氧化石墨烯对多壁碳纳米管掺配水泥砂浆强度、压敏性能与微观结构的影响

多壁碳纳米管(MWCNTs)对水泥基材料可起到增强增韧的作用。但MWCNTs易在水泥浆体中团聚,目前国内外对如何深化氧化石墨烯(GO)在水泥浆体中分散MWCNTs的报道较为罕见。采用吸光度试验考察了木质素磺酸钠(MN)存在时,GO对MWCNTs在模拟水泥水化孔隙液的饱和氢氧化钙溶液(CH)中分散性能的影响,并研究了GO对MWCNTs掺配砂浆力学性能、电热性能、电阻率及压敏性的影响。吸光度测试表明MN、GO、MWCNTs质量比为3∶1∶9时,MWCNTs分散达到最佳,力学性能测试表明当MWCNTs、GO最佳掺量分别为0.45wt%、0.05wt%时,28天抗折抗压强度比相同MWCNTs掺量的试件分别提高了27.3%、20.9%,电阻率降低了18.2%,电阻变化率提高了72.6%。微观结构测试表明GO能进一步促进MWCNTs在水泥基材料中分散,促进水泥水化进程,密实了水泥石结构,对MWCNT掺配砂浆强度有协同增长作用,提高了压敏性能。本研究采用GO分散MWCNT的方法可扩展到其他碳基纳米增强剂,并为发展自感知智能化水泥基材料提供了一种新的途径。     

电阻率法研究引气剂对水泥浆体化学收缩及氯离子渗透性的影响

研究了引气剂对硅酸盐水泥浆体的电阻率、化学收缩、物理力学性能及氯离子渗透性的影响。结果表明,掺入引气剂使水泥浆体的流动度增大,凝结时间延长,早期水化速率加快,化学收缩增大。水泥浆体的电阻率在凝结前随着引气剂掺量的增加而增大,在硬化后则随着掺量的增加而减小。在28d龄期时,0.04%掺量内的引气剂对硬化浆体的抗压强度影响较小,其强度损失率低于5%,氯离子迁移系数随掺量的增大而减小。随引气剂掺量的变化,水泥浆体的电阻率与化学收缩、抗压强度和氯离子迁移系数均存在很好的定量关系。通过水泥浆体的电阻率发展曲线可以预测其化学收缩、强度与氯离子渗透性的变化规律。     

氧化石墨烯水泥浆体流变性能的定量化研究（英文）

采用流变仪和激光共聚焦显微镜对不同氧化石墨烯(GO)掺量的新拌水泥浆体的流变参数以及浆体微观形态进行了定量化研究,并采用Modified-Bingham(M-B)模型和Herschel-Bulkley(H-B)模型对所测数据进行了拟合处理,提出了GO影响新拌水泥浆体的作用机理。结果表明,GO的掺入可以使新拌浆体中在减水剂作用下分散的水泥颗粒发生再次凝聚,形成重组絮凝结构,且随着GO掺量的增加,重组絮凝结构的数量越多,从而使得浆体流变性发生显著变化。一方面,新拌浆体的塑性粘度、屈服应力以及触变性随GO掺量的提高而显著增加。另一方面,GO的掺入提高了新拌浆体的临界剪切速率,使其在较大剪切速率下的流变行为仍然表现为剪切变稀;降低了浆体的剪切增稠程度,提高了浆体的稳定性。     

氧化石墨烯对水泥净浆流动度及水泥石结构和性能的影响

采用Hummers法及超声破碎分散法制备了氧化石墨烯(GO)纳米相分散液,研究了GO对水泥净浆流动度和水泥石微观结构的影响,用FT-IR、AFM、XRD及SEM对GO及水泥石结构进行了表征。结果表明GO的掺入降低了净浆流动性,每增加0.01%的GO需要增加0.02%的聚羧酸系减水剂(PCs)以保持水泥净浆流动度在3 h内在200 mm以上,GO的掺入能够使水泥石的微观结构发生明显的变化,当GO/PCs掺量为0.01%/0.24%~0.03%/0.28%时,水化龄期7 d的水泥石出现了大量分散均匀的花状微晶体,当GO/PCs掺量为0.05%/0.32%~0.07%/0.36%时,同龄期水泥石中出现大量的片状晶体,在水化龄期延长到28 d时有转化为密实结构的趋势,结果说明GO具有调控水泥水化产物形貌的能力及增强增韧的作用,此研究结果对于提高水泥基材料的力学性能具有重要意义。     

氧化石墨烯复掺石墨烯对水泥砂浆力学性能的提升及机理研究

采用高温还原氧化石墨烯(GO)方法制备石墨烯(G),利用GO对G的助分散效果将G与GO同时掺入砂浆中(即复掺)以改善水泥砂浆力学性能。通过不同含量G与GO混合溶液的吸光度测试,研究了GO对G的分散作用,结果表明当G与GO浓度比(C_G/C_(GO))为4/5时,GO对G的助分散效果最佳。然后保持吸光度测试中C_G/C_(GO),研究了不同G含量对复掺的水泥砂浆抗折抗压强度的影响。研究表明同等掺量下,复掺GO与G更能增强砂浆的力学性能,C_G/C_(GO)在3/5,4/5时提升效果较优,且复掺GO与G对砂浆早期力学性能提升效果更明显;TG测试表明复掺水泥的水化速度快于单掺G水泥。微观测试研究表明GO与G同时掺入水泥,既可以发挥GO对G的助分散效果,又能对水泥起到协同增强作用,促进了水泥的水化,水化产物晶型更加规整。研究采用GO助分散G的方法,既可以发挥GO对G的助分散效果,又能对水泥起到协同增强功效。     

氧化石墨烯对水泥基复合材料微观结构和力学性能的影响（英文）

研究了不同掺量下氧化石墨烯(GO)对水泥石以及胶砂微观结构和力学性能的影响。含16.5%水的水泥浆、0.05%GO及3倍于水泥的沙子共混物作为添加剂制备成砂浆。通过SEM、液氮吸附仪和一系列标准实验分别对水泥石的微观形态、孔隙结构、抗压抗折强度以及水泥净浆的流动度、黏度、凝结时间进行表征;考察不同GO掺量下水泥水化放热的变化情况。结果表明:GO对水泥浆有显著增稠和促凝作用;GO的掺入可以有效降低水泥的水化放热量;GO对水泥石有显著的增强增韧效果,28天龄期时,GO质量分数为0.05%的水泥石,3、7和28 d抗压强度和抗折强度同比对照组分别增加52.4%、46.5%、40.4%和86.1%、68.5%、90.5%,胶砂的抗压强度和抗折强度同比对照组分别增加43.2%、33%、24.4%和69.4%、106.4%、70.5%;GO在水泥硬化过程中对水泥石中晶体产物的产生有促进作用并能规整晶体的排布而形成针状晶体簇,改善水泥石中的孔结构,降低水泥石中微孔的体积,增加水泥石的密实度,对水泥石有显著地增强增韧效果。     

常温下硝酸铵钙对硫铝酸盐水泥的早强作用

研究了常温下硝酸铵钙对硫铝酸盐水泥浆体的流动度、凝结时间、抗压强度、电阻率及浆体内部温度、水化热、水化产物和孔结构的影响,对硝酸铵钙的早强作用机理进行了分析。结果表明,当硝酸铵钙的掺量从0增大到5%时,水泥浆体的初始流动度明显增大,凝结时间显著缩短,6 h,1,3,7和28 d抗压强度均显著提高,电阻率变化速率曲线峰值出现的时间逐渐提前,水泥浆体内部温度逐渐升高,温峰出现时间提前;其掺量在2%以内时,水泥水化放热速率明显加快,1 d累积放热量略有增大,钙矾石的生成速率及生成量均增大,硬化水泥浆体的平均孔径、总孔体积和孔隙率减小。由于硝酸铵钙能够明显加快硫铝酸盐水泥的水化进程,使其早期强度显著提高,因此可用作早强剂。     

氧化石墨烯对水泥基渗透结晶型防水材料抗渗性能的影响

研究了木质素磺酸钠(MN)对氧化石墨烯(GO)在模拟水泥水化孔隙液中的分散能力的影响,并研究了MN分散的GO对水泥基渗透结晶型防水材料(CCCW)对水泥砂浆抗渗性能的影响。通过吸光度试验、Zeta电位及原子力显微镜(AFM)研究表明,当MN与GO的质量比为3∶1时,GO在饱和氢氧化钙溶液中的分散性最佳;砂浆力学强度测试表明,当GO掺量为水泥质量的0.03%时,3天、28天的抗折抗压强度相较于不掺入MN的GO砂浆分别提高了39.13%和39.37%、33.84%和33.48%;砂浆抗渗压力和氯离子扩散系数比标准砂浆试件分别提高了160.0%和下降了50.6%;抗渗性能测试表明,当GO掺量为水泥质量的0.03%时,GO改性CCCW涂层抗渗压力比含CCCW的涂层提高了116.7%;微观测试表明,GO促进了水化反应,并在砂浆基质中发挥了填充作用和模板作用,增强了水化产物的密实度,使得砂浆和CCCW抗渗性能增加了。本文提供了一种GO改性CCCW来提升水泥砂浆的抗渗性能,在涂层防水效果和降低CCCW材料成本等应用价值得到提升。     

橡胶对水泥基材料干燥收缩性能的影响

为了考察橡胶增加水泥基材料干燥收缩量的机制,以橡胶水泥砂浆作为研究对象,采用毛细管张力理论分析了造成水泥砂浆干燥收缩的因素。使用压汞试验研究橡胶/水泥砂浆的孔结构,并进行了弹性模量和干燥收缩试验。研究结果表明,橡胶掺入会降低水泥砂浆的弹性模量,增加其孔隙率和干燥收缩量,且相同掺量条件下,小粒径橡胶的作用效果更明显。基于试验数据,考虑橡胶掺入对砂浆弹性模量的折减系数KE和橡胶掺入对毛细孔(孔径50nm的孔隙)数量的增加系数K_h,拟合了橡胶对水泥砂浆干燥收缩的影响参数δ_(mr)。     

水泥中MgO膨胀剂水化产生的膨胀应力表征

本文研制了一套膨胀应力测试装置,并以此为基础测试了约束条件下MgO膨胀剂(MEA)压实体和掺MgO膨胀剂水泥浆体中水化产生的膨胀应力;采用X射线衍射法定量分析了MgO的含量,并计算MgO的水化程度。结果表明:活性指数为23s和46s的MgO膨胀剂压实体水化22d产生的膨胀应力分别为38.9MPa和62.7MPa;掺水泥浆体的膨胀应力随MEA掺量增大、MEA活性指数提高和MgO水化程度增加而增大,不掺MgO膨胀剂的水泥浆体63d时的收缩应力为1.3MPa,掺12%活性指数为23s和46s的MgO膨胀剂水泥浆体在63d时的膨胀应力分别为1.8MPa和3.0MPa。     

Physico-chemical deformations of solidifying cementitious systems: multiscale modelling

At early stages of hydration and in autogenous conditions (no mass transfer with the outside), solidifying cementitious systems exhibit dimensional variations following two main processes: Le Chatelier contraction (also called chemical shrinkage) and self-desiccation shrinkage causing autogenous shrinkage. Chemical shrinkage results from the difference between the specific volumes of reactants (anhydrous cement and water) and hydration products. Early-age autogenous shrinkage is generally attributed to the development of a negative capillary pressure in the porous network related to the water consumption by the hydration reactions. If restrained, deformations associated to these shrinkages can induce the development of internal stresses high enough to generate cracking of the hardening material. The purpose of this study is to propose a multiscale approach to model the rate of self-desiccation shrinkage of cementitious materials at very early-age, between 0 and 48 h. Within the first hours, Le Chatelier contraction is computed from a formulation suggested in a later work which is based on the chemical equations of hydration and the specific volume of each phase. Then, when the setting of the cement paste takes place, the autogenous shrinkage is calculated according to the evolution of the capillary pressure and the stiffness of the cement paste. The stiffness is calculated by applying a classical homogenization method. Computed results are discussed and analyzed. Good agreements between experiments and simulations are achieved and a sensitivity study is performed to assess the influence of the cement fineness and the aggregate volume fraction on early-age autogenous strain.     

Influence of entrained air voids on pore water pressure and volume change of concrete before and during setting

The paper discusses the role of entrained air voids on the transformation from liquid to solid of cement based materials (paste, mortar, concrete). The discussion is based on pore water pressure and volume change measurements. Air pores seem to contribute to increased rate of autogenous shrinkage in the time before the “knee-point” (i.e. in the few hours before autogenous shrinkage rate becomes significantly lower than the chemical shrinkage rate), and an earlier appearance of the knee-point. Through setting and shortly after, air pores alter the pore water pressure evolution in that they act as a buffer, and thereby reduce the pressure decrease and the subsequent autogenous shrinkage, as well as friction against panels in slipforming. The influence on plastic shrinkage does not seem to be significant.     

Characterizing cement paste containing SRA modified nanoSiO2 and evaluating its strength development and shrinkage behavior

In this study, shrinkage reducing admixture (SRA) was grafted on NanoSiO₂ (NS) surfaces to synthesize novel core-shell (NS@SRA) particles and improve dispersion of NS in cement paste. The synthesized NS@SRA was characterized by Fourier transform infrared spectroscopy, dynamic light scattering, and thermogravimetric analysis. A series of tests were performed to investigate the effects of NS@SRA addition on the compressive strength and shrinkage of cement paste. It is found that NS@SRA increases the strength of cement paste, especially at later ages. Unlike conventional NS, which significantly increases autogenous shrinkage of cement paste, addition of NS@SRA does not appreciably affect autogenous shrinkage of the paste at early ages. Based on dispersion and zeta potential measurements of NS and NS@SRA particles in synthetic pore solution, we propose that hydration products around NS@SRA may result in gradual separation of SRA from the core. The released SRA may reduce shrinkage and mitigate cracking of cement composites at later ages.     

A Stochastic Multi-Scale Model for Prediction of the Autogenous Shrinkage Deformations of Early-age Concrete

Autogenous shrinkage is defined as the bulk deformation of a closed, isothermal, cement-based material system, which is not subjected to external forces. It is associated with the hydration process of the cement paste. From the viewpoint of engineering practice, autogenous shrinkage deformations result in an increase of tensile stresses, which may lead to cracking of early-age concrete. Since concrete is a multi-phase composite with different material compositions and microscopic configurations at different scales, autogenous shrinkage does not only depend on the hydration of the cement paste, but also on the mechanical properties of the constituents and of their distribution. In this paper, a stochastic multi-scale model for early-age concrete is presented, which focuses on the prediction of autogenous shrinkage deformations. In this model, concrete is divided into three different levels according to the requirement of separation of scales. These levels are the cement paste, the mortar, and the concrete. A specific representative volume element (RVE) for each scale is described by introducing stochastic parameters. Different scales are linked by means of the asymptotic expansion theory. A set of autogenous shrinkage experiments on the cement paste, the mortar, and the concrete is conducted and used for validation of the developed multi-scale model. Furthermore, the influence of the type and the volume fraction of the aggregate on autogenous shrinkage is studied. Besides, a combined optimum of fine and coarse aggregates is determined. The analysis results show that the proposed model can effectively estimate the autogenous shrinkage deformations of concrete at early-age by taking the influence of the material composition and configuration into consideration.     

Strain and thermal expansion coefficients of various cement pastes during hydration at early ages

Cement pastes undergo elevated temperature histories due to hydration heat liberation at early ages. Thermal expansion coefficients of cement paste and concrete change with age, showing a decrease after mixing, a subsequent minimum and then a gradual increase. These changes contribute to thermal strain. In this study, effects of water–cement ratio and cement type on volume changes in early-age cement pastes were experimentally examined using a newly developed apparatus capable of simultaneously determining both thermal expansion coefficient and total strain of cement pastes. The dependence of the thermal expansion coefficient on hydration was affected by water–cement ratio, cement type, elevated temperature history and particularly by the free water content of the cement pastes, while the relationship between thermal expansion coefficient and free water content varied with water–cement ratio. A notable increase in thermal expansion coefficient at early ages was observed when water–cement ratio was low and alite content in cement was high. At a water–cement ratio of 0.30, low-heat Portland cement paste resulted in a small total strain while moderate-heat and ordinary Portland cement pastes showed larger strains. Because no particular difference was observed in the thermal strains, shrinkage in the low-heat Portland cement paste was attributed to autogenous strain. At a water–cement ratio of 0.40, self-desiccation had a significant influence upon autogenous shrinkage and dependence of thermal expansion coefficient on hydration, and the effect of the mineral composition of cements was notable. However, for cement pastes with a water cement ratio of 0.55, no significant effects of self-desiccation were observed, probably because considerable excess water was present.     

Early-age autogenous cracking of cementitious matrices: physico-chemical analysis and micro/macro investigations

High-performance cement-based materials, characterized by low water-to-cement (W/C) ratio and high cement content, are sensitive to early-age cracking because their autogenous shrinkage rate and magnitude are particularly high during this period. This article firstly presents experimental tools especially designed for the measurement of free and restrained autogenous shrinkage at early-age. Then, the results of a multi-parameter experimental study conducted on three different types of binder are analyzed. The physico-chemical deformations of cement pastes and mortars were measured from the very early-age up to several days in saturated and autogenous conditions to investigate the effects of binder, water-to-binder ratio, presence of aggregates and temperature on the driving-mechanisms leading to early-age autogenous cracking. Complementary tests such as hydration rate measurement and microscopic observations were also performed. Among the three binders used, the blast furnace slag cement shows higher chemical strain, for a given quantity of chemically-bound water, and higher early-age autogenous shrinkage. The presence of aggregates generates a local restraining effect of cement paste deformations, leading to the formation of microcracks in the surrounding cement paste. Ring test results reveal that the first through crack of cement pastes systematically appears for maximal internal stress values lower than the material tensile strength, estimated with three-point flexural tests. This phenomenon may be due to diffuse damage of the cementitious matrix, whose deformations are partially restrained.     

Changes in pore structure and mercury contact angle of hardened cement paste depending on relative humidity

Hardened cement paste (hcp) is a porous heterogeneous material consisting of dispersed particles like Calcium Silicate Hydrates (C-S-H). These are of micron to nanometer size forming pores on a nanometer scale. Thus, hcp can be regarded as a colloidal system. Surface forces play a dominant role. Adsorbed water molecules interact with the surface. Capillary condensation occurs in the pores below bulk conditions acting in form of capillary and disjoning forces. All these forces are able to alter the structure and properties of the hardened cement paste depending on the moisture content. Pore size distributions were measured with mercury intrusion porosimetry on hcp specimens, which had been prestored over the entire range of relative humidity. Swelling and shrinkage of hcp tubes were also determined. The pore size distribution is corrected for each humidity step regarding the particular porosity, contact angle and volume change. The pore size distribution as a function of relative humidity is nonlinear and characterized by an extreme value in the medium range of humidity.     

Effect of fly ash fineness on compressive strength and pore size of blended cement paste

This paper presents an experimental investigation on the effect of fly ash fineness on compressive strength, porosity, and pore size distribution of hardened cement pastes. Class F fly ash with two fineness, an original fly ash and a classified fly ash, with median particle size of 19.1 and 6.4 μm respectively were used to partially replace portland cement at 0%, 20%, and 40% by weight. The water to binder ratio (w/b) of 0.35 was used for all the blended cement paste mixes.Test results indicated that the blended cement paste with classified fly ash produced paste with higher compressive strength than that with original fly ash. The porosity and pore size of blended cement paste was significantly affected by the replacement of fly ash and its fineness. The replacement of portland cement by original fly ash increased the porosity but decreased the average pore size of the paste. The measured gel porosity (5.7–10 nm) increased with an increase in the fly ash content. The incorporation of classified fly ash decreased the porosity and average pore size of the paste as compared to that with ordinary fly ash. The total porosity and capillary pores decreased while the gel pore increased as a result of the addition of finer fly ash at all replacement levels.     

氧化石墨烯增强水泥复合材料的断裂性能

将氧化石墨烯(GO)加入水泥砂浆中,以提高其抗裂性和韧性。通过三点弯曲梁法测试了GO增强水泥砂浆试件的断裂性能,采用双K断裂模型分析了GO掺量对改性水泥砂浆断裂参数的影响。结果表明:GO提高了水泥砂浆试件的起裂韧度,当GO掺量（与胶凝材料质量比）为0.01%~0.07%时,较对照组分别提高了13.4%、25.4%、24.6%和16.7%,但对失稳韧度的影响有限,不同GO掺量水泥砂浆的断裂能较对照组提高了10.7%~33.3%。结合微观试验发现,GO主要通过影响水泥水化过程,优化孔结构,促进高密度水化产物生成,提高水化产物间的粘结力,进而抑制微裂缝生成和发展。