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Surface Free Energy Components of Clay-Synthetic Humic Acid Complexes from Contact-Angle Measurements

Published online by Cambridge University Press:  02 April 2024

Claire Jouany
Claire Jouany*
Affiliation:
I.N.R.A., Science du Sol, 78026 Versailles, Cedex, France
*
1Present address: I.N.R.A., Station d'Agronomie, Chemin de Borde-Rouge, Auzeville, B.P. 27, 31326 Castanet-Tolosan, Cedex, France.
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Abstract

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The surface free energy components of clay-organic complexes were determined to assess to what extent an organic adsorbate modified the surface properties of the mineral, insofar as the stability of soil aggregates is concerned. Adsorption isotherms for two synthetic, humic acid-like polymers were determined on a Ca-montmorillonite. From contact-angle measurements performed on dry surfaces, the surface free energy properties of the clay-organic complexes were determined using the two-liquid-phases method (water and hydrocarbons). This method allows both the dispersive and nondispersive components of the solid surface free energy, γDS and γPS, to be determined. The results show that a very small amount of polymer (1% by weight) adsorbed on the external surfaces of the montmorillonite decreased markedly the surface free energy components of the clay: γDS decreased from 75 to 28 mJ/m2 for polycondensate catechol (PC) and from 75 to 30 mJ/m2 for polycondensate catechol triglycine (PCT), whereas γPS ranged from 35 to 16 mJ/m2 (PC) and from 35 to 17 mJ/m2 (PCT). Although their chemical compositions were different, both polymers similarly modified γDS and γPS. Increasing the amount of polymer adsorbed (from 1% to 3.5% by weight) affected mostly γPS, which became as low as 5 mJ/m2; meanwhile, γDS decreased from 30 to 23 mJ/m2. Possibly, the molecular orientation of the adsorbate changed in the process of dehydration. Following adsorption of synthetic humic acid-like polymers, dry Ca-montmorillonite complexes displayed γS values < 50 mJ/m2, which were consistent with the solid-water contact angles measured in air.

Résumé

Résumé

Les composantes de l’énergie libre de surface sont mesurées pour des complexes organo-minéraux. Cette étude est menée dans le but de vérifier de quelle manière un revêtement organique modifie les propriétés de surface du minéral et peut jouer sur la stabilité structurale. On a déterminé les isothermes d'adsorption sur une montmorillonite calcique pour deux polymères synthétiques modèles d'acides humiques. L’énergie libre de surface des complexes organo-minéraux est calculée à partir de la mesure des angles de contact obtenus sur des surfaces déshydratées avec la méthode à deux phases liquides (eau et hydrocarbures). Cette méthode permet de déterminer à la fois γPS et γDS, qui sont respectivement la composante polaire et la composante dispersive de l’énergie de surface γS. Les résultats montrent qu'une quantité très faible de polymère (1% en poids) adsorbé sur les surfaces externes de la montmorillonite diminue de manière importante les composantes de l’énergie libre de surface du minéral: γDS diminue de 75 à 28 mJ/m2 pour le polycondensat catéchol (PC) et de 75 à 30 mJ/m2 pour le polycondensat catéchol triglycine (PCT), alors que γPS varie de 35 à 16 mJ/m2 (PC) et de 35 à 17 mJ/m2 (PCT). Bien que leurs compositions chimiques soient différentes, les deux polymères modifient pareillement γPS et γDS. Une augmentation sensible des quantités adsorbées (de 1% à 3,5% en poids) affecte principalement γPS qui diminue jusqu’à une valeur de 5 mJ/m2, alors que γDS passe de 30 à 23 mJ/m2. Ces modifications importantes sont attribuées à un changement d'orientation des polymères adsorbés, susceptible de s’être produit au cours de la déshydratation. Après adsorption de polymères synthétiques modèles d'acides humiques, la montmorillonite calcique à l’état sec présente des valeurs de γS inférieures à 50 mJ/m2 qui sont en accord avec les angles de contact solide-eau-vapeur qui sont mesurés.

Keywords

AdsorptionAggregate stabilityHumic acidMontmorilloniteSurface free energyWettability
Type
Research Article
Information
Clays and Clay Minerals , Volume 39 , Issue 1 , February 1991 , pp. 43 - 49
Copyright
Copyright © 1991, The Clay Minerals Society

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