Recent advances in chemical sensors for soil analysis: a review

The continuously rising interest in chemical sensors' applications in environmental monitoring, for soil analysis in particular, is owed to the sufficient sensitivity and selectivity of these analytical devices, their low costs, their simple measurement setups, and the possibility to perform online and in-field analyses with them. In this review the recent advances in chemical sensors for soil analysis are summarized. The working principles of chemical sensors involved in soil analysis; their benefits and drawbacks; and select applications of both the single selective sensors and multisensor systems for assessments of main plant nutrition components, pollutants, and other important soil parameters (pH, moisture content, salinity, exhaled gases, etc.) of the past two decades with a focus on the last 5 years (from 2017 to 2021) are overviewed

Thermal Bimorph Micro-Cantilever Based Nano-Calorimeter for Sensing of Energetic Materials

The objective of this study is to develop a robust portable nano-calorimeter sensor for detection of energetic materials, primarily explosives, combustible materials and propellants. A micro-cantilever sensor array is actuated thermally using bi-morph structure consisting of gold (Au: 400 nm) and silicon nitride (Si3N4: 600 nm) thin film layers of sub-micron thickness. An array of micro-heaters is integrated with the microcantilevers at their base. On electrically activating the micro-heaters at different actuation currents the microcantilevers undergo thermo-mechanical deformation, due to differential coefficient of thermal expansion. This deformation is tracked by monitoring the reflected ray from a laser illuminating the individual microcantilevers (i.e., using the optical lever principle). In the presence of explosive vapors, the change in bending response of microcantilever is affected by the induced thermal stresses arising from temperature changes due to adsorption and combustion reactions (catalyzed by the gold surface). A parametric study was performed for investigating the optimum values by varying the thickness and length in parallel with the heater power since the sensor sensitivity is enhanced by the optimum geometry as well as operating conditions for the sensor (e.g., temperature distribution within the microcantilever, power supply, concentration of the analyte, etc.). Also, for the geometry present in this study the nano-coatings of high thermal conductivity materials (e.g., Carbon Nanotubes: CNTs) over the microcantilever surface enables maximizing the thermally induced stress, which results in the enhancement of sensor sensitivity. For this purpose, CNTs are synthesized by post-growth method over the metal (e.g., Palladium Chloride: PdCl2) catalyst arrays pre-deposited by Dip-Pen Nanolithography (DPN) technique. The threshold current for differential actuation of the microcantilevers is correlated with the catalytic activity of a particular explosive (combustible vapor) over the metal (Au) catalysts and the corresponding vapor pressure. Numerical modeling is also explored to study the variation of temperature, species concentration and deflection of individual microcantilevers as a function of actuation current. Joule-heating in the resistive heating elements was coupled with the gaseous combustion at the heated surface to obtain the temperature profile and therefore the deflection of a microcantilever by calculating the thermally induced stress and strain relationship. The sensitivity of the threshold current of the sensor that is used for the specific detection and identification of individual explosives samples - is predicted to depend on the chemical kinetics and the vapor pressure. The simulation results showed similar trends with the experimental results for monitoring the bending response of the microcantilever sensors to explosive vapors (e.g., Acetone and 2-Propanol) as a function of the actuation current

Microcantilever biosensors

The cross-sensitivity of microcantilever sensors presents a major obstacle in the development of a commercially viable microcantilever biosensor for point of care testing. This thesis concerns electrothermally actuated bi-material microcantilevers with piezoresistive read out, developed for use as a blood coagulometer. Thermal properties of the sensor environment including the heat capacity and thermal conductivity affect the ‘thermal profile’ onto which the higher frequency mechanical signal is superimposed. In addition, polymer microcantilevers are known to have cross-sensitivity to relative humidity due to moisture absorption in the beam. However it is not known whether any of these cross sensitivities have a significant impact on performance of the sensor during pulsed mode operation or following immersion into liquid. When analysing patient blood samples, any change in signal that is not caused by the change in blood viscosity during clotting could lead to a false result and consequently an incorrect dose of anticoagulants may be taken by the patient. In order to address these issues three aspects of the operation of polymer bi-material strip cantilevers has been researched and investigated: relative humidity; viscosity/density, and thermal conductivity of a liquid environment. The relative humidity was not found to affect the resonant frequency of a microcantilever operated in air, or to affect the ability of the cantilever to measure clot times. However, a decrease in deflection with increasing relative humidity of the SmartStrip microcantilever beams is observed at 1.1 ± 0.4 μm per 1% RH, and is constant with temperature over the range 10 – 37 °C, which is an issue that should be considered in quality control. In this study, the SmartStrip was shown to have viscosity sensitivity of 2 cP within the range 0.7 – 15.2 cP, and it was also shown that the influence of inertial effects is negligible in comparison to the viscosity. To investigate cross-sensitivity to the thermal properties of the environment, the first demonstration of a cantilever designed specifically to observe the thermal background is presented. Characterisation experiments showed that the piezoresistive component of the signal was minimised to -0.8% ± 0.2% of the total signal by repositioning the read out tracks onto the neutral axis of the beam. Characterisations of the signal in a range of silicone oils with different thermal conductivities gave a resolution to thermal conductivity of 0.3 Wm-1K-1 and resulted in a suggestion for design improvements in the sensor: the time taken for the thermal background signal to reach a maximum can be increased by increasing the distance between the heater and sensor, thus lessening the impact of the thermal crosstalk within the cantilever beam. A preliminary investigation into thermal properties of clotting blood plasma showed that the sensor can distinguish the change between fresh and clotted plasma

Theoretical Analysis of Laterally Vibrating Microcantilever Sensors in a Viscous Liquid Medium

Dynamically driven microcantilevers are normally excited into resonance in the out-of-plane flexural mode. The beam\u27s resonant frequency and quality factor are used to characterize the devices. The devices are well suited for operation in air, but are limited in viscous liquid media due to the increased viscous damping. In order to improve these characteristics, other vibration modes such as the in-plane (or lateral) flexural mode are investigated. In this work, microcantilevers vibrating in the in-plane flexural mode (or lateral direction) in a viscous liquid medium are investigated. The hydrodynamic forces on the microcantilever as a function of both Reynolds number and aspect ratio (thickness over width) are first calculated using a combination of numerical methods and Stokes\u27 solution. The results allowed for the resonant frequency, quality factor, and mass sensitivity to be investigated as a function of both beam geometry and medium properties. The predicted resonant frequency and quality factor for several different laterally vibrating beams in water are also found to match the trends given by experimentally determined values found in the literature. The results show a significant improvement over those of similar devices vibrating in the out-of-plane flexural mode. The resonant frequency increases by a factor proportional to the inverse of the beam\u27s aspect ratio. Moreover, the resonant frequency of a laterally vibrating beam shows a smaller decrease when immersed in water (5-10% compared to ~50% for transversely vibrating beams) and, as the viscosity increases, the resonant frequency decreases slower compared to beams excited transversely. The quality factor is found to increase by a factor of 2-4 or higher depending on the medium of operation and the beam geometry. Due to the increased resonant frequency and the decreased effective mass of the beam (compared to beams excited transversely), the estimated mass sensitivity of a laterally excited microcantilever is found to be much larger (up to two orders of magnitude). The improvement in these characteristics is expected to yield much lower limits of detection in liquid-phase bio-chemical sensing applications

Online Chemical Sensor Signal Processing Using Estimation Theory: Quantification of Binary Mixtures of Organic Compounds in the Presence of Linear Baseline Drift and Outliers

Compact sensor systems for on-site monitoring of groundwater for trace organic compounds in the liquid phase are currently under development in our laboratories. Potential challenges include sensor baseline drift and the presence of outliers in the data, along with difficulties extracting the contribution of individual BTEX compound (benzene, toluene, ethylbenzene, and xylenes) from the sensor response to mixtures containing multiple chemically similar compounds. As a first step, the approach presented here permits online estimation of analyte concentrations in binary mixtures of BTEX compounds in the presence of linear baseline drift and outliers. This paper investigates a sensor signal-processing approach based on estimation theory, specifically, Kalman filter (KF), extended KF, and discrete low-pass filter. The approach permits online linear baseline drift correction, filtering of outlier points, and estimation of analyte concentration(s) in binary mixtures and single analyte samples, before the sensor response reaches steady state. Sensor signals from mixtures of BTEX compounds were analyzed because these compounds are good indicators of accidental releases of fuel and oil into groundwater. Models were first developed for the sensor response so that estimation theory can be used to obtain the sensor parameters. The baseline-drift correction technique uses KF to perform online linear extrapolation or interpolation. The presented combination of sensor signal-processing techniques was simultaneously tested using actual measured data. Unknown sensor parameters and identification of analytes in samples were obtained within a relatively short period of time (8 min or less for the present sensor system), well before the sensor response reaches equilibrium

Integrated microcantilever fluid sensor as a blood coagulometer

The work presented concerns the improvement in mechanical to thermal signal of a microcantilever fluid probe for monitoring patient prothrombin time (PT) and international normalized ratio (INR) based on the physical measurement of the clotting cascade. The current device overcomes hydrodynamic damping limitations by providing an internal thermal actuation force and is realised as a disposable sensor using an integrated piezoresistive deflection measurement. Unfortunately, the piezoresistor is sensitive to thermal changes and in the current design the signal is saturated by the thermal actuation. Overcoming this problem is critical for demonstrating a blood coagulometer and in the wider field as a microsensor capable of simultaneously monitoring rheological and thermal measurements of micro-litre samples. Thermal, electrical, and mechanical testing of a new design indicates a significant reduction in the thermal crosstalk and has led to a breakthrough in distinguishing the mechanical signal when operated in moderately viscous fluids (2-3 cP). A clinical evaluation has been conducted at The Royal London Hospital to measure the accuracy and precision of the improved microcantilever fluid probe. The correlation against the standard laboratory analyser INR, from a wide range of patient clotting times(INR 0.9-6.08) is equal to 0.987 (n=87) and precision of the device measured as the percentage coefficient of variation, excluding patient samples tested < 3 times, is equal to 4.00% (n=64). The accuracy and precision is comparable to that of currently available point-of-care PT/INR devices. The response of the fluid probe in glycerol solutions indicates the potential for simultaneous measurement of rheological and thermal properties though further work is required to establish the accuracy and range of the device as a MEMS based viscometer

A Robust Method for Tuning Photoacoustic Gas Detectors

Detection of gases in industrial contexts is of great importance for ensuring safety in storage and transport, so as to limit atmospheric pollution and precisely control industrial and agricultural processes. Although chemical sensors are in widespread use, solid-state infrared detectors for gas sensing promise numerous advantages over conventional catalytic detectors in terms of sensitivity, calibration requirements, and lifetime. The laser-modulation photoacoustic approach is an alternative. Compared to other approaches, it provides more precise measurements with a stable zero baseline, as well as having significantly less complicated optics than cavity ringdown approaches. One enduring problem, though, is the relatively long time required to make photoacoustic measurements. The key contribution of this paper to the industrial context is twofold: first, we show how a sensitive dual-buffer acoustic resonator may be fabricated using 3D printing, and secondly we describe a method for localizing the peak absorption more rapidly than stepping a laser through the gas absorption profile. Modelling of the proposed approach demonstrates its potential, and the expected results are confirmed using an extensive experimental setup for the detection of methane in air