Influence of lignin content in cellulose pulp on paper durability.

Paper degradation on a macroscopic scale is characterised primarily by yellowing, an increase in brittleness, and other destructive changes caused by the hydrolysis of glycoside bonds and oxidation reactions. Until now, lignin has been believed to cause these changes. However, contemporary analysis has not confirmed this assumption and has attributed low paper resistance to ageing with acidification owing to the production in acid environments that involve aluminium sulfate. In view of the common belief this manuscript presents studies on the accelerated ageing of papers with different lignin contents that are produced in neutral environments. To achieve the objective, artificially aged papers under conditions of increased humidity and temperature were investigated using chromatographic (SEC) and spectroscopic (FTIR and UV-Vis spectroscopy) techniques. Mechanical tests were used to determine the decrease in tensile properties of the samples. We observed no effects of the lignin content on the ageing rate of paper produced at neutral pH. This work also reveals the extent to which spectroscopic methods are useful for studying the papers containing lignin.

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.

DeNOx Abatement over Sonically Prepared Iron-Substituted Y, USY and MFI Zeolite Catalysts in Lean Exhaust Gas Conditions.

Iron-substituted MFI, Y and USY zeolites prepared by two preparation routes-classical ion exchange and the ultrasound modified ion-exchange method-were characterised by micro-Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and ultraviolet (UV)/visible diffuse reflectance spectroscopy (UV/Vis DRS). Ultrasound irradiation, a new technique for the preparation of the metal salt suspension before incorporation to the zeolite structure, was employed. An experimental study of selective catalytic reduction (SCR) of NO with NH3 on both iron-substituted reference zeolite catalysts and those prepared through the application of ultrasound conducted during an ion-exchange process is presented. The prepared zeolite catalysts show high activity and selectivity in SCR deNOx abatement. The MFI-based iron catalysts, especially those prepared via the sonochemical method, revealed superior activity in the deNOx process, with almost 100% selectivity towards N2. The hydrothermal stability test confirmed high stability and activity of MFI-based catalysts in water-rich conditions during the deNOx reaction at 450 °C.

Generalised two-dimensional correlation analysis of the Co, Ce, and Pd mixed oxide catalytic systems for methane combustion using in situ infrared spectroscopy.

The process of methane combustion over the surface of a catalyst is still not fully understood. The identification of the reaction path and the intermediates created during catalysis is crucial for understanding the transformation of methane molecules. Two-dimensional (2D) correlation spectroscopy was engaged as a tool for the quantitative analysis of a series of temperature-dependent infrared spectra registered in situ during methane combustion. The prepared samples of catalysts were based on a Co, Pd and Ce mixed oxide adsorbed on an aluminium oxide layer deposited on kanthal steel. The registered spectra were transformed into 2D synchronous and asynchronous contour maps. The sequential order of spectral intensity changes was determined, and the resolution enhancement of overlapping IR bands by 2D correlation was demonstrated. The changes in the bands' intensity and information about band position can be correlated with a specific bond, and thus, the possible process intermediates can be identified. The 2DCoS analysis proved to be a powerful tool for band enhancement and revealed the changes occurring within the analysed catalyst systems as responses to increased temperature.

Antimicrobial Properties of Silver Cations Substituted to Faujasite Mineral.

A goal of our study was to find an alternative to nano-silver-based antimicrobial materials which would contain active silver immobilized in a solid matrix that prevents its migration into the surrounding environment. In this study, we investigated whether silver cations dispersed in an atomic form and trapped in an ion-exchanged zeolite show comparable antimicrobial activity to silver nanoparticles (NPs). The biocidal active material was prepared from the sodium form of faujasite type zeolite in two steps: (1) exchange with silver cations, (2) removal of the external silver oxide NPs by elution with Na2EDTA solution. The modified biocidal zeolite was then added to paper pulp to obtain sheets. The zeolite paper samples and reference samples containing silver NPs were tested in terms of biocidal activity against an array of fungi and bacteria strains, including Escherichia coli, Serratia marcescens, Bacillus subtilis, Bacillus megaterium, Trichoderma viride, Chaetomium globosum, Aspergillus niger, Cladosporium cladosporioides, and Mortierella alpina. The paper with the modified faujasite additive showed higher or similar antibacterial and antifungal activities towards the majority of tested microbes in comparison with the silver NP-filled paper. A reverse effect was observed for the Mortierella alpina strain.

2D-COS of in situ µ-Raman and in situ IR spectra for structure evolution characterisation of NEP-deposited cobalt oxide catalyst during n-nonane combustion.

New catalytic systems are still in development to meet the challenge of regulations concerning the emission of volatile organic compounds (VOCs). This is because such compounds have a significant impact on air quality and some of them are toxic to the environment and human beings. The catalytic combustion process of VOCs over non-noble metal catalysts is of great interest to researchers. The high conversion parameters and cost effective preparation makes them a valuable alternative to monoliths and noble metal catalysts. In this study, the cobalt catalyst was prepared by non-equilibrium plasma deposition of organic precursor on calcined kanthal steel. Thus prepared, cobalt oxide based microstructural short-channel reactors were tested for n-nonane combustion and the catalyst surfaces were examined by in situ µ-Raman spectroscopy and in situ infrared spectroscopy. The spectra collected at various temperatures were used in generalised two-dimensional correlation analysis to establish the sequential order of spectral intensity changes and correlate the simultaneous changes in bands selectively coupled by different interaction mechanisms. The 2D synchronous and asynchronous contour maps were proved to be a valuable extension to the standard analysis of the temperature dependent 1D spectra.

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.

Towards determination of absolute molar mass of cellulose polymer by size exclusion chromatography with mulitple angle laser light scattering detection.

The study focuses on determination of a set of crucial parameters for molar mass calculation of cellulose from the results of size exclusion chromatography coupled with multiple angle laser light scattering (MALLS) and differential refractive index (DRI) detectors. In the present work, cellulose has been derivatised to obtain cellulose tricarbanilate (CTC) soluble in tetrahydrofuran (THF). The parameters of Rayleigh scattering in the MALLS detector: refractive index increment (dn/dc) and second virial coefficient (A2) of CTC in THF were determined for laser wavelength 658nm. In order to avoid errors resulting from cellulose derivatisation by-products present in the CTC solution, the so called "on-line" method of measuring dn/dc and A2 was applied. Based on the A2 determination, its influence on cellulose molar mass calculations and cellulose molecular dimensions were critically assessed. The latter includes evaluation of artificially aged cellulose towards conceivable branching by conformation plot analysis.

Molecular degradation of ancient documents revealed by 1H HR-MAS NMR spectroscopy.

For centuries mankind has stored its knowledge on paper, a remarkable biomaterial made of natural cellulose fibers. However, spontaneous cellulose degradation phenomena weaken and discolorate paper over time. The detailed knowledge of products arising from cellulose degradation is essential in understanding deterioration pathways and in improving durability of cultural heritage. In this study, for the first time, products of cellulose degradation were individually detected in solid paper samples by means of an extremely powerful proton HR-MAS NMR set-up, in combination to a wise use of both ancient and, as reference, artificially aged paper samples. Carboxylic acids, in addition to more complex dicarboxylic and hydroxy-carboxylic acids, were found in all samples studied. Since these products can catalyze further degradation, their knowledge is fundamental to improve conservation strategies of historical documents. Furthermore, the identification of compounds used in ancient production techniques, also suggests for artifacts dating, authentication and provenance.

Note: Light ageing with simultaneous colorimetry via fibre optics reflection spectrometry.

In this article, the design and characteristics of a micro-fadeometer is presented. The technique allows for a non-(micro-) destructive evaluation of the light fastness of colorants on various materials and can be used to directly assess valuable materials, such as heritage objects, and develop safer display strategies to promote their preservation. The presented instrument has several benefits over standard light ageing methods--low operating cost, non-damaging, real time measurement of induced changes for kinetics studies, and automated high throughput screening of materials. A selection of data is presented to demonstrate the flexibility of the presented instrument and illustrate how it can be used to evaluate museum lighting and oxygen-free display of heritage objects.

Vibrational spectroscopy to study degradation of natural dyes. Assessment of oxygen-free cassette for safe exposition of artefacts.

An important issue connected with conservation chemistry is how to improve the storage and exposure conditions in order to suppress the fading and degradation of dyes and other components of paintings. Although the oxygen-free exposure cassettes are commonly known in museums, there is still lack of information in the literature about the effect of anoxic conditions on the degradation of dyes. This study is an attempt to start a database formation on the dyes degradation. Five commercial dyes (indigo, dragon's blood, curcumin, madder, carminic acid) were submitted to accelerated ageing by exposure to intensive light in the visible range in both oxygen-free (anoxia) and -rich conditions. Degradation of the samples was investigated by several analytical techniques (attenuated total reflectance infrared spectroscopy, Raman spectroscopy, reflectance UV-Vis spectroscopy, X-ray fluorescence spectroscopy and optical microscopy). The conclusions are based on the estimators (derived from the determination of colour differences from Vis spectra and from the changes in FTIR and Raman vibrational bands intensity). According to them, only indigo, dragon's blood and curcumin show greater stability in anoxic conditions in comparison with oxygen-rich ones while madder, carminic acid undergo greater degradation.

Size exclusion chromatography and viscometry in paper degradation studies. New Mark-Houwink coefficients for cellulose in cupri-ethylenediamine.

The paper deals with the application of size exclusion chromatography (SEC) for the studies of paper degradation phenomena. The goal is to solve some of the technical problems connected with the calibration of multi-detector SEC system and to find the correlation between SEC and viscometric results of degree of polymerization of cellulose. The results gathered for the paper samples degraded by acidic air pollutant (NO(2)) are used as an example of SEC-MALLS application. From the correlation between intrinsic viscosities and absolute value of molecular masses obtained with SEC/MALLS (Multi Angle Laser Light Scattering) technique, Mark-Houwink coefficients for cellulose in cupri-ethylenediamine solution were determined. Thus obtained coefficients were used for the determination of viscometric degree of polymerization (molecular mass) of the aged samples. An excellent correlation was found between the chromatographic values of molecular masses obtained with SEC-UV/VIS detection and the viscometric ones utilizing the improved values of Mark-Houwink coefficients.