Influence of Polycarboxylate Superplasticizer on Rheological Behavior in Cement Paste

Molecular structures of polycarboxylate(PCE) superplasticizer significantly affect the rheological properties of cement paste. Consequently, we employed self-synthesized PCE copolymers with different carboxylic densities to investigate their influence on the rheological behavior of cement paste. Three typical rheological models were applied to analyze the rheological properties, including Power-law model, Bingham model as well as Herschel-Buikley model. In addition, the thixotropical performances of cement paste in the presence of PCE with different carboxylic densities were investigated. The results show that the carboxylic density of PCE greatly influences the dispersing performance of PCE superplasticizers. As carboxylic density increases, the dispersing capability of PCE improves, and P(PEG1-AA6) possesses the strongest dispersing capability, the initial fluidity and 1 h fluidity of cement paste are both the highest, and cement paste has the lowest viscosity and the smallest hysteresis loop.     

木质素磺酸钠聚羧酸减水剂的制备研究

以木质素磺酸钠作为聚羧酸减水剂的合成原料,在水溶液中与聚羧酸减水剂单体进行接枝共聚反应,制得木质素磺酸钠聚羧酸减水剂,并对其制备工艺进行优化,得到最优实验方案为:木质素磺酸钠质量分数为16%,PEG-1000和MA的物质的量比为0.9∶1.0,丙烯酸与马来酸酐物质的量比为2.8∶1.0,聚合时间为3h,酯化时间为4h,最优条件下制得的产品的水泥净浆流动度(掺量为0.2%,水灰质量比为0.29)为241mm。红外测试表明木质素磺酸钠分子结构上成功接上了聚氧乙烯基、酯基、羧酸基及酰胺基等官能团。     

功能性官能团改性高效聚羧酸减水剂研究

本文针对自制的高效聚羧酸减水剂(PC1),通过接枝共聚的方法在聚合物主链上分别引入磺酸基和酰胺基官能团,考察了磺酸基和酰胺基对PC1综合性能的影响.研究了它们的引入量对水泥的净浆流动性、砂浆流动性、流动度保持性、抗压强度比、抗折强度比等性能.实验结果表明:当磺酸基的引入量为羧基含量的20%～25%(mol比)时,可显著提高减水剂PC1对水泥的分散性和分散保持性.而酰胺基的引入对PC1的综合性能影响不大,但可显著改善PC1在水中的溶解性和稳定性.     

不同黏土对掺减水剂水泥净浆流动度影响

目的 研究4种不同黏土对掺聚羧酸减水剂及萘系减水剂水泥净浆流动度的影响规律并从黏土的吸附性能角度探究其影响机理.方法 采用水泥净浆流动度试验方法比较了4种黏土对掺聚羧酸减水剂水泥净浆流动度的影响,通过TOC总有机碳测试仪测定了4种黏土对聚羧酸减水剂的吸附量.结果 4种黏土对水泥净浆流动度的影响差异较大,其中钙基蒙脱土和钠基蒙脱土的掺量为2％时,掺聚羧酸减水剂水泥净浆已基本没有流动度,掺萘系减水剂的水泥净浆流动度也有所下降,但降幅稍小,而伊利土和高岭土对掺减水剂水泥净浆流动度无明显负面影响;钙基蒙脱土和钠基蒙脱土对聚羧酸减水剂的吸附量较大,伊利土、高岭土对聚羧酸减水剂的吸附能力和水泥相当.结论蒙脱土对掺聚羧酸减水剂水泥净浆流动度负面影响极为严重,而伊利土和高岭土对掺减水剂水泥净浆基本没有负面影响.     

Synthesis of a Novel Polycarboxylate Superplasticizer with Carboxyl Group as Side Chain Terminal Group to Enhance Its Clay Tolerance

The dispersion ability of polycarboxylate superplasticizer(PCE) in fresh concrete was much impeded by clay impurities. To improve the dispersion of PCE in the clay-contained concrete, a novel PCE with carboxyl as a specific branched chain terminal group was synthesized, using modified polyether as the raw material which was prepared through esterification between hexahydrophthalic anhydride(HHPA) and isobutenyl polyoxyethylene ether(IPEG) with hydroxy as the terminal group. The esterification product and PCE molecular structure were characterized by infrared spectroscopy and ~1HNMR resonance. The results confirmed that the product molecular structure was a comb-type copolymer with long-chain terminal carboxyl group and PEO attached directly to the backbone chain. The as-synthesized PCEs had favorable dispersibility in cement than conventional PCE in the presence of montmorillonite(Mmt) clay. This can be attributed to the introduction of electronegative carboxyl to PCE long-chain terminal group, which reduces the adsorption of PCE on Mmt, and thus improves the tolerance of PCE to the Mmt.     

聚羧酸系高效减水剂PC的合成及性能研究

以甲基丙烯酸、聚乙二醇1000、对甲苯磺酸、对苯二酚、过硫酸铵和甲基丙烯磺酸钠为原料,采用两步法合成出新型聚羧酸系高效减水剂(简称PC)。将合成的PC与目前广泛使用的萘系高效减水剂(简称FDN)相比,具有更加优异的性能,具体表现为:在掺量很少情况下,水泥净浆就具有较高的流动度;当掺量相同时,其对水泥净浆流动度远超FDN。此外,它与水泥的相容性好,具有缓凝及明显抑制水泥净浆流动度经时损失性能,对混凝土也能表现出显著的减水增强性,是一种性能优良,适合于配制高强、超高强混凝土的高效减水剂。     

Effect of competitive adsorption between sodium tripolyphosphate and naphthalene superplasticizer on fluidity of cement paste

The adsorption amount, ζ-potential of cement particles and fluidity of cement paste were tested to research the competitive adsorption between naphthalene superplasticizer(FDN) and STPP. The experimental results showed that the presence of STPP could significantly improve the fluidity of cement paste and reduce the fluidity loss with FDN. There existed a competitive adsorption between STPP and FDN. STPP and calcium ions formed complexes; they preferentially adsorbed onto surface of cement particles and preempt adsorption points of FDN; and it reduced adsorption amount of FDN. In the absence of STPP, saturation adsorption amount of FDN was 5.93 mg/g; but when the dosage of STPP was 0.1%, it reduced to 4.3 mg/g(about 72.5%). The adsorption amount of FDN was reduced by STPP, but ζ-potential of cement particles enhanced and fluidity of cement paste increased because of strong negative charge effect of the complexes. Adsorption of the complexes would delay Ca2+ into liquid and inhibit formation of active adsorption points. Then, content of FDN in liquid increased with the addition of STPP and ζ-potential of cement particles became stable. In this way, fluidity loss of cement paste reduced.     

Adsorption mechanism of polycarboxylate-based superplasticizer in CFBC ash-Portland cement paste

Circulating fluidized bed combustion （CFBC） ash exhibits the desirable pozzolanic activity which makes it a potential supplementary cementitious material to replace cement for concrete production. However, the high unburnt carbon content and porous surface structure of CFBC ash may adsorb water reducer and thereby significantly reduce the efficiency of water-reducing agents. The adsorption mechanism of polycarboxylate superplasticizer in CFBC ash-Portland cement paste was investigated by ultraviolet-visible spectrophotometer, and the conception of ＂invalid adsorption site＂ of CFBC ash was presented. The results show that the adsorption behavior of polycarboxylate superplasticizer in coal ash-Portland cement paste can be described by Langmuir isothermal adsorption equation. The adsorption capacity of CFBC ash-Portland cement paste is higher than that of pulverized coal combustion （PCC） fly ash-Portland cement paste. Moreover, the adsorption amount of polycarboxylate superplasticizer increases with the ratio of ash-to-cement in the paste. At last, the fluidity of CFBC ash-Portland cement paste is lower than that of the PCC fly ash paste. This work suggests that when CFBC ash is used as concrete admixture, the poor flowability of the cementitious system due to the high adsorption of water and water-reducing agent should be taken into consideration.     

UNIFORMITY ASSESSMENT OF CARBON FIBRES DISPERSION IN CEMENT PASTE BY IMPEDANCE MEASUREMENTS

An alternating current was applied to measure the impedance of a hardened cement paste with various contents of carbon fibres. When the free water content in the hardened cement paste is 90%-98%, and the measuring frequency 500Hz, an approximate linear relationship was found between fibre content and impedance of the composite. Based on this relationship , a new attempt was made to evaluate the dispersion uniformity of carbon fibres in cement paste by impedance measurement. The standard deviation S and the coefficient of vriation S/Xi     

氨基磺酸盐系高效减水剂的改性研究

氨基磺酸盐系减水剂具有高减水率、抑制混凝土塌落度经时损失等优点,但泌水严重,限制了其在混凝土中的应用。本文根据“分子设计”原则,通过单体A和单体U引入适当的官能团,对传统氨基磺酸盐系高效减水剂进行改性,测试了产品对水泥净浆流动度、流动度经时损失和泌水率的影响。试验表明,单体A的改性效果优于单体U,以9%的单体A改性后,减水剂的分散性和分散保持性能好,泌水率显著降低。     

矿物掺合料对自密实混凝土抗氯离子渗透性的影响

耐久性是自密实混凝土（SCC）的重要性质。本文应用电通量法研究了掺粉煤灰、矿渣的SCC抗氯离子渗透性能,通过对单掺和复掺时SCC电通大小的分析发现：粉煤灰和矿渣都能改善SCC的抗氯离子渗透性能,矿渣提高SCC的抗氯离子渗透性能要优于粉煤灰,二者复掺对SCC抗氯离子渗透的复合叠加效应并不明显。其机理是粉煤灰和矿渣提高水泥石密实性,强化混凝土界面过渡区,粉煤灰、矿渣物理化学吸附作用能固结Cl-,降低Cl-渗透性。SCC中掺入掺合料能减少离析、避免泌水,达到自密实效果,粉煤灰对混凝土流动增大的作用效果要优于磨细矿渣的效果。掺合料复掺对自密实混凝土强度具有复合叠加效应,混凝土28 d强度等级可提高1～2级。     

The Competitive Adsorption Characteristics of Welan Gum and Superplasticizer in Cement Mortar

Welan gum has been widely used in oil cement and grouting materials for its excellent rheological properties and anti-bleeding,and most of all,being friendly to the environment.However,when welan gum was added,the fluidity of mortar decreased sharply,so it should be used together with a superplasticizer to enable good workability.With its powerful charge density in the molecular structure,the competitive adsorption between welan gum and other admixtures happened remarkably during the addition process.Consequently,we experimentally studied on the bleeding rate and rheological properties of cement slurry,fluidity and mechanical properties of mortar with welan gum mixed with superplasticizer,aiming at understanding the competitive adsorption phenomenon by application of welan gum mixed with superplasticizer.By measuring the hydration heat and zeta potential,the mechanism of interaction of welan gum with superplasticizer was deduced and explained.The results showed that it could ensure a good dispersion effect when welan gum is mixed with the two kinds of superplasticizer.Welan gum had little impact on the naphthalene superplasticizer,but did have a substantial influence on polycarboxylate.In practice,adding welan gum after PCE acted with cement for 2 min could effectively avoid the competitive adsorption and then achieve better performance.On this viewpoint for mortar with PCE,new delay release welan gum needs further research and development.     

功能调整材料对水泥浆体流动性影响

使用自行研制的H管分别研究了不同功能调整材料对水泥浆体流动性的影响,得到不同种类矿物掺合料和增稠剂对水泥浆体流动性改性规律:粉煤灰掺量的增加引起浆体流动性先增加后减小;矿粉掺量越大,浆体流动性越大;硅灰和增稠剂掺量越大,浆体流动性越差。H管对水泥浆体流动性变化十分敏感,可以准确快速评价不同功能调整材料对水泥浆体流动性影响。     

聚羧酸减水剂在水泥和泥土表面的吸附行为

采用有机碳测定仪研究了水泥、泥土和水体系中聚羧酸减水剂吸附量与吸附时间、减水剂浓度、体系温度的关系。同时,对减水剂吸附模型和吸附热进行了分析,探讨了聚羧酸减水剂在水泥、泥土颗粒表面的吸附特性。结果表明:水泥和泥土对聚羧酸减水剂的吸附量随时间延长不断增加,最后达到平衡,同时,泥土比水泥对减水剂的吸附量要大,泥土的掺入量为0.5%就会大大降低水泥净浆的流动度;聚羧酸减水剂的吸附基本符合Langmuir等温吸附模型,水泥和泥土对减水剂的饱和吸附量分别为3.7mg/g和10.1mg/g;水泥和泥土对聚羧酸减水剂的吸附量随温度的增大而减小,其吸附是一个放热过程。     

Rheological properties of self-compacting concrete paste containing chemical admixtures

Self-compacting concrete (SCC) was used for the filling layer of CRTSIII plate ballastless track, which needs excellent workability. The rheological properties of SCC cement paste containing chemical admixtures (CA) such as polycarboxylate-based superplasticizer (PCE), air-entraining agent (AE) and defoamer (DF) were investigated using a Brookfield R/S SST2000 soft solid tester with a vane geometry spindle. The cementitious materials were designed as one, two and, three components systems by addition of ordinary portland cement (OPC) with these chemical admixtures. The rheological properties of one-component system (PCE paste) were improved with increasing the content of PCE. For two components systems of PCE-AE and PCE-DF, yield stress and plastic viscosity reduced firstly and increased afterward with the increasing of AE content. And the plastic viscosity reached the optimum when the content of AE is 0.004wt%. In general, the trend of yield stress and plastic viscosity decreased with the increasing of the DF content. For three components systems, PCE-AE-DF systems, the rheological properties were improved compared with the sample with AE or DF, which attributed to mixes of the active components mentioned above (CA) which could have a synergetic effect.     

The influence of steel slag with high Al2O3 content on the initial hydration of cement

The initial hydration of steel slag with high Al₂O₃ content and its influence on the initial hydration of cement were investigated in this study. Steel slag with high Al₂O₃ content may contain much calcium aluminate mineral but very little gypsum. The steel slag hydrates much more quickly than cement in the initial hydration period, producing many flake products which have a great influence on the fluidity, initial setting time, and adsorption level of superplasticizer of paste. Replacing part of cement by steel slag with high Al₂O₃ content can change the hydration condition of calcium aluminate mineral of the cement by decreasing the gypsum to calcium aluminate mineral ratio, resulting in accelerating the hydration rate of calcium aluminate mineral in the initial hydration period. Paste containing steel slag with high Al₂O₃ content has a shorter initial setting time, higher adsorption level of superplasticizer, and greater loss in fluidity than the pure cement paste.     

矿粉对水泥和混凝土性能的影响

为了探寻矿粉细度及掺入量对水泥和混凝土性能的影响,通过试验测试方法,分析了矿粉和水泥的基本性质,研究了超细矿粉和普通矿粉的掺量对水泥基材料标准稠度、凝结时间、流动度和力学性能的影响.结果表明：普通矿粉使水泥净浆标准稠度需水量下降,而超细矿粉则增加标准稠度需水量,两种矿粉都使水泥净浆凝结时间略微延长.普通矿粉可以改善水泥净浆的流动度,超细矿粉的加入则降低了水泥净浆的流动度.普通矿粉和超细矿粉降低水泥净浆早期（7 d）抗压强度,提高后期（28 d）抗压强度,掺10％～50％的普通矿粉的水泥净浆28 d抗压强度提高2.9％～9.7％,掺入超细矿粉28 d抗压强度提高3.9％～20.1％,普通矿粉和超细矿粉的最佳掺量为10％～30％;两种矿粉替代10％～50％水泥所配制的混凝土的强度得到了明显的提高.     

结合分形理论的水泥絮凝研究

目的对水泥絮凝进行定量化研究,找出其微观结构与宏观性质的联系.方法用“激光颗粒分布测量仪”测试了不同水泥絮凝颗粒的粒度分布,分析了各絮凝颗粒的分形特征,探讨了分形维数与水泥比表面积、净浆流动度的关系.结果水泥絮凝颗粒的粒度分布具有很好的自相似性,属于典型的无规三维分形体;且分形维数越大,比表面积越大,水泥净浆流动度越小.结论用分形维数对抽象的水泥絮凝粒度分布进行定量描述是可行的,从分形维数可以推断出比表面积和净浆流动度等宏观性质的变化趋势.     

水泥3D打印喷头中浆体的流动分析

针对水泥浆体在流经水泥3D打印样机喷头结构时沾黏、流动性差的问题,提出一种基于多松弛参数格子玻尔兹曼方法（MRT-LBM）的模型,研究幂律流体在单螺杆机构中的流动特性. 采用MRT-LBM修正模型,对水泥浆体在喷头中的流动情况进行数值模拟,得到水泥浆体在喷头装置内不同位置处的速度分布情况,为水泥3D打印喷头结构提出改进方案. 通过已有理论解的泊肃叶流对修正后的MRT-LBM模型进行详细论述,并将解析解与MRT-LBM修正模型得到的结果进行对比,验证分段幂律模型的可行性. 最后,改变晶格节点的数量（10~500）,计算实验结果与理论结果的相对误差,结果表明修正后的MRT-LBM模型是稳定的.     

羧酸型减水剂与水泥的相容性研究

选用含有亲水性羧基、酸酐基、磺酸基、聚环氧乙烷侧链的单体共聚合成了3种羧酸型减水剂,针对4种不同产地的P.O 42.5水泥,测定了在较低水灰比（mw/mc=0.29）下水泥净浆流动度及30 min经时变化,混凝土坍落度及180 min经时变化.净浆流动度30 min损失小于13.8%,混凝土坍落度60 min损失小于15%.3种羧酸型减水剂与不同水泥均具有良好的相容性.