Elena Leonidovna Gromnitskaya, Igor Vladimirovich Danilov, Vadim Veniaminovich Brazhkin
{"title":"高压下的多元醇:弹性特性的超声波对比研究","authors":"Elena Leonidovna Gromnitskaya, Igor Vladimirovich Danilov, Vadim Veniaminovich Brazhkin","doi":"10.1039/d4cp03667k","DOIUrl":null,"url":null,"abstract":"We carried out an experimental ultrasonic study of polyhydric alcohols with the general chemical formula C<small><sub>n</sub></small>H<small><sub>n+2</sub></small>(OH)<small><sub>n</sub></small> with an increasing number of OH groups: glycerol (<em>n</em>=3), erythritol (<em>n</em>=4), xylitol (<em>n</em>=5), sorbitol (<em>n</em>=6). The baric and temperature dependences of the elastic characteristics of these substances in the crystalline and glassy states were studied both under isothermal compression up to 1 GPa and during the isobaric heating of 77-295 K. For glycerol, glasses were obtained at different cooling rates, glass-liquid transitions were studied at different pressures. All the studied glasses have lower elastic moduli than the same substances in the crystalline state at the same pressure-temperature conditions. We obtained a cascade of glass-supercooled liquid-crystal transitions during heating of glassy erythritol. In the series of substances with <em>n</em>=3,4,5 the bulk moduli show a tendency to decrease with increasing <em>n</em>. However, sorbitol (<em>n</em>=6) unexpectedly has the highest elastic moduli among the studied substances in both the glassy and crystalline states. The studied glassformers show a general tendency to increase the glass transition temperature T<small><sub>g</sub></small> and the fragility coefficient <em>m</em> with increasing <em>n</em>.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"76 1","pages":""},"PeriodicalIF":2.9000,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Polyhydric alcohols under high pressure: comparative ultrasonic study of elastic properties\",\"authors\":\"Elena Leonidovna Gromnitskaya, Igor Vladimirovich Danilov, Vadim Veniaminovich Brazhkin\",\"doi\":\"10.1039/d4cp03667k\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"We carried out an experimental ultrasonic study of polyhydric alcohols with the general chemical formula C<small><sub>n</sub></small>H<small><sub>n+2</sub></small>(OH)<small><sub>n</sub></small> with an increasing number of OH groups: glycerol (<em>n</em>=3), erythritol (<em>n</em>=4), xylitol (<em>n</em>=5), sorbitol (<em>n</em>=6). The baric and temperature dependences of the elastic characteristics of these substances in the crystalline and glassy states were studied both under isothermal compression up to 1 GPa and during the isobaric heating of 77-295 K. For glycerol, glasses were obtained at different cooling rates, glass-liquid transitions were studied at different pressures. All the studied glasses have lower elastic moduli than the same substances in the crystalline state at the same pressure-temperature conditions. We obtained a cascade of glass-supercooled liquid-crystal transitions during heating of glassy erythritol. In the series of substances with <em>n</em>=3,4,5 the bulk moduli show a tendency to decrease with increasing <em>n</em>. However, sorbitol (<em>n</em>=6) unexpectedly has the highest elastic moduli among the studied substances in both the glassy and crystalline states. The studied glassformers show a general tendency to increase the glass transition temperature T<small><sub>g</sub></small> and the fragility coefficient <em>m</em> with increasing <em>n</em>.\",\"PeriodicalId\":99,\"journal\":{\"name\":\"Physical Chemistry Chemical Physics\",\"volume\":\"76 1\",\"pages\":\"\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2024-11-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Physical Chemistry Chemical Physics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4cp03667k\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical Chemistry Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4cp03667k","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
我们对化学通式为 CnHn+2(OH)n,且羟基数目不断增加的多元醇进行了超声波实验研究:甘油(n=3)、赤藓糖醇(n=4)、木糖醇(n=5)和山梨醇(n=6)。研究了这些物质在结晶和玻璃状态下的弹性特征的巴氏和温度依赖性,包括在等温压缩至 1 GPa 和在 77-295 K 等压加热时的弹性特征。对于甘油,在不同的冷却速率下获得了玻璃,在不同的压力下研究了玻璃-液体转变。在相同的压力-温度条件下,所有研究的玻璃的弹性模量都低于结晶状态下的相同物质。在加热赤藓糖醇的过程中,我们获得了玻璃-过冷液晶转变的级联。在 n=3、4、5 的一系列物质中,随着 n 的增加,体积模量呈下降趋势。然而,在所研究的物质中,山梨醇(n=6)在玻璃态和结晶态的弹性模量都出乎意料地最高。所研究的玻璃转化物显示出玻璃转化温度 Tg 和脆性系数 m 随 n 的增大而增大的普遍趋势。
Polyhydric alcohols under high pressure: comparative ultrasonic study of elastic properties
We carried out an experimental ultrasonic study of polyhydric alcohols with the general chemical formula CnHn+2(OH)n with an increasing number of OH groups: glycerol (n=3), erythritol (n=4), xylitol (n=5), sorbitol (n=6). The baric and temperature dependences of the elastic characteristics of these substances in the crystalline and glassy states were studied both under isothermal compression up to 1 GPa and during the isobaric heating of 77-295 K. For glycerol, glasses were obtained at different cooling rates, glass-liquid transitions were studied at different pressures. All the studied glasses have lower elastic moduli than the same substances in the crystalline state at the same pressure-temperature conditions. We obtained a cascade of glass-supercooled liquid-crystal transitions during heating of glassy erythritol. In the series of substances with n=3,4,5 the bulk moduli show a tendency to decrease with increasing n. However, sorbitol (n=6) unexpectedly has the highest elastic moduli among the studied substances in both the glassy and crystalline states. The studied glassformers show a general tendency to increase the glass transition temperature Tg and the fragility coefficient m with increasing n.
期刊介绍:
Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions.
The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.