纳米压痕技术应用于水泥基材料的研究进展

水泥基复合材料作为一种重要的土木工程材料,在国民经济建设中起着举足轻重的作用。目前人们对于其力学性能的研究主要集中于抗压、抗折等宏观力学性能,相比之下,对其微观力学性能的研究较少。鉴于材料的宏观力学性能很大程度上依赖于其微观结构及微观力学性能,因此,从微观层面去探究水泥基材料的性能机理已成为目前研究的热点之一。随着材料微观测试技术的发展,目前纳米压痕技术已成为最先进的定量表征水泥基材料微观力学性能的测试手段。然而水泥基材料是一种非均质材料,其水化产物含有多种成分,导致人们在物相划分和定量分析时常常受到经验性的束缚,因此水泥基材料的性能远未达到人们预期的要求。通过极大似然或最小二乘法对压痕数据进行解卷积处理,可实现实验结果定量化,大大地改变了之前人为划分物相引起的不准确性的状况,使得研究问题的方法提升到一个新的高度。纳米压痕技术不仅可以测试水泥熟料成分(硅酸三钙(C_3S)、硅酸二钙(C_2S)、铝酸三钙(C_3A)等)的弹性模量和硬度,还可测试水泥基材料水化产物(不同密度的水化硅酸钙凝胶(C-S-H)、氢氧化钙(CH)等)的微观力学性能及水化产物未填充的孔隙。通过改变实验加载制度,尤其是持荷的停留时间,能够在很短的时间内测得微观蠕变模量并且可以定量预测水泥基材料的宏观徐变性能;将其与其他微观测试手段(SEM、EDS等)联用来揭示水泥基材料紧密混合相的微观力学性质,能够区分出具有强烈重叠微观力学性质的化学相,这使得纳米压痕技术成为更精确的物相分析方法;通过观测界面过渡区微观结构的变化情况,可以为界面过渡区强度理论提供一定的理论补充和技术支持。本文主要介绍了纳米压痕技术的基本原理和样品制备,并从纳米压痕技术研究水泥基材料水化产物分相及微观力学特性、蠕变性能以及界面特性三个方面阐述了其在水泥基材料中的研究现状和相关成果,对目前研究中存在的问题进行了分析,并展望了其在水泥基材料研究中的发展趋势,以期为它更广泛深入地检测和研究水泥基材料微观性能提供参考。     

硅酸二钙及以其为主要矿物的低钙水泥的研究进展

硅酸二钙是一种钙含量较低的硅酸盐胶凝矿物,与传统高钙硅酸盐矿物硅酸三钙相比,其具有石灰石消耗少、生成能耗低、水化热低、水化产物中氢氧化钙含量少等显著特点,发展以硅酸二钙为主要矿物的低钙水泥符合节能减排和可持续发展的要求,是水泥工业发展的重要方向。对硅酸二钙的结构、晶型转变及水化活性的研究情况进行了综合评述,并对以硅酸二钙为主要矿物的低钙水泥的组成、性能及存在的主要问题进行了介绍。在此基础上,指出了以硅酸二钙为主要矿物的低钙水泥研发的技术方向。     

SiC和Si_3N_4粉体的太赫兹时域光谱研究

采用太赫兹时域光谱装置测试SiC和Si3N4粉体在0.4～2.4 THz的透射光谱,研究SiC和Si3N4粉体对太赫兹波的吸收性能与其电导率的关系,分析SiC和Si3N4粉体对太赫兹波的散射特性。结果表明,SiC是一种半导体材料,其内部含有较多可以自由移动的载流子,对太赫兹波的吸收较强;Si3N4是绝缘性很好的材料,对太赫兹波的吸收很小;SiC和Si3N4粉体对太赫兹波的散射作用属于瑞利散射,但是测试波长比粉体粒径大得多,散射效果不明显。     

磁控溅射超薄金属膜在太赫兹波段的光学特性

采用THz时域光谱测试技术，对Fe扣Co的超薄金属膜在0.2～2，5THz波段的吸收特性、透射特性以及折射率进行了研究。在室温并去除水份影响的氮气环境中，获得了不同种类扣不同厚度的薄金属膜在太赫兹波段的时域谱．利用Origin7．0扣Matlab7，0软件处理得到这些金属薄膜对太赫兹波的透射率，吸收系数扣折射率．对比发现金属超薄膜在太赫兹波段的光学特性随薄膜厚度以及太赫兹波频率的变化有很大的改变，也就是具有明显的尺寸效应．同时根据所得到的折射率开口吸收系数还可以理论上计算出不同种类与厚度的超薄金属膜在太赫兹波段的复介电函数．     

等离子体中太赫兹波传输及成像探测特性研究

本文根据散射矩阵方法模拟等离子体并建立了非均匀等离子体理论模型,并在此基础上计算了0.1 THz^10 THz频段的全波段太赫兹波在其中的传输特性。根据介质阻挡放电原理在实验室环境下搭建等离子体射流产生装置并产生非均匀等离子体,进行了太赫兹时域光谱(THz-TDS)以及宽带太赫兹源在等离子体中的透射光谱测量以及太赫兹波对等离子体遮挡下目标物的反射成像的试验。理论和实验结果均表明,较高频太赫兹波在等离子体中有良好的穿透性,这为太赫兹波在黑障区的通信以及雷达探测应用打下研究基础。     

太赫兹成像技术在爆炸物检测中的应用

太赫兹波是一种电磁波,我们通常所说的太赫兹波的频率一般在0.1到10T赫兹之间。太赫兹波兼有微波和红外线的特点,在测量领域具有很广泛的应用。本论文简要介绍了太赫兹波的特性以及测量原理,同时指出其在爆炸物检测中的应用。     

地面背景材料的太赫兹特性研究进展

介绍了常见的地面环境天空、海洋和地面以及地面背景材料,主要有水、绿色植物、土壤、沙粒、岩石等材料。概述了地面背景材料对太赫兹波的吸收、反射、散射等电磁特性。研究发现,水、绿色植物、土壤、沙粒、岩石等地面背景材料在太赫兹波段主要表现出低反射特征,可为太赫兹目标特征控制技术的研究提供数据支撑。     

石墨烯场效应管及其在太赫兹技术中的应用

石墨烯是单原子厚度的二维碳同素异形体材料,因其出色的电学、热学、光学及力学特性而被广泛应用于生物检测、医学、新能源、微电子、射频电路等领域。正是凭借着石墨烯独一无二的材料特性,石墨烯基场效应管(GFETs)比传统的硅基晶体管具有更高的迁移率、微缩空间及特征频率。此外,石墨烯零带隙的对称圆锥形能带结构,以及在受外部激发下形成的负电导率特性(太赫兹频段),使得GFETs能广泛应用于太赫兹功能器件中,也为实现太赫兹技术商业化提供了一种兼容当前半导体产业技术的低成本选择。针对硅基晶体管发展面临的尺度瓶颈,本文综述了GFETs器件的基本结构、射频/太赫兹领域的主要特性以及制备工艺,并举例说明了其在太赫兹技术领域的最新应用。     

水泥基材料无机/有机复合内养护剂的研究进展

无机/有机复合吸水材料具有一定的亲水基团和三维网络结构,吸水性、保水性和释水性优异,是水泥基材料重要的内养护剂之一。通过在水泥基材料中引入无机/有机复合吸水材料,利用其吸-释水特性可自动调节水泥基材料内部相对湿度,促进水化反应,减少水泥基材料自收缩和早期开裂等现象,提高力学性能和耐久性。概述了无机/有机复合内养护剂(CICA)的制备方法、结构特征以及吸-释水行为;综述了CICA对水泥基材料水化进程、微观结构、宏观性能和耐久性的影响;展望了CICA在混凝土应用的发展前景,为CICA在水泥基内养护中的应用提供一定理论指导和技术参考。     

超材料吸波器的极化特性研究进展

超材料由于具有吸波特性而引起了人们的极大兴趣.简要介绍了超材料产生吸波的原理,并着重阐述了吸波超材料在微波段、光波段以及太赫兹波段的极化特性和相应超材料吸波器结构的模拟及实验研究进展.这种超材料的吸波特性在军事和民用上具有潜在的应用价值.     

Effects of cement size distribution on capillary pore structure of the simulated cement paste

The evolution of tricalcium silicate (C₃S) microstructure during hydration is tri-dimensionally simulated based on an “Integrated Particle Kinetics Model”. The hydration degree, the contact surfaces between the hydrated particles, the hydraulic radius and the capillary pore size distribution of the simulated cement paste at various degrees of hydration are calculated. Three examples of the C₃S microstructure development with different size distributions are presented. The effects of the cement size distribution on pore structure of cement paste are demonstrated and the results are discussed. In these examples, the cement size distribution varies between 3–40, 5–40 and 10–40 μm, respectively.     

Revisiting the microstructure of hydrated tricalcium silicate––a comparison to Portland cement

The microstructures of 0.40 w/s-ratio pastes of tricalcium silicate (C₃S), alite and Portland cement have been studied at the hydration times 24 h and 1 month. A field-emission SEM (FE-SEM) was used to obtain high-resolution backscattered electron images. Comparison revealed no microstructural differences between C₃S and alite, but there were considerable differences in microstructure between C₃S and Portland cement pastes. The microstructure of the C₃S paste was simpler than that of the Portland cement, and could be described by a few characteristic features. Distribution of the reaction products differed substantially in the two systems. While hollow shells (Hadley grains) were a prominent feature of the Portland cement paste, their occurrence was more limited in the C₃S and alite pastes. Hollow shells were restricted to grains smaller than about 5 μm in the C₃S and alite pastes, and gapped hollow shells were not a common feature.     

纳米SiO2改性聚合物水泥基复合材料早期微观结构及性能

利用纳米SiO₂(nano SiO₂)早期可促进聚合物水泥基复合材料水化速率、提升其力学性能、改善其界面过渡区(ITZ)性能及优化其孔隙结构等特点,借助XRD、SEM、EDS、显微硬度(MH)及压汞(MIP)等试验,揭示了nano SiO₂对聚合物水泥基复合材料早期性能影响的微观机制。结果表明:当nano SiO₂掺量为2wt%时,聚合物水泥基复合材料的力学性能最优,3 d和7 d龄期抗压强度分别为57.5 MPa和67.3 MPa,较仅仅掺加聚合物的水泥基复合材料分别提高了12.7%和13.9%;nano SiO₂的掺入改变了聚合物水泥基复合材料水化产物数量及微观形貌。对于ITZ性能,nano SiO₂掺入后,聚合物水泥硬化浆体-骨料的ITZ厚度减小,形貌变得更加致密;ITZ的钙硅比因nano SiO₂的加入变小而其显微硬度变大;此外,nano SiO₂加入后可以进一步填充聚合物水泥基复合材料更加细小的孔隙,使其凝胶孔比例变高,最可几孔径变小,大大优化了聚合物水泥基复合材料的孔隙结构。      

Ni2O3对C3S形成过程的影响及其固溶效应

C3S是水泥熟料中最重要的矿物,杂质离子固溶进入C3S晶格并促进其单斜型或三方型稳定存在,研究离子在C3S中的固溶作用机理,能更深入了解阿利特的微结构及性质。利用化学分析、XRD、DTA及相图分析,研究Ni2O3对C3S形成过程的影响及其固化效应。结果表明:Ni2O3主要以+2价的形式在CaO-Si O2二元体系中存在,因其优先与Si O2反应形成固溶体,f-CaO随Ni2O3掺量递增而增大;当Ni2O3掺量大于其CaO-Si O2二元体系固溶极限时,f-CaO变化趋势呈相反趋势,且促进C3S形成效应明显。通过最小二乘法及Ni2O3固溶度的精确界定,可推导出Ni2O3在C3S中的固溶反应分子式为:(Ca3-0.53xNi0.53x)(Si1-0.47xNi0.47x)O5(x=0.0442)。     

Formation of thaumasite in synthetic cement mineral slurries

In order to investigate the effect of alite polymorphism on the susceptibility of cements to thaumasite formation, slurries were prepared from magnesium sulphate solution and mixtures of calcium carbonate with synthetic cement preparations plus additions of 0%, 1% or 2% w/w alumina. Two synthetic cement preparations were used; a co-prepared mixture of monoclinic alite (C₅₄S₁₆AM) with β-C₂S (designated A) and a 99% pure, primarily triclinic C₃S (designated B). The slurries were prepared after the manner of Gaze [Cement Concrete Res. 27(2) (1997) 259] and maintained in a state of continual agitation at 5 °C for 100 days. After this period, the slurries were dried and characterised using X-ray diffraction. In slurries made with A, both ettringite and thaumasite (or a solid solution thereof) were detected, the apparent ratio of the former to the latter increasing with alumina addition. No gypsum was detected. In slurries made with B, the only sulphate phase detected was gypsum.

This interesting observation leads to a number of avenues for discussion;

• that alumina must be present in sufficient quantities within the clinker or gel structure, rather than as an addition, to initiate TF;

• that TF is only initiated by C₂S, not C₃S;

• that TF cannot be initiated by triclinic C₃S.

     

低场核磁共振技术在水泥基材料中的应用

近年来,核磁共振技术已经成为表征水泥基材料水化进程、非化学结合水量和孔结构的一种重要手段。简单介绍了核磁共振基本原理和低场核磁共振主要参数;阐述了低场核磁共振技术在水泥基材料测试中的应用,主要包括水化进程、孔结构、水分迁移和扩散等方面的内容;展望了低场核磁共振技术在水泥基材料研究中的应用前景。     

掺珍珠岩水泥石孔分形维数及其与孔结构、强度的关系

通过压汞法测试不同龄期掺0-40%珍珠岩掺合料水泥石的孔结构参数,利用分形理论的相关知识研究这些水化物的孔体积分形特征,计算它们的孔分形维数D=3.3～3.5,分析并探讨该水泥石孔分形维数与孔结构参数、抗压强度之间的关系.结果表明水泥石孔分形维数与孔隙率、孔径、孔表面积有密切的关系,随着孔分形维数增大,孔隙率提高,孔径扩大、孔表面积增大,孔结构就越劣化,对应的材料抗压强度下降.因此孔体积分形维数可用于综合评定材料的孔结构特性.     

Depercolation threshold of porosity in model cement: approach by morphological evolution during hydration

The depercolation threshold of porosity is an important parameter to assess the permeability of cement-based materials. The depercolation threshold is usually defined as the porosity whereby the volume fraction of connected pores in the cement paste decreases to zero. In this paper, the depercolation threshold is defined and determined with respect to the morphological development of pore space during hydration. The morphology of solid phase and pore structure is studied on model cement simulated by the SPACE system, using stereological theory. The influences of particle size distribution and water to cement ratio (w/c) on the depercolation threshold of porosity are discussed. It is found that particle size distribution of cement has significant influence on the depercolation threshold of porosity. The depercolation threshold is higher for finer cement system. However, the influence of w/c on the depercolation threshold of porosity is negligible. For a model cement of moderate fineness, depercolation is not possible at a relatively high w/c (say, 0.6), because the porosity of cement paste remains above the depercolation threshold even at complete hydration.     

Terahertz sources and detectors and their application to biological sensing

Terahertz spectroscopy has long been used as an important measurement tool in fields such as radio astronomy, physical chemistry, atmospheric studies and plasma research. More recently terahertz technology has been used to develop an exciting new technique to investigate the properties of a wide range of biological materials. Although much research remains before a full understanding of the interaction between biomaterials and terahertz radiation is developed, these initial studies have created a compelling case for further scientific study. Also, the potential development of practical tools to detect and identify biological materials such as biological-warfare agents and food contaminants, or of medical diagnostic tools, is driving the need for improved terahertz technology. In particular, improved terahertz sources and detectors that can be used in practical spectroscopy systems are needed. This paper overviews some of the recent measurements of the terahertz spectra of biomaterials and the ongoing efforts to create an all-solid-state technology suitable not only for improved scientific experiments but also for military and commercial applications.