萘系减水剂混凝土钢筋的电化学腐蚀

腐蚀电位监测、线性极化和交流阻抗测试等方法研究混凝土中添加萘系减水剂对钢筋腐蚀行为的影响.发现添加萘系减水剂的混凝土,其电阻和极化电阻大幅增加,其中以添加0.2%萘系减水剂的增幅最明显.适量的萘系减水剂有利于改善混凝土的孔隙结构,增强混凝土的密实性和抗渗透性能,从而减缓混凝土的钢筋腐蚀.     

分散剂表面吸附特性和相关电化学性质对煤浆分散体系流变特性的影响

采用１７种不同变质程度的中国煤，详细研究了一种阴离子型分散剂在煤表面的吸附特性及其相关的表面电化学性质对煤成浆性及浆体流变特性的影响。结果表明，煤成浆性及浆体流变性并不单独取决于煤对分散剂的吸附量和煤表面动电位的大小。反映煤成浆性的浆体最高煤浆浓度取决于分散剂在煤表面的Ｌａｎｇｍｕｉｒ饱和吸附量Γｓ和相应动电位ξｓ的乘积Γｓ×ξｓ，而浆体流变指数则依赖于两者比值的大小Γｓ／ξｓ。表明水煤浆分散体系中煤颗粒的分散一方面是靠静电分散作用来实现，另一方面，分散剂在煤表面的吸附所产生的非静电分散作用也起了重要作用。同时，分散剂的表面吸附使煤表面产生的吸附荷电效应不能过高，否则，会对流体流变性不利。     

聚羧酸减水剂分子结构对水泥分散速度的影响

本文通过设计不同的分子内酸醚比值(A/E值)、分子量和聚合物分子量组成方式制备了系列聚羧酸减水剂。采用GPC方法监测了样品的分子量、聚醚转化率和聚合物分子量增长历程。采用净浆流动度测试方法表征了不同搅拌时间条件下聚合物的分散性能。用TOC方法测试了聚合物掺量与吸附量的关系,并监测了180min内吸附量随时间的变化规律。实验结果表明:提高聚合物中酸醚比值或者分子量能小幅加快聚合物的分散速度,但会劣化分散性能。适当提高前期聚合物分子量能有效加快其相对吸附速度和分散速度,满足快分散或低温施工需求;降低前期聚合物分子量则能降低相对吸附速度和分散速度,满足快速损失混凝土体系和降低减水剂敏感性需求。最为重要的是,针对性调整分子结构组成对聚合物整体吸附能力和分散能力不造成明显影响。     

氟镧镨掺杂对铈基抛光粉微结构、颗粒特征及抛光性能的影响

以Ce_2(CO_3)_3为前驱体,La_2(CO_3)3和Pr_2(CO_3)_3为掺杂试剂,NH_4F为氟化剂制备铈基抛光粉,研究了F/La/Pr掺杂对铈基抛光粉的物相结构、表面形貌、表面Zeta电位和抛蚀量的影响。XRD,Raman光谱和Zeta电位分析表明:F的引入可以显著地减小铈基抛光粉的晶粒尺寸、增大其晶格缺陷和颗粒表面Zeta电位,且同时掺La-Pr比单独掺La对增大其晶格缺陷和颗粒表面Zeta电位影响更大。SEM分析表明,F的引入有利于颗粒的球形化,掺入La或Pr有利于改善颗粒的聚集状态。抛光测试分析表明:抛蚀量的大小与相应铈基抛光粉的颗粒表面Zeta电位和晶格缺陷成正比。     

磺化木质素系聚合物的结构及其在氧化铝上的吸附特性

以造纸黑液中的碱木质素为主要原料,通过磺化和缩聚反应制备了磺化木质素高分子聚合物SBAL.TEM和1H-NMR测试结果表明SBAL是以木质素的疏水骨架为中心,以磺酸基和羧基组成亲水性侧链的球形结构.GPC测试结果表明其重均分子量达到了24880 Da,是碱木质素的7.38倍,电位滴定测试结果表明,其磺化度达到2.70 mmol.g-1.通过流变曲线、吸附等温线、zeta电位、XPS测试研究了其对氧化铝在水中的分散机理及其吸附特性.掺SBAL的氧化铝浆体,在pH=3～12范围内SBAL对其具有良好的分散降黏作用.溶液pH对SBAL的分子构型和吸附特性有较大的影响,随pH增加,SBAL中磺酸基、羧基和酚羟基逐渐电离,分子的伸展程度逐渐增大.随pH增加,SBAL在氧化铝上的吸附质量减少,吸附层由致密逐渐变得疏松,pH小于等电点时以静电吸附为主,pH大于等电点时以非静电的特性吸附为主.当SBAL的用量小于临界值(0.5 wt%)时,其在氧化铝表面形成单分子层吸附,在颗粒间起到静电排斥作用;当用量大于临界值时,其在颗粒表面形成聚集体吸附而起到空间位阻作用.     

不同相对分子质量对接枝磺化木质素水煤浆分散剂吸附分散性能的影响

采用接枝磺化缩聚法制备了不同相对分子质量碱木质素系水煤浆分散剂(GCL3J系列),研究相对分子质量对水煤浆吸附分散性能的影响。流变学研究结果表明,具有三维空间网络结构的GCL3J分散降黏性能均优于具有线性结构的萘系分散剂。等温吸附和Zeta电位测试结果表明,GCL3J在煤粒表面的吸附特征属于Langmuir型单分子层吸附,随着相对分子质量的增加,其在煤粒上的吸附量逐渐减少,吸附作用力逐渐增强,并逐渐以疏水作用吸附为主。中等相对分子质量的GCL3J-3(M_w为31 500 Da,特性黏度为8.06 mL/g)在煤粒表面吸附后,具有适宜的吸附量和吸附强度,且负电性最高,对水煤浆具有最优的分散降黏作用。     

利用分散稳定性分析仪研究水煤浆的稳定性

采用Turbiscan Lab浓缩体系分散稳定性分析仪研究了改性木质素系分散剂（GCL3S）和萘系分散剂（FDN）对水煤浆稳定性及浆体中煤颗粒沉降行为的影响。结果表明,水煤浆中煤粒沉降行为为差异沉降,在水煤浆制备过程中,煤颗粒之间会发生团聚,掺1.0％GCL3S的水煤浆清液区高度及平均沉降速率仅为掺FDN的68％,木质素系分散剂制备的水煤浆稳定性能优于萘系。分散稳定性分析仪不仅可以用于水煤浆的稳定性分析,还有助于揭示分散剂对水煤浆的稳定作用机理。     

Brij类表面活性剂与Laponite纳米颗粒的相互作用及其稳定乳液的研究

通过表面张力、Zeta电位和流变学参数的测定, 研究了聚氧乙烯烷基醚类非离子型表面活性剂(Brij 30和Brij 35)在合成锂皂石(Laponite)纳米颗粒表面的吸附及对Laponite水分散体系中颗粒间相互作用和体系粘度的影响. 结果表明, 这类表面活性剂能显著地吸附在Laponite颗粒表面上, 且吸附量随其分子中POE链长短而不同. 这种吸附没有改变Laponite粒子的带电性质, 但一定程度地降低了Laponite颗粒Zeta电位; 吸附也会减弱颗粒间的相互作用, 降低体系的粘度. 实验以Laponite和Brij为乳化剂, 制备了O/W型乳状液. 乳液稳定性变化和乳液粒径分布结果表明, 体系中Brij的浓度较低时, 乳液的性质主要是由Laponite颗粒决定的; 而Brij浓度较高时, 则主要取决于Brij表面活性剂. 高速剪切含Brij的Laponite水分散体系, 剪切后表面张力随时间的变化表明, 剪切作用会使得吸附在Laponite颗粒表面的Brij分子不同程度地解吸下来. 这也意味着乳液制备时, 高速剪切作用也会造成Brij分子自Laponite颗粒表面的脱附, 这可能是非离子表面活性剂与阳离子表面活性剂对负电固体颗粒稳定乳液影响不同的原因.     

分散剂表面吸附特性和相关电化学性质对煤浆分散体系流变特性…

采用１７种不同变质程度的中国煤，详细研究了一种阴离子型分散剂在煤表面的吸附特性及其相关的表面电化学性质对煤成浆性及浆体流变特性的影响。结果表明，煤成浆性及浆体流变性并不单独取决于煤对分散剂的吸附量和煤表面动电位的大小。     

木质素磺酸盐在烯酰吗啉颗粒表面的吸附特性

考察了常用分散剂木质素磺酸钠(Sodium Lignosulfonate, SLS)在烯酰吗啉(Dimethomorph, DMM)上的吸附性能, 并测试了吸附SLS后DMM颗粒表面Zeta电位和接触角的变化, 从理论上探讨了分散剂的吸附对农药颗粒表面物化性能的影响, 指导农药分散剂的开发. 结果显示, 浓度为0~10 g/L时, SLS在DMM表面呈现双层吸附; 低浓度(0~1.0 g/L)时, 吸附等温线符合Langmuir方程. SLS在DMM表面上的吸附属于自发、 放热吸附过程, 吸附力主要包括疏水作用、 范德华力和氢键作用力. SLS在DMM表面吸附后提高了其Zeta电位, 且SLS磺化度越高其提高作用越明显. 随着SLS溶液浓度增大, DMM在SLS溶液中的接触角先减小后增大, 到70º~80º后趋于稳定.     

Release characteristics of semi-volatile heavy metals during co-combustion of sewage sludge and coal under the O<Subscript>2</Subscript>/CO<Subscript>2</Subscript> atmosphere

Oil well cementing is a vital operation to assure casing stability and zonal isolation for oil and gas exploration. However, some scenarios demand the cemented region to withstand high thermal gradients and imposed deformations, as occurs in the case of oil wells subjected to cyclic steam injection at temperatures up to 250 °C, to reduce oil viscosity and to increase well pressure to facilitate heavy oil recovery. In this paper, the hydration of ductile special cement systems using styrene-butadiene latex (SBR) and carboxylated styrene-butadiene latex (XSBR) addition was studied by conduction calorimetry. The resulting heat flow curves, presented in log–log plots, were used to analyze the influence of those copolymers on the hydration stages of three families of cement pastes of different complexity. The simpler cement systems (SCCS) contained water, oil well Portland cement class G and SBR or XSBR in its composition. In medium complexity systems silica fume was added and in the higher complexity ones (HCCS), superplasticizer as well. The primary objective of adding those copolymers into the Portland cement paste is to obtain higher ductility properties after setting, silica fume to have good thermal stability up to 300 °C, while superplasticizer was added to guarantee good workability. Rheological tests were carried out to evaluate the effect of the copolymers on the composite viscosity. Thermogravimetric analysis of selected SCCS and HCCS samples was performed to quantify the main formed phases up to 24 h of cement hydration. From the obtained results, it was noticed that SBR and XSBR addition substantially affects hydration kinetics at all early age stages. Starting from pre-induction and induction periods, the main observed effect during these stages, was related to the increased viscosity of the pastes, which was higher in XSBR containing pastes, retarding the hydration reactions of respective following stages, when compared to pastes with the same cementitious matrix without copolymer addition.     

Evaluation of the Dispersing Properties of Polycarboxylate-Type Superplasticizers with Different Molecular Weight in Cement Systems

In order to evaluate the dispersing properties of polycarboxylate-type superplasticizers (PCs) with different molecular weight in cement pastes, PCs with different molecular weight (low, medium, high) were synthesized, and used as superplasticizer for cement suspensions. The effect of molecular weight of PC on the zeta potential, adsorption, fluidity of the corresponding cement suspensions was investigated systematically, and total interparticle potential energy between particles was calculated. The results show that, the higher molecular weight of PC, the larger adsorption amount of PC. PC with medium molecular weight presents a better dispersing property than PC with high molecular weight, while PC with low molecular weight falls in between. The maintaining dispersing ability of PC for cement particles is weakened gradually with the increasing of molecular weight. The changing rule of total interparticle potential energy produced by PC is in accordance with the changing rule of dispersing property of PC in cement pastes. This indicates that the calculated results of total interparticle potential energy further support the explanation of dispersing property difference of PC in theory. This article uses the sum of electrostatic energy and steric hindrance potential as the total interparticle potential energy to evaluate the dispersing property of PC for the first time, which is meaningful for evaluation of dispersing property of polymer dispersant adsorbed on particle surfaces.     

Influence of superabsorbent polymers on hydration of cement pastes with low water-to-binder ratio

Internal curing with superabsorbent polymers (SAP) is a method for promoting hydration of cement and limiting self-desiccation, shrinkage and cracking in high-performance, and ultra high-performance concrete with low water-to-binder ratio. SAP are introduced in the dry state during mixing and form water-filled inclusions by absorbing pore solution. The absorbed solution is later released to the cement paste during hydration of the cement. In this paper, cement pastes with low water-to-binder ratios incorporating superplasticizer and different dosages of SAP and corresponding additional water were prepared. Reference cement pastes without SAP but with the same amount of water and superplasticizer were also mixed. Isothermal calorimetry was used to measure hydration heat flow. Water entrainment by means of SAP increased the degree of hydration at later hydration times in a manner similar to increasing the water-to-binder ratio. Addition of SAP also delayed the main calorimetric hydration peak compared to the reference pastes, however, in a less prominent manner than the increase in water-to-cement ratio.     

Effects of cyclodextrin-modified polycarboxylate superplasticizers on the dispersion and hydration properties of cement paste

Abstract

A new series of poly (AA-co-β-CD-A-co-TPEG) (PACDs) copolymers were prepared by the copolymerization of a novel monovinyl β-cyclodextrin monomer (β-CD-A), acrylic acid and isoprenyl oxy polyethylene glycol (TPEG-2400), which could be used as superplasticizers and shown excellent dispersion ability. Therefore, this work mainly investigated the adsorption behavior, dispersing properties as well as hydration behavior of cement pastes. Optical microscopy was employed to describe dispersing performance. X-ray diffraction (XRD) and TGA/DTG were utilized to account for the cement hydration process. We found that the PACDs with β-CD-A exhibited outstanding dispersion ability. In addition, the performances of the PACDs were monitored by evaluating the setting time and fluidity of the cement paste. The results clearly shown that the setting time was longer and slump loss was smaller than that of PACD₀ that without β-CD-A. Therefore, PACDs with the proper content of β-CD pendants had excellent performances due to the steric hindrance of the CD moieties.     

Physical and chemical studies on cement containing sugarcane molasses

Molasses is generally used as a grinding aid in cement and as a water reducer and retarder in concrete. In China, the output primarily consists of sugarcane molasses. In this paper, the effects of sugarcane molasses on the physical performance and hydration chemistry of conventional Portland cement were investigated. The setting times, the normal consistency of cement pastes, the compressive strengths and fluidities of the mortars were respectively determined according to Chinese Standard GB/T 1346, GB/T17671 and GB/T 2419. The effect of molasses on the hydration kinetics of cement was investigated using a calorimeter. The hydration products and pore size distribution of the cement pastes were analysed by X-ray powder diffraction, differential scanning calorimetry and a mercury injection apparatus. The results show that a small amount of sugarcane molasses retards the setting and hardening of cement paste and increases the fluidity of cement mortar, while excess molasses accelerates the setting and hardening. Molasses improves significantly the compressive strength at 3d due to the decrease of porosity. The addition of 1.0 % molasses accelerates the formation of ettringite, prevents the second hydration of aluminate phase and delays the hydration of C₃S.     

聚羧酸减水剂在水泥水化过程中的微观表现

采用SEM、IR、XRD、pH值和电导率等分析手段研究了聚羧酸减水剂对水泥水化初期的影响,结果表明,聚羧酸减水剂具有减缓水泥的初期水化作用,水泥水化产物的聚合度随水化时间增加而增大,但晶型不改变。在水泥中添加0．3％聚羧酸减水剂,32．5#水泥3d、7d和28d的抗压强度分别提高了50．9％、40．4％、35％。     

Surface Behavior of Aminosulfonate Formaldehyde Condensates and Its Dispersion Effect on Cement Paste

The surface physicochemical properties of aminosulfonate formaldehyde condensates (ASP) and naphthalene sulfonate formaldehyde condensates (FDN) and the dispersion effect on cement paste were investigated. The results showed that these two superplastcizers could hardly reduce the surface tension of aqueous solution, and the surface activity and foam production was rather weak. The adsorption of ASP and FDN on the cement particles followed the Langmuir adsorption equation, characterized as monolayer adsorption. The maximum adsorptive amount of ASP on the cement particles was 3.83 mg/g at 20°C, and the adsorption rate constant was 1.00 s^?1, which were less than those of FDN, respectively. The ζ potential of cement particles containing ASP was larger than that containing FDN, and the loss of ζ potential was much less. Study on the XPS spectrograms presented that, the thickness of adsorption layer of ASP on the cement particles was 7.26 nm, while that of FDN was 1.50 nm. It could be concluded that the electrostatic repulsion effect and steric repulsion effect of ASP were stronger than those of FDN, hence ASP had better dispersion effect and fluidity‐retaining ability on the cement paste. When the dosage of superplasticizer was 0.5 wt% of the cement, the fluidity of cement paste with adding ASP was 270 mm, while that with adding FDN was only 150 mm at a mass ratio of water to cement of 0.28. The residual fluidity of cement paste with adding ASP was 167 mm with 2.5 h elapsed at an initial fluidity of 200 mm, while that with adding FDN was only 101 mm.     

聚羧酸系高效减水剂合成工艺的优化研究

以甲基烯丙基聚氧乙烯醚(HPEG)和丙烯酸(AA)为单体,以过氧化氢-抗坏血酸(H2 O2-Vc)为氧化还原引发体系,以巯基丙酸(MPA)为链转移剂,共聚合成了HPEGAA型聚羧酸减水剂.研究了合成温度、酸醚比及引发剂用量对聚羧酸减水剂分散性能的影响.结果表明,聚羧酸减水剂的最佳合成工艺为:n(AA):n(HPEG)=...     

Adsorbing behavior of polycarboxylate superplasticizer in the presence of the ester group in side chain

The effect of the ester group in side chain on adsorbing behavior and dispersion of polycarboxylate superplasticizer (PC) was studied by comparing the performance of two types of PC. The fluidity of cement paste was tested to discuss the dispersing ability and dispersing retention ability of PC. The total organic carbon analyzer was used to measure the adsorption amount, and the adsorption layer was obtained by x-ray photoelectron spectroscopy. Fourier-transform infrared spectroscopy, nuclear magnetic resonance, and pH value were used to verify the stability of the ester group, and the electrokinetic properties of cement particle were confirmed using the zeta potential measurement. The results show that the ester group in side chain reduces the initial dispersing ability while it increases the dispersing retention ability. The dispersing retention ability depends on the increase of adsorption amount and adsorption layer in 5–60 minutes, and the greater increase leads to the better dispersing retention ability. The ester group can be decomposed to release carboxyl group to enhance the adsorbing ability of PC under the condition of cement hydration, which is the main reason for the greater increase of adsorption amount and adsorption layer and the improvement in dispersing retention ability. It suggests that grafting the ester group is a good way to enhance the dispersing retention ability.     

Effects of poly(ethylene glycol) branch chain linkage mode on polycarboxylate superplasticizer performance

Polycarboxylate superplasticizers (PCs) with ether linkages and ester linkages between the main chains and the poly(ethylene glycol) (PEG) branch chains were synthesized, respectively. The effects of the PCs molecule linkage mode on the performance of concrete paste were investigated using the slump loss test and thermogravimetric analysis and analyzing fluidity, absorption, and setting time. Results showed that the linkage between main chains and PEG branch chains in PCs molecules had an important influence on the performance of cement paste and concrete prepared from them. PCs with ester linkages can endow the cement paste with higher fluidity and higher water‐reduction ratio resulting from the higher absorption amount on the cement particles. This is related with the alternating distribution of the carboxyl groups and branch chains of PEG when different macromonomers are involved in the preparation of PCs. PCs containing ester linkages are more vulnerable than PCs with ether linkages in an alkali environment, leading to quicker slump loss and shorter setting times. In contrast, PCs with ether linkages had excellent fluidity and slump flow stability. A slightly different ettringite hydration product was observed during the early period of the hydration of cement paste that employed these two PCs. Copyright © 2012 John Wiley & Sons, Ltd.