Determining weathering-induced heterogeneous oxidation profiles of polyethylene, polypropylene and polystyrene using laser-induced breakdown spectroscopy.

Weathering-induced polymer degradation is typically heterogeneous which plays an integral part in fragmentation. Despite that, the current selection of techniques to investigate such heterogeneities, especially beneath the sample surface, is sparse. We introduce Laser-induced Breakdown Spectroscopy (LIBS) as an analytical tool and evaluate its performance for depth profiling. Three types of polymers were selected (polyethylene, polypropylene, and polystyrene) that were aged under controlled conditions. We demonstrate that LIBS can detect heterogeneous oxidation on the surface and inside the samples. The results reveal that different oxidation behaviors are linked to the sample's lattice structure and the subsequent formation of microcracks. This implies that LIBS is beneficial to give additional insights into the weathering and degradation behavior of environmentally relevant plastics.

Carbon-based biosensors from graphene family to carbon dots: A viewpoint in cancer detection.

According to the latest report by International Agency for Research on Cancer, 19.3 million new cancer cases and 10 million cancer deaths were globally reported in 2020. Early diagnosis can reduce these numbers significantly, and biosensors have appeared to be a solution to this problem as, unlike the traditional methods, they have low cost, rapid process, and do not need experts present on site for use. These devices have been incorporated to detect many cancer biomarkers and measure cancer drug delivery. To design these biosensors, a researcher must know about their different types, properties of nanomaterials, and cancer biomarkers. Among all types of biosensors, electrochemical and optical biosensors are the most sensitive and promising sensors for detecting complicated diseases like cancer. The carbon-based nanomaterial family has attracted lots of attention due to their low cost, easy preparation, biocompatibility, and significant electrochemical and optical properties. In this review, we have discussed the application of graphene and its derivatives, carbon nanotubes (CNTs), carbon dots (CDs), and fullerene (C60), for designing different electrochemical and optical cancer-detecting biosensors. Furthermore, the application of these carbon-based biosensors for detecting seven widely studied cancer biomarkers (HER2, CEA, CA125, VEGF, PSA, Alpha-fetoprotein, and miRNA21) is reviewed. Finally, various fabricated carbon-based biosensors for detecting cancer biomarkers and anticancer drugs are comprehensively summarized as well.

New Functional Polymer Materials via Click Chemistry-Based Modification of Cellulose Acetate.

Cellulose acetate (CA) was partially acrylated, and the resulting cellulose acetate acrylate (acryl-substitution degree of 0.2) underwent quantitative thio-Michael click reactions with various thiols. A toolbox of functional CA polymers was obtained in this way, and their properties were studied. The modification with fatty alkyl thiols led to hydrophobic materials with large water drop contact angles. Octadecylthio-, butoxycarbonylpropylthio-, and furanylthio-modifications formed highly transparent materials. The new derivative CAASFur disintegrated completely under industrial composting conditions. Films of modified CA polymers were cast and investigated in terms of barrier properties. The nanocomposite of CAAS18 compounded with a synthetic layered silicate (hectorite) of a large aspect ratio showed permeabilities as low as 0.09 g mm m-2 day-1 for water vapor and 0.16 cm3 mm m-2 day-1 atm-1 for oxygen. This portfolio of functional CA polymers opens the door to new applications.

3D Printed Cellulose-Based Filaments-Processing and Mechanical Properties.

Cellulose is an abundant and sustainable material that is receiving more and more attention in different industries. In the context of additive manufacturing, it would be even more valuable. However, there are some challenges to overcome in processing cellulose-based materials. Therefore, this study used a new thermoplastic cellulose-based granulate to show its potential in filament extrusion and the fused filament fabrication printing process. Furthermore, the mechanical properties were investigated. It was shown that filaments with a suitable and uniform diameter could be produced. A parameter study for printing revealed that adhesion of the material on the bed and between layers was an issue but could be overcome with a suitable set of parameters. Tensile bars with different orientations of 0°, +/-45°, and 90° were printed and compared with injection-molded samples. It could be shown that different mechanisms (single strand breakage, shear failure) caused fracture for different printing orientations. In comparison with injection-molding, the printed parts showed lower mechanical properties (moduli of 74-95%, a tensile strength of 47-69%, and an elongation at break of 29-60%), but an improvement could be seen compared with earlier reported direct granule printing. The study showed that FFF is a suitable process for the new cellulose-based material to fabricate samples with good mechanical properties.

Influence of Sample Wetting Method on ESC-Behavior of PMMA under Dynamic Fatigue Crack Propagation.

Environmental stress cracking (ESC) is one of the most prominent failure mechanisms for polymer components. The high sensitivity of plastics in regard to environmental influences has always meant that plastics as materials have been viewed very critically in outdoor applications. Recently, the massive occurrence of microplastics in the environment means that questions about the long-term stability of plastic parts and the studies of plastic fragmentation are of great scientific interest. ESC behavior also plays an important role in connection with the formation of microplastics. In this work, the influence of two different sample wetting methods on ESC behavior was investigated. In case A, the sample was in situ wetted with the medium during the measurement by using a sponge. In case B, the sample was wetted by storage in the medium prior to measurement. Different stress cracking agents (SCA) were examined for polymethylmethacrylate (PMMA). Fracture-mechanical fatigue crack propagation (FCP) tests were carried out to quantitatively determine the sensitivity to ESC. Correlations between the absorption behavior and the ESC behavior of the SCA and the resulting morphological phenomena were established. Depending on the wetting method, significant differences in FCP were observed. The in situ wetting of the samples (case A) during the FCP measurement with ethylene glycol (EG) and with deionized water (DI) led to a significant shift in the crack propagation curves to higher ∆K-compared to the PMMA reference. In the case of n-heptane (NH), a more brittle crack propagation behavior was observed due to the chemical interaction with PMMA. The previously immersed samples (case B) give different results. Storage in NH and EG showed no influence on the crack propagation behavior. Samples immersed in DI showed a completely different course of crack growth. At a certain load, a sudden deceleration of the crack propagation and thus a horizontal curve could be seen. Above a certain ∆K value, crack growth began again. Depending on the immersion time (14, 30, or 60 days), this so-called stepped behavior shifted to lower da/dN values.

Novel Expandable Epoxy Beads and Epoxy Particle Foam.

Expanded polymeric beads offer the advantage of being able to produce parts with complex geometries through a consolidation process. However, established polymeric beads are made of thermoplastics, deform and melt beyond their temperature services. In this manuscript, a new technique is proposed to fabricate expandable epoxy beads (EEBs), then expand and fuse them to produce epoxy particle foams (EPFs). This technique is called solid-state carbamate foaming technique. For production of EEBs, a mixture of epoxy, carbamate and hardener is prepared and poured into a 10 mL syringe. The mixture is manually extruded into 60 °C water to obtain a cylindric shape. The extrudate is then further cured to obtain an epoxy oligomer behaving rheological tan delta 3 and 2 at 60 °C. The extrudate is cut into pellets to obtain EEBs. The EEBs are then loaded into an aluminum mold and placed in an oven at 160 °C to expand, fuse to obtain EPFs of 212 kg/m3 and 258 kg/m3. The obtained EPFs provide a Tg of 150-154 °C. The fusion boundaries in EPFs are well formed. Thus, the produced EPFs exhibit a compressive modulus of 50-70 MPa, with a torsion storage modulus at 30 °C of 34-56 MPa.

Comparison of Melting Processes for WPC and the Resulting Differences in Thermal Damage, Emissions and Mechanics.

The necessity for resource-efficient manufacturing technologies requires new developments within the field of plastic processing. Lightweight design using wood fibers as sustainable reinforcement for thermoplastics might be one solution. The processing of wood fibers requires special attention to the applied thermal load. Even at low processing temperatures, the influence of the dwell time, temperature and shear force is critical to ensure the structural integrity of fibers. Therefore, this article compares different compounding rates for polypropylene with wood fibers and highlights their effects on the olfactory, visual and mechanical properties of the injection-molded part. The study compares one-step processing, using an injection-molding compounder (IMC), with two-step processing, using a twin-scew-extruder (TSE), a heating/cooling mixer (HCM) and an internal mixer (IM) with subsequent injection molding. Although the highest fiber length was achieved by using the IMC, the best mechanical properties were achieved by the HCM and IM. The measured oxidation induction time and volatile organic compound content indicate that the lowest amount of thermal damage occurred when using the HCM and IM. The advantage of one-time melting was evened out by the dwell time. The reinforcement of thermoplastics by wood fibers depends more strongly on the structural integrity of the fibers compared to their length and homogeneity.

Degradation of low-density polyethylene to nanoplastic particles by accelerated weathering.

When plastics enter the environment, they are exposed to abiotic and biotic impacts, resulting in degradation and the formation of micro- and nanoplastic. Microplastic is ubiquitous in every environmental compartment. Nevertheless, the underlying degradation processes are not yet fully understood. Here, we studied the abiotic degradation of commonly used semi-crystalline, low-density polyethylene (LDPE) in a long-term accelerated weathering experiment combining several macro- and microscopic methods. Based on our observations, the degradation of LDPE proceeds in three stages. Initially, LDPE objects are prone to abrasion, followed by a period of surface cracking. A large number of secondary particles with a high degree of crystallinity are formed, with sizes down to the nanometer scale. These particles consist of highly polar oligomers leading to agglomeration in the final stage. We therefore suppose that weathered microplastic and nanoplastic particles will attach to colloidal environmental matter. This offers an explanation for the absence of free nanoplastic particles in natural samples.

Foam 3D Printing of Thermoplastics: A Symbiosis of Additive Manufacturing and Foaming Technology.

Due to their light-weight and cost-effectiveness, cellular thermoplastic foams are considered as important engineering materials. On the other hand, additive manufacturing or 3D printing is one of the emerging and fastest growing manufacturing technologies due to its advantages such as design freedom and tool-less production. Nowadays, 3D printing of polymer compounds is mostly limited to manufacturing of solid parts. In this context, a merged foaming and printing technology can introduce a great alternative for the currently used foam manufacturing technologies such as foam injection molding. This perspective review article tackles the attempts taken toward initiating this novel technology to simultaneously foam and print thermoplastics. After explaining the basics of polymer foaming and additive manufacturing, this article classifies different attempts that have been made toward generating foamed printed structures while highlighting their challenges. These attempts are clustered into 1) architected porous structures, 2) syntactic foaming, 3) post-foaming of printed parts, and eventually 4) printing of blowing agents saturated filaments. Among these, the latest approach is the most practical route although it has not been thoroughly studied yet. A filament free approach that can be introduced as a potential strategy to unlock the difficulties to produce printed foam structures is also proposed.

Impact of Enzymatic Degradation on the Material Properties of Poly(Ethylene Terephthalate).

With macroscopic litter and its degradation into secondary microplastic as a major source of environmental pollution, one key challenge is understanding the pathways from macro- to microplastic by abiotic and biotic environmental impact. So far, little is known about the impact of biota on material properties. This study focuses on recycled, bottle-grade poly(ethylene terephthalate) (r-PET) and the degrading enzyme PETase from Ideonella sakaiensis. Compact tension (CT) specimens were incubated in an enzymatic solution and thermally and mechanically characterized. A time-dependent study up to 96 h revealed the formation of steadily growing colloidal structures. After 96 h incubation, high amounts of BHET dimer were found in a near-surface layer, affecting crack propagation and leading to faster material failure. The results of this pilot study show that enzymatic activity accelerates embrittlement and favors fragmentation. We conclude that PET-degrading enzymes must be viewed as a potentially relevant acceleration factor in macroplastic degradation.

Investigations on Epoxy-Carbamate Foams Modified with Different Flame Retardants for High-Performance Applications.

In transport sectors such as aviation, automotive and railway, materials combining a high lightweight potential with high flame retardant properties are in demand. Polymeric foams are suitable materials as they are lightweight, but often have high flammability. This study focuses on the influence of different flame retardants on the burning behavior of Novolac based epoxy foams using Isophorone Diamine carbamate (B-IPDA) as dual functional curing and blowing agent. The flame retardant properties and possible modifications of these foams are systematically investigated. Multiple flame retardants, representing different flame retardant mechanisms, are used and the effects on the burning behavior as well as mechanical and thermal properties are evaluated. Ammonium polyphosphate (APP), used with a filler degree of 20 wt.% or higher, functions as the best performing flame retardant in this study.

Investigation of the Thermal and Hydrolytic Degradation of Polylactide during Autoclave Foaming.

Polylactide (PLA) is one of the most important bioplastics worldwide and thus represents a good potential substitute for bead foams made of the fossil-based Polystyrene (PS). However, foaming of PLA comes with a few challenges. One disadvantage of commercially available PLA is its low melt strength and elongation properties, which play an important role in foaming. As a polyester, PLA is also very sensitive to thermal and hydrolytic degradation. Possibilities to overcome these disadvantages can be found in literature, but improving the properties for foaming of PLA as well as the degradation behavior during foaming have not been investigated yet. In this study, reactive extrusion on a twin-screw extruder is used to modify PLA in order to increase the melt strength and to protect it against thermal degradation and hydrolysis. PLA foams are produced in an already known process from the literature and the influence of the modifiers on the properties is estimated. The results show that it is possible to enhance the foaming properties of PLA and to protect it against hydrolysis at the same time.

New Insights on Expandability of Pre-Cured Epoxy Using a Solid-State CO2-Foaming Technique.

Foaming an epoxy is challenging because the process involves the curing reaction of epoxy and hardener (from monomer to oligomer, to a gel and a final three-dimensional crosslinked network) and the loading of gas phase into the epoxy phase to develop the cellular structure. The latter process needs to be carried out at the optimum curing stage of epoxy to avoid cell coalescence and to allow expansion. The environmental concern regarding the usage of chemical blowing agent also limits the development of epoxy foams. To surmount these challenges, this study proposes a solid-state CO2 foaming of epoxy. Firstly, the resin mixture of diglycidylether of bisphenol-A (DGEBA) epoxy and polyamide hardener is pre-cured to achieve various solid-state sheets (preEs) of specific storage moduli. Secondly, these preEs undergo CO2 absorption using an autoclave. Thirdly, CO2 absorbed preEs are allowed to free-foam/expand in a conventional oven at various temperatures; lastly, the epoxy foams are post-cured. PreE has a distinctive behavior once being heated; the storage modulus is reduced and then increases due to further curing. Epoxy foams in a broad range of densities could be fabricated. PreE with a storage modulus of 4 × 104-1.5 × 105 Pa at 30 °C could be foamed to densities of 0.32-0.45 g/cm3. The cell morphologies were revealed to be star polygon shaped, spherical and irregularly shaped. The research proved that the solid-state CO2-foaming technique can be used to fabricate epoxy foams with controlled density.

Tailoring Epoxy Resin Foams by Pre-Curing with Neat Amine Hardeners and Its Derived Carbamates.

The use of amine-based carbamates with their dual function, acting as amine curing agents and CO2 blowing agents after their decomposition without by-products, are promising for ecofriendly epoxy foams as high-performance materials. However, controlling cell morphology requires a proper adjustment of the viscosity at the foaming step. The viscosity is altered not only by blending neat amine and its derived carbamate at a fixed pre-curing time, but also by changing the pre-curing time at a fixed blend ratio. Within this study, diglycidylether of bisphenol A (DGEBA) epoxy resin is mixed with different blend ratios of isophorone diamine (IPDA) and its derived carbamate (B-IPDA). The systems are characterized by DSC and rheology experiments to identify the pre-curing effects on the derived epoxy foams. Epoxy foams at a blend ratio of 30/70w IPDA/B-IPDA showed the best foam morphology and an optimum Tg compared to other blend ratios. Furthermore, it was found that both pre-curing times, 2 h and 3 h, for the 30/70w IPDA/B-IPDA system reveal a more homogeneous cell structure. The study proves that the blending of neat amine and carbamate is beneficial for the foaming performance of carbamate systems.

Insights into the Bead Fusion Mechanism of Expanded Polybutylene Terephthalate (E-PBT).

Expandable polystyrene (EPS) and expanded polypropylene (EPP) dominate the bead foam market. As the low thermal performance of EPS and EPP limits application at elevated temperatures novel solutions such as expanded polybutylene terephthalate (E-PBT) are gaining importance. To produce parts, individual beads are typically molded by hot steam. While molding of EPP is well-understood and related to two distinct melting temperatures, the mechanisms of E-PBT are different. E-PBT shows only one melting peak and can surprisingly only be molded when adding chain extender (CE). This publication therefore aims to understand the impact of thermal properties of E-PBT on its molding behavior. Detailed differential scanning calorimetry was performed on neat and chain extended E-PBT. The crystallinity of the outer layer and center of the bead was similar. Thus, a former hypothesis that a completely amorphous bead layer enables molding, was discarded. However, the incorporation of CE remarkably reduces the crystallization and re-crystallization rate. As a consequence, the time available for interdiffusion of chains across neighboring beads increases and facilitates crystallization across the bead interface. For E-PBT bead foams, it is concluded that sufficient time for polymer interdiffusion during molding is crucial and requires adjusted crystallization kinetics.

Transparent PC/PMMA Blends with Enhanced Mechanical Properties via Reactive Compounding of Functionalized Polymers.

Reactive compounding of terminally phenolic OH-functionalized polycarbonate (PC) with epoxy-functionalized polymethylmethacrylate (PMMA) prepared by copolymerization with glycidyl methacrylate was investigated. It was spectroscopically demonstrated that a PC/PMMA copolymer was formed during the melt reaction of the functional groups. Zirconium acetylacetonate could catalytically accelerate this reaction. Correlations of the phenomenological (optical and mechanical) properties with the molecular level and mesoscopic (morphological) structure were discussed. By the investigated reactive compounding process, transparent PC/PMMA blends with two-phase morphologies were obtained in a continuous twin-screw extruder, which, for the first time, combined the high transmission of visible light with excellent mechanical performance (e.g., synergistically improved tensile and flexural strength and high scratch resistance). The transparency strongly depended on (a) the degree of functionalization in both PC and PMMA, (b) the presence of the catalyst, and (c) the residence time of the compounding process. The in-situ-formed PC/PMMA copolymer influenced the observed macroscopic properties by (a) a decrease in the interphase tension, leading to improved and stabilized phase dispersion, (b) the formation of a continuous gradient of the polymer composition and thus of the optical refractive indices in a diffuse mesoscopic interphase layer separating the PC and PMMA phases, and (c) an increase in the phase adhesion between PC and PMMA due to mechanical polymer chain entanglement in this interphase.