Analysis of C-S-H gel and cement paste by small-angle neutron scattering

The role of small-angle X-ray and neutron scattering (SAXS and SANS) in the characterization of cement is briefly reviewed. The unique information obtainable from SANS analysis of C-S-H gel in hydrating cement is compared with that obtainable by other neutron methods. Implications for the nature of C-S-H gel, as detected by SANS, are considered in relation to current models. Finally, the application of the SANS method to cement paste is demonstrated by analyzing the effects of calcium chloride acceleration and sucrose retardation on the resulting hydrated microstructure.     

Effects of decalcification on the microstructure and surface area of cement and tricalcium silicate pastes

Thin coupons of white portland cement (WPC) and tricalcium silicate paste were decalcified by leaching in concentrated ammonium nitrate solutions, resulting in calcium-to-silicon molar ratios (C/S) ranging from 3.0 (control) down to 0.3. The microstructure and surface area were measured using both small-angle neutron scattering (SANS) and nitrogen gas sorption. The intensity in the SANS data regime corresponding to the volume fractal C-S-H gel phase increased significantly on leaching, and the total surface area per unit specimen volume measured by SANS doubled on leaching from C/S=3.0 to near C/S=1.0. The nitrogen BET surface area of the WPC pastes, expressed in the same units, increased on decalcification as well, although not as sharply. The primary cause of these changes is a transformation of the high-density “inner product” C-S-H gel, which normally has a low specific surface area as measured by SANS and nitrogen gas sorption, into a morphology with a high specific surface area. The volume fractal exponent corresponding to the C-S-H gel phase decreased with decalcification from 2.3 to 2.0, indicating that the equiaxed 5 nm C-S-H globule building blocks that form the volume fractal microstructure of normal, unleached cement paste are transformed by decalcification into sheetlike structures of increasing thickness.     

A multi-technique investigation of the nanoporosity of cement paste

The nanometer-scale structure of cement paste, which is dominated by the colloidal-scale porosity within the C-S-H gel phase, has a controlling effect on concrete properties but is difficult to study due to its delicate structure and lack of long-range order. Here we present results from three experimental techniques that are particularly suited to analyzing disordered nanoporous materials: small-angle neutron scattering (SANS), weight and length changes during equilibrium drying, and nanoindentation. Particular attention is paid to differences between pastes of different ages and cured at different temperatures. The SANS and equilibrium drying results indicate that hydration of cement paste at 20 °C forms a low-density (LD) C-S-H gel structure with a range of gel pore sizes and a relatively low packing fraction of solid particles. This fine structure may persist indefinitely under saturated conditions. However, if the paste is dried or is cured at elevated temperatures (60 °C or greater) the structure collapses toward a denser (less porous) and more stable configuration with fewer large gel pores, resulting in a greater amount of capillary porosity. Nanoindentation measurements of pastes cured at different temperatures demonstrate in all cases the existence of two C-S-H structures with different characteristic values of the indentation modulus. The average value of the modulus of the LD C-S-H is the same for all pastes tested to date, and a micromechanical analysis indicates that this value corresponds to the denser and more stable configuration of LD C-S-H. The experimental results presented here are interpreted in terms of a previously proposed quantitative “colloid” model of C-S-H gel, resulting in an improved understanding of the microstructural changes associated with drying and heat curing.     

Application of small-angle neutron scattering (SANS) to the study of coal porosity

Pore size distribution functions of coals of different rank obtained from small-angle neutron scattering data are quantitatively consistent with data obtained from adsorption measurements. The agreement will provide a firm foundation for using SANS to probe coal porosity under conditions where conventional gas adsorption techniques are inappropriate.     

Investigation of the microstructure of alkali-activated cements by neutron scattering

Significant research has been devoted to understanding and modeling the neutron scattering behavior of Portland cement pastes. The present work examines the potential of neutron scattering to noninvasively evaluate the properties of alternative cementitious materials encountered in the field. To interpret the scattering of both alkali-activated and slag-cement systems, alternative models to those typically adopted for Portland cement pastes were considered. Investigation of alkali-activated and slag-cement coupons were conducted for different sample thickness (∼0.5, 1, 2, 4, 6, 8 and 12 mm) over a wide scattering vector (Q) range (0.0005<Q>0.03 nm⁻¹ and 0.04<Q>4 nm⁻¹) on both ultra (USANS) and conventional small-angle neutron scattering (SANS) spectrometers. This wide Q range allowed determination of the fractal properties of the microstructure as well as the radius of the main scattering particle in the material. An empirical correction for multiple scattering was made based on the Dexter-Beeman equation and demonstrated that for thicker sample widths the theory correlated reasonably well. Alkali-activated fly ash was found to have the largest R value while the OPC and slag mix exhibited the largest Guinier radius. This difference was attributed to variations in the extent of multiple scattering for the samples. Successful application of this model was limited to sample thickness ≥1 mm. A combined power law-Sabine expression was also utilized to successfully model the SANS data over a Q range of 0.04-4 nm⁻¹.     

Water dynamics in cement paste at early age prepared with pozzolanic volcanic ash and Ordinary Portland Cement using quasielastic neutron scattering

Early age hydration kinetics of Portland cement with pozzolanic volcanic ash was examined using quasielastic neutron scattering. Volcanic ash consisting of two different particle sizes was used to prepare cement pastes with different ratios of Portland cement to volcanic ash. The concentration of the volcanic ash played a major role in the bound water index and self-diffusion coefficients of hydration water confined in the cement paste. An increase in the particle size of the volcanic ash affected the degree of hydration by allowing more free and mobile water in the gel pores, suggesting that volcanic ash may not have completely reacted during the experimental time frame. This study shows that the particle size along with variation in volcanic ash composition governs the early age hydration process in volcanic ash cements.     

Structure and swelling behaviour of hydrophilic epoxy networks investigated by SANS

Structure of hydrophilic epoxy networks swollen in deuterated water has been investigated by small-angle neutron scattering (SANS). Two series of the networks were prepared by end-linking reaction of α,ω-diamino terminated poly(oxypropylene)-block-poly(oxyethylene)-block-poly(oxypropylene) (POP-POE-POP), α,ω-diamino terminated poly(oxypropylene) (POP) and diglycidyl ether of Bisphenol A propoxylate (PDGEBA). In the first series, prepared using functionalized POP-POE-POP and PDGEBA, hydrophilicity of the networks was controlled via cross-linking density of the networks, changing the initial ratio of reactives. In the second series, POP-POE-POP was gradually substituted by POP of the same molecular weight, enabling a control of hydrophilicity of the networks at essentially constant crosslinking density in this way. Microphase separated structure of the networks swollen in deuterated water with composition variations on nanometer scale was found by SANS. The scattering data were fitted to the Percus-Yevick model, approximating the swollen network by an idealized system of spheres dispersed in the matrix. Satisfactory fits in the region of the interference scattering peak were obtained giving values 30-70 Å for the average radius of the spherical regions. Radius of the spheres increases with increasing hydrophobicity of the networks (growing POP content and/or network crosslinking density).     

缓凝剂对水泥浆中自由水状态演变的影响

用低场核磁共振技术考察了HN-1型缓凝剂对水泥浆体中可蒸发水的横向弛豫时间(T2)及状态演变过程的影响。结果表明:在初始水化阶段的150 min内,水泥浆GR(添加缓凝剂HN-1的水泥净浆)的弛豫峰峰形和峰顶位置均无明显变化,水泥浆G(纯水泥净浆)的弛豫峰峰形变窄且峰顶位置从2.15 ms迁移至0.95 ms,说明缓凝剂HN-1主要通过改变水泥浆体中不同状态水的存留时间来改变其水化进程。随养护时间的延长,硬化水泥石W0.44和WR0.5中可挥发水弛豫峰分布范围分别从0.11~4.75 ms变为0.08~0.58 ms、0.24~4.23 ms变为0.11~2.35 ms,总体趋向于短弛豫时间,表明水泥石中毛细水逐渐向凝胶水和物理结合水转化,水泥石养护龄期延长至25 d时,其内部凝胶结构水含量超过90%。利用XRD考察了缓凝剂对水泥浆水化产物的影响,结果表明:缓凝剂只改变水泥浆水化过程,对最终水化产物晶型及晶型结构不存在任何影响。     

Crosslink distribution of epoxy networks studied by small-angle neutron scattering

Crosslink distribution of epoxy networks of diglycidyl ether of bisphenol A (DGEBA) cured with stoichiometric amounts of meta-phenylene diamine (mPDA) was examined by small-angle neutron scattering (SANS). A monodisperse DGEBA resin with the smallest molecular weight was used to enhance the crosslink density and to simplify the network structure for deuterium-labelling. Meta-phenylene-d₄ diamine (mPDAd₄) was applied to label definitively the crosslinks. SANS measurements covered a reciprocal space range from 0.016 to 0.220 Å^?1 or, equivalently, real-space distances from 400 to 30 Å. Application of SANS on the deuterium-labelled epoxy networks consistently produces a constant excess intensity over the unlabelled epoxy networks. Since the scattering intensity from total correlation of the network was negligible, as evident from measurements of SANS on the unlabelled epoxy networks and small-angle X-ray scattering on the epoxy networks, the constant excess SANS intensity can only be attributed to a uniform spatial distribution of the amine curing agent. In other words, the crosslinks are distributed uniformly throughout the epoxy network.     

Phase transition in swollen gels

Summary The temperature dependences of the small-angle neutron scattering (SANS) from solutions and networks of poly (N,N-diethylacrylamide) (PDEAAm), or from the copolymer of DEAAm and 5 mol.% sodium methacrylate (MNa) in deuterated water were measured. In the low-temperature range (T<30°C, expanded state) the SANS curves have features typical of scattering from polymer coils. At elevated temperatures (T>60°C, collapsed state) the character of SANS curves changes, indicating that in both networks and solutions compact globular structures are formed. The presence of MNa (i.e. of charges on the chains) shifts the temperature of the transition range from the expanded to the collapsed state towards higher temperature by 10–15°C.On leave from the Institute of Macromolecular Chemistry, Czechoslovak Academy of Sciences     

Calcium Silicate Hydrates Studied by Small-Angle Neutron Scattering (SANS)

Small-angle neutron scattering (SANS) was used to study calcium silicate hydrate (C-S-H) formed via pozzolanic reaction between calcium oxide and ultrafine silica in water or polymer solutions at a temperature of 20°C. The SANS profile of this product was consistent with a structure that consisted of platelets with maximum diameters of ∼20 nm (± 5 nm) in the x – y plane, which was similar to a structure that had been deduced in previous work via X-ray diffractometry. The presence of two different types of superplasticizer in solution (at a concentration of 10 g/L) had no significant effect on its formation kinetics or its SANS profile.     

Gel-size dependence of temperature-induced microphase separation in weakly-charged polymer gels

The gel-size dependence of microphase separation in weakly-charged gels of N-isopropylacrylamide (NIPA) and 1-vinylimidazole (VI) copolymers has been investigated using swelling measurement, small-angle neutron scattering (SANS), and dynamic and static light scattering (DLS/SLS). It is known that weakly-charged polymer gels undergo microphase separation in a poor solvent as a result of competing interactions involving hydrophobic attraction versus electrostatic repulsion. The microphase separation is characterized by a scattering maximum in SANS intensity functions of which Bragg spacing, Λ, is around 20-30 nm. However, when gel size was reduced to the order of Λ, no microphase separation was observed. Instead, a typical scattering of isolated spherical particles was clearly observed. On the basis of the experimental evidence, we conclude that microphase separation has its own wavelength independent of gel size, and nanometer-order gels, i.e., nanogels, do not undergo microphase separation.     

NMR diffusion and relaxation studies during cement hydration—A non-destructive approach for clarification of the mechanism of internal post curing of cementitious materials

Internal post-curing of hardening cement pastes by addition of alginate spheres, which contain 98% of water, is studied by non-destructive ¹H NMR measurements of transverse relaxation time and self-diffusion. The onset and amount of water transition from the alginate gel used as additive with temporary delayed release of water to cement pastes was observed continuously during the dormant and accelerated period of cement hydration. During hydration, the water transition from the alginate into the cement matrix as well as the development of pore size is monitored quantitatively by studying the time dependence of characteristic peaks in the transverse relaxation time distribution. Comparison between samples without and with internal post curing shows that the addition of alginate gel does not influence the pore size in the micropore region. NMR diffusion studies demonstrate that the physically bound pore water has sufficient mobility to ensure homogeneous distribution of water from the alginate source into the surrounding cement matrix during the dormant and accelerated period.     

C-S-H/PCE凝胶对掺磷渣水泥的低温促凝早强性能研究

探讨C-S-H/PCE凝胶对掺磷渣硅酸盐水泥的低温促凝早强性能的影响,并通过上清液pH值、Ca²⁺浓度和化学结合水量分析其对水化的影响机理。低温下(8℃) C-S-H/PCE凝胶能有效缩短混凝土终凝时间,并提高早期强度,当掺量5%时,混凝土终凝时间缩短近6 h,16 h、24 h和3 d抗压强度比分别为160%、150%和110%,且不影响2.5 h混凝土工作性能。C-S-H/PCE凝胶能使低温下掺磷渣硅酸盐水泥浆体处于高pH状态,加速早期水泥矿相离子溶解,提高Ca²⁺过饱和度,加速后期析晶过程,提高化学结合水量,从而促进掺磷渣硅酸盐水泥的水化,实现低温促凝早强。     

NMR studies of hydrating cement: A spin-spin relaxation study of the early hydration stage

The early stages of cement hydration were investigated by proton spin-spin relaxation time (T_c) measurements because these experiments can be performed much faster (in several seconds) than the characteristic time for a change in hydration evolution. In addition, comparing the free induction decays of nuclear magnetization and its spin echoes allows the separation of solid-like and liquid-like proton groups. The values of T₂ and the associated magnetization fractions were monitored for cement pastes with different water/cement ratios in the first 20 hours of hydration.

Results show that already at the time of the first measurement, i.e. six minutes after mixing dry white cement powder with water, a quasi steady state is reached with protons distributed in three groups: loosely bound water (in the gel coatings and interstital spaces between coated clinker grains with T₂ of several ms), tightly bound water (T₂ 100μs) and water/hydroxyl protons in crystalline structure (T₂ 10 μs). The values of T₂ and their associated magnetizations are fairly constant during the first several hours with the solid-like components only slowly growing at the expense of the liquid one. The fraction of the loosely bound water as well as the absolute value of its T₂ increases with increasing w/c ratio. These data indicate that although nothing vigorous is happening in the dormant period of cement hydration there is a continuous growth of the solid matrix.     

Dynamic light scattering and small-angle neutron scattering studies on phenolic resin solutions

Solution properties of unfractionated phenolic resins prepared by polycondensation of phenol and formaldehyde using oxalic acid as a catalyst were investigated by dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The hydrodynamic radius, obtained by DLS experiments with 1 vol % solution in acetone, and the correlation length, ξ, of the Ornstein-Zernike equation, obtained by SANS experiments with 10 vol % solution in tetrahydrofuran, obey a power-law relation as a function of z-average molecular weight estimated by gel permeation chromatography, with scaling exponents of 0.57 and 0.27, respectively. These behaviors are unaffected by polymerization conditions, such as initial phenol-to-formaldehyde molar ratio in the range from 0.9 to 1.5, catalyst concentration with oxalic acid-to-phenol molar ratio from 0.01 to 0.1, and reaction time within the period in which the polymer remains soluble. SANS curves for polymers prepared under different conditions are sufficiently superimposed onto a single curve with the reduced variables, ξ⁻²I(q) and ξq. These results indicate that unfractionated phenolic resins have a self-similar structure with respect to the molecular weight.     

胶凝组分粒度特性对水泥性能影响的研究评述

介绍了具有胶凝活性的粉煤灰、矿渣、纳米材料的颗粒特性对水泥性能影响的研究,包括颗粒级配区间的优化、颗粒尺寸分布模型以及矿物掺合料的作用机理.细度对水泥强度的贡献很大,特别是在水化初期;目前大多研究中的紧密堆积模型采用fuller分布,可改善浆体的结构;高活性胶凝颗粒、水泥颗粒和低活性胶凝颗粒分别取代细、中和粗颗粒区间,可优化区间提高整体性能.最后对目前国内外研究成果的总结分析,展望了胶凝组分粒度特性的未来研究方向.     

Effect of Heat Treatment on the Pore Structure and Drying Shrinkage Behavior of Hydrated Cement Paste

The effect of a short heat treatment on hydrated cement paste has been investigated by measuring the weight and length changes of specimens as they undergo various combinations of heating, drying, and resaturation. Heating a cement paste to 60°C coarsens the capillary pore system, decreases the volume of mesopores, and increases the degree of polymerization of the silicates. In addition, the saturated weight of the paste is permanently decreased by a heat treatment. This weight loss can be explained by conversion of bound hydroxyl groups into liquid water during polymerization of the C-S-H gel phase. These experiments help reconcile and interpret published results describing the properties of cement cured at various temperatures, the effects of a short heat treatment on cement paste, and the thermal expansion behavior of saturated and dry cement paste.     

醇及醇胺类物质助磨效果量化评价方法的研究

通过实验室小磨试验,研究了三种醇及醇胺类物质的掺量与水泥样品45μm筛余、均匀性系数及标准稠度用水量的关系,建立了醇及醇胺类助磨剂助磨效果的量化评价方法。以助磨剂掺量为横坐标,分别以样品45μm筛余、均匀性系数及水泥标准稠度用水量为纵坐标绘制曲线,用纵坐标的变化值(与空白样相比)表征助磨效果的差异;曲线拐点对应的横坐标为助磨剂的饱和掺量,对应的纵坐标为达到最大助磨效果时的颗粒(或性能)特征。助磨剂的饱和掺量越小,饱和掺量对应的45μm筛余越小、均匀性系数越大及水泥标准稠度用水量越大时,该助磨剂的助磨效果越好。     

Neutron Polarization Analysis for Biphasic Solvent Extraction Systems

We performed neutron polarization analysis (NPA) of extracted organic phases containing complexes, comprised of Zr(NO₃)₄ and tri-n-butyl phosphate, which enabled decomposition of the intensity distribution of small-angle neutron scattering (SANS) into the coherent and incoherent scattering components. The coherent scattering intensity, containing structural information, and the incoherent scattering compete over a wide range of magnitude of scattering vector, q, specifically when q is larger than q* ≈ 1/R_g, where R_g is the radius of gyration of scatterer. Therefore, it is important to determine the incoherent scattering intensity exactly to perform an accurate structural analysis from SANS data when R_g is small, such as the aforementioned extracted coordination species. Although NPA is the best method for evaluating the incoherent scattering component for accurately determining the coherent scattering in SANS, this method is not used frequently in SANS data analysis because it is technically challenging. In this study, we successfully demonstrated that experimental determination of the incoherent scattering using NPA is suitable for sample systems containing a small scatterer with a weak coherent scattering intensity, such as extracted complexes in biphasic solvent extraction systems.