Deciphering the role of water and a zinc-doping process in a polyol-based approach for obtaining Zn/Co/Al-based spinels: toward "green" mesoporous inorganic pigments.

Two new families of zinc/cobalt/aluminum-based pigments, with a unique composition, were obtained through the polyol method. The hydrolysis process of a mixture of Co(CH3COO)2, Zn(acac)2 and Al(acac)3 (acac- = acetylacetonate ion) in 1,4-butanediol afforded dark blue gels (wPZnxCo1-xAl), in the presence of a supplementary amount of water, and light green powders (PZnxCo1-xAl), respectively, for the water-free procedure (x = 0, 0.2, 0.4). The calcination of the precursors yielded dark green (wZnxCo1-xAl) and blue (ZnxCo1-xAl) products. XRD measurements and Rietveld refinement indicate the co-existence of three spinel phases, in different proportions: ZnxCo1-xAl2O4, Co3O4 and the defect spinel, γ-Al2.67O4. The Raman scattering and XPS spectra are in agreement with the compositions of the samples. The morphology of wZnxCo1-xAl consists of large and irregular spherical particle aggregates (ca. 5-100 mm). Smaller agglomerates (ca. 1-5 mm) with a unique silkworm cocoon-like hierarchical morphology composed of cobalt aluminate cores covered with flake-like alumina shells are formed for ZnxCo1-xAl. TEM and HR-TEM analyses revealed the formation of crystalline, polyhedral particles of 7-43 nm sizes for wZnxCo1-xAl, while for ZnxCo1-xAl, a duplex-type morphology, with small (7-13 nm) and larger (30-40 nm) particles, was found. BET assessment showed that both series of oxides are mesoporous materials, with different pore structures, with the water-free samples exhibiting the largest surface areas due, most likely, to the high percent of aluminum oxide. A chemical mechanism is proposed to highlight the role of the water amount and the nature of the starting compounds in the hydrolysis reaction products and, further, in the morpho-structural features and composition of the resulting spinel oxides. The CIE L*a*b* and C* colorimetric parameters indicate that the pigments are bright, with a moderate degree of luminosity, presenting an outstanding high blueness.

Fly-Ash Evaluation as Potential EOL Material Replacement of Cement in Pastes: Morpho-Structural and Physico-Chemical Properties Assessment.

The main objective of the study was to produce alternative binder materials, obtained with low cost, low energy consumption, and low CO2 production, by regenerating end-of-life (EOL) materials from mineral deposits, to replace ordinary Portland cement (OPC). The materials analyzed were ash and slag from the Turceni thermal power plant deposit, Romania. These were initially examined for morphology, mineralogical composition, elemental composition, degree of crystallinity, and heating behavior, to determine their ability to be used as a potential source of supplementary cementitious materials (SCM) and to establish the activation and transformation temperature in the SCM. The in-situ pozzolanic behavior of commercial cement, as well as cement mixtures with different percentages of ash addition, were further observed. The mechanical resistance, water absorption, sorptivity capacity, resistance to alkali reactions (ASR), corrosion resistance, and resistance to reaction with sulfates were evaluated in this study using low-vacuum scanning electron microscopy.

Multifunctional Platforms Based on Graphene Oxide and Natural Products.

Background and objectives: In the last few years, graphene oxide has attracted much attention in biomedical applications due to its unique physico-chemical properties and can be used as a carrier for both hydrophilic and/or hydrophobic biomolecules. The purpose of this paper was to synthesize graphene oxide and to obtain multifunctional platforms based on graphene oxide as a nanocarrier loaded with few biologically active substances with anticancer, antimicrobial or anti-inflammatory properties such as gallic acid, caffeic acid, limonene and nutmeg and cembra pine essential oils. Materials and Methods: Graphene oxide was obtained according to the method developed by Hummers and further loaded with biologically active agents. The obtained platforms were characterized using FTIR, HPLC, TGA, SEM, TEM and Raman spectroscopy. Results: Gallic acid released 80% within 10 days but all the other biologically active agents did not release because their affinity for the graphene oxide support was higher than that of the phosphate buffer solution. SEM characterization showed the formation of nanosheets and a slight increase in the degree of agglomeration of the particles. The ratio I2D/IG for all samples was between 0.18 for GO-cembra pine and 0.27 for GO-limonene, indicating that the GO materials were in the form of multilayers. The individual GO sheets were found to have less than 20 µm, the thickness of GO was estimated to be ~4 nm and an interlayer spacing of about 2.12 Å. Raman spectroscopy indicated that the bioactive substances were adsorbed on the surface and no degradation occurred during loading. Conclusions: These findings encourage this research to further explore, both in vitro and in vivo, the biological activities of bioactive agents for their use in medicine.