Measurement method of major and minor components of porcelain insulators

Abstract

The present invention provides a method for measuring the major and minor components of porcelain insulators. The measuring method comprises the following steps: determining the measuring range of the main elements according to the chemical composition of each type of porcelain insulator. Selecting a plurality of standard samples according to the measuring range of the main elements. Performing X-ray fluorescence spectrum detection on the plurality of standard samples respectively to obtain a plurality of corresponding fluorescence spectrum data of the standard samples. Establishing a mapping relationship between the fluorescence spectrum value corresponding to each major element and the element content according to the plurality of corresponding fluorescence spectrum data of the standard samples. Determining the element content of each major element in the porcelain insulator to be tested based on the mapping relationship between the fluorescence spectrum value corresponding to each major element and the element content according to the fluorescence spectrum data of the object to be tested. The above-mentioned method for measuring the major and minor components of porcelain insulators is based on the method of X-ray fluorescence spectrum detection for determination, has short steps, short determination cycle, low intensity, and high accuracy and precision of the determination results.

Description

Technical Field

[0001] The invention relates to the field of porcelain insulator detection, and in particular to a method for measuring primary and secondary quantitative components of a porcelain insulator. Background Art

[0002] Porcelain insulators are important components in power plants and substation equipment. They are an important component of mechanical connection and electrical insulation of transmission lines and should have good mechanical and electrical properties.

[0003] At present, the inspection and test items for the porcelain parts of power grid insulators entering the grid are mainly conventional tests (appearance, size, shape and position deviation, porosity, temperature cycle, etc.), electrical tests (impact withstand voltage, power frequency voltage, radio interference, visible corona voltage, contamination, breakdown voltage, etc.) and mechanical tests (bending, stretching, torsional damage, compression, electromechanical damage, etc. composite tests), internal pressure. The composition of porcelain insulators is only controlled by internal process control documents during the production of porcelain blanks, and the components are tested by chemical analysis. The analysis process has complicated steps, long cycles and high intensity. Summary of the invention

[0004] The main purpose of the present invention is to provide a method for measuring the major and minor components of a porcelain insulator, so as to solve the technical problems of detecting components by chemical analysis method, complicated steps, long cycle and high intensity of analysis process.

[0005] To achieve the above object, the present invention provides a method for measuring the major and minor components of a porcelain insulator, comprising the following steps:

[0006] According to the chemical composition of each type of porcelain insulator, the measurement range of the main element oxides is determined; wherein the main element oxides include silicon oxide, aluminum oxide, iron oxide, titanium oxide and potassium oxide.

[0007] A plurality of standard samples are selected according to the measurement range of the main element oxide; the content of each main element oxide in the plurality of standard samples is distributed within the measurement range corresponding to the main element oxide.

[0008] X-ray fluorescence spectrum detection is performed on multiple standard samples respectively to obtain multiple corresponding standard sample fluorescence spectrum data; the standard sample fluorescence spectrum data includes the fluorescence spectrum values ​​of the main elements corresponding to the main element oxides in the standard samples.

[0009] A mapping relationship between the fluorescence spectrum value corresponding to each main element and the element content is established according to the plurality of corresponding fluorescence spectrum data of standard samples.

[0010] X-ray fluorescence spectrum detection is performed on the porcelain insulator to be tested to obtain fluorescence spectrum data of the object to be tested, and the fluorescence spectrum data of the object to be tested includes the fluorescence spectrum values ​​of each main element in the porcelain insulator to be tested.

[0011] According to the fluorescence spectrum data of the object to be tested, based on the mapping relationship between the fluorescence spectrum value corresponding to each main element and the element content, the element content of each main element in the porcelain insulator to be tested is determined.

[0012] According to an embodiment of the present application, the measuring range of the silicon oxide is 0-80%, the measuring range of the aluminum oxide is 0-90%, the measuring range of the iron oxide is 0-14%, the measuring range of the titanium oxide is 0-5%, and the measuring range of the potassium oxide is 0-5%.

[0013] The content of each main element oxide in the plurality of standard samples is distributed within the measurement range corresponding to the main element oxide and satisfies the following conditions:

[0014] In the measuring range of silicon oxide and the measuring range of aluminum oxide, there is at least one standard sample in each 10% gradient range, and there are 1-2 standard samples in the measuring range within 10%.

[0015] In the measurement range of the iron oxide, the measurement range of the titanium oxide and the measurement range of the potassium oxide, there is at least one standard sample in each 1% gradient range.

[0016] According to an embodiment of the present application, the number of standard samples of the plurality of standard samples is 15, and the plurality of standard samples are YSS068-2013, YSBC13803-94, YSS066-2013, YSS065-2013, YSS064-2013, ZBM1082, GBW07146, GBW03115, GBW07451, GBW07302a, YSS064-2013 A mixture of GBW07146 and GBW07302a in a mass ratio of 3:7, a mixture of YSS065-2013 and YSS064-2013 in a mass ratio of 1:1, a mixture of GBW07146 and YSS064-2013 in a mass ratio of 3:7, a mixture of GBW07146 and GBW07302a in a mass ratio of 8:2, and a mixture of GBW07146 and GBW07451 in a mass ratio of 1:1.

[0017] According to an implementation manner of the present application, in the step of performing X-ray fluorescence spectrometry detection, the tube voltage of the high-voltage X-ray tube is 8 kV, the tube current is 50 μA, the end window is an Ag target, and the Kα line of silicon, the Kα line of aluminum, the Kα line of titanium, the Kα line of iron, and the Kα line of potassium are measured.

[0018] According to an embodiment of the present application, in the step of performing X-ray fluorescence spectroscopy detection, the method for preparing a test sample includes:

[0019] The solvent and the sample are mixed evenly at a mass ratio of 10:1, and 4-5 drops of a release agent are added, and the mixture is melted in a melting furnace at 1100°C for 25 minutes, cooled and solidified in a mold, and demolded to obtain a test sample. The sample is a standard sample or a porcelain insulator to be tested. The solvent is a mixed solvent of lithium tetraborate and lithium metaborate in a mass ratio of 2:1. The release agent is an ammonium bromide solution.

[0020] According to an embodiment of the present application, the step of establishing a mapping relationship between the fluorescence spectrum value corresponding to each main element and the element content according to the plurality of corresponding standard sample fluorescence spectrum data includes:

[0021] According to the matrix effect of each main element and the influence of the spectral line overlap of each main element, the linear relationship between the fluorescence spectrum value corresponding to each main element and the element content is corrected to obtain the mapping relationship.

[0022] According to the implementation of the present application, the mapping relationship between the fluorescence spectrum value corresponding to each main element and the element content is:

[0023] )+b.

[0024] in, is the mass fraction of each main element, %. is the mass fraction of the interfering element that interferes with the corresponding main element, %. a and b are the slope and intercept of the calibration curve, respectively. is the fluorescence intensity of each main element, cps. is the fluorescence intensity of the overlapping lines, cps. is the line overlap correction factor. is the influence coefficient of the interfering element on the main element.

[0025] According to the implementation of the present application, when the main element is silicon, the corresponding interfering elements are aluminum and potassium. is the mass fraction of silicon, is the mass fraction of aluminum element and the mass fraction of potassium element.

[0026] When the main element is aluminum, the corresponding interfering elements are silicon and potassium. is the mass fraction of aluminum, is the mass fraction of silicon element and the mass fraction of potassium element.

[0027] In the case where the main element is iron, the corresponding interfering element is titanium. is the mass fraction of iron, is the mass fraction of titanium element.

[0028] When the main element is titanium, the corresponding interfering elements are potassium and iron. is the mass fraction of titanium, is the mass fraction of potassium and the mass fraction of iron.

[0029] When the main element is potassium, the corresponding interfering elements are silicon and aluminum. is the mass fraction of potassium, is the mass fraction of silicon and the mass fraction of aluminum.

[0030] According to an embodiment of the present application, according to the fluorescence spectrum data of the object to be tested, based on the mapping relationship between the fluorescence spectrum value corresponding to each main element and the element content, the step of determining the element content of each main element in the porcelain insulator to be tested includes:

[0031] The standard curves of each main element were established based on the mapping relationship between the fluorescence spectrum values ​​corresponding to each main element and the element content.

[0032] Substitute the fluorescence spectrum value of each main element in the fluorescence spectrum data of the object to be tested into the corresponding main element standard curve to determine the element content of each main element in the porcelain insulator to be tested.

[0033] According to an embodiment of the present application, the method further includes: analyzing the accuracy and precision of the measurement method.

[0034] In the above-mentioned method for measuring the major and minor components of porcelain insulators, the measurement range of each main element oxide is determined, and multiple standard samples are selected. The range of standard samples is widely distributed, and the mapping relationship between the fluorescence spectrum value and the element content established by the fluorescence spectrum data measured is close to the actual mapping relationship between the two, so the accuracy and precision of the measured element content are high. The above-mentioned method for measuring the major and minor components of porcelain insulators is based on the method of X-ray fluorescence spectrum detection, with short steps, short measurement cycle, low intensity, and high accuracy and precision of the measurement results. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying creative work.

[0036] Figure 1 It is a schematic diagram of the structure of an X-ray fluorescence spectrometer.

[0037] Figure 2 This is a diagram of the working principle of X-ray fluorescence spectrometry.

[0038] The realization of the purpose, functional features and advantages of the present invention will be further explained in conjunction with the implementation methods and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0039] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0040] It should be noted that all directional indications (such as up, down, etc.) in the embodiments of the present invention are only used to explain the relative position relationship, movement status, etc. between the components under a certain specific posture (as shown in the accompanying drawings). If the specific posture changes, the directional indication will also change accordingly.

[0041] In addition, in the present invention, the descriptions such as "first", "second", etc. are only used for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" or "second" may explicitly or implicitly include at least one of the features.

[0042] Furthermore, the technical solutions between the various embodiments of the present invention may be combined with each other, but this must be based on the fact that they can be implemented by ordinary technicians in the field. When the combination of technical solutions is mutually contradictory or cannot be implemented, it should be deemed that such combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0043] The present invention provides a method for measuring the major and minor components of a porcelain insulator, comprising the following steps:

[0044] S100: Determine the measurement range of main element oxides according to the chemical composition of each type of porcelain insulator; wherein the main element oxides include silicon oxide, aluminum oxide, iron oxide, titanium oxide and potassium oxide.

[0045] The chemical composition of various types of porcelain insulators in the power system is statistically analyzed, and the main element oxides include silicon oxide, aluminum oxide, iron oxide, titanium oxide and potassium oxide. The distribution range of each main element oxide in each type of porcelain insulator is determined, and it is used as the applicable range for the main and secondary component detection of porcelain insulators in this method, see Table 3. The measurement range of each main element oxide is determined according to the chemical composition of the porcelain insulator. The measurement range of the main element oxide needs to cover the main element oxide content range of different types of porcelain insulators, so as to select suitable standard samples and improve the applicable scope of the measurement method. The main elements corresponding to the main element oxides of silicon oxide, aluminum oxide, iron oxide, titanium oxide and potassium oxide are silicon, aluminum, iron, titanium and potassium, respectively.

[0046] In some embodiments, the measuring range of the silicon oxide is 0-80%, the measuring range of the aluminum oxide is 0-90%, the measuring range of the iron oxide is 0-14%, the measuring range of the titanium oxide is 0-5%, and the measuring range of the potassium oxide is 0-5%.

[0047] S200: selecting a plurality of standard samples according to the measurement range of the main element oxide; the content of each main element oxide in the plurality of standard samples is distributed within the measurement range corresponding to the main element oxide.

[0048] Since there are five main element oxides that need to be measured, each main element oxide has a corresponding measurement range. All standard samples need to cover the measurement of each main element oxide as a whole and be distributed as evenly as possible. That is, there is at least one standard sample in different gradient ranges.

[0049] S300: Performing X-ray fluorescence spectrum detection on a plurality of standard samples respectively to obtain a plurality of corresponding fluorescence spectrum data of the standard samples; the fluorescence spectrum data of the standard samples include fluorescence spectrum values ​​of the main elements corresponding to the oxides of the main elements in the standard samples.

[0050] See also Figure 1 and Figure 2 The principle of X-ray fluorescence spectrometry is as follows: the X-ray beam emitted by the X-ray tube of the X-ray fluorescence spectrometer excites the sample to be tested, generating X-ray fluorescence characteristic spectrum lines, which are sent to the detector for detection after passing through the collimator and the spectroscopic crystal, so as to quantitatively analyze each element in the sample. X-ray fluorescence characteristic spectrum lines are element characteristic spectrum lines formed by the energy released by the outer electrons of atoms (such as K, L, M layers) of different elements in the sample absorbing the energy of the X-ray beam and transitioning to orbits farther away from the nucleus (such as L, M, N layers). Common characteristic spectrum lines include K, L, M (α, β, γ) series, etc.

[0051] Specifically, the method includes preparing test samples and blank test samples from each standard sample respectively, and then using an X-ray fluorescence spectrometer to detect the samples to obtain corresponding fluorescence spectrum data of the standard samples.

[0052] S400: Establishing a mapping relationship between the fluorescence spectrum value corresponding to each main element and the element content according to the plurality of corresponding standard sample fluorescence spectrum data.

[0053] In this step, a mapping relationship can be determined between the fluorescence spectrum value corresponding to each main element and the content of the element.

[0054] S500: Perform X-ray fluorescence spectrum detection on the porcelain insulator to be tested to obtain fluorescence spectrum data of the object to be tested, wherein the fluorescence spectrum data of the object to be tested includes fluorescence spectrum values ​​of main elements in the porcelain insulator to be tested.

[0055] In the same way, the porcelain insulator to be tested is subjected to X-ray fluorescence spectrum detection to obtain fluorescence spectrum data of the object to be tested.

[0056] S600: Determine the element content of each main element in the porcelain insulator to be tested according to the fluorescence spectrum data of the object to be tested and based on the mapping relationship between the fluorescence spectrum value corresponding to each main element and the element content.

[0057] Substitute the fluorescence spectrum values ​​of each main element in the fluorescence spectrum data of the object to be tested into the mapping relationship to determine the element content of each main element. On this basis, the content of each main element oxide can be determined according to the composition of the molecular formula of each main element oxide.

[0058] In general, the method for measuring the major and minor components of porcelain insulators adopted by the present invention is to apply the principle of X-ray fluorescence spectroscopy to quickly detect the major and minor components of porcelain insulators. Compared with the existing detection technology, the present invention has significant improvements and progress in quality monitoring, detection efficiency, work intensity, field application, economic benefits, etc.

[0059] In the above-mentioned method for measuring the major and minor components of porcelain insulators, the measurement range of each main element oxide is determined, and multiple standard samples are selected. The range of standard samples is widely distributed, and the mapping relationship between the fluorescence spectrum value and the element content established by the fluorescence spectrum data measured is close to the actual mapping relationship between the two, so the accuracy and precision of the measured element content are high. The above-mentioned method for measuring the major and minor components of porcelain insulators is based on the method of X-ray fluorescence spectrum detection, with short steps, short measurement cycle, low intensity, and high accuracy and precision of the measurement results.

[0060] In some embodiments, the content of each main element in the plurality of standard samples is distributed within the measurement range of the corresponding main element and satisfies the following conditions: within the measurement range of the silicon oxide and the measurement range of the aluminum oxide, there is at least one standard sample in each 10% gradient range, and within the measurement range of 10%, there are 1-2 standard samples. Within the measurement range of the iron oxide, the measurement range of the titanium oxide, and the measurement range of the potassium oxide, there is at least one standard sample in each 1% gradient range.

[0061] Referring to Table 1, taking the measurement range of the aforementioned main element oxides as an example: the measurement range of silicon oxide is 0-80%, the measurement range of aluminum oxide is 0-90%, the measurement range of iron oxide is 0-14%, the measurement range of titanium oxide is 0-5%, and the measurement range of potassium oxide is 0-5%.

[0062] Table 1 Applicable scope of the detection method for the main and secondary components of porcelain insulators

[0063]

[0064] In the measurement range of silicon oxide and the measurement range of aluminum oxide, there is at least one standard sample in each 10% gradient range, such as 0% to 10% for one gradient, 20% to 30% for one gradient, 20% to 40% for one gradient, and so on, that is, there is at least one sample in each 10% gradient. Furthermore, the main element contents of two standard samples in adjacent gradients differ by about 10%.

[0065] Accordingly, there are 1-2 standard samples within the measurement range of 10%.

[0066] In the measurement range of the iron oxide, the measurement range of the titanium oxide and the measurement range of the potassium oxide, there is at least one standard sample in each 1% gradient range, such as 0%~1% is a gradient, 2%~3% is a gradient, 13%~14% is a gradient, and so on, that is, there is at least one sample in each 1% gradient. Furthermore, the main element content of two standard samples in adjacent gradients differs by about 1%.

[0067] Under this condition, within the measurement range of the main elements, each main element, regardless of its content, has standard samples evenly distributed in different gradients. This ensures that the mapping relationship between the fluorescence spectrum values ​​established by the measured fluorescence spectrum data and the element content is close to the actual mapping relationship between the two, so the measured element content has high accuracy and precision.

[0068] In some embodiments, the number of standard samples of the plurality of standard samples is 15, and the plurality of standard samples are YSS068-2013, YSBC13803-94, YSS066-2013, YSS065-2013, YSS064-2013, ZBM1082, GBW07146, GBW03115, GBW07451, GBW07302a, YSS064-2013, and G A mixture of BW07302a in a mass ratio of 3:7, a mixture of YSS065-2013 and YSS064-2013 in a mass ratio of 1:1, a mixture of GBW07146 and YSS064-2013 in a mass ratio of 3:7, a mixture of GBW07146 and GBW07302a in a mass ratio of 8:2, a mixture of GBW07146 and GBW07451 in a mass ratio of 1:1.

[0069] The content of oxides of each element in each standard sample is shown in Table 2.

[0070] Table 2 Distribution of oxide contents of each element in standard samples used to establish multivariate linear regression analysis model

[0071]

[0072] As shown in Table 2, the above standard samples fully meet the measurement range of the main elements, and the standard samples are evenly distributed in different gradients, so that the mapping relationship between the fluorescence spectrum value and the element content established by the measured fluorescence spectrum data is close to the actual mapping relationship between the two, so the accuracy and precision of the measured element content are high. The above standard samples are all standard samples of the relevant national sample library.

[0073] In some embodiments, in the step of performing X-ray fluorescence spectrum detection, the tube voltage of the high-voltage X-ray tube is 8 kV, the tube current is 50 μA, the end window is an Ag target, and the Kα line of silicon, the Kα line of aluminum, the Kα line of titanium, the Kα line of iron, and the Kα line of potassium are measured. Figure 2 Under this condition, relatively accurate X-ray fluorescence spectrum values ​​can be obtained.

[0074] In some embodiments, in the step of performing X-ray fluorescence spectroscopy detection, the method of preparing the test sample includes:

[0075] The solvent and the sample are mixed evenly at a mass ratio of 10:1, and 4-5 drops of a release agent are added, and the mixture is melted in a melting furnace at 1100°C for 25 minutes, cooled and solidified in a mold, and demolded to obtain a test sample. The sample is a standard sample or a porcelain insulator to be tested. The solvent is a mixed solvent of lithium tetraborate and lithium metaborate in a mass ratio of 2:1. The release agent is an ammonium bromide solution.

[0076] When preparing the test sample, a method of preparing the sample by melting can be used. In order to eliminate the particle size effect and mineral effect in the standard sample and effectively reduce the matrix effect, the embodiment of the present invention adopts a glass melting method to prepare the sample, with lithium tetraborate-lithium metaborate (mass ratio of 2:1) as the solvent and ammonium bromide solution as the demolding agent. Exemplarily, the process of the present invention uses an analytical balance (precision: 0.0001g) to weigh a quantitative solvent and a test sample (mass ratio of 10:1), mix the sample and the solvent evenly, add 4-5 drops of demolding agent, place it in a melting furnace for melting (temperature and time are 1100°C, 25min), and after the melting is completed, transfer it to a pre-heated mold for cooling, solidification and demolding. The melting piece surface in contact with the bottom of the mold is the surface to be tested. The glass melting piece test sample should have a regular appearance, a smooth surface, a uniform overall appearance, and no defects such as sand holes and bubbles, otherwise the test sample should be re-prepared.

[0077] Prepare a blank sample as a background reference. Replace the test sample with an equal weight of solvent and repeat the above steps.

[0078] In some embodiments, the step of establishing a mapping relationship between the fluorescence spectrum value corresponding to each main element and the element content according to the plurality of corresponding standard sample fluorescence spectrum data includes:

[0079] According to the matrix effect of each main element and the influence of the spectral line overlap of each main element, the linear relationship between the fluorescence spectrum value corresponding to each main element and the element content is corrected to obtain the mapping relationship.

[0080] Since the elements in the standard samples are complex and their contents vary greatly, the influence of matrix effect and spectral line overlap needs to be considered. See Table 3.

[0081] Table 3 Characteristic X-ray fluorescence characteristic spectral line energy table of major and minor elements in porcelain insulators

[0082]

[0083] For example, the Kα spectrum of silicon is 1.74KeV, and the Kβ spectrum of aluminum is 1.55KeV, and there may be overlap between the two spectrum lines. Therefore, when determining the mapping relationship between the fluorescence spectrum value of silicon and the element content, aluminum is an interfering element of silicon, and the matrix effect of each main element and the influence of the overlap of the spectrum lines of each main element must be considered to correct the mapping relationship so that the corrected mapping relationship is closer to the real mapping relationship.

[0084] In some embodiments, the mapping relationship between the fluorescence spectrum value corresponding to each main element and the element content (also referred to as an analysis model) is:

[0085] )+b.

[0086] in, is the mass fraction of each main element, %. is the mass fraction of the interfering element that interferes with the corresponding main element, %. a and b are the slope and intercept of the calibration curve, respectively. is the fluorescence intensity of each main element, cps. is the fluorescence intensity of the overlapping lines, cps. is the line overlap correction factor. is the influence coefficient of the interfering element on the main element.

[0087] In some embodiments, when the main element is silicon, the corresponding interfering elements are aluminum and potassium. is the mass fraction of silicon, is the mass fraction of aluminum element and the mass fraction of potassium element.

[0088] When the main element is aluminum, the corresponding interfering elements are silicon and potassium. is the mass fraction of aluminum, is the mass fraction of silicon element and the mass fraction of potassium element.

[0089] In the case where the main element is iron, the corresponding interfering element is titanium. is the mass fraction of iron, is the mass fraction of titanium element.

[0090] When the main element is titanium, the corresponding interfering elements are potassium and iron. is the mass fraction of titanium, is the mass fraction of potassium and the mass fraction of iron.

[0091] When the main element is potassium, the corresponding interfering elements are silicon and aluminum. is the mass fraction of potassium, is the mass fraction of silicon and the mass fraction of aluminum.

[0092] In some embodiments, according to the fluorescence spectrum data of the object to be tested, based on the mapping relationship between the fluorescence spectrum value corresponding to each main element and the element content, the step of determining the element content of each main element in the porcelain insulator to be tested includes:

[0093] The standard curves of each main element were established based on the mapping relationship between the fluorescence spectrum values ​​corresponding to each main element and the element content.

[0094] Substitute the fluorescence spectrum value of each main element in the fluorescence spectrum data of the object to be tested into the corresponding main element standard curve to determine the element content of each main element in the porcelain insulator to be tested.

[0095] In some embodiments, the method further includes: analyzing the accuracy and precision of the measurement method.

[0096] The specific steps include:

[0097] Calculate the detection limit of each element in the standard sample,

[0098] Formula (2)

[0099] In the formula, is the detection limit of each element, %; m is the fluorescence intensity per unit content, cps; is the fluorescence intensity of the blank background, cps; t is the measurement time of the analysis line and background, s.

[0100] The accuracy (trueness and precision) of the analytical test method.

[0101] Verify the accuracy of the test method:

[0102] When this method is used to test standard samples, if the difference between the test value and the standard value is no more than 0.7 times the allowable difference specified in Table 4 (according to GB / T 6900-2016 "Chemical Analysis Methods for Aluminum-Silicon Refractories"), the accuracy of the established analysis model meets the requirements.

[0103] Table 4 Allowable difference of analysis values

[0104]

[0105] Assessing the precision of the test method:

[0106] According to the standard GB / T 6379.2-2004 "Accuracy (Trueness and Precision) of measurement methods and results Part 2: Basic method for determining the repeatability and reproducibility of standard measurement methods", a precision test was carried out. q groups of samples with different contents were selected, and this method was used to carry out n times of detection under repeatability conditions using the same equipment. The relative standard deviation RSD of the detection value of each element was calculated. If the relative standard deviation RSD≤2%, it means that the precision of this method meets the requirements.

[0107] The above technical solutions of the present invention are only preferred embodiments of the present invention, and the patent scope of the present invention is not limited thereto. All equivalent structural changes made by using the contents of the present invention specification and drawings under the technical concept of the present invention, or directly / indirectly applied in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A method for measuring the major and minor components of a porcelain insulator, characterized in that: The following steps are involved: Determine the measurement range of main element oxides according to the chemical composition of each type of porcelain insulator; wherein the main element oxides include silicon oxide, aluminum oxide, iron oxide, titanium oxide and potassium oxide; Selecting a plurality of standard samples according to the measurement range of the main element oxide; the content of each main element oxide in the plurality of standard samples is distributed within the measurement range corresponding to the main element oxide; Performing X-ray fluorescence spectrum detection on a plurality of standard samples respectively to obtain a plurality of corresponding fluorescence spectrum data of the standard samples; the fluorescence spectrum data of the standard samples include fluorescence spectrum values ​​of the main elements corresponding to the oxides of the main elements in the standard samples; Establishing a mapping relationship between the fluorescence spectrum value corresponding to each main element and the element content according to the plurality of corresponding standard sample fluorescence spectrum data; Performing X-ray fluorescence spectrum detection on the porcelain insulator to be tested to obtain fluorescence spectrum data of the object to be tested, wherein the fluorescence spectrum data of the object to be tested includes fluorescence spectrum values ​​of each main element in the porcelain insulator to be tested; According to the fluorescence spectrum data of the object to be tested, based on the mapping relationship between the fluorescence spectrum value corresponding to each main element and the element content, determine the element content of each main element in the porcelain insulator to be tested; The step of establishing a mapping relationship between the fluorescence spectrum value corresponding to each main element and the element content according to the plurality of corresponding standard sample fluorescence spectrum data comprises: According to the matrix effect of each main element and the influence of the spectral line overlap of each main element, the linear relationship between the fluorescence spectrum value corresponding to each main element and the element content is corrected to obtain the mapping relationship; The mapping relationship between the fluorescence spectrum value corresponding to each main element and the element content is: )+b； in, is the mass fraction of each main element, %; is the mass fraction of the interfering element that interferes with the corresponding main element, %; , b are the slope and intercept of the calibration curve, respectively; is the fluorescence intensity of each main element, cps; is the fluorescence intensity of the overlapping lines, cps; is the spectral line overlap correction factor; is the influence coefficient of the interfering element on the main element; When the main element is silicon, the corresponding interfering elements are aluminum and potassium. is the mass fraction of silicon, are the mass fraction of aluminum and potassium; When the main element is aluminum, the corresponding interfering elements are silicon and potassium. is the mass fraction of aluminum, is the mass fraction of silicon and potassium; In the case where the main element is iron, the corresponding interfering element is titanium. is the mass fraction of iron, is the mass fraction of titanium; When the main element is titanium, the corresponding interfering elements are potassium and iron. is the mass fraction of titanium, is the mass fraction of potassium and iron; When the main element is potassium, the corresponding interfering elements are silicon and aluminum. is the mass fraction of potassium, is the mass fraction of silicon and the mass fraction of aluminum.

2. The measuring method according to claim 1, characterized in that: The measuring range of silicon oxide is 0-80%, the measuring range of aluminum oxide is 0-90%, the measuring range of iron oxide is 0-14%, the measuring range of titanium oxide is 0-5%, and the measuring range of potassium oxide is 0-5%; The content of each main element oxide in the plurality of standard samples is distributed within the measurement range corresponding to the main element oxide and satisfies the following conditions: In the measuring range of silicon oxide and the measuring range of aluminum oxide, there is at least one standard sample in each 10% gradient range, and there are 1-2 standard samples in the measuring range within 10%; In the measuring range of the iron oxide, the measuring range of the titanium oxide and the measuring range of the potassium oxide, there is at least one standard sample in each 1% gradient range.

3. The measuring method according to claim 2, characterized in that: The number of standard samples of the plurality of standard samples is 15, and the plurality of standard samples are YSS068-2013, YSBC13803-94, YSS066-2013, YSS065-2013, YSS064-2013, ZBM1082, GBW07146, GBW03115, GBW07451, GBW07302a, YSS064-2013 and GBW07 A mixture of YSS065-2013 and YSS064-2013 in a mass ratio of 1:1, a mixture of GBW07146 and YSS064-2013 in a mass ratio of 3:7, a mixture of GBW07146 and GBW07302a in a mass ratio of 8:2, a mixture of GBW07146 and GBW07451 in a mass ratio of 1:

1.

4. The measuring method according to claim 1, characterized in that: In the step of performing X-ray fluorescence spectrum detection, the tube voltage of the high-voltage X-ray tube is 8 kV, the tube current is 50 μA, the end window is an Ag target, and the Kα line of silicon, the Kα line of aluminum, the Kα line of titanium, the Kα line of iron, and the Kα line of potassium are measured.

5. The measuring method according to claim 1, characterized in that: In the step of performing X-ray fluorescence spectroscopy detection, the method for preparing the test sample comprises: The solvent and the sample are mixed evenly in a mass ratio of 10:1, and 4-5 drops of a release agent are added, and the mixture is placed in a melting furnace and melted at 1100°C for 25 minutes, cooled and solidified in a mold, and demolded to obtain a test sample; the sample is a standard sample or a porcelain insulator to be tested; the solvent is a mixed solvent of lithium tetraborate and lithium metaborate in a mass ratio of 2:1; and the release agent is an ammonium bromide solution.

6. The measuring method according to claim 1, characterized in that: According to the fluorescence spectrum data of the object to be tested, based on the mapping relationship between the fluorescence spectrum value corresponding to each main element and the element content, the step of determining the element content of each main element in the porcelain insulator to be tested includes: The standard curves of the main elements are established based on the mapping relationship between the fluorescence spectrum values ​​corresponding to the main elements and the element contents; Substitute the fluorescence spectrum value of each main element in the fluorescence spectrum data of the object to be tested into the corresponding main element standard curve to determine the element content of each main element in the porcelain insulator to be tested.

7. The measuring method according to any one of claims 1 to 6, characterized in that: Also includes: The accuracy and precision of the measurement method were analyzed.

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