A prediction method for the anti-leaching performance of high-energy borosilicate glass and its application

Abstract

The present invention proposes a method and application for predicting the leaching resistance of high-radiation borosilicate glass. The method comprises the following steps: S1, obtaining the oxide composition of the high-radiation borosilicate glass; S2, predicting the mass loss per unit surface area of ​​the high-radiation borosilicate glass in a static leaching test according to the formula #imgabs0#; where: L is the mass loss per unit surface area of ​​the high-radiation borosilicate glass, #imgabs1# i is the influence coefficient of the ith oxide component in the high-radiation borosilicate glass on the anti-leaching performance, #imgabs2# ij The first i and j The interaction between the oxide components and the influence coefficient of anti-leaching performance, #imgabs3# i With #imgabs4# j The first i Species and j The present invention can quickly and accurately predict the mass loss per unit surface area of ​​high-radiation borosilicate glass under static leaching test conditions, greatly improving the efficiency of optimizing the composition ratio of high-radiation glass, shortening the research cycle and reducing costs.

Description

Technical Field

[0001] The present invention belongs to the technical field of high-level radioactive nuclear waste solidification treatment, and in particular relates to a method for predicting the anti-leaching performance of high-level borosilicate glass and its application. Background Art

[0002] Vitrification involves calcining and fusing high-level radioactive liquid waste (HLW) with a glass matrix to form a stable glass solid. This technology is currently a widely accepted and developed method for treating HLW worldwide. By immobilizing radionuclides within a flexible glass network, it achieves atomic-scale solidification of various toxic elements, preventing their migration into the external environment. Borosilicate glass has become the preferred substrate for vitrification due to its excellent chemical stability and low melting temperature. HLW, after being solidified in borosilicate glass, is typically disposed of deep underground, isolating it from the biosphere for tens to millions of years. However, groundwater inevitably intrudes into containment facilities, slowly corroding the engineering barriers and ultimately contacting the HLW vitrified structure. Upon contact with groundwater, the HLW vitrified structure begins to dissolve and release radionuclides into the near-field environment, posing a significant threat to the ecological environment. Therefore, the vitrified structure must possess excellent chemical durability to minimize the migration of radionuclides.

[0003] Therefore, the chemical durability of the solid body is a key performance indicator that is focused on during the development stage of laboratory glass formulations. At present, a variety of methods such as dynamic leaching test (ASTM C1662) and static leaching test (ASTM C1285-02, ASTMC1220-2017) are commonly used internationally to quickly evaluate the chemical durability of glass solid bodies. my country's nuclear industry (EJ 1186-2005) mainly refers to the static leaching test standard as the evaluation method for the chemical durability of high-radiation borosilicate glass solid bodies. This method uses deionized water as the leaching liquid, and maintains the ratio of the surface area of ​​the glass solid body sample to the volume of the immersion liquid at 10.0 m -1 ±0.5 m -1 The chemical durability of the glass solid was evaluated by static immersion in a temperature environment of 90°C ± 1°C for 28 days, based on the mass loss per unit surface area of ​​the sample. Currently, there is a lack of a predictive method for quickly and accurately evaluating the anti-leaching performance of high-radiation borosilicate glass solids in my country.

[0004] One of the purposes of optimizing the formula composition of high-radiation glass is to maximize the anti-leaching performance of the glass solid. Due to the lack of a predictive method suitable for quickly and accurately evaluating the anti-leaching performance of high-radiation borosilicate glass solids in my country, most of the current methods are based on literature and experience, qualitatively increasing the chemical composition of silicon oxide and aluminum oxide to enhance the durability of the glass, and then preparing glass solid samples through high-temperature melting. Then, anti-leaching performance tests lasting more than a month are carried out to determine further formula composition optimization plans. However, there are problems such as long formula development cycle and high cost. Summary of the Invention

[0005] In view of this, the present invention provides a method for predicting the anti-leaching performance of high-radiation borosilicate glass and its application. The prediction method can directly predict the mass loss per unit surface area of ​​high-radiation borosilicate glass under static leaching test conditions based on a given glass composition, so that the glass composition can be adjusted according to the predicted value to obtain a specific component ratio with the expected anti-leaching performance, reducing the time and money costs of "trial and error" formula development.

[0006] The technical solution of the present invention is achieved as follows:

[0007] In a first aspect, the present invention provides a method for predicting the anti-leaching performance of high-energy borosilicate glass, comprising the following steps:

[0008] S1. Obtaining the oxide component of the high-radiation borosilicate glass;

[0009] S2. According to the formula , predicting the mass loss per unit surface area of ​​the high-radiation borosilicate glass in a static leaching test;

[0010] Where, L is the predicted value of mass loss per unit surface area of ​​the high-energy borosilicate glass, i The first i The influence coefficient of the oxide components on the anti-leaching performance, ij The first i and j The interaction between the oxide components and the influence coefficient of anti-leaching performance, i and j The first i Species and j The mass fraction of the oxide components.

[0011] The deviation between the predicted value and the measured value of mass loss per unit surface area is <±20%.

[0012] Based on the intrinsic connection between the composition and properties of high-radiative borosilicate glass, a method for predicting the anti-leaching properties of high-radiative borosilicate glass solids in my country was established. Based on the quantitative calculation of the oxide components of a given high-radiative borosilicate glass, the anti-leaching properties of the high-radiative borosilicate glass formula were predicted, which can greatly improve the efficiency of optimizing the high-radiative borosilicate glass composition, shorten the formula research cycle, and reduce the formula research cost.

[0013] On the basis of the above technical solution, further, the oxide components of the high-radiation borosilicate glass, calculated by mass fraction, include 35-55% SiO2, 5-20% B2O3, 0-10% Al2O3, 0-10% CaO, 5-18% Na2O and 12-25% of other components.

[0014] On the basis of the above technical solution, further, the oxide components of the high-radiation borosilicate glass, calculated by mass fraction, include 43.5~49.5% SiO2, 13~18% B2O3, 3~6% Al2O3, 5~8% CaO, 10.0~13% Na2O and 17~21% of other components.

[0015] On the basis of the above technical solution, further, the influence coefficient of SiO2 on anti-leaching performance is -3.0, the influence coefficient of B2O3 on anti-leaching performance is 8.5, the influence coefficient of Na2O on anti-leaching performance is 32.0, the influence coefficient of Al2O3 on anti-leaching performance is 4.0, the influence coefficient of CaO on anti-leaching performance is 50.0, the influence coefficient of the remaining components on anti-leaching performance is -10.0, the influence coefficient of the interaction between B2O3 and Al2O3 on anti-leaching performance is -150.0, and the influence coefficient of the interaction between Na2O and CaO on anti-leaching performance is -310.0.

[0016] By screening quadratic terms in the regression analysis to optimize the model, and eliminating those with insignificant effects from all possible quadratic terms affecting anti-leaching performance, the two quadratic terms with the most significant impact on anti-leaching performance were ultimately selected, and the model achieved optimal goodness of fit. Specifically, the interaction between B2O3 and Al2O3, and the interaction between Na2O and CaO, had the most significant impact on anti-leaching performance.

[0017] For a given high-radiation borosilicate glass composition, it is only necessary to compare the mass fraction of each oxide component with the corresponding That The predicted value of the anti-leaching performance of the high-radiation borosilicate glass can be obtained by multiplying and accumulating the values ​​and performing natural logarithm transformation.

[0018] Various oxide components in high-radiation borosilicate glass i and ij The values ​​are shown in Table 1 below.

[0019] Table 1 Oxide components i and ij Value

[0020]

[0021] On the basis of the above technical solution, further, the remaining components include multiple ones of Li2O, ZrO2, La2O3, Nd2O3, CeO2, Cs2O, Fe2O3, NiO, Cr2O3, MnO and SrO.

[0022] On the basis of the above technical solution, the static leaching test is further carried out by statically leaching the high-radiation borosilicate glass in deionized water at 89°C to 91°C, maintaining the ratio of the surface area of ​​the high-radiation borosilicate glass to the volume of deionized water at 9.5 m -1 ~10.5m -1 After 28 days, the mass loss per unit surface area of ​​the high-radiation borosilicate glass was calculated.

[0023] In a second aspect, the present invention provides an application of the above prediction method in the formulation design of high-radiation borosilicate glass.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] (1) The present invention provides a simple and quick method for predicting the anti-leaching performance of high-radiation borosilicate glass. By simply inputting the main components of the high-radiation borosilicate glass formula, the anti-leaching performance of the glass formula can be quickly predicted.

[0026] (2) The prediction method provided by this invention can determine the design direction of glass composition and calculate the composition ratio with better performance, providing guidance for the development of high-radiation borosilicate glass formulas. Compared with traditional formula design methods, it can save a lot of experimental time and trial and error costs. DETAILED DESCRIPTION

[0027] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0028] Example 1

[0029] This embodiment provides a method for predicting the leaching resistance of high-radiative borosilicate glass. Given a high-radiative borosilicate glass, the glass comprises the following oxide composition by mass: 46.0% SiO2, 13.0% B2O3, 12.0% Na2O, 2.0% Li2O, 4.0% Al2O3, 5.0% CaO, 2.0% BaO, 2.5% ZrO2, 2.5% La2O3, 1.5% CeO2, 2.5% MoO3, 0.5% Cr2O3, 1.0% Fe2O3, 0.5% NiO, 0.2% Rb2O, 0.3% Y2O3, 0.5% TeO2, 2.0% Nd2O3, 0.5% MnO, 1.0% Cs2O, and 0.5% SrO.

[0030] The above prediction method was used to obtain the mass loss per unit surface area of ​​the high-radiation borosilicate glass in the leaching test, which was 7.4 g / m 2 .

[0031] A high-radiative borosilicate glass batch was prepared according to the above proportions. SiO₂, B₂O₃, Al₂O₃, ZrO₂, La₂O₃, Nd₂O₃, CeO₂, MoO₃, Fe₂O₃, NiO, Cr₂O₃, TeO₂, and MnO were introduced as oxides, while the remaining components were introduced as carbonates. The batch was mixed thoroughly and melted in a high-temperature furnace at 1150°C for 2 hours. The molten glass was poured into a preheated cylindrical graphite crucible and subsequently annealed in a heat treatment furnace at 450°C for 2 hours. After annealing and cooling, a high-radiative borosilicate glass sample was obtained.

[0032] The high-radiation borosilicate glass sample was cut into pieces with a surface area of ​​approximately 400 mm 2 The cylindrical shape is obtained and each surface is polished to obtain the test sample for anti-leaching experiment.

[0033] The test sample was statically leached in deionized water at 90℃±1℃, maintaining the ratio of the test sample surface area to the deionized water volume at 10.0 m -1 ±0.5 m -1 After 28 days of leaching, the mass loss per unit surface area was 8.5 g / m 2 , which deviates from the predicted value by about 15%.

[0034] Example 2

[0035] This embodiment provides a method for predicting the leaching resistance of high-radiation borosilicate glass. The specific operation is the same as that of Example 1, except that: to improve the leaching resistance of high-radiation borosilicate glass, under the condition that the waste inclusion rate remains unchanged, the following components are adjusted based on the predicted value of the mass loss per unit surface area in the leaching test, calculated as follows: 47.5% SiO2, 15.0% B2O3, 10.0% Na2O, 2.5% Li2O, 3.0% Al2O3, 5.0% CaO, 1.0% BaO, 2.5% ZrO2, 2.5% La2O3, 1.5% CeO2, 2.5% MoO3, 0.5% Cr2O3, 1.0% Fe2O3, 0.5% NiO, 0.2% Rb2O, 0.3% Y2O3, 0.5% TeO2, 2.0% Nd2O3, 0.5% MnO, 1.0% Cs2O, 0.5% SrO.

[0036] The above prediction method shows that the mass loss per unit surface area of ​​the high-radiation borosilicate glass in the leaching test is 6.3 g / m 2 .

[0037] After the test sample completed the 28-day leaching experiment, the mass loss per unit surface area was measured to be 6.2 g / m 2 , which deviates from the predicted value by about 2%, and the anti-leaching performance of the glass formula is improved.

[0038] Example 3

[0039] This embodiment provides a method for predicting the leaching resistance of high-radiation borosilicate glass. The specific operation is the same as that of Example 1, except that: to further improve the leaching resistance of high-radiation borosilicate glass, the following components are adjusted based on the predicted value of mass loss per unit surface area in the leaching test, calculated as follows: 49.5% SiO2, 14.5% B2O3, 13.0% Na2O, 0.0% Li2O, 6.0% Al2O3, 0.0% CaO, 1.0% BaO, 2.5% ZrO2, 2.5% La2O3, 1.5% CeO2, 2.5% MoO3, 0.5% Cr2O3, 1.0% Fe2O3, 0.5% NiO, 0.2% Rb2O, 0.3% Y2O3, 0.5% TeO2, 2.0% Nd2O3, 0.5% MnO, 1.0% Cs2O, 0.5% NiO, 0.6% Br2O3, 0.7% Cr2O3, 0.8% Br2O3, 0.9% Cr2O3, 1.0% Br2O3, 0.9% Cr2O3, 1.0% Br2O3, 0.9% Cr2O3, 0.9 ...0.9% Br2O3, 0.9% Br2O3, 0.9% Br2O3, 0.9% Br2O3, 0.9% Br2O3, 0.9% Br2O3, 0.9 SrO.

[0040] The mass loss per unit surface area of ​​the high-radiation borosilicate glass obtained by the above prediction method is 3.5 g / m 2 .

[0041] After the test sample completed the 28-day leaching experiment, the mass loss per unit surface area was measured to be 3.2 g / m 2 , which deviates from the predicted value by about 9%, and the anti-leaching performance of the glass formula is further improved.

[0042] Example 4

[0043] This embodiment provides a method for predicting the leaching resistance of high-energy borosilicate glass. The specific operation is the same as that of Example 1, except that the following components are adjusted while keeping the contents of other components unchanged. The following components are adjusted in terms of oxide mass fraction: 43.5% SiO2, 18.0% B2O3, 11.5% Na2O, 0.0% Li2O, 5.0% Al2O3, 5.0% CaO, 1.0% BaO, 2.5% ZrO2, 2.5% La2O3, 1.5% CeO2, 2.5% MoO3, 0.5% Cr2O3, 1.0% Fe2O3, 0.5% NiO, 0.2% Rb2O, 0.3% Y2O3, 0.5% TeO2, 2.0% Nd2O3, 0.5% MnO, 1.0% Cs2O, and 0.5% SrO.

[0044] The mass loss per unit surface area of ​​the leaching test of the high-radiation borosilicate glass obtained by the above prediction method is 6.5 g / m 2 .

[0045] After the test sample completed the 28-day leaching experiment, the mass loss per unit surface area was measured to be 7.2 g / m 2 , which deviates from the predicted value by about 11%.

[0046] Example 5

[0047] This embodiment provides a method for predicting the leaching resistance of high-radiation borosilicate glass. The specific operation is the same as that of Example 1, except that: a high-radiation borosilicate glass is given, comprising the following oxide composition by mass fraction: 35.0% SiO2, 20.0% B2O3, 5.0% Na2O, 0.0% Li2O, 10.0% Al2O3, 10.0% CaO, 1.2% BaO, 2.9% ZrO2, 2.9% La2O3, 1.8% CeO2, 2.9% MoO3, 0.6% Cr2O3, 1.2% Fe2O3, 0.6% NiO, 0.2% Rb2O, 0.4% Y2O3, 0.6% TeO2, 2.4% Nd2O3, 0.6% MnO, 1.2% Cs2O, and 0.5% SrO.

[0048] The mass loss per unit surface area of ​​the high-radiation borosilicate glass obtained by the above prediction method is 3.9 g / m2 .

[0049] After the test sample completed the 28-day leaching experiment, the mass loss per unit surface area was measured to be 3.2 g / m 2 , which deviates from the predicted value by about 18%.

[0050] Example 6

[0051] This embodiment provides a method for predicting the leaching resistance of high-radiative borosilicate glass. The specific operation is the same as that of Example 1, except that: a given high-radiative borosilicate glass includes the following oxide composition by mass percentage: 55.0% SiO2, 5.0% B2O3, 18.0% Na2O, 5.0% Li2O, 0.0% Al2O3, 0.0% CaO, 1.0% BaO, 2.5% ZrO2, 2.5% La2O3, 1.5% CeO2, 2.5% MoO3, 0.5% Cr2O3, 1.0% Fe2O3, 0.5% NiO, 0.2% Rb2O, 0.3% Y2O3, 0.5% TeO2, 2.0% Nd2O3, 0.5% MnO, 1.0% Cs2O, and 0.5% SrO.

[0052] The mass loss per unit surface area of ​​the high-radiation borosilicate glass obtained by the above prediction method is 20.3 g / m 2 .

[0053] After the test sample completed the 28-day leaching experiment, the mass loss per unit surface area was measured to be 23.7 g / m 2 , which deviates from the predicted value by about 17%.

[0054] Comparative Example 1

[0055] This embodiment provides a method for predicting the leaching resistance of high-radiative borosilicate glass. The specific operation is the same as that of Example 1, except that: a given high-radiative borosilicate glass includes the following oxide composition by mass percentage: 36.0% SiO2, 11.0% B2O3, 3.0% Na2O, 6.0% Li2O, 20.0% Al2O3, 3.0% CaO, 1.3% BaO, 3.1% ZrO2, 3.1% La2O3, 1.8% CeO2, 3.1% MoO3, 0.6% Cr2O3, 1.2% Fe2O3, 0.6% NiO, 0.3% Rb2O, 0.4% Y2O3, 0.6% TeO2, 2.5% Nd2O3, 0.6% MnO, 1.2% Cs2O, and 0.6% SrO.

[0056] The contents of Na2O and Al2O3 in the waste glass are not within the applicable range of the prediction method. The mass loss per unit surface area of ​​the high-radiation borosilicate glass obtained by the above prediction method is 0.1 g / m 2 .

[0057] After 28 days of leaching, the mass loss per unit surface area of ​​the tested sample was 13.7 g / m 2 , which is quite different from the predicted value, and the deviation between the predicted value and the measured value is greater than 99%.

[0058] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for predicting the anti-leaching performance of high-energy borosilicate glass, characterized in that: The following steps are involved: S1. Obtaining the oxide component of the high-radiation borosilicate glass; S2, according to the formula , predicting the mass loss per unit surface area of ​​the high-radiation borosilicate glass in a static leaching test; Wherein, L is the mass loss per unit surface area of ​​the high-energy borosilicate glass, L i is the influence coefficient of the ith oxide component in the high-radiation borosilicate glass on the anti-leaching performance, L ij is the influence coefficient of the interaction between the i-th and j-th oxide components in the high-radiation borosilicate glass on the anti-leaching performance, x i with x j is the mass fraction of the i-th and j-th oxide components in the high-radiation borosilicate glass; The oxide components of the high-radiation borosilicate glass, calculated by mass fraction, include 35-55% SiO2, 5-20% B2O3, 0-10% Al2O3, 0-10% CaO, 5-18% Na2O and 12-25% of other components; The influence coefficient of SiO2 on anti-leaching performance is -3.0, the influence coefficient of B2O3 on anti-leaching performance is 8.5, the influence coefficient of Na2O on anti-leaching performance is 32.0, the influence coefficient of Al2O3 on anti-leaching performance is 4.0, the influence coefficient of CaO on anti-leaching performance is 50.0, the influence coefficient of other components on anti-leaching performance is -10.0, the influence coefficient of the interaction between B2O3 and Al2O3 on anti-leaching performance is -150.0, and the influence coefficient of the interaction between Na2O and CaO on anti-leaching performance is -310.

0.

2. The method for predicting the anti-leaching performance of high-radiation borosilicate glass according to claim 1, wherein: The oxide components of the high-radiation borosilicate glass, calculated by mass fraction, include 43.5-49.5% SiO2, 13-18% B2O3, 3-6% Al2O3, 5-8% CaO, 10.0-13% Na2O and 17-21% of other components.

3. The method for predicting the anti-leaching performance of high-radiation borosilicate glass according to claim 1, wherein: The remaining components include various ones of Li2O, ZrO2, La2O3, Nd2O3, CeO2, Cs2O, Fe2O3, NiO, Cr2O3, MnO and SrO.

4. The method for predicting the anti-leaching performance of high-radiation borosilicate glass according to claim 1, wherein: The static leaching test is to statically leach the high-radiative borosilicate glass in deionized water at 89°C to 91°C, maintaining a surface area ratio of the high-radiative borosilicate glass to the volume of deionized water of 9.5 m -1 ~10.5m -1 After 28 days, the mass loss per unit surface area of ​​the high-radiation borosilicate glass was calculated.

5. Use of the prediction method according to any one of claims 1 to 4 in formula design of high-radiation borosilicate glass.

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