František Kačík

Properties Characterization of Chemically Modified Hemp Hurds

The effect of chemical treatment of hemp hurds slices in three solutions (EDTA (Ethylenediaminetetraacetic acid), NaOH and Ca(OH)2) on the properties of natural material was discussed in this paper. Changes in the morphology, chemical composition and structure as well as thermal stability of hemp hurds before and after their modification were investigated by using FTIR (Fourier transform infrared spectroscopy), XRD (X-ray powder diffraction analysis) and TG (thermogravimetry)/DSC (differential scanning calorimetry). Size exclusion chromatography (SEC) measurements were used for determination of degree of cellulose polymerization of hemp hurd samples. Chemical modification is related to the partial removal of non-cellulosic components of lignin, hemicellulose and pectin as well as waxes from the surface of hemp hurd slices. Another effect of the chemical treatment applied is connected with increasing the crystallinity index of cellulose determined by FTIR and XRD methods. Decrease in degree of cellulose polymerization and polydispersity index in chemically modified hemp hurds compared to the original sample was observed. Increase in thermal stability of treated hemp hurd was found. The most significant changes were observed in alkaline treated hemp hurds by NaOH.

Effects of thermal treatment on chemical, mechanical and colour traits in Norway spruce wood.

In several different branches of the wood industry heat treatment is a growing application as it changes the chemical, mechanical, physical and biological properties of wood. Investigations using wet chemical analyses, Fourier transform infrared spectroscopy, size exclusion chromatography, and CIELab colour system have been conducted to study the changes in Norway spruce wood subjected to temperature up to 270°C over a 30 min time period. The results showed that mass loss (ML), total crystallinity index (TCI) of cellulose, total colour difference (ΔE*), and the content of lignin and extractives increased with the temperature, whereas degree of polymerization (DP) of cellulose, modulus of rupture (MOR), modulus of elasticity (MOE), lightness difference (ΔL*), and the content of holocellulose, cellulose and hemicelluloses all decreased with the thermal treatment. Relationships between temperature and the examined wood traits were all fitted by exponential curves. Power law relationships were found to fit the trends for DP of cellulose with ΔE*, ΔL*, and TCI of cellulose. Also found were power law regressions for the content of hemicelluloses with MOE, MOR, ΔL*, and ML. Temperatures ranging from 20 to 187°C formed a compact cluster, clearly separated from the higher examined temperatures in the multivariate wood trait space.

Release of Terpenes from Fir Wood during Its Long-Term Use and in Thermal Treatment

Building structures made from fir wood are often attacked by wood-destroying insects for which the terpenes it contains serve as attractants. One of the possibilities for extending the lifetime of structures is to use older wood with a lower content of terpenes and/or thermally modified wood. The study evaluated the levels of terpenes in naturally aged fir wood (108, 146, 279, 287 and 390 years) and their decrease by thermal treatment (the temperature of 60 °C and 120 °C, treatment duration of 10 h). Terpenes were extracted from wood samples by hexane and analyzed by gas-chromatography mass-spectrometry (GC-MS). The results indicate that recent fir wood contained approximately 60 times more terpenes than the oldest wood (186:3.1 mg/kg). The thermal wood treatment speeded up the release of terpenes. The temperature of 60 °C caused a loss in terpenes in the recent fir wood by 62%, the temperature of 120 °C even by >99%. After the treatment at the temperature of 60 °C the recent fir wood had approximately the same quantity of terpenes as non-thermally treated 108 year old wood, i.e., approximately 60–70 mg/kg. After the thermal treatment at the temperature of 120 °C the quantity of terpenes dropped in the recent as well as the old fir wood to minimum quantities (0.7–1.1 mg/kg). The thermal treatment can thus be used as a suitable method for the protection of fir wood from wood-destroying insects.

Chemical alterations of pine wood saccharides during heat sterilisation

Alterations in saccharides during heat sterilisation of pine wood (Pinus sylvestris L.) were investigated. The mass loss, extractives, lignin, cellulose, holocellulose and hemicelluloses were determined. Changes in saccharides were evaluated by the determination of monosaccharides in wood, size exclusion chromatography (SEC) as well as Fourier transform infrared (FTIR) spectroscopy. During heat sterilisation of pine wood the slight mass loss, an increase in extractives and a decrease in lignin and polysaccharides were observed. Hemicelluloses are degraded approximately twice as fast as cellulose. The degree of polymerisation of cellulose decreases approximately by 10% and it increases in holocellulose (by approx. 8%) as a result of a faster degradation of shorter hemicellulose chains. FTIR spectroscopy shows that sterilisation results in the deacetylation of cellulose and the formation of new carbonyl groups, an increase in the total crystallinity index (TCI) and a decrease in the lateral order index (LOI) and the hydrogen-bond intensity (HBI).

Relationship between the decrease of degree of polymerisation of cellulose and the loss of groundwood pulp paper mechanical properties during accelerated ageing

During natural ageing, paper undergoes colour changes and becomes brittle. It is mainly due to the degradation of cellulose, the main component of paper fibres. From the viewpoint of conservation/protection of paper-based information carriers, as well as of the utilisation of secondary fibres, knowledge of the impact of a decrease of the degree of polymerisation (DP) of cellulose on mechanical properties of paper becomes of key importance. In this paper, correlations between the decrease of DP of cellulose and the loss of paper folding endurance (FE) using three model samples (pure cellulose, groundwood pulp paper, and degraded groundwood pulp paper) at accelerated ageing were investigated. The existence of such correlations between DP and FE is supported by experimental results; the correlations are linear for pure cellulose and groundwood pulp paper ageing, while exponential correlation was observed in case of degraded groundwood pulp paper. The results indicate that the rate of paper degradation can be evaluated by means of the rate of glycosidic bonds breaking in cellulosic polymer chains both for cellulose and groundwood pulp paper.

Thermal degradation of natural and treated hemp hurds under air and nitrogen atmosphere

Sustainability goals are essential driving principles for the development of innovative materials in the construction industry. Natural fibers represent an attractive alternative as reinforcing material due to good mechanical properties and sustainability prerequisites. The study has been focused on the comparative investigation of chemical and physical treatments of hemp hurds and their influence on the thermal behavior of main hemp constituents in air and nitrogen atmosphere. Thermal decomposition of hemp hurds involves several parallel reactions related to heat and mass transfer processes. A comparison of DSC and TG/DTG results of hemp hurds samples before and after treatments demonstrates a better thermal stability for treated samples. It is caused by changes in chemical composition due to a partial removal of non-cellulosic components from hemp hurds structure, an increase in cellulose content and decrease in its degree of polymerization. The results show different thermal behavior of the hurds samples heated under nitrogen and air atmosphere. Based on DTG records, several-stage process of mass loss has been found for the samples under air, whereas only two-stage process under nitrogen.

Alkaline and Alkaline/oxidation pre-treatments of spruce wood (Picea abies) - Impact on the quality of kraft pulp

A comparable series of specimens from spruce wood were pre-treated with sodium hydroxide, sodium hydroxide and hydrogen peroxide, or per-acetic acid sequences. The pre-treatments reduced the yield of pulps and their Kappa number noticeably, diminished the degree of polymerization moderately, and increased their brightness. One-step peroxide bleaching of pulps from the pre-treated spruce wood resulted in their higher brightness compared to bleached pulp from sound wood. From the viewpoint of improved properties of pulp, the most efficient were the sodium hydroxide/per-acetic acid and per-acetic acid/sodium hydroxide sequences. The pre-treatments did not influence mechanical strength of the obtained pulps significantly.

The onset of hazel wood formation in Norway spruce (Picea abies [L.] Karst.) stems

Key messageFungal infection was outlined as a potential reason for the onset of indented annual growth ring formation during the juvenile phase of hazel wood growth. Annual growth ring indentations resulted from the formation of disturbed zones which originated solely in close proximity to leaf traces.ContextHazel wood is an abnormal type of woody tissue that is formed as a result of exogenous stimuli that may trigger long-term responses in the cambium. Cambial responses produce anatomical alterations in the surrounding xylem tissue that can be observed as an indentation of annual growth rings. The chemical profiles of lignan hydroxymatairesinol may provide an indication of its possible role in the protection of a living tree against the spread of a fungal or microbial infection at the onset of indentation.AimsThe objectives of this study were to reveal the anatomical differences in the altered woody tissue of Picea abies hazel wood at both the onset and the later stages of annual growth ring indentation and to determine the chemical profiles for hydroxymatairesinol upon elicitation by a fungal infection in the disturbed zones.MethodsLight and scanning electron microscopy observations were carried out on radial, tangential, and cross sections of hazel wood zones separated from P. abies stems. Concentrations of hydroxymatairesinol were determined for both the disturbed zones and the non-indented zones using a gradient high-performance liquid chromatography.ResultsThe formation of disturbed zones was accompanied by significant changes in both the direction and width of the tracheids which produced an abnormal formation of intertwined and twisted tracheids. Fungal hyphae, radial cell wall cracks, and unusually large cross-field pitting were all found in the tracheids of the disturbed zones.ConclusionThe content of hydroxymatairesinol in the acetone extract determined from the disturbed zones was 3.4 times greater than that present in the non-disturbed tissues. By means of vascular dysfunction in the leaf traces, host trees responded to the fungal infection by plugging the lumens of conductive leaf trace tissue and filling the vascular pathway with polyphenolic compound deposits.

The Effects of Heat Treatment on the Chemical Alterations of Oak Wood

Samples prepared from oak (Quercusrobur L.) wood were exposed to heat treatment at temperatures of 160, 180, 200 and 220 oC for 3, 6, 9 and 12 hours. In both untreated and thermally treated wood there were determined extractives and lignin by National Renewable Energy Laboratory (NREL) procedures, cellulose by Seiferts method, holocellulose according to Wise, hemicelluloses as difference between holocellulose and cellulose. Monosaccharides were determined by high performance liquid chromatography (NREL).The results show that hemicelluloses are less stable at thermal treatment than cellulose. The amounts of lignin and extractives rose by increasing both temperature and time of the treatment while the amounts of hemicelluloses decreased. Thermal treatment also resulted in significant decreases of the yields of non-glucosic saccharides. Degradation of carbohydrates can cause the deterioration of mechanical properties of wood.

Influence of Chemical Treatment on Chemical Changes of Fir Wood

Many chemicals are used to prolong wood lifetime and protect wood against wood-destroying organisms and fire but there is not sufficient information about their possible corrosive effects on wood and its structural components from the perspective of long-term exposition in unsuitable condition. This study evaluated the combined effects of inorganic chemicals (borates, phosphates containing ammonia, sulphates with metal cations, chlorides) and wet-thermal accelerated ageing (T=80 °C, RH=65 %, for 30 days) on chemical composition of treated wood. Used analyses indicated that selected chemicals cause a decomposition of all wood constituents in varying degrees. Cellulose was degraded in the greatest extent due to acidic sulphates (Fe3+, Cu2+) and almost no deterioration of polysaccharides was caused with H3BO3. A negative effect on lignin had almost only Na2B4O7.10H2O and NaCl. At the same time the amount of extractives in hot water and acetone and ash content were compared at all samples. The wet-thermal ageing played an important role in wood degradation, but the effect of chemical treatment was certainly stronger.