硬化水泥净浆基于纳米压痕的相态识别与水化程度计算

采用纳米原位压痕手段测量硬化水泥净浆中单一相态的代表性微观力学性能,并采用纳米点阵压痕研究各相态的含量。研究对象囊括水灰比为0.3、0.4、0.5的纯水泥净浆和水灰比为0.3情况下含50%、70%矿渣掺量复合体系,共5种配比,以表征它们的相态分布和微观力学性质的异同点。掺矿渣的试件中含有明显多的复合相,因此提出三相模型测算复合相中未水化物的体积分数。此外,提出基于纳米压痕技术计算纯水泥和掺矿渣水泥试件水化程度的方法,结果吻合于热重分析的结果,其中纯水泥净浆中复合相较少,计算得到的水化程度优于对掺矿渣水泥试件的计算。     

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。     

基于土体isotache模型的硬化水泥净浆微观徐变预测

水泥基材料是一种应变率敏感性材料,充分掌握水泥基材料的应变率效应对其力学性能和变形的影响可保障混凝土结构的安全设计。采用连续刚度测试（CSM）研究不同应变率下硬化水泥净浆微观徐变特征,试样的水灰比为0.3、0.4和0.5,CSM的最大压入深度为30 μm,应变率分别为0.01 s^-1、0.05 s^-1、0.1 s^-1和0.5 s^-1,并讨论土体的isotache模型表征硬化水泥净浆微观徐变行为的适用性。结果表明,在0.01~0.5 s^-1应变率范围内,微观尺度上的硬化水泥净浆存在唯一的h_vp-P-ε关系,与土体isotache模型的ε_vp-σ-ε关系类似,该关系可由归一化后的h_vp-P/（P_N/P_N0.05）曲线和P_N/P_N0.05-ε曲线来表征。采用h_vp-P/（P_N/P_N0.05）曲线和P_N/P_N0.05-ε曲线可预测不同应变率下硬化水泥净浆加载阶段的h_vp-P曲线,预测结果与实测结果基本吻合,表明可以采用土体的isotache模型来预测硬化水泥净浆微观尺度上的徐变行为。     

水泥净浆搅拌机间隙过大的调修

水泥净浆搅拌机是制水泥标准稠度净浆的专用设备,本文先对其工作原理进行简单介绍,并分析其间隙过大故障产生的原因,最后提出如何进行调修。     

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。     

从纳米水化硅酸钙到水泥净浆弹性性能多尺度递推模型

混凝土具有多尺度结构特征,其力学性能受到不同水化产物组分及微观结构的影响。基于分子动力学方法、化学计量法和均质化方法,建立了从纳米尺度水化硅酸钙（C-S-H）到水泥净浆弹性性能多尺度递推模型,其计算结果与实验数据吻合较好。基于该模型的计算结果可得：C-S-H凝胶中44%的孔隙率致使其体积模量、剪切模量和杨氏模量分别降低了约66%、53%和55%。当水灰比从0.3变化至0.5时,水泥净浆的体积模量、剪切模量和杨氏模量分别降低了约39%、30%和32%;LD C-S-H和毛细孔的体积分数分别增大了13%和20%。水化产物中C-S-H的体积分数越大,或水泥熟料中硅酸三钙的质量分数越大,水泥净浆的弹性参数越大。该模型为水泥基材料微观调控提供了指导。     

水泥净浆搅拌机转速示值误差测量值的不确定度评定

本文对水泥净浆搅拌机叶片转速示值误差测量值的不确定度进行了分析计算,给出测量值的扩展不确定度。     

水泥净浆搅拌机叶片转速示值误差测量结果的不确定度评定

本文对水泥净浆搅拌机叶片转速示值误差测量结果的不确定度进行了分析计算,主要分析测量过程中存在的不确定度来源,找出影响测量结果的主要因素,最终给出测量结果的不确定度评定报告。     

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。     

Investigation of strength and hydration characteristics in nano-silica incorporated cement paste

A hydration model for Portland cement pastes modified with nano-silica in partial substitution is formulated based on the nucleation growth process from microstructural investigations over time. The model is calibrated against thermogravimetry, X-ray diffraction and calorimetry data for four different substitution rates from 0 to 12 wt% and is validated by backscattered electron microscopy. Finite element based compressive strength predictions using representative volume element analysis of the nano modified cement pastes agreed with the experimental values. The model predictions indicate that a rate of 8 wt% is the optimum replacement level of cement by nano-silica leading to a high density matrix promoting a maximum mechanical strength.     

铅离子对复合磷酸盐磷酸镁水泥水化硬化特性的影响

研究了铅离子对复合磷酸盐磷酸镁水泥水化硬化特性的影响及其在复合磷酸盐磷酸镁水泥中的稳定性。实验结果表明,复合磷酸盐磷酸镁水泥抗压强度随着铅离子掺量的增加而降低,其中硝酸铅掺量达到10%时,复合磷酸盐磷酸镁水泥的各个龄期的抗压强度发生明显下降。铅离子对复合磷酸盐磷酸镁水泥凝结时间没有明显影响。在复合磷酸盐磷酸镁水泥水化过程中,铅离子对水泥体系的pH值影响不大,但能够造成水泥水化放热峰出现的时间延迟,水化放热的总量减少并影响主要水化产物的结晶程度。在复合磷酸盐磷酸镁水泥水化反应后期,当硝酸铅掺量达到10%以上时,在水化产物中出现了较为明显的Pb2P2O7的衍射峰。复合磷酸盐磷酸镁水泥固化铅离子的浸出毒性试验结果(43μg/L)远低于国家标准要求(5mg/L)。     

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.     

Properties of 3D-printed fiber-reinforced Portland cement paste

First insights into a 3D-printed composite of Portland cement paste and reinforcing short fibers (carbon, glass and basalt fibers, 3–6 mm) are presented, resulting in novel materials that exhibit high flexural (up to 30 MPa) and compressive strength (up to 80 MPa). Alignment of the fibers, caused by the 3D-printing process is observed, opening up the possibility to use the print path direction as a means to control fiber orientation within the printed structures. Apart from completely dense cementitious bodies, hierarchically structured bodies, displaying precisely adjusted macroporosity, are presented, the latter exhibiting a unique combination of strength and materials efficiency.     

超长侧链型聚羧酸梳形共聚物对水泥早期水化的影响

选用了一组超长侧链型聚羧酸梳形共聚物作为水泥体系的分散剂,通过水化热测定、强度试验和扫描电镜等表征手段,研究了超长侧链型聚羧酸梳形共聚物分散剂对水泥早期水化的影响.研究发现,超长侧链型聚羧酸梳形共聚物比普通聚羧酸梳形共聚物具有加速水泥水化、提高水泥基材料强度的作用.扫描电镜得到的形貌结果发现,超长侧链型聚羧酸梳形共聚物的掺入改变了水化产物的形貌,并且侧链越长,呈絮状的C-S-H凝胶和呈针状的钙矾石晶体明显增加.这说明超长侧链型聚羧酸加速了C-S-H凝胶和钙矾石晶体的形成,促进了水泥混凝土体系早期强度的形成.     

甲酸钙对硫铝酸盐水泥早期水化过程的影响

利用维卡仪、水化放热速率、XRD、TG-DSC和SEM等测试手段,研究了甲酸钙(Ca(HCOO)2)对硫铝酸盐水泥凝结时间、水化历程和水化产物及微观形貌的影响。结果表明,Ca(HCOO)2可明显促进硫铝酸盐水泥的凝结,并缩短初凝和终凝时间间隔;显著缩短了硫铝酸盐水泥的水化诱导期,且使水化加速期提前,使第一水化热峰值提高32%,但对水化稳定期的水化放热速率无明显影响;Ca(HCOO)2可以提高硫铝酸盐水泥水化环境的碱度,在早期提高了水化产物钙矾石(AFt)的结晶度,水化早期生成的水化产物结构致密,但并不改变水化稳定期的水化产物和微观形貌。     

The effect of synthesis conditions on the efficiency of C-S-H seeds to accelerate cement hydration

C-S-H seeding is a promising approach to accelerate cement hydration in a very effective way. Until now little is known about the way the C-S-H seeds work and how they affect the properties of the hydrated cement paste. To be able to analyse this in detail it is necessary to have a preparation method for the C-S-H seeds, which is reproducible and able to prepare seeds with defined properties. The present work describes two methods for the synthesis of C-S-H seeds, a mechanochemical approach and a sol-gel synthesis. A factorial design of experiments setup was used to find those parameters, which affect the efficiency of the C-S-H seeds to accelerate cement hydration and to adjust these parameters in order to achieve the optimized seeds, which are very effective accelerators. Heat flow calorimetry shows that the dormant period of cement hydration can be eliminated by the use of the optimized C-S-H seeds and compressive strength tests show a multiplication of early compressive strength even at very low concentrations of seeds, indicating that an optimization of the synthesis by factorial design of experiments is a promising way for further studies on the mode of action of C-S-H seeds.     

Near-infrared spectroscopy investigation on the hydration degree of a cement paste

Near-infrared spectroscopy is a fast and easy-to-perform technique characterized by high sensitivity regarding water containing systems and for this reason it is a suitable tool for investigating structural modifications of hydrating cementing materials, even if the lack of knowledge in this field makes the interpretation of NIR vibrational bands very difficult. In this paper, the NIR spectrum of a hydrated ordinary Portland cement is extensively investigated and an interpretation of the different bands is proposed on the basis of both experimental evidence and reference to literature. The obtained results were applied to the investigation of cement hydration lasting up to 28 days, analyzing the variations detectable in the shape of the spectrum as the reaction went on. The degree of this variation, quantified through area calculations of the main significant bands, revealed a broad agreement with the degree of hydration of the paste measured by thermal methods. The findings of this research supply a solid foundation for future in-field application of NIR spectroscopy, for example, for investigations on cements with different hydration behavior, or to evaluate the effect of additives on cement pastes and, at a further level, for cement quality control.