CN113624792A - Test method for determining content of ferrotungsten components - Google Patents
Test method for determining content of ferrotungsten components Download PDFInfo
- Publication number
- CN113624792A CN113624792A CN202111079161.0A CN202111079161A CN113624792A CN 113624792 A CN113624792 A CN 113624792A CN 202111079161 A CN202111079161 A CN 202111079161A CN 113624792 A CN113624792 A CN 113624792A
- Authority
- CN
- China
- Prior art keywords
- ferrotungsten
- alloy
- sample
- test method
- ferrotungsten alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/2202—Preparing specimens therefor
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Abstract
The invention provides a test method for determining the content of ferrotungsten components, which comprises the following steps: mixing a pre-oxidation reagent and the ferrotungsten alloy, pre-oxidizing, and evaporating to dryness to obtain the pre-oxidized ferrotungsten alloy; mixing the preoxidized ferrotungsten alloy and the mixed solvent, adding ammonium iodide, heating and melting to prepare a glass sample wafer, and obtaining a sample to be tested; the method has the advantages that the component analysis is carried out on the sample to be tested by adopting the X-ray fluorescence method fuse piece analysis, so that the component content result of the ferrotungsten alloy is obtained, the test method can complete the determination of multiple elements such as tungsten, iron, thallium, phosphorus, manganese, silicon and the like in ferrotungsten at one time by adopting the X-ray fluorescence method fuse piece analysis, the detection efficiency is improved, the fuse piece analysis does not relate to the improvement of the particle effect problem in tabletting analysis, and the accuracy is high.
Description
Technical Field
The invention relates to the technical field of chemical analysis, in particular to a test method for determining the content of ferrotungsten components.
Background
In the national standard GB7731.1-87, ferrotungsten is dissolved by acid, then the content of tungsten is measured by a cinchonine gravimetric method, the middle part relates to multiple times of filtration, ignition and constant weight, and the later independent measurement of thallium is carried out, the process is complicated, and the time is 3-5 days. Phosphorus, manganese, silicon and the like in the ferrotungsten alloy can be detected by a national standard method or by inductively coupled plasma, but the process is complicated.
CN110455783A discloses a method for rapidly analyzing tungsten, manganese, copper, silicon and phosphorus in ferrotungsten, which comprises: preparing tungsten-manganese-copper-silicon-phosphorus standard samples with different concentrations by taking a tungsten-iron standard sample, high-purity iron with iron content higher than 99.99 wt% and a standard solution of silicon-manganese-copper-phosphorus as standard raw materials; dissolving a standard sample by using a first acid solution to form a standard solution; measuring the spectral line intensity of tungsten, manganese, copper, silicon and phosphorus in a standard solution by using an inductively coupled plasma atomic emission spectrometer, and drawing a calibration curve by taking the element concentration as a horizontal coordinate and the spectral line intensity as a vertical coordinate; selecting a sensitive level or a sub-sensitive level spectral line of each element in the calibration curve as an analysis line; dissolving a ferrotungsten sample to be detected by adopting a second acid solution which is the same as the first acid solution to obtain a sample solution; and measuring the spectral line intensity of tungsten, manganese, copper, silicon and phosphorus in the sample solution, and obtaining the content of tungsten, manganese, copper, silicon and phosphorus according to an analysis line. However, the method cannot simultaneously obtain the measurement results of multiple elements such as tungsten, thallium, phosphorus, manganese, silicon and the like.
CN107632015A discloses a method for determining the content of tungsten in ferrotungsten, which comprises the following steps: mixing the weighed ferrotungsten sample, phosphoric acid and perchloric acid, heating until the liquid level is calm after the mixed solution emits clean perchloric acid smoke; adding perchloric acid, and heating until the liquid level is calm after the mixed solution is completely smoked by perchloric acid; adding perchloric acid into the mixed solution for the third time, mixing, heating until perchloric acid smoke is emitted from the mixed solution and bubbles are generated for 5-10 seconds; adding a dilute phosphoric acid solution into the mixed solution, cooling to room temperature, and diluting with dilute phosphoric acid to obtain a mother solution; transferring part of mother liquor and a container which is added with dilute phosphoric acid in advance, sequentially adding a thiocyanate solution, a stannous chloride solution, dilute sulfuric acid and a titanium trichloride solution, mixing and developing to obtain a developing solution; measuring the absorbance of the developing solution; and calculating to obtain the content of tungsten in the ferrotungsten sample according to the measured absorbance value and the established working curve function. However, the method cannot simultaneously obtain the measurement results of multiple elements such as tungsten, thallium, phosphorus, manganese, silicon and the like.
CN107941788A discloses an ICP-OES method for determining the content of tungsten in ferrotungsten, which comprises the following steps: making a standard curve: preparing n standard solutions with the tungsten mass concentration of 40-80%, detecting the light intensity value of each standard solution by using a plasma emission spectrometer, and drawing a concentration-light intensity standard curve through the concentration and the corresponding light intensity value; n is more than or equal to 2; preparing a solution to be detected: mixing ferrotungsten, the mixed acid solution and hydrogen peroxide, and heating to completely dissolve the ferrotungsten to obtain a sample to be detected; detecting a sample to be detected by using a plasma emission spectrometer to obtain a corresponding light intensity value; and obtaining the mass concentration of tungsten in the sample to be detected through the concentration-light intensity standard curve and the light intensity value, and then calculating to obtain the tungsten content in the ferrotungsten. However, the method cannot simultaneously obtain the measurement results of multiple elements such as tungsten, thallium, phosphorus, manganese, silicon and the like.
Therefore, it is necessary to develop a testing method which is simple to operate, has high accuracy and can complete the measurement of multiple elements such as tungsten, thallium, phosphorus, manganese, silicon and the like in the ferrotungsten alloy at one time.
Disclosure of Invention
In order to solve the technical problems, the invention provides a test method for measuring the content of ferrotungsten components, the test method can complete the measurement of multiple elements such as tungsten, iron, thallium, phosphorus, manganese, silicon and the like in ferrotungsten at one time by adopting X-ray fluorescence method fuse piece analysis, the method improves the detection efficiency, and the fuse piece analysis does not relate to the improvement of the particle effect problem in tabletting analysis and has high accuracy.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a test method for determining the content of ferrotungsten components, which comprises the following steps:
(1) mixing a pre-oxidation reagent and the ferrotungsten alloy, and performing pretreatment to obtain the preoxidized ferrotungsten alloy;
(2) mixing a mixed solvent with the preoxidized ferrotungsten alloy in the step (1), adding ammonium iodide, heating and melting to prepare a glass sample wafer, and obtaining a sample to be tested;
(3) and (3) analyzing the components of the sample to be tested in the step (2) by adopting X-ray fluorescence method fuse piece analysis to obtain a component content result of the ferrotungsten alloy.
The method comprises the steps of pre-oxidizing a ferrotungsten sample by nitric acid and hydrogen peroxide, wherein the pre-oxidizing is to convert simple substance elements in ferrotungsten alloy into oxides to prevent corrosion of a platinum-gold crucible, evaporating to dryness at a low temperature on an electric heating plate, adding a mixed flux comprising anhydrous lithium tetraborate and lithium metaborate after cooling to better melt the sample and prepare a glass sample wafer for fluorescence analysis, adding a certain amount of ammonium iodide reagent to promote the fluidity of the sample so as to smoothly demould and shape the sample wafer, and melting the sample wafer on a sample melting machine to prepare the glass sample wafer. The same method is adopted to manufacture a standard sample wafer to complete a ferrotungsten fluorescence curve, the curve is used for analyzing a sample to be detected, and the contents of elements such as tungsten, iron, silicon, manganese, phosphorus and the like in ferrotungsten can be obtained at one time.
As a preferable technical scheme of the invention, the pretreatment in the step (1) comprises pre-oxidation and evaporation to dryness which are sequentially carried out;
in the present invention, the pre-oxidation is carried out in a platinum-gold crucible.
Preferably, the pre-oxidation reagent in step (1) comprises nitric acid and hydrogen peroxide in a volume ratio of 1 (1-1.4), such as 1:1, 1:1.1, 1:1.2, 1:1.3, or 1:1.4, but not limited to the recited values, and other combinations not recited in this range are also applicable.
The pre-oxidation reagent adopts nitric acid and hydrogen peroxide with a specific volume ratio, so that ferrotungsten samples can be effectively decomposed, simple substance elements can be oxidized, and the platinum-gold crucible is prevented from being corroded.
Preferably, the nitric acid has a concentration of 65 to 68 wt%, and may be, for example, 65 wt%, 65.5 wt%, 66 wt%, 66.5 wt%, 67 wt%, 67.5 wt%, 68 wt%, or the like, but is not limited to the recited values, and other combinations not recited within this range are also applicable.
Preferably, the concentration of the hydrogen peroxide is 30 to 40 wt%, for example, 30 wt%, 32 wt%, 34 wt%, 36 wt%, 38 wt%, or 40 wt%, etc., but is not limited to the recited values, and other combinations not recited in this range are also applicable.
In a preferred embodiment of the present invention, the ratio of the pre-oxidized reagent to the ferrotungsten alloy is 1mL (0.03-0.04) g, and may be, for example, 1:0.03, 1:0.032, 1:0.034, 1:0.036, 1:0.038 or 1:0.04, but is not limited to the above-mentioned values, and other combinations not shown in the above range are also applicable.
Preferably, the tungsten content in the ferrotungsten alloy of step (1) is 75-79 wt%, for example 75 wt%, 75.5 wt%, 76 wt%, 76.5 wt% or 77 wt%, etc., but not limited to the recited values, and other combinations not recited in this range are also applicable.
Preferably, the ferrotungsten alloy of step (1) has an iron content of 21 to 25 wt%, such as 23 wt%, 23.5 wt%, 24 wt%, 24.5 wt%, or 25 wt%, but not limited to the recited values, and other combinations not recited in this range are also applicable.
Preferably, the ferrotungsten alloy in step (1) has an average particle size of 0.08 to 0.09mm, for example, 0.08mm, 0.082mm, 0.084mm, 0.086mm, 0.088mm, or 0.09mm, but not limited to the above-mentioned values, and other combinations not listed in this range are also applicable.
Preferably, the pretreatment time in step (1) is 40-60min, such as 40min, 42min, 44min, 46min, 48min, 50min, 52min, 54min, 56min, 58min or 60min, but not limited to the recited values, and other combinations not recited in this range are also applicable.
Preferably, the temperature for evaporation to dryness is 150 ℃ to 220 ℃, for example, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃ or 220 ℃, etc., but not limited to the recited values, and other combinations not recited in the scope are also applicable.
The invention adopts low-temperature evaporation for evaporation, so as to achieve complete oxidation effect and avoid crucible corrosion and splashing caused by later melting.
As a preferable technical solution of the present invention, after the steam drying is finished, the pre-oxidized ferrotungsten alloy is cooled.
Preferably, the mixed solvent in step (2) includes anhydrous lithium tetraborate and lithium metaborate in a mass ratio of (2-2.2):1, which may be, for example, 2:1, 2.02:1, 2.04:1, 2.06:1, 2.08:1, 2.1:1, 2.12:1, 2.14:1, 2.16:1, 2.18:1 or 2.2:1, but is not limited to the recited values, and other combinations not recited within this range are equally applicable.
Preferably, the mass ratio of the ferrotungsten alloy after pre-oxidation to the mixed solvent in the mixing in the step (2) is 1 (18-20), and may be, for example, 1:18, 1:18.5, 1:19, 1:19.5, or 1:20, but is not limited to the above-mentioned values, and other combinations not listed in this range are also applicable.
Preferably, the mass ratio of the ammonium iodide in the step (2) to the pre-oxidized ferrotungsten alloy is 1 (4-6), and may be, for example, 1:4, 1:4.2, 1:4.4, 1:4.6, 1:4.8, 1:5, 1:5.2, 1:5.4, 1:5.8 or 1:6, but not limited to the values listed, and other combinations not listed within this range are also applicable.
The ammonium iodide and the preoxidized ferrotungsten alloy limit a specific mass ratio, so that the mobility is the best, the fluorescence intensity is the most stable, and the problem that an available glass sample cannot be prepared due to poor mobility is avoided.
As a preferred embodiment of the present invention, the temperature of the heat-melting in the step (2) is 1000-1100 ℃, for example, 1000 ℃, 1010 ℃, 1020 ℃, 1030 ℃, 1040 ℃, 1050 ℃, 1060 ℃, 1070 ℃, 1080 ℃, 1090 ℃, or 1100 ℃, etc., but not limited to the values listed, and other combinations not listed in this range are also applicable.
Preferably, the time for heating and melting in step (2) is 10-20min, such as 10min, 12min, 14min, 16min, 18min or 20min, but not limited to the recited values, and other combinations not recited in the range are also applicable.
As a preferable technical scheme of the invention, before the sample to be tested is analyzed in the step (3), the component analysis is carried out on the standard sample by adopting X-ray fluorescence method fuse piece analysis to obtain a ferrotungsten fluorescence curve.
Preferably, the ferrotungsten fluorescence curve is adopted to analyze the result of the X-ray fluorescence method fuse piece analysis of the sample to be tested, so as to obtain the component content result of the ferrotungsten alloy.
As a preferred technical scheme of the invention, the test method comprises the following steps:
(1) mixing a pre-oxidation reagent and the ferrotungsten alloy, and performing pretreatment to obtain the preoxidized ferrotungsten alloy; the pretreatment comprises pre-oxidation and evaporation to dryness which are sequentially carried out; the pre-oxidation reagent comprises nitric acid and hydrogen peroxide in a volume ratio of 1 (1-1.4); the concentration of the nitric acid is 65-68 wt%; the concentration of the hydrogen peroxide is 30-40 wt%; the proportion of the pre-oxidized reagent to the ferrotungsten alloy is 1mL (0.03-0.04 g); the tungsten content in the ferrotungsten alloy is 75-79 wt%; the iron content in the ferrotungsten alloy is 21-25 wt%; the average grain diameter of the ferrotungsten alloy is 0.08-0.09 mm; after the steaming is finished, cooling the preoxidized ferrotungsten alloy;
(2) mixing a mixed solvent with the preoxidized ferrotungsten alloy in the step (1), adding ammonium iodide, heating and melting to prepare a glass sample wafer, and obtaining a sample to be tested; the mixed solvent comprises anhydrous lithium tetraborate and lithium metaborate in a mass ratio of (2-2.2) to 1; the mass ratio of the tungsten-iron alloy and the mixed solvent after preoxidation in the mixing is 1 (18-20); the mass ratio of the ammonium iodide to the preoxidized ferrotungsten alloy is 1 (4-6); the temperature of the heating and melting is 1000-1100 ℃; the heating and melting time is 10-20 min;
(3) analyzing the components of the sample to be tested in the step (2) by adopting X-ray fluorescence method fuse piece analysis to obtain a component content result of the ferrotungsten alloy; before analyzing the sample to be detected, performing component analysis on a standard sample by adopting X-ray fluorescence method fuse piece analysis to obtain a ferrotungsten fluorescence curve; and analyzing the result of the X-ray fluorescence method fuse piece analysis of the sample to be detected by adopting the ferrotungsten fluorescence curve to obtain the component content result of the ferrotungsten alloy.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) according to the test method for determining the content of the ferrotungsten component, provided by the invention, the X-ray fluorescence method is adopted for fuse analysis, so that the determination of multiple elements such as tungsten, iron, thallium, phosphorus, manganese, silicon and the like in ferrotungsten can be completed at one time, and the detection efficiency is high;
(2) according to the test method for determining the content of the ferrotungsten component, provided by the invention, the problem of improving the particle effect in tabletting analysis is not involved in the analysis of the fuse pieces in the test method, the detection accuracy is improved, and the error is less than or equal to 0.4%.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
First, an embodiment
Example 1
The embodiment provides a test method for determining the content of ferrotungsten components, which comprises the following steps:
(1) mixing a pre-oxidation reagent and ferrotungsten with the average particle size of 0.088mm according to the proportion of 10mL:0.3g, wherein the pre-oxidation reagent comprises nitric acid and hydrogen peroxide in a volume ratio of 1:1, the concentration of the nitric acid is 66 wt%, the concentration of the hydrogen peroxide is 30 wt%, the content of tungsten and iron in the ferrotungsten is 76.44 wt% and 22.15 wt%, respectively, performing pretreatment for 60min, wherein the pretreatment comprises pre-oxidation and evaporation to dryness at 150 ℃, and cooling to obtain the preoxidized ferrotungsten;
(2) mixing the preoxidized ferrotungsten alloy and a mixed solvent according to the mass ratio of 1 to (20), adding ammonium iodide, heating and melting for 15min at 1050 ℃ to prepare a glass sample, and obtaining a sample to be tested, wherein the mixed solvent comprises anhydrous lithium tetraborate and lithium metaborate according to the mass ratio of 67:33, and the ammonium iodide is added, and the mass ratio of the ammonium iodide to the preoxidized ferrotungsten alloy is 1: 5;
(3) and (3) analyzing components of the standard sample wafer by adopting X-ray fluorescence method fuse piece analysis to obtain a ferrotungsten fluorescence curve, analyzing the components of the sample to be tested in the step (2) by adopting X-ray fluorescence method fuse piece analysis, and analyzing the result of the X-ray fluorescence method fuse piece analysis of the sample to be tested by adopting the ferrotungsten fluorescence curve to obtain the component content result of the ferrotungsten.
Example 2
The embodiment provides a test method for determining the content of ferrotungsten components, which comprises the following steps:
(1) mixing a pre-oxidation reagent and ferrotungsten with the average particle size of 0.088mm according to the proportion of 10mL:0.3g, wherein the pre-oxidation reagent comprises nitric acid and hydrogen peroxide in a volume ratio of 1:1, the concentration of the nitric acid is 65 wt%, the concentration of the hydrogen peroxide is 30 wt%, the contents of tungsten and iron in the ferrotungsten are respectively 76.44 wt% and 22.15 wt%, performing pretreatment for 40min, wherein the pretreatment comprises pre-oxidation and evaporation to dryness at 220 ℃, and cooling to obtain the preoxidized ferrotungsten;
(2) mixing the preoxidized ferrotungsten alloy and a mixed solvent according to the mass ratio of 1:20, adding ammonium iodide, heating and melting at 1050 ℃ for 15min to prepare a glass sample, and obtaining a sample to be tested, wherein the mixed solvent comprises anhydrous lithium tetraborate and lithium metaborate according to the mass ratio of 67:33, and the ammonium iodide is added, and the mass ratio of the ammonium iodide to the preoxidized ferrotungsten alloy is 1: 5;
(3) and (3) analyzing components of the standard sample wafer by adopting X-ray fluorescence method fuse piece analysis to obtain a ferrotungsten fluorescence curve, analyzing the components of the sample to be tested in the step (2) by adopting X-ray fluorescence method fuse piece analysis, and analyzing the result of the X-ray fluorescence method fuse piece analysis of the sample to be tested by adopting the ferrotungsten fluorescence curve to obtain the component content result of the ferrotungsten.
Example 3
The embodiment provides a test method for determining the content of ferrotungsten components, which comprises the following steps:
(1) mixing a pre-oxidation reagent and ferrotungsten with the average particle size of 0.088mm according to the proportion of 10mL:0.3g, wherein the pre-oxidation reagent comprises nitric acid and hydrogen peroxide in a volume ratio of 1:1, the concentration of the nitric acid is 68 wt%, the concentration of the hydrogen peroxide is 30 wt%, the contents of tungsten and iron in the ferrotungsten are respectively 76.44 wt% and 22.15 wt%, performing pretreatment for 50min, the pretreatment comprises sequential pre-oxidation and evaporation to dryness at 180 ℃, and then cooling to obtain the preoxidized ferrotungsten;
(2) mixing the preoxidized ferrotungsten alloy and a mixed solvent according to the mass ratio of 1:20, adding ammonium iodide, heating and melting at 1050 ℃ for 15min to prepare a glass sample, and obtaining a sample to be tested, wherein the mixed solvent comprises anhydrous lithium tetraborate and lithium metaborate according to the mass ratio of 67:33, and the ammonium iodide is added, and the mass ratio of the ammonium iodide to the preoxidized ferrotungsten alloy is 1: 5;
(3) and (3) analyzing components of the standard sample wafer by adopting X-ray fluorescence method fuse piece analysis to obtain a ferrotungsten fluorescence curve, analyzing the components of the sample to be tested in the step (2) by adopting X-ray fluorescence method fuse piece analysis, and analyzing the result of the X-ray fluorescence method fuse piece analysis of the sample to be tested by adopting the ferrotungsten fluorescence curve to obtain the component content result of the ferrotungsten.
In examples 1 to 3, the contents of tungsten, iron, silicon, manganese, phosphorus and other elements in ferrotungsten can be obtained at one time.
Example 4
The embodiment provides a test method for determining the content of ferrotungsten components, which is different from the test method in embodiment 1 only in that the volume ratio of nitric acid to hydrogen peroxide in the pre-oxidation reagent in step (1) is 1:2, and the rest is the same as that in embodiment 1. The test result shows that the sample still corrodes the platinum-gold crucible after the glass sample is continuously melted after being pre-oxidized and evaporated to dryness in the volume ratio state.
Example 5
The embodiment provides a test method for determining the content of ferrotungsten components, which is different from the test method in embodiment 1 only in that the volume ratio of nitric acid to hydrogen peroxide in the pre-oxidation reagent in step (1) is 1:1.5, and the rest is the same as that in embodiment 1. The test result shows that the sample melting effect is normal after pre-oxidation and evaporation to dryness in the volume ratio state, and the corrosion phenomenon does not exist.
Example 6
This example provides a test method for determining the content of ferrotungsten components, which differs from example 1 only in that the temperature for evaporating to dryness in step (1) is 140 ℃, and the rest is the same as example 1. The test results show that the preoxidation and evaporation-to-dryness time is longer at the temperature, and the phenomenon that the hydrolysis of the sample causes the final result to be lower exists.
Example 7
This example provides a test method for determining the content of ferrotungsten components, which differs from example 1 only in that the temperature for evaporating to dryness in step (1) is 260 ℃, and the rest is the same as example 1. The test results show that the pre-oxidation and evaporation time at this temperature is very short and there is splashing of the individual samples.
Example 8
This example provides a test method for determining the content of ferrotungsten alloy components, which differs from example 1 only in that the mixed solvent described in step (2) includes anhydrous lithium tetraborate and lithium metaborate in a mass ratio of 1:1, and the rest is the same as example 1. In the test, the glass sample sheet prepared by melting is not clear enough, and the sample sheet is not easy to form.
Example 9
This example provides a test method for determining the content of ferrotungsten alloy components, which differs from example 1 only in that the mixed solvent described in step (2) includes anhydrous lithium tetraborate and lithium metaborate in a mass ratio of 2:1, and the rest is the same as example 1. In the test, the sample is found to be incompletely melted, not easy to form a sheet and poor in flowability.
Second, comparative example
Comparative example 1
This comparative example provides a test method for determining the content of the ferrotungsten alloy components, which differs from example 1 only in that only a single lithium tetraborate is added in step (2) without adding a mixed solvent, and the rest is the same as example 1. The test result shows that the sample is not melted completely, and the glass sample sheet is not bright and has a large shadow in the middle.
Comparative example 2
This comparative example provides a test method for determining the content of the ferrotungsten alloy components, which differs from example 1 only in that ammonium iodide is not added in step (2), and the rest is the same as example 1. The test results showed that the sample was poorly flowable without the addition of ammonium iodide and the sample could not be transferred to a platinum gold mold.
Comparative example 3
This comparative example provides a test method for determining the content of components of ferrotungsten alloy, which differs from example 1 only in that component measurement is performed using inductively coupled plasma in step (3), and the rest is the same as example 1. The inductively coupled plasma spectrometer is used for testing ferrotungsten, and a sample processing method in an experiment can only test silicon, manganese and phosphorus elements in the ferrotungsten, so that the result is unstable and the data deviation is large because the tungsten content is easy to hydrolyze.
Third, test and results
The calculation formula of the error of each element in the ferrotungsten alloy is shown as the formula (1).
The test results of the above examples and comparative examples are shown in table 1.
TABLE 1
From table 1, the following points can be seen:
(1) it can be seen from the data of examples 1, 2, 3, and 5 that the selected test conditions all meet the experimental requirements;
(2) the sample corrosion platinum gold crucible method in example 4 was not available;
(3) in the experiments of examples 6 and 7, tungsten hydrolysis or sample splashing is easy to occur, so that the test result is very low, and the method is not applicable;
(4) the mixed flux selected in examples 8 and 9 was not suitable for fusing to a usable glass-like sheet.
The method after the optimization of the experiment is completely suitable for the joint measurement of tungsten, silicon, manganese, phosphorus and other elements in ferrotungsten by a fluorescence method.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A test method for measuring the content of ferrotungsten components is characterized by comprising the following steps:
(1) mixing a pre-oxidation reagent and the ferrotungsten alloy, and performing pretreatment to obtain the preoxidized ferrotungsten alloy;
(2) mixing a mixed solvent with the preoxidized ferrotungsten alloy in the step (1), adding ammonium iodide, heating and melting to prepare a glass sample wafer, and obtaining a sample to be tested;
(3) and (3) analyzing the components of the sample to be tested in the step (2) by adopting X-ray fluorescence method fuse piece analysis to obtain a component content result of the ferrotungsten alloy.
2. The test method according to claim 1, wherein the pretreatment of step (1) comprises pre-oxidation and evaporation to dryness, which are sequentially performed;
preferably, the pre-oxidation reagent comprises nitric acid and hydrogen peroxide in a volume ratio of 1 (1-1.4);
preferably, the concentration of the nitric acid is 65-68 wt%;
preferably, the concentration of the hydrogen peroxide is 30-40 wt%.
3. The test method of claim 2, wherein the ratio of pre-oxidized reagent to ferrotungsten is 1mL (0.03-0.04) g;
preferably, the tungsten content in the ferrotungsten alloy in the step (1) is 75-79 wt%;
preferably, the content of iron in the ferrotungsten alloy in the step (1) is 21-25 wt%;
preferably, the ferrotungsten alloy in the step (1) has an average grain diameter of 0.08-0.09 mm.
4. The test method according to claim 2, wherein the time of the pretreatment of step (1) is 40-60 min;
preferably, the temperature for evaporation to dryness is 150-.
5. The test method according to claim 2, wherein after the steaming is finished, the pre-oxidized ferrotungsten alloy is cooled.
6. The test method according to any one of claims 1 to 5, wherein the mixed solvent of the step (2) comprises anhydrous lithium tetraborate and lithium metaborate in a mass ratio of (2-2.2): 1;
preferably, the mass ratio of the tungsten-iron alloy and the mixed solvent after pre-oxidation in the mixing in the step (2) is 1 (18-20).
7. The test method according to any one of claims 1 to 6, wherein the mass ratio of the ammonium iodide in the step (2) to the pre-oxidized ferrotungsten alloy is 1 (4-6).
8. The test method as claimed in any one of claims 1 to 7, wherein the temperature for heating and melting in step (2) is 1000-1100 ℃;
preferably, the time for heating and melting in the step (2) is 10-20 min.
9. The test method according to any one of claims 1 to 8, wherein before the sample to be tested is analyzed in the step (3), the composition of the standard sample is analyzed by using X-ray fluorescence melting analysis to obtain a ferrotungsten fluorescence curve;
preferably, the ferrotungsten fluorescence curve is adopted to analyze the result of the X-ray fluorescence method fuse piece analysis of the sample to be tested, so as to obtain the component content result of the ferrotungsten alloy.
10. The test method according to any one of claims 1 to 9, characterized in that it comprises the following steps:
(1) mixing a pre-oxidation reagent and the ferrotungsten alloy, and performing pretreatment to obtain the preoxidized ferrotungsten alloy; the pretreatment comprises pre-oxidation and evaporation to dryness which are sequentially carried out; the pre-oxidation reagent comprises nitric acid and hydrogen peroxide in a volume ratio of 1 (1-1.4); the concentration of the nitric acid is 65-68 wt%; the concentration of the hydrogen peroxide is 30-40 wt%; the proportion of the pre-oxidized reagent to the ferrotungsten alloy is 1mL (0.03-0.04 g); the tungsten content in the ferrotungsten alloy is 75-79 wt%; the iron content in the ferrotungsten alloy is 21-25 wt%; the average grain diameter of the ferrotungsten alloy is 0.08-0.09 mm; after the steaming is finished, cooling the preoxidized ferrotungsten alloy;
(2) mixing a mixed solvent with the preoxidized ferrotungsten alloy in the step (1), adding ammonium iodide, heating and melting to prepare a glass sample wafer, and obtaining a sample to be tested; the mixed solvent comprises anhydrous lithium tetraborate and lithium metaborate in a mass ratio of (2-2.2) to 1; the mass ratio of the tungsten-iron alloy and the mixed solvent after preoxidation in the mixing is 1 (18-20); the mass ratio of the ammonium iodide to the preoxidized ferrotungsten alloy is 1 (4-6); the temperature of the heating and melting is 1000-1100 ℃; the heating and melting time is 10-20 min;
(3) analyzing the components of the sample to be tested in the step (2) by adopting X-ray fluorescence method fuse piece analysis to obtain a component content result of the ferrotungsten alloy; before analyzing the sample to be detected, performing component analysis on a standard sample by adopting X-ray fluorescence method fuse piece analysis to obtain a ferrotungsten fluorescence curve; and analyzing the result of the X-ray fluorescence method fuse piece analysis of the sample to be detected by adopting the ferrotungsten fluorescence curve to obtain the component content result of the ferrotungsten alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111079161.0A CN113624792A (en) | 2021-09-15 | 2021-09-15 | Test method for determining content of ferrotungsten components |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111079161.0A CN113624792A (en) | 2021-09-15 | 2021-09-15 | Test method for determining content of ferrotungsten components |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113624792A true CN113624792A (en) | 2021-11-09 |
Family
ID=78390013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111079161.0A Pending CN113624792A (en) | 2021-09-15 | 2021-09-15 | Test method for determining content of ferrotungsten components |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113624792A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06249768A (en) * | 1993-02-26 | 1994-09-09 | Fuji Electric Co Ltd | Preparation of sample for fluorescent x-ray analysis |
| KR20040027087A (en) * | 2002-09-27 | 2004-04-01 | 주식회사 포스코 | Sample compound method for alloy iron fluorescent x-ray analysis and the sample pretreatment method thereof |
| CN109358080A (en) * | 2018-12-14 | 2019-02-19 | 南京钢铁股份有限公司 | A kind of MTG YBCO bulk-X fluorescence spectrum method measuring ferro-molybdenum major and minor component |
| CN110455783A (en) * | 2019-07-23 | 2019-11-15 | 衡阳华菱钢管有限公司 | Quickly analyze the method for tungsten copper-manganese silicon phosphorus in ferrotungsten |
| CN111879801A (en) * | 2020-06-23 | 2020-11-03 | 邯郸钢铁集团有限责任公司 | Preparation method of glass sample for XRF analysis based on acid oxidation low alloy steel sample |
-
2021
- 2021-09-15 CN CN202111079161.0A patent/CN113624792A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06249768A (en) * | 1993-02-26 | 1994-09-09 | Fuji Electric Co Ltd | Preparation of sample for fluorescent x-ray analysis |
| KR20040027087A (en) * | 2002-09-27 | 2004-04-01 | 주식회사 포스코 | Sample compound method for alloy iron fluorescent x-ray analysis and the sample pretreatment method thereof |
| CN109358080A (en) * | 2018-12-14 | 2019-02-19 | 南京钢铁股份有限公司 | A kind of MTG YBCO bulk-X fluorescence spectrum method measuring ferro-molybdenum major and minor component |
| CN110455783A (en) * | 2019-07-23 | 2019-11-15 | 衡阳华菱钢管有限公司 | Quickly analyze the method for tungsten copper-manganese silicon phosphorus in ferrotungsten |
| CN111879801A (en) * | 2020-06-23 | 2020-11-03 | 邯郸钢铁集团有限责任公司 | Preparation method of glass sample for XRF analysis based on acid oxidation low alloy steel sample |
Non-Patent Citations (1)
| Title |
|---|
| 赵靖 等: "熔融制样-X射线荧光光谱法测定生铁中硅锰磷", 冶金分析, no. 07, pages 76 - 80 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103808558B (en) | The digestion procedure of vanadium nitrogen ferrotitanium hybrid alloys core-spun yarn and detection method | |
| CN103149074A (en) | Molten sample preparation method of molybdenum, manganese, vanadium or chromium iron alloy sample for X-ray fluorescence spectroscopy | |
| CN103149073A (en) | Molten sample preparation method of silicon-iron, silicon-calcium-barium, silicon-manganese, aluminum-iron or titanium-iron alloy sample for X-ray fluorescence spectroscopy | |
| CN107132263A (en) | The method of testing of aluminium composition in aluminium etching solution | |
| CN110865069A (en) | Method for measuring titanium content in ferrochrome alloy by using inductively coupled plasma emission spectrometer | |
| CN106990098A (en) | The method of each element content in simultaneous determination aluminium electrolyte | |
| CN108037088B (en) | Method for accurately measuring titanium carbide in carbide slag | |
| CN108051542A (en) | A kind of aluminum content tests method in silico-aluminum, silicon-aluminium-barium alloy | |
| CN113624792A (en) | Test method for determining content of ferrotungsten components | |
| KR20090067862A (en) | Method of making portable analysis kit for rapid measurement of hf concentration in mixed solution | |
| CN106290438A (en) | A kind of X-ray fluorescence spectra fusion method measures the method for Calcium Fluoride Content in fluorite | |
| CN111220598A (en) | Method for rapidly measuring content of titanium dioxide in ilmenite | |
| CN116818679A (en) | Method for measuring trace sulfur | |
| JP2007108064A (en) | Specimen forming material and absorption analyzer equipped with film made of the same specimen forming material | |
| CN112683611B (en) | Digestion solution and method for determining element content in refined aluminum ingot for remelting | |
| CN112129744B (en) | Chemical phase analysis method for lithium in ore | |
| CN113670835A (en) | Method for analyzing phosphorus content in serpentine | |
| CN114323867A (en) | Method for analyzing and detecting uranium content in natural triuranium octoxide | |
| CN110631874A (en) | Sample pretreatment method for determining content of silicon element in polymer and method for determining content of silicon element in polymer | |
| Mather et al. | Coulometric-acidimetric titration of fluoride in acetic anhydride | |
| CN111879652B (en) | Correction method of hydrogen determination instrument | |
| CN113984475B (en) | Digestion liquid and method for determining element content in tungsten-copper material | |
| Pflug et al. | The determination of free acid in plutonium solutions | |
| CN112129753B (en) | Method for detecting chloride content in electrolyte for lithium ion battery | |
| CN110873695B (en) | Method for measuring phosphorus content in ferroniobium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |