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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1986

Molten salt corrosion of SiC and Si3N4

The most severe type of corrosion encountered in heat engines is corrosion by molten sodium sulfate, formed by the reaction of ingested sodium chloride and sulfur impurities in the fuel. This problem was studied extensively for superalloys, but only recently examined for ceramics. This problem is addressed with laboratory studies to understand the fundamental reaction mechanisms and with burner studies to provide a more realistic simulation of the conditions encountered in a heat engine. In addition the effect of corrosion on the strengths of these materials was assessed. Each of these aspects will be reviewed and some ideas toward possible solutions will be discussed.

Jacobson, N. S.↗
NASA NTRS1985

Molten salt corrosion of SiC: Pitting mechanism

Thin films of Na2SO4 and Na2CO3 at 1000 C lead to severe pitting of sintered alpha-SiC. These pits are important as they cause a strength reduction in this material. The growth of product layers is related to pit formation for the Na2CO3 case. The early reaction stages involve repeated oxidation and dissolution to form sodium silicate. This results in severe grain boundary attack. After this a porous silica layer forms between the sodium silicate melt and the SiC. The pores in this layer appear to act as paths for the melt to reach the SiC and create larger pits.

Jacobson, N. S.↗
NASA NTRS1988

Molten-salt corrosion of silicon nitride. I - Sodium carbonate. II - Sodium sulfate

An experimental study of the corrosion of Si3N4 under thin films of Na2CO3 at 1000 C has been conducted using both pure Si3N4 and Si3N4 with various additives. The reaction mechanism is shown to consist of: (1) the decomposition of Na2CO3 and the formation of Na2SiO3; (2) rapid oxidation; and (3) the formation of a protective silica layer below the silicate. In the second part, the corrosion mechanism of Si3N4 + Na2SO4/O2 at 1000 C was studied for both pure and additive-containing Si3N4. The reaction of Si3N4 + Na2SO4 was found to involve an initial period of slow weight loss (due to Na2SO4 vaporization and oxidation-dissolution) followed by further oxidation or the near termination of the reaction, depending on the Si3N4 additive.

Fox, Dennis S.↗
NASA NTRS1988

Molten salt corrosion of SiC and Si3N4

Industrial systems such as heat engines and heat exchangers involve harsh environments. The structural materials are subjected to high temperatures as well as corrosive gases and condensed phases. Past experience with metal alloys has shown that these condensed phases can be particularly corrosive and are often the limiting factor in the operation of these systems. In a heat engine the most common condensed corrodent is Na2SO4 whereas in a heat exchanger an oxide slag may be present. The primary emphasis is on Na2SO4 induced corrosion, however, similarities and differences to oxide slag are also discussed. The extensive research on corrosion of metal alloys has led to understanding and controlling corrosion for these materials. Currently silicon based ceramics are prime candidates for the applications discussed. Therefore it is important to understand the effects of condensed phase deposits on this emerging class of high temperature materials. Both the thermodynamic and strength of the ceramic is also examined. Finally some control strategies for corrosion of silicon based ceramics are explored.

Jacobson, Nathan S.↗
NASA NTRS1986

Kinetics and mechanism of corrosion of SiC by molten salts

Corrosion of sintered alpha-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 coupled with morphology observations leads to a detailed corrosion mechanism. In all cases the corrosion reactions occur primarily in the first few hours. In the Na2CO3/CO2 case, rapid oxidation and dissolution lead to a thick layer of silicate melt in about 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 carbide, and a silicate melt forms above this. In addition, SiO2 and regenerated Na2SO4 form at the melt/gas interface due to reaction of silicate with SO3 and SO2 + O2. The reaction slows when the lower silica layer becomes nonporous.

Jacobson, N. S.↗
NASA NTRS1986

Corrosion pitting of SiC by molten salts

The corrosion of SiC by thin films of Na2CO3 and Na2SO4 at 1000 C is characterized by a severe pitting attack of the SiC substrate. A range of different Si and SiC substrates were examined to isolate the factors critical to pitting. Two types of pitting attack are identified: attack at structural discontinuities and a crater-like attack. The crater-like pits are correlated with bubble formation during oxidation of the SiC. It appears that bubbles create unprotected regions, which are susceptible to enhanced attack and, hence, pit formation.

Jacobson, N. S.↗
NASA NTRS1987

Corrosion of SiC by Molten Salt

Advanced ceramic materials considered for wide range of applications as in gas turbine engines and heat exchangers. In such applications, materials may be in corrosive environments that include molten salts. Very corrosive to alloys. In order to determine extent of problem for ceramic materials, corrosion of SiC by molten salts studied in both jet fuel burners and laboratory furnaces. Surface of silicon carbide corroded by exposure to flame seeded with 4 parts per million of sodium. Strength of silicon carbide decreased by corrosion in flame and tube-furnace tests.

Jacobson, Nathan S.↗
NASA NTRS1975

Stress corrosion cracking of Ti-8Al-1 Mo-1V in molten salts

The stress corrosion cracking (SCC) behavior of Ti-8Al-1 Mo-1V has been studied in several molten salt environments. Extensive data are reported for the alloy in highly pure LiCl-KCl. The influence of the metallurgical heat treatment and texture, and the mechanical microstructure show similarities with aqueous solutions at lower temperature. The fracture path and cracking modes are also similar to that found in other environments. The influence of H2O and H(-) in molten LiCl-KCl lead to the conclusion that hydrogen does not play a major role in crack extension in this environment.

Smyrl, W. H.↗
NASA NTRS1996

Corrosion of Mullite by Molten Salts

The interaction of molten salts of different Na2O activities and mullite is examined with furnace and burner tests. The more-acidic molten salts form small amounts of Al2O3; the more-basic molten salts form various Na2O-Al2O3-SiO2 compounds. The results are interpreted using the Na2O-Al203-SiO2 ternary phase diagram, and some possible diffusion paths are discussed. The generally higher melting points of Na2O-Al2O3-SiO2 compounds lead to better behavior of mullite in molten salts, as compared to SiO2-protected ceramics such as SiC. Mullite-coated SiC is discussed, and the corrosion behavior is evaluated.

Jacobson, Nathan S.↗
NASA NTRS1996

Coating Silicon-Based Ceramics With Durable Mullite

Improved plasma-spraying process deposits mullite on silicon carbide substrates. Prevents formation of amorphous mullite by maintaining high temperature of sprayed deposite to allow crystallization to occur. Deposited mullite adheres to substrate and exhibits little or no cracking during thermal cycling. Provides substantially greater resistance to oxidation in dry air and corrosion by molten salt. Process expected useful in depositing mullite on substrates made of other silicon-based ceramics and other ceramic substrates having coefficients of thermal expansion similar to those of mullite.

Miller, Robert A.↗
NASA NTRS1984

Mechanism of strength degradation for hot corrosion of alpha-SiC

Sintered alpha SiC was corroded by thin films of Na2SO4 and Na2CO3 molten salts at 1000%. This hot corrosion attack reduced room temperature strengths by as much as 50%. Strength degradation was porportional to the degree and uniformity of corrosion pitting attack as controlled by the chemistry of the molten salt. Extensive fractography identified corrosion pits as the most prevalent source of failure. A fracture mechanics treatment of the strength/pit depth relationship produced an average K sub IC equal to 2.6 MPa sub m 1/2, which is consistent with published values.

Smialek, J. L.↗
NASA NTRS1986

Mechanism of strength degradation for hot corrosion of alpha-SiC

Sintered alpha SiC was corroded by thin films of Na2SO4 and Na2CO3 molten salts at 1000 percent. This hot corrosion attack reduced room temperature strengths by as much as 50 percent. Strength degradation was proportional to the degree and uniformity of corrosion pitting attack as controlled by the chemistry of the molten salt. Extensive fractography identified corrosion pits as the most prevalent source of failure. A fracture mechanics treatment of the strength/pit depth relationship produced an average K sub IC equal to 2.6 MPa sub m 1/2, which is cnsistent ith published values.

Smialek, James L.↗
NASA NTRS1995

Durability of Silica-Protected Ceramics in Combustion Atmospheres

This overview of oxidation and corrosion effects on silica-protected ceramics and composites is divided into two parts: (1) External effects and (2) Internal effects. In regard to the first part, the literature indicates silica the best of the common protective oxides in pure oxygen. However in actual applications, there are four major degradation routes which must be considered: (1) Formation of SiO(g); (2) water vapor enhancement of oxidation rate of Si(OH)4 volatiles; (3) low level metal cation enhancement of oxidation rate; and (4) molten salt and slag corrosion. Several protective coating concepts have been discussed, which may minimize these effects. Internal effects deal with a microcrack providing a path for oxygen ingress to the oxygen sensitive fiber and fiber coating. This is a critical area of study for theses materials. Possible solutions involve a fluid glass to fill the cracks and/or oxygen getting along the walls of the crack.

Jacobson, Nathan S.↗
NASA NTRS1999

Key Durability Issues with Mullite-Based Environmental Barrier Coatings for Si-Based Ceramics

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.

Lee, Kang N.↗
NASA NTRS2000

Key Durability Issues with Mullite-Based Environmental Barrier Coatings for Si-Based Ceramics

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.

Lee, Kang N.↗
NASA NTRS1987

Fluoride salts and container materials for thermal energy storage applications in the temperature range 973 to 1400 K

Multicomponent fluoride salt mixtures were characterized for use as latent heat of fusion heat storage materials in advanced solar dynamic space power systems with operating temperatures in the range of 973 to 1400 K. The melting points and eutectic composition for many systems with published phase diagrams were verified, and several new eutectic compositions were identified. Additionally, the heats of fusion of several binary and ternary eutectics and congruently melting intermediate compounds were measured by differential scanning calorimetry. The extent of corrosion of various metals by fluoride melts was estimated from thermodynamic considerations, and equilibrium conditions inside a containment vessel were calculated as functions of the initial moisture content of the salt and free volume above the molten salt. Preliminary experimental data on the corrosion of commercial, high-temperature alloys in LiF-19.5CaF2 and NaF-27CaF2-36MgF2 melts are presented and compared to the thermodynamic predictions.

Misra, Ajay K.↗