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.     

减水剂对高掺量粉煤灰砂浆性能的影响

研究了萘系高效减水剂（FDN）和木质素磺酸钙（LS）对高掺量粉煤灰砂浆性能的影响,测定了减水剂在胶凝颗粒表面的吸附、对水泥颗粒表面zeta电位等方面的影响。结果表明,和FDN相比,LS对砂浆的减水率较低,而对砂浆流动度保持能力较优;当掺量为0.4 wt%时,两者对砂浆稳定性的影响几乎一样。当掺量低于0.4 %时,LS的减水率和FDN接近是因为其具有较强的引气作用和FDN在胶凝颗粒表面吸附不完全;LS保持砂浆流动性能力较好是由于它的缓凝作用以及吸附LS的水泥颗粒表面zeta电位较稳定导致的。为了更好地将LS应用在高掺量粉煤灰砂浆中,可以从提高其减水率方面对其进行改性。     

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。     

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.     

Effect of PCEs with Different Functional Groups on the Performance of Cement Paste

The adsorption behaviors and dispersing properties of polycarboxylate superplasticizer(PCE) with different functional groups were systematically analyzed to reveal the theory and methods of modifying PCE molecular structures and regulating PCE performances. By substituting carboxylic groups with sulfonic groups, ester groups or acylamino groups, respectively, modified PCEs with different functional groups were synthesized. Results show that introducing low amount of ester groups or sulfonic groups into the PCE molecules has no negative effects on the fluidity of cement paste, while introducing acylamino groups into PCE molecules significantly weakens the fluidity of cement paste. At low amount(when the molar ratio of sodium methallyl sulfonate to TPEG is lower than 0.4), the rapid adsorption of sulfonic groups onto the cement particles contributes to the high dispersing performance of the sulfonic group modified PCEs. When the substitution ratio of acrylic acid by sulfonic acid is higher than 0.4, the viscosity and the yield stress of cement paste increases sharply. Redundant sulfonic groups lead to the excessive charge density of the PCE, which contributes to the inhomogeneous adsorption on the cement grains and hence results in the decline of the dispersing performance. Substitution of carboxylic group by acylamino group or ester group slightly changes the viscosity as well as the yield stress of cement paste. Introducing sulfonic group into PCE molecule improves the adsorption behavior of PCEs, while introducing ester group or acylamino group into PCE depresses the adsorption properties.     

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.     

Effects of CFB Ash on the Adsorption Mechanism of Polycarboxylate Superplasticiser

The effects of circulating fluid bed(CFB) ash on the adsorption performance of polycarboxylate superplasticiser and the mechanism of this influence on the dispersive property of the polycarboxylate superplasticiser were investigated by determing the cement paste fluidity, total organic carbon adsorption, infrared spectroscopic analyses and ζ potential test. The experimental results show that the addition of an inorganic salt into the mixture to change the content of SO_4~(2-)and Fe_2 O_3 can improve the adaptability between the CFB ash and polycarboxylate superplasticiser. Adsorption may occur between the polycarboxylate superplasiciser and Fe_2 O_3, SO_4~(2-)or other components in CFB ash, leading to a significant reduction in paste fluidity. As the content of Na_2 SO_4 in CFB ash reaches 3% or Fe_2 O_3 reaches 9%, the paste loses its liquidity. The organic carbon content in the liquor decreases with an increase in Na2_ SO_4 or Fe_2 O_3 content. Adding some Ba(NO_3)_2 and Na_2 S to the liquor can recover the organic carbon content to a certain extent, and the absolute value of ζ potential will increase. The addition of Ba(-NO_3)_2 or Na_2 S reduces the adsorption property of Na_2 SO_4 or Fe_2 O_3 in CFB ash on the polycarboxylate superplasticiser.     

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。     

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.     

Effect of delay released welan gum on the performance of cement mortar

Welan gum is widely applied in environmental admixtures due to its good thickening and rheological properties. With its powerful charge density in the molecular structure, the competitive adsorption between welan gum and other admixtures happened remarkably during the addition process. So controlling the releasing rate of welan gum will be able to improve the competitive adsorption, while having no disadvantages to its thickening and workability at the same time. The investigation of influences of the delay released welan gum (DRWG) on the fluidity and strength of cement mortar, bleeding rate and rheological properties of cement paste, adsorption amount and zeta potential of clinker single mineralogical phases, shows that there will be a better mortar workability and certain improvement in mortar strength with DRWG. For mortar with DRWG, the standing bleeding rate is 0, and there is less thixotropic, less adsorption, and a lower zeta potential value on the surface of clinker mineralogical phases.     

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.     

Relaxation study of cement based grouting material using nuclear magnetic resonance

Aiming at actual condition of poor effect of hole sealing for the reason of poor cement paste fluidity in the process of coal mine gas drainage, by adding a water reducing agent, cement paste for hole sealing was produced. The changes of initial distribution, weighted average values and total relaxation signal intensity of transverse relaxation time (T₂) of water in pure cement paste and water reducing agent added cement paste were studied with low field proton nuclear magnetic resonance (NMR). The results show that there are four peaks in T₂ distribution curves of cement paste: the first peak is related to the bound water in flocculation, the second and the third peaks are related to the water in flocculation, water reducing agent makes it extending towards the long relaxation time, increasing its liquidity, and the fourth peak is related to the free water. By using weighted average values of T₂ and total relaxation signal intensity, hydration process of cement pastes could be roughly divided into four stages: the initial period, reaction period, accelerated period and steady period. By analyzing the periods, it makes sure that the grouting process should be completed in the reaction period in the site, and the drainage process should be started in the steady period. The results have great guiding significance to the hole sealing and methane drainage.     

Effect of polycarboxylate-type superplasticizer on the paste fluidity based on the water film thickness of flocs

The excess water film theory and the properties of flocs are integrated to examine the effect of the polycarboxylate-type superplasticizer on the paste fluidity.The theory states that excess water can surround the flocs rather than the particles and that the cell consists of a floc and a superficial water film.Experiments on limestone powder pastes were conducted to verify the theory.The superplasticizer dosage(sp%)and the water–powder ratio by volume(Vw/Vp)were systematically varied.A sedimentation balance method was used to measure the size distribution of the flocs in the limestone powder pastes.The water film thickness(WFT)of flocs was then calculated and shown to determine the paste fluidity.Based on this WFT of flocs,the effect of the sp on the paste fluidity was determined and then compared with the effect of water.     

ACS新型高效减水剂的研究(1)-减水剂的合成和其在水泥颗粒表面的吸附

根据聚合物分子设计原理,通过乙烯类单体的自由基溶液共聚合制备了分子链中含阴离子基团和支链的共聚物,制备了对水泥颗粒具有良好分散作用和分散稳定作用的混凝土用丙烯酸接枝共聚型高效减水剂（ACS）。用红外光谱表征了基结构。对照商品萘系高效减水剂FDN,研究了ACS在水泥颗粒表面的吸附。吸附量和ζ－电位的测定表明,ACS分子可吸附到水泥颗粒表面,其极限吸附量为1．97mg/g吸附后,水泥颗粒表面ζ－电位由＋10mV变成－15mV。     

Synthesis of a macromer, MPEGAA, used to prepare an AMPS-modified polyacrylic acid superplasticizer

A macromer, methoxypolyethylene glycol acrylate （MPEGAA）, was synthesized by direct esterification using methoxypolyethylene glycol （MPEG-1200） and acrylic acid （AA） as the main materials. MPEGAA was then used to prepare a polyacrylic acid superplasticizer modified with 2-acrylamido-2- methylpropane sulfonic acid （AMPS）. A single-factor test was performed to investigate the effects of the molar ratio of acid to alcohol （n（AA）/n（MPEG））, inhibitor amount, catalyst amount, temperature, and time of esterification on the synthesis of MPEGAA. The experimental results showed that the optimal esterification conditions were as follows： n（AA）/n（MPEG）, 3.5：1; amount of hydroquinone （as an inhibitor）, 1.2%; amount of para-toluenesulfonic acid （as a catalyst）, 5.5%; reaction temperature, 95 ~C; and reaction time, 6 h. The AMPS- modified polyacrylic acid superplasticizer prepared under the optimal esterification conditions enabled the achievement and maintenance of high cement dispersibility. At an admixture amount of 0.15%, the cement paste fluidity was initially as high as 300 mm, and then decreased to 315 mm after 1 h and to 290 mm after 2 h.     

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。     

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。     

磺化淀粉-聚羧酸复合减水剂的制备与表征

由于保护环境的原因,以天然高分子为原料来合成高效减水剂已经成为混凝土外加剂研究领域的新热点.本文研究了采用磺化糊精取代部分功能大单体来合成复合聚羧酸减水剂的方法.结果显示:当磺化糊精取代功能单体40%、复合聚羧酸减水剂掺量为0.5%时,水泥净浆的初始流动度达255,mm,1,h 后其流动度仍为250,mm.淀粉酸解后,增加亲水的羟基基团导致初期水化缓慢,而增加 Zeta 电位使水泥颗粒更易于分散.在复合减水剂中,长链 Starch 与短链的聚羧酸减水剂主链将被吸附于水泥颗粒表面上,交替发生静电与空间位阻作用,起到了增加减水率和降低缓凝的效果.     

Design and preparation of high elastic modulus self-compacting concrete for pre-stressed mass concrete structures

Requirements of self-compacting concrete (SCC) applied in pre-stressed mass concrete structures include high fluidity, high elastic modulus, low adiabatic temperature rise and low drying shrinkage, which cannot be satisfied by ordinary SCC. In this study, in order to solve the problem, a few principles of SCC design were proposed and the effects of binder amount, fly ash (FA) substitution, aggregate content and gradation on the workability, temperature rise, drying shrinkage and elastic modulus of SCC were investigated. The results and analysis indicate that the primary factor influencing the fluidity was paste content, and the main methods improving the elastic modulusof SCC were a lower sand ratio and an optimized coarse aggregate gradation. Lower adiabatic temperature rise and drying shrinkage were beneficial for decreasing the cement content. Further, based on the optimization of mixture, a C50 grade SCC (with binder amount of only 480 kg/ m3, fly ash substitution of 40%, sand ratio of 51% and proper coarse aggregate gradation (V _{5-10 mm}: V _{10-16 mm}: V _{16-20 mm}= 30%: 30%:40%)) with superior workability was successfully prepared. The temperature rise and drying shrinkage of the prepared SCC were significantly reduced, and the elastic modulus reached 37.6 GPa at 28 d.     

ACS新型高效减水剂的研究（3）—对水泥颗粒产生分散—流化作用的机理

研究了丙烯酸接枝共聚型高效减水剂ACS对水泥浆产生分散－流化作用的机理。对添加ACS的体系水泥胶粒表面ζ－电位的测定表明,静电斥力是产生分散－流化作用的物理因素之一。ACS靶链中n值对流动度的影响证明了立体位阻效应的存在。表面张力是第三个物理因素。通过测定ACS对水泥水化的影响和ACS共聚物相对粘度在碱性条件下的变化,表明对水泥水化的抑制和分子徐放是产生分散－流化作用的化学因素。