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.     

Poly(propylene)/Clay Nanocomposites Prepared by Reactive Compounding with an Epoxy Based Masterbatch

Summary: Poly(propylene) (PP)/clay nanocomposites have been prepared via a novel reactive compounding approach, in which an epoxy based masterbatch consisting of 20 wt.‐% clay was introduced to poly(propylene) with the aid of a maleic anhydride grafted PP (MAPP). The masterbatch was prepared using a recently developed “slurry compounding” technique. After melt compounding, most clay particles have been exfoliated and dispersed into small stacks with several clay layers. WAXD data shows that the dispersion of clay is better at low clay content or high MAPP content. Due to the novelty of the preparation process and complication of the system, the tensile properties of nanocomposites exhibit some unique tendencies with varying the content of MAPP or masterbatch. It is believed that the yield strength and Young's modulus can be dramatically improved after minimizing the excess of unreacted epoxy and optimizing the dispersion of clay.

TEM micrograph of PP/clay nanocomposites prepared with epoxy based masterbatch.     

Influence of Different Woven Geometry in Poly(propylene) Woven Composites

Summary: The difference between the melting temperatures of poly(propylene) (PP) fibre and random poly(propylene‐co‐ethylene) (PPE) was exploited in order to establish processing conditions for an all PP composite. Under these conditions the matrix must be a liquid in order to ensure good wetting and impregnation at the fibres, though the temperature must not be too high to avoid melting the fibres. The high chemical compatibility of the two components allowed creation of strong physico‐chemical interactions, which favour strong interfacial adhesion. The static and dynamic mechanical properties and morphology of poly(propylene) woven fabric reinforced random PPE composites have been investigated with reference to the woven geometry that influenced the properties of the woven composites. Among the various cloth architectures that were used in the PP‐PPE composites, the satin weave imparted overall excellent mechanical properties due to the weave parameters, such as high float length and fibre count, low interlace point and crimp angle, etc. Morphology of the composite has been investigated by macro photography and scanning electron microscopy. Images from scanning electron microscopy provided confirmation of the above results by displaying the consolidation and good fibre‐matrix wetting of the composites.

Loss modulus of poly(propylene) woven‐matrix composites with different types of woven geometry.     

Evaluation of Coupling Agents in Poly(propylene)/Fly Ash Composites: Effect on Processing and Mechanical Properties

Composites containing 50 wt.‐% fly ash in a PP homopolymer were prepared via batch mixing and compression moulding. The following coupling agents were evaluated: Lubrizol Solplus C800, N,N′‐(1,3‐phenylene)dimaleimide, γ‐methacryloxypropyltrimethoxysilane and maleic‐anhydride‐grafted PP. At the filler level investigated, C800 gave the best balance of composite strength and toughness. In the latter case filler‐matrix adhesion appeared weaker relative to γ‐MPS, BMI and m‐PP, all of which gave excessively strong filler‐matrix adhesion leading to a reduction in composite toughness. The unexpected weakness of the C800/fly ash interaction may be related to removal of surface calcium ions from the fly ash via reaction of a single calcium ion with two C800 molecules.

     

Influence of Reactice Processing on the Properties of PP/Glass Fiber Composites Compatibilized with Silane

Summary: Composites of PP reinforced with 20 wt.‐% of short glass fibers were prepared by extrusion using VTES as a coupling agent. The addition of VTES was performed via in‐situ functionalization of PP and by a two‐step process in which PP was functionalized before the composite preparation. The obtained samples were characterized using rheometry, mechanical tests and microscopy. Both processes allowed the fiber/matrix interaction to increase. It was found that the VTES content affected the viscosity of the system by means of three different mechanisms: reduction of β‐scission reactions, decrease of fiber sliding and plasticizing effect on the matrix. Whereas the first two mechanisms increased the viscosity of the final composite after unreacted VTES removal, the third one reduced the viscosity during the process and contributed to fiber‐length preservation. The effects of VTES and peroxide contents on the Young's modulus were closely related to their effects on the final fiber length, indicating the effectiveness of using VTES as a coupling agent. Comparison between in‐situ functionalization and the two‐step process with prefunctionalization showed that in‐situ functionalization led to a lower degree of chain breakage, even when it was performed in the presence of peroxide.

Scanning electron micrographs of PP/glass fiber composite prepared without coupling agent.     

Ethylene Butyl Acrylate Glycidyl Methacrylate Terpolymer as an Interfacial Agent for Isotactic Poly(propylene)/Wood Flour Composites

Summary: This paper presents the results of an experimental investigation concerning the use of an ethylene butyl acrylate and glycidyl methacrylate (EBAGMA) terpolymer as an interfacial agent for isotactic poly(propylene)/wood flour (iPP/WF) composites at various filler ratios (10, 20 and 30 wt.‐%). The effects of the EBAGMA terpolymer on the morphology, tensile properties, impact strength and water uptake of the iPP/WF composites were studied and the results were compared with those obtained with maleated poly(propylene) (MAPP) used as a compatibilizer. Initially, the mixing process was performed in a calendaring unit at 170 °C for pre‐homogenization of the filler in the matrix. Composites made out of these combinations were then ground and injected into a standard mold at 180 °C in the absence and the presence of compatibilizer. The results indicated that both EBAGMA terpolymer and MAPP improved the interactions between iPP and WF, and induced a better dispersion of wood particles in the polymer matrix, as revealed by scanning electron microscopy (SEM). Furthermore, tensile properties and impact strength were also increased. Another important effect was on the water absorption property, which was significantly lower for the samples with EBAGMA and MAPP. However, EBAGMA terpolymer produced better enhancement of the properties of the iPP/WF composites compared to the compatibilized samples with MAPP.

SEM micrographs of the fracture surface of iPP/WF composites (70/30 wt.‐%): (a) without compatibilizer; (b) with 10 pph EBAGMA; (c) with 10 pph MAPP. Magnification was ×500.     

Investigation Into Poly(propylene)/Montmorillonite/Calcium Carbonate Nanocomposites

Summary: A novel method was used to prepare poly(propylene)/montmorillonite/calcium carbonate nanocomposites by melt‐mixing, using pristine montmorillonite (MMT), hexadecyltrimethylammonium bromide (C16), calcium carbonate (CaCO₃) and a matrix in a twin‐screw extruder. Two different sizes of calcium carbonate were used (nanosized CaCO₃ and micron‐sized CaCO₃, the average sizes being 60 nm and 12 μm respectively). The nanocomposite structure was evidenced using X‐ray diffraction (XRD), transmission electron microscopy (TEM) and high resolution electronic microscopy (HREM). Tensile tests and Izod notch impact tests suggested that the incorporation of nanosized CaCO₃ into PP/montmorillonite nanocomposites increased the mechanical properties of the composites, but the improvement in the micro‐sized CaCO₃‐filled PP/montmorillonite nanocomposites was found to be minimal. The thermal stability and flammability properties were characterized by thermogravimetric analysis (TGA) and a cone calorimeter respectively.

     

Preparation and Characterization of Polycarbonate/Poly(propylene)/Attapulgite Ternary Nanocomposites with the Morphology of Encapsulation

Summary: Ternary nanocomposites based on polycarbonate (PC), poly(propylene) (PP), and attapulgite (AT) were prepared via the method of two‐step melt blending, by which the AT was blended with PP prior to compound with PC. Structure and properties of the ternary PC/PP/AT nanocomposites were investigated. The degradation of PC triggered by AT during direct blending process can be inhibited effectively by using two‐step melt blending. It was found that the morphology of encapsulation structure like sandbag was formed in PC matrix, where PP encapsulated AT fibrillar single crystals. DSC experiments showed that in PC/PP/AT ternary nanocomposites, AT had a strong heterophase nucleation effect on PP, resulting in the enhancement of crystallization degree and the crystallization temperature of PP. DMA and mechanical property results showed that the ternary nanocomposites exhibited good balanced toughness and stiffness.

TEM photograph of PC/PP/AT ternary nanocomposite.     

A Reactive Flame Retardant as a Poly(propylene)‐Sized Glass Adhesion Promoter

Summary: Contact‐mode AFM adhesion strength measurements were employed in order to investigate the capability of PBBMA FR as an adhesion promoter in PP composites. The reactive FR exhibited superior coupling properties in comparison to conventional coupling agents such as PP‐g‐ma introduced in reinforced PP composites.

AFM image showing the recess carved out by the AFM tip in a PBBMA layer deposited on glass treated with APS.     

Grafting of Hindered Amine Stabilizer in Poly(propylene) Films under γ‐Irradiation

Summary: In this paper, the grafting of a hindered amine stabilizer (HAS) is studied in isotactic poly(propylene) (PP) films under γ‐irradiation. The HAS used has a definite structure that combines a hindered amine functionality and a UV‐absorbing unit (benzylidene malonate ester group) detectable at 308 nm in the UV spectrum of PP film and 314 nm in chloroform. The stabilizer is added to the polymer at various concentration ratios: 0.1, 0.2, and 0.3 wt.‐%. The percentage of HAS grafting in the PP film at various additive concentrations is determined as a function of γ‐radiation dose in the range of 0–100 kGy by direct spectroscopic measurements through the absorption band of the stabilizer in the UV spectra of the PP film. The percentage of free HAS extracted with chloroform from the PP film versus the radiation dose is determined by UV spectroscopy for all the additive concentrations used. This study reveals that only 80% of the HAS is grafted on the 100 kGy irradiated PP matrix independent of the additive concentration used. However, the percentage of HAS grafted on PP films displays an exponential dependence on γ‐radiation dose. These results are consistent with the data obtained on the free HAS content. γ‐Irradiation grafting of HAS in the PP is accompanied by the oxidative degradation of the polymer substrate that is evaluated by increasing the carbonyl index and reducing significantly the oxidation induction time of the PP films.

The percentage of hindered amine stabilizer grafted to the PP film as a function of γ‐radiation dose.     

Influence of Low‐Molecular‐Weight Diamines in the Direct Imidation of Poly(propylene)‐Grafted Maleic Anhydride by Melt Reaction

Aminated poly(propylene) was prepared by reacting aliphatic primary diamines with maleic‐anhydride‐functionalized poly(propylene) by in situ melt reaction. Around 60–70% of the initial acid groups had reacted to form amide and imide groups as confirmed by the almost complete disappearance of the maleic anhydride peak in FT‐IR spectra. The molecular weight of the diamines had an influence on changes in molecular structure of the PP‐g‐NH₂ as a result of secondary reactions such as chain extension and cross‐linking. PP‐g‐NH₂ and polycarbonate were pressed into two‐layer films and their adhesion strength was measured. The results showed that PP‐g‐NH₂ was a very effective adhesion promoter.

     

The Effect of Particle Matrix Adhesion on the Mechanical Properties of Silica Filled Cyanate Ester Composites

Summary: The effect of silica and its surface treatment on the mechanical properties of composites was studied as part of the evaluation of cyanate ester matrices as potential electronic encapsulants. Three filler surface treatments were used, as a qualitative interfacial adhesion scale, in an attempt to gauge the magnitude of interfacial adhesion between untreated filler and the cyanate ester matrix. There was strong interfacial adhesion between matrix and untreated filler. The level of silica content most affected composite modulus and fracture toughness. Filler surface treatment most affected composite strength and fracture toughness/energy. Composite fracture was found to occur via crack pinning and/or crack blunting depending on the strength of adhesion. The composites evaluated were found to possess suitable mechanical properties for potential use as electronic encapsulants.

     

Polybenzimidazolium‐Based Solid Electrolytes

A series of methyl, benzyl, and mixed polybenzimidazolium halides was synthesised and characterised by NMR spectroscopy. Membranes were formed and ion exchanged with hydroxides. These membranes are of interest for use in potentially platinum‐free anionic exchange membrane fuel cells. Crosslinked membranes were obtained by the addition of α,α′‐dibromo‐p‐xylene to the casting solution. The ion conductivity of membranes was determined by impedance spectroscopy. A hydroxide conductivity of 29 mS · cm^?1 at 26 °C and 58 mS · cm^?1 at 60 °C was obtained. The thermal and hydrolytic stability was investigated and a pathway for hydrolytic degradation proposed. Hydroxide ions react at the 2 position, the intermediate carbinol opens to the amine–amide, and further degrades under chain scission to diamine and carboxylic acid.

     

Interpenetrating Polymer Networks of Hydrocarbon and Fluorocarbon Polymers: Epoxy/Fluorinated Acrylic Macromonomers

A fluorinated acrylic resin was synthesized for use as a co‐monomer with a commercially available epoxy resin for UV‐cured interpenetrating polymer network preparation. Hybrid IPN networks were achieved with morphology ranging from a co‐continuous IPN to complete phase separation simply by changing monomer ratios. Highly hydrophobic coatings with good adhesion properties on glass substrates were obtained.

     

Comparative Characterization of PP Nano‐ and Microcomposites by In‐Mold Shrinkage Measurements and Structural Characteristics

Poly(propylene)‐clay nanocomposites and poly(propylene) containing conventional inorganic fillers such as calcium carbonate (CaCO₃) and glass fiber were used in a comparative study focusing on dimensional stability, structure, mechanical and thermal properties. Micro‐ and nanocomposites were prepared by melt blending in a twin‐screw extruder. The relative influence of each filler was observed from dimensional stability measurements and structural analysis by WAXD, TEM, and thermal and mechanical properties. At equal filler loadings, PP/clay nanocomposites exhibit an improvement in dimensional stability and were the only composites capable of reduced shrinkage in both in‐flow and cross‐flow directions. The flexural modulus of PP increased nearly 20% by compounding with 4% organoclay, as compared to a similar performance obtained by compounding with 10 wt.‐% of CaCO₃ or approximately 6 wt.‐% of glass fiber. The HDT and thermal stability of PP were enhanced by using nanoclay as filler.

     

Regenerative Recycling of Automotive Polymer Components: Poly(propylene) Based Car Bumpers

There is a dramatic loss in the mechanical performances at the end of the first life application of bumpers made by a poly(propylene) matrix (PP) and an ethylene‐propylene rubber copolymer as dispersed phase. The use of specific additives during the recycling strongly enhances the mechanical properties of these items. The on purpose designed additive contained a regenerative agent and an antioxidant system. The mixing action of the recycling process re‐establishes the phase compatibility; the antioxidants inhibit oxidation, which speeds up the degradation reactions in the recycling process; eventually the regenerative agent joins short chains possessing suitable reactive groups. These three effects play a different role in restoring original material performance in dependence of the recycling process: for instance the regenerative agent may be nearly useless if chain scission is not the dominant process in the recycling operation and the interfacial adhesion between rubber and the matrix does not assure automatically a ductile mechanical behaviour under impact conditions.

SEM micrograph of the fractured surface of the used bumper recycled with additives.     

A New Biodegradable Flexible Composite Sheet from Poly(lactic acid)/Poly(ε‐caprolactone) Blends and Micro‐Talc

The influence of talc loading on phase morphology of PLA/PCL/talc composites and improvement in resulting properties are reported. Talc‐based composites of PLA/PCL blends were prepared by melt blending. SEM analysis demonstrates that PLA appears as discrete domain phase, while PCL acts as a bulk phase in the blend. Talc addition decreases PLA domain sizes and voids in the matrix. This results in significant improvement of oxygen and water vapor barrier properties of composite by 33 and 25%, respectively, at 3 wt.‐% talc loading. DSC shows that talc acted as nucleating agent for PCL phase in the composite and improves its crystallinity. Various theoretical models based on dispersion and filler geometry are used to predict the tensile modulus and oxygen permeability.

     

Ex Situ Solvent‐Assisted Preparation of Magnetic Poly(propylene) 8nocomposites Filled with Fe@FeO Nanoparticles

Isotactic PP nanocomposites filled with Fe@FeO nanoparticles are fabricated by a facile ex situ method. The nanofillers are dispersed in a boiling PP/xylene solution. X‐ray diffraction is used to determine the nanofiller effects on the crystallinity of PP. The crystallinity along the (040) plane is found to decrease with the incorporation of nanoparticles. Thermal properties and crystallinity are studied by TGA and DSC, respectively. Enhanced thermal stability and influenced crystallinity are observed in the PP nanocomposites compared with those of pure PP. An increased dielectric property without percolation threshold is observed. In addition, the nanocomposites are found to exhibit ferromagnetic properties.

     

Factors Effecting the Performance of Montmorillonite/Magnesium Hydroxide/Poly(propylene) Ternary Composites, 1

A two‐level factorial experimental design was used to examine the combined effects of o‐MMT gallery polarity, surface modification of MDH, MA‐g‐PP and antioxidant addition, together with processing variables, on the burning behaviour and thermal stability of ternary composites based on PP, MDH and o‐MMT. Regression equations highlighted the detrimental effect of o‐MMT intercalants and possible improvement in the dispersion of o‐MMT at higher MDH levels. A polar gallery environment (providing quat OH groups) led to increased char formation, and MA‐g‐PP combined with o‐MMT led to a higher oxidation onset temperature. Addition of o‐MMT to PP/MDH composites can lead to a reduction in the level of MDH required for effective flame retardation.