Polymer Composites

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.

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.

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.

A perfluorinated alkyl ether diacyl fluoride prepolymer (molecular weight about 1500) was coreacted with Epon 828 epoxy resin and diamino diphenyl sulfone to obtain an elastomer-toughened, glass-cloth composite. Improvements in flexural toughness, impact resistance, and water resistance, without loss of strength, modulus of elasticity or a lowering of the glass-transition temperature, were realized over those of the unmodified composite. Factors concerning optimization of the process are discussed. Results suggest that a simultaneously interpenetrating polymer network may be formed which gives rise to a measured improvement in composite mechanical properties.

An attempt is made to develop tough, moisture resistant, high char yield epoxy resins by means of novel bisimide amine (BIA) hardener curing agents and a state-of-the-art epoxy resin system. The BIAs are isolated as mixtures containing monomer, oligomer, and polymeric species, and then characterized by elemental analysis and high pressure liquid chromatography. The bisimide amine-cured epoxies (IMEs) were characterized with respect to moisture absorption, thermal properties, and physical and mechanical properties, as well as in the role of matrices in Celion 6000/IME composites. The relative toughness characteristics of each IME formulation was measured by the 10 deg off-axis tensile test, measuring the uniaxial tensile strength, shear strength, and shear-strain-to-failure of the composite systems.

Studies were performed to synthesize new ether modified, flexibilized aromatic diamine hardeners for curing epoxy resins. The effect of moisture absorption on the glass transition temperatures of a tetraglycidyl epoxy, MY 720, cured with flexibilized hardeners and a conventional aromatic diamine was studied. Unidirectional composites, using epoxy-sized Celion 6000 graphite fiber as the reinforcement, were fabricated. The room temperature and 300 F mechanical properties of the composites, before and after moisture exposure, were determined. The Mode I interlaminar fracture toughness of the composites was characterized using a double cantilever beam technique to calculate the critical strain energy release rate.

The nonisothermal crystallization kinetics of PEEK APC-2 and of 450G neat resin PEEK material were compared using a differential scanning calorimeter to monitor heat flow during crystallization; the effects of cooling rate on the crystallization temperature, the degree of crystallinity, and the conversion rate were investigated. A modified Avrami (1940) analysis was used to describe nonisothermal crystallization kinetics. It was found that, compared with the 450G neat resin PEEK, the nonisothermal crystallization of the PEEK APC-2 composite is characterized by higher initiation temperature, higher heat flow maximum temperature, and greater relative conversion by primary processes.

Criteria have been developed for identifying, characterizing, and quantifying fracture modes in high-modulus graphite-fiber/resin unidirectional composites subjected to off-axis tensile loading. Procedures are described which use sensitivity analyses and off-axis data to determine the uniaxial strength of fiber composites. It was found that off-axis composites fail by three fracture modes which produce unique fracture surface characteristics. The stress that dominates each fracture mode and the load angle range of its dominance can be identified. Linear composite mechanics is adequate to describe quantitatively the mechanical behavior of off-axis composites. The uniaxial strengths predicted from off-axis data are comparable to those measured in uniaxial tests.

The objective of this study is to determine the energy dissipation processes in polymer-matrix composites during impact of ballistic projectiles. These processes include heat, fiber deformation and breakage, matrix deformation and fracture, and interfacial delamination. In this study, experimental measurements were made, using specialized specimen designs and test methods, to isolate the energy consumed by each of these processes during impact in the ballistic range. Using these experiments, relationships between material parameters and energy dissipation were examined. Composites with the same matrix but reinforced with Kevlar, PE, and graphite fabric were included in this study. These fibers were selected based on the differences in their intrinsic properties. Matrix cracking was found to be one of the most important energy absorption mechanisms during impact, especially in ductile samples such as Spectra-900 PE and Kevlar-49 reinforced polymer. On the contrary, delamination dominated the energy dissipation in brittle composites such as graphite reinforced materials. The contribution from frictional forces was also investigated and the energy partitioning among the different processes evaluated.

A complete stress analysis and reliable failure criteria are essential for important structural applications of composites in order to fully utilize their unique properties. The inhomogeneity, anisotropy and inelasticity of many composites make the use of experimental methods indispensable. Among the experimental techniques, transmission photoelasticity has been extended to birefringent composites in recent years. The extension is not straight-forward, in view of the complex nature of the photoelastic response of such model materials. This paper very briefly reviews the important developments in the subject and then describes the theoretical basis for a new method of determining the individual values of principal stresses in composite models. The method consists in drilling very small holes at points where the state of stress has to be determined. Experiments are then described which verify the theoretical predictions. The limitations of the method are pointed out and it is concluded that valuable information concerning the state of stress in a composite model can be obtained through the suggested method.

Thermal properties, flammability, and selected mechanical properties of eight different graphite composite panels fabricated using four different resin matrices and two types of graphite reinforcement were investigated and compared with the properties of an epoxy composite, MXB 7203. The resin matrices included XU71775/H795, a blend of vinyl poly(styrylpyridine) and bismaleimide; H795, a bismaleimide; Cycom 6162, a phenolic; and PSP 6022M, a poly(styrylpyridine). The graphite fiber was AS-4 used in the form of tape or fabric. It was found that the XU71775/H795 blend with the graphite tape was the optimum design giving the lowest heat release rate, while the control epoxy panel exhibited the highest total heat release and heat release rates, highest smoke and CO evolution, highest mass losses, and lowest oxygen index of all the composites tested.

The effect of processing variables on the flammability and mechanical properties of state-of-the-art and advanced resin matrices for graphite composites were studied. Resin matrices which were evaluated included state-of-the-art epoxy, phenolic-novolac, phenolic-Xylok, two types of bismaleimides, benzyl, polyethersulfone, and polyphenylsulfone. Comparable flammability and thermochemical data on graphite-reinforced laminates prepared with these resin matrices are presented, and the relationship of some of these properties to the anaerobic char yield of the resins is described.

Experimental results are presented that show that the structure of carbon fibers induces molecular orientation of liquid crystal polymers. X-ray diffraction data are used to demonstrate final collinearity of the polymer molecular axis and carbon fiber axis independent of fabrication approaches or prefabrication orientation of the polymer relative to the carbon fiber direction. The final degree of polymer molecular orientation approximately equals the degree of carbon basal plane orientation within the carbon fiber.

A testing program was conducted to determine the time-temperature response of the principal compliances of a unidirectional graphite/epoxy composite. It was shown that the two components of the compliance matrix are time and temperature independent. In addition, the compliance matrix is symmetric for the viscoelastic composite. The time-temperature superposition principle is used to determine shift factors. It was shown that the shift factors are independent of fiber orientation for fiber angles that vary from 10 to 90 deg with respect to the load direction.

Dynamic mechanical measurement results are presented for the case of carbon fiber-reinforced, epoxy matrix composite laminates subjected to loading perpendicular to the lamination plane, as well as for neat epoxy resin under the same conditions, where temperatures ranged between 20 and 200 C and deformation levels lie within the linear viscoelastic region. In-phase and out-of-phase stiffnesses are found to become superposed, forming master curves that cover a 12-decade frequency range. The application of a master curve scaling procedure shows that the in-phase stiffness has the same shape, and out-of-phase stiffness has the same dispersion, for all laminates irrespective of stacking sequence and are, in turn, nearly identical to those for the neat epoxy resin. An empirical function is found for the relaxation modulus which, when converted to a dynamic modulus, yields good overall agreement for both of the dynamic stiffness components as a function of frequency.

The Iosipescu shear test, developed initially in the 1960s for use with homogeneous, isotropic structural materials such as metals, has been adapted during the past ten years for use with composite materials. Much of this development work has taken place at the University of Wyoming, where a very efficient test fixture configuration has been developed, and extensive test results have been generated. Many other research groups have also adopted the test method during the past five years. As a result, the American Society for Testing and Materials (ASTM) is presently in the final stages of making the Iosipescu shear test an ASTM standard. The test method is described and its range of applications indicated, including examples of typical data.

A method is presented for tailoring plate and shell composite structures for optimal forced damped dynamic response. The damping of specific vibration modes is optimized with respect to dynamic performance criteria including placement of natural frequencies and minimization of resonance amplitudes. The structural composite damping is synthesized from the properties of the constituent materials, laminate parameters, and structural geometry based on a specialty finite element. Application studies include the optimization of laminated composite beams and composite shells with fiber volume ratios and ply angles as design variables. The results illustrate the significance of damping tailoring to the dynamic performance of composite structures, and the effectiveness of the method in optimizing the structural dynamic response.

The amounts of resin weight loss and fiber weight loss in four PMR-polyimide graphite fiber composites were calculated from the composite weight losses and the fiber/resin ratios of the composites after long term thermo-oxidative aging in 600 F air. The accelerating effect of graphite fiber on resin weight loss, compared to neat resin weight loss, indicated the presence of a deleterious resin/fiber thermo-oxidative interaction, presumably due to fiber impurities. Similarly, the decelerating effect of the protective matrix resin on fiber weight loss, compared to bare fiber weight loss, was also demonstrated. The amount of hydrazine-indigestible resin and the amount of loose surface graphite fiber that formed during 600 deg F exposure of the composites were quantitatively determined. The indigestible residual resin was also qualitatively studied by scanning electron microscopy.

Computerized infrared analysis is applied to the characterization of a glass-reinforced crosslinked polyester. The method of factor analysis determines the number of independent components which constitute the polymeric matrix. Subsequently, the spectra of those components are fitted by a least-squares criterion to spectra of the multicomponent matrix, or, if the glass spectrum is included as an additional component, to the spectra of composites. The least-squares coefficients yield the matrix composition in terms of the initial reactant composition and the extent of crosslinking.

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.

Studies were performed to determine the toughness characteristics of composites prepared from modified addition-type polyimides, using Celion 6000 graphite fiber as the reinforcement. The polyimides were prepared from aromatic diamines containing flexibilizing ether connecting groups. The composite flexural and short beam shear strengths were determined at room temperature and elevated temperatures. Composite toughness was evaluated using 10 deg off axis tensile tests and double cantilever beam fracture tests at room temperature. The effects of the flexibilized resin structure on composite mechanical properties, toughness characteristics, and thermo-oxidative stability are discussed.

A mechanics theory is developed for predicting the physical thermal, hygral and mechanical properties (including various strengths) of unidirectional intraply hybrid composites (UIHC) based on unidirectional properties of the constituent composites. Procedures are described which can use this theory in conjunction with composite mechanics computer codes and general purpose structural analysis finite element programs for the analysis/design of structural components made from intraply hybrid angleplied laminates (IHAL). Comparisons with limited data show that this theory predicts mechanical properties of UIHC and flexural stiffnesses of IHAL which are in good agreement with experimental data. The theory developed herein makes it possible to design and optimize structural components from IHAL based on a large class of available constituent fibers.

Short beam testing was used to determine the shear properties of laminates consisting of T-300 and Celion 3000 and 6000 graphite fibers, in epoxy, hot melt and solvent bismaleimide, polyimide and polystyrylpyridine (PSP). Epoxy, composites showed the highest interlaminar shear strength, with values for all other resins being substantially lower. The dependence of interlaminar shear properties on the fiber-resin interfacial bond and on resin wetting characteristics and mechanical properties is investigated, and it is determined that the lower shear strength of the tested composites, by comparison with epoxy resin matrix composites, is due to their correspondingly lower interfacial bond strengths. An investigation of the effect of the wettability of carbon fiber tow on shear strength shows wetting variations among resins that are too small to account for the large shear strength property differences observed.

Temperature-frequency dependence of alpha, beta, and gamma transitions was determined using a Rheometrics dynamic spectrometer on a series of unidirectional Celion 6000/N-phenylnadimide (PN) modified PMR polyimide composites. The objective was to see if any correlations exist between crosslinked network structure and dynamic mechanical properties. Variation in crosslinked network structures was achieved by altering the polyimide formulation through addition of various quantities of PN into the standard PMR-15 composition. As a control, PMR-15 composite system exhibited well-defined alpha, beta, and gamma transitions in the regions of 360, 100, and -120 C, respectively. Their activation energies were estimated to be 232, 60, and 14 kcal/mole, respectively. Increasing the amount of PN concentration caused lowering of the activation energies of the three relaxations, a decrease of the glass transition temperature, and increasing intensities of the three damping peaks, compared to the control PMR-15 counterpart. These dynamic mechanical responses were in agreement with formation of a more flexible copolymer from PN and PMR-15 prepolymer.

Crack extension during fatigue loading is one of the primary causes of failure in engineering materials. While the fatigue crack resistance of homogeneous and even adhesive systems has received detailed study and characterization, relatively few and scattered results are available for fiber composites. One difficulty with obtaining such data for composites is their tendency to develop complex patterns of intra- and interlaminar damage which expand in a stable manner during fatigue. Such damage usually does not severely reduce the load carrying capacity of a structure but the complexity of the damage geometry has so far frustrated efforts to apply any unifying theories of growth. Measurement of the rate of macroscopic crack growth, through thickness crack extension, has been possible for certain composites and crack direction where the stable damage is constrained. These include cracks in 0°/90° laminates, woven fabric laminates, chopped strand mat laminates, sheet molding (SMC) materials, and short fiber reinforced thermoplastics. Macroscopic interlaminar cracks in continuous fiber systems have also received some recent attention. Fatigue crack growth in glass fiber composites for which most data are available, involves significant contributions from both static and cyclic load effects. A simple model for predicting fatigue crack growth rates from traditional S-N curve and fracture toughness data has proven useful for certain well behaved systems. Limited study has also been made of the effects of moisture and salt water on the fatigue crack growth rate.