Resin–Sisal and Wood Flour Composites Made from Unsaturated Polyester Thermosets

Short fibers and wood flour were selected as fillers in the production of two types of unsaturated polyester composites (bisphenolic and isophthalic-based thermosets). Sisal fibers were subjected to washing in order to remove the organic coating on the fibers (which were originally prepared for cord manufacture) and to maleic anhydride (MAN) esterification. The effect of these treatments on the thermomechanical properties of the composites, as well as on the mechanical properties (flexural and compression) and water absorption was investigated. All the results are coincident in showing the improved interfacial adhesion obtained by washing and mainly by esterification of the fibers. Additionally, hybrid wood flour sisal composites were prepared and their mechanical properties compared to those of the one-filler composites. The hybrid composites showed improved modulus and maximum stress.     

Effect of Fiber Surface Modification on the Interfacial and Mechanical Properties of Kenaf Fiber-Reinforced Thermoplastic and Thermosetting Polymer Composites

The surfaces of kenaf fibers were treated with three different silane coupling agents. 3-glycidoxypropyltrimethoxy silane (GPS), 3-aminopropyltriethoxy silane (APS), and 3-methacryloxypropyltrimethoxy silane (MPS). Among them, the most effective one for the property improvement was GPS when it was applied to the kenaf fiber surfaces at 0.5 wt%. Thermoplastic polypropylene (PP) and thermosetting unsaturated polyester (UPE) matrix composites with chopped kenaf fibers untreated and treated at different GPS concentrations from 0.1 wt% to 5 wt% were fabricated using compression molding technique. The present study demonstrates that the interfacial, flexural, tensile, and dynamic mechanical properties of both kenaf/PP and kenaf/UPE composites importantly depend on the GPS treatments done at different concentrations. The greatest property improvement of both thermoplastic and thermosetting polymer composites was obtained with the silane treatment at 0.5 wt% and the mechanical properties were comparable with E-glass composites prepared the same polymer matrix under the corresponding fiber length and fiber loading. The results also agreed with each other with regard to their interfacial shear strength, flexural properties, tensile properties, storage modulus, with support of fracture surfaces of the composites.     

Effect of Inorganic Fillers on Morphology and Mechanical Properties of PA66/POE-g-MAH/Filler Composites

Composites of polyamide 66 (PA66)/maleic anhydride grafted poly(ethylene-co-octene) (POE-g-MAH)/nano-calcium carbonate (nano-CaCO₃) and PA66/POE-g-MAH/talc were prepared by a one-step blending method. Morphology, crystallization, and mechanical properties of the composite materials were characterized with respect to different amounts of both inorganic fillers, nano-CaCO₃ and talc. Results showed that the tensile yield strength and tensile modulus of the composites were increased remarkably with introduction of nano-CaCO₃ or talc, but the notched impact strength was significantly lowered for both kinds of composites. Mechanical properties exhibited little difference between the PA66/POE-g-MAH/nano-CaCO₃ and PA66/POE-g-MAH/talc composites both for the different shapes and sizes of nano-CaCO₃ and the flake-like talc. Results of scanning electron microscopy exhibited agglomeration of the fillers. Differential scanning colorimetry analysis suggested that introduction of the inorganic fillers cause the crystallinity of PA66 to decrease by heterogeneous nucleation. The study provides a basic investigation on polymer/elastomer/rigid filler composites.     

Studies on interface in polyester/fly-ash particulate composites

Fly ash (FA)-general purpose unsaturated polyester resin (GPR) particulate composites have been made. The effect of surface treatment of FA with two different silane coupling agents (CAs) on the mechanical properties like tensile, flexural, impact strength and hardness, thermal properties like thermal stability and morphological properties (SEM) of FA-GPR composites are studied. The properties of FA-CA-GPR are also compared with that of GPR and CaCO₃ -GPR. An enhancement in the tensile, flexural, and impact strength and moduli are observed when FA is surface treated with CA. Hardness is also found to increase with CA-treated FA-filled GPR. A suitable mechanism for the chemical reaction taking place at the interface in the presence of CAs is proposed.     

Mechanical strength and thermal stability of magnesium silicate filled polypropylenes

Mineral fillers are widely used to improve the mechanical properties of polypropylene, but at the same time they may cause some degradation of polymer, especially if the stabilization is insufficient. Two different kinds of silicate minerals, talc and serpentinite, were used as fillers for homo- and copolypropylene, and their influence on mechanical properties and degradation was investigated. The mechanical properties of filled polypropylene were tested at room temperature using tensile and impact tests. GC-MS technique was used to characterize the degradation of compounds. The results revealed differences in the mechanical properties: talc filled polypropylene had higher tensile strength, rigidity and impact strength properties than serpentinite filled. The oxidation stability of filled polypropylene measured by the oven method showed lower values in the case of serpentinite filled polypropylene. In the beginning of pyrolysis there was no significant difference between talc and serpentinite filled polypropylene in the formation of degradation products, as was observed by GC-MS. In a slightly higher temperature and longer incubation time PP-serpentinite compound started to form more small molecular weight degradation products than PP-talc due to stronger catalytical effects of the serpentinite surfaces. The characterization methods used here provided us new information to understand the role of mineral fillers in degradation processes. The results of DSC measurement yielded information on the effects of the filler crystallization and thermal degradation. Talc, for example, was shown to be better nucleation agent than serpentinite for PP.     

Improving the properties of polypropylene–wood flour composites by utilization of maleated adhesion promoters

Polymer composites filled with natural organic fillers have gained a significant interest during the last few years, because of several advantages they can offer compared with properties of inorganic-mineral fillers. However, these composites (based, in most cases, on polyolefins) often show a reduction in some mechanical properties. This is mainly due to the problems regarding dispersion of the polar filler particles in the non-polar polymer matrix and their interfacial adhesion with polymer chains. In this work, polypropylene–wood flour composites were prepared and the effect of the addition of a maleated polypropylene was investigated. The two materials were compounded by an industrial co-rotating twin screw extruder, with two different compositions, without and with addition of Licomont AR504^® (maleic anhydride-grafted polypropylene wax). The extruded material was then compression molded, which provided the specimens for tensile and impact tests. Water uptake was measured; the morphology of the fracture surfaces of the samples coming out from mechanical tests was investigated through SEM analysis. Rheological characterization was carried out as well. The addition of the adhesion promoter allowed a decrease in water uptake; mechanical properties were improved as well, especially elastic modulus and tensile strength; impact strength increased in the case of unnotched samples, while notched ones did not show remarkable differences. SEM analysis of the fracture surfaces also showed an overall change in the morphology as a consequence of the utilization of the adhesion promoter.     

Effect of Filler Treatment on Crystallization,Morphology and Mechanical Properties of Polypropylene/Calcium Carbonate Composites

Pimelic acid (PA) was used as a new surface modifier for CaCO₃. The effects of PA treatment on the crystallization, morphology, and mechanical properties of PP/CaCO₃ composites were investigated. Fourier transform infrared (FTIR) spectroscopy analysis revealed that PA bonded to CaCO₃ and formed a calcium pimelate surface layer after reacting with CaCO₃. The results of wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), and polarized light microscopy (PLM) proved that the PA treated CaCO₃ induced a large amount of β -iPP and decreased the spherulitic size of PP. The results of scanning electron microscopy (SEM) showed that the PA treatment enhanced the interfacial adhesion between the filler and the matrix, indicating the improvement of the compatibility between PP and CaCO₃. The toughness of the composites was improved by the more ductile β -form spherulites. When 1% of PA treated CaCO₃ was added, the notched impact strength reached its maximum, a value of 19.79 kJ/m², which was 3.64 times greater than that of the pure PP.     

Discontinuous basalt and glass fiber reinforced PP composites from textile prefabricates: effects of interfacial modification on the mechanical performance

Spun and blown basalt fibers and their PP matrix composites were investigated. The composites were manufactured by hot pressing technology from carded and needle punched prefabricate using PP fiber as matrix material. Glass and blown basalt fibers were treated with reaction product of maleic acid-anhydride and sunflower oil while spun basalt fibers had a surface coating of silane coupling agent. Fibers were investigated with tensile tests while composites were subjected to static and dynamic mechanical tests. The results show that blown basalt fibers have relatively poor mechanical properties, while spun basalt fibers are comparable with glass fibers regarding geometry and mechanical performance. The static and dynamic mechanical properties of glass and spun basalt fiber reinforced composites are similar and are higher than blown basalt fiber reinforced composites. Results were supported with SEM micrographs.     

Effect of interfacial debonding and matrix cracking on mechanical properties of multidirectional composites

In composites, debonding at the fiber–matrix interface and matrix cracking due to loading or residual stresses can effect the mechanical properties. Here three different architectures — 3-directional orthogonal, 3-directional 8-harness satin weave and 4-directional in-plane multidirectional composites — are investigated and their effective properties are determined for different volume fractions using unit cell modeling with appropriate periodic boundary conditions. A cohesive zone model (CZM) has been used to simulate the interfacial debonding, and an octahedral shear stress failure criterion is used for the matrix cracking. The debonding and matrix cracking have significant effect on the mechanical properties of the composite. As strain increases, debonding increases, which produces a significant reduction in all the moduli of the composite. In the presence of residual stresses, debonding and resulting deterioration in properties occurs at much lower strains. Debonding accompanied with matrix cracking leads to further deterioration in the properties. The interfacial strength has a significant effect on debonding initiation and mechanical properties in the absence of residual stresses, whereas, in the presence of residual stresses, there is no effect on mechanical properties. A comparison of predicted results with experimental results shows that, while the tensile moduli E ₁₁, E ₃₃and shear modulus G ₁₂ match well, the predicted shear modulus G ₁₃ is much lower.     

Thermal Stabilities of Poly(Vinyl Chloride)/Calcium Carbonate (PVC/CaCO3) Composites

Poly(vinyl chloride)/calcium carbonate (PVC/CaCO₃) composites with micrometer or nanometer CaCO₃ as fillers were prepared by the solution blending method. The thermogravimetric analysis (TGA) of the composite films conducted in N₂ atmosphere showed that the addition of the CaCO₃ fillers could improve their thermal stabilities. It was also found that the nanometer CaCO₃ filler provided better thermal stabilities than the micrometer fillers even with a smaller amount. The mechanism of the improvements was investigated by a facile chemical analysis developed to examine the thermal stabilizing effect of calcium carbonate particles with different sizes in PVC/CaCO₃ composites after the pyrolysis of the samples in an air atmosphere in an oven.     

Composites from Brazilian natural fibers with polypropylene: mechanical and thermal properties

Brazil has a well established ethanol production program based on sugarcane. Sugarcane bagasse and straw are the main by-products that may be used as reinforcement in natural fiber composites. Current work evaluated the influence of fiber insertion within a polypropylene (PP) matrix by tensile, TGA and DSC measurements. Thus, the mechanical properties, weight loss, degradation, melting and crystallization temperatures, heat of melting and crystallization and percentage of crystallinity were attained. Fiber insertion in the matrix improved the tensile modulus and changed the thermal stability of composites (intermediary between neat fibers and PP). The incorporation of natural fibers in PP promoted also apparent T _c and ΔH _c increases. As a conclusion, the fibers added to polypropylene increased the nucleating ability, accelerating the crystallization process, improving the mechanical properties and consequently the fiber/matrix interaction.     

Calcium Sulfate as High-Performance Filler for Polylactide (PLA) or How to Recycle Gypsum as By-product of Lactic Acid Fermentation Process

Reinforcing of polylactide (PLA) with fillers can be an interesting solution to reduce its global price and to improve specific properties. Starting from calcium sulfate (gypsum) as by-product of the lactic acid fermentation process, novel high performance composites have been produced by melt-blending PLA and this filler after a previous specific dehydration performed at 500°C for min. 1 h. Due to PLA sensitivity towards hydrolysis, it has first been demonstrated that formation of β-anhydrite II (AII) by adequate thermal treatment of calcium sulfate hemihydrate is a prerequisite. Then, the modification of filler interfacial properties with different coating agents such as stearic acid (SA) and stearate salts has been considered. The effect of surface treatment on molecular, thermal and mechanical properties has been examined together with the morphology of the resulting composites. To take advantage of the improved lubricity and better wetting characteristics, the filler was coated by up to 2% (by weight) SA. The coating of the filler leads to PLA–AII composites that surprisingly exhibit thermal stability, cold crystallization and enhanced impact properties. Such remarkable performances can be accounted for by the good filler dispersion as evidenced by SEM–BSE imaging of fractured surfaces. As far as tensile proprieties are concerned, notable utilization of uncoated filler or filler coated by stearate salts leads to PLA–AII composites characterized by higher tensile strength and Young's modulus values. The study represents a new approach in formulating new melt-processable grades with improved characteristic features by using PLA as polymer matrix.     

Lignocellulosic composites with grafted polystyrene interfaces

The effects of surface grafting of a polymer onto lignocellulosic fiber surface and processing methods on both the interfacial interactions and the resulting composite properties of the fiber-reinforced thermoplastic composites were investigated. Chemithermomechanical pulp (CTMP) wood fiber was used as a reinforcement, which has been chemically modified by radical polymer grafting of styrene onto the fiber surfaces. The chemically modified CTMP fiber was then compounded with polystyrene (PS). Two different processing methods, both compression and injection moldings, were performed to prepare the wood-fiber-reinforced composites. Experimental results showed that surface modification of wood fiber leads to an obvious increase in mechanical properties of the fiber-reinforced composites as compared to the untreated fiber composites. The enhancement of mechanical properties is much greater through injection molding compared with compression molding owing to occurrence of orientation, and better mixing and interaction between the fiber and the matrix by injection molding. An improvement in fiber wetting properties and adhesion by the matrix was observed through scanning electron microscopy for the surface grafted fiber reinforced composites. Untreated wood fiber exhibited a smooth surface without adhered polymer, indicating poor adhesion, while polymer attached to the surface was seen on treated cellulose fiber due to the higher fiber-matrix interactions.     

Nanocomposites Prepared by Solution Blending: Microstructure and Mechanical Properties

Composites of poly(vinyl chloride) (PVC) filled with micron‐ and nanosized calcium carbonate (CaCO₃) particles were prepared by solution blending. The influences of particle size and CaCO₃ content on the microstructure and mechanical properties of the PVC composites were investigated by means of polarized optical microscopy and mechanical testing. The polarized optical microscope images revealed that nanosized CaCO₃ particles were more agglomerated than micron‐sized CaCO₃ particles and the amount of agglomerates increased with increasing particle content. PVC/CaCO₃‐0.22 composites (PVC nanocomposite filled with 220‐nm‐particle‐sized CaCO₃) 5 phr CaCO₃ content had the maximum tensile strength. The Young's modulus of all composites increased with increasing particle content. The energy at break of all composites showed a decreasing trend as a function of CaCO₃ content and varied with particle size.     

Dielectric properties of short sisal/coir hybrid fibre reinforced natural rubber composites

The dielectric properties, such as dielectric constant, volume resistivity and dielectric loss factor, of sisal/coir hybrid fibre reinforced natural rubber composites have been studied as a function of fibre loading, fibre ratio, frequency, chemical modification of fibres and the presence of a bonding agent. The dielectric constant values have been found to be higher for fibre filled systems than pure natural rubber. This has been attributed to the polarization exerted by the incorporation of fibres into the matrix. Dielectric constant values were observed to be decreased with increase in frequency due to the decreased interfacial and orientation polarization at higher frequencies. Whereas dielectric constant increases with fibre loading because of the increment in number of polar groups after the addition of hydrophilic lignocellulosic fibres. The volume resistivity of the composites was found to be decreased with fibre loading and a percolation threshold has been obtained at 15.6% volume of fibres. Fibre treatment, such as alkali, acetylation, benzoylation, peroxide and permanganate, were carried out to improve the adhesion between fibres and matrix. The dielectric constant values were lower for systems consisting of fibres subjected to chemical treatments due to the increased hydrophobicity of fibres. The addition of a two-component dry bonding agent consisting of hexamethylene tetramine and resorcinol, used for the improvement of interfacial adhesion between the matrix and fibres, reduced the dielectric constant of the composites. When the weight percentage of sisal fibre was increased in the total fibre content of the hybrid composites, the dielectric constant was found to increase. The added fibres and different chemical treatments for them increased the dielectric dissipation factor. A dielectric relaxation has been observed at a frequency of 5 MHz.     

Influence of gelatin on the properties of hydroxyapatite–polyacrylamide nanocomposite as a potential bone substitute

The controlled integration of organic and inorganic components confers superior mechanical properties onto natural bone. The present work adds to the continuing efforts of designing a natural bone-like structure. In this study, the hydroxyapatite (HAP) impregnated polymeric composites of polyacrylamide (PAM) and the same with gelatin have been synthesized by a suspension polymerization method in order to study their blood compatibility, water sorption behavior, and mechanical properties; and network parameters, such as average molecular weight between crosslinks (M _c), crosslink density (q) have been calculated. Both, HAP–PAM and PAM–gelatin–HAP composites were characterized using techniques like Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) studies, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The composites were also evaluated for their mechanical properties like compressive strength and modulus (E).     

Modification of Wood Flour Surfaces by Esterification with Acid Chlorides: Use in HDPE/Wood Flour Composites

Modification of wood fiber/flour (WF) surfaces can improve their compatibility with hydrophobic plastic matrices and reduce composite water uptake. WF was esterified with octanoyl chloride and palmitoyl chloride. Modified WF was analyzed by FT-IR. More extensive esterification occurred in highly polar dimethylformamide (DMF) than in much less polar CHCl₃ or methyl tert-butyl ether (MTBE). DMF penetrates into the fiber far more than CHCl₃ or MTBE, making more –OH groups available for esterification. Increasing the acid chloride chain length from C₈ to C₁₆ decreased the mole fraction of esterification. Longer chains cover surface –OH groups, retarding reactions with nearby hydroxyls after esterification. Longer chain acid chlorides also have lower reactivity and penetrate into the hydrophilic wood fiber more slowly. Modified wood flour surfaces were covered by a hydrophobic layer of ester groups (SEM). Modified wood flour surfaces and WF/HDPE composite fracture surfaces were studied by SEM. C₈-modified wood flour (60 wt%)/HDPE composites exhibited far less water absorption after 24 h and 216 h immersions compared with unmodified WF (60 wt%)/HDPE composites. Water absorption continues over the 216 h period. Esterified WF/HDPE composites exhibited lower flexural strengths and moduli. In contrast to C₈-esterification, the addition of maleated polypropylene (MAPP) to WF/HDPE composites improved composite mechanical performance and gave similar water absorption properties to C₈-esterified WF composites.     

Thermal Properties and Fire Resistance of Jute-Reinforced Composites

The thermal behaviour, fire resistance and mechanical properties of jute-reinforced composites with vinylester and resol matrix were studied. Organically modified clay was added to the polymeric matrix in order to enhance the properties of the composites. An inhomogeneous distribution of the nanoreinforcement in the polymer was observed by X-ray diffraction. Thermogravimetric analyses revealed that the addition of clay to the resol resin by sonication enhanced the thermal resistance of the jute-reinforced composite at temperatures higher than 300°C. The fire resistance of the composites was evaluated by means of a cone calorimeter. A diminution in the peak of the heat release rate was observed when clay was added to the polymeric matrix. On the other hand, neither the time to ignition nor the total heat evolved was significantly reduced by the clay addition. Additionally, an increment in the flexural modulus as well as in the flexural strength of the resol composites was observed when the clay was added to the matrix. The fiber–matrix interface of the composites was studied by scanning electron microscopy. It was observed that as the clay dispersion degree was increased the interface quality was diminished in the resol composites.     

Interphase phenomena in superconductive polymer-ceramic nanocomposites

Dynamic mechanical properties (elastic moduli, phase angle) for superconducting (SC) polymer–ceramic composites based on Y₁Ba₂Cu₃O_7?x SC oxide ceramic and superhighmolecular polyethylene have been investigated. The analysis of the obtained data shows a strong interaction of the polymeric binder with the surface of the ceramic grains. It is concluded that changes of packing and structure of the macromolecules occur at the ceramic–polymer interface. This is confirmed by melting enthalpy measurements of SC polymer–ceramic composites of different filler content. Scanning electron microscopy studies of the high temperature SC composites showed that the ceramic grains are evenly covered by the binder for both amorphous and crystalline polymers. EPR (electron paramagnetic resonance) spectra of polymer–ceramic composites have shown that the intensity of the EPR signals of Cu²⁺(1) depends on the nature and the content of binder. The Mn, Co, Zn, Ni containing superconducting composites have been obtained by frontal polymerization.     

Polymer‐filler derived ceramics with low shrinkage using PCS/SiC/Al mixture

Active Al and inert SiC powders were dispersed in the polycarbosilane to manufacture SiC ceramic composites by a new process of active‐filler‐controlled pyrolysis of polymer. 40 wt% of active Al fillers, 40 wt% of inert SiC fillers and 20 wt% of PCS, were homogenized. The samples were obtained by pyrolysis at 1100 °C for different soaking time. The results showed that due to the incorporation of active Al fillers, formation of crystallite phases such as Al₄C₃, Al₄Si₃ and AlN occured due to the of reaction of Al particles with the polymer decomposition products and the reactive nitrogen atmosphere. The microstructural and mechanical characterization results of the composites are presented in the paper. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)