Ultrahigh-Temperature Ceramics

journal

J. Am. Ceram. Soc., 84 [10] 224551 (2001)

Mechanical Properties of Silicon Oxycarbide Ceramic Foams

Paolo Colombo*,
Dipartimento di Chimica Applicata e Scienza dei Materiali, Universita ` di Bologna, Viale Risorgimento 2, 40136 Bologna, Italy

John R. Hellmann* and David L. Shelleman*

Materials Research Institute, Department of Material Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802 The mechanical properties of ceramic foams obtained through a novel process that uses the direct foaming and pyrolysis of preceramic polymer/polyurethane solutions were investigated. The elastic modulus, flexural strength, and compressive strengths were obtained for foams in the as-pyrolyzed condition; values up to 7.1 GPa, 13 MPa, and 11 MPa, respectively, were obtained. The strength of the foam was virtually unchanged at temperatures up to 1200C in air; however, long-term exposure at 1200C led to a moderate degradation in strength, which was attributed to the evolution of intrastrut porosity during the oxidation of residual free carbon, as well as devitrification of the foams struts. I. Introduction II. Experimental Procedure (1) Materials In this study, the typical polyurethane component in the preceramic polymer polyurethane (PU) foam was obtained from a mixture of two polyether polyols (Tercarol 3 (hydroxyl number of 56 mg KOH/g, viscosity of 500 mPas at 25C, molecular weight (MW) of 3000) and Tercarol 1 (hydroxyl number of 168 mg KOH/g, viscosity of 280 mPas at 25C, MW 1000), each supplied by EniChem, San Donato Milanese, Italy), amine catalysts (Niax A1 and Niax A-33), surfactants (polydimethyl siloxane copolymers SC250 and SH205, Goldschmidt Italia, Pandino (CR), Italy), a blowing agent (dichloromethane, CH2Cl2), and polymeric MDI isocyanate (Tedimon 31 (polyphenylmethane polyisocyanate), viscosity of 180 250 mPas at 25C, with 31% NCO; EniChem). This mixture, when used by itself, produces a semirigid PU foam. The preceramic polymer used in this study was a thermosetting methyl-hydroxyl-siloxane (SR350, General Electric, Silicone Products Division, Waterford, NY), which can cross-link at room temperature through the amine-catalyzed condensation of SiOOH groups. Its pyrolysis in an inert atmosphere yields a SixOyCz ceramic, with a weight loss of 16%.12 Silicon oxycarbide (SiOC) ceramics prepared from preceramic polymer routes are thermochemically stable, at least up to 1200C in air, and show compositional or microstructural modifications only after extended periods of time at elevated temperature.13 Although CH2Cl2 was chosen as the solvent, it also serves as a physical blowing agent for the PU system and is compatible with both the PU precursors and the preceramic polymer. After blowing, the PU is phase-separated as small islands (typically 510 m in size) embedded in a silicone resin matrix. During pyrolysis, the polyurethane decomposes (leaving a limited free-carbon residue11), and the preceramic polymer is converted to a ceramic material. (2) Preparation and Characterization of Foams A solution of SR350 polymer in dichloromethane was added to the polyol mixture (polyol amine catalysts surfactant) and 2245 fashion, including a wide range of nitrides, carbides, and oxides. Tailoring the pyrolysis conditions and the chemistry of the polyurethane backbone allows manipulation of the resulting stoichiometry, carbon content, interstrut and intrastrut porosity, and subsequent mechanical, elastic, and chemical characteristics of the foam.9 11 However, to date, little has been reported on the thermochemical and thermomechanical durability of silicon-oxycarbide-based foams that have been produced using the direct foaming process. The objective of this study was to examine the interdependence of foam structure, strength, elastic modulus, fracture toughness, and oxidation resistance at room temperature and after hightemperature oxidative exposure at 800 and 1200C.

ceramics possess properties that are of interest for several engineering applications. These properties include low bulk density, low net thermal conductivity, low dielectric constant, high specific strength and stiffness, excellent resistance to thermochemical corrosion, and excellent thermal shock resistance.1 4 The properties of ceramic foams are influenced by their relative density and morphology (open cell versus closed cell), as well as the properties of the struts that comprise the cell walls.1,2 Numerous methods for manufacturing cellular ceramics with open- and closed-cell morphologies have been developed over the last twenty years. Ceramic slurry deposition on sacrificial polymer foam preforms followed by sintering,5 direct foaming from polymeric precursors or ceramic sols,6,7 and chemical vapor deposition (CVD) of ceramics onto carbon foam preforms8 are among those methods that have been demonstrated for the manufacture of ceramic foams with requisite microstructures and macrostructures for good thermomechanical behavior. Recent results in our laboratories on the direct foaming of preceramic polymer/polyurethane solutions, followed by pyrolysis at elevated temperature in an inert gas ambient, have proven useful for fabricating silicon-oxycarbide-based foams to near-net shape, and with excellent room-temperature mechanical properties.9 The approach offers significant advantages over other ceramic foam fabrication techniques in that it is a simple, one-step process that allows the fabrication of foams to complex net shapes by casting into molds. Selection of the appropriate preceramic polymer (and fillers) offers the ability to fabricate a variety of ceramics in this
ELLULAR

R. Rajcontributing editor

Manuscript No. 187946. Received February 9, 2001; approved May 21, 2001. Invited paper for the 2nd International Workshop on Ultrahigh Temperature Polymer Derived Ceramics (Boulder, CO, July 2329, 2000). *Member, American Ceramic Society. Author to whom correspondence should be addressed.

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Journal of the American Ceramic SocietyColombo et al. Table I. Summary of Mechanical and Elastic Properties of Different Foams

Vol. 84, No. 10

Density (g/cm3)

F (MPa)

F (MPam3/mF)

mF

C (MPa)

C (MPam3/mC)

mC

Elastic modulus, E (GPa)

Fracture toughness, KIC (MPam1/2)

0.274 0.009 0.400 0.011 0.447 0.01 0.450 0.027 0.500 0.015 0.526 0.01 0.550 0.012 0.558 0.013 0.400 0.011 0.450 0.027 0.500 0.015 0.550 0.012 0.400 0.011 0.450 0.027 0.500 0.015 0.550 0.012 0.400 0.011 0.450 0.027 0.500 0.015 0.550 0.012 0.400 0.011 0.450 0.027 0.500 0.015 0.550 0.012

1.81 0.24 (5) 3.69 0.28 (9) 4.63 0.89 (5) 3.66 0.57 (10) 7.00 1.27 (10) 5.95 0.69 (6) 11.17 1.05 (10) 6.43 0.74 (8) 4.45 1.11 (10) 4.41 0.41 (6) 8.55 1.24 (9) 12.08 2.67 (8) 4.72 0.62 (5) 4.94 0.27 (5) 9.00 0.84 (5) 10.75 1.39 (7) 3.73 0.97 (5) 4.08 0.48 (5) 7.62 0.82 (5) 13.13 2.70 (5) 2.29 0.31 (5) 2.36 0.21 (5) 4.85 0.75 (5) 7.47 0.85 (5)

1.89 3.79 4.94 3.88 7.50 6.21 11.59 6.69 4.84 4.19 9.04 13.05 4.91 5.01 9.29 11.28 4.05 4.25 7.96 14.13 2.40 2.42 5.11 7.76

7.6 15.0 4.4 6.3 5.0 7.2 10.1 9.1 4.3 4.8 6.6 4.3 8.8 15.6 9.2 7.0 3.5 7.4 10.5 6.1 6.2 13.8 5.6 7.7

1.31 0.51 (9) 3.32 0.74 (10) 3.76 1.52 (9) 3.85 0.94 (10) 7.30 1.64 (10) 8.45 2.07 (10) 8.98 3.04 (10) 9.90 1.78 (9) 3.19 0.99 (5) 3.43 0.96 (5) 4.79 0.62 (5) 7.76 0.39 (5) 6.01 1.02 (5) 6.60 0.49 (5) 9.30 0.79 (5) 10.19 0.87 (5) 2.98 0.67 (5) 3.33 0.69 (5) 5.06 0.67 (5) 8.57 0.70 (5) 2.33 0.75 (5) 2.88 0.68 (5) 4.31 0.75 (5) 5.61 0.54 (5)
HT 1200C HT 800C 1200C 800C

Room temperature

1.46 3.60 4.23 4.20 7.92 9.25 10.60 9.97 3.50 3.74 5.02 7.87 6.34 6.75 9.56 10.48 3.21 3.65 5.30 8.82 2.57 3.11 4.50 5.80

2.7 4.4 2.8 3.6 4.4 3.7 4.6 3.0 2.9 3.1 5.7 19.6 6.1 13.6 10.3 10.4 3.9 3.7 6.7 8.8 2.8 3.7 6.5 8.1

1.60 0.30 (5) 3.54 0.50 (9) 4.30 0.50 (5) 4.94 0.70 (10) 5.57 0.13 (10) 5.24 0.27 (6) 7.40 0.37 (10) 6.05 0.48 (5) n/m n/m n/m n/m n/m n/m n/m n/m 3.29 0.20 (5) 3.53 0.35 (5) 5.02 0.28 (5) 7.08 0.29 (5) 2.28 0.30 (5) 2.66 0.27 (5) 3.56 0.31 (5) 4.95 0.38 (5)

n/m 0.16 0.01 (8) n/m 0.16 0.01 (5) 0.25 0.01 (5) n/m 0.24 0.07 (5) n/m n/m n/m n/m n/m n/m n/m n/m n/m n/m n/m n/m n/m n/m n/m n/m n/m

The value after the plus-or-minus sign () indicates the standard deviation; value within the parentheses is the reported number of specimens tested. Flexural and compressive characteristic strength (F and C, respectively) were determined by the maximum likelihood method, using WeibPar software.14 n/m not measured.

excess dichloromethane was evaporated. Then, a stoichiometric amount of isocyanate was added and the expansion reaction of the mixture was started by mechanical stirring. The final preceramicpolymer:polyurethane weight ratio in the foam was 1:1. Because of the presence of amine catalysts, a more-or-less complete crosslinking of the silicone resin occurs via a condensation of silanols and the release of water. The silicone resin was preconditioned by heating for various amounts of time at 100150C, to control the amount of SiOOH groups that are present, which affects the rising profile of the foams (chemical expansion). Different final foam densities (0.27 0.56 g/cm3) were obtained by varying the amount of dichloromethane and catalysts, the mold temperature (which was 1735C), and the polyether polyols ratio in the PU precursor mixture (which affects the viscosity and the rising characteristics). Foaming occurred within a very short time after stirring, and the foams were conditioned for 24 h at 30C before pyrolysis for 1 h at 1200C in a flux of nitrogen gas (99.99% pure, with a heating rate of 2C/min). The foam morphology was characterized using scanning electron microscopy (SEM) (Cambridge Instruments, Cambridge, U.K.), and the geometrical features were derived using image analysis software (Image-Pro Plus, Media Cybernetics, Silver Spring, MD). The bulk (apparent) density of the foams was computed from the weight:volume ratio; the true density was measured on powdered samples using a helium pycnometer. The crystalline phase assemblage was characterized by X-ray diffractometry (XRD) (Model 1730/1820, Philips Research Laboratories, Eindhoven, The Netherlands), using CuK radiation (40 kV, 40 mA). The coefficient of thermal expansion (CTE) was measured using a dilatometer (Model 402E, Netzsch, Selb, Germany) in flowing nitrogen gas or in air, at a heating rate of 10C/min. Simultaneous differential thermal analysis and thermogravimetry (DTA/TGA) were performed using a thermobalance (Model STA409, Netzsch) in different atmospheres (air or nitrogen, at a heating rate of 10C/min).

The mechanical and elastic behavior was investigated in air on samples in the as-pyrolyzed condition at room temperature (samples labeled RT), 800C (samples labeled 800C), and 1200C (samples labeled 1200C), as well as after a long-term oxidation treatment (12 h at 800C (samples labeled HT 800C) or 12 h at 1200C (samples labeled HT 1200C) in static air), to assess the effect of exposure to aggressive environments on the foams. The mechanical property test specimens were sectioned from panels (dimensions of 20 cm 14 cm 2 cm) that were obtained by casting the solution into a closed aluminum mold. The specimens were cut before pyrolysis to avoid shape distortions that sometimes occur during the pyrolysis of a large panel. The flexural strength was measured by four-point bending (inner span of 10 mm, outer span of 20 mm) on specimens with dimensions of 45 mm 6 mm 6 mm, using a universal testing machine (Model 4202, Instron, Danvers, MA) with a cross-head speed of 0.5 mm/min. The crushing strength was measured by compression testing, using alumina loading rams and a cross-head speed of 0.5 mm/min, on samples with a nominal size of 6 mm 6 mm 12 mm. Strength data were analyzed using two-parameter Weibull statistics, with a maximum likelihood approach to estimating the characteristic strength and Weibull modulus.14 The fracture toughness was measured using the single-edgenotched-beam method in three-point bending (span of 30 mm), with a notch depth that was 50% of the specimen thickness. The elastic modulus was measured at room temperature in air, using ultrasonic sound velocity and acoustic resonance methods.15 III. Results and Discussion

(1) Physical and Morphological Characterization To produce a sufficient number of specimens for testing, different panels of the same nominal density were fabricated. Weight loss during pyrolysis in nitrogen was 55%, which indicated that residual carbon that was derived from the decomposition of the PU backbone is retained in the foams (the ceramic

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yield for pure SR350 polymer is 84% at 1200C), in agreement with prior work.11 Carbon analyses, which were performed using a carbon determinator (Model CS-244, LECO, St. Joseph, MI) with an oxidation accelerator, confirmed that the SiOC foam contained more carbon (29.6 0.9 wt%) than the SiOC ceramic obtained from the direct pyrolysis of the SR350 silicone resin (14.1 0.7 wt%.) The variability in density of the pyrolyzed samples was small (based on 50 samples per unit of density, a standard deviation of 2.5% was observed), which indicated that the sample fabrication process is quite reproducible. The measured densities are given in Table I. The typical cell morphology, as a function of density, is illustrated in Fig. 1. The average cell size varies linearly with the foam density, from 100 40 m for the 0.55 g/cm3 samples to 600 145 m for the 0.27 g/cm3 samples. The cells are regularly shaped, with no evidence of preferential orientation, and seem to have interconnected pores; i.e., the foams can be considered to be predominantly open-celled. Some closed cells are present (10% 20%), and the number of closed cells increases as the foam density increases. The cell walls and the struts are mostly dense, with only occasional closed porosity present. No macroscopic cracks or defects are observed in the ceramic foams after pyrolysis. The CTE of the ceramic foams (at 201200C) is 3.50 106 0.19 106 K1. All the SiOC foams that have been pyrolyzed at 1200C are X-ray amorphous.

(2) Mechanical Properties The flexural and compressive strengths (F and C, respectively) for the samples, as a function of temperature, as well as after long-term oxidative exposure, are given in Table I. The room-temperature compressive and flexural strengths, as a function of bulk density, are presented in Weibull fashion in Fig. 2. Although at least thirty samples are needed to determine accurate Weibull parameters, we were limited in the number of samples available for this study. As such, the Weibull data listed in this study were obtained solely to compare sample behavior and is not intended to represent true material parameters. In agreement with prior studies,1,2,16 the strengths increase as the bulk density increases. Figure 3 presents the flexural and compression relative-strength data, as a function of the relative density, and is compared with the behavior that is expected for completely open-cell or closed-cell foams, according to models proposed by Ashby,1 Gibson and Ashby,2 and Brezny and Green.16 We used the pycnometrically determined value of 2.12 g/cm3 for the density, 97.9 GPa for the Youngs modulus (E), and 153 MPa for the modulus of rupture (MOR) as reference values for the SiOC strut and cell-wall material.12 Ashbys theory1,2 indicates that the relative strength of a cellular material is related to its relative density via the expression C s s

Fig. 1.

Morphologic characteristics of the foams produced in this study (densities of (a) 0.40, (b) 0.45, (c) 0.50, and (d) 0.55 g/cm3).

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Journal of the American Ceramic SocietyColombo et al.

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Fig. 2.

Strength distributions as a function of foam density for samples measured in (a) flexure and (b) compression. F is the failure probability.

where C is a dimensionless constant and the exponent m is 32 or 2, depending on if the cell morphology is open cell or closed cell, respectively. Similarly, the relative elastic modulus is related to relative density as E C Es s

where n 2 for open-cell foams or n 3 for closed-cell foams. A linear-regression fit of the room-temperature strengths yields exponents of 2.3 and 3.6 for the bending strength and compression strength (with correlation coefficients of R 0.92 and 0.97), respectively. Similarly, a plot of relative elastic modulus versus relative density for the as-pyrolyzed specimens at room temperature yields a relative density exponent of 1.83, with R 0.97. In

Fig. 3. Comparison of room-temperature flexural and compressive relative-strength data for behavior expected for open-cell versus closed-cell foams (after Ashby,1 Gibson and Ashby,2 and Brezny and Green16).

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Ashbys model,1,2 the morphology of the open-cell foams consists of interconnected ligaments (struts), and the cells do not have any cell walls (thus, the structure is totally open); such a morphology is generally obtained in ceramic foams that are produced using the replica method (so-called reticulated foams). In contrast, in the same model, the morphology of closed-cell foams consists of cells in which the cell walls are completely retained and do not contain any openings (cell windows). In our case, the morphology of the foams obtained from the direct foaming method, as shown in Fig. 1, is much more similar to a closed foam, in that the cell walls are largely retained. However, the foams can be considered to have an interconnected porosity (and, thus, can still be considered to be open cell), because some openings (cell windows) are present in most of the cell walls. Thus, it is reasonable that the strength data for our samples are more descriptive to what the model predicts for closed-cell foams. The lack of a rigorous fit to Ashbys theory1,2 may be due to several factors, such as the presence of macrostructural inhomogeneities (a distribution of cell sizes), the presence of mixed closed and open cells, the volume fraction of solids in the cell faces (hybrid cell wallsi.e., those containing some openings certainly contribute to a different stress distribution than if the foam has a completely open-cell or closed-cell structure), the presence of closed voids or defects in the struts, or variations in the (strut) strength or strut microstructure, relative to the density.16 For example, the unexpectedly low flexural strength that has been recorded for some specimens with high density (0.558 g/cm3) can be attributed to the presence of an abnormally large amount of voids or microdefects in the struts, which are derived from the decomposition of the PU component in the foam. This observation, in turn, is due to a change in the type and ratio of polyols (and,

thus, compatibility with the silicone resin) in the PU mixture, to vary the rheological and rising characteristics of the starting solution. The high-temperature flexural and compressive strengths of the materials in the as-pyrolyzed condition and after oxidative exposure for 12 h at 800 and 1200C are shown in Fig. 4. (To improve the readability, the data relative to the foam with a density of 0.274 g/cm3 have been omitted in the figure. They are reported in Table I.) The trend of increasing strength with increasing bulk density is maintained at high temperature, in both the as-pyrolyzed and oxidized specimens. No significant modification in strength is observed, relative to the room-temperature, as-pyrolyzed strengths for samples tested at 800 and 1200C. The higher strength that is exhibited in compression by the foams when tested at 1200C might be attributed to viscoelastic deformation phenomena that possibly occur in the material. Oxidative exposure at 800C yields no strength modification; however, the 1200C oxidized specimens do experience a reduction of 30% in both F and C, as well as in E (see Table I). The mechanical properties of the foams produced with this method are superior to those reported in the literature for porous ceramics of similar density that have been produced using conventional technology (e.g., reticulated foams17). This result may be due to the lack of macroscopic defects in the struts and cell walls, such as the hollow features that are typical of conventionally manufactured reticulated foams.4 In fact, materials that have been obtained by gelcasting also display better mechanical properties, because of the dense structure of the ceramic struts.18 TGA studies (Fig. 5) suggest that the strength degradation during long-term oxidative exposure at 1200C may be attributed to the loss of carbon from the struts and cell walls of the foams.

Fig. 4. (a) Flexural strength and (b) compression strength of SiOC foams, measured at various temperatures and after oxidation treatments, as a function of bulk density.

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Fig. 5. Weight loss of a SiOC foam pyrolyzed sample, as a function of heating temperature or heating time (at 800 and 1200C). Analysis was performed in nitrogen and air.

The nitrogen TGA results in Fig. 5(a) reveal that the polymer-toceramic conversion was completed with the processing schedule that was adopted for the pyrolyzed specimens; in fact, the weight loss in nitrogen was 1% for all temperatures and times investigated. TGA performed in air showed a weight loss of 1.5 wt% during the reheating of pyrolyzed specimens in the temperature interval of 600 800C, which is linked to the burnoff of some of the residual free carbon, in agreement with earlier work.19 However, the weight loss at 800C occurs quickly and then ends (Fig. 5(b)) with no further change in weight up to times of 12 h. In contrast, a significantly larger weight loss (2.6%) is observed for samples that have been exposed to 1200C in air, with a noticeable reduction in weight loss rate at long times, possibly because of the competition between CO2 evolution and the formation of a passivating silica scale on the foam struts (CO2 evolution has been observed when Fourier transform infrared (FTIR) analysis was performed on the gas that was released during an oxidation test19). Carbon analysis has indicated carbon contents of 29.2 0.5 and 24.7 0.6 wt%, after the 800 and 1200C treatments, respectively. Compared with the starting carbon content of 29.6 0.9 wt% in the as-pyrolyzed specimens, it is apparent that the residual free carbon is consumed more aggressively at 1200C than at 800C, at least for oxidation times of up to 12 h. SEM fractographic analysis of the foams has revealed an increase in the strut porosity in oxidized specimens (Fig. 6(a)(c)), because of the burnout of PU-derived carbon-rich islands. Moreover, the formation of cracks in the struts is observed for samples that have been oxidized at 1200C; this phenomenon is possibly due to either the evolution and release of CO2 during oxidation or fracture of the silica scale during rapid cooling from the oxidation temperatures. Powder XRD revealed that the samples oxidized at 800C remained X-ray amorphous; however, the foams began to devitrify during oxidation at 1200C. Minor quantities of cristobalite formed in SiOC foams that were oxidized for long times at 1200C. Notably, the same treatment that was performed on a bulk SiOC ceramic that was obtained from the direct pyrolysis of SR350 silicone resin did not produce the same change in crystalline-phase assemblage; i.e., the specimen remained amorphous.19 The difference in devitrification behavior between bulk SiOC and the foams may possibly be attributed to the oxidation of residual carbon that remained from the PU precursor, which yields heterogeneous nucleation sites for the crystallization of silica. A possible solution to the observed limited stability of the SiOC ceramic foams when exposed to an oxidative environment at high temperature would be the use of a smaller amount of PU precursors when fabricating the material. This practice, in fact, has been recently demonstrated,19 wherein foams that were prepared with only 30% of the amount of PU used in these experiments showed no decrease in strength after exposure in air at 1200C for 12 h.

Fig. 6. SEM micrographs of (a) the strut microstructure in the aspyrolyzed foam, (b) the strut after oxidation at 800C, and (c) the strut after oxidation at 1200C. Foam density was 0.5 g/cm3.

IV.

Summary

In summary, we have demonstrated a novel process for the near-net-shape fabrication of silicon oxycarbide (SiOC) cellular ceramics via the direct foaming and pyrolysis of preceramic polymer/polyurethane solutions. The approach offers substantial flexibility in producing foams with controlled cell size and morphology, bulk density, and residual carbon content. The strength of the foams produced in this manner is superior to that of most foams produced commercially and is virtually unaffected by short-term high-temperature exposure in air. Modifications in strength are observed only after long-term exposure at 1200C in

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air. The modification in strength is attributed to the evolution of intrastrut porosity that is due to oxidation of residual free carbon, accompanied by devitrification of the SiOC and/or the passivating silica scale that forms during oxidation.

Acknowledgments
The authors wish to thank Dr. M. Modesti (University of Padova, Italy) for formulating and tailoring the composition of the polyurethane mixture used in this study, and Mr. N. Phelps for the help in the characterization of the specimens. They are also indebted to Prof. D. Green (Pennsylvania State University) for the numerous helpful discussions.

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