Optically transparent composites reinforced with plant fiber-based nanofibers

The fibrillation of pulp fiber was attempted by two methods, a high-pressure homogenizer treatment and a grinder treatment. The grinder treatment resulted in the successful fibrillation of wood pulp fibers into nanofibers. The nanofibers demonstrate promising characteristics as reinforcement material for optically transparent composites. Due to the size effect, the nanofiber-reinforced composite retains the transparency of the matrix resin even at high fiber content such as 70 wt %. Since the nanofiber is an aggregate of semi-crystalline extended cellulose chains, its addition also contributes to a significant improvement in the thermal expansion properties of plastics while maintaining its ease of bending. Cellulose nanofibers have tremendous potential as a future resource since they are produced in a sustainable manner by plants, one of the most abundant organic resources on earth. PACS 81.05.Lg; 81.05.Qk     

Sorption characteristics of water,oil and diesel in cellulose nanofiber reinforced corn starch resin/ramie fabric composites

Nowadays, utilisation of biodegradable materials has become necessary in order to maintain global environmental and ecological balance. Fully biodegradable nano 'Green' textile composites have been prepared from cellulose nanofibers reinforced corn starch resin and ramie fabric. Nanofibers having dimensions of approximately 1 μm long and 20–30 nm in diameter are used in the study. The nanofibers were incorporated in corn starch resin via ball mill mixing using ceramic balls. Textile composites were fabricated by pasting the reinforced resin onto the ramie fabric and by hot compression molding technique. Interactions at the fiber–matrix interface and the compatibility between cellulose and corn starch resin molecules will affect the properties of the system. The well dispersed cellulose nanofibers contribute higher interfacial area and good fiber networking within the matrix resin. This will lead to better barrier properties. Sorption characteristics of water, oil and diesel in the textile composites were analysed and the influence of nano fibers and macro fibers on the transport phenomena was investigated. The kinetics of sorption-diffusion process was investigated. Kinetic parameters such as n, k, diffusion coefficient, permeability, solubility parameter, % swelling index, etc., were analysed. The presence of cellulose nanofibers influences the sorption mechanism. The water sorption mechanism in the nanocomposites was found to exhibit slight deviation from Fickian mode. Structure–property relationships of the nanocomposites were evaluated.     

Two-nozzle electrospinning of (MWNT/PU)/PU nanofibrous composite mat with improved mechanical and thermal properties

Composite nanofibrous mat composed of neat polyurethane (PU) and multiwalled carbon nanotubes/polyurethane (MWNT/PU) nanofibers have been fabricated by one-step angled two-nozzle electrospinning. The morphological, thermal, and mechanical properties of the electrospun nanofibers were evaluated. The diameters of electrospun neat PU and composite nanofibers ranged from 239 to 1058 nm. The two-nozzle electrospun (MWNT/PU)/PU composite nanofibers showed curly, and randomly-oriented fibers with interfiber bonding, and were generally bigger in size than single-nozzle electrospun nanofibers. The tensile strength of the neat PU composite nanofiber mat obtained from two-nozzle electrospinning was 25% higher than that obtained from neat PU single-nozzle electrospinning. The incorporation of MWNTs in the composite nanofiber increased the tensile strength by as much as 64% without reducing elongation, made the composite nanofiber more thermally stable, and improved the melting zone. The present results showed that side-by-side angled two-nozzle electrospinning can improve the quality of the electrospun nanofibers that could have potential application in different fields such as filtration, protective clothing and tissue engineering.     

Nano-fibrillation of pulp fibers for the processing of transparent nanocomposites

Pulp fibers were fibrillated uniformly into nano-sized fibers using a grinder with a specially designed set of grinding disks. To investigate the effect of the fibrillation through the grinder on the physical properties of the composites, dissolved pulp fibers were subjected to various passes through the grinder, and the resulting fibrillated pulp fibers were used to make fibrillated pulp fibers/acrylic resin composites. Scanning electron microscopy observations showed that at above five passes, the structure of the fibrillated pulp fibers did not change significantly. The light transmittances of the composites were increased to 80% up to five passes through the grinder, and did not change after further passes. However, the tensile test and thermal expansion analysis indicated that a degradation of the fibrillated pulp occurred during the grinding treatment. To evaluate the fiber degradation, the degree of crystallinity and degree of polymerization of cellulose were measured. Both decreased as the number of passes through the grinder increased. In addition, to reduce the thermal expansion of composites, the fibrillated pulp fibers were additionally treated by sulfuric acid. The thermal expansion of composites was decreased, because the amorphous region of cellulose was removed. PACS 81.05.Lg; 81.05.Qk; 81.07.-b     

Poly(Butylene Terephthalate)/Single Wall Carbon Nanotubes Composite Nanofibers by Electrospinning

Poly(buthylene terephthalate)(PBT)/single wall carbon nanotubes (SWCNTs) composite nanofibers were prepared by electrospinning. The effect of carbon nanotubes on the morphology, crystallization, and mechanical properties of the electrospun composite nanofibers were investigated by SEM, DSC, and tensile testing, respectively. SEM observations indicated that the presence of SWCNTs resulted in finer nanofibers for lower loading; however, a broader distribution, especially for the higher diameter ranges was found for nanofibers with higher amounts of carbon nanotubes. SWCNTs accelerated crystallization and acted as a nucleating agent; the degree of crystallinity increased with increasing content of SWCNTs, followed by a moderate decrease at higher content. Specific tensile strength and modulus of the PBT/SWCNTs composite nanofibers mats were higher than that of neat PBT nanofibers mat. However, the elongation at break of composite nanofibers mats was lower than that of the neat PBT nanofibers mat.     

Synergistic Effect of Polyhedral Oligomeric Silsesquioxane and Multiwalled Carbon Nanotubes on the Flame Retardancy and the Mechanical and Thermal Properties of Epoxy Resin

A novel polyhedral oligomeric silsesquioxane containing phosphorus and boron (PB-POSS) was synthesized. The resulting PB-POSS and multiwalled carbon nanotubes (MWCNTs) were incorporated into an epoxy resin (EP) to prepare PB-POSS/MWCNTs/EP composites through a solution mixing method. The synergistic effect of MWCNTs and PB-POSS on the thermal and mechanical properties and the flame retardancy of these flame retardant composites were studied. The experimental results showed that the introduction of PB-POSS or MWCNTs further improved the LOI values of the epoxy resin, and the highest LOI value (32.8%) was obtained for the formulation containing 14.6 wt% PB-POSS and 0.4 wt% MWCNTs. In addition, the incorporation of both PB-POSS and MWCNTs significantly improved the thermal and mechanical properties of the composites. The mechanical properties of composites containing 14.7 wt% PB-POSS and 0.3 wt% MWCNTs reached the maximum. The impact strength and flexural strength increased by 42% and 7%, respectively, compared to the neat epoxy resin. Thus, a combination of PB-POSS and MWCNTs in the appropriate ratio could effectively enhance the thermal and mechanical properties and the flame retardancy of the epoxy resin matrix.     

SEM characterization of anatomical variation in chitin organization in insect and arthropod cuticles

The cuticles of insects and arthropods have some of the most diverse material properties observed in nature, so much so that it is difficult to imagine that all cutciles are primarily composed of the same two materials: a fibrous chitin network and a matrix composed of cuticle proteins. Various factors contribute to the mechanical and optical properties of an insect or arthropod cuticle including the thickness and composition. In this paper, we also identified another factor that may contribute to the optical, surface, and mechanical properties of a cuticle, i.e. the organization of chitin nanofibers and chitin fiber bundles. Self-assembled chitin nanofibers serve as the foundation for all higher order chitin structures in the cuticles of insects and other arthropods via interactions with structural cuticle proteins. Using a technique that enables the characterization of chitin organization in the cuticle of intact insects and arthropod exoskeletons, we demonstrate a structure/function correlation of chitin organization with larger scale anatomical structures. The chitin scaffolds in cuticles display an extraordinarily diverse set of morphologies that may reflect specific mechanical or physical properties. After removal of the proteinaceous and mineral matrix of a cuticle, we observe using SEM diverse nanoscale and micro scale organization of in-situ chitin in the wing, head, eye, leg, and dorsal and ventral thoracic regions of the periodical cicada Magicicada septendecim and in other insects and arthropods. The organization of chitin also appears to have a significant role in the organization of nanoscale surface structures. While microscale bristles and hairs have long been known to be chitin based materials formed as cellular extensions, we have found a nanostructured layer of chitin in the cuticle of the wing of the dog day annual cicada Tibicen tibicens, which may be the scaffold for the nanocone arrays found on the wing. We also use this process to examine the chitin organizations in the fruit fly, Drosophila melanogaster, and the Atlantic brown shrimp, Farfantepenaeus aztecus. Interestingly many of the homologous anatomical structures from diverse arthropods exhibit similar patterns of chitin organization suggesting that a common set of parameters, govern chitin organization.     

Thermoplastic starch nanocomposites reinforced with cellulose nanocrystals: effect of plasticizer on properties

The objective of this study was to characterize cellulose nanocrystals /TPS-based nanocomposites. Nanocrystalline cellulose was isolated from cotton linters using sonochemical method and characterized through WXRD, TEM, and FTIR. These nanocrystals were then dispersed in glycerol and sorbitol plasticized starch using a Fluko high shear homogenizer in varying proportions and films were cast. The films were characterized using WXRD, SEM, and mechanical properties. TEM images of nanocrystals revealed a diameter of 20–30 nm and length 200–300 nm. XRD results for nanocomposite films for both the plasticizers showed 2θ peaks at 14.8°, 16.7,° and 22.5°. Elastic modulus increased with addition of cellulose nanocrystals and tan δ shifted toward higher temperature for both the plasticizers. Mechanical properties improved more than 200% for both glycerol and sorbitol plasticized nanocomposites.     

Modification of Epoxy Resin with Cycloaliphatic-Epoxy Oligosiloxane for Light-Emitting Diode (LED) Encapsulation Application

A novel cycloaliphatic-epoxy oligosiloxane (EHDM) was incorporated into 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (ERL-4221) for use as a light-emitting diode (LED) encapsulant. EHDM, with reactable epoxy groups and flexible Si-O-Si chains, was obtained by the hydrolytic condensation reaction between 2-(3,4-epoxycyclo-hexyl)ethyl-trimethoxysilane (EHETMS) and dimethyldiethoxylsilane (DMDES). The results of Fourier transform infrared spectroscopy, ²⁹Si nuclear magnetic resonance, and gel permeation chromatography indicated that EHDM had a narrow molecular weight distribution and high epoxy graft degree. The thermal and mechanical properties, morphologies, and light transmittance of the cured neat epoxy resin and EHDM-modified epoxy were investigated by differential scanning calorimetry, thermogravimetric analysis, tensile and impact testing, scanning electron microscopy, and ultraviolet-visible spectrophotometry. The experimental results demonstrated that the cured EHDM-10 hybrimer with 10 pph of EHDM relative to ERL-4221 maintained the neat ERL-4221 epoxy transmittance of 85% at 450 nm. With respect to the corresponding properties of the neat epoxy resin, EHDM-10 hybrimer possessed a higher glass transition temperature, better thermal stability, better fracture toughness, and lower water absorption ratio, indicating EHDM effectively improved the properties of ERL-4221 for LED packaging applications.     

The mechanical efficiency of natural materials

The materials of nature, for example cellulose, lignin, keratin, chitin, collagen and hydroxyapatite, and the structures made from them, for example bamboo, wood, antler and bone, have a remarkable range of mechanical properties. These can be compared by presenting them as material property charts, well known for the materials of engineering. Material indices (significant combinations of properties) can be plotted on to the charts, identifying materials with extreme values of an index, suggesting that they have evolved to carry particular modes of loading, or to sustain large tensile or flexural deformations, without failure. This paper describes a major revision and update of a set of property charts for natural material published some 8 years ago by Ashby et al. with examples of their use to study mechanical efficiency in nature.     

Supermolecular structure and orientation of blown cellulosic films

N-Methylmorpholine-N-oxide (NMMO) technology provides new possibilities for shaping fibers and films from cellulose. We discuss a blow-extrusion technique can be applied to a cellulose-amine oxide dope, yielding blown cellulosie films. Process parameters, such as the draw down ratio and the blow ratio, can be used to control the mechanical film properties in both the machine and transverse directions. In this way, a wide range of properties is covered, and a completely balanced film can be manufactured. The film thickness can be made as small as 5 μm, and the membrane properties can be varied by the conditions of precipitation. The blown cellulosic films exhibit a partially crystalline supermolecular structure and, depending on the coagulation conditions, a symmetrical or asymmetrical homogeneous morphology and pore structure. Generally, a uniplanar orientation type was found, the chains being parallel to the film surface. Around the surface normal, the chain orientation can be varied from nearly random to strongly uniaxial, in this way determining the mechanical properties in the machine and transverse directions. As compared with the conventional viscose processing route of cellophane, the blown film's NMMO processing route is less complicated and friendlier to the environment. Blown films can be made much thinner, and the mechanical properties are superior to viscose films. Possible application fields of blown cellulose films are food casings, particularly small sausage casings, packaging, and membranes.     

Thermal and mechanical properties and micro-mechanism of SiO2/epoxy nanodielectrics

In addition to electrical insulation properties, the thermal properties of nanodielectrics, such as glass transition temperature, thermal expansion coefficients, thermal conductivity, and mechanical properties, including Young's modulus, bulk modulus, and shear modulus, are also very important. This paper describes the molecular dynamics simulations of epoxy resin doped with SiO₂ nanoparticles and with SiO₂ nanoparticles that have been surface grafted with hexamethyldisilazane (HMDS) at 10% and 20% grafting rates. The results show that surface grafting can improve certain thermal and mechanical properties of the system. Our analysis indicates that the improved thermal performance occurs because the formation of thermal chains becomes easier after the surface grafting treatment. The improved mechanical properties originate from two causes. First, doping with SiO₂ nanoparticles inhibits the degree of movement of molecular chains in the system. Second, the surface grafting treatment weakens the molecular repulsion between SiO₂ and epoxy resin, and the van der Waals excluded region becomes thinner. Thus, the compatibility between SiO₂ nanoparticles and polymers is improved by the grafting treatment. The analysis method and conclusions in this paper provide guidance and reference for the future studies of the thermal and mechanical properties of nanodielectrics.     

Processing and properties of carbon nanofibers reinforced epoxy powder composites

Commercially available CNFs (diameter 30–300 nm) have been used to develop both bulk and coating epoxy nanocomposites by using a solvent-free epoxy matrix powder. Processing of both types of materials has been carried out by a double-step process consisting in an initial physical premix of all components followed by three consecutive extrusions. The extruded pellets were grinded into powder and sieved. Carbon nanofibers powder coatings were obtained by electrostatic painting of the extruded powder followed by a curing process based in a thermal treatment at 200 °C for 25 min. On the other hand, for obtaining bulk carbon nanofibers epoxy composites, a thermal curing process involving several steps was needed. Gloss and mechanical properties of both nanocomposite coatings and bulk nanocomposites were improved as a result of the processing process. FE-SEM fracture surface microphotographs corroborate these results. It has been assessed the key role played by the dispersion of CNFs in the matrix, and the highly important step that is the processing and curing of the nanocomposites. A processing stage consisted in three consecutive extrusions has reached to nanocomposites free of entanglements neither agglomerates. This process leads to nanocomposite coatings of enhanced properties, as it has been evidenced through gloss and mechanical properties. A dispersion limit of 1% has been determined for the studied system in which a given dispersion has been achieved, as the bending mechanical properties have been increased around 25% compared with the pristine epoxy resin. It has been also demonstrated the importance of the thickness in the nanocomposite, as it involves the curing stage. The complex curing treatment carried out in the case of bulk nanocomposites has reached to reagglomeration of CNFs.     

Modification of BPDA-ODA Polyimide Films by Diimides

Diimides 4,4′-oxydiphenylene diphthalylimide (PT-ODA-PT) and diphenylbiphenyltetracarboxyimide (A-BPDA-A) of an evident affinity to polyimides have been dispersed in a matrix of poly(4,4′-oxydiphenylene biphenyltetracarboxyimide) (BPDA-ODA). Changes in thermal and mechanical properties of BPDA-ODA films modified by diimides have been found to depend on the amount of diimide added and the conditions of film preparation (stretching). It has been established that diimides can play two different roles. When dissolved in polyimide, they act as plasticizers improving the segment mobility of BPDA-ODA chains, which may be critically needed to achieve the better molecular packing. The films plasticized by diimides show lower T _g and the order–disorder transition temperature; the unstretched films exhibit better tensile properties, compared to unmodified films. However, dispersed beyond the limit of solubility in polyimides, diimides have detrimental effects on mechanical properties of the films. Though changes of the thermal properties of compositions derived from BPDA-ODA polyimide and microparticular diimides are less expressed than those of polyimide films plasticized by diimides, the compositions have poorer ultimate strength and shorter elongation at break. The conclusion may be drawn that the mechanical properties of the films modified by microparticular diimide are mainly controlled not by the interfacial interaction matrix–microparticles, but more likely by the much stronger macromolecular chain–chain interaction.     

Mechanical and Tribological Properties of Self-Reinforced Polyphenylene Sulfide Composites

25%, 50%, and 75% polyphenylene sulfide (PPS) long fiber reinforced PPS resin were prepared by a hot pressing method. Neat resin PPS and PPS fiber samples were also prepared to compare with the self-reinforced PPS composites. The reinforcing fibers were preheat treated at 240°C for 24 h. The tribological properties of the self-reinforced PPS composites against an AISI 1045 steel ring were determined by a block on ring type friction tester. Differential scanning calorimetry (DSC) results indicated that a higher degree of crystallinity was retained in the self-reinforced PPS composites than in neat PPS resin after hot pressing. Therefore, the addition of PPS fiber improved both the mechanical and tribological properties of PPS resin significantly. Dynamic mechanical analysis (DMA) demonstrated that the PPS fibers increased the glass transition temperature (Tg) of the PPS resin. SEM images of the fracture surfaces indicated that the toughness of the samples increased with increasing PPS fiber content. Additionally, PPS fibers improved the tribological properties of PPS resin by significantly reducing the friction coefficient and wear rate.     

High Optical Transparency and Low Dielectric Constant Polyimides Containing Trifluoromethyl and Cyclohexane Groups

A series of novel polyimides (PIs) were polymerized from 4,4′-(cyclohexane-1,4-diylbis (oxy))bis(3-(trifluoromethyl)aniline) (1) and 1,4-bis((4-amino-2-(trifluoromethyl) phenoxy)methyl)cyclohexane (2), with two aromatic tetracarboxylic dianhydrides using the typical one-step method. The inherent viscosity of these resulting PIs were in the range of 0.53–0.91 dl/g in N,N-dimethylacetamide (DMAc) at 30°C. They were readily soluble in numerous solvents, such as N-methyl-2-pyrrolidone (NMP), DMAc, N,N-dimethylformamide (DMF), meta-cresol (m-Cresol), and dimethylsulfoxide (DMSO). The PI films showed high optical transparency and were colorless with an ultraviolet-visible absorption cut-off wavelength around 330 nm, and a low dielectric constants of 2.49–2.93 at 1 MHz. The PIs also showed good thermal properties. Their glass-transition temperatures (T _g) were higher than 337°C, and the temperatures of 10% weight loss in air and nitrogen were higher than 412°C and 417°C. Furthermore, the PI films possessed good mechanical properties with tensile strengths of 54–71 MPa, elongations at break of 11.6%–17.3% and low moisture absorption (<1.34%). Due to their properties, these PIs could be considered as materials for photoelectric and micro-electronic applications.     

Thermoluminescence characterization of functionalized grafted polymers and its application for radiation dosimetry at low doses

Functionalized polymers were prepared by radiation-induced graft copolymerization of binary monomer system acrylic acid/acrylamide (AAc/AAm) onto low-density polyethylene (LDPE) and polypropylene (PP) films using direct radiation-grafting technique. Sulfonation was carried out for the prepared grafted copolymers using concentrated sulfuric acid (97%) at 60 ^°C for 15 min. The grafted and sulfonated grafted films found to have good properties such as thermal stability and hydrophilic properties. The sulfonated grafted films found to have a better hydrophilic character than the grafted ones due to ionic character resulted by this conversion. The thermoluminescence (TL) characteristics of a set of grafted and sulfonated films have been studied with regard to their use as off-line dosimeters in radiotherapy. The structural characterization has been performed by means of infrared spectroscopy. Their TL responses have been tested with radiotherapy beams of ⁶⁰Co photons in the dose range 0.1–7 Gy. The dosimetric characterization has yielded a very good reproducibility and is independent of the radiation energy. The TL signal is not influenced by the dose rate and exhibits a very low thermal fading. Moreover, the sensitivity of the samples compares favorably with that of the standard TLD100 dosimeters. Finally, at the same dose, the TL response for LDPE-g-P (AAm/AAc) films is higher than the PP-$g$-P(AAm$/$AAc), and the sulfonated grafted films are more sensitive to radiation than the grafted ones.     

Mechanical Properties and Morphology of Polylactide Composites with Acrylic Impact Modifier

Polylactide (PLA) composites with acrylic impact modifier BPM, i.e., PLA/BPM composites, were produced by the melt blending method. The effects of BPM on the thermal properties, melting behaviors, and dynamic mechanical properties of the PLA/BPMs were investigated by thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. Tensile strength, flexural strength, and modulus of the injection molded specimens were measured by an Instron tensile machine. The influence of BPM on the impact strength of injection molded PLA/BPM composites was examined using an impact tester. The morphology of cryofractured surfaces and fracture surfaces of the composites after the tensile and impact testing was also investigated using scanning electron microscope. The test results show that the composites with BPM possess better flexibility when compared with neat PLA. However, the notched Izod impact strength showed improvement only when the BPM content was higher than 15 wt%.     

Temperature dependence of the stress transfer for thermal resistance polymer composites by X-ray diffraction

Temperature dependence of the stress transfer from the matrix resin to the incorporated fiber has been measured for poly(p-phenylene benzobisoxazole) (PBO) fiber/bismaleimide (BMI) resin composite by a novel X-ray diffraction method. At 120°C, stress transfer and tensile strength of the PBO/BMI composite are superior to that of the PBO/epoxy composite, due to the excellent thermal resistance and good mechanical property of BMI resins. The PBO/BMI composite possesses good adhesion and excellent mechanical properties at high temperature, which are suitable for thermal resistance applications.     

Evaluation of the geopolymer/nanofiber interfacial bond strength and their effects on Mode-I fracture toughness of geopolymer matrix at high temperature

The present article has reported the effects of several nanofiller’s aspect ratio, length and interfacial strength on Mode-I fracture toughness (K_IC) of geopolymer as the matrix of continuous fibre reinforced composites. These nanofillers have been chosen based on the variations in the surface chemistry and nature of interfacial bonding with geopolymer, which include Carbon, Alumina and Silicon carbide. Geopolymer matrix was subjected to the addition of single volume fraction, 2% of each type of nanofiller with two aspect ratios, designated as nanoparticles and nanofibers. Notched beam flexure tests (SEVNB) of neat and each nanofiller reinforced samples suggest that, while baseline K_IC of neat geopolymer improved with heat treatment, nanofibers with high interfacial bond strength showed maximum capability in further improving K_IC. Among those nanofibers, 2 vol% Silicon Carbide Whisker (SCW) showed the largest improvement in K_IC of geopolymer, which is ~164%. After heat treatment at 650 °C, SCW reinforcement was also found to be effective, with only ~28% lower than the reinforcing performance at 250 °C, while the performance of Alumina Nanofiber reinforced geopolymer notably reduced. SEM and EDS analysis suggested that the inhomogeneity in neat geopolymer and length of nanofibers control the reinforcing capability as well as crack propagation resistance of geopolymer. For instance, minimum length of nanofillers to toughen this geopolymer at 250 °C was required as ~2 μm. The results further suggested that the sample failure occurred due to the dominance of tensile failure of nanofibers over the interfacial separation.