Olivier Verkinderen

Simultaneous Synchrotron WAXD and Fast Scanning (Chip) Calorimetry: On the (Isothermal) Crystallization of HDPE and PA11 at High Supercoolings and Cooling Rates up to 200 °C s−1

An experimental setup, making use of a Flash DSC 1 prototype, is presented in which materials can be studied simultaneously by fast scanning calorimetry (FSC) and synchrotron wide angle X-ray diffraction (WAXD). Accumulation of multiple, identical measurements results in high quality, millisecond WAXD patterns. Patterns at every degree during the crystallization and melting of high density polyethylene at FSC typical scanning rates from 20 up to 200 °C s(-1) are discussed in terms of the temperature and scanning rate dependent material crystallinities and crystal densities. Interestingly, the combined approach reveals FSC thermal lag issues, for which can be corrected. For polyamide 11, isothermal solidification at high supercooling yields a mesomorphic phase in less than a second, whereas at very low supercooling crystals are obtained. At intermediate supercooling, mixtures of mesomorphic and crystalline material are generated at a ratio proportional to the supercooling. This ratio is constant over the isothermal solidification time.

Effect of Compression on the Molecular Arrangement of Itraconazole–Soluplus Solid Dispersions: Induction of Liquid Crystals or Exacerbation of Phase Separation?

Predensification and compression are unit operations imperative to the manufacture of tablets and capsules. Such stress-inducing steps can cause destabilization of solid dispersions which can alter their molecular arrangement and ultimately affect dissolution rate and bioavailability. In this study, itraconazole-Soluplus solid dispersions with 50% (w/w) drug loading prepared by hot-melt extrusion (HME) were investigated. Compression was performed at both pharmaceutically relevant and extreme compression pressures and dwell times. The starting materials, powder, and compressed solid dispersions were analyzed using modulated differential scanning calorimetry (MDSC), X-ray diffraction (XRD), small- and wide-angle X-ray scattering (SWAXS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), and broadband dielectric spectroscopy (BDS). MDSC analysis revealed that compression promotes phase separation of solid dispersions as indicated by an increase in glass transition width, occurrence of a peak in the nonreversing heat flow signal, and an increase in the net heat of fusion indicating crystallinity in the systems. SWAXS analysis ruled out the presence of mesophases. BDS measurements elucidated an increase in the Soluplus-rich regions of the solid dispersion upon compression. FTIR indicated changes in the spatiotemporal architecture of the solid dispersions mediated via disruption in hydrogen bonding and ultimately altered dynamics. These changes can have significant consequences on the final stability and performance of the solid dispersions.

Effect of the GO Reduction Method on the Dielectric Properties, Electrical Conductivity and Crystalline Behavior of PEO/rGO Nanocomposites

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.