Henri Balard

Characterization and modification of fillers for paints and coatings

This paper highlights the possibility of inverse gas chromatography for the surface characterization of common fillers (CaCO3, talc, SiO2,⋯) for paints and coatings. Divided solids are described, on the one hand, by the dispersive component of their surface energy and, on the other, by a specific parameter indicating their acid-base interaction potential. The role of the surface morphology at a molecular level is also examined. It is demonstrated that steric effects play an important role in the adsorption of probes on lamellar solids like talc. The consequences of surface treatments as well as examples of practical applications are also reported.

INFLUENCE OF WATER ON THE RETENTION OF ORGANIC PROBES ON CLAYS STUDIED BY IGC

Oil recovery is strongly related to the wettability of reservoir rocks that are formed of quartz grains attached by mineral hydroxides and clay minerals. Illites and kaolinites are the most active due to their high specific surface areas and electrical charge densities. Therefore, these minerals’ relative affinities for oil or water when in contact with a water-oil mix are of great importance. In order to model such a complex system, we used a mix of organic model molecules of the oil constituents and water vapor. Their interactions were estimated by inverse gas chromatography (IGC). IGC experiments were performed using a carrier gas with controlled humidity. By means of IGC at infinite dilution conditions, the dispersive component of the surface energy, γsd, was determined. A strong decrease of γsd, due to water molecules shielding the highest-energy sites, was observed. The energetic surface heterogeneity of the clays was examined using IGC at finite concentration conditions, allowing the determination of organic probe adsorption isotherms in the presence of water. From these isotherms, adsorption energy distribution functions were computed for propanol-2 and pyridine probes. Water mainly modifies the illite distribution functions, whereas practically no change was observed in the case of kaolinite. This observation is related to the higher hydrophilicity of illite as compared with kaolinite, and explains the different behaviors of the 2 clay families in oil reservoirs.

Influence of specific surface area of pyrogenic silicas on their heat of immersion in water and on their surface properties assessed using inverse gas chromatography.

The heat of immersion and the surface properties of pyrogenic silicas were examined using microcalorimetry and inverse gas chromatography at finite concentration (FC-IGC). The microcalorimetric measurements showed a regular decrease of the heat of immersion, in water, per area unit with an increase in the surface areas. The desorption isotherms were established using FC-IGC. It is observed that BET constant value goes through a minimum, whereas the shapes of distribution function of the adsorption energies of isopropanol are changing. All results could be interpreted using a model of formation of the pyrogenic silica in the flame, which explains the change of surface functionality and geometry occurring around 200 m2/g.

AN ASSESSMENT OF THE SURFACE PROPERTIES OF MILLED ATTAPULGITE USING INVERSE GAS CHROMATOGRAPHY

The most common means of reducing the particle size of solids is by grinding, a process which can affect the surface properties and the behavior of the solid in later stages (granulation, compaction, etc.), and which can influence the end-use properties of the final product. Inverse gas chromatography (IGC) measurements were used here to evaluate the influence of grinding, in a ball mill, on attapulgite. The milling experiments were performed in dry media for various periods. After 30 min of grinding, significant decreases in the particle size and specific surface areas were observed when calculated using different probes. No noticeable variation in the surface properties was observed by IGC either at infinite dilution or at finite concentration, however. In particular, the distribution functions of the adsorption energies (DFAE), giving information about the surface heterogeneity for both an apolar probe (octane) and a polar probe (isopropanol), remained unchanged, regardless of the grinding time. The stability of the surface energy with respect to the grinding process was seen to be related to the particular fibrous structure of the attapulgite clay.

Evolution of the surface polar character of pyrogenic silicas, with their grafting ratios by dimethylchlorosilane, studied by microcalorimetry.

The interactions of water, hexamethyldisiloxane, and dodecane with pyrogenic silica samples, modified by a controlled partial silylation with dimethyldichlorosilane, were studied by microcalorimetry and wettability measurements. The samples, having a coverage ratio lower than dimethylsilyl (DMS) monolayer capacity ( approximately 2.6 DMS/nm(2)), show a regular and linear decrease of their heat of immersion into water with the coverage ratio and correlate with the increase of residual silanol groups. Two critical coverage ratios were evidenced at about 25 and 50% of the DMS monolayer capacity, the grafted silica remaining hydrophilic, below 25% being strongly hydrophobic beyond. The heat of immersion into hexamethyldisiloxane decreases until 50% of the DMS monolayer whereas that of dodecane remains independent of the grafting ratio. This study demonstrates that the water/residual free silica surface plays the main role in the stabilization of the W/O Pickerings emulsions.

Study of the interaction polybutadiene/fillers using inverse gas chromatography.

In this study, the coupling of IGC-ID analysis and carbon blacks impregnation with increasing ratios of polymer allow us to highlight the affinity of the polymer to the solid surface. The variations of the dispersive component of the surface energy and of the nanomorphology index are monitored versus the degree of carbon black impregnation. A clear correlation between the decrease in the dispersive component of the surface energy and the increase in the nanomorphological index is observed. The PBu macromolecules shield progressively the slot shaped sites on the carbon blacks surface. IGC reveals clear differences in surface properties between CB of different grades.

Chlorination of talc surface

Abstract Talc has become an important filler for polyolefins but the optimum properties of filled polymer compositions are only achieved when using surface modified talcs. The possibility of chlorinating talc, using CCl 4 at 600°, is demonstrated.