Aromatic Polyimide/MWCNT Hybrid Nanocomposites: Structure,Dynamics, and Properties

Two series of hybrid polyimide (PI)/multiwalled carbon nanotube (MWCNT) nanocomposites were prepared including COOH-functionalized or pristine nanotubes, and their structure, morphology and dynamics/mechanical properties at 20°C–500°C were studied using WAXD (Wide-angle X-ray diffraction), AFM (Atomic force microscopy), TEM (transmission electron microscopy), DSC (Differential scanning calorimetry), DMA (Dynamic mechanical analysis), CRS (creep rate spectroscopy) techniques, and stress–strain testing. The impact of nanofiller loadings of 0.125, 0.25, 0.5, or 1 wt% relative to PI was evaluated. Specific changes in the matrix morphology and different quality of nanotube dispersion in the nanocomposites with amorphous and semicrystalline matrices were determined. The best nanotube dispersion was observed in the composites with 0.5 wt% MWCNT-COOH. A peculiar high temperature dynamics, different for amorphous, and semicrystalline matrices, was revealed in these nanocomposites. The most dramatic changes in high temperature dynamics and a pronounced dynamic heterogeneity as well as substantially enhanced mechanical properties at room temperature were revealed in the case of a semicrystalline PI matrix. The results were treated in terms of the synergistic impact of nanotubes and matrix crystallites on dynamics in the intercrystalline regions of PI (“combined constrained dynamics effect”) and the peculiar interfacial dynamics.     

Influence of chemical treatments on the interfacial adhesion between sisal fibre and different biodegradable polymers

The influence of chemical treatments on the interfacial adhesion of sisal fibres and biodegradable matrices were studied in the present work. For that purpose, four different polymers were used: polycaprolactone (PCL), cellulose acetate, MaterBi Z (a commercial starch/polycaprolactone blend) and MaterBi Y (a commercial starch/cellulose derivatives blend). Alkaline and acetylation treatments were performed on sisal fibres. Properties were determined by means of tensile tests, adhesion measurements and contact angle determination. The interfacial shear strength was correlated with the hydrophilic character of the material.     

Effects of Replacement of Part of the Silica Reinforcement with Hybrid Modified Microcrystalline Cellulose on the Properties of their Rubber Composites

Hybrid modified microcrystalline cellulose (HMCC), with SiO₂ nanoparticles being in-situ loaded on the surface of microcrystalline cellulose (MCC), was obtained through a sol-gel process of tetraethoxysilane (TEOS) by using ammonia as catalyst. HMCC was characterized by thermogravimetric analysis and scanning electron microscopy. The results showed that the spherical nano-SiO₂ particles had been loaded successfully on the surface of the MCC with a loading ratio of approximately 10%. Then the HMCC was used in high vinyl solution-polymerized styrene butadiene rubber (SSBR)/silica compounds to replace part of the silica, and its effects on the physio-mechanical and dynamic mechanical properties of the vulcanizates were investigated. The results showed that the HMCC samples had improved physio-mechanical properties and lower heat build-up than that of MCC ones. Dynamic mechanical analysis (DMA) showed that the tanδ value of the compounds decreased at 60°C while increased obviously at 0°C, which meant that the tires would have improved wet-skid resistance while maintaining low rolling resistance when HMCC was used in tire tread compounds. As observed from scanning electron microscopy (SEM) photos, the sizes of the HMCC were in-situ decreased from 20–90 µm to 0.5–10 µm during the processing of the rubber compounds. Compared with MCC, the interfacial adhesion between HMCC and rubber was also improved greatly.     

Damping Properties of Ethylene-Vinyl Acetate Rubber/Nitrile Butadiene Rubber Blends

The damping and mechanical properties of ethylene-vinyl acetate rubber (EVM)/nitrile butadiene rubber (NBR) blends, with BIPB (bis (tert-butyl peroxy isopropyl) benzene) as curing agent, were investigated by DMA. It was proved by mechanical performance, DMA and crosslink density data that a chemical crosslinking reaction occurred between EVM and NBR. A new tan δ peak appeared between 40°C and 60°C in EVM/NBR = 80/20, which we suggest was due to a new molecular chain generated between EVM and NBR. Thus, the effective damping temperature range (EDTR) of EVM/NBR = 80/20 was widened from 31.6°C of EVM and 31.7°C of NBR to 40.7°C. The addition of sulfur, as a curing agent for NBR, greatly raised the height of the damping peak of EVM/NBR blend, but only slightly widened the EDTR at a cost of deterioration of mechanical performance. Zinc diacrylate (Zn (Ac)₂), as a possible graft addition to the blends, enlarged the damping peak of EVM/NBR, especially widening the EDTR of EVM/NBR = 80/20 to 50.9°C, but with a decline of mechanical properties. PVC was partially miscible with EVM/NBR blends and dramatically widened the EVM/NBR = 80/20 EDTR to 62.4°C.     

Interphase sizing temperature effect of LaRC PETI-5 on the dynamic mechanical thermal properties of carbon fiber/BMI composites

The dynamic mechanical thermal properties of carbon fiber-reinforced bismaleimide (BMI) composites processed using polyacrylonitrile(PAN)-based carbon fibers unsized and sized with LaRC PETI-5 amic acid oligomer as interphase material at 150°C, 250°C, and 350°C were investigated by means of dynamic mechanical thermal analysis. It was found that the storage modulus, loss modulus, tan δ and the peak temperature significantly depend on the sizing temperature as well as on the presence and absence of LaRC PETI-5 sizing interphase. The result showed that the carbon fiber/BMI composite sized at 150°C had the highest storage modulus at a measuring temperature of 250°C. The storage modulus decreased with increasing sizing temperature from 150°C to 350°C, being influenced by interdiffusion and co-reaction between the LaRC PETI-5 interphase and the BMI matrix resin. The present result is quite consistent with the interfacial result reported earlier in term of interfacial shear strength and interlaminar shear strength of carbon fiber/BMI composites. It is addressed that in the present composite system the sizing temperature of LaRC PETI-5 interphase critically influences not only the interfacial properties but also the dynamic mechanical thermal properties and its control is also important.     

Dynamic mechanical characterization of relaxations in poly(oxymethylene), miscible blends,and oriented filaments

Multifrequency dynamic mechanical analysis (DMA) data were obtained for molded poly(oxymethylene) (POM) and its blends from-150°C to 150°C. Because of the high crystallinity, the assignment of the glass transition in POM has been controversial in the literature. Low and high glass transition temperature (T _g) phenolated compounds, including poly(vinyl phenol), were found to be miscible with POM. The shift of the β transition in the POM blends favors an assignment of the β transition detected at ?3°C(1 Hz), not the ?80°C γ transition, as the T _g in semicrystalline POM because the latter is invariant with diluent. The peak at the β transition in pure POM is weak and can only be seen clearly by DMA measurements on samples that have not “aged” at ambient temperature. This is further evidence that the β transition arises from a cooperative glass-transition-like motion. The γ transition is not influenced by aging because it is due to a concerted localized main chain motion. The β transition of an oriented POM filament can be seen in the DMA flexural loss spectrum at-18°C (1 Hz), but not in a tensile loss spectrum. The broad a relaxation was detected at about 110°C (1 Hz) in molded POM and its blends, while it was shifted to about 135°C in the higher crystallinity, oriented system. The α peak is also independent of diluent, consistent with a crystalline origin for this transition, as was proposed earlier.     

Thermal,Mechanical, and Dielectric Properties of a Dielectric Elastomer for Actuator Applications

Dielectric elastomers (DE) are a new type of electro-active material, which is able to produce a large degree of deformation under electrical stimulation. The thermal, mechanical, and dielectric properties of the most widely used dielectric acrylic elastomer (VHB 4910), commercially available from the company 3M, were studied by differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), dynamic mechanical analysis (DMA), and broadband dielectric spectroscopy (BDS) analyzer, respectively. DSC experiments on the VHB 4910 showed a glass transition at about ?40°C. VHB 4910 started to lose weight at about 250°C from the TGA study. The results of DMA indicated the storage modulus of VHB 4910 increased with frequency and had a strong temperature dependence of elasticity. The dielectric constant of VHB 4910 increased as a function of temperature up to 0°C, followed by a drop till 100°C. The mechanical and electrical efficiency of dielectric elastomer actuators (DEA) of VHB 4910 were analyzed. It was demonstrated that the actuation performance is dominated by the mechanical properties of the elastomer and is less influenced by the frequency and the temperature dependence of the dielectric properties; this may be used to guide the design of actuator configurations, as well as the choice of actuator materials.     

The physicochemical characteristics of oxidized polysaccharides

The paper presents the results obtained in studies of the physicochemical characteristics of modified polysaccharides prepared by the catalytic oxidation of starch with molecular oxygen in an alkaline medium. The amorphous-crystalline structure of starch was partially retained after oxidation. The differential scanning calorimetry data were used to determine the specific heat capacity of oxidized polysaccharides in the vitreous state over the temperature range 10–160°C and the enthalpy and temperature characteristics of fusion of amorphous-crystalline lamellae. The structural and thermodynamic parameters of crystallites (surface free energy, enthalpy, and entropy) were calculated. The segmental mobility of oxidized polysaccharide macromolecules and the transition from the vitreous to high-elasticity state were observed at T _g = 187.7°C, and the transition to the viscous-flow state, above 209°C. The pyrolysis of the polymer began after the unfreezing of its segmental mobility and was accompanied by the release of water and carbon dioxide and the formation of a large amount of coke foam.     

Effect of cellulose–lignin interactions on char structural changes during fast pyrolysis at 100–350 °C

This study investigates the cellulose–lignin interactions during fast pyrolysis at 100–350 °C for better understanding fundamental pyrolysis mechanism of lignocellulosic biomass. The results show that co-pyrolysis of cellulose and lignin (with a mass ratio of 1:1) at temperatures < 300 °C leads to a char yield lower than the calculated char yield based on the addition of individual cellulose and lignin pyrolysis. The difference between the experimental and calculated char yields increases with temperature, from ～2% 150 °C to ～6% at 250 °C. Such differences in char yields provide direct evidences on the existence of cellulose–lignin interactions during co-pyrolysis of cellulose and lignin. At temperatures below 300 °C, the reductions in both lignin functional groups and sugar structures within the char indicate that co-pyrolysis of cellulose and lignin enhances the release of volatiles from both cellulose and lignin. Such an observation could be attributed to two possible reasons: (1) the stabilization of lignin-derived reactive species by cellulose-derived reaction intermediates as hydrogen donors, and (2) the thermal ejection of cellulose-derived species due to micro-explosion of liquid intermediates from lignin. In contrast, at temperatures ≥ 300 °C, co-pyrolysis of cellulose and lignin increases char yields, i.e., with the difference between the experimental and calculated char yields increasing from ～1% at 300 °C to ～8% at 350 °C. The results indicate that the cellulose-derived volatiles are difficult to diffuse through the lignin-derived liquid intermediates into the vapor phase, leading to increased char formation from co-pyrolysis of cellulose and lignin as temperature increases. Such an observation is further supported by the increased retention of cellulose functional groups in the char from co-pyrolysis of cellulose and lignin.     

Understanding of redox behavior of Ni–YSZ cermets

The oxidation of Ni–YSZ cermet as well the reduction of re-oxidized Ni–YSZ cermet was investigated by using temperature-programmed oxidation (TPO), temperature-programmed reduction (TPR) and scanning electron microscope (SEM). The scanning electron microscope (SEM) photographs and temperature-programmed reduction (TPR) profiles indicated that the sintering of smaller nickel oxide crystallites to larger aggregates occurred concurrently with the formation of smaller nickel oxide crystallites from the oxidation of nickel at 800 °C, and the sintering of smaller nickel oxide crystallites at 600 °C was slower than that at 800 °C. The SEM results showed that each Ni particle was separated into a lot of smaller NiO particles during oxidation. The TPO profiles showed that two kinds of nickel particles exist in the anode reduced at 800 and 600 °C, one with high activity towards oxidation for the nickel crystallites directly from reduction, and another one with low activity towards oxidation for the sintered nickel particles. The Ni–YSZ anodes reduced at higher temperature showed higher re-oxidation temperature than the one reduced at lower temperature because of the accelerated passivating and sintering of the smaller nickel particles at higher temperature. The re-oxidation profiles were almost unchanged during redox cycling at 600 °C, whereas the re-oxidation peak temperature decreased during redox cycling at 800 °C, indicating that the primary nickel grains split to smaller ones upon cyclic reduction at higher temperature.     

X-ray diffraction study of temperature dependence of Nairit polychloroprene permolecular structure

With use of the X-ray technique the permolecular structure of Nairit polychloroprene has been investigated. It is shown that the relative degree of crystallinity decreases with the increase in the polymerization temperature. At relatively low temperatures (18–30°C), in Nairits intensive formation of nuclei occurs and simultaneously existing crystallites collapse. Although mean sizes of crystallites decrease, the degree of crystallinity increases. At higher temperatures (above 30°C) melting of existing crystallites and decrease in the number of nuclei lead to decrease in crystallinity and mean sizes of crystallites.     

Crystallization Behavior of Amorphous Poly(l-Lactide)

Amorphous poly(l-lactide) (PLLA) was annealed in two different ways: amorphous samples were heated at a given temperature to induce crystallization (one-step annealing); and amorphous samples were first crystallized at a low temperature and subsequently annealed at a higher temperature than the crystallization temperature. Samples thus prepared were measured by DSC. The original amorphous sample exhibited an exothermic peak at about 100°C (exothermic peak I), an exothermic peak just below the melting point (exothermic peak II), and an endothermic peak when it was melted. Exothermic peak I was caused by cold crystallization. When the melting points of PLLA samples, heat-treated in various ways, were plotted as a function of annealing temperature, there was discontinuity at about 120°C. From analyses of wide-angle X-ray diffraction patterns, it was found that when amorphous PLLA was crystallized at a temperature below 120°C, crystallites of the β-form formed, and when annealed at a temperature above 120°C, crystallites of the α-form grew. Thus, exothermic peak I was attributed to cold crystallization of the β-form, and peak II was caused by the phase transition of the β-form to a more stable form.     

Formation of reaction intermediates and primary volatiles during acid-catalysed fast pyrolysis of cellulose in a wire-mesh reactor

This study aims to understand the fundamental reaction mechanisms during fast pyrolysis of the acid-impregnated cellulose in a wire-mesh reactor at 40–450 °C and 20 °C/s, via quantifying key compounds in the reaction intermediates and primary volatiles. Acid impregnation reduces the onset reaction temperature of cellulose pyrolysis. During acid-catalysed cellulose pyrolysis, 1,6-anhydro-β-d-glucofuranose (AGF), levoglucosenone (LGO) and 5-hydroxymethylfurfural (5-HMF) are identified as major products in the primary volatiles, and the formation of levoglucosan is greatly suppressed. At temperatures < 100 °C, acid catalyses hydrolysis reactions to produce glucose, which is further dehydrated to AGF at 120 °C. At temperatures > 160 °C, acid enhances the dehydration of glucose, levoglucosan and AGF to produce 5-HMF and LGO as major primary products. Once produced, those products can be easily released into the vapour phase, as either aerosols via thermal ejection or vapours via evaporation. As the pyrolysis temperature increases to 240 °C, aromatic compounds can be identified in the primary volatiles, indicating condensation reactions also play important roles during acid-catalysed cellulose pyrolysis under the conditions. As a result, char formation becomes the favoured pathway during acid-catalysed cellulose pyrolysis at temperatures > 300 °C.     

Synthesis of nanocrystalline ZnO nanobelts via pyrolytic decomposition of zinc acetate nanobelts and their gas sensing behavior

The pyrolytic decomposition of layered basic zinc acetate (LBZA) nanobelts (NBs) into nanocrystalline ZnO NBs is investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL). We also report on the gas sensing response of the resulting ZnO nanomaterial to CO. The LBZA NBs are grown at 65 °C in an aqueous solution of zinc acetate dihydrate. AFM and SEM results show as-grown products possess the characteristic layered structure of the LBZA crystals. XRD and XPS results show that annealing as-grown products at 210 °C in air causes a transformation from zinc acetate to nanocrystalline ZnO NBs via thermal decomposition. The ZnO crystalline domain size increases with temperature from 9.2 nm at 200 °C to 94 nm at 1000 °C, as measured from XRD. SEM shows evidence of sintering at 600 °C. The thickness of the NBs, determined via AFM, ranges from 10 to 50 nm and remains approximately constant with annealing temperature. XPS confirmed the chemical transformation from zinc acetate to ZnO and showed a significant remaining zinc hydroxide component for the ZnO NBs consistent with published results. PL measurements at room temperature show a blue shift in peak emission as the nanobelts change from LBZA to ZnO at 200 °C. Above this transition temperature, the ZnO nanobelts possess strong band edge emission at 390 nm and little broad band emission in the visible region. The AFM and SEM images reveal that the crystallites within the nanobelts orientate in rows along the long axis during annealing. This structure provides a high surface area to volume ratio of aligned nanoparticles which is beneficial for gas sensing applications. Gas sensors fabricated from 400 °C annealed nanobelts showed a response of 1.62 when exposed to 200 ppm of CO in dry air at 400 °C, as defined by the ratio of resistance before and during exposure. This indicates that ZnO nanostructures obtained by thermal decomposition of LBZA NBs could provide a cost effective route to high sensitivity gas sensors.     

Evolution of the phase-structure state during annealing of Fe-ZrN films grown by magnetron sputtering

The evolution of the phase-structure state of Fe-ZrN films grown by RF magnetron sputtering and annealed at T = 200–650°C has been studied by transmission electron microscopy, high-resolution electron microscopy, and X-ray diffraction analysis. It has been found that the initial state of the film contains 1- to 5-nm crystallites of α-Fe-based solid solution supersaturated with nitrogen. The number of such crystallites increases, the concentration of nitrogen in them decreases and 2- to 10-nm nanocrystallites of ZrN and Fe2N nitride phases appear after annealing. The formation of zirconium nitride at the first stage (200–500°C) is associated with a decrease in the degree of supersaturation of the α-Fe lattice with nitrogen. At a higher annealing temperature (650°C), a decrease in the nitrogen concentration in the lattices of both the bcc Fe and zirconium nitride phase leads to the formation of iron nitride crystallites.     

Microstructural Evolution and Its Effect on Mechanical Properties of Isotactic Polypropylene by Shear Plastic Deformation at Elevated Temperatures

Isotactic polypropylene (iPP) was plastically shear deformed by equal channel angular extrusion (ECAE) at extrusion temperatures varied from 45 to 125°C (25 mm/min). The evolutions of morphology and crystal orientation were studied by reflected optical microscopy (ROM), scanning electron microscopy (SEM), and X-ray diffraction. It was found that the original spherulites were deformed into nearly ellipsoids with their long axis tilted at an angle away from the flow direction. Azimuthal scanning results revealed that two preferred crystal orientations were formed after ECAE. The crystal plasticity was activated by increasing the extrusion temperature, followed by fast rotation of crystallites toward the shear direction. The thermal mechanical analysis (TMA) indicated that low extrusion temperature was favorable to fix the molecular orientation. The iPP samples processed at the investigated temperatures displayed a significant increase in the impact strength, especially for those extruded at 45°C and 65°C. The tensile results revealed a greater elongation at break in the samples deformed at low temperatures (45°C and 65°C) but not in those deformed at high temperatures (85°C or above).     

Ultrasound-assisted dyeing of cellulose acetate

The possibility of reducing the use of auxiliaries in conventional cellulose acetate dyeing with Disperse Red 50 using ultrasound technique was studied as an alternative to the standard procedure. Dyeing of cellulose acetate yarn was carried out by using either mechanical agitation alone, with and without auxiliaries, or coupling mechanical and ultrasound agitation in the bath where the temperature range was maintained between 60 and 80 °C.The best results of dyeing kinetics were obtained with ultrasound coupled with mechanical agitation without auxiliaries (90% of bath exhaustion value at 80 °C). Hence the corresponding half dyeing times, absorption rate constants according to Cegarra–Puente modified equation and ultrasound efficiency were calculated confirming the synergic effect of sonication on the dyeing kinetics. Moreover the apparent activation energies were also evaluated and the positive effect of ultrasound added to mechanical agitation was evidenced by the lower value (48 kJ/mol) in comparison with 112 and 169 kJ/mol for mechanical stirring alone with auxiliaries and without, respectively.Finally, the fastness tests gave good values for samples dyed with ultrasound technique even without auxiliaries. Moreover color measurements on dyed yarns showed that the color yield obtained by ultrasound-assisted dyeing at 80 °C of cellulose acetate without using additional chemicals into the dye bath reached the same value yielded by mechanical agitation, but with remarkably shorter time.     

Damping Properties of Blends Based on EVM

The mechanical and damping properties of blends of ethylene-vinyl acetate rubber (VA content >40% wt) (EVM)/ethylene-propylene-diene copolymer (EPDM) and EVM/nitrile butadiene rubber (NBR), both with 1.4 phr BIPB (bis (tert-butyl peroxy isopropyl) benzene) as curing agent, were investigated by dynamic mechanical analysis (DMA). The effect of added polyvinyl chloride (PVC), amido donor N-cyclohexyl-2-benzothiazole sulfonamide (CZ), and dicumyl peroxide (DCP) as a substitute curing agent, on the damping and mechanical properties of both rubber blends were studied. The results showed that in EVM/EPDM/PVC blends, EPDM was immiscible with EVM and could not expand the damping range of EVM at low temperature. PVC was miscible with EVM and dramatically improved the damping property of EVM at high temperature while keeping good mechanical performance. In EVM/NBR/PVC blends, PVC was partially miscible with EVM/NBR blends and remarkably widened the effective damping temperature range (EDTR) from 41.1°C for EVM/NBR to 62.4°C. Curing agents BIPB and DCP had a similar influence on EVM/EPDM blends. DCP, however, dramatically raised the height of tan δ peak of EVM/NBR = 80/20 and expanded its EDTR to 64.9°C. CZ had no obvious influence on the EVM/EPDM blends cured with BIPB. However, a small content of CZ enlarged the tan δ peak of EVM/NBR = 80/20 in both height and width, but at the cost of a deterioration of mechanical performance.     

The permeation of gases through symmetric and asymmetric (Loeb-Type) cellulose acetate membranes

Significant differences have been observed in the steady-state permeation of gases through symmetric and asymmetric (Loeb-type) cellulose acetate membranes. The studies were made with O₂, N₂, Ar, Kr, Xe, and CO₂ in the temperature range from -5 to 85°C and at subatmospheric pressures. The differences in permeation behavior may reflect structural differences between the symmetric membranes and the dense surface layer (“skin”) of the asymmetric membranes. The overall mechanism of gas permeation through the symmetric membranes appears to be one of “solution-diffusion,” similar to that observed with many other nonporous polymeric membranes. In the case of the asymmetric membranes, this mechanism is probably modified by the presence of micropores or other imperfections in the dense surface layer. Cellulose acetate exhibits two second-order transitions in the presence of the penetrant gases, one between 60 and 70°C and the other near 15°C. The transitions were observed with both types of membranes.     

Phase velocity and attenuation of 9 GHz hypersound in polycrystalline nickel films as a function of quartz-substrate temperature

Using a movable narrow beam of 9 GHz hypersound and wedge-shaped evaporated Ni films, the phase velocity and attenuation of longitudinal as well as of transverse hypersound was determined at a temperature of 2 K by multiple-beam interferometry in these Ni films. They were evaporated onto a quartz substrate at substrate temperatures ranging from 50°C to 500°C. The macroscopic moduliK (bulk modulus) andG (shear modulus) can be obtained from the measured phase velocities. WhereasK appears independent on substrate temperature and agrees within experimental error with theoretical prediction deduced from known elastic constants of the crystallites, the observed shear modulusG possesses at a substrate temperature of 50°C only 2/3 of the predicted value and increases with substrate temperature by reaching the theoretical value at about 300°C.