Method for measuring silicon, manganese and phosphorus in manganese-silicon alloy by X-ray fluorescence energy disperse spectroscopy

Abstract

The invention relates to a method for determining silicon, manganese and phosphorus in manganese-silicon alloy by using an X-ray fluorescence energy spectrometer, which comprises the following steps: irradiating a sample subjected to sample pressing by using X-rays of the X-ray fluorescence energy spectrometer, and exciting chemical elements with to-be-determined percentage content in a to-be-detected sample, so that element atoms emit X fluorescence with respective characteristics after being excited; by measuring the intensity of fluorescence excitation energy of different elements and establishing a mathematical model of the X fluorescence intensity and content of the elements, the percentage content of various elements in the detected sample is finally obtained, and the method has the beneficial effects that the content of silicon, manganese and phosphorus in the manganese-silicon alloy can be rapidly, stably and accurately detected, no chemical medicine is needed, and the method is simple and convenient to operate. The method has the advantages of high analysis speed, short detection period, high accuracy, no personal error, no material consumption, simplicity and easiness in operation, no pollutant emission, environmental protection and safety.

Description

Technical Field

[0001] The invention relates to the technical field of silicon, manganese and phosphorus content in manganese-silicon alloys, and in particular to a method for measuring silicon, manganese and phosphorus in manganese-silicon alloys using an X-ray fluorescence spectrometer. Background Art

[0002] Manganese silicon alloy is an extremely important raw material for steelmaking. It plays the role of deoxidation and adding necessary components in steelmaking, which directly affects the quality of steelmaking. However, the chemical analysis steps of manganese silicon alloy content are cumbersome. Not only is the analysis time particularly long (usually more than 5 hours), the analysis results are not accurate, which wastes manpower, material and financial resources, and seriously restricts the control of steelmaking composition. In addition, a large amount of chemicals are used in the analysis of manganese silicon alloy content, which pollutes the environment. This has long been a problem that steel companies have been urgently trying to solve in recent decades. Summary of the invention

[0003] In order to overcome the shortcomings of the prior art, the present invention provides a method for determining silicon, manganese and phosphorus in manganese silicon alloy by using an X-ray fluorescence spectrometer. The method comprises the following steps: the X-rays of the X-ray fluorescence spectrometer are used to irradiate a sample sheet after sample pressing, so as to excite the chemical elements of the sample to be tested, so that the element atoms emit their own characteristic X-ray fluorescence after being excited. The intensity of the fluorescence excitation energy of different elements is measured, and a mathematical model of the X-ray fluorescence intensity and content of the element is established to finally obtain the content of various elements in the sample to be tested, and then obtain the percentage of each element in the sample. No chemical reagents are required, and the analysis is performed directly by irradiating the sample with X-rays to excite the fluorescence energy after the sample is pressed. The method has the advantages of fast analysis speed, short detection cycle, high accuracy, no human error, no material consumption, simple and easy operation, no pollutant emission, and environmental safety.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions:

[0005] A method for determining silicon, manganese and phosphorus in a manganese-silicon alloy by an X-ray fluorescence spectrometer is provided. The method is implemented by an X-ray fluorescence spectrometer. The specific steps of the method for determining silicon, manganese and phosphorus in a manganese-silicon alloy by an X-ray fluorescence spectrometer are as follows:

[0006] S1. Sample preparation

[0007] Cleaning the grinding mortar for grinding the sample with the test sample of the silicon-manganese alloy to be prepared;

[0008] The test sample with a particle size of less than 1 mm to be prepared is loaded into a ceramic crucible, with the loading amount being 90-100%;

[0009] Place the grinding mortar filled with the sample into the grinder, grind for 80 seconds, then take it out and bag it;

[0010] S2. Sample pressing

[0011] Clean the sample pressing machine and each sample pressing mold;

[0012] According to the specifications of the sample pressing machine, a feeder is placed in the sample pressing tank. The feeder is a concentric circle structure sleeve. The test sample is placed in the inner cylinder of the feeder.

[0013] Use a sample leveler to contact the surface of the test sample in the inner tube of the feeder with the bottom flat surface of the sample leveler, gently rotate the sample leveler to make the test sample flat, and then take out the sample leveler;

[0014] Put boric acid on the surface of the test sample in the inner cylinder of the feeder, and then evenly sprinkle boric acid into the outer cylinder of the feeder, lift the feeder vertically and lightly, and take the feeder out vertically in the sample pressing tank. During the process of taking out, make sure that there is no adhesion between the sample and the feeder, and sweep the boric acid around the edge of the feeder and the base of the sample pressing machine into the sample pressing tank;

[0015] According to the specifications of the sample pressing machine, place the top seat on the top of the test sample in the sample pressing tank and make sure it is level and not tilted;

[0016] The sample pressing machine performs sample pressing, and after the sample pressing is completed, the sample is removed;

[0017] S3. Analyze the element content by detecting the fluorescence excitation energy of the elements in the sample through X-ray fluorescence method

[0018] Select a standard sample of silicon-manganese alloy with determined content of each element in the manganese-silicon alloy, press the sample and put it into an X-ray fluorescence spectrometer, set the X-ray fluorescence excitation energy conditions of each element composition in the standard sample on the X-ray fluorescence spectrometer, and irradiate the sample of the standard sample with X-rays;

[0019] The standard sample is irradiated by X-rays in the X-ray fluorescence spectrometer to obtain the intensity of the fluorescence excitation energy generated by each element;

[0020] Based on a series of standard samples with determined element contents and their corresponding fluorescence excitation energy intensities, a mathematical relationship curve between the intensity of fluorescence excitation energy of each element in the manganese-silicon alloy and the content of each element is drawn in an X-ray fluorescence spectrometer, and a mathematical formula for the intensity and percentage of each element in the manganese-silicon alloy is obtained based on the mathematical relationship curve;

[0021] The pressed sample of the test sample is placed in an X-ray fluorescence spectrometer, and the X-ray fluorescence excitation energy conditions of the elements in the test sample are set on the X-ray fluorescence spectrometer. The sample of the test sample is irradiated with X-rays to obtain the intensity of the fluorescence excitation energy generated by each element in the test sample. The intensity value of the excitation energy of each element is substituted into the mathematical formula of the intensity of each element in the manganese silicon alloy and the percentage of each element to obtain the percentage of each element in the manganese silicon alloy.

[0022] Furthermore, the loading amount and grinding time of the test sample in S1 are required to be consistent in repeated tests of the same type of test samples.

[0023] Furthermore, after the sample is depressed in S2, the sample surface must not be touched, and the burrs around the sample are cleaned with a sample spoon, and the boric acid dust is blown away with an ear bulb.

[0024] Furthermore, the chemical composition of the standard sample in S3 and the test sample is the same.

[0025] Furthermore, the test conditions of the X-ray fluorescence spectrometer for the standard sample and the test sample in S3 are the same.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] This method can quickly, stably and accurately detect the silicon, manganese and phosphorus contents in manganese silicon alloys without the need for chemicals. It can be directly analyzed by grinding the powder into tablets. It has the advantages of fast analysis speed, short detection cycle, high accuracy, no human error, no material consumption, simple and easy operation, no pollutant emissions, and environmental safety. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The present invention discloses a flow chart of a method for determining silicon, manganese and phosphorus in manganese-silicon alloy by using an X-ray fluorescence spectrometer.

[0029] Figure 2 It is a trend chart of the comparison analysis of Si in the manganese silicon alloy of the present invention.

[0030] Figure 3 It is a comparative analysis trend diagram of Mn of the manganese-silicon alloy of the present invention.

[0031] Figure 4 It is a comparative analysis trend diagram of the manganese silicon alloy P of the present invention. DETAILED DESCRIPTION

[0032] The specific implementation of the present invention will be further described below in conjunction with the accompanying drawings:

[0033] [Example] Figure 1 As shown, a method for determining silicon, manganese and phosphorus in manganese-silicon alloy by X-ray fluorescence spectrometer is implemented by X-ray fluorescence spectrometer. 30 manganese-silicon alloy test samples are taken for X-ray fluorescence spectrometer to test the Si, Mn and P contents therein. The specific determination steps are as follows:

[0034] S1. Sample preparation

[0035] Clean the grinding bowl of the grinding sample with the manganese silicon alloy sample to be prepared; put the manganese silicon alloy sample with a particle size of less than 1 mm into a ceramic crucible with a volume of 30 mL, and the loading amount is 100%, which is equivalent to 30 mL of the sample in the ceramic crucible. The mass of the manganese silicon alloy sample is obtained according to the particle size and volume of the manganese silicon alloy sample; put the manganese silicon alloy sample in the sample bowl into a grinder, grind for 80 seconds, and then take it out and bag it;

[0036] S2. Sample pressing

[0037] Clean the sample pressing machine and each sample pressing mold; place the feeder in the sample pressing tank according to the specifications of the sample pressing machine. The feeder is a concentric circle structure sleeve. Place the manganese silicon alloy sample in the inner cylinder of the feeder; hold the sample flattener with your hand, and make the horizontal plane at the bottom of the sample flattener contact the surface of the manganese silicon alloy sample in the inner cylinder of the feeder, then gently rotate the sample flattener to make the manganese silicon alloy sample flat, and then take out the sample flattener; put boric acid on the surface of the manganese silicon alloy sample in the inner cylinder of the feeder, and then evenly sprinkle the boric acid into the outer cylinder of the feeder, lift the feeder vertically and take it out vertically in the sample pressing tank. During the removal process, confirm that the sample is not in contact with the feeder. There is adhesion. If the feeder and the manganese silicon alloy sample are adhered during the vertical lifting process, the manganese silicon alloy pressing fails. It is necessary to re-measure the manganese silicon alloy sample and re-fill it into the pressing groove until it is confirmed that there is no adhesion between the feeder and the manganese silicon alloy sample. Sweep the boric acid around the edge of the feeder and the base of the pressing machine into the pressing groove; according to the specifications of the pressing machine, put the top seat on the top of the manganese silicon alloy sample in the pressing groove and confirm that it is horizontal and not tilted; the pressing machine presses the sample, and removes the sample after the pressing is completed. The sample must be flat, smooth and crack-free when pressing; do not touch the surface of the sample when taking it to avoid affecting the measurement results. Use a sample spoon to clean the burrs around the sample, and use an ear cleaning bulb to blow away the boric acid dust;

[0038] S3. Analyze the element content by detecting the fluorescence excitation energy of the elements in the sample through X-ray fluorescence method

[0039] Select a standard sample of manganese silicon alloy with determined content of each element, press the sample and put it into an X-ray fluorescence spectrometer, set the X-ray fluorescence excitation energy conditions of each element composition in the standard sample on the X-ray fluorescence spectrometer, and irradiate the sample of the standard sample with X-rays;

[0040] The standard sample is irradiated by X-rays in the X-ray fluorescence spectrometer to obtain the intensity of the fluorescence excitation energy generated by each element;

[0041] Based on a series of standard samples with determined element contents and their corresponding fluorescence excitation energy intensities, a mathematical relationship curve between the intensity of fluorescence excitation energy of each element in the manganese-silicon alloy and the content of each element is drawn in an X-ray fluorescence spectrometer, and a mathematical formula for the intensity and percentage of each element in the manganese-silicon alloy is obtained based on the mathematical relationship curve;

[0042] According to the intensity of the fluorescence energy of each element in the standard sample obtained by this X-ray fluorescence spectrometer, the percentage formula of each element in the sample is obtained.

[0043] Si=3.295352+15.0595053*I Si

[0044] Mn=8.157581+58.767222*I Mn

[0045] P=0.026457+0.061534*I P

[0046] Among them, Si-the percentage of silicon in the sample; Mn-the percentage of manganese in the sample; P-the percentage of phosphorus in the sample;

[0047] I Si - the intensity of silicon in the sample obtained in the X-ray fluorescence spectrum; I Mn - the intensity of manganese in the sample obtained in the X-ray fluorescence spectrum; I P -The intensity of phosphorus in the sample obtained in the X-ray fluorescence spectrum.

[0048] The pressed samples of the test samples are placed in the same X-ray fluorescence spectrometer, and the X-ray fluorescence excitation energy conditions of the elements in the test samples are set on the X-ray fluorescence spectrometer. The samples of the test samples are irradiated with X-rays to obtain the intensity of the fluorescence excitation energy generated by each element in the test samples. The intensity value of the energy that each element should be excited is substituted into the mathematical formula of the intensity of each element in the manganese silicon alloy and the percentage of each element to obtain the percentage of each element in the manganese silicon alloy.

[0049] like Figure 2-Figure 4 As shown in the figure, the Si, Mn, and P percentages of 30 manganese silicon alloy test samples were compared with the Si, Mn, S, and P percentages obtained by traditional chemical testing. The results are as follows:

[0050]

[0051] Test statistic t=0.268<t 0.975 =2.042, there is no significant difference in Si content of manganese silicon alloy detected by X-fluorescence spectrum pressing method and chemical analysis method.

[0052]

[0053]

[0054] Test statistic t=1.297>t 0.975=2.042, there is no significant difference in the Mn content of manganese silicon alloy detected by X-fluorescence spectrum pressing method and chemical analysis method.

[0055]

[0056] Test statistic t=1.643<t 0.975 =2.042, there is no significant difference in the P content of manganese silicon alloy detected by X-ray fluorescence spectrum pressing method and chemical analysis method.

[0057] t is the statistical value of the experimental difference data; t 0.975 is the statistical standard value of the experimental difference data, t<t 0.975 Prove that there is no significant difference in the experimental difference data, t>t 0.975 This proves that there are significant differences in the test difference data.

[0058] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical solutions and concepts of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A method for determining silicon, manganese and phosphorus in manganese-silicon alloy by X-ray fluorescence spectrometer, the method is implemented by X-ray fluorescence spectrometer, characterized in that: The specific steps of the method for determining silicon, manganese and phosphorus in manganese-silicon alloy by X-ray fluorescence spectrometer are as follows: S1. Sample preparation Cleaning the grinding mortar for grinding the sample with the test sample of the manganese silicon alloy to be prepared; The test sample with a particle size of less than 1 mm to be prepared is loaded into a ceramic crucible, with the loading amount being 90-100%; Place the grinding mortar filled with the sample into the grinder, grind for 80 seconds, then take it out and bag it; S2. Sample pressing Clean the sample pressing machine and each sample pressing mold; According to the specifications of the sample pressing machine, a feeder is placed in the sample pressing tank. The feeder is a concentric circle structure sleeve. The test sample is placed in the inner cylinder of the feeder. Use a sample leveler to contact the surface of the test sample in the inner tube of the feeder with the bottom flat surface of the sample leveler, gently rotate the sample leveler to make the test sample flat, and then take out the sample leveler; Put boric acid on the surface of the test sample in the inner cylinder of the feeder, and then evenly sprinkle boric acid into the outer cylinder of the feeder, lift the feeder vertically and lightly, and take the feeder out vertically in the sample pressing tank. During the process of taking out, make sure that there is no adhesion between the sample and the feeder, and sweep the boric acid around the edge of the feeder and the base of the sample pressing machine into the sample pressing tank; According to the specifications of the sample pressing machine, place the top seat on the top of the test sample in the sample pressing tank and make sure it is level and not tilted; The sample pressing machine performs sample pressing, and after the sample pressing is completed, the sample is removed; S3. Analyze the element content by detecting the fluorescence excitation energy of the elements in the sample through X-ray fluorescence method Select a standard sample of manganese silicon alloy with determined content of each element, press the sample and put it into an X-ray fluorescence spectrometer, set the X-ray fluorescence excitation energy conditions of each element composition in the standard sample on the X-ray fluorescence spectrometer, and irradiate the sample of the standard sample with X-rays; The standard sample is irradiated by X-rays in the X-ray fluorescence spectrometer to obtain the intensity of the fluorescence excitation energy generated by each element; Based on a series of standard samples with determined element contents and their corresponding fluorescence excitation energy intensities, a mathematical relationship curve between the intensity of fluorescence excitation energy of each element in the manganese-silicon alloy and the content of each element is drawn in an X-ray fluorescence spectrometer, and a mathematical formula for the intensity and percentage of each element in the manganese-silicon alloy is obtained based on the mathematical relationship curve; The pressed sample of the test sample is placed in an X-ray fluorescence spectrometer, and the X-ray fluorescence excitation energy conditions of the elements in the test sample are set on the X-ray fluorescence spectrometer. The sample of the test sample is irradiated with X-rays to obtain the intensity of the fluorescence excitation energy generated by each element in the test sample. The intensity value of the excitation energy of each element is substituted into the mathematical formula of the intensity of each element in the manganese silicon alloy and the percentage of each element to obtain the percentage of each element in the manganese silicon alloy.

2. The method for determining silicon, manganese and phosphorus in manganese-silicon alloy by X-ray fluorescence spectrometer according to claim 1, characterized in that: The loading amount and grinding time of the test sample in S1 are required to be consistent in repeated tests of the same type of test samples.

3. The method for determining silicon, manganese and phosphorus in manganese-silicon alloy by X-ray fluorescence spectrometer according to claim 1, characterized in that: After the sample is depressed in S2, the sample surface must not be touched. The burrs around the sample are cleaned with a sample spoon, and the boric acid dust is blown away with an ear cleaning bulb.

4. The method for determining silicon, manganese and phosphorus in manganese-silicon alloy by X-ray fluorescence spectrometer according to claim 1, characterized in that: The chemical compositions of the standard sample and the test sample in S3 are the same.

5. The method for determining silicon, manganese and phosphorus in manganese-silicon alloy by X-ray fluorescence spectrometer according to claim 1, characterized in that: The test conditions of the X-ray fluorescence spectrometer for the standard sample and the test sample in S3 are the same.

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