Processing,Structure, and Properties of PAN/MWNT Composite Fibers

Conventional dry‐jet wet fiber spinning techniques were used to fabricate continuous PAN/MWNT composite fibers with up to 20 wt.‐% nanotube loading. PAN at the MWNT interface exhibited lower solubility under thermodynamically favorable conditions than in bulk PAN, indicating good interfacial interaction. Due to the PAN/MWNT interaction at the interface, thermal shrinkage decreases with increasing MWNT loading (5 to 20 wt.‐%). For high MWNT loadings, PAN/MWNT composite fiber at 15 wt.‐% MWNT loading showed an axial electrical conductivity of 1.24 S · m^?1. For all loadings, PAN/MWNT composite fibers exhibited higher tensile moduli than theoretically predicted by rule‐of‐mixture calculations, suggesting good reinforcement of the PAN by MWNT.

     

Properties of Poly(3‐hydroxybutyric acid) Composites with Flax Fibres Modified by Plasticiser Absorption

Natural fibre‐biopolymer composites have been prepared from flax and polyhydroxybutyrate (PHB). The flax was modified by drying, followed by plasticiser absorption to replace the water lost to prevent embrittlement. This protects the fibres from problems associated with their water content and changes in water content due to equilibration with the environment. Flax and PHB showed good interfacial adhesion, which was decreased when plasticisers were present. Some plasticiser migrated from the flax to PHB and caused complex changes in the glass transition, crystallisation and crystallinity of the PHB. Morphology of the composites was examined by scanning electron microscopy (SEM) and optical microscopy (OM), SEM provided information on the interfacial adhesion through fractography. OM showed extensive transcrystallinity along the fibre surfaces. Dynamic mechanical analysis was used to measure elastic and damping characteristics and their relation to composition and morphology.

SEM micrograph of the PHB‐plasticiser‐flax system PHB‐PEG‐flax.     

Biocomposites Made from Short Abaca Fiber and Biodegradable Polyesters

Natural fiber‐reinforced biodegradable polyester composites were prepared from biodegradable polyesters and surface‐untreated or ‐treated abaca fibers (length ca. 5 mm) by melt mixing and subsequent injection molding. Poly(butylene succinate)(PBS), polyestercarbonate (PEC)/poly(lactic acid)(PLA) blend, and PLA were used as biodegradable polyesters. Esterifications using acetic anhydride and butyric anhydride, alkali treatment, and cyanoethylation were performed as surface treatments on the fiber. The flexural moduli of all the fiber‐reinforced composites increased with fiber content. The effect of the surface treatment on the flexural modulus of the fiber‐reinforced composites was not so pronounced. The flexural strength of PBS composites increased with fiber content, and esterification of the fiber by butyric anhydride gave the best result. For the PEC/PLA composites, flexural strength increased slightly with increased fiber content (0–20 wt.‐%) in the case of using untreated fiber, while it increased considerably in the case of using the fiber esterified by butyric anhydride. For the PLA composite, flexural strength did not increase with the fiber reinforcement. The result of soil‐burial tests showed that the composites using untreated fiber have a higher weight loss than both the neat resin and the composites made using acetylated fiber.

Flexural modulus of PBS composites as a function of fiber content.     

A Review on Pineapple Leaf Fibers,Sisal Fibers and Their Biocomposites

Summary: The use of lignocellulosic fibers, pineapple leaf fiber (PALF) and sisal as reinforcements in thermoplastic and thermosetting resins for developing low cost and lightweight composites is an emerging field of research in polymer science and technology. Although, these biofibers have several advantages, such as low densities, low cost, nonabrasive nature, high filling level possible, low energy consumption, high specific properties, biodegradability, etc., over synthetic fibers, the absorption of moisture by untreated biofibers, poor wettability, and insufficient adhesion between the polymer matrix and fiber deteriorate the mechanical properties of composites made up of these biofibers. Therefore, the modification of these fibers is a key area of research at present to obtain optimum fiber‐matrix properties. This review article is concerned with the structure, composition and properties of PALF and sisal, the chemical modifications of these fibers and PALF/sisal‐reinforced thermosets, thermoplastics, rubber, cement, hybrids and biocomposites.

Scanning electron micrograph of tensile fractured surface of alkali treated sisal fiber (magnification ×500).     

Influence of Screw Speed on Electrical and Rheological Percolation of Melt‐Mixed High‐Impact Polystyrene/MWCNT Nanocomposites

The influence of screw speed on the electrical and rheological percolation of HIPS/MWCNT composites prepared via melt mixing was investigated. Microscopic examination of these composites using POM, FESEM and HRTEM revealed optimum MWCNT dispersion was achieved at intermediate screw speeds. On addition of MWCNTs to HIPS, the electrical conductivity of HIPS increased by up to 12 orders of magnitude. At screw speeds up to 100 rpm an electrical percolation of 1–3 wt.‐% was achieved. This increased to 3–5 wt.‐% when the screw speed was increased to 150 rpm. The onset of a rheological percolation was detected for an MWCNT loading of 5 wt.‐%, irrespective of screw speed employed. An up‐shift in the Raman G‐band of 24 cm^?1 was observed, implying strong interfacial interaction between HIPS and MWCNTs.

     

Laccases to Improve the Whiteness in a Conventional Bleaching of Cotton

This study reports for the first time on the enhancement of the bleaching effect achieved on cotton using laccase enzyme. Laccases applied in short‐time batchwise or pad‐dry processes prior to conventional peroxide bleaching, improved the end fabric whiteness. The whiteness level reached in the combined enzymatic/peroxide process was comparable to the whiteness in two consecutive peroxide bleaches.

Effect of 10 min laccase pre‐treatment at 60 °C, pH 5 on fabrics whiteness before and after a conventional hydrogen peroxide bleaching.     

Functionalized Graphene–PVDF Foam Composites for EMI Shielding

Novel foam composites comprising functionalized graphene (f‐G) and polyvinylidene fluoride (PVDF) were prepared and electrical conductivity and electromagnetic interference (EMI) shielding efficiency of the composites with different mass fractions of f‐G have been investigated. The electrical conductivity increases with the increase in concentration of f‐G in insulating PVDF matrix. A dramatic change in the conductivity is observed from 10^?16 S · m^?1 for insulating PVDF to 10^?4 S · m^?1 for 0.5 wt.% f‐G reinforced PVDF composite, which can be attributed to high‐aspect‐ratio and highly conducting nature of f‐G nanofiller, which forms a conductive network in the polymer. An EMI shielding effectiveness of ≈20 dB is obtained in X‐band (8–12 GHz) region and 18 dB in broadband (1–8 GHz) region for 5 wt.% of f‐G in foam composite. The application of conductive graphene foam composites as lightweight EMI shielding materials for X‐band and broadband shielding has been demonstrated and the mechanism of EMI shielding in f‐G/PVDF foam composites has been discussed.

     

Sheet‐Molded Polyolefin Natural Fiber Composites for Automotive Applications

The use of natural fibers as reinforcing filler in thermoplastics is a relatively new application and has great potential in replacing glass fiber products in automotive industry. However, most of the research in this area has been focused primarily on flax fiber. In the first part of the work presented here, hemp fiber non‐woven mats are used exclusively in combination with a poly(propylene) matrix to study the mechanical properties of natural fiber mat thermoplastics (NMT) in the absence of binder. Film stacking was used as the method of preparation. The results show that hemp‐based NMT have comparable or even higher strength properties as compared with conventional flax‐based thermoplastics. A value of 63 MPa for the flexural strength is achieved at a fiber content of 64 wt.‐%. The influence of the compression ratio on the mechanical properties and density of NMT is also reported. A definite increase in strength is observed with increasing compression together with a much more uniform density profile. In the second part of this study, a unique combination of random hemp fibers, non‐woven mats and poly(propylene) films was employed in film stacking to evaluate strength properties and economic implications. The same fiber content (64 wt.‐%) was maintained in the final NMT by replacing 78 wt.‐% of the mats by random fibers. Preliminary tests reveal better mechanical properties especially in terms of impact energy, which is 50 to 100% higher, as compared with different mats‐only/poly(propylene) combinations. Further, a net saving of 40% in fiber cost is anticipated by replacing 78% non‐woven mats with an equivalent amount of random fibers. Overall results of this study indicate that hemp‐based NMT are promising candidates in automotive applications where high specific stiffness is required.

Tensile Strength of different NMTs and GMT.     

Novel Glass Fiber‐Reinforced Composites Having a UV and Peroxy Curable Fluoropolymer Matrix

Novel glass fiber‐reinforced composites were prepared from E‐glass fibers and perfluoropolyether (PFPE), polyurethane acrylate, and methacrylate resins. The PFPE resins were synthesized by a two‐step process and formulated with reactive acrylic diluents obtaining two compositions with different viscosity and fluorine content. These formulations were photocrosslinked by UV‐A radiation and characterized by tensile and dynamic‐mechanical properties as well as by impact resistance. The two UV cured fluoropolymer compositions are high modulus (> 1 GPa), polyphasic materials characterized by a fracture toughness higher than conventional polymer matrices, like epoxies and unsaturated polyesters. Unidirectional laminate composites were also prepared by hand lay‐up and crosslinked both photochemically and thermally. Mechanical characterization of glass fiber‐reinforced composites was carried out by tensile tests and shear adhesion measurements, showing a good fluoropolymer‐glass adhesion strength (ca. 9 MPa). Surface characterization of composites by static contact angle measurements allowed the calculation of the total surface tension γ_s according to Wu's harmonic mean approximation. Surface tension is very low (< 20 mN/m) suggesting a preferential stratification of PFPE segments at the material‐air interface.

     

Polymeric Toughening of Particle Filled Cyanate Ester Composites

Summary: The present study examines the effect of polymeric tougheners on the performance of silica filled cyanate ester composites. The polymeric tougheners used have been shown to enhance cyanate ester tougheners in binary toughener/matrix systems. Tougheners that were able to form a favourable phase‐separated morphology resulted in the greatest increase in crack resistance. The addition of these tougheners resulted in minimal loss of strength, and a slight decrease in modulus. Importantly the viscosity of the compounded systems was low enough for them to be readily processable. Whilst conserving most secondary properties, toughener addition did result in a slight increase in composite hydrolytic degradation. This issue was linked to the additive/ additive compounding processes. Removal of this extra moisture should eliminate this concern, permitting the used of these composites in electronic applications.

Effect of ETBN content on the crack resistance of particle filled cyanate ester composites and SEM image of 15 matrix wt.‐% ETBN.     

Preparation and Characterization of Organic/Inorganic Polymer Composites Based on Mg‐Silicates

Summary: An organic‐inorganic hybrid material consisting of a 3‐(methacryloxy)propyl functionalized SiO₂/MgO framework was synthesized. This hybrid was successfully reacted with styrene, butyl acrylate and butyl methacrylate via a free radical emulsion polymerization to form polymer composites. The polymer composites were investigated by means of FT‐IR spectroscopy, TGA, DSC and rheometry. It is shown that the polymer is linked covalently to the organic/inorganic hybrid. Although the polymer content is rather low, the composites exhibit a polymer‐like character and enhanced mechanical properties compared to the corresponding homopolymers.

     

The Anisotropy of Fibrillar Silicate/Rubber Nanocomposites

Summary: Fibrillar silicate (FS)/rubber nanocomposites were successfully prepared by directly mixing modified FS with rubber matrix. It is found that FS could be separated into nano‐fibrils with diameters less than 100 nm by the shear forces during mixing. The stress‐strain characteristics of these composites are similar to those for short micro‐fiber/rubber composites (SFRC). Nevertheless, these FS/rubber composites have some outstanding advantages over the conventional SFRC, even though the reinforcing effect of FS is restricted due to its small shape aspect ratio. More importantly, the differences in mechanical properties of the composites in the two different directions show that SBR/FS and NBR/FS composites both exhibit obvious anisotropy, which strongly depends on the preparation process, FS concentration, and rubber matrix. These factors were thoroughly investigated in this paper, and it can be concluded that the anisotropy of the composites was due to the orientation of nano‐fibrils.

     

Preparation and Mechanical Properties of Long Glass Fiber Reinforced PA6 Composites Prepared by a Novel Process

Summary: Long glass fiber reinforced PA6 (LGF/PA6) prepregs were prepared by impregnating PA6 oligomer melt into reinforcing glass fiber followed by subsequent solid‐state polymerization (SSP) to obtain LGF/PA6 composite pellets. A conventional injection‐molding machine suitable for short glass fiber reinforced composites was applied to the processing of the prepared composites, which reduced the fiber length in the final products. Mechanical properties, thermal property, and fiber length distribution of injection molding bars were investigated. Scanning electron microscopy (SEM) was used to observe the impact fracture surfaces and the surfaces of glass fiber after the SSP. It was found that the LGF/PA6 composites were of favorable mechanical properties, especially the impact strength, although the average length of glass fiber was rather short. By this novel process, the content of glass fiber in composite could be high up to 60 wt.‐% and the maximum level of heat distortion temperature (HDT) was close to the melting temperature of PA6. SEM images indicated the favorable interfacial properties between the glass fiber and matrix. The glass fiber surfaces were further observed by SEM after removing the matrix PA6 with a solvent, the results showed that PA6 macromolecules were grafted onto the surface. Furthermore, the grafting amount of PA6 was increased with SSP time.

SEM images of impact fracture surfaces of LGF/PA6 composites (left) and of glass fiber surfaces after removing PA6 with 5 h SSP (right).     

Methionine‐Containing Poly(amino acid) Hybrid Fibers via Self‐Assembly at Aqueous Interface

Summary: Using sulfonium groups to create a novel fiber material, methionine‐containing hybrid fibers were prepared from S‐methylated poly(L ‐methionine) and poly(L ‐lysine, L ‐methionine) solutions with gellan solution by polyion complex (PIC) formation via self‐assembly at the aqueous interface. The breaking strain of the PIC fibers were increased by incorporation of methionine residues into the poly(L ‐lysine). These findings may provide a new approach for preparing a wool‐like fiber in aqueous media using the synthetic water‐soluble methionine‐containing poly(amino acid)s.

SEM image of Met‐containing PIC fiber: (a) poly[Met¹⁹Met(SMe)⁸¹]‐gellan fiber (magnification, ×500).     

Blends of a Main Chain Liquid‐Crystalline Polyester with a Diepoxide and with a Diepoxide/Amine Mixture Prepared in a Twin‐Screw Extruder

Summary: Blending of the commercial LC‐polyester Rodrun LC‐3000 with the bisphenol‐A‐diglycidyl ether based diepoxide DOW D.E.R.330 alone and with the mixture of the diamine (MCDEA) and D.E.R.330 by means of a twin‐screw extruder has been investigated. Conditions to suppress curing of epoxide and amine during blending have been established. Due to the very low solubility of Rodrun in the diepoxide only LCP‐rich blends with a minimum content of 60 wt.‐% Rodrun could be obtained. The blends were investigated by SEM and thermal analysis (DSC, DMTA). Binary blends are immiscible while ternary blends appear miscible from DMTA up to 30 wt.‐% of epoxy/amine.

SEM micrograph of Rodrun moulded at 230 °C.     

Hydroxyapatite Reinforced Chitosan and Polyester Blends for Biomedical Applications

Summary: Hydroxyapatite, chitosan, and aliphatic polyester were compounded using a twin‐screw extruder. The polyesters include poly(ε‐caprolactone) (PCL), poly(lactic acid) , poly(butylene succinate) (PBS), and poly(butylene terephthalate adipate). The mass fraction of chitosan ranged from 17.5 to 45%, while that of HA ranged from 10 to 30%. These blends were injection molded and evaluated for thermal, morphological, and mechanical properties. The addition of hydroxyapatite decreased the crystallinity in chitosan/PBS blends, while in blends containing chitosan/PCL, the crystallinity increased. Addition of hydroxyapatite significantly decreased the tensile strength and elongation of polyester/hydroxyapatite composites as well as chitosan/polyester/hydroxyapatite composites with elongations undergoing decreases over an order of magnitude. The tensile strength of the composite was dictated by the adhesion of HA to the chitosan/polyester matrix. The tensile strength of composites containing hydroxyapatite could be predicted using the Nicolai and Narkis equation for weak filler adhesion (K ≈ 1.21). Tensile‐fractured and cryogenically‐fractured surface indicates extensive debonding of hydroxyapatite crystals from the matrix, indicating weak adhesion. The adhesion of hydroxyapatite was higher for pure polyester than those containing chitosan and polyester. The modulus of the composites registered modest increase. The two main diffraction peaks observed using WAXS are unaffected by the amount of chitosan or hydroxyapatite.

     

A New Network Composite Material Based on Soy Dreg Modified with Polyurethane Prepolymer

A series of biodegradable, soy‐protein‐based, composite materials was prepared by introducing castor‐oil‐based polyurethane prepolymer (PUP) into soy dreg (SD) without the addition of plasticizers, via extrusion and a compression‐molding process. The effects of the NCO/OH molar ratio and the PUP content on the structure and properties of the resulting materials were studied by Fourier‐transform infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry, dynamic mechanical thermal analysis, tensile testing, swelling experiments, and biodegradability testing. The results revealed that the ? NCO group in the PUP played a vital role in improving the compatibility and elasticity, as a result of the formation of a cross‐linking network structure with the ? NH₂, ? NH, and ? OH groups in SD containing protein and cellulose. Increasing the NCO/OH molar ratio to 2.0 resulted in an enhancement of the degree of cross‐linking, leading to a higher tensile strength (24 MPa), glass‐transition temperature (52 °C) and water‐resistivity of the composite materials. The unreacted SD also served as a filler in the cross‐linked networks and enhanced the tensile strength of the composites. The biodegradation testing showed that the composites exhibited biodegradability under the condition of fungus culture.

     

An NMR‐MOUSE® for Analysis of Thin Objects

A special unilateral NMR sensor has been designed for investigations of thin samples with a thickness of less than 1 mm and of surface effects of polymers. For use with the bar‐magnet NMR‐MOUSE®, the so‐called “crazy coil” is introduced with a low penetration depth. It is a flat meander coil etched on a printed circuit board with wiggles in the conductors. The design of the new coil and FEM simulations of the B ₁ field are presented. Different applications are discussed by means of illustrative examples. They are the detection of surface damage in rubber samples, the swelling and drying of a latex membrane exposed to cyclohexane vapor mimicking a chemical sensor, and the drying of a thin sprayed adhesive layer.

Bar‐magnet NMR‐MOUSE® with crazy coil.     

A Model for the Elastoplastic Behavior of Isotactic Poly(propylene) Below the Yield Point

Observations are reported on isotactic poly(propylene) (iPP) in a series of tensile loading‐unloading tests with a constant strain rate at room temperature. A constitutive model is developed for the elastoplastic behavior of a semicrystalline polymer at isothermal uniaxial deformations with small strains. The stress‐strain relations are determined by 5 adjustable parameters which are found by fitting the experimental data.

The stress σ (MPa) versus strain ε in a tensile loading‐unloading test with the maximum strain ε_max = 0.09. Circles: experimental data. Solid line: results of numerical simulation.     

The Reinforcement of Elastomeric Networks by Fillers

Summary: The mechanisms involved in rubber reinforcement are discussed. A better molecular understanding of these mechanisms can be obtained by combining characterization of the mechanical behavior with an analysis of the chain segmental orientation accompanying deformation. While the strain dependence of the stress is the most common quantity used to assess the effect of filler addition, experimental determination of segmental orientation can be used to quantify the interfacial interactions between the elastomeric matrix and the mineral inclusions.

SEM micrograph of natural rubber containing 10 wt.‐% of organomodified clay.