Search NASA⌕ Search

Engineering topics

Hurwitz, F. I.

Publications and source records attributed to Hurwitz, F. I..

At least 19 records

Tailoring Silicon Oxycarbide Glasses for Oxidative Stability

Blackglas(Trademark) polysiloxane systems produce silicon oxycarbide glasses by pyrolysis in inert atmosphere. The silicon oxycarbides evidence oxidative degradation that limits their lifetime as composite matrices. The present study characterizes bonding rearrangements in the oxycarbide network accompanying increases in pyrolysis temperature. It also addresses the changes in susceptibility to oxidation due to variations in the distribution of Si bonded species obtained under different processing conditions. The study is carried out using Si-29 nuclear magnetic resonance (NMR) spectroscopy and a design of experiments approach to model the oxidation behavior. The NMR results are compared with those obtained by thermogravimetric analysis (TGA). Samples pyrolyzed under inert conditions are compared to those pyrolyzed in reactive ammonia environments.

Hurwitz, F. I.↗

Preceramic Polymers for Use as Fiber Coatings

Polymeric precursors to Si-C-O, SI-B-N and Si-C were evaluated for use as ceramic interfaces in ceramic matrix composites. Use of the preceramic polymers allows for easy dip coating of fibers from dilute solutions of a polymer, which are then pyrolyzed to obtain the ceramic. SCS-0 fibers (Textron Specialty Materials, Lowell, MA) were coated with polymers from three systems: polysilsesquioxanes, polyborosilazanes and polycarbosilanes. The polysilsesquioxane systems were shown to produce either silicon oxycarbide or silicon oxynitride, depending on the pyrolysis conditions, and demonstrated some promise in an RBSN (reaction-bonded silicon nitride) matrix model system. Polyborosilazanes were shown, in studies of bulk polymers, to give rise to oxidation resistant Si-B-N ceramics which remain amorphous to temperatures of 1600 C, and should therefore provide a low modulus interface. Polycarbosilanes produce amorphous carbon-rich Si-C materials which have demonstrated oxidation resistance.

Heimann, P. J.↗

Silsesquioxane-derived ceramic fibres

Fibers formed from blends of silsesquioxane polymers were characterized to study the pyrolytic conversion of these precursors to ceramics. The morphology of fibers pyrolyzed to 1400 C revealed primarily amorphous glasses whose conversion to beta-SiC is a function of both blend composition and pyrolysis conditions. Formation of beta-SiC crystallites within the glassy phase is favored by higher than stoichiometric C/Si ratios, while carbothermal reduction of Si-O bonds to form SiC with loss of SiO and CO occurs at higher methyl/phenylpropyl silsesquioxane (lower C/Si) ratios. As the carbothermal reduction is assumed to be diffusion controlled, the fibers can serve as model systems to gain understanding of the silsesquioxane pyrolysis behavior, and therefore are useful in the development of polysilsesquioxane-derived ceramic matrices and coatings as well.

Hurwitz, F. I.↗

Nicalon/siliconoxycarbide ceramic composites

A number of polymers of differing molecular structure, viscosity, copolymer composition, and production procedures, screened for production of strong, tough Nicalon/siliconoxycarbide composites, are discussed. Variables during polymer synthesis include pH, water/methoxy ratio and phenyl/methyl ratio. Final processing temperatures of the composites range from 1200 deg to 1400 deg C. The filler is derived from pyrolysis of the 50 phenyl/50 methyl silsesquioxane copolymer pyrolyzed to 650 deg C, then milled to less than 1-micron powder. Composite samples were fractured to evaluate the influence of matrix composition, final fabrication temperature, and use of filler on the composite mode of failure, modulus, strain capability, and strength. Incorporation of filler was found to increase matrix compressive strength and to influence matrix shrinkage and cracking.

Hurwitz, F. I.↗

Silsesquioxanes as precursors to ceramic composites

Silsesquioxanes having the general structure RSiO(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 source 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, F. I.↗

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 uniaxial composites are tested in tension. Failure of both uniaixial 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, F. I.↗

Carbon-rich ceramic composites from ethynyl aromatic precrusors

A number of polyfunctional aromatic acetylenes thermally polymerize at low temperatures (180 C) and pyrolyze with greater than 90 char yield. In nonoxidizing environments, they are thermally stable to 1450 C. These monomers were chosen as the basis of a model system to study the fabrication and mechanical properties of continuous filament ceramic matrix composite. Composites were fabricated from aryl poly(acetylenes), SiC particulate filler and graphite, Avco SiC, Nicalon and Nextel fibers. Microstructure, physical and mechanical properties are reported.

Hurwitz, F. I.↗

A ceramic matrix composite based on polymerization and pyrolysis of ethynylated aromatics

A number of ethynylated aromatic monomers recently have been synthesized which thermally homopolymerize and copolymerize to produce rigid, highly cross-linked polymers with high thermal stability (Tg of about 450 C). On pyrolysis, these polymers lose few volatiles (more than 85 percent char yield) to yield carbon bodies of relatively low porosity. These properties render the ethynylated aromatics of significant interest as matrices for high temperature composites. Incorporation of a SiC particle filler in the matrix improves the rheology of the system and minimizes shrinkage during pyrolysis. Several unidirectional composites have been fabricated combining a graphite or boria-alumina-silica continuous reinforcement with an ethynylated aromatic polymer matrix and SiC filler. Thermogravimetric analysis of composite pyrolysis behavior was used to determine reaction kinetics and to establish a composite fabrication cycle. Composites retained 95 percent of their green weight on pyrolysis. Microstructure of the green and pyrolyzed composites is characterized for materials pyrolyzed at 600 C in vacuum and argon as well as for laminates heated at 1200 C in argon following pyrolysis.

Hurwitz, F. I.↗

Off-axis tensile properties and fracture in a unidirectional graphite/polyimide composite (Celion 6000/PMR 15)

Tensile properties of unidirectional Celion 6000 graphite/PMR 15 polyimide composites prepared by hot molding and cold molding processes were measured at room temperature and 316 C, the upper use temperature of the polyimide resin, at both 45 and 90 deg to the fiber axis. The resulting fractures were characterized by scanning electron microscopy and materialographic techniques. Variation in tensile properties with processing history occurred in the elastic modulus and strain to failure for specimens loaded at 90 deg at 316 C, and in the fracture stress, and hence the in-plane shear stress, for those loaded at 45 deg at room temperature. Significant plastic deformation was observed in the 45 deg orientation at 316 C for material produced by both processing methods. In general, fracture occurred by both failure within the matrix and at the fiber-matrix interface; the degree of interfacial failure increased with temperature. Secondary cracking below the primary fracture surface was also observed.

Harper, J.↗

Method and apparatus for gripping uniaxial fibrous composite materials

A strip specimen is cut from a unidirectional strong, brittle fiber composite material, and the surfaces of both ends of the specimen are grit blasted. The specimen is then placed between metal load transfer members having grit blasted surfaces. Sufficient compressive stress is applied to the load transfer members to prevent slippage during testing at both elevated temperatures and room temperatures. The need for adhesives, load pads, and other secondary composite processing is eliminated. This gripping system was successful in tensile testing, creep rupture testing, and fatigue testing uniaxial composite materials at 316 C.

Whittenberger, J. D.↗

Application of Iosipescu specimen geometry to determination of shear strength in unidirectional composites

The Iosipescu (1967) test method, in conjunction with a finite element analysis of anisotropic, unidirectionally reinforced composite specimens, can be used to derive composite shear strength values despite the small size of the samples used. When such a specimen is loaded parallel to the fiber direction, fracture occurs by shear within a narrow region near the center of the specimen; this is consistent with the maximum shear area determined by finite element analysis. The resulting fracture surface, as observed, is characteristic of shear failure, occurring either within the matrix or at the fiber-matrix interface. Problems of compressive and mixed mode failure which accrue to short beam shear specimens are by the present method precluded.

Hurwitz, F. I.↗

Dynamic mechanical characterization of cure of a polyimide-graphite fiber composite (PMR 15/Celion 6000)

Dynamic mechanical studies of thermosetting PMR 15 polyimide/Celion 6000 composites were used to characterize cure behavior. Variation in composite shear modulus with cure time for laminates partially cured under 3.45 MPa pressure was compared with that of laminates fully cured under pressure to select a partially cured system whose behavior corresponded with that of the pressure-cured composites. An empirical kinetic model was developed that relates relative composite shear moduli to cure time and temperature. This model, coupled with standard statistical techniques, was used in the determination of an overall activation energy, E = 145 kj/mole (35 kcal/mole) and order of reaction, n, for the cure reaction(s). The empirical relationship defining dynamic modulus as a function of time and temperature remained linear well into the glassy region. Changes in dynamic glass-transition temperature and in the breadth of the transition peaks with cure time are discussed. Shear modulus and damping were found to be more sensitive measures of relative extent of cure than Fourier transform infrared spectroscopy.

Hurwitz, F. I.↗

The effect of a coating on the thermo-oxidative stability of Celion 6000 graphite fiber/PMR 15 polyimide composites

The thermooxidative stability in air at 316 C of unidirectional, uncoated and aluminum-coated Celion 6000 graphite fiber/PMR 15 polyimide composites has been determined for exposure times up to nominally 2000 h. Comparison of the weight loss data and microstructural integrity reveals that a thin aluminum-foil coating can provide significant protection from oxidation. A quantitative description of the average depth of the reaction zone and the maximum length of cracks produced during oxidation as a function of time in uncoated Celion 6000/PMR 15 are given.

Hurwitz, F. I.↗

Forced torsional properties of PMR composites with varying nadic ester concentrations and processing histories

PMR polyimide resin was prepared from 4,4'-methylenedianiline, the dimethyl ester of 3,3',4,4'-benzophenonetetracarboxylic acid and the monomethyl ester of 5-norbornene-2,3-dicarboxylic acid (NE). The NE group serves as a chain terminator and crosslinking site. PMR/Celion 6000 composites were fabricated from resins having varying NE concentrations using two molding processes, and the laminates characterized in forced torsion. Glass transition temperatures (T(g)) of 360-390 C were observed in the crosslinked resins, as compared with the literature value of 284 C reported for the uncrosslinked system. T(g) did not decrease with decreasing NE concentrations over the range from 2.0 to 1.25 moles. Stoichiometry, within the range studied, showed little influence on shear properties; however, a 25% variation in matrix shear modulus with processing was observed. The G(12) values determined in forced torsion were in excellent agreement with those reported from tensile tests of + or - 45 deg laminates. A branching and possible secondary crosslink mechanism is proposed based on dynamic mechanical behavior and infrared spectra of the composites.

Hurwitz, F. I.↗

On determination of fibre fraction in continuous fibre composite materials

It is pointed out that the fiber volume fraction is probably the most important parameter influencing the properties of fibrous composite materials. The present investigation is concerned with questions regarding the accurate determination of this parameter. It is found that an estimate of the fiber volume fraction based on determinations from several coupons taken from different regions of a laminate is not accurate. At present fiber volume fractions are not directly measured but rather are calculated from the fiber weight fraction and densities of the composite and fiber. Image analysis techniques can and should be applied to determine fiber volume fraction. However, several factors have to be considered in this connection. It is necessary to make many measurements of the local fiber area fractions, and the preparation of representative planar cross sections parallel to the fiber axis may be difficult.

Whittenberger, J. D.↗

Application of a gripping system to test a uniaxial graphite fiber reinforced composite /PMR 15/Celion 6000/ in tension at 316 C

A gripping system has been developed to test uniaxial, 0 deg orientation PMR 15/Celion 6000 composites at elevated temperatures. The method involves compression of grit-blasted laminate between grit-blasted metal to give a non-slipping interface for load transfer. Tensile testing at both 316 C and room temperature indicated that deformation was elastic to fracture and that the variation in tensile properties for one laminate is the same as that for several panels. In addition, the tensile properties for uniaxial PMR 15/Celion 6000 are identical at 316 C and room temperature. For nominally 51 volume percent fiber, the elastic modulus is 119.6 GPa, the fracture stress is 1370 MPa, and the strain to fracture is about 1.15 percent. In addition, data are presented which indicate that the gripping system can be used for long term, elevated temperature testing of composite materials.

Whittenberger, J. D.↗

Influence of excess diamine on properties of PMR polyimide resins and composites

By varying the stoichiometry of the reactants in the preparation of PMR polyimide resin, changes occur in molecular weight distribution which influence the rheological properties and thus the processability of the resin, as well as the mechanical properties of the composite. The influence of 1-10 percent molar excess MDA on the molecular weight distribution and rheological properties of an imidized PMR system were exposed. Molecular weight distribution is characterized by gel permeation chromatography of the imidized molding compound; shear viscosity is related to changes in average molecular weight. The thermo-oxidative stability at 600 F, glass transition temperature, flexural and interlaminar shear properties of PMR polyimide/Celion 6000 graphite fiber composites are compared as a function of the percent excess MDA in the monomer reactant mixture.

Hurwitz, F. I.↗