Engineering PapersSearch

Engineering topics

Vannucci, R. D.

Publications and source records attributed to Vannucci, R. D..

At least 19 records

Improved PMR Polyimides For Heat-Stable Laminates

Second-generation PMR-type polyimides (PMR-II polyimides) of enhanced thermo-oxidative stability prepared by substitution of para-aminostyrene (PAS) end caps for nadic-ester (NE) end caps used in prior PMR-II polyimides. Laminates unidirectionally reinforced with graphite fibers and made with PAS-capped resins exhibited thermo-oxidative stabilities significantly greater than those of similar laminates made with NE-capped PMR-II resins. One new laminate exhibited high retention of weight and strength after 1,000 h of exposure to air at 371 degrees C.

Vannucci, R. D.

High molecular weight first generation PMR polyimides for 343 C applications

The effect of molecular weight on 343 C thermo-oxidative stability (TOS), mechanical properties, and processability, of the first generation PMR polyimides was studied. Graphite fiber reinforced PMR-15, PMR-30, PMR-50, and PMR-75 composites (corresponding to formulated molecular weights of 1500, 3000, 5000, and 7500, respectively) were fabricated using a simulated autoclave process. The data reveal that while alternate autoclave cure schedules are required for the high molecular weight resins, low void laminates can be fabricated which have significantly improved TDS over PMR-15, with only a small sacrifice in mechanical properties.

Malarik, D. C.

Autoclavable addition polyimides for 371 C composite applications

Studies were conducted to improve the thermo-oxidative stability (TOS) of PMR type polyimides by the substitution of para-aminostyrene (PAS) for the nadic ester endcap in second generation PMR polyimides (PMR-2). The nadic endcap which provides the PMR polyimides with their relative ease of fabrication, both by limiting the molecular weight of the prepolymer and by undergoing the final addition cure without volatiles, is also the weak link with regard to TOS. A polyimide formulated with PAS endcaps, called V-CAP, utilizes a two step reaction sequence similar to that of the PMR polyimides and can be easily autoclave molded into low void composite materials. Resin studies included two formulations of both PMR-2 and V-CAP, corresponding to n=9 and n=14 prepolymer stoichiometry. Unidirectional reinforced T40R graphite fiber laminates were fabricated from each of the resins was post-cured in either air at 385 C or nitrogen at 400 C. Composite specimens were aged in air at 371 C and mechanical properties were measured at 371 C before and after exposure.

Vannucci, R. D.

Autoclavable addition polyimides for 371 C composite applications

Studies were conducted to improve the thermo-oxidative stability (TOS) of PMR type polyimides by the substitution of para-aminostyrene (PAS) for the nadic ester endcap in second generation PMR polyimides (PMR-2). The nadic endcap which provides the PMR polyimides with their relative ease of fabrication, both by limiting the molecular weight of the prepolymer and by undergoing the final addition cure without volatiles, is also the weak link with regard to TOS. A polyimide formulated with PAS endcaps, called V-CAP, utilizes a two step reaction sequence similar to that of the PMR polyimides and can be easily autoclave molded into low void composite materials. Resin studies included two formulations of both PMR-2 and V-CAP, corresponding to n = 9 and n = 14 prepolymer stoichiometry. Unidirectional reinforced T40R graphite fiber laminates were fabricated from each of the resins was post-cured in either air at 385 C or nitrogen at 400 C. Composite specimens were aged in air at 371 C and mechanical properties were measured at 371 C before and after exposure.

Vannucci, R. D.

Effect of solution concentration and aging conditions on PMR-15 resin

High performance liquid chromatography is utilized to evaluate the effect of temperature, solution concentration, and aging time on PMR-15 resin solutions. Fifty- and 70-wt percent PMR-15 resin solutions were prepared from the mixture of 5-norbornene-2,3-dicarboxylic ester (NE) acid, 4.4'-methylenedianiline (MDA), methanol, and 3,3',4.4.-benzophenonetetracarboxylic dimethyl ester (BTDE) acid solution. It is observed that in PMR-15 resin solution aged for 35 days at room temperature NE and MDA react to form amide and imide intermediates. The precipitation data reveal that in the 70-wt percent solution precipitation occurs after 12 days and in the 50-wt percent solution after 20 days; however, at lower temperatures (-11 C, and 2 C) no precipitation is detected. It is concluded that storage of resin solutions and powders at reduced temperatures extends shelf life by reducing the rate of imide formation.

Roberts, G. D.

Properties of autoclaved Gr/PI composites made from improved tack PMR-15 prepreg

Autoclave processing studies were conducted, using improved tack PMR-15 prepreg, to determine the effect of tack enhancing PMR resin modifications on composite processability and mechanical properties. Improved tack graphite fiber reinforced PMR-15 prepregs were prepared and exposed to ambient conditions for various times and then autoclave molded into composites. Composite specimens were prepared and tested for flexural and interlaminar shear strengths at room temperature and 316 C. The retention of flexural and interlaminar shear strength as a function of exposure in air at 316 C was also determined. The results show that the modified PMR resin solutions provide prepreg with improved tack and drape retention characteristics without adversely affecting processability or mechanical properties of autoclave molded graphite fiber reinforced PMR-15 composites.

Vannucci, R. D.

Graphite/PMR polyimide composites with improved toughness

The toughness of composites made with modified PMR (polymerization of monomer reactants) polyimides and Celion 6000 graphite fibers was studied. Various types/levels of monomer reactants containing flexible links were incorporated into PMR resin compositions used to prepare composites. The composites were evaluated for toughness using instrumented drop weight and 10 deg off axis tensile tests at room temperature, and for strength using flexure and short beam shear tests at room temperature and at elevated temperature. The effect of resin composition on composite processability, thermo-oxidative stability, toughness and mechanical properties are discussed.

Vannucci, R. D.

Graphite/PMR polyimide composites with improved toughness

The toughness of composites made with modified PMR (Polymerization of monomer reactants) polyimides and Celion 6000 graphite fibers was studied. Various types/levels of monomer reactants containing flexible links were incorporated into PMR resin compositions used to prepare composites. The composites were evaluated for toughness using instrumented drop weight and 10 deg off axis tensile tests at room temperature, and for strength using flexure and short beam shear tests at room temperature and at elevated temperature. The effect of resin composition on composite processability, thermo-oxidative stability, toughness and mechanical properties are discussed.

Vannucci, R. D.

PMR-15 polyimide modifications for improved prepreg tack

The use of mixed solvents and of modified monomeric ester reactants was investigated as a means of improving the tack and drape retention characteristics of PMR-15 polyimide prepreg. Methanol, ethanol, 1-propanol and 1-butanol were used to prepare the esters, prepreg solutions, and T-300 graphite fabric and Celion 6000 unidirectional fiber prepregs. The tack retention characteristics of the T-300 fabric prepreg after exposure to simulated use conditions were determined using a simple lap shear test. Drape was qualitatively assessed by visually monitoring the deformability of the prepreg. Thermo-oxidative stability and mechanical properties retention of the Celion 6000 grahite fiber composites were determined as a function of exposure time in air at 600 F.

Vannucci, R. D.

Curing agent for polyepoxides and epoxy resins and composites cured therewith

A curing for a polyepoxide is described which contains a divalent aryl radical such as phenylene a tetravalent aryl radical such as a tetravalent benzene radical. An epoxide is cured by admixture with the curing agent. The cured epoxy product retains the usual properties of cured epoxides and, in addition, has a higher char residue after burning, on the order of 45% by weight. The higher char residue is of value in preventing release to the atmosphere of carbon fibers from carbon fiber-epoxy resin composites in the event of burning of the composite.

Serafini, T. T.

Lower-curing-temperature PMR polyimides

Studies were performed to achieve a lower-curing-temperature PMR polyimide. The use of m-aminostyrene as the end-cap instead of the monoalkyl ester of 5-normbornene-2,3 dicarboxylic acid was investigated in typical PMR formulations. Model compound studies were also performed. Differential scanning calorimetry studies were performed on model compounds and neat resins to establish their melting and curing characteristics. The elevated temperature weight loss characteristics of neat resins and graphite fiber composites were determined. The room temperature and short-time 260 C (500 F) mechanical properties of the composites were also determined. The use of m-aminostyrene end-caps reduced the final cure temperature of PMR resins by about 55 C (100 F), but the composites prepared with these resins are limited to use temperatures of about 260 C (500 F).

Serafini, T. T.

Properties of PMR Polyimide composites made with improved high strength graphite fibers

High strength, intermediate modulus graphite fibers were obtained from various commercial suppliers, and were used to fabricate PMR-15 and PMR-2 polyimide composites. The effects of the improved high strength graphite fibers on composite properties after exposure in air at 600 F were investigated. Two of the improved fibers were found to have an adverse effect on the long term performance of PMR composites. The influence of various factors such as fiber physical properties, surface morphology and chemical composition were also examined.

Vannucci, R. D.

Properties of PMR polyimide composites made with improved high strength graphite fibers

Recent graphite fiber developments have resulted in high strength, intermediate modulus graphite fibers having improved thermo-oxidative resistance. These improved fibers, obtained from various commercial suppliers, were used to fabricate PMR-15 and PMR-11 polyimide composites. Studies were performed to investigate the effects of the improved high strength graphite fibers on composite properties after exposure in air at 600 F. The use of the more oxidatively resistant fibers did not result in improved performance at 600 F. Two of the improved fibers were found to have an adverse effect on the long-term performance of PMR composites. The influence of various factors such as fiber physical properties, surface morphology and chemical composition are also discussed.

Vannucci, R. D.

Effects of graphite fiber stability on the properties of PMR polyimide composites

The effect of the stability of graphite fibers on composite properties after exposure in air at 600 F was investigated. Composites were fabricated from PMR-15 and PMR-2 monomer solutions, using HTS-2 and Celion 6000 graphite fibers as the reinforcement. The effect of long-term exposure in air at 600 F on composite weight loss and mechanical properties was determined. These composites exhibited a significantly increased lifetime at that temperature compared to composites fabricated from HTS fiber sold prior to 1975. The effect of the PMR-15 and PMR-II resin compositions on long-term composite performance at 600 F is also discussed.

Delvigs, P.

Characterization of PMR polyimides: Correlation of ester impurities with composite properties

The presumed relationship of chemical impurities to final composite properties was investigated for PMR-polyimide resin. Ester/acid solutions of one monomer were aged at selected temperatures and chemical changes were monitored spectroscopically. At selected intervals, graphite fiber reinforced composite panels were fabricated. Changes in resin processing characteristics and composite properties were determined. The correlation of these data are discussed as are related characterization studies of PMR-polyimide resin.

Lauver, R. W.

Stability of PMR-polyimide monomer solutions

The stability of alcohol solutions of norborneyl capped PMR-polyimide resins was monitored during storage at ambient and subambient temperatures. Chemical changes during storage were determined spectroscopically using nuclear magnetic resonance. Resin processability and cured resin quality were determined by fabrication of unidirectional, graphite fiber composites using aged solutions and testing of selected composite properties. PMR-15 solutions exhibit nominally two weeks of useful life and PMR-2 solutions exhibit nominally two days of useful life at ambient conditions. The limiting factor is precipitation of imide reaction produces from the monomer solutions. Both solutions exhibit substantially longer useful lifetimes in subambient storage. PMR-15 shows no precipitation after several months storage at subambient temperatures. PMR-2 solutions do exhibit precipitates after extended subambient storage, however, the precipitates formed under these conditions can be redissolved. The chemical implications of these observations are discussed.

Lauver, R. W.

High char imide-modified epoxy matrix resins

The synthesis of a class of bis(imide-amine) curing agents for epoxy matrix resins is discussed. Glass transition temperatures and char yield data of an epoxy cured with various bis(imide-amines) are presented. The room temperature and 350 F mechanical properties, and char yields of unidirectional graphite fiber laminates prepared with conventional epoxy and imide-modified epoxy resins are presented.

Serafini, T. T.

Stability of PMR-polyimide monomer solutions

The stability of alcohol solutions of norbornenyl capped PMR-polyimide resins (both PMR-15 and PMR-II) has been monitored during storage at ambient and subambient (5 C and -18 C) temperatures. PMR-15 solutions exhibit nominally two weeks of useful life and PMR-II solutions exhibit nominally two days of useful life at ambient conditions. The limiting factor is precipitation of imide reaction products from the monomer solutions. Both solutions exhibit substantially longer useful lifetimes in subambient storage. PMR-15 shows no precipitation after several months storage at subambient temperatures. PMR-II solutions do exhibit precipitates after extended subambient storage (nominally three months at -18 C), however, the precipitates formed under these conditions can be redissolved. The chemical implications of these observations are discussed.

Lauver, R. W.