{"title":"溶质不会结晶!相图揭开结晶 \"魔法 \"的神秘面纱","authors":"James D. Martin","doi":"10.1016/j.matt.2024.08.011","DOIUrl":null,"url":null,"abstract":"<div><div>Crystals are ubiquitous in nature and technology. Despite the importance of understanding mechanisms of crystallization, conventional theories have proved inadequate. Consideration of phase diagrams reveals that these theories’ failings result from thermodynamically invalid assumptions, including that solutes are the crystallizing phase and that <em>K</em><sub><em>sp</em></sub> describes solubility. Thermodynamics requires that the nutrient (solvent) be the crystallizing phase. This perspective provides tools to rigorously characterize a phase diagram to explicitly determine the components of the crystallizing system and the influence of the diluent on the liquidus of the nutrient. It is shown that diluents can change the liquidus of the nutrient but do not participate in the rate-determining step of crystal growth. The rate-determining step is found to be the propagation of the crystalline phase boundary through a melt-like intermediate. This transition-zone theory model accurately describes crystal growth rates for all concentration-temperature conditions and resolves “riddles” of crystal morphology and growth rates.</div></div>","PeriodicalId":388,"journal":{"name":"Matter","volume":"7 10","pages":"Pages 3290-3316"},"PeriodicalIF":17.3000,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Solutes don’t crystallize! Insights from phase diagrams demystify the “magic” of crystallization\",\"authors\":\"James D. Martin\",\"doi\":\"10.1016/j.matt.2024.08.011\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Crystals are ubiquitous in nature and technology. Despite the importance of understanding mechanisms of crystallization, conventional theories have proved inadequate. Consideration of phase diagrams reveals that these theories’ failings result from thermodynamically invalid assumptions, including that solutes are the crystallizing phase and that <em>K</em><sub><em>sp</em></sub> describes solubility. Thermodynamics requires that the nutrient (solvent) be the crystallizing phase. This perspective provides tools to rigorously characterize a phase diagram to explicitly determine the components of the crystallizing system and the influence of the diluent on the liquidus of the nutrient. It is shown that diluents can change the liquidus of the nutrient but do not participate in the rate-determining step of crystal growth. The rate-determining step is found to be the propagation of the crystalline phase boundary through a melt-like intermediate. This transition-zone theory model accurately describes crystal growth rates for all concentration-temperature conditions and resolves “riddles” of crystal morphology and growth rates.</div></div>\",\"PeriodicalId\":388,\"journal\":{\"name\":\"Matter\",\"volume\":\"7 10\",\"pages\":\"Pages 3290-3316\"},\"PeriodicalIF\":17.3000,\"publicationDate\":\"2024-10-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Matter\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2590238524004430\",\"RegionNum\":1,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Matter","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2590238524004430","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
Solutes don’t crystallize! Insights from phase diagrams demystify the “magic” of crystallization
Crystals are ubiquitous in nature and technology. Despite the importance of understanding mechanisms of crystallization, conventional theories have proved inadequate. Consideration of phase diagrams reveals that these theories’ failings result from thermodynamically invalid assumptions, including that solutes are the crystallizing phase and that Ksp describes solubility. Thermodynamics requires that the nutrient (solvent) be the crystallizing phase. This perspective provides tools to rigorously characterize a phase diagram to explicitly determine the components of the crystallizing system and the influence of the diluent on the liquidus of the nutrient. It is shown that diluents can change the liquidus of the nutrient but do not participate in the rate-determining step of crystal growth. The rate-determining step is found to be the propagation of the crystalline phase boundary through a melt-like intermediate. This transition-zone theory model accurately describes crystal growth rates for all concentration-temperature conditions and resolves “riddles” of crystal morphology and growth rates.
期刊介绍:
Matter, a monthly journal affiliated with Cell, spans the broad field of materials science from nano to macro levels,covering fundamentals to applications. Embracing groundbreaking technologies,it includes full-length research articles,reviews, perspectives,previews, opinions, personnel stories, and general editorial content.
Matter aims to be the primary resource for researchers in academia and industry, inspiring the next generation of materials scientists.