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At least 721 records · Page 40

Belite cements and their activation

Belite cements, BCs, containing mainly belite, alite and calcium aluminates, are currently used as low heat cements. These binders produce high amounts of C–S–H gel and have very good durability properties which are reviewed. Additional advantages include: (i) lower limestone demand, with lower associated CO{sub 2} emissions; (ii) lower energy demand; (iii) lower kiln operating temperature, which means lowering CO{sub 2} and NO{sub x} emissions from fuel burning; and (iv) lower temperature increase at early hydration age. However, early-age strength developments are not competitive with those of Portland cements. Hence, to improve their early-age strength developments is a research priority known as activation. This enhancement can be attained by three compatible approaches: (i) chemical, (ii) physical; and (iii) admixture activations. The current research status for BCs activation is reviewed including: cost-effective element substitutions to stabilize high-temperature forms; fast cooling, milling and mild temperature hydration as physical activation; and the use of C–S–H seeds as admixture activation. After discussion of the resulting microstructures, a research outlook is exercised.

36 MATERIALS SCIENCE↗

Physicochemical properties of the Portland cement-based mortar exposed to deep seafloor conditions at a depth of 1680 m

Achieving breakthroughs in marine technologies requires the development of infrastructures submerged in deep-sea environments, whose physicochemical effects on cement-based materials considerably differ from those of shallow seas. However, very few studies focused on the cement-based materials subjected to deep-sea conditions. This work investigates the changes in the compressive strength and phase composition of the cement mortar kept on the seafloor with a depth of 1680 m for 608 d. The mortar specimens salvaged from the seafloor exhibited severe visible damages, including softened mashy structures and significantly decreased compressive strengths. The obtained X-ray diffraction, scanning electron microscopy, and nuclear magnetic resonance data revealed that the dissolution of portlandite, decalcification of calcium (alumino) silicate hydrate, and formation of brucite, magnesium (alumino) silicate hydrate, a hydrotalcite-like phase, thaumasite, and ettringite likely contributed to the disintegration of mortar, which could be further accelerated by the low temperature of the deep-sea environment.

36 MATERIALS SCIENCE↗

Atomic structure and phase assemblages in novel M-(N)-A-S-H materials

This paper investigates the atomic structure and phase assemblages in new sodium-stabilized magnesium aluminosilicate hydrate (M-(N)-A-S-H) cementitious binders. Results indicate that in the absence of Ca{sup 2+}, Mg{sup 2+} promotes a binder atomic structure of Si-Al tetrahedral sheets and octahedral Mg sheets with hydrated Na{sup +} cations likely in the interlayer sites similar to trioctahedral micas (phyllosilicates). NMR studies verify the incorporation of Al in tetrahedral silicate sheets. XRD demonstrates the ability of these regions to nucleate and form zeolites (i.e., sodalite) as well as the formation of Mg-Al layered double hydroxide (LDH) phases (i.e., meixnerite), which is expected due to high concentrations of Mg and Al. TGA results indicate that M-(N)-A-S-H possesses chemically bound water and hydroxyl units similar to other Mg binders. These results evince the critical role of Mg to form unique atomic structures and durability-linked phases in low-calcium alkali-activated materials.

36 MATERIALS SCIENCE↗

Resting time effect on the rheological behavior of cement paste in presence of superplasticizer

Rheology has been widely used to describe the flow properties of fresh cement-based suspensions. Nevertheless, the effect of early hydration product formation on rheology, and the effect of shear on breaking of hydration bonds is not fully understood. Therefore, the characterization of the time-dependency of rheology has become necessary to predict precisely the behavior of concrete during placement. In this paper, variations in the resting time in between rheological tests were imposed to evaluate the effects on the development of internal structure of the mixture using different dispersing agents. Increasing resting time in between measurements mainly enhances viscosity, but the magnitude seems strongly dependent on the dispersant used. However, the effect of the employed procedure, as two procedures were evaluated, seems to have a stronger influence on the time-evolution of the rheological properties than changing the resting time in between measurements.

36 MATERIALS SCIENCE↗

Chemistry of the interaction between an alkoxysilane-based impregnation treatment and cementitious phases

Chemical compatibility with a wide range of materials is among the features that has driven the use of alkoxysilanes as consolidants in built structures. Such compatibility is particularly important in cementitious materials where the reaction with portlandite may generate C-S-H gel, one of the main hydration phases of OPC. The cementitious matrix is a complex system, however, and the reaction of its many phases with alkoxysilanes, while poorly understood, may determine treatment efficacy. This article describes a detailed study of the individual interactions between an oligomeric alkoxysilane-based impregnation treatment previously shown to interact with the portlandite present in cement paste and the cementitious phases generated in ordinary portland cement hydration. The findings show that both portlandite and C-S-H gel interact with the silicon oligomers in the hydrolysed impregnation treatment to generate a C-S-H gel (in the case of portlandite) and a rise in C-S-H gel mean chain length (MCL). Ettringite is also altered in the presence of alkoxysilanes, transforming to gypsum and AH{sub 3}. Its transformation generates a tetrahedral aluminium that is taken up into a high silicon gel sourced from the treatment to form an amorphous aluminosilicate gel. Monocarboaluminate and katoite also partially decompose in the interaction with the product, whereas gibbsite remains unaffected.

36 MATERIALS SCIENCE↗

Effect of ZnO on the whiteness of white Portland cement clinker

The addition of ZnO to significantly improve the Hunter whiteness of white Portland cement (WPC) clinkers is introduced in this paper. The effects of ZnO on the whiteness of WPC were studied by chroma analysis, X-ray diffraction (XRD), the Rietveld method, hydration heat measurements and SEM-EDS. The results showed that adding ZnO increased the visible light reflectance, increased the brightness (L{sup ⁎}), and reduced the yellowness (b{sup ⁎}) of WPC clinker with high Fe{sub 2}O{sub 3}. Therefore, ZnO can increase the whiteness of WPC clinker. Zn was mainly distributed in the amorphous phase and unquantifiable crystalline phase (ACn), and then dissolved in the silicate phase. ZnO stabilized R-C{sub 3}S, reduced the crystallization of C{sub 3}A, and increased the ACn content. ZnO increased the amount of Fe in the ACn and minerals, thereby reducing the formation of C{sub 4}AF and improving whiteness. ZnO increased the accumulated heat of hydration but prolonged the induction period. This method provides a new approach for the WPC industry to broaden sources of raw materials and improve product quality.

36 MATERIALS SCIENCE↗

Microstructural refinement of cement paste internally cured by polyacrylamide composite hydrogel particles containing silica fume and nanosilica

Supplementary cementitious materials were incorporated into hydrogel-based internal curing agents to improve the hydration, microstructure, and ultimately strength of internally cured high-performance cement paste. Polyacrylamide composite hydrogel particles containing amorphous silica – either silica fume or nanosilica – and two different polymer network crosslink densities were synthesized and incorporated into cement paste. The presence of silica and low crosslink density increased the absorption capacity of the particles in pore solution. Micrographs of internally cured paste indicated a significant improvement in hydrogel-related void-filling ability and an increase in void size for low crosslink density particles containing silica. Compressive strength and electrical resistivity increased at later ages for paste samples containing particles with higher silica dosage. The relationship between extent of hydration, void size, and void-filling activity was found to strongly influence the paste's long-term strength and is thus an important structure-property relationship to consider when selecting hydrogels for internal curing purposes.

36 MATERIALS SCIENCE↗

Carbonation of model cement pastes: The mineralogical origin of microstructural changes and shrinkage

This study explored the reactive processes of atmospheric carbonation and the consequences with respect to cementitious materials. Two model pastes were used: hydrated C{sub 3}S (including C-S-H and portlandite) and a paste prepared by hydrating a blend of C{sub 3}S and nanosilica (including C-S-H only). The two pastes were carbonated under accelerated conditions in the laboratory. The resulting mineralogical assemblage was examined using X-ray diffraction, thermogravimetric analysis and nuclear magnetic resonance. The microstructural changes were studied by X-ray tomography and porosimetry, and their macroscopic impacts were evaluated through gas diffusion and shrinkage measurements. The use of model pastes allowed for the evaluation of the change in solid volume induced by the carbonation of C-S-H. C-S-H decalcification and subsequent silica chain polymerisation were found responsible for carbonation shrinkage (and potentially cracking). Finally, the results highlight the protective role of portlandite: portlandite helped in limiting C-S-H decalcification and then reducing carbonation shrinkage and cracking.

36 MATERIALS SCIENCE↗

Evidence of formation of an amorphous magnesium silicate (AMS) phase during alkali activation of (Na-Mg) aluminosilicate glasses

Highlights: • No hydrotalcite-group phase is formed as Al preferentially incorporates into zeolites. • Mg forms an amorphous Mg silicate (AMS) phase. • AMS is a more depolymerized phase when compared to Mg silicate hydrate (M-S-H). • High charge density of Mg effectively stabilizes depolymerized silicates in AMS phase. • Existence of AMS phase should be considered as possibility in Mg-rich AAMs. There is some ambiguity regarding the fate of Mg during the alkali activation of Mg-rich precursors within the broader field of alkali activated materials (AAMs). The present work addresses this issue by studying the reaction products in AAMs synthesized from (Na-Mg) aluminosilicate glasses. Here, instead of magnesium silicate hydrate (M-S-H) phase, Mg exclusively forms an amorphous magnesium silicate (AMS) phase. Compared to M-S-H, AMS is a more depolymerized phase, which has not previously been well documented. The formation of AMS seems to be driven by the high charge density of the Mg cation which effectively stabilizes the depolymerized silicate species. We also show that the lack of hydrotalcite-group phases is due to aluminum depletion by zeolite formation. This work highlights the need to consider the existence of the AMS phase in Mg-containing AAMs, especially in complex systems, where its identification may be difficult.

36 MATERIALS SCIENCE↗

Intrinsic reactivity and dissolution characteristics of tetracalcium aluminoferrite

Tetracalcium aluminoferrite is one of the main phases of Portland cement, the dissolution characteristics of which however have not been fully revealed. This work adopted first-principles calculations and Mössbauer spectroscopy as well as X-ray diffraction analysis to clarify the intrinsic reactivity of different species of tetracalcium aluminoferrite crystals. Ca ions are the most reactive species of tetracalcium aluminoferrite and Al ions are slightly more reactive than Fe ions. Moreover, the tetrahedral Al and Fe ions are more reactive than the octahedral Al and Fe ions. These indicate dissolution characteristics of tetracalcium aluminoferrite crystals, namely, Ca ions dissolve first and the tetrahedral species dissolve faster than the octahedral species. After the initial dissolution, the dissolved ions nucleate and grow on the defective surface of C{sub 4}AF and the C{sub 4}AF residues are fully hydroxylated. The further hydration thereafter becomes the complex dissolution with the nucleation and growth of hydration products.

36 MATERIALS SCIENCE↗

Near-field infrared microscopy: A novel analytic mapping technique to nanocharacterize calcium silicate-based cement materials

Infrared imaging via scattering-type scanning near-field optical microscopy (s-SNOM) allows chemical mapping of organic and inorganic materials with nanoscale spatial resolution. However, its potential adaptation to the complex multiphase structure of Portland cement is yet to be explored. Here we demonstrate the successful implementation of s-SNOM to spatially resolve coexisting chemical phases in tricalcium silicate, Portland cement's main compound, with 20-nm resolution. We found that s-SNOM is sensitive to different anhydrous polymorphic phases, revealing nanoscale domains that are ‘invisible’ to other microscopic techniques. Furthermore, s-SNOM's ability to distinguish the unhydrated and hydrated phases signifies its great promise as an analytical tool to study the complex hydration process of cement. The key to s-SNOM's application was nano-modifying the surface roughness of the cement samples, allowing nanoscale infrared imaging without topographical artifacts. Our study opens a window for infrared spectral microscopy in cement and other porous inorganic materials.

36 MATERIALS SCIENCE↗

Reactivity in cement pastes bearing fine fraction concrete and glass from construction and demolition waste: Microstructural analysis of viability

Converting construction and demolition waste (CDW) into secondary raw materials is one of the priorities of environmental policy and circular economy strategy. This study analysed the variation in eco-efficient paste reactivity with OPC replacement ratio (5% to 10%) and hydration time (2 d, 28 d and 90 d). Three types of CDW were explored: two (calcareous and siliceous) consisting of fine (4 AH{sub 13} and C{sub 4}AcH{sub 11}, ettringite and portlandite, were the same as observed in OPC hydration. These findings attest to the scientific viability recycling such CDWs as mineral additions in eco-cement manufacture and consequently eliminating the need for stockpiling these materials at recycling/storage plants.

36 MATERIALS SCIENCE↗

Factors affecting the reactivity of slag at early and late ages

This study investigates the difference between the reactivity of slag in NaOH solution (w/s = 100) and in cement paste (w/b = 0.4). The reactivity of slag is much higher in NaOH solution than in cement paste. When the NaOH solution is saturated with portlandite, the rate of reaction of slag decreases to approach that in cement paste. This suggests that the slower reaction of slag in cement paste might be due to the presence of calcium ions released by the clinker phases. At 28 days, relative humidity measurements indicate that water is only present in pores less than 6 nm. Above 6 nm, hydration cannot take place due to the lack of water. From a thermodynamic point of view, the small size of water filled pores may slow down the slag reaction due to the high concentration of species in solution required for hydrate growth to balance the increase of the surface energy.

36 MATERIALS SCIENCE↗

In-situ neutron radiography of pore-water movement in portland cement mortar under subzero temperature exposure: Insights from D 2 O-H 2 O systems

Neutron radiography was employed in this study to monitor real-time pore water movement in portland cement mortar exposed to subzero temperatures, providing novel insights into freeze-thaw (F-T) damage mechanisms. Deuterated water (D 2 O) was used to hydrate the cement in the mortar specimens, and the pore structure was saturated with water (H 2 O), allowing for a contrast that enabled detailed tracking of water movement predominantly in the pore structure. Furthermore, the mortar sample was placed on a chiller plate set to subzero temperatures, thereby providing a one-dimensional temperature gradient vertically in the sample. Neutron radiography revealed that unfrozen water migrated upward as the freezing front advanced, which can create hydraulic pressure within the mortar microstructure and may contribute to the initiation and propagation of microcracks during F-T cycles. Additional characterization of the concrete made with D 2 O showed a marked contrast to the samples made with H 2 O, including delayed hydration, diminished compressive strength, and greater porosity. Therefore, while mortar made with D 2 O allowed for greater neutron contrast to the pores filled with H 2 O, further study is required to produce mortars with similar properties to those made with H 2 O. In addition, further refinement is needed to the radiography experiment to allow for greater control of temperatures and potential quantification of the water concentration.

Air-void system↗

Ammonium sulfate leaching of NaOH-treated monazite

Rare earth elements (REEs) can be extracted from monazite under aggressive decomposition and leaching conditions. Much of the waste rocks are removed prior to the extraction process to minimize the costs and waste generation, which is difficult with coal byproducts. The possibility of extracting REEs from low-grade monazite concentrates under relatively mild conditions has been explored to simulate the extraction of REEs from coal byproducts. It has been found that monazite can be decomposed in 10 to 50 % NaOH solutions at 80 °C, with the resulting hydrous oxide being subjected to the ammonium sulfate leaching at pH 4. Further, the ς-potential measurements conducted in the presence of the lixiviant suggest that the NH 4+ ions displace the hydrated Ln 3+ ions from the surface of Ln(OH) 3 (s) by an ion-exchange mechanism, which may be driven by the large differences in the hydration enthalpies between the charged species involved. This approach may be advantageous over acid leaching, including the regeneration of spent lixiviant, lower chemical consumption, and leaching at higher pH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interfacial Hydrogen-Bond Dynamics in Transition Metal Compounds

Understanding how water behaves when confined within atomic layers of active transition-metal carbides, nitrides, and carbonitrides is essential for uncovering the fundamental principles needed to engineer solid–liquid interfaces at the atomic scale. Yet, how lattice element chemistry and surface termination groups collectively regulate the structure and mobility of such interlayer water remains poorly understood. Here, we present a composition-controlled investigation of interlayer water dynamics in layered transition-metal nitride, carbide, and carbonitride systems using a systematic integration of quasi-elastic neutron scattering (QENS), ab initio molecular dynamics (AIMD) simulations, and density functional theory (DFT) calculations. QENS measurements show that nitride-rich systems host mobile, translationally diffusing water with thermally activated self-diffusion coefficients on the order of 10 –10 m 2 s –1 , whereas mixed C/N lattices confine water to localized, nontranslational motion that is insensitive to temperature. AIMD and DFT reveal that lattice C/N chemistry and surface functional group composition reshape the first hydration layer by modulating the surface electronic structure and termination-dependent hydrogen-bond networks, leading to pronounced differences in water ordering and thermal resilience. On the other hand, fully carbide systems exhibit intermediate behavior, highlighting that water mobility is not primarily controlled by the hydration level alone but by the coupling between lattice composition and surface chemistry. Overall, this study establishes how surface chemistry and lattice composition jointly control interfacial hydrogen bond dynamics, offering a mechanistic framework for designing transition-metal layered materials with tailored interfacial transport properties.

Hydration↗

Nanometer-Scale Correlations in Aqueous Salt Solutions

The intermediate-range (1–4 nm) correlation of cations, an- ions, and water in aqueous alkaline earth salt solutions is measured using synchrotron X-ray diffraction. We differentiate from the entire solution structure factor, S(Q), a separate region at low Q (<1 °A-1) containing local diffraction maxima (pre-peaks) that indicate nanometer-scale oscillatory behavior. These features are quantitatively reproduced with classical molecular dynamics simulations. At high concentrations, the pre-peaks emerge from correlations arising from existence of small quasi close-packed lattice- like structures comprised of cation hydration spheres. We also analyze the concentration dependence of the pre-peak and discuss the overall results in light of the rich literature dealing with intermediate-range correlations underlying universal phenomena in concentrated electrolytes. The authors were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is operated by Battelle for the U.S. Department of Energy under Contract No. DE-AC05-76RL01830. Computing resources were generously allocated by PNNL's Institutional Computing program. DOE Contract No. DEAC02- 06CH11357 supports operation of the Advanced Photon Source at Argonne National Laboratory.

Chemical physics, nucleation, Madelung potential↗

Deciphering Photochemical Reaction Pathways of Aqueous Tetrachloroauric Acid by X-ray Transient Absorption Spectroscopy

Photolysis reaction pathways of [Au(III)Cl 4 ] - in aqueous solution have been investigated by time-resolved X-ray absorption spectroscopy. Ultraviolet excitation directly breaks the Au-Cl bond in [Au(III)Cl 4 ] - to form [Au(II)Cl 3 ] - that becomes highly reactive within 79 ps. Disproportionation of [Au(II)Cl 3 ] - generates [Au(I)Cl 2 ] - , which is stable for ≤ 10 mu s. In contrast, intense near-infrared lasers photolyze water to generate hydrated electrons, which then reduce [Au(III)Cl 4 ] - to [Au(II)Cl 3 ] - at 5 ns. Hydrated electrons further induce a chain reaction from [Au(II)Cl 3 ] - to [Au(0)Cl] - by successively removing one Cl - . The zero-valency Au anions quickly polymerize and condense to form Au nanoparticles, which become the dominating product after 400 s. Here our results reveal that the condensation of zero-valency Au starts with dimerization of gold clusters coordinated with chloride ions rather than direct condensation of pristine Au atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗