硅酸盐学报

不同势函数下类粒化高炉矿渣玻璃体结构的分子动力学模拟

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姚羽涵 ¹ , 王亚丽 ¹ , 崔素萍 ¹ , 刘辉 ¹ , 王卉 ²

硅酸盐学报 | 研究论文 2024,52(11): 3594-3605

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硅酸盐学报 |研究论文 2024 , 52 (11) : 3594 -3605

不同势函数下类粒化高炉矿渣玻璃体结构的分子动力学模拟

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姚羽涵¹, 王亚丽¹, 崔素萍¹, 刘辉¹, 王卉²

作者信息

^1．北京工业大学材料科学与工程学院，北京 100124

^2．北京建筑材料科学研究总院有限公司，北京 100041

通讯作者:

崔素萍（1964—），女，博士，教授。

作者简介:

姚羽涵（1994—），男，博士研究生。

Molecular Dynamics Simulation of Glass Structure in Granulated Blast Furnace Slag

Yuhan YAO¹, Yali WANG¹, Suping CUI¹, Hui LIU¹, Hui WANG²

Affiliations

^1.College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China

^2.Beijing Building Materials Academy of Sciences Research, Beijing 100041, China

Corresponding Author:

CUI Suping (1964—), female, Ph.D., Professor. E-mail: cuisuping@bjut.edu.cn

YAO Yuhan (1994—), male, Doctoral candidate. E-mail: yaoyuhan1994@126.com

出版时间: 2024-11-20 doi: 10.14062/j.issn.0454-5648.20230872

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摘要

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分子动力学模拟作为粒化高炉矿渣中玻璃体结构研究手段的准确性受到势函数选择的影响。本工作分别采用Buckingham势、Broyden-Moré-Hénon（BMH）势、Miyake势和SHIK势模拟了不同化学组成类矿渣玻璃体的随机网络结构特征，并从局部有序结构、网络形成体聚合行为和网络改性体团簇行为等方面对比了模拟结果与实验结果的匹配性。结果表明：Buckingham势、BMH势和Miyake势更适合玻璃体局部有序结构的模拟；而SHIK在玻璃体中不同类型氧原子含量及Qⁿ分布随化学组成变化的趋势模拟上具有更高的稳定性；网络改性体的团簇行为更适合采用定义了金属离子间相互作用势的SHIK势和BMH势。

关键词

粒化高炉矿渣 / 玻璃体 / 分子动力学模拟 / 势函数 / 随机网络结构

Abstract

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Introduction

Granulated blast furnace slag (GBFS) has been widely applied in Marine cement, low-carbon cement, alkali-activated cementitious materials, and geopolymer cementitious materials due to its excellent potential hydration activity and hydration product optimization ability. The glass phase (SGP) is the predominant active mineral in GBFS, and its ionic dissolution ability in an alkaline environment directly influences the hydration activity of GBFS. Therefore, establishing the correlation between the structural characteristic and their hydration properties is imperative for optimizing the utilization of GBFS. Accurately describing the structural characteristics of SGP remains a pivotal challenge that has yet to be resolved. The hydration activity of GBFS can be partially elucidated by investigating the structural characteristics of alkali earth metal aluminosilicate glass using molecular dynamics (MD) simulation. Given the influence of potential functions on the accuracy of MD simulation results, it is imperative to undertake a comparative investigation into SGP structure simulation employing different potential functions. This paper compared the locally ordered structure, oxygen atom type, polymerization behavior, and clustering behavior using four different potentials: Buckingham potential, Broyden-Moré-Hénon (BMH) potential, Miyake potential, and SHIK potential. The accuracy and reference ability of the simulation is achieved by comparing the matched degree between the simulation results and experimental data, thereby providing a valuable reference for investigating the nanostructure and hydration characteristics of SGP in GBFS using MD simulations.

Methods

The SGP structure was simulated using molecular dynamics with the Buckingham potential, BMH potential (optimized based on mineral crystal structure), Miyake potential (combining multiple potential functions), and SHIK potential (optimized through first-principles molecular dynamics). The initial random configuration of the SGP structure, consisting of 3 000 Ca, Si, Al, Mg, and O ions, was generated using the Amorphous Cell module in Materials Studio software. The proportions of different ion types in the SGP structure were determined based on the chemical composition of industrial GBFS and encompassed variations within a specific range for the mass ratio of SiO₂/Al₂O₃ and quaternary alkalinity. A Large-scale Atomic/Molecular Massively Parallel Simulator was employed to calculate the MD process with periodic boundaries in real units using an integral step size of 0.8 fs. The simulation process involved six stages of relaxation to simulate the quench granulation process observed in industrial GBFS.

The laboratory synthesis of SGP utilizes chemically pure SiO₂, Al₂O₃, CaO, and MgO powders with a chemical composition matching referenced in the MD simulation. The homogenized oxide powder is melted in a Muffle furnace using a graphite crucible. The melting process occurs at 1 500 ℃ for 2 h, followed by quench cooling using an ice water mixture at 0 ℃. After crushing and grinding the cooled SGP block with an agate grinder, the resulting fine powder (200-mesh) is selected for X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and ²⁹Si solid-state magic-angle spinning nuclear magnetic resonance (MAS NMR) experiments. These experimental results are used to evaluate the accuracy of the MD simulation findings.

Results and discussion

The MD simulation results of SGP structures under all potential functions are consistent with the glass random network model. The optimization of Buckingham potential, BMH potential, and Miyake potential parameters pertains to specific crystal structures, offering advantages over SHIK potential in simulating local ordered structure characteristics. Furthermore, a comparison between the MD simulation results and XPS experimental data reveals that Buckingham potential, BMH potential, and Miyake potential exhibit contrasting or localized fluctuation patterns in bridging oxygen, non-bridging oxygen, and free oxygen contents compared to the experimental findings. Notably, an increase in alkalinity leads to a decrease in non-bridging oxygen content, according to some simulation results; however, this contradicts the charge balance principle of glass structure. In comparison, the variation trend of non-bridging oxygen and bridging oxygen under SHIK potential aligns with the outcomes observed in XPS experiments.

The experimental results from ²⁹Si MAS NMR indicate that SGP primarily consists of Q⁰ and Q¹ types [SiO₄]. However, the simulation results using all potential functions exhibit a significantly higher degree of polymerization for [SiO₄], with a large number of Q³ and Q⁴ types present. This discrepancy can be attributed to the short time scale of the simulation process, leading to an abundance of free oxygen. These findings highlight inherent technical limitations in MD simulations for accurately predicting the quantitative distribution of Qⁿ. Notably, only the SHIK potential simulations demonstrate consistent trends with experimental observations, whereas Buckingham potential, BMH potential, and Miyake potential fail to capture the decreasing trend in polymerization degree as the SiO₂/Al₂O₃ mass ratio decreases and alkalinity increases. Combined with the quantitative XRD data, the clustering behavior of Ca remained largely unaltered in the Miyake potential as the local enrichment of Ca increased; however, a transition from isolated Ca to clustered Ca was observed in both BMH and SHIK potentials.

Conclusions

The main conclusions of this paper are summarized as follows. Buckingham, BMH and Miyake potential exhibit suitability for simulating local ordered structure. Moreover, SHIK potential has higher stability in simulating the effect of chemical composition on the content variation trend of different types of oxygen and the Qn distribution. Lastly, SHIK potential and BMH potential, which define the interaction forces between metal ions, are more suitable for the clustering behavior as network modifiers. This study demonstrates that for the optimization of MD simulation of SGP in GBFS, it is a reasonable approach to add the potential parameters governing ion interactions and optimize the existing potential based on Ab initio molecular dynamics simulations of target structure characteristics.

Key words

granulated blast-furnace slag / glass phase / molecular dynamics simulation / potential function / random network structure

引用本文

姚羽涵, 王亚丽, 崔素萍, 刘辉, 王卉. 不同势函数下类粒化高炉矿渣玻璃体结构的分子动力学模拟. 硅酸盐学报, 2024 , 52 (11) : 3594 -3605 . DOI: 10.14062/j.issn.0454-5648.20230872

Yuhan YAO, Yali WANG, Suping CUI, Hui LIU, Hui WANG. Molecular Dynamics Simulation of Glass Structure in Granulated Blast Furnace Slag[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (11) : 3594 -3605 . DOI: 10.14062/j.issn.0454-5648.20230872

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北京市科技计划(Z221100007522002)

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2024年第52卷第11期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230872

接收时间：2023-11-15
首发时间：2026-10-22
出版时间：2024-11-20

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出版历史

收稿日期：2023-11-15
修回日期：2023-12-28

基金

北京市科技计划(Z221100007522002)

作者信息

^1．北京工业大学材料科学与工程学院，北京 100124

^2．北京建筑材料科学研究总院有限公司，北京 100041

通讯作者:

崔素萍（1964—），女，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230872

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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