Study of Hydrophilic Properties of Polysaccharides

In this research, the structural characteristics, specific surface area, sorption of water vapor, and wetting enthalpy of various polysaccharides (cellulose, hemicelluloses, starch, pectin, chitin, and chitosan) have been studied. It was confirmed that crystallites are inaccessible for water, and therefore water molecules can interact only with polar groups in noncrystalline (amorphous) domains of biopolymers. The isotherms of water vapor sorption for various polysaccharides had sigmoid shapes, which can be explained by the absorption of water molecules in heterogeneous amorphous domains having clusters with different packing densities. The method of contributions of polar groups to sorption of water molecules was used, which allowed to derivate a simple calculating equation to describe the shape of sorption isotherms. The wetting of biopolymers with water was accompanied by a high exothermic thermal effect, in direct proportion to the amorphicity degree. The sorption values and wetting enthalpies of amorphous domains of biopolymers were calculated, which allowed to find the hydrophilicity index and compare the hydrophilicity of the various polysaccharides.

Analysis of Spontaneous Ignition of Grass: Chemical Oxidation and Water Vapor Sorption

Self-heating of biomass by chemical oxidation, which can cause spontaneous ignition, is a safety and management concern. This process can be accelerated by aerobic fermentation and water vapor sorption. The chemical oxidation and water vapor sorption of grass were studied in a laboratory oven, measuring the variations in weight and the internal temperature of a sphere with grass within a flexible polymeric network. Both processes were simulated to prove that the proposed mathematical model could fit the experimental data. It was observed that the water vapor sorption capacity of the grass was high, so the experimental increase in the internal temperature of a spherical body was around 47 K, from 73°C to 120°C. This fact can be very important because the chemical oxidation of grass accelerates at high temperatures. For scaling, simulation programs were used to study the sorption and oxidation processes with an increase in internal temperature in spherical bodies and infinite plane slabs. These results can be used to obtain those of other geometric symmetries by interpolation. It was deduced that at 70°C and with vapor sorption, the ignition time can be around 3 days to 5 days, while without vapor sorption, the ignition times can be around 110 days to 140 days. For 35°C the ignition times with vapor sorption can be around 12 days to 18 days, while without vapor sorption the ignition times can be around 3700 days to 4500 days. These results can be of interest for warehouses of similar biomass and for forestry research and management groups of wildfires. Graphical Abstract

Materials on Plant Leaf Surfaces are Deliquescent in a Variety of Environments

Many materials on plant leaf surfaces are hygroscopic, and they impact foliar applied agrochemicals, foliar water uptake, gas exchange and stomatal density. Few studies are available on the nature of these substances, and we quantify how hygroscopic these materials are. Water vapor sorption experiments on twelve leaf washes were conducted and analyzed with inductively coupled plasma-optical emission spectroscopy and X-ray diffraction. Oils were found in all Eucalyptus samples studied. The leaf materials can deliquesce and form an aqueous solution in a variety of environments where plants grow, including glasshouses and by the ocean. All plant materials studied were hygroscopic. For mangroves that excrete salt to the leaf surfaces, significant sorption occurred at high humidity of a total of 316 mg (~0.3 mL) over 6-10 leaves. These fitted a Guggenheim, Anderson, and de Boer isotherm; mostly due to sodium chloride, though other more hygroscopic materials were also present.

Siloxane Matrix Molecular Weight Influences the Properties of Nanocomposites Based on Metal Complexes and Dielectric Elastomer

Siloxane-based elastomers are some of the most sought-after materials for the construction of actuators and equipment for energy harvesting devices. This article focuses on changes of the mechanical (breaking stress, breaking strain, Young’s modulus) and dielectric properties for elastomers prepared with silicones, induced by the variation of molecular weight of the matrix, with three different silicone polymers having 60,000 g/mol, 150,000 g/mol, and 450,000 g/mol (from GPC measurements). Multiple siloxane elastomers were crosslinked with methyltriacetoxysilane using the sol-gel route. The dielectric permittivity values of the elastomers were also enhanced with two different complex structures containing siloxane bond and 3d transition metals as filler materials for polydimethylsiloxane polymers with various molecular weights. The dielectric spectroscopy tests demonstrated a small decrease (5%) for the values of the dielectric permittivity in relation to increased molecular weight of the siloxane polymer, both for samples prepared with pure polymer and for samples with metal complexes. The samples of nanocomposites showed a >50% increase of dielectric permittivity values relative to samples prepared of pure siloxane elastomer. The thermal tests demonstrated that the nanocomposites retained thermal stability similar with samples prepared of pure siloxane elastomer. The behavior under controlled conditions of humidity showed a trend of increased water vapor sorption with increasing molecular weight but an overall hydrophobic stable character of nanocomposites.

Water vapor sorption behavior of bamboo pertaining to its hierarchical structure

Bamboo is an anisotropic, hierarchical, and hygroscopic material. Moisture transport in bamboo is one of the most fundamental properties affecting almost all other physical and mechanical properties of the material. This study investigated the water vapor sorption behaviors of bamboo at various structural levels: cell walls, cells (with pits) and bamboo blocks. The specimens with two sorption directions, longitudinal (L) and transverse (T), were measured by saturated salt solution method and dynamic vapor sorption. The parallel exponential kinetics model was used to analyze the sorption kinetics. The results showed that at the cell wall level, the sorption rate and equilibrium moisture content (EMC) of cell wall in the L specimens were larger than those in the T specimens. The differences were probably caused by the looser cell wall layers in the L specimens. At the cellular scale, pits in the cell wall resulted in an enhanced sorption rate and EMC of the T specimens compared with the L specimens where the pits in the parenchyma cells were only distributed in the lateral walls but not in end walls. At the macro scale, the sorption rate and moisture content of bamboo blocks were largely controlled by the vessel cells. As a hierarchically-structured plant, bamboo performs the biological function of moisture transport at all these scales. This work helps improve the understanding of water transport behavior in bamboo, which may lead to better bamboo drying and impregnation processes.

Characterization of an Isostructural MOF Series of Imidazolate Frameworks Potsdam by Means of Sorption Experiments with Water Vapor

Sorption measurements of water vapor on an isoreticular series of Imidazolate Frameworks Potsdam (IFP), based on penta-coordinated metal centers with secondary building units (SBUs) connected by multidentate amido-imidate-imidazolate linkers, have been carried out at 303.15 K. The isotherm shapes were analyzed in order to gain insight into material properties and compared to sorption experiments with nitrogen at 77.4 K and carbon dioxide at 273.15 K. Results show that water vapor sorption measurements are strongly influenced by the pore size distribution while having a distinct hysteresis loop between the adsorption and desorption branch in common. Thus, IFP-4 and -8, which solely contain micropores, exhibit H4 (type I) isotherm shapes, while those of IFP-1, -2 and -5, which also contain mesopores, are of H3 (type IV) shape with three inflection points. The choice of the used linker substituents and transition metals employed in the framework has a tremendous effect on the material properties and functionality. The water uptake capacities of the examined IFPs are ranging 0.48 mmol g−1 (IFP-4) to 6.99 mmol g−1 (IFP-5) and comparable to those documented for ZIFs. The water vapor stability of IFPs is high, with the exception of IFP-8.