The injection molding ability of long glass fiber reinforced polyamide pellets was studied. The injection moldable materials were produced by a melt impregnation process of continuous fiber rovings. The rovings were chopped to pellets of 9 mm length. Chopped pellets with a variation in the degree of impregnation and fiber concentration were studied. The injection molded samples were analyzed for fiber concentration, fiber length, and fiber orientation. Dumbbell-shaped tensile bars were made to evaluate the mechanical properties. The fibers in the tensile bars had a high orientation in the flow direction and minor fiber concentration gradients were observed. The fiber lengths decreased with fiber concentration from 1.6 mm for a 2 vol% to 0.6 mm for a 25 vol% system. The tensile and impact properties increased considerably with fiber concentration. A low degree of impregnation in the pellets of the fibers resulted in somewhat lower tensile and impact properties.
The solution and adsorption behavior of a series of diblock copolymers of hydrophobic poly(dimethyl siloxane) and hydrophilic poly(2-ethyl-2-oxazoline) was studied. These block copolymers formed large polydisperse micelles in an aqueous solution. The critical micelle concentration was lower than 2 mg L-1. The adsorption kinetics of these polymers onto macroscopically flat oxide surfaces was studied with reflectometry in stagnation point flow. Both blocks of the copolymers had affinity for silica, and only the hydrophobic block had affinity for the titania surface. Nevertheless, the adsorption curves on silica and titania had similar features. The adsorption kinetics was affected by the exchange rate between micelles and free polymers. For short polymer chains the exchange rate was fast compared with the time necessary for diffusion across the diffusive layer. Before the micelles arrived at the surface, they had already broken up into unimers. Because the critical micelle concentration was very low, the experimental adsorption rate was determined by the diffusion of micelles toward the surface. This was not the case for the longest polymer chain; the exchange between micelles and unimers was relatively slow. The micelles did not adsorb directly, and the adsorption rate was determined by the exchange of polymers between micelles and solution. For all polymer samples the adsorption increases linearly as a function of time, up to very high adsorbed amounts where it reaches a plateau. The adsorbed amount on silica is considerably higher than found for titania. The poly(dimethyl siloxane) was anchored more strongly to the silica surface than to titania; the density of the adsorbed layer could therefore become higher.
The adsorption of graft copolymers of poly(acrylamide) (PAAm, backbone) and poly(ethylene oxide) (PEO, side chains) from aqueous solution onto silica and titania was studied with reflectometry. Two high-molar-mass copolymers were used with different PEO graft densities (10 and 18% w/w PEO in copolymers G10 and G18, respectively). On titania only the PAAm backbone adsorbs and the PEO does not. This results in adsorbed amounts of 0.83 and 0.85 mg m-2, respectively, which is about the same as that for a PAAm homopolymer. On silica the situation is reversed: now the PEO side chains adsorb and the PAAm backbone does not. The adsorption as a function of time shows a maximum, before the stable plateau is reached. The adsorbed amount on silica is much higher than that on titania: in the final plateau it is 1.35 and 1.2 mg m-2 for G18 and G10, respectively. On silica the polymers form longer loops and tails so that more molecules can be accommodated at the surface. The overshoot on silica depends on the polymer concentration, suggesting that it is not caused by a conformational change of the adsorbed layer but by exchange with polymer molecules from solution. Differences in graft distribution and graft density in the polymer sample are probably responsible for the displacement. The average number of grafts per polymer is rather low. On statistical grounds there should be an appreciable polydispersity in graft distribution and in graft density. Molecules in which the grafts are clustered in a few groups can displace molecules with more regularly separated grafts, and molecules with a high graft density can displace those with a lower number of side chains. The newly arriving molecules can then adsorb in a flatter conformation with a lower adsorbed amount as the extra loss in conformational entropy is compensated by the gain in adsorption energy.
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