Blume, R.; Hävecker, M.; Knudsen, J.; Knop-Gericke, A.; Rupprechter, G.

2018-07-01

Due to the need of sustainable energy sources, methane dry reforming is a useful reaction for conversion of the greenhouse gases CH4 and CO2 to synthesis gas (CO  +  H2). Syngas is the basis for a wide range of commodity chemicals and can be utilized for fuel production via Fischer–Tropsch synthesis. The current study focuses on spectroscopic investigations of the surface and reaction properties of a ZrO2/Pt inverse model catalyst, i.e. ZrO2 particles (islands) grown on a Pt(1 1 1) single crystal, with emphasis on in situ near ambient pressure x-ray photoelectron spectroscopy (NAP-XPS) during MDR reaction. In comparison to technological systems, model catalysts facilitate characterization of the surface (oxidation) state, surface adsorbates, and the role of the metal-support interface. Using XPS and infrared reflection absorption spectroscopy we demonstrated that under reducing conditions (UHV or CH4) the ZrO2 particles transformed to an ultrathin ZrO2 film that started to cover (wet) the Pt surface in an SMSI-like fashion, paralleled by a decrease in surface/interface oxygen. In contrast, (more oxidizing) dry reforming conditions with a 1:1 ratio of CH4 and CO2 were stabilizing the ZrO2 particles on the model catalyst surface (or were even reversing the strong metal support interaction (SMSI) effect), as revealed by in situ XPS. Carbon deposits resulting from CH4 dissociation were easily removed by CO2 or by switching to dry reforming conditions (673–873 K). Thus, at these temperatures the active Pt surface remained free of carbon deposits, also preserving the ZrO2/Pt interface.

Atomic layer deposited TaCy metal gates: Impact on microstructure, electrical properties, and work function on HfO2 high-k dielectrics

NASA Astrophysics Data System (ADS)

Triyoso, D. H.; Gregory, R.; Schaeffer, J. K.; Werho, D.; Li, D.; Marcus, S.; Wilk, G. D.

2007-11-01

TaCy has been reported to have the appropriate work function for negative metal-oxide semiconductor metal in high-k metal-oxide field-effect transistors. As device size continues to shrink, a conformal deposition for metal gate electrodes is needed. In this work, we report on the development and characterization of a novel TaCy process by atomic layer deposition (ALD). Detailed physical properties of TaCy films are studied using ellipsometry, a four-point probe, Rutherford backscattering spectrometry (RBS), x-ray photoelectron spectroscopy (XPS), and x-ray diffraction (XRD). RBS and XPS analysis indicate that TaCy films are near-stoichiometric, nitrogen free, and have low oxygen impurities. Powder XRD spectra showed that ALD films have a cubic microstructure. XPS carbon bonding studies revealed that little or no glassy carbon is present in the bulk of the film. Excellent electrical properties are obtained using ALD TaCy as a metal gate electrode. Well-behaved capacitance-voltage characteristics with ALD HfO2 gate dielectrics are demonstrated for TaCy thicknesses of 50, 100, and 250 Å. A low fixed charge (˜2-4×10-11 cm-2) is observed for all ALD HfO2/ALD TaCy devices. Increasing the thickness of ALD TaCy results in a decrease in work function (4.77 to 4.54 eV) and lower threshold voltages.

Study of GO-Cu2O and RGO-Cu nanocomposite monolayer sheets prepared by modified Langmuir Blodgett route

NASA Astrophysics Data System (ADS)

Botcha, V. Divakar; Sutar, D. S.; Major, S. S.

2018-07-01

The modified Langmuir-Blodgett (MLB) technique has been improvised and extended to transfer GO-Cu2O nanocomposite monolayer sheets, by introducing Cu2+ ions into the subphase at room temperature. Morphological studies of as-transferred sheets revealed the presence of closely spaced GO monolayer sheets, with slightly enhanced roughness. XPS studies of as-transferred sheets confirmed the presence of copper, either as metallic Cu or Cu2O, along with significant Cu(OH)2 component, but TEM results confirmed the formation of Cu2O nanocrystallites of size (7 ± 2) nm, distributed uniformly over GO sheets. After heat treatment in vacuum at 400 °C, the nanocomposite sheets were covered with a uniform distribution of larger size nanoparticles. Based on Raman, XPS and TEM studies it has been confirmed that heat treatment at 400 °C in vacuum results in the formation of agglomerated Cu nanoparticles of size (23 ± 9) nm distributed uniformly over reduced graphene oxide (RGO) sheets. The electrical characterization of nanocomposite sheets on SiO2/Si in back-gated FET geometry revealed that the electrical conductivity of as-transferred GO-Cu2O sheets was similar to that usually observed for GO monolayer sheets. The RGO-Cu sheets also displayed electrical conductivity and field effect mobility values comparable to those reported for RGO sheets obtained by chemical/thermal reduction, and was unaffected by the presence of Cu nanoparticles.

Problems at the Leading Edge of Space Weathering as Revealed by TEM Combined with Surface Science Techniques

NASA Astrophysics Data System (ADS)

Christoffersen, R.; Dukes, C. A.; Keller, L. P.; Rahman, Z.; Baragiola, R. A.

2015-11-01

Analytical field-emission TEM techniques cross-correlated with surface analyses by X-ray photoelectron spectroscopy (XPS) provides a unique two-prong approach for characterizing how solar wind ion processing contributes to space weathering.

Magnesium oxide grafted carbon nanotubes based impedimetric genosensor for biomedical application.

PubMed

Patel, Manoj Kumar; Ali, Md Azahar; Srivastava, Saurabh; Agrawal, Ved Varun; Ansari, S G; Malhotra, Bansi D

2013-12-15

Nanostructured magnesium oxide (size<10nm) grafted carboxyl (COOH) functionalized multi-walled carbon nanotubes (nMgO-cMWCNTs) deposited electrophoretically onto indium tin oxide (ITO) coated glass electrode and have been utilized for Vibrio cholerae detection. Aminated 23 bases single stranded DNA (NH2-ssDNA) probe sequence (O1 gene) of V. cholerae has been covalently functionalized onto nMgO-cMWCNTs/ITO electrode surface using EDC-NHS chemistry. This DNA functionalized MgO grafted cMWCNTs electrode has been characterized using X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical techniques. The results of XPS studies reveal that sufficient O-C=O groups present at the nMgO-cMWCNTs surface are utilized for DNA binding. The results of hybridization studies conducted with fragmented target DNA (ftDNA) of V. cholerae using electrochemical impedance spectroscopy (EIS) reveal sensitivity as 3.87 Ω ng(-1) cm(-2), detection limit of ~21.70 ng µL(-1) in the linear range of 100-500 ng µL(-1) and stability of about 120 days. The proposed DNA functionalized nMgO-cMWCNTs nanomatrix provides a novel impedimetric platform for the fabrication of a compact genosensor device for biomedical application. © 2013 Elsevier B.V. All rights reserved.

Core-level spectra and binding energies of transition metal nitrides by non-destructive x-ray photoelectron spectroscopy through capping layers

NASA Astrophysics Data System (ADS)

Greczynski, G.; Primetzhofer, D.; Lu, J.; Hultman, L.

2017-02-01

We present the first measurements of x-ray photoelectron spectroscopy (XPS) core level binding energies (BE:s) for the widely-applicable group IVb-VIb polycrystalline transition metal nitrides (TMN's) TiN, VN, CrN, ZrN, NbN, MoN, HfN, TaN, and WN as well as AlN and SiN, which are common components in the TMN-based alloy systems. Nitride thin film samples were grown at 400 °C by reactive dc magnetron sputtering from elemental targets in Ar/N2 atmosphere. For XPS measurements, layers are either (i) Ar+ ion-etched to remove surface oxides resulting from the air exposure during sample transfer from the growth chamber into the XPS system, or (ii) in situ capped with a few nm thick Cr or W overlayers in the deposition system prior to air-exposure and loading into the XPS instrument. Film elemental composition and phase content is thoroughly characterized with time-of-flight elastic recoil detection analysis (ToF-E ERDA), Rutherford backscattering spectrometry (RBS), and x-ray diffraction. High energy resolution core level XPS spectra acquired with monochromatic Al Kα radiation on the ISO-calibrated instrument reveal that even mild etching conditions result in the formation of a nitrogen-deficient surface layer that substantially affects the extracted binding energy values. These spectra-modifying effects of Ar+ ion bombardment increase with increasing the metal atom mass due to an increasing nitrogen-to-metal sputter yield ratio. The superior quality of the XPS spectra obtained in a non-destructive way from capped TMN films is evident from that numerous metal peaks, including Ti 2p, V 2p, Zr 3d, and Hf 4f, exhibit pronounced satellite features, in agreement with previously published spectra from layers grown and analyzed in situ. In addition, the N/metal concentration ratios are found to be 25-90% higher than those obtained from the corresponding ion-etched surfaces, and in most cases agree very well with the RBS and ToF-E ERDA values. The N 1 s BE:s extracted from capped TMN films, thus characteristic of a native surface, show a systematic trend, which contrasts with the large BE spread of literature "reference" values. Hence, non-destructive core level XPS employing capping layers provides an opportunity to obtain high-quality spectra, characteristic of virgin in situ grown and analyzed TMN films, although with larger versatility, and allows for extracting core level BE values that are more reliable than those obtained from sputter-cleaned N-deficient surfaces. Results presented here, recorded from a consistent set of binary TMN's grown under the same conditions and analyzed in the same instrument, provide a useful reference for future XPS studies of multinary materials systems allowing for true deconvolution of complex core level spectra.

X-ray photoelectron spectroscopy for characterization of wood surfaces in adhesion studies

Treesearch

James F. Beecher; Charles R. Frihart

2005-01-01

X-ray photoelectron spectroscopy (XPS) is one of a set of tools that have been used to characterize wood surfaces. Among the advantages of XPS are surface sensitivity, identification of nearly all elements, and frequently, discrimination of bonding states. For these reasons, XPS seemed to be an appropriate tool to help explain the differences in bond strength under wet...

Single-layer ZnS supported on Au(111): A combined XPS, LEED, STM and DFT study

DOE PAGES

Deng, Xingyi; Sorescu, Dan C.; Lee, Junseok

2016-12-31

Single-layer of ZnS, consisting of one atomic layer of ZnS(111) plane, has been grown on Au(111) and characterized using X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). While the LEED measurement indicates a coincidence structure of ZnS-(3×3)/Au(111)-(4×4), high resolution STM images reveal hexagonal unit cells of 6.7×6.7 Å 2 and 11.6×11.6 Å 2, corresponding to √3 and 3 times the unit cell of the ideal zincblende ZnS-(1×1), respectively, depending on the tunneling conditions. Calculations based on density functional theory (DFT) indicate a significantly reconstructed non-planar structure of ZnS single-layer on Au(111) with 2/3 ofmore » the S anions being located nearly in the plane of the Zn cations and the rest 1/3 of the S anions protruding above the Zn plane. In conclusion, the calculated STM image shows similar characteristics to those of the experimental STM image. Additionally, the DFT calculations reveal the different bonding nature of the S anions in ZnS single-layer supported on Au(111).« less

Growth of ultra-thin TiO 2 films by spray pyrolysis on different substrates

NASA Astrophysics Data System (ADS)

Oja Acik, I.; Junolainen, A.; Mikli, V.; Danilson, M.; Krunks, M.

2009-12-01

In the present study TiO 2 films were deposited by spray pyrolysis method onto ITO covered glass and Si (1 0 0) substrates. The spray solution containing titanium(IV) isopropoxide, acetylacetone and ethanol was sprayed at a substrate temperature of 450 °C employing 1-125 spray pulses (1 s spray and 30 s pause). According to AFM, continuous coverage of ITO and Si substrates with TiO 2 layer is formed by 5-10 and below 5 spray pulses, respectively. XPS studies revealed that TiO 2 film growth on Si substrate using up to 4 spray pulses follows 2D or layer-by-layer-growth. Above 4 spray pulses, 3D or island growth becomes dominant irrespective of the substrate. Only 50 spray pulses result in TiO 2 layer with the thickness more than XPS measurement escape depth as any signal from the substrate could not be detected. TiO 2 grain size remains 30 nm on ITO and increases from 10-20 nm to 50-100 nm on Si substrate with the number of spray pulses from 1 to 125.

SiGe derivatization by spontaneous reduction of aryl diazonium salts

NASA Astrophysics Data System (ADS)

Girard, A.; Geneste, F.; Coulon, N.; Cardinaud, C.; Mohammed-Brahim, T.

2013-10-01

Germanium semiconductors have interesting properties for FET-based biosensor applications since they possess high surface roughness allowing the immobilization of a high amount of receptors on a small surface area. Since SiGe combined low cost of Si and intrinsic properties of Ge with high mobility carriers, we focused the study on this particularly interesting material. The comparison of the efficiency of a functionalization process involving the spontaneous reduction of diazonium salts is studied on Si(1 0 0), SiGe and Ge semiconductors. XPS analysis of the functionalized surfaces reveals the presence of a covalent grafted layer on all the substrates that was confirmed by AFM. Interestingly, the modified Ge derivatives have still higher surface roughness after derivatization. To support the estimated thickness by XPS, a step measurement of the organic layers is done by AFM or by profilometer technique after a O2 plasma etching of the functionalized layer. This original method is well-adapted to measure the thickness of thin organic films on rough substrates such as germanium. The analyses show a higher chemical grafting on SiGe substrates compared with Si and Ge semiconductors.

Study on the surface sulfidization behavior of smithsonite at high temperature

NASA Astrophysics Data System (ADS)

Lv, Jin-fang; Tong, Xiong; Zheng, Yong-xing; Xie, Xian; Wang, Cong-bing

2018-04-01

Surface sulfidization behavior of smithsonite at high temperature was investigated by X-ray powder diffractometer (XRD) along with thermodynamic calculation, X-ray photoelectron spectroscopy (XPS) and electron probe microanalysis (EPMA). The XRD and thermodynamic analyses indicated that the smithsonite was decomposed into zincite at high temperatures. After introducing a small amount of pyrite, artificial sulfides were formed at surface of the obtained zincite. The XPS analyses revealed that the sulfide species including zinc sulfide and zinc disulfide were generated at the zincite surface. The EPMA analyses demonstrated that the film of sulfides was unevenly distributed at the zincite surface. The average concentration of elemental sulfur at the sample surface increased with increasing of pyrite dosage. A suitable mole ratio of FeS2 to ZnCO3 for the surface thermal modification was determined to be about 0.3. These findings can provide theoretical support for improving the process during which the zinc recovery from refractory zinc oxide ores is achieved by xanthate flotation.

Improved flotation performance of hematite fines using citric acid as a dispersant

NASA Astrophysics Data System (ADS)

Luo, Xi-mei; Yin, Wan-zhong; Sun, Chuan-yao; Wang, Nai-ling; Ma, Ying-qiang; Wang, Yun-fan

2016-10-01

In this study, citric acid was used as a dispersant to improve the flotation performance of hematite fines. The effect and mechanism of citric acid on the reverse flotation of hematite fines were investigated by flotation tests, sedimentation experiments, scanning electron microscopy (SEM), zeta-potential measurements, and X-ray photoelectron spectroscopy (XPS). The results of SEM analysis and flotation tests reveal that a strong heterocoagulation in the form of slime coating or coagulation in hematite fine slurry affects the beneficiation of hematite ores by froth flotation. The addition of a small amount of citric acid (less than 300 g/t) favorably affects the reverse flotation of hematite fines by improving particle dispersion. The results of sedimentation experiments, zeta-potential measurements, and XPS measurements demonstrate that citric acid adsorbs onto hematite and quartz surfaces via hydrogen bonding, thereby reducing the zeta potentials of mineral surfaces, strengthening the electrical double-layer repulsion between mineral particles, and dispersing the pulp particles.

Friction and Wear of Iron in Corrosive Media

NASA Technical Reports Server (NTRS)

Rengstorff, G. W. P.; Miyoshi, K.; Buckley, D. H.

1982-01-01

Friction and wear experiments were conducted with elemental iron exposed to various corrosive media including two acids, base, and a salt. Studies involved various concentrations of nitric and sulfuric acids, sodium hydroxide, and sodium chloride. Load and reciprocating sliding speed were kept constant. With the base NaOH an increase in normality beyond 0.01 N resulted in a decrease in both friction and wear. X-ray photoelectron spectroscopy (XPS) analysis of the surface showed a decreasing concentration of ferric oxide (Fe2O3) on the iron surface with increasing NaOH concentration. With nitric acid (HNO3) friction decreased in solutions to 0.05 N, beyond which no further change in friction was observed. The concentration of Fe2O3 on the surface continued to increase with increasing normality. XPS analysis revealed the presence of sulfates in addition of Fe2O3 on surfaces exposed to sulfuric acid and iron chlorides but no sodium on surfaces exposed to NaCl.

Investigation of the interfacial reaction between metal and fluorine-contained polyimides

NASA Astrophysics Data System (ADS)

Yang, Ching-Yu; Chen, J. S.; Hsu, S. L. C.

2005-07-01

In this work, thin metal films (Cr and Ta) were deposited on fluorine-contained polyimides, 6FDA-BisAAF, and 6FDA-PPD. The chemical states of the metal/polyimide samples were characterized by using x-ray photoelectron spectroscopy (XPS). XPS analysis reveals that metal-C, C-O, and metal-O bondings are present in metallized 6FDA-BisAAF and 6FDA-PPD. C-F bonds are observed in bare 6FDA-BisAAF and 6FDA-PPD however, they are not seen in the metallized samples. Disappearance of the C-F bonding is attributed to the disruption of CF3 side groups from the main chains of 6FDA-BisAAF and 6FDA-PPD when the chains are exposed to the plasma during the metal deposition. Nevertheless, the disruption of CF3 side groups also creates sites for the formation of metal-C or C-O bondings, which provide a positive adhesion strength at the metal/polyimide interface, as revealed by the tape test.

Facile fabrication of BiVO4 nanofilms with controlled pore size and their photoelectrochemical performances

NASA Astrophysics Data System (ADS)

Feng, Chenchen; Jiao, Zhengbo; Li, Shaopeng; Zhang, Yan; Bi, Yingpu

2015-12-01

We demonstrate a facile method for the rational fabrication of pore-size controlled nanoporous BiVO4 photoanodes, and confirmed that the optimum pore-size distributions could effectively absorb visible light through light diffraction and confinement functions. Furthermore, in situ X-ray photoelectron spectroscopy (XPS) reveals more efficient photoexcited electron-hole separation than conventional particle films, induced by light confinement and rapid charge transfer in the inter-crossed worm-like structures.We demonstrate a facile method for the rational fabrication of pore-size controlled nanoporous BiVO4 photoanodes, and confirmed that the optimum pore-size distributions could effectively absorb visible light through light diffraction and confinement functions. Furthermore, in situ X-ray photoelectron spectroscopy (XPS) reveals more efficient photoexcited electron-hole separation than conventional particle films, induced by light confinement and rapid charge transfer in the inter-crossed worm-like structures. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06584d

Structural, optical and electronic properties of K2Ba(NO3)4 crystal

NASA Astrophysics Data System (ADS)

Isaenko, L. I.; Korzhneva, K. E.; Goryainov, S. V.; Goloshumova, A. A.; Sheludyakova, L. A.; Bekenev, V. L.; Khyzhun, O. Y.

2018-02-01

Nitrate crystals reveal nonlinear optical properties and could be considered as converters of laser radiation in the short-wave region. The conditions for obtaining and basic properties of K2Ba(NO3)4 double nitrate crystals were investigated. Crystal growth was implemented by slow cooling in the temperature range of 72-49 °C and low rate evaporation. The structural analysis of K2Ba(NO3)4 formation on the basis of two mixed simple nitrate structures is discussed. The main groups of oscillations in K2Ba(NO3)4 crystal were revealed using Raman and IR spectroscopy, and the table of vibrations for this compound was compiled. The electronic structure of K2Ba(NO3)4 was elucidated in the present work from both experimental and theoretical viewpoints. In particular, X-ray photoelectron spectroscopy (XPS) was employed in the present work to measure binding energies of the atoms constituting the titled compound and its XPS valence-band spectrum for both pristine and Ar+ ion-bombarded surfaces. Further, total and partial densities of states of constituent atoms of K2Ba(NO3)4 have been calculated. The calculations reveal that the O 2p states dominate in the total valence-band region of K2Ba(NO3)4 except of its bottom, where K 3p and Ba 5p states are the principal contributors, while the bottom of the conduction band is composed mainly of the unoccupied O 2p states, with somewhat smaller contributions of the N 2p∗ states as well. With respect to the occupation of the valence band by the O 2p states, the present band-structure calculations are confirmed by comparison on a common energy scale of the XPS valence-band spectrum and the X-ray emission O Kα band for the K2Ba(NO3)4 crystal under study. Furthermore, the present calculations indicate that the K2Ba(NO3)4 compound is a direct-gap material.

Highly efficient removal of heavy metals by polymer-supported nanosized hydrated Fe(III) oxides: behavior and XPS study.

PubMed

Pan, Bingjun; Qiu, Hui; Pan, Bingcai; Nie, Guangze; Xiao, Lili; Lv, Lu; Zhang, Weiming; Zhang, Quanxing; Zheng, Shourong

2010-02-01

The present study developed a polymer-based hybrid sorbent (HFO-001) for highly efficient removal of heavy metals [e.g., Pb(II), Cd(II), and Cu(II)] by irreversibly impregnating hydrated Fe(III) oxide (HFO) nanoparticles within a cation-exchange resin D-001 (R-SO(3)Na), and revealed the underlying mechanism based on X-ray photoelectron spectroscopy (XPS) study. HFO-001 combines the excellent handling, flow characteristics, and attrition resistance of conventional cation-exchange resins with the specific affinity of HFOs toward heavy metal cations. As compared to D-001, sorption selectivity of HFO-001 toward Pb(II), Cu(II), and Cd(II) was greatly improved from the Ca(II) competition at greater concentration. Column sorption results indicated that the working capacity of HFO-001 was about 4-6 times more than D-001 with respect to removal of three heavy metals from simulated electroplating water (pH approximately 4.0). Also, HFO-001 is particularly effective in removing trace Pb(II) and Cd(II) from simulated natural waters to meet the drinking water standard, with treatment volume orders of magnitude higher than D-001. The superior performance of HFO-001 was attributed to the Donnan membrane effect exerted by the host D-001 as well as to the impregnated HFO nanoparticles of specific interaction toward heavy metal cations, as further confirmed by XPS study on lead sorption. More attractively, the exhausted HFO-001 beads can be effectively regenerated by HCl-NaCl solution (pH 3) for repeated use without any significant capacity loss. (c) 2009 Elsevier Ltd. All rights reserved.

Polyethylene imine modified hydrochar adsorption for chromium (VI) and nickel (II) removal from aqueous solution.

PubMed

Shi, Yuanji; Zhang, Tao; Ren, Hongqiang; Kruse, Andrea; Cui, Ruofan

2018-01-01

An adsorbent hydrochar was synthesized from corn cobs and modified with polyethylene imine (PEI). The hydrochars before and after modification were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis. FTIR and XPS revealed that the PEI was grafted onto the hydrochar via ether and imine bonds formed with glutaraldehyde. The maximum adsorption capacities for Cr(VI) (33.663mg/g) and Ni(II) (29.059mg/g) on the modified hydrochars were 365% and 43.7% higher, respectively, than those on the unmodified hydrochar. A pseudo-second-order model described the adsorption of Ni(II) and Cr(VI) on all the adsorbents. The adsorption of Cr(VI) was endothermic, spontaneous, increased disorder, and obeyed the Langmuir model. By contrast, the adsorption of Ni(II) was exothermic, spontaneous, decreased disorder, and obeyed the Freundlich model. XPS confirmed that the adsorption sites and mechanisms for Ni(II) and Cr(VI) on the modified hydrochars were different. Copyright © 2017 Elsevier Ltd. All rights reserved.

Deposition and characterization of stoichiometric films of V2O5 on Pd(111)

NASA Astrophysics Data System (ADS)

Feng, Xu; Abdel-Rahman, Mohammed K.; Kruppe, Christopher M.; Trenary, Michael

2017-10-01

A simple and efficient method has been used to grow V2O5 thin films on Pd(111) at a substrate temperature of 300 K through physical vapor deposition by heating a fine powder of V2O5 in a non-oxidative, UHV environment. X-ray photoelectron spectroscopy (XPS), reflection absorption infrared spectroscopy (RAIRS) and low energy electron diffraction (LEED) were used to characterize the thin films. When the as-grown films exceed a minimum thickness, characteristic features of V2O5 were revealed by XPS and RAIRS, which confirms the presence of stoichiometric V2O5. LEED indicates no long range order of the as-grown films at 300 K. Annealing to temperatures between 600 and 700 K causes a reduction of V2O5 to VO2 as identified by XPS and the formation of ordered structures as determined by LEED, and VO2 is predominant after annealing to 800 K. After further annealing to 1000 K, only an ordered form of V2O3 is present on Pd(111).

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

Yoshimoto, Shinya, E-mail: yosshi@issp.u-tokyo.ac.jp; Shiozawa, Yuichiro; Koitaya, Takanori

Electronic states and electrical conductivity of the native oxide Si(111) surface adsorbed with an electron donor tetrakis(dimethylamino)ethylene (TDAE) were investigated using ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy (XPS), and independently driven four-probe conductivity measurements. The formation of positively charged TDAE species is confirmed by the downward shift of the vacuum level by 1.45 eV, the absence of HOMO level in the valence band, and observation of the positively charged state in the N 1s XPS spectra. Si 2p XPS spectra and four-probe conductivity measurements revealed that TDAE adsorption induces an increase in downward band bending and a reduction in electrical resistancemore » of the surface, respectively. The sheet conductivity and the electron density of the surface are 1.1 μS/◻ and 4.6 × 10{sup 9} cm{sup −2}, respectively, after TDAE adsorption, and they are as high as 350% of the original surface. These results demonstrate that the electron density of the semiconductor surface is successfully controlled by the electron donor molecule TDAE.« less

Application of modern surface analytical tools in the investigation of surface deterioration processes

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1983-01-01

Surface profilometry and scanning electron microscopy were utilized to study changes in the surface of polymers when eroded. The X-ray photoelectron spectroscopy (XPS) and depth profile analysis indicate the corrosion of metal and ceramic surfaces and reveal the diffusion of certain species into the surface to produce a change in mechanical properties. Ion implantation, nitriding and plating and their effects on the surface are characterized. Auger spectroscopy analysis identified morphological properties of coatings applied to surfaces by sputter deposition.

Characterization of fossil remains using XRF, XPS and XAFS spectroscopies

NASA Astrophysics Data System (ADS)

Zougrou, I. M.; Katsikini, M.; Pinakidou, F.; Brzhezinskaya, M.; Papadopoulou, L.; Vlachos, E.; Tsoukala, E.; Paloura, E. C.

2016-05-01

Synchrotron radiation micro-X-Ray Fluorescence (μ-XRF), X-ray photoelectron (XPS) and X-ray Absorption Fine Structure (XAFS) spectroscopies are applied for the study of paleontological findings. More specifically the costal plate of a gigantic terrestrial turtle Titanochelon bacharidisi and a fossilized coprolite of the cave spotted hyena Crocuta crocuta spelaea are studied. Ca L 2,3-edge NEXAFS and Ca 2p XPS are applied for the identification and quantification of apatite and Ca containing minerals. XRF mapping and XAFS are employed for the study of the spatial distribution and speciation of the minerals related to the deposition environment.

X-ray photoelectron spectroscopy and atomic force microscopy characterization of the effects of etching Zn xCd 1- xTe surfaces

NASA Astrophysics Data System (ADS)

George, M. A.; Azoulay, M.; Jayatirtha, H. N.; Burger, A.; Collins, W. E.; Silberman, E.

1993-10-01

X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) was used for the first time to characterize the chemical composition of modified surfaces of Zn xCd 1- xTe single crystals. These surface treatments were selected for their relevance to device preparation procedures. The XPS peaks indicated an increase of the tellurium and a depletion of the cadmium concentrations upon etching in bromine methanol solution. AFM revealed the formation of pronounced Te inclusions. Higher x values correlated with a decrease in residual bromine left on the surface, while cut and polished samples had higher oxide concentrations and increased bromination of the surface than cleaved samples.

Intrinsic ferromagnetism in nanocrystalline Mn-doped ZnO depending on Mn concentration.

PubMed

Subramanian, Munisamy; Tanemura, Masaki; Hihara, Takehiko; Soga, Tetsuo; Jimbo, Takashi

2011-04-01

The physical properties of Zn(1-x)Mn(x)O nanoparticles synthesized by thermal decomposition are extensively investigated by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman light scattering and Hysteresis measurements. XRD and XPS spectra reveal the absence of secondary phase in nanocrystalline ZnO doped with 5% or less Mn; and, later confirms that the valance state of Mn to be 2+ for all the samples. Raman spectra exhibit a peak at 660 cm(-1) which we attribute to the intrinsic lattice defects of ZnO with increasing Mn concentration. Overall, our results demonstrate that ferromagnetic properties can be realized while Mn-doped ZnO obtained in the nanocrystalline form.

Synthesis of TiN/a-Si3N4 thin film by using a Mather type dense plasma focus system

NASA Astrophysics Data System (ADS)

Hussain, T.; R., Ahmad; Khalid, N.; A. Umar, Z.; Hussnain, A.

2013-05-01

A 2.3 kJ Mather type pulsed plasma focus device was used for the synthesis of a TiN/a-Si3N4 thin film at room temperature. The film was characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The XRD pattern confirms the growth of polycrystalline TiN thin film. The XPS results indicate that the synthesized film is non-stoichiometric and contains titanium nitride, silicon nitride, and a phase of silicon oxy-nitride. The SEM and AFM results reveal that the surface of the synthesized film is quite smooth with 0.59 nm roughness (root-mean-square).

A ToF-SIMS and XPS study of protein adsorption and cell attachment across PEG-like plasma polymer films with lateral compositional gradients

NASA Astrophysics Data System (ADS)

Menzies, Donna J.; Jasieniak, Marek; Griesser, Hans J.; Forsythe, John S.; Johnson, Graham; McFarland, Gail A.; Muir, Benjamin W.

2012-12-01

In this work we report a detailed X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) study of poly(ethylene glycol) PEG-like chemical gradients deposited via plasma enhanced chemical vapour deposition (PECVD) at two different load powers using diethylene glycol dimethyl ether (DG) as a monomer. Principal component analysis (PCA) was applied to the ToF-SIMS data both before and after protein adsorption on the plasma polymer thin films. Results of the PCA loadings indicated a higher content of hydrocarbon fragments across the higher load power gradient, which adsorbed higher amounts of proteins. Gradients deposited at a lower load power retained a higher degree of monomer like functionality as did the central region directly underneath the knife edge electrode. Analysis of the adsorption of serum proteins (human serum albumin and fetal bovine serum) was monitored across the gradient films and increased with decreasing ether (PEG-like) film chemistries. The effect of protein incubation time on the levels adsorbed fetal bovine serum on the plasma polymer films was critical, with significantly more protein adsorbing after 24 hour incubation times on both gradient films. The attachment of HeLa cells on the gradients appeared to be dictated not only by the surface chemistry, but also by the adsorption of serum proteins. XPS analysis revealed that at surface ether concentrations of less than 70% in the gradient films, significant increases in protein and cell attachment were observed.

Surface-and bulk-properties of EPDM rubber modified by electron beam irradiation

NASA Astrophysics Data System (ADS)

Majumder, Papiya Sen; Bhowmick, Anil K.

1999-01-01

Electron beam initiated grafting of trimethylol propane triacrylate (TMPTA) onto ethylene propylene diene monomer (EPDM) has been carried out over a wide range of irradiation doses (0-200 kGy) using a fixed concentration (10%) of TMPTA. The samples have been both surface and bulk modified. Infrared (IR) studies indicate increased peak absorbances at 1730, 1260, 1120 and 1019 cm -1 upto 50 kGy and hence increased CO and C-O-C concentrations. The results are further supported by X-ray photoelectron spectroscopy (XPS) studies. The surface energy of EPDM increases from 46.5 to 60.7 mJ/m 2 on irradiation of the surface modified samples to 50 kGy dose, due to increased contribution of γSAB and γS(-). The results have been explained with the help of IR and XPS data. The values of tensile strength of the surface modified samples have not changed very significantly, while the moduli values have increased at the cost of the elongation at break. DMTA studies have shown changes in Tg and tan δmax on modification of the surface. The surface morphology of the modified and irradiated samples reveals acrylate flow marks at high magnification.

13C NMR and XPS characterization of anion adsorbent with quaternary ammonium groups prepared from rice straw, corn stalk and sugarcane bagasse

NASA Astrophysics Data System (ADS)

Cao, Wei; Wang, Zhenqian; Zeng, Qingling; Shen, Chunhua

2016-12-01

Despite amino groups modified crop straw has been intensively studied as new and low-cost adsorbent for removal of anionic species from water, there is still a lack of clear characterization for amino groups, especially quaternary ammonium groups in the surface of crop straw. In this study, we used 13C NMR and XPS technologies to characterize adsorbents with quaternary ammonium groups prepared from rice straw, corn stalk and sugarcane bagasse. 13C NMR spectra clearly showed the presence of quaternary ammonium groups in lignocelluloses structure of modified crop straw. The increase of nitrogen observed in XPS survey spectra also indicated the existence of quaternary ammonium group in the surface of the adsorbents. The curve fitting of high-resolution XPS N1s and C1s spectra were conducted to probe the composition of nitrogen and carbon contained groups, respectively. The results showed the proportion of quaternary ammonium group significantly increased in the prepared adsorbent's surface that was dominated by methyl/methylene, hydroxyl, quaternary ammonium, ether and carbonyl groups. This study proved that 13C NMR and XPS could be successfully utilized for characterization of quaternary ammonium modified crop straw adsorbents.

Surface Analysis of 4-Aminothiophenol Adsorption at Polycrystalline Platinum Electrodes

NASA Technical Reports Server (NTRS)

Rosario-Castro, Belinda I.; Fachini, Estevao R.; Contes, Enid J.; Perez-Davis, Marla E.; Cabrera, Carlos R.

2008-01-01

Formation of self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) on polycrystalline platinum electrodes has been studied by surface analysis and electrochemistry techniques. The 4-ATP monolayer was characterized by cyclic voltammetry (CV), Raman spectroscopy, reflection absorption infrared (RAIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV) experiments give an idea about the packing quality of the monolayer. RAIR and Raman spectra for 4-ATP modified platinum electrodes showed the characteristic adsorption bands for neat 4-ATP indicating the adsorption of 4-ATP molecules on platinum surface. The adsorption on platinum was also evidenced by the presence of sulfur and nitrogen peaks by XPS survey spectra of the modified platinum electrodes. High resolution XPS studies and RAIR spectrum for platinum electrodes modified with 4-ATP indicate that molecules are sulfur-bonded to the platinum surface. The formation of S-Pt bond suggests that ATP adsorption gives up an amino terminated SAM. Thickness of the monolayer was evaluated via angle-resolved XPS (AR-XPS) analyses. Derivatization of 4-ATP SAM was performed using 16-Br hexadecanoic acid.

Multicenter study on costs associated with two surgical procedures: GreenLight XPS 180 W versus the gold standard transurethral resection of the prostate.

PubMed

Benejam-Gual, J M; Sanz-Granda, A; Budía, A; Extramiana, J; Capitán, C

2014-01-01

To analyze the costs associated with two surgical procedures for lower urinary tract symptoms secondary to benign prostatic hyperplasia: GreenLight XPS 180¦W versus the gold standard transurethral resection of the prostate. A multicenter, retrospective cost study was carried out from the National Health Service perspective, over a 3-month time period. Costs were broken down into pre-surgical, surgical and post-surgical phases. Data were extracted from records of patients operated sequentially, with IPSS=15, Qmax=15 mL/seg and a prostate volume of 40-80mL, adding only direct healthcare costs (€, 2013) associated with the procedure and management of complications. A total of 79 patients sequentially underwent GL XPS (n: 39) or TURP (n: 40) between July and October, 2013. Clinical outcomes were similar (94.9% and 92.5%, GL XPS and TURP, respectively) without significant differences (P=.67). The average direct cost per patient was reduced by €114 in GL XPS versus TURP patients; the cost was higher in the surgical phase with GL XPS (difference: €1,209; P<.001) but was lower in the post-surgical phase (difference: €-1,351; P<.001). The GreenLight XPS 180-W laser system is associated with a reduction in costs with respect to transurethral resection of prostate in the surgical treatment of LUTS secondary to PBH. This reduction is due to a shorter inpatient length of stay that offsets the cost of the new technology. Copyright © 2013 AEU. Published by Elsevier Espana. All rights reserved.

An in situ XPS study of L-cysteine co-adsorbed with water on polycrystalline copper and gold

NASA Astrophysics Data System (ADS)

Jürgensen, Astrid; Raschke, Hannes; Esser, Norbert; Hergenröder, Roland

2018-03-01

The interactions of biomolecules with metal surfaces are important because an adsorbed layer of such molecules introduces complex reactive functionality to the substrate. However, studying these interactions is challenging: they usually take place in an aqueous environment, and the structure of the first few monolayers on the surface is of particular interest, as these layers determine most interfacial properties. Ideally, this requires surface sensitive analysis methods that are operated under ambient conditions, for example ambient pressure x-ray photoelectron spectroscopy (AP-XPS). This paper focuses on an AP-XPS study of the interaction of water vapour and l-Cysteine on polycrystalline copper and gold surfaces. Thin films of l-Cysteine were characterized with XPS in UHV and in a water vapour atmosphere (P ≤ 1 mbar): the structure of the adsorbed l-Cysteine layer depended on substrate material and deposition method, and exposure of the surface to water vapour led to the formation of hydrogen bonds between H2O molecules and the COO- and NH2 groups of adsorbed l-Cysteine zwitterions and neutral molecules, respectively. This study also proved that it is possible to investigate monolayers of biomolecules in a gas atmosphere with AP-XPS using a conventional laboratory Al-Kα x-ray source.

A combined ToF-SIMS and XPS study for the elucidation of the role of water in the performances of a Post-Plasma Process using LaMnO3+δ as catalyst in the total oxidation of trichloroethylene

NASA Astrophysics Data System (ADS)

Nuns, N.; Beaurain, A.; Dinh, M. T. Nguyen; Vandenbroucke, A.; De Geyter, N.; Morent, R.; Leys, C.; Giraudon, J.-M.; Lamonier, J.-F.

2014-11-01

LaMnO3+δ which is an environment-friendly and inexpensive material has been previously used as catalyst in Post-Plasma Catalysis (PPC) in the total oxidation of trichloroethylene (TCE) which is a solvent widely used in dry cleaning and degreasing processes. It has been shown that the process efficiency increases in moist air (RH = 18%).The issue we want to address herein is the effect of water on the location of chlorine at the surface of the catalyst as chlorine is able to alter the catalyst structure, activity and stability. Therefore, a combined Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS) and X-ray Photoelectron Spectroscopy (XPS) study has been carried out on the fresh LaMnO3+δ catalyst (LM) and used catalysts after performing PPC with TCE diluted in dry synthetic air (LM0) or with industrial air containing water (LM18; 18 stands for the Relative Humidity) and CO2 (about 560 ppmv) at a temperature of 150 °C. XPS and ToF-SIMS results both show the presence of chlorine on the tested catalysts whose amount increases by exposure of the catalyst to the reactive mixture in dry synthetic air. XPS results reveal that chlorine is present as both chloride ion and covalent chlorine on LM0 while organic chlorinated residues are absent on LM18 catalyst. ToF-SIMS study indicates that lanthanum excess as oxide(hydroxide) partially covering the perovskite mainly transforms into LaOCl and to a minor extent into LaCl3. Extent of Mn chlorination seems to be favored over LM0 having a higher MnClx±/MnOCl± ionic ratio compared to LM18. Furthermore ToF-SIMS clearly identifies C1 chlorinated organic ions, mainly CH2Cl+ and CHCl2-, on LM0 which may contribute to the XPS Cl organic component. From the combined ToF-SIMS and XPS results it is found that water delays the surface degradation extent of the perovskite into related (oxy)(hydroxy)chlorinated inorganic phases by less molecular chlorine and related chlorine species on the catalyst surface. A reaction scheme of Cl removal over LaMnO3+δ emphasing the role of water is given taking into account the detection of ToF-SIMS ions representative of the successive Mn intermediate states. As a consequence water allows tuning the degradation pathways of the main intermediate of the reaction, dichloroacetyl chloride (DCAC), which decomposes to give phosgene, HCCl3 and CCl4 by a successive Cl incorporation over (oxy)(hydroxy)chorinated perovskite or/and Mn species while COx species are likely formed over the perovskite.

XPS characterization of silver exchanged ETS-10 and mordenite molecular sieves.

PubMed

Anson, A; Maham, Y; Lin, C C H; Kuznicki, T M; Kuznicki, S M

2009-05-01

Silver exchanged molecular sieves ETS-10 (Ag-ETS-10) and mordenite (Ag-mordenite) were dehydrated under vacuum at temperatures between 100 degrees C-350 degrees C. Changes in the state of the silver were studied using X-ray photoelectron spectroscopy (XPS). Silver cations in titanosilicate Ag-ETS-10 are fully reduced to Ag(0) at temperatures as low as 150 degrees C. The characteristic features of the XPS spectrum of silver in this Ag-ETS-10 species correspond to only metallic silver. The signal for metallic silver is not observed in the XPS spectrum of aluminosilicate Ag-mordenite, indicating that silver cations are not reduced, even after heating to 350 degrees C.

Segregation Phenomena in Size-Selected Bimetallic CuNi Nanoparticle Catalysts

DOE PAGES

Pielsticker, Lukas; Zegkinoglou, Ioannis; Divins, Nuria J.; ...

2017-10-25

Surface segregation, restructuring, and sintering phenomena in size-selected copper–nickel nanoparticles (NPs) supported on silicon dioxide substrates were systematically investigated as a function of temperature, chemical state, and reactive gas environment. Using near-ambient pressure (NAP-XPS) and ultrahigh vacuum X-ray photoelectron spectroscopy (XPS), we showed that nickel tends to segregate to the surface of the NPs at elevated temperatures in oxygen- or hydrogen-containing atmospheres. It was found that the NP pretreatment, gaseous environment, and oxide formation free energy are the main driving forces of the restructuring and segregation trends observed, overshadowing the role of the surface free energy. The depth profile ofmore » the elemental composition of the particles was determined under operando CO 2 hydrogenation conditions by varying the energy of the X-ray beam. The temperature dependence of the chemical state of the two metals was systematically studied, revealing the high stability of nickel oxides on the NPs and the important role of high valence oxidation states in the segregation behavior. Atomic force microscopy (AFM) studies revealed a remarkable stability of the NPs against sintering at temperatures as high as 700 °C. The results provide new insights into the complex interplay of the various factors which affect alloy formation and segregation phenomena in bimetallic NP systems, often in ways different from those previously known for their bulk counterparts. In conclusion, this leads to new routes for tuning the surface composition of nanocatalysts, for example, through plasma and annealing pretreatments.« less

Adsorption study of copper phthalocyanine on Si(111)(√3 × √3)R30°Ag surface

NASA Astrophysics Data System (ADS)

Menzli, S.; Ben Hamada, B.; Arbi, I.; Souissi, A.; Laribi, A.; Akremi, A.; Chefi, C.

2016-04-01

The adsorption of copper phthalocyanine (CuPc) molecules on Si(111)(√3 × √3)R30°Ag surface is studied at room temperature under ultra high vacuum. Crystallographic, chemical and electronic properties of the interface are investigated by low energy electron diffraction (LEED), ultraviolet and X-ray photoemission spectroscopies (UPS, XPS) and X-ray photoemission diffraction (XPD). LEED and XPD results indicate that after one monolayer deposition the molecular layer is highly ordered with a flat lying adsorption configuration. The corresponding pattern reveals the coexistence of three symmetrically equivalent orientations of molecules with respect to the substrate. XPS core level spectra of the substrate reveal that there is no discernible chemical interaction between molecules and substrate; however there is evidence of Fermi level movement. During the growth, the work function was found to decrease from 4.90 eV for the clean substrate to 4.35 eV for the highest coverage (60 monolayers). Within a thickness of two monolayer deposition an interface dipole of 0.35 eV and a band bending of 0.2 eV have been found. UPS spectra indicate the existence of a band bending of the highest occupied molecular orbital (HOMO) of 0.55 eV. The changes in the work function, in the Fermi level position and in the HOMO state have been used to determine the energy level alignment at the interface.

Empirical optimization of DFT  +  U and HSE for the band structure of ZnO.

PubMed

Bashyal, Keshab; Pyles, Christopher K; Afroosheh, Sajjad; Lamichhane, Aneer; Zayak, Alexey T

2018-02-14

ZnO is a well-known wide band gap semiconductor with promising potential for applications in optoelectronics, transparent electronics, and spintronics. Computational simulations based on the density functional theory (DFT) play an important role in the research of ZnO, but the standard functionals, like Perdew-Burke-Erzenhof, result in largely underestimated values of the band gap and the binding energies of the Zn 3d electrons. Methods like DFT  +  U and hybrid functionals are meant to remedy the weaknesses of plain DFT. However, both methods are not parameter-free. Direct comparison with experimental data is the best way to optimize the computational parameters. X-ray photoemission spectroscopy (XPS) is commonly considered as a benchmark for the computed electronic densities of states. In this work, both DFT  +  U and HSE methods were parametrized to fit almost exactly the binding energies of electrons in ZnO obtained by XPS. The optimized parameterizations of DFT  +  U and HSE lead to significantly worse results in reproducing the ion-clamped static dielectric tensor, compared to standard high-level calculations, including GW, which in turn yield a perfect match for the dielectric tensor. The failure of our XPS-based optimization reveals the fact that XPS does not report the ground state electronic structure for ZnO and should not be used for benchmarking ground state electronic structure calculations.

Empirical optimization of DFT  +  U and HSE for the band structure of ZnO

NASA Astrophysics Data System (ADS)

Bashyal, Keshab; Pyles, Christopher K.; Afroosheh, Sajjad; Lamichhane, Aneer; Zayak, Alexey T.

2018-02-01

ZnO is a well-known wide band gap semiconductor with promising potential for applications in optoelectronics, transparent electronics, and spintronics. Computational simulations based on the density functional theory (DFT) play an important role in the research of ZnO, but the standard functionals, like Perdew-Burke-Erzenhof, result in largely underestimated values of the band gap and the binding energies of the Zn3d electrons. Methods like DFT  +  U and hybrid functionals are meant to remedy the weaknesses of plain DFT. However, both methods are not parameter-free. Direct comparison with experimental data is the best way to optimize the computational parameters. X-ray photoemission spectroscopy (XPS) is commonly considered as a benchmark for the computed electronic densities of states. In this work, both DFT  +  U and HSE methods were parametrized to fit almost exactly the binding energies of electrons in ZnO obtained by XPS. The optimized parameterizations of DFT  +  U and HSE lead to significantly worse results in reproducing the ion-clamped static dielectric tensor, compared to standard high-level calculations, including GW, which in turn yield a perfect match for the dielectric tensor. The failure of our XPS-based optimization reveals the fact that XPS does not report the ground state electronic structure for ZnO and should not be used for benchmarking ground state electronic structure calculations.

Electron spectroscopy analysis

NASA Technical Reports Server (NTRS)

Gregory, John C.

1992-01-01

The Surface Science Laboratories at the University of Alabama in Huntsville (UAH) are equipped with x-ray photoelectron spectroscopy (XPS or ESCA) and Auger electron spectroscopy (AES) facilities. These techniques provide information from the uppermost atomic layers of a sample, and are thus truly surface sensitive. XPS provides both elemental and chemical state information without restriction on the type of material that can be analyzed. The sample is placed into an ultra high vacuum (UHV) chamber and irradiated with x-rays which cause the ejection of photoelectrons from the sample surface. Since x-rays do not normally cause charging problems or beam damage, XPS is applicable to a wide range of samples including metals, polymers, catalysts, and fibers. AES uses a beam of high energy electrons as a surface probe. Following electronic rearrangements within excited atoms by this probe, Auger electrons characteristic of each element present are emitted from the sample. The main advantage of electron induced AES is that the electron beam can be focused down to a small diameter and localized analysis can be carried out. On the rastering of this beam synchronously with a video display using established scanning electron microscopy techniques, physical images and chemical distribution maps of the surface can be produced. Thus very small features, such as electronic circuit elements or corrosion pits in metals, can be investigated. Facilities are available on both XPS and AES instruments for depth-profiling of materials, using a beam of argon ions to sputter away consecutive layers of material to reveal sub-surface (and even semi-bulk) analyses.

Silver deposition on stainless steel container surfaces in contact with disinfectant silver aqueous solutions

NASA Astrophysics Data System (ADS)

Petala, M.; Tsiridis, V.; Mintsouli, I.; Pliatsikas, N.; Spanos, Th.; Rebeyre, P.; Darakas, E.; Patsalas, P.; Vourlias, G.; Kostoglou, M.; Sotiropoulos, S.; Karapantsios, Th.

2017-02-01

Silver is the preservative used on the Russian segment of the International Space Station (ISS) to prevent microbial proliferation within potable water supplies. Yet, in the frame of the European Automated Transfer Vehicle (ATV) missions to ISS, silver depletion from water has been detected during ground transportation of this water to launch site, thereby indicating a degradation of water quality. This study investigates the silver loss from water when in contact with stainless steel surfaces. Experiments are conducted with several types of stainless steel surfaces being exposed to water containing 10 or 0.5 mg/L silver ions. Results show that silver deposits on stainless steel surfaces even when a passivation layer protects the metallic surface. The highest protection to silver deposition is offered by acid passivated and electropolished SS 316L. SEM and XPS experiments were carried out at several locations of the sample area that was in contact with the Ag solution and found similar morphological (SEM) and compositional (sputter-etch XPS) results. The results reveal that silver deposits uniformly across the wetted surface to a thickness larger than 3 nm. Moreover, evidence is provided that silver deposits in its metallic form on all stainless steel surfaces, in line with a galvanic deposition mechanism. Combination of ICP-MS and XPS results suggests a mechanism for Ag deposition/reduction with simultaneous substrate oxidation resulting in oxide growth at the exposed stainless steel surface.

XPS and bioactivity study of the bisphosphonate pamidronate adsorbed onto plasma sprayed hydroxyapatite coatings

NASA Astrophysics Data System (ADS)

McLeod, Kate; Kumar, Sunil; Smart, Roger St. C.; Dutta, Naba; Voelcker, Nicolas H.; Anderson, Gail I.; Sekel, Ron

2006-12-01

This paper reports the use of X-ray photoelectron spectroscopy (XPS) to investigate bisphosphonate (BP) adsorption onto plasma sprayed hydroxyapatite (HA) coatings commonly used for orthopaedic implants. BPs exhibit high binding affinity for the calcium present in HA and hence can be adsorbed onto HA-coated implants to exploit their beneficial properties for improved bone growth at the implant interface. A rigorous XPS analysis of pamidronate, a commonly used nitrogenous BP, adsorbed onto plasma sprayed HA-coated cobalt-chromium substrates has been carried out, aimed at: (a) confirming the adsorption of this BP onto HA; (b) studying the BP diffusion profile in the HA coating by employing the technique of XPS depth profiling; (c) confirming the bioactivity of the adsorbed BP. XPS spectra of plasma sprayed HA-coated discs exposed to a 10 mM aqueous BP solution (pamidronate) for periods of 1, 2 and 24 h showed nitrogen and phosphorous photoelectron signals corresponding to the BP, confirming its adsorption onto the HA substrate. XPS depth profiling of the 2 h BP-exposed HA discs showed penetration of the BP into the HA matrix to depths of at least 260 nm. The bioactivity of the adsorbed BP was confirmed by the observed inhibition of osteoclast (bone resorbing) cell activity. In comparison to the HA sample, the HA sample with adsorbed BP exhibited a 25-fold decrease in primary osteoclast cells.

XPS Study of Oxide/GaAs and SiO2/Si Interfaces

NASA Technical Reports Server (NTRS)

Grunthaner, F. J.; Grunthaner, P. J.; Vasquez, R. P.; Lewis, B. F.; Maserjian, J.; Madhukar, A.

1982-01-01

Concepts developed in study of SiO2/Si interface applied to analysis of native oxide/GaAs interface. High-resolution X-ray photoelectron spectroscopy (XPS) has been combined with precise chemical-profiling technique and resolution-enhancement methods to study stoichiometry of transitional layer. Results are presented in report now available.

Theoretical modeling of the uranium 4f XPS for U(VI) and U(IV) oxides

NASA Astrophysics Data System (ADS)

Bagus, Paul S.; Nelin, Connie J.; Ilton, Eugene S.

2013-12-01

A rigorous study is presented of the physical processes related to X-Ray photoelectron spectroscopy, XPS, in the 4f level of U oxides, which, as well as being of physical interest in themselves, are representative of XPS in heavy metal oxides. In particular, we present compelling evidence for a new view of the screening of core-holes that extends prior understandings. Our analysis of the screening focuses on the covalent mixing of high lying U and O orbitals as opposed to the, more common, use of orbitals that are nominally pure U or pure O. It is shown that this covalent mixing is quite different for the initial and final, core-hole, configurations and that this difference is directly related to the XPS satellite intensity. Furthermore, we show that the high-lying U d orbitals as well as the U(5f) orbital may both contribute to the core-hole screening, in contrast with previous work that has only considered screening through the U(5f) shell. The role of modifying the U-O interaction by changing the U-O distance has been investigated and an unexpected correlation between U-O distance and XPS satellite intensity has been discovered. The role of flourite and octahedral crystal structures for U(IV) oxides has been examined and relationships established between XPS features and the covalent interactions in the different structures. The physical views of XPS satellites as arising from shake processes or as arising from ligand to metal charge transfers are contrasted; our analysis provides strong support that shake processes give a more fundamental physical understanding than charge transfer. Our theoretical studies are based on rigorous, strictly ab initio determinations of the electronic structure of embedded cluster models of U oxides with formal U(VI) and U(IV) oxidation states. Our results provide a foundation that makes it possible to establish quantitative relationships between features of the XPS spectra and materials properties.

Corrosive effects of fluoride on titanium: investigation by X-ray photoelectron spectroscopy, atomic force microscopy, and human epithelial cell culturing.

PubMed

Stájer, Anette; Ungvári, Krisztina; Pelsoczi, István K; Polyánka, Hilda; Oszkó, Albert; Mihalik, Erzsébet; Rakonczay, Zoltán; Radnai, Márta; Kemény, Lajos; Fazekas, András; Turzó, Kinga

2008-11-01

High fluoride (F(-)) concentrations and acidic pH impair the corrosion resistance of titanium (Ti). Effects of F(-)-containing caries-preventive prophylactic rinses, and gels on Ti were investigated by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Human epithelial cell attachment and proliferation were investigated by dimethylthiazol-diphenyl tetrazolium bromide (MTT) and protein content assays. Aqueous 1% NaF solution (3800 ppm F(-), pH 4.5) or high (12,500 ppm) F(-) content gel (pH 4.8) strongly corroded the surface and modified its composition. XPS revealed formation of a strongly bound F(-)-containing complex (Na(2)TiF(6)). AFM indicated an increase in roughness (R(a)) of the surfaces: 10-fold for the NaF solution and smaller for the gel or a mouthwash (250 ppm F(-), pH 4.4). MTT revealed that cell attachment was significantly increased by the gel, but was not disturbed by either the mouthwash or the NaF. Cell proliferation determined by MTT decreased significantly only for the NaF-treated samples; protein content assay experiments showed no such effect. This study indicates that epithelial cell culturing results can depend on the method used, and the adverse effects of a high F(-) concentration and low pH should be considered when prophylactic gels are applied by patients with Ti implants or other dental devices.

Study of fission-product segregation in used CANDU fuel by X-ray photoelectron spectroscopy (XPS) II

NASA Astrophysics Data System (ADS)

Hocking, William H.; Duclos, A. Michael; Johnson, Lawrence H.

1994-03-01

A thorough investigation of the grain-boundary chemistry of used CANDU fuel from one intact element has been conducted by X-ray photoelectron spectroscopy (XPS). Selected findings from more extensive XPS measurements on other used CANDU fuels exposed to storage conditions are included for comparison. Cesium, rubidium, tellurium and barium have been commonly observed, often reaching high degrees of surface enrichment, although their relative abundances can vary widely with a complex dependence on the fuel irradiation history. Lower concentrations of cadmium, molybdenum, strontium and iodine have also been occasionally detected. Except for iodine, chemical-shift data are indicative of oxidized species, possibly uranates. Segregation at monolayer-level coverages has been demonstrated by sequential XPS analysis and argon-ion sputtering. Calculations based on an idealized thin-film model are consistent with the depth profiles. The interpretation of these results is discussed in the context of previous studies, especially on LWR fuels.

X-ray Photoelectron Spectroscopy (XPS), Rutherford Back Scattering (RBS) studies

NASA Technical Reports Server (NTRS)

Neely, W. C.; Bozak, M. J.; Williams, J. R.

1993-01-01

X-ray photoelectron spectroscopy (XPS), Rutherford Back Scattering (RBS) studies of each of sample received were completed. Since low angle X-ray could not be performed because of instrumentation problems, Auger spectrometry was employed instead. The results of these measurements for each of the samples is discussed in turn.

Pinus Pinaster surface treatment realized in spatial and temporal afterglow DBD conditions

NASA Astrophysics Data System (ADS)

Lecoq, E.; Clément, F.; Panousis, E.; Loiseau, J.-F.; Held, B.; Castetbon, A.; Guimon, C.

2008-04-01

This experimental work deals with the exposition of Pinus Pinaster wood samples to a DBD afterglow. Electrical parameters like duty cycle and injected energy in the gas are being varied and the modifications induced by the afterglow on the wood are analysed by several macroscopic and microscopic ways like wettability, XPS analyses and also soaking tests of treated wood in a commercial fungicide solution. Soaking tests show that plasma treatment could enhance the absorption of fungicide into the wood. The wettability results point out that the plasma treatment can inflict on the wood different surface properties, making it hydrophilic or hydrophobic, when varying electrical parameters. XPS analyses reveal several chemical modifications like an increase of the O/C ratio and the presence of carboxyl groups on the surface after plasma treatments.

Gallium-containing polymer brush film as efficient supported Lewis acid catalyst in a glass microreactor.

PubMed

Munirathinam, Rajesh; Ricciardi, Roberto; Egberink, Richard J M; Huskens, Jurriaan; Holtkamp, Michael; Wormeester, Herbert; Karst, Uwe; Verboom, Willem

2013-01-01

Polystyrene sulfonate polymer brushes, grown on the interior of the microchannels in a microreactor, have been used for the anchoring of gallium as a Lewis acid catalyst. Initially, gallium-containing polymer brushes were grown on a flat silicon oxide surface and were characterized by FTIR, ellipsometry, and X-ray photoelectron spectroscopy (XPS). XPS revealed the presence of one gallium per 2-3 styrene sulfonate groups of the polymer brushes. The catalytic activity of the Lewis acid-functionalized brushes in a microreactor was demonstrated for the dehydration of oximes, using cinnamaldehyde oxime as a model substrate, and for the formation of oxazoles by ring closure of ortho-hydroxy oximes. The catalytic activity of the microreactor could be maintained by periodic reactivation by treatment with GaCl3.

Chrome-free Samarium-based Protective Coatings for Magnesium Alloys

NASA Astrophysics Data System (ADS)

Hou, Legan; Cui, Xiufang; Yang, Yuyun; Lin, Lili; Xiao, Qiang; Jin, Guo

The microstructure of chrome-free samarium-based conversion coating on magnesium alloy was investigated and the corrosion resistance was evaluated as well. The micro-morphology, transverse section, crystal structure and composition of the coating were observed by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive spectroscopy (EDS) and X- ray photoelectron spectroscopy (XPS), respectively. The corrosion resistance was evaluated by potentiodynamic polarization curve and electrochemical impedance spectroscopy (EIS). The results reveal that the morphology of samarium conversion coating is of crack-mud structure. Tiny cracks distribute in the compact coating deposited by samarium oxides. XRD, EDS and XPS results characterize that the coating is made of amorphous and trivalent-samarium oxides. The potentiodynamic polarization curve, EIS and OCP indicate that the samarium conversion coating can improve the corrosion resistance of magnesium alloys.

Compositions of surface layers formed on amalgams in air, water, and saline.

PubMed

Hanawa, T; Gnade, B E; Ferracane, J L; Okabe, T; Watari, F

1993-12-01

The surface layers formed on both a zinc-free and a zinc-containing dental amalgam after polishing and aging in air, water, or saline, were characterized using x-ray photoelectron spectroscopy (XPS) to determine the compositions of the surface layers which might govern the release of mercury from amalgam. The XPS data revealed that the formation of the surface layer on the zinc-containing amalgam was affected by the environment in which the amalgam was polished and aged, whereas that on the zinc-free amalgam was not affected. In addition, among the elements contained in amalgam, zinc was the most reactive with the environment, and was preferentially dissolved from amalgam into water or saline. Mercury atoms existed in the metallic state in the surface layer.

Impact of Microstructure on MoS 2 Oxidation and Friction

DOE PAGES

Curry, John F.; Wilson, Mark A.; Luftman, Henry S.; ...

2017-07-31

In this work, we demonstrate the role of microstructure in the friction and oxidation behavior of the lamellar solid lubricant molybdenum disulfide (MoS 2). We report on systematic investigations of oxidation and friction for two MoS 2 films with distinctively different microstructures—amorphous and planar/highly-ordered—before and after exposure to atomic oxygen (AO) and high-temperature (250 °C) molecular oxygen. A combination of experimental tribology, molecular dynamics simulations, X-ray photoelectron spectroscopy (XPS), and high-sensitivity low-energy ion scattering (HS-LEIS) was used to reveal new insights about the links between structure and properties of these widely utilized low-friction materials. Initially, ordered MoS 2 films showedmore » a surprising resistance to both atomic and molecular oxygens (even at elevated temperature), retaining characteristic low friction after exposure to extreme oxidative environments. Finally, XPS shows comparable oxidation of both coatings via AO; however, monolayer resolved compositional depth profiles from HS-LEIS reveal that the microstructure of the ordered coatings limits oxidation to the first atomic layer.« less

Impact of Microstructure on MoS 2 Oxidation and Friction

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

Curry, John F.; Wilson, Mark A.; Luftman, Henry S.

In this work, we demonstrate the role of microstructure in the friction and oxidation behavior of the lamellar solid lubricant molybdenum disulfide (MoS 2). We report on systematic investigations of oxidation and friction for two MoS 2 films with distinctively different microstructures—amorphous and planar/highly-ordered—before and after exposure to atomic oxygen (AO) and high-temperature (250 °C) molecular oxygen. A combination of experimental tribology, molecular dynamics simulations, X-ray photoelectron spectroscopy (XPS), and high-sensitivity low-energy ion scattering (HS-LEIS) was used to reveal new insights about the links between structure and properties of these widely utilized low-friction materials. Initially, ordered MoS 2 films showedmore » a surprising resistance to both atomic and molecular oxygens (even at elevated temperature), retaining characteristic low friction after exposure to extreme oxidative environments. Finally, XPS shows comparable oxidation of both coatings via AO; however, monolayer resolved compositional depth profiles from HS-LEIS reveal that the microstructure of the ordered coatings limits oxidation to the first atomic layer.« less

A first-principles core-level XPS study on the boron impurities in germanium crystal

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

Yamauchi, Jun; Yoshimoto, Yoshihide; Suwa, Yuji

2013-12-04

We systematically investigated the x-ray photoelectron spectroscopy (XPS) core-level shifts and formation energies of boron defects in germanium crystals and compared the results to those in silicon crystals. Both for XPS core-level shifts and formation energies, relationship between defects in Si and Ge is roughly linear. From the similarity in the formation energy, it is expected that the exotic clusters like icosahedral B12 exist in Ge as well as in Si.

Dielectric relaxation and electronic structure of double perovskite Sr{sub 2}FeSbO{sub 6}

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

Dutta, Alo; Sinha, T. P.; Shannigrahi, Santiranjan

2008-09-15

The dielectric property and the electronic structure of a double perovskite, Sr{sub 2}FeSbO{sub 6} (SFS) synthesized by solid state reaction technique are investigated. The x-ray diffraction of the sample taken at room temperature shows cubic phase. The scanning electron micrograph of the sample also confirms the formation of the single phase of the material. We have measured the capacitance and conductance of SFS in a frequency range from 50 Hz to 1 MHz and in a temperature range from 163 to 463 K. A relaxation is observed in the entire temperature range as a gradual decrease in {epsilon}{sup '}({omega}) andmore » as a broad peak in {epsilon}{sup ''}({omega}). The frequency dependent electrical data are analyzed in the framework of conductivity and electric modulus formalisms. The frequencies corresponding to the maxima of the imaginary electric modulus at various temperatures are found to obey an Arrhenius law with an activation energy of 0.74 eV. The Cole-Cole model is used to study the dielectric relaxation of SFS. The scaling behavior of imaginary part of electric modulus suggests that the relaxation describes the same mechanism at various temperatures. The frequency dependent conductivity spectra follow the universal power law. The electronic structure of the SFS is studied by x-ray photoemission spectroscopy (XPS). Its valence band consists mainly of the oxygen 2p-states hybridized with the Fe 3d-states. The XPS spectra are investigated by the first principles full potential linearized augmented plane wave method. The angular momentum projected total and partial density of states obtained from first principles calculation are used to analyze the XPS results of the sample. The calculated electronic structures of SFS are qualitatively similar to those of the XPS spectra in terms of spectral features, energy positions, and relative intensities. The electronic structure calculation reveals that the electrical properties of SFS are dominated by the interaction between transition-metal and oxygen ions.« less

Performance and Durability of Thin Film Thermocouple Array on a Porous Electrode.

PubMed

Guk, Erdogan; Ranaweera, Manoj; Venkatesan, Vijay; Kim, Jung-Sik

2016-08-23

Management of solid oxide fuel cell (SOFC) thermal gradients is vital to limit thermal expansion mismatch and thermal stress. However, owing to harsh operation conditions of SOFCs and limited available space in stack configuration, the number of techniques available to obtain temperature distribution from the cell surface is limited. The authors previously developed and studied a thermocouple array pattern to detect surface temperature distribution on an SOFC in open circuit conditions. In this study, the performance in terms of mechanical durability and oxidation state of the thin film thermoelements of the thermocouple array on the porous SOFC cathode is investigated. A thin-film multi-junction thermocouple array was sputter deposited using a magnetron sputter coater. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) characterisation techniques were carried out to understand characteristics of the thin film before and after temperature (20 °C-800 °C) measurement. Temperature readings from the sensor agreed well with the closely placed commercial thermocouple during heating segments. However, a sensor failure occurred at around 350 °C during the cooling segment. The SEM and XPS tests revealed cracks on the thin film thermoelements and oxidation to the film thickness direction.

Performance and Durability of Thin Film Thermocouple Array on a Porous Electrode

PubMed Central

Guk, Erdogan; Ranaweera, Manoj; Venkatesan, Vijay; Kim, Jung-Sik

2016-01-01

Management of solid oxide fuel cell (SOFC) thermal gradients is vital to limit thermal expansion mismatch and thermal stress. However, owing to harsh operation conditions of SOFCs and limited available space in stack configuration, the number of techniques available to obtain temperature distribution from the cell surface is limited. The authors previously developed and studied a thermocouple array pattern to detect surface temperature distribution on an SOFC in open circuit conditions. In this study, the performance in terms of mechanical durability and oxidation state of the thin film thermoelements of the thermocouple array on the porous SOFC cathode is investigated. A thin-film multi-junction thermocouple array was sputter deposited using a magnetron sputter coater. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) characterisation techniques were carried out to understand characteristics of the thin film before and after temperature (20 °C–800 °C) measurement. Temperature readings from the sensor agreed well with the closely placed commercial thermocouple during heating segments. However, a sensor failure occurred at around 350 °C during the cooling segment. The SEM and XPS tests revealed cracks on the thin film thermoelements and oxidation to the film thickness direction. PMID:27563893

Synthesis of graphene oxide and reduced graphene oxide by needle platy natural vein graphite

NASA Astrophysics Data System (ADS)

Rathnayake, R. M. N. M.; Wijayasinghe, H. W. M. A. C.; Pitawala, H. M. T. G. A.; Yoshimura, Masamichi; Huang, Hsin-Hui

2017-01-01

Among natural graphite varieties, needle platy vein graphite (NPG) has very high purity. Therefore, it is readily used to prepare graphene oxide (GO) and reduced graphene oxide (rGO). In this study, GO and rGO were prepared using chemical oxidation and reduction process, respectively. The synthesized materials were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) spectroscopy. XRD studies confirmed the increase of the interlayer spacing of GO and rGO in between 3.35 to 8.66 A°. AFM studies showed the layer height of rGO to be 1.05 nm after the reduction process. TEM micrographs clearly illustrated that the prepared GO has more than 25 layers, while the rGO has only less than 15 layers. Furthermore, the effect of chemical oxidation and reduction processes on surface morphology of graphite were clearly observed in FESEM micrographs. The calculated RO/C of GO and rGO using XPS analysis are 5.37% and 1.77%, respectively. The present study revealed the successful and cost effective nature of the chemical oxidation, and the reduction processes for the production of GO and rGO out of natural vein graphite.

Surface analysis characterisation of gum binders used in modern watercolour paints

NASA Astrophysics Data System (ADS)

Sano, Naoko; Cumpson, Peter J.

2016-02-01

Conducting this study has demonstrated that not only SEM-EDX but also XPS can be an efficient tool for characterising watercolour paint surfaces. We find that surface effects are mediated by water. Once the powdered components in the watercolour come into contact with water they dramatically transform their chemical structures at the surface and show the presence of pigment components with a random dispersion within the gum layer. Hence the topmost surface of the paint is confirmed as being composed of the gum binder components. This result is difficult to confirm using just one analytical technique (either XPS or SEM-EDX). In addition, peak fitting of C1s XPS spectra suggests that the gum binder in the commercial watercolour paints is probably gum arabic (by comparison with the reference materials). This identification is not conclusive, but the combination techniques of XPS and SEM shows the surface structure with material distribution of the gum binder and the other ingredients of the watercolour paints. Therefore as a unique technique, XPS combined with SEM-EDX may prove a useful method in the study of surface structure for not only watercolour objects but also other art objects; which may in future help in the conservation for art.

Native oxides formation and surface wettability of epitaxial III-V materials: The case of InP and GaAs

NASA Astrophysics Data System (ADS)

Gocalinska, A.; Rubini, S.; Pelucchi, E.

2016-10-01

The time dependent transition from hydrophobic to hydrophilic states of the metalorganic vapour phase epitaxy (MOVPE) grown InP, GaAs and InAs is systematically documented by contact angle measurements. Natural oxides forming on the surfaces of air-exposed materials, as well as the results of some typical wet chemical process to remove those oxides, were studied by X-ray photoemission spectroscopy (XPS), revealing, surprisingly, a fundamental lack of strong correlations between the surface oxide composition and the reported systematic changes in hydrophobicity.

Surface characteristics, mechanical properties, and cytocompatibility of oxygen plasma-implanted porous nickel titanium shape memory alloy.

PubMed

Wu, S L; Chu, Paul K; Liu, X M; Chung, C Y; Ho, J P Y; Chu, C L; Tjong, S C; Yeung, K W K; Lu, W W; Cheung, K M C; Luk, K D K

2006-10-01

Good surface properties and biocompatibility are crucial to porous NiTi shape memory alloys (SMA) used in medical implants, as possible nickel release from porous NiTi may cause deleterious effects in the human body. In this work, oxygen plasma immersion ion implantation (O-PIII) was used to reduce the amount of nickel leached from porous NiTi alloys with a porosity of 42% prepared by capsule-free hot isostatic pressing. The mechanical properties, surface properties, and biocompatibility were studied by compression tests, X-ray photoelectron spectroscopy (XPS), and cell culturing. The O-PIII porous NiTi SMAs have good mechanical properties and excellent superelasticity, and the amount of nickel leached from the O-PIII porous NiTi is much less than that from the untreated samples. XPS results indicate that a nickel-depleted surface layer predominantly composed of TiO(2) is produced by O-PIII and acts as a barrier against out-diffusion of nickel. The cell culturing tests reveal that both the O-PIII and untreated porous NiTi alloys have good biocompatibility. (c) 2006 Wiley Periodicals, Inc

Bioleaching of two different genetic types of chalcopyrite and their comparative mineralogical assessment.

PubMed

Deng, Sha; Gu, Guohua; Ji, Jing; Xu, Baoke

2018-02-01

The bioleaching of two different genetic types of chalcopyrite by the moderate thermophile Sulfobacillus thermosulfidooxidans was investigated by leaching behaviors elucidation and their comparative mineralogical assessment. The leaching experiment showed that the skarn-type chalcopyrite (STC) revealed a much faster leaching rate with 33.34% copper extracted finally, while only 23.53% copper was bioleached for the porphyry-type chalcopyrite (PTC). The mineralogical properties were analyzed by XRD, SEM, XPS, and Fermi energy calculation. XRD indicated that the unit cell volume of STC was a little larger than that of PTC. SEM indicated that the surface of STC had more steps and ridges. XPS spectra showed that Cu(I) was the dominant species of copper on the surfaces of the two chalcopyrite samples, and STC had much more copper with lower Cu 2p 3/2 binding energy. Additionally, the Fermi energy of STC was much higher than that of PTC. These mineralogical differences were in good agreement with the bioleaching behaviors of chalcopyrite. This study will provide some new information for evaluating the oxidation kinetics of chalcopyrite.

Characterization of tetraethylene glycol passivated iron nanoparticles

NASA Astrophysics Data System (ADS)

Nunes, Eloiza da Silva; Viali, Wesley Renato; da Silva, Sebastião William; Coaquira, José Antonio Huamaní; Garg, Vijayendra Kumar; de Oliveira, Aderbal Carlos; Morais, Paulo César; Jafelicci Júnior, Miguel

2014-10-01

The present study describes the synthesis and characterization of iron@iron oxide nanoparticles produced by passivation of metallic iron in tetraethylene glycol media. Structural and chemical characterizations were performed using transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Mössbauer spectroscopy. Pomegranate-like core@shell nanoparticulate material in the size range of 90-120 nm was obtained. According to quantitative phase analysis using Rietveld structure refinement the synthesized iron oxide was identified as magnetite (Fe3O4) whereas the iron to magnetite mass fractions was found to be 47:53. These findings are in good agreement with the data obtained from Mössbauer and thermal gravimetric analysis (TGA). The XPS data revealed the presence of a surface organic layer with higher hydrocarbon content, possibly due to the tetraethylene glycol thermal degradation correlated with iron oxidation. The room-temperature (300 K) saturation magnetization measured for the as-synthesized iron and for the iron-iron oxide were 145 emu g-1 and 131 emu g-1, respectively. The measured saturation magnetizations are in good agreement with data obtained from TEM, XRD and Mössbauer spectroscopy.

Surface characterisation of ethylene propylene diene rubber upon exposure to aqueous acidic solution

NASA Astrophysics Data System (ADS)

Mitra, Susanta; Ghanbari-Siahkali, Afshin; Kingshott, Peter; Hvilsted, Søren; Almdal, Kristoffer

2006-07-01

Two types of pure ethylene propylene diene rubbers were exposed to two different acids for varying period of time. Surface characterisation was carried out using X-ray photoelectron spectroscopy (XPS). Two EPDM rubbers selected for this study were comparable in co-monomer compositions but significantly different with respect to molar mass and the presence of long chain branching. Both rubbers contained 5-ethylidene-2-norbornene (ENB) as diene. Solution cast films of pure EPDM samples were exposed in two different acidic solutions, viz. chromosulphuric (Cr (VI)/H 2SO 4) and sulphuric acid (H 2SO 4) (20%, v/v) at ambient temperature from 1 to 12 weeks. XPS analysis indicated that several oxygenated species were formed on the surface of both rubbers after exposure. It was postulated from the XPS analyses that both aqueous acidic solutions attacked the olefinic double bonds (C dbnd C) of ENB. Furthermore, 20% Cr (VI)/H 2SO 4 also attacked the allylic carbon-hydrogen (C sbnd H) bonds of ENB resulting in more oxygenated species on the surface compared to 20% H 2SO 4 under identical conditions. Cr (VI) in the 20% Cr (VI)/H 2SO 4 was found to play an important role in alteration of surface chemistry. Studies using a model system consisting of EPDM mixed with Cr (VI) and Cr (III) salts revealed that the change of oxidation state from Cr (VI) to Cr (III) as a consequence of direct involvement of Cr (VI) in the chemical alteration of EPDM surfaces. Interestingly, the presence of long chain branching and molar mass did not significantly influence the chemical processes owing to the acid treatment.

Kinetics of electron-induced decomposition of CF2Cl2 coadsorbed with water (ice): A comparison with CCl4

NASA Astrophysics Data System (ADS)

Faradzhev, N. S.; Perry, C. C.; Kusmierek, D. O.; Fairbrother, D. H.; Madey, T. E.

2004-11-01

The kinetics of decomposition and subsequent chemistry of adsorbed CF2Cl2, activated by low-energy electron irradiation, have been examined and compared with CCl4. These molecules have been adsorbed alone and coadsorbed with water ice films of different thicknesses on metal surfaces (Ru; Au) at low temperatures (25 K; 100 K). The studies have been performed with temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), and x-ray photoelectron spectroscopy (XPS). TPD data reveal the efficient decomposition of both halocarbon molecules under electron bombardment, which proceeds via dissociative electron attachment (DEA) of low-energy secondary electrons. The rates of CF2Cl2 and CCl4 dissociation increase in an H2O (D2O) environment (2-3×), but the increase is smaller than that reported in recent literature. The highest initial cross sections for halocarbon decomposition coadsorbed with H2O, using 180 eV incident electrons, are measured (using TPD) to be 1.0±0.2×10-15 cm2 for CF2Cl2 and 2.5±0.2×10-15 cm2 for CCl4. RAIRS and XPS studies confirm the decomposition of halocarbon molecules codeposited with water molecules, and provide insights into the irradiation products. Electron-induced generation of Cl- and F- anions in the halocarbon/water films and production of H3O+, CO2, and intermediate compounds COF2 (for CF2Cl2) and COCl2, C2Cl4 (for CCl4) under electron irradiation have been detected using XPS, TPD, and RAIRS. The products and the decomposition kinetics are similar to those observed in our recent experiments involving x-ray photons as the source of ionizing irradiation.

A perspective on two chemometrics tools: PCA and MCR, and introduction of a new one: Pattern recognition entropy (PRE), as applied to XPS and ToF-SIMS depth profiles of organic and inorganic materials

NASA Astrophysics Data System (ADS)

Chatterjee, Shiladitya; Singh, Bhupinder; Diwan, Anubhav; Lee, Zheng Rong; Engelhard, Mark H.; Terry, Jeff; Tolley, H. Dennis; Gallagher, Neal B.; Linford, Matthew R.

2018-03-01

X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) are much used analytical techniques that provide information about the outermost atomic and molecular layers of materials. In this work, we discuss the application of multivariate spectral techniques, including principal component analysis (PCA) and multivariate curve resolution (MCR), to the analysis of XPS and ToF-SIMS depth profiles. Multivariate analyses often provide insight into data sets that is not easily obtained in a univariate fashion. Pattern recognition entropy (PRE), which has its roots in Shannon's information theory, is also introduced. This approach is not the same as the mutual information/entropy approaches sometimes used in data processing. A discussion of the theory of each technique is presented. PCA, MCR, and PRE are applied to four different data sets obtained from: a ToF-SIMS depth profile through ca. 100 nm of plasma polymerized C3F6 on Si, a ToF-SIMS depth profile through ca. 100 nm of plasma polymerized PNIPAM (poly (N-isopropylacrylamide)) on Si, an XPS depth profile through a film of SiO2 on Si, and an XPS depth profile through a film of Ta2O5 on Ta. PCA, MCR, and PRE reveal the presence of interfaces in the films, and often indicate that the first few scans in the depth profiles are different from those that follow. PRE and backward difference PRE provide this information in a straightforward fashion. Rises in the PRE signals at interfaces suggest greater complexity to the corresponding spectra. Results from PCA, especially for the higher principal components, were sometimes difficult to understand. MCR analyses were generally more interpretable.

Versatile technique for assessing thickness of 2D layered materials by XPS

NASA Astrophysics Data System (ADS)

Zemlyanov, Dmitry Y.; Jespersen, Michael; Zakharov, Dmitry N.; Hu, Jianjun; Paul, Rajib; Kumar, Anurag; Pacley, Shanee; Glavin, Nicholas; Saenz, David; Smith, Kyle C.; Fisher, Timothy S.; Voevodin, Andrey A.

2018-03-01

X-ray photoelectron spectroscopy (XPS) has been utilized as a versatile method for thickness characterization of various two-dimensional (2D) films. Accurate thickness can be measured simultaneously while acquiring XPS data for chemical characterization of 2D films having thickness up to approximately 10 nm. For validating the developed technique, thicknesses of few-layer graphene (FLG), MoS2 and amorphous boron nitride (a-BN) layer, produced by microwave plasma chemical vapor deposition (MPCVD), plasma enhanced chemical vapor deposition (PECVD), and pulsed laser deposition (PLD) respectively, were accurately measured. The intensity ratio between photoemission peaks recorded for the films (C 1s, Mo 3d, B 1s) and the substrates (Cu 2p, Al 2p, Si 2p) is the primary input parameter for thickness calculation, in addition to the atomic densities of the substrate and the film, and the corresponding electron attenuation length (EAL). The XPS data was used with a proposed model for thickness calculations, which was verified by cross-sectional transmission electron microscope (TEM) measurement of thickness for all the films. The XPS method determines thickness values averaged over an analysis area which is orders of magnitude larger than the typical area in cross-sectional TEM imaging, hence provides an advanced approach for thickness measurement over large areas of 2D materials. The study confirms that the versatile XPS method allows rapid and reliable assessment of the 2D material thickness and this method can facilitate in tailoring growth conditions for producing very thin 2D materials effectively over a large area. Furthermore, the XPS measurement for a typical 2D material is non-destructive and does not require special sample preparation. Therefore, after XPS analysis, exactly the same sample can undergo further processing or utilization.

Versatile technique for assessing thickness of 2D layered materials by XPS

DOE PAGES

Zemlyanov, Dmitry Y.; Jespersen, Michael; Zakharov, Dmitry N.; ...

2018-02-07

X-ray photoelectron spectroscopy (XPS) has been utilized as a versatile method for thickness characterization of various two-dimensional (2D) films. Accurate thickness can be measured simultaneously while acquiring XPS data for chemical characterization of 2D films having thickness up to approximately 10 nm. For validating the developed technique, thicknesses of few-layer graphene (FLG), MoS 2 and amorphous boron nitride (a-BN) layer, produced by microwave plasma chemical vapor deposition (MPCVD), plasma enhanced chemical vapor deposition (PECVD), and pulsed laser deposition (PLD) respectively, were accurately measured. The intensity ratio between photoemission peaks recorded for the films (C 1s, Mo 3d, B 1s) andmore » the substrates (Cu 2p, Al 2p, Si 2p) is the primary input parameter for thickness calculation, in addition to the atomic densities of the substrate and the film, and the corresponding electron attenuation length (EAL). The XPS data was used with a proposed model for thickness calculations, which was verified by cross-sectional transmission electron microscope (TEM) measurement of thickness for all the films. The XPS method determines thickness values averaged over an analysis area which is orders of magnitude larger than the typical area in cross-sectional TEM imaging, hence provides an advanced approach for thickness measurement over large areas of 2D materials. The study confirms that the versatile XPS method allows rapid and reliable assessment of the 2D material thickness and this method can facilitate in tailoring growth conditions for producing very thin 2D materials effectively over a large area. Furthermore, the XPS measurement for a typical 2D material is non-destructive and does not require special sample preparation. Furthermore, after XPS analysis, exactly the same sample can undergo further processing or utilization.« less

Versatile technique for assessing thickness of 2D layered materials by XPS.

PubMed

Zemlyanov, Dmitry Y; Jespersen, Michael; Zakharov, Dmitry N; Hu, Jianjun; Paul, Rajib; Kumar, Anurag; Pacley, Shanee; Glavin, Nicholas; Saenz, David; Smith, Kyle C; Fisher, Timothy S; Voevodin, Andrey A

2018-03-16

X-ray photoelectron spectroscopy (XPS) has been utilized as a versatile method for thickness characterization of various two-dimensional (2D) films. Accurate thickness can be measured simultaneously while acquiring XPS data for chemical characterization of 2D films having thickness up to approximately 10 nm. For validating the developed technique, thicknesses of few-layer graphene (FLG), MoS 2 and amorphous boron nitride (a-BN) layer, produced by microwave plasma chemical vapor deposition (MPCVD), plasma enhanced chemical vapor deposition (PECVD), and pulsed laser deposition (PLD) respectively, were accurately measured. The intensity ratio between photoemission peaks recorded for the films (C 1s, Mo 3d, B 1s) and the substrates (Cu 2p, Al 2p, Si 2p) is the primary input parameter for thickness calculation, in addition to the atomic densities of the substrate and the film, and the corresponding electron attenuation length (EAL). The XPS data was used with a proposed model for thickness calculations, which was verified by cross-sectional transmission electron microscope (TEM) measurement of thickness for all the films. The XPS method determines thickness values averaged over an analysis area which is orders of magnitude larger than the typical area in cross-sectional TEM imaging, hence provides an advanced approach for thickness measurement over large areas of 2D materials. The study confirms that the versatile XPS method allows rapid and reliable assessment of the 2D material thickness and this method can facilitate in tailoring growth conditions for producing very thin 2D materials effectively over a large area. Furthermore, the XPS measurement for a typical 2D material is non-destructive and does not require special sample preparation. Therefore, after XPS analysis, exactly the same sample can undergo further processing or utilization.

Versatile technique for assessing thickness of 2D layered materials by XPS

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

Zemlyanov, Dmitry Y.; Jespersen, Michael; Zakharov, Dmitry N.

X-ray photoelectron spectroscopy (XPS) has been utilized as a versatile method for thickness characterization of various two-dimensional (2D) films. Accurate thickness can be measured simultaneously while acquiring XPS data for chemical characterization of 2D films having thickness up to approximately 10 nm. For validating the developed technique, thicknesses of few-layer graphene (FLG), MoS 2 and amorphous boron nitride (a-BN) layer, produced by microwave plasma chemical vapor deposition (MPCVD), plasma enhanced chemical vapor deposition (PECVD), and pulsed laser deposition (PLD) respectively, were accurately measured. The intensity ratio between photoemission peaks recorded for the films (C 1s, Mo 3d, B 1s) andmore » the substrates (Cu 2p, Al 2p, Si 2p) is the primary input parameter for thickness calculation, in addition to the atomic densities of the substrate and the film, and the corresponding electron attenuation length (EAL). The XPS data was used with a proposed model for thickness calculations, which was verified by cross-sectional transmission electron microscope (TEM) measurement of thickness for all the films. The XPS method determines thickness values averaged over an analysis area which is orders of magnitude larger than the typical area in cross-sectional TEM imaging, hence provides an advanced approach for thickness measurement over large areas of 2D materials. The study confirms that the versatile XPS method allows rapid and reliable assessment of the 2D material thickness and this method can facilitate in tailoring growth conditions for producing very thin 2D materials effectively over a large area. Furthermore, the XPS measurement for a typical 2D material is non-destructive and does not require special sample preparation. Furthermore, after XPS analysis, exactly the same sample can undergo further processing or utilization.« less

XPS studies of Mg doped GDC (Ce0.8Gd0.2O2-δ) for IT-SOFC

NASA Astrophysics Data System (ADS)

Tyagi, Deepak; Rao, P. Koteswara; Wani, B. N.

2018-04-01

Fuel Cells have gained much attention as efficient and environment friendly device for both stationary as well as mobile applications. For intermediate temperature SOFC (IT-SOFC), ceria based electrolytes are the most promising one, due to their higher ionic conductivity at relatively lower temperatures. Gd doped ceria is reported to be having the highest ionic conductivity. In the present work, Mg is codoped along with Gd and the electronic structure of the constituents is studied by XPS. XPS confirm that the Cerium is present in +4 oxidation state only which indicates that electronic conduction can be completely avoided.

Synthesis of a new photoreactive derivative of dipyridamole and its use in the manufacture of artificial surfaces with low thrombogenicity.

PubMed

Aldenhoff, Y B; Pijpers, A P; Koole, L H

1997-01-01

Photoimmobilization of dipyridamole (Persantin) was accomplished through the use of a new synthetic conjugate molecule, 1. Persantin is a powerful inhibitor of platelet activation and aggregation and is widely used as a vasodilator. Conjugate 1 consists of triply protected dipyridamole [three of the four hydroxyl groups carry a tert-butyldimethylsilyl (TBDMS) protective group) and the photoreactive 4-azidobenzoyl group. A short hydrophilic spacer chain, derived from triethylene glycol, separates the protected dipyridamole system and the photoreactive group. Compound 1 was immobilized on polyurethane sheets (Pellethane D-55) through irradiation with ultraviolet (UV) light, and the protective groups were removed afterward. The resulting modified polyurethane surfaces were characterized by different physicochemical techniques: UV extinction, contact angle measurements (captive bubble technique), and X-ray photoelectron spectroscopy (XPS). The UV extinction measurements showed the presence of 13 +/- 1 nmol of immobilized dipyridamole/cm2. The contact angle measurements revealed that the modified surface was markedly more hydrophilic than the control (i.e. unmodified polyurethane). XPS measurements clearly established the presence of immobilized dipyridamole in the outermost layers of the modified surface. This was especially clear from the XPS spectra recorded at a low take-off angle (approximately 6 degrees). Furthermore, the XPS spectra showed that the TBDMS protective groups had been quantitatively removed during the deprotection/washing treatment. The in vitro blood compatibility of the modified surface was studied with the thrombin generation assay as developed in our group, as well as with scanning electron microscopy. The thrombin generation test produced a lag time of 1275 s for the modified surface, as opposed to 569 s for the control. Scanning electron microscopy showed that far fewer platelets adhere to the modified surface (approximately 7 x 10(3)/mm2) as compared to the control (approximately 6 x 10(2)/mm2). Taken together, the experimental data reveal that the modified surface has excellent blood compatibility in vitro. It is discussed that the use of conjugate 1 leads to simultaneous exposure of dipyridamole at the modified surface and to a marked increase of the surface hydrophilicity, which is likely to hamper adsorption of plasma proteins. The combination of these effects is uniquely related to the molecular buildup of 1. Conjugate 1 will be used in future work that is aimed at preparing small-caliber polyurethane vascular grafts with a blood compatible lumenal surface.

New quaternary thallium indium germanium selenide TlInGe2Se6: Crystal and electronic structure

NASA Astrophysics Data System (ADS)

Khyzhun, O. Y.; Parasyuk, O. V.; Tsisar, O. V.; Piskach, L. V.; Myronchuk, G. L.; Levytskyy, V. O.; Babizhetskyy, V. S.

2017-10-01

Crystal structure of a novel quaternary thallium indium germanium selenide TlInGe2Se6 was investigated by means of powder X-ray diffraction method. It was determined that the compound crystallizes in the trigonal space group R3 with the unit cell parameters a = 10.1798(2) Å, c = 9.2872(3) Å. The relationship with similar structures was discussed. The as-synthesized TlInGe2Se6 ingot was tested with X-ray photoelectron spectroscopy (XPS) and X-ray emission spectroscopy (XES). In particular, the XPS valence-band and core-level spectra were recorded for initial and Ar+ ion-bombarded surfaces of the sample under consideration. The XPS data allow for statement that the TlInGe2Se6 surface is rigid with respect to Ar+ ion-bombardment. Particularly, Ar+ ion-bombardment (3.0 keV, 5 min duration, ion current density fixed at 14 μA/cm2) did not cause substantial modifications of stoichiometry in topmost surface layers. Furthermore, comparison on a common energy scale of the XES Se Kβ2 and Ge Kβ2 bands and the XPS valence-band spectrum reveals that the principal contributions of the Se 4p and Ge 4p states occur in the upper and central portions of the valence band of TlInGe2Se6, respectively, with also their substantial contributions in other portions of the band. The bandgap energy of TlInGe2Se6 at the level of αg=103 cm-1 is equal to 2.38 eV at room temperature.

X-ray Photoelectron Spectroscopy study of CaV1-xMoxO3-δ

NASA Astrophysics Data System (ADS)

Belyakov, S. A.; Kuznetsov, M. V.; Shkerin, S. N.

2018-06-01

An investigation was carried out on perovskite-based derivatives of CaV1-xMoxO3-δ using X-ray Photoelectron Spectroscopy (XPS). According to the XRD pattern, the area of homogeneity covers the region from x = 0 to x = 0.6. Wide XPS-peaks of Ca, V, Mo and O are observed, signalling that elements are presented in multiple states. A model for explaining the large chemical shifts of XPS peaks due to different charging effects on different parts of the sample surface is proposed.

Ni-CeO2 spherical nanostructures for magnetic and electrochemical supercapacitor applications.

PubMed

Murugan, Ramachandran; Ravi, Ganesan; Vijayaprasath, Gandhi; Rajendran, Somasundharam; Thaiyan, Mahalingam; Nallappan, Maheswari; Gopalan, Muralidharan; Hayakawa, Yasuhiro

2017-02-08

The synthesis of nanoparticles has great control over the structural and functional characteristics of materials. In this study, CeO 2 and Ni-CeO 2 spherical nanoparticles were prepared using a microwave-assisted method. The prepared nanoparticles were characterized via thermogravimetry, X-ray diffraction (XRD), Raman, FTIR, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometry (VSM) and cyclic voltammetry (CV). The pure CeO 2 sample exhibited a flake-like morphology, whereas Ni-doped CeO 2 showed spherical morphology with uniform shapes. Spherical morphologies for the Ni-doped samples were further confirmed via TEM micrographs. Thermogravimetric analyses revealed that decomposition varies with Ni-doping in CeO 2 . XRD revealed that the peak shifts towards lower angles for the Ni-doped samples. Furthermore, a diamagnetic to ferromagnetic transition was observed in Ni-doped CeO 2 . The ferromagnetic property was attributed to the introduction of oxygen vacancies in the CeO 2 lattice upon doping with Ni, which were confirmed by Raman and XPS. The pseudo-capacitive properties of pure and Ni-doped CeO 2 samples were evaluated via cyclic voltammetry and galvanostatic charge-discharge studies, wherein 1 M KOH was used as the electrolyte. The specific capacitances were 235, 351, 382, 577 and 417 F g -1 corresponding to the pure 1%, 3%, 5% and 7% of Ni doped samples at the current density of 2 A g -1 , respectively. The 5% Ni-doped sample showed an excellent cyclic stability and maintained 94% of its maximum specific capacitance after 1000 cycles.

Gallium-containing polymer brush film as efficient supported Lewis acid catalyst in a glass microreactor

PubMed Central

Munirathinam, Rajesh; Ricciardi, Roberto; Egberink, Richard J M; Huskens, Jurriaan; Holtkamp, Michael; Wormeester, Herbert; Karst, Uwe

2013-01-01

Summary Polystyrene sulfonate polymer brushes, grown on the interior of the microchannels in a microreactor, have been used for the anchoring of gallium as a Lewis acid catalyst. Initially, gallium-containing polymer brushes were grown on a flat silicon oxide surface and were characterized by FTIR, ellipsometry, and X-ray photoelectron spectroscopy (XPS). XPS revealed the presence of one gallium per 2–3 styrene sulfonate groups of the polymer brushes. The catalytic activity of the Lewis acid-functionalized brushes in a microreactor was demonstrated for the dehydration of oximes, using cinnamaldehyde oxime as a model substrate, and for the formation of oxazoles by ring closure of ortho-hydroxy oximes. The catalytic activity of the microreactor could be maintained by periodic reactivation by treatment with GaCl3. PMID:24062830

Applications of XPS in the characterization of Battery materials

DOE PAGES

Shutthanandan, Vaithiyalingam; Nandasiri, Manjula; Zheng, Jianming; ...

2018-05-26

In this study, technological development requires reliable power sources where energy storage devices are emerging as a critical component. Wide range of energy storage devices, Redox-flow batteries (RFB), Lithium ion based batteries (LIB), and Lithium-sulfur (LSB) batteries are being developed for various applications ranging from grid-scale level storage to mobile electronics. Material complexities associated with these energy storage devices with unique electrochemistry are formidable challenge which needs to be address for transformative progress in this field. X-ray photoelectron spectroscopy (XPS) - a powerful surface analysis tool - has been widely used to study these energy storage materials because of itsmore » ability to identify, quantify and image the chemical distribution of redox active species. However, accessing the deeply buried solid-electrolyte interfaces (which dictates the performance of energy storage devices) has been a challenge in XPS usage. Herein we report our recent efforts to utilize the XPS to gain deep insight about these interfaces under realistic conditions with varying electrochemistry involving RFB, LIB and LSB.« less

Hydrolysis condensation reactions of titanium alkoxides in thin films: A study of the steric hindrance effect by X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Barlier, Vincent; Bounor-Legaré, Véronique; Boiteux, Gisèle; Davenas, Joël; Léonard, Didier

2008-06-01

An original approach based on X-ray photoelectron spectroscopy (XPS) is proposed to study the influence of the surrounding humidity on the hydrolysis-condensation reactions of five titanium alkoxides in thin films. More precisely, the influence of the nature of the ligands (propoxide, butoxide, isopropoxide, phenoxide, and 9H-carbazole-9-yl-ethyl-oxy) on the reaction rate was evidenced. The reaction advancement was evaluated by comparing XPS chemical compositions to theoretical compositions calculated for all the possible rates. XPS chemical environment information allowed validating the reliability of this approach through the evaluation of the condensation state. In both approaches, the influence of the steric hindrance on the reactivity of titanium alkoxides was highlighted to be similar to what has been previously observed in solution. Theses results corroborate the validity of our XPS approach to determine titanium alkoxide hydrolysis-condensation reactions in the specific application of thin films.

Applications of XPS in the characterization of Battery materials

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

Shutthanandan, Vaithiyalingam; Nandasiri, Manjula; Zheng, Jianming

In this study, technological development requires reliable power sources where energy storage devices are emerging as a critical component. Wide range of energy storage devices, Redox-flow batteries (RFB), Lithium ion based batteries (LIB), and Lithium-sulfur (LSB) batteries are being developed for various applications ranging from grid-scale level storage to mobile electronics. Material complexities associated with these energy storage devices with unique electrochemistry are formidable challenge which needs to be address for transformative progress in this field. X-ray photoelectron spectroscopy (XPS) - a powerful surface analysis tool - has been widely used to study these energy storage materials because of itsmore » ability to identify, quantify and image the chemical distribution of redox active species. However, accessing the deeply buried solid-electrolyte interfaces (which dictates the performance of energy storage devices) has been a challenge in XPS usage. Herein we report our recent efforts to utilize the XPS to gain deep insight about these interfaces under realistic conditions with varying electrochemistry involving RFB, LIB and LSB.« less

New Pt/Alumina model catalysts for STM and in situ XPS studies

NASA Astrophysics Data System (ADS)

Nartova, Anna V.; Gharachorlou, Amir; Bukhtiyarov, Andrey V.; Kvon, Ren I.; Bukhtiyarov, Valerii I.

2017-04-01

The new Pt/alumina model catalysts for STM and in situ XPS studies based on thin alumina film formed over the conductive substrate are proposed. Procedure of platinum deposition developed for porous alumina was adapted for the model alumina support. The set of Pt/AlOx-film samples with the different mean platinum particle size was prepared. Capabilities of in situ XPS investigations of the proposed catalysts were demonstrated in study of NO decomposition on platinum nanoparticles. It is shown that proposed model catalysts behave similarly to Pt/γ-Al2O3 and provide the new opportunities for the instrumental studies of platinum catalysts due to resolving several issues (charging, heating, screening) that are typical for the investigation of the porous oxide supported catalysts.

Insights into electrochemical reactions from ambient pressure photoelectron spectroscopy.

PubMed

Stoerzinger, Kelsey A; Hong, Wesley T; Crumlin, Ethan J; Bluhm, Hendrik; Shao-Horn, Yang

2015-11-17

The understanding of fundamental processes in the bulk and at the interfaces of electrochemical devices is a prerequisite for the development of new technologies with higher efficiency and improved performance. One energy storage scheme of great interest is splitting water to form hydrogen and oxygen gas and converting back to electrical energy by their subsequent recombination with only water as a byproduct. However, kinetic limitations to the rate of oxygen-based electrochemical reactions hamper the efficiency in technologies such as solar fuels, fuel cells, and electrolyzers. For these reactions, the use of metal oxides as electrocatalysts is prevalent due to their stability, low cost, and ability to store oxygen within the lattice. However, due to the inherently convoluted nature of electrochemical and chemical processes in electrochemical systems, it is difficult to isolate and study individual electrochemical processes in a complex system. Therefore, in situ characterization tools are required for observing related physical and chemical processes directly at the places where and while they occur and can help elucidate the mechanisms of charge separation and charge transfer at electrochemical interfaces. X-ray photoelectron spectroscopy (XPS), also known as ESCA (electron spectroscopy for chemical analysis), has been used as a quantitative spectroscopic technique that measures the elemental composition, as well as chemical and electronic state of a material. Building from extensive ex situ characterization of electrochemical systems, initial in situ studies were conducted at or near ultrahigh vacuum (UHV) conditions (≤10(-6) Torr) to probe solid-state electrochemical systems. However, through the integration of differential-pumping stages, XPS can now operate at pressures in the torr range, comprising a technique called ambient pressure XPS (AP-XPS). In this Account, we briefly review the working principles and current status of AP-XPS. We use several recent in situ studies on model electrochemical components as well as operando studies performed by our groups at the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory to illustrate that AP-XPS is both a chemically and an electrically specific tool since photoelectrons carry information on both the local chemistry and electrical potentials. The applications of AP-XPS to oxygen electrocatalysis shown in this Account span well-defined studies of (1) the oxide/oxygen gas interface, (2) the oxide/water vapor interface, and (3) operando measurements of half and full electrochemical cells. Using specially designed model devices, we can expose and isolate the electrode or interface of interest to the incident X-ray beam and AP-XPS analyzer to relate the electrical potentials to the composition/chemical state of the key components and interfaces. We conclude with an outlook on new developments of AP-XPS end stations, which may provide significant improvement in the observation of dynamics over a wide range of time scales, higher spatial resolution, and improved characterization of boundary or interface layers (solid/solid and liquid/solid).

Layer uniformity in glucose oxidase immobilization on SiO 2 surfaces

NASA Astrophysics Data System (ADS)

Libertino, Sebania; Scandurra, Antonino; Aiello, Venera; Giannazzo, Filippo; Sinatra, Fulvia; Renis, Marcella; Fichera, Manuela

2007-09-01

The goal of this work was the characterization, step by step, of the enzyme glucose oxidase (GOx) immobilization on silicon oxide surfaces, mainly by means of X-Ray photoelectron spectroscopy (XPS). The immobilization protocol consists of four steps: oxide activation, silanization, linker molecule deposition and GOx immobilization. The linker molecule, glutaraldehyde (GA) in this study, must be able to form a uniform layer on the sample surface in order to maximize the sites available for enzyme bonding and achieve the best enzyme deposition. Using a thin SiO 2 layer grown on Si wafers and following the XPS Si2p signal of the Si substrate during the immobilization steps, we demonstrated both the glutaraldehyde layer uniformity and the possibility to use XPS to monitor thin layer uniformity. In fact, the XPS substrate signal, not shielded by the oxide, is suppressed only when a uniform layer is deposited. The enzyme correct immobilization was monitored using the XPS C1s and N1s signals. Atomic force microscopy (AFM) measurements carried out on the same samples confirmed the results.

Influence of Ga vacancies, Mn and O impurities on the ferromagnetic properties of GaN micro- and nanostructures

NASA Astrophysics Data System (ADS)

Guzmán, G.; Escudero, R.; Silva, R.; Herrera, M.

2018-04-01

We present a study of the influence of gallium vacancy (VGa) point defects on the ferromagnetic properties of GaN:Mn and GaN:Mn,O micro- and nanostructures. Results demonstrate that the generation of these point defects enhances the ferromagnetic signal of GaN:Mn microstructures, while incorporation of oxygen as an impurity inhibits this property. XPS measurements revealed that Mn impurities in ferromagnetic GaN:Mn samples mainly exhibit a valence state of 2+. Cathodoluminescence (CL) spectra from Mn-doped GaN samples displayed emissions centered at about 1.97 eV, attributed to transitions between the 4T1-6A1 states of the Mn2+ d orbitals, and emissions centered at 2.45 and 2.9 eV, associated with the presence of VGa. CL measurements also revealed a blue shift of the GaN band-edge emission generated by the expansion of the wurtzite lattice due to Mn incorporation, which was confirmed by XRD measurements. These latter measurements also revealed an amorphization of GaN:Mn due to the incorporation of oxygen as impurities. The GaN:Mn samples were synthesized by thermal evaporation of GaN and MnCO3 powders onto Ni0.8Cr0.2/Si(100) in a horizontal furnace operated at low vacuum. The residual air inside the system was used as a source of oxygen during the synthesis of Mn and O co-doped GaN nanostructures. Mn and O impurities were incorporated into the nanostructures at different concentrations by varying the growth temperature. Energy Dispersive Spectroscopy, XRD, and XPS measurements confirmed that the obtained samples predominantly consisted of GaN.

Zinc phthalocyanine nanowires based flexible sensor for room temperature Cl2 detection

NASA Astrophysics Data System (ADS)

Devi, Pooja; Saini, Rajan; Singh, Rajinder; Mahajan, A.; Bedi, R. K.; Aswal, D. K.; Debnath, A. K.

2018-04-01

We have fabricated highly sensitive and Cl2 selective flexible sensor by depositing solution processed zinc phthalocyanine nanowires onto the flexible PET substrate and studied its Cl2 sensing characteristics in Cl2 concentration range 5-1500 ppb. The flexible sensor has a minimum detection limit as low as 5 ppb of Cl2 and response as high as 550% within 10 seconds. Interestingly, the sensor exhibited enhanced and faster response kinetics under bending conditions. The gas sensing mechanism of sensor has been discussed on the basis of XPS and Raman spectroscopic studies which revealed that zinc ions were the preferred sites for Cl2 interactions.

Temperature dependent selective detection of hydrogen and acetone using Pd doped WO3/reduced graphene oxide nanocomposite

NASA Astrophysics Data System (ADS)

Kaur, Jasmeet; Anand, Kanica; Kohli, Nipin; Kaur, Amanpreet; Singh, Ravi Chand

2018-06-01

Reduced graphene oxide (RGO) and Pd doped WO3 nanocomposites were fabricated by employing electrostatic interactions between poly (diallyldimethylammonium chloride) (PDDA) modified Pd doped WO3 nanostructures and graphite oxide (GO) and studied for their gas sensing application. XRD, Raman, FTIR, FESEM-EDX, TEM, TGA, XPS and Photoluminescence techniques were used for characterization of as-synthesized samples. Gas sensing studies revealed that the sensor with optimized doping of 1.5 mol% Pd and 1 wt% GO shows temperature dependent selectivity towards hydrogen and acetone. The role of WO3, Pd and RGO has been discussed in detail for enhanced sensing performance.

Understanding of sub-band gap absorption of femtosecond-laser sulfur hyperdoped silicon using synchrotron-based techniques

PubMed Central

Limaye, Mukta V.; Chen, S. C.; Lee, C. Y.; Chen, L. Y.; Singh, Shashi B.; Shao, Y. C.; Wang, Y. F.; Hsieh, S. H.; Hsueh, H. C.; Chiou, J. W.; Chen, C. H.; Jang, L. Y.; Cheng, C. L.; Pong, W. F.; Hu, Y. F.

2015-01-01

The correlation between sub-band gap absorption and the chemical states and electronic and atomic structures of S-hyperdoped Si have been extensively studied, using synchrotron-based x-ray photoelectron spectroscopy (XPS), x-ray absorption near-edge spectroscopy (XANES), extended x-ray absorption fine structure (EXAFS), valence-band photoemission spectroscopy (VB-PES) and first-principles calculation. S 2p XPS spectra reveal that the S-hyperdoped Si with the greatest (~87%) sub-band gap absorption contains the highest concentration of S2− (monosulfide) species. Annealing S-hyperdoped Si reduces the sub-band gap absorptance and the concentration of S2− species, but significantly increases the concentration of larger S clusters [polysulfides (Sn2−, n > 2)]. The Si K-edge XANES spectra show that S hyperdoping in Si increases (decreased) the occupied (unoccupied) electronic density of states at/above the conduction-band-minimum. VB-PES spectra evidently reveal that the S-dopants not only form an impurity band deep within the band gap, giving rise to the sub-band gap absorption, but also cause the insulator-to-metal transition in S-hyperdoped Si samples. Based on the experimental results and the calculations by density functional theory, the chemical state of the S species and the formation of the S-dopant states in the band gap of Si are critical in determining the sub-band gap absorptance of hyperdoped Si samples. PMID:26098075

Hydrotalcite-based CeNiAl mixed oxides for SO2 adsorption and oxidation.

PubMed

Zhao, Ling; Kang, Qi; Guan, Xiongfei; Martyniuk, Christopher J

2018-06-05

The impact of Ce on SO 2 adsoption and oxidation was studied over a series of flower-like hydrotalcite-based CeNiAl mixed oxides. Combined with XRD, BET, pyridine chemisorption, CO 2 -TPD, XPS and H 2 -TPR results, it revealed that introduction of Ce into NiAlO generates new centers for oxygen storage and release, promotes the enhancement of Lewis acid strength, increases weakly and strongly alkaline sites, and increases ability for SO 2 adsorption and oxidation. Furthermore, in situ Fourier transform infrared spectroscopy revealed that adsorbed SO 2 molecules formed surface bidentate binuclear sulfate. Taken together, we propose that the addition of Ce 4+ to NiAlO acts to improve this compound as major adsorbent for SO 2 .

Conformal SiO2 coating of sub-100 nm diameter channels of polycarbonate etched ion-track channels by atomic layer deposition

PubMed Central

Sobel, Nicolas; Lukas, Manuela; Spende, Anne; Stühn, Bernd; Trautmann, Christina

2015-01-01

Summary Polycarbonate etched ion-track membranes with about 30 µm long and 50 nm wide cylindrical channels were conformally coated with SiO2 by atomic layer deposition (ALD). The process was performed at 50 °C to avoid thermal damage to the polymer membrane. Analysis of the coated membranes by small angle X-ray scattering (SAXS) reveals a homogeneous, conformal layer of SiO2 in the channels at a deposition rate of 1.7–1.8 Å per ALD cycle. Characterization by infrared and X-ray photoelectron spectroscopy (XPS) confirms the stoichiometric composition of the SiO2 films. Detailed XPS analysis reveals that the mechanism of SiO2 formation is based on subsurface crystal growth. By dissolving the polymer, the silica nanotubes are released from the ion-track membrane. The thickness of the tube wall is well controlled by the ALD process. Because the track-etched channels exhibited diameters in the range of nanometres and lengths in the range of micrometres, cylindrical tubes with an aspect ratio as large as 3000 have been produced. PMID:25821688

Functionalization of nanocrystalline diamond films with phthalocyanines

NASA Astrophysics Data System (ADS)

Petkov, Christo; Reintanz, Philipp M.; Kulisch, Wilhelm; Degenhardt, Anna Katharina; Weidner, Tobias; Baio, Joe E.; Merz, Rolf; Kopnarski, Michael; Siemeling, Ulrich; Reithmaier, Johann Peter; Popov, Cyril

2016-08-01

Phthalocyanine (Pc) derivatives containing different central metal atoms (Mn, Cu, Ti) and different peripheral chains were synthesized and comprehensively characterized. Their interaction with nanocrystalline diamond (NCD) films, as-grown by hot-filament chemical vapor deposition or after their modification with oxygen plasma to exchange the hydrogen termination with oxygen-containing groups, was studied by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The elemental composition as determined by XPS showed that the Pc were grafted on both as-grown and O-terminated NCD. Mn, Cu and Ti were detected together with N stemming from the Pc ring and S in case of the Ti-Pc from the peripheral ligands. The results for the elemental surface composition and the detailed study of the N 1s, S 2p and O 1s core spectra revealed that Ti-Pc grafted better on as-grown NCD but Cu-Pc and Mn-Pc on O-terminated films. Samples of Mn-Pc on as-grown and O-terminated NCD were further investigated by NEXAFS spectroscopy. The results showed ordering of the grafted molecules, laying flat on the H-terminated NCD surface while only the macrocycles were oriented parallel to the O-terminated surface with the peripheral chains perpendicular to it.

Modification of bamboo-based activated carbon using microwave radiation and its effects on the adsorption of methylene blue

NASA Astrophysics Data System (ADS)

Liu, Qing-Song; Zheng, Tong; Li, Nan; Wang, Peng; Abulikemu, Gulizhaer

2010-03-01

Modification of bamboo-based activated carbon was carried out in a microwave oven under N 2 atmosphere. The virgin and modified activated carbons were characterized by means of low temperature N 2 adsorption, acid-base titration, point of zero charge (pH pzc) measurement, FTIR and XPS spectra. A gradual decrease in the surface acidic groups was observed during the modification, while the surface basicity was enhanced to some extent, which gave rise to an increase in the pH pzc value. The species of the functional groups and relative content of various elements and groups were given further analysis using FTIR and XPS spectra. An increase in the micropores was found at the start, and the micropores were then extended into larger ones, resulting in an increase in the pore volume and average pore size. Adsorption studies showed enhanced adsorption of methylene blue on the modified activated carbons, caused mainly by the enlargement of the micropores. Adsorption isotherm fittings revealed that Langmuir and Freundlich models were applicable for the virgin and modified activated carbons, respectively. Kinetic studies exhibited faster adsorption rate of methylene blue on the modified activated carbons, and the pseudo-second-order model fitted well for all of the activated carbons.

Band line-up determination at p- and n-type Al/4H-SiC Schottky interfaces using photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Kohlscheen, J.; Emirov, Y. N.; Beerbom, M. M.; Wolan, J. T.; Saddow, S. E.; Chung, G.; MacMillan, M. F.; Schlaf, R.

2003-09-01

The band lineup of p- and n-type 4H-SiC/Al interfaces was determined using x-ray photoemission spectroscopy (XPS). Al was deposited in situ on ex situ cleaned SiC substrates in several steps starting at 1.2 Å up to 238 Å nominal film thickness. Before growth and after each growth step, the sample surface was characterized in situ by XPS. The analysis of the spectral shifts indicated that during the initial deposition stages the Al films react with the ambient surface contamination layer present on the samples after insertion into vacuum. At higher coverage metallic Al clusters are formed. The band lineups were determined from the analysis of the core level peak shifts and the positions of the valence bands maxima (VBM) depending on the Al overlayer thickness. Shifts of the Si 2p and C 1s XPS core levels occurred to higher (lower) binding energy for the p-(n-)type substrates, which was attributed to the occurrence of band bending due to Fermi-level equilibration at the interface. The hole injection barrier at the p-type interface was determined to be 1.83±0.1 eV, while the n-type interface revealed an electron injection barrier of 0.98±0.1 eV. Due to the weak features in the SiC valence bands measured by XPS, the VBM positions were determined using the Si 2p peak positions. This procedure required the determination of the Si 2p-to-VBM binding energy difference (99.34 eV), which was obtained from additional measurements.

Polyphenylsilole multilayers--an insight from X-ray electron spectroscopy and density functional theory.

PubMed

Diller, Katharina; Ma, Yong; Luo, Yi; Allegretti, Francesco; Liu, Jianzhao; Tang, Ben Zhong; Lin, Nian; Barth, Johannes V; Klappenberger, Florian

2015-12-14

We present a combined investigation by means of X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy of condensed multilayers of two polyphenylsiloles, namely hexaphenylsilole (HPS) and tetraphenylsilole (TPS). Both compounds exhibit very similar spectroscopic signatures, whose interpretation is aided by density functional theory (DFT) calculations. High-resolution XPS spectra of the Si 2p and C 1s core levels of these multilayers indicate a positively charged silicon ion flanked by two negatively charged adjacent carbon atoms in the silole core of both molecules. This result is corroborated quantitatively by DFT calculations on isolated HPS (TPS) molecules, which show a natural bond orbital partial charge of +1.67 e (+1.58 e) on the silicon and -0.34 e (-0.58 e) on the two neighbouring carbon atoms in the silole ring. These charges are conserved in direct contact with a Cu(111) substrate for films of submonolayer coverage, as evidenced by the Si 2p XPS data. The C K-edge NEXAFS spectra of HPS and TPS multilayers exhibit distinct and differing features. Their main characteristics reappear in the simulated spectra and are assigned to the different inequivalent carbon species in the molecule. The angle-dependent measurements hardly reveal any dichroism, i.e., the molecular π-systems are not uniformly oriented parallel or perpendicular with respect to the surface. Changes in the growth conditions of TPS, i.e., a reduction of the substrate temperature from 240 K to 80 K during deposition, lead to a broadening of both XPS and NEXAFS signatures, as well as an upward shift of the Si 2p and C 1s binding energies, indicative of a less ordered growth mode at low temperature.

Surface analysis of glass fibres using XPS and AFM: case study of glass fibres recovered from the glass fibre reinforced polymer using chemical recycling

NASA Astrophysics Data System (ADS)

Nzioka, A. M.; Kim, Y. J.

2018-01-01

In this study, we present the results of an experimental study of the use of the X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) to characterise the coatings of the recovered E - glass fibres. The recovered E - glass fibres were obtained using chemical recycling process coupled with ultrasound cavitation. The objective of this study was to analyse the impact of chemical recycling and the ultrasound cavitation process on the sizing properties of the recovered fibres. We obtained the recovered fibres and sized using 1 wt% 3 - aminopropyltriethoxysilane (APS). Part of the sized fibres was washed with acetone and analysed all the sample fibres using AFM and XPS. Results showed the different composition of sizing after extraction using acetone. We compared the results of this study with that of virgin clean glass fibres.

Simple quantification of surface carboxylic acids on chemically oxidized multi-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Gong, Hyejin; Kim, Seong-Taek; Lee, Jong Doo; Yim, Sanggyu

2013-02-01

The surface of multi-walled carbon nanotube (MWCNT) was chemically oxidized using nitric acid and sulfuric-nitric acid mixtures. Thermogravimetric analysis, transmission electron microscopy and infrared spectroscopy revealed that the use of acid mixtures led to higher degree of oxidation. More quantitative identification of surface carboxylic acids was carried out using X-ray photoelectron spectroscopy (XPS) and acid-base titration. However, these techniques are costly and require very long analysis times to promptly respond to the extent of the reaction. We propose a much simpler method using pH measurements and pre-determined pKa value in order to estimate the concentration of carboxylic acids on the oxidized MWCNT surfaces. The results from this technique were consistent with those obtained from XPS and titration, and it is expected that this simple quantification method can provide a cheap and fast way to monitor and control the oxidation reaction of MWCNT.

Self-repairing vanadium-zirconium composite conversion coating for aluminum alloys

NASA Astrophysics Data System (ADS)

Zhong, Xin; Wu, Xiaosong; Jia, Yuyu; Liu, Yali

2013-09-01

In this paper, new self-repairing vanadium-zirconium composite conversion coating was prepared and investigated by Electrochemical impedance spectra (EIS), Scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. EIS results showed that V-Zr conversion coating with hydrogen peroxide modified (VZO) revealed an increasing corrosion resistance in corrosive media which meant a certain self-repairing effect. SEM comparison photos also disclosed that VZO treated with scratches was gradually ameliorated from the initial cracked configuration to fewer cracks and more fillers through an immersion of 3.5% NaCl solution. XPS results demonstrated that the content of vanadium on VZO increased and zirconium declined when immersed in the corrosive solution. This explained further that the self-repairing ability could be related to vanadium. From the above results, we inferred possible structures of VZO and proposed that self-repairing effect was achieved through a hydrolysis condensation polymerization process of vanadate in the localized corrosion area.

XPS study of the effect of hydrocarbon contamination on polytetrafluoroethylene (teflon) exposed to atomic oxygen

NASA Technical Reports Server (NTRS)

Golub, Morton A.; Wydeven, Theodore; Cormia, Robert D.

1991-01-01

The presence of hydrocarbon contamination on the surface of polytetrafluoroethylene (PTFE) markedly affects the oxygen uptake, and hence the wettability, of this polymer when exposed to an oxygen plasma. As revealed by X-ray photoelectron spectroscopy (XPS) analysis, the oxygen-to-carbon ratio (O/C) for such a polymer can increase sharply, and correspondingly the fluorine-to-carbon ratio (F/C) can decrease sharply, at very short exposure times; at longer times, however, such changes in the O/C and F/C ratios reverse direction, and these ratios then assume values similar to those of the unexposed PTFE. The greater the extent of hydrocarbon contamination in the PTFE, the larger are the amplitudes of the 'spikes' in the O/C- and F/C-exposure time plots. In contrast, a pristine PTFE experiences a very small, monotonic increase of surface oxidation or O/C ratio with time of exposure to oxygen atoms, while the F/C ratio is virtually unchanged from that of the unexposed polymer (2.0). Unless the presence of adventitious hydrocarbon is taken into account, anomalous surface properties relating to polymer adhesion may be improperly ascribed to PTFE exposed to an oxygen plasma.

Effects of K and Pt promoters on the performance of cobalt catalyst supported on CNTs

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

Zabidi, Noor Asmawati Mohd, E-mail: noorasmawati-mzabidi@petronas.com.my; Ali, Sardar, E-mail: alikhan-635@yahoo.com; Subbarao, Duvvuri, E-mail: duvvuri-subbarao@petronas.com.my

2014-10-24

This paper presents a comparative study on the effects of incorporation of potassium (K) and platinum (Pt) as promoters on the physicochemical properties of cobalt catalyst. The catalyst was prepared by a wet impregnation method on a CNTs support. Samples were characterized using transmission electron microscopy (TEM), H{sub 2}-temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) techniques. Fischer-Tropsch Synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H{sub 2}/CO = 2v/v and space velocity, SV of 12 L/g.h for 5 hours. The K-promoted and Pt-promoted Co catalysts have different physicochemical properties and catalytic performances comparedmore » to that of the un-promoted Co catalyst. XPS analysis revealed that K and Pt promoters induced electronic modifications as exhibited by the shifts in the Co binding energies. Incorporation of 0.06 wt% K and 0.06 wt% Pt in Co/CNTs catalyst resulted in an increase in the CO conversion and C{sub 5+} selectivity and a decrease in methane selectivity. Potassium was found to be a better promoter for Co/CNTs catalyst compared to platinum.« less

Effects of K and Pt promoters on the performance of cobalt catalyst supported on CNTs

NASA Astrophysics Data System (ADS)

Zabidi, Noor Asmawati Mohd; Ali, Sardar; Subbarao, Duvvuri

2014-10-01

This paper presents a comparative study on the effects of incorporation of potassium (K) and platinum (Pt) as promoters on the physicochemical properties of cobalt catalyst. The catalyst was prepared by a wet impregnation method on a CNTs support. Samples were characterized using transmission electron microscopy (TEM), H2-temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) techniques. Fischer-Tropsch Synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/ CO = 2v / v and space velocity, SV of 12 L/g.h for 5 hours. The K-promoted and Pt-promoted Co catalysts have different physicochemical properties and catalytic performances compared to that of the un-promoted Co catalyst. XPS analysis revealed that K and Pt promoters induced electronic modifications as exhibited by the shifts in the Co binding energies. Incorporation of 0.06 wt% K and 0.06 wt% Pt in Co/CNTs catalyst resulted in an increase in the CO conversion and C5+ selectivity and a decrease in methane selectivity. Potassium was found to be a better promoter for Co/CNTs catalyst compared to platinum.

UHV AFM based colloidal probe studies of adhesive properties of VAlN hard coatings

NASA Astrophysics Data System (ADS)

Wiesing, M.; de los Arcos, T.; Grundmeier, G.

2018-01-01

The adhesion of polystyrene (PS) on V0.27Al0.29N0.44 and the related influence of the oxidation states of both surfaces was investigated using X-Ray Photoelectron Spectroscopy (XPS) and Colloidal Force Spectroscopy (CFS) in Ultra-High Vacuum (UHV). Complementary, the intimate relation between the adhesion force, the chemical structure and surface polarizability was investigated by XPS valence band spectroscopy and the calculation of non-retarded Hamaker coefficients using Lifshitz theory based on optical data as derived from Reflection Electron Energy Loss Spectroscopy (REELS) spectra. The combined electron and force spectroscopic analysis of the interaction forces disclosed quantitatively the separation of the adhesion force in van der Waals and Lewis acid-base contributions. Further, the surface polarizability of VAlN was shown to be unaffected by oxygen incorporation due to the formation of an only gradually oxidized surface comprising a range of vanadium oxidation states. In contrast, the adhesion force analysis revealed additional Lewis acid-base interactions between the oxidized and non-oxidized VAlN surfaces and carboxyl groups present in the surface of PS after an oxidative oxygen beam treatment.

Formation and stability of dense arrays of Au nanoclusters on hexagonal boron nitride/Rh(111)

NASA Astrophysics Data System (ADS)

Patterson, Matthew C.; Habenicht, Bradley F.; Kurtz, Richard L.; Liu, Li; Xu, Ye; Sprunger, Phillip T.

2014-05-01

We have studied the nucleation and growth of Au clusters at submonolayer and greater coverages on the h-BN nanomesh grown on Rh(111) by means of scanning tunneling microscopy (STM), x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). STM reveals that submonolayer Au deposited at 115 K nucleates within the nanomesh pores and remains confined to the pores even after warming to room temperature. Whereas there is a propensity of monoatomic high islands at low temperature, upon annealing, bi- and multilayer Au clusters emerge. Deposition of higher coverages of Au similarly results in Au clusters primarily confined to the nanomesh pores at room temperature. XPS analysis of core-level electronic states in the deposited Au shows strong final-state effects induced by restricted particle size dominating for low Au coverage, with indications that larger Au clusters are negatively charged by interaction through the h-BN monolayer. DFT calculations suggest that the structure of the Au clusters transitions from monolayer to bilayer at a size between 30 and 37 atoms per cluster, in line with our experiment. Bader charge analysis supports the negative charge state of deposited Au.

Synthesis and characterization of novel 4-Tetra-4-Tolylsulfonyl ZnPc thin films for optoelectronic applications

NASA Astrophysics Data System (ADS)

Khalil, Salah; Tazarki, Helmi; Souli, Mehdi; Guasch, Cathy; Jamoussi, Bassem; Kamoun, Najoua

2017-11-01

Novel 4-Tetra-4-Tolylsulfonyl:zinc phthalocyanine and simple zinc phthalocyanine were synthesized. Our materials were grown on glass substrates by spin coating technique. Thin films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electronic micrograph (SEM), atomic force microscopy (AFM), spectrophotometer and Hall effect measurement. X-ray spectra reveal that 4-Tetra-4-Tolylsulfonyl:zinc phthalocyanine (4T4TS:ZnPc) and zinc phthalocyanine (ZnPc) thin films have a monoclinic crystalline structure in β phase. The surface properties and chemical composition were detailed using XPS measurement. SEM were used to investigate the surface morphology for 4T4TS:ZnPc and ZnPc thin films. Atomic force microscopy images have shown a decrease in surface roughness after substitution. Optical properties were investigated by measuring transmission and reflection spectra. Electrical properties were studied and the different electrical parameters was measured and compared on glass, silicon and tin dioxide substrates by Hall Effect technique. All obtained results indicate an improvement in physical properties of 4T4TS:ZnPc which allows used it in optoelectronic applications.

Effect of Cr doping on the structural, morphological, optical and electrical properties of indium tin oxide films

NASA Astrophysics Data System (ADS)

Mirzaee, Majid; Dolati, Abolghasem

2015-03-01

We report on the preparation and characterization of high-purity chromium (0.5-2.5 at.%)-doped indium tin oxide (ITO, In:Sn = 90:10) films deposited by sol-gel-mediated dip coating. The effects of different Cr-doping contents on structural, morphological, optical and electrical properties of the films were characterized by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), UV-Vis spectroscopy and four-point probe methods. XRD showed high phase purity cubic In2O3 and indicated a contraction of the lattice with Cr doping. FESEM micrographs show that grain size decreased with increasing the Cr-doping content. A method to determine chromium species in the sample was developed through the decomposition of the Cr 2 p XPS spectrum in Cr6+ and Cr3+ standard spectra. Optical and electrical studies revealed that optimum opto-electronic properties, including minimum sheet resistance of 4,300 Ω/Sq and an average optical transmittance of 85 % in the visible region with a band gap of 3.421 eV, were achieved for the films doped with Cr-doping content of 2 at.%.

Reduced graphene oxide growth on 316L stainless steel for medical applications

NASA Astrophysics Data System (ADS)

Cardenas, L.; MacLeod, J.; Lipton-Duffin, J.; Seifu, D. G.; Popescu, F.; Siaj, M.; Mantovani, D.; Rosei, F.

2014-07-01

We report a new method for the growth of reduced graphene oxide (rGO) on the 316L alloy of stainless steel (SS) and its relevance for biomedical applications. We demonstrate that electrochemical etching increases the concentration of metallic species on the surface and enables the growth of rGO. This result is supported through a combination of Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), scanning electron microscopy (SEM), density functional theory (DFT) calculations and static water contact angle measurements. Raman spectroscopy identifies the G and D bands for oxidized species of graphene at 1595 cm-1 and 1350 cm-1, respectively, and gives an ID/IG ratio of 1.2, indicating a moderate degree of oxidation. XPS shows -OH and -COOH groups in the rGO stoichiometry and static contact angle measurements confirm the wettability of rGO. SEM and AFM measurements were performed on different substrates before and after coronene treatment to confirm rGO growth. Cell viability studies reveal that these rGO coatings do not have toxic effects on mammalian cells, making this material suitable for biomedical and biotechnological applications.

Cohort study comparing prostate photovaporisation with XPS 180W and HPS 120W laser.

PubMed

López, B; Capitán, C; Hernández, V; de la Peña, E; Jiménez-Valladolid, I; Guijarro, A; Pérez-Fernández, E; Llorente, C

2016-01-01

Prostate photovaporisation with Greenlight laser for the surgical treatment of benign prostate hyperplasia has rapidly evolve to the new XPS 180W. We have previously demonstrated the safety and efficacy of the HPS 120W. The aim of this study was to assess the functional and safety results, with a year of follow-up, of photovaporisation using the XPS 180W laser compared with its predecessor. A cohort study was conducted with a series of 191 consecutive patients who underwent photovaporisation between 1/2008 and 5/2013. The inclusion criteria were an international prostate symptom score (IPSS) >15 after medical failure, a prostate volume <80 cm(3) and a maximum flow <15 mL/s. We assessed preoperative and intraoperative variables (energy used, laser time and total surgical time), complications, catheter hours, length of stay and functional results (maximum flow, IPSS, prostate-specific antigen and prostate volume) at 3, 6 and 12 months. We analysed the homogeneity in preoperative characteristics of the 2 groups through univariate analysis techniques. The postoperative functional results were assessed through an analysis of variance of repeated measures with mixed models. A total of 109 (57.1%) procedures were performed using HPS 120W, and 82 (42.9%) were performed using XPS. There were no differences between the preoperative characteristics. We observed significant differences both in the surgical time and effective laser time in favour of the XPS system. This advantage was 11% (48 ± 15.7 vs. 53.8 ± 16.2, p<.05) and 9% (32.8 ± 11.7 vs. 36 ± 11.6, p<.05), respectively. There were no statistically significant differences in the rest of the analysed parameters. The technical improvements in the XPS 180W system help reduce surgical time, maintaining the safety and efficacy profile offered by the HPS 120W system, with completely superimposable results at 1 year of follow-up. Copyright © 2015 AEU. Publicado por Elsevier España, S.L.U. All rights reserved.

Spontaneous desorption and phase transitions of self-assembled alkanethiol and alicyclic thiol monolayers chemisorbed on Au(111) in ultrahigh vacuum at room temperature.

PubMed

Ito, Eisuke; Kang, Hungu; Lee, Dongjin; Park, Joon B; Hara, Masahiko; Noh, Jaegeun

2013-03-15

Scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) were used to examine the surface structure and adsorption conditions of hexanethiol (HT) and cyclohexanethiol (CHT) self-assembled monolayers (SAMs) on Au(111) as a function of storage period in ultrahigh vacuum (UHV) conditions of 3×10(-7) Pa at room temperature (RT). STM imaging revealed that after storage for 7 days, HT SAMs underwent phase transitions from c(4×2) phase to low coverage 4×√3 phase. This transition is due to a structural rearrangement of hexanethiolates that results from the spontaneous desorption of chemisorbed HT molecules on Au(111) surface. XPS measurements showed approximately 28% reduction in sulfur coverage, which indicates desorption of hexanethiolates from the surfaces. Contrary to HT SAMs, the structural order of CHT SAMs with (5×2√3)R35° phase completely disappeared after storage for 3 or 7 days. XPS results show desorption of more than 80% of the cyclohexanethiolates, even after storage for 3 days. We found that spontaneous desorption of CHT molecules on Au(111) in UHV at RT occurred quickly, whereas spontaneous desorption of HT molecules was much slower. Thermal desorption spectroscopy (TDS) results suggest CHT SAMs in UHV at RT can desorb more efficiently than HT SAMs due to formation of thiol desorption fragments that result from chemical reactions between surface hydrogen atoms and thiolates on Au(111) surfaces. This study clearly demonstrated that organic thiols chemisorbed on gold surfaces are desorbed spontaneously in UHV at RT and van der Waals interactions play an important role in determining the structural stability of thiolate SAMs in UHV. Copyright © 2012 Elsevier Inc. All rights reserved.

Determination of trace metals in TSP and PM2.5 materials collected in the Metropolitan Area of Monterrey, Mexico: A characterization study by XPS, ICP-AES and SEM-EDS

NASA Astrophysics Data System (ADS)

González, Lucy T.; Longoria Rodríguez, F. E.; Sánchez-Domínguez, M.; Cavazos, Aleyda; Leyva-Porras, C.; Silva-Vidaurri, L. G.; Askar, Karim Acuña; Kharissov, B. I.; Villarreal Chiu, J. F.; Alfaro Barbosa, J. M.

2017-11-01

The concentration levels of trace metals of toxicological importance were evaluated in the total suspended particles (TSP) and particulate matter smaller than 2.5 μm (PM2.5) collected in the Metropolitan Area of Monterrey (MAM) in Mexico. Samples were characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy with an energy-dispersive spectroscopy system (SEM-EDS). In addition, the data were statistically treated by the methodology of Pearson Correlation (PC) and Principal Components Analysis (PCA) to identify the possible emitting sources. Surface analysis of the particulate matter (PM) by XPS revealed that the most abundant elements were Ca, Al, Na, Zn, Cu and Mg. The deconvolution of the Ca2p, Zn2p and Cu2p signals showed that the main contributors were CaCO3, ZnO and Cu/Cu2O, respectively. The bulk analysis of the PM by ICP-AES showed Fe, Cu and Zn as the most abundant elements. Fe-rich particles presented two different morphologies: the prismatic particles were associated with a natural origin, while the spherical particles with anthropogenic sources. The Zn and Cu were predominantly observed in the sampling stations with high vehicular traffic, and the emitting sources were associated with the burning of fuels from automobiles and the wear of the tires and brakes. The highest concentration of Pb was detected in the sampling station located near the industrial zones, and its cause was associated with the ceramic and glass industries, the burning of fuel oil in power plants and the production of lead-based batteries for automobiles.

Influence of square wave anodization on the electronic properties and structures of the passive films on Ti in sulfuric acid solution

NASA Astrophysics Data System (ADS)

Long, Y.; Li, D. G.; Chen, D. R.

2017-12-01

Two types of square wave anodization (type 1 and type 2) were employed in this work to form a passive film on Ti in a 0.5 M H2SO4 solution. The influences of the anodization potential and duration on the electronic properties and structures of the passive films were studied by Mott-Schottky plots, auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The results showed that the donor density, ND, of the passive film decreased and the flat band potential, EFB, shifted to the positive direction with the increase of the anodization duration and high anodization potential irrespective of whether type 1 or type 2 was used. Moreover, the passive film that formed on Ti using type 1 had a lower donor density and a more positive flat band potential than that on Ti using type 2 at one fixed anodization duration (only exchanging the anodization order of 1 V and the high potential). XPS analysis revealed that the outmost passive film was only composed of TiO2, the inner passive film was mainly composed of TiO2 with some amount of TiO and Ti2O3, and the TiO2 concentration in the outermost passive film increased with the increase of the anodization duration and the high potential in the case of using type 1 or type 2, implying an increased degree of crystallinity. The AES results showed that the O/Ti atomic ratio of the passive film obviously increased with the increasing anodization duration and high potential, demonstrating the increased homogeneous characteristic of the passive film; this was in agreement with the Mott-Schottky and XPS results.

Surface Characterization of Polymer Blends by XPS and ToF-SIMS

PubMed Central

Chan, Chi Ming; Weng, Lu-Tao

2016-01-01

The surface properties of polymer blends are important for many industrial applications. The physical and chemical properties at the surface of polymer blends can be drastically different from those in the bulk due to the surface segregation of the low surface energy component. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary mass spectrometry (ToF-SIMS) have been widely used to characterize surface and bulk properties. This review provides a brief introduction to the principles of XPS and ToF-SIMS and their application to the study of the surface physical and chemical properties of polymer blends. PMID:28773777

Comparative study on Ga1-xZnxN1-yOy oxynitride synthesized by different techniques for application in photocatalytic hydrogen production

NASA Astrophysics Data System (ADS)

Menon, Sumithra Sivadas; Baskar, K.; Singh, Shubra

2017-06-01

Hydrogen evolution by overall water splitting has emerged as a potential method for green energy generation due to the introduction of highly efficient photocatalysts active under visible region of spectra. In the present work, we focus on a comparative study of the properties of Ga1-xZnxN1-yOy oxynitride samples synthesized by two techniques and their effect on the sample properties. The samples were prepared by both traditional nitridation technique and solution combustion method. Room temperature photoluminescence studies revealed the introduction of additional energy levels above the valence band which in turns broadens the valence band and subsequently reduces the band gap. The band gap narrowing was further confirmed using diffuse reflectance spectroscopy and Valence band X-ray photoelectron spectroscopy (VB-XPS). It was also realized from VB XPS that the reduction of band gap in both the samples was due to upshift of valence band without affecting the conduction band. The presence of disorder activated modes in the samples was examined using temperature dependent Raman spectroscopy. In this work we corroborate the theoretical prediction reported by Al-Jassim et. al that the bandgap narrowing mechanism in ZnO rich solid solution and GaN rich solid solution is asymmetric and a significant bandgap reduction could be observed for ZnO rich solid solution than GaN rich.

Morphological evolution in dewetting polystyrene/polyhedral oligomeric silsesquioxane thin film bilayers.

PubMed

Paul, Rituparna; Karabiyik, Ufuk; Swift, Michael C; Hottle, John R; Esker, Alan R

2008-05-06

Morphological evolution in dewetting thin film bilayers of polystyrene (PS) and a polyhedral oligomeric silsesquioxane (POSS), trisilanolphenyl-POSS (TPP), was studied as a function of annealing temperature and annealing time. The results demonstrate unique dewetting morphologies in PS/TPP bilayers at elevated temperatures that are significantly different from those typically observed in dewetting polymer/polymer bilayers. During temperature ramp studies by optical microscopy (OM) in the reflection mode, PS/TPP bilayers form cracks with a weak optical contrast at approximately 130 degrees C. The crack formation is attributed to tensile stresses within the upper TPP layer. The weak optical contrast of the cracks observed in the bilayers for annealing temperatures below approximately 160 degrees C is consistent with the cracking and dewetting of only the upper TPP layer from the underlying PS layer. The optical contrast of the morphological features is significantly enhanced at annealing temperatures of >160 degrees C. This observation suggests dewetting of both the upper TPP and the lower PS layers that results in the exposure of the silicon substrate. Upon annealing the PS/TPP bilayers at 200 degrees C in a temperature jump experiment, the upper TPP layer undergoes instantaneous cracking as observed by OM. These cracks in the upper TPP layer serve as nucleation sites for rapid dewetting and aggregation of the TPP layer, as revealed by OM and atomic force microscopy (AFM). X-ray photoelectron spectroscopy (XPS) results indicated that dewetting of the lower PS layer ensued for annealing times >5 min and progressed up to 90 min. For annealing times >90 min, OM, AFM, and XPS results revealed complete dewetting of both the layers with the formation of TPP encapsulated PS droplets.

Local Structure and Surface Properties of CoxZn1-xO Thin Films for Ozone Gas Sensing.

PubMed

Catto, Ariadne C; Silva, Luís F da; Bernardi, Maria Inês B; Bernardini, Sandrine; Aguir, Khalifa; Longo, Elson; Mastelaro, Valmor R

2016-10-05

A detailed study of the structural, surface, and gas-sensing properties of nanostructured Co x Zn 1-x O films is presented. X-ray diffraction (XRD) analysis revealed a decrease in the crystallization degree with increasing Co content. The X-ray absorption near-edge structure (XANES) and X-ray photoelectron spectroscopies (XPS) revealed that the Co 2+ ions preferentially occupied the Zn 2+ sites and that the oxygen vacancy concentration increased as the amount of cobalt increased. Electrical measurements showed that the Co dopants not only enhanced the sensor response at low ozone levels (ca. 42 ppb) but also led to a decrease in the operating temperature and improved selectivity. The enhancement in the gas-sensing properties was attributed to the presence of oxygen vacancies, which facilitated ozone adsorption.

Giant crystal-electric-field effect and complex magnetic behavior in single-crystalline CeRh3Si2

NASA Astrophysics Data System (ADS)

Pikul, A. P.; Kaczorowski, D.; Gajek, Z.; Stȩpień-Damm, J.; Ślebarski, A.; Werwiński, M.; Szajek, A.

2010-05-01

Single-crystalline CeRh3Si2 was investigated by means of x-ray diffraction, magnetic susceptibility, magnetization, electrical resistivity, and specific-heat measurements carried out in wide temperature and magnetic field ranges. Moreover, the electronic structure of the compound was studied at room temperature by cerium core-level x-ray photoemission spectroscopy (XPS). The physical properties were analyzed in terms of crystalline electric field and compared with results of ab initio band-structure calculations performed within the density-functional theory approach. The compound was found to crystallize in the orthorhombic unit cell of the ErRh3Si2 type (space group Imma No.74, Pearson symbol: oI24 ) with the lattice parameters a=7.1330(14)Å , b=9.7340(19)Å , and c=5.6040(11)Å . Analysis of the magnetic and XPS data revealed the presence of well-localized magnetic moments of trivalent cerium ions. All the physical properties were found to be highly anisotropic over the whole temperature range studied and influenced by exceptionally strong crystalline electric field with the overall splitting of the 4f1 ground multiplet exceeding 5700 K. Antiferromagnetic order of the cerium magnetic moments at TN=4.70(1)K and their subsequent spin rearrangement at Tt=4.48(1)K manifest themselves as distinct anomalies in the temperature characteristic of all the physical properties investigated and exhibit complex evolution in an external magnetic field. A tentative magnetic B-T phase diagram, constructed for B parallel to the b axis being the easy magnetization direction, shows very complex magnetic behavior of CeRh3Si2 , similar to that recently reported for an isostructural compound CeIr3Si2 . The electronic band-structure calculations corroborated the antiferromagnetic ordering of the cerium magnetic moments and well-reproduced the experimental XPS valence-band spectrum.

Surface and electronic structure of Bi-Ca-Sr-Cu-O superconductors studied by LEED, UPS and XPS

NASA Astrophysics Data System (ADS)

Shen, Z.-X.; Lindberg, P. A. P.; Wells, B. O.; Lindau, I.; Spicer, W. E.; Mitzi, D. B.; Eom, C. B.; Kapitulnik, A.; Geballe, T. H.; Soukiassian, P.

1989-02-01

Single crystal and polycrystalline samples of Bi2CaSr2Cu2O8 have been studied by various surface sensitive techniques, including low energy electron diffraction (LEED), ultraviolet photoemission spectroscopy (UPS) and x-ray photoemission spectroscopy (XPS). The surface structure of the single crystals was characterized by LEED to be consistent with that of the bulk structure. Our data suggest that Bi2CaSr2Cu2O8 single crystals are very stable in the ultrahigh vacuu. No change of XPS spectra with temperature was observed. We have also studied the electronic structure of Bi2Sr2CuO6, which has a lower superconducting transition temperature Tc. Comparing the electronic structure of the two Bi-Ca-Sr-Cu-O superconductors, an important difference in the density of states near EF was observed which seems to be related to the difference in Tc.

Morphological and XPS study of ball milled Fe1-xAlx (0.3≤x≤0.6) alloys

NASA Astrophysics Data System (ADS)

Rajan, Sandeep; Kumar, Anil; Vyas, Anupam; Brajpuriya, Ranjeet

2018-05-01

The paper presents mechanical and XPS study of ball milled Fe1-xAlx (0.3≤x≤0.6) alloys. The author prepared the solid solution of Fe(Al) with different composition of Al by using mechanical alloying (MA) technique. The MA process induces a progressive dissolution of Al into Fe, resulted in the formation of an extended Fe(Al) solid solution with the bcc structure after 5 hr of milling. The SEM Images shows that the initial shape of particles disappeared completely, and their structure became a mixture of small and large angular-shaped crystallites with different sizes. The TEM micrograph also confirms the reduction in crystallite size and alloy formation. XPS study shows the shift in the binding energy position of both Fe and Al Peaks provide strong evidence of Fe(Al) phase formation after milling.

XPS studies of nitrogen doping niobium used for accelerator applications

NASA Astrophysics Data System (ADS)

Yang, Ziqin; Lu, Xiangyang; Tan, Weiwei; Zhao, Jifei; Yang, Deyu; Yang, Yujia; He, Yuan; Zhou, Kui

2018-05-01

Nitrogen doping study on niobium (Nb) samples used for the fabrication of superconducting radio frequency (SRF) cavities was carried out. The samples' surface treatment was attempted to replicate that of the Nb SRF cavities, which includes heavy electropolishing (EP), nitrogen doping and the subsequent EP with different amounts of material removal. The surface chemical composition of Nb samples with different post treatments has been studied by XPS. The chemical composition of Nb, O, C and N was presented before and after Gas Cluster Ion Beam (GCIB) etching. No signals of poorly superconducting nitrides NbNx was found on the surface of any doped Nb sample with the 2/6 recipe before GCIB etching. However, in the depth range greater than 30 nm, the content of N element is below the XPS detection precision scope even for the Nb sample directly after nitrogen doping treatment with the 2/6 recipe.

Novel durable bio-photocatalyst purifiers, a non-heterogeneous mechanism: accelerated entrapped dye degradation into structural polysiloxane-shield nano-reactors.

PubMed

Dastjerdi, Roya; Montazer, Majid; Shahsavan, Shadi; Böttcher, Horst; Moghadam, M B; Sarsour, Jamal

2013-01-01

This research has designed innovative Ag/TiO(2) polysiloxane-shield nano-reactors on the PET fabric to develop novel durable bio-photocatalyst purifiers. To create these very fine nano-reactors, oppositely surface charged multiple size nanoparticles have been applied accompanied with a crosslinkable amino-functionalized polysiloxane (XPs) emulsion. Investigation of photocatalytic dye decolorization efficiency revealed a non-heterogeneous mechanism including an accelerated degradation of entrapped dye molecules into the structural polysiloxane-shield nano-reactors. In fact, dye molecules can be adsorbed by both Ag and XPs due to their electrostatic interactions and/or even via forming a complex with them especially with silver NPs. The absorbed dye and active oxygen species generated by TiO(2) were entrapped by polysiloxane shelter and the presence of silver nanoparticles further attract the negative oxygen species closer to the adsorbed dye molecules. In this way, the dye molecules are in close contact with concentrated active oxygen species into the created nano-reactors. This provides an accelerated degradation of dye molecules. This non-heterogeneous mechanism has been detected on the sample containing all of the three components. Increasing the concentration of Ag and XPs accelerated the second step beginning with an enhanced rate. Further, the treated samples also showed an excellent antibacterial activity. Copyright © 2012 Elsevier B.V. All rights reserved.

Local Fine Structural Insight into Mechanism of Electrochemical Passivation of Titanium.

PubMed

Wang, Lu; Yu, Hongying; Wang, Ke; Xu, Haisong; Wang, Shaoyang; Sun, Dongbai

2016-07-20

Electrochemically formed passive film on titanium in 1.0 M H2SO4 solution and its thickness, composition, chemical state, and local fine structure are examined by Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure. AES analysis reveals that the thickness and composition of oxide film are proportional to the reciprocal of current density in potentiodynamic polarization. XPS depth profiles of the chemical states of titanium exhibit the coexistence of various valences cations in the surface. Quantitative X-ray absorption near edge structure analysis of the local electronic structure of the topmost surface (∼5.0 nm) shows that the ratio of [TiO2]/[Ti2O3] is consistent with that of passivation/dissolution of electrochemical activity. Theoretical calculation and analysis of extended X-ray absorption fine structure spectra at Ti K-edge indicate that both the structures of passivation and dissolution are distorted caused by the appearance of two different sites of Ti-O and Ti-Ti. And the bound water in the topmost surface plays a vital role in structural disorder confirmed by XPS. Overall, the increase of average Ti-O coordination causes the electrochemical passivation, and the dissolution is due to the decrease of average Ti-Ti coordination. The structural variations of passivation in coordination number and interatomic distance are in good agreement with the prediction of point defect model.

A preliminary view on adsorption of organics on ice at temperatures close to melting point

NASA Astrophysics Data System (ADS)

Kong, Xiangrui; Waldner, Astrid; Orlando, Fabrizio; Artiglia, Luca; Ammann, Markus; Bartels-Rausch, Thorsten

2016-04-01

Ice and snow play active roles in the water cycle, the energy budget of the Earth, and environmental chemistry in the atmosphere and cryosphere. The uptake of trace gases from the atmosphere may induce changes in the structure of the surface layer of ice crystals and has important consequences for atmospheric chemistry and the climate system. However, a molecular-level understanding of trace gas adsorption on ice is still missing, and also little is known about the impurity-induced ice-surface disorder in the context of environmental relevance. It is a general challenge to apply highly sensitive experimental approaches to ambient air conditions, e.g. studies of volatile surfaces, because of the strict requirements of vacuum experimental conditions. In this study, we employed synchrotron-based X-ray Photoelectron Spectroscopy (XPS) and partial electron yield Near Edge X-ray Absorption Fine Structure (NEXAFS) in a state-of-the-art Near-Ambient Pressure Photoelectron (NAPP) spectroscopy end station. The NAPP enables to utilize the surface sensitive experimental methods, XPS and NEXAFS with electron detection, on volatile surfaces, i.e. ice at temperatures approaching zero degree Celsius. XPS and NEXAFS provide unique information of hydrogen bonding network, surface concentration of organic adsorbates, depth profile of dopants in the ice, and acid-base dissociation on the surfaces. For instance, a few carboxylic acids, e.g. acetic acid and formic acid, have been recently studied by XPS and NEXAFS in NAPP. Amines are a group of nitrogen-containing basic organics with atmospheric relevance. Only few studies have been focused on amines, and atmospheric models rarely take account of them due to the limitation of knowledge. Several amines have been found to play active roles in the processes of aerosol formation, e.g. dimethylamine (DMA), trimethylamine (TMA) and 1-propanamine. In this study, we will focus on one of these three amines after pre-tests, and perform core-level spectroscopies to reveal the behaviour of adsorption and dissociation on ice. Additionally, pure ice and amine doped ice will be compared for their surface structure change at different temperatures, which will indicate the differences of surface disordering caused by different factors. For instance, we will have a chance to know better if impurities will cause local disordering, i.e. forming hydration shell, which challenges the traditional picture of a homogenous disordered doped ice surface. The findings of this study could not only improve our understanding of how acidic organics adsorb to ice, and of their chemical properties on ice, but also have potentials to know better the behaviour of pure ice at temperatures approaching to the melting point.

Schottky Barrier Height of Pd/MoS2 Contact by Large Area Photoemission Spectroscopy.

PubMed

Dong, Hong; Gong, Cheng; Addou, Rafik; McDonnell, Stephen; Azcatl, Angelica; Qin, Xiaoye; Wang, Weichao; Wang, Weihua; Hinkle, Christopher L; Wallace, Robert M

2017-11-08

MoS 2 , as a model transition metal dichalcogenide, is viewed as a potential channel material in future nanoelectronic and optoelectronic devices. Minimizing the contact resistance of the metal/MoS 2 junction is critical to realizing the potential of MoS 2 -based devices. In this work, the Schottky barrier height (SBH) and the band structure of high work function Pd metal on MoS 2 have been studied by in situ X-ray photoelectron spectroscopy (XPS). The analytical spot diameter of the XPS spectrometer is about 400 μm, and the XPS signal is proportional to the detection area, so the influence of defect-mediated parallel conduction paths on the SBH does not affect the measurement. The charge redistribution by Pd on MoS 2 is detected by XPS characterization, which gives insight into metal contact physics to MoS 2 and suggests that interface engineering is necessary to lower the contact resistance for the future generation electronic applications.

The adsorption of methyl iodide on uranium and uranium dioxide: Surface characterization using X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES)

NASA Astrophysics Data System (ADS)

Dillard, J. G.; Moers, H.; Klewe-Nebenius, H.; Kirch, G.; Pfennig, G.; Ache, H. J.

1984-09-01

The adsorption of methyl iodide on uranium and on uranium dioxide has been studied at 25 °C. Surfaces of the substrates were characterized before and after adsorption by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The XPS binding energy results indicate that CH 3I adsorption on uranium yields a carbide-type carbon, UC, and uranium iodide, UI 3. On uranium dioxide the carbon electron binding energy measurements are consistent with the formation of a hydrocarbon, —CH 3-type moiety. The interpretation of XPS and AES spectral features for CH 3I adsorption on uranium suggest that a complex dissociative adsorption reaction takes place. Adsorption of CH 3I on UO 2 occurs via a dissociative process. Saturation coverage occurs on uranium at approximately two langmuir (1 L = 10 -6 Torr s) exposure whereas saturation coverage on uranium dioxide is found at about five langmuir.

Samarium electrodeposited acetate and oxide thin films on stainless steel substrate characterized by XPS

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

Myhre, Kristian; Burns, Jonathan; Meyer, Harry

Characterization of a samarium thin film deposited on a stainless steel substrate using molecular electrodeposition was carried out using a Thermo Scientific K-Alpha X-ray photoelectron spectrometer. We studied two types of samarium electrodeposition samples, one as-deposited and one heated to 700 °C in an air flow. Survey scans include peaks coming from the stainless steel substrate, such as Fe and Cr. An X-ray photoelectron spectroscopy (XPS) survey spectrum, Sm 3d, C 1s, and O 1s narrow scans are shown. It was determined that the heating process decomposed the deposited Sm acetate to Sm 2O 3 using XPS.

Samarium electrodeposited acetate and oxide thin films on stainless steel substrate characterized by XPS

DOE PAGES

Myhre, Kristian; Burns, Jonathan; Meyer, Harry; ...

2016-06-01

Characterization of a samarium thin film deposited on a stainless steel substrate using molecular electrodeposition was carried out using a Thermo Scientific K-Alpha X-ray photoelectron spectrometer. We studied two types of samarium electrodeposition samples, one as-deposited and one heated to 700 °C in an air flow. Survey scans include peaks coming from the stainless steel substrate, such as Fe and Cr. An X-ray photoelectron spectroscopy (XPS) survey spectrum, Sm 3d, C 1s, and O 1s narrow scans are shown. It was determined that the heating process decomposed the deposited Sm acetate to Sm 2O 3 using XPS.

Combined soft and hard X-ray ambient pressure photoelectron spectroscopy studies of semiconductor/electrolyte interfaces

DOE PAGES

Starr, David E.; Favaro, Marco; Abdi, Fatwa F.; ...

2017-05-18

The development of solar fuel generating materials would greatly benefit from a molecular level understanding of the semiconductor/electrolyte interface and changes in the interface induced by an applied potential and illumination by solar light. Ambient pressure photoelectron spectroscopy techniques with both soft and hard X-rays, AP-XPS and AP-HAXPES respectively, have the potential to markedly contribute to this understanding. In this paper we initially provide two examples of current challenges in solar fuels material development that AP-XPS and AP-HAXPES can directly a ddress. This will be followed by a brief description of the distinguishing and complementary characteristics of soft and hardmore » X-ray AP-XPS and AP-HAXPES and best approaches to achieving monolayer sensitivity in solid/aqueous electrolyte studies. In particular we focus on the detection of surface adsorbed hydroxyl groups in the presence of aqueous hydroxide anions in the electrolyte, a common situation when investigating photoanodes for solar fuel generating applications. Finally, the article concludes by providing an example of a combined AP-XPS and AP-HAXPES study of a semiconductor/aqueous electrolyte interface currently used in water splitting devices specifically the BiVO 4/aqueous potassium phosphate electrolyte interface.« less

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

Sohn, H.; Camacho-Bunquin, J.; Langeslay, R. R.

Well-defined, isolated, single-site organovanadium(III) catalyst on SiO 2 [(SiO 2)V(Mes)(THF)] were synthesized via surface organometallic chemistry, and fully characterized using a combination of analytical and spectroscopic techniques (EA, ICP, 1H NMR, TGA-MS, EPR, XPS, DR-UV/Vis, UV-Raman, DRIFTS, XAS). The catalysts exhibit unprecedented reactivity in liquid- and gas-phase alkene/alkyne hydrogenation. Catalyst poisoning experiments revealed that 100% of the V sites are active for hydrogenation.

RECENT XPS STUDIES OF THE EFFECT OF PROCESSING ON NB SRF SURFACES

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

Hui Tian; Binping Xiao; Michael Kelley

XPS studies have consistently shown that Nb surfaces for SRF chiefly comprise of a few nm of Nb2O5 on top of Nb metal, with minor amounts of Nb sub-oxides. Nb samples after BCP/EP treatment with post-baking at the various conditions have been examined by using synchrotron based XPS. Despite the confounding influence of surface roughness, certain outcomes are clear. Lower-valence Nb species are always and only associated with the metal/oxide interface, but evidence for an explicit layer structure or discrete phases is lacking. Post-baking without air exposure shows decreased oxide layer thickness and increased contribution from lower valence species, butmore » spectra obtained after subsequent air exposure cannot be distinguished from those obtained prior to baking, though the SRF performance improvement remains.« less

Dysprosium electrodeposition from a hexaalkylguanidinium-based ionic liquid

NASA Astrophysics Data System (ADS)

Berger, Claudia A.; Arkhipova, Maria; Maas, Gerhard; Jacob, Timo

2016-07-01

The rare-earth element dysprosium (Dy) is an important additive that increases the magnetocrystalline anisotropy of neodymium magnets and additionally prevents from demagnetizing at high temperatures. Therefore, it is one of the most important elements for high-tech industries and is mainly used in permanent magnetic applications, for example in electric vehicles, industrial motors and direct-drive wind turbines. In an effort to develop a more efficient electrochemical technique for depositing Dy on Nd-magnets in contrast to commonly used costly physical vapor deposition, we investigated the electrochemical behavior of dysprosium(iii) trifluoromethanesulfonate in a custom-made guanidinium-based room-temperature ionic liquid (RTIL). We first examined the electrodeposition of Dy on an Au(111) model electrode. The investigation was carried out by means of cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS). The initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). CV measurements revealed a large cathodic reduction peak, which corresponds to the growth of monoatomic high islands, based on STM images taken during the initial stages of deposition. XPS identified these deposited islands as dysprosium. A similar reduction peak was also observed on an Nd-Fe-B substrate, and positively identified as deposited Dy using XPS. Finally, we varied the concentration of the Dy precursor, electrolyte flow and temperature during Dy deposition and demonstrated that each of these parameters could be used to increase the thickness of the Dy deposit, suggesting that these parameters could be tuned simultaneously in a temperature-controlled flow cell to enhance the thickness of the Dy layer.The rare-earth element dysprosium (Dy) is an important additive that increases the magnetocrystalline anisotropy of neodymium magnets and additionally prevents from demagnetizing at high temperatures. Therefore, it is one of the most important elements for high-tech industries and is mainly used in permanent magnetic applications, for example in electric vehicles, industrial motors and direct-drive wind turbines. In an effort to develop a more efficient electrochemical technique for depositing Dy on Nd-magnets in contrast to commonly used costly physical vapor deposition, we investigated the electrochemical behavior of dysprosium(iii) trifluoromethanesulfonate in a custom-made guanidinium-based room-temperature ionic liquid (RTIL). We first examined the electrodeposition of Dy on an Au(111) model electrode. The investigation was carried out by means of cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS). The initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). CV measurements revealed a large cathodic reduction peak, which corresponds to the growth of monoatomic high islands, based on STM images taken during the initial stages of deposition. XPS identified these deposited islands as dysprosium. A similar reduction peak was also observed on an Nd-Fe-B substrate, and positively identified as deposited Dy using XPS. Finally, we varied the concentration of the Dy precursor, electrolyte flow and temperature during Dy deposition and demonstrated that each of these parameters could be used to increase the thickness of the Dy deposit, suggesting that these parameters could be tuned simultaneously in a temperature-controlled flow cell to enhance the thickness of the Dy layer. Electronic supplementary information (ESI) available. See DOI: 10.1039/C6NR01351A

Semiconductor/dielectric interface engineering and characterization

NASA Astrophysics Data System (ADS)

Lucero, Antonio T.

The focus of this dissertation is the application and characterization of several, novel interface passivation techniques for III-V semiconductors, and the development of an in-situ electrical characterization. Two different interface passivation techniques were evaluated. The first is interface nitridation using a nitrogen radical plasma source. The nitrogen radical plasma generator is a unique system which is capable of producing a large flux of N-radicals free of energetic ions. This was applied to Si and the surface was studied using x-ray photoelectron spectroscopy (XPS). Ultra-thin nitride layers could be formed from 200-400° C. Metal-oxide-semiconductor capacitors (MOSCAPs) were fabricated using this passivation technique. Interface nitridation was able to reduce leakage current and improve the equivalent oxide thickness of the devices. The second passivation technique studied is the atomic layer deposition (ALD) diethylzinc (DEZ)/water treatment of sulfur treated InGaAs and GaSb. On InGaAs this passivation technique is able to chemically reduce higher oxidation states on the surface, and the process results in the deposition of a ZnS/ZnO interface passivation layer, as determined by XPS. Capacitance-voltage (C-V) measurements of MOSCAPs made on p-InGaAs reveal a large reduction in accumulation dispersion and a reduction in the density of interfacial traps. The same technique was applied to GaSb and the process was studied in an in-situ half-cycle XPS experiment. DEZ/H2O is able to remove all Sb-S from the surface, forming a stable ZnS passivation layer. This passivation layer is resistant to further reoxidation during dielectric deposition. The final part of this dissertation is the design and construction of an ultra-high vacuum cluster tool for in-situ electrical characterization. The system consists of three deposition chambers coupled to an electrical probe station. With this setup, devices can be processed and subsequently electrically characterized without exposing the sample to air. This is the first time that such a system has been reported. A special air-gap C-V probe will allow top gated measurements to be made, allowing semiconductor-dielectric interfaces to be studied during device processing.

Nanostructured PdO Thin Film from Langmuir-Blodgett Precursor for Room-Temperature H2 Gas Sensing.

PubMed

Choudhury, Sipra; Betty, C A; Bhattacharyya, Kaustava; Saxena, Vibha; Bhattacharya, Debarati

2016-07-06

Nanoparticulate thin films of PdO were prepared using the Langmuir-Blodgett (LB) technique by thermal decomposition of a multilayer film of octadecylamine (ODA)-chloropalladate complex. The stable complex formation of ODA with chloropalladate ions (present in subphase) at the air-water interface was confirmed by the surface pressure-area isotherm and Brewster angle microscopy. The formation of nanocrystalline PdO thin film after thermal decomposition of as-deposited LB film was confirmed by X-ray diffraction and Raman spectroscopy. Nanocrystalline PdO thin films were further characterized by using UV-vis and X-ray photoelectron spectroscopic (XPS) measurements. The XPS study revealed the presence of prominent Pd(2+) with a small quantity (18%) of reduced PdO (Pd(0)) in nanocrystalline PdO thin film. From the absorption spectroscopic measurement, the band gap energy of PdO was estimated to be 2 eV, which was very close to that obtained from specular reflectance measurements. Surface morphology studies of these films using atomic force microscopy and field-emission scanning electron microscopy indicated formation of nanoparticles of size 20-30 nm. These PdO film when employed as a chemiresistive sensor showed H2 sensitivity in the range of 30-4000 ppm at room temperature. In addition, PdO films showed photosensitivity with increase in current upon shining of visible light.

Comparative study of different carbon-supported Fe2O3-Pt catalysts for oxygen reduction reaction.

PubMed

Tellez-Cruz, M M; Padilla-Islas, M A; Pérez-González, M; Solorza-Feria, O

2017-11-01

One of the challenges in electrocatalysis is the adequate dispersion of the catalyst on an appropriate porous support matrix, being up to now the most commonly used the carbon-based supports. To overcome this challenge, carbon supports must first be functionalized to guide the catalyst's nucleation, thereby, improving the dispersion and allowing the use of smaller amount of the catalyst material to achieve a higher electrochemically active surface area. This study present the effect of functionalized Vulcan carbon XC72 (FVC) and functionalized Black Pearl carbon (FBPC) as supports on the catalytic activity of decorated Fe 2 O 3 with Pt. Both carbons were functionalized with HNO 3 and subsequently treated with ethanolamine. Fe 2 O 3 nanoparticles were synthesized by chemical reduction and decorated with platinum by epitaxial growth. Pt and Fe 2 O 3 structural phases were identified by XRD and XPS; the Pt content was measured by XPS, and results showed to a high Pt content in Fe 2 O 3 -Pt/FBPC. TEM micrographs reveal nanoparticles with an average size of 2 nm in both supported catalysts. The Fe 2 O 3 -Pt/FVC catalyst presents the highest specific activity and mass activity, 0.21 mA cm -2 Pt and 140 mA mg Pt -1 , respectively, associated to the appropriate distribution of platinum on the Fe 2 O 3 nanoparticles.

Enhancement of the photocatalytic activity of TiO(2) by doping it with calcium ions.

PubMed

Akpan, U G; Hameed, B H

2011-05-01

Titanium dioxide (TiO(2)) with an enhanced photocatalytic activity was developed by doping it with calcium ions through a sol-gel method. The developed photocatalysts were characterized by Fourier transform infrared (FTIR) spectroscopy, N(2) physisorption, X-ray photoelectron spectroscopy (XPS), and X-ray diffraction. Their surface morphologies were studied using surface scanning electron microscopy (SEM). The XPS analyses confirmed the presence of Ti, O, Ca, and C in the Ca-doped TiO(2) sample. The activities of the catalysts were evaluated by photocatalytic degradation of an azo dye, acid red 1 (AR1), using UV light irradiation. The results of the investigations revealed that the samples calcined at 300 °C for 3.6h in a cyclic (2 cycles) mode had the best performance. Lower percentage dopant, 0.3-1.0 wt.%, enhanced the photocatalytic activity of TiO(2), with the best at 0.5 wt.% Ca-TiO(2). The performance of 0.5 wt.% Ca-TiO(2) in the degradation of AR1 was far superior to that of a commercial anatase TiO(2) Sigma product CAS No. 1317-70-0. The effect of pH on the degradation of AR1 was studied, and the pH of the dye solution exerted a great influence on the degradation of the dye. Copyright © 2011 Elsevier Inc. All rights reserved.

Acquisition and evolution of plant pathogenesis-associated gene clusters and candidate determinants of tissue-specificity in xanthomonas.

PubMed

Lu, Hong; Patil, Prabhu; Van Sluys, Marie-Anne; White, Frank F; Ryan, Robert P; Dow, J Maxwell; Rabinowicz, Pablo; Salzberg, Steven L; Leach, Jan E; Sonti, Ramesh; Brendel, Volker; Bogdanove, Adam J

2008-01-01

Xanthomonas is a large genus of plant-associated and plant-pathogenic bacteria. Collectively, members cause diseases on over 392 plant species. Individually, they exhibit marked host- and tissue-specificity. The determinants of this specificity are unknown. To assess potential contributions to host- and tissue-specificity, pathogenesis-associated gene clusters were compared across genomes of eight Xanthomonas strains representing vascular or non-vascular pathogens of rice, brassicas, pepper and tomato, and citrus. The gum cluster for extracellular polysaccharide is conserved except for gumN and sequences downstream. The xcs and xps clusters for type II secretion are conserved, except in the rice pathogens, in which xcs is missing. In the otherwise conserved hrp cluster, sequences flanking the core genes for type III secretion vary with respect to insertion sequence element and putative effector gene content. Variation at the rpf (regulation of pathogenicity factors) cluster is more pronounced, though genes with established functional relevance are conserved. A cluster for synthesis of lipopolysaccharide varies highly, suggesting multiple horizontal gene transfers and reassortments, but this variation does not correlate with host- or tissue-specificity. Phylogenetic trees based on amino acid alignments of gum, xps, xcs, hrp, and rpf cluster products generally reflect strain phylogeny. However, amino acid residues at four positions correlate with tissue specificity, revealing hpaA and xpsD as candidate determinants. Examination of genome sequences of xanthomonads Xylella fastidiosa and Stenotrophomonas maltophilia revealed that the hrp, gum, and xcs clusters are recent acquisitions in the Xanthomonas lineage. Our results provide insight into the ancestral Xanthomonas genome and indicate that differentiation with respect to host- and tissue-specificity involved not major modifications or wholesale exchange of clusters, but subtle changes in a small number of genes or in non-coding sequences, and/or differences outside the clusters, potentially among regulatory targets or secretory substrates.

Characterization of bimetallic Fe/Pd nanoparticles by grape leaf aqueous extract and identification of active biomolecules involved in the synthesis.

PubMed

Luo, Fang; Yang, Die; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravi

2016-08-15

This paper reports the detailed composition and morphology of one-step green synthesized bimetallic Fe/Pd nanoparticles (NPs) using grape leaf aqueous extract and identification of active biomolecules involved in the synthesis employing various techniques. Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) revealed that Fe/Pd NPs were polydispersed and quasi-spherical with a diameter ranging from 2 to 20nm. X-ray Photoelectron Spectroscopy (XPS) and Energy Dispersive X-ray Spectroscopy (EDS) provided evidence for the composition of Fe and Pd and for their species existing on the surface of Fe/Pd NPs. In addition, biomolecules in the grape leaf aqueous extract were identified but their functions are still unclear. Biomolecules in the aqueous extract such as methoxy-phenyl-oxime, N-benzoyl-2-cyano-histamine, 2-ethyl-phenol, 1,2-benzenediol, β-hydroxyquebracamine, hydroquinone, 2-methoxy-4-vinylphenol, 5-methyl-2-furancarboxaldehyde, 4-(3-hydroxybutyl)-3,5,5-trimethyl-2-cyclohexen and some polyphenolic compounds were identified as reducing and capping agents, which were studied by Chromatography-Mass Spectroscopy (GC-MS), XPS and Fourier Transform Infrared Spectroscopy (FTIR). Our finding suggests a new insight into cost-effective, simple, and environmentally benign production of bimetallic Fe/Pd NPs. Copyright © 2016 Elsevier B.V. All rights reserved.

Sequestration of Ag(I) from aqueous solution as Ag(0) nanostructures by nanoscale zero valent iron (nZVI)

NASA Astrophysics Data System (ADS)

Zhang, Yalei; Yan, Jing; Dai, Chaomeng; Li, Yuting; Zhu, Yan; Zhou, Xuefei

2015-11-01

This study investigates the application of nanoparticle zero valent iron (nZVI) to sequester Ag(I) as Ag(0) nanostructures from aqueous solution. Batch experiments were performed with nZVI exposed to aqueous Ag(I) to investigate the effects of environmental parameters, including nZVI dose, temperature and pH. High temperature facilitates Ag(I) sequestration, and the rate constants are determined to be 0.02, 0.12, and 0.31 mg L/m2 at 30, 50, and 60 °C, respectively. Ag(I) sequestration was adversely affected by adding nitric acid to the solution due to significant acid washing, decreasing the available nZVI active sites. Characterization techniques including TEM, XRD, and HR-XPS revealed that nZVI is oxidized to lepidocrocite and magnetite/maghemite and confirmed the formation of nanocrystalline silver. HR-XPS analysis indicated that Ag2O forms rapidly as an intermediate due to Ag(I) adsorption onto the FeOOH layer. The Ag(0) nanostructures that are formed are fractal, spherical, and dendritic or rod-like, respectively, in morphology by FE-TEM images at different Ag/Fe mass ratios. A general reaction model for the interaction Ag(I) with nZVI is proposed. Our results suggest that nZVI is effective for Ag(I) removal.

X-ray photoelectron spectroscopy for identification of morphological defects and disorders in graphene devices

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

Aydogan, Pinar; Suzer, Sefik, E-mail: suzer@fen.bilkent.edu.tr; Polat, Emre O.

The progress in the development of graphene devices is promising, and they are now considered as an option for the current Si-based electronics. However, the structural defects in graphene may strongly influence the local electronic and mechanical characteristics. Although there are well-established analytical characterization methods to analyze the chemical and physical parameters of this material, they remain incapable of fully understanding of the morphological disorders. In this study, x-ray photoelectron spectroscopy (XPS) with an external voltage bias across the sample is used for the characterization of morphological defects in large area of a few layers graphene in a chemically specificmore » fashion. For the XPS measurements, an external +6 V bias applied between the two electrodes and areal analysis for three different elements, C1s, O1s, and Au4f, were performed. By monitoring the variations of the binding energy, the authors extract the voltage variations in the graphene layer which reveal information about the structural defects, cracks, impurities, and oxidation levels in graphene layer which are created purposely or not. Raman spectroscopy was also utilized to confirm some of the findings. This methodology the authors offer is simple but provides promising chemically specific electrical and morphological information.« less

The electronic characterization of biphenylene—Experimental and theoretical insights from core and valence level spectroscopy

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

Lüder, Johann; Sanyal, Biplab; Eriksson, Olle

In this paper, we provide detailed insights into the electronic structure of the gas phase biphenylene molecule through core and valence spectroscopy. By comparing results of X-ray Photoelectron Spectroscopy (XPS) measurements with ΔSCF core-hole calculations in the framework of Density Functional Theory (DFT), we could decompose the characteristic contributions to the total spectra and assign them to non-equivalent carbon atoms. As a difference with similar molecules like biphenyl and naphthalene, an influence of the localized orbitals on the relative XPS shifts was found. The valence spectrum probed by photoelectron spectroscopy at a photon energy of 50 eV in conjunction withmore » hybrid DFT calculations revealed the effects of the localization on the electronic states. Using the transition potential approach to simulate the X-ray absorption spectroscopy measurements, similar contributions from the non-equivalent carbon atoms were determined from the total spectrum, for which the slightly shifted individual components can explain the observed asymmetric features.« less

Interfacial microanalysis of rubber tyre-cord adhesion and the influence of cobalt

NASA Astrophysics Data System (ADS)

Fulton, W. Stephen; Smith, Graham C.; Titchener, Keith J.

2004-01-01

The effect of cobalt-containing adhesion promoters on the structure and morphology of rubber-brass and rubber-tyre-cord interfaces before and after ageing has been investigated by X-ray photoelectron spectroscopy (XPS) depth profiling, glancing incidence X-ray diffraction (XRD) and transmission electron microscopy (TEM). The effect the cobalt adhesion promoters had upon the interface morphology as they suppressed the growth of crystalline dendrites normally associated with the ageing process was imaged in TEM using samples prepared by the focused ion beam (FIB) milling technique. XPS depth profiling through the interfaces revealed that different types of adhesion promoter influenced the amount and distribution of cobalt ions in the bonding layer. XRD demonstrated the influence that cobalt had upon the structure of the interface and subsequent crystallinity, with a lesser degree of crystallinity being associated with better adhesion performance. From the results a model for the effect of the Co chemistry of the adhesion promotor has been developed.

The effects of surface pretreatment and nitrogen tetroxide purification on the corrosion rate of Type 304L stainless steel

NASA Technical Reports Server (NTRS)

Blue, G. D.; Moran, C. M.

1985-01-01

Corrosion rates of 304L stainless steel coupons in MON-1 oxidizer have been measured as a function of cleaning procedures employed, surface layer positions, propellant impurity levels, and short-term exposure durations (14 to 90 days). Of special interest was propellant contamination by buildup of soluble iron, which may cause flow decay. Surface treatments employed were combinations of cleaning, pickling, and passivation procedures. Propellants used were MIL-SPEC MON-1 and several types of purified NTO (i.e., low water, low chloride) which may, at a later time, be specified as spacecraft grade. Pretest coupon surface analysis by X-ray photoelectron spectroscopy (XPS-ESCA) has revealed important differences, for the different cleaning procedures, in the make-up of the surface layer, both in composition and state of chemical combination of the elements involved. Comparisons will be made of XPS/ESCA data, for different cleaning procedures, for specimens before and after propellant exposure.

Catalyst-free growth of Al-doped SnO2 zigzag-nanobelts for low ppm detection of organic vapours

NASA Astrophysics Data System (ADS)

Sinha, Sudip Kumar; Ghosh, Saptarshi

2016-10-01

In this effort, we report on development of specific sensors dedicated for detection of two of these volatiles, namely ethanol and acetone, below the prescribed statutory limits. Single crystalline Al-doped SnO2 zigzag nanobelt structures were deposited on Si substrate by a catalyst-free thermal evaporation method. The Al-doped SnO2 zigzag nanostructures exhibit high sensitivity and repeatability together with coveted features like fast response and excellent stability. Structural attributes involving the crystal quality and morphology of Al-doped SnO2 zigzag nanobelts were analyzed using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy and transmission electron microscopy. The microscopic images revealed formation of randomly oriented 'zigzag-like' nanobelts with characteristic width between 60 nm and 200 nm and length of 50-300 μm. The Al-doping was observed to have a discerning effect in enhancing the sensitivity in comparison to the pristine nanowires by creating excess oxygen vacancies in the crystal lattice, confirmed through XPS and PL spectra.

Adsorption behavior of glycidoxypropyl-trimethoxy-silane on titanium alloy Ti-6.5Al-1Mo-1V-2Zr

NASA Astrophysics Data System (ADS)

Liu, Jian-hua; Zhan, Zhong-wei; Yu, Mei; Li, Song-mei

2013-01-01

The adsorption behavior of glycidoxypropyl-trimethoxy-silane (GTMS) on titanium alloy Ti-6.5Al-1Mo-1V-2Zr was investigated by using X-ray photoelectron spectroscopy (XPS), Tafel polarization test, and electrochemical impedance spectroscopy (EIS). From the XPS results, it was found that the silane coverage on the titanium surface generally increased with GTMS concentration, with a slight decrease at concentration of 0.1%. Based on the relationship between isoelectronic point (IEP) of titanium surface and the pH values of silane solutions, adsorption mechanisms at different concentrations were proposed. The surface coverage data of GTMS on titanium surface was also derived from electrochemical measurements. By linear fitting the coverage data, it revealed that the adsorption of GTMS on the titanium alloy surface at 30 °C was of a physisorption-based mechanism, and obeyed Langmuir adsorption isotherm. The adsorption equilibrium constant (Kads) and free energy of adsorption process (ΔGads) were calculated to elaborate the mechanism of GTMS adsorption.

Effect of Electron Beam Irradiation on Structural and Optical Properties of Cu-Doped In2O3 Films Prepared by RF Magnetron Sputtering

NASA Astrophysics Data System (ADS)

Krishnan, R. Reshmi; Sanjeev, Ganesh; Prabhu, Radhakrishna; Pillai, V. P. Mahadevan

2018-02-01

Undoped and Cu-doped In2O3 films were prepared by radiofrequency magnetron sputtering technique. The effects of Cu doping and high-energy electron beam irradiation on the structural and optical properties of as-prepared films were investigated using techniques such as x-ray diffraction, x-ray photoelectron spectroscopy (XPS), lateral scanning electron microscopic image analysis, energy-dispersive x-ray (EDX) spectroscopy, micro-Raman, and ultraviolet-visible (UV-vis) spectroscopy. Moderate doping of Cu in In2O3 enhanced the intensity of (222) peak, indicating alignment of crystalline grains along <111>. Electron beam irradiation promoted orientation of crystalline grains along <111> in undoped and moderately Cu-doped films. EDX spectroscopic and XPS analyses revealed incorporation of Cu2+ ions in the lattice. The transmittance of Cu-doped films decreased with e-beam irradiation. Systematic reduction of the bandgap energy with increase in Cu doping concentration was seen in unirradiated and electron-beam-irradiated films.

Density control of dodecamanganese clusters anchored on silicon(100).

PubMed

Condorelli, Guglielmo G; Motta, Alessandro; Favazza, Maria; Nativo, Paola; Fragalà, Ignazio L; Gatteschi, Dante

2006-04-24

A synthetic strategy to control the density of Mn12 clusters anchored on silicon(100) was investigated. Diluted monolayers suitable for Mn12 anchoring were prepared by Si-grafting mixtures of the methyl 10-undecylenoate precursor ligand with 1-decene spectator spacers. Different ratios of these mixtures were tested. The grafted surfaces were hydrolyzed to reveal the carboxylic groups available for the subsequent exchange with the [Mn12O12(OAc)16(H2O)4]4 H2O2 AcOH cluster. Modified surfaces were analyzed by attenuated total reflection (ATR)-FTIR spectroscopy, X-ray photoemission spectroscopy (XPS), and AFM imaging. Results of XPS and ATR-FTIR spectroscopy show that the surface mole ratio between grafted ester and decene is higher than in the source solution. The surface density of the Mn12 cluster is, in turn, strictly proportional to the ester mole fraction. Well-resolved and isolated clusters were observed by AFM, using a diluted ester/decene 1:1 solution.

Preparation, Characterization and Intracellular Imaging of 2,4-Dichlorophenoxyacetic Acid Conjugated Gold Nanorods.

PubMed

Jia, Jin-Liang; Jin, Xiao-Yong; Liu, Qing-Le; Liang, Wen-Long; Lin, Miao-Shan; Xu, Han-Hong

2016-05-01

Visualizing the biodistribution of pesticides inside living cells is great importance for enhancing targeting of pesticides. Here we reported for the first time that gold nanorods (Au NRs) with size of 39.4 nm x 11.3 nm could be used as a fluorescent tracer to examine the distribution of a typical herbicide, 2,4-dichlorophenoxyacetic acid (2,4-D), in tobacco bright yellow 2 (BY-2) cells. The nanostructures of hybrid materials were analyzed by using Raman spectra and X-ray photoelectron spectroscopy (XPS), including spectra assignments and electronic property. These data revealed 2,4-D has successfully conjugated MP-Au NRs according to Raman and XPS. The biodistribution of the conjugates inside BY-2 cells was directly examined at 12 and 24 h by the two-photon microscopy. The intensity of two-photon luminescence (TPL) inside cells demonstrated that the conjugates could be localized and excluded by BY-2 cells. Thus, this labeling approach opens up new avenues to the facile and efficient labeling of pesticides.

Electron-beam-induced post-grafting polymerization of acrylic acid onto the surface of Kevlar fibers

NASA Astrophysics Data System (ADS)

Xu, Lu; Hu, Jiangtao; Ma, Hongjuan; Wu, Guozhong

2018-04-01

The surface of Kevlar fibers was successfully modified by electron beam (EB)-induced post-grafting of acrylic acid (AA). The generation of radicals in the fibers was confirmed by electron spin resonance (ESR) measurements, and the concentration of radicals was shown to increase as the absorbed dose increased, but decrease with increasing temperature. The influence of the synthesis conditions on the degree of grafting was also investigated. The surface microstructure and chemical composition of the modified Kevlar fibers were characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The SEM images revealed that the surface of the grafted fibers was rougher than those of the pristine and irradiated fibers. XPS analysis confirmed an increase in C(O)OH groups on the surface of the Kevlar fibers, suggesting successful grafting of AA. These results indicate that EB-induced post-grafting polymerization is effective for modifying the surface properties of Kevlar fibers.

DOE ZERH Case Study: BrightLeaf Homes, McCormick Avenue, Brookfield, IL

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

none,

2015-09-01

Case study of a DOE 2015 Housing Innovation Award winning production home in the cold climate that got a HERS 38 without PV, with staggered 2x4 studs every 8”on a 2x6 plate with dense-packed R-25 cellulose, basement with 3” XPS exterior and 2: XPS under slab; a vented attic with spray foam top plates and R-60 blown cellulose; 96% AFUE furnace, 14 SEER AC, plus fresh air intake.

Growth and Electronic Structure of Heusler Compounds for Use in Electron Spin Based Devices

DTIC Science & Technology

2015-06-01

either Co– or MnSi– initiated films on c(4x4) GaAs. Studies using x - ray photoemission spectroscopy (XPS), STM/STS, and transmission electron microscopy...Co– or MnSi– initiated films on c(4x4) GaAs. Studies using x - ray photoemission spectroscopy (XPS), STM/STS, and transmission electron microscopy (TEM...diagram of the Palmstrøm lab in-situ growth and char- acterization setup, with 6 MBE growth chambers, 3 scanning probe microscopes, an x - ray

Highly-branched anisotropic hybrid nanoparticles at surfaces.

NASA Astrophysics Data System (ADS)

Tsukruk, Vladimir

2009-03-01

We present a brief overview of our recent studies on combined hybrid anisotropic structures composed of inorganic nanoparticles and highly branched molecules such as modified silsesquioxanes polyhedra cores (POSS) with mixed hydrophobic-hydrophilic tails and silver nanowires with functionalized star block copolymer with embedded gold nanoparticles (nanocobs). We demonstrate two-stage melting of that branched POSS and their ability to form monolayer and multilayered LB structures. On the other hand, we observed that silver-BCP-gold nanocobs display extremely bright Raman scattering caused by surface enhanced Raman effect with very different longitudinal and transversal optical properties as revealed by high-resolution confocal Raman microscopy. To study these hybrid nanostructures we applied combined AFM, SEM, TEM, XPS, SERS, UV-vis, and XR techniques.

Unimpeded permeation of water through biocidal graphene oxide sheets anchored on to 3D porous polyolefinic membranes

NASA Astrophysics Data System (ADS)

Mural, Prasanna Kumar S.; Jain, Shubham; Kumar, Sachin; Madras, Giridhar; Bose, Suryasarathi

2016-04-01

3D porous membranes were developed by etching one of the phases (here PEO, polyethylene oxide) from melt-mixed PE/PEO binary blends. Herein, we have systematically discussed the development of these membranes using X-ray micro-computed tomography. The 3D tomograms of the extruded strands and hot-pressed samples revealed a clear picture as to how the morphology develops and coarsens over a function of time during post-processing operations like compression molding. The coarsening of PE/PEO blends was traced using X-ray micro-computed tomography and scanning electron microscopy (SEM) of annealed blends at different times. It is now understood from X-ray micro-computed tomography that by the addition of a compatibilizer (here lightly maleated PE), a stable morphology can be visualized in 3D. In order to anchor biocidal graphene oxide sheets onto these 3D porous membranes, the PE membranes were chemically modified with acid/ethylene diamine treatment to anchor the GO sheets which were further confirmed by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and surface Raman mapping. The transport properties through the membrane clearly reveal unimpeded permeation of water which suggests that anchoring GO on to the membranes does not clog the pores. Antibacterial studies through the direct contact of bacteria with GO anchored PE membranes resulted in 99% of bacterial inactivation. The possible bacterial inactivation through physical disruption of the bacterial cell wall and/or reactive oxygen species (ROS) is discussed herein. Thus this study opens new avenues in designing polyolefin based antibacterial 3D porous membranes for water purification.3D porous membranes were developed by etching one of the phases (here PEO, polyethylene oxide) from melt-mixed PE/PEO binary blends. Herein, we have systematically discussed the development of these membranes using X-ray micro-computed tomography. The 3D tomograms of the extruded strands and hot-pressed samples revealed a clear picture as to how the morphology develops and coarsens over a function of time during post-processing operations like compression molding. The coarsening of PE/PEO blends was traced using X-ray micro-computed tomography and scanning electron microscopy (SEM) of annealed blends at different times. It is now understood from X-ray micro-computed tomography that by the addition of a compatibilizer (here lightly maleated PE), a stable morphology can be visualized in 3D. In order to anchor biocidal graphene oxide sheets onto these 3D porous membranes, the PE membranes were chemically modified with acid/ethylene diamine treatment to anchor the GO sheets which were further confirmed by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and surface Raman mapping. The transport properties through the membrane clearly reveal unimpeded permeation of water which suggests that anchoring GO on to the membranes does not clog the pores. Antibacterial studies through the direct contact of bacteria with GO anchored PE membranes resulted in 99% of bacterial inactivation. The possible bacterial inactivation through physical disruption of the bacterial cell wall and/or reactive oxygen species (ROS) is discussed herein. Thus this study opens new avenues in designing polyolefin based antibacterial 3D porous membranes for water purification. Electronic supplementary information (ESI) available: SEM micrographs of porous PE with and without maleated PE, X-ray micro-computed tomogram of porous extruded PE, FTIR spectra of GO, XPS wide spectra of untreated and GO immobilized PE and Raman spectra of PE and GO. See DOI: 10.1039/c6nr01356b

XPS and UPS studies on electronic structure of Li 2O

NASA Astrophysics Data System (ADS)

Tanaka, Satoru; Taniguchi, Masaki; Tanigawa, Hisashi

2000-12-01

The adsorption behavior of H 2O on Li 2O was studied by X-ray photo electron spectroscopy (XPS) and ultraviolet photo electron spectroscopy (UPS). XPS and UPS spectra of Li 2O single crystals which were exposed to different pressure of H 2O vapor were observed. In O(1s) region, two peaks were observed and they were assigned to O(1s) in precipitated LiOH on the surface and O(1s) in Li 2O. After H 2O exposure, a peak broadening and an appearance of a new peak were observed at the higher binding energy region than O(1s) in Li 2O. They were attributed to surface -OH and H 2O molecule adsorbed on the surface. The adsorption behavior of H 2O was discussed from the observation of electronic structure in Li 2O surface.

Investigation of local environments in Nafion-SiO(2) composite membranes used in vanadium redox flow batteries.

PubMed

Vijayakumar, M; Schwenzer, Birgit; Kim, Soowhan; Yang, Zhenguo; Thevuthasan, S; Liu, Jun; Graff, Gordon L; Hu, Jianzhi

2012-04-01

Proton conducting polymer composite membranes are of technological interest in many energy devices such as fuel cells and redox flow batteries. In particular, polymer composite membranes, such as SiO(2) incorporated Nafion membranes, are recently reported as highly promising for the use in redox flow batteries. However, there is conflicting reports regarding the performance of this type of Nafion-SiO(2) composite membrane in the redox flow cell. This paper presents results of the analysis of the Nafion-SiO(2) composite membrane used in a vanadium redox flow battery by nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier Transform Infra Red (FTIR) spectroscopy, and ultraviolet-visible spectroscopy. The XPS study reveals the chemical identity and environment of vanadium cations accumulated at the surface. On the other hand, the (19)F and (29)Si NMR measurement explores the nature of the interaction between the silica particles, Nafion side chains and diffused vanadium cations. The (29)Si NMR shows that the silica particles interact via hydrogen bonds with the sulfonic groups of Nafion and the diffused vanadium cations. Based on these spectroscopic studies, the chemical environment of the silica particles inside the Nafion membrane and their interaction with diffusing vanadium cations during flow cell operations are discussed. This study discusses the origin of performance degradation of the Nafion-SiO(2) composite membrane materials in vanadium redox flow batteries. Copyright © 2011 Elsevier Inc. All rights reserved.

Investigation of Local Environments in Nafion-SiO2 Composite Membranes used in Vanadium Redox Flow Batteries

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

Vijayakumar, M.; Schwenzer, Birgit; Kim, Soowhan

2012-04-01

The proton conducting polymer composite membranes are of technological interest in many energy devices such as fuel cells and redox flow batteries. In particular, the polymer composite membranes such as SiO2 incorporated Nafion membranes are recently reported as highly promising for the redox flow batteries. However, there is conflicting reports regarding the performance of this Nafion-SiO2 composite membrane in the redox flow cell. This paper presents results of the analysis of the Nafion-SiO2 composite membrane used in a vanadium redox flow battery by nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier Transformed Infra Red (FTIR) spectroscopy, and ultravioletmore » visible spectroscopy. The XPS study reveals the chemical identity and environment of vanadium cations accumulated at the surface. On the other hand, the 19F and 29Si NMR measurement explores the nature of the interaction between the silica particles, Nafion side chains and diffused vanadium cations. The 29Si NMR shows that the silica particles interaction via hydrogen bonds to the sulfonic groups of Nafion and diffused vanadium cations. Based on these spectroscopic studies, the chemical environment of the silica particles inside the Nafion membrane and their interaction with diffusing vanadium cations during flow cell operations are discussed. This study discusses the origin of performance degradation of the Nafion-SiO2 composite membrane materials in vanadium redox flow batteries.« less

Surface chemical reactions induced on pyrite by ion bombardment

NASA Astrophysics Data System (ADS)

Ruano, Gustavo; Pomiro, Fernando; Ferrón, Julio

2018-01-01

Through X-ray photoemission spectroscopy (XPS), we studied the chemical changes induced in a natural crystal of pyrite (FeS2) upon exposure to 4.5 keV He+ beam. We found an important reducing effect induced by ion bombardment leading to the production of iron embedded in the pyrite matrix. Through a combination of the usual Doniach-Sunjic treatment and Factor Analysis of XPS yields, we were able of analyzing the full Fe 2p XPS signal. We could in this way distinguish Fe compounds with the same binding energy for the Fe 2p3/2 yield. Our results show that He+ bombardment disrupts the ionic environment producing S2-2 and S0, Fe2+ and Fe3+ ions, and the reduction to metallic iron. The remaining pyrite matrix does not passivate the embedded iron structures, which are readily oxidized under air exposure. The oxide formed resembled that of magnetite from the XPS point of view. Further He+ bombardment proved to be efficient to reduce the iron oxide back to iron again.

Preparation of gallium nitride surfaces for atomic layer deposition of aluminum oxide

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

Kerr, A. J.; Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093; Chagarov, E.

2014-09-14

A combined wet and dry cleaning process for GaN(0001) has been investigated with XPS and DFT-MD modeling to determine the molecular-level mechanisms for cleaning and the subsequent nucleation of gate oxide atomic layer deposition (ALD). In situ XPS studies show that for the wet sulfur treatment on GaN(0001), sulfur desorbs at room temperature in vacuum prior to gate oxide deposition. Angle resolved depth profiling XPS post-ALD deposition shows that the a-Al{sub 2}O{sub 3} gate oxide bonds directly to the GaN substrate leaving both the gallium surface atoms and the oxide interfacial atoms with XPS chemical shifts consistent with bulk-like charge.more » These results are in agreement with DFT calculations that predict the oxide/GaN(0001) interface will have bulk-like charges and a low density of band gap states. This passivation is consistent with the oxide restoring the surface gallium atoms to tetrahedral bonding by eliminating the gallium empty dangling bonds on bulk terminated GaN(0001)« less

Comparative study of the native oxide on 316L stainless steel by XPS and ToF-SIMS

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

Tardio, Sabrina, E-mail: s.tardio@surrey.ac.uk; Abel, Marie-Laure; Castle, James E.

2015-09-15

The very thin native oxide film on stainless steel, of the order of 2 nm, is known to be readily modified by immersion in aqueous media. In this paper, X-ray photoelectron spectroscopy (XPS) and time of flight secondary ions mass spectrometry are employed to investigate the nature of the air-formed film and modification after water emersion. The film is described in terms of oxide, hydroxide, and water content. The preferential dissolution of iron is shown to occur on immersion. It is shown that a water absorbed layer and a hydroxide layer are present above the oxide-like passive film. The concentrations ofmore » water and hydroxide appear to be higher in the case of exposure to water. A secure method for the peak fitting of Fe2p and Cr2p XPS spectra of such films on their metallic substrates is described. The importance of XPS survey spectra is underlined and the feasibility of C{sub 60}{sup +} SIMS depth profiling of a thin oxide layer is shown.« less

Using carbonized low-cost materials for removal of chemicals of environmental concern from water.

PubMed

Weidemann, Eva; Niinipuu, Mirva; Fick, Jerker; Jansson, Stina

2018-06-01

Adsorption on low-cost biochars would increase the affordability and availability of water treatment in, for example, developing countries. The aim of this study was to identify the precursor materials and hydrochar surface properties that yield efficient removal of compounds of environmental concern (CEC). We determined the adsorption kinetics of a mixture containing ten CECs (octhilinone, triclosan, trimethoprim, sulfamethoxasole, ciprofloxacin, diclofenac, paracetamol, diphenhydramine, fluconazole, and bisphenol A) to hydrochars prepared from agricultural waste (including tomato- and olive-press wastes, rice husks, and horse manure). The surface characteristics of the hydrochars were evaluated via diffuse reflectance infrared spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and N 2 -adsorption. Kinetic adsorption tests revealed that removal efficiencies varied substantially among different materials. Similarly, surface analysis revealed differences among the studied hydrochars and the degree of changes that the materials undergo during carbonization. According to the DRIFTS data, compared with the least efficient adsorbent materials, the most efficient hydrochars underwent more substantial changes during carbonization.

Structural and magnetic characterization of copper sulfonated phthalocyanine grafted onto treated polyethylene

NASA Astrophysics Data System (ADS)

Reznickova, A.; Kolska, Z.; Orendac, M.; Cizmar, E.; Sajdl, P.; Svorcik, V.

2016-08-01

This study focuses on high density polyethylene (HDPE) activated by Ar plasma treatment, subsequently grafted with copper sulfonated phthalocyanine (CuPc) especially pointing out to the surface and magnetic properties of those composites. Properties of pristine PE and their plasma treated counterparts were studied by different experimental techniques: X-ray photoelectron spectroscopy (XPS), UV-vis spectroscopy, zeta potential and by electron spin resonance (ESR). XPS analysis confirmed the successful grafting of phthalocyanine. The highest absorption was found for the sample grafted with bCuPc for 1 h. Electrokinetic analysis also confirmed the plasma treatment and also subsequent CuPc grafting influence significantly the surface chemistry and charge. These results correspond well with XPS determination. ESR studies confirmed the presence of CuPc grafted on HDPE. It was found, that grafting is mediated by magnetically inactive functional groups, rather than radicals. Magnetic properties of CuPc do not seem to change significantly after grafting CuPc on polyethylene surface.

X-ray photoelectron and mass spectroscopic study of electron irradiation and thermal stability of polytetrafluoroethylene

NASA Technical Reports Server (NTRS)

Wheeler, Donald R.; Pepper, Stephen V.

1990-01-01

Polytetrafluoroethylene (PTFE) was subjected to 3 keV electron bombardment and then heated in vacuum to 300 C. The behavior of the material as a function of radiation dose and temperature was studied by X-ray photoelectron spectroscopy (XPS) of the surface and mass spectroscopy of the species evolved. A quantitative comparison of the radiation dose rate with that in other reported studies showed that, for a given total dose, the damage observed by XPS is greater for higher dose rates. Lightly damaged material heated to 300 C evolved saturated fluorocarbon species, whereas unsaturated fluorocarbon species evolved from heavily damaged material. After heating the heavily damaged material, those features in the XPS that were associated with damage diminished, giving the appearance that the radiation damage annealed. The apparent annealing of the radiation damage was found to be due to the covering of the network by saturated fragments that easily diffused through the decomposed material to the surface region upon heating.

Fluorinated graphenes as advanced biosensors - effect of fluorine coverage on electron transfer properties and adsorption of biomolecules

NASA Astrophysics Data System (ADS)

Urbanová, Veronika; Karlický, František; Matěj, Adam; Šembera, Filip; Janoušek, Zbyněk; Perman, Jason A.; Ranc, Václav; Čépe, Klára; Michl, Josef; Otyepka, Michal; Zbořil, Radek

2016-06-01

Graphene derivatives are promising materials for the electrochemical sensing of diverse biomolecules and development of new biosensors owing to their improved electron transfer kinetics compared to pristine graphene. Here, we report complex electrochemical behavior and electrocatalytic performance of variously fluorinated graphene derivatives prepared by reaction of graphene with a nitrogen-fluorine mixture at 2 bars pressure. The fluorine content was simply controlled by varying the reaction time and temperature. The studies revealed that electron transfer kinetics and electrocatalytic activity of CFx strongly depend on the degree of fluorination. The versatility of fluorinated graphene as a biosensor platform was demonstrated by cyclic voltammetry for different biomolecules essential in physiological processes, i.e. NADH, ascorbic acid and dopamine. Importantly, the highest electrochemical performance, even higher than pristine graphene, was obtained for fluorinated graphene with the lowest fluorine content (CF0.084) due to its high conductivity and enhanced adsorption properties combining π-π stacking interaction with graphene regions with hydrogen-bonding interaction with fluorine atoms.Graphene derivatives are promising materials for the electrochemical sensing of diverse biomolecules and development of new biosensors owing to their improved electron transfer kinetics compared to pristine graphene. Here, we report complex electrochemical behavior and electrocatalytic performance of variously fluorinated graphene derivatives prepared by reaction of graphene with a nitrogen-fluorine mixture at 2 bars pressure. The fluorine content was simply controlled by varying the reaction time and temperature. The studies revealed that electron transfer kinetics and electrocatalytic activity of CFx strongly depend on the degree of fluorination. The versatility of fluorinated graphene as a biosensor platform was demonstrated by cyclic voltammetry for different biomolecules essential in physiological processes, i.e. NADH, ascorbic acid and dopamine. Importantly, the highest electrochemical performance, even higher than pristine graphene, was obtained for fluorinated graphene with the lowest fluorine content (CF0.084) due to its high conductivity and enhanced adsorption properties combining π-π stacking interaction with graphene regions with hydrogen-bonding interaction with fluorine atoms. Electronic supplementary information (ESI) available: SEM, HRTEM, and AFM images the sheet in pristine graphene sample, survey XPS spectrum, high resolution C 1s XPS spectrum, and Raman spectrum of pristine graphene precursor used for controlled fluorination, survey and high resolution F 1s XPS spectra of the CF0.084, CF0.158, and CF0.218 samples, EDS chemical mapping of fluorine in CF0.158, contact angle measurement of CF0.084, CF0.158, CF0.218, and HOPG, and additional electrochemical data. See DOI: 10.1039/c6nr00353b

Electronic structure and phase separation of superconducting and nonsuperconducting KxFe2-ySe2 revealed by x-ray photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Oiwake, M.; Ootsuki, D.; Noji, T.; Hatakeda, T.; Koike, Y.; Horio, M.; Fujimori, A.; Saini, N. L.; Mizokawa, T.

2013-12-01

We have investigated the electronic structure of superconducting (SC) and nonsuperconducting (non-SC) KxFe2-ySe2 using x-ray photoemission spectroscopy (XPS). The spectral shape of the Fe 2p XPS is found to depend on the amount of Fe vacancies. The Fe 2p3/2 peak of the SC and non-SC Fe-rich samples is accompanied by a shoulder structure on the lower binding energy side, which can be attributed to the metallic phase embedded in the Fe2+ insulating phase. The absence of the shoulder structure in the non-SC Fe-poor sample allows us to analyze the Fe 2p spectra using a FeSe4 cluster model. The Fe 3d-Se 4p charge-transfer energy of the Fe2+ insulating phase is found to be ˜2.3 eV which is smaller than the Fe 3d-Fe 3d Coulomb interaction of ˜3.5 eV. This indicates that the Fe2+ insulating state is the charge-transfer type in the Zaanen-Sawatzky-Allen scheme. We also find a substantial change in the valence-band XPS as a function of Fe content and temperature. The metallic state at the Fermi level is seen in the SC and non-SC Fe-rich samples and tends to be enhanced with cooling in the SC sample.

MBE growth of few-layer 2H-MoTe2 on 3D substrates

NASA Astrophysics Data System (ADS)

Vishwanath, Suresh; Sundar, Aditya; Liu, Xinyu; Azcatl, Angelica; Lochocki, Edward; Woll, Arthur R.; Rouvimov, Sergei; Hwang, Wan Sik; Lu, Ning; Peng, Xin; Lien, Huai-Hsun; Weisenberger, John; McDonnell, Stephen; Kim, Moon J.; Dobrowolska, Margaret; Furdyna, Jacek K.; Shen, Kyle; Wallace, Robert M.; Jena, Debdeep; Xing, Huili Grace

2018-01-01

MoTe2 is the least explored material in the Molybdenum-chalcogen family. Molecular beam epitaxy (MBE) provides a unique opportunity to tackle the small electronegativity difference between Mo and Te while growing layer by layer away from thermodynamic equilibrium. We find that for a few-layer MoTe2 grown at a moderate rate of ∼6 min per monolayer, a narrow window in temperature (above Te cell temperature) and Te:Mo ratio exists, where we can obtain pure phase 2H-MoTe2. This is confirmed using reflection high-energy electron diffraction (RHEED), Raman spectroscopy and X-ray photoemission spectroscopy (XPS). For growth on CaF2, Grazing incidence X-ray diffraction (GI-XRD) reveals a grain size of ∼90 Å and presence of twinned grains. In this work, we hypothesis the presence of excess Te incorporation in MBE grown few layer 2H-MoTe2. For film on CaF2, it is based on >2 Te:Mo stoichiometry using XPS as well as 'a' and 'c' lattice spacing greater than bulk 2H-MoTe2. On GaAs, its based on observations of Te crystallite formation on film surface, 2 × 2 superstructure observed in RHEED and low energy electron diffraction, larger than bulk c-lattice spacing as well as the lack of electrical conductivity modulation by field effect. Finally, thermal stability and air sensitivity of MBE 2H-MoTe2 is investigated by temperature dependent XRD and XPS, respectively.

Structural Evolution of Nanoscale Zero-Valent Iron (nZVI) in Anoxic Co2+Soultion : Interactional Performance and Mechanism

NASA Astrophysics Data System (ADS)

Dai, C.; Zhang, Y.

2015-12-01

The nanoscale particle and low oxidation reduction potential make nano zero-valent iron (nZVI) an efficient sorbent and reductant for treating many kinds of organic contaminants and heavy metals.The structures of nanoscale zero-valent iron (nZVI) particles are evolving in reactions, and the reactions are influenced by the evolved structures. In order to understand the detail removal process, it is important to investigate the interactions between reactions and structural evolution. In this work, reactions between nZVI and Co2+ at different initial concentrations in anoxic aqueous solutions (to eliminate the effects of O2) were tracked for 10 days using a variety of methods including inductively coupled plasma optical emission spectrometry (ICP-OES), high resolution-transmission electron microscopy (HR-TEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM). Continuous removal and reduction of Co2+ by nZVI caused by structural evolution were revealed in reaction processes. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the corrosion rate of nZVI, was deemed as the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results showed that the formation and dissolution of sheet structure impacts on the ratio of Fe (0) on nZVI's surface and the surface reduction of Co2+. The cavity structure provides the possibility of Co migrating from surface to inside of nZVI leading a continuous removal. A subacidity condition could accelerate the evolution to improve the removal of Co2+ and the results of structural controlled reactions further indicated that the removal was suspended by sheet structure and enhanced by cavity structure. The results in this study revealed "structural influence" for fully and dynamically understanding nZVI's reactions.

Corrosion behavior of austenitic alloy 690 under anodic and cathodic potentials

NASA Astrophysics Data System (ADS)

Dutta, R. S.; Dey, G. K.; Lobo, A.; Purandare, R.; Kulkarni, S. K.

2002-05-01

The corrosion behavior of austenitic alloy 690 in a solution-annealed condition has been evaluated with the application of anodic as well as cathodic potentials in an acidic chloride solution at room temperature (RT). In a 0.5M H2SO4 + 0.5M NaCl solution, the alloy displayed active-passive pitting behavior with the application of an anodic potential. Surface films, formed at the onset and later stage of the passive region, were characterized using X-ray photoelectron spectroscopy (XPS). The XPS revealed that the surface film formed at the onset of passivity (+ 100 mV SCE) consisted of Cr(OH)3, without any Fe+3/Fe+2. The presence of nickel in the film was found in a transition state of Ni+2 and Ni0. The passive film formed at the higher anodic potential (+ 700 mV SCE) consisted of Cr2O3 without any Fe+3/Fe+2 or even Ni+2/Ni0. Microscopic studies of alloy 690 after anodic polarization in an acidic chloride solution revealed pitting, which was found to be initiated at large, faceted TiN-type inclusions. The susceptibility of the alloy to hydrogen embrittlement has been investigated by conducting cathodic charging of the tensile samples in a 0.5M H2SO4 solution at RT and by subsequent tensile testing of the charged samples in air at a strain rate of 1.3 × 10-4 s-1 up to fracture. An indication toward hydrogen-induced ductility loss was noticed for the samples of the alloy, which is believed to be attributable to a hydrogen-enhanced microvoid growth process. Since the microvoid growth process occurs at the last stage of fracture, the effect of hydrogen on the ductility of the alloy is little.

Incorporation of silver nanoparticles on the surface of orthodontic microimplants to achieve antimicrobial properties

PubMed Central

Venugopal, Adith; Muthuchamy, Nallal; Tejani, Harsh; Gopalan, Anantha-Iyengar; Lee, Kwang-Pill; Lee, Heon-Jin

2017-01-01

Objective Microbial aggregation around dental implants can lead to loss/loosening of the implants. This study was aimed at surface treating titanium microimplants with silver nanoparticles (AgNPs) to achieve antibacterial properties. Methods AgNP-modified titanium microimplants (Ti-nAg) were prepared using two methods. The first method involved coating the microimplants with regular AgNPs (Ti-AgNP) and the second involved coating them with a AgNP-coated biopolymer (Ti-BP-AgNP). The topologies, microstructures, and chemical compositions of the surfaces of the Ti-nAg were characterized by scanning electron microscopy (SEM) equipped with energy-dispersive spectrometer (EDS) and X-ray photoelectron spectroscopy (XPS). Disk diffusion tests using Streptococcus mutans, Streptococcus sanguinis, and Aggregatibacter actinomycetemcomitans were performed to test the antibacterial activity of the Ti-nAg microimplants. Results SEM revealed that only a meager amount of AgNPs was sparsely deposited on the Ti-AgNP surface with the first method, while a layer of AgNP-coated biopolymer extended along the Ti-BP-AgNP surface in the second method. The diameters of the coated nanoparticles were in the range of 10 to 30 nm. EDS revealed 1.05 atomic % of Ag on the surface of the Ti-AgNP and an astounding 21.2 atomic % on the surface of the Ti-BP-AgNP. XPS confirmed the metallic state of silver on the Ti-BP-AgNP surface. After 24 hours of incubation, clear zones of inhibition were seen around the Ti-BP-AgNP microimplants in all three test bacterial culture plates, whereas no antibacterial effect was observed with the Ti-AgNP microimplants. Conclusions Titanium microimplants modified with Ti-BP-AgNP exhibit excellent antibacterial properties, making them a promising implantable biomaterial. PMID:28127534

Comparative study on the deposition of silicon oxide permeation barrier coatings for polymers using hexamethyldisilazane (HMDSN) and hexamethyldisiloxane (HMDSO)

NASA Astrophysics Data System (ADS)

Mitschker, F.; Schücke, L.; Hoppe, Ch; Jaritz, M.; Dahlmann, R.; de los Arcos, T.; Hopmann, Ch; Grundmeier, G.; Awakowicz, P.

2018-06-01

The effect of the selection of hexamethyldisiloxane (HMDSO) and hexamethyldisilazane (HMDSN) as a precursor in a microwave driven low pressure plasma on the deposition of silicon oxide barrier coatings and silicon based organic interlayers on polyethylene terephthalate (PET) and polypropylene (PP) substrates is investigated. Mass spectrometry is used to quantify the absolute gas density and the degree of depletion of neutral precursor molecules under variation of oxygen admixture. On average, HMDSN shows a smaller density, a higher depletion and the production of smaller fragments. Subsequently, this is correlated with barrier performance and chemical structure as a function of barrier layer thickness and oxygen admixture on PET. For this purpose, the oxygen transmission rate (OTR) is measured and Fourier transformed infrared (FTIR) spectroscopy as well as x-ray photoelectron spectroscopy (XPS) is performed. HMDSN based coatings exhibit significantly higher barrier performances for high admixtures of oxygen (200 sccm). In comparison to HMDSO based processes, however, a higher supply of oxygen is necessary to achieve a sufficient degree of oxidation, cross-linking and, therefore, barrier performance. FTIR and XPS reveal a distinct carbon content for low oxygen admixtures (10 and 20 sccm) in case of HMDSN based coatings. The variation of interlayer thickness also reveals significantly higher OTR for HMDSO based coatings on PET and PP. Barrier performance of HMDSO based coatings improves with increasing interlayer thickness up to 10 nm for PET and PP. HMDSN based coatings exhibit a minimum of OTR without interlayer on PP and for 2 nm interlayer thickness on PET. Furthermore, HMDSN based coatings show distinctly higher bond strengths to the PP substrate.

Combined use of FE-SEM+EDS, ToF-SIMS, XPS, XRD and OM for the study of ancient gilded artefacts

NASA Astrophysics Data System (ADS)

Ingo, G. M.; Riccucci, C.; Pascucci, M.; Messina, E.; Giuliani, C.; Biocca, P.; Tortora, L.; Fierro, G.; Di Carlo, G.

2018-07-01

Gilded brooches dating back to 16th-17th centuries CE were investigated by means of integrated and complementary analytical techniques such as high spatial resolution field emission scanning electron microscopy coupled with energy dispersive X-ray spectrometry (FE-SEM+EDS), time of flight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and optical microscopy (OM). The results reveal in detail the surface and subsurface morphology and the chemical features of the micrometric decorative Au layer that has been deposited by means of the so-called fire-gilding technique based on the use of an amalgam. Moreover, the results allow to recognise chlorine, sulphur and phosphorous species as the main degradation agents and to identify the corrosion products naturally formed during the long-term interaction with the burial soil constituents. The findings show also that the galvanic coupling between the two dissimilar metals, i.e. Cu and Au, lead to enhancement of corrosion phenomena causing the spalling of the gold thin film and the disfigurement of the object. From a conservation point of view, the results suggest a targeted use of low-toxic inhibitors to hinder the detrimental role of chlorine as possible responsible of future further severe degradation phenomena. In conclusions, the micro and nano-chemical, structural and morphological investigations in a depth range from a few nanometers to micrometers have revealed the complex nature of corroded surface of ancient gold coated artefacts, highlighting some specific aspects related to their peculiar degradation mechanisms thus extending the scientific relevance of the tailored use of complementary and integrated surface and subsurface analytical techniques for the investigation of ancient coated artefacts.

Boron difluoride dibenzoylmethane derivatives: Electronic structure and luminescence

NASA Astrophysics Data System (ADS)

Tikhonov, Sergey A.; Vovna, Vitaliy I.; Osmushko, Ivan S.; Fedorenko, Elena V.; Mirochnik, Anatoliy G.

2018-01-01

Electronic structure and optical properties of boron difluoride dibenzoylmethanate and four of its derivatives have been studied by X-ray photoelectron spectroscopy, absorption and luminescence spectroscopy and quantum chemistry (DFT, TDDFT). The relative quantum luminescence yields have been revealed to correlate with charge transfers of HOMO-LUMO transitions, energy barriers of aromatic substituents rotation and the lifetime of excited states in the investigated complexes. The bathochromic shift of intensive bands in the optical spectra has been observed to occur when the functional groups are introduced into p-positions of phenyl cycles due to destabilizing HOMO levels. Calculated energy intervals between electronic levels correlate well with XPS spectra structure of valence and core electrons.

X-Ray photoelectron Spectroscopy Applications

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

Engelhard, Mark H.; Droubay, Timothy C.; Du, Yingge

2017-01-03

With capability for obtaining quantitative elemental composition, chemical and electronic state, and overlayer thickness information from the top ~10 nm of a sample surface, X-ray Photoelectron Spectroscopy (XPS) or Electron Spectroscopy for Chemical Analysis (ESCA) is a versatile and widely used technique for analyzing surfaces. The technique is applied to a host of materials, from insulators to conductors in virtually every scientific field and sub-discipline. More recently, XPS has been extended under in-situ and operando conditions. Following a brief introduction to XPS principles and instrument components, this article exemplifies widely ranging XPS applications in material and life sciences.

Facile fabrication of BiVO4 nanofilms with controlled pore size and their photoelectrochemical performances.

PubMed

Feng, Chenchen; Jiao, Zhengbo; Li, Shaopeng; Zhang, Yan; Bi, Yingpu

2015-12-28

We demonstrate a facile method for the rational fabrication of pore-size controlled nanoporous BiVO(4) photoanodes, and confirmed that the optimum pore-size distributions could effectively absorb visible light through light diffraction and confinement functions. Furthermore, in situ X-ray photoelectron spectroscopy (XPS) reveals more efficient photoexcited electron-hole separation than conventional particle films, induced by light confinement and rapid charge transfer in the inter-crossed worm-like structures.

Characterization of nanostructured CuO-porous silicon matrix formed on copper-coated silicon substrate via electrochemical etching

NASA Astrophysics Data System (ADS)

Naddaf, M.; Mrad, O.; Al-zier, A.

2014-06-01

A pulsed anodic etching method has been utilized for nanostructuring of a copper-coated p-type (100) silicon substrate, using HF-based solution as electrolyte. Scanning electron microscopy reveals the formation of a nanostructured matrix that consists of island-like textures with nanosize grains grown onto fiber-like columnar structures separated with etch pits of grooved porous structures. Spatial micro-Raman scattering analysis indicates that the island-like texture is composed of single-phase cupric oxide (CuO) nanocrystals, while the grooved porous structure is barely related to formation of porous silicon (PS). X-ray diffraction shows that both the grown CuO nanostructures and the etched silicon layer have the same preferred (220) orientation. Chemical composition obtained by means of X-ray photoelectron spectroscopic (XPS) analysis confirms the presence of the single-phase CuO on the surface of the patterned CuO-PS matrix. As compared to PS formed on the bare silicon substrate, the room-temperature photoluminescence (PL) from the CuO-PS matrix exhibits an additional weak `blue' PL band as well as a blue shift in the PL band of PS (S-band). This has been revealed from XPS analysis to be associated with the enhancement in the SiO2 content as well as formation of the carbonyl group on the surface in the case of the CuO-PS matrix.

Apatite Formation and Biocompatibility of a Low Young’s Modulus Ti-Nb-Sn Alloy Treated with Anodic Oxidation and Hot Water

PubMed Central

Tanaka, Hidetatsu; Mori, Yu; Noro, Atsushi; Kogure, Atsushi; Kamimura, Masayuki; Yamada, Norikazu; Hanada, Shuji; Masahashi, Naoya; Itoi, Eiji

2016-01-01

Ti-6Al-4V alloy is widely prevalent as a material for orthopaedic implants because of its good corrosion resistance and biocompatibility. However, the discrepancy in Young’s modulus between metal prosthesis and human cortical bone sometimes induces clinical problems, thigh pain and bone atrophy due to stress shielding. We designed a Ti-Nb-Sn alloy with a low Young’s modulus to address problems of stress disproportion. In this study, we assessed effects of anodic oxidation with or without hot water treatment on the bone-bonding characteristics of a Ti-Nb-Sn alloy. We examined surface analyses and apatite formation by SEM micrographs, XPS and XRD analyses. We also evaluated biocompatibility in experimental animal models by measuring failure loads with a pull-out test and by quantitative histomorphometric analyses. By SEM, abundant apatite formation was observed on the surface of Ti-Nb-Sn alloy discs treated with anodic oxidation and hot water after incubation in Hank’s solution. A strong peak of apatite formation was detected on the surface using XRD analyses. XPS analysis revealed an increase of the H2O fraction in O 1s XPS. Results of the pull-out test showed that the failure loads of Ti-Nb-Sn alloy rods treated with anodic oxidation and hot water was greater than those of untreated rods. Quantitative histomorphometric analyses indicated that anodic oxidation and hot water treatment induced higher new bone formation around the rods. Our findings indicate that Ti-Nb-Sn alloy treated with anodic oxidation and hot water showed greater capacity for apatite formation, stronger bone bonding and higher biocompatibility for osteosynthesis. Ti-Nb-Sn alloy treated with anodic oxidation and hot water treatment is a promising material for orthopaedic implants enabling higher osteosynthesis and lower stress disproportion. PMID:26914329

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

Kaspar, Tiffany C.; Sushko, Peter V.; Bowden, Mark E.

Epitaxial thin films of Cr2-xTixO3 were deposited by oxygen-plasma-assisted molecular beam epitaxy (OPA-MBE) for 0.04 ≤ x ≤ 0.26. Ti speciation is verified by both x-ray photoelectron spectroscopy (XPS) and Ti K-edge x-ray absorption near-edge spectroscopy (XANES) to be Ti4+. Substitution of Ti for Cr in the corundum lattice is confirmed by modeling of the Ti K-edge extended x-ray absorption fine structure (EXAFS). Room temperature electrical transport measurements confirm the highly insulating nature of Ti-doped Cr2O3, despite the presence of aliovalent Ti4+. The resistivity of highly pure, undoped Cr2O3 was measured to be three orders of magnitude higher than formore » Ti-doped Cr2O3. Although the formation of Cr vacancies in Ti-doped Cr2O3 is found by density functional theory (DFT) calculations to be the energetically preferable defect compensation mechanism to maintain charge neutrality, an analysis of the XPS and EXAFS data reveal the presence of both Cr vacancies and oxygen interstitials at intermediate and high Ti concentrations, with a weak trend towards Cr vacancies as the Ti concentration increases. At low Ti concentrations, a strong dependence of the XPS Ti 2p core level peak width on concentration is observed. This dependence is attributed to the presence of widely spaced Ti dopants, which renders compensation of two or three Ti by a single oxygen interstitial or Cr vacancy, respectively, less probable. Instead, defect clusters of unknown type occur, although they may involve Cr vacancies. The defect compensation model developed here provides insight into previous, conflicting reports of n-type versus p-type conductivity in Ti-doped Cr2O3 at high temperature, and will inform future studies to exploit the wide variety of electronic and magnetic properties of corundum-structure oxides.« less

Nitrogen-doped carbon dots originating from unripe peach for fluorescent bioimaging and electrocatalytic oxygen reduction reaction.

PubMed

Atchudan, Raji; Edison, Thomas Nesakumar Jebakumar Immanuel; Lee, Yong Rok

2016-11-15

This paper reports the robust hydrothermal synthesis of nitrogen doped carbon dots (N-CDs) using the unripe fruit of Prunus persica (peach) as the carbon precursor and aqueous ammonia as the nitrogen source. The optical properties of synthesized N-CDs were characterized by ultraviolet visible (UV-Vis) and fluorescence spectroscopy techniques. The synthesized N-CDs were emitted blue light when excitated with a portable UV lamp. The materials with the optical properties were characterized further by high resolution transmission electron microscope (HRTEM), X-ray diffraction (XRD), Raman, Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS). The mean size of the N-CDs was approximately 8nm, as calculated from the HRTEM image. The d-spacing of N-CDs, calculated using Bragg law, was approximately 0.21nm, which was consistent with the interlayer distance calculated from the HRTEM image. FT-IR spectroscopy and XPS revealed the presence of the phytoconstituents functionalities of peach fruit over the N-CDs surface and a high level of nitrogen doping on carbon dots (CDs) was confirmed by XPS studies. These results suggest that the unripe fruit extract of peach is an ideal candidate for the preparation of N-CDs. The resulting N-CDs showed excellent optical properties in water. The synthesized N-CDs exhibited a high fluorescence quantum yield and low cytotoxicity, and can be used as fluorescence imaging probes. In addition, the N-CDs were catalytically activite towards the oxygen reduction reaction (ORR). The N-CDs exhibited good catalytic activity in an alkaline medium (0.1M KOH) with a remarkable ORR of approximately 0.72V vs reversible hydrogen electrode (RHE), and O2 reduction follows mainly a 2 electron pathway by being reduced to hydrogen peroxide. The 2-electron reduction pathway is used in industry for H2O2 production. Copyright © 2016 Elsevier Inc. All rights reserved.

Textural, Structural and Biological Evaluation of Hydroxyapatite Doped with Zinc at Low Concentrations

PubMed Central

Predoi, Daniela; Iconaru, Simona Liliana; Deniaud, Aurélien; Chevallet, Mireille; Michaud-Soret, Isabelle; Buton, Nicolas; Prodan, Alina Mihaela

2017-01-01

The present work was focused on the synthesis and characterization of hydroxyapatite doped with low concentrations of zinc (Zn:HAp) (0.01 < xZn < 0.05). The incorporation of low concentrations of Zn2+ ions in the hydroxyapatite (HAp) structure was achieved by co-precipitation method. The physico-chemical properties of the samples were characterized by X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy (SEM), zeta-potential, and DLS and N2-BET measurements. The results obtained by XRD and FTIR studies demonstrated that doping hydroxyapatite with low concentrations of zinc leads to the formation of a hexagonal structure with lattice parameters characteristic to hydroxyapatite. The XRD studies have also shown that the crystallite size and lattice parameters of the unit cell depend on the substitutions of Ca2+ with Zn2+ in the apatitic structure. Moreover, the FTIR analysis revealed that the water content increases with the increase of zinc concentration. Furthermore, the Energy Dispersive X-ray Analysis (EDAX) and XPS analyses showed that the elements Ca, P, O, and Zn were found in all the Zn:HAp samples suggesting that the synthesized materials were zinc doped hydroxyapatite, Ca10−xZnx(PO4)6(OH), with 0.01 ≤ xZn ≤ 0.05. Antimicrobial assays on Staphylococcus aureus and Escherichia coli bacterial strains and HepG2 cell viability assay were carried out. PMID:28772589

Identification of the mechanism that confers superhydrophobicity on 316L stainless steel

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

Escobar, Ana M.; Llorca-Isern, Nuria; Rius-Ayra, Oriol

This study develops a rapid method to confer superhydrophobicity on 316L stainless steel surfaces with an amphiphilic reagent such as dodecanoic acid. The highest contact angle (approaching 173°) was obtained after forming hierarchical structures with a non-aqueous electrolyte by an electrolytic process. Our goal was to induce superhydrophobicity directly on 316L stainless steel substrates and to establish which molecules cause the effect. The superhydrophobic behaviour is analysed by contact angle measurements, scanning electron microscopy (SEM), IR spectroscopy and atomic force microscopy (AFM). The growth mechanism is analysed using FE-SEM, TOF-SIMS and XPS in order to determine the molecules involved inmore » the reaction and the growth. The TOF-SIMS analysis revealed that the Ni{sup 2+} ions react with lauric acid to create an ester on the stainless steel surface. - Highlights: • This study develops a rapid and facile approach to impart superhydrophobicity properties to 316L stainless steel surfaces with an amphiphilic reagent such as dodecanoic acid. Surface character changes from superhydrophilicity to superhydrophobicity. • This process changes the surface character from superhydrophilicity to superhydrophobicity. • The process based on electrolysis of a nickel salt in lauric acid provides superhydrophobic behaviour in 316L stainless steel. • The growth mechanism is proposed as a mode island (Volmert- Weber mode). • TOF-SIMS and XPS provided the identification of the molecules involved in the surface modification reaction on AISI 316L inducing superhydrophobicity.« less

Cesium power: low Cs+ levels impart stability to perovskite solar cells.

PubMed

Deepa, Melepurath; Salado, Manuel; Calio, Laura; Kazim, Samrana; Shivaprasad, S M; Ahmad, Shahzada

2017-02-01

Towards increasing the stability of perovskite solar cells, the addition of Cs + is found to be a rational approach. Recently triple cation based perovskite solar cells were found to be more effective in terms of stability and efficiency. Heretofore they were unexplored, so we probed the Cs/MA/FA (cesium/methyl ammonium/formamidinium) cation based perovskites by X-ray photoelectron spectroscopy (XPS) and correlated their compositional features with their solar cell performances. The Cs + content was found to be optimum at 5%, when incorporated in the (MA 0.15 FA 0.85 )Pb(I 0.85 Br 0.15 ) 3 lattice, because the corresponding device yielded the highest fill factor compared to the perovskite without Cs + and with 10% Cs + . XPS studies distinctly reveal how Cs + aids in maintaining the expected stoichiometric ratios of I : Pb 2+ , I : N and Br : Pb 2+ in the perovskites, and how the valence band (VB) edge is dependent on the Cs + proportion, which in turn governs the open circuit voltage. Even at a low content of 5%, Cs + resides deep within the absorber layer, and ensures minimum distortion of the VB level (compared to 0% and 10% Cs + perovskites) upon Ar + sputtering, thus allowing the formation of a stable robust material that delivers excellent solar cell response. This study which brings out the role of Cs + is anticipated to be of paramount significance to further engineer the composition and improve device performances.

Poly(dimethyl siloxane) surface modification with biosurfactants isolated from probiotic strains.

PubMed

Pinto, S; Alves, P; Santos, A C; Matos, C M; Oliveiros, B; Gonçalves, S; Gudiña, E; Rodrigues, L R; Teixeira, J A; Gil, M H

2011-09-15

Depending on the final application envisaged for a given biomaterial, many surfaces must be modified before use. The material performance in a biological environment is mainly mediated by its surface properties that can be improved using suitable modification methods. The aim of this work was to coat poly(dimethyl siloxane) (PDMS) surfaces with biosurfactants (BSs) and to evaluate how these compounds affect the PDMS surface properties. BSs isolated from four probiotic strains (Lactococcus lactis, Lactobacillus paracasei, Streptococcus thermophilus A, and Streptococcus thermophilus B) were used. Bare PDMS and PDMS coated with BSs were characterized by contact angle measurements, infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). The influence of the surface modifications on the materials blood compatibility was studied through thrombosis and hemolysis assays. The cytotoxicity of these materials was tested against rat peritoneal macrophages. AFM results demonstrated the successful coating of the surfaces. Also, by contact angle measurements, an increase of the coated surfaces hydrophilicity was seen. Furthermore, XPS analysis indicated a decrease of the silicon content at the surface, and ATR-FTIR results showed the presence of BS characteristic groups as a consequence of the modification. All the studied materials revealed no toxicity and were found to be nonhemolytic. The proposed approach for the modification of PDMS surfaces was found to be effective and opens new possibilities for the application of these surfaces in the biomedical field. Copyright © 2011 Wiley Periodicals, Inc.

Peptide surface modification of P(HEMA-co-MMA)-b-PIB-b-P(HEMA-co-MMA) block copolymers.

PubMed

Ojha, Umaprasana; Feng, Dingsong; Chandekar, Amol; Whitten, James E; Faust, Rudolf

2009-06-02

Peptide surface modification of poly[(methyl methacrylate-co-hydroxyethyl methacrylate)-b-isobutylene-b-(methyl methacrylate-co-hydroxyethyl methacrylate)] P(MMA-co-HEMA)-b-PIB-b-P(MMA-co-HEMA) triblock copolymers with different HEMA/MMA ratios has been accomplished using an efficient synthetic procedure. The triblock copolymers were reacted with 4-fluorobenzenesulfonyl chloride (fosyl chloride) in pyridine to obtain the activated polymers [poly{(methyl methacrylate-co-fosyloxyethyl methacrylate)-b-isobutylene-b-(methyl methacrylate-co-fosyloxyethyl methacrylate)}] P(MMA-co-FEMA)-b-PIB-b-P(MMA-co-FEMA), with an activating efficiency of 80-90%. The resulting polymers were soluble in chloroform, and their solutions were used to coat thin uniform films with a predetermined thickness on smooth steel surfaces. The presence of reactive activating groups on the film surface was confirmed by X-ray photoelectron spectroscopy (XPS), dye labeling, and confocal laser scanning microscopic studies. Activation of the triblock copolymer films was also achieved under heterogeneous conditions in polar (acetonitrile) and nonpolar (hexanes) media. The extent of activation was controlled by varying the dipping time and polarity of the medium. Peptide attachment was accomplished by immersing the coated steel strips into aqueous buffer solution of Gly-Gly or GYIGSR. XPS and solubility studies revealed successful attachment of peptides to the polymer surface. Virtually all remaining activating groups were successfully replaced in the subsequent step by a treatment with Tris(hydroxymethyl)amino methane in a buffered methanol/water mixture.

Titanium composite conversion coating formation on CRS In the presence of Mo and Ni ions: Electrochemical and microstructure characterizations

NASA Astrophysics Data System (ADS)

Eivaz Mohammadloo, H.; Sarabi, A. A.

2016-11-01

There have been an increasing interest in finding a replacement for the chromating process due to environmental and health concerns. Hence, in this study Chrome-free chemical conversion coatings were deposited on the surface of cold-rolled steel (CRS) on the basis of Titanium (TiCC), Titanium-Nickel (TiNiCC) and titanium-molybdate (TiMoCC) based conversion coating solutions. The surface characterization was performed by field emission scanning electron microscope (FESEM), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and contact angle measuring device. Also, the corrosion behavior was assessed by the means of potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) measurements. FESEM and AFM study show that the TiNiCC is denser and more uniform than that TiCC and TiMoCC since, TiMoCC conversion coating presents network feature, and there were abundant micro-cracks on the surface of the coating. XPS results confirmed the precipitation of Ti and Ni oxide/hydroxide, Mn dioxide/trioxide on the surface of different Ti-based conversion coatings. Electrochemical results revealed that all Ti-based conversion coatings have better anti-corrosion properties than bare CRS. Moreover, TiNiCC treatment inhibited the corrosion of CRS to a significant degree (polarization resistance (Rp) = 5510 Ω cm2) in comparison with TiCC (Rp = 2705 Ω cm2) and TiMoCC (Rp = 805 Ω cm2).

Effects of the low Earth orbit space environment on the surface chemistry of Kapton polyimide film: An XPS study

NASA Technical Reports Server (NTRS)

Lee, Myung; Rooney, William; Whiteside, James

1992-01-01

Kapton H (DuPont Trademark) polyimide specimens exposed to the low earth (LEO) space environment suffered significant weathering with surface erosions of approximately 8.0 microns. Despite these effects, no significant changes in bulk chemistry were observed. X-ray photoelectron spectroscopy (XPS) was used to determine local changes induced from approximately 25 percent in 1980 vintage ground control specimens to nearly 53 percent in space exposed specimens. The greatest increase was observed for the divalent oxygen moieties, although a slight increase in carbonyl oxygen was also measured. Furthermore, the chemical shifts of all XPS peaks of space-exposed Kapton are shifted to higher energy. This is consistent with a higher oxidation state of the space exposed surface. Finally, space exposed specimens had distinct silicon peaks (2p 100 eV and 2s 149 eV) in their XPS spectra in agreement with widespread reports of silicon contamination throughout the LDEF satellite. These results are discussed in terms of surface reactivity of the polyimide exposed to the LEO environment and the chemical nature of contaminants deposited on flight surfaces due to satellite outgassing.

Study of mesoporous CdS-quantum-dot-sensitized TiO2 films by using X-ray photoelectron spectroscopy and AFM

PubMed Central

Wojcieszak, Robert; Raj, Gijo

2014-01-01

Summary CdS quantum dots were grown on mesoporous TiO2 films by successive ionic layer adsorption and reaction processes in order to obtain CdS particles of various sizes. AFM analysis shows that the growth of the CdS particles is a two-step process. The first step is the formation of new crystallites at each deposition cycle. In the next step the pre-deposited crystallites grow to form larger aggregates. Special attention is paid to the estimation of the CdS particle size by X-ray photoelectron spectroscopy (XPS). Among the classical methods of characterization the XPS model is described in detail. In order to make an attempt to validate the XPS model, the results are compared to those obtained from AFM analysis and to the evolution of the band gap energy of the CdS nanoparticles as obtained by UV–vis spectroscopy. The results showed that XPS technique is a powerful tool in the estimation of the CdS particle size. In conjunction with these results, a very good correlation has been found between the number of deposition cycles and the particle size. PMID:24605274

Interfaces in heterogeneous catalytic reactions: Ambient pressure XPS as a tool to unravel surface chemistry

DOE PAGES

Palomino, Robert M.; Hamlyn, Rebecca; Liu, Zongyuan; ...

2017-04-27

In this paper we provide a summary of the recent development of ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and its application to catalytic surface chemistry. The methodology as well as significant advantages and challenges associated with this novel technique are described. Details about specific examples of using AP-XPS to probe surface chemistry under working reaction conditions for a number of reactions are explained: CO oxidation, water-gas shift (WGS), CO 2 hydrogenation, dry reforming of methane (DRM) and ethanol steam reforming (ESR). In conclusion, we discuss insights into the future development of the AP-XPS technique and its applications.

Interfaces in heterogeneous catalytic reactions: Ambient pressure XPS as a tool to unravel surface chemistry

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

Palomino, Robert M.; Hamlyn, Rebecca; Liu, Zongyuan

In this paper we provide a summary of the recent development of ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and its application to catalytic surface chemistry. The methodology as well as significant advantages and challenges associated with this novel technique are described. Details about specific examples of using AP-XPS to probe surface chemistry under working reaction conditions for a number of reactions are explained: CO oxidation, water-gas shift (WGS), CO 2 hydrogenation, dry reforming of methane (DRM) and ethanol steam reforming (ESR). In conclusion, we discuss insights into the future development of the AP-XPS technique and its applications.

XPS study of ruthenium tris-bipyridine electrografted from diazonium salt derivative on microcrystalline boron doped diamond.

PubMed

Agnès, Charles; Arnault, Jean-Charles; Omnès, Franck; Jousselme, Bruno; Billon, Martial; Bidan, Gérard; Mailley, Pascal

2009-12-28

Boron doped diamond (BDD) functionalization has received an increasing interest during the last few years. Such an infatuation comes from the original properties of BDD, including chemical stability or an electrochemical window, that opens the way for the design of (bio)sensors or smart interfaces. In such a context, diazonium salts appear to be well suited for BDD functionalization as they enable covalent immobilization of functional entities such as enzymes or DNA. In this study we report microcrystalline BDD functionalization with a metallic complex, ruthenium tris(bipyridine), using the p-(tris(bipyridine)Ru(2+))phenyl diazonium salt. Electrografting using cyclic voltammetry (CV) allowed the formation of a ruthenium complex film that was finely characterized using electrochemistry and X-ray photoelectron spectroscopy (XPS). Moreover, we showed that chronopotentiometry (CP) is a convenient tool to monitor Ru complex film deposition through the control of the electrochemical pulse parameters (i.e. current density and pulse duration). Finally, such a control was demonstrated through the correlation between electrochemical and XPS characterizations.

In situ formation of the active sites in Pd-Au bimetallic nanocatalysts for CO oxidation: NAP (near ambient pressure) XPS and MS study.

PubMed

Bukhtiyarov, A V; Prosvirin, I P; Saraev, A A; Klyushin, A Yu; Knop-Gericke, A; Bukhtiyarov, V I

2018-06-07

Model bimetallic Pd-Au/HOPG catalysts have been investigated in the CO oxidation reaction using a combination of NAP XPS and MS techniques. The samples have shown catalytic activity at temperatures above 150 °C. The redistribution of Au and Pd on the surface depending on the reaction conditions has been demonstrated using NAP XPS. The Pd enrichment of the bimetallic particles' surface under reaction gas mixture has been shown. Apparently, CO adsorption induces Pd segregation on the surface. Heating the sample under reaction conditions above 150 °C decomposes the Pd-CO state due to CO desorption and reaction and simultaneous Pd-Au alloy formation on the surface takes place. Cooling back down to RT results in reversible Pd segregation due to Pd-CO formation and the sample becomes inactive. It has been shown that in situ studies are necessary for investigation of the active sites in Pd-Au bimetallic systems.

Functionalization to control microstructural, optical, electronic and wetting properties of metal oxide surfaces

NASA Astrophysics Data System (ADS)

Singh, Jagdeep

This thesis focuses on engineering the surface chemistry of oxide surfaces in order to control their microstructural, optical, electronic and wetting properties. Several different types of experiments have been performed to tailor the properties of silicon oxide, titanium dioxide, and zinc oxide surfaces. Applications of this work include organic electronics, sensors and nanomanufacturing. Adsorption of 3-mercaptopropyltrimethoxysilane (MPS) on hydroxylated silicon oxide substrates by immersion in MPS solution or exposure to MPS vapor has been compared using X-ray photoelectron spectroscopy (XPS). To aid the interpretation, MPS has also been cryogenically condensed in ultrahigh vacuum (UHV) onto gold surfaces. Condensation of MPS vapor on gold in the absence of water does not result in MPS polymerization, as evidenced by multilayer desorption upon warming to room temperature. The C1s XPS spectrum has been used to infer the relative abundance of methoxy groups. Vapor-deposition on hydroxylated silicon oxide leads to an unpolymerized MPS monolayer consisting of molecules with two methoxy groups. UV induced hydrophilicity of titanium dioxide surfaces could possibly be used to provide a means of registration and alignment in high-rate nanomanufacturing applications or to induce transfer of nanoelements. In order to understand the nature and magnitude of intermolecular forces, force-distance curves have been measured on TiO2. Toward the goal of possibly using light to induce nanoparticle transfer, force curves have been recorded using an SiO2 colloidal probe before and after irradiating the TiO 2 surface with UV light. In order to eliminate the effects of capillary forces, the relative humidity has been kept below 1% by flowing either N 2 or N2/O2 (1:1) into the AFM chamber. In a dry nitrogen environment, no difference is observed in adhesive forces measured with and without UV exposure. Gold-coated atomic force microscope (AFM) tips functionalized with amine-, hydroxyl, carboxylic acid, and methyl-terminated alkanethiol molecules have been used to probe the adhesive forces of polystyrene and poly(acrylic acid) films in dry air (relative humidity < 0.5%). XPS and contact angle measurements confirm the quality and uniformity of similarly treated gold surfaces and the polymer films. XPS indicates that the amine-functionalized thiol films are protonated and comprised of multilayers. Toward the goal of modifying its optical properties, ZnO nanorod surfaces have been modified using 3-mercaptopropyltriethoxysilane (MPTES) and 1-propanethiol (PPT), and XPS has been used to investigate the changes occurring on the nanorods after surface modification. XPS reveals that in the case of MPTES-modified nanorods, bonding occurs via both S-Zn and Si-O-Zn bond formation. For comparison, 3-mercaptopropyltrimethoxysilane (MPTMS), dodecanethiol and methanethiol have been adsorbed on sputter-cleaned Zn-terminated ZnO (0001) in ultrahigh vacuum (UHV). In this case, XPS indicates that bonding of thiols on ZnO surfaces occurs via S-Zn bond formation. Photoluminescence spectroscopy has been used to study the effect of surface functionalization on the optical properties of the nanorods. MPTES- and PPT-functionalized nano-ZnO show an increase in intensity of the UV emission peak relative to the unfunctionalized nanorods due to reduced probability of surface dependent non-radiative processes. A decrease in the visible peak in both cases is believed to be due to passivation of surface defects. A simple method for encapsulating zinc oxide nanoparticles within an organic matrix has been discovered that consists of dispersing them in an ethanolic solution, adding an organothiol and stirring while heating. Electron microscopy, photoemission, Raman spectroscopy and thermal gray metric analyses demonstrate that partial dissolution of the oxide occurs accompanied by encapsulation within a matrix consisting of a 1:2 zinc-thiol complex. Using this methodology, it is possible to surround ZnO within diverse matrices, including fluorescent ones. (Abstract shortened by UMI.)

A novel electrolyte salt additive for lithium-ion batteries with voltages greater than 4.7 V

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

Li, Yunchao; Wan, Shun; Veith, Gabriel M.

2016-11-07

Here, lithium bis(2-methyl-2-fluoromalonato)borate (LiBMFMB), as an additive in conventional electrolyte for LiNi 0.5Mn 1.5O 4, exhibits improved coulombic efficiencies and cycling stability. Cyclic voltammograms indicate the cells with additive form good SEIs during the first cycle whereas no additive cell needs more cycles to form a functional SEI. XPS reveals LiBMFMB could reduce the decomposition of LiPF 6 salt and solvents, resulting in thinner SEI.

Isolated, well-defined organovanadium(iii) on silica: Single-site catalyst for hydrogenation of alkenes and alkynes

DOE PAGES

Sohn, H.; Camacho-Bunquin, J.; Langeslay, R. R.; ...

2017-05-03

Well-defined, isolated, single-site organovanadium(III) catalyst on SiO 2 [(SiO 2)V(Mes)(THF)] were synthesized via surface organometallic chemistry, and fully characterized using a combination of analytical and spectroscopic techniques (EA, ICP, 1H NMR, TGA-MS, EPR, XPS, DR-UV/Vis, UV-Raman, DRIFTS, XAS). The catalysts exhibit unprecedented reactivity in liquid- and gas-phase alkene/alkyne hydrogenation. Catalyst poisoning experiments revealed that 100% of the V sites are active for hydrogenation.

Preparation and characterization of the nanoporous ultrathin multilayer films based on molybdenum polyoxometalate (Mo 38) n

NASA Astrophysics Data System (ADS)

Wang, L.; Jiang, M.; Wang, E. B.; Duan, L. Y.; Hao, N.; Lan, Y.; Xu, L.; Li, Z.

2003-11-01

Ultrathin multilayer films of the wheel-shaped molybdenum polyoxometalate cluster (Mo 38) n and poly(allylamine hydrochloride)(PAH) have been prepared by the layer-by-layer (LbL) self-assembly method. The ((Mo 38) n/PAH) m multilayer films have been characterized by X-ray photoelectron spectra (XPS) and atomic force microscopy (AFM). UV-VIS measurements reveal regular film growth with each (Mo 38) n adsorption. The electrochemistry behavior of the film at room temperature was investigated.

Synthesis and antibacterial properties of water-dispersible silver nanoparticles stabilized by metal-carbon σ-bonds

NASA Astrophysics Data System (ADS)

Kawai, Koji; Narushima, Takashi; Kaneko, Kotaro; Kawakami, Hayato; Matsumoto, Miyuki; Hyono, Atsushi; Nishihara, Hiroshi; Yonezawa, Tetsu

2012-12-01

The synthesis of 4-diazoniumcarboxylbenzene fluoroborate, a new water-soluble stabilizer for metal nanoparticles (NPs), is described. A stable dispersion of Ag NPs in water was successfully produced by a simultaneous aqueous reduction of this diazonium salt and silver nitrate by NaBH4. UV-vis spectra, TEM images, XRD patterns, and XPS spectra of the obtained Ag NPs revealed that they were stabilized by Ag-C σ-bonds. These NPs showed excellent antimicrobial properties against Staphylococcus aureus.

Rapid reductive degradation of aqueous p-nitrophenol using nanoscale zero-valent iron particles immobilized on mesoporous silica with enhanced antioxidation effect

NASA Astrophysics Data System (ADS)

Tang, Lin; Tang, Jing; Zeng, Guangming; Yang, Guide; Xie, Xia; Zhou, Yaoyu; Pang, Ya; Fang, Yan; Wang, Jiajia; Xiong, Weiping

2015-04-01

In this study, nanoscale zero-valent iron particles immobilized on mesoporous silica (nZVI/SBA-15) were successfully prepared for effective degradation of p-nitrophenol (PNP). The nZVI/SBA-15 composites were characterized by N2 adsorption/desorption, transmission electron microscopy (TEM), UV-vis spectrum and X-ray photoelectron spectroscopy (XPS). Results showed that abundant ultrasmall nanoscale zero-valent iron particles were formed and well dispersed on mesoporous silica (SBA-15). Batch experiments revealed that PNP removal declined from 96.70% to 16.14% as solution pH increased from 3.0 to 9.0. Besides, degradation equilibrium was reached within 5 min, which was independent of initial PNP concentration. Furthermore, only a little PNP elimination on SBA-15 indicated that nZVI immobilized on mesoporous silica was mainly responsible for the target contaminant removal. The UV-vis spectrum and XPS measurement confirmed that the PNP removal was a reductive degradation process, which was further proved by the detected intermediates using gas chromatography-mass spectrometry (GC/MS). The excellent antioxidation ability had been discovered with more than 80% of PNP being removed by nZVI/SBA-15 treated with 30 days' exposure to air. These results demonstrated the feasible and potential application of nZVI/SBA-15 composites in organic wastewater treatment.

Protein adsorption and biomimetic mineralization behaviors of PLL-DNA multilayered films assembled onto titanium

NASA Astrophysics Data System (ADS)

Gao, Wenli; Feng, Bo; Ni, Yuxiang; Yang, Yongli; Lu, Xiong; Weng, Jie

2010-11-01

Titanium and its alloys are frequently used as surgical implants in load bearing situations, such as hip prostheses and dental implants, owing to their biocompatibility, mechanical and physical properties. In this paper, a layer-by-layer (LBL) self-assembly technique, based on the polyelectrolyte-mediated electrostatic adsorption of poly-L-lysine (PLL) and DNA, was used to the formation of multilayer on titanium surfaces. Then bovine serum albumin (BSA) adsorption and biomimetic mineralization of modified surfaces were studied. The chemical composition and wettability of assembled substrates were investigated by X-ray photoelectron spectroscopy (XPS), fluorescence microscopy and water contact angle measurement, respectively. The XPS analysis indicated that the layers were assembled successfully through electrostatic attractions. The measurement with ultraviolet (UV) spectrophotometer revealed that the LBL films enhanced ability of BSA adsorption onto titanium. The adsorption quantity of BSA on the surface terminated with PLL was higher than that of the surface terminated with DNA, and the samples of TiOH/P/D/P absorbed BSA most. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) showed that samples of assembled PLL or/and DNA had better bioactivity in inducing HA formation. Thus the assembling of PLL and DNA onto the surface of titanium in turn via a layer-by-layer self-assembly technology can improve the bioactivity of titanium.

Facile green synthesis of fluorescent N-doped carbon dots from Actinidia deliciosa and their catalytic activity and cytotoxicity applications

NASA Astrophysics Data System (ADS)

Arul, Velusamy; Sethuraman, Mathur Gopalakrishnan

2018-04-01

Green synthesis of fluorescent nitrogen doped carbon dots (N-CDs) using Actinidia deliciosa (A. deliciosa) fruit extract as a carbon precursor and aqueous ammonia as a nitrogen dopant is reported here. The synthesized N-CDs were characterized by high resolution transmission electron microscopy (HR-TEM), energy dispersive spectroscopy (EDS), selected area electron diffraction (SAED), UV-Visible spectroscopy (UV-Vis), fluorescence spectroscopy, Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The average size of the N-CDs was approximately 3.59 nm and the calculated inter layer distance was found to be 0.21 nm. Raman spectroscopy and SAED pattern revealed the graphitic nature of the synthesized N-CDs. The N-CDs were found to emit intense blue color at 405 nm under the excitation of 315 nm. The doping of nitrogen over the surface of the N-CDs was confirmed by EDS, FT-IR and XPS studies. The synthesized N-CDs were found to exhibit excellent catalytic activity in the reduction of Rhodamine-B using sodium borohydrate. The MTT assay was used to evaluate the cytotoxicity and biocompatibility of N-CDs towards L-929 and MCF-7 cells. From the results obtained, it was found that the N-CDs exhibit low cytotoxicity and superior biocompatibility on both L-929 and MCF-7 cells.

In Situ Chemical Imaging of Solid-Electrolyte Interphase Layer Evolution in Li–S Batteries

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

Nandasiri, Manjula I.; Camacho-Forero, Luis E.; Schwarz, Ashleigh M.

Parasitic reactions of electrolyte and polysulfide with the Li-anode in lithium sulfur (Li-S) batteries lead to the formation of solid-electrolyte interphase (SEI) layers, which are the major reason behind severe capacity fading in these systems. Despite numerous studies, the evolution mechanism of the SEI layer and specific roles of polysulfides and other electrolyte components are still unclear. Here, we report an in-situ X-ray photoelectron spectroscopy (XPS) and chemical imaging analysis combined with ab initio molecular dynamics (AIMD) computational modeling to gain fundamental understanding regarding the evolution of SEI layers on Li-anodes within Li-S batteries. A multi-modal approach involving AIMD modelingmore » and in-situ XPS characterization uniquely reveals the chemical identity and distribution of active participants in parasitic reactions as well as the SEI layer evolution mechanism. The SEI layer evolution has three major stages: the formation of a primary composite mixture phase involving stable lithium compounds (Li 2S, LiF, Li 2O etc); and formation of a secondary matrix type phase due to cross interaction between reaction products and electrolyte components, which is followed by a highly dynamic mono-anionic polysulfide (i.e. LiS 5) fouling process. In conclusion, these new molecular-level insights into the SEI layer evolution on Li- anodes are crucial for delineating effective strategies for the development of Li–S batteries.« less

In Situ Chemical Imaging of Solid-Electrolyte Interphase Layer Evolution in Li–S Batteries

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

Nandasiri, Manjula I.; Camacho-Forero, Luis E.; Schwarz, Ashleigh M.

Parasitic reactions of electrolyte and polysulfide with the Li-anode in lithium sulfur (Li-S) batteries lead to the for-mation of solid electrolyte interphase (SEI) layers, which are the major reason behind severe capacity fading in these systems. Despite numerous studies, the evolution mechanism of the SEI layer and specific roles of polysulfides and oth-er electrolyte components are still unclear. We report an in-situ X-ray photoelectron spectroscopy (XPS) and chemical imaging analysis combined with ab initio molecular dynamics (AIMD) computational modeling to gain fundamental understanding regarding the evolution of SEI layers on Li-anodes within Li-S batteries. A multi-modal approach in-volving AIMD modelingmore » and in-situ XPS characterization uniquely reveals the chemical identity and distribution of active participants in parasitic reactions as well as the SEI layer evolution mechanism. The SEI layer evolution has three major stages: the formation of a primary composite mixture phase involving stable lithium compounds (Li2S, LiF, Li2O etc); and formation of a secondary matrix type phase due to cross interaction between reaction products and elec-trolyte components, which is followed by a highly dynamic mono-anionic polysulfide (i.e. LiS5) fouling process. These new molecular-level insights into the SEI layer evolution on Li- anodes are crucial for delineating effective strategies for the development of Li–S batteries.« less

Tuning Surface Chemistry of Polyetheretherketone by Gold Coating and Plasma Treatment

NASA Astrophysics Data System (ADS)

Novotná, Zdeňka; Rimpelová, Silvie; Juřík, Petr; Veselý, Martin; Kolská, Zdeňka; Hubáček, Tomáš; Borovec, Jakub; Švorčík, Václav

2017-06-01

Polyetheretherketone (PEEK) has good chemical and biomechanical properties that are excellent for biomedical applications. However, PEEK exhibits hydrophobic and other surface characteristics which cause limited cell adhesion. We have investigated the potential of Ar plasma treatment for the formation of a nanostructured PEEK surface in order to enhance cell adhesion. The specific aim of this study was to reveal the effect of the interface of plasma-treated and gold-coated PEEK matrices on adhesion and spreading of mouse embryonic fibroblasts. The surface characteristics (polarity, surface chemistry, and structure) before and after treatment were evaluated by various experimental techniques (gravimetry, goniometry, X-ray photoelectron spectroscopy (XPS), and electrokinetic analysis). Further, atomic force microscopy (AFM) was employed to examine PEEK surface morphology and roughness. The biological response of cells towards nanostructured PEEK was evaluated in terms of cell adhesion, spreading, and proliferation. Detailed cell morphology was evaluated by scanning electron microscopy (SEM). Compared to plasma treatment, gold coating improved PEEK wettability. The XPS method showed a decrease in the carbon concentration with increasing time of plasma treatment. Cell adhesion determined on the interface between plasma-treated and gold-coated PEEK matrices was directly proportional to the thickness of a gold layer on a sample. Our results suggest that plasma treatment in a combination with gold coating could be used in biomedical applications requiring enhanced cell adhesion.

Enhanced removal of humic acid from aqueous solution by novel stabilized nano-amorphous calcium phosphate: Behaviors and mechanisms

NASA Astrophysics Data System (ADS)

Jiang, Ling; Li, Yiming; Shao, Yi; Zhang, Yong; Han, Ruiming; Li, Shiyin; Wei, Wei

2018-01-01

Stabilized nano-amorphous calcium phosphate (nACP) was prepared using polyethylene glycol as stabilizer to obtain a nanosized amorphous adsorbent. The produced nACP was evaluated by using XRD, FTIR, SEM and X-ray photoelectron spectroscopy (XPS). The sedimentation test demonstrated that nACP exhibited better stability than crystallized hydroxyapatite. The adsorption efficiency of the nACP material for aqueous humic acid (HA) was evaluated from the point of view of medium pH, adsorption time, temperature, and ionic strength, as well as the presences of metal ions. The results of the study showed very good adsorption performance towards aqueous HA. The Sips modeling results revealed that the stabilized nACP adsorbent had a considerably high adsorption capacity (248.3 mg/g) for HA at 298 K. The adsorption data fitted well into pseudo-second order and Elovich kinetic models. XPS analyses indicated that HA retention on nACP material might be due to the surface complexation reaction between oxygen-containing group and calcium of HA and nACP, respectively. Moreover, the HA adsorption capacity of nACP could still keep more than 86% after four adsorption-desorption cycles. By taking into account all results it was concluded that the nACP adsorbent leveraged its stability in combination with its high uptake capacity to offer a great promise for HA adsorption from water.

Characterisation of well-adhered ZrO2 layers produced on structured reactors using the sonochemical sol-gel method

NASA Astrophysics Data System (ADS)

Jodłowski, Przemysław J.; Chlebda, Damian K.; Jędrzejczyk, Roman J.; Dziedzicka, Anna; Kuterasiński, Łukasz; Sitarz, Maciej

2018-01-01

The aim of this study was to obtain thin zirconium dioxide coatings on structured reactors using the sonochemical sol-gel method. The preparation method of metal oxide layers on metallic structures was based on the synergistic combination of three approaches: the application of ultrasonic irradiation during the synthesis of Zr sol-gel based on a precursor solution containing zirconium(IV) n-propoxide, the addition of stabilszing agents, and the deposition of ZrO2 on the metallic structures using the dip-coating method. As a result, dense, uniform zirconium dioxide films were obtained on the FeCrAlloy supports. The structured reactors were characterised by various physicochemical methods, such as BET, AFM, EDX, XRF, XRD, XPS and in situ Raman spectroscopy. The results of the structural analysis by Raman and XPS spectroscopy confirmed that the metallic surface was covered by a ZrO2 layer without any impurities. SEM/EDX mapping revealed that the deposited ZrO2 covered the metallic support uniformly. The mechanical and high temperature tests showed that the developed ultrasound assisted sol-gel method is an efficient way to obtain thin, well-adhered zirconium dioxide layers on the structured reactors. The prepared metallic supports covered with thin ZrO2 layers may be a good alternative to layered structured reactors in several dynamics flow processes, for example for gas exhaust abatement.

Biosorption of Cadmium by Non-Toxic Extracellular Polymeric Substances (EPS) Synthesized by Bacteria from Marine Intertidal Biofilms

PubMed Central

Camacho-Chab, Juan Carlos; Chan-Bacab, Manuel Jesús; Aguila-Ramírez, Ruth Noemí; Bartolo-Pérez, Pascual; Tabasco-Novelo, Carolina; Gaylarde, Christine; Ortega-Morales, Benjamín Otto

2018-01-01

Cadmium is a major heavy metal found in polluted aquatic environments, mainly derived from industrial production processes. We evaluated the biosorption of solubilized Cd2+ using the extracellular polymeric substances (EPS) produced by Bacillus sp. MC3B-22 and Microbacterium sp. MC3B-10 (Microbactan); these bacteria were originally isolated from intertidal biofilms off the coast of Campeche, Mexico. EPS were incubated with different concentrations of cadmium in ultrapure water. Residual Cd2+ concentrations were determined by Inductive Coupled Plasma-Optic Emission Spectrometry and the maximum sorption capacity (Qmax) was calculated according to the Langmuir model. EPS were characterized by X-ray photoelectron spectroscopy (XPS) before and after sorption. The Qmax of Cd2+ was 97 mg g−1 for Microbactan and 141 mg g−1 for MC3B-22 EPS, these adsorption levels being significantly higher than previously reported for other microbial EPS. In addition, XPS analysis revealed changes in structure of EPS after biosorption and showed that amino functional groups contributed to the binding of Cd2+, unlike other studies that show the carbohydrate fraction is responsible for this activity. This work expands the current view of bacterial species capable of synthesizing EPS with biosorbent potential for cadmium and provides evidence that different chemical moieties, other than carbohydrates, participate in this process. PMID:29439486

In Situ Chemical Imaging of Solid-Electrolyte Interphase Layer Evolution in Li–S Batteries

DOE PAGES

Nandasiri, Manjula I.; Camacho-Forero, Luis E.; Schwarz, Ashleigh M.; ...

2017-05-03

Parasitic reactions of electrolyte and polysulfide with the Li-anode in lithium sulfur (Li-S) batteries lead to the formation of solid-electrolyte interphase (SEI) layers, which are the major reason behind severe capacity fading in these systems. Despite numerous studies, the evolution mechanism of the SEI layer and specific roles of polysulfides and other electrolyte components are still unclear. Here, we report an in-situ X-ray photoelectron spectroscopy (XPS) and chemical imaging analysis combined with ab initio molecular dynamics (AIMD) computational modeling to gain fundamental understanding regarding the evolution of SEI layers on Li-anodes within Li-S batteries. A multi-modal approach involving AIMD modelingmore » and in-situ XPS characterization uniquely reveals the chemical identity and distribution of active participants in parasitic reactions as well as the SEI layer evolution mechanism. The SEI layer evolution has three major stages: the formation of a primary composite mixture phase involving stable lithium compounds (Li 2S, LiF, Li 2O etc); and formation of a secondary matrix type phase due to cross interaction between reaction products and electrolyte components, which is followed by a highly dynamic mono-anionic polysulfide (i.e. LiS 5) fouling process. In conclusion, these new molecular-level insights into the SEI layer evolution on Li- anodes are crucial for delineating effective strategies for the development of Li–S batteries.« less

Tunable Stoichiometry of BCxNy Thin Films Through Multitarget Pulsed Laser Deposition Monitored via In Situ Ellipsometry (Postprint)

DTIC Science & Technology

2014-02-05

X - ray photoelectron spectroscopy (XPS), Raman spectroscopy , and atomic ...calculate thickness, n and k. X - ray photoelectron spectroscopy (XPS), Raman spectroscopy , and atomic force microscopy (AFM) were all performed on each of the... X - ray photoelectron spectroscopy (XPS) and Raman spectroscopy were used to measure and compare the composition of the films.6 In this paper,

Arsenopyrite and pyrite bioleaching: evidence from XPS, XRD and ICP techniques.

PubMed

Fantauzzi, Marzia; Licheri, Cristina; Atzei, Davide; Loi, Giovanni; Elsener, Bernhard; Rossi, Giovanni; Rossi, Antonella

2011-10-01

In this work, a multi-technical bulk and surface analytical approach was used to investigate the bioleaching of a pyrite and arsenopyrite flotation concentrate with a mixed microflora mainly consisting of Acidithiobacillus ferrooxidans. X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and X-ray-induced Auger electron spectroscopy mineral surfaces investigations, along with inductively coupled plasma-atomic emission spectroscopy and carbon, hydrogen, nitrogen and sulphur determination (CHNS) analyses, were carried out prior and after bioleaching. The flotation concentrate was a mixture of pyrite (FeS(2)) and arsenopyrite (FeAsS); after bioleaching, 95% of the initial content of pyrite and 85% of arsenopyrite were dissolved. The chemical state of the main elements (Fe, As and S) at the surface of the bioreactor feed particles and of the residue after bioleaching was investigated by X-ray photoelectron and X-ray excited Auger electron spectroscopy. After bioleaching, no signals of iron, arsenic and sulphur originating from pyrite and arsenopyrite were detected, confirming a strong oxidation and the dissolution of the particles. On the surfaces of the mineral residue particles, elemental sulphur as reaction intermediate of the leaching process and precipitated secondary phases (Fe-OOH and jarosite), together with adsorbed arsenates, was detected. Evidence of microbial cells adhesion at mineral surfaces was also produced: carbon and nitrogen were revealed by CHNS, and nitrogen was also detected on the bioleached surfaces by XPS. This was attributed to the deposition, on the mineral surfaces, of the remnants of a bio-film consisting of an extra-cellular polymer layer that had favoured the bacterial action. © Springer-Verlag 2011

Zinc-Containing Magnetic Oxides Stabilized by a Polymer: One Phase or Two?

PubMed

Baird, Nicholas; Losovyj, Yaroslav; Yuzik-Klimova, Ekaterina Yu; Kuchkina, Nina V; Shifrina, Zinaida B; Pink, Maren; Stein, Barry D; Morgan, David Gene; Wang, Tianhao; Rubin, Mikhail A; Sidorov, Alexander I; Sulman, Esther M; Bronstein, Lyudmila M

2016-01-13

Here we developed a new family of Zn-containing magnetic oxides of different structures by thermal decomposition of Zn(acac)2 in the reaction solution of preformed magnetite nanoparticles (NPs) stabilized by polyphenylquinoxaline. Upon an increase of the Zn(acac)2 loading from 0.15 to 0.40 mmol (vs 1 mmol of Fe(acac)3), the Zn content increases, and the Zn-containing magnetic oxide NPs preserve a spinel structure of magnetite and an initial, predominantly multicore NP morphology. X-ray photoelectron spectroscopy (XPS) of these samples revealed that the surface of iron oxide NPs is enriched with Zn, although Zn species were also found deep under the iron oxide NP surface. For all the samples, XPS also demonstrates the atom ratio of Fe(3+)/Fe(2+) = 2:1, perfectly matching Fe3O4, but not ZnFe2O4, where Fe(2+) ions are replaced with Zn(2+). The combination of XPS with other physicochemical methods allowed us to propose that ZnO forms an ultrathin amorphous layer on the surface of iron oxide NPs and also diffuses inside the magnetite crystals. At higher Zn(acac)2 loading, cubic ZnO nanocrystals coexist with magnetite NPs, indicating a homogeneous nucleation of the former. The catalytic testing in syngas conversion to methanol demonstrated outstanding catalytic properties of Zn-containing magnetic oxides, whose activities are dependent on the Zn loading. Repeat experiments carried out with the best catalyst after magnetic separation showed remarkable catalyst stability even after five consecutive catalytic runs.

Dysprosium electrodeposition from a hexaalkylguanidinium-based ionic liquid.

PubMed

Berger, Claudia A; Arkhipova, Maria; Maas, Gerhard; Jacob, Timo

2016-08-07

The rare-earth element dysprosium (Dy) is an important additive that increases the magnetocrystalline anisotropy of neodymium magnets and additionally prevents from demagnetizing at high temperatures. Therefore, it is one of the most important elements for high-tech industries and is mainly used in permanent magnetic applications, for example in electric vehicles, industrial motors and direct-drive wind turbines. In an effort to develop a more efficient electrochemical technique for depositing Dy on Nd-magnets in contrast to commonly used costly physical vapor deposition, we investigated the electrochemical behavior of dysprosium(iii) trifluoromethanesulfonate in a custom-made guanidinium-based room-temperature ionic liquid (RTIL). We first examined the electrodeposition of Dy on an Au(111) model electrode. The investigation was carried out by means of cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS). The initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). CV measurements revealed a large cathodic reduction peak, which corresponds to the growth of monoatomic high islands, based on STM images taken during the initial stages of deposition. XPS identified these deposited islands as dysprosium. A similar reduction peak was also observed on an Nd-Fe-B substrate, and positively identified as deposited Dy using XPS. Finally, we varied the concentration of the Dy precursor, electrolyte flow and temperature during Dy deposition and demonstrated that each of these parameters could be used to increase the thickness of the Dy deposit, suggesting that these parameters could be tuned simultaneously in a temperature-controlled flow cell to enhance the thickness of the Dy layer.

Autoclave growth, magnetic, and optical properties of GdB6 nanowires

NASA Astrophysics Data System (ADS)

Han, Wei; Wang, Zhen; Li, Qidong; Liu, Huatao; Fan, Qinghua; Dong, Youzhong; Kuang, Quan; Zhao, Yanming

2017-12-01

High-quality single crystalline gadolinium hexaboride (GdB6) nanowires have been successfully prepared at very low temperatures of 200-240 °C by a high pressure solid state (HPSS) method in an autoclave with a new chemical reaction route, where Gd, H3BO3, Mg and I2 were used as raw materials. The crystal structure, morphology, valence, magnetic and optical absorption properties were investigated using XRD, FESEM, HRTEM, XPS, SQUID magnetometry and optical measurements. HRTEM images and SAED patterns reveal that the GdB6 nanowires are single crystalline with a preferred growth direction along [001]. The XPS spectrum suggests that the valence of Gd ion in GdB6 is trivalent. The effective magnetic momentum per Gd3+ in GdB6 is about 6.26 μB. The optical properties exhibit weak absorption in the visible light range, but relatively strong absorbance in the NIR and UV range. Low work function and high NIR absorption can make GdB6 nanowires a potential solar radiation shielding material for solar cells or other NIR blocking applications.

The crystallization behavior of amorphous Ge2Sb2Te5 films induced by a multi-pulsed nanosecond laser

NASA Astrophysics Data System (ADS)

Fan, T.; Liu, F. R.; Li, W. Q.; Guo, J. C.; Wang, Y. H.; Sun, N. X.; Liu, F.

2017-09-01

In this paper, accumulated crystallization of amorphous Ge2Sb2Te5 (a-GST) films induced by a multi-pulsed nanosecond (ns) excimer laser was investigated by x-ray diffraction (XRD), atomic force microscopy, field-emission scanning electron microscopy, x-ray photoelectron spectroscopy (XPS) and a spectrophotometer. XRD analyses revealed that detectable crystallization was firstly observed in the preferred orientation (200), followed by the orientations (220) and (111) after two pulses. Optical contrast, determined by crystallinity as well as surface roughness, was found to retain a linear relation within the first three pulses. A layered growth mechanism from the top surface to the interior of a-GST films was used to explain the crystallization behavior induced by the multi-pulse ns laser. XPS analyses for bond rearrangement and electronic structure further suggested that the crystallization process was performed by generating new bonds of Ge-Te and Sb-Te after laser irradiations. This paper presents the potential of multi-level devices and tunable thermal emitters based on controllable crystallization of phase-change materials.

Tribological properties and surface chemistry of silicon carbide at temperatures to 1500 C

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1981-01-01

Silicon carbide surfaces were heated to 1500 C in a vacuum and analyzed at room temperature with X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The basic unit of the surfaces was considered as a plane of a tetrahedron of either SiC4 and CSi4 composition. AES spectra were obtained from 250-1500 C, with an analysis depth of 1 nm revealed the presence of little Si and mostly graphite. XPS analysis depth was 2 nm or less, and Si was found in the second 1 nm. Sliding friction tests with single-crystal silicon carbide in contact with iron in a vacuum were characterized by a stock-slip value. The coefficient of friction increased with increasing temperature up to 400 C, then decreased with increasing temperature from 400-600 C. Reheating surfaces to 800 C after preheating them to that temperature produced no changes in AES readings. It is concluded that the maximum density of silicon and silicon-carbide is at 800 C, and the higher the sliding temperature, the more metal that is transferred.

Chemistry Characterization of Jet Aircraft Engine Particulate by XPS: Results from APEX III

NASA Technical Reports Server (NTRS)

Vander Wal, Randy L.; Bryg, Victoria M.

2014-01-01

This paper reports XPS analysis of jet exhaust particulate from a B737, Lear, ERJ, and A300 aircraft during the APEX III NASA led field campaign. Carbon hybridization and bonding chemistry are identified by high-resolution scans about the C1s core-shell region. Significant organic content as gauged by the sp3/sp2 ratio is found across engines and platforms. Polar oxygen functional groups include carboxylic, carbonyl and phenol with combined content of 20 percent or more. By lower resolution survey scans various elements including transition metals are identified along with lighter elements such as S, N, and O in the form of oxides. Burning additives within lubricants are probable sources of Na, Ba, Ca, Zn, P and possibly Sn. Elements present and their percentages varied significantly across all engines, not revealing any trend or identifiable cause for the differences, though the origin is likely the same for the same element when observed. This finding suggests that their presence can be used as a tracer for identifying soots from aircraft engines as well as diagnostic for monitoring engine performance and wear.

The synergistic effects of combining the high energy mechanical milling and wet milling on Si negative electrode materials for lithium ion battery

NASA Astrophysics Data System (ADS)

Hou, Shang-Chieh; Su, Yuh-Fan; Chang, Chia-Chin; Hu, Chih-Wei; Chen, Tsan-Yao; Yang, Shun-Min; Huang, Jow-Lay

2017-05-01

The submicro-sized and nanostructured Si aggregated powder is prepared by combinational routes of high energy mechanical milling (HEMM) and wet milling. Milled Si powder is investigated by particle size analyzer, SEM, TEM, XPS and XRD as well as the control ones. Its electrode is also investigated by in situ XRD and electrochemical performance. Morphology reveals that combining the high energy mechanical milling and wet milling not only fracture primary Si particles but also form submicro-sized Si aggregates constructed by amorphous and nanocrystalline phases. Moreover, XPS shows that wet milling in ethanol trigger Sisbnd Osbnd CH2CH3 bonding on Si surface might enhance the SEI formation. In situ XRD analysis shows negative electrode made of submicro-sized Si aggregated powder can effectively suppress formation of crystalline Li15Si4 during lithiation and delithiation due to amorphous and nanocrystalline construction. Thus, the submicro-sized Si powder with synergistic effects combining the high energy mechanical milling and wet milling in ethanol as negative electrode performs better capacity retention.

Effect of dielectric barrier discharge treatment on surface nanostructure and wettability of polylactic acid (PLA) nonwoven fabrics

NASA Astrophysics Data System (ADS)

Ren, Yu; Xu, Lin; Wang, Chunxia; Wang, Xiaona; Ding, Zhirong; Chen, Yuyue

2017-12-01

Polylactic acid (PLA) nonwoven fabrics are treated with atmospheric dielectric barrier discharge (DBD) plasma to improve surface wettability. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) show that micro- to nano-scale textures appear on the treated PLA surfaces dependent on the treatment time. X-ray photoelectron spectroscopy (XPS) analysis reveals that the DBD plasma treatments result in decreased carbon contents and increased oxygen contents as well as slightly increased nitrogen contents. The water contact angle decreases sharply with the increase of the DBD plasma treatment time. The super hydrophilic PLA surfaces (the water contact angle reached 0°) are obtained when the treatment time is longer than 90 s. Ninety days after the DBD plasma treatment, the XPS analysis shows that Csbnd O/Csbnd N and Cdbnd O/Osbnd Cdbnd O percentages decline for all treatment groups. However, the water contact angle is kept constant at 0° for the groups treated above 90 s, which could be due to the oxidized nano-structured layer on the DBD plasma treated PLA surfaces.

A new method of nanocrystalline nickel powder formation by magnetron sputtering on the water-soluble substrates

NASA Astrophysics Data System (ADS)

Tučkutė, S.; Urbonavičius, M.; Lelis, M.; Maiorov, M.; Díaz Ordaz, J. R.; Milčius, D.

2018-01-01

Due to the accurate and relatively easy control magnetron sputtering is an attractive technique for the synthesis of metallic particles. This work describes a new method of nickel powder production by depositing nickel on the surface of sodium chloride particles which were used as the template and are soluble in water. Ni powder with flake-like structure was obtained after washing Ni coated salt particles in ultrasonic cleaner. Salt particles and nickel powder were characterized using scanning electron microscope (SEM), energy-dispersive x-ray spectrometer, XRD and X-ray photoelectron spectroscopy (XPS) techniques. SEM images showed that thickness of the received Ni particles varied in the nanoscale and depended on the magnetron deposition time but did not depend on the size of salt particles. On the other hand initial size of the salt particles was successfully employed a measure to control lateral dimensions of Ni powder. XRD and XPS analysis results revealed that Ni particles had metallic core and oxidized shell which was a cause of the slightly deteriorated magnetic properties.

Anatomy of a Visible Light Activated Photocatalyst for Water Splitting

DOE PAGES

Phivilay, Somphonh Peter; Roberts, Charles; Gamalski, Andrew; ...

2018-06-08

The supported mixed oxide (Rh 2-yCr yO 3)/(Ga 1-xZn x)(N 1-xO x) photocatalyst, highly active for splitting of H 2O, was extensively characterized for its bulk and surface properties with the objective of developing fundamental structure-photoactivity relationships. Raman and UV-vis spectroscopy revealed that the molecular and electronic structures, respectively, of the oxynitride (Ga 1-xZn x)(N 1-xO x) support are not perturbed by the deposition of the (Rh 2-yCr yO 3) NPs. Photoluminescence (PL) spectroscopy, however, showed that the oxynitride (Ga 1-xZn x)(N 1-xO x) support is the source of excited electrons/holes and the (Rh 2-yCr yO 3) NPs greatly reducemore » the undesirable recombination of photoexcited electron/holes by acting as efficient electron traps as well as increase the lifetimes of the excitons. High Resolution-XPS and High Sensitivity-LEIS surface analyses reveal that the surfaces of the (Rh 2-yCr yO 3) NPs consist of Rh +3 and Cr +3 mixed oxide species. In Situ AP-XPS help to reveal that the Rh+3 and surface N atoms are involved in water splitting. Dispersed RhOx species on the (Ga 1-xZn x)(N 1-xO x) support and on CrO x NPs were found to be the photocatalytic active sites for H 2 generation and N and Zn sites from the (Ga 1-xZn x)(N 1-xO x) support are the photocatalytic active site for O 2 generation. The current investigation establishes the fundamental structure-photoactivity relationships of these visible light activated photocatalysts.« less

Anatomy of a Visible Light Activated Photocatalyst for Water Splitting

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

Phivilay, Somphonh Peter; Roberts, Charles; Gamalski, Andrew

The supported mixed oxide (Rh 2-yCr yO 3)/(Ga 1-xZn x)(N 1-xO x) photocatalyst, highly active for splitting of H 2O, was extensively characterized for its bulk and surface properties with the objective of developing fundamental structure-photoactivity relationships. Raman and UV-vis spectroscopy revealed that the molecular and electronic structures, respectively, of the oxynitride (Ga 1-xZn x)(N 1-xO x) support are not perturbed by the deposition of the (Rh 2-yCr yO 3) NPs. Photoluminescence (PL) spectroscopy, however, showed that the oxynitride (Ga 1-xZn x)(N 1-xO x) support is the source of excited electrons/holes and the (Rh 2-yCr yO 3) NPs greatly reducemore » the undesirable recombination of photoexcited electron/holes by acting as efficient electron traps as well as increase the lifetimes of the excitons. High Resolution-XPS and High Sensitivity-LEIS surface analyses reveal that the surfaces of the (Rh 2-yCr yO 3) NPs consist of Rh +3 and Cr +3 mixed oxide species. In Situ AP-XPS help to reveal that the Rh+3 and surface N atoms are involved in water splitting. Dispersed RhOx species on the (Ga 1-xZn x)(N 1-xO x) support and on CrO x NPs were found to be the photocatalytic active sites for H 2 generation and N and Zn sites from the (Ga 1-xZn x)(N 1-xO x) support are the photocatalytic active site for O 2 generation. The current investigation establishes the fundamental structure-photoactivity relationships of these visible light activated photocatalysts.« less

Electrophoretically deposited reduced graphene oxide platform for food toxin detection

NASA Astrophysics Data System (ADS)

Srivastava, Saurabh; Kumar, Vinod; Ali, Md Azahar; Solanki, Pratima R.; Srivastava, Anchal; Sumana, Gajjala; Saxena, Preeti Suman; Joshi, Amish G.; Malhotra, B. D.

2013-03-01

Reduced graphene oxide (RGO) due to its excellent electrochemical properties and large surface area, has recently aroused much interest for electrochemical biosensing application. Here, the chemically active RGO has been synthesized and deposited onto an indium tin oxide (ITO) coated glass substrate by the electrophoretic deposition technique. This novel platform has been utilized for covalent attachment of the monoclonal antibodies of aflatoxin B1 (anti-AFB1) for food toxin (AFB1) detection. The electron microscopy, X-ray diffraction, and UV-visible studies reveal successful synthesis of reduced graphene oxide while the XPS and FTIR studies suggest its carboxylic functionalized nature. The electrochemical sensing results of the anti-AFB1/RGO/ITO based immunoelectrode obtained as a function of aflatoxin concentration show high sensitivity (68 μA ng-1 mL cm-2) and improved detection limit (0.12 ng mL-1). The association constant (ka) for antigen-antibody interaction obtained as 5 × 10-4 ng mL-1 indicates high affinity of antibodies toward the antigen (AFB1).Reduced graphene oxide (RGO) due to its excellent electrochemical properties and large surface area, has recently aroused much interest for electrochemical biosensing application. Here, the chemically active RGO has been synthesized and deposited onto an indium tin oxide (ITO) coated glass substrate by the electrophoretic deposition technique. This novel platform has been utilized for covalent attachment of the monoclonal antibodies of aflatoxin B1 (anti-AFB1) for food toxin (AFB1) detection. The electron microscopy, X-ray diffraction, and UV-visible studies reveal successful synthesis of reduced graphene oxide while the XPS and FTIR studies suggest its carboxylic functionalized nature. The electrochemical sensing results of the anti-AFB1/RGO/ITO based immunoelectrode obtained as a function of aflatoxin concentration show high sensitivity (68 μA ng-1 mL cm-2) and improved detection limit (0.12 ng mL-1). The association constant (ka) for antigen-antibody interaction obtained as 5 × 10-4 ng mL-1 indicates high affinity of antibodies toward the antigen (AFB1). Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr32242d

Chemical states of surface oxygen during CO oxidation on Pt(1 1 0) surface revealed by ambient pressure XPS

DOE PAGES

Yu, Youngseok; Koh, Yoobin Esther; Lim, Hojoon; ...

2017-10-20

Here, the study of CO oxidation on Pt(110) surface is revisited using ambient pressure x-ray photoemission spectroscopy. When the surface temperature reaches the activation temperature for CO oxidation under elevated pressure conditions, both the α-phase of PtO 2 oxide and chemisorbed oxygen are formed simultaneously on the surface. Due to the exothermic nature of CO oxidation, the temperature of the Pt surface increases as CO oxidation takes place. As the CO/O 2 ratio increases, the production of CO 2 increases continuously and the surface temperature also increases. Interestingly, within the diffusion limited regions, the amount of surface oxide changes littlemore » while the chemisorbed oxygen is reduced.« less

Role of Ni doping on transport properties of ZnO thin films

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

Dar, Tanveer Ahmad, E-mail: tanveerphysics@gmail.com; Agrawal, Arpana; Sen, Pratima

2015-06-24

Nickel doped (Ni=0.05) and undoped Zinc Oxide (ZnO) thin films have been prepared by Pulsed laser deposition (PLD) technique. The structural analysis of the films was done by X-ray diffraction (XRD) studies which reveal absence of any secondary phase in the prepared samples. UV transmission spectra show that Ni doping reduces the transparency of the films. X-ray Photoelectron spectroscopy (XPS) also shows the presence of metallic Ni along with +2 oxidation state in the sample. Low temperature magneto transport properties of the ZnO and NiZnO films are also discussed in view of Khosla fisher model. Ni doping in ZnO resultsmore » in decrease in magnitude of negative MR.« less

The oxidation state of iron and manganese in polymetallic nodules from the Central Indian Ocean Basin

NASA Astrophysics Data System (ADS)

Ganwani, Girish; Meena, Samay Singh; Ram, Sahi; Bijlani, N.; Bhatia, Beena; Tripathi, R. P.

2018-05-01

The study of oxidation states of iron (Fe) and manganese (Mn) in polymetallic nodules were carried out by means of X-ray photoelectron spectroscopic techniques. The polymetallic nodules were collected from different locations of the Central Indian Ocean Basin (CIOB). The Mn/Fe ratio allowed the differentiation of these nodules from their origin: "hydrogeneous" or "hydrothermal". The binding energies of Mn 2p3/2 (ranging from 641.5 to 642.4 ev), Fe 2p3/2 (ranging from 711.0 to 711.8 ev) and O 1s (ranging from 530.2 to 530.9 ev) from XPS reveal that most of manganese is in Mn4+ and iron is in Fe3+ state.

Chemical states of surface oxygen during CO oxidation on Pt(1 1 0) surface revealed by ambient pressure XPS

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

Yu, Youngseok; Koh, Yoobin Esther; Lim, Hojoon

Here, the study of CO oxidation on Pt(110) surface is revisited using ambient pressure x-ray photoemission spectroscopy. When the surface temperature reaches the activation temperature for CO oxidation under elevated pressure conditions, both the α-phase of PtO 2 oxide and chemisorbed oxygen are formed simultaneously on the surface. Due to the exothermic nature of CO oxidation, the temperature of the Pt surface increases as CO oxidation takes place. As the CO/O 2 ratio increases, the production of CO 2 increases continuously and the surface temperature also increases. Interestingly, within the diffusion limited regions, the amount of surface oxide changes littlemore » while the chemisorbed oxygen is reduced.« less

Influence of Temperature on Corrosion Behavior of 2A02 Al Alloy in Marine Atmospheric Environments

PubMed Central

Cao, Min; Liu, Li; Fan, Lei; Yu, Zhongfen; Li, Ying; Oguzie, Emeka E.; Wang, Fuhui

2018-01-01

The corrosion behavior of 2A02 Al alloy under 4 mg/cm2 NaCl deposition at different temperatures (from 30 to 80 °C) has been studied. This corrosion behavior was researched using mass-gain, scanning electron microscopy-SEM, laser scanning confocal microscopy-LSCM, X-ray photoelectron spectroscopy-XPS and other techniques. The results showed and revealed that the corrosion was maximal at 60 °C after 200 h of exposure. The increase of temperature not only affected the solubility of oxygen gas in the thin film, but also promoted the transport of ions (such as Cl−), and the formation of protective AlO(OH), which further affects the corrosion speed. PMID:29401690

XPS and ToF-SIMS analysis of natural rubies and sapphires heat-treated in a reducing (5 mol% H 2/Ar) atmosphere

NASA Astrophysics Data System (ADS)

Achiwawanich, S.; James, B. D.; Liesegang, J.

2008-12-01

Surface effects on Mong Hsu rubies and Kanchanaburi sapphires after heat treatment in a controlled reducing atmosphere (5 mol% H 2/Ar) have been investigated using advanced surface science techniques including X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Visual appearance of the gemstones is clearly affected by the heat treatment in a reducing atmosphere. Kanchanaburi sapphires, in particular, exhibit Fe-containing precipitates after the heat treatment which have not been observed in previous studies under an inert atmosphere. Significant correlation between changes in visual appearance of the gemstones and variations in surface concentration of trace elements, especially Ti and Fe are observed. The XPS and ToF-SIMS results suggest that; (1) a reducing atmosphere affects the oxidation state of Fe; (2) dissociation of Fe-Ti interaction may occur during heat treatment.

Destruction behavior of hexabromocyclododecanes during incineration of solid waste containing expanded and extruded polystyrene insulation foams.

PubMed

Takigami, Hidetaka; Watanabe, Mafumi; Kajiwara, Natsuko

2014-12-01

Hexabromocyclododecanes (HBCDs) have been used for flame retardation mainly in expanded polystyrene (EPS) and extruded polystyrene (XPS) insulation foams. Controlled incineration experiments with solid wastes containing each of EPS and XPS were conducted using a pilot-scale incinerator to investigate the destruction behavior of HBCDs and their influence on the formation of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/DFs). EPS and XPS materials were respectively blended with refuse derived fuel (RDF) as input wastes for incineration. Concentrations of HBCDs contained in the EPS- and XPS-added RDFs, were 140 and 1100 mg kg(-1), respectively. In which γ-HBCD was dominant (68% of the total HBCD content) in EPS-added RDF and α-HBCD accounted for 73% of the total HBCDs in XPS-added RDF. During the incineration experiments with EPS and XPS, primary and secondary combustion zones were maintained at temperatures of 840 °C and 900 °C. The residence times of waste in the primary combustion zone and flue gas in the secondary combustion zone was 30 min and three seconds, respectively. HBCDs were steadily degraded in the combustion chambers and α-, β-, and γ-HBCD behaved similarly. Concentration levels of the total HBCDs in the bag filter exit gas for the two experiments with EPS and XPS were 0.7 and 0.6ngmN(-3), respectively. HBCDs were also not detected (<0.2 ng g(-1)) in the bottom and fly ash samples. From the obtained results, it was calculated that HBCDs were sufficiently destroyed in the whole incineration process with destruction efficiencies of more than 99.9999 for both of EPS and XPS cases. For PBDD/DFs, the levels detected in the bottom and fly ash samples were very low (0.028 ng g(-1) at maximum). In the case of XPS-added experiment, 2,3,7,8-TeBDD and 2,3,7,8-TeBDF were determined in the flue gas at levels (0.05-0.07 ng mN(-3)) slightly over the detection limits in the environmental emission gas samples, suggesting HBCDs in XPS are possibly a precursor of detected PBDD/DFs. Operational care should be taken when the ratio of HBCD-containing polystyrene is increased in the input wastes just to make sure of formation prevention and emission control of PBDD/DFs. The concentrations and congener patterns of PCDD/DFs and dl-PCBs in the samples during the three experiments were not affected by an addition of HBCDs. Copyright © 2014 Elsevier Ltd. All rights reserved.

Plasmonic properties of Ag nanoparticles embedded in GeO2-SiO2 matrix by atom beam sputtering.

PubMed

Mohapatra, Satyabrata

2016-02-07

Nanocomposite thin films containing Ag nanoparticles embedded in the GeO2-SiO2 matrix were synthesized by the atom beam co-sputtering technique. The structural, optical and plasmonic properties and the chemical composition of the nanocomposite thin films were studied by transmission electron microscopy (TEM) with energy dispersive X-ray spectroscopy (EDX), UV-visible absorption spectroscopy and X-ray photoelectron spectroscopy (XPS). UV-visible absorption studies on Ag-SiO2 nanocomposites revealed the presence of a strong localized surface plasmon resonance (LSPR) peak characteristic of Ag nanoparticles at 413 nm, which showed a blue shift of 26 nm (413 to 387 nm) along with a significant broadening and drastic decrease in intensity with the incorporation of 16 at% of Ge into the SiO2 matrix. TEM studies on Ag-GeO2-SiO2 nanocomposite thin films confirmed the presence of Ag nanoparticles with an average size of 3.8 nm in addition to their aggregates with an average size of 16.2 nm. Thermal annealing in air resulted in strong enhancement in the intensity of the LSPR peak, which showed a regular red shift of 51 nm (from 387 to 438 nm) with the increase in annealing temperature up to 500 °C. XPS studies showed that annealing in air resulted in oxidation of excess Ge atoms in the nanocomposite into GeO2. Our work demonstrates the possibility of controllably tuning the LSPR of Ag nanoparticles embedded in the GeO2-SiO2 matrix by single-step thermal annealing, which is interesting for optical applications.

Enhanced room temperature ferromagnetism in Ni doped SnO2 nanoparticles: A comprehensive study

NASA Astrophysics Data System (ADS)

Ahmed, Ateeq; Ali, T.; Naseem Siddique, M.; Ahmad, Abid; Tripathi, P.

2017-08-01

We emphasized on a detailed investigation of the structural, optical, and magnetic properties of pure and Ni-doped SnO2 nanoparticles (NPs) synthesized by a sol-gel process. An extensive structural study has been carried out using various characterization techniques. The X-ray Diffraction (XRD) spectra show the formation of the single phase tetragonal structure of pure and Ni-doped SnO2 NPs without any noticeable impurity phase such as NiO. XRD results indicate that the crystallite size of SnO2 is found to be decreased with Ni doping, which has also been confirmed by the Field Emission Scanning Electron Microscopy study. X-ray Photoelectron Spectroscopy (XPS) measurements displayed a clear sign for Ni2+ ions occupying the lattice sites of Sn4+ in the SnO2 host which also gives clear evidence for the formation of single phase Sn1-xNixO2 NPs. The optical analysis shows a significant decrease in the energy gap of SnO2, i.e., (from 3.71 eV to 3.28 eV) as Ni concentration increases which may be correlated with the core level valence band XPS analysis. Photoluminescence studies show that Ni doping creates oxygen vacancies due to dissimilar ionic radii of Ni2+ and Sn4+. Superconducting quantum interference device measurements revealed that the Ni doped SnO2 NPs exhibit strong ferromagnetic behavior at room temperature and this analysis has been well fitted with a simple relationship to find out magnetic parameters proposed by Stearns and Cheng et al. Hence, our results demonstrate that Ni-doping has strong impact on the structural, optical, and magnetic properties.

Morphological, chemical and structural characterisation of deciduous enamel: SEM, EDS, XRD, FTIR and XPS analysis.

PubMed

Zamudio-Ortega, C M; Contreras-Bulnes, R; Scougall-Vilchis, R J; Morales-Luckie, R A; Olea-Mejía, O F; Rodríguez-Vilchis, L E

2014-09-01

The purpose of this study was to characterise the enamel surface of sound deciduous teeth in terms of morphology, chemical composition, structure and crystalline phases. The enamel of 30 human deciduous teeth was examined by: Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray Spectroscopy (EDS), X-ray Powder Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), and X-ray Photoelectron Spectroscopy (XPS). Chemical differences between incisors and canines were statistically evaluated using the Mann-Whitney U test (p ≤ 0.05). Three enamel patterns were observed by SEM: 'mostly smooth with some groves', 'abundant microporosities' and 'exposed prisms'. The average Ca/P molar ratios were 1.37 and 1.03 by EDS and XPS, respectively. The crystallite size determined by XRD was 210.82 ± 16.78 Å. The mean ratio between Ca bonded to phosphate and Ca bonded to hydroxyl was approximately 10:1. The enamel of sound deciduous teeth showed two main patterns: 'mostly smooth with some groves' and 'abundant microporosities'. 'Exposed prisms' was a secondary pattern. There were slight variations among the Ca/P molar ratios found by EDS and XPS, suggesting differences in the mineral content from the enamel surface to the interior. The crystalline phases found in enamel were hydroxyapatite and carbonate apatite, with major type B than type A carbonate incorporation.

Oxidation of palladium on Au(111) and ZnO(0001) supports

DOE PAGES

Lallo, J.; Tenney, S. A.; Kramer, A.; ...

2014-10-21

The oxidation of supported Pd-deposits on Au(111) and ZnO(0001) single crystals has been studied by x- ray photoemission spectroscopy (XPS). Oxidation has been carried out ex-situ in a high-pressure cell with subsequent vacuum-transfer and characterization by XPS in ultrahigh vacuum (UHV), as well as using in-situ characterization by synchrotron based near-ambient pressure XPS. On Au(111) alloying of Pd with the substrate competes with oxidation and only sufficiently thick Pd films have been found to oxidize. For Pd on ZnO the oxidation conditions depend on the amount of deposited Pd. Thicker Pd deposits behave similar to bulk Pd, while thinner filmsmore » oxidize already at lower temperatures. Interestingly, for very small amounts of Pd, in-situ XPS shows full oxidation at room temperature and at less than 0.6 mbar O₂ pressure. This indicates a lowering of the kinetic barriers for oxidation of very small supported Pd-clusters. The formed oxide is, however, not stable in UHV and a slow reduction is observed. The instability of this oxide indicates that the Pd-oxide formed at the interface to ZnO may have different chemical properties compared to bulk PdO or surface oxides on Pd.« less

Preparation of PVA/Co/Ag film and evaluation of its magnetic and microstructural properties

NASA Astrophysics Data System (ADS)

Banerjee, M.; Sachdev, Preeti; Mukherjee, G. S.

2012-05-01

PVA/Co/Ag film has been prepared by sputtering Co followed by Ag in polyvinyl alcohol (PVA) matrix film by IBS technique, so as to get a 9 nm (thick) layer of Co metal nanoparticles followed by a protective 4 nm (thick) layer of Ag nanoparticles. Grazing incidence x-ray diffraction (GIXRD) pattern of the film reveals the formation of nanocrystalline Co with hcp phase. GIXRD pattern also indicates that there is no change in the crystalline structure of PVA even after sputtering of the metallic nanoparticles. The average particle size of Co nanoparticles as evaluated using Scherrer formula is found to be about 2.64 nm. UV visible absorption pattern of the film sample showed SPR peaks of Co and Ag metals in their nano size level embedded in the PVA matrix system. XPS study confirms the metallic nature of Co and Ag nanoparticles; and the depth profiling study reveals that both the metal nanoparticles have been embedded in the PVA matrix system. Surface morphology of such film has been studied using AFM; and the magnetic behaviour of the film studied by using MOKE shows soft ferromagnetic behaviour in this PVA/Co/Ag system.

Plasma assisted synthesis of vanadium pentoxide nanoplates

NASA Astrophysics Data System (ADS)

Singh, Megha; Sharma, Rabindar Kumar; Kumar, Prabhat; Reddy, G. B.

2015-08-01

In this work, we report the growth of α-V2O5 (orthorhombic) nanoplates on glass substrate using plasma assisted sublimation process (PASP) and Nickel as catalyst. 100 nm thick film of Ni is deposited over glass substrate by thermal evaporation process. Vanadium oxide nanoplates have been deposited treating vanadium metal foil under high vacuum conditions with oxygen plasma. Vanadium foil is kept at fixed temperature growth of nanoplates of V2O5 to take place. Samples grown have been studied using XPS, XRD and HRTEM to confirm the growth of α-phase of V2O5, which revealed pure single crystal of α- V2O5 in orthorhombic crystallographic plane. Surface morphological studies using SEM and TEM show nanostructured thin film in form of plates. Uniform, vertically aligned randomly oriented nanoplates of V2O5 have been deposited.

Oligodeoxyribonucleotide association with single-walled carbon nanotubes studied by SPM.

PubMed

Lahiji, Roya R; Dolash, Bridget D; Bergstrom, Donald E; Reifenberger, Ronald

2007-11-01

Studies have been performed on both as-received and chemically oxidized single-walled carbon nanotubes (SWCNTs) grown by two different growth methods to better understand the preferential association of the oligodeoxyribonucleotide T30 (ODN) with SWCNTs. Samples of T30 ODN:SWCNT were examined under ambient conditions using non-contact scanning probe microscope (SPM) techniques. The resulting images show different morphologies ranging from tangled networks of SWCNTs to individual, well-dispersed isolated SWCNTs as the sonication time is increased. SPM images of well-dispersed, as-received SWCNTs reveal isolated features that are 1.4 to 2.8 nm higher than the bare SWCNT itself. X-ray photoemission spectroscopy (XPS) confirmed these features to be T30 ODN in nature. Chemically oxidizing the SWCNTs before sonication is found to be an effective way to increase the number of T30 ODN features.

Quantification of Efficiency of Beneficiation of Lunar Regolith

NASA Technical Reports Server (NTRS)

Trigwell, Steve; Lane, John; Captain, James; Weis, Kyle; Quinn, Jacqueline; Watanabe, Fumiya

2011-01-01

Electrostatic beneficiation of lunar regolith is being researched at Kennedy Space Center to enhance the ilmenite concentration of the regolith for the production of oxygen in in-situ resource utilization on the lunar surface. Ilmenite enrichment of up to 200% was achieved using lunar simulants. For the most accurate quantification of the regolith particles, standard petrographic methods are typically followed, but in order to optimize the process, many hundreds of samples were generated in this study that made the standard analysis methods time prohibitive. In the current studies, X-ray photoelectron spectroscopy (XPS) and Secondary Electron microscopy/Energy Dispersive Spectroscopy (SEM/EDS) were used that could automatically, and quickly, analyze many separated fractions of lunar simulant. In order to test the accuracy of the quantification, test mixture samples of known quantities of ilmenite (2, 5, 10, and 20 wt%) in silica (pure quartz powder), were analyzed by XPS and EDS. The results showed that quantification for low concentrations of ilmenite in silica could be accurately achieved by both XPS and EDS, knowing the limitations of the techniques. 1

Perspective: Chemical reactions in ionic liquids monitored through the gas (vacuum)/liquid interface.

PubMed

Maier, F; Niedermaier, I; Steinrück, H-P

2017-05-07

This perspective analyzes the potential of X-ray photoelectron spectroscopy under ultrahigh vacuum (UHV) conditions to follow chemical reactions in ionic liquids in situ. Traditionally, only reactions occurring on solid surfaces were investigated by X-ray photoelectron spectroscopy (XPS) in situ. This was due to the high vapor pressures of common liquids or solvents, which are not compatible with the required UHV conditions. It was only recently realized that the situation is very different when studying reactions in Ionic Liquids (ILs), which have an inherently low vapor pressure, and first studies have been performed within the last years. Compared to classical spectroscopy techniques used to monitor chemical reactions, the advantage of XPS is that through the analysis of their core levels all relevant elements can be quantified and their chemical state can be analyzed under well-defined (ultraclean) conditions. In this perspective, we cover six very different reactions which occur in the IL, with the IL, or at an IL/support interface, demonstrating the outstanding potential of in situ XPS to gain insights into liquid phase reactions in the near-surface region.

Naval Arctic Research Laboratory (NARL) Subsurface Containment Berm Investigation

DTIC Science & Technology

2015-10-01

Southwest UTM Universal Transverse Mercator XPS Extruded Polystyrene WGS World Geodetic System ERDC/CRREL TR-15-15 1 1 Introduction In 1996, under...layers of extruded polystyrene (XPS) board insula- tion at approximately 1.0 m below the ground surface for the length of the berm. The XPS was...ply- wood installed during the trench construction. We attempted probing in Dew Line Road and in the area adjacent to the Navy Hangar and Treat- ment

Core Level Shifts of Hydrogenated Pyridinic and Pyrrolic Nitrogen in the Nitrogen-Containing Graphene-Based Electrocatalysts: In-Plane vs Edge Defects

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

Matanovic, Ivana; Artyushkova, Kateryna; Strand, Matthew B.

A combination of N 1s X-ray photoelectron spectroscopy (XPS) and first principles calculations of nitrogen-containing model electrocatalysts was used to elucidate the nature of the nitrogen defects that contribute to the binding energy (BE) range of the N 1s XPS spectra of these materials above ~400 eV. Experimental core level shifts were obtained for a set of model materials, namely N-doped carbon nanospheres, Fe–N–carbon nanospheres, polypyrrole, polypyridine, and pyridinium chloride, and were compared to the shifts calculated using density functional theory. The results confirm that the broad peak positioned at ~400.7 eV in the N 1s XPS spectra of N-containingmore » catalysts, which is typically assigned to pyrrolic nitrogen, contains contributions from other hydrogenated nitrogen species such as hydrogenated pyridinic functionalities. Namely, N 1s BEs of hydrogenated pyridinic-N and pyrrolic-N were calculated as 400.6 and 400.7 eV, respectively, using the Perdew–Burke–Ernzerhof exchange-correlation functional. A special emphasis was placed on the study of the differences in the XPS imprint of N-containing defects that are situated in the plane and on the edges of the graphene sheet. Density functional theory calculations for BEs of the N 1s of in-plane and edge defects show that hydrogenated N defects are more sensitive to the change in the chemical environment in the carbon matrix than the non-hydrogenated N defects. In conclusion, calculations also show that edge-hydrogenated pyridinic-N and pyrrolic-N defects only contribute to the N 1s XPS peak located at ~400.7 eV if the graphene edges are oxygenated or terminated with bare carbon atoms.« less

Core Level Shifts of Hydrogenated Pyridinic and Pyrrolic Nitrogen in the Nitrogen-Containing Graphene-Based Electrocatalysts: In-Plane vs Edge Defects

DOE PAGES

Matanovic, Ivana; Artyushkova, Kateryna; Strand, Matthew B.; ...

2016-12-07

A combination of N 1s X-ray photoelectron spectroscopy (XPS) and first principles calculations of nitrogen-containing model electrocatalysts was used to elucidate the nature of the nitrogen defects that contribute to the binding energy (BE) range of the N 1s XPS spectra of these materials above ~400 eV. Experimental core level shifts were obtained for a set of model materials, namely N-doped carbon nanospheres, Fe–N–carbon nanospheres, polypyrrole, polypyridine, and pyridinium chloride, and were compared to the shifts calculated using density functional theory. The results confirm that the broad peak positioned at ~400.7 eV in the N 1s XPS spectra of N-containingmore » catalysts, which is typically assigned to pyrrolic nitrogen, contains contributions from other hydrogenated nitrogen species such as hydrogenated pyridinic functionalities. Namely, N 1s BEs of hydrogenated pyridinic-N and pyrrolic-N were calculated as 400.6 and 400.7 eV, respectively, using the Perdew–Burke–Ernzerhof exchange-correlation functional. A special emphasis was placed on the study of the differences in the XPS imprint of N-containing defects that are situated in the plane and on the edges of the graphene sheet. Density functional theory calculations for BEs of the N 1s of in-plane and edge defects show that hydrogenated N defects are more sensitive to the change in the chemical environment in the carbon matrix than the non-hydrogenated N defects. In conclusion, calculations also show that edge-hydrogenated pyridinic-N and pyrrolic-N defects only contribute to the N 1s XPS peak located at ~400.7 eV if the graphene edges are oxygenated or terminated with bare carbon atoms.« less

The Gaussian-Lorentzian Sum, Product, and Convolution (Voigt) functions in the context of peak fitting X-ray photoelectron spectroscopy (XPS) narrow scans

NASA Astrophysics Data System (ADS)

Jain, Varun; Biesinger, Mark C.; Linford, Matthew R.

2018-07-01

X-ray photoelectron spectroscopy (XPS) is arguably the most important vacuum technique for surface chemical analysis, and peak fitting is an indispensable part of XPS data analysis. Functions that have been widely explored and used in XPS peak fitting include the Gaussian, Lorentzian, Gaussian-Lorentzian sum (GLS), Gaussian-Lorentzian product (GLP), and Voigt functions, where the Voigt function is a convolution of a Gaussian and a Lorentzian function. In this article we discuss these functions from a graphical perspective. Arguments based on convolution and the Central Limit Theorem are made to justify the use of functions that are intermediate between pure Gaussians and pure Lorentzians in XPS peak fitting. Mathematical forms for the GLS and GLP functions are presented with a mixing parameter m. Plots are shown for GLS and GLP functions with mixing parameters ranging from 0 to 1. There are fundamental differences between the GLS and GLP functions. The GLS function better follows the 'wings' of the Lorentzian, while these 'wings' are suppressed in the GLP. That is, these two functions are not interchangeable. The GLS and GLP functions are compared to the Voigt function, where the GLS is shown to be a decent approximation of it. Practically, both the GLS and the GLP functions can be useful for XPS peak fitting. Examples of the uses of these functions are provided herein.

XUV Photometer System (XPS): New Dark-Count Corrections Model and Improved Data Products

NASA Astrophysics Data System (ADS)

Elliott, J. P.; Vanier, B.; Woods, T. N.

2017-12-01

We present newly updated dark-count calibrations for the SORCE XUV Photometer System (XPS) and the resultant improved data products released in March of 2017. The SORCE mission has provided a 14-year solar spectral irradiance record, and the XPS contributes to this record in the 0.1 nm to 40 nm range. The SORCE spacecraft has been operating in what is known as Day-Only Operations (DO-Op) mode since February of 2014. In this mode it is not possible to collect data, including dark-counts, when the spacecraft is in eclipse as we did prior to DO-Op. Instead, we take advantage of the position of the XPS filter-wheel, and collect these data when the wheel position is in a "dark" position. Further, in this mode dark data are not always available for all observations, requiring an extrapolation in order to calibrate data at these times. To extrapolate, we model this with a piece-wise 2D nonlinear least squares surface fit in the time and temperature dimensions. Our model allows us to calibrate XPS data into the DO-Op phase of the mission by extrapolating along this surface. The XPS version 11 data product release benefits from this new calibration. We present comparisons of the previous and current calibration methods in addition to planned future upgrades of our data products.

XPS/NEXAFS spectroscopic and conductance studies of glycine on AlGaN/GaN transistor devices

NASA Astrophysics Data System (ADS)

Myers, Matthew; Khir, Farah Liyana Muhammad; Home, Michael A.; Mennell, Christopher; Gillbanks, Jeremy; Tadich, Anton; Baker, Murray V.; Nener, Brett D.; Parish, Giacinta

2018-03-01

We report on a study using a combination of XPS/NEXAFS and conductivity measurements to develop a fundamental understanding of how dipolar molecules interact with the heterostructure device surface and affect the device conductivity of AlGaN/GaN heterostructure-based transistors. In such structures, which are increasingly being investigated for chemical and biological sensing, a 2-dimensional electron gas spontaneously forms at the layer interface that is sensitive to the charge characteristics of the exposed surface. Glycine, chosen for this study because it is the simplest of the amino acids and is known to form a zwitterionic configuration when stabilized through intermolecular interactions, was evaporated under ultra-high vacuum conditions onto the device surface and subsequently both XPS/NEXAFS and conductivity measurements were conducted. NEXAFS spectra show a preferential orientation for the Glycine molecules on the surface and evidence for both neutral and zwitterionic species on the surface. In situ conductivity measurements suggest that the negatively charged carboxylate group is closest to the surface. These results are a unique and pivotal contribution to the previous and at times conflicting literature on the zwitterionic nature of Glycine.

XPS and EELS characterization of Mn2SiO4, MnSiO3 and MnAl2O4

NASA Astrophysics Data System (ADS)

Grosvenor, A. P.; Bellhouse, E. M.; Korinek, A.; Bugnet, M.; McDermid, J. R.

2016-08-01

X-ray Photoelectron Spectroscopy (XPS) and Electron Energy Loss Spectroscopy (EELS) are strong candidate techniques for characterizing steel surfaces and substrate-coating interfaces when investigating the selective oxidation and reactive wetting of advanced high strength steels (AHSS) during the continuous galvanizing process. However, unambiguous identification of ternary oxides such as Mn2SiO4, MnSiO3, and MnAl2O4 by XPS or EELS, which can play a significant role in substrate reactive wetting, is difficult due to the lack of fully characterized standards in the literature. To resolve this issue, samples of Mn2SiO4, MnSiO3 and MnAl2O4 were synthesized and characterized by XPS and EELS. The unique features of the XPS and EELS spectra for the Mn2SiO4, MnSiO3 and MnAl2O4 standards were successfully derived, thereby allowing investigators to fully differentiate and identify these oxides at the surface and subsurface of Mn, Si and Al alloyed AHSS using these techniques.

X-ray photoemission studies of Zn doped Cu 1- xTl xBa 2Ca 2Cu 3- yZn yO 10- δ ( y = 0, 2.65) superconductors

NASA Astrophysics Data System (ADS)

Khan, Nawazish A.; Mumtaz, M.; Ahadian, M. M.; Iraji-zad, Azam

2007-03-01

The X-ray photoemission (XPS) measurements of Cu 1- xTl xBa 2Ca 2Cu 3- yZn yO 10- δ ( y = 0, 2.65) superconductors have been performed and compared. These studies revealed that the charge state of thallium in the Cu 0.5Tl 0.5Ba 2O 4- δ charge reservoir layer in Zn doped samples is Tl 1+, while it is a mix of Tl 1+ and Tl 2+ in Zn free samples. The binding energy of Ba atoms in the Zn doped samples is shifted to higher energy, which when considered along with the presence of Tl 1+ suggested that it more efficiently directed the carriers to ZnO 2 and CuO 2 planes. The evidence of improved inter-plane coupling witnessed in X-ray diffraction is also confirmed by XPS measurements of Ca atoms in the Zn doped samples. The shift of the valance band spectrum in these Zn doped samples to higher energies suggested that the electrons at the top edge of the valance band were tied to a higher binding energy (relative to samples without Zn doping), which most likely resulted in a much lower energy state of the system in the superconducting state. The stronger superconducting state arising out of these effects is witnessed in the form of increased Tc( R = 0), Jc and the extent of diamagnetism in the final compound.

Improved microwave shielding behavior of carbon nanotube-coated PET fabric using plasma technology

NASA Astrophysics Data System (ADS)

Haji, Aminoddin; Semnani Rahbar, Ruhollah; Mousavi Shoushtari, Ahmad

2014-08-01

Four different procedures were conducted to load amine functionalized multiwall carbon nanotube (NH2-MWCNT) onto poly (ethylene terephthalate) (PET) fabric surface to obtain a microwave shielding sample. Plasma treated fabric which was subsequently coated with NH2-MWCNT in the presence of acrylic acid was chosen as the best sample. Surface changes in the PET fabrics were investigated by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Wide-angle X-ray diffraction was used to study the crystalline structure of the PET fabric. The microwave shielding performance of the PET fabrics in term of reflection loss was determined using a network analyzer at X-band (8.2-12.4 GHz). The XPS results revealed that the carbon atomic percentage decreased while the oxygen atomic percentage increased when the fabric was plasma treated and coated with NH2-MWCNT. The SEM images showed that the NH2-MWCNTs were homogenously dispersed and individually separated in the surface of fabric. Moreover, the structural studies showed that the crystalline region of the fabrics was not affected by NH2-MWCNT and plasma treatment. The best microwave absorbing properties were obtained from the plasma treated fabric which was then coated with 10% NH2-MWCNT in the presence of acrylic acid. It showed a minimum reflection loss of ∼-18.2 dB about 11 GHz. Proper attachments of NH2-MWCNT on the PET fabric surface was explained in the suggested mechanism in which hydrogen bonding and amide linkage are responsible for the achievement of microwave shielding properties with high durability.

Highly efficient removal of chlorotetracycline from aqueous solution using graphene oxide/TiO2 composite: Properties and mechanism

NASA Astrophysics Data System (ADS)

Li, Zhaoqian; Qi, Mengyu; Tu, Chunyan; Wang, Weiping; Chen, Jianrong; Wang, Ai-Jun

2017-12-01

The extensive usage of chlorotetracycline (CTC) has caused the persistence of antibiotic residues in aquatic environments, resulting in serious threat to human health and ecosystems. In this study, graphene oxide/titanium dioxide (GO/TiO2) nanocomposite was successfully synthesized via in situ hydrolysis of tetra-n-butyl titanate (Ti(BuO)4) to TiO2 particles on GO sheets and used as adsorbent for efficient adsorptive removal of CTC from aqueous solution. The prepared GO/TiO2 was characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transformed infrared (FT-IR), Raman spectroscopy and X-ray photoelectron (XPS). Adsorption kinetics, isotherms and thermodynamics were systematically investigated to evaluate the adsorption properties of GO/TiO2. Adsorption mechanism was further analyzed by FT-IR, UV-vis and XPS. The results indicated that adsorption kinetics closely followed the pseudo-second order model; the maximum adsorption capacity determined by Langmuir model was 261.10 mg g-1 at 298 K and the thermodynamic studies revealed that the adsorption of CTC onto the GO/TiO2 was a spontaneous and endothermic process. Moreover, the interactions between CTC and GO/TiO2 were presumed to be ligand exchange between CTC and TiO2, while the π-π electron donor-acceptor interaction, hydrogen bond and cation-π bonding were constructed between CTC and GO. Finally, the prepared GO/TiO2 was successfully applied for the efficient removal of CTC from Wu River water.

How much surface coating of hydrophobic azithromycin is sufficient to prevent moisture-induced decrease in aerosolisation of hygroscopic colistin powder?

PubMed Central

Zhou, Qi (Tony); Loh, Zhi Hui; Yu, Jiaqi; Sun, Si-ping; Gengenbach, Thomas; Denman, John A.; Li, Jian; Chan, Hak-Kim

2017-01-01

Aerosolisation performance of hygroscopic particles of colistin could be compromised at elevated humidity due to increased capillary forces. Co-spray drying colistin with a hydrophobic drug is known to provide a protective coating on the composite particle surfaces against moisture-induced reduction in aerosolisation performance; however, the effects of component ratio on surface coating quality and powder aerosolisation at elevated relative humidities are unknown. In this study, we have systematically examined the effects of mass ratio of hydrophobic azithromycin on surface coating quality and aerosolisation performance of the co-spray dried composite particles. Four combination formulations with varying drug ratios were prepared by co-spray drying drug solutions. Both of the drugs in each combination formulation had similar in vitro deposition profiles, suggesting that each composite particle comprise two drugs in the designed mass ratio, which is supported by XPS and ToF-SIMS data. XPS and ToF-SIMS measurements also revealed that 50 % by weight (or 35 % by molecular fraction) of azithromycin in the formulation provided a near-complete coating of 96.5 % (molar fraction) on the composite particle surface, which is sufficient to prevent moisture-induced reduction in FPFrecovered and FPFemitted. Higher azithromycin content did not increase coating coverage, while contents of azithromycin lower than 20 %w/w did not totally prevent the negative effects of humidity on aerosolisation performance. This study has highlighted that a critical amount of azithromycin is required to sufficiently coat the colistin particles for short-term protection against moisture. PMID:27255350

Dehydration of the Uranyl Peroxide Studtite, [UO 2(η 2-O 2)(H 2O) 2]·2H 2O, Affords a Drastic Change in the Electronic Structure: A Combined X-ray Spectroscopic and Theoretical Analysis

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

Vitova, Tonya; Pidchenko, Ivan; Biswas, Saptarshi

The dehydration of studtite, [UO 2(2-O 2)(H 2O)2]·2H 2O, to metastudtite, [UO 2(2-O 2)(H 2O) 2], uranyl peroxide minerals that are major oxidative alteration phases of UO2 under conditions of geological storage, has been studied using X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy. XPS of the U 4f region shows small but significant differences between studtite and metastudtite, with the 4f binding energy of studtite the highest reported for a uranyl mineral studied by this technique. Further information on the changes in the electronic structure was elucidated using U M4-edge High Energy Resolution XANES (HR-XANES) spectroscopy, which directly probesmore » f-orbital states. The transition from the 3d to the 5f* orbital is sensitive to variations of the U=Oaxial bond length and to changes in the bond covalency. We report evidences that the covalence in the uranyl fragment decreases upon dehydration. Photoluminescence spectroscopy at near liquid helium temperatures reveals significant spectral differences between the two materials, correlating with the X-ray spectroscopy results. A theoretical investigation has been conducted on the structures of both studtite and metastudtite and benchmarked to the HR-XANES spectra. These illustrate the sensitivity of the 3d to the 5f * transition towards U=Oaxial bond variation.« less

Biomolecule-controlled hydrothermal synthesis of C-N-S-tridoped TiO2 nanocrystalline photocatalysts for NO removal under simulated solar light irradiation.

PubMed

Wang, Yawen; Huang, Yu; Ho, Wingkei; Zhang, Lizhi; Zou, Zhigang; Lee, Shuncheng

2009-09-30

In this study, C-N-S-tridoped titanium dioxide (TiO(2)) nanocrystals were synthesized by using a facile hydrothermal method in the presence of a biomolecule l-cysteine. This biomolecule could not only serve as the common source for the carbon, sulfur and nitrogen tridoping, but also could control the final crystal phases and morphology. The resulting materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption and UV-vis diffuse reflectance spectroscopy. XPS analysis revealed that S was incorporated into the lattice of TiO(2) through substituting oxygen atoms, N might coexist in the forms of N-Ti-O and Ti-O-N in tridoped TiO(2) and most C could form a mixed layer of carbonate species deposited on the surface of TiO(2) nanoparticles. The photocatalytic activities of the samples were tested on the removal of NO at typical indoor air level in a flow system under simulated solar light irradiation. The tridoped TiO(2) samples showed much higher removal efficiency than commercial P25 and the undoped counterpart photocatalyst. The enhanced visible light photocatalytic activity of C-N-S-tridoped TiO(2) nanocrystals was explained on the basis of characterizations. The possible formation process of the monodispersed C-N-S-tridoped anatase TiO(2) nanocrystals was also proposed. This study provides a new method to prepare visible light active TiO(2) photocatalyst.

Atomic force microscopy and X-ray photoelectron spectroscopy study of NO2 reactions on CaCO3 (1014) surfaces in humid environments.

PubMed

Baltrusaitis, Jonas; Grassian, Vicki H

2012-09-13

In this study, alternating current (AC) mode atomic force microscopy (AFM) combined with phase imaging and X-ray photoelectron spectroscopy (XPS) were used to investigate the effect of nitrogen dioxide (NO2) adsorption on calcium carbonate (CaCO3) (101̅4) surfaces at 296 K in the presence of relative humidity (RH). At 70% RH, CaCO3 (101̅4) surfaces undergo rapid formation of a metastable amorphous calcium carbonate layer, which in turn serves as a substrate for recrystallization of a nonhydrated calcite phase, presumably vaterite. The adsorption of nitrogen dioxide changes the surface properties of CaCO3 (101̅4) and the mechanism for formation of new phases. In particular, the first calcite nucleation layer serves as a source of material for further island growth; when it is depleted, there is no change in total volume of nitrocalcite, Ca(NO3)2, particles formed whereas the total number of particles decreases. This indicates that these particles are mobile and coalesce. Phase imaging combined with force curve measurements reveals areas of inhomogeneous energy dissipation during the process of water adsorption in relative humidity experiments, as well as during nitrocalcite particle formation. Potential origins of the different energy dissipation modes within the sample are discussed. Finally, XPS analysis confirms that NO2 adsorbs on CaCO3 (101̅4) in the form of nitrate (NO3(-)) regardless of environmental conditions or the pretreatment of the calcite surface at different relative humidity.

XPS and Raman studies of Pt catalysts supported on activated carbon

NASA Astrophysics Data System (ADS)

Tyagi, Deepak; Varma, Salil; Bharadwaj, S. R.

2018-04-01

Activated carbon is a widely used support for dispersing noble metals in addition to its many applications. We have prepared platinum catalyst supported on activated carbon for HI decomposition reaction of I-S thermochemical process of hydrogen generation. These catalysts were characterized by XPS and Raman before and after using for the reaction. It was observed that platinum is present in zero oxidation state, while carbon is present is both sp2 and sp3 hybridized forms along with some amount of it bonded to oxygen.

A critical study of the role of the surface oxide layer in titanium bonding

NASA Technical Reports Server (NTRS)

Dias, S.; Wightman, J. P.

1983-01-01

Scanning electron microscope/X-ray photoelectron spectroscopy (SEM/XPS) analysis of fractured adhesively bonded Ti 6-4 samples is discussed. The text adhesives incuded NR 056X polyimide, polypheylquinoxaline (PPQ), and LARC-13 polyimide. Differentiation between cohesive and interfacial failure was based on the absence of presence of a Ti 2p XPS photopeak. In addition, the surface oxide layer on Ti-(6A1-4V) adherends is characterized and bond strength and durability are addressed. Bond durability in various environmental conditions is discussed.

High permittivity polyaniline-barium titanate nanocomposites with excellent electromagnetic interference shielding response

NASA Astrophysics Data System (ADS)

Saini, Parveen; Arora, Manju; Gupta, Govind; Gupta, Bipin Kumar; Singh, Vidya Nand; Choudhary, Veena

2013-05-01

Organic conductive polymers are at the forefront of materials science research because of their diverse applications built around their interesting and unique properties. This work reports for the first time a correlation between the structural, electrical, and electromagnetic properties of polyaniline (PANI)-tetragonal BaTiO3 (TBT) nanocomposites prepared by in-situ emulsion polymerization. XRD studies and HRTEM micrographs of these nanocomposites clearly revealed the incorporation of TBT nanoparticles in the conducting PANI matrix. EPR and XPS measurements reveal that increase in loading level of BaTiO3 results in a reduction of the doping level of PANI. The Ku-Band (12.4-18 GHz) network analysis of these composites shows exceptional microwave shielding response with absorption dominated total shielding effectiveness (SET) value of -71.5 dB (blockage of more than 99.99999% of incident radiation) which is the highest value reported in the literature. Such a high attenuation level, which critically depends on the fraction of BaTiO3 is attributed to optimized dielectric and electrical attributes. This demonstrates the possibility of using these materials in stealth technology and for making futuristic radar absorbing materials (RAMs).Organic conductive polymers are at the forefront of materials science research because of their diverse applications built around their interesting and unique properties. This work reports for the first time a correlation between the structural, electrical, and electromagnetic properties of polyaniline (PANI)-tetragonal BaTiO3 (TBT) nanocomposites prepared by in-situ emulsion polymerization. XRD studies and HRTEM micrographs of these nanocomposites clearly revealed the incorporation of TBT nanoparticles in the conducting PANI matrix. EPR and XPS measurements reveal that increase in loading level of BaTiO3 results in a reduction of the doping level of PANI. The Ku-Band (12.4-18 GHz) network analysis of these composites shows exceptional microwave shielding response with absorption dominated total shielding effectiveness (SET) value of -71.5 dB (blockage of more than 99.99999% of incident radiation) which is the highest value reported in the literature. Such a high attenuation level, which critically depends on the fraction of BaTiO3 is attributed to optimized dielectric and electrical attributes. This demonstrates the possibility of using these materials in stealth technology and for making futuristic radar absorbing materials (RAMs). Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00634d

Novel applications of X-ray photoelectron spectroscopy on unsupported nanoparticles

NASA Astrophysics Data System (ADS)

Kostko, Oleg; Xu, Bo; Jacobs, Michael I.; Ahmed, Musahid

X-ray photoelectron spectroscopy (XPS) is a powerful technique for chemical analysis of surfaces. We will present novel results of XPS on unsupported, gas-phase nanoparticles using a velocity-map imaging (VMI) spectrometer. This technique allows for probes of both the surfaces of nanoparticles via XPS as well as their interiors via near edge X-ray absorption fine structure (NEXAFS) spectroscopy. A recent application of this technique has confirmed that arginine's guanidinium group exists in a protonated state even in strongly basic solution. Moreover, the core-level photoelectron spectroscopy can provide information on the effective attenuation length (EAL) of low kinetic energy electrons. This contradictory value is important for determining the probing depth of XPS and in photolithography. A new method for determining EALs will be presented.

Carbon in olivine single crystals analyzed by the 12C(d, p) 13C method and by photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Oberheuser, Gert; Kathrein, Hendrik; Demortier, Guy; Gonska, Horst; Freund, Friedemann

1983-06-01

Carbon subsurface concentration profiles in olivine single crystals from San Carlos, Arizona, and the Sergebet Island. Red Sea, containing total carbon between 60-180 wt.-ppm, were analyzed by means of the 12C(d. p) 13C nuclear reaction and by x-ray induced photoelectron spectroscopy (XPS) in combination with acid etching and with Ar + ion sputtering respectively, between 200-930 K. The (d, p) analysis reveals equilibrium subsurface C profiles extending 1-2 μm or more into the bulk. Their steepness is a function of temperature. Typical mean C concentrations at 300 K in the resolvable layers, 0-0.6, 0.6-1.2, and 1.2-1.8 μm. are 1.8, and 0.6 wt.-%, corresponding to enrichment factors over the mean bulk C concentration of the order of 100, 40 and 30 respectively. In the topmost atomic layers analyzed by XPS the carbon is enriched by a factor of the order of 1000, decreasing with increasing temperature. The results suggest that the carbon is in a truly dissolved state and highly mobile, subject to a reversible subsurface segregation. Most probably local lattice strain associated with the solute C species provide the driving force for this diffusional process. The C diffusion coefficient was determined from the (d, p) data below 300 K: D= 10 -13 exp(-7.8/RT) [m 2· sec -1; KJ · mole -1] and from XPS data between 450-925 K: D = 10 -14 exp(-6/RT) [m 2 · sec -1; KJ · mole -1] The estimated error of the preexponential factors is ± one order of magnitude, that of the activation energies ±3.5 and ±2 KJ mole -1 respectively.

Effect of sulfur hexafluoride gas and post-annealing treatment for inductively coupled plasma etched barium titanate thin films

PubMed Central

2014-01-01

Aerosol deposition- (AD) derived barium titanate (BTO) micropatterns are etched via SF6/O2/Ar plasmas using inductively coupled plasma (ICP) etching technology. The reaction mechanisms of the sulfur hexafluoride on BTO thin films and the effects of annealing treatment are verified through X-ray photoelectron spectroscopy (XPS) analysis, which confirms the accumulation of reaction products on the etched surface due to the low volatility of the reaction products, such as Ba and Ti fluorides, and these residues could be completely removed by the post-annealing treatment. The exact peak positions and chemicals shifts of Ba 3d, Ti 2p, O 1 s, and F 1 s are deduced by fitting the XPS narrow-scan spectra on as-deposited, etched, and post-annealed BTO surfaces. Compared to the as-deposited BTOs, the etched Ba 3d 5/2 , Ba 3d 3/2 , Ti 2p 3/2 , Ti 2p 1/2 , and O 1 s peaks shift towards higher binding energy regions by amounts of 0.55, 0.45, 0.4, 0.35, and 0.85 eV, respectively. A comparison of the as-deposited film with the post-annealed film after etching revealed that there are no significant differences in the fitted XPS narrow-scan spectra except for the slight chemical shift in the O 1 s peak due to the oxygen vacancy compensation in O2-excessive atmosphere. It is inferred that the electrical properties of the etched BTO film can be restored by post-annealing treatment after the etching process. Moreover, the relative permittivity and loss tangent of the post-annealed BTO thin films are remarkably improved by 232% and 2,695%, respectively. PMID:25249824

Atomistic characterisation of Li+ mobility and conductivity in Li(7-x)PS(6-x)Ix argyrodites from molecular dynamics simulations, solid-state NMR, and impedance spectroscopy.

PubMed

Pecher, Oliver; Kong, Shiao-Tong; Goebel, Thorsten; Nickel, Vera; Weichert, Katja; Reiner, Christof; Deiseroth, Hans-Jörg; Maier, Joachim; Haarmann, Frank; Zahn, Dirk

2010-07-26

The atomistic mechanisms of Li(+) ion mobility/conductivity in Li(7-x)PS(6-x)I(x) argyrodites are explored from both experimental and theoretical viewpoints. Ionic conductivity in the title compound is associated with a solid-solid phase transition, which was characterised by low-temperature differential scanning calorimetry, (7)Li and (127)I NMR investigations, impedance measurements and molecular dynamics simulations. The NMR signals of both isotopes are dominated by anisotropic interactions at low temperatures. A significant narrowing of the NMR signal indicates a motional averaging of the anisotropic interactions above 177+/-2 K. The activation energy to ionic conductivity was assessed from both impedance spectroscopy and molecular dynamics simulations. The latter revealed that a series of interstitial sites become accessible to the Li(+) ions, whilst the remaining ions stay at their respective sites in the argyrodite lattice. The interstitial positions each correspond to the centres of tetrahedra of S/I atoms, and differ only in terms of their common corners, edges, or faces with adjacent PS(4) tetrahedra. From connectivity analyses and free-energy rankings, a specific tetrahedron is identified as the key restriction to ionic conductivity, and is clearly differentiated from local mobility, which follows a different mechanism with much lower activation energy. Interpolation of the lattice parameters as derived from X-ray diffraction experiments indicates a homogeneity range for Li(7-x)PS(6-x)I(x) with 0.97 < or = x < or = 1.00. Within this range, molecular dynamics simulations predict Li(+) conductivity at ambient conditions to vary considerably.

Surface passivation and aging of InGaAs/InP heterojunction phototransistors

NASA Astrophysics Data System (ADS)

Park, Min-Su; Razaei, Mohsen; Barnhart, Katie; Tan, Chee Leong; Mohseni, Hooman

2017-06-01

We report the effect of different surface treatment and passivation techniques on the stability of InGaAs/InP heterojunction phototransistors (HPTs). An In0.53Ga0.47As surface passivated with aqueous ammonium sulfide ((NH4)2S), aluminum oxide (Al2O3) grown by atomic layer deposition (ALD), and their combination is evaluated by using Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). All samples were kept in the air ambient, and their performances were periodically measured to investigate their long-term stability. Raman spectroscopy revealed that the peak intensity of the GaAs-like longitudinal optical phonon of all passivated samples is decreased compared with that of the control sample. This is attributable to the diminution of the carriers near the passivated surfaces, which was proven by extracted surface potential (Vs). The Vs of all passivated samples was decreased to less than half of that for the control sample. XPS evaluation of As3d spectra showed that arsenic oxides (As2O3 and As2O5) on the surfaces of the samples can be removed by passivation. However, both Raman and XPS spectra show that the (NH4)2S passivated sample reverts back over time and will resemble the untreated control sample. When capped with ALD-grown Al2O3, passivated samples irrespective of the pretreatment show no degradation over the measured time of 4 weeks. Similar conclusions are made from our experimental measurement of the performance of differently passivated HPTs. The ALD-grown Al2O3 passivated devices show an improved optical gain at low optical powers and long-term stability.

Combined PIXE and XPS analysis on republican and imperial Roman coins

NASA Astrophysics Data System (ADS)

Daccà, A.; Prati, P.; Zucchiatti, A.; Lucarelli, F.; Mandò, P. A.; Gemme, G.; Parodi, R.; Pera, R.

2000-03-01

A combined PIXE and XPS analysis has been performed on a few Roman coins of the republican and imperial age. The purpose was to investigate via XPS the nature and extent of patina in order to be capable of extracting PIXE data relative to the coins bulk. The inclusion of elements from the surface layer, altered by oxidation and inclusion, is a known source of uncertainty in PIXE analyses of coins, performed to assess the composition and the provenance.

Organometallic chemical vapor deposition of silicon nitride films enhanced by atomic nitrogen generated from surface-wave plasma

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

Okada, H.; Kato, M.; Ishimaru, T.

2014-02-20

Organometallic chemical vapor deposition of silicon nitride films enhanced by atomic nitrogen generated from surface-wave plasma is investigated. Feasibility of precursors of triethylsilane (TES) and bis(dimethylamino)dimethylsilane (BDMADMS) is discussed based on a calculation of bond energies by computer simulation. Refractive indices of 1.81 and 1.71 are obtained for deposited films with TES and BDMADMS, respectively. X-ray photoelectron spectroscopy (XPS) analysis of the deposited film revealed that TES-based film coincides with the stoichiometric thermal silicon nitride.

Characterization of atmospheric pressure plasma treated wool/cashmere textiles: Treatment in nitrogen

NASA Astrophysics Data System (ADS)

Zanini, Stefano; Citterio, Attilio; Leonardi, Gabriella; Riccardi, Claudia

2018-01-01

We performed atmospheric pressure plasma treatments of wool/cashmere (15/85%) textiles with a dielectric barrier discharge (DBD) in nitrogen. The chemical properties of the plasma treated samples were investigated with attenuated total reflectance Fourier transform infrared (FTIR/ATR) spectroscopy, X-ray photoelectron microscopy (XPS), and fatty acid gas chromatographic analysis. Changes in mechanical properties and tactile performance of textiles after the plasma treatment were determined using the KES-F system. The analyses reveal significant surface modification of the treated fabrics, which enhances their surface wettability.

Surface study of stainless steel electrode deposition from soil electrokinetic (EK) treatment using X-ray photoelectron spectroscopy (XPS)

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

Embong, Zaidi, E-mail: zaidi@uthm.edu.my; Research Centre for Soft Soils; Johar, Saffuwan

2015-04-29

Electrokinetic (EK) remediation relies upon application of a low-intensity direct current through the soil between stainless steel electrodes that are divided into a cathode array and an anode array. This mobilizes charged species, causing ions and water to move toward the electrodes. Metal ions and positively charged organic compounds move toward the cathode. Anions such as chloride, fluoride, nitrate, and negatively charged organic compounds move toward the anode. Here, this remediation techniques lead to a formation of a deposition at the both cathode and anode surface that mainly contributed byanion and cation from the remediated soil. In this research, Renggam-Jerangaumore » soil species (HaplicAcrisol + RhodicFerralsol) with a surveymeter reading of 38.0 ± 3.9 μR/hr has been investigation in order to study the mobility of the anion and cation under the influence electric field. Prior to the EK treatment, the elemental composition of the soil and the stainless steel electrode are measured using XRF analyses. Next, the soil sample is remediated at a constant electric potential of 30 V within an hour of treatment period. A surface study for the deposition layer of the cathode and anode using X-ray Photoelectron spectroscopy (XPS) revealed that a narrow photoelectron signal from oxygen O 1s, carbon, C 1s silica, Si 2p, aluminium, Al 2p and chromium, Cr 2p exhibited on the electrode surface and indicate that a different in photoelectron intensity for each element on both electrode surface. In this paper, the mechanism of Si{sup 2+} and Al{sup 2+} cation mobility under the influence of voltage potential between the cathode and anode will be discussed in detail.« less

Surface modification of several dental substrates by non-thermal, atmospheric plasma brush.

PubMed

Chen, Mingsheng; Zhang, Ying; Sky Driver, M; Caruso, Anthony N; Yu, Qingsong; Wang, Yong

2013-08-01

The purpose of this study was to reveal the effectiveness of non-thermal atmospheric plasma brush in surface wettability and modification of four dental substrates. Specimens of dental substrates including dentin, enamel, and two composites Filtek Z250, Filtek LS Silorane were prepared (∼2mm thick, ∼10mm diameter). The prepared surfaces were treated for 5-45s with a non-thermal atmospheric plasma brush working at temperatures from 36 to 38°C. The plasma-treatment effects on these surfaces were studied with contact-angle measurement, X-ray photoemission spectroscopy (XPS) and scanning electron microscopy (SEM). The non-thermal atmospheric argon plasma brush was very efficient in improving the surface hydrophilicity of four substrates studied. The results indicated that water contact angle values decreased considerably after only 5s plasma treatment of all these substrates. After 30s treatment, the values were further reduced to <5°, which was close to a value for super hydrophilic surfaces. XPS analysis indicated that the percent of elements associated with mineral in dentin/enamel or fillers in the composites increased. In addition, the percent of carbon (%C) decreased while %O increased for all four substrates. As a result, the O/C ratio increased dramatically, suggesting that new oxygen-containing polar moieties were formed on the surfaces after plasma treatment. SEM surface images indicated that no significant morphology change was induced on these dental substrates after exposure to plasmas. Without affecting the bulk properties, a super-hydrophilic surface could be easily achieved by the plasma brush treatment regardless of original hydrophilicity/hydrophobicity of dental substrates tested. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Surface modification of several dental substrates by non-thermal, atmospheric plasma brush

PubMed Central

Chen, Mingsheng; Zhang, Ying; Driver, M. Sky; Caruso, Anthony N.; Yu, Qingsong; Wang, Yong

2013-01-01

Objective The purpose of this study was to reveal the effectiveness of non-thermal atmospheric plasma brush in surface wettability and modification of four dental substrates. Methods Specimens of dental substrates including dentin, enamel, and two composites Filtek Z250, Filtek LS Silorane were prepared (~2 mm thick, ~10 mm diameter). The prepared surfaces were treated for 5–45 s with a non-thermal atmospheric plasma brush working at temperatures from 36 to 38 °C. The plasma-treatment effects on these surfaces were studied with contact-angle measurement, X-ray photoemission spectroscopy (XPS) and scanning electron microscopy (SEM). Results The non-thermal atmospheric argon plasma brush was very efficient in improving the surface hydrophilicity of four substrates studied. The results indicated that water contact angle values decreased considerably after only 5 s plasma treatment of all these substrates. After 30 s treatment, the values were further reduced to <5°, which was close to a value for super hydrophilic surfaces. XPS analysis indicated that the percent of elements associated with mineral in dentin/enamel or fillers in the composites increased. In addition, the percent of carbon (%C) decreased while %O increased for all four substrates. As a result, the O/C ratio increased dramatically, suggesting that new oxygen-containing polar moieties were formed on the surfaces after plasma treatment. SEM surface images indicated that no significant morphology change was induced on these dental substrates after exposure to plasmas. Significance Without affecting the bulk properties, a super-hydrophilic surface could be easily achieved by the plasma brush treatment regardless of original hydrophilicity/hydrophobicity of dental substrates tested. PMID:23755823

Analysis of microstructure in electro-spark deposited IN718 superalloy

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

Anisimov, E.; Khan, A.K.; Ojo, O.A., E-mail: olanr

2016-09-15

The microstructure of electro-spark deposited (ESD) superalloy IN718 was studied by the use of scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) techniques. In converse to general assumption, the extremely high cooling rate involved in the ESD process did not produce partitionless solidification that is devoid of second phase microconstituents in the material, nano-sized Laves phase and MC carbide particles were observed within the deposited layer. Notwithstanding the several thermal cycles involved in the process, the extremely low heat input of the process produced a deposited region that is free ofmore » the main strengthening phase of the alloy, γ″ phase precipitates, which is in contrast to what have been reported on laser deposition. Nevertheless, application of the standard full heat treatment of the alloy resulted in extensive formation of the γ″ phase precipitates and δ phase precipitates, the most stable secondary phase of the alloy, with nearly, if not complete, dissolution of the Laves phase particles. Furthermore, the XPS analysis done in the study revealed the formation of nano-oxides within the deposited layer, which increased the microhardness of the superalloy in the as-deposited condition and inhibited its grain growth during post-process heat treatment. The microstructure analysis done in this work is crucial to the understanding of properties of the superalloy processed by the ESD technique. - Highlights: •Electron microscopy analyses of electro-spark deposited IN 718 superalloy were performed. •Nano-sized secondary phase particles were observed within the deposited layer. •The study shows that the ESD did not produce partitionless solidification of the alloy.« less

Arsenic(V) removal from groundwater using nano scale zero-valent iron as a colloidal reactive barrier material.

PubMed

Kanel, Sushil Raj; Greneche, Jean-Mark; Choi, Heechul

2006-03-15

The removal of As(V), one of the most poisonous groundwater pollutants, by synthetic nanoscale zero-valent iron (NZVI) was studied. Batch experiments were performed to investigate the influence of pH, adsorption kinetics, sorption mechanism, and anionic effects. Field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Mossbauer spectroscopy were used to characterize the particle size, surface morphology, and corrosion layer formation on pristine NZVI and As(V)-treated NZVI. The HR-TEM study of pristine NZVI showed a core-shell-like structure, where more than 90% of the nanoparticles were under 30 nm in diameter. Mössbauer spectroscopy further confirmed its structure in which 19% were in zero-valent state with a coat of 81% iron oxides. The XRD results showed that As(V)-treated NZVI was gradually converted into magnetite/maghemite corrosion products over 90 days. The XPS study confirmed that 25% As(V) was reduced to As(III) by NZVI after 90 days. As(V) adsorption kinetics were rapid and occurred within minutes following a pseudo-first-order rate expression with observed reaction rate constants (Kobs) of 0.02-0.71 min(-1) at various NZVI concentrations. Laser light scattering analysis confirmed that NZVI-As(V) forms an inner-sphere surface complexation. The effects of competing anions revealed that HCO3-, H4SiO4(0), and H2PO4(2-) are potential interfering agents in the As(V) adsorption reaction. Our results suggest that NZVI is a suitable candidate for As(V) remediation.

Gd-Complexes of New Arylpiperazinyl Conjugates of DTPA-Bis(amides): Synthesis, Characterization and Magnetic Relaxation Properties.

PubMed

Ba-Salem, Abdullah O; Ullah, Nisar; Shaikh, M Nasiruzzaman; Faiz, Mohamed; Ul-Haq, Zaheer

2015-04-29

Two new DTPA-bis(amide) based ligands conjugated with the arylpiperazinyl moiety were synthesized and subsequently transformed into their corresponding Gd(III) complexes 1 and 2 of the type [Gd(L)H2O]·nH2O. The relaxivity (R1) of these complexes was measured, which turned out to be comparable with that of Omniscan®, a commercially available MRI contrast agent. The cytotoxicity studies of these complexes indicated that they are non-toxic, which reveals their potential and physiological suitability as MRI contrast agents. All the synthesized ligands and complexes were characterized with the aid of analytical and spectroscopic methods, including elemental analysis, 1H-NMR, FT-IR, XPS and fast atom bombardment (FAB) mass spectrometry.

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

PubMed

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

2011-08-01

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

Enhancement of acid treated g-C3N4sbnd Cu2O photocatalytic activity by PEG under visible light irradiation

NASA Astrophysics Data System (ADS)

Zuo, Shiyu; Xu, Haiming; Liao, Wei; Sun, Lei; Li, Qiang; Zan, Jie; Zhang, Binyang; Li, Dongya; Xia, Dongsheng

2018-05-01

In this study, g-C3N4sbnd Cu2O was successfully synthesized in the presence of PEG-400 surfactant via an acid treatment hydrothermal method and a high-temperature calcination method. The structures and properties of as-synthesized samples were characterized using a range of techniques, such as XPS, TEM, PL and BET. The g-C3N4sbnd Cu2O heterojunction exhibits the enhanced photocatalytic performance and high stability. It is revealed that the addition of PEG can promote the heterojunction effect of g-C3N4sbnd Cu2O, effectively improving the crystallinity and specific surface area of the photocatalyst, separation efficiency of photocarriers, and light absorption, thus enhancing the photocatalytic performance.

Preparation and characterisation of carbon-free Cu(111) films on sapphire for graphene synthesis

NASA Astrophysics Data System (ADS)

Lehnert, J.; Spemann, D.; Surjuse, S.; Mensing, M.; Grüner, C.; With, P.; Schumacher, P.; Finzel, A.; Hirsch, D.; Rauschenbach, B.

2018-03-01

This work presents an investigation of carbon formed on polycrystalline Cu(111) thin films prepared by ion beam sputtering at room temperature on c-plane Al2O3 after thermal treatment in a temperature range between 300 and 1020°C. The crystallinity of the Cu films was studied by XRD and RBS/channeling and the surface was characterised by Raman spectroscopy, XPS and AFM for each annealing temperature. RBS measurements revealed the diffusion of the Cu into the Al2O3 substrate at high temperatures of > 700°C. Furthermore, a cleaning procedure using UV ozone treatment is presented to remove the carbon from the surface which yields essentially carbon-free Cu films that open the possibility to synthesize graphene of well-controlled thickness (layer number).

A comparative theoretical study on core-hole excitation spectra of azafullerene and its derivatives

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

Deng, Yunfeng; Department of Physics, Guizhou University, Guiyang 550025; Gao, Bin, E-mail: bin.gao@uit.no

2014-03-28

The core-hole excitation spectra—near-edge x-ray absorption spectroscopy (NEXAFS), x-ray emission spectroscopy (XES), and x-ray photoelectron spectroscopy (XPS) shake-up satellites have been simulated at the level of density functional theory for the azafullerene C{sub 59}N and its derivatives (C{sub 59}N){sup +}, C{sub 59}HN, (C{sub 59}N){sub 2}, and C{sub 59}N–C{sub 60}, in which the XPS shake-up satellites were simulated using our developed equivalent core hole Kohn-Sham (ECH-KS) density functional theory approach [B. Gao, Z. Wu, and Y. Luo, J. Chem. Phys. 128, 234704 (2008)] which aims for the study of XPS shake-up satellites of large-scale molecules. Our calculated spectra are generally inmore » good agreement with available experimental results that validates the use of the ECH-KS method in the present work. The nitrogen K-edge NEXAFS, XES, and XPS shake-up satellites spectra in general can be used as fingerprints to distinguish the azafullerene C{sub 59}N and its different derivatives. Meanwhile, different carbon K-edge spectra could also provide detailed information of (local) electronic structures of different molecules. In particular, a peak (at around 284.5 eV) in the carbon K-edge NEXAFS spectrum of the heterodimer C{sub 59}N–C{sub 60} is confirmed to be related to the electron transfer from the C{sub 59}N part to the C{sub 60} part in this charge-transfer complex.« less

Structural and surface properties of CuO-ZnO-Cr{sub 2}O{sub 3} catalysts and their relationship with selectivity to higher alcohol synthesis

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

Campos-Martin, J.M.; Fierro, J.L.G.; Guerrero-Ruiz, A.

1995-10-01

A series of copper-zinc-chromium catalysts of different compositions and calcination temperatures has been prepared, characterized by several techniques (BET specific surface area, XRD, gravimetric TPR, TPD-CO, and XPS), and tested under high alcohol synthesis (HAS) conditions. CO hydrogenation was carried out at reaction temperatures of 523-598 K and 50 bar total pressure. The influence of catalyst composition, calcination temperature, and surface characteristics on the HAS selectivity was studied. The optimum HAS yields were found in the low Cr content region, but chromium was needed. Although chromium oxide does not seem to be involved in the catalytic site, its presence inmore » the catalyst composition is essential, owing to the larger specific surfaces and catalyst stability obtained at the highest reaction temperatures. For low Cr content composition, the temperature-programmed reduction (TPR) profiles were shifted to higher temperatures and simultaneously larger CO{sub 2} amounts were found in the temperature-programmed desorption profiles of adsorbed CO (TPD-CO). Photoelectron spectra (XPS) revealed that the oxidation state of copper is Cu{sup 2+} in the calcined catalysts and Cu{sup O} in the reduced ones; Cu{sup +} was only stabilized in a CuCr{sub 2}O{sub 4} spinel in the Cr-rich catalysts. These features derived from catalyst characterization are discussed in the framework of the catalytic behaviour for HAS synthesis. 53 refs., 7 figs., 4 tabs.« less

A P25/(NH4)xWO3 hybrid photocatalyst with broad spectrum photocatalytic properties under UV, visible, and near-infrared irradiation

NASA Astrophysics Data System (ADS)

Yang, Linfen; Liu, Bin; Liu, Tongyao; Ma, Xinlong; Li, Hao; Yin, Shu; Sato, Tsugio; Wang, Yuhua

2017-04-01

In this study, a series of hybrid nanostructured photocatalysts P25/(NH4)xWO3 nanocomposites with the average crystallite size of P25 and (NH4)xWO3 of the sample was calculated to be about 30 nm and 130 nm, were successfully synthesized via a simple one-step hydrothermal method. The as-obtained samples was characterized by transmission electron microscopy (TEM), which implies that the P25/(NH4)xWO3 nanocomposites are fabricated with favourable nanosizd interfacial. The XPS results confirmed that the obtained sample consists of mixed chemical valences of W5+ and W6+, the low-valance W5+ sites could be the origin of NIR absorption. As revealed by optical absorption results, P25/(NH4)xWO3 nanocomposites possess high optical absorption in the whole solar spectrum of 200-2500 nm. Benefiting from this unique photo-absorption property and the synergistic effect of P25 and (NH4)xWO3, broad spectrum response photocatalytic activities covering UV, visible and near infrared regions on degradation of Rhodamine B have been realized by P25/(NH4)xWO3 nanocomposites. Meanwhile, the stability of photocatalysts was examined by the XRD and XPS of the photocatalysts after the reaction. The results show that P25/(NH4)xWO3 photocatalysts has a brilliant application prospect in the energy utilization to solve deteriorating environmental issues.

The characterization of Cr secondary oxide phases in ZnO films studied by X-ray spectroscopy and photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Chiou, J. W.; Chang, S. Y.; Huang, W. H.; Chen, Y. T.; Hsu, C. W.; Hu, Y. M.; Chen, J. M.; Chen, C.-H.; Kumar, K.; Guo, J.-H.

2011-03-01

X-ray absorption near-edge structure (XANES), X-ray emission spectroscopy (XES), and X-ray photoemission spectroscopy (XPS) were used to characterize the Cr secondary oxide phases in ZnO films that had been prepared using a co-sputtering method. Analysis of the Cr L3,2-edge XANES spectra reveals that the intensity of white-line features decreases subtly as the sputtering power increases, indicating that the occupation of Cr 3 d orbitals increases with Cr concentration in (Zn, Cr)O films. The O K-edge spectra show that the intensity of XANES features of (Zn, Cr)O films is lower than those of ZnO film, suggesting enhanced occupation of O 2 p-derived states through O 2 p-Cr 3 d hybridization. The XES and XPS spectra indicate that the line shapes in the valence band of (Zn, Cr)O films are quite different from those of ZnO and that the Cr 2O 3 phase dominates the spinel structure of (Zn, Cr)O films increasingly as the Cr sputtering power is increased. Over all results suggest that the non-ferromagnetic behavior of (Zn, Cr)O films can be attributed to the dominant presence of Cr 2O 3, whereas the bulk comprise phase segregations of Cr 2O 3 and/or ZnCr 2O 4, which results them the most stable TM-doped ZnO material against etching.

The effect of gradient boracic polyanion-doping on structure, morphology, and cycling performance of Ni-rich LiNi0.8Co0.15Al0.05O2 cathode material

NASA Astrophysics Data System (ADS)

Chen, Tao; Li, Xiang; Wang, Hao; Yan, Xinxiu; Wang, Lei; Deng, Bangwei; Ge, Wujie; Qu, Meizhen

2018-01-01

A gradient boracic polyanion-doping method is applied to Ni-rich LiNi0.8Co0.15Al0.05O2 (NCA) cathode material in this study to suppress the capacity/potential fade during charge-discharge cycling. Scanning electron microscope (SEM) results show that all samples present spherical morphology and the secondary particle size increases with increasing boron content. X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) results demonstrate that boracic polyanions are successfully introduced into the bulk material and more enriched in the outer layer. XPS analysis further reveals that the valence state of Ni3+ is partly reduced to Ni2+ at the surface due to the incorporation of boracic polyanions. From the electrochemical measurements, B0.015-NCA electrode exhibits excellent cycling performance, even at high potential and elevated temperature. Moreover, the SEM images illustrate the presence of cracks and a thick SEI layer on pristine particles after 100 cycles at high temperature, while the B0.015-NCA particles show an intact structure and thin SEI layer. Electrochemical impedance spectroscopy confirms that the boracic polyanion doping could hinder the impedance increase during cycling at elevated temperature. These results clearly indicate that the gradient boracic polyanion-doping contributes to the remarkable enhancement of structure stability and cycling performance of NCA.

Treatment for GaSb surfaces using a sulphur blended (NH4)2S/(NH4)2SO4 solution

NASA Astrophysics Data System (ADS)

Murape, D. M.; Eassa, N.; Neethling, J. H.; Betz, R.; Coetsee, E.; Swart, H. C.; Botha, J. R.; Venter, A.

2012-07-01

A sulphur based chemical, [(NH4)2S/(NH4)2SO4] to which S has been added, not previously reported for the treatment of (1 0 0) n-GaSb surfaces, is introduced and benchmarked against the commonly used passivants Na2S·9H2O and (NH4)2S. The surfaces of the treated material were studied by scanning electron microscopy (SEM), Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). It has been found that the native oxides present on the GaSb surface are more effectively removed when treated with ([(NH4)2S/(NH4)2SO4] + S) than with (NH4)2S or Na2S·9H2O, as evidenced by the ratio of the O506 eV to Sb457 eV AES peaks. XPS results reveal that Sb2S3/Sb2S5 "replaces" Sb2O3/Sb2O5, suggesting that sulphur atoms substitute oxygen atoms in Sb2O3/Sb2O5 to form Sbsbnd S. It seems sulphurization only partially removes Ga2O3. Treatment with ([(NH4)2S/(NH4)2SO4] + S) also results in a noteworthy improvement in the current-voltage (I-V) characteristics of Au/n-GaSb Schottky contacts compared to those fabricated on as-received material.

A P25/(NH4)xWO3 hybrid photocatalyst with broad spectrum photocatalytic properties under UV, visible, and near-infrared irradiation

PubMed Central

Yang, Linfen; Liu, Bin; Liu, Tongyao; Ma, Xinlong; Li, Hao; Yin, Shu; Sato, Tsugio; Wang, Yuhua

2017-01-01

In this study, a series of hybrid nanostructured photocatalysts P25/(NH4)xWO3 nanocomposites with the average crystallite size of P25 and (NH4)xWO3 of the sample was calculated to be about 30 nm and 130 nm, were successfully synthesized via a simple one-step hydrothermal method. The as-obtained samples was characterized by transmission electron microscopy (TEM), which implies that the P25/(NH4)xWO3 nanocomposites are fabricated with favourable nanosizd interfacial. The XPS results confirmed that the obtained sample consists of mixed chemical valences of W5+ and W6+, the low-valance W5+ sites could be the origin of NIR absorption. As revealed by optical absorption results, P25/(NH4)xWO3 nanocomposites possess high optical absorption in the whole solar spectrum of 200–2500 nm. Benefiting from this unique photo-absorption property and the synergistic effect of P25 and (NH4)xWO3, broad spectrum response photocatalytic activities covering UV, visible and near infrared regions on degradation of Rhodamine B have been realized by P25/(NH4)xWO3 nanocomposites. Meanwhile, the stability of photocatalysts was examined by the XRD and XPS of the photocatalysts after the reaction. The results show that P25/(NH4)xWO3 photocatalysts has a brilliant application prospect in the energy utilization to solve deteriorating environmental issues. PMID:28368032

Comparative study of GeO 2/Ge and SiO 2/Si structures on anomalous charging of oxide films upon water adsorption revealed by ambient-pressure X-ray photoelectron spectroscopy

DOE PAGES

Mori, Daichi; Oka, Hiroshi; Hosoi, Takuji; ...

2016-09-02

The energy difference between the oxide and bulk peaks in X-ray photoelectron spectroscopy (XPS) spectra was investigated in this paper for both GeO 2/Ge and SiO 2/Si structures with thickness-controlled water films. This was achieved by obtaining XPS spectra at various values of relative humidity (RH) of up to ~15%. The increase in the energy shift is more significant for thermal GeO 2 on Ge than for thermal SiO 2 on Si above ~10 -4% RH, which is due to the larger amount of water molecules that infiltrate into the GeO 2 film to form hydroxyls. Analyzing the origins ofmore » this energy shift, we propose that the positive charging of a partially hydroxylated GeO 2 film, which is unrelated to X-ray irradiation, causes the larger energy shift for GeO 2/Ge than for SiO 2/Si. A possible microscopic mechanism of this intrinsic positive charging is the emission of electrons from adsorbed water species in the suboxide layer of the GeO 2 film to the Ge bulk, leaving immobile cations or positively charged states in the oxide. Finally, this may be related to the reported negative shift of flat band voltages in metal-oxide-semiconductor diodes with an air-exposed GeO 2 layer.« less

A P25/(NH4)xWO3 hybrid photocatalyst with broad spectrum photocatalytic properties under UV, visible, and near-infrared irradiation.

PubMed

Yang, Linfen; Liu, Bin; Liu, Tongyao; Ma, Xinlong; Li, Hao; Yin, Shu; Sato, Tsugio; Wang, Yuhua

2017-04-03

In this study, a series of hybrid nanostructured photocatalysts P25/(NH 4 ) x WO 3 nanocomposites with the average crystallite size of P25 and (NH 4 ) x WO 3 of the sample was calculated to be about 30 nm and 130 nm, were successfully synthesized via a simple one-step hydrothermal method. The as-obtained samples was characterized by transmission electron microscopy (TEM), which implies that the P25/(NH 4 ) x WO 3 nanocomposites are fabricated with favourable nanosizd interfacial. The XPS results confirmed that the obtained sample consists of mixed chemical valences of W 5+ and W 6+ , the low-valance W 5+ sites could be the origin of NIR absorption. As revealed by optical absorption results, P25/(NH 4 ) x WO 3 nanocomposites possess high optical absorption in the whole solar spectrum of 200-2500 nm. Benefiting from this unique photo-absorption property and the synergistic effect of P25 and (NH 4 ) x WO 3 , broad spectrum response photocatalytic activities covering UV, visible and near infrared regions on degradation of Rhodamine B have been realized by P25/(NH 4 ) x WO 3 nanocomposites. Meanwhile, the stability of photocatalysts was examined by the XRD and XPS of the photocatalysts after the reaction. The results show that P25/(NH 4 ) x WO 3 photocatalysts has a brilliant application prospect in the energy utilization to solve deteriorating environmental issues.

Structural and electrochemical analysis of chemically synthesized microcubic architectured lead selenide thin films

NASA Astrophysics Data System (ADS)

Bhat, T. S.; Shinde, A. V.; Devan, R. S.; Teli, A. M.; Ma, Y. R.; Kim, J. H.; Patil, P. S.

2018-01-01

The present work deals with the synthesis of lead selenide (PbSe) thin films by simple and cost-effective chemical bath deposition method with variation in deposition time. The structural, morphological, and electrochemical properties of as-deposited thin films were examined using characterization techniques such as X-ray diffraction spectroscopy (XRD), field-emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), galvanostatic charge-discharge and electrochemical impedance spectroscopy. XRD reveals formation of rock salt phase cubic structured PbSe. FE-SEM images show the formation of microcubic structured morphology. The existence of the PbSe is confirmed from the XPS analysis. On the other hand, CV curves show four reaction peaks corresponding to oxidation [PbSe and Pb(OH)2] and reduction (PbO2 and Pb(OH)2) at the surface of PbSe thin films. The PbSe:2 sample deposited for 80 min. shows maximum specific capacitance of 454 ± 5 F g- 1 obtained at 0.25 mA cm- 2 current density. The maximum energy density of 69 Wh kg- 1 was showed by PbSe:2 electrode with a power density of 1077 W kg- 1. Furthermore, electrochemical impedance studies of PbSe:2 thin film show 80 ± 3% cycling stability even after 500 CV cycles. Such results show the importance of microcubic structured PbSe thin film as an anode in supercapacitor devices.

Structure, spectra and thermal, mechanical, Faraday rotation properties of novel diamagnetic SeO2-PbO-Bi2O3-B2O3 glasses

NASA Astrophysics Data System (ADS)

Chen, Qiuling; Su, Kai; Li, Yantao; Zhao, Zhiwei

2018-06-01

Faraday rotation diamagnetic glass has attracted research attentions in photonics, sensing and magneto optical devices due to their high refractive index, wide transmittance in UV and Fourier transform infrared (FT-IR) range and temperature independent Faraday rotation. Selenite modified heavy metal oxides glasses with composition of xSeO2-(10-x) B2O3-45PbO-45Bi2O3 (x = 0, 1, 5 and 10mol%) and 15%SeO2-40%PbO-45%Bi2O3 have been fabricated by melt-quenching method in present study. The influence of SeO2 on glass forming ability, thermal, mechanical properties and Faraday rotation were evaluated through X-ray Diffraction (XRD), Fourier transforms infrared spectra (FT-IR), Raman, X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), Vicker's hardness and Verdet constant measurements. XRD spectra reveal that the good vitrification was achieved for glass with SeO2 amounts ≤10% even without B2O3. FT-IR, Raman and XPS spectra ascertain the existence of characteristic vibration of SeO4, SeO3, PbO4, BiO3 and BO3 units. The incorporation of SeO2 increases the connectivity of glassy network by increasing the Tg, thermal stability and mechanical hardness. The small band gap, high polarizable Se4+ ions and isolated SeO3 units contribute to Faraday rotation improvement.

Effects of thermal annealing on the structural and optical properties of carbon-implanted SiO2.

PubMed

Poudel, P R; Paramo, J A; Poudel, P P; Diercks, D R; Strzhemechny, Y M; Rout, B; McDaniel, F D

2012-03-01

Amorphous carbon (a-C) nanoclusters were synthesized by the implantation of carbon ions (C-) into thermally grown silicon dioxide film (-500 nm thick) on a Si (100) wafer and processed by high temperature thermal annealing. The carbon ions were implanted with an energy of 70 keV at a fluence of 5 x 10(17) atoms/cm2. The implanted samples were annealed at 1100 degrees C for different time periods in a gas mixture of 96% Ar+4% H2. Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and High Resolution Transmission Electron Microscopy (HRTEM) were used to study the structural properties of both the as-implanted and annealed samples. HRTEM reveals the formation of nanostructures in the annealed samples. The Raman spectroscopy also confirms the formation of carbon nano-clusters in the samples annealed for 10 min, 30 min, 60 min and 90 min. No Raman features originating from the carbon-clusters are observed for the sample annealed further to 120 min, indicating a complete loss of implanted carbon from the SiO2 layer. The loss of the implanted carbon in the 120 min annealed sample from the SiO2 layer was also observed in the XPS depth profile measurements. Room temperature photoluminescence (PL) spectroscopy revealed visible emissions from the samples pointing to carbon ion induced defects as the origin of a broad 2.0-2.4 eV band, and the intrinsic defects in SiO2 as the possible origin of the -2.9 eV bands. In low temperature photoluminescence spectra, two sharp and intense photoluminescence lines at -3.31 eV and -3.34 eV appear for the samples annealed for 90 min and 120 min, whereas no such bands are observed in the samples annealed for 10 min, 30 min, and 60 min. The Si nano-clusters forming at the Si-SiO2 interface could be the origin of these intense peaks.

Self-assembly and graft polymerization route to Monodispersed Fe3O4@SiO2--polyaniline core-shell composite nanoparticles: physical properties.

PubMed

Reddy, Kakarla Raghava; Lee, Kwang-Pill; Kim, Ju Young; Lee, Youngil

2008-11-01

This study describes the synthesis of monodispersed core-shell composites of silica-modified magnetic nanoparticles and conducting polyaniline by self-assembly and graft polymerization. Magnetic ferrite nanoparticles (Fe3O4) were prepared by coprecipitation of Fe+2 and Fe+3 ions in alkaline solution, and then silananized. The silanation of magnetic particles (Fe3O4@SiO2) was carried out using 3-bromopropyltrichlorosilane (BPTS) as the coupling agent. FT-IR spectra indicated the presence of Fe--O--Si chemical bonds in Fe3O4@SiO2. Core-shell type nanocomposites (Fe3O4@SiO2/PANI) were prepared by grafting polyaniline (PANI) on the surface of silanized magnetic particles through surface initiated in-situ chemical oxidative graft polymerization. The nanocomposites were characterized by high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), Fourier transform infrared (FTIR) spectra, UV-visible spectroscopy, photoluminescence (PL) spectra, electrical conductivity and magnetic characteristics. HRTEM images of the nanocomposites revealed that the silica-modified magnetic particles made up the core while PANI made up the shell. The XPS spectrum revealed the presence of silica in the composites, and the XRD results showed that the composites were more crystalline than pure PANI. PL spectra show that composites exhibit photoluminescent property. Conductivity of the composites (6.2 to 9.4 x 10(-2) S/cm) was higher than that of pristine PANI (3.7 x 10(-3) S/cm). The nanocomposites exhibited superparamagnetism. Formation mechanism of the core-shell structured nanocomposites and the effect of modified magnetic nanoparticles on the electro-magnetic properties of the Fe3O4@SiO2/PANI nanocomposites are also investigated. This method provides a new strategy for the generation of multi-functional nanocomposites that composed of other conducting polymers and metal nanoparticles.

Investigation of the mechanical and chemical characteristics of nanotubular and nano-pitted anodic films on grade 2 titanium dental implant materials.

PubMed

Weszl, Miklós; Tóth, Krisztián László; Kientzl, Imre; Nagy, Péter; Pammer, Dávid; Pelyhe, Liza; Vrana, Nihal E; Scharnweber, Dieter; Wolf-Brandstetter, Cornelia; Joób F, Árpád; Bognár, Eszter

2017-09-01

The objective of this study was to investigate the reproducibility, mechanical integrity, surface characteristics and corrosion behavior of nanotubular (NT) titanium oxide arrays in comparison with a novel nano-pitted (NP) anodic film. Surface treatment processes were developed to grow homogenous NT and NP anodic films on the surface of grade 2 titanium discs and dental implants. The effect of process parameters on the surface characteristics and reproducibility of the anodic films was investigated and optimized. The mechanical integrity of the NT and NP anodic films were investigated by scanning electron microscopy, surface roughness measurement, scratch resistance and screwing tests, while the chemical and physicochemical properties were investigated in corrosion tests, contact angle measurement and X-ray photoelectron spectroscopy (XPS). The growth of NT anodic films was highly affected by process parameters, especially by temperature, and they were apt to corrosion and exfoliation. In contrast, the anodic growth of NP film showed high reproducibility even on the surface of 3-dimensional screw dental implants and they did not show signs of corrosion and exfoliation. The underlying reason of the difference in the tendency for exfoliation of the NT and NP anodic films is unclear; however the XPS analysis revealed fluorine dopants in a magnitude larger concentration on NT anodic film than on NP surface, which was identified as a possible causative. Concerning other surface characteristics that are supposed to affect the biological behavior of titanium implants, surface roughness values were found to be similar, whereas considerable differences were revealed in the wettability of the NT and NP anodic films. Our findings suggest that the applicability of NT anodic films on the surface of titanium bone implants may be limited because of mechanical considerations. In contrast, it is worth to consider the applicability of nano-pitted anodic films over nanotubular arrays for the enhancement of the biological properties of titanium implants. Copyright © 2017 Elsevier B.V. All rights reserved.

Overview of xeroderma pigmentosum proteins architecture, mutations and post-translational modifications.

PubMed

Feltes, Bruno César; Bonatto, Diego

2015-01-01

The xeroderma pigmentosum complementation group proteins (XPs), which include XPA through XPG, play a critical role in coordinating and promoting global genome and transcription-coupled nucleotide excision repair (GG-NER and TC-NER, respectively) pathways in eukaryotic cells. GG-NER and TC-NER are both required for the repair of bulky DNA lesions, such as those induced by UV radiation. Mutations in genes that encode XPs lead to the clinical condition xeroderma pigmentosum (XP). Although the roles of XPs in the GG-NER/TC-NER subpathways have been extensively studied, complete knowledge of their three-dimensional structure is only beginning to emerge. Hence, this review aims to summarize the current knowledge of mapped mutations and other structural information on XP proteins that influence their function and protein-protein interactions. We also review the possible post-translational modifications for each protein and the impact of these modifications on XP protein functions. Copyright © 2014 Elsevier B.V. All rights reserved.

Graphene Membranes for Atmospheric Pressure Photoelectron Spectroscopy.

PubMed

Weatherup, Robert S; Eren, Baran; Hao, Yibo; Bluhm, Hendrik; Salmeron, Miquel B

2016-05-05

Atmospheric pressure X-ray photoelectron spectroscopy (XPS) is demonstrated using single-layer graphene membranes as photoelectron-transparent barriers that sustain pressure differences in excess of 6 orders of magnitude. The graphene serves as a support for catalyst nanoparticles under atmospheric pressure reaction conditions (up to 1.5 bar), where XPS allows the oxidation state of Cu nanoparticles and gas phase species to be simultaneously probed. We thereby observe that the Cu(2+) oxidation state is stable in O2 (1 bar) but is spontaneously reduced under vacuum. We further demonstrate the detection of various gas-phase species (Ar, CO, CO2, N2, O2) in the pressure range 10-1500 mbar including species with low photoionization cross sections (He, H2). Pressure-dependent changes in the apparent binding energies of gas-phase species are observed, attributable to changes in work function of the metal-coated grids supporting the graphene. We expect atmospheric pressure XPS based on this graphene membrane approach to be a valuable tool for studying nanoparticle catalysis.

Upgrade of the Surface Spectrometer at NEPOMUC for PAES, XPS and STM Investigations

NASA Astrophysics Data System (ADS)

Zimnik, S.; Lippert, F.; Hugenschmidt, C.

2014-04-01

The characterization of the elemental composition of surfaces is of great importance for the understanding of many surface processes, such as surface segregation or oxidation. Positron-annihilation-induced Auger Electron Spectroscopy (PAES) is a powerful technique for gathering information about the elemental composition of only the topmost atomic layer of a sample. The upgraded surface spectrometer at NEPOMUC (NEtron induced POsitron source MUniCh) enables a comprehensive surface analysis with the complementary techniques STM, XPS and PAES. A new X-ray source for X-ray induced photoelectron spectroscopy (XPS) was installed to gather additional information on oxidation states. A new scanning tunneling microscope (STM) is used as a complementary method to investigate with atomic resolution the surface electron density. The combination of PAES, XPS and STM allows the characterization of both the elemental composition, and the surface topology.

Using “Tender” x-ray ambient pressure x-Ray photoelectron spectroscopy as a direct probe of solid-liquid interface

DOE PAGES

Axnanda, Stephanus; Crumlin, Ethan J.; Mao, Baohua; ...

2015-05-07

We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquidmore » and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt²⁺ and Pt⁴⁺ interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.« less

Using “Tender” x-ray ambient pressure x-Ray photoelectron spectroscopy as a direct probe of solid-liquid interface

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

Axnanda, Stephanus; Crumlin, Ethan J.; Mao, Baohua

We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquidmore » and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt²⁺ and Pt⁴⁺ interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.« less

Metal ion interaction with phosphorylated tyrosine analogue monolayers on gold.

PubMed

Petoral, Rodrigo M; Björefors, Fredrik; Uvdal, Kajsa

2006-11-23

Phosphorylated tyrosine analogue molecules (pTyr-PT) were assembled onto gold substrates, and the resulting monolayers were used for metal ion interaction studies. The monolayers were characterized by X-ray photoelectron spectroscopy (XPS), infrared reflection-absorption spectroscopy (IRAS), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), both prior to and after exposure to metal ions. XPS verified the elemental composition of the molecular adsorbate and the presence of metal ions coordinated to the phosphate groups. Both the angle-dependent XPS and IRAS results were consistent with the change in the structural orientation of the pTyr-PT monolayer upon exposure to metal ions. The differential capacitance of the monolayers upon coordination of the metal ions was evaluated using EIS. These metal ions were found to significantly change the capacitance of the pTyr-PT monolayers in contrast to the nonphosphorylated tyrosine analogue (TPT). CV results showed reduced electrochemical blocking capabilities of the phosphorylated analogue monolayer when exposed to metal ions, supporting the change in the structure of the monolayer observed by XPS and IRAS. The largest change in the structure and interfacial capacitance was observed for aluminum ions, compared to calcium, magnesium, and chromium ions. This type of monolayer shows an excellent capability to coordinate metal ions and has a high potential for use as sensing layers in biochip applications to monitor the presence of metal ions.

Extended study on oxidation behaviors of UN0.68 and UN1.66 by XPS

NASA Astrophysics Data System (ADS)

Luo, Lizhu; Hu, Yin; Pan, Qifa; Long, Zhong; Lu, Lei; Liu, Kezhao; Wang, Xiaolin

2018-04-01

The surface oxidation behaviors of UN0.68 and UN1.66 thin films are investigated by X-ray photoelectron spectroscopy (XPS), and the traditional U4f/N1s, O1s, valence band spectra as well as the unconventional U4d and U5d spectra are collected for the understanding of their oxidation behavior in-depth. Similar asymmetrical peak shape of the U4f spectra to uranium is observed for both uranium nitrides, despite of a slight shift to higher energy side for UN1.66 clean surface. However, significant difference among the corresponding spectra of UN0.68 and UN1.66 during oxidation reveals the distinctive properties of each own. The coexistence of UO2-x, UO2 and UO2-x.Ny on UN0.68 surface results in the peculiar features of U4f spectra as well as the others within the XPS energy scale, where peaks of the oxidized species firstly shift to higher energy side compared to the clean surface, and then return closely towards those of stoichiometric UO2. For UN1.66, the generation of U-N-O ternary compounds on the surface is identified with the symmetrical U4f peaks at 379.9eV and 390.8 eV, which locate intermediate between UO2 and UN1.66, and gradually expanding to higher energy side during the progressive oxidation. Furthermore, the formation of N-O species on UN1.66 surface is also detected as an oxidation product. The metallic character of UN1.66 is identified by the intense signal at Fermi level, which is greatly suppressed by the increasing oxygen exposure and implies the weakening metallic properties of the as-generated U-N-O compounds. Higher uranium oxides, such as UO3 and U4O9, are deduced to be the final oxidation products, and a multistage mechanism for UN1.66 following the exposure to oxygen is discussed.

Molecular beam epitaxial growth and characterization of InSb{sub 1-x}N{sub x} on GaAs for long wavelength infrared applications

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

Patra, Nimai C.; Bharatan, Sudhakar; Li, Jia

2012-04-15

Recent research progress and findings in InSbN have attracted great attention due to its use in long wavelength infrared applications. A large bandgap reduction in InSb resulting from high N incorporation with minimal crystal defects is challenging due to relatively small atomic size of N. Hence optimization of growth conditions plays an important role in the growth of high-quality InSbN epilayers for device purposes. In this paper, we report on the correlation of structural, vibrational, electrical, and optical properties of molecular beam epitaxially grown InSbN epilayers grown on GaAs substrates, as a function of varying growth temperatures. Two dimensional growthsmore » of InSb and InSbN were confirmed from dynamic reflection high energy electron diffraction patterns and growth parameters were optimized. High crystalline quality of the epilayers is attested to by a low full width at half maximum of 200 arcsec from high resolution x-ray diffraction (HRXRD) scans and by the high intensity and well-resolved InSb longitudinal optical (LO) and 2{sup nd} order InSb LO mode observed from micro-Raman spectroscopy. The N incorporation in these InSbN epilayers is estimated to be 1.4% based on HRXRD simulation. X-ray photoelectron spectroscopy (XPS) studies reveal that most of the N present in the layers are in the form of In-N bonding. Variation of the lattice disorder with growth temperature is correlated with the types of N bonding present, the carrier concentration and mobility, observed in the corresponding XPS spectra and Hall measurements, respectively. XPS analysis, HRXRD scans, and Raman spectral analysis indicate that lower growth temperature favors In-N bonding which dictates N incorporation in the substitutional sites and lattice disorder, whereas, high growth temperature promotes the formation of In-N-Sb bonding. The best room temperature and 77 K electrical transport parameters and maximum redshift in the absorption edge have been achieved in the InSbN epilayer grown in the 290 deg. C {approx} 330 deg. C temperature range.« less

Molecular beam epitaxial growth and characterization of InSb1 - xNx on GaAs for long wavelength infrared applications

NASA Astrophysics Data System (ADS)

Patra, Nimai C.; Bharatan, Sudhakar; Li, Jia; Tilton, Michael; Iyer, Shanthi

2012-04-01

Recent research progress and findings in InSbN have attracted great attention due to its use in long wavelength infrared applications. A large bandgap reduction in InSb resulting from high N incorporation with minimal crystal defects is challenging due to relatively small atomic size of N. Hence optimization of growth conditions plays an important role in the growth of high-quality InSbN epilayers for device purposes. In this paper, we report on the correlation of structural, vibrational, electrical, and optical properties of molecular beam epitaxially grown InSbN epilayers grown on GaAs substrates, as a function of varying growth temperatures. Two dimensional growths of InSb and InSbN were confirmed from dynamic reflection high energy electron diffraction patterns and growth parameters were optimized. High crystalline quality of the epilayers is attested to by a low full width at half maximum of 200 arcsec from high resolution x-ray diffraction (HRXRD) scans and by the high intensity and well-resolved InSb longitudinal optical (LO) and 2nd order InSb LO mode observed from micro-Raman spectroscopy. The N incorporation in these InSbN epilayers is estimated to be 1.4% based on HRXRD simulation. X-ray photoelectron spectroscopy (XPS) studies reveal that most of the N present in the layers are in the form of In-N bonding. Variation of the lattice disorder with growth temperature is correlated with the types of N bonding present, the carrier concentration and mobility, observed in the corresponding XPS spectra and Hall measurements, respectively. XPS analysis, HRXRD scans, and Raman spectral analysis indicate that lower growth temperature favors In-N bonding which dictates N incorporation in the substitutional sites and lattice disorder, whereas, high growth temperature promotes the formation of In-N-Sb bonding. The best room temperature and 77 K electrical transport parameters and maximum redshift in the absorption edge have been achieved in the InSbN epilayer grown in the 290 °C ˜ 330 °C temperature range.

O electrolyte for bio-application

NASA Astrophysics Data System (ADS)

Naddaf, M.; Almariri, A.

2014-09-01

Porous silicon (PS) has been prepared in the dark by anodic etching of n+-type (111) silicon substrate in a HF:HCl:C2H5OH:H2O2:H2O electrolyte. The processed PS layer is characterized by means of photoluminescence (PL) spectroscopy, scanning electron microscope (SEM), water contact angle (CA) measurements, Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and micro-Raman scattering. The CA of fresh PS layer is found to be ~142°. On aging at ambient conditions, the CA decreases gently to reach ~133° after 3 month, and then it is stabilized for a prolonged time of aging. The visible PL emission from the PS layer also exhibits a good stability against aging time. The FTIR and XPS measurements and analysis show that the stable aged PS layer has rather SiO2-rich surface. The micro/nanostructure nature of the PS layer is revealed from SEM and micro-Raman results and correlated to CA results. Stable hydrophobic surface of oxidized PS layer is attractive for bio-applications. The efficiency of the produced PS layers as an entrapping template for specific immobilization of IgG2a antibody via physical absorption process is demonstrated.

XANES and EXAFS investigation of uranium incorporation on nZVI in the presence of phosphate.

PubMed

Qiu, Muqing; Wang, Min; Zhao, Qingzhou; Hu, Baowei; Zhu, Yuling

2018-06-01

Effect of phosphate on the reduction of U(VI) on nZVI was determined by batch, XPS, XANES and EXAFS techniques. The batch experiments showed that nZVI was quite effective for the removal of uranium under the anaerobic conditions, whereas the addition of phosphate enhanced uranium removal over wide pH range. At low pH, the reduction of U(VI) to U(IV) significantly decreased with increasing phosphate concentration by XPS and XANES analysis. According to EXAFS analysis, the occurrence of UU shell at 10 mg/L phosphate and pH 4.0 was similar to that of U (IV) O 2 (s), whereas the UP and UFe shells were observed at 50 mg/L phosphate, revealing that reductive co-precipitate (U (IV) O 2 (s)) and precipitation of uranyl-phosphate were observed at low and high phosphate, respectively. The findings are crucial for the prediction of the effect of phosphate on the speciation and binding of uranium by nZVI at low pH, which is significant in controlling the mobility of U(VI) in contaminated environments. Copyright © 2018 Elsevier Ltd. All rights reserved.

Low-temperature thermal reduction of graphene oxide: In situ correlative structural, thermal desorption, and electrical transport measurements

NASA Astrophysics Data System (ADS)

Lipatov, Alexey; Guinel, Maxime J.-F.; Muratov, Dmitry S.; Vanyushin, Vladislav O.; Wilson, Peter M.; Kolmakov, Andrei; Sinitskii, Alexander

2018-01-01

Elucidation of the structural transformations in graphene oxide (GO) upon reduction remains an active and important area of research. We report the results of in situ heating experiments, during which electrical, mass spectrometry, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and transmission electron microscopy (TEM) measurements were carried out correlatively. The simultaneous electrical and temperature programmed desorption measurements allowed us to correlate the onset of the increase in the electrical conductivity of GO by five orders of magnitude at about 150 °C with the maxima of the rates of desorption of H2O, CO, and CO2. Interestingly, this large conductivity change happens at an intermediate level of the reduction of GO, which likely corresponds to the point when the graphitic domains become large enough to enable percolative electronic transport. We demonstrate that the gas desorption is intimately related to (i) the changes in the chemical structure of GO detected by XPS and Raman spectroscopy and (ii) the formation of nanoscopic holes in GO sheets revealed by TEM. These in situ observations provide a better understanding of the mechanism of the GO thermal reduction.

Difference in charge transport properties of Ni-Nb thin films with native and artificial oxide

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

Trifonov, A. S., E-mail: trifonov.artem@phys.msu.ru; Physics Faculty, Lomonosov Moscow State University, Moscow 119991; Lubenchenko, A. V.

2015-03-28

Here, we report on the properties of native and artificial oxide amorphous thin film on a surface of an amorphous Ni-Nb sample. Careful measurements of local current-voltage characteristics of the system Ni-Nb / NiNb oxide/Pt, were carried out in contact mode of an atomic force microscope. Native oxide showed n-type conductivity, while in the artificial one exhibited p-type one. The shape of current-voltage characteristic curves is unique in both cases and no analogical behavior is found in the literature. X-ray photoelectron spectroscopy (XPS) measurements were used to detect chemical composition of the oxide films and the oxidation state of themore » alloy components. Detailed analysis of the XPS data revealed that the structure of natural Ni-Nb oxide film consists of Ni-NbO{sub x} top layer and nickel enriched bottom layer which provides n-type conductivity. In contrast, in the artificial oxide film Nb is oxidized completely to Nb{sub 2}O{sub 5}, Ni atoms migrate into bulk Ni-Nb matrix. Electron depletion layer is formed at the Ni-Nb/Nb{sub 2}O{sub 5} interface providing p-type conductivity.« less

Structural characterization of oxidized titanium surfaces

NASA Astrophysics Data System (ADS)

Jobin, M.; Taborelli, M.; Descouts, P.

1995-05-01

Oxidized titanium surfaces resulting from various processes have been structurally characterized by means of scanning force microscopy, x-ray photoemission spectroscopy (XPS), x-ray diffraction, and electron energy-loss spectroscopy (EELS) with losses in the 0-100 eV range. It has been found that the surface morphology has a granular structure for electropolished titanium and for titanium evaporated on mica at low substrate temperature (570 K), but changes to flat terraces for the films evaporated at higher temperature (770 K). Angular-dependent XPS has revealed the presence of a Ti2O3 suboxide at the Ti/TiO2 interface for electropolished titanium. Dry oxidation has been performed at 770 and 970 K on both weakly and highly crystallized evaporated titanium films oriented along (0001). In the case of underlying crystallized metallic titanium, the resulting TiO2 films are crystallized with the anatase (004) orientation for oxidation at 770 K and with rutile (200) orientation for oxidation at 970 K. EELS spectra interpreted in terms of the molecular orbitals of a (TiO6)8- cluster show that the local octahedral environment of titanium atoms is preserved on native oxides, even if these oxides are not crystallized.

In situ observations of the atomistic mechanisms of Ni catalyzed low temperature graphene growth.

PubMed

Patera, Laerte L; Africh, Cristina; Weatherup, Robert S; Blume, Raoul; Bhardwaj, Sunil; Castellarin-Cudia, Carla; Knop-Gericke, Axel; Schloegl, Robert; Comelli, Giovanni; Hofmann, Stephan; Cepek, Cinzia

2013-09-24

The key atomistic mechanisms of graphene formation on Ni for technologically relevant hydrocarbon exposures below 600 °C are directly revealed via complementary in situ scanning tunneling microscopy and X-ray photoelectron spectroscopy. For clean Ni(111) below 500 °C, two different surface carbide (Ni2C) conversion mechanisms are dominant which both yield epitaxial graphene, whereas above 500 °C, graphene predominantly grows directly on Ni(111) via replacement mechanisms leading to embedded epitaxial and/or rotated graphene domains. Upon cooling, additional carbon structures form exclusively underneath rotated graphene domains. The dominant graphene growth mechanism also critically depends on the near-surface carbon concentration and hence is intimately linked to the full history of the catalyst and all possible sources of contamination. The detailed XPS fingerprinting of these processes allows a direct link to high pressure XPS measurements of a wide range of growth conditions, including polycrystalline Ni catalysts and recipes commonly used in industrial reactors for graphene and carbon nanotube CVD. This enables an unambiguous and consistent interpretation of prior literature and an assessment of how the quality/structure of as-grown carbon nanostructures relates to the growth modes.

Structure and Infrared Emissivity Properties of the MAO Coatings Formed on TC4 Alloys in K2ZrF6-Based Solution

PubMed Central

Li, Ying; Hu, Dan; Xi, Zhengping

2018-01-01

Micro-arc oxidation (MAO) ceramic coatings were formed on TC4 alloy surface in silicate and metaphosphate electrolytes based with K2ZrF6 for various concentrations. X-ray diffraction (XRD), Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) were used to characterize the phase composition, microstructure and chemical compositions of the coatings. The infrared emissivity of the coatings was measured at 50 °C in a wavelength range of 8–20 µm. The microstructural observations all revealed the typical porousstructures. Moreover, adecline in roughness and thickness of the prepared coatings can be observed when the concentration of K2ZrF6 increases. Combined with the results of XRD and XPS, it was found that all the oxides existed as the amorphous form in the coatings except the TiO2 phase. The coatings exhibited the highest infrared emissivity value (about 0.89) when the concentration of K2ZrF6 was 6 g/L, which was possibly attributed to the defect microstructure and the optimal role of ZrO2. PMID:29414841

Reduced graphene oxide-induced recrystallization of NiS nanorods to nanosheets and the improved Na-storage properties.

PubMed

Pan, Qin; Xie, Jian; Zhu, Tiejun; Cao, Gaoshao; Zhao, Xinbing; Zhang, Shichao

2014-04-07

Preparation of two-dimensional (2D) graphene-like materials is currently an emerging field in materials science since the discovery of single-atom-thick graphene prepared by mechanical cleavage. In this work, we proposed a new method to prepare 2D NiS, where reduced graphene oxide (rGO) was found to induce the recrystallization of NiS from nanorods to nanosheets in a hydrothermal process. The process and mechanism of recrystallization have been clarified by various characterization techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) mapping, and X-ray photoelectron spectroscopy (XPS). The characterization of ex situ NiS/rGO products by SEM and EDS mapping indicates that the recrystallization of NiS from nanorods to nanosheets is realized actually through an exfoliation process, while the characterization of in situ NiS/rGO products by SEM, TEM, and EDS mapping reveals the exfoliation process. The XPS result demonstrates that hydrothermally assisted chemical bonding occurs between NiS and rGO, which induces the exfoliation of NiS nanorods into nanosheets. The obtained NiS/rGO composite shows promising Na-storage properties.

Flame retardancy and thermal behavior of intumescent flame-retardant EVA composites with an efficient triazine-based charring agent

NASA Astrophysics Data System (ADS)

Xu, Bo; Ma, Wen; Wu, Xiao; Qian, Lijun; Jiang, Shan

2018-04-01

Intumescent flame retardant (IFR) EVA composites were prepared based on a hyperbranched triazine charring-foaming agent (HTCFA) and ammonium polyphosphate (APP). The synergistic effect of HTCFA and APP on the flame retardancy and thermal behavior of the composites were investigated through flammability tests, cone calorimeter measurements, thermogravimetric analysis (TGA) including evolved gas analysis (TG-IR) and residue analysis (Fourier transform infrared (FTIR), laser Raman spectroscopy (LRS), x-ray Photoelectron Spectroscopy (XPS) and scanning electron microscopy (SEM)). The flammability test results showed HTCFA/APP (1/3) system presented the best synergistic effect in flame-retardant EVA composites with the highest LOI value and UL-94 V-0 rating. As for cone calorimeter results, IFR changed the combustion behavior of EVA and resulted in remarkable decrease of flammability and smoke product. TGA results showed the synergistic effect between APP and HTCFA could strengthen the char-forming ability of composites. TG-IR results indicated the melt viscosities and gas release with increasing temperature were well-correlated for EVA/IFR composite. The residue analysis results from SEM, LRS, FT-IR and XPS revealed IFR promoted forming more compact graphitic char layer, connected by rich P–O–C and P–N structures.

Induced wettability and surface-volume correlation of composition for bovine bone derived hydroxyapatite particles

NASA Astrophysics Data System (ADS)

Maidaniuc, Andreea; Miculescu, Florin; Voicu, Stefan Ioan; Andronescu, Corina; Miculescu, Marian; Matei, Ecaterina; Mocanu, Aura Catalina; Pencea, Ion; Csaki, Ioana; Machedon-Pisu, Teodor; Ciocan, Lucian Toma

2018-04-01

Hydroxyapatite powders characteristics need to be determined both for quality control purposes and for a proper control of microstructural features of bone reconstruction products. This study combines bulk morphological and compositional analysis methods (XRF, SEM-EDS, FT-IR) with surface-related methods (XPS, contact angle measurements) in order to correlate the characteristics of hydroxyapatite powders derived from bovine bone for its use in medical applications. An experimental approach for correlating the surface and volume composition was designed based on the analysis depth of each spectral method involved in the study. Next, the influences of powder particle size and forming method on the contact angle between water drops and ceramic surface were evaluated for identifying suitable strategies of tuning hydroxyapatite's wettability. The results revealed a preferential arrangement of chemical elements at the surface of hydroxyapatite particles which could induce a favourable material behaviour in terms of sinterability and biological performance.

Insight into the adsorption mechanisms of vanadium(V) on a high-efficiency biosorbent (Ti-doped chitosan bead).

PubMed

Liu, Xin; Zhang, Lingfan

2015-08-01

In this present study, a new chitosan bead modified with titanium ions (TiCB) was prepared and employed for the adsorption of vanadium ions from aqueous solutions. Batch adsorption experiments were performed to research the effect of various factors, including pH, temperature, contact time and initial concentration of vanadium(V) ions. The adsorption of vanadium was followed by the pseudo second-order kinetic and the Langmuir isotherm model, with a remarkable maximum adsorption capacity of 210 mg/g. The analysis of thermodynamic parameters (ΔG°, ΔH° and ΔS°) revealed that the nature of adsorption was feasible, spontaneous (ΔG°<0) and endothermic (ΔH°>0) process. FTIR, EDS, EMI and XPS studies suggested that the mechanisms of adsorption were possibly attributed to electrostatic attraction, ligand-exchange and redox reaction between TiCB and vanadium ions. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis and characterization of thermally stable zirconia based mesoporous nanosilica with metalloporphyrin encapsulation

NASA Astrophysics Data System (ADS)

Nadeem, Saad; Iqbal, Farukh; Mutalib, Mohamed Ibrahim Abdul; Abdullah, Bawadi; Shaharun, Maizatul Shima

2017-10-01

Metal composite materials-48 (MCM-48) with silica zirconia mesoporous matrix (having a Zr/Si ratio of 0.02) has been developed successfully using autogenous conditions and Copper tetra phenyl porphyrin (CuTPP) inclusion via flexible ligand approach. Thermo gravimetric analysis (TGA) was used to study the thermal stability which gives the stability up to 700°C, Fourier transform infrared spectroscopy (FTIR) for the functional group attachment also confirmed the MCM-48 structure and the Zirconia addition and X-Ray photon spectroscopy (XPS) for the binding energies and bonding also revealed the surface Zr4+ states. DRS-UV-Vis study for the photophysical behaviour, visible light activation and band gap reduction which reduced from 5.6 to 2.8 eV. All the characterizations have confirmed that nanoscale mesoporous silica with successful inclusion of zirconia in the matrix and the encapsulation of CuTPP was confirmed via diffuse reflectance (DR Uv-Vis) spectroscopy.

Direct Electrodeposition of UO2 from Uranyl Bis(trifluoromethanesulfonyl)imide Dissolved in 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide Room Temperature Ionic Liquid System

DOE PAGES

Freiderich, John W.; Wanigasekara, Eranda P.; Sun, Xiao-Guang; ...

2013-11-11

Our study demonstrates a direct electrodeposition of UO 2 at a Pt cathode from a solution of uranyl bis(trifluoromethanesulfonyl)imide [UO 2(NTf 2) 2)] in a bulk room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIM +NTf 2 –). Cyclic voltammetry (CV) studies revealed two reduction waves corresponding to the conversion of uranium(VI) to uranium(IV), and a mechanism for the overall electroreduction is proposed. A controlled-potential experiment was performed, holding the reduction potential at–1.0 V for 24 h to obtain a brown-black deposit of UO 2 on the Pt cathode. The Faradaic efficiency of the reduction process was determined to be >80%. Themore » UO 2deposit was characterized by powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).« less

Tunable-color luminescence via energy transfer in NaCa13/18Mg5/18PO4:A (A = Eu2+/Tb3+/Mn2+, Dy3+) phosphors for solid state lighting.

PubMed

Li, Kai; Fan, Jian; Mi, Xiaoyun; Zhang, Yang; Lian, Hongzhou; Shang, Mengmeng; Lin, Jun

2014-11-17

A series of NaCa13/18Mg5/18PO4(NCMPO):A (A = Eu(2+)/Tb(3+)/Mn(2+), Dy(3+)) phosphors have been prepared by the high-temperature solid-state reaction method. The X-ray diffraction (XRD) and Rietveld refinement, X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), cathodoluminescence (CL), decay lifetimes, and PL quantum yields (QYs) were utilized to characterize the phosphors. The pure crystalline phase of as-prepared samples has been demonstrated via XRD measurement and Rietveld refinements. XPS reveals that the Eu(2+)/Tb(3+)/Mn(2+) can be efficiently doped into the crystal lattice. NCMPO:Eu(2+)/Tb(3+)/Mn(2+) phosphors can be effectively excited under UV radiation, which show tunable color from purple-blue to red including white emission based on energy transfer from Eu(2+) to Tb(3+)/Mn(2+) ions. Under low-voltage electron beam bombardment, the NCMPO:A (A = Eu(2+)/Tb(3+)/Mn(2+), Dy(3+)) display their, respectively, characteristic emissions with different colors, and the CL spectrum of NCMPO:0.04Tb(3+) has the comparable intensity to the ZnO:Zn commercial product. In addition, the calculated CIE coordinate of NCMPO:0.04Tb(3+) (0.252, 0.432) is more saturated than it (0.195, 0.417). These results reveal that NCMPO:A (A = Eu(2+)/Tb(3+)/Mn(2+), Dy(3+)) may be potential candidate phosphors for WLEDs and FEDs.

The influence of A-site rare-earth for barium substitution on the chemical structure and ferroelectric properties of BZT thin films

NASA Astrophysics Data System (ADS)

Ostos, C.; Martínez-Sarrión, M. L.; Mestres, L.; Delgado, E.; Prieto, P.

2009-10-01

Rare-earth ( RE) doped Ba(Zr,Ti)O 3 (BZT) thin films were prepared by rf-magnetron sputtering from a Ba 0.90Ln0.067Zr 0.09Ti 0.91O 3 ( Ln=La, Nd) target. The films were deposited at a substrate temperature of 600 °C in a high oxygen pressure atmosphere. X-ray diffraction (XRD) patterns of RE-BZT films revealed a <001> epitaxial crystal growth on Nb-doped SrTiO 3, <001> and <011> growth on single-crystal Si, and a <111>-preferred orientation on Pt-coated Si substrates. Scanning electron microscopy (SEM) showed uniform growth of the films deposited, along with the presence of crystals of about half-micron size on the film's surface. Transmission electron microscopy (TEM) evidenced high crystalline films with thicknesses of about 100 nm for 30 min of sputtering. Electron-probe microanalysis (EPMA) corroborated the growth rate (3.0-3.5 nm/min) of films deposited on Pt-coated Si substrates. X-ray photoelectron spectroscopy (XPS), in depth profile mode, showed variations in photoelectron Ti 2 p doublet positions at lower energies with spin-orbital distances characteristic of BaTiO 3-based compounds. The XPS analysis revealed that lanthanide ions positioned onto the A-site of the BZT-perovskite structure increasing the MO 6-octahedra distortion ( M=Ti, Zr) and, thereby, modifying the Ti-O binding length. Polarization-electric field hysteresis loops on Ag/ RE-doped BZT/Pt capacitor showed good ferroelectric behavior and higher remanent polarization values than corresponding non-doped system.

Plasma enhancement of in vitro attachment of rat bone-marrow-derived stem cells on cross-linked gelatin films.

PubMed

Prasertsung, I; Kanokpanont, S; Mongkolnavin, R; Wong, C S; Panpranot, J; Damrongsakkul, S

2012-01-01

In this work, nitrogen, oxygen and air glow discharges powered by 50 Hz AC power supply are used for the treatment of type-A gelatin film cross-linked by a dehydrothermal (DHT) process. The properties of cross-linked gelatin were characterized by contact angle measurement, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) analysis. The results showed that the water contact angle of gelatin films decrease with increasing plasma treatment time. The treatment of nitrogen, oxygen and air plasma up to 30 s had no effects on the surface roughness of the gelatin film as revealed by AFM results. The XPS analysis showed that the N-containing functional groups generated by nitrogen and air plasma, and O-containing functional groups generated by oxygen and air plasmas were incorporated onto the film surface, the functional groups were found to increase with increasing treatment time. An in vitro test using rat bone-marrow-mesenchym-derived stem cells (MSCs) revealed that the number of cells attached on plasma-treated gelatin films was significantly increased compared to untreated samples. The best enhancement of cell attachment was noticed when the film was treated with nitrogen plasma for 15-30 s, oxygen plasma for 3 s, and air plasma for 9 s. In addition, among the three types of plasmas used, nitrogen plasma treatment gave the best MSCs attachment on the gelatin surface. The results suggest that a type-A gelatin film with water contact angle of 27-28° and an O/N ratio of 1.4 is most suitable for MSCs attachment.

Analysis of XPS spectra of Fe 2+ and Fe 3+ ions in oxide materials

NASA Astrophysics Data System (ADS)

Yamashita, Toru; Hayes, Peter

2008-02-01

Samples of the iron oxides Fe 0.94O, Fe 3O 4, Fe 2O 3, and Fe 2SiO 4 were prepared by high temperature equilibration in controlled gas atmospheres. The samples were fractured in vacuum and high resolution XPS spectra of the fractured surfaces were measured. The peak positions and peak shape parameters of Fe 3p for Fe 2+ and Fe 3+ were derived from the Fe 3p XPS spectra of the standard samples of 2FeO·SiO 2 and Fe 2O 3, respectively. Using these parameters, the Fe 3p peaks of Fe 3O 4 and Fe 1- yO are analysed. The results indicate that high resolution XPS techniques can be used to determine the Fe 2+/Fe 3+ ratios in metal oxides. The technique has the potential for application to other transition metal oxide systems.

Depth profile composition studies of thin film CdS:Cu2S solar cells using XPS and AES

NASA Astrophysics Data System (ADS)

Bhide, V. G.; Salkalachen, S.; Rastogi, A. C.; Rao, C. N. R.; Hegde, M. S.

1981-09-01

Studies of the surface composition and depth profiles of thin film CdS:Cu2S solar cells based on the techniques of X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) are reported. Specimens were fabricated by the thermal deposition of polycrystalline CdS films onto silver-backed electrodes predeposited on window glass substrates, followed by texturization in hot HCl and chemical plating in a hot CuCl(I) bath for a few seconds to achieve the topotaxial growth of CuS films. The XPS and AES studies indicate the junction to be fairly diffused in the as-prepared cell, with heat treatment in air at 210 C sharpening the junction, improving the stoichiometry of the Cu2S layer and thus improving cell performance. The top copper sulfide layer is found to contain impurities such as Cd, Cl, O and C, which may be removed by mild Ar(+) ion beam etching. The presence of copper deep in the junction is invariably detected, apparently in the grain boundary region in the form of CuS or Cu(2+) trapped in the lattice. It is also noted that the nominal valence state of copper changes abruptly from Cu(+) to Cu(2+) across the junction.

Examining the temperature behavior of stainless steel surfaces exposed to hydrogen plasmas in the Lithium Tokamak eXperiment (LTX)

NASA Astrophysics Data System (ADS)

Bedoya, Felipe; Allain, Jean Paul; Kaita, Robert; Lucia, Matthew; St-Onge, Denis; Ellis, Robert; Majeski, Richard

2014-10-01

The Materials Analysis Particle Probe (MAPP) is an in-situ diagnostic designed to characterize plasma-facing components (PFCs) in tokamak devices. MAPP is installed in LTX at Princeton Plasma Physics Laboratory. MAPP's capabilities include remotely operated XPS acquisition and temperature control of four samples. The recent addition of a focused ion beam allows XPS depth profiling analysis. Recent published results show an apparent correlation between hydrogen retention and temperature of Li coated stainless steel (SS) PFCs exposed to plasmas like those of LTX. According to XPS data, the retention of hydrogen by the coated surfaces decreases at above 180 °C. In the present study MAPP will be used to study the oxidation of Li coatings as a function of time and temperature of the walls when Li coatings are applied. Experiments in the ion-surface interaction experiment (IIAX) varying the hydrogen fluence on the SS samples will be also performed. Conclusions resulting from this study will be key to explain the PFC temperature-dependent variation of plasma performance observed in LTX. This work was supported by U.S. DOE Contracts DE-AC02-09CH11466, DE-AC52-07NA27344 and DE-SC0010717.

Electron-spectroscopy and -diffraction study of the conductivity of CVD diamond ( 0 0 1 )2×1 surface

NASA Astrophysics Data System (ADS)

Kono, S.; Takano, T.; Shimomura, M.; Goto, T.; Sato, K.; Abukawa, T.; Tachiki, M.; Kawarada, H.

2003-04-01

A chemical vapor deposition as-grown diamond (0 0 1) single-domain 2 × 1 surface was studied by electron-spectroscopy and electron-diffraction in ultrahigh vacuum (UHV). In order to change the surface conductivity (SC) of the diamond in UHV, three annealing stages were used; without annealing, annealing at 300 °C and annealing at 550 °C. From low energy electron diffraction and X-ray photoelectron spectroscopic (XPS) studies, an existence of SC was suggested for the first two stages of annealing and an absence of SC was suggested for the last stage of annealing. Changes in C KVV Auger electron spectroscopic spectra, C KVV Auger electron diffraction (AED) patterns and C 1s XPS peak positions were noticed between the annealing stages at 300 and 550 °C. These changes are interpreted as such that the state of hydrogen involvement in a subsurface of diamond (0 0 1)2 × 1 changes as SC changes. In particular, the presence of local disorder in diamond configuration in SC subsurface is pointed out from C KVV AED. From C 1s XPS peak shifts, a lower bound for the Fermi-level for SC layers from the valence band top is presented to be ˜0.5 eV.

Photo-catalytic decolourisation of toxic dye with N-doped titania: a case study with Acid Blue 25.

PubMed

Chakrabortty, Dhruba; Gupta, Susmita Sen

2013-05-01

Dyes are one of the hazardous water pollutants. Toxic Acid Blue 25, an anthraquinonic dye, has been decolourised by photo-catalysing it with nitrogen doped titania in aqueous medium. The photo catalyst was prepared from 15% TiCl3 and 25% aqueous NH3 solution as precursor. XRD and TEM revealed the formation of well crystalline anatase phase having particle size in the nano-range. BET surface area of the sample was higher than that of pure anatase TiO2. DRS showed higher absorption of radiation in visible range compared to pure anatase TiO2. XPS revealed the presence of nitrogen in N-Ti-O environment. The experimental parameters, namely, photocatalyst dose, initial dye concentration as well as solution pH influence the decolourisation process. At pH 3.0, the N-TiO2 could decolourise almost 100% Acid Blue 25 within one hour. The influence of N-TiO2 dose, initial concentration of Acid Blue 25 and solution pH on adsorption-desorption equilibrium is also studied. The adsorption process follows Lagergren first order kinetics while the modified Langmuir-Hinselwood model is suitably fitted for photocatalytic decolourisation of Acid Blue 25.

Rapid degradation of phenol by ultrasound-dispersed nano-metallic particles (NMPs) in the presence of hydrogen peroxide: A possible mechanism for phenol degradation in water.

PubMed

Singh, Jiwan; Yang, Jae-Kyu; Chang, Yoon-Young

2016-06-15

The present study was carried out to investigate the degradation of phenol by ultrasonically dispersed nano-metallic particles (NMPs) in an aqueous solution of phenol. Leaching liquor from automobile shredder residue (ASR) was used to obtain the NMPs. The prepared NMPs were analyzed by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and by X-ray diffraction (XRD). The SEM images show that the diameters of the NMPs were less than 50 nm. An SEM-EDX elemental analysis reveals that Fe was the most commonly found element (weight %) in the NMPs. The FTIR and XRD peaks indicate the presence of metals oxides on the surfaces of the NMPs. The results of the XPS analysis indicate that various elements (e.g., C, O, Zn, Cu, Mn, Fe) are present on the surfaces of the NMPs. The effects of the NMP dose, the initial solution pH, and of different concentrations of phenol and H2O2 on the phenol degradation characteristics were evaluated. The results of this study demonstrate that phenol degradation can be improved by increasing the amount of NMPs, whereas it is reduced with an increase in the phenol concentration. The degradation of phenol by ultrasonically dispersed NMPs followed the pseudo-first-order kinetics. The probable mechanism of phenol degradation by ultrasonically dispersed NMPs was the oxidation of phenol caused by the hydroxyl radicals produced during the reaction between H2O2 and the NMPs during the ultrasonication process. Copyright © 2016 Elsevier Ltd. All rights reserved.

Low toxic maghemite nanoparticles for theranostic applications.

PubMed

Kuchma, Elena A; Zolotukhin, Peter V; Belanova, Anna A; Soldatov, Mikhail A; Lastovina, Tatiana A; Kubrin, Stanislav P; Nikolsky, Anatoliy V; Mirmikova, Lidia I; Soldatov, Alexander V

2017-01-01

Iron oxide nanoparticles have numerous and versatile biological properties, ranging from direct and immediate biochemical effects to prolonged influences on tissues. Most applications have strict requirements with respect to the chemical and physical properties of such agents. Therefore, developing rational design methods of synthesis of iron oxide nanoparticles remains of vital importance in nanobiomedicine. Low toxic superparamagnetic iron oxide nanoparticles (SPIONs) for theranostic applications in oncology having spherical shape and maghemite structure were produced using the fast microwave synthesis technique and were fully characterized by several complementary methods (transmission electron microscopy [TEM], X-ray diffraction [XRD], dynamic light scattering [DLS], X-ray photoelectron spectroscopy [XPS], X-ray absorption near edge structure [XANES], Mossbauer spectroscopy, and HeLa cells toxicity testing). TEM showed that the majority of the obtained nanoparticles were almost spherical and did not exceed 20 nm in diameter. The averaged DLS hydrodynamic size was found to be ~33 nm, while that of nanocrystallites estimated by XRD waŝ16 nm. Both XRD and XPS studies evidenced the maghemite (γ-Fe 2 O 3 ) atomic and electronic structure of the synthesized nanoparticles. The XANES data analysis demonstrated the structure of the nanoparticles being similar to that of macroscopic maghemite. The Mossbauer spectroscopy revealed the γ-Fe 2 O 3 phase of the nanoparticles and vibration magnetometry study showed that reactive oxygen species in HeLa cells are generated both in the cytoplasm and the nucleus. Quasispherical Fe 3+ SPIONs having the maghemite structure with the average size of 16 nm obtained by using the fast microwave synthesis technique are expected to be of great value for theranostic applications in oncology and multimodal anticancer therapy.

Photoelectron spectroscopic studies of ultra-thin CuPc layers on a Si(111)-(√3 × √3)R30°-B surface

NASA Astrophysics Data System (ADS)

Menzli, S.; Laribi, A.; Mrezguia, H.; Arbi, I.; Akremi, A.; Chefi, C.; Chérioux, F.; Palmino, F.

2016-12-01

The adsorption of copper phthalocyanine (CuPc) molecules on Si(111)-(√3 × √3)R30°-B surface is investigated at room temperature under ultra-high vacuum. Crystallographic, chemical and electronic properties of the interface are investigated by low energy electron diffraction (LEED), ultraviolet and X-ray photoemission spectroscopies (UPS, XPS) and X-ray photoemission diffraction (XPD). LEED and XPD results shed light on the growth mechanism of CuPc on this substrate. At one monolayer coverage the growth mode was characterized by the formation of crystalline 3D nanoislands. The molecular packing deduced from this study appears very close to the one of the bulk CuPc α phase. The 3D islands are formed by molecules aligned in a standing manner. XPS core level spectra of the substrate reveal that there is no discernible chemical interaction between molecules and substrate. However there is charge transfer from molecules to the substrate. During the growth, the work function (WF) was found to decrease from 4.50 eV for the clean substrate to 3.70 eV for the highest coverage (30 monolayers). Within a thickness of two monolayers deposition, an interface dipole of 0.50 eV was found. A substrate band bending of 0.25 eV was deduced over all the range of exposure. UPS spectra indicate the existence of a band bending of the highest occupied molecular orbital (HOMO) of 0.30 eV. The changes in the work function, in the Fermi level position and in the onset of the molecular HOMO state have been used to determine the energy level alignment at the interface.

A comparison study of the start-up of a MnOx filter for catalytic oxidative removal of ammonium from groundwater and surface water.

PubMed

Cheng, Ya; Li, Ye; Huang, Tinglin; Sun, Yuankui; Shi, Xinxin; Shao, Yuezong

2018-03-01

As an efficient method for ammonium (NH 4 + ) removal, contact catalytic oxidation technology has drawn much attention recently, due to its good low temperature resistance and short start-up period. Two identical filters were employed to compare the process for ammonium removal during the start-up period for ammonium removal in groundwater (Filter-N) and surface water (Filter-S) treatment. Two types of source water (groundwater and surface water) were used as the feed waters for the filtration trials. Although the same initiating method was used, Filter-N exhibited much better ammonium removal performance than Filter-S. The differences in catalytic activity among these two filters were probed using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and compositional analysis. XRD results indicated that different manganese oxide species were formed in Filter-N and Filter-S. Furthermore, the Mn3p XPS spectra taken on the surface of the filter films revealed that the average manganese valence of the inactive manganese oxide film collected from Filter-S (FS-MnO x ) was higher than in the film collected from Filter-N (FN-MnO x ). Mn(IV) was identified as the predominant oxidation state in FS-MnO x and Mn(III) was identified as the predominant oxidation state in FN-MnO x . The results of compositional analyses suggested that polyaluminum ferric chloride (PAFC) used during the surface water treatment was an important factor in the mineralogy and reactivity of MnO x . This study provides the theoretical basis for promoting the wide application of the technology and has great practical significance. Copyright © 2017. Published by Elsevier B.V.

Study on swift heavy ions induced modifications of Ag-ZnO nanocomposite thin film

NASA Astrophysics Data System (ADS)

Singh, S. K.; Singhal, R.; Siva Kumar, V. V.

2017-03-01

In the present work, swift heavy ion (SHI) irradiation induced modifications in structural and optical properties of Ag-ZnO nanocomposite thin films have been investigated. Ag-ZnO nanocomposite (NCs) thin films were synthesized by RF magnetron sputtering technique and irradiated with 100 MeV Ag7+ ions at three different fluences 3 × 1012, 1 × 1013 and 3 × 1013 ions/cm2. Rutherford Backscattering Spectrometry revealed Ag concentration to be ∼8.0 at.%, and measured thickness of the films was ∼55 nm. Structural properties of pristine and irradiated films have been analyzed by X-ray diffraction analysis and found that variation in crystallite size of the film with ion irradiation. X-ray photoelectron spectroscopy (XPS) indicates the formation of Ag-ZnO nanocomposite thin film with presence of Ag, Zn and O elements. Oxidation state of Ag and Zn also estimated by XPS analysis. Surface plasmon resonance (SPR) of Ag nanoparticle has appeared at ∼475 nm in the pristine thin film, which is blue shifted by ∼30 nm in film irradiated at fluence of 3 × 1012 ions/cm2 and completely disappeared in film irradiated at higher fluences, 1 × 1013 and 3 × 1013 ions/cm2. A marginal change in the optical band gap of Ag-ZnO nanocomposite thin film is also found with increasing ion fluence. Surface morphology of pristine and irradiated films have been studied using Atomic Force Microscopy (AFM). Raman and Photo-luminance (PL) spectra of nanocomposite thin films have been investigated to understand the ion induced modifications such as lattice defects and disordering in the nanocomposite thin film.

Fluorine-doped carbon nanotubes as an efficient metal-free catalyst for destruction of organic pollutants in catalytic ozonation.

PubMed

Wang, Jing; Chen, Shuo; Quan, Xie; Yu, Hongtao

2018-01-01

Metal-free carbon materials have been presented to be potential alternatives to metal-based catalysts for heterogeneous catalytic ozonation, yet the catalytic performance still needs to be enhanced. Doping carbon with non-metallic heteroatoms (e.g., N, B, and F) could alter the electronic structure and electrochemical properties of original carbon materials, has been considered to be an effective method for improving the catalytic activity of carbon materials. Herein, fluorine-doped carbon nanotubes (F-CNTs) were synthesized via a facile method and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The as-synthesized F-CNTs exhibited notably enhanced catalytic activity towards catalytic ozonation for the degradation of organic pollutants. The oxalic acid removal efficiency of optimized F-CNTs was approximately two times as much as that of pristine CNTs, and even exceeded those of four conventional metal-based catalysts (ZnO, Al 2 O 3 , Fe 2 O 3 , and MnO 2 ). The XPS and Raman studies confirmed that the covalent CF bonds were formed at the sp 3 C sites instead of sp 2 C sites on CNTs, not only resulting in high positive charge density of C atoms adjacent to F atoms, but remaining the delocalized π-system with intact carbon structure of F-CNTs, which then favored the conversion of ozone molecules (O 3 ) into reactive oxygen species (ROS) and contributed to the high oxalic acid removal efficiency. Furthermore, electron spin resonance (ESR) studies revealed that superoxide radicals (O 2 - ) and singlet oxygen ( 1 O 2 ) might be the dominant ROS that responsible for the degradation of oxalic acid in these catalytic systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Harvesting visible light with MoO3 nanorods modified by Fe(iii) nanoclusters for effective photocatalytic degradation of organic pollutants.

PubMed

Alam, U; Kumar, S; Bahnemann, D; Koch, J; Tegenkamp, C; Muneer, M

2018-02-07

The photocatalytic performance of MoO 3 is limited due to its weak visible light absorption ability and quick recombination of charge carriers. In the present work, we report the facile synthesis of Fe(iii)-grafted MoO 3 nanorods using a hydrothermal method followed by an impregnation technique with the aim of enhancing the light harvesting ability and photocatalytic efficiency of MoO 3 . The prepared samples were characterized through the standard analytical techniques of XRD, SEM-EDS, TEM, XPS, UV-Vis-DRS, FT-IR, TG-DTA and PL spectrophotometry. XPS and TEM analyses reveal that Fe(iii) ions are successfully grafted onto the surface of the MoO 3 nanorod with intimate interfacial contact. The photocatalytic performances of the prepared samples were investigated by studying the degradation of methylene blue (MB), rhodamine B (RhB) and 4-nitrophenol (4-NP) under visible light irradiation. The surface-modified MoO 3 with Fe(iii) ions showed excellent photocatalytic activity towards the degradation of the above-mentioned pollutants, where Fe(iii) ions act as effective cocatalytic sites to produce hydroxyl radicals through multi-electron reduction of oxygen molecules. The improved photocatalytic activity could be ascribed to the effective separation of charge carriers and efficient production of hydroxyl radicals via the rapid capture of electrons by Fe(iii) through a well-known photoinduced interfacial charge transfer mechanism. Based on scavenger analysis study, a mechanism for the enhanced photocatalytic activity has been discussed and proposed. The concept of surface grafting onto large bandgap semiconductors with ubiquitous elements opens up a new avenue for the development of visible-light-responsive photocatalysts with excellent photocatalytic activity.

Surface modification of nitrogen-doped carbon nanotubes by ozone via atomic layer deposition

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

Lushington, Andrew; Liu, Jian; Tang, Yongji

The use of ozone as an oxidizing agent for atomic layer deposition (ALD) processes is rapidly growing due to its strong oxidizing capabilities. However, the effect of ozone on nanostructured substrates such as nitrogen-doped multiwalled carbon nanotubes (NCNTs) and pristine multiwalled carbon nanotubes (PCNTs) are not very well understood and may provide an avenue toward functionalizing the carbon nanotube surface prior to deposition. The effects of ALD ozone treatment on NCNTs and PCNTs using 10 wt. % ozone at temperatures of 150, 250, and 300 °C are studied. The effect of ozone pulse time and ALD cycle number on NCNTs and PCNTsmore » was also investigated. Morphological changes to the substrate were observed by scanning electron microscopy and high resolution transmission electron microscopy. Brunauer-Emmett-Teller measurements were also conducted to determine surface area, pore size, and pore size distribution following ozone treatment. The graphitic nature of both NCNTs and PCNTs was determined using Raman analysis while x-ray photoelectron spectroscopy (XPS) was employed to probe the chemical nature of NCNTs. It was found that O{sub 3} attack occurs preferentially to the outermost geometric surface of NCNTs. Our research also revealed that the deleterious effects of ozone are found only on NCNTs while little or no damage occurs on PCNTs. Furthermore, XPS analysis indicated that ALD ozone treatment on NCNTs, at elevated temperatures, results in loss of nitrogen content. Our studies demonstrate that ALD ozone treatment is an effective avenue toward creating low nitrogen content, defect rich substrates for use in electrochemical applications and ALD of various metal/metal oxides.« less

Low toxic maghemite nanoparticles for theranostic applications

PubMed Central

Zolotukhin, Peter V; Belanova, Anna A; Soldatov, Mikhail A; Lastovina, Tatiana A; Kubrin, Stanislav P; Nikolsky, Anatoliy V; Mirmikova, Lidia I

2017-01-01

Background Iron oxide nanoparticles have numerous and versatile biological properties, ranging from direct and immediate biochemical effects to prolonged influences on tissues. Most applications have strict requirements with respect to the chemical and physical properties of such agents. Therefore, developing rational design methods of synthesis of iron oxide nanoparticles remains of vital importance in nanobiomedicine. Methods Low toxic superparamagnetic iron oxide nanoparticles (SPIONs) for theranostic applications in oncology having spherical shape and maghemite structure were produced using the fast microwave synthesis technique and were fully characterized by several complementary methods (transmission electron microscopy [TEM], X-ray diffraction [XRD], dynamic light scattering [DLS], X-ray photoelectron spectroscopy [XPS], X-ray absorption near edge structure [XANES], Mossbauer spectroscopy, and HeLa cells toxicity testing). Results TEM showed that the majority of the obtained nanoparticles were almost spherical and did not exceed 20 nm in diameter. The averaged DLS hydrodynamic size was found to be ~33 nm, while that of nanocrystallites estimated by XRD waŝ16 nm. Both XRD and XPS studies evidenced the maghemite (γ-Fe2O3) atomic and electronic structure of the synthesized nanoparticles. The XANES data analysis demonstrated the structure of the nanoparticles being similar to that of macroscopic maghemite. The Mossbauer spectroscopy revealed the γ-Fe2O3 phase of the nanoparticles and vibration magnetometry study showed that reactive oxygen species in HeLa cells are generated both in the cytoplasm and the nucleus. Conclusion Quasispherical Fe3+ SPIONs having the maghemite structure with the average size of 16 nm obtained by using the fast microwave synthesis technique are expected to be of great value for theranostic applications in oncology and multimodal anticancer therapy. PMID:28919740

How Much Surface Coating of Hydrophobic Azithromycin Is Sufficient to Prevent Moisture-Induced Decrease in Aerosolisation of Hygroscopic Amorphous Colistin Powder?

PubMed

Zhou, Qi Tony; Loh, Zhi Hui; Yu, Jiaqi; Sun, Si-Ping; Gengenbach, Thomas; Denman, John A; Li, Jian; Chan, Hak-Kim

2016-09-01

Aerosolisation performance of hygroscopic particles of colistin could be compromised at elevated humidity due to increased capillary forces. Co-spray drying colistin with a hydrophobic drug is known to provide a protective coating on the composite particle surfaces against moisture-induced reduction in aerosolisation performance; however, the effects of component ratio on surface coating quality and powder aerosolisation at elevated relative humidities are unknown. In this study, we have systematically examined the effects of mass ratio of hydrophobic azithromycin on surface coating quality and aerosolisation performance of the co-spray dried composite particles. Four combination formulations with varying drug ratios were prepared by co-spray drying drug solutions. Both of the drugs in each combination formulation had similar in vitro deposition profiles, suggesting that each composite particle comprises two drugs in the designed mass ratio, which is supported by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) data. XPS and ToF-SIMS measurements also revealed that 50% by weight (or 35% by molecular fraction) of azithromycin in the formulation provided a near complete coating of 96.5% (molar fraction) on the composite particle surface, which is sufficient to prevent moisture-induced reduction in fine particle fraction (FPF)recovered and FPFemitted. Higher azithromycin content did not increase coating coverage, while contents of azithromycin lower than 20% w/w did not totally prevent the negative effects of humidity on aerosolisation performance. This study has highlighted that a critical amount of azithromycin is required to sufficiently coat the colistin particles for short-term protection against moisture.

Oxidation and deprotonation of synthetic Fe{sup II}-Fe{sup III} (oxy)hydroxycarbonate Green Rust: An X-ray photoelectron study

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

Mullet, M.; Guillemin, Y.; Ruby, C.

X-ray photoelectron spectroscopy (XPS) was used to investigate chemical bonding and distribution of iron and oxygen species at the surface of Green Rusts (GRs). GRs with variable composition, i.e. Fe{sup II}{sub 6(1-x)}Fe{sup III}{sub 6x}O{sub 12}H{sub 2(7-3x)} CO{sub 3}.3H{sub 2}O where the Fe{sup III} molar fraction of the positively charged hydroxide sheets, x=[Fe(III)]/[Fe(total)] belongs to [1/3, 1], were synthesised under an inert atmosphere. The broadened Fe(2p{sub 3/2}) spectra were fitted using Gupta and Sen multiplets peaks and additional satellite and surface features. The [Fe(III)]/[Fe(total)] surface atomic ratios closely agree with the x ratios expected from the bulk composition, which gives amore » high degree of confidence on the validity of the proposed fitting procedure. The valence band spectra are also reported and show dependencies on iron speciation. The O(1s) spectra revealed the presence of O{sup 2-}, OH{sup -} species and adsorbed water. The hydroxyl component decreases with increasing x values, i.e. with the amount of ferric iron, while the oxide component increases. This study provides direct spectroscopic evidence of the deprotonation of hydroxyl groups that occurs simultaneously with the oxidation of ferrous iron within the GR structure. - Graphical abstract: X-ray photoelectron spectroscopy (XPS) is used to investigate chemical bonding and distribution of iron and oxygen species at the surface of Green Rust (GR) compounds. First spectroscopic evidence of the deprotonation of hydroxyls groups occurring simultaneously to the oxidation of Fe(II) into Fe(III) species is provided.« less

Neutron vibrational spectroscopic studies of novel tire-derived carbon materials.

PubMed

Li, Yunchao; Cheng, Yongqiang; Daemen, Luke L; Veith, Gabriel M; Levine, Alan M; Lee, Richard J; Mahurin, Shannon M; Dai, Sheng; Naskar, Amit K; Paranthaman, Mariappan Parans

2017-08-23

Sulfonated tire-derived carbons have been demonstrated to be high value-added carbon products of tire recycling in several energy storage system applications including lithium, sodium, potassium ion batteries and supercapacitors. In this communication, we compared different temperature pyrolyzed sulfonated tire-derived carbons with commercial graphite and unmodified/non-functionalized tire-derived carbon by studying the surface chemistry and properties, vibrational spectroscopy of the molecular structure, chemical bonding such as C-H bonding, and intermolecular interactions of the carbon materials. The nitrogen adsorption-desorption studies revealed the tailored micro and meso pore size distribution of the carbon during the sulfonation process. XPS and neutron vibrational spectra showed that the sulfonation of the initial raw tire powders could remove the aliphatic hydrogen containing groups ([double bond splayed left]CH 2 and -CH 3 groups) and reduce the number of heteroatoms that connect to carbon. The absence of these functional groups could effectively improve the first cycle efficiency of the material in rechargeable batteries. Meanwhile, the introduced -SO 3 H functional group helped in producing terminal H at the edge of the sp 2 bonded graphite-like layers. This study reveals the influence of the sulfonation process on the recovered hard carbon from used tires and provides a pathway to develop and improve advanced energy storage materials.

Monitoring N3 dye adsorption and desorption on TiO2 surfaces: a combined QCM-D and XPS study.

PubMed

Wayment-Steele, Hannah K; Johnson, Lewis E; Tian, Fangyuan; Dixon, Matthew C; Benz, Lauren; Johal, Malkiat S

2014-06-25

Understanding the kinetics of dye adsorption and desorption on semiconductors is crucial for optimizing the performance of dye-sensitized solar cells (DSSCs). Quartz crystal microbalance with dissipation monitoring (QCM-D) measures adsorbed mass in real time, allowing determination of binding kinetics. In this work, we characterize adsorption of the common RuBipy dye N3 to the native oxide layer of a planar, sputter-coated titanium surface, simulating the TiO2 substrate of a DSSC. We report adsorption equilibrium constants consistent with prior optical measurements of N3 adsorption. Dye binding and surface integrity were also verified by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy (XPS). We further study desorption of the dye from the native oxide layer on the QCM sensors using tetrabutylammonium hydroxide (TBAOH), a commonly used industrial desorbant. We find that using TBAOH as a desorbant does not fully regenerate the surface, though little ruthenium or nitrogen is observed by XPS after desorption, suggesting that carboxyl moieties of N3 remain bound. We demonstrate the native oxide layer of a titanium sensor as a valid and readily available planar TiO2 morphology to study dye adsorption and desorption and begin to investigate the mechanism of dye desorption in DSSCs, a system that requires further study.

Synthesis of a Novel Phosphorus-Containing Flame Retardant Curing Agent and Its Application in Epoxy Resins.

PubMed

Zhang, Hongkun; Xu, Miaojun; Li, Bin

2016-03-01

A novel phosphorus-containing compound diphenyl-(2,5-dihydroxyphenyl)-phosphine oxide defined as DPDHPPO was synthesized and used as flame retardant and curing agent for epoxy resins (EP). The chemical structure was well characterized by Fourier transform infrared (FTIR) spectroscopy, 1H, 13C and 31P nuclear magnetic resonance. The flame retardant properties, combusting performances and thermal degradation behaviors of the cured epoxy resins were investigated by limiting oxygen index (LOI), vertical burning tests (UL-94), cone calorimeter and thermogravimetric analysis (TGA) tests. The morphologies and chemical compositions of char residues for cured epoxy resins were investigated by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. The water resistant properties were evaluated by putting the samples into distilled water at 70 degrees C for 168 h. The results revealed that the EP/40 wt% DPDHPPO/60 wt% PDA thermosets successfully passed UL-94 V-0 flammability rating and the LOI value was as high as 31.9%. The cone tests results revealed that the incorporation of DPDHPPO efficiently reduced the combustion parameters of epoxy resins thermosets, such as heat release rate (HRR), total heat release (THR) and so on. The TGA results indicated that the introduction of DPDHPPO promoted epoxy resins matrix decomposed ahead of time compared with that of pure EP and led to a higher char yield and thermal stability at high temperature. The morphological structures and analysis of XPS of char residues revealed that DPDHPPO benefited to the formation of a sufficient, compact and homogeneous char layer with rich flame retardant elements on the epoxy resins materials surface during combustion. After water resistance tests, EP/40 wt% DPDHPPO/60 wt% PDA thermosets still remained excellent flame retardancy, the moisture absorption of epoxy resins thermosets decreased with the increase of DPDHPPO contents in the thermosets due to the existing of P-C bonds and the rigid aromatic hydrophobic structure.

Effect of TiO2, ZrO2, and TiO2-ZrO2 on the performance of CuO-ZnO catalyst for CO2 hydrogenation to methanol

NASA Astrophysics Data System (ADS)

Xiao, Jie; Mao, Dongsen; Guo, Xiaoming; Yu, Jun

2015-05-01

The influence of TiO2, ZrO2, and TiO2-ZrO2 mixed oxide on the catalytic performance of CuO-ZnO catalyst in the methanol synthesis from CO2 hydrogenation was studied. The catalysts were prepared by oxalate co-precipitation method and characterized by TGA, N2 adsorption, XRD, reactive N2O adsorption, XPS, H2-TPR, H2-TPD, and CO2-TPD techniques. Characterization results reveal that all the additives improve the CuO dispersion in the catalyst body and increase the Cu surface area and adsorption capacities of CO2 and H2. The results of catalytic test reveal that the additives increase both the CO2 conversion and methanol selectivity, and TiO2-ZrO2 mixed oxide is more effective than single components of TiO2 or ZrO2. Moreover, the activity of methanol synthesis is correlated directly with CO2 adsorption capacity over the catalysts.

Growth, Crystal Structure, Theoretical Analysis and Properties of Te4+-Doped KTiOPO4

NASA Astrophysics Data System (ADS)

Liu, Lintao; Yao, Qian; Zhang, Junying; Dong, Weimin; Li, Jing; Wang, Jiyang; Boughton, Robert I.

2018-04-01

A single crystal of Te4+-doped KTiOPO4(Te:KTP) has been grown by the flux method. The electronic structure and density of states of KTiOPO4 (KTP) and Te:KTP were calculated from first principles. As the results reveal, there is no change in the space group or lattice structure of Te:KTP, but that some increase in lattice parameters occurred. The chemical composition of Te:KTP was analyzed using x-ray photoelectron spectroscopy (XPS). The possible existence of Ti3+ has been evaluated by measuring the electron paramagnetic resonance spectrum, and the results reveal that the ion is absent from this crystal. It was observed that Te4+ doping reduces the conductivity of the crystal from measurements of its conductivity at different temperatures and frequencies, indicating that Te:KTP has excellent electro-optical properties. The effect of Te4+ doping on the second harmonic generation in KTP was also studied. The thermal expansion, thermal diffusivity, thermal conductivity and specific heat capacity of KTP and Te:KTP were determined.

Polymorphism and metal-induced structural transformation in 5,5'-bis(4-pyridyl)(2,2'-bispyrimidine) adlayers on Au(111).

PubMed

Hötger, Diana; Carro, Pilar; Gutzler, Rico; Wurster, Benjamin; Chandrasekar, Rajadurai; Klyatskaya, Svetlana; Ruben, Mario; Salvarezza, Roberto C; Kern, Klaus; Grumelli, Doris

2018-05-31

Metal-organic coordination networks self-assembled on surfaces have emerged as functional low-dimensional architectures with potential applications ranging from the fabrication of functional nanodevices to electrocatalysis. Among them, bis-pyridyl-bispyrimidine (PBP) and Fe-PBP on noble metal surfaces appear as interesting systems in revealing the details of the molecular self-assembly and the effect of metal incorporation on the organic network arrangement. Herein, we report a combined STM, XPS, and DFT study revealing polymorphism in bis-pyridyl-bispyrimidine adsorbed adlayers on the reconstructed Au(111) surface. The polymorphic structures are converted by the addition of Fe adatoms into one unique Fe-PBP surface structure. DFT calculations show that while all PBP phases exhibit a similar thermodynamic stability, metal incorporation selects the PBP structure that maximizes the number of metal-N close contacts. Charge transfer from the Fe adatoms to the Au substrate and N-Fe interactions stabilize the Fe-PBP adlayer. The increased thermodynamic stability of the metal-stabilized structure leads to its sole expression on the surface.

Adsorption-desorption mechanism of phosphate by immobilized nano-sized magnetite layer: interface and bulk interactions.

PubMed

Zach-Maor, Adva; Semiat, Raphael; Shemer, Hilla

2011-11-15

Phosphate adsorption mechanism by a homogenous porous layer of nano-sized magnetite particles immobilized onto granular activated carbon (nFe-GAC) was studied for both interface and bulk structures. X-ray Photoelectron Spectroscopy (XPS) analysis revealed phosphate bonding to the nFe-GAC predominantly through bidentate surface complexes. It was established that phosphate was adsorbed to the magnetite surface mainly via ligand exchange mechanism. Initially, phosphate was adsorbed by the active sites on the magnetite surface, after which it diffused into the interior of the nano-magnetite layer, as indicated by intraparticle diffusion model. This diffusion process continues regardless of interface interactions, revealing some of the outer magnetite binding sites for further phosphate uptake. Desorption, using NaOH solution, was found to be predominantly a surface reaction, at which hydroxyl ions replace the adsorbed phosphate ions only at the surface outer biding sites. Five successive fix-bed adsorption/regeneration cycles were successfully applied, without significant reduction in the nFe-GAC adsorption capacity and at high regeneration efficiency. Copyright © 2011 Elsevier Inc. All rights reserved.

Quantitative depth profiling of Ce(3+) in Pt/CeO2 by in situ high-energy XPS in a hydrogen atmosphere.

PubMed

Kato, Shunsuke; Ammann, Markus; Huthwelker, Thomas; Paun, Cristina; Lampimäki, Markus; Lee, Ming-Tao; Rothensteiner, Matthäus; van Bokhoven, Jeroen A

2015-02-21

The redox property of ceria is a key factor in the catalytic activity of ceria-based catalysts. The oxidation state of well-defined ceria nanocubes in gas environments was analysed in situ by a novel combination of near-ambient pressure X-ray Photoelectron Spectroscopy (XPS) and high-energy XPS at a synchrotron X-ray source. In situ high-energy XPS is a promising new tool to determine the electronic structure of matter under defined conditions. The aim was to quantitatively determine the degree of cerium reduction in a nano-structured ceria-supported platinum catalyst as a function of the gas environment. To obtain a non-destructive depth profile at near-ambient pressure, in situ high-energy XPS analysis was performed by varying the kinetic energy of photoelectrons from 1 to 5 keV, and, thus, the probing depth. In ceria nanocubes doped with platinum, oxygen vacancies formed only in the uppermost layers of ceria in an atmosphere of 1 mbar hydrogen and 403 K. For pristine ceria nanocubes, no change in the cerium oxidation state in various hydrogen or oxygen atmospheres was observed as a function of probing depth. In the absence of platinum, hydrogen does not dissociate and, thus, does not lead to reduction of ceria.

A room temperature ethanol sensor made from p-type Sb-doped SnO2 nanowires.

PubMed

Wu, Jyh Ming

2010-06-11

A p-type ethanol sensor with a response time of approximately 8.3 s at room temperature was produced by SnO(2):Sb nanowires. The electrical properties of p-type SnO(2) nanowires are stable with a hole concentration of 1.544 x 10(17) cm(-3) and a field-effect mobility of 22 cm(2) V(-2) S(-1). X-ray photoelectron spectroscopy (XPS) and Hall measurement revealed that as-synthesized nanowires exhibit p-type behavior. A comprehensive investigation of the p-type sensing mechanism is reported.

Low temperature synthesis of hexagonal ZnO nanorods and their hydrogen sensing properties

NASA Astrophysics Data System (ADS)

Qurashi, Ahsanulhaq; Faiz, M.; Tabet, N.; Alam, Mir Waqas

2011-08-01

The growth of hexagonal ZnO nanorods was demonstrated by low temperature chemical synthesis approach. X-ray diffraction (XRD) analysis revealed a wurtzite hexagonal structure of the ZnO nanorods. The optical properties were measured by UV-vis spectrophotometer at room temperature. X-ray photoelectron spectroscopy (XPS) confirmed high purity of the ZnO nanorods. The hydrogen sensor made of the ZnO nanorods showed reversible response. The hydrogen gas tests were carried out in presence of ambient air and the influence of operation temperature on the hydrogen gas sensing property of ZnO nanorods was also investigated.

High rate dry etching of (BiSb)2Te3 film by CH4/H2-based plasma

NASA Astrophysics Data System (ADS)

Song, Junqiang; Shi, Xun; Chen, Lidong

2014-10-01

Etching characteristics of p-type (BiSb)2Te3 films were studied with CH4/H2/Ar gas mixture using an inductively coupled plasma (ICP)-reactive ion etching (RIE) system. The effects of gas mixing ratio, working pressure and gas flow rate on the etch rate and the surface morphology were investigated. The vertical etched profile with the etch rate of 600 nm/min was achieved at the optimized processing parameters. X-ray photoelectron spectroscopy (XPS) analysis revealed the non-uniform etching of (BiSb)2Te3 films due to disparate volatility of the etching products. Micro-masking effects caused by polymer deposition and Bi-rich residues resulted in roughly etched surfaces. Smooth surfaces can be obtained by optimizing the CH4/H2/Ar mixing ratio.

Two novel penetrating coordination polymers based on flexible S-containing dicarboxylate acid with sensing properties towards Fe3+ and Cr2O72- ions

NASA Astrophysics Data System (ADS)

Chen, Zhiwei; Mi, Xiuna; Wang, Suna; Lu, Jing; Li, Yunwu; Li, Dacheng; Dou, Jianmin

2018-05-01

Two new coordination polymers (CPs), namely, {[Zn(L)(bpp)]·DMF}n (1) and {[Zn(L)(bpe)]·DMF}n (2) (L = 2,2'-[benzene-1,3-diylbis(methanediylsulfanediyl)]dibenzoic acid, bpp= 1,3-bis(4-pyridyl)propane, bpe = 1,2-Bis(4-pyridyl)ethylene, DMF = N,N-Dimethylformamide), have been solvothermally synthesized and fully characterized. Complex 1 displays a 2D→2D three-fold"false" interpenetrating structure while complex 2 possesses a novel 3-D 4-connected structure with fascinating self-penetrating moieties. The luminescence studies reveal that these complexes exhibited excellent selectivity for Fe3+ and Cr2O72- ions in DMF. The sensing mechanism was investigated through PXRD, XPS , EDS mapping measurements, and discussed in details.

Lattice and Valence Electronic Structures of Crystalline Octahedral Molybdenum Halide Clusters-Based Compounds, Cs2[Mo6X14] (X = Cl, Br, I), Studied by Density Functional Theory Calculations.

PubMed

Saito, Norio; Cordier, Stéphane; Lemoine, Pierric; Ohsawa, Takeo; Wada, Yoshiki; Grasset, Fabien; Cross, Jeffrey S; Ohashi, Naoki

2017-06-05

The electronic and crystal structures of Cs 2 [Mo 6 X 14 ] (X = Cl, Br, I) cluster-based compounds were investigated by density functional theory (DFT) simulations and experimental methods such as powder X-ray diffraction, ultraviolet-visible spectroscopy, and X-ray photoemission spectroscopy (XPS). The experimentally determined lattice parameters were in good agreement with theoretically optimized ones, indicating the usefulness of DFT calculations for the structural investigation of these clusters. The calculated band gaps of these compounds reproduced those experimentally determined by UV-vis reflectance within an error of a few tenths of an eV. Core-level XPS and effective charge analyses indicated bonding states of the halogens changed according to their sites. The XPS valence spectra were fairly well reproduced by simulations based on the projected electron density of states weighted with cross sections of Al K α , suggesting that DFT calculations can predict the electronic properties of metal-cluster-based crystals with good accuracy.

Dynamic XPS measurements of ultrathin polyelectrolyte films containing antibacterial Ag–Cu nanoparticles

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

Taner-Camcı, Merve; Suzer, Sefik, E-mail: suzer@fen.bilkent.edu.tr

Ultrathin films consisting of polyelectrolyte layers prepared by layer-by-layer deposition technique and containing also Ag and Cu nanoparticles exhibit superior antibacterial activity toward Escherichia coli. These films have been investigated with XPS measurements under square wave excitation at two different frequencies, in order to further our understanding about the chemical/physical nature of the nanoparticles. Dubbed as dynamical XPS, such measurements bring out similarities and differences among the surface structures by correlating the binding energy shifts of the corresponding XPS peaks. Accordingly, it is observed that the Cu2p, Ag3d of the metal nanoparticles, and S2p of cysteine, the stabilizer and themore » capping agent, exhibit similar shifts. On the other hand, the C1s, N1s, and S2p peaks of the polyelectrolyte layers shift differently. This finding leads us the claim that the Ag and Cu atoms are in a nanoalloy structure, capped with cystein, as opposed to phase separated entities.« less

Lab-based ambient pressure X-ray photoelectron spectroscopy from past to present

NASA Astrophysics Data System (ADS)

Arble, Chris; Jia, Meng; Newberg, John T.

2018-05-01

Chemical interactions which occur at a heterogeneous interface between a gas and substrate are critical in many technological and natural processes. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) is a powerful spectroscopy tool that is inherently surface sensitive, elemental and chemical specific, with the ability to probe sample surfaces in the presence of a gas phase. In this review, we discuss the evolution of lab-based AP-XPS instruments, from the first development by Siegbahn and coworkers up through modern day systems. A comprehensive overview is given of heterogeneous experiments investigated to date via lab-based AP-XPS along with the different instrumental metrics that affect the quality of sample probing. We conclude with a discussion of future directions for lab-based AP-XPS, highlighting the efficacy for this in-demand instrument to continue to expand in its ability to significantly advance our understanding of surface chemical processes under in situ conditions in a technologically multidisciplinary setting.

Quantitative analysis of Si1-xGex alloy films by SIMS and XPS depth profiling using a reference material

NASA Astrophysics Data System (ADS)

Oh, Won Jin; Jang, Jong Shik; Lee, Youn Seoung; Kim, Ansoon; Kim, Kyung Joong

2018-02-01

Quantitative analysis methods of multi-element alloy films were compared. The atomic fractions of Si1-xGex alloy films were measured by depth profiling analysis with secondary ion mass spectrometry (SIMS) and X-ray Photoelectron Spectroscopy (XPS). Intensity-to-composition conversion factor (ICF) was used as a mean to convert the intensities to compositions instead of the relative sensitivity factors. The ICFs were determined from a reference Si1-xGex alloy film by the conventional method, average intensity (AI) method and total number counting (TNC) method. In the case of SIMS, although the atomic fractions measured by oxygen ion beams were not quantitative due to severe matrix effect, the results by cesium ion beam were very quantitative. The quantitative analysis results by SIMS using MCs2+ ions are comparable to the results by XPS. In the case of XPS, the measurement uncertainty was highly improved by the AI method and TNC method.

Modifications of Graphite and Multiwall Carbon Nanotubes in the Presence of Urea

NASA Astrophysics Data System (ADS)

Duraia, El-Shazly M.; Fahami, Abbas; Beall, Gary W.

2018-02-01

The effect of high-energy ball milling on two carbon allotropes, graphite and multiwall carbon nanotubes (MWCNT) in the presence of urea has been studied. Samples were investigated using Raman spectroscopy, x-ray diffraction, scanning electron microscope (SEM) and x-ray photoelectron spectroscopy (XPS). Nitrogen-doped graphene has been successfully synthesized via a simple scalable mechanochemistry method using urea and graphite powder precursors. XPS results revealed the existence of the different nitrogen atoms configurations including pyridine, pyrrodic and graphitic N. SEM observations showed that the graphene nanosheets morphology become more wrinkles folded and crumbled as the milling time increased. The ID/IG ratio also increased as the milling time rose. The presence of both D' and G + D bands at 1621 cm-1 and 2940 cm-1, respectively, demonstrated the nitrogen incorporation in the graphene lattice Two factors contribute to the used urea: first it helps to exfoliate graphite into graphene, and second it preserves the graphitic structure from damage during the milling process as well as acting as a solid-state nitrogen source. Based on the phase analysis, the d-spacing of MWCNT samples in the presence of urea decreased due to the mechanical force in the milling process as the milling time increased. On the other hand, in the graphite case, due to its open flat surface, the graphite (002) peak shifts toward lower two theta as the milling time increase. Such findings are important and could be used for large-scale production of N-doped graphene, diminishing the use of either dangerous chemicals or sophisticated equipment.

Two Keggin-type heteropolytungstates with transition metal as a central atom: Crystal structure and magnetic study with 2D-IR correlation spectroscopy

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

Chai, Feng; Chen, YiPing, E-mail: ypchen007@sina.com; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002

2013-06-01

Two Keggin-type heteropolytungstates, [Co(phen)₃]₃[CoW₁₂O₄₀]·9H₂O 1 (phen=1,10-phenanthroline) and [Fe(phen)₃]₂[FeW₁₂O₄₀]·H₃O·H₂O 2, have been synthesized via the hydrothermal technique and characterized by single crystal X-ray diffraction analyses, IR, XPS, TG analysis, UV–DRS, XRD, thermal-dependent and magnetic-dependent 2D-COS IR (two-dimensional infrared correlation spectroscopy). Crystal structure analysis reveals that the polyanions in compound 1 are linked into 3D supramolecule through hydrogen bonding interactions between lattice water molecules and terminal oxygen atoms of polyanion units, and [Co(phen)₃]²⁺ cations distributed in the polyanion framework with many hydrogen bonding interactions. The XPS spectra indicate that all the Co atoms in 1 are +2 oxidation state, the Fe atomsmore » in 2 existing with +2 and +3 mixed oxidation states. - Graphical abstract: The magnetic-dependent synchronous 2D correlation IR spectra of 1 (a), 2 (b) over 0–50 mT in the range of 600–1000 cm⁻¹, the obvious response indicate two Keggin polyanions skeleton susceptible to applied magnetic field. Highlights: • Two Keggin-type heteropolytungstates with transition metal as a central atom has been obtained. • Compound 1 forms into 3D supramolecular architecture through hydrogen bonding between water molecules and polyanions. • Magnetic-dependent 2D-IR correlation spectroscopy was introduced to discuss the magnetism of polyoxometalate.« less

The effect of surface charge on photocatalytic degradation of methylene blue dye using chargeable titania nanoparticles.

PubMed

Azeez, Fadhel; Al-Hetlani, Entesar; Arafa, Mona; Abdelmonem, Yasser; Nazeer, Ahmed Abdel; Amin, Mohamed O; Madkour, Metwally

2018-05-08

Herein, a simple approach based on tailoring the surface charge of nanoparticles, NPs, during the preparation to boost the electrostatic attraction between NPs and the organic pollutant was investigated. In this study, chargeable titania nanoparticles (TiΟ 2 NPs) were synthesized via a hydrothermal route under different pH conditions (pH = 1.6, 7.0 and 10). The prepared TiΟ 2 NPs were fully characterized via various techniques including; transmission electron microscopy (TEM), X-ray diffraction (XRD), N 2 adsorption/desorption, X-ray photoelectron spectroscopy (XPS), Ultraviolet-visible spectroscopy (UV-Vis) and dynamic light scattering (DLS). The influence of the preparation pH on the particle size, surface area and band gap was investigated and showed pH-dependent behavior. The results revealed that upon increasing the pH value, the particle size decreases and lead to larger surface area with less particles agglomeration. Additionally, the effect of pH on the surface charge was monitored by XPS to determine the amount of hydroxyl groups on the TiO 2 NPs surface. Furthermore, the photocatalytic activity of the prepared TiΟ 2 NPs towards methylene blue (MB) photodegradation was manifested. The variation in the preparation pH affected the point of zero charge (pH PZC ) of TiO 2 NPs, subsequently, different photocatalytic activities based on electrostatic interactions were observed. The optimum efficiency obtained was 97% at a degradation rate of 0.018 min -1 using TiO 2 NPs prepared at pH 10.

Comparative study of GeO{sub 2}/Ge and SiO{sub 2}/Si structures on anomalous charging of oxide films upon water adsorption revealed by ambient-pressure X-ray photoelectron spectroscopy

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

Mori, Daichi; Kawai, Kentaro; Morita, Mizuho

2016-09-07

The energy difference between the oxide and bulk peaks in X-ray photoelectron spectroscopy (XPS) spectra was investigated for both GeO{sub 2}/Ge and SiO{sub 2}/Si structures with thickness-controlled water films. This was achieved by obtaining XPS spectra at various values of relative humidity (RH) of up to ∼15%. The increase in the energy shift is more significant for thermal GeO{sub 2} on Ge than for thermal SiO{sub 2} on Si above ∼10{sup −4}% RH, which is due to the larger amount of water molecules that infiltrate into the GeO{sub 2} film to form hydroxyls. Analyzing the origins of this energy shift,more » we propose that the positive charging of a partially hydroxylated GeO{sub 2} film, which is unrelated to X-ray irradiation, causes the larger energy shift for GeO{sub 2}/Ge than for SiO{sub 2}/Si. A possible microscopic mechanism of this intrinsic positive charging is the emission of electrons from adsorbed water species in the suboxide layer of the GeO{sub 2} film to the Ge bulk, leaving immobile cations or positively charged states in the oxide. This may be related to the reported negative shift of flat band voltages in metal-oxide-semiconductor diodes with an air-exposed GeO{sub 2} layer.« less

Photofunctionalization and non-thermal plasma activation of titanium surfaces.

PubMed

Henningsen, Anders; Smeets, Ralf; Hartjen, Philip; Heinrich, Oliver; Heuberger, Roman; Heiland, Max; Precht, Clarissa; Cacaci, Claudio

2018-03-01

The aim of this study was to compare UV light and non-thermal plasma (NTP) treatment regarding the improvement of physical material characteristics and cell reaction on titanium surfaces in vitro after short-term functionalization. Moderately rough (Ra 1.8-2.0 μm) sandblasted and acid-etched titanium disks were treated by UV light (0.05 mW/cm 2 at λ = 360 nm and 2 mW/cm 2 at λ = 250 nm) or by NTP (24 W, -0.5 mbar) of argon or oxygen for 12 min each. Surface structure was investigated by scanning electron microscopy, confocal microscopy and X-ray photoelectron spectroscopy (XPS). Hydrophilicity was assessed by dynamic contact angle measurement. Cell attachment, viability, cell proliferation and cytotoxicity were assessed in vitro using murine osteoblast-like cells. UV irradiation or NTP treatment of titanium surfaces did not alter the surface structure. XPS analysis revealed a significantly increased oxidation of the surface and a decrease of carbon after the use of either method. NTP and UV light led to a significant better cell attachment of murine osteoblasts; significantly more osteoblasts grew on the treated surfaces at each time point (p < 0.001). UV light as well as NTP modified the surface of titanium and significantly improved the conditions for murine osteoblast cells in vitro. However, results indicate a slight advantage for NTP of argon and oxygen in a short time interval of surface functionalization compared to UV. UV light and NTP are able to improve surface conditions of dental implants made of titanium.

Improved reliability from a plasma-assisted metal-insulator-metal capacitor comprising a high-k HfO2 film on a flexible polyimide substrate.

PubMed

Meena, Jagan Singh; Chu, Min-Ching; Kuo, Shiao-Wei; Chang, Feng-Chih; Ko, Fu-Hsiang

2010-03-20

We have used a sol-gel spin-coating process to fabricate a new metal-insulator-metal (MIM) capacitor comprising a 10 nm-thick high-k thin dielectric HfO(2) film on a flexible polyimide (PI) substrate. The surface morphology of this HfO(2) film was investigated using atomic force microscopy and scanning electron microscopy, which confirmed that continuous and crack-free film growth had occurred on the film surface. After oxygen (O(2)) plasma pretreatment and subsequent annealing at 250 degrees C, the film on the PI substrate exhibited a low leakage current density of 3.64 x 10(-9) A cm(-2) at 5 V and a maximum capacitance density of 10.35 fF microm(-2) at 1 MHz. The as-deposited sol-gel film was completely oxidized when employing O(2) plasma at a relatively low temperature (ca. 250 degrees C), thereby enhancing the electrical performance. We employed X-ray photoelectron spectroscopy (XPS) at both high and low resolution to examine the chemical composition of the film subjected to various treatment conditions. The shift of the XPS peaks towards higher binding energy, revealed that O(2) plasma treatment was the most effective process for the complete oxidation of hafnium atoms at low temperature. A study of the insulator properties indicated the excellent bendability of our MIM capacitor; the flexible PI substrate could be bent up to 10(5) times and folded to near 360 degrees without any deterioration in its electrical performance.

Hidden relationship between the electrical conductivity and the Mn 2p core-level photoemission spectra in La{sub 1-x}Sr{sub x}MnO{sub 3}

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

Hishida, T.; Ohbayashi, K.; Saitoh, T.

2013-01-28

Core-level electronic structure of La{sub 1-x}Sr{sub x}MnO{sub 3} has been studied by x-ray photoemission spectroscopy (XPS). We first report, by the conventional XPS, the well-screened shoulder structure in Mn 2p{sub 3/2} peak, which had been observed only by hard x-ray photoemission spectroscopy so far. Multiple-peak analysis revealed that the Mn{sup 4+} spectral weight was not proportional to the nominal hole concentration x, indicating that a simple Mn{sup 3+}/Mn{sup 4+} intensity ratio analysis may result in a wrong quantitative elemental analysis. Considerable weight of the shoulder at x = 0.0 and the fact that the shoulder weight was even slightly goingmore » down from x = 0.2 to 0.4 were not compatible with the idea that this weight simply represents the metallic behavior. Further analysis found that the whole Mn 2p{sub 3/2} peak can be decomposed into four portions, the Mn{sup 4+}, the (nominal) Mn{sup 3+}, the shoulder, and the other spectral weight located almost at the Mn{sup 3+} location. We concluded that this weight represents the well-screened final state at Mn{sup 4+} sites, whereas the shoulder is known as that of the Mn{sup 3+} states. We found that the sum of these two spectral weight has an empirical relationship to the conductivity evolution with x.« less

Al-doped TiO{sub 2} mesoporous material supported Pd with enhanced catalytic activity for complete oxidation of ethanol

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

Zhu, Jing, E-mail: mlczjsls123@163.com; Mu, Wentao, E-mail: mwt15035687833@163.com; Su, Liqing, E-mail: suliqing0163@163.com

Pd catalysts supported on Al-doped TiO{sub 2} mesoporous materials were evaluated in complete oxidation of ethanol. The catalysts synthesized by wet impregnation based on evaporation-induced self-assembly were characterized by X-ray diffraction, measurement of pore structure, XPS, FT-IR, temperature programmed reduction and TEM. Characteristic results showed that the aluminium was doped into the lattice of mesoporous anatase TiO{sub 2} to form Al-O-Ti defect structure. Catalytic results revealed that Al-doped catalysts were much more active than the pristine one, especially at low temperature (≤200 °C). This should be ascribed to the introduction of aluminium ions that suppressed the strong metal-support interaction andmore » increased the active sites of Pd oxides, enhanced the stabilized anatase TiO{sub 2}, improved well dispersed high valence palladium species with high reducibility and enriched chemisorption oxygen. - Graphical abstract: Al-doped Pd/TiO{sub 2} exhibited optimal catalytic performance for ethanol oxidation and CO{sub 2} yield by the suppression of SMSI. - Highlights: • Palladium catalysts supported on Al-doped TiO{sub 2} mesoporous materials were studied. • The introduction of Al can enhance anatase stabilization and increase defect TiO{sub 2}. • The Pd/Al-TiO{sub 2} catalysts show higher ethanol conversion and CO{sub 2} yield than Pd/TiO{sub 2}. • The influence of Al on SMSI and catalytic performance were evaluated by TPR and XPS.« less

Shadow-casted ultrathin surface coatings of titanium and titanium/silicon oxide sol particles via ultrasound-assisted deposition.

PubMed

Karahan, H Enis; Birer, Özgür; Karakuş, Kerem; Yıldırım, Cansu

2016-07-01

Ultrasound-assisted deposition (USAD) of sol nanoparticles enables the formation of uniform and inherently stable thin films. However, the technique still suffers in coating hard substrates and the use of fast-reacting sol-gel precursors still remains challenging. Here, we report on the deposition of ultrathin titanium and titanium/silicon hybrid oxide coatings using hydroxylated silicon wafers as a model hard substrate. We use acetic acid as the catalyst which also suppresses the reactivity of titanium tetraisopropoxide while increasing the reactivity of tetraethyl orthosilicate through chemical modifications. Taking the advantage of this peculiar behavior, we successfully prepared titanium and titanium/silicon hybrid oxide coatings by USAD. Varying the amount of acetic acid in the reaction media, we managed to modulate thickness and surface roughness of the coatings in nanoscale. Field-emission scanning electron microscopy and atomic force microscopy studies showed the formation of conformal coatings having nanoroughness. Quantitative chemical state maps obtained by x-ray photoelectron spectroscopy (XPS) suggested the formation of ultrathin (<10nm) coatings and thickness measurements by rotating analyzer ellipsometry supported this observation. For the first time, XPS chemical maps revealed the transport effect of ultrasonic waves since coatings were directly cast on rectangular substrates as circular shadows of the horn with clear thickness gradient from the center to the edges. In addition to the progress made in coating hard substrates, employing fast-reacting precursors and achieving hybrid coatings; this report provides the first visual evidence on previously suggested "acceleration and smashing" mechanism as the main driving force of USAD. Copyright © 2016 Elsevier B.V. All rights reserved.

Deuterium permeation behaviors in tungsten implanted with nitrogen

NASA Astrophysics Data System (ADS)

Liang, Chuan-hui; Wang, Dongping; Jin, Wei; Lou, Yuanfu; Wang, Wei; Ye, Xiaoqiu; Chen, Chang-an; Liu, Kezhao; Xu, Haiyan; Wang, Xiaoying; Kleyn, Aart W.

2018-07-01

Surface modification of tungsten due to the cooling species nitrogen seeded in the divertor region, i.e., by nitrogen ion implantation or re-deposition, is considered to affect the permeation behavior of H isotopes. This work focuses on the effect of nitrogen ion implantation into tungsten (W-N) on the deuterium gas-driven permeation behavior. For comparison, both permeation in tungsten implanted with W ion (W-W) and without implantation (pristine W) are studied. These three samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photo-electron spectroscopy (XPS). The SEM results revealed that the W-W sample has various voids on the surface, and the W-N sample has a rough surface with pretty fine microstructures. These are different from the pristine W sample with a smooth and compact surface. The XRD patterns show the disappearance of crystallinity on both W-W and W-N sample surfaces. It indicates that the ion implantation process results in an almost complete conversion from crystalline to amorphous in the sample surfaces. The sputter-depth profiling XPS spectra show that the implanted nitrogen prefers to form a 140 nm thick tungsten nitride layer. In permeation experiments, it was found that the D permeability is temperature dependent. Interestingly, the W-N sample presented a lower D permeability than the W-W sample, but higher than the pristine W sample. Such behavior implies that tungsten nitride acts as a permeation barrier, while defects created by ions implantation can promote permeability. The possible permeation mechanism correlated with sample surface composition and microstructure is consequently discussed in this work.

Study on Cr(VI) Leaching from Cement and Cement Composites

PubMed Central

Palascakova, Lenka; Kanuchova, Maria

2018-01-01

This paper reports an experimental study on hexavalent chromium leaching from cement samples and cement composites containing silica fume and zeolite additions that were subjected to various leaching agents. The water-soluble Cr(VI) concentrations in cements ranged from 0.2 to 3.2 mg/kg and represented only 1.8% of the total chromium content. The presence of chromium compounds with both chromium oxidation states of III and VI was detected in the cement samples by X-ray photoelectron spectroscopy (XPS). Leaching tests were performed in a Britton-Robinson buffer to simulate natural conditions and showed increased dissolution of Cr(VI) up to 6 mg/kg. The highest amount of leached hexavalent chromium was detected after leaching in HCl. The findings revealed that the leaching of chromium from cements was higher by 55–80% than that from the cement composites. A minimum concentration was observed for all cement samples when studying the relationship between the soluble Cr(VI) and the cement storage time. PMID:29690550

Study on Cr(VI) Leaching from Cement and Cement Composites.

PubMed

Estokova, Adriana; Palascakova, Lenka; Kanuchova, Maria

2018-04-22

This paper reports an experimental study on hexavalent chromium leaching from cement samples and cement composites containing silica fume and zeolite additions that were subjected to various leaching agents. The water-soluble Cr(VI) concentrations in cements ranged from 0.2 to 3.2 mg/kg and represented only 1.8% of the total chromium content. The presence of chromium compounds with both chromium oxidation states of III and VI was detected in the cement samples by X-ray photoelectron spectroscopy (XPS). Leaching tests were performed in a Britton-Robinson buffer to simulate natural conditions and showed increased dissolution of Cr(VI) up to 6 mg/kg. The highest amount of leached hexavalent chromium was detected after leaching in HCl. The findings revealed that the leaching of chromium from cements was higher by 55⁻80% than that from the cement composites. A minimum concentration was observed for all cement samples when studying the relationship between the soluble Cr(VI) and the cement storage time.

Proline adsorption on TiO 2(1 1 0) single crystal surface: A study by high resolution photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Fleming, G. J.; Adib, K.; Rodriguez, J. A.; Barteau, M. A.; Idriss, H.

2007-12-01

The surface chemistry and binding of DL-proline were investigated on the oxidised (stoichiometric) and reduced (sub-stoichiometric) TiO 2(1 1 0) single crystal surfaces. TiO 2 was chosen as the substrate as it best represents the surface of a biomedical implant, which bio-molecules interact with during the healing of bone/teeth fractures (molecular recognition). High resolution X-ray photoelectron spectroscopy (HR-XPS) studies of the C1s and N1s regions revealed that DL-proline is present in two forms (dissociated and zwitterionic) on the oxidised TiO 2 surface. On TiO 2(1 1 0) surfaces reduced by Ar + sputtering, a significant increase in the amount of zwitterionic proline at the surface was detected when compared with the oxidised surface. Study of the temperature effect showed that in both cases the zwitterionic structure was the less stable structure. The reason for its relative instability appears to be thermodynamic.

Flexible regenerated cellulose/polypyrrole composite films with enhanced dielectric properties.

PubMed

Raghunathan, Sreejesh Poikavila; Narayanan, Sona; Poulose, Aby Cheruvathur; Joseph, Rani

2017-02-10

Flexible regenerated cellulose/polypyrrole (RC-PPy) conductive composite films were prepared by insitu polymerization of pyrrole on regenerated cellulose (RC) matrix using ammonium persulphate as oxidant. FTIR, XPS and XRD analysis of RC-PPy composite films revealed strong interaction between polypyrrole (PPy) and RC matrix. XRD results indicated that crystalline structure of RC matrix remains intact even after composite formation. SEM micrographs revealed the formation of a continuous conductive network of PPy particles in the RC matrix, leading to significant improvement in electrical and dielectric properties. The electrical conductivity of RC-PPy composites with 12wt% of PPy was 3.2×10 -5 S/cm, which is approximately seven fold higher than that of RC. Composites showed high dielectric constant and low dielectric loss values, which is essential in capacitor application. Copyright © 2016 Elsevier Ltd. All rights reserved.

Investigating the stability of cathode materials for rechargeable lithium ion batteries

NASA Astrophysics Data System (ADS)

Huang, Yiqing

Lithium ion batteries are widely used in portable electronic devices and electric vehicles. However, safety is one of the most important issues for the Li-ion batteries' use. Some cathode materials, such as LiCoO 2, are thermally unstable in the charged state. Upon decomposition these cathode materials release O2, which could react with organic electrolyte, leading to a thermal runaway. Thus understanding the stability of the cathode materials is critical to the safety of lithium ion batteries. Olivine-type LiMnPO4 is a promising cathode material for lithium ion batteries because of its high energy density. We have revealed the critical role of carbon in the stability and thermal behaviour of olivine MnPO 4 obtained by chemical delithiation of LiMnPO4. (Li)MnPO 4 samples with various particle sizes and carbon contents were studied. Carbon-free LiMnPO4 obtained by solid state synthesis in O 2 becomes amorphous upon delithiation. Small amounts of carbon (0.3 wt.%) help to stabilize the olivine structure, so that completely delithiated crystalline olivine MnPO4 can be obtained. Larger amount of carbon (2 wt.%) prevents full delithiation. Heating in air, O2, or N 2 results in structural disorder (< 300 °C), formation of an intermediate sarcopside Mn3(PO4)2 phase (350 -- 450 °C), and complete decomposition to Mn2P2O 7 on extended heating at 400 °C. Carbon protects MnPO4 from reacting with environmental water, which is detrimental to its structural stability. We not only studied the crystalline olivine MnPO4, but also investigated the amorphous products obtained from carbon-free LiMnPO 4. We have revealed the Mn dissolution phenomenon during chemical delithiation of LiMnPO4, which causes the amorphization of olivine MnPO 4. Properties of crystalline-MnPO4 obtained from carbon-coated LiMnPO4 and of amorphous product resulting from the delithiation of pure LiMnPO4 were studied and compared. The P-rich amorphous phases in the latter are considered to be MnHP2O7 and MnH2P2O7 from XAS and XPS analysis. Safety of batteries not only depends on the stability of the active materials, but also the interactions between the active materials and electrolyte. Thus we study the stability between the cathode materials and the electrolyte. The thermal stability of electrochemically delithiated Li0.1N 0.8C0.15Al0.05O2 (NCA), FePO4 (FP), Mn0.8Fe0.2PO4 (MFP), hydrothermally synthesized VOPO4, LiVOPO4 and electrochemically lithiated Li2VOPO4 is investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis, coupled with mass spectrometry (TGA-MS). The thermal stability is found in the order: NCA< VOPO4< MFP< FP=LiVOPO4=Li2VOPO4. Sealed capsule high pressure experiments show a phase transformation of VOPO4 → HVOPO4 → H2VOPO4 when VOPO4 reacts with electrolyte (1 M LiPF6 in EC: DMC=1:1) between 200 and 300 °C. Finally, we characterize the lithium storage and release mechanism of V2O5 aerogels by x-ray photoelectron spectroscopy (XPS). We study the influence of n--butyllithium (n--BuLi) treatments on the electrochemical performance of the aerogel. In addition to fully reversible V reduction and oxidation due to the intercalation reaction, we observe the formation of LiOH species that are only partially reversible. This is attributed to reaction with the interlayer water and is considered responsible for the gradual capacity fade. The n--BuLi treated aerogels display a higher capacity than those without and our XPS analysis reveals an additional reversible formation of Li2O.

Impact of ambient environment on the electronic structure of CuPc/Au sample

NASA Astrophysics Data System (ADS)

Sinha, Sumona; Mukherjee, M.

2018-02-01

The performances of organic devices are crucially connected with their stability in the ambient environment. The impact of 24 h. Ambient environment exposure to the electronic structures of about 12 nm thick CuPc thin film on clean Au substrate have been studied employing UV photoemission spectroscopy technique. X-ray photoemission spectroscopy (XPS) was used to find out the origin of the change of the electronic structures in the sample with the exposure. The XPS study suggests that the oxidation occurs at the CuPc thin film. Due to the adsorption of oxygen in the CuPc film from the ambient air, charge carriers are formed within the CuPc film. Moreover, the XPS results imply that the CuPc film is sufficiently thinner for diffusing oxygen molecules through it and gets physically absorbed on Au substrate during the ambient exposure. Consequently, the hole injection barrier height of pristine CuPc film, grown on Au substrate, is reduced by about 0.50 eV and work-function of the pristine CuPc sample is enhanced by around 0.25 eV in the exposure. The findings will help to understand the mechanism that governs the degradation of performance of CuPc based devices in ambient environment.

Characterization of Natural Dyes and Traditional Korean Silk Fabric by Surface Analytical Techniques.

PubMed

Lee, Jihye; Kang, Min Hwa; Lee, Kang-Bong; Lee, Yeonhee

2013-05-15

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) and X-ray photoelectron spectroscopy (XPS) are well established surface techniques that provide both elemental and organic information from several monolayers of a sample surface, while also allowing depth profiling or image mapping to be carried out. The static TOF-SIMS with improved performances has expanded the application of TOF-SIMS to the study of a variety of organic, polymeric and biological materials. In this work, TOF-SIMS, XPS and Fourier Transform Infrared (FTIR) measurements were used to characterize commercial natural dyes and traditional silk fabric dyed with plant extracts dyes avoiding the time-consuming and destructive extraction procedures necessary for the spectrophotometric and chromatographic methods previously used. Silk textiles dyed with plant extracts were then analyzed for chemical and functional group identification of their dye components and mordants. TOF-SIMS spectra for the dyed silk fabric showed element ions from metallic mordants, specific fragment ions and molecular ions from plant-extracted dyes. The results of TOF-SIMS, XPS and FTIR are very useful as a reference database for comparison with data about traditional Korean silk fabric and to provide an understanding of traditional dyeing materials. Therefore, this study shows that surface techniques are useful for micro-destructive analysis of plant-extracted dyes and Korean dyed silk fabric.

Spectroellipsometric, AFM and XPS probing of stainless steel surfaces subjected to biological influences

NASA Astrophysics Data System (ADS)

Vinnichenko, M.; Chevolleau, Th; Pham, M. T.; Poperenko, L.; Maitz, M. F.

2002-11-01

Surface modification of austenitic stainless steel (SS) 316L after incubation in growing cell cultures and cell-free media as control has been studied. The following treatments were applied: mouse fibrosarcoma cells L929 for 3 and 7 days, polymorphonuclear neutrophils for 3 and 7 days and human osteosarcoma cells SAOS-2 for 7 and 14 days. Cells were enzymatically removed in all cases. The modified surfaces were probed in comparison with untreated ones by means of spectroscopic ellipsometry (SE), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). XPS shows the appearance of the peak of bonded nitrogen at 400.5 eV characteristic for adsorbed proteins on the surface for each type of cells and for the cell-free medium. Migration of Ni in the adsorbed layer is observed in all cases for samples after the cell cultures. The protein layer thickness is ellipsometrically determined to be within 2.5-6.0 nm for all treated samples with parameterization of its optical constants in Cauchy approach. The study showed that for such biological treatments of the SS the protein layer adsorption is the dominating process in the first 2 weeks, which could play a role in the process of corrosion by complex forming properties with metal ions.

XPS study of the surface chemistry of UO2 (111) single crystal film

NASA Astrophysics Data System (ADS)

Maslakov, Konstantin I.; Teterin, Yury A.; Popel, Aleksej J.; Teterin, Anton Yu.; Ivanov, Kirill E.; Kalmykov, Stepan N.; Petrov, Vladimir G.; Springell, Ross; Scott, Thomas B.; Farnan, Ian

2018-03-01

A (111) air-exposed surface of UO2 thin film (150 nm) on (111) YSZ (yttria-stabilized zirconia) before and after the Ar+ etching and subsequent in situ annealing in the spectrometer analytic chamber was studied by XPS technique. The U 5f, U 4f and O 1s electron peak intensities were employed for determining the oxygen coefficient kO = 2 + x of a UO2+x oxide on the surface. It was found that initial surface (several nm) had kO = 2.20. A 20 s Ar+ etching led to formation of oxide UO2.12, whose composition does not depend significantly on the etching time (up to 180 s). Ar+ etching and subsequent annealing at temperatures 100-380 °C in vacuum was established to result in formation of stable well-organized structure UO2.12 reflected in the U 4f XPS spectra as high intensity (∼28% of the basic peak) shake-up satellites 6.9 eV away from the basic peaks, and virtually did not change the oxygen coefficient of the sample surface. This agrees with the suggestion that a stable (self-assembling) phase with the oxygen coefficient kO ≈ 2.12 forms on the UO2 surface.

Surface chemical study on the covalent attachment of hydroxypropyltrimethyl ammonium chloride chitosan to titanium surfaces

NASA Astrophysics Data System (ADS)

Xu, Xiaofen; Wang, Ling; Guo, Shengrong; Lei, Lei; Tang, Tingting

2011-10-01

An anti-microbial and bioactive coating could not only reduce the probability of infection related to titanium implants but also support the growth of surrounding osteogenic cells. Our previous study has showed that hydroxypropyltrimethyl ammonium chloride chitosan (HACC) with a DS (degrees of substitution) of 18% had improved solubility and significantly higher antibacterial activities against three bacteria which were usually associated with infections in orthopaedics. In the current study, HACC with a DS of 18% coating was bonded to titanium surface by a three-step process. The titanium surface after each individual reaction step was analyzed by X-ray photoelectron spectroscopy (XPS) and attenuated total reflection (ATR) of Fourier-transformed infrared (FT-IR) spectroscopy. The XPS results demonstrated that there were great changes in the atomic ratios of C/Ti, O/Ti, and N/Ti after each reaction step. The XPS high resolution and corresponding devolution spectra of carbon, oxygen, nitrogen, and titanium were also in good coordination with the anticipated reaction steps. Additionally, the absorption bands around 3365 cm -1 (-OH vibration), 1664 cm -1 (Amide I), 1165 cm -1 ( νas, C-O-C bridge), and the broad absorption bands between 958 cm -1 and 1155 cm -1 (skeletal vibrations involving the C-O stretching of saccharide structure of HACC) verified that HACC was successfully attached to titanium surface.

Thickness and composition of ultrathin SiO2 layers on Si

NASA Astrophysics Data System (ADS)

van der Marel, C.; Verheijen, M. A.; Tamminga, Y.; Pijnenburg, R. H. W.; Tombros, N.; Cubaynes, F.

2004-07-01

Ultrathin SiO2 layers are of importance for the semiconductor industry. One of the techniques that can be used to determine the chemical composition and thickness of this type of layers is x-ray photoelectron spectroscopy (XPS). As shown by Seah and Spencer [Surf. Interface Anal. 33, 640 (2002)], it is not trivial to characterize this type of layer by means of XPS in a reliable way. We have investigated a series of ultrathin layers of SiO2 on Si (in the range from 0.3 to 3 nm) using XPS. The samples were also analyzed by means of transmission electron microscopy (TEM), Rutherford backscattering (RBS), and ellipsometry. The thickness of the SiO2 layers (d) was determined from the XPS results using three different approaches: the ``standard'' equation (Seah and Spencer) for d, an overlayer-substrate model calculation, and the QUASES-Tougaard [Surf. Interface Anal. 26, 249 (1998), QUASES-Tougaard: Software package for Quantitative Analysis of Surfaces by Electron Spectroscopy, version 4.4 (2000); http://www.quases.com] method. Good agreement was obtained between the results of XPS analyses using the ``standard'' equation, the overlayer-substrate model calculation, and RBS results. The QUASES-Tougaard results were approximately 62% above the other XPS results. The optical values for the thickness were always slightly higher than the thickness according to XPS or RBS. Using the model calculation, these (relatively small) deviations from the optical results could be explained as being a consequence of surface contaminations with hydrocarbons. For a thickness above 2.5 nm, the TEM results were in good agreement with the results obtained from the other techniques (apart from QUASES-Tougaard). Below 2.5 nm, significant deviations were found between RBS, XPS, and optical data on the one hand and TEM results on the other hand; the deviations became larger as the thickness of the SiO2 decreased. This effect may be related to interface states of oxygen, which have been investigated [D. A. Muller, T. Sorsch, S. Moccio, F. H. Baumann, K. Evans-Lutterodt, and G. Timp, Nature (London) 399, 758 (1999); D. A. Muller and J. B. Neaton, Structure and Energetics of the Interface Between Si and Amorphous SiO2 in Fundamental Aspects of Silicon Oxidation, edited by Y. J. Chabal (Springer, Berlin, 2001), pp. 219-246.] by means of high-resolution electron energy loss spectroscopy measurements of the O K edge in ultrathin gate oxides of SiO2. .

In-situ preparation of N-TiO2/graphene nanocomposite and its enhanced photocatalytic hydrogen production by H2S splitting under solar light.

PubMed

Bhirud, Ashwini P; Sathaye, Shivaram D; Waichal, Rupali P; Ambekar, Jalindar D; Park, Chan-J; Kale, Bharat B

2015-03-21

Highly monodispersed nitrogen doped TiO2 nanoparticles were successfully deposited on graphene (N-TiO2/Gr) by a facile in-situ wet chemical method for the first time. N-TiO2/Gr has been further used for photocatalytic hydrogen production using a naturally occurring abundant source of energy i.e. solar light. The N-TiO2/Gr nanocomposite composition was optimized by varying the concentrations of dopant nitrogen and graphene (using various concentrations of graphene) for utmost hydrogen production. The structural, optical and morphological aspects of nanocomposites were studied using XRD, UV-DRS, Raman, XPS, FESEM, and TEM. The structural study of the nanocomposite shows existence of anatase N-TiO2. Further, the details of the components present in the composition were confirmed with Raman and XPS. The morphological study shows that very tiny, 7-10 nm sized, N-TiO2 nanoparticles are deposited on the graphene sheet. The optical study reveals a drastic change in absorption edge and consequent total absorption due to nitrogen doping and presence of graphene. Considering the extended absorption edge to the visible region, these nanocomposites were further used as a photocatalyst to transform hazardous H2S waste into eco-friendly hydrogen using solar light. The N-TiO2/Gr nanocomposite with 2% graphene exhibits enhanced photocatalytic stable hydrogen production i.e. ∼5941 μmol h(-1) under solar light irradiation using just 0.2 gm nanocomposite, which is much higher as compared to P25, undoped TiO2 and TiO2/Gr nanocomposite. The enhancement in the photocatalytic activity is attributed to 'N' doping as well as high specific surface area and charge carrier ability of graphene. The recycling of the photocatalyst shows a good stability of the nanocomposites. This work may provide new insights to design other semiconductor deposited graphene novel nanocomposites as a visible light active photocatalyst.

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

Amusan, Akinwumi A., E-mail: akinwumi.amusan@ovgu.de; Kalkofen, Bodo; Burte, Edmund P.

Silver (Ag) layers were deposited by remote plasma enhanced atomic layer deposition (PALD) using Ag(fod)(PEt{sub 3}) (fod = 2,2-dimethyl-6,6,7,7,8,8,8-heptafluorooctane-3,5-dionato) as precursor and hydrogen plasma on silicon substrate covered with thin films of SiO{sub 2}, TiN, Ti/TiN, Co, Ni, and W at different deposition temperatures from 70  to 200 °C. The deposited silver films were analyzed by x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM) with energy dispersive x-ray spectroscopy, four point probe measurement, ellipsometric measurement, x-ray fluorescence (XRF), and x-ray diffraction (XRD). XPS revealed pure Ag with carbon and oxygen contamination close to the detectionmore » limit after 30 s argon sputtering for depositions made at 120 and 200 °C substrate temperatures. However, an oxygen contamination was detected in the Ag film deposited at 70 °C after 12 s argon sputtering. A resistivity of 5.7 × 10{sup −6} Ω cm was obtained for approximately 97 nm Ag film on SiO{sub 2}/Si substrate. The thickness was determined from the SEM cross section on the SiO{sub 2}/Si substrate and also compared with XRF measurements. Polycrystalline cubic Ag reflections were identified from XRD for PALD Ag films deposited at 120 and 200 °C. Compared to W surface, where poor adhesion of the films was found, Co, Ni, TiN, Ti/TiN and SiO{sub 2} surfaces had better adhesion for silver films as revealed by SEM, TEM, and AFM images.« less

Graphene nanoplate-MnO2 composites for supercapacitors: a controllable oxidation approach

NASA Astrophysics Data System (ADS)

Huang, Huajie; Wang, Xin

2011-08-01

Graphene nanoplate-MnO2 composites have been synthesized by oxidising part of the carbon atoms in the framework of graphene nanoplates at ambient temperature. The composites were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). It was found that the oxidation extent of the carbon atoms in the graphene framework in these composites was dependent on the reaction time, which also influenced their microstructure, morphology and electrochemical properties. Compared with MnO2 nanolamellas, the nanocomposite prepared with a reaction time of 3 h reveals better electrochemical properties as a supercapacitor electrode material.Graphene nanoplate-MnO2 composites have been synthesized by oxidising part of the carbon atoms in the framework of graphene nanoplates at ambient temperature. The composites were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). It was found that the oxidation extent of the carbon atoms in the graphene framework in these composites was dependent on the reaction time, which also influenced their microstructure, morphology and electrochemical properties. Compared with MnO2 nanolamellas, the nanocomposite prepared with a reaction time of 3 h reveals better electrochemical properties as a supercapacitor electrode material. Electronic supplementary information (ESI) available: Fig. S1, AFM image (5 μm × 5 μm) of graphene nanoplate-MnO2 composite obtained at 3 h; Fig. S2, nitrogen adsorption/desorption isotherm of graphene nanoplate-MnO2 composite obtained at 3 h. See DOI: 10.1039/c1nr10229j

Green synthesis of stabilized spherical shaped gold nanoparticles using novel aqueous Elaeis guineensis (oil palm) leaves extract

NASA Astrophysics Data System (ADS)

Ahmad, Tausif; Bustam, Mohamad Azmi; Irfan, Muhammad; Moniruzzaman, Muhammad; Anwaar Asghar, Hafiz Muhammad; Bhattacharjee, Sekhar

2018-05-01

In the last decade, development of bioinspired protocols to synthesize gold nanoparticles (AuNPs) using plants and their extracts have been dealt by researchers due to their low cost, renewability and non-toxic features. A simple, cheap and ecofriendly method is reported to synthesize stabilized AuNPs of size 35-75 nm at room temperature using aqueous Elaeis guineensis (oil palm) leaves extract without addition of any external agent. Oil palm leaves mediated AuNPs were characterized using FTIR, UV-vis spectrophotometer, EDAX, XPS, FESEM, TEM, DLS and TGA. FTIR spectra results revealed contribution of phenolic, carboxylic, amines and amides in reduction of trivalent gold ions and stabilization of formed gold atoms. Reaction solution color change and UV-vis spectra confirmed reduction of gold ions to generate gold atoms. Reaction mechanism explained the role of phenolic compounds in reduction reaction using FTIR and UV-vis spectra results. EDAX and XPS results further validated the formation of metallic gold particles through bioreduction of gold ions. Crystal structure of metallic gold particles was confirmed through XRD peaks indexing to (111), (200), (220) and (311) planes. TEM and FESEM particles size measurements exhibited the formation of nanostructured AuNPs. Synthesis of well scattered and spherical shaped AuNPs was revealed through FESEM and TEM images. The excellent stability of AuNPs was shown through high negative zeta potential value (-14.7 ± 4.68 mV) and uniform dispersion in aqueous media. Our results disclosed the excellent potential of Elaeis guineensis (oil palm) leaves as reducing and stabilizing agents in green synthesis of well scattered spherical shaped AuNPs, which can be employed as strong candidates in medical drug delivery and industrial applications.

Structural and Electrical Characterization of SiO2 Gate Dielectrics Deposited from Solutions at Moderate Temperatures in Air.

PubMed

Esro, Mazran; Kolosov, Oleg; Jones, Peter J; Milne, William I; Adamopoulos, George

2017-01-11

Silicon dioxide (SiO 2 ) is the most widely used dielectric for electronic applications. It is usually produced by thermal oxidation of silicon or by using a wide range of vacuum-based techniques. By default, the growth of SiO 2 by thermal oxidation of silicon requires the use of Si substrates whereas the other deposition techniques either produce low quality or poor interface material and mostly require high deposition or annealing temperatures. Recent investigations therefore have focused on the development of alternative deposition paradigms based on solutions. Here, we report the deposition of SiO 2 thin film dielectrics deposited by spray pyrolysis in air at moderate temperatures of ≈350 °C from pentane-2,4-dione solutions of SiCl 4 . SiO 2 dielectrics were investigated by means of UV-vis absorption spectroscopy, spectroscopic ellipsometry, XPS, XRD, UFM/AFM, admittance spectroscopy, and field-effect measurements. Data analysis reveals smooth (R RMS < 1 nm) amorphous films with a dielectric constant of about 3.8, an optical band gap of ≈8.1 eV, leakage current densities in the order of ≈10 -7 A/cm 2 at 1 MV/cm, and high dielectric strength in excess of 5 MV/cm. XPS measurements confirm the SiO 2 stoichiometry and FTIR spectra reveal features related to SiO 2 only. Thin film transistors implementing spray-coated SiO 2 gate dielectrics and C 60 and pentacene semiconducting channels exhibit excellent transport characteristics, i.e., negligible hysteresis, low leakage currents, high on/off current modulation ratio on the order of 10 6 , and high carrier mobility.

Fabrication and characterization of ultrathin dextran layers: Time dependent nanostructure in aqueous environments revealed by OWLS.

PubMed

Saftics, Andras; Kurunczi, Sándor; Szekrényes, Zsolt; Kamarás, Katalin; Khánh, Nguyen Quoc; Sulyok, Attila; Bősze, Szilvia; Horvath, Robert

2016-10-01

Surface coatings of the polysaccharide dextran and its derivatives are key ingredients especially in label-free biosensors for the suppression of non-specific binding and for receptor immobilization. Nevertheless, the nanostructure of these ultrathin coatings and its tailoring by the variation of the preparation conditions have not been profoundly characterized and understood. In this work carboxymethylated dextran (CMD) was prepared and used for fabricating ultrathin surface coatings. A grafting method based on covalent coupling to aminosilane- and epoxysilane-functionalized surfaces was applied to obtain thin CMD layers. The carboxyl moiety of the CMD was coupled to the aminated surface by EDC-NHS reagents, while CMD coupling through epoxysilane molecules was performed without any additional reagents. The surface analysis following the grafting procedures consisted of X-ray photoelectron spectroscopy (XPS), attenuated total reflection infrared spectroscopy (ATR-IR), spectroscopic ellipsometry, atomic force microscopy (AFM) and optical waveguide lightmode spectroscopy (OWLS). The XPS and AFM measurements showed that the grafting resulted in a very thin dextran layer of a few nanometers. The OWLS method allowed devising the structure of the interfacial dextran layers by the evaluation of the optogeometrical parameters. The alteration in the nanostructure of the CMD layer with the chemical composition of the silane coverage and the pH of the grafting solution was revealed by in situ OWLS, specifically, lain down chains were found to be prevalent on the surface under neutral and basic conditions on epoxysilylated surfaces. The developed methodologies allowed to design and fabricate nanometer scale CMD layers with well-controlled surface structure, which are very difficult to characterize in aqueous environments using present instrumentations and highly hydrated surface layers. Copyright © 2016 Elsevier B.V. All rights reserved.

An Electrochemical, Microtopographical and Ambient Pressure X-Ray Photoelectron Spectroscopic Investigation of Si/TiO 2/Ni/Electrolyte Interfaces

DOE PAGES

Lichterman, Michael F.; Richter, Matthias H.; Hu, Shu; ...

2015-12-05

The electrical and spectroscopic properties of the TiO 2/Ni protection layer system, which enables stabilization of otherwise corroding photoanodes, have been investigated in contact with electrolyte solutions by scanning-probe microscopy, electrochemistry and in-situ ambient pressure X-ray photoelectron spectroscopy (AP-XPS). Specifically, the energy-band relations of the p +-Si/ALD-TiO 2/Ni interface have been determined for a selected range of Ni thicknesses. AP-XPS measurements using tender X-rays were performed in a three-electrode electrochemical arrangement under potentiostatic control to obtain information from the semiconductor near-surface region, the electrochemical double layer (ECDL) and the electrolyte beyond the ECDL. The degree of conductivity depended on themore » chemical state of the Ni on the TiO 2 surface. At low loadings of Ni, the Ni was present primarily as an oxide layer and the samples were not conductive, although the TiO 2 XPS core levels nonetheless displayed behavior indicative of a metal-electrolyte junction. In contrast, as the Ni thickness increased, the Ni phase was primarily metallic and the electrochemical behavior became highly conductive, with the AP-XPS data indicative of a metal-electrolyte junction. Electrochemical and microtopographical methods have been employed to better define the nature of the TiO 2/Ni electrodes and to contextualize the AP-XPS results.« less

Investigation of significantly high barrier height in Cu/GaN Schottky diode

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

Garg, Manjari, E-mail: meghagarg142@gmail.com; Kumar, Ashutosh; Singh, R.

2016-01-15

Current-voltage (I-V) measurements combined with analytical calculations have been used to explain mechanisms for forward-bias current flow in Copper (Cu) Schottky diodes fabricated on Gallium Nitride (GaN) epitaxial films. An ideality factor of 1.7 was found at room temperature (RT), which indicated deviation from thermionic emission (TE) mechanism for current flow in the Schottky diode. Instead the current transport was better explained using the thermionic field-emission (TFE) mechanism. A high barrier height of 1.19 eV was obtained at room temperature. X-ray photoelectron spectroscopy (XPS) was used to investigate the plausible reason for observing Schottky barrier height (SBH) that is significantlymore » higher than as predicted by the Schottky-Mott model for Cu/GaN diodes. XPS measurements revealed the presence of an ultrathin cuprous oxide (Cu{sub 2}O) layer at the interface between Cu and GaN. With Cu{sub 2}O acting as a degenerate p-type semiconductor with high work function of 5.36 eV, a high barrier height of 1.19 eV is obtained for the Cu/Cu{sub 2}O/GaN Schottky diode. Moreover, the ideality factor and barrier height were found to be temperature dependent, implying spatial inhomogeneity of barrier height at the metal semiconductor interface.« less

Microwave-assisted preparation of nitrogen-doped biochars by ammonium acetate activation for adsorption of acid red 18

NASA Astrophysics Data System (ADS)

Wang, Li; Yan, Wei; He, Chi; Wen, Hang; Cai, Zhang; Wang, Zixuan; Chen, Zhengzheng; Liu, Weifeng

2018-03-01

Nitrogen-doped biochars derived from Phragmites australis (PA) were prepared using ammonium chloride (AC) and ammonium acetate (AA) as nitrogen sources by phosphoric acid activation via microwave assisted treatment. Their physicochemical properties, acid red 18 (AR18) adsorption performance and possible mechanisms were systematically evaluated. Nitrogen was successfully doped onto the biochar's surface in the formation of pyrrole-N, pyridine-N and oxidized-N with pyridine-N being the major component (64%). The pHiep and basic foundational groups of the biochars increased consequently however their surface areas slightly decreased. The adsorption kinetic data were best fit to the pseudo-second order model and the equilibrium data were well simulated by Freundlich model for all biochars, indicating the important role of chemical interactions. The maximum AR18 adsorption capacities of PAB-AA and PAB-AC were 1.41 and 1.18 times higher compared with the non N-doped biochar, which were mainly attributed to the π-π EDA interaction between the pyridine-N and AR18 as revealed by the comparison of XPS analyses before and after AR18 adsorption. Meanwhile, other mechanisms such as pore filling effect, Lewis acid-base interaction, electrostatic attraction and hydrogen bonding also existed as demonstrated by BET, XPS and FTIR analyses.

Microwave-Accelerated Surface Modification of Plasmonic Gold Thin Films with Self-Assembled Monolayers of Alkanethiols

PubMed Central

Grell, Tsehai A.J.; Alabanza, Anginelle M.; Gaskell, Karen; Aslan, Kadir

2013-01-01

A rapid surface modification technique for the formation of self-assembled monolayers (SAMs) of alkanethiols on gold thin films using microwave heating in less than 10 min is reported. In this regard, SAMs of two model alkanethiols, 11-mercaptoundecanoic acid (11-MUDA, to generate a hydrophilic surface) and undecanethiol (UDET, a hydrophobic surface), were successfully formed on gold thin films using selective microwave heating in 1) a semi-continuous and 2) a continuous fashion and at room temperature (24 hours, control experiment, no microwave heating). The formation of SAMs of 11-MUDA and UDET were confirmed by contact angle measurements, Fourier–transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The contact angles for water on SAMs formed by the selective microwave heating and conventional room temperature incubation technique (24 hours) were measured to be similar for 11-MUDA and UDET. FT-IR spectroscopy results confirmed that the internal structure of SAMs prepared using both microwave heating and at room temperature were similar. XPS results revealed that the organic and sulfate contaminants found on bare gold thin films were replaced by SAMs after the surface modification process was carried out using both microwave heating and at room temperature. PMID:24083414

Adsorption-oxidation of hydrogen sulfide on Fe/walnut-shell activated carbon surface modified by NH3-plasma.

PubMed

Ning, Ping; Liu, Sijian; Wang, Chi; Li, Kai; Sun, Xin; Tang, Lihong; Liu, Gui

2018-02-01

Walnut-shell activated carbon (WSAC) supported ferric oxide was modified by non-thermal plasma (NTP), and the removal efficiency for hydrogen sulfide over Fe/WSAC modified by dielectric barrier discharge (DBD) was significantly promoted. The sample modified for 10min and 6.8kV output (30V input voltage) maintained 100% H 2 S conversion over a long reaction time of 390min. The surface properties of adsorbents modified by NTP under different conditions were evaluated by the methods of X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) analysis and in-situ Fourier transform infrared spectroscopy (FTIR), to help understand the effect of the NTP treatment. NTP treatment enhanced the adsorption capacity of Fe/WSAC, which could due to the formation of micro-pores with sizes of 0.4, 0.5 and 0.75nm. XPS revealed that chemisorbed oxygen changed into lattice oxygen after NTP treatment, and lattice oxygen is beneficial for H 2 S oxidation. From the in-situ FTIR result, transformation of the reaction path on Fe/WSAC was observed after NTP modification. The research results indicate that NTP is an effective method to improve the surface properties of the Fe/WSAC catalyst for H 2 S adsorption-oxidation. Copyright © 2017. Published by Elsevier B.V.

Surface modification of malachite with ethanediamine and its effect on sulfidization flotation

NASA Astrophysics Data System (ADS)

Feng, Qicheng; Zhao, Wenjuan; Wen, Shuming

2018-04-01

Ethanediamine was used to modify the mineral surface of malachite to improve its sulfidization and flotation behavior. The activation mechanism was investigated by adsorption experiments, X-ray photoelectron spectroscopy (XPS) analysis, and zeta potential measurements. Microflotation experiments showed that the flotation recovery of malachite was enhanced after the pretreatment of the mineral particles with ethanediamine prior to the addition of Na2S. Adsorption tests revealed that numerous sulfide ion species in the pulp solution were transferred onto the mineral surface through the formation of more copper sulfide species. This finding was confirmed by the results of the XPS measurements. Ethanediamine modification not only increased the contents of copper sulfide species on the malachite surface but also enhanced the reactivity of the sulfidization products. During sulfidization, Cu(II) species on the mineral surface were reduced into Cu(I) species, and the percentages of S22- and Sn2- relative to the total S increased after modification, resulting in increased surface hydrophobicity. The results of zeta potential measurements showed that the ethanediamine-modified mineral surface adsorbed with more sulfide ion species was advantageous to the attachment of xanthate species, thereby improving malachite floatability. The proposed ethanediamine modification followed by sulfidization xanthate flotation exhibits potential for industrial application.

Band alignment of 2D WS2/HfO2 interfaces from x-ray photoelectron spectroscopy and first-principles calculations

NASA Astrophysics Data System (ADS)

Zhu, H. L.; Zhou, C. J.; Tang, B. S.; Yang, W. F.; Chai, J. W.; Tay, W. L.; Gong, H.; Pan, J. S.; Zou, W. D.; Wang, S. J.; Chi, D. Z.

2018-04-01

We report on the growth of two-dimensional (2D) WS2 on high-k HfO2/Si substrates by reactive sputtering deposition. Raman, x-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy characterizations indicate that the 2D WS2 layers exhibit high-quality crystallinity and exact stoichiometry. Through high-resolution XPS valence spectra, we find a type I alignment at the interface of monolayer WS2/HfO2 with a valence band offset (VBO) of 1.95 eV and a conduction band offset (CBO) of 1.57 eV. The VBO and CBO are also found to increase up to 2.24 eV and 2.09 eV, respectively, with increasing WS2 layers. This is consistent with the results obtained from our first-principles calculations. Our theoretical calculations reveal that the remarkable splitting and shift of the W 5 d z 2 orbital originating from interlayer orbital coupling in thicker WS2 films induce a reduction of its bandgap, leading to an increase in both the VBO and CBO. This observation can be attributed to the asymmetric splitting at different high symmetric k-points caused by the interlayer orbital coupling.

Homogeneously dispersed CeO2 nanoparticles on exfoliated hexaniobate nanosheets

NASA Astrophysics Data System (ADS)

Marques, Thalles M. F.; Strayer, Megan E.; Ghosh, Anupama; Silva, Alexandre; Ferreira, Odair P.; Fujisawa, Kazunori; Alves da Cunha, Jose R.; Abreu, Guilherme J. P.; Terrones, Mauricio; Mallouk, Thomas E.; Viana, Bartolomeu C.

2017-12-01

Hexaniobate nanosheets derived from the parent compound K4Nb6O17 have been decorated with CeO2 nanoparticles by ion exchange with aqueous cerium (IV) solution. Very homogeneous CeO2 nanoparticle decoration of the hexaniobate sheets can be achieved by this method and the resulting composites may absorb visible light. HRTEM images show that ∼3.0 nm diameter CeO2 nanoparticles adhere to hexaniobate nanosheets that are exfoliated and then restacked prior to Ce deposition. The interfacial interaction between CeO2 nanoparticles and nanosheets would be due to an electrostatic attraction mechanism. Raman and XRD measurements have given strong evidence that CeO2 nanoparticles have fluorite structure. EDS, FTIR and XPS results suggest almost complete exchange of TBA+ and K+ by Ce4+. Cerium ion exchange on the acid exchanged parent compound, H2.9K1.1Nb6O17, revealed that the extent of Ce ion exchange is much greater in case of nanosheets, which may be rationalized by the larger surface area available after exfoliation. XPS measurements show that the ratio of Ce4+/Ce3+ is around 4.4, in agreement with the formation of fluorite structure (CeO2). Thus, these CeO2 nanoparticle/nanosheet composites may be useful for catalytic processes.

High sensitivity flat SiO2 fibres for medical dosimetry

NASA Astrophysics Data System (ADS)

Abdul Sani, Siti. F.; Alalawi, Amani I.; Azhar, Hairul A. R.; Amouzad Mahdiraji, Ghafour; Tamchek, Nizam; Nisbet, A.; Maah, M. J.; Bradley, D. A.

2014-11-01

We describe investigation of a novel undoped flat fibre fabricated for medical radiation dosimetry. Using high energy X-ray beams generated at a potential of 6 MV, comparison has been made of the TL yield of silica flat fibres, TLD-100 chips and Ge-doped silica fibres. The flat fibres provide competitive TL yield to that of TLD-100 chips, being some 100 times that of the Ge-doped fibres. Pt-coated flat fibres have then been used to increase photoelectron production and hence local dose deposition, obtaining significant increase in dose sensitivity over that of undoped flat fibres. Using 250 kVp X-ray beams, the TL yield reveals a progressive linear increase in dose for Pt thicknesses from 20 nm up to 80 nm. The dose enhancement factor (DEF) of (0.0150±0.0003) nm-1 Pt is comparable to that obtained using gold, agreeing at the 1% level with the value expected on the basis of photoelectron generation. Finally, X-ray photoelectron spectroscopy (XPS) has been employed to characterize the surface oxidation state of the fibre medium. The charge state of Si2p was found to lie on 103.86 eV of binding energy and the atomic percentage obtained from the XPS analysis is 22.41%.

Effect of Pb2+ ions on ilmenite flotation and adsorption of benzohydroxamic acid as a collector

NASA Astrophysics Data System (ADS)

Xu, Longhua; Tian, Jia; Wu, Houqin; Lu, Zhongyuan; Yang, Yaohui; Sun, Wei; Hu, Yuehua

2017-12-01

The effects of Pb2+ ions on ilmenite flotation and adsorption of benzohydroxamic acid (BHA) as a collector were investigated using microflotation tests, zeta potential measurements, adsorption analysis, Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The microflotation results indicate that the addition of Pb2+ significantly improves the recovery of ilmenite using BHA as a collector. A maximum recovery of 88.46% is obtained at pH 8.12 in the presence of Pb2+; a maximum recovery of 45% is obtained at the same pH using BHA alone. At pHs below 8.0, lead nitrate are mainly present in the solution as Pb2+ and PbOH+, while at pHs above 8.0, the predominant components are Pb(OH)2(s) and Pb(OH)3-. The adsorption of these lead species influences the zeta potential of ilmenite and the number of activated sites on the ilmenite surface. FTIR and XPS analyses reveal that lead species and BHA react with the metal sites on the ilmenite surface. The lead species in solution are either adsorbed onto the ilmenite surface, which increases the surface activity of ilmenite, or react with BHA in solution to form complexes of lead and BHA.

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

Wang, Yan; Pan, Cheng-Ling; Xiao, Li-Na

Three new supramolecular compounds based on triethylenediamine and different polyoxometalates [W{sup VI}{sub 3}V{sup V}{sub 3}O{sub 19}H]{l_brace}[Cu(HDABCO)]{sub 2}(H{sub 2}O){r_brace} (1), [P{sub 2}Mo{sup VI}{sub 18}O{sub 62}][HDABCO]{sub 2}[H{sub 2}DABCO]{sub 2}.12 H{sub 2}O (2) and [Mo{sup VI}{sub 7.5}W{sup VI}{sub 0.5}O{sub 27}][Cu(HDABCO)]{sub 2}.2 H{sub 3}O.2 H{sub 2}O (3) (DABCO=triethylenediamine) have been synthesized hydrothermally and characterized by IR, TG, XPS and X-ray diffraction analyses. Crystal structure analyses reveal that compound 1 exhibits a face-centered cubic packing motif, compound 2 displays a supramolecular structure constructed form the 'chains' arranged hexagonally, compound 3 contains [Mo{sub 7.5}W{sub 0.5}O{sub 27}]{sub {infinity}} chain decorated by [Cu(HDABCO)]{sup 2+} cations, which was thenmore » packed into a layer structure. These results show that the same organonitrogen combining with the different POMs will yield different supramolecular networks. -- Graphical abstract: Three new supramolecular compounds based on triethylenediamine and different polyoxometalates have been hydrothermally synthesized and characterized by IR, XPS, TG, elemental analysis and X-ray diffraction analysis.« less

Bioaccumulation characterization of uranium by a novel Streptomyces sporoverrucosus dwc-3.

PubMed

Li, Xiaolong; Ding, Congcong; Liao, Jiali; Du, Liang; Sun, Qun; Yang, Jijun; Yang, Yuanyou; Zhang, Dong; Tang, Jun; Liu, Ning

2016-03-01

The biosorption mechanisms of uranium on an aerobic bacterial strain Streptomyces sporoverrucosus dwc-3, isolated from a potential disposal site for (ultra-)low uraniferous radioactive waste in Southwest China, were evaluated by using transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis, Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), proton induced X-ray emission (PIXE) and enhanced proton backscattering spectrometry (EPBS). Approximately 60% of total uranium at an initial concentration of 10mg/L uranium nitrate solution could be absorbed on 100mg S. sporoverrucosus dwc-3 with an adsorption capacity of more than 3.0mg/g (wet weight) after 12hr at room temperature at pH3.0. The dynamic biosorption process of S. sporoverrucosus dwc-3 for uranyl ions was well described by a pseudo second-order model. S. sporoverrucosus dwc-3 could accumulate uranium on cell walls and within the cell, as revealed by SEM and TEM analysis as well as EDX spectra. XPS and FT-IR analysis further suggested that the absorbed uranium was bound to amino, phosphate and carboxyl groups of the cells. Additionally, PIXE and EPBS results confirmed that ion exchange also contributed to the adsorption process of uranium. Copyright © 2015. Published by Elsevier B.V.

Comparative analysis of electrophysical properties of ceramic tantalum pentoxide coatings, deposited by electron beam evaporation and magnetron sputtering methods

NASA Astrophysics Data System (ADS)

Donkov, N.; Mateev, E.; Safonov, V.; Zykova, A.; Yakovin, S.; Kolesnikov, D.; Sudzhanskaya, I.; Goncharov, I.; Georgieva, V.

2014-12-01

Ta2O5 ceramic coatings have been deposited on glass substrates by e-beam evaporation and magnetron sputtering methods. For the magnetron sputtering process Ta target was used. X-ray diffraction measurements show that these coatings are amorphous. XPS survey spectra of the ceramic Ta2O5 coatings were obtained. All spectra consist of well-defined XPS lines of Ta 4f, 4d, 4p and 4s; O 1s; C 1s. Ta 4f doublets are typical for Ta2O5 coatings with two main peaks. Scanning electron microscopy and atomic force microscopy images of the e-beam evaporated and magnetron sputtered Ta2O5 ceramic coatings have revealed a relatively flat surface with no cracks. The dielectric properties of the tantalum pentoxide coatings have been investigated in the frequency range of 100 Hz to 1 MHz. The electrical behaviour of e-beam evaporated and magnetron sputtered Ta2O5 ceramic coatings have also been compared. The deposition process conditions principally effect the structure parameters and electrical properties of Ta2O5 ceramic coatings. The coatings deposited by different methods demonstrate the range of dielectric parameters due to the structural and stoichiometric composition changes

A spectroscopic study for understanding the speciation of Cr on palm shell based adsorbents and their application for the remediation of chrome plating effluents.

PubMed

Kushwaha, Shilpi; Sreedhar, B; Sudhakar, Padmaja P

2012-07-01

Palm shell based adsorbents prepared under five different thermochemical conditions have been shown to be quite effective for removal of chromium (III and VI) from aqueous solutions. X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared Spectroscopy (FT-IR) have been used to determine information about the speciation and binding of chromium on the adsorbents under study. X-ray photoelectron spectroscopy (XPS) studies indicate that oxidation of lignin moieties takes place concurrently to Cr(VI) reduction and leads to the formation of hydroxyl and carboxyl functions. The maximum adsorption capacity for hexavalent chromium was found to be about 313 mg/g in an acidic medium using PAPSP. This is comparable to other natural substrates and ordinary adsorbents. The efficacy of the adsorbents under study to remove chromium from plating waste water has been demonstrated. Copyright © 2012 Elsevier Ltd. All rights reserved.

A novel X-ray photoelectron spectroscopy study of the Al/SiO2 interface

NASA Technical Reports Server (NTRS)

Hecht, M. H.; Vasquez, R. P.; Grunthaner, F. J.; Zamani, N.; Maserjian, J.

1985-01-01

The nondestructive measurement of the chemical and physical characteristics of the interface between bulk SiO2 and thick aluminum films is reported. Both X-ray phototelectron spectroscopy (XPS) and electrical measurements of unannealed, resistively evaporated Al films on thermal SiO2 indicate an atomically abrupt interface. Post metallization annealing at 450 C induces reduction of the SiO2 by the aluminum, at a rate consistent with the bulk reaction rate. The XPS measurement is performed from the SiO2 side after the removal of the Si substrate with XeF2 gas and thinning of the SiO2 layer with HF:ETOH. This represents a powerful new approach to the study of metal-insulator and related interfaces.

1300929

NASA Image and Video Library

2013-08-15

ARTHUR BROWN (AST, AEROSPACE METALLIC MATERIALS) LOADS A CERAMIC COATED SILICON WAFER INTO A KRATOS (ELECTRON SPECTROSCOPY FOR CHEMICAL ANALYSIS) TO PERFORM X-RAY PHOTOELECTRON SPECTROSCOPY (XPS). XPS IS A TECHNIQUE THAT ANALYZES THE SURFACE CHEMISTRY OF A SAMPLE BY IRRADIATING IT WITH X-RAYS AND MEASURING THE NUMBER AND KINETIC ENERGY OF ELECTRON THAT ESCAPE.

[Quantitative surface analysis of Pt-Co, Cu-Au and Cu-Ag alloy films by XPS and AES].

PubMed

Li, Lian-Zhong; Zhuo, Shang-Jun; Shen, Ru-Xiang; Qian, Rong; Gao, Jie

2013-11-01

In order to improve the quantitative analysis accuracy of AES, We associated XPS with AES and studied the method to reduce the error of AES quantitative analysis, selected Pt-Co, Cu-Au and Cu-Ag binary alloy thin-films as the samples, used XPS to correct AES quantitative analysis results by changing the auger sensitivity factors to make their quantitative analysis results more similar. Then we verified the accuracy of the quantitative analysis of AES when using the revised sensitivity factors by other samples with different composition ratio, and the results showed that the corrected relative sensitivity factors can reduce the error in quantitative analysis of AES to less than 10%. Peak defining is difficult in the form of the integral spectrum of AES analysis since choosing the starting point and ending point when determining the characteristic auger peak intensity area with great uncertainty, and to make analysis easier, we also processed data in the form of the differential spectrum, made quantitative analysis on the basis of peak to peak height instead of peak area, corrected the relative sensitivity factors, and verified the accuracy of quantitative analysis by the other samples with different composition ratio. The result showed that the analytical error in quantitative analysis of AES reduced to less than 9%. It showed that the accuracy of AES quantitative analysis can be highly improved by the way of associating XPS with AES to correct the auger sensitivity factors since the matrix effects are taken into account. Good consistency was presented, proving the feasibility of this method.

Chemical state analysis of heavily phosphorus-doped epitaxial silicon films grown on Si (1 0 0) by X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Lee, Minhyeong; Kim, Sungtae; Ko, Dae-Hong

2018-06-01

In this work, we investigated the chemical bonding states in highly P-doped Si thin films epitaxially grown on Si (0 0 1) substrates using high-resolution X-ray photoelectron spectroscopy (HR-XPS). HR-XPS P 2p core-level spectra clearly show spin-orbital splitting between P 2p1/2 and P 2p3/2 peaks in Si films doped with a high concentration of P. Moreover, the intensities of P 2p1/2 and P 2p3/2 peaks for P-doped Si films increase with P concentrations, while their binding energies remained almost identical. These results indicate that more P atoms are incorporated into the substitutional sites of the Si lattice with the increase of P concentrations. In order to identify the chemical states of P-doped Si films shown in XPS Si 2p spectra, the spectra of bulk Si were subtracted from those of Si:P samples, which enables us to clearly identify the new chemical state related to Sisbnd P bonds. We observed that the presence of the two well-resolved new peaks only for the Si:P samples at the binding energy higher than those of a Sisbnd Si bond, which is due to the strong electronegativity of P than that of Si. Experimental findings in this study using XPS open up new doors for evaluating the chemical states of P-doped Si materials in fundamental researches as well as in industrial applications.

In-situ XPS analysis of oxidized and reduced plasma deposited ruthenium-based thin catalytic films

NASA Astrophysics Data System (ADS)

Balcerzak, Jacek; Redzynia, Wiktor; Tyczkowski, Jacek

2017-12-01

A novel in-situ study of the surface molecular structure of catalytically active ruthenium-based films subjected to the oxidation (in oxygen) and reduction (in hydrogen) was performed in a Cat-Cell reactor combined with a XPS spectrometer. The films were produced by the plasma deposition method (PEMOCVD). It was found that the films contained ruthenium at different oxidation states: metallic (Ru0), RuO2 (Ru+4), and other RuOx (Ru+x), of which content could be changed by the oxidation or reduction, depending on the process temperature. These results allow to predict the behavior of the Ru-based catalysts in different redox environments.

Transformation of multiwall carbon nanotubes to onions with layers cross-linked by sp3 bonds under high pressure and shear deformation

NASA Astrophysics Data System (ADS)

Pankov, A. M.; Bredikhina, A. S.; Kulnitskiy, B. A.; Perezhogin, I. A.; Skryleva, E. A.; Parkhomenko, Yu. N.; Popov, M. Yu.; Blank, V. D.

2017-08-01

A pressure-induced phase transition of multiwall carbon nanotubes (MWNT) to a new structure at room temperature is studied using a shear diamond anvil cell, X-ray photoelectron spectra (XPS), transmission electron microscope (TEM) and Raman procedures. We observe a cardinal pressure-induced change in the nanoparticles shape from multi-shell tubes to multi-shell spheres. MWNT transforms to onions with layers cross-linked by sp3 bonds under the 45-65 GPa compressive stress combined with shear deformation at room temperature. TEM and XPS results show that about 40% of the carbon atoms in the new phase are sp3-bounded.

Investigating early stages of biocorrosion with XPS: AISI 304 stainless steel exposed to Burkholderia species

NASA Astrophysics Data System (ADS)

Johansson, Leena-Sisko; Saastamoinen, Tuomas

1999-04-01

We have investigated the interactions of an exopolymer-producing bacteria, Burkholderia sp. with polished AISI 304 stainless steel substrates using X-ray photoelectron spectroscopy (XPS). Steel coupons were exposed to the pure bacteria culture in a specially designed flowcell for 6 h during which the experiment was monitored in situ with an optical microscope. XPS results verified the formation of biofilm containing extracellular polymer on all the samples exposed to bacteria. Sputter results indicated that some ions needed for metabolic processes were trapped within the biofilm. Changes in the relative Fe concentration and Fe 2p peak shape indicated that also iron had accumulated into the biofilm.

Physical and Chemical Behaviors of HCl on Ice Surface: Insights from an XPS and NEXAFS Study

NASA Astrophysics Data System (ADS)

Kong, X.; Waldner, A.; Orlando, F.; Birrer, M.; Artiglia, L.; Ammann, M.; Bartels-Rausch, T.

2016-12-01

Ice and snow play active roles for the water cycle, the energy budget of the Earth, and environmental chemistry in the atmosphere and cryosphere. Trace gases can be taken up by ice, and physical and chemical fates of the impurities could modify surface properties significantly and consequently influence atmospheric chemistry and the climate system. However, the understanding of chemical behaviour of impurities on ice surface are very poor, which is largely limited by the difficulties to apply high sensitivity experimental approaches to ambient air conditions, e.g. studies of volatile surfaces, because of the strict requirements of vacuum experimental conditions. In this study, we employed synchrotron-based X-ray photoelectron spectroscopy (XPS) and partial electron yield Near Edge X-ray Absorption Fine Structure (NEXAFS) in a state-of-the-art near-ambient pressure photoelectron (NAPP) spectroscopy end station. The NAPP enables to utilize the surface sensitive experimental methods, XPS and NEXAFS, on volatile surfaces, i.e. ice at temperatures approaching 0°C. XPS and NEXAFS together provide unique information of hydrogen bonding network, dopants surface concentration, dopant depth profile, and acidic dissociation on the surfaces1. Taking the advantages of the highly sensitive techniques, the adsorption, dissociation and depth profile of Hydrogen Chloride (HCl) on ice were studied. In brief, two states of Chloride on ice surface are identified from the adsorbed HCl, and they are featured with different depth profiles along the ice layers. Combining our results and previously reported constants from literatures (e.g. HCl diffusion coefficients in ice)2, a layered kinetic model has been constructed to fit the depth profiles of two states of Chloride. On the other side, pure ice and doped ice are compared for their surface structure change caused by temperature and the presence of HCl, which shows how the strong acid affect the ice surface in turn. 1. Orlando, F., et al., Top Catal 2016, 59, 591-604. 2. Huthwelker, T.; Malmstrom, M. E.; Helleis, F.; Moortgat, G. K.; Peter, T., J Phys Chem A 2004, 108, 6302-6318.

X-ray photoelectron spectroscopic evidence for bacteria-enhanced dissolution of hornblende

NASA Astrophysics Data System (ADS)

Kalinowski, B. E.; Liermann, L. J.; Brantley, S. L.; Barnes, A.; Pantano, C. G.

2000-04-01

An Arthrobacter species capable of extracting Fe from hornblende was isolated from a soil from the Adirondacks, NY (USA). This bacteria isolate, used in batch experiments with hornblende, accelerated the release of Fe from hornblende without measurably affecting Al release. The isolate produces both low molecular weight organic acids (LMWOA) and a catecholate siderophore. Polished hornblende (glass and crystal) discs were analyzed with X-ray photoelectron spectroscopy (XPS) before and after incubation with growing Arthrobacter sp. to investigate whether the bacteria caused a distinguishable chemical signature on the upper 100 Å of mineral surface. After removal of the arthrobacter grown on hornblende crystal or glass substrates using lysozyme, XPS revealed surface depletion of Fe for samples grown for several days in buffered (crystal) and unbuffered (crystal and glass) media. Fe/Si ratios of hornblende surfaces dissolved under biotic conditions are significantly lower than Fe/Si ratios on surfaces dissolved under abiotic conditions for similar amounts of time. Enhanced Fe release and the formation of Fe-depleted surfaces is inferred to be caused by catechol complexation at the mineral surface. Because natural siderophore was not isolated in sufficient quantities to run bacteria-free leaching experiments, parallel investigations were run with a commercially available siderophore (desferrioxamine B). Desferrioxamine B was observed to enhance release of Fe, Si, and Al from hornblende both with and without added bacteria. Formation of desferrioxamine-Fe surface complexes were probed by studying the multiple splitting and shift in intensities of the N 1s line analyzed by XPS on siderophore ± Fe on gold surfaces and siderophore + hornblende crystal surfaces. Based upon the observed formation of an hydroxamate (desferrioxamine) surface complex on hornblende, we infer that catecholate siderophores, such as those produced by the arthrobacter, also complex on the hornblende surface. Surface complexation is favored because of the extremely high association constants for siderophore + Fe(III). X-ray photoelectron spectroscopic data is therefore consistent with a model wherein enhanced Fe release by these bacteria or desferrioxamine B is caused by Fe-siderophore complexation at the silicate surface. Such complexation presumably weakens bonds between the Fe and the oxide lattice, causing enhanced Fe leaching and an Fe-depleted surface. Some leaching may also be due to LMWOA, although this is interpreted to be of secondary importance.

Effective role of deposition duration on the growth of V2O5 nanostructured thin films

NASA Astrophysics Data System (ADS)

Sharma, Rabindar Kumar; Saini, Sujit Kumar; Singh, Megha; Reddy, G. B.

2016-05-01

In this report, vanadium pentoxide nanostructured thin films (NSTs) with nanoplates (NPs) have synthesized on Ni coated glass substrate employing plasma assisted sublimation process (PASP), as a function of deposition/growth durations. The effect of deposition durations on the morphological, structural, vibrational, and compositional properties have been investigated one by one. The structural and vibrational studies endorsed that the grown NPs have only orthorhombic phase, no other sub oxide phases are recorded in the limit of resolution. The morphological results of all samples using SEM, revealed that the features, coverage density, and alignments of NPs are greatly controlled by deposition duration and the best sample is obtained for 25 min (S2). Further, the more insight information is accomplished by HRTEM/SAED on the best featured sample, which confirmed the single crystalline nature of NPs. The XPS result again confirmed the compositional purity and the nearly stoichiometric nature of NPs.

Enhanced vanadium (V) reduction and bioelectricity generation in microbial fuel cells with biocathode

NASA Astrophysics Data System (ADS)

Qiu, Rui; Zhang, Baogang; Li, Jiaxin; Lv, Qing; Wang, Song; Gu, Qian

2017-08-01

Microbial fuel cells (MFCs) represent a promising approach for remediation of toxic vanadium (V) contaminated environment. Herein, enhanced V(V) reduction and bioelectricity generation are realized in MFCs with biocathode. Synergistically electrochemical and microbial reductions result in the nearly complete removals of V(V) within 7 d operation with initial concentration of 200 mg L-1. Maximum power density of 529 ± 12 mW m-2 is obtained. Electrochemical tests reveal that biocathode promotes electron transfers and reduces charge transfer resistance. XPS analysis confirms that V(IV) is the main reduction product, which precipitates naturally under neutral conditions. High-throughput 16S rRNA gene sequencing analysis indicates that the newly appeared Dysgonomonas is responsible for V(V) reduction and Klebsiella contributes mainly to bioelectricity generation in MFCs with biocathode. This study further improves the performance of remediating V(V) contaminated environment based on MFC technology.

Amination of activated carbon for enhancing phenol adsorption: Effect of nitrogen-containing functional groups

NASA Astrophysics Data System (ADS)

Yang, Guo; Chen, Honglin; Qin, Hangdao; Feng, Yujun

2014-02-01

To study the contribution of different nitrogen-containing functional groups to enhancement of phenol adsorption, the aminated activated carbons (AC) were characterized by N2 adsorption/desorption, XPS, Boehm titration, and pH drift method and tested for adsorption behaviors of phenol. Adsorption isotherm fitting revealed that the Langmuir model was preferred for the aminated ACs. The adsorption capacity per unit surface area (qm/SSABET) was linearly correlated with the amount of pyridinic and pyrrolic N, which suggested that these two functional groups played a critical role in phenol adsorption. The enhancement of adsorption capacity was attributed to the strengthened π-π dispersion between phenol and basal plane of AC by pyridinic, pyrrolic N. The adsorption kinetics was found to follow the pseudo-second-order kinetic model, and intraparticle diffusion was one of the rate-controlling steps in the adsorption process.

Experimental and Theoretical Investigation of Thiazolyl Blue as a Corrosion Inhibitor for Copper in Neutral Sodium Chloride Solution.

PubMed

Feng, Li; Zhang, Shengtao; Qiang, Yujie; Xu, Yue; Guo, Lei; Madkour, Loutfy H; Chen, Shijin

2018-06-19

The anticorrosion effect of thiazolyl blue (MTT) for copper in 3% NaCl at 298 K was researched by electrochemical methods, scanning electron-microscopy (SEM), and atomic force microscopy (AFM). The results reveal that MTT can protect copper efficiently, with a maximum efficiency of 95.7%. The corrosion inhibition mechanism was investigated by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectral (FT-IR), and theoretical calculation. The results suggest that the MTT molecules are adsorbed on metal surface forming a hydrophobic protective film to prevent copper corrosion. It also indicates that the MTT and copper form covalent bonds. The molecular dynamic simulation further gives the evidence for adsorption. The adsorption isotherm studies demonstrate that a spontaneous, mixed physical and chemical adsorption occurs, which obeys Langmuir adsorption isotherm. The present research can help us better understand the corrosion inhibition process and improve it.

Dissolution of lanthanide alumino-silicate oxynitride glasses

NASA Astrophysics Data System (ADS)

Bois, L.; Barré, N.; Guillopé, S.; Guittet, M. J.; Gautier-Soyer, M.; Duraud, J. P.; Trocellier, P.; Verdier, P.; Laurent, Y.

2000-01-01

The aqueous corrosion behavior of lanthanide aluminosilicate glasses has been studied under static conditions ( T=96°C, duration=1 and 3 months, glass surface area/leachate volume, S/ V=0.3 cm -1) by means of solution and solid analyses. It was found that these glasses exhibit a high chemical durability. The influence of yttrium, magnesium and nitrogen, which are supposed to improve the mechanical properties, on the chemical durability, has been investigated. After a one-month experiment, lanthanum and yttrium releases were found to be about 10 -7 mol l -1, while silicon and aluminum releases were about 10 -5 mol l -1. Yttrium seems to improve the chemical durability. The presence of nitrogen does not seem to modify the glass constituents releases, but seems to improve the surface state of the altered glass. XPS experiments reveal that lanthanum and yttrium are more concentrated near the surface (20-30 Å) of the glass after the leaching test.

Self-buckled effect of cubic Cu3N film: Surface stoichiometry

NASA Astrophysics Data System (ADS)

Mukhopadhyay, Arun Kumar; Roy, Avishek; Das, Sadhan Chandra; Wulff, Harm; Hippler, Rainer; Majumdar, Abhijit

2018-05-01

We report the surface stoichiometry of cubic Cu3N films as function of nitrogen concentration (N/Cu). The film is deposited at 1Pa showing self-buckled (surface peels off) effect as it is exposed to ambient air at atmospheric pressure whereas at 5 Pa, the film shows no such effect. The spectroscopic (X-ray photoelectron spectroscopy (XPS)) analysis suggests that the presence of nitride layer is not the prime cause but the surface oxidation playing a major role for the self-buckling effect. Grazing incidence X-ray diffraction (GIXRD) confirms the formation of a crystalline Cu3N phase of the film. Atomic force microscopic (AFM) study reveals that the 1Pa film shows a lower roughness as compared to 5 Pa films and furthermore, Fast Fourier Transform (FFT) analysis shows a fourfold symmetric structure (both modes of pattern-orientation) in both the deposited films.

Casein mediated green synthesis and decoration of reduced graphene oxide

NASA Astrophysics Data System (ADS)

Maddinedi, Sireesh Babu; Mandal, Badal Kumar; Vankayala, Raviraj; Kalluru, Poliraju; Tammina, Sai Kumar; Kiran Kumar, H. A.

This research is mainly focusing on one-step biosynthesis of graphene from graphene oxide and its stabilization using naturally occurring milk protein, casein. The synthesis of casein reduced graphene oxide (CRGO) was completed within 7 h under reflux at 90 °C with the formation of few layered fine graphene nanosheets. UV-Vis, XRD, XPS analysis data revealed the reduction process of the graphene oxide. Results of FT-IR, HPLC and TEM analysis have shown that the ensuing material consists of graphene decorated with casein molecules. Aspartic acid and glutamic acid residue present in casein molecules are responsible for the reduction of graphene oxide.

Surfactant Mediated Growth of Co on MgO(111)

NASA Astrophysics Data System (ADS)

Johnson-Steigelman, H. Trevor; Parihar, Somendra S.; Lyman, Paul F.

2010-03-01

Monolayer films of Co were deposited using an electrostatic electron-beam evaporator on single-crystal MgO(111)- √3 x√3 R 30^o substrates held at room temperature, with subsequent annealing of temperatures 400 C to 800 C. These films were characterized using low-energy electron diffraction (LEED), x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and x-ray diffraction (XRD). After short anneals of 400 C, AFM, LEED, and XPS suggest that islanding has occurred at the surface. XPS and XRD indicate the presence of elemental Co. 1-2 ML films of Ag were examined as a potential surfactant to aid in the growth of smooth Co films. Despite the fact that Ag itself formed islands, it was found that the presence of Ag did have a surfactant effect upon the thin-film growth of Co on Ag/MgO(111)- √3 x√3 R 30^o. Co islands were still present, but much more smooth than islands formed without Ag. XPS and AFM suggest strongly that Ag floated to the top of these samples at temperatures above 400 ^oC.

Enargite oxidation: A review

NASA Astrophysics Data System (ADS)

Lattanzi, Pierfranco; Da Pelo, Stefania; Musu, Elodia; Atzei, Davide; Elsener, Bernhard; Fantauzzi, Marzia; Rossi, Antonella

2008-01-01

Enargite, Cu 3AsS 4, is common in some deposit types, e.g. porphyry systems and high sulphidation epithermal deposits. It is of environmental concern as a potential source of arsenic. In this communication, we review the current knowledge of enargite oxidation, based on the existing literature and our own original data. Explicit descriptions of enargite oxidation in natural environments are scarce. The most common oxidized alteration mineral of enargite is probably scorodite, FeAsO 4.2H 2O, with iron provided most likely by pyrite, a phase almost ubiquitously associated with enargite. Other secondary minerals after enargite include arsenates such as chenevixite, Cu 2Fe 2(AsO 4) 2(OH) 4.H 2O, and ceruleite, Cu 2Al 7(AsO 4) 4.11.5H 2O, and sulphates such as brochantite, Cu 4(SO 4)(OH) 6, and posnjakite, Cu 4(SO 4)(OH) 6·H 2O. Detailed studies of enargite field alteration at Furtei, Sardinia, suggest that most alteration occurs through dissolution, as testified by the appearance of etch pits at the surface of enargite crystals. However, apparent replacement by scorodite and cuprian melanterite was observed. Bulk oxidation of enargite in air is a very slow process. However, X-ray photoelectron spectroscopy (XPS) reveals subtle surface changes. From synchrotron-based XPS it was suggested that surface As atoms react very fast, presumably by forming bonds with oxygen. Conventional XPS shows the formation, on aged samples, of a nanometer-size alteration layer with an appreciably distinct composition with respect to the bulk. Mechanical activation considerably increases enargite reactivity. In laboratory experiments at acidic to neutral pH, enargite oxidation/dissolution is slow, although it is accelerated by the presence of ferric iron and/or bacteria such as Acidithiobacillus ferrooxidans and Sulfolobus BC. In the presence of sulphuric acid and ferric iron, the reaction involves dissolution of Cu and formation of native sulphur, subsequently partly oxidized to sulphate. At alkaline pH, the reactivity of enargite is apparently slightly greater. XPS spectra of surfaces conditioned at pH 11 have been interpreted as evidence of formation of a number of surface species, including cupric oxide and arsenic oxide. Treatment with hypochlorite solutions at pH 12.5 quickly produces a coating of cupric oxide. Electrochemical oxidation of enargite typically involves low current densities, confirming that the oxidation process is slow. Important surface changes occur only at high applied potentials, e.g. + 0.74 V vs. SHE. It is confirmed that, at acidic pH, the dominant process is Cu dissolution, accompanied (at + 0.56 V vs. SHE, pH = 1) by formation of native sulphur. At alkaline pH, a number of surface products have been suggested, including copper and arsenic oxides, and copper arsenates. XPS studies of the reacted surfaces demonstrate the evolution of Cu from the monovalent to the divalent state, the formation of As-O bonds, and the oxidation of sulphur to polysulphide, sulphite and eventually sulphate. In most natural and quasi-natural (mining) situations, it is expected that enargite reactivity will be slow. Moreover, it is likely that the release of arsenic will be further slowed down by at least temporary trapping in secondary phases. Therefore, an adequate management of exposed surfaces and wastes should minimize the environmental impact of enargite-bearing deposits. In spite of an increasing body of data, there are several gaps in our knowledge of enargite oxidation. The exact nature of most mechanisms and products remains poorly constrained, and there is a lack of quantitative data on the dependence on parameters such as pH and dissolved oxygen.

Chemical conversion of sulphur dioxide on Eyjafjallajökull's volcanic ash from the 2010 eruption

NASA Astrophysics Data System (ADS)

Dupart, Yoan; Burel, Laurence; Delichere, Pierre; George, Christian; D'Anna, Barbara

2013-04-01

Volcanic eruptions induce important climatic and weather modifications. When volcanic ashes are emitted into the atmosphere they can travel for several weeks according to their size distribution and altitude of the emission. Eyjafjallajökull eruption, between April 14th and May 23th, is considered as a medium-size eruption. The upper level winds advected ashes over the UK and continental Europe. During volcanic eruptions high amounts of SO2 were injected into the atmosphere (from 50 to 200 ppbv)[1]. Previous works showed that SO2 could be convert into sulfate on mineral dust surfaces under dark conditions[2]. However, no conversion has been studied with real volcanic ashes and under day conditions (light exposure). For this study, real Eyjafjallajökull's ashes samples, collected on the 2010.04.18 at Seljavellir, were used. The ashes were deposited on a horizontal cylindrical coated-wall flow tube reactor surrounded by 5 fluorescent lamps (340-420 nm). The kinetic studies revealed that the presence of UV-A irradiation enhanced the conversion of SO2 on ashes samples. Moreover chemical analyses as XPS, Ion Chromatography and SEM were performed on volcanic ashes before and after exposition to SO2. XPS and ion chromatography analyzes showed that the presence of light increase the SO2 uptake on ashes surfaces and convert it into ions sulphate. Beside SEM analyses disclosed that the conversion takes place systematically on an iron oxide site . By combining kinetics and chemical analysis we are able to propose a new mechanism for the SO2 conversion on mineral surfaces under light conditions. 1. Self, S., et al., Volatile fluxes during flood basalt eruptions and potential effects on the global environment: A Deccan perspective. Earth and Planetary Science Letters, 2006. 248(1-2): p. 518-532. 2. Zhang et al., Heterogeneous Reactions of Sulfur Dioxide on Typical Mineral Particles, J. Phys. Chem. B, 2006

Reciprocal interaction between dental alloy biocorrosion and Streptococcus mutans virulent gene expression.

PubMed

Zhang, Songmei; Qiu, Jing; Ren, Yanfang; Yu, Weiqiang; Zhang, Fuqiang; Liu, Xiuxin

2016-04-01

Corrosion of dental alloys is a major concern in dental restorations. Streptococcus mutans reduces the pH in oral cavity and induces demineralization of the enamel as well as corrosion of restorative dental materials. The rough surfaces of dental alloys induced by corrosion enhance the subsequent accumulation of plaque. In this study, the corrosion process of nickel-chromium (Ni-Cr) and cobalt-chromium (Co-Cr) alloys in a nutrient-rich medium containing S. mutans was studied using inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray photoelectron spectroscopy (XPS) and electrochemical corrosion test. Our results showed that the release of Ni and Co ions increased, particularly after incubation for 3 days. The electrochemical corrosion results showed a significant decrease in the corrosion resistance (Rp) value after the alloys were immersed in the media containing S. mutans for 3 days. Correspondingly, XPS revealed a reduction in the relative dominance of Ni, Co, and Cr in the surface oxides after the alloys were immersed in the S. mutans culture. After removal of the biofilm, the pre-corroded alloys were re-incubated in S. mutans medium, and the expressions of genes associated with the adhesion and acidogenesis of S. mutans, including gtfBCD, gbpB, fif and ldh, were evaluated by detecting the mRNA levels using real-time reverse transcription polymerase chain reaction (RT-PCR). We found that the gtfBCD, gbpB, ftf and Idh expression of S. mutans were noticeably increased after incubation with pre-corroded alloys for 24 h. This study demonstrated that S. mutans enhanced the corrosion behavior of the dental alloys, on the other hand, the presence of corroded alloy surfaces up-regulated the virulent gene expression in S. mutans. Compared with smooth surfaces, the rough corroded surfaces of dental alloys accelerated the bacteria-adhesion and corrosion process by changing the virulence gene expression of S. mutans.

Surface functionalization of thin-film diamond for highly stable and selective biological interfaces

PubMed Central

Stavis, Courtney; Clare, Tami Lasseter; Butler, James E.; Radadia, Adarsh D.; Carr, Rogan; Zeng, Hongjun; King, William P.; Carlisle, John A.; Aksimentiev, Aleksei; Bashir, Rashid; Hamers, Robert J.

2011-01-01

Carbon is an extremely versatile family of materials with a wide range of mechanical, optical, and mechanical properties, but many similarities in surface chemistry. As one of the most chemically stable materials known, carbon provides an outstanding platform for the development of highly tunable molecular and biomolecular interfaces. Photochemical grafting of alkenes has emerged as an attractive method for functionalizing surfaces of diamond, but many aspects of the surface chemistry and impact on biological recognition processes remain unexplored. Here we report investigations of the interaction of functionalized diamond surfaces with proteins and biological cells using X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and fluorescence methods. XPS data show that functionalization of diamond with short ethylene glycol oligomers reduces the nonspecific binding of fibrinogen below the detection limit of XPS, estimated as > 97% reduction over H-terminated diamond. Measurements of different forms of diamond with different roughness are used to explore the influence of roughness on nonspecific binding onto H-terminated and ethylene glycol (EG)-terminated surfaces. Finally, we use XPS to characterize the chemical stability of Escherichia coli K12 antibodies on the surfaces of diamond and amine-functionalized glass. Our results show that antibody-modified diamond surfaces exhibit increased stability in XPS and that this is accompanied by retention of biological activity in cell-capture measurements. Our results demonstrate that surface chemistry on diamond and other carbon-based materials provides an excellent platform for biomolecular interfaces with high stability and high selectivity. PMID:20884854

Investigation of HCl-based surface treatment for GaN devices

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

Okada, Hiroshi, E-mail: okada@ee.tut.ac.jp; Department of Electrical and Electronic Information Engineering, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, Toyohashi 441-8580; Shinohara, Masatohi

2016-02-01

Surface treatments of GaN in HCl-based solutions are studied by X-ray photoelectron spectroscopy (XPS) and electrical characterization of fabricated GaN surfaces. A dilute-HCl treatment (HCl:H{sub 2}O=1:1) at room temperature and a boiled-HCl treatment (undiluted HCl) at 108°C are made on high-temperature annealed n-GaN. From the XPS study, removal of surface oxide by the dilute-HCl treatment was found, and more thoroughly oxide-removal was confirmed in the boiled-HCl treatment. Effect of the surface treatment on electrical characteristics on AlGaN/GaN transistor is also studied by applying treatment processes prior to the surface SiN deposition. Increase of drain current is found in boiled-HCl treatedmore » samples. The results suggest that the boiled-HCl treatment is effective for GaN device fabrication.« less

Model systems in heterogeneous catalysis: towards the design and understanding of structure and electronic properties.

PubMed

Pan, Q; Li, L; Shaikhutdinov, S; Fujimori, Y; Hollerer, M; Sterrer, M; Freund, H-J

2018-05-29

We discuss in this paper two case studies related to nano-particle catalyst systems. One concerns a model system for the Cr/SiO2 Phillips catalyst for ethylene polymerization and here we present XPS data to complement the previously published TPD, IRAS and reactivity studies to elucidate the electronic structure of the system in some detail. The second case study provides additional information on Au nano-particles supported on ultrathin MgO(100)/Ag(100) films where we had observed a specific activity of the particle's rim at the metal-oxide interface with respect to CO2 activation and oxalate formation, obviously connected to electron transfer through the MgO film from the metal substrate underneath. Here we present XPS and Auger data, which allows detailed analysis of the observed chemical shifts. This analysis corroborates previous findings deduced via STM.

Oxidation of MnO(100) and NaMnO2 formation: Characterization of Mn2+ and Mn3+ surfaces via XPS and water TPD

NASA Astrophysics Data System (ADS)

Feng, Xu; Cox, David F.

2018-09-01

The oxidation of clean and Na precovered MnO(100) has been investigated by X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and temperature programmed desorption (TPD) of adsorbed water. XPS results indicate that Mn3O4-like and Mn2O3-like surfaces can be formed by various oxidation treatments of clean and nearly-stoichiometric MnO(100), while a NaMnO2-like surface can be produced by the oxidation of MnO(100) pre-covered with multilayers of metallic Na. Water TPD results indicate that water adsorption/desorption is sensitive to the available oxidation states of surface Mn cations, and can be used to distinguish between surfaces exposing Mn2+and Mn3+ cations, or a combination of these oxidation states. Carbon dioxide and water TPD results from the NaMnO2-like surface indicate that pre-adsorbed water blocks the uptake of CO2, while water displaces pre-adsorbed CO2. No indication of a strong reactive interaction is observed between CO2, water and the NaMnO2-like surface under the conditions of our study.

Composite Behavior of a Novel Insulated Concrete Sandwich Wall Panel Reinforced with GFRP Shear Grids: Effects of Insulation Types.

PubMed

Kim, JunHee; You, Young-Chan

2015-03-03

A full-scale experimental program was used in this study to investigate the structural behavior of novel insulated concrete sandwich wall panels (SWPs) reinforced with grid-type glass-fiber-reinforced polymer (GFRP) shear connectors. Two kinds of insulation-expanded polystyrene (EPS) and extruded polystyrene (XPS) with 100 mm thickness were incased between the two concrete wythes to meet the increasing demand for the insulation performance of building envelope. One to four GFRP shear grids were used to examine the degree of composite action of the two concrete wythes. Ten specimens of SWPs were tested under displacement control subjected to four-point concentrated loads. The test results showed that the SWPs reinforced with GFRP grids as shear connectors developed a high degree of composite action resulting in high flexural strength. The specimens with EPS foam exhibited an enhanced load-displacement behavior compared with the specimens with XPS because of the relatively stronger bond between insulation and concrete. In addition, the ultimate strength of the test results was compared to the analytical prediction with the mechanical properties of only GRFP grids. The specimens with EPS insulation presented higher strength-based composite action than the ones with XPS insulation.

Ultra-high vacuum surface analysis study of rhodopsin incorporation into supported lipid bilayers.

PubMed

Michel, Roger; Subramaniam, Varuni; McArthur, Sally L; Bondurant, Bruce; D'Ambruoso, Gemma D; Hall, Henry K; Brown, Michael F; Ross, Eric E; Saavedra, S Scott; Castner, David G

2008-05-06

Planar supported lipid bilayers that are stable under ambient atmospheric and ultra-high-vacuum conditions were prepared by cross-linking polymerization of bis-sorbylphosphatidylcholine (bis-SorbPC). X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were employed to investigate bilayers that were cross-linked using either redox-initiated radical polymerization or ultraviolet photopolymerization. The redox method yields a more structurally intact bilayer; however, the UV method is more compatible with incorporation of transmembrane proteins. UV polymerization was therefore used to prepare cross-linked bilayers with incorporated bovine rhodopsin, a light-activated, G-protein-coupled receptor (GPCR). A previous study (Subramaniam, V.; Alves, I. D.; Salgado, G. F. J.; Lau, P. W.; Wysocki, R. J.; Salamon, Z.; Tollin, G.; Hruby, V. J.; Brown, M. F.; Saavedra, S. S. J. Am. Chem. Soc. 2005, 127, 5320-5321) showed that rhodopsin retains photoactivity after incorporation into UV-polymerized bis-SorbPC, but did not address how the protein is associated with the bilayer. In this study, we show that rhodopsin is retained in supported bilayers of poly(bis-SorbPC) under ultra-high-vacuum conditions, on the basis of the increase in the XPS nitrogen concentration and the presence of characteristic amino acid peaks in the ToF-SIMS data. Angle-resolved XPS data show that the protein is inserted into the bilayer, rather than adsorbed on the bilayer surface. This is the first study to demonstrate the use of ultra-high-vacuum techniques for structural studies of supported proteolipid bilayers.

Comparing XPS on bare and capped ZrN films grown by plasma enhanced ALD: Effect of ambient oxidation

NASA Astrophysics Data System (ADS)

Muneshwar, Triratna; Cadien, Ken

2018-03-01

In this article we compare x-ray photoelectron spectroscopy (XPS) measurements on bare- and capped- zirconium nitride (ZrN) films to investigate the effect of ambient sample oxidation on the detected bound O in the form of oxide ZrO2 and/or oxynitride ZrOxNy. ZrN films in both bare- and Al2O3/AlN capped- XPS samples were grown by plasma-enhanced atomic layer deposition (PEALD) technique using tetrakis dimethylamino zirconium (TDMAZr) precursor, forming gas (5% H2, rest N2) inductively coupled plasma (ICP), and as received research grade process gases under identical process conditions. Capped samples were prepared by depositing 1 nm thick PEALD AlN on ZrN, followed by additional deposition of 1 nm thick ALD Al2O3, without venting of ALD reactor. On bare ZrN sample at room temperature, spectroscopic ellipsometry (SE) measurements with increasing ambient exposure times (texp) showed a self-limiting surface oxidation with the oxide thickness (dox) approaching 3.7 ± 0.02 nm for texp > 120 min. In XPS data measured prior to sample sputtering (tsput = 0), ZrO2 and ZrOxNy were detected in bare- samples, whereas only ZrN and Al2O3/AlN from capping layer were detected in capped- samples. For bare-ZrN samples, appearance of ZrO2 and ZrOxNy up to sputter depth (dsput) of 15 nm in depth-profile XPS data is in contradiction with measured dox = 3.7 nm, but explained from sputtering induced atomic inter-diffusion within analyzed sample. Appearance of artifacts in the XPS spectra from moderately sputtered (dsput = 0.2 nm and 0.4 nm) capped-ZrN sample, provides an evidence to ion-bombardment induced modifications within analyzed sample.

Surface Chemical Studies on Pyrite in the Presence of Polysaccharide-Based Flotation Depressants.

PubMed

Rath; Subramanian; Pradeep

2000-09-01

The interaction of dextrin and guar gum with pyrite has been investigated through adsorption, flotation, and electrokinetic measurements. The adsorption densities of the polysaccharides onto pyrite reveal a region of higher adsorption density in the pH range 7.5-11, with a maximum around pH 10 for both polymers. The isotherms exhibit Langmuirian behavior. The adsorption density of guar gum onto pyrite is higher than that of dextrin. Electrokinetic measurements indicate a decrease in the electrophoretic mobility values in proportion to the concentration of the polymer added. Co-precipitation tests confirm polymer-ferric species interaction in the bulk solution, especially in the pH range 5.5-8.5. The pH range for higher adsorption, significant co-precipitation, and appreciable depression of pyrite encompass each other. XPS and FTIR spectroscopic studies provide evidence in support of chemical interaction between hydroxylated pyrite and the hydroxyl groups of the polymeric depressants. Copyright 2000 Academic Press.

Synthesis and characterization of Ag@polycarbazole coaxial nanocables and their enhanced dispersion behavior

NASA Astrophysics Data System (ADS)

Zahoor, Ahmad; Teng, Qiu; Wang, Haiqiao; Choudhry, M. A.; Li, Xiaoyu

2011-06-01

Ag@polycarbazole coaxial nanocables (CNCs) have been successfully fabricated by the oxidative polymerization of carbazole over Ag nanowires (NWs) in acetonitrile. The morphology of Ag NWs and CNCs was studied by employing a transmission electron microscope (TEM) and a scanning electron microscope (SEM), which showed them to be a monodisperse material. The thickness of the polymer sheath was found to be 5 nm to 8 nm by observation under a high-resolution transmission electron microscope (HR-TEM). Energy dispersive X-ray spectroscopy (EDS), FT-IR and Raman measurements were used to characterize the polymer sheath, which demonstrated it to be a carbon material in polycarbazole form. X-ray photoelectron spectroscopy (XPS) was used for an interfacial study, which revealed that Ag surface atoms remained intact during polymer growth. In the end, zeta potential showed that the dispersion stability of Ag NWs increased due to polymer encapsulation, which is significant to obtain a particular alignment for anisotropic measurement of electrical conductivity.

Neutron vibrational spectroscopic studies of novel tire-derived carbon materials

DOE PAGES

Li, Yunchao; Cheng, Yongqiang; Daemen, Luke L.; ...

2017-08-11

Sulfonated tire-derived carbons have been demonstrated to be high value-added carbon products of tire recycling in several energy storage system applications including lithium, sodium, potassium ion batteries and supercapacitors. In this paper, we compared different temperature pyrolyzed sulfonated tire-derived carbons with commercial graphite and unmodified/non-functionalized tire-derived carbon by studying the surface chemistry and properties, vibrational spectroscopy of the molecular structure, chemical bonding such as C–H bonding, and intermolecular interactions of the carbon materials. The nitrogen adsorption–desorption studies revealed the tailored micro and meso pore size distribution of the carbon during the sulfonation process. XPS and neutron vibrational spectra showed thatmore » the sulfonation of the initial raw tire powders could remove the aliphatic hydrogen containing groups ([double bond splayed left]CH 2 and –CH 3 groups) and reduce the number of heteroatoms that connect to carbon. The absence of these functional groups could effectively improve the first cycle efficiency of the material in rechargeable batteries. Meanwhile, the introduced –SO 3H functional group helped in producing terminal H at the edge of the sp 2 bonded graphite-like layers. Finally, this study reveals the influence of the sulfonation process on the recovered hard carbon from used tires and provides a pathway to develop and improve advanced energy storage materials.« less

Charge transfer and injection barrier at the metal-organic interfaces

NASA Astrophysics Data System (ADS)

Yan, Li

2002-09-01

The metal-organic interface plays a critical role in determining the functionality and performance of many innovative organic based devices. It has attracted extensive research interests in recent years. This thesis presents investigations of the electronic structures of organic materials, such as tris-(8-hydroxyquinoline) aluminum (Alq3) and copper phthalocyanine (CuPc), during their interface formation with metals. The characterization is accomplished by X-ray and ultraviolet photoelectron spectroscopes (XPS and UPS) and inverse photoelectron spectroscopy (IPES). As discussed herein, both occupied and unoccupied electronic states at the interfaces are carefully examined in different aspects. In Chapter 4, the charge transfer and chemical reaction at various metal/Alq3 interfaces are investigated using XPS and UPS to study the electron injection into the Alga film. Electron transfer from the low work function metal and Al/LiF(CsF) bilayer to the Alga has been observed. The role of the dielectric and possible chemistry at the interface are discussed in comparison of the low work function metals. Further in Chapter 5, the origin of the metal-interface dipole and the estimation of charge injection barrier is explored using several organic materials. A thermodynamic equilibrium model is extended to explain the relation between the charge transfer process ad the interface dipole. Further, in Chapter 6 the combination of XPS, UPS and IPES detailed the evolution of both occupied and unoccupied energy states during the alkali metal doping. The energy gap modification in organic due to metal doping is observed directly for the spectra. Chapter 7 provides stability study of the organic thin films under x-ray and UV light. The results verify the usability of UPS and XPS for the organic materials used in the thesis. Chapter 7 also shows the secondary ion mass spectroscopy results of metal diffusion in organic thin films.

The preparation of polytrifluorochloroethylene (PCTFE) micro-particles and application on treating bearing steel surfaces to improve the lubrication effect for copper-graphite (Cu/C)

NASA Astrophysics Data System (ADS)

Lu, Hailin; Zhang, Pengpeng; Ren, Shanshan; Guo, Junde; Li, Xing; Dong, Guangneng

2018-01-01

Contact mechanical seal is a normal technology applied on middle axis of liquid rocket turbo pump, and the kinetic and static seal rings contact low temperature rocket propellant. Copper-graphite (Cu/C) composite as an excellent self-lubrication material was widely used in aerospace industry, this study took Cu/C as ball and bearing steel as disk to investigate the tribology properties, and distilled water were used to simulate the lox tribology performances. This study prepared polytrifluorochloroethylene (PCTFE) micro-particles which were coated on the oxide surfaces of bearing steel disk at temperature of 150 °C. The tribology results showed that the oxide surfaces treated with micro PCTFE particles have lower fiction coefficient and lower wear rate than original disk in water, and the wear morphology revealed that the treated surfaces obviously had less Cu/C composite transfer film than original disk. Meanwhile SEM, EDS, XRD, XPS and light microscope etc revealed that PCTFE micro-particles could associate with the oxide surfaces and caused higher water contact angle, due to the properties of the fluorine-containing composite may cause the good lubrication effect in water. Thus this technology shows great potential to enhance tribological performances for aerospace industry on a large scale.

Study of annealing time on sol-gel indium tin oxide films on glass

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

De, A.; Biswas, P.K.; Manara, J.

2007-07-15

Indium and tin salt-based precursors maintaining In:Sn atomic ratio as 90:10 were utilized for the development of sol-gel dip coated indium tin oxide films (ITO) on SiO{sub 2} coated ({approx} 200 nm thickness) soda lime silica glass substrate. The gel films were initially cured in air at {approx} 450 deg. C to obtain oxide films of physical thickness {approx} 250 nm. These were then annealed in 95% Ar-5% H{sub 2} atmosphere at {approx} 500 deg. C. The annealing time was varied from 0.5 h to 5 h. Variation of annealing time did not show any considerable change of transmittance inmore » the visible region. Thermal emissivity ({epsilon} {sub d}, 0.67-0.79) of the films were evaluated from their hemispherical spectral reflectance. These passed through a minima with increasing annealing time as the reflectivity of the films in the mid-IR passed through a maxima. The microstructure of the films revealed systematic growth of the ITO grains. XRD and XPS studies revealed the presence of both In and Sn metals in addition to the metal oxides. The energy dispersive X-ray (EDX) analysis showed little lowering of tin content in the films with increasing annealing time.« less

Synchrotron-based ambient pressure X-ray photoelectron spectroscopy of hydrogen and helium

DOE PAGES

Zhong, Jian-Qiang; Wang, Mengen; Hoffmann, William H.; ...

2018-03-01

Contrary to popular belief, it is possible to obtain X-ray photoelectron spectra for elements lighter than lithium, namely hydrogen and helium. The literature is plagued with claims of this impossibility, which holds true for lab-based X-ray sources. However, this limitation is merely technical and is related mostly to the low X-ray photoionization cross-sections of the 1s orbitals of hydrogen and helium. Here, we show that, using ambient pressure X-ray photoelectron spectroscopy (XPS), a bright-enough X-ray source allows the study of these elusive elements. This has important implications in the understanding of the limitations of one of the most useful techniquesmore » in materials science, and moreover, it potentially opens the possibility of using XPS to directly study the most abundant element in the universe.« less

Arsenic doped p-type zinc oxide films grown by radio frequency magnetron sputtering

NASA Astrophysics Data System (ADS)

Fan, J. C.; Zhu, C. Y.; Fung, S.; Zhong, Y. C.; Wong, K. S.; Xie, Z.; Brauer, G.; Anwand, W.; Skorupa, W.; To, C. K.; Yang, B.; Beling, C. D.; Ling, C. C.

2009-10-01

As-doped ZnO films were grown by the radio frequency magnetron sputtering method. As the substrate temperature during growth was raised above ˜400 °C, the films changed from n type to p type. Hole concentration and mobility of ˜6×1017 cm-3 and ˜6 cm2 V-1 s-1 were achieved. The ZnO films were studied by secondary ion mass spectroscopy, x-ray photoelectron spectroscopy (XPS), low temperature photoluminescence (PL), and positron annihilation spectroscopy (PAS). The results were consistent with the AsZn-2VZn shallow acceptor model proposed by Limpijumnong et al. [Phys. Rev. Lett. 92, 155504 (2004)]. The results of the XPS, PL, PAS, and thermal studies lead us to suggest a comprehensive picture of the As-related shallow acceptor formation.

Synchrotron-based ambient pressure X-ray photoelectron spectroscopy of hydrogen and helium

NASA Astrophysics Data System (ADS)

Zhong, Jian-Qiang; Wang, Mengen; Hoffmann, William H.; van Spronsen, Matthijs A.; Lu, Deyu; Boscoboinik, J. Anibal

2018-02-01

Contrary to popular belief, it is possible to obtain X-ray photoelectron spectra for elements lighter than lithium, namely hydrogen and helium. The literature is plagued with claims of this impossibility, which holds true for lab-based X-ray sources. However, this limitation is merely technical and is related mostly to the low X-ray photoionization cross-sections of the 1s orbitals of hydrogen and helium. In this letter, we show that, using ambient pressure X-ray photoelectron spectroscopy (XPS), a bright-enough X-ray source allows the study of these elusive elements. This has important implications in the understanding of the limitations of one of the most useful techniques in materials science, and moreover, it potentially opens the possibility of using XPS to directly study the most abundant element in the universe.

Thermal decomposition study of manganese sulfide (MnS) nanoparticles

NASA Astrophysics Data System (ADS)

Tailor, Jiten P.; Khimani, Ankurkumar J.; Chaki, Sunil H.; Deshpande, M. P.

2018-05-01

The as-synthesized manganese sulfide (MnS) nanoparticles were used for the thermal study. The nanoparticles were synthesized by simple wet chemical route at ambient temperature. The photoelectron binding energy and chemical composition of MnS nanoparticles was analyzed by X-ray photoelectron spectroscopy (XPS). The thermogravimetric (TG), differential thermogravimetric (DTG) and differential thermal analysis (DTA) were carried out on the as-synthesized MnS nanoparticles. The thermocurves were recorded in inert N2 atmosphere in the temperature range of ambient to 1173 K. The heating rates employed were 5, 10, 15 and 20 K/min. The thermodynamic parameters like activation energy (Ea), enthalpy change (ΔH), entropy change (ΔS) and change in Gibbs free energy (ΔG) of as-synthesized MnS nanoparticles were determined using Kissinger method. The obtained XPS and thermal results are discussed.

Synchrotron-based ambient pressure X-ray photoelectron spectroscopy of hydrogen and helium

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

Zhong, Jian-Qiang; Wang, Mengen; Hoffmann, William H.

Contrary to popular belief, it is possible to obtain X-ray photoelectron spectra for elements lighter than lithium, namely hydrogen and helium. The literature is plagued with claims of this impossibility, which holds true for lab-based X-ray sources. However, this limitation is merely technical and is related mostly to the low X-ray photoionization cross-sections of the 1s orbitals of hydrogen and helium. Here, we show that, using ambient pressure X-ray photoelectron spectroscopy (XPS), a bright-enough X-ray source allows the study of these elusive elements. This has important implications in the understanding of the limitations of one of the most useful techniquesmore » in materials science, and moreover, it potentially opens the possibility of using XPS to directly study the most abundant element in the universe.« less

Long-Term Stability of Photovoltaic Hybrid Perovskites achieved by Graphene Passivation via a Water- and Polymer-Free Graphene Transfer Method

NASA Astrophysics Data System (ADS)

Tseng, W.-S.; Jao, M.-H.; Hsu, C.-C.; Wu, C.-I.; Yeh, N.-C.

Organic-inorganic hybrid perovskites such as CH3NH3PbX3 (X = I, Br) have been intensively studied in recent years because of their rapidly improving photovoltaic power conversion efficiency. However, severe instability of these materials in ambient environment has been a primary challenge for practical applications. To address this issue, we employ high-quality PECVD-grown graphene to passivate the hybrid perovskites. In contrast to existing processes for transferring graphene from the growth substrates to other surfaces that involve either polymer or water, which are incompatible with photovoltaic applications of these water-sensitive hybrid perovskites, we report here a new water- and polymer-free graphene transferring method. Studies of the Raman, x-ray and ultraviolet photoemission spectroscopy (XPS and UPS) demonstrated excellent quality of monolayer PECVD-grown graphene samples after their transfer onto different substrates with the water- and polymer-free processing method. In particular, graphene was successfully transferred onto the surface of CH3NH3PbI3 thin films with sample quality intact. Moreover, XPS and UPS studies indicated that even after 3 months, the fully graphene-covered perovskite films remained spectroscopically invariant, which was in sharp contrast to the drastic changes, after merely one week, in both the XPS and UPS of a control CH3NH3PbI3 sample without graphene protection. Beckman Inst. in Caltech. Dragon Gate Program in Taiwan.

XPS studies of MgO based magnetic tunnel junction structures

NASA Astrophysics Data System (ADS)

Read, John; Mather, Phil; Tan, Eileen; Buhrman, Robert

2006-03-01

The very high tunneling magnetoresistance (TMR) obtained in MgO magnetic tunnel junctions (MTJ)^(1,2) motivates the investigation of the electronic properties of the MgO barrier layer and the study of the ferromagnetic metal - MgO interface chemistry. Such large TMR values are predicted by theory due to the high degree of order apparent in the barrier and electrode materials. However, as grown ultra-thin MgO films generally contain defects that can influence electron transport properties through the creation of low energy states within the bulk MgO band-gap. We will report the results of x-ray photoelectron spectroscopy (XPS) studies of (001) textured ultra-thin MgO layers that are prepared by RF magnetron sputtering and electron beam evaporation on ordered ferromagnetic electrodes and in ordered MTJ structures with and without post growth vacuum annealing. XPS spectra for both MgO deposition techniques clearly indicate a surface oxygen species that is likely bound by defects in the oxide^(3) in half-formed junctions and improvements in MgO quality after counter electrode deposition. We will discuss our results regarding the chemical properties of the oxide and its interfaces directed towards possibly providing guidance to engineer improved MgO MTJ devices. [1] S.S.P. Parkin et. al., Nature Materials, 3, 862 (2004). [2] S. Yuasa et. al., Nature Materials, 3, 868 (2004). [3] E. Tan et. al. , Phys. Rev. B. , 71, 161401 (2005).

Rondorfite-type structure — XPS and UV–vis study

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

Dulski, M., E-mail: mateusz.dulski@smcebi.edu.pl; A.Chelkowski Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice; Bilewska, K., E-mail: kbilewska@us.edu.pl

2015-10-15

Highlights: • Structural and spectroscopic characterization of chlorosilicate mineral, rondorfite. • Characterization of main photoemission lines and valence band spectra. • The study of color origin’s using UV–vis spectroscopy. • Analysis of structural changes in context of origin of natural fluorescence. • Discussion of a new application possibilities of analyzed mineral - Abstract: This paper focuses on X-ray diffraction, X-ray photoelectron and UV–vis spectroscopy of two different (green, orange) rondorfite samples. The differences in the sample color originate from various O/Cl ratios. The orange color was found to be related either to the isomorphic substitution of Fe{sup 3+}/Al{sup 3+} formore » Mg{sup 2+}, the presence of atypical [MgO{sub 4}] tetrahedrons in crystal structure or electronegativity of the sample. The tetrahedron is known to be very prone to accumulation of impurities and substitute atoms. Moreover, the XPS data showed tetrahedrally coordinated Mg{sup 2+} and isomorphic substitution of Al{sup 3+}/Fe{sup 3+} for Mg{sup 2+}, which influences local disordering and the point defects density and distribution. Non-equilibrium chlorine positions inside the crystal cages as well as Ca-Cl bonds have also been found. The XPS measurements as a function of temperature indicate occurrence of a structural transformation at about 770 K which is accompanied by a rotation of silicate tetrahedra within magnesiosilicate pentamer and luminescence disappearance.« less

Characterization of Natural Dyes and Traditional Korean Silk Fabric by Surface Analytical Techniques

PubMed Central

Lee, Jihye; Kang, Min Hwa; Lee, Kang-Bong; Lee, Yeonhee

2013-01-01

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) and X-ray photoelectron spectroscopy (XPS) are well established surface techniques that provide both elemental and organic information from several monolayers of a sample surface, while also allowing depth profiling or image mapping to be carried out. The static TOF-SIMS with improved performances has expanded the application of TOF-SIMS to the study of a variety of organic, polymeric and biological materials. In this work, TOF-SIMS, XPS and Fourier Transform Infrared (FTIR) measurements were used to characterize commercial natural dyes and traditional silk fabric dyed with plant extracts dyes avoiding the time-consuming and destructive extraction procedures necessary for the spectrophotometric and chromatographic methods previously used. Silk textiles dyed with plant extracts were then analyzed for chemical and functional group identification of their dye components and mordants. TOF-SIMS spectra for the dyed silk fabric showed element ions from metallic mordants, specific fragment ions and molecular ions from plant-extracted dyes. The results of TOF-SIMS, XPS and FTIR are very useful as a reference database for comparison with data about traditional Korean silk fabric and to provide an understanding of traditional dyeing materials. Therefore, this study shows that surface techniques are useful for micro-destructive analysis of plant-extracted dyes and Korean dyed silk fabric. PMID:28809257

In vivo characterization of magnesium alloy biodegradation using electrochemical H2 monitoring, ICP-MS, and XPS.

PubMed

Zhao, Daoli; Wang, Tingting; Nahan, Keaton; Guo, Xuefei; Zhang, Zhanping; Dong, Zhongyun; Chen, Shuna; Chou, Da-Tren; Hong, Daeho; Kumta, Prashant N; Heineman, William R

2017-03-01

The effect of widely different corrosion rates of Mg alloys on four parameters of interest for in vivo characterization was evaluated: (1) the effectiveness of transdermal H 2 measurements with an electrochemical sensor for noninvasively monitoring biodegradation compared to the standard techniques of in vivo X-ray imaging and weight loss measurement of explanted samples, (2) the chemical compositions of the corrosion layers of the explanted samples by XPS, (3) the effect on animal organs by histology, and (4) the accumulation of corrosion by-products in multiple organs by ICP-MS. The in vivo biodegradation of three magnesium alloys chosen for their widely varying corrosion rates - ZJ41 (fast), WKX41 (intermediate) and AZ31 (slow) - were evaluated in a subcutaneous implant mouse model. Measuring H 2 with an electrochemical H 2 sensor is a simple and effective method to monitor the biodegradation process in vivo by sensing H 2 transdermally above magnesium alloys implanted subcutaneously in mice. The correlation of H 2 levels and biodegradation rate measured by weight loss shows that this non-invasive method is fast, reliable and accurate. Analysis of the insoluble biodegradation products on the explanted alloys by XPS showed all of them to consist primarily of Mg(OH) 2 , MgO, MgCO 3 and Mg 3 (PO 4 ) 2 with ZJ41 also having ZnO. The accumulation of magnesium and zinc were measured in 9 different organs by ICP-MS. Histological and ICP-MS studies reveal that there is no significant accumulation of magnesium in these organs for all three alloys; however, zinc accumulation in intestine, kidney and lung for the faster biodegrading alloy ZJ41 was observed. Although zinc accumulates in these three organs, no toxicity response was observed in the histological study. ICP-MS also shows higher levels of magnesium and zinc in the skull than in the other organs. Biodegradable devices based on magnesium and its alloys are promising because they gradually dissolve and thereby avoid the need for subsequent removal by surgery if complications arise. In vivo biodegradation rate is one of the crucial parameters for the development of these alloys. Promising alloys are first evaluated in vivo by being implanted subcutaneously in mice for 1month. Here, we evaluated several magnesium alloys with widely varying corrosion rates in vivo using multiple characterization techniques. Since the alloys biodegrade by reacting with water forming H 2 gas, we used a recently demonstrated, simple, fast and noninvasive method to monitor the biodegradation process by just pressing the tip of a H 2 sensor against the skin above the implant. The analysis of 9 organs (intestine, kidney, spleen, lung, heart, liver, skin, brain and skull) for accumulation of Mg and Zn revealed no significant accumulation of magnesium in these organs. Zinc accumulation in intestine, kidney and lung was observed for the faster corroding implant ZJ41. The surfaces of explanted alloys were analyzed to determine the composition of the insoluble biodegradation products. The results suggest that these tested alloys are potential candidates for biodegradable implant applications. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The presence of Ti(II) centers in doped nanoscale TiO2 and TiO2-xNx

NASA Astrophysics Data System (ADS)

Mikulas, Tanya; Fang, Zongtang; Gole, James L.; White, Mark G.; Dixon, David A.

2012-06-01

Unusual trends are observed in the Ti (2s, 2p) XPS spectra of Fe(II) doped TiO2 and TiO2-xNx. The binding energy of Ti (2s, 2p) initially decreases with increasing Fe(II) concentration, as expected, but increases at higher Fe(II) doping levels. Density functional theory is used to analyze the results. The observed VB-XPS and core level XPS spectra are consistent with the facile charge transfer sequence Ti(IV) + Fe(II) → Ti(III) + Fe(III) followed by Ti(III) + Fe(II) → Ti(II) + Fe(III). The formed Ti(II) sites may be relevant to nanoparticle catalysis on TiO2 surfaces.

Quantification of the toxic hexavalent chromium content in an organic matrix by X-ray photoelectron spectroscopy (XPS) and ultra-low-angle microtomy (ULAM)

NASA Astrophysics Data System (ADS)

Greunz, Theresia; Duchaczek, Hubert; Sagl, Raffaela; Duchoslav, Jiri; Steinberger, Roland; Strauß, Bernhard; Stifter, David

2017-02-01

Cr(VI) is known for its corrosion inhibitive properties and is, despite legal regulations, still a potential candidate to be added to thin (1-3 μm) protective coatings applied on, e.g., electrical steel as used for transformers, etc. However, Cr(VI) is harmful to the environment and to the human health. Hence, a reliable quantification of it is of decisive interest. Commonly, an alkaline extraction with a photometric endpoint detection of Cr(VI) is used for such material systems. However, this procedure requires an accurate knowledge on sample parameters such as dry film thickness and coating density that are occasionally associated with significant experimental errors. We present a comprehensive study of a coating system with a defined Cr(VI) pigment concentration applied on electrical steel. X-ray photoelectron spectroscopy (XPS) was employed to resolve the elemental chromium concentration and the chemical state. Turning to the fact that XPS is extremely surface sensitive (<10 nm) and that the lowest commonly achievable lateral resolution is a number of times higher than the coating thickness (∼2 μm), a bulk analysis was achieved with XPS line scans on extended wedge-shaped tapers through the coating. For that purpose a special sample preparation step performed on an ultra-microtome was required prior to analysis. Since a temperature increase leads to a reduction of Cr(VI) we extend our method on samples, which were subjected to different curing temperatures. We show that our proposed approach now allows to determine the elemental and Cr(VI) concentration and distribution inside the coating.

Structural and mechanical properties of Al-C-N films deposited at room temperature by plasma focus device

NASA Astrophysics Data System (ADS)

Z, A. Umar; R, Ahmad; R, S. Rawat; M, A. Baig; J, Siddiqui; T, Hussain

2016-07-01

The Al-C-N films are deposited on Si substrates by using a dense plasma focus (DPF) device with aluminum fitted central electrode (anode) and by operating the device with CH4/N2 gas admixture ratio of 1:1. XRD results verify the crystalline AlN (111) and Al3CON (110) phase formation of the films deposited using multiple shots. The elemental compositions as well as chemical states of the deposited Al-C-N films are studied using XPS analysis, which affirm Al-N, C-C, and C-N bonding. The FESEM analysis reveals that the deposited films are composed of nanoparticles and nanoparticle agglomerates. The size of the agglomerates increases at a higher number of focus deposition shots for multiple shot depositions. Nanoindentation results reveal the variation in mechanical properties (nanohardness and elastic modulus) of Al-C-N films deposited with multiple shots. The highest values of nanohardness and elastic modulus are found to be about 11 and 185 GPa, respectively, for the film deposited with 30 focus deposition shots. The mechanical properties of the films deposited using multiple shots are related to the Al content and C-N bonding.

BiVO4 -TiO2 Composite Photocatalysts for Dye Degradation Formed Using the SILAR Method.

PubMed

Odling, Gylen; Robertson, Neil

2016-09-19

Composite photocatalyst films have been fabricated by depositing BiVO4 upon TiO2 via a sequential ionic layer adsorption reaction (SILAR) method. The photocatalytic materials were investigated by XRD, TEM, UV/Vis diffuse reflectance, inductively coupled plasma optical emission spectrometry (ICP-OES), XPS, photoluminescence and Mott-Schottky analyses. SILAR processing was found to deposit monoclinic-scheelite BiVO4 nanoparticles onto the surface, giving successive improvements in the films' visible light harvesting. Electrochemical and valence band XPS studies revealed that the prepared heterojunctions have a type II band structure, with the BiVO4 conduction band and valence band lying cathodically shifted from those of TiO2 . The photocatalytic activity of the films was measured by the decolourisation of the dye rhodamine 6G using λ>400 nm visible light. It was found that five SILAR cycles was optimal, with a pseudo-first-order rate constant of 0.004 min(-1) . As a reference material, the same SILAR modification has been made to an inactive wide-band-gap ZrO2 film, where the mismatch of conduction and valence band energies disallows charge separation. The photocatalytic activity of the BiVO4 -ZrO2 system was found to be significantly reduced, highlighting the importance of charge separation across the interface. The mechanism of action of the photocatalysts has also been investigated, in particular the effect of self-sensitisation by the model organic dye and the ability of the dye to inject electrons into the photocatalyst's conduction band. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ambient pressure XPS and IRRAS investigation of ethanol steam reforming on Ni–CeO 2(111) catalysts: An in situ study of C–C and O–H bond scission

DOE PAGES

Liu, Zongyuan; Duchon, Tomas; Wang, Huanru; ...

2016-03-31

Ambient-Pressure X-ray Photoelectron Spectroscopy (AP-XPS) and Infrared Reflection Absorption Spectroscopy (AP-IRRAS) have been used to elucidate the active sites and mechanistic steps associated with the ethanol steam reforming reaction (ESR) over Ni–CeO 2(111) model catalysts. Our results reveal that surface layers of the ceria substrate are both highly reduced and hydroxylated under reaction conditions while the small supported Ni nanoparticles are present as Ni 0/NixC. A multifunctional, synergistic role is highlighted in which Ni, CeO x and the interface provide an ensemble effect in the active chemistry that leads to H 2. Ni 0 is the active phase leading tomore » both C–C and C–H bond cleavage in ethanol and it is also responsible for carbon accumulation. On the other hand, CeO x is important for the deprotonation of ethanol/water to ethoxy and OH intermediates. The active state of CeO x is a Ce 3+(OH) x compound that results from extensive reduction by ethanol and the efficient dissociation of water. Additionally, we gain an important insight into the stability and selectivity of the catalyst by its effective water dissociation, where the accumulation of surface carbon can be mitigated by the increased presence of surface OH groups. As a result, the co-existence and cooperative interplay of Ni 0 and Ce 3+(OH) x through a metal–support interaction facilitate oxygen transfer, activation of ethanol/water as well as the removal of coke.« less

Electrochemical Corrosion and In Vitro Bioactivity of Nano-Grained Biomedical Ti-20Nb-13Zr Alloy in a Simulated Body Fluid

PubMed Central

Kumar, Madhan; Drew, Robin; Al-Aqeeli, Nasser

2017-01-01

The bioactivity and the corrosion protection for a novel nano-grained Ti-20Nb-13Zr at % alloy were examined in a simulated body fluid (SBF). The effect of the SPS’s temperature on the corrosion performance was investigated. The phases and microstructural details of the developed alloy were analyzed by XRD (X-ray Diffraction), SEM (Scanning Electron Microscopy), and TEM (Transmission Electron Microscope). The electrochemical study was investigated using linear potentiodynamic polarization and electrochemical impedance spectroscopy in a SBF, and the bioactivity was examined by immersing the developed alloy in a SBF for 3, 7, and 14 days. The morphology of the depositions after immersion was examined using SEM. Alloy surface analysis after immersion in the SBF was characterized by XPS (X-ray Photoelectron Spectroscopy). The results of the bioactivity test in SBF revealed the growth of a hydroxyapatite layer on the surface of the alloy. The analysis of XPS showed the formation of protective oxides of TiO2, Ti2O3, ZrO2, Nb2O5, and a Ca3(PO4)2 compound (precursor of hydroxyapatite) deposited on the alloy surface, indicating that the presented alloy can stimulate bone formation. The corrosion resistance increased by increasing the sintering temperature and the highest corrosion resistance was obtained at 1200 °C. The improved corrosion protection was found to be related to the alloy densification. The bioactivity and the corrosion resistance of the developed nanostructured alloy in a SBF renders the nanostructured Ti-20Nb-13Zr alloy a promising candidate as an implant material. PMID:29280956

Mechanism of in situ surface polymerization of gallic acid in an environmental-inspired preparation of carboxylated core-shell magnetite nanoparticles.

PubMed

Tóth, Ildikó Y; Szekeres, Márta; Turcu, Rodica; Sáringer, Szilárd; Illés, Erzsébet; Nesztor, Dániel; Tombácz, Etelka

2014-12-30

Magnetite nanoparticles (MNPs) with biocompatible coatings are good candidates for MRI (magnetic resonance imaging) contrasting, magnetic hyperthermia treatments, and drug delivery systems. The spontaneous surface induced polymerization of dissolved organic matter on environmental mineral particles inspired us to prepare carboxylated core-shell MNPs by using a ubiquitous polyphenolic precursor. Through the adsorption and in situ surface polymerization of gallic acid (GA), a polygallate (PGA) coating is formed on the nanoparticles (PGA@MNP) with possible antioxidant capacity. The present work explores the mechanism of polymerization with the help of potentiometric acid-base titration, dynamic light scattering (for particle size and zeta potential determination), UV-vis (UV-visible light spectroscopy), FTIR-ATR (Fourier-transformed infrared spectroscopy by attenuated total reflection), and XPS (X-ray photoelectron spectroscopy) techniques. We observed the formation of ester and ether linkages between gallate monomers both in solution and in the adsorbed state. Higher polymers were formed in the course of several weeks both on the surface of nanoparticles and in the dispersion medium. The ratio of the absorbances of PGA supernatants at 400 and 600 nm (i.e., the E4/E6 ratio commonly used to characterize the degree of polymerization of humic materials) was determined to be 4.3, similar to that of humic acids. Combined XPS, dynamic light scattering, and FTIR-ATR results revealed that, prior to polymerization, the GA monomers became oxidized to poly(carboxylic acid)s due to ring opening while Fe(3+) ions reduced to Fe(2+). Our published results on the colloidal and chemical stability of PGA@MNPs are referenced thoroughly in the present work. Detailed studies on biocompatibility, antioxidant property, and biomedical applicability of the particles will be published.

Chemical and Morphological Characterization of Magnetron Sputtered at Different Bias Voltages Cr-Al-C Coatings

PubMed Central

Obrosov, Aleksei; Gulyaev, Roman; Zak, Andrzej; Ratzke, Markus; Naveed, Muhammad; Dudzinski, Wlodzimierz; Weiß, Sabine

2017-01-01

MAX phases (M = transition metal, A = A-group element, and X = C/N) are of special interest because they possess a unique combination of the advantages of both metals and ceramics. Most attention is attracted to the ternary carbide Cr2AlC because of its excellent high-temperature oxidation, as well as hot corrosion resistance. Despite lots of publications, up to now the influence of bias voltage on the chemical bonding structure, surface morphology, and mechanical properties of the film is still not well understood. In the current study, Cr-Al-C films were deposited on silicon wafers (100) and Inconel 718 super alloy by dc magnetron sputtering with different substrate bias voltages and investigated using Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD), Atomic Force Microscopy (AFM), and nanoindentation. Transmission Electron Microscopy (TEM) was used to analyze the correlation between the growth of the films and the coating microstructure. The XPS results confirm the presence of Cr2AlC MAX phase due to a negative shift of 0.6–0.9 eV of the Al2p to pure aluminum carbide peak. The XRD results reveal the presence of Cr2AlC MAX Phase and carbide phases, as well as intermetallic AlCr2. The film thickness decreases from 8.95 to 6.98 µm with increasing bias voltage. The coatings deposited at 90 V exhibit the lowest roughness (33 nm) and granular size (76 nm) combined with the highest hardness (15.9 GPa). The ratio of Al carbide to carbide-like carbon state changes from 0.12 to 0.22 and correlates with the mechanical properties of the coatings. TEM confirms the columnar structure, with a nanocrystalline substructure, of the films. PMID:28772516