Coagulative Nucleation in the Copolymerization of Methyl Methacrylate-Butyl Acrylate under Monomer-Starved Conditions.

Coagulative nucleation in the copolymerization of methyl methacrylate-butyl acrylate (MMA-BA) via semicontinuous emulsion heterophase polymerization (SEHP) under monomer-starved conditions in latexes with high solid content (50.0 wt %) and low concentrations of surfactant is reported. The SEHP technique allows the obtention of latex with high colloidal stability and has potential industrial application in polymer synthesis. High instantaneous conversions (>90%) and a high-ratio polymerization rate/addition rate (Rp/Ra) ≥ 0.9 were obtained at low times until the final copolymerization, which confirmed the starved conditions in the systems at the highest surfactant concentrations. The particle size exhibited a linear size increment at conversions between 0 and 40% induced by homogeneous nucleation, a transition region between 40 and 50%, and non-linear behavior at higher conversions by coagulative nucleation. These three behaviors were also observed in the particle surfactant coverage area (Sc), Z-potential, particle coagulation rate (dNp/dt) by the Smoluchowski model, final particle size (Dpz), and number particle (Np) through the reaction. By means of transmission electron microscopy (TEM) images, the onset of coagulation was observed from 50% of conversion until the end of the reaction. In addition, in both processes of copolymerization, tacticity was displayed (mainly syndiotacticity).

Characterization and Electrical Properties of PVA Films with Self-Assembled Chitosan-AuNPs/SWCNT-COOH Nanostructures.

Nanostructured films with electrical conductivity in the semiconductor region were prepared in a polymeric matrix of poly(vinyl alcohol) (PVA) with nanostructures of chitosan-gold nanoparticles (AuNPs)/single-wall carbon nanotubes carboxylic acid functionalized (SWCNT-COOH) (chitosan-AuNPs/SWCNT-COOH) self-assembled. Dispersion light scattering (DLS) was used to determine the average particle sizes of chitosan-AuNPs, z-average particle size (Dz) and number average particle size (Dn), and the formation of crystalline domains of AuNPs was demonstrated by X-ray diffraction (XRD) patterns and observed by means of transmission electron microscopy (TEM). The electrostatic interaction was verified by Fourier transform infrared spectroscopy (FTIR). The electrical conductivity of PVA/chitosan-AuNPs/SWCNT-COOH was determined by the four-point technique and photocurrent. The calculated Dn values of the chitosan-AuNPs decreased as the concentration of gold (III) chloride trihydrate (HAuCl4·3H2O) increased: the concentrations of 0.4 and 1.3 mM were 209 and 90 nm, respectively. Average crystal size (L) and number average size (D) of the AuNPs were calculated in the range of 13 to 24 nm. Electrical conductivity of PVA/chitosan-AuNPs/SWCNT-COOH films was 3.7 × 10-5 σ/cm determined by the four-point technique and 6.5 × 10-4 σ/cm by photocurrent for the SWCNT-COOH concentration of 0.5 wt.% and HAuCl4·3H2O concentration of 0.4 mM. In this investigation, the protonation of the amine group of chitosan is fundamental to prepare PVA films with nanostructures of self-assembled chitosan-AuNPs/SWCNT-COOH.

Photocatalytic Degradation of Diclofenac Using Al2O3-Nd2O3 Binary Oxides Prepared by the Sol-Gel Method.

This paper reports the sol-gel synthesis of Al2O3-Nd2O3 (Al-Nd-x; x = 5%, 10%, 15% and 25% of Nd2O3) binary oxides and the photodegradation of diclofenac activated by UV light. Al-Nd-based catalysts were analyzed by N2 physisorption, XRD, TEM, SEM, UV-Vis and PL spectroscopies. The inclusion of Nd2O3 in the aluminum oxide matrix in the 10-25% range reduced the band gap energies from 3.35 eV for the γ-Al2O3 to values as low as 3.13-3.20 eV, which are typical of semiconductor materials absorbing in the UV region. γ-Al2O3 and Al-Nd-x binary oxides reached more than 92.0% of photoconverted diclofenac after 40 min of reaction. However, the photocatalytic activity in the diclofenac degradation using Al-Nd-x with Nd2O3 contents in the range 10-25% was improved with respect to that of γ-Al2O3 at short reaction times. The diclofenac photoconversion using γ-Al2O3 was 63.0% at 10 min of UV light exposure, whereas Al-Nd-15 binary oxide reached 82.0% at this reaction time. The rate constants determined from the kinetic experiments revealed that the highest activities in the aqueous medium were reached with the catalysts with 15% and 25% of Nd2O3, and these compounds presented the lowest band gap energies. The experimental results also demonstrated that Nd2O3 acts as a separator of charges favoring the decrease in the recombination rate of electron-hole pairs.