CN114166879A - Method for manufacturing glass beads for fluorescent X-ray analysis device - Google Patents
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- 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
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Abstract
The present invention provides a method for manufacturing glass beads for a fluorescent X-ray analysis device. In the present invention, a lithium borate flux is used to produce glass beads with little deterioration over time. In the method for producing glass beads for a fluorescent X-ray analyzer, a material to be measured is dissolved in a lithium borate-based flux together with an oxide of an alkaline earth metal to produce glass beads.
Description
Technical Field
The present invention relates to a method for producing glass beads for a fluorescent X-ray analysis apparatus.
Background
Conventionally, a fluorescent X-ray analysis method has been widely used which performs qualitative and quantitative analysis of an element contained in a sample by analyzing a fluorescent X-ray generated from the sample irradiated with a primary X-ray. In the fluorescent X-ray analysis, the analysis result varies depending on the chemical combination of the sample (so-called inhomogeneous effects such as mineral effect and particle size effect). In order to suppress variation in the analysis results, a glass bead method is used (see patent document 1 below). Glass beads that change stably with time are also used as drift correction samples for fluorescent X-ray analyzers (see patent document 2 below).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 9-61320
Patent document 2: japanese patent laid-open publication No. 2010-204087
Disclosure of Invention
Problems to be solved by the invention
The glass beads are produced by dissolving a material containing an element to be analyzed in a flux and heating the resultant solution. Here, the energy of the fluorescent X-ray of the element to be analyzed may be the same as or similar to the energy of the fluorescent X-ray of the element contained in the flux. In this case, the fluorescent X-ray due to the element contained in the flux may hinder accurate analysis. Therefore, a lithium borate flux composed of an element that is not an analysis target of the fluorescent X-ray analysis method may be used. However, glass beads produced using a lithium borate flux are susceptible to changes over time because they deliquesce over time. Therefore, in the case of a calibration sample, an inspection sample, and the like of an apparatus which is particularly required to be stable for a long period of time, glass beads in which glass beads are covered with a polymer film or glass beads in which a coating layer such as DLC (diamond like carbon) is applied to the surface may be used as in patent document 1.
The present invention has been made in view of the above problems, and an object thereof is to provide a method for producing glass beads with little deterioration with time using a lithium borate flux, and a method for calibrating a fluorescent X-ray analyzer using the glass beads.
Means for solving the problems
The method for producing glass beads for a fluorescent X-ray analyzer according to claim 1 of the present invention is characterized in that a material to be measured is dissolved in a lithium borate-based flux together with an oxide of an alkaline earth metal.
The method for producing glass beads according to claim 2 of the present invention is characterized in that the alkaline earth metal is magnesium or calcium or both of them.
The method for producing glass beads according to claim 3 of the present invention is characterized in that the alkaline earth metal is magnesium, and the content of the oxide of the alkaline earth metal is 5% by mass or more.
The method for producing glass beads according to claim 4 of the present invention is characterized in that the alkaline earth metal is magnesium, and the content of the oxide of the alkaline earth metal is 12% by mass or less.
The method for producing glass beads according to claim 5 of the present invention is characterized in that the alkaline earth metal is calcium, and the content of the oxide of the alkaline earth metal is 10% by mass or more.
The method for producing glass beads according to claim 6 of the present invention is characterized in that the alkaline earth metal is calcium, and the content of the oxide of the alkaline earth metal is 35% by mass or less.
The calibration sample for a fluorescent X-ray analysis device according to claim 7 of the present invention is produced by the method according to any one of claims 1 to 6.
The method for calibrating a fluorescent X-ray analyzer according to claim 8 of the present invention is characterized in that the fluorescent X-ray analyzer is calibrated using a calibration sample for a fluorescent X-ray analyzer described in claim 7.
Effects of the invention
According to the inventions described in claims 1 to 8, glass beads with little deterioration with time can be produced using a lithium borate flux, and a fluorescent X-ray analyzer can be calibrated using the glass beads.
Drawings
Fig. 1 is a flowchart showing a method for producing glass beads and an analysis method according to an embodiment of the present invention.
Fig. 2 is an image of the surfaces of sample B and the comparative sample.
Fig. 3 is an image of the surfaces of sample B and the comparative sample.
FIG. 4 is a flow chart illustrating a method for calibrating a fluorescent X-ray analysis device.
Detailed Description
Preferred embodiments (hereinafter, referred to as embodiments) for carrying out the present invention will be described below with reference to the accompanying drawings. FIG. 1 is a flowchart showing a method for producing glass beads and a method for analyzing the same.
First, the material to be measured, the oxide of the alkaline earth metal, and the lithium borate flux are weighed (S102). Specifically, for example, the material of the measurement object contains chlorine (Cl) and sulfur (S), which are elements of the analysis object. Lithium borate flux such as lithium tetraborate (Li)2B4O7). The alkaline earth metal is magnesium (Mg), calcium (Ca), strontium (Sr), or barium (Ba), and the oxide of the alkaline earth metal is an oxide of these elements. Hereinafter, a case where the oxide of the alkaline earth metal is magnesium oxide (MgO) and a case where the oxide of the alkaline earth metal is calcium oxide (CaO) will be described. In step S102, the mass of the material containing chlorine and sulfur, lithium tetraborate, magnesium oxide, and/or calcium oxide is measured.
Here, the content of magnesium oxide with respect to the total mass of the material to be measured, the oxide of the alkaline earth metal, and the lithium borate flux is 5% by mass or more, preferably 10% by mass or more. The greater the content of magnesium oxide relative to the total mass, the more the durability of the formed glass beads to deliquescence can be improved.
The content of magnesium oxide is 12% by mass or less with respect to the entire mass. If the content of magnesium oxide is too large relative to the entire mass, undissolved magnesium oxide is generated in the step of performing dissolution described later. The dissolved magnesium oxide and the undissolved magnesium oxide are different in state and cause a non-uniform effect, etc., and the analysis accuracy of the fluorescent X-ray analysis is lowered. The content of magnesium oxide with respect to the entire mass is measured so as to be 12% by mass or less, thereby preventing the generation of undissolved magnesium oxide.
Similarly, when the oxide of the alkaline earth metal is calcium oxide, the content of calcium oxide with respect to the entire mass is 10% by mass or more, preferably 25% by mass or more. Further, the content of calcium oxide with respect to the entire mass is preferably 35% by mass or less.
Subsequently, the weighed materials to be measured, the oxide of the alkaline earth metal, and the lithium borate flux are mixed, heated, and dissolved (S104). Specifically, for example, a weighed material to be measured, magnesium oxide and/or calcium oxide, and lithium tetraborate are mixed and placed in a platinum crucible and mixed. Further, a release agent may be appropriately mixed depending on the material to be measured. Then, the platinum crucible was placed on a heating furnace such as an electric furnace, and the platinum crucible was heated at 1000 ℃ for 10 minutes.
Next, the platinum crucible is cooled (S106). Specifically, for example, after melting, the platinum crucible is taken out from the heating furnace and cooled to normal temperature for about 30 minutes. Thereby completing the glass beads.
Subsequently, measurement and analysis are performed (S108). Specifically, the glass beads taken out of the platinum crucible were disposed in a fluorescent X-ray analysis apparatus. The glass beads are irradiated with primary X-rays inside the fluorescent X-ray analysis device, and the material to be measured emits unique fluorescent X-rays. The fluorescent X-ray analyzer measures the intensity and energy of the fluorescent X-ray. The fluorescent X-ray analyzer analyzes the material to be measured by a known technique such as a calibration curve method or an FP (basic Parameter) method based on the intensity and energy of the fluorescent X-ray.
Next, the effects of the present invention will be described based on the experimental results. First, in order to verify the effect of the present invention, the inventors produced a plurality of samples a, B, and C in accordance with the steps S102 to S106 shown in fig. 1. Further, the inventors prepared a comparative sample containing no oxide of an alkaline earth metal by a conventional technique. Here, sample a is a sample in which the mass ratio of magnesium oxide to the entire mass is 8%. Sample B was a sample in which the mass ratio of magnesium oxide to the entire mass was 11%. Sample C was a sample in which the mass ratio of calcium oxide to the entire mass was 11%. The materials to be measured were chlorine and sulfur, and the materials to be measured and lithium tetraborate contained in sample a, sample B, sample C and the comparative sample were all the same in mass.
After the glass beads were produced, the inventors allowed part of each of sample a, sample B, sample C and the comparative sample to pass for 4 hours or 40 hours in a humidified environment or an unhumidified environment. Then, the fluorescence X-ray intensities of the Cl-Ka line, S-Ka line, Mg-Ka line and Ca-Ka line were measured for each sample in accordance with the procedure of S108 shown in FIG. 1. In addition, it is known that, in general, even if the time elapsed after producing glass beads under the same conditions is the same, the deliquescence rate is high in one of the glass beads that has elapsed in a high humidity environment.
Table 1 shows the measurement results for the comparative samples. Table 1 shows the strength ratio measured immediately after the production of the glass beads and the strength ratio measured after 4 hours and 40 hours have elapsed in a humidified environment after the production of the glass beads. In table 1, "intensity ratio with respect to elapsed time 0 h" is a ratio of intensity in the case of elapsed time of 4 hours or 40 hours to intensity in the case of elapsed time of 0 hour (that is, immediately after the glass beads are produced) under the same humidification conditions. In table 1, "intensity ratio of humidified state to non-humidified state" is a ratio of intensity in the humidified state to intensity in the non-humidified state under the same elapsed time condition. Further, since the comparative sample contained no magnesium oxide or calcium oxide, the Mg-Ka line and Ca-Ka line were not detected.
[ TABLE 1 ]
As shown in Table 1, the longer the elapsed time, the smaller the intensity of the Cl-K.alpha.line and the S-K.alpha.line. In particular, the strength after 40 hours had passed was about 30% of the strength immediately after the production of the glass beads. That is, it is known that the comparative sample is degraded with time, causing deliquescence of the glass beads, and the accuracy of the fluorescent X-ray analysis is degraded with time.
Table 2 shows the measurement results for sample a. Table 2 shows the intensity ratio measured immediately after the end of S106 and the intensity ratios measured after 4 hours and 40 hours have elapsed in the non-humidified environment and the humidified environment, respectively, after S106.
[ TABLE 2 ]
As shown in table 2, the longer the elapsed time, the smaller the intensity of the CI-K α line and the S-K α line, but the smaller the intensity reduction degree compared to table 1. For example, the strength after 40 hours has elapsed is about 80% of the strength immediately after the production of the glass beads. Therefore, it is found that the magnesium oxide mixed in the sample a reduces the running speed of deliquescence of the glass beads due to aging deterioration, and reduces the decrease in measurement accuracy due to aging variation.
Table 3 shows the measurement results for sample B. Table 3 shows the intensity ratio measured immediately after the end of S106 and the intensity ratios measured after 4 hours and 40 hours have elapsed in the non-humidified environment and the humidified environment, respectively, after S106.
[ TABLE 3 ]
As shown in Table 3, the intensity of the Cl-K.alpha.line and the S-K.alpha.line became slightly smaller as the elapsed time became longer, but the degree of decrease in intensity was smaller as compared with that of Table 2. For example, the strength after 40 hours has elapsed is about 95% of the strength immediately after the production of the glass beads. Therefore, it is found that by increasing the mass ratio of magnesium oxide mixed in sample a, the speed of the glass beads advancing due to deliquescence is reduced, and the reduction in measurement accuracy due to the change with time can be further reduced.
Table 4 shows the measurement results for sample C. Table 4 shows the intensity ratio measured immediately after the end of S106 and the intensity ratios measured after 4 hours and 40 hours have elapsed in the non-humidified environment and the humidified environment, respectively, after S106.
[ TABLE 4 ]
As shown in table 4, the strength after the lapse of 40 hours was about 90% to 95% of the strength immediately after the production of the glass beads. Therefore, it is found that even if the alkaline earth oxide mixed in the material to be measured is calcium oxide, the running speed of the deliquescence of the glass beads due to the temporal degradation is reduced, and the degradation of the measurement accuracy due to the temporal change can be reduced.
Fig. 2 and 3 are images of the surfaces of sample B and the comparative sample. Specifically, the left side of each of fig. 2 (a) to 3 (B) is an image of sample B, and the right side is an image of a contrast sample. Fig. 2 (a) shows an image captured immediately after the glass beads are produced. Fig. 2 (b) is an image taken after 4 hours in a humidified environment after the glass beads were produced. Fig. 3 (a) is an image obtained by measuring the glass beads after 4 hours in a humidified environment, and then taking the image after the measurement. Fig. 3 (b) shows an image obtained by measuring the glass beads after 40 hours in a humidified environment, and then taking the image after the measurement.
As shown in fig. 2 (a), no deliquescence was observed on the surfaces of sample B and the comparative sample immediately after the production of the glass beads. As shown in fig. 2 (B), even after 4 hours had elapsed in a humidified environment after the production of the glass beads, no deliquescence was observed on the surfaces of the sample B and the comparative sample before the measurement. However, as shown in fig. 3 (a), it is known that when a comparative sample after 4 hours has passed after the production of glass beads is measured (that is, when the surface of the comparative sample is irradiated with X-rays once), the surface of the comparative sample is deliquesced. On the other hand, even when sample B was measured after 4 hours after the production of glass beads, no deliquescence was observed on the surface of sample B.
As shown in fig. 3 (b), when the comparative sample after 40 hours had passed after the production of glass beads was measured, the surface of the comparative sample was deliquesced in a larger area than that of fig. 3 (a). On the other hand, even when sample B after 40 hours had passed after the production of glass beads was measured, a part of the surface of sample B was deliquesced, but the degree of progress of deliquescence was slight as compared with the comparative sample.
As described above, when the glass beads are produced using the lithium borate flux, if the alkaline earth metal oxide is not mixed with the material to be measured as in the conventional case, the deliquescence progresses within 40 hours, and accurate analysis cannot be performed. However, by mixing an oxide of an alkaline earth metal, the deliquescence proceeding speed can be slowed down. Thus, even if a situation occurs in which measurement cannot be performed immediately after the production of the glass beads, measurement can be performed at a later time, and therefore, the convenience of the measuring staff is improved.
In particular, when a characteristic change (so-called device drift) of the fluorescent X-ray analyzer occurs, a calibration sample such as a test sample for testing whether or not the characteristic change occurs or a drift correction sample for correcting the characteristic change is suitable for glass beads with little deterioration with time. The method for producing glass beads according to the present invention is particularly suitable for producing the test sample and the calibration sample.
Fig. 4 is a flowchart showing a method of calibrating a fluorescent X-ray analyzer using the test sample and the calibration sample prepared by the above-described method. First, measurement is performed using a test sample (S402). Specifically, the test sample is irradiated with X-rays once, and the test sample is analyzed by, for example, a calibration curve method or an FP method based on the intensity and energy of the fluorescent X-rays. Here, the content of each element contained in the test sample is known. Therefore, based on the known content of each element and the analysis result, it can be judged whether or not the device drift is generated.
If the device drift does not occur (no in S404), the device correction is not necessary, and the present flow ends. On the other hand, if the device drift occurs (yes in S404), the process proceeds to S406.
In S406, before the drift correction is performed a predetermined number of times (no in S406), measurement is performed using a calibration sample (S408). Specifically, the calibration sample is irradiated with X-rays once, and the intensity of the fluorescent X-rays is measured for each energy. Then, the drift is corrected based on the measurement result (S410). Specifically, for example, the value of the drift correction coefficient is changed using the fluorescent X-ray intensity obtained by measuring the calibration sample. When the correction of the drift is completed, the process returns to S402.
In S406, when the drift is corrected a predetermined number of times (yes in S406), the calibration curve is reproduced when the calibration curve method is used, and the device sensitivity curve is reproduced when the FP method is used (S412). In S412, even if drift correction is performed, the characteristics of the device change to such an extent that accurate analysis cannot be performed using the conventional calibration curve or device sensitivity curve. Thus, a new calibration curve or device sensitivity curve is created. The formation of a calibration curve or device sensitivity curve is performed using known techniques.
The predetermined number of times in S406 is set within a device correctable range by drift correction, for example, 2 times. The calibration of the fluorescent X-ray analysis apparatus is completed by the above steps.
The present invention is not limited to the above-described embodiments, and various modifications are possible. The above-exemplified magnesium oxide and calcium oxide are examples of the oxide of the alkaline earth metal, and the oxide of the alkaline earth metal mixed in the material to be measured may be strontium oxide or barium oxide. Further, although the case of using lithium tetraborate as the lithium borate-based flux has been described, the lithium borate-based flux may be lithium metaborate (LiBO)2) Or a mixture of lithium tetraborate and lithium metaborate.
The mass ratio of the oxide of the alkaline earth metal to the entire mass is not limited to the above and may be set as appropriate, but it is preferable that no unmelted substance is generated. Table 5 shows the results of an experiment conducted to determine whether or not an unmelted object was formed, based on the mass ratio of the alkaline earth metal oxide to the entire mass. In Table 5, "good" means that no unmelted object was generated, and "poor" means that unmelted object was generated. When an unmelted object is generated, it is preferable that the unmelted object is not generated because the analysis accuracy of the fluorescent X-ray analysis is lowered by the inhomogeneous effect or the like.
[ TABLE 5 ]
| Mass ratio (%) | 5 | 8 | 11 | 12 | 13 | 18 | 25 | 30 | 35 | 36 |
| MgO | ○ | ○ | ○ | ○ | × | × | × | × | × | × |
| Cao | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × |
As shown in table 5, when the oxide of the alkaline earth metal is magnesium oxide, the content of magnesium oxide with respect to the entire mass is preferably 12% by mass or less. When the oxide of the alkaline earth metal is calcium oxide, the content of calcium oxide with respect to the entire mass is preferably 35% by mass or less.
Claims (8)
1. A method for producing glass beads for a fluorescent X-ray analyzer, characterized in that a material to be measured is dissolved in a lithium borate-based flux together with an oxide of an alkaline earth metal.
2. The method of manufacturing a glass bead for a fluorescent X-ray analysis device according to claim 1,
the alkaline earth metal is magnesium or calcium or both.
3. The method of manufacturing a glass bead for a fluorescent X-ray analysis device according to claim 2,
the alkaline earth metal is magnesium, and the alkaline earth metal is magnesium,
the content of the alkaline earth metal oxide is 5% by mass or more.
4. The method of producing a glass bead for a fluorescent X-ray analysis device according to claim 2 or 3,
the alkaline earth metal is magnesium, and the alkaline earth metal is magnesium,
the content of the oxide of the alkaline earth metal is 12% by mass or less.
5. The method of manufacturing a glass bead for a fluorescent X-ray analysis device according to claim 2,
the alkaline earth metal is calcium, and the alkaline earth metal is calcium,
the content of the oxide of the alkaline earth metal is 10% by mass or more.
6. The method of producing a glass bead for a fluorescent X-ray analysis device according to claim 2 or 3,
the alkaline earth metal is calcium, and the alkaline earth metal is calcium,
the content of the oxide of the alkaline earth metal is 35% by mass or less.
7. A calibration sample for a fluorescent X-ray analyzer produced by the method according to claim 1.
8. A method of calibrating a fluorescent X-ray analyzer using the calibration sample according to claim 7.
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| JP2022047401A (en) | 2022-03-24 |
| CN114166879B (en) | 2023-09-26 |
| JP7076835B2 (en) | 2022-05-30 |
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