萘系高效减水剂的吸附特性及吸附模型

采用水泥水化体系和粉煤灰非水化体系2种浆体,研究萘系高效减水剂(polynaphthalene sulphonate,PNS)的吸附特性及对净浆流动性的影响,更有助于深刻认识PNS的作用机理。结果表明:掺PNS的2种净浆初始扩展度及扩展度经时损失规律相同,但吸附量均随时间延长而增大,说明水泥水化并非流动度经时损失的唯一原因。高掺量的PNS在水泥颗粒表面吸附量明显大于低掺量的,但X射线光电子能谱测试表明水泥颗粒表面的C原子所占比例相差不大,说明PNS在水泥颗粒表面存在不同的吸附形态。提出了PNS动态吸附模型,即:PNS存在尾式、环式和卧式等多种吸附形态,而且3种吸附形态会随时间和吸附量的变化而变化,吸附形态的转变是导致PNS塑化浆体流动性损失的重要原因之一。     

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。     

外加剂添加时间对水泥浆体吸附和分散性能的影响

通过分析外加剂添加时间对水泥浆体吸附、Zeta电位、流动度的影响及其相互关系,研究了萘系高效减水剂和聚羧酸系高效减水剂对普通硅酸盐水泥浆体吸附及分散性能的影响.结果表明:随减水剂添加时间的延迟,水泥颗粒对萘系减水剂和聚羧酸减水剂的吸附量均急剧降低至趋于平缓;减水剂添加时间对水泥浆体吸附、电位与流动度之间关系的影响不同,随着添加时间的延长,减水剂吸附量降低、电位绝对值减小;萘系高效减水剂最佳掺加时间为加水后10 min左右,此时水泥颗粒对减水剂分子的吸附量偏低,对应的水泥浆体达到最佳的流动度;聚羧酸系高效减水剂与水同掺时吸附量最大,对应水泥浆体的流动度也最大.     

葡萄糖酸钠对萘系高效减水剂塑化水泥浆体流动性的影响(英文)

研究了掺萘系高效减水剂浆体中同时掺入葡萄糖酸钠时,对水泥浆体流动性和流动性损失的影响。适量的葡萄糖酸钠可显著提高浆体初始流动度,并降低流动度损失。采用紫外分光光度计、zeta电位仪、X衍射仪和扫描电子显微镜测试了浆体对萘系高效减水剂的吸附量、水泥颗粒表面电位、水化产物钙矾石X衍射峰值强度和微观形貌。结果表明:在同等萘系高效减水剂掺量下,葡萄糖酸钠延缓了钙矾石的生成,并与萘系减水剂在水泥颗粒表面形成竞争吸附,导致了水化过程中萘系高效减水剂消耗量的降低,增加了高效减水剂在水泥颗粒表面的有效吸附量。     

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。     

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。     

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。     

水泥和黏土矿物对不同减水剂的吸附特性

采用有机碳测定仪和紫外分光光度计,分别研究了聚羧酸减水剂、萘系减水剂和木质素磺酸钠在水泥、高岭土和蒙脱石颗粒表面的吸附特性,并对掺高岭土和蒙脱石的水泥净浆的流动度和黏度进行了测试,用三维视频显微镜观察了三种颗粒的形貌特征。结果表明:水泥、高岭土和蒙脱石对不同减水剂的吸附量不同;水泥比高岭土和蒙脱石对萘系减水剂的吸附量大,高岭土和蒙脱石比水泥对聚羧酸和木质素磺酸钠减水剂的吸附量大;水泥和高岭土颗粒表面较平滑,蒙脱石表面较粗糙;在掺入不同减水剂的水泥浆体中,蒙脱石和高岭土的掺入都会降低浆体流动度,提高浆体黏度,并且蒙脱石的影响更大。     

硅烷改性聚羧酸减水剂-Na2SO4-水泥体系分散及流变性能的研究

采用γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570),丙烯酸(AA)以及甲基烯丙基聚氧乙烯醚(HPEG)单体,通过自由基聚合法合成了硅烷改性聚羧酸减水剂(SPC).试验研究了引入硅烷官能团后,减水剂分子成分、电荷密度以及对Na2SO4-水泥体系分散及流变性能的影响规律.研究结果表明,在SPC红外特征峰中发现了Si-O的伸缩振动峰,说明SPC成功引入硅烷官能团;电荷密度测试表明,PC比SPC具有较高的-COO-含量;通过分散性能、流变性能及吸附量测试,表明与PC相比,SPC能够通过≡Si-OH与水泥颗粒表面的-OH发生化学缩合反应,提高减水剂分子在Na2SO4-水泥体系中对水泥颗粒表面的吸附能力,降低屈服应力和塑性粘度,从而提高减水剂对水泥浆体的分散及流变性能.     

氨基磺酸系高效减水剂对水泥的分散作用研究

研究了氨基磺酸系新型高效减水剂ASP对水泥净浆的分散作用机理。对照商品萘系高效减水剂FDN，研究了掺加减水剂后水泥胶粒的ζ电位及水泥颗粒对减水剂的吸附量。结果表明，掺加ASP和FDN后水泥颗粒的ζ电位基本相同，而ASP在水泥颗粒的吸附量较FDN的小，ASP对水泥的良好分散作用是由静电斥力和空间位阻共同作用的结果。ζ     

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.     

Adsorption characteristics of superplasticizers on cement component minerals

Adsorption characteristics of various superplasticizers on portland cement component minerals were investigated. Adsorption isotherms of various types of superplasticizers and ζ-potentials of cement component minerals at the maximum adsorption of the superplasticizers were measured. The value of the adsorption isotherm was calculated from the amount of the superplasticizer adsorbed on a cement component mineral in an equilibrated solution. The maximum amounts of adsorption and the adsorption isotherms varied with types of component mineral and superplasticizer. For all types of superplasticizers, a larger amount of superplasticizer was adsorbed on C₃A and C₄AF than C₃S and C₂S. However, the equilibrated concentration of each superplasticizer at the maximum adsorption was not influenced by types of superplasticizer. Without superplasticizer, C₃S and C₂S had negative ζ-potential. On the contrary, C₃A and C₄AF had positive ζ-potential. Therefore, accelerated coagulation of cement particles might occur due to their electrostatic potentials that are opposite each other. However, all component minerals of cement had negative ζ-potential when they were mixed with any superplasticizer. Fluidity of fresh cement paste is improved due to electrostatic repulsion acting between particles.     

The fluidity of fly ash-cement paste containing naphthalene sulfonate superplasticizer

The zeta potential measurement indicated that the surface potential of fly ash was different from ordinary Portland cement (OPC) in both sign and value. Hence, the Derjaguin-Landau-Verway-Overbeek (DLVO) theory for dispersion-flocculation of heterogeneous particles with different surface potentials was applied to explain the influence of fly ash on the rheology of cement paste containing naphthalene sulfonate superplasticizer. For the fly ash-cement paste without superplasticizer, the sign of zeta potential of fly ash was different from OPC. Thus, the extent of the potential energy barrier between particles was small or even showed negative value, and the change in the rheology of the fly ash-cement paste was mainly dependent on the bulk solid volume of fly ash, which was related to available free water for fluidizing paste. For the fly ash-cement paste with naphthalene sulfonate superplasticizer, fly ash and cement had the same sign and dispersed well due to higher potential barrier. The extent of potential energy barrier depended on the absolute value of surface potential, which was represented by a function of the amount of adsorbed superplasticizer. The bulk solid volume of fly ash also affected the change in flow ability, but the effect of potential energy barrier between particles was superior to that of the bulk solid volume of fly ash.     

The effect of the kind of calcium sulfate in cements on the dispersing ability of poly β-naphthalene sulfonate condensate superplasticizer

Many studies have been carried out to prevent the incompatibility problem between poly β-naphthalene sulfonate condensate superplasticizer (PNS) and cements. Several of them suggested that the effect of SO₄²⁻ concentration on adsorption equilibrium might be more important for the performance of PNS than the effect of ionic strength on electrostatic repulsion. In this study, the influence mechanism of the kind of calcium sulfate in cements on the performance of PNS was analyzed in regards to SO₄²⁻ concentration change with time elapse. It was found that SO₄²⁻ concentration change was affected by two kinds of calcium sulfate, gypsum and hemihydrate. In case of using the cement containing mainly hemihydrate, SO₄²⁻ concentration in the solution phase of cement paste initially after mixing is high; however, it decreases rapidly with time elapse. The adsorbed amount of PNS onto surface of cement particle is limited just after mixing because the SO₄²⁻ concentration is high and increases with decreasing SO₄²⁻ concentration. As a result, the flow loss of cement paste decreases.     

Organic admixtures and cement particles: Competitive adsorption and its macroscopic rheological consequences

In this work, we study the competitive adsorption in cement paste between a superplasticizer and a so-called viscosity agent along with the competitive adsorption between the same superplasticizer and a retarder. We develop a new protocol using dynamic light scattering, which allows for distinguishing the relative adsorption of different fractions of admixtures when introduced simultaneously in cement paste. Our results show that the result of competitive adsorption is not only a matter of admixture chemical structures or physical properties but is also very dependent on surface coverage. We identify from our results, similarly to other authors in polymer literature, three main competitive adsorption regimes. We finally show that the outcome of competitive adsorption measured at the microscopic scale can explain the measured macroscopic variations in rheology in terms of yield stress and viscosity.     

高效减水剂与水泥及掺混合材水泥的相容性研究

通过对掺高效减水剂水泥净浆流动性及流动性损失的测定试验,研究了高效减水剂与水泥及掺混合材水泥的相容性。试验结果表明,同一种高效减水剂与不同水泥的相容性不同;矿渣和粉煤灰都能改善水泥与高效减水剂的相容性;复掺粉煤灰和矿渣比矿渣单掺时改善效果好。     

聚醚侧链聚羧酸类减水剂的结构及应用性能

通过大分子反应,合成了一类主链带羧基、磺酸基,支链带聚氧乙烯基醚的聚羧酸系高效减水剂。利用IR和1H NMR表征了其结构,并通过对减水剂溶液表面张力、水泥颗粒表面吸附量以及溶液的电导率的测定,发现研制的减水剂能降低水的表面张力,并被吸附在水泥颗粒表面从而降低了水泥颗粒的表面能,使得水泥净浆有较好的分散作用,实验表明本研究制备的聚羧酸系减水剂对水泥颗粒有较好的分散作用。     

Effect of molecular weight of sulfanilic acid-phenol-formaldehyde condensate on the properties of cementitious system

The effect of the molecular weight of sulfanilic acid-phenol-formaldehyde condensate (SPF) on the properties of cementitious system was investigated. It is found that SPF with the molecular weight of 35,000 Dalton (Da) gives a good adsorption capacity on the surface of the cement particles, hence a larger zeta potential to cement particles and a good fluidity to the cement paste. In addition, this fraction has a high chelating capacity to calcium in the cement slurry, causing a long retardation of the cementitious system. However, the fractions of a high molecular weight (42,000 Da, and 45,000 Da) exhibit lower bleed water as a percentage of total mix water (BWP). It can be deduced that there is an ideal molecular weight for the best performances of the superplasticizer investigated, which can be used for optimizing the technical parameters in the preparation.     

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。