Institute of Fundamental Technological Research

4D printing is the additive manufacturing (3D printing) of objects that can transform their shape in a controlled and predictable way when subjected to external stimuli. A thermo-responsive shape memory polymer (SMP) is a highly suitable material to 4D print smart devices, due to its actuation function and the capability of recovering its original shape from the deformed one upon heating. This study presents the results of employing an epoxy resin in the additive manufacturing of complex-shaped smart devices with shape-morphing properties using laser stereolithography (SLA). To quantify the shape memory behaviour of the shape memory epoxy (SMEp), we first investigate the thermomechanical properties of the 3D-printed specimens in a tensile testing machine coupled with an environmental thermal chamber. This approach allows us to determine the shape fixity and recovery of SMEp. Next, we propose effective designs of complex-shaped devices, with the aim of promoting shape morphing through micro-actuators and compliant joints acting as active regions in combination with multiplying mechanisms or kinematic chains in each of the devices. We manufacture the complex-shaped prototypes by using SLA directly from the computer-aided designs. The shape memory trials of the 3D-printed prototypes reveal quite precise shape recovery of the devices, illustrating their shape-memory. In fact, the inclusion of micro-actuators and compliant joints within the complex-geometry devices allows for local triggering, deformation and recovery, resulting in a prompt response of the devices to heat. Therefore, innovative designs, along with the suitable smart material and high-quality manufacturing process, lead to 4D printed devices with fast actuation and shape-morphing properties. Overall, this research may contribute to the development of smart materials and 4D printing technology for applications in fields such as biomedical engineering, robotics, transport and aerospace engineering.

Shape memory polymers,Shape memory epoxy,Shape morphing structures,Laser stereolithography,3D and 4D printing

Multifunctional polyurethane shape memory polymers (PU-SMPs) have been of increasing interest in various applications. Here we report structure characterization, detailed methodology, and obtained results on the identification of functional properties of a thermoset PU-SMP (MP4510) with glass transition temperature of 45 C. The stable, chemically crosslinked network of this thermoset PU-SMP results in excellent shape memory behavior. Moreover, the proximity of the activation temperature range of this smart polymer to room and body temperature enables the PU-SMP to be used in more critical industrial applications, namely fast-response actuators. The thermomechanical behavior of a shape memory polymer determines the engineering applications of the material. Therefore, investigation of the shape memory behavior of this class of commercial PU-SMP is of particular importance. The conducted structural characterization confirms its shape memory properties. The shape fixity and shape recovery properties were determined by a modified experimental approach, considering the polymer’s sensitivity to external conditions, i.e., the temperature and humidity variations. Three thermomechanical cycles were considered and the methodology used is described in detail. The obtained shape fixity ratio of the PU-SMP was approximately 98% and did not change significantly in the subsequent cycles of the thermomechanical loading due to the stability of chemical crosslinks in the thermoset materials structure. The shape recovery was found to be approximately 90% in the first cycle and reached a value higher than 99% in the third cycle. The results confirm the effect of the thermomechanical training on the improvement of the PU-SMP shape recovery after the first thermomechanical cycle as well as the effect of thermoset material stability on the repeatability of the shape memory parameters quantities.

polyurethane shape memory polymer, thermomechanical loading program, shape fixity, shape recovery

The present work discusses the effects of reduced graphene oxide (rGO) on the nonlinear viscoelastic behavior, or the Payne effect, of silica/styrene-butadiene rubber compounds. The volume fraction of unmodified silica was constant, while the amount of rGO in these hybrid filler compounds varied. Dynamic-mechanical analysis (DMA) in strain sweep mode showed that adding a small quantity of rGO to the silica-filled compounds resulted in diminished network formation of unmodified silica as well as a reduced Payne effect and corresponding energy dissipation. The state of silica dispersion in the presence of rGO in the rubber matrix was predicted by calculating the work of adhesion in a three-component system and detected by scanning electron microscopy. It was observed that the dispersion of the unmodified silica was improved by the addition of only 0.25 or 0.5 phr rGO, which may be due to the improved silica-rubber interactions that occur during mixing and/or reduced silica flocculation after mixing, as measured by DMA in time sweep mode. The synergy between silica and small quantities of rGO (0.25 or 0.5 phr) resulted in an enhancement in mechanical strength (45%) and abrasion resistance (63%), as well as a reduction in heat build-up (23%). This hybrid system can be considered an alternative to silane modification of silica in green tire technology.

The present study discusses the effects of graphenic particles on the kinetics of sulfur vulcanization in styrene butadiene rubber composites. Using data obtained from a cure rheometer and fitted by an autocatalytic model, it was verified that graphenic particles follow our recently established catalytic-networking model for the effect of particles on the sulfur vulcanization of rubber, regardless of the type of particles. The magnitude of the catalytic and networking effects depends on surface chemistry and interfacial interactions of particles with rubber that can be tailored by the chemical reduction of graphene oxide. Accordingly, the reduction process decreased the catalytic effect due to the elimination of surface functional groups and increased the networking effect due to the enhancement of filler–rubber interactions and immobilization of rubber. The latter was verified by differential scanning calorimetry and bound rubber measurements.

graphene oxide, interfacial interactions, rubber composites, surface chemistry, vulcanization kinetics, wettability

W ramach pracy przeprowadzono bilans energetyczny poliuretanu z pamięcią kształtu PU-SMP o temperaturze zeszklenia Tg = 25 °C w procesie rozciągania. Celem było oszacowanie ilości pracy mechanicznej niezbędnej do odkształcenia, ilości energii dyssypowanej oraz energii zmagazynowanej, tj. ukrytej w elementach zmienionej struktury tego polimeru. Dla wyższej prędkości odkształcania otrzymano wyższe wartości pracy zużytej na odkształcenie nieodwracalne oraz wyższe wartości ciepła dyssypowanego. Przeprowadzona analiza energetyczna procesu odkształcania wykazała, że praca zużyta na odkształcenie nieodwracalne nie magazynuje się w PU-SMP, tylko dysypuje. Może to mieć związek ze specyficzną budową polimeru z pamięcią kształtu, potwierdzoną przez badania strukturalne i odpowiadającą za jego właściwości.

Various quantities of reduced graphene-oxide (rGO) were added into silica-filled styrene-butadiene rubber (SBR) to make hybrid-filler composites. The non-linear viscoelastic behavior and corresponding energy dissipation of silica/rGO hybrid-filler and silica-filled composites were compared. Dynamic-mechanical analysis (DMA) of the hybrid-filler composites in strain-sweep showed that adding small quantity of rGO results in diminished silica network and reduced storage and loss modulus in silica-filled composites. Moreover, the synergy between silica and small quantities of rGO results in reduction of heat build-up (23%). The hybridization of silica/rGO was done without surface modification. This hybrid-filler system can be considered as an alternative to silane-modification of silica in industry.