A method for intelligent diagnosis of mass spectrometry operation faults

Abstract

This invention provides an intelligent diagnostic method for mass spectrometry operation faults. It identifies the characteristics of typical operation fault types based on the mass spectrometry operation faults, and through a wide-range scan of the mass-to-nucleus ratio of the mass spectrometer (including the mass-to-nucleus ratio of carrier gas, air, and the analyte gas), selects the dynamic change characteristic relationship of the signal under different mass-to-nucleus ratios. Combined with the characteristic types of mass spectrometry operation faults, it uses techniques such as time correlation analysis and co-correlation to achieve real-time perception and diagnosis of operation faults, and provides maintenance prompts for different types of faults.

Description

Technical Field

[0001] This invention relates to the field of mass spectrometry operation fault technology, and specifically to an intelligent diagnostic method for mass spectrometry operation faults. Background Technology

[0002] Currently, mass spectrometry is applicable to the detection and analysis of numerous gases and can also analyze various reaction processes involving the escape of gases. Due to the inherent characteristics of mass spectrometry's operation and specific working conditions, such as thermodynamic conditions like pressure and temperature at a fixed vacuum level, and the diverse types of gases being analyzed under varying thermodynamic conditions, operational malfunctions often occur during gas detection and analysis using mass spectrometry. These malfunctions differ from hardware or software failures. They primarily occur when the diverse characteristics of the analyzed object and its wide / variable operating conditions prevent reliable detection and analysis. When such operational malfunctions occur, the core hardware and software of the mass spectrometer are not yet compromised.

[0003] like Figure 1As shown, the main operational failures during mass spectrometry detection include the following five categories: 1) Sampling gas path blockage. The root cause of this problem is that the sampled gas contains components that are highly condensable. Before sampling, the gas is at a high temperature and does not condense. However, when it enters the sampling channel of the mass spectrometer, the temperature drops synchronously due to the pressure decrease, causing condensation at specific locations in the sampling pipeline. This continuous and intense condensation will cause blockage of the sampling gas path. In this case, although mass spectrometry detection can still be performed, the data is meaningless. 2) Air leakage at various connection points. During mass spectrometry detection, the internal cavity is in a high vacuum state, and there are many connection points around the internal cavity, especially various connection flanges and their sealing components. Under normal operating conditions, a very small amount of air leakage may occur in these sealing parts, forming background gas for the mass spectrometer, which does not affect the working state and detection results of the mass spectrometer. However, if it operates at a high vacuum for a long time, and the gas being analyzed may contain corrosive components, concentrated air leakage may occur at certain points in time, which will greatly affect the operating state of the mass spectrometer. 3) Gas evolution on the surface of the vacuum chamber. When the vacuum chamber and core components of a mass spectrometer operate under vacuum conditions, they experience adsorption, permeation, desorption, and precipitation of certain gases. For example, the material of the vacuum chamber has strong adsorption properties for water and hydrogen ions. In some tests, if there is a high concentration of water and hydrogen ions, they will be adsorbed and permeate into the interior of the vacuum chamber material, while in other tests they will be desorbed and precipitated. These components will interfere with normal mass spectrometry detection. 4) Mass spectrometry ion source contamination. Similar to the adsorption and permeation of some ions, some components ionize at the ionization source during gas detection, forming charged ions. These components easily adhere to the ionization source, and continuous occurrence will lead to ion source contamination, thereby forming other gaseous components during detection and interfering with normal mass spectrometry detection. 5) Mass spectrometry vacuum pressure fluctuations. During mass spectrometry detection, environmental conditions, operating conditions, and other issues can cause pressure fluctuations inside the vacuum chamber. These fluctuations will lead to signal distortion during the detection process.

[0004] The five typical types of mass spectrometry (MS) malfunctions described above will directly interfere with the MS's gas detection and may even affect the normal operation of the equipment. However, the occurrence of these malfunctions does not necessarily cause the MS to shut down or trigger an alarm, and they may not even be directly detected during operation. This allows the detection process to continue, and the MS can still ionize the gas, perform mass analysis, and collect ion signals, but the actual signal output will reflect the results under the malfunction conditions. To detect these malfunctions promptly and effectively, avoid wasting operating time or affecting subsequent tests, and prevent potential damage to the MS equipment, it is necessary to utilize the MS output signal to sense and analyze the presence of malfunctions in real time, determine the type of malfunction, issue an alarm, and take effective measures to eliminate the malfunction, thereby achieving intelligent real-time detection of MS malfunctions.

[0005] However, since mass spectrometry malfunctions are caused by the diversity of internal and external testing conditions, they do not directly lead to the mass spectrometer's inability to function properly. The detection signal can still be output, but it no longer represents the physical parameters of the actual test object; instead, it reflects the characteristics of the malfunction. Faced with such typical malfunctions, when the test object is also operating under wide and varied conditions, it is often impossible to directly perceive them manually. Therefore, it is difficult to effectively distinguish between a malfunction and dynamic changes in the test object. This results in the detection process continuing even when a malfunction occurs, potentially causing significant damage to the equipment.

[0006] Because malfunctions in mass spectrometry operation can lead to invalid output signals and even the potential for equipment damage, the accumulation of these factors necessitates real-time detection and monitoring of malfunctions. However, current methods for diagnosing malfunctions still rely on traditional manual analysis, primarily falling into two categories: one involves interpreting data that significantly impacts mass spectrometry operation, identifying extreme anomalies such as extremely high or low signals, or unexpected data occurrences; the other involves recognizing various alarm messages generated by the mass spectrometer, such as readings exceeding the acceptable range for vacuum chamber pressure.

[0007] The aforementioned methods of diagnosing operational faults through manual interpretation of mass spectrometry data and alarm notifications have several technical shortcomings: 1) Fault diagnosis cannot achieve rapid real-time perception. Both methods are typical post-event analyses, and a rough judgment can only be made after the mass spectrometer continues operating for a period of time after the fault occurs, causing a more significant impact. This fails to provide prompt alerts after a fault occurs, thus failing to protect the operation of the mass spectrometer. 2) Fault types cannot be identified in a timely manner. Because the occurrence of mass spectrometry operational faults cannot be detected immediately, subsequent effects continue, leading to cross-interference between fault types and other influencing factors. For example, blockage in the sampling gas path can cause a decrease in pressure within the mass spectrometer vacuum chamber over time, resulting in continuous evacuation by the mass spectrometer vacuum environment, or other secondary reactions. The interaction of multiple factors makes direct fault identification impossible. 3) Post-event analysis and maintenance of operational faults are extremely difficult. Different types of mass spectrometer operational faults often require different maintenance measures. If the fault type is unknown, it will be impossible to utilize different technical means for mass spectrometer maintenance. As for the post-failure judgment of operational failures, various calibration and inspection methods are usually used. These methods require the gradual elimination of problems one by one, which requires a lot of time and effort.

[0008] The core of the aforementioned technical deficiency lies in the failure to effectively analyze the mass spectrometry detection output signal. In fact, the characterization information of a mass spectrometry malfunction, from its initial appearance to its rapid development, is already integrated into the output signal. Furthermore, different types of malfunctions have their own typical signal characteristics. Because the mass spectrometry detection signal is a three-dimensional dynamic signal under different mass-to-nucleus ratios, a full-range mass-to-nucleus ratio scan would reveal the actual operating status of the mass spectrometer. In actual testing, users often neglect the detection of background gases, such as carrier gas and air, assuming these changes are noise or interference components and thus ignoring them. Even when detected, their dynamic changes are often overlooked. This approach renders the analysis of the detected object completely incapable of determining the malfunction of the mass spectrometer.

[0009] In summary, there is a need to develop an intelligent diagnostic method for mass spectrometry operation faults. Summary of the Invention

[0010] In view of the problems existing in the prior art, the present invention provides an intelligent diagnosis method for mass spectrometry operation faults. For typical faults that may occur during the operation of mass spectrometry gas detection, the method utilizes the characteristics of the fault itself in the mass spectrometry data to diagnose the type and probability of the fault in real time, so as to avoid the fault from causing continuous impact on the equipment.

[0011] To achieve this objective, the present invention adopts the following technical solution:

[0012] The purpose of this invention is to provide an intelligent diagnostic method for mass spectrometry operation faults, including the following:

[0013] Mass spectrometry is used for detection, and a wide range of mass-to-nucleus ratio (MTBR) scanning is performed. The wide range of MTBR scanning includes performing relevant MTBR scanning on the carrier gas, air and the gas components to be tested, monitoring the mass spectrometry output signal in real time, analyzing the derivative of the ion current intensity signal with time for different MTBRs, and / or analyzing whether the ion current intensity signal for different MTBRs exceeds the limit.

[0014] Correlation analysis and / or over-limit analysis are performed on the signal data with different mass-to-nucleus ratios obtained from the analysis, and the features are compared with the mass spectrometry operation fault feature library to intelligently diagnose the existence and type of mass spectrometry operation faults.

[0015] The mass spectrometry operation fault feature library is obtained by summarizing known mass spectrometry operation faults and updating it with new mass spectrometry operation fault features obtained from diagnosis.

[0016] As a preferred technical solution of the present invention, the mass spectrometer output signal is monitored in real time. If the derivative of the ion current intensity signal of the relative mass-to-nucleus ratio of the carrier gas and air with time decreases sharply and falls below the threshold almost simultaneously, and correspondingly, the derivative of the ion current intensity signal of the relative mass-to-nucleus ratio of the gas component to be measured increases sharply and exceeds the threshold almost simultaneously, it can be diagnosed that there is a mass spectrometer operation fault, and the fault type is sampling gas path blockage.

[0017] As a preferred technical solution of the present invention, the mass spectrometer output signal is monitored in real time. If the derivative of the ion current intensity signal of the carrier gas relative mass ratio with time suddenly decreases and falls below the threshold, and correspondingly, the derivative of the ion current intensity signal of the air relative mass ratio with time almost simultaneously increases and exceeds the threshold, it can be diagnosed that there is a mass spectrometer operation fault, and the fault type is air leakage at the connection point.

[0018] It should be noted that for fault types such as sampling gas path blockage or air leakage at connection points, those skilled in the art can set thresholds according to the actual situation. For example, the threshold corresponding to a sudden decrease in the derivative of the ion current intensity signal with time is -100, and the threshold corresponding to a sudden increase is 100.

[0019] As a preferred technical solution of the present invention, the mass spectrometer output signal is monitored in real time. If the ion current intensity signal of the relevant mass-to-nucleus ratio of H2 and / or H2O exceeds the threshold and continues to increase, the continuous increase includes: the ion current intensity signal of the relevant mass-to-nucleus ratio of H2 exceeds the ion current intensity signal of the relevant mass-to-nucleus ratio of O2, and / or, the ion current intensity signal of the relevant mass-to-nucleus ratio of H2O exceeds the ion current intensity signal of the relevant mass-to-nucleus ratio of N2. It can be diagnosed that there is a mass spectrometer operation fault, and the fault type is gas evolution on the surface of the vacuum chamber.

[0020] It should be noted that for fault types involving gas evolution at the vacuum chamber surface, common components are H2 and H2O. Those skilled in the art can set relevant thresholds based on whether the gas being measured contains H2 and H2O. As a process mass spectrometry operational fault, exceeding the threshold indicates the possible presence of gas evolution at the vacuum chamber surface. Only when the ion current intensity signal exceeds the threshold and continues to increase, causing the H2 signal to exceed that of O2 in the air, and / or the H2O signal to exceed that of N2 in the air, can the fault type be confirmed as gas evolution at the vacuum chamber surface. As a preferred technical solution of this invention, real-time monitoring of the mass spectrometer output signal is performed. If the signal-to-noise ratio (SNR) of the relevant mass-to-nucleus ratio of the uncertain component is ≥3, and the ion current intensity signal continues to increase, causing the SNR to be ≥10, it can be diagnosed that a mass spectrometer operational fault exists, and the fault type is ion source contamination.

[0021] It should be noted that for fault types of ion source contamination, uncertain components are often high mass-to-nucleus ratio and cyclic components. As a process mass spectrometry operation fault, a signal-to-noise ratio ≥3 indicates the possible presence of uncertain components. Only when the ion current intensity signal continues to increase, resulting in a signal-to-noise ratio ≥10, can the fault type be determined to be ion source contamination.

[0022] As a preferred technical solution of the present invention, the mass spectrometer output signal is monitored in real time. If the ion current intensity signal of the relevant mass-to-nucleus ratio of the carrier gas exceeds a first limit, and / or if the derivative of the ion current intensity signal of the relevant mass-to-nucleus ratio of the carrier gas with time exceeds a second limit, it can be diagnosed that there is a mass spectrometer operation fault, and the fault type is vacuum pressure fluctuation; wherein, the first limit and the second limit are obtained based on historical data during the normal operation of the mass spectrometer.

[0023] As a preferred technical solution of the present invention, mass spectrometry is used for detection, and a wide range mass-to-nucleus ratio scan is performed. The wide range mass-to-nucleus ratio scan includes performing relevant mass-to-nucleus ratio scans on the carrier gas, air and the gas components to be tested, monitoring the mass spectrometry output signal in real time, analyzing the derivative of the ion current intensity signal with time for different mass-to-nucleus ratios, and / or analyzing whether the ion current intensity signal for different mass-to-nucleus ratios exceeds the limit.

[0024] First, a diagnostic process for real-time operational faults is implemented. These faults include sampling gas path blockage, air leakage at connection points, and vacuum pressure fluctuations. The derivatives of the ion current intensity signals of the relevant mass-to-nucleus ratios of the carrier gas, air, and analyte components over time are analyzed, and correlation analysis and / or limit analysis are performed. If a real-time operational fault is diagnosed, operation is stopped, and fault type analysis is conducted, with alarm prompts and verification and updates to the mass spectrometry operational fault feature library. If no real-time operational fault is diagnosed, a diagnostic process for process-related operational faults is implemented. These faults include gas evolution on the vacuum chamber surface and ion source contamination. The ion current intensity signals of the relevant mass-to-nucleus ratios of H2 and / or H2O and uncertain components are analyzed, with correlation analysis and / or limit analysis performed. If a process-related operational fault is diagnosed, operation is stopped, and fault type analysis is conducted, with alarm prompts and verification and updates to the mass spectrometry operational fault feature library. If no process-related operational fault is diagnosed, valid mass spectrometry operational data can be obtained.

[0025] As a preferred embodiment of the present invention, the carrier gas includes Ar, and the air includes N2 and O2.

[0026] Compared with existing technical solutions, the present invention has at least the following beneficial effects:

[0027] This invention identifies the characteristics of typical operational fault types in mass spectrometry. By scanning a wide range of mass-to-nucleus ratios (CNRs) of mass spectrometers, including the CNRs of carrier gas, air, and the analyte gas, it selects the dynamic change characteristics of signals under different CNRs. Combined with the characteristic types of mass spectrometry operational faults, it employs techniques such as time correlation analysis and co-correlation to achieve real-time perception and diagnosis of operational faults, while providing maintenance prompts for different types of faults. Attached Figure Description

[0028] Figure 1 This is a schematic diagram of a typical operational failure during mass spectrometry operation;

[0029] Figure 2 This is a logic diagram of the technical solution for the intelligent diagnosis method for mass spectrometry operation faults described in this invention.

[0030] Figure 3 This is a three-dimensional mass spectrometry image of an example of a blocked sampling gas path in a specific embodiment of the present invention;

[0031] Figure 4 This is a three-dimensional mass spectrometry image of an example of air leakage at the connection point in a specific embodiment of the present invention;

[0032] Figure 5 This is a three-dimensional mass spectrometry image of an example of gas evolution on the surface of a vacuum cavity in a specific embodiment of the present invention;

[0033] Figure 6 This is a logic flowchart of an intelligent diagnosis method for mass spectrometry operation faults in a specific embodiment of the present invention;

[0034] Figure 7 This is the three-dimensional mass spectrometry spectrum corresponding to the methanol blockage in Example 1 of this invention;

[0035] Figure 8 This is a curve showing the specific mass-to-nucleus ratio signal change in Embodiment 1 of the present invention. Detailed Implementation

[0036] like Figure 2 As shown, this invention focuses on identifying the characteristics of typical operational fault types in mass spectrometry. By scanning a wide range of mass-to-nucleus ratios (CNRs) of the mass spectrometer, including the CNRs of carrier gas, air, and the analyte gas components, it selects the dynamic change characteristics of the signal under different CNRs. Combined with the characteristic types of mass spectrometry operational faults, it employs techniques such as time correlation analysis and co-correlation to achieve real-time perception and diagnosis of operational faults, while providing maintenance prompts for different types of faults.

[0037] The main working mechanism of the technical solution described in this invention is that the characteristics of mass spectrometry operation faults can be characterized by the mass spectrometry output signal. Typical operation faults cause extreme interference and influence on the mass spectrometry signal. When the mass spectrometer performs a wide range of mass-to-nucleus ratio scans on all possible gas phase components, each type of feature will produce changes in the mass spectrometry signal with its own essential laws, including the dynamic changes of the signal under a specific mass-to-nucleus ratio, as well as the coupling and correlation changes between signals of different mass-to-nucleus ratios. These changes all reflect the gas phase component changes behind the fault. Therefore, the extraction of mass spectrometry operation fault features and actual diagnosis are based on the judgment of the change law of gas phase component signals.

[0038] The main working principle of the technical solution described in this invention is to use a wide range of mass-to-nucleus ratio scanning in mass spectrometry to analyze and judge in real time whether the changes in the mass spectrometry signal are consistent with the fault characteristics based on the characteristics of the operational fault, thereby realizing the diagnosis of mass spectrometry operational faults.

[0039] Typical characteristics of mass spectrometry operation failure:

[0040] 1) Blockage in the sampling gas path

[0041] The essence of sampling gas path blockage lies in the presence of easily condensable components in the analyte gas. These components condense and accumulate in the mass spectrometer sampling and transmission pipeline, thus completely blocking the gas pipeline. Figure 1 As shown, there are clear characteristics of component changes before and after blockage, including the inability of carrier gas and air components to enter, while the condensed portion of the gas phase component to be analyzed is concentrated and extracted into the mass spectrometer vacuum chamber, forming a rapidly increasing signal. Figure 3 The image shows a three-dimensional mass spectrometry spectrum of an example of a blocked sampling gas path. The fault characteristics are as follows: the derivatives of the carrier gas and air component signals are approximately a rapidly decreasing step, that is, the derivative of the signal with time suddenly approaches negative infinity, and the changes of the two signals are positively correlated with each other, with a correlation coefficient of 1; while the condensed component in the analyte gas is approximately a steeply increasing step, that is, the derivative of the signal with time suddenly approaches positive infinity, and it is negatively correlated with the changes of the carrier gas and air signals, with a correlation coefficient of -1.

[0042] The mathematical expression for this type of mass spectrometry operation fault diagnosis after feature extraction is:

[0043] (1.a)

[0044] (1.b)

[0045] (1.c)

[0046] (1.d)

[0047] In Equation 1, time td represents the time when the operational fault occurs. , The mass spectrometry detection signal represents different mass-to-nucleus ratios. If i=28 or 32, it is the mass-to-nucleus ratio of the air component. If i=r, it is the mass-to-nucleus ratio of the carrier gas. If j=k, it is the mass-to-nucleus ratio of the gas phase group to be analyzed. When the time difference is 0 Correlation analysis is performed, where i and j correspond to mass spectrometry detection signals with mass-to-nucleus ratios of i and j, respectively. Through the series of relationships in Equation 1, the changes in a specific mass-to-nucleus ratio and their correlations can be analyzed, thus forming the mathematical characteristics of gas path blockage. This allows for intelligent perception and fault diagnosis of such mass spectrometry operational malfunctions.

[0048] 2) Air leakage at the connection point

[0049] The essence of air leakage at the connection point lies in the rapid entry of air components into the mass spectrometer vacuum chamber. The air entering the chamber differs from the air content in the gas being analyzed. Figure 4 The image shows a three-dimensional mass spectrometry spectrum of an example of air leakage at a connection point. The air component in the analyte gas exhibits a typical stable signal, while the air leakage at the connection point shows a different signal. Figure 4 The signal shown grows rapidly, and the characteristic of the component changes before and after the leak is a significant decrease in the carrier gas signal and an increase in the air component signal. The fault characteristics of the three-dimensional mass spectrometry spectrum are: the carrier gas derivative approximates a rapidly decreasing step, meaning the signal's time derivative suddenly approaches negative infinity; while the air component signal approximates a steeply increasing step, meaning the signal's time derivative suddenly approaches positive infinity; moreover, the carrier gas and air signal changes are negatively correlated, with a correlation coefficient of -1. The mathematical expression for this type of mass spectrometry operational fault diagnosis after feature extraction is:

[0050] (2.a)

[0051] (2.b)

[0052] (2.c)

[0053] The series of relations in Equation 2 is completely different from that in Equation 1. This difference reflects Figure 3 , 4 Similarly, through the series of relationships in Equation 2, intelligent perception and fault diagnosis can be achieved for mass spectrometer operation faults such as air leakage at connection points.

[0054] 3) Gas evolution on the surface of the vacuum chamber

[0055] The surface of the vacuum chamber of a mass spectrometer is prone to adsorbing some highly permeable small molecule gases, such as H2 and H2O. These gases will permeate and precipitate during mass spectrometry detection. The precipitation process can be characterized by a signal with a specific mass-to-nucleus ratio. If the amplitude of such precipitated gases is too large, it will interfere with the detection results of the mass spectrometer.

[0056] Vacuum chamber gas extraction is used in detection processes containing easily permeable gaseous components, such as H2 and H2O. Figure 5 The image shows a three-dimensional mass spectrometry spectrum of an example of gas precipitation on the surface of a vacuum chamber. If such components were present in previous tests, causing adsorption of these components on the vacuum chamber material, and if effective baking and removal are not performed before subsequent tests, they will precipitate in subsequent tests and continue to increase over time, potentially affecting the reliability of the mass spectrometry data. The fault characteristics of the three-dimensional mass spectrometry spectrum are: a continuous increase in the signal of specific components H2 and H2O. The mathematical expression extracted from the features of this type of mass spectrometry operation fault diagnosis is the series of relationships in Equation 3.

[0057] (3.a)

[0058] (3.b)

[0059] 4) Ion source contamination

[0060] When the ion source of a mass spectrometer is contaminated with some gaseous components, some gases will desorb from the ion source surface or even undergo secondary reactions as the mass spectrometer continues to operate. The gaseous components contained in these gases are different from those precipitated from the vacuum chamber; they are often gaseous components other than the gas being measured, such as large hydrocarbon molecules. Their release process is similar to... Figure 5 The results shown are similar, except for the different mass-to-nucleus ratio ranges in the mass spectra. The characteristic of a faulty three-dimensional mass spectra is: uncertain mass spectral signals of macromolecular gaseous components. The anomaly far exceeded the limit. Or it may continue to grow. The mathematical expression for the feature extraction of this type of mass spectrometry operation fault diagnosis is the series relationship in Equation 4. This indicates the predictable maximum mass-to-nucleus ratio range for the mass spectrometer detection target. This indicates that the gas phase component k is not within this range.

[0061] (4.a)

[0062] (4.b)

[0063] In addition, the presence of ion source contamination can also be diagnosed based on the signal-to-noise ratio. If the signal-to-noise ratio of the ion current intensity signal of the relevant mass-to-nucleus ratio of the uncertain component is ≥3, and the ion current intensity signal continues to increase, making the signal-to-noise ratio ≥10, it can be diagnosed that there is a mass spectrometer operation fault, and the fault type is ion source contamination.

[0064] 5) Vacuum pressure fluctuation

[0065] The vacuum level is consistently monitored during mass spectrometry detection and is maintained at a stable vacuum state by various vacuum pumps. The operating pressure depends on the actual working conditions of the vacuum pumps in the test mode and may be affected by external environmental factors and the analyte gas. For example, the presence of dust in the analyte gas can affect the operation of the vacuum pump. Such situations often interfere with the dynamic changes of the carrier gas, causing drift or significant fluctuations in the carrier gas-mass spectrometry signal. The fault characteristics of the three-dimensional mass spectrometry spectrum are: the signal value or its derivative under the carrier gas-nuclear ratio exceeds the conventional limit. The mathematical expression extracted from the features of this type of mass spectrometry operation fault diagnosis is the series relationship in Equation 5. The conventional limit can be obtained from historical data during normal mass spectrometry operation.

[0066] (5.a)

[0067] (5.b)

[0068] The feature extraction of the typical operational faults of mass spectrometry described above can be expressed by different types of relationships. For types of operational faults beyond the five categories mentioned above, similar methods can be used to extract relevant relationships. Similarly, when multiple operational faults occur simultaneously, although the probability is small, the overall diagnosis must still rely on the dynamic relationships described above.

[0069] The specific implementation scheme of this invention is divided into two modules: real-time operational fault diagnosis and process operational fault diagnosis. The former, as the main module, mainly targets sampling gas blockage, air leakage, and vacuum pressure fluctuations, performing real-time fault interpretation. The latter, as a sub-module, targets vacuum chamber gas evolution and ion source contamination, employing time-segmented analysis. The logical flow of the implementation process is as follows: Figure 6 As shown, the specific implementation steps are as follows:

[0070] Real-time fault diagnosis process:

[0071] 1) Mass spectrometry operating parameter settings

[0072] Before mass spectrometry can detect gases, the mass-to-nucleus ratio (CNR) scanning range must be set. The CNR should cover at least all possible gas phase components, including carrier gas, air components, known gas phase components to be analyzed, and possible unknown components. At the same time, the ionization mode of the mass spectrometer and its ionization energy setting must be able to ionize all components. If a soft ionization mode or low ionization energy is used, some gas phase components will not be ionized, making it impossible to track and search for all gas phase components.

[0073] 2) Acquisition of three-dimensional dynamic mass spectrometry spectrum

[0074] After setting it up as described in step 1, the mass spectrometer performs the gas detection process and obtains a three-dimensional dynamic spectrum of time, mass-to-nucleus ratio and ion current intensity, thus obtaining real-time dynamic data of the three-dimensional spectrum.

[0075] 3) Feature signal tracking and data differentiation analysis

[0076] Real-time data extraction of carrier gas, air components, and vacuum degree monitoring in the three-dimensional dynamic mass spectrometry spectrum, namely, real-time reading of specific mass-to-nucleus ratio data of gas phase components such as carrier gas and air, differentiation of the three types of time-varying sequences, and determination of whether there are abnormal fluctuations based on the derivative relationships in the series of relations 1, 2, and 5. If there are abnormal fluctuations, proceed to step 4; otherwise, it is normal operation.

[0077] 4) Correlation analysis

[0078] Extract the data of each component in step 3 and perform time correlation analysis according to Equations 1 and 2.

[0079] 5) Feature comparison

[0080] Based on historical data in the mass spectrometry operation fault feature library, analyze and diagnose the types of operation faults according to the categories of relationships 1, 2, and 5.

[0081] 6) Mass spectrometry operation fault prompts

[0082] After determining the type of mass spectrometer malfunction based on steps 4 and 5, an alarm is triggered and operation is recommended to be stopped. Subsequently, the malfunctions are resolved and maintenance is performed. The reliability of the malfunction analysis is verified based on the troubleshooting and maintenance measures. The historical analysis process and maintenance information are loaded into the mass spectrometer malfunction characteristic database and maintenance information database, respectively, for updating.

[0083] Process fault diagnosis procedure:

[0084] 7) Submodule data retrieval

[0085] If step 6 still cannot determine the type of mass spectrometer malfunction, load its three-dimensional dynamic mass spectrometry data into the process fault diagnosis module. After importing the data, use the equivalent characteristic spectrum method of mass spectrometry quantitative analysis technology to perform three-dimensional mass spectrometry analysis and obtain the production rate of various gas phase components.

[0086] 8) Separation of gas phase component signals

[0087] Using the analysis data of various gas phase components from step 7, determine whether there are any types of gas phase components that exceed the types of the test object, and whether there is any release of permeation components.

[0088] 9) Operational Fault Types

[0089] Based on formulas 3 and 4, and combined with historical data from the mass spectrometry operation fault feature library, determine whether there is mass spectrometry ion source contamination or vacuum chamber gas leakage. If no such faults exist, the three-dimensional dynamic data of the mass spectrometry is normal, forming valid mass spectrometry operation data. If an operation fault exists, proceed to step 10.

[0090] 10) Troubleshooting and Verification

[0091] If the extracted analyte data is compared to samples outside the specified range, it is determined to be ion source contamination; if the extracted permeate data is compared to samples outside the specified range, it is determined to be over-permeation, i.e., gas evolution on the vacuum chamber surface. After the initial fault type is determined, fault information is provided and handling suggestions are given, an alarm is triggered and operation is advised to be stopped. Afterwards, the operational faults of the mass spectrometer are troubleshooted and maintained. The reliability of the operational fault analysis is verified based on the troubleshooting and maintenance measures. The historical data of the analysis process and maintenance information are respectively loaded into the mass spectrometer operational fault characteristic database and maintenance information database for updating.

[0092] In this invention, the mass spectrometry operation fault feature library is the cumulative result of actual mass spectrometry. Its initial setting gives the routine operation analysis data according to the relationship 1-5, and it can be continuously verified and supplemented through this process in the later stage.

[0093] To better illustrate the present invention and facilitate understanding of its technical solutions, typical but non-limiting embodiments of the present invention are as follows:

[0094] Example 1

[0095] Mass spectrometry was performed on methanol gas, which is easily condensable, using Ar gas as the carrier gas. Figure 7 The three-dimensional mass spectra corresponding to methanol blockage are shown, and the dynamic changes of all gas phase components are displayed in real time, based on... Figure 7 Extract the mass spectrometry ion flux intensity variation signals at specific mass-to-nucleus ratios from the series of equations 1, such as... Figure 8 As shown, the signal of the carrier gas with a characteristic mass-to-nucleus ratio (m / z=40) drops sharply around 52 minutes, while the signal of the methanol gas (m / z=31) rises in the opposite direction. There is a clear negative correlation between the two, with a correlation coefficient of -1. This indicates that the gas sampling transmission pipeline is blocked by methanol. At this point, methanol gas phase injection is stopped to protect the mass spectrometer's operation, effectively initiating equipment maintenance. The blockage and condensation are gradually removed using the vacuum state of the mass spectrometer. Without methanol injection, only carrier gas is injected. After 65 minutes, the methanol signal is still present, but there is still no carrier gas signal, indicating a severe blockage. However, the maintenance measures are effective. After nearly 30 minutes of operation, the sampling gas flow is cleared, and the carrier gas signal recovers sharply, confirming the correctness of the fault diagnosis.

[0096] Through the above simple practical examples, it can be shown that the dynamic changes in the mass spectrometer spectrum can not only reflect the changes in the gas to be analyzed, but also directly reflect the operational fault information of the mass spectrometer. The characteristics of such faults are relatively obvious. Through the relationship formula of this invention, intelligent real-time perception and fault diagnosis can be realized. Combined with the technical verification of maintenance, the accuracy of interpreting operational faults can be greatly improved.

[0097] This invention, based on the typical characteristics of mass spectrometry operational faults, which are manifested in the three-dimensional dynamic spectral information of mass spectrometry, extracts and condenses different characteristic manifestations into various relational formulas. Combined with an operational fault feature database, this forms an intelligent real-time perception and fault diagnosis method. Therefore, this invention has the following advantages: 1) It can track and analyze various types of mass spectrometry operational faults in real time, intelligently determining the fault type using typical relational formulas of different fault characteristics, and providing relevant alarm prompts and handling suggestions. 2) It can achieve rapid alarm for mass spectrometry operational faults, avoiding the continued impact of such faults and even damage to equipment hardware. 3) The intelligent operational fault diagnosis method no longer relies on the experience of professionals, allowing for more scientific prediction, while continuously improving the accuracy of judgment using accumulated information from the database. 4) At the mathematical level, the relational formulas of this invention are consistent with the physical meaning of mass spectrometry operational faults and are easily implemented using various intelligent algorithm programs.

[0098] The present invention has been illustrated with the above embodiments to illustrate its detailed structural features. However, the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must rely on the above detailed structural features to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions for the components used in the present invention, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0099] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0100] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0101] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A method for intelligent diagnosis of mass spectrometry operation faults, characterized in that, Includes the following: Mass spectrometry is used for detection, and a wide range of mass-to-nucleus ratio (MTBR) scanning is performed. The wide range of MTBR scanning includes performing relevant MTBR scanning on the carrier gas, air and the gas components to be tested, monitoring the mass spectrometry output signal in real time, analyzing the derivative of the ion current intensity signal with time for different MTBRs, and / or analyzing whether the ion current intensity signal for different MTBRs exceeds the limit. Correlation analysis and / or over-limit analysis are performed on the signal data with different mass-to-nucleus ratios obtained from the analysis, and the features are compared with the mass spectrometry operation fault feature library to intelligently diagnose the existence and type of mass spectrometry operation faults. The mass spectrometry operation fault feature library is obtained by summarizing known mass spectrometry operation faults and updating it with new mass spectrometry operation fault features obtained from diagnosis.

2. The intelligent diagnosis method for mass spectrometry operation faults according to claim 1, characterized in that, By monitoring the mass spectrometer output signal in real time, if the derivative of the ion current intensity signal of the relative mass ratio of the carrier gas and air with time decreases sharply and falls below the threshold almost simultaneously, and correspondingly, the derivative of the ion current intensity signal of the relative mass ratio of the analyte gas component increases sharply and exceeds the threshold almost simultaneously, it can be diagnosed that there is a mass spectrometer operation fault, and the fault type is sampling gas path blockage.

3. The intelligent diagnosis method for mass spectrometry operation faults according to claim 1, characterized in that, By monitoring the mass spectrometer output signal in real time, if the derivative of the ion current intensity signal of the carrier gas relative mass ratio with time suddenly decreases and falls below the threshold, and correspondingly, the derivative of the ion current intensity signal of the air relative mass ratio with time almost simultaneously increases and exceeds the threshold, it can be diagnosed that there is a mass spectrometer operation fault, and the fault type is air leakage at the connection point.

4. The intelligent diagnosis method for mass spectrometry operation faults according to claim 1, characterized in that, Real-time monitoring of the mass spectrometer output signal reveals that if the ion current intensity signal of the relevant mass-to-nucleus ratio of H2 and / or H2O exceeds the threshold and continues to increase, the continuous increase includes: the ion current intensity signal of the relevant mass-to-nucleus ratio of H2 exceeding the ion current intensity signal of the relevant mass-to-nucleus ratio of O2, and / or, the ion current intensity signal of the relevant mass-to-nucleus ratio of H2O exceeding the ion current intensity signal of the relevant mass-to-nucleus ratio of N2, it can be diagnosed that there is a mass spectrometer operation fault, and the fault type is gas evolution on the surface of the vacuum chamber.

5. The intelligent diagnosis method for mass spectrometry operation faults according to claim 1, characterized in that, If the signal-to-noise ratio (SNR) of the ion current intensity signal with the relevant mass-to-nucleus ratio of uncertain components is ≥3 and the ion current intensity signal continues to increase, resulting in an SNR ≥10, it can be diagnosed that there is a mass spectrometer operation fault, and the fault type is ion source contamination.

6. The intelligent diagnosis method for mass spectrometry operation faults according to claim 1, characterized in that, By real-time monitoring of the mass spectrometer output signal, if the ion current intensity signal of the carrier gas relative to the mass-to-nucleus ratio exceeds the first limit, and / or if the derivative of the ion current intensity signal of the carrier gas relative to the mass-to-nucleus ratio with time exceeds the second limit, it can be diagnosed that there is a mass spectrometer operation fault, and the fault type is vacuum pressure fluctuation; wherein, the first limit and the second limit are obtained based on historical data during the normal operation of the mass spectrometer.

7. The intelligent diagnosis method for mass spectrometry operation faults according to claim 1, characterized in that, Mass spectrometry is used for detection, and a wide range of mass-to-nucleus ratio (MTBR) scanning is performed. The wide range of MTBR scanning includes performing relevant MTBR scanning on the carrier gas, air and the gas components to be tested, monitoring the mass spectrometry output signal in real time, analyzing the derivative of the ion current intensity signal with time for different MTBRs, and / or analyzing whether the ion current intensity signal for different MTBRs exceeds the limit. First, a real-time operational fault diagnosis process is performed. These real-time operational faults include sampling gas path blockage, air leakage at connection points, and vacuum pressure fluctuations. The derivatives of the ion current intensity signals of the relevant mass-to-nucleus ratios of the carrier gas, air, and analyte components over time are analyzed, and correlation analysis and / or limit analysis are performed. If a real-time operational fault is diagnosed, on the one hand, operation is stopped, and on the other hand, fault type analysis is performed, and alarm prompts are issued, and the mass spectrometer operational fault feature library is verified and updated. If no real-time operational fault is diagnosed, a process-based operational fault diagnosis process is initiated. These process-based operational faults include gas evolution on the vacuum chamber surface and ion source contamination. Ion current intensity signals for H2 and / or H2O, and uncertain components with relevant mass-to-nucleus ratios are analyzed, and correlation analysis and / or limit exceedance analysis are performed. If a process-based operational fault is diagnosed, operation is stopped, and fault type analysis is conducted, resulting in alarm prompts and verification and updating of the mass spectrometry operational fault feature library. If no process-based operational fault is diagnosed, valid mass spectrometry operational data can be obtained.

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