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At least 127 records · Page 7

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↗

Topological origin of phase separation in hydrated gels

Depending on their composition, hydrated gels can be homogeneous or phase-separated, which, in turn, affects their dynamical and mechanical properties. However, the nature of the structural features, if any, that govern the propensity for a given gel to phase-separate remains largely unknown. Here, we argue that the propensity for hydrated gels to phase-separate is topological in nature. We employ reactive molecular dynamics simulations to model the early-age precipitation of calcium–alumino–silicate–hydrate (Csingle bondAsingle bondSsingle bondH) gels with varying compositions, i.e., (CaO) 1.7 (Al 2 O 3 ) x (SiO 2 ) 1 – x (H 2 O) 3.7 + x . By adopting topological constraint theory, we investigate the structural origin of phase separation in hydrated gels. We report the existence of a homogeneous-to-phase-separated transition, wherein Si-rich (x ≤ 0.10) Csingle bondAsingle bondSsingle bondH gels are homogeneous, whereas Al-rich (x > 0.10) Csingle bondAsingle bondSsingle bondH gels tend to phase-separate. Furthermore, we demonstrate that this transition is correlated to a topological flexible-to-rigid transition within the atomic network. Finally, we reveal that the propensity for topologically-overconstrained gels to phase-separate arises from the existence of some internal stress within their atomic network, which acts as an energy penalty that drives phase separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Intrinsic mechanical properties and seeding effect of tobermorite synthesized in supercritical water

This publication reports for the first time the physiochemical, the intrinsic mechanical properties and the seed effect of anomalous Al-substituted 11 Å tobermorite synthesized via the innovative supercritical hydrothermal flow process at 400 °C and 25 MPa. This approach allows synthesizing highly crystalline tobermorite fibers in only 8 s, with characteristics very close to the natural tobermorite. The anomalous 11 Å tobermorite exhibits aluminosilicate chains with a high polymerisation degree and a less defective structure compared to materials produced via the conventional hydrothermal method. Furthermore, the intrinsic mechanical properties of Al-tobermorite synthesized in supercritical water are investigated for the first time by High-Pressure XRD. This Al-substituted 11 Å tobermorite is characterised by higher incompressibility along the b-axis and bulk modulus K0 in comparison with what is commonly observed for other synthetic tobermorite. The tobermorite acts as nucleation points to trigger the quick formation of the hydration product in Portland cement paste.

Calcium silicate hydrate↗

The structure of CaO–MgO–Al 2 O 3 –SiO 2 melts and glasses doped with FeO X –NiO

Neutron and x-ray diffraction measurements have been performed on CaO–MgO–Al 2 O 3 –SiO 2 (CMAS) glasses doped with NiO–Fe X O at room temperature, along with x-ray measurements on aerodynamically levitated liquids at ≥2000 K. The disordered structures have been modeled using empirical potential structure refinement to investigate the relation between the aluminosilicate network and the modifying cations. The SiO 4 and AlO 4 tetrahedra are found to have wider Si–O and Al–O bond distance distributions in the glass, and the first Ca–O n coordination shell is highly distorted, redistributing different populations of long and short bonds between the liquid and the glass. The addition of Fe and Ni at low aluminosilicate content increases the number of free oxygens not bonded to AlO 4 or SiO 4 . Mg–O and Fe–O are both found to be predominantly fourfold and fivefold in the liquid and glassy states. Despite these low coordination numbers, their bond angle distributions indicate that they are predominantly in nontetrahedral-type geometries, with ferrous and ferric iron possessing similar coordination environments. The Ca–O and Mg–O average coordination numbers and enthalpies of solution are consistent with their higher reactivity within relatively acidic aluminosilicate melts.

36 MATERIALS SCIENCE↗

A pyroxene-based quantum magnet with multiple magnetization plateaus

Pyroxenes (AMX 2 O 6 ) consisting of infinite one-dimensional edge-sharing MO 6 chains and bridging XO 4 tetrahedra are fertile ground for finding quantum materials. Thus, here, we have studied calcium cobalt germanate (CaCoGe 2 O 6 ) and calcium cobalt silicate (CaCoSi 2 O 6 ) crystals in depth. Heat capacity data show that the spins in both compounds are dominantly Ising-like, even after being manipulated by high magnetic fields. On cooling below the Néel temperatures, a sharp field–induced transition in magnetization is observed for CaCoGe 2 O 6 , while multiple magnetization plateaus beneath the full saturation moment are spotted for CaCoSi 2 O 6 . Our analysis shows that these contrasting behaviors potentially arise from the different electron configurations of germanium and silicon, in which the 3d orbitals are filled in the former but empty in the latter, enabling electron hopping. Thus, silicate tetrahedra can aid the interchain superexchange pathway between cobalt(II) ion centers, while germanate ones tend to block it during magnetization.

Science & Technology - Other Topics↗

Waste-to-Energy (WTE)-derived Low-Carbon-Footprint Concrete (LCFC)

The construction industry is estimated to generate around 600 million tons of concrete and demolition waste annually in the US. In comparison, Waste-To-Energy (WTE) plants generate about 6.6 million tons of ash from the combustion of municipal solid waste.1–4 Research has been ongoing for decades to upcycle WTE-ash and C&D waste.

36 MATERIALS SCIENCE↗

Oxygen isotope cosmothermometer.

Variations in oxygen isotopic abundances of meteoritic minerals, chondrules, whole meteorites, and planets are discussed in terms of a model involving isotopic exchange between primordial dust and a cooling solar nebular gas. From the temperature-dependence of the isotopic fractionation factors, temperatures have been assigned to the processes of initial condensation, chondrule formation, and planetary accretion. Separated phases from carbonaceous chondrites fall into three isotopic groups representing widely differing conditions of formation: (1) low-iron olivine and pyroxene, and calcium-aluminum silicates condensed at temperatures above 1000 K; (2) high-iron olivine and pyroxene melted to form chondrules after prior cooling and exchange to temperatures of 530-620 K; and (3) hydrous silicates condensed at temperatures below 400 K.

Onuma, N.↗

The chemistry of Saudi Arabian sand: A deposition problem on helicopter turbine airfoils

Recent operations in the Persian Gulf have exposed military helicopter turbines to excessive amounts of ingested sand. Fine particles, less than 10 microns, are able to bypass the particle separators and enter the cooling and combustion systems. The initial sand chemistry varies by location, but is made up of a calcium aluminum silicate glass, SiO2 low quartz (Ca,Mg) CO3 dolomite, CaCO3 calcite, and occasionally CaCl rocksalt. The sand reacts in the hot combustion gases and deposits onto the turbine vanes as CaSO4, glass, and various crystalline silicates. Deposits up to 0.25 in. thick have been collected. Although cooling hole plugging is a considerable problem, excessive corrosion is not commonly observed due to the high melting point of GaSO4.

Smialek, James L.↗

The Chemistry of Saudi Arabian Sand - A Deposition Problem on Helicopter Turbine Airfoils

Operations in the Persian Gulf have exposed military helicopter turbines to excessive amounts of ingested sand. Fine particles, less than 10 microns, are able to bypass the particle separators and enter the cooling and combustion systems. The initial sand chemistry varies by location, but is made up of a calcium aluminum silicate glass, SiO2 low quartz, (Ca,Mg)CO3 dolomite, CaCO3 calcite, and occasionally NaCl rocksalt. The sand reacts in the hot combustion gases and deposits onto the turbine vanes as CaSO4, glass, and various crystalline silicates. Deposits up to 5 mm thick have been collected. Although cooling hole plugging is a considerable problem, excessive corrosion is not commonly observed due to the high melting point of CaSO4.

Smialek, James L.↗

Self-organization of the earth's biosphere-geochemical or geophysiological?

We explore the implications of indicating the biosphere's self-organization by the trend over time of the net entropic flow from the Earth's surface, the actual physical boundary of virtually all biotic mass. This flow, derived from the radiative surface entropy budget, is approximately inversely related to the surface temperature when the solar incident flux remains constant. In the geophysiological ('gaian') interpretation, biospheric self-organization has increased with the progressive colonization of the continents and evolutionary developments in the land biota, as a result of surface cooling arising from biotic enhancement of weathering. The key site for this self-organization is at the interface between land and atmosphere, the soil, where carbon is sequestered by its reaction (as carbonic and organic acids) with calcium magnesium silicates. Along with disequilibrium (steady-state) levels of carbon dioxide in the atmosphere, the occurrence of differentiated soil is the critical material evidence for biospheric self-organization, whether it be geophysiological or geochemical (ie., purely result of inorganic reactions). The computed equilibrium levels of carbon dioxide and corresponding equilibrium temperatures in the past are dramatically different from the steady-state levels. With future solar luminosity increase, the biospheric capacity for climatic regulation will decrease, leading to the ending of self-organization some two billion years from now. The Earth's surface will then approach chemical equilibrium with respect to the carbonate-silicate cycle.

Schwartzman, David W.↗

Hubble Space Telescope observations of planetary nebulae in the magellanic clouds. 2: SMP 85, a young planetary

We have obtained Hubble Space Telescope Planetary Camera images in the (O III) lambda 5007 A emission line, and Faint Object Spectrograph (FOS) UV spectrophotometry of the low-excitation planetary nebula SMP 85 in the Large Magellanic Cloud. By combining these results with existing optical spectrophotometry, absolute flux measurements, and dynamical and density information, we have been able to construct a fully self-consistent nebular model. This proves that SMP 85 is a dense, young, carbon-rich object which started to be ionized about 500-1000 years ago, and which contains a substantial inner reservoir of atomic or molecular gas, probably in the form of many small cloudlets. These cloudlets have been ejected at a velocity not exceeding 6 km/s, a result which, together with the morphology is an important clue to mass loss during late asymptotic giant branch (AGB) evolution. We have directly detected the central star through its UV continuum emission, and from both Zanstra techniques and nebular modeling derive a stellar temperature of 46000 +/- 2000 K, a stellar luminosity of 7300 +/- 700 solar luminosity, and a core mass of 0.63-0.67 solar mass. The nebular analysis also demonstrates that there is severe depletion of the nebular gases onto dust grains, most likely of the calcium magnesium silicate variety; a surprising result in view of the carbon-rich nature of the ionized nebula.

Dopita, Michael A.↗

Internal strain analysis of ceramics using scanning laser acoustic microscopy

Quantitative studies of material behavior characteristics are essential for predicting the functionality of a material under its operating conditions. A nonintrusive methodology for measuring the in situ strain of small dimeter (to 11 microns) ceramic fibers under uniaxial tensile loading and the local internal strains of ceramics and ceramic composites under flexural loading is introduced. The strain measurements and experimentally observed mechanical behavior are analyzed in terms of the microstructural development and fracture behavior of each test specimen evaluated. Measurement and analysis of Nicalon silicon carbide (SiC) fiber (15 microns diameter) indicate that the mean elastic modulus of the individual fiber is 185.3 GPa. Deviations observed in the experimentally determined elastic modulus values between specimens were attributed to microstructural variations which occur during processing. Corresponding variations in the fracture surface morphology were also observed. The observed local mechanical behavior of a lithium alumino-silicate (LAS) glass ceramic, a LAS/SiC monofilament composite, and a calcium alumino-silicate (CAS)/SiC fully reinforced composite exhibits nonlinearities and apparent hysteresis due to the subcritical mechanical loading. Local hysteresis in the LAS matrices coincided with the occurrence of multiple fracture initiation sites, localized microcracking, and secondary cracking. The observed microcracking phenomenon was attributed to stress relaxation of residual stresses developed during processing, and local interaction of the crack front with the microstructure. The relaxation strain and stress predicted on apparent mechanical hysteresis effects were defined and correlated with the magnitude of the measured fracture stress for each specimen studied. This quantitative correlation indicated a repeatable measure of the stress at which matrix microcracking occurred for stress relief of each material system. Stress relaxation occurred prior to the onset of steady state cracking conditions. The relaxation stress occurred at 18.5 percent of the fracture stress in LAS and 11.0 percent of the yield stress in CAS/SiC. The relaxation stress ratio was dependent upon the dominant fracture mode of the LAS/SiC specimens. Relaxation stress ratios greater than 0.30 were observed for specimens which fractured due to shear at the fiber matrix interface; specimens which fracture due to tensile cracking had relaxation stress ratios less than 0.30. The stress relaxation ratio appeared to be a specific characteristic of the glass ceramic material. The measured stress relaxation for LAS indicated a measure of the inherent residual stresses in the material due to processing and suggested localized toughening mechanisms for brittle material structures.

Kent, Renee M.↗

Thermodynamic Modeling of Calcium and Magnesium Partitioning Between Sulfide and Silicate and Implications for Mercury’s Differentiation

Mercury is the least oxidized terrestrial planet of the solar system and is enriched in sulfur, which may be saturated in its mantle, possibly forming Ca- and Mg-rich sulfides. Using literature experimental data, we developed a thermodynamic model for calcium and magnesium partitioning between sulfide and silicate melts to enhance our understanding of the chemical equilibria involved in Mercury’s mantle-crust differentiation. Our models show that temperature and carbon abundance in sulfide have a positive effect on Ca partitioning into sulfides, while pressure decreases it. In addition, carbon abundance and sulfur concentration in the silicate melt are the primary controls on Mg partitioning, both favoring Mg partitioning into sulfides. Our results will be used to better understand the abundance as well as presence of calcium and magnesium sulfides within Mercury’s mantle and crust.

Taylor McCombs↗

Calorimetric Measurements of the Thermodynamic Properties of RE-Silicate Coating Materials

Thermodynamic quantities of coatings materials and siliceous debris-induced corrosion products are crucial to understand in order to develop mitigation strategies necessary to improve the durability of gas-turbine engines. Siliceous induced corrosion can occur when debris consisting mainly of CaO-MgO-Al2O3-SiO2 (CMAS) is ingested by aircraft engines during and after take-off, which sticks to hot surfaces and forms calcium rare-earth silicate oxyapatites. In this work, high-temperature oxide melt drop solution calorimetry (HT drop solution calorimetry) was used to obtain the enthalpies of formation for RE silicate (RE2Si2O7, RE2SiO5 where RE = Yb, Er, Y, Dy, Nd, Lu and Gd) environmental barrier coatings (EBCs) and the calcium RE silicate oxyapatite Ca2RE8(SiO4)6O2 (RE = Yb, Er, Y, Dy, Nd, Gd and Sm) corrosion products. Trends in the enthalpy of formation as a function of the ionic potential of the rare-earth cations in their related crystallographic sites are discussed.

Costa, Gustavo↗

Acoustic Emission Analysis of Damage Progression in Thermal Barrier Coatings Under Thermal Cyclic Conditions

Damage evolution of electron beam-physical vapor deposited (EBVD-PVD) ZrO2-7 wt.% Y2O3 thermal barrier coatings (TBCs) under thermal cyclic conditions was monitored using an acoustic emission (AE) technique. The coatings were heated using a laser heat flux technique that yields a high reproducibility in thermal loading. Along with AE, real-time thermal conductivity measurements were also taken using infrared thermography. Tests were performed on samples with induced stress concentrations, as well as calcium-magnesium-alumino-silicate (CMAS) exposure, for comparison of damage mechanisms and AE response to the baseline (as-produced) coating. Analysis of acoustic waveforms was used to investigate damage development by comparing when events occurred, AE event frequency, energy content and location. The test results have shown that AE accumulation correlates well with thermal conductivity changes and that AE waveform analysis could be a valuable tool for monitoring coating degradation and provide insight on specific damage mechanisms.

calcium-magnesium-alumino-silicate (CMAS)↗