Effects of functionality and stereochemistry of small organic molecules on the hydration of tricalcium silicate

The retardation and the maximum rate of tricalcium silicate (C₃S) hydration induced by organic molecules were rarely measured as a function of their molar concentration and prevent us to identify the effect of specific functional groups carried by the molecules. In this study, the maximum rate of C₃S hydration which is proportional to the maximum heat flow and the retardation led by different concentrations of organic molecules was determined using the monitored calorimetric curves of the C₃S pastes. The effect of the charge, functionality and stereochemistry was studied by using a set of sugar alcohols (d-glucitol, d-galactitol…), sugar acid anions (d-gluconate, d-galactarate…), carboxylate (adipate) and amines with functionalized sulfonate, carboxylate and phosphonate groups (EDTA, EDTMP…).This study reveals that the maximum rate of C₃S hydration is enhanced in the presence of the organic molecules and that the retardation is increased with their concentration. The nature of the ending functional group of the molecules (hydroxyl, hydroxy-carboxylate, carboxylate, sulfonate or phosphonate), their main chain group (hydrocarbon or polyol chain) and the stereochemistry of their hydroxyl groups are shown to play a role.     

Adhesion properties of soy protein crosslinked with organic calcium silicate hydrate hybrids

The objective of this work was to investigate if inorganic calcium silicate hydrate (CSH) hybrids would improve soy protein wet adhesion properties. 3‐aminopropyltriethoxysilane (APTES) was used as a crosslinking agent to make covalent linkage between organic soy protein and inorganic CSH phases. Soy protein–calcium silicate hydrate (MSP‐CSH) composites with different mole ratio of APTES were prepared and the effect of crosslinking reaction on physicochemical properties such as thermal, rheological, FTIR spectroscopic, and morphological and adhesion properties were studied with physical aging effect. Covalent linkage was observed between CSH and soy protein using the FTIR technique. With aging effect, the denaturation temperature (T_d) and enthalpies (ΔH_d) of each fraction of soy protein increased in DSC thermograms, representing higher thermal stability, and the viscoelasticity of the composites also increased. The roughly coated surface of the MSP‐CSH composite was observed in SEM images. All these changes further confirmed the interaction between CSH and soy protein molecules. Dry and wet adhesion strength of the MSP‐CSH composites was higher than the control MSP alone. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40693.     

The effect of pressure on tricalcium silicate hydration at different temperatures and in the presence of retarding additives

The hydration of tricalcium silicate (C₃S) is accelerated by pressure. However, the extent to which temperature and/or cement additives modify this effect is largely unknown. Time-resolved synchrotron powder diffraction has been used to study cement hydration as a function of pressure at different temperatures in the absence of additives, and at selected temperatures in the presence of retarding agents. The magnitudes of the apparent activation volumes for C₃S hydration increased with the addition of the retarders sucrose, maltodextrin, aminotri(methylenephosphonic acid) and an AMPS copolymer. Pressure was found to retard the formation of Jaffeite relative to the degree of C₃S hydration in high temperature experiments. For one cement slurry studied without additives, the apparent activation volume for C₃S hydration remained close to ~ ? 28 cm³ mol^? 1 over the range 25 to 60 °C. For another slurry, there were possible signs of a decrease in magnitude at the lowest temperature examined.     

The effect of ionic polymers on the hydration of C3S

Composite materials were prepared from C₃S and 12% (1) vinyl sulfonic acid (2) p-styrene sulfonic acid. The hydration of the composite systems were compared to that of neat C₃S for different ages up to 90 d, by DTA-TG, IR and XRD. The polymers were found to retard the hydration of the silicate due to the interaction between the Ca²⁺ ions, released during the hydration of C₃S, and the sulfonate group of the polymers.     

Effect of calcium formate on the hydration of tricalcium silicate

The effect of 0, 0.5, 1.0, 2.0, 4.0 and 6.0% of calcium formate on the hydration of C₃S has been studied. Free lime determinations, non-evaporable water content, pH of the liquid phase, zeta potential, thermal analysis and infrared spectral studies have been made for understanding the mechanism of action of calcium formate. Results indicate that calcium formate acts as an accelerator up to 2%. Above this concentration, the excess of it has practically no effect.     

Effect of gypsum on C3S hydration

The effect of gypsum on the early stages of C₃S hydration is explored by means of DTA, high-resolution STEM, and liquid phase studies.     

The effect of dicalcium silicate (C2S) and tricalcium silicate (C3S) on the thermal stability of vinyl-type polymer concrete

The effect of anhydrous cement on the thermal stability of vinyl-type polymer concretes has been studied by investigating the interaction between the polymers and the calcium compounds of cement. It was proven from differential scanning calorimetry that C₂S and C₃S have a significant effect on the thermal stability of polymethyl methacrylate and polystyrene. From infrared analysis, the reaction mechanism appears to occur between the calcium oxide in the filler and the -CH₂- groups in the polymer. Polymer concrete containing 17 wt% C₂S maintained excellent strength after exposure for 30 days to 25% brine solutions and to air at 238°C.     

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。     

Pore solution in alkali-activated slag cement pastes. Relation to the composition and structure of calcium silicate hydrate

In this work, the relationship between the composition of pore solution in alkali-activated slag cement (AAS) pastes activated with different alkaline activator, and the composition and structure of the main reaction products, has been studied. Pore solution was extracted from hardened AAS pastes. The analysis of the liquids was performed through different techniques: Na, Mg and Al by atomic absorption (AA), Ca ions by ionic chromatography (IC) and Si by colorimetry; pH was also determined. The solid phases were analysed by XRD, FTIR, solid-state ²⁹Si and ²⁷Al NMR and BSE/EDX.The most significant changes in the ionic composition of the pore solution of the AAS pastes activated with waterglass take place between 3 and 24 h of reaction. These changes are due to the decrease of the Na content and mainly to the Si content. Results of ²⁹Si MAS NMR and FTIR confirm that the activation process takes place with more intensity after 3 h (although at this age, Q² units already exist). The pore solution of the AAS pastes activated with NaOH shows a different evolution to this of pastes activated with waterglass. The decrease of Na and Si contents progresses with time.The nature of the alkaline activator influences the structure and composition of the calcium silicate hydrate formed as a consequence of the alkaline activation of the slag. The characteristic of calcium silicate hydrate in AAS pastes activated with waterglass is characterised by a low structural order with a low Ca/Si ratio. Besides, in this paste, Q³ units are detected. The calcium silicate hydrate formed in the pastes activated with NaOH has a higher structural order (higher crystallinity) and contains more Al in its structure and a higher Ca/Si ratio than those obtained with waterglass.     

Physicochemical effects of nanosilica on C3A/C3S hydration

In this paper, C₃A-gypsum and C₃A-C₃S-gypsum model cement systems with and without nanosilica were studied. The effects of nanosilica on the early stage cement hydration, particularly C₃A hydration, were assessed through the heat of hydration (isothermal calorimetry), phase assemblage (quantitative X-ray diffraction), zeta potential, ion concentration measurements, and morphology (scanning electron microscopy) examinations. The results indicate that while promoting C₃S hydration, nanosilica retarded C₃A hydration in both the systems studied. The retardation was caused by the adsorption and coverage of nanosilica on C₃A surfaces through the electrostatic interaction, thus decreasing the C₃A dissolution rate and hindering the precipitation of hydration products. Consequently, the reduced gypsum consumption rate and the seeding effect of nanosilica further promoted C₃S hydration. These findings suggest that nanosilica and other silica-based nanoparticles can physicochemically influence hydration of cement-based materials, and a better understanding of these influencing mechanisms can help optimize performances of nanoparticle-modified cement-based materials.     

Effect of temperature on the microstructure of calcium silicate hydrate (C-S-H)

Temperature affects the properties of concrete through its effect on the hydration of cement and its associated microstructural development. This paper focuses on the modifications to C-S-H induced by isothermal curing between 5 and 60 °C. The results show that as the temperature increases (within the range studied) the C/S ratio of C-S-H changes only slightly, with a higher degree of polymerisation of silicate chains, but there is a significant decrease in its bound water content and an increase of apparent density of 25%. This increase seems to come from a different packing of C-S-H at the nanoscale. As a consequence of these changes, the microstructure of the cement paste is much coarser and porous, which explains the lower final strengths obtained by curing at elevated temperatures.     

THF hydrate crystal growth inhibition with small anionic organic compounds and their synergistic properties with the kinetic hydrate inhibitor poly(N-vinylcaprolactam)

Small, cationic tetraalkylammonium ions (particularly for alkyl=butyl or pentyl) are known to inhibit tetrahydrofuran (THF) and natural gas hydrate crystal growth and have been used as synergists for commercial kinetic hydrate inhibitor polymers (KHIs), such as N-vinylcaprolactam polymers, for a number of years. The ability for small, organic anionic molecules to inhibit (THF) hydrate crystal growth and their potential as KHI synergists in blends with poly(N-vinylcaprolactam) have been investigated. Several series of sodium alkyl carboxylates, sulphates and sulphonates were synthesised. It was found that none of these molecules were capable of inhibiting THF hydrate crystal growth as well as the best tetraalkylammonium salts. Alkyl carboxylates appeared to be more effective as inhibitors than the sulphonates or sulphates. The most effective anionic THF hydrate crystal growth inhibitors had butyl or pentyl groups, with alkyl branching at the tail (i.e. iso- rather than n-isomers) being advantageous. Anionic carboxylate molecules, particularly with isopentyl or isobutyl groups, showed some kinetic inhibition synergy with poly(N-vinylcaprolactam) lowering the onset and catastrophic hydrate formation temperatures in high pressure (78 bar) constant cooling experiments with Structure II hydrates by 1–2 °C when dosed at 2500 ppm compared with using 2500 ppm polymer alone. This synergism was however less than the best tetraalkylammonium salts (alkyl=n-butyl or n-pentyl) at the same test conditions. Sodium butyl sulphonate and sodium 4-methylpentanoate did not prevent hydrate agglomeration with 3.6% brine and decane at 25% water cut in stirred sapphire cells when dosed at 20,000 ppm based on the aqueous phase, whereas 10,000–20,000 ppm active material of several commercially available anti-agglomerants gave fine transportable slurries and no hydrate deposits at the same conditions.     

Influence of aluminium on the conversion of calcium silicate hydrate gels into 11 Å tobermorite at 90°C and 120°C

Mixtures of CaO and colloidal silica with and without γ-A?₂O₃, CaO and alkali-bearing A?₂O₃-SiO₂ gels, or CaO and clinoptilolite were treated hydrothermally at 90°C or 120°C for 4 hr – 4 weeks. Reaction seemed always to proceed through formation of C-S-H gels to 11 Å tobermorite. In the absence of A?, tobermorite crystallized more rapidly at c/S = 1.0 than at C/S = 0.8 but in the presence of A?, it crystallized more rapidly at Ca/(Si + A?) = 0.8 than at Ca/(Si + A? = 1.0. Where the starting materials contained both A? and alkali the tobermorite showed anomalous thermal behaviour similar to that of the natural mineral from Loch Eynort, but where they contained A? but no alkali, the thermal behaviour of the tobermorite was complex.     

The effect of water-to-cement ratio on the hydration kinetics of tricalcium silicate cements: Testing the two-step hydration hypothesis

Recent efforts to model tricalcium silicate based cements assume a two-step hydration mechanism where, in the first step, the empty space between cement particles rapidly fills with a low density calcium silicate hydrate (C-S-H) and in the second step, the thus formed C-S-H densifies slowly. This gives rise to models that nicely mimic the shape of experimentally observed hydration calorimetry curves and explains the transition between Stage 3 (acceleration) and Stage 4 (decreasing rate) hydration as well as post Stage 4 continued slow reaction. If this mechanism is correct, however, one would expect that the amount of heat energy released should increase with available space between particles, i.e. with water-to-cement ratio. A series of experiments, wherein the water-to-cement ratio was systematically varied showed little or no increase in total heat released when the water-to-cement ratio was doubled or tripled suggesting that the two-step mechanism may need revision.     

蛋白质与有机小分子反应机理的研究

评述了有机小分子与蛋白质的相互作用机理的研究结果和研究方法。     

Reactive molecular simulation on the ordered crystal and disordered glass of the calcium silicate hydrate gel

Modifying the properties of modern concrete highlights the decoding the molecular structure of C–S–H gel, which is the main binding phase in the cementitious materials. In this paper, the structural, dynamical and mechanical properties were investigated by using C–S–H glassy model and its crystal analog tobermorite 11 Å to represent the disordered and ordered molecular structure. By using reactive force field molecular simulation, the structural discrepancy for ordered and disordered phase was illustrated in respect of silicate chain skeletons, local structure of the calcium oxygen octahedrons and hydroxyl distribution. In the glassy model, the local structure of C–S–H gel, with defective silicate chains and distorted calcium sheet, is similar to the silicate glass phase of metallic ions. Furthermore, to predict the mechanical properties of the C–S–H gel and tobermorite, uniaxial tension testing by the reactive force field coupled with both the mechanical response and chemical response during the large tensile deformation process. During the tensile process, water molecules, attacking the Si–O and Ca–O bond, are detrimental to the cohesive force development in the C–S–H gel.     

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.     

C3S and C2S hydration in the presence of Na2CO3 and Na2SO4

This study analyses the behavior of calcium silicates C₃S and C₂S hydrated in two alkaline media, Na₂CO₃ and Na₂SO₄. The silicates were synthesized with laboratory reagents and hydrated in water, to which solid‐state alkaline activators with 4 wt% Na₂CO₃ or 4 wt% Na₂SO₄ were added. Two‐ and 28‐day mechanical strength values were determined and the reaction products were characterized with XRD, SEM/EDX, and ²⁹Si and ²³Na MAS NMR. The findings showed that the presence of Na₂CO₃ hastened hydration kinetics and stimulated early‐age mechanical strength development in both silicates. The most significant effect of sodium sulfate, however, was observed in the 28‐day material in both silicates, in which it raised strength by stimulating the precipitation of C–S–H gels with a high percentage of Q² units.     

Models for the composition and structure of calcium silicate hydrate (C---S---H) gel in hardened tricalcium silicate pastes

Models for the structure of C---S---H gels occuring in hardened C₃S cement pastes are considered and compared to some examples in which composition and silicate anion structure have been investigated experimentally.