Some microrheological aspects of wood-pulp fibres subjected to fatigue loading

Wood-pulp fibres are recognized as concentrically-layered, laminated composite tubes of structural reinforcing material, the cellulose microfibrils, embedded in a cementing matrix of hemicellulose and lignin. When the single fibres are subjected to cyclic mechanical action, their morphological behaviour is characterized by the fatigue growth of micro-voids and surface damage which individually and collectively give rise to stress concentrations, and eventually crack development. The progressive damage phenomena, evinced by the surface imaging and optical sectioning techniques through utilizing confocal laser scanning microscopy, are understood to be consequences of the cumulative material micromechanical degradation and subsequent microstructural breakdown of the cellulose microfibrillar framework. This structural breakdown is believed to effect the fibrillation and flexibilization of the fibres This revised version was published online in August 2006 with corrections to the Cover Date.     

Defibration mechanisms of autohydrolyzed Eucalyptus wood chips

The objective of this study was to evaluate the influence of autohydrolysis on mechanical defibration of Eucalyptus wood chips. The autohydrolysis process changed notably the mechanical properties of Eucalyptus chips. The removal of mainly hemicelluloses undoubtedly decreased the overall pulp yield. Hemicellulose losses cannot be solely accounted for the changes in the wood and pulp properties, because the autohydrolysis also caused changes in lignin. When comparing the mechanical pulp fibers of the original wood chips with the fibers resulting from the autohydrolyzed wood material, it was clear that the rupture point shifted from the secondary wall to the middle lamella, confirmed by X-ray photoelectron spectroscopy measurements. This study revealed the mechanical behavior of autohydrolyzed wood chips and can provide useful information for integration of mechanical pulp mills into the biorefinery concept in the future.     

Relationship between the decrease of degree of polymerisation of cellulose and the loss of groundwood pulp paper mechanical properties during accelerated ageing

During natural ageing, paper undergoes colour changes and becomes brittle. It is mainly due to the degradation of cellulose, the main component of paper fibres. From the viewpoint of conservation/protection of paper-based information carriers, as well as of the utilisation of secondary fibres, knowledge of the impact of a decrease of the degree of polymerisation (DP) of cellulose on mechanical properties of paper becomes of key importance. In this paper, correlations between the decrease of DP of cellulose and the loss of paper folding endurance (FE) using three model samples (pure cellulose, groundwood pulp paper, and degraded groundwood pulp paper) at accelerated ageing were investigated. The existence of such correlations between DP and FE is supported by experimental results; the correlations are linear for pure cellulose and groundwood pulp paper ageing, while exponential correlation was observed in case of degraded groundwood pulp paper. The results indicate that the rate of paper degradation can be evaluated by means of the rate of glycosidic bonds breaking in cellulosic polymer chains both for cellulose and groundwood pulp paper.     

Characteristics of kenaf fibre/epoxy composites subjected to thermal degradation

Kenaf fibres are receiving much attention in the natural fibre composite industry due to its potential as polymer reinforcements. However, like all natural fibres, kenaf fibres have lower thermal resistance as compared to synthetic fibres. In this current work, the characteristics of kenaf fibre/epoxy composites, both treated and untreated using alkalization process, exposed to high temperature were studied. Thermogravimetric analysis (TGA) was used to study the thermal decomposition behaviour of treated and untreated kenaf/epoxy composites as well as their components, kenaf fibre and neat epoxy from room temperature up to 600 °C. The weight loss and physical changes of these samples were observed through furnace pyrolysis. Surface morphology of the composites after degradation was observed using scanning electron microscopy (SEM). The results from the TGA showed that the addition of kenaf fibres into the epoxy slightly improves both the charring and thermal stability of the samples. However, it was observed that alkalization causes reduction in these behaviours for the kenaf/epoxy composite. Generally, increased exposure time causes higher weight loss of the composites only up to 150 °C. At higher temperature, duration of exposure has little influence on the weight loss. Fibre-matrix debondings were observed on degraded samples implying mechanical degradation of the composites had occurred.     

Swelling of mechanical pulp fines

The objective of the study was to determine the swelling of different types of mechanical pulp fines. The physical and chemical characteristics of the fines were also examined. It was found that the degree of swelling correlates with the proportion of fibrillar material, that is fibrillar content of the fines. The fines with the lowest fibrillar content had a swelling comparable to mechanical pulp fibres (0.69g/g), whereas the fines with a high fibrillar content had a swelling comparable to neverdried kraft pulp fibres (1.41g/g). Hemicellulose content and charge could not explain the differences in swelling of different types of the mechanical pulp fines. While the lignin content appears to be an important factor in the degree of swelling of mechanical pulp fines, the results suggest that structural differences between the particles are also important. The bulk elastic modulus was determined by measuring the change in swelling for a known change in osmotic pressure. All the mechanical pulp fines had a high bulk elastic modulus compared to kraft fines. However, fibrillar fines had a lower bulk elastic modulus than flakelike fines. Mechanical pulp fines, both fibrillar and flakelike varieties, did not hornify appreciably. The swelling of both the fines and the fibre fractions increased slightly with the specific energy consumption in the refining.     

Volatile organic compounds in paper—an approach for identification of markers in aged books

Volatile organic compounds emitted from historical books made from cotton/linen rag and wood pulp paper have been studied. Different profiles were obtained using different solid-phase microextraction (SPME) fibres to access the compounds involved in the decomposition reactions occurring in cotton/linen rag and wood pulp paper upon natural ageing and precocious/accelerated degradation. Contact headspace solid-phase extraction coupled with gas chromatography/time-of-flight mass spectrometry (GC-TOF-MS) was improved as a non-destructive methodology for the analysis of historical books. Potential markers of cellulose degradation—linear hydrocarbons, linear aldehydes, and 2-furfural—together with potential markers of cotton/linen rag paper (isopropylic esters) were identified. Chiral analysis (SPME-c-GC-TOF-MS) showed that only the enantiomer (S)-2-ethyl-1-hexanol is present as an emanation compound in both types of paper. Validation studies for a larger number of books are being done.     

以制浆造纸产业为平台的生物炼制新模式

本文通过分析木质生物质炼制与制浆造纸工业之间的关系,提出以制浆造纸产业为平台的生物炼制模式。在蒸煮制浆前,增加对原料预抽提处理,提取半纤维素等成分用于生产乙醇燃料和（或）其他化工化学品,抽提残渣则采用传统化学法、高得率法或有机溶剂法制浆,实现植物纤维原料多组分分离综合利用。该模式给制浆造纸产业提供一条可持续发展的新思路。     

Monitoring the polymerization process of polypyrrole films by thermogravimetric and X-ray analysis

Bio-composite fibers were developed from wood pulp and polypropylene (PP) by an extrusion process. The thermo-physical and mechanical properties of wood pulp-PP composite fibers, neat PP and wood pulp were studied using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). The thermal stability of bio-composite fibers was found to be significantly higher than pure wood pulp. An understanding into the melting behaviour of the composite system was obtained which would assist in selecting a suitable temperature profile for the extruder during processing. The visco-elastic properties of bio-composite fibers were also revealed from the study. The generated bio-composite fibers were also characterized using Fourier transform infrared spectroscopy (FTIR) to understand the nature of chemical interaction between wood pulp reinforcement and PP matrix. The use of maleated polypropylene (MAPP) as a compatibilizer was investigated in relation to the fiber microstructure. Changes in absorption peaks were observed in FTIR spectra of bio-composite fibers as compared to the pure wood pulp which indicated possible chemical linkages between the fiber and polymer matrix.     

Changes in lignin and cellulose by irradiation

The effect of high-energy radiation on wood and cellulose was investigated. By irradiation of beech wood, changes in lignin, in carbohydrates and in wood structure take place. Furthermore, new lignin carbohydrate complexes are formed. A way is shown to prevent undesirable reactions. Irradiated pulp possesses a lower degree of polymerization and a higher accessibility for chemical reactions. Processing irradiated pulp to viscose fibres will be more efficient.     

Application of spectroscopic techniques for the study of paper documents: A survey

For many centuries paper was the main material for recording cultural achievements all over the world. Paper is mostly made from cellulose with small amounts of organic and inorganic additives, which allow its identification and characterization and may also contribute to its degradation. Prior to 1850, paper was made entirely from rags, using hemp, flax and cotton fibres. After this period, due to the enormous increase in demand, wood pulp began to be commonly used as raw material, resulting in rapid degradation of paper. Spectroscopic techniques represent one of the most powerful tools to investigate the constituents of paper documents in order to establish its identification and its state of degradation. This review describes the application of selected spectroscopic techniques used for paper characterization and conservation. The spectroscopic techniques that have been used and will be reviewed include: Fourier-Transform Infrared spectroscopy, Raman spectroscopy, Nuclear Magnetic Resonance spectroscopy, X-Ray spectroscopy, Laser-based Spectroscopy, Inductively Coupled Mass Spectroscopy, Laser ablation, Atomic Absorption Spectroscopy and X-Ray Photoelectron Spectroscopy.     

Reinforced absorbent material: a cellulosic composite of TEMPO-oxidized MFC and CTMP fibres

This research aims to develop new materials based on renewable resources that can fulfill the functions necessary in the absorption core of a disposable diaper. Absorbent foam was recently produced from softwood kraft pulp by TEMPO oxidation, disintegration and freeze drying. In this study, the TEMPO-oxidized MFC was mixed with pulp fibres, thus forming a cellulosic composite, in an attempt to improve the mechanical stability of the freeze-dried absorbent material. The fibres were added in different amounts and the freeze-dried materials were evaluated for their absorption and retention properties. The results of this study suggest that the composite material has a better mechanical stability than the absorbent foam without fibres. It was shown that using spruce CTMP fibres in the composite resulted in better absorption and retention capacities than in a composite with softwood kraft pulp fibres. The higher stiffness of the CTMP fibres is a probable explanation for this difference. For the composite material with CTMP fibres, liquid porosimetry showed that pore size distribution was more or less retained when put under load. Furthermore, it was seen that the retention properties reached a maximum around 85 % CTMP fibres and 15 % TEMPO-oxidized MFC. In the centrifuge retention test, the retention of the TEMPO-oxidized MFC in the composite material reached about the same capacity as conventional superabsorbent polymers.     

Fibre porosity development of dissolving pulp during mechanical and enzymatic processing

Dissolving grade pulps are used as raw material for manufacture of regenerated cellulose fibres and their use is constantly growing. Despite intensive research, there is still a need to develop cellulose dissolution-regeneration processes that would be economically viable, fulfil the pre-conditions of sustainability and would be able to meet the strict product quality requirements. The basis for creation of such a process is in deep understanding of the biomass structure and factors affecting the cellulose modification and dissolution. In this paper, the effects of the mechanical and enzymatic pre-treatments on the pore structure and alkaline solubility of dissolving grade pulp are discussed. Formation of micro- and macropores in the pulp fibres during mechanical shredding was found to correlate with the susceptibility of the fibres to enzymatic hydrolysis. The fibre porosity development during the processing was studied by a modified solute exclusion approach, which revealed differences between the effect of mild enzyme or acid hydrolysis on the pore structure of fibres. The dissolution of the modified fibres in NaOH/ZnO was evaluated and found to correlate with overall pore volume and accessible surface area analysed by the modified solute exclusion method.     

Dynamic-mechanical analysis of the photo-degradation of long glass fibre reinforced polypropylene: Mechanical properties' changes

Polypropylene matrix composites, with different degrees of reinforcement with long glass fibres, are employed in different fields of the industry, such as aeronautics or automotive. Samples of the material were exposed to artificial accelerated photo-ageing in UV chamber (Heraeus Xenotest 150S). Their high content of glass fibres causes a surface degradation that can seriously affect mechanical properties. Therefore, dynamic mechanical and tensile tests were carried out in order to compare the changes of the properties with exposure time. These modifications are accompanied with microscopic changes in the crystallinity as can be seen in the thermal analysis experiments.     

Effect of the combination of biobeating and NFC on the physico-mechanical properties of paper

The combined effect of enzymatic treatment (biobeating) and NFC addition on the mechanical and physical properties of a papermaking pulp suspension was investigated. The influence of pH, consistency of pulp and reaction time of the enzyme on the pulp strength was evaluated by measuring the breaking length of paper sheets made thereof. The results showed that the enzymatic treatment improved mechanical properties of fibres without modifying drainability. After biobeating, NFC was added to the enzyme-treated pulps. Mechanical properties were enhanced, obtaining length at break values similar to those observed in commercial printing/writing paper. Opacity remained constant, whereas porosity was gradually reduced as more amount of NFC was added. The presence of NFC also reduced drainability, although it remained at suitable levels for the papermaking industry. The results suggest that the combination of biobeating and NFC addition can be considered as an alternative to mechanical beating.     

Production of microfibrillated cellulose from unbleached kraft pulp of Kenaf and Scotch Pine and its effect on the properties of hardwood kraft: microfibrillated cellulose paper

This work investigated the effect of using Kenaf bast fibre kraft pulps compared to Scotch Pine kraft pulps for producing microfibrillated cellulose (MFC) and its employment for improving mechanical and physical properties of handsheets made from unbleached kraft hardwood pulp. It was shown that MFC based on Kenaf fibres can be produced at higher consistencies [>5 % (w/w)] compared to when Scotch Pine is employed [≈2 % (w/w)] as raw material. The possibility of using a higher consistency when processing Kenaf is beneficial for the processing in microfluidizers. The rheological properties of the products were shown to be consistent with what is known for MFC-based systems. The studies indicate that the mechanical properties of handsheets from unbleached kraft hardwood pulp can be improved by replacing part of the unbleached kraft hardwood pulp fibres with either unbleached kraft Kenaf pulp or unbleached Scotch Pine kraft pulp. However, the same levels of improvements were obtained when using only a small amount [≈6 % (w/w)] of MFC based on Kenaf or Scotch Pine, when introduced into the system either as a dry strength additive or by coating pre-made handsheets. Finally, it was shown that the incorporation of MFC in handsheets decreases the air-permeability; this effect became amplified when the MFC was applied as a coating onto the handsheets.     

Cellulose structural arrangement in relation to spectral changes in tensile loading FTIR

In order to utilise wood and wood fibres in advanced materials, a better understanding of the mechanical material characteristics and the interactions among the components is necessary. For this purpose, FTIR was explored together with mechanical loading as a means of studying the molecular responses to the loading of spruce wood and cellulose paper material. A linear shift of absorption bands was detected as the loading was applied. In relation to the applied stress these shifts were higher under moist conditions than under dry ones but they were similar with regard to the strains applied. There were no shifts detected in bands related to lignin or the hemicelluloses. The results are interpreted as reflecting a parallel arrangement of the load bearing component, the cellulose ordered structure, and the moisture accessible regions in the cellulose microfibril structure. This therefore represents an equal strain loaded system.     

Effect of thermal-treatment of wood fibres on properties of flat-pressed wood plastic composites

This study aimed to enhance the dimensional stability of flat-pressed wood plastic composites (WPCs) containing fast growing wood fibres by a thermal-treatment method. The wood fibres were treated at three different temperatures (120, 150, or 180 °C) for 20 or 40 min in a laboratory autoclave. The WPC panels were made from dry-blended Eucalyptus camaldulensis wood fibres and polypropylene (PP) powder (50:50 by weight) using a conventional flat-press process under laboratory conditions. Thickness swelling and water absorption of the WPC panels significantly decreased with increasing the treatment temperature and time. The thermal-treatment of eucalyptus wood fibres slightly decreased the screw withdrawal resistance of the WPC panels as compared to the reference panels while the flexural properties and internal bond strength were more seriously affected by the treatment. The present study revealed that the thermal-treatment of the wood fibres significantly improved the dimensional stability of the WPC panels.     

Nanofibrillated cellulose/nanographite composite films

Though research into nanofibrillated cellulose (NFC) has recently increased, few studies have considered co-utilising NFC and nanographite (NG) in composite films, and, it has, however been a challenge to use high-yield pulp fibres (mechanical pulps) to produce this nanofibrillar material. It is worth noting that there is a significant difference between chemical pulp fibres and high-yield pulp fibres, as the former is composed mainly of cellulose and has a yield of approximately 50 % while the latter is consist of cellulose, hemicellulose and lignin, and has a yield of approximately 90 %. NFC was produced by combining TEMPO (2,2,6,6-tetramethypiperidine-1-oxyl)-mediated oxidation with the mechanical shearing of chemi-thermomechanical pulp (CTMP) and sulphite pulp (SP); the NG was produced by mechanically exfoliating graphite. The different NaClO dosages in the TEMPO system differently oxidised the fibres, altering their fibrillation efficiency. NFC–NG films were produced by casting in a Petri dish. We examine the effect of NG on the sheet-resistance and mechanical properties of NFC films. Addition of 10 wt% NG to 90 wt% NFC of sample CC2 (5 mmol NaClO CTMP-NFC homogenised for 60 min) improved the sheet resistance, i.e. from that of an insulating pure NFC film to 180 Ω/sq. Further addition of 20 (CC3) and 25 wt% (CC4) of NG to 80 and 75 wt% respectively, lowered the sheet resistance to 17 and 9 Ω/sq, respectively. For the mechanical properties, we found that adding 10 wt% NG to 90 wt% NFC of sample HH2 (5 mmol NaClO SP-NFC homogenised for 60 min) improved the tensile index by 28 %, tensile stiffness index by 20 %, and peak load by 28 %. The film’s surface morphology was visualised using scanning electron microscopy, revealing the fibrillated structure of NFC and NG. This methodology yields NFC–NG films that are mechanically stable, bendable, and flexible.     

Influence of the wood fibre filler on the internal recycling of poly(vinyl chloride)-based composites

The recycling of internal waste of poly(vinyl chloride) (PVC) and wood fibre-reinforced PVC composite was investigated and compared. Twenty extrusion-milling cycles were performed and the mechanical and thermal properties evaluated. This comparison provided evidence of the influence of the vegetable fibres on the thermo-mechanical degradation of the composite material. Up to five cycles, the composite properties remained stable. But after 10 cycles and especially at 20 cycles, the flexural strength increased, whereas the other mechanical properties remained almost constant. At the same time, a decrease of the degradation temperature revealed a deterioration of the molecular structure. The PVC properties remained constant, whereas a great increase in the impact strength was observed after 20 cycles without deterioration of the molecular structure. The different behaviours between the composite and the PVC were explained by the influence of the fibres, which accelerated the PVC degradation, characterized by dehydrochlorination followed by crosslinking reactions.     

Surface treated cellulose fibres in flame retarded PP composites

Polypropylene-based composites were prepared containing non-treated and various treated cotton fibre and wood flakes. A correlation was observed among the fibre treatment and compounding parameters, mechanical and discoloration properties. The structural changes in fibres were demonstrated by Raman spectroscopic and DSC measurements. The possibility for forming cellulose fibre containing flame retardant composites was also investigated. The efficiency of various treatments on compounding, discoloration and mechanical properties enhance in the following order: no treatment < non ionic surfactant < reactive silicone segment containing non ionic surfactant < special silylation treatment. The best results obtained with the special silylation treatment were explained with the more organophilic character and by the thermal stability of the treated fibres. Cellulose fibre as a polyol-charring component and ammonium-polyphosphate together constitute a high performance intumescent flame retardant system in the PP matrix.