Kinetics and Mechanism of Corrosion of SiC by Molten Salts

Corrosion of sintered α-SiC under thin films of Na₂CO₃/CO₂, Na₂SO₄/O₂, and Na₂SO₄/SO₃ was investigated at 1000°C. Chemical analysis was used to follow silicate and silica evolution as a function of time. This information couples with morphology observations leads to a detailed corrosion mechanism. In all cases the corrosion reactions occur primarily in the first few hours. In Na₂CO₃/CO₂ case, rapid oxidation and dissolution lead to a thick layer of silicate melt in ∼0.25 h. After this, silica forms a protective layer on the carbide. In the Na₂SO₄/O₂ case, a similar mechanism occurs. In the Na₂SO₄/SO₃ case, a porous nonprotective layer of SiO₂ grows directly on the carbidem and a silicate melt forms above this. In addition due to reaction of silicate with SO₃ and SO₂+O₂. The reaction slows when the lower silica layer becomes nonporous.     

Disproportionation of SO2 in Bubbles Within Soda-Containing Glasses

Deposits of S⁰; and Na₂SO₄ together in bubbles within production float glass are generated by disproportionation of SO₂, derived from dissolved SO₃, in company with Na₂O from the interior bubble surfaces. This reaction proceeds rapidly in molten glass and also at temperatures well below T_g.     

Hot Corrosion of Sintered α-Sic at 1000°C

The hot corrosion of sintered α-Sic by thin films of Na₂SO₄ and Na₂CO₃ was studied at 1000°C in controlled gas atmospheres. Under all conditions corrosion led to 10 to 20 times the amount of SiO₂ formed in pure oxidation after a 48-h exposure. In addition, small amounts of sodium silicate formed. Melts of Na₂SO₄/SO₃ caused uniform pitting of the Sic substrate; Na₂CO₃/CO₂ melts caused localized pitting and grain-boundary attack. In all cases the protective SiO₂ layer dissolved to form silicate, leading to corrosion. In the sulfate case, free carbon in the Sic promotes this process. In all cases the presence of liquid films is responsible for rapid transport rates and the subsequent rapid reaction.     

Investigation of the Phase Diagram for the Pseudobinary System Li2SO4–La2(SO4)3 and Its Ionic Conductivity

The phase diagram of the pseudobinary system Li₂SO₄–La₂(SO₄)₃ has been investigated by means of X-ray diffraction and differential thermal analysis. LiLa(SO₄)₂ is formed by a peritectic reaction in this system; the peritectic temperature is 653±3°C. The eutectic reaction of Li₂SO₄ and LiLa(SO₄)₂ occurs at 553±3°C; the composition at the eutectic point is 17 mol% La₂(SO₄)₃. LiLa(SO₄)₂ is monoclinic with a=1.375 nm, b=0.6744 nm, c=0.7068 nm, and β=105.4°. The ionic conductivity of LiLa(SO₄)₂ has been studied from room temperature to 350°C and is found to be relatively low at room temperature or at lower temperatures. Its activation energy is 0.66 eV. Thus it is not suitable as a fast ion conductor.     

Melting Reactions of Soda-Lime-Silicate Glasses Containing Sodium Sulfate

Various Na₂SO₄-Na₂CO₃-CaCO₃-SiO₂ combinations were studied by differential thermal analysis to elucidute the role of Na₂SO₄ in soda-lime-silica glassmelting reactions. It was found that Na₂SO₄ encourages the formation of wollastonite at 850° to 900°C. The solid-state reaction of Na₂Ca(CO₃)₂ occurs very readily at temperatures in the vicinity of 400°C. The Na₂Ca(CO₃)₂ must therefore be considered a major constituent in glass batches containing both soda ash and limestone .     

Vaporization Kinetics of Na2SO4 from 900° to 1200°C

Continuous weight-change measurements were used to determine the vaporization kinetics of Na₂SO₄ from 900° to 1200°C in 150 torr O₂. Simple evaporation of the sulfate was indicated. An activation energy for vaporization of 71 kcal/mol was calculated. Vaporization results obtained for Na₂SO₄ on oxide substrates indicated an Na₂SO₄-Cr₂O₃ reaction; however, no Na₂SO₄-ZrO₂ reaction was observed.     

Hot Corrosion Behavior of Barium Aluminosilicate-Coated C/SiC Composites at 900°C

Barium aluminosilicates (BAS) were coated on the carbon fiber-reinforced silicon carbide composites (C/SiC) as environmental barriers. The hot corrosion behavior of the coated composites was studied at 900°C in dry air and water vapor, respectively. The molten Na₂SO₄ was used as the corrosion reactant. The results indicate that the BAS coatings can effectively block the attack of molten Na₂SO₄ to C/SiC composites in dry air. However, the coated composites degrade rapidly when exposed to molten Na₂SO₄ coupled with water vapor. It is found that the BAS is corroded by Na₂SO₄ melt with the formation of BaSO₄, resulting in the destruction of BAS structure, which makes the coating lose its protection to the C/SiC composites in water vapor.     

Solid-State SO2 Sensor Using a Sodium-Ionic Conductor and a Metal–Sulfide Electrode

All solid-state sulfur oxides (SO _x ) sensor devices combined with a sodium ionic conductor (Na₅DySi₄O₁₂) disk and metal sulfide-sensing electrodes synthesized via solution routes have been systematically investigated for the detection of SO₂ in the range of 20–200 ppm at 150–400°C. Among the various sulfide-sensing electrodes tested, the metal monosulfide-based electrodes gave good SO₂ sensitivity at 400°C. The Pb_{1− x} Cd _x S ( x =0.1, 0.2)-based solid electrolyte sensor element showed the best sensing characteristics, i.e., the EMF response was almost linear to the logarithm of SO₂ concentration in the range between 40 and 400 ppm, with a 90% response time to 100 ppm SO₂ of about 3–15 min, and also showed high selectivity to SO₂ at 400°C.     

Effect of Counterions on Synthesis of Mesoporous Silica by the Route of Template

Mesoporous silica materials with ordered hexagonal and parallel-arranged pore channel have been synthesized using cetyl trimethylammonium bromide as a template and Na₂SO₄ as counterions. Their ordered mesostructures were characterized by infrared spectroscopy, X-ray diffraction patterns, scanning electron microscopy, transmission electron microscopy, and nitrogen sorption analysis. The effects of Na₂SO₄ concentration on variations of morphology, specific surface area, and pore size were discussed; the results show that a high concentration of Na₂SO₄ induces the formation of crystal threads with a "tubules-within-tubule" structure, and also leads to mesoporous silica materials with spherical, fabaceous, sheet-like, or prismatic shapes. The results also show that a high concentration of Na₂SO₄ can make the pore size decrease, but cannot change pore wall thickness, demonstrating the stability of the hexagonal-shaped pores.     

Static-Fatigue Life of Ce-TZP and Si3N4 in a Corrosive Environment

Stress rupture testing was performed in four-point flexure at 1000°C to determine the effects of Na₂SO₄-induced corrosion on the static-fatigue life of a Ce-TZP and a MgO-doped Si₃N₄. The results showed that the static-fatigue life of the Ce-TZP was unaffected by this corrosive environment. However, the static-fatigue life of a MgO-doped Si₃N₄ was reduced by the introduction of Na₂SO₄.     

Size Control of α-Al2O3 Platelets Synthesized in Molten Na2SO4 Flux

α-Al₂O₃ platelet powders were synthesized in molten Na₂SO₄ flux. The size of α-Al₂O₃ platelets was significantly reduced when partially decomposed rather than pure Al₂(SO₄)₃ was used as the source of Al₂O₃; a further reduction in the platelet size was realized through additional seeding with nanosized α-Al₂O₃ seeds. The addition of microsized α-Al₂O₃ platelet seeds significantly influenced the platelet morphology of the final powder, as well. The platelet size of the final powder was in direct proportion to the size of the platelet seeds, and was in reverse proportion to the cube root of the platelet seed content.     

Kinetics and Mechanism of Hot Corrosion of γ-Y2Si2O7 in Thin-Film Na2SO4 Molten Salt

γ-Y₂Si₂O₇ is a promising candidate material both for high-temperature structural applications and as an environmental/thermal barrier coating material due to its unique properties such as high melting point, machinability, thermal stability, low linear thermal expansion coefficient (3.9 × 10⁻⁶/K, 200°–1300°C), and low thermal conductivity (<3.0 W/m·K above 300°C). The hot corrosion behavior of γ-Y₂Si₂O₇ in thin-film molten Na₂SO₄ at 850°–1000°C for 20 h in flowing air was investigated using a thermogravimetric analyzer (TGA) and a mass spectrometer (MS). γ-Y₂Si₂O₇ exhibited good resistance against Na₂SO₄ molten salt. The kinetic curves were well fitted by a paralinear equation: the linear part was caused by the evaporation of Na₂SO₄ and the parabolic part came from gas products evolved from the hotcorrosion reaction. A thin silica film formed under the corrosion scale was the key factor for retarding the hot corrosion. The apparent activation energy for the corrosion of γ-Y₂Si₂O₇ in Na₂SO₄ molten salt with flowing air was evaluated to be 255 kJ/mol.     

India as a Hot Corrosion-Resistant Stabilizer for Zirconia

After showing that india (In₂O₃) resisted high-temperature reaction with SO₃/Na₂SO₄ and vanadate melts, we prepared india-stabilized zirconia (ISZ) by a proprietary sol–gel process, and tested the material for corrosion resistance to 700–900°C molten vanadates. ISZ was superior to yttria-stabilized zirconia (YSZ) in vanadate resistance at 700°C, and essentially equivalent at 900°C. Certain differences were observed between the vanadate-induced corrosion/destabilization of ISZ and that of YSZ.     

Hot Corrosion of Silica

The high-temperature corrosion of bulk silica glass was studied in pure oxygen and in SO₃-containing oxygen atmospheres in the presence of liquid sulfate deposits at temperatures of 700° and 1000°C. No reaction and devitrification were observed without Na₂SO₄ on the surface. The wetting of the silica by the sulfate, the tendency toward basic fluxing, and the crystallization of the silica incrased with the activity of Na₂O. The most extensive degradation of vitreous silica occurred by crystallization, and the resulting spalling under basic conditions and thermal cycling at basic conditions were parabolic. This behavior is explained by a model in which the crystallization is controlled by sodium at the glass-crystal interface and its diffusion into the glass. This sodium diffuses into the glass before crystallization and is swept ahead of the crystallization front.     

Na2SO4-lnduced Corrosion of Si3N4 Coated with Chemically Vapor Deposited Ta2O5

Hot isostatically pressed Si₃N₄ was coated with chemically vapor-deposited Ta₂O₅, and subjected to oxidative and corrosive environments to determine the feasibility of using a Ta₂O₅ coating for protecting Si₃N₄ from hot corrosion. The coated structure was relatively stable at 1000^deg;C in pure O₂. However, the Ta₂O₅-Si₃N₄ system became unstable in an environment containing Na₂SO₄ and O₂ at 1000^deg;C because (1) Ta₂O₅ and Na₂SO₄ reacted rapidly to form NaTaO₃ and (2) subsequently NaTaO₃ interacted destructively with the underlying Si₃N₄ substrate to form a molten phase.     

Refining in the Glassmelting Process

Refining mechanisms for a soda-lime glassmelt containing bubbles are proposed, based on photographic observations and data in literature. The equation expressing the removal of bubbles from the glassmelt by ascension has been derived from a linear relation between bubble size and time. Experimental and theoretical studies have shown that heterogeneous bubble nucleation occurs during refining. An additive relation between SiO₂ (sand) dissolving tune and the theoretical refining time resulting from heterogeneous bubble nucleation has been verified for As₂O₃+ NaNO₃, Na₂SO₄, and NaCl additions to a soda-lime glass batch.     

Morphology of Zirconia Synthesized Hydrothermally from Zirconium Oxychloride

Monoclinic zirconia has been synthesized hydrothermally from zirconium oxychloride in the range 20–100 MPa, 250–650°C, for run duration from 20 to 100 h and in the presence of NaOH, Na₂CO₃, Na₂SO₄, NH₄F, HNO₃, and H₂SO₄ additives. Isometric, platelike, and elongated crystal morphologies were obtained depending on the additive. Both spherulitic and isolated textures were encountered with H₂SO₄. Growth of isometric crystals follows a general dissolution–precipitation mechanism. For H₂SO₄, two growth steps were identified: an early spherulitic step followed by an isolated crystals step resulting from Ostwald ripening of preexisting spherulites. The formation of spherulites is consistent with the specific properties of the sulfuric hydrothermal medium.     

Synthesis of Anatase-Type TiO2 Nanocrystallites Via a Redox Route

Anatase nanocrystallites showing high surface area (∼62 m²/g) and good photocatalytic property have been obtained by pyrolyzing at 600°C for 4 h an ammonium titanyl double sulfate precursor (α-(NH₄)₂TiO(SO₄)₂) synthesized via a redox approach, that is, by oxidizing an aqueous solution of titanium trichloride (TiCl₃) with ammonium peroxodisulfate ((NH₄)₂S₂O₈), followed by reacting with ammonium sulfate ((NH₄)₂SO₄).     

Molten-Salt Corrosion of Silicon Nitride: II, Sodium Sulfate

The corrosion mechanism of Si₃N₄+ Na₂SO₄/O₂ at 1000°C was investigated. Corrosion of both pure and additive-containing Si₃N₄ was studied. The reaction of Si₃N₄+ Na₂SO₄ consists of an initial period of slow weight loss due to Na₂SO₄ vaporization and oxidation-dissolution. This initial period was the same for all forms of Si₃N₄. A second region consisted of further oxidation or near termination of reaction, depending on the additive in the Si₃N₄. A 5- to 10-μm yttrium depletion zone was found after corrosion for the Si₃N₄ with yttria additives. For comparison, Si and SiC were corroded under similar conditions. These materials corroded substantially faster than all forms of Si₃N₄.     

Burner Rig Hot Corrosion of Silicon Carbide and Silicon Nitride

A number of commercially available SiC and Si₃N₄ materials were exposed to 1000°C for 40 h in a high-velocity, pressurized burner rig as a simulation of an aircraft turbine environment. Na impurities (2 ppm) added to the burner flame resulted in molten Na₂SO₄ deposition, attack of the SiC and Si₃N₄, and formation of substantial Na₂O. x (SiO₂) corrosion product. Room-temperature strength of the materials decreased as a result of the formation of corrosion pits in SiC and grain-boundary dissolution and pitting in Si₃N₄.