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1.
Ionoluminescence (IL) and photoluminescence (PL) spectra for different rare earth ions (Sm3+ and Dy3+) activated YAlO3 single crystals have been induced with 100 MeV Si7+ ions with fluence of 7.81×1012 ions cm?2. Prominent IL and PL emission peaks in the range 550–725 nm in Sm3+ and 482–574 nm in Dy3+ were recorded. Variation of IL intensity in Dy3+ doped YAlO3 single crystals was studied in the fluence range 7.81×1012–11.71×1012 ions cm?2. IL intensity is found to be high in lower ion fluences and it decreases with increase in ion fluence due to thermal quenching as a result of an increase in the sample temperature caused by ion beam irradiation. Thermoluminescence (TL) spectra were recorded for fluence of 5.2×1012 ions cm?2 on pure and doped crystals at a warming rate of 5 °C s?1 at room temperature. Pure crystals show two glow peaks at 232 (Tg1) and 328 °C (Tg2). However, in Sm3+ doped crystals three glow peaks at 278 (Tg1), 332 (Tg2) and 384 °C (Tg3) and two glow peaks at 278 (Tg1) and 331 °C (Tg2) in Dy3+ was recorded. The kinetic parameters (E, b s) were estimated using glow peak shape method. The decay of IL intensity was explained by excitation spike model.  相似文献   

2.
Copper tungstate (CuWO4) crystals were synthesized by the sonochemistry (SC) method, and then, heat treated in a conventional furnace at different temperatures for 1 h. The structural evolution, growth mechanism and photoluminescence (PL) properties of these crystals were thoroughly investigated. X-ray diffraction patterns, micro-Raman spectra and Fourier transformed infrared spectra indicated that crystals heat treated and 100 °C and 200 °C have water molecules in their lattice (copper tungstate dihydrate (CuWO4·2H2O) with monoclinic structure), when the crystals are calcinated at 300 °C have the presence of two phase (CuWO4·2H2O and CuWO4), while the others heat treated at 400 °C and 500 °C have a single CuWO4 triclinic structure. Field emission scanning electron microscopy revealed a change in the morphological features of these crystals with the increase of the heat treatment temperature. Transmission electron microscopy (TEM), high resolution-TEM images and selected area electron diffraction were employed to examine the shape, size and structure of these crystals. Ultraviolet–Visible spectra evidenced a decrease of band gap values with the increase of the temperature, which were correlated with the reduction of intermediary energy levels within the band gap. The intense photoluminescence (PL) emission was detected for the sample heat treat at 300 °C for 1 h, which have a mixture of CuWO4·2H2O and CuWO4 phases. Therefore, there is a synergic effect between the intermediary energy levels arising from these two phases during the electronic transitions responsible for PL emissions.  相似文献   

3.
The kinetics of the C6H5 reactions with CH3OH and C2H5OH has been measured by pulsed-laser photolysis/mass-spectrometry (PLP/MS) employing acetophenone as the radical source. Kinetic modeling of the benzene formed in the reactions over the temperature range 306–771 K allows us to reliably determine the total rate constants for H-abstraction reactions. In order to improve our low temperature measurements down to 304 K we have also applied the cavity ring-down spectrometric technique using nitrosobenzene as the radical source. Both sets of data agree closely. A weighted least-squares analysis of the two complementary sets of data for the two reactions gave the total rate constants k(CH3OH) = (7.82 ± 0.44) × 1011 exp [?(853 ± 30)/T] and k(C2H5OH) = (5.73 ± 0.58) × 1011 exp [?(1103 ± 44)/T] cm3 mol?1 s?1 for the temperature range studied. Theoretically, four possible product channels of the C6H5 + CH3OH reaction producing C6H6 + CH3O, C6H6 + CH2OH, C6H5OH + CH3 and C6H5OCH3 + H and five possible product channels of the C6H5 + C2H5OH reaction producing C6H6 + C2H5O, C6H6 + CH2CH2OH, C6H6 + CH3CHOH, C6H5OH + CH3CH2 and C6H5OCH2CH3 + H have been computed at the G2M//B3LYP/6?311+G(d, p) level of theory. The hydrogen abstraction channels were predicted to have lower energy barriers than those for the substitution reactions and their rate constants were calculated by the microcanonical variational transition state theory at 200–3000 K. The predicted rate constants are in good agreement with the experimental values. Significantly, the rate constant for the CH3OH reaction with C6H5 was found to be greater than that for the C2H5OH reaction and both reactions were found computationally to be dominated by H-abstraction from the hydroxyl group attributable to the affinity of the phenyl toward the OH group and the predicted lower energy barriers for the OH attack.  相似文献   

4.
Silicate mineral hemimorphite has been investigated concerning its TL, IR and EPR properties. A broad TL peak around 180 °C and a weaker and narrower peak around 360 °C were found in a sample annealed at 600 °C for 1 h and then irradiated. The deconvolution using the CGCD method revealed peaks around 132, 169, 222 and 367 °C. The reflectivity measurements showed several bands in the NIR region due to H2O, OH and Al–OH complexes. No band was observed in the visible region. The thermal treatments were carried out from ∼110 to 940 °C and dehydration was observed, first causing a diminishing optical absorption in general and the disappearance of water and hydroxyl absorption bands. The EPR spectrum of natural hemimorphite, presented Cu2+ signals at g = 2.4 and g = 2.1 plus E1′ signal superposed to Fe3+ signal around g = 2.0.  相似文献   

5.
K. Russel Raj  P. Murugakoothan 《Optik》2012,123(12):1082-1086
Single crystals of semiorganic material 3-aminophenol orthophosphoric acid (denoted as 3-amphph) of size 29 × 17 × 4 mm3 have been grown by the slow evaporation of an aqueous solution of deionized water at 50 °C. The crystal belongs to orthorhombic system with the non centrosymmetric space group P212121. The lattice parameter values of 3-amphph crystal are a = 4.481(2) Å, b = 9.782(4) Å and c = 18.326(4) Å. The grown crystals are subjected to single crystal XRD studies to identify its morphology and structure. Optical transmittance and second harmonic generation of the grown crystals have been studied by UV–Vis–NIR spectrum and Kurtz powder technique respectively. The transmittance of 3-amphph crystal has been used to calculate the refractive index n, the extinction coefficient k, reflectance R and both the real (?r) and imaginary (?i) components of the dielectric constant as a function of wavelength. The optical band gap of 3-amphph is 4.05 eV with direct transition. The anisotropic mechanical behavior of 3-amphph has been analyzed using Vickers microhardness test. The mechanism of growth is revealed by carrying out chemical etching using water as etchant.  相似文献   

6.
Proton transfer in water–hydroxyl mixed overlayers on a Pt(1 1 1) surface was studied by a combination of laser induced thermal desorption (LITD) method and spatially-resolved X-ray photoelectron spectroscopy (micro-XPS). The modulated pattern OH + H2O/H2O/OH + H2O was initially prepared by the LITD method; vacant area with a 400 μm width was first formed in the mixed OH + H2O overlayer by irradiation of focused laser pulses, and followed by refilling the vacant area with pure H2O. Spatial distribution changes of OH and H2O were measured as a function of time with the micro-XPS technique, which indicated that H2O molecules in the central region flow into the OH + H2O region. From quantitative analyses using a diffusion equation, we found that the proton transfer in the mixed overlayer consists of at least two pathways: direct proton transfer from H2O to OH in the nearest site and the proton transfer to the next-nearest site via H3O+ formation. The time scale of first and second path was estimated to be 5.2 ± 0.9 ns and 48 ± 12 ns at 140 K, respectively. In the presence of water capping layer, however, the rate of proton transfer is reduced by an order of magnitude, which would be explained by peripatetic behavior of proton into H2O capping layer.  相似文献   

7.
《Current Applied Physics》2009,9(5):1125-1128
Sodium bitartrate monohydrate (SBTMH) a new organometallic nonlinear optical material, with molecular formula, [C4H5NaO6 · H2O] has been synthesized at ambient temperature. Spectral, thermal and optical techniques have been employed to characterize the new material. Bulk single crystals of size 13 × 4 × 4 mm3 of SBTMH have been grown by slow cooling method. The unit cell parameters of the grown crystal were determined by single crystal XRD. Functional groups present in the sample were identified by FTIR spectral analysis. Thermal stability of SBTMH was determined using TGA/DTA. The grown crystals exhibit nonlinear properties. The dielectric response of the crystal with varying frequencies was studied. The optical transparency range and the lower cut-off wavelength of the material were identified from the UV–vis–NIR absorption spectrum.  相似文献   

8.
The Cr 2p and O 1s binding energy (BE) levels have been calculated by first principles methods for different models of hydroxylated (0001)-Cr2O3 surfaces. Several surface terminations have been considered. The calculations allow us to reproduce the O 1s shifts between O in oxide and OH groups. It is found that two main effects account for the OH binding energy shifts. On the one hand, the increased covalency of the O–H bond with respect to the Cr–O bond, lowers the electronic O (1s and 2p) energy, and in consequence the BE of the core levels (O 1s) are higher. On the other hand, the lower the OH coordination number, the higher the valence and core levels energy, and the lower the BE. Consequently, mono-coordinated hydroxyls have a binding energy near that of O2? in the oxide (ΔBEOH–O = ? 0.2–0.0 eV). Two-fold coordinated hydroxyls have a slightly higher BE (ΔBEOH–O = + 0.3 eV). Three-fold coordinated OH groups have a higher binding energy (ΔBEOH–O = + 0.6?0.7 eV), corresponding to that experimentally measured for OH groups. Finally, water adsorbed above OH groups exhibits a still higher BE (ΔBEHOH–O = + 0.9–1.0 eV). The ΔBE are slightly under-estimated under the initial state approximation, and overestimated under the final state (Z + 1) approximation.  相似文献   

9.
《Solid State Ionics》2006,177(19-25):1597-1600
Upon reduction, originally fully transparent and insulating ytterbium alumina garnet single crystals, Yb3Al5O12, become deeply colored and electrically conducting with a conductivity of the order of 10 3 Ω 1 cm 1 in the temperature range of 550 °C to 1000 °C. The redox kinetics of the material is studied by means of conductivity relaxation experiments performed at oxidising and reducing conditions. Good agreement is obtained with an optical study into the redox kinetics of Yb3Al5O12.  相似文献   

10.
《Current Applied Physics》2010,10(5):1349-1353
Single crystals of semiorganic material calcium dibromide bis(glycine) tetrahydrate were grown from aqueous solution. The crystal belongs to monoclinic system, with a = 13.261(5) Å, b = 6.792(2) Å, c = 15.671(9) Å and β = 91.68(4)°. The presence of the elements in the title compound was confirmed by energy dispersive X-ray analysis. The solubility and metastable zone width were found. The grown crystals were tested by powder XRD, FTIR, Thermo Gravimetric and Differential Thermal Analysis, UV–vis–NIR analysis, dielectrical and mechanical studies. The transmittance of calcium dibromide bis(glycine) tetrahydrate crystal has been used to calculate the refractive index n, the extinction coefficient K and both the real ɛr and imaginary ɛi components of the dielectric constant as functions of wavelength. The optical band gap of calcium dibromide bis(glycine) tetrahydrate is 3.23 eV.  相似文献   

11.
Bulk single crystals of glycinium maleate have been grown from aqueous solution by slow evaporation method by optimizing the growth parameters within a period of 15 days. From X-ray diffraction analysis, the crystal was found to crystallize in monoclinic structure (space group C2/c) with a = 17.866 Å, b = 5.684 Å, c = 17.408 Å and β = 112.65°. Presence of characteristic functional groups was confirmed in FTIR analysis. UV–Vis spectral analysis has revealed the absence of any high absorbance region between the wavelengths ranging from 300 to 900 nm. The optical band gap was calculated and found to be 3.91 eV. The activation energy for conduction at different frequencies was calculated and found to decrease from 0.54 eV to 0.41 eV as frequency increased from 100 Hz to 2 MHz. The dielectric behavior, conduction mechanism and the optical characterization of the glycinium maleate single crystals are being reported for the first time.  相似文献   

12.
La(OH)3/Ni(OH)2 nanocables and La(OH)3 nanorods were synthesized by the reaction of KOH with La(NO3)3 and Ni(NO3)2 at 180 °C under a hydrothermal conditions. X-ray diffraction, transmission electron microscopy and thermal analyses indicated that the nanocable consists of La(OH)3 core and Ni(OH)2 outer shell. The diameters of the La(OH)3 nanorods range from 20 to 30 nm and the lengths range from 150 to 1000 nm. The thickness of the Ni(OH)2 coating ranges from 10 to 20 nm. The formation mechanism of the nanocables is discussed.  相似文献   

13.
Nickel based porous solid was synthesized with 20 kHz ultrasonic irradiation. The reaction of Ni(II) nitrate hexahydrate with 1,3,5-benzene tricarboxylic acid in N,N-Dimethylformamide (DMF) as the sole solvent under ultrasonic radiation produced porous Ni-BTC MOF. Choice of correct solvent for the ultrasonic treatment was proven important. The effect of varying ultrasonic powers (40%, 60% and 80% of 750 W) along with different temperature conditions (50 °C, 60 °C, 70 °C and 80 °C) influenced the respective yield. A very high yield of 88% Ni-BTC MOF was obtained from 80% ultrasonic power at 60 °C. BET surface areas of the MOF crystals measured by N2 gas adsorption isotherms were in the range of 960–1000 m2/g.  相似文献   

14.
Michael A. Henderson 《Surface science》2010,604(13-14):1197-1201
Temperature programmed desorption (TPD), electron energy loss spectroscopy (ELS) and low energy electron diffraction (LEED) were used to study the interaction of molecular oxygen with the (2 × 1) reconstructed surface of hematite α-Fe2O3(011­2) under UHV conditions. The (2 × 1) surface is formed from vacuum annealing of the ‘ideal’ (1 × 1) surface and possesses Fe2+ surface sites based on ELS. While O2 does not stick to the (1 × 1) surface at 120 K, the amount of O2 that can be reversibly adsorbed at 120 K on the (2 × 1) surface was estimated to be ~ 0.5 ML (where 1 ML is defined as the Fe3+ surface coverage on the ideal (1 × 1) surface), with additional O2 that is irreversibly adsorbed based on subsequent H2O TPD. Molecularly and dissociatively adsorbed O2 modifies the surface chemistry of H2O both in terms of enhanced OH stability (relative to either the (1 × 1) or (2 × 1) surfaces) and in the blocking of H2O adsorption sites. While O2 adsorption at 120 to 300 K does not transform the (2 × 1) surface into the (1 × 1) surface, the influence of O2 on the (2 × 1) surface involves both charge transfer from surface Fe2+ sites and formation of an ordered c(2 × 2) structure resulting from O2 dissociation.  相似文献   

15.
A batch production for fabrication of LREBa2Cu3Oy (LRE: Sm, Gd, NEG) “LRE-123” pellets are developed in air and Ar-1% O2 using a novel thin film Nd-123 seeds grown on MgO crystals. The SEM and XRD results conformed that the quality and orientation of the seed crystals are excellent. On the other hand, new seeds can withstand temperatures >1100 °C, as a result, the cold seeding process was applied even to grow Sm-123 material in Air. The trapped field observed in the best 45 mm single-grain puck of Gd-123 was in the range of 1.35 T and 0.35 T at 77.3 K and 87.3 K, respectively. The average trapped field at 77.3 K in the 24 mm diameter NEG-123 samples batch lies between 0.9 and 1 T. The maximum trapped field of 1.2 T was recorded at the sample surface. Further, the maximum trapped field of 0.23 T at 77 K was recorded in a sample with 16 mm diameter of Sm-123 with 3 mol% BaO2 addition. As a result we made more then 130 single grain pucks within a couple of months. Taking advantage of the single grain batch processed material, we constructed self-made chilled levitation disk, which was used on the open day of railway technical research Institute. More then 150 children stood on the levitation disk and revel the experience of levitation. The present results prove that a high-performance good-quality class of LREBa2Cu3Oy material can be made by using a novel thin film Nd-123 seeds.  相似文献   

16.
From aqueous NaOH/Ca(OH)2/NaAl(OH)4 mixtures, after allowing short reaction times we observed the precipitation of Ca(OH)2(s) at lower, and a mixture of Ca(OH)2(s) and a layered double hydroxide, hydrocalumite (HC) at higher aluminate concentrations. From the maximum aluminate concentration, at which the equilibrium solid phase is still portlandite (i.e., further increase in the aluminate concentration results in HC appearing in the precipitate beside the portlandite), the concentration based solubility products of two polymorphs of HC with the formula of [Ca2Al(OH)6]OH·nH2O (differing in n) has been estimated and was found to be log LHC=−11.4 at 25 °C and −12.1 at 75 °C, respectively (where LHC=[Ca2+]2[Al(OH)4][OH]3) and at constant ionic strength (I=1 M NaCl). To the best of our knowledge, this is the first published estimate for the solubility product of hydrocalumite. Additionally, from the composition obtained for NaOH/Ca(OH)2/NaAl(OH)4 mother liquors in equilibrium with Ca(OH)2(s), attempts were made to extract the formation constant of the ion pair CaAl(OH)4+. It was found, that the effects caused by the supposed formation of this solution species are too small to be reliably determined, which allowed an upper estimate for its formation constant, K, to be suggested in the temperature range of 25–75 °C (K<200 and 40 M−1 at 25 and 75 °C, respectively).  相似文献   

17.
In this paper, we report our results on the synthesis of Mg-Al and Zn-Al-layered double hydroxides using the laser ablation in the liquid technique. To prepare these layered double hydroxides (LDH) we first began with the laser generation of a Mg (or zinc) target submerged in deionized water and then ablated an aluminum target submerged in the previously prepared Mg-deionized water suspensions (Mg-dw) to produce Mg-Al LDH and in Zn-dw to prepare Zn-Al LDH. In these ablation tests, the Mg ablation duration was selected to vary from 5 to 60 min, while the Al ablation duration was kept constant at 30 min for all samples. The generated Mg-Al LDH was a gel-like and well crystallized nanoparticles of a rod-like shape and were arranged in a well-organized pattern. When the Mg ablation duration between 25 and 35 min, the synthesized nanocrystals were stoichiometric with a formula of Mg6Al2(OH)184.5(H2O), the interlayer distance (d(0 0 3)-spacing) was 7.8 Å and the average grain size was 8.0 nm. The synthesized Zn-Al LDH revealed various lamellar thin plate-like nanostructures of hexagonal morphologies. The average diameters of these structures was about 500 nm and the thickness of a single layer was approximately about 6.0 nm. The XRD diffraction peaks were indexed in hexagonal lattice with ao=3.07 Å and co=15.12 Å. These indexes were (0 0 2), (0 0 4), and (0 0 8) and the corresponding interlayer distances, d-spacing (Å), were 7.56 (0 0 2), 3.782 (0 0 4), and 1.891 (0 0 8), respectively.  相似文献   

18.
Lithium borate (LBO) single crystals doped with Cu and Ag (0.25 mol% each) (Li2B4O7:Cu,Ag) are grown by the Czochralski method. The thermoluminescence readout on Li2B4O7:Cu,Ag crystals showed three glow peaks at~375, 441 and 516 K for the heating rate of 1  K/s. The thermoluminescence sensitivity of the grown Li2B4O7:Cu,Ag single crystals is found to be 5 times TLD-100 and a linear dose response in the range 1 mGy to 1 kGy. The glow curve deconvolution reveals nearly first order kinetics for all the three peaks with trap depths 0.77, 1.25 and 1.34 eV respectively and corresponding frequency factors 1.6×109, 1.3×1013 and 6.8×1011 s?1. The continuous wave optically stimulated luminescence (CW-OSL) measurements were performed on the LBO:Cu,Ag single crystals using blue light stimulation. The traps responsible for the three thermoluminescence peaks in Li2B4O7:Cu,Ag are found to be OSL sensitive. The qualitative correlation between TL peaks and CW-OSL response is established. The photoluminescence studies show that in case of co-doping of Ag in LBO:Cu the emission at 370 nm in Cu states dominates over the transitions in Ag states implying doping of Ag plays a role as sensitizer when co-doped with Cu and increases overall emission.  相似文献   

19.
Single crystals of (Bi1−xPbx)2Sr2Ca2Cu3O10+δ (x = 0 and 0.16) (sizes up to 3 × 2 × 0.1 mm3) have been grown by means of a newly developed “vapour-assisted travelling solvent floating zone” technique (VA-TSFZ). Post-annealing under high pressure of O2 (up to 10 MPa at T = 500 °C) was applied to enhance Tc (up to 111 K) and improve the homogeneity of the crystals (ΔTc  1 K). The structure of both Pb-free and Pb-doped Bi-2223 was refined for the first time from single crystal X-ray diffraction (XRD) data. The unit cell of the average structure is pseudo-tetragonal with a = 5.4210(7), b = 5.4133(6) and c = 37.010(7) Å, and a = 5.395(1), b = 5.413(1) and c = 37.042(11) Å, for the Pb-free and the Pb-doped phase, respectively. An incommensurate modulation in the direction of one of the short cell vectors has been defined (q  0.21 a1), however, the structure can be conveniently described in a supercell with a fivefold volume (a = 27.105(4) Å). With respect to the “non-modulated” structure, one additional oxygen atom for ten initial O was found to be inserted into the BiO layers. The superconducting anisotropy of Bi-2223 was found to be ∼50, from measurements of the lower critical field. The anisotropy of Bi-2223 is significantly reduced compared to that of Bi-2212, and this accounts for the enhanced irreversibility fields in Bi-2223. Furthermore, Bi-2223 has a higher critical current density, and a reduced magnetic relaxation rate compared to Bi-2212, which are both signatures of more effective pinning in Bi-2223 due to its reduced anisotropy.  相似文献   

20.
《Solid State Ionics》2006,177(3-4):237-244
Ongoing studies of the KHSeO4–KH2PO4 system aiming at developing novel proton conducting solids resulted in the new compound K2(HSeO4)1.5(H2PO4)0.5 (dipotassium hydrogenselenate dihydrogenphosphate). The crystals were prepared by a slow evaporation of an aqueous solution at room temperature. The structural properties of the crystals were characterized by single-crystal X-ray analysis: K2(HSeO4)1.5(H2PO4)0.5 (denoted KHSeP) crystallizes in the space group P 1¯ with the lattice parameters: a = 7.417(3) Å, b = 7.668(2) Å, c = 7.744(5) Å, α = 71.59(3)°, β = 87.71(4)° and γ = 86.04(6)°. This structure is characterized by HSeO4 and disordered (HxSe/P)O4 tetrahedra connected to dimers via hydrogen bridges. These dimers are linked and stabilized by additional hydrogen bonds (O–H–O) and hydrogen bridges (O–H…O) to build chains of dimers which are parallel to the [0, 1, 0] direction at the position x = 0.5.The differential scanning calorimetry diagram showed two anomalies at 493 and 563 K. These transitions were also characterized by optical birefringence, impedance and modulus spectroscopy techniques. The conductivity relaxation parameters of the proton conductors in this compound were determined in a wide temperature range. The transport properties in this material are assumed to be due to H+ protons hopping mechanism.  相似文献   

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