Hydration kinetics and microstructure development of normal and NaAlO2-activated Al-doped β-C2S pastes

Sodium aluminate (NaAlO₂) can be used to accelerate hydration of Portland cements. Here, we compare the use of NaAlO₂ solutions with deionized water on the hydration of Al-doped β-C₂S. The microstructure development of hydration product C-S-H obtained from hydrated Al-doped β-C₂S was investigated. NaAlO₂ significantly improved the hydration kinetics of Al-doped β-C₂S due to the enhancement in the precipitation of calcium hydroxide and stimulation of C-(A)-S-H nucleation and increased the early-age mechanical strength of Al-doped β-C₂S pastes. NaAlO₂ promoted the incorporation of Al in the C-(A)-S-H structure and accelerated the formation of C-(A)-S-H phases containing tetra-, penta- and hexa-coordinated Al in its composition. The alkali cations modified the electrostatic equilibrium of the C-(A)-S-H, thus promoting the development of the nano-mechanical properties.     

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.     

C–(N)–S–H and N–A–S–H gels: Compositions and solubility data at 25°C and 50°C

Calcium silicate hydrates containing sodium [C–(N)–S–H], and sodium aluminosilicate hydrates [N–A–S–H] are the dominant reaction products that are formed following reaction between a solid aluminosilicate precursor (eg, slags, fly ash, metakaolin) and an alkaline activation agent (eg NaOH) in the presence of water. To gain insights into the thermochemical properties of such compounds, C–(N)–S–H and N–A–S–H gels were synthesized with compositions: 0.8≤Ca/Si≤1.2 for the former, and 0.25≤Al/Si≤0.50 (atomic units) for the latter. The gels were characterized using thermogravimetric analysis (TGA), scanning electron microscopy with energy‐dispersive X‐ray microanalysis (SEM‐EDS), and X‐ray diffraction (XRD). The solubility products (K_S0) of the gels were established at 25°C and 50°C. Self‐consistent solubility data of this nature are key inputs required for calculation of mass and volume balances in alkali‐activated binders (AABs), and to determine the impacts of the precursor chemistry on the hydrated phase distributions; in which, C–(N)–S–H and N–A–S–H compounds dominate the hydrated phase assemblages.     

Alkali activation of a novel calcium‐silicate hydraulic binder with CaO/SiO2 = 1.1

A quasi‐amorphous low‐calcium‐silicate hydraulic binder, with an overall CaO/SiO₂ (C/S) molar ratio of 1.1, was produced. This cementitious material was then hydrated with aqueous solutions containing 3 wt% alkalis (either NaOH, Na₂CO₃ or Na₂SiO₃). The evolution of the hydration processes of the samples were monitored by compressive strength testing, XRD, FTIR, ²⁹Si and ²⁷Al MAS NMR, isothermal calorimetry and TGA. It was found that the nearly exclusive hydration product formed was a C‐S‐H phase with a semi‐crystalline structure. More importantly, the paste prepared with the Na₂SiO₃ solution developed compressive strength values similar to those of ordinary portland cements (OPC) with faster early age kinetics. In addition, the isothermal calorimetry results indicated that these new hydraulic binders present much lower heat of hydration values compared with a traditional OPC. The results presented here open the possibility of producing cement with a compressive strength comparable to that of OPC but with lower CO₂ emissions during the production process and with lower hydration heat related problems during the production of concrete structures.     

Gel Composition and Strength Properties of Alkali‐Activated Oyster Shell‐Volcanic Ash: Effect of Synthesis Conditions

The gel composition and mechanical properties of alkali‐activated oyster shell‐volcanic ash were investigated at different NaOH concentrations (8, 12, and 15M) and curing temperatures (60°C and 80°C) in wet and dry conditions. XRD, FTIR, SEM‐EDS, and TGA‐DSC were used for microstructural characterization of the binder. The gel composition of the system was found to be influenced by NaOH concentration and was not affected when curing temperature was varied from 60°C to 80°C. The main phase was N,C–A–S–H for all alkali‐activated oyster shell‐volcanic ash, with C–S–H as secondary phase for some samples and contains high percentage of iron. The splitting at υ₃ = 1400–1494 cm^?1 on FTIR spectra corresponded to the elimination of the degeneracy due to the distortion of CO₃^2? group. The high degree of splitting indicated that this carbonate group is linked to Ca²⁺. The compressive strength was influenced by curing temperature and the formation of a secondary phase. The compressive strength in dry condition increased roughly between 28 and 180 d for some samples, while in wet condition, the partial dissolution of Si–O–Si bonds of some silicate phases resulted in a reduction of strength.     

Hydrothermal Treatment of a Silica Sand Complex with Lime

The feasibility of using relatively low-purity silica as the starting material for hydrothermal solidification was investigated from the consideration of effective utilization of natural resources. Hydrothermal solidification was performed at 140°–180°C for periods ranging from 2 to 40 h using a mixture of 80% silica sand (containing 67% quartz, 22% clay minerals (mica, clinochlore, and kaolinite), and 7% feldspar) and 20% Ca(OH)₂. Within the range of experimental conditions, the flexural strength of the solidified bodies increased with increased treatment temperature and treatment time, reaching values of up to 20 MPa. The flexural strength was proportional to the amount of, but independent of the type of, reaction products. Hydrogarnet and C-S-H were formed in the initial stages of the reaction; the amount of these phases tended to decrease, and 1.1 nm tobermorite formed as the reaction further progressed. These results indicated that hydrogarnet and C-S-H were precursors of 1.1 nm tobermorite.     

Aqueous Solubility Diagrams for Cementitious Waste Stabilization Systems: II, End-Member Stoichiometries of Ideal Calcium Silicate Hydrate Solid Solutions

Solubility in the fully hydrated CaO–SiO₂–H₂O system can be best described using two ideal C-S-H-(I) and C-S-H-(II) binary solid solution phases. The most recent structural ideas about the C-S-H gel permit one to write stoichiometries of polymerized C-S-H-(II) end-members as hydrated precursors of the stable tobermorite and jennite minerals in the form of 5Ca(OH)₂·6SiO₂·5H₂O and 10Ca(OH)₂·6SiO₂·6H₂O, respectively. For thermodynamic modeling purposes, it is more convenient to express the number of basic silica and portlandite units in these stoichiometries using the coefficients n _Si and n _Ca. Thermodynamic solid-solution aqueous-solution equilibrium modeling by applying the Gibbs energy minimization (GEM) approach shows the best generic fits to the available experimental solubility data at solid 0.8 < Ca/Si < 2.0 if both stoichiometry and thermodynamic constants of the end-members are normalized to n _Si= 1.0 ± 0.3. Recommended stoichiometries and thermodynamic data for the C-S-H end-members provide a reliable basis for the subsequent multicomponent extension of the ideal C-S-H solid solution model by incorporation of end-members for the (radio)toxic elements or trace metals.     

Effect of Silicate Anion Structure on Fixation of Chloride Ions by Calcium Silicate Hydrates

Calcium silicate hydrates, CaO–SiO₂-H₂O (C-S-H), were studied as a chloride fixation material. C-S-H of two different CaO/SiO₂ ratios were synthesized and burned with calcium chloride in a temperature range from 600° to 1000°C. Minerals with a chemical composition of CaO·SiO₂·CaCl₂ and 9CaO·6SiO₂·CaCl₂ were identified by X-ray diffraction analysis. Comparing the diffraction intensity, it was found that the most efficient chloride fixation was attained when burned at 800°C. Changes in the morphology of silicate anion associated with burning and fixation of the chloride were studied in terms of chloride fixation capability using the trimethylsililation technique. It was confirmed that some silicate anions formed a glassy infinite chain where the chloride ions were fixed as a solid solution.     

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.     

盐湖地区混凝土的长期腐蚀产物与腐蚀机理

运用XRD,DTA—TG,SEM—EDAX和IR方法研究了盐湖地区暴露20a的实际混凝土工程的腐蚀产物,发现了混凝土在盐湖卤水腐蚀条件下3种类型的化学腐蚀。首次报道了盐湖卤水中的碱金属离子对水化硅酸钙(CSH)的两种腐蚀产物,即水化硅酸钙水硅酸镁CSH—MSH的过渡产物含水硅酸钙镁凝胶(C1—xMx)1．15～1．70SH(x＝0．22～0．39)以及Na离子取代Ca的碱硅凝胶产物(C1—xNx)1.85～1．60SH(x＝0．39～0．63)。此外,还提出了水泥的3种水化产物即氢氧钙石(CH)、水化铝酸钙(C3AH6)和水化硅酸钙(CSH)在盐湖地区的化学腐蚀机理。     

Highly Reactive β-Dicalcium Silicate: II, Hydration Behavior at 25°C Followed by 29Si Nuclear Magnetic Resonance

The hydration behavior at 25°C of highly reactive β-dicalcium silicate synthesized from hillebrandite (Ca₂(SiO₃)(OH)₂) was studied over a period of 7 to 224 d using ²⁹Si magic-angle spinning nuclear magnetic resonance (MAS NMR). The hydration product, C-S-H, contains Q² and Q¹ silicate tetrahedra, the chemical shifts of which are independent of the water/solid (w/s) ratio and curing time. Until the reaction is completed, the amounts of Q¹ and Q² formed are independent of the w/s ratio, being determined only by the degree of reaction. The ratio Q²/Q¹ increases as the reaction progresses and as the curing time becomes longer. From the values of Q²/Q¹, it appears that the hydrate is a mixture of dimers and short single-chain polymers. The Ca/Si ratio of the hydrate is high, taking values close to 2.0, but the Ca/Si ratio does not influence the Q²/Q¹ ratio. It was also found that the NMR peak intensities allow quantitative assessment similar to XRD.     

铬酸钙溶解动力学研究及溶解度测定

为了认识了解铬酸钙的溶解规律,同时获得补充铬酸钙的溶解度数据,实验在2 L压力釜内进行,通过测定50、80、100℃下溶液中铬浓度随时间的变化,结合经验公式并使用工具软件O rigin求出了其溶解速率常数和级数。经过足够长时间得到的不变的铬酸钙浓度记为该温度下的溶解度。实验结果表明,沸腾条件下,铬酸钙溶解速率大大加快,随温度升高,铬酸钙溶解度单调下降。统计分析表明,误差较小,结果有较好的可信度。     

Hydrothermal Solidification of Kaolinite–Quartz–Lime Mixtures

The strength development of hydrothermally solidified kaolinite–quartz–lime systems with kaolinite as the aluminum source was studied. The starting materials were mixed so that the Ca/(Si + Al) atomic ratio was in the range 0.23 to 0.25, and the Al/(Si + Al) ratio was between 0 to 0.50. Specimens were formed by uniaxial pressing and hydrothermal treatment under saturated steam pressure at 200°C for 2 to 20 h. For quartz-rich systems with Al/(Si + Al) = 0 and 0.05, strength development by the formation of calcium silicate hydrates, such as C–S–H and tobermorite (Ca₅(Si₆O₁₈H₂)·(4H₂O), was observed. On the other hand, in the case of kaolinite-rich systems with Al/(Si + Al) = 0.24 to 0.50, strength development by the formation of hydrogarnet (Ca₃Al₂(SiO₄)(OH)₈) was recognized, resulting in flexural strengths between 15 to 20 MPa. It is proposed that strength development is related to the formation of mesopores (∼0.04 μm) that accompanied formation of the hydrogarnet.     

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.     

Hydration Reactivity of Crystalline and Vitrified Diopside under Hydrothermal Conditions

Hydration reactivity of diopside in both the crystalline and amorphous (glassy) phase was studied under hydrothermal conditions. Samples were treated in an autoclave at 200°C in saturated vapor for 24 and 72 h. The progress of hydration was determined by X-ray powder diffractometry and IR spectroscopy. Results indicated that crystalline diopside possessed poor hydraulic activity. However, once vitrified it proved to be much more reactive. The principal hydration products found for the glassy diopside after 24 and 72 h of treatment were calcium silicate hydrate (xonotlite) and magnesium silicate hydrates (chrysotile and tremolite).     

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％,...     

Crystallization of calcium silicate hydrates on the surface of nanomaterials

The poorly crystalline calcium silicate hydrate (C‐S‐H) is the primary binding phase in portland cement concrete. In this paper, the influence of adding anatase phase nano‐TiO₂, nano‐SiO₂, graphene oxide (GO), and multiwalled carbon nanotubes (CNT) on the crystallization and morphology of C‐S‐H are systematically investigated through tests. C‐S‐H gels were prepared using the double decomposition method, and the nanomaterial additions of nano‐TiO₂, nano‐SiO₂, GO, and CNT were 2 wt%, 2 wt%, 0.5 wt%, and 0.5 wt%, respectively. X‐ray diffraction (XRD) results show that a more crystalline nanostructure of C‐S‐H is induced by the addition of nano‐TiO₂ or GO. This phenomenon is further confirmed by the transmission electron microscopy (TEM) observations. The TEM observations demonstrate that C‐S‐H would grow on the crystal face of TiO₂ to form nanocrystalline regions with a lattice fringe spacing of 3.0 Å. When incorporated with GO, it will form a square lattice structure with a lattice constant of 3.1 Å on the surface of GO and later change to the lattice fringe structure with a spacing of 3.1 Å on the region bit away the GO surface. However, when adding nano‐SiO₂ or CNT, these nanocrystalline regions are not observed. Further characterization through scanning electron microscopy (SEM) and atomic force microscopy (AFM) has been performed to investigate the effect of nanomaterials on C‐S‐H morphology. Different nanomaterials take a different morphology of C‐S‐H: sheet‐shape structures for pure C‐S‐H, rod‐shape with for C‐S‐H with nano‐TiO₂, and granular agglomeration for C‐S‐H with nano‐SiO₂. C‐S‐H with GO or CNT forms a structure of C‐S‐H growing on the templates.     

Interactions between Polymeric Dispersants and Calcium Silicate Hydrates

To better understand the mechanism of interaction between hydrating silicate-based cements and polymeric dispersants of the type used as superplasticizers in modern construction concretes, two different types of polymeric dispersant were added (at concentrations of 1 and 10 g/L) during the synthesis of calcium silicate hydrate (C-S-H) via the pozzolanic reaction in dilute slurries of lime and reactive silica, at Ca/Si ratios in the range of 0.66–1.50. Although both polymers gave degrees of adsorption of >79% in all cases studied, no significant structural modifications of the resulting C-S-H products were observed via X-ray diffraction or ²⁹Si magic angle spinning–nuclear magnetic resonance. These results differ from recent work in which it was shown that similar types of polymer could intercalate into the interlayers of C-S-H that was made using an alternative process. It is suggested that the process by which the C-S-H is formed may have a strong influence on whether C-S-H can intercalate polymers. This observation is relevant to understanding the fate of such polymers in concrete.