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.

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.

Rheology in the Presence of Carbon Dioxide (CO2) to Study the Melt Behavior of Chemically Modified Polylactide (PLA).

For the preparation of polylactide (PLA)-based foams, it is commonly necessary to increase the melt strength of the polymer. Additives such as chain extenders (CE) or peroxides are often used to build up the molecular weight by branching or even crosslinking during reactive extrusion. Furthermore, a blowing agent with a low molecular weight, such as carbon dioxide (CO2), is introduced in the foaming process, which might affect the reactivity during extrusion. Offline rheological tests can help to measure and better understand the kinetics of the reaction, especially the reaction between the polymer and the chemical modifier. However, rheological measurements are mostly done in an inert nitrogen atmosphere without an equivalent gas loading of the polymer melt, like during the corresponding reactive extrusion process. Therefore, the influence of the blowing agent itself is not considered within these standard rheological measurements. Thus, in this study, a rheometer equipped with a pressure cell is used to conduct rheological measurements of neat and chemical-modified polymers in the presence of CO2 at pressures up to 40 bar. The specific effects of CO2 at elevated pressure on the reactivity between the polymer and the chemical modifiers (an organic peroxide and as second choice, an epoxy-based CE) were investigated and compared. It could be shown in the rheological experiments that the reactivity of the chain extender is reduced in the presence of CO2, while the peroxide is less affected. Finally, it was possible to detect the recrystallization temperature Trc of the unmodified and unbranched sample by the torque maximum in the rheometer, representing the tear off of the stamp from the sample. Trc was about 13 K lower in the CO2-loaded sample. Furthermore, it was possible to detect the influences of branching and gas loading simultaneously. Here the influence of the branching on Trc was much higher in comparison to a gas loading.

Evaluation of the Zero Shear Viscosity, the D-Content and Processing Conditions as Foam Relevant Parameters for Autoclave Foaming of Standard Polylactide (PLA).

In this comprehensive study, the influence of (i) material specific properties (e.g., molecular weight, zero shear viscosity, D-content) and (ii) process parameters (e.g., saturation temperature, -time, -pressure, and pressure drop rate) on the expansion behavior during the autoclave foaming process were investigated on linear Polylactide (PLA) grades, to identify and evaluate the foam relevant parameters. Its poor rheological behavior is often stated as a drawback of PLA, that limits its foamability. Therefore, nine PLA grades with different melt strength and zero shear viscosity were systematically chosen to identify whether these are the main factors governing the foam expansion and whether there is a critical value for these rheological parameters to be exceeded, to achieve low density foams with fine cells. With pressure drop induced batch foaming experiments, it could be shown that all of the investigated PLA grades could be foamed without the often used chemical modifications, although with different degrees of expansion. Interestingly, PLAs foaming behavior is rather complex and can be influenced by many other factors due to its special nature. A low molecular weight combined with a high ability to crystallize only lead to intermediate density reduction. In contrast, a higher molecular weight (i.e., increased zero shear viscosity) leads to significant increased expandability independent from the D-content. However, the D-content plays a crucial role in terms of foaming temperature and crystallization. Furthermore, the applied process parameters govern foam expansion, cell size and crystallization.

Chemical Modification and Foam Processing of Polylactide (PLA).

Polylactide (PLA) is known as one of the most promising biopolymers as it is derived from renewable feedstock and can be biodegraded. During the last two decades, it moved more and more into the focus of scientific research and industrial use. It is even considered as a suitable replacement for standard petroleum-based polymers, such as polystyrene (PS), which can be found in a wide range of applications-amongst others in foams for packaging and insulation applications-but cause strong environmental issues. PLA has comparable mechanical properties to PS. However, the lack of melt strength is often referred to as a drawback for most foaming processes. One way to overcome this issue is the incorporation of chemical modifiers which can induce chain extension, branching, or cross-linking. As such, a wide variety of substances were studied in the literature. This work should give an overview of the most commonly used chemical modifiers and their effects on rheological, thermal, and foaming behavior. Therefore, this review article summarizes the research conducted on neat and chemically modified PLA foamed with the conventional foaming methods (i.e., batch foaming, foam extrusion, foam injection molding, and bead foaming).