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.     

葡萄糖酸钠与聚羧酸减水剂的复合效应研究

研究了聚羧酸减水剂与葡萄糖酸钠的复合使用对水泥浆体的凝结时间、净浆流动性、强度、水化热的影响,并采用XRD分析水泥水化产物的变化。结果表明:适量的葡萄糖酸钠能显著提高聚羧酸减水剂的分散性和分散保持性,改善水泥与聚羧酸减水剂的适应性,延长凝结时间,并使3 d7、d强度有所提高;单掺葡萄糖酸钠使水泥水化第2放热峰出现时间延迟2 h,但温峰值及水化热与空白样基本持平,1 d、7 d CH的生成量减少。复合使用葡萄糖酸钠与聚羧酸减水剂时,水泥净浆水化温峰出现时间延迟15 h,水化温峰提高,1 d、7 d CH的生成量较单掺葡萄糖酸钠时有所增大。     

一种高精准水泥浆体流动性测定装置

针对传统净浆流动度测试方法灵敏度不高、测试范围窄的问题,设计了一系列不同口径的玻璃管(H管)。通过对不同水灰比、不同掺量减水剂条件下水泥浆体的流变特点的对比分析,得到不同H管对应净浆流动度测试范围和减水剂最佳掺量测试方法。H管不仅灵敏度高、测试范围广,而且还可以反映浆体粘度,是一套比较全面准确的水泥浆体流动性测试方法。     

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.     

Multi-level flocculation structures of fresh cement paste by confocal laser scanning microscope

Under saturation dosage of all kinds of SP, the free water amount was examined by centrifuge. The distribution of solution and flocculation microstructures in fresh cement paste was observed in three- dimensional space by confocal laser scanning microscope（CLSM）. Results indicate that SP can increase the free water amount by destroying the flocculated cement particle structure and different free water amount is released by different kinds of SP. The changes of the size of flocculation structures and the dispersion of solution were obviously detected with confocal laser scanning microscope： the size of flocculation structures was smaller and more dispersed in fresh cement paste with polycarboxylate superplasticizer, but the size of flocculation structures was bigger and cannot be dispersed uniformly in fresh cement paste with others SP. The multi- level flocculation structures theoretical model of fresh cement paste was then set up. The theory indicates that different kinds of SP with different dispersion strength will open the flocculation structures at different levels, which in turn present different water reducing rate.     

高效减水剂分散、助磨与减水复合效应实验研究

研究了高效减水剂与胶凝材料共粉磨时间高效减水剂对物料分散性和物料物磨效率的影响,以及共粉磨法与同掺法对高效减水剂减水效果的影响,结果表明,高效减水剂的存在有助于改善粉磨物料分散性,并可提高粉磨效率。与同掺法相比,采用共粉磨法可提高高效减水剂的减水效果,且水泥净浆稠度经过变化小,从而表明,用共粉磨改性超细水泥配制高性能砼时,用水量相同情况下,其初始坍 落度较同掺法时大,而坍 落度损失较小。     

聚合物-水泥基注浆材料早期流变及水化特性

为制备满足复杂地层加固工程需求的高性能水泥基注浆材料,探究以偏铝酸钠(SA)、聚羧酸(Sp)及高吸水性树脂(SAP)为组分的聚合物体系及其掺量对新拌水泥浆体流变特性与泌水率的影响,并采用水化放热监测与倒置荧光显微技术,对不同体系下水泥浆体早期水化进程及微米级颗粒的悬浮分散形态进行分析.结果表明:新拌水泥浆液流动性和泌水率与SA、SAP掺量呈负相关,随Sp掺量增加而提高. Sp及SAP延缓了水泥早期水化进程,改性样延迟近1 h进入水化诱导期,诱导期内水化放热速率显著降低.在不同掺量SA的促凝效应、Sp的分散效应以及SAP的"水库"作用下,新拌水泥浆液表现为初始及经时流动度大于200 mm的高流态期可分别被控制在10、20、30 min内且析水率小于5%(稳定性浆液),接近临界期时流动度陡降、流变参数突增并迅速凝结的流变特性.结合微观结构观测结果,建立了新拌水泥浆体流变演化模型,揭示多聚合物协调效应下水泥浆体呈现分散-储水-流变-水化的早期流变机制.     

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。     

聚羧酸超塑化剂的性能研究

研究了含有亲水性羧基、酸酐基团、磺酸基、聚环氧乙烷侧链的三种羧酸类共聚物对水泥浆体流变性能和水泥粒子表面Zeta电位的影响，并与萘系高效减水剂进行了对比．在改善水泥浆体的流变性能方面，三种聚羧酸超塑化剂的最佳掺量和饱和掺量均为0．3％～0．45％；对水泥粒子表面Zeta电位的影响方面聚羧酸超塑化剂远小于萘系高效减水剂，证实了两类减水剂的分散作用机理的区别．[编者按]     

Adsorption of superplasticizers in fly ash blended cement pastes and its rheological effects

The adsorption of superplasticizers in fly ash blended cement paste and its rheological effects were investigated.It is shown that the absorption of superplasticizer on portland cement particles is very different from that on fly ash particles.The fly ash particles have smooth surfaces and are negatively charged,so its adsorption capacity is weaker than the portland cement particles.The amount of adsorbed SP in the fly ash blended cement paste depends highly on the replacement proportion of portland cement with fly ash,and to a much less extent on the nature of the fly ash.However,the amount of adsorbed superplasticizer does not correspond well the ζ-potential of the solid particles,due the strong adsorbing capacities of the Portland cement particles.When fly ash replaces portland cement in the paste,the rheological behavior is radically changed,which is closely related to the fineness and density of the ash.The packing and agglomeration of the solid particles are the controlling factors on the rheological parameters of the fresh paste,instead of the amount and type of adsorbed superplasticizer.     

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。     

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     

Probing development of microstructure of early cement paste using 1H low-field NMR

Development of microstructure of early cement paste (0–6 h) was investigated with ¹H low-field NMR. It was found that T ₂ (transverse relaxation time) distributions of fresh cement paste were bimodal and two peaks were ‘long component’ and ‘short component’. Separation degree of two peaks was a sign of exchange of water within flocculation and outside flocculation. Factors such as water cement ratio, specific surface area and dosage of superplasticizer had influences on the separation degree: the separation degree increased with the water cement ratio; the separation degree of cement paste prepared with cement with a high specific surface area was zero; dosage of superplasticizer will decrease separation degree. Results also suggested that T ₂ distribution gradually moved to the left and T ₂ of long component and initial fluidity were linearly correlated.     

Synthesis of new polyether polycarboxylate superplasticizer

The effects of various factors on the synthesis process and the performances of product, including batch feeding way and the dosage of the radical initiator, the system concentration, the reaction temperature and the reaction time were discussed. A kind of polycarboxylate superplasticizer with allyl alcohol polyethylene glycol, maleic anhydride and methacrylic acid sulfonic sodium as main raw materials has been synthesized. Their relative effectiveness as dispersants was evaluated in cement paste by measuring paste fluidity. The optimum parameters of technology and the appropriate proportion of raw materials were obtained. As a result, the new high performance superplasticizer suitable for high-performance concrete has been synthesized. The structure of copolymer was characterized and analyzed by FT-IR spectra. Results indicated that product copolymer structure was consistent with the ideal molecular structure designed.     

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.     

水泥沥青浆体中减水剂与乳化沥青的竞争吸附行为

为揭示水泥沥青砂浆(CA砂浆)中水泥对乳化沥青和减水剂的吸附规律,采用微量热仪分析了减水剂、乳化沥青(单掺及同掺)对水泥水化诱导期的延迟作用.采用"固含法"研究了减水剂种类对水泥-乳化沥青经时吸附规律的影响,以及减水剂在不同添加顺序时对水泥-乳化沥青经时吸附规律的影响.采用偏光显微镜对减水剂作用下水泥-乳化沥青的吸附行为进行了原位观测.结果表明:CA砂浆中的乳化沥青和减水剂均能显著延迟水泥的水化诱导期,两者同掺使延迟作用产生了明显的协同效应;聚羧酸减水剂与乳化沥青对水泥的吸附作用存在明显的竞争关系,两者同掺时水泥优先吸附减水剂分子,减水剂耗尽后,水泥再吸附乳化沥青.减水剂后掺时可使部分吸附的乳化沥青发生解吸附.     

低需水的新拌水泥浆体流变性研究

在对水泥浆体流变模型和流变性能影响因素分析的基础上，研究了外加剂掺量、SO3含量、矿渣掺量等对新拌水泥浆流变性能的影响。用旋转粘度计对新拌水泥浆进行了动态检测，低需水量水泥的新拌水泥浆具有良好的流变性能，同时它的流变模型符合宾汉姆流变模型。     

液体低碱复合速凝剂的试验研究

采用四组分复合的方法合成了一种液体低碱复合速凝剂．性能测试结果表明,这种液体速凝剂满足国内现行建材行业标准对喷射混凝土用速凝剂一等品的要求,并与常用高效减水剂适应性较好,适应性明显优于粉状高碱固体商品速凝剂．通过采用SEM测试手段对水泥硬化体微观结构进行深入分析,阐述了促进早期水泥水化和硬化的速凝机理．     

硅灰与氧化石墨烯对硬化水泥浆体的复合增强效应

研究了硅灰与氧化石墨烯复掺时对硬化水泥浆体力学性能的影响. 分别进行了普通水泥浆体、内掺质量分数10%的硅灰水泥、外掺质量分数0.8%的氧化石墨烯复合聚羧酸减水剂（GOPCs）水泥浆体以及同时内掺硅灰与外掺GOPCs的水泥浆体的配制. 对4种硬化水泥浆体的抗折强度、抗压强度以及90 d龄期孔隙率进行了测定,同时采用X射线衍射仪及扫描电子显微镜对水泥水化产物进行分析,并将4种样品的力学性能进行比较. 结果表明,当掺10%硅灰时,硬化水泥浆体90 d抗压强度比空白样提高了3.6%,抗折强度提高了9.6%;当只使用氧化石墨烯复合聚羧酸减水剂而不掺硅灰时,抗压强度提高了11.9%,抗折强度提高了15.3%;当硅灰与氧化石墨烯复掺时,抗压强度提高了22.7%,抗折强度提高了38.6%. 孔隙率的变化以及XRD、SEM分析证实了这一结果. 因此,硅灰与氧化石墨烯复合聚羧酸减水剂对硬化水泥浆体具有复合增强作用.     

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.