Determination of the adsorption character of cellulose fibres using surface tension and surface charge

The reactivity and adsorption properties of cellulose fibres are critical for successful treatment because behavior during the finishing process is determined by both structure and surface properties. The fine structure of natural cellulose fibres i.e. cotton, is different from the regular viscose, modal and new types of regenerated cellulose fibres i.e. lyocell, which are clarified by different hydrophilic/hydrophobic character of fibres and different adsorption properties. Tensiometry, seldom used in fibre characterization was used to obtain the differences in the adsorption properties of different cellulose fibres. The surface tension, contact angle and adsorption were measured, and then compared with various methods for determining water adsorption. Currently some additional methods especially sensitive to surface properties (electrokinetic properties of fibres) are being applied in order to characterize the adsorption character and reactivity of the fibre surfaces. The streaming potential was measured due to the fact that the interaction properties are strongly influenced by electric charges on the surface, and from these values the zeta potential (ζ) was calculated as a function of the pH and the surfactant concentration in the liquid phase. As with the results of fibre reactivity and adsorption properties obtained by conventional methods, the electrokinetic character of the materials and their adsorption ability determined using the tensiometry also show the same phenomena. The natural fibres have the smaller hydrophilic character and they are less reactive than the regenerated ones, so the ζ_max of cotton is the highest and the contact angle ϕ the greatest [1, 2, 3] Electronic Publication     

Mechanical properties of alkali treated plant fibres and their potential as reinforcement materials. I. hemp fibres

In this study a thorough analysis of physical and fine structure of hemp fibre bundles, namely surface topography, diameter, cellulose content and crystallinity index, have been presented. The fibre bundles have been alkalised and physical and mechanical properties analysed. Alkalisation was found to change the surface topography of fibre bundles and the diameter decreased with increased concentration of caustic soda. Cellulose content increase slightly at lower NaOH concentrations and decrease at higher NaOH concentrations. The crystallinity index decrease with increase in caustic soda concentration up to 0.24% NaOH beyond which, it decreases with increase in NaOH concentration. It was also found that the tensile strength and stiffness increases with increase in the concentration of NaOH up to a limit. Tensile strength and Young’s modulus increase with decrease in cellulose content, while crystalline cellulose decreases slightly but with improved crystalline packing order resulting in increased mechanical properties. Similar observations are elucidated by the crystallinity index. Alkalised hemp fibre bundles were found to exhibit a similar specific stiffness to steel, E-glass and Kevlar 29 fibres. The results also show that crystallinity index obtained following alkalisation has a reverse correlation to the mechanical properties. Stiffer alkalised hemp fibre bundles are suitable candidates as reinforcements to replace synthetic fibres. The improvement in mechanical properties of alkali treated hemp fibre bundles confirms their use as reinforcement materials.     

Influence of fibre-surface treatment on structural,thermal and mechanical properties of jute

Jute fibres, an environmentally and ecologically friendly product, were chemically modified by treatment with 1.26 M (5 wt%) solution of NaOH solution at room temperature for 2, 4 and 8 h. The above samples were characterized by small angle X-ray scattering (SAXS) technique and XRD for macromolecular and microstructural parameters of fibres before and after alkali treatment where as FT-IR and SEM was used for fine structural details and morphological studies of the fibres. Differential scanning calorimetry (DSC) and instron 1185 analyzed thermal and mechanical behaviour of the fibres. Comparison and analysis of results confirmed some changes in the macromolecular structure and microstructure of the fibres after chemical treatment due to swelling of macromolecules and removal of some non-crystalline constituents of the fibres. The findings conclude that change in crystallinity developed after alkali treatment resulting improvement in mechanical strength of the fibres. However, the removal of structural constituents after alkali treatment leads the thermal decomposition temperature of the cellulose went down to 360.62 °C after 8 h alkali treatment from 365.26 °C for raw jute fibre.     

Preparation, structure and mechanical properties of all-hemp cellulose biocomposites

All-hemp (Cannabis Sativa L.) cellulose composites were prepared by a mechanical blending technique followed by hot pressing and water–ethanol regeneration. The alkali treated fibres were ground and sieved to a size ranging from 45 μm to 500 μm. Introduction of fibres into 12% w/v cellulose N-methyl-morpholine-N-oxide (NMMO) solution was performed with low solution viscosity at 100 °C. The solid mixtures were cut and heat pressed between heated glass and PTFE plates at 85 °C to obtain a flat smooth-surfaced composite sheet of approximately 0.2 mm thickness. The cellulose was regenerated in a 50:50 water–ethanol mixture that subsequently removed NMMO and stabilizer (Irganox 1010, Ciba) from the composite. FTIR and X-ray diffraction measurements were performed to investigate the structural change of cellulose from fibre into partially regenerated composite. Composition and thermal stability of composites were investigated using thermogravimetry. A broadening of the scattering of the main crystalline plane (0 0 2) and a depression of the maximum degradation temperature of fibre were observed. The observations revealed a structural change in the fibres. The mechanical properties of composites depended on size, surface area, crystallinity and the structural swelling of fibres.     

Cell wall structure and formation of maturing fibres of moso bamboo (Phyllostachys pubescens) increase buckling resistance

The mechanical stability of the culms of monocotyledonous bamboos is highly attributed to the proper embedding of the stiff fibre caps of the vascular bundles into the soft parenchymatous matrix. Owing to lack of a vascular cambium, bamboos show no secondary thickening growth that impedes geometrical adaptations to mechanical loads and increases the necessity of structural optimization at the material level. Here, we investigate the fine structure and mechanical properties of fibres within a maturing vascular bundle of moso bamboo, Phyllostachys pubescens, with a high spatial resolution. The fibre cell walls were found to show almost axially oriented cellulose fibrils, and the stiffness and hardness of the central part of the cell wall remained basically consistent for the fibres at different regions across the fibre cap. A stiffness gradient across the fibre cap is developed by differential cell wall thickening which affects tissue density and thereby axial tissue stiffness in the different regions of the cap. The almost axially oriented cellulose fibrils in the fibre walls maximize the longitudinal elastic modulus of the fibres and their lignification increases the transverse rigidity. This is interpreted as a structural and mechanical optimization that contributes to the high buckling resistance of the slender bamboo culms.     

Extrusion and mechanical properties of highly filled cellulose fibre–polypropylene composites

This study focused on manufacturing of highly filled cellulose fibre–polypropylene composites and evaluation of the mechanical properties of the composites. Cellulose fibre reinforced polypropylene composites with up to 60 wt% of fibres with and without coupling agent were manufactured by extrusion. In order to achieve consistent feeding of the fibres into the extruder a pelletization technique was used where the fibres were pressed into pellets. Two commercial grades of cellulose fibres were used in the study, bleached sulfite and bleached kraft fibres. Fibre dimension measurements showed that the pelletization process and extrusion at high fibre loading caused the most severe fibre breakage. Flexural testing showed that increased fibre loading made the composites stiffer but reduced the toughness. Addition of maleic anhydride grafted coupling agent (MAPP) increased the stiffness and strength of the composites significantly. In general, there was no significant difference in the mechanical properties between the composites with kraft and sulfite fibres. An interesting finding was that the flexural modulus and strength of the MAPP modified cellulose fibre–polypropylene composites were not higher than what has previously been reported for wood flour–polyolefin composites. Scanning electron microscopy showed that addition of coupling agent improved the interfacial adhesion between the fibres and polypropylene matrix.     

Structure and properties of coir fibres

In this paper, early research on the structure and properties of coir fibres has been critically reviewed. Gaps in the scientific information on the structure and properties of coir fibre have been identified. Attempts made to fill some of these gaps include the evaluation of mechanical properties (as functions of the retting process, fibre diameter and gauge lengths of fibre, as well as of the strain rates) and fracture mechanisms using optical and scanning electron microscopy. The deformation mechanism of coir fibre resulting in certain observed properties has been discussed with the existing knowledge of the structure of plant fibres as a basis. It is concluded that more refined models need to be developed for explaining the observed mechanical properties of coir fibres. Some of the suggestions for further work include relating properties of fibres to factors like the chemical composition of the fibre and the size and number of cells, size of lumen, variation in micro-fibril angle within each cell and between different cells of the same fibre, and understanding the deformation of the whole fibre in terms of deformation of individual micro-components. Further work is required on the effects of mechanical, thermal and thermomechanical, chemical treatments to modify the structure and mechanical properties of these fibres in such a way as to make them more suitable as reinforcements in polymer, clay and cement matrices.     

Short sisal fibre reinforced bacterial cellulose polylactide nanocomposites using hairy sisal fibres as reinforcement

“Hairy” bacterial cellulose coated sisal fibres were created using a simple slurry dipping process. Neat sisal fibres were coated with BC to create (i) a dense BC coating around the fibres or (ii) “hairy” fibres with BC oriented perpendicular to the fibre surface. These fibres were used to produce hierarchical sisal fibre reinforced BC polylactide (PLLA) nanocomposites. The specific surface area of the BC coated fibres increased when compared to neat sisal. Single fibre tensile tests revealed no significant difference in the tensile modulus and tensile strength of “hairy fibres”. However, when sisal fibres were coated with a dense BC layer, the mechanical fibre properties decreased. The tensile, flexural and visco-elastic properties of the hierarchical PLLA nanocomposites reinforced by both types of BC coated sisal fibres showed significant improvements over neat PLLA.     

Production of carbon fibres from a pyrolysed and graphitised liquid crystalline cellulose fibre precursor

Regenerated cellulose fibres, spun from a liquid crystalline precursor, were pyrolysed at temperatures in the range 400–2,500?°C. Raman spectroscopy and X-ray diffraction showed that the degree of graphitisation of the fibre increased with increasing temperature. Electron microscopy, however, suggested that the fibres have a skin–core structure. This observation was confirmed by micro-Raman analysis, whereupon the ratio of the intensities of the D and G bands shows that the skin consists of a graphitised structure, whereas the core consists of significantly less graphitised material. The contributions of the graphitised skin and the inner core to the potential mechanical properties of the fibres were also assessed by following the position of the 2D Raman band during tensile deformation of the fibre. The Raman band shift rate against strain was used to evaluate the fibre modulus, which suggested a modulus of ~140 GPa for the skin and 40?GPa for the core, respectively. If this incomplete graphitisation could be overcome, then there is potential to produce carbon fibres from these novel precursor materials.     

All-cellulose composites of regenerated cellulose fibres by surface selective dissolution

All-cellulose composites of Lyocell and high modulus/strength cellulose fibres were successfully prepared using a surface selective dissolution method. The effect of immersion time of the fibres in the solvent during composite’s preparation and the effect of the starting fibre’s structure on their properties were investigated. Scanning electron microscopy, X-ray diffraction, dynamic mechanical analysis, and tensile testing were used to assess the structure and properties of the composites. These all-cellulose composites of regenerated cellulose fibres demonstrate a promising route to biocomposites with excellent mechanical and thermal properties which can also be tuned depending upon a selection of fibres and preparation parameters.     

Flax fibre and its composites – A review

In recent years, the use of flax fibres as reinforcement in composites has gained popularity due to an increasing requirement for developing sustainable materials. Flax fibres are cost-effective and offer specific mechanical properties comparable to those of glass fibres. Composites made of flax fibres with thermoplastic, thermoset, and biodegradable matrices have exhibited good mechanical properties. This review presents a summary of recent developments of flax fibre and its composites. Firstly, the fibre structure, mechanical properties, cost, the effect of various parameters (i.e. relative humidity, various physical/chemical treatments, gauge length, fibre diameter, fibre location in a stem, oleaginous, mechanical defects such as kink bands) on tensile properties of flax fibre have been reviewed. Secondly, the effect of fibre configuration (i.e. in forms of fabric, mat, yarn, roving and monofilament), manufacturing processes, fibre volume, and fibre/matrix interface parameters on the mechanical properties of flax fibre reinforced composites have been reviewed. Next, the studies of life cycle assessment and durability investigation of flax fibre reinforced composites have been reviewed.     

The hierarchical structure and mechanics of plant materials

The cell walls in plants are made up of just four basic building blocks: cellulose (the main structural fibre of the plant kingdom) hemicellulose, lignin and pectin. Although the microstructure of plant cell walls varies in different types of plants, broadly speaking, cellulose fibres reinforce a matrix of hemicellulose and either pectin or lignin. The cellular structure of plants varies too, from the largely honeycomb-like cells of wood to the closed-cell, liquid-filled foam-like parenchyma cells of apples and potatoes and to composites of these two cellular structures, as in arborescent palm stems. The arrangement of the four basic building blocks in plant cell walls and the variations in cellular structure give rise to a remarkably wide range of mechanical properties: Young''s modulus varies from 0.3 MPa in parenchyma to 30 GPa in the densest palm, while the compressive strength varies from 0.3 MPa in parenchyma to over 300 MPa in dense palm. The moduli and compressive strength of plant materials span this entire range. This study reviews the composition and microstructure of the cell wall as well as the cellular structure in three plant materials (wood, parenchyma and arborescent palm stems) to explain the wide range in mechanical properties in plants as well as their remarkable mechanical efficiency.     

Polyoxymethylene composites with natural and cellulose fibres: Toughness and heat deflection temperature

Cellulose and abaca fibre reinforced polyoxymethylene (POM) composites were fabricated using an extrusion coating (double screw) compounding followed by injection moulding. The long cellulose or abaca fibres were dried online with an infrared dryer and impregnated fibre in matrix material by using a special extrusion die. The fibre loading in composites was 30 wt.%. The tensile properties, flexural properties, Charpy impact strength, falling weight impact strength, heat deflection temperature and dynamic mechanical properties were investigated for those composites. The fibre pull-outs, fibre matrix adhesion and cracks in composites were investigated by using scanning electron microscopy. It was observed that the tensile strength of composites was found to reduce by 18% for abaca fibre and increase by 90% for cellulose fibre in comparison to control POM. The flexural strength of composites was found to increase by 39% for abaca fibre and by 144% for cellulose fibre. Due to addition of abaca or cellulose fibre both modulus properties were found to increase 2-fold. The notched Charpy impact strength of cellulose fibre composites was 6-fold higher than that of control POM. The maximum impact resistance force was shorted out for cellulose fibre composites. The heat deflection temperature of abaca and cellulose fibre composites was observed to be 50 °C and 63 °C higher than for control POM respectively.     

Influence of aqueous medium on mechanical properties of conventional and new environmentally friendly regenerated cellulose fibers

Comparative investigations between the new lyocell fibers and the regular viscose and modal types were made in order to explain the reasons for the differences in the mechanical properties of the fibers. The purpose was a systematic analysis of structure characteristics and of influence of aqueous medium on the mechanical properties. The properties determined in the wet state reflect the effect of the aqueous medium on the changes in the supermolecular structure during wet treatments [1, 2]. The new lyocell fibers consist of longer molecules and have a higher degree of crystallinity. Smaller but longer crystallites are oriented in the fiber axis direction and the voids structure is similar to that of viscose fibers [3]. Good mechanical properties are conditioned by the structure of the lyocell fibers, above all by high values of the orientation factor and crystallinity index. Sorption properties place lyocell fibers between the viscose and modal fibers. The water influence on the mechanical properties of lyocell fibers is considerably smaller compared to the viscose and modal fibers. Received: 18 September 2000 / Reviewed and accepted: 20 September 2000     

Microtexture and structure of boron nitride fibres by transmission electron microscopy, X-ray diffraction, photoelectron spectroscopy and Raman scattering

Continuous boron nitride fibres have been fabricated by melt spinning and pyrolysis of poly[2,4,6-tris(methylamino)borazine]. The longitudinal mechanical properties depend on mechanical stress and temperature applied during the conversion process. High-performance and low-performance fibres were characterized in order to find relationship between structure and physical properties. In all the cases, photoelectron spectroscopy (XPS) analysis proves that the chemical composition of the fibre is close to stoichiometric BN. The crystallite sizes were measured by means of X-ray diffraction (XRD) and Raman techniques. Cross-sections of separated fibres were investigated by high-resolution electron microscopy (HREM) and transmission electron microscopy (TEM). All the BN fibres have a hexagonal turbostratic structure. With increasing stress and temperature, the tensile strength and the elastic modulus increase. In the high-performance fibres, the 002 layers with an increased distance (about 0.35 nm) showed a mean stacking sequence near to graphite and a preferred orientation of the 002 layers parallel to the fibre axis.     

Creep behaviour and structural characterization at high temperatures of Nicalon SiC fibres

Two types of Nicalon SiC fibres having different structures have been examined. Their mechanical properties and their microstructures have been studied up to 1300° C. The fall in strength above 1000° C has been shown to be due to the microcrystallization of the fibre structure. Under low loads this change in structure led to a shrinkage of the fibre. The fibres were found to creep at temperatures above 1000° C when loads greater than a threshold level were applied. The creep of the fibres has been shown to be controlled by the changes which occur to the fibre structure. Degradation of the fibres on heating in air or argon has been shown to depend on SiO₂ and free carbon, which have been shown to exist in the fibre.     

Lenzing LYOCELL: Potentiale und Chancen einer neuen Fasergeneration

Lenzing LYOCELL – chances of a new generation of manmade fibres Cellulose is natures most important organic constructional and functional polymeric material and correspondigly has a variety of excellent and very specific properties. These properties can be used for a large number of products and can also be specifically modified as soon as it is possible to dissolve the cellulose and then to regenerate it in the desired shape. The progress in the development of the new Lyocell fibre, the better understanding of its performance and the possibilities to modify it, but also several completely new applications of the Lyocell process for other products show that the direct regeneration of cellulose from a solution in an organic solvent opens the path for a completely new utilisation of this outstanding property potential. Lyocell therefore not only offers the chance for a new generation of cellulosic fibres – also for new applications – but altogether also for a renaissance of cellulose for a large variety of products, where on the one side cellulose has been substituted during the last decades by synthetic polymers but where on the other side several completely new applications will be accessible for this outstanding polymer.     

Review: Current international research into cellulosic fibres and composites

The following paper summarises a number of international research projects being undertaken to understand the mechanical properties of natural cellulose fibres and composite materials. In particular the use of novel techniques, such as Raman spectroscopy, synchrotron x-ray and half-fringe photoelastic methods of measuring the physical and micromechanical properties of cellulose fibres is reported. Current single fibre testing procedures are also reviewed with emphasis on the end-use in papermaking. The techniques involved in chemically modifying fibres to improve interfacial adhesion in composites are also reviewed, and the use of novel fibre sources such as bacterial and animal cellulose. It is found that there is overlap in current international research into this area, and that there are complementary approaches and therefore further combining of these may make further progress possible. In particular a need to measure locally the adhesion properties and deformation processes of fibres in composites, with different chemical treatments, ought to be a focus of future research.     

Diameter dependence of the apparent tensile modulus of hemp fibres: A morphological,structural or ultrastructural effect?

The aim of this paper is to investigate the origin of the diameter-dependence of Young’s modulus in hemp fibres. In view of the considerable experimental difficulties encountered when determining the 3D morphology of elementary fibres, the influence of the fibre morphology and size on the E-modulus is studied using a mathematical model. An approach based on the 3D elastic theory is used to construct a model of the fibre structure, and to predict its mechanical properties. We clearly show that the modulus is dependent on the size of the lumen and on the outer fibre diameter. This structural effect, induced by the cylindrical geometry, the multi-layered organisation, and the orientation of the cellulose microfibrils only partly explains the large, experimentally determined dispersion of apparent E-modulus, as a function of fibre diameter. Ultrastructural parameters, such as cellulose crystallinity and microfibril angles, are identified to be the main factors involved in this dependence.     

Mechanical properties and failure of etched UHMW-PE fibres

The structural hierarchy of fibrillar ultra-high molecular weight polyethylene (UHMW-PE) fibres is investigated and related to fibre mechanical properties. Chemical etching has been used to change the surface properties of these UHMW-PE fibres through the removal of a skin layer and UHMW-PE oxidation. The physical and chemical changes to the fibre surface introduced by etching affect single-fibre mechanical properties. The effects of etchant and etching time on failure properties and mechanisms is discussed. The decrease in failure strain and strength with etching is associated with the change from an energy-absorbing fibril delamination failure to brittle fracture.