{"title":"三元 CaO-Al2O3-Fe2O3 体系中钙铝铁氧体在固相反应过程中的形成","authors":"Svetlana V. Samchenko, Andrey V. Korshunov","doi":"10.1016/j.conbuildmat.2024.139117","DOIUrl":null,"url":null,"abstract":"<div><div>The ferrite phase in the cement composition has a reduced heat release during hydration, improves mechanical properties and increases the corrosion resistance of cement materials. In this article, the formation of C<sub>2</sub>A<sub>x</sub>F<sub>1–x</sub>-type aluminoferrites in the CaO–Al<sub>2</sub>O<sub>3</sub>–Fe<sub>2</sub>O<sub>3</sub> system during solid-phase reactions was studied. A system of empirical equations has been proposed that allows calculating the thermodynamic functions (Δ<sub>f</sub><em>H</em>°<sub>298</sub>, Δ<sub>f</sub><em>G</em>°<sub>298</sub>) of the formation of calcium aluminoferrites of any composition within a continuous series C<sub>2</sub>A<sub>0</sub><sub>.</sub><sub>667</sub>F<sub>0</sub><sub>.</sub><sub>333</sub> (C<sub>6</sub>A<sub>2</sub>F) – C<sub>2</sub>F. Analysis of the various pathways of aluminoferrites formation has been conducted, taking into consideration the formation of intermediate phases in the ternary system. Based on a comparison of experimental data for mixtures of C+F, C+A, and C+A+F, a temperature sequence for phase formation (C<sub>2</sub>F, CF, amorphous [CA]<sub>am</sub>, C<sub>2</sub>(A)F, CA, C<sub>12</sub>A<sub>7</sub>, C<sub>2</sub>A<sub>x</sub>F<sub>1–x</sub>, eutectic liquid) in ternary oxide systems has been established. It has been shown that the amorphous aluminate phase present in the reaction system within the temperature range of 850–1100°C plays a crucial role in the formation of aluminoferrites. Among the investigated ternary oxide mixtures, whose initial composition corresponds to the stoichiometries of C<sub>6</sub>A<sub>2</sub>F, C<sub>4</sub>AF, C<sub>6</sub>AF<sub>2</sub>, and C<sub>8</sub>AF<sub>3</sub>, only a certain aluminoferrite (brownmillerite), with a sufficiently high yield (∼53 wt% at 1200 °C), is formed in a 4 C+A+F mixture. An explanation has been proposed for the similarity in morphology between the sintered α-Fe<sub>2</sub>O<sub>3</sub> and the calcined products of the C+F and C+A+F oxide mixtures when <em>T</em>>1000°C. The results of this work can be used to improve existing technologies and develop new methods for the production of iron-rich binders and additives based on calcium ferrites and aluminoferrites. The results of this work allow us to clarify the patterns of phase formation of calcium aluminoferrites under conditions of solid-phase reactions.</div></div>","PeriodicalId":288,"journal":{"name":"Construction and Building Materials","volume":"455 ","pages":"Article 139117"},"PeriodicalIF":7.4000,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Formation of calcium aluminoferrites in the ternary CaO–Al2O3–Fe2O3 system during solid-phase reactions\",\"authors\":\"Svetlana V. Samchenko, Andrey V. Korshunov\",\"doi\":\"10.1016/j.conbuildmat.2024.139117\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The ferrite phase in the cement composition has a reduced heat release during hydration, improves mechanical properties and increases the corrosion resistance of cement materials. In this article, the formation of C<sub>2</sub>A<sub>x</sub>F<sub>1–x</sub>-type aluminoferrites in the CaO–Al<sub>2</sub>O<sub>3</sub>–Fe<sub>2</sub>O<sub>3</sub> system during solid-phase reactions was studied. A system of empirical equations has been proposed that allows calculating the thermodynamic functions (Δ<sub>f</sub><em>H</em>°<sub>298</sub>, Δ<sub>f</sub><em>G</em>°<sub>298</sub>) of the formation of calcium aluminoferrites of any composition within a continuous series C<sub>2</sub>A<sub>0</sub><sub>.</sub><sub>667</sub>F<sub>0</sub><sub>.</sub><sub>333</sub> (C<sub>6</sub>A<sub>2</sub>F) – C<sub>2</sub>F. Analysis of the various pathways of aluminoferrites formation has been conducted, taking into consideration the formation of intermediate phases in the ternary system. Based on a comparison of experimental data for mixtures of C+F, C+A, and C+A+F, a temperature sequence for phase formation (C<sub>2</sub>F, CF, amorphous [CA]<sub>am</sub>, C<sub>2</sub>(A)F, CA, C<sub>12</sub>A<sub>7</sub>, C<sub>2</sub>A<sub>x</sub>F<sub>1–x</sub>, eutectic liquid) in ternary oxide systems has been established. It has been shown that the amorphous aluminate phase present in the reaction system within the temperature range of 850–1100°C plays a crucial role in the formation of aluminoferrites. Among the investigated ternary oxide mixtures, whose initial composition corresponds to the stoichiometries of C<sub>6</sub>A<sub>2</sub>F, C<sub>4</sub>AF, C<sub>6</sub>AF<sub>2</sub>, and C<sub>8</sub>AF<sub>3</sub>, only a certain aluminoferrite (brownmillerite), with a sufficiently high yield (∼53 wt% at 1200 °C), is formed in a 4 C+A+F mixture. An explanation has been proposed for the similarity in morphology between the sintered α-Fe<sub>2</sub>O<sub>3</sub> and the calcined products of the C+F and C+A+F oxide mixtures when <em>T</em>>1000°C. The results of this work can be used to improve existing technologies and develop new methods for the production of iron-rich binders and additives based on calcium ferrites and aluminoferrites. The results of this work allow us to clarify the patterns of phase formation of calcium aluminoferrites under conditions of solid-phase reactions.</div></div>\",\"PeriodicalId\":288,\"journal\":{\"name\":\"Construction and Building Materials\",\"volume\":\"455 \",\"pages\":\"Article 139117\"},\"PeriodicalIF\":7.4000,\"publicationDate\":\"2024-11-16\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Construction and Building Materials\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0950061824042594\",\"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}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Construction and Building Materials","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0950061824042594","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}
Formation of calcium aluminoferrites in the ternary CaO–Al2O3–Fe2O3 system during solid-phase reactions
The ferrite phase in the cement composition has a reduced heat release during hydration, improves mechanical properties and increases the corrosion resistance of cement materials. In this article, the formation of C2AxF1–x-type aluminoferrites in the CaO–Al2O3–Fe2O3 system during solid-phase reactions was studied. A system of empirical equations has been proposed that allows calculating the thermodynamic functions (ΔfH°298, ΔfG°298) of the formation of calcium aluminoferrites of any composition within a continuous series C2A0.667F0.333 (C6A2F) – C2F. Analysis of the various pathways of aluminoferrites formation has been conducted, taking into consideration the formation of intermediate phases in the ternary system. Based on a comparison of experimental data for mixtures of C+F, C+A, and C+A+F, a temperature sequence for phase formation (C2F, CF, amorphous [CA]am, C2(A)F, CA, C12A7, C2AxF1–x, eutectic liquid) in ternary oxide systems has been established. It has been shown that the amorphous aluminate phase present in the reaction system within the temperature range of 850–1100°C plays a crucial role in the formation of aluminoferrites. Among the investigated ternary oxide mixtures, whose initial composition corresponds to the stoichiometries of C6A2F, C4AF, C6AF2, and C8AF3, only a certain aluminoferrite (brownmillerite), with a sufficiently high yield (∼53 wt% at 1200 °C), is formed in a 4 C+A+F mixture. An explanation has been proposed for the similarity in morphology between the sintered α-Fe2O3 and the calcined products of the C+F and C+A+F oxide mixtures when T>1000°C. The results of this work can be used to improve existing technologies and develop new methods for the production of iron-rich binders and additives based on calcium ferrites and aluminoferrites. The results of this work allow us to clarify the patterns of phase formation of calcium aluminoferrites under conditions of solid-phase reactions.
期刊介绍:
Construction and Building Materials offers an international platform for sharing innovative and original research and development in the realm of construction and building materials, along with their practical applications in new projects and repair practices. The journal publishes a diverse array of pioneering research and application papers, detailing laboratory investigations and, to a limited extent, numerical analyses or reports on full-scale projects. Multi-part papers are discouraged.
Additionally, Construction and Building Materials features comprehensive case studies and insightful review articles that contribute to new insights in the field. Our focus is on papers related to construction materials, excluding those on structural engineering, geotechnics, and unbound highway layers. Covered materials and technologies encompass cement, concrete reinforcement, bricks and mortars, additives, corrosion technology, ceramics, timber, steel, polymers, glass fibers, recycled materials, bamboo, rammed earth, non-conventional building materials, bituminous materials, and applications in railway materials.