The nanogranular nature of C-S-H

Despite its ubiquitous presence as binding phase in all cementitious materials, the mechanical behavior of calcium-silicate-hydrates (C-S-H) is still an enigma that has deceived many decoding attempts from experimental and theoretical sides. In this paper, we propose and validate a new technique and experimental protocol to rationally assess the nanomechanical behavior of C-S-H based on a statistical analysis of hundreds of nanoindentation tests. By means of this grid indentation technique we identify in situ two structurally distinct but compositionally similar C-S-H phases heretofore hypothesized to exist as low density (LD) C-S-H and high density (HD) C-S-H, or outer and inner products. The main finding of this paper is that both phases exhibit a unique nanogranular behavior which is driven by particle-to-particle contact forces rather than by mineral properties. We argue that this nanomechanical blueprint of material invariant behavior of C-S-H is a consequence of the hydration reactions during which precipitating C-S-H nanoparticles percolate generating contact surfaces. As hydration proceeds, these nanoparticles pack closer to center on-average around two characteristic limit packing densities, the random packing limit (η=64%) and the ordered face-centered cubic (fcc) or hexagonal close-packed (hcp) packing limit (η=74%), forming a characteristic LD C-S-H and HD C-S-H phase.     

Balancing strength and toughness of calcium-silicate-hydrate via random nanovoids and particle inclusions: Atomistic modeling and statistical analysis

As the most widely used manufactured material on Earth, concrete poses serious societal and environmental concerns which call for innovative strategies to develop greener concrete with improved strength and toughness, properties that are exclusive in man-made materials. Herein, we focus on calcium silicate hydrate (C-S-H), the major binding phase of all Portland cement concretes, and study how engineering its nanovoids and portlandite particle inclusions can impart a balance of strength, toughness and stiffness. By performing an extensive +600 molecular dynamics simulations coupled with statistical analysis tools, our results provide new evidence of ductile fracture mechanisms in C-S-H – reminiscent of crystalline alloys and ductile metals – decoding the interplay between the crack growth, nanovoid/particle inclusions, and stoichiometry, which dictates the crystalline versus amorphous nature of the underlying matrix. We found that introduction of voids and portlandite particles can significantly increase toughness and ductility, specially in C-S-H with more amorphous matrices, mainly owing to competing mechanisms of crack deflection, voids coalescence, internal necking, accommodation, and geometry alteration of individual voids/particles, which together regulate toughness versus strength. Furthermore, utilizing a comprehensive global sensitivity analysis on random configuration-property relations, we show that the mean diameter of voids/particles is the most critical statistical parameter influencing the mechanical properties of C-S-H, irrespective of stoichiometry or crystalline or amorphous nature of the matrix. This study provides new fundamental insights, design guidelines, and de novo strategies to turn the brittle C-S-H into a ductile material, impacting modern engineering of strong and tough concrete infrastructures and potentially other complex brittle materials.     

Preparation and properties of calcium silicate hydrate-poly(vinyl alcohol) nanocomposite materials

Summary A series of calcium silicate hydrate (C-S-H)-polymer nanocomposite (C-S-HPN) materials were prepared by incorporating poly(vinyl alcohol) (PVA) into the inorganic layers of C-S-H during precipitation of quasicrystalline C-S-H from aqueous solution. The as synthesized C-S-HPN materials were characterized by Fourier-transform infrared photoacoustic (FTIRPAS) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy/energy dispersed spectroscopy (SEM/EDS), thermogravimetric analysis (TG), differential thermogravimetry (DTG) and differential scanning calorimetry (DSC). The XRD peaks of C-S-HPN materials suggest the intermediate organizations presenting both intercalation of PVA and exfoliation of C-S-H. The SEM micrographs of C-S-H, PVA and C-S-HPN materials with different PVA contents exhibit the significant differences in their morphologies. Effects of the material compositions on the thermal stability of a series of C-S-HPN materials along with PVA and C-S-H were studied by TG, DTG and DSC. Three significant decomposition temperature ranges were observed in the TG curves of all C-S-HPN materials.     

Structural characterization of C-S-H and C-A-S-H samples—Part II: Local environment investigated by spectroscopic analyses

Spectroscopic studies (¹H, ²³Na and ²⁷Al MAS NMR and Raman spectroscopy) have been used to characterize three series of C-S-H samples (0.8<Ca/Si<1.7): one C-S-H series, one aluminum inserted C-S-H series (named C-A-S-H series), and one sodium and aluminum inserted C-S-H series (named C-N-A-S-H series). Previous Rietveld analyses have been performed on the two first series and have clearly shown that (1) a unique ‘tobermorite M defect’ structural model allows to describe the C-S-H structure whatever the Ca/Si ratio and (2) the insertion of aluminum into the C-S-H structure led to the degradation of the crystallinity and to a systematic increase of the basal spacing of about 2 Å regardless the Ca/(Si+Al) ratio (at a constant Al/Si ratio of 0.1). Spectroscopic investigations indicate that the main part of the Al atoms is readily incorporated into the interlayer region of the C-S-H structure. Al atoms are mainly inserted as four-fold coordinated aluminates in the dreierketten silicate chain (either in bridging or paired tetrahedra) at low Ca/Si ratio. Four-fold aluminates are progressively replaced by six-fold coordinated aluminates located into the interlayer region of the C-S-H structure and bonded to silicate chains. Investigation of the hydrogen bonding in C-S-H indicates that the main part of the hydrogen bonds is intra-main layer, and thus explains the low stacking cohesion of the C-S-H structure leading to its nanometric crystal size and the OD character of the tobermorite like structures.     

Carbonation study and determination of cement to sand ratio in hardened cement mortar by X-ray photoelectron spectroscopy

The determination of cement and sand content in an aged cement mortar is a challenging problem for civil engineers. Techniques like x-ray diffraction (XRD), thermogravimetric analysis (TGA) and electrochemical impedance spectroscopy (EIS) are well established, which can give some insight of the hydrated products. The present study is an attempt to use x-ray photoelectron spectroscopy (XPS) technique for the evaluation of ordinary Portland cement (OPC), sand (aggregate) composition and carbonation study in hardened cement mortar. Carbonation analysis and cement to sand ratio for all mortar compositions has been determined and studied in detail in the present work. The C 1s spectra of cement mortar with ratios 1:1, 1:3 and 1:6 shows carbonate formation on the surface with 21, 40 and 32 atomic percent, respectively. An increase in SiO₂ content corresponding to sand is observed for all three mortar mix. The formation of silica gel due to carbonation has not been observed in the mortar samples. The cement to sand ratio for all three mortar mixes is found to be in 20–30 percent error limit due to the heterogeneous nature of the mortar system.     

Use of DTA-TG in the evaluation of autoclaved cement-based systems: Part I. Cement-brick waste blends

Fired-clay products such as bricks, tiles and pavers, are made in large volumes for use in a variety of construction applications throughout the world. A significant proportion of them ends up being a waste product either during their production process or the demolition of buildings. High pressure steam curing or autoclaving has proven extremely versatile for the manufacture of cement-based building products incorporating waste materials such as fly-ash and blast furnace slag. The nature of hydration products in an autoclaved cement based system incorporating different amounts of finely ground brick waste was investigated by means of thermal analysis and XRD, and is the subject of this paper.This revised version was published online in November 2005 with corrections to the Cover Date.     

Phase transformation on heating of an aged cement paste

The standard cement paste (C-43-St) was studied previously by static heating, SH, immediately after 1 month hydration at w/c = 0.4 [J. Therm. Anal. Calorim. 69 (2002) 187]. This paste after 5-year ageing (unprotected from contact with air) was subject to thermal analysis in air and in argon (DTA, DTG and TG), to XRD at various temperatures, T, in a high temperature chamber, to mass spectroscopy (MS) and to IR spectroscopy. The aim of this study was to compare the results of SH (fresh paste) and of TG (the aged one), to verify the assumptions made on SH interpretation and to check the change in hydration products with ageing as measured by phase transformation on heating (ΔM versus the final mass). The sorbed water (EV), escaping at 110 °C from the fresh paste, was bound on ageing with a higher energy and escaped at higher temperatures. The joint water content of hydrates and of C-S-H gel increased on ageing by 1–2% in the dense paste C-43-St and did not change in the less compact one C-43-I. C-S-H gel transformed on heating above 600 °C into C₂S and C₃S. Portlandite content did not change on ageing. In the air atmosphere it became partly carbonated, which was accompanied by an increase in mass between 500 and 600 °C. Carbon dioxide and/or carbonate ions to form carbonates, were sorbed during ageing and were present in the aged paste in some form undetectable by XRD (amorphous or crypto-crystalline). Sensitivity to carbonation ΔM(700–800 °C) increased highly with ageing.     

Dynamic behaviors of water contained in calcium-silicate-hydrate gel at different temperatures studied by quasi-elastic neutron scattering spectroscopy

The dynamic behaviors of water contained in calcium-silicate-hydrate(C-S-H) gel with different water content values from 10%to 30%(by weight),are studied by using an empirical diffusion model(EDM) to analyze the experimental data of quasi-elastic neutron scattering(QENS) spectra at measured temperatures ranging from 230 K to 280 K.In the study,the experimental QENS spectra with the whole Q-range are considered.Several important parameters including the bound/immobile water elastic coefficient A,the bound water index BWI,the Lorentzian with a half-width at half-maximum(HWHM) Γ_1(Q) and Γ_2(Q),the self-diffusion coefficients D_(t1) and D_(t2) of water molecules,the average residence times τ_(01)and τ_(02),and the proton mean squared displacement(MSD)(u~2) are obtained.The results show that the QENS spectra can be fitted very well not only for small Q(≤1 A~1) but also for large Q.The bound/immobile water fraction in a C-S-H gel sample can be shown by the fitted BWI.The distinction between bound/immobile and mobile water,which includes confined water and ultra-confined water,can be seen by the fitted MSD.All the MSD tend to be the smallest value below 0.25 A~2(the MSD of bound/immobile water) as the Q increases to 1.9 A~1 no matter what the temperature and water content are.Furthermore,by the abrupt changes of the fitted values of D_(t1),τ_(01),and Γ_1(Q),a crossover temperature at 250 K,namely the liquid-to-crystal-like transition temperature,can be identified for confined water in large gel pores(LGPs) and/or small gel pores(SGPs) contained in the C-S-H gel sample with 30% water content.     

固体核磁共振技术在水泥基材料研究中的应用

水泥基材料组分、结构复杂,其水化过程、水化产物组成和结构表征是研究中的难点.一维固体核磁共振谱图可定性或定量分析胶凝材料（水泥及矿物掺合料）的水化程度、水化产物（特别是非晶相）的种类和结构,从而揭示胶凝材料的组成、外加剂和环境等因素对水泥基材料水化过程的影响.而二维核磁共振谱可进一步研究不同或同种原子核之间的连接情况,从而明确水化产物中的掺杂、取代,以及有机外加剂在水泥浆体中的分散情况.因此,固体核磁共振技术可获取其它方法难以获得的信息,有力促进水泥水化及其微观结构的研究.     

利用X光散射实验研究C-S-H的微观结构

为了了解波特兰水泥中的水化硅酸钙(C-S-H)的微观结构,对有无含添加剂superplasticizers(SPs)、从5天到68天的不同老化时间的波特兰水泥样品的X光散射实验,实验数据结果分析表明C-S-H中钙硅层间距的大小是0.98±0.01nm,结果说明波特兰水泥样品中C-S-H中钙硅层间距与样品是否含SPs以及样品的老化时间无关。