离子固溶对阿利特介稳结构及性能的影响
摘要
硅酸三钙(C3S)的固溶体阿利特是硅酸盐水泥熟料的最主要矿物，决定着熟料强度高低。深入研究离子固溶对阿利特结构及水化硬化性能的影响，对提高硅酸盐水泥强度具有重要意义。本文采用XRD结合Rietveld方法、热释光、微量热仪、FTIR、DSC、ICP-OES及SAED等，以合成阿利特单矿为研究对象，研究了Na~+、Mg~(2+)等离子尤其多离子复合效应对阿利特结构及性能的影响及关系。
从离子的化学结构出发，归纳并提出结构差异因子D，发现离子取代位置依D值由Ca至Si递变性变化，稳定C3S多晶态范围呈类“几”字形规律；基于此，提出了离子稳定C3S高温型由离子固溶所致晶格扭曲畸变，阻碍原子位移相变所致，且进一步的实验验证了此规律和机制。
对Na~+、Al~(3+)等离子单掺的研究发现，C3S晶格常数随离子固溶量线性变化。高掺量Mg和Ba可分别稳定M3和T3型；Al高掺量时取代Si比例增加并稳定T3型。碱金属和Al~(3+)离子异价置换形成空位缺陷，显著提高C3S早期水化活性。
Na~+、Mg~(2+)等七种典型离子复合掺杂主要稳定阿利特为M3型，Mg~(2+)和Al~(3+)，尤其P5+对高温型稳定能力最强。不含Mg或Al阿利特以T3型为主；P2O5≥0.5%(质量分数，下同)时，以R型为主。阿利特晶格常数随离子固溶量线性变化，并在晶型相界点、固溶极限或固溶机理改变处存在拐点，符合Vegard固溶体定律。Al约1/3取代Ca，2/3取代Si；Fe2O3＜0.4%时，Fe取代Ca，＞0.4%时，取代Ca和Si。无论取代Ca还是Si，固溶离子均不影响[SiO4]四面体配位价键结构。随阿利特结构对称性提高，[SiO4]四面体对称性提高，自T3型开始，基本达正四面体对称结构。阿利特结构介稳性与晶型及固溶离子种类及含量有关。
多离子复合掺杂阿利特活性较纯C3S高，但主水化反应延缓。异价置换离子形成缺陷复杂，对阿利特缺陷特征影响大，对水化动力学过程影响更显著，且缺陷类型比浓度的影响更重要。Fe及P尤其是Fe对水化影响最大，Fe使早期活性显著降低，诱导期延长，水化延缓。在晶型相界处，阿利特原始热释光强度突变，同晶型阿利特原始热释光强度与水化放热活性呈相关性，并主要体现在化学反应控制过程，这与以俘获电子形式亚稳储藏能量向化学能的转化有关。
阿利特晶型及活性受煅烧温度及冷却速率影响。经700和800℃热处理M3型阿利特转变为T3型。靠近分解温度煅烧的阿利特活性高，尤其1350℃热处理呈现高活性和热释光性，与1350℃稍高于分解温度，且十分接近泰曼温度有关。
MgO≥1%时，阿利特易磨性显著降低，强度下降；若不考虑离子固溶的影响，本研究涉及的R型阿利特强度最高，三斜T2、T3以及单斜M3型强度相近。
Tricalcium silicate (C3S) solid solutions known as alites are the principle phaseof clinker, responsible for strength development. Therefore, it is important to study theeffects of substituents on the metastable structure and hydraulic properties of alite. Inthis dissertation, the effects of foreign ions doping such as Na~+、Mg~(2+)etc. especiallytheir combined doping on the crystal structure and property were studied throughsynthetic alites by XRD with the Rietveld method, petrographic analysis,thermoluminescence, isothermal calorimetry, FTIR, DSC, ICP-OES, and SAED.
Based on ions’ chemical structure, a quantity called structure difference factor D(referred to Ca~(2+)) was defined. The substitution position changed gradually from Ca toSi with the increase of D. The stabilization range of high temperature polymorphs ofC3S exhibited “几” font with D. Based on this result, it is believed that thestabilization of high temperature polymorphs of C3S was due to the distortion in thestructure caused by ionic substitution, which could block atomic displacement and goagainst phase transformation. The ion-stabilization law and mechanism were provedby the further experiments.
The effects of single doping with Na~+, Al~(3+)etc. on the structure and property ofC3S were investigated. It was found that the lattice parameters of C3S were relatedlinearly to the amount of substituent ions. Mg~(2+)and Ba~(2+)favoured the stabilization ofM3and T3-type alite respectively at high concentration. Al~(3+)replaced Ca~(2+)as well asSi4+, but the substitution for Si4+increased with higher Al~(3+)concentration and resultedin the stabilization of T3-type alite. The initial reaction of C3S with Al~(3+)and alkaliswere dramatically increased compared with pure C3S, due to the vacancy defectcaused by heterovalent substitution.
Furthermore, the effects of combined doping with seven typical foreign ionssuch as Na~+, Mg~(2+)etc. on the structure and property of alite were studied. Thecombined doping with typical concentrations of various ions mainly promotedM3-type alite stabilization. Mg~(2+)and Al~(3+)had the most significant influence on thestabilization of the higher-temperature forms of alite, and the absence of either Mg orAl resulted in the stabilization of T3-type alite. Alite with P2O5≥0.5%(mass fraction,the same below) mainly resulted in the stabilization of R-type alite. The latticeparameters of alites changed linearly with the amount of substituent ions. But forparticular concentration at the solid solubility limit, phase transformation boundary, orwhere substitution patterns changed, inflection point appeared in the curve, followingthe Vegard’s law. About one third of Al could replace Ca, and two thirds of Al couldreplace Si. A small amount of Fe2O3(less than0.4%) mainly replaced Ca, andreplaced Si as well in higher concentration. The valence bond structure of [SiO4]tetrahedron was basically not affected by ion substitution whether for Ca or Si. The structure character of [SiO4] tetrahedron depended on the structural symmetry of alite.As the structural symmetry of ion-stabilized alite increased (T1→T2→T3→M3→R)，the higher symmetry of [SiO4] tetrahedron was attained.[SiO4] tetrahedron in T3polymorph got to symmetrical structure of regular tetrahedron. The structuralmetastability of alite directly correlated with the polymorphic form of alite and thekind and amount of incorporated foreign ions.
The activity of alites with multiple foreign ions doping was increased comparedwith pure C3S, but the main reaction was retarded. Heterovalent substitutions had themost significant influence on the crystal defects due to their complex substitution,which resulted in significant effects on the hydration kinetics of alite. The hydrationbehavior of alite did not depend much on the concentrations of defects as the types ofdefects. Fe and P, especially Fe had the most significant influence on the hydrationkinetics. The initial reaction of alite with Fe doping was decreased, the inductionperiod was prolonged, and the main hydration was slowed down. There was an abruptchange in the original thermoluminescence(TL) intensity of alite around the phasetransformation boundary. The hydration reactivity of alites of the same polymorphicform was related with their intensity of the original TL, and this correlation wasmainly reflected in the chemical-controled stage. The metastable energy stored astraped electrons transforming into chemical energy has been believed to account forthis phenomenon.
The alite polymorphsim and activity were directly affected by the calciningtemperature and cooling rate. T3form was stabilized for M3-type alites heat treated at700°C and800°C. The hydration activity of both pure C3S and typical alite wasincreased after heat treatment, especially for samples treated near the decompositiontemperature. Both pure C3S and alite treated at1350°C showed high activity andintense TL, most probably because1350°C was slightly higher than thedecomposition temperature, and very close to the Tammann temperature.
The grindability of alite was decreased with MgO≥1%and resulted in asignificant decrease in the compressive strength. In the experimental research scope,the strengths of R polymorph had the highest strength, and the compressive strengthsof T2, T3and M3were similar regardless of substituent ion’s content.
从离子的化学结构出发，归纳并提出结构差异因子D，发现离子取代位置依D值由Ca至Si递变性变化，稳定C3S多晶态范围呈类“几”字形规律；基于此，提出了离子稳定C3S高温型由离子固溶所致晶格扭曲畸变，阻碍原子位移相变所致，且进一步的实验验证了此规律和机制。
对Na~+、Al~(3+)等离子单掺的研究发现，C3S晶格常数随离子固溶量线性变化。高掺量Mg和Ba可分别稳定M3和T3型；Al高掺量时取代Si比例增加并稳定T3型。碱金属和Al~(3+)离子异价置换形成空位缺陷，显著提高C3S早期水化活性。
Na~+、Mg~(2+)等七种典型离子复合掺杂主要稳定阿利特为M3型，Mg~(2+)和Al~(3+)，尤其P5+对高温型稳定能力最强。不含Mg或Al阿利特以T3型为主；P2O5≥0.5%(质量分数，下同)时，以R型为主。阿利特晶格常数随离子固溶量线性变化，并在晶型相界点、固溶极限或固溶机理改变处存在拐点，符合Vegard固溶体定律。Al约1/3取代Ca，2/3取代Si；Fe2O3＜0.4%时，Fe取代Ca，＞0.4%时，取代Ca和Si。无论取代Ca还是Si，固溶离子均不影响[SiO4]四面体配位价键结构。随阿利特结构对称性提高，[SiO4]四面体对称性提高，自T3型开始，基本达正四面体对称结构。阿利特结构介稳性与晶型及固溶离子种类及含量有关。
多离子复合掺杂阿利特活性较纯C3S高，但主水化反应延缓。异价置换离子形成缺陷复杂，对阿利特缺陷特征影响大，对水化动力学过程影响更显著，且缺陷类型比浓度的影响更重要。Fe及P尤其是Fe对水化影响最大，Fe使早期活性显著降低，诱导期延长，水化延缓。在晶型相界处，阿利特原始热释光强度突变，同晶型阿利特原始热释光强度与水化放热活性呈相关性，并主要体现在化学反应控制过程，这与以俘获电子形式亚稳储藏能量向化学能的转化有关。
阿利特晶型及活性受煅烧温度及冷却速率影响。经700和800℃热处理M3型阿利特转变为T3型。靠近分解温度煅烧的阿利特活性高，尤其1350℃热处理呈现高活性和热释光性，与1350℃稍高于分解温度，且十分接近泰曼温度有关。
MgO≥1%时，阿利特易磨性显著降低，强度下降；若不考虑离子固溶的影响，本研究涉及的R型阿利特强度最高，三斜T2、T3以及单斜M3型强度相近。
Tricalcium silicate (C3S) solid solutions known as alites are the principle phaseof clinker, responsible for strength development. Therefore, it is important to study theeffects of substituents on the metastable structure and hydraulic properties of alite. Inthis dissertation, the effects of foreign ions doping such as Na~+、Mg~(2+)etc. especiallytheir combined doping on the crystal structure and property were studied throughsynthetic alites by XRD with the Rietveld method, petrographic analysis,thermoluminescence, isothermal calorimetry, FTIR, DSC, ICP-OES, and SAED.
Based on ions’ chemical structure, a quantity called structure difference factor D(referred to Ca~(2+)) was defined. The substitution position changed gradually from Ca toSi with the increase of D. The stabilization range of high temperature polymorphs ofC3S exhibited “几” font with D. Based on this result, it is believed that thestabilization of high temperature polymorphs of C3S was due to the distortion in thestructure caused by ionic substitution, which could block atomic displacement and goagainst phase transformation. The ion-stabilization law and mechanism were provedby the further experiments.
The effects of single doping with Na~+, Al~(3+)etc. on the structure and property ofC3S were investigated. It was found that the lattice parameters of C3S were relatedlinearly to the amount of substituent ions. Mg~(2+)and Ba~(2+)favoured the stabilization ofM3and T3-type alite respectively at high concentration. Al~(3+)replaced Ca~(2+)as well asSi4+, but the substitution for Si4+increased with higher Al~(3+)concentration and resultedin the stabilization of T3-type alite. The initial reaction of C3S with Al~(3+)and alkaliswere dramatically increased compared with pure C3S, due to the vacancy defectcaused by heterovalent substitution.
Furthermore, the effects of combined doping with seven typical foreign ionssuch as Na~+, Mg~(2+)etc. on the structure and property of alite were studied. Thecombined doping with typical concentrations of various ions mainly promotedM3-type alite stabilization. Mg~(2+)and Al~(3+)had the most significant influence on thestabilization of the higher-temperature forms of alite, and the absence of either Mg orAl resulted in the stabilization of T3-type alite. Alite with P2O5≥0.5%(mass fraction,the same below) mainly resulted in the stabilization of R-type alite. The latticeparameters of alites changed linearly with the amount of substituent ions. But forparticular concentration at the solid solubility limit, phase transformation boundary, orwhere substitution patterns changed, inflection point appeared in the curve, followingthe Vegard’s law. About one third of Al could replace Ca, and two thirds of Al couldreplace Si. A small amount of Fe2O3(less than0.4%) mainly replaced Ca, andreplaced Si as well in higher concentration. The valence bond structure of [SiO4]tetrahedron was basically not affected by ion substitution whether for Ca or Si. The structure character of [SiO4] tetrahedron depended on the structural symmetry of alite.As the structural symmetry of ion-stabilized alite increased (T1→T2→T3→M3→R)，the higher symmetry of [SiO4] tetrahedron was attained.[SiO4] tetrahedron in T3polymorph got to symmetrical structure of regular tetrahedron. The structuralmetastability of alite directly correlated with the polymorphic form of alite and thekind and amount of incorporated foreign ions.
The activity of alites with multiple foreign ions doping was increased comparedwith pure C3S, but the main reaction was retarded. Heterovalent substitutions had themost significant influence on the crystal defects due to their complex substitution,which resulted in significant effects on the hydration kinetics of alite. The hydrationbehavior of alite did not depend much on the concentrations of defects as the types ofdefects. Fe and P, especially Fe had the most significant influence on the hydrationkinetics. The initial reaction of alite with Fe doping was decreased, the inductionperiod was prolonged, and the main hydration was slowed down. There was an abruptchange in the original thermoluminescence(TL) intensity of alite around the phasetransformation boundary. The hydration reactivity of alites of the same polymorphicform was related with their intensity of the original TL, and this correlation wasmainly reflected in the chemical-controled stage. The metastable energy stored astraped electrons transforming into chemical energy has been believed to account forthis phenomenon.
The alite polymorphsim and activity were directly affected by the calciningtemperature and cooling rate. T3form was stabilized for M3-type alites heat treated at700°C and800°C. The hydration activity of both pure C3S and typical alite wasincreased after heat treatment, especially for samples treated near the decompositiontemperature. Both pure C3S and alite treated at1350°C showed high activity andintense TL, most probably because1350°C was slightly higher than thedecomposition temperature, and very close to the Tammann temperature.
The grindability of alite was decreased with MgO≥1%and resulted in asignificant decrease in the compressive strength. In the experimental research scope,the strengths of R polymorph had the highest strength, and the compressive strengthsof T2, T3and M3were similar regardless of substituent ion’s content.
引文
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