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This study investigated the influence of carboxyl-terminated butadiene acrylonitrile (CTBN) liquid rubbers on the microcracking response of polymeric composite materials to cryogenic cycling. Matrices of carbon fiber/epoxy prepregs were modified with different concentrations of two CTBN liquid rubbers. The glass transition temperature and the interlaminar shear strength of the laminate systems were depressed as a result of the presence of CTBN in the epoxy phase. An increase in total rubber concentration with the continuous phase was found to decrease and in some cases eliminate microcracking in laminates exposed to cryogenic cycling.

A model prepreg system was used to evaluate the effect of cure temperature on microcracking in polymeric composite materials exposed to cryogenic cycling. Symmetric and unsymmetric carbon fiber/epoxy laminates were fabricated to examine the development of thermal stresses and microcracks at cryogenic temperatures. The residual strains and theoretical curvatures of the laminates were calculated from the composite properties and correlated with the microcrack density and experimentally observed curvatures. Higher cure temperatures resulted in higher stress free temperatures and residual strains in the laminates, which corresponded directly to increased levels of microcracking.

A new family of particulate modifiers was incorporated into an epoxy-based model film adhesive system and the performance was evaluated. The particulate modifiers were selected to include a range of particle sizes, chemistry, and functionality. Thermal analysis, lap shear, and fracture energy tests were performed to characterize the performance of the adhesives. The mechanisms of failure for the adhesives were analyzed in relation to the particle modifier characteristics. Significant differences were found for mode I fracture energy when comparing adhesively joined composite specimens in cocured and bonded situations. Large preformed particle modified adhesives had nearly the same G IC values for both cocured and bonded applications, while the G IC values for the much smaller core-shell particle modified adhesives differed significantly. All particle modified adhesives provided an improvement in mode II fracture toughness over that of the control such that the laminates failed either in compression (through-thickness direction) or through delamination of the prepreg plies.

A key aspect of composite technology lies in the ability to design a part to a specific strength and thickness. Recently, new applications were identified where it was desirable to vary the density in specific areas of a part. In this work, a model prepreg system was modified with fine metal and thermoplastic particles for specific weight tailoring. These particles were placed on the prepreg surface, forming a partially interlayer modified composite when laid up and cured. Experiments were performed on the specific gravity and fracture toughness of laminates made from the prepregs. The results showed that it is possible to tailor the density of a composite system without changing the manufacturing process or fracture toughness requirements.

A review is presented that focuses on preformed particle modification of high performance thermosetting resins and composite systems. The modifiers reviewed consist of thermoplastic and rubber preformed particles with no size limitations. Both organic and inorganic preformed polymer particles are considered but not glass or hollow spheres. In this text, preformed particles are defined as those which do not require phase separation and remain in the shape in which they were added to the neat resin or composite. Therefore, these particles may be developed prior to the resin formulation and then added to the thermosetting resin or developed in situ (during resin formulation) before the resin is catalyzed or cured. This technical review of preformed particle modification of thermosetting resins and composite systems summarizes the utilization of these materials and their performance.

Model cyanate ester resins containing different quantities of epoxy functional butadiene-acrylonitrile rubber (ETBN) to improve the fracture performance were developed as matrices for composites. With the elastomeric modification, the resin systems exhibited rheological characteristics inappropriate for laminate fabrication by conventional resin transfer molding (RTM). To fabricate the carbon fiber based laminates in one liquid molding operation successfully, a process named bleed resin transfer molding (BRTM) was established. The BRTM process combines features of RTM and resin film infusion processes (RFI) and was therefore appropriate for processing high viscosity matrix resins. A novel catalyst was selected for the cyanate ester resin that provided enough latency for the impregnation steps in the BRTM process. Through the use of thermal analytical tools, a high degree of phase separation and conversion was obtained. The conversion and the glass transition temperature were found not to decrease with increasing elastomer content, which is in contradiction to most toughening modifications. Mode I and Mode II interlaminar fracture toughness were found to increase significantly with increasing elastomer content. In Mode I, an increase of up to 140% was observed. Collectively, this work showed that through the use of the BRTM technique, matrices with toughness improvements usually only achieved by prepreg systems can be processed in an RTM-like manner.

Porosity in cured honeycomb parts was investigated using model prepreg systems and compared with a commercial solvent produced prepreg. Woven glass fabric was used as the reinforcement in both of the systems. Three main solvents were identified in the commercial prepreg. These solvents were found to cause porosity or reduce thermal properties in model solvent prepreg based laminates when used either separately or in combination. Lowering the solvent content reduced the porosity in the prepreg but was limited by resin staging. The high level of porosity, resulting from solvents, found in these commercial prepreg systems motivated the investigation of the feasibility of changing the method of impregnation from solvent to hot-melt. Hot-melt model prepreg produced essentially void-free laminates as well as honeycomb parts. Model prepreg produced by hot-melt impregnation was found to be more robust, providing the capability of changing the degree of resin impregnation in the fiber bed. A low level of impregnation resulted in the best fillets to the honeycomb core, while still producing essentially void free parts. The use of both solid and liquid carboxyl-functional elastomers was incorporated in the epoxy based resin to provide flow control and self-adhesive characteristics. Mechanical properties of both the model hot-melt and commercial prepreg based honeycomb structures and laminates were compared. The model hot-melt prepreg was found to have better cured properties along with the necessary prepreg characteristics providing an optimized self-adhesive controlled flow prepreg system.

The effects of fiber tension, line speed, and impregnation temperature and pressure in the prepregging process used to manufacture a commercial high temperature toughened epoxy prepreg were investigated in a Design of Experiments (DOE) to understand core crush in honeycomb composite structures. The prepregs developed in this DOE were characterized by tack, permeation, optical microscopy, and frictional resistance. Of these methods, frictional resistance was found to correlate with core crush. Tack, permeation, and optical microscopy provided a basis for understanding this relationship through impregnation and morphology. Prepregs manufactured with high fiber tension showed greater crush and less frictional resistance than prepregs with manufactured low fiber tension. These low tension prepregs were found to have more fibers at the prepreg surface, allowing them to grip the adjacent surface and resist slippage. By identifying the key factors influencing honeycomb core crush, the prepregging process was modified, producing a crush-resistant prepreg for end use manufacture.

A controlled-flow epoxy-based model prepreg resin system was developed. The formulation of the model controlled-flow resin was designed from performance information obtained from a commercially available controlled-flow resin, presently used in the aircraft industry. Thermoanalytical techniques including rheometry were used to provide the necessary information to develop the model system along with a formulation methodology developed by Seferis and co-workers. The model resin formulation, which was a combination of tetraglycidyl ether of methylenedianiline (TGMDA), diglycidyl ether of bisphenol-A (DGEBA), carboxyl-modified butadiene/acrylonitrile rubber (CMBN), carboxyl-terminated butadiene / acrylonitrile rubber (CTBN), bisphenol-A (BPA), diaminodiphenyl sulfone (DDS), and dicyandiamide (DICY), was hot-melt impregnated into unidirectional carbon fibers on a laboratory scale hot-melt prepreg machine. A two-parameter, three-level design of experiments was performed on the prepreg processing parameters in which impregnation temperature and pressure were varied. Thus, a total of nine different experimental prepregs were produced and characterized by resin content, extent of impregnation, and tack. The results from the characterization of the nine experimental prepregs are compared with the effects of the prepreg processing conditions. These results are also compared with the results generated for the commercial controlled-flow resin. Collectively, this work provides a fundamental basis by which the analysis and rational utilization of controlled-flow matrix prepregs can be effected.