Effect of silica fume on pore structure and chloride diffusivity of low parosity cement pastes

This paper presents the results of an experimental investigation on the effect of silica fume on pore structure and diffusivity of low porosity cement pastes. For cement pastes with w/c ratios in the range of 0.20 to 0.30, a 10% replacement of the cement with silica fume only reduced the total porosity to a small extent. However, a refinement of the pore size distribution took place in such a way that the content of larger pores was reduced for decreasing w/c ratio. For pure portland cement pastes the effect of a certain constant change of w/c ratio on the chloride diffusivity was substantially higher at high w/c ratios than at low w/c ratios. A 10% replacement with silica fume reduced the chloride diffusivity for all w/c ratios so much that the effect of w/c ratio became less important.     

Preparation and characterization of a porous silicate material from silica fume

A porous silicate material derived from silica fume was successfully prepared and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FT-IR) spectroscopy, Thermogravimetry and Differential thermal gravity (TG-DTG), N₂ adsorption and desorption isotherms, and scanning electron microscopy (SEM). Raw silica fume was analyzed by XRD, FT-IR and SEM. The analysis results of silica fume indicated that SiO₂ in silica fume is mainly determined as amorphous state, and that the particles of raw silica fume exhibited characteristic spherical structure with a diameter of from 50 nm to 200 nm. The preparation of the porous silicate material involved two steps. The first step was the extraction of the SiO ₃ ^2? leachate from raw silica fume. The maximum value of SiO ₃ ^2? extraction yield was obtained under the following conditions: reaction temperature of 120 °C, reaction time of 120 min, NaOH concentration of 15%, and alkali to SiO₂ molar ratio of 2. The second step was the preparation of the porous silicate material though the reaction of SiO ₃ ^2? leachate and Ca(OH)₂ suspension liquid. The optimum preparation conditions were as follows: preparation temperature of 90 °C, preparation time of 1.5 h, Si/Ca molar ratio of 1 : 1, and stirring rate of 100 r/min. The BET surface area and pore size of the porous silicate material were 220.7 m²·g^?1 and 8.55 cm³/g, respectively. The porous silicate material presented an amorphous and unordered structure. The spectroscopic results indicated that the porous silicate material was mainly composed of Si, Ca, O, C, and Na, in the form of Ca²⁺, SiO ₃ ^2? , CO ₃ ^2? and Na⁺ ions, respectively, which agreed with the XRD, TG-DSC, and FT-IR data. The N₂ adsorption-desorption isotherm mode indicates that the porous silicate material belonged to a typical mesoporous material. The porous silicate material presented efficiency for the removal of formaldehyde: it showed a formaldehyde adsorption capacity of 8.01 mg/g for 140 min at 25 °C.     

Microcrystalline calcium hydroxide in Portland cement pastes of low water/cement ratio

A microcrystalline form of calcium hydroxide has been observed in Portland cement pastes of low water/cement ratio by transmission electron microscopy of sections thinned from bulk, hardened pastes. The typical morphology is of clusters of microcrystals in the form of lamellae 10nm thick, parallel to the basal plane. The lamellae tend to be aligned although the perfection of the alignment is variable. The clusters are embedded in the hydrate gel.     

An investigation on microstructure of cement paste containing fly ash and silica fume

In this study, high-calcium fly ash (HCFA) and silica fume (SF) were used as mineral admixtures. The effect of these admixtures on the microstructure of cement paste was investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The reaction of HCFA and SF with portlandite, which occurs in Portland cement (PC), forms a new calcium-silicate-hydrate (C-S-H) gel.     

The influence of silica fume on the mono/di silicate anion ratio during the hydration of CSF-containing cement paste

The influence of silica fume addition on silicate polymerization during hydration of portland cement pastes was studied. Trimethylsilyl derivatives were identified by gas-liquid chromatography. DTA/TGA method was applied for determination of the free lime content in hyrated paste samples. The obtained results point to the conclusion that pozzolanic reaction causes the shift towards Si-anion dimerization during hydration of csf-blended cement pastes.     

硅灰和减水剂对硅酸三钙水化调控机理的研究

采用XRD、精密水化微量热、ESEM、EDS和NMR等测试技术,研究了硅灰和聚羧酸减水剂对C3S水化的影响。结果表明：聚羧酸减水剂的掺入抑制了C3S的早期水化放热,而硅灰消耗了C3S水化产生的CH,促进了C3S的水化.两者都使C3S水化产物C-S-H凝胶的形貌由针棒状发生了转变,且其硅氧四面体的聚合状态有较大不同,尤其是硅灰显著影响了C-S-H凝胶硅氧四面体聚合状态中Q1、Q2的含量。     

The tricalcium silicate hydration in the presence of active silica

The influence of active silica upon the tricalcium silicate hydration was studied. On the microcalorimetric curves a considerable acceleration of the process with dormant period elimination was observed. The reason for this is the lowering of calcium ions concentration in the solution as they are consumed, rapidly by the CSH phase formation of a low C/S ratio. Basing on these results the authors presume that the delaying factor of C₃S hydration process is the quasi-stationary layer supersaturated with calcium ions surrounding the anhydrous grains of tricalcium silicate.     

Influence of silica fume on the microstructure of cement pastes: New insights from 1H NMR relaxometry

¹H NMR has been used to characterise white Portland cement paste incorporating 10 wt.% of silica fume. Samples were measured sealed throughout the hydration without sample drying. Paste compositions and C–S–H characteristics are calculated based on ¹H NMR signal intensities and relaxation analysis. The results are compared with a similar study of plain white cement paste. While the presence of silica fume has little influence on C–S–H densities, the chemical composition is impacted. After 28 days of sealed hydration, the Ca/(Si + Al) ratio of the C–S–H is 1.33 and the H₂O/(Si + Al) ratio is 1.10 when 10% of silica fume is added to the white cement. A densification of the C–S–H with time is observed. There are no major changes in capillary, C–S–H gel and interlayer pore sizes for the paste containing silica fume compared to the plain white cement paste. However, the gel/interlayer water ratio increases in the silica fume blend.     

The microstructural and hardening behaviour of tricalcium silicate pastes in the presence of calcium chloride

A sequential examination of strength development in terms of microhardness was studied during paste hydration of C₃S in the presence of 2 and 5% CaCl₂ and at w/s ratios of 0.3 or 0.5. An attempt has been made to relate strength with microstructural features studied by means of Scanning Electron Microscopy. Generally, at earlier periods it was found that the 2% addition of CaCl₂ gave the strongest material; the effect was most pronounced in the 6-month sample of the series with 0.3 w/s. The high strength for the sample prepared at a w/s ratio of 0.3 may be related to a high CaO/SiO₂ C-S-H-phase, low porosity, and possibly a hydrated calcium hydroxy chloride complex. The pore size distribution was also measured. In general, the higher the porosity the lower the strengths but the relationship was not perfectly linear even on the semi-logarithmic plot.     

Hydration characteristics of monocalcium aluminate at a low water/solid ratio

The hydration characteristics of calcium monoaluminate were studied using an effective water/aluminate ratio of 0.15 at 20° or 80°C, from a few minutes of two months. The material hydrated at 80°C shows a large shrinkage while at the lower temperature a continuous expansion occurs. The product at 80°C shows a much higher strength than that hydrated at 20°C. The main initial hydration products are 2Ca0, Aℓ₂0₃, 8H₂0 and alumina gel. Microcracks are developed in the products hydrated at 20°C while at the higher temperature a very compact mass results. The data indicate that it is possible to obtain a durable high alumina cement by using a low water/cement ratio and hydrating at higher temperatures, and under these conditions C₃AH₃---C₃AH₆ bond is favoured.     

Effect of water-to-cementitious materials ratio and silica fume on the autogenous shrinkage of concrete

This paper presents an experimental study on the autogenous shrinkage of Portland cement concrete (OPC) and concrete incorporating silica fume (SF). The results were compared with that of the total shrinkage (including drying shrinkage and part of the autogenous shrinkage) of the concrete specimens dried in 65% relative humidity after an initial moist curing of 7 days. The water-to-cementitious materials (w/c) ratio of the concrete studied was in the range of 0.26 to 0.35 and the SF content was in the range of 0% to 10% by weight of cement.The results confirmed that the autogenous shrinkage increased with decreasing w/c ratio, and with increasing SF content. The results showed that the autogenous shrinkage strains of the concrete with low w/c ratio and SF developed rapidly even at early ages. At the w/c ratio of 0.26, the autogenous shrinkage strains of the SF concrete were more than 100 micro strains at 2 days. For all the concretes studied, 60% or more of the autogenous shrinkage strain up to 98 days occurred in the first 2 weeks after concrete casting. The results indicated that most of the total shrinkage of the concrete specimens with very low w/c ratio and SF exposed to 65% relative humidity after an initial moist curing of 7 days did not seem to be due to the drying shrinkage but due to the autogenous shrinkage.     

Morphology and microstructure of autoclaved slag-clinker pastes in presence and absence of silica sand

Morphology and microstructure of autoclaved slag-clinker and slag-clinker-sand mixtures were undertaken using scanning electron microscopy. The microstructure of autoclaved slag-clinker hydration products displayed nearly amorphous, fibrous and radial plates of CSH phase, large cubes of hydrogarnet-like hydrates (mainly as C₃ASH₄) as well as hexagonal precipitations of calcium hydroxide. The hydration of slag-clinker-sand mixture (an optimum composition) was associated with the formation of semi-crystalline low-lime tobermorite (mainly as CSH(I)) as well as fibrous and massive plates of crystalline 11Å tobermorite as the main hydration products. The strength development could also be related with the microstructure of the formed hydrates.     

不同水灰比和流动度对水泥抗压强度的影响

<正>1问题的提出及分析在日常处理水泥质量用户投诉的过程中,不管什么环境温度和湿度条件下,我们都会碰到养护到期的混凝土表面起粉起砂现象,而所用水泥包括袋重在内的各项品质指标现场抽检结果均合格。分析认为,这主要是拌合水偏多,振动时比重轻的混合材浮在面上,造成了表面胶结能力差而引起的。     

On the frictional contribution to the viscosity of cement and silica pastes in the presence of adsorbing and non adsorbing polymers

This paper is devoted to the role of hydrodynamic lubrication in the flow of dense suspensions of non-Brownian cement or silica particles. The role of hydrodynamic lubrication is ambiguous since it is primarily a source of viscous dissipation but, by preventing direct contact between particles and friction, it may facilitate flow. We show that in the concentration and shear rate regimes investigated here direct contact friction between cement or silica particles is contributing to the overall energy dissipation. Addition of water-soluble polymers, either adsorbing or not adsorbing, was used as a mean to control friction. We show that, independently of the adsorption capacity of the polymer, it is the non adsorbed polymer which, thanks to hydrodynamic lubrication, prevents direct contacts and reduces the overall energy dissipation. This leads to the counterintuitive situation where by increasing the interstitial fluid viscosity, the suspension viscosity is decreased. When hydrodynamic lubrication is no longer able to avoid direct frictional contact, dilatant and shear-thickening behaviors set in.     

Tobermorite/jennite- and tobermorite/calcium hydroxide-based models for the structure of C-S-H: applicability to hardened pastes of tricalcium silicate, β-dicalcium silicate, Portland cement, and blends of Portland cement with blast-furnace slag, metakaolin, or silica fume

The purpose of this article is to discuss the applicability of the tobermorite-jennite (T/J) and tobermorite-‘solid-solution’ calcium hydroxide (T/CH) viewpoints for the nanostructure of C-S-H present in real cement pastes. The discussion is facilitated by a consideration of the author's 1992 model, which includes formulations for both structural viewpoints; its relationship to other recent models is outlined. The structural details of the model are clearly illustrated with a number of schematic diagrams. Experimental observations on the nature of C-S-H present in a diverse range of cementitious systems are considered. In some systems, the data can only be accounted for on the T/CH structural viewpoint, whilst in others, both the T/CH and T/J viewpoints could apply. New data from transmission electron microscopy (TEM) are presented. The ‘inner product’ (Ip) C-S-H in relatively large grains of C₃S or alite appears to consist of small globular particles, which are ≈4-8 nm in size in pastes hydrated at 20 °C but smaller at elevated temperatures, ≈3-4 nm. Fibrils of ‘outer product’ (Op) C-S-H in C₃S or β-C₂S pastes appear to consist of aggregations of long thin particles that are about 3 nm in their smallest dimension and of variable length, ranging from a few nanometers to many tens of nanometers. The small size of these particles of C-S-H is likely to result in significant edge effects, which would seem to offer a reasonable explanation for the persistence of Q⁰(H) species. This would also explain why there is more Q⁰(H) at elevated temperatures, where the particles seem to be smaller, and apparently less in KOH-activated pastes, where the C-S-H has foil-like morphology. In blended cements, a reduction in the mean Ca/Si ratio of the C-S-H results in a change from fibrillar to a crumpled-foil morphology, which suggests strongly that as the Ca/Si ratio is reduced, a transition occurs from essentially one-dimensional growth of the C-S-H particles to two-dimensional; i.e., long thin particles to foils. Foil-like morphology is associated with T-based structure. The C-S-H present in small fully hydrated alite grains, which has high Ca/Si ratio, contains a less dense product with substantial porosity; its morphology is quite similar to the fine foil-like Op C-S-H that forms in water-activated neat slag pastes, which has a low Ca/Si ratio. It is thus plausible that the C-S-H in small alite grains is essentially T-based (and largely dimeric). Since entirely T-based C-S-H is likely to have different properties to C-S-H consisting largely of J-based structure, it is possible that the C-S-H in small fully reacted grains will have different properties to the C-S-H formed elsewhere in a paste; this could have important implications.     

低水泥浇注料中纯铝酸钙水泥和SiO_2微粉的“老化”试验

为了探讨纯铝酸钙水泥结合的低水泥浇注料"老化"的原因和影响因素,将SiO2微粉以及不同粒度、不同物相组成(CA相含量)、不同新鲜程度的纯铝酸钙水泥在温度为(20±1)℃、相对湿度>75%的潮湿环境中摊成厚度为2.5 cm左右的料层,放置一定时间(分别为0、3、7、14、28 d)使其老化,然后分别将它们与特级矾土(≤5、≤0.088 mm)、磷酸盐分散剂和减水剂等其他原料一起配制成浇注料,通过测定浇注料的可工作时间、初始流动性和早期(6 h)养护强度,来表征这些原料的老化速度.结果表明:(1)纯铝酸钙水泥的cA含量和细度越高,其老化速度越快.(2)"新鲜"的铝酸盐水泥比存放一段时间后的水泥的老化速度更快.(3)SiO2微粉的老化会导致浇注料的流动性变差,可工作时间变短.     

Morphology and microstructure of autoclaved clinker and slag-lime pastes in presence and in absence of silica sand

Development of microstructure in four hydrothermal reactions has been undertaken using scanning electron microscopy. These are clinker, clinker-sand, slag-lime and slag-lime-sand hydrothermal reactions. The microstructure of clinker hydration products displayed crumpled foils and tabular masses of calcium silicate hydrates; few cubic crystals of hydrogarnet appeared only during the initial stage of the reaction. In clinker-sand mixture the C-S-H phase was the only product identified. In slag-lime hydration the microstructure displayed both of the hydrogarnet crystals and the C-S-H phase. The hydration of slag-lime-sand mixture (an optimum composition) was associated with the formation of ill-crystallized tobermorite and crystalline 11A tobermorite as the main products.     

Effect of calcium to silica ratio on the synthesis of calcium silicate hydrate in high alkaline desilication solution

High alkaline desilication solution (DSS), a high volume byproduct from the pretreatment of high-alumina fly ash, was used as low-cost mother liquor for the synthesis of calcium silicate hydrate (C-S-H). Through the combined analysis of X-ray diffraction, thermogravimetric analysis, X-ray fluorescence, ²⁹Si MAS NMR, and Brunauer-Emmett-Teller, the relationship between chemical composition and structure of C-S-H synthesized under Ca/Si of 0.83:1 to 2.0:1 was investigated. Silicon conversion and yield of product have a positive correlation with Ca/Si. Sodium uptake in C-S-H is inhibited as Ca/Si increases. The formation of sodium in C-S-H transfers from “bound Na” to “mobile Na” and aluminum from tetrahedrally coordinated Al (IV) to octahedrally coordinated Al (VI). The increase of Ca/Si leads to shortening of silicate chain and formation of more dimers, which causes more water bound in C-S-H. The mechanism of calcium addition on silicate chain obtained from DFT calculation primarily results from more interlayer calcium occurrence to affect bridging tetrahedron and cationic bounding states reorganization. Reasonable control for Ca/Si momentously contributes to the adjustment for composition and structure of C-S-H synthesized in DSS.     

On loci of acrylonitrile polymerization with bisulfite-persulfate initiators under the conditions of low water/monomer ratio

In the preparation of acrylonitrile–vinylacetate copolymer (93:7 in weight) by continuous polymerization in aqueous medium using the complete mixing type reactor, the author and co-workers studied the effects of the water/monomer ratio on polymer properties and polymerization. They reported that the structure of a polymer particle becomes more compact with decreasing water/monomer ratio. This was noted in studying the physical properties of the polymer and the formation of polymer particles in this system. ^1,2 Here the author has performed kinetic studies based on the results of polymerization to determine the loci of the polymerization in the range of water/monomer ratio roughly from 1.75 to 4.0. Most of the primary radicals from the initiators attack the monomers in the aqueous phase to form monomer radicals attached to initiator fragments, and most of the monomer radicals grow to form polymer radicals until termination occurs in the aqueous phase. Hence, the loci of polymerization in this system are not the surfaces and inner parts of the polymer particles, the diameters of which are roughly from 20 to 60 μm observed by a microscope, but the aqueous phase excluding these particles.