Nanostructure and mechanical properties of aromatic polyamide and reactive organoclay nanocomposites

Aromatic polyamide/organoclay nanocomposites were synthesized using the solution blending technique. Treatment of montmorillonite clay with p-phenylenediamine produced reactive organophilic clay for good compatibility with the matrix. Polyamide chains were prepared by condensing a mixture of 1,4-phenylenediamine and 4-4′-oxydianiline with isophthaloyl chloride under anhydrous conditions. These chains were end capped with carbonyl chloride using 1% extra acid chloride near the end of reaction to develop the interactions with organoclay. The dispersion and structure–property relationship were monitored using FTIR, XRD, FE-SEM, TEM, DSC and tensile testing of the thin films. The structural investigations confirmed the formation of delaminated and disordered intercalated morphology with nanoclay loadings. This morphology of the nanocomposites resulted in their enhanced mechanical properties. The tensile behavior and glass transition temperature significantly augmented with increasing organoclay content showing a greater interaction between the two disparate phases.     

Effect of stabilizer on the mechanical,morphological and thermal properties of compatibilized high density polyethylene/ethylene vinyl acetate copolymer/organoclay nanocomposites

In this work, the effects of a phosphate containing stabilizer on the mechanical, morphological and thermal properties of a compatibilized high density polyethylene (HDPE)/ethylene vinyl acetate (EVA) blend containing an ammonium quaternary salts modified montmorillonite were studied from both statistical and experimental aspects. According to the results obtained from simultaneous implementation of analysis of variance (ANOVA) and mean effect assessment, the formulations designed based on the optimized coupling of stabilizer into organoclay/compatibilizer system exhibited the highest tensile properties among the prepared samples. From experimental point of view, the d-spacing measurements and microscopy observations through X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively, revealed that the stabilizer not only favored the penetration of the polymeric chains between the silicate layers but also contributed to provide finer dispersion of the minor phase in the matrix. Thermal characterizations using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) showed that the stabilizer could play a role in prevention of the organic modifier of the nanoclay to undergo thermo-oxidative degradation by hindering the SN₂ nucleophilic substitution reactions between alkyl ammonium chains and oxygen molecules. This, we believe, is responsible for the properties enhancement, since the protective role of stabilizer might inhibit the formation of destructive degradation products which could collapse the organoclay tactoids and also deactivate the anhydride groups of the compatibilizer.     

Slide-ring materials using topological supramolecular architecture

We have recently developed a novel type of gel called slide-ring gel or topological gel by using the supramolecular architecture with topological characteristics. In this gel, polymer chains with bulky end groups exhibit neither covalently cross-links as in chemical gels nor attractive interactions as in physical gels but are topologically interlocked by figure-of-eight cross-links. Hence, these cross-links can pass along the polymer chains freely to equalize the tension of the threading polymer chains similarly to pulleys; this is called pulley effect. The slide-ring gel is a new cross-linking concept for the polymer network as well as a real example of a slip-link model or sliding gel, which was previously considered only theoretically. Here we review the synthesis, structure, and mechanical properties of the slide-ring gels with freely movable cross-linking junctions based primarily on our recent studies. The pulley effect of the slide-ring gels has been recently confirmed by mechanical measurements, small-angle neutron scattering (SANS), small-angle X-ray scattering (SAXS), quasi-elastic light scattering (QELS), etc. This concept can be applied to not only gels but also to a wide variety of polymeric materials without solvents. In particular, the slide-ring elastomer shows remarkable scratch-proof properties to be applied to coating materials for automobile, cell phone, mobile computer, fishing rod, golf club and so on.     

Electrospun PHBV/PEO co-solution blends: Microstructure,thermal and mechanical properties

Blending allows to tailor and modulate the properties of selected polymers. Blends of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and polyethylene oxide (PEO) were fabricated by electrospinning in different weight ratios i.e. 100:0, 80:20, 70:30, 50:50, 0:100.In order to evaluate the influence of PEO addition on the final properties of PHBV, a complete microstructural, thermal and mechanical characterization of PHBV/PEO blends has been performed. The two neat polymeric membranes were also considered for the sake of comparison. The following characterization techniques were employed: scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy, simultaneous thermogravimetric and differential analyses (TG-DTA), differential scanning calorimetry (DSC), and uniaxial tensile tests.All electrospun mats consisted of randomly oriented and uniform fibers. It has been observed that the microstructure of PHBV/PEO was remarkably affected by blend composition. The average fiber size ranged between 0.5 μm and 2.6 μm. It resulted that the electrospun polymeric blends consisted of separate crystalline domains associated to an amorphous interdisperse phase. PHBV/PEO blends presented intermediate mechanical properties, in terms of tensile modulus and ultimate tensile stress, with respect to the two neat components.     

Nanomechanics of advanced polymer fibres

The micro/nano-structural evolution before and after tensile/compressive loading, fatigue and ultimately, failure has been studied by Raman (and IR) microspectroscopy for PBO, PET, PA66, PP, silk and hair using three probes: the low wavenumber collective modes at <150 cm⁻¹ as representatives of the crystalline/ordered and amorphous chains, the stretching and bending modes, as representative of the C–C/C–N polymeric backbone, and the localized vibrations (OH, NH) to probe the inter-macromolecule segment distance. The wavenumber and bandwidth distribution across fibre diameters reveal different types of skin/core heterogeneity. The in situ analysis at different strain/pressure levels shows that amorphous chains in the fibre accommodate the stress differently. The post mortem analysis shows that amorphous domains can be highly stressed during the failure and the remnant stress can be measured.     

Rubber-toughened polyamide 6/clay nanocomposites

Toughening of polyamide 6 (PA6) based nanocomposites (PN’s), with 3 wt% organically modified montmorillonite (OMMT), was investigated by blending with up to 40 wt% of maleinized styrene–ethylene/butadiene–styrene copolymer (mSEBS). The nanostructure of the PA6 matrix did not change on blending with mSEBS, nor did the nature of the two polymeric phases on addition of OMMT. The morphology of the rubber particles in the PN’s was homogeneous, with particle sizes larger than those of the corresponding blends, due to limitations imposed by the clay on the compatibilizing effect of the mSEBS. All the PN’s were ductile and, despite the incorporation of rubber, showed higher small strain tensile properties than those of the corresponding blends. Super-tough nanocomposites were obtained with 30 wt% mSEBS. The critical interparticle distance to attain super-toughness (τ_c) was slightly larger in the blends than in the PN’s, indicating that an increased modulus of the matrix on addition of OMMT leads to smaller τ_c values.     

Effects of ozone exposure on the structural,mechanical and barrier properties of select plastic packaging films

The effects of ozone (O₃) gas exposure at various concentrations and treatment times on structural, mechanical and barrier properties of polyethylene and polyamide films were investigated. Changes in the structure of the films were monitored using an FT‐IR spectrometer. The results showed that O₃ treatment affected polyethylene and polyamide films differently. While O₃ treatment caused formation of oxygen‐containing functional groups and degradation of polymeric chains in polyethylene films, O₃ treatment of polyamide films significantly increased the –C–N– stretch observed at 1125 cm^?1 in the FT‐IR spectra. The changes in the mechanical properties of polyethylene films depended on the O₃ treatment conditions (temperature and O₃ concentration were the most significant), but an increase in tensile strength of polyamide films was observed regardless of the treatment conditions. Permeability to O₂ for both types of films decreased with increasing O₃ treatment time. Copyright © 2003 John Wiley & Sons, Ltd.     

Formation and surface modification of self-assembled films with acrylated hyperbranched poly(ester-amine) as the outmost layer

An acrylated hyperbranched poly(ester-amine) (HPEA) synthesized from piperazine and trimethylolpropanetriacrylate at a molar ratio of 1:1.42 was used as the polycation to form self-assembled films by layer-by-layer dipping with poly(sodium-p-styrenesulfonate) as the polyanion. The surface morphology and hydrophilicity of the films with HPEA as the outmost layer were controlled by adjusting the solution pH of HPEA. Due to the existence of many acrylate groups, the films with HPEA as the outmost layer were further reacted with a series of reagents, including piperazine, piperidine, laurylamine and p-phenylenediamine. The surface reactions of the films depended on both the nature of the reagents and the morphology of the initial surface. In the presence of the strong basic amines, piperazine and piperidine, the films dissolved extensively into the solution. In the case of laurylamine, a modified film with an opaque appearance was obtained due to the crystallization of long alkyl chains. With the weak basic amine p-phenylenediamine as the reactant, the film was effectively modified without any change in the surface morphology.     

聚硅氧烷聚脲的结构与性能研究

利用４，４＇－二异氰酸酯二苯醚与胺丙基封端的聚二甲基硅氧烷反应，合成了一类新型聚硅氧烷聚脲嵌段共聚物。结合热分析、动态力学分析以及小角Ｘ光散射的结果对其结构进行了表征。另外还采用紫外吸收、荧光光谱分析、热失重分析和应力－应变分析等手段研究了这一体系的耐热性、抗光老化性及其力学性能。结果表明，将ＭＤＩ中的亚甲基换成醚键后，有利于防止聚脲分子在光作用下形成醌式结构，提高了聚脲的抗光老化性能。醚键的引入     

Toughened carbon/epoxy composites made by using core/shell particles

Toughened epoxy resin composites have been prepared by resin-transfer moulding by using a range of toughening agents. Two types of epoxy-functional preformed toughening particles were investigated and have a three-layer morphology in which the inner core is crosslinked poly(methyl methacrylate), the intermediate layer is crosslinked poly(butyl acrylate) rubber and the outer layer is a poly[(methyl methacrylate)-co-(ethyl acrylate)-co-(glycidyl methacrylate)]. The presence of glycidyl groups in the outer layer facilitates chemical reaction with the matrix epoxy resin during curing. Comparisons were made with acrylic toughening particles that have a similar structure, but which do not have the epoxy functionality in the outer shell, and with a conventional carboxy-terminated butadiene acrylonitrile (CTBN) liquid rubber toughening agent. The composites were characterised by using tensile, compression and impact testing. The fracture surfaces and sections through the moulded composites were examined by means of optical and scanning electron microscopy. Short-beam shear tests and fragmentation tests were used to investigate the interfacial properties of the composites. In general, use of the epoxy-functionalised toughening particles gave rise to superior properties compared with both the non-functionalised acrylic toughening particles and CTBN.     

The influence of organic additives on the morphologic and crystalline properties of SnO2 obtained by spray pyrolysis deposition

The paper presents a comparative analysis of the SnO₂ thin layers, obtained via spray pyrolysis deposition (SPD), using polymeric precursors with different compositions and concentrations. The changes in the crystalline structure (X-ray diffraction), morphology and surface energy (atomic force microscopy and contact angle) and electric (electrical conductivity) properties of the layers were investigated. The photocatalytic efficiency of the samples was tested considering these layers' future applications in removing organic pollutants.     

Effect of glycerol cross-linking and hard segment content on the shape memory property of polyurethane block copolymer

Effect of glycerol cross-linking and hard segment content on the shape memory property of polyurethane block copolymer is comprehensively investigated. Phase separation of hard and soft segment is dependent on glycerol cross-linking and hard segment content as judged from FT-IR and DSC data. Hydrogen bonding and dipole–dipole interaction between hard segments provides strong interaction between copolymer chains in addition to chemical cross-linking by glycerol. As the hard segment content increases, the copolymer shows better tensile mechanical properties and higher melting temperature of soft segment (T _m). Effect of glycerol cross-linking on mechanical properties and T _m of soft segment is low compared to hard segment effect. Although XRD peak at 2θ = 19.5° is observed, clear difference between the copolymers with various hard segment and cross-linking content is not observed. Significant increase in shape recovery rate in the case of 30 wt% hard segment copolymer is observed after glycerol cross-linking. The drastic change of the properties of polyurethane block copolymer is discussed in the point of copolymer chain interaction.     

Imaging aerogels at the molecular level

Aerogels are a special class of open-cell foams that have an ultrafine cell/pore size (<50 nm), high surface area (400–1000 m² g^–1), and an ultrastructure composed of interconnected colloidal-like particles or polymeric chains with characteristic dimensions of 10 nm. The purpose of this paper is to directly image a series of resorcinol-formaldehyde (RF) and silica aerogels by high resolution transmission electron microscopy (HRTEM). A new vertical replication technique allows us to examine aerogels at the molecular level in situ so that differences in polymeric and colloidal aerogels can be visualized. Such information is crucial for nano-engineering the structure and properties of these novel materials.     

Microstructure and mechanical properties of accelerated sprayed concrete

Considering the different hydration processes of concrete without accelerator, sprayed concrete with low-alkali accelerator not only presents short setting times and high early-age mechanical properties but also yields different hydration products. This study presents an analysis of the mechanical properties of concrete with and without accelerator and sprayed concrete with three water–binder (w/b) ratios and four dosages of fly ash (FA) after different curing ages. It also examines the setting time, mineral composition, thermogravimetric–differential scanning calorimetry curves and microscopic images of cement pastes with different accelerator amounts. Furthermore, the setting time and microstructure of accelerated sprayed concrete with different w/b ratios and FA contents are examined. Results show that the retarded action of gypsum disappears in the accelerated cement–accelerator–water system. C₃A is quickly hydrated to form calcium aluminate hydrate (CAH) crystals, and a mesh structure is formed by ettringite, albite and CAH. A large amount of hydration heat improves the hydration rate of the cement clinker mineral and the resulting density, thereby improving mechanical properties at early curing ages. The setting times of the pastes increase with increasing w/b ratio and FA dosage. Thus, the hydration level, microstructure and morphology of the hydration products also change. Models of mechanical properties as functions of w/b, FA and curing age, as well as the relationship between compressive strength and splitting tensile strength, are established.     

Functionalized cellulose nanocrystals as biobased nucleation agents in poly(l-lactide) (PLLA) – Crystallization and mechanical property effects

The important industrial problem of slow crystallization of poly(l-lactide) (PLLA) is addressed by the use of cellulose nanocrystals as biobased nucleation reagents. Cellulose nanocrystals (CNC) were prepared by acid hydrolysis of cotton and additionally functionalized by partial silylation through reactions with n-dodecyldimethylchlorosilane in toluene. Such silylated cellulose nanocrystals (SCNC) were dispersible in tetrahydrofuran and chloroform, and formed stable suspensions. Nanocomposite films of PLLA and CNC or SCNC were prepared by solution casting. The effects of surface silylation of cellulose nanocrystals on morphology, non-isothermal and isothermal crystallization behavior, and mechanical properties of these truly nanostructured composites were investigated. The unmodified CNC formed aggregates in the composites, whereas the SCNC were well-dispersed and individualized in PLLA. As a result, the tensile modulus and tensile strength of the PLLA/SCNC nanocomposite films were more than 20% higher than for pure PLLA with only 1 wt.% SCNC, due to crystallinity effects and fine dispersion.     

Structure and properties of ultrafine silk fibers produced by <Emphasis Type="Italic">Theriodopteryx ephemeraeformis</Emphasis>

Theriodopteryx ephemeraeformis commonly known as bag worms produce ultrafine silk fibers that are remarkably different than the common domesticated (Bombyx mori) and wild (Saturniidae) silk fibers. Bag worms are considered as pests and commonly infect trees and shrubs. Although it has been known that the cocoons (bags) produced by bag worms are composed of silk, the structure and properties of the silk fibers in the bag worm cocoons have not been studied. In this research, the composition, morphology, physical structure, thermal stability, and tensile properties of silk fibers produced by bag worms were studied. Bag worm silk fibers have considerably different amino acid contents from those of the common silks. The physical structure of the bag worm silk fibers is also considerably different compared with B. mori and common wild silk fibers. Bag worm’s silk fibers have lower tensile strength (3.2 g/denier) and Young’s modulus (45 g/denier) but similar breaking elongation (15.3%) compared with B. mori silk. However, the tensile strength and Young’s modulus of bag worm fibers are similar to those of the common Saturniidae wild silk fibers. Bag worm silk fibers could be useful for some of the applications currently using the B. mori and wild silk fibers.     

Microwave synthesis of calcium bismuth niobate thin films obtained by the polymeric precursor method

The crystal structure, surface morphology and electrical properties of layered perovskite calcium bismuth niobate thin films (CaBi₂Nb₂O₉-CBN) deposited on platinum coated silicon substrates by the polymeric precursor method have been investigated. The films were crystallized in a domestic microwave and in a conventional furnace. X-ray diffraction and atomic force microscopy analysis confirms that the crystallinity and morphology of the films are affected by the different annealing routes. Ferroelectric properties of the films were determined with remanent polarization P_r and a drive voltage V_c of 4.2 μC/cm² and 1.7 V for the film annealed in the conventional furnace and 1.0 μC/cm² and 4.0 V for the film annealed in microwave furnace, respectively. A slight decay after 10⁸ polarization cycles was observed for the films annealed in the microwave furnace indicating a reduction of the domain wall mobility after interaction of the microwave energy with the bottom electrode.     

Influence of carbon nanotube-polymeric compatibilizer masterbatches on morphological, thermal, mechanical, and tribological properties of polyethylene

Study was made of the effect of multiwall carbon nanotubes (MWCNTs) and polymeric compatibilizer on thermal, mechanical, and tribological properties of high density polyethylene (HDPE). The composites were prepared by melt mixing in two steps. Carbon nanotubes (CNTs) were melt mixed with maleic anhydride grafted polyethylene (PEgMA) as polymeric compatibilizer to produce a PEgMA-CNT masterbatch containing 20 wt% of CNTs. The masterbatch was then added to HDPE to prepare HDPE nanocomposites with CNT content of 2 or 6 wt%. The unmodified and modified (hydroxyl or amine groups) CNTs had similar effects on the properties of HDPE-PEgMA indicating that only non-covalent interactions were achieved between CNTs and matrix. According to SEM studies, single nanotubes and CNT agglomerates (size up to 1 μm) were present in all nanocomposites regardless of content or modification of CNTs. Addition of CNTs to HDPE-PEgMA increased decomposition temperature, but only slight changes were observed in crystallization temperature, crystallinity, melting temperature, and coefficient of linear thermal expansion (CLTE). Young’s modulus and tensile strength of matrix clearly increased, while elongation at break decreased. Measured values of Young’s moduli of HDPE-PEgMA-CNT composites were between the values of Young’s moduli for longitudinal (E₁₁) and transverse (E₂₂) direction predicted by Mori-Tanaka and Halpin-Tsai composite theories. Addition of CNTs to HDPE-PEgMA did not change the tribological properties of the matrix. Because of its higher crystallinity, PEgMA possessed significantly different properties from HDPE matrix: better mechanical properties, lower friction and wear, and lower CLTE in normal direction. Interestingly, the mechanical and tribological properties and CLTEs of HDPE-PEgMA-CNT composites lie between those of PEgMA and HDPE.     

Preparation and tribological behavior of Cu-nanoparticle polyelectrolyte multilayers obtained by spin-assisted layer-by-layer assembly

Polyelectrolyte multilayers (PEMs) fabricated by spin-assisted layer-by-layer assembly technique were used as nanoreactors for in-situ synthesis Cu nanoparticles. Chemical reaction within the PEMs was initiated by a reaction cycle in which Cu²⁺ was absorbed into the polymer-coated substrate and then reduced in NaBH₄ solutions. Repeating the above process resulted in an increase in density of the nanoparticles and further growth in the dimension of the particles initially formed. So, different Cu-nanoparticle polyelectrolyte multilayers were formed in the process. The friction and wear properties of Cu-nanoparticle PEMs formed by different reaction cycles were investigated on a microtribometer against a stainless steel ball. The PEMs reinforced with Cu nanoparticles, prepared under the best preparation conditions, possess good tribological behavior, because of the weakened adhesion between the PEMs and the substrate and decreased mobility of the polymeric chains in the presence of excessive Cu nanoparticles generated at larger reaction cycles.     

Structure and properties of cocoons and silk fibers produced by <Emphasis Type="Italic">Hyalophora cecropia</Emphasis>

This paper shows that silk fibers produced by cecropia (Hyalophora cecropia) have similar tensile properties but different amino acid composition than that of mulberry (Bombyx mori) silk. The cecropia fibers are also much finer and have better strength and modulus than tasar silk, the most common non-mulberry silk. Cecropia is one of the largest silk producing moths and has similar lifecycle to that of mulberry silk but is easier to grow and produces larger cocoons than mulberry silk. In this study, we have characterized the composition, morphology, physical and tensile properties, and thermal behavior of the cecropia silk. Cecropia cocoons have a three tier structure and are larger (750 mg) than the cocoons produced by B. mori (650 mg). Fibers in the three layers in cecropia cocoons have tensile properties similar to that of B. mori silk but are finer (1.7–2 denier) and have higher strength (3.8–4.3 g/denier) and modulus (68–92 g/denier) than tasar silk.