Aging law of spruce wood

Abstract

Accelerated aging of spruce wood samples have been carried out by thermo-hydro (TH) treatments. These treatments were applied to accelerate the chemical reactions that take place during the natural aging of wood. In order to avoid dissimilar chemical reactions between the TH treatments and the natural aging, mild temperatures (between 100 and 150°C) have been selected at low relative humidity (RH). The mechanical properties of non-aged, natural aged and accelerated aged spruce wood have been compared. It is apparent that longitudinal Young's modulus of accelerated aged wood increase slightly at the beginning of the treatment and is followed by a reduction. Along the radial direction, Young's modulus remains almost unchanged. On the other hand the radial strength is severely reduced. From these results, the relative radial strength has been fitted on the chemical kinetic law. The rate constant of this law has been calculated and the treatment temperature and wood moisture content have been integrated. Finally this law has been extrapolated to standard climatic conditions in order to predict the loss of strength of old wood by knowing its age and its mean climate history of temperature and RH (ambiance condition).     

Alkaline degradation of spruce and beech wood

Summary The alkaline delignification of spruce and beech wood is accomplished in three phases. The first phase results in a decrease of yield down to 83...80%, the second one in a decrease from 83...80% to 64...61% and the third one in a yeld drop from 64...61% to 50...46%. The amount of polysaccharides removed in the first phase was 22%, in the second phase 5...6% and in the third phase 10% of the total polysaccharides in the original wood. The amount of lignin removed in the first phase of delignification was 9...11% in the second phase 53...54% and in the third phase 28% of the total lignin in the original wood. The polysaccharides extracted in the second and third phase amounted to 70...78% of the polysaccharides removed in the first delignification phase. For an entire characterization of the delignification reaction not only the course of lignin removal is of importance but also the course of the polysaccharide extraction. The results show that for a two-stage alkali-oxygen-cooking technology the optimum yield after initial partial alkaline delignification lies in the range of 64...61%.     

Pressurized hot water extraction of Norway spruce hemicelluloses using a flow-through system

Norway spruce saw meal was extracted with pressurized hot water at 120–240°C using a flow-through system. Only small amounts of hemicelluloses were extracted at 120–160°C, but dissolution was significantly enhanced when higher extraction temperatures were applied. All hemicelluloses but only 15% of lignin were removed from wood at 220°C, and even less lignin was extracted at lower temperatures. Partial degradation of cellulose seemed to take place only at 240°C. Of the total amount of extracted hemicelluloses, 4–22% was hydrolyzed to monosaccharides. Although the average molar masses of extracted hemicelluloses decreased with increasing extraction temperature, even at 240°C the extracted carbohydrates occurred, on average, as polysaccharides. Polysaccharides with an average molar mass of 31 kDa were obtained at 170°C. The molecular-mass characteristics and yield of carbohydrates depend on the extraction temperature, which should be chosen based on the end use of the isolated hemicelluloses.     

Improved water repellency of black spruce wood surfaces after treatment in carbon tetrafluoride plasmas

Plasma treatments for black spruce wood (Picea mariana (Mill.) B.S.P.), a widespread forest species from Canada, were carried out in order to waterproof the exposed surfaces. Experiments were performed using inductively coupled argon plasma with carbon tetrafluoride as the gaseous precursor for plasma-enhanced chemical vapor deposition of functional fluoropolymer coatings on wood. Analysis of the wettability through water contact angle measurements showed water-repellent characteristics, with static contact angles up to 130° depending on plasma exposure time, CF₄ concentration in the Ar/CF₄ plasma, and plasma source-to-substrate distance. X-ray photoelectron spectroscopy investigations of plasma-treated wood surfaces confirmed the growth of a thin, fluorocarbon layer with fluorine atomic concentrations close to 50 % on highly hydrophobic wood surfaces. Estimation of the thickness of the coatings by stylus profilometry revealed that a minimum layer thickness of about 80 nm is required to obtain water repellant wood surfaces with minimum water uptake. This complete set of data indicates that fluorocarbon-containing plasmas represent a very promising approach for improving the durability of wood products in wet and humid conditions.     

Differential calometric analysis of wood and wood components

Summary The prolysis of cellulose, hemicelluloses, lignin preparations, and wood was studied by differential calorimetric analysis (DCA) for the range of 25° to 800° C. The test samples included powdered and filter paper celluloses; hardwood xylan; softwood galactoglucomannans, compression wood galactan, and arabinogalactan; a synthetic (DHP), sulfuric acid, Björkman, Brownell, and cellulase lignins; and unextracted and extracted hardwoods and softwoods. Heats of reaction were determined from the DCA thermal transition areas. Distinct differences were found between the thermograms of each hemicellulose and lignin sample. Although wood species could not be separated thermally, hardwood and softwood thermograms differed because of the hemicellulose degradation pattern.Trade names and company names are included for the benefit of the reader and do not imply any endorsement or preferential treatment of the product by the U.S. Department of Agriculture.Formerly Research Technologist, Forest Products Laboratory, Forest Service, U.S. Department of Agriculture. The Laboratory is maintained at Madison, Wis. 53705, in cooperation with the University of Wisconsin. Present address: The Pennsylvania State University, University Park, Pennsylvania 16802.     

Proton magnetic resonance techniques for characterization of water in wood: application to white spruce

Summary Two new proton magnetic resonance techniques, relaxation spectra and relaxation selective imaging, have been used to investigate the distribution of water in samples of normal white spruce sapwood, heartwood, and juvenile wood as well as two rehydrated heartwood samples containing incipient decay and compression wood respectively. It is demonstrated that the spin-spin (T₂) relaxation behavior in wood is best presented as a continuous spectrum of relaxation times. Spectra of T₂ for white spruce show separate peaks corresponding to the different water environments. Bound water gives a peak with an T₂ time of about 1 ms and lumen water gives a distribution of T₂ times in the range of 10 to 100 ms. The lumen water T₂ time is a function of the wood cell radius. Consequently, the different cell lumen radii distributions for spruce sapwood, juvenile wood, and compression wood are readily distinguishable by the shape of their T₂ spectra. Water environments which are separable on a T₂ spectrum may be imaged separately. Imaging has been carried out in one dimension for bound water and lumen water of a spruce sapwood sample at four different moisture contents ranging from 100% to 17%. For the first time, we demonstrate that above the fibre saturation point the moisture density profile of the bound water is largely independent of moisture content. The feasibility and utility of using these techniques for internal scanning of logs and lumber is discussed. These techniques should provide new insights into the wood drying process.We would like to thank Michael Weiss of the Biological Science Electron Microscopy Facility at the University of British Columbia for his assistance with the microscopy and image analysis. This research was supported by grants from the Natural Sciences and Engineering Research Council of Canada and the Canadian Forestry Service     

Impregnation of Norway spruce (Picea abies L. Karst.) wood by hydrophobic oil and dispersion patterns in different tissues

Wood from Norway spruce (Picea abies L. Karst.) is biologicallydegraded in exposed conditions. It also has anatomical featuresthat make it difficult to impregnate with preservatives by currentlyavailable industrial processes. In the study reported here,we used the new Linotech process to impregnate Norway sprucewood with hydrophobic linseed oil and then quantified its uptakeand dispersal in anatomically distinct wood tissues. We alsoinvestigated the effects of the wood moisture content on theresults of the impregnation. Samples (500 x 25 x 25 mm) weretaken from 15 trees in a coniferous forest in northern Sweden(64° 10' N, 160–320 m a.s.l.). The parameters forthe Linotech process were 2–3 h treatment time at 0.8–1.4MPa and 60–140°C. To determine the level of uptake,the linseed oil was extracted from the impregnated wood usingmethyl-tertiary-butyl-ether. The uptake was quantitatively analysedby comparing X-ray microdensitometry values obtained followingimpregnation both before and after oil removal. In earlywood,initial moisture content had an obvious effect on the impregnationresult. Six times more oil was taken up when the moisture contentwas greater than ~150 per cent than when it was less than 30per cent. Theoretical calculations, based on density levels,suggest that the water-filled porosity of the wood (water volumedivided by porosity volume) was positively correlated with thelinseed oil uptake, and more strongly correlated in earlywoodthan in latewood. There were also significant differences inuptake between different wood tissues; heartwood/mature woodand heartwood/juvenile wood showed 10–20 per cent weightincreases due to linseed oil uptake, compared with 30–50per cent in sapwood/mature wood. Examination by scanning electronmicroscopy confirmed these uptake patterns. The moisture contentafter impregnation was about 5 per cent, irrespective of theLinotech process parameters, tissue type and initial moisturecontent. In conclusion, the impregnation process used here resultsin high levels of well-dispersed linseed oil uptake and shouldfacilitate drying.     

Liquid penetration of precompressed wood VII: combined treatment of precompression and extraction in hot water on the liquid penetration of wood

The object of this study was to determine the cause of differences in the improvement in liquid penetration of precompressed wood species. The maximum amount of water uptake by the capillary rise method and changes in the aspirated pits seen with scanning electron microscopy before and after of preextraction and precompression were investigated using heartwood samples of four softwoods. The height of penetration and the weight by the capillary rise method for preextractive wood powders are discussed. Three wood species andLarix leptolepis showed marked increases in the amount of solution uptake after precompressed treatment only.Larix leptolepis wood required compression after extraction by boiling in water. These differences among wood species were caused by the accumulation of extractive material. It was also recognized that the accumulative material inLarix wood has plasticity and that inPseudotsuga is brittle. Based on these results it was found that it is difficult to destroy aspirated pits in the former and easy in the latter. On the other hand, the difference in penetration of each wood species was caused by the quantity and quality of the extraction material in addition to the extent of the wettability of the surface of the cell cavity as well as aspirated pit.Part of this report was presented at the 46th annual meeting of the Japan Wood Research Society, Kumamoto, April 1996     

Polyelectrolyte swelling behavior of chlorite delignified spruce wood fibers

Summary A coarse thermomechanical Asplund pulp was prepared from Norway spruce (Picea abies). The pulp was delignified to different degrees using acidified sodium chlorite. The swelling behavior (measured as water retention value=WRV) of the resulting pulps was studied under various chemical conditions (pH and conc. of NaCl). It is shown that chlorite-delignified pulps have an appreciable polyelectrolytic character. Whereas the WRV of an Asplund pulp does not respond to changes in the chemical environment, the delignified pulp has a WRV of 155 at pH 3 and 250 at pH 9. Compared under the same chemical conditions, the WRV increases with increasing degree of delignification (<70%) and is approximately constant at high degrees of delignification (>70%).The authors are indebted to Mr. Claes Beer at Sund-Defibrator, who assisted with the preparation of the Asplund pulp     

Strength properties of black spruce wood under different treatment

Summary The effect of various forms of treatment — chemical, thermal and pressure — on the tensile properties of wood was investigated. Spruce was impregnated in water, sodium sulfite and/or sodium bicarbonate, and heated at temperatures ranging from 20 to 190 °C. At the end of cooking (190 °C), decompression was applied both slowly and suddenly.A rise in temperature, an increase in heating time, from 4 to 10 min. at 190 °C, as well as fast pressure release influenced the tensile strength. The chemical treatment resulted in lignin sulfonation while carboxylation produced fiber swelling and, consequently, tensile strength decreased.The authors wish to thank the FCAR (Québec), NSERC (Canada) and Stake Tech. Co. for their financial support     

Dynamic crushing characteristics of spruce wood under large deformations

An extensive series of large deformation crushing tests with spruce wood specimens was conducted. Material orientation, lateral constraint and loading rate were varied. Regarding material orientation, a reduction in the softening effect and the general force level was observed with a higher fiber-load angle. A comparison with characteristics gained by application of Hankinson’s formula showed discrepancies in compression strength and the beginning of the hardening effect. Lateral constraint of the specimens caused a multiaxial stress state in the specimens, which was quantified with the applied measuring method. Further, a higher force level compared to specimens without lateral constraint and significant hardening effect at large deformations resulted. Thus, the influence of a multiaxial stress state on the force level could be determined. An increase in the loading rate led to higher force levels at any displacement value and material orientation.     

Studies on holocellulose and alpha-cellulose from spruce wood using cryo-ultramicrotomy

Summary Cryo-ultramicrotomy was applied to holocellulose and alpha-cellulose from spruce wood (Picea abies Karst.) for a light and electron microscopical study of the removal of lignin during chlorite delignification and the changes in swelling during delignification and alkali extraction. The swelling state of the fibre walls during each stage of treatment was well preserved, and distinct differences could be observed. Staining with uranyl acetate brought out the fine structure of the fibre walls down to the range of elementary fibrils.Submitted by Deutsche Forschungsgemeinschaft. The assistance of Dr. D. Grosser at the light microscope and of Miss U. Schwarz with the chemical analysis is greatly appreciated.     

Variation of measured cross-sectional cell dimensions and calculated water vapor permeability across a single growth ring of spruce wood

A statistical study of the cell dimensions in a growth ring of spruce along the radial and tangential directions is performed. The data are used to study the variation of the cell vapor permeability in the growth ring. Studying cell rows within one growth ring, the frequency distributions of the cell wall thickness in the radial direction and of the lumen dimension in the tangential direction are found to be both unimodal. In contrast, the frequency distributions of these dimensions in the other directions are bimodal, where the different modes can be attributed to earlywood and latewood. Analysis of the bimodal distributions results in the determination of threshold values of cell wall thickness and the lumen dimension for earlywood and latewood tracheids. The cell dimensions are used to predict cell porosity and water vapor permeability distribution within a growth ring. The bimodal frequency distributions of the tangential cell wall thickness and the radial lumen dimension provide an explanation for the observed bimodal frequency distribution of the cell water vapor permeability both in radial and in tangential directions. Contrary to measured macroscopic vapor permeability results, the tracheid geometry results in lower cell vapor permeability in radial than in tangential direction. This confirms that rays play an important role in the vapor permeability of wood, as they can be considered as pathways for vapor transport in radial direction. The dataset analyzed in this paper leads to a set of parameters characterizing the earlywood and latewood cell dimensions. Such characterization can be used, for example, for producing synthetic data for computational modeling studies.     

The enzymatic decomposition of neutral and acid polysaccharides from spruce wood

Summary Finely ground spruce wood (Picea abies (L.) Karst.) was incubated with various commercial enzyme preparations; the incubation liquid was analysed for the presence and volume of uronic acids and neutral sugars. The tested enzyme preparations dissolved neutral and acid sugar from the woodpowder. The most effective enzyme preparations were cellulolytic enzymes with some hemicellulolytic activites. This applied to the decomposition of neutral polysaccharide as well as to polyuronide. The polysaccharides in the cell wall were almost completely broken down to low molecular weight sugars by these preparations. Pectinase preparations, on the other hand, had lower efficacy in decomposing neutral and acid polysaccharides. A difference in efficacy of the enzyme preparations in decomposing heart- or sapwood could not be ascertained.     

Effect of severe thermal treatment on spruce and beech wood lignins

? The structure, proportion and mode of assembly of lignin, celluloses and hemicelluloses have marked effects on the reaction mechanisms during thermal treatment and therefore have a strong influence on the quality of the final product. The effect of treatment conditions, including severe conditions (up to 553 K) and treatment duration (up to 8 h) on the structure of native spruce and beech lignins was studied.

? Lignin content was determined by the Klason method and lignin structure was evaluated by thioacidolysis.

? The results highlighted the strong reactivity of the native spruce and beech lignins towards severe heat treatments. The distinct susceptibility of syringyl (S) and guaiacyl (G) units towards thermal treatment is confirmed by comparing the data for beech and spruce samples. The most severe treatment of spruce wood (280 °C) induced a dramatic enrichment in lignin content together with the almost complete disappearance of G lignin units, whereas a more moderate treatment substantially changed lignin structure by degradation reactions that affect the p-hydroxyphenyl (H) and G lignin units similarly.

? Thioacidolysis revealed that the thermal treatment induces the appearance of vinyl ether structures in spruce lignins. The decreased yield of the G and S thioacidolysis monomers reflects the progressive disappearance of G and S lignin units only involved in β-O-4 bonds and the formation of condensed linkages in proportions related to treatment severity. In severe conditions, β-O-4 linked S units are more degraded than their G homologues.

     

Effects of temperature and sulfonation on shear deformation of spruce wood

Summary The effects of temperature and sulfonation on the deformation of spruce wood at conditions comparable to those during screw press impregnation prior to mechanical pulping were studied using a dynamic testing method. In addition to the physical properties of wood, shear fracture surfaces obtained at different deformation temperatures and at different sulfonation levels were studied using scanning electron microscopy (SEM).The results showed that the failure energy of wood decreased gradually with increased deformation temperature in the tested range of 20–95 °C, due to thermal softening of the material. In addition to thermal treatment, the failure energy could also be reduced by sulfite treatment of the wood before deformation, and decreased with increasing sulfonation degree.The SEM analysis showed that increasing the deformation temperature causes the fracture plane to travel around the fiber walls instead of through them, thus exposing a smoother wood surface with less fiber damage. At a given deformation temperature, particularly at the lower temperatures, sulfonation improves fiber separation.Financial support from the Swedish National Board for Industrial and Technical Development (NUTEK) is gratefully acknowledged     

Microstructure,strength and structural integrity of heat-treated beech and spruce wood

Abstract

Heat treatment of wood is an effective method by which to improve the dimensional stability and biological durability, but the mechanical strength is decreased at the same time. Besides chemical modification of cell-wall constituents, physical weakening of the microstructure owing to heat-induced defects may also contribute to strength loss. Therefore, anatomical properties of heat-treated beech (Fagus sylvatica L.) and spruce (Picea abies Karst.), studied by light microscopic and scanning electron microscopic analysis, and their interrelation with strength properties and structural integrity were investigated. For determination of structural integrity, the high-energy–multiple-impact (HEMI) test was applied. Microscopic analyses showed frequent formation of radial cracks in heat-treated beech close to the rays as well as tangential cracks in the latewood of spruce. In addition, the modulus of rupture was more affected by the heat treatments than the resistance to impact milling (RIM) determined by the HEMI test, because RIM is based on multiple fractures on the microlevel that are not affected by the formation of intercellular cracks or other defects due to the heat treatment. It was concluded that heat-induced defects in the wood microstructure contribute to the substantial strength loss of thermally modified timber.     

Aging and fossilization of wood and its components

Summary Aging of wood begins with the cutting of a tree. The subsequent changes of the wood substance proceed very slowly and depend on environmental conditions. In a hot, dry desert climate wooden objects and cellulose textiles are preserved for several millenia, whereas their degradation is accelerated by conditions which favor the attack of microorganisms.Two conditions under which aging processes take place can be distinguished: a) aerobic conditions as prevailing in wooden buildings, sculptures etc.; b) anaerobic conditions valid for wooden items buried in the ground or submerged in water such as foundation pillars, ships etc. Submersion and underground embedding initiate the very slow process of fossilization in which the cell wall substance is transformed into highly condensed compounds (coalification) or is substituted by minerals (silicification).The various wood components are subjected to different kinds of degradation and conversion. The polysaccharides disappear with aging and seem to be more sensitive than lignin. Although more resistant, the lignin is converted chemically and its structure differs increasingly from its original state. Even extractives may survive millions of years.Academy Lecture presented at the IAWA IUFRO Wood Anatomy Symposium 1990, in Zürich, Switzerland, on 24th July 1990I wish to express my gratitude to members of my staff who have been involved in the study of ancient and fossilized wood as well as of Egyptian linen for the past 23 years: Monika Friedl, Margarete Przyklenk, Manfred Stoll, Ulrike Wegener, Maria Wenzkowski. Many thanks to the guests in my laboratory who worked in this field and whose results were included in this report: Yoon Soo Kim (Kwangju, Korea), Renzo Tomellini (Rome, Italy). And last but not least I am much indebted to several colleagues who provided me with slides or gave permission to reproduce their figures for the Academy Lecture: Takeshi Furuno (Matsue, Shimane, Japan) Dietger Grosser (Munich, FRG), John I. Hedges (Seattle, Wash., USA), Per Hoffmann (Bremerhaven, FRG), John R. Obst (Madison, Wisc., USA). Sylvia Schoske (Munich, FRG)     

Liquid water absorption in uncoated Norway spruce (Picea abies) claddings as affected by origin and wood properties

Abstract

Uncoated Norway spruce specimens from different spatial positions within stems from two origins with different growth conditions were exposed to liquid water over a prolonged time, and apparent diffusion coefficients and rates of void filling were calculated from sorption curves. Both apparent diffusion and rate of void filling were significantly affected by origin and by the difference between inner and outer boards. The differences between inner and outer boards were explained by heartwood proportion and density, but some effects of origin remained when these properties were accounted for. The apparent diffusion coefficient was reduced by increasing density, and increased by increasing heartwood proportion. Void filling rate was reduced by both increasing density and increasing heartwood proportion. Since the effect of heartwood proportion was more pronounced in the material from the highly productive area, it may have been confounded with properties of juvenile wood.     

Utilization of wood cell wall components

This article summarizes current utilizations of wood cell wall components in relation to biorefinery of woody biomass as a separation method of its constituents. Especially, utilization of isolated lignins, involving transformation and molding, are demonstrated with respect to productions of carbon fibers and their further functionalization, such as developments of activated carbon fibers and electrodes for second battery and electric double-layer capacitor.