Hurwitz, Frances I. — Page 2 | Engineering Papers

NASA NTRS1993

Syntheses, structures and properties of polycarbosilanes formed directly by polymerization of Alkenylsilanes

Vinylsilane polymerizes to form predominantly a carbosilane polymer using dimethyltitanocene catalyst. This is in contrast to alkylsilanes, which afford polysilanes under the same conditions. The mechanism of polymerization of alkenylsilanes has been shown to be fundamentally different from that for the polymerization of alkylsilanes. The silyl substitute apparently activates a double bond to participate in a number of polymerization processes in this system, particularly hydrosilation. Isotopic labeling indicates the involvement of silametallocyclic intermediates, accompanied by extensive nuclear rearrangement. Polymers and copolymers derived from alkenylsilanes have relatively high char yields even for conditions which afford low molecular weight distributions. Formation of crystalline beta-SiC is optimum for a copolymer of an alkylsilane and an alkenylsilane having a silane/carbosilane backbone ratio of 85/15 and a C/Si ratio of 1.3/1.

Masnovi, John↗

NASA NTRS1992

Approaches to polymer-derived CMC matrices

The use of polymeric precursors to ceramics permits the fabrication of large, complex-shaped ceramic matrix composites (CMC's) at temperatures which do not degrade the fiber. Processing equipment and techniques readily available in the resin matrix composite industry can be adapted for CMC fabrication using this approach. Criteria which influence the choice of candidate precursor polymers, the use of fillers, and the role of fiber architecture and ply layup are discussed. Three polymer systems, polycarbosilanes, polysilazanes, and polysilsesquioxanes, are compared as candidate ceramic matrix precursors.

Hurwitz, Frances I.↗

NASA NTRS1992

Polymeric precursors for fibers and matrices

Candidate polymeric precursors for ceramic fiber and matrix processing are discussed, with a view to the advantages and disadvantages of this approach relative to existing alternatives. The properties of ceramic products thus derived are noted to strongly depend on the molecular weight and structure of the starting polymer; in particular, the ceramic's composition and morphology are dependent on the character and extent of crosslinking, as well as on the path of pyrolysis. While large and complex structural ceramic components may ultimately be obtainable by these means, the polymer-precursor method is still in its developmental infancy.

Hurwitz, Frances I.↗

NASA NTRS1992

Approaches to polymer-derived CMC matrices

The use of polymeric precursors to ceramics permits the fabrication of large, complex-shaped ceramic matrix composites (CMC's) at temperatures which do not degrade the fiber. Processing equipment and techniques readily available in the resin matrix composite industry can be adapted for CMC fabrication using this approach. Criteria which influence the choice of candidate precursor polymers, the use of fillers, and the role of fiber architecture and ply layup are discussed. Three polymer systems, polycarbosilanes, polysilazanes, and polysilsesquioxanes, are compared as candidate ceramic matrix precursors.

Hurwitz, Frances I.↗

NASA NTRS1991

Polymeric routes to silicon carbide and silicon oxycarbide CMC

An overview of two approaches to the formation of ceramic composite matrices from polymeric precursors is presented. Copolymerization of alkyl- and alkenylsilanes (RSiH3) represents a new precursor system for the production of Beta-SiC on pyrolysis, with copolymer composition controlling polymer structure, char yield, and ceramic stoichiometry and morphology. Polysilsesquioxanes which are synthesized readily and can be handled in air serve as precursors to Si-C-O ceramics. Copolymers of phenyl and methyl silsesquioxanes display rheological properties favorable for composite fabrication; these can be tailored by control of pH, water/methoxy ratio and copolymer composition. Composites obtained from these utilize a carbon coated, eight harness satin weave Nicalon cloth reinforcement. The material exhibits nonlinear stress-strain behavior in tension.

Hurwitz, Frances I.↗

NASA NTRS1991

Polymeric routes to silicon carbide and silicon oxycarbide CMC

An overview of two approaches to the formation of ceramic composite matrices from polymeric precursors is presented. Copolymerization of alkyl- and alkenylsilanes (RSiH3) represents a new precursor system for the production of Beta-SiC on pyrolysis, with copolymer composition controlling polymer structure, char yield, and ceramic stoichiometry and morphology. Polysilsesquioxanes which are synthesized readily and can be handled in air serve as precursors to Si-C-O ceramics. Copolymers of phenyl and methyl silsesquioxanes display rheological properties favorable for composite fabrication; these can be tailored by control of pH, water/methoxy ratio and copolymer composition. Composites obtained from these utilize a carbon coated, eight harness satin weave Nicalon cloth reinforcement. The material exhibits nonlinear stress-strain behavior in tension.

Hurwitz, Frances I.↗

NASA NTRS1990

Nicalon/siliconoxycarbide ceramic composites

A series of silsesquioxane copolymers was synthesized by acid hydrolysis and condensation of trimethoxysilanes of the form RSi(OCH3)3, where R = methyl or phenyl. By varying pH, water/methoxy and methyl/phenyl ratios, the molecular structure, polymer rheology and ceramic composition can be controlled. The polymers form an amorphous siliconoxycarbide on pyrolysis. Composites of Nicalon/siliconoxycarbide were fractured in four-point flexure and in tension to evaluate the influence of matrix composition, final fabrication temperature and use of filler on composite mode of failure, modulus, strain capability and strength. Incorporation of filler was found to increase matrix compressive strength. Employment of processing temperatures of 1375 to 1400 C enhanced strain to failure and reduced the tendency toward brittle fracture. Mixed mode (compression/shear and tension/shear) failures were observed in flexural samples processed to the higher temperatures, giving rise to nonlinear stress-strain curves. Tensile samples pyrolyzed to 1400 C showed linear-elastic behavior and failed by fracture of fiber bundles. Matrix material was found to be adherent to the fiber surface after failure. These results demonstrate the need for tensile testing to establish composite behavior.

Hurwitz, Frances I.↗

NASA NTRS1989

Polymer derived Nicalon/Si-C-O composites - Processing and mechanical behavior

Ceramic matrix composites fabricated using Nicalon fiber and several polysilsesquioxane-derived Si-C-O matrices were characterized by optical and SEM and in four-point bending. In the matrix material linear shrinkages of up to 19 percent were observed for the vinylmethyl copolymer pyrolyzed to 1200 C, and up to 13 percent for the phenylmethyl material pyrolyzed to the same temperature, resulting in considerable matrix cracking. Under four-point loading, most composite samples fractured in a brittle manner as the result of strong fiber-matrix bonding. Flexural strengths, moduli, and ultimate strain varied with fiber sizing and processing parameters. Testing and analysis is being applied to promote more fibrous pullout during fracture.

Hurwitz, Frances I.↗

NASA NTRS1988

Fibers And Composites Derived From Silsesquioxanes

In new method, silsesquioxane powders blended to control ratio of carbon to silicon. Powders melted, and excess silanol groups condense with evolution of water. When melt attains suitable viscosity, extruded into fibers through die or drawn into fibers from melt at uniform rate. Fibers cured and heat treated. Enables easy fabrication of thermally stable fibers from inexpensive silsesquioxane precursors. Impregnation of fibers and preforms without solvent minimizes both shrinkage and formation of voids resulting from volatilization of trapped solvent.

Hurwitz, Frances I.↗

NASA NTRS1987

Ceramic matrix and resin matrix composites: A comparison

The underlying theory of continuous fiber reinforcement of ceramic matrix and resin matrix composites, their fabrication, microstructure, physical and mechanical properties are contrasted. The growing use of organometallic polymers as precursors to ceramic matrices is discussed as a means of providing low temperature processing capability without the fiber degradation encountered with more conventional ceramic processing techniques. Examples of ceramic matrix composites derived from particulate-filled, high char yield polymers and silsesquioxane precursors are provided.

Hurwitz, Frances I.↗

NASA NTRS1987

Silsesquioxanes as precursors to ceramic composites

Silsesquioxanes having the general structure RSiO sub 1.5, where R = methyl, propyl, or phenyl, melt flow at 70 to 100 C. Above 100 C, free -OH groups condense. At 225 C further crosslinking occurs, and the materials form thermosets. Pyrolysis, with accompanying loss of volatiles, takes place at nominally 525 C. At higher temperatures, the R group serves as an internal carbon soruce for carbo-thermal reduction to SiC accompanied by the evolution of CO. By blending silsesquioxanes with varying R groups, both the melt rheology and composition of the fired ceramic can be controlled. Fibers can be spun from the melt which are stable in argon in 1400 C. The silsesquioxanes also were used as matrix precursors for Nicalon and alpha-SiC platelet reinforced composites.

Hurwitz, Frances I.↗

NASA NTRS1987

Ceramic matrix and resin matrix composites - A comparison

The underlying theory of continuous fiber reinforcement of ceramic matrix and resin matrix composites, their fabrication, microstructure, physical and mechanical properties are contrasted. The growing use of organometallic polymers as precursors to ceramic matrices is discussed as a means of providing low temperature processing capability without the fiber degradation encountered with more conventional ceramic processing techniques. Examples of ceramic matrix composites derived from particulate-filled, high char yield polymers and silsesquioxane precursors are provided.

Hurwitz, Frances I.↗

NASA NTRS1986

Ethynylated aromatics as high temperature matrix resins

Difunctional and trifunctional arylacetylenes were used as monomers to form thermoset matrix resin composites. Composites can be hot pressed at 180 C to react 80 percent of the acetylene groups. Crosslinking is completed by postcuring at 350 C. The postcured resins are thermally stable to nominally 460 C in air. As a result of their high crosslink density, the matrix exhibits brittle failure when unaxial composites are tested in tension. Failure of both uniaxial tensile and flexural specimens occurs in shear at the fiber matrix interface. Tensile fracture stresses for 0 deg composites fabricated with 60 v/o Celion 6K graphite fiber were 827 MPa. The strain to failure was 0.5 percent. Composites fabricated with 8 harness satin Celion cloth (Fiberite 1133) and tested in tension also failed in shear at tensile stresses of 413 MPa.

Hurwitz, Frances I.↗

NASA NTRS1986

Polymer precursors for ceramic composites

The fiber composite approach to reinforced ceramics provides the possibility of achieving ceramics with high fracture toughness relative to monolithics. Fabrication of ceramic composites, however, demands low processing temperatures to avoid fiber degradation. Formation of complex shapes further requires small diameter fibers as well as techniques for infiltrating the matrix between fibers. Polymers offer low temperature processability, control of rheology not available with ceramic powders, and should serve as precursors to matrix fibers. In recent years, a number of polysilanes and polysilezanes were investigated as potential presursors. A review of candidate polymers is presented, including recent studies of silsesquioxanes.

Hurwitz, Frances I.↗