Carmen-Mihaela Popescu

Spectral Characterization of Eucalyptus Wood

The main difficulties in wood and pulp analyses arise principally from their numerous components with different chemical structures. Therefore, the basic problem in a specific analytical procedure may be the selective separation of the main carbohydrate-derived components from lignin due to their chemical association and structural coexistence. The processing of the wood determines some structural modification in its components depending on the type of wood and the applied procedure. Fourier transform infrared (FT-IR) spectrometry and X-ray diffraction have been applied to analyze Eucalyptus g. wood chips and unbleached and chloritebleached pulp. The differences between samples have been established by examination of the spectra of the fractions obtained by successive extraction (acetone extractives, acetone free extractive samples, hemicelluloses, and lignins) by evaluating the derivative spectra, band deconvolution, etc. The energy and the hydrogen bonding distance have been evaluated. The relationship between spectral characteristics and sample composition has been established, as well as the variation of the degree of crystallinity after pulping and bleaching. The integral absorption and lignin/carbohydrate ratios calculated from FT-IR spectra of the IR bands assigned to different bending or stretching in lignin groups are stronger in the spectrum of eucalyptus chips than those from brown stock (BS) pulp spectra because of the smaller total amount of lignin in the latter. FT-IR spectra clearly show that after chlorite bleaching the structure of the wood components is partially modified or removed. Along with FT-IR data, the X-ray results confirmed the low content of lignin in the pulp samples by increasing the calculated values of the crystalline parameters. It was concluded that FT-IR spectroscopy can be used as a quick method to differentiate Eucalyptus globulus samples.

Structural analysis of photodegraded lime wood by means of FT-IR and 2D IR correlation spectroscopy

In this study the weathering behavior of lime wood (Tillia cordata Mill.) has been examined using FT-IR and 2D IR correlation spectroscopy, which evidenced chemical changes induced by exposure to weathering conditions. It was showed that lignin is most sensitive component to the photodegradation processes as indicated by considerable decreases in the intensities of the characteristic aromatic lignin band at 1505cm(-1) and other associated bands. By 2D correlation spectroscopy has been demonstrated that the moment of CO from carboxyl and acetyl groups in hemicelluloses is changing first, followed by the CC of aromatic skeletal, CO in non-conjugated ketones, carboxyl groups and lactones, absorbed O-H and conjugated C-O groups in quinones. The carbonyl formation corresponded well with lignin degradation, indicating a close relationship between them. Comparing the rate of carbonyl formation and lignin decay clearly showed that the former is remarkably higher than the latter, indicating the formation of carbonyl bands at 1738cm(-1) probably resulted from not only lignin oxidation but also from reactions occurring in other components of the wood. Quinine formation is combined with the decay of aromatic structures and the formation of conjugated carbonyl groups.

The water vapour sorption behaviour of acetylated birch wood: how acetylation affects the sorption isotherm and accessible hydroxyl content

The water vapour sorption isotherms and sorption kinetics of birch (Betula pendula L) acetylated to different levels have been determined using a dynamic vapour sorption (DVS) apparatus. A DVS instrument was also used to determine the accessible hydroxyl content in the wood samples using deuterium exchange. The results are reported in terms of the reduced equilibrium moisture content (EMCR), in which the moisture content per unit mass of wood substance is used for the calculation. As the level of acetylation of the wood samples increased there was a corresponding reduction in EMCR of the wood samples, which was accompanied by a decrease in hysteresis in the same order. The sorption kinetics were also determined using the DVS and analysed using the parallel exponential kinetics model, in which the sorption kinetics curve is composed of two processes (labelled fast and slow). Using this analysis, it is possible to calculate two pseudo-isotherms associated with the two processes. The sorption isotherm is a composite of the sorption isotherms associated with the fast process water and the slow process water and there are significant differences in behaviour between the two. It is suggested in this paper that the fast process is related to diffusion limited kinetics, whereas the slow process is a relaxation-limited phenomenon. The reduction in accessible OH content due to acetylation was well correlated with the weight gain due to acetylation, although the relationship did not exactly correspond with that theoretically determined.

A near infrared spectroscopic study of the structural modifications of lime (Tilia cordata Mill.) wood during hydro-thermal treatment.

The modifications and/or degradation of lime (Tillia cordata) wood components during wood heat treatment under low temperature at about 140°C and 10% percentage of relative humidity were evaluated. The aim of this study was to obtain results by simple NIR coupled with second derivative, principal component analysis and two dimensional correlation spectroscopy in order to better understand how these techniques are able to evaluate structural differences resulted under hydro-thermal treatment of the wood over a period of 504h. The NIR spectra of treated samples were compared with the reference one. Due to the broad bands in the NIR spectra, the assignment and modifications occurring during treatment is difficult, therefore the second derivative principal component analysis were applied. Principal component analysis by first two components was able to differentiate the samples series, PC1 being considered as the time axis, and PC2 as the axis representing the structural modification of wood components. 2D NIR correlation spectroscopy was able to estimate the sequential order of the groups variations under the hydro-thermal treatment time as external perturbation, indicating as first moment changes the OH and CO groups from carbohydrates and lignin, followed by CarH, CH and CH2 groups from lignin, cellulose and hemicelluloses.

Structural study of photodegraded acrylic-coated lime wood using Fourier transform infrared and two-dimensional infrared correlation spectroscopy.

The weathering of acrylic films and acrylic-coated lime wood (Tillia cordata Mill.) were examined using Fourier transform infrared (FT-IR) and two-dimensional infrared correlation spectroscopy. The obtained results showed chemical changes induced by exposure to weathering conditions, in both films and coated wood. The observed spectral changes of the acrylic films refer to the absorption band assigned to the C–O stretching, which progressively decreases with increasing exposure time. In the spectra of treated wood samples the main signal indicating the advance of oxidation during the photodegradation exposure is the gradual increase and broadening of the band in the carbonyl region. This is due to the formation of the non-hydrogen bonded aliphatic carboxylic acids and γ-lactone structures in the acrylic resin and of the nonconjugated ketones, carboxyl groups, and lactones in wood. As a consequence, the increase of the 1734 cm−1 band is due to the degradation of lignin from wood surface. These observations are also supported by the decreased intensities of the bands at 1598 and 1505 cm−1, assigned to C=C of aromatic skeletal (lignin). The relative intensity of the characteristic aromatic lignin band at 1505 cm−1 decreases up to 25% of its original value after weathering, being less than half of the value obtained for uncoated wood. Two-dimensional infrared (2D IR) correlation spectroscopy was used to identify the sequence of the modifications of the different stretching vibrations bands under the weathering conditions, the method allowing the prediction of the order of degradation reactions. The acrylic resin degradation starts with the formation of radicals by abstraction of the tertiary hydrogen atoms of the methyl acrylate units and the α–CH3 groups from the ethyl methacrylate units. The subsequent decomposition and oxidation led to the formation of alcohol groups, hydroperoxides, ketones, and/or carboxylic acid groups. The 2D IR correlation spectra of weathered impregnated wood also revealed the elimination of low molecular weight compounds following the degradation of lignin and carbohydrates components from wood.

Evaluation of the thermal stability and set recovery of thermo-hydro-mechanically treated lime ( Tilia cordata ) wood

The effect of the thermo-hydro-mechanical (THM) densification in a closed system on the set recovery and thermal stability of lime (Tilia cordata) wood was evaluated. The THM densification process consists of four steps: plastification, densification, post-treatment and cooling. The THM-densified wood samples were subjected to three different post-treatment temperatures, and for each one, three different periods were used. Comparison between THM-densified wood sample without and with post-treatment at different temperatures and times was made. The set recovery tests showed that the post-treatment at higher temperatures and times improves the dimensional stability of the samples suggesting a permanent fixation of the transversal compression, but also reduces their thermal stability, by having lower temperatures corresponding to the maximum decomposition rate, lower values for the mass loss at the end of decomposition stage and lower values for the kinetic parameters. The samples with post-treatments at lower temperatures showed high set recovery values and exhibited higher values for the temperatures corresponding to the maximum decomposition rate, lower values for the mass loss at the end of the stage and higher activation energies and reaction orders.

Thermal behavior of biodegraded lime wood

The effects of the soft-rot fungus Trichoderma viride Pers., on the thermal behavior of lime wood (Tillia cordata Mill.) were investigated. The lime wood pieces were inoculated with the fungus over a 12-week period. At pre-established time intervals two samples were withdrawn from the medium and analyzed by thermogravimetry and differential calorimetry, and the results were correlated with mass loss. Fungal activity was indicated by continuous decrease of sample mass. Modification of the wood because of the presence of the fungus was evidenced by structural changes that affected its thermal properties, both in respect to the hydrophilicity of the wood (evidenced mainly in desorption process) and in its decomposition behavior. The shape of DTG curves depends on the exposure time of wood to the action of microorganisms. The peak temperature assigned to the decomposition of wood components increases, while the global kinetic parameters for the main peak decrease with increasing exposure time of the wood to the attack by microorganisms. The increased characteristic temperatures of water desorption and cellulose decomposition processes and lower thermal stability could be explained by newly formed structures, mainly the oxidized ones.

Characterization of Fungal-Degraded Lime Wood by X-Ray Diffraction and Cross-Polarization Magic-Angle-Spinning 13C-Nuclear Magnetic Resonance Spectroscopy

X-ray diffraction, scanning electron microscopy (SEM), and solid-state cross-polarization magic-angle-spinning (CP/MAS) 13C-NMR spectroscopy were applied to determine changes over time in the morphology and crystallinity of lime wood (Tilia cordata Miller) generated by the soft-rot fungi. Wood samples were inoculated with Trichoderma viride Pers for various durations up to 84 days. Structural and morphological modifications were assessed by comparing the structural features of decayed lime wood samples with references. Significant morphology changes such as defibration or small cavities were clearly observed on the SEM micrographs of lime wood samples exposed to fungi. Following the deconvolution process of the diffraction patterns, the degree of crystallinity, apparent lateral crystallite size, the proportion of crystallite interior chains, and the cellulose fraction have been determined. It was found that all crystallographic data vary with the duration of exposure to fungi. The degree of crystallinity and cellulose fraction tend to decrease, whereas the apparent lateral crystallite size and the proportion of crystallite interior chains increase with prolonged biodegradation processes. The most relevant signals in CP/MAS 13C-NMR spectra were assigned according to literature data. The differences observed were discussed in terms of lignin and cellulose composition: by fixing the lignin reference signal intensity, the cellulose and hemicelluloses moieties showed a relative decrease compared to the lignin signals in decayed wood.

Structural changes of wood during hydro-thermal and thermal treatments evaluated through NIR spectroscopy and principal component analysis

Spruce wood samples were subjected to different conditions of thermal and hydro-thermal treatment by varying the temperature, relative humidity and period of exposure. The obtained treated samples were evaluated using near infrared spectroscopy (NIR), principal component analysis (PCA) and hierarchical cluster analysis (HCA) in order to evidence the structural changes which may occur during the applied treatment conditions. Following this, modification in all wood components were observed, modifications which were dependent on the temperature, amount of relative humidity and also the treatment time. Therefore, higher variations were evidenced for samples treated at higher temperatures and for longer periods. At the same time, the increase in the amount of water vapours in the medium induced a reduced rate of side chains and condensation reactions occurring in the wood structure. Further, by PCA and HCA was possible to discriminate the modifications in the wood samples according to treatment time and amount of relative humidity.

Thermogravimetric Analysis of Photodegraded Acrylic Coated Lime Wood

A series of experiments were carried out to investigate the photodegradation of lime wood (Tilia cordata Mill.) coated with acrylic copolymer during artificial UV/Vis light irradiation for 600 h. Photodegradation of the Paraloid B72 films and Paraloid B72 treated lime wood samples was evaluated by thermogravimetry throughout the irradiation period of 100 h. The results obtained indicate a shifting of the DTG maxima to lower temperatures, which may be related to a decrease in the stability of the copolymer and wood during photodegradation. The decrease of weight loss with increasing time of exposure was observed, while the global kinetic parameters for the main peak increases when increasing exposure time of wood to the UV light. Even when the surface of the wood was covered with a thin layer of acrylic resin, some photodegradation reactions of the wood surface occurred. The modifications in the wood structure may be influenced by the newly formed structures from acrylic resin photodegradation.