基于分子动力学水分和离子在水化硅酸钙纳米孔道中的传输特性研究

水化硅酸钙凝胶是水泥水化产物中最基本的粘结相,水分子和离子在凝胶孔中的传输从根本上决定着水泥混凝土材料的服役寿命.采用分子动力学方法系统地研究了水分子、氯离子和钠离子在1nm、2nm、3nm和4nm的水化硅酸钙凝胶孔中的传输过程.基于径向分布函数和均方位移的离子轨迹分析发现在纳米孔道中离子和水分子展现出异于毛细水的分子结构和动力学特性:水分子有序性排布、离子大量在界面吸附和扩散速度急剧下降.这种分子结构与动力学的特性是因为水化硅酸钙界面处硅链中的非桥接氧会与水分子形成稳定的氢键连接,而钠离子可以形成Na-O化学键,同时表面的钙离子也可以与氯离子形成CaCl2团簇体.此外,随着孔径的增大,离子和水分子的扩散系数逐渐由0.15×10-9m2/s、0.7×10-9m2/s增大到1.3×10-9m2/s、3×10-9m2/s,这很接近于实验测得的毛细水的扩散系数,说明在纳米尺度上,孔径的约束和界面化学键作用是决定离子和水分子传输的关键因素.     

湿度对水化硅酸钙力学性能影响的分子动力学模拟

水化硅酸钙(C-S-H)是水泥水化产物中最重要的组成成分,是水泥基材料的主要胶凝相。C-S-H层间水对其纳米结构和力学性能会产生显著影响。利用分子动力学研究了不同湿度C-S-H在结构和力学性能方面的差异。通过原子径向分布函数和浓度分布、弹性常数以及应力应变关系分析了湿度对C-S-H结构和弹性性质以及拉伸、压缩、剪切力学性能和变形性能的影响。结果表明:湿度增加会导致C-S-H中Si、Ca原子近程范围内的O原子集聚增多,还会导致C-S-H层间距离增大,分层更加明显,同时会降低C-S-H的弹性性质;湿度的增加会降低C-S-H拉伸、压缩、剪切力学性能和变形性能;湿度对抗拉与抗剪强度影响较大,对抗压强度影响较小,对拉伸时的变形性能影响最大,对压缩时的变形性能影响最小。     

化学外加剂与水化硅酸钙相互作用的分子动力学研究进展EI北大核心CSCD

掺入化学外加剂是提升水泥基材料性能的有效方法。然而,各类化学外加剂在分子尺度上的作用机制仍需进一步明晰。水化硅酸钙(C–S–H)作为水泥水化的主要产物,控制着水泥基材料的各项宏观性能。分子动力学模拟可在分子/原子尺度上揭示化学外加剂分子与C–S–H的相互作用及其对C–S–H性能的影响。综述了近年来针对有机和无机化学外加剂与C–S–H在分子尺度上的相互作用及其对C–S–H性能影响机理的分子动力学研究进展,并展望了关于化学外加剂–(C–S–H)体系分子动力学模拟的后续研究方向。总结的化学外加剂包括有机小分子、树脂和纤维、水溶性聚合物等有机外加剂,以及(改性)石墨烯、硅烯、碳纳米管、各类纳米粒子等无机外加剂。分子动力学模拟研究重点关注各类外加剂与C–S–H界面的相互作用,这一作用的理解有助于揭示外加剂对C–S–H材料力学性能的提升机理。此外,针对有机小分子、水溶性聚合物及部分纳米粒子等外加剂,大量研究采用分子动力学方法,揭示此类外加剂对C–S–H层状结构的吸附、插层、聚集阻塞等微观作用,从而阐明这些外加剂对C–S–H力学性能、传输性能,乃至收缩行为的作用机理。这些认识,为有效提升水泥基材料性能、外加剂分子结构设计提供理论启发。     

分子动力学模拟研究钙硅摩尔比对水化硅酸钙结构与力学性能的影响

水化硅酸钙(C-S-H)作为硅酸盐水泥基材料的主要结合相,对水泥基材料的耐久性、物理力学性能有显著影响。本文构建了钙硅摩尔比(Ca/Si)从1.1到1.9的5个C-S-H模型,并通过分子动力学模拟了C-S-H 模型沿x、y和z方向的纳米压痕测试,然后采用典型的Oliver-Pharr方法分别计算它们的压痕模量和硬度。模拟结果表明:随着钙硅摩尔比的增加,C-S-H的密度会逐渐降低,水硅摩尔比会逐渐增加,平均硅链长会有所降低;C-S-H的力学性能受钙硅摩尔比的影响很大,随着钙硅摩尔比的增加,硅链缺陷程度增加,钙硅片层状结构的稳定性会相应降低,C-S-H结构抵抗外界变形荷载的能力减弱,从而导致压痕模量和硬度降低。平行于钙硅层方向的压痕模量和硬度值比较接近,而垂直于钙硅层方向的值略低,C-S-H近似于横观各向同性结构。随着钙硅摩尔比的增加,三个方向的值逐渐接近,C-S-H具有从横观各向同性变为各向同性的趋势。     

离子水化的分子动力学模拟

采用分子动力学模拟的方法在 2 98 1 5K及无限稀释条件下对Li+、Na+、K+、F- 、Cl- 5种单个离子的水化现象进行研究 模拟得到了离子溶液体系一幅清晰的微观物理图像 ,阳离子周围的水分子以氧来靠近阳离子 ,而阴离子周围的水分子则以其中某一个氢来逼近阴离子 提出了一个“水化因子”的新概念来定量地表征离子水化的强弱 ,阳离子水化的强弱顺序为Li+>Na+>K+ 阴离子水化强弱顺序为F- >Cl- 对于水化作用较强的Li+,其虽有第二配位圈 ,但并无水化 离子的Pauling半径大小是决定离子水化强弱的关键因素 ,这些信息将为建立相应的分子热力学模型提供基础     

水化硅酸钙回收污水中磷的试验研究

采用合成水化硅酸钙进行污水除磷试验,以模拟污水为研究对象,考察了接触时间、Ca2+浓度、初始pH值、干扰离子等因素对除磷效果的影响,在利用水化硅酸钙回收实际污水中磷的试验发现,在处理8h后除磷量达到101 mg/g,折合P2O5含量超过常用的水溶性磷肥过磷酸钙,且产物经酸处理后将快速释磷,在1h后磷释放率接近100％,...     

分子动力学模拟水化硅酸钙Ca4Si6O14(OH)4·2H2O的结构

为了在原子水平上再现硅酸盐水泥的主要水化产物水化硅酸钙的结构,以Hamid模型为基础建立初始结构,采用分子动力学方法这一物质结构研究的新手段,模拟低钙比的Ⅰ型水化硅酸钙[Ca4Si6O14(OH)4·2H2O,C-S-H(Ⅰ)]的结构;根据模拟结果,比较分析水合硅酸钙晶体与无定形水化硅酸钙在结构上的异同,并且通过与实验数据的比较验证模拟结果的可靠性。模拟结果表明:水合硅酸钙晶体的结构长、短程确实都有序,而其无定形态的C-S-H(Ⅰ)只存在近程有序的结构特点,因为后者中Ca—O、Si—O、O—O及Si—Si等原子对的径向分布函数随着原子间距的增大而逐渐趋于1;C-S-H(Ⅰ)的基本结构单元为硅氧四面体,并且Si的最近邻Si数目为2,即硅氧四面体以Q2的形式连接而呈链状;模拟得到的Si与O、Ca与O的间距分别为0.162nm和0.264nm,Si的O配位数为4,这些结构参数基本与实验值相符合,说明模拟结果能够再现C-S-H(Ⅰ)的结构。     

水化硅酸钙的结构及其变化

基于水化硅酸钙应用范围的扩展和混凝土的发展趋势,阐述了水化硅酸钙结构及其变化的研究进展。详细分析了无机和有机组分等因素对水化硅酸钙存在状态的影响。分析了水化硅酸钙与无机或有机组分间的相互结合原理。同时指出有机组分对水化硅酸钙组成结构的影响,是需要进一步深入研究的课题。     

水化硅酸钙凝胶的研究进展

水化硅酸钙(C-S-H)凝胶是影响水泥基胶凝材料宏观力学性能与长期耐久性的核心组分,阐明结构和性能间的关联关系有利于实现C-S-H凝胶的合成及推广应用。本文首先对C-S-H凝胶不同阶段的典型结构进行了综述,并引出结构与性能间的内在联系;随后,介绍水热合成法对不同结构C-S-H凝胶的精确调控,并详细阐述了合成要素对其组成、形貌以及结构的影响规律;最后,综述了合成C-S-H凝胶在相关应用领域的基础研究。本文聚焦于C-S-H凝胶构效关系的梳理总结以及C-S-H凝胶工程应用的前景探索,可为充分完善水泥水化机理、开发高性能绿色化建材提供理论参考。     

无机外加剂中各离子对水化硅酸钙的影响研究进展

近年来,随着混凝土技术的发展,外加剂已成为制备混凝土的重要辅助材料,但外加剂引入的各种离子对水化硅酸钙(C-S-H)的结构及形貌有较大影响.因此综合评述了无机外加剂中不同离子对C-S-H组成、结构及微观形貌的影响:Al3+能够直接参与C-S-H结构的构建;Na+、K+、Cl-可以加速水化反应,促进C-S-H凝胶的生成;...     

Heteroepitaxial Growth of Calcium Silicate Hydrate on Calcium Germanate Hydrate

The hydration of tricalcium silicate at 25°C was accelerated by seeding with 5 wt% tricalcium germanate. Based on heat evolution, seeding resulted in the elimination of the induction period. However, the shape of the hydration peak remained the same. Because tricalcium germanate hydrates first, the microstructure of the calcium silicate hydrate which subsequently forms is influenced by the calcium germanate hydrate morphology. Calcium silicate hydrate formed in the presence of calcium germanate hydrate exhibits the morphology typical of the latter. Acceleration of hydration and morphological variation indicate heteroepitaxial growth.     

Pore Structure of Calcium Silicate Hydrate in Hydrated Tricalcium Silicate

Adsorption of N₂ and water vapor was studied in completely hydrated tricalcium silicate and in fully hydrated tricalcium silicate from which Ca(OH)₂ had been extracted. Compared with results obtained using N₂, water vapor adsorption led to increased values for small-pore volume, peak shifts to smaller sizes, and decreased values for large-pore volume. Marked hysteresis was observed in the case of water vapor adsorption; the resorption branch apparently represents the true pore structure. Extraction of Ca(OH)₂ from the paste increased the calculated volume of small pores strikingly, suggesting that adsorption is hindered by Ca(OH)₂; this tendency is more obvious in water vapor adsorption. The adsorption measurements indicate the existence of two kinds of pores, i.e. a wider intergel-particle pore and a smaller pore existing within the gel particle. The latter pore was further classified into intercrystallite and intracrystallite pores.     

Developments in TEM Nanotomography of Calcium Silicate Hydrate

This investigation was designed to explore the possibility of using transmission electron microscope (TEM) tomography on cement‐based systems gain a greater understanding of their nanostructure and pore network. The preliminary results show a clearly a well‐defined pore network at the nanoscale, with pore size approximately 1.7–2.4 nm in diameter and spaced around 5–8 nm apart. A comparison of small angle X‐ray scattering data with 2‐D TEM images analyzed with the Fourier slice theorem documents an excellent structural correlation.     

水分子和离子在地聚合物胶凝材料中的分子动力学研究

地聚合物是一种具有三维网状结构的水泥基胶凝材料,其主要水化产物是水合硅酸铝钠凝胶(NASH).在工程应用中,氯盐侵蚀与硫酸盐侵蚀是影响耐久性的主要原因.运用分子动力学方法,研究NaCl溶液与Na2SO4溶液在NASH凝胶纳米孔道中的传输特性.结果表明,NaCl溶液与Na2SO4溶液在凝胶孔道的非饱和传输过程中,呈现出明显的毛细吸附现象,NASH凝胶界面呈现亲水性与电负性.Na2SO4溶液的侵入速率明显低于NaCl溶液,硫酸根离子对水分子侵入的抑制作用强于氯离子.     

Synthesis of Calcium Silicate Hydrate in Highly Alkaline System

Synthesis of calcium silicate hydrate (C‐S‐H) was conducted over the range of 50°C–90°C and C/S ratio of 0.86–2.14 in the highly alkaline Na₂O–CaO–SiO₂–H₂O system for silicon utilization in high alumina fly ash. Structural change in C‐S‐H formed in the highly alkaline system was investigated using XRD and ²⁹Si MAS NMR spectra. X‐ray photoelectron spectroscopy was used to confirm the amount of sodium ions in C‐S‐H. Conversion of Si may reach 99% under optimum conditions. A higher degree of polymerization of silicate was obtained at lower temperature and C/S ratio. Na⁺ was confirmed to exist as Na–OSi and Na–OH. The amount of Na⁺ is the least at C/S ratio of 1.43, which conform to the prediction of topological constraint theory. High Ca/Si ratio leads to the increasing in Na⁺ combined in the interlayer. Increasing in the Na⁺ concentration in the system also increases the amount of Na⁺ combined in the interlayer and reduces the polymerization. Ion exchange was proven to be an effective way to remove Na⁺ combined in the interlayer of C‐S‐H.     

Nanostructure of Calcium Silicate Hydrate Gels in Cement Paste

High-resolution electron microscopy study of calcium silicate hydrate (C-S-H) gels in ordinary portland cement (OPC) and a slag/OPC blend has been performed. Nanocrystalline regions on the scale of ∼5 nm or less in C-S-H are found in both cement pastes, and they are formed after a curing time as brief as 7 d. A change in the d -spacing of the nanocrystalline regions with time is observed for the first time, which is believed to correspond to the development of C-S-H with time. The nanoheterogeneous nature of C-S-H is demonstrated and correlated to the strong Ca:Si ratio fluctuations that are observed.     

Structures and Phase Relations of Aluminum-Substituted Calcium Silicate Hydrate

The structures of aluminum-substituted calcium silicate hydrate (C-S-H) forming in a series of aqueous suspensions formulated with colloidal silica, reactive alumina, and lime and aged for 1 year have been studied using ²⁹Si and ²⁷Al magic angle spinning nuclear magnetic resonance spectroscopy (with and without cross polarization (CP)), solution pH, electron microscopy, and X–ray diffraction. As in earlier work dealing with the nature of C-S-H in the system CaO-SiO₂H₂O₂ two aluminum-substituted C-S-H phases, having distinctly different anionic structures on the atomic level (Q₂ versus Q₁Q₂), were found to extend into the system CaO-Al₂O₃-SiO₂-H₂O₂ X-ray diffraction patterns of the two aluminum-containing C-S-H phases are nearly identical, suggesting that their intermediate-range order is very similar, but MASNMR spectra show that these two phases have markedly different silicate structures on the atomic-level scale. Both C-S-H structures can accommodate approximately 5 mol% of Al₂O₃ in tetrahedral and possibly octahedral coordination as well.