Preparation of LiMn2O4 thin films by aqueous solution deposition

Cathode material LiMn₂O₄ thin films were prepared by aqueous solution deposition using lithium acetate and manganese acetate as starting materials. The structures, morphologies, and the first discharge specific capacity of the thin films were investigated as a function of annealing temperature and time. The cycling properties of the thin films were also examined. The results show that LiMn₂O₄ thin films prepared by this method are homogenous and crack-free. The thin film annealed at 750°C for 30 min has good rechargeability. The capacity loss per cycle is about 0.05% after being cycled 100 times.     

Dynamic mechanical analysis and thermal properties of LLDPE/EVA/modified silica nanocomposites

The effect of hexamethylene disilazane modified nanosilica on the dynamic mechanical analysis (DMA), crystallization, melting and thermal degradation behavior of linear low density polyethylene/ethylene vinyl acetate copolymer (LLDPE/EVA) blends are explored.Detailed DMA analysis is carried out in order to investigate the reinforcing behavior of nanosilica adopting Kerner–Nielson model. Oxidative degradation and thermal stabilities of samples are also studied by the thermogravimetery analysis. The high content of nanosilica particles results in significant shift of degradation temperature to higher temperatures in the oxygen atmosphere. This behavior might be attributed to the barrier properties of nanoparticles against oxygen and gaseous degradation products. However, incorporation of modified nanosilica into LLDPE/EVA blend is decreased the onset of degradation temperature of the unfilled system. In nitrogen atmosphere, no changes are observed in the thermal degradation range and only a reduction is documented in the onset of degradation temperature. Considering important role of onset of degradation temperature, activation energy of starting of degradation temperature is calculated utilizing Kissinger-Ozawa model in both oxygen and nitrogen atmospheres. Results showed that activation energy of degradation reaction is decreased by ∼ 20 kJ/mol. This decrease is owing to the release of modifiers from the nanoparticles.     

Preparation,structure and thermal properties of polylactide/sepiolite nanocomposites with and without organic modifiers

Polylactide-based nanocomposites containing unmodified and organic modified sepiolite were prepared through a solution casting method. The structure and properties of materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). From the results it can be concluded that the bundles of sepiolite have been dispersed into small aggregates containing several nanorods without destroying the crystal structure. Sepiolite nanofibers were well dispersed in the PLA matrix, exhibiting a randomly orientation with the contact among them in all cases. But the thermal stability of nanocomposites has been improved more by introducing unmodified sepiolite than that with organic modified sepiolite, which has also been confirmed by molecular dynamics simulation results that hydrophobic parts of organic modifiers could prevent the interaction between PLA molecules and sepiolite surface.     

Influence of carboxylic functionalization of MWCNTs on the thermal properties of MWCNTs/DGEBA/EMI-2,4 nanocomposites

The influence of carboxylic functionalization (COOH-functionalization) of multi-walled carbon nanotubes (MWCNTs) on the thermal properties of MWCNTs/diglycidyl ether of bisphenol A/2-ethyl-4-methylimidazole (MWCNTs/DGEBA/EMI-2,4) nanocomposites was studied using DSC and TGA. The results showed that, at the initial curing stage, activation energy E decreases with increasing curing degree α, moreover, COOH-functionalization of MWCNTs decreases E. Therefore, COOH-functionalization of MWCNTs does not change the autocatalytic cure reaction mechanism of MWCNTs/DGEBA/EMI-2,4 system and has catalytic effect on the curing process. Then, at the later curing stage, carboxylated MWCNTs (COOH-MWCNTs) increase the inflexions of the curves of E vs. α less than purified MWCNTs, indicating that COOH-MWCNTs delay the vitrification less than purified MWCNTs. Furthermore, COOH-functionalization of MWCNTs also improves the thermal stability of nanocomposites.     

PHBV nanocomposites based on organomodified montmorillonite and halloysite: The effect of clay type on the morphology and thermal and mechanical properties

The aim of this study was to evaluate the effect of the addition of two types of nanoparticles, organomodified montmorillonite Cloisite® 30B (C-30B), and a tubular like clay, halloysite (HNT), on the morphology and thermal and mechanical properties of poly(hydroxybutyrate-co-hydroxyvalerate) – PHBV nanocomposites. TEM and WAXD results showed a combination of a few tactoids and a partially exfoliated structure for PHBV/C-30B nanocomposites and a good dispersion of HNT in the PHBV matrix. DSC analysis indicated a lower nucleation density with the addition of nanoparticles. Furthermore, the presence of C-30B led to the formation of double melting peaks, related to different crystalline phases. However, a higher melting temperature was obtained for PHBV/HNT nanocomposites. A general increase in the Young’s modulus was observed. However, for PHBV/C-30B nanocomposites, this enhancement was at the expense of the strain at break and impact strength, probably due to the degradation of the polymer during processing.     

Synthesis of solid solution Er2−xCexW3O12 and studies of their thermal expansion behavior

The syntheses and structures of Er_2−xCe_xW₃O₁₂ were studied. It was found that pure phases could form only for 0.0 ≦ x ≦ 0.4 and 1.5 ≦ x ≦ 2.0. Compounds with 0 ≦ x ≦ 0.4 have the hydrated orthorhombic structure at room temperature and transform to unhydrated orthorhombic one above 135 °C whereas samples with 1.5 ≦ x ≦ 2.0 crystallize in monoclinic structure. Thermal expansion properties of Er_2−xCe_xW₃O₁₂ were studied with high temperature X-ray powder diffraction. Samples with 0 ≦ x ≦ 0.4 exhibit negative thermal expansion in temperature range of 200-800 °C and higher cerium content leads to more negative thermal expansion coefficient. However, compounds with 1.5 ≦ x ≦ 2.0 show positive thermal expansion owing to the edge-sharing polyhedra.     

Effects of milling on the thermal stability of synthetic hydromagnesite

Hydromagnesite is a basic magnesium carbonate that undergoes an endothermic decomposition with water and carbon dioxide release in the temperature range of 200-550 °C. Due to this thermal behaviour it has been studied as flame retardant filler for polymers in cable applications. For this purpose the particle size distribution should be optimized, as it is in most cases responsible for decrease in final composite mechanical properties. This work describes the variations found in the thermal behaviour of hydromagnesite associated with the process of particle size reduction. Air jet micronization was compared with mechanical milling. Thermogravimetry and differential scanning calorimetry were used to study thermal decomposition. FTIR spectroscopy and XRD analysis of the solid residue after heating were used to follow structural changes. Decomposition behaviour of synthetic hydromagnesite was shown to be dependent of the applied particle size reduction process. A remarkable increase in the decomposition rate was observed for the milled sample, which was attributed to the introduction of defects in the crystalline structure during the mechanical milling. Therefore, it was concluded that the mechanical milling process may affect the thermal decomposition of hydromagnesite and therefore its characteristics as flame retardant.     

Hygroscopicity and bulk thermal expansion in Y2W3O12

Negative thermal expansion material, Y₂W₃O₁₂ has been synthesized by the solid-state method and bulk thermal expansion of the material has been investigated from 300 to 1100 K. The material reversibly forms a trihydrate composition whose X-ray diffraction pattern can be indexed to an orthorhombic unit cell with a = 10.098(1) Å, b = 13.315(3) Å, c = 9.691(4) Å. The cell volume of the hydrated pattern is 7% smaller than the unhydrated cell volume. According to the dilatometric studies, the material shows a 3-6% increase in the linear strain at about 400 K, which can be attributed to the removal of water. Sintering the material at 1473 K leads to large grain size of >100 μm, which results in a large hysteresis in the bulk thermal expansion behavior. Hot pressing at 1273 K under a uniaxial pressure of 25 MPa results in a fine-grained (2-5 μm) ceramic. Glazing the ceramic prevents moisture pick up and a linear thermal expansion over the entire temperature range 1100-300 K and an average linear thermal expansion co-efficient of −9.65 × 10⁻⁶/K is observed. The effect of water on the thermal expansion behavior of this system is discussed.     

Effects of delignification in the production of plant-based cellulose nanofibers for optically transparent nanocomposites

The pulp-making procedures prior to nanofibrillation require considerable chemical treatments to leach the matrix substances. In particular, the sodium chlorite (NaClO₂) solution treatment is cyclically applied to remove lignin. In this study, we clarified the effects of delignification in the production of cellulose nanofibers and nanocomposites through a comparison of plants with lignin (2 year old lignified mature bamboo culms) and without lignin (immature bamboo shoot culms). We concluded that the NaClO₂ treatment might have degraded the cellulose nanofibers, as we found that the morphology and properties of the cellulose nanofibers extracted from mature bamboo had no advantages over the nanofibers from immature bamboo. In addition, the light transmittance of the cellulose nanocomposites from immature bamboo was higher even at lower wavelengths.     

Influence of highly branched poly(amido amine) on the properties of hyperbranched polyurethane/clay nanocomposites

The fascinating architecture of hyperbranched polymer imparts a truck load of novel properties to the material. Epoxy resin modified Mesua ferrea L. seed oil based hyperbranched polyurethane (MHBPU) nanocomposites were prepared by in situ technique using s-triazine based highly branched poly(amido amine) (HBPAA) modified organo-nanoclay. The HBPAA was synthesized by A₂ + B₃ technique with good yield (>75%) using urea and s-triazine. The formation of the polymer was confirmed with the help of ¹H NMR, FTIR, UV spectroscopic, and measurements of solution viscosity with other physical properties. This HBPAA was successfully utilized to swell the montmorillonite organo-nanoclay as the interlayer gallery distance increases up to 8.2 Å, obtained by XRD study. The FTIR further confirmed the presence of interactions of the HBPAA moiety with the organo-clay layers. The formation of nanocomposites was confirmed by FTIR, XRD, SEM, TEM and rheological studies. The improvements of tensile strength (1.7 times) and scratch hardness (2.3 times) along with the dramatic enhancement of thermostability and flame retardancy without compromising impact resistance, bending, and elongation at break of the nanocomposites compared to pristine MHBPU thermoset are the noticeable credits of the present investigation. The results signify the great potential of the studied materials for various advanced applications.     

Hybrid self-assembled multilayer film formed by alternating layers of H4SiW12O40 and 1,10-diaminodecane (DAD)

A hybrid self-assembled multilayer film was prepared by alternating adsorption of H₄SiW₁₂O₄₀ and 1,10-diaminodecane. The film was uniformly deposited and was found to be photochromic, as monitored by the UV spectroscopy. The film was also studied by X-ray photoelectron spectroscopy.     

Structure and properties of ternary manganese nitride Mn3CuNy thin films fabricated by facing target magnetron sputtering

Deposition of Mn₃CuN_y thin films on single crystal Si (1 0 0) at various substrate temperatures (T_sub) by facing target magnetron sputtering is reported. The crystal structure and composition were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results confirmed that the crystalline antiperovskite Mn₃CuN_y thin film with (2 0 0) highly preferred texture had been obtained at T_sub = 180 °C. Furthermore, for the resulting Mn₃CuN_y thin film, it showed different properties compared with the bulk counterpart. There was a paramagnetic to ferrimagnetic transition at 225 K with decreasing temperature. The change of the lattice constant with temperature presented positive thermal expansion behavior and no structural transition was observed. The average linear thermal expansion coefficient (α) is 2.49 × 10⁻⁵ K⁻¹ from 123 K to 298 K. More interestingly, the temperature dependence of resistivity displayed a semiconductor-like behavior, i.e. an obvious monotonous decrease of resistivity with increasing temperature.     

Effects of carbon nanotubes and carbon fiber reinforcements on thermal conductivity and ablation properties of carbon/phenolic composites

The ablation properties and thermal conductivity of carbon nanotube (CNT) and carbon fiber (CF)/phenolic composites were evaluated for different filler types and structures. It was found that the mechanical and thermal properties of phenolic-polymer matrix composites were improved significantly by the addition of carbon materials as reinforcement. The concentrations of CF and CNT reinforcing materials used in this study were 30 vol% and 0.5 wt%, respectively. The thermal conductivity and thermal diffusion of the different composites were observed during ablation testing, using an oxygen–kerosene (1:1) flame torch. The thermal conductivity of CF mat/phenolic composites was higher than that of random CF/phenolic composites. Both CF mat and CNT/phenolic composites exhibited much better thermal conductivity and ablation properties than did neat phenolic resin. The more conductive carbon materials significantly enhanced the heat conduction and dissipation from the flame location, thereby minimizing local thermal damage.     

Influences of clay and manufacturing on fire resistance of organoclay/thermoset nanocomposites

The organoclay GFRP nanocomposites are prepared using the vacuum assisted resin transfer moulding method. Two grades of organophilic clay with three content levels, three types of thermosetting resins (polyester, vinyl ester and epoxy), and three nanoclay dispersion techniques are investigated. To understand the effects of these factors on the fire performance, Taguchi design of experiments (DoE) method is employed and preferred combinations of factors are determined using a one-step and a proposed two-step GLM ANOVA. The one-step ANOVA is applied directly on the experimental results, while the two-step ANOVA is conducted on the signal-to-noise ratios obtained from the Taguchi analysis. The combination of mechanical and ultrasonic dispersing procedure has been found to have considerable influence on the of nanoclay distribution. While both approaches provide insights into the influences of each fabrication factor, the two-step gives a better prediction of the favourable response combination for the nanocomposites when validated with experiments.     

Thermal expansion studies of Gd2Mo3O12 and Gd2W3O12

Simultaneous thermogravimetric/differential thermal analysis of Gd₂Mo₃O₁₂ showed an irreversible phase transition at 1178 K where as Gd₂W₃O₁₂ showed reversible phase transition at 1433 K, which were confirmed by powder X-ray diffraction. The thermal expansion behavior of α-Gd₂Mo₃O₁₂ (room temperature phase), β-Gd₂Mo₃O₁₂ (phase obtained by heating Gd₂Mo₃O₁₂ at 1223 K) and Gd₂W₃O₁₂ have been investigated using high temperature X-ray diffractometer. The cell volume of α-Gd₂Mo₃O₁₂, β-Gd₂Mo₃O₁₂ and Gd₂W₃O₁₂, fit into polynomial expression with respect to temperature, showed positive thermal expansion up to 1073, 1173 and 1173 K, respectively. The average volume expansion coefficients for α-Gd₂Mo₃O₁₂, β-Gd₂Mo₃O₁₂ and Gd₂W₃O₁₂ are 39.52 × 10⁻⁶, 21.23 × 10⁻⁶ and 37.96 × 10⁻⁶ K⁻¹, respectively.     

Synthesis, thermal stability, and photocatalytic activity of nanocrystalline titanium carbide

Titanium carbide (TiC) was prepared via one simple route by the reaction of metallic magnesium powders with titanium dioxide (TiO₂) and potassium acetate (CH₃COOK) in an autoclave at 600 °C and 8 h. Phase structure and morphology were characterized by X-ray powder diffraction (XRD) and Scanning electron microscopy (SEM). The results indicated that the product was cubic TiC, which consisted of particles with an average size of about 100 nm in diameter. The product was also studied by the thermogravimetric analysis (TGA) and its photocatalysis. It had good thermal stability and oxidation resistance below 350 °C in air. In addition, we discovered that the cubic TiC powders exhibited photocatalytic activity in degradation of Rhodamine-B (RhB) under 500 W mercury lamp light irradiation.     

Polyimide/sepiolite nanocomposite films: Preparation, morphology and properties

Polyimide/sepiolite nanocomposite films have been prepared via an in situ polymerization method. The process involves the dispersion of sepioite in N,N-dimethylacetamide, polycondensation of 2,2′-bis [4-(3,4-dicarboxyphenoxy) phenyl] propane dianhydride and 4,4′-oxydianiline in the presence of sepiolite suspension to form poly(amic acid), and the thermal imidization of poly(amic acid)/sepiolite nanocomposite. The morphology, thermal and mechanical performance, and water absorption of nanocomposite films were systematically studied with various sepiolite contents. The results indicated that sepiolite was dispersed homogeneously at a nanometer scale in polyimide matrix. Owing to such nanodispersion of sepiolite, the polyimide/sepiolite nanocomposite films exhibit dramatic improvements on the mechanical properties and the coefficient of thermal expansion while fine thermal stability and low water absorption capacity were also maintained. When the sepiolite content increased to 16% the polyimide/sepiolite nanocomposite film achieved as much as 41% and 94% increase on the tensile strength and modulus respectively, and 50% decreased in coefficient of thermal expansion.     

Effect of surfactant treatment on thermal stability and mechanical properties of CNT/polybenzoxazine nanocomposites

The mechanical and thermo-mechanical properties of polybenzoxazine nanocomposites containing multi-walled carbon nanotubes (MWCNTs) functionalized with surfactant are studied. The results are specifically compared with the corresponding properties of epoxy-based nanocomposites. The CNTs bring about significant improvements in flexural strength, flexural modulus, storage modulus and glass transition temperature, T_g, of CNT/polybenzoxazine nanocomposites at the expense of impact fracture toughness. The surfactant treatment has a beneficial effect on the improvement of these properties, except the impact toughness, through enhanced CNT dispersion and interfacial interaction. The former four properties are in general higher for the CNT/polybenzoxazine nanocomposites than the epoxy counterparts, and vice versa for the impact toughness. The addition of CNTs has an ameliorating effect of lowering the coefficient of thermal expansion (CTE) of polybenzoxazine nanocomposites in both the regions below and above T_g, whereas the reverse is true for the epoxy nanocomposites. This observation has a particular implication of exploiting the CNT/polybenzoxazine nanocomposites in applications requiring low shrinkage and accurate dimensional control.     

Characterization and properties of transparent cellulose nanowhiskers-based graphene nanoplatelets/multi-walled carbon nanotubes films

Transparent cellulose nanowhiskers (CNW)/graphene (GN) and CNW/multi-wall carbon nanotube (MWCNT) films were obtained by ultrasonication assisted mechanically stirring followed by solvent casting methods. GN has more significant influence on the properties of CNW film than MWCNT does because GN exhibits strong interaction with CNW by its adsorption on the surface of GN. Thermal behaviors of CNW-based composite films were greatly affected by addition of GN or MWCNT. The melting peak and initial degradation temperature increase by 23.5 and 24 °C, and by 78 °C and 94 °C for the composite films containing 5 wt% MWCNT and 5 wt% GN, respectively. The composites show the contact angles of 61.9° for GN included film and 46.9° for MWCNT included film, which is higher than that of pure CNW film (42.8°).     

Evaluation of thermal,mechanical, and electrical properties of PVDF/GNP binary and PVDF/PMMA/GNP ternary nanocomposites

Graphene nanoplatelet (GNP) was incorporated into poly(vinylidene fluoride) (PVDF) and PVDF/poly(methyl methacrylate) (PMMA) blend to achieve binary and ternary nanocomposites. GNP was more randomly dispersed in binary composites compared with ternary composites. GNP exhibited higher nucleation efficiency for PVDF crystallization in ternary composites than in binary composites. GNP addition induced PVDF crystals with higher stability; however, PMMA imparted opposite effect. The binary composite exhibited lower thermal expansion value than PVDF; the value further declined (up to 28.5% drop) in the ternary composites. The storage modulus of binary and ternary composites increased to 23.1% and 53.9% (at 25 °C), respectively, compared with PVDF. Electrical percolation threshold between 1 phr and 2 phr GNP loading was identified for the two composite systems; the ternary composites exhibited lower electrical resistivity at identical GNP loadings. Rheological data confirmed that the formation of GNP (pseudo)network structure was assisted in the ternary system.