Distribution of chemical components in the walls of kraft and bisulphite pulp fibres

Summary Fines removed from the surfaces of Pinus radiata fibres by beating were identified and characterised in terms of microfibril orientations in the surfaces of beaten fibres. Fines fractions subjected to chemical analyses were selected so that chemical component data could be related to specific layers or lamellae in fibre walls.Carbohydrate distributions within the walls of kraft fibres differed from those in bisulphite fibres. In the kraft fibres, glucomannan increased and other hemicelluloses decreased from the primary wall to the outer lamellae of the S₂ layer of the secondary wall. In the bisulphite fibres, hemicelluloses were uniformly distributed throughout the outer wall layers, i. e., the primary wall and the S₁ and outer lamellae of the S₂ layers of the secondary wall. More galactan but less arabinan, xylan, and glucomannan were found in the outer layers than in the inner layers of the bisulphite fibres. Carbohydrate distributions were determined for a range of bisulphite pulp yields (53 to 80 percent).The outer layers of the bisulphite fibres contained more Klason lignin than the inner layers. Acid-soluble lignin contents were similar in the inner and outer layers.Helpful discussions with Dr. V. D. Harwood are gratefully acknowledged.     

Chemical modification and wetting of medium density fibreboard panels produced from fibres treated with maleated polypropylene wax

Medium density fibreboard (MDF) was produced from fibres treated with maleated polypropylene wax. The objectives of this study were to investigate the effect of fibre treatment with maleated polypropylene wax on the advancing and receding contact angle and wicking of MDF panels by the Wilhelmy plate method; to verify the chemical reactions occurring between fibres and maleated polypropylene wax by infrared spectroscopy, and to verify if there are relationships with the water absorption of panels. Three maleated polypropylene wax contents (0, 3, 5%) and two resin types (urea–formaldehyde, UF and melamine–urea–formaldehyde, MUF) were considered in this study. Our results showed that the treatment increased the advancing contact angle of panels bonded with UF resin. The receding contact angles of MDF panels produced from treated fibres with 5% maleated polypropylene wax content were also increased by the treatment. Also, the wicking was reduced by the treatment independent of the maleated polypropylene wax content. Reductions of the wicking were 59% for panels bonded with UF resin and 73% for panels bonded with MUF. Relationships between the wicking and water absorption were observed. Chemical analysis realized by infrared spectroscopy did not detect the presence of an esterification reaction between wood fibres and anhydride groups of the maleated polypropylene wax. This suggests, therefore, that an esterification reaction did not take place or that chemical modifications were so small that they are not visible by infrared spectroscopy.     

Determination of the cellulose and lignin content on wood fibre surfaces of eucalypts as a function of genotype and site

We compared the chemical composition of wood fibres and fibre surfaces of several eucalypt species and hybrids originating from various growth sites in South Africa. The objective was to test for differences in chemical surface composition due to genetics or site with the ultimate aim to facilitate a tailor-made supply of wood for pulping that results in an optimal blend of fibres that can be pulped together with similar yields. This, however, requires a sound knowledge of the fibre properties. The surface functionality on the single fibre level is a key property, because it determines how good inter-fibre bonding will be when paper is formed, which depends amongst other fibre properties on the amount of free hydroxyl groups that are available and therefore on the cellulose content on the fibre surface. The cellulose and lignin content on the fibre surface were determined with chemical force microscopy, a variation of atomic force microscopy. Since the general bulk composition of the fibre and the surface composition might differ, both parameters were determined. We found significant differences in the cellulose and lignin content on fibre surfaces, with regard to genotype and site, respectively. In some, but not all, cases, the surface composition of wood fibres followed the bulk composition, and differences were generally more pronounced. Differences due to genotype were significant, especially with regard to the surface lignin content—but variation due to site was also distinctly recognisable. This variation in surface functionality could be the reason why some pulpwood blends result in a lower pulp yield and different quality.     

Behavioural analysis of a nonionic detergent in the kraft pulp washing process using cryo-time-of-flight secondary ion mass spectrometry and cryo-scanning electron microscopy

In order to understand the kraft pulp decolouring mechanism on using a nonionic detergent, the pulp washing process and the resulting pulp handsheets were investigated by examining the brightness, kappa number, thioacidolysis product yield, and dewatering efficiency in the pressing sheet making process. The pulp decolouring could be attributed to a decrease in the lignin content and an improvement in the dewatering efficiency. Furthermore, the detergent distribution in the aqueous pulp suspension obtained during the pulp washing process was visualised using cryo-time-of-flight secondary ion mass spectrometry/scanning electron microscopy (cryo-TOF-SIMS/SEM). The detergent was clearly observed at the transverse surface of the pulp fibre cell wall and was also detected in the lumen of the fibres, suggesting the permeation of the detergent into the pulp fibre cell wall. Based on these results, the pulp decolouring mechanism can be proposed as follows: the detergent permeates into the pulp fibre cell wall and promotes the solution-exchange between the inside and the outside parts of the fibre cell wall, finally washing away the chromophoric substances such as lignin and its degradation products owing to the enhanced dewatering efficiency.     

Variability in fibre and parenchyma cell walls of temperate and tropical bamboo culms of different ages

This study tries to clarify the conflicting results from previous studies on cell wall thickening in bamboo culms by applying light and transmission electron microscopy in combination with image analysis. It focused on both fibre and parenchyma wall thickness of both temperate (Phyllostachys spp.) and tropical (Gigantochloa levis and Dendrocalamus asper) bamboo species of different ages in the light of their suitability for the wood industry. The observations indicated a great heterogeneity in cell wall thickness and cell wall layering pattern of fibres within one culm. Nested design ANOVA’s revealed a rising trend in wall thickness of late maturing fibres and parenchyma cells during the first year but significant wall thickening during later years could not be demonstrated. The high variability within one culm and between culms of the same age from 1 year on is partly masking a clear increased cell wall thickening at higher age. Nevertheless, the highest mean values for fibre wall thickness were recorded in culms of 44 months old or older, suggesting that some kind of late cell wall maturing can take place within one culm.     

Structural variability of vascular bundles and cell wall in rattan stem

Summary Anatomical investigations on six species ofCalamus demonstrate that fibre wall thickness and fibre percentage within the vascular bundles vary more than the vascular bundle size and number per unit area. Both fibre wall thickness and fibre percentage decrease consistently from the basal (order) to the top (younger) internodes of the stem and from the periphery to the centre at a given internode. The increase of wall thickness with age is more pronounced in fibres than in cortical and ground parenchyma. The thickening of the fibre wall with increasing stem density results from the deposition of additional lamellae. This appears to impart stiffness and determines the breaking behaviour of rattan both within the stem and among the species. The fracture mode of the fibres depends on the fibrillar orientation, which differs between broad and narrow lamellae.The first author is grateful to the Director Kerala Forest Research Institute (KFRI) for approving the collaborative research programme with the Institut für Holzbiologie und Holzschutz der Bundesforschungsanstalt für Forst und Holzwirtschaft. He is also indebted to the International Development Research Centre, Canada, for sponsoring the visiting programme under the project: Rattan (India) 3-P-86-0236: KFRI/109/1987. Thanks are due to Mrs. G. Weiner for her cooperation and Mr. P.K. Thulasidas (KFRI) for technical assistance in field collection     

Preparation and characterization of electroless nickel-coated cellulose fibres

The aim of this project was to fabricate electroless nickel-coated cellulose fibres. Ultimately, these nickel-coated cellulose fibres will be used to develop a cost-effective polymer composite for electromagnetic interference (EMI) shielding and/or electrostatic discharge (ESD) applications. An attempt has been made to impart electrical conductivity onto cellulose fibres via an electroless nickel plating process. The aim was to achieve a homogeneous, continuous layer of Ni on the cellulose fibres, and the plating conditions were optimized to achieve this. The relationship between the coating morphology and the performance of the coated fibre was also of interest. Testing was carried out using cellulose filter paper and then loose cellulose fibres. Scanning electron microscopic (SEM) images of nickel-coated filter paper showed that nickel particles are bonded to the cellulose fibres. The coating appeared more compacted and continuous as plating time increased, corresponding to lower surface resistivity. This observation suggested a correlation between morphology and electrical conductivity of the coating. For nickel-coated cellulose fibres, after optimization of plating conditions, a uniform deposition of nickel particles around the cellulose surfaces was confirmed by SEM images. EDS and XRD results confirmed similar coating could be produced on filter paper and cellulose fibres. SEM images of cross-sectioned nickel-coated cellulose fibres illustrated nickel particles had penetrated into the inner walls of the cellulose fibres. This impregnation of the fibres should act to increase the bonding between nickel coating and cellulose fibres. These nickel-impregnated cellulose fibres could now be incorporated into a polymer matrix to create an electrically conducting composite with the right processing parameters.     

Theory of X-ray measurement of microfibril angle in wood

Summary A diffraction intensity function for material bodies composed of arrays of crystalline fibres such as occurs with the cellulose of wood has been derived. It is implied in the analysis that the crystalline fibres making up the body have fibre symmetry- that there is a tendency for groups of fibres to have one set of crystal axes parallel while in the orthogonal direction the axes assume a low degree of order. It is further assumed that the patterns of the angular arrangement of the fibre groups relative to one axis of the body is independent of the direction about that axis. These conditions are believed to be compatible with the cellulosic structure found in wood. Thus it becomes possible to calculate the expected diffraction intensity profiles of realistic (and therefore complex) models of wood. This has aided the interpretation of the reflections from the (040) crystal planes of cellulose which are contaminated by low level reflections from other crystal planes, and it has been found that it might be possible by conjoint analysis of the paratropic (002) reflections and the diatropic (040) reflections to measure the complete cell wall planar microfibril angle distribution and the shape of the cell wall cross-section.This work is supported by the New Zealand Foundation for Research Science and Technology under contract # UOC 401     

Deformation of wet wood under combined shear and compression

During refining of mechanical pulp, a process occurring at high speed at temperatures of 140–160°C, the flexibility and bonding ability of wood fibres are increased. To understand the mechanical behaviour of the fibres in this operation, deformations at low speed of wet wood specimens at 50°C were studied under two different combinations of shear and compression loadings. The results were compared with the behaviour of wet wood in pure compression. Some features of the deformation that occurred in earlywood were analysed using an image analysis procedure. During pure compression the cell walls bend independently of the shape of the fibre cells and their cell wall thickness. Under combined shear and compression, however, mainly the corners of the fibre cells get deformed. In a second deformation performed in compression, the fibre cells follow the same deformation pattern as given by the first deformation type whether in compression or in combined shear and compression. The interpretation was that permanent defects in the cells themselves were introduced already in the first load cycle of the wood samples. The load combination with lower shear gave the same permanent strain as the case of pure compression but using less energy.     

Water sorption,surface structure and surface energy characteristics of wood composite fibres refined at different pressures

During fibre processing, wood fibres are subjected to a range of physical and chemical conditions sufficient to slightly alter their chemical composition and hence their ultimate performance when used in the manufacture of wood fibre-based composites. In order to better understand the effects of refiner conditions on material performance, wood fibres were subjected to processing at different refiner pressures (4, 6, 8 and 10 bar) and subsequently dried in a flash drier. The fibres were analysed for changes in surface area, surface energy, surface structure and water vapour sorption characteristics. The methods applied were nitrogen adsorption utilising the Brunauer–Emmett–Teller theory, inverse gas chromatography, scanning electron microscopy and dynamic vapour sorption. It was found that increasing refiner pressure resulted in fibres of lower surface area, accompanied by increasing dispersive surface energies up to operating refiner pressures of 8 bar. It was found with fibres refined at different pressures that as the refiner pressure increased the equilibrium moisture content of the fibre decreased at the set relative humidities. However, it was also noted that the hysteresis was not significantly different between each of the refiner pressures. The results suggest that different refiner pressures can be used to tune the surface characteristics which may be beneficial to product development and the improvement of the environmental profile of the wood fibre composites.     

Effects of pulp freezing and frozen pulp storage on fibre characteristics

Summary A requirement of long-term research on pulp fibres in that the material for study be stored for prolonged periods without deterioration and without changes in properties. In this paper effects of pulp freezing and thawing and of frozen pulp storage on fibre, wet web, and handsheet properties are discussed. A variety of radiata pine kraft pulps, a radiata pine sodium bisulphite pulp, and silver beech and hard beech (Nothofagus species) kraft pulps are examined.The expanded walls and diameters of beaten fibres were contracted by pulp freezing. This behaviour made fibres less flexible and less able to collapse during papermaking operations. The freezing treatment also caused fibre kinks and other fibre configurations which existed in a pulp before freezing to be fixed into position and made somewhat resistant to straightening when in strained wet webs. It was found that extents of fibre kink can be varied depending on the degree to which fibre configurations are forced into a pulp network before freezing. Increasing periods of frozen storage caused the intensity and distribution of bonds redeveloped by the freezing treatment to be progressively modified. Fibre walls were, however, not contracted further by increasing periods of frozen storage.The technical assistance of Miss D. Brookes is gratefully acknowledged     

三肽纤维素酯的制备及应用研究

以微晶纤维素为原料,芴甲氧羰基-L-脯氨酸(FMOC-L-Pro-OH)、芴甲氧羰基-L-缬氨酰-L-苯丙氨酸(FMOC-L-Val-L-Phe-OH)和3,5-二硝基苯甲酸为衍生化试剂,经酰氯化、酯化、肽链的延长和氨基的修饰等反应,合成了末端氨基被修饰的三肽纤维素酯(TPC)。通过实验证实三肽若要与纤维素成酯,必须采用先酯化后肽链延长的方式,其中关键步骤为酯化反应,其反应条件为:纤维素在LiCl/DMAc溶液中的质量浓度为20 g/L,温度100℃,n(酰氯)∶n(纤维素中羟基总量)为3∶1,反应时间20 h。再通过肽链延长、氨基修饰反应,最终可得到取代度为2.15的三肽纤维素酯。经过FT-IR、TG、XRD和元素分析等多种分析手段测试可知,3,5-二硝基苯甲酸对肽链末端进行了成功的修饰,该反应路径可行。酯化反应的产物根据沉淀析出液不同,内部氢键产生也不相同,可得到功能不同的三肽纤维素酯。TPC的应用实验结果表明,以甲醇为沉淀析出液的纤维素酯,是良好的肠溶包衣材料,具有遮光性强崩解迅速的特点,但其生理毒性有待进一步研究;以水为沉淀析出液的纤维素酯,被制成手性涂敷柱后,综合了刷型固定相与纤维素固定相的两大优势,拆分能力强大高效,耐化学性极佳,适用范围比以往涂敷柱更广泛,尤其适用于四氢呋喃流动相体系。     

On the fine structure of bamboo fibres

Summary The thick-walled bamboo fibres exhibit a polylamellate structure with alternating broad and narrow lamellae. Characteristically the cellulose fibrils in the broad lamellae are oriented almost parallel to the longitudinal axis of the fibre (2–20°), whereby there is a gradual but only slight increase in the angle from middle lamella to lumen. The narrow lamellae consist of fibrils oriented almost perpendicular to the cell axis (85–90°); this angle remains constant in all the successive narrow lamellae. The concentration of lignin is higher in the narrow lamellae than in the broad ones. Xylan seems to occur in a higher concentration in the narrow lamellae. The pits between the fibres are bordered. The results are discussed in relation to earlier data on wall structure and development. A model for the thick-walled bamboo fibre is presented with a new terminology for the various lamellae.We are thankful to Mrs. R. Schultze and Miss B. Schröder for their technical assistance. Grateful acknowledgement is also due to Dr. D. Keyser and Mrs. K. Hoffmann for the SEM facilities and to Prof. Dr. J. Bauch and Mrs. R. Endeward for the UV-microspectrophotometry. Prof. T. E. Timell (Syracuse) and Dr. O. Faix were helpful with the preparation of hydrofluoric acid concentrations.     

Mechanical properties of flax fibres treated by alkaline,enzyme and steam-heat

In recent years there has been interest in using flax fibres to produce composites because of a number of attributes, including low density, biodegradability and high mechanical properties. It was found that treatment of flax fibres may be required to improve the bond quality with a resin. These treatments also have an impact on the properties of the fibres themselves. The objective of this project was to evaluate the impact of three treatment methods on the mechanical properties of flax fibres. The three treatment methods were alkaline, enzyme and steam-heat. After treatment, flax fibres were tested in tension using a universal test machine. Results showed that tensile strength and Young's modulus of flax fibre can be enhanced significantly by the three treatment methods, compared with untreated flax fibres. Enzyme treatment was shown to be the best approach to improve mechanical properties of flax fibre than alkaline and steam-heat treatment.     

Adhesive/fibre interaction in medium density fibreboard

Summary Qualitative and quantitative Jamin-Lebedeff interference microscopy was used in combination with embedding and thin sectioning to study the interaction between phenol-formaldehyde or urea-formaldehyde resins, and the fibre surface of medium density fibreboard from a wide range of commercial sources. Interference microscopy was used to measure the refractive indices of both resins to enable positive identification of resin within the board. Contact angle between resin and fibre surface was measured to provide an estimate of the degree of wetting of the fibre. Phenol-formaldehyde resin showed significantly lower contact angles and therefore better fibre wetting when compared with urea-formaldehyde. Phenol-formaldehyde tended to form a thin layer on the fibre surface while urea-formaldehyde tended to form large compressed droplets or patches of resin between the fibres. It is suggested that by improving the wetting properties of urea-formaldehyde resin, significant improvements in internal bond strength may be achieved.The authors gratefully acknowledge the assistance of Fletcher Wood Panels (NZ) Ltd, Canterbury Timber Products (NZ) Ltd and ICI (NZ) Ltd in providing materials and financial support. The authors acknowledge the assistance of Dr J. M. Uprichard, Dr R. Franich, Mr J. McLaughlan (FRI) and Dr R. Naylor (A. C. Hatrick (NZ) Ltd) in the preparation of this report     

Effect of silvicultural practices on fibre properties of Eucalyptus wood from short-rotation plantations

The effect of nitrogen addition and weed management on fibre properties of wood from 6.5-year-old Eucalyptus grandis and E. tereticornis from intensively managed short-rotation plantations were investigated. Trees for analyses were sampled from plots with zero nitrogen input (n = 4), plots with high level (187 kg N ha^?1) nitrogen input (n = 4), plots from which weed growth was not removed throughout the rotation (n = 4) and plots from which weeds were removed periodically (n = 4). Fibre characteristics were evaluated on wood samples collected from base, breast height, 50, 75 and 100 % of merchantable bole height of trees. Though N input and weed management improved tree growth significantly irrespective of species, the treatment effects did not cause any significant change in fibre characteristics such as fibre length, fibre diameter, lumen width and wall thickness. Longest and widest fibres were observed at the outer most radial portion of wood in all cases. In general, within tree fibre length varied significantly along the radial direction of wood. Fibre diameter, lumen width and wall thickness lacked any specific pattern between species and treatments. Runkel ratio and felting and flexibility coefficients values showed high pulping quality of wood irrespective of species and treatments. The study concluded that the fibre properties that influence pulpwood quality of Eucalyptus have not been affected by silvicultural practices, like fertilizer input and weed management, aimed at improving productivity of short-rotation eucalypt plantations.     

The fracture behaviour of single wood fibres is governed by geometrical constraints: in situ ESEM studies on three fibre types

In situ tensile tests were performed in an environmental scanning electron microscope (ESEM) on earlywood, transition wood and latewood cells of Norway spruce (Picea abies [L.] Karst.). In order to examine the single wood fibres in a wet state, a specially designed tensile testing stage with a cooling device was built. The fracture behaviour of the cell types was studied at high resolution while straining. Different failure mechanisms were observed for the three tissue types. The thin-walled earlywood fibres showed tension buckling which gave rise to crack initiation and resulted in low tensile strength, whereas thick-walled latewood fibres predominately failed by transverse crack propagation without fibre folding.     

TEM/FE-SEM studies on tension wood fibres of Acer spp., Fagus sylvatica L. and Quercus robur L.

Tension wood (TW) fibres from maple, beech and oak were analysed with special emphasis on the cell wall fine structure and deposition of aromatic compounds within the gelatinous layer (GL). For this purpose, transmission electron microscopy (TEM) was applied after section staining with potassium permanganate. There was evidence for the occurrence of aromatic compounds in the GLs of fibres of all three species. Some GLs showed a concentric sub-layering. Hence, conclusions about the biosynthetic activities during cell wall formation in TW could be derived. Additional information about structural characteristics of TW fibres were obtained by means of field emission electron microscopy. High-resolution micrographs of cell walls were used for measurements of diameter and microfibril angle (MFA) of cellulose aggregates (CAG). CAG of 7 nm were observed although their diameter varied greatly in the GLs. MFA in the secondary wall of TW was slightly smaller than in opposite wood. The microscopic methods provided complementary ultrastructural and topochemical information on tension wood fibres. The subcellular localisation of aromatic compounds and the observations of the ultrastructural morphology will contribute to the understanding of origin and functionality of TW and its characteristic GL.     

Ultrastructural features affecting mechanical properties of wood fibres

The purpose of this review is to re-examine some of the existing knowledge on the ultrastructure of softwood fibres and modelling of the hygroelastic properties of these fibres. The motivation is that the ultrastructure of wood fibres has a strong influence on fibre properties such as stiffness and hygroexpansion. This structure-property relationship can be modelled with, for instance, composite mechanics to assess the influence of ultrastructure on the fibre properties that in turn control the engineering properties of wood fibre composites and other wood-based materials. Comprehensive information about the ultrastructure is presented that can be useful in modelling the hygroelastic behaviour of wood fibres. Many attempts to model ultrastructure-property relationships that have been carried out over the years are reviewed. Even though models suffer from limiting approximations at some level, they have been useful in revealing valuable insights that can help to clarify experimentally determined behaviour of wood fibres. Still, many modelling approaches in the literature are of limited applicability, not the least when it comes to geometry of the fibre structure. Therefore, an example of finite element modelling of geometrically well-characterized fibres is given. This approach is shown to be useful to asses the influence of the commonly neglected irregular shape on elastic behaviour and stress state in wood fibres. Comparison is also made with an analytical model which assumes cylindrical fibre shape. Predictions of the elastic properties made with analytical modelling of cylindrical fibres and with finite element modelling of geometrically characterized fibres are in concert, but the stress state and failure predictions only show qualitative similarity. It can be concluded that calculations on fibres with the irregular and more realistic geometry combined with experiments on single fibres are necessary for a better and more quantitative understanding of the hygroelastic behaviour and particularly failure of wood fibres. It is hoped that this paper can provide a foundation and an inspiration for modelling, in combination with experiments and microscopy, for better predictions of the mechanical behaviour of wood fibres and wood fibre composites.     

Ultrastructural features affecting mechanical properties of wood fibres

Abstract

The purpose of this review is to re-examine some of the existing knowledge on the ultrastructure of softwood fibres and modelling of the hygroelastic properties of these fibres. The motivation is that the ultrastructure of wood fibres has a strong influence on fibre properties such as stiffness and hygroexpansion. This structure–property relationship can be modelled with, for instance, composite mechanics to assess the influence of ultrastructure on the fibre properties that in turn control the engineering properties of wood fibre composites and other wood-based materials. Comprehensive information about the ultrastructure is presented that can be useful in modelling the hygroelastic behaviour of wood fibres. Many attempts to model ultrastructure–property relationships that have been carried out over the years are reviewed. Even though models suffer from limiting approximations at some level, they have been useful in revealing valuable insights that can help to clarify experimentally determined behaviour of wood fibres. Still, many modelling approaches in the literature are of limited applicability, not the least when it comes to geometry of the fibre structure. Therefore, an example of finite element modelling of geometrically well-characterized fibres is given. This approach is shown to be useful to asses the influence of the commonly neglected irregular shape on elastic behaviour and stress state in wood fibres. Comparison is also made with an analytical model which assumes cylindrical fibre shape. Predictions of the elastic properties made with analytical modelling of cylindrical fibres and with finite element modelling of geometrically characterized fibres are in concert, but the stress state and failure predictions only show qualitative similarity. It can be concluded that calculations on fibres with the irregular and more realistic geometry combined with experiments on single fibres are necessary for a better and more quantitative understanding of the hygroelastic behaviour and particularly failure of wood fibres. It is hoped that this paper can provide a foundation and an inspiration for modelling, in combination with experiments and microscopy, for better predictions of the mechanical behaviour of wood fibres and wood fibre composites.