Microstructural, mechanical and mass transport properties of isotropic and capillary alginate gels

Macroscopically homogeneous and inhomogeneous calcium alginate gels are formed via internal or external addition of various amounts of calcium to an alginate solution. The externally formed gels contain parallel aligned capillary structures. The mechanical and mass transport properties and the microstructure of the differently set gels were characterized by rheological measurements, fluorescence recovery after photobleaching (FRAP) and transmission electron microscopy (TEM). TEM images show a zone of distorted anisotropic gel structure in the vicinity of the capillaries as well as indications of a lower degree of void connectivity. The diffusion rates of dextran at large distances from the capillaries were fast and capillary gels showed a plastic behaviour in comparison to the internally set gels. The results presented show large functional differences between the internally and externally set gels, which cannot be explained by the presence of capillaries alone

The impact of interfaces in laminated packaging on transport of carboxylic acids

The permeability of oleic and acetic acid through low density polyethylene (LDPE) and ethylene acrylic acid (EAA) have been measured using diffusion cells. In addition, the permeability through combinations of LDPE and EAA in the form of laminates with different numbers of layers has been determined. Oleic acid shows an almost 30 times higher permeability compared to acetic acid, which was partly explained by the adsorption of oleic acid to the film surface during the permeability experiment. In addition, the permeability is lower for both oleic and acetic acid in the laminates compared to the pure films. The decreased permeability can be explained by the presence of crystalline domains close to the interface. This is supported by SAXS data which suggests an ordering of polymer chains in the EAA film close to the interface. In summary, the results show that it is possible to create barrier materials with decreased permeability, which is interesting for example in the packaging industry. (C) 2016 Elsevier B.V. All rights reserved

Water pores in alkyl ketene dimer (AKD) dispersions studied by NMR diffusometry and optical microscopy

Water borne alkyl ketene dimer (AKD) dispersions have been investigated by means of optical microscopy and NMR diffusometry (NMR-D). In two different formulations, different amounts of entrapped water in pores with different sizes are obtained, which can be compared to a waterin-oil-in-water (w/o/w) dispersion. It is shown that the amount of entrapped water inside the AKD particles can conveniently be measured with the NMR-D technique. The pore size is however not obtained correctly from the NMR-D experiment. Due to the small size of the water pores, the pore size is underestimated when measured with NMR-D. This effect is investigated in more detail by Brownian dynamic simulations from which a correction factor is obtained that allows a more correct value of the pore size from NMR-D measurements. When the pore size is too small to be observed by optical microscopy, typically below 0.5 mu m, NMR diffusometry combined with Brownian dynamic simulations are shown to be a rapid and reliable tool for quantifying the porosity in these types of systems

Chocolate Swelling during Storage Caused by Fat or Moisture Migration

Quantification of swelling in dark chocolate subjected to fat or moisture migration was conducted using a new method based on confocal chromatic displacement sensor. The nondestructive method allowed for the height profile of dark chocolate samples to be scanned with a sensitivity of ± 2.8 μm. By performing multiple scans on each sample prior to and after being subjected to fat or moisture migration, the induced swelling could be quantified. Applying the new method on confectionery systems revealed that fat and moisture migration generate different swelling behavior/kinetics in dark chocolate during storage. Moisture migration resulted in a rapid swelling once a water activity of 0.8 was reached in the chocolate, probably by interaction and absorption of moisture by the particulate solids. Fat migration also affected the swelling behavior in chocolate, possibly by inducing phase transitions in the continuous cocoa butter phase. Migrating fat also proved to induce a more pronounced swelling than the same amount of absorbed moisture which further consolidated that the observed swelling caused by fat or moisture migration is a result of significant different mechanisms. © 2012 Institute of Food Technologists®

Effect of Gelatin Gelation Kinetics on Probe Diffusion Determined by FRAP and Rheology

The time-dependent diffusion and mechanical properties of gelatin in solution, in the gel state, and during the sol/gel transition were determined using fluorescence recovery after photobleaching (FRAP) and rheology. The parameters in the experimental design were 2% w/w and 5% w/w gelatin concentration; 15, 20, and 25 degrees C end quench temperatures; and Na-2-fluorescein, 10 kDa FITC-dextran, and 500 kDa FITC-dextran as diffusion probes. The samples were monitored in solution at 60 degrees C, during quenching, for 75 min at end quench temperatures and after 1, 7, and 14 days of storage at the end quench temperature. The effect of temperature on the probe diffusion was normalized by determining the free diffusion of the probes in pure water for the different temperatures. The results gained by comparing FRAP and rheology showed that FRAP is able to capture structural changes in the gelatin before gelation occurs, which was interpreted as a formation of transient networks. This was clearly seen for 2% w/w gelatin and 20 and 25 degrees C end quench temperatures. The structural changes during sol/gel transition are detected only by the larger probes, giving information about the typical length scales in the gelatin structure. The normalized diffusion rate increased after 7 and 14 days of storage. This increase was most pronounced for fluorescein but was also seen for the larger probes

Probe diffusion in κ-carrageenan gels determined by fluorescence recovery after photobleaching

The effects of free volume and heterogeneity on probe diffusion in κ-carrageenan gels were determined by fluorescence recovery after photobleaching (FRAP) and rheology. By changing the ionic conditions, biopolymer concentration and end temperature, different microstructures and aggregation kinetics in the κ-carrageenan gels were evaluated. The results of the FRAP measurements were compared to transmission electron microscopy (TEM) and nuclear magnetic resonance diffusometry (NMRd) data from previous studies. The results showed that the free diffusion rates of the probe (FITC dextran) in water were influenced by both temperature and ionic conditions. The free diffusion values were used for normalization of the diffusion rates in the κ-carrageenan gel measurements. The compatibility between FITC dextran with different molecular weights (10 and 500 kDa) and κ-carrageenan was evaluated. The results showed that the larger FITC dextran probe phase separates; therefore only the 10 kDa FITC dextran probe was used in the FRAP experiments. FRAP measurements and NMRd probe diffusion in combination with TEM in κ-carrageenan revealed that the void space, degree of aggregation and heterogeneity influence the probe diffusion rate. The κ-carrageenan gelation was analyzed at different end temperatures using rheology and FRAP. The FITC dextran probe diffusion was not influenced by κ-carrageenan aggregation, regardless of rheological gelation kinetics and storage modulus near the gel point. This indicates that the average void space between the gel strands is larger than the size of the probe. Good correlation between the microstructure and the probe diffusion rate in κ-carrageenan gel with different ionic conditions and constant biopolymer concentration were obtained with TEM and FRAP

Determination of local diffusion properties in heterogeneous biomaterials

The coupling between structure and diffusion properties is essential for the functionality of heterogeneous biomaterials. Structural heterogeneity is defined and its implications for time-dependent diffusion are discussed in detail. The effect of structural heterogeneity in biomaterials on diffusion and the relevance of length scales are exemplified with regard to different biomaterials such as gels, emulsions, phase separated biopolymer mixtures and chocolate. Different diffusion measurement techniques for determination of diffusion properties at different length and time scales are presented. The interplay between local and global diffusion is discussed. New measurement techniques have emerged that enable simultaneous determination of both structure and local diffusion properties. Special emphasis is given to fluorescence recovery after photobleaching (FRAP). The possibilities of FRAP at a conceptual level is presented. The method of FRAP is briefly reviewed and its use in heterogeneous biomaterials, at barriers and during dynamic changes of the structure is discussed

Impact of pre-crystallization process on structure and product properties in dark chocolate

Dark chocolate microstructures with different structure densities, i.e., close-packing of the fat crystal lattice, and homogeneity i.e., evenness and connectivity of the fat crystal network, were created by βVI- seeding or conventional pre-crystallization with various degrees of temper and were evaluated with respect to storage stability. The structure characterization was conducted by measuring the strength of the cocoa butter crystal network with traction tests combined with DSC melting curves. Subsequent storage stability was evaluated with DigiEye technique for fat bloom development and gravimetrical techniques for fat/moisture migration. The two pre-crystallization processes generated significantly different structures and storage stability. Well-tempered βVI-seeding resulted in a dense and homogenous chocolate structure directly after solidification, which was optimal in order to retard fat bloom and fat migration. However, a too high structure density generated heterogeneous structures with reduced ability to withstand fat bloom. A lower structure density exhibited optimal resistance against moisture migration. © 2012 Elsevier Ltd. All rights reserved