Development of Aluminosilicate Aerogel Impregnated Oxide Foams for Structurally Integrated Thermal Protection Systems
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Hurwitz, Frances I.↗
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Results for “aluminosilicates”
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Thermochemical interactions between Ca2Sm8(SiO4)6O2 apatite and molten calcium–magnesium-aluminosilicate (CMAS)
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Narottam P. Bansal↗
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↗
Deciphering the non-linear impact of Al on chemical durability of silicate glass
The role of Al in aluminosilicate glasses remains somewhat a mystery: at low concentrations, it increases the resistance to hydrolysis of the glass, whereas at high concentrations an opposite effect is observed. To understand the origin of the phenomenon on a fundamental atomistic scale, we performed 577 MD simulations and applied potential mean force (PMF) calculations to estimate the activation barriers for hydrolysis and to statistically correlate them with local structural features of the glass. Models of pure silicate and aluminosilicate glasses are constructed and investigated. PMF simulation results are further validated by the experimental measurements and revealed that Al is very easy to dissociate, but it also increases the glass chemical durability through significantly increasing both the strength of Si and network connectivity of the glass. In contrast, at high Al concentration, preferential dissolution of Al weakens the silicate network, which it supposes to strengthen, and so the glass resistance becomes poor. Through PMF calculations, we evaluated the activation barriers for dissociating bonds around Al as 0.49 eV, which is less than a half of the energy to dissociate bonds around Si in pure silicate (1.22 eV) and around Si in aluminosilicate glass (1.34 eV), all these energy differences being statistically significant. Molecular structural level investigation revealed that Si with Al as a second neighbor in the glass network has a significantly higher activation energy for dissociation than Si in pure silicate glass. Furthermore, the proposed approach opens the way to the development of quantitative predictive models of glass durability.
36 MATERIALS SCIENCE↗
Evaluation of coal-associated sediments, wastes, and AMD sludge in the Southern Appalachian Basin as feedstock materials for REE and Li recovery
Critical minerals (CM) such as rare earth elements (REE+) and Lithium (Li) are essential to technological innovation, energy transitions, global economic and defense security, necessitating the search for unconventional resources and efficient recovery methods to avert supply chain disruptions. Here, this study evaluates coal-associated sediments (underclay and roof rock) and wastes from the Pennsylvanian Pottsville Formation of the Southern Appalachian Basin (SAB) as potential feedstocks for CM recovery. A total of 34 samples (15 underclays, 12 roof rocks, 5 Acid Mine Drainage (AMD) sludges, and 2 coal mining wastes) were characterized using XRD, XRF, ICP-MS, and μ-XRF analytical methods. The REE+ and Li concentrations of these materials ranged from 46.8 to 334.4 ppm and from 11.1 to 519 ppm, respectively, with one underclay sample (Hendrix 3456) yielding the highest values for both. Bulk mineralogy for all samples was dominated by aluminosilicate clay phases, particularly illite and kaolinite. All samples exhibited REY def, rel% values >26% and C outl indices that ranged from 0.69 to 0.94, classifying their REE ore potential as Category II (Promising) as defined by Seredin and Dai (2012). Extractability tests (EPA method 3051 A) yielded low REE+ and Li recoveries, with maximum values of 3.3% and 3.6%, respectively, suggesting associations with resistant minerals like clay and phosphates. Elemental mapping indicates that REE+ is associated with phosphate, whereas statistical analysis suggests that REE+ are associated with aluminosilicates, suggesting heterogeneous associations or minimal phosphate contribution. Li also correlated positively with Al 2 O 3 , indicating an aluminosilicate host. This study highlights the potential of coal-associated sediments in the SAB.
Clay minerals↗
First-Principles Study of n -Butane Monomolecular Cracking and Dehydrogenation on Two-Dimensional-Zeolite Model Systems: Reaction Mechanisms and Effects of Spatial Confinement
Two-dimensional (2D) ultrathin (~0.5 nm) aluminosilicate bilayer films, consisting of hexagonal prisms (a.k.a. double 6-membered rings D6R) with acidic bridging hydroxyl groups exposed on the surface, have been previously synthesized on a Ru(0001) surface as a zeolite model system. These structures are helpful for mimicking zeolite catalysts with D6R building blocks, such as chabazite. We performed density functional theory calculations to investigate the monomolecular cracking and dehydrogenation of n-butane molecules over the acidic hydroxyl groups of the 2D model system and compared the reaction energetics with that in bulk chabazite. The intrinsic activation energy barrier is the highest for dehydrogenation and lowest for central C–C bond cracking in bulk chabazite. The trend of intrinsic energy barriers for dehydrogenation and terminal and central C–C bond cracking is reproduced on the 2D aluminosilicate film. Overall, the activation barriers are higher on the 2D film than in bulk chabazite due to the lack of confinement in the former. We further explored the effects of the zeolite channel size on the n-butane adsorption and monomolecular cracking using different bulk nanoporous zeolite frameworks (TON, MEL, MEI, and VFI). We found that as the confinement of channels decreases, n-butane adsorption becomes weaker, and the intrinsic energy barrier of terminal C–C cracking increases. The activation energy barriers (dehydrogenation and terminal and central C–C cracking) on the 2D bilayer film surface, which may be considered as zeolite cages at the infinite cage size limit, are close to that in VFI with a relatively large channel size. Comparing the reaction pathway of n-butane terminal C–C cracking in 3D nanocages and on the surface of the 2D aluminosilicate film revealed that stabilizing the transition states in the 3D nanocages is responsible for the decrease in the intrinsic energy barriers for bulk zeolites.
36 MATERIALS SCIENCE↗
Multilayer article having stabilized zirconia outer layer and chemical barrier layer
A multilayer article includes a substrate that includes at least one of a ceramic compound and a Si-containing metal alloy. An outer layer includes stabilized zirconia. Intermediate layers are located between the outer layer and the substrate and include a mullite-containing layer and a chemical barrier layer. The mullite-containing layer includes 1) mullite or 2) mullite and an alkaline earth metal aluminosilicate. The chemical barrier layer is located between the mullite-containing layer and the outer layer. The chemical barrier layer includes at least one of mullite, hafnia, hafnium silicate and rare earth silicate (e.g., at least one of RE.sub.2 SiO.sub.5 and RE.sub.2 Si.sub.2 O.sub.7 where RE is Sc or Yb). The multilayer article is characterized by the combination of the chemical barrier layer and by its lack of a layer consisting essentially of barium strontium aluminosilicate between the mullite-containing layer and the chemical barrier layer. Such a barium strontium aluminosilicate layer may undesirably lead to the formation of a low melting glass or unnecessarily increase the layer thickness with concomitant reduced durability of the multilayer article. In particular, the chemical barrier layer may include at least one of hafnia, hafnium silicate and rare earth silicate.
Lee, Kang N.↗
Allophane on Mars: Significance for Chemical Weathering and Soil Development
It has been suggested that allophane or related poorly crystalline aluminosilicates are present on Mars, and that they comprise the high-silica phase detected by the Thermal Emission Spectrometer (TES) in Surface Type 2 materials (Michalski et al., 2005). Using new laboratory spectra of allophanic materials, we (Rampe et al., this meeting) have detected allophane on the Martian surface via spectral modeling of TES data. We find that ST2 materials in the Northern Plains are consistent with a significant amount of high-silica allophane-like materials. In addition, we find that allophane may be present in some areas of ancient highlands (TES surface type 1), but spectra of those regions are more consistent with aluminous allophane. The presence of allophane and its chemical variability have important implications for chemical weathering and soil development on Mars. Allophane-like materials are amorphous or poorly crystalline hydrous aluminosilicates formed from chemical weathering of glasses, feldspars, and other silicates (cf. Parfitt, 2009). True allophane is a combination of SiO2, Al2O3 and H2O where Al:Si ranges from ~0.5-2. Aluminosilicate gels are amorphous and chemically similar to allophane but can have higher SiO2 contents. The presence of allophane indicates low-temperature chemical weathering and provides constraints on alteration conditions, limiting pH to circum-neutral (~4.5-8). Our model results indicate that weathering occurred in the relatively young northern plains of Mars. The high-silica allophane-like material present there implies little silica mobility through the soil column, which suggests that weathering involved small amounts of liquid water, consistent with our previous models of weathering in ice-rich soils (Kraft et al., 2007). The aluminous allophane indicated by our spectral models to be present in the highlands suggest that those regions experienced greater amounts of SiO2 leaching and weathering in those soils may have involved much larger amounts of water. The presence of allophane-like materials suggests that these weathering regimes were not influenced by the acidic weathering that appears to have affected other areas of Mars and has been proposed as a planetwide alteration process (Hurowitz and McLennan, 2007). Soil development in basaltic material (typically tephra) on Earth usually leads to formation of andosols. Although we do not suggest a one-to-one analogy between dark basaltic Martian soils and andosols, there may be important similarities, as andosols are typified by significant production of allophane as well as poorly crystalline Fe-hydroxides. The detection of allophane on Mars suggests a positive utility of an andosol model for Martian soils, particularly when coupled with the ubiquitous presence of Feoxide materials on Mars. An andosol model of soil formation is mineralogically consistent with palagonite models for the formation of Martian dust (cf. Banin et al., 1992; Morris et al., 2001), which suggests a possible genetic relationship of dust and bright soils to the broader soil layer of Mars.
Kraft, M. D.↗
Composite media for non-oxidative ethane dehydrogenation, and related ethane activation systems and method of processing an ethane-containing stream
A composite media for non-oxidative C 2 H 6 dehydrogenation comprises an aluminosilicate zeolite matrix, and an EDH catalyst on one or more of an external surface of the aluminosilicate zeolite matrix and internal surfaces within pores of the aluminosilicate zeolite matrix. The EDH catalyst comprises one or more of Fe, Zn, Pt, Ga, alloys thereof, and oxides thereof. A C 2 H 6 activation system, and a method of processing a C 2 H 6 -containing stream are also described.
Wang, Lucun↗
Revisiting metastable immiscibility in SiO 2 –Al 2 O 3 : Structure and phase separation of supercooled liquids and glasses
Understanding and controlling liquid–liquid phase separation in aluminosilicates is crucial for optimizing glass properties. However, the metastable nature of aluminosilicates’ phase separation has made it difficult to study experimentally, and uncertainty persists regarding the compositional and temperature extents of the miscibility gap. Here, we present new experimental evidence that suggests a consolute temperature between 1440 and 1590°C and endmember compositions of 7 and 62 mol.% Al 2 O 3 for the phase-separated glasses. Using containerless melt processing, deeply supercooled liquids over the 0–60 mol.% Al 2 O 3 range are probed with in situ small- and wide-angle X-ray scattering, which simultaneously reveals changes in nanoscale density heterogeneity and atomic structure. Correlations between phase separation and atomic coordination environments are compared for liquids and glasses. Pair distribution function analysis shows mean O–(Si + Al) coordination increases with Al 2 O 3 content and decreases with temperature.
36 MATERIALS SCIENCE↗
Corrosion-Resistant Plug Materials for Geothermal Well Fluid Control
Conventional cements and plugs are challenged by corrosion in CO 2 -rich and extreme geothermal environments, due to the hostile chemistry and high temperatures. Thermite-based sealing and well intervention technologies are being applied in the oil and gas industry, combining the energy delivery capability of thermite materials with the sealing characteristics of low melt temperature alloys. The thermite reaction products (ceramics) and the sealing alloys used in these plugs both have very attractive corrosion properties, and their operating envelopes extend into geothermal conditions. Thermite plugs and platforms, without supplemental sealing materials, have been considered for nuclear waste isolation, carbon sequestration, and geothermal applications due to the geochemical stability of the ceramic product and its very high service temperature. This study addresses corrosion resistance of the thermite reaction products. A range of engineered thermite systems which yield thermite reaction products including pure aluminum oxide, feldspar, or aluminosilicate solid solutions (in addition to the iron produced in thermite reactions) was developed. These materials were evaluated for their strong acid resistance (pH 1), carbonate resistance (sodium carbonate) and thermal shock resistance (600 °C heating → cold water quenching repeated three times). Performance of different materials was evaluated based on the changes in mechanical properties, water-fillable porosity, phase changes under stress conditions. The aluminosilicate product exhibited very good corrosion resistance, both from material loss and strength perspectives, while the other products performed with varying degrees of stability. This paper presents the results of the thermite corrosion studies and describes the novel tools being deployed, and under development, to satisfy challenging barrier and intervention applications.
02 PETROLEUM↗
Accelerated carbonation and structural transformation of blast furnace slag by mechanochemical alkali-activation
Alternative cements and production routes are necessary to offset the considerable global CO 2 emissions of Portland cement production. The combination of alkali-activation and mechanochemical milling in a CO 2 rich atmosphere is a promising green direction for synthesizing cementitious material as it upcycles hazardous material (slag) while capturing wt% of CO 2 during synthesis. We investigate the resulting structural transformations incurred during synthesis and hydration using a suite of characterization techniques including solid-state 27 Al, 29 Si, and 13 C NMR. The local aluminosilicate network structure of the processed clinker is best described by a melilite-type structure. Upon hydration, the network polymerizes to form a calcium, sodium aluminosilicate hydrate gel. The synthesis route also creates various metastable carbonates and bicarbonates from captured CO 2 and alkali-additives that transform into stable carbonate phases like calcite, aragonite, and gaylussite, after hydration. These findings indicate accelerated carbonation reactions occur during clinker production and demonstrates novelty as a green cement technology.
36 MATERIALS SCIENCE↗
Towards new zero-thermal-expansion materials: Li-free quartz solid solutions stuffed with transition metal cations
Stuffed aluminosilicate quartz solid solutions (Qss) represent the main functional component of state-of-the-art zero-thermal-expansion glass-ceramics. For the first time, we present the synthesis of Li-, Mg- and Zn-free Qss solely stuffed with transition metal cations (Fe 2+ , Ni 2+ , Co 2+ ); partial Li + co-doping enables also significant Mn 2+ incorporation. Further, they were obtained by glass powder crystallization; Qss crystals exhibit compositionally tunable coefficients of thermal expansion (CTEs), from - 2 × 10 -6 K -1 to ~10 × 10 -6 K -1 in the range 30–300 °C. Co 2+ -bearing crystals exhibit the closest-to-zero CTE value (0.2 ×10 -6 K -1 ) and the most isotropic behavior in the whole Qss family, opening up new perspectives for the development of Li-free low-expansion materials. From a structural point of view, we identified the unit cell volume (and not the pseudo-hexagonality of the aluminosilicate framework) as the key structural parameter leading to low or negative CTEs in Qss, with a linear correlation extending to non-stuffed non-silicate quartz-like phases.
36 MATERIALS SCIENCE↗
Iodine Capture by Ag-Loaded Solid Sorbents Followed by Ag Recycling and Iodine Immobilization: An End-to-End Process
Here, this article demonstrates the complete process of I 2(g) capture using Ag-exchanged faujasite (AgX) and Ag-exchanged mordenite (AgZ) zeolite sorbents, the recovery of Ag for recyclability of iodine capture, and the immobilization of iodide (from the elution process) into an iodosodalite waste form, which is chemically and environmentally stable. The gaseous iodine, I 2(g) , was captured in the AgX via chemisorption by Ag and converted to AgI within the aluminosilicate zeolite frameworks. The elution reaction in Na 2 S resulted in the precipitation of Ag 2 S and dissolution of I – and Na + into the aqueous solution, where powdered sorbent showed higher conversion efficiency than the granular form, which is attributed to Na 2 S-solution diffusion limitations in the granules. The Ag 2 S-containing aluminosilicate precipitates were filtered out of the solution, and the filtrate (aqueous solution) was used to synthesize iodosodalite to immobilize iodide. The iodine capture using the recovered Ag 2 S-containing sorbents shows equivalent iodine loadings to the AgX starting material of Q e = 0.355 g/g for powdered material and 0.255 g/g for granular material, demonstrating the potential recycling of Ag for iodine capture as Ag 2 S-based sorbents.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
X-ray spectral microanalysis of composition of individual lunar regolith particles
Determinations were made of the chemical compositions of selected olivine crystals, spherical particles ranging in size from 170 to 350 micrometer, spinels, and magnetic particles. The olivines contain 30 to 50 mole percent fayalite. The spherical particles of various colors are aluminosilicate glasses, significantly enriched in CaO compared with the mean composition of the regolith. The degree of coloration depends on the FeO content and also the admixtures TiO2, MnO, and Cr2O3. Compositionally, the spinel was interpreted to be chromopicotites. Magnetic particles were shown to be complex intergrowths of nickelous iron and aluminosilicates. The composition of the metallic phase of one particle (in percent) was: Fe - 86, Ni - 13.6, and Co - 0.16 in combination with plagioclase and microinclusions of ilmenite in silicate. Kamacite was determined in another intergrowth of Fe, Ni, and Co.
Ilin, N. P.↗
Fibrous refractory composite insulation
A refractory composite insulating material was prepared from silica fibers and aluminosilicate fibers in a weight ratio ranging from 1:19 to 19:1, and about 0.5 to 30% boron oxide, based on the total fiber weight. The aluminosilicate fiber and boron oxide requirements may be satisfied by using aluminoborosilicate fibers and, in such instances, additional free boron oxide may be incorporated in the mix up to the 30% limit. Small quantities of refractory opacifiers, such as silicon carbide, may be also added. The composites just described are characterized by the absence of a nonfibrous matrix.
Leiser, D. B.↗
Vapor deposited emittance/catalysis coatings for superalloys in heatshield applications
Statically oxidized Inconel 617 and MA 956 superalloys were prepared with vapor deposited aluminosilicate layers and exposed to temperatures which simulated reentry conditions. The aluminosilicate layers were 1-2 microns thick. The trials consisted of exposures to 1500-2300 F heat while surface temperatures were monitored with pyrometers. Analyses were then performed of the catalytic activity, oxidation phenomena, and radiative properties after thermal cycling the specimens for 8 hr. Both alloys were found to be catalytic to the recombination processes of dissociated species in the reentry environment. The coatings reduced the catalytic activity by 40 percent for both alloys but did not change the emittance. An enhanced Cr depletion zone was detected in the Inconel samples, implying that the coating did not prevent diffusion loss of Cr. The coated MA 956, on the other hand, gained weight over the course of the trials.
Clark, R. K.↗
Channel waveguides in glass via silver-sodium field-assisted ion exchange
Multimode channel waveguides have been formed in sodium aluminosilicate glass by field-assisted diffusion of Ag(+) ions from vacuum-evaporated Ag films. The two-dimensional refractive index profiles of the waveguides were controlled by varying the diffusion time, the diffusion temperature, and the electric field strength. Estimates of the diffusion rate through a strip aperture were obtained, assuming the electric field was strong 120-240 V/mm. The maximum change in refractive index in the sodium aluminosilicate glasses was estimated near 65 percent of the change in soda-lime silicate glass. The physical properties of the glasses are given in a table.
Forrest, K.↗