Surface properties of distinct nanofibrillated celluloses assessed by inverse gas chromatography

The adhesion and surface properties of nanocelluloses are an important issue to consider when using this material for composites production, in food packaging or coatings, as well as for determining the influence of added functional groups. In the present work, the surface properties of two nanofibrillated celluloses obtained by mild 2,2,6,6-tetramethylpiperidine-1- oxyl radical (TEMPO)-mediated oxidation with distinct mechanical treatment intensity in a homogenizer (5 and 15 passes), and one nanofibrillated cellulose obtained by enzymatic process, were thoroughly assessed by inverse chromatography, at infinite dilution conditions. The dispersion component of the surface energy ( s d) was 42-46 mJ m-2 at 40 ºC for the TEMPO nanofibres and 52 mJ m-2 for the enzymatic nanocellulose. It was confirmed, based on the determination of the specific components of the works of adhesion and enthalpies of adsorption with polar probes, that the surfaces of the materials have a more Lewis acidic than Lewis basic character. Regarding TEMPO nanofibres, a slight increase of Lewis acidity/basicity ratio seemed to occur for the more nanofibrillated material (15-passes). Higher specific interactions with polar probes were found for enzymatic nanocellulose. The higher values of s d and specific interactions observed for the enzymatic nanocellulose could partly be due to the higher crystallinity of this sample. On the other hand, the increase of the acidity/basicity ratio (as well as of the s d value) for the 15-passes vs. 5-passes TEMPO nanofibres was attributed to a higher exposition of the hydroxyl groups of cellulose at the surface of the former material

Prediction of inter-particle adhesion force from surface energy and surface roughness

Fine powder flow is a topic of great interest to industry, in particular for the pharmaceutical industry; a major concern being their poor flow behavior due to high cohesion. In this study, cohesion reduction, produced via surface modification, at the particle scale as well as bulk scale is addressed. The adhesion force model of Derjaguin-Muller-Toporov (DMT) was utilized to quantify the inter-particle adhesion force of both pure and surface modified fine aluminum powders (∼8 μm in size). Inverse Gas Chromatography was utilized for the determination of surface energy of the samples, and Atomic Force Microscopy was utilized to evaluate surface roughness of the powders. Surface modification of the original aluminum powders was done for the purpose of reduction in cohesiveness and improvement in flowability, employing either silane surface treatment or dry mechanical coating of nano-particles on the surface of original powders. For selected samples, the AFM was utilized for direct evaluation of the particle pull-off force. The results indicated that surface modification reduced the surface energy and altered the surface nano-roughness, resulting in drastic reduction of the inter-particle adhesion force. The particle bond number values were computed based on either the inter-particle adhesion force from the DMT model or the inter-particle pull-off force obtained from direct AFM measurements. Surface modification resulted in two to three fold reductions in the Bond number. In order to examine the influence of the particle scale property such as the Bond number on the bulk-scale flow characterization, Angle of Repose measurements were done and showed good qualitative agreements with the Bond number and acid/base surface characteristics of the powders. The results indicate a promising method that may be used to predict flow behavior of original (cohesive) and surface modified (previously cohesive) powders utilizing very small samples

Bromination of double-walled carbon nanotubes

Double-walled carbon nanotubes (DWCNTs) synthesized by catalytic chemical vapor deposition (CCVD) have been functionalized by bromine vapor at room temperature. At least two different bromine species were detected in the product using X-ray photoelectron spectroscopy (XPS) and thermal gravimetric analysis. The primary form is negatively charged Br2 molecules exhibiting an intense resonance at ∼238 cm−1 in the Raman spectrum. The electron transfer from the nanotubes to the adsorbed molecules is detected from C 1s XPS and near-edge X-ray absorption fine structure spectra. The optical absorption spectra reveal that although the metallic nanotubes are more reactive to Br2, the outer semiconducting nanotubes also readily interact with Br2 adsorbates. The secondary bromine form is attributed to covalent C-Br bonding, and its possible sources are discussed in the light of quantum-chemical calculations. Analysis of the XPS, Raman, and optical absorption spectra of the Br-DWCNTs annealed at 100-170 ° C indicates preservation of a part of bromine molecules in samples that affects the electronic and vibration properties of nanotubes