Transcrystallinity in Surface Modified Aramid Fiber Reinforced Nylon 66 Composites

Aramid (kevlar‐49) fibers were surface treated by two different methods to induce roughness and then used to produce unidirectional nylon 66 based composites. The transcrystallinity generated around the treated fibers was characterized by SEM and polarized light microscopy and compared with the regular transcrystalline layers produced by pristine aramid under the same processing conditions. The treated fibers generated a double transcrystalline layer, the inner layer being thinner and more compact than the regular nylon 66 transcrystallinity. In addition, mechanical testing of the composites showed the longitudinal Young's modulus of the treated fiber composites to be significantly higher than the control in a wide range of fiber volume fractions.

Polarized light microscopy picture of double transcrystallinity in Br/NH₃ treated aramid fiber reinforced nylon 66.     

Mechanical and Thermal Properties of Poly(L‐lactide) Incorporating Various Inorganic Fillers with Particle and Whisker Shapes

Poly(L ‐lactide) (PLLA) composites incorporating various inorganic fillers (ifR‐PLA) were prepared by the melt blending technique, and their mechanical and thermal properties were evaluated. The filler types influenced the mechanical properties of ifR‐PLA; for those incorporating particle‐ and whisker‐type fillers the tensile moduli were 3.1–3.7 and 3.7–4.5 GPa, respectively, and the flexural moduli were 4.1–4.8 and 4.8–6.1 GPa. It was found that the tensile strength and modulus, as well as the flexural modulus, of ifR‐PLA incorporating whisker‐type fillers increased in proportion to the volume percent of the fillers (V_f). The flexural strength of ifR‐PLA incorporating 9Al₂O₃ · 2B₂O₃ whiskers showed a similar increase, while that of ifR‐PLA incorporating CaCO₃ whiskers showed a decrease with increasing V_f. This difference may be because the 9Al₂O₃ · 2B₂O₃ with its large aspect ratio kept its original fibrous shape, while the CaCO₃ lost its fibrous shape during the blending process. However, the reinforcing effect of these fillers was relatively low compared with that known for the corresponding composites of the conventional polymeric materials, probably because of the poor surface adhesion of PLLA to the fillers.

Comparison of effect on storage moduli of different fillers.     

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).     

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).     

Well‐Controlled Microcellular Biodegradable PLA/Silk Composite Foams Using Supercritical CO2

PLA biodegradable composites reinforced with various silk fibroin powder contents (0, 1, 3, 5 and 7 wt.‐%) were prepared by solution processing technique using CH₂Cl₂ as solvent. After that the composites and virgin PLA were foamed by using supercritical CO₂. The influence of silk contents on PLA/silk fibroin powder composite foams were investigated by using SEM, XRD and DSC. Compared with PLA foam, the composite foams exhibited a reduction in cell size and increase in cell density at high silk content. With an increase in saturation temperature and pressure, the cell size was increasing and both the cell density and foam density were decreased simultaneously.

     

Intercalated Polycarbonate/Clay Nanocomposites: Nanostructure Control and Foam Processing

Intercalated polycarbonate (PC)/clay nanocomposites (PCCN)s have been prepared successfully through the melt intercalation method in the presence of a compatibilizer. The internal structure and morphology of the PCCNs has been established by using wide‐angle X‐ray diffraction (WAXD) analyses and transmission electron microscopic (TEM) observations. The morphology of these nanocomposites and degradation of the PC matrix after nanocomposites preparation can be controlled by varying surfactants used for the modification of clay and compatibilizer. The intercalated PCCNs exhibited remarkable improvements of mechanical properties when compared with PC without clay. We also discuss foam processing of one representative PCCN using supercritical CO₂ as a foaming agent.

TEM bright field image of intercalated polycarbonate/synthetic fluorohectorite nanocomposite.     

Effect of Maleated Compatibilizer on Performance of PLA/Wheat Straw‐Based Green Composites

In this study, the use of PLA‐g‐MA is investigated as a potential method for improving interfacial adhesion between agricultural residues and PLA, with the goal of enhancing mechanical properties. Compatibilization was achieved by using PLA‐g‐MA prepared via reactive extrusion. Green renewable and compatibilized PLA/wheat straw composites were extruded and injection‐molded. Addition of 3 and 5 phr PLA‐g‐MA to the composites resulted in significant improvements in tensile strength (20%) and flexural strength (14%) of the composites, matching that of the neat polymer. The observed improvement in strength was attributed to the good interfacial adhesion between the fiber and matrix.

     

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.

     

Control of Biodegradability of Polylactide via Nanocomposite Technology

Polymer/layered silicate nanocomposite technology is not only suitable for the significant improvement of mechanical and various other materials properties of virgin polymers, it is also suitable to enhance the rate of biodegradation of biodegradable polymers such as polylactide. The biodegradability of polylactide in nanocomposites completely depends upon both the nature of pristine layered silicates and surfactants used for the modification of layered silicate, and we can control the biodegradability of polylactide via judicious choice of organically modified layered silicate.

Biodegradation of neat PLA and various PLA/OMLS nanocomposites recovered from compost with time.     

Dynamic Mechanical and Thermal Properties of Phenylethynyl‐Terminated Polyimide Composites Reinforced With Expanded Graphite Nanoplatelets

Summary: This article reports on the dynamic mechanical and thermal properties of thermosetting phenylethynyl‐terminated polyimide (PETI‐5) composites reinforced with expanded graphite (EG) nanoplatelets having various average particle sizes and content. The EG nanoplatelets with varying particle sizes were prepared by different pulverization techniques through intercalation and exfoliation of natural graphite flakes. The effect of the EG particle size and concentration of the thermal behavior of PETI‐5/EG composites was investigated with several thermal analysis methods (DMA, TMA, and DSC). The storage modulus dynamic mechanical properties and glass transition temperature significantly increased with increasing concentration of EG nanoreinforcements regardless of size. The coefficient of thermal expansion significantly decreased, especially in the glass transition region.

     

Tensile Fracture and Failure Behavior of Thermoplastic Starch with Unidirectional and Cross‐Ply Flax Fiber Reinforcements

Thermoplastic starch (MaterBi®) based composites containing flax fibers in unidirectional and crossed‐ply arrangements were produced by hot pressing using the film stacking method. The flax content was varied in three steps, viz. 20, 40 and 60 wt.‐%. Static tensile mechanical properties (stiffness and strength) of the composites were determined on dumbbell specimens. During their loading the acoustic emission (AE) was recorded. Burst type AE signal characteristics (amplitude, width) were traced to the failure mechanisms and supported by fractographic inspection. The mechanical response and failure mode of the composites strongly depended on the flax content and the flax fiber lay‐up. It was established that the tensile strength increases until 40 wt.‐% flax fiber content but stays almost constant above this value. In the case of 40 wt.‐% unidirectional fiber reinforcement, the tensile strength of the composite was 3 times greater than that of the pure starch matrix. The flax fiber reinforcement increased the tensile modulus of the pure starch by several orders of amplitude.

SEM picture of the fracture surface of a composite with UD flax reinforcement.     

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.

     

Novel High‐Strength Thermoplastic Starch Reinforced by in situ Poly(lactic acid) Fibrillation

In recent years TPS has attracted more and more research interest as a promising replacement for commodity polymers in some applications. In this paper, a novel manufacturing technology to produce PLA fiber reinforced biodegradable TPS composite, and the microstructure and tensile properties of the composite, were first reported. PLA micro/sub‐micro fibers were generated in situ by elongational flow during die extrusion and subsequent hot stretching. The addition of 10% PLA significantly increased the drawability of TPS. Compared to direct extrusion, hot stretching tripled the tensile strength of the composite to 34 MPa. Extensive PLA fibrillation was evident in the composite. The generated PLA fibers measured ca. 400 nm in diameter with a large L/D ratio.

     

Flexural Behaviour of Fibre‐Reinforced Syntactic Foams

Summary: Syntactic foams containing 0.9, 1.76, 2.54, 3.54 and 4.5 vol.‐% of E‐glass fibres in the form of chopped strands were processed and subjected to three‐point bending tests. The results showed that introduction of chopped strand fibres into the syntactic foam system increased the flexural strength. The values increased with the amount of fibres in the foam system except for the one containing 3.5 vol.‐% of fibres, which showed a lower value than other fibre‐reinforced systems, thereby deviating from the trend. This exception was attributed to the difference in processing route adopted for this particular fibre‐bearing foam. However, in general, the incorporation of chopped strand fibres improved the flexural behaviour of the syntactic foam system without much variation in density, thus making reinforced syntactic foams to act as better and improved core materials for sandwich applications.

Fibre‐debonding and protuberance, and river pattern in a failed sample.     

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.

     

Thermoplastic Polyurethane Nanocomposites Produced via Impregnation of Long Carbon Nanotube Forests

TPU was infiltrated into vertically aligned, 3.5 mm‐long MWNT forests to produce continuously reinforced anisotropic nanocomposites, and thermomechanical and electrical testing has revealed multifunctionality which shows promise for numerous applications. A 1000% increase in the storage modulus at 70 °C was observed as compared to the neat TPU, and these continuously aligned composites showed electrical conductivity two orders‐of‐magnitude greater (≈1.5 S · cm^?1) than randomly aligned composites prepared using CNTs from these forests. The heightened improvement for the continuously reinforced composite appears to be owed to the extremely high aspect ratio of these CNTs and the interconnected network which remains after infiltration.

     

Microcellular Foamed Wood‐Plastic Composites by Different Processes: a Review

Wood fiber reinforced polymer composites represent a relatively small but rapidly growing material class, extensively applied in interior building applications and in the automotive industry. The polymer‐wood fiber composites utilize fibers as reinforcing filler in the polymer matrix and are known to be advantageous over the neat polymers in terms of the materials cost and mechanical properties such as stiffness and strength. Wood fiber reinforced polymer composites are microcellularly processed to create a new class of materials with unique properties. Most manufacturers are evaluating new alternatives of foamed composites that are lighter and more like wood. Foamed wood composites accept screws and nails like wood, more so than their non‐foamed counterparts. They have other advantages such as better surface definition and sharper contours and corners than non‐foamed profiles, which are created by the internal pressure of foaming. This paper represents a review on microcellular wood fiber reinforced polymer composites obtained by different processes (batch, injection molding, extrusion, and compression molding process) and includes an overview of foaming agents (physical and chemical) and the foaming of wood fiber‐polymer composites (changes in phase morphology, formation of polymer‐gas solution, cell nucleation, and cell growth control).

     

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.

     

High Temperature Thermosets With a Low Coefficient of Thermal Expansion

Summary: Polymeric thermosetting composites can be used as metal substitutes for certain applications if they possess high temperature stability in air, low coefficient of thermal expansion (CTE), and sufficient flexural strength, in combination with competitive costs. Commercial bismaleimide, bisnadimide, and cyanate ester thermosetting materials were selected due to their excellent thermal stability. Low CTEs were achieved by adding high loading levels of fused silica or silicon nitride fillers. Several optimized composites were fabricated by varying the materials, composition, and cure conditions. Characteristic composite properties, such as CTE, thermal stability, glass transition temperature (T_g), flexural strength, and filler distribution were investigated. The best system developed consists of Matrimide 5292, a commercial two‐component bismaleimide resin, filled with 75% Silbond FW100EST, and additionally reinforced with 0.5% Twaron short fibers. This composite is distinguished by a CTE around 15 ppm · K⁻¹, a T_g around 340 °C, flexural strength above 100 MPa, and attractive material costs.

Matrimid 5292 (75%)/Silbond FW100AST (24.5%), and Twaron 2 mm short fibers (0.5%). Three fibers are visible, embedded and well dispersed in the matrix.     

From PET Nanofibrils to Nanofibrillar Single‐Polymer Composites

The preparation of nanofibrillar composite (NFC) materials using single‐polymer nanofibrils as starting materials is described. Such a possibility is offered by (i) the concept of polymer/polymer NFCs, which have recently been manufactured and represent a further development in the field of microfibril‐reinforced composites, and (ii) the opportunity to isolate neat nanofibrils through selective dissolving of the second blend component. The resulting nanofibrillar single‐polymer composites are characterized by superior mechanical properties (the tensile modulus and strength are improved up to 350%), competing with glass‐fiber‐reinforced PET.