Theoretical models for creep slip of nailed joints between wood and wood-based materials

Summary Applying modern methods of analyzing floor, wall, and connection subsystems in light-frame wood buildings requires information on the stiffness of nailed joints under long-term loads. Because this information can best be derived by testing nail-joint specimens under constant loads, theoretical procedures were developed that use test data for constant loads to predict stiffness under variable in-service loads; five nonlinear, viscous-viscoelastic models were develpoed on the basis of existing formulations of creep and mechanisms of load transfer between nails and wood. The models incorporated the modified superposition and strain-hardening principles in describing responses to discrete or continuous loading functions. Tests have shown that the models closely predict creep slip of typical nailed joints.This research was jointly supported by the Forest Research Laboratory, Oregon State University, and the Cooperative State Research Service, U.S. Department of Agriculture, Special Grant 85-CRSR-2-2553. This is Paper 2288 of the Forest Research LaboratoryFormerly Graduate Research Assistant Forest Research Laboratory     

Chemical mechanism of fire retardance of boric acid on wood

It is commonly accepted that the fire retardant mechanism of boric acid is a physical mechanism achieved by the formation of a coating or protective layer on the wood surface at high temperature. Although a char-forming catalytic mechanism has been proposed by some researchers, little direct experimental support has been provided for such a chemical mechanism. In this paper, new experimental results using thermal analysis, cone calorimetry (CONE), and gas chromatography–Fourier transform infrared spectroscopy (GC–FTIR) analysis are presented and the fire retardant mechanism of boric acid on wood is discussed. Basswood was treated with boric acid, guanylurea phosphate (GUP), and GUP–boric acid. Treated wood was then analyzed by thermogravimetry (TG/DTG), differential thermal analysis (DTA), CONE, and GC–FTIR analysis. Thermogravimetry showed that the weight loss of basswood treated with boric acid was about three times that of untreated or GUP-treated wood at 165°C, a temperature at which GUP is stable. The DTA curve showed that boric acid treated basswood has an exothermal peak at 420°C, indicating the exothermal polymerization reaction of charring. CONE results showed that boric acid and GUP had a considerable synergistic fire retardant effect on wood. The GC–FTIR spectra indicated that compounds generated by boric acid treated wood are different than those generated by untreated wood. We conclude that boric acid catalyzes the dehydration and other oxygen-eliminating reactions of wood at a relatively low temperature (approximately 100–300°C) and may catalyze the isomerization of the newly formed polymeric materials by forming aromatic structures. This contributes partly to the effects of boric acid on promoting the charring and fire retardation of wood. The mechanism of the strong fire retardant synergism between boric acid and GUP is due to the different fire retardant mechanisms of boric acid and GUP and the different activation temperatures of these two chemicals.The Forest Products Laboratory is maintained in cooperation with the University of Wisconsin. This article was written and prepared by U.S. Government employees on official time, and it is therefore in the public domain and not subject to copyright. The use of trade or firm names in this publication is for reader information and does not imply endorsement by the U.S. Department of Agriculture of any product or service.     

Variation of the phenolic hydroxyl group content in wood lignins

Summary The phenolic hydroxyl group content of wood lignin has been determined in situ by a periodate oxidation method for four softwood and six hardwood species. Hardwood lignins, in contrast to softwood lignins, showed a significant variation among different species in this functional group content which decreased with an increase in the proportion of syringyl units in the wood lignin.Financial support from the Empire State Paper Research Associates is greatly appreciated     

Pyrolysis reactions of Japanese cedar and Japanese beech woods in a closed ampoule reactor

The chemical structures of hemicellulose and lignin are different for two distinct types of wood, i.e., softwood and hardwood. Such differences are expected to affect pyrolysis behavior. In this article, the differences are discussed for Japanese cedar wood (a softwood) and Japanese beech wood (a hardwood) pyrolyzed in a closed ampoule reactor (N₂/600°C/40–600 s). Oven-dried samples were used to eliminate the influence of initial water. Demineralized samples (prepared by acid washing) were also used to determine the influence of the minerals contained in the wood samples. As a result, some features were disclosed for secondary char (coke) formation, char reactivity, tar formation, and subsequent decomposition.     

Microstructure of wood char

Summary Past research on the combustion and pyrolysis of wood have often indicated a link between wood microstructure and its observed properties in fire exposure. The present research, after utilizing an instrumented fire exposure shown to simulate actual fire conditions, examines the microstructure of fire damaged wood and considers the implications of microstructural changes seen on the burning process.Differences in microstructural detail between wood and char, as well as fissure geometry, were shown to be consistent. The demarcation between damaged and undamaged wood was shown to be extremely small (several cell layers in thickness). The resulting microstructural observations are considered in light of published kinetic data on wood combustion and current theories and data on thermal degradation of wood.The authors wish to acknowledge the general support of the University of California Forest Products Laboratory as well as grant support to the University of California Berkeley Fire Research Group (NSF-Rann-S-22053, NFPCA-S-22584), University of California Berkeley Electron Microscopy Lab. (NSF-GB-38359) and the University of California, Davis Department of Botany (NSF-GB-29653). In addition we would also like to thank Dr. Arno P. Schniewind, University of California Forest Products Laboratory and Dr. R. Falk, University of California, Davis, Department of Botany     

A reexamination of some deviations from Darcy's Law in coniferous wood

Summary A number of workers have noted a marked decrease of wood permeability with increasing specimen length, and to date a model proposed by Bramhall has been used to explain the phenomenon. This describes the effect of random blockages on the permeability of an anisotropic porous medium. However, the model does not allow for the fact that transverse flow may allow longitudinal flow paths to circumvent blockages to some extent, so some deviation from it can be expected. The issue is an important one if laboratory experiments are to be used as a basis for the prediction of the behaviour of wood during impregnation or drying on a commercial scale. A modified model which allows for transverse flow is therefore developed. New experimental evidence which cannot be explained by the Bramhall model, but which can be explained by the new model, is presented.This paper was written while the author was Heritage Visiting Scientist at the Forest Products Laboratory, U.S. Department of Agriculture, and Visiting Professor at the Department of Forestry, University of Wisconsin, both at Madison, Wisconsin, USA. This support is gratefully acknowledged. The author would also like to thank Messrs. J. Ambler, M. C. Breese and S. H. Turner, who carried out some of the experimental work, and staff at the Commonwealth Forestry Institute, Oxford, who provided the Juniperus procera material tested     

Measurements of compression creep of wood at humidity changes

Summary Uniaxial compression creep tests of tubular spruce specimens loaded in uniaxial compression are reported. The relative humidity in the interior of the tube is varied in a controlled manner. The results indicate that creep is greatly increased in magnitude by simultaneous humidity changes of either sign.Thanks are due to Dr. John Zahn of Forest Products Laboratory, Madison, Wisconsin, for various helpful advice, as well as for arranging the manufacture of test specimens in his laboratory. Thanks are also due to Forest Products Laboratory of the U.S. Department of Agriculture, Madison, Wisconsin, for funding a large part of this work under subcontract FP-81-0389.     

Micropores and mesopores in the cell wall of dry wood

To investigate micropores and mesopores in the cell walls of dry wood, CO₂ gas and N₂ gas adsorption onto dry wood were measured at ice-water temperature (273 K) and liquid nitrogen temperature (77 K). CO₂ gas adsorption isotherms obtained were used for determining micropore volumes smaller than 0.6 nm by the HK method (Horvath-Kawazoe method), and N₂ gas adsorption isotherms obtained were used for determining the mesopore volume between 2 nm and 50 nm by the Barrett-Joyner-Halenda (BJH) method. Micropores and mesopores existed in cell walls of dry wood, and the cumulative pore volume was much larger for micropores than for mesopores. Micropores in the cell wall of dry wood decreased with elevating heat treatment temperature, and the decreased micropore was reproducible by wetting and drying. Mesopores did not decrease so much with elevating heat treatment temperature. Micropore volumes for the softwood Hinoki and the hardwood Buna were compared. A larger amount of micropores existed in hardwood Buna than in softwood Hinoki, and this relationship was considered to correspond to the difference in thermal softening properties for lignin in water-swollen Hinoki and Buna. This result probably indicates that micropores in the cell walls of dry wood relate to the structure of lignin.     

Attempts to understand the nature of phenolic and etherified components of wood lignin

Summary Periodate oxidation, because of its high selectivity in degrading phenolic nuclei, has been combined with nitrobenzene oxidation and phenyl nucleus exchange techniques to investigate the nature of wood lignin in situ. For both softwood and hardwood, the phenolic and etherified components of wood lignin have been shown to differ significantly in chemical composition, and the etherified lignin structure appears to be substantially more condensed.Financial support from the Empire State Paper Research Associate (ESPRA) and by the NRICGP of USDA (No. 93-37103-9318) is greatly appreciated     

The validity of the use of SEM/EDAX as a tool for the detection of UF resin penetration into wood cell walls in particleboard

Summary The interpretation of data from scanning electron microscopy (SEM) combined with energy dispersive analysis of X-rays (EDAX) is dependent on the size of the excitation volume, the magnitude of which for organic materials such as wood has been little studied. From the analysis of a model system comprised of a thin layer of gold sandwiched between two layers of an epoxy plastic, it was shown that about 90% of all excitations arise from a volume about 6 m wide and 4 m deep. However, these dimensions vary with the orientation of the gold relative to the specimen surface, and the specimen tilt. Theoretical predictions based on these data support, but not conclusively, the previously published SEM/EDAX evidence of the penetration of urea formaldehyde resins into the wood cell wall in particleboard manufacture.This paper was written while A. J. Bolton was Heritage Visiting Scientist at the Forest Products Laboratory, U.S. Department of Agriculture, and Visiting Professor at the Department of Forestry, University of Wisconsin, both at Madison, Wisconsin, U.S.A. This support is gratefully acknowledged. The authors would also like to acknowledge the assistance of E. Edwards in machining the SEM specimens     

The mechanism of the Mäule colour reaction introduction of methylated syringyl nuclei into softwood lignin

Summary Ezo spruce (Picea jezoensis) wood meal and milled wood lignin were successively reduced with sodium borohydride, methylated with methanol-HCl, oxidized with Fremy's salt, reduced with sodium dithionite, and methylated with diazomethane. Permanganate oxidation of the treated milled wood lignin showed that 0.08–0.1/C9 units of 3,4,5-trimethoxyphenyl groups were introduced into the softwood lignin. Although hardwood meal (beech, Fagus crenata) methylated with diazomethane gave a purple-red colour with the Mäule test, the treated softwood meal gave only a dark brown colour. The aromatic nuclei of lignin were broken down by the Mäule treatment. The consumption of permanganate by treated softwood lignin was higher than by hardwood lignin, which suggests that the guaiacyl nuclei were broken down severely. It is proposed that the purple-red colour obtained from methylated hardwood lignin with the Mäule colour test is generated by reaction of syringyl groups which were liberated by -ether cleavage under the permanganate oxidation conditions.     

Prehydrolysis of beechwood

Summary The kinetics of the isothermal prehydrolysis of beechwood at 160°C and 170°C were investigated. It was shown that the hydrolysis of the hemicellulose portion was realised in two phases. The depth and rate of the first rapid prehydrolysis phase and the second slow phase depend on the temperature used. The lignin content in the prehydrolysed chips increased with the duration of the prehydrolysis due to the easily removable hemicellulose portion. The maximum amount of lignin extracted was gained after 45–60 minutes of isothermal prehydrolysis at 160°C with the yield decrease to 82–80 per cent and at 170°C with the yield decrease to 70–68 per cent. At the temperature of 160°C the amount of the lignin portion extracted was about 5 per cent and at 170°C at about 10 per cent of the whole lignin content in wood. The extraction of the whole hemicellulose portion present in wood was attained at 160°C after 5 hours prehydrolysis time, at 170°C after 80 minutes.By the prehydrolysis of hardwood to 30 per cent loss of the wood substance highly purified dissolving pulp was prepared by AQ catalysed sodium pulping. The pulp attained was characterised by a high alpha-cellulose content over 97 per cent and a low solubility in solutions of alkali. The sulphur-free delignification together with the low consumption of active chlorine (1.5–1.7 per cent) cause less environmental pollution.     

Microstructure of wood char

Summary The exposure of wood treated with a commercial fire retardant chemical to fire conditions resulted in different patterns of char and fissure development than are seen in untreated whole wood. In addition microstructural observations demonstrated the existence of particulate fire retardant residues in char from treated wood. The source and mode of growth of these particles is considered as well as effects of fire retardants on crack growth, char development and overall appearance of chars from treated wood.The authors wish to acknowledge the general support of the University of California Berkeley Fire Research Group (NSF-RANN-S-22053, NFPCa-S-22584), University of California Berkeley Electron Microscopy Lab. (NSF-GB-38359) and the University of California, Davis Department of Botany (NSF-GB-29653). In addition we would also like to thank Dr. Arno P. Schniewind, University of California Forest Products Laboratory and Dr. R. Falk, University of California, Davis, Department of Botany     

Ultrastructural implications of gamma-irradiation of wood

Summary An attempt is made in this study to relate the gamma-irradiation induced degradation of wood samples to their lignin content and distribution in the cell wall. Samples of Douglas-fir and yellow-poplar were submitted to increasing doses of gamma-irradiation and subsequently extracted with a dilute NaOH solution or with DMSO, prior to SEM observation. Other samples were observed in TEM. The irradiation-extraction procedure degraded the hardwood more than the softwood. In both species, the middle lamella was more resistant than the secondary wall. The S3 layer in Douglas-fir and the warty layer in yellow-poplar appeared to be more resistant than the other secondary wall layers. Some difference was also observed in radiation stability between tracheids or fibres and ray cells. This procedure is suggested as a method for studying lignin distribution in the wood cell wall.This research was conducted as part of a thesis submitted by the first author in partial fulfilment of the requirements for the Master of Science degree at the State University of New York College of Environmental Science and Forestry, Syracuse, New York. The authors wish to thank Dr. John A. Meyer who carried out the irradiation procedure. The first author also whishes to express gratitude to the Belgian American Educational Foundation, Inc., The Fondation Francqui and Mister Charles Berolzheimer, Research Director of the California Cedar Products Company, for having provided financial support for this study     

Determination and use of moisture diffusion coefficient to characterize drying of northern red oak (Quercus rubra)

Summary Diffusion analysis can be used to estimate the time required to dry lumber. However, more accurate calculations require additional information on the relationship between the diffusion coefficient as a function of moisture content and on the effects of temperature, equilibrium moisture content, board thickness, and air velocity on drying time and moisture gradients. The primary objectives of this study were (1) to determine the diffusion coefficient of northern red oak (Quercus rubra) as a function of moisture content and (2) to compare experimentally determined sorption times and moisture content gradients with those calculated by the diffusion model. The diffusion coefficient was found to increase approximately exponentially with moisture content over a range of 6 to 30 percent at 43°C. This relationship was similar in both adsorption and desorption tests. Experimental adsorption and desorption times and desorption moisture content gradients were compared with finite difference solutions to the diffusion equation. Practical uses of solutions to the diffusion equation are illustrated for kiln drying wood that has first been predried to below the fiber saturation point. Drying time is also related to variable kiln conditions and board thickness.This research was partially funded under the U. S. Department of Agriculture Competitive Grant programThe Forest Products Laboratory is maintained in cooperation with the University of Wisconsin. This article was written and prepared by U.S. Government employees on official time     

Distribution of lignin in normal and tension wood

Summary The distribution of lignin in normal and tension wood of four hardwood species has been studied by examination in the electron microscope of the lignin skeletons remaining after removal of the polysaccharides with hydrofluoric acid. In normal wood fibers, the S₁ had a higher lignin concentration than the S₂ layer, which was not as highly lignified as in conifer tracheids. Vessels had a high concentration of lignin in both normal and tension wood, while the extent of lignification of the parenchyma was variable.In tension wood fibers, the S₁ and S₂ layers were highly lignified. A thick, unlignified G-layer was often associated with an extremely thin S₂ layer with a high concentration of lignin. In both normal and tension wood, the lignin had the same orientation as the cellulose micro-fibrils in the different cell wall layers. The results confirm the earlier conclusion that, in the species investigated, the same amount of lignin is present in gelatinous as in normal fibers. Evidently, the lignification mechanism operates normally in the non-gelatinous layers of the fibers, as well as in the vessels and in the parenchyma of tension wood.

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Zusammenfassung Die Ligninverteilung im Normalholz und im Druckholz von vier Laubhölzern wurde untersucht. Die Ligningerüste, die nach der Entfernung der Polysaccharide durch Fluorwasser-stoffsäure übrigblieben, wurden im Elektronenmikroskop beobachtet. In den Normalholzfasern hatte die S₁-eine höhere Ligninkonzentration als die S₂-Schicht, die weniger lignifiziert war als in den Koniferentracheiden. Die Gefäße hatten eine hohe Ligninkonzentration in sowohl Normal-als in Zugholz, während der Lignifizierungsgrad der Parenchymzellen variierte.In den Zugholzfasern waren die S₁- und S₂-Schichten völlig lignifiziert. Eine dicke, unlignifizierte G-Schicht war oft mit einer außerordentlich dünnen S₂-Schicht, die eine hohe Ligninkonzentration zeigte, verbunden. Sowohl im Normal- wie auch im Zugholz besaß das Lignin dieselbe Orientierung wie die Cellulosemikrofibrillen in den verschiedenen Zellwandschichten. Die Ergebnisse bestätigen den früheren Schluß, daß in den hier untersuchten Laubhölzern in den gelatinösen und in den normalen Fasern dieselbe Ligninmenge vorliegt. Offenbar läuft der Mechanismus der Lignifizierung in den S₁- und S₂-Schichten der gelatinösen Fasern des Zugholzes normal ab.

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This investigation was supported by the United States Department of Agriculture, Forest Service, through Forest Service Research Grant No. 1, which is hereby gratefully acknowledged.     

The fractal estimation of wood color variation by the triangular prism surface area method

Color variations of the surfaces of fifteen wood species were characterized by fractal dimension of the triangular prism surface area method. Softwood and hardwood indicated apparently different in the mean fractal dimensions of red and green colors. Red color behaved steadier in softwood than in hardwood and green color varied comparatively stronger in hardwood than in softwood. No evident differences between softwood and hardwood were found in the variation of blue color of all the specimens. Following the low-to-high value order of the mean fractal dimensions, three types of combination of red (R), green (G) and blue (B) colors were found: RGB, RBG and BGR. There also existed six types of fractal dimension distribution; namely, plane, included plane, concave, convex, zigzag, and hilly distributions. Fractal dimensions across the grain changed greatly whereas those along the grain became relatively steady. The characteristic difference of color variation was defined for each species, which was inferred to characterize its own unique appearance of surface color. For color matching of wood parts, fractal dimension quantitatively furnishes essential information of color variation in local and overall features. Such evaluation can be efficiently carried out with few measurements along the grain and by detecting a single color (red, green or blue) only. Received 5 May 2000     

Studies of the degradation and protection of wood surfaces

Summary Large weight losses occurred in thin veneers of radiata pine (P. radiata) during natural weathering due mainly to loss of lignin and hemicelluloses. This was demonstrated by direct chemical analysis and by spectrocopic techniques. Treatment of veneers with dilute aqueous solutions of the recognized surface stabilizing compound chromium trioxide was found to dramatically restrict weight loss during weathering, but similar applications of ferric compound were less effective (Evans, Schmalzl 1989). In order to rationalize these protective effects FTIR internal reflectance spectroscopy was used to study chemical changes taking place at the wood surface upon treatment and during weathering. The spectra obtained provide direct evidence for the modification and stabilization of the lignin aromatic system with aqueous chromium trioxide and to a lesser extent with ferric salts. It is postulated that photostable lignin complexes are formed. The implications of these findings for the development of improved surface stabilizing compounds for wood are discussed briefly.The authors wish to thank the following: Tom Syers and Lloyd Vickers (C.S.I.R.O., Division of Forestry and Forest Products); Helen Neave, and Clive Hilliker (Australian National University, Department of Forestry) for technical assistance, and the Stanley Melbourne Bruce fund for financially supporting part of the work     

Multivariate modeling of acoustomechanical response of 14-year-old suppressed loblolly pine (<Emphasis Type="Italic">Pinus taeda</Emphasis>) to variation in wood chemistry,microfibril angle and density

The polymeric angle and concentration within the S₂ layer of the softwood fiber cell wall are very critical for molecular and microscopic properties that influence strength, stiffness and acoustic velocity of wood at the macroscopic level. The main objective of this study was to elucidate the effect of cellulose, hemicellulose, lignin, microfibril angle and density on acoustic velocity and material mechanical properties of 14-year-old suppressed loblolly pine. Cellulose, hemicellulose and density are consistently the most important drivers of strength, stiffness and velocity. Cellulose and lignin are the highest and lowest contributor to velocity, respectively, with lignin acting as a sound wave dispersant, while cellulose is the most important conductor of sound wave at the molecular level, while hemicellulose acts as a special coupling agent between these components. The polymeric constituents are thus important drivers of sound wave propagation at the molecular level, while density played a subsequent role at the macroscale.     

Modelling moisture-related mechanical properties of wood Part I: Properties of the wood constituents

Summary By starting with simple concepts of the molecular structure and building up through the various levels of organisation in the wood cell wall it is possible to construct a model that simultaneously predicts the variation with moisture content change of both the longitudinal Young's modulus and longitudinal shrinkage of wood. To do this it is first necessary to define the stiffness and swelling characteristics of the lignin, hemicellulose and cellulose constituents of the wood as moisture content changes. It is suggested here that it is the bound fraction of the sorbed water that is responsible for the changes in swelling stress as well as for change in stiffness in the lignin and hemicellulose. The magnitudes of the stiffness of each of the constituents appear to be quite closely circumscribed by experimental values for longitudinal Young's modulus and shrinkage of wood and it is apparent that the stiffness characteristics of the in situ constituents are compatible with available experimental evidence for extracted lignin and hemicellulose and for native cellulose.