ATR-FTIR spectroscopy and spectroscopic imaging of solvent and permeant diffusion across model membranes

The uptake and diffusion of solvents across polymer membranes is important in controlled drug delivery, effects on drug uptake into, for example, infusion bags and containers, as well as transport across protective clothing. Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy has been used to monitor the effects of different solvents on the diffusion of a model compound, 4-cyanophenol (CNP) across silicone membrane and on the equilibrium concentration of CNP obtained in the membrane following diffusion. ATR-FTIR spectroscopic imaging of membrane diffusion was used to gain an understanding of when the boundary conditions applied to Fick's second law, used to model the diffusion of permeants across the silicone membrane do not hold. The imaging experiments indicated that when the solvent was not taken up appreciably into the membrane, the presence of discrete solvent pools between the ATR crystal and the silicone membrane can affect the diffusion profile of the permeant. This effect is more significant if the permeant has a high solubility in the solvent. In contrast, solvents that are taken up into the membrane to a greater extent, or those where the solubility of the permeant in the vehicle is relatively low, were found to show a good fit to the diffusion model. As such these systems allow the ATR-FTIR spectroscopic approach to give mechanistic insight into how the particular solvents enhance permeation. The solubility of CNP in the solvent and the uptake of the solvent into the membrane were found to be important influences on the equilibrium concentration of the permeant obtained in the membrane following diffusion. In general, solvents which were taken up to a significant extent into the membrane and which caused the membrane to swell increased the diffusion coefficient of the permeant in the membrane though other factors such as solvent viscosity may also be important.

Caking strength of granulated clay under frozen conditions

Transport of particulate clay occurs during some extremely cold weather conditions typically in the winter in the far North area. During the transport and temporary storage time, the clay may cake inside a rail or road wagon or in a silo, and consequently be difficult to be discharged from the containers. This paper studied caking strength of a granulated clay powder with a certain water moisture content of 18% for influences of temperature, packing stress and freezing time. The temperature tested was -5 oC, -10 oC and -20 oC. Because the clay powder may be packed at different bed depth, the study was undertaken across the packing stress range at 8.3 kPa (1 m bed depth), 25.0 kPa (3 m) and 75.0 kPa (9 m). Freezing time varied between 4 hours (transport) and 18 hours (overnight). During the tests, failure of caked materials was measured using a QTS texture analyzer and the caking strength of frozen samples was calculated. Influences on freeze caking of granular clay in storage or transport are discussed briefly. Some conclusions are made at the end of the paper,including recommendations for practical methods for mitigating these problems.