减缩型聚羧酸减水剂提高混凝土早期抗裂性的作用研究

减缩型聚羧酸减水剂(SRPC)是一类兼具减缩与减水双重作用的新型混凝土外加剂,它对混凝土早期抗裂性的作用将影响其在工程中的应用。本文利用平板抗裂试验对比测试了掺SRPC、聚羧酸减水剂(PCE)及小分子减缩剂(SRA)的混凝土早期抗裂性,并通过对表面张力、收缩率、孔结构、水化热等参数的分析,讨论了SRPC影响混凝土抗裂性的作用机理。试验结果表明,尽管SRPC在掺量0.15%(质量分数)下的减缩效果弱于掺量1.5%(质量分数)的SRA,但SRPC表现出更佳的早期抗裂性能。机理分析表明,SRPC除了与SRA都是通过降低孔溶液表面张力及改变毛细孔结构从而减少混凝土的收缩外,还通过延缓水泥水化速率、降低早期水化放热量、抑制混凝土中水分蒸发等作用,改善混凝土的早期抗裂性。     

减缩剂外涂对混凝土性能的影响及作用机理

内掺减缩剂可有效降低混凝土收缩,但存在掺量大和影响混凝士强度发展等诸多问题.研究了减缩剂外涂对混凝土力学性能、收缩抗裂性能、孔结构和水化产物的影响.结果表明:减缩剂外涂混凝士的减缩效果明显;减缩剂外涂对混凝土和胶砂强度有一定的提高作用;与基准混凝土相比,减缩剂外涂可明显降低水泥石总孔隙率和孔径小于100nm毛细孔的数量;外涂减缩剂作用区域中的水泥水化产物更趋于丰富.     

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.     

Design and function of novel superplasticizers for more durable high performance concrete (superplast project)

In this article we shall describe our quest and ultimate success in furthering our understanding of the action of superplasticizers on the rheology of cement and concrete. By specifically producing superplasticizers with varied architectures, we have been able to show the important structural features of the macromolecules that lead to a successful superplasticizer or water reducing agent. Both polycarboxylate and lignosulfonate polymers have been investigated. Using both non-reactive model MgO powders, three different types of cement blends, the adsorption behaviour and the effect on the rheological properties of these two important superplasticizer families have been used to further develop a conceptual model for superplasticizer — cement behaviour. This paper will deal mainly with the conceptual model, the materials and methods used to asses the polymer adsorption behaviour and rheological properties of the systems studied. We shall briefly describe the adsorption of the polymers onto the different surfaces and their influence on surface charge and rheology and the influence of the various ionic species found in cement pore solutions that may influence polymer-cement affinity. The key factors are shown to be the effective adsorbed polymer thickness and the induced surface charge which can be influenced by the polymer architecture, the pore solution composition and the initial particle surface charge.     

Modeling the hydration of concrete incorporating fly ash or slag

Granulated slag from metal industries and fly ash from the combustion of coal are industrial by-products that 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, the hydration of concrete containing fly ash or slag is much more complex compared with that of Portland cement. In this paper, the production of calcium hydroxide in cement hydration and its consumption in the reaction of mineral admixtures is considered in order to develop a numerical model that simulates the hydration of concrete containing fly ash or slag. The heat evolution rates of fly ash- or slag-blended concrete is determined by the contribution of both cement hydration and the reaction of the mineral admixtures. The proposed model is verified through experimental data on concrete with different water-to-cement ratios and mineral admixture substitution ratios.     

减缩剂对碱激发煤矸石-矿渣胶凝材料性能的影响

本文探讨了减缩剂(SRA)对碱激发煤矸石-矿渣(AACGS)胶凝材料力学性能和干燥收缩的影响,进一步分析掺入SRA后水化热、水化产物及微观结构的变化规律。结果表明:掺入3%(质量分数)SRA明显降低了AACGS胶凝材料的力学性能,但随着水化的进行,降低幅度逐渐减小;随着SRA掺量的增加,干燥收缩显著减小。微观分析表明,SRA的掺入没有导致新的水化产物生成,但延缓了水化反应,抑制了碱激发材料早期的聚合反应,增加了碱激发胶凝材料的孔隙率,这也是SRA使AACGS胶凝材料力学性能降低的原因。SRA并没有明显改变孔隙溶液中碱金属离子的浓度,水化进程的延缓和固相结构的形成是其降低AACGS砂浆干燥收缩的主要原因。     

Investigation into relations among technological properties, hydration kinetics and early age hydration of self-leveling underlayments

Technological properties such as flow value, setting times, compressive strength and early age dimensional stability as linear shrinkage and expansion have been studied for two types of self-leveling underlayments (SLU) in which the kind of calcium sulfates was varied. The influence on hydration kinetics has been measured by isothermal heat flow calorimetry. The results obtained for the technological properties change significantly when different kinds of calcium sulfates are used. The basic trend for the results changes when the composition changes from a calcium aluminate cement system to a Portland cement system. Additionally, there was an interesting relationship to final dimensional stability and shape of heat evolution curve. Moreover the time to reach plateau of dimensional stability was related to the development of compressive strength. In the meanwhile, using hemihydrate in Portland cement systems caused low compressive strength and significant expansion. On the other hand, in the results of XRD measurements, the first genesis of Ettringite corresponded to the first shrinkage of SLU. Interesting results related with technological properties and hydration kinetics or the results of XRD other than these above results were obtained.     

The origin of early age expansions induced in cementitious materials containing shrinkage reducing admixtures

Studies on the early-age shrinkage behavior of cement pastes, mortars, and concretes containing shrinkage reducing admixtures (SRAs) have indicated these mixtures frequently exhibit an expansion shortly after setting. While the magnitude of the expansion has been noted to be a function of the chemistry of the cement and the admixture dosage; the cause of the expansion is not clearly understood. This investigation uses measurements of autogenous deformation, X-ray diffraction, pore solution analysis, thermogravimetry, and scanning electron microscopy to study the early-age properties and describe the mechanism of the expansion in OPC pastes made with and without SRA. The composition of the pore solution indicates that the presence of the SRA increases the portlandite oversaturation level in solution which can result in higher crystallization stresses which could lead to an expansion. This observation is supported by deformation calculations for the systems examined.     

Influence of nucleation seeding on the hydration kinetics and compressive strength of alkali activated slag paste

Addition of pure calcium silicate hydrate (C–S–H) to alkali-activated slag (AAS) paste resulted in an earlier and larger hydration rate peak measured with isothermal calorimetry and a much higher compressive strength after 1 d of curing. This is attributed to a nucleation seeding effect, as was previously established for Portland cement and tricalcium silicate pastes. The acceleration of AAS hydration by seeding indicates that the early hydration rate is controlled by nucleation and growth. For the experiments reported here, the effect of C–S–H seed on the strength development of AAS paste between 1 d and 14 d of curing depended strongly on the curing method. With sealed curing the strength continued to increase, but with underwater curing the strength decreased due to cracking. This cracking is attributed to differential stresses arising from chemical and autogenous shrinkage. Similar experiments were also performed on Portland cement paste.     

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).     

Impact of admixtures on the hydration kinetics of Portland cement

Most concrete produced today includes either chemical additions to the cement, chemical admixtures in the concrete, or both. These chemicals alter a number of properties of cementitious systems, including hydration behavior, and it has been long understood by practitioners that these systems can differ widely in response to such chemicals.In this paper the impact on hydration of several classes of chemicals is reviewed with an emphasis on the current understanding of interactions with cement chemistry. These include setting retarders, accelerators, and water reducing dispersants. The ability of the chemicals to alter the aluminate–sulfate balance of cementitious systems is discussed with a focus on the impact on silicate hydration. As a key example of this complex interaction, unusual behavior sometimes observed in systems containing high calcium fly ash is highlighted.     

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.     

超缓凝剂SRA的研制与应用研究

以蔗糖为主要原料研制出一种超效缓凝剂（简称SRA）；并着重进行了SRA对水泥水化进程、凝结硬化、强度发展的影响试验，同时进行SRA作水泥稳定粒料路面基层延迟成型剂的应用试验。试验结果表明：（1）当SRA掺量为0．045％时可将终凝时间延长到10h；合理掺量的SRA能明显延缓水泥的早期水化，对强度发展无不利影响：SRA掺量过大（达0．48％）会促进凝结并影响强度形成。（2）SRA用作水泥稳定粒料路面基层的延迟成型剂的最佳掺量在0．05％～0．06％：用SRA可降低因延迟压实对水泥稳定粒料基层的强度和干密度的影响，可把延迟成型时间延长到9h；在成型延迟4h，6h，9h后，掺入SRA的水泥稳定粒料的强度和干容度损失明显小于未掺外加剂的混合料在相同延迟成型务件下的强度损失。（3）在延迟成型时间比较长时，SRA比木钙具有更为明显的延迟成型效果．且具更明显的技术经济性。     

高性能聚羧酸减缩材料的研发(Ⅲ)——高分子聚合物(HP-SRA)的作用机理

通过对比,研究了采用自行研发的高分子聚合物(HP-SRA)与Eclipse-Floor减缩剂(Eclipse-SRA)2种减缩材料在降低水泥颗粒表面上的平均吸附率、溶液表面张力和蒸发速率、提高溶液动力黏度、减少水泥砂浆收缩和改善孔结构分布等方面的作用。结果表明,水泥颗粒表面对高分子聚合物(HP-SRA)的平均吸附率小于10%;高分子聚合物(HP-SRA)可显著降低溶液表面张力和蒸发速率,大幅提高溶液动力黏度;高分子聚合物(HPSRA)对水泥砂浆减缩效果显著,在其掺入量为0.30%(质量分数)时,水泥砂浆在3 d和28 d养护龄期时的收缩率分别下降了48.6%和20.2%。     

The influence of water removal techniques on the composition and microstructure of hardened cement pastes

The removal of water from hardened cement paste for analysis or to arrest ongoing hydration has been reported to affect the composition of hydrated phases and microstructure. The effect that arresting the hydration of hardened cement paste by replacing the pore water with acetone before drying, and by removing the water by freeze, vacuum and oven drying has on the hardened cement paste has been investigated. Two pastes were studied, a cemented iron hydroxide floc where a high proportion of ordinary Portland cement (OPC) had been replaced by pulverised fuel ash, and a pure hydrated OPC. The results showed that none of the water removal techniques caused any major deterioration in the composition and microstructure of the hardened cement pastes studied, but the pores appeared better preserved after arresting hydration using acetone quenching. Freeze drying appeared to cause more cracking of the microstructure than the other water removal techniques.     

Early-age behavior of materials with a cement matrix

Materials with a cement matrix classically present early-age volume variations (shrinkage and/or swelling). This intrinsic early-age behavior strongly influences the length of time the buildings and structures will last because of the micro-cracking and cracking that results from it. One explanation for the macroscopic shrinkage is the presence of pore pressure in the porous medium. In this study, fine modeling of the coupling mechanism behind these internal strains is proposed. The chemical reaction associated with hydration is considered as the main force behind the hydric and mechanical evolutions in an endogenous configuration. Thus, the influence of chemical contraction, porosity, pore-size distribution and pore pressure are central to the study in the light of the numerical and experimental results obtained. A self-leveling layer of mortar of sulfo-aluminous concrete base was used.     

Reaction mechanisms of concrete admixtures

Concrete admixtures influence the kinetic of cement hydration mainly during the dormant period. The dominant influence of admixtures seems to lie in different bound forces between dissociated ions in the pore water solution. Repulsive forces characterize the solvation process while attractive forces dominate during crystallization. These changes of ion bound forces lead twice to volume changes during phase transitions of hydration. Volume changes measured with an immersion weighing setup show clearly the effect of concrete admixtures on cement reaction. Retarder agents produce a volume swelling while accelerators force an immediate shrinkage behaviour. A mechanism as introduced by Le Chatelier involving a solution-crystallization step seems to describe the hydration process most adequately. As long as repulsive forces dominate, a volume swelling occurs and no strength gain can take place. The dormant period is defined by the length of the swelling process. Hardening and strength growth start at the point at which volume shrinkage appears.     

Influence of a fine glass powder on cement hydration: Comparison to fly ash and modeling the degree of hydration

This paper reports the results of an investigation carried out to understand the influence of a fine glass powder on cement hydration. The pozzolanicity of the glass powder and a Class F fly ash for comparison was evaluated using strength activity index over a period of time, and a rapid electrical conductivity based method. Flame emission spectroscopy and electrical conductivity tests were used to quantify the alkali release from glass powder, and gain information on the rate of alkali release. It was found that the glass powder releases only a very small fraction of sodium ions into the solution. It was observed that the glass powder modified pastes show higher non-evaporable water contents than the plain paste and fly ash modified pastes, indicating that glass powder facilitates enhancement in cement hydration. An expression has been developed for the change in non-evaporable water content as a result of enhancement in cement hydration and the hydration of the cement replacement material. The efficiency of any cement replacement material with age in the paste system can be quantified using this parameter. Based on this parameter, a 5% cement replacement with glass powder was found to be effective at the chosen water-to-cementing materials ratio (w/cm), whereas at higher replacement levels, the dilution effect dominates. A model to predict the combined degree of hydration of cement pastes incorporating more than one cementing material is outlined. The measured and predicted combined degrees of hydration agree well.     

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.     

内掺硅烷乳液憎水剂对混凝土性能的影响

通过强度测试、水化热实验、热重分析、毛细吸水实验以及压汞实验研究了内掺硅烷乳液憎水剂对混凝土强度以及毛细吸水性能的影响规律及其机理.结果表明:高掺量硅烷乳液一定程度上抑制水泥水化,从而导致混凝土早龄期抗压强度和劈裂抗拉强度下降以及28 d养护后水泥净浆试块中毛细孔的体积增大.毛细吸水实验表明:28 d龄期混凝土毛细吸水...