RESUMEN

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.

RESUMEN

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.

RESUMEN

In the original publication [...].

RESUMEN

Due to their lightweight potential and good eco-balance, thermoplastic hybrid composites with natural fiber reinforcement have long been used in the automotive industry. A good alternative to natural fibers is wood fibers, which have similar properties but are also a single-material solution using domestic raw materials. However, there has been hardly any research into wood fibers in thermoplastic back-injected hybrid composites. This article compares the bond strength of an injection molded rib from polypropylene (PP) and wood fibers to different non-wovens. The non-wovens consisted of wood fibers (spruce) or alternatively natural fibers (kenaf, hemp), both with a polypropylene matrix. Pull-off and instrumented puncture impact tests show that, given similar parameters, the natural and wood-fiber-hybrid composites exhibit very similar trends in bond strength. Further tests using viscosity measurements, microscopy, and computed tomography confirm the results. Wood-fiber-reinforced thermoplastic hybrid composites can thus compete with the natural fiber composites in terms of their mechanical behavior and therefore present a good alternative in technical semi-structural applications.

RESUMEN

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.

Asunto(s)

RESUMEN

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.

Asunto(s)

RESUMEN

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.

RESUMEN

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.

RESUMEN

This study focuses on the effect of part geometry and infill degrees on effective mechanical properties of extrusion additively manufactured stainless steel 316L parts produced with BASF's Ultrafuse 316LX filament. Knowledge about correlations between infill degrees, mechanical properties and dimensional deviations are essential to enhance the part performance and further establish efficient methods for the product development for lightweight metal engineering applications. To investigate the effective Young's modulus, yield strength and bending stress, standard testing methods for tensile testing and bending testing were used. For evaluating the dimensional accuracy, the tensile and bending specimens were measured before and after sintering to analyze anisotropic shrinkage effects and dimensional deviations linked to the infill structure. The results showed that dimensions larger than 10 mm have minor geometrical deviations and that the effective Young's modulus varied in the range of 176%. These findings provide a more profound understanding of the process and its capabilities and enhance the product development process for metal extrusion-based additive manufacturing.

RESUMEN

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.

RESUMEN

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.

RESUMEN

Polystyrene foams have become more and more important owing to their lightweight potential and their insulation properties. Progress in this field is expected to be realized by foams featuring a microcellular morphology. However, large-scale processing of low-density foams with a closed-cell structure and volume expansion ratio of larger than 10, exhibiting a homogenous morphology with a mean cell size of approximately 10 µm, remains challenging. Here, we report on a series of 4,4'-diphenylmethane substituted bisamides, which we refer to as kinked bisamides, acting as efficient supramolecular foam cell nucleating agents for polystyrene. Self-assembly experiments from solution showed that these bisamides form supramolecular fibrillary or ribbon-like nanoobjects. These kinked bisamides can be dissolved at elevated temperatures in a large concentration range, forming dispersed nano-objects upon cooling. Batch foaming experiments using 1.0 wt.% of a selected kinked bisamide revealed that the mean cell size can be as low as 3.5 µm. To demonstrate the applicability of kinked bisamides in a high-throughput continuous foam process, we performed foam extrusion. Using 0.5 wt.% of a kinked bisamide yielded polymer foams with a foam density of 71 kg/m3 and a homogeneous microcellular morphology with cell sizes of ≈10 µm, which is two orders of magnitude lower compared to the neat polystyrene reference foam with a comparable foam density.

RESUMEN

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.

RESUMEN

The effect of plasma treatment of the multi-walled carbon nanotube (MWCNT) surface on the fracture toughness of an aerospace grade epoxy resin and its unidirectional (UD) carbon fiber prepreg laminates has attracted scientific interest. A prepreg route eliminates the possible risk of carbon nanotube filtration by unidirectional carbon fibers. X-ray photoelectron spectroscopy results suggested that oxygen atom concentration at the nanotube surface was increased from 0.9% to 3.7% after plasma modification of the carbon nanotubes. A low number (up to 0.5 wt.%) of MWCNTs was added to epoxy resin and their carbon fiber prepreg laminates. Transmission electron micrographs revealed that the plasma treatment resulted in a better dispersion and distribution of MWCNTs in the epoxy resin. Plasma-treated MWCNTs resulted in a more pronounced resistance to the crack propagation of epoxy resin. During the production of the reference and nanotube-modified prepregs, a comparable prepreg quality was achieved. Neat nanotubes agglomerated strongly in the resin-rich regions of laminates lowering the interlaminar fracture toughness under mode I and mode II loading. However, plasma-treated nanotubes were found mostly as single particles in the resin-rich regions of laminates promoting higher energy dissipation during crack propagation via a CNT pull-out mechanism.

RESUMEN

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.

RESUMEN

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.

RESUMEN

Bead foams serve in a wide variety of applications, from insulation and packaging to midsoles in shoes. However, the currently used materials are limited to somewhat low temperature or exhibit significant changes in modulus in the temperature range of many applications due to their glass transition. By comparison, polycarbonate (PC) exhibits almost constant mechanics for temperatures up to 130 °C. Therefore, it appears as an advantageous base material for bead foams. The aim of the publication is to provide comprehensive data on the properties of expanded PC (EPC) in comparison to already commercially available expanded polypropylene, EPP, and expanded polyethylene-terephthalate, EPET. A special focus is set on the thermo-mechanical properties as these are the most lacking features in current materials. In this frame, dynamic mechanical analysis, and tensile, bending, compression and impact tests at room temperature (RT), 80 °C, and 110 °C are conducted for the three materials of the same density. Already at RT, EPC exhibits superior mechanics compared to its peers, which becomes more pronounced toward higher temperature. This comes from the low sensitivity of properties to temperature as EPC is used below its glass transition. In summary, EPC proves to be an outstanding foam material over a broad range of temperatures for structural applications.

RESUMEN

Due to their appealing properties such as high-temperature dimensional stability, chemical resistance, compressive strength and recyclability, new-generation foams based on engineering thermoplastics such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) have been gaining significant attention. Achieving low-density foams without sacrificing the mechanical properties is of vital importance for applications in the field of transportation and construction, where sufficient compressive strength is desired. In contrast to numerous research studies on PET foams, only a limited number of studies on PBT foams and in particular, on extruded PBT foams are known. Here we present a novel route to extruded PBT foams with densities as low as 80 kg/m3 and simultaneously with improved compressive properties manufactured by a tandem reactive-extrusion process. Improved rheological properties and therefore process stability were achieved using two selected 1,3,5-benzene-trisamides (BTA1 and BTA2), which are able to form supramolecular nanofibers in the PBT melt upon cooling. With only 0.08 wt % of BTA1 and 0.02 wt % of BTA2 the normalized compressive strength was increased by 28% and 15%, respectively. This improvement is assigned to the intrinsic reinforcing effect of BTA fibers in the cell walls and struts.

RESUMEN

Two different blend ratios of polyamide 66 (PA66) and poly (2,6-dimethyl-1,4-phenylene ether) (PPE) (60/40 and 40/60 w/w) were produced via melt mixing. A styrene-maleic anhydride copolymer (SMA) was utilized at various contents from 2.5-15 wt% to compatibilize the immiscible blend system. The influence of SMA content and blend ratio was investigated based on (thermo-) mechanical and morphological properties of the PA66/PPE blends. Correlations between the interaction of SMA with the blend partners were established. For 60/40 blends, a droplet-sea morphology was visualized by transmission electron microscopy, wherein no major changes were seen upon SMA addition. In the case of 40/60 blends, strong coalescence was found in the binary blend. Up to 5 wt% SMA, the coalescence was inhibited by the interfacial activity of SMA, whereas 10 wt% SMA initiated a disperse-to-co-continuous transition, which was completed at 15 wt% SMA. An enhancement of tensile properties was achieved for all blends possessing SMA, where the maximum concentration of 15 wt% resulted in the highest elongation at break and tensile strength values. The relative improvement of the tensile properties was higher with the PPE-rich blend (40/60) which was attributed to a partial emulsification of the PPE phases forming a bimodal PPE domain size distribution with nano-droplets in the range of 60-160 nm.

RESUMEN

Upcoming efficient air-borne wind energy concepts and communication technologies applying lighter-than-air platforms require high-performance barrier coatings, which concomitantly and nonselectively block permeation not only of helium but also of ozone and water vapor. Similarly, with the emergence of green hydrogen economy, lightweight barrier materials for storage and transport of this highly diffusive gas are very much sought-after, particularly in aviation technology. Here the fabrication of ultraperformance nanocomposite barrier liners by spray coating lamellar liquid crystalline dispersions of high aspect ratio (∼20 000) silicate nanosheets mixed with poly(vinyl alcohol) on a PET substrate foil is presented. Lightweight nanocomposite liners with 50 wt % filler content are obtained showing helium and hydrogen permeabilities as low as 0.8 and 0.6 cm3 µm m-2 day-1 atm-1, respectively. This exhibits an improvement up to a factor of 4 × 103 as compared to high-barrier polymers such as ethylene vinyl alcohol copolymers. Furthermore, ozone resistance, illustrated by oxygen permeability measurements at elevated relative humidity (75% r.h.), and water vapor resistance are demonstrated. Moreover, the technically benign processing by spray coating will render this barrier technology easily transferable to real lighter-than-air technologies or irregular- and concave-shaped hydrogen tanks.