Study on activation of fluorogypsum by sodium sulfate and sodium nitrite.

Given the issues related to poor hydration activity, long setting time and low early strength of industrial by-product fluorogypsum (FG), the composite modifiers (Na2SO4 and NaNO2) were utilized to enhance its reactivity. The investigation of the mechanism involved the utilization of contemporary analytical methods, including X-ray diffraction (XRD), 1H low-field nuclear magnetic resonance (NMR), and Scanning electron microscope and Energy Dispersive Spectrometer (SEM-EDS). The results demonstrated that the incorporation of modifiers significantly enhanced both the hydration rate and activity of fluorogypsum. The optimum concentration of the composite modifier was found to be 1.5 wt% Na2SO4 and 0.5 wt% NaNO2. The addition of modifiers (1.5 wt% Na2SO4 and 0.5 wt% NaNO2) significantly shortens the setting time of FG paste, reducing it by approximately 500 min compared to the control sample. After 28 days of curing, the flexural strength and compressive strength of the fluorogypsum sample containing modifiers (1.5 wt% Na2SO4 and 0.5 wt% NaNO2) increased by 55.5 % (reaching 4.2 MPa) and 31.5 % (reaching 37.6 MPa), respectively. The modifiers facilitate the transformation from anhydrite (CaSO4, AH) to dihydrate gypsum (CaSO4·2H2O, DH). Both NaNO2 and Na2SO4 alter the growth rates of different crystal axes during DH crystal growth, transforming them into prismatic and needle-shaped DH. The prismatic and needle-shaped DH crystals were arranged in layers, resulting in a compact structure with low hole content and few pores, which led to increased density of the hardened paste and higher strength. The current study provides evidence that the inclusion of composite modifiers greatly improves the activity of FG, making it more efficient in the field of building materials.

Revealing the solid solution tendency of tungsten ions in phases of Ordinary Portland cement clinker: A study based on experiments and DFT calculations.

The collaborative utilization of solid waste through cement kiln represents a highly effective approach in the current era for harnessing solid waste resources. In this paper, density functional theory simulations is used to predict the substitution tendency of tungsten (W) in Ordinary Portland cement (OPC) clinker. By employing experimental design, X-ray diffraction testing, and element distribution spectrum analysis, the doping preference of W ions in OPC clinker was comprehensively investigated. The findings demonstrate that a minor fraction of WO3 firstly infiltrates C4AF through the substitution of Fe atoms, whereas the majority of WO3 infiltrates C3S and C2S secondly by substituting Si atoms, with negligible infiltration observed in C3A finally. The substitution of Fe with W exhibits a lower formation energy compared to other ions, thereby indicating its preference for the formation of solid solutions in C4AF. This preference is primarily determined by the overlapping distribution of WO and FeO bond order-bond length and their similar electron contributions in spatial distribution. However, it should be noted that the newly formed WO bond has weaker strength than the FeO bond, which may explain the limited solubility of W in C4AF. The in-depth investigation of these fundamental issues is expected to offer an effective approach for enhancing solubility of W in OPC clinker through increasing content of C4AF and silicate minerals, thereby providing valuable guidance for synthesizing OPC clinker using W-bearing solid wastes.

Effects of AH3 and AFt on the Hydration-Hardening Properties of the C4A3S¯-CS¯-H2O System.

This study aimed to reveal the effects of the hydration products AH3 and AFt phases on the hydration and hardening properties of calcium sulfoaluminate (CSA) cement. In addition, the effects of anhydrite (CS¯) and gypsum (CS¯H2) on the properties of CSA cement were compared. Calcium sulfoaluminate (C4A3S¯) was synthesized with analytical reagents, and the C4A3S¯-CS¯-H2O system with different molar ratios of CS¯ and C4A3S¯ was established. The phase compositions and contents of AFt and AH3 were determined by X-ray diffraction (XRD), Rietveld quantitative phase analysis, and thermogravimetric analysis (TG). The effects of pore structure and hydration product morphology on mechanical properties were analyzed by mercury intrusion porosity (MIP) and scanning electron microscopy (SEM). The results showed that the compressive strength exhibited a correlation with the AH3 content. In the case of relatively sufficient anhydrite or gypsum, C4A3S¯ has a high degree of hydration, and the AH3 content can be considered to contribute more to the strength of the hardened cement paste. When anhydrite was selected, the combined and interlocked AFt crystals were covered or wrapped by a large amount of AH3. The mechanical properties of the hardened cement paste mixed with anhydrite were better than those of that mixed with gypsum.

Activation behavior of the novel CO2 foaming agent for mining on fly ash.

Although there have been many research results on the chemical activation of fly ash (FA) as a supplementary cementitious material (SCM) in cementitious materials. However, there is a lack of research on the use of CO2 foaming agent (sodium bicarbonate and potassium aluminum sulfate) to activate fly ash. In this experiment, the effects of CO2 foaming agent, sodium bicarbonate, and potassium aluminum sulfate on the activity of FA mixed paste were investigated. The mechanism of FA activation by activator was revealed by selective acid dissolution, QXRD, BSE-EDS statistical analysis, and quantitative analysis of TGA. The results showed that the remaining fly ash amounts of MG, SBG, and PASG after 28 days were 17.5%, 25.9%, and 43.3% lower than those of the control group, respectively. In addition, potassium aluminium sulphate promoted hydration to generate more CH to activate the FA. Sodium bicarbonate promoted hydration and produces more CH to activate FA by generating nano-CaCO3. The mixture of sodium bicarbonate and potassium aluminum sulfate took advantage of both nano-CaCO3 and potassium aluminum sulfate to promote silicate hydration to provide CH. As a result, the two synergistically activate FA. The above results show that CO2 foaming agents can be used not only as foaming agents to prepare lightweight materials, but also as chemical activators to activate solid waste. This will have a high practical application value.

Exploring Exact Effects of Various Factors on Chloride Diffusion in Cracked Concrete: ABAQUS-Based Mesoscale Simulations.

Chloride ion attack is a major cause of concrete durability problems, and existing studies have rarely addressed the effects of damage zones. In this paper, an improved mesoscale model including five phases was constructed using the finite element software ABAQUS to study the diffusivity of chloride ions in cracked concrete. It was found that the damage zone is negligible when the crack width is less than 50 µm, while the width and depth of the damage zone are about 15 times the crack width and 15% of the crack depth when the crack is greater than 50 µm. The results show that the diffusion of chloride is greatly influenced by the crack width, while it is little-influenced by the crack shape. Low water-cement ratio and adequate hydration of the concrete are also key factors affecting chloride diffusion. In contrast, regular rounded aggregates have a positive effect on reducing chloride diffusion compared to irregularly shaped aggregates, and this effect becomes weaker with increasing service time. In addition, the protective layer can effectively prevent the diffusion of chloride in concrete. Therefore, when designing marine concrete, efforts should be made to ensure that the concrete has a low water-cement ratio, adequate hydration, less cracking and a protective layer.

Chain structure and ß conformation of poly(9,9-dioctylfluorene) (PFO) with different molecular weights delivering from the solution to the film in a drop-casting process.

Over the last decade, considerable attention has been paid to the formation mechanism of the ordered ß conformation for PFO both in the solution and film to prepare high-efficiency optoelectronic devices. However, the process of solvent evaporation and aggregates transferred from the solution to the film also play key roles in forming ordered structures, which have been neglected. In this study, the influence of molecular weight on the above process was systematically studied using techniques such as SLS/DLS, UV-Vis, PL, and TEM. Five samples with different Mw ranging from 25 100 Da to 117 000 Da were obtained by the precipitation fractionation method. In dilute THF solution, the molecular chains were in α conformation without aggregates. In films, as the molecular weight increased, the content of ß conformation and ordered structure increased first and then decreased. By studying the solvent evaporation process, for the first time, we propose a possible mechanism for the transformation process of chain structure and ß conformation from the solution to the film, which involves three stages. This study reveals the transformation process of the chain structure and ß conformation of PFO from the solution to the film and its relationship with the molecular weight, which provides theoretical and practical versions for in-depth understanding and control of the formation of the ordered structure in high-efficiency films.

Revealing the substitution preference of zinc in ordinary Portland cement clinker phases: A study from experiments and DFT calculations.

Ordinary Portland cement (OPC) clinker mainly consist four minerals, tricalcium silicate (C3S), dicalcium silicate (C2S,), tricalcium aluminate (C3A), and tetracalcium aluminoferrite (C4AF). To learn the doping behaviors of Zn in OPC clinker, a series of samples were prepared by calcinating the mixtures of CaCO3, SiO2, Al2O3, Fe2O3, and ZnO. Our results from energy-dispersive spectroscopy, X-ray diffraction and density functional theoretical simulations show that a small amount of ZnO enter C3S and C2S by replacing Ca ions while most incorporate into C4AF by substituting Fe atoms, resulting in a decrease of C3A in OPC as dosage increases. Further analyses from partial density of states and distributions of bond order-bond length indicate that the doping preference can be ascribed to the similar electron contributions and small structure distortions between host and guest ions. Unlike the strong Fe‒O bond, the newly formed Zn‒O is much weaker. The weak Zn‒O may be responsible for the limited solubility of Zn in C4AF. These results provide a possibility of increasing solubility of Zn in OPC clinker by increasing the contents of C3A and C4AF, thus will be very meaningful in the synthesis of OPC clinker by utilizing Zn-bearing alternative raw materials.

Insights on Substitution Preference of Pb Ions in Sulfoaluminate Cement Clinker Phases.

The doping behaviors of Pb in sulfoaluminate cement (SAC) clinker phases were systematically studied combined with density functional theoretical simulations and experiments. The results present that, in the three composed minerals of C4A3S, C2S, and C4AF, Pb ions prefer to incorporate into C4A3S by substituting Ca ions. Further analyses from partial density of states, electron density difference, and local distortions show that such doping preference can be attributed to the small distortions as Pb introduced at Ca sites of C4A3S. The results and clear understandings on the doping behaviors of Pb ions may provide valuable information in guiding the synthesis of Pb-bearing SAC clinker, thus should draw broad interests in fields from sustainable production of cement and environmental protection.

Improving the Mechanical Properties of Sulfoaluminate Cement-Based Grouting Material by Incorporating Limestone Powder for a Double Fluid System.

To improve the hardening performance of sulfoaluminate cement-based grouting material (SCGM) and reduce its cost, limestone powder was adopted to replace anhydrite in the control SCGM. The influence of the replacement rate of limestone powder on the hydration, hardening strength, expansion, and microstructure evolution of the SCGM was systematically researched. The results indicated that replacing anhydrite with limestone powder in SCGM can improve the flowability, shorten the setting time, and enhance the compressive strength at early and late stages. When the replacement rate of limestone powder was 20%, the compressive strength of SCGM for 6 h and 28 days increased by 146.41% and 22.33%, respectively. These enhancements were attributed to the fact that fine limestone powder can accelerate the early hydration reaction rate and promote the formation of ettringite due to its nucleation effect. Moreover, due to the presence of limestone powder, mono-carbonate (Mc) can be formed, which would densify the microstructure and refine the pore structure of the hardened SCGM.

Revealing the Microstructure Evolution and Carbonation Hardening Mechanism of ß-C2S Pastes by Backscattered Electron Images.

ß-dicalcium silicate (ß-C2S) minerals were prepared. The compositions, microstructures, and distributions of the carbonation products of hardened ß-C2S paste were revealed by X-ray diffraction (XRD), Fourier transform-infrared (FT-IR) spectroscopy, and backscattered electron (BSE) image analysis. The results show that a dense hardened paste of ß-C2S can be obtained after 24 h of carbonation curing. The hardened pastes are composed of pores, silica gel, calcium carbonate, and unreacted dicalcium silicate, with relative volume fractions of 1.3%, 42.1%, 44.9%, and 11.7%, respectively. The unreacted dicalcium silicate is encapsulated with a silica gel rim, and the pores between the original dicalcium silicate particles are filled with calcium carbonate. The sufficient carbonation products that rapidly formed during the carbonation curing process, forming a dense microstructure, are responsible for the carbonation hardening of the ß-C2S mineral.

Effects of Aluminum Sulfate and Quicklime/Fluorgypsum Ratio on the Properties of Calcium Sulfoaluminate (CSA) Cement-Based Double Liquid Grouting Materials.

Grouting materials are used frequently in grouting reinforcement projects, such as mining and coastal engineering. Double liquid grouting materials are mostly used because of the fast setting and high early strength properties when the two slurries are mixed together but high fluidity when the two slurries are separated. In our study, double liquid grouting materials were developed from CSA cement (slurry A), quicklime and fluorgypsum (slurry B). Aluminum sulfate was added in slurry B in order to counteract any adverse effects caused by the fluorgypsum, such as the decreased early compressive strength and the prolonged setting time. The effects of aluminum sulfate content and the quicklime/fluorgypsum ratio on the setting time, hydration heat, and compressive strength of the double liquid grouting materials were investigated, and the hydration products were characterized through thermogravimetry-differential thermal analysis (TG-DTA), X-ray Diffraction (XRD), and Scanning Electron Microscope (SEM) tests. The results show that the addition of aluminum sulfate can shorten the setting time and increase compressive strength at both early and later ages. Considering the setting time and compressive strength of double liquid grouting material at the same time, the optimum content of aluminum sulfate was found to be 2%, and the optimum ratio of quicklime/fluorgypsum was found to be 2:8. The values of the optimum content of aluminum sulfate and ratio of quicklime/fluorgypsum were verified from theoretical analysis.

Polyurethane/Red Mud Composites with Flexibility, Stretchability, and Flame Retardancy for Grouting.

Flexibility, stretchability, and flame retardancy are of ever increasing importance in constructing grouting materials. Herein, a simple and effective strategy to make organic-inorganic composite grouting material in a "flexible, stretchable, and flame retardant" way was based on the excellent synergistic interactions among polyurethane prepolymer, red mud, polyethylene glycol, and trimethylolpropane. The resultant polyurethane/red mud composite grouting material with three-dimensional network structure presented a favorable flexibility, desirable compressive strength of 29.2 MPa at 50% compression state, and a good elongation at 15.1%. The grouting material was mainly composed of amorphous polyurethane and crystalline red mud, and its probable formation mechanism was reaction of prepolymer with H2O, polyethylene glycol and trimethylolpropane under vigorous stirring in the presence of catalyst. Furthermore, the grouting material possessed favorable thermal stability, flame retardancy and repairment performance for roadway cracks. This work may open a simple and convenient avenue for the massive engineering application of red mud and preparation of flexible organic-inorganic hybrid grouting material.

An active dealkalization of red mud with roasting and water leaching.

The research has focused on the dealkalization of red mud after active roasting and water leaching, which is obtained from bauxite during alumina production. The main factors such as roasting temperature, roasting time, water leaching stage, leaching temperature, leaching reaction time and liquid to solid ratio were investigated. The mechanism of dealkalization was in-depth studied by using ICP-AES, XRD, TG-DSC, SEM-EDS and leaching kinetic. The results show that the dealkalization rate reached 82% under the condition of roasting temperature of 700 °C, roasting time of 30 min, four stage water leaching, liquid to solid ratio of 7 mL/g, leaching temperature of 90 °C and reaction time of 60 min. The diffraction peak of Na6CaAl6Si6(CO3)O24 · 2H2O in red mud was decreased during the active roasting process, whereas the mineral phases of NaOH · H2O and Na2Ca(CO3)2 were appeared. The content of alkali obviously decreased and the grade of other elements increased during the process of active roasting and water leaching, which was in favor of next application process of red mud. The water leaching was controlled by internal diffusion of SCM and the apparent activation energy was 22.63 kJ/mol.