Institut für Holztechnologie Dresden

This report describes ways in which the properties of wood might be improved by application of silica and other inorganic nanosols. Topics covered are: the synthesis and modification of inorganic nanosols, and methods of applying them to wood to improve its mechanical properties; the use of modified silica sols to realise flame retardant, water repellent and antimicrobial properties; recent nanosol applications for protecting ThermoWood, for restoring and preserving wooden cultural artefacts, and as auxiliaries for improving commercial wood lacquers.

A critical review of bark anatomical terms is undertaken to stimulate the discussion on bark terminology. Suggestions are made for a standardised usage of the corresponding terms for facilitating the communication between people working on bark anatomy. A tentative glossary of terms is given at the end of the paper.

Smoke flavourings are produced on a large scale and have been applied to a variety of food products for more than 30 years. The use of them has many advantages compared to traditional smoking techniques. Among others, the amount of (known) toxic compounds deriving from combustion processes can be more easily controlled in smoke flavourings. In order to ensure safe products, a new European Regulation requests data on the composition and lays down, in particular, the maximum permitted concentrations for selected polycyclic aromatic hydrocarbons (PAHs). This review compiles results published on the chemical composition of liquid smoke flavouring primary products, partly in relation to production process parameters, and the analytical methods involved. The methods cover chromatographic techniques for analysis of specific compounds including extraction methods and clean-up procedures. Analysis of sensorial and bulk parameters such as acidity and total phenolic compounds are described as well as they are used as standard methods for analysis of liquid smoke flavourings. A special section is devoted to discussing the analysis of PAHs.

Wood-plastic composites from bio-based polymers and wood fibers (bio-WPC) provide an improved sustainability and carbon footprint compared to conventional composites. Actually, the implementation of this approach into industrial applications is hindered by the missing knowledge on the mechanical and thermo-mechanical properties of such bio-WPC. In this study, the properties of a bio-WPC from bio-based polyamide 11 (PA 11) and chemically modified beech fibers were investigated. The chemical modification of the beech fibers by an alkaline treatment with an aqueous solution of sodium hydroxide (NaOH) was done to support the melt processing and adhesion to the PA 11 matrix. Analysis of the modified fibers by Thermogravimetric Analysis (TGA) proved an increased thermal stability, as identified by an increase of the extrapolated TGA onset temperature from 290 to 330 °C. This improvement resulted from hemicellulose removal, as confirmed through Attenuated Total Reflection Infrared Spectroscopy (ATR-FTIR). Consequently, mechanical and thermo-mechanical analysis of the processed bio-WPC showed an increase in elastic modulus and storage modulus of the composites by the chemical treatment of the fibers. This effect was attributed to an increased number of hydrogen bonds between the modified beech fibers and the PA 11 matrix. The overall mechanical properties of the investigated bio-WPCs support their use as sustainable construction material for technical applications.

Highly swellable lignin derivatives were prepared by cross-linking of oxidatively preactivated spruce organosolv lignin (OSL) with poly(ethylene) glycol diglycidyl ether (PEGDGE). The lignin gels obtained are considered to be an environmentally friendly alternative to synthetic hydrogels and superabsorbents and represent a novel type of lignin based functional materials. For their application, it is not only the absorption of water in terms of hydrogel swelling that plays an important role, but also the adsorption and retention of moisture by the corresponding xerogels. To reveal the mechanisms involved in moistening and reswelling of the lignin gels, the interaction of water vapor with lyophilized xerogels was investigated and compared with sorption characteristics of parent lignin. The chemical structure of PEGDGE-modified lignin was investigated using attenuated total reflectance Fourier-transformed infrared spectroscopy and selective aminolysis and was related to its sorption and swelling characteristics. Bound and free water in hydrogels was determined by differential scanning calorimetry and by measuring the free swelling capacity of the gels. Moisture sorption of OSL and PEGDGE-modified lignin xerogels was determined using dynamic vapor sorption analysis. In order to determine monolayer and multilayer sorption parameters, sorption data were fitted to the Brunauer-Emmett-Teller and the Guggenheim-Anderson-de Boer model. Swelling properties of the hydrogels and moisture sorption of the corresponding xerogels were found to be strongly dependent on the degree of chemical modification with PEGDGE: Total and free water content of hydrogels decrease with increasing cross-linking density; on the other hand, water bound in hydrogels and moisture sorption of xerogels at high levels of water activity strongly increase, presumably because of the hydration of hydrophilic oligo(oxyethylene) and oligo(oxyethylene) glycol substituents, which lead to moisture diffusion into the xerogel matrix, plasticization, and swelling of the gels.

The axial variation of bark thickness and quantitative anatomical features of Eucalyptus globulus bark were analysed for one site based on individual measurements of ten 15-year-old trees at six height levels (DBH, 5%, 15%, 35%, 55% and 75% of total tree height). The parameters studied were: length, tangential diameter and percentage of sieve tubes; length, width, cell wall thickness and percentage of fibres; height and percentage of rays; percentage of sclereids in the secondary phloem. Bark thickness decreases from base to top of the tree. Fibre width and wall thickness decrease from base upwards. No distinct axial patterns of variation were observed for the other biometric variables studied. Parenchyma is the main cell type of the bark (50%) followed by fibres (27.9%), rays (12.1%), sieve tubes (2.7%), and sclereids (7.3%). The cell type proportions vary significantly within the tree, i.e., parenchyma, ray and sclereid proportions decrease, fibre and sieve tube proportions increase towards the top of the tree.

Four carboxymethyl cellulose samples derived from the synthesis concept of “reaction in reactive microstructures” were characterised in detail by combination of different analytical techniques. Fractionation of one of the samples according to water-solubility into four fractions revealed that a non-statistical distribution of the substituents occurred for all fractions. Endoglucanase fragmentation of three samples was performed followed by analytical and preparative SEC. The multi-detected analytical SEC proved samples of high degree of substitution up to 1.9 to be intensively degraded, supporting the proposed block-like substitution pattern. The detailed investigation of soluble fragmentation products by preparative SEC, hydrolysis and anion exchange chromatography with pulsed amperometric detection revealed that all samples contain fragments of much higher DS values than the average DS of the starting material. On the other hand, high quantities of degradation products of low DS or almost no substitution occurred. Therefore, a structure can be proposed with segments of very high DS alternating with areas of limited substitution. The result clearly showed that the high substituted fragments were dominated by 2,3,6-tri-O-CMG.

Abstract Fine structural studies on the needles of damaged fir (Abies alba Mill.) and spruce [Picea abics (L.) Karst.] trees from forest dieback areas in the Black Forest . The fine structural changes in the variously damaged needles of fir and spruce trees from forest dieback areas have been investigated with special reference to cytoplasmie organization in the vascular bundles, mesophyll tissue and cuticle. The results are compared with those available for a few plants affected both by natural and artificial stress factors, especially air pollutants.

Abstract Scanning electron microscopical investigations on stomatal wax plugs of fir and spruce needles after fumigation and acid rain treatment Alterations of stomatal wax plugs of fir and spruce needles have been investigated in order to demonstrate the effects of different air pollutants. After acid rain treatment, and in addition to SO 2 fumigation, heavily melted wax crystals were observed. It is assumed that acid rain causes mainly the changes of the stomatal wax plugs.

Abstract The following compounds were identified as male pheromone components of the longhorn beetles Hylotrupes bajulus and Pyrrhidium sanguineum : (3 R )‐3‐hydroxy‐2‐hexanone [(3 R )‐ 1 ], (2 S ,3 R )‐2,3‐hexanediol [(2 S ,3 R )‐ 4 ] and (2 R ,3 R )‐2,3‐hexanediol [(2 R ,3 R )‐ 4 ]. The syntheses of enantiomerically pure samples, enantiomeric separation by chiral gas chromatography and unambiguous structure assignment of the target compounds are described.

Since cross-linked hydrogels from oxyethylated lignins (OELs) are progressively more regarded as water-retaining soil improvements based on sustainable and biorenewable resources, an effort is made here to gain some insight into the biodegradation behavior of these materials. For this purpose, model soils with defined sand/lignin and sand/OEL ratios were incubated in a closed system under laboratory conditions, and carbon dioxide evolved by microbial lignin and OEL decomposition was determined. OELs with different oxyethylation/cross-linking degrees and water absorption capacities were included into the experiments and compared with respective types of parent technical soft wood and hard wood lignins. The results suggest a medium- to long-term biodegradability of OELs ensuring a long-term functionality of the hydrogel materials on the one hand and a subsequent integration of respective degradation products into the natural carbon cycles on the other hand. It was found that the short-term carbon mineralization rates of OELs are markedly lower compared to that of parent lignins and strongly dependent on (1) lignin type, (2) cross-linking/oxyethylation degrees of OEL, (3) corresponding swelling properties, and (4) OEL concentrations in model soils.

)-H azidated materials under electrocatalytic conditions. The functionalized polymers were obtained with high retention of mass average molecular mass and high functionalization through chemo-selective mangana-electrocatalysis. Our strategy proved to be broadly applicable to a variety of homo- and copolymers. Polyethylene, polypropylene as well as post-consumer polystyrene materials were functionalized by this approach, thereby avoiding the use of hypervalent-iodine reagents in stoichiometric quantities by means of electrocatalysis. This study, hence, represents a chemical oxidant-free polymer functionalization by electro-oxidation. The electrocatalysis proved to be scalable, which highlights its unique feature for a green hydrogen economy by means of the hydrogen evolution reaction (HER).

Abstract The article contains sections titled: 1. Occurrence and Functions 2. Structure and Biosynthesis 3. Physical Properties 4. Chemical Properties 4.1. Kraft Pulping 4.2. Sulfite Pulping 4.3. Other Pulping Processes 4.4. Pulp Bleaching 4.5. Yellowing Reactions 5. Commercial Lignins 6. Analysis 6.1. Detection and Quantification 6.2. Isolation 6.3. Spectroscopic Methods 6.4. Degradation Methods 6.5. Molar Mass Determination 7. Uses 8. Toxicology

Abstract Infection and Deterioration of Spruce Root Wood by Fornes annosus . The paper describes the mode of infection and subsequent deterioration of spruce root wood by Fornes annosus using light and electronmicroscopic observations. In the secondary xylem the overall penetration of cell walls is effected by means of microhyphae which produce boreholes. The degradation of cell walls is initiated in the S 2 layer by diffusion of enzymes along the cellulose fibrils with subsequent hydrolysis of the amorphic incrusting substances.

When bonding wood for structural applications, the wood–adhesive bond is influenced by a variety of factors. Besides the physical and mechanical properties of wood species, their chemical composition, e.g. wood extractives, can play a role in bonding wooden surfaces. A two-component polyurethane system (2C PUR) was chosen to better adapt to the current adhesion problem. The influence of extractives on crosslinking was determined by Attenuated Total Reflection-Fourier Transform Infrared Spectrometer (ATR-FTIR) and on the rheological behavior in terms of gel point and storage modulus. Therefore, 2C PUR was mixed with 10% of eight common wood extractives separately. Furthermore, the mechanical properties of beech wood (Fagus sylvatica L.) bonded with extractive enriched adhesive were tested by means of tensile shear strength tests and evaluation of wood failure. These results of ATR-FTIR clearly show that the majority of crosslinking was terminated after 12 hr. Acetic acid and linoleic acid expedited the isocyanate conversion during the first 2.5 hr. The curing in terms of gel point and storage modulus of 2C PUR was accelerated by starch, gallic acid, linoleic acid, and acetic acid. Heptanal, pentanal, 3-carene, and limonene decelerated the curing. All extractives lowered the storage modulus determined after 12 hr. The bonding of beech wood with extractive–adhesive blends showed a slight decrease of the mechanical properties, with the exception of a marginal increase in the case of linoleic acid and pentanal.In summary, it can be said that 2C PUR is sensitive to the influence of wood extractives and can therefore be partly held responsible for adhesion problems occurring when extractives in surface-wide and higher contents are available.

PEGylated or oxyethylated lignins (OEL) have recently become a hot topic as precursors for novel lignin-based and sustainable materials or active substances such as hydrogels, aerogels, carbogels, dispersants, and surfactants. Since functional properties of OEL and the resulting materials are strongly affected by the degree of oxyethylation (DOE) of phenolic hydroxyl groups (OH phen ), analytical techniques for its determination are crucial. OELs with different levels of modification were obtained by reacting lignins from different pulping procedures with varying amounts of poly(ethylene) glycol-α,ω-diglycidyl ether (PEGDGE). Parent lignins and OELs were characterized by means of selective aminolysis that is subsequent preacetylation and selective deacetylation of aromatic acetates of preacetylated lignin/OEL with pyrrolidine. The reaction product 1-acetyl pyrrolidine was quantified using GC/FID. The DOE of OEL, obtained by subtraction of OH phen content before and after lignin oxyethylation, was found to be in the range between 53.4% and 70.0%. Selective aminolysis has been shown to be very accurate for OEL analysis but is very time-consuming. Thus, it was the aim to investigate the extent to which FTIR features of acetylated lignin and OEL relate to OH phen contents and DOE of OEL as obtained by aminolysis. Strong linear correlations ( R 2 = 0.94–0.97) were found between OH phen contents of lignin/OEL and IR vibrations related to phenolic and aliphatic acetoxy groups. The results demonstrate that, with appropriate calibration, FTIR spectroscopy combined with sample preacetylation is a promising tool for a rapid and accurate determination of the DOE of OELs.

The work aimed to study the influence of replacing virgin wood fibres by recycled fibres, made from recovered medium-density fibreboards (MDF) by thermo-mechanical pulping, on the physical-mechanical properties and formaldehyde release of urea-formaldehyde (UF)-bonded MDF. It was found that replacement of 33% virgin fibres by recycled fibres decreased significantly the thickness swelling and water absorption of the UF-bonded MDF and mitigated the formaldehyde release. However, supplanting 33% of virgin fibres by recycled fibres had a negative impact on the internal bond strength. UF-bonded MDF with higher amounts of recycled fibres (67 and 100%) could not be produced without applying the hybrid bonding technology, i.e. adding small quantities of polymeric diphenylmethane diisocyanate to the UF resin. MDF made from 100% recycled fibres showed significantly lower thickness swelling values as well as a drastic drop in the formaldehyde release compared with boards made from virgin wood fibres.

Abstract Aus einigen gesundheitsschädigenden Teakvarietäten konnte ein toxisches Chinon C 15 H 14 O 2 isoliert werden. Nach den Ergebnissen des Abbaues und der Synthese handelt es sich um Desoxylapachol (2‐[γ.γ‐Dimethyl‐allyl]‐naphthochinon‐(1.4) (I).

Quantitative changes of certain anatomical characters during bark development of Quercus robur L., Ulmus glabra Huds., Populus tremula L. and Betula pendula Roth were analysed.

Sodium carboxymethylcellulose (NaCMC) with varying degrees of substitution (DS) was investigated with different analytical methods in order to characterize the functional group distribution. The following methods were tested and adapted: high-resolution 13C NMR spectroscopy in the solid state (13C CP/MAS NMR) and 13C NMR spectroscopy on solutions of NaCMC samples with a reduced molar mass. Partial degradation was accomplished by ultrasonic means and with the enzyme endoglucanase. Combining the two techniques resulted in the greatest reduction in molar mass and hence in the best spectral resolution. Analysis of the NaCMC fragments following ultrasonic and/or endoglucanase degradation also reveals another interesting experimental finding. It appears that ultrasonic degradation is favored at unsubstituted areas near the center of the chain. These methods were compared with the following already familiar techniques of analysis: titrimetric techniques; 13C and 1H NMR spectroscopy as well as HPLC on completely hydrolysed solutions (hydrolysis with perchloric acid, trifluoroacetic acid and sulfuric acid). All of the methods characterize the samples as a series with increasing DS, the values of which range from 0.9 to 2.4. Methods that permit analysis of the partial degree of substitution produced the distribution x2 > x6 > x3. Therefore, they are in principle suited for determining the functionalization pattern of the NaCMC samples relative to one another. The most suitable method can therefore be selected according to the objectives and the apparatus available. However, the measured values do exhibit considerable spread, variances of approx. 20%, thus, place restrictions on using the values of DS or xi in absolute comparisons beyond these methods.