Acetylene detection based on diode laser QEPAS: combined wavelength and residual amplitude modulation

Quartz-enhanced photoacoustic spectroscopy (QEPAS) is demonstrated for acetylene detection at atmospheric pressure and room temperature with a fiber-coupled distributed feedback (DFB) diode laser operating at ~1.53 μm. An efficient approach for gas concentration calibration is demonstrated. The effect of residual amplitude modulation on the performance of wavelength modulated QEPAS is investigated theoretically and experimentally. With optimized spectrophone parameters and modulation depth, a minimum detectable limit (1σ) of ~2 part-per-million volume (ppmv) was achieved with an 8.44-mW diode laser, which corresponds to a normalized noise equivalent coefficient (1σ) of 6.16 × 10^?8 cm^?1 W/Hz^1/2.     

Compact QEPAS sensor for trace methane and ammonia detection in impure hydrogen

A compact two-gas sensor based on quartz-enhanced photoacoustic spectroscopy (QEPAS) was developed for trace methane and ammonia quantification in impure hydrogen. The sensor is equipped with a micro-resonator to confine the sound wave and enhance QEPAS signal. The normalized noise-equivalent absorption coefficients (1σ) of 2.45×10^?8 cm^?1?W/ $\sqrt{}$ Hz and 9.1×10^?9 cm^?1?W/ $\sqrt{}$ Hz for CH₄ detection at 200 Torr and NH₃ detection at 50 Torr were demonstrated with the QEPAS sensor configuration, respectively. The influence of water vapor on the CH₄ channel was also investigated.     

Di-urethanesil hybrid electrolytes doped with Mg(CF3SO3)2

Two siloxane-based di-urethanesil frameworks incorporating poly(oxyethylene) (POE) chains have been synthesized by the sol–gel process and doped with magnesium triflate (Mg(CF₃SO₃)₂) with the goal of developing electrolytes for the fabrication of solid-state rechargeable magnesium batteries. In these matrices, short POE chains are covalently bonded to the siloxane network via urethane linkages. The xerogels have been represented by the notation d-Ut(Y) _n Mg(CF₃SO₃)₂, where Y?=?300 and 600 represents the average molecular weight of the POE chains and n stands for salt composition (molar ratio of OCH₂CH₂ units per Mg²⁺). Xerogels with compositions ranging from 2?≤?n?<?∞ were prepared. A crystalline POE/Mg(CF₃SO₃)₂ complex of unknown stoichiometry is formed in the d-Ut(300) _n Mg(CF₃SO₃)₂ materials with n?≤?6 and in the d-Ut(600) _n Mg(CF₃SO₃)₂ materials with n?≤?5. The organically modified silicate electrolytes with the highest conductivity of the d-Ut(300) _n Mg(CF₃SO₃)₂ and d-Ut(600) _n Mg(CF₃SO₃)₂ series are the samples with n?=?6 (3.9?×?10^?8 S cm^?1 at 26 °C and 8.7?×?10^?5 S cm^?1 at 97 °C) and n?=?100 (2.63?×?10^?7 S cm^?1 at 20 °C and 1.4?×?10^?5 S cm^?1 at 85 °C), respectively. Since the electrolytes for Mg batteries that have been proposed up to now have many intrinsic problems and although the room temperature conductivity values exhibited by the systems developed in the present study are still low in view of practical application, this work opens new directions for the development of solid-state Mg ion electrolytes.     

Off-beam quartz-enhanced photoacoustic spectroscopy with LEDs

A photoacoustic ozone sensor based on quartz-enhanced photoacoustic spectroscopy is presented. Instead of a laser, a UV-LED at 285 nm is utilized as light source. Using an acoustical resonator in off-beam configuration, it is feasible to align the light of the LED through the resonator tube. The sensor is integrated in a miniaturized flow-through gas cell which allows fast gas exchange. The sensor performance and the influence of the speed of sound on the measurement signal are investigated. For the detection of ozone in the Hartley band, a detection limit of S = 1.27 ± 0.08 ppmv (1σ) and a noise equivalent absorption sensitivity of D = (3.02 × 10^?8 ± 1 × 10^?10) cm^?1W(Hz)^?1/2 have been achieved.     

Single-QCL-based absorption sensor for simultaneous trace-gas detection of CH4 and N2O

A quantum cascade laser (QCL)-based absorption sensor for the simultaneous dual-species monitoring of CH₄ and N₂O was developed using a novel compact multipass gas cell (MGC). This sensor uses a thermoelectrically cooled, continuous wave, distributed feedback QCL operating at ~7.8 µm. The QCL wavelength was scanned over two neighboring CH₄ (1275.04 cm^?1) and N₂O (1274.61 cm^?1) lines at a 1 Hz repetition rate. Wavelength modulation spectroscopy (f = 10 kHz) with second harmonic (2f) detection was performed to enhance the signal-to-noise ratio. An ultra-compact MGC (16.9 cm long and a 225 ml sampling volume) was utilized to achieve an effective optical path length of 57.6 m. With such a sensor configuration, a detection limit of 5.9 ppb for CH₄ and 2.6 ppb for N₂O was achieved, respectively, at 1-s averaging time.     

Preparation and characterization of a new PEO-PPG blend polymer electrolyte system

This paper reports on preparation and characterization of thin films of a new zinc ion conducting blended polymer electrolyte system containing polyethylene oxide [PEO] and polypropylene glycol [PPG] complexed with zinc triflate [Zn(CF₃SO₃)₂] salt. The room temperature ionic conductivity (σ _298K) data of such PEO-PPG polymer blends prepared by solution casting technique were found to be of the order of 10^?5 S cm^?1, whereas the optimized composition containing 90:10 wt% ratio of PEO and PPG possessed an appreciably high ionic conductivity of 7.5?×?10^?5 S cm^?1. Subsequently, six different weight percentages of zinc triflate viz., 2.5, 5, 7.5, 10, 12.5 and 15, respectively, were added into the above polymer blend and resulting polymer-salt complexes were characterized by means of various analytical tools. Interestingly, the best conducting specimen namely 87.5 wt% (PEO:PPG)-12.5 wt% Zn(CF₃SO₃)₂ exhibited an enhanced room temperature ionic conductivity of 6.9?×?10^?4 S cm^?1 with an activation energy of 0.6 eV for ionic conduction. The present XRD results have indicated the occurrence of characteristic PEO peaks and effects of salt concentration on the observed intensity of these diffraction peaks. Appropriate values of degree of crystallinity for different samples were derived from both XRD and DSC analyses, while an examination of surface morphology of the blended polymer electrolyte system has revealed the formation of homogenous spherulites involving a rough surface and relevant zinc ionic transport number was found to be 0.59 at room temperature for the best conducting polymer electrolyte system thus developed.     

Multi-band infrared CO2 absorption sensor for sensitive temperature and species measurements in high-temperature gases

A continuous-wave laser absorption diagnostic, based on the infrared CO₂ bands near 4.2 and 2.7 μm, was developed for sensitive temperature and concentration measurements in high-temperature gas systems using fixed-wavelength methods. Transitions in the respective R-branches of both the fundamental υ ₃ band (~2,350 cm^?1) and combination υ ₁ + υ ₃ band (~3,610 cm^?1) were chosen based on absorption line-strength, spectral isolation, and temperature sensitivity. The R(76) line near 2,390.52 cm^?1 was selected for sensitive CO₂ concentration measurements, and a detection limit of <5 ppm was achieved in shock tube kinetics experiments (~1,300 K). A cross-band, two-line thermometry technique was also established utilizing the R(96) line near 2,395.14 cm^?1, paired with the R(28) line near 3,633.08 cm^?1. This combination yields high temperature sensitivity (ΔE” = 3,305 cm^-1) and expanded range compared with previous intra-band CO₂ sensors. Thermometry performance was validated in a shock tube over a range of temperatures (600–1,800 K) important for combustion. Measured temperature accuracy was demonstrated to be better than 1 % over the entire range of conditions, with a standard error of ~0.5 % and µs temporal resolution.     

Mid-infrared fiber-coupled QCL-QEPAS sensor

An innovative spectroscopic system based on an external cavity quantum cascade laser (EC-QCL) coupled with a mid-infrared (mid-IR) fiber and quartz enhanced photoacoustic spectroscopy (QEPAS) is described. SF₆ has been selected as a target gas in demonstration of the system for trace gas sensing. Single mode laser delivery through the prongs of the quartz tuning fork has been obtained employing a hollow waveguide fiber with inner silver–silver iodine (Ag–AgI) coatings and internal core diameter of 300 μm. A detailed design and realization of the QCL fiber coupling and output collimator system allowed almost practically all (99.4 %) of the laser beam to be transmitted through the spectrophone module. The achieved sensitivity of the system is 50 parts per trillion in 1 s, corresponding to a record for QEPAS normalized noise-equivalent absorption of 2.7 × 10^?10 W cm^?1 Hz^?1/2.     

Growth,spectral and laser properties of Nd3+:Na2La4(WO4)7 crystal

A Nd³⁺:Na₂La₄(WO₄)₇ crystal with dimensions of ? 17 × 30 mm³ was grown by the Czochralski method. The thermal expansion coefficients of Nd³⁺:Na₂La₄(WO₄)₇ crystal are 1.32 × 10^?5 K^?1 along c-axis and 1.23 × 10^?5 K^?1 along a-axis, respectively. The spectroscopic characteristics of Nd³⁺:Na₂La₄(WO₄)₇ crystal were investigated. The Judd–Ofelt theory was applied to calculate the spectral parameters. The absorption cross sections at 805 nm are 2.17 × 10^?20 cm² with a full width at half maximum (FWHM) of 15 nm for π-polarization, and 2.29 × 10^?20 cm² with a FWHM of 14 nm for σ-polarization. The emission cross sections are 3.19 × 10^?20 cm² for σ-polarization and 2.67 × 10^?20 cm² for π-polarization at 1,064 nm. The fluorescence quantum efficiency is 67 %. The quasi-cw laser of Nd³⁺:Na₂La₄(WO₄)₇ crystal was performed. The maximum output power is 80 mW. The slope efficiency is 7.12 %. The results suggest Nd³⁺:Na₂La₄(WO₄)₇ crystal as a promising laser crystal fit for laser diode pumping.     

X-ray structure refinement and ionic conductivity of Na6.69Ca3.355(SO4)6Cl0.77F0.63

The structure of Na_6.69Ca_3.355(SO₄)₆Cl_0.77F_0.63, isostructural with fluorapatite, was determined by X-ray powder diffraction methods. The results of Rietveld refinement revealed a space group P6₃/m with lattice parameters of a?=?9.477 (2) Å, c?=?6.865 (5) Å. Final refinement led to R _F?=?1.83 % and R _B?=?7.64 %. The location of Na⁺ ions in the M (2) sites surrounding the channels was related particularly to the high polarizability of the Ca²⁺. The ionic conductivity over a wide range of temperature was investigated according to the complex impedance method. The highest overall conductivity values were found at σ _500 °C?=?1.03?×?10^?5?S?cm^?1 and E_a?=?0.70 eV.     

Blends of hexanoyl chitosan/epoxidized natural rubber doped with EMImTFSI

Hexanoyl chitosan soluble in THF is prepared by acyl modification of chitosan. Epoxidation natural rubber (ENR25) (25 mol%) is chosen to blend with hexanoyl chitosan. Films of hexanoyl chitosan/ENR25 blends containing lithium bis(trifluoromethanesulfonyl)imide (LiN(CF₃SO₂)₂) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImTFSI) are prepared by solution casting technique. FTIR results suggested that LiN(CF₃SO₂)₂ salt interacted with hexanoyl chitosan, ENR25, and EMImTFSI. EMImTFSI interacted with hexanoyl chitosan and ENR25 to form EMIm⁺-hexanoyl chitosan and EMIm⁺-ENR25 complexes, respectively. The effect of EMImTFSI on the morphology and thermal properties of the blends is investigated by polarized optical microscopy (POM) and differential scanning calorimetry (DSC), respectively. The ionic conductivity of the electrolytes is measured by electrochemical impedance spectroscopy (EIS). Upon addition of 12 wt% EMImTFSI, a maximum conductivity of 1.3 × 10^?6 S cm^?1 is achieved. Methods based on impedance spectroscopy and FTIR are employed to study the transport properties of the prepared polymer electrolytes. The ac conductivity was found to obey universal law, σ(ω)?=?σ _dc ?+?Aω ^S . The temperature dependence of exponent s is interpreted by the small polaron hopping (SPH) model.     

CW DFB RT diode laser-based sensor for trace-gas detection of ethane using a novel compact multipass gas absorption cell

The development of a continuous wave, thermoelectrically cooled (TEC), distributed feedback diode laser-based spectroscopic trace-gas sensor for ultra-sensitive and selective ethane (C₂H₆) concentration measurements is reported. The sensor platform used tunable diode laser absorption spectroscopy (TDLAS) and wavelength modulation spectroscopy as the detection technique. TDLAS was performed using an ultra-compact 57.6 m effective optical path length innovative spherical multipass cell capable of 459 passes between two mirrors separated by 12.5 cm and optimized for the 2.5–4 μm range TEC mercury–cadmium–telluride detector. For an interference-free C₂H₆ absorption line located at 2,976.8 cm^?1, a 1σ minimum detection limit of 740 pptv with a 1 s lock-in amplifier time constant was achieved.     

Studies on structural and electrical properties of Mg<Subscript>0. 5+y</Subscript> (Zr<Subscript>2-y</Subscript>Fe<Subscript>y</Subscript>) <Subscript>2</Subscript> (PO<Subscript>4</Subscript>) <Subscript>3</Subscript> ceramic electrolytes

The sample of Mg_{0. 5+y} (Zr_1-y Fe_y) ₂ (PO₄) ₃ (0.0 ≤y ≤0.5) was synthesized using the sol-gel method. The structures of the samples were investigated using X-ray diffraction and Fourier transform infrared spectroscopy measurement. XRD studies showed that samples had a monoclinic structure which was iso-structured with the parent compound, Mg_0.5Zr (PO₄) ₃. The complex impedance spectroscopy was carried out in the frequency range 1–6 MHz and temperature range 303 to 773 K to study the electrical properties of the electrolytes. The substitutions of Fe³⁺ with Zr⁴⁺ in the Mg_0.5Zr (PO₄) ₃ structure was introduced as an extrainterstitial Mg²⁺ ion in the modified structured. The compound of Mg_0.5+y (Zr_1-y Fe_y)₂(PO₄)₃ with y?=?0.4 gives a maximum conductivity value of 1.25?×?10^?5 S cm^?1 at room temperature and 7.18?×?10^?5 S cm^?1 at 773 K. Charge carrier concentration, mobile ion concentration, and ion hopping rate are calculated by fitting the conductance spectra to power law variation, σ _ac (ω)?=?σ _o ? +?Aω ^α . The charge carrier concentration and mobile ion concentration increases with increase of Fe³⁺ inclusion. This implies the increase in conductivity of the compounds was due to extra interstitial Mg²⁺ ions.     

Simultaneous detection of 14NO and 15NO using Faraday modulation spectroscopy

We describe a technique of simultaneous detection of ¹⁴NO and ¹⁵NO by means of Faraday Modulation Spectroscopy (FAMOS) based on a cw distributed feedback quantum cascade laser (QCL) operating near 5.4 μm. FAMOS is a spectroscopic method for selective, sensitive, and time-resolved detection of free radical molecules such as NO, in the mid-infrared spectral region. The selected spectral lines are the Q (1.5) for ¹⁵NO located at 1842.76 cm^?1 and the P (9.5) for ¹⁴NO located at 1842.93 cm^?1. The detection limit (1σ) of 6 ppb $/\sqrt{\mathrm{Hz}}$ for ¹⁵NO and 62 ppb $/\sqrt{\mathrm{Hz}}$ for ¹⁴NO has been achieved. The simultaneous detection was performed using a fast laser frequency switching between the two isotopologues with a time resolution of 2 s. The isotope ratio (δ ¹⁵N) has been determined with a precision (1σ) of 0.52‰ at 800-s averaging time for 100 ppm NO-gas with a time resolution of 2 s. δ ¹⁵N is determined after NO release from nitrite by chemical reduction with potassium iodine.     

Detection of C2H2 and HCl using mid-infrared degenerate four-wave mixing with stable beam alignment: towards practical in situ sensing of trace molecular species

A stable and convenient optical system to realize the forward phase-matching geometry for degenerate four-wave mixing (DFWM) is demonstrated in the mid-infrared spectral region by measuring DFWM signals generated in acetylene (C₂H₂) and hydrogen chloride (HCl) molecules by probing the fundamental ro-vibrational transitions. IR laser pulses tunable from 2900 cm^?1 to 3350 cm^?1 with a 0.025 cm^?1 linewidth were obtained using a laser system composed of an injection seeded Nd:YAG laser, a dye laser, and a frequency mixing unit. At room temperature and atmospheric pressure, a detection limit of 35 ppm (～ 9.5×10¹⁴ molecules/cm³) for C₂H₂ was achieved in a gas flow of a C₂H₂/N₂ mixture by scanning the P(11) line of the (010(11)⁰)–(0000⁰0⁰) band. The detection limit of the HCl molecule was measured to be 25 ppm (～6.8×10¹⁴ molecules/cm³) in the same environment by probing the R(4) line. The dependences of signal intensities on molecular concentrations and laser pulse energies were demonstrated using C₂H₂ as the target species. The variations of the signal line shapes with changes in the buffer gas pressures and laser intensities were recorded and analyzed. The experimental setup demonstrated in this work facilitates the practical implementation of in situ, sensitive molecular species sensing with species-specific, spatial and temporal resolution in the spectral region of 2.7–3.3 μm (3000–3700 in cm^?1), where various molecular species important in combustion have absorption bands.     

Lithium diffusion in Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-based electrodes: a joint analysis of electrochemical impedance,cyclic voltammetry,pulse chronoamperometry,and chronopotentiometry data

In order to establish the mechanism and to determine the parameters of lithium transport in electrodes based on lithium-vanadium phosphate (Li₃V₂(PO₄)₃), the kinetic model was designed and experimentally tested for joint analysis of electrochemical impedance (EIS), cyclic voltammetry (CV), pulse chronoamperometry (PITT), and chronopotentiometry (GITT) data. It comprises the stages of sequential lithium-ion transfer in the surface layer and the bulk of electrode material’s particles, including accumulation of lithium in the bulk. Transfer processes at both sites are of diffusion nature and differ significantly, both by temporal (characteristic time, τ) and kinetic (diffusion coefficient, D) constants. PITT data analysis provided the following D values for the predominantly lithiated and delithiated forms of the intercalation material: 10^?9 and 3 × 10^?10 cm² s^?1, respectively, for transfer in the bulk and 10^?12 cm² s^?1 for transfer in the thin surface layer of material’s particles. D values extracted from GITT data are in consistency with those obtained from PITT: 3.5–5.8 × 10^?10 and 0.9–5 × 10^?10 cm² s^?1 (for the current and currentless mode, respectively). The D values obtained from EIS data were 5.5 × 10^?10 cm² s^?1 for lithiated (at a potential of 3.5 V) and 2.3 × 10^?9 cm² s^?1 for delithiated (at a potential 4.1 V) forms. CV evaluation gave close results: 3 × 10^?11 cm² s^?1 for anodic and 3.4 × 10^?11 cm² s^?1 for cathodic processes, respectively. The use of complex experimental measurement procedure for combined application of the EIS, PITT, and GITT methods allowed to obtain thermodynamic E,c dependence of Li₃V₂(PO₄)₃ electrode, which is not affected by polarization and heterogeneity of lithium concentration in the intercalate.     

A quantum cascade laser-based optical feedback cavity-enhanced absorption spectrometer for the simultaneous measurement of CH4 and N2O in air

Optical feedback cavity-enhanced absorption spectroscopy (OF CEAS) has been demonstrated with a thermoelectrically cooled continuous wave distributed feedback quantum cascade laser (QCL) operating at wavelengths around 7.84 μm. The QCL is coupled to an optical cavity which creates an absorption pathlength greater than 1000 m. The experimental design allows optical feedback of infra-red light, resonant within the cavity, to the QCL, which initiates self-locking at each TEM₀₀ cavity mode frequency excited. The QCL linewidth is narrowed to below the mode linewidth, greatly increasing the efficiency of injection of light into the cavity. At the frequency of each longitudinal cavity mode, the absorption coefficient of an intracavity sample is obtained from the transmission at the mode maximum, measured with a thermoelectrically cooled detector: spectral line profiles of CH₄ and N₂O in ambient air were recorded simultaneously and with a resolution of 0.01386 cm^?1. A minimum detectable absorption coefficient of 5.5×10^?8 cm^?1 was demonstrated after an averaging time of 1 s for this completely thermoelectrically cooled system. The bandwidth-normalised limit for a single cavity mode is 5.6×10^?9 cm^?1?Hz^?1/2 (1σ).     

T-shape microresonator-based quartz-enhanced photoacoustic spectroscopy for ambient methane monitoring using 3.38-μm antimonide-distributed feedback laser diode

This paper reports on the development of a gas sensor involving a newly available 3.38-μm distributed feedback laser in combination with a novel T-shape microresonator-based quartz-enhanced photoacoustic spectroscopy (T-mR QEPAS), capable of simultaneous monitoring of multi-species (such as CH₄, H₂CO, HCl, C₂H₄) using the same QEPAS spectrophone. As a first demonstration, monitoring of ambient methane (CH₄) was achieved at atmospheric pressure with a 1σ detection limit of 400 ppbv (parts per billion by volume) in an integration time of 10 s and a water vapor concentration of 1.15 vol% (11,500 ppm) in the atmosphere, which is very suitable for field measurement of CH₄ emission.     

Properties of a gel polymer electrolyte based on lithium salt with poly(vinyl butyral)

Poly(vinyl butyral) (PVB) is of particular interest because of its low cost, extremely wide temperature work range (? 20 to 120 °C), and efficient chemical stability. In this study, a gel polymer electrolyte (GPE) containing Li⁺ ions was fabricated by using dimethylacetylamine (DMA), lithium perchlorate (LiClO₄), and PVB. The experimental results indicated that a highly transparent GPE with a high ionic conductivity (σ) could be obtained by mixing glue (DMA with a PVB content of 10 wt%) with a LiClO₄ content of 6 wt%. It was found that the ionic conductivity (σ) of the GPE depended on the LiClO₄ content, and the GPE with a LiClO₄ content of 6 wt% exhibited a maximum σ of 7.73 mS cm^?1, a viscosity coefficient of 3360 mPa s, and a transmittance greater than 89% (visible region) at room temperature. Furthermore, PVB improved the electrolyte solution leakage, and the LiClO₄ was used as an ion supply source for the high σ of the GPE.     

Relaxation des Natrium-Grundzustandes bei Stößen mit den stabilen Helium- und Wasserstoff-Isotopen

The spin-polarization of the optically pumped Na-groundstate is investigated in presence of the stable He- and H₂-isotopes. The following disorientation cross sections are derived from the pressure dependence of the relaxation rate:σ=(16.2±2.0) · 10^?26 cm² for He³ σ=(2.4±0.5) · 10^?26 cm² for He⁴ σ=(3.9±1.5) · 10^?26 cm² for H₂ σ=(2.3±1.0) · 10^?26 cm² for D₂. These values can be compared with theoretical cross sections based on two relaxation models and indicate the existence of a relaxation mechanism involving the exchange of the electronic alkali-spin with the nuclear spin of the foreign gas.