Strain-stabilized perovskites: The perovskite materials used for solar cells and light-emitting diodes (which are black in color) are generally less stable at room temperature than the electronically inactive nonperovskite phases (which are yellow in color). Steele et al. show that for CsPbI 3 , strain induced in a thin film after annealing the material to 330°C and then rapidly cooling it to room temperature kinetically trapped the black phase. Grazing-incidence wide-angle x-ray scattering revealed the crystal distortions and texture formation created by interfacial strain. Science , this issue p. 679
The effect of the reduction method to prepare reduced graphene oxide (rGO) on the melt linear viscoelastic properties, electrical conductivity, polymer matrix crystalline behavior and dielectric properties of PEO-rGO nanocomposites was investigated. Reduction was performed chemically with either sodium borohydride (NaBH4) or hydrazine monohydrate (N2H4·H2O) or both reduction agents consecutively as well as thermally at 1000 °C. The different reduction methods resulted in exfoliated rGO sheets with different types and amounts of remaining functional groups, as indicated by FT-IR, Raman, TGA and XRD characterization. Moreover, their electrical conductivity ranged between 10−4 and 10−1 S/cm, with the consecutive use of both chemical reduction agents being far superior. PEO nanocomposites with filler loadings of 0.5 wt %, 1 wt % and 2 wt % were prepared by solvent mixing. The rGO fillers affected the melt linear viscoelastic and crystalline behavior of the PEO matrix and resulted in nanocomposites with a substantially increased electrical conductivity. Despite the wide variability in filler conductivity, the effects on the polymer nanocomposite properties were less distinctive. A correlation was obtained between the reduction of the mobility of the polymer chains (evaluated by the glass transition temperature) and the dielectric strength of the interfacial polarisation originating from the effective entrapment of GO/rGO filler charges at the interface with the less conductive PEO. Thus, favorable interactions of the polar PEO with the filler led to reduced mobility of the PEO chains and thereby a more effective entrapment of the filler charges at the PEO interface.
Although semi-crystalline polymers are associated with considerably better mechanical properties and thermal stability compared to their amorphous counterparts, using them as feedstock for Fused Filament Fabrication still poses some major challenges. Hence, the development of printed part crystallinity during printing should be fully understood in order to control the developed weld strength, as well as part shrinkage and warpage. Infrared thermography was utilized to record the thermal history of deposited layers while printing a single-layer wall geometry, employing two PA 6/66 copolymers with distinct molecular weights as feedstock. Print settings were varied to establish which settings are essential to effectively monitor final part crystallinity. The resulting temperature profiles were simulated in a Fast Scanning Chip Calorimetry device that allows for the rapid heating and cooling rates experienced by the printed polymer. Both liquefier temperature and print speed were found to have very little influence on the total attained crystallinity. It became apparent that the build plate, set at a temperature above the polymer’s glass transition temperature, imposes a considerable annealing effect on the printed part. A reduced molecular weight was observed to enhance crystallinity even more strongly. The presented methodology proves that Fast Scanning Chip Calorimetry is an effective tool to assess the impact of both print parameters and feedstock characteristics on the crystallization behavior of semi-crystalline polymers over the course of printing.
One of the main drawbacks of Fused Filament Fabrication is the often-inadequate mechanical performance of printed parts due to a lack of sufficient interlayer bonding between successively deposited layers. The phenomenon of interlayer bonding becomes especially complex for semi-crystalline polymers, as, besides the extremely non-isothermal temperature history experienced by the extruded layers, the ongoing crystallization process will greatly complicate its analysis. This work attempts to elucidate a possible relation between the degree of crystallinity attained during printing by mimicking the experienced thermal history with Fast Scanning Chip Calorimetry, the extent of interlayer bonding by performing trouser tear fracture tests on printed specimens, and the resulting crystalline morphology at the weld interface through visualization with polarized light microscopy. Different printing conditions are defined, which all vary in terms of processing parameters or feedstock molecular weight. The concept of an equivalent isothermal weld time is utilized to validate whether an amorphous healing theory is capable of explaining the observed trends in weld strength. Interlayer bond strength was found to be positively impacted by an increased liquefier temperature and reduced feedstock molecular weight as predicted by the weld time. An increase in liquefier temperature of 40 °C brings about a tear energy value that is three to four times higher. The print speed was found to have a negligible effect. An elevated build plate temperature will lead to an increased degree of crystallinity, generally resulting in about a 1.5 times larger crystalline fraction compared to when printing occurs at a lower build plate temperature, as well as larger spherulites attained during printing, as it allows crystallization to occur at higher temperatures. Due to slower crystal growth, a lower tie chain density in the amorphous interlamellar regions is believed to be created, which will negatively impact interlayer bond strength.
Biobased and biodegradable polyhydroxyalkanoates (PHAs) have great potential as sustainable packaging materials. However, improvements in their processing and mechanical properties are necessary. In this work, the influence of melt processing conditions on the mechanical properties and microstructure of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) is examined using a full factorial design of experiments (DoE) approach. We have found that strict control over processing temperature, mold temperature, screw speed, and cooling time leads to highly increased elongation at break values, mainly under influence of higher mold temperatures at 80 °C. Increased elongation of the moldings is attributed to relaxation and decreased orientation of the polymer chains together with a homogeneous microstructure at slower cooling rates. Based on the statistically substantiated models to determine the optimal processing conditions and their effects on microstructure variation and mechanical properties of PHBHHx samples, we conclude that optimizing the processing of this biopolymer can improve the applicability of the material and extend its scope in the realm of flexible packaging applications.