János Móczó

Determination of the surface characteristics of particulate fillers by inverse gas chromatography at infinite dilution: a critical approach.

CaCO3 fillers were investigated by inverse gas chromatography (IGC) to determine the dispersion component of their surface tension as well as their acid-base character. Because of the high energy of the filler surface, it readily adsorbs water, thus the parameters measured by IGC depend on the conditioning temperature, as well as on the measurement conditions. As a consequence, the determined surface characteristics are not material constants; different fillers or the effect of coating can be compared only under standard conditions. The use of the same conditioning and measurement temperature eliminates the effect of measurement time. Under appropriate standard conditions the acid-base characteristics of the filler can be determined reliably. However, the accuracy of the determination and the value of the derived parameters depend very much on the selected approach and on the acid-base constants used for the probe molecules. A critical analysis of the approaches used in the current literature pointed out those that yield the most reasonable and accurate values. The results prove that the surface of CaCO3 is strongly basic in character. Coating significantly reduces basicity. Surprisingly, the filler coated with an amount of stearic acid resulting in minimum surface tension showed relatively strong acidity, which indicates a coating exceeding monolayer coverage and/or the uneven distribution of the surfactant on the surface.

Acid-base interactions and interphase formation in particulate-filled polymers

Particulate-filled composites were prepared from CaCO 3 and polymer matrices of various acid-base characters. Interfacial interaction of the components was characterized by the reversible work of adhesion, which was calculated either from dipole-dipole or acid-base interactions. The thickness of the spontaneously formed interlayer was derived from the tensile strength of the composites. The results proved that acid-base interactions play an important role in interphase formation. The strength of interfacial adhesion is determined by the joint effect of dispersion forces and acid-base interactions. Stronger interaction leads to a thicker interphase with decreased mobility. Treatment of CaCO 3 with an aliphatic fatty acid leads to a decrease in the strength of interaction, and to changes both in the thickness and properties of the interphase. In composites containing coated fillers, acid-base interactions influence composite properties less due to the neutral character of the surface.

Biocomposite from polylactic acid and lignocellulosic fibers: structure-property correlations

PLA biocomposites were prepared using three corn cob fractions and a wood fiber as reference. The composites were characterized by tensile testing, scanning electron microscopy (SEM) and polarization optical microscopy (POM). Micromechanical deformation processes were followed by acoustic emission measurements. The different strength of the components was proved by direct measurements. Two consecutive micromechanical deformation processes were detected in composites containing the heavy fraction of corncob, which were assigned to the fracture of soft and hard particles, respectively. The fracture of soft particles does not result in the failure of the composites that is initiated either by the fracture of hard particles or by matrix cracking. Very large particles debond easily from the matrix resulting in catastrophic failure at very low stresses. At sufficiently large shear stresses large particles break easily during compounding, thus reinforcement depending on interfacial adhesion was practically the same in all composites irrespectively of initial fiber characteristics.

Thermoplastic starch/wood composites: Interfacial interactions and functional properties

Thermoplastic starch (TPS)/wood composites were prepared from starch plasticized with 36 wt% glycerol. The components were homogenized by dry-blending, extruded and injection molded to tensile bars. Tensile properties, structure, deformation, water adsorption and shrinkage were determined as a function of wood content, which changed between 0 and 40 vol% in 7 steps. The modification of TPS with wood particles improves several properties considerably. Stiffness and strength increases, and the effect is stronger for fibers with larger aspect ratio. Wood fibers reinforce TPS considerably due to poor matrix properties and strong interfacial interactions, the latter resulting in the decreased mobility of starch molecules and in the fracture of large wood particles during deformation. Strong interfacial adhesion leads to smaller water absorption than predicted from additivity, but water uptake remains relatively large even in the presence of wood particles. The shrinkage of injection molded TPS parts is very large, around 10%, and dimensional changes occur on a very long timescale of several hundred hours. Shrinkage decreases to a low level already at 15-20 vol% wood content rendering the composites good dimensional stability.

Adhesion and micromechanical deformation processes in PLA/CaSO4 composites

PLA/CaSO4 composites were prepared from uncoated and stearic acid coated filler particles in a wide composition range. The strength of interfacial adhesion was estimated quantitatively with three independent methods. Structure was characterized by DSC, XRD and SEM measurements, while mechanical properties by tensile and instrumented impact tests. The results proved that adhesion is twice as strong in composites prepared with the uncoated particles than in those containing the coated filler. Coating changes also local deformation processes around the particles. Although debonding is the dominating micromechanical deformation process in all composites, local plastic deformation is larger around coated particles. The extent of this deformation depends very much also on the local distribution of particles. The final properties and performance of the composites depend unambiguously on the micromechanical deformation processes occurring during loading, on debonding and the subsequent plastic deformation. Stearic acid used for the coating of the filler seems to dissolve in the polymer and locally change its properties.

Adsorption of surfactants on CaCO3 and its effect on surface free energy

A CaCO3 filler was coated with various mono- and dicarboxylic acids in a dry-blending process. The coated fillers were characterized by various techniques, including dissolution experiments, thermal analysis (differential scanning calorimetry) and inverse gas chromatography (IGC) to determine the amount of surfactant needed to achieve monolayer coverage; IGC proved to be the most convenient, reliable and universal method for this purpose. The dispersion component of the surface tension and the specific interaction potential of the coated filler can be derived from the results, but indirect conclusions can be also drawn from them about the orientation of the molecules on the filler surface and the structure of the layer formed. The coverage of the filler with an organic compound leads to a decrease both in the dispersion component of the surface tension and in the acid–base character of the filler surface. In the case of monocarboxylic acids the amount needed for monolayer coverage depends on the chemical structure of the surfactant. Linear chains are assumed to orientate vertically to the surface, while increasing chain length, branches as well as unsaturations lead to a less regular arrangement of the molecules, to a looser structure. At the same surface coverage, the surface tension of the filler covered by aliphatic monocarboxylic acids is the same for all compounds. The adsorption of dicarboxylic acids is more complicated and the decrease in surface tension is significantly smaller than for monocarboxylic compounds.

Physical ageing and molecular mobility in PLA blends and composites

Poly(lactic acid) (PLA) blends and composites were prepared from thermoplastic starch, poly(butylene-adipate-co-terephtalate), polycarbonate, wood flour and CaSO4 in a wide range of compositions. The thermal transitions of PLA were studied by differential scanning calorimetry. The detailed analysis of the transitions of PLA/thermoplastic starch blends indicated that they all are determined by the molecular mobility of PLA chains. Blending changes molecular mobility, and thus it often decreases glass transition temperature and modifies the extent of enthalpy relaxation. All other transitions and characteristics, i.e. cold crystallization, melting and the corresponding enthalpies, change accordingly. Increased molecular mobility accelerates also the physical ageing of the polymer. The interaction between PLA and the various components used for modification changed in a wide range, but no direct correlation was found between the strength of interaction and molecular mobility.