Microstructural analysis of plain and reinforced mortars under chloride-induced deterioration

This paper reports the results of microstructural analysis of plain and steel-reinforced mortar specimens deteriorated by chlorides that were admixed or introduced through chloride ingress. The electrical properties of mortars were measured and their microstructural characteristics were investigated using quantitative image analysis techniques. The influence of chloride ions on mortar microstructure are discussed in terms of hydration and corrosion products. The research reveals that chlorides will induce changes in the chemical compositions and morphology of cement hydration products, and thereby exert influence on ion transport in the mortar specimens. The electrical properties of plain and reinforced mortars are not only related to the presence of chlorides in the pore system but are also influenced by the pore structure characteristics. The cementitious matrix undergoes certain alterations in conditions of the combined effects of: cement hydration, chloride ion transport and chemical binding mechanisms. To this end the pore structure characteristics appeared to be a significantly contributing factor in the process of chloride-induced corrosion in reinforced cement-based materials.     

不同pH值碱性电解水对砂浆工作性能和强度的影响

碱性电解水具有强碱性、高活性、离子性和吸附性等优点,本文利用不同pH值(9.5、10.5、11.5)的碱性电解水制备粉煤灰砂浆,并在粉煤灰取代率为0%、15%及30%(质量分数)的条件下,系统研究了不同pH值碱性电解水对粉煤灰砂浆的工作性能、力学性能以及Ca(OH)₂等水泥水化产物含量的影响规律,并利用XRD、SEM等微观试验对比分析了不同pH值的粉煤灰净浆的结构组成和微观形貌特征。试验结果表明:随着pH值的提高,相较于普通自来水粉煤灰砂浆,碱性电解水粉煤灰砂浆的流动度、抗压强度和抗折强度逐渐提高,水化产物Ca(OH)₂含量逐渐降低。当碱性电解水pH值为10.5,粉煤灰取代率为15%时,碱性电解水粉煤灰砂浆的早期强度和流动度的改善效果达到最佳,28 d的抗压强度和抗折强度较普通水砂浆分别提高了8.4%和12.5%。同时,相较于普通自来水净浆,不同pH值的碱性电解水净浆的团簇化和颗粒化均表现得更加明显,这对于促进水泥水化进程,提高砂浆流动性,激发粉煤灰早期活性起到了积极作用,除了生成更多的C-S-H凝胶体和Ca(OH)₂等水化产物以外,还生成了钾长石等其他水化产物。     

己二酸对掺石灰石粉水泥浆性能的影响

为探究掺加石灰石粉的水泥浆中加入己二酸的作用效果,对添加己二酸的掺石灰石粉水泥浆体流动性、强度、水化热及化学结合水的影响规律进行了研究.利用X射线衍射和扫描电镜技术手段对其机理进行分析.结果表明:己二酸的加入提高了掺石灰石粉水泥浆体的流动度、3 d强度、早期水化温升值和早期水化结合水量,掺入己二酸在3d时生成更多的水化碳铝酸钙,水化产物结构更加致密.     

煤矸石对硅酸盐水泥水化历程的影响

从强度、反应程度、孔溶液碱度和SEM等方面,研究了煤矸石作为水泥辅助胶凝材料的水化情况,并与Ⅱ级粉煤灰进行比较。试验结果表明:煤矸石发生火山灰反应时间比粉煤灰早,且发生火山灰反应所需的碱度值比粉煤灰低;掺煤矸石水泥水化样的早期抗压强度比粉煤灰水泥水化样低,但7d到28d强度增长速率明显大于相同掺量的粉煤灰水泥,相同28d抗压强度的条件下,煤矸石掺量比粉煤灰的掺量高10%。     

29Si Magic-Angle-Spinning Nuclear Magnetic Resonance Study of Hydrated Cement Paste and Mortar

This paper presents ²⁹Si magic-angle-spinning nuclear magnetic resonance measurements that trace the cement hydration process in cement paste and mortar specimens made from ordinary portland cement, type I. These specimens were moist-cured for 3, 7, 14, and 28/31 d at temperatures ranging from 21° to 80°C. Compressive strength for all tested specimens was also determined. The results show that the degree of hydration ( Q ¹+ Q ²) and the compressive strength increase with curing times and temperatures. However, at 80°C, the compressive strength decreases while the degree of hydration increases.     

海水和矿物掺合料对硫铝酸盐水泥砂浆性能的影响

本文研究了不同拌和水以及海水拌和时粉煤灰和硅灰掺量对硫铝酸盐水泥(SAC)砂浆力学性能和表观孔隙率以及净浆凝结时间、化学收缩、孔溶液pH值和氯离子结合能力等的影响,并通过XRD、SEM和EDS分析水泥水化产物和微观结构。结果表明,海水能加快SAC早期水化并提高其早期强度,但后期强度和淡水拌和时无明显差别。粉煤灰和硅灰均会延长SAC凝结时间,对早期抗压强度不利,而掺加质量分数为5.0%和7.5%的硅灰能提高SAC砂浆28 d抗压强度。硅灰掺量增加时会提高用水量和表观孔隙率,降低流动性,使水泥化学收缩增大,降低净浆pH值且减少氯离子结合量;粉煤灰能够提高砂浆流动性,减少水泥化学收缩,但掺量越大对SAC砂浆抗压强度和抗折强度越不利,掺质量分数为10%的粉煤灰可小幅提高氯离子结合量且减小表观孔隙率。     

环氧水泥砂浆的改性机理

通过对环氧改性水泥净浆的水化程度和砂浆的孔结构研究，借助于扫描电镜分析，探讨了聚合物对水泥砂浆的改性机理。聚合物的存在一方面延缓了水泥的水化速度，另一方面改善了硬化浆体的毛细孔结构，一部分聚合物在硬化浆体中形成不连续的薄膜。所以聚合物的改性作用是上述两方面的综合作用。     

X-ray absorption study of drying cement paste and mortar

X-ray absorption was used to observe water evaporation with hydration time in paste and mortar specimens, with the aim of studying the influence of water/cement (w/c) ratio, presence of aggregates, curing conditions on drying during early hydration. For the samples subjected to surface drying immediately after mixing, there exists a moisture gradient within the internal part of the specimen. However, obvious top-down drying only occurs within a small zone near the surface for early age cement pastes and mortars. The evaporation rate of water is very high in the first day after casting and is drastically reduced afterwards due to the formation of a microstructure that greatly improves specimens resistance to moisture loss. Mortars reveal a slightly lower evaporation rate since the aggregate increases the length of the transport route because of a larger tortuosity. However, the effect of sealed curing is much more important than the tortuosity effect of the aggregates.     

磺化淀粉开发用作新型水泥减水剂的研究

以氯磺酸为磺化试剂,半干法制备了磺化淀粉,并对其用作水泥减水剂的性能进行了系统的研究。结果表明:磺化淀粉减水率随磺酸基取代度增加而增加,当其取代度达到0.060 4,质量分数为0.3%时测得的水泥净浆减水率、净浆标准凝结时间和3 d、28 d砂浆强度等各项指标均达到高效减水剂的国标要求,磺化淀粉对水泥还具有一定的缓凝作用。通过XRD和SEM,对掺加了磺化淀粉的水泥材料进行了微观结构表征,结果表明:磺化淀粉掺入水泥浆后,由于缓凝作用导致初期水化反应发展缓慢;而经较长时间(如28 d)后硬化水泥结构比基准样密实、强度更高。而且磺化淀粉掺量0.3%(质量分数)即可达到高效减水剂的要求,比现有的高效减水剂掺量都低。     

Effect of the Interfacial Transition Zone on the Conductivity of Portland Cement Mortars

The electrical conductivity of portland cement mortars was determined experimentally as a function of the volume fraction of sand and the degree of hydration. The results were analyzed using theoretical models that represent the mortars as three-phase, interactive composites. The three phases are the matrix paste, the aggregate, and the thin interfacial transition zone between the two. The microstructure and properties of the conductive phases (the transition zone and the matrix paste) were determined by a micrometer-scale microstructural model, and were used in conjunction with random-walk algorithms and differential-effective medium theory to determine the overall mortar conductivities. The presence of the transition zone was not found to significantly affect the global electrical conductivity of the mortar. However, there were significant differences in conductivity between the transition zone and matrix pastes when examined on a local level. These differences were found to vary with hydration and were most significant when the degree of hydration was between 0.5 and 0.8.     

不同细度水泥的水化特性及其对水泥砂浆自愈合性能的影响

研究了不同细度水泥的水化热、水化产物和力学性能,以及水泥细度和养护条件对预制裂缝的水泥砂浆强度恢复率和裂缝愈合的影响.结果表明:随着水泥比表面积增大,水泥水化放热量峰值越高,相同龄期下的水化程度越高;预制裂缝试块在自然养护、标准养护和水中养护90 d后的强度恢复率呈现出来相似的规律,均随着细度增加而逐渐减小;比表面积为254 m2/kg和407 m2/kg的水泥制成的砂浆试块,预制裂缝的初始最大宽度都为0.070 mm,前者水中养护90 d后裂缝基本愈合;而后者的裂缝愈合率只有57.1%.     

水泥-乳化沥青-环氧乳液复合胶浆硬化机理研究

针对水泥路面表面损伤修补材料应当具有良好的适应性、界面粘结强度高和较强耐久性等特点,对砂浆类修补材料进行复合改性,研发出一种新型有机-无机类复合修补材料--CAE复合胶浆.对不同龄期的CAE砂浆进行抗折、抗压试验以及冲击韧性试验并采用XRD、红外光谱和SEM等微观测试方法研究其硬化机理.研究结果表明,环氧乳液掺量为30％时,CAE复合胶浆抗折强度与普通砂浆差别不大,抗压强度较普通砂浆低,但冲击韧性显著提高.加入乳化沥青和环氧乳液能够延缓水泥水化但不能阻碍水化进程,环氧乳液能够在CAE复合胶浆中完全固化,乳化沥青和环氧乳液固化形成的网络结构与水泥水化产物相互交织穿插,有效改善了CAE复合胶浆材料的孔隙结构.     

Influence of solution chemistry on the hydration of polished clinker surfaces—a study of different types of polycarboxylic acid-based admixtures

The influence of two different types of polycarboxylic acid-based superplasticizers (homo- [HP] and copolymer [CP]) on the early hydration of Portland cement clinker is investigated. Polished clinker surfaces are hydrated in aqueous phase extracted from cement paste with and without superplasticizers as well as in saturated Ca(OH)₂/CaSO₄ solution and in deionized water. Scanning electron microscopy (SEM) is used to characterize the early hydration products after 30 min and after 24 h of hydration. Contrary to the hydration reaction with deionized water, in the presence of ionic solutions, the texture and morphology of the clinker surface are significantly altered, and amorphous and crystalline hydration products, mainly ettringite, are formed. The amount and type of ettringite formed are strongly related to solution chemistry and type of superplasticizer. In the presence of superplasticizers, the formation of hydration products and ettringite is reduced and the hydration of the surface is suppressed. Furthermore, the rate of hydration in mortar is studied in the presence of the two admixtures by measuring the temperature evolution as a function of time. The concentration-dependent delay in temperature evolution correlates well with the microscopic observations of different amounts of ettringite formation.     

掺石灰石粉水泥的水化过程及微观结构

用微量热仪测定了含石灰石粉水泥浆体的水化放热。用扫描电镜观察了掺石灰石粉水泥硬化浆体的微观结构。试验结果表明:一定细度的石灰石粉可加速水泥的水化,掺石灰石粉水泥的水化放热量低于不掺石灰石粉水泥的水化放热量。水泥硬化浆体中沿着石灰石粉片状方解石晶体的边缘容易形成平整断面。     

减缩剂对水泥基材料水化和孔结构的影响(英文)

通过对水泥净浆水化放热量、Ca(OH)2的含量和化学结合水量及水泥砂浆的孔结构的测定,研究减缩剂对水泥基材料水化和孔结构的影响.结果表明:减缩剂会延缓水泥的水化,且随着龄期的发展,延缓作用渐弱.具体表现为减缩剂会降低水泥水化放热的峰值,延迟峰值出现的时间,减小水化放热量;减缩剂能够减小水泥净浆的化学结合水量;龄期为3d时,掺减缩剂的净浆中Ca(OH)2的含量明显低于空白样的,28d时与空白样的相当;减缩剂能够减小水泥砂浆中多害孔和有害孔的孔体积,增加无害孔的孔体积.另外还对减缩剂在水泥基材料中存在的形态提出设想.     

铜渣-水泥复合胶凝材料力学性能研究

铜渣以5%、10%、15%的比例取代水泥制备铜渣-水泥复合胶凝材料.研究铜渣对水泥基胶凝材料标准稠度用水量、凝结时间、净浆抗压强度、胶砂抗折与抗压强度的影响,并利用XRD、TG/DSC和SEM-EDS技术手段分析掺入铜渣后水泥基胶凝材料物相和微观形貌的变化.研究结果表明:铜渣掺入会使水泥胶凝材料的标准稠度用水量增加,凝结时间延长,一定程度上提高水泥胶凝材料的抗折、抗压强度;铜渣-水泥胶凝材料的主要水化产物和水泥胶凝材料类似,并有Fe(OH)3/Fe(OH)2凝胶生成.铜渣-水泥复合胶凝材料微观结构较水泥胶凝材料密实.     

石蜡胶囊的制备及其对砂浆热导和力学性能的影响

为解决固-液相变材料封装问题,以石蜡为芯材,陶粒颗粒为载体,水泥为封装材料制备了石蜡胶囊.分析了石蜡胶囊的基本性质,测试了石蜡胶囊的DSC曲线;并将石蜡胶囊掺入砂浆中,研究了掺入石蜡胶囊对砂浆热导和力学性能的影响.研究表明:使用水泥封装后,石蜡胶囊的密封性好,高温下不会发生泄露;石蜡胶囊掺入砂浆中,对砂浆力学性能影响较小,且可降低砂浆的导热系数和水泥水化温度,并推迟水化温度峰值的出现.     

纳米颗粒对道路粉煤灰混凝土耐磨性能的影响及作用机理

为探讨纳米颗粒对道路粉煤灰混凝土耐磨性能的影响,采用纳米材料和超细粉煤灰等量取代水泥制备了纳米改性粉煤灰水泥砂浆,在此基础上制备出三种纳米改性道路粉煤灰混凝土:纳米SiO2 (NS)混凝土、纳米SiC(NC)混凝土和纳米复掺混凝土,并研究了两种纳米材料对粉煤灰水泥砂浆力学性能和道路粉煤灰混凝土耐磨性能的影响及作用机理.结果表明:混凝土中掺入纳米材料能显著提高其耐磨性能.单掺NS混凝土中NS最优掺量为2％,单掺NC混凝土中NC最优掺量为3％;而复掺2％ NS、2％ NC时,纳米复掺混凝土耐磨性最佳,与基准混凝土相比,磨损量降低了75％.分析认为:纳米材料的表面效应、活性效应和微集料填充效应使其具有较大的表面能,在水泥浆体中与Ca(OH)2晶体发生二次水化反应,改善了Ca(OH)2的取向程度,强化了水泥石微细观结构,优化了水泥基体内孔径分布与孔结构,使其更加密实,从而提高了道路粉煤灰混凝土的耐磨性能.     

In situ double torsion fracture studies of cement mortar and cement paste inside a scanning electron microscope

The characteristics of microcracking in cement and high strength mortar have been investigated by fracture experiments of small (33×11×1.1mm) double torsion (DT) type specimens, inside the specimen chamber of a conventional scanning electron microscope. The control of incremental crack growth, at less than a micron, is finer than has been reported before. The cracking path is tortuous and quite branched both around and through fine aggregate particles, thus absorbing significantly more energy than a corresponding straight crack. In the vicinity of the main crack tip a zone of diffuse microcracking was observed which may be regarded as a “process zone”. These two observations suggest that fracture mechanics models utilising discrete straight single cracks should only be used with circumspection. In cement paste there also appeared to be a transition from predominantly intergranular to transgranular fracture with increased age of hydration.     

An evaluation of the sulfate resistance of cementitious material accelerated with alkali-free and alkaline admixtures: Laboratory vs. field

A comparison between conventional length change measurements (cement paste, mortar and shotcrete) and ion chromatographic, pH and conductivity measurements (cement paste suspensions) is made in order to find out a relationship between the sulfate resistance of laboratory and field prepared specimens. A correlation between the linear expansion of shotcrete specimens and both the total amount of adsorbed sulfates [ion chromatography (IC) measurements] and the SO₄²⁻⇔OH⁻ exchange (pH and conductivity measurements) within the cement binders is found. Furthermore, a good correlation between the long-term expansion of shotcrete and the short-term expansion of cement paste specimens is observed. On the other hand, no correlation exists between the linear expansion of shotcrete and laboratory mortar specimens. This suggests that the laboratory investigation of the more reactive cementitious material with respect to sulfate ions might be taken as a trustworthy and reproducible evaluation of the sulfate resistance of shotcrete in the field.