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.

Laser Linewidth Analysis and Filtering/Fitting Algorithms for Improved TDLAS-Based Optical Gas Sensor.

Tunable Diode Laser Absorption Spectroscopy (TDLAS) has been widely applied in in situ and real-time monitoring of trace gas concentrations. In this paper, an advanced TDLAS-based optical gas sensing system with laser linewidth analysis and filtering/fitting algorithms is proposed and experimentally demonstrated. The linewidth of the laser pulse spectrum is innovatively considered and analyzed in the harmonic detection of the TDLAS model. The adaptive Variational Mode Decomposition-Savitzky Golay (VMD-SG) filtering algorithm is developed to process the raw data and could significantly eliminate the background noise variance by about 31% and signal jitters by about 12.5%. Furthermore, the Radial Basis Function (RBF) neural network is also incorporated and applied to improve the fitting accuracy of the gas sensor. Compared with traditional linear fitting or least squares method (LSM), the RBF neural network brings along the enhanced fitting accuracy within a large dynamic range, achieving an absolute error of below 50 ppmv (about 0.6%) for the maximum 8000 ppmv methane. The proposed technique in this paper is universal and compatible with TDLAS-based gas sensors without hardware modification, allowing direct improvement and optimization for current optical gas sensors.

Temperature Measurements by Wavelength Modulation Diode Laser Absorption Spectroscopy with Logarithmic Conversion and 1f Signal Detection.

A new version of a sensor for temperature measurements in the case of strong laser intensity fluctuation was developed. It was based on tunable diode laser absorption spectroscopy (TDLAS) with wavelength modulation, logarithmic conversion of the absorption signal, and detection of the first harmonic of the modulation frequency. The efficiency of the technique was demonstrated under experimental conditions with excess multiplicative noise. Temperature was evaluated from the ratio of integrated absorbance of two lines of the water molecule with different lower energy levels. Two algorithms of data processing were tested, simultaneous fitting of two spectral ranges with selected absorption lines and independent fitting of two absorption lines profiles. The correctness of the gas temperature evaluation was verified by simultaneous measurements with a commercial thermocouple. An error in temperature evaluation of less than 40 at 1000 K was achieved even when processing a single scan of the diode lasers.

Portable TDLAS Sensor for Online Monitoring of CO2 and H2O Using a Miniaturized Multi-Pass Cell.

We designed a tunable diode laser absorption spectroscopy (TDLAS) sensor for the online monitoring of CO2 and H2O concentrations. It comprised a small self-design multi-pass cell, home-made laser drive circuits, and a data acquisition circuit. The optical and electrical parts and the gas circuit were integrated into a portable carrying case (height = 134 mm, length = 388 mm, and width = 290 mm). A TDLAS drive module (size: 90 mm × 45 mm) was designed to realize the function of laser current and temperature control with a temperature control accuracy of ±1.4 mK and a current control accuracy of ±0.5 µA, and signal acquisition and demodulation. The weight and power consumption of the TDLAS system were only 5 kg and 10 W, respectively. Distributed feedback lasers (2004 nm and 1392 nm) were employed to target CO2 and H2O absorption lines, respectively. According to Allan analysis, the detection limits of CO2 and H2O were 0.13 ppm and 3.7 ppm at an average time of 18 s and 35 s, respectively. The system response time was approximately 10 s. Sensor performance was verified by measuring atmospheric CO2 and H2O concentrations for 240 h. Experimental results were compared with those obtained using a commercial instrument LI-7500, which uses non-dispersive infrared technology. Measurements of the developed gas analyzer were in good agreement with those of the commercial instrument, and its accuracy was comparable. Therefore, the TDLAS sensor has strong application prospects in atmospheric CO2 and H2O concentration detection and ecological soil flux monitoring.

An Improved WMS-2f/1f Spectral Fitting Method Using Orthogonal Test in Initial Parameters Selection.

This paper proposes an improved wavelength modulation spectroscopy with the 2nd harmonics normalized by the 1st harmonics (WMS-2f/1f) spectral fitting method using the orthogonal test in selection of the initial parameters. The method is implemented and validated experimentally in measurement of the temperature of diluted H2O in air (1 atm, 291K, 0.7%) by the WMS-2f/1f technique. The transition center wavelength targets near 1344 nm. Results demonstrate that the sum-square-error (SSE) between the calculated and measured WMS-2f/1f spectral profiles decreases significantly within given updating times when the optimized initial parameters are used. Compared to the conventional method, the optimized initial parameters can make the fitting routine converge more efficiently. The temperature of the vapor inferred from the proposed spectral fitting method are in good agreement with the true values.

Research on Methane Measurement and Interference Factors in Coal Mines.

The detection of methane has always been an important part of coal mine safety. In order to improve the methane measurement accuracy in coal mines and to determine the influence of environmental interference factors on the measurement results, we designed a spherical, experimental chamber simulating the on-site environment of an underground coal mine containing methane, in which various environmental interference factors can be superimposed. The simulation chamber can generate a uniform and controllable dust environment, a controllable methane environment with concentrations below that which would trigger an alarm, controllable humidity, and environments characterized by other interference factors. Based on computational simulations of the experimental chamber with varying dust-particle-concentration distributions using a single particle size, an optimal design for the chamber has been realized in terms of the rapid mixing of dust and the flow field. Finally, we constructed an underground methane concentration measurement system for coal mines and assessed the influences of different dust concentrations and relative humidity values on the performance of methane measurements, providing a means for improving the measurement accuracy of underground coal mine, spectral, absorption-type methane sensors.

Development and Validation of a Tunable Diode Laser Absorption Spectroscopy System for Hot Gas Flow and Small-Scale Flame Measurement.

TDLAS (tunable diode laser absorption spectroscopy) is an important gas analysis method that can be employed to obtain characteristic parameters non-invasively by the infrared absorption spectra of tracer molecules such as CH4, H2O and O2. In this study, a portable H2O-based TDLAS system with a dual optical path was developed with the aim of assessing the combustion characteristics of flammable gases. Firstly, a calculation method of gas characteristics including temperature and velocity combining absorption spectra and a HITRAN database was provided. Secondly, to calibrate and validate this TDLAS system precisely, a pressure vessel and a shock tube were introduced innovatively to generate static or steady flow fields with preset constant temperatures, pressures, or velocities. Static tests within environment pressures up to 2 MPa and steady flow field tests with temperatures up to 1600 K and flow velocities up to 950 m/s were performed for verification. It was proved that this system can provide an accurate values for high temperature and velocity gas flows. Finally, an experimental investigation of CH4/air flames was conducted to test the effectiveness of the system when applied to small diffusion flames. This TDLAS system gave satisfactory flame temperature and velocity data owing to the dual optical path design and high frequency scanning, which compensated for scale effects and pulsation of the flame. This work demonstrates a valuable new approach to thermal hazard analysis in specific environments.

Tomographic Absorption Spectroscopy for H2O Transport in a Laminar Jet with Inverse Concentration Gradient.

We report a tomographic absorption spectroscopy (TAS) study of water vapor transport in a laminar jet issuing into the ambient. The jet was generated using compressed dry air that was straightened by a honeycomb and a smooth contraction nozzle. A TAS scheme using the water vapor in the ambient as absorbing species and the absorption line near 1368.598 nm was proposed to study the H2O transport in the laminar jet with an inverse concentration gradient. One-dimensional tomography was conducted at various heights above the nozzle, and the results were validated by the predictions from computational fluid dynamics (CFD) simulations. Particularly, the variations in the concentration gradient in the shear layer at different heights were captured. The 2D distribution of water concentration in the dry laminar jet was obtained experimentally. The present study shows that TAS has great potential in the research of mass transfer and scalar field of gaseous flows.

Tunable Diode Laser Absorption Spectroscopy Based Temperature Measurement with a Single Diode Laser Near 1.4 µm.

The rapidly changing and wide dynamic range of combustion temperature in scramjet engines presents a major challenge to existing test techniques. Tunable diode laser absorption spectroscopy (TDLAS) based temperature measurement has the advantages of high sensitivity, fast response, and compact structure. In this invited paper, a temperature measurement method based on the TDLAS technique with a single diode laser was demonstrated. A continuous-wave (CW), distributed feedback (DFB) diode laser with an emission wavelength near 1.4 µm was used for temperature measurement, which could cover two water vapor (H2O) absorption lines located at 7153.749 cm-1 and 7154.354 cm-1 simultaneously. The output wavelength of the diode laser was calibrated according to the two absorption peaks in the time domain. Using this strategy, the TDLAS system has the advantageous of immunization to laser wavelength shift, simple system structure, reduced cost, and increased system robustness. The line intensity of the two target absorption lines under room temperature was about one-thousandth of that under high temperature, which avoided the measuring error caused by H2O in the environment. The system was tested on a McKenna flat flame burner and a scramjet model engine, respectively. It was found that, compared to the results measured by CARS technique and theoretical calculation, this TDLAS system had less than 4% temperature error when the McKenna flat flame burner was used. When a scramjet model engine was adopted, the measured results showed that such TDLAS system had an excellent dynamic range and fast response. The TDLAS system reported here could be used in real engine in the future.

Measurement of Atmospheric CO2 Column Concentrations Based on Open-Path TDLAS.

Monitoring of CO2 column concentrations is valuable for atmospheric research. A mobile open-path system was developed based on tunable diode laser absorption spectroscopy (TDLAS) to measure atmospheric CO2 column concentrations. A laser beam was emitted downward from a distributed feedback diode laser at 2 µm and then reflected by the retroreflector array on the ground. We measured the CO2 column concentrations over the 20 and 110 m long vertical path. Several single-point sensors were distributed at different heights to provide comparative measurements for the open-path TDLAS system. The results showed that the minimum detection limit of system was 0.52 ppm. Some similarities were observed in trends from the open-path TDLAS system and these sensors, but the average of these sensors was more consistent with the open-path TDLAS system values than the single-point measurement. These field measurements demonstrate the feasibility of open-path TDLAS for measuring the CO2 column concentration and monitoring carbon emission over large areas.

A Portable Tunable Diode Laser Absorption Spectroscopy System for Dissolved CO2 Detection Using a High-Efficiency Headspace Equilibrator.

Continuous observation of aquatic pCO2  at the ocean surface, with a sensitive response time and high spatiotemporal resolution, is essential for research into the carbon biogeochemical cycle. In this work, a portable tunable diode laser absorption spectroscopy (TDLAS) system for dissolved CO2 detection in surface seawater, coupled with a home-made headspace equilibrator, allowing real time underway measurements, is described. Both the optical detection part and sample extraction part were integrated together into a compact chamber. An empirical equation suitable for this system was acquired, which can convert the concentration from the gas-phase to the aqueous-phase. A monitoring precision of 0.5% was obtained with time-series measurement, and the detection limits of 2.3 ppmv and 0.1 ppmv were determined with 1 s and 128 s averaging time, respectively. Sampling device used in this work was ameliorated so that the response time of system reduced by about 50% compared to the traditional 'shower head' system. The fast response time reached the order of 41 s when the final concentration span was 3079 ppmv. For1902 ppmv, this figure was as short as 20 s. Finally, a field underway measurement campaign was carried out and the results were briefly analyzed. Our work proved the feasibility of the TDLAS system for dissolved CO2 rapid detection.

A Compact Model for Lyophilizer Equipment Capability Estimation.

This work presents a compact model for the equipment capability limit of a common configuration of pharmaceutical lyophilizers, a product chamber separated from the condenser by a duct and isolation valve, at a wide range of design parameters. The equipment capability limit is one of the most important characteristics determining the lyophilization design space for a particular product, container, and equipment combination. Experimental measurements of equipment capability are time-consuming and expensive, especially at the production scale. Numerical modeling using computational fluid dynamics may reduce the number of experiments and provide insights into the physics of the process with high resolution. The computational fluid dynamics (CFD) modeling has been used in this work to develop a compact model for lyophilizer equipment capability. This eliminates the need for end users to create a full CFD model of the equipment and process. Full CFD and compact model simulations for laboratory and pilot-scale lyophilizers have been compared with tunable diode laser absorption spectroscopy measurements of the water vapor mass flow during ice slab tests. The compact model results average deviation from the experimental data is within 10%, whereas the full CFD simulations are within 5%. The compact model is based on several key parameters which are the main characteristics of a lyophilizer affecting the equipment capability curve. These parameters are discussed, and their effect on the modeling results is shown.

A Software Tool for Lyophilization Primary Drying Process Development and Scale-up Including Process Heterogeneity, I: Laboratory-Scale Model Testing.

Freeze-drying is a deceptively complex operation requiring sophisticated design of a robust and efficient process that includes understanding and planning for heterogeneity across the batch and shifts in parameters due to vial or lyophilizer changes. A software tool has been designed to assist in process development and scale-up based on a model that includes consideration of the process heterogeneity. Two drug formulations were used to test the ability of the new tool to develop a freeze-drying cycle and correctly predict product temperatures and drying times. Model inputs were determined experimentally, and the primary drying heterogeneous freeze-drying model was used to design drying cycles that provided data to verify the accuracy of model-predicted product temperature and primary drying time. When model inputs were accurate, model-predicted primary drying times were within 0.1 to 15.9% of experimentally measured values, and product temperature accuracy was between 0.2 and 1.2°C for three vial locations, center, inner edge, and outer edge. However, for some drying cycles, differences in vial heat transfer coefficients due to changes in shelf and product temperature as well as altered product resistance due to product temperature-dependent microcollapse increased inaccuracy (up to 28.6% difference in primary drying time and 5.1°C difference in product temperature). This highlights the need for careful determination of experimental conditions used to calculate model inputs. In future efforts, full characterization of location- and shelf temperature-dependentKv as well as location- and product temperature-dependentRp will enhance the accuracy of the predictions by the model within the user-friendly software.

Equipment Capability Measurement of Laboratory Freeze-Dryers: a Comparison of Two Methods.

The objective of this investigation was to evaluate two methods for measuring the maximum sublimation rate that a freeze-dryer will support-the minimum controllable pressure method and the choke point method. Both methods gave equivalent results, but the minimum controllable pressure method is preferred, since it is easier, faster, and less subjective. The ratio of chamber pressure to condenser pressure corresponding to the onset of choked flow was considerably higher in this investigation (up to about 20:1) than in previously published reports. This ratio was not affected by the location of the pressure gauge on the condenser; that is, on the foreline of the vacuum pump versus on the body of the condenser itself. The total water loss due to sublimation as measured by tunable diode laser absorption spectroscopy was consistently within 5% of gravimetrically determined weight loss, regardless of whether the measurement took place during choked versus non-choked process conditions.

A high-performance system of multiple gas-exchange chambers with a laser spectrometer to estimate leaf photosynthesis, stomatal conductance, and mesophyll conductance.

Direct measurements of ecophysiological processes such as leaf photosynthesis are often hampered due to the excessive time required for gas-exchange measurements and the limited availability of multiple gas analyzers. Although recent advancements in commercially available instruments have improved the ability to take measurements more conveniently, the amount of time required for each plant sample to acclimate to chamber conditions has not been sufficiently reduced. Here we describe a system of multiple gas-exchange chambers coupled with a laser spectrometer that employs tunable diode laser absorption spectroscopy (TDLAS) to measure leaf photosynthesis, stomatal conductance, and mesophyll conductance. Using four gas-exchange chambers minimizes the time loss associated with acclimation for each leaf sample. System operation is semiautomatic, and leaf temperature, humidity, and CO2 concentration can be regulated and monitored remotely by a computer system. The preliminary results with rice leaf samples demonstrated that the system is capable of high-throughput measurements, which is necessary to obtain better representativeness of the ecophysiological characteristics of plant samples.

Hydrogen Sensor Based on Tunable Diode Laser Absorption Spectroscopy.

A laser-based hydrogen (H2) sensor using wavelength modulation spectroscopy (WMS) was developed for the contactless measurement of molecular hydrogen. The sensor uses a distributed feedback (DFB) laser to target the H2 quadrupole absorption line at 2121.8 nm. The H2 absorption line exhibited weak collisional broadening and strong collisional narrowing effects. Both effects were investigated by comparing measurements of the absorption linewidth with detailed models using different line profiles including collisional narrowing effects. The collisional broadening and narrowing parameters were determined for pure hydrogen as well as for hydrogen in nitrogen and air. The performance of the sensor was evaluated and the sensor applicability for H2 measurement in a range of 0-10 %v of H2 was demonstrated. A precision of 0.02 %v was achieved with 1 m of absorption pathlength (0.02 %v∙m) and 1 s of integration time. For the optimum averaging time of 20 s, precision of 0.005 %v∙m was achieved. A good linear relationship between H2 concentration and sensor response was observed. A simple and robust transmitter-receiver configuration of the sensor allows in situ installation in harsh industrial environments.

Development of a Dew/Frost Point Temperature Sensor Based on Tunable Diode Laser Absorption Spectroscopy and Its Application in a Cryogenic Wind Tunnel.

We have proposed a sensor for real-time and online measurement of dew/frost point temperature using tunable diode laser absorption spectroscopy (TDLAS) technique. Initial experiments have demonstrated its feasibility and technical advantages in comparison to a chilled mirror hygrometer (CMH). The TDLAS sensor we developed has a dew/frost point temperature range from -93 °C to + 14.5 °C, with a measurement uncertainly of less than 2%, and a response time of about 0.8 s, which is much faster than that of the chilled mirror hygrometer (ranging from several minutes to several hours). A TDLAS-based dew/frost point sensor has many advantages, such as rapid and continuous measurements, low frost point temperature sensing, high accuracy, and non-intrusiveness. Such a sensor would be useful for dew/frost point temperature determinations in various applications. In a cryogenic wind tunnel, real-time dew/frost point temperature measurements are helpful in preventing the formation of condensed liquid and ice, which can affect the model geometry and lead to unreliable test data.

Determination of the Maximum Temperature in a Non-Uniform Hot Zone by Line-of-Site Absorption Spectroscopy with a Single Diode Laser.

A new algorithm for the estimation of the maximum temperature in a non-uniform hot zone by a sensor based on absorption spectrometry with a diode laser is developed. The algorithm is based on the fitting of the absorption spectrum with a test molecule in a non-uniform zone by linear combination of two single temperature spectra simulated using spectroscopic databases. The proposed algorithm allows one to better estimate the maximum temperature of a non-uniform zone and can be useful if only the maximum temperature rather than a precise temperature profile is of primary interest. The efficiency and specificity of the algorithm are demonstrated in numerical experiments and experimentally proven using an optical cell with two sections. Temperatures and water vapor concentrations could be independently regulated in both sections. The best fitting was found using a correlation technique. A distributed feedback (DFB) diode laser in the spectral range around 1.343 µm was used in the experiments. Because of the significant differences between the temperature dependences of the experimental and theoretical absorption spectra in the temperature range 300⁻1200 K, a database was constructed using experimentally detected single temperature spectra. Using the developed algorithm the maximum temperature in the two-section cell was estimated with accuracy better than 30 K.

Mathematical Methods and Algorithms for Improving Near-Infrared Tunable Diode-Laser Absorption Spectroscopy.

Tunable diode laser absorption spectroscopy technology (TDLAS) has been widely applied in gaseous component analysis based on gas molecular absorption spectroscopy. When dealing with molecular absorption signals, the desired signal is usually interfered by various noises from electronic components and optical paths. This paper introduces TDLAS-specific signal processing issues and summarizes effective algorithms so solve these.

Experimental Aspects of Measuring the Vial Heat Transfer Coefficient in Pharmaceutical Freeze-Drying.

One of the current methods for cycle optimization in primary drying to is develop a graphical design space based on quality by design (QbD). In order to construct the design space, the vial heat transfer coefficient (Kv) is needed. This paper investigated experimental factors that can affect the Kv result, examined the relationship between the batch average Kv and Kv values for individual vials, and recommended best practices for measuring Kv. Factors investigated included the technique for measuring ice temperature, shelf temperature, the use of a radiation shield on the door of the freeze-dry chamber, and shelf spacing. All experiments reported here used a chamber pressure of 100 mTorr. The most important factor was the technique for ice temperature measurement, where it is important to assure that any restrictions to vapor flow at the top of the vial are the same between monitored and non-monitored vials. Another factor that was found to play a role was the shelf temperature whereby the lower the shelf temperature, the larger the "edge effect," and the larger the average Kv. Factors that were found to not have a significant effect were the use of a radiation shield inside the chamber door and the shelf spacing. Being aware of these factors and knowing best practices when determining the vial heat coefficient will lead to more accurate design spaces and better cycle optimization.