Constitutive response of calcium‐silicate‐hydrate layers under combined loading

Calcium‐silicate‐hydrate (C‐S‐H) is the main hydration product for ordinary Portland cement (OPC) materials that exhibits a layered structure containing interfaces that controls the system response to shear deformation at the nanometer scale. In this work, we used molecular statics simulations to study the mechanical behavior of an atomistic model of C‐S‐H under combined loading conditions that are typical of structural applications of these materials. Combined loading is implemented by first compressing or stretching the atomistic structure to impose an external hydrostatic pressure, and then loading the system through both heterogeneous and homogeneous shear deformation. By utilizing two different shear methodologies, we were able to isolate the interface behavior from the bulk response. Our results show several qualitative similarities with that of macroscale cementitious materials including pressure sensitivity of the maximum shear strength and strength asymmetry in compression and tension. This indicates that the well‐known cohesive‐frictional behavior of cementitious materials is fundamental to interfaces between C‐S‐H grains at the nanoscale. Comparing differences in our results with nanoindentation experiments motivate future investigations of the effect of C‐S‐H particle size and morphology on strength scaling properties at the mesoscale. These mesoscale model interactions should include the normal‐stress or pressure dependency that we observe.     

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.     

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.     

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.     

3D Nanotomography of calcium silicate hydrates by transmission electron microscopy

Calcium silicate hydrate (C-S-H), is the principal hydration product of Portland cement that mainly contributes to the physical and mechanical properties of concrete. This paper aims to investigate the three-dimensional structure of C-S-H with Ca/Si ratios of 1.0 and 1.6 at the nanoscale using electron tomography. The 3D reconstructions and selected region of interest analysis confirm that the morphology of both C-S-H materials are foil-like structures. The difference between the two materials is the density of elongated structures. C-S-H with Ca/Si ratio 1.6 is clearly composed of denser particles compared to the other C-S-H material due to overlapping of the foil-like structure. Pore analysis shows that C-S-H 1.0 and C-S-H 1.6 have porosities 69.2% and 49.8% respectively. Pore size distribution also reveals that C-S-H 1.0 has pore size range between 0-250 nm and C-S-H 1.6 between 0-100 nm. The pore network's size of C-S-H 1.0 is significantly larger than 1.6. This study illustrates the capability of using electron tomography to determine the 3D nanoscale structure of cementitious products and to distinguish between C-S-H 1.0 and 1.6.     

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.     

水泥的碳酸化工艺研究

通过设计正交实验,测定碳酸化水泥复合胶凝材料与纯水泥的水化产物及观察硬化浆体的微观形貌,研究了水泥的碳酸化工艺条件。结果表明：碳酸化水泥复合胶凝材料3d、28d的抗压强度普遍高于纯水泥,且强度等级由42．5提高至52．5;水量、碳酸化温度对碳酸化复合胶凝材料3d抗压强度有显著影响,且水量的影响作用较大;水泥的碳酸化最佳工艺条件为水量：0．2％、CO2压力：0．2MPa、碳酸化温度：25℃、碳酸化时间：30min;复合胶凝材料3d水化产物中有CaCO3微晶析出,28d水化产物中有较多的碳铝酸钙生成。     

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.     

High calcium cementless fly ash binder with low environmental footprint: Optimum Taguchi design

Despite the myriad of research efforts on exploiting fly ash as an alternative binder, its current role in industry is largely restricted to the supplementary use, which enables only partial replacement of conventional portland cement. Herein, we propose an unprecedented binder composite with the promising early-age strength, which is cost-effective and reduces the CO₂ footprint compared with portland cement. The major constituent is fly ash occupying 76.4%-80.3% by the total mass of the constituents, while calcium oxide, nanosilica, and the minimum amounts of sodium-based activators are added to induce the early-age strength development. Optimization of the composition via the Taguchi design of experiments produced the early (7-day) compressive strength of 16.18 MPa. This value is encouraging considering that it is comparable to that of conventional portland cement and that a cementless composition with the minimum amounts of sodium-based activators was employed. The extensive materials analysis demonstrates that the starting Ca/Na molar ratio and the amount of nanosilica play instrumental roles in strength development by influencing the formation of key reaction products, which include the sodium-substituted AFm phase (the U-phase), katoite and portlandite. Overall, the promising early-age strength coupled with the significantly decreased amount of sodium-based chemicals and the reduced CO₂ footprint will lay a foundation for development of low-cost, environmentally friendly binder in diverse industries.     

Examination of gamma-irradiated calcium silicate hydrates. Part I: Chemical-structural properties

The chemical-structural properties of synthetic calcium silicate hydrate (C-S-H) with C/S (Ca/Si) ratios of 0.75, 1 and 1.33 were studied after gamma irradiation-absorbed doses ranging from 0.145 to 0.784 MGy and compared with those of control specimens. The results showed that the total water content given by thermogravimetric analysis and the dimension of the basal spacing given by x-ray diffraction were comparable for control and irradiated samples, which indicate that the interlayer water content did not change. The morphology, C/S ratios, and silicate mean chain length were also found to be unaltered by the absorbed gamma doses.     

碳酸化对普通硅酸盐水泥水化性能的影响

通过控制加水量来调节普通硅酸盐水泥的碳酸化程度。通过对硬化浆体水化产物的种类及含量进行分析,研究了在不同的加水量下,碳酸化对普通硅酸盐水泥水化性能的影响。结果表明：在加水量为0.2%～7%的范围内,碳酸化增重率由0.133%增至6.8%;普通硅酸盐水泥经碳酸化后,生成CaCO3晶体颗粒;f-CaO的含量由1.584%下降至0.198%;随着碳酸化增重率的增大,碳酸化水泥的标准稠度用水量由0.28增至0.42;碳酸化降低了普通硅酸盐水泥3 d、28 d抗压强度,尤其对3 d抗压强度影响更为明显;碳酸化生成的CaCO3易与水泥中的C3A反应生成碳铝酸钙;碳酸化抑制普通硅酸盐水泥的早期水化,但对后期水化影响较小。     

Characterization of C–S–H and C–A–S–H phases by electron microscopy imaging,diffraction, and energy dispersive X‐ray spectroscopy

Improving concrete sustainability by increasing durability requires a detailed knowledge about microstructural properties. Due to the nanoscale nature of hydrate phases that determine concrete properties, microstructural characterization remains a challenge. Analytical electron microscopy offers promising techniques to characterize cement hydrates. In this study, electron microscopy imaging, diffraction, and energy dispersive X‐ray spectroscopic information are combined in order to compare the structural properties of calcium silicate hydrate (C–S–H) and calcium aluminum silicate hydrate (C–A–S–H) phases. Results are shown for 28 days hydrated C–(A)–S–H of portland cement and cement containing ground granulated blast‐furnace slag (GGFBS). Electron diffraction patterns of single fibrous C–S–H and foil‐like C–A–S–H phases reveal a nanocrystalline structure. Also, it is shown by electron diffraction pattern that the crystal structures of C–S–H and C–A–S–H phases are similar. It is confirmed that the crystal structure of 14 Å tobermorite serves as good base for the structure of C–S–H. The electron diffraction patterns of fibrous C–S–H show streaks which indicate stacking faults, proofing that polymerization of silicate chains in C–S–H is limited. Here, we demonstrate for the first time that the dreierketten silicate chains contained in the C–S–H structure are oriented in parallel to the long axis of C–S–H fibers. This finding should be implemented in modeling of crystal growth of C–S–H.     

二氧化碳矿化养护混凝土技术及新型材料研究进展

CO₂矿化养护技术利用早期成型后的混凝土材料和CO₂之间的碳酸化反应和产物沉积过程实现产品力学强度等特性的提升,主要关注的是预养护/早期水化成型后的混凝土中胶凝成分和CO₂之间的矿化反应（即加速碳酸化）。此过程中胶凝材料的水化过程不再是强度形成的主要反应,因此为了充分实现矿化成型和CO₂固定,实现环境效益最大化,研究者近几年积极开发具有CO₂矿化潜力的碱金属矿物材料,并探究其反应后对于混凝土微观结构和性能的促进效应。本文综述了CO₂矿化养护技术在新型混凝土材料方面的研究进展,分别对传统混凝土采用的水化活性硅酸钙材料、水化惰性硅酸钙材料、镁基水泥材料以及工业固废材料等进行了具体介绍,比较了在不同材料与CO₂反应特性以及养护后建材制品性能优化方面的最新成果,并对CO₂矿化养护技术的后续发展进行了展望。主要建议：一是着眼于微观反应机制和矿物材料特性,开发有效的矿化反应强化方法;二是开发水化惰性的低钙硅比硅酸钙材料;三是将工业固废资源化与矿化养护技术结合,实现固废和气废利用流程耦合,推进特定工艺开发和装置研发。     

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％,...     

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.     

Effects of chitosan and zirconia on setting time,mechanical strength,and bioactivity of calcium silicate‐based cement

In this research, we aimed at improving the setting properties and biocompatibility of the mineral trioxide aggregate‐like cements while maintaining the main chemical formula. Consequently, chitosan and zirconium oxide were added to the cement instead of bismuth oxide to improve the mechanical behavior, limit the possible toxicity, and enhance the bioactivity of the cements. Adding zirconia resulted in a shorter setting time and adding chitosan contributed to the setting time, mechanical strength, and biocompatibility at the same time. Thus, cements containing both chitosan and zirconia had the shortest setting time, highest compressive strength, and apatite‐forming ability.     

New insight into design of highly ordered calcium silicate hydrate with graphene oxide

Calcium silicate hydrate (C–S–H) is the main hydration product of cement and the most important binder that plays a pivotal role in the mechanical properties of concrete. However, one of the major drawbacks of C–S–H is its high brittleness and low flexural strength due to its disordered structure at the nano- and micro-scales. Therefore, this study adopts graphene oxide (GO) to modify the structure of C–S–H, and investigates the effects of synthetic methods on the structure of C–S–H–GO composites. In this study, the highly ordered C–S–H–GO composite is successfully synthesized and exhibits itself the high toughness. Moreover, the formation mechanism of the highly ordered C–S–H–GO composite is explored and discussed, which provides a new insight into the design of high-toughness cement-based materials.     

钙硅比对水化硅酸钙加速碳化的影响

废弃水泥石、钢渣等碳酸化固定CO2不仅可以缓解温室效应还可以实现废弃物的再利用,同时制备出性能优良的建材制品。为了研究废弃水泥石矿物组成的碳酸化机理,探讨了钙硅比对水化硅酸钙加速碳化的影响。结果表明:随着钙硅比增加,水化硅酸钙(C-S-H)碳化率逐渐降低,高钙硅比的C-S-H具有相对粗大的孔结构使得早期的碳化速率增加;碳化产物中文石、球霰石、方解石在不同钙硅比时所占比例不同,钙硅比≤0.67时文石占较大比例,钙硅比≥1.00时方解石为主要碳化产物,钙硅比=0.83时球霰石含量最大;加速碳化条件下形成的碳酸钙分解温度分成两部分,在400~620℃范围内文石和球霰石都分解,方解石在650~800℃范围内分解。     

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.     

Molecular and submolecular scale effects of comb‐copolymers on tri‐calcium silicate reactivity: Toward molecular design

The impact of organic compounds on the processing and reactivity of inorganic materials has been a source of inspiration for materials scientists for decades and continues to trigger novel and innovative applications in a broad range of disciplines. However, molecular design of such compounds to reach targeted properties remains challenging, particularly for reactive and multicomponent systems. This outstanding challenge is met here by combining a model cement, hosting different coupled reactions of dissolution, nucleation and growth, together with comb‐copolymers that offer large and well‐controlled variations of their molecular architecture. We show that silicate reactivity is affected by a combination of molecular and submolecular scale effects of these polymers. The first can be described by scaling laws from polymer physics, whereas the second involves specific chemical interactions. In particular, the ability of these polymers to hinder dissolution appears to be crucial, something for which strong experimental evidence is provided.