A method for quantitative analysis of glass powder based on scanning electron microscope energy spectrum analysis

Abstract

The application discloses a glass powder quantitative analysis method based on scanning electron microscope energy spectrum analysis, and belongs to the technical field of glass powder composition analysis. The method is that: surface treatment is performed on sample glass powder, then the sample glass powder is uniformly mixed with to-be-detected sample glass powder, and energy spectrum analysis is performed on the sample glass powder and the to-be-detected sample glass powder under the same microscope field of view. The sample glass powder is surface treated, so that the particle morphology of the sample glass powder is changed to be large or deformed, the sample glass powder can be well distinguished from the to-be-detected sample glass powder under the electron microscope, data of the sample and the to-be-detected sample under the same time and the same machine state can be obtained, after calibration of two groups of data, errors caused by machine and other component interference can be eliminated, and quantitative analysis is realized.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of component analysis of glass powder, and particularly relates to a glass powder quantitative analysis method based on scanning electron microscope energy spectrum analysis. BACKGROUND

[0002] As an important analysis tool for modern research, a scanning electron microscope is mainly used for observation and analysis of micro-area morphology, structure and composition of a sample, has a wide range of use and simple operation. After slight treatment or without treatment, block materials, thin films, powders and even biological macromolecules can be observed. Compared with an electron probe and a transmission electron microscope, energy spectrum analysis of the scanning electron microscope has the advantages of fast analysis speed and low testing cost, but it is generally considered that the accuracy of the analysis result is lower than that of the electron probe and the transmission electron microscope, and only qualitative and semi-quantitative analysis can be achieved.

[0003] Glass powder is a complex system composed of various oxides, and the analysis of its components needs accurate qualitative and quantitative analysis. There are a large number of studies at home and abroad using scanning electron microscope energy spectrum to analyze the components of glass powder, but at present, these studies all use the method of directly testing the sample to be measured or respectively testing the standard sample and the sample to be measured, and the accuracy of the obtained data cannot be evaluated, and the error is large. SUMMARY

[0004] To solve the above technical problems, the application provides a glass powder quantitative analysis method based on scanning electron microscope energy spectrum analysis, and the technical scheme is as follows.

[0005] A glass powder quantitative analysis method based on scanning electron microscope energy spectrum analysis: surface treatment is performed on a standard sample glass powder, and then the standard sample glass powder is uniformly mixed with a sample to be measured glass powder, and energy spectrum analysis is performed under the same microscope field of view.

[0006] The surface treatment includes acid treatment or grinding treatment.

[0007] When the surface treatment is acid treatment, the acid treatment includes the following steps.

[0008] S1: the standard sample glass powder is mixed with acid, ultrasonic dispersion is performed while stirring, washed with deionized water until the ion concentration is lower than 25 muS / cm, dried, and a glass powder with rough surface is obtained. The acid first etches the surface of the glass powder, roughens the surface, and facilitates subsequent coating. After coating, the glass powder is combined more closely with the organic acid.

[0009] Further, the acid is dilute nitric acid, dilute hydrochloric acid or hydrofluoric acid.

[0010] Preferably, the concentration of the acid is 2-10%; preferably, the mass ratio of the standard sample glass powder to the acid is 1:(8-20). Too low an amount of the acid added will result in poor coating effect; too high an amount will result in excessive etching of the glass surface, which will affect the accuracy of the subsequent energy spectrum analysis data.

[0011] S2: uniformly mix the powder of the dried product in S1 with a first dispersant and a coating agent, wash with deionized water, and then dry again to obtain the acid-treated standard sample glass powder.

[0012] Further, the first dispersant comprises a rosin-alcohol solution, a glycol solution or a polyvinylpyrrolidone solution, etc.

[0013] Further, the coating agent is an organic acid; preferably, the coating agent comprises castor oil acid, stearic acid or lauric acid.

[0014] The addition of the first dispersant and the coating agent can make the standard sample glass powder and the to-be-tested sample glass powder have obvious differences in appearance, so as to facilitate the differentiation between the two kinds of particles during scanning electron microscopy and energy spectrum analysis.

[0015] In step S2, the mass ratio of the powder of the dried product, the first dispersant and the coating agent is 1:(10-15):(0.02-0.05). Too low an amount of the first dispersant and the coating agent added will result in no obvious change in appearance, and the standard sample glass powder and the to-be-tested sample glass powder cannot be differentiated during electron microscopy and energy spectrum analysis; however, too high an amount will result in too thick coating, which will affect the energy spectrum data.

[0016] The grinding treatment comprises uniformly mixing the standard sample glass powder with a second dispersant, ball milling, washing with deionized water, drying to obtain flaky standard sample glass powder. The ball milling can deform the standard sample glass powder, changing it from a granular shape to a flaky shape, and can better differentiate the standard sample glass powder from the to-be-tested sample glass powder.

[0017] Further, the second dispersant comprises an organic solvent; preferably, the second dispersant is a glycol solution. More preferably, the concentration of the glycol solution is 8-12%.

[0018] Preferably, the mass ratio of the standard sample glass powder to the second dispersant is 1:(1.5-2.5). Too little second dispersant will result in agglomeration of the glass powder after ball milling, failing to achieve good dispersion effect; too much second dispersant will increase the number of times of washing with deionized water, increasing cost.

[0019] The energy spectrum analysis is performed as follows: uniformly mix the surface-treated standard sample glass powder and the to-be-tested sample glass powder, uniformly sprinkle them on the conductive glue on the sample stage of the scanning electron microscope, observe under 5000 times magnification, and when the two kinds of glass powder with different appearances are clearly displayed in the field of view, simultaneously perform element point scanning analysis of the energy spectrum of the two kinds of samples.

[0020] The present application can distinguish the sample glass powder to be measured from the standard sample glass powder under the electron microscope by surface treatment of the standard sample glass powder to make the particle morphology larger or deformed, and can obtain the data of the standard sample and the sample to be measured under the same time and the same machine state, and can eliminate the error caused by the machine and other components after calibration of the two sets of data, and realize quantitative analysis. BRIEF DESCRIPTION OF DRAWINGS

[0021] In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the drawings needed in the specific embodiments or the prior art description will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0022] Figure 1 The scanning electron microscope image of the standard sample glass powder after surface treatment and the sample glass powder to be measured in Example 1 of the present application;

[0023] Figure 2 The scanning electron microscope image of the standard sample glass powder after surface treatment and the sample glass powder to be measured in Example 4 of the present application. DETAILED DESCRIPTION

[0024] In order to make the purpose, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be described clearly and completely below in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0025] Example 1

[0026] A glass powder quantitative analysis method based on scanning electron microscope energy spectrum analysis, comprising the following steps:

[0027] (1) The standard sample glass powder and the concentrated hydrochloric acid with a concentration of 8.6% are mixed according to the mass ratio of 1:9, and are dispersed by ultrasonic stirring for 20 minutes. The ion concentration is washed to be lower than 25 μS / cm with deionized water, and the surface roughened standard sample glass powder is obtained after drying.

[0028] (2) The standard sample glass powder treated in step (1), the dispersant rosin-alcohol solution and the coating agent castor oil acid are mixed according to the mass ratio of 1:12:0.04, stirred for 1 hour, washed with deionized water, and dried to obtain the standard sample glass powder after surface treatment.

[0029] (3) The sample glass powder treated in step (2) is mixed with the sample glass powder to be measured, and is uniformly scattered on the conductive glue on the scanning electron microscope sample table. The observation is magnified 5000 times. After the two different morphologies of the glass powder are clearly displayed in the field of view, the element point scanning analysis of the energy spectrum is performed on the two samples simultaneously. Figure 1 As shown in the figure, the sample glass powder and the sample glass powder to be measured can be distinguished under the electron microscope, and the difference in appearance is obvious, so that the data can be attributed when the energy spectrum is hit subsequently.

[0030] Example 2

[0031] A glass powder quantitative analysis method based on scanning electron microscope energy spectrum analysis includes the following steps:

[0032] (1) The sample glass powder and 10% concentrated nitric acid are mixed in a mass ratio of 1:15, and are ultrasonically dispersed while stirring. The ion concentration is washed to be lower than 25 μS / cm with deionized water. The surface roughened sample glass powder is obtained after drying.

[0033] (2) The sample glass powder treated in (1), the dispersant ethylene glycol solution and the coating agent stearic acid are mixed in a mass ratio of 1:12:0.04, stirred for 1 hour, washed with deionized water, and dried to obtain the surface treated sample glass powder.

[0034] (3) The sample glass powder treated in (2) is mixed with the sample glass powder to be measured, and is uniformly scattered on the conductive glue on the scanning electron microscope sample table. The observation is magnified 5000 times. After the two different morphologies of the glass powder are clearly displayed in the field of view, the element point scanning analysis of the energy spectrum is performed on the two samples simultaneously.

[0035] Example 3

[0036] A glass powder quantitative analysis method based on scanning electron microscope energy spectrum analysis includes the following steps:

[0037] (1) The sample glass powder and 2% concentrated hydrofluoric acid are mixed in a mass ratio of 1:12, and are ultrasonically dispersed while stirring. The ion concentration is washed to be lower than 25 μS / cm with deionized water. The surface roughened sample glass powder is obtained after drying.

[0038] (2) The sample glass powder treated in (1), the dispersant polyvinylpyrrolidone solution and the coating agent lauric acid are mixed in a mass ratio of 1:12:0.04, stirred for 1 hour, washed with deionized water, and dried to obtain the surface treated sample glass powder.

[0039] (3) The sample glass powder after step (2) is mixed with the sample glass powder to be measured, and is uniformly scattered on the conductive glue on the sample stage of the scanning electron microscope, and is observed at 5000 times magnification. After the two different morphologies of the glass powder are clearly displayed in the field of view, the element point scanning analysis of the energy spectrum is performed on the two samples.

[0040] Example 4

[0041] The embodiment provides a glass powder quantitative analysis method based on scanning electron microscope energy spectrum analysis, and comprises the following steps:

[0042] (1) The sample glass powder and a 10% ethylene glycol solution are mixed according to a mass ratio of 1:2, and are placed in a horizontal ball mill. The high-speed ball milling is performed for 4 hours. The sample glass powder is cleaned with deionized water, and is dried to obtain sample glass powder in the shape of a sheet.

[0043] (2) The sample glass powder after step (1) is mixed with the sample glass powder to be measured, and is uniformly scattered on the conductive glue on the sample stage of the scanning electron microscope, and is observed at 5000 times magnification. After the two different morphologies of the glass powder are clearly displayed in the field of view, the element point scanning analysis of the energy spectrum is performed on the two samples. As shown in FIG. 2, the sample glass powder and the sample glass powder to be measured can be distinguished under the electron microscope, and the difference in the shape is obvious, so that the data can be attributed when the energy spectrum is subsequently hit. Figure 2

[0044] The embodiment of the application is compared with the energy spectrum analysis of the sample glass powder without surface treatment, the non-sample and the sample non-in-situ, as shown in Table 1. In the table, G0 represents the sample glass powder, which is a sample with a known formula; G1 represents the sample glass powder to be measured; the non-sample is comparative example 1, and the sample non-in-situ is comparative example 2.

[0045] Table 1 Energy spectrum analysis results of the sample glass powder of examples 1-4, the sample glass powder without surface treatment, the non-sample and the sample non-in-situ

[0046]

[0047] As can be seen, comparative example 1 is not added with the sample for testing, and the data obtained cannot be calibrated, and only the proportion of each element can be roughly measured, and the accuracy completely depends on the equipment; as compared with the proportion of each element of G0 in comparative example 2 and examples 1-4, the formula still has a large deviation.

[0048] Comparative example 2 is added with the sample, but is not tested in-situ. The sample is separately measured, and the data obtained can be calibrated by comparing the sample, but the data stability and reproducibility are insufficient because the measurement is not performed at the same time under the state of the machine and the sample, and the Δ value is large and not reliable when the data is calibrated.

[0049] ​The data obtained in Examples 1-4 is stable, and it can be seen that although the value of G0 varies in each test, the data of G1 also varies by a corresponding amount according to the amount of variation in G0, which confirms that the effects of factors such as machine current and voltage, sample state, etc. are substantially eliminated, and a stable Δ value is obtained, so that according to the G0 formula, the G0 test value and the G1 test value, three sets of data are calibrated, and the formula of G1 can be accurately calculated.

[0050] It should be noted that the technical features of the above embodiments can be combined in any manner. In order to make the description simple, all possible combinations of the technical features in the above embodiments are not described, however, as long as the combination of the technical features does not exist contradictory, it should be considered as the scope of the description. The above embodiments only express several implementation manners of the present application, and the description is more specific and detailed, but it should not be understood as a limitation on the scope of the patent. It should be pointed out that for those skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are all within the scope of the present application. Therefore, the scope of the patent of the present application should be subject to the appended claims.

Claims

1. A method for quantitative analysis of glass powder based on scanning electron microscope energy spectrum analysis, characterized in that: The standard glass powder is surface treated, then mixed evenly with the glass powder to be tested, and placed under the same microscope field for energy spectrum analysis; The surface treatment includes acid treatment or grinding treatment; The acid treatment comprises the following steps: S1: mixing the standard glass powder with acid, dispersing it ultrasonically while stirring, washing it with deionized water until the ion concentration is lower than 25 μS / cm, and drying it to obtain a glass powder with a rough surface; the concentration of the acid is 2-10%; S2: uniformly mixing the powder of the dried product described in S1 with the first dispersant and the coating agent, washing with deionized water, and then drying again to obtain an acid-treated standard glass powder; the mass ratio of the dried product powder, the first dispersant, and the coating agent is 1:(10-15):(0.02-0.05); The grinding process includes uniformly mixing the standard sample glass powder with a second dispersant, ball milling, washing with deionized water, and drying to obtain a flaky standard sample glass powder.

2. The glass powder quantitative analysis method based on scanning electron microscope energy spectrum analysis according to claim 1, characterized in that: In step S1, the acid is dilute nitric acid, dilute hydrochloric acid or hydrofluoric acid; And / or, the mass ratio of the standard glass powder to the acid is 1:(8-20).

3. The method for quantitative analysis of glass powder based on scanning electron microscope energy spectrum analysis according to claim 1, characterized in that: In step S2, the first dispersant includes a rosin-alcohol solution, an ethylene glycol solution or a polyvinyl pyrrolidone solution.

4. The method for quantitative analysis of glass powder based on scanning electron microscope energy spectrum analysis according to claim 1, characterized in that: In step S2, the coating agent is an organic acid.

5. The method for quantitative analysis of glass powder based on scanning electron microscope energy spectrum analysis according to claim 4, characterized in that: The coating agent includes ricinoleic acid, stearic acid or lauric acid.

6. The method for quantitative analysis of glass powder based on scanning electron microscope energy spectrum analysis according to claim 1, characterized in that: The second dispersant includes an organic solvent.

7. The method for quantitative analysis of glass powder based on scanning electron microscope energy spectrum analysis according to claim 1, characterized in that: The second dispersant is an ethylene glycol solution; the concentration of the ethylene glycol solution is 8-12%; And / or, the mass ratio of the standard glass powder to the second dispersant is 1:(1.5-2.5).

8. The method for quantitative analysis of glass powder based on scanning electron microscope energy spectrum analysis according to claim 1, characterized in that: The energy spectrum analysis is to mix the surface-treated standard glass powder and the sample glass powder evenly, sprinkle them evenly on the conductive glue on the scanning electron microscope sample stage, and observe them at a magnification of 5000 times. After two glass powders with different morphologies are clearly displayed in the field of view, the two samples are simultaneously subjected to energy spectrum element point scanning analysis.

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