Effect of stearic acid treatment on the properties of aligned short hemp fibre mats and their potential use as reinforcement in polypropylene matrix composites

The main objective of this study was to assess the effect of stearic acid vapour treatment on hemp fibre mats produced using dynamic sheet forming, and the potential use of these treated mats as reinforcement in polypropylene matrix composites. Stearic acid was successfully applied through vapour treatment, appearing to form a layer on fibre surfaces. It was found that the presence of stearic acid increased hydrophobicity and thermal stability of fibre mats. It was also found to increase thermal stability of polypropylene matrix composites as well as their strength.

     

Investigations on the recycling of hemp and sisal fibre reinforced polypropylene composites

Microscopic, mechanical, rheological and thermal tests were carried out in order to determine the recycling behaviour of PP/vegetal fibre composites. Different composites using hemp and sisal were characterized. All results were compared with PP-g-MA/hemp composites and PP/glass fibre composites.The results prove that mechanical properties are well conserved with the reprocessing of PP/vegetal fibre composites but that there is poor adhesion between the fibres and PP without any treatment. The addition of PP-g-MA shows an improvement of the bonding evidenced by MEB pictures. Vegetal fibres induce an increase in the percentage of crystallinity χ_c and in the crystallization temperature T_c which can be explained by the nucleating ability of the fibres improving crystallization of PP. The Newtonian viscosity η₀ decreases with cycles, indicating a decrease in molecular weight and chain scissions induced by reprocessing. The decrease of fibre length with reprocessing could be another reason for viscosity decrease.     

Thermal and crystallization studies of short flax fibre reinforced polypropylene matrix composites: Effect of treatments

The effect of fibre treatments on thermal stability of flax fibre and crystallization of flax fibre/polypropylene composites was investigated. For thermal stability study, flax fibres have been treated using maleic anhydride, maleic anhydride polypropylene copolymer, vinyltrimethoxy silane and alkalization. In order to compare thermal stability of flax fibres thermogravimetry (TG) analysis has been used. Kinetic parameters have been determined by Kissinger method. Results showed that all treatments improved thermal stability of flax fibres. For crystallinity analysis, three different techniques have been used, differential scanning calorimetry analysis (DSC), pressure–volume–temperature (PVT) measurements for analysis of volume shrinkage and polarized optical microscopy (POM). All techniques results showed that addition of flax fibre increased crystallization rate. Besides, depending on fibre surface treatment and crystallization temperature, flax fibre/PP composites can show transcrystallinity.     

Rigidity analysis of polypropylene/vegetal fibre composites after recycling

Polypropylene/hemp or sisal fibre composites exhibit interesting recyclability [Bourmaud A, Baley C. Investigations on the recycling of hemp and sisal fibre-reinforced polypropylene composites. Polymer Degradation and Stability 2007;92(6):1034-45]. The obtained results prove that the tensile modulus of these polypropylene/vegetal fibre composites is well conserved with the number of reprocessing cycles. In this work, we investigated the relationship between the mechanical properties of the fibres and those of the composites by taking the influence of the recycling into account.In the first part of this study we carried out nanoindentation and tensile tests on vegetal fibres to obtain transversal and longitudinal Young's moduli. The experimental values were then introduced into micromechanical models, taking the aspect ratio changes into account, to estimate the stiffness of the PP/vegetal fibre injected composites before and after recycling. The first results show an interesting correlation between experimental results and model predictions; however a general underestimation of tensile stiffness of composites can be noticed.     

Natural source compatibilizers for olive waste/recycled polypropylene matrix composites

A simple, environmentally friendly process was developed for surface hydrophobization of cellulose-rich waste to improve their compatibility with recycled polypropylene (rPP), helping reduce costs while recycling environmentally problematic waste such as solid olive waste (also called olive pomace). In this study, an improvement of the interfacial bonding strength between the hydrophilic waste particles and the hydrophobic matrix was achieved by surface hydrophobization of the waste using a ring-opening polymerization reaction of epoxidized soy-bean oil (ESBO) with SnCl₂ as a catalyst. The treatment on cellulose based filter paper led to a contact angle of 128°. The composite containing treated olive pomace has shown an increase in the elongation of 92% and an increase in the stress at yield of 15%, indicating improved compatibility.     

Mechanical and biodegradation performance of short natural fibre polyhydroxybutyrate composites

The work outlined in this paper describes the evaluation of polyhydroxybutyrate (PHB) based natural fibre composites via an extrusion – injection moulding process. Virgin PHB was compounded with two different naturally occuring plant fibres, hemp and jute, and a third, regenerated cellulose fibre, lyocell. Composite materials containing 10–30 wt% of each type of fibre were obtained by twin screw extrusion and the resultant material was injection moulded to produce tensile samples suitable for mechanical characterisation. Mechanical properties were determined using tensile, impact and flexural testing. Melt flow index and water absorption studies were also carried out on the biocomposite materials, and Fourier transform infrared spectroscopy was used to examine the bonding between the polymer and each fibre type. The rate of biodegradation was also observed by placing composite samples in compost and measuring weight loss weekly. The biocomposites produced using this method were shown to have increased rates of biodegradation whilst exhibiting significantly improved flexural properties.     

Investigations of the microchemistry of interlayers in fibre/matrix composites

The potential applicability of analytical transmission electron microscopy is demonstrated for the characterization of the microchemistry of interlayers in fibre-reinforced composites with glass matrices.     

Effect of l-Arginine treatment on the in vitro stability of electrospun aligned chitosan nanofiber mats

Chitosan (Cs) mats obtained by electrospinning are potentially ideal scaffolds for tissue engineering. This technique allows obtaining nanometric fibrous structures with preferred orientation, which in turn enable cells to align themselves and produce extracellular matrix along desired orientations. In this study, we fabricated aligned Cs electrospun nanofiber mats and investigated the role of the amino acid l-Arginine (L-Arg) as stabilizing agent. Morphological, chemical, mechanical and biological characterizations were performed on untreated and L-Arg treated nanofibrous mats showing the role of L-Arg as biomimetic stabilizer. L-Arg acts as chemical stabilizer of nanofibrous mats, providing improved wettability behavior, mechanical properties and stability even after 60 days in aqueous medium in comparison to untreated mats. Moreover, preliminary biological tests demonstrated favorable cell-material interactions implying physiological responses in terms of viability and proliferation. The proposed L-Arg-treated Cs mats can be considered as potential scaffolds for highly oriented tissue patterning.     

Accelerated weathering of unbleached and bleached Kraft wood fibre reinforced polypropylene composites

In this paper, combined moisture/ultraviolet (UV) weathering performance of unbleached and bleached Kraft wood fibre reinforced polypropylene (PP) composites was studied. Composites containing 40 wt% fibre with 3 wt% of a maleated polypropylene (MAPP) coupling agent were fabricated using extrusion followed by injection moulding. Composite mechanical properties were evaluated, before and after accelerated weathering for 1000 h, by tensile and impact testing. Differential scanning calorimetry (DSC), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) were also carried out to assess the changes occurring during accelerated weathering. Bleached fibre composites initially showed higher tensile and impact strengths, as well as higher thermal stability and greater crystallinity. During accelerated weathering, both unbleached and bleached fibre composites reduced tensile strength (TS) and Young's modulus (YM), with the extent of the reduction found to be similar for both unbleached and bleached fibre composites. Evidence supported that the reduction of TS and YM was due to PP chain scission, degradation of lignin and reduced fibre-matrix interfacial bonding.     

Characterization of the coating layer on glass fibre used as reinforcement in polyepoxyde matrix

R glass fibre for the reinforcement of epoxy matrices has been coated with epoxy prepolymer (as film-former or sizing agent) or γAPS aminosilane (as coupling agent) or a mixture of these two products. The structure of the coating layer and its interaction capabilities with fibre and matrix have been studied by coupled calorimetry-gravimetry of sorption of different model reactants and by Fourier Transform infra-red analysis.     

Silane treatment in polypropylene composites: Adsorption and coupling

The study of the effect of eight silane coupling agents on mechanical properties of PP/CaCO₃ composites showed that the application of certain compounds leads to the reactive coupling of the components. The adsorption of the silanes on the surface of the filler was studied by a dissolution method, while the structure of the adsorbed layer was determined by FTIR spectroscopy and GPC measurements. Model reactions and an FTIR study were carried out to reveal possible coupling reactions of PP and the active silanes. The results showed that amino-functional silane coupling agents adsorb on the surface of the filler, polycondensation taking place and a polysiloxane layer of high molecular weight forms as a result. The model reactions indicated that during processing, PP oxidizes even in the presence of stabilizers and oxygen-containing functional groups form on the polymer chains. These easily react with the amino functionality of the silane coupling agents strongly bonding the polymer to the treated filler.     

Crystallisation of polypropylene matrix in composites filled with wooden parts of rapeseed straw

Nucleation ability of native and modified rapeseed straw during the polypropylene crystallization from the melt was investigated by the DSC method. Composites were made from isotactic polypropylene and lignocellulosic material using extrusion and injection moulding techniques. They were obtained using polypropylenes differing with respect to melt flow rates and different varieties of rapeseed straw. Chemical modification was carried out in two stages: through mercerisation and treatment with acetic acid anhydride. In the course of investigations, it was found that both native and modified rapeseed straw acted as an active nucleant of polypropylene crystallisation characterised by low values of MFR indices. It was found that for polypropylenes with high MFR values, the values of crystallization temperatures and crystallization half-time in composites were identical when compared with non-filled polymers. The investigations demonstrated that there were insignificant differences among composites containing straw from different varieties of rapeseed. The analysis of crystallization temperatures confirmed that rapeseed straw modification failed to change this parameter of the crystallization process. A similar tendency was observed in the case of changes of the half-time crystallization process. Moreover, the analysis of the crystallization temperature and crystallization half-time showed that the presence in composites of lignified rapeseed straw particles played an important role in the crystallization conditions.     

Solid-state shear pulverization as effective treatment for dispersing lignocellulose nanofibers in polypropylene composites

Lignocellulose nanofibers (LCNFs) were prepared by the wet-disk milling of wood flour and were subsequently used as a reinforcing filler for a polypropylene (PP) polymer matrix. The specific surface area and the smallest fiber width of the LCNFs were found to be 106 m²/g and 20 nm, respectively. Solid-state shear pulverization (SSSP) using a batch-type kneader was performed at a temperature lower than the PP melting point in order to improve the dispersion of the LCNFs in the PP matrix, which also contained 5 wt% maleic anhydride-grafted PP. The SSSP treatment improved LCNF dispersion; this was determined through optical and scanning electron microscopy observations. The improvement in LCNF dispersion after the SSSP treatment increased the Young’s moduli, yield strengths, and toughnesses of the resulting composites. The composites showed higher Young’s moduli and yield strengths that those of the neat PP matrix; this was true in the case of both the tensile and the bending tests. However, the impact strengths of the composites were not significantly different from that of the neat matrix. Finally, the crystallization rate of the PP matrix also increased with the increase in LCNF dispersion.     

Thermoplastic composites based on flax fibres and polypropylene: Influence of fibre length and fibre volume fraction on mechanical properties

Natural-fibre-mat-reinforced thermoplastic (NMT) composites based on flax fibre mats and a Polypropylene (PP) matrix were manufactured using (i) a film-stacking method and (ii) a paper making process. The influence of fibre length and fibre content on stiffness and strength is reported and compared with data for glass-mat-reinforced thermoplastic (GMT) composites, including the influence of using maleic-anhydride grafted PP. The data is also compared with existing micromechanical models like Kelly-Tyson and Cox-Krenchel for strength and stiffness, respectively. A good agreement was found between theory and experiment in case of stiffness while in case of strength the experimental values fall well below the theoretical predictions. Results indicated that NMTs are of interest for low-cost engineering applications and can compete with commercial GMTs, especially when a high stiffness per unit weight is desirable. Results also indicated that the key area for future development lies not only in improved adhesion but mainly in improving the fibre strength.     

Transcrystallization in nanofiber bundle/isotactic polypropylene composites: effect of matrix molecular weight

Polyamide 66 (PA 66) nanofiber bundles were first electrospun and then introduced into isotactic polypropylene (iPP) melts to prepare nanofiber bundle/iPP composites. To reveal the influences of matrix molecular weight (M _n ) on the transcrystalline layer, three kinds of iPP with different M _n were adopted. Polarized optical microscope was employed to investigate the transcrystallinity. In the presence of PA 66 nanofiber bundle, the heterogeneous nucleation distinctly happened in iPP melts. Moreover, the higher the iPP M _n , the denser the nuclei. Both a decrease in matrix M _n and an increase in isothermal crystallization temperature led to an increase in the induction time. The maximum temperature at which the transcrystalline layer can be optically observed increased with the increase of M _n . The growth rate of transcrystallinity decreased with the increasing M _n and crystallization temperature. Moreover, selective melting of the transcrystalline layers confirmed that it was merely composed of α form crystal for all composites.     

Grafting polypropylene and treatment of calcium carbonate to improve structure and properties of polypropylene composites

In this paper, calcium carbonate was chemically treated with two kinds of dicarboxylic acids before compounding with polypropylene in the presence of dicumyl peroxide (DCP). It was observed that the mixture of dicarboxylic acids could improve the crystallization and impact strength properties of calcium carbonate/polypropylene composite. With further addition of DCP, more PP-g-MA was produced in the blend, resulting in PP composites with larger β-phase content and improved mechanical properties. In the experiments, the maximum K _β value of 52.0 % was obtained. The elongation at break of composite increased from 252 % for PP composite with untreated calcium carbonate to 444 % for PP composite with chemically treated calcium carbonate.     

Cellulose nanocrystal surface functionalization for the controlled sorption of water and organic vapours

The surface grafting of cellulose nanocrystals (CNC) is a valuable tool to increase opportunities for their application. This work had several goals designed to improve CNC: reduction of hornification, increased re-dispersibility after CNC drying, and tuning of the surface graft to enhance the adsorption of particular molecules. To achieve this, the CNC surfaces were modified chemically with aromatic surface grafts using widely employed methods: the creation of urethane linkages, silylation and esterification. Even a low degree of grafting sufficed to increase water contact angles to as much as 96°. The analysis of water sorption isotherms showed that at high water activities, capillary condensation could be suppressed and hysteresis was decreased. This indicates that hornification was significantly suppressed. However, although the contact angles increased, the water sorption isotherms were changed only slightly because of reduced hysteresis. The grafts were not able to shield the surface from water vapour sorption. A comparison of the sorption isotherms of anisole and cyclohexane, sorbates with a similar surface area, showed that the sorption of anisole was three times higher than that of cyclohexane. The specific sorption of aromatic molecules was achieved and the most efficient methodology was the esterification of CNC with carboxylic acids containing a flexible linker between the aromatic moiety and ester bond.     

Wetting behavior of flax fibers as reinforcement for polypropylene

The wetting behavior of several flax (cellulose as reference) and polypropylene fibers is characterized by measuring the wetting rates (penetration velocities) of a series of liquids using the capillary rise technique. This present paper aims to provide a deeper understanding of the complex nature of natural fibers and their surface properties. The fiber surface tensions are estimated from plots of the normalized wetting rate as a function of the surface tension of the liquids assuming, in analogy to Zisman's method, that the maximum of the normalized wetting rate corresponds to the solid surface tension. The estimated surface tensions of the investigated flax fibers indicate that all the fibers are quite "hydrophobic." The method used to separate the fibers from the rest of the plants has a large influence on the estimated fiber surface tensions. In the case of polypropylene (PP) fibers, the estimated surface tension corresponds well with literature data. Grafting small amounts of maleic acid anhydrite (MAH) onto the PP surfaces will not affect the wetting behavior and, therefore, the surface tension, whereas grafting larger amounts (10 wt%) of MAH causes the polymer surface tension to increase significantly. Additional pH-dependent zeta-potential measurements show that even the "pure" PP-fibers contain acidic surface functions, possibly due to further processing at elevated temperatures (thermal degradation or other aging processes).     

Study of the wettability properties of polypropylene nonwoven mats by low‐pressure oxygen plasma treatment

Surface modification by plasma treatment is widely used for textiles and polymeric materials. Plasma processes are environmentally friendly and reduce chemicals and energy consumption. This study reports the effect of cold, low‐pressure oxygen plasma on the wettability properties of polypropylene (PP) nonwoven mats. The wetting properties were examined using contact angle, surface energy, and diameters of the drop after 20 s of treatment. It was found that plasma treatment had a significant effect on the wettability of PP fibers. The ageing for 90 days had no significant effect on the wettability. It was also shown that the morphology of the fibers was not affected by the plasma treatment. Copyright © 2007 John Wiley & Sons, Ltd.     

Time-scale through-thickness interphase in polymer matrix composites including hygrothermal treatment

For the first time, the physical effects of long-term environmental conditions on through-thickness interphase in polymer matrix composites (PMCs) were studied. Atomic force microscopy (AFM) -based Peak Force Quantitative Nanomechanical Mapping (PF QNM) technique was utilized to study the effects of heat and humidity on the mechanical properties of interphase at nanometer resolution. Samples were aged with a heat of 60 °C and relative humidity of 90% for up to 2 years. The width of the interphase is uneven and ‘river-like’ through the thickness in unaged and aged composites. The width of interphase depends on its location and the degree of moisture saturation. The difference in thickness of the interphase, through the thickness, reduces with exposure time. While the mechanism of expansion and shrinkage of interphase is different through-thickness, the range of material modulus is almost the same through-thickness in unaged and aged conditions. Rate of debonding increases from unaged to one-year aged and reduces in the second year of exposure.