Nanocrystalline cerium oxide coated fiber optic gas sensor

A clad-modified fiber optic sensor with nanocrystalline CeO₂ is proposed for gas detection. As-prepared and annealed CeO₂ (500 °C) samples have been used as gas sensing media. The spectral characteristics of the fiber optic gas sensor are studied for various concentrations of ammonia, ethanol and methanol gases (0–500 ppm). The sensor exhibits linear variation in the spectral peak intensity with the gas concentration. The characteristics of the sensor are also studied for gas selectivity. The time response characteristics of the sensor are reported.     

Hole traps and thermoluminescence in Li2B4O7:Be

A trapped-hole centre with a high thermal stability is studied in Li₂B₄O₇:Be. EPR spectrum demonstrates a hyperfine splitting due to interaction of the trapped hole with a ⁹Be nucleus. The hole is trapped at the common vertex (bridging oxygen) of two adjacent BO₄ tetrahedra when Be²⁺ substitutes for B³⁺ in one of them. The centre is stable up to ≈500 K. The high-temperature thermoluminescence peak at 510–575 K occurs when the released holes recombine with trapped electrons. This peak shows an ultraviolet exciton-like luminescence band and also luminescence bands of casual impurities.     

Vibrational spectrum of Li2B4O7 crystals

The polarized infrared reflection spectra of Li₂B₄O₇ were studied in the spectral range 80–1600 cm^?1 and compared with Raman spectra. From the spectrum dispersion analysis, the frequencies, damping, and dielectric oscillator strengths were determined for all vibrational modes observed. A calculation of the effective charges and an analysis of the chemical-bond types of the Li₂B₄O₇ crystal structural units were carried out on the basis of the obtained data.     

Surface charging at the (1 0 0) surface of Cu doped and undoped Li2B4O7

We have compared the photovoltaic charging of the (1 0 0) surface termination for Cu doped and undoped Li₂B₄O₇. While the surface charging at the (1 0 0) surface of Li₂B₄O₇ is significantly greater than observed at (1 1 0) surface, the Cu doping plays a role in reducing the surface photovoltage effects. With Cu doping of Li₂B₄O₇, the surface photovoltaic charging is much diminished at the (1 0 0) surface. The density of states observed with combined photoemission and inverse photoemission remains similar to that observed for the undoped material, except in the vicinity of the conduction band edge.     

Glass formation in the system Li2B4O7–Pb3O4–CuO using X-ray diffraction

X-ray diffraction was performed to construct the phase diagram for the ternary Li₂B₄O₇–Pb₃O₄–CuO glass system. Three principal regions were identified: (1) a glass-forming region observed at the composition (75 < Li₂B₄O₇ < 100) mol%, (0 < CuO < 35) mol% and (0 < Pb₃O₄ < 70) mol% in the ternary system, and (100 ? x) mol% Li₂B₄O₇–x mol% Pb₃O₄ where x = 0 up to 70, (100 ? y) mol% Li₂B₄O₇–y mol% CuO where y = 0 up to 25 in the binary system;. (2) a crystalline region: all compositions prepared from the binary system Pb₃O₄–CuO and the ternary system containing Li₂B₄O₇ up to 60 mol%; (3) a partially crystalline region formed between the glass and crystalline regions.     

Critical view on TL/OSL properties of Li2B4O7 nanoparticles doped with Cu,Ag and co-doping Cu,Ag: Dose response study

Small size (25 nm) Li₂B₄O₇ nanoparticles doped with different concentrations of Cu, Ag and co-doped with Cu, Ag were prepared by solid state sintering at 700 °C. The crystalline phase and particle sizes analysis were carried out by XRD and TEM. FTIR study reveals the formation of vibrational bonds at 1600–1200 cm⁻¹, 1500–700 cm⁻¹, 950–870 cm⁻¹ and 870–415 cm⁻¹. The kinetic parameters of the TL glow curves were evaluated using CGCD procedure in R-software. The CW-OSL decay curves were fitted with third order exponential decay curves and photoionization cross sections of each component were evaluated. The lifetime of the main TL dosimetric peak were also calculated to check the stability of the signal. Dose responses of the synthesized Li₂B₄O₇ nanoparticles for both the TL and CW-OSL were studied in the range of 0.02 mGy to50 Gy and found to be linear upto this range. Fading of the CW-OSL decay curves were also studied. The MDD of the synthesized samples were also calculated and observed to be 15 μGy.     

TL and OSL studies on lithium borate single crystals doped with Cu and Ag

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.     

Enhanced ethanol sensing properties of TeO2/In2O3 core–shell nanorod sensors

TeO₂/In₂O₃ core–shell nanorods were fabricated using thermal evaporation and sputtering methods. The multiple networked TeO₂/In₂O₃ core–shell nanorod sensor showed responses of 227–632%, response times of 50–160 s, and recovery times of 190–220 s at ethanol (C₂H₅OH) concentrations of 50–250 ppm at 300 °C. The response values are 1.6–2.9 times higher and the response and recovery times are also considerably shorter than those of the pristine TeO₂ nanorod sensor over the same C₂H₅OH concentration range. The origin of the enhanced ethanol sensing properties of the core–shell nanorod sensor is discussed.     

Li2B4O7晶体的晶格振动光谱

在室温下测量了Li₂B₄O₇单晶的各种振动类的偏振Raman散射谱和该晶体粉末样品的红外吸收谱(200—4000cm^-1)。根据LO-TO劈裂的实验结果,计算出该晶体极化模的有效电荷和振子强度。通过与BBO和LBO晶体的结构和B—O伸缩振动模频率比较,得出:Li₂B₄O₇晶体可能有较大的非线性光学系数。 关键词：     

New scheme for dual readout of dose in polycrystalline Li2B4O7 irradiated with synchrotron X-rays from Indus-2

A new thermoluminescent (TL) dosimeter readout scheme was developed which allows for the measurement of both the single incident dose and the accumulated dose from multiple irradiations, through a novel dual readout procedure. Undoped, Mn doped and Cu doped polycrystalline Li₂B₄O₇ pallets were irradiated by synchrotron X-rays from Indus-2 with different dose. Thermoluminescence glow curves were taken at various heating rates. Two glow peaks were observed in each sample. TL intensities of different samples were compared and it was found that TL counts are more in Cu doped Li₂B₄O₇ sample. TL counts under each peak were calculated and a fixed ratio for two peaks was obtained. A new method of reading out the two peaks separately was formalized, allowing for greater flexibility in the use of TL based personnel dose monitoring devices.     

Facile synthesis of SnO2–ZnO core–shell nanowires for enhanced ethanol-sensing performance

The design of core–shell heteronanostructures is powerful tool to control both the gas selectivity and the sensitivity due to their hybrid properties. In this work, the SnO₂–ZnO core–shell nanowires (NWs) were fabricated via two-step process comprising the thermal evaporation of the single crystalline SnO₂ NWs core and the spray-coating of the grainy polycrystalline ZnO shell for enhanced ethanol sensing performance. The as-obtained products were investigated by X-ray diffraction, scanning electron microscopy, and photoluminescence. The ethanol gas-sensing properties of pristine SnO₂ and ZnO–SnO₂ core–shell NW sensors were studied and compared. The gas response to 500 ppm ethanol of the core–shell NW sensor increased to 33.84, which was 12.5-fold higher than that of the pristine SnO₂ NW sensor. The selectivity of the core–shell NW sensor also improved. The response to 100 ppm ethanol was about 14.1, whereas the response to 100 ppm liquefied petroleum gas, NH₃, H₂, and CO was smaller, and ranged from 2.5 to 5.3. This indicates that the core–shell heterostructures have great potential for use as gas sensing materials.     

Thermoluminescence studies on Cu-doped Li2B4O7 single crystals

Lithium tetraborate (Li₂B₄O₇) is a tissue equivalent material and single crystals of this material doped with Cu are promising for dosimetric applications. In the present study highly transparent single crystals of lithium tetraborate (Li₂B₄O₇) doped with Cu (0.5 wt%) have been grown using the Czochralski technique. The Li₂B₄O₇:Cu crystals were studied using photoluminescence, X-ray diffraction (XRD), UV-vis transmission, time resolved fluorescence and thermoluminescence (TL) techniques. The TL readout of Li₂B₄O₇:Cu crystals showed two well-defined glow peaks at 402 K (peak-1) and 513 K (peak-2) for a 4 K/s heating rate. While the low temperature TL peak-1 fades completely within 24 h at room temperatures, the main dosimetric peak-2 remains the same. The TL sensitivity of the grown single crystal is found to be 3.3 times that of a conventional TL phosphor, TLD-100. The Li₂B₄O₇:Cu crystals showed a linear TL dose-response in the range from 1 mGy to 1 kGy. The TL analysis using a variable dose method revealed first order kinetics for both the peaks. Trap depth and frequency factor for peak-1 were found to be 0.81 eV and 5.2×10⁹ s⁻¹, whereas for peak-2 the values were 1.7 eV and 1.7×10¹⁶ s⁻¹, respectively.     

Radioluminescent mechanism of Li2B4O7:Cu crystal

The structure of the radioluminescent (RL) spectrum of Li₂B₄O₇:Cu crystal is complex, having no normal Gauss peaks. The RL spectrum recorded showed one sharp and strong peak near 365 nm. For the purpose of explaining this phenomenon, we used the self-trapped exciton (STE) model to analyze experimental data of absorption spectrum, emission spectrum, radioluminescence spectrum and decay-time curves. We found a short lifetime component (of the order of ns) from phosphorous signals of Li₂B₄O₇:Cu. We realized that the short lifetime component related to inherent signal of host lattice and the d-p transitions of Cu⁺. This result is applicable in the detector system with high time resolution.     

Ionic conductivity in borate glasses with three types of mixed alkali cations

We have investigated the temperature- and frequency-dependent ionic conductivity in (Li_0.67 ? xNa_0.33 Rb_x)₂B₄O₇ (LNRBO) glasses with x = 0, 0.07, 0.2, 0.33, 0.47, and 0.6. The mixed alkali effect of the ternary mixed alkali system LNRBO is compared with that of the binary mixed alkali systems (Li_1 ? xNa_x)₂B₄O₇ (LNBO), (Li_1 ? xRb_x)₂B₄O₇ (LRBO) and the single alkali glass Rb₂B₄O₇ (RBO). From the results of the dc conductivity and dc activation energy, we observe that the LNRBO system exhibits the combined characteristic of binary mixed alkali systems LNBO and LRBO. It is found that the power-law exponent n for binary alkali glass is the same as that for ternary alkali glass but it is lower than that for single alkali glass. This indicates that the dimensionality of conducting pathway in the mixed alkali glasses of LNBO, LRBO and LNRBO is lower than that in the single alkali RBO. We discuss the concentration dependence of the dc conductivity and dc activation energy in the framework of the bond valence technique to reverse Monte Carlo produced structural model [Phys. Rev. Lett. 90, 155507 (2003)].     

Microwave dielectric properties of the 5.5Li<Subscript>2</Subscript>O–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>–7TiO<Subscript>2</Subscript> ceramics

A new Li₂O–Nb₂O₅–TiO₂ (LNT) ceramic with the Li₂O:Nb₂O₅:TiO₂ mole ratio of 5.5:1:7 was prepared by solid state reaction route. The phase and structure of the ceramic were characterized by X-ray diffraction and scanning electron microscopy (SEM). The microwave dielectric properties of the ceramics were studied using a network analyzer. The microwave dielectric ceramic has low sintering temperature (∼1075°C) and good microwave dielectric properties of ε _r=42, Q×f=16900 GHz (5.75 GHz), and τ _f =63.7 ppm/°C. The addition of B₂O₃ can effectively lower the sintering temperature from 1075 to 875°C and does not induce degradation of the microwave dielectric properties. Obviously, the LNT ceramics can be applied to microwave low temperature-cofired ceramics (LTCC) devices.     

Characteristics of high sensitivity ethanol gas sensors based on nanostructured spinel Zn1−xCoxAl2O4

Nanocrystalline powders of Zn_1−xCo_xAl₂O₄ (x = 0, 0.2, 0.4, 0.6, 0.8, 1.0) mixed oxides, with cubic spinel structure were successfully prepared by the ethylene glycol mediated citrate sol-gel method. The structure and crystal phase of the powders were characterized by X-ray diffraction (XRD) and microstructure by transmission electron microscopy (TEM). X-ray diffraction results showed that the samples were in single phase with the space group Fd-3m. TEM analysis showed that the powders with spherical shape were uniform in particle size of about 17-24 nm with mesoporous in nature. Further investigations were carried out by FT-IR. Thick films of as-prepared Zn_1−xCo_xAl₂O₄ powders were fabricated using screen-printing technique. The response of Zn_1−xCo_xAl₂O₄ based thick films towards different reducing gases (liquefied petroleum gas, hydrogen, hydrogen sulfide, ethanol gas and ammonia) was investigated. The sensor response largely depends on the composition, temperature and the test gas species. The Co (cobalt) content has a considerable influence on the gas-sensing properties of Zn_1−xCo_xAl₂O₄. Especially, Zn_0.4Co_0.6Al₂O₄ composition exhibited high response with better selectivity to 100 ppm C₂H₅OH gas at 150 °C. The instant response (∼7 s) and fast recovery (∼16 s) are the main features of this sensor.     

Effect of dibutyl phthalate as plasticizer on high-molecular weight poly(vinyl chloride)–lithium tetraborate-based solid polymer electrolytes

A series of different composition of polymer electrolytes-based on poly(vinyl chloride) (PVC) as host polymer, lithium tetraborate (Li₂B₄O₇) as dopant salt, and dibutyl phthalate (DBP) as plasticizer were prepared by solution casting method. The interaction between the PVC, Li₂B₄O₇, and DBP were studied by Fourier transform infrared. The shifting, broadening, and splitting of transmission peaks were the evidences of complexation. The highest ionic conductivity polymer electrolyte of 2.83 × 10⁻⁶ S/cm was achieved at ambient temperature upon addition of 30 wt.% of DBP. In addition, the temperature-dependent conductivity, frequency-dependent conductivity, dielectric permittivity, and modulus studies were performed. The temperature-dependent conductivity of the polymer electrolytes was found to obey the Arrhenius behavior. The thermal stability of polymer electrolytes was verified by thermogravimetric analysis. The lower in glass transition temperature was proven in differential scanning calorimetry, whereas the higher amorphous region within the polymer matrix was demonstrated in X-ray diffraction.     

Enhanced luminescence of Tb by efficient energy transfer from Ce in Sr2B5O9Cl host

Ce³⁺ and Tb³⁺ co-doped Sr₂B₅O₉Cl phosphors with intense green emission were prepared by the conventional high-temperature solid-state reaction technique. A broad band centered at about 315 nm was found in phosphor Sr₂B₅O₉Cl: Ce³⁺, Tb³⁺ excitation spectrum, which was attributed to the 4f-5d transition of Ce³⁺. The typical sharp line emissions ranging from 450 to 650 nm were originated from the ⁵D₄ → ⁷F_J (J = 6, 5, 4, 3) transitions of Tb³⁺ ions. The photoluminescence (PL) intensity of green emission from Tb³⁺ was enhanced remarkably by co-doping Ce³⁺ in the Tb³⁺ solely doped Sr₂B₅O₉Cl phosphor because of the dipole-dipole mechanism resonant energy transfer from Ce³⁺ to Tb³⁺ ions. The energy transfer process was investigated in detail. In light of the energy transfer principles, the optimal composition of phosphor with the maximum green light output was established to be Sr_1.64Ce_0.08Tb_0.1Li_0.18B₅O₉Cl by the appropriate adjustment of dopant concentrations. The PL intensity of Tb³⁺ in the phosphor was enhanced about 40 times than that of the Tb³⁺ single doped phosphor under the excitation of their optimal excitation wavelengths.     

Synthesis and characterization of thermoluminescent Li2B4O7 nanophosphor

Lithium borate (Li₂B₄O₇) is a low Z_eff, tissue equivalent material that is commonly used for medical dosimetry using the thermoluminescence (TL) technique. Nanocrystals of lithium borate were synthesized by the combustion method for the first time in the laboratory. TL characteristics of the synthesized material were studied and compared with those of commercially available microcrystalline Li₂B₄O₇. The optimum pre-irradiation annealing condition was found to be 300 °C for 10 min and that of post-irradiation annealing was 300 °C for 30 min. The synthesized Li₂B₄O₇ nanophosphor has very poor sensitivity for low doses of gamma up to 10¹ Gy whereas from 10¹ to 4.5×10² Gy this phosphor exhibits a linear response and then from 4.5×10² to 10³ Gy it shows supralinearity. Thermoluminescence properties of Li₂B₄O₇ nanophosphor doped with Cu has also been investigated in this paper. It shows low fading and a linear response over a wide range of gamma radiation from 1×10² to 5×10³ Gy. Therefore the synthesized lithium borate nanophosphor doped with Cu may be used for high dose measurements of gamma radiations.     

Nanophase ZnV2O4 as stable and high capacity Li insertion electrode for Li-ion battery

Spinel ZnV₂O₄ nanoparticles are synthesized by a hydrothermal method and its properties are characterized using XRD, SEM, TEM, and electrochemical test. The structural and morphological characterizations show that ZnV₂O₄ sample has high purity and well crystallization with crystal size less than 20 nm. The as prepared electrode shows stable capacity over 660 mAh g⁻¹ in the voltage range of 0.01–3.0 V at 50 mA g⁻¹. The reaction mechanism with lithium ion is also investigated through ex-XRD and -TEM. It shows that the pristine ZnV₂O₄ is transformed to isostructural spinel Li_xV₂O₄ (x close to 7.6) and metal Zn phase during the first lithiation process. Then the spinel Li_xV₂O₄ seems to perform a topotactic intercalation reaction mechanism and that the in-situ formed Li_xV₂O₄ can still keep its spinel matrix while allowing more than 5.7 lithium reversibly into/out over 50 cycles.