固态碱组分碱矿渣水泥的研制及其水化机理和性能的研究

本研究针对液态碱组分碱矿渣水泥的缺陷,研制成功了强度标号达425R～625R的固态碱组分碱矿渣水泥,并对这种新型胶凝材料的生产工艺、水化机理、物理力学性能和耐久性进行了深入的研究。 运用现代测试手段详细研究了矿渣玻璃体的微观结构,发现矿渣玻璃体具有主要由富钙相和富硅相组成的微观分相结构,并且各相的存在状态和性质有很大的差异。在这一发现的基础上,本研究很好地解释了矿渣水硬活性的潜在性以及固态碱组分碱矿渣水泥的水化机理。研究表明,固态碱组分碱矿渣水泥的水化过程中没有诱导期或诱导期相当短,该水化过程主要经历矿渣的解体、新相的形成和长大、水化产物的缩聚和“混凝”三个阶段,其水化产物主要是沸石类矿物,另外还有少量的低碱性水化硅酸钙C-S-H(Ⅰ)。 研究表明,固态碱组分碱矿渣水泥属于低热水泥;其水泥石的孔隙率较小,且孔径大于10~3A的有害孔所占的比例较小;其抗渗性、抗冻性、抗碳化性能及抗化学腐蚀性等耐久性能良好。通过试验证实了用这种水泥配制的混凝土不会发生因碱集料反应而引起的膨胀破坏。 本研究研制成功的固态碱组分碱矿渣水泥不仅性能优良,而且充分利用工业废渣、成本低廉、生产工艺简单、使用方便,具有重要的实用意义。     

养护温度对矿渣硫铝酸盐水泥水化的影响机理

研究了5℃、20℃和40℃养护下矿渣硫铝酸盐水泥的强度发展、水化放热、干燥收缩、水化产物及孔结构演变。结果表明,不同于硅酸盐水泥,矿渣硫铝酸盐水泥早期水化生成较多钙矾石,但累计放热量较低。养护温度越高,矿渣硫铝酸盐水泥石的早期力学强度越高;但20℃下后期抗压强度显著提升,远超过其他温度。相应的,源自小孔内水分蒸发产生的较大孔壁压力,20℃下水泥石表现出最显著的收缩行为。     

基于中心粒子水化模型的水泥水化动力学研究

在K.B.Park提出的中心粒子水化模型的基础上,考虑内、外部水化产物的具体特征以及自由水与水化产物接触相界面积的减小导致水泥水化速率减小这2个因素,建立硅酸盐水泥的微观水化模型,并用于预测水化速率随水化程度的变化关系。结果表明,在水泥的整个水化过程中,修正的微观水化模型都能够更真实地反应水泥水化速率与水化程度变化的关系。     

低水灰比对硅酸盐水泥水化程度的影响

研究了低水灰比硅酸盐水泥的水化程度，并利用XRD和SEM分析了其水化产物的微观结构。结果表明在低水灰比条件下，水泥的水化程度较低，其硬化水泥浆体中存在较多的未水化水泥；同时由于自身的密实性增强和体系的低孔隙率，使水泥水化产物的结晶、生长情况也受到影响。     

利用红外和核磁技术分析矿渣硅酸盐复合胶凝材料的水化产物

采用傅里叶红外光谱(FTIR)和高分辨29Si固体核磁共振技术(NMR),研究了不同水化龄期的水泥-矿渣复合胶凝硬化浆体的微观结构。结果表明:纯硅酸盐水泥随着水化时间的增长,水化程度变大,聚合度增加,生成更多的长链水化硅酸钙(C-S-H)凝胶;矿渣硅酸盐水泥试样水化早期主要生成二聚体凝胶,随着龄期增长,逐渐转变为长链型凝胶,平均链长逐渐增加;随着矿渣掺量的增加,激发矿渣所需时间增长,早期Q~2(1Al)很少,但随着龄期延长,矿渣逐渐被激发,C-A-S-H凝胶变多。     

C-S-H纳米晶种及其对水泥水化硬化的促进作用综述

近些年来的研究发现，将一些纳米粒子加入到水泥中，可以为水化产物提供更多形核位点，降低水化产物的形核势垒，加快水泥的水化进程。这些纳米材料包括纳米SiO₂、纳米CaCO₃、纳米TiO₂、碳纳米管、纳米水化硅酸钙(C-S-H)等。其中，人工合成的纳米C-S-H晶种与水泥水化产物C-S-H凝胶具有相似的化学组成，是C-S-H凝胶的良好的形核基质，在众多晶种材料中，对水泥水化的加速作用最为显著，成为近年来的研究热点。到目前为止，众多学者围绕C-S-H微/纳米材料的成核方式、制备方法及对水泥水化的促进机理进行了大量研究，发现采用共沉淀法在聚合物存在的条件下制备的纳米C-S-H晶种成核剂遵循非经典成核方式，其具有纳米级的晶粒尺寸和良好的分散稳定性。将纳米C-S-H晶种以一定掺量加入到水泥中，可以充当水泥水化产物C-S-H凝胶的额外成核位点，极大地降低了C-S-H凝胶的成核势垒，有效地促进了水泥水化速率和早期强度的发展，尤其可以显著提升水泥1 d龄期以内的强度。与常用的早强剂相比，这种纳米C-S-H晶种成核剂除具有掺量低、早强效果好、...     

甲酸钙对硫铝酸盐水泥早期水化过程的影响

利用维卡仪、水化放热速率、XRD、TG-DSC和SEM等测试手段,研究了甲酸钙(Ca(HCOO)2)对硫铝酸盐水泥凝结时间、水化历程和水化产物及微观形貌的影响。结果表明,Ca(HCOO)2可明显促进硫铝酸盐水泥的凝结,并缩短初凝和终凝时间间隔;显著缩短了硫铝酸盐水泥的水化诱导期,且使水化加速期提前,使第一水化热峰值提高32%,但对水化稳定期的水化放热速率无明显影响;Ca(HCOO)2可以提高硫铝酸盐水泥水化环境的碱度,在早期提高了水化产物钙矾石(AFt)的结晶度,水化早期生成的水化产物结构致密,但并不改变水化稳定期的水化产物和微观形貌。     

水泥水化过程计算机模拟研究——CEMHYD3D系统分析与模拟实现

分析了水泥水化过程计算机模拟这一领域最有代表性的模拟系统--CEMHYD3D的建模过程,以CCRL Cement 133水泥为例,对不同水灰比条件下的水泥水化过程进行了实际模拟计算,对水化热、水化程度、水化过程中主要反应物和产物的变化情况进行了预测.研究表明,CEMHYD3D的模拟结果与实验所揭示的规律一致性较好,尤其是该软件在物相成分变化规律方面的预测对于水化机理的研究很有意义.     

碳酸化钢渣和矿渣作硅酸盐水泥混合材水化性能研究

通过对钢渣碳酸化前后的硅酸盐相提取及水化放热性能和将碳酸化钢渣和矿渣作为混合材的硅酸盐水泥的胶砂强度和水化产物种类的测定,以及对它们微观形貌的观察,研究了碳酸化钢渣对胶凝体系水化性能的影响.结果表明,碳酸化使钢渣中硅酸盐相的含量由47.06％下降至14.38％;碳酸化促进了钢渣的早期水化,抑制其后期水化;在配比相同的条件下,碳酸化钢渣-矿渣-硅酸盐熟料体系试样的3、28d抗压强度较未碳酸化钢渣-矿渣-硅酸盐熟料体系试样的高;碳酸化生成的CaCO3促进了熟料的水化;碳酸化钢渣促进了胶凝体系中AFt的生成,且生成水合碳铝酸钙.     

复合外加剂对铬铁渣基复合材料水化机理的影响

采用X射线粉末衍射(XRD)、差热-热重同步热分析仪(TG-DSC)、扫描电子显微镜(SEM)等分析铬铁渣基复合材料的水化产物的物相组成、微观结构和形貌特征,用甲醇法测定了复合材料的孔隙率。研究了复合外加剂对复合材料水化性能的影响及其作用机理。研究表明:掺入外加剂能显著提高复合材料的早期强度,水化初期大量的钙矾石(AFt)和水化硅酸钙凝胶(C-SH)是复合材料早期强度的主要来源,水化后期外加剂能促进铬铁渣、矿渣等的二次水化反应,使其水化速度增长较快。C-S-H凝胶的不断形成和增多及其对体系孔隙的填充使复合材料的结构更加致密。     

A multi-phase kinetic model to simulate hydration of slag–cement blends

Ground granulated blast furnace slag, which shows cementitious behavior (latent hydraulic activity) and pozzolanic characteristics (reaction with lime), has been widely used as a mineral admixture in normal and high strength concretes. Hydration of slag–blended cement is much more complex than that of ordinary Portland cement because of the mutual interactions between the cement hydration and the slag reaction. This paper presents a kinetic hydration model for cement–slag blends. The proposed model analyzes the slag reaction separate from cement hydration by considering the production of calcium hydroxide in cement hydration and its consumption in slag reactions. The amount of free water and the amount of calcium hydroxide left in the system were adopted as the control indicators for determining the slag reaction. Using the proposed model, the reaction ratio of slag can be evaluated as a function of curing age, considering the influences of the water to binder ratio, the slag replacement ratio and the curing temperature. Furthermore, the amount of chemically-bound water (self-cementing properties), calcium hydroxide (pozzolanic capabilities), and the heat released from hydration are evaluated by determining the contributions from both the cement hydration and the slag reaction. The evaluated results show good accordance with the experimental results.     

The hydration of slag,part 2: reaction models for blended cement

The hydration of slag-blended cement is studied by considering the interaction between the hydrations of slag and Portland cement clinker. Three reaction models for the slag-blended cement are developed based on stoichiometric calculations. These models correlate the compositions of the unhydrated slag-blended cement with the quantities and compositions of the hydration products. The model predictions are further used to calculate some properties of hydrating slag cement pastes, including the molar fractions of products, the water retention, chemical shrinkage and porosities of pastes. The models are validated by comparing the model predictions with the measurements and proven to be successful in quantifying the hydration products, predicting the composition of the main hydration product (C-S-H) and calculating the properties of the hydration process. The model predictions show that as the slag proportions in the blended cement changes, water retention in the hydration products changes only slightly if compared to that of Portland cement, but the chemical shrinkage can vary in a wide range, depending on the slag hydration degree in the cement.     

Simulation of a temperature rise in concrete incorporating fly ash or slag

Granulated slag from metal industries and fly ash from the combustion of coal are among the industrial by-products and have been widely used as mineral admixtures in normal and high strength concrete. Due to the reaction between calcium hydroxide and fly ash or slag, compared with Portland cement, the hydration of concrete containing fly ash or slag is much more complex. In this paper, by considering the producing of calcium hydroxide in cement hydration and the consumption of it in the reaction of mineral admixtures, a numerical model is proposed to simulate the hydration of concrete containing fly ash or slag. The heat evolution rate of fly ash or slag blended concrete is determined from the contribution of both cement hydration and the reaction of mineral admixtures. Furthermore, a temperature rise in blended concrete is evaluated based on the degree of hydration of cement and mineral admixtures. The proposed model is verified with experimental data on the concrete with different water-to-cement ratios and mineral admixtures substitution ratios.     

Three-dimensional computer modeling of slag cement hydration

A newly developed version of a three-dimensional computer model for simulating the hydration and microstructure development of slag cement pastes is presented in this study. It is based on a 3-D computer model for Portland cement hydration (CEMHYD3D) which was originally developed at NIST, taken over in the authors’ group and further developed. Features like the digitized 3-D microstructure, the cellular automata (CA) algorithm for simulating the random walking, phase transformation for simulating the chemical reactions, are retained. But, the 3-D microstructure was reconstructed allowing for slag particles as binder in the system. Algorithms and rules are developed to account for the interaction between Portland cement hydration and slag reaction in the paste, of which the mechanisms were revealed in the studies by Chen and Brouwers [(2007) J Mater Sci 42(2):428; (2007) J Mater Sci 42(2):444] Methods for considering the various factors on the reactivity of slag in hydrating slag cement pastes are proposed, mainly for the oxide composition of slag and the alkalinity in the pore solution composition. A comparison between the model predictions and the experimental results in literature shows that the presented computer model can successfully predict the hydration process and the microstructure development of hydrating slag cement paste.     

循环流化床固硫灰渣低收缩水泥的制备及性能

通过分别使用循环流化床(CFBC)固硫灰、渣代替部分原材料制备低收缩水泥熟料,加入质量分数为10%的石膏即得到CFBC固硫灰、渣低收缩水泥,然后利用X射线衍射、扫描电镜等方法研究水与水泥的质量比(简称水灰比)对CFBC固硫灰渣低收缩水泥水化程度、抗压强度和线性膨胀率的影响。结果表明,随着水灰比的增加,CFBC固硫灰渣低收缩水泥的主要水化产物钙矾石数量增多,未水化的硅酸二钙含量减少,水化程度增大;而该水泥线性膨胀率与水灰比呈正比关系,抗压强度与其呈反比关系;利用固硫灰制备的水泥早期膨胀率随着水化时间而增大,但后期由于石膏量的不足,膨胀率则随着水化时间而减小。     

A method for predicting the alkali concentrations in pore solution of hydrated slag cement paste

The alkalinity of the pore liquid in hardened cement paste or concrete is important for the long-term evaluation of alkali-silica reaction (ASR) expansion and corrosion prevention of steel bar in steel reinforced structures among others. It influences the reactivity of supplementary cementitious materials as well. This paper focuses on the alkali binding in hydrated slag cement paste and a method for predicting the alkali concentrations in the pore solution is developed. The hydration of slag cement is simulated with a computer-based model CEMHYD3D. The amount of alkalis released by the cement hydration, quantities of hydration products, and volume of the pore solution are calculated from the model outputs. A large set of experimental results reported in different literatures are used to derive the alkali-binding capacities of the hydration products and practical models are proposed based on the computation results. It was found that the hydrotalcite-like phase is a major binder of alkalis in hydrated slag cement paste, and the C?CS?CH has weaker alkali-binding capacity than the C?CS?CH in hydrated Portland cement paste. The method for predicting the alkali concentrations in the pore solution of hydrated slag cement paste is used to investigate the effects of different factors on the alkalinity of pore solution in hydrated slag cement paste.     

垃圾焚烧炉渣-粉煤灰复合水泥的性能研究

研究了垃圾焚烧炉渣及粉煤灰单掺和复掺时硬化水泥浆体的力学性能和水化机理,比较了两者的活性,探讨了两者作为辅助性胶凝材料利用的可行性.研究表明:掺有垃圾焚烧炉渣及粉煤友的复合水泥,其强度均有不同程度的下降,它们的掺入在一定程度上延缓了水泥的水化过程,且垃圾焚烧炉渣的水化反应活性稍高于粉煤灰;掺垃圾焚烧炉渣及粉煤灰的复合水泥中重金属离子浸出量小,在等掺20%的条件下,浸出量远低于国家标准,说明在一定的情况下,焚烧炉渣及粉煤灰作为辅助性胶凝材料使用是安全的.     

The influence of blast-furnace slag hydration products on microcracking of concrete

New hydration products of ground granulated blast-furnace slag are formed during the hydration process of Portland slag cement concrete. Spatial distribution of microcracks in concrete is related also to newly formed slag hydrates. The chemical composition of hydration products is variable and unstable. The Si/Ca ratios rise in hydration products near the unhydrated slag core significantly. There is also a certain increase of Mg and Al content in the central parts of hydration rims. The scope of the paper is to find a relation between slag hydration products and the process of microcracking. The amount of microcracks was reduced in concretes with a lower content of vitreous fraction where the slag basicity was high. Neoformation of hydration products is accompanied by volume changes, which can lead to concrete microcracking.     

Nanoscale mechanical properties of concrete containing blast furnace slag and fly ash before and after thermal damage

Portland cement blended with waste products such as blast furnace slag and fly ash are frequently used to create more sustainable concrete, but their nanoscale mechanical behavior, particularly after thermal damage, has not been well-studied. Here, nanoindentation experiments confirm that concrete produced with blended cements contains hydration products with nearly identical nanoscale mechanical properties to the hydration products found in concretes produced with ordinary Portland cement. The volume fractions of the hydration products, particularly calcium-silicate-hydrate (C-S-H) phases, are formed in different proportions with the addition of fly ash and blast furnace slag. After exposure to fire damage, the nanoscale behavior of concretes produced with fly ash and slag also matches the nanoscale behavior of conventional concretes. This suggests that any macroscopic differences between fire damage behavior of blended cement concrete and ordinary Portland cement concrete must have origins in a larger length scale.