Pub Date : 2025-12-10DOI: 10.1016/j.jnoncrysol.2025.123916
Yue Mi , Cong Ao , Qingyang Shen , Zhehui Sun , Qinghuang Zhang , Binchang Zhang , Lixiong Han , Jun Xie , Dehua Xiong
This study investigated the effects of the Mg/B mass ratio on the structure, high-temperature rheological behavior, and dielectric properties of MgO-Al2O3-B2O3-SiO2 based boron aluminosilicate glass. The results indicated that after the substitution of B2O3 for MgO, the contents of both [BO3] and [BO4] units increased; however, the dominant coordination gradually shifted from [BO4] to [BO3]. Notably, variations in the Mg/B ratio significantly altered the coordination environment of Al3+, leading to an increase in the content of [AlO5] units from 28.80 % to 45.11 %. These structural changes resulted in an increased degree of polymerization but a weakened network rigidity. Consequently, the coefficient of thermal expansion (CTE), glass transition temperature (Tg), flexural strength, dielectric constant, and dielectric loss were all reduced. At an optimized Mg/B mass ratio of 0.12, the glass sample exhibited a favorable combination of dielectric properties (dielectric constant = 4.48 @10 GHz, dielectric loss = 2.0 × 10–3 @10 GHz) and a low fiber drawing temperature (1301 °C), which is suitable for the production of glass fibers.
{"title":"Effect of B2O3 on the structure and properties of low-dielectric boron aluminosilicate glass used for glass fibers","authors":"Yue Mi , Cong Ao , Qingyang Shen , Zhehui Sun , Qinghuang Zhang , Binchang Zhang , Lixiong Han , Jun Xie , Dehua Xiong","doi":"10.1016/j.jnoncrysol.2025.123916","DOIUrl":"10.1016/j.jnoncrysol.2025.123916","url":null,"abstract":"<div><div>This study investigated the effects of the Mg/B mass ratio on the structure, high-temperature rheological behavior, and dielectric properties of MgO-Al<sub>2</sub>O<sub>3</sub>-B<sub>2</sub>O<sub>3</sub>-SiO<sub>2</sub> based boron aluminosilicate glass. The results indicated that after the substitution of B<sub>2</sub>O<sub>3</sub> for MgO, the contents of both [BO<sub>3</sub>] and [BO<sub>4</sub>] units increased; however, the dominant coordination gradually shifted from [BO<sub>4</sub>] to [BO<sub>3</sub>]. Notably, variations in the Mg/B ratio significantly altered the coordination environment of Al<sup>3+</sup>, leading to an increase in the content of [AlO<sub>5</sub>] units from 28.80 % to 45.11 %. These structural changes resulted in an increased degree of polymerization but a weakened network rigidity. Consequently, the coefficient of thermal expansion (CTE), glass transition temperature (T<sub>g</sub>), flexural strength, dielectric constant, and dielectric loss were all reduced. At an optimized Mg/B mass ratio of 0.12, the glass sample exhibited a favorable combination of dielectric properties (dielectric constant = 4.48 @10 GHz, dielectric loss = 2.0 × 10<sup>–3</sup> @10 GHz) and a low fiber drawing temperature (1301 °C), which is suitable for the production of glass fibers.</div></div>","PeriodicalId":16461,"journal":{"name":"Journal of Non-crystalline Solids","volume":"674 ","pages":"Article 123916"},"PeriodicalIF":3.5,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145749076","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-10DOI: 10.1016/j.jnoncrysol.2025.123914
Ivone Regina de Oliveira , Isabela dos Santos Gonçalves , Julia Marinzeck de Alcantara Abdala , Bianca Lapadula Heckert Franklin de Abreu , Gustavo Luiz Bueno Cardoso , Gilmar Patrocínio Thim , Tiago Moreira Bastos Campos
Bioactive glasses are recognized for their ability to release ions and induce apatite formation in physiological media. However, conventional glasses often cause a marked increase in pH during dissolution, which may lead to cytotoxic effects. In this study, chlorinated bioactive glasses were synthesized via a hydrolytic sol–gel route using tetraethyl orthosilicate (TEOS) and calcium chloride, aiming to obtain materials with efficient ionic release and controlled pH response. Samples were thermally treated at 500 °C, 600 °C, and 700 °C and characterized by FTIR, Raman spectroscopy, specific surface area (BET), scanning electron microscopy (SEM), and ionic release tests. The chlorinated bioactive glass calcined at 500 °C exhibited the most promising combination of characteristics: presence of hydroxyl groups (–OH), a structure predominantly composed of Q² units, high specific surface area (31.75 m² g⁻¹), well-defined mesoporosity, high ionic release (∼2000 µS cm⁻¹), and effective control of pH increase in aqueous media. These properties directly contribute to bioactivity and indicate that this material can be incorporated into biomedical formulations without the need for prior neutralization steps, in contrast to many conventional bioactive glasses. The results also demonstrate that the hydrolytic sol–gel route enables the synthesis of chlorinated bioactive glasses with tunable structure and dissolution profiles, overcoming limitations associated with more complex routes, such as those based on ion-exchange resins or precursors like metasilicate. The ability to combine high ionic release with low impact on pH represents a relevant advance in the design of bioceramics for regenerative and dental applications.
{"title":"Hydrolytically synthesized chlorinated bioactive glasses: Structural reticulation and controlled ion release without alkaline shift","authors":"Ivone Regina de Oliveira , Isabela dos Santos Gonçalves , Julia Marinzeck de Alcantara Abdala , Bianca Lapadula Heckert Franklin de Abreu , Gustavo Luiz Bueno Cardoso , Gilmar Patrocínio Thim , Tiago Moreira Bastos Campos","doi":"10.1016/j.jnoncrysol.2025.123914","DOIUrl":"10.1016/j.jnoncrysol.2025.123914","url":null,"abstract":"<div><div>Bioactive glasses are recognized for their ability to release ions and induce apatite formation in physiological media. However, conventional glasses often cause a marked increase in pH during dissolution, which may lead to cytotoxic effects. In this study, chlorinated bioactive glasses were synthesized via a hydrolytic sol–gel route using tetraethyl orthosilicate (TEOS) and calcium chloride, aiming to obtain materials with efficient ionic release and controlled pH response. Samples were thermally treated at 500 °C, 600 °C, and 700 °C and characterized by FTIR, Raman spectroscopy, specific surface area (BET), scanning electron microscopy (SEM), and ionic release tests. The chlorinated bioactive glass calcined at 500 °C exhibited the most promising combination of characteristics: presence of hydroxyl groups (–OH), a structure predominantly composed of Q² units, high specific surface area (31.75 m² g⁻¹), well-defined mesoporosity, high ionic release (∼2000 µS cm⁻¹), and effective control of pH increase in aqueous media. These properties directly contribute to bioactivity and indicate that this material can be incorporated into biomedical formulations without the need for prior neutralization steps, in contrast to many conventional bioactive glasses. The results also demonstrate that the hydrolytic sol–gel route enables the synthesis of chlorinated bioactive glasses with tunable structure and dissolution profiles, overcoming limitations associated with more complex routes, such as those based on ion-exchange resins or precursors like metasilicate. The ability to combine high ionic release with low impact on pH represents a relevant advance in the design of bioceramics for regenerative and dental applications.</div></div>","PeriodicalId":16461,"journal":{"name":"Journal of Non-crystalline Solids","volume":"674 ","pages":"Article 123914"},"PeriodicalIF":3.5,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145749077","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-10DOI: 10.1016/j.jnoncrysol.2025.123915
Jinfeng Liu , Yaqiong Liang , Guoliang Xu , Fu Wang , Qilong Liao , Jing Wang , Jun Zhang , Junwei Dong , Guanghua Li , Yunlong Luo , Huachao He , Caijun Zhou
This study systematically investigates the effects of substituting SiO2 with the network formers B2O3 and P2O5 on the melting behavior, structure, optical performance and chemical strengthening properties of the SiO2-Al2O3Na2O-K2O-MgO glass system. In-situ melting experiments enable real-time observation of bubble nucleation, migration, and elimination during glass melting, revealing the dynamic evolution process. The result shows that adding the clarifying agent Na2SO4·10H2O promoted the formation of large bubbles in the glass melt and significantly reduced bubble elimination time. The addition of B2O3 reduces the melt viscosity and melting temperature, thereby accelerating bubble removal. In contrast, the addition of P2O5 makes it difficult to eliminate bubbles. XRD analysis reveale that the NaAlSiO4 crystal phase formed when the P2O5 content was 3 mol%, and that the transmittance in the 320–500 nm range is approximately 0.6 % lower than that the other samples. FSM-6000LE results indicate that with the content of B2O3 increase, surface compressive stress (CS) increase, while depth of layer (DOL) decrease. However, with the increase of P2O5, the CS decrease and DOL increase. In conclusion, this paper provides a theoretical basis for optimizing the melting process and properties of high-alumina-silicate glass.
{"title":"The effect of B2O3 and P2O5 in bubble evolution and property modulation of high-alumina-silicate glass","authors":"Jinfeng Liu , Yaqiong Liang , Guoliang Xu , Fu Wang , Qilong Liao , Jing Wang , Jun Zhang , Junwei Dong , Guanghua Li , Yunlong Luo , Huachao He , Caijun Zhou","doi":"10.1016/j.jnoncrysol.2025.123915","DOIUrl":"10.1016/j.jnoncrysol.2025.123915","url":null,"abstract":"<div><div>This study systematically investigates the effects of substituting SiO<sub>2</sub> with the network formers B<sub>2</sub>O<sub>3</sub> and P<sub>2</sub>O<sub>5</sub> on the melting behavior, structure, optical performance and chemical strengthening properties of the SiO<sub>2</sub>-Al<sub>2</sub>O<sub>3<img></sub>Na<sub>2</sub>O-K<sub>2</sub>O-MgO glass system. In-situ melting experiments enable real-time observation of bubble nucleation, migration, and elimination during glass melting, revealing the dynamic evolution process. The result shows that adding the clarifying agent Na<sub>2</sub>SO<sub>4</sub>·10H<sub>2</sub>O promoted the formation of large bubbles in the glass melt and significantly reduced bubble elimination time. The addition of B<sub>2</sub>O<sub>3</sub> reduces the melt viscosity and melting temperature, thereby accelerating bubble removal. In contrast, the addition of P<sub>2</sub>O<sub>5</sub> makes it difficult to eliminate bubbles. XRD analysis reveale that the NaAlSiO<sub>4</sub> crystal phase formed when the P<sub>2</sub>O<sub>5</sub> content was 3 mol%, and that the transmittance in the 320–500 nm range is approximately 0.6 % lower than that the other samples. FSM-6000LE results indicate that with the content of B<sub>2</sub>O<sub>3</sub> increase, surface compressive stress (CS) increase, while depth of layer (DOL) decrease. However, with the increase of P<sub>2</sub>O<sub>5</sub>, the CS decrease and DOL increase. In conclusion, this paper provides a theoretical basis for optimizing the melting process and properties of high-alumina-silicate glass.</div></div>","PeriodicalId":16461,"journal":{"name":"Journal of Non-crystalline Solids","volume":"674 ","pages":"Article 123915"},"PeriodicalIF":3.5,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145749079","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-07DOI: 10.1016/j.jnoncrysol.2025.123904
Tao Li , Chen Su , Pengcheng Zhang , Siming Xiao , Yifan Ruan , Shengfeng Guo
MoCoB bulk metallic glass (BMG) exhibits very high thermal stability and outstanding mechanical properties. However, their wide applications are still limited due to the poor glass forming ability (GFA) and critical preparing conditions, particularly the need for low oxygen content. This study systematically investigated the effects of oxygen on the properties of MoCoB BMG. A small amount of oxygen incorporation (≤1064 ppm) significantly enhanced the GFA, increasing the critical diameter from 1.2 mm to 2 mm, due to a reduced thermodynamic driving force for crystallization. Moreover, the addition of 676 ppm oxygen simultaneously improves the mechanical properties of MoCoB BMG with the microhardness of 1347 HV, compressive strength of above 5000 MPa, nanohardness of 19 GPa, and Young's modulus of 300 GPa through strengthening local chemical bonds by the addition of oxygen. The high-oxygen-content specimens (2111 ppm) show exceptional corrosion resistance with a self-corrosion current density of 1.259 × 10–7A/cm2 in 3.5 wt. % NaCl solution. This can be attributed to the formation of a denser CoMoO4 composite oxide layer and suppression of passive film dissolution. These findings could provide a comprehensive understanding of the effects of oxygen on the BMGs, and help with the development of high-performance and cost-effective Mo-based BMGs.
{"title":"Effect of oxygen on the glass forming ability, mechanical properties and corrosion resistance of Mo-based bulk metallic glass","authors":"Tao Li , Chen Su , Pengcheng Zhang , Siming Xiao , Yifan Ruan , Shengfeng Guo","doi":"10.1016/j.jnoncrysol.2025.123904","DOIUrl":"10.1016/j.jnoncrysol.2025.123904","url":null,"abstract":"<div><div>MoCoB bulk metallic glass (BMG) exhibits very high thermal stability and outstanding mechanical properties. However, their wide applications are still limited due to the poor glass forming ability (GFA) and critical preparing conditions, particularly the need for low oxygen content. This study systematically investigated the effects of oxygen on the properties of MoCoB BMG. A small amount of oxygen incorporation (≤1064 ppm) significantly enhanced the GFA, increasing the critical diameter from 1.2 mm to 2 mm, due to a reduced thermodynamic driving force for crystallization. Moreover, the addition of 676 ppm oxygen simultaneously improves the mechanical properties of MoCoB BMG with the microhardness of 1347 HV, compressive strength of above 5000 MPa, nanohardness of 19 GPa, and Young's modulus of 300 GPa through strengthening local chemical bonds by the addition of oxygen. The high-oxygen-content specimens (2111 ppm) show exceptional corrosion resistance with a self-corrosion current density of 1.259 × 10<sup>–7</sup>A/cm<sup>2</sup> in 3.5 wt. % NaCl solution. This can be attributed to the formation of a denser CoMoO<sub>4</sub> composite oxide layer and suppression of passive film dissolution. These findings could provide a comprehensive understanding of the effects of oxygen on the BMGs, and help with the development of high-performance and cost-effective Mo-based BMGs.</div></div>","PeriodicalId":16461,"journal":{"name":"Journal of Non-crystalline Solids","volume":"674 ","pages":"Article 123904"},"PeriodicalIF":3.5,"publicationDate":"2025-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145749078","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-06DOI: 10.1016/j.jnoncrysol.2025.123903
S. Zhang , H.Y. Song , M.R. An
Rare earth (RE) alloying critically enhances Mg alloys, yet the atomistic origins of RE-driven strengthening mechanism remain elusive. Through hybrid molecular dynamics/Monte Carlo simulations, we investigate the impact of the Y concentration, short-range ordering (SRO), and temperature on the mechanical properties of the Mg alloys, specifically revealing the interaction mechanism between SRO structures and dislocation. Results demonstrate that Y solutes preferentially form localized SRO structures, which are beneficial for promoting the solid-state amorphization of the alloys. As Y concentration increases, the dominant strengthening mechanism shifts from conventional solid solution strengthening to a synergistic interplay of solid solution strengthening and SRO-induced local amorphization — elevating critical resolved shear stress by up to 50 % versus random solid solutions. Crucially, the SRO structures suppress dislocation glide via atomic-scale pinning. Furthermore, the mechanical properties of the alloys containing SRO exhibit anomalous temperature sensitivity due to the temperature-dependent stability of the SRO structures. These findings provide fundamental insights for designing advanced high-performance Mg alloys.
{"title":"Unraveling the impact of short-range ordering on the strengthening mechanisms in Mg-Y Alloys","authors":"S. Zhang , H.Y. Song , M.R. An","doi":"10.1016/j.jnoncrysol.2025.123903","DOIUrl":"10.1016/j.jnoncrysol.2025.123903","url":null,"abstract":"<div><div>Rare earth (RE) alloying critically enhances Mg alloys, yet the atomistic origins of RE-driven strengthening mechanism remain elusive. Through hybrid molecular dynamics/Monte Carlo simulations, we investigate the impact of the Y concentration, short-range ordering (SRO), and temperature on the mechanical properties of the Mg alloys, specifically revealing the interaction mechanism between SRO structures and dislocation. Results demonstrate that Y solutes preferentially form localized SRO structures, which are beneficial for promoting the solid-state amorphization of the alloys. As Y concentration increases, the dominant strengthening mechanism shifts from conventional solid solution strengthening to a synergistic interplay of solid solution strengthening and SRO-induced local amorphization — elevating critical resolved shear stress by up to 50 % versus random solid solutions. Crucially, the SRO structures suppress dislocation glide via atomic-scale pinning. Furthermore, the mechanical properties of the alloys containing SRO exhibit anomalous temperature sensitivity due to the temperature-dependent stability of the SRO structures. These findings provide fundamental insights for designing advanced high-performance Mg alloys.</div></div>","PeriodicalId":16461,"journal":{"name":"Journal of Non-crystalline Solids","volume":"674 ","pages":"Article 123903"},"PeriodicalIF":3.5,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692942","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-03DOI: 10.1016/j.jnoncrysol.2025.123890
Weiwei Wang , Hui Yan , Xin Cao , Jiwen Jiang , Junfei Liu , Shou Peng
In this study, a series of novel lead-free Bi2O3–B2O3–ZnO–BaO–CuO low-melting glasses with varying content of CuO were prepared, and these matrix glass powder were then used to form composite glass with varying additions of β-eucryptite. The effects of the content of CuO and β-eucryptite on the structure, thermal properties, sealing performance and microstructure of the low-melting glasses were investigated. Structural analysis indicates that the glasses were composed of [BiO3], [BiO6], [BO3] and [BO4] basic units, and the amounts of [BiO3] and [BiO6] units decreased with increasing content of CuO, while the transformation of [BO4] to [BO3] led to a gradual increase in the amount of [BO3], which loosened the glass structure. The coefficient of thermal expansion (CTE) of the glasses gradually increased, while the characteristic temperature (Tg and Td) and sealing temperature showed the opposite trend. The results also indicated that the CTE of the composite glasses decreased significantly with an increase in the external addition of β-eucryptite, and the sealing temperature did not increase substantially. Optimal comprehensive performance was observed at a β-eucryptite content of 6 %, resulting in a lower CTE of 87 × 10–7 / °C and sealing temperature of 415 °C. Following sealing, the factors affecting the sealing strength and fracture mechanism of the sealing glasses were examined. The composite glasses are well-suitable as sealing materials for vacuum glazing, meeting the requirements for low-melting sealing glass and exhibiting a favorable market prospect.
{"title":"Effects of CuO and β-eucyptite on the structure, properties and fracture mechanism of a low-melting glass for vacuum glazing","authors":"Weiwei Wang , Hui Yan , Xin Cao , Jiwen Jiang , Junfei Liu , Shou Peng","doi":"10.1016/j.jnoncrysol.2025.123890","DOIUrl":"10.1016/j.jnoncrysol.2025.123890","url":null,"abstract":"<div><div>In this study, a series of novel lead-free Bi<sub>2</sub>O<sub>3</sub>–B<sub>2</sub>O<sub>3</sub>–ZnO–BaO–CuO low-melting glasses with varying content of CuO were prepared, and these matrix glass powder were then used to form composite glass with varying additions of β-eucryptite. The effects of the content of CuO and β-eucryptite on the structure, thermal properties, sealing performance and microstructure of the low-melting glasses were investigated. Structural analysis indicates that the glasses were composed of [BiO<sub>3</sub>], [BiO<sub>6</sub>], [BO<sub>3</sub>] and [BO<sub>4</sub>] basic units, and the amounts of [BiO<sub>3</sub>] and [BiO<sub>6</sub>] units decreased with increasing content of CuO, while the transformation of [BO<sub>4</sub>] to [BO<sub>3</sub>] led to a gradual increase in the amount of [BO<sub>3</sub>], which loosened the glass structure. The coefficient of thermal expansion (CTE) of the glasses gradually increased, while the characteristic temperature (T<sub>g</sub> and T<sub>d</sub>) and sealing temperature showed the opposite trend. The results also indicated that the CTE of the composite glasses decreased significantly with an increase in the external addition of β-eucryptite, and the sealing temperature did not increase substantially. Optimal comprehensive performance was observed at a β-eucryptite content of 6 %, resulting in a lower CTE of 87 × 10<sup>–7</sup> / °C and sealing temperature of 415 °C. Following sealing, the factors affecting the sealing strength and fracture mechanism of the sealing glasses were examined. The composite glasses are well-suitable as sealing materials for vacuum glazing, meeting the requirements for low-melting sealing glass and exhibiting a favorable market prospect.</div></div>","PeriodicalId":16461,"journal":{"name":"Journal of Non-crystalline Solids","volume":"674 ","pages":"Article 123890"},"PeriodicalIF":3.5,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651844","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-02DOI: 10.1016/j.jnoncrysol.2025.123865
Mattias Edén, Baltzar Stevensson
The degree of disorder across the subnanometer scale of an oxide glass is largely governed by the relative propensities of its network formers () and modifiers to coordinate the bridging oxygen (BO) and non-bridging oxygen (NBO) species, as well as the (non)preferential interlinking of the various network-forming polyhedra. This paper and its sequel examine the bonding-preference concept, which quantifies the degree of preference or reluctance of two atom species to interlink. Unified and consistent definitions of bonding preferences are presented along with critical reviews of previous reports in the field, which remain sparse due to the substantial experimental challenges to quantify bonding preference in glasses and rendering computational modeling the main tool. Because the preference/reluctance for bond formation marks the deviation from a statistical atom/ion intermixing, a rigorous formulation of the latter is required. Potential pitfalls for defining the statistical reference case are discussed. With particular focus on glasses with ={Al, B, Si} as network formers, this article targets the (relative) –BO/NBO and –BO/NBO bonding preferences pertaining to the first coordination shells of the {, , O} species in the glass, while the preferential –O– interlinking and –O associations are examined in the sequel article.
氧化玻璃在亚纳米尺度上的无序程度在很大程度上取决于其网络形成物(F)和修饰剂(M)协调桥接氧（BO）和非桥接氧（NBO）的相对倾向，以及各种网络形成多面体的（非）优先互连。本文及其后续文章研究了键偏好概念，该概念量化了两个原子物种相互连接的偏好或不情愿程度。本文提出了键合偏好的统一和一致的定义，并对该领域以前的报告进行了批判性的回顾，由于在量化玻璃中的键合偏好和渲染计算建模的主要工具方面存在实质性的实验挑战，这些报告仍然很少。由于键形成的偏好/不情愿标志着与统计原子/离子混合的偏差，因此需要对后者进行严格的表述。讨论了定义统计参考案例的潜在缺陷。本文特别关注以F={Al， B， Si}为网络形成物的玻璃，研究了玻璃中{F， M， O}物质的第一配位壳层对F - bo /NBO和M - bo /NBO键的（相对）偏好，而在后续文章中研究了F - O - F '互联和Mz+ -FOp键的偏好。
{"title":"Quantifying bonding preferences in oxide glass structures across a sub-nanometer scale. I. First coordination sphere","authors":"Mattias Edén, Baltzar Stevensson","doi":"10.1016/j.jnoncrysol.2025.123865","DOIUrl":"10.1016/j.jnoncrysol.2025.123865","url":null,"abstract":"<div><div>The degree of disorder across the subnanometer scale of an oxide glass is largely governed by the relative propensities of its network formers (<span><math><mi>F</mi></math></span>) and modifiers <span><math><mrow><mo>(</mo><mi>M</mi><mo>)</mo></mrow></math></span> to coordinate the bridging oxygen (BO) and non-bridging oxygen (NBO) species, as well as the (non)preferential interlinking of the various network-forming polyhedra. This paper and its sequel examine the bonding-preference concept, which quantifies the degree of preference or reluctance of two atom species to interlink. Unified and consistent definitions of bonding preferences are presented along with critical reviews of previous reports in the field, which remain sparse due to the substantial experimental challenges to quantify bonding preference in glasses and rendering computational modeling the main tool. Because the preference/reluctance for bond formation marks the deviation from a statistical atom/ion intermixing, a rigorous formulation of the latter is required. Potential pitfalls for defining the statistical reference case are discussed. With particular focus on glasses with <span><math><mi>F</mi></math></span>={Al, B, Si} as network formers, this article targets the (relative) <span><math><mi>F</mi></math></span>–BO/NBO and <span><math><mi>M</mi></math></span>–BO/NBO bonding preferences pertaining to the first coordination shells of the {<span><math><mi>F</mi></math></span>, <span><math><mi>M</mi></math></span>, O} species in the glass, while the preferential <span><math><mi>F</mi></math></span>–O–<span><math><msup><mrow><mi>F</mi></mrow><mrow><mo>′</mo></mrow></msup></math></span> interlinking and <span><math><msup><mrow><mi>M</mi></mrow><mrow><mi>z</mi><mo>+</mo></mrow></msup></math></span>–<span><math><mi>F</mi></math></span>O<span><math><msub><mrow></mrow><mrow><mi>p</mi></mrow></msub></math></span> associations are examined in the sequel article.</div></div>","PeriodicalId":16461,"journal":{"name":"Journal of Non-crystalline Solids","volume":"673 ","pages":"Article 123865"},"PeriodicalIF":3.5,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681988","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-01DOI: 10.1016/j.jnoncrysol.2025.123900
Cheng Wang , Yanqing Fu , Chengwei Gao , Shiliang Kang , Linling Tan , Lingling Jiang , Zhongchao Wu , Shixun Dai , Changgui Lin
Acousto-optic (AO) devices have attracted significant attention in laser technology owing to their excellent light modulation capabilities through acoustic-optical interactions. However, significant challenges still exist for AO materials in balancing excellent AO properties with the thermal stability and damage resistance needed for high-power laser systems. Herein, a series of xGeS2-(100-x)As2S3 chalcogenide glass were developed, and the correlation between GeS2-induced structural modifications and thermal, mechanical and AO properties were comprehensively explored. The introduction of GeS2 leads to the gradual replacement of [AsS3] pyramids with more stable [GeS4] tetrahedra in the glass network, resulting in significantly enhanced glass network connectivity. The optimized 90GeS2–10As2S3 glass exhibits excellent AO properties, low thermos-optic coefficient, and high laser damage threshold, demonstrating distinct advantages over TeO2 crystal and commercially available As2S3, Ge33As12Se55 and Ge15Sb24S61 glasses, providing a new material option for the development of high-performance AO devices.
{"title":"Structural and near-infrared acousto-optic properties of GeS2-As2S3 chalcogenide glass","authors":"Cheng Wang , Yanqing Fu , Chengwei Gao , Shiliang Kang , Linling Tan , Lingling Jiang , Zhongchao Wu , Shixun Dai , Changgui Lin","doi":"10.1016/j.jnoncrysol.2025.123900","DOIUrl":"10.1016/j.jnoncrysol.2025.123900","url":null,"abstract":"<div><div>Acousto-optic (AO) devices have attracted significant attention in laser technology owing to their excellent light modulation capabilities through acoustic-optical interactions. However, significant challenges still exist for AO materials in balancing excellent AO properties with the thermal stability and damage resistance needed for high-power laser systems. Herein, a series of xGeS<sub>2</sub>-(100-x)As<sub>2</sub>S<sub>3</sub> chalcogenide glass were developed, and the correlation between GeS<sub>2</sub>-induced structural modifications and thermal, mechanical and AO properties were comprehensively explored. The introduction of GeS<sub>2</sub> leads to the gradual replacement of [AsS<sub>3</sub>] pyramids with more stable [GeS<sub>4</sub>] tetrahedra in the glass network, resulting in significantly enhanced glass network connectivity. The optimized 90GeS<sub>2</sub>–10As<sub>2</sub>S<sub>3</sub> glass exhibits excellent AO properties, low thermos-optic coefficient, and high laser damage threshold, demonstrating distinct advantages over TeO<sub>2</sub> crystal and commercially available As<sub>2</sub>S<sub>3</sub>, Ge<sub>33</sub>As<sub>12</sub>Se<sub>55</sub> and Ge<sub>15</sub>Sb<sub>24</sub>S<sub>61</sub> glasses, providing a new material option for the development of high-performance AO devices.</div></div>","PeriodicalId":16461,"journal":{"name":"Journal of Non-crystalline Solids","volume":"673 ","pages":"Article 123900"},"PeriodicalIF":3.5,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681984","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-29DOI: 10.1016/j.jnoncrysol.2025.123892
Yunliang Cui, Siwei Chen, Lufan Li, Xinquan Wang, Jiaying Liu
To elucidate how Ca2+ governs hydration and structural evolution in N-A-S-H gels, this study employs reactive molecular dynamics with ReaxFF simulating systems from calcium-free to full calcium substitution. Moderate calcium substitution (∼25 %) markedly accelerates early polycondensation, increases highly polymerized Si3 and Si4 fractions, and yields compact, continuous three-dimensional networks. Further calcium incorporation intensifies electrostatic shielding and coordination competition, weakening Si-O-(Si/Al) linkages and producing fragmented networks. Bond-order and geometry analyses reveal that Al-O bonds are longer than Si-O bonds, with increasing calcium shortening Al-O via enhanced electrostatic polarization; O-Si-O angles concentrate near 109.5°, while Si-O-Si peaks (∼140°) exhibit rightward shift and broadening with calcium, reflecting increased structural disorder; O-Al-O distributions broaden considerably, with five-coordinate aluminum comprising 65–80 % of environments. Nanoporosity evaluation shows calcium incorporation increases pore volume from ∼22 % (low substitution) to >28 % (high calcium), whereas optimal low-calcium systems exhibit smaller porosity and denser networks. These nanoscale characteristics directly correlate with macroscopic mechanical properties: optimal calcium substitution (∼25 %) balances accelerated polymerization with dense network formation, yielding superior load-bearing capacity and durability, while excessive calcium compromises structural integrity. Overall, appropriate Ca2+ levels promote framework formation through bridging and charge compensation, while excessive calcium suppresses cross-linking—thereby determining gel density, stability, and mechanical performance.
为了阐明Ca2+如何控制N-A-S-H凝胶中的水合作用和结构演化，本研究采用反应分子动力学和ReaxFF模拟系统，从无钙到全钙取代。适度的钙取代（~ 25%）显著加速了早期缩聚，增加了高度聚合的Si3和Si4馏分，并产生紧凑、连续的三维网络。钙的进一步掺入会加剧静电屏蔽和配位竞争，削弱Si- o -(Si/Al)键并产生碎片化网络。键序和几何分析表明，Al-O键比Si-O键长，钙的增加通过增强静电极化使Al-O缩短；O-Si-O角集中在109.5°附近，而Si-O-Si峰（~ 140°）随着钙的增加而向右移动和变宽，反映了结构无序性的增加；O-Al-O分布范围大大扩大，五坐标铝占环境的65 - 80%。纳米孔隙度评估显示，钙掺入使孔隙体积从22%（低取代）增加到28%（高钙），而最佳的低钙体系具有更小的孔隙度和更致密的网络。这些纳米级特征与宏观力学性能直接相关：最佳的钙取代（~ 25%）平衡了加速聚合和密集网络形成，产生了卓越的承载能力和耐久性，而过量的钙会损害结构完整性。总的来说，适当的Ca2+水平通过桥接和电荷补偿促进框架的形成，而过量的钙抑制交联，从而决定凝胶密度、稳定性和机械性能。
{"title":"Atomistic insights into the hydration behavior of N-A-S-H Gel via Ca2+ substitution: A molecular dynamics simulation study","authors":"Yunliang Cui, Siwei Chen, Lufan Li, Xinquan Wang, Jiaying Liu","doi":"10.1016/j.jnoncrysol.2025.123892","DOIUrl":"10.1016/j.jnoncrysol.2025.123892","url":null,"abstract":"<div><div>To elucidate how Ca<sup>2+</sup> governs hydration and structural evolution in N-A-S-H gels, this study employs reactive molecular dynamics with ReaxFF simulating systems from calcium-free to full calcium substitution. Moderate calcium substitution (∼25 %) markedly accelerates early polycondensation, increases highly polymerized Si<sup>3</sup> and Si<sup>4</sup> fractions, and yields compact, continuous three-dimensional networks. Further calcium incorporation intensifies electrostatic shielding and coordination competition, weakening Si-O-(Si/Al) linkages and producing fragmented networks. Bond-order and geometry analyses reveal that Al-O bonds are longer than Si-O bonds, with increasing calcium shortening Al-O via enhanced electrostatic polarization; O-Si-O angles concentrate near 109.5°, while Si-O-Si peaks (∼140°) exhibit rightward shift and broadening with calcium, reflecting increased structural disorder; O-Al-O distributions broaden considerably, with five-coordinate aluminum comprising 65–80 % of environments. Nanoporosity evaluation shows calcium incorporation increases pore volume from ∼22 % (low substitution) to >28 % (high calcium), whereas optimal low-calcium systems exhibit smaller porosity and denser networks. These nanoscale characteristics directly correlate with macroscopic mechanical properties: optimal calcium substitution (∼25 %) balances accelerated polymerization with dense network formation, yielding superior load-bearing capacity and durability, while excessive calcium compromises structural integrity. Overall, appropriate Ca<sup>2+</sup> levels promote framework formation through bridging and charge compensation, while excessive calcium suppresses cross-linking—thereby determining gel density, stability, and mechanical performance.</div></div>","PeriodicalId":16461,"journal":{"name":"Journal of Non-crystalline Solids","volume":"673 ","pages":"Article 123892"},"PeriodicalIF":3.5,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145616010","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-28DOI: 10.1016/j.jnoncrysol.2025.123872
Nikolay V. Alekseechkin
Analysis of experimental DSC and Avrami curves for the crystallization of metallic glasses based on a new theoretical model of grain-boundary nucleated transformations provides insight into their structure on a mesoscopic scale. In many cases, calorimetric measurements yield two-peak non-isothermal DSC curves and three-stage Avrami plots. It is shown that such shapes of these curves demonstrate nucleation at grain boundaries and thus indicate the grain structure of metallic glasses, which refutes the generally accepted idea of glass as a homogeneous “frozen” liquid obtained as a result of avoiding crystallization. To clarify the conditions for obtaining the indicated curves, isothermal and non-isothermal surface-nucleated crystallization of a spherical particle is considered within the framework of a simple analytical model of nucleation and growth. It is shown that both of these manifestations of grain structure in calorimetric experiments occur only in a certain range of values of the control parameter. In addition, non-isothermality plays a key role in the appearance of two-peak DSC curves.
{"title":"Crystallization of metallic glass as a grain-boundary nucleated process: experimental and theoretical evidence for the grain structure of metallic glasses","authors":"Nikolay V. Alekseechkin","doi":"10.1016/j.jnoncrysol.2025.123872","DOIUrl":"10.1016/j.jnoncrysol.2025.123872","url":null,"abstract":"<div><div>Analysis of experimental DSC and Avrami curves for the crystallization of metallic glasses based on a new theoretical model of grain-boundary nucleated transformations provides insight into their structure on a mesoscopic scale. In many cases, calorimetric measurements yield two-peak non-isothermal DSC curves and three-stage Avrami plots. It is shown that such shapes of these curves demonstrate nucleation at grain boundaries and thus indicate the grain structure of metallic glasses, which refutes the generally accepted idea of glass as a homogeneous “frozen” liquid obtained as a result of avoiding crystallization. To clarify the conditions for obtaining the indicated curves, isothermal and non-isothermal surface-nucleated crystallization of a spherical particle is considered within the framework of a simple analytical model of nucleation and growth. It is shown that both of these manifestations of grain structure in calorimetric experiments occur only in a certain range of values of the control parameter. In addition, non-isothermality plays a key role in the appearance of two-peak DSC curves.</div></div>","PeriodicalId":16461,"journal":{"name":"Journal of Non-crystalline Solids","volume":"673 ","pages":"Article 123872"},"PeriodicalIF":3.5,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145616009","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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