CN112051290B - Ferromolybdenum sample, preparation method thereof and method for measuring component content in ferromolybdenum alloy - Google Patents
Ferromolybdenum sample, preparation method thereof and method for measuring component content in ferromolybdenum alloy Download PDFInfo
- Publication number
- CN112051290B CN112051290B CN202010939869.8A CN202010939869A CN112051290B CN 112051290 B CN112051290 B CN 112051290B CN 202010939869 A CN202010939869 A CN 202010939869A CN 112051290 B CN112051290 B CN 112051290B
- Authority
- CN
- China
- Prior art keywords
- ferromolybdenum
- sample
- release agent
- melting
- container
- 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.)
- Active
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
- G01N23/223—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
-
- 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
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 application relates to the field of component analysis, in particular to a ferromolybdenum sample and a preparation method thereof, and a determination method of component content in a ferromolybdenum alloy. A preparation method of a ferromolybdenum sample comprises the following steps: adding anhydrous lithium tetraborate, ferromolybdenum, sodium nitrate and lithium carbonate into a container; then, adding a release agent for the first time to carry out pre-oxidation treatment; carrying out first-stage melting, and then cooling to room temperature; and after the release agent is added for the second time, the second-stage melting is carried out, and then the cooling is carried out. In the process of preparing the ferromolybdenum sample, the release agent is added twice at different times, so that the total release agent consumption can be reduced, and the waste and loss of the release agent are avoided; and the problems that the release agent is added once to cause the cracking and the demoulding are not easy to occur due to the local excess of the release agent are solved; meanwhile, the sample is not easy to crack.
Description
Technical Field
The application relates to the field of component analysis, in particular to a ferromolybdenum sample and a preparation method thereof, and a determination method of component content in a ferromolybdenum alloy.
Background
The ferromolybdenum is an alloy of molybdenum and iron, and is mainly used as an additive of molybdenum during steel making. The ferromolybdenum contains a certain amount of impurity elements such as phosphorus, copper, silicon and the like, has certain influence on the performance of steel, and has limitation on the content of the impurity elements in technical conditions. Therefore, it is necessary to analyze the composition of impurity elements in ferromolybdenum.
For example, the prior art discloses that components in ferromolybdenum are analyzed by using X-ray fluorescence, but the prior art has the problems of large measurement result error and inaccurate detection result.
Disclosure of Invention
The embodiment of the application aims to provide a ferromolybdenum sample, a preparation method thereof and a method for determining component content in a ferromolybdenum alloy, and aims to solve the problem that existing ferromolybdenum component analysis is inaccurate.
The application provides a preparation method of a ferromolybdenum sample, wherein the ferromolybdenum standard sample is suitable for measuring the content of molybdenum, phosphorus, silicon, tin or copper in a ferromolybdenum alloy by an X-ray fluorescence melting method, and the preparation method comprises the following steps:
adding anhydrous lithium tetraborate, ferromolybdenum, sodium nitrate and lithium carbonate into a container; then, adding a release agent for the first time to carry out pre-oxidation treatment;
carrying out first-stage melting, and then cooling to room temperature;
The second stage of melting was carried out after the second addition of the mold release agent, and then cooling was carried out.
In some embodiments of the first aspect of the present disclosure, the anhydrous lithium tetraborate, the ferromolybdenum, the sodium nitrate, and the lithium carbonate are in a mass ratio of 3: (0.1-0.3): (0.4-0.6): 0.4-0.6);
optionally, the mass ratio of the anhydrous lithium tetraborate, the ferromolybdenum, the sodium nitrate and the lithium carbonate is 3: 0.2: 0.5: 0.5.
in some embodiments of the first aspect of the present application, the step of pre-oxidation treatment comprises:
sequentially preserving the heat at the temperature of 340-; preserving the heat at the temperature of 450-520 ℃ for 190-220 s; preserving the heat at 600-700 ℃ for 550-650 s; and keeping the temperature at 700-750 ℃ for 190-220 s.
In some embodiments of the first aspect of the present application, the release agent comprises lithium bromide;
optionally, the mass ratio of the lithium bromide in the first-time added release agent to the ferromolybdenum is (1-3): 500, a step of;
optionally, the mass ratio of the lithium bromide in the second-time added mold release agent to the ferromolybdenum is (0.5-1): 500, a step of;
optionally, the release agent is 800-1000g/l lithium bromide water solution.
In some embodiments of the first aspect of the present application, the temperature of the first stage melting is 1100-; the static melting time is 200-300s, and the swing time is 400-500 s.
In some embodiments of the first aspect of the present application, the second melting step comprises static melting at 1000-1100 ℃ for 100-200s, and swinging at 1100-1200 ℃ for 120-140 s.
In some embodiments of the first aspect of the present application, before adding the anhydrous lithium tetraborate, the ferromolybdenum, the sodium nitrate, and the lithium carbonate to the vessel, further comprising:
adding lithium tetraborate into the container, then carrying out heat treatment at 950 +/-20 ℃ for 180-200s, taking out the container and carrying out wall hanging in a rotating way, carrying out heat treatment at 950 +/-20 ℃ for 30-50s after 30-50s, then taking out the container and carrying out wall hanging in a rotating way again;
optionally, the material of the container is a platinum alloy material;
optionally, the container is a platinum alloy crucible.
In some embodiments of the first aspect of the present application, the step of adding the anhydrous lithium tetraborate, the ferromolybdenum, the sodium nitrate, and the lithium carbonate to the vessel comprises:
and adding the ferromolybdenum, the sodium nitrate, the lithium carbonate and part of anhydrous lithium tetraborate into the container, uniformly stirring, and paving the rest anhydrous lithium tetraborate on the surface.
In a second aspect of the present application, a ferromolybdenum sample is provided, and the ferromolybdenum sample is prepared by the preparation method of the ferromolybdenum sample provided in the first aspect.
The third aspect of the present application provides a method for determining the component content in a ferromolybdenum alloy, including:
testing the fluorescence intensity of the ferromolybdenum standard sample by using an X-ray fluorescence spectrometer and drawing a standard curve;
testing the fluorescence intensity of the ferromolybdenum sample by using an X-ray fluorescence spectrometer; and corresponding the fluorescence intensity to a standard curve to obtain the component content.
The ferromolybdenum sample, the preparation method thereof and the determination method of the component content in the ferromolybdenum alloy provided by the embodiment of the application have the following beneficial effects:
in the application, in the process of preparing the ferromolybdenum sample, the release agent is added twice at different times, so that the total release agent consumption can be reduced, and the waste and loss of the release agent are avoided; and the problems that the release agent is added once to cause the cracking and the demoulding are not easy to occur due to the local excess of the release agent are solved; the release agent is added for the second time between the two melting stages, so that the ferromolybdenum oxide after being melted and formed can be mixed with the release agent again, a good demoulding effect is achieved, and meanwhile, the sample is not prone to cracking.
In addition, when the ferromolybdenum sample provided by the embodiment of the application is suitable for measuring the content of molybdenum, phosphorus, silicon, tin or copper in the ferromolybdenum by an X-ray fluorescence melting method, the test result is more accurate and is almost the same as the wet test result. By adopting the method for measuring the components in the ferromolybdenum through the ferromolybdenum sample, the problems of complicated detection steps, more detection reagents, long detection period and the like are solved, and meanwhile, the test data can be accurately obtained.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The currently used ferromolybdenum chemical analysis method in the industry is as follows: a weight method for measuring the content of molybdenum, iron and molybdenum, a weight method for measuring lead molybdate, an ammonium metavanadate titration method and a weight method for 8-hydroxyquinoline of GB/T5059.1-2014; measuring the content of molybdenum, iron and silicon in GB/T5059.5-2014 by a sulfuric acid dehydration gravimetric method and silicon-molybdenum blue spectrophotometry; GB/T5059.6-2007 Mo-Fe-P content determination by bismuth-P-Mo blue spectrophotometry and Mo blue spectrophotometry; the flame atomic absorption spectrometry method for measuring the content of the molybdenum, iron and copper in GB/T5059.3-2014; GB/T5059.4-1988 ferromolybdenum chemical analysis method polarography is used for measuring tin content and the like. However, the 5 kinds of ferromolybdenum chemical analysis belongs to the traditional chemical analysis method, the operation steps of the analysis process are complicated, the used reagents are more, and the inspection period is long.
The application provides a ferromolybdenum sample for determining the content of molybdenum, phosphorus, silicon, tin or copper in a ferromolybdenum alloy based on an X-ray fluorescence melting method.
The ferromolybdenum sample and the preparation method thereof, and the method for measuring the content of components in the ferromolybdenum alloy according to the embodiment of the present application will be specifically described below.
A preparation method of a ferromolybdenum sample is suitable for measuring the contents of molybdenum, phosphorus, silicon, tin or copper in a ferromolybdenum alloy by an X-ray fluorescence melting method, and comprises the following steps:
adding anhydrous lithium tetraborate, ferromolybdenum, sodium nitrate and lithium carbonate into a container; then, adding a release agent for the first time to carry out pre-oxidation treatment;
carrying out first-stage melting, and then cooling to room temperature;
and after the release agent is added for the second time, the second-stage melting is carried out, and then the cooling is carried out.
Further, in some embodiments, it is desirable to pretreat the container, including:
adding lithium tetraborate into the container, then carrying out heat treatment at 950 +/-20 ℃ for 180-200s, taking out the container and carrying out wall hanging in a rotating way, carrying out heat treatment at 950 +/-20 ℃ for 30-50s after 30-50s, then taking out the container and carrying out wall hanging in a rotating way again;
adding lithium tetraborate for twice heat treatment and hanging the wall. Illustratively, the temperature of the first heat treatment may be 930 ℃, 940 ℃, 950 ℃, 970 ℃, or the like. The time of the heat treatment may be 180s, 190s, 192s, 195s, or 200s, and so on.
The temperature of the first heat treatment may be 930 ℃, 940 ℃, 950 ℃, 970 ℃, or the like. The time for the heat treatment may be 30s, 32s, 35s, 37s, 39s, 40s, 47s, 49s, or 50s, or the like.
Illustratively, the material of the container is a platinum alloy material; for example, the container is a platinum alloy crucible.
In order to avoid the reaction between the molten ferromolybdenum and the container, the molten lithium tetraborate is hung on the inner wall of the container, and the ferromolybdenum is separated from the container to avoid the ferromolybdenum from damaging the container. Accordingly, lithium tetraborate can separate ferromolybdenum from platinum alloy; the condition that ferromolybdenum forms eutectic mixture with platinum alloy at high temperature and the integrity of the platinum crucible is damaged is avoided.
Twice melting and twice wall hanging, wherein the first melting time (180-200s) is longer, so that the problem of uneven first melting is avoided by reasonably controlling the melting times and the melting time of each time, and the wax-like protective film on the inner wall of the container is more compact, in order to avoid excessive melting of the first wall-hung lithium tetraborate, and the second melting time (30-50s) is shorter.
It is understood that in other embodiments of the present application, the preparation of the ferromolybdenum sample may be performed directly using the vessel after having been pretreated; alternatively, the container may be another container made of platinum alloy or a container made of a material that does not react with ferromolybdenum.
And preparing a ferromolybdenum sample after the pretreatment of the container is finished.
Adding anhydrous lithium tetraborate, ferromolybdenum, sodium nitrate and lithium carbonate into a container; then, a release agent is added for the first time to carry out pre-oxidation treatment.
In chemical analysis, sodium peroxide is often used as an oxidizing agent, but when a platinum crucible is used for melting, the corrosion of the sodium peroxide is too strong, so that the platinum crucible is not favorable for long-term use, and the splashing is easily caused due to violent reaction. Sodium nitrate (melting point of 306.8 ℃, boiling point of 380 ℃) is heated to more than 380 ℃ and then decomposed into sodium nitrite and oxygen, nitrogen and oxygen are released at 400-600 ℃, nitrogen monoxide is released at 700 ℃, a small amount of nitrogen dioxide and nitrogen monoxide are generated only at 775-865 ℃, and the strong oxidizing capability is achieved. The melting point of the lithium carbonate is 723 ℃, carbon dioxide can be decomposed when the melting point is close to the boiling point, the carbon dioxide has the capacity of oxidizing metals such as molybdenum, iron and the like in the ferro-molybdenum alloy, and has smaller gas evolution amount, so that the lithium carbonate can play a role in fully oxidizing and properly stirring a melt, and does not bring out materials due to violent gas evolution.
Illustratively, the mass ratio of anhydrous lithium tetraborate, ferromolybdenum, sodium nitrate and lithium carbonate is 3: (0.1-0.3): (0.4-0.6): 0.4-0.6); for example, 3: 0.1:0.4:0.4, 3:0.2:0.4:0.5, 3:0.3: 0.5: 0.5, 3:0.2: 0.6: 0.4, 3:0.2: 0.5: 0.5, 3:0.3: 0.6: 0.6, and so on.
Excessive sodium nitrate causes violent reaction, is easy to splash, causes low results, and causes incomplete oxidation when the amount of the sodium nitrate is small. Besides the capacity of oxidizing metals such as molybdenum, iron and the like, the lithium carbonate is also beneficial to adjusting the melt fluidity and the pH value; in addition, during the preparation process, the factors that the molybdenum has a large oxidized molecular weight and is easy to deposit at the bottom are also considered; thus, in some embodiments of the present application, the mass ratio of anhydrous lithium tetraborate, ferromolybdenum, sodium nitrate, and lithium carbonate is 3: (0.1-0.3): (0.4-0.6): 0.4-0.6); the splashing caused by excessive reaction of the sodium nitrate and the like can be avoided, and enough oxidability can be provided; the lithium carbonate can be ensured to provide enough gas evolution quantity to provide gas for fully oxidizing and stirring the melt, and the material is not brought out by violent gas evolution.
Illustratively, the step of adding anhydrous lithium tetraborate, ferromolybdenum, sodium nitrate, and lithium carbonate to the vessel comprises:
and adding the ferromolybdenum, the sodium nitrate, the lithium carbonate and part of anhydrous lithium tetraborate into the container, uniformly stirring, and paving the rest anhydrous lithium tetraborate on the surface. The method can ensure that the ferromolybdenum sample is fully contacted with the oxidant, and meanwhile, the pre-oxidation is carried out in a sealed space, so that the reaction speed of the oxidant and the ferromolybdenum sample is improved; and secondly, covering with an anhydrous lithium tetraborate fusing agent, wrapping the oxidized sample in the middle, and enabling the oxidized sample to be better and more thoroughly and uniformly mixed with lithium tetraborate in the fusing process.
After adding anhydrous lithium tetraborate, ferromolybdenum, sodium nitrate and lithium carbonate into a container, adding a release agent into the container for the first time to carry out pre-oxidation treatment.
In this example, the mold release agent was 800-1000g/l aqueous lithium bromide. For example, the concentration of the aqueous lithium bromide solution may be 800g/l, 850g/l, 900g/l, 950g/l, 1000g/l, and so forth.
The mass ratio of the lithium bromide to the ferromolybdenum in the release agent added for the first time is (1-3): 500, a step of; for example, the ratio of 1:500, 1.3: 500. 1.6: 500. 2:500, 2.5:500, or 3: 500.
In an embodiment of the present application, the step of pre-oxidation treatment comprises:
sequentially preserving the heat at the temperature of 340-; preserving the heat at the temperature of 450-520 ℃ for 190-220 s; preserving the heat at 600-700 ℃ for 550-650 s; and keeping the temperature at 700-750 ℃ for 190-220 s.
In other words, in the present embodiment, the pre-oxidation treatment is performed in four stages. The temperature of the first stage is 340-360 ℃ (for example, 340 ℃, 342 ℃, 348 ℃, 350 ℃, 360 ℃ and the like), and the heat preservation time is 190-220s (for example, 190s, 195s, 200s, 210s, 220s and the like); then, the pre-oxidation is performed in the second stage, the temperature in the second stage is 450-520 ℃ (for example, 450 ℃, 458 ℃, 468 ℃, 478 ℃, 495 ℃, 510 ℃, 520 ℃ and the like), and the holding time is 190-220s (for example, 190s, 196s, 203s, 215s, 220s and the like); then, the pre-oxidation is performed in the third stage at 600-700 deg.C (for example, 600 deg.C, 612 deg.C, 624 deg.C, 636 deg.C, 658 deg.C, 675 deg.C, 688 deg.C, 690 deg.C, 700 deg.C, etc.). Then, the oxidation is performed in the fourth stage, wherein the temperature in the fourth stage is 700-750 deg.C (such as 700 deg.C, 712 deg.C, 724 deg.C, 736 deg.C, 745 deg.C, 750 deg.C, etc.), and the holding time is 190-220s (such as 190s, 196s, 203s, 215s, 220s, etc.).
Ferromolybdenum is easy to alloy with platinum or form a eutectic mixture at a high temperature, so that the integrity of a platinum crucible is damaged, and the platinum crucible is used as a valuable article and must ensure absolute safety during melting operation, so that ferroalloy samples such as ferromolybdenum cannot be directly melted to prepare samples. After the ferromolybdenum is subjected to preoxidation treatment, the reducibility of the ferromolybdenum is completely disappeared, so that the ferromolybdenum can be melted and prepared into a sample.
The melting point of the lithium tetraborate is 921 ℃, so that the lithium tetraborate protective layer is still in a solid state in the whole pre-oxidation process, the reducing substance cannot be directly contacted with the container, the ferromolybdenum is prevented from reacting with the container (such as a platinum alloy crucible) in the oxidation process, and the whole pre-oxidation temperature is below 900 ℃.
Sodium nitrate (melting point 306.8 ℃, boiling point 380 ℃) is heated to more than 380 ℃ and then decomposed into sodium nitrite and oxygen, nitrogen and oxygen are released at 400-600 ℃, nitric oxide, a small amount of nitrogen dioxide and nitrous oxide are released at 700 ℃, and the sodium nitrate has strong oxidizing capability.
The melting point of the lithium carbonate is 723 ℃, carbon dioxide can be decomposed when the melting point is close to the boiling point, the carbon dioxide has the capacity of oxidizing metals such as molybdenum, iron, manganese and the like in the ferro-molybdenum alloy, and has a small gas evolution amount, so that the lithium carbonate can play a role in fully oxidizing and properly stirring a melt, and materials brought by violent gas evolution do not exist. The addition of lithium carbonate is also beneficial to adjusting the melt fluidity and the pH value.
In this embodiment, the pre-oxidation is performed in four stages to ensure that the molybdenum, iron, copper, and tin elements in the ferromolybdenum alloy are sufficiently oxidized. According to the different melting points of lithium tetraborate, sodium nitrate and lithium carbonate, the pre-oxidation heating temperature is divided into four sections, so that different substances fully react in each temperature section to play the role of the substances, and the heat preservation time of different stages is controlled respectively to ensure that molybdenum, iron, copper and tin elements in the ferromolybdenum alloy are fully oxidized.
In other embodiments of the present application, the pre-oxidation treatment may also be performed in other treatment manners, so as to achieve the purpose of fully oxidizing the molybdenum, iron, copper, and tin elements in the ferromolybdenum alloy.
The pre-oxidation treatment is followed by a first stage melting and then cooling to room temperature (e.g., 20-30 c, which may be 25 c).
The first stage melting makes ferromolybdenum and other materials completely melted, and improves the uniformity of the sample.
In the embodiment of the present application, the temperature of the first stage melting is 1100-; wherein the static melting time is 200-300s (for example, 200s, 220s, 250s, 260s, 280s, or 300s, etc.), and the swing time is 400-500s (for example, 400s, 410s, 430s, 470s, 490s, or 500s, etc.).
Lithium tetraborate has a melting point of 921 deg.c and is capable of melting to a liquid state when the melt temperature is above this temperature. After experiments, the lithium tetraborate shows better fluidity when the temperature is higher than 1050 ℃, and is beneficial to sample dissolution and uniform mixing, but the sample melting temperature also needs to consider the tolerance degree of a sample melting furnace.
In addition, the fusing agent and the tested elements are volatilized to different degrees along with the rise of the temperature, particularly the volatilization of the release agent is severe, and finally the glass sheet is difficult to release. Therefore, the temperature of the first stage melting is determined to be 1100-.
The melting time determines the homogeneity of the sample; the melting time in the first stage can ensure that materials such as ferromolybdenum and the like are completely melted, and twice of the melting time is adopted for swinging, so that the uniformity of a sample can be improved.
It should be noted that in other embodiments of the present application, the temperature of the first stage melting may be higher for a high temperature resistant vessel, and the time may be further increased.
After the first stage melting, the second stage melting is carried out after the release agent is added for the second time, and then the mixture is cooled.
In this example, the first and second addition of release agents were lithium bromide solutions in water at the same concentration. In other embodiments, the concentrations of the release agents added at the two times may also be different. The release agent added for the second time is 800-1000g/l lithium bromide aqueous solution.
The mass ratio of the lithium bromide to the ferromolybdenum in the release agent added for the second time is (0.5-1): 500; for example, the ratio of 0.5:500, 0.6: 500. 0.7: 500. 0.9:500 or 1: 500.
The release agent added for the first time is partially lost after the melting in the first stage, which easily causes the sample to crack, and the release is not good, so the release agent is added for the second time before the melting in the second stage.
The method of adding the release agent twice can reduce the dosage of the release agent for the first time, avoid the release agent loss caused by excessive addition of the release agent for the first time and the problems of easy cracking of samples, poor release and the like caused by incapability of controlling proper addition amount, and the mass ratio of the lithium bromide to the ferromolybdenum added into the release agent for the second time is (0.5-1): 500, the total addition of the release agent can be reduced, the release effect is better, and the sample is not easy to crack.
In this embodiment, the second stage melting step comprises static melting at 1100 ℃ for 100-.
Illustratively, the temperature of the static melt may be 1000 ℃, 1050 ℃, 1070 ℃, 1090 ℃, 1100 ℃, or the like. The static melting time may be 100s, 120s, 130s, 150s, or 200s, etc., and the rocking time may be 120s, 123s, 128s, 130s, or 140s, etc.
Because the molecular weight of the molybdenum oxide is larger, the molybdenum oxide is easy to deposit on the bottom in the first stage of melting, so that the uniformity of one melting cannot be completely uniform, and the melting in two stages can improve the uniformity.
The purpose of the rocking is to give better fluidity to the sample, and to protect the container, the second stage melting at the above time and temperature ensures complete melting of the glass sheet and better fluidity, so that the various oxides and borates are fully and uniformly combined.
It is understood that in other embodiments of the present application, other values may be selected for the process parameters of the second stage to ensure that the various oxides are sufficiently and uniformly combined with the borate.
And after the second stage of melting is finished, pouring the sample into a preheated mold while the sample is hot, naturally cooling the sample into a glass sheet, and attaching a mark.
The ferromolybdenum sample and the preparation method thereof provided by the embodiment of the application have at least the following advantages:
adding a release agent for the first time before pre-oxidation treatment; the mold release agent is added a second time after the first stage melting. The release agent is added twice, so that the total amount of the release agent can be saved, the problem that a sample is easy to crack is avoided, and the release agent has the advantage of easy release in the preparation process.
Further, in some embodiments of the present application, the pre-oxidation treatment is performed in four stages, so that the material is sufficiently oxidized while the container is separated from the molten ferromolybdenum, and the reaction between the container and the molten ferromolybdenum is avoided.
Further, in some embodiments of the present application, the mass ratio of anhydrous lithium tetraborate, the ferromolybdenum, the sodium nitrate, and the lithium carbonate is 3: (0.1-0.3):(0.4-0.6):(0.4-0.6). Can ensure that ferromolybdenum is fully oxidized to obtain a uniform molten mass, and can avoid the occurrence of splashing and material carrying-out.
The embodiment of the application also provides a ferromolybdenum sample, and the ferromolybdenum standard sample is prepared by the preparation method of the ferromolybdenum sample.
By adopting the ferromolybdenum standard sample provided by the embodiment of the application, the rapid, safe and accurate fusion determination of the contents of molybdenum, silicon, phosphorus, copper and tin in the ferromolybdenum alloy can be realized on an X-ray fluorescence spectrometer. The method effectively overcomes the mineral effect and the particle effect of the ferroalloy, solves the problem of large error of the measurement result caused by the sample size effect and the mineral effect of a powder tabletting method on the one hand, is not limited by a furnace special for a centrifugal casting method on the other hand, and also avoids the problem that the loss of the sample is possibly caused by splashing in the processes of sample dissolution, concentration and the like of the sample by using nitric acid to influence the detection result.
The application also provides a method for measuring the component content in the ferro-molybdenum alloy, which comprises the following steps:
testing the fluorescence intensity of the ferromolybdenum standard sample by using an X-ray fluorescence spectrometer and drawing a standard curve;
testing the fluorescence intensity of the ferromolybdenum sample by using an X-ray fluorescence spectrometer; and corresponding the fluorescence intensity to a standard curve to obtain the component content.
Further, in some embodiments of the present application, a ferromolybdenum standard sample is prepared by the above-mentioned ferromolybdenum sample preparation method for ferromolybdenum with known composition; preparing a test sample by adopting the same method for ferromolybdenum of a sample to be tested; testing the fluorescence intensity of the ferromolybdenum standard sample by using an X-ray fluorescence spectrometer and drawing a standard curve; testing the fluorescence intensity of the ferromolybdenum sample by using an X-ray fluorescence spectrometer; and corresponding the fluorescence intensity to a standard curve to obtain the component content. The features and properties of the present application are described in further detail below with reference to examples.
Example 1
This example provides a ferromolybdenum sample, which is prepared by the following steps:
1. chemical reagent preparation
Approved analytical reagents and tertiary water in accordance with GB/T6682 were used in the analysis unless otherwise stated.
Anhydrous lithium tetraborate: and (3) a solid.
Lithium carbonate: and (3) a solid.
Sodium nitrate: and (3) a solid.
Lithium bromide solution (1000 g/L): slowly adding 100g of lithium bromide solid into a beaker filled with 40mL of distilled water in advance (stirring while adding the reagent), stirring for 2-3 min after the reagent is added, adding 50mL of water again, continuously stirring until the reagent is completely dissolved, cooling to room temperature, diluting to 100mL with water, and storing in a reagent bottle for later use.
2 instruments and utensils
An X-ray fluorescence spectrometer; a high-frequency melting furnace; a platinum-yellow crucible (material 95% Pt-5% Au); crucible cover (ceramic, inside diameter)
)。
3 crucible wall hanging
4.0000g of lithium tetraborate is accurately weighed in a platinum alloy crucible, the lithium tetraborate is melted for 180s at 950 +/-20 ℃ of a high-frequency melting machine, the platinum crucible is taken out after the lithium tetraborate is melted, the crucible is slowly rotated at 45 degrees, the crucible is put into the high-frequency melting machine for melting for 30s at 950 +/-20 ℃ after being cooled for 30s, the platinum crucible is taken out again, the crucible is slowly rotated at 45 degrees, and a layer of compact wax-like protective film is formed on the inner wall of the crucible after the lithium tetraborate is cooled.
Preparation of 4 ferromolybdenum samples
1.0000g of anhydrous lithium tetraborate, 0.2000g of ferromolybdenum sample, 0.5000g of sodium nitrate and 0.5000g of lithium carbonate are added into a platinum crucible; uniformly stirring a sample and a reagent; the surface was covered with 2.0000g of anhydrous lithium tetraborate. The reagents and samples were weighed to. + -. 0.0002 g.
After 8 drops of lithium bromide are added along the periphery of the reagent, the reagent is placed on a high-frequency melting furnace and enters a pre-oxidation stage of a sample (the temperature/time of the first stage is 350 ℃/200s, the temperature/time of the second stage is 500 ℃/200s, the temperature/time of the third stage is 650 ℃/600s, and the temperature/time of the fourth stage is 720 ℃/200 s).
After the pre-oxidation operation is finished, the first melting stage of the sample is carried out, the melting temperature is 1100 ℃ (the static melting is 200s, the swinging time is 400s), and the melt is cooled to the room temperature in the crucible after the first melting stage is finished. Then 1 drop of lithium bromide was added to the cooled crucible and then passed to the second melting stage. The second melting stage comprises: static melting temperature/time 1000 deg.C/100 s, swing time/temperature 1100 deg.C/120 s.
And after the melting is finished, pouring the sample into a preheated mold while the sample is hot, naturally cooling the sample into a glass sheet, and attaching a mark.
The ferromolybdenum sample provided in example 1 can be used for testing the content of components in the ferromolybdenum alloy by an X-ray fluorescence spectrometer.
The embodiment also provides a test method, which comprises the following steps:
testing the fluorescence intensity of the ferromolybdenum standard sample by using an X-ray fluorescence spectrometer and drawing a standard curve;
the ferromolybdenum sample of example 1 was tested for fluorescence intensity using an X-ray fluorescence spectrometer; and corresponding the fluorescence intensity to a standard curve to obtain the component content.
Test example 1
The same two groups of raw materials are adopted, wherein one group adopts the method provided by the embodiment 1 to measure the content of each element in the ferromolybdenum; another group differs from the method provided in example 1 in that the content of raw material in the ferromolybdenum is tested in the first melting stage, melting temperature 1150 ℃. The measurement results are shown in table 1.
TABLE 1 Effect of different temperatures on the measurement results
| Temperature/. degree.C | 1100 | 1150 | Authentication value |
| Mo | 64.86 | 65.00 | 64.84 |
| Si | 0.105 | 0.095 | 0.10 |
| P | 0.0458 | 0.0436 | 0.044 |
| Cu | 0.337 | 0.324 | 0.33 |
| Sn | 0.0022 | 0.0021 | 0.0020 |
As can be seen from table 1, the melting temperature of the first melting stage is either 1100 ℃ or 1150 ℃ to obtain relatively accurate test results.
Test example 2
And (3) measuring the contents of molybdenum, silicon, phosphorus, copper and tin in the ferromolybdenum alloy by using an X-ray fluorescence melting method.
The operating conditions of the X-ray fluorescence spectrometer are shown in table 2.
TABLE 2 instrumental measurement conditions
In order to determine the precision of the method provided in example 1, 11 samples were prepared according to the preparation method of the ferromolybdenum sample provided in example 1, wherein the standard sample of ferromolybdenum with the same type national standard number of GSB2012-11, and their relative standard deviations were calculated, and the results are shown in table 3.
Table 3 precision test results (n ═ 11)
As can be seen from the results in Table 3, the measured values deviate little from the standard values, and the results are accurate and precise.
To further verify the accuracy of the method provided in example 1, four samples of ferromolybdenum as a raw material entering the factory were randomly sampled and tested by the method provided in example 1 and compared with the values measured by wet chemical analysis, and the results are shown in table 4. Chemical wet analysis method: mo is measured by adopting an 8-hydroxyquinoline gravimetric method, Cu, P and Si are measured by adopting an inductively coupled plasma emission spectrum, and Sn element is measured by adopting an atomic fluorescence spectrometry.
TABLE 4 comparison of the results of the wet determination with the method of the present application
In conclusion, the ferromolybdenum standard sample obtained by the method provided by the embodiment of the application is used for determining the contents of molybdenum, silicon, phosphorus, copper and tin in the ferromolybdenum alloy by an X-ray fluorescence melting method, and has the advantages of high analysis precision, high analysis speed and consistency with the determination result of a chemical method. The result obtained by the method provided by the embodiment of the application is consistent with the value obtained by a wet method. The method has accurate and reliable analysis result and meets the requirement of daily analysis.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (8)
1. A preparation method of a ferromolybdenum sample is suitable for measuring the content of molybdenum, phosphorus, silicon, tin or copper in a ferromolybdenum alloy by an X-ray fluorescence melting method, and is characterized by comprising the following steps:
adding anhydrous lithium tetraborate, ferromolybdenum, sodium nitrate and lithium carbonate into a container; then, adding a release agent for the first time to carry out pre-oxidation treatment;
carrying out first-stage melting, and then cooling to room temperature;
after the release agent is added for the second time, the second-stage melting is carried out, and then the mixture is cooled;
the release agent added for the first time and the release agent added for the second time are lithium bromide aqueous solutions; the mass ratio of the lithium bromide in the first-time added release agent to the ferromolybdenum is (1-3): 500, a step of; the mass ratio of the lithium bromide in the release agent added for the second time to the ferromolybdenum is (0.5-1): 500, a step of;
the pre-oxidation treatment step comprises: sequentially preserving the heat at the temperature of 340-; preserving the heat at the temperature of 450-520 ℃ for 190-220 s; preserving the heat at 600-700 ℃ for 550-650 s; and heat preservation at 700-750 ℃ for 190-220 s;
the temperature of the first-stage melting is 1100-1200 ℃; the static melting time is 200-300s, and the swing time is 400-500 s;
the second stage melting step comprises static melting at 1000-1100 ℃ for 100-200s, and swinging at 1100-1200 ℃ for 120-140 s.
2. The method for preparing a ferromolybdenum sample according to claim 1,
the mass ratio of the anhydrous lithium tetraborate to the ferromolybdenum to the sodium nitrate to the lithium carbonate is 3: (0.1-0.3):(0.4-0.6):(0.4-0.6).
3. The method for preparing a ferromolybdenum sample according to claim 2, wherein the mass ratio of the anhydrous lithium tetraborate, the ferromolybdenum, the sodium nitrate, and the lithium carbonate is 3: 0.2: 0.5: 0.5.
4. the method for preparing a ferromolybdenum sample according to claim 1,
the release agent is 800-1000g/L lithium bromide aqueous solution.
5. The method for preparing a ferromolybdenum sample according to any one of claims 1 to 4, characterized in that before adding said anhydrous lithium tetraborate, said ferromolybdenum, said sodium nitrate and said lithium carbonate to said container, it further comprises:
adding lithium tetraborate into the container, then carrying out heat treatment at 950 +/-20 ℃ for 180-200s, taking out the container and carrying out wall hanging in a rotating way, carrying out heat treatment at 950 +/-20 ℃ for 30-50s after 30-50s, then taking out the container and carrying out wall hanging in a rotating way again;
the container is made of a platinum alloy material;
the container is a platinum alloy crucible.
6. The method for preparing a ferromolybdenum sample according to any one of claims 1 to 4, wherein the step of adding the anhydrous lithium tetraborate, the ferromolybdenum, the sodium nitrate, and the lithium carbonate in the container includes:
and adding the ferromolybdenum, the sodium nitrate, the lithium carbonate and part of anhydrous lithium tetraborate into the container, uniformly stirring, and paving the rest anhydrous lithium tetraborate on the surface.
7. A ferromolybdenum sample prepared by the method for preparing a ferromolybdenum sample according to any one of claims 1 to 6.
8. A method for measuring the component content in a ferromolybdenum alloy is characterized by comprising the following steps:
testing the fluorescence intensity of the ferromolybdenum standard sample by using an X-ray fluorescence spectrometer and drawing a standard curve;
testing the ferromolybdenum sample of claim 7 for fluorescence intensity using an X-ray fluorescence spectrometer; and corresponding the fluorescence intensity to a standard curve to obtain the component content.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010939869.8A CN112051290B (en) | 2020-09-09 | 2020-09-09 | Ferromolybdenum sample, preparation method thereof and method for measuring component content in ferromolybdenum alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010939869.8A CN112051290B (en) | 2020-09-09 | 2020-09-09 | Ferromolybdenum sample, preparation method thereof and method for measuring component content in ferromolybdenum alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112051290A CN112051290A (en) | 2020-12-08 |
| CN112051290B true CN112051290B (en) | 2022-07-29 |
Family
ID=73611494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010939869.8A Active CN112051290B (en) | 2020-09-09 | 2020-09-09 | Ferromolybdenum sample, preparation method thereof and method for measuring component content in ferromolybdenum alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112051290B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114850414B (en) * | 2022-05-20 | 2023-10-31 | 广东韶钢松山股份有限公司 | Preparation method of particle steel molten sheet and method for measuring particle steel components |
| CN115389298A (en) * | 2022-07-29 | 2022-11-25 | 攀钢集团西昌钢钒有限公司 | Method for detecting contents of copper, silicon, phosphorus, tin and antimony in ferromolybdenum |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2971726B2 (en) * | 1994-02-25 | 1999-11-08 | 理学電機工業株式会社 | Low dilution glass bead method |
| CN107543748A (en) * | 2017-08-22 | 2018-01-05 | 抚顺新钢铁有限责任公司 | Fuse piece combined type release method in iron oxide ore x-ray fluorescence analysis |
-
2020
- 2020-09-09 CN CN202010939869.8A patent/CN112051290B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112051290A (en) | 2020-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112051290B (en) | Ferromolybdenum sample, preparation method thereof and method for measuring component content in ferromolybdenum alloy | |
| CN101832891B (en) | Iron alloy fusing sample preparation method for X-ray fluorescence spectrum analysis | |
| CN103149074B (en) | X-ray fluorescence spectra analyzes the MTG YBCO bulk method of molybdenum, manganese, vanadium or ferrochrome sample | |
| CN101592571B (en) | Method for detecting contents of alloying elements in ferrotitanium and ferrovanadium by X-fluorescence fusion method | |
| CN102253030B (en) | Method for determining impurity content in high-titanium slag | |
| CN102607934A (en) | X-ray fluorescence spectroscopy analysis fusion sample preparation method of aluminum, manganese, calcium and iron alloy | |
| CN102426122A (en) | Sample preparation method by fusing medium-carbon ferrochrome and high-carbon ferrochrome | |
| CN101135617B (en) | Vanadium-nitrogen alloy resolution method | |
| CN103149073B (en) | X-ray fluorescence spectra analyzes the MTG YBCO bulk method of ferrosilicon, Si-Ca-Ba, silicomanganese, ferro-aluminum or ferro-titanium sample | |
| CN102156142A (en) | Method for analyzing ferrosilicon alloy components for X-ray fluorescence spectrum analysis | |
| CN102331364A (en) | Melted sampling method for aluminum magnesium calcium iron alloy for X-ray fluorescence spectrum analysis | |
| CN103994994B (en) | The analysis method of silicon in vanadium iron | |
| CN106442073A (en) | Fusion sample preparation method for X-ray fluorescence analysis of element contents of silicon and phosphorus in silicon-manganese ball alloy | |
| CN103884730A (en) | X-ray fluorescence spectrometer analysis method for determining elements of silicon-manganese alloy or ferrosilicon alloy | |
| CN102200511A (en) | Method for determining silicon and manganese contents of silicon-manganese alloy by using X-ray fluorescence melting method | |
| CN114486968B (en) | Method for measuring contents of titanium, silicon, manganese, phosphorus, aluminum and copper in ferrotitanium by using dissolution-melting method sample-X-ray fluorescence spectrometry | |
| CN110646452A (en) | Method for measuring major elements in ferrochrome alloy by X fluorescence fuse link method | |
| CN111060369A (en) | Preparation method of alloy melting sample | |
| CN112461878B (en) | Method for measuring content of ferronickel in carbonyl ferronickel alloy powder | |
| JPS6362695B2 (en) | ||
| CN113155879A (en) | Method for measuring contents of silicon dioxide and calcium fluoride in fluorite | |
| CN113671107A (en) | Method for analyzing content of ferric oxide in serpentine | |
| CN113049619A (en) | Preparation method of XRF analysis iron oxide scrap sample molten glass sheet | |
| CN111239172A (en) | Method for determining phosphorus content in coal | |
| AU2007216909B2 (en) | Copper X-ray flux composition |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |