Atolo A. Tuinukuafe , David X. Rademacher , Tina M. Nenoff , Jessica M. Rimsza
{"title":"Enhanced pozzolanic reactivity in hydrogen-form zeolites as supplementary cementitious materials","authors":"Atolo A. Tuinukuafe , David X. Rademacher , Tina M. Nenoff , Jessica M. Rimsza","doi":"10.1016/j.cemconcomp.2024.105790","DOIUrl":null,"url":null,"abstract":"<div><div>Pozzolans rich in silica and alumina react with lime to form cementing compounds and are incorporated into portland cement as supplementary cementitious materials (SCMs). However, pozzolanic reactions progress slower than portland cement hydration, limiting their use in modern construction due to insufficient early-age strength. Hence, alternative SCMs that enable faster pozzolanic reactions are necessary including synthetic zeolites, which have high surface areas and compositional purity that indicate the possibility of rapid pozzolanic reactivity. Synthetic zeolites with varying cation composition (Na-zeolite, H-zeolite), SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> ratio, and framework type were evaluated for pozzolanic reactivity via Ca(OH)<sub>2</sub> consumption using ion exchange and in-situ X-ray diffraction experiments. Na-zeolites exhibited limited exchange reactions with KOH and Ca(OH)<sub>2</sub> due to the occupancy of acid sites by Na<sup>+</sup> and hydroxyl groups. Meanwhile, H-zeolites readily adsorbed K<sup>+</sup> and Ca<sup>2+</sup> from a hydroxide solution by exchanging cations with H<sup>+</sup> at Brønsted acid sites or cation adsorption at vacant acid sites. By adsorbing cations, the H-zeolite reduced the pH and increased Ca<sup>2+</sup> solubility to promote pozzolanic reactions in a system where Ca(OH)<sub>2</sub> dissolution/diffusion was a rate limiting factor. High H-zeolite reactivity resulted in 0.8 g of Ca(OH)<sub>2</sub> consumed per 1 g of zeolites after 16 h of reaction versus 0.4 g of Ca(OH)<sub>2</sub> consumed per 1 g of Na-zeolite. The H-zeolite modulated the pore fluid alkalinity and created a low-density amorphous silicate phase via mechanisms analogous to two-step C-S-H nucleation experiments. Controlling these reaction mechanisms is key to developing next generation pozzolanic cementitious systems with comparable hydration rates to portland cement.</div></div>","PeriodicalId":9865,"journal":{"name":"Cement & concrete composites","volume":"154 ","pages":"Article 105790"},"PeriodicalIF":10.8000,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Cement & concrete composites","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0958946524003639","RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CONSTRUCTION & BUILDING TECHNOLOGY","Score":null,"Total":0}
引用次数: 0
Abstract
Pozzolans rich in silica and alumina react with lime to form cementing compounds and are incorporated into portland cement as supplementary cementitious materials (SCMs). However, pozzolanic reactions progress slower than portland cement hydration, limiting their use in modern construction due to insufficient early-age strength. Hence, alternative SCMs that enable faster pozzolanic reactions are necessary including synthetic zeolites, which have high surface areas and compositional purity that indicate the possibility of rapid pozzolanic reactivity. Synthetic zeolites with varying cation composition (Na-zeolite, H-zeolite), SiO2/Al2O3 ratio, and framework type were evaluated for pozzolanic reactivity via Ca(OH)2 consumption using ion exchange and in-situ X-ray diffraction experiments. Na-zeolites exhibited limited exchange reactions with KOH and Ca(OH)2 due to the occupancy of acid sites by Na+ and hydroxyl groups. Meanwhile, H-zeolites readily adsorbed K+ and Ca2+ from a hydroxide solution by exchanging cations with H+ at Brønsted acid sites or cation adsorption at vacant acid sites. By adsorbing cations, the H-zeolite reduced the pH and increased Ca2+ solubility to promote pozzolanic reactions in a system where Ca(OH)2 dissolution/diffusion was a rate limiting factor. High H-zeolite reactivity resulted in 0.8 g of Ca(OH)2 consumed per 1 g of zeolites after 16 h of reaction versus 0.4 g of Ca(OH)2 consumed per 1 g of Na-zeolite. The H-zeolite modulated the pore fluid alkalinity and created a low-density amorphous silicate phase via mechanisms analogous to two-step C-S-H nucleation experiments. Controlling these reaction mechanisms is key to developing next generation pozzolanic cementitious systems with comparable hydration rates to portland cement.
期刊介绍:
Cement & concrete composites focuses on advancements in cement-concrete composite technology and the production, use, and performance of cement-based construction materials. It covers a wide range of materials, including fiber-reinforced composites, polymer composites, ferrocement, and those incorporating special aggregates or waste materials. Major themes include microstructure, material properties, testing, durability, mechanics, modeling, design, fabrication, and practical applications. The journal welcomes papers on structural behavior, field studies, repair and maintenance, serviceability, and sustainability. It aims to enhance understanding, provide a platform for unconventional materials, promote low-cost energy-saving materials, and bridge the gap between materials science, engineering, and construction. Special issues on emerging topics are also published to encourage collaboration between materials scientists, engineers, designers, and fabricators.