CN112834486B - Method for measuring chromium content in nickel-based alloy - Google Patents
Method for measuring chromium content in nickel-based alloy Download PDFInfo
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Abstract
Hair brushThe invention discloses a method for measuring the content of chromium in a nickel-based alloy, which comprises the following specific measurement steps: (1) detecting the total components of the sample in a semi-quantitative way; (2) preparation of sample solution K S Cr (ii) a (3) Determining chromium element in the sample in advance; (4) preparing a calibration solution; (5) analyzing a sample; (6) and (4) processing test data. The detection method provided by the invention is convenient to operate and accurate in detection, greatly improves the efficiency and accuracy of detecting the content of the chromium element in the nickel-based alloy, widens the detection range of determining the content of the chromium element in the nickel-based alloy by an ICP method, and is suitable for determining the content of the chromium element in various grades of nickel-based alloys.
Description
Technical Field
The invention belongs to the technical field of metallurgical material analysis, and particularly relates to a method for measuring the content of a chromium element in a nickel-based alloy.
Background
The nickel-based alloy mainly comprises main elements such as Ni, Cr, Mo, Fe and the like, and different alloy elements have certain influence on various properties of the nickel-based alloy, so that the method is very critical to accurate determination of the elements in the nickel-based alloy.
At present, the fixed value detection standard of the chromium element of the nickel-based alloy is as follows: YS/T539.4-2009 Ni-based alloy powder chemical analysis method part 4: the detection range of the method for determining the amount of chromium by the oxidative titration of ammonium persulfate is 2 to 30 percent. The detection standard needs to dissolve a sample by acid, uses silver nitrate as a catalyst in a sulfuric acid-phosphoric acid medium, uses ammonium persulfate for oxidation and other steps, and has the disadvantages of complicated detection steps and long detection period. Meanwhile, the detection range cannot completely cover the content range of the tungsten element in the conventional nickel-based alloy. Meanwhile, a conventional method can be used for rapidly determining the chromium element in the nickel-based alloy, namely, the X-ray fluorescence spectrometry (conventional method) for determining the multi-element content of the GB/T36164-2018 high alloy steel, wherein the detection range of the chromium element is 10-25%. The conventional method has high detection speed, but has low detection precision and accuracy. The detection range of the method can not completely cover the content range of tungsten element in the conventional nickel-based alloy.
Regarding the ICP spectrometry, there are advantages of wide linear range, low detection limit, less interference and easy elimination, and related technicians also use the ICP spectrometry to detect chromium in nickel-based alloys, but the detection range of chromium is generally less than 25%. Similar detection criteria are: GB/T2457integral 2009 nickel-iron-phosphorus, manganese, chromium, copper, cobalt and silicon content determination inductively coupled plasma atomic emission spectrometry, wherein the detection range of chromium element is 0.05% -1.0%, and the detection range is too narrow to meet the detection range of chromium content in the current nickel-based alloy.
The method disclosed by the invention is used for accurately controlling the chromium element in the nickel-based alloy by applying the ICP spectrometer substrate matching method, greatly improving the efficiency and accuracy of detecting the chromium element content in the nickel-based alloy, widening the detection range of determining the chromium element content in the nickel-based alloy by the ICP method and being suitable for determining the chromium element content in various grades of nickel-based alloys.
Disclosure of Invention
The invention aims to provide a method for measuring the content of chromium element in nickel-based alloy.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for measuring the content of chromium element in nickel-based alloy adopts an ICP spectrometer matrix matching method to measure, and comprises the following specific measuring steps:
(1) semi-quantitative detection of total components of sample
Measuring the total components of the sample by adopting a semi-quantitative method, and recording the mass fraction of the chromium element as A 0 ；
(2) Preparation of sample solution K S Cr
Weighing 0.10-0.20 g of sample, putting the sample into a 200mL polytetrafluoroethylene beaker, adding 1-3 mL of hydrofluoric acid, 10-20 mL of hydrochloric acid, 1-2 mL of nitric acid and 1-2 mL of phosphoric acid, heating until the sample is completely dissolved, adding 3-5 mL of perchloric acid, heating to the perchloric acid to start smoking, continuing smoking for 2-3 min, and fixing the volume in a 100-200 mL volumetric flask to obtain the product;
(3) the content of chromium element in the sample is measured in advance
a) Preparation of Primary calibration solution K 0 Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction of the chromium element in the calibration solution is W 0 ，W 0 ＝A 0 + (1% -10%); according to the full-component semi-quantitative detection result of the sample, adding elements with the mass fraction of more than 1% in the sample into the volumetric flask, so that the mass fraction of each element in the chromium element calibration solution is the same as the detection result in the step (1); then adding 1-2 mL of phosphoric acid and 3-5 mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2-3 min, diluting the mixture to a scale with water, and shaking up the mixture to obtain the product;
b) preparation of blank solution K 0 : and K 0 Cr The preparation method is consistent, but the chromium element standard solution is not added;
c) measurement of K by ICP spectrometer 0 And K 0 Cr Net strength of 0 And I 0 Cr ；
d) Measurement of sample solution K by ICP spectrometer S Cr Net strength of (I) S Cr ；
e) The approximate percent chromium in the sample solution, W, was calculated according to the following equation S Cr
(4) Preparation of calibration solutions
a) Preparing chromium element low-standard calibration solution K l Cr : transferring a certain amount of chromium standard solution into a volumetric flask to ensure that the chromium in the calibration solution is divided by massNumber W l Cr ＝70％W S Cr ～90％W S Cr (ii) a According to the full-component semi-quantitative detection result of the sample, adding elements with the mass fraction of more than 1% in the sample into the volumetric flask, so that the mass fraction of each element in the chromium element calibration solution is the same as the detection result in the step (1); then adding 1-2 mL of phosphoric acid and 3-5 mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2-3 min, diluting the mixture to a scale with water, and shaking up the mixture to obtain the product;
b) preparing a chromium element high-standard calibration solution K h Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution h Cr ＝110％W S Cr ～130％W S Cr (ii) a Adding elements with mass fractions of more than 5% in the sample into the volumetric flask according to the full-component semi-quantitative detection result of the sample, so that the mass fractions of the elements in the chromium element calibration solution are the same as the detection result in the step (1); then adding 1-2 mL of phosphoric acid and 3-5 mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2-3 min, diluting the mixture to a scale with water, and shaking up the mixture to obtain the product;
(5) analyzing a sample;
a) measuring low-standard calibration solution K by using ICP spectrometer l Cr Analyzing the net intensity or intensity ratio of the spectral line;
b) measurement of sample solution K by ICP spectrometer S Cr Analyzing the net intensity or intensity ratio of the spectral line;
c) measuring high-standard calibration solution K by using ICP spectrometer h Cr Analyzing the net intensity or intensity ratio of the spectral line;
d) the measurement was repeated 3 times in this order, and the low-standard calibration solution K was calculated separately l Cr Sample solution K S Cr And high standard calibration solution K h Cr Intensity average value of l Cr And I S Cr And I h Cr 。
(6) And (6) processing test data.
The mass fraction W of chromium in the sample was calculated by the following equation Cr Values are expressed in%;
specifically, the invention relates to a method for determining the content of chromium in a nickel-based alloy, wherein the method comprises the following steps: in the step (1), the full-component semi-quantitative detection of the sample comprises the following steps:
a) when the sample is in a crumb shape, semi-quantitative detection can be performed by adopting a scanning electron microscope spectroscopy;
b) when the sample is in a block shape, semi-quantitative detection can be performed by adopting a direct-reading spectrometer;
c) when the sample is in a block shape, semi-quantitative detection can be performed by a fluorescence spectrometer.
Specifically, the invention relates to a method for determining chromium content in a nickel-based alloy, wherein the method comprises the following steps: the calibration solution K in the step (3) 0 Cr Mass fraction W of medium chromium element 0 ：
a) When the content of chromium element A in the sample is 0 When the content is less than or equal to 1%, W 0 ＝A 0 +(1％～2％)；
b) When the content of chromium element in the sample is 1% < A 0 When the content is less than or equal to 10%, W 0 ＝A 0 +(2％～5％)；
c) When the content of chromium element A in the sample is 0 When > 10%, W 0 ＝A 0 +(5％～10％)。
Specifically, the invention relates to a method for determining chromium content in a nickel-based alloy, wherein the method comprises the following steps: the chromium element low-standard calibration solution K in the step (4) l,Cr Chromium element high-standard calibration solution K h Cr Mass fraction W of medium chromium element l,Cr And W h Cr Respectively as follows:
a) when the content of the chromium element A in the sample is 0 When the content is less than or equal to 1%, W l Cr ＝70％W S Cr ～75％W S C r，W h Cr ＝125％W S Cr ～130％W S Cr ；
b) When the content of chromium element in the sample is 1% < A 0 When the content is less than or equal to 10%, W l Cr ＝75％W S Cr ～80％W S Cr ，W h Cr ＝120％W S Cr ～125％W S Cr ；
c) When the sample isContent of medium chromium element A 0 When > 10%, W l Cr ＝80％W S Cr ～90％W S C r，W h Cr ＝110％W S Cr ～120％W S Cr 。
The invention creatively provides a method for measuring the content of chromium in nickel-based alloy, and the method is suitable for measuring the content of chromium in various grades of nickel-based alloy. The detection method provided by the invention is convenient to operate and accurate in detection, greatly improves the efficiency and accuracy of detecting the content of the chromium element in the nickel-based alloy, widens the detection range of determining the content of the chromium element in the nickel-based alloy by an ICP method, and is suitable for determining the content of the chromium element in various grades of nickel-based alloys.
Detailed Description
Example 1: and (3) determining the content of the chromium element in the nickel-based alloy sample 1 to be tested.
1. Detecting the total components of the sample in a semi-quantitative way;
the sample 1 to be measured is a crumb-shaped sample, and the total components of the sample are semi-quantitatively determined by a scanning electron microscope spectroscopy, and the components are shown in the following table 1.
TABLE 1 semi-quantitative Total composition (%)
| Element(s) | Cr | Ni | Fe | Co | Nb | Cu | Mn | Mo | Al |
| Sample No. 1 | 0.12 | 60.38 | 1.57 | 0.1 | 0.1 | 33 | 2.13 | 0.1 | 1.65 |
A is shown from the detection result 0 Is 0.12%.
2. Preparation of sample solution K S Cr
Weighing 0.20g of sample in a 200mL polytetrafluoroethylene beaker, adding 1mL of hydrofluoric acid, 20mL of hydrochloric acid, 2mL of nitric acid and 1mL of phosphoric acid, heating until the sample is completely dissolved, adding 3mL of perchloric acid, heating the perchloric acid to begin smoking, continuing smoking for 2min, and fixing the volume in a 100mL volumetric flask.
3. The content of chromium element in the sample is measured in advance
a) Preparation of Primary calibration solution K 0 Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution 0 0.12% + 1.88%; adding elements with mass fractions of more than 1% in the sample into the volumetric flask according to the full-component semi-quantitative detection result of the sample, so that the mass fractions of the elements in the chromium element calibration solution are the same as the detection result in the step (1), and the full-component semi-quantitative detection result shows that the elements with mass fractions of more than 1% in the sample and the mass fractions thereof are respectivelyNi: 60.38%, Fe: 1.57%, Cu: 33%, Mn: 2.13%, Al: 1.65 percent; then adding 1mL of phosphoric acid and 3mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2min, diluting the mixture with water to a scale, and shaking up the mixture to obtain the cigarette filter tip;
b) preparation of blank solution K 0 With calibration solution K 0 Cr The preparation method is consistent, but no chromium standard solution is added;
c) measurement of K by ICP spectrometer 0 And K 0 Cr Net strength of 0 Is 37.1, I 0 Cr 195285.0;
d) determination of the Net intensity I of the sample solution Using an ICP spectrometer S Cr 13539.6;
e) the approximate percent chromium in the sample solution was calculated according to the following formula:
by calculating to obtain W S Cr It was 0.139%.
4. Preparing a calibration solution;
a) preparing chromium element low-standard calibration solution K l Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution l Cr ＝70％W S Cr 0.097%; and (3) according to the full-component semi-quantitative detection result of the sample, adding elements with the mass fraction of more than 1% in the sample into the volumetric flask, so that the mass fraction of each element in the chromium element calibration solution is the same as the detection result in the step (1), and the full-component semi-quantitative detection result shows that the elements with the mass fraction of more than 1% in the sample and the mass fractions thereof are respectively Ni: 60.38%, Fe: 1.57%, Cu: 33%, Mn: 2.13%, Al: 1.65 percent; then adding 1mL of phosphoric acid and 3mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2min, diluting the mixture with water to a scale, and shaking up the mixture to obtain the cigarette filter tip;
b) preparing a chromium element high-standard calibration solution K h Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution h Cr ＝130％W S Cr 0.181%; and (2) according to the full-component semi-quantitative detection result of the sample, adding elements with the mass fraction of more than 1% in the sample into the volumetric flask, so that the mass fraction of each element in the chromium element calibration solution is the same as the detection result in the step (1), and the full-component semi-quantitative detection result shows that the elements with the mass fraction of more than 1% in the sample and the mass fractions thereof are respectively Ni: 60.38%, Fe: 1.57%, Cu: 33%, Mn: 2.13%, Al: 1.65 percent; then adding 1mL of phosphoric acid and 3mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2min, diluting the mixture with water to a scale, and shaking up the mixture to obtain the cigarette filter tip;
5. analyzing a sample;
a) measuring low-standard calibration solution K by using ICP spectrometer l Cr Analyzing the net intensity of the spectral line;
b) measurement of sample solution K by ICP spectrometer S Cr Analyzing the net intensity of the spectral line; (ii) a
c) Measuring high-standard calibration solution K by using ICP spectrometer h Cr The net intensity at the analytical line; (ii) a
d) The measurement was repeated 3 times in this order, and the calibration solution K was calculated separately l Cr Sample solution K S Cr And calibration solution K h Cr Intensity average value of l Cr And I S Cr And I h Cr 。
TABLE 2 calibration solutions and samples Net Strength (c/s)
| Number of detections | Low standard calibration solution K l Cr | Sample solution K S Cr | High-standard calibration solution K h Cr |
| 1 | 9678.1 | 13523.5 | 17409.4 |
| 2 | 9653.6 | 13547.1 | 17445.2 |
| 3 | 9644.9 | 13552.4 | 17429.8 |
| Mean value of | 9658.9 | 13541.0 | 17428.1 |
6. And (6) processing test data.
The mass fraction W of chromium in the sample was calculated by the following equation Cr Values are expressed in%;
by calculating to obtain W Cr It was 0.139%.
7. Precision test
Sample 1 was measured in parallel 11 times in the same manner, and the measured values and Relative Standard Deviations (RSD) of the results are shown in Table 3.
TABLE 3 precision test results (%)
8. Accuracy test
A standard sample 212X4002 with chromium content similar to that of the main element in the sample to be measured is selected and measured according to the same method, and the authentication value and the measured value of the result are shown in Table 4.
Table 4 accuracy test results (%)
| Standard sample numbering | Element(s) | Authentication value | Measured value |
| 212X4002 | Cr | 0.084 | 0.082 |
Example 2: and (3) determining the content of the chromium element in the nickel-based alloy sample 2 to be tested.
1. Detecting the total components of the sample in a semi-quantitative way;
the sample 2 to be measured is a block sample, and the components are determined semi-quantitatively by direct-reading spectrometry according to the following table 5.
TABLE 5 semi-quantitative Total composition (%)
| Element(s) | Cr | Ni | Fe | Mo | Nb | Cu | Mn | Co | Al |
| Sample 2 | 1.94 | 67.19 | 1.08 | 26.43 | 0.21 | 0.01 | 0.48 | 0.13 | 0.45 |
A is shown from the detection result 0 The content was 1.94%.
2. Preparation of sample solution K S Cr
Sampling drill cuttings of a sample 2 to be detected according to sample preparation requirements, weighing 0.15g of the sample in a 200mL polytetrafluoroethylene beaker, adding 2mL of hydrofluoric acid, 15mL of hydrochloric acid, 2mL of nitric acid and 2mL of phosphoric acid, heating until the sample is completely dissolved, adding 4mL of perchloric acid, heating the perchloric acid to smoke, continuing to smoke for 2min, and fixing the volume in a 100mL volumetric flask.
3. The content of chromium element in the sample is measured in advance
a) Preparation of a Primary calibration solution K 0 Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution 0 1.94% + 3.06%; and (3) according to the full-component semi-quantitative detection result of the sample, adding elements with the mass fraction of more than 1% in the sample into the volumetric flask, so that the mass fraction of each element in the chromium element calibration solution is the same as the detection result in the step (1), and the full-component semi-quantitative detection result shows that the elements with the mass fraction of more than 1% in the sample and the mass fractions thereof are respectively Ni: 67.19%, Fe: 1.08%, Mo: 26.43 percent; then adding 2mL of phosphoric acid and 4mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2min, diluting the mixture with water to a scale, and shaking up the mixture to obtain the cigarette filter tip;
b) preparation of blank solution K 0 With calibration solution K 0 Cr The preparation method is consistent, but no chromium standard solution is added;
c) measurement of K by ICP spectrometer 0 And K 0 Cr Net strength of 0 Is 53.2, I 0 Cr 482010.2;
d) determination of the Net intensity I of the sample solution Using an ICP spectrometer S Cr 194474.4;
e) the approximate percent chromium in the sample solution was calculated according to the following formula:
by calculating to obtain W S Cr The content was 2.02%.
4. Preparing a calibration solution;
a) preparing chromium element low-standard calibration solution K l Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution l Cr ＝75％W S Cr 1.515%; according to the total composition of the sampleAnd (3) adding elements with mass fractions of more than 1% in the sample into the volumetric flask, so that the mass fractions of the elements in the chromium element calibration solution are the same as the detection result in the step (1), and the full-component semi-quantitative detection result shows that the elements with mass fractions of more than 1% in the sample and the mass fractions thereof are respectively Ni: 67.19%, Fe: 1.08%, Mo: 26.43 percent; then adding 2mL of phosphoric acid and 4mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2min, diluting the mixture with water to a scale, and shaking up the mixture to obtain the cigarette filter tip;
b) preparing a chromium element high-standard calibration solution K h Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution h Cr ＝125％W S Cr 2.525%; and (3) according to the full-component semi-quantitative detection result of the sample, adding elements with the mass fraction of more than 1% in the sample into the volumetric flask, so that the mass fraction of each element in the chromium element calibration solution is the same as the detection result in the step (1), and the full-component semi-quantitative detection result shows that the elements with the mass fraction of more than 1% in the sample and the mass fractions thereof are respectively Ni: 67.19%, Fe: 1.08%, Mo: 26.43 percent; then adding 2mL of phosphoric acid and 4mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2min, diluting the mixture with water to a scale, and shaking up the mixture to obtain the cigarette filter tip;
5. analyzing a sample;
a) measuring low-standard calibration solution K by using ICP spectrometer l,Cr Analyzing the net intensity of the spectral line;
b) measurement of sample solution K by ICP spectrometer S,Cr Analyzing the net intensity of the spectral line;
c) measuring high-standard calibration solution K by using ICP spectrometer h,Cr The net intensity at the analytical line;
d) the measurement was repeated 3 times in this order, and the calibration solution K was calculated separately l Cr Sample solution K S Cr And calibration solution K h Cr Intensity average value of l Cr And I S Cr And I h Cr 。
TABLE 6 neat Strength (c/s) of calibration solutions and samples
| Number of detections | Low standard calibration solution K l Cr | Sample solution K S Cr | High-standard calibration solution K h Cr |
| 1 | 150496.3 | 194493.5 | 233112.6 |
| 2 | 150467.1 | 194469.2 | 233131.2 |
| 3 | 150484.9 | 194477.8 | 233105.1 |
| Mean value of | 150482.8 | 194480.2 | 233116.3 |
6. And (6) processing test data.
The mass fraction W of chromium element was calculated by the following equation Cr Values are expressed in%;
by calculating to obtain W Cr The content was 2.05%.
7. Precision test
The sample 2 to be tested was measured in parallel 11 times in the same manner, and the measured values and Relative Standard Deviations (RSD) of the results are shown in Table 7.
TABLE 7 precision test results (%)
8. Accuracy test
A standard sample IARM 257A with the chromium content similar to the main content elements in the sample to be measured is selected and measured according to the same method, and the authentication value and the measured value of the result are shown in Table 8.
Table 8 accuracy test results (%)
| Standard sample numbering | Element(s) | Authentication value | Measured value |
| IARM 257A | Cr | 1.57 | 1.59 |
Example 3: and (3) determining the content of the chromium element in the nickel-based alloy sample 3 to be tested.
1. Detecting the total components of the sample in a semi-quantitative way;
the sample 3 to be measured is a block sample, and the components are determined semi-quantitatively by adopting an X fluorescence spectrometry method, and are shown in the following table 9.
TABLE 9 semi-quantitative Total content (%)
| Element(s) | Cr | Ni | Fe | Mo | Ti | Cu | Mn | Co | Al |
| Sample 3 | 7.56 | 65.78 | 0.36 | 3.07 | 5.51 | 0.03 | 0.13 | 13.79 | 3.56 |
A is shown from the detection result 0 It was 7.56%.
2. Determining the sample dissolving condition;
sampling drill cuttings of a sample 3 to be detected according to sample preparation requirements, weighing 0.20g of the sample in a 200mL polytetrafluoroethylene beaker, adding 1mL of hydrofluoric acid, 20mL of hydrochloric acid, 2mL of nitric acid and 1mL of phosphoric acid, heating until the sample is completely dissolved, adding 3mL of perchloric acid, heating the perchloric acid and starting smoking. And (5) continuing smoking for 3min, and then fixing the volume in a 100mL volumetric flask.
3. The content of chromium element in the sample is measured in advance
a) Preparation of a Primary calibration solution K 0 Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution 0 7.56% + 2.44%; and (3) according to the full-component semi-quantitative detection result of the sample, adding elements with the mass fraction of more than 1% in the sample into the volumetric flask, so that the mass fraction of each element in the chromium element calibration solution is the same as the detection result in the step (1), and the full-component semi-quantitative detection result shows that the elements with the mass fraction of more than 1% in the sample and the mass fractions thereof are respectively Ni: 65.78%, Mo: 3.07%, Ti: 5.51%, Co: 13.79, Al: 3056; then adding 1mL of phosphoric acid and 3mL of perchloric acid into the mixture, heating the perchloric acid to smoke, continuously smoking for 3min, diluting the mixture with water to a scale and shaking the mixture uniformly to obtain the product;
b) preparation of blank solution K 0 With calibration solution K 0 Cr The preparation method is consistent, but no chromium standard solution is added;
c) measurement of K by ICP spectrometer 0 And K 0 Cr Net strength of 0 Is 43.1, I 0 Cr 901773.6;
d) determination of the Net intensity I of the sample solution Using an ICP spectrometer S Cr 720156.3;
e) the approximate percent chromium in the sample solution was calculated according to the following formula:
by calculating to obtain W S Cr The content was 7.99%.
4. Preparing a calibration solution;
a) preparing chromium element low-standard calibration solution K l Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution l Cr ＝78％W S Cr 6.23%; and (3) according to the full-component semi-quantitative detection result of the sample, adding elements with the mass fraction of more than 1% in the sample into the volumetric flask, so that the mass fraction of each element in the chromium element calibration solution is the same as the detection result in the step (1), and the full-component semi-quantitative detection result shows that the elements with the mass fraction of more than 1% in the sample and the mass fractions thereof are respectively Ni: 65.78%, Mo: 3.07%, Ti: 5.51%, Co: 13.79, Al: 3056; then adding 1mL of phosphoric acid and 3mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 3min, diluting the mixture with water to a scale, and shaking up the mixture to obtain the cigarette filter tip;
b) preparing chromium element high-standard calibration solution K h Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution h Cr ＝123％W S Cr 9.83%; and (3) according to the full-component semi-quantitative detection result of the sample, adding elements with the mass fraction of more than 1% in the sample into the volumetric flask, so that the mass fraction of each element in the chromium element calibration solution is the same as the detection result in the step (1), and the full-component semi-quantitative detection result shows that the elements with the mass fraction of more than 1% in the sample and the mass fractions thereof are respectively Ni: 65.78%, Mo: 3.07%, Ti: 5.51%, Co: 13.79, Al: 3056; then adding 1mL of phosphoric acid and 3mL of perchloric acid into the mixture, heating the perchloric acid to smoke, continuously smoking for 3min, diluting the mixture with water to a scale and shaking the mixture uniformly to obtain the product;
5. analyzing a sample;
a) measuring low-standard calibration solution K by using ICP spectrometer l,Cr Analyzing the net intensity of the spectral line;
b) measurement of sample solution K by ICP spectrometer S,Cr Analyzing the net intensity of the spectral line;
c) measuring high-standard calibration solution K by using ICP spectrometer h,Cr The net intensity at the analytical line;
d) the measurement was repeated 3 times in this order, and the calibration solution K was calculated separately l Cr Sample solution K S Cr And calibration solution K h Cr Intensity average value of l Cr And I S Cr And I h Cr 。
TABLE 10 neat Strength (c/s) of calibration solutions and samples
6. And (6) processing test data.
The mass fraction W of chromium element was calculated by the following equation Cr Values are expressed in%;
by calculating to obtain W Cr The content was 7.91%.
7. Precision test
The sample 2 to be tested was measured in parallel 11 times in the same manner, and the measured values and Relative Standard Deviations (RSD) of the results are shown in Table 11.
TABLE 11 precision test results (%)
8. Accuracy test
A standard sample 210X 11979 with the chromium content similar to the main content element in the sample to be measured is selected and measured according to the same method, and the authentication value and the measured value of the result are shown in the table 12.
TABLE 12 accuracy test results (%)
| Standard sample numbering | Element(s) | Authentication value | Measured value |
| 210X 11979 | Cr | 8.07 | 8.10 |
Example 4: and (4) determining the content of the chromium element in the nickel-based alloy sample 4 to be tested.
1. Detecting the total components of the sample in a semi-quantitative way;
the sample 4 to be measured is a crumb-like sample, and the total components of the sample are semi-quantitatively determined by a scanning electron microscope spectroscopy, and the components are shown in the following table 13.
TABLE 13 semi-quantitative Total composition (%)
| Element(s) | Cr | Ni | Fe | Mo | Nb | Cu | Mn | Co | Al |
| Sample No. 4 | 10.91 | 42.78 | 37.16 | 5.07 | 0.01 | 0.01 | 0.05 | 0.02 | 0.22 |
A is shown from the detection result 0 The content was 10.91%.
2. Determining the sample dissolving condition;
weighing 0.15g of sample in a 200mL polytetrafluoroethylene beaker, adding 2mL of hydrofluoric acid, 15mL of hydrochloric acid, 2mL of nitric acid and 2mL of phosphoric acid, heating until the sample is completely dissolved, adding 4mL of perchloric acid, heating the perchloric acid and starting smoking. And (5) keeping smoking for 2min, and then fixing the volume in a 100mL volumetric flask.
3. The content of chromium element in the sample is measured in advance
a) Preparation of Primary calibration solution K 0 Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution 0 10.91% + 9.09%; and (3) according to the full-component semi-quantitative detection result of the sample, adding elements with the mass fraction of more than 1% in the sample into the volumetric flask, so that the mass fraction of each element in the chromium element calibration solution is the same as the detection result in the step (1), and the full-component semi-quantitative detection result shows that the elements with the mass fraction of more than 1% in the sample and the mass fractions thereof are respectively Ni: 42.78%, Fe: 37.16%, Mo: 5.07 percent; then adding 2mL of phosphoric acid and 4mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2min, diluting the mixture with water to a scale, and shaking up the mixture to obtain the cigarette filter tip;
b) preparation of blank solution K 0 With calibration solution K 0 Cr The preparation method is consistent, but no chromium standard solution is added;
c) measurement of K by ICP spectrometer 0 And K 0 Cr Net strength of 0 Is 46.6, I 0 Cr 1786886.7;
d) determination of the Net intensity I of the sample solution Using an ICP spectrometer S Cr 1015401.2;
e) the approximate percent chromium in the sample solution was calculated according to the following formula:
by calculating to obtain W S Cr The content was 11.36%.
4. Preparing a calibration solution;
a) preparing chromium element low-standard calibration solution K l Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution l Cr ＝80％W S Cr 9.088%; according to the full-component semi-quantitative detection result of the sample, elements with the mass fraction of more than 1 percent in the sample are added into the volumetric flask, so that the mass fraction of each element in the chromium element calibration solution is the same as the detection result in the step (1), and the full-component semi-quantitative detection result is displayedThe elements with mass fractions of more than 1% in the sample are shown as Ni: 42.78%, Fe: 37.16%, Mo: 5.07 percent; then adding 2mL of phosphoric acid and 4mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2min, diluting the mixture with water to a scale, and shaking up the mixture to obtain the cigarette filter tip;
b) preparing a chromium element high-standard calibration solution K h Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution h Cr ＝120％W S Cr 13.632%; and (3) according to the full-component semi-quantitative detection result of the sample, adding elements with the mass fraction of more than 1% in the sample into the volumetric flask, so that the mass fraction of each element in the chromium element calibration solution is the same as the detection result in the step (1), and the full-component semi-quantitative detection result shows that the elements with the mass fraction of more than 1% in the sample and the mass fractions thereof are respectively Ni: 42.78%, Fe: 37.16%, Mo: 5.07 percent; then adding 2mL of phosphoric acid and 4mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2min, diluting the mixture with water to a scale, and shaking up the mixture to obtain the cigarette filter tip;
5. analyzing a sample;
a) measuring low-standard calibration solution K by using ICP spectrometer l,Cr Analyzing the net intensity of the spectral line;
b) measurement of sample solution K by ICP spectrometer S,Cr Analyzing the net intensity of the spectral line;
c) measuring high-standard calibration solution K by using ICP spectrometer h,Cr The net intensity at the analytical line;
d) the measurement was repeated 3 times in this order, and the calibration solution K was calculated separately l Cr Sample solution K S Cr And calibration solution K h Cr Intensity average value of l Cr And I S Cr And I h Cr 。
TABLE 14 calibration solutions and samples Net Strength (c/s)
| Number of detections | Low standard calibration solution K l Cr | Sample solution K S Cr | High-standard calibration solution K h Cr |
| 1 | 804506.6 | 1015436.1 | 1255481.6 |
| 2 | 804545.1 | 1015478.4 | 1255462.4 |
| 3 | 804506.6 | 1015483.5 | 1255459.7 |
| Mean value of | 804519.4 | 1015466.0 | 1255467.9 |
6. And (6) processing test data.
The mass fraction W of chromium element was calculated by the following equation Cr Values are expressed in%;
by calculatingGo out W Cr The content was 11.21%.
7. Precision test
The sample 2 to be tested was measured in parallel 11 times in the same manner, and the measurement values and the Relative Standard Deviation (RSD) of the results are shown in Table 15.
TABLE 15 precision test results (%)
8. Accuracy test
A standard sample BCS/SS-CRM387/1 with the chromium content similar to the main content elements in the sample to be measured is selected and measured according to the same method, and the authentication value and the measured value of the result are shown in a table 16.
TABLE 16 accuracy test results (%)
| Standard sample numbering | Element(s) | Authentication value | Measured value |
| BCS/SS-CRM 387/1 | Cr | 11.35 | 11.39 |
Example 5: and (3) determining the content of the chromium element in the nickel-based alloy sample 5 to be tested.
1. Detecting the total components of the sample in a semi-quantitative way;
the sample 5 to be measured is a block sample, and the components are determined semi-quantitatively by direct-reading spectrometry according to the following table 17.
TABLE 17 semi-quantitative Total composition (%)
| Element(s) | Cr | Ni | Fe | Mo | Nb | Cu | Mn | Co | Al |
| Sample No. 5 | 18.56 | 53.13 | 18.15 | 2.94 | 5.16 | 0.64 | 0.13 | 0.38 | 0.62 |
A is shown from the detection result 0 The content was 18.56%.
2. Determining the sample dissolving condition;
sampling drill cuttings of a sample 5 to be detected according to sample preparation requirements, weighing 0.10g of the sample in a 200mL polytetrafluoroethylene beaker, adding 1mL of hydrofluoric acid, 10mL of hydrochloric acid, 1mL of nitric acid and 1mL of phosphoric acid, heating until the sample is completely dissolved, adding 3mL of perchloric acid, heating the perchloric acid and starting smoking. And (5) continuing smoking for 2min, and then fixing the volume in a 100mL volumetric flask.
3. The content of chromium element in the sample is measured in advance
a) Preparation of Primary calibration solution K 0 Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution 0 18.56% + 6.44%; and (3) according to the full-component semi-quantitative detection result of the sample, adding elements with the mass fraction of more than 1% in the sample into the volumetric flask, so that the mass fraction of each element in the chromium element calibration solution is the same as the detection result in the step (1), and the full-component semi-quantitative detection result shows that the elements with the mass fraction of more than 1% in the sample and the mass fractions thereof are respectively Ni: 53.13%, Fe: 18.15%, Mo: 2.94%, Nb: 5.16 percent; then adding 1mL of phosphoric acid and 3mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2min, diluting the mixture with water to a scale, and shaking up the mixture to obtain the cigarette filter tip;
b) preparation of blank solution K 0 With calibration solution K 0 Cr The preparation method is consistent, but no chromium standard solution is added;
c) measurement of K by ICP spectrometer 0 And K 0 Cr Net strength of 0 Is 51.2, I 0 Cr 2233867.1;
d) determination of the Net intensity I of the sample solution Using an ICP spectrometer S Cr 1693620.2;
e) the approximate percent chromium in the sample solution was calculated according to the following equation:
by calculating to obtain W S Cr The content was 18.95%.
4. Preparing a calibration solution;
a) preparing chromium element low-standard calibration solution K l Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution l Cr ＝90％W S Cr 17.055%; and (3) according to the full-component semi-quantitative detection result of the sample, adding elements with the mass fraction of more than 1% in the sample into the volumetric flask, so that the mass fraction of each element in the chromium element calibration solution is the same as the detection result in the step (1), and the full-component semi-quantitative detection result shows that the elements with the mass fraction of more than 1% in the sample and the mass fractions thereof are respectively Ni: 53.13%, Fe: 18.15%, Mo: 2.94%, Nb: 5.16 percent; then adding 1mL of phosphoric acid and 3mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2min, diluting the mixture with water to a scale, and shaking up the mixture to obtain the cigarette filter tip;
b) preparing a chromium element high-standard calibration solution K h Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution h Cr ＝110％W S Cr 20.845%; and (3) according to the full-component semi-quantitative detection result of the sample, adding elements with the mass fraction of more than 1% in the sample into the volumetric flask, so that the mass fraction of each element in the chromium element calibration solution is the same as the detection result in the step (1), and the full-component semi-quantitative detection result shows that the elements with the mass fraction of more than 1% in the sample and the mass fractions thereof are respectively Ni: 53.13%, Fe: 18.15%, Mo: 2.94%, Nb: 5.16 percent; then adding 1mL of phosphoric acid and 3mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2min, diluting the mixture with water to a scale, and shaking up the mixture to obtain the cigarette filter tip;
5. analyzing a sample;
a) measurement of calibration solution K Using ICP spectrometer l,Cr Analyzing the net intensity of the spectral line;
b) measurement of sample solution K by ICP spectrometer S,Cr Analyzing the net intensity of the spectral line;
c) measurement of calibration solution K Using ICP spectrometer h,Cr Analyzing the net intensity of the spectral line;
d) the measurement was repeated 3 times in this order, and the calibration solution K was calculated separately l Cr Sample solution K S Cr And calibration solution K h Cr Intensity average value of l Cr And I S Cr And I h Cr 。
TABLE 18 calibration solutions and samples Net Strength (c/s)
| Number of detections | Low standard calibration solution K l Cr | Sample solution K S Cr | High-standard calibration solution K h Cr |
| 1 | 1520458.3 | 1693620.2 | 1881150.5 |
| 2 | 1523152.6 | 1694156.3 | 1884219.2 |
| 3 | 1524897.4 | 1696814.8 | 1883319.4 |
| Mean value of | 1522836.1 | 1694863.8 | 1882896.4 |
6. And (6) processing test data.
The mass fraction W of chromium element was calculated by the following equation Cr Numerical values are expressed in%;
by calculating to obtain W Cr It was 18.86%.
7. Precision test
The test sample 5 was measured in parallel 11 times in the same manner, and the measured values and Relative Standard Deviations (RSD) of the results are shown in Table 19.
TABLE 19 precision test results (%)
8. Accuracy test
A standard sample BS 718D with chromium content similar to the main content element in the sample to be measured is selected and measured according to the same method, and the authentication value and the measured value of the result are shown in Table 20.
TABLE 20 accuracy test results (%)
| Reference sample number | Element(s) | Authentication value | Measured value |
| BS 718D | Cr | 18.32 | 18.26 |
Example 6: and (3) determining the content of the chromium element in the nickel-based alloy sample 6 to be tested.
1. Semi-quantitative detection of all components of the sample;
the sample 6 to be measured is a block sample, and the components are determined semi-quantitatively by adopting an X fluorescence spectrometry method, as shown in Table 13 below.
TABLE 21 semi-quantitative Total composition (%)
| Element(s) | Cr | Ni | Fe | Mo | Nb | Cu | Mn | Si | C |
| Sample 3 | 31.36 | 45.12 | 19.01 | 0.01 | 1.01 | 0.01 | 1.57 | 1.16 | 0.39 |
A is shown from the detection result 0 It was 31.36%.
2. Preparation of sample solution K S Cr
Weighing 0.10g of sample in a 200mL polytetrafluoroethylene beaker, adding 3mL of hydrofluoric acid, 10mL of hydrochloric acid, 2mL of nitric acid and 2mL of phosphoric acid, heating until the sample is completely dissolved, adding 5mL of perchloric acid, heating the perchloric acid to begin smoking, and keeping smoking for 2min and then fixing the volume in a 100mL volumetric flask.
3. Determining chromium element in the sample in advance;
a) preparation of Primary calibration solution K 0 Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution 0 31.36% + 8.64%; and (2) according to the full-component semi-quantitative detection result of the sample, adding elements with the mass fraction of more than 1% in the sample into the volumetric flask, so that the mass fraction of each element in the chromium element calibration solution is the same as the detection result in the step (1), and the full-component semi-quantitative detection result shows that the elements with the mass fraction of more than 1% in the sample and the mass fractions thereof are respectively Ni: 45.12%, Fe: 19.01Percent, Nb: 1.01%, Mn: 1.57%, Si: 1.16 percent; then adding 2mL of phosphoric acid and 5mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2min, diluting the mixture with water to a scale, and shaking up the mixture to obtain the cigarette filter tip;
b) preparation of blank solution K 0 With calibration solution K 0 Cr The preparation method is consistent, but no chromium standard solution is added;
c) measurement of K by ICP spectrometer 0 And K 0 Cr Net strength of (I) 0 Is 52,3 and I 0 Cr 3642384.5;
d) determination of the Net intensity I of the sample solution Using an ICP spectrometer S Cr 2822847.2;
e) the approximate percent chromium in the sample solution was calculated according to the following formula:
by calculating to obtain W S Cr The content was 31.00%.
4. Preparing a calibration solution;
a) preparing chromium element low-standard calibration solution K l,Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution l,Cr ＝90％W S Cr 27.90%; and (3) according to the full-component semi-quantitative detection result of the sample, adding elements with the mass fraction of more than 1% in the sample into the volumetric flask, so that the mass fraction of each element in the chromium element calibration solution is the same as the detection result in the step (1), and the full-component semi-quantitative detection result shows that the elements with the mass fraction of more than 1% in the sample and the mass fractions thereof are respectively Ni: 42.78%, Fe: 37.16%, Mo: 5.07 percent; then adding 2mL of phosphoric acid and 5mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2min, diluting the mixture with water to a scale, and shaking up the mixture to obtain the cigarette filter tip;
b) preparing a chromium element high-standard calibration solution K h Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the calibration solution h Cr ＝110％W S Cr 34.10%; according toAnd (2) adding elements with mass fractions larger than 1% in the sample into the volumetric flask, so that the mass fractions of the elements in the chromium element calibration solution are the same as the detection result in the step (1), and the full-component semi-quantitative detection result shows that the elements with mass fractions larger than 1% in the sample and the mass fractions thereof are respectively Ni: 42.78%, Fe: 37.16%, Mo: 5.07 percent; then adding 2mL of phosphoric acid and 5mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2min, diluting the mixture with water to a scale, and shaking up the mixture to obtain the cigarette filter tip;
5. sample analysis
a) Measuring low-standard calibration solution K by using ICP spectrometer l,Cr The net intensity at the analytical line;
b) measurement of sample solution K by ICP spectrometer S,Cr Analyzing the net intensity of the spectral line;
c) measuring high-standard calibration solution K by using ICP spectrometer h,Cr Analyzing the net intensity of the spectral line;
d) the measurement was repeated 3 times in this order, and the calibration solution K was calculated separately l Cr Sample solution K S Cr And calibration solution K h Cr Intensity average value of l Cr And I S Cr And I h Cr 。
TABLE 22 calibration solutions and samples Net Strength (c/s)
| Number of detections | Low-standard calibration solution K l,Cr | Sample solution K S,Cr | High-standard calibration solution K h,Cr |
| 1 | 2549668.4 | 2822791.4 | 3114273.5 |
| 2 | 2549704.6 | 2822847.2 | 3114312.3 |
| 3 | 2549697.3 | 2822879.5 | 3114297.8 |
| Mean value of | 2549690.1 | 2822839.4 | 3114294.5 |
6. Processing of test data
The mass fraction W of chromium element was calculated by the following equation Cr Values are expressed in%;
by calculating to obtain W Cr The content was 30.90%.
7. Precision test
The sample 6 to be tested was measured in parallel 11 times in the same manner, and the measured values and Relative Standard Deviations (RSD) of the results are shown in Table 23.
TABLE 23 precision test results (%)
8. Accuracy test
A standard sample NH35-45Mic with the chromium content similar to the main content element in the sample to be measured is selected and measured according to the same method, and the authentication value and the measured value of the result are shown in a table 24.
TABLE 24 accuracy test results (%)
| Reference sample number | Element(s) | Authentication value | Measured value |
| NH35-45Mic | Cr | 33.59 | 33.47 |
Claims (4)
1. A method for measuring the content of chromium element in nickel-based alloy is characterized in that an ICP spectrometer matrix matching method is adopted for measurement, and the specific measurement steps are as follows:
(1) semi-quantitative detection of total components of sample
The total components of the sample are measured by adopting a semi-quantitative method, and the mass fraction of the chromium element is recorded as A 0 ；
(2) Preparation of sample solution K S Cr
Weighing 0.10-0.20 g of sample in a 200mL polytetrafluoroethylene beaker, adding 1-3 mL of hydrofluoric acid, 10-20 mL of hydrochloric acid, 1-2 mL of nitric acid and 1-2 mL of phosphoric acid, heating until the sample is completely dissolved, adding 3-5 mL of perchloric acid, heating until the perchloric acid begins to smoke, continuing to smoke for 2-3 min, and fixing the volume in a 100-200 mL volumetric flask to obtain the product;
(3) the content of chromium element in the sample is measured in advance
a) Preparing a chromium element primary calibration solution K 0 Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction of the chromium element in the primary chromium element calibration solution is W 0 ，W 0 =A 0 + (1% -10%); adding elements with mass fractions of more than 1% in the sample into the volumetric flask according to the full-component semi-quantitative detection result of the sample, so that the mass fractions of the elements in the primary chromium calibration solution are the same as the detection result in the step (1); then adding 1-2 mL of phosphoric acid and 3-5 mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2-3 min, diluting the mixture to a scale with water, and shaking up the mixture to obtain the product;
b) preparation of blank solution K 0 : and K 0 Cr The preparation method is consistent, but the standard solution of chromium element is not added;
c) measurement of K by ICP spectrometer 0 And K 0 Cr Net strength ofI 0 AndI 0 Cr ；
d) measurement of sample solution K by ICP spectrometer S Cr Net strength ofI S Cr ；
e) The approximate percent chromium in the sample solution, W, was calculated according to the following equation S Cr
(4) Preparation of calibration solutions
a) Preparing chromium element low-standard calibration solution K l Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the chromium element low-standard calibration solution l Cr =70%W S Cr ～90%W S Cr (ii) a Adding the sample into the volumetric flask according to the full-component semi-quantitative detection result of the sample, wherein the mass fraction of the sample is more than or equal to1% of elements, wherein the mass fraction of each element in the chromium element low-standard calibration solution is the same as the detection result in the step (1); then adding 1-2 mL of phosphoric acid and 3-5 mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2-3 min, diluting the mixture to a scale with water, and shaking up the mixture to obtain the product;
b) preparing chromium element high-standard calibration solution K h Cr : transferring a certain amount of chromium element standard solution into a volumetric flask to ensure that the mass fraction W of the chromium element in the chromium element high-standard calibration solution h Cr =110%W S Cr ～130%W S Cr (ii) a Adding elements with mass fractions of more than 5% in the sample into the volumetric flask according to the full-component semi-quantitative detection result of the sample, so that the mass fractions of the elements in the chromium element high-grade calibration solution are the same as the detection result in the step (1); then adding 1-2 mL of phosphoric acid and 3-5 mL of perchloric acid into the mixture, heating the perchloric acid to begin smoking, continuing smoking for 2-3 min, diluting the mixture to a scale with water, and shaking up the mixture to obtain the product;
(5) sample analysis
a) Measuring low-standard calibration solution K of chromium element by utilizing ICP spectrometer l Cr Analyzing the net intensity or intensity ratio of the spectral line;
b) measurement of sample solution K by ICP spectrometer S Cr Analyzing the net intensity or intensity ratio of the spectral line;
c) measuring high-grade calibration solution K of chromium element by using ICP spectrometer h Cr Analyzing the net intensity or intensity ratio of the spectral line;
d) repeating the measurement 3 times in this order, and calculating the chromium low-standard calibration solution K l Cr Sample solution K S Cr And chromium element high-standard calibration solution K h Cr Average value of net intensity of l Cr ' and I S Cr ' and I h Cr '；
(6) Processing of test data
The mass fraction W of chromium in the sample was calculated by the following equation Cr Values are expressed in%;
2. the method for determining the content of chromium in a nickel-based alloy according to claim 1, wherein the method comprises the following steps: the step (1) of semi-quantitative detection of all components of the sample:
a) when the sample is in a crumb shape, semi-quantitative detection is carried out by adopting a scanning electron microscope spectroscopy;
b) when the sample is in a block shape, semi-quantitative detection is performed by a direct-reading spectrometer or semi-quantitative detection is performed by a fluorescence spectrometer.
3. The method for determining the content of chromium in a nickel-based alloy according to claim 1, wherein: the chromium element primary calibration solution K in the step (3) 0 Cr Mass fraction W of medium chromium element 0 ：
a) When the content of chromium element A in the sample is 0 When the content is less than or equal to 1%, W 0 =A 0 +（1%～2%）；
b) When the content of the chromium element in the sample is 1% < A 0 When the content is less than or equal to 10%, W 0 =A 0 +（2%～5%）；
c) When the content of the chromium element A in the sample is 0 When > 10%, W 0 =A 0 +（5%～10%）。
4. The method for determining the content of chromium in a nickel-based alloy according to claim 1, wherein the method comprises the following steps: the chromium element low-standard calibration solution K in the step (4) l Cr Chromium element high-standard calibration solution K h Cr Mass fraction W of medium chromium element l Cr And W h Cr Respectively as follows:
a) when the content of chromium element A in the sample is 0 When the content is less than or equal to 1%, W l Cr =70%W S Cr ～75%W S C r；W h Cr =125%W S Cr ～130%W S Cr ；
b) When the content of chromium element in the sample is 1% < A 0 When the content is less than or equal to 10%, W l Cr =75%W S Cr ～80%W S Cr ；W h Cr =120%W S Cr ～125%W S Cr ；
c) When the chromium element in the sample containsQuantity A 0 When > 10%, W l Cr =80%W S Cr ～90%W S C r；W h Cr =110%W S Cr ～120%W S Cr 。
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