Method and system for determining target gas concentration in a fluid environment - Patents.com

Abstract

To provide a system and method for determining a target gas concentration in a fluid environment by using a gas sensor that improves the efficiency and accuracy of measurements of the gas sensor.SOLUTION: An improvement includes acquiring measurements of electrical characteristics of a gas sensor at different temperatures, acquiring measurements during a transition between a first temperature and a second temperature, acquiring more frequent measurements, detecting when the gas sensor has reached equilibrium, using multiple sensors, accounting offsets and drifts into consideration, reducing the time when the sensor is not live; using various algorithms, or any combination thereof.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a system and method for determining gas concentration in a fluid environment. [Background technology]

[0002] A large number of gas sensors are known in the art. The gas concentration can be measured by observing the change in the electrical properties of the sensor (current, voltage, capacitance, resistance, etc.). Thus, resistive sensors, capacitive sensors, and semiconductor sensors such as transistor or diode sensors are known in the art.

[0003] As a specific example, thin-film PdNi alloy resistors have been used to detect and measure the concentration of gases such as hydrogen. Hydrogen is soluble in PdNi, and the resistivity of thin-film PdNi alloys increases when exposed to hydrogen, with the increase being proportional to the square root of the hydrogen partial pressure. Some gas sensors, such as those with a PdNi lattice, may exhibit an increase in resistance or a change in capacitance or semiconducting properties with increasing concentrations of H2. For example, resistance may increase linearly with the square root of hydrogen in the PdNi lattice, which is related to the pressure of gaseous H2 as described by Sievert's law.

[0004] For a particular application, a gas sensor system may be designed to detect the pressure of a target gas, e.g., H2. However, in addition to the target gas pressure, there may be factors that affect the gas sensor measurement. For example, the temperature of the gas sensor may affect the measurement. To address this issue, a heater may be used to maintain the gas sensor within a desired temperature range. In addition to temperature, other factors may affect the gas sensor measurement, such as the bias voltage applied to the gas sensor or the overall pressure of the fluid environment. These measurements are also prone to errors due to baseline drift associated with aging or the presence of unwanted gases, as well as shifts in the sensor characteristics. For example, if a table were created that correlates the partial pressure of hydrogen with the resistance of the sensor (assuming that the resistance is associated with the same sensor temperature), over time these correlations will become less accurate, due to the previous example. Thus, making measurements based on this table will result in errors. One solution to this problem is to employ a system that performs calibrations and performs gas measurements at two different temperatures.

[0005] Non-target gases, such as O2, can also affect the measurements of gas sensors. The presence of non-target gases can affect or interfere with target gas measurements in at least two ways. First, the sensor may read too high or too low because the sensor is responding to both the target and non-target gases. In this regard, the effect of non-target gases can be thought of as an offset to the target gas reading. Second, the presence of non-target gases can change how the sensor measures the target gas. For example, non-target gases can occupy receptor sites within or on the surface of the lattice. This results in fewer available receptor sites, decreasing the sensitivity of the sensor to the target gas. As another example, in a PdNi gas sensor, the presence of oxygen in the lattice can affect the resistive or capacitive properties of the sensor. Thus, an oxygen-permeable lattice may respond to the presence of hydrogen in a different way than if the lattice was not permeable to oxygen. When oxygen permeates through the lattice, hydrogen adsorbs to produce molecules such as H2O and OH. These molecules, by themselves, can affect the resistive or capacitive properties of the gas sensor.

[0006] One attempted solution to reduce the effects of non-target gases may be to use a blocking coating on the gas sensor to filter such non-target gases. However, such filters may reduce the sensitivity or response time of the gas sensor. Another attempted solution may be to use multiple gas sensors to specifically detect non-target gases and determine and consider the concentration information of the non-target gases. However, such a solution may be expensive and / or increase the complexity of the system. Yet another attempted solution is to simply limit the application of gas sensing applications to those that do not contain interfering gases. A solution to the drift problem is to repeatedly manually recalibrate the drifting sensors.

[0007] For the above reasons, there is a need for a method and system for accurately and efficiently measuring gas concentrations that provides continuous or minimally interrupted readings while maintaining or exceeding the accuracy, response time, and precision requirements for hydrogen measurement and hydrogen monitoring applications, as well as providing benefits including, but not limited to, reducing or eliminating the need for calibration requiring a reference gas. Summary of the Invention

[0008] The present invention relates to methods and systems that can efficiently and accurately measure gas concentration or gas content in a fluid environment. The methods and systems include the use of devices and techniques that take measurements at different temperatures, take measurements during transitions between a first temperature and a second temperature, take more frequent measurements, detect when a gas sensor has reached equilibrium, use multiple sensors, account for offset and drift, reduce the time a sensor is not live, use algorithms or combinations thereof. As a result, the systems and methods of the present application reduce or eliminate the need for periodic calibration in some hydrogen measurement and hydrogen monitoring applications, physically achieve the accuracy, response time and precision of current hydrogen measurement and monitoring products, and reduce or eliminate gaps in hydrogen reporting. [Brief description of the drawings]

[0009] [Figure 1] This is an embodiment of the present invention. [Diagram 2] We show an equilibrium detector that flags stable points in the data. [Figure 3A] The principle of operation is shown when using two gas sensors, where a multi-temperature (MT) sensor (a sensor used at two temperatures) can send corrections towards a single-temperature (ST) sensor (a sensor used at one temperature) and the ST sensor can send stability information back to the MT sensor. [Figure 3B]1 shows a flow diagram of a method for measuring gas concentrations using a two gas sensor system, where a first gas sensor is used at a single temperature and a second gas sensor is used at two temperatures. [Figure 3C] The state machine for dual temperature sensor operation is shown, where LT is the "low temperature state", ELT is the "end of low temperature state", HT is the "high temperature state", and EHT is the "end of high temperature state". [Figure 3D] An example of dual sensor operation is shown. [Figure 4A] 1 shows resistance measurements of a gas sensor exposed to multiple hydrogen gas concentrations, where the temperature of the resistive sensing element is modulated by a sine wave throughout the test. [Figure 4B] 4B shows the amplitude frequency response associated with the resistance measurement of FIG. 4A. [Figure 4C] 4C shows hydrogen as a function of amplitude frequency response from FIG. 4B. [Figure 4D] The hydrogen concentrations calculated on the data from FIG. 4B using the calibration table in FIG. 4C are shown. [Figure 4E] The accuracy of overall hydrogen concentration measurements using the thermal sine wave operating method shown in Figures 4A and 4B is shown. [Diagram 5] The principle of two sensor operation is shown, where each sensor operates in MT mode and the temperature transitions are staggered so that one sensor is always live. [Figure 6A] Two isotherms are shown associated with a gas sensor operating at two temperatures, each isotherm being defined by a piecewise calibration. [Figure 6B] The difference between the two isotherms shown in Figure 6A and how the Delta-R measurements can be examined to generate a hydrogen reading. [Figure 6C] A comparison of hydrogen measurement performance on the same data set is shown. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The detailed description set forth below with reference to the accompanying drawings is intended to be a description of the presently preferred embodiments of the invention, and is not intended to represent the only forms in which the invention may be constructed or utilized. The description sets forth the functions and sequences of steps for constructing and operating the invention with reference to the illustrated embodiments. However, it will be understood that the same or equivalent functions and sequences may be accomplished by various embodiments that are intended to be encompassed within the spirit and scope of the invention.

[0011] The present invention is directed to a system and method for determining a target gas concentration in a fluid environment, such as a hydrogen concentration in the fluid environment, by measuring a change in an electrical characteristic of a gas sensor at at least two different temperatures, as disclosed in U.S. Provisional Application No. 62 / 830,182, filed April 5, 2019, which is incorporated herein by reference in its entirety. The measurement of the electrical characteristic of the gas sensor at two different temperatures can be used to calculate the gas concentration or can be used to calibrate or correct the measurement of the electrical characteristic of the gas sensor at a single temperature. Preferably, the system and method can determine the gas concentration continuously without loss of accuracy. By way of example only, the system may include a gas sensor as described in U.S. Patent Application No. 14 / 624,400, filed February 17, 2015, which is incorporated herein by reference in its entirety. Referring to FIG. 1, in some embodiments, the sensor tube includes a gas sensor, which includes a die having a gas resistor, a temperature resistor, and a heater, and two gas sensors are connected to each electronics set. The gas resistor may be a hydrogen resistor. Methods for measuring gas concentrations include a variety of techniques, as described below, which can be used alone, or in any combination thereof, to improve the accuracy of measuring gas concentrations in a fluid environment.

[0012] Ability to calculate gas transients at two temperatures One method for improving the measurement of gas concentrations in a fluid environment is to monitor the system response (how the electrical characteristics of the sensor (output) change as a function of sensor temperature and environmental conditions (inputs)) by dynamically measuring the electrical characteristics (current, voltage, capacitance, resistance, etc.) of the gas sensor while it is changing between two different temperatures. This two temperature operation involves the gas sensor being at a first temperature for a first period of time, transitioning to a second temperature for a second period of time (first transition period), being at the second temperature for a third period of time, and transitioning back to the first temperature for a fourth period of time (second transition period).

[0013] Alternatively, the gas sensor may transition to a third temperature for a fourth period (second transition period). The third temperature may be the same as the first temperature, or the third temperature may be different from the first temperature. Preferably, if the second temperature is an increase in temperature from the first temperature, the third temperature is a decrease in temperature. Conversely, if the second temperature is a decrease in temperature from the first temperature, the third temperature may be an increase in temperature from the second temperature. Thus, the change in temperature may follow a waveform, but the amplitude and period need not be the same.

[0014] During the transition period, the electrical properties of the gas sensor are also in a transient state, and are referred to as a transient electrical response, or simply a transient response. For example, a gas sensor may have a transient resistance response to changing temperature, which can be analyzed to calculate a live hydrogen reading, even during an unstable transient response. This can be done by analyzing the amplitude and / or phase of the response. The system response may include a transient response, or it may be a response without a transient, such as when a change in temperature causes a Pd sensor to change resistance immediately, just as any resistor changes resistance with temperature. This can also cause instability in the Pd sensor when hydrogen is present, as hydrogen must slowly migrate in and out of the lattice to reach a new equilibrium state, resulting in secondary effects that are time-dependent.

[0015] The transient electrical response can be highly dependent on the coatings on the die, especially their hydrogen resistance. Multiple coatings / passivation layers are used on various elements of the die, such as between the palladium-nickel grid and the environment. Coatings are therefore selected for their permeability to hydrogen so that the transient response can be more easily used to calculate hydrogen concentration. Coatings impede the transfer of hydrogen from the measurand to the sensor or from the sensor to the measurand, so they introduce a delay (i.e., add a time constant) and affect the transient response. Coating thickness, coating density, and many other parameters that are loosely or tightly controlled affect that time constant. A delay or change in the transient time can help identify the presence or lack of hydrogen. For example, if hydrogen is present, there can be an overshoot or undershoot in the step response of the hydrogen sensor with a change in die temperature. Due to hydrogen equilibrium, the balance between the sensor element (e.g., palladium-nickel sensor) and the surrounding hydrogen is disrupted and it can take a while for the system to reach equilibrium (i.e., when the measurement is stable). In other words, the lattice that can be reached has an equilibrium resistance or steady state behavior (e.g., the resistance that the gas sensor reaches given enough time, assuming the partial pressure of hydrogen and the temperature of the gas sensor remain constant), which is a function of the partial pressure of hydrogen in the surrounding environment. Changes in the partial pressure of hydrogen in the environment will not be translated into a lattice instantly, but will take time to reach a new equilibrium based on the sensor temperature, the dielectric constant of the coating, etc. This time can be minutes to hours. The time it takes the system to reach equilibrium can be controlled and used to advantage in measuring as well as classifying the environment. For example, the more hydrogen in the sensor, the longer it will take to reach equilibrium. By calibrating the transient response to known hydrogen concentrations, a model (such as the sinusoidal model described herein) can be developed that measures hydrogen as a function of the measured transient response.

[0016] Repeated heat waveform function Rather than simply varying the temperature of the sensor from a first temperature to a second temperature, the temperature of the gas sensor is kept at a constant state of change. Preferably, the temperature of the gas sensor can be varied repeatedly in a pattern called a repeating thermal waveform. In this manner, the electrical characteristics of the gas sensor can be at a constant system response to a repeating thermal waveform, such as a sine wave. By constantly monitoring and measuring the transient response, the amplitude and / or phase of the transient response can be measured using a short-time Fourier transform (STFT) or wavelet analysis. The concentration of hydrogen affects the transient response, so the frequency response can be used to measure hydrogen. This frequency response includes an amplitude frequency response and a phase frequency response. A table with an interpolation or regression function is created using several calibration points that relate the amplitude, phase, or both of the frequency response to the hydrogen concentration. The amplitude frequency response is the amplitude of the spectrum of frequencies related to the electrical characteristics in response to the excitation. The phase frequency response is the phase of the spectrum of frequencies related to the electrical characteristics in response to the excitation. As an example, a spectrum can be generated by recording data of the electrical characteristics of the response by sampling said data at a rate (sample frequency) over a period of time defined by the total number of samples (window length) and generating a discrete Fourier transform (DFT) using a fast Fourier transform (FFT) algorithm. The process of performing a Fourier transform on a short segment in time of the signal is called a short-time Fourier transform (STFT). The sample frequency and window length can be selected based on the desired bandwidth, spectral resolution, processing delay, etc.

[0017] In a conventional multi-temperature sensor, the transition from one temperature to another causes a disruptive transient response that makes the hydrogen measurement inaccurate for a period of time after the transition. It is very difficult to factor in the hydrogen concentration with a disruptive transient response. In a system that uses a repetitive thermal waveform approach, the system is always in a known and controlled thermal transient response and therefore the system can be characterized from the nature of the repetitive thermal waveform. Although the system can be nonlinear, when modulated with a repetitive thermal waveform to excite the system, the amplitude and phase delay of the transient response can be related to the concentration of hydrogen.

[0018] Preferably, the sinusoidal excitation has a single frequency, making characterization of the system response in the frequency domain mathematically simpler than characterization of other repetitive waveforms that contain multiple frequencies. It has been observed that the system response to a thermal sine wave is nonlinear, so the response contains multiple frequencies. The use of multiple sinusoidal frequencies for excitation is described below, but the frequency associated with each sine wave must be carefully selected. Having a system response that contains multiple frequencies from a single frequency excitation is preferable to a system response to an excitation with multiple frequencies, because each frequency component of the excitation will give rise to multiple frequency responses at the output, resulting in a complex mix of frequencies in the response. For example, a repetitive waveform that induces a step change in temperature will result in a system response that theoretically contains an infinite number of sine waves, complicating the model implemented for hydrogen calculated as a function of the response. An example of the resistance response of a gas sensor excited by a thermal sine wave at multiple hydrogen concentrations is shown in FIG. 4A. In this example, the period of the sine wave is 8 minutes, and the amplitude of the thermal waveform ranges from 50°C to 150°C. The hydrogen concentrations shown in FIG. 4A-4D are volumetric concentrations in absolute values ​​at 1 atmosphere with a nitrogen background gas.

[0019] A model utilizing a calibration table based on the system response can produce the benefit of baseline drift removal for multi-temperature systems without the negative downtime aspect of being unable (or at least very difficult) to accurately calculate hydrogen during transients due to temperature transitions. For example, by using a STFT of the transient response with a window length equal to the number of samples contained in one period of the repeating thermal waveform, in this example a sine wave (8 minutes), the amplitude associated with the fundamental frequency of the excitation can be measured over time. FIG. 4B shows an example of this calculation based on the transient response, which is the resistive response shown from FIG. 4A. A transfer function or calibration table can then be created that relates gas concentration to frequency response (such as amplitude frequency response and / or phase frequency response). FIG. 4C shows a calibration table for hydrogen generated based on the amplitude frequency response data from FIG. 4B. Using this model (FIG. 4C), the data from FIG. 4B can be used to generate a hydrogen reading. This is shown in FIG. 4D.

[0020] The long-term accuracy of this model can be affected if the fundamental system response changes. For example, foreign material depositing on the sensor will slow the response time, effectively changing the sensor characteristics. Without some way to account for this, the accuracy of the hydrogen readings will decrease. (See the decrease in accuracy across multiple hydrogen concentrations shown in Figure 4E). Also, while there are no gaps in the hydrogen calculations due to temperature transitions, changes in hydrogen concentrations that share frequency components with the fundamental frequency of excitation will affect the hydrogen calculations and cause unwanted spikes in the readings. Therefore, when these transitions occur, it may be beneficial to add additional filtering and / or other signal processing techniques, such as masking the hydrogen readings until the environment stabilizes to minimize or eliminate these spikes. This effect can be observed in Figure 4D, where large spikes can be seen in the hydrogen readings as the applied hydrogen concentration transitions from one value to another. Additional filtering and signal processing (including masking) can be used to minimize or eliminate these spikes.

[0021] There are several approaches to using this model to correct for changes in the system response (i.e., changes in the time constant) for single sensor applications. One method would allow the end user to apply known partial pressures of gas (e.g., hydrogen) to the sensor and allow the instrument to generate several frequency responses, and use this data to mathematically add corrections to the existing frequency response calibration table. This can be repeated with additional known partial pressures of hydrogen for greater accuracy. It is assumed that this manual calibration is performed less frequently than a single temperature sensor to maintain hydrogen measurement performance. Another method would allow the instrument to switch, either automatically or triggered externally, to the two temperature method of operation. This method would allow accurate hydrogen readings to be captured. The instrument would then switch back to the thermal repeat waveform, obtain a new frequency response, and mathematically add corrections to the existing frequency response calibration table. One assumption is that the partial pressure of hydrogen to which the sensor is exposed is constant throughout this process. Another assumption is that this process is performed conservatively and, in some applications, provides preferred performance over sensors utilizing only the two temperature method. While there may still be gaps in the hydrogen readings during switchover to the two temperature method of operation, these gaps will likely be infrequent compared to the two temperature method of operation, or may be caused when there is an acceptable time to have gaps in the hydrogen readings.

[0022] There are several ways to reduce or eliminate the effect of hydrogen transitions that contain frequency components in the sensor response. As mentioned before, when using a calibration table of amplitude frequency response (Figure 4C), these shared frequency components cause large errors in the hydrogen calculation (shown in Figure 4D). One approach to reduce this effect would be to simply mask the final hydrogen calculation when a large change in the hydrogen calculation is detected. The drawback is that there will be gaps in the readings, especially when the partial pressure of hydrogen around the sensor is more dynamic. An alternative approach is to use multiple sine waves at specific target frequencies, amplitudes, and phases to regulate the temperature of the sensor. The final repeating thermal waveform is composed of the superposition of each sine wave, i.e., the waveform is defined as a sum of sine waves, each of which can be described by its amplitude, frequency, and phase. The system response to this waveform is composed of the superposition of the system response (output) to each sine wave that makes up the thermal waveform (input). If the frequencies of the thermal waveform inputs are well separated (meaning there is a low frequency waveform and a high frequency waveform), the output corresponding to each input frequency can be distinguished using common signal filtering techniques such as bandpass or notch filtering. To calculate hydrogen, each frequency has a corresponding frequency response calibration table. Lower frequency excitations have been found in experiments to have better resolution in hydrogen measurements, but they share more frequency components with hydrogen transitions, resulting in larger errors during transitions. If multiple frequencies are used, the instrument can switch to using data from a higher frequency excitation when a transition is detected by analyzing the stability of the frequency response of the lower frequency excitation. Once the system is determined to be stable again, the instrument will switch to using data from the lower frequency excitation.

[0023] The disadvantage of using multiple excitation frequencies in a thermal repetitive waveform is that the total energy of the system response must be conserved and shared across all resulting frequencies. The resulting frequency response corresponding to each frequency contains only a fraction of the signal energy of the frequency response of a single-frequency (single sine wave) excitation. This reduces the signal-to-noise ratio (SNR) of the final hydrogen calculation. The signal energy can be increased by increasing the temperature change (amplitude, or maximum and minimum temperatures) of the thermal excitation. However, this is limited by physical factors (maximum temperature of the material, environmental temperature, etc.).

[0024] By way of example only, the temperature change may range from about 30 degrees Celsius to about 180 degrees Celsius. Preferably, the temperature change ranges from 35 degrees Celsius to about 180 degrees Celsius. More preferably, the temperature change ranges from 40 degrees Celsius to about 180 degrees Celsius. Experiments have shown that the greater the change in temperature (sine wave amplitude), the greater the sensitivity to hydrogen using the amplitude frequency response. This makes it easier to distinguish the partial pressure of hydrogen and results in less noise in the final calculation. However, because the sensor response to hydrogen is a function of temperature (the time constant of the system decreases as the temperature increases), the system response is distorted. That is, when the sensor is excited using a thermal sine wave, the phase of the resistance to a constant applied hydrogen is not constant. The phase delay increases during the trough of the sine wave (temperature is at its lowest value) and the phase delay decreases during the peak of the sine wave (temperature is at its highest value). Additionally, the sensitivity of the sensor is a function of the sensor temperature. The result of these effects is a distortion of the thermal sine wave used for excitation, consisting of multiple harmonics in the resistive response.

[0025] The system may include a control loop and a feedback loop to control the temperature cycle. In the sinusoidal method, the control loop constantly tracks a sine-shaped time wave. A temperature sensor measures the temperature of the die, and the temperature measurement is fed into a digital control loop. The heater can be adjusted so that the correct heat is output to achieve the desired temperature of the gas sensor. The heater can be controlled by a controller to utilize constant transients, so any waveform can be used, including sawtooth, square, or random waveforms.

[0026] In some embodiments, the period of the waveform may not be fixed. In some multi-temperature embodiments, the repeating waveform does not have a fixed period. In some dual temperature embodiments, the repeating waveform may or may not have a fixed period. In some embodiments, the amplitude, phase, waveform, and period may not be consistent over time. While there are several applications for sine waves, when the system is driven from a heater and the gas environment to which the hydrogen sensor is exposed is measured, different tools can be used to analyze the response.

[0027] In a linear system, when excited with one frequency, the output contains only the same single frequency. Because the system of the present application is nonlinear, when one frequency goes in, multiple frequencies come out (response). Thus, the present invention utilizes a pure sine wave to induce a response in the hydrogen sensor, which may include multiple frequencies of different amplitudes and phases, and low amplitude and low power, but said changes will be diagnostic of the hydrogen concentration. However, the fundamental frequency of the hydrogen sensor will follow the frequency of the temperature change (system excitation) and its amplitude must be related to its original waveform, the driving waveform. Because the system is nonlinear, harmonics at higher frequencies will also be displayed, but the fundamental frequency will match the fundamental frequency (lowest frequency component) of the temperature regulation. Such a system will not have a gap during a temperature transient where the gas concentration cannot be calculated. Thus, while a conventional gas sensor takes several minutes to respond to a change in temperature and then waits a minute or more before another live hydrogen reading is taken, in a sine wave system, the gas measurement is live and can be made continuously because the temperature of the sensor is continuously regulated by the thermal waveform. Thus, hydrogen can be measured continuously. In other words, measurements are taken within seconds, as opposed to regular hydrogen measurements, which can have gaps of an hour or more between measurements.

[0028] An important aspect is the distinction between forcing a thermal waveform on the die and observing the response of the hydrogen resistance. In the absence of hydrogen, the hydrogen resistance response can be a time- and frequency-scaled replica of the driving waveform. There is little shift or distortion. If the gas sensor is placed in a hydrogen environment, differences in the waveform are seen. Those differences are related to the time constant for hydrogen to pass through the coating layer or for the hydrogen sensor to reach equilibrium with its environment. As the temperature of the Pd matrix changes, hydrogen is forced in and out of the lattice and through the coating. The rate at which hydrogen passes through the coating and the rate at which the hydrogen resistance reaches equilibrium with its environment can be exploited. All of these physical processes take time. Some of them are very fast, while others are within the operating frequency used for the measurement. The amplitude and phase frequency response of the sensor when some hydrogen is applied depends on the behavior of the system, which also determines the time constant. A calibration table can be generated based on this information.

[0029] Having two different temperatures at which hydrogen concentration measurements can be made allows for calculations or measurements with minimal or no drift or offset. However, using a sinusoidal temperature waveform, the hydrogen concentration can be read live and continuously with minimal or no drift, taking into account the environmental conditions discussed above. Thus, the hydrogen concentration measurement can be determined in real time, and the measurement can be determined with minimal or no gaps due to response to temperature transients. With conventional sensors, a reliable measurement is determined at the end of a period to allow time for the system to reach equilibrium. In such cases, a means of determining whether the sensor has reached equilibrium is required. Using a sinusoidal waveform eliminates the need for the gas sensor to reach equilibrium before the gas concentration measurement can be determined.

[0030] Thus, in some embodiments, a method for determining a target gas concentration in a fluid environment includes exposing a gas sensor to the fluid environment, the gas sensor having an electrical characteristic that varies as a function of the target gas concentration, modulating a temperature of the gas sensor, the modulation being in the form of a repetitive thermal waveform that induces a system response in the electrical characteristic (e.g., a transient response), monitoring the electrical characteristic during the step of modulating the temperature of the gas sensor, and calculating the target gas concentration as a function of a frequency response of the electrical characteristic of the gas sensor. The frequency response may be an amplitude frequency response of the electrical characteristic, a phase frequency response of the electrical characteristic, or both the amplitude frequency response and the phase frequency response of the electrical characteristic.

[0031] Preferably, the repetitive thermal waveform is a sinusoidal wave. In some embodiments, the repetitive thermal waveform is generated by a single frequency sinusoidal excitation. In some embodiments, the repetitive thermal waveform is generated by a plurality of superimposed sinusoidal frequencies, each sinusoidal frequency having a corresponding frequency response calibration table (e.g., amplitude frequency response and / or phase frequency response). The plurality of sinusoids includes a first set of sinusoidal waves having a first set of frequencies and a second set of sinusoidal waves having a second set of frequencies (each set of sinusoidal waves having a frequency response calibration table, such as an amplitude frequency response calibration table and / or a phase frequency response calibration table), the first set of frequencies is lower than the second set of frequencies (i.e., the frequency values ​​or range of frequency values ​​in the first set is lower than the frequency values ​​or range of frequency values ​​in the second set), and the calculation of the target gas concentration is based on the frequency response (e.g., the amplitude frequency response and / or the phase frequency response) of the first set of frequencies or one of the second set of frequencies. For example, the target gas concentration can be based on the first set of frequency responses or the second set of frequencies. In other words, the frequency response for a set of frequencies can be filtered out. A cutoff between low and high frequencies can be determined to improve the accuracy of the gas measurement or calculation.

[0032] A calibration table based on the system response can be generated. Preferably, the calibration table is generated by correlating gas concentrations with frequency responses (e.g., amplitude frequency response, phase frequency response, or both) measured using a short-time Fourier transform of the system response. The table can be used to generate hydrogen readings that do not degrade over time in specific environmental conditions.

[0033] In some embodiments, the shift in system response is corrected by applying a known partial pressure of the gas to the sensor, allowing the sensor to generate a second frequency response (e.g., an amplitude frequency response, a phase frequency response, or both), and applying a correction to the calibration table based on the second frequency response.

[0034] In an embodiment, the calibration table can be modified by enabling the sensor to generate a second frequency response, changing an operational mode of the gas sensor to operate at two temperatures, alternating a temperature of the gas sensor between a first temperature and a second temperature while the gas sensor is exposed to a fluid environment, allowing the temperature of the gas sensor to remain at the first temperature for a first period of time, transition from the first temperature to the second temperature for a second period of time and remain at the second temperature for a third period of time, monitoring an electronic characteristic of the gas sensor during the second and fourth period of time, calculating a gas concentration as a function of the electronic characteristic, and calculating a correction based on the second frequency response and the calculated gas concentration.

[0035] The systems and methods described herein can be used to calculate gas concentrations continuously and in real time.

[0036] Balanced detector function In some embodiments, to achieve accurate gas concentration readings, the environment must be stable and the sensor system must be at equilibrium. However, the amount of time spent at a constant temperature (the first and third periods above) can be variable based on the equilibrium state of the sensor. Thus, the time spent at a temperature depends on the system and the environment reaching equilibrium, which is unknown. Conventional systems are time-based and use multi-temperature operation for auto-calibration, and in order to calculate an accurate calibration, the sensor measurements corresponding to each sensor temperature must be at equilibrium, but it is not known whether the system and environment have reached equilibrium. A multi-temperature modality auto-calibration is performed to generate a potential calibration for the sensor. If the environment was not at equilibrium, or if the sensor was not at equilibrium in response to the temperature change of the sensor, the calibration would be inaccurate. Therefore, it is necessary to determine whether the results of the calibration make sense and, if necessary, whether the calibration is accepted or rejected. In other words, a determination is made, in part or in whole, after the sensor measurement data is obtained, as to whether the calibration calculated from the sensor measurement data is accurate. If the calibration is deemed inaccurate, the sensor measurement data is not used and the calibration must be retried. With this approach, there are often periods when the system has been stable for a very long time and a multi-temperature equation measurement may occur sooner than scheduled. Other times, the system has not stabilized for a long time, but a temperature transition is scheduled just before equilibrium is reached, effectively wasting an attempt to obtain a measurement. Using an equilibrium detector eliminates the decision factor of obtaining data after a sensor measurement by first determining if the system and environment have reached equilibrium before taking a measurement at one temperature and moving to the next, ensuring that the calibration is accurate and no time is wasted.

[0037] Currently, whether the system has reached equilibrium is time-based. The time it takes the system to reach equilibrium in response to temperature changes in the sensor is fixed and set to have enough time for most sensors to reach equilibrium. This fixed time is based on experimental data. However, environmental changes can make the readings unstable and the system needs more time to stabilize, but this information is not strictly used in the current implementation.

[0038] While the heating element of the gas sensor may drive the temperature, regulation of the die temperature is from a temperature sensor on the die, and a portion of the die is maintained at a particular temperature, which may not be the same temperature for all portions or phases of operation, but typically goes through a particular sequence. Thus, to obtain a complete cycle of the multi-temperature system and perform measurements, the sensor may be at one temperature for a first period and transition to a second temperature for a second period, during which the existing program may reschedule the temperature periods if instability is detected. Such instability may include a large change in the environmental temperature, or a large change in the measured electrical characteristic of the sensor, a threshold value for said parameter determined by experiment. For example, the system may repeat a third period at the second temperature when the first period at the first temperature is normally scheduled, in order to quickly obtain sensor measurement data related to the second temperature condition. This may be performed so that the autocalibration can be calculated sooner, rather than proceeding through all the periods normally scheduled (a fourth period to transition to the first temperature, a second period to transition to the second temperature, and finally a third period at the second temperature may be repeated). These control points are therefore fixed in timing in conventional systems.

[0039] However, more adaptive balance detectors offer some unique characteristics and help eliminate unknown timing factors. For example, the balance detector can indicate the state of hydrogen resistance. In the present invention, a PID type heater control loop is used to vary the temperature of the sensor. The balance detector determines whether the gas sensor has reached equilibrium as well as the environment in which the sensor is set has reached equilibrium in response to temperature changes. The manner in which equilibrium is determined is based on physical measurements such as temperature, resistance, power to heat the sensor, as well as more advanced information such as the hydrogen reading calculated using a model that the sensor is using and the parameters that generate said hydrogen reading within the model. These characteristics can be statistically analyzed and processed using techniques such as filtering or averaging, and calculation of variance (or related metrics). These metrics can be updated as new data is ingested and additional metrics such as change over time (first derivative), change over time (second derivative), etc. are created. The thresholds for these metrics are determined experimentally and depend on the accuracy requirements of the desired application.

[0040] For example, the temperature of the gas sensor die may be changing, or the gas concentration of the environment may be changing. To know if the sensor is at equilibrium, a firmware routine checks the metrics above and determines if the sensor is at equilibrium based on empirically determined thresholds. Figure 2 shows an example of an equilibrium detector that determines when the sensor reaches equilibrium after a change in hydrogen as well as a change in sensor temperature.

[0041] Thus, in some embodiments, a system and method for determining a target gas concentration in a fluid environment includes exposing a gas sensor to the fluid environment, the gas sensor having an electronic characteristic that varies as a function of the target gas concentration, alternatingly controlling a temperature of the gas sensor between a first temperature and a second temperature while the gas sensor is exposed to the fluid environment, where the temperature of the gas sensor remains at the first temperature for a first period of time, transitions from the first temperature to the second temperature for a second period of time, remains at the second temperature for a third period of time, transitions from the second temperature to the third temperature for a fourth period of time, continuously monitoring an electrical characteristic of the gas sensor during the second and fourth periods of time, and calculating the target gas concentration as a function of a system response (e.g., a transition response) in the electrical characteristic of the gas sensor measured during the second and fourth periods of time as the temperature transitions between the first and second temperatures. To further improve the accuracy of the readings, the system can determine whether the gas sensor has reached equilibrium using an equilibrium detector.

[0042] 2 sensor function In some embodiments, rather than having one gas sensor that changes temperature, two gas sensors can be used in parallel. In some embodiments, the hydrogen reading of the two-temperature sensor is interrupted every time the sensor switches temperature. Because it uses a multi-temperature equation, its accuracy does not degrade over time, but there may be gaps in the readings to accommodate for temperature transitions. Instead, a single-temperature sensor (with no temperature transitions at all) can be used, which has a live reading (e.g., approximately 1 sample / second in the present invention) but from which it gets an accurate hydrogen reading every time the second sensor goes through a temperature cycle, which can be anywhere between once an hour and once every few days, to correct for any baseline sensor drift. The assumption is that the accuracy of the single-temperature sensor will not degrade beyond the application's specifications before the two-temperature / multi-temperature sensor can send a correction to it.

[0043] The first sensor operates at a single temperature (single temperature sensor) so that it can measure hydrogen at all times without interruption. The second sensor calculates hydrogen using a two-temperature method (two-temperature sensor) by being at the first temperature for a first period of time, transitioning to the second temperature for a second period of time, at the second temperature for a third period of time, and transitioning back to the third temperature for a fourth period of time. The third temperature can be the same as the first temperature, or a different temperature. The second sensor can take into account drift over time (due to instability, oxidation, interfering gases such as CO or H2S), but only has intermittent but reliable hydrogen measurements, and the second sensor can pass these measurements to the first sensor as a calibration. In other words, as each auto-calibration is completed, information is fed forward from the second sensor to the first, "live" sensor.

[0044] FIG. 3A shows an example of output from a two-sensor embodiment, with a first sensor (lower curve) representing a hydrogen concentration reading and a second sensor (upper square wave) representing the results of a gas sensor employing a two-temperature method, the results of the second sensor being used to calibrate the output of the first sensor. FIG. 3A shows the ST sensor indicating that hydrogen is stable (1) and the MT sensor beginning to cycle its own temperature. When this temperature cycle is complete, the ST sensor indicates that hydrogen is stable (2). The correction is blended into the hydrogen reading of the ST sensor (3). When the process repeats, the ST sensor indicates that hydrogen is stable (4) and the MT sensor begins to cycle its temperature again. If the ST sensor indicates variability in hydrogen concentration (5), the MT sensor cancels the cycle and returns to the baseline.

[0045] FIG. 3B shows a flow diagram illustrating the process. When the process begins, the system determines whether the first and second gas sensors are in equilibrium. If not, the system waits and continues to check whether both sensors have reached equilibrium. If both gas sensors reach equilibrium, the hydrogen concentration reading of the first gas sensor (single temperature sensor) is recorded, while the resistance (or some other electrical property) of the second gas sensor (two temperature sensor) is recorded. Next, the time since the gas sensor was last in equilibrium is determined, and if the time since last equilibrium for the gas sensor is greater than a predetermined time, any previous readings are invalidated. Then, the second gas sensor is changed to another operating temperature (i.e., to the second temperature if it was previously operating at the first temperature), and the process repeats again to determine whether the sensor is in equilibrium. If there are valid readings from a full cycle (the second gas sensor has recorded readings from each of the two temperatures, and the first sensor has recorded hydrogen readings associated with each of the two temperatures for the second gas sensor), calculation of a correction can begin. First, the change in gas concentration (e.g., percent change in hydrogen concentration) from the previous reading of the first gas sensor is calculated. Then, the change in the electrical property (e.g., resistance) of the second gas sensor corresponding to the change in gas concentration of the first sensor is calculated. The second gas sensor can then calculate the concentration of hydrogen associated with the most recent sensor temperature based on the change in resistance due to the change in temperature of the second gas sensor and the change in hydrogen recorded by the first gas sensor. This concentration of hydrogen calculated by the two temperatures is considered to be more accurate than the hydrogen concentration calculated by the single temperature sensor. The difference between the single temperature sensor and this reading, if any, is considered to be the error in the single temperature sensor. A correction factor is calculated to counter this error in the single temperature sensor reading and blended into its own hydrogen reading. A second gas sensor is switched to the other operating temperature and the process is repeated.

[0046] 3C, when the second gas sensor reaches the end of the low temperature state (ELT) as determined by the equilibrium detector, it is transitioned to the high temperature state (HT). The end of the high temperature state (EHT) is again determined by the equilibrium detector, it is transitioned back to the low temperature state (LT) and the process repeats.

[0047] FIG. 3D shows the experimental data for this process. FIG. 3D contains three sets of data: a live hydrogen calculation for the two-temperature sensor (MT sensor readings), a hydrogen calculation for the two-temperature sensor (calculated) using the multi-temperature equation, and a live hydrogen calculation for the single-temperature sensor. The sensor was exposed to multiple hydrogen concentrations (5% H2 / N2, 2% H2 / N2, 5% H2 / N2, then 1% H2 / N2, all at 1 atmosphere absolute pressure). Looking at the live hydrogen calculation for the two-temperature sensor (MT sensor readings), spikes in the readings are seen from time to time. These spikes are the result of temperature transitions and can last from minutes to hours depending on the sensor response time, the magnitude of the temperature change, and the hydrogen in the Pd lattice. It can be seen that the (calculated) hydrogen calculation from the multi-temperature equation for the two-temperature sensor is updated much less frequently than the live readings. Reading updates can only occur at the end of a two-temperature sensor temperature state, which can be seen in the figure using the aforementioned spikes as markers. As previously mentioned, these less frequent updates in hydrogen readings calculated from the multi-temperature equation are believed to be accurate and do not degrade over time. To benefit from this, when these calculations are updated, they are fed forward to the live single-temperature sensor readings (ST sensor readings). To allow the multi-temperature equations to be used when hydrogen concentration is changed between temperatures (associated with the two-temperature sensor), the single-temperature sensor must record the change in hydrogen that is associated with the resistance measurement used in the multi-temperature equations. This is described in more detail in the "Single-Temperature Sensor Feedback Function" section below.

[0048] Accordingly, in some embodiments, a system and method for determining a concentration of a target gas in a flowing environment includes exposing a first gas sensor to the flowing environment, the first gas sensor having an electrical characteristic that varies as a function of a target gas concentration; exposing a second gas sensor to the flowing environment, the second gas sensor having an electrical characteristic that varies as a function of a target gas concentration; and controlling a temperature of the second gas sensor alternately between a first temperature and a second temperature while the second gas sensor is exposed to the flowing environment, where the second gas sensor The method includes the steps of: remaining at the first temperature for a first period of time, transitioning from the first temperature to the second temperature for a second period of time, remaining at the second temperature for a third period of time, and transitioning from the second temperature to the third temperature for a fourth period of time; monitoring an electrical characteristic of the second gas sensor for the second and fourth periods of time; and calculating a target gas concentration as a function of the electrical characteristic of the first gas sensor, where data from the second gas sensor is used to correct for baseline sensor drift of the first gas sensor. Preferably, the first gas sensor operates at a single temperature.

[0049] A second sensor using a repeating thermal waveform The two sensor functionality described above can be combined with a repeating thermal waveform functionality, as previously described, such that instead of the second sensor implementing a two temperature approach, the second sensor can be in a constant state of temporal response to a repeating thermal waveform, such as a sine wave. The second gas sensor passes a correction to the first gas sensor to keep it calibrated.

[0050] Single temperature sensor feedback function In some embodiments, a single temperature sensor, a two-temperature sensor, or self-calibrating sensors working together can account for environmental changes. For example, a single temperature sensor can indicate a change in hydrogen if one occurs (e.g., by measuring it using resistance measurements and a calibration table), and can calculate a multi-temperature correction by understanding and quantifying the change. When the multi-temperature equation is valid, it is assumed that the resistance measurements associated with the two temperatures correspond to the same partial pressure of hydrogen. That is, if the partial pressure of hydrogen changes between the two measurements, the hydrogen calculation using the equation is inaccurate. However, over the period in which the two-temperature sensor records resistance at each of the two sensors, the single temperature sensor can track the change, if any, in the partial pressure of hydrogen. If any change is detected by the single temperature sensor, the two-temperature sensor can use its own calibration information to adjust one of the resistance measurements. A "corrected" resistance value is a resistance value adjusted to the value that it would have been if the hydrogen concentration had not changed. This value is only known because a two-temperature sensor is sensitive to temperature transitions and cannot track changes while a single temperature sensor can. Thus, data from one of the sensors can be used in other sensors, such as a first gas sensor reporting changes in the partial pressure of hydrogen detected at the first gas sensor to a second gas sensor.

[0051] In other words, the two-sensor method can be used with a second sensor that also uses the two-temperature method, but if the partial pressure of hydrogen changes between the equilibrium state of the second sensor at a first time period (Temperature 1) and the equilibrium state of the second sensor at a third time period (Temperature 2), the first sensor can pass on the magnitude of the change in partial pressure of hydrogen to the second sensor. This change can be compensated for using the sensitivity of the second sensor to hydrogen at one of the two temperatures, so that the second sensor can still perform an auto-calibration in such a way that drift can be removed (information is fed back from the first "live" sensor to the second sensor, allowing the second sensor to complete its auto-calibration despite changes in the environment). This is described mathematically as follows:

[0052]

number

[0053] X0 and Y0 are the hydrogen partial pressure readings of the ST sensor, which are related to the actual applied hydrogen partial pressure values ​​X and Y, respectively, and the offset C offset Additionally, X0 is the reading when the MT sensor was at temperature T2, and Y0 is the reading when the MT sensor was at temperature T1.

[0054]

number

[0055] where m T2 and b T2 are the sensitivities and offsets associated with the T2 isotherm, and m T1 and b T1 are the sensitivity and offset associated with the T1 isotherm. Furthermore, R T2 is the measured resistance related to the partial pressure X of hydrogen at temperature T2, and R T1Let be the unknown resistance associated with the partial pressure X of hydrogen at temperature T1.

[0056] These can be combined with the following multi-temperature equation to solve for X:

[0057]

number

[0058] lastly,

[0059]

number

[0060] where R′ is the actual measured resistance value acquired by the MT sensor at temperature T1 when hydrogen concentration Y is applied.

[0061] Taking the difference in partial pressure of the hydrogen reading at the ST sensor removes the offset and results in the following equation:

[0062]

number

[0063] The unknown X is solved for using only known values. Other isotherms can also be used to solve it in a similar fashion. Thus, the offsets cancel each other out.

[0064] Two dual temperature sensor functions In some embodiments, two sensors as described above can be used, but both sensors use a two-temperature hydrogen measurement method. The periods of each sensor are staggered or offset, so that the live sensor is always in the first period (Temperature 1) or the third period (Temperature 2), while the other sensor is in a transition period (second or fourth), as shown in FIG. 5. The live sensor alternates between the first gas sensor (upper square wave) and the second gas sensor (lower square wave) each time a transition occurs between their states. Therefore, when one sensor is going through a transient response, it is more difficult to calculate the hydrogen it fluctuates with, while the other sensor is in equilibrium. When the results of the readings of the two gas sensors are combined, a continuous gas concentration reading is shown (lower line).

[0065] Thus, in some embodiments in which the first gas sensor operates at two temperatures, the step of measuring the gas concentration further includes alternatingly controlling the temperature of the first gas sensor between the first temperature and the second temperature while the first gas sensor is exposed to the gas, where the temperature of the first gas sensor remains at the first temperature for a first period of time, transitions from the first temperature to the second temperature for a second period of time, remains at the second temperature for a third period of time, and transitions from the second temperature to the third temperature for a fourth period of time; where the temperatures of the first gas sensor and the second gas sensor are staggered such that the first gas sensor is in the first period or the third period of time of the first gas sensor, and the second gas sensor is in the second period or the fourth period of time of the second gas sensor. In other words, when the first gas sensor is in its first period, the second gas sensor is in its second period (transition period), and when the first gas sensor is in its second period (transition period), the second gas sensor is in its first period (or third period).

[0066] Secondary isotherm function In some embodiments, a two-temperature method can be used, but instead of using lines to describe the resistance as a function of hydrogen at each isotherm, a second order polynomial is used. As mathematically described below, the two temperatures (c T1 and c T2 ) can be removed, and the resistance (R T1 and R T2 ) has three coefficients aT1 and a T2 , b T1 and b T2 , and cT1 and c T2 is the given quadratic function.

[0067]

number

[0068] Then, the equations are linearly subtracted.

[0069]

number

[0070] Solving for the partial pressure of hydrogen (√H2), we get two solutions:

[0071]

number

[0072] The solution that is closest to the operating region of the isotherm is shown below (other solutions give negative or excessively large hydrogen partial pressure calculations, despite the dip in the isotherm):

[0073]

number

[0074] Piecewise linear isotherm function The sensitivity of a system refers to how effectively the resistance (or other electrical property) of a gas sensor changes with hydrogen content. The sensitivity of a sensor is not necessarily constant throughout the entire range of hydrogen contents. A gas sensor may have different sensitivities when exposed to different hydrogen contents. Therefore, it is useful to take into account the changing sensitivity based on the hydrogen content of the tested environment.

[0075] Factors that affect the sensitivity of a gas sensor include the composition of the sensor (e.g., the ratio of palladium / nickel) and the temperature of the gas sensor. The more palladium in the sensor, the greater the resistance change with respect to hydrogen; thereby, the more sensitive the gas sensor. In addition, the lower the temperature, the more sensitive the gas sensor. The palladium content and the operating temperature can be determined based on the performance requirements of the product application.

[0076] The two temperature method is enabled by the use of two isotherms, sensitivity and altitude difference (resistance as a function of hydrogen partial pressure at a given temperature), based on the partial pressure of hydrogen the sensor is measuring, and can give the best information available, i.e., for concentrations between X0 and X1, use sensitivity and altitude difference A0, for concentrations between X1 and X2, use sensitivity and altitude difference A1, etc. across the full range of hydrogen.

[0077] 6A to 6C, ΔR(RT2-RT1) is within the range of R' in Region 3:

[0078]

number

[0079]

number

[0080]

number

[0081] The standard multi-temperature equations shown above still apply, but the value G 3_T1 , G 3_T2 , R base_3T1 , and R base_3T2 Every ΔR(R T2 -R T1 ) fall into different domains, the aforementioned variables associated with that domain will be used. These variables are determined during calibration.

[0082] As shown in FIG. 6B, ΔR(R T2 -R T1 The difference of the isotherms can be taken to determine within what region ) falls.

[0083] Figure 6C shows a comparison of various methods of interpolating the isotherm, as well as a comparison against a calibration table of a single temperature sensor using a piecewise linear fit. It is observed that using standard linear regression for the isotherm can result in much larger errors in the model, compared to using piecewise linear regression (as shown in Figure 6B) or quadratic regression (quadratic polynomial regression).

[0084] Piecewise quadratic isotherm function Another feature of the present invention is the use of a second order polynomial isotherm, but with different sets of coefficients used for different hydrogen regions, as described in the piecewise linear isotherm section.

[0085] General nonlinear calibration function The isotherms can be written as nth order polynomials, power functions, or similar nonlinear functions. The coefficients of these isotherms can typically be determined for a wafer as a function of base resistance or sensitivity. During calibration, the nonlinear isotherm function can be calibrated using two points (known hydrogen partial pressure and resistance) that are adjusted to fit the two points using a linear transformation.

[0086] Multi-temperature limit transition function Two-temperature operation requires a significant temperature difference between the first and second temperatures, and as a result, the transition periods between temperature states induce undesirable transient responses in the hydrogen sensor, which typically lead to a reduction in measurement capability, and in the worst case, loss of measurement capability. Alternatively, n number of temperature states can be added between temperature A and temperature A+N, such that only a small increase or decrease in temperature occurs at a time, thereby reducing the magnitude of the undesirable transient responses. That is, the sensor may be at temperature A for a first period of time, then transition to temperature A+1 for a second period of time, remain at temperature A+1 for a third period of time, transition to temperature A+2 for a fourth period of time, transition to temperature A+N for the n-1th period of time, and remain at temperature A+N for the nth period of time. The sensor may return to temperature A in the reverse order. Assuming, hydrogen may be calculated live at each of the temperature states with the highest accuracy, and may be calculated with a potentially reduced accuracy during the transition states. The measurements from temperatures A and A+N are used in a two-temperature formula to calculate hydrogen with the offset removed.

[0087] To reduce undesirable transients, the step from one temperature to the next can be made small enough so that any undesirable transients are very small and short-lived, to the point that there are essentially no interrupted readings of hydrogen.

[0088] As just one example, the large step from the first temperature to the second temperature may be approximately 20° C. In order for the gas sensor to obtain a reliable measurement, it must reach equilibrium, which may take 30 minutes. Thus, 30 minutes must elapse before the gas sensor is live again. On the other hand, if small steps of 1° C. are used instead of taking the full large step of 20° C., less time is required to reach equilibrium, and the gas sensor may be live again after 30 seconds instead of 30 minutes. The gas sensor can then perform measurements in multiple spaced small steps approaching the full large step of 20° C., and a multi-temperature equation is utilized to calculate the hydrogen concentration at each small step. This technique effectively reduces the amount of time that the system cannot be measured at equilibrium and does not have to rely on a transient response during the transition period.

[0089] Heater power correction function In an environment free of interfering gases, with constant hydrogen partial pressure and constant sensor operating temperature, the resistance should be constant (except for small drifts due to instabilities). However, as the environmental heat load at the die changes (due to environmental temperature, flow rate, etc.), the sensor resistance changes. This resistance change can be compensated for by using the measured power used to maintain the sensor die temperature. The correction assumes that the resistance adjustment is proportional to the heater power measurement. The compensated resistance is equal to the measured resistance plus an adjustment value as described below.

[0090]

number

[0091] During the ceremony,

[0092]

number

[0093] The heater power factor α, when used to compensate for the measured resistance, effectively normalizes the resistance to that with no power.

[0094] Temperature dependent heater power correction function Correction of heater power where the heater power factor is also a function of operating temperature.

[0095] Hydrogen dependent heater power correction function In the heater power correction method, the heater power factor can also be a function of hydrogen partial pressure.

[0096] Heater power function for calculating environmental temperature In the two-temperature method, the power required to heat the die to equilibrium in the first period (Temperature 1) and the third period (Temperature 2) can be measured and recorded. Assuming that the environment temperature and heat load on the die are constant, the temperature of the environment can be calculated using the linear function described below:

[0097] aP T1 Let be the heater power of the die at temperature T1. bP T2 Let be the heater power of the die at temperature T2. cT env Let be the unknown environmental temperature lower than T1 and T2.

[0098] Then:

[0099]

number

[0100] Using the information from T1, solve the following equation:

[0101]

number

[0102] Also, in its complete form,

[0103]

number

[0104] The foregoing description of the preferred embodiments and features of the present invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications, variations, and combinations are possible in light of the above teachings. It is intended that the scope of the invention be limited not by this detailed description, but by the appended claims and the equivalents of the appended claims.

Claims

1. A method for determining a target gas concentration of a target gas in a fluid environment, the method comprising: (a) exposing a first gas sensor to the fluid environment, the first gas sensor having an electrical characteristic that varies as a function of the target gas concentration; (b) exposing a second gas sensor to the fluid environment, the second gas sensor having an electrical characteristic that varies as a function of the target gas concentration; (c) alternatingly controlling a temperature of the second gas sensor between a first temperature and a second temperature while the second gas sensor is exposed to the fluid environment, wherein the temperature of the second gas sensor is maintained at the first temperature for a first period of time, transitions from the first temperature to the second temperature for a second period of time, remains at the second temperature for a third period of time, and transitions from the second temperature to a third temperature for a fourth period of time; (d) monitoring the electrical characteristic of the second gas sensor during the second time period and the fourth time period; and (e) calculating the target gas concentration as a function of the electrical characteristic of the first gas sensor, where data from the second gas sensor is used to correct for baseline sensor drift of the first gas sensor; A method comprising:

2. The method of claim 1, wherein the first gas sensor operates at a single temperature.

3. The method of claim 2, wherein the second gas sensor is in a state of constant system response to a repeating thermal waveform.

4. The method of claim 3, wherein the first gas sensor reports to the second gas sensor the change in partial pressure of the target gas detected by the first gas sensor.

5. The method of claim 1, wherein the first gas sensor is configured to operate at two temperatures, controlling a temperature of the first gas sensor alternately between a first temperature and a second temperature while the first gas sensor is exposed to the fluid environment, comprising: the temperature of the first gas sensor is maintained at the first temperature for a first period of time, transitions from the first temperature to the second temperature for a second period of time, is maintained at the second temperature for a third period of time, and transitions from the second temperature to a third temperature for a fourth period of time; the temperature of the first gas sensor and the temperature of the second gas sensor are staggered such that when the first gas sensor is in the first period or the third period of the first gas sensor, the second gas sensor is in the second period or the fourth period of the second gas sensor. The method of claim 1.

6. The method of claim 1, wherein the data from the second gas sensor includes the electrical characteristics of the second gas sensor during the second period.

7. The method of claim 1, wherein the data from the second gas sensor includes the electrical characteristics of the second gas sensor during the fourth period.

8. The method of claim 1, wherein the data from the second gas sensor includes the electrical characteristics of the second gas sensor during the second period and during the fourth period.

9. A method for determining a target gas concentration of a target gas in a fluid environment, the method comprising: (a) exposing a first gas sensor to the fluid environment, the first gas sensor having an electrical characteristic that varies as a function of the target gas concentration; (b) exposing a second gas sensor to the fluid environment, the second gas sensor having an electrical characteristic that varies as a function of the target gas concentration. (c) during step (b), modulating the temperature of the second gas sensor, the modulation being in the form of a repetitive thermal waveform that induces a frequency response in the electrical characteristic of the second gas sensor. (d) during step (c), monitoring the electrical characteristic of the second gas sensor; (e) calculating the target gas concentration as a function of the electrical characteristic of the first gas sensor; (f) using the second gas sensor to correct the target gas concentration calculated by the first gas sensor, wherein data from the second gas sensor is used to correct for baseline sensor drift of the first gas sensor; A method comprising:

10. The method of claim 9, wherein the first gas sensor operates at a single temperature.

11. The method of claim 9, wherein the temperature of the first gas sensor is adjusted, the adjustment being in the form of a repeating thermal waveform that induces a frequency response in the electrical characteristics of the first gas sensor.

12. The method of claim 9, wherein the data from the second gas sensor used to correct the target gas concentration is a function of the frequency response of the electrical characteristics of the second gas sensor.

Images