Accelerated aging of Nylon 6.6 fibers used in parachutes has been conducted by following the tensile strength loss under both thermal-oxidative and 100% relative humidity conditions. Thermal-oxidative studies (air circulating ovens) were performed for time periods of weeks to years at temperatures ranging from 37 °C to 138 °C. Accelerated aging humidity experiments (100% RH) were performed under both an argon atmosphere to examine the 'pure' hydrolysis pathway, and under an oxygen atmosphere (oxygen partial pressure close to that occurring in air) to mimic true aging conditions. As expected the results indicated that degradation caused by humidity is much more important than thermal-oxidative degradation. Surprisingly when both oxygen and humidity were present the rate of degradation was dramatically enhanced relative to humidity aging in the absence of oxygen. This significant and previously unknown phenomena underscores the importance of careful accelerated aging that truly mimics real world storage conditions. Published by Elsevier Ltd.
Conventional high-temperature compression stress-relaxation (CSR) experiments (e.g., using a Shawbury-Wallace relaxometer) measure the force periodically at room temperature. In this paper, we first describe modifications that allow the force measurements to be made isothermally and show that such measurements lead to more accurate estimates of sealing force decay. We then use conventional Arrhenius analysis and linear extrapolation of the high-temperature (80--110 C) CSR results for two commercial butyl o-ring materials (Butyl-A and Butyl-B) to show that Butyl-B is predicted to have approximately three times longer lifetime at room temperature (23 C). To test the linear extrapolation assumed by the Arrhenius approach, we conducted ultrasensitive oxygen consumption measurements from 110 C to room temperature for the two butyl materials. The results indicated that linear extrapolation of the high temperature CSR results for Butyl-A was reasonable whereas a significant curvature to a lower activation energy was observed for Butyl-B below 80 C. Using the oxygen consumption results to extrapolate the CSR results from 80 C to 23 C resulted in the conclusion that Butyl-B would actually degrade much faster than Butyl-A at 23 C, the opposite of the earlier conclusion based solely on extrapolation of the high-temperature CSR results. Since samples of both materials that had aged in the field for {approx}20 years at 23 C were available, it was possible to check the predictions using compression set measurements made on the field materials. The comparisons were in accord with the extrapolated predictions made using the ultrasensitive oxygen consumption measurements, underscoring the power of this extrapolation approach.
The authors have shown that the hydroperoxide species in {gamma}-irradiated {sup 13}C-polyethylene can be directly observed by {sup 13}C MAS NMR spectroscopy. The experiment was performed without the need for special sample preparation such as chemical derivatization or dissolution. Annealing experiments were employed to study the thermal decomposition of the hydroperoxide species and to measure an activation energy of 98 kJ/mol. EPR spectroscopy suggests that residual polyenyl and alkylperoxy radicals are predominantly trapped in interracial or crystalline regions, while the peroxy radicals observed after UV-photolysis of hydroperoxides are in amorphous regions.
Failure models based on the Palmgren-Miner concept that material damage is cumulative have been derived and used mainly for fatigue life predictions for metals and composite materials. The authors review the principles underlying such models and suggest ways in which they may be best applied to polymeric materials in temperature environments. They first outline expectations when polymer degradation data can be rigorously time-temperature superposed over a given temperature range. For a step change in temperature after damage has occurred at an initial temperature in this range, the authors show that the remaining lifetime at the second temperature should be linearly related to the aging time prior to the step. This predicted linearity implies that it should be possible to estimate the remaining and therefore the service lifetime of polymers by completing the aging at an accelerated temperature. They refer to this generic temperature-step method as the Wear-out approach. They next outline the expectations for Wear-out experiments when time-temperature superposition is invalid. Experimental Wear-out results are then analyzed for one material where time-temperature superposition is valid and for another where evidence suggests it is invalid. In analyzing the data, they introduce a procedure that they refer to as time-degradation superposition. This procedure not only utilizes all of the experimental data instead of a single point from each data set, but also allows them to determine the importance of any interaction effects.
Over the past two decades, Sandia has developed a variety of specialized analytical techniques for evaluating the long-term aging and stability of cable insulation and other related materials. These techniques have been applied to cable reliability studies involving numerous insulation types and environmental factors. This work has allowed the monitoring of the occurrence and progression of cable material deterioration in application environments, and has provided insights into material degradation mechanisms. It has also allowed development of more reliable lifetime prediction methodologies. As a part of the FAA program for intrusive inspection of aircraft wiring, they are beginning to apply a battery of techniques to assessing the condition of cable specimens removed from retired aircraft. It is anticipated that in a future part of this program, they may employ these techniques in conjunction with accelerated aging methodologies and models that the authros have developed and employed in the past to predict cable lifetimes. The types of materials to be assessed include 5 different wire types: polyimide, PVC/Glass/Nylon, extruded XL-polyalkene/PVDF, Poly-X, and XL-ETFE. This presentation provides a brief overview of the main techniques that will be employed in assessing the state of health of aircraft wire insulation. The discussion will be illustrated with data from their prior cable aging studies, highlighting the methods used and their important conclusions. A few of the techniques that they employ are widely used in aging studies on polymers, but others are unique to Sandia. All of their techniques are non-proprietary, and maybe of interest for use by others in terms of application to aircraft wiring analysis. At the end of this report is a list showing some leading references to papers that have been published in the open literature which provide more detailed information on the analytical techniques for elastomer aging studies. The first step in the investigation of aircraft wiring is to evaluate the applicability of their various techniques to aircraft cables, after which they expect to identify a limited subset of techniques which are appropriate for each of the major aircraft wiring types. The techniques of initial interest in the studies of aging aircraft wire are as follows: optical microscopy; mandrel bend test; tensile test/elongation at break; density measurements; modulus profiling/(spatially-resolved micro-hardness); oxygen induction time/oxygen induction temperature (by differential scanning calorimetry); solvent-swelling/gel fraction; infrared spectroscopy (with chemical derivatization as warranted); chemiluminescence; thermo-oxidative wear-out assessment; The first two techniques are the simplest and quickest to apply; those further down the list tend to be more information rich and in some cases more sensitive, but also generally more specialized and more time consuming to run. Accordingly, the procedure will be to apply the simplest tests for purposes of preliminary screening of large numbers of samples. For any given material type, it can be expected that only a limited number of the other techniques will prove to be useful, and therefore, the more specialized techniques will be used on a limited number of selected samples. Samples of aircraft wiring have begun to be released to the authors in late April; they include in this report some limited and preliminary data on these materials.
The so-called Palmgren-Miner concept that degradation is cumulative, and that failure is therefore considered to be the direct result of the accumulation of damage with time, has been known for decades. Cumulative damage models based on this concept have been derived and used mainly for fatigue life predictions for metals and composite materials. The authors review the principles underlying such models and suggest ways in which they may be best applied to polymeric materials in temperature environments. The authors first consider cases where polymer degradation data can be rigorously time-temperature superposed over a given temperature range. For a step change in temperature after damage has occurred at an initial temperature in this range, they show that the remaining lifetime at the second temperature should be linearly related to the aging time prior to the step. This predicted linearity implies that it may be possible to estimate the remaining lifetime of polymeric materials aging under application ambient conditions by completing the aging at an accelerated temperature. They refer to this generic temperature-step method as the Wear-out approach. They then outline the expectations for Wear-out experiments when time-temperature superposition is invalid, specifically describing the two cases where so-called interaction effects are absent and are present. Finally, they present some preliminary results outlining the application of the Wear-out approach to polymers. In analyzing the experimental Wear-out results, they introduce a procedure that they refer to as time-damage superposition. This procedure not only utilizes all of the experimental data instead of a single point from each data set, but also allows them to determine the importance of any interaction effects.
The {gamma}-irradiated-oxidation of pentacontane (C{sub 50}H{sub 102}) and the polymer polyisoprene was investigated as a function of oxidation level using {sup 17}O nuclear magnetic resonance (NMR) spectroscopy. It is demonstrated that by using {sup 17}O labeled O{sub 2} gas during the {gamma}-irradiation process, details about the oxidative degradation mechanisms can be directly obtained from the analysis of the {sup 17}O NMR spectra. Production of carboxylic acids is the primary oxygen-containing functionality during the oxidation of pentacontane, while ethers and alcohols are the dominant oxidation product observed for polyisoprene. The formation of ester species during the oxidation process is very minor for both materials, with water also being produced in significant amounts during the radiolytic oxidation of polyisoprene. The ability to focus on the oxidative component of the degradation process using {sup 17}O NMR spectroscopy demonstrates the selectivity of this technique over more conventional approaches.
{sup 13}C-enriched polyethylene was subjected to {gamma}-irradiation in the presence of air at 25 and 80 C for total doses ranging from 71 to 355 kGy. Significant quantities of hydroperoxides were detected in the 25 C irradiated sample by {sup 13}C magic angle spinning NMR spectroscopy. This method of detection was performed on the solid polymer and required no chemical derivatization or addition of solvent. The chemical stability and subsequent products of the hydroperoxide species were studied by annealing the irradiated samples in air at temperatures ranging from 22 to 110 C. A time-temperature superposition analysis provided an activation energy of 108 kJ/mol for the hydroperoxide decomposition process. The primary products of hydroperoxide decomposition were ketones and secondary alcohols with lesser amounts of acids and esters. EPR measurements suggest that the reactive hydroperoxide species reside in the amorphous phase of polyethylene, consistent with degradation occurring in the amorphous phase.
We have been working for many years to develop better methods for predicting the lifetimes of polymer materials. Because of the recent interest in extending the lifetimes of nuclear weapons and the importance of environmental seals (o-rings, gaskets) for protecting weapon interiors against oxygen and water vapor, we have recently turned our attention to seal materials. Perhaps the most important environmental o-ring material is butyl rubber, used in various military applications. Although it is the optimum choice from a water permeability perspective, butyl can be marginal from an aging point-of-view. The purpose of the present work was to derive better methods for predicting seal lifetimes and applying these methods to an important butyl material, Parker compound B6 12-70.
We have been working for many years to develop improved methods for predicting the lifetimes of polymers exposed to air environments and have recently turned our attention to seal materials. This paper describes an extensive study on a butyl material using elevated temperature compression stress-relaxation (CSR) techniques in combination with conventional oven aging exposures. The results initially indicated important synergistic effects when mechanical strain is combined with oven aging, as well as complex, non-Arrhenius behavior of the CSR results. By combining modeling and experiments, we show that diffusion-limited oxidation (DLO) anomalies dominate traditional CSR experiments. A new CSR approach allows us to eliminate DLO effects and recover Arrhenius behavior. Furthermore, the resulting CSR activation energy (E{sub a}) from 125 C to 70 C is identical to the activation energies for the tensile elongation and for the oxygen consumption rate of unstrained material over similar temperature ranges. This strongly suggests that the same underlying oxidation reactions determine both the unstrained and strained degradation rates. We therefore utilize our ultrasensitive oxygen consumption rate approach down to 23 C to show that the CSR E{sub a} likely remains unchanged when extrapolated below 70 C, allowing very confident room temperature lifetime predictions for the butyl seal.
Interpretation of compression stress-relaxation (CSR) experiments for elastomers in air is complicated by (1) the presence of both physical and chemical relaxation and (2) anomalous diffusion-limited oxidation (DLO) effects. For a butyl material, the authors first use shear relaxation data to indicate that physical relaxation effects are negligible during typical high temperature CSR experiments. They then show that experiments on standard CSR samples ({approximately}15 mm diameter when compressed) lead to complex non-Arrhenius behavior. By combining reaction kinetics based on the historic basic autoxidation scheme with a diffusion equation appropriate to disk-shaped samples, they derive a theoretical DLO model appropriate to CSR experiments. Using oxygen consumption and permeation rate measurements, the theory shows that important DLO effects are responsible for the observed non-Arrhenius behavior. To minimize DLO effects, they introduce a new CSR methodology based on the use of numerous small disk samples strained in parallel. Results from these parallel, minidisk experiments lead to Arrhenius behavior with an activation energy consistent with values commonly observed for elastomers, allowing more confident extrapolated predictions. In addition, excellent correlation is noted between the CSR force decay and the oxygen consumption rate, consistent with the expectation that oxidative scission processes dominate the CSR results.
For elastomers that will be used in applications involving long lifetimes, it is often necessary to first carry out and model accelerated aging experiments at higher than ambient temperatures, and then extrapolate the results in order to make lifetime predictions at the use temperature. Continuing goals in such endeavors are to better understand potential problems with such modeling approaches and to find ways of improving confidence in the predictions when the data are extrapolated. In this paper we will address several important issues involved in these procedures for elastomers exposed to air (oxygen), and discuss some potentially useful techniques and approaches which can increase confidence in lifetime predictions.
Because of the need to significantly extend the lifetimes of weapons, and because of potential implications of environmental O-ring failure on degradation of critical internal weapon components, the authors have been working on improved methods of predicting and verifying O-ring lifetimes. In this report, they highlight the successful testing of a new predictive method for deriving more confident lifetime extrapolations. This method involves ultrasensitive oxygen consumption measurements. The material studied is an EPDM formulation use for the environmental O-ring the W88. Conventional oven aging (155 C to 111 C) was done on compression molded sheet material; periodically, samples were removed from the ovens and subjected to various measurements, including ultimate tensile elongation, density and modulus profiles. Compression stress relaxation (CSR) measurements were made at 125 C and 111 C on disc shaped samples (12.7 mm diameter by 6 mm thick) using a Shawbury Wallace Compression Stress Relaxometer MK 2. Oxygen consumption measurements were made versus time, at temperatures ranging from 160 C to 52 C, using chromatographic quantification of the change in oxygen content caused by reaction with the EPDM material in sealed containers.
In order to probe the response of silicone door gasket materials to a postulated severe accident in an Italian nuclear power plant, compression stress relaxation (CSR) and compression set (CS) measurements were conducted under combined radiation (approximately 6 kGy/h) and temperature (up to 230{degrees}C) conditions. By making some reasonable initial assumptions, simplified constant temperature and dose rates were derived that should do a reasonable job of simulating the complex environments for worst-case severe events that combine overall aging plus accidents. Further simplification coupled with thermal-only experiments allowed us to derive thermal-only conditions that can be used to achieve CSR and CS responses similar to those expected from the combined environments that are more difficult to simulate. Although the thermal-only simulations should lead to sealing forces similar to those expected during a severe accident, modulus and density results indicate that significant differences in underlying chemistry are expected for the thermal-only and the combined environment simulations. 15 refs., 31 figs., 15 tabs.
The simplest general kinetic schemes applicable to the oxidation of polymers are presented, discussed and analyzed in terms of the underlying kinetic assumptions. For the classic basic autoxidation scheme (BAS), which involves three bimolecular termination steps and is applicable mainly to unstabilized polymers, typical assumptions used singly or in groups include (1) long kinetic chain length, (2) a specific ratio of the termination rate constants and (3) insensitivity to the oxygen concentration (e.g., domination by a single termination step). Steady-state solutions for the rate of oxidation are given in terms of one, two, three, or four parameters, corresponding respectively to three, two, one, or zero kinetic assumptions. The recently derived four-parameter solution predicts conditions yielding unusual dependencies of the oxidation rate on oxygen concentration and on initiation rate, as well as conditions leading to some unusual diffusion-limited oxidation profile shapes. For stabilized polymers, unimolecular termination schemes are typically more appropriate than bimolecular. Kinetics incorporating unimolecular termination reactions are shown to result in very simple oxidation expressions which have been experimentally verified for both radiation-initiated oxidation of an EPDM and thermoxidative degradation of nitrile and chloroprene elastomers.
Cables have been identified as critical components requiring detailed technical evaluation for extending the lifetime of Light Water Reactors beyond 40 years. This paper highlights some of the DOE-sponsored cable aging studies currently underway at Sandia. These studies are focused on two important issues: the validity of the often-used Arrhenius thermal aging prediction method and methods for predicting lifetimes in combined thermal-radiation environments. Accelerated thermal aging results are presented for three cable jacket and insulation materials, which indicate that hardening of the outside surface has an Arrhenius temperature dependence and correlates well with reductions in ultimate tensile elongation. This suggests that the indentor approach is a promising NDE technique for cable jacket and unjacketed insulation materials installed in thermally-dominated regions of nuclear power plants.
The Arrhenius relation predicts a linear relation between log of time to property change and inverse absolute temperature, with the Arrhenius activation energy E{sub a} given from the slope. For a nitrile rubber, Arrhenius behavior is observed for elongation vs air-oven aging temperature, with a E{sub a} of 22 kcal/mol. Confidence in extrapolation to low temperatures can be increased by measuring oxygen consumption. From 95 to 52 C, the E{sub a} for oxygen consumption is identical to that for elongation; however, below 52 C, the E{sub a} for oxygen consumption drops slightly to 18 kcal/mol, indicating that the extrapolation assumption probably overestimates the tensile property lifetime by a factor of about 2 at 23 C.
The Arrhenius approach assumes a linear relation between log time to material property change and inverse absolute temperature. For elastomers, ultimate tensile elongation results are often used to confirm Arrhenius behavior, even though the ultimate tensile strength is non-Arrhenius. This paper critically examines the Arrhenius approach. Elongation vs air-oven aging temperature for a nitrile rubber, gives an E{sub a} of 22 kcal/mol; however this does not hold for the tensile strength, indicating degradation. Modulus profiling shows heterogeneity at the earliest times at 125 C, caused by diffusion-limited oxidation (DLO). Tensile strength depends on the force at break integrated over the cross section, and nitrile rubbers aged at different temperatures experience different degrees of degradation in the interior. Modulus at the surface, however, is not affected by DLO anomalies. Severe mechanical degradation will occur when the edge modulus increases by an order of magnitude. 7 figs, 3 refs.
The author reports experimental measurements for the argon and oxygen permeability coefficients for the new EPDM material (SR793B-80) used for the environmental o-ring seals of the W88. The results allow the author to refine the argon gas analysis modeling predictions for W88 surveillance units. By comparing early surveillance results (up to four years in the field) with the modeling, the author shows that (1) up to this point in time, leakage past the seals is insignificant and (2) the argon approach should be able to inexpensively and easily monitor both integrated lifetime water leakage and the onset of any aging problems. Finally, the author provides a number of pieces of evidence indicating that aging of the SR793B-80 material will not be significant during the expected lifetime of the W88.
This paper describes the connection between mechanical degradation of common cable materials in radiation and elevated temperature environments and density increases caused by the oxidation which leads to this degradation. Two techniques based on density changes are suggested as potential non-destructive evaluation (NDE) procedures which may be applicable to monitoring the mechanical condition of cable materials in power plant environments. The first technique is direct measurement of density changes, via a density gradient column, using small shavings removed from the surface of cable jackets at selected locations. The second technique is computed X-ray tomography, utilizing a portable scanning device.
To allow more reliable estimates to be made of the amount of water that permeates through weapon environmental seals, we have generated extensive water permeability coefficient data for numerous o-ring materials, including, weapon-specific formulations of EPDM, butyl, fluorosilicone and silicone. For each material, data were obtained at several temperatures, ranging typically from 21[degrees]C to 80[degrees]C; for selected materials, the effect of relative humidity was monitored. Two different experimental techniques were used for most of the measurements, a permeability cup method and a weight gain/loss approach using, a sensitive microbalance. Good agreement was found between the results from the two methods, adding confidence to the reliability of the measurements. Since neither of the above methods was sufficiently sensitive to measure the water permeability of the butyl material at low temperatures, a third method, based on the use of a commercial instrument which employs a water-sensitive infrared sensor, was applied under these conditions.
In two earlier reports, we derived a time-temperature-dose rate superposition methodology, which, when applicable, can be used to predict cable degradation versus dose rate, temperature and exposure time. This methodology results in long-term predictive capabilities at the low dose rates appropriate to ambient nuclear power plant aging environments. The methodology was successfully applied to numerous important cable materials used in nuclear applications and the extrapolated predictions were verified by comparisons with long-term (7 to 12 year) results for similar or identical materials aged in nuclear environments. In this report, we test the methodology on three crosslinked polyolefin (CLPO) and two ethylene propylene rubber (EPR) cable insulation materials. The methodology applies to one of the CLPO materials and one of the EPR materials, allowing predictions to be made for these materials under low dose-rate, low temperature conditions. For the other materials, it is determined that, at low temperatures, a decrease in temperature at a constant radiation dose rate leads to an increase in the degradation rate for the mechanical properties. Since these results contradict the fundamental assumption underlying time-temperature-dose rate superposition, this methodology cannot be applied to such data. As indicated in the earlier reports, such anomalous results might be expected when attempting to model data taken across the crystalline melting region of semicrystalline materials. Nonetheless, the existing experimental evidence suggests that these CLPO and EPR materials have substantial aging endurance for typical reactor conditions. 28 refs., 26 figs., 3 tabs.
In this report, we provide a detailed discussion of methodology of predicting cable degradation versus dose rate, temperature, and exposure time and its application to data obtained on a number of additional nuclear power plant cable insulation (a hypalon, a silicon rubber and two ethylenetetrafluoroethylenes) and jacket (a hypalon) materials. We then show that the predicted, low-dose-rate results for our materials are in excellent agreement with long-term (7 to 9 years), low dose-rate results recently obtained for the same material types actually aged under nuclear power plant conditions. Based on a combination of the modelling and long-term results, we find indications of reasonably similar degradation responses among several different commercial formulations for each of the following generic'' materials: hypalon, ethylenetetrafluoroethylene, silicone rubber and PVC. If such generic'' behavior can be further substantiated through modelling and long-term results on additional formulations, predictions of cable life for other commercial materials of the same generic types would be greatly facilitated. Finally, to aid utilities in their cable life extension decisions, we utilize our modelling results to generate lifetime prediction curves for the materials modelled to data. These curves plot expected material lifetime versus dose rate and temperature down to the levels of interest to nuclear power plant aging. 18 refs., 30 figs., 3 tabs.
Analyses of the internal argon gas concentrations monitored on surveillance units of the W84 indicates that field aging of this weapon for times up to {approximately}4 years does not lead to important increases in the rate at which water leaks into the interior of the weapon. This implies that the EPDM environmental seals used on the W84 do not age significantly over this time period. By comparing the percentages of oxygen and argon in the internal atmosphere, an estimate of the oxygen consumption rate is made for a typical W84 unit. The argon gas analysis approach is then applied to the W88, which is sealed with a new EPDM material. Predictive expressions are derived which relate the anticipated argon gas concentrations of future, field-returned units to their water leakage rates. The predictions are summarized in convenient plots, which can be immediately and easily applied to surveillance data as reported. Since the argon approach is sensitive enough to be useful over the entire lifetime of the W88, it can be used to point out leaking units and to determine whether long-term aging has any significant effect on the new EPDM material. 11 refs., 10 figs., 3 tabs.
Diffusion-limited (heterogeneous) oxidation effects are often important for studies of polymer degradation. Such effects are common in polymers subjected to ionizing radiation at relatively high dose rate. To better understand the underlying oxidation processes and to aid in the planning of accelerated aging studies, it would be desirable to be able to monitor and quantitatively understand these effects. In this paper, we briefly review a theoretical diffusion approach which derives model profiles for oxygen surrounded sheets of material by combining oxygen permeation rates with kinetically based oxygen consumption expressions. The theory leads to a simple governing expression involving the oxygen consumption and permeation rates together with two model parameters {alpha} and {beta}. To test the theory, gamma-initiated oxidation of a sheet of commercially formulated EPDM rubber was performed under conditions which led to diffusion-limited oxidation. Profile shapes from the theoretical treatments are shown to accurately fit experimentally derived oxidation profiles. In addition, direct measurements on the same EPDM material of the oxygen consumption and permeation rates, together with values of {alpha} and {beta} derived from the fitting procedure, allow us to quantitatively confirm for the first time the governing theoretical relationship. 17 refs., 3 figs.
Whenever a new elastomer is formulated or an old formulation is modified, it is important to estimate the material's anticipated lifetime in various use environments. For extended lifetimes (years) this often requires the application of accelerated aging techniques which typically involve the modelling of results obtained at higher-than-ambient environmental stress levels. For many practical applications of elastomers, air is present during environmental exposures -- this usually implies that important oxidation effects underly the degradation of the material. Unfortunately, exposure of elastomers to air during aging often results in inhomogeneously oxidized samples, a complication which impacts attempts both to understand the oxidation process and to extrapolate accelerated exposures to long-term conditions. As has been clear for many years, in order to confidently extrapolate shorter-term accelerated simulations to long-term, air-aging conditions, one must be able to monitor and quantitatively understand diffusion-limited oxidation effects. In this review we will highlight some of the recent developments in both experimental techniques and theoretical modelling of relevance to this goal. 28 refs., 12 figs.