矿物掺和料与再生骨料对水泥强度和收缩性能的影响

矿物掺和料与再生骨料应用于水泥制品中是废弃物资源化利用的重要途径。为了研究矿物掺和料与再生骨料对水泥强度和收缩性能的影响,设计不同掺和料掺合比例与再生骨料取代率,进行不同龄期的强度、干燥收缩和早期自收缩测试。结果表明,粉煤灰降低水泥强度,而矿粉可提高水泥后期强度;粉煤灰和矿粉对水泥的干燥收缩有抑制作用,但对水泥早期自收缩有促进作用;再生骨料能够提高水泥强度,而对水泥的收缩性能无明显影响。     

海水环境下矿物掺合料对硫铝酸盐水泥的水化影响

研究了海水环境下掺入硅灰、粉煤灰、矿渣对硫铝酸盐水泥抗压强度、化学收缩和水化产物的影响规律.结果表明:当硅灰的掺量为2.5%时,水泥浆体的抗压强度比空白组高.矿渣掺量为10%的水泥浆体28 d抗压强度明显超过掺入硅灰和粉煤灰时的强度,60 d强度高于空白组.掺入2.5%硅灰后,水泥浆体的化学收缩增大;在水化早期,粉煤灰和矿渣的火山灰活性很低,导致水泥浆体的化学收缩降低.掺入10%硅灰加快了硫铝酸盐水泥3 d水化反应,钙矾石生成量增多,水泥浆体早期强度比掺其它掺合料有所提高,但体积过快膨胀会破坏其内部结构,对水泥浆体的强度发展不利.     

Thermal behavior of cement matrix with high-volume mineral admixtures at early hydration age

Thermal cracks that usually occur in mass concrete are closely related to the thermal behavior of cement matrix, such as heat liberation, temperature rise and thermal shrinkage. Cement pastes added with large-volume mineral admixtures that are usually used for thermal controlling were cast into well-sealed plastic cylinder and covered by heat insulation materials to simulate the pseudo-adiabatic condition of mass concrete. The deformation and temperature rise of cement specimens under the heat insulation condition have been examined at early hydration age. Results show that with addition of fly ash, coal gangue and blast furnace slag the heat liberation and peak temperature of cement paste decrease, while its total shrinkage increases.There is no shrinkage but expansion of the pastes during the temperature rise process, which may be ascribed to the complete compensation of the shrinkage by thermal dilation of the pastes. The thermal dilation coefficient (TDC) of cement paste changes drastically with the hydration duration, and it is also related to the addition of mineral admixtures.     

Effect of mineral filler type on autogenous shrinkage of self-compacting concrete

Based on an experimental programme, including autogenous shrinkage tests on concrete, ultrasonic monitoring of fresh concrete, and mercury intrusion porosimetry, the influence of the filler type on the autogenous shrinkage of self-compacting concrete has been investigated. The onset of percolating structure formation (time zero) is influenced by the filler type due to a possible accelerating effect of the filler on the cement hydration. Limestone filler accelerates the hydration process, and reduces time zero, while this is not the case when using quartzite filler. Using fly ash, showing only a slight acceleration, a slight reduction of time zero is obtained. A very significant swelling peak is noticed during the first day. This swelling peak is not a measuring artefact, but is caused mainly by water absorption on the filler surface and resulting disjoining pressure. Some part of the swelling peak might also be caused by Ca(OH)₂ crystallisation. The fineness of the filler is an important factor for this swelling behaviour, although also the nature of the filler seems to have an influence. The superplasticiser also interacts with the fillers, influencing the swelling behaviour. The different filler types used in this study did not lead to significant differences in critical pore diameter of the microstructure. This might explain why no significant differences have been found in final autogenous shrinkage values using the different filler types.     

Relation between the molecular structure and the efficiency of superabsorbent polymers (SAP) as concrete admixture to mitigate autogenous shrinkage

Superabsorbent polymers (SAP) were studied as admixtures for mitigating the autogenous shrinkage of a high-strength concrete. The presence of Ca²⁺ ions in the alkaline solution modified the kinetics of the liquid uptake and release when compared to that in other saline solutions and distilled water. SAP with high density of anionic functional groups took up the cement pore solution quickly, but greatly released it subsequently. The cross-linking density had no pronounced influence on the behaviour of such SAP. SAP with lower density of anionic groups did not release the liquid over the time of experiment. All SAP counteracted autogenous shrinkage during the acceleration period of cement hydration. For the materials which released the absorbed pore solution no effect on autogenous shrinkage was found beyond the initial period. SAP materials which did not release the absorbed solution in the experiments with liquids continued the mitigation of autogenous shrinkage during the deceleration period. The internal curing had no negative effect on the compressive strength of the mortar.     

Changes in microstructures and physical properties of polymer-modified mortars during wet storage

The decrease in strength of tile adhesive mortars during wet storage was investigated. In a first approach, the water resistance of the polymer phases was tested on structures isolated from the mortar and in situ. It was observed that cellulose ether and polyvinyl alcohol structures are water-soluble. Subsequent investigations on polymer mobility within the mortar showed that the migrating pore water transports cellulose ether and polyvinyl alcohol during periods of water intrusion and drying. This leads to enrichments at the mortar-substrate interface. In contrast, latices interacting with the cement are water-resistant, and therefore, immobile in the mortar. Further experiments revealed that the mortar underwent considerable volume changes depending on the storage condition. Cracking occurred mainly close to the mortar-tile interface, cement hydrates grew within these shrinkage or expansion cracks. Test results revealed that the strength decrease of wet stored tile adhesives is caused by different mechanisms related to cement hydration, volume changes of the mortar, and reversible swelling of latex films.     

粉煤灰-偏高岭土-石粉对混凝土微结构及早期收缩的影响研究

以偏高岭土、粉煤灰和石粉作为复合掺和料,结合混凝土孔结构、界面过渡区(ITZ)及水化热等表征研究多元复合掺合料对混凝土抗压强度及早期收缩性能的影响.研究结果表明:粉煤灰-偏高岭土-石灰石粉多元复合掺和料对混凝土抗压强度有促进作用,其28 d龄期强度增长10%以上,降低孔隙率,减少混凝土试样200 h收缩率13%~23%,且收缩率随着石粉含量增加和偏高岭土含量增加而降低.偏高岭土复合掺和料加速了水泥水化反应过程,促进了CSH凝胶的快速形成,密实了界面过渡区.     

水泥-硅灰/粉煤灰体系强度、收缩性能与微观结构研究

为研究硅灰及粉煤灰对不同养护龄期的水泥浆体强度及收缩性能的影响,以水胶比为0.29的水泥浆体为基体,设计制备了五种硅灰及粉煤灰掺量的复合水泥浆体,借助量热仪和压汞仪测试表征了不同复合水泥浆体的水化放热特性以及孔结构组成,分析了水化放热量、孔隙率等参数随硅灰和粉煤灰掺量增加的变化规律,建立了复合浆体抗压强度与孔结构以及水化特性与收缩应变之间的量化关系。结果表明,掺入粉煤灰会大幅降低水泥净浆早期抗压强度,但对减小自收缩应变和干缩应变极为有利。掺入硅灰能明显提高净浆3 d抗压强度,但当硅灰掺量超过10%(质量分数)后,净浆3 d自收缩应变及28 d干缩应变增加极为明显。掺入硅灰会使水泥水化诱导期开始和结束的时间提前,还会增加水化反应级数和各阶段的反应速率常数值,导致水泥-硅灰复合浆体的水化放热总量和放热速率相较于水泥-粉煤灰体系大幅增加。粉煤灰和硅灰的掺入均能有效细化水泥浆体内部孔结构,提高凝胶孔比例,大幅降低大孔比例。复合浆体的72 h水化放热总量和3 d自收缩应变呈现正相关关系,而孔隙率和抗压强度呈现明显的负相关关系。     

碱-矿渣水泥性能研究及应用

研究了碱-矿渣水泥水化产物组成、水泥石孔结构和孔液成分、力学性能、水化热、抗化学腐蚀性能和对钢筋的钝化作用等;并对混凝土的力学性能、干缩变形、耐久性和对外加剂的适应性等进行了研究。结果表明,碱-矿渣水泥具有早强、高強、低水化热和高耐久性等优良性能,但是干缩较大;选择适当的外加剂可以改善部分性能。介绍了利用该水泥的特性在多种工程中的应用情况。     

The influence of sodium and potassium hydroxide on volume changes in cementitious materials

This research investigates the influence of alkali hydroxides on unrestrained volume changes. A detailed multi-method approach is used to characterize the progress of cement hydration, autogenous and drying volume changes (i.e., shrinkage), autogenous RH decrease, compressive strength development, solid and liquid phases and the pore structure. It is noted that under autogenous conditions, alkalis magnify shrinkage; while upon external drying the extent of shrinkage is more similar. This is contrary to expectations which suggest that the reduction in the water activity and the negative pressure developed in the liquid phase, produced by alkali enrichment, should reduce shrinkage. Analysis of the autogenous RH decrease, pore solution chemistry and the mechanical properties indicates that the bulk shrinkage response is linked to multiple parameters including: (1) increased self-desiccation at early ages, (2) a reduction in the strength (and stiffness) of alkali-enriched systems and (3) liquid saturation effects.     

NMR diffusion and relaxation studies during cement hydration—A non-destructive approach for clarification of the mechanism of internal post curing of cementitious materials

Internal post-curing of hardening cement pastes by addition of alginate spheres, which contain 98% of water, is studied by non-destructive ¹H NMR measurements of transverse relaxation time and self-diffusion. The onset and amount of water transition from the alginate gel used as additive with temporary delayed release of water to cement pastes was observed continuously during the dormant and accelerated period of cement hydration. During hydration, the water transition from the alginate into the cement matrix as well as the development of pore size is monitored quantitatively by studying the time dependence of characteristic peaks in the transverse relaxation time distribution. Comparison between samples without and with internal post curing shows that the addition of alginate gel does not influence the pore size in the micropore region. NMR diffusion studies demonstrate that the physically bound pore water has sufficient mobility to ensure homogeneous distribution of water from the alginate source into the surrounding cement matrix during the dormant and accelerated period.     

蔗糖对水泥水化历程的影响

通过研究蔗糖对水泥凝结时间、水化热、化学收缩及抗压强度等的影响,探讨了蔗糖对水泥水化历程的影响规律及调凝机理。结果表明;蔗糖的掺量存在一个临界值,低于此掺量时,随着蔗糖掺量的增加,凝结时间逐渐延长;高于此掺量时,凝结时间迅速从最大值回落,直至促凝,净浆强度显著降低。在蔗糖作用下,预诱导期出现一个温度高峰,且峰值随掺量的增大而升高,加速期温峰逐渐减小且后移,水泥水化8h内,化学收缩随蔗糖掺量的增大而增加,化学收缩随掺量的增大而降低。蔗糖对水泥浆具有增溶作用,促进铝酸三钙及中间相的水解,加速钙钒石的生成。     

纳米SiO_2对硅酸盐水泥水化放热特性的影响

以硅灰为对比,利用微量热仪研究了纳米SiO2对硅酸盐水泥24 h内水化历程、水化放热特性的影响.研究结果表明:掺入纳米SiO2的水泥试样24 h内水化历程也可划分为类似于纯硅酸盐水泥水化的5个阶段;纳米SiO2的掺入,促使诱导期、加速期和减速期的出现提前,缩短了诱导期持续的时间;提高了水化开始时的放热速率,使第二放热峰的出现提前,增大了水化放热量.     

Combined effect of expansive and shrinkage reducing admixtures to obtain stable and durable mortars

In order to improve the dimensional stability of cement based mortars, the effects produced on cement hydration of a shrinkage reducer (propyleneglycol ether based—SRA) and an expansive admixture (calcium oxide based—EXP) were investigated. Mortar samples (prepared without admixtures or with SRA or EXP or SRA and EXP) were compared through compressive strength measurements, water evaporation, restrained shrinkage and restrained expansion measurements. Setting time and free expansion were also detected on cement paste specimens.

A synergistic effect on the shrinkage reduction was observed when the shrinkage reducing admixture and the expansive agent were used together. In order to clarify this phenomenon, the hydration of cement pastes containing these kinds of admixtures was followed by ESEM-FEG (environmental scanning electron microscopy–field emission gun), TG (thermogravimetry), specific surface area measurements (by BET—Brunauer–Emmet–Teller-method) and XRDS (X-ray diffraction spectroscopy).     

水胶比和组成对补偿收缩胶凝材料的水化反应的影响

在不同水胶比条件下，利用等温量热法测量了不同组成的补偿收缩胶凝材料的水化放热速率和放热量曲线，以评价其水化特性及其对强度和膨胀性能的影响。随着水胶比逐渐降低，水化受到抑制。在水胶比为0．3时，补偿收缩胶凝材料的总放热量和水化放热速率有明显降低。由矿物掺和料、膨胀剂和硅酸盐水泥组成的复合胶凝材料的总放热量和水化放热速率较低，但后期水化放热增加量较大。水胶比大于0．4后，水胶比的变化对复合胶凝材料的水化过程影响很小。     

Study on the hydration heat of binder paste in high-performance concrete

High-performance concrete (HPC) is a type of new concrete materials developed in the recent 10 years. Compared with normal strength concrete (NSC), HPC is made with lower water-binder ratio (W/B), larger dosage of superplasticizer and addition of different types of mineral admixtures. The objective of the article was to evaluate the effect of W/B, superplasticizer and mineral admixtures on the hydration heat of the binder paste in HPC. The testing results showed that the hydration heat reduced with the decrease of W/B of the binder paste. The total hydration heat did not decrease with the incorporation of superplasticizer containing retarding component, however, the hydration exothermic process was delayed. Mineral admixtures greatly reduced the hydration heat and the exothermic rate and prolonged the arrival time of the highest temperature, particularly when two or three types of mineral admixtures were added at the same time (double adding and triple adding). The influence of these three factors on hydration heat may counteract the deficiency of high hydration heat at early stage due to high cement content and high-strength cement usually used in HPC. This way, the influence of temperature stress is alleviated and the durability of concrete is enhanced.     

Interactions between shrinkage reducing admixtures (SRA) and cement paste's pore solution

Shrinkage reducing admixtures (SRA) have been developed to combat shrinkage cracking in concrete elements. While SRA has been shown to have significant benefits in reducing the magnitude of drying and autogenous shrinkage, it has been reported that SRA may cause a negative side effect as it reduces the rate of cement hydration and strength development in concrete. To examine the influence of SRA on cement hydration, this study explores the interactions between SRA and cement paste's pore solution. It is described that SRA is mainly composed of amphiphilic (i.e., surfactant) molecules that when added to an aqueous solution, accumulate at the solution-air interface and can significantly reduce the interfacial tension. However, these surfactants can also self-aggregate in the bulk solution (i.e., micellation) and this may limit the surface tension reduction capacity of SRA. In synthetic pore solutions, SRA is observed to form an oil-water-surfactant emulsion that may or may not be stable. Specifically, at concentrations above a critical threshold, the mixture of SRA and pore fluid is unstable and can separate into two distinct phases (an SRA-rich phase and an SRA-dilute phase). Further, chemical analysis of extracted pore solutions shows that addition of SRA to the mixing water depresses the dissolution of alkalis in the pore fluid. This results in a pore fluid with lower alkalinity which causes a reduction in the rate of cement hydration. This may explain why concrete containing SRA shows a delayed setting and a slower strength development.     

Hydration and properties of calcium silicate pastes

Microstructures developed in hydrated tricalcium and β-dicalcium silicates paste are related to physical properties of strength, rigidity and shrinkage. Paste microstructure was altered by the use of admixtures and by temperature variations during hydration. Strength, both compressive and tensile, is essentially independent of changes in microstructure and depends primarily on porosity. However, the paste rigidity as estimated from the modulus of elasticity, measured by a new ultrasonic pulse velocity technique, is affected by changes in the CSH material promoted by some admixtures, e.g., calcium chloride. The size of calcium hydroxide crystals may influence total paste shrinkage, although other factors, such as pore size distribution, have not yet been fully assessed.     

Interactions of polymers and organic admixtures on portland cement hydration

Interaction of polymers and other organic admixtures on Portland cement hydration is reviewed. This has been compiled in a systematic way. First hydration of Portland cement is described in short. Later, interaction with 4 important components of Portland cement is discussed. Finally interphase effects in polymer modified hydraulic cement are discussed. It is concluded that polymers and organic admixtures interact with the components of Portland cement when they come in contact with water. This interaction is due to ionic binding, causing cross-links which inhibit the film formation property of polymers and influence considerably the crystallisation process during the hardening of concrete. Some low molecular weight organic substances also have a considerable influence on Portland cement during its reaction with water.     

复掺高性能矿物掺合料对高强机制砂混凝土性能的影响

为定量研究S105矿粉与其他矿物掺合料共同作用对C80高强机制砂混凝土的和易性、抗压强度和干燥收缩性能的影响规律,通过试验得到不同龄期(3 d、7 d、28 d、60 d)下,S105矿粉单掺,以及掺S105矿粉的同时以不同含量的微珠、超细矿粉、硅灰分别取代水泥时,高强机制砂混凝土的坍落度、扩展度、抗压强度和干燥收缩率,并利用图表分析及拌合物实际状态对比等对其性能的变化趋势进行分析。结果表明:在一定掺量范围内复掺多种矿物掺合料,有利于提高高强机制砂混凝土的和易性和抗压强度,并显著减小其干燥收缩。在保证混凝土和易性良好的条件下,相比于单掺S105矿粉,S105矿粉与不同矿物掺合料双掺对提高混凝土的综合性能有更显著的作用。综合考虑对和易性、抗压强度和干燥收缩性能的影响,当超细矿粉取代水泥的质量分数为3%时,即水泥与S105矿粉和超细矿粉的质量比为33:11:1时,高强机制砂混凝土的性能处于较好的水平,其粘聚性和流动性都有显著改善,其3 d和60 d抗压强度分别增长3.1%和5.1%,其干燥收缩率则减小了4.0%。