Water uptake determination

Experiment 1. To determine the water uptake of radish seeds... 

Equation (6.20) determines the maximum degree of swelling and the maximum pore radius of a liquid-equilibrated membrane. This relation suggests that the external gas pressure over the bulk water phase, which is in direct contact with the membrane, controls membrane swelling. The observa-hon of different water uptake by vapor-equilibrated and by liquid water-equilibrated PEMs, denoted as Schroeder s paradox, is thus not paradoxical because an obvious disparity in the external conditions that control water uptake and swelling lies at its root cause. 

Duplessix et al. used water vapor pressure isotherm (i.e., water uptake vs external relative humidity) data combined with simultaneous isotherm differential microcalorimeter analysis to determine the average heat of absorption per water molecule for 1200 EW acid form samples. Hysteresis was seen between sorption and subsequent desorption curves at 25 °C, and nonzero water content remained at zero relative humidity, indicating the presence of tightly... 

Different models determine A in different ways. Nation exhibits a water-uptake isotherm as shown in Figure 7. The dashed line in the figure shows the effects of Schroeder s paradox, where there is a discontinuous jump in the value of A. Furthermore, the transport properties have different values and functional forms at that point. Most models used correlate A with the water-vapor activity, since it is an easily calculated quantity. An exception to this is the model of Siegel et al., ° which assumes a simple mass-transfer relationship. There are also models that model the isotherm either by Flory—Huggins theory" or equilibrium between water and hydrated protons in the membrane and water vapor... 

The tensile properties of BCB/BMI are not affected by the absorption of water as shown in Table II. Future studies will be done to determine the effect of water uptake on the mechanical properties at elevated temperatures. 

Fat absorption and binding properties are determined by mixing food ingredients with fats and oils, and after a separation step (centrifugation) the amount of oil absorbed is measured. The test is similar to water uptake, that is, the method includes steps of subdivision, agitation, separation, and measurement. 

Laboratory research in this area is conducted by suspending a porous box of desiccant very close to the surface of a film balance. The rate of water uptake is determined by weighing at various times. This way the retardation of evaporation may be measured as a function of film pressure and correlated with other properties of the monolayer determined by the same method. As might be expected, the resistance to evaporation that a monolayer provides is enhanced by those conditions that promote the most coherent films, most notably high film pressures and straight-chain compounds. To see how this is quantified, consider the Example 7.3. 

Water uptake ability is a measure of the amount of water that a sample can imbibe under specified centrifugation conditions. The amount and composition of the sample need to be known. Samples need to be blended in the presence of excess liquid. After centrifugation, the amount of protein in the supernatant (i.e., protein lost from the sample) and the volume of supernatant can be measured to accurately determine water uptake ability. Alternatively, WUAcan be measured from the pellet itself. Both calculation methods are presented here. 

Expressible moisture and water uptake ability measure different properties. Figure B5.3.2 shows the very different cation and anion dependencies of these methods using fish samples. Figure B5.3.3 shows that the pH profiles are also different. It is also apparent that WUA is often >100%, while expressible moisture must, of necessity, be <100%. Figure B5.3.4 shows an example where expressible moisture was actually correlated with a separate and independent functional measurement. In this case, the binding of cooked fish muscle as determined by a subjective sensory panel pulling samples of fish apparently paralleled the moisture retention of the raw fish (moisture retention = 1 - expressible moisture). Ideally, functional properties should show such correlations with other properties of interest in food systems. 

Ling and Negendank have determined the water uptake of frog muscle from humid air (Fig. 35)255. After taking up 3—5% of the total amount, a co-operative adsorption of water is observed like a capillar or multilayer-condensation. 

A series of articles were published by Ennari et al. on MD simulation of transport processes in Poly(Ethylene Oxide) and sulfonic acid-based polymer electrolyte.136,137 The work was started by the determination of the parameters for the ions missing from the PCFF forcefield made by MSI (Molecular Simulations Inc.), to create a new forcefield, NJPCFF. In the models, the proton is represented as a hard ball with a positive charge. Zhou et al. used the similar approach to model Nation.138 The repeating unit of Nafion (Fig. 17) was optimized using ab initio VAMP scheme. The protons were modeled with hydronium ions. Three unit cell or molecular models were used for the MD simulation. The unit cell contains 5000 atoms 20 pendent side chains, and branched Nafion backbone created with the repeating unit. Their water uptakes or water contents were 3, 13, or 22 IEO/SO3, which correspond to the room temperature water uptakes at 50% relative humidity (RH), at 100% RH, and in liquid water respectively.18 The temperature was initially set at a value between 298.15 and 423.15 K under NVE ensemble with constant particle number, constant volume (1 bar), and constant energy. 

Ion selective membranes are the active, chemically selective component of many potentiometric ion sensors (7). They have been most successfully used with solution contacts on both sides of the membrane, and have been found to perform less satisfactorily when a solid state contact is made to one face. One approach that has been used to improve the lifetime of solid state devices coated with membranes has been to improve the adhesion of the film on the solid substrate (2-5). However, our results with this approach for plasticized polyvinylchloride (PVC) based membranes suggested it is important to understand the basic phenomena occurring inside these membranes in terms of solvent uptake, ion transport and membrane stress (4,6). We have previously reported on the design of an optical instrument that allows the concentration profiles inside PVC based ion sensitive membranes to be determined (7). In that study it was shown that water uptake occurs in two steps. A more detailed study of water transport has been undertaken since water is believed to play an important role in such membranes, but its exact function is poorly understood, and the quantitative data available on water in PVC membranes is not in good agreement (8-10). One key problem is to develop an understanding of the role of water uptake in polymer swelling and internal stress, since these factors appear to be related to the rapid failure of membranes on solid substrates. 

The release profile depends on 1) the annulus thickness, ie. the internal and external diameters 2) the swelling solution concentrations, both inside and outside the suppository 3) the period of swelling both inside and outside 4) the composition of the hydrogel which determines the water uptake and consequently the permeability of the drug through the matrix. 

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