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.