阅读说明：本技术 一种低含量α-石英标准样品的制备方法及应用 (Preparation method and application of low-content alpha-quartz standard sample ) 是由 任国涛 李婷婷 刘萍 张利新 郑德胜 于 2018-11-29 设计创作，主要内容包括：一种低含量α-石英标准样品的制备方法。其制备步骤为：选取与被测物质相匹配的硅质耐火材料基质物质A,其不含α-石英含量,以及已知石英含量的标准物质B；将基质物质A和标准物质B按比例混磨均匀使其α-石英含量达到目标值,实际测试定值后即为低含量α-石英的标准样品。本发明改进了目前硅砖残余石英含量的测试方法仅采用高含量(>96%)石英标准物质一点比对的方法；可以按照化学分析的基本方法采用合适浓度含量的系列标准物质,从而建立线性的X射线衍射强度和α-石英含量的函数关系,定量测试并计算出被测样品中残余石英相的含量,不确定度在可接受范围。方法更加科学合理,并易于推广应用。(A preparation method of a low-content alpha-quartz standard sample. The preparation method comprises the following steps: selecting a siliceous refractory material matrix substance A matched with a measured substance, wherein the siliceous refractory material matrix substance A does not contain alpha-quartz content and a standard substance B with known quartz content; and uniformly mixing and grinding the matrix substance A and the standard substance B in proportion to enable the alpha-quartz content to reach a target value, and obtaining a standard sample with low alpha-quartz content after actual test and fixed value. The invention improves the method that the existing method for testing the residual quartz content of the silica brick only adopts a one-point comparison method of high-content (> 96%) quartz standard substances; the method can adopt a series of standard substances with proper concentration content according to a basic method of chemical analysis, thereby establishing a linear function relation between the X-ray diffraction intensity and the alpha-quartz content, quantitatively testing and calculating the content of residual quartz phase in a tested sample, and the uncertainty is in an acceptable range. The method is more scientific and reasonable and is easy to popularize and apply.)

1. A preparation method of a low-content alpha-quartz standard sample is characterized by comprising the following steps: the preparation method comprises the following steps: selecting a silica refractory material consistent with a matrix of a measured substance as a matrix substance A, wherein the alpha-quartz content of the matrix substance A is zero, and selecting a standard substance B with known quartz content; and uniformly mixing and grinding the matrix substance A and the standard substance B in proportion to enable the alpha-quartz content to reach a target value, and obtaining a standard sample with low alpha-quartz content after the value is fixed.

2. The method for preparing a low α -quartz standard sample according to claim 1, wherein: the adding mass of the standard substance B is X, and the calculation mode is as follows:

X × quartz content of the standard substance B/(mass + X of the base substance a) = α -quartz content target value.

3. The method for preparing a low α -quartz standard sample according to claim 1, wherein: the particle size distribution range of the matrix material A is consistent with that of the standard material B.

4. The method for preparing a low α -quartz standard sample according to claim 3, wherein: the grinding process of the matrix substance A comprises the following steps: selecting a silica brick sample with zero residual alpha-quartz content, removing the skin, coarsely crushing in a crushing machine, fully grinding in a tungsten carbide vibration grinding machine, detecting the granularity after grinding, comparing with the granularity of a standard substance B, adding a fully ground substrate substance A, pure water and a zirconium grinding ball into the grinding machine when the ground granularity is larger than that of the standard substance B, carrying out wet grinding, testing the granularity distribution of the ground edge in a wet state until the granularity and the distribution are consistent with the granularity range of the standard substance B, and then evaporating, drying, grinding and bottling for later use.

5. The method for preparing a low α -quartz standard sample according to claim 4, wherein: the particle size range of the standard substance B is 10 μm or less.

6. Use of a low-content α -quartz standard sample prepared using the preparation method of claim 1 in a quantitative test method for residual α -quartz phase content in silica refractory.

7. Use of a low α -quartz standard sample according to claim 6 for testing the residual quartz phase content of a silica refractory, characterized in that: the detection method adopts a plurality of alpha-quartz standard samples in a linear relation to carry out X-ray diffraction quantitative analysis on the residual quartz content in the silica brick refractory material.

Technical Field

The invention relates to the technical field of refractory materials, in particular to a preparation method and application of a low-content alpha-quartz standard sample.

Background

At present, the quantitative detection method of the residual quartz content of the silica refractory material in China is YB/T172-2000, which is based on an alpha-quartz standard sample with the alpha-quartz content of more than 98 percent, but how the standard sample is obtained by the method is not specified. The popular method is to purchase a commercial quartz standard sample or prepare the sample by the user, and the content of the commercial quartz standard sample such as American SRM quartz standard sample is 96-97 percent, and the content range of 98 percent and above is difficult to achieve. The conventional X-ray diffraction method can only be a qualitative or semi-quantitative method, because standard samples without proper content can not be quantitatively measured like chemical component analysis, and the conventional detection of the residual quartz content in the silicon refractory material is generally low (< 10%), so that the measured content and the used standard samples present larger concentration deviation and bring larger uncertainty. Therefore, it is important to accurately and quantitatively detect the content of the residual quartz and select or prepare a standard quartz sample with the content consistent with that of the detected sample.

Disclosure of Invention

In order to overcome the defects in the background art, the first technical problem to be solved by the invention is to provide a preparation method of a low-content alpha-quartz standard sample, and the alpha-quartz standard sample with the content consistent with that of a sample to be detected is prepared. The second technical problem to be solved by the invention is that the low-content alpha-quartz series standard sample prepared by the method can be used for more accurately and quantitatively detecting the residual quartz content in the silica brick by adopting an X-ray diffraction detection method. The invention aims to find out a preparation method of a low-content alpha-quartz standard sample so as to prepare a proper standard sample, so that the quantitative analysis of the residual quartz phase in the silica brick detected by X-ray powder diffraction is more reasonable, scientific and easy to operate.

In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of a low-content alpha-quartz standard sample comprises the following preparation steps: selecting a silica refractory material consistent with a matrix of a measured substance as a matrix substance A, wherein the alpha-quartz content of the matrix substance A is zero, and selecting a standard substance B with known quartz content; and uniformly mixing and grinding the matrix substance A and the standard substance B in proportion to enable the alpha-quartz content to reach a target value, and obtaining a standard sample with low alpha-quartz content after the value is fixed.

In order to further improve the technical scheme, the adding mass of the standard substance B is X, and the calculation mode is as follows:

The quartz content of X × standard substance B/(mass + X of base substance a) ═ a-quartz content target value.

In order to further improve the technical scheme, the particle size distribution range of the matrix material A and the particle size distribution range of the standard material B are consistent.

In order to further improve the technical scheme, the grinding process of the matrix substance A comprises the following steps: selecting a silica brick sample with zero residual alpha-quartz content, removing the skin, coarsely crushing in a crushing machine, fully grinding in a tungsten carbide vibration grinding machine, detecting the granularity after grinding, comparing with the granularity of a standard substance B, further performing wet grinding when the ground granularity is larger than the granularity of the standard substance B, adding a substrate substance A, pure water and zirconium grinding balls which are fully ground in the grinding machine, performing wet grinding, testing the granularity distribution of the ground edges in a wet state until the granularity and the distribution are consistent with the granularity range of the standard substance B, and then evaporating, drying, grinding and bottling for later use.

In order to further improve the technical scheme, the invention requires that the particle size range of the standard substance B is less than 10 μm.

The application of the low-content alpha-quartz standard sample prepared by the preparation method in a quantitative test method for testing the residual alpha-quartz phase content in the silica refractory material is disclosed.

In order to further improve the technical scheme, the invention relates to a detection method for carrying out X-ray diffraction quantitative analysis on the content of residual quartz in the silica brick refractory material by adopting a plurality of alpha-quartz standard samples in a linear relation.

Compared with the prior art, the invention has the beneficial effects that: the method improves the method for testing the residual quartz content of the silica brick at present and only adopts a one-point comparison method of high-content quartz; the method can adopt a series of standard substances with proper concentration and content according to a basic method of chemical analysis, thereby establishing a linear functional relation between the X-ray diffraction intensity and the content, quantitatively testing and calculating the quantity value of the residual quartz in the tested sample, and ensuring that the uncertainty is in an acceptable range, thereby being more scientific and reasonable and easy to popularize and apply.

Drawings

FIG. 1 is an XRD diffraction pattern of the quartz content of matrix material A in the specific example.

FIG. 2 is a particle size composition diagram of the matrix material A in step S1 in the specific example.

FIG. 3 is a composition diagram of the grain size of the standard substance B in the specific example.

FIG. 4 is a particle size composition diagram of the matrix material A in step S4 in the specific example.

Fig. 5 is an XRD diffraction pattern of a standard sample with an alpha-quartz content target value of 3.0%.

Detailed Description

The present invention will be explained in detail by the following examples, which are intended to protect all technical improvements involved within the scope of the present invention.

Firstly, preparing a standard sample preparation example with an alpha-quartz content target value of 3.0 percent:

S1, a silica refractory matrix material A free of residual silica content is prepared. Selecting a silica brick sample used for many years, wherein the XRD diffraction pattern of the quartz content of the silica brick sample is shown in figure 1, removing the skin, firstly coarsely crushing in a crushing machine, then fully grinding in a tungsten carbide vibration grinding machine, and detecting the granularity by a laser granularity analyzer to form a composition shown in figure 2. From FIG. 2, it can be seen that the particle size ranges are D10:2.187 μm; d50:6.847 μm; d90:25.788 μm.

S2, selecting a standard substance B with known quartz content, wherein the standard substance B is a standard substance B of a commercial SRM, the quartz content is 96.56% + -0.40%, the particle size composition is shown in figure 3, and both the particle size and the distribution are less than 10 μm.

S3, comparing the particle sizes of the matrix substance A and the standard substance B, D10:2.187 μm; d50:6.847 μm; the D90:25.788 μm and the standard substance B do not meet the requirement of less than 10 μm in particle size range and distribution, and the grinding mode needs to be further replaced to grind to the required particle size.

S4, selecting a high-efficiency mixing and grinding machine, adding a certain amount of the matrix material A in the step S1, adding pure water and grinding balls made of materials in a certain proportion, selecting a proper grinding tank, carrying out wet grinding, testing the particle size distribution of the ground edges in a wet state while grinding the edges, grinding for a plurality of times until the particle size and the distribution meet the target requirements of less than 10 mu m, wherein the particle size and the distribution are shown in figure 4, and then evaporating, drying, grinding and bottling for later use.

S5, calculating the mass ratio of the matrix substance A to the standard substance B: firstly, weighing the standard substance B in the step S2 as a standard sample with known quartz content, and performing wet mixing with the matrix substance A in the step S1, wherein the total mass of the matrix substance A weighed is 10.0000g, x: known Standard sample B weight (g)

Calculating according to a calculation formula: x × 96.56%/(10.0000 + X) ═ 3.0%

X＝0.3206g

S6, preparing an alpha-quartz standard sample with an alpha-quartz content target value of 3.0 percent: and (4) accurately weighing the matrix substance A and the standard substance B according to the mass of the matrix substance A and the standard substance B calculated in the step S5, fully mixing the matrix substance A and the standard substance B in a wet state, and finally evaporating, drying and bottling the mixture to obtain the finished product of the low-content alpha-quartz standard sample.

Secondly, performing laboratory fixed value detection verification on the prepared low-content alpha-quartz standard sample:

taking a plurality of grams of the prepared standard sample to be detected, drying and pressing the sample into a powder sample, respectively and independently preparing and testing the sample for 5 times on a Bruker D8X ray diffractometer according to a conventional detection method, and obtaining the following residual quartz content results:

number of times	№1	№2	№3	№4	№5
						residual quartz content%	2.95	2.84	2.89	2.83	2.88

The XRD diffraction pattern of the prepared standard sample having the target value of α -quartz content of 3.0% is shown in fig. 5.

(fifth).

2.88%. approximately.2.9% C.average residual Quartz%

S0.048 CV 1.7% S, test standard deviation; CV: coefficient of variation of test

And calculating uncertainty: u (x) ═ R/C0.06% (R test tolerance 0.15; C2.33; N5 test times)

The extended uncertainty (K ═ 2, 95%) U ═ 2U (x) ≈ 0.2% with 0.12%. U: expanding uncertainty; u (x) standard uncertainty.

Third, conclusion

The assigned value of the alpha-quartz standard sample (internal control) is 2.9 percent, and the uncertainty is 0.2 percent. (K2, 95% confidence).