Oxidation of Zirconium Diboride–Silicon Carbide at 1500°C at a Low Partial Pressure of Oxygen

The oxidation behavior of zirconium diboride containing 30 vol% silicon carbide particulates was investigated under reducing conditions. A gas mixture of CO and ∼350 ppm CO₂ was used to produce an oxygen partial pressure of ∼10⁻¹⁰ Pa at 1500°C. The kinetics of the growth of the reaction layer were examined for reaction times of up to 8 h. Microstructures and chemistries of reaction layers were characterized using scanning electron microscopy and X-ray diffraction analysis. The kinetic measurements, the microstructure analysis, and a thermodynamic model indicate that oxidation in CO–CO₂ produced a non-protective oxide surface scale.     

The role of microstructure on high-temperature oxidation behavior of hafnium carbide

Microstructure development of the products formed upon oxidation of hafnium carbide (HfC_x, x = 0.65, 0.81, or 0.94) at 1300°C and 0.8 mbar oxygen pressure was investigated using Raman spectroscopy, X-ray diffraction, electron microscopy, and electron energy-loss spectroscopy. For all specimens a multilayered oxide scale was observed featuring an outermost porous hafnia layer and an interlayer adjacent to the parent carbide containing hafnia interspersed with carbon. The outermost hafnia features coarse pores presumably formed during initial stages of oxidation to allow rapidly evolving gaseous products to escape from the oxidation front. As the oxidation scale thickens, diffusional resistance results in slower oxidation rates and smaller quantities of gaseous products that are removed via networks of increasingly fine pores until the local oxygen partial pressure is sufficiently low to selectively oxidize the parent carbide. Electron microscopy studies suggest that the oxidation sequence at this stage begins with the transformation of parent carbide to an amorphous material having empirical formula HfO₂C_x that subsequently phase separates into hafnia and carbon domains. Hafnia polymorphs in the phase-separated region vary from cubic to monoclinic as grains coarsen from ca. 2–20 nm, respectively. Immediately adjacent to the phase-separated region is carbon-free mesoporous hafnia whose pore morphology is inherited from that of prior carbon domains. The average pore size and pore volume fraction observed in mesoporous hafnia are consistent with predictions from kinetic models that ascribe gaseous diffusion through a pore network as the rate determining step in oxidation behavior of hafnium carbide. These observations imply that high-temperature oxidation behavior of hafnium carbide under the employed test conditions is linked to microstructure development via phase separation and coarsening behaviors of an initially formed amorphous HfO₂C_x product.     

New insight into the formation and oxygen barrier mechanism of carbonaceous oxide interlayer in a multicomponent carbide

Early transition metal carbides are considered to be superior candidate materials for oxidizing environments at temperatures exceeding 2000°C. Generally, the remarkable oxidation resistance is largely attributed to a carbonaceous oxide interlayer (eg, Hf–O–C, Zr–O–C, and Ta–O–C), located at the interface between the external oxide layer and internal carbide (eg, HfC, ZrC, and TaC), acting as the primary oxygen barrier. However, the oxygen barrier mechanism of the carbonaceous oxide interlayer remains unclear. Herein, through studying the oxidation behavior of a novel multicomponent carbide Hf_0.5Zr_0.3Ti_0.2C in oxidizing environments up to 2500°C, the oxygen barrier mechanism of the carbonaceous oxide was recently revealed. We found that the oxygen barrier resulted from the slow oxygen diffusion through the inner grains of Hf-Zr–Ti–O due to the presence of carbon formed at the grain boundaries because of the existence of compact external oxide layer, beneath which the Hf–Zr–Ti–O–C interlayer possesses much lower oxygen activity and temperature that allow carbon to exist stably. This as-formed carbon strongly retarded the fast diffusion of oxygen along the grain boundaries of oxides. Additionally, desirable synergisms of the designed multicomponent system, particularly, the outward short-circuit diffusion of Ti, lead to the self-healing of the external oxide layer, evidently enhancing integral protection performance against oxidizing environments.     

Kinetics of the Graphite-Uranium Dioxide Reaction from 1400° to 1756°C

The reaction of microspheres of UO_z with graphite was studied from 1400° to 1756°C. When a spherically symmetrical layer of carbide was produced around the UO₂ core, only UC₂ was formed, and the diffusion of oxygen through this layer was rate-controlling. The Arrhenius relation for this system is k_D= 21.0 exp(−90, 000/ RT ) cm²/s
The reaction of a geometrically nonsymmetrical configuration of UO₂ and UC₂ was also studied. Comparison of the reactions in the symmetrical and nonsymmetrical systems demonstrated that the kinetic behavior of the two systems is quite different and that the conversion in the nonsymmetrical system was 2 to 5 times faster. The importance of these observations to kinetic results reported in the literature for analogous systems is discussed.     

Oxidation of Single Crystals of Hafnium Carbide in a Temperature Range of 600° to 900°C

The isothermal oxidation of HfC single crystals with (100) orientation was carried out using an electromicrobalance at temperatures of 600° to 900°C at an oxygen pressure of 2 to 8 kPa. Nonisothermal oxidation was performed by a simultaneous thermogravimetry-differential thermal analysis-mass spectrometry analysis. A polished cross section of the oxidized crystal was observed by backscattered electron imaging in a scanning electron microscope. Quantitative chemical analysis for Hf, O, and C and their elemental profiles in the HfC and oxide scale was carried out by wavelength dispersive X-ray microanalysis. It was found that the oxide scale consists of two regions, zones 1 and 2, both of which showed the existence of carbon. The carbon content at the middle point of zone 1 was about twice that in zone 2, which contained 7 to 14 at.% carbon. Zone 1 showed an almost compact and pore-free phase; its thickness remained constant (1 to 2 μm) after a prolonged time. The thickness of zone 2 increased linearly with time. The oxidation mechanism including interfacial reaction responsible for the deposition of carbon is discussed.     

Reaction of Iradium with Metal Carbides in the Temperature Range of 1923 to 2400 K

The reactions of titanium carbide and hafnium carbide with iridium have been studied in thin film couples fabricated by vapor deposition processes. The reaction product layers after exposure in the temperature range of 1923 to 2400 K are dependent on the stoichiometry of the metal carbide layers and range from simple solid solutions to MIr_x compounds. The observed microstructures are predictable from available thermochemical data. The morphology of residual carbon in the reacted metal carbide-iridium product layer varies from interfacial deposits to uniform carbon dispersion and depends upon exposure temperature and metal carbide stoichiometry.     

Industrial Diamond Substitutes: I, Physical and X-Ray Study of Hafnium Carbide

A study of hard materials in an effort to find possible substitutes for industrial diamonds led to research on hafnium carbide. This compound was prepared from a mixture of hafnium dioxide and lampblack in a carbon resistance furnace by solid-state reaction or from a melt. Some factors affecting the combined carbon content of the re- action products were qualitatively evaluated. A hafnium carbide prepared from a melt at a temperature slightly above 2800°C. with no holding time had a combined carbon content within 98% of the theoretical value. A curve was obtained by plotting combined carbon against cubic unit- cell dimension (a₀) for the hafnium carbide- "hafnium monoxide" solid solution series. Extrapolation gave 4.641 ± 0.001 a.u. for the cell edge of hafnium carbide of theoretical composition; a₀ was observed as high as 4.640 a.u. Density values within 99% of theoretical were obtained. Knoop microindentation hardness measurements with both dry and oil-immersion objectives indicated a hardness in the silicon carbide range. Owing to its high cost and relatively low hard- ness, hafnium carbide is presently not considered to be a promising substitute for industrial diamonds.     

Oxidation Kinetics of Hafnium Carbide in the Temperature Range of 480° to 600°C

The isothermal oxidation of HfC powders was carried out at temperatures of 480° to 600°C at oxygen pressure of 4, 8, and 16 kPa, using an electromicrobalance. The oxidized product was identified by X-ray analysis, Raman spectroscopy, X-ray photoelectron spectroscopy, and electron diffraction, and the morphology of the oxidized grains was observed by scanning electron microscopy. Oxidation proceeds by two processes: a diffusion-controlled process operates up to about 50% oxidation and a phase-boundary-controlled process operates above about 50% oxidation. The activation energies for both processes are the same (197 ± 15 kJ.mol⁻¹). The change in the oxidation process is associated with the generation of cracks on the grains, resulting from the growth or expansion stress due to the formation of monoclinic HfO₂ microcrystallites less than 3 nm in size. In the latter process, the thickness of the diffusion layer is kept constant, being time-independent, which allows the process to apparently obey the phase-boundary-controlled reaction.     

Preparation of Barium Titanate Films at 55°C by an Electrochemical Method

Work by previous investigators has shown that BaTiO₃ films can be synthesized from solution over temperature ranges from 80°C to greater than 200°C. In the present work, electrically insulating crystalline films of BaTiO₃ have been electrochemically deposited on titanium substrates at temperatures as low as 55°C. Auger spectroscopic analyses with depth profiling indicate that a titanium oxide layer whose thickness is governed by current density acts as a precursor to BaTiO₃. Formation of BaTiO₃ is found to be favored only in highly alkaline solutions. This is consistent with the phase stability reported for the Ba─Ti─CO₂─H₂O system at 25°C. Lower processing temperatures (55°C) favor the formation of thick, electrically resistive, and wellcrystallized BaTiO₃ films, apparently due to increased oxygen solubility in the electrolyte solution. Films produced at 100°C are much thinner and are electrically conductive due to fissures and pores in their microstructure. Initial studies on the effect of current density indicate the formation of thinner and porous films with thicker titanium oxide intermediate layers.     

Thermal Expansion of Three Group IVA Carbides to 2700°C

X-ray thermal expansion measurements on arc- cast carbides of titanium, zirconium, and hafnium are reported. The coefficients of thermal expansion for these materials from room temperature to 2700°C are 9.5 ± 0.3 × 10^−6/0C, 7.6 ± 0.2 × 10^−6/0C, and 7.3 ± 0.2 × 10^−6/0C, respectively.     

Interdiffusion of Calcium in Soda-Lime-Silica Glass at 880° to 1308°C

The interdiffusion of calcium in soda-lime-silica glass under the action of a concentration gradient was studied. Pairs of glass blocks differing by 2.9 mole % in CaO content were fused together to form diffusion couples and were held at 880° to 1308°C. The couples were allowed to cool to room temperature and the diffusion which had taken place was measured by optical interferometry and by an electron microprobe. The diffusion coefficients varied from 4.4 × 10⁻¹⁰cm²/sec at 880°C to 8.0 × 10⁻⁸ cm²/sec at 1308°C. The activation energy was 42,000 cal/mole. It is concluded that oxygen diffuses simultaneously with the calcium, maintaining the electrical neutrality of the glass.     

Lifetime-Applied Stress Response in Air of a SiC-Based Nicalon-Fiber-Reinforced Composite with a Carbon Interfacial Layer: Effects of Temperature (300° to 1150°C)

The lifetimes in air as a function of applied flexure stress and temperature (300–1150°C) are described for a Si–O–C based (Nicalon) fiber plain-weave cloth reinforced SiC-matrix composite (∼7% closed porosity) with an ∼0.3 µm thick carbon interfacial layer. The measured lifetimes of both samples with and without an external SiC seal coating were similar and decreased with applied flexural stress (for stresses greater than ∼90 MPa) and with temperature. At temperatures of ≥600°C, the external CVD SiC coating had negligible effect on the lifetimes; however, at 425°C, a detectable improvement in the lifetime was observed with an external SiC coating. When the applied stress was decreased below an apparent "threshold stress" (e.g., ∼90 MPa) for tests conducted at temperatures ≤950°C, no failures were observed for times of ≥1000 h. Electron microscopy observations show that the interfacial carbon layer is progressively removed during tests at 425° and 600°C. In these cases, failure is associated with fiber failure and pullout. At 950° and 1150°C, the carbon interface layer is eliminated and replaced by a thick silica layer due to the oxidation of the Nicalon fiber and the SiC matrix. This results in embrittling the composite.     

Oxidation Behavior of Chemically-Vapor-Deposited Silicon Carbide and Silicon Nitride from 1200° to 1600°C

The isothermal oxidation of pure CVD SiC and Si₃N₄ has been studied for 100 h in dry, flowing oxygen from 1200° to 1600°C in an alumina tube furnace. Adherent oxide formed at temperatures to 1550°C. The major crystalline phase in the resulting silica scales was alpha-cristobalite. Parabolic rate constants for SiC were within an order of magnitude of literature values. The oxidation kinetics of Si₃N₄ in this study were not statistically different from that of SiC. Measured activation energies were 190 kJ/mol for SiC and 186 kJ/mol for Si₃N₄. Silicon oxynitride did not appear to play a role in the oxidation of Si₃N₄ under the conditions herein. This is thought to be derived from the presence of ppm levels of sodium impurities in the alumina furnace tube. It is proposed that sodium modifies the silicon oxynitride, rendering it ineffective as a diffusion barrier. Material recession as a function of oxide thickness was calculated and found to be low. Oxidation behavior at 1600°C differed from the lower temperatures in that silica spallation occurred after exposure.     

Silica-pillared graphene sheets with iron–nitrogen units as an oxygen reduction catalyst

Graphene layers with silica pillars which widen the interlayer distance and functionalize the space as micropores have been prepared as one of the new porous carbon materials. In this study, the silica-pillared graphene with Fe–N units as a catalytic active site for cathodic oxygen reduction was formed as a new type of carbonaceous noble-metal-free oxygen reduction catalysts with the ordered pore structure. The formation of the pillared carbon was performed by introducing silylating reagents as the pillar source and also as the nitrogen source of the units in the graphite oxide interlayer spaces, introducing the Fe ions, and heat treatment in vacuum at 500 °C. The X-ray diffraction (XRD) patterns showed the ordered layered structure. The X-ray absorption fine structure (XAFS) of the Fe-K edge showed that the unit was a square planar Fe–N₄ moiety. The catalytic activity for the O₂ reduction was demonstrated by measurements using rotating disk electrodes with the pillared carbon fixed on the surface and immersed in an oxygen-saturated acidic solution. The activity was enhanced by the combination of the nitrogen containing compound to the silylating reagent and using the nitrogen-rich silylating reagent.     

Some Properties of Hafnium Oxide, Hafnium Silicate, Calcium Hafnate, and Hafnium Carbide

The behavior of hafnium oxide was studied particularly in the temperature range 1500° to 18OO°C. Properties of HfO₂ at these temperatures and its reactions with ZrO₂, SiO₂, and CaO are given in terms of lattice and other physical measurements, many of which are new. Mono-clinic hafnium oxide is stable to 1700°C., which is 600° higher than the corresponding inversion temperature of zirconia. Otherwise HfO₂ closely resembles ZrO₂ (a) in its lattice dimensions and sintering behavior, (b) in forming a high-temperature tetragonal phase closely resembling tetragonal ZrO₂, (c) in forming a continuous series of solid solutions with ZrOz, (d) in forming with silica a single compound (HfO₂.SiO₂) similar to zircon, (e) in forming a carbide, (f) in uniting with up to 40% CaO to form cubic solid solutions; thereafter a compound CaO.Hf O₂ appears which is very similar to the corresponding zirconia compound.     

High-Temperature Oxidation at 1500° and 1600°C of SiC/Graphite Coated with Sol–Gel-Derived HfO2

Oxidation of SiC compositionally graded (SCGed) graphite coated with HfO₂ derived from HfCl₄ by a sol–gel process was performed at 1500° and 1600°C in a flowing gas mixture of Ar and O₂ (80/20 kPa). SCGed graphite was produced by reaction of graphite with either molten Si or SiO gas at 1450°C. The sol–gel-derived HfO₂ precursor was deposited on SCGed graphite by a dip-coating method. Isothermal and cyclic oxidation of uncoated- and HfO₂-coated SCGed graphite was studied by monitoring overall weight change using an electro-microbalance. Scanning electron microscopy with energy-dispersive X-ray analysis was used to observe the surfaces and cross-sections of the oxidized HfO₂-coated SCGed graphite. The formation of HfSiO₄ was confirmed on the outer layer of the oxidized sample, beneath which a thin silica layer was formed. The improved oxidation resistance of SCGed graphite by coating with HfO₂ is discussed on the basis of the formation of these two layers.     

Solid-State Reaction Between Titanium Carbide and Titanium Metal

The solid-state reaction between titanium and titanium carbide to form substoichiometric titanium carbide was studied by annealing single-crystal diffusion couples at T = 1350° to 1525°C. The thickness of the epitaxially grown carbide layer was almost an order of magnitude greater than that predicted from published values for chemical diffusion of carbon through titanium carbide. A value of 424 exp[–368 kJ/mol/RT] cm²/s is calculated for the chemical diffusivity of carbon from the diffusion-couple data of the present study. This anomalously rapid diffusion of carbon is associated with short-circuit diffusion along platelets of Ti₂C which develop parallel to {111} planes in TiC during the reaction. The Ti₂C platelets extend from the original Ti-TiC interface to the moving reaction front and also grow from the original interface into the original carbide crystal.     

Alumina/NiCu Laminate under Thermal Shock up to 1000°C: I, Experimental

The mechanical behavior of an alumina/NiCu laminate under thermal shock loading was investigated. The maximum thermal shock temperature was 1000°C. The laminate architecture was the cause of a basic change in the cracking mechanisms, manifested in a dramatic increase in the mechanical residual strength over that of monolithic alumina. The laminated system was constructed by alternating alumina layers coated with copper films with nickel interlayers and joining them by a combination of liquid-state (brazing) and solid-state (diffusion) bonding. The material system was tested by water quenching square-shaped laminated specimens initially at temperatures of up to 1000°C. Three-point bending tests revealed the mechanical strength before and after thermal shock, and SEM analysis described the damage mechanisms and the extent of debonding at the alumina/NiCu interfaces.     

Kinetics of the Reaction of UC2 and Nitrogen from 1500° to 1700°C

The kinetics of the reaction of UC₂ spheres with nitrogen was studied from 1500° to 1700°C. A metallographic method was used to determine the time-dependent conversion of UC₂ to U(C,N) and free C. The conversion appeared to be controlled by the diffusion of solid carbon in solution to sites where it could precipitate as free carbon. These sites were the surface of the sphere and particles of free carbon that existed within the original UC₂. An increased distribution of these internal sites decreased the distance for carbon diffusion and resulted in an increased rate of reaction. The UC₂ appeared to undergo a very rapid initial reaction that resulted in the uptake of 1 to 5 at.% nitrogen in the UC₂ at these temperatures.     

Oxidation Kinetics of Silicon Carbide Crystals and Ceramics: I, In Dry Oxygen

The oxidation kinetics of several single-crystal and polvcrystalline silicon carbide materials and single-crystal silicon in dry oxygen over the temperature range 1200° to 1500°C were fitted to the linear-parabolic model of Deal and Grove. The lower oxidation rates of silicon carbide compared to silicon can be rationalized by additional consumption of oxidant in oxidizing carbon to carbon dioxide. The (000J) Si face of the silicon carbide platelets exhibited lower parabolic oxidation rates than the (0001) C face, by a factor of 10 at 1200°C. Apparent activation energies increased from a value of ∼120 kJ/mol below 1400°C to a value of ∼300 kJ/mol above this temperature. The (0001) Si face exhibited this high activation energy over the entire temperature range. The controlled nucleation thermally deposited material exhibited the highest oxidation rates of the polycrystalline materials followed by the hot-pressed and sintered α-silicon carbides. In general, the oxidation rates of the polycrystalline materials were bracketed by the oxidation rates of the basal planes of the single-crystal materials. Higher impurity concentrations and higher density of nucleation sites led to a greater susceptibility to crystallization of the scale which significantly complicated the oxidation behaviors observed. When crystallization of the oxide scale occurred in the form of a layer of spherulitic cristobalite crystals, a retardation of the oxidation rates was observed. An accelerated oxidation behavior was found when this coherent layer was superseded by the formation of fine mullite crystals.