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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Bridging the gap between NMR measured mean silicate chain length and nano-scale silicate polymorphism of calcium silicate hydrates

Variable stoichiometry and silicate polymorphism in calcium-silicate-hydrates (C-S-H) has impeded the revelation of point defects distribution in the silicate tetrahedral network of C-S-H, which resembles tobermorite crystal structure with some bridging tetrahedra (BT) and paired tetrahedra (PT) vacancies in dreierketten chains. Here we use a computational approach to characterize silicate polymorphism by introducing the vacancy ratio of BT to PT (α) and establishing a three-term empirical mean chain length (MCL) formula for different calcium-to‑silicon ratios (Ca/Si) ranging from 1.2 to 2.3. The formula identifies BT and PT controls at low and high α respectively and allows an inverse mapping of polymorphic range based on NMR experiments. The proposed computational framework quantitatively describes silicate polymorphs and links NMR-measured MCL to C-S-H atomistic configurations at the molecular level.

36 MATERIALS SCIENCE↗
DOE OSTI2021

In situ TEM observation of calcium silicate hydrate nanostructure at high temperatures

Fire poses a substantial threat to concrete structures because calcium silicate hydrate (C-S-H) is not thermally stable at high temperatures. Herein, in situ TEM at temperatures from 20 to 800 °C was conducted to study the thermal-induced structural changes in C-S-H. We captured C-S-H shrinks at an average rate of 0.02 μm{sup 2}/{sup o}C upon heating with three stages observed, including induction, constant, and rapid periods. Our observation revealed that an 800 nm pore could be healed during pore structure evolution owing to the reconstruction and deformation among C-S-H blocks. The Ca/Si ratio was dropped at higher temperatures because of the leakage of calcium ions from the C-S-H structure to form CaO precipitates. The temperature-driven phase transformation and degradation were also detected using electron diffraction that C-S-H was transformed into metastable calcium silicate minerals above 800 °C. This work provides insights into the nanoscale transformation of C-S-H at high temperatures.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Normal and anomalous self-healing mechanism of crystalline calcium silicate hydrates

The origin of different stability of crystalline calcium silicate hydrates was investigated. The tobermorite crystal has been used as an analog of cement hydrate that is being mostly manufactured material on earth. Normal tobermorite is thermally unstable and transforms to amorphous at low pressure. Meanwhile, anomalous tobermorite with high Al content does not significantly transform under high pressure or high temperature. Conducted X-ray absorption spectroscopy explains the weak stability of normal tobermorite which was originally hypothesized by the role of zeolitic Ca ions in the cavities of silicate chains. Atomic simulations reproduced the experimentally observed trend of pressure behavior once the ideal structures were modified to account for the Al content as well as the chain defects. The simulations also suggested that the stability of tobermorite under stress could be rationalized as a self-healing mechanism in which the structural instabilities were accommodated by a global sliding of the CaO layer.

36 MATERIALS SCIENCE↗
DOE OSTI2021

New insights into the mechanism governing the elasticity of calcium silicate hydrate gels exposed to high temperature: A molecular dynamics study

When exposed to fire, the integrity of cement-based materials is governed by thermally-induced changes in the mechanical properties of their binding phase, i.e., the calcium–silicate–hydrate (C–S–H) gel. However, the effect of temperature on the structure, density, and mechanical properties of C–S–H remains only partially known. Here, based on reactive molecular dynamics simulations, we reveal the nature of thermally-induced damage in C–S–H gels. In general, we show that, at the atomic scale, exposure to high temperature results in partial dehydration, volumetric shrinkage, disordering, and stiffening in the C–S–H grains. However, we show that the thermal response of C–S–H strongly depends on its chemical composition, wherein C–S–H systems associated with lower Ca/Si molar ratios are able to undergo higher temperatures before amorphization. Based on these results, we demonstrate that the stiffness of C–S–H gels (i.e., including porosity—as probed by nanoindentation) is governed by a competition between the stiffening of the grains and the decrease in packing density—wherein the latter eventually become predominant.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Plastic deformation mechanism of calcium-silicate hydrates determined by deviatoric-stress Raman spectroscopy

Highlights: • C-(A-)S-H samples under stress were characterized at the bond and grain level. • Small angle scattering showed that 720 MPa reduced grain thickness by 30%. • In-situ Raman showed that cross-linked C-A-S-H slips along its intralayer. • However, in-situ Raman showed that C-S-H slips along the interlayer. • In-situ Raman also showed a growth in CaCO{sub 3}, indicating fracture in both samples. Creep of the cement matrix affects the structural stability of concrete. In Portland cements, the creep is largely controlled by the binding phase calcium-(aluminum-)silicate-hydrate, or C-(A-)S-H. This phase has a lamellar structure and under deviatoric stress aligns its c-axis with the principal stress. However, the limiting resistance to this reorientation is unknown at the nanocrystalline level. Small-angle X-ray scattering shows that the lamellae thickness decreases under 100's MPa deviatoric stress. Deviatoric stress Raman spectroscopy shows that there are two ways that this break-up can occur. If the material's silicate chains are cross-linked, then strain in SiO bonds does not increase above certain stresses, indicating a relaxation adjacent to the SiO bond. If the chains are not cross-linked, then the silicate chains are broken up by rastering against each other, introducing defects. These results show that the plastic deformation of C-(A-)S-H is relevant for Portland cement creep.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Uniaxial stress increases layer stacking disorder in calcium silicate hydrates with low calcium content

The long-term stress response of concrete is controlled by the intergrain and intragrain interactions of calcium-silicate-hydrates (C-S-H), nanocrystalline forms of tobermorites. To investigate both types of interactions, we examined the deviatoric stress response of 11 Å tobermorite powder with X-ray diffraction, finding that its layer stacking (i.e., sliding) disorder significantly increases. A similar experiment was performed on nanocrystalline C-S-H powders before and after applying a 360 MPa uniaxial stress. Layer stacking disorder (in the form of intragrain deformation) increases when there is low water content and when the basal spacing is large. We also find that grains with a smaller thickness-to-diameter aspect ratio are first to develop preferred orientation (in the form of intergrain sliding), facilitated by gel water. Furthermore, these findings show that intragrain deformations in C-S-H can occur at relatively low stresses and provide insights into the creep mechanism of C-S-H.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Coordination environment of Si in calcium silicate hydrates, silicate minerals, and blast furnace slags: A XANES database

Understanding the silicate polymerization of calcium silicate hydrate (C-S-H) gel and its crystalline polymorphs is important in cement science. NMR can determine Si environments, but the measurement can be time-consuming and provides no spatial information. X-ray absorption near-edge structure (XANES) spectroscopy is a fast tool for probing Si coordination, possibly with spatial information. However, there lacks an understanding of Si K-edge XANES spectra of cement-related silicate phases. Here, a Si K-edge XANES spectral database of nanocrystalline C-S-H, C-S-H minerals, blast-furnace slags, and metakaolin is provided. Si K-edge of C-S-H minerals shifts to higher energies with higher polymerized Si and lower CaSi connectivity in the Si second nearest neighbor shell. Si K-edge energy shows weak correlations with Ca/Si ratio, average SiO bond length, and SiO{sub 4} distortion due to the structural complexity of silicates. The substitution of Al for Si shifts the Si K-edge of tobermorite and slags to higher energies.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Mechanical Characterization of Low Modulus Polymer-Modified Calcium-Silicate-Hydrate (C-S-H) Binder

Calcium-silicate-hydrate (C-S-H) represents a key microstructural phase that governs the mechanical properties of concrete at a large scale. Defects in the C-S-H phase are also responsible for the poor ductility and low tensile strength of concrete. Manipulating the microstructure of C-S-H can lead to new cementitious materials with improved structural performance. This paper presents an experimental investigation aiming to characterize a new synthetic polymer-modified synthetic calcium-silicate-hydrate (C-S-H)/styrene-butadiene rubber (SBR) binder. The new C-S-H/SBR binder is produced by calcining calcium carbonate and mixing this with fumed silica (SiO 2 ), deionized water and SBR. Mechanical, physical, chemical and microstructural characterization was conducted to measure the properties of new hardened C-S-H binder. Results from the experimental investigation demonstrate the ability to engineer a new C-S-H binder with low elastic modulus and improved toughness and bond strength by controlling the SBR content and method of C-S-H synthesis. The new binder suggests the possible development of a new family of low-modulus silica-polymer binders that might fit many engineering applications such as cementing oil and gas wells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Probing Carbon Mineralization Mechanisms in Pore and Bulk Fluids by Harnessing Architected Calcium Silicates

The ability to synthesize materials with well-controlled pore structures gives us unprecedented control over probing fluid interactions with reactive interfaces and advancing calibrated insights into coupled chemo-morphological interactions. One of the primary challenges in developing crystalline silicate materials lies in achieving ordered pore structures. Existing approaches of producing amorphous mesoporous metal silicates via sol–gel methods and heat-treatment of these materials to produce crystalline phases cause the pore structures in the amorphous phases to collapse. To overcome this challenge, carbon coating of amorphous mesoporous calcium silicate particles is carried out to retain the pore structure, while the material is heated to produce crystalline calcium silicate with calcium sulfate inclusions. The pore diameter in these materials is about 3.9 nm, with a surface area and a pore volume of 28.75 m 2 /g and 0.092 cm 2 /g, respectively. The mechanisms of carbon mineralization are investigated by reacting architected calcium silicate with 1 M Na 2 CO 3 and monitoring the evolution in the structural phases using operando wide-angle X-ray scattering (WAXS) measurements. Formation of stable calcium carbonate polymorph or calcite and metastable calcium carbonate polymorph or vaterite in pore and bulk fluids, respectively, resulting from the reaction between Na 2 CO 3 and CaSiO 3 , are noted. The mechanisms associated with carbon mineralization are delineated using ReaxFF molecular dynamics (MD) simulations. The surface dissolution reaction is initiated by 2H + ions that replace a Ca 2+ ion in the Ca–silicate matrix. Ca 2+ ions in the solution initially react with water to form calcium hydroxide and eventually form calcium (bi)carbonate. A slow and gradual increase in the formation of sodium silicate in the solution resulting from the reactions of silicic acid or the silicon dioxide reaction with sodium hydroxide is noted. When carbon mineralization occurs in environments bearing interfacial fluids, calcite is the dominant calcium carbonate polymorph, as determined using experiments with pore fluids and molecular-scale simulations. In conclusion, these studies provide fundamental insights into the mechanisms underlying the carbon mineralization of calcium silicate informed by experiments and molecular-scale simulations.

Calcium↗
DOE OSTI2020

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. Additionally, 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.

42 ENGINEERING↗
DOE OSTI2020

Estimation of Sorption Behavior of Europium to Calcium Silicate Hydrate by Thermal Analysis - 20172

High-level radioactive waste generated from reprocessing processes will be disposed in a geological disposal that is deep underground. Calcium silicate hydrate is formed as a secondary mineral in the repository via the reaction of calcium ions leaching from the cement and the silicic acid dissolved from the host rocks. In this study, the sorption behavior of europium, which is also known as a chemical analog of americium, on calcium silicate hydrate was examined. The solid phase was analyzed via thermogravimetry- differential thermal analysis, differential scanning calorimetry, Raman spectroscopy, fluorescence spectroscopy, and fluorescence lifetime analysis. To understand the behavior of calcium silicate hydrate under conditions saturated with groundwater, the study samples were analyzed using the above methods, except for deferential scanning calorimetry, without a drying process. The results of the differential scanning calorimetry analyses showed that the temperatures for the endothermic peaks of calcium silicate hydrate for the lower Ca/Si ratios were larger than those for the higher Ca/Si ratios for coexistent conditions of europium ions. Hence, the relationships of the temperatures of the endothermic peaks and the Ca/Si ratios were reversed by the addition of europium ions. These study results suggest that calcium silicate hydrate can immobilize europium ions, thus preventing the production of colloidal forms. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS1981

Thermodynamics and kinetics of the sulfation of porous calcium silicate

The sulfation of plasma sprayed calcium silicate in flowing SO2/air mixtures at 900 and 1000 C was investigated thermogravimetrically. Reaction products were analyzed using electron microprobe and X-ray diffraction analysis techniques, and results were compared with thermodynamic predictions. The percentage, by volume, of SO2 in air was varied between 0.036 and 10 percent. At 10 percent SO2 the weight gain curve displays a concave downward shoulder early in the sulfation process. An analytical model was developed which treats the initial process as one which decays exponentially with increasing time and the subsequent process as one which decays exponentially with increasing weight gain. At lower SO2 levels the initial rate is controlled by the reactant flow rate. At 1100 C and 0.036 percent SO2 there is no reaction, in agreement with thermodynamic predictions.

Miller, R. A.↗
DOE OSTI2021

Initial hydration process of calcium silicates in Portland cement: A comprehensive comparison from molecular dynamics simulations

As the main components of Portland cement, calcium silicates show substantial differences in their hydration reactivity which have not been fully explained. A comprehensive comparison of the initial hydration process of calcium silicates, namely dicalcium silicate (C{sub 2}S) and tricalcium silicate (C{sub 3}S), was conducted using molecular dynamics simulations. The initial hydration process was divided into three stages using cut-off times of 0.001 ns and 3 ns. The hydration of M{sub 3}-C{sub 3}S (010) was more evident than that of β-C{sub 2}S (100), supported by the hydroxylation degree, radial distribution function, atomic density profile, etc. The coordination number of the surface Ca atoms might be the underlying reason for such a difference. Interactions between cement surfaces and water molecules were mainly characterised by solid OH bonding and Ca-water O bonding. Dissolution of Ca atoms was observed, although quite scarce, while no dissolution of Si atoms was observed.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Effects of pH on the nano/micro structure of calcium silicate hydrate (C-S-H) under sulfate attack

Calcium silicate hydrate (C-S-H), the most important Portland cement hydration product, determines the mechanical properties and durability of cementitious materials. In marine environment, C-S-H often suffers from sulfate attack – one of the most common and severe degradations for concrete. pH is considered as a critical factor in determining the deterioration behavior of C-S-H during sulfate attack, of which the significance may be overlooked. This study focused on the role of pH on the deterioration of C-S-H in terms of the composition and nano/micro structure under sulfate attack. The results show that lowering pH aggravates the decalcification of C-S-H, whereas a strong alkaline condition is beneficial to increase the resistance to deterioration. An increase in the mean chain length together with the proportion of large pores (>10 nm) is observed when C-S-H is subjected to low-pH sulfate attack (pH = 10–12), resulting in a relatively loose structure. The deep analysis on defective tobermorite model reveals that calcium at the interlayer of C-S-H nanostructure is readily removed under sulfate attack, thereby improving the potential of Si-O-Si groups formation and increases the mean chain length of C-S-H.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Effective cation exchange capacity of calcium silicate hydrates (C-S-H)

The binding of alkalis and calcium to calcium silicate hydrate (C-S-H) can be measured by cation exchange using cobalt hexamine solution with adapted pH. The effective cation exchange capacity (CEC) decreased at higher Ca/Si in C-S-H. A maximum of charge{sub exch}/Si of 0.08–0.10 was measured at Ca/Si = 0.8 decreasing to 0.01–0.02 at Ca/Si = 1.6. At high Ca/Si, only a minor fraction of Ca was present at exchangeable sites, while most of the Ca{sup 2+} present in interlayer or surface was specifically bound and thus not exchangeable. In contrast, sodium was present only at exchangeable sites in the C-S-H, more at low than at high Ca/Si. An increase of pH in the presence of 100 mmol/L NaOH increased the effective CEC of C-S-H by 5–10% indicating a limited influence of pH on the deprotonation of the silanol groups.

36 MATERIALS SCIENCE↗
DOE OSTI2021

New insights into creep characteristics of calcium silicate hydrates at molecular level

The fundamental mechanisms under concrete creep are far from being fully understood, especially at the molecular level. Hereby, a calcium-silicate-hydrate (C-S-H) molecular model is developed to explain, for the first time, the creep characteristics at various stress states, temperature levels and water contents, which are not accessible experimentally. Rather tensile and compressive loadings, C-S-H only creeps under shear loadings originating from the sliding of the calcium silicate layers over each other as the interlayer component (water and ions) acts as a lubricator. A heterogeneous creep characteristic is observed. Elevated temperature reduces the interlayer lubricator viscosity and weakens the interfacial adhesion between the layers and the interlayer lubricator, which accelerates C-S-H creep. The removal of interlayer water enhances the creep resistance, resulting from the reduced interlayer space and enhanced interfacial adhesion. The atomic-level mechanisms explain the inter-CSH-particle behaviours at the microscale, which bridges the gap between atomistic simulation and microcosmic phenomenon.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Iron incorporation in synthetic precipitated calcium silicate hydrates

Effect of Fe{sup 3+} on the precipitation of synthetic calcium silicate hydrates (C-S-H) under controlled conditions has been evaluated. Using extremely basic either initial calcium nitrate or sodium silicate solutions (pH > 11), incipient formation of ferrihydrite in both solutions was observed. In this case both C-S-H and iron-containing siliceous hydrogarnet are formed. For pH < 11, ferrihydrite was absent. Only C-S-H is formed. The presence of magnetically dilute Fe{sup 3+} in the C-S-H was shown by EPR and the atomic Fe/Si ratio of the C-S-H phase was shown to be between 0.01% and 0.1% by measuring and modelling the {sup 29}Si spin-lattice relaxation in NMR experiments. A uniform distribution of Fe{sup 3+} when C-S-H precipitates in the absence of initial ferrihydrite is obtained. When initial ferrihydrite is present, a non-uniform distribution of Fe{sup 3+} is found and the concentration of Fe{sup 3+} in the C-S-H is merely 3% of the overall iron concentration, suggesting the initial formation of ferrihydrite restricts the incorporation of iron into C-S-H.

36 MATERIALS SCIENCE↗