Nylon 6.6 accelerating aging studies: II. Long-term thermal-oxidative and hydrolysis results

Long-term (greater than 5 year exposures), low-temperature (as low as 37 °C) accelerated oven aging results were obtained for Nylon 6.6 fibers under thermo-oxidative conditions (air aging with an oxygen partial pressure of 13.2 cmHg in Albuquerque). To assess the importance of humidity on aging, experiments were also conducted under a combination of 100% RH plus 13.2 cmHg of oxygen partial pressure at temperatures ranging from 138 °C to 64 °C plus an additional experiment at 70% RH and 80 °C. The low-temperature tensile strength results showed that the Arrhenius activation energy under the pure oxidative degradation conditions dropped from ∼96 kJ/mol above ∼100 °C-∼30 kJ/mol below this temperature, indicative of a transition in the oxidative chemistry at low temperatures. Earlier work by our group on the same material concluded that hydrolytic degradation effects dominated oxidation effects at higher aging temperatures. However, the current long-term, low-temperature comparisons lead to the conclusion that humidity is not an important aging factor below ∼50 °C. By extrapolating time-temperature superposed oxidative degradation data using the low-temperature activation energy, we obtain predictions at 21 °C. At this temperature, we estimate that a tensile strength loss of 50% takes on the order of 70 years. The 21 °C predictions are shown to be reasonably consistent with long-term (up to 38 year) ambient results on similar Nylon materials removed from field-aged parachutes. Although the estimated average exposure temperature varies from parachute to parachute, the highest average temperature is estimated to be on the order of 21 °C.     

Durability of a polymer with triple-shape properties

A series of cyclic thermo-mechanical measurements was conducted on segregated poly(ester urethane) to study substantial changes in triple-shape properties as a result of hydrolytic aging (80 °C). Prior to the analysis of aging effects, a concept of triple-shape testing was elaborated, starting with the implementation of two distinct programming units. The first one included a deformation at 60 °C to ?_m1 = 100% (temporary shape B) and its fixing through soft segment crystallization by cooling to −20 °C under constant strain. The second one consisted of a deformation at −20 °C to ?_m2 = 200% (temporary shape A) and its stabilization through soft segment vitrification as achieved by cooling to −60 °C under fixed strain constraint. Then, gradual heating of the polymer from below to above its thermal transition temperatures gave two independent shape recovery responses in the reverse order of shape fixing: A → B through passing the glass transition by heating from −60 to 23 °C and B → C (back to the permanent shape), when heating the material from 23 to 60 °C and thus above its soft segment melting temperature. In a progressive approach, the storage of loading history through the sequential fixing of two temporary shapes was proven by the development of shape recovery stresses under constrained environment. With the implementation of the two testing methods several aging-related effects could be detected. Good shape fixing abilities ≥90% for both shapes were found and contrasted by significant changes in shape recoverabilities and stress storage capacities. Further insights derived from differential scanning calorimetry (DSC) measurements, indicating an aging-related growth in soft segment crystallinity, and dynamic mechanical analysis (DMA), suggesting a plasticizer effect of water onto the polymer matrix and that aging favoured an increase in cross-linking density.     

Laboratory accelerated and natural weathering of styrene-ethylene-butylene-styrene (SEBS) block copolymer

Indoor accelerated and outdoor weathering of polystyrene-b-(ethylene-co-butylene)-b-styrene (SEBS) was studied by infrared spectroscopy. Accelerated conditions involved simultaneous exposure of specimens to ultraviolet-visible radiation between 295 nm and 450 nm and each of four temperature/relative humidity (RH) environments, i.e., (a) 30 °C ± 1 °C at <1% RH, (b) 30 °C ± 1 °C at 80% RH, (c) 55 °C ± 1 °C at <1% RH, and (d) 55 °C ± 1 °C at 80% RH. Outdoor exposure was conducted in Gaithersburg, MD, in two different time periods. Similar photooxidative mechanisms were operative under all conditions. In the case of indoor accelerated exposure, the rate of photooxidation was found to depend strongly on temperature. Unlike the exposure at 55 °C, moisture-assisted photooxidation was insignificant at 30 °C. A quantitative study on the synergistic effect of environmental stressors revealed that the degrading effect of combined temperature and moisture on photooxidation was greater than the sum of the two effects exerted independently. Outdoor weathered specimens exhibited significantly slower photooxidation. Acceleration of photooxidation ranged from 2.5 to 10 times in comparison to the outdoor exposure, depending on the indoor accelerated conditions.     

Antioxidant behavior of a novel sulfur-bearing hindered phenolic antioxidant with a high molecular weight in polypropylene

A novel sulfur-bearing hindered phenolic antioxidant with a molecular weight of 1305.9 (SAO) was successfully synthesized via thiol-acrylate Michael addition reaction and its structure was clarified by nuclear magnetic resonance (NMR) and fourier transform infrared spectra (FTIR). The short-term oxidation induction time (OIT) of polypropylene (PP) compounds obtained at 210 °C showed that the OIT value of SAO-containing PP was higher than that of PP using Chinox 1035 with a molecular weight of 642.9 as a stabilizer. Long-term accelerated thermal aging test of PP compounds in an air oven at 150 °C, however, exhibited that the aging resistance of SAO-stabilizing PP was inferior to that of 1035-containing PP, quite contrary to their respective short-term effect on PP stabilization. The possible reasons of this contradiction were discussed from the viewpoint of the antioxidants' molecular structure and the limitations of the OIT approach in lifetime prediction.     

The effect of ozone and high temperature on polymer degradation in polymer core composite conductors

The next generation High Temperature Low Sag Polymer Core Composite Conductors can experience harsh in-service environments including high temperature and highly concentrated ozone. In some extreme cases, it is possible that the conductors will experience temperatures of up to 180 °C and ozone concentrations as high as 1% (10,000 ppm). Therefore, the goal of this work was to understand the degradation mechanisms in a high temperature epoxy, which could be used in the conductors at temperatures as high as 140 °C in the presence of 1% ozone. Then, the combined aging data for the epoxy were compared to the aging results from room temperature aging in 1% ozone and aging in air at 140 and 180 °C. In addition, important but limited aging testing was also performed on a set of PCCC rods to verify some of the observations from the neat resin experiments. It was determined that the mass loss, volumetric shrinkage, and flexural strength reductions of the epoxy aged at 140 °C were driven almost entirely by temperature and that the effect of 1% ozone at that temperature can be thought of as insignificant for aging times up to 90 days. The composite rods displayed postcuring at 140 °C and were also unaffected by the presence of ozone at aging time lengths of 90 days. Up to this time aging the polymer and composite specimens in atmospheric 180 °C resulted in the most drastic changes in both physical and mechanical properties, except viscoelasticity where the polymer specimens aged at 140 °C with 1% ozone showed the greatest increase in the storage modulus. The least amount of degradation to the materials was found to occur after aging at room temperature in 1% ozone.     

Investigation of the influence of different commercial softeners on the stability of poly(lactic acid) fabrics during storage

We have studied the potential degradation of poly(lactic acid)-based fabrics treated with commercial softeners and stored under two sets of conditions for one year. Initial wet-processing caused a fall in molecular weight of about 28%, irrespective of after-treatment. Storage at 40 °C and 80% RH produced further degradation which, with few exceptions, was aggravated by the presence of softeners. Ultimately, all samples degraded beyond the point of commercial usefulness. No clear distinction could be made between the effects of softeners having differing compositions. In contrast, fabrics stored under milder conditions of 23 °C and 50% RH showed no significant time-dependent polymer degradation, irrespective of the treatment applied. There were slight changes in tensile properties and some evidence of physical structural effects having occurred, which we attribute to physical aging. However, we do not believe these to be so serious as to call into question the long-term viability of PLA-based textile products.     

Thermal-oxidative aging of DGEBA/EPN/LMPA epoxy system: Chemical structure and thermal-mechanical properties

The evolvement of chemical structure and thermal-mechanical properties of diglycidyl ether of bisphenol-A and novolac epoxy resin blends cured with low molecular polyamide (DGEBA/EPN/LMPA system) during thermal-oxidative aging were investigated by Attenuated Total Reflectance Fourier Transform Infrared spectrometry (ATR-FTIR) and Dynamic Mechanical Thermal Analysis (DMTA). The results revealed that the chemical reactions during thermal-oxidative aging contained oxidation and chain scission. Some possible chemical reaction processes were given. There was a new compound formed during aging processes and the change of its glass transition temperature (T_g) with aging time followed an exponential law. In addition, the changes of dynamic mechanical behavior of this epoxy system aged at four different temperatures (110 °C, 130 °C, 150 °C, 170 °C) were compared. An empirical formula was obtained through kinetic analysis and this formula can be used to predict the oxidative degree of the surface at different aging temperature.     

Lifetime prediction of ABS polymers based on thermoanalytical data

The service life of ABS polymer, stabilized by 2-(3,5-di-tert-butyl-4-hydroxyanilino)-4,6-bis(octylthio)-1,3,5-triazine and containing 50% of a modifying rubber component, was estimated from oxidative induction times measured by DSC in isothermal mode in the temperature interval 140–170°C. The lifetime of ABS powder at the actual temperature of drying was predicted by linear extrapolation according to Arrhenius. However, the extrapolated value was much longer than the real lifetime determined from the long-term oven aging tests at 70 and 90°C, simulating the industrial drying process. The effect of changes in the apparent activation energy of oxidation due to antioxidant consumption during polymer aging is discussed.     

Sensor integration in rubber gaskets for structural health monitoring made by compression molding

This research work shows the integration process and characterization of a miniaturized strain gauge sensor in rubber O-rings for structural health monitoring (SHM). Strain gauges have been successfully embedded during compression molding, which is a commonly used fabrication method of rubber components. The sensor signal is correlated with the contact pressure of the gasket that abates over time due to aging processes. This can be exploited for lifetime prediction. Embedding sensors into rubber applying compression molding is a novel method that allows the integration into non-liquid elastomers. The strain gauge resistance correlates linearly to the contact pressure. An artificial aging test exhibits an exponential decrease in the resistance caused by the relaxation processes during the accelerated aging of the elastomer at 70 °C for 72 h. Uniaxial tensile testing with dumbbell specimens reveals the influence of the integrated sensors. It is demonstrated that the influence heavily depends on the sensor size.     

Lifetime predictions for semi-crystalline cable insulation materials: I. Mechanical properties and oxygen consumption measurements on EPR materials

Long-term accelerated aging studies (up to 7 years of aging) were conducted on four typical EPR materials used as cable insulation in nuclear power plant safety applications with the goal of establishing lifetime estimates at typical aging conditions of ∼50 °C. The four materials showed slow to moderate changes in mechanical properties (tensile elongation) until just before failure where abrupt changes occurred (so-called “induction-time” behavior). Time-temperature superposition was applied to derive shift factors and probe for Arrhenius behavior. Three of the materials showed reasonable time-temperature superposition with the empirically derived shift factors yielding an approximate Arrhenius dependence on temperature. Since the elongation results for the fourth material could not be successfully superposed, consistency with Arrhenius assumptions was impossible. For this material the early part of the mechanical degradation appeared to have an Arrhenius activation energy E_a of ∼100 kJ/mol (24 kcal/mol) whereas the post-induction degradation data had an E_a of ∼128 kJ/mol. Oxygen consumption measurements were used to confirm the 100 kJ/mol E_a found from early-time elongation results and to show that the chemistry responsible before the induction time is likely to remain unchanged down to 50 °C. Reasonable extrapolations of the induction-time results indicated 50 °C lifetimes exceeding 300 years for all four materials.     

Constitutive model calibration of the time and temperature-dependent behavior of high density polyethylene

HDPE is commonly used in pipelines and piping for industrial and societal infrastructure. Like most polymers, HDPE's mechanical properties are sensitive to temperature and show time dependent properties. The temperature effect on both the short and long term compressive and tensile behavior of HDPE, in a combined manner, have not been investigated thoroughly in the past. Especially the constitutive behavior of HDPE, incorporating temperature effects on its long and short term behavior, could be essential when designing such infrastructural components. Hence, the temperature effect on the short and long term response in tension and compression of HDPE is investigated in this study. The short term tensile and compressive stress-strain behavior at 23, 40, 60, and 80 °C were obtained through experiments at constant displacement rate and temperature. Tensile and compressive stress relaxation (e.g. long term) behavior at 23, 40, 50, 60, 70, and 80 °C were investigated through stress relaxation tests. The experimental results from the short term tests showed that both the tensile and compression moduli and yield strength of HDPE decrease linearly with the increase in temperature. It is also shown from the long term test that relaxation modulus in tension and compression are highly dependent on temperature. Based on the experimental results, the constitutive three network model (TNM) was calibrated and implemented in a FEA model, which was then validated through a three point bending (3 PB) relaxation test with a prescribed temperature profile. The FEA model and the calibrated model results agree markedly well with the experimental results, which indicates that the model can be used reliably to predict the temperature dependent short and long term behavior of HDPE in design and analysis of HDPE components.     

Effect of Aging on Mechanical Properties of Resorcinol-Formaldehyde Gels

Resorcinol-Formaldehyde gels have been prepared in aqueous solutions. After a gelification stage at 80°C, an aging was performed in water or acetic acid solutions at ambient temperature or in the parent liquid at 80°C for different durations. Shear modulus of gels immersed in water is measured using the 3 points bending technique. The evolution of elastic constant with time depends on the pH of aging solution. The strengthening is more pronounced for aging under acidic conditions than in water. Nevertheless when the aging stage is performed at 80°C for a few days, quite identical values of shear modulus are obtained comparatively to acid treatment. The enhancement of mechanical properties of RF gels in acidic conditions is related to polycondensation reaction rates.     

Lifetime predictions of EPR materials using the Wear-out approach

The Wear-out approach for lifetime prediction, based on cumulative damage concepts, is applied to several ethylene propylene rubber (EPR) cable insulation materials. EPR materials typically follow “induction-time” behavior in which their material properties change very slowly until just before failure, precluding the use of such time-dependent properties to predict failure. In the Wear-out approach, a material that has been aged at its ambient aging temperature T_a or at a low accelerated aging temperature is subsequently aged at a higher “Wear-out” temperature T_w in order to cause the material to reach its “failure” condition. In the simplest case, which involves the same chemical processes underlying degradation at T_a and T_w, a linear relationship is predicted between the time spent at T_a and the time required at T_w to complete the degradation. Data consistent with this expectation are presented for one of the EPR insulation materials. When the degradation chemistry at the two temperatures is different, a linear relationship between the time spent at T_a and the time required at T_w to complete the degradation is not generally expected. Even so, the Wear-out results for a second EPR material, which has evidence of changing chemistry, are reasonably linear and therefore useful from a predictive point-of-view. The Wear-out approach can therefore be used to transform non-predictive time-dependent material property results into predictive lifetime estimates. As a final example, the Wear-out approach is applied to an EPR insulation that had been aged in a nuclear power plant environment (∼51 °C) for times up to 23 years to show its likely viability for the hundreds of years predicted at this aging temperature from accelerated aging tests on EPR insulation materials.     

Effects of ultraviolet radiation, temperature and moisture on aging of coatings and sealants - A chemical and rheological study

Photodegradation of polymeric materials leads to significant modifications in both chemical properties and mechanical-rheological behaviors over time. Thus, it is important to characterize both properties to gain a better understanding of the durability of the materials. In this contribution, the chemorheological tools based upon Fourier transform infrared (FTIR) spectroscopy and dynamic mechanical thermal analysis (DMTA) were used to study the effects of temperature and moisture on photodegradation of a model sealant/coating system based upon a styrene-butadiene-styrene triblock copolymer. Specimens were exposed coincidentally to ultraviolet-visible radiation between 295 nm and 600 nm, and one of four different combinations of temperature and relative humidity (RH), i.e., (a) 30 °C and <1% RH, (b) 30 °C and 80% RH, (c) 55 °C and <1% RH, and (d) 55 °C and 80% RH. The rate of photodegradation was examined in terms of formation of oxidation species and evolution of mechanical-rheological data, including glass transition temperatures, moduli, and the number of effective crosslinked butadiene chains per unit volume per exposure time. Environmental exposure resulted in similar degradation modes for all four environments but the rate of photodegradation was found to depend strongly on temperature. Conversely, the role of moisture on photodegradation was not significant. The study shows that chemical modification can be directly related to the corresponding rheological modifications. In addition, the relative stability of styrene and butadiene against photodegradation as a function of temperature and moisture was compared.     

Compression set of thermoplastic polyurethane under different thermal-mechanical-moisture conditions

Elastomeric materials are used in the manufacture of structural dampeners due to their high damping coefficient and ease of production. However, elastomers, and in particular thermoplastic polyurethanes (TPU), are susceptible to degradation from environmental conditions. Samples of TPU were investigated, in terms of their mechanical properties, under the influence of four factors; time (up to 10 weeks thermal exposure), temperature (20-80 °C), strain (10% and 25%) and moisture (pre-soak/testing in water). Compression, hardness and compression set tests were used to determine the major contributors to the degradation process. It was found that pure thermal loading at 70 °C for 10 weeks did not result in any changes in material properties, other than an initial drying phase causing an increase in hardness of 2-3 Shore D. The compression set values were found to be heavily dependent on the test temperature, with a significant increase in compression set being seen between 70 and 80 °C. The presence of water (introduced by testing in water) acted as a plasticiser and resulted in a larger amount of compression set, than testing in the absence of water. The level of compression set was shown to be insensitive to the strain level. Overall, it was found, for the conditions tested, that temperature was the major driving force behind the compression set of the TPU material.     

Storage Stability Study of Salicylate-based Poly(anhydride-esters)

Storage stability was evaluated on a biodegradable salicylate-based poly(anhydride-ester) to elucidate the effects of storage conditions over time. The hydrolytically labile polymer samples were stored in powdered form at five relevant storage temperatures (−12 °C, 4 °C, 27 °C, 37 °C, 50 °C) and monitored over four weeks for changes in color, glass transition temperature, molecular weight, and extent of hydrolysis. Samples stored at lower temperatures remained relatively constant with respect to bond hydrolysis and molecular weight. Whereas, samples stored at higher temperatures displayed significant hydrolysis. For hydrolytically degradable polymers, such as these poly(anhydride-esters), samples are best stored at low temperatures under an inert atmosphere.     

Impact of formic/acetic acid and ammonia pre-treatments on chemical structure and physico-chemical properties of Miscanthus x giganteus lignins

Miscanthus x giganteus was treated with formic acid/acetic acid/water (30/50/20 v/v) for 3 h at 107 °C and 80 °C, and soaking in aqueous ammonia (25% w/w) for 6 h at 60 °C. The effects of these fractionation processes on chemical structure, physico-chemical properties and antioxidant activity of extracted lignins were investigated. Lignins were characterized by their purity, carbohydrate composition, thermal stability, molecular weight and by Fourier transform infrared (FTIR), 1H and quantitative 13C nuclear magnetic resonance (NMR), adiabatic broadband {13C-1H} 2D heteronuclear (multiplicity edited) single quantum coherence (g-HSQCAD). The radical scavenging activity towards 2,2-diphenyl-1-picrylhydrazyl (DPPH) was also investigated. Formic/acetic acid pretreatment performed in milder conditions (80 °C for 3 h) gave a delignification percentage of 44.7% and soaking in aqueous ammonia 36.3%.Formic/acetic acid pretreatment performed in harsh conditions (107 °C for 3 h) was more effective for extensive delignification (86.5%) and delivered the most pure lignin (80%). The three lignin fractions contained carbohydrate in different extent: 3% for the lignin obtained after the formic/acetic acid pretreatment performed at 107 °C (FAL-107), 5.8% for the formic/acetic acid performed at 80 °C (FAL-80) and 13.7% for the ammonia lignin (AL). The acid pretreatment in harsh conditions (FAL-107) resulted in cleavage of β-O-4′ bonds and aromatic C-C. Repolymerisation was thought to originate from formation of new aromatic C-O linkages. Under milder conditions (FAL-80) less β-O-4′ linkages were broken and repolymerisation took place to a lesser extent. Ammonia lignin was not degraded to a significant extent and resulted in the highest weight average 3140 g mol⁻¹. Despite the fact of FAL-107 repolymerisation, significant phenolic hydroxyls remained free, explaining the greater antioxidant activity.     

Comparison of enthalpy relaxation between two different molecular masses of a bisphenol-A polycarbonate

Summary The present work is an extension of an earlier study that compared the stress relaxation between two molecular masses of a bisphenol-A polycarbonate due to thermal aging. The enthalpy relaxation of the same materials has been characterized. First, by measuring the change in enthalpy loss (ΔH_a) and fictive temperature (T_f) as a function of aging temperature (T_a) ranging from -25 to 120°C, using differential scanning calorimetry. For the limited aging time of 120 h, ΔH_a and T_f changes were only appreciable for (T_g -70 K)<T_a<T_g . While the influence of molecular mass was somewhat discernible, enthalpy measurements were not as sensitive as stress relaxation tests in differentiating molecular mass effects. In a second investigation, the kinetics of enthalpy relaxation upon isothermal aging at 130°C was evaluated using the peak shift method and found to be comparable to literature values. The plot of ΔH_a as a function of log (aging time) showed two distinct regions: a brief non-linear portion (less than 1 h aging) which is followed by a linear relationship as typically reported in the literature. In contrast to the linear region, the non-linear relaxation behaviour of the poorly aged state does not appear to be dependent on molecular mass.     

Correlation of antioxidant depletion and mechanical performance during thermal degradation of an HTPB elastomer

Thermal degradation studies of a stabilized HTPB based elastomer were conducted at temperatures from 50 °C to 110 °C. The concentration of extractable antioxidant (AO2246) in the polymer was quantified via AO extraction and a gas chromatography-based method using internal standards. The decrease in extractable AO levels as a function of time and temperature was evaluated and correlated with mechanical property changes. Most importantly, AO depletion features were found to be temperature dependent. At elevated temperatures (>80 °C) extractable AO levels decreased rapidly and faster than the concurrent loss in mechanical properties. While extractable AO concentrations decrease quickly, the material is able to maintain some useful mechanical properties, perhaps via non-extractable or grafted AO species formed during degradation providing additional protection. At lower aging temperatures extractable or free AO levels decreased more slowly than the mechanical properties. Therefore, for condition monitoring purposes a universal correlation between AO levels and aging state or material condition could not be established. Most importantly, however, loss of mechanical properties and oxidative degradation is observed at lower temperatures despite significant levels of free antioxidant in the material. The antioxidant appears to be limited in its effectiveness to completely prevent degradation reactions, or only fractions of the total AO available are actually involved in the inhibition process.     

Thermal oxidation of clay-nanoreinforced polypropylene

The thermo-oxidation process at low temperatures for a montmorillonite-nanoreinforced polypropylene (PP) was studied. Experimental aging kinetic data at 100, 80 and 60 °C have been obtained and compared with a computational simulation in which a kinetic model based on the closed loop approach was used. As a result, it has been found that the montmorillonite role is not limited to a role of inert filler in the polymer matrix but induces a slight catalytic effect leading to induction period reduction. This effect has been well simulated by increasing initial hydroperoxyde concentration. The consequences of kinetic control by oxygen diffusion have also been investigated by using micro ATR-FTIR mapping to assess concentration profiles of the oxidation products across the sample thickness. It has been found that the oxidized layer thickness is close to 17 μm for the pure polypropylene whereas it is around 10 μm for the nanocomposite at 100 °C. These profile variations have been attributed to differences in oxygen diffusion coefficient values. Simulations based on the kinetic model including diffusion-reaction coupling describe these profiles well.