Regenerated cellulosic fibres undergo a process described as scission-reordering during hydrolysis in solutions of mineral acid. This occurs within disordered polymer regions at lateral crystal interfaces, which are accessible to aqueous agents through the pore spaces and polymer free volume. This process is distinct from that of oligomersolubilsation, which occurs within disordered polymer regions in series between crystal domains, where no effective template exists for recrystallisation. The degradation of series disorder will have the greatest influence on fibre tensile properties, which fall dramatically even at low levels of hydrolysis. The mechanics of fibrillation are most sensitive to the degradation of lateral disorder, which occurs at a higher rate constant. Soft-touch fabric processing may therefore be possible under conditions where there is a reduced influence on tensile performance. A kinetic model has been proposed to describe the hydrolysis and recrystallisation pathways, which shows that lyocell has longer but thinner crystal domains than viscose or modal fibres, and also a tighter distribution of lateral crystal sizes. Lyocell also has a lower proportion of series disorder and also thinner regions of lateral disorder. This is consistent with the overall greater crystallinity of the original lyocell fibre and the also of the final microscrystalline product.
The Lewis-acid catalytic reactions of magnesium chloride with regenerated cellulosic fibres under baking conditions can be interpreted using existing semi-crystalline morphological models. Reaction at 180°C is associated with chain scission, which takes place randomly within the accessible regions of the fibre structure. This causes a rapid reduction in the cellulose degree of polymerization, which stabilizes at a limiting value, analogous to that observed with wet-state mineral acid catalysed hydrolysis. A slower scission-reaction is also observed, believed to be due to the liberation of single glucan units from crystallite ends, again analogous to wetstate mineral acid hydrolysis. Dry-state catalysis is promoted by thermal molecular motion, allowing migration of catalyst ions and also conformational flexing of the cellulose polymer, which also induces a small amount of recrystallisation at crystallite lateral surfaces. Differences in the dry-state reaction have been observed for lyocell, viscose and modal regenerated fibres, which can be related to differences in crystallinity and resulting accessibility of the magnesium chloride catalyst. For lyocell the accessibility towards magnesium chloride is lower than found with mineral acids, which may be significant in the development of treatments to promote mechanical fibrillation, without sacrificing fibre tensile properties.
CPMAS carbon-13 NMR has been used to follow structural changes affecting regenerated cellulose fibres during hydrolysis by mineral acids. The C4 envelope of regenerated cellulose was deconvoluted into separate peaks, for ordered (crystal), part-ordered (surface) and disordered (non-crystal) polymer, which allowed calculation of average crystal lateral sizes, in good agreement with WAXD data. A geometrical model has been used to describe recrystallisation at lateral crystal faces, occurring within a disordered boundary surrounding the crystal interior. A onedimensional relaxation-diffusion model has also been constructed, appropriate to the spinodal structure of lyocell. This has provided estimates of proton T 1q relaxation times for pure crystalline (cellulose II) and non-crystalline cellulose, around 24 and 4.5 ms, respectively, at a 45 kHz B 1 field. From the model, crystalline and non-crystalline regions in lyocell are estimated to each be around 2.5 nm thickness for a material of 50% crystallinity, consistent with the 2-3 nm dimensions derived from C4 peak devonvolution.
A combination of techniques have been used to characterise lyocell regenerated cellulose fibre subjected to low-moisture thermal-catalytic reactions with zinc chloride Lewis acid. Application from non-swelling ethanol reduces catalyst accessibility, but at high temperatures migration takes place through the internal fibre morphology. The extent of chain scission is reduced at lower temperatures, leading to a higher leveling-off degree of polymerisation (LODP). In contrast, application of zinc chloride from water results in a lower LODP, due to the more even distribution of catalyst. The weights of extractable polymer material increase according to two separate rate constants, following established semicrystalline models. A higher Arrhenius activation energy for chain scission is seen for zinc chloride application from ethanol, which may be due to the physical mobilisation of the cellulose polymer at high temperature, associated with a cellulose T g . This may also aid recrystallisation. Cellulose dehydration endotherms and pyrolysis exotherms are shifted to lower temperature for application of zinc chloride from ethanol compared to water, which may be the result of a higher local concentration of catalyst and a faster reaction onset.
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