Dominika Pawcenis

Nanoscale analysis of degradation processes of cellulose fibers.

Mapping the morphological and nano-mechanical properties of cellulose fibers within paper sheets or textile products at the nano-scale level by using atomic force microscopy is a challenging task due to the huge surface level variation of these materials. However this task is fundamental for applications in forensic or cultural heritage sciences and for the industrial characterization of materials. In order to correlate between nano-mechanical properties and local nanometer scale morphology of different layers of cellulose fibers, a new strategy to prepare samples of isolated cellulose fibers was designed. This approach is based on immobilizing isolated fibers onto glass slides chemically pretreated so as to promote cellulose adhesion. The experiments presented here aim at the nano-scale characterization of fibers in paper samples aged under different external agents (relative humidity, temperature) in such a way as to promote hydrolysis and oxidation of polymers. The observed variability of local mechanical properties of paper fibers was related to varying degrees of cellulose polymerization induced by artificial aging.

Effect of thermal treatment on potato starch evidenced by EPR, XRD and molecular weight distribution.

Effect of heating of the potato starch on damages of its structure was investigated by quantitative electron paramagnetic resonance (EPR) spectroscopy, X‐ray diffraction and determination of the molecular weight distribution. The measurements were performed in the temperature range commonly used for starch modifications optimizing properties important for industrial applications. Upon thermal treatment, because of breaking of the polymer chains, diminishing of the average molecular weights occurred, which significantly influences generation of radicals, evidenced by EPR. For the relatively mild conditions, with heating parameters not exceeding temperature 230 °C and time of heating equal to 30 min a moderate changes of both the number of thermally generated radicals and the mean molecular weight of the starch were observed. After more drastic thermal treatment (e.g. 2 h at 230 °C), a rapid increase in the radical amount occurred, which was accompanied by significant reduction of the starch molecular size and crystallinity. Experimentally established threshold values of heating parameters should not be exceeded in order to avoid excessive damages of the starch structure accompanied by the formation of the redundant amount of radicals. This requirement is important for industrial applications, because significant destruction of the starch matrix might annihilate the positive influence of the previously performed intentional starch modification. Copyright

Mark–Houwink–Sakurada coefficients determination for molar mass of silk fibroin from viscometric results. SEC-MALLS approach

The results on the changes of molar mass distributions and average molar masses in Bombyx mori fibroin with use of size exclusion chromatography (SEC) and viscometry, respectively, are presented in terms of the determination of Mark–Houwink–Sakurada coefficients, which are lacking in the literature. SEC was applied in configuration of light scattering and differential refractive index and multi angle laser light scattering detectors (SEC-DRI-MALLS). The coefficients calculated from the correlation between intrinsic viscosities and the absolute value of molar masses obtained using the SEC-MALLS technique are equal to: K = 1.813 × 10−4 dm3 g−1 (±1.74 × 10−5), α = 0.614 (±0.068). The value of the parameter α shows that silk fibroin molecules in an LiBr solution behave like a flexible polymer molecule in a thermodynamically good solvent. The results are discussed with focus on the applicability of glass capillary viscometry and size exclusion chromatography for assessment of silk based materials condition with particular reference to the preservation artifacts and ancient textiles.

Paper material containing Ag cations immobilised in faujasite: synthesis, characterisation and antibacterial effects

The study is devoted to manufacturing and characterising a new paper material with antimicrobial properties, as an alternative to paper containing silver nanoparticles (NPs) which are claimed to be harmful to the ecosphere. In place of silver NPs, the new material contains faujasite mineral (from the faujasite group) exchanged with silver cations which are firmly attached to the material’s lattice. The material was obtained by typical ion exchange and additional elution with EDTA salt to dispose of the remaining silver oxide NPs. Thus, modified faujasite was then added to paper pulp. The new, modified paper showed better quality in terms of acidity, tensile strength and cellulose degree of polymerisation compared to paper containing Ag NPs. The visual quality of the paper is also better than that containing Ag NPs. The new material shows high potential for use in food and pharmaceutics packaging.

Effect of ball-milling on crystallinity index, degree of polymerization and thermal stability of cellulose

A combined study of crystallinity index (CI), degree of polymerisation (DP) and thermal stability of cellulose was carried out for monitoring the effect of ball-milling. DP and CI are two fundamental quantities that describe the physico-chemical behaviour of cellulose. Milling is a common strategy to reduce cellulose crystallinity. In this work, four different commercially available celluloses were milled at 30, 60 and 120 min, and the changes in DP and CI were monitored using spectroscopic, diffraction and chromatographic techniques. Evolved gas analysis-mass spectrometry (EGA-MS) was also used to evaluate the changes in apparent activation energy (Ea) of the pyrolysis reaction upon different milling times by using model-free isoconversional methods. The results showed substantial decrease in CI values and moderate changes in DP after two-hours of ball-milling. Ea were found in the range 110-140 kJ/mol, and were reduced by 10% on average after two hours of ball-milling.