氧化石墨烯/水泥复合净浆的化学收缩特性及预测模型

为了揭示氧化石墨烯/水泥复合净浆(GO/C)的化学收缩特性,采用体积法对不同水灰比(0.3、0.4、0.5)和不同氧化石墨烯(GO)质量分数(0wt%、0.01wt%、0.02wt%、0.03wt%、0.04wt%、0.05wt%)的水泥复合净浆试件化学收缩进行了测定。试验结果显示:随着水灰比的增加,GO/C化学收缩显著增大。同水灰比条件下掺有氧化石墨烯的GO/C试件前期化学收缩较普通水泥净浆有所下降,当GO质量分数为0.04wt%时,收缩值达到最小;在后期水化中,GO/C试件的化学收缩增长速度明显快于普通水泥净浆。分析表明,GO对水泥净浆孔结构的调控作用和对水化产物氢氧化钙晶体的键合行为是其影响水泥净浆化学收缩性能的主要原因。同时,通过收缩模型与试验值对比发现,现有的普通水泥化学收缩模型无法精准预测GO/C的化学收缩情况,因此,为考虑GO的影响,试验在吴浪模型的基础上,引入K(ξ,t)函数作为影响参数,并通过曲线拟合得到其具体表达式,从而建立起适用于GO/C化学收缩的预测模型。     

粉煤灰、石灰石粉复掺对水泥净浆工作性能的影响

通过检测水泥净浆流动度和Marsh时间,研究了不同掺量粉煤灰与石灰石粉对水泥浆体的工作性能的影响。结果表明,粉煤灰单掺掺量为20%的水泥浆体工作性能最优,单掺石灰石粉的水泥浆体随着掺量增加流动度呈线性增长;复掺掺量分别为20%、30%,粉煤灰和石灰石粉等量时,水泥浆体工作性能最好;通过对水泥、粉煤灰和石灰石粉的粒径分析,从微观角度分析了不同级配的水泥浆体的工作性能。     

石墨烯在水泥净浆中的分散特性

为解决石墨烯(G)在水泥浆中均匀分散及其功能化水泥基材料时掺量过高的难题,选择一种兼顾高导电性与水溶性的石墨烯(G-SD)作为导电填料,研究了聚羧酸减水剂(PCE)存在时,木质素磺酸钠(MN)对G-SD在模拟水泥水化孔隙液的饱和氢氧化钙溶液(CH)中分散能力的影响及其对水泥净浆的导电性能、电热性能、融雪化冰和热电性能的影响。吸光度测试表明,当MN与G-SD质量比为3∶1时,G-SD的分散性最佳。电学性能测试发现,石墨烯水泥基材料的渗滤阀值为0.4%,阀值下试件的电热性能良好,在外加30 V电压下通电20 min,试件温度可达320℃,40 min内可将4 cm厚冰层完全融化,具有优异的融雪化冰潜力。热电性能研究表明,当G-SD掺量为0.1% 时,试件的Seebeck系数为154.4 μV/K。以上研究表明,G-SD能在极低掺量下赋予水泥基材料优异的电、热及热电等功能特性。     

氧化石墨烯增强水泥基复合材料的力学性能及微观结构

本文采用改进的Hummers法制备了氧化石墨烯（Graphene oxide,GO）悬浮液,通过FTIR、XRD和AFM等测试技术对GO晶体结构和尺寸形态进行了表征,考察了GO掺量和水灰比的变化对GO增强水泥基复合材料力学性能和微观结构的影响。结果表明：GO增强水泥基复合材料抗折抗压强度随GO掺量增加而先提高后降低,且对于抗折强度增强效果远超过抗压强度,当GO掺量为0.03%时,抗折强度达到最大值13.72 MPa;高水灰比条件下掺入GO对水泥胶砂强度的提高更显著;通过SEM对GO增强水泥基复合材料微观结构进行表征,发现GO能够优化水泥水化产物的微观结构形态,细化晶体尺寸,形成更加致密均匀的网络结构,从而改善水泥基复合材料的宏观性能。     

氧化石墨烯对水泥水化晶体形貌的调控作用及对力学性能的影响

用Hummers法制备了氧化石墨烯(GO)并用超声波将其分散制备了纳米片层分散液,用XRD和AFM表征了分散的效果。研究了不同含氧量GO对水泥水化晶体微观形貌及胶砂耐折强度和抗压强度的影响,结果表明含氧量为18.65%和25.53%的GO可使水泥水化产物成为花朵状微晶体,而且形状统一、分布均匀,具有显著的增韧增强效果。研究结果也说明了GO能够调控水泥水化晶体产物的形状和尺寸,GO对于水泥水化反应产物具有促进作用和模板效应。研究结果对于提高混凝土建筑的抗裂缝和耐久性具有积极的意义。     

氧化石墨烯调控水泥基材料形成大规模规整结构及其性能表征

将制备的GO与减水剂和拌合水超声处理后用于制备水泥基复合材料,研究结果表明,GO纳米片层在水泥基体中达到了均匀分散,水泥水化产物成为了规整形状的多面体状水化晶体,通过其交织交联形成了大规模规整致密的微观结构。当GO掺量为0.03%时,尺寸为30~190nm GO的水泥基复合材料28d时的抗压强度和抗折强度比对照样品分别提高了78.8%和112.7%,尺寸为110~410nm GO的水泥基复合材料的抗压强度和抗折强度分别提高了72.3%和93.9%,水泥基复合材料的耐久性显著提高。同时提出了水泥基复合材料微观结构形成机理。     

氧化石墨烯水泥基复合材料的性能及研究进展

水泥基材料在建筑领域应用广泛,但其存在抗弯强度低、抗裂性和韧性差等缺点,因此改善水泥基材料性能一直是建筑材料领域研究的热点之一.氧化石墨烯(GO)是在石墨烯基面和边缘修饰了含氧官能团的一种二维衍生石墨烯材料,具有蜂窝状的结构形貌,亲水性、分散性和反应活性好.将GO加入水泥基材料中,可促进花状形貌晶体的形成,并加速水化进程的成核速度,使其形成致密的交联结构,进而细化水泥浆体的空隙,有效降低孔隙率,从而增强水泥基材料的力学性能,但流动性等有所降低.因此研究人员主要从微观作用机理、静态力学性能及耐久性等方面开展了深入研究,并取得了丰硕的成果.GO自身较大比表面积的结构性质致使水泥基复合材料流变性差,利用硅灰(SF)和氧化石墨烯包覆硅灰(GOSF)等外加剂对GO进行改性,从而提高GO水泥浆体的流动性.基于微观结构作用机理,对比不同GO掺量、试件尺寸、水灰比下的抗压强度和抗弯强度的增长率,分析GO水泥基复合材料的力学性能的增强机理.GO对水泥基材料抗压、抗拉、抗弯强度增长率存在较大差异,其中抗弯强度提高幅度最大.GO对硅酸盐水泥力学性能的提高程度较磷酸镁钾水泥更为显著.对于动态力学性能,不同应变率下裂纹扩展路径存在差异,在高应变率下GO的增强效应更为显著.水泥基材料工作环境中各类离子化合物及酸碱度对其基体有消极的影响,GO对其耐久性有明显的提高作用.本文对近年来GO水泥基复合材料的研究状况进行梳理,分析其微观结构作用机理、流动性、力学性能及耐久性等,阐述了目前国内外的研究状况及存在的问题,并展望了GO水泥基复合材料未来的发展趋势.     

氧化石墨烯及其分散方法对水泥基材料微观结构和力学性能的影响研究进展

氧化石墨烯(GO)因其出色的性能在改善水泥基材料微观结构、力学性能上均有很好的应用前景。然而,GO的增强效果很大程度上取决于其在水泥基体中的分散性。总结了近年来GO在水泥基材料中的研究成果,重点综述了GO的分散方式、分散机理以及相应的力学性能改善机理;对比了不同GO分散方式的优缺点,分析了GO分散前后对水泥基材料微观结构和力学性能的影响;提出了目前研究存在的问题,并对未来研究趋势进行展望;旨在为后续GO在水泥基材料中的稳定应用提供参考,以促进制备高效功能化的GO水泥基复合增强材料。     

基于碟片法的溶蚀作用下水泥净浆微观结构演变研究

溶蚀作用下水泥基材料的微结构变化导致混凝土材料服役性能退化。为了克服传统试验因试样厚度影响而产生的脱钙不均匀现象,以NH4NO3溶液对约1mm的碟片状水泥净浆试件进行加速脱钙,通过控制质量损失来控制溶蚀程度。然后把质量损失作为衡量溶蚀程度的参数,结合压汞法(MIP)、环境扫描电子显微镜(ESEM)及能谱分析(EDS),研究不同溶蚀程度下水泥净浆的微观形貌、化学组成和孔隙结构变化规律。试验结果表明:试件钙硅比(Ca/Si)与质量损失大致呈两段线性关系。在第一阶段,水泥浆体试件Ca/Si逐渐降低,氢氧化钙(CH)分解,质量损失10%试件中CH已被严重溶蚀;水化硅酸钙(C-S-H)凝胶的Ca/Si随着溶蚀程度增加而降低,证明C-S-H凝胶第一阶段已开始分解。在第二阶段,主要表现为C-S-H凝胶继续分解。试验还发现,溶蚀后水泥净浆试件内部孔径小于50nm的孔略微增加,50~200nm的孔含量有部分减少;孔径大于200nm的多害孔大量增加。     

Numerical homogenization of hardened cement paste

Based upon a three-dimensional computer-tomography of hardened cement paste, a finite-element mesh at micrometer length scale is introduced. Effective material properties are obtained through numerical homogenization techniques using representative volume elements. Statistical tests, two- and three-dimensional computations and a comparison with experimental data are shown. For the hydration products of hardened cement paste a visco-plastic constitutive equation of Perzyna type including isotropic damage is introduced. The inelastic material parameters are identified solving an optimization problem through a combination of a stochastic genetic algorithm and the deterministic Levenberg-Marquardt method. The time-consuming evaluations of the corresponding objective function are distributed within a network environment automatically.     

Pore structure of hardened cement paste and mortar

The paper describes an experimental investigation into the pore structure of hardened cement paste and mortar. The pore structure was studied using mercury porosimeter. Ordinary portland cement and natural river sand were used. Pore structure determination was carried out for both the cement paste and mortar mixes over four hydration periods and five water-cement ratios. The threshold radius which was found to be prominent in the hardened cement paste, flattens out as the fine aggregate content increased.     

Improvement of mechanical properties by incorporating graphene oxide into cement mortar

ABSTRACT

As a two-dimensional nanomaterial, graphene oxide has attracted much attention for its use in reinforcing cementitious materials. However, the dispersion of graphene oxide in cementitious materials has been found unsatisfactory due to crosslinking of divalent calcium ions. In this study, we propose a modified mixing procedure to improve graphene oxide dispersion in cement mortar by utilizing silica sand to mechanically separate graphene oxide nanosheets. Apart from the improved graphene oxide dispersion, adhesion between sand and cement matrix is also believed to be enhanced due to the improved roughness of the sand surface. According to our mechanical properties study, with the introduction of 0.02% by weight graphene oxide in cement mortar, compressive strength was significantly improved by more than 25% and tensile splitting and flexural strength were improved by around 15%. In a microstructural investigation, the interfacial transition zone in cement mortar was found to be denser due to the addition of graphene oxide. Moreover, graphene oxide incorporated cement mortar also showed pore structure refinement and porosity reduction. Therefore, improvement in mechanical properties may result from an improved interfacial transition zone and a more refined pore structure with the introduction of a small quantity of well-dispersed graphene oxide nanosheets.     

氧化石墨烯纳米片层对水泥基复合材料的增韧效果及作用机制

通过氧化和超声波分散制备了氧化石墨烯（GO）纳米片层分散体系,研究了GO纳米片层对水泥基复合材料的增韧效果及作用机制。用EDS、FTIR、XRD、SEM和AFM对GO纳米片层的结构进行了表征。研究结果表明：所得GO含氧量为32.3wt%,GO纳米片层的厚度为6 nm左右,在GO片层表面含有羟基、羧基和磺酸基等活性基团。水泥基复合材料的SEM形貌及力学性能测定结果表明：当GO掺量为0.03wt%时,GO能够使水泥水化产物形成花朵状晶体,并使水泥基复合材料的拉伸强度、抗折强度和压缩强度比对照样品分别提高了65.5%、60.7%和38.9%。提出了GO纳米片层对水泥水化产物的模板调控机制,揭示了花状晶体的形成过程。     

Simulation of water permeability and water vapor diffusion through hardened cement paste

The transport properties of cement-based materials significantly affect their durability. This results from the fact that most of the damaging reagents are transported, often solved in water, through the open pore space into the microstructure. This paper focuses on simulating water permeation (movement under a gradient of pressure) and water vapor diffusion (movement under a gradient of concentration) through hardened cement paste (hcp). The main goal is to derive the water permeability and the water vapor diffusion coefficient directly from the morphology of the 3D microstructure. For this purpose microtomographic images of a hcp made of ordinary Portland cement are used to represent the microstructure and especially the pore space through which the moisture transport will occur. With the use of a skeletonization algorithm, also known as “thinning algorithm”, the skeleton or centerline of the pore space is extracted. This skeleton is in a second step converted into a transportation network of cylindrical tubes. Bernoulli's law is applied to every tube for simulating water permeation. The permeability coefficient is then calculated by using Darcy's law. In the case of water vapor diffusion the diffusion coefficient is calculated using Fick's law. An erratum to this article is available at .     

硬化水泥浆体弹性模量细观力学模型

应用复合材料力学理论和有孔介质力学(Poromechanics)理论建立了一个描述硬化硅酸盐水泥浆体弹性模量的细观力学模型, 将硬化水泥浆体从不同尺度上划分为4个层次, 即C-S-H凝胶、 水泥水化产物、 水泥浆体骨架和水泥浆体, 分别应用不同的细观力学模型予以描述: 将C-S-H视为饱和的有孔介质; 应用Mori-Tanaka模型描述水泥水化产物的弹性性质; 应用三相模型(Three-phase model)模拟水泥浆体骨架的有效弹性模量; 最后, 再次应用Mori-Tanaka模型和有孔介质理论, 计算水泥浆体的排水和不排水弹性模量(Drained and undrained elastic moduli)。该模型所需要的参数为水泥浆体各个组成部分的自身弹性性质, 使用方便。通过预测文献中的实测结果, 证明了该模型的有效性。      

Characterization of the mechanical damage of a chemically degraded cement paste

Cement-based materials as concrete interact with their environment. In the presence of aqueous mediums, dissolutions and precipitations of solid species composing the cement paste induce a chemical damage, which may affect the structure integrity. This paper presents a mechanical characterization of the Young modulus evolution of chemically damaged cement paste, based on a microstructural approach coupled to a reactive-transport model. The method has been successfully applied to cement pastes leached by pure water. It is concluded that the capillary porosity and its spatial distribution within the material are the parameters, which mainly rule the stiffness evolution.     

Comparative investigation on nanomechanical properties of hardened cement paste

Three types of nanomechanical methods including static nanoindentation, modulus mapping and peak-force quantitative nanomechanical mapping (QNM) were applied to investigate the quantitative nanomechanical properties of the same indent location in hardened cement paste. Compared to the nanoindentation, modulus mapping and peak-force QNM allow for evaluating local mechanical properties of a smaller area with higher resolution. Beside, the ranges of elastic modulus distribution measured by modulus mapping and peak-force QNM are relatively greater than that obtained from nanoindentation, which may be due to a result of the shaper probe and local confinement effect between multiple phases. Moreover, the average value of elastic modulus obtained using peak-force QNM were consistent with those obtained by modulus mapping, while the different in modulus probability distribution could be related to the different nanomechancial theories and contact forces. The probability distributions of elastic modulus measured using nanomechanical methods to provide a basis for the different types of phases existing in cement paste. Based on the observation with high spatial resolution, cement paste can be likely found as nanocalse granular material, in which different submicron scale or basic nanoscale grain units pack together. It indicates that the peak-force QNM can effectively provide an effective insight into the nanostructure characteristic and corresponding nanomechanical properties of cement paste.     

Micromachining of hardened Portland cement pastes using femtosecond laser pulses

Femtosecond laser pulses (30 fs in length) of various energies were utilised for production of single and multiple overlapping ablation sites on flat polished surfaces of hardened Portland cement pastes. In order to assess the sizes of the ablation sites and possible subsurface laser-induced damage, the ablation sites were investigated using environmental scanning electron microscopy (ESEM) – both from normal top–down view and in cross-sections. Furthermore, approximately 10-μm wide notches were produced using femtosecond pulses on cylindrical microspecimens (150 μm in diameter) of hardened Portland cement pastes. In addition to electron microscopy observations, several microspecimens were investigated using synchrotron-based X-ray computed microtomography (SRμCT). The results suggest that production of “damage-free” samples for micromechanical testing of hardened Portland cements pastes is possible.

---

Résumé Des impulsions laser (de durée 30 fs) et d’énergie variable ont été utilisées pour produire une ablation ponctuelle ou linéique à la surface d’un ciment durci de type Portland et préalablement polie. Pour déterminer la taille des impacts et d’éventuels dommages causés par le laser sous la surface, les points d’impact ont été visualisés à l’aide de la technique de l’ESEM (microscope électronique à balayage environnemental). De plus, des piliers de 10 micromètres de diamètre environ ont été réalisés par ablation femtoseconde sur des échantillons cylindriques de 150 microns de diamètre. Pour compléter les observations faites au microscope électronique, certains échantillons ont été observés grace à la technique SRμCT (synchrotron-based X-ray computed microtomography). Les résultats montrent que la production d’échantillons non-endommagés de ciment de type Portland pour des tests micro-mécaniques ultérieurs est possible.

     

氧化锌对纳米羟基磷灰石/壳聚糖复合骨水泥理化性能的影响

质量比为70∶30的n-HA/CS复合材料与适量ZnO粉末的共混物为固相,选用合适的固化液,按照适当的固/液比例进行调和,制备出一种在空气、生理盐水及血液或体液中均可快速固化的新型n-HA/CS复合骨水泥,考查了ZnO含量对该骨水泥理化性能的影响.结果表明:当ZnO与复合材料质量比为1∶8、固化液与固相粉末比例(L/P)为1.2ml/g时,所制备的复合骨水泥抗压强度和固化时间均较佳,能够满足临床操作的需要.ZnO/复合材料质量比分别为1∶8和1∶5的骨水泥在生理盐水中的pH值随浸泡时间的延长而逐渐升高,前者在第20d时pH值维持在7.28左右,而后者在第20d时的pH值接近7.40,均与人体的pH环境相近.当ZnO/复合材料质量比为1∶8时,骨水泥对水的接触角最小,表明其具有良好的润湿性能.ZnO含量越高,骨水泥的吸水率越低,这对于保持骨水泥植入体内后的体积稳定性具有重要价值.SEM观察发现,固化后的骨水泥中含有大量微孔,有利于营养物质的传递及代谢废物的排泄,并利于新生骨组织的长入及爬行替代.