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At least 37 records · Page 2

Effect of High Temperature Storage on AC Characteristics of Polymer Tantalum Capacitors

Replacement of MnO2 with conductive polymers as cathode materials in chip tantalum capacitors allows for a substantial reduction of the equivalent series resistance (ESR), improvement of frequency characteristics, and elimination of the possibility of ignition during failures. One of the drawbacks of chip polymer tantalum capacitors (CPTCs) is a relatively poor long-term stability at high temperatures. In this work, variations of capacitance, dissipation factor, and ESR in different types of capacitors including automotive grade parts from three manufacturers have been monitored during storage at temperatures from 100 ºC to 175 ºC for up to 18,000 hours. Results show that ESR is the most and capacitance the least sensitive to degradation parameter. Times to parametric failures have been simulated using a Weibull-Arrhenius model that allowed for assessments of activation energies of the degradation and prediction of times to failure at the use temperature. Degradation of CPTCs was explained by thermo-oxidative processes in conductive polymers that result in exponential increasing of the resistivity with time of ageing. This process starts after a certain incubation period that depends on packaging materials and design and corresponds to the time that is necessary to form delamination between the encapsulating molding compound and lead frame. The effectiveness of the existing qualification procedures to assure stable operation of CPTCs is discussed.

Aging↗

Effect of High Temperature Storage on AC Characteristics of Polymer Tantalum Capacitors

Replacement of MnO2 with conductive polymers as cathode materials in chip tantalum capacitors allows for a substantial reduction of the equivalent series resistance (ESR), improvement of frequency characteristics, and elimination of the possibility of ignition during failures. One of the drawbacks of chip polymer tantalum capacitors (CPTCs) is a relatively poor long-term stability at high temperatures. In this work, variations of capacitance, dissipation factor, and ESR in different types of capacitors including automotive grade parts from three manufacturers have been monitored during storage at temperatures from 100 ºC to 175 ºC for up to 18,000 hours. Results show that ESR is the most and capacitance the least sensitive parameter to degradation. Times to parametric failures have been simulated using a Weibull-Arrhenius model that allowed for assessments of activation energies of the degradation and prediction of times to failure at the use temperature. Degradation of CPTCs was explained by thermo-oxidative processes in conductive polymers that result in exponential increase of the resistivity with time of aging. This process starts after a certain incubation period that depends on packaging materials and design and corresponds to the time that is necessary to form delamination between the encapsulating molding compound and lead frame. The effectiveness of the existing qualification procedures to assure stable operation of CPTCs is discussed.

high temperature storage (HTS)↗

Adjusting Measured Weight Loss of Aged Graphite Fabric/PMR-15 Composites

The purposes of this study were to evaluate the growth of the surface damage layer in polymer matrix composites (PMC's) fabricated with graphite fabric reinforcement and to determine the effects of the cut-surface degradation on the overall thermo-oxidative (TOS) stability of these materials. Four important conclusions were made about the TOS behavior of T650-35/PNIR- 15 fabric-reinforced composites: (1) Three stages of composite weight loss were seen on the plot of weight loss versus aging time; (2) the depth of the cut-edge damage is related to the composite thickness; (3) the actual weight loss realized by a mechanical test specimen that has had all the aging-induced cut-edge damage removed during the preparation process is significantly less than the weight loss measured using specimens with a high percentage of cut edges exposed to the damaging environment; and (4) an extrapolation of a section of the weight loss curve can be used to obtain a more correct estimate of the actual weight loss after extended periods of aging at elevated temperatures.

Bowles, Kenneth J.↗

Thermo-oxidative stability studies of Celion 6000/PMR-15 unidirectional composites, PMR-15, and Celion 6000 fiber

Experimental results on the influence of the thermooxidative resistance characteristics of the fiber and matrix resin on the thermal stability of isothermally aged Celion 6000/PMR-15 matrix resin composites are presented. SEM studies reveal that extreme oxidative erosion of the graphite fiber occurs at elevated temperatures in the presence of the polyimide matrix. The activation energy of oxidation of the composite was shown to be greater than those of the fiber and the matrix resin.

Bowles, Kenneth J.↗

A comparison of fiber effects on polymer matrix composite oxidation

A number of thermo-oxidative stability studies addressing the effects of fiber reinforcement on composite thermal stability and influence of geometry on the results of aging studies were performed at NASA-Lewis. The information presented herein, a compilation of some results from these studies, shows the influence of the reinforcement fibers on the oxidative degradation of various PMR-15 composites. Reinforcement of graphite and ceramics were studied and three composite oxidation mechanisms were observed. One was a dominant attack of the reinforcement fiber, the second was the aggressive oxidation of the matrix material, and the third was interfacial degradation.

Bowles, Kenneth J.↗

Comparison of Graphite Fabric Reinforced PMR-15 and Avimid N Composites After Long Term Isothermal Aging at Various Temperatures

Extensive effort is currently being expended to demonstrate the feasibility of using high-performance, polymer-matrix composites as engine structural materials over the expected operating lifetime of the aircraft, which can extend from 18,000 to 30,000 hr. The goal is to develop light-weight, high-strength, and high-modulus materials for use in higher temperature sections of advanced 21 st century aircraft propulsion systems. To accomplish this goal, it is necessary to pursue the development of thermal and mechanical durability models for graphite-fiber-reinforced, polymer-matrix composites. Numerous investigations have been reported regarding the thermo-oxidative stability (TOS) of the polyimide PMR-15 (1-5). A significant amount of this work has been directed at edge and geometry effects, reinforcement fiber influences, and empirical modeling of high-temperature weight loss behavior. It is yet to be determined if the information obtained from the PMR-15 composite tests is applicable to other polyimide-matrix composites. The condensation-curing polymer Avimid N is another advanced composite material often considered for structural applications at high temperatures. Avimid N has better thermo-oxidative stability than PMR-15 (6), but the latter is more easily processed. The most comprehensive study of the thermo-oxidative stability of Avimid N neat resin and composites at 371 (infinity)C is found in Salin and Seferis (7). The purposes of the work described herein were to compare the thermal aging behavior of these two matrix polymers and to determine the reasons for and the consequences of the difference in thermal durability. These results might be of some use in improving future polymer development through the incorporation of the desirable characteristics of both polyimides.

Bowles, Kenneth J.↗

Mechanical behavior of polyamide-6 after combined photo-oxidative and hygrothermal aging

The effect of moisture on the photo-oxidative degradation of polyamide-6 (PA-6) was studied by analyzing the mechanical response after two different accelerated aging procedures. In the first aging procedure, the PA-6 was only exposed to ultra-violet (UV) radiation at 60 °C. In the second procedure, the same duration of UV radiation was periodically interrupted while the relative humidity was raised to 100%. Diffusion-limited and nominally homogeneous degradation conditions were investigated using bulk and film specimens, respectively. Accelerated UV aging reduced the ductility of PA-6, but the additional hygrothermal exposure had no effect on the ductility or strength, indicating that humidity did not influence the photo-oxidation of PA-6. In conclusion, this finding contrasts with previous studies that found thermo-oxidation of PA-6 was accelerated by moisture.

36 MATERIALS SCIENCE↗

Effect of fiber reinforcement on thermo-oxidative stability and mechanical properties of polymer matrix composites

A number of studies have investigated the thermooxidative behavior of polymer matrix composites. Two significant observations have been made from these research efforts: (1) fiber reinforcement has a significant effect on composite thermal stability; and (2) geometric effects must be considered when evaluating thermal aging data. The polyimide PMR-15 was the matrix material used in these studies. The control composite material was reinforced with Celion 6000 graphite fiber. T-4OR graphite fibers, along with some very stable ceramic fibers were selected as reinforcing fibers because of their high thermal stability. The ceramic fibers were Nicalon (silicon carbide) and Nextel 312 (alumina-silica-boron oxide). The mechanical properties of the two graphite fiber composites were significantly different, probably owing to variations in interfacial bonding between the fibers and the polyimide matrix. Three oxidation mechanisms were observed: (1) the preferential oxidation of the Celion 6000 fiber ends at cut surfaces, leaving a surface of matrix material with holes where the fiber ends were originally situated; (2) preferential oxidation of the composite matrix; and (3) interfacial degradation by oxidation. The latter two mechanisms were also observed on fiber end cut surfaces. The fiber and interface attacks appeared to initiate interfiber cracking along these surfaces.

Bowles, K. J.↗

Effect of fiber reinforcements on thermo-oxidative stability and mechanical properties of polymer matrix composites

A number of studies have investigated the thermo-oxidative behavior of polymer matrix composites. Two significant observations have been made from these research efforts: (1) fiber reinforcement has a significant effect on composite thermal stability; and (2) geometric effects must be considered when evaluating thermal aging data. A compilation of some results from these studies is presented, and this information shows the influence of the reinforcement fibers on the oxidative degradation of various polymer matrix composites. The polyimide PMR-15 was the matrix material that was used in these studies. The control composite material was reinforced with Celion 6000 graphite fiber. T-40R graphite fibers, along with some very stable ceramic fibers were selected as reinforcing fibers because of their high thermal stability. The ceramic fibers were Nicalon (silicon carbide) and Nextel 312 (alumina-silica-boron oxide). The mechanical properties of the two graphite fiber composites were significantly different, probably owing to variations in interfacial bonding between the fibers and the polyimide matrix. The Celion 6000/PMR-15 bond is very tight but the T-40/PMR-15 bond is less tight. Three oxidation mechanisms were observed: (1) the preferential oxidation of the Celion 6000 fiber ends at cut surfaces, leaving a surface of matrix material with holes where the fiber ends were originally situated; (2) preferential oxidation of the composite matrix; and (3) interfacial degradation by oxidation. The latter two mechanisms were also observed on fiber end cut surfaces. The fiber and interface attacks appeared to initiate interfiber cracking along these surfaces.

Bowles, Kenneth J.↗

Structure-Property Relationship in High Tg Thermosetting Polyimides

This viewgraph presentation gives an overview of the structure-property relationship in high glass transition temperatures (T(sub g)) thermosetting polyimides. The objectives of this work are to replace MDA in PMR-15 with 2,2-substituted benzidine and to evaluate the thermo-oxidative stability and mechanical properties of DMBZ-15 against PMR-15. Details are given on the T(sub g) of polyimide resins, the x-ray crystal structure of 2,2-Bis(trifluoro)benzidine (BFBZ), the isothermal aging of polyimide resins at 288 C under 1 atm of circulating air, the compressive strength of polyimide composites, and a gas evaluation profile of DMBZ-15 polyimide resins.

Chuang, Kathy C.↗

Thermal stability relationships between PMR-15 resin and its composites

A study was conducted to investigate the relationship between the thermo-oxidative stability of PMR-15 matrix resin and the stability of graphite-fiber-reinforced composites that contain this resin as the matrix material. Three areas were investigated. The first was the effect of fiber/matrix interfacial bond strength on the isothermal aging weight loss of composites. By using type-A graphite fibers produced by Hercules, it was possible to study composites reinforced with fibers that were processed to receive different surface treatments. One of the fibers was untreated, a second fiber was treated by oxidation to enhance fiber/matrix bonding, and the third type of fiber was coated with an epoxy sizing. These treatments produced three significantly different interfacial bond strengths. The epoxy sizing on the third fiber was quickly oxidized from the bare fiber surfaces at 288, 316, and 343 C. The weight loss due to the removal of the sizing was constant at 1.5 percent. This initial weight loss was not observed in thermo-oxidative stability studies of composites. The PMR-15 matrix satisfactorily protected the reinforcemnt at all three temperatures.

Bowles, Kenneth J.↗

Longtime Durability of PMR-15 Matrix Polymer at 204, 260, 288, and 316 C

Isothermal weight loss studies at the Glenn (Lewis) Research Center were conducted at four temperatures (204, 260, 288, and 316 C) with specimens of varied geometric shapes to investigate the mechanisms involved in the thermal degradation of PMR-15. Both neat resin behavior and composite behaviors were studied. Two points of interest in these studies are the role(s) of oxygen in the mechanisms involved in the thermo-oxidative degradation of these composite materials and the dimensional changes that occur during their useable lifetime. Specimen dimensional changes and surface layer growth were measured and recorded. It was shown that physical and chemical changes take place as a function of time and location in PMR-15 neat resin and composites as aging takes place in air at elevated temperatures. These changes initiate at the outer surfaces of both materials and progress inward following the oxygen as it proceeds by diffusion into the central core of each material. Microstructural changes cause changes in density, material shrinkage (strains), glass transition temperature, dimension, dynamic shear modulus, and compression properties. These changes also occur slowly dividing the polymer material into two distinct parts: a visibly undamaged core section between two visibly damaged surface layers. The surface layer has a significant effect on compression properties of thinner specimens, but the visibly undamaged core material controls these properties for specimens having eight or more plies. It was demonstrated that there are three different mechanisms involved in the degradation of PMR-15 during aging at elevated temperatures. These are a weight gain, a small weight fraction bulk material weight loss, and a large mass fraction weight loss concentrated at the surface of the polymer or composite. At the higher temperatures (260 C and above), the surface loss predominates. Below 260 C, the surface loss and the bulk core loss become more equivalent. Between 175 and 260 C, the initial weight change is due to a weight gain mechanism with a visible lifetime that diminishes as the aging temperature increases.

Bowles, Kenneth J.↗

The Effects of Fiber Surface Modification and Thermal Aging on Composite Toughness and Its Measurement

A detailed experimental study was conducted to establish the structure-property relationships between elevated temperature aging and fiber-matrix bonding, Mode 2 interlaminar fracture toughness, and failure modes of carbon fiber/PMR-15 composites. The fiber-matrix adhesion was varied by using carbon fibers with different surface treatments. Short beam shear tests were used to quantify the interfacial shear strength afforded by the use of the different fiber surface treatments. The results of the short beam shear tests showed that, for times up to 1000 hr, the aging process caused no changes in the bulk of the three composite materials that would degrade the shear properties of the material. Comparisons between the interlaminar shear strengths (ILSS) measured by the short beam shear tests and the GIIC test results, as measured by the ENF test, indicated that the differences in the surface treatments significantly affected the fracture properties while the effect of the aging process was probably limited to changes at the starter crack tip. The fracture properties changed due to a shift in the fracture from an interfacial failure to a failure within the matrix when the fiber was changed from AU-4 to AS-4 or AS-4G. There appears to be an effect of the fiber/matrix bonding on the thermo-oxidative stability of the composites that were tested. The low bonding afforded by the AU 1 fiber resulted in weight losses about twice those experienced by the AS 1 reinforced composites, the ones with the best TOS.

Bowles, Kenneth J.↗

The Effects of Fiber Surface Modification and Thermal Aging on Composite Toughness And its Measurement

A detailed experimental study was conducted to establish the structure-property relationships between elevated temperature aging and (I) fiber-matrix bonding, (2) Mode II interlaminar fracture toughness, and (3) failure modes of carbon fiber/PMR-15 composites. The fiber-matrix adhesion was varied by using carbon fibers with different surface treatments. Short beam shear tests were used to quantify the interfacial shear strength afforded by the use of the different fiber surface treatments. The results of the short beam shear tests definitely showed that, for aging times up to 1000 hr, the aging process caused no observable changes in the bulk of the three composite materials that---would degrade the shear properties of the material. Comparisons between the interlaminar shear strength (ILSS) measured by the short beam shear tests and the GII c test results, as measured by the ENF test, indicated that the differences in the surface treatments significantly affected the fracture properties while the effect of the aging process was probably limited to changes at the starter crack tip. The fracture properties changed due to a shift in the fracture from an interfacial failure to a failure within the matrix when the fiber was changed from AU-4 to AS-4 or AS-4G. There appears to be an effect of the fiber/matrix bonding on the thermo-oxidative stability of the composites that were tested. The low bonding afforded by the AU-4 fiber resulted in weight losses about twice those experienced by the AS-4 reinforced composites, the ones with the best TOS.

Bowles, Kenneth J.↗

Cyclopentadiene evolution during pyrolysis-gas chromatography of PMR polyimides

The effect of formulated molecular weight (FMW), extent of cure, and cumulative aging on the amount of cyclopentadiene (CPD) evolved from Polymerization of Monomeric Reactants (PMR) polyimides were investigated by pyrolysis-gas chromotography (PY-GC). The PMR polyimides are additional crosslinked resins formed from an aromatic diamine, a diester of an aromatic tetracarboxylic acid and a monoester of 5-norbornene-2, 3-dicarboxylic acid. The PY-GC results were related to the degree of crosslinking and to the thermo-oxidative stability (weight loss) of PMR polyimides. Thus, PY-GC has shown to be a valid technique for the characterization of PMR polyimide resins and composites via correlation of the CPD evolved versus the thermal history of the PMR sample.

Alston, William B.↗

Structure-to-property relationships in addition cured polymers. 4: Correlations between thermo-oxidative weight losses of norbornenyl cured polyimide resins and their composites

Relationships are identified between the thermo-oxidative stability (TOS) at 316 C of a wide variety of PMR (polymerization of monomeric reactants) addition cured polyimide resins and their corresponding graphite fiber composites. Weight loss results at 316 C confirmed the expected relationship of increasing aliphatic endcap content with decreasing TOS. Moreover, the resin TOS study also showed an unexpected linear correlation of decreasing weight loss to increasing ratio of benzylic diamine to aliphatic endcap in the range of the stoichiometries studied. Only after long term 316 C aging does the dianhydride used with the benzylic diamines become an additional factor in influencing the amount of PMR resin and composite weight losses. Also, the benzylic systems consistently showed much lower resin and composite weight losses at 316 C than the corresponding nonbenzylic norbornenyl resins and composites, except when the nonbenzylic diamine monomer does not contain a connecting group. Instead, this diamine resulted in a 316 C resin and composite weight loss that was only competitive with benzylic type diamines. Results show excellent correlation between TOS of all graphite fiber PMR composites and resins.

Alston, William B.↗

Second generation PMR polyimide/fiber composites

A second generation polymerization monomeric reactants (PMR) polyimdes matrix system (PMR 2) was characterized in both neat resin and composite form with two different graphite fiber reinforcements. Three different formulated molecular weight levels of laboratory prepared PMR 2 were examined, in addition to a purchased experimental fully formulated PMR 2 precurser solution. Isothermal aging of graphite fibers, neat resin samples and composite specimens in air at 316 C were investigated. Humidity exposures at 65 C and 97 percent relative humidity were conducted for both neat resin and composites for eight day periods. Anaerobic char of neat resin and fire testing of composites were conducted with PMR 15, PMR 2, and an epoxy system. Composites were fire tested on a burner rig developed for this program. Results indicate that neat PMR 2 resins exhibit excellent isothermal resistance and that PMR 2 composite properties appear to be influenced by the thermo-oxidative stability of the reinforcing fiber.

Cavano, P. J.↗

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.↗