The use of atomic force microscopy in investigating particle caking mechanisms

Spray-dried materials are being used increasingly in industries such as food, detergent and pharmaceutical manufacture. Spray-dried sodium carbonate is an important product that has a great propensity to cake; its moisture-sorption properties are very different to the crystalline and amorphous species, with a great affinity for atmospheric moisture. This work demonstrates how the noncontact surface analysis of individual particles using atomic force microscopy can highlight the possible mechanisms of unwanted agglomeration. The nondestructive nature of this method allows cycling of localised humidity in situ and repeated scanning of the same particle area. The resulting topography and phase scans showed that humidity cycling caused changes in the distribution of material phases that were not solely dependent on topographical changes. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A comparison of compacting and caking behavior of carbonate-based washing powders

Two types of sodium carbonate powder produced by spray drying (SD) and dry neutralization (DN) were studied for their compaction properties using a uniaxial compression tester. A comparison was also made with Persil washing powder. Dry neutralized sodium carbonate showed greater resistance to compression and also produced a weaker compact when compressed to 100 kPa. Spray-dried sodium carbonate had an absence of fine particles but compacted easily. Differential scanning calorimetry (DSC) showed that both types of powder were predominantly amorphous in nature. Moisture sorption measurements showed that both powders behaved in a similar way below 50% relative humidity (RH). However, dry neutralized sodium carbonate had a high moisture affinity above this RH. Particle structures were also examined using scanning electron microscopy, showing the heterogeneous interior of the spray-dried particles. © 2013 Copyright Taylor and Francis Group, LLC.

Micropartículas de quitosana estruturadas com aerosil®: estabilidade, adsorção, encapsulação e liberação de substâncias ativas

Biodegradable microspheres used as controlled release systems are important in pharmaceutics. Chitosan biopolymer represents an attractive biomaterial alternative because of its physicochemical and biological characteristics. Chitosan microspheres are expected to become promising carrier systems for drug and vaccine delivery, especially for non-invasive ways oral, mucosal and transdermal routes. Controlling the swelling rate and swelling capacity of the hydrogel and improving the fragile nature of microspheres under acidic conditions are the key challenges that need to be overcomed in order to enable the exploration of the full pharmaceutical potential use of these microparticles. Many studies have focused on the modification of chitosan microsphere structures with cross-linkers, various polymers blends and new organic-inorganic hybrid systems in order to obtain improved properties. In this work, microspheres made of chitosan and nanosized hydrophobic silica (Aerosil R972) were produced by a method consisting of two steps. First, a preparation of a macroscopically homogeneous chitosan-hydrophobic silica dispersion was prepared followed by spray drying. FTIR spectroscopy, X-ray powder diffraction, differential scanning calorimetry, thermal gravimetric analysis, scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (TEM) were used to characterize the microspheres. Also, the were conducted acid stability, moisture sorption capacity, release properties and biological assays. The chitosan-hydrophobic silica composite microspheres showed improved thermal degradation, lower water affinity, better acid stability and ability to retard rifampicin and propranolol hydrochloride (drug models) release under simulated physiological conditions. In vitro biocompatibility studies indicated low cytotoxicity and low capacity to activate cell production of the pro-inflammatory mediator nitric oxide. The results show here encourage further studies on the use of the new chitosan-hydrophobic silica composite microspheres as drug carrier systems via oral or nasal routes.

The effects of formulation and processing on surface characteristics and functional properties of dairy powders

The objectives of this thesis were to (i) study the effect of increasing protein concentration in milk protein concentrate (MPC) powders on surface composition and sorption properties; (ii) examine the effect of increasing protein content on the rehydration properties of MPC; (iii) study the physicochemical properties of spraydried emulsion-containing powders having different water and oil contents; (iv) analyse the effect of protein type on water sorption and diffusivity properties in a protein/lactose dispersion, and; (v) characterise lactose crystallisation and emulsion stability of model infant formula containing intact or hydrolysed whey proteins. Surface composition of MPC powders (protein contents 35 - 86 g / 100 g) indicated that fat and protein were preferentially located on the surface of powders. Low protein powder (35 g / 100 g) exhibited lactose crystallisation, whereas powders with higher protein contents did not, due to their high protein: lactose ratio. Insolubility was evident in high protein MPCs and was primarily related to insolubility of the casein fraction. High temperature (50 °C) was required for dissolution of high protein MPCs (protein content > 60 g / 100 g). The effect of different oil types and spray-drying outlet temperature on the physicochemical properties of the resultant fat-filled powders was investigated and showed that increasing outlet temperature reduced water content, water activity and tapped bulk density, irrespective of oil type, and increased solvent-extractable free fat for all oil types and onset of glass transition (Tg) and crystallisation (Tcr) temperature. Powder dispersions of protein/lactose (0.21:1), containing either intact or hydrolysed whey protein (12 % degree of hydrolysis; DH), were spray-dried at pilot scale. Moisture sorption analysis at 25 °C showed that dispersions containing intact whey protein exhibited lactose crystallisation at a lower relative humidity (RH). Dispersions containing hydrolysed whey protein had significantly higher (P < 0.05) water diffusivity. Finally, a spray-dried model infant formula was produced containing hydrolysed or intact whey as the protein with sunflower oil as the fat source. Reconstituted, hydrolysed formula had a significantly (P < 0.05) higher fat globule size and lower emulsion stability than intact formula. Lactose crystallisation in powders occurred at higher RH for hydrolysed formula. In conclusion, this research has shown the effect of altering the protein type, protein composition, and oil type on the surface composition and physical properties of different dairy powders, and how these variations greatly affect their rehydration characteristics and storage stability.

Sustainable Catalysis : Rational Pd Loading on MIL-101Cr-NH2 for More Efficient and Recyclable Suzuki-Miyaura Reactions

Palladium nanoparticles have been immobilized into an amino-functionalized metal-organic framework (MOF), MIL-101Cr-NH2, to form Pd@MIL-101Cr-NH2. Four materials with different loadings of palladium have been prepared (denoted as 4-, 8-, 12-, and 16wt%Pd@MIL-101Cr-NH2). The effects of catalyst loading and the size and distribution of the Pd nanoparticles on the catalytic performance have been studied. The catalysts were characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) spectroscopy, powder X-ray diffraction (PXRD), N-2-sorption isotherms, elemental analysis, and thermogravimetric analysis (TGA). To better characterize the palladium nanoparticles and their distribution in MIL-101Cr-NH2, electron tomography was employed to reconstruct the 3D volume of 8wt%Pd@MIL-101Cr-NH2 particles. The pair distribution functions (PDFs) of the samples were extracted from total scattering experiments using high-energy X-rays (60keV). The catalytic activity of the four MOF materials with different loadings of palladium nanoparticles was studied in the Suzuki-Miyaura cross-coupling reaction. The best catalytic performance was obtained with the MOF that contained 8wt% palladium nanoparticles. The metallic palladium nanoparticles were homogeneously distributed, with an average size of 2.6nm. Excellent yields were obtained for a wide scope of substrates under remarkably mild conditions (water, aerobic conditions, room temperature, catalyst loading as low as 0.15mol%). The material can be recycled at least 10times without alteration of its catalytic properties.

Evaluation of thermo-physical properties and drying kinetics of carrots in a convective hot air drying system

This paper presents an experimental study on the evolution of carrot properties along convective drying by hot air at different temperatures (50ºC, 60ºC and 70ºC). The thermo-physical properties calculated were: specific heat, thermal conductivity, diffusivity, enthalpy, heat and mass transfer coefficients. Furthermore, the data of drying kinetics were treated and adjusted according to the three empirical models: Page, Henderson & Pabis and Logarithmic. The sorption isotherms were also determined and fitted using the GAB model. The results showed that, generally, the thermo-physical properties presented a decline during the drying process, and the decrease was faster for the temperature of 70ºC. It was possible to verify that the Page model presented the best prediction ability for the representation of kinetics of the drying process. The GAB model used to fit the sorption isotherms showed a good prediction capacity and, at a given water activity, despite some variations, the amount of water sorbed increased with the decrease of drying temperature.

Thermodynamic properties of water sorption of jackfruit (Artocarpus heterophyllus Lam.) as a function of moisture content

The Jackfruit tree is one of the most significant trees in tropical home gardens and perhaps the most widespread and useful tree in the important genus Artocarpus. The fruit is susceptible to mechanical and biological damage in the mature state, and some people find the aroma of the fruit objectionable, particularly in confined spaces. The dehydration process could be an alternative for the exploitation of this product, and the relationship between moisture content and water activity provides useful information for its processing and storage. The aim of this study was to determine the thermodynamic properties of the water sorption of jackfruit (Artocarpus heterophyllus Lam.) as a function of moisture content. Desorption isotherms of the different parts of the jackfruit (pulp, peduncle, mesocarp, peel, and seed) were determined at four different temperatures (313.15, 323.15, 333.15, and 343.15 K) in a water activity range of 0.02-0.753 using the static gravimetric method. Theoretical and empirical models were used to model the desorption isotherms. An analytical solution of the Clausius-Clapeyron equation was proposed to calculate the isosteric heat of sorption, the differential entropy, and Gibbs' free energy using the Guggenhein-Anderson-de Boer and Oswin models considering the effect of temperature on the hygroscopic equilibrium.

Thermodynamic properties of water sorption of jackfruit (Artocarpus heterophyllus Lam.) as a function of moisture content

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Moisture adsorption characteristics of ginger slices

The moisture adsorption characteristics of dried ginger slices was studied to determine the effect of storage conditions on moisture adsorption for the purpose of shelf life prediction, selection of appropriate packaging materials, evaluate the goodness-of-fit of sorption models, and determine the thermodynamics of moisture adsorption for application in drying. There was a highly significant effect (p < 0.05) of water activity (a w), temperature, and pre-treatment on the equilibrium moisture content (EMC) of the dried ginger slices. At constant a w, the EMC decreased as temperature increased. The EMC of all samples increased as the a w increased at constant temperature. The sorbed moisture of the unpeeled ginger slices was higher than the peeled while those of unblanched samples were higher than the blanched. Henderson equation allows more accurate predictions about the isotherms with the lowest %RMS, and therefore, it describes best the adsorption data followed by GAB, Oswin, and Halsey models in that order. The monolayer moisture generally decreased with temperature for all samples. The isosteric heat decreased with moisture content approaching the asymptotic value or the latent heat of vaporization of pure water (∆Hst = 0) while the entropy of sorption was observed to increase with moisture content.

Study of adsorption isotherms of green coconut pulp

O Brasil é considerado um dos maiores produtores e consumidores de frutas tropicais. O coco verde (Cocos nucifera L.) se destaca tanto em termos de produção e consumo quanto em quantidade de resíduos gerada por indústrias de água de coco e pelo consumo in natura. Portanto, existe uma necessidade de aproveitamento deste subproduto. Este trabalho teve por objetivo estudar as isotermas de adsorção da polpa de coco verde e determinação do calor isostérico de sorção. As isotermas de adsorção para as temperaturas de 30, 40, 50, 60 e 70 °C foram analisadas e evidenciaram curvas do tipo III, típicas de alimentos ricos em açúcares. Os dados experimentais de umidade de equilíbrio foram correlacionados por modelos da literatura. O modelo de GAB apresentou melhor concordância com os dados experimentais, entre os modelos avaliados. O calor isostérico de sorção é considerado um indicativo de forças atrativas intermoleculares entre os sítios de sorção de vapor de água, consequentemente, um importante fator para predizer a vida de prateleira de produtos desidratados.

Study of the enthalpy-entropy mechanism from water sorption of orange seeds (C. sinensis cv. Brazilian) for the use of agro-industrial residues as a possible source of vegetable oil production

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of maltodextrin and arabic gum in water vapor sorption thermodynamic properties of vacuum dried pineapple pulp powder

Moisture equilibrium data of pineapple pulp (PP) powders with and without additives - 18% maltodextrin (MD) or 18% gum Arabic (GA) - were determined at 20, 30, 40 and 50 degrees C by using the static gravimetric method in a water activity range of 0.06-0.90. The obtained isotherms were sigmoid, typical type 111, and the Guggenhein-Anderson-de Boer (GAB) model was fitted to the experimental data of equilibrium moisture content versus water activity. Addition of additives was shown to affect the isotherms in such a way that, at the same water activity, samples PP + GA and PP + MD presented lower equilibrium moisture content and were not so affected by varying temperature. The net isosteric heats of sorption of pulp powders with additives were higher (less negative) than those of pineapple pulp powders, suggesting that there are more active polar sites in the product without addition of GA or MD. An empirical exponential relationship could describe the heat of sorption dependence on the material moisture content. (C) 2007 Elsevier Ltd. All rights reserved.

Physical, Thermal and Water-Sorption Properties of Passion Fruit Seeds

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Nickel sorption capacity of ground xylem of Quercus ilex trees and effects of selected ligands present in the xylem sap

In this work the influence of four different ligands present in the xylem sap of Quercus ilex (histidine, citric, oxalic and aspartic acids) on Ni(II) adsorption by xylem was investigated. Grinded xylem was trapped in acrylic columns and solutions of Ni(II), in the absence and presence of the four ligands prepared in KNO(3) 0-1 mol L(-1) at pH 5.5, were percolated through the column. Aliquots of solutions were recovered in the column end for Ni determination by graphite furnace atomic absorption spectrometry (GFAAS). The experimental. data to describe Ni sorption by xylem in both the presence and absence of ligands was better explained by the Freundlich isotherm model. The decreasing affinity order of ligands for Ni was: oxalic acid > citric acid > histidine > aspartic acid. On the other hand, the Ni(II) adsorption by xylem increased following the inverse sequence of ligands. Potentiometric titrations of acidic groups were carried out to elucidate the sorption site groups available in Q. ilex xylem. The potentiometric titration has shown three sorption sites: pK(a) 2.6 (57.7% of the sorption sites), related to monobasic aliphatic carboxylic acids or nitrogen aromatic bases, pK(a) 8.1 (9.6%) and pK(a) 9.9 (32.7%), related to phenolic groups. (C) 2008 Elsevier GmbH. All rights reserved.