阅读说明：本技术 一种轻烧镁球高温熔融x射线荧光分析方法 (Light-burned magnesium ball high-temperature melting X-ray fluorescence analysis method ) 是由 席云荣 邵海秀 何际多 刘秀秀 黄建国 于 2020-12-31 设计创作，主要内容包括：本发明公开了一种轻烧镁球高温熔融X射线荧光分析方法,包括以下步骤：1)轻烧镁球磨制制样；2)制备校准样品；3)制备校准样品样片；4)混合后脱模剂添加量的精度控制；5)高温熔样炉放置坩埚操作时间和熔样炉温度的控制；6)校准曲线的建立；7)待测样品元素的测定；8)氧化镁测量条件的设置；9)二氧化硅测量条件的设置；本发明对轻烧镁球中镁元素和硅元素含量用X射线荧光光谱方法进行分析,可应用于轻烧镁球中镁和硅含量元素的测定,能够实现轻烧镁球的快速全面快速分析,检验周期约为60min,优于同类高温熔融X射线荧光分析的检验周期,实现对于轻烧镁球中镁元素和硅元素含量准确、快速检验的要求。(The invention discloses a light-burned magnesium ball high-temperature melting X-ray fluorescence analysis method, which comprises the following steps: 1) grinding the lightly-sintered magnesium balls to prepare samples; 2) preparing a calibration sample; 3) preparing a calibration sample wafer; 4) controlling the precision of the addition amount of the release agent after mixing; 5) controlling the operation time of placing a crucible in the high-temperature sample melting furnace and the temperature of the sample melting furnace; 6) establishing a calibration curve; 7) measuring elements of a sample to be measured; 8) setting magnesium oxide measurement conditions; 9) setting the measurement condition of the silicon dioxide; the method analyzes the contents of the magnesium element and the silicon element in the light-burned magnesium balls by using an X-ray fluorescence spectrum method, can be applied to the determination of the magnesium and silicon content elements in the light-burned magnesium balls, can realize the rapid and comprehensive rapid analysis of the light-burned magnesium balls, has the inspection period of about 60min, is superior to the inspection period of the similar high-temperature melting X-ray fluorescence analysis, and meets the requirements on the accurate and rapid inspection of the contents of the magnesium element and the silicon element in the light-burned magnesium balls.)

1. A light-burned magnesium ball high-temperature melting X-ray fluorescence analysis method is characterized by comprising the following steps:

1) grinding a sample by using a light-burned magnesium ball: the grinding granularity is more than or equal to 180 meshes, the quantitative amount of a magnesium-carbon ball sample put into a mortar for grinding is 60 +/-2 grams, and the grinding time is 100 seconds;

2) preparation of calibration samples: preparing a calibration sample for establishing a calibration curve, wherein the element contained in the calibration sample is one or two of magnesium element and silicon element;

3) preparing a calibration sample wafer: mixing the burned calibration sample with a flux, melting at a high temperature, uniformly mixing, pouring into a preheated platinum-gold mold, and cooling to prepare a calibration sample wafer;

4) precision control of addition amount of release agent after mixing: accurately dropwise adding 0.5ml +/-0.05 ml of 30% ammonium bromide solution by using a micropipette;

5) controlling the operation time of placing a crucible in the high-temperature sample melting furnace and the temperature of the sample melting furnace: opening a furnace cover, placing a crucible, keeping the temperature of the sample melting furnace to be not lower than 970 ℃, prolonging the early-stage heating time by about 1min when the temperature of the sample melting furnace is reduced to 950 ℃, and keeping the magnesium oxide to be lower than a standard value by 0.08-0.19%; after the melting is finished, taking out the crucible within 30 seconds after the prompt tone of the high-temperature sample melting furnace;

6) establishing a calibration curve: respectively measuring the fluorescence intensity values of magnesium element and silicon element in the prepared calibration sample wafer by using an X-ray fluorescence spectrometer, correcting elements by using a theoretical alpha coefficient, establishing a calibration curve of element content and the corrected fluorescence intensity value, and obtaining the slope and intercept of the calibration curve;

7) and (3) determination of elements of the sample to be detected: preparing a sample wafer of the sample to be detected according to the method for preparing the sample wafer of the calibration sample in the step 2, and analyzing the sample wafer of the sample to be detected by using an X-ray fluorescence spectrometer to obtain fluorescence intensity values after correcting magnesium and silicon elements;

8) setting of magnesium oxide measurement conditions: crystal RX35 SPC, target Rh40kV 70mA, 2 theta 21.050 degree, PHA 100-326;

9) setting of silica measurement conditions: crystal RX4 SPC, target Rh40kV 70mA, 2 theta 144.780 degree, PHA 102-319.

2. The method for analyzing the high-temperature melting X-ray fluorescence of the light-burned magnesium spheres as claimed in claim 1, wherein the flux in the step 3 is a mixed flux of lithium tetraborate and lithium metaborate, the mass ratio of the lithium tetraborate to the lithium metaborate is 67:33, and the mass ratio of the flux to the sample is 16: 1; the mixed flux is weighed to be 8.0g, the light-burned magnesium ball sample is weighed to be 0.5g, the proportion of the platinum yellow crucible is 95% + 5%, and the diameter of the bottom is more than or equal to 35 mm.

3. The method for high-temperature melting X-ray fluorescence analysis of the light-burned magnesium spheres as claimed in claim 1, wherein the high-temperature melting temperature in the step 3 is 1000 ℃ and the melting time is 15 min.

4. The method for carrying out high-temperature melting X-ray fluorescence analysis on the light-burned magnesium spheres according to claim 1, wherein when the addition amount of the mold release agent in the step 4 is 0.6ml, the magnesium oxide is lower than a standard value by 0.09-0.21%; when the addition amount of the release agent is 0.4ml, the magnesium oxide is higher than the standard value by 0.12-0.29%.

5. The method for high-temperature melting X-ray fluorescence analysis of a light-burned magnesium ball according to claim 1, wherein the melting in the step 5 is completed, and when the crucible is taken out 90 seconds after the prompt sound of the high-temperature melting furnace, the bottom of the sample piece is cooled after the sample piece is molded, and bubbles are formed at the bottom, so that the sample piece cannot be used.

6. The method for high-temperature melting X-ray fluorescence analysis of the light-burned magnesium spheres as claimed in claim 1, wherein the X-ray fluorescence spectrometer in the step 6 is a Nippon Rigaku 14 type wavelength dispersion spectrometer, and both magnesium and silicon are fixed channels.

Technical Field

The invention relates to the technical field of light-burned magnesium ball assay, in particular to a high-temperature melting X-ray fluorescence analysis method for light-burned magnesium balls.

Background

The soft-burned magnesium balls are used as a flux commonly used in iron and steel works, and have the functions of slag discharging, slag component adjustment, alkalinity, viscosity and reaction capacity in iron-making and steel-making smelting processes in the works. The purpose is to react with the metal to produce a metal having the required composition and temperature.

In order to meet the requirement of production inspection indexes, the light-burned magnesium balls are inspected in a laboratory according to GB/T3286.1-2012, the first part of a limestone and dolomite chemical analysis method: measurement of calcium oxide and magnesium oxide content Complex titration and flame atomic absorption Spectroscopy "and GB/T3286.2-2012 limestone and Dolomite chemical analysis method second part: determination of the silica content silicon molybdenum blue spectrophotometry and perchloric acid dehydration gravimetric method. When the test is carried out by referring to the national standard method, operations such as acidolysis, constant volume, fractionation, titration and the like are required to be carried out after the mixed solvent is melted. About 4 hours is needed for one sample, for large-scale inspection in steel plants, the inspection amount of the light-burned magnesium balls is about 20 batches per day at present, the defects of low efficiency, long time, multiple occupied times and high labor intensity of workers exist in actual inspection operation, and the rhythm of the existing inspection task is also seriously restricted and influenced.

It is known that the laboratory test unit uses a new technology of fluorescence analysis after melting at high temperature for the light-burned magnesium balls, but in a specific operation, the magnesium oxide test needs to obtain the calculation result of the ignition loss, and then the fluorescence data is calibrated. When the detection of the ignition decrement of the light-burned magnesium balls is carried out according to the GB/T3286.8 standard of determination of ignition decrement of limestone and dolomite chemical analysis method, about 3 hours is needed, and meanwhile, the detection is greatly influenced by the environmental humidity, so that the detection error is easily caused, the calibration coefficient in the fluorescence detection is influenced, and the accuracy of the light-burned magnesium balls is improved. Therefore, a light-burned magnesium ball high-temperature melting X-ray fluorescence analysis method needs to be designed to solve the problems of long detection time, low efficiency and detection error in the existing light-burned magnesium ball fluorescence detection.

Disclosure of Invention

Aiming at the problems in the prior art, the invention aims to provide a high-temperature melting X-ray fluorescence analysis method for light-burned magnesium balls.

The technical scheme adopted by the invention for solving the technical problems is as follows: a light-burned magnesium ball high-temperature melting X-ray fluorescence analysis method comprises the following steps:

1) grinding a sample by using a light-burned magnesium ball: the grinding granularity is more than or equal to 180 meshes, the quantitative amount of a magnesium-carbon ball sample put into a mortar for grinding is 60 +/-2 grams, and the grinding time is 100 seconds;

2) preparation of calibration samples: preparing a calibration sample for establishing a calibration curve, wherein the element contained in the calibration sample is one or two of magnesium element and silicon element;

3) preparing a calibration sample wafer: mixing the burned calibration sample with a flux, melting at a high temperature, uniformly mixing, pouring into a preheated platinum-gold mold, and cooling to prepare a calibration sample wafer;

4) precision control of addition amount of release agent after mixing: accurately dropwise adding 0.5ml +/-0.05 ml of 30% ammonium bromide solution by using a micropipette;

5) controlling the operation time of placing a crucible in the high-temperature sample melting furnace and the temperature of the sample melting furnace: opening a furnace cover, placing a crucible, keeping the temperature of the sample melting furnace to be not lower than 970 ℃, prolonging the early-stage heating time by about 1min when the temperature of the sample melting furnace is reduced to 950 ℃, and keeping the magnesium oxide to be lower than a standard value by 0.08-0.19%; after the melting is finished, taking out the crucible within 30 seconds after the prompt tone of the high-temperature sample melting furnace;

6) establishing a calibration curve: respectively measuring the fluorescence intensity values of magnesium element and silicon element in the prepared calibration sample wafer by using an X-ray fluorescence spectrometer, correcting elements by using a theoretical alpha coefficient, establishing a calibration curve of element content and the corrected fluorescence intensity value, and obtaining the slope and intercept of the calibration curve;

7) and (3) determination of elements of the sample to be detected: preparing a sample wafer of the sample to be detected according to the method for preparing the sample wafer of the calibration sample in the step 2, and analyzing the sample wafer of the sample to be detected by using an X-ray fluorescence spectrometer to obtain fluorescence intensity values after correcting magnesium and silicon elements;

8) setting of magnesium oxide measurement conditions: crystal RX35 SPC, target Rh40kV 70mA, 2 theta 21.050 degree, PHA 100-326;

9) setting of silica measurement conditions: crystal RX4 SPC, target Rh40kV 70mA, 2 theta 144.780 degree, PHA 102-319.

Specifically, the flux in the step 3 is a mixed flux of lithium tetraborate and lithium metaborate, wherein the mass ratio of the lithium tetraborate to the lithium metaborate is 67:33, and the mass ratio of the flux to the sample is 16: 1; the mixed flux is weighed to be 8.0g, the light-burned magnesium ball sample is weighed to be 0.5g, the proportion of the platinum yellow crucible is 95% + 5%, and the diameter of the bottom is more than or equal to 35 mm.

Specifically, the high-temperature melting temperature in the step 3 is 1000 ℃, and the melting time is 15 min.

Specifically, when the addition amount of the release agent in the step 4 is 0.6ml, the magnesium oxide is lower than a standard value by 0.09-0.21%; when the addition amount of the release agent is 0.4ml, the magnesium oxide is higher than the standard value by 0.12-0.29%.

Specifically, when the melting in step 5 is completed and the crucible is taken out after 90 seconds after the prompt tone of the high-temperature sample melting furnace, the bottom of the sample piece is cooled after the sample piece is formed, and the sample piece cannot be used.

Specifically, the X-ray fluorescence spectrometer in step 6 is a japanese physical Rigaku 14 type wavelength dispersion spectrometer, and both the magnesium element and the silicon element are fixed channels.

The invention has the following beneficial effects:

the high-temperature melting X-ray fluorescence analysis method for the light-burned magnesium balls, which is designed by the invention, can be used for analyzing the contents of magnesium and silicon in the light-burned magnesium balls by using an X-ray fluorescence spectrum method, can be applied to the determination of the contents of the magnesium and the silicon in the light-burned magnesium balls, can realize the rapid, comprehensive and rapid analysis of the light-burned magnesium balls, has the inspection period of about 60min, is superior to the inspection period of the similar high-temperature melting X-ray fluorescence analysis, and meets the requirements on accurate and rapid inspection of the contents of the magnesium and the silicon in the light-burned magnesium balls.

Drawings

FIG. 1 is a graph of the working curve of the magnesium oxide established in the present invention. (y-1.5962 Xx-8.2815, correlation coefficient 0.988006)

Figure 2 is a graph of the silica work curve established by the present invention. (y-3.1206 Xx-0.59038, correlation coefficient 0.995972)

FIG. 3 is a diagram of the PHA region of magnesium oxide in the present invention.

FIG. 4 is a diagram of the PHA region of silica in the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be described in further detail in the following clearly and completely with reference to the accompanying drawings in the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

As shown in fig. 1-4, a method for analyzing light-burned magnesium balls by high-temperature melting X-ray fluorescence comprises the following steps:

1) grinding a sample by using a light-burned magnesium ball: the grinding granularity is more than or equal to 180 meshes, the quantitative amount of a magnesium-carbon ball sample put into a mortar for grinding is 60 +/-2 grams, and the grinding time is 100 seconds.

2) Preparation of calibration samples: preparing a calibration sample for establishing a calibration curve, wherein the calibration sample respectively comprises different types of elements with different contents, namely one or two of magnesium element and silicon element, and the used calibration sample can be a national standard substance or a mixture of the national standard substance and a high-purity reagent.

3) Preparing a calibration sample wafer: mixing the burned calibration sample with a flux, melting at 1000 ℃ for 15min, pouring the mixture into a preheated platinum-gold mold after uniform mixing, and cooling to prepare a calibration sample wafer;

the flux is a mixed flux of lithium tetraborate and lithium metaborate, wherein the mass ratio of the lithium tetraborate to the lithium metaborate is 67:33, and the mass ratio of the flux to the sample is 16: 1; the mixed flux is weighed to be 8.0g, the light-burned magnesium ball sample is weighed to be 0.5g, the proportion of the platinum yellow crucible is 95% + 5%, and the diameter of the bottom is more than or equal to 35 mm.

4) Precision control of addition amount of release agent after mixing: accurately dropwise adding 0.5ml +/-0.05 ml of 30% ammonium bromide solution by using a micropipette; the addition amount of the release agent is in a required range, and when the addition amount of the release agent is 0.6ml, the magnesium oxide is lower than a standard value of 0.09-0.21%; when the addition amount of the release agent is 0.4ml, the magnesium oxide is higher than the standard value by 0.12-0.29%.

5) Controlling the operation time of placing a crucible in the high-temperature sample melting furnace and the temperature of the sample melting furnace: after the furnace cover is opened and the crucible is placed, the temperature of the sample melting furnace cannot be lower than 970 ℃, so that the phenomenon that the temperature is too much reduced to cause the lengthening of the temperature rise time and the inconsistent melting time is avoided, when the temperature of the sample melting furnace is reduced to 950 ℃, the early temperature rise time is lengthened by about 1min, and the magnesium oxide is lower than the standard value by 0.08-0.19%;

after the melting is finished, taking out the crucible within 30 seconds after the prompt tone of the high-temperature sample melting furnace; when the crucible is taken out after 90 seconds after the sample melting furnace is finished, bubbles exist at the bottom of the sample wafer after the sample wafer is formed and cooled, and the crucible cannot be used.

6) Establishing a calibration curve: respectively measuring the fluorescence intensity values of magnesium and silicon elements in the prepared calibration sample wafer by using an X-ray fluorescence spectrometer, correcting the elements by using a theoretical alpha coefficient, establishing a calibration curve of the element content and the corrected fluorescence intensity value, and obtaining the slope and intercept of the calibration curve;

the X-ray fluorescence spectrometer is a Nippon Rigaku 14 type wavelength dispersion spectrometer, and both magnesium element and silicon element are fixed channels.

7) And (3) determination of elements of the sample to be detected: and (3) preparing a sample wafer of the sample to be detected according to the method for preparing the sample wafer of the calibration sample in the step (2), and analyzing the sample wafer of the sample to be detected by using an X-ray fluorescence spectrometer to obtain the fluorescence intensity values of the corrected magnesium and silicon elements.

8) Setting of magnesium oxide measurement conditions: crystal RX35 SPC, target Rh40kV 70mA, 2 theta 21.050 degree, PHA 100-326.

9) Setting of silica measurement conditions: crystal RX4 SPC, target Rh40kV 70mA, 2 theta 144.780 degree, PHA 102-319.

The invention discloses an embodiment:

1) preparation of calibration samples

Firstly, preparing calibration samples for establishing a calibration curve, wherein the calibration samples respectively comprise elements with different types and different contents. Wherein the number of the calibration samples should meet the requirement of the precision of the calibration curve, and the larger the number, the better the calibration curve.

The invention adopts the national standard substance and the way of matching the national standard substance with the high-purity reagent to prepare the calibration sample. The adopted national standard substances comprise GBW03128 (brucite), GBW03129 (brucite), YSBC28726-2014 (magnesite), YSBC28726a-2014 (magnesite), YSBC28727-2014 (magnesite) and YSBC28728-2014 (magnesite).

2) Preparation of a series of calibration sample coupons

About 5.0g of calibration sample is weighed, dried in a muffle furnace at 175 ℃ to constant weight, cooled to room temperature, and placed in a desiccator for use. And firing the mixed flux in a muffle furnace at 500 ℃ for 4 hours, taking out, cooling to room temperature, and placing in a dryer for later use. Weighing 8.0g of mixed flux into a platinum yellow crucible, weighing 0.5g of sample into the crucible, stirring uniformly, dropwise adding 0.5ml of 30% ammonium bromide solution by using a micropipette, and placing the mixture into a sample melting furnace which is preheated to 1000 ℃ for melting for 15 min. When the crucible is placed, the rapid operation is required, and the temperature of the sample melting furnace is ensured not to be lower than 970 ℃. And (4) taking out the crucible within 30 seconds after the sample melting is finished and the prompt tone, placing the crucible on a horizontal table, and cooling to room temperature. Taking out the sample, and pasting the serial number for later use.

3) Establishment of calibration Curve

Respectively measuring the fluorescence intensity values of magnesium and silicon elements of the prepared analysis sample by using an X-ray fluorescence spectrometer, correcting the elements by using a theoretical alpha coefficient, and establishing a working curve between the element content and the corrected fluorescence intensity as shown in a figure 1-2; wherein the measured parameters of the respective elements are shown in fig. 3-4.

4) Determination of elements in a sample to be tested

Obtaining a sample wafer for X-ray fluorescence spectrum analysis of the sample to be detected according to the method in the step 2), and analyzing the sample wafer by using an X-ray fluorescence spectrometer.

The present invention is not limited to the above embodiments, and any structural changes made under the teaching of the present invention shall fall within the scope of the present invention, which is similar or similar to the technical solutions of the present invention.

The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.