过硫磷石膏矿渣水泥浆性能优化研究

通过磷石膏预处理、提高减水剂掺量、添加硫铝酸盐水泥熟料和提高蒸养温度的方法,对过硫磷石膏矿渣水泥浆的物理力学性能进行了优化研究,并通过XRD、SEM对其水化过程和机理进行了探讨。结果表明,磷石膏经钢渣预处理可以缩短过硫磷石膏矿渣水泥浆的凝结时间;适当提高减水剂掺量可以在缩短水泥浆凝结时间的同时显著提高其早期和中后期强度;掺加硫铝酸盐水泥熟料可以显著缩短水泥浆凝结时间并提高其28d强度;合理控制蒸养温度,可以提高水泥浆早期强度且加快模具周转,提高生产效率。     

水泥-磷石膏基复合胶凝材料的早期强度及耐水性研究

将磷石膏和水泥按照一定的比例制成磷石膏试件,通过控制水泥掺量以及有机硅油掺量,研究水泥对磷石膏材料的强度以及耐水性的影响。研究表明:掺加水泥不能有效提高复合胶凝材料的强度及耐水性;掺加有机硅油能有效改善和提升磷石膏试件的耐水性;当磷石膏试件中掺有水泥的条件下,掺加有机硅油会使磷石膏试件发生膨胀甚至产生裂纹,从而降低磷石膏试件的强度。     

水泥-磷石膏基复合胶凝体系早期强度及体积稳定性研究

通过分析养护方法、水泥掺量等工艺参数或方法,研究了磷石膏复合胶凝材料早期强度及在不同环境条件下体积的变化规律。研究结果表明:掺加水泥不能有效提高复合胶凝材料的强度,反而会降低其早期强度;水泥掺量低于5%的水泥-磷石膏基复合胶凝材料在养护过程中呈现收缩性,而水泥掺量高于10%的复合胶凝材料呈现膨胀性,且在14d时收缩率达到最大,此后膨胀率逐渐降低。在湿度较大的养护环境中,水泥-磷石膏复合胶凝材料体积趋于膨胀;而在湿度较低的养护环境中,水泥-磷石膏复合胶凝材料体积趋于收缩。     

石灰-水泥-粉煤灰改性磷石膏对水泥物理性能的影响研究

采用石灰、水泥、粉煤灰对磷石膏进行改性处理,测定了改性磷石膏中硫酸根的溶解性能,对比了原状磷石膏与改性磷石膏对水泥物理性能的影响,并结合X射线衍射（XRD）和扫描电镜（SEM）分析了改性前后磷石膏对水泥不同龄期水化产物的影响。结果表明：随着石灰掺量的增加改性磷石膏的pH逐渐增大,当石灰掺量为4%（质量分数）时磷石膏的pH达到12.22,此时磷石膏中的可溶性磷、氟转化成难溶性的磷酸盐、氟化钙;随着水泥和粉煤灰掺量的增加,改性磷石膏的溶解性能呈现降低趋势。当石灰掺量为4%、水泥掺量为10%（质量分数）、粉煤灰掺量为10%（质量分数）时,改性磷石膏经过7 d养护在水中浸泡8 h所得滤液中硫酸根的质量浓度为0.30 g/L,比未改性磷石膏在水中浸泡8 h所得滤液中硫酸根的质量浓度降低了81.8%。与掺加未改性磷石膏的水泥浆体相比,掺加改性磷石膏的水泥浆体的水灰质量比由0.41降低到0.38、初凝时间和终凝时间分别缩短34.6%和27.2%、28 d抗压强度提高21.1%。石灰、水泥、粉煤灰改性处理磷石膏后,生成的水化硅酸钙和钙矾石等水硬性产物包裹在石膏颗粒表面,使硫酸根在水中的溶出速率降低,减少了对水泥中铝酸三钙的影响,使得硬化体内部结构变得致密、力学性能显著提高。     

基于电解锰渣-磷石膏复合胶凝材料的制备与表征

为了有效提高电解锰渣资源化利用水平,针对电解锰渣化学成分和矿物组成特点,以电解锰渣为主要原料,通过辅加磷石膏、水泥、矿粉制备胶凝材料;在固定矿粉与水泥掺量的基础上,通过改变磷石膏的掺量,研究不同硫酸盐掺量对复合胶凝材料力学性能的影响。研究结果表明,制备的复合胶凝材料中电解锰渣、磷石膏、矿粉、水泥最佳质量配比为50:20:20:10,其硬化体14 d抗压强度可达20.62 MPa,而软化系数为0.80。电解锰渣-磷石膏复合胶凝材料的水化产物主要是钙矾石、C-S-H、和C-A-S-H。水化14 d后的硬化体浸出液中污染物浓度均在《地表水环境质量标准》(GB 3838—2002)中Ⅴ类水体标准的限值内,其中Cr、Cu、Zn、As、Pb、Cd等重金属浓度可达到Ⅰ类水体的标准,硬化体具有良好的环境稳定性。     

改性磷石膏对石膏矿渣水泥水化过程的影响研究

采用质量分数为5％～25％的改性磷石膏、15％的硅酸盐水泥熟料、60％～80％的矿渣混合磨细制成石膏矿渣水泥,研究了改性磷石膏掺量对石膏矿渣水泥浆体的抗压强度、水化热、孔溶液pH值及水化产物的影响情况.结果表明,掺入改性磷石膏使得石膏矿渣水泥的3 d、7 d抗压强度降低,其掺量为10％、15％时,水泥的28 d、90 d抗压强度超过普通硅酸盐水泥.在3 d至90 d龄期内,水泥孔溶液pH值随龄期增长而逐渐增大.在相同龄期时,随着改性磷石膏掺量的增大,水泥孔溶液pH值减小,水化放热峰出现时间延缓.微观分析表明,掺入改性磷石膏后,28 d龄期时的水泥水化产物主要为钙矾石和C-S-H凝胶,水化产物的生成量在改性磷石膏掺量为15％时最多.     

磷石膏基复合胶凝材料的性能优化及机理研究

采用水泥、矿渣粉、粉煤灰和减水剂对磷石膏进行改性。最终得到的磷石膏基复合胶凝材料的强度为原状磷石膏的2倍,软化系数从0.5提高至0.8。磷石膏基复合胶凝材料的比强度和孔隙率之间存在明显的线性关系,随着孔隙率的减小比强度增加。通过扫描电镜（SEM）对磷石膏基复合胶凝材料微观形貌的演变过程进行表征,发现随着矿渣粉、水泥、粉煤灰和减水剂的掺加,基体由疏松转变为致密;主要的水化产物二水石膏从针状转变为棒状或片状,并且出现了水化硅酸钙（C-S-H）凝胶,其填充于体系内部的孔隙并将二水石膏连成整体。利用X射线衍射（XRD）分析和傅里叶变换红外吸收光谱（FT-IR）测试对水化产物的微观结构进行研究。结果表明,复合体系中的主要产物为二水石膏,但是由于可用水量的减少,体系中仍剩余少量磷石膏未水化。     

未预处理磷石膏砖的研究

本文研究磷石膏制砖另一种配料方式的可行性.以磷石膏为主要原料,添加石子、水泥和外加剂可制备符合JC422-91<非烧结普通粘土砖>标准的磷石膏砖.探讨了外加剂的种类及比例、粗集料掺量以及不同水固比和水泥用量对制砖物理性能的影响,并通过XRD、SEM分析磷石膏砖的水化产物.实验结果显示:当采用1%三聚氰胺,水泥用量为10%,粗集料掺量为20%且水固比为0.12时,制得的磷石膏砖的抗压强度值为18.6 MPa.     

磷石膏稳定红黏土的压缩特性及微观机理

针对红黏土特殊工程性质以及磷石膏固废资源的浪费现象,通过固结试验,以水泥为固化剂,研究不同配合比下磷石膏稳定红黏土的压缩特性,并基于微观结构和矿物组成分析压缩模量变化的机理。结果表明,素红黏土为中压缩性,磷石膏稳定红黏土为中、低压缩性。混合料压缩模量随磷石膏掺量增加先增大后减小,水泥与磷石膏质量比为1∶3时压缩模量最大。各因素对混合料压缩模量的影响程度依次为竖向荷载>水泥掺量>磷石膏掺量。混合料压缩模量与水泥掺量、磷石膏掺量可通过二元三次函数关系拟合。随着磷石膏掺量增加,水泥的水化反应、吸附作用以及钙矾石的生成使混合料孔隙率降低,当水泥与磷石膏质量比为1∶3时,孔隙率最小。当磷石膏掺量继续增大,溶液呈酸性,钙矾石溶解,游离氧化铁减少,团聚体内的胶结作用与咬合作用降低,压缩模量减小。     

提高磷石膏基水泥早期性能的研究

通过磷石膏预处理和添加超细硅酸盐水泥熟料的方法,对提高磷石膏基水泥早期性能进行了研究,并通过XRD、SEM对其水化过程和机理进行了探讨。结果表明,磷石膏经钢渣预处理,或采用超细熟料粉作为碱性激发剂,均能显著改善磷石膏基水泥的早期强度和凝结特性,两种措施同时采用时,能制备出3d抗压强度超过10MPa,28d抗压强度达49MPa以上的磷石膏基水泥。钢渣固结或固化了磷石膏中缓凝的可溶性杂质,超细粉磨使熟料自身水化加快并同时促进了矿渣水化,是磷石膏基水泥早期水化性能提高的原因。     

矿渣对阿利特-硫铝酸钡钙水泥水化硬化过程的影响

通过对水泥力学性能、水化速率和水泥硬化浆体孔结构的测定,结合XRD、SEM分析,研究了矿渣对阿利特-硫铝酸钡钙水泥水化硬化过程的影响。研究结果表明:掺入矿渣后,水泥的早期强度下降幅度较大,但后期强度下降幅度较小。在试验掺量范围内,当矿渣掺量为20%时,该水泥各龄期抗压强度下降幅度最小,其后期抗压强度接近纯熟料水泥;加入矿渣后,水泥水化热明显降低,矿渣在受到碱激发与硫铝酸盐双重激发作用下发生二次水化反应,使水泥水化速率有一定增加而出现第三个放热峰;矿渣二次水化反应有效地改善了硬化水泥浆体的孔结构,使水泥后期强度逐渐增加。     

Properties and hydration of blended cements with steelmaking slag

The present research study investigates the properties and hydration of blended cements with steelmaking slag, a by-product of the conversion process of iron to steel. For this purpose, a reference sample and three cements containing up to 45% w/w steel slag were tested. The steel slag fraction used was the “0-5 mm”, due to its high content in calcium silicate phases. Initial and final setting time, standard consistency, flow of normal mortar, autoclave expansion and compressive strength at 2, 7, 28 and 90 days were measured. The hydrated products were identified by X-ray diffraction while the non-evaporable water was determined by TGA. The microstructure of the hardened cement pastes and their morphological characteristics were examined by scanning electron microscopy. It is concluded that slag can be used in the production of composite cements of the strength classes 42.5 and 32.5 of EN 197-1. In addition, the slag cements present satisfactory physical properties. The steel slag slows down the hydration of the blended cements, due to the morphology of contained C₂S and its low content in calcium silicates.     

Effect of large amounts of natural pozzolan addition on properties of blended cements

In this study, the effects of 35, 45, and 55 wt.% natural pozzolan addition on the properties of blended cement pastes and mortars were investigated. Blended cements with 450 m²/kg Blaine fineness were produced from a Turkish volcanic tuff in a laboratory mill by intergrinding portland cement clinker, natural pozzolan, and gypsum. The cements were tested for particle size distribution, setting time, heat of hydration, compressive strength, alkali-silica activity, and sulfate resistance. Cement pastes were tested by TGA for Ca(OH)₂ content and by XRD for the crystalline hydration products. The compressive strength of the mortars made with blended cements containing large amounts of natural pozzolan was lower than that of the portland cement at all tested ages up to 91 days. Blended cements containing large amounts of pozzolan exhibited much less expansion with respect to portland cement in accelerated alkali-silica test and in a 36-week sulfate immersion test.     

水泥熟料与辅助性胶凝材料优化匹配的基础研究进展(Ⅰ)——物理效应

本文分析了复合水泥性能较差的本质原因,并指出优化水泥浆的初始堆积状态和水化进程是改善复合水泥性能的根本途径。在分析经典颗粒堆积模型和水泥颗粒级配模型优缺点的基础上,提出了复合水泥的颗粒级配模型,显著提高了新拌水泥浆体的初始堆积密度(最大固含量提高10%),以改善复合水泥的性能。     

A gap-graded particle size distribution for blended cements: Analytical approach and experimental validation

To increase the packing density of blended cement paste, a gap-graded particle size distribution (PSD) was theoretically deduced and modified according to the wet density of actual paste. Then experiments were conducted to validate the hypothesis of improvement of the properties of blended cements by the gap-graded PSDs proposed. The experimental results show that the gap-graded PSD resulted in a decreased water requirement and an increased packing density of blended cement paste, and modified gap-graded PSDs gave further effects. The heat of hydration of gap-graded blended cement pastes released slowly in the first 24 h and increased rapidly afterward. The microstructure of gap-graded blended cements was much more homogeneous and denser than that of reference blended cement, therefore both early and late mechanical properties of low clinker gap-graded blended cements were improved significantly and even higher than those of Portland cement.     

Determining the water–cement ratio, cement content, water content and degree of hydration of hardened cement paste: Method development and validation on paste samples

We propose a new method to estimate the initial cement content, water content and free water/cement ratio (w/c) of hardened cement-based materials made with Portland cements that have unknown mixture proportions and degree of hydration. This method first quantifies the composition of the hardened cement paste, i.e. the volumetric fractions of capillary pores, hydration products and unreacted cement, using high-resolution field emission scanning electron microscopy (FE-SEM) in the backscattered electron (BSE) mode and image analysis. From the obtained data and the volumetric increase of solids during cement hydration, we compute the initial free water content and cement content, hence the free w/c ratio. The same method can also be used to calculate the degree of hydration. The proposed method has the advantage that it is quantitative and does not require comparison with calibration graphs or reference samples made with the same materials and cured to the same degree of hydration as the tested sample. This paper reports the development, assumptions and limitations of the proposed method, and preliminary results from Portland cement pastes with a range of w/c ratios (0.25–0.50) and curing ages (3–90 days). We also discuss the extension of the technique to mortars and concretes, and samples made with blended cements.     

Investigation of blended cement hydration by isothermal calorimetry and thermal analysis

Hydration of portland cement pastes containing three types of mineral additive; fly ash, ground-granulated slag, and silica fume was investigated using differential thermal analysis, thermogravimetric analysis (DTA/TGA) and isothermal calorimetry. It was shown that the chemically bound water obtained using DTA/TGA was proportional to heat of hydration and could be used as a measure of hydration. The weight loss due to Ca(OH)₂ decomposition of hydration products by DTA/TGA could be used to quantify the pozzolan reaction. A new method based on the composition of a hydrating cement was proposed and used to determine the degree of hydration of blended cements and the degree of pozzolan reaction. The results obtained suggested that the reactions of blended cements were slower than portland cement, and that silica fume reacted earlier than fly ash and slag.     

Influence of the fineness of pozzolan on the strength of lime natural-pozzolan cement pastes

The fineness of a cement is an important factor affecting the rate of strength development. This paper examines the importance of the fineness of natural pozzolans to the strength development of lime-pozzolan cements (LPCs). A natural pozzolan from Bolivia, which is typical of natural pozzolans found in South and Central America, was ground to various finenesses, blended with lime with a mass ratio of 80:20, and the resulting LPC was used to make hardened cement paste cylinders. In some pastes 4% sodium sulphate or 4% sodium chloride activator was used to enhance strength development. Strength of the cylinders were measured at ages from 3 to 90 days during continuous moist curing at 50°C. The experimental results show that there is a good linear correlation between the Blaine fineness of the natural pozzolan and compressive strength at all ages and for all pastes. The fineness of the natural pozzolan has its most significant effect on early strength gain. The addition of chemical activator increases both the rate of strength gain and the sensitivity of strength gain to fineness.     

碱对硅酸盐水泥水化硬化性能的影响

系统地研究了以碱含量不同、存在形式各异的熟料所制水泥的水化液相成分、水化程度、水化产物和硬化浆体微观结构,揭示了碱对硅酸盐水泥水化硬化性能影响的机理。水泥水化时,熟料中的碱迅速溶入水化液相,使液相中[OH-]升高、[Ca~(2+)]降低。由此促进水泥早期水化,并阻滞了后期水化的发展。所以,高碱水泥凝结快,1～3d硬化浆体的孔隙少、强度高;7～28d硬化浆体的孔隙多、强度低。     

水泥熟料与辅助性胶凝材料优化匹配的基础研究进展(Ⅱ)——化学效应

在分析水泥熟料与辅助性胶凝材料水化程度、填充能力和强度贡献率的基础上,提出了水泥熟料与辅助性胶凝材料优化匹配原则。利用该原则,可在降低水泥熟料用量、提高辅助性胶凝材料(特别是低活性辅助性胶凝材料)掺量的同时,显著改善复合水泥的强度、体积稳定性等性能,实现水泥熟料、矿渣等胶凝材料的高效利用。