Zirconium tungstate/cyanate ester nanocomposites with tailored thermal expansivity

The dimensional stability of polymer matrix composites can be enhanced by reducing the mismatch in the coefficient of thermal expansion (CTE) between the high CTE polymer matrix and low CTE fiber reinforcements, which leads to development of residual stresses and matrix microcracking. A potential strategy to diminish these residual stresses involves development of polymer nanocomposites with well dispersed nanoparticles that reduce the extent of mismatch in CTE. In this work, we explore the potential for development of bulk polymer nanocomposites with tailored thermal expansivity through incorporation of zirconium tungstate nanoparticles that are characterized by a negative CTE in a unique low viscosity bisphenol E cyanate ester (BECy) thermosetting polymer matrix. Incorporation of up to 10 vol.% whisker-like nanoparticles, synthesized by a hydrothermal method, results in a 20% reduction in the CTE of the polymer matrix. However, the nanoparticles exert a dramatic catalytic effect on the cure reaction of BECy resin and subsequently decrease the onset temperature of the glass transition for the cured polymer network, at high filler loadings.     

Interfacial enhancement of nano-SiO2/polypropylene composites

The authors proposed an approach for manufacturing nano-SiO₂/polypropylene (PP) composites by in situ reactive processing. The key issue lies in that the nanoparticles were covalently bonded to the matrix polymer via polyurethane (PU) elastomer and PP-g-NH₂. Unlike the previous techniques based on graft polymerization, the present one did not need to pretreat the nanoparticles. Taking the advantages of rubber-type grafting polymer (i.e. PU) and interfacial reactive compatibilization with PP-g-NH₂, a synergetic toughening effect was observed for the PP nanocomposites. Only very low concentrations of nano-SiO₂ (1.5–2.5 vol.%) and PU (<4 vol.%) were sufficient to greatly increase notched impact strength of PP. Meanwhile, tensile properties of the nanocomposites were also slightly enhanced.     

Chemical and thermal reduction of graphene oxide and its electrically conductive polylactic acid nanocomposites

Graphene oxide (GO) was reduced with biocompatible glucose and polyvinylpyrrolidone (PVP) and incorporated in polylactic acid (PLA). The thermal reduction of GO during the compression molding of PLA was also studied to delineate the reduction efficiencies from thermal and chemical processes. Results indicate that glucose is more effective in the reduction of GO (rGO-g) with a much higher electrical conductivity than PVP and thermally treated GO. Even rGO-g was also highly efficient in improving the electrical conductivity of PLA. The composite with ∼1.25 vol.% of rGO-g exhibited a high conductivity of ∼2.2 S/m due to the chemical reduction of GO with glucose and the thermal reduction of rGO-g during the compression molding process.     

In situ thermal reduction of graphene oxide for high electrical conductivity and low percolation threshold in polyamide 6 nanocomposites

Electrically conductive and thermally stable polyamide 6 (PA 6) nanocomposites were prepared through one-step in situ polymerization of ε-caprolactam monomer in the presence of electrically insulating and thermally unstable graphene oxide (GO) nanosheets. These nanocomposites show a low percolation threshold of ∼0.41 vol.% and high electrical conductivity of ∼0.028 S/m with only ∼1.64 vol.% of GO. Thermogravimetric analysis and X-ray photoelectron spectroscopy results of GO before and after thermal treatment at the polymerization temperature indicate that GO was reduced in situ during the polymerization process. X-ray diffraction patterns and scanning electron microscopy observation confirm the exfoliation of the reduced graphene oxide (RGO) in the PA 6 matrix. The low percolation threshold and high electrical conductivity are attributed to the large aspect ratio, high specific surface area and uniform dispersion of the RGO nanosheets in the matrix. In addition, although GO has a poor thermal stability, its PA 6 nanocomposite is thermally stable with a satisfactory thermal stability similar to those of neat PA 6 and PA 6/graphene nanocomposite. Such a one-step in situ polymerization and thermal reduction method shows significant potential for the mass production of electrically conductive polymer/RGO nanocomposites.     

Electrical properties of Pb(Mg1/3Nb2/3)O3-PbTiO3 ceramics modified with WO3

Ferroelectrics 0.67Pb (Mg_1/3Nb_2/3)O₃-0.33PbTiO₃ (PMN-PT) + x mol% WO₃ (x=0.1, 0.5, 1, 2) were prepared by columbite precursor method. Electrical properties of WO₃-modified ferroelectrics were investigated. X-ray diffraction (XRD) was used to identify crystal structure, and pyrochlore phase were observed in 0.67Pb (Mg_1/3Nb_2/3)O₃-0.33PbTiO₃+2 mol% WO₃. Dielectric peak temperature decreased with WO₃ doping, indicating that W⁶⁺ incorporated into PMN-PT lattice. Lattice constant, pyrochlore phase and grain size contribute to the variation of K_max. Both piezoelectric constant (d₃₃) and electromechanical coupling factors (k_p) were enhanced by doping 0.1 mol% WO₃, which results from the introduction of “soft” characteristics into PMN-PT, while further WO₃ addition was detrimental. We consider that the two factors, introduction of “soft” characteristics and the formation of pyrochlore phase, appear to act together to cause the variation of piezoelectric properties of 0.67PMN-0.33PT ceramics doping with WO₃.     

Multi-walled carbon nanotubes reinforced Al2O3 nanocomposites: Mechanical properties and interfacial investigations

Well-dispersed multi-walled carbon nanotubes (CNTs) reinforced Al₂O₃ nanocomposites were successfully fabricated by hot-pressing. The resulting promising improvements in fracture toughness, by 94% and 65% with 2 and 5 wt.% CNTs addition respectively, compared with monolithic Al₂O₃, were attributed to the good dispersion of CNTs within the matrix, crack-bridging by CNTs and strong interfacial connections between the CNTs and the matrix. The interfacial phase characteristics between CNTs and Al₂O₃ were investigated via combined techniques. It is believed that a possible aluminium oxy-carbide as the primary interfacial phase was produced via a localized carbothermal reduction process. This interface phase presumably has good chemical compatibility and strong connections with both CNTs and the matrix and led nanocomposites to higher fracture toughness.     

Thermal, dielectric and microwave absorption properties of polyaniline-CoFe2O4 nanocomposites

The present paper deals with the synthesis of conducting ferromagnetic polyaniline-CoFe₂O₄ (PC) nanocomposites via one-step chemical oxidative polymerization of aniline in the presence of CoFe₂O₄ nanoparticles (30-40 nm). These nanocomposites of PC have been characterized by high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and vibrating sample magnetometer (VSM). Extended thermal analysis has revealed that the activation energy of these nanocomposites varies from 75.3 to 84.3 kJ/mol as compared to the activation energy of 50.3 kJ/mol for polyaniline-DBSA. In addition, dielectric and microwave absorption properties of the nanocomposites have been measured in the frequency range of 12.4-18 GHz (Ku-band) which demonstrate that more than 99% attenuation of microwaves (SE_A = 21.5 dB) has been achieved using these nanocomposites. Systematic investigations reveal that the CoFe₂O₄ nanoparticles in the polyaniline matrix have phenomenal effect in determining the microwave absorption properties of the nanocomposites.     

Polymer/bioactive glass nanocomposites for biomedical applications: A review

Nanoscale bioactive glasses have been gaining attention due to their reported superior osteoconductivity when compared to conventional (micron-sized) bioactive glass materials. The combination of bioactive glass nanoparticles or nanofibers with polymeric systems enables the production of nanocomposites with potential to be used in a series of orthopedic applications, including scaffolds for tissue engineering and regenerative medicine. This review presents the state of art of the preparation of nanoscale bioactive glasses and corresponding composites with biocompatible polymers. The recent developments in the preparation methods of nano-sized bioactive glasses are reviewed, covering sol–gel routes, microemulsion techniques, gas phase synthesis method (flame spray synthesis), laser spinning, and electro-spinning. Then, examples of the preparation and properties of nanocomposites based on such inorganic bionanomaterials are presented, obtained using various polymer matrices, including polyesters such as poly(hydroxybutyrate), poly(lactic acid) and poly(caprolactone), and natural-based polymers such as polysaccharides (starch, chitin, chitosan) or proteins (silk fibroin, collagen). The physico-chemical, mechanical, and biological advantages of incorporating nanoscale bioactive glasses in such biodegradable nanocomposites are discussed and the possibilities to expand the use of these materials in other nanotechnology concepts aimed to be used in different biomedical applications are also highlighted.     

CeF3 nanoparticles: synthesis and characterization

CeF₃ nanoparticles 5-10 nm in size were prepared using the polyol method. CeCl₃ and HF were heated up in ethylene glycol. At a temperature of 180 °C crystalline CeF₃ nanoparticles were formed. The material was washed with ethanol, centrifugated and dried. The particles were characterized by EDX, XRD and TEM.     

Crystal growth and spectral properties of Pr:La2(WO4)3

Pr³⁺-doped La₂(WO₄)₃ single crystal with dimensions up to Ø 20 mm × 35 mm has been grown by the Czochralski method. The structure of the Pr³⁺:La₂(WO₄)₃ crystal was determined by the X-ray powder diffraction and the Pr³⁺ concentration in this crystal was determined. The absorption and fluorescence spectra of Pr³⁺:La₂(WO₄)₃ crystal were measured at room temperature, and the fluorescence lifetime of main emission multiplets were estimated from the recorded decay curves. The spectral properties related to laser performance of the crystal were evaluated.     

Characterization of epoxy functionalized graphite nanoparticles and the physical properties of epoxy matrix nanocomposites

This work presents a novel approach to the functionalization of graphite nanoparticles. The technique provides a mechanism for covalent bonding between the filler and matrix, with minimal disruption to the sp² hybridization of the pristine graphene sheet. Functionalization proceeded by covalently bonding an epoxy monomer to the surface of expanded graphite, via a coupling agent, such that the epoxy concentration was measured as approximately 4 wt.%. The impact of dispersing this material into an epoxy resin was evaluated with respect to the mechanical properties and electrical conductivity of the graphite–epoxy nanocomposite. At a loading as low as 0.5 wt.%, the electrical conductivity was increased by five orders of magnitude relative to the base resin. The material yield strength was increased by 30% and Young’s modulus by 50%. These results were realized without compromise to the resin toughness.     

Effect of carbon nanofibers (CNFs) content on thermal and mechanical properties of CNFs/SiC nanocomposites

Carbon nanofibers dispersed β-SiC (CNFs/SiC) nanocomposites were prepared by hot-pressing via a transient eutectic phase route at 1900 °C for 1 h under 20 MPa in Ar. The effects of additional CNFs content between 1 and 10 wt.% were investigated, based on densification, microstructure, thermal and mechanical properties. The CNFs/SiC nanocomposites by the CNFs contents below 5 wt.% exhibited excellent relative densities over 98% with well dispersed CNFs. However, the CNFs/SiC nanocomposites containing the CNFs of 10 wt.% possessed a relative density of 92%, accompanying CNFs agglomerates and many pores located inside the agglomerates. The three point bending strength gradually decreased with the increase of CNFs content, but the indentation fracture toughness increased to 5.7 MPa m^1/2 by the CNFs content of 5 wt.%. The thermal conductivity was enchanced with the increase of CNFs content and represented a maximum value of 80 W/mK at the CNFs content of 5 wt.%.     

Improving the flexural and thermomechanical properties of amino-functionalized carbon nanotube/epoxy composites by using a pre-curing treatment

A prior thermal (pre-curing) treatment of mixtures of epoxy monomer and amino-functionalized carbon nanotubes (CNTs) was used to promote a chemical reaction between the matrix and the reinforcement, favouring the formation of a strong interface. Samples of epoxy resin and different weight percentages of amino-functionalized multi-walled CNTs were prepared with and without the pre-curing treatment (150 °C, 1 h). The degree of dispersion of the nanofiller was better when this pre-curing treatment was used. This allowed a higher CNT content while keeping a high sample homogeneity. Without the pre-curing step, the addition of CNTs increases both the flexural strength and strain to failure by 45%. Moreover, with the pre-curing step, the nanocomposite with 0.25 wt.% CNTs presents an increase of flexural strength by 58% and strain to failure by 68% regard to neat epoxy resin.     

Determination of Young’s modulus in polyester-Al2O3 and epoxy-Al2O3 nanocomposites using the Digital Image Correlation method

Young’s modulus of nano-composite systems composed of unsaturated polyester and epoxy resins with alumina nanoparticles of different sizes has been experimentally estimated. The nanoparticles used were spherical alpha-Al₂O₃ having 30-40 and 200 nm in diameter. Young’s modulus was estimated using an inverse problem that is solved by means of the classical Levenberg-Marquardt technique. A cantilever beam under bending was used in the experiments and the experimental procedure was performed using the Digital Image Correlation method, which is a well-established optical-numerical method for estimating full-field displacement. Experimental results indicate that Young’s modulus increases with increasing nanoparticle volume fraction. Finally, the estimated Young’s moduli were compared with classical theoretical models, showing that the experimental results are in agreement with literature data.     

Preparation and photocatalytic activity of WO3/TiO2 nanocomposite particles

A novel photocatalyst WO₃/TiO₂ nanocomposite was prepared through a hydrothermal method by using cetyltrimethylammonium bromide (CTAB) as surfactant. The obtained WO₃/TiO₂ was characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), transmission electron microscope (TEM) and diffused reflectance spectroscopy (DRS). Photocatalytic experiments indicate that the nanocomposites show much higher photoactivity than that of pure TiO₂ in the photodegradation reaction of Rhodamine B (RhB). The increased photoactivity of WO₃/TO₂ may be attributed to the improvement of the light absorption properties and the slow down of the recombination between the photoexcited electrons and holes during the photoreaction.     

Nanocomposite BaSO4/Y2O3:Eu powders prepared by heterogeneous nucleation processing

Forming core–shell-structured phosphor particles is an effect way to improve the properties of the rare-earth-doped inorganic luminescent systems, as well as to achieve a reduction in the amount of expensive rare earth metal. Heterogeneous nucleation processing is a commonly used method to prepared core–shell-structured particles. A nanocomposite BaSO₄/Y₂O₃:Eu³⁺ powder was prepared by coating BaSO₄ submicrospheres with nano-Y₂O₃:Eu³⁺ particles via heterogeneous nucleation processing. Thermogravimetric analysis and differential scanning calorimetry (TGA/DSC) were utilized to reveal the mechanism of the homogenous precipitation reaction process. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS) were utilized to characterize the BaSO₄/Y₂O₃:Eu³⁺ core–shell-structured phosphor particles. By controlling the hydrolysis of urea, BaSO₄ particles are well coated with the shell of Y₂O₃:Eu³⁺, and the nucleation of coating materials is predominantly heterogeneous rather than homogeneous. Photoluminescence spectra were utilized as well. The BaSO₄/Y₂O₃:Eu³⁺ particles show a red emission corresponding to ⁵D₀–⁷F₂ of Eu³⁺ under the excitation of ultraviolet.     

Synthesis of La(Mg0.5Ti0.5)O3 ceramics for microwave applications

La(Mg_0.5Ti_0.5)O₃ ceramics were prepared by a non-conventional chemical route, which was based on the Pechini method. For the synthesis of La(Mg_0.5Ti_0.5)O₃ powders, special attention was paid to calcination and milling conditions. Powder morphology and composition were evaluated. Fine La(Mg_0.5Ti_0.5)O₃ powders were obtained at lower temperatures than by conventional methods. Sintering under different conditions was also tested. Dense La(Mg_0.5Ti_0.5)O₃ ceramics were obtained at lower temperatures showing a single phase composition and a homogeneous microstructure. Preliminary dielectric characterization at microwave frequencies was also performed.     

A detailed thermal analysis of nanocomposites filled with SiO2, AlN or boehmite at varied contents and a review of selected rules of mixture

In order to investigate and compare the thermal and mechanical properties of nanocomposites filled with various nanoparticles multiple experiments have been carried out. The aim of this study was to enhance the thermal and mechanical properties of epoxy resin for fiber reinforces structures by the addition of nanoparticles. These altered properties were analyzed and reconciled with each other as well as compared to data developed from different rules of mixture. A hot curing epoxy system based on bisphenol-A (DGEBA) has been filled with different contents of silicon dioxide (SiO₂), aluminum nitride (AlN) and boehmite nanoparticles to examine the effects in the material’s thermal and mechanical behavior with variable filler materials and contents compared to the unfilled epoxy. The glass transition temperature fluctuates very little with varied filler content. The coefficient of thermal expansion can be reduced with increasing filler content. This improvement recurs also in thermal conductivity and during dynamic mechanical analysis. Several rules of mixture have been applied to be verified on the basis of varied materials and filler contents. The results did not always match the experiments. The deviations are ascribed to the influence of interphases that build up in the vicinity of the nanoparticles during the process of curing.