Abstract:

Three nanosilicas with different silanol contents were prepared by treatment of hydrophilic fumed silica with dimethyldichlorosilane. This treatment reduced the silanol content and produced the particle agglomeration of the nanosilicas. Thermoplastic polyurethane (TPU) adhesives containing nanosilicas were prepared and characterized by FTIR spectroscopy, differential scanning calorimetry (DSC), plate-plate rheology, dynamic mechanical thermal analysis (DMTA), transmission electron microscopy (TEM) and stress-strain testing. Adhesive strength was obtained from T-peel tests of PVC/polyurethane adhesive joints. The addition of hydrophilic nanosilicas favoured the degree of phase separation between the hard (i.e. isocyanate+chain extender) and soft (i.e. polyol) segments in the TPUs; the higher the silanol content on the surface of silica, the higher the degree of phase separation, and the crystallinity of the polyurethane (due to the soft segments) was also increased. Hydrogen bonds between the ester carbonyl groups in the TPU and the silanol groups on the silica surface were created and more favoured by increasing the silanol content. The tensile strength increased and the elongation at break of the polyurethane decreased by increasing the silanol content of the nanosilica. Addition of nanosilica increased the immediate adhesion of the polyurethane adhesives to PVC, irrespective of the silanol content on the nanosilica. The higher the mechanical and the rheological properties of the polyurethanes containing nanosilicas with different silanol content, the higher the final adhesive strength.

Author affiliation: Vega Baudrit, José. Universidad de Costa Rica; Costa Rica

Author affiliation: Navarro Bañón, Virtudes. Universidad de Alicante; España

Author affiliation: Vazquez, Patricia Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina

Author affiliation: Martín Martínez, Jose Miguel. Universidad de Alicante; España

Abstract:

Three nanosilicas with different silanol contents were prepared by treatment of hydrophilic fumed silica with dimethyldichlorosilane. This treatment reduced the silanol content and produced the particle agglomeration of the nanosilicas. Thermoplastic polyurethane (TPU) adhesives containing nanosilicas were prepared and characterized by FTIR spectroscopy, differential scanning calorimetry (DSC), plate–plate rheology, dynamic mechanical thermal analysis (DMTA), transmission electron microscopy (TEM) and stress–strain testing. Adhesive strength was obtained from T-peel tests of PVC/polyurethane adhesive joints. The addition of hydrophilic nanosilicas favoured the degree of phase separation between the hard (i.e. isocyanate+chain extender) and soft (i.e. polyol) segments in the TPUs; the higher the silanol content on the surface of silica, the higher the degree of phase separation, and the crystallinity of the polyurethane (due to the soft segments) was also increased. Hydrogen bonds between the ester carbonyl groups in the TPU and the silanol groups on the silica surface were created and more favoured by increasing the silanol content. The tensile strength increased and the elongation at break of the polyurethane decreased by increasing the silanol content of the nanosilica. Addition of nanosilica increased the immediate adhesion of the polyurethane adhesives to PVC, irrespective of the silanol content on the nanosilica. The higher the mechanical and the rheological properties of the polyurethanes containing nanosilicas with different silanol content, the higher the final adhesive strength.

Author affiliation: Vega Baudrit, José. Universidad de Costa Rica; Costa Rica

Author affiliation: Navarro Bañón, Virtudes. Universidad de Alicante; España

Author affiliation: Vazquez, Patricia Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina

Author affiliation: Martín Martínez, José Miguel. Universidad de Alicante; España

Abstract:

Solar selective paints, with the addition of Co3O4 as a pigment, are used to improve energetic efficiency in solar collectors.Although Co3O4 has been obtained by different methods, references about combustion synthesis are scarce. Co3O4 powders havebeen synthesized by stoichiometric and non-stoichiometric routes using aspartic acid (Asp) or tri-hydroxi-methyl-aminomethane(Tris) as fuels. The samples were calcined in air at 500 °C. They were characterized by X-ray diffraction, scanning electronmicroscopy, transmission electron microscopy, thermogravimetric analysis, differential scanning calorimetry, Fourier transforminfrared spectrum and the specific surface area of the samples was determined by means of the Brunauer?Emmett?Tellertechnique. The optical properties of pigments were assessed by means of a spectrophotometer. In all cases, powders exhibited thecrystalline structure of Co3O4. A minimum crystallite average size of 29 nm was observed for powders obtained by the?stoichiometric/Asp? combustion route, while a maximum value of 41 nm was stated for powders obtained by the ?nonstoichiometric/Asp?combustion process. The average particle size ranged between 50 and 100 nm. The powders obtained by the?stoichiometric/Asp? method were selected to study their optical properties; their solar absorption value was 86%. Solar selectivesurfaces composed by Co3O4 pigments and an alkyd resin were obtained and applied over copper or aluminum substrates. In both cases, solar absorptance was of 93% and comparable with similar solar selective surfaces, but the thermal emittance value washigher than 90%, as a consequence of the large width of the films.

Author affiliation: Gardey Merino, María Celeste. Universidad Tecnológica Nacional; Argentina

Author affiliation: Fernández de Rapp, M. EMilia. Ministerio de Defensa. Instituto de Investigaciones Científicas y Técnicas para la Defensa; Argentina

Author affiliation: Pinto, Monica. Instituto Nacional de Tecnología Industrial; Argentina

Author affiliation: Etchechoury, M. Elisa. Instituto Nacional de Tecnología Industrial; Argentina

Author affiliation: Lassa, Maria Silvina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Argentino de Nivología, Glaciología y Ciencias Ambientales. Provincia de Mendoza. Instituto Argentino de Nivología, Glaciología y Ciencias Ambientales. Universidad Nacional de Cuyo. Instituto Argentino de Nivología, Glaciología y Ciencias Ambientales; Argentina

Author affiliation: Martín Martínez, Jose Miguel. Universidad de Alicante; España

Author affiliation: Lascalea, Gustavo Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Argentino de Nivología, Glaciología y Ciencias Ambientales. Provincia de Mendoza. Instituto Argentino de Nivología, Glaciología y Ciencias Ambientales. Universidad Nacional de Cuyo. Instituto Argentino de Nivología, Glaciología y Ciencias Ambientales; Argentina

Author affiliation: Vazquez, Patricia Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina

Abstract:

Fumed nanosilicas with different degree of silanization were used to obtain nanosilica-polyurethane (TPU) composites to modify their rheological and mechanical properties. The higher the silanol content of the nanosilica, the higher the storage modulus and the thermal stability of the silica-TPU composite. DMTA experiments confirmed that the TPU-silica interactions increased by increasing the silanol content of the nanosilica.

Author affiliation: Martín Martínez, Jose Miguel. Universidad de Alicante; España

Author affiliation: Vazquez, Patricia Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina

Author affiliation: Vega Baudrit, José. Universidad Nacional de Costa Rica; Costa Rica

Author affiliation: Navarro Bañón, Virtudes. Universidad de Alicante; España

Abstract:

Thermoplastic polyurethane (TPU) adhesives containing nanosilicas with different specific surface area and silanol group content were prepared and characterized by FTIR spectroscopy, differential scanning calorimetry (DSC), thermogravimetry (TGA), X-ray diffraction, plate-plate rheology, dynamical–mechanical–thermal analysis (DMTA), transmission electron microscopy (TEM), and strain–stress test. Adhesive strength was obtained from T-peel tests of PVC/polyurethane adhesive joints. Formation of agglomerates of nanosilica particles within the polyurethane matrix were favoured by increasing the silanol content likely due to stronger hydrogen bond interactions between the silanol groups on the nanosilica over those between the polyurethane and the nanosilica. As a consequence, inter-urethane bonds formation rather than ester-urethane bonds were favoured, leaving the soft segment chains more free to interact between them. Thus, addition of nanosilica favoured the phase segregation in the thermoplastic polyurethane. The increase in specific surface area and silanol content in the nanosilica, generally enhanced the degree of phase separation in the polyurethane, being less marked for nanosilicas with more than 200 m2/g and 0.60 mmol SiOH/gsilica. On the other hand, the addition of the nanosilica improved the tensile strength and elongation at break, and the viscoelastic properties of the polyurethane. The immediate adhesive strength of PVC/polyurethane adhesive joints increased in the filled adhesives and it was determined by the rheological properties of the polyurethane–nanosilica mixtures. By increasing the time after joint formation, the crystallization of the polyurethane was produced giving higher adhesive strength and although a cohesive failure in the PVC was always obtained, a slight though progressive increase in joint strength was found with the passage of time with the ordering of the three systems (PU-0.45, PU-0.60 and PU-0.90) remaining unchanged with the PU-0.60 system the stronger and the PU-0.90 system the weaker. This is in agreement with the trends in the viscoelastic and mechanical properties of the filled adhesives.

Author affiliation: Vega Baudrit, José. Universidad Nacional. Facultad de ciencias exactas y naturales. Laboratorio de polimeros; Costa Rica

Author affiliation: Sibaja Ballester, María. Universidad Nacional. Facultad de ciencias exactas y naturales. Laboratorio de polimeros; Costa Rica

Author affiliation: Vazquez, Patricia Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo En Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina

Author affiliation: Torregrosa-Macia, Rosa. Universidad de Alicante. Departamento de química inorgánica. Laboratorio de adhesión y adhesivos; España

Author affiliation: Martın-Martınez, Jose Miguel. Universidad de Alicante. Departamento de química inorgánica. Laboratorio de adhesión y adhesivos; España

Abstract:

Thermoplastic polyurethane (TPU) adhesives containing nanosilicas with different specific surface area and silanol group content were prepared and characterized by FTIR spectroscopy, differential scanning calorimetry (DSC), thermogravimetry (TGA), X-ray diffraction,plate-plate rheology, dynamical–mechanical–thermal analysis (DMTA), transmission electron microscopy (TEM), and strain–stress test. Adhesive strength was obtained from T-peel tests of PVC/polyurethane adhesive joints. Formation of agglomerates of nanosilica particles within the polyurethane matrix were favoured by increasing the silanol content likely due to stronger hydrogen bond interactions between the silanol groups on the nanosilica over those between the polyurethane and the nanosilica. As a consequence, inter-urethane bonds formation rather than ester-urethane bonds were favoured, leaving the soft segment chains more free to interact between them. Thus, addition of nanosilica favoured the phase segregation in the thermoplastic polyurethane. The increase in specific surface area and silanol content in the nanosilica, generally enhanced the degree of phase separation in the polyurethane, being less marked for nanosilicas with more than 200 m2/g and 0.60 mmol SiOH/gsilica. On the other hand, the addition of the nanosilica improved the tensile strength and elongation at break, and the viscoelastic properties of the polyurethane. The immediate adhesive strength of PVC/polyurethane adhesive joints increased in the filled adhesives and it was determined by the rheological properties of the polyurethane–nanosilica mixtures. By increasing the time after joint formation, the crystallization of the polyurethane was produced giving higher adhesive strength and although a cohesive failure in the PVC was always obtained, a slight though progressive increase in joint strength was found with the passage of time with the ordering of the three systems (PU-0.45, PU-0.60 and PU-0.90) remaining unchanged with the PU-0.60 system the stronger and the PU-0.90 system the weaker. This is in agreement with the trends in the viscoelastic and mechanical properties of the filled adhesives.

Author affiliation: Vega Baudrit, José. Universidad Nacional. Laboratorio de polimeros; Costa Rica

Author affiliation: Sibaja Ballestero, María. Universidad Nacional. Laboratorio de polimeros; Costa Rica

Author affiliation: Vazquez, Patricia Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina

Author affiliation: Torregrosa Maciá, Rosa. Universidad de Alicante. Departamento de química inorgánica; España

Author affiliation: Martín Martínez, Jose Miguel. Universidad de Alicante. Departamento de química inorgánica; España

Abstract:

En este trabajo se presentan los resultados obtenidos al modificar superficialmente una sílice pirogénica hidrófila comercial, con una superficie específica de 200 m2 /g, a la que se le injertó 3-aminopropiltrietoxisilano. La nanosílice modificada se añadió a adhesivos de poliuretano termoplástico en metiletilcetona. El material obtenido se caracterizó mediante sus propiedades mecánicas, térmicas, reológicas y adhesivas. Los resultados obtenidos se compararon con los de adhesivos de poliuretano sin sílice y con sílice sin modificar, preparados bajo las mismas condiciones experimentales.

Author affiliation: Vega Baudrit, José. Universidad Nacional. Escuela de Química. Laboratorio de Polímeros; Costa Rica

Author affiliation: Sibaja Ballestero, María. Universidad Nacional. Escuela de Química. Laboratorio de Polímeros; Costa Rica

Author affiliation: Martín Martinez, José Miguel. Universidad de Alicante. Departamento de Química Inorgánica. Laboratorio de Adhesión y Adhesivos; España

Author affiliation: Vazquez, Patricia Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina

Abstract:

The objective of this work was to synthesize nanosilicas with different degree of hydrophobicity by the sol-gel method, using tetraethyl orthosilicate as a precursor. For this purpose, 3-aminopropyl triethoxysilane (APS) and 1,1,1,3,3,3-hexamethyldisilazane (HMDS), were added during synthesis as modifiers. A commercial biopolymer (Hexamoll Dinch, BASF) intended for packaging of apples, was added to the new nanosilicas. The materials obtained were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, potentiometric titration, porosity, specific surface area and hydrophobicity/ hydrophilicity by wetting test. Colorimetry was used to evaluate change in apple pulp color after contact with the different silicas.

Facultad de Ciencias Exactas