含硅烷官能团聚羧酸减水剂对水泥浆体流动性和力学性能的影响

用γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)部分或全部取代聚羧酸减水剂合成过程中的丙烯酸(AA)单体,通过自由基聚合合成了一系列不同组成的硅烷改性聚羧酸减水剂(SPC)。研究了引入硅烷官能团后,减水剂对水泥净浆流动度的影响规律。采用总有机碳分析法(TOC)研究了硅烷改性聚羧酸减水剂的吸附行为。最后评价了其对水泥砂浆强度发展的影响。结果表明:聚羧酸减水剂(PC)分子中羧基含量越高,其在水泥颗粒表面的吸附量越大,对水泥浆体的分散性越好;在减水剂分子结构中引入硅氧烷官能团,水解生成的硅羟基可以作为吸附基团,提高减水剂分子在水泥颗粒表面的吸附能力,从而提高减水剂对水泥的分散能力;且硅羟基在水泥表面的吸附为化学吸附,因此其吸附能力大于羧基官能团(—COOH);聚异丁烯醇聚氧乙烯醚和KH570的摩尔比为1∶1或1∶2的共聚物有利于砂浆7、28d抗压强度的发展。     

硅烷改性聚羧酸减水剂对水泥浆体流动性及水化进程的影响

通过自由基聚合法,利用γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)部分或完全取代聚羧酸减水剂合成过程中的丙烯酸(AA)单体,合成了硅烷改性聚羧酸减水剂。研究了硅烷改性聚羧酸减水剂在水泥颗粒表面的吸附行为以及对水泥浆体分散性能的影响,并研究了硅烷改性聚羧酸减水剂对水泥水化进程的影响。结果表明:硅烷部分取代丙烯酸可提高聚羧酸减水剂在水泥颗粒表面的吸附量,提高了水泥浆体流动度;相对于传统聚羧酸减水剂,可更大程度延缓水泥水化进程,但可提高水泥3 d水化程度;而硅烷全部取代丙烯酸,聚羧酸减水剂对水泥吸附、分散性能下降,对水泥水化延缓程度增强,对水泥水化程度无提高效果。     

选择性吸附对含磷酸基减水剂在水泥-微斜长石粉浆体中分散性能的影响

石粉岩性和表面积对聚羧酸减水剂吸附行为的影响是决定减水剂在机制砂混凝土中分散性能的关键因子。基于增强石粉界面减水剂吸附、改善浆体流动性的基本思路，对比研究了常规聚羧酸减水剂和引入磷酸基的减水剂对水泥–微斜长石粉浆体流变行为的影响。引入磷酸基可以提高减水剂在微斜长石粉表面的吸附，改善混合体系的堆积密实度，同时增加固体颗粒表面平均间距，提高了减水剂在水泥–微斜长石粉浆体中的分散性能，有效降低了浆体表观粘度。体系中微斜长石粉含量增加，含磷酸基减水剂相比仅含羧基的减水剂性能更优异。     

改性木质素高效减水剂作用机理的研究

以桉木硫酸盐法制浆黑液为原料,经过4步改性反应即氧化、羟甲基化、磺化和接枝共聚,得到改性木质素高效减水剂(MLS)。通过对MLS的表面张力、电荷密度、表面吸附量和流动度等性能分析,研究高效改性木质素减水剂的减水作用机理。黑液经过4步改性反应,有效地引入了活性基团,制备出的MLS的表面活性和电荷密度得到了提高;MLS通过在水泥颗粒表面形成吸附层达到减水作用,当MLS的掺加量为0.5%时,在水泥颗粒表面吸附量达到最高,减水效果已接近高效减水剂的水平。     

硫酸盐对聚羧酸减水剂吸附量及吸附动力学的影响

在研究聚羧酸减水剂在水泥颗粒表面的吸附量、吸附速率的基础上,运用不同吸附动力学模型对试验结果进行拟合。吸附量测试结果表明:掺0.5%、1.0%Na2SO4会显著降低聚羧酸减水剂在水泥颗粒表面的吸附量,但掺0.1%、0.2%的Na2SO4有利于聚羧酸减水剂的吸附;CaSO4·2H2O对聚羧酸减水剂的吸附量影响不显著。吸附速率测试及拟合结果表明:硫酸盐对聚羧酸减水剂在水泥颗粒表面吸附动力学的影响规律符合Langmuir准二级吸附动力学模型,Na2SO4通过改变聚羧酸减水剂在水泥颗粒表面的准二级吸附速率常数影响聚羧酸减水剂吸附达到平衡的时间,0.2%、1.0%掺量的Na2SO4均延迟了聚羧酸减水剂达到吸附平衡的时间。掺0.2%Na2SO4使准二级吸附速率常数较不掺硫酸盐时有所提高;掺1.0%Na2SO4的准二级吸附速率常数较不掺硫酸盐时大大降低;CaSO4·2H2O对准二级吸附速率常数的影响较Na2SO4要小。     

水泥基体系中聚羧酸系高效减水剂的化学结构对其性能的影响(英文)

研究了不同结构的聚羧酸系高效减水剂对水泥净浆性能的影响。以马来酸酐和烯丙基聚氧乙烯醚为主要单体,采用自由基聚合方法合成了3种不同分子结构的减水剂。用Fourier变换红外光谱表征减水剂分子的结构。此外,用水泥净浆扩展度、量热测试和吸附率测试分析减水剂对水泥净浆性能的影响。结果表明:具有较低侧链密度、中等电荷密度和最高相对分子质量的减水剂分子表现出最佳分散性能和在水泥颗粒上的最高吸附率,因此具有最强的缓凝作用。     

不同结构聚羧酸减水剂在吸附质浆体表面的吸附-分散效应

为考察不同侧链密度的减水剂分子在水泥-钠基膨润土浆体中的吸附-分散效应,以丙烯酸和2-甲基丙-2-烯基聚乙二醇醚自由基共聚法,通过调整链转移剂构建出适当主链长度且不同侧链密度的聚羧酸减水剂.采用GPC、Zeta电位、TOC、流动度测试技术表征,着重考察了相近主链长度、不同侧链密度的减水剂在水泥-钠基膨润土混合浆体中的吸附-分散特性.结果 表明:侧链密度设计越高,主链长度同步减小,减水剂分子初始吸附量越小;内掺钠基膨润土后在分散性能方面侧链密度高的占优势,且内掺量越大,侧链密度高的减水剂抗泥质吸附能力越强.     

聚羧酸减水剂分子结构中丙烯酸酯单元的缓释机理及其温度敏感性

以丙烯酸羟乙酯(HEA)或丙烯酸羟丙酯(HPA)为功能单体,与丙烯酸(AA)、甲基烯丙醇聚氧乙烯醚(HPEG)通过自由基共聚制备两类丙烯酸酯改性的聚羧酸减水剂PCHEA和PCHPA。通过测试PCE、PCHEA、PCHPA在25℃与60℃对水泥的分散性能,发现丙烯酸酯改性的PCE可用于提高水泥混凝土流动性的经时保持能力。同时,高温下酯基的加速水解可有效缓解高温下水泥混凝土流动性损失过快的问题。测试在25℃与60℃碱性溶液水解后的电荷密度与吸附量,研究其缓释工作机理及温度敏感性表明,在水泥浆体中,PCHEA、PCHPA链段中酯基不断水解生成羧基,导致聚合物分子中电荷密度逐渐增加,PCHEA的水解速率比PCHPA快。由于酯基在水泥浆体溶液碱性作用下不断水解而导致其在水泥颗粒表面的吸附量逐渐增加,表现出缓释行为。     

磷酸盐与聚羧酸减水剂竞争吸附机理

本文通过ICP测定三聚磷酸钠、六偏磷酸钠、磷酸二氢钠、磷酸钠在水泥颗粒表面的吸附量,采用TOC分析了水泥颗粒表面对聚羧酸减水剂吸附量的影响规律,同时结合水化热、XRD及水泥浆体流动性的经时变化,研究了磷酸盐与聚羧酸减水剂共同作用下普通硅酸盐水泥的水化历程。结果表明:磷酸盐和聚羧酸减水剂复合体系中,一方面,磷酸盐、聚羧酸减水剂被吸附在未水化水泥颗粒表面,磷酸盐与聚羧酸减水剂之间存在竞争吸附,造成总吸附量减少,但吸附层厚度增加,显著影响减水剂分散性。另一方面,由于吸附层的存在而阻止自由水分子靠近,抑制水泥水化,延缓了放热峰,阻碍了水化反应。在水化的最初阶段,由于磷酸盐的缓凝作用,使得水化过程中自由水和聚羧酸减水剂的消耗减慢,缓凝效果为六偏磷酸钠三聚磷酸钠磷酸二氢钠磷酸钠。随着吸附时间的延长,在磷酸盐与聚羧酸减水剂二元体系中,由于竞争吸附造成对PC的吸附量低于单独聚羧酸减水剂体系的现象得到改善,研究结果可为磷酸盐与聚羧酸减水剂的相容性研究提供参考。     

聚羧酸减水剂分子结构中丙烯酸酯单元的缓释机理及其温度敏感性EI北大核心CSCD

以丙烯酸羟乙酯（HEA）或丙烯酸羟丙酯（HPA）为功能单体,与丙烯酸（AA）、甲基烯丙醇聚氧乙烯醚（HPEG）通过自由基共聚制备两类丙烯酸酯改性的聚羧酸减水剂PCHEA和PCHPA。通过测试PCE、PCHEA、PCHPA在25℃与60℃对水泥的分散性能,发现丙烯酸酯改性的PCE可用于提高水泥混凝土流动性的经时保持能力。同时,高温下酯基的加速水解可有效缓解高温下水泥混凝土流动性损失过快的问题。测试在25℃与60℃碱性溶液水解后的电荷密度与吸附量,研究其缓释工作机理及温度敏感性表明,在水泥浆体中,PCHEA、PCHPA链段中酯基不断水解生成羧基,导致聚合物分子中电荷密度逐渐增加,PCHEA的水解速率比PCHPA快。由于酯基在水泥浆体溶液碱性作用下不断水解而导致其在水泥颗粒表面的吸附量逐渐增加,表现出缓释行为。     

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.     

Competitive adsorption between superplasticizer and retarder molecules on mineral binder surface

In a self-levelling mortar based on the ternary binder system ordinary Portland cement (OPC), calcium aluminate cement (CAC) and anhydrite, a polycarboxylate-based superplasticizer (PC) showed no plasticizing effect in combination with citrate retarder while good flowability was observed with tartrate. The mechanism behind the incompatibility between PC and citrate was investigated by means of adsorption and zeta potential measurements. Also, anionic charge densities of the admixtures were compared. Adsorption measurements revealed that, in presence of citrate, PC adsorption drops dramatically to less than 10% of dosage added, implying a complete loss of fluidity in the paste. In presence of tartrate, however, PC adsorption remains high enough to still provide good flowability. In contrast, adsorption of casein biopolymer is not much affected by addition and type of retarder. Thus it provides high fluidity with both retarders. Comparison of specific anionic charge density of Ca²⁺ retarder complexes and PC reveals a direct correlation between their adsorption behaviour and anionic charge density. Admixtures with higher anionic charge density show higher affinity to the binder surface and thus adsorb preferredly. When several admixtures are present, molecules with lower anionic charge density will adsorb only if, after adsorption of the admixture with higher anionic charge, a cationic surface charge and enough adsorption area still exists. The incompatibility problem between PC and citrate in the self-levelling mortar formulation was solved by increasing the anionic charge density of the PC molecule. Similar to casein, adsorption of this modified PC is not much influenced by retarder molecules.     

SiO2纳米粒子改性填充PC的力学与流变性能

采用SiO2纳米粒子填充改性聚碳酸酯(PC),为使无机纳米粒子在基体PC中分散均匀,经硅烷偶联剂KH-550对SiO2纳米粒子进行表面处理,分析了改性SiO2纳米粒子对复合材料机械与加工性能的影响,并对复合材料进行了分析表征,探讨了无机刚性纳米粒子填充改性典型工程塑料PC的特点并探索其增强增韧的机理,研究了复合物的粘流变性能. 结果表明,改性SiO2纳米粒为球形,在PC基体中分散均匀,湿法改性制备的PC/SiO2纳米粒子复合材料的力学拉伸性能和流变性能最好.     

关于水泥与超塑化剂相适应性的几个问题

从水泥化学角度讨论了预拌混凝土的经与超塑化剂相适应性的几个问题。超塑化剂主要是大量吸附在水泥颗粒表面的水化产物上而不是吸附在未水化水泥颗粒表面。水泥与超塑化剂相适应性不好主要是水泥化产物吸附大量的超塑化剂所致。凡是加速水泥初期水化的因素，特别是使水泥凝结加速的因素如Ｃ，Ａ含量过高、ＳＯ３掺量过少、碱含量高以及掺入内比表面积大的火山灰质混合材等均使水泥与超塑化剂的相适应性变差。据此，提出了生产与超塑     

梳型聚羧酸高效减水剂的合成和应用性能述评

介绍了梳型聚羧酸高效减水剂合成研究及对水泥应用上的高分散性能。梳型聚羧酸高效减水剂分为甲基丙烯酸类共聚物和马来酸酐类共聚物,介绍了合成梳型聚羧酸高效减水剂的主要组分大分子单体的制备、聚合和合成结构的控制方法。综合国内外的研究成果简要介绍了聚羧酸混凝土高效减水剂分子结构和性能的关系、测试和表征方法、对水泥颗粒的分散机理等。     

Retardation effect of styrene-acrylate copolymer latexes on cement hydration

Interactions between styrene-acrylate latexes and cement are investigated with emphasis of the charge properties of the polymer particles by means of calorimetry, adsorption measurement, and confocal laser scanning microscope. Three latexes with varied surface charges of polymer particles were prepared by respectively using methacrylic acid (MAA), sodium styrene sulfonate (SSS) and methyl poly(ethylene glycol) methacrylate (MPEGMA) as water soluble monomers during synthesis. It is found that the polymer latexes retard cement hydration in two manners, namely the delaying effect represented by a delayed hydration peak and the slowing down effect characterized by a reduced main hydration peak during the acceleration period. The delaying effect is closely related to the concentration of carboxylic groups existing in the latex, while the depression effect of hydration rate is majorly caused by the adsorption of polymer particles on surface of cement grains and proportional to the total charge density of polymer particles.     

聚醚型聚羧酸减水剂的合成和表征及对水泥的微观作用机制

本文以聚醚、丙烯酸、丙烯酸羟乙酯为原料,通过自由基聚合法合成了聚羧酸减水剂JS-PCE和BT-PCE。通过正交优化所得的JS-PCE合成条件为:聚合温度25 ℃,抗坏血酸-巯基丙酸混液、丙烯酸滴加时间分别为3 h、2.5 h,酸醚物质的量比为4.25∶1,引发剂加量为聚醚质量的1.10%。添加JS-PCE的水泥净浆流动度达230 mm,表现出较好的流动性。采用界面化学及电化学等方法探究了减水剂对水泥的微观作用机制,结果表明聚羧酸减水剂在水泥颗粒表面存在饱和吸附量,其与水泥颗粒存在强吸附作用,因此产生分散和减水作用。流变行为分析得出JS-PCE和BT-PCE的最佳折固掺量分别为0.3%、0.4%。     

In-situ measurement of viscoelastic properties of fresh cement paste by a microrheology analyzer

A microrheology analyzer was adapted to in-situ follow the development of viscoelastic properties of fresh cement pastes (FCPs) for the first time. It enables a non-disturbing measurement on the FCPs through monitoring the mean square displacement of cement particles, which gives an insight into the elastic and viscous properties of materials from a microstructural point of view. Various parameters including elastic index, macroscopic viscosity index, storage modulus, loss modulus and Maxwell parameters were obtained to quantitatively analyze the viscoelastic properties of FCPs. Results indicate that these parameters show a progressive increase with time at first and then stay stable. The incorporation of superplasticizer significantly decreases these parameters and their growth rates. Moreover, superplasticizer could evidently weaken the elastic feature of the FCP due to its effects of improving the dispersion of cement grains and retarding cement hydration. The effects of superplasticizer are more pronounced at lower water to cement ratio.     

纳米SiO2对聚羧酸减水剂的吸附作用研究

采用红外光谱、紫外-可见分光光度计研究了纳米SiO2对聚羧酸减水剂的吸附作用,并利用纳米粒度zeta电位仪、旋转粘度计研究了纳米SiO2吸附减水剂后对其分散性以及新拌水泥浆体流动性的影响.研究结果表明,纳米SiO2对聚羧酸减水剂存在吸附作用,吸附量随减水剂浓度的增大而增加,当减水剂浓度增加到5g/L时,吸附量趋近饱和.纳米SiO2对聚羧酸减水剂的吸附作用,使其团聚粒径增大,粒径分布曲线整体向大颗粒方向偏移,分散性大大降低.将纳米SiO2溶于拌和水中,先加入水泥搅拌,然后再加入减水剂搅拌,可减小纳米SiO2对减水剂的吸附,增大减水剂的利用效率,提高水泥浆体的流动性.     

抗泥型聚羧酸减水剂的制备及性能

以甲基丙烯酸（MAA）、甲基丙烯酸羟乙酯（HEMA）为单体,过氧化氢（H₂O₂）/抗坏血酸（Vc）为引发剂,甲基烯丙基磺酸钠（SMAS）为链转移剂,合成了一种抗泥型聚羧酸减水剂,通过红外光谱（FTIR）、凝胶渗透色谱（GPC）对聚合物进行结构表征,通过水泥净浆流动度、蒙脱土层间官能团、X射线衍射和吸附量测试,对其分散性能及抑制蒙脱土机理进行了探究。结果显示：合成的抗泥型聚羧酸减水剂在摩尔比为2.5：1时分散性能最佳,当减水剂折固掺量为0.25%时,水泥初始净浆流动度为268mm;与普通聚羧酸减水剂相比,合成的抗泥型减水剂对蒙脱土敏感性较低,与蒙脱土作用后的层间未出现抗泥型减水剂的特征官能团,层间距为1.40nm,抗泥型减水剂在蒙脱土上的吸附量远小于普通减水剂的吸附量。