Engineering Papers⌕ Search

Engineering topics

Jacobson, Nathan S.

Publications and source records attributed to Jacobson, Nathan S..

At least 91 records · Page 5

Mass Spectrometric Identification of Si-O-H(g) Species from the Reaction of Silica with Water Vapor at Atmospheric Pressure

A high-pressure sampling mass spectrometer was used to detect the volatile species formed from SiO2 at temperatures between 1200C and 1400C in a flowing water vapor/oxygen gas mixture at 1 bar total pressure. The primary vapor species identified was Si(OH)4. The fragment ion Si(OH)3+,' was observed in quantities 3 to 5 times larger than the parent ion Si(OH)4+. The Si(OH)3+ intensity was found to have a small temperature dependence and to increase with the water vapor partial pressure as expected. In addition, SiO(OH)+ believed to be a fragment of SiO(OH)2, was observed. These mass spectral results were compared to the behavior of silicon halides.

Opila, Elizabeth J.↗

Environmental Effects on Non-oxide Ceramics

Non-oxide ceramics such as silicon carbide (SiC) and silicon nitride (Si3N4) are promising materials for a wide range of high temperature applications. These include such diverse applications as components for heat engines, high temperature electronics, and re-entry shields for space vehicles. Table I lists a number of selected applications. Most of the emphasis here will be on SiC and Si3N4. Where appropriate, other non-oxide materials such as aluminum nitride (AlN) and boron nitride (BN) will be discussed. Proposed materials include both monolithic ceramics and composites. Composites are treated in more detail elsewhere in this volume, however, many of the oxidation/corrosion reactions discussed here can be extended to composites. In application these materials will be exposed to a wide variety of environments. Table I also lists reactive components of these environments.It is well-known that SiC and Si3N4 retain their strength to high temperatures. Thus these materials have been proposed for a variety of hot-gas-path components in combustion applications. These include heat exchanger tubes, combustor liners, and porous filters for coal combustion products. All combustion gases contain CO2, CO, H2, H2O, O2, and N2. The exact gas composition is dependent on the fuel to air ratio or equivalence ratio. (Equivalence ratio (EQ) is a fuel-to-air ratio, with total hydrocarbon content normalized to the amount of O2 and defined by EQ=1 for complete combustion to CO2 and H2O). Figure 1 is a plot of equilibrium gas composition vs. equivalence ratio. Note that as a general rule, all combustion atmospheres are about 10% water vapor and 10% CO2. The amounts of CO, H2, and O2 are highly dependent on equivalence ratio.

Jacobson, Nathan S.↗

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.↗

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.↗

Volatile Hydroxide Species of Common Protective Oxides and their Role in High Temperature Corrosion

Thermodynamic data for volatile hydroxides and oxyhydroxides formed from the reaction of water vapor with Cr2O3, SiO2, A12O3, Y2O3,. and ZrO2 were assembled. The volatile species formed at temperatures between 800 and 2200K in model combustion environments containing 10% water vapor and 10% oxygen at 1 and 10 bar total pressure were calculated using free energy minimization techniques. Assuming an acceptable maximum vapor pressure limit for volatile species of 10 bar, an upper use temperature for these oxides was determined at 1 and 10 bar total pressure. The dependence of these volatile species on both water vapor and oxygen pressure was determined.

Opila, Elizabeth J.↗

Double-Knudsen-Cell Apparatus Measures Alloy-Component Activities

Double-Knudsen-cell apparatus provides molecular beam from selected one of two Knudsen cells. Both cells maintained at same temperature. Molecular beam directed into mass spectrometer for measurement of vapor pressure of selected material component. Designed to minimize undesired thermal gradients, provides appropriate translation to place selected cell in position for sampling, and minimizes mixing of molecular beams from cells.

Jacobson, Nathan S.↗

New generation of plasma-sprayed mullite coatings on silicon carbide

Mullite is promising as a protective coating for silicon-based ceramics in aggressive high-temperature environments. Conventionally plasma-sprayed mullite on SiC tends to crack and debond on thermal cycling. It is shown that this behavior is due to the presence of amorphous mullite in the conventionally sprayed mullite. Heating the SiC substrate during the plasma spraying eliminated the amorphous phase and produced coatings with dramatically improved properties. The new coating exhibits excellent adherence and crack resistance under thermal cycling between room temperature and 1000 to 1400 C. Preliminary tests showed good resistance to Na2CO3-induced hot corrosion.

Lee, Kang N.↗

Chemical Stability of the Fiber Coating/Matrix Interface in Silicon-Based Ceramic Matrix Composites

Carbon and boron nitride are used as fiber coatings in silicon-based composites. In order to assess the long-term stability of these materials, reactions of carbon/Si3N4 and BN/SiC were studied at high temperatures with Knudsen effusion, coupon tests, and microstructural examination. In the carbon/Si3N4 system, carbon reacted with Si3N4 to form gaseous N2 and SiC. The formation of SiC limited further reaction by physically separating the carbon and Si3N4. Consequently, the development of high p(N2) at the interface, predicted from thermochemical calculations, did not occur, thus limiting the potential deleterious effects of the reaction on the composite. Strong indications of a reaction between BN and SiC were shown by TEM and SIMS analysis of the BN/SiC interface. In long-term exposures, this reaction can lead to a depletion of a BN coating and/or an unfavorable change of the interfacial properties, limiting the beneficial effects of the coating.

Lee, Kang N.↗

Thermochemical Degradation Mechanisms for the Reinforced Carbon/Carbon Panels on the Space Shuttle

The wing leading edge and nose cone of the Space Shuttle are fabricated from a reinforced carbon/carbon material (RCC). The material attains its oxidation resistance from a diffusion coating of SiC and a glass sealant. During re-entry, the RCC material is subjected to an oxidizing high temperature environment, which leads to degradation via several mechanisms. These mechanisms include oxidation to form a silica scale, reaction of the SiO2 with the SiC to evolve gaseous products, viscous flow of the glass, and vaporization of the glass. Each of these is discussed in detail. Following extended service and many missions, the leading-edge wing surfaces have exhibited small pinholes. A chloridation/oxidation mechanism is proposed to arise from the NaCl deposited on the wings from the sea-salt laden air in Florida. This involves a local chloridation reaction of the SiC and subsequent re-oxidation at the external surface. Thermodynamic calculations indicate the feasibility of these reactions at active pits. Kinetic calculations predict pore depths close to those observed.

Jacobson, Nathan S.↗

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.↗

Refractory Oxide Coatings on Sic Ceramics

Silicon carbide with a refractory oxide coating is potentially a very attractive ceramic system. It offers the desirable mechanical and physical properties of SiC and the environmental durability of a refractory oxide. The development of a thermal shock resistant plasma-sprayed mullite coating on SiC is discussed. The durability of the mullite/SiC in oxidizing, reducing, and molten salt environments is discussed. In general, this system exhibits better behavior than uncoated SiC. Areas for further developments are discussed.

Lee, Kang N.↗

Chemical Reactions in the Processing of Mosi2 + Carbon Compacts

Hot-pressing of MoSi2 powders with carbon at high temperatures reduces the siliceous grain boundary phase in the resultant compact. The chemical reactions in this process were examined using the Knudsen cell technique. A 2.3 wt pct oxygen MoSi2 powder and a 0.59 wt pct oxygen MoSi2 powder, both with additions of 2 wt pct carbon, were examined. The reduction of the siliceous grain boundary phase was examined at 1350 K and the resultant P(SiO)/P(CO) ratios interpreted in terms of the SiO(g) and CO(g) isobars on the Si-C-O predominance diagram. The MoSi2 + carbon mixtures were then heated at the hot-pressing temperature of 2100 K. Large weight losses were observed and could be correlated with the formation of a low-melting eutectic and the formation and vaporization of SiC.

Jacobson, Nathan S.↗

Corrosion of Silicon-Based Ceramics in Combustion Environments

The processes of passive oxidation, deposit-induced corrosion, active oxidation, scale/substance interactions, and scale volatility are presently studied in the case of high-purity SiC and Si3N4 in pure oxygen, giving attention to such secondary elements in the ceramics as water and CO2 oxidants, combustion environment impurities, and thermal cycling. Deposit-induced corrosion is discussed for the cases of NaSO4 as well as vanadate and oxide-slag deposits; issues associated with the active-to-passive oxidation transition are noted.

Jacobson, Nathan S.↗

Volatile species in halide-activated-diffusion coating packs

An atmospheric pressure sampling mass spectrometer was used to identify the vapor species generated in a halide-activated cementation pack. Pack powder mixtures containing a Cr-Al binary masteralloy powder, an NH4Cl activator salt, and either ZrO2 or Y2O3 (or neither) were analyzed at 1000 C. Both the equilibrium calculations for the pack and mass spectrometer results indicated that volatile AlCl(x) and CrCl(y) species were generated by the pack powder mixture; in packs containing the reactive element oxide, volatile ZrCl(z) and YCl(w) species were formed by the conversion of their oxide sources.

Bianco, Robert↗

Reactions of silicon carbide and silicon(IV) oxide at elevated temperatures

The reaction between SiC and SiO2 has been studied in the temperature range 1400-1600 K. A Knudsen cell in conjunction with a vacuum microbalance and a high-temperature mass spectrometer was used for this study. Two systems were studied - 1:1 SiC (2 wt pct excess carbon) and SiO2; and 1:1:1 SiC, carbon, and SiO2. In both cases the excess carbon forms additional SiC within the Knudsen cell and adjusts to the direct reaction of stoichiometric SiC and SiO2 to form SiO(g) and CO(g) in approximately a 3:1 ratio. These results are interpreted in terms of the Si-C-O stability diagram.

Jacobson, Nathan S.↗

High-temperature durability considerations for HSCT combustor

The novel combustor designs for the High Speed Civil Transport will require high temperature materials with long term environmental stability. Higher liner temperatures than in conventional combustors and the need for reduced weight necessitates the use of advanced ceramic matrix composites. The combustor environment is defined at the current state of design, the major degradation routes are discussed for each candidate ceramic material, and where possible, the maximum use temperatures are defined for these candidate ceramics.

Jacobson, Nathan S.↗

Reactions of SiC with H2/H2O/Ar mixtures at 1300 C

Thermochemical modeling anticipates the existence of three reaction regions for the case of a sintered alpha-SiC with 5 percent H2/H2O/Ar at 1300 C, depending on the initial water vapor or, equivalently, oxygen, content of the gas stream. While a high oxygen content leads to SiC-protecting SiO2 surface film formation and limits consumption of the SiC through passive oxidation, intermediate oxygen contents lead to SiO and CO formation and rapid SiC consumption. In this intermediate region, reaction rates appear to be controlled by H2O gas-phase transport to the sample; reacted microstructures exhibit extensive grain-boundary attack in this region. Very low oxygen content is predicted to selectively remove carbon, with free silicon formation.

Jacobson, Nathan S.↗