Eric Balnois

CHARACTERISTIC FEATURES OF THE MAJOR COMPONENTS OF FRESHWATER COLLOIDAL ORGANIC MATTER REVEALED BY TRANSMISSION ELECTRON AND ATOMIC FORCE MICROSCOPY

Organic biopolymers such as humic substances and polysaccharides account for the majority of freshwater NOM. Their role in natural systems is largely dependent upon their supramolecular microscopic structure which cannot be determined by bulk chemical measurements alone. Microscopic techniques were developed so as to permit the systematic observation of several colloidal-sized organic macromolecules with variable structures. This paper describes the characteristic structures of some reference compounds representative of the major organic components of natural waters. Polyacrylic acid, alginic acid and schizophyllan in addition to humic substances and polysaccharides isolated from natural freshwaters were examined by transmission electron microscopy (TEM) and atomic force microscopy (AFM). The techniques were optimized for the observation of the aquatic biopolymers. Colloidal organic matter isolated from natural freshwaters was also observed by TEM and AFM and compared with the standard images of colloidal organic matter.

Sample preparation techniques for the observation of environmental biopolymers by atomic force microscopy

Although the structural characterization of environmental biopolymers is of prime importance in order to understand their roles in the natural environment, only limited analytical techniques are available that allow the determination of their morphologies and size distributions, due mainly to the complexity, heterogeneity and polydispersity of these organic colloids. Atomic force microscopy (AFM) has become an important technique for direct imaging of biomolecules with a sub nanometer resolution. This paper describes a systematic optimization of the AFM sample preparation technique prior to direct observation under ambient conditions. Three preparation methods (drop deposition, adsorption, ultracentrifugation) were tested on two reference compounds: a humic substance and a polysaccharide. The methods were evaluated using, where possible, quantitative analysis of the AFM images. The results indicated that each of the commonly used preparation techniques had potential artefacts, but when used in concert, structural parameters corresponding to those measured in solution could be determined. AFM height measurements performed under conditions of variable humidity demonstrated no observable structural effects on the biopolymers.

Characterization of Norwegian natural organic matter: Size, diffusion coefficients, and electrophoretic mobilities

Eighteen Norwegian NOM samples were analyzed by AFM, TEM, FCS, and CE. The TEM and AFM gave complementary, but not identical, information regarding the conformation of the NOM. A large majority of the material in all samples appeared as points with a size of approximately 2 nm or less. FCS gave values for diffusion coefficients which were in the range 2.1–3.0 × 10−10 m2 s−1. This corresponds to molecular diameters of between 1.6 and 2.0 nm, in reasonable agreement with both TEM and AFM. Electropherograms, using absorbance at 200 nm, were all dissimilar except for the Gjerstad and Hellerudmyra sample pairs, for which no major differences were observed. CE was also carried out using both fluorescence (excitation at 325, 457, and 488 nm) and UV-absorbance (200, 210, 254, and 288 nm) detection on three of the NOM samples. The different modes of detection and wavelengths gave qualitatively similar electropherograms. Calculated EPMs of the major sample components were in the range -2.0 to -5.0 10−8 m2 s−1 V−1.

An AFM study of the effect of chemical treatments on the surface microstructure and adhesion properties of flax fibres

The mechanical properties of fibre-reinforced polymer composites are largely dependant on the adhesion between the matrix and the fibre. In order to enhance the interaction between flax fibres and unsaturated polyester resins, raw fibres were chemically modified using sodium hydroxide, sodium hydroxide plus acetic anhydride and formic acid-based treatments. The physical properties of the modified fibres were investigated by means of the atomic force microscopy. At first, the morphological analysis of the surfaces shows that after the chemical treatments, the fibres surface appear to be less heterogeneous in topology and smoother. Nonetheless, no significant roughness difference was found between the different treatments. Secondly, adhesion forces measurements were performed between a standard AFM silicon nitride tip and the fibres. The adhesion forces were found to vary according to the chemical treatment. The sodium hydroxide-based treatment was found to increase the adhesion force between the fibre and the AFM tip whereas the lowest adhesion force was found for the formic acid- based treated fibre. These results were attributed to the different hydrophilic character of the modified fibres. Due to the importance of the water layer adsorbed on the fibres, the adhesion forces between the AFM tip and the different samples are found to be mainly dominated by capillary forces in relation with the fibres surface hydrophilicity.

Measuring adhesion forces between model polysaccharide films and PLA bead to mimic molecular interactions in flax/PLA biocomposite

Natural fiber-reinforced polymers or biocomposites are becoming increasingly popular as an environment friendly alternative to traditional glass fiber-reinforced thermoplastics. The mechanical properties of reinforced biocomposites, such as flax/polylactic acid (PLA), are largely governed by the level of interfacial interactions between the two constituents apart from their intrinsic properties. The hierarchical organization of various polysaccharides present in natural fibers results in complex mechanisms at the interface which are still poorly understood and difficult to analyze through a traditional approach that rely on indirect assessments. The possibility of measuring direct adhesion force between individual particles using the colloidal force microscopy has been exploited here by developing an experimental set-up in which a micrometer colloidal PLA bead is brought into close contact with molecularly smooth polysaccharide surfaces that mimic the main constituents of flax fibers, cellulose, hemicellulose, and pectins. Adhesion force measurements performed under ambient and low relative humidity conditions indicate that cellulose/PLA is the weakest interface in the biocomposite. Moreover, the results emphasize the important role of water molecules for the more hydrophilic polymers in flax fibers that takes place in the fundamental forces involved in the adhesion phenomena at the biocomposite interface.