A study of transcrystallinity and its effect on the interface in flax fibre reinforced composite materials

Cellulose fibres have long been used in the plastics industry as cost-cutting materials. Nowadays they are recognised as a potential replacement for glass fibres for use as reinforcing agents in composite materials. They have a number of certain advantages over glass fibres, such as low cost, high strength-to-weight ratio, biodegradability and ease of processing. In this study crystallisation from the melt of two different isotactic polypropylene matrices (iPP) in the presence of flax (Linum usitatissinum) fibres of four different types (green flax, dew retted flax, Duralin^® treated flax and stearic acid sized flax) was examined. The effect of processing parameters such as crystallisation temperature and cooling rate was investigated using hot stage optical microscopy. Differential scanning calorimetry (DSC) was used to investigate the inner morphology of the transcrystalline (TC) layer. Scanning electron microscopy (SEM) and X-ray diffraction were used in an attempt to identify the origin of the TC layer in connection with the structural characteristics of the fibres. The effect of transcrystallinity upon the mechanical properties of the interface was assessed using the single fibre fragmentation test. It was found that the interfacial adhesion is improved by the presence of a TC layer.     

Fibre/matrix adhesion of cellulose fibres in PLA,PP and MAPP: A critical review of pull-out test,microbond test and single fibre fragmentation test results

The present work deals with the practical fibre/matrix adhesion of regenerated cellulose fibres (lyocell) and bast fibre bundles (flax, kenaf) in different matrices (polylactide-PLA, polypropylene-PP, maleic-anhydride-grafted polypropylene-MAPP). The influence of different testing procedures (pull-out test, microbond test, fragmentation test) on the fibre/matrix characteristics is discussed. The results of the different tests showed the same trends, but the absolute values differ. Clearly higher interfacial shear strength (IFSS) for cellulose fibres was found in PLA and MAPP in comparison to PP due to higher polarity. In addition, bast fibres displayed higher apparent IFSS values compared to lyocell because of their rougher surface and their chemical composition. The apparent IFSS of the pull-out test resulted in higher values compared to results obtained from the fragmentation test. This phenomenon is explained by different stress distributions due to variable specimen geometry, different behaviour of failure and the friction which occurs between fibre and matrix during fibre pull-out in the pull-out test.     

Effect of transcrystalline morphology on interfacial adhesion in cellulose/polypropylene composites

A study was conducted on the effect of cotton cellulose fibres on the crystallization behaviour of isotactic polypropylene (PP) from the melt and the resulting morphology. When the PP was allowed to crystallize isothermally at 131° C, the cotton fibres acted as nucleating agents and a transcrystalline phase was created around the fibres. Quench cooling of the melt prevented the occurrence of such a phase. Transcrystalline layers of different thicknesses were created by interrupting the isothermal crystallization at certain intervals and quenching the melt. The effect of these morphologies on interfacial shear stress transfer was investigated using the single-fibre fragmentation test. It was found that the transcrystalline morphology at the fibre/matrix interface improved the shear transfer considerably when a tensile load was applied in the fibre direction. One mechanism is proposed to be particularly responsible for this increase: slow cooling favours the kinetics of the approach of PP molecules, and hence interfacial adsorption, which yields an ordered transcrystalline PP interphase having a high density of intermolecular secondary bonds with the cellulose surface. An increase in the shear transfer efficiency with increasing thickness of the transcrystalline layer was also observed.     

Determination of interfacial shear strength of white rot fungi treated hemp fibre reinforced polypropylene

Short untreated and white rot fungi treated hemp fibre, polypropylene (PP) and maleated polypropylene (MAPP) coupling agent were extruded and injection moulded into composite tensile test specimens. The tensile properties of untreated and treated fibre and their composites were measured. The fibre length distributions in the composite were obtained by dissolving the PP/MAPP matrix in boiling xylene to extract the fibre. Both the Single Fibre Pull-Out test and the Bowyer and Bader model were used to determine the interfacial shear strength (IFSS) of these composites. IFSS was found to be lower for the Single Fibre Pull-Out test, which was considered to be largely due to axial loading of fibre and the resulting Poisson’s contraction occurring during this technique. This suggests that the Bowyer and Bader model provides a more relevant value of IFSS for composites. The results obtained from both methods showed that IFSS of the treated fibre composites was higher than that for untreated fibre composites. This supports that the hemp fibre interfacial bonding with PP was improved by white rot fungi treatment.     

Mechanical properties of flax fibre/polypropylene composites. Influence of fibre/matrix modification and glass fibre hybridization

The effect of fibre treatments and matrix modification on mechanical properties of flax fibre bundle/polypropylene composites was investigated. Treatments using chemicals such as maleic anhydride, vinyltrimethoxy silane, maleic anhydride-polypropylene copolymer and also fibre alkalization were carried out in order to modify the interfacial bonding between fibre bundles and polymeric matrix. Composites were produced by employing two compounding ways: internal mixing and extrusion. Mechanical behaviour of both flax fibre bundle and hybrid glass/flax fibre bundle composites was studied. Fracture surfaces were investigated by scanning electron microscopy. Results suggest that matrix modification led to better mechanical performance than fibre surface modification. A relevant fact is that silanes or MA grafted onto PP matrix lead to mechanical properties of composites even better than those for MAPP modification, and close to those for glass fibre/PP.     

Influence of the Physical Structure of Flax Fibres on the Mechanical Properties of Flax Fibre Reinforced Polypropylene Composites

This study investigates the influence of the physical structure of flax fibres on the mechanical properties of polypropylene (PP) composites. Due to their composite-like structure, flax fibres have relatively weak lateral bonds which are in particular present in flax fibres that are often used in natural fibre mat reinforced thermoplastics (NMT). These weak bonds can be partly removed by combing the fibres. In order to study the influence of the physical structure of flax fibres on NMT tensile and flexural properties, uncombed and combed flax fibre reinforced PP composites were manufactured via a wet laid process. The influence of improved fibre-matrix adhesion was studied using maleic-anhydride grafted PP. Results indicated that the flax physical structure has a significant effect on flax-PP composite properties and that the flax fibre reinforced PP properties are similar to values predicted with existing micromechanical models. The tensile modulus of flax-PP composites can fairly compete with commercial glass mat reinforced thermoplastic (GMT) modulus, the strength, however, both tensile and flexural, can not. In order to rise the strength of flax fibre reinforced PP composites to the level of GMT strength, the flax fibres have to be further isolated to elementary flax fibres.     

Effect of amphiphilic coupling agent on heat flow and dielectric properties of flax–polypropylene composites

The study on heat transport in composites is of fundamental importance in engineering design and for tailoring thermal and mechanical behaviour of materials. In this study, the thermal conductivity and thermal diffusivity of flax reinforced polypropylene (PP) composites were determined at room temperature. Chemical modification in the form of a biodegradable zein coating was applied to the flax nonwovens. The effect of fibre loading and chemical modification on the thermo-physical properties was investigated. Dielectric permittivity studies were also evaluated and the dielectric constant of fibre reinforced composites was found to be higher than that of PP. The heat flow and crystallinity effects of the composites were also determined by differential scanning calorimetric (DSC) studies. Zein modification of the flax fibres resulted in a decrease of thermal conductivity and diffusivity which was attributed to a decrease in velocity and mean free path of phonons due to increase in interfacial adhesion.     

Effect of additives on the interfacial strength of poly(l-lactic acid) and poly(3-hydroxy butyric acid)-flax fibre composites

The interfacial shear strength (IFSS), evaluated by single fibre pull-out tests was quantified for various biopolymer-flax fibre composites that were modified with additives. The additives included a plasticiser (glycerol triacetate) (GTA) absorbed onto/into the fibres, 4,4′-thiodiphenol (TDP) that is capable of forming hydrogen bonds between the matrix and cellulose from the fibres, and a hyperbranched polyester (HBP) to impart improved fracture toughness. Fibres were washed with acetone to remove the surface impurities and dried under vacuum before absorption of plasticiser and adsorption of thiodiphenol. It was found that the different additives significantly influenced the IFSS for the biopolymer-flax fibre systems while extraction with acetone had a no effect on the IFSS compared with the untreated fibres. The use of TDP imparted the most significant increase in IFSS whilst the HBP had an opposing effect. The use of ESEM corroborated with the findings of the single fibre pull-out tests.     

Switchgrass (Panicum virgatumL.) as a reinforcing fibre in polypropylene composites

In this study the switchgrass (Panicum virgatumL.), a biomass crop being developed in North America and Europe, was tested as a stiffening and reinforcing agent in polypropylene (PP) composites with and without maleic anhydride grafted PP (MAPP) as a compatibiliser and to evaluate the effect of pulping and different sources of switchgrass on composite characteristics. The refiner pulping yield for two switchgrass varieties was estimated between 70–80%. The addition of 30% (by weight) switchgrass pulp resulted in an increase of the flexural modulus by a factor of about 2.5 compared to pure polypropylene. Which was only slightly lower than values found for jute and flax. The flexural strength of PP composites reinforced with pulped switchgrass and MAPP was almost doubled compared to pure PP and approached values found for jute and flax. The compatibilising effect of MAPP has been visualised by micrographs. The good mechanical properties are achieved despite the severe fibre length reduction as a result of thermoplastic compounding which is shown by fibre length analysis. The impact strength of switchgrass/PP composites was much lower than for pure PP. The use of different switchgrass varieties and harvesting time had a minor to no effect on the mechanical performance of the respective composites. The chemical composition of different varieties was fairly constant. The low price and the relatively good mechanical characteristics should make switchgrass an attractive fibre for filling and stiffening in thermoplastic composites. Further improvement of composite mechanical properties should be possible.     

Single fibre pull-out test versus short beam shear test: comparing different methods to assess the interfacial shear strength

Mechanical characteristics of fibre-reinforced composites are decisively influenced by the fibre/matrix interactions. This work is focused on the comparison of the single fibre pull-out test and the short beam shear test to assess the main advantages of both methods in terms of resource requirements and reliability. Lyocell fibres are used raw and enzymatic modified in thermoplastic (PLA and PP, both methods) as well as thermoset (PTP and Biresin, only short beam shear test) matrices. The IFSS values of the pull-out test are all in the range from 10.93 ± 3.63 to 14.87 ± 5.22 N/mm². The results of the short beam shear test provide significant differences in apparent ILSS for the analysed fibre/matrix combinations. The results of the single fibre pull-out test show no significant differences in IFSS and have a higher variance, but enable a better estimation of the potential of the examined fibre–matrix combination.     

Environmental Durability of Flax Fibres and their Composites based on Polypropylene Matrix

The environmental degradation behaviour of flax fibres and their polymer composites are explored. New upgraded Duralin flax fibres, which have been treated by a novel treatment process for improved moisture and rot sensitivity were studied. Environmental studies showed that these upgraded Duralin flax fibres absorb less moisture than untreated Green flax fibres, whereas the mechanical properties of the treated fibres were retained, if not improved. The effect of this novel flax fibre treatment on the environmental behaviour of natural-fibre-mat-reinforced thermoplastics (NMTs) is investigated by monitoring the moisture absorption and swelling, and measuring the residual mechanical properties of the flax/polypropylene composites at different moisture levels. The moisture absorption and swelling of the upgraded flax fibre composites is approximately 30% lower than that of composites based on Green flax fibres.     

Synergy of matrix and fibre modification on adhesion between carbon fibres and poly(vinylidene fluoride)

Interfacial properties between carbon fibres and poly(vinylidene fluoride) (PVDF) were tuned by modifying both constituents. Atmospheric plasma fluorination (APF) was utilised to tailor the surface composition of carbon fibres, which resulted in an incorporation of up to 3.7 at.% of fluorine functionalities in to the fibre surfaces. The PVDF matrix was modified by blending pure PVDF with maleic anhydride (MAH) grafted PVDF. Both fibre and matrix modifications act in synergy with improvements of up to 50% in the apparent interfacial shear strength (IFSS) above the level of pure fibre or matrix modification. Modification of both constituents led to the formation of various interactions at the fibre/matrix interface namely dispersive and polar (H-bonds) between (modified) PVDF and the fluorine as well as oxygen functionalities on the fibre surfaces. The apparent IFSS between the modified fibres and matrix reaches a maximum of 42 MPa, which is almost the tensile strength of the pure PVDF. The improvements in apparent IFSS in single fibre model composites for both fibre and matrix modifications translated to a seven times improvement in the interlaminar shear strength of unidirectional composites.     

Could biopolymers reinforced by randomly scattered flax fibre be used in structural applications?

Thermoplastics reinforced by natural fibres are mainly used for fitting-up products in the automotive industry. The aim of this work is to study the tensile properties of natural fibre-biopolymer composites in order to determine whether or not, biocomposites may replace glass fibre reinforced unsaturated polyester resins. The materials used are flax fibre, polylactic acid (PLA), l-polylactide acid (PLLA), poly(3-hydroxylbutyrate) (PHB), polycaprolactone and starch thermoplastic (MaterBi® Z), poly(butylene succianate) (PBS) and poly(butylene adipate-co-terephtalate) (PBAT). The tensile properties of the flax fibres have already been determined [C. Baley, Analysis of the flax fibres tensile behaviour and analysis of the tensile stiffness increase, Comp Part A 2002;33:939–948]. The composites are manufactured using a film stacking technique. After studying the processing parameters, these are then adapted to each thermoplastic composites. Test samples are cut out from the composites to test their mechanical properties under tensile loading conditions. These tensile properties are then compared to those of similar polypropylene flax composites. Preliminary results show that the tensile properties are improved with the fibre volume fraction. The tensile strength and Young’s modulus of PLLA and PLA flax composites are greater than those of similar PP/flax fibre composites. The specific tensile strength and modulus of flax fibre/PLLA composite have proved to be very close to those of glass fibre polyester composites.     

Effect of material and process parameters on the mechanical properties of unidirectional and multidirectional flax/polypropylene composites

Unidirectional (UD) and multidirectional (MD) flax/polypropylene composites were studied. Flax with varying retting degree and boiled flax was used as reinforcement for the UD composites and unmodified and maleic acid anhydride modified polypropylene (MAA-PP) was used as matrix. Multidirectional flax/polypropylene composites were manufactured on laboratory scale and on pilot scale. They were made from needle-punched hybrid flax/PP non-wovens. Normally retted flax as well as boiled flax was used. For the specimens made on pilot scale, a third kind of flax, namely bleached flax was also studied. The influence of different process times and temperatures on the mechanical properties of the composites was analysed. Generally, the composites have adequate good mechanical properties. The unidirectional composites of boiled flax combined with MAA-PP show the best mechanical properties. Contrary to the UD composites, flax treatment did not lead to the expected property improvements for MD composites.     

The tensile deformation of flax fibres as studied by X-ray scattering

Small and wide-angle X-ray scattering experiments with in-situ deformation of dry flax fibres have been carried out. An increase in the (200) peak intensity during deformation has been attributed to strain-induced crystallisation of the cellulose microfibrils, and provides evidence that the non-crystalline cellulose chains are initially oriented. However, no change in the equatorial small-angle streak (from cellulose microfibrils), the meridional reflection (from a crystalline/non-crystalline repeat along the fibre), or the microfibril orientation was seen.     

Characterisation of interphase nanoscale property variations in glass fibre reinforced polypropylene and epoxy resin composites

The local microstructure can be altered significantly by various fibre surface modifications, causing property differences between the interphase region and the bulk matrix. By using tapping mode phase imaging and nanoindentation tests based on the atomic force microscope (AFM), a comparative study of the sized fibre surface topography and modulus as well as the local mechanical property variation in the interphase of E-glass fibre reinforced epoxy resin and E-glass fibre reinforced modified polypropylene (PPm) matrix composites was conducted. The phase imaging AFM was found a highly useful tool for probing the interphase with much detailed information. Nanoindentation experiments indicated the chemical interaction during processing caused by a gradient profile in the modulus across the interphase region of γ-aminopropyltriethoxy silane (γ-APS) and polyurethane (PU)-sized glass fibre reinforced epoxy composite. The interphase with γ-APS/PU sizing is much softer than the PPm matrix, while the interphase with the γ-APS/PP sizing is apparently harder than the matrix, in which the modulus was constant and independent of distance away from the fibre surface. The interphase thickness varied between less than 100 and ≈300 nm depending on the type of sizing and matrix materials. Based on a careful analysis of ‘boundary effect’, nanoindentation with sufficient small indentation force was found to enable measuring of actual interphase properties within 100 nm region close to the fibre surface. Special emphasis is placed on the effects of interphase modulus on mechanical properties and fracture behaviour. The interphase with higher modulus and transcrystalline microstructure provided simultaneous increase in the tensile strength and the impact toughness of the composites.     

Carbon nanotube grafted silica fibres: Characterising the interface at the single fibre level

Model polymer composites containing carbon nanotube (CNT) grafted fibres provide a means to investigate the influence of nanostructures on interfacial properties. Well-aligned nanotubes, with controllable length, were grown on silica fibres by using the injection chemical vapour deposition method, leading to a significant increase of the fibre surface area. In single fibre tensile tests, this CNT growth reaction reduced the fibre strength, apparently due to catalyst etching; however, the fibre modulus increased significantly. Contact angle measurements, using the drop-on-fibre method, indicated an excellent wettability of the CNT-grafted fibres by poly(methyl methacrylate) (PMMA). PMMA model composites were fabricated and studied using the single fibre fragmentation tests. A dramatic improvement (up to 150%) of the apparent interfacial shear strength (IFSS) was obtained for the composites containing CNT-grafted fibres. The improvement of IFSS was also influenced by the length and morphology of the grafted CNTs.     

Reinforcement of polypropylene with hemp fibres

Noil hemp fibre (NHF) is a kind of textile hemp fibre after deep degumming from scutched hemp fibre (SHF), mechanically-degummed hemp fibre. Both NHF and SHF with strong mechanical properties are good candidates as reinforcing fibres for plastics such as polypropylene (PP). The PP/NHF and PP/SHF composites were blended via internal mixing process. The effect of fibres on the morphology, thermal resistance and reinforcement of the composites were investigated. PP/NHF composites showed higher impact strength, lower flexural strength than PP/SHF at the corresponding loading because NHF has smaller diameter and better thermal resistance than SHF. Meanwhile, NHF has the similar reinforcement to tensile strength with SHF. The effect of maleic anhydride polypropylene (MAPP) on the fibre-resin interface bonding was also comparatively studied. With increasing amount of MAPP, the tensile, flexural and impact strengths of PP/NHF and PP/SHF increased, respectively. The morphology of PP/SHF and PP/NHF results well showed that MAPP improved the interaction of the fibres with PP through chemical adhesion.     

Matrix morphology and fibre pull-out strength of T700/PPS and T700/PET thermoplastic composites

The main objective of this fundamental study was to investigate effects of processing conditions and resulting matrix morphology on interfacial bond strength of fibre reinforced thermoplastic composites. Using a hot stage microscope, single fibre pull-out samples were produced with T700S high strength carbon fibre and two semicrystalline thermoplastic matrices, polyphenylene sulphide (PPS) and polyethylene terephthalate (PET), respectively. Processing temperatures and cooling histories were the major variables in sample preparation. The T700S fibre had no clear effect on the surrounding PPS and PET matrix morphology, as long as direct cooling at constant rates was selected. A transcrystalline phase around the fibres could be induced in the T700S/PPS system, if isothermal crystallization was carried out at 227°C. Fibre pull-out tests were conducted at room temperature and two basic failure paths were observed, i.e. debonding at the fibre-matrix interface and cohesive failure of the matrix close to the fibre surface. The results indicate that slow cooling rate and a resulting coarse spherulitic morphology around the fibres correlate with high interfacial shear strength. In fact somewhat higher strength values were obtained for samples with transcrystalline layers around the fibres.     

Carbon nanotube grafted carbon fibres: A study of wetting and fibre fragmentation

Carbon nanotubes (CNTs) were grafted on IM7 carbon fibres using a chemical vapour deposition method. The overall grafting process resulted in a threefold increase of the BET surface area compared to the original primary carbon fibres (0.57 m²/g). At the same time, there was a degradation of fibre tensile strength by around 15% (depending on gauge length), due to the dissolution of iron catalyst into the carbon; the modulus was not significantly affected. The wetting behaviour between fibres and poly(methyl methacrylate) (PMMA) was directly quantified using contact angle measurements for drop-on-fibre systems and indicated good wettability. Single fibre fragmentation tests were conducted on hierarchical fibre/PMMA model composites, demonstrating a significant (26%) improvement of the apparent interfacial shear strength (IFSS) over the baseline composites. The result is associated with improved stress transfer between the carbon fibres and surrounding matrix, through the grafted CNT layer. The improved IFSS was found to correlate directly with a reduced contact angle between fibre and matrix.