Kinetic Modeling of the Gas Antisolvent Process for Synthesis of 5‐Fluorouracil Nanoparticles

Mathematical modeling for 5‐fluorouracil (5‐FU) nanoparticle synthesis via gas antisolvent (GAS) process was investigated. 5‐FU was precipitated from a dimethyl sulfoxide (DMSO) solution using CO₂ as antisolvent. The particle size was controlled by nucleation and growth rates, therefore, the kinetic modeling study is essential. Thermodynamic modeling was applied to determine optimal operating conditions for experimental 5‐FU synthesis. Kinetic parameters were evaluated by fitting the particle size distribution predicted by the model to experimental data. The experimental and modeling results indicated that the particle size decreased with increasing the antisolvent addition rate.     

Thermal degradation behavior and kinetic studies of polyacrylamide gel in TiO2 nanoparticles synthesis

Polyacrylamide gel (PAMG) method is a simple, fast and cheap method used for the synthesis of a wide variety of nanopowders. However, no adequate results have been reported on the thermal degradation behavior of PAMG which can be very effective on the final product properties. In this work, thermal degradation behavior of PAMG in the presence of TiCl₄ as a precursor salt for synthesis of TiO₂ nanoparticles was examined in comparison with linear polyacrylamide (LPAM) and pure PAMG by thermogravimetry/differential thermal analysis. Their thermal degradation kinetics was investigated, as well. The results showed that thermal degradation of all samples occurred in two stages at different onset temperatures. Despite the high thermal stability of pure PAMG compared to LPAM, the presence of TiCl₄ as a mineral material in PAMG structure decreases the thermal degradation onset temperature, considerably. Furthermore for LPAM and PAMG, majority of weight loss occurs in the second stage, but in PAMG with TiCl₄ the weight loss occurs mainly at the first stage. For more detailed investigation, residual materials were characterized by Fourier transform infrared spectroscopy and X-ray diffraction (XRD) techniques, attributing this trend to the presence of mineral materials in PAMG structure. XRD and transmission electron microscopy were also applied to confirm anatase crystalline structure and nanoscale distribution of the TiO₂ particles synthesized via PAMG method.     

Effect of carbon nanotubes on dynamic mechanical properties,TGA, and crystalline structure of polypropylene

This paper is devoted to the preparation of thermoplastic nanocomposites of polypropylene (PP) and different amounts of single‐walled carbon nanotubes (SWNTs) in the range 0.25–2 wt %. The effect of SWNT content on the dynamic mechanical behavior, thermal degradation, crystalline structure, and the kinetic crystallizability of PP were studied. The results obtained from dynamic mechanical thermal analyzer (DMTA) showed that the maximum storage modulus was achieved when 1 wt % SWNT was added into the pristine polymer. Thermal stability of the nanocomposites was measured by thermogravimetric analyzer (TGA). From the TGA results, it was found that the weight fraction of PP which was located at the interface for the nanocomposite containing 0.5% SWNT was about 60%, and this value did not change much with the addition of higher amounts of SWNT. Moreover, the thickness of the interface between PP and SWNT was estimated to be of the order of 10¹ nm which is very close to the radii of gyration of PP molecular chains. Wide angle X‐ray diffractometer (WAXD) was used to explore the crystalline structure of water and slow‐cooled samples. It was found that the crystallization of PP in 040 lattice plane increased for the nanocomposites compared with PP for both cooling rates studied. It was also found that the kinetic crystallizability values were nearly the same for PP and the nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

In situ emulsion polymerization and characterization of PVAc nanocomposites including colloidal silica nanoparticles for wood specimens bonding

Polyvinyl acetate (PVAc) nanocomposites for wood adhesives containing different amounts of colloidal silica nanoparticles (CSNs) were synthesized via in situ one-step emulsion polymerization. The adhesion strength of wood specimens bonded by PVAc nanocomposites was investigated by the tensile test. Thermal properties of PVAc nanocomposites were also characterized by differential scanning calorimetry and thermogravimetric analysis. Rheological and morphological properties of the PVAc nanocomposites were investigated using rheometric mechanical spectrometry and field emission scanning electron microscopy (FESEM), respectively. The obtaining results showed that the shear strength of PVAc nanocomposite including 1 wt. % CSNs has the highest shear and tensile strength about 4.7 and 3.2 MPa, respectively. A small increment of T_g (~3 °C) and considerable increment of the ash content proved the enhancement of PVAc thermal characterization in the presence of CSNs. FESEM results showed uniform dispersion of nanoparticles throughout the PVAc matrix due to using the in situ emulsion polymerization process. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48570.     

Strain‐rate‐dependent mechanical properties of polypropylene separator for lithium‐ion batteries

The mechanical integrity of battery separators is critical for battery safety and durability. A comprehensive study of strain‐rate‐dependent tensile and puncture properties of a polypropylene lithium‐ion battery separator is presented here with a new model. Due to anisotropy of the polymeric membrane, tensile testing was conducted for different directions. Results showed that tensile strength and elastic modulus were increased 1000% and 500%, respectively, for different directions. It was also demonstrated that tensile strength changed 10 to 25% with strain rate (1.67 × 10^?4 to 1.67 × 10^?1 s^?1) for different directions. An equation was obtained for the first time for flow stress versus strain rate at varied tensile directions with respect to machine direction. Moreover, puncture testing was performed and it was shown that puncture strength was increased 140% with increasing strain rate from 0.25 to 250 mm min^?1. Two failure modes were also observed in puncture samples. Finally, Eyring's model was used to calculate activation enthalpy of the porous polypropylene separator. © 2020 Society of Chemical Industry     

Electrical and mechanical properties of BZT − xBCT lead-free piezoceramics

In this study, lead-free (1 − x)Ba(Zr_0.2Ti_0.8)O₃ − x(Ba_0.7Ca_0.3)TiO₃ compositions are synthesized via conventional solid oxide route, and the ceramics are fabricated with normal sintering in air. The effects of composition fluctuations on dielectric, piezoelectric, and mechanical properties are investigated. The phase structure and the microstructure are analyzed with X-ray diffraction and scanning electron microscopy. The best dielectric and piezoelectric properties of ε_r = 11 207 and d₃₃ = 330 pC/N were obtained for BZT−0.35BCT and BZT−0.5BCT ceramics, respectively. The mechanical behavior—in terms of Vickers hardness and compressive and flexural strengths—was investigated, and the best mechanical behavior was found in the vicinity of the phase transition boundary with x values between 0.5 and 0.6.     

Co-doping effects of (Al,Ti, Mg) on the microstructure and electrical behavior of ZnO-based ceramics

Co-doped ZnO-based ceramics using Al, Ti, and Mg ions in different ratios were synthesized with the objective to investigate the doping effects on the crystalline features, microstructure and the electrical behavior. For Al and Ti doping, a coexistence of crystalline phases was shown with a major wurtzite ZnO structure and secondary spinel phases (ZnAl₂O₄, Zn₂TiO₄, or Zn_aTi_bAl_cO_d), while Mg doping did not alter significantly the structural features of the wurtzite ZnO phase. The electrical behavior induced by Al, Ti, and Mg co-doping in different ratios was investigated using Raman, electron paramagnetic resonance (EPR) and ²⁷Al and ⁶⁷Zn solid-state nuclear magnetic resonance (NMR). Al doping induces a high electrical conductivity compared to other doping elements. In particular, shallow donors from Zn_i-Al_Zn defect structures are inferred from the characteristic NMR signal at about 185 ppm; that is, quite far from the usual oxygen coordinated Al. The Knight shift effect emanating from a highly conducting Al-doped ZnO ceramics was considered as the origin of this observation. Oppositely, as Ti doping leads to the formation of secondary spinel phases, EPR analysis shows a high concentration of Ti³⁺ ions which limit the electrical conductivity. The correlation between the structural features at the local order, the involved defects and the electrical behavior as function of the doping process are discussed.