Hydroxymethylation of technical lignins from South American sources with potential use in phenolic resins

This work investigates the valorization of sodium lignosulfonate, kraft, and organosolv lignins from South America. A detailed characterization of the lignins and their chemical modification by hydroxymethylation through its reaction with formaldehyde were performed. The characterization included measurements of moisture, ash, carbohydrate contents, elemental and thermogravimetric analysis, and functional groups, molar mass distributions by Fourier transform infrared spectroscopy, and size exclusion chromatography, respectively. Also, reactive aromatic hydrogens ( HAr) were quantified by the measurement of phenolic hydroxyl groups (P-OH) content by UV–Vis spectroscopy. The different initial formaldehyde/lignin weight ratios (0.07, 1.47), temperatures (40, 50, and 70 C), and pHs (9, 11); and the following of hydroxymethylation reactions by UV–Vis spectroscopy were investigated. All lignins resulted attractive for the use as replacement of phenol in phenolic resins, but sodium lignosulfonate was the most appropriate due to its water solubility. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47712.Fil: Taverna, María Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina. Universidad Tecnológica Nacional; ArgentinaFil: Felissia, Fernando Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Materiales de Misiones. Universidad Nacional de Misiones. Facultad de Ciencias Exactas Químicas y Naturales. Instituto de Materiales de Misiones; ArgentinaFil: Area, Maria Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Materiales de Misiones. Universidad Nacional de Misiones. Facultad de Ciencias Exactas Químicas y Naturales. Instituto de Materiales de Misiones; ArgentinaFil: Estenoz, Diana Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Nicolau, Verónica Viviana. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Tecnológica Nacional; Argentin

Another look at nagyagite from the type locality, Sacarimb, Romania: Replacement, chemical variation and petrogenetic implications

Extensive compositional heterogeneity is displayed by Pb-Sb-Au tellurides from the type locality at S $\check{\rm{a}}$ c $\check{\rm{a}}$ rîmb. These phases are collectively considered as varieties of nagyágite in the absence of crystal chemical data confirming the presence of distinct, but topologically closely related compounds. Chemical heterogeneity is seen relative to ‘normal’ nagyágite, with close to the ideal composition Pb3[Pb1.8(Sb1.1,As0.1)1.2]Σ3S6 (AuTe2), which is the primary and common type in the deposit. A modified formula, (Pb3S3)[(Pb2−x )(Sb,As,Te b )1+x (S3−y Te y )]Σ6(Au1−z−w Te2+z S w ), accounts for the chemical variation observed. Values of x (0.2 to 1.15) express substitution of Pb by Sb+As for Me2 in sulfosalt modules in the case of Au-depleted and low-Au nagyágite, and by Sb+As+Te b in high-As and low-Pb varieties (b = x+1−(Sb+As) = 0.24 to 0.29). Excess Te compensates for Au deficiency in the telluride layer, with substitution by S also observed; empirical values of z and w are 0 to 0.45 and 0 to 0.32, respectively. Minor substitution of Te for S (y < 0.17) is noted in all varieties except low-Au. These varieties are formed during replacement of the ‘normal’ type as seen in overprinting relationships in those veins reactivated during rotation of the duplex fault-system responsible for vein formation. Replacement is by coupled dissolution-reprecipitation reactions, as indicated by pseudomorphism of one nagyágite type by another in all cases. Variable rates of both molar-excess and -deficit reaction are invoked to explain the observed chemical and textural modifications. Low-Pb nagyágite is also present in zoned platelets where it grows over resorbed cores of ideal composition. Such platelets are instead interpreted as products of self-patterning in a residual precipitate. A marked depletion in the Au content of some nagyágite lamellae is considered to be a diffusion driven Te for Au substitution in the presence of Te-bearing fluid. Replacement of ‘normal’ nagyágite by other varieties can be linked to high fluid acidity, whereas replacement by galena-altaite symplectites relates to changes in the fTe2/fS2 within a narrow domain defined by coexistence of these two minerals. Nagyágite is a mineral with modular crystal chemistry and is able to adjust to variable rates of fluid infiltration by subtle chemical substitutions. The behavior of nagyágite will map and assist coupling between dissolution and precipitation during such reactions.C. L. Ciobanu, N. J. Cook, A. Pring, G. Damian and N. Căprar