The ultrastructure of cellulose from wood

Summary During the delignification of wood several processes overlap one another. One of these is the penetration of the wood samples by the delignifying solution. Penetration tests under different conditions show that there is almost no difference in the penetration depth of wood samples penetrated by diffusion only and of wood samples treated with pressure. In both cases the pits are closed during the flow of fluids. Vacuum treated samples show better penetration and most of the pits in these samples remain open. The distribution of fluids within the cell walls takes place in the intercellular spaces, in small openings in the compound middle lamella and in the secondary wall 1 as well as in very fine pores in the secondary wall 2. The penetration of a wood sample is greatly facilitated if the sample is mechanically injured. A slowly proceeding delignification with ethylene sulphite shows that the delignification obviously starts in the S 1 layer and proceeds from there towards the compound middle lamella and the S 2 layer. In the first stages of lignin removal the compound middle lamella is also attacked, the attack beginning at the border of the pit chambers.     

The ultrastructure of cellulose from wood

Summary Since in these studies wood is used as basic material for the isolation of cellulose the structure and the composition of this planty substance were considered in greater detail. New measurements of the fiber dimensions and the thickness of the cell wall layers of typical springwood and summerwood tracheids in combination with data obtained from literature led to a model showing the most probable distribution of cellulose, polyoses, and lignin within the cell wall. The ultrastructural composition of the wood cell wall has been deduced from the properties and the behaviour of the cell wall components. The described model will be the basis for subsequent considerations.

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Zusammenfassung Da bei diesen Untersuchungen Holz das Ausgangsmaterial zur Isolierung von Cellulose bildet, wurden die Struktur und die Zusammensetzung dieser pflanzlichen Substanz näher betrachtet. Neue Messungen der Faserdimensionen und der Dicke der einzelnen Wandschichten typischer Früh- und Spätholztracheiden in Verbindung mit Literaturwerten führten zu einem Modell, das die wahrscheinlichste Verteilung von Cellulose, Polyosen und Lignin innerhalb der Zellwand zeigt. Die ultrastrukturelle Zusammensetzung der verholzten Zellwand wurde aus den Eigenschaften und dem Verhalten der Zellwandkomponenten abgeleitet. Das beschriebene Modell wird die Grundlage für nachfolgende Betrachtungen bilden.

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Dedicated in appreciation to my esteemed teacher Prof. Dr.-Ing. Georg Jayme, on the occasion of his 70th birthday.     

Effect of adding steam-exploded wood flour to thermoplastic polymer/wood composite

The effect of steam-exploded wood flour (SE) added to wood flour/plastic composite was examined using SE from beech, Japanese cedar, and red meranti and three kinds of thermoplastic polymer: polymethylmethacrylate, polyvinyl chloride, and polystyrene. Addition of SE increased the fracture strength and water resistance of the composite board to an extent dependent on the polymer species and the composition of wood/SE/polymer. However, water resistance decreased with the increasing proportion of SE when SE meranti was added. Effects of the wood species of SE on the properties of resulting board were small. An increased moisture content of wood flour or SE (or both) increased the variation of board performance.     

Protection of wood particle board against termites

Summary Particle boards are of increasing economic importance. Without special treatment they are destroyed by termites. Deterioration of unprotected material as well as possibilities and present knowledge of preservation against termite attack are briefly described. Recent laboratory experiments with particle board treated to make it resistant to humidity and basidiomycete fungi showed that only one organic preservative out of four protected the boards also against termite attack; one of two water-soluble preservatives gave promising results. Heterotermes indicola (Wasmann) from India proved to be more aggressive and resistant to the preservatives than Coptotermes amanii (Sjöstedt) from Kenya and Nasutitermes nigriceps (Haldemann) from Guatemala. Kalotermes flavicollis (Fabr.) from Italy was also very tolerant to the fungicidal preservatives. Further development of treatments of particle board against termites is required.Part of this paper was prepared for the World Consultation on the Use of Wood in Housing, Vancouver, B. C., Canada, July 5–16, 1971.     

Ultrastructure of wood cellulose substrates during enzymatic hydrolysis

Summary The ultrastructure of holocellulose and alpha-cellulose from Pinus radiata D. Don was examined after treatment with cellulase for either 24 hours or 7 days. A procedure for localising the enzyme in situ using phosphotungstic acid is described. The pattern of degradation differed between the two substrates with alpha-cellulose being much more susceptible to hydrolysis than holocellulose. In both substrates the primary wall showed evidence of hydrolysis after 24 hours and was completely hydrolysed after 7 days. In holocellulose after 7 days treatment, hydrolysis of the secondary wall was confined to localised areas of the S3 layer sometimes penetrating into the S2 region. In contrast, alpha-cellulose showed uniform degradation across the secondary wall. Enzyme did not appear to penetrate the holocellulose but full penetration occurred in alpha-cellulose, the enzyme being closely associated with individual microfibrils. The reasons for these differences in degradation pattern are discussed.     

Ammonia sorption isotherms of wood and cotton cellulose

Summary Sorption isotherms of ammonia were measured on cellulosic materials, such as beech and birch wood, as well as on cotton cellulose, the object being to obtain information on the nature of interaction between the wood and the ammonia by means of application of various sorption theories. As a result several analogies between the sorption of ammonia vapour and water vapour could be observed.—The isotherms displayed the typical S-shape and developed a hysteresis along the adsorption and desorption lines. The sorbate films reached a thickness of 4–6 molecular layers. The lowering of enthalpy of the ammonia vapour appeared to be the propelling force of the sorption process, as in the case with the uptake of water vapour.—In contrast to water isotherms, however, ammonia isotherms cannot be reproduced with the same specimen. Each sorption cycle brought a loss of substance and a reduction of the fibre saturation capacities of the adsorbent. In ammonia vapour the fibre saturation points were found at sorbate concentrations twice as high as in water vapour. The hysteresis between the adsorption and desorption processes also appeared with ammonia vapour; however, the continuous changes of the adsorbent, caused by chemical interaction with ammonia, produced heavy displacements. The specific surface area of the samples in ammonia was approximately twice the size of that in water, but the extensions varied greatly during the sorption cycles.These investigations have been supported by the Zentenarfonds of the Swiss Federal Institute of Technology.     

Movement in a board of impermeable wood during drying

 Creep and sorptive-mechano-effect are defined in terms of complementary partial derivatives. The nett strain and the distribution of mechanical strain in a board of rectangular cross-section is predicted where the board is dried by the progression of a square front. The effects of creep and sorptive-mechano-effect are considered separately and when both are effective. Received 20 September 1999     

Effect of intermittent heat treatment on crystallinity in wood cellulose

The effect of intermittent heat treatment on cellulose crystallites in wood was studied to evaluate quantitatively the changes of crystallinity induced by intermittent and continuous heating. The changes in crystallinity were found to be strongly affected by the intermittent heat treatment. The increased crystallinity, the width of the crystals, and the piezoelectric properties were the same for the first intermittent heating as for continuous heating. Further intermittent heating for the same time duration and temperature had no effect on the above properties, probably due to the stopping of the thermal reaction during the interval. Our results suggested that intermittent heat treatment has certain critical cooling temperatures that stop the thermal reaction and are closely related to the duration of the interval. Samples once exposed to a certain duration of heat treatment and then cooled need more time, about twice that of the first duration of intermittent heating compared with continuous heating, to reach maximum crystallinity in wood cellulose.     

Properties of PP/wood flour/organomodified montmorillonite nanocomposites

In this research, composites based on polypropylene (PP), beech wood flour, and organomodified montmorillonite (OMMT) were prepared and characterized for their properties. The blend nanocomposites were prepared by melt mixing of PP/WF at 50% weight ratios with various amounts of OMMT (0, 3, and 6 per hundred compounds (phc)) in a Hakee internal mixer. Then the samples were made by injection molding. The influence of organomodified montmorillonite contents on clay dispersion, physical and mechanical properties of PP/wood flour composites were investigated. Results indicated that the flexural strength and modulus, tensile strength and modulus increased by addition of 3 per hundred compounds (phc) of organomodified montmorillonite (OMMT), but decreased with 6 phc OMMT addition. However, impact strength, water absorption and thickness swelling of the composites decreased with increasing nanoclay loading. X-ray diffraction patterns (XRD) and transmission electron microscopy (TEM) revealed that the nanocomposites formed were intercalated. Also, morphological findings showed that samples containing 3 phc of OMMT had higher order of intercalation.     

Enzymatic degradation of cellulose,cellulose derivatives and hemicelluloses in relation to the fungal decay of wood

Summary Cellulases and hemicellulases (mannanase and xylanase) from culture filtrates of various fungi, including a brown rot fungus, Polyporus schweinitzii and a soft rot fungus, Chaetomium globosum, have been isolated and characterized. Investigations of their molecular weights, pH- and temperature optima and stabilities indicate that hydrolases of the wood destroying fungi are very similar to one another and to hydrolases from various other plant organisms. Substrate specificities and the effect of substituents on the natural substrates have also been investigated. Routine tests for mannanase and xylanase were carried out with model substrates (mannan from Tubera salep, xylan from wheat straw), but preliminary tests with complex hemicelluloses isolated from wood showed that these too could be broken down to monoor oligosaccharides. The results presented are discussed in relation to possible roles of the various enzymes in vivo.Paper presented at the Int. Wood Chemistry Symposium, Seattle, 3. IX. 1969.With support of the Deutsche Forschungsgemeinschaft.     

Thermoplastic flow behavior of steamed wood flour under heat and compression

In this study the thermoplastic flow behavior of steamed wood flour was investigated. First it was demonstrated that steamed Japanese beech flour flowed out of the nozzle under compression at high temperature in a thermal flow test with a capillary rheometer. The effects of the steaming temperature, steaming time, compressive pressure, and moisture content of wood flour on the thermal flow temperature were examined. It was shown that the higher the steaming temperature and compressive pressure, the lower the thermal flow temperature. Also, the thermal flow temperature of the sample steamed at 200°C for 20 min became lowest and increasingly higher over time. Furthermore, the thermal flow temperature became linearly low with increasing moisture content of the sample under 15%, whereas it became essentially constant over 15%. It is clarified that compressive pressure and moisture content as well as the steaming conditions profoundly affect the thermoplastic flow behavior of steamed wood flour.     

Dynamic-mechanical analysis and SEM morphology of wood flour/polypropylene composites

Introduction It is well known that over the past few decades, polymers have replaced many conventional materials, such as metal and wood in many applications. This is due to the advantages of polymers over conventional materials (Maurizio et al. 1998; Adr…     

Laminar sorption and swelling theory for wood and cellulose

Summary The known requirements for the sorption and swelling of wood are reviewed. These are shown to be compatible, in the case of softwoods, with the following simplified model. The fibers are continuous with either rectangular or circular cross sections and lumen of the same shape with a constant size. The fiber walls consist of concentric lamina made up of small repeating units 100 Å by 100 Å, consisting of a microcrystalline core surrounded by an amorphous sheath. All sorption and swelling occurs at the surfaces of or within the amorphous sheath. The major portion of the sorption and swelling is inter-laminar with just sufficient intra-laminar sorption and swelling to avoid laminar distortion. Calculations give the generally accepted internal sorption surface for water of about 200 square meters per gram. The portion of the total sorption that is intra-laminar varies from 5 ... 20 percent in going from wood with a specific gravity of 0.3 ... 1.0. Thickness of sorption in water molecules per sorption site vary from 6.1 ... 4.9 for inter-laminar sorption and 0.35 ... 1.35 for intra-laminar sorption in going from wood with a specific gravity of 0.3 to one of 1.0. Similar values are obtained from experimental swelling data where lumen cross sections change. Similar calculations for super swelling of wood and pulps show that laminar separations may become sufficiently great to be microscopically visible. The calculations show that bound water fiber saturation points for wood normally fall in the range of 25 ... 40 percent. Super swollen wood, chemically isolated fibers and beaten fibers may as a result of reduced restraints have fiber saturation points greater than 150 percent. The latter are attributed to dispersion or diffusion forces rather than the conventional bound water forces of hydrogen bonding for intact wood.

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Zusammenfassung Die bekannten Bedingungen für die Sorption und Quellung von Holz werden erörtert. Sie sind auf Nadelholz unter Anwendung des folgenden, vereinfachten Modells anwendbar. Die Fasern sind durchgehend und haben rechteckigen oder kreisförmigen Querschnitt, mit Zellhohlräumen gleicher Form und konstanter Größe. Die Faserwände bestehen aus konzentrisch angeordneten Schichten, die wiederum aus kleinen, sich wiederholenden 100 ×100 großen Einheiten zusammengesetzt sind; diese wiederum bestehen aus einem mikrokristallinen Kern, umgeben von einer amorphen Auflagerung. Alle Sorptions- und Quellungsvorgänge finden an der Oberfläche oder innerhalb dieser amorphen Auflagerung statt; sie spielen sich in der Hauptsache in der Schicht selbst ab (inter-laminar), jedoch findet genügend Zwischenschicht-Sorption und-Quellung (intra-laminar) statt, um Verformungen der Schichten zu vermeiden. Durch Berechnung erhält man die allgemein anerkannte Größe der inneren Sorptionsfläche für Wasser von etwa 200 m²/g. Der Anteil der intra-laminaren Sorption an der Gesamtsorption schwankt zwischen 5 und 20% bei Holz mit Rohdichten von 0.3 bis 1.0. Die Schichtdicke der sorbierten Wassermoleküle je Sorptionsstelle liegt für inter-laminare Sorption zwischen 6.1 und 4.9, und für intra-laminare Sorption zwischen 0.35 und 1.35 bei Holz mit Rohdichten zwischen 0.3 bis 1.0. Ähnliche Werte ergaben sich aus experimentell ermittelten Quellungsdaten bei Zellhohlräumen mit sich änderndem Querschnitt. Vergleichbare Berechnungen der Super-Quellung des Holzes und des Zellstoffes zeigen, daß laminare Abtrennungen so groß werden können, daß sie mikroskopisch sichtbar werden. Sie zeigen ferner, daß die Fasersättigungspunkte bei gebundenem Wasser meist zwischen 25 und 40% liegen. Extrem gequollenes Holz, chemisch herausgelöste und gemahlene Fasern können aufgrund verringerter Behinderung Fasersättigungspunkte über 150% erreichen. Diese letztere Erscheinung ist eher den Dispersions- oder Diffusionskräften zuzuschreiben als den Kräften aus Wasserstoffbrücken des gebundenen Wassers im intakten Holz.

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Paper No. 2743 of the Journal Series of the N. C. State University Agricultural Experiment Station, Raleigh, North Carolina.

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Anselme Payen award paper of the Cellulose, Wood and Fiber Div., Am. Chem. Soc. presented at their 156th National Meeting in Atlantic City, New Jersey, September, 1968.     

Study of crystalline behavior of heat-treated wood cellulose during treatments in water

The crystalline behavior of heat-treated wood cellulose treated at 85% relative humidity (RH), in water, or boiled in water after heat treatment was investigated. The normal increased crystallinity was significantly depressed for samples that were oven-dried and then treated in 85% RH or in water. In the case of boiling-water treatment, a more pronounced increased in crystallinity was initially observed, which then decreased gradually. The crystallinity decreased more than untreated wood for samples that were heat treated for long periods and was slightly higher than the decreased crystallinity from the beginning of the above two treatments. On the other hand, no significant change in crystallinity was observed for samples of increased crystallinity or decreased crystallinity that were treated under high-moisture conditions, for all three treatments. The results show that the crystalline state of wood cellulose heat treated under oven dry or high-moisture conditions behave differently if treated in water after heat treatment. Results suggested that the mechanism of crystallization might be different for samples that are subjected to heat treatment under oven-dry and high-moisture conditions.     

脲醛树脂胶粘剂添加剂不同配比研究*

为降低生产成本、开发新型木材胶粘剂添加剂,选用羧甲基纤维素钠和细沙为主要原料,面粉为辅料,并研究其成分配比对胶粘剂人造板产品质量及加工成本的影响。结果表明：当添加剂中羧甲基纤维素钠、面粉、细沙质量百分比为3∶30∶67时,成本比传统添加剂降低了33%,面粉使用量减少了70%。     

The thermoosmotic effect in wood

Summary Water vapor pressures computed from stationary state data for moist wood (Choong 1963) are used to infer changes in the logarithm of vapor pressure per unit change in Kelvin temperature, d ln p/dT, for comparison with corresponding values from a thermodynamic model. The model evaluates the overall heat of transfer associated with passage of vapor through wood, and hence quantifies the thermoosmotic effect. Results of the comparison verify the existence of a constant vapor entropy for wood in the stationary state.     

Preliminary study of viscoelastic properties of MAPP-modified wood flour/polypropylene composites

Viscoelastic properties of maleated polypropylene (MAPP)-modified wood flour/polypropylene composites (WPC) were investigated by both a compression stress relaxation method and dynamic mechanical analyses (DMA). Three wood to polymer ratios (40:60, 60:40, and 80:20) and five MAPP loading levels (0, 1, 2, 4 and 8%) were used to study their effects on the viscoelastic properties of MAPP-WPC. The results show that: 1) higher wood to polymer ratio corresponds to higher stress relaxation levels for unmodified WPC. The modification with MAPP has an obvious effect on the stress relaxation of MAPP-WPC at higher wood to polymer ratios (60:40 and 80:20), but almost no effect at the 40:60 wood to polymer ratio. The optimal MAPP loading level for the wood to polymer ratio of 60:40 appears at 1%; 2) the storage modulus reaches its maximum at a MAPP loading level of 1% for wood to polymer ratios of 40:60 and 60:40, while for the 80:20 wood to polymer ratio, a higher storage modulus is observed at higher MAPP loading levels, which is quite consistent with the stress relaxation results. The results suggested that a suitable loading level of MAPP has a positive effect on the viscoelastic properties of WPC at higher wood to polymer ratios. Excessive MAPP loading would have resulted in adverse effects.     

Synergistic effect of melamine polyphosphate and aluminum hypophosphite on mechanical properties and flame retardancy of HDPE/wood flour composites

In this paper, the influence of melamine polyphosphate (MPP) and aluminum hypophosphite (AHP) on mechanical properties, flame retardancy and thermal degradation of high-density polyethylene/wood flour composites (HDPE/WF) was investigated. The synergistic effect of MPP and AHP was investigated. Polyethylene grafted with maleic anhydride (PE-g-MAH) was used as coupling agent. The experimental data demonstrated that the HDPE/WF composites with 35 wt% MPP/AHP (3:2) could achieve a LOI value of 29.6 % and UL-94 V-0 rating. In addition, the cone value also revealed that the heat release rate and the smoke production rate were clearly reduced. SEM results showed that the synergistic system (MPP/AHP = 3:2) could form a dense and thick char layer and good adhesion between wood flour and HDPE matrix, which prevented the transfer of heat flux and fuel gases. Incorporation of MPP and AHP improved the thermal stability of HDPE/wood flour as observed from the thermogravimetric analysis results and also enhanced the thermal resistance of char layer at high temperature based on scanning electron microscopy observation.