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Disclosed here is a process for making mullite fibers wherein a hydrolizable silicon compound and an aluminum compound in the form of a difunctional aluminum chelate are hydrolized to form sols using water and an alcohol with a catalytic amount of hydrochloric acid. The sols are mixed in a molar ratio of aluminum to silicon of 3 to 1 and, under polycondensation conditions, a fibrous gel is formed. From this gel the mullite fibers can be produced.
Plasma-sprayed mullite (3Al2O3 central dot 2SiO2) and mullite/yttria-stabilized-zirconia (YSZ) dual layer coatings have been developed to protect silicon-based ceramics from environmental attack. Mullite-based coating systems show excellent durability in air. However, in combustion environments, corrosive species such as molten salt or water vapor penetrate through cracks in the coating and attack the Si-based ceramics along the interface, Thus modification of the coating system for enhanced crack-resistance is necessary for long-term durability in combustion environments. Other key durability issues include interfacial contamination and coating/substrate bonding. Interfacial contamination leads to enhanced oxidation and interfacial pore formation, while weak coating/substrate bonding leads to rapid attack of the interface by corrosive species, both of which can cause premature failure of the coating. Interfacial contamination can be minimized by limiting impurities in coating and substrate materials. The interface may be modified to improve the coating/substrate bond.
Plasma-sprayed mullite (3Al2O3.2SiO2) and mullite/yttria-stabilized-zirconia (YSZ) dual layer coatings have been developed to protect silicon -based ceramics from environmental attack. Mullite-based coating systems show excellent durability in air. However, in combustion environments, corrosive species such as molten salt or water vapor penetrate through cracks in the coating and attack the Si-based ceramics along the interface. Thus the modification of the coating system for enhanced crack-resistance is necessary for long-term durability in combustion environments. Other key durability issues include interfacial contamination and coating/substrate bonding. Interfacial contamination leads to enhanced oxidation and interfacial pore formation, while a weak coating/substrate bonding leads to rapid attack of the interface by corrosive species, both of which can cause a premature failure of the coating. Interfacial contamination can be minimized by limiting impurities in coating and substrate materials. The interface may be modified to improve the coating/substrate bond.
Current state-of-the-art environmental barrier coatings (EBCs) for Si-based ceramics consist of three layers: a silicon bond coat, an intermediate mullite (3Al2O3-2SiO2) or mullite + BSAS (1-xBaO-xSrO-Al2O3-2SiO2) layer, and a BSAS top coat. Areas of concern for long-term durability are environmental durability, chemical compatibility, silica volatility, phase stability, and thermal conductivity. Variants of this family of EBCs were applied to monolithic SiC and melt infiltrated SiC/SiC composites. Reaction between BSAS and silica results in low melting (approx. 1300 C) glasses at T > 1400 C, which can cause the spallation of the EBC. At temperatures greater than 1400 C, the BSAS top coat also degrades by formation of a porous structure, and it suffers significant recession via silica volatilization in water vapor-containing atmospheres. All of these degradation mechanisms can be EBC life-limiting factors. BSAS undergoes a very sluggish phase transformation (hexagonal celsian to monoclinic celsian), the implications of which are not fully understood at this point. There was evidence of rapid sintering at temperatures as low as 1300 C, as inferred from the sharp increase in thermal conductivity.
A silicon-base ceramic substrate is provided with a mullite chemical barrier/thermal barrier coating uniformly bonded to a surface. The coating is substantially free of amorphous mullite.
We report on the temperature-dependent structural studies on the mullite-type Bi{sub 2}Fe{sub 4}O{sub 9} compound. The crystal structures were determined using both powder X-ray diffraction and single crystal neutron diffraction. The thermal expansion of the cell parameters from smallest to largest occurred in the order a<c<b; their expansion behavior was fit using either linear or nonlinear regression according to the region of choice. The anisotropic thermal expansion was monitored with respect to the expansion coefficients, anisotropy factor, and polyhedral geometry. At 900 K an abrupt change of the anisotropy factor is observed which correlates with a slope in the BiO{sub 6} polyhedral volume. At the same temperature the FeO{sub 4} tetrahedral distortion starts to increase. The temperature-dependent stereochemically activity of the Bi{sup 3+} 6s{sup 2} lone electron pair was probed by the absolute value of eccentricity parameter. This parameter shows a significant drop at around 773 K. Additionally, the average crystal size and micro-strain of the powder samples were studied. A healing of intrinsic defects is observed with respect to a decreasing micro-strain followed by crystal growth above about 900 K. The temperature-dependent infrared spectra were described in three distinct zones. Deconvolution of the absorption features between 370 cm{sup -1} and 1000 cm{sup -1} required nine fitted bands, and the decomposed Pseudo-Voigt elements were assigned to Fe-O stretching, Fe-O-Fe bending and O-Fe-O bending vibrations. The shift of the observed modes was described with respect to temperature. An effective linewidth parameter {Delta}corr was determined by autocorrelation analysis between 740 cm{sup -1} and 900 cm{sup -1} for each temperature-dependent spectrum. The break of the slope of {Delta}corr at about 773 K was interpreted as the change of some vibrational modes of the FeO{sub 4} tetrahedra. The intrinsic effects observed around 773 K are responsible for extrinsic parameter changes found around 900 K. - Graphical abstract: Temperature-dependent stereochemical activity (eccentricity |{Phi}{sub i}|) of the Bi{sup 3+} 6s{sup 2} lone electron pair directing in the non-bonded region of the Bi-O coordination in the Bi{sub 2}Fe{sub 4}O{sub 9} iron framework (given as polyhedra). Highlights: Black-Right-Pointing-Pointer Complex expansion-contraction mechanism explains anisotropic thermal expansion. Black-Right-Pointing-Pointer Bi 6s{sup 2} lone electron pair sphericity influences analyses by FTIR autocorrelation. Black-Right-Pointing-Pointer Intrinsic effects at 773 K are responsible for extrinsic parameter changes at 900 K.
Graphical abstract: - Highlights: • Anisotropic lattice thermal expansion of Bi{sub 2}Ga{sub 4}O{sub 9} was modeled using extended Grüneisen first-order approximation. • The model includes harmonic, quasi-harmonic and intrinsic anharmonic contributions to the internal energy. • Temperature dependent Raman frequency shift and line-width was analyzed using symmetric phonon decay channel. - Abstract: We report the lattice thermal expansion and the temperature-dependent phonon behavior of the mullite-type Bi{sub 2}Ga{sub 4}O{sub 9} complex oxide. The thermal expansion was studied using composite data collected from powder and single crystal X-ray diffraction between 100 K and 1273 K. The lattice expansion occurred in the order of a < c < b. The anisotropic expansion behavior was monitored with respect to thermal expansion coefficients and the anisotropy factor. The volume thermal expansion was expressed using an extended Grüneisen first-order approximation to the zero-pressure equation of state; the model includes harmonic, quasi-harmonic and intrinsic anharmonic contributions to the internal energy as a function of temperature. The temperature dependent Raman spectra were collected from a single crystal between 78 K and 1273 K. The shift of the frequencies and the broadening of the line-widths with increasing temperature helped to analyze the anharmonicity and the thermal behavior of some phonons.
Highlights: • Chemical solution deposited La-doped Bi{sub 2}Fe{sub 4}O{sub 9} thin film. • Structural, electrical and multiferroic properties were investigated. • La-doped Bi{sub 2}Fe{sub 4}O{sub 9} exhibited enhanced electrical and multiferroic properties. - Abstract: Thin films of (Bi{sub 2−x}La{sub x})Fe{sub 4}O{sub 9} (x = 0 and x = 0.05) were prepared on Pt(1 1 1)/Ti/SiO{sub 2}/Si(1 0 0) substrates by using a chemical solution deposition method to investigate structural, microstructural, electrical and multiferroic properties. Both the thin films were crystallized in mullite type phases with orthorhombic structures containing no secondary and impurity phases, which was confirmed by X-ray diffraction and Raman spectroscopy studies. The (Bi{sub 1.95}La{sub 0.05})Fe{sub 4}O{sub 9} thin film exhibited improved electrical and multiferroic properties at room-temperature. The leakage current density of the (Bi{sub 1.95}La{sub 0.05})Fe{sub 4}O{sub 9} thin film was one order of magnitude lower than that of the Bi{sub 2}Fe{sub 4}O{sub 9} thin film. Furthermore, in the thin film form, (Bi{sub 2−x}La{sub x})Fe{sub 4}O{sub 9} exhibited better stability against electrical breakdowns and enhanced multiferroic properties.
Mullite-type $R$Mn 2 O 5 ($R$ = Y, rare-earth element) ceramics are of ongoing research attention because of their interesting crystal-chemical and magnetic properties. We report nuclear and magnetic structures of NdMnTiO 5 together with its spectroscopic, thermogravimetric, and magnetic properties. The polycrystalline sample is prepared by solid-state synthesis and characterized from neutron and X-ray powder diffraction data Rietveld refinements. NdMnTiO 5 crystallizes in the orthorhombic space group $Pbam$ with metric parameter $a$ = 755.20(1) pm, $b$ = 869.91(1) pm, $c$ = 582.42(1) pm, and $V$ = 382.62(1) 10 6 pm 3 . The Mn 3+ and Ti 4+ cations are observed to be located in the octahedral and pyramidal sites, respectively. The vibrational features in these polyhedral sites are characterized by Raman and Fourier transform infrared spectroscopes. The higher decomposition temperature of NdMnTiO 5 , compared to other $R$Mn 2 O 5 phases, is explained in terms of the higher bond strength of Ti-O bonds than those of Mn-O bonds. Temperature-dependent DC magnetic susceptibility suggests a paramagnetic to antiferromagnetic phase transition at 43(1) K. Inverse susceptibility in the paramagnetic region above 120 K follows the Curie-Weiss law, resulting in a magnetic moment of 6.33(1) μ B per formula unit. Neutron diffraction data collected at 7.5 K reveal that the magnetic moments of Nd 3+ and Mn 3+ in NdMnTiO 5 are incommensurately ordered with a propagation vector $k$ = (0, 0.238, 0.117).
Mullite-type Al{sub 6−x}B{sub x}O{sub 9} compounds were studied by means of powder diffraction and spectroscopic methods. The backbones of this structure are chains of edge-connected AlO{sub 6} octahedra crosslinked by AlO- and BO-polyhedra. Rietveld refinements show that the a and b lattice parameters can be well resolved, thus representing an orthorhombic metric. A continuous decrease of the lattice parameters most pronounced in c-direction indicates a solid solution for Al{sub 6−x}B{sub x}O{sub 9} with 1.09≤x≤2. A preference of boron in 3-fold coordination is confirmed by {sup 11}B MAS NMR spectroscopy and Fourier calculations based on neutron diffraction data collected at 4 K. Distance Least Squares modeling was performed to simulate a local geometry avoiding long B-O distances linking two octahedral chains by planar BO{sub 3} groups yielding split positions for the oxygen atoms and a strong distortion in the octahedral chains. The lattice thermal expansion was calculated using the Grüneisen first-order equation of state Debye-Einstein-Anharmonicity model. - Graphical abstract: Local distortion induced by boron linking the octahedral chains. - Highlights: • Decreasing lattice parameters indicate a solid solution for Al{sub 6−x}B{sub x}O{sub 9} (1.09≤x≤2). • B-atoms induce a local distortion of neighboring AlO{sub 6} octahedra. • A preference of boron in BO{sub 3} coordination is confirmed by {sup 11}B MAS NMR spectroscopy. • An optimized structural model for Al{sub 6−x}B{sub x}O{sub 9} is presented.
The crystal structure and disorder phenomena of Al{sub 4}B{sub 2}O{sub 9}, an aluminum borate from the mullite-type family, were studied using automated diffraction tomography (ADT), a recently established method for collection and analysis of electron diffraction data. Al{sub 4}B{sub 2}O{sub 9}, prepared by sol-gel approach, crystallizes in the monoclinic space group C2/m. The ab initio structure determination based on three-dimensional electron diffraction data from single ordered crystals reveals that edge-connected AlO{sub 6} octahedra expanding along the b axis constitute the backbone. The ordered structure (A) was confirmed by TEM and HAADF-STEM images. Furthermore, disordered crystals with diffuse scattering along the b axis are observed. Analysis of the modulation pattern implies a mean superstructure (AAB) with a threefold b axis, where B corresponds to an A layer shifted by ½a and ½c. Diffraction patterns simulated for the AAB sequence including additional stacking disorder are in good agreement with experimental electron diffraction patterns. - Graphical abstract: Crystal structure and disorder phenomena of B-rich Al{sub 4}B{sub 2}O{sub 9} studied by automated electron diffraction tomography (ADT) and described by diffraction simulation using DISCUS. - Highlights: • Ab-initio structure solution by electron diffraction from single nanocrystals. • Detected modulation corresponding mainly to three-fold superstructure. • Diffuse diffraction streaks caused by stacking faults in disordered crystals. • Observed streaks explained by simulated electron diffraction patterns.
High-entropy materials (HEMs) represent a new class of solid solutions containing at least five different elements. Their compositional diversity makes them promising as platforms for the development of functional materials. We synthesized new HEMs in a mullite-type structure and present five compounds, i.e., Bi 2 (Al 0.25 Ga 0.25 Fe 0.25 Mn 0.25 ) 4 O 9 and A 2 Mn 4 O 10 with variations of A = Nd, Sm, Y, Er, Eu, Ce, and Bi, demonstrating the vast accessible composition space. By combining scattering, microscopy, and spectroscopy techniques, we show that our materials are mixed solid solutions. Remarkably, when following their crystallization in situ using X-ray diffraction and X-ray absorption spectroscopy, we find that the HEMs form through a metastable amorphous phase without the formation of any crystalline intermediates. We expect that our synthesis is excellently suited to synthesizing diverse HEMs and therefore will have a significant impact on their future exploration.
We developed a broadband two-layer anti-reflection (AR) coating for use on a sapphire half-wave plate (HWP) and an alumina infrared (IR) filter for the cosmic microwave background (CMB) polarimetry. Measuring the faint CMB B-mode signals requires maximizing the number of photons reaching the detectors and minimizing spurious polarization due to reflection with an off-axis incident angle. Sapphire and alumina have high refractive indices of 3.1 and are highly reflective without an AR coating. This paper presents the design, fabrication, quality control, and measured performance of an AR coating using thermally sprayed mullite and Duroid 5880LZ. This technology enables large optical elements with diameters of 600 mm. We also present a thermography-based nondestructive quality control technique, which is key to assuring good adhesion and preventing delamination when thermal cycling. We demonstrate the average reflectance of about 2.6% (0.9%) for two observing bands centered at 90/150 (220/280) GHz. At room temperature, the average transmittance of a 105 mm square test sample at 220/280 GHz is 83%, and it will increase to 90% at 100 K, attributed to reduced absorption losses. Therefore, our developed layering technique has proved effective for 220/280 GHz applications, particularly in addressing dielectric loss concerns. This AR coating technology has been deployed in the cryogenic HWP and IR filters of the Simons Array and the Simons observatory experiments and applies to future experiments such as CMB-S4.
Systematic development and evaluation of ceramic fiber Mullite are summarized: (1) Major reductions in thermal protection system weight have been achieved by reducing the density and thermal conductivity of the insulation by 20 and 25 percent; (2) already adequate structural margins-of-safety have been greatly enhanced by increasing the tensile strength and strain-to-failure capabilities of the insulation by factors of 3 and 2; (3) cost effectiveness has been increased through the achievement of a high degree of uniformity and reproducibility of properties and through process simplification and binder modifications; and (4) maximization of multimission capability at surface temperatures of 1644 K has been achieved through firing cycle adjustments and the development of a material with high dimensional stability.
The microstructures of mullite composition fibers were examined by transmission electron microscopic techniques and by X-ray diffraction analyses. Both spun and monofilament fiber structures contained little porosity, nor did the degree of porosity change after heating the monofilament to 1205 C for one half hour. Thermal exposure produced crystallite growth and nucleation from the amorphous phase in all three of the spun fibers. After 116 hours at 1426 C, the crystallites of the standard spun fibers became contiguous. In addition, the surface crystallites of these fibers were found to be more than twice as large as the interior crystallites.
Glassy fibrous mullite coatings exhibit noncatalytic surface characteristics which limit surface temperature rise under certain convective heat flux conditions. Thermal conductivity design curves provide good agreement with test results. The inclusion of shine-in effects results in improved accuracy of transient temperature gradient predictions for the materials.
It has been shown that a ceramic mullite fiber/mullite insulation has adequate margins-of-safety based on minimum strengths for the critical thermostructural conditions of the shuttle mission. Introduction into the design of the new lower density foam bond material provides cold soak and cold entry capability at 116 K (-250 F). Finally, design solutions to the coating cracking tendencies have been identified and the solution analytically verified with three dimensional thermostructural analysis.
The materials studied are described along with the apparatus and the experimental techniques employed. The results of the measurements involving two REI Silica materials and a Mod 1 B REI Mullite are listed in a table. Measurements were conducted at unusually high temperature differences to detect 'shine-through' radiation transparency. Photographs are presented of the high-temperature guarded hot plate assembly.