We have used a dynamic density functional theory ͑DDFT͒ for polymeric systems, to simulate the formation of micro phases in a melt of an asymmetric block copolymer, A n B m ( f A ϭ1/3), both in the bulk and in a thin film. In the DDFT model a polymer is represented as a chain of springs and beads. A spring mimics the stretching behavior of a chain fragment and the spring constant is calculated with the Gaussian chain approximation. Simulations were always started from a homogeneous system. We have mainly investigated the final morphology, adopted by the system. First, we have studied the bulk behavior. The diblock copolymer forms a hexagonal packed array of A-rich cylinders, embedded in a B-rich matrix. Film calculations have been done by confining a polymer melt in a slit. Both the slit width and surface-polymer interactions were varied. With the outcomes a phase diagram for confined films has been constructed. Various phases are predicted: parallel cylinders (C ʈ ), perpendicular cylinders (C Ќ ), parallel lamellae (L ʈ ), and parallel perforated lamellae (CL ʈ ). When the film surfaces are preferentially wet by either the A or the B block, parallel oriented microdomains are preferred. A perpendicular cylindrical phase is stable when neither the A nor B block preferentially wets the surfaces. The predicted phase diagram is in accordance with experimental data in the literature and explains the experimentally observed differences between films of asymmetric block copolymers with only two parameters: the film thickness and the energetic preference of the surface for one of the polymer blocks. We have also observed, that confinement speeds up the process of long range ordering of the microdomains.

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A dynamic density functional theory for polymeric systems has been used to investigate the influence of surface fields on the morphology of thin films of asymmetric diblock copolymers, which form cylinders in a bulk system. We have found that noncylindrical structures become stable when one of the blocks is strongly attracted by the surfaces. When the interaction between the surface and the polymer was increased, two transitions occur: (a) from parallel oriented cylinders to parallel oriented perforated lamellae (C | f CL|) and (b) from this perforated lamellae to lamellae (CL| f L|). It has also been observed that the microstructure becomes much more sensitive to the film thickness in the case where the surfaces strongly attract one of the polymer blocks. The influence of the surfaces seems to be limited to a region with a size of the order of one domain-domain distance.

Salt crystallization at surfaces is an important problem for buildings and monuments. We do not consider the formation of salt crystals as such, but focus on transport properties of ions in a drying porous medium. We deal with the first phase of the drying process, where the water is still uniformly distributed throughout the medium. An approximate model is presented, which accounts for both convection and diffusion. It is shown that the key parameter is the Peclet number at the evaporating surface, Pe≡hL/εD, where h, L, ε, and D are the drying rate, sample size, porosity, and diffusion constant, respectively. When Pe≪1 (diffusion dominates over convection) the ions remain uniformly distributed throughout the system. Strong accumulation at the evaporating surface occurs for Pe≫1 (convection dominates over diffusion). Crossover behavior is found for Pe≈1. Therefore, it is likely that the first crystals will be formed both in the bulk and at the interfaces of the material when Pe≪1. For high values of Pe the density peak at the evaporating surface will reach the saturation concentration long before it is reached in the bulk of the material. As a consequence, the salt starts to crystallize at the interfaces.

Knowledge on moisture transport in wood is important for understanding its utilization, durability and product quality. Moisture transport processes in wood can be studied by Nuclear Magnetic Resonance (NMR) imaging. By combining NMR imaging with relaxometry, the state of water within wood can be identified, i.e. water bound to the cell wall, and free water in the cell lumen/vessel. This paper presents how the transport of water can be monitored and quantified in terms of bound and free water during water uptake and drying. Three types of wood from softwood to hardwood were selected covering a range of low to high density wood; pine sapwood and oak and teak. A calibration is performed to determine the different water states in each different wood type and to convert the NMR signal into moisture content. For all wood types, water transport appeared to be internally limited during both uptake and drying. In case of water uptake, free water was observed only after the cell walls were saturated with bound water. In case of drying, the loss of bound water starts only after vanishing of free water, irrespective of the position. Obviously, there is always a local thermodynamic equilibrium of bound and free water for both uptake and drying. Finally, we determined the effective diffusion coefficient (D eff ). Experimentally determined diffusion constants were compared with those derived by the diffusion models for conceptual understanding of transport mechanism. We found that diffusion in the cell wall fibers plays a critical role in the transport process.