矿渣-水泥复合胶凝体系低温水化动力学研究

研究了低温下矿渣-水泥复合胶凝体系的水化反应特性和水化反应动力学.研究表明:低温下,复合胶凝体系的水化放热速率随着矿渣掺量的增加和环境温度的降低而下降;非蒸发水含量随着矿渣掺量的增加呈现降低的趋势;对已有水泥水化动力学方程进行计算,得到了低温条件下复合胶凝体系的动力学参数以及不同阶段反应速率和水化度间的关系,通过计算获得的动力学参数,可以对低温条件下复合胶凝体系不同反应阶段水化反应程度进行预测;在水化早期,复合胶凝体系中矿渣水化程度较低,消耗少量Ca(OH)2,使生成C-S-H凝胶的Ca/Si降低较少.在水化后期,复合胶凝体系中矿渣水化消耗较多的Ca(OH)2,使生成C-S-H凝胶的Ca/Si降低较多.矿渣掺量为50％时,硬化浆体C-S-H凝胶的Ca/Si远小于纯水泥体系.     

水泥–矿渣复合胶凝材料中矿渣的水化特性

通过对不同矿渣掺量时水泥–矿渣复合胶凝材料中矿渣的反应程度、硬化浆体中Ca（OH）2含量以及水化硅酸钙（C–S–H）凝胶的Ca/Si比（Ca和Si的摩尔比）的测定,研究复合胶凝材料体系中矿渣的水化特性。结果表明：在水泥–矿渣复合胶凝材料中,矿渣掺量越大,矿渣反应程度越低,但矿渣掺量≤70%时,对矿渣的反应程度影响不大。高温养护可提高早期矿渣的反应程度,但阻碍其后期的进一步水化。矿渣早期水化生成外部水化产物时消耗一定的Ca（OH）2,使硬化浆体中Ca（OH）2含量降低,矿渣水化吸收Ca（OH）2中的Ca2＋,使生成的C–S–H凝胶的Ca/Si比降低较少;在水化后期,矿渣生成内部水化产物不再消耗较多的Ca（OH）2,使C–S–H凝胶的Ca/Si比降低相对较多,硬化浆体中Ca（OH）2含量有增加的趋势,保证硬化浆体的长期稳定性。     

大掺量钢渣复合胶凝材料早期水化性能和浆体结构

通过对胶凝材料早期水化放热性能和水化产物种类的测定,以及对硬化浆体显微形貌和孔结构的观察,研究了大掺量钢渣复合胶凝材料的早期水化性能和硬化浆体结构.结果表明:钢渣具有弱胶凝性能,早期活性低,大掺量钢渣使复合胶凝材料的水化诱导期延长,水化放热量降低,但对水泥早期的水化产物形成过程影响很小.大掺量钢渣复合胶凝材料早期的硬化浆体结构较疏松,孔隙率高于纯水泥浆体,且大孔数量较多.     

等28d抗压强度条件下粉煤灰和矿渣对C50混凝土后期性能的影响

在28 d抗压强度相近的前提下,制备了纯水泥混凝土、大掺量粉煤灰混凝土、大掺量矿渣混凝土,测定了不同混凝土的后期抗压强度、抗氯离子渗透性,以及胶凝材料的化学结合水、硬化浆体中的Ca(OH)2含量.结果表明:含大掺量矿物掺合料的混凝土的后期强度和抗氯离子渗透性均明显高于纯水泥混凝土;大掺量矿渣混凝土的后期强度高于同掺量的大掺量粉煤灰混凝土;复合胶凝材料的后期水化程度增长率明显高于纯水泥;复合胶凝材料硬化浆体中后期Ca(OH)2含量明显低于纯水泥硬化浆体.     

水泥-矿渣复合胶凝材料硬化浆体的微观结构

利用压汞法、扫描电子显微镜和透射电子显微镜研究了两种不同养护条件下水泥-矿渣复合胶凝材料硬化浆体的微观结构.结果表明:常温养护3d龄期时,随着矿渣的掺入和掺量的增加,硬化浆体的孔隙率越大,大孔含量越多;硬化浆体微观形貌显示,掺矿渣试样的反应程度比纯水泥试样更低,密实程度较差.水化后期,复合胶凝材料的水化程度虽然比纯水泥试样低,但复合试样的孔隙率更低,孔径细化.纯水泥试样中水化硅酸钙(C-S-H)凝胶的微观形貌呈单向分布的纤维状,而复合胶凝材料试样中矿渣反应生成的C-S-H凝胶呈三维分布的箔片状,能更有效的隔断和填充连通的孔隙.在高温养护条件下,掺矿渣复合胶凝材料硬化浆体早期和后期孔隙率均较低,高温激发了矿渣早期的活性.     

高温养护下粉煤灰效应机理研究

大体积混凝土施工过程中,为降低水化热而采用大量的粉煤灰替代水泥,故对高掺量粉煤灰水泥的水化硬化机理进行深入系统的研究具有重要的意义.以大掺量粉煤灰胶凝材料硬化浆体为研究对象,结合XRD、FTIR、NMR等测试分析,研究高养护制度下粉煤灰掺量对其水化相C-S-H凝胶硅氧四面体聚合程度的影响规律.结果表明:高温养护的硬化浆体,其水化相C-S-H凝胶硅氧四面体聚合程度和Al原子取代Si原子的程度,在各个养护龄期始终高于常温养护的硬化浆体.     

水泥-矿渣复合胶凝材料硬化浆体的微观结构（英文）

利用压汞法、扫描电子显微镜和透射电子显微镜研究了两种不同养护条件下水泥-矿渣复合胶凝材料硬化浆体的微观结构。结果表明:常温养护3 d龄期时,随着矿渣的掺入和掺量的增加,硬化浆体的孔隙率越大,大孔含量越多;硬化浆体微观形貌显示,掺矿渣试样的反应程度比纯水泥试样更低,密实程度较差。水化后期,复合胶凝材料的水化程度虽然比纯水泥试样低,但复合试样的孔隙率更低,孔径细化。纯水泥试样中水化硅酸钙(C-S-H)凝胶的微观形貌呈单向分布的纤维状,而复合胶凝材料试样中矿渣反应生成的C-S-H凝胶呈三维分布的箔片状,能更有效的隔断和填充连通的孔隙。在高温养护条件下,掺矿渣复合胶凝材料硬化浆体早期和后期孔隙率均较低,高温激发了矿渣早期的活性。     

养护制度对高掺花岗岩石粉UHPC性能的影响

研究了三种养护制度条件下,高掺(22％)花岗岩石粉UHPC力学性能(3 d、28 d和180 d抗压/抗折强度)和胶凝浆体C-S-H凝胶微结构(水化程度、平均分子链长(MCL)和直链中的[SiO4](Q2))的变化规律.结果表明:同一龄期抗压/抗折强度、胶凝浆体水化程度、C-S-H凝胶MCL和Q2相对含量变化规律由高到低依次为压蒸养护、蒸汽养护和标准养护;随着养护温度和压力增加,其后期强度和胶凝材料水化程度增幅逐渐降低,且不利于后期C-S-H凝胶MCL发展.高掺花岗岩石粉的UHPC胶凝浆体中常温下的水化产物主要包括C-S-H凝胶、AFt和Ca(OH)2,随着养护温度和压力的升高,AFt和Ca(OH)2相对含量降低;至210℃2 MPa时,XRD图谱中两相消失且出现Tobermorite衍射峰,即高温高压环境促进了C-S-H凝胶向Tobermorite晶体转化.     

不同矿物掺合料对蒸养水泥水化产物与力学性能的影响

为探讨矿物掺合料对预制装配式混凝土水化产物与力学性能的影响,采用20％的镍铁渣粉、锂渣粉、钢渣粉与矿渣粉分别取代水泥,在早期80℃蒸养7h条件下制备了水泥净浆与砂浆,对比研究了镍铁渣粉、锂渣粉、钢渣粉与矿渣粉对7h和28 d龄期蒸养水泥水化产物和力学性能的影响.结果 表明:除了C-S-H与Ca(OH)2外,7h蒸养水泥的水化产物主要为AFm与Ca4Al2O6(CO3)0.5(OH)·11.5H2O,28 d蒸养水泥的水化产物主要为Ca4Al2O6(CO3)0.5(OH)·11.5H2O和Ca4Al2O6(CO3)·11H2O,矿物掺合料对蒸养水泥水化产物种类影响较小;掺镍铁渣粉、锂渣粉、钢渣粉、矿渣粉后,7h蒸养水泥的化学结合水含量分别达到了纯水泥的93.27％、102.22％、90.24％、102.22％,28 d蒸养水泥的化学结合水含量分别达到了纯水泥的93.76％、95.08％、86.27％、95.68％,掺锂渣粉与矿渣粉可以显著提高7h蒸养水泥的水化程度,掺钢渣粉的效果最差;此外,掺锂渣粉、钢渣粉、矿渣粉改变了蒸养7h水泥浆体C-S-H的形貌,除了纤维状C-S-H外,掺锂渣粉水泥浆体中还有蜂窝状C-S-H形成,掺钢渣粉水泥浆体与掺矿渣粉水泥浆体中还有球形与薄片状C-S-H形成;掺锂渣粉可以提高早期80℃蒸养7h水泥胶砂的抗压与抗折强度,但四种矿物掺合料均不能改善28 d蒸养水泥胶砂的力学性能.     

化学驱动与热力学驱动下复合胶凝体系的水化特性研究

为了解复合胶凝材料体系水化放热特性,以及化学驱动与热力学驱动对复合胶凝材料体系的水化放热影响,研究了不同掺量的粉煤灰/矿粉-水泥二元复合胶凝体系的水化热发展,同时探究了不同早强剂掺量以及不同温度对粉煤灰-水泥二元复合胶凝体系水化放热的影响。结果表明:粉煤灰、矿粉均会降低二元复合胶凝体系水化放热速率,但矿粉活性比粉煤灰高,对水化放热速率以及最终累计放热量影响较小;化学驱动可以显著提高体系水化放热速率,促进早期水化发展,但不改变最终累计放热量;热力学驱动作用效果更显著,可以大幅提高体系放热曲率以及累计放热量。以化学反应速率为判据构建两种驱动的联系能有效地设计混合驱动模式。     

Initial hydration of tricalcium silicate as studied by secondary neutrals mass spectrometry: II. Results and discussion

The hydration of tricalcium silicate (C₃S) was studied by secondary neutrals mass spectrometry (SNMS), a method that enables determination of the Ca/Si ratio of the formed calcium silicate hydrate (C-S-H) phase with an extremely low information depth. It was found that the magnitude of this parameter within the hydrate layer formed at the surface of the nonhydrated C₃S is not constant and increases with increasing distance from the liquid-solid interface. It was also found that, at a constant distance from the surface, the Ca/Si ratio declines with hydration time. The kinetics of the hydration process is characterized by a very fast initial reaction, followed by a dormant period and a subsequent period of renewed hydration. The rate of hydration becomes distinctly accelerated by elevated temperature and retarded by the presence of sucrose, while NaCl affects the initial hydration kinetics only to a small degree.     

Stoichiometry of Slag Hydration with Calcium Hydroxide

The stoichiometry of the reaction between ground granulated blast furnace slag (GGBFS) having an empirical formula of C_7.88S_7.39M₃A and calcium hydroxide (CH) was investigated. Scanning electron microscopy (SEM) was used to determine the slag consumption as well as the Ca/Si ratio in calcium silicate hydrate gel (C-S-H) products. A tentative stoichiometric ratio of 2.6 mol of CH consumed per mole of slag reacted was determined using two methods. By combining consumption data determined separately for slag and CH a molar stoichiometry of 2.79 was found. Similarly, by directly determining the Ca/Si ratio in the C-S-H gel product, a range for the molar stoichiometry between 1.65 and 3.42 was found. Finally, a comparison of the stoichiometry of the slag/CH reaction was made with slag/portland cement hydration. The basic features of both appear similar. In the C-S-H gel around slag grains, a calcium-to-silica ratio of 1.3 to 1.4 was found for both slag/CH and slag/cement systems.     

分子动力学模拟研究钙硅摩尔比对水化硅酸钙结构与力学性能的影响

水化硅酸钙(C-S-H)作为硅酸盐水泥基材料的主要结合相,对水泥基材料的耐久性、物理力学性能有显著影响。本文构建了钙硅摩尔比(Ca/Si)从1.1到1.9的5个C-S-H模型,并通过分子动力学模拟了C-S-H 模型沿x、y和z方向的纳米压痕测试,然后采用典型的Oliver-Pharr方法分别计算它们的压痕模量和硬度。模拟结果表明:随着钙硅摩尔比的增加,C-S-H的密度会逐渐降低,水硅摩尔比会逐渐增加,平均硅链长会有所降低;C-S-H的力学性能受钙硅摩尔比的影响很大,随着钙硅摩尔比的增加,硅链缺陷程度增加,钙硅片层状结构的稳定性会相应降低,C-S-H结构抵抗外界变形荷载的能力减弱,从而导致压痕模量和硬度降低。平行于钙硅层方向的压痕模量和硬度值比较接近,而垂直于钙硅层方向的值略低,C-S-H近似于横观各向同性结构。随着钙硅摩尔比的增加,三个方向的值逐渐接近,C-S-H具有从横观各向同性变为各向同性的趋势。     

Solubility and structure of calcium silicate hydrate

The poorly crystalline calcium silicate hydrate (C-S-H) phases that form near room temperature, which include the technically important C-S-H gel phase formed during the hydration of Portland cement, have a broad similarity to the crystalline minerals tobermorite and jennite, but are characterized by extensive atomic imperfections and structural variations at the nanometer scale. Relationships between the aqueous solubility and chemical structure are reported for specimens formed by different preparation methods and with a broad range of compositions. Both new and previously published data show that these phases generate a family of solubility curves in the CaO-SiO₂-H₂O system at room temperature. As demonstrated by ²⁹Si magic-angle spinning (MAS) NMR data and by charge balance calculations, the observed solubility differences arise from systematic variations in Ca/Si ratio, silicate structure, and Ca-OH content. Based on this evidence, the solubility curves are interpreted as representing a spectrum of metastable phases whose structures range from purely tobermorite-like to largely jennite-like. These findings give an improved understanding of the structure of these phases and reconcile some of the discrepancies in the literature regarding the structure of C-S-H at high Ca/Si ratios.     

The composition of the C-S-H phases in portland cement pastes

The composition of the calcium silicate hydrate (C-S-H) present in Portland cement pastes from eight days to five years old, and in concrete samples ten years old, has been determined by electron probe micro-analysis. The dependence of C-S-H composition on water/cement ratios has also been studied. When the cement is only partially hydrated inner and outer hydrate layers are seen around alite grains. These hydrates have different chemical compositions. With progressive hydration it becomes impossible to distinguish the inner from outer hydrates without a reference alite grain. At this stage two distinct C-S-H compositions can still be found by microanalysis. After further hydration a single CSH composition predominates. The calcium content of C-S-H varies significantly with water/cement ratio and there is new evidence to suggest that in the C-S-H structure Mg replaces Ca, and that Al, S and Fe replace Si.     

Effect of calcium to silica ratio on the synthesis of calcium silicate hydrate in high alkaline desilication solution

High alkaline desilication solution (DSS), a high volume byproduct from the pretreatment of high-alumina fly ash, was used as low-cost mother liquor for the synthesis of calcium silicate hydrate (C-S-H). Through the combined analysis of X-ray diffraction, thermogravimetric analysis, X-ray fluorescence, ²⁹Si MAS NMR, and Brunauer-Emmett-Teller, the relationship between chemical composition and structure of C-S-H synthesized under Ca/Si of 0.83:1 to 2.0:1 was investigated. Silicon conversion and yield of product have a positive correlation with Ca/Si. Sodium uptake in C-S-H is inhibited as Ca/Si increases. The formation of sodium in C-S-H transfers from “bound Na” to “mobile Na” and aluminum from tetrahedrally coordinated Al (IV) to octahedrally coordinated Al (VI). The increase of Ca/Si leads to shortening of silicate chain and formation of more dimers, which causes more water bound in C-S-H. The mechanism of calcium addition on silicate chain obtained from DFT calculation primarily results from more interlayer calcium occurrence to affect bridging tetrahedron and cationic bounding states reorganization. Reasonable control for Ca/Si momentously contributes to the adjustment for composition and structure of C-S-H synthesized in DSS.     

钢渣水化产物的特性(英文)

用X射线衍射分析、水化热的测量、化学结合水量的测定、孔结构的测定、扫描电镜观察及强度测试研究了钢渣的水化产物的特性。结果表明:钢渣硬化浆体中主要含有水化硅酸钙(C–S–H)凝胶、Ca(OH)2、惰性组分[RO相、铁酸二钙(C2F)和Fe3O4]和未水化的胶凝相[硅酸三钙(C3S)和硅酸二钙(C2S)];总体而言,钢渣的水化过程与水泥的水化过程相似;钢渣早期的水化速率远低于水泥,但钢渣后期,尤其是90d之后的水化速率高于水泥的。钢渣水化产生的C–S–H凝胶不具有良好的胶凝性能,凝胶之间的相互黏结也不牢固,因此钢渣砂浆的强度很低。     

Crystal defects and hydration I. Influence of lattice defects

The hydration of calcium silicates occurs by a series of complex, interrelated processes. A study conducted to determine the role of calcium silicate grain lattice defects in these processes found two processes at work during early hydration (0 to 5 minutes): (i) adsorption on the grain, followed by (ii) a chemical reaction to form the first C-S-H hydrate. The lattice defects in the grain have a direct relationship to the length of the induction period, and the number of defects, or degree of crystal disorder, directly influences the amount of enhanced reactivity.     

Influence of activator type on hydration kinetics, hydrate assemblage and microstructural development of alkali activated blast-furnace slags

The hydration of two slags with different Al₂O₃ contents activated with sodium hydroxide and hydrous sodium metasilicate (commonly named water glass) is studied using a multi-method approach. In all systems, C-S-H incorporating aluminium and a hydrotalcite-like phase with Mg/Al ratio ~ 2 are the main hydration products. The C-S-H gels present in NaOH activated pastes are more crystalline and contain less water; a calcium silicate hydrate (C-S-H) and a sodium rich C-N-S-H with a similar Ca content are observed at longer hydration times. The activation using NaOH results in high early strength, but strength at 7 days and longer is lower than for the sodium metasilicate systems. The drastic difference in C-S-H structure leads to a coarser capillary porosity and to lower compressive strength for the NaOH activated than for the sodium metasilicate activated slags at the same degree of slag reaction.