Pair distribution function analysis of nanostructural deformation of calcium silicate hydrate under compressive stress

Despite enormous interest in calcium silicate hydrate (C–S–H), its detailed atomic structure and intrinsic deformation under an external load are lacking. This study demonstrates the nanostructural deformation process of C–S–H in tricalcium silicate (C₃S) paste as a function of applied stress by interpreting atomic pair distribution function (PDF) based on in situ X‐ray scattering. Three different strains in C₃S paste under compression were compared using a strain gauge, Bragg peak shift, and the real space PDF. PDF refinement revealed that the C–S–H phase mostly contributed to PDF from 0 to 20 Å whereas crystalline phases dominated that beyond 20 Å. The short‐range atomic strains exhibited two regions for C–S–H: I) plastic deformation (0‐10 MPa) and II) linear elastic deformation (>10 MPa), whereas the long‐range deformation beyond 20 Å was similar to that of Ca(OH)₂. Below 10 MPa, the short‐range strain was caused by the densification of C–S–H induced by the removal of interlayer or gel‐pore water. The strain is likely to be recovered when the removed water returns to C–S–H.     

Mineralogical Characterizations and Reaction Path Modeling of the Pozzolanic Reaction of Fly Ash–Lime Systems

Mineralogical studies show that fly ash–lime systems without NaOH produced Al-rich calcium silicate hydrates and a small amount of ettringite. The presence of NaOH accelerates the pozzolanic reaction of fly ash. Fly ash–lime systems with NaOH produced Al-rich calcium silicate hydrates, calcite, meixnerite, and NaX-type zeolite (or zeolite precursor) after 28 days of reaction time. Carbonation of alkali-activated fly ash–lime systems call for specific studies. The experimental work was supplemented with reaction path modeling, which provided a quantitative procedure to decipher the chemical nature of fly ash hydration and cementitious system formation.     

Surface properties of cement hydration products. I. Pore structure of calcium silicate hydrates prepared in a suspension form

Adsorption–desorption isotherms of water vapour at 30° were determined on preparations of calcium silicate hydrates of different molar ratios of lime/silica before and after free lime and free silica extractions. From these isotherms specific surface areas were measured and total pore structure analysis was evaluated. A surface layer thickness (t) curve for the adsorption of water vapour on calcium silicate hydrates was constructed, based on experimental curves previously published for the number of layers adsorbed on a variety of non-porous solids with the same heat of adsorption as the calcium silicate hydrates. The existence of both wide pores and micropores was detected in the calcium silicate hydrates. When the samples were free from uncombined lime and silica the micropores were estimated to have an average hydraulic radius of 4–5 Å, whereas the wide pores had an average size of 10 Å. Wide pores up to 200 Å also exist. The pores were predominantly parallel plates.     

Hydrothermal alkaline treatment of oil shale ash for synthesis of tobermorites

The hydrothermal alkaline activation of the oil shale fly ash was studied using SEM/EDX, XRD and ²⁹Si and ²⁷Al high-resolution MAS-NMR spectra. The silicon in the original fly ashes was completely converted into calcium-alumino-silicate hydrates, mainly into 1.1 nm tobermorite structure during 24 h treatment under hydrothermal conditions at 160 °C in the presence of NaOH. The local structure of synthesized tobermorite samples implies long silicate chains with small number of bridging sites. The results obtained in the study prove that the oil shale fly ash can be used for production of Al-substituted tobermorites.     

Sodium silicate activated slag‐fly ash binders: Part I – Processing,microstructure, and mechanical properties

Alkali silicate activated slag and class F fly ash‐based binders are ambient curing, structural materials that are feasible replacements for ordinary Portland cement (OPC). They exhibit advantageous mechanical properties and less environmental impact than OPC. In this work, five sodium silicate activated slag‐fly ash binder mixtures were developed and their compressive and flexural strengths were studied as a function of curing temperature and time. It was found that the strongest mixture sets at ambient temperature and had a Weibull average flexural strength of 5.7 ± 1.5 MPa and Weibull average compressive strength of 60 ± 8 MPa at 28 days. While increasing the slag/fly ash ratio accelerated the strength development, the cure time was decreased due to the formation of calcium silicate hydrate (C–S–H), calcium aluminum silicate hydrate (C–A–S–H), and (Ca,Na) based geopolymer. The density, microstructure, and phase evolution of ambient‐cured, heat‐cured, and heat‐treated binders were studied using pycnometry, scanning electron microscopy, energy dispersive X‐ray spectroscopy (SEM‐EDS), and X‐ray diffraction (XRD). Heat‐cured binders were more dense than ambient‐cured binder. No new crystalline phases evolved through 28 days in ambient‐ or heat‐cured binders.     

Heteroepitaxial Growth of Calcium Silicate Hydrate on Calcium Germanate Hydrate

The hydration of tricalcium silicate at 25°C was accelerated by seeding with 5 wt% tricalcium germanate. Based on heat evolution, seeding resulted in the elimination of the induction period. However, the shape of the hydration peak remained the same. Because tricalcium germanate hydrates first, the microstructure of the calcium silicate hydrate which subsequently forms is influenced by the calcium germanate hydrate morphology. Calcium silicate hydrate formed in the presence of calcium germanate hydrate exhibits the morphology typical of the latter. Acceleration of hydration and morphological variation indicate heteroepitaxial growth.     

氧化镁微膨胀水泥-粉煤灰胶凝材料的膨胀性能及孔结构特征

研究低钙粉煤灰对氧化镁微膨胀水泥的膨胀性能与水泥石孔结构的影响。粉煤灰强烈抑制氧化镁膨胀,粉煤灰的质量分数大于20％左右时,氧化镁膨胀几乎被完全抵消。粉煤灰降低早期强度,但随着龄期的增长,粉煤灰使强度增加的作用逐渐体现,对较长龄期的强度而言,适当掺人粉煤灰反而是有利的,如粉煤灰掺量高达35％时,其3a强度比纯水泥的还高。粉煤灰能促使水泥石孔隙细化,适当掺人粉煤灰可以改善氧化镁微膨胀水泥的水泥石孔结构。     

Temperature effects on local structure,phase transformation,and mechanical properties of calcium silicate hydrates

This study aims to elucidate the effect of heating on the local atomic arrangements, structure, phase transformation, and mechanical properties of synthesized calcium–silicate–hydrate (C–S–H). The alteration in the atomic arrangement of the synthesized C–S–H (Ca/Si =0.8) and the formation of crystalline phases that occurred in three distinct transformation stages of dehydration (105°C–200°C), decomposition (300°C–600°C), and recrystallization (700°C–1000°C) were investigated via powder X-ray diffraction, ²⁹Si nuclear magnetic resonance spectroscopy, and thermogravimetric analysis. Further, the deformation of the local atomic bonding environment and variations in mechanical properties during the three stages were assessed via pair distribution function analysis based on in-situ total X-ray scattering. The results revealed that the C–S–H paste before heating exhibited a lower elastic modulus in real space than that in the reciprocal space in the initial loading stage because water molecules acted as a lubricant in the interlayer. At the dehydration stage, the strain as a function of external loading exhibited irregular deformation owing to the formation of additional pores induced by the evaporation of free moisture. At the decomposition stage, the structural deformation of the main d-spacing (d ≈ 3.0 Å) was similar to that of the real space before the propagation of microcracks. At the recrystallization stage, the elastic modulus increased to 48 GPa owing to the thermal phase transformation of C–S–H to crystalline β-wollastonite. The results provide direct experimental evidence of the microstructural and nanostructural deformation behavior of C–S–H pastes after exposure to high temperature under external loading.     

Effects of temperature on the atomic structure of synthetic calcium–silicate–deuterate gels: A neutron pair distribution function investigation

Due to the nanocrystallinity of the calcium–silicate–hydrate (C–S–H) gel in ordinary Portland cement-based paste combined with the presence of nanoscale heterogeneities such as varying calcium-to-silicon ratios and incorporation of aluminum in the structure, standard characterization techniques fail to fully capture the complex atomic structure and nanoscale morphology of this important binder phase. Here, neutron pair distribution function (PDF) analysis is applied to a range of deuterated C–S–H gels with varying Ca/Si ratios (denoted C–S–D). In situ temperature measurements reveal that the local atomic bonding environments in C–S–D gel undergo large structural rearrangements due to exposure to elevated temperature (above ~ 200 °C), including the collapse of the C–S–D gel interlayer spacing to 9.6 Å and the emergence of a disordered dicalcium silicate phase (similar to larnite). At lower elevated temperatures, the atom–atom correlations are dominated by scattering from deuterium atoms and therefore can be used to quantify the dehydration kinetics.     

Improved evidence for the existence of an intermediate phase during hydration of tricalcium silicate

Tricalcium silicate (Ca₃SiO₅) with a very small particle size of approximately 50 nm has been prepared and hydrated for a very short time (5 min) by two different modes in a paste experiment, using a water/solid-ratio of 1.20, and by hydration as a suspension employing a water/solid-ratio of 4000. A phase containing uncondensed silicate monomers close to hydrogen atoms (either hydroxyl groups or water molecules) was formed in both experiments. This phase is distinct from anhydrous tricalcium silicate and from the calcium-silicate-hydrate (C-S-H) phase, commonly identified as the hydration product of tricalcium silicate. In the paste experiment, approximately 79% of silicon atoms were present in the hydrated phase containing silicate monomers as determined from ²⁹Si{¹H} CP/MAS NMR. This result is used to show that the hydrated silicate monomers are part of a separate phase and that they cannot be attributed to a hydroxylated surface of tricalcium silicate after contact with water. The phase containing hydrated silicate monomers is metastable with respect to the C-S-H phase since it transforms into the latter in a half saturated calcium hydroxide solution. These data is used to emphasize that the hydration of tricalcium silicate proceeds in two consecutive steps. In the first reaction, an intermediate phase containing hydrated silicate monomers is formed which is subsequently transformed into C-S-H as the final hydration product in the second step. The introduction of an intermediate phase in calculations of the early hydration of tricalcium silicate can explain the presence of the induction period. It is shown that heterogeneous nucleation on appropriate crystal surfaces is able to reduce the length of the induction period and thus to accelerate the reaction of tricalcium silicate with water.     

Cl-对高钙粉煤灰硬化水泥浆体的影响

研究了高钙粉煤灰硬化水泥浆体中Cl^-的扩散和渗透规律，以及Cl^-对高钙粉煤灰硬化水泥浆体性能的影响，并探讨了氯盐对高钙粉煤灰水泥浆体产生破坏的机理。试验结果表明，高钙粉煤灰的掺量以及水灰比和水化时间对Cl^-的扩散都有影响。     

石灰-水泥-粉煤灰改性磷石膏对水泥物理性能的影响研究

采用石灰、水泥、粉煤灰对磷石膏进行改性处理,测定了改性磷石膏中硫酸根的溶解性能,对比了原状磷石膏与改性磷石膏对水泥物理性能的影响,并结合X射线衍射（XRD）和扫描电镜（SEM）分析了改性前后磷石膏对水泥不同龄期水化产物的影响。结果表明：随着石灰掺量的增加改性磷石膏的pH逐渐增大,当石灰掺量为4%（质量分数）时磷石膏的pH达到12.22,此时磷石膏中的可溶性磷、氟转化成难溶性的磷酸盐、氟化钙;随着水泥和粉煤灰掺量的增加,改性磷石膏的溶解性能呈现降低趋势。当石灰掺量为4%、水泥掺量为10%（质量分数）、粉煤灰掺量为10%（质量分数）时,改性磷石膏经过7 d养护在水中浸泡8 h所得滤液中硫酸根的质量浓度为0.30 g/L,比未改性磷石膏在水中浸泡8 h所得滤液中硫酸根的质量浓度降低了81.8%。与掺加未改性磷石膏的水泥浆体相比,掺加改性磷石膏的水泥浆体的水灰质量比由0.41降低到0.38、初凝时间和终凝时间分别缩短34.6%和27.2%、28 d抗压强度提高21.1%。石灰、水泥、粉煤灰改性处理磷石膏后,生成的水化硅酸钙和钙矾石等水硬性产物包裹在石膏颗粒表面,使硫酸根在水中的溶出速率降低,减少了对水泥中铝酸三钙的影响,使得硬化体内部结构变得致密、力学性能显著提高。     

Decalcification shrinkage of cement paste

Decalcification of cement paste in concrete is associated with several modes of chemical degradation including leaching, carbonation and sulfate attack. The primary aim of the current study was to investigate the effects of decalcification under saturated conditions on the dimensional stability of cement paste. Thin (0.8 mm) specimens of tricalcium silicate (C₃S) paste, white portland cement (WPC) paste, and WPC paste blended with 30% silica fume (WPC/30% SF) were decalcified by leaching in concentrated solutions of ammonium nitrate, a method that efficiently removes calcium from the solid while largely preserving silicate and other ions. All pastes were found to shrink significantly and irreversibly as a result of decalcification, particularly when the Ca/Si ratio of the C-S-H gel was reduced below ∼ 1.2. Since this composition coincides with the onset of structural changes in C-S-H such as an increase in silicate polymerization and a local densification into sheet-like morphologies, it is proposed that the observed shrinkage, here called decalcification shrinkage, is due initially to these structural changes in C-S-H at Ca/Si ∼ 1.2 and eventually to the decomposition of C-S-H into silica gel. In agreement with this reasoning, the blended cement paste exhibited greater decalcification shrinkage than the pure cement pastes due to its lower initial Ca/Si ratio for C-S-H gel. The similarities in the mechanisms of decalcification shrinkage and carbonation shrinkage are also discussed.     

Calcium hydroxide distribution and calcium silicate hydrate composition in tricalcium silicate and β-dicalcium silicate pastes

Pastes of tricalcium silicate (C₃S) and β-dicalcium silicate (C₂S) 23 years old were studied by electron probe microanalysis. In both cases, regions consisting entirely or largely of calcium hydroxide and of CSH were distinguished on a scale of 2–50 μm. The regions high in CSH accounted for 75–80 percent of the whole in the C₃S paste and about 96 percent in the C₂S paste; these values are much higher than those initially occupied by anhydrous starting materials. Within the high CSH areas, no compositional variation was detected that could have corresponded to the so-called inner and outer hydrates. The ratio of mean Ca to mean Si in the high CSH areas was found to be 1.72 for the C₃S paste and 1.78 for the C₂S paste with an exciting beam energy of 10 keV.     

Self-cementitious properties of fly ashes from CFBC boilers co-firing coal and high-sulphur petroleum coke

Self-cementitious properties of fly ash from circulating fluidized bed combustion boiler co-firing coal and high-sulphur petroleum coke (CPFA) were investigated. CPFA was self-cementitious which was affected by its fineness and chemical compositions, especially the contents of SO₃ and free lime (f-CaO). Higher contents of SO₃ and f-CaO were beneficial to self-cementitious strength; the self-cementitious strength increases with a decrease of its 45 μm sieve residue. The expansive ratio of CPFA hardened paste was high because of generation of ettringite (AFt), which was influenced by its water to binder ratio (W/A), curing style and grinding of the ash. The paste cured in water had the highest expansive ratio, and grinding of CPFA was beneficial to its volume stability. The hydration products of CPFA detected by X-ray diffraction (XRD) and scanning electron microscopy (SEM) were portlandite, gypsum, AFt and hydrated calcium silicate (C-S-H).     

Influence of nucleation seeding on the hydration kinetics and compressive strength of alkali activated slag paste

Addition of pure calcium silicate hydrate (C–S–H) to alkali-activated slag (AAS) paste resulted in an earlier and larger hydration rate peak measured with isothermal calorimetry and a much higher compressive strength after 1 d of curing. This is attributed to a nucleation seeding effect, as was previously established for Portland cement and tricalcium silicate pastes. The acceleration of AAS hydration by seeding indicates that the early hydration rate is controlled by nucleation and growth. For the experiments reported here, the effect of C–S–H seed on the strength development of AAS paste between 1 d and 14 d of curing depended strongly on the curing method. With sealed curing the strength continued to increase, but with underwater curing the strength decreased due to cracking. This cracking is attributed to differential stresses arising from chemical and autogenous shrinkage. Similar experiments were also performed on Portland cement paste.     

Mechanical properties and microstructure evaluation of fly ash - Slag geopolymer foaming materials

The existing fly ash-slag foaming geopolymer materials generally have the shortcomings of low fly ash content and low porosity. It is urgent to develop geopolymer foaming materials with high fly ash content and high porosity. Using fly ash and slag as the main raw materials, geopolymer foaming materials were prepared by alkali activation. The effects of activator content and sodium silicate modulus on the macroscopic mechanical properties, pore structures and microstructures of geopolymer foaming materials were studied. The experimental results showed that when the activator content was 21% (wt.) and the modulus of sodium silicate was 1, the specimen exhibited the best performance. The compressive strength of the specimen reached 2.18 MPa at 28 d, the porosity was 63.07%, and the average pore sizes of macroscopic pores were 920 μm. Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) and Scanning Electron Microscopy and Energy Dispersive Spectrometer (SEM-EDS) analysis showed that when the content of activator was 21% and the modulus of sodium silicate was 1, the reaction grade of the system was the highest, reached 55.12%, meanwhile the main product Sodium silicate hydrate (N-A-S-H) gel produced the largest amount. The fractal dimension calculations showed that the spatial complexity of a specimen with large pores was greater than that of a specimen with small pores. This study can provide a basis for the design of geopolymer foaming materials with high proportion of fly ash and high porosity.     

Fast microwave syntheses of fly ash based porous geopolymers in the presence of high alkali concentration

Microwave synthesis of porous fly ash geopolymers was achieved using a household microwave oven. Fly ash paste containing SiO₂ and Al₂O₃ component was mixed with sodium silicate (Na₂SiO₃) solutions at different concentrations of sodium hydroxide (NaOH) of 2, 5, 10, and 15 M, which were used as NaOH activators of geopolymerization. The mass ratio of Na₂SiO₃/NaOH was fixed at 2.5 with SiO₂/Al₂O₃ at 2.69. After the fly ash and alkali activators were mixed for 1 min until homogeneous, the geopolymer paste was cured for 1 min using household microwave oven at different output powers of 200, 500, 700, and 850 W. Porous geopolymers were formed immediately. Micro X-ray CT and SEM results showed that the porous structure of the geopolymers was developed at higher NaOH concentrations when using 850 W power of the microwave oven. These results derive from the immediate increase of the temperature in the geopolymer paste at higher NaOH concentrations, meaning that aluminosilicate bonds formed easily in the geopolymers within 1 min.     

The Coexistence of the Poly(phospho-siloxo) Networks and Calcium Phosphates on the Compressive Strengths of the Acid-Based Geopolymers Obtained at Room Temperature

This work aims to investigate the coexistence of the poly(phospho-siloxo) networks and calcium phosphates on the compressive strengths of the acid-based geopolymers obtained at room temperature. Waste fired brick and phosphoric acid were used as an aluminosilicate and chemical reagent, respectively. Calcium aluminate hydrate was prepared by mixing calcium hydroxide from the calcined eggshell and calcined bauxite. Calcium silicate hydrate was obtained by the mixture of rice husk ash and calcium hydroxide. The molar ratios CaO/Al₂O₃ and CaO/SiO₂ in the calcium aluminate and calcium silicate hydrates are equals to 1.0. The X-ray patterns of the acid-based geopolymers indicate the broad hump structure between 18 and 38°(2θ). In addition to this broad band, those from the mixture of calcium sources show the reflection peaks of monetite and brushite. The compressive strength of the reference is 56.43 MPa. Those obtained with the addition of 10, 20, 40 and 50 g of calcined eggshell are 30.15, 22.85, 21.16 and 13.47 MPa, respectively. The ones from calcium aluminate hydrate are 32.62, 31.58, 17.83 and 16.33 MPa, respectively. Whereas those containing calcium silicate hydrate are 44.02, 42.71, 40.19 and 18.59 MPa, respectively. This work demonstrates that the formation of calcium phosphates in the structure of the acid-based geopolymers decreases the poly(phospho-siloxo) chains and therefore reduces their compressive strengths. The moderate addition of calcium silicate hydrate reduces slightly the compressive strengths of the acid-based geopolymers which can be comparable to the one of CEM II 42.5R.

     

Relations between structure and mechanical properties of autoclaved aerated concrete

Laboratory specimens of autoclaved aerated concrete were produced under varying conditions, mainly with cement and lime as binders. The type and amount of reaction products, the porosity and the pore size distribution were studied. Shrinkage and compressive strength were measured. The reaction products belonged to the tobermorite group of calcium silicate hydrates and the term crystallinity was defined as the percentage of 11.3 Å tobermorite out of the total amount of calcium silicate hydrates. The shrinkage decreased with increasing crystallinity while the compressive strength increased up to an optimum value. The strength also increased with increasing amounts of hydrates and with decreasing porosity. Other features of the reaction products were indicated by thermal behaviour and micropore size distributions and may have been of importance for the mechanical properties of the material.