The most revealing indicator for oxidative processes or state of degraded plastics is usually carbonyl formation, a key step in materials degradation as part of the carbon cycle for man-made materials. Hence, the identification and quantification of carbonyl species with infrared spectroscopy have been the method of choice for generations, thanks to their strong absorbance and being an essential intermediate in carbon oxidation pathways. Despite their importance, precise identification and quantification can be challenging and rigorous fully traceable data are surprisingly rare in the existing literature. An overview of the complexity of carbonyl quantification is presented by the screening of reference compounds in solution with transmission and polymer films with ATR IR spectroscopy, and systematic data analyses. Significant variances in existing data and their past use have been recognized. Guidance is offered how better measurements and data reporting could be accomplished. Experimental variances depend on the combination of uncertainty in exact carbonyl species, extinction coefficient, contributions from neighboring convoluting peaks, matrix interaction phenomena and instrumental variations in primary IR spectral acquisition (refractive index and penetration depth for ATR measurements). In addition, diverging sources for relevant extinction coefficients may exist, based on original spectral acquisition. For common polymer degradation challenges, a relative comparison of carbonyl yields for a material is easily accessible, but quantification for other purposes, such as degradation rates and spatially dependent interpretation, requires thorough experimental validation. All variables highlighted in this overview demonstrate the significant error margins in carbonyl quantification, with exact carbonyl species and extinction coefficients already being major contributors on their own.
A series of networks is introduced with systematically varied network heterogeneity and high overall values of average glass transition temperature (Tg), based on polymerization of rigid acrylate and aromatic thiol monomers. The curing behavior, chain dynamics, and microstructure of these networks were investigated through a combination of dynamic mechanical analysis and infrared spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and x-ray scattering, respectively. The maximum Tg achieved during cure can be related to the breadth of the mechanical loss tangent, as others have previously suggested, as well as the temperature dependence of the chain dynamics in the network as monitored by 1H NMR. In addition, the microstructures of the networks are characterized by periodic, fractal microgels with characteristic length scales of ca. 20–40 nm. Intriguingly, this structural motif persists in the more homogeneous networks exhibiting comparatively narrow glass transitions and chain dynamics, indicating that dynamically homogeneous networks can still exhibit significant compositional heterogeneity at the mesoscale.
The current COVID-19 pandemic has resulted in globally constrained supplies for face masks and personal protective equipment (PPE). Production capacity is limited in many countries and the future course of the pandemic will likely continue with shortages for high quality masks and PPE in the foreseeable future. Hence, expectations are that mask reuse, extended wear and similar approaches will enhance the availability of personal protective measures. Repeated thermal disinfection could be an important option and likely easier implemented in some situations, at least on the small scale, than UV illumination, irradiation or hydrogen peroxide vapor exposure. An overview on thermal responses and ongoing filtration performance of multiple face mask types is provided. Most masks have adequate material properties to survive a few cycles (i.e. 30 min disinfection steps) of thermal exposure in the 75°C regime. Some are more easily affected, as seen by the fusing of plastic liner or warping, given that preferred conditioning temperatures are near the softening point for some of the plastics and fibers used in these masks. Hence adequate temperature control is equally important. As guidance, disinfectants sprayed via dilute solutions maintain a surface presence over extended time at 25 and 37°C. Some spray-on alcohol-based solutions containing disinfectants were gently applied to the top surface of masks. Neither moderate thermal aging (less than 24 h at 80 and 95°C) nor gentle application of surface disinfectant sprays resulted in measurable loss of mask filter performance. Subject to bio-medical concurrence (additional checks for virus kill efficiency) and the use of low risk non-toxic disinfectants, such strategies, either individually or combined, by offering additional anti-viral properties or short term refreshing, may complement reuse options of professional masks or the now ubiquitous custom-made face masks with their often unknown filtration effectiveness.
The current COVID-19 pandemic is stretching both the global supply for face masks and personal protective equipment (PPE). Production capacity is severely limited in many countries. This is a call for the R&D community, particularly to those in the polymer degradation and stability field. We have not only an opportunity but an obligation to engage and collaborate with virology and bio-medical experts. We require comparative R&D for extended, reuse and recyclability options. There is urgent need for large scale institutional approaches and methods that can be quickly applied locally by non-experts with limited resources.
Park, Jong R.; Van Guyse, Joachim F.R.; Podevyn, Annelore; Bolle, Eleonore C.L.; Bock, Nathalie; Linde, Carl E.; Celina, Mathias C.; Hoogenboom, Richard; Dargaville, Tim R.
Four drug-conjugated poly(2-alkyl-2-oxazoline) (PAOx) networks with different hydrophobicity were synthesized via copolymerization of either 2-methyl-, 2-ethyl-, 2-propyl- or 2-butyl-2-oxazoline with the functional monomer, 2-dec-9-enyl-2-oxazoline. The incorporation of a labile ester linkage between the polymer and the drug benazepril allowed for sustained drug release over periods of months with the release rates strongly depending on the hydrophobicity of the polymer pendant groups. Drug loading of 13 ± 2 wt% was used with 10 mol% crosslinking sites simply by tuning the thiol-ene stoichiometry. The networks exhibited negligible cell toxicity but cell repulsion was observed for hydrogels based on poly(2-methyl-2-oxazoline) and poly(2-ethyl-2-oxazoline) while those based on poly(2-n-propyl-2-oxazoline) and poly(2-n-butyl-2-oxaoline) showed cell adhesion. These results suggest that PAOx networks have great potential as drug delivery devices for long-lasting drug release applications.
The TED-GC–MS analysis is a two-step method. A sample is first decomposed in a thermogravimetric analyzer (TGA) and the gaseous decomposition products are then trapped on a solid-phase adsorber. Subsequently, the solid-phase adsorber is analyzed with thermal desorption gas chromatography mass spectrometry (TDU-GC–MS). This method is ideally suited for the analysis of polymers and their degradation processes. Here, a new entirely automated system is introduced which enables high sample throughput and reproducible automated fractioned collection of decomposition products. The fractionated collection together with low temperatures reduces the risk of contamination, improves instrumental stability and minimizes maintenance efforts. Through variation of the two main parameters (purge gas flow and heating rate) it is shown how the extraction process can be optimized. By measuring the decomposition products of polyethylene it is demonstrated that compounds with masses of up to 434 Da can be detected. This is achieved despite the low temperature (˜40 °C) of the solid-phase adsorber and the low thermal desorption temperature of 200 °C in the TDU unit. It is now shown that automated TED-GC–MS represents a new flexible multi-functional method for comprehensive polymer analyses. Comparable polymer characterization was previously only achievable through a combination of multiple independent analytical methods. This is demonstrated by three examples focused on practical challenges in materials analysis and identification: The first one is the analysis of wood plastic composites for which the decomposition processes of the polymer and the bio polymer (wood) could be clearly distinguished by fractionated collection using sequential adsorbers. Secondly, a fast quantitative application is shown by determining the weight concentrations of an unknown polyolefin blend through comparison with a reference material. Additionally, the determination of microplastic concentrations in environmental samples is becoming an increasingly important analytical necessity. It is demonstrated that with TED-GC–MS calibration curves showing good linearity for the most important precursors for microplastic, even complex matrix materials (suspended particulate matter) can be successfully analyzed.
The application, continued performance, and degradation behavior of polymers often depends on their interaction with small organic or gaseous volatiles. Understanding the underlying permeation and diffusion properties of materials is crucial for predicting their barrier properties (permeant flux), drying behavior, solvent loss or tendency to trap small molecules, as well as their interaction with materials in the vicinity due to off-gassing phenomena, perhaps leading to compatibility concerns. Further, the diffusion of low M w organics is also important for mechanistic aspects of degradation processes. Based on our need for improved characterization methods, a FTIR-based spectroscopic gas/volatile quantification setup was designed and evaluated for determination of the diffusion, desorption and transport behavior of small IR-active molecules in polymers. At the core of the method, a modified, commercially available IR transmission gas cell monitors time-dependent gas concentration. Appropriate experimental conditions, e.g. desorption or permeation under continuous flow or static gas conditions, are achieved using easily adaptable external components such as flow controllers and sample ampoules. This study presents overview approaches using the same IR detection methodology to determine diffusivity (desorption into a static gas environment, continuous gas flow, or intermittent desorption) and permeability (static and dynamic flow detection). Further, the challenges encountered for design and setup of IR gas quantification experiments, related to calibration and gas interaction, are presented. These methods establish desorption and permeation behavior of solvents (water and methanol), CO 2 off-gassing from foam, and offer simultaneous measurements of the permeation of several gases in a gas mixture (CO 2 , CO and CH 4 ) through polymer films such as epoxy and Kapton. They offer complementary guidance for material diagnostics and understanding of basic properties in sorption and transport behavior often of relevance to polymer degradation or materials reliability phenomena.
The use of self-assembling, pre-polymer materials in 3D printing is rare, due to difficulties of facilitating printing with low molecular weight species and preserving their reactivity and/or functions on the macroscale. Akin to 3D printing of small molecules, examples of extrusion-based printing of pre-polymer thermosets are uncommon, arising from their limited rheological tuneability and slow reactions kinetics. The direct ink write (DIW) 3D printing of a two-part resin, Epon 828 and Jeffamine D230, using a self-assembly approach is reported. Through the addition of self-assembling, ureidopyrimidinone-modified Jeffamine D230 and nanoclay filler, suitable viscoelastic properties are obtained, enabling 3D printing of the epoxy–amine pre-polymer resin. A significant increase in viscosity is observed, with an infinite shear rate viscosity of approximately two orders of magnitude higher than control resins, in addition to, an increase in yield strength and thixotropic behavior. Printing of simple geometries is demonstrated with parts showing excellent interlayer adhesion, unachievable using control resins.
A new approach is presented for conducting and extrapolating combined environment (radiation plus thermal) accelerated aging experiments. The method involves a novel way of applying the time-temperature-dose rate (t-T-R) approach derived many years ago, which assumes that by simultaneously accelerating the thermal-initiation rate (from Arrhenius T-only analysis) and the radiation dose rate R by the same factor x, the overall degradation rate will increase by the factor x. The dose rate assumption implies that equal dose yields equal damage, which is equivalent to assuming the absence of dose-rate effects (DRE).Aplot of inverse absolute temperature versus the log of the dose rate is used to indicate experimental conditions consistent with themodel assumptions, which can be derived along lines encompassing so-called matched accelerated conditions (MAC lines). Aging trends taken along MAC lines for several elastomers confirms the underlying model assumption and therefore indicates, contrary to many past published results, that DRE are typically not present. In addition, the MAC approach easily accommodates the observation that substantial degradation chemistry changes occur as aging conditions transition R-T space from radiation domination (high R, low T) to temperature domination (low R, high T). The MAC-line approach also suggests an avenue for gaining more confidence in extrapolations of accelerated MAC-line data to ambient aging conditions by using ultrasensitive oxygen consumption (UOC) measurements taken along the MAC line both under the accelerated conditions and at ambient. From UOC data generated under combined R-T conditions, this approach is tested and quantitatively confirmed for one of thematerials. In analogy to the wear-out approach developed previously for thermo-oxidative aging, the MAC-line concept can also be used to predict the remaining lifetimes of samples extracted periodically from ambient environments.
This report catalogues the results of a project exploring the incorporation of organometallic compounds into thermosetting polymers as a means to reduce their residual stress. Various syntheses of polymerizable ferro cene derivatives were attempted with mixed success. Ultimately, a diamine derivative of ferrocene was used as a curing agen t for a commercial epoxy resin, where it was found to give similar cure kinetics and mechanical properties in comparison to conventional curing agents. T he ferrocen e - based material is uniquely able to relax stress above the glass transition, leading to reduced cure stress. We propose that this behavior arises from the fluxional capacity of ferrocene. In support of this notion, nuclear magnetic resonance spectroscopy indicates a substantial increase in chain flexibility in the ferrocene - containing network. Although t he utilization of fluxionality is a novel approach to stress management in epoxy thermosets, it is anticipated to have greater impact in radical - cured ther mosets and linear polymers.
Physical stress relaxation in rubbery, thermoset polymers is limited by cross-links, which impede segmental motion and restrict relaxation to network defects, such as chain ends. In parallel, the cure shrinkage associated with thermoset polymerizations leads to the development of internal residual stress that cannot be effectively relaxed. Recent strategies have reduced or eliminated such cure stress in thermoset polymers largely by exploiting chemical relaxation processes, wherein temporary cross-links or otherwise transient bonds are incorporated into the polymer network. Here, we explore an alternative approach, wherein physical relaxation is enhanced by the incorporation of organometallic sandwich moieties into the backbone of the polymer network. A standard epoxy resin is cured with a diamine derivative of ferrocene and compared to conventional diamine curing agents. The ferrocene-based thermoset is clearly distinguished from the conventional materials by reduced cure stress with increasing cure temperature as well as unique stress relaxation behavior above its glass transition in the fully cured state. The relaxation experiments exhibit features characteristic of a physical relaxation process. Furthermore, the cure stress is observed to vanish precipitously upon deliberate introduction of network defects through an increasing imbalance of epoxy and amine functional groups. We postulate that these beneficial properties arise from fluxional motion of the cyclopentadienyl ligands on the polymer backbone.
When diethanolamine (DEA) is used as a curative for a DGEBA epoxy, a rapid “adduct-forming” reaction of epoxide with the secondary amine of DEA is followed by a slow “gelation” reaction of epoxide with hydroxyl and with other epoxide. Through an extensive review of previous investigations of simpler, but chemically similar, reactions, it is deduced that at low temperature the DGEBA/DEA gelation reaction is “activated” (shows a pronounced induction time, similar to autocatalytic behavior) by the tertiary amine in the adduct. At high temperature, the activated nature of the reaction disappears. The impact of this mechanism change on the kinetics of the gelation reaction, as resolved with differential scanning calorimetry, infrared spectroscopy, and isothermal microcalorimetry, is presented. It is shown that the kinetic characteristics of the gelation-reaction of the DGEBA/DEA system are similar to other tertiary-amine activated epoxy reactions and consistent with the anionic polymerization model previously proposed for this class of materials. Principle results are the time-temperature-transformation diagram, the effective activation energy, and the upper stability temperature of the zwitterion initiator of the activated gelation reaction. It is established that the rate of epoxide consumption cannot be generically represented as a function only of temperature and degree of epoxy conversion. The complex chemistry active in the material requires specific consideration of the dilute intermediates in the reaction sequence in order to define a model of the reaction kinetics applicable to all time-temperature cure histories.
The aim of this study was to alter polymerization chemistry to improve network homogeneity in free-radical crosslinked systems. It was hypothesized that a reduction in heterogeneity of the network would lead to improved mechanical performance. Experiments and simulations were carried out to investigate the connection between polymerization chemistry, network structure and mechanical properties. Experiments were conducted on two different monomer systems - the first is a single monomer system, urethane dimethacrylate (UDMA), and the second is a two-monomer system consisting of bisphenol A glycidyl dimethacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) in a ratio of 70/30 BisGMA/TEGDMA by weight. The methacrylate systems were crosslinked using traditional radical polymeriza- tion (TRP) with azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO) as an initiator; TRP systems were used as the control. The monomers were also cross-linked using activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) as a type of controlled radical polymerization (CRP). FTIR and DSC were used to monitor reac- tion kinetics of the systems. The networks were analyzed using NMR, DSC, X-ray diffraction (XRD), atomic force microscopy (AFM), and small angle X-ray scattering (SAXS). These techniques were employed in an attempt to quantify differences between the traditional and controlled radical polymerizations. While a quantitative methodology for characterizing net- work morphology was not established, SAXS and AFM have shown some promising initial results. Additionally, differences in mechanical behavior were observed between traditional and controlled radical polymerized thermosets in the BisGMA/TEGDMA system but not in the UDMA materials; this finding may be the result of network ductility variations between the two materials. Coarse-grained molecular dynamics simulations employing a novel model of the CRP reaction were carried out for the UDMA system, with parameters calibrated based on fully atomistic simulations of the UDMA monomer in the liquid state. Detailed metrics based on network graph theoretical approaches were implemented to quantify the bond network topology resulting from simulations. For a broad range of polymerization parameters, no discernible differences were seen between TRP and CRP UDMA simulations at equal conversions, although clear differences exist as a function of conversion. Both findings are consistent with experiments. Despite a number of shortcomings, these models have demonstrated the potential of molecular simulations for studying network topology in these systems.
We are studying PMDI polyurethane with a fast catalyst, such that filling and polymerization occur simultaneously. The foam is over-packed to tw ice or more of its free rise density to reach the density of interest. Our approach is to co mbine model development closely with experiments to discover new physics, to parameterize models and to validate the models once they have been developed. The model must be able to repres ent the expansion, filling, curing, and final foam properties. PMDI is chemically blown foam, wh ere carbon dioxide is pr oduced via the reaction of water and isocyanate. The isocyanate also re acts with polyol in a competing reaction, which produces the polymer. A new kinetic model is developed and implemented, which follows a simplified mathematical formalism that decouple s these two reactions. The model predicts the polymerization reaction via condensation chemis try, where vitrification and glass transition temperature evolution must be included to correctly predict this quantity. The foam gas generation kinetics are determined by tracking the molar concentration of both water and carbon dioxide. Understanding the therma l history and loads on the foam due to exothermicity and oven heating is very important to the results, since the kinetics and ma terial properties are all very sensitive to temperature. The conservation eq uations, including the e quations of motion, an energy balance, and thr ee rate equations are solved via a stabilized finite element method. We assume generalized-Newtonian rheology that is dependent on the cure, gas fraction, and temperature. The conservation equations are comb ined with a level set method to determine the location of the free surface over time. Results from the model are compared to experimental flow visualization data and post-te st CT data for the density. Seve ral geometries are investigated including a mock encapsulation part, two configur ations of a mock stru ctural part, and a bar geometry to specifically test the density model. We have found that the model predicts both average density and filling profiles well. However, it under predicts density gradients, especially in the gravity direction. Thoughts on m odel improvements are also discussed.
The accelerated aging behavior and aging state of a 30 year old field retrieved polysulfide elastomer was examined. The material is used as an environmental thread sealant for a stainless steel bolt in a steel threaded insert in an aluminum assembly. It is a two component curable polysulfide elastomer that is commercially available in a similar formulation as was applied 30 years ago. The primary goal of this study was to establish if aging over 30 years under moderate aging conditions (mostly ambient temperature and humidity) resulted in significant property changes, or if accelerated aging could identify developing aging pathways which would prevent the extended use of this material. The aging behavior of this material was examined in three ways: A traditional accelerated thermo-oxidative aging study between 95 to 140°C which focused on physical and chemical properties changes, an evaluation of the underlying oxidation rates between RT and 125°C, and an assessment of the aging state of a small 30 year old sample. All three data sets were used to establish aging characteristics, their time evolution, and to extrapolate the observed behavior to predict performance limits at RT. The accelerated aging study revealed a relatively high average activation energy of ~130 kJ/mol which gives overconfident performance predictions. Oxidation rates showed a decreasing behavior with aging time and a lower E a of ~84 kJ/mol from time - temperature superposition , but also predicted sufficient additional performance at RT. Consistent with these projections for extended RT performance, only small changes were observed for the 30 year old material. Extrapolations using this partially aged material also predict ongoing use as a viable option. Unexpected RT degradation could only develop into a concern should the oxidation rate not trend lower over time as was observed at elevated temperature. Considering all data acquired in this limited aging study , there are no immediately apparent concerns with this material for ongoing use. ACKNOWLEDGEMENTS We thank Lisa Deibler for providing us with a small sample of field aged and new commercial material.
Elastomers are often degraded when exposed to air or high humidity for extended times (years to decades). Lifetime estimates normally involve extrapolating accelerated aging results made at higher than ambient environments. Several potential problems associated with such studies are reviewed, and experimental and theoretical methods to address them are provided. The importance of verifying time-temperature superposition of degradation data is emphasized as evidence that the overall nature of the degradation process remains unchanged versus acceleration temperature. The confounding effects that occur when diffusion-limited oxidation (DLO) contributes under accelerated conditions are described, and it is shown that the DLO magnitude can be modeled by measurements or estimates of the oxygen permeability coefficient (POx) and oxygen consumption rate (Φ). POx and Φ measurements can be influenced by DLO, and it is demonstrated how confident values can be derived. In addition, several experimental profiling techniques that screen for DLO effects are discussed. Values of Φ taken from high temperature to temperatures approaching ambient can be used to more confidently extrapolate accelerated aging results for air-aged materials, and many studies now show that Arrhenius extrapolations bend to lower activation energies as aging temperatures are lowered. Best approaches for accelerated aging extrapolations of humidity-exposed materials are also offered.
The degradation in electrical contact resistance of a contact pair sliding while submerged in silicone fluid has been investigated. While the contamination of electrical contacts by silicone vapors or migrating species at elevated temperature due to decomposition in electric arcs is well known, the present degradation mechanism appears to arise from chemical reactions in the silicone fluid at room temperature, catalyzed by the presence of the freshly-abraded metal surface. As a result of these reactions, a deposit containing Si, C and O forms in the vicinity of mechanical contact. The specific contact metals present and the availability of dissolved oxygen in the fluid have a dramatic influence on the quantity of reaction product formed. The chemistry of the deposit, proposed formation mechanisms, the impact on electrical contact resistance and mitigation strategies are discussed.
We are developing computational models to help understand manufacturing processes, final properties and aging of structural foam, polyurethane PMDI. Th e resulting model predictions of density and cure gradients from the manufacturing process will be used as input to foam heat transfer and mechanical models. BKC 44306 PMDI-10 and BKC 44307 PMDI-18 are the most prevalent foams used in structural parts. Experiments needed to parameterize models of the reaction kinetics and the equations of motion during the foam blowing stages were described for BKC 44306 PMDI-10 in the first of this report series (Mondy et al. 2014). BKC 44307 PMDI-18 is a new foam that will be used to make relatively dense structural supports via over packing. It uses a different catalyst than those in the BKC 44306 family of foams; hence, we expect that the reaction kineti cs models must be modified. Here we detail the experiments needed to characteriz e the reaction kinetics of BKC 44307 PMDI-18 and suggest parameters for the model based on these experiments. In additi on, the second part of this report describes data taken to provide input to the preliminary nonlinear visco elastic structural response model developed for BKC 44306 PMDI-10 foam. We show that the standard cu re schedule used by KCP does not fully cure the material, and, upon temperature elevation above 150°C, oxidation or decomposition reactions occur that alter the composition of the foam. These findings suggest that achieving a fully cured foam part with this formulation may be not be possible through therma l curing. As such, visco elastic characterization procedures developed for curing thermosets can provide only approximate material properties, since the state of the material continuously evolves during tests.
As part of the Light Water Reactor Sustainability Program, science - based engineering approaches were employed to address cable degradation behavior under a range of exposure environments. Experiments were conducted with the goal to provide best guidance for aged material states, remaining life and expected performance under specific conditions for a range of cable materials. Generic engineering tests , which focus on rapid accelerated aging and tensile elongation , were combined with complementar y methods from polymer degradation science. Sandia's approach, building on previous years' efforts, enabled the generation of some of the necessary data supporting the development of improved lifetime predictions models, which incorporate known material b ehaviors and feedback from field - returned 'aged' cable materials. Oxidation rate measurements have provided access to material behavior under low dose rate thermal conditions, where slow degradation is not apparent in mechanical property changes. Such da ta have shown aging kinetics consistent with established radiati on - thermal degradation models. ACKNOWLEDGEMENTS We gratefully acknowledge ongoing technical support at the LICA facility and extensive sample handling provided by Maryla Wasiolek and Don Hans on. Sam Durbin and Patrick Mattie are recognized for valuable guidance throughout the year and assistance in the preparation of the final report. Doug Brunson is appreciated for sample analysis, compilation and plotting of experimental data.
Nuclear energy is one industry where aging of safety-related materials and components is of great concern. Many U.S. nuclear power plants are approaching, or have already exceeded, 40 years of age. Analysis comparing the cost of new plant construction versus long-term operation under extended plant licensing through 60 years strongly favors the latter option. To ensure the safe, reliable, and cost-effective long-term operation of nuclear power plants, many systems, structures, and components must be evaluated. Furthermore, as new analytical techniques and testing approaches are developed, it is imperative that we also validate, and if necessary, improve upon the previously employed Institute of Electrical and Electronic Engineers (IEEE) qualification standards originally written in 1974. Fortunately, this daunting task has global support, particularly in light of the new social and political climate surrounding nuclear energy in a post-Fukushima era.
We are developing computational models to elucidate the expansion and dynamic filling process of a polyurethane foam, PMDI. The polyurethane of interest is chemically blown, where carbon dioxide is produced via the reaction of water, the blowing agent, and isocyanate. The isocyanate also reacts with polyol in a competing reaction, which produces the polymer. Here we detail the experiments needed to populate a processing model and provide parameters for the model based on these experiments. The model entails solving the conservation equations, including the equations of motion, an energy balance, and two rate equations for the polymerization and foaming reactions, following a simplified mathematical formalism that decouples these two reactions. Parameters for the polymerization kinetics model are reported based on infrared spectrophotometry. Parameters describing the gas generating reaction are reported based on measurements of volume, temperature and pressure evolution with time. A foam rheology model is proposed and parameters determined through steady-shear and oscillatory tests. Heat of reaction and heat capacity are determined through differential scanning calorimetry. Thermal conductivity of the foam as a function of density is measured using a transient method based on the theory of the transient plane source technique. Finally, density variations of the resulting solid foam in several simple geometries are directly measured by sectioning and sampling mass, as well as through x-ray computed tomography. These density measurements will be useful for model validation once the complete model is implemented in an engineering code.
All polymers are intrinsically susceptible to oxidation, which is the underlying process for thermally driven materials degradation and of concern in various applications. There are many approaches for predicting oxidative polymer degradation. Aging studies usually are meant to accelerate oxidation chemistry for predictive purposes. Kinetic models attempt to describe reaction mechanisms and derive rate constants, whereas rapid qualification tests should provide confidence for extended performance during application, and similarly TGA tests are meant to provide rapid guidance for thermal degradation features. What are the underlying commonalities or diverging trends and complications when we approach thermo-oxidative aging of polymers in such different ways? This review presents a brief status report on the important aspects of polymer oxidation and focuses on the complexity of thermally accelerated polymer aging phenomena. Thermal aging and lifetime prediction, the importance of DLO, property correlations, kinetic models, TGA approaches, and a framework for predictive aging models are briefly discussed. An overall perspective is provided showing the challenges associated with our understanding of polymer oxidation as it relates to lifetime prediction requirements.
A selective literature review was conducted to assess whether currently available accelerated aging and original qualification data could be used to establish operational margins for the continued use of cable insulation and jacketing materials in nuclear power plant environments. The materials are subject to chemical and physical degradation under extended radiationthermal- oxidative conditions. Of particular interest were the circumstances under which existing aging data could be used to predict whether aged materials should pass loss of coolant accident (LOCA) performance requirements. Original LOCA qualification testing usually involved accelerated aging simulations of the 40-year expected ambient aging conditions followed by a LOCA simulation. The accelerated aging simulations were conducted under rapid accelerated aging conditions that did not account for many of the known limitations in accelerated polymer aging and therefore did not correctly simulate actual aging conditions. These highly accelerated aging conditions resulted in insulation materials with mostly inert aging processes as well as jacket materials where oxidative damage dropped quickly away from the air-exposed outside jacket surface. Therefore, for most LOCA performance predictions, testing appears to have relied upon heterogeneous aging behavior with oxidation often limited to the exterior of the cable cross-section a situation which is not comparable with the nearly homogenous oxidative aging that will occur over decades under low dose rate and low temperature plant conditions. The historical aging conditions are therefore insufficient to determine with reasonable confidence the remaining operational margins for these materials. This does not necessarily imply that the existing 40-year-old materials would fail if LOCA conditions occurred, but rather that unambiguous statements about the current aging state and anticipated LOCA performance cannot be provided based on original qualification testing data alone. The non-availability of conclusive predictions for the aging conditions of 40-year-old cables implies that the same levels of uncertainty will remain for any re-qualification or extended operation of these cables. The highly variable aging behavior of the range of materials employed also implies that simple, standardized aging tests are not sufficient to provide the required aging data and performance predictions for all materials. It is recommended that focused studies be conducted that would yield the material aging parameters needed to predict aging behaviors under low dose, low temperature plant equivalent conditions and that appropriately aged specimens be prepared that would mimic oxidatively-aged 40- to 60- year-old materials for confirmatory LOCA performance testing. This study concludes that it is not sufficient to expose materials to rapid, high radiation and high temperature levels with subsequent LOCA qualification testing in order to predictively quantify safety margins of existing infrastructure with regard to LOCA performance. We need to better understand how cable jacketing and insulation materials have degraded over decades of power plant operation and how this aging history relates to service life prediction and the performance of existing equipment to withstand a LOCA situation.
Liquid foams are viscoelastic liquids, exhibiting a fast relaxation attributed to local bubble motions and a slow response due to structural evolution of the intrinsically unstable system. In this work, these processes are examined in unique organic foams that differ from the typically investigated aqueous systems in two major ways: the organic foams (1) posses a much higher continuous phase viscosity and (2) exhibit a coarsening response that involves coalescence of cells. The transient and dynamic relaxation responses of the organic foams are evaluated and discussed in relation to the response of aqueous foams. The change in the foam response with increasing gas fraction, from that of a Newtonian liquid to one that is strongly viscoelastic, is also presented. In addition, the temporal dependencies of the linear viscoelastic response are assessed in the context of the foam structural evolution. These foams and characterization techniques provide a basis for testing stabilization mechanisms in epoxy-based foams for encapsulation applications.
Polymer foams are used as encapsulants to provide mechanical, electrical, and thermal isolation for engineered systems. In fire environments, the incident heat flux to a system or structure can cause foams to decompose. Commonly used foams, such as polyurethanes, often liquefy and flow during decomposition, and evolved gases can cause pressurization and ultimately failure of sealed containers. In systems safety and hazard analyses, numerical models are used to predict heat transfer to encapsulated objects or through structures. The thermo-mechanical response of systems involving coupled foam decomposition, liquefaction, and flow can be difficult to predict. Predicting pressurization of sealed systems is particularly challenging. To mitigate the issues caused by liquefaction and flow, hybrid polyurethane cyanate ester foams have been developed that have good adhesion and mechanical properties similar to currently used polyurethane and epoxy foams. The hybrid foam decomposes predictably during decomposition. It forms approximately 50 percent by weight char during decomposition in nitrogen. The foam does not liquefy. The charring nature of the hybrid foam has several advantages with respect to modeling heat transfer and pressurization. Those advantages are illustrated by results from recent radiant heat transfer experiments involving encapsulated objects, as well as results from numerical simulations of those experiments.
Both conventional and combinatorial approaches were used to study the pore formation process in epoxy based polymer systems. Sandia National Laboratories conducted the initial work and collaborated with North Dakota State University (NDSU) using a combinatorial research approach to produce a library of novel monomers and crosslinkers capable of forming porous polymers. The library was screened to determine the physical factors that control porosity, such as porogen loading, polymer-porogen interactions, and polymer crosslink density. We have identified the physical and chemical factors that control the average porosity, pore size, and pore size distribution within epoxy based systems.
Many weapons components (e.g. firing sets) are encapsulated with blown foams. Foam is a strong lightweight material--good compromise between conflicting needs of structural stability and electronic function. Current foaming processes can lead to unacceptable voids, property variations, cracking, and slipped schedules which is a long-standing issue. Predicting the process is not currently possible because the material is polymerizing and multiphase with changing microstructure. The goals of this project is: (1) Produce uniform encapsulant consistently and improve processability; (2) Eliminate metering issues/voids; (3) Lower residual stresses, exotherm to protect electronics; and (4) Maintain desired properties--lightweight, strong, no delamination/cracking, and ease of removal. The summary of achievements in the first year are: (1) Developed patentable chemical foaming chemistry - TA; (2) Developed persistent non-curing foam for systematic evaluation of fundamental physics of foams--Initial testing of non-curing foam shows that surfactants very important; (3) Identified foam stability strategy using a stacked reaction scheme; (4) Developed foam rheology methodologies and shear apparatuses--Began testing candidates for shear stability; (5) Began development of computational model; and (6) Development of methodology and collection of property measurements/boundary conditions for input to computational model.
The U.S. is addicted to petroleum--a dependency that periodically shocks the economy, compromises national security, and adversely affects the environment. If liquid fuels remain the main energy source for U.S. transportation for the foreseeable future, the system solution is the production of new liquid fuels that can directly displace diesel and gasoline. This study focuses on advanced concepts for biofuel factory production, describing three design concepts: biopetroleum, biodiesel, and higher alcohols. A general schematic is illustrated for each concept with technical description and analysis for each factory design. Looking beyond current biofuel pursuits by industry, this study explores unconventional feedstocks (e.g., extremophiles), out-of-favor reaction processes (e.g., radiation-induced catalytic cracking), and production of new fuel sources traditionally deemed undesirable (e.g., fusel oils). These concepts lay the foundation and path for future basic science and applied engineering to displace petroleum as a transportation energy source for good.
The optimization of piezo-electric PVDF polymers for adaptive optics in space environments was discussed. The fundamental correlation between chemical and physical features of various PVDF copolymers and piezoelectric properties was analyzed. Using LEO solar ultraviolet data, total UV energy depositions were estimated as equivalent radiation doses with significant doses predicted for the thin films. A good retention of piezo properties during γ-irradiation was observed despite concurrent polymer damage with crosslinking and morphological changes.
Thin polymer films have been identified as one of the major enabling technologies for future space-based systems. Potential devices include those based on piezoelectric bimorph polymers that deform when a charge is deposited, for example, from an electron gun. The thin-film and lightweight nature of the polymeric devices will allow them to be launched more readily and deployed to operating conditions once in orbit. Until now little work has been done aimed at investigating the performance of piezoelectric properties of PVDF and its copolymers and the prediction of their long-term stability in low Earth orbit (LEO) environmental conditions. In this paper, the piezoelectric properties of PVDF and the copolymers formed from polymerization of vinylidene fluoride and trifluoroethylene (TrFE) or hexafluoropropylene (HFP) have been studied over a broad temperature range simulating that expected in LEO. The temperatures experienced by unprotected polymers on low altitude spacecraft have previously been reported as ranging from approximately -100 C to +130 C as the polymer/spacecraft passes in and out of the Earth's shadow. To examine the effects of temperature on the piezoelectric properties of poled PVDF, P(VDF-TrFE) and P(VDF-HFP) the d{sub 33} piezoelectric coefficients and electric displacement-electric field (D-E) hysteresis loops were measured up to 160 C for the d{sub 33} measurements and from -80 to +110 C for the D-E loops. The room temperature d{sub 33} coefficient of PVDF homopolymer films, annealed for extended periods at 50, 80 and 125 C, dropped rapidly within a few days of heating, then remained unchanged for periods of up to 300 days. In contrast, the TrFE copolymer exhibited greater thermal stability than the homopolymer, with the d{sub 33} remaining almost unchanged from the pre-annealing value after heating at 50, 80 and 125 C. The HFP copolymer exhibited poor retention of d33 at temperatures above 80 C. For all three polymers short term annealing at 160 C reduced the d{sub 33} to zero. The decrease in d{sub 33} for the TrFE copolymer was correlated with the change in Curie temperature upon annealing of the copolymer, as observed by differential scanning calorimetry (DSC). Unlike radiation damage, which may occur from vacuum UV and atomic oxygen in LEO, the depoling of the polymers on exposure to elevated temperatures was attributed to a physical randomization of the morphology rather than a chemical degradation process. In situ D-E loop measurements over the temperature range -80 to +110 C showed that the remnant polarization of the TrFE copolymer was more stable than the PVDF homopolymer. These results suggest that the TrFE copolymer appears to have a better overall performance in thermal extremes compared with PVDF or an HFP copolymer.
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.
A hydroxy-terminated polybutadiene (HTPB)/isophorone diisocyanate (IPDI) elastomer is commonly used as propellant binder material. The thermal degradation of the binder is believed to be an important parameter governing the performance of the propellant. The aging of these binders can be monitored by mechanical property measurements such as modulus or tensile elongation. These techniques, however, are not easily adapted to binder agents that are dispersed throughout a propellant. In this paper the authors investigated solid state NMR relaxation times as a means to predict the mechanical properties of the binder as a function of aging time. {sup 1}H spin-lattice and spin-spin relaxation times were found to be insensitive to the degree of thermal degradation of the elastomer. Apparently these relaxation times depend on localized motions that are only weakly correlated with mechanical properties. A strong correlation was found between the {sup 13}C cross-polarization (CP) NMR time constant, T{sub cp}, and the tensile elongation at break of the elastomer as a function of aging time. A ramped-amplitude CP experiment was shown to be less sensitive to imperfections in setting critical instrumental parameters for this mobile material.
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.