{"title":"偏磷酸钴锌和焦磷酸盐玻璃中的钴:结构、配位和热性能","authors":"Jana Holubová, Zdeněk Černošek","doi":"10.1016/j.jnoncrysol.2025.123782","DOIUrl":null,"url":null,"abstract":"<div><div>The interaction of cobalt in a wide compositional range was studied in Co-Zn phosphate glasses. Metaphosphate glasses xCoO-(50-x)ZnO-50P<sub>2</sub>O<sub>5</sub>, i.e. glasses with the same anion, and glasses in which the anion simultaneously changes from metaphosphate to pyrophosphate with increasing cobalt concentration, <em>meta-pyro</em> series, yCoO-(50–0.75y)ZnO-(50–0.25y)P<sub>2</sub>O<sub>5</sub>, were prepared. XRF, Raman spectra and <sup>31</sup>P MAS NMR confirmed the desired chemical composition of all the prepared glasses. The electronic spectra demonstrated both the tetrahedral and octahedral coordination of the Co(+II). The combination with Raman spectroscopy showed a predominant tetrahedral coordination. A simple chemical model of <em>meta-pyro</em> series was proposed. The Co-O(P) bond was found to be considerably polar, thereby increasing the density of weak interactions in the glass network, which in turn caused an increase in T<sub>g</sub> with increasing Co content in both series. It was determined that the coefficient of thermal expansion increases with rising cobalt concentration. This is related to the assumption of a higher amplitude of vibrations of the Co-O(P) bond compared to the Zn-O(P) bond, indicating the increasing asymmetry of the Morse potential. The compositional dependence of density and molar volume indicates the increasing compactness of the glass structure with increasing cobalt content.</div></div>","PeriodicalId":16461,"journal":{"name":"Journal of Non-crystalline Solids","volume":"668 ","pages":"Article 123782"},"PeriodicalIF":3.5000,"publicationDate":"2025-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Cobalt in Co-Zn metaphosphate and pyrophosphate glasses: Structure, coordination and thermal properties\",\"authors\":\"Jana Holubová, Zdeněk Černošek\",\"doi\":\"10.1016/j.jnoncrysol.2025.123782\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The interaction of cobalt in a wide compositional range was studied in Co-Zn phosphate glasses. Metaphosphate glasses xCoO-(50-x)ZnO-50P<sub>2</sub>O<sub>5</sub>, i.e. glasses with the same anion, and glasses in which the anion simultaneously changes from metaphosphate to pyrophosphate with increasing cobalt concentration, <em>meta-pyro</em> series, yCoO-(50–0.75y)ZnO-(50–0.25y)P<sub>2</sub>O<sub>5</sub>, were prepared. XRF, Raman spectra and <sup>31</sup>P MAS NMR confirmed the desired chemical composition of all the prepared glasses. The electronic spectra demonstrated both the tetrahedral and octahedral coordination of the Co(+II). The combination with Raman spectroscopy showed a predominant tetrahedral coordination. A simple chemical model of <em>meta-pyro</em> series was proposed. The Co-O(P) bond was found to be considerably polar, thereby increasing the density of weak interactions in the glass network, which in turn caused an increase in T<sub>g</sub> with increasing Co content in both series. It was determined that the coefficient of thermal expansion increases with rising cobalt concentration. This is related to the assumption of a higher amplitude of vibrations of the Co-O(P) bond compared to the Zn-O(P) bond, indicating the increasing asymmetry of the Morse potential. The compositional dependence of density and molar volume indicates the increasing compactness of the glass structure with increasing cobalt content.</div></div>\",\"PeriodicalId\":16461,\"journal\":{\"name\":\"Journal of Non-crystalline Solids\",\"volume\":\"668 \",\"pages\":\"Article 123782\"},\"PeriodicalIF\":3.5000,\"publicationDate\":\"2025-09-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Non-crystalline Solids\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0022309325003989\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"MATERIALS SCIENCE, CERAMICS\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Non-crystalline Solids","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022309325003989","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, CERAMICS","Score":null,"Total":0}
引用次数: 0
摘要
研究了钴在不同组分范围内与磷酸钴锌玻璃的相互作用。制备了具有相同阴离子的偏磷酸玻璃xCoO-(50-x)ZnO- 50p2o5,以及阴离子随钴浓度增加而同时由偏磷酸变为焦磷酸的偏磷酸玻璃yCoO-(50-0.75y)ZnO-(50-0.25y)P2O5。XRF,拉曼光谱和31P MAS NMR证实了所有制备的玻璃所需的化学成分。电子能谱显示Co(+II)具有四面体配位和八面体配位。拉曼光谱的结合显示出主要的四面体配位。提出了一种简单的元热系化学模型。Co- o (P)键是相当极性的,从而增加了玻璃网络中弱相互作用的密度,这反过来又导致Tg随两个系列中Co含量的增加而增加。结果表明,随着钴浓度的升高,热膨胀系数增大。这与Co-O(P)键比Zn-O(P)键的振动振幅更高的假设有关,表明莫尔斯势的不对称性增加。密度和摩尔体积的组分依赖性表明,随着钴含量的增加,玻璃结构的致密性增加。
Cobalt in Co-Zn metaphosphate and pyrophosphate glasses: Structure, coordination and thermal properties
The interaction of cobalt in a wide compositional range was studied in Co-Zn phosphate glasses. Metaphosphate glasses xCoO-(50-x)ZnO-50P2O5, i.e. glasses with the same anion, and glasses in which the anion simultaneously changes from metaphosphate to pyrophosphate with increasing cobalt concentration, meta-pyro series, yCoO-(50–0.75y)ZnO-(50–0.25y)P2O5, were prepared. XRF, Raman spectra and 31P MAS NMR confirmed the desired chemical composition of all the prepared glasses. The electronic spectra demonstrated both the tetrahedral and octahedral coordination of the Co(+II). The combination with Raman spectroscopy showed a predominant tetrahedral coordination. A simple chemical model of meta-pyro series was proposed. The Co-O(P) bond was found to be considerably polar, thereby increasing the density of weak interactions in the glass network, which in turn caused an increase in Tg with increasing Co content in both series. It was determined that the coefficient of thermal expansion increases with rising cobalt concentration. This is related to the assumption of a higher amplitude of vibrations of the Co-O(P) bond compared to the Zn-O(P) bond, indicating the increasing asymmetry of the Morse potential. The compositional dependence of density and molar volume indicates the increasing compactness of the glass structure with increasing cobalt content.
期刊介绍:
The Journal of Non-Crystalline Solids publishes review articles, research papers, and Letters to the Editor on amorphous and glassy materials, including inorganic, organic, polymeric, hybrid and metallic systems. Papers on partially glassy materials, such as glass-ceramics and glass-matrix composites, and papers involving the liquid state are also included in so far as the properties of the liquid are relevant for the formation of the solid.
In all cases the papers must demonstrate both novelty and importance to the field, by way of significant advances in understanding or application of non-crystalline solids; in the case of Letters, a compelling case must also be made for expedited handling.