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Four carbon blacks with different specific surface areas and surface chemistries (C32, C71, C159 and C178) were analyzed by transmission electron microscopy (TEM) and nitrogen adsorption isotherms at 77 K. Their surface chemistries were analyzed by X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis coupled with mass spectrometry (TGA-MS) and inverse gas chromatography (IGC). The carbon blacks contained 2.7–5.8 wt% volatiles corresponding to single bondOH, Csingle bondO, Cdouble bond; length as m-dashO and COO groups. The surface chemistry parameters obtained with the different experimental techniques were inter-related by using chemometric statistical analysis tools. The application of this methodology showed that the carbon blacks with lower specific surface area (C32 and C71) had basic character (electron donor) mainly due to Cdouble bond; length as m-dashO and Csingle bondO groups, whereas the carbon black with the highest specific surface area (C178) showed acidic character (acceptor electron) due to its high content of OH groups. Moreover, the total surface energy and the dispersive component of the surface energy of the carbon blacks increased with the increase of their specific surface area. In general the specific interactions of the carbon blacks also increased with the increase of their specific surface area although C71 is exceptional due to higher oxygen content corresponding to Csingle bondO groups.

Four carbon blacks with different specific surface areas and surface chemistries (C32, C71, C159 and C178) were analyzed by transmission electron microscopy (TEM) and nitrogen adsorption isotherms at 77 K. Their surface chemistries were analyzed by X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis coupled with mass spectrometry (TGA-MS) and inverse gas chromatography (IGC). The carbon blacks contained 2.7–5.8 wt% volatiles corresponding to single bondOH, Csingle bondO, Cdouble bond; length as m-dashO and COO groups. The surface chemistry parameters obtained with the different experimental techniques were inter-related by using chemometric statistical analysis tools. The application of this methodology showed that the carbon blacks with lower specific surface area (C32 and C71) had basic character (electron donor) mainly due to Cdouble bond; length as m-dashO and Csingle bondO groups, whereas the carbon black with the highest specific surface area (C178) showed acidic character (acceptor electron) due to its high content of OH groups. Moreover, the total surface energy and the dispersive component of the surface energy of the carbon blacks increased with the increase of their specific surface area. In general the specific interactions of the carbon blacks also increased with the increase of their specific surface area although C71 is exceptional due to higher oxygen content corresponding to Csingle bondO groups.

The properties of composites depend mainly on the interfacial interactions between filler and matrix that can be related to the adhesion between filler and polymer matrix. In this study the work of cohesion between the carbon black particles – Wcoh – and the thermodynamic work of adhesion – Wa – between four carbon blacks of different specific surface area and surface chemistry (nature and content of carbon–oxygen functional groups) and thermoplastic polyurethane were calculated by means of inverse gas chromatography (IGC) at infinite dilution. IGC derived data indicated that the work of adhesion increased by increasing the surface area of the carbon black, but the opposite trend was found in Wa/Wcoh and work of cohesion. According to the Wa/Wcoh values the filler particles should be well dispersed into the polyurethane matrix giving homogenous composites. The carbon black-thermoplastic polyurethane interactions determined by plate–plate rheology showed the same trend than that for the Wa/Wcoh values. However, the thermodynamic work of adhesion values derived from IGC were not in agreement with the carbon black-polyurethane interfacial interactions, likely due to the dominant effect of the carbon black in reducing the crystallinity and increasing the degree of phase separation of the thermoplastic polyurethane.

The properties of composites depend mainly on the interfacial interactions between filler and matrix that can be related to the adhesion between filler and polymer matrix. In this study the work of cohesion between the carbon black particles – Wcoh – and the thermodynamic work of adhesion – Wa – between four carbon blacks of different specific surface area and surface chemistry (nature and content of carbon–oxygen functional groups) and thermoplastic polyurethane were calculated by means of inverse gas chromatography (IGC) at infinite dilution. IGC derived data indicated that the work of adhesion increased by increasing the surface area of the carbon black, but the opposite trend was found in Wa/Wcoh and work of cohesion. According to the Wa/Wcoh values the filler particles should be well dispersed into the polyurethane matrix giving homogenous composites. The carbon black-thermoplastic polyurethane interactions determined by plate–plate rheology showed the same trend than that for the Wa/Wcoh values. However, the thermodynamic work of adhesion values derived from IGC were not in agreement with the carbon black-polyurethane interfacial interactions, likely due to the dominant effect of the carbon black in reducing the crystallinity and increasing the degree of phase separation of the thermoplastic polyurethane.