Structural,Electrical, Mechanical,and Thermal Properties of Electrospun Poly(lactic acid)/Polyaniline Blend Fibers

Conducting electrospun fiber mats based on PLA and PAni blends were obtained with average diameter values between 87 and 1 006 nm with PAni quantities from 0 to 5.6 wt.‐%. Structural characteristics of fiber mats were compared to cast films with the same amount of PAni and studied by SEM, SAXS, and AFM. Thermal properties of fiber mats and cast films were compared by DSC analyses. Mechanical properties of fiber mats were also evaluated. It was found that electrospinning process governs the crystal structure of the fibers and strongly affects fiber properties. New properties of PLA/PAni blends are reported due to the size fiber reduction.

     

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).     

Structure Property Correlation of Thermally Treated Hemp Fiber

Summary: Hemp (Cannabis sativa L.) is an important ligno‐cellulosic raw material for the manufacture of cost‐effective environmentally friendly composite materials. Hemp plant samples of different initial condition (stem and bast fibers) were subjected to heating varying the temperature (from 160 to 260 °C) and the ambient heating environment (air and inert atmosphere). Weight measurements showed that all heat treatment resulted in a reduced weight of hemp. Those treated in air showed drastic decline in weight compared with those treated under nitrogen, especially at a temperature higher than 220 °C. Observation using optical and scanning microscope showed the possibilities of opening up of the fiber bundles in both heating environments. However, higher temperature and presence of air had a more severe effect on fibers and associated tissues compared to effects under nitrogen. Heat treatment at 220 °C under nitrogen seemed to provide enough fiber opening without affecting tissues of the fibers.

SEM micrograph of the cross‐section of hemp fiber heat treated in air environment.     

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.     

Ultrafine Electrospun Polyamide‐6 Fibers: Effects of Solvent System and Emitting Electrode Polarity on Morphology and Average Fiber Diameter

Summary: In the present contribution, polyamide‐6 (PA‐6) solutions were prepared in various pure and mixed‐solvent systems and later electrospun with the polarity of the emitting electrode being either positive or negative. The PA‐6 concentration in the as‐prepared solutions was fixed at 32% w/v. Some of the solution properties, i.e., shear viscosity, surface tension, and conductivity, were measured. Irrespective of the polarity of the emitting electrode, only the electrospinning of PA‐6 solution in formic acid (85 wt.‐% aqueous solution) produced uniform electrospun fibers, while solutions of PA‐6 in m‐cresol or sulfuric acid (either 20 or 40 wt.‐% aqueous solution) did not. In the mixed‐solvent systems, formic acid (85 wt.‐% aqueous solution) was blended with m‐cresol, sulfuric acid (either 20 or 40 wt.‐% aqueous solution), acetic acid, or ethanol in the compositional range of 10–40 vol.‐% (based on the amount of the minor solvent). Generally, the average fiber diameter increased with increasing amount of the minor solvent or liquid. Interestingly, the diameters of the fibers obtained under the negative electrode polarity were larger than those obtained under the positive one.

Optical images of electrospun fibers from solutions of polyamide‐6 in a mixed solvent of 85 wt.‐% formic acid and 20 vol.‐% m‐cresol under positive (left) and negative (right) electrode polarity.     

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.     

Cover: Macromol. Mater. Eng. 3/2005

Summary: A novel human hair protein hybrid fiber was developed by combining (i) the high‐efficiency extraction technique for preparing human hair proteins and (ii) the watery hybridization spinning method using gellan and chitosan. The resulting human hair protein‐gellan‐chitosan hybrid fibers are conveniently produced by simply mixing the 7–35 wt.‐% human hair protein‐1.0 wt.‐% gellan aqueous solution and the 1.0 wt.‐% chitosan‐0.15 M acetic acid solution at 50 °C, followed by pulling out to spin the human hair protein‐gellan‐chitosan ternary complex thus formed at the aqueous solution interface. By use of this simple procedure and ambient spinning condition, the human hair proteins were successfully incorporated into the fiber matrix of gellan‐chitosan, without any denaturation and degradation. The hybrid fiber can also be recognized as a new type of the regenerated human hair keratin fiber, because of its high purity and content of human hair keratin types I and II. Mechanical strength of the human hair protein‐gellan‐chitosan fiber varies from 108 to 153 MPa, depending on the contents of the human hair proteins. SEM observation revealed that the incorporated human hair proteins were found as the particles (1–10 μm) on the fiber surface. The type I and II keratins in the fiber matrices were rapidly biodegraded by chymotrypsin within 30 min, and the digested fragments slowly released from the fiber matrices. Thus, the human hair hybrid fiber is a very promising material to have a broad spectrum of applications as the engineering fibers, particularly for the medical uses, because the human hair proteins are easily available, biocompatible, and bioresorbable materials.

Gellan‐chitosan hybrid fiber (a), human hair protein‐gellan‐chitosan hybrid fiber (b).     

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.

     

Preparation of Nano‐Polyethylene Fibers and Floccules by Extrusion Polymerization Under Atmospheric Pressure Using the SBA‐15‐Supported Cp2ZrCl2 Catalytic System

Summary: Nano‐polyethylene fibers and floccules were prepared under atmospheric pressure via ethylene extrusion polymerization in suit, using the SBA‐15‐supported Cp₂ZrCl₂ catalytic system. The major morphology units in the samples were fibers and floccules. The diameter of the single nano‐fibers was 120–200 nm. The single nano‐fibers could aggregate to form fiber aggregates and bundles. The number of PE floccules increased with extension of polymerization time, while the melting point of PE with nano‐fibers was little higher than that of common polyethylene.

SEM micrograph of the nano‐polyethylene fibers produced at a polymerization time of 60 min: micro‐fibers and floccule surface morphologies.     

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.     

Fabrication of Aligned Poly(L‐lactide) Fibers by Electrospinning and Drawing

A new target collector was designed for taking up aligned nanofibers by electrospinning. The collector consists of a rotor around which several fins were attached for winding electrospun filaments continuously in large amounts. The alignment of the nanofibers wound on the collector was affected by the electrospinning conditions, such as the needle‐to‐collector distance and the applied voltage, but not by the rotation speed of the collector. At a voltage of 0.5 kV · cm^?1, about 60% of the fibers were found to be aligned within an angle of ± 5° relative to the rotational direction of the collector. The fiber alignment was improved to 90% by drawing the fiber bundle 2–3 times at 110 °C. The drawing was also effective for crystal orientation of the fibers as revealed by WAXD. The drawn fibers show improved mechanical properties.

     

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).     

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.     

Phenolic Thermoset Matrix Reinforced with Sugar Cane Bagasse Fibers: Attempt to Develop a New Fiber Surface Chemical Modification Involving Formation of Quinones Followed by Reaction with Furfuryl Alcohol

Summary: A new chemical modification of sugar cane bagasse fibers for phenolic thermoset composites is presented. It consists in creating quinones in the lignin portions of fiber and react them with furfuryl alcohol to create a coating around the fiber more compatible with the phenolic resins used to prepare polymeric matrix. Sodium periodate was used in suitable conditions to oxidize mainly phenolic syringyl and guaiacyl units of the lignin polymer to create quinones, which were characterized by UV‐visible diffuse reflectance spectroscopy by comparison with model compounds. The reactivity of furfuryl alcohol (FA) with fibers was greatly enhanced after they were oxidized: 13% weight percent gain compared to 2% without oxidation. Chemical analysis of unmodified and FA‐modified fibers have shown an important degradation of hemicelluloses and a slight one of cellulose which almost maintains its crystallinity. A 25% decrease of strength and length properties of the fibers after FA chemical treatment was measured by dynamic mechanical analysis. The lignin‐like proportion of the fiber was greatly enhanced after the FA‐treatment. This was confirmed by thermal analysis, DSC, and TGA experiments, on unmodified and FA‐modified fibers. SEM analysis of the fibers and of phenolic composites with modified fibers have confirmed the FA grafting and shown a better compatibility at the interface between the chemically modified fibers and the phenolic matrix. Nevertheless, the chemical treatment of the fibers decreased the impact strength of the composite, which could be caused by the fiber damage suffered during the chemical modification and for the more intense adhesion at the interface, which in some cases decrease somewhat the impact strength.

Cross photomicrography of FA‐modified sugar cane bagasse fiber (600×).     

Poly(ethylene oxide)‐block‐poly[2‐(dimethylamino)ethyl methacrylate] as Strengthening Agent in Paper: Dynamic Mechanical Characterization

To enhance adhesion properties of PEO on wood fibers, block polymers of PEO and 2‐(dimethylamino)ethyl methacrylate were synthesized. The polymers were further modified to obtain strongly cationic species. The resulting polymers were used as additives in paper sheets. Papers were studied by DMA in a controlled‐humidity chamber. Addition of the PEO block co‐polymers enhanced paper strength. The strength of the paper sheets was highest when polymer with molecular weight of 400 kg · mol^?1 was used as an additive. Highly cationic block co‐polymers increased moduli of paper sheets more than their weakly cationic analogs, which indicated strong interaction with fiber surfaces. Strength of the paper sheets decreased both with increased temperature and humidity.

     

Morphology,Thermal and Mechanical Properties of Poly(propylene) Fibre‐Matrix Composites

Preparation and properties of poly(propylene)‐poly(propylene) composites have been investigated. Poly(propylene) fibres of varying diameter have been incorporated in a random ethylene co‐poly(propylene). The composites prepared from the same semi‐crystalline polymer in the matrix and reinforcement have lead to inherently strong interfacial bonding between the two phases of the same polymer. The composites demonstrated enhanced stiffness, which increased with fibre diameter. The structure, thermal, static and mechanical properties of poly(propylene) long fibre reinforced random co‐poly(propylene) composites have been studied with reference to the fibre diameter. The matrix and fibre components retained their separate melting temperatures. After melting, the two phases remained separate and showed their individual crystallization temperatures on cooling, and melting temperatures on a second heating. The melting temperature of the poly(propylene) fibres increased after formation of the composites. The compression molding of the composites at a temperature below the melting temperature of the fibres caused annealing of the fibre crystals. By incorporation of long poly(propylene) fibre into random co‐poly(propylene), the glass transition, storage and static modulus have been found to be increasing and composite with the largest fibre diameter shows better properties. Transcrystallization of the matrix poly(propylene) was observed.

Optical microscopy of composites with fibre diameter 68 μm.     

Rigid‐Rod Polymers: Synthesis,Processing, Simulation,Structure, and Properties

Synthesis, structure, and properties of rigid‐rod polymers with special emphasis on poly(p‐phenylene benzobisoxazole) (PBO) and poly(p‐phenylene benzobisthiazole) (PBZT) have been reviewed. Recent studies on chemical modifications and molecular simulations have also been given. After nearly 20 years of research and development, PBO fiber was commercialized in the late 1990s. However, due to processing difficulties, the concept of the so called molecular composites has not been successful. Development of the high compressive strength M5 and dihydroxy‐PBI fibers clearly suggest that there is potential for further developing properties of this class of materials. Opto‐electronic properties have also been reviewed.

Synthesis of PBZT.     

Determination of Mechanical Properties of Thermoplastics Suitable for Micro Systems

Aircraft and aerospace industry as well as medical and automotive engineering continuously develop smaller and lighter system components. Therefore it is not only important to be able to produce micro parts but also to provide properties for dimensioning and design. This paper explains to what extent mechanical properties from the macro‐range are also valid for micro structures. Thereby the modulus of elasticity as well as stress and strain at the yield point are regarded as relevant properties for the part dimensioning. Systematic investigations with tensile bars of different size show that the geometry‐dependent property changes are obviously not specific for the material classes of amorphous or semi‐crystalline thermoplastics, respectively. That is why a single material testing of micro samples is necessary to determine valid properties for this range. On the other hand the determination known from the classic materials science of plastics that lower temperatures as well as higher loading rates lead to a stiffer material behaviour, is also appropriate for the micro range. The measurements prove that the influence of temperature is much higher than the one of deformation rate. The influence of the production conditions on the mechanical behaviour of test specimen made of semi‐crystalline thermoplastics is demonstrated by using a varied cooling process. The correlation between the resulting different morphological structures and the changes in the mechanical properties is pointed up on the basis of microscopic views.

Micro tensile testing machine at the IKV.     

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.     

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.