High-Sensitivity Differential Helmholtz Photoacoustic System Combined with the Herriott Multipass Cell and Its Application in Seed Respiration.

A highly sensitive photoacoustic detection system using a differential Helmholtz resonator (DHR) combined with a Herriott multipass cell is presented, and its implementation to sub-ppm level carbon dioxide (CO2) detection is demonstrated. Through the utilization of erbium-doped optical fiber amplifier (EDFA), the laser power was amplified to 150 mW. Within the multipass cell, a total of 22 reflections occurred, contributing to an impressive 33.6 times improvement in the system sensitivity. The normalized noise equivalent absorption coefficient (NNEA) was 8.64 × 10-11 cm-1·W·Hz-1/2 [signal-to-noise ratio, (SNR) = 1] and according to the Allan variance analysis, a minimum detection limit of 500 ppb could be achieved for CO2 at 1204 s, which demonstrates the long-term stability of the system. The system was applied to detect the respiration of rice and upland rice seeds. It is demonstrated that the system can monitor and distinguish the respiration intensity and respiration rate of different seeds in real time.

A Coin-Sized Oxygen Laser Sensor Based on Tunable Diode Laser Absorption Spectroscopy Combining a Toroidal Absorption Cell.

Laser gas sensors with small volume and light weight are in high demand in the aerospace industry. To address this, a coin-sized oxygen (O2) sensor has been successfully developed based on a small toroidal absorption cell design. The absorption cell integrates a vertical-cavity surface-emitting laser (VCSEL) and photodetector into a compact unit, measuring 90 × 40 × 20 mm and weighing 75.16 g. Tunable diode laser absorption spectroscopy (TDLAS) is used to obtain the O2 spectral line at 763 nm. For further improving the sensitivity and robustness of the sensor, wavelength modulation spectroscopy (WMS) is utilized for the measurement. The obtained linear correlation coefficient is 0.9994. Based on Allen variance analysis, the sensor achieves an impressive minimum detection limit of 0.06% for oxygen concentration at an integration time of 318 s. The pressure-dependent relationship has been validated by accounting for the pressure factor in data processing. To affirm its efficacy, the laser spectrometer underwent continuous atmospheric O2 measurement for 24 h, showcasing its stability and robustness. This development introduces a continuous online laser spectral sensor with potential applications in manned spaceflight scenarios.

Self-calibrated NICE-OHMS based on an asymmetric signal: theoretical analysis and experimental validation.

As an ultra-sensitive detection technique, the noise-immune cavity enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) technique has great potential for assessment of the concentration of trace gases. To determine gas concentrations at the ppt or lower level with high accuracy, it is desirable that the technique exhibits self-calibration (or calibration-free) capabilities. Although being sensitive, NICE-OHMS has so far not demonstrated any such ability. To remedy this, this paper provides a self-calibrated realization of NICE-OHMS that is based on a switching of the feedback target of the DeVoe-Brewer (DVB) locking procedure from the modulation frequency of the frequency modulation spectroscopy (FMS) to the cavity length, which creates an asymmetrical signal whose form and size can be used to unambiguously assess the gas concentration. A comprehensive theoretical model for self-calibrated NICE-OHMS is established by analyzing the shift of cavity modes caused by intracavity absorption, demonstrating that gas absorption information can be encoded in both the laser frequency and the NICE-OHMS signal. To experimentally verify the methodology, we measure a series of dispersion signals under different levels of absorbance using a built experimental setup. An instrument factor and the partial pressure are obtained by fitting the measured signal through theoretical expressions. Our results demonstrate that fitted values are more accurate for higher partial pressures than for lower. To improve on the accuracy at low partial pressures, it is shown that the instrument factor obtained by fitting the signal at large partial pressures (in this case, above 7.8 µTorr) can be set to a fixed value for all fits. By this, the partial pressures can be assessed with a relative error below 0.65%. This technique has the potential to enable calibration-free ultra-sensitive gas detection.

Rate constant and branching ratio of the reaction of ethyl peroxy radicals with methyl peroxy radicals.

The cross-reaction of ethyl peroxy radicals (C2H5O2) with methyl peroxy radicals (CH3O2) (R1) has been studied using laser photolysis coupled to time resolved detection of the two different peroxy radicals by continuous wave cavity ring down spectroscopy (cw-CRDS) in their AÃ-X̃ electronic transition in the near-infrared region, C2H5O2 at 7602.25 cm-1, and CH3O2 at 7488.13 cm-1. This detection scheme is not completely selective for both radicals, but it is demonstrated that it has great advantages compared to the widely used, but unselective UV absorption spectroscopy. Peroxy radicals were generated from the reaction of Cl-atoms with the appropriate hydrocarbon (CH4 and C2H6) in the presence of O2, whereby Cl-atoms were generated by 351 nm photolysis of Cl2. For different reasons detailed in the manuscript, all experiments were carried out under excess of C2H5O2 over CH3O2. The experimental results were best reproduced by an appropriate chemical model with a rate constant for the cross-reaction of k = (3.8 ± 1.0) × 10-13 cm3 s-1 and a yield for the radical channel, leading to CH3O and C2H5O, of (ϕ1a = 0.40 ± 0.20).

An Ab Initio Investigation on Relevant Oligomerization Reactions of Toluene Diisocyanate (TDI).

2,4- and 2,6-isomers of toluene diisocyanates (2,4-TDI and 2,6-TDI) are important raw materials in the polyurethane industry. These reactive compounds associate even under ambient conditions to form oligomers, changing the physicochemical properties of the raw material. Kinetically and thermodynamically relevant dimerization reactions were selected based on G3MP2B3 calculations from all possible dimers of phenyl isocyanate using these isocyanates as proxies. As it turned out, only the formation of the diazetidine-2,4-dione ring (11-dimer, uretdione) resulted in a species having an exothermic enthalpy of formation (-30.4 kJ/mol at 298.15 K). The oxazetidin-2-one ring product (1-2-dimer) had a slightly endothermic standard enthalpy of formation (37.2 kJ/mol at 298.15 K). The mechanism of the relevant cyclodimerization reactions was investigated further for 2,4-TDI and 2,6-TDI species using G3MP2B3 and SMD solvent model for diazetidine as well as oxazetidin-2-one ring formation. The formation of the uretdione ring structures, from the 2,4-TDI dimer with both NCO groups in the meta position for each phenyl ring and one methyl group in the para and one in the meta position, had the lowest-lying transition state (Δ#E0= 94.4 kJ/mol) in the gas phase. The one- and two-step mechanisms of the TDI cyclotrimerization were also studied based on the quasi-G3MP2B3 (qG3MP2B3) computational protocol. The one-step mechanism had an activation barrier as high as 149.0 kJ/mol, while the relative energies in the two-step mechanism were significantly lower for both transition states in the gas phase (94.7 and 60.5 kJ/mol) and in ODCB (87.0 and 54.0 kJ/mol).

Resonant photoacoustic spectrometer enhanced by multipass absorption for detecting atmospheric CH4 at the ppb-level.

A resonant photoacoustic spectrometer (PAS) was developed for detecting trace atmospheric CH4. The sensitivity of the PAS was significantly increased via a Herriott-type multipass cell with a beam pattern concentrated in the cavity. The effective optical pathlength of the PAS can be optimized to 6.8 m with 34 reflections and a diameter of 6 mm. A distributed feedback diode laser at 1,653 nm was employed as the light source, and wavelength modulation spectroscopy was used for the 2nd harmonic signal to reduce the noise of the system. The resonant cell of PA and optimal modulation frequency were obtained by varying the measurements. In comparison with a single path, the sensitivity of the multipass strategy was improved 13 times. To evaluate the long-term stability and minimum detection limit (MDL) of the system, an Allan variance analysis was performed, and the analysis illustrated that the MDL accomplished 116 ppb at an average time of 84 s. The system was utilized for 2 days test campaign to validate the feasibility and robustness of the sensor. The system provides a promising technique for online monitoring of greenhouse gasses.

High-Efficient Ultrathin PdCuMo Porous Nanosheets with Abundant Defects for Oxygen Reduction Reaction.

To reduce the over-dependence on Pt, Pd-based catalysts have become one of the most effective candidates for oxygen reduction reaction (ORR). In order to further accelerate the ORR kinetics and strengthen the catalytic performance of Pd catalysts, component optimization and morphology design have been adopted. Although great progress has been made, it is still difficult to obtain porous ultrathin nanosheets with excellent performance by a simple method. Here, ultrathin PdCuMo porous nanosheets (PdCuMo NSs) were successfully prepared. This structure possessed a large specific surface area with rich cavities and structural defects, significantly enhancing its ORR performance. In special, the mass activity of PdCuMo NSs was 1.46 A mg-1 at 0.90 V, which was 12.2, 8.6, and 2.7 times as high as that of Pd/C, Pt/C, and PdCuMo nanoparticles (PdCuMo NPs), respectively. In addition, it had an excellent ability to resist CO poisoning and exhibited remarkable long-term stability.

Simultaneous measurement of liquid film thickness and temperature on metal surface.

The flow and evaporation of liquid films widely exist in various industrial fields. The investigation into liquid films is essential to design and optimize the relevant industrial processes. In this work, a simultaneous measurement method of liquid film thickness and temperature on metal surface based on diode laser absorption spectroscopy (DLAS) was proposed, and a corresponding measurement system was developed. First, static liquid films of 200-800 µm on the horizontal metal plate were studied, ultrasonic pulse-echo method (UPEM) and thermocouple were employed to compare with DLAS data. It revealed that the relative deviations of film thicknesses and temperatures measured by different methods were 3.3% and 2.0%, respectively. Furthermore, the evaporation processes of static liquid films were investigated. For the liquid films with different initial thicknesses (490.0/624.6/744.5 µm), the average relative deviations of the film thicknesses and temperatures measured by different methods were 0.1%/0.8%/4.1% and 0.1%/2.6%/3.0%, respectively. Finally, the flow processes of liquid films at different initial temperatures (40.0/60.0/80.0 °C) on the inclined metal plate were researched. It was found that the variation trends of the liquid film thicknesses and temperatures measured by different methods were in good agreement. In the stable stages of flow processes, the average relative deviations of liquid film thicknesses and temperatures measured by different methods were 9.0%/8.4%/5.1% and 3.6%/1.2%/2.5%, respectively. This work is helpful to understand the heat and mass transfer mechanisms in the evaporation and flow processes of liquid films.

Palm-Sized Laser Spectrometer with High Robustness and Sensitivity for Trace Gas Detection Using a Novel Double-Layer Toroidal Cell.

A palm-sized laser spectrometer has been developed for detecting trace gases based on tunable diode laser absorption spectroscopy in combination with a novel double-layer toroidal cell. With the benefit of a homemade electronic system and compact optical design, the physical dimensions of the sensor are minimized to 24 × 15× 16 cm3. A toroidal absorption cell, with 84 reflections in 2 layers for an effective optical path length of 8.35 m, was used to enhance the absorption signals of gaseous species. A homemade electronic system was designed for implementing a distributed feedback (DFB) diode laser controller, an analog lock-in amplifier, data acquisition, and communication. Calibration-free scanned wavelength modulation spectroscopy was employed to determine the concentration of the gas and reduce the random fluctuations from electronical noise and mechanical vibration. The measurement of CH4 in ambient air was demonstrated using a DFB laser at 1.653 µm. The rise time and fall time for renewing the gas mixture are approximately 16 and 14 s, respectively. Vibration and temperature tests have been carried out for verifying the performance of the spectrometer, and standard deviations of 0.38 ppm and 0.11 ppm for 20 ppm CH4 at different vibration frequencies and temperatures, respectively, have been determined. According to the Allan deviation analysis, the minimum detection limit for CH4 can reach 22 ppb at an integration time of 57.8 s. The continuous measurement of atmospheric CH4 for 2 days validated the feasibility and robustness of our laser spectrometer, providing a promising laser spectral sensor for deploying in unmanned aerial vehicles or mobile robots.

Implementation of the toroidal absorption cell with multi-layer patterns by a single ring surface.

We developed a type of toroidal multi-pass cell with multi-layer patterns based on the off-axis model. The effective path length of the original toroidal multi-pass cell is extended several roundtrips in comparison with the single-layer pattern, since the inner surface of the toroidal multi-pass cell is more efficiently utilized. The light pattern has been achieved by using the simple ring surface, which is easy to fabricate. The exact analytical equations for the design of the toroidal multi-pass cell were derived based on analytical vector calculations. A series of numerical ray tracing simulations is presented, and the maximum theoretical optical path length that can be reached is 30 m with a setup of 5 cm column radius. Furthermore, two practical spot patterns are demonstrated with a path length of 8.3 m for a two-layer pattern and 10 m for a three-layer pattern, with respective effective volumes of 63 mL and 94 mL. Furthermore, the fringe effect is substantially reduced to less than 0.5% by the usage of our designed mask.

Optimization of leakage detection system for vials based on two-line tunable diode laser absorption spectroscopy.

The leakage detection system of vials based on two-line water-vapor tunable diode laser absorption spectroscopy (TDLAS) developed in our previous work was first employed to investigate the instantaneous leakage processes of sealed vials. It showed that the leakage states of the vials with medicines cannot be accurately determined in a short time after the opening. Therefore, an optimized system was developed with two-line oxygen TDLAS method by the measurement of defined oxygen leakage coefficient, and it was then utilized to study the instantaneous leakage processes of sealed vials. It revealed that when the stoppers of the sealed vials were opened, the oxygen leakage coefficients increased immediately and then reach stable. It indicated that the optimized system was not affected by the water absorption of medicines. Furthermore, 15 vials with known leakage states were measured. It showed that the oxygen leakage coefficients of fully-open vials were obviously larger than that of sealed vials, and the maximum standard deviation of oxygen leakage coefficients for ten measurements of a single vial was 0.03%. The sealed vials with different leakage degrees were then investigated by inserting the needles with different sizes (0.5/1/2/3.5 mm) into the vials. It revealed that the time required for the oxygen leakage coefficients to reach stable was shorter for the vials with larger leakage degree, i.e., larger needle size inserted. It showed that non-invasive, fast response and high-accuracy leakage detection of vials can be realized by the optimized system.

Development of a two-line DLAS sensor for liquid film measurement.

The simultaneous measurements of multiple parameters (film thickness, temperature, etc.) of the liquid films are crucial for the design and optimization of relevant industrial processes. Here, a sensor based on diode-laser absorption spectroscopy (DLAS) was developed to simultaneously measure liquid water film thicknesses and temperatures by combining two diode lasers at different wavenumber positions, 6718.2 cm-1 and 7040.8 cm-1. Serious beam steering effects can be avoided by adding an integrating sphere to improve the performance of the sensor for the investigations of dynamic films. The measurement accuracies of this sensor were firstly validated by a calibration tool with known film thicknesses and temperatures. It revealed that the averaged deviations between the measured film thicknesses/temperatures and the corresponding known parameters were 4.58% and 1.34%, respectively. The sensor was then employed to study liquid film evaporation processes on a horizontal quartz glass plate. The imaging method and the thermocouple were simultaneously employed to obtain the film thicknesses and temperatures to compare with the DLAS results. It showed that the average evaporation rates of the liquid films were 0.34/0.41/0.57 µm/s at different temperatures (340/360/390 K) of the heat gun outlet, respectively, and the evaporation rates increased with the increasing film temperatures. The whole evaporation process can be tracked with the sensor. Furthermore, the sensor was applied to simultaneously determine the variations of liquid film thicknesses and temperatures in a flow channel. It was found that the film temperatures remained almost constant during passage of low-amplitude surface waves at the film temperatures 308/315/323 K.

Simultaneous detection of atmospheric CO and CH4 based on TDLAS using a single 2.3 µm DFB laser.

A laser-based spectrometer with a physical size of 60× 30 ×25 cm3 has been developed to continuously monitor CO and CH4 in atmosphere based on tunable diode laser absorption spectroscopy (TDLAS). Two neighboring lines of CO and CH4 around 2.3 µm were selected as candidates for simultaneous measurement by a single diode distributed feedback (DFB) laser. A special Herriott-type multipass absorption cell, with a 72 m optical path length, was designed and used to enhance the absorption signals of sample gases. Normalized wavelength modulation spectroscopy was applied to improve the sensitivity and robustness of the spectrometer and it was implemented on a home-made electronic system based on field programmable gate array (FPGA). Meanwhile, the electronic system controlled the temperature and current of DFB laser with the precision of 0.01 °C and 40 ppm. The 2nd-harmonic signals normalized by the corresponding 1st-harmonic signals for both CO and CH4 are of high linear response to their concentrations in the range of 0.046-4.6 ppm and 0.487-48.7 ppm, respectively. According to the Allan variance, respective minimum detection limits for CO and CH4 are 0.73 ppb and 36 ppb at 122 s and 137 s. As an application example, the spectrometer has been validated through real-time and in-situ measurement of atmospheric CO and CH4 for 48 h.

Quantum state-to-state study for (H-(D-),HD) collisions on two potential energy surfaces.

Quantum time-dependent wave-packet calculations have been carried out to explore the state-to-state dynamics of the ion-molecule (H-(D-),HD) collisions on two accurate ab initio potential energy surfaces in the collision energy range 0.2-1.2 eV. Total and final state-resolved integral and differential cross sections are elaborated in detail. The differential cross sections vary substantially with the collision energy, turning from predominantly backward-scattering at low collision energies to forward and sideways scattering bias at relatively high collision energies. The rebound, stripping and time-delayed mechanisms are found to be possible in (H-(D-),HD) collisions. A set of quasi-classical trajectory calculations were performed, and the results indicate that the backward-scattering peak is caused by the low impact parameter trajectories, while the trajectories of high impact parameter are responsible for the forward scattering. A set of representative state-to-state differential cross sections at collision energies 0.6 and 1.2 eV are also presented. Different reaction mechanisms are dominant in (H-(D-),HD) collisions at different collision energies, resulting in different product rovibrational state distributions. The differences between the dynamics results based on the two potential energy surfaces are also discussed.

A portable low-power integrated current and temperature laser controller for high-sensitivity gas sensor applications.

A low-noise, low power, high modulation-bandwidth design integrated laser current and temperature driver with excellent long-term stability is described. The current driver circuit is based on the Hall-Libbrecht design. A high sensitivity and a stable driver current were obtained using a differential amplifier and an integral amplifier. The set-point voltage for the current driver came from an ultra-compact, ultra-low temperature coefficient voltage reference chip or the digital to analog convertor output of a microcontroller or a modulation signal. An integral temperature chip, referred to as ADN8834, was used to drive the thermoelectric cooler controller of the distributed feedback (DFB) laser. The internal amplifier acquired the feedback current of the temperature sensor. The proportional-integral-derivative parameters such as proportion, integration, and derivative were set by external resistors. The short- and long-term stability and linearity of the developed laser driver were tested using a DFB laser with a central wavelength of 6991 cm-1. The laser driver was validated for high-sensitivity gas sensing of CO2 and C2H2 via a laser absorption spectroscopy experiment. The limits of detection were less than 11.5 ppm and 0.124 ppm for CO2 and C2H2, respectively. Direct absorption measurements and the 1-f and 2-f demodulation signals confirmed the capabilities of the proposed laser driver system in high-sensitivity gas sensing applications. The driver unit can readily be accommodated into many portable laser sensing devices for industrial applications.

High-speed multi-pass tunable diode laser absorption spectrometer based on frequency-modulation spectroscopy.

We report a multi-pass tunable diode laser absorption spectrometer based on the frequency-modulation spectroscopy (FMS) technique. It has the advantage of high scan speed and is immune to the etalon effect. A multi-pass Herriott-type cell was used in the spectrometer to increase the effective optical length to 17.5 m and compact the physical dimensions of the spectrometer to 60×30×30 cm3. Noise due to low-frequency fluctuation of the laser power and the 1/f noise in the rapid detection are sufficiently reduced by FMS. Interference fringes are effectively suppressed when the modulation frequency equals to integer or half-integer times of their free spectral range (FSR). An absorption line of C2H2 around 1.51 µm was recorded with the spectrometer to demonstrate its capabilities. The response frequency of the spectrometer is up to 100 kHz (10 µs) thanks to the high modulation frequency of FMS. The detection sensitivity of the spectrometer is about 240 ppb (3σ) at 100 kHz measurement repetition rate. The amplitude of the absorption signal is highly linear to the C2H2 concentration in the range of 300 ppb -100 ppm. Based on the Allan variation, the detection limit was determined to be 18 ppb with a detection time of 166 s.

Simultaneous Measurements of CO and CO2 Employing Wavelength Modulation Spectroscopy Using a Signal Averaging Technique at 1.578 µm.

A resolved line pair was selected for simultaneous measurement of carbon monoxide (CO) and carbon dioxide (CO2) in the near-infrared (NIR) region. The spectral lines of CO and CO2 at 1.578 µm were measured by wavelength modulation spectroscopy (WMS)-2 f and the absorption was enhanced with a multipass absorption cell. The white noise was further reduced by averaging technology. The detection sensitivity (1σ) for the system is estimated at 2.63 × 10-7 cm-1 for direct absorption spectroscopy. The ultimate detection limits of CO2 and CO mixed with pure N2 at 75 Torr are 29 parts per million (ppm) and 47 ppm, respectively. It is demonstrated that the signal is highly linear with the concentration in the range of 100-800 ppm. Based on an Allan variation analysis, the minimum detectable limit of CO2 and CO is 7.5 and 14 ppm, respectively. The response time of the system is about 30 s and a relationship of temperature dependence was obtained. As an example, an in situ measurement of exhaust of alkane combustion emission is presented.

Pressure-Dependent Detection of Carbon Monoxide Employing Wavelength Modulation Spectroscopy Using a Herriott-Type Cell.

Wavelength modulation spectroscopy (WMS) combined with a multipass absorption cell has been used to measure a weak absorption line of carbon monoxide (CO) at 1.578 µm. A 0.95m Herriott-type cell provides an effective absorption path length of 55.1 m. The WMS signals from the first and second harmonic output of a lock-in amplifier (WMS-1 f and 2 f, respectively) agree with the Beer-Lambert law, especially at low concentrations. After boxcar averaging, the minimum detection limit achieved is 4.3 ppm for a measurement time of 0.125 s. The corresponding normalized detection limit is 84 ppm m Hz-1/2. If the integrated time is increased to 88 s, the minimum detectable limit of CO can reach to 0.29 ppm based on an Allan variation analysis. The pressure-dependent relationship is validated after accounting for the pressure factor in data processing. Finally, a linear correlation between the WMS-2 f amplitudes and gas concentrations is obtained at concentration ratios less than 15.5%, and the accuracy is better than 92% at total pressure less than 62.7 Torr.

[Study on the Spiral-Torus Herriott Type Cell].

With the rapid development of social economy, the environmental pollution and the ecological destruction are continuously deteriorating while sudden environmental pollution incidents occur frequently. Real-time monitoring harmful gases of the air take advantages of spectroscopic techniques for concentration measurement. Multipass optical cells are -widely used in absorption spectrometry technique to improve gas detection sensitivity under the condition of weak absorption. This paper proposes a spiral-torus type multipass optical device base on the structure of Herriott type cell. The optical device consists of multiple torus concave mirrors in a spiral way. Incident light propagates along with radical and axial direction in winding staircase pattern. The faculae on the inner wall present a spiral-type. The entrance and exit apertures are separated due to the spiral trace of optical rays, which increases the accessible adjustment of the apparatus. The effective optical length can be adjusted based on the proportional relationship to the reflective times. This device is characterized with easy adjustment and excellent mechanical performance due to its cylindrical structure. Based on ABCD matrix, the stability of the system was analyzed and the relationship between the number of reflections and the incident angle were discussed. With optical simulation software, we designed a device for separating polarized light, and the characteristics of its rotation was studied.

[Design of inhalable particulate matters measurement based on the Mie scattering extinction].

The concentration of inhalable particle is an important indicator in atmospheric environment monitor. Based on Mie scattering extinction, a precise testing instrument which can measure the concentration of inhalable particles at the atmospheric was designed by three-wavelength method in combination with the algorithm of distributed function. The dependence of extinction index on the spectrum was calculated based on Mie scattering theory in this article. Furthermore, the signal of time domain is integrated in the data processing to reduce the effect of error caused by multi-peak of spectra. The PM2.5 and PM10 were collected simultaneously in particle selection. Three different wave-lengths of lasers were coupled into an optical fiber by coupler (3 in 1) and passed through the sample cell. The attenuated light was detected by a PIN. Output of the detector was converted, amplified, displayed and stored by electronic system. Finally, the data were transmitted and shared in network through the 3G wireless module. The average particle size and concentration of inhalable particles were measured by this device at the same time. The technical specifications of the detector were verified by experiment, the experimental results indicate that the detection sensitivity of the system is 0.01 microg m(-3), the responsive time of system is approximately 90 s and it is suitable for measuring particulate matter concentrations of atmosphere.