Low-cycle fatigue behavior of flexible 3D printed thermoplastic polyurethane blends for thermal energy storage/release applications

Thermal energy storage (TES) materials constituted by a microencapsulated paraffin having a melting temperature of 6°C and a thermoplastic polyurethane (TPU) matrix were prepared through fused deposition modeling. Scanning electron microscope (SEM) micrographs demonstrated that the microcapsules were homogeneously distributed within the matrix, with a rather good adhesion within the layers of 3D printed specimens, even at elevated concentrations of microcapsules. The presence of paraffin capsules having a rigid polymer shell lead to a stiffness increase, associated to a decrease in the stress and in the strain at break. Tensile and compressive low-cycles fatigue tests showed that the presence of microcapsules negatively affected the fatigue resistance of the samples, and that the main part of the damage occurred in the first fatigue cycles. After the first 10 loading cycles at 50% of the stress at break, a decrease in the elastic modulus ranging from 60% for neat TPU to 80% for composite materials was detected. This decrease reached 40% of the original value at 90% of the stress at break after 10 cycles. Differential scanning calorimetry tests on specimens after fatigue loading highlighted a substantial retention of the original TES capability, in the range of 80%–90% of the pristine value, even after 1000 cycles, indicating that the integrity of the capsules was maintained and that the propagation of damage during fatigue tests took probably place within the surrounding polymer matrix. It could be therefore concluded that it is possible to apply the developed blends in applications where the materials are subjected to cyclic stresses, both in tensile and compressive mode.     

New ways to improve the damping properties in high‐performance thermoplastic vulcanizates

The incorporation of viscoelastic materials represents an effective strategy to reduce the vibratory level of structural components. Thermoplastic vulcanizates (TPVs) are a special type of viscoelastic material that combines the elastomeric properties of rubbers with the easy processing of thermoplastics. In the present work, we propose innovative ways to improve the damping properties of high‐performance TPVs by using rubbers with carboxylic functionalities. For that, TPVs from physical blends of carboxylated hydrogenated acrylonitrile butadiene rubber (XHNBR) and polyamide 6 (PA6) were prepared. The chain dynamics of different mixed crosslink systems containing peroxide, metal oxides and hindered phenolic antioxidants were investigated in order to find the most suitable strategy to design a high‐performance TPV system with upgraded damping properties. The results indicate that the damping performance of the TPV system can be tailored by controlling the type and magnitude of the bonding interactions between the mixed crosslink system and the XHNBR rubber phase. Therefore, this study demonstrates the potential of TPV systems containing carboxylic rubbers as high‐performance damping materials. © 2020 Society of Chemical Industry     

Chemically Responsive Elastomers Exhibiting Unity‐Order Refractive Index Modulation

Chameleons are masters of light, expertly changing their color, pattern, and reflectivity in response to their environment. Engineered materials that share this tunability can be transformative, enabling active camouflage, tunable holograms, and novel colorimetric medical sensors. While progress has been made in creating artificial chameleon skin, existing schemes often require external power, are not continuously tunable, and may prove too stiff or bulky for applications. Here, a chemically tunable, large‐area metamaterial is demonstrated that accesses a wide range of colors and refractive indices. An ordered monolayer of nanoresonators is fabricated, then its optical response is dynamically tuned by infiltrating its polymer substrate with solvents. The material shows a strong magnetic response with a dependence on resonator spacing that leads to a highly tunable effective permittivity, permeability, and refractive index spanning negative and positive values. The unity‐order index tuning exceeds that of traditional electro‐optic and photochromic materials and is robust to cycling, providing a path toward programmable optical elements and responsive light routing.     

Surface modification of TiO2 particles with 12-hydroxy stearic acid and the effect of particle size on the mechanical and thermal properties of thermoplastic polyurethane urea elastomers

The efficient surface modification of titanium dioxide (TiO₂) particles with different sizes was first carried out with “water only method” (Appl. Surf. Sci. 2018, 447, 664–672) developed in our group using 12-hydroxy stearic acid (12-HSA) as the modifier. The 12-HSA-modified TiO₂ particles with different sizes were then used to explore their effect on the mechanical and thermal properties of a thermoplastic polyurethane urea (TPUU) elastomer with superior mechanical and thermal properties produced newly in our lab using nonsymmetric alicyclic diisocyanate and diamine. Orthogonal experimental results showed that the order of impact of each factor on the modification efficiency of TiO₂ particles was: Temperature > time > modifier content. It was found that, in the nanometer (≤100 nm) range, smaller particles were more helpful to enhance the tensile strength of the TPUU elastomer, while larger ones to increase more significantly the elongation at break. Besides, the TiO₂/polyurethane urea nanocomposites exhibited much better thermomechanical performance than the pristine TPUU elastomer, and the thermomechanical performance of the nanocomposites increased with decreasing particle size.     

Crystallization-Directed Anisotropic Electroactuation in Selectively Solvated Olefinic Thermoplastic Elastomers: A Thermal and (Electro)Mechanical Property Study

Dielectric elastomers (DEs), a class of soft electroactive polymers that change size upon exposure to an external electric field, constitute an increasingly important class of stimuli-responsive polymers due primarily to their large actuation strains, facile and low-cost fabrication, scalability, and mechanical robustness. Unless purposefully constrained, most DEs exhibit isotropic actuation wherein size changes are the same in all actuation directions. Previous studies of DEs containing oriented, stiff fibers have demonstrated, however, that anisotropic actuation along a designated direction is more electromechanically efficient since this design eliminates energy expended in nonessential directions. To identify an alternative, supramolecular-level route to anisotropic electroactuation, we investigate the thermal and mechanical properties of novel thermoplastic elastomer gels composed of a selectively solvated olefinic block copolymer that not only microphase-separates but also crystallizes upon cooling from the solution state. While these materials possess remarkable mechanical attributes (e.g., giant strains in excess of 4000%), their ability to be strain-conditioned enables huge anisotropic actuation levels, measured to be greater than 30 from the ratio of orthogonal actuation strains. This work establishes that crystallization-induced anisotropic actuation can be achieved with these DEs.     

Microencapsulation of sulfur by calcium alginate

The sulfur blooms on surface of rubber compounds cause loss of the needed tack for formation of multiply articles like tires. Although insoluble sulfur can be used to mitigate this problem, it is expensive to manufacture with a complex and hazardous process. This work examines an alternative approach that involves microencapsulation of soluble sulfur in alginate-based matrix. The formulations and procedures are developed and evaluated. Alginate crosslinking time, controlled temperature change (e.g., from 10 to 36°C), and the drying method were found to be critical to achieving high encapsulation efficiencies. The higher temperature (36°C) helped with the mass transfer limited removal of CS₂ used for dissolving sulfur, and treatment of crosslinked beads with oil prior to air-drying improved sulfur encapsulation. Formulated beads had higher than 65% sulfur content (>80%, oil-free basis) with almost 90% of the beads being <150 μm. The process parameters can be adjusted to make even smaller beads.     

The influence of MWCNT and hybrid (MWCNT/nanoclay) fillers on performance of EPDM-CIIR blends in nuclear applications: Mechanical,hydrocarbon transport,and gamma-radiation aging characteristics

Blends of EPDM and chlorobutyl (CIIR) rubbers are used in nuclear plants where they have to withstand the combined effect of radiation and hydrocarbon aging. To improve their mechanical properties as well as hydrocarbon and gamma radiation resistance, the blends are reinforced with 0.5, 1, 1.5, and 2 phr of MWCNT. The increase in mechanical properties was highest for 1.5 phr MWCNT with 69% increase in tensile strength. The improvement in properties was correlated to MWCNT dispersion and filler–polymer interactions, which were confirmed by TEM and FTIR analysis. Hydrocarbon transport coefficients decreased on addition of MWCNT. The nanocomposites were exposed to 0.5, 1, and 2 MGy cumulative doses of gamma radiation. Depending on the radiation dose, crosslinking and/or chain scission occurred causes changes in physical properties. MWCNT reinforcement reduced the magnitude of changes in mechanical and transport properties after γ-irradiation. ESR and FTIR spectra provided qualitative information on free radical formation and chemical changes due to γ-rays exposure. To further enhance the properties, hybrid nanocomposites with 1.5 phr MWCNT and varying nanoclay contents (0.5, 1, 1.5, 2, and 5 phr) were prepared. Due to synergism between MWCNT and nanoclay, the hybrid composites had superior properties with hybrid containing 5 phr nanoclay giving 98% increase in tensile strength.