Interference correction method for analyzing trace element content in high-temperature alloy by high-resolution glow discharge mass spectrometry

Abstract

The invention relates to the technical field of inorganic mass spectrometry analysis and testing, in particular to an interference correction method for analyzing the content of trace elements in high-temperature alloy by high-resolution glow discharge mass spectrometry, which comprises the following steps: screening out interference elements corresponding to the trace elements from high-temperature alloy components to be detected; the method comprises the following steps: taking a series of metal samples which do not contain trace elements to be detected and have different interference element contents as standard samples, and obtaining a relation model between the interferent concentration and the actual interference element content; determining the interferent concentration of the high-resolution GDMS analysis of the to-be-detected sample based on the relation model, and correcting the high-resolution GDMS analysis result of the trace elements of the to-be-detected sample. The problem that trace elements or macroelements in the high-temperature alloy interfere with trace elements is solved, and accurate detection of the trace elements in the presence of interference elements under the condition of limited GDMS resolution in the prior art is realized.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of inorganic mass spectrometric analysis testing, and in particular to a method for interference correction for high-resolution glow discharge mass spectrometric analysis of trace element content in high-temperature alloy. BACKGROUND

[0002] Trace elements in high-temperature alloy directly affect the organization and performance of the material, and accurate and efficient measurement of trace elements is one of the prerequisites for improving the production quality of the material and ensuring the safe service of the material throughout its life cycle. For example, the addition of rare earth Y element in high-temperature alloy can effectively improve the high-temperature mechanical properties and organizational stability of the alloy, and in particular can improve the high-temperature stability of high-temperature alloy used in the fields of aviation, aerospace, nuclear power, etc. The single crystal high-temperature alloy DD5 contains trace elements C, B, Hf, etc., which can play a role in strengthening the grain boundary, so that the alloy has good high-temperature mechanical properties, oxidation resistance and corrosion resistance.

[0003] The trace elements in high-temperature alloy are interfered by micro or constant elements, for example, the trace or constant elements Ti, Cr with a content greater than 0.1% interfere with the trace analysis elements Y, Nb, Sr. High-resolution GDMS can be used to analyze trace elements in high-temperature alloy, and the high-resolution mode (resolution up to 10000) of the double-focusing mass analyzer is combined with the information on the source and degree of interference received by the analysis element to select appropriate analysis isotopes and resolution for interference elimination; but when the mass number interference is more serious (in the process of mass spectrometric analysis, since some ions or molecules have the same mass number as the elements to be measured, the phenomenon of interference on the analysis results is mass number interference, and the required resolution is greater than 20000), high-resolution GDMS cannot completely separate the interference, resulting in high test data or false positives. SUMMARY

[0004] In view of the above analysis, the present application aims to provide a method for interference correction for high-resolution glow discharge mass spectrometric analysis of trace element content in high-temperature alloy, which solves at least one of the problems in the prior art high-resolution GDMS analysis, such as the interference of trace elements in high-temperature alloy by micro or constant elements and the low detection accuracy, and the resolution of high-resolution GDMS cannot meet the requirements.

[0005] The purpose of the present application is mainly achieved by the following technical solutions:

[0006] A method for interference correction for high-resolution glow discharge mass spectrometric analysis of trace element content in high-temperature alloy, comprising:

[0007] S1: selecting interference elements corresponding to trace elements in high-resolution GDMS analysis from the components of the high-temperature alloy to be measured;

[0008] S2: taking a series of metal samples without the trace elements to be detected and with different contents of interference elements as standard samples, obtaining a relationship model between the interference element concentration in high-resolution GDMS analysis and the actual content of the interference element;

[0009] S3: determining the interference element concentration in high-resolution GDMS analysis of the sample to be detected based on the relationship model, and correcting the high-resolution GDMS analysis result of the trace elements in the sample to be detected with the interference element concentration in high-resolution GDMS analysis of the sample to be detected.

[0010] Preferably, step S1 comprises:

[0011] S101: determining the interference elements corresponding to the trace elements in high-resolution GDMS analysis based on the components of the high-temperature alloy and the analysis atmosphere of high-resolution GDMS;

[0012] S102: selecting standard samples with different contents of interference elements to perform high-resolution GDMS analysis, obtaining the corresponding interference element concentration in high-resolution GDMS determination; the standard samples contain trace or constant interference elements in the sample to be detected, and the interference elements form interference substances with the high-resolution GDMS determination atmosphere in high-resolution GDMS determination, and the content of the trace or constant interference elements in the standard samples is known, and the relationship model between the interference element concentration and the actual content of the interference element in the standard samples is a linear relationship model.

[0013] Preferably, the interference correction method comprises:

[0014] Step S2 comprises: performing linear fitting analysis on the interference element concentration of different standard samples obtained by measurement and the actual content of the corresponding interference elements, and constructing a linear relationship model therebetween.

[0015] Preferably, the interference substances comprise:

[0016] Oxide ions: MO + ;

[0017] Nitride ions: MN + ;

[0018] Hydroxide ions: MOH + ;

[0019] Argonide ions: M Ar + ;

[0020] M is an interference element.

[0021] Preferably, the interference element is one or more of Ni, Cr, Fe, Co, Nb, Ti, and Mo.

[0022] Preferably, the mass fraction of the interference elements in the standard sample and the sample to be detected is ≤30%.

[0023] Preferably, step S3 comprises:

[0024] S301: obtaining the actual content of trace or constant interference elements in the sample to be measured based on the analysis of the trace or constant interference elements in the sample to be measured by a traditional standard method;

[0025] S302: obtaining the concentration of trace or constant interference elements in the sample to be measured based on the actual content of trace or constant interference elements in the sample to be measured obtained in step S2 by using the relationship model obtained in step S2;

[0026] S303: selecting the sample to be measured for high-resolution GDMS analysis to obtain the concentration of trace elements determined by high-resolution GDMS; and completing the correction of the content of trace elements in the sample to be measured by deducting the concentration of trace or constant interference elements obtained in step S5 from the concentration of trace elements determined by high-resolution GDMS.

[0027] Preferably, the correlation degree of linear fitting analysis in step S301 is greater than or equal to 0.998, and / or the linear fitting analysis in step S301 is performed by using a data analysis software.

[0028] Preferably, in step S302, the actual content of trace or constant interference elements in the sample to be measured is obtained based on the analysis of the trace or constant interference elements in the sample to be measured by a traditional standard method, and the inductively coupled plasma-mass spectrometry (ICP-MS), inductively coupled plasma-atomic emission spectrometry (ICP-AES) or titration method can be used.

[0029] Preferably, in step S302, the actual content of trace or constant interference elements in the sample to be measured obtained in step S301 is substituted into the linear relationship model obtained in step S2 to obtain the concentration of trace or constant interference elements in the sample to be measured.

[0030] Compared with the prior art, the present application can at least achieve one of the following beneficial effects:

[0031] (1) The present application constructs the relationship model of the concentration of interference elements and the actual content of interference elements in the standard sample by fitting analysis, and obtains the concentration of trace or constant interference elements in the sample to be measured based on the relationship model, and then deducts the background, removes the interference elements in high-resolution GDMS, improves the detection accuracy, and solves the problems of interference of trace elements by trace or constant elements in high-temperature alloy and low detection accuracy in the high-resolution GDMS analysis in the prior art; at the same time, the method of the present application realizes the accurate detection of trace elements in the presence of interference elements under the limited GDMS resolution of the prior art.

[0032] (2) The present application introduces a standard sample containing an interfering element and not containing a target trace element, carries out high-resolution GDMS analysis on the standard sample, obtains the corresponding high-resolution GDMS measured interfering substance concentration, further establishes a linear relationship model with a higher correlation between the actual content of the interfering element and the interfering substance concentration, and further obtains the trace or constant interfering substance concentration in the sample to be tested from the actual content of the trace or constant interfering element in the sample to be tested for background deduction, thereby solving the problems of mass number interference of trace elements in high-temperature alloys by trace or constant elements in high-resolution GDMS analysis and low detection precision in the prior art.

[0033] (3) The present application carries out high-resolution GDMS analysis on a standard sample with an actual content of the interfering element ≤ 30%, obtains the corresponding high-resolution GDMS measured interfering substance concentration, further establishes a linear relationship model with a higher correlation between the actual content of the interfering element and the interfering substance concentration, and further obtains the trace or constant interfering substance concentration in the sample to be tested from the actual content of the trace or constant interfering element in the sample to be tested for background deduction, thereby solving the problems of mass number interference of trace elements in high-temperature alloys by trace or constant elements in high-resolution GDMS analysis and low detection precision in the prior art.

[0034] Other features and advantages of the present application will be set forth in the following description, and in part will become apparent from the description, or can be learned by practice of the present application. The objects and other advantages of the present application will be realized and achieved by means of the instrumentalities and combinations pointed out in the description and appended claims. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 The linear correlation curve of the Ti content and the interfering substance 49 Ti 40 Ar + concentration in Example 1.

[0036] Figure 2 The linear correlation curve of the Cr content and the interfering substance 53 Cr 40 Ar + concentration in Example 2.

[0037] Figure 3 The linear correlation curve of the Ti content and the interfering substance 48 Ti 36 Ar + concentration in Example 3.

[0038] Figure 4 The linear correlation curve of the Ti content and the interfering substance 49 Ti 40 Ar + intensity in Comparative Example 1.

[0039] Figure 5 For the Cr content in Comparative Example 2 and the interferent 53 Cr 40 Ar + linear correlation curve of intensity. DETAILED DESCRIPTION

[0040] The preferred embodiments of the present application will be described in detail with reference to the drawings, which form a part of this description, and which are illustrative of embodiments of the present application and are not intended to limit the present application, wherein like reference numerals designate like elements in the various views.

[0041] In one aspect, the present application discloses a method for correcting interference for high-resolution glow discharge mass spectrometry analysis of trace element content in high-temperature alloy, comprising:

[0042] S1: selecting interference elements corresponding to trace elements in high-resolution GDMS analysis from components of the high-temperature alloy to be measured;

[0043] S2: taking a series of metal samples without the trace element to be measured and with different contents of interference elements as standard samples, obtaining a relationship model between the concentration of the interferent in high-resolution GDMS analysis of the standard samples and the actual content of the interference elements;

[0044] S3: determining the concentration of the interferent in high-resolution GDMS analysis of the sample to be measured based on the relationship model, correcting the high-resolution GDMS analysis result of the trace element in the sample to be measured with the concentration of the interferent in high-resolution GDMS analysis of the sample to be measured, and obtaining a more accurate trace element content.

[0045] Applicants have found that, due to the influence of various factors, there is no stable correlation between the concentration of volatile matter generated from the metal elements in the analysis sample and the metal element content in the analysis sample in high-resolution GDMS analysis. When the metal element content changes, the correlation between the two changes.

[0046] Compared with the prior art, the present application constructs a relationship model between the concentration of the interferent and the actual content of the interference element in the standard sample by fitting analysis, and obtains the concentration of the trace or constant interferent in the sample to be measured based on the relationship model, and then performs background deduction, removes the interferent in high-resolution GDMS, improves the detection accuracy, and solves the problems of interference of trace or constant elements in high-temperature alloy on trace elements and low detection accuracy in high-resolution GDMS analysis in the prior art. At the same time, the method of the present application realizes accurate detection of trace elements in the presence of interference elements under the limited GDMS resolution condition of the prior art.

[0047] It should be noted that although high-purity argon is usually selected as the atmosphere in GDMS analysis, there are inevitably a small amount of nitrogen, oxygen and water vapor impurities, so the common interfering substances in GDMS analysis include:

[0048] Oxide ions: such as MO + ; Nitride ions: such as M N + ; Hydroxide ions: MOH + ; Argon ions: M Ar + ; M is the interfering element.

[0049] When M Ar + , MO + and the like have the same mass-to-charge ratio as the trace element cation generated by excitation, it will be difficult to separate and identify the mass spectrum analysis, and further cause mass number interference.

[0050] Specifically, the interfering element in the high-temperature alloy can be one or more of Ni, Cr, Fe, Co, Nb, Ti and Mo.

[0051] Specifically, the high-resolution GDMS determination atmosphere contains Ar and one or more impurity elements; the impurity element can be N, O or H.

[0052] Preferably, the relationship model between the concentration of the interfering substance and the actual content of the interfering element can be a linear relationship model.

[0053] Specifically, step S1 comprises:

[0054] S101: determining the interfering element corresponding to the trace element in the high-resolution GDMS analysis based on the components of the high-temperature alloy and the high-resolution GDMS analysis atmosphere;

[0055] S102: selecting standard samples with different contents of interfering elements to perform high-resolution GDMS analysis to obtain the corresponding interfering substance concentration of high-resolution GDMS determination; the standard sample contains trace or constant interfering elements in the sample to be measured, and the interfering element and the high-resolution GDMS determination atmosphere form an interfering substance in the high-resolution GDMS determination, and the content of the trace or constant interfering element in the standard sample is known and the standard sample does not contain the trace element in the sample to be measured.

[0056] Specifically, step S2 comprises: linear fitting analysis of the interfering substance concentration of different standard samples obtained by measurement and the actual content of the corresponding interfering element, and constructing a linear relationship model therebetween.

[0057] The applicant has found that the concentration of the interference in the GDMS analysis index is related to the actual content of the corresponding interference element, and maintains good correlation within a certain range, which can be used for quantitative analysis; and the signal strength of the interference in the GDMS analysis index is poorly correlated with the actual content of the corresponding interference element, and is difficult to be used for quantitative analysis.

[0058] Compared with the prior art, the present application introduces a standard sample containing an interference element but not containing a target trace element, performs high-resolution GDMS analysis on the standard sample, obtains the corresponding interference concentration determined by high-resolution GDMS, further establishes a linear relationship model with high correlation between the actual content of the interference element and the interference concentration, and further obtains the micro or constant interference concentration in the sample to be tested from the actual content of the micro or constant interference element in the sample to be tested for background deduction, thereby solving the problems of mass number interference of micro or constant elements on trace elements in high-temperature alloys and low detection accuracy in high-resolution GDMS analysis in the prior art.

[0059] The applicant has further found that the correlation between the interference concentration of the standard sample and the actual content of the corresponding interference element is related to the actual content of the interference element: the high-temperature alloy system is an alloy system mainly containing nickel, when the content of the constant interference element and the micro interference element in the standard sample exceeds 30% in addition to nickel, the correlation between the interference concentration and the actual content of the corresponding interference element decreases due to the influence of unknown factors between elements; only when the content of the constant interference element and the micro interference element is ≤30%, the interference concentration of the standard sample is in an approximately linear relationship with the actual content of the corresponding interference element, and the correlation is ≥0.998.

[0060] Specifically, the mass fraction of the interference element in the standard sample and the sample to be tested is ≤30%, thereby obtaining a linear relationship model with high correlation between the interference concentration of the standard sample and the actual content of the corresponding interference element, obtaining the accurate actual content of the micro or constant interference element in the sample to be tested based on the model, and obtaining the micro or constant interference concentration in the sample to be tested from the actual content of the micro or constant interference element in the sample to be tested for background deduction, thereby removing the interference in high-resolution GDMS and improving the detection accuracy.

[0061] Compared with the prior art, the present application introduces a standard sample containing an interference element but not containing a target trace element, performs high-resolution GDMS analysis on the standard sample, obtains the corresponding interference concentration determined by high-resolution GDMS, further establishes a linear relationship model with high correlation between the actual content of the interference element and the interference concentration, and further obtains the micro or constant interference concentration in the sample to be tested from the actual content of the micro or constant interference element in the sample to be tested for background deduction, thereby solving the problems of mass number interference of micro or constant elements on trace elements in high-temperature alloys and low detection accuracy in high-resolution GDMS analysis in the prior art.

[0062] Specifically, high-purity argon gas is selected in step S1, containing a small amount of nitrogen, oxygen and water vapor impurities, and the common interference substances in GDMS analysis include:

[0063] Oxide ions: such as MO + Nitride ions: such as MN + Hydroxide ions: MOH + Argon ions: M Ar + M is an interference element.

[0064] When M Ar + , MO + and the like have the same mass-to-charge ratio as the trace element cations generated by excitation, it will be difficult to separate and identify the mass spectrum analysis, and further cause mass number interference.

[0065] Specifically, the interference elements in the high-temperature alloy can be one or more of Ni, Cr, Fe, Co, Nb, Ti and Mo.

[0066] It should be noted that the concentration of the interference substance in the standard sample obtained by high-resolution GDMS analysis in step S2 is completely different from the concentration of the interference element in the corresponding standard sample. The interference element in the standard sample during GDMS analysis mainly exists in the form of element cation, and a small amount exists in the form of interference substance. The element cation and the interference substance will be identified and detected separately in GDMS analysis because of their different mass-to-charge ratios.

[0067] Specifically, step S3 includes:

[0068] S301: analyzing the actual content of trace or constant interference elements in the sample to be measured based on the traditional standard method;

[0069] S302: obtaining the concentration of trace or constant interference substances in the sample to be measured from the actual content of trace or constant interference elements in the sample to be measured based on the relationship model obtained in step S2;

[0070] S303: selecting the sample to be measured for high-resolution GDMS analysis to obtain the concentration of trace elements determined by high-resolution GDMS; after deducting the concentration of trace or constant interference substances in the sample to be measured obtained in step S5, the correction of the content of trace elements in the sample to be measured is completed.

[0071] Specifically, the linear fitting analysis in step S301 can be performed by using data analysis software.

[0072] Specifically, the actual content of the trace or constant interference elements in the sample to be measured obtained in step S302 based on the traditional standard method can be analyzed by inductively coupled plasma mass spectrometry (ICP-MS) or inductively coupled plasma atomic emission spectrometry (ICP-AES) or titration method.

[0073] Specifically, step S302 includes: substituting the actual content of the trace or constant interference elements in the sample to be measured obtained in step S301 into the linear relationship model obtained in step S301 to obtain the concentration of the trace or constant interference elements in the sample to be measured.

[0074] In order to further illustrate the technical solutions of the present application, the following examples and comparative examples are further provided:

[0075] Example 1

[0076] The present embodiment discloses an interference correction method for high-resolution glow discharge mass spectrometry analysis of trace element content in high-temperature alloy, comprising the following steps:

[0077] S1: Based on the components of high-temperature alloy and the analysis atmosphere of high-resolution GDMS, determine the interference elements corresponding to the trace elements during high-resolution GDMS analysis; When analyzing the trace elements in nickel-based high-temperature alloy GH4169 by high-resolution GDMS, due to the complexity of the matrix elements of GH4169 (including Ni, Cr, Fe, Co, Nb, Ti, Mo, etc.), the ionization efficiency of trace elements is greatly affected, and the combination of multiple matrix elements with Ar, O, H and other gas elements forms serious interference to trace elements. For example, the only mass number 89 of trace element Y is seriously interfered by the argon compound ion of interference element Ti 49 Ti 40 Ar + The interference is serious, and the theoretical resolution required for interference separation is 20252. In high-resolution mode (resolution is 10000), it is difficult to completely separate.

[0078] S2: Select standard samples with different contents of interference elements for high-resolution GDMS analysis to obtain the corresponding interference concentration determined by high-resolution GDMS; The standard sample contains trace or constant interference elements in the sample to be measured, and the interference elements form interference in high-resolution GDMS determination with the high-resolution GDMS determination atmosphere. The content of trace or constant interference elements in the standard sample is known, and the standard sample does not contain trace elements in the sample to be measured;

[0079] The accurate content of Ti in the nickel-based alloy sample was obtained by testing using a set of nickel-based alloy samples with different Ti contents as standard samples by ICP-AES method (reference ASTM E2594-20) and ICP-MS method (reference ASTM 2823-17). The accurate determination of Y element in the nickel-based alloy sample was carried out by ICP-MS method (reference ASTM 2823-17), and the content of Y was less than 0.1 μg / g. The results are shown in Table 1.

[0080] Table 1 Linear correlation equation data

[0081]

[0082] Note: The actual concentration of trace elements in the bracket in the table is the actual concentration of trace elements in the standard sample.

[0083] S3: Linear fitting analysis was performed on the concentration of the interference substance of different standard samples obtained by measurement and the actual content of the corresponding interference element, and a linear relationship model was constructed. A set of nickel-based alloy samples with known Ti content and Y content less than 0.1 μg / g were determined by high-resolution GDMS, and the concentration of sample interference substance TiAr + (m / z = 89) was collected, and a linear curve with the content of element Ti as the abscissa and the generated interference substance TiAr + concentration as the ordinate was drawn, and the linear correlation equation was obtained. The results are shown in Table 1, and the linear curve is shown in Figure 1 .

[0084] S4: Based on the traditional standard method, the actual content of trace or constant interference elements in the sample to be measured was obtained by analyzing the trace or constant interference elements in the sample to be measured. The accurate content of Ti in the high-temperature alloy GH4169 was obtained by testing the Ti element in the high-temperature alloy GH4169 by ICP-AES method (reference ASTM E2594-20). The concentration of interference substance TiAr + was calculated by using the established linear correlation equation, and the results are shown in Table 2.

[0085] Table 2 Test results

[0086]

[0087] S5: Based on the linear relationship model obtained in step S3, the concentration of trace or constant interference substance in the sample to be measured was obtained from the actual content of trace or constant interference elements in the sample to be measured, as shown in Table 2.

[0088] S6: Selecting the sample to be tested for high-resolution GDMS analysis to obtain the trace element concentration determined by high-resolution GDMS; and correcting the trace element content of the sample to be tested by deducting the trace or constant interferent concentration obtained in step S5, as shown in Table 2.

[0089] In this embodiment, the content of the interference element Ti has a good linear relationship with the concentration of the interferent TiAr + , and the correlation coefficient R 2 = 0.998. The data in Table 2 show that after high-resolution glow discharge mass spectrometry testing and interference deduction correction, the test result of the trace element Y in the nickel-based high-temperature alloy GH4169 is completely consistent with the analysis result by the classical ICP-MS method, and the analysis accuracy is higher.

[0090] Embodiment 2

[0091] The embodiment discloses an interference correction method for high-resolution glow discharge mass spectrometry analysis of trace element content in a high-temperature alloy, comprising the following steps:

[0092] S1: determining the interference elements corresponding to the trace elements during high-resolution GDMS analysis based on the components of the high-temperature alloy and the analysis atmosphere of the high-resolution GDMS; when the trace elements in the nickel-based high-temperature alloy DD5 are analyzed by the high-resolution GDMS, the DD5 matrix elements usually include more than ten kinds of Ni, Cr, Fe, Al, Ti, Mo, Re, etc., the multiple matrix elements directly affect the ionization efficiency of the trace elements, and the combination of the matrix elements and the gas elements causes serious mass spectrometric interference to the trace elements, for example, the unique mass number 93 of the trace element Nb is seriously interfered by the argon compound ion 53 Cr 40 Ar + , and the theoretical resolution required for interference separation is 27732, which is difficult to completely separate in the high-resolution mode (with a resolution of 10000).

[0093] S2: selecting standard samples with different contents of interference elements for high-resolution GDMS analysis to obtain the corresponding interferent concentrations determined by high-resolution GDMS; the standard samples contain trace or constant interference elements in the sample to be tested, and the interference elements form interferents with the high-resolution GDMS analysis atmosphere during high-resolution GDMS determination, the content of the trace or constant interference elements in the standard sample is known, and the standard sample does not contain the trace elements in the sample to be tested;

[0094] A group of nickel-based alloy samples with different Cr contents are used for testing by titration (reference GB / T223.11) to obtain the accurate content of Cr in the nickel-based alloy samples. The Nb element in the nickel-based alloy samples is accurately determined by the ICP-MS method (reference ASTM 2823-17), and the results are shown in Table 3.

[0095] Table 3 Linear correlation equation data

[0096] Note: The actual concentration of trace elements in the standard sample is in the brackets in the table.

[0097] S3: Linear fitting analysis was performed on the concentration of the interference substance obtained by measuring different standard samples and the actual content of the corresponding interference element to construct a linear relationship model between the two. A group of nickel-based alloy samples with known Cr content and Nb content less than 0.1 μg / g were measured by high-resolution GDMS, and the concentration of the interference substance CrAr + (m / z = 93) was collected, and a linear curve was drawn with the element Cr content as the abscissa and the generated interference substance CrAr + concentration as the ordinate, and the linear correlation equation was obtained. The results are shown in Table 3, and the linear curve is shown in Figure 2 .

[0098] S4: Based on the analysis of trace or constant interference elements in the sample to be tested by the traditional standard method, the actual content of trace or constant interference elements in the sample to be tested was obtained. The titration method (reference GB / T223.11) was used to test the Cr element in high-temperature alloy DD5, and the accurate content of Cr was obtained. The concentration of the interference substance CrAr+ in DD5 was calculated using the established linear correlation equation, and the results are shown in Table 4.

[0099] Table 4 Test results

[0100]

[0101] S5: Based on the linear relationship model obtained in step S3, the concentration of trace or constant interference elements in the sample to be tested was obtained from the actual content of trace or constant interference elements in the sample to be tested. The high-temperature alloy DD5 sample with known Cr content was measured by high-resolution glow discharge mass spectrometry, and the concentration at the mass-to-charge ratio m / z = 93 was collected to obtain the apparent concentration of 93Nb, i.e., the concentration sum of Nb element and interference substance CrAr+. After deducting the corresponding interference substance CrAr+ concentration in high-temperature alloy DD5, the true concentration of the element 93 to be tested, Nb, was obtained, and the results are shown in Table 4. The accuracy of the test results of this method was compared by inductively coupled plasma mass spectrometry (ICP-MS, reference ASTM E2823-17).

[0102] S6: Selecting the sample to be tested for high-resolution GDMS analysis to obtain the trace element concentration determined by high-resolution GDMS; and subtracting the concentration of the trace or constant interferent in the sample to be tested obtained in step S5 to complete the correction of the trace element content of the sample to be tested, as shown in Table 4.

[0103] In this embodiment, the content of the interference element Cr has a good linear relationship with the concentration of the interferent CrAr + , R 2 = 0.999. The data in Table 4 show that after high-resolution glow discharge mass spectrometry testing and interference subtraction correction, the test result of the trace element Nb in the nickel-based high-temperature alloy DD5 is completely consistent with the classical ICP-MS analysis result, and the detection accuracy is higher.

[0104] Embodiment 3

[0105] The embodiment discloses an interference correction method for high-resolution glow discharge mass spectrometry analysis of trace element content in a high-temperature alloy, comprising the following steps:

[0106] S1: determining the interference element corresponding to the trace element during high-resolution GDMS analysis based on the components of the high-temperature alloy and the analysis atmosphere of the high-resolution GDMS; and analyzing the trace element in the nickel-based high-temperature alloy K417 by high-resolution glow discharge mass spectrometry (GDMS), wherein the matrix elements of K417 are Ni, Cr, Co, Mo, Al, Ti and the like, which form serious interference to the trace element, for example, the trace element Sr, which has four mass numbers of 84, 86, 87 and 88, and research finds that 84 Sr is least interfered, so 84Sr is selected as the analysis isotope, and the interference of the argon compound ion 48 Ti 36 Ar + interferes with 84Sr, and the theoretical resolution required for interference separation is 40000, which is difficult to completely separate in the high-resolution mode (the resolution is 10000).

[0107] S2: selecting standard samples with different contents of interference elements for high-resolution GDMS analysis to obtain the corresponding interference concentration determined by high-resolution GDMS; the standard sample contains trace or constant interference elements in the sample to be tested, and the interference elements form an interferent with the high-resolution GDMS determination atmosphere during high-resolution GDMS determination, the content of the trace or constant interference element in the standard sample is known, and the standard sample does not contain the trace element in the sample to be tested;

[0108] A set of nickel-based alloy samples with different Ti contents were tested using the ICP-AES method (refer to ASTM E2594-20) to obtain the accurate Ti content in the nickel-based alloy samples. The Sr element in the nickel-based alloy samples was accurately determined using the ICP-MS method (refer to ASTM 2823-17), and the results are shown in Table 5.

[0109] Table 5 Data on linear correlation equations Note: The values ​​in parentheses in the table represent the actual concentrations of trace elements in the standard samples.

[0110] S3: Linear fitting analysis was performed on the concentrations of interfering substances and the actual contents of the corresponding interfering elements in different standard samples obtained from the measurements, and a linear relationship model between the two was constructed; a group of nickel-based alloy samples with known Ti content and Sr content less than 0.1 μg / g were measured using high-resolution GDMS, and the interfering substances TiAr were collected from the samples. + The concentration of (m / z = 84) was plotted with the elemental Ti content on the x-axis and the generated interference TiAr on the y-axis. + The linear correlation equation was obtained by plotting the concentration on the ordinate of the linear curve. The results are shown in Table 5. (The linear curve is shown in...) Figure 3 .

[0111] S4: The actual content of trace or constant interfering elements in the test sample was obtained based on traditional standard methods. The Ti element in the high-temperature alloy K417 was tested using ICP-AES (referencing ASTM E2594-20) to obtain the accurate Ti content. The established linear correlation equation was used to calculate the interfering substance TiAr in K417. + Concentrations, results are shown in Table 6.

[0112] Table 6. Experimental Results

[0113]

[0114] S5: Based on the linear relationship model obtained in step S3, the concentration of trace or constant interfering elements in the sample to be tested is obtained from the actual content of trace or constant interfering elements in the sample to be tested, as shown in Table 2.

[0115] S6: Select the sample to be tested for high-resolution GDMS analysis to obtain the trace element concentration determined by high-resolution GDMS; use high-resolution GDMS to determine the concentration of the high-temperature alloy K417 sample with known Ti content, and collect the concentration at the mass-to-nucleus ratio m / z = 84. 84 The apparent concentration of Sr is the sum of Sr elemental and the interfering substance TiAr. + The concentration and deduction of the corresponding interference TiAr in the high-temperature alloy K417. +Concentration, the measured element 84 The true concentration of Sr was obtained, and the results are shown in Table 6. The accuracy of the test results of the method was compared by using the ICP-MS method (refer to ASTM E2823-17).

[0116] In this embodiment, the content of the interference element Ti and the intensity of the interference TiAr + There is a good linear relationship between the concentration and the intensity of the interference TiAr 2 (m / z = 89), and R + = 0.9991. The data in Table 6 show that after the high-resolution glow discharge mass spectrometry test and the interference correction, the test results of the trace element Sr in the nickel-based high-temperature alloy K417 are consistent with the analysis results of the classic ICP-MS method, and the detection accuracy is higher.

[0117] Comparative Example 1

[0118] This comparative example discloses a method for correcting interference of trace element Y in high-temperature alloy GH4169 by high-resolution glow discharge mass spectrometry (GDMS), which establishes a linear correlation equation between the content of the interference element and the intensity of the interference, and quantifies the intensity of the interference; the rest are the same as in Example 1:

[0119] A group of nickel-based alloy samples with known Ti content and Y content less than 0.1 μg / g were determined by high-resolution GDMS, and the intensity of the interference TiAr + (m / z = 89) of the sample was collected, a linear curve with the content of the element Ti as the abscissa and the intensity of the generated interference TiAr + as the ordinate was drawn, and a linear correlation equation was obtained, the results are shown in Table 7, and the linear curve is shown in Figure 4 .

[0120] In this comparative test, the content of the interference element Ti and the intensity of the interference TiAr 2 have no good linear relationship (R 2 = 0.914), and cannot be used for interference correction of trace elements in high-temperature alloys.

[0121] Linear correlation equation data in Table 7

[0122]

[0123] Comparative Example 2

[0124] This comparative example discloses a method for correcting interference of trace element content in high-temperature alloy by high-resolution glow discharge mass spectrometry, which is different from Example 2 in that the content of the standard sample Cr does not satisfy ≤30%, and the rest is the same as in Example 2.

[0125] Linear correlation equation data is shown in Table 8 and Figure 5 :

[0126] Table 8 linear correlation equation data

[0127]

[0128] Note: The actual concentration of trace elements in the standard sample in the brackets in the table.

[0129] The test value of trace element Nb is measured based on the linear correlation equation, as shown in Table 9:

[0130] Table 9 test results

[0131]

[0132] From the above, the content of Cr in the standard sample of the comparative example 2 is too large, which leads to the decrease of the correlation degree of the linear relationship model of the standard sample, and the measured content of Nb is even negative, which obviously cannot accurately measure the content of trace element Nb.

[0133] The above is only the preferred specific embodiment of the present application, but the protection scope of the present application is not limited to this, any person skilled in the art can easily think of the changes or replacements within the technical range disclosed by the present application, which should be covered in the protection scope of the present application.

Claims

1. An interference correction method for high-resolution glow discharge mass spectrometry analysis of trace element content in high-temperature alloys, characterized in that, include: S1: Screening out the interfering elements corresponding to trace elements in high-resolution GDMS analysis from the high-temperature alloy components to be tested; S2: Using a series of metal samples that do not contain the trace elements to be measured and have different contents of interfering elements as standard samples, obtain a model of the relationship between the concentration of interfering substances and the actual content of interfering elements during high-resolution GDMS analysis of the standard samples. S3: Determine the concentration of interfering substances in the high-resolution GDMS analysis of the sample to be tested based on the aforementioned relationship model, and use the concentration of interfering substances in the high-resolution GDMS analysis of the sample to be tested to correct the high-resolution GDMS analysis results of trace elements in the sample to be tested.

2. The interference correction method for high-resolution glow discharge mass spectrometry analysis of trace element content in high-temperature alloys according to claim 1, characterized in that, Step S1 includes: S101: Based on the high-temperature alloy composition and the high-resolution GDMS analysis atmosphere, determine the interfering elements corresponding to trace elements during high-resolution GDMS analysis. S102: Select standard samples with different levels of interfering elements for high-resolution GDMS analysis to obtain the corresponding concentration of interfering substances determined by high-resolution GDMS; the standard samples contain trace or major interfering elements from the test samples. During high-resolution GDMS determination, the interfering elements react with the high-resolution GDMS determination atmosphere to form interfering substances. The content of trace or major interfering elements in the standard samples is known, and the standard samples do not contain trace elements from the test samples.

3. The interference correction method for high-resolution glow discharge mass spectrometry analysis of trace element content in high-temperature alloys according to claim 1, characterized in that, Step S2 includes: performing linear fitting analysis on the concentration of interfering substances in different standard samples obtained by measurement and the actual content of the corresponding interfering elements, and constructing a linear relationship model between the two.

4. The interference correction method for high-resolution glow discharge mass spectrometry analysis of trace element content in high-temperature alloys according to claim 1, characterized in that, The interfering substances include: Oxide ion: MO + ; Nitrogenide ions: MN + ; Hydroxide ion: MOH + ; Argon compound ions: M Ar + ; M represents the interference element.

5. The interference correction method for high-resolution glow discharge mass spectrometry analysis of trace element content in high-temperature alloys according to claim 4, characterized in that, The interfering element is one or more of Ni, Cr, Fe, Co, Nb, Ti, and Mo.

6. The interference correction method for high-resolution glow discharge mass spectrometry analysis of trace element content in high-temperature alloys according to claim 5, characterized in that, The mass fraction of interfering elements in the standard sample and the sample to be tested is ≤30%.

7. The interference correction method for high-resolution glow discharge mass spectrometry analysis of trace element content in high-temperature alloys according to any one of claims 1-6, characterized in that, Step S3 includes: S301: Based on traditional standard methods, the actual content of trace or constant interfering elements in the sample to be tested is obtained by analyzing the trace or constant interfering elements in the sample to be tested. S302: Based on the relationship model obtained in step S2, the concentration of trace or constant interfering elements in the sample to be tested is obtained from the actual content of trace or constant interfering elements in the sample to be tested. S303: Select the sample to be tested for high-resolution GDMS analysis to obtain the trace element concentration determined by high-resolution GDMS; subtract the concentration of trace or major interfering substances in the sample to be tested obtained in step S5 from the trace element concentration determined by high-resolution GDMS to complete the correction of the trace element content of the sample to be tested.

8. The interference correction method for high-resolution glow discharge mass spectrometry analysis of trace element content in high-temperature alloys according to claim 7, characterized in that, In step S301, the correlation of the linear fitting analysis is ≥0.998, and / or, the linear fitting analysis in step S301 is performed using data analysis software.

9. The interference correction method for high-resolution glow discharge mass spectrometry analysis of trace element content in high-temperature alloys according to claim 7, characterized in that, In step S302, the actual content of trace or constant interfering elements in the sample to be tested is obtained by analyzing the trace or constant interfering elements in the sample based on traditional standard methods. Inductively coupled plasma mass spectrometry, inductively coupled plasma atomic emission spectrometry, or titration can be used.

10. The interference correction method for high-resolution glow discharge mass spectrometry analysis of trace element content in high-temperature alloys according to claim 7, characterized in that, Step S302 includes: substituting the actual content of trace or constant interfering elements in the sample to be tested obtained in step S301 into the relational model obtained in step S2 to obtain the concentration of trace or constant interfering substances in the sample to be tested.

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