The impact of Al2O3 amount on the synthesis of CASH samples and their influence on the early stage hydration of calcium aluminate cement

In this work the impact of Al₂O₃ amount on the synthesis (200?°C; 4–8?h) of calcium aluminium silicate hydrates (CSAH) samples and their influence on the early stage hydration of calcium aluminate cement (CAC) was examined. It was found that the amount of Al₂O₃ plays an important role in the formation of calcium aluminate hydrates (CAH) because in the mixtures with 2.7% Al₂O₃ only calcium silicate hydrates (CSH) intercalated with Al³⁺ ions were formed. While in the mixtures with a higher amount of Al₂O₃ (5.3–15.4%), calcium aluminate hydrate – C₃AH₆, is formed under all experimental conditions. It is worth noting that the largest quantity of mentioned compound was obtained after 4?h of hydrothermal treatment, in the mixtures with 15.4% of Al₂O₃. It was proved that synthesized C₃AH₆ remain stable up to 300?°C and at higher temperature (945?°C) recrystallized to mayenite (Ca₁₂Al₁₄O₃₃), which reacted with the rest part of CaO and amorphous structure compound, resulting in the formation of gehlenite (Ca₂Al₂SiO₇). Moreover, the synthesized C₃AH₆ addition induced the early stage of CAC hydration. Besides, in the samples with an addition, the induction period was effectively shortened: in a case of pure CAC (G70) paste, hydration takes about 6–6.5?h, while with addition – only 2–2.5?h. The synthesized and calcinated compounds was characterized by using XRD and STA analysis.     

Influence of self heating and Li2SO4 addition on the microstructural development of calcium aluminate cement

Hydrated Calcium Aluminate Cement (CAC) is known to have a complex microstructure involving different phase assemblages strongly dependant on the temperature. This work presents an experimental approach to study the microstructure of CAC pastes from the first minute of hydration with controlled time-temperature histories up to several months of curing. The self heating usually occurring in the CAC concrete is considered and its influence on the growth and assemblage of the hydration products and subsequent space filling is shown. Quantification of the degree of CA hydration by BSE image analysis is used to understand the evolution of phases throughout the hydration process. Lithium sulphate is commonly used to control the setting time of CAC based materials. It is shown that this promotes the formation of more stable hydrates, but slightly reduces the extent of CA hydration.     

Alkali-activated blends of calcium aluminate cement and slag/diatomite

The present study deals with the formulation of new cementitious materials via the alkaline activation of an industrial by-product (blast furnace slag) or a natural rock (diatomite) in the presence of reactive aluminium sourced from calcium aluminate cement (CAC). Two blends, one containing 20% CAC and 80% slag and the other 20% CAC and 80% diatomite, were prepared and activated with sodium sulphate or a sodium hydroxide solution. The hardened materials were characterised with X-ray diffraction (XRD) as well as ²⁷Al and ²⁹Si nuclear magnetic resonance (NMR) and tested for their 2-day mechanical strength. The main reaction product was a cementitious gel that precipitated with crystalline phases such as ettringite, U phase and katoite. While the slag blend reacted to generate a C–(A)–S–H-like gel under moderately alkaline conditions, diatomite reactivity proved to be very low under such conditions. The greater reactivity of both slag and diatomite at high pH (high alkalinity) favoured their interaction with CAC.     

Studies on scaling of membranes in desalination by direct contact membrane distillation: CaCO3 and mixed CaCO3/CaSO4 systems

Scaling of membranes by CaCO₃ and CaSO₄-CaCO₃ is of considerable concern in membrane desalination processes. It is particularly relevant for porous crossflow hollow fiber-based membrane distillation (MD) processes which can achieve high water recovery and can encounter heavy precipitation of scaling salts. Therefore an analysis of the scaling potential for CaCO₃ and mixed CaSO₄-CaCO₃ systems is presented first in terms of the saturation index profiles throughout the crossflow hollow fiber membrane module as a function of the location in the module for feed solutions resulting from high water recovery. Scaling experiments during DCMD with tap water, CaCO₃ and mixed CaSO₄/CaCO₃ were conducted over a wide range of values of saturation index (SI) (10<SI_calcite<64, 1.1<SI_Gypsum<1.5) using porous fluorosilicone coated crossflow hollow fiber membrane desalination modules. The effects of flow rates, flow patterns (cross vs. parallel flow) and the nature of the membrane surface on possible scaling scenarios were further investigated for the scaling salt CaSO₄. Experimental results at high saturation indices show that even when the precipitation rate was fast in the CaCO₃ system at elevated temperatures or high concentrations, no significant loss in water vapor permeation was observed suggesting no effect of scaling on membrane flux. However, for a few of the mixed CaSO₄-CaCO₃ systems, the water vapor flux dropped somewhat. Possible explanations have been provided and a method to solve this problem has been illustrated. Fast feed flow rate resulted in a shortened induction period. Crossflow flow pattern and the nature of the hydrophobic porous coating on the membrane surface were proven to be helpful in developing the resistance to scaling. Results of modeling show that concentration polarization effects are far more important than temperature polarization effects.     

The effect of SiO2 additions on barium aluminate cement formation and properties

Barium aluminate cements have been synthesized by barium carbonate, alumina, kaolin and colloidal silica as starting materials. The effects of the source of SiO₂ and of firing temperature on phase formation and physical properties of the fired cements have been studied. Cement samples were characterized using XRD, SEM, EDX. The setting time and heat of hydration of cements were also evaluated. The barium aluminate cements were mixed in castables. Cold crushing strengths evaluated, and values compared to those obtained using calcium aluminate cement (Secar 71). Mixtures of BaCO₃ and Al₂O₃ were targeted to produce BaAl₂O₄; which had fast set time, expansive behavior and lower strength compared to samples with SiO₂ additions. SiO₂ additions, regardless of source, resulted in BaAl₂Si₂O₈ (celsian) formation. The prepared samples had short setting times and higher mechanical properties in comparison with standard calcium aluminate cement.     

Hydrophilic CaCO3 nanoparticles designed for poly (ethylene terephthalate)

In this work, a new kind of the hydrophilic CaCO₃ nanoparticles modified by polyethylene glycol phosphate (PGP) was designed for the in-situ preparation of poly (ethylene terephthalate) (PET). It was confirmed that PGP induced the growth of calcite and coated the surface of calcite by the covalent bond. PGP not only adjusts the morphology and the size of CaCO₃ nanoparticles, but also solve the main problems in the in-situ preparation of CaCO₃/PET: (a) the reaction of CaCO₃ with TPA; (b) the agglomeration of CaCO₃ nanoparticles. Compared to the nanocomposite filled with the pure CaCO₃, the resulting nanocomposite filled with the modified CaCO₃ exhibits a better dispersion of the nanoparticles, a higher polymerization degree and a better thermal stability. The results related to the covalent bond formed by PGP on the surface of CaCO₃ and PET during the polymerization of the nanocomposite.     

Strengthening effect and mechanism of titanium extraction slag on the mechanical property of calcium aluminate cement

In heavy oil recovery, calcium aluminate cement (CAC) is in the working environment of “low-temperature hardening and ultrahigh temperature service.” However, the formation of C₃AH₆ under low temperatures results in a decrease in strength and reduce the cementing quality. In this study, titanium extraction slag (TES) was used to inhibit CAC strength deterioration. TES, characterized by a high Ti content, presents challenges in terms of utilization and poses significant ecological risks owing to its large accumulation. Cementite hydration with 0%, 20%, 30%, and 40% TES relative to CAC was examined at 30 °C for 28 d. The high C₃AH₆ content of the pure CAC increased the strength deterioration, pore size, and cementite carbonation. With 20% TES, a dilution effect was observed without strength improvement. Furthermore, 30% TES generated layered double hydroxides and converted C–S–H into C–A–S–H, thereby increasing compressive strength. By-products were generated with 40% TES, which inhibited the strength development while generating C–A–S–H to maintain the compressive strength. Therefore, TES can inhibit the strength decline of CAC, and the byproducts of the LDH structure can improve corrosion resistance.     

Current understanding of cellulose ethers impact on the hydration of C3A and C3A-sulphate systems

The impact of cellulose ethers (CE) on C₃A hydration was examined to support the understanding of the retarding effect of CE on cement hydration. In this sense, we successively studied the CE adsorption on ettringite and calcium hydroaluminates, and then the CE influence during C₃A hydration in presence or absence of calcium sulphate. We emphasized a phase-specific adsorption of CE depending on CE chemistry. Besides, in addition of CE, we highlighted a gradual slowing down of C₃A dissolution as well as ettringite and calcium hydroaluminates precipitation. Again, a great impact of CE chemistry and CE adsorption behaviour were noticed. Thus, HECs induce always a stronger adsorption on calcium hydroaluminates and a longer C3A hydration delays than HPMCs.     

The effect of Cr2O3 and P2O5 additions on the phase transformations during the formation of calcium sulfoaluminate C4A3S¯

The study describes the influence of chromium and phosphorus additions on the phase transformations during the formation of the calcium sulfoaluminate Ca₄Al₆SO₁₆ from CaCO₃-Al₂O₃-CaSO₄ mixtures. The temperatures of decarbonation reaction were measured by means of differential thermal analysis. The enthalpy variations at different heating temperatures were determined by isothermal calorimetry. The results show that the Cr₂O₃ and P₂O₅ additions lower the onset temperature of decarbonation. The energy requirement at high temperature of the doped mixtures is less, compared to that of mixtures without dopants. The formation of solid solutions is followed by X-ray diffraction. The higher concentrations of additives hinder the formation of the C₄A₃S¯ phase.     

Early C3A hydration in the presence of different kinds of calcium sulfate

Hydration reactions of C₃A with various amounts of calcium sulfate hemihydrate, gypsum or a mixture of the two, were investigated by isothermal microcalorimetry, and a monitoring of the ionic concentrations of diluted suspensions. This study shows that sulfate type used modifies the early C₃A–CaSO₄ hydration products and the rate of this hydration. The fast initial AFm formation observed before ettringite precipitation in the C₃A–gypsum system is avoided as soon as hemihydrate is present in the suspension. This was attributed to higher super saturation degrees and then higher nucleation frequency with regard to the ettringite obtained in the presence of hemihydrate. Moreover, replacement of gypsum by hemihydrate also leads to an increase of the ettringite formation rate during at least the five first hours under experimental conditions.     

Influence of MgO on the formation of Ca3SiO5 and 3CaO·3Al2O3·CaSO4 minerals in alite-sulphoaluminate cement

The influence of MgO on the formation of Ca₃SiO₅ and 3CaO·3Al₂O₃·CaSO₄ minerals in alite-sulphoaluminate cement is reported in this paper. The results show that adding a suitable amount of MgO can lower the clinkering temperature, promote the formation of Ca₃SiO₅ and 3CaO·3Al₂O₃·CaSO₄ minerals, and help in the coexistence of the two minerals in the clinker. MgO may obviously decrease the formation of Ca₃Al₂O₆, and increase the SiO₂ content incorporated into the interstitial phase.     

Effects of magnetic field on the crystallization of CaCO3 using permanent magnets

Permanent magnets of different intensities were used to investigate the effect of a magnetic field on the crystal growth of calcite suspended in a fluidized bed. The magnets were fixed on the suspended bed where the crystal grew. The growth rates of calcite were measured at various levels of supersaturation (σ), pH, and ionic strength (I) using the constant-composition technique. The calcite growth rates in the presence of the magnetic field were lower than those in the absence of the magnetic field, and higher magnetic intensity yielded a lower growth rate. The effect of a magnetic field on CaCO₃ polymorphism was also studied. The percentage of polymorphs was dependent on the magnetization time. Aragonite was the predominant polymorphic form in the precipitate mixture, which was induced spontaneously by changing the solution pH after the supersaturated solution had been magnetized for 48 h.     

Reactivation and remaking of calcium aluminate pellets for CO2 capture

CaO-based pellets supported with aluminate cements show superior performance in carbonation/calcination cycles for high-temperature CO₂ capture. However, like other CaO-based sorbents, their CO₂ carrying activity is reduced after increasing numbers of cycles under high-temperature, high-CO₂ concentration conditions. In this work the feasibility of their reactivation by steam or water and remaking (reshaping) was investigated. The pellets, prepared from three limestones, Cadomin and Havelock (Canada) and Katowice (Poland, Upper Silesia), were tested in a thermogravimetric analyzer (TGA). The cycles were performed under realistic CO₂ capture conditions, which included calcination in 100% CO₂ at temperatures up to 950 °C. Typically, after 30 cycles, samples were hydrated for 5 min with saturated steam at 100 °C in a laboratory steam reactor (SR). Moreover, larger amounts of pellets were cycled in a tube furnace (TF), hydrated with water and reshaped, and tested to determine their CO₂ capture activity in the TGA. It was found that, after the hydration stage, pellets recovered their activity, and more interestingly, pellets that had experienced a longer series of cycles responded more favorably to reactivation. Moreover, it was found that conversion of pellets increased after about 70 cycles (23%), reaching 33% by about cycle 210, with no reactivation step. Scanning electron microscope (SEM) analyses showed that the morphology of the low-porosity shell formed at the pellet surface during cycles, which limits conversion, was eliminated after a short period (5 min) of steam hydration. The nitrogen physisorption analyses (BET, BJH) of reshaped spent pellets from cycles in the TF confirmed that sorbent surface area and pore size distribution were similar to those of the original pellets. The main alumina compound in remade pellets as determined by XRD was mayenite (Ca₁₂Al₁₄O₃₃). These results showed that, with periodic hydration/remaking steps, pellets can be used for extended times in CO₂ looping cycles, regardless of capture/regeneration conditions.     

Effects of grinding and firing conditions on CaAl2Si2O8 phase formation by solid-state reaction of kaolinite with CaCO3

The effects of grinding and firing conditions on CaAl₂Si₂O₈ phase formation by solid-state reaction of kaolinite with CaCO₃ were investigated by differential thermal analysis (DTA)–thermogravimetry (TG), X-ray powder diffraction (XRD) and ²⁹Si and ²⁷Al MAS NMR. Unground and ground samples showed similar crystallization behavior at about 850 °C, and the crystallizing temperature was relatively unaffected by grinding. On the other hand, the crystalline products were strongly influenced by the grinding. Gehlenite (Ca₂Al₂SiO₇) was the dominant phase in the unground samples but layer-structured CaAl₂Si₂O₈ was dominant in the ground samples, together with a small amount of anorthite, which is the stable phase. The amount of anorthite gradually increased with higher firing temperature, the sample fired at 1000 °C being almost completely anorthite. Grinding treatment before firing was effective in accelerating the decomposition of CaCO₃ and extending the temperature range for the formation of CaAl₂Si₂O₈, a phase with local structure similar to that of layered CaAl₂Si₂O₈.     

Hydrothermal transformation of the calcium aluminum oxide hydrates CaAl2O4·10H2O and Ca2Al2O5·8H2O to Ca3Al2(OH)12 investigated by in situ synchrotron X-ray powder diffraction

The hydrothermal transformation of calcium aluminate hydrates were investigated by in situ synchrotron X-ray powder diffraction in the temperature range 25 to 170 °C. This technique allowed the study of the detailed reaction mechanism and identification of intermediate phases. The material CaAl₂O₄·10H₂O converted to Ca₃Al₂(OH)₁₂ and amorphous aluminum hydroxide. Ca₂Al₂O₅·8H₂O transformed via the intermediate phase Ca₄Al₂O₇·13H₂O to Ca₃Al₂(OH)₁₂ and gibbsite, Al(OH)₃. The phase Ca₄Al₂O₇·19H₂O reacted via the same intermediate phase to Ca₃Al₂(OH)₁₂ and mainly amorphous aluminum hydroxide. The powder pattern of the intermediate phase is reported.     

Effect of Ti5Si3 on wear properties of Ti3Si(Al)C2

Near-fully dense Ti₃Si(Al)C₂/Ti₅Si₃ composites were synthesized by in situ hot pressing/solid–liquid reaction process under a pressure of 30 MPa in a flowing Ar atmosphere at 1580 °C for 60 min. Compared to monolithic Ti₃Si(Al)C₂, Ti₃Si(Al)C₂/Ti₅Si₃ composites exhibit higher hardness and improved wear resistance, but a slight loss in flexural strength (about 26% lower than Ti₃Si(Al)C₂ matrix). In addition, Ti₃Si(Al)C₂/Ti₅Si₃ composites maintain a high fracture toughness (K_IC = 5.69–6.79 MPa m^1/2). The Ti₃Si(Al)C₂/30 vol.%Ti₅Si₃ composite shows the highest Vickers hardness (68% higher than that of Ti₃Si(Al)C₂) and best wear resistance (the wear resistance increases by 2 orders of magnitude). The improved properties are mainly ascribed to the contribution of hard Ti₅Si₃ particles, and the strength degradation is mainly due to the lower Young's modulus and strength of Ti₅Si₃.     

Improvement of coke resistance of Ni/Al2O3 catalyst in CH4/CO2 reforming by ZrO2 addition

This work investigates the improvement of Ni/Al₂O₃ catalyst stability by ZrO₂ addition for H₂ gas production from CH₄/CO₂ reforming reactions. The initial effect of Ni addition was followed by the effect of increasing operating temperature to 500–700 °C as well as the effect of ZrO₂ loading and the promoted catalyst preparation methods by using a feed gas mixture at a CH₄:CO₂ ratio of 1:1.25. The experimental results showed that a high reaction temperature of 700 °C was favored by an endothermic dry reforming reaction. In this reaction the deactivation of Ni/Al₂O₃ was mainly due to coke deposition. This deactivation was evidently inhibited by ZrO₂, as it enhances dissociation of CO₂ forming oxygen intermediates near the contact between ZrO₂ and nickel where the deposited coke is gasified afterwards. The texture of the catalyst or BET surface area was affected by the catalyst preparation method. The change of the catalyst texture resulted from the formation of ZrO₂–Al₂O₃ composite and the plugging of Al₂O₃ pore by ZrO₂. The 15% Ni/10% ZrO₂/Al₂O₃ co-impregnated catalyst showed a higher BET surface area and catalytic activity than the sequentially impregnated catalyst whereas coke inhibition capability of the promoted catalysts prepared by either method was comparable. Further study on long-term catalyst stability should be made.     

The intercalation of C60-containing PEO into layered MnPS3

This paper reports the synthesis and magnetism of a new polymer-inorganic intercalation nanocomposite based on a C₆₀-containing poly(ethylene oxide) (C₆₀-PEO) into layered MnPS₃, which is characterized by XRD, IR and thermal analyses. The lattice expansion (Δd) of the intercalation nanocomposite is about 9.3 Å indicating the successful intercalation. And the charge balance is maintained by K⁺ ions coordinating with PEO chain of C₆₀-PEO polymer, which come from the pre-intercalation compound Mn_1−xPS₃[K_2x(H₂O)_y]. Magnetic measurements indicate that the intercalation nanocomposite (C₆₀-PEO/MnPS₃) exhibits a magnetic phase transition from paramagnetism to ferrimagnetism at about 40 K. And the distinctive hysteresis of M-H relationship further confirms that it is a low temperature ferrimagnetic nanocomposite.     

基于WO3-MoO3和TiO2/CdS复合电极的光电致变色器件

电致变色广泛应用于智能窗领域,但电致变色材料仍需外部电源驱动,将太阳能电池与电致变色材料结合起来的光电致变色器件可实现无需外部供电的智能变色调控。性能优异的变色阴极和光阳极是当下光电致变色器件的研究热点。通过水热法制备WO₃-MoO₃薄膜,研究其电致变色性能;通过水热法结合连续离子层沉积法制备TiO₂/CdS复合薄膜,研究其光电转换性能。最后将WO₃-MoO₃薄膜和TiO₂/CdS复合薄膜分别作为光电致变色器件的变色阴极、光阳极构建WO₃/MoO₃-TiO₂/CdS光电致变色器件。WO₃/MoO₃-TiO₂/CdS光电致变色器件具有较大的光学调制范围(630nm处为41.99%)、更高的着色效率(35.787%),将其作为智能窗应用在现代建筑、通行工具等领域具有重要应用价值。