Dipole co-operative motions in an A-type carbonated apatite,Sr10(AsO4)6CO3

Relaxation of reorientable electric dipoles in A -type carbonated strontium arsenate, an apatite, has been studied with the thermally stimulated currents method. The fractional polarization technique permitted registration, in the range 9–428 K, of a separate current vs temperature curve for each small range of dipole-reorientation activation energies. Interpretation of these on a simple Debye model revealed four compensation temperatures, −100, 175, 392 and 573°C, with associated relaxation times τ_c = 2 × 10⁻⁶, 9 × 10⁻⁷, 2 × 10⁻⁶, and 1 × 10⁻⁵s, respectively. It is proposed that (1) the reorientable dipoles are primarily carbonate ions, and that (2) the co-operative phenomena associated with the 175°C and 392dgC temperatures are, respectively, a quasi-statically stabilized monoclinic-to-hexagonal phase transition and the onset of dynamical stabilization of the hexagonal phase.     

New SERS feature of β‐carotene: consequences for quantitative SERS analysis

While recording SERS spectra of pure β‐carotene at sub‐micromole concentrations for reference purpose, we discovered an unusual spectral response never reported before. In pre‐resonance conditions with the 532‐nm line, SERS of β‐carotene with AgNPs exhibits among the strong υ(CC) mode at 1512 cm⁻¹ unshifted from normal Raman spectrum, additional strong bands at 1649, 1575 and 1387 cm⁻¹ as well as other medium bands not observed in the Raman spectrum of the crystalline powder. Such behavior is explained in terms of selection rules relaxation upon cyclohexene terminal rings of the β‐carotene interaction with the NP surface. AFM images of the SERS system suggested dimers and trimers clustering of the nanoparticles with adsorbed β‐carotene. In light of the new SERS feature the consequences in correct interpretation of the SERS imaging from complex biosystems containing carotenoids are discussed. Relative intensity ratio of the β‐carotene band at 1512 cm⁻¹ and water against concentration allowed a reliable SERS calibration curve for 50 to 500 nmol l⁻¹ concentration range and provided quantitative SERS assessment of the carotenoid content in the sea urchin (Paracentrotus lividus) gonads extracts. Copyright © 2015 John Wiley & Sons, Ltd.     

Optical-feedback cavity-enhanced absorption spectroscopy with a quantum-cascade laser yields the lowest formaldehyde detection limit

We report on the first application of Optical Feedback-Cavity Enhanced Absorption Spectroscopy to formaldehyde trace gas analysis at mid-infrared wavelengths. A continuous-wave room-temperature, distributed-feedback quantum cascade laser emitting around 1,769 cm^?1 has been successfully coupled to an optical cavity with finesse 10,000 in an OF-CEAS spectrometer operating on the ν₂ fundamental absorption band of formaldehyde. This compact setup (easily transportable) is able to monitor H₂CO at ambient concentrations within few seconds, presently limited by the sample exchange rate. The minimum detectable absorption is 1.6 × 10^?9 cm^?1 for a single laser scan (100 ms, 100 data points), with a detectable H₂CO mixing ratio of 60 pptv at 10 Hz. The corresponding detection limit at 1 Hz is 5 × 10^?10 cm^?1, with a normalized figure of merit of 5 × 10^?11cm $^{-1}/\sqrt{\rm Hz}$ (100 data points recorded in each spectrum taken at 10 Hz rate). A preliminary Allan variance analysis shows white noise averaging down to a minimum detection limit of 5 pptv at an optimal integration time of 10 s, which is significantly better than previous results based on multi-pass or cavity-enhanced tunable QCL absorption spectroscopy.     

Development of proton conducting biopolymer membrane based on agar–agar for fuel cell

A proton-conducting polymer electrolyte based on agar and ammonium nitrate (NH₄NO₃) has been prepared through solution casting technique. The prepared polymer electrolytes were characterized by impedance spectroscopy, X-ray diffraction, and Fourier transform infra-red spectroscopy. Impedance analysis shows that sample with 60 wt.% NH₄NO₃ has the highest ionic conductivity of 6.57 × 10⁻⁴ S cm⁻¹ at room temperature. As a function of temperature, the ionic conductivity exhibits an Arrhenius behaviour increasing from 6.57 × 10⁻⁴ S cm⁻¹ at room temperature to 1.09 × 10⁻³ S cm⁻¹ at 70 °C. Transport parameters of the samples were calculated using Wagner’s polarization method and thus shows that the increase in conductivity is due to the increase in the number of mobile ions. Fuel cell has been constructed with the highest proton conductivity polymer 40agar/60NH₄NO₃ and the open circuit voltage is found to be 558 mV.

     

Fluctuations of acoustic field in a granular medium

Results of an experimental study of sound propagation in a granular medium are presented. It is found that, in the case of excitation of a harmonic signal with a constant amplitude, the acoustic response of a single grain strongly varies in time. The dependence of the harmonic component amplitudes in the response spectrum on the level of signal excitation proves to be nonmonotonic and also strongly varies in time. The most intense fluctuations are observed in the subharmonic component of the propagating signal. The intensity fluctuation spectra of the harmonic components of the response are obtained for the frequency range of 10⁻⁴−10⁻¹ Hz. A possible mechanism that may be responsible for the slow fluctuations of an acoustic field in a granular medium is discussed.

     

Growth of wurtzite GaN films on αAl2O3 substrates using light-radiation heating metal-organic chemical vapor deposition

Epitaxial growth of high-quality hexagonal GaN films on sapphire substrates using light-radiation heating metal-organic chemical vapor deposition (LRH-MOCVD) is first reported. The deposition temperature is 950 °C, about 100 °C lower than that in normal rf-heating MOCVD growth. The FWHM of GaN (0002) peak of the X-ray diffraction rocking curve is 8.7 arc  min. Photoluminescence spectrum of GaN film shows that there is a very strong band-edge emission and no “yellow-band” luminescence. Hall measurement indicates that the n-type background carrier concentration of GaN film is 1.7×10¹⁸ cm^-3 and the Hall mobility of it is 121.5 cm²/V s. It is suggested that the radiation of light in GaN growth enhances the dissociation of ammonia and decreases the disadvantages of the parasite reaction between trimethylgallium and ammonia. Received: 20 August 1998 / Accepted: 30 October 1998 / Published online: 10 March 1999     

Accurate intensity calibration for low wavenumber (−150 to 150 cm−1) Raman spectroscopy using the pure rotational spectrum of N2

We report on an accurate intensity calibration method for low wavenumber Raman spectroscopy. It uses the rotational Raman spectrum of N₂. The intensity distributions in the rotational Raman spectra of diatomic molecules are theoretically well established. They can be used as primary intensity standards for intensity calibration. The intensity ratios of the Stokes and anti‐Stokes transitions originating from the same rotational levels are not affected by thermal population. Taking the effect of rotation–vibration interactions appropriately into account, we are able to calculate these intensity ratios theoretically. The comparison between the observed and calculated ratios of the N₂ pure rotational spectrum provides an accurate relative sensitivity curve (error ~5 × 10⁻⁴) in the wavenumber region of −150 to 150 cm⁻¹. We determine the temperature of water solely from the low wavenumber Raman spectra, using a thus calibrated spectrometer. The Raman temperature shows an excellent agreement with the thermocouple temperature, with only 0.5 K difference. The present calibration technique will be highly useful in many applications of low wavenumber quantitative Raman spectroscopy. Copyright © 2015 John Wiley & Sons, Ltd.     

The high-resolution spectrum of the ν1 (A1) band of 12CD3F

The spectrum of the ν₁ (A₁) band of ¹²CD₃F has been recorded with a resolution of 0.010 cm⁻¹ and deconvolved to 0.005 cm⁻¹. Over 1050 transitions have been assigned with K ≤ 16 and J ≤ 42. The spectrum is highly perturbed, exhibiting avoided crossings in most of the observed sub-bands. The origin of most of the local and global resonances has been determined and the coupling constants estimated. Due to the complexity of the spectrum resulting from the 24 potential interacting states in the region, the assigned frequencies were fitted in a restricted manner (K ≤ 3, J ≤ 15), to obtain the following effective constants for the band: ν₀ = 2090.8118(20) cm⁻¹, α^A = 1.19743 × 10⁻² cm⁻¹, and α^B = −1.8489 × 10⁻³ cm⁻¹. From an unrestricted least-squares analysis, fixing the above parameters the β's (D_v^x = D₀^x − β_v^x) were calculated to be β^J = 1.7776 × 10⁻⁷ cm⁻¹, β^JK = 8.3406 × 10⁻⁷ cm⁻¹, and β^K = −6.3829 × 10⁻⁷ cm⁻¹. These constants serve as good starting parameters for the global analysis necessary to fully analyze the 5-μm region of the ¹²CD₃F spectrum.     

Synthesis and characterization of proton-conducting polymer electrolyte based on polyacrylonitrile (PAN)

Solid polymer electrolytes based on polyacrylonitrile (PAN) doped with ammonium iodide (NH₄I) have been prepared by solution casting method with different molar ratios of polymer and salt using DMF as solvent. The XRD pattern confirms the dissociation of salt. The FTIR analysis confirms the complex formation between the polymer and the salt. A shift in glass transition temperature (T _g ) of the PAN/NH₄I electrolytes has been observed from the DSC thermograms, which indicates the interaction between the polymer and the salt. The conductivity analysis shows that the polymer electrolyte with 20 mol% NH₄I has the highest conductivity equal to 1.106 × 10⁻³ S cm⁻¹ at room temperature. The activation energy (E _a ) has been found to be low for the highest conductivity sample. The dielectric permittivity (ε*) and modulus (M*) have been calculated from the alternating current (AC) impedance spectroscopy in the frequency range 42 Hz–1 MHz. The DC polarization measurement shows that the conductivity is mainly due to ions.

     

Magnetism origin of Mn-doped ZnO nanoclusters

ZnMnO nanoclusters were synthesized by the sol–gel method. The structural and magnetic characters were investigated. The XRD spectrum shows ZnMnO nanoclusters are hexagonal wurtzite structures and a small quantity of ZnMn₂O₄ phase is also present in the spectrum. The percentages of Zn and Mn elements in the ZnMnO nanostructure are 97% and 3%, respectively, which are induced from XPS data. EPR spectrum with g=1.9961$g=1.9961$ shows the signal of Mn²⁺. The magnetization curve measured at room temperature shows a hysteresis loop. XRD and XPS analyses prove that ferromagnetic ordering arises from ZnMn₂O₄ in all probability.     

Heavy Quark Hadron Mass Scale

Without the spin interactions the hadron masses within a multiplet are degenerate. The light quark hadron degenerate multiplet mass spectrum is extended from the 3 quark ground state multiplets at J^P = 0⁻, ½⁺, 1⁻ to include the excited states which follow the spinorial decomposition of SU(2) × SU(2). The mass scales for the 4, 5, 6,… quark hadrons are obtained from the degenerate multiplet mass m₀/M = n²/α with n = 4, 5, 6,… The 4, 5, 6,… quark hadron degenerate multiplet masses follow by splitting of the heavy quark mass scales according to the spinorial decomposition of SU(2) × SU(2).     

Resonance Raman study of He+ ion implanted nanostructured ZnS

ZnS nanocrytsals of size ∼2.5 nm were prepared by chemical precipitation technique. Pressed pellets of nanostructured ZnS were implanted with He⁺ ions at doses of 5 × 10¹⁴, 1 × 10¹⁵ and 5 × 10¹⁵ ions/cm². Raman spectra of both unimplanted and He⁺ ion implanted samples were recorded with ultraviolet (UV) excitation. LO, 2LO, 2TO, (LO + TA) and (2TO − TA) modes of ZnS were observed in the resonance Raman spectra of the unimplanted nanostructured ZnS samples. In addition, a surface mode was observed at 294 cm⁻¹. With the implantation of He⁺ ions, the 2TO mode disappeared and 2LO mode became prominent and this observation was attributed to the decrease in band gap of ZnS nanocrytsals due to ion implantation. The exciton–LO phonon coupling strength was determined from the intensity ratio of 2LO to LO modes and it was observed that the exciton–LO phonon coupling strength increases with increase in implantation dose. In the present work, we report for the first time the observation of 2TO mode in the resonance Raman spectrum of nanostructured ZnS and also the modification of exciton–LO phonon coupling strength of semiconductor nanoparticles by ion implantation. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the arsenite minerals leiteite ZnAs2O4, reinerite Zn3(AsO3)2 and cafarsite Ca5(Ti,Fe,Mn)7(AsO3)12·4H2O

The selected arsenite minerals leiteite, reinerite and cafarsite have been studied by Raman spectroscopy. Density functional theory (DFT) calculations enabled the position of the AsO₂²⁻ symmetric stretching mode at 839 cm⁻¹, the antisymmetric stretching mode at 813 cm⁻¹ and the deformation mode at 449 cm⁻¹ to be calculated. The Raman spectrum of leiteite shows bands at 804 and 763 cm⁻¹ assigned to the As₂O₄²⁻ symmetric and antisymmetric stretching modes. The most intense Raman band of leiteite is the band at 457 cm⁻¹ and is assigned to the ν₂ As₂O₄²⁻ bending mode. A comparison of the Raman spectrum of leiteite is made with the arsenite minerals reinerite and cafarsite. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of GZO thickness and annealing temperature on the structural,electrical and optical properties of GZO/Ag/GZO sandwich films

The GZO/Ag/GZO sandwich films were deposited on glass substrates by RF magnetron sputtering of Ga-doped ZnO (GZO) and ion-beam sputtering of Ag at room temperature. The effect of GZO thickness and annealing temperature on the structural, electrical and optical properties of these sandwich films was investigated. The microstructures of the films were studied by X-ray diffraction (XRD). X-ray diffraction measurements indicate that the GZO layers in the sandwich films are polycrystalline with the ZnO hexagonal structure and have a preferred orientation with the c-axis perpendicular to the substrates. For the sandwich film with upper and under GZO thickness of 40 and 30 nm, respectively, it owns the maximum figure of merit of 5.3 × 10⁻² Ω⁻¹ with a resistivity of 5.6 × 10⁻⁵ Ω cm and an average transmittance of 90.7%. The electrical property of the sandwich films is improved by post annealing in vacuum. Comparing with the as-deposited sandwich film, the film annealed in vacuum has a remarkable 42.8% decrease in resistivity. The sandwich film annealed at the temperature of 350 °C in vacuum shows a sheet resistance of 5 Ω/sq and a transmittance of 92.7%, and the figure of merit achieved is 9.3 × 10⁻² Ω⁻¹.     

Low noise field-effect transistor for integrated strain sensing in microelectromechanical systems at 77 K

We have fabricated a strain-sensing field-effect transistor (FET) from a GaAs/AlGaAs heterostructure containint a near surface two-dimensional electron gas. At 77 K the FET shows a typical transconductance of 30 μS and small signal drain-source resistance of 30 MO. The charge noise has a flat spectrum at high frequencies with magnitude 0.7eHz^−1/2and a 1/fnoise corner of approximately 1 kHz. The strain response, due to the piezoelectric effect, shows a noise limited strain sensitivity <4×10⁻⁹Hz^−1/2. Integrated strain sensing FETs offer advantages in small GaAs/AlGaAs microelectromechanical systems.     

Thermal dependence of conduction properties in the Bi2O3Pb2OF2 system

Conduction properties of bismuth-lead oxyfluorides (Bi,Pb)₂(O,F)₃ have been investigated by complex impedance analysis. A special attention has been drawn to a hexagonal solid solution Bi_(1−x)Pb_xO_(1.5−x)F_x (0.45⩽x⩽0.741 at 770 K), which is isostructural with ALa₂O₃. Conductivity values range from 3 × 10⁻⁵ to 3 × 10⁻² (ω cm)⁻¹ at 585 K. A minimum associated with a maximum in activation energy is observed for the composition x = 0.5 i.e. BiPbO₂F.     

Effect on ion dissociation in MWCNT-based polymer nanocomposite

Polymer nanocomposite has been proven to improve the property of polymer salt complex. Organo-modified clay and inorganic oxides are the most commonly used filler for polymer nanocomposite (PNC). However, single wall carbon nanotube (SWCNT)/multiwall carbon nanotube (MWCNT) are becoming popular filler for PNC for their high surface area and high mechanical stability. In this work, a series of PNC sample has been prepared by using polyethylene oxide (PEO)-polydimethylsiloxane (PDMS) blend as polymer matrix, an optimized salt stoichiometry of Ö/Li ~15, and surface-modified MWCNT as filler. The effect of ion-polymer and ion-MWCNT interaction in the polymer nanocomposite has been investigated by using XRD, SEM, FTIR, and electrical study. X-ray diffraction pattern confirms the dispersion of MWCNT inside the polymer chain and modifies the structural parameter of the polymer matrix. FTIR spectra indicate inclusion of MWCNT inside the polymer salt complex which changes the ion dissociation/association in the polymer host matrix. Further, the changes in structural, thermal, and electrical property of the polymer salt complex system have been studied by using SEM, DSC, and impedance analysis. Dc conductivity study shows that optimized PNC sample has conductivity of 8.04 × 10⁻⁵ S cm⁻¹. This is almost two order enhancement from pure polymer salt system (10⁻⁶ S cm⁻¹).

     

The crystal spectra of very weak transitions

The weak absorption system of crystalline naphthalene at 3200 å has been measured at 4°K in polarized light. Previous work at 20°K is supplemented by a number of newly recorded absorption lines, and by re-measurement of the frequencies of all lines at the lower temperature.

The spectrum is compared with the vapour spectrum and corresponding bands identified so far as possible. Exciton resonance effects are analysed and discussed. The analysis discloses that the important b _{3 g} vibrations of upper state frequencies 438 and 911 cm^-1 are both reduced by 5 per cent in the crystal, and smaller changes are identified in other vibrations. Comparison with the vapour spectrum shows that vibrationally induced bands, even when relatively strong, are little influenced by intermolecular forces, whereas very weak pure electronic bands give evidence of much greater effects.     

Quantitative detection of adulterated olive oil by Raman spectroscopy and chemometrics

Commercially available extra virgin olive oils are often adulterated with some other cheaper edible oils with similar chemical compositions. A set of extra virgin olive oil samples adulterated with soybean oil, corn oil and sunflower seed oil were characterized by Raman spectra in the region 1000–1800 cm⁻¹. Based on the intensity of the Raman spectra with vibrational bands normalized by the band at 1441 cm⁻¹ (CH₂), external standard method (ESM) was employed for the quantitative analysis, which was compared with the results achieved by support vector machine (SVM) methods. By plotting the adulterant content of extra virgin olive oil versus its corresponding band intensity in the Raman spectrum at 1265 cm⁻¹, the calibration curve was obtained. Coefficient of determination (R²) of each curve was 0.9956, 0.9915 and 0.9905 for extra virgin olive oil samples adulterated with soybean oil, corn oil and sunflower seed oil, respectively. The mean absolute relative errors were calculated as 7.41, 7.78 and 9.45%, respectively, with ESM, while they were 5.10, 6.96 and 4.55, in the SVM model, respectively. The prediction accuracy shows that the ESM based on Raman spectroscopy is a promising technique for the authentication of extra virgin olive oil. The method also has the advantages of simplicity, time savings and non‐requirement of sample preprocessing; especially, a portable Raman system is suitable for on‐site testing and quality control in field applications. Copyright © 2011 John Wiley & Sons, Ltd.     

One-step chemically vapor deposited hybrid 1T-MoS2/2H-MoS2 heterostructures towards methylene blue photodegradation

The photocatalytic degradation of methylene blue is a straightforward and cost-effective solution for water decontamination. Although many materials have been reported so far for this purpose, the proposed solutions inflicted high fabrication costs and low efficiencies. Here, we report on the synthesis of tetragonal (1T) and hexagonal (2H) mixed molybdenum disulfide (MoS₂) heterostructures for an improved photocatalytic degradation efficiency by means of a single-step chemical vapor deposition (CVD) technique. We demonstrate that the 1T-MoS₂/2H-MoS₂ heterostructures exhibited a narrow bandgap ∼ 1.7 eV, and a very low reflectance (<5%) under visible-light, owing to their particular vertical micro-flower-like structure. We exfoliated the CVD-synthesised 1T-MoS₂/2H-MoS₂ films to assess their photodegradation properties towards the standard methylene blue dye. Our results showed that the photo-degradation rate-constant of the 1T-MoS₂/2H-MoS₂ heterostructures is much greater under UV excitation (i.e., 12.5 × 10⁻³ min⁻¹) than under visible light illumination (i.e., 9.2 × 10⁻³ min⁻¹). Our findings suggested that the intermixing of the conductive 1T-MoS₂ with the semi-conducting 2H-MoS₂ phases favors the photogeneration of electron-hole pairs. More importantly, it promotes a higher efficient charge transfer, which accelerates the methylene blue photodegradation process.