硼硅酸盐玻璃热导率混合碱效应的结构起源探索

doi:10.16552/j.cnki.issn1001-1625.2025.1057

摘要/Abstract

摘要：

非晶材料的热输运机制与其微观结构间的内在关联尚未阐明，尤其是微观结构变化如何调控不同振动模式（传播子、扩散子和局域子）的热输运行为，多年来这一直是凝聚态物理与材料科学领域的探索热点。本文以65.0SiO₂·5.0B₂O₃·7.5CaO·4.9MgO·xK₂O·（17.6-x）Na₂O（x=0~17.6）系列硼硅酸盐玻璃为研究对象，系统探究了钠、钾离子替换对热导率的影响及其微观结构起源。通过热导率测试，发现该系列玻璃的热导率性质呈现典型的混合碱效应，即随着钾离子逐渐取代钠离子，玻璃的热导率呈非线性下降趋势。基于Agne半经验模型，将该系列玻璃的总热导率分解为传输子和扩散子两种热振动模式，其中传播子热振动模式随着钠、钾替换基本保持不变；扩散子模式对热导率的贡献则呈现出与总热导率一致的混合碱效应。拉曼光谱的峰位和峰形演化揭示了该系列玻璃由钠、钾离子替换引起的Si—O—Si键角分布变化，结合热导物理机制阐释了该系列玻璃热导率性质混合碱效应的可能微观结构起源。

关键词: 硼硅酸盐玻璃, 混合碱效应, 热导率, 扩散子, 传播子, 结构无序性

Abstract:

Thermal transport in amorphous materials is primarily governed by two vibrational modes： propagons， which resemble lattice waves in crystals， and diffusons. However， the mechanism by which glass composition modulates these two modes remains insufficiently understood. To address this gap， this study investigated a series of borosilicate glasses with the composition 65.0SiO₂·5.0B₂O₃·7.5CaO·4.9MgO·xK₂O·（17.6-x）Na₂O （x=0~17.6）， to elucidate the impact of Na-K substitution on thermal conductivity and uncover its atomic-scale structural origins. Thermal conductivity measurements demonstrate that this glass series exhibits a typical mixed-alkali effect， characterized by a nonlinear decrease in thermal conductivity as potassium ions gradually replace sodium ions. To clarify the physical nature of this nonlinear behavior， the total thermal conductivity was decomposed into contributions from propagons and diffusons based on the semi-empirical model proposed by Agne et al. The decomposition results indicate that the contribution from propagons remains essentially constant throughout the substitution process. In stark contrast， the thermal transport contribution from diffusons exhibits a pronounced nonlinear decline that mirrors the trend of the total thermal conductivity. This confirms that the suppression of diffuson-mediated thermal transport is the dominant factor driving the mixed-alkali effect in this glass series. Detailed Raman spectroscopic characterization was employed to probe the structural evolution underpinning these thermal property changes. The spectral analysis reveals that the coexistence of dissimilar alkali ions （Na⁺ and K⁺） induces local structural strain due to ionic radius and field strength mismatch. This strain manifests as a variation in the distribution of Si—O—Si bond angles， evidenced by the shift of the characteristic Raman band near 1 090 cm^-1. This bond angle distortion enhances the short-range disorder of the glass network， thereby disrupting the vibrational synergy and reducing the energy transfer efficiency of the diffusons. In conclusion， this study not only deepens the fundamental understanding of thermal transport in amorphous solids but also provides a theoretical basis for designing glass materials with tailored thermal conductivities via composition engineering.

Key words: borosilicate glass, mixed-alkali effect, thermal conductivity, diffuson, propagon, structural disorder

中图分类号:

TQ171

周群丰, 周和敏, 朱永昌, 崔竹, 乔昂, 陶海征. 硼硅酸盐玻璃热导率混合碱效应的结构起源探索[J]. 硅酸盐通报, 2026, 45(3): 787-793.

ZHOU Qunfeng, ZHOU Hemin, ZHU Yongchang, CUI Zhu, QIAO Ang, TAO Haizheng. Exploring Structural Origin of Mixed-Alkali Effect on Thermal Conductivity in Borosilicate Glass[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(3): 787-793.

图/表 4

图1 钠钾替换系列硼硅酸盐玻璃的量热曲线、Tg和CTE随R的变化关系

Fig.1 Calorimetric curves， Tg， and CTE for Na-K substitution borosilicate glass series as a function of R

图2 钠钾替换系列硼硅酸盐玻璃的κ、κdiff与κprop随R的变化关系

Fig.2 κ， κdiff， and κprop as a function of R for Na-K substitution borosilicate glass series

表1 25 ℃下钠钾替换系列硼硅酸盐玻璃的ρ、 vL、 vT、 vs、κ和κdiff

Table 1 ρ， vL， vT， vs， κ， and κdiff of Na-K substitution borosilicate glass series at 25 ℃

R	ρ/（g·cm^-3）	v_L/（m·s^-1）	v_T/（m·s^-1）	v_s/（m·s^-1）	κ/（W·m^-1·K^-1）	κ_diff/（W·m^-1·K^-1）
0	2.530	6 240	3 430	4 367	0.919	0.689
0.2	2.522	6 230	3 420	4 357	0.912	0.676
0.4	2.517	6 160	3 390	4 313	0.898	0.660
0.5	2.514	6 130	3 370	4 290	0.883	0.653
0.6	2.511	6 100	3 340	4 260	0.874	0.644
0.8	2.501	5 990	3 290	4 190	0.843	0.627
1.0	2.475	5 780	3 180	4 047	0.812	0.600

图3 钠钾替换系列硼硅酸盐玻璃的拉曼光谱和1 090 cm-1附近特征峰峰位（ν）随R的变化关系

Fig.3 Raman spectra and variation of characteristic peak position （ν） near 1 090 cm-1 as a function of R for Na-K substitution borosilicate glass series

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