Dwarf Cavendish as a Source of Natural Fibers in Poly(propylene)‐Based Composites

Summary: Composite materials were prepared by compounding and hot‐pressing PP or MAPP and lignocellulosic fibers extracted from the rachis of Musa acuminate Colla var. Dwarf Cavendish banana tree. The fibers were used as raw filler or after a chemical treatment expected to remove most of the extractible compounds. The resulting materials were characterized using SEM, DSC, DMA, tensile tests and water sorption experiments. All results show that the main aspect involved in the interfacial adhesion between the polar filler and the non‐polar matrix is the extraction of lignin and fatty substances. This results in higher values of the degree of crystallinity and crystallization temperature of the matrix, higher mechanical properties and lower water sensitivity.

Scanning electron micrograph showing the cross section of the lignocellulosic filler obtained from rachis of banana tree: (a) raw, and (b) extracted fibers.     

In‐Situ Fiberized Poly(ethylene terephthalate) as a Reinforcement to Poly(propylene) Matrix

The reinforced poly(propylene) (PP)/poly(ethylene terephthalate) (PET) in‐situ fiberized composites were prepared by extrusion‐drawing‐injection molding. The influences of PET weight fraction (f_w) on the PET fiberization, phase morphology, and mechanical properties of the composites, together with their functional mechanisms were studied by contrast to the normal‐blended materials without drawing. The results show that as the f_w rises from 0 to 20%, the number of PET fibers increases, whereas their diameter and dispersity decrease till f_w = 15% and then increase, and the number of remained PET particles tends to rise. These changes of PET fiberization and phase morphology with f_w were attributed to the consequence of the combined actions of breakup, coalescence, and deformation of the PET dispersed phase in the PP matrix during the extrusion drawing. Correspondingly, the tensile strength (σ_t) and Young's modulus (E) of the in‐situ composites increase till f_w = 15% and then decrease, with maximum gains of σ_t and E of about 20 and 70% relative to the neat PP, respectively. This σ_t/f_w relation was ascribed to the counterbalanced result between the reinforcing effect of the dispersed phase on matrix and the interfacial flaw effect of two immiscible phases, while the E/f_w relation was considered as a representation of the rigidizing effect of the fibers on the matrix being controlled by both their number and diameter.

In‐situ PET fibres (PET/PP = 85/15) in an as‐drawn filament.     

Unmodified and Modified Surface Sisal Fibers as Reinforcement of Phenolic and Lignophenolic Matrices Composites: Thermal Analyses of Fibers and Composites

Summary: The study and development of polymeric composite materials, especially using lignocellulosic fibers, have received increasing attention. This is interesting from the environmental and economical viewpoints as lignocellulosic fibers are obtained from renewable resources. This work aims to contribute to reduce the dependency on materials from nonrenewable sources, by utilizing natural fibers (sisal) as reinforcing agents and lignin (a polyphenolic macromolecule obtained from lignocellulosic materials) to partially substitute phenol in a phenol‐formaldehyde resin. Besides, it was intended to evaluate how modifications applied on sisal fibers influence their properties and those of the composites reinforced with them, mainly thermal properties. Sisal fibers were modified by either (i) mercerization (NaOH 10%), (ii) esterification (succinic anhydride), or (iii) ionized air treatment (discharge current of 5 mA). Composites were made by mould compression, of various sisal fibers in combination with either phenol‐formaldehyde or lignin‐phenol‐formaldehyde resins. Sisal fibers and composites were characterized by thermogravimetry (TG) and DSC to establish their thermal stability. Scanning electron microscopy (SEM) was used to investigate the morphology of unmodified and modified surface sisal fibers as well as the fractured composites surface. Dynamic mechanical thermoanalysis (DMTA) was used to examine the influence of temperature on the composite mechanical properties. The results obtained for sisal fiber‐reinforced phenolic and lignophenolic composites showed that the use of lignin as a partial substitute of phenol in phenolic resins in applications different from the traditional ones, as for instance in other than adhesives is feasible.

Micrograph of the impact fracture surface of phenolic composite reinforced with mercerized sisal fiber (500 X).     

Mechanical Behavior and Fracture Toughness of Poly(L‐lactic acid)‐Natural Fiber Composites Modified with Hyperbranched Polymers

Summary: The use of hyperbranched polymers (HBP) with hydroxy functionality as modifiers for poly(L ‐lactic acid) (PLLA)‐flax fiber composites is presented. HBP concentrations were varied from 0 to 50% v/v and the static and dynamic tensile properties were investigated along with interlaminar fracture toughness. Upon addition of HBP, the tensile modulus and dynamic storage modulus (E′) both diminished, although a greater decline was noticed in the static modulus. The elongation of the composites with HBP showed a pronounced increase as large as 314% at 50% v/v HBP. The loss factor (tan δ) indicated a lowering of the glass transition temperature (T_g) due to a change in crystal morphology from large, mixed perfection spherulites to finer, smaller spherulites. The change in T_g could have also resulted from some of the HBP being miscible in the amorphous phase, which caused a plasticizing effect of the PLLA. The interlaminar fracture toughness measured as the critical strain energy release rate (G_IC) was significantly influenced by HBP. At 10% v/v HBP, G_IC was at least double that of the unmodified composite and a rise as great as 250% was achieved with 50% v/v. The main factor contributing to high fracture toughness in this study was better wetting of the fibers by the matrix when the HBP was present. With improved ductility of the matrix, it caused ductile tearing along the fiber‐matrix interface during crack propagation.

ESEM photograph of propagation region of the interlaminar fracture toughness specimens with 30% v/v of HBP.     

Flexural Creep Behavior of Unidirectional and Cross‐Ply All‐Poly(propylene) (PURE®) Composites

The long‐term viscoelastic behavior of reinforced all‐poly(propylene) composites was studied by flexural creep tests. Both unidirectional and cross‐ply laminates were prepared from PURE® coextruded tapes by vacuum bag molding in an autoclave. The specimens were subjected to isothermal creep tests at different temperatures ranging from 20 to 80 °C under an applied load. The time‐temperature superposition principle was verified for the creep data. An Arrhenius type relationship was found to better describe the shift data obtained from the creep tests. The activation energies relating to the different reinforcement architecture and different relaxation process were calculated.

     

Morphology and Photophysical Properties of Electrospun Light‐Emitting Polystyrene/Poly(p‐phenylene ethynylene) Fibers

Ultra‐thin fibers, consisting of blends of a PPE derivative and polystyrene, with average diameters ranging from 430 to 1 200 nm, were produced by electrospinning. The electrospinnability was significantly improved by adding pyridinium formate to the spinning solution. FT‐IR spectroscopy was used to confirm the composition of the electrospun fibers and their morphology was probed by SEM. The optical properties of the as‐prepared solutions, pristine and annealed fibers, and corresponding spin‐coated and solution‐cast films were investigated by UV‐vis spectroscopy. A comparison of the PL emission spectra revealed aggregation of PPE molecules in the electrospun materials but the extent of aggregation can be reduced if the materials are annealed above the glass transition temperature.

     

国内外植物纤维增强水泥基复合材料的研究

自然界广泛存在的植物纤维的形态具有长径比大,比强度高,比表面积大等优点。纤维在抑制混凝土裂缝发展中具有重要的作用,研究开发植物纤维增强水泥基复合材料不仅能降低混凝土的造价,而且有利于环保和可持续发展,具有深远的意义。文章综述了植物纤维的性能与增强作用、在混凝土应用中的研究进展、发展前景和存在的一些问题。     

Lignocellulosic Flour from Cladodes of Opuntia ficus‐indica Reinforced Poly(propylene) Composites

Summary: A lignocellulosic flour was obtained by grinding dried cladodes of Opuntia ficus‐indica. It was used as low cost natural filler in PP and the effect of the treatment of the filler with MAPP was also investigated. The morphology and thermal properties of these composites were evaluated by SEM and DSC, respectively. MAPP coating resulted in a better adhesion between the filler and the matrix and higher homogeneity of the material. A decrease of the degree of crystallinity of the PP matrix in presence of the untreated filler was observed. Dynamic mechanical analysis and tensile properties were also studied. High‐strain tensile properties display enhanced mechanical properties for MAPP treated‐based composites only. When conditioned in highly moist atmosphere (98% RH), both the water uptake and water diffusion coefficient decrease when the filler was treated. These effects were ascribed to the promoting interfacial adhesion induced by the coating treatment. In liquid water, this increased adhesion between the filler and the matrix results in a higher weight loss of the material. It is due to the removal of the grafted polymer from the material during the dissolution of part of the filler.

SEMs of freshly fractured surface for a PP film filled with 10 wt.‐% of MAPP treated OFI cladode (top) and calcium oxalate crystallite within the PP matrix for a 3 wt.‐% filled composite (bottom).     

Thermoset lactic acid‐based resin as a matrix for flax fibers

Thermoset composites were produced from flax fibers and a novel lactic acid (LA)‐based thermoset resin. This resin is based on methacrylated, star‐shaped oligomers of LA. The main purpose of this work was to evaluate whether this resin can be used to produce structural composites from flax fibers. Composites were prepared by spray impregnation followed by compression molding at elevated temperature. The tests showed that composites can be produced with as much as 70 wt% fiber. The composites were evaluated by tensile testing, flexural testing, charpy impact test, dynamic mechanical thermal analysis (DMTA), and low‐vacuum scanning electron microscopy. The ageing properties in high humid conditions were evaluated, the Young's modulus ranged from 3 GPa to 9 GPa in the best case. This work shows that structural composites can be produced from renewable material. It is clear from the results that these composites have properties that make them suitable for furniture, panels, or automotive parts. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dynamic Mechanical and Thermal Properties of Modified Poly(propylene) Wood Fiber Composites

Dynamic mechanical and thermal properties of poly(propylene) (PP)/wood fiber composites have been studied using Dynamic Mechanical Analysis (DMA). In order to modify the PP matrix maleated poly(propylene) (PPMA) and poly(butadiene‐styrene) rubber were used as compatibilizer and impact modifier, respectively. tan δ peak temperature of the compatibilized systems was found to increase in comparison to that of composites without coupling agent, indicating improved adhesion and interaction between PP matrix and wood fibers. The storage modulus (E′)‐temperature (T) relationship of all composites is characterized by two transition points. The E′ of compatibilized composites exhibits higher values than those of the uncompatibilized ones at low temperatures (up to the β‐relaxation). In the temperature interval from β‐transition to 60 °C, the composites containing PPMA have lower modulus, and above 60 °C the E′‐T curves tend to converge. DSC indicates that the wood fibers act as nucleating agent for PP. Maleated poly(propylene) slightly retards the crystallization rate, resulting in a composite structure, composed mainly of large spherulites, with a higher crystallinity index. Fourier Transform Infrared (FT‐IR) microscopy was also applied to explore the interface between wood fibers and PP matrix. The strong absorption band at 1 738 cm^?1 in the IR spectrum scanned at the interfacial region between the fiber and matrix indicated that PPMA had probably reacted either by formation of ester bonds or hydrogen bonding with hydroxyl groups from cellulose.

Optical micrograph of PPWF composite in polarized light.     

Wood‐fiber‐reinforced poly(lactic acid) composites: Evaluation of the physicomechanical and morphological properties

This article presents the results of a study of the processing and physicomechanical properties of environmentally friendly wood‐fiber‐reinforced poly(lactic acid) composites that were produced with a microcompounding molding system. Wood‐fiber‐reinforced polypropylene composites were also processed under similar conditions and were compared to wood‐fiber‐reinforced poly(lactic acid) composites. The mechanical, thermomechanical, and morphological properties of these composites were studied. In terms of the mechanical properties, the wood‐fiber‐reinforced poly(lactic acid) composites were comparable to conventional polypropylene‐based thermoplastic composites. The mechanical properties of the wood‐fiber‐reinforced poly(lactic acid) composites were significantly higher than those of the virgin resin. The flexural modulus (8.9 GPa) of the wood‐fiber‐reinforced poly(lactic acid) composite (30 wt % fiber) was comparable to that of traditional (i.e., wood‐fiber‐reinforced polypropylene) composites (3.4 GPa). The incorporation of the wood fibers into poly(lactic acid) resulted in a considerable increase in the storage modulus (stiffness) of the resin. The addition of the maleated polypropylene coupling agent improved the mechanical properties of the composites. Microstructure studies using scanning electron microscopy indicated significant interfacial bonding between the matrix and the wood fibers. The specific performance evidenced by the wood‐fiber‐reinforced poly(lactic acid) composites may hint at potential applications in, for example, the automotive and packaging industries. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4856–4869, 2006     

Mechanical and Thermal Properties of Flexible Poly(propylene) Composites

Summary: The melting temperature difference between poly(propylene) (PP) fibre and random poly(propylene‐co‐ethylene) (PPE) was exploited to establish processing conditions for all‐PP composite. Under these conditions, the matrix must be liquid to ensure good wetting and impregnation of fibres, though temperatures must be low enough to avoid melting of fibres. The high chemical compatibility of the two components allowed creation of strong physico‐chemical interactions, favouring strong interfacial adhesion. Static and dynamic mechanical properties and morphology of all‐PP composites were investigated according to method of preparation and compared with the behaviour of hot compacted composites, prepared under different moulding conditions. The composites were compacted with varying pressure and time, and mechanical and thermal properties of the resulting sheets were measured. With increased moulding time, more fibres melted or their original properties deteriorated. Fast cooling or quenching caused imperfect morphology. Moulding pressure played an important role. Morphology of the optimum hot compacted composite was investigated using scanning electron microscopy before and after tensile testing. Tensile fracture surfaces showed a melted phase epitaxially crystallised onto the remaining orientated phase. Compacted composites showed fibre shapes under a thin layer of PPE with all of the gaps between fibres filled by melted PPE matrix.

SEM of compacted all‐PP composite without quenching.     

Preparation and properties of biocomposites composed of glycerol‐based epoxy resins,tannic acid,and wood flour

After polyglycerol polyglycidyl ether (PGPE) and glycerol polyglycidyl ether (GPE) were mixed with tannic acid (TA) in ethanol and without solvent at epoxy/hydroxyl ratio 1/1, the obtained GPE‐TA and PGPE‐TA solutions were mixed with wood flour (WF), prepolymerized at 50°C, and subsequently compressed at 160°C for 3 h to give GPE‐TA/WF and PGPE‐TA/WF biocomposites with WF content 50–70 wt %, respectively. The storage moduli of the biocomposites in the rubbery state at more than 80°C were much higher than that of the control cured resins. The PGPE‐TA/WF composites had higher tensile modulus and rather lower tensile strength than PGPE‐TA. On the other hand, both the tensile modulus and strength of GPE‐TA/WF were much higher than those of GPE‐TA (2.4 GPa and 37 MPa). Those values of GPE‐TA/WF increased with WF content, became maximal values (5.1 GPa and 51 MPa) at WF content 60 wt %, and were lowered at 70 wt %. FE‐SEM analysis of the fractured surface of the biocomposites revealed that WF is tightly incorporated into the crosslinked epoxy resins. As a result of optimization of the epoxy/hydroxyl molar ratio for GPE‐TA/WF composite with WF content 60 wt %, the composite prepared at the ratio of 1.0/0.8 showed the highest tensile modulus and strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanical and Morphological Studies of Poly(propylene)‐Filled Eggshell Composites

Poly(propylene) (PP) composites were prepared by using eggshell (ES) as filler and their mechanical properties were compared with those using talc (TA) and calcium carbonate (CC) of different grain sizes (X₅₀). A decrease in impact strength and deformation at break with increase in filler content was observed. The PP composite with ES (X₅₀ = 8.4 µm) was stiffer than those with CC (X₅₀ = 0.7 µm). The hybrid composite PP‐ES‐TA showed a similar stiffness as the PP‐TA composites due to the similar morphology of TA (X₅₀ = 0.5 µm) and ES, when TA was replaced up to 75 wt.‐% by ES. SEM study revealed evidence of improved interfacial bonding between PP and ES in theirs composites.

     

Ionized‐Air‐Treated Curaua Fibers as Reinforcement for Phenolic Matrices

Curaua fibers were treated with ionized air to improve the fiber/phenolic matrix adhesion. The treatment with ionized air did not change the thermal stability of the fibers. The impact strength increased with increase in the fiber treatment time. SEM micrographs of the fibers showed that the ionized air treatment led to separation of the fiber bundles. Treatment for 12 h also caused a partial degradation of the fibers, which prompted the matrix to transfer the load to a poorer reinforcing agent during impact, thereby decreasing the impact strength of the related composite. The composites reinforced with fibers treated with ionized air absorbed less water than those reinforced with untreated fibers.

     

Ternary Poly(styrene‐co‐acrylonitrile)/Poly(vinyl chloride) Blend Composites with Multi‐Walled Carbon Nanotubes and Enhanced Physical Characteristics

We report a ternary system of poly(styrene‐co‐acrylonitrile) (SAN), poly(vinyl chloride) (PVC), and multi‐walled carbon nanotube (MWCNT) composites prepared by both a solution blending method and the SOAM. The MWCNT content in the composites was optimized by both TGA and mechanical characterization of binary mixtures of SAN/MWCNT and PVC/MWCNT composites. The dispersion of MWCNTs in the miscible SAN/PVC blends was characterized by FT‐Raman spectroscopy, FE‐SEM, and FE‐TEM. The distribution of MWCNTs in the SAN/PVC blends was examined in terms of their wetting coefficients and minimization of the interfacial energy. Composites prepared using the SOAM method showed superior physical properties to the SAN/PVC blends and SAN/PVC/MWCNT composites prepared using the solution blending method.

     

Synergistic Reinforcement of Highly Oriented Poly(propylene) Tapes by Sepiolite Nanoclay

This paper reports the properties of highly oriented nanocomposite tapes based on isotactic PP and needle‐like sepiolite nanoclay, obtained by a solid state drawing process. The intrinsic 1D character of sepiolite allows its exploitation in 1D objects, such as oriented polymer fibres and tapes, where it can be uniaxially oriented upon drawing. A synergistic increase in mechanical properties is presented for highly drawn tapes (λ ≤ 20) and low filler loadings (≤2.5 wt.‐%), which can not be simply explained by micromechanical composite models. Instead, mechanical properties are intimately related to the dispersion state of the nanoclays in PP, the rheological properties of the nanocomposites and the polymer morphology.

     

Potassium‐Based Geopolymer Composites Reinforced with Chopped Bamboo Fibers

Bamboo is a fast‐growing, readily available natural material with tensile specific strength equivalent to that of steel (250–625 MPa/g/cm³). In the pursuit of sustainable construction materials, a composite was made with potassium polysialate siloxo geopolymer as the matrix and randomly oriented chopped bamboo fibers (Guadua angustifolia) from the Amazon region as the reinforcement. Four‐point flexural strength testing of the geopolymer composite reinforced with bamboo fibers was carried out according to ASTM standard C78/C78M‐10^e1. Potassium‐based metakaolin geopolymer reinforced with 5 wt% (8 vol%) untreated bamboo fibers yielded 7.5 MPa four‐point flexural strength. Scanning electron microscopy and optical microscopy were used to investigate the microstructure. In addition, X‐ray diffraction was used to confirm the formation of geopolymer.     

Fabrication and Properties of Vegetable‐Oil‐Based Glass Fiber Composites by Ring‐Opening Metathesis Polymerization

Glass fiber biobased composites have been prepared by ROMP of a commercially available vegetable oil derivative possessing an unsaturated bicyclic moiety, and DCPD. The resins and the corresponding composites have been characterized thermophysically and mechanically. Higher DCPD content yields materials with higher glass transition temperatures. Glass fibers significantly improve the tensile modulus of the resin from 28.7 to 168 MPa. These biobased composites utilize only a limited amount of a petroleum‐based monomer, while employing substantial amounts of a renewable resource.

     

Fabrication of High Performance Fly Ash/Mica/Poly(ether-ether-ketone) Hybrid Composites

This paper deals with the preparation and characterization of poly(ether-ether-ketone) (PEEK) fly ash mica hybrid composites containing filler 5:15, 10:10 and 15:5 fly ash mica combinations loading. The performances and properties of the resulting 20 wt% loading of fly ash mica/PEEK hybrid composites were examined. The resulting hybrid composites of 20 wt% fly ash and mica with varying combinations exhibit the optimum improvement of mechanical properties and dielectric strength. MDSC showed the decrease in the crystallization temperature (Tc) with varying combinations of fly ash and mica. The morphology of fly ash/mica/PEEK hybrid composites was studied by SEM.