Preparation of nano‐reinforced thermal conductive natural rubber composites

Natural rubber (NR) composites highly filled with nano‐α‐alumina (nano‐α‐Al₂O₃) modified in situ by the silane coupling agent bis‐(3‐triethoxysilylpropyl)‐tetrasulfide (Si69) were prepared. The effects of various modification conditions and filler loading on the properties of the nano‐α‐Al₂O₃/NR composites were investigated. The results indicated that the preparation conditions for optimum mechanical (both static and dynamic) properties and thermal conductivity were as follows: 100 phr of nano‐α‐Al₂O₃, 6 phr of Si69, heat‐treatment time of 5 min at 150°C. Furthermore, two other types of fillers were also investigated as thermally conductive reinforcing fillers for the NR systems: (1) hybrid fillers composed of 100 phr of nano‐α‐Al₂O₃ and various amounts of the carbon black (CB) N330 and (2) nano‐γ‐Al₂O₃, the particles of which are smaller than those of nano‐α‐Al₂O₃. The hybrid fillers had better mechanical properties and dynamic performance with higher thermal conductivity, which means that it can be expected to endow the rubber products serving under dynamic conditions with much longer service life. The smaller sized nano‐γ‐Al₂O₃ particles performed better than the larger‐sized nano‐α‐Al₂O₃ particles in reinforcing NR. However, the composites filled with nano‐γ‐Al₂O₃ had lower thermal conductivity than those filled with nano‐α‐Al₂O₃ and badly deteriorated dynamic properties at loadings higher than 50 phr, both indicating that nano‐γ‐Al₂O₃ is not a good candidate for novel thermally conductive reinforcing filler. POLYM. COMPOS., 37:771–781, 2016. © 2014 Society of Plastics Engineers     

Preparation and properties of nano‐Al2O3 particles/polyester/epoxy resin ternary composites

This article presents the results of an experimental study on the preparation and properties of new ternary composites composed of nano‐Al₂O₃ particles, polyester, and epoxy resin. The ternary composites were prepared by the addition of the nano‐Al₂O₃ particles in a binary matrix, with elevated viscosity, of the epoxy resin modified by the polyester. The nano‐Al₂O₃ particles were previously located and dispersed in the polyester phase. The study showed that the ternary system was a type of nanoscale dispersed composite with high strength and toughness as well as modulus, combined with excellent dielectric and heat‐resistance properties. All related properties of the composites were remarkably superior to those of both the binary matrix and the unmodified epoxy resin. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 70–77, 2002     

YCrO3/Al2O3 Core‐Shell Design: The Effect of the Nanometric Al2O3‐Shell on Dielectric Properties

We report a novel strategy to improve the dielectric properties of the biferroic YCrO₃ ceramic compound through interface conduction control by means of an insulating Al₂O₃ using a core‐shell design. The YCrO₃ particles were covered with several layers of insulating Al₂O₃ using the atomic layer deposition technique to produce the core‐shell structure. TEM images reveal homogeneous and well‐defined Al₂O₃ coatings of ~8, ~60, and ~130 nm thickness. XRD shows the Al₂O₃‐shell to be amorphous. The dielectric characteristics of the sintered nano‐composite were investigated in the 100 Hz–1 MHz frequency range and temperature between 300 and 580 K. As the Al₂O₃‐shell thickness covering the YCrO₃ particles is increased, a decrease of the dielectric permittivity, loss tangent and AC conductivity values was found in the whole range of temperatures and frequencies. Furthermore, the rounded hysteresis loop, typical of conductive ceramic is restored as the insulating Al₂O₃ layer becomes thicker. This behavior is explained because the insulating Al₂O₃‐shell acts as internal barrier layer localizing the surface charges on the sintered grain boundaries. This fact was confirmed by Electron Beam Induced Current technique where a clear contrast at the grain boundaries confirms the charge localization at the YCrO₃/Al₂O₃ interface. These results also reveal that the Al₂O₃‐shell induces another conductive mechanism when the insulating Al₂O₃ layer becomes thicker. Nonetheless, this new strategy is an effective approach to suppress the parasitic conductivity in polycrystalline multiferroic ceramics and increasing thus the multifuncionality.     

Effect of nanoparticles on the performance of thermally conductive epoxy adhesives

Microsized or nanosized α‐alumina (Al₂O₃) and boron nitride (BN) were effectively treated by silanes or diisocyanate, and then filled into the epoxy to prepare thermally conductive adhesives. The effects of surface modification and particle size on the performance of thermally conductive epoxy adhesives were investigated. It was revealed that epoxy adhesives filled with nanosized particles performed higher thermal conductivity, electrical insulation, and mechanical strength than those filled with microsized ones. It was also indicated that surface modification of the particles was beneficial for improving thermal conductivity of the epoxy composites, which was due to the decrease of thermal contact resistance of the filler‐matrix through the improvement of the interface between filler and matrix by surface treatment. A synergic effect was found when epoxy adhesives were filled with combination of Al₂O₃ nanoparticles and microsized BN platelets, that is, the thermal conductivity was higher than that of any sole particles filled epoxy composites at a constant loading content. The heat conductive mechanism was proposed that conductive networks easily formed among nano‐Al₂O₃ particles and micro‐BN platelets and the thermal resistance decreased due to the contact between the nano‐Al₂O₃ and BN, which resulted in improving the thermal conductivity. POLYM. ENG. SCI., 50:1809–1819, 2010. © 2010 Society of Plastics Engineers     

Preparation of core–shell structured alumina–polyaniline particles and their application for corrosion protection

Polyaniline (PANI) was synthesized by chemical oxidative polymerization of aniline (ANI) in the presence of alumina (Al₂O₃) particles. The polymerization of ANI occurred preferentially on the surfaces of the particles, resulting core–shell structured alumina–polyaniline (Al₂O₃‐PANI) particles. Morphology examination showed that with decreasing of the weight ratio of Al₂O₃/ANI in the reactants, the thickness of the PANI layer increased and changed from an even surface morphology to a particulate morphology. UV–vis and Fourier transformed infrared (FTIR) spectra indicated that there is no chemical interaction between the PANI layer and the Al₂O₃ surfaces. The PANI layer adhered well to the particles and can be used as anticorrosive fillers for polymer coatings. Enhanced corrosion protection performance was achieved for the emeraldine base (EB) form of PANI deposited Al₂O₃ particles (Al₂O₃‐EB) filled epoxy coating on carbon steel in 3.0 wt % aqueous NaCl solution. The particles demonstrate both excellent corrosion protection performance and lower cost, which will be of great importance in practical applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4372–4377, 2006     

Development of highly reinforced maleated natural rubber nanocomposites based on sol–gel‐derived nano alumina

In the present study, sol–gel synthesized alumina (Al₂O₃) nanoparticles were characterized by Fourier transform infrared spectra, X‐ray diffraction, field‐emission scanning electron microscopy. Then, Al₂O₃ nanoparticles were employed to improve cure, mechanical, and thermal properties of maleated natural rubber (MNR) nanocomposites. The MNR nanocomposite with 2 phr nano Al₂O₃ exhibited excellent value of cure rate index and exceptionally high value of mechanical properties like modulus and tensile strength in comparison to unfilled MNR compound. Thermogravimetric analysis indicated that nano Al₂O₃ was able to improve the thermal stability of MNR composites to some extent. Additionally, the present study revealed that the interfacial interaction between MNR and nano Al₂O₃ was far better than that between NR and nano Al₂O₃ as confirmed from crosslinking degree measurement and morphological analysis. The present article offers a fresh approach to prepare high performance nano Al₂O₃‐based MNR compounds for future industrial application. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46248.     

Preparation and formation mechanism of Al-Si/Al2O3 core-shell structured particles fabricated via steam corrosion

In this study, Al-Si/Al₂O₃ core-shell structured particles were fabricated via pressurized steam corrosion for 1 h followed by heating for 3 h at 1100 °C. After steam corrosion, a layer composed of disordered crystals covered the surfaces of the Al-Si alloy particles. After heating, Al-Si/Al₂O₃ core-shell structured particles with complete shells were prepared. The thickness of the shell was approximately 2 μm, and it enclosed the Al-Si alloy core. The shell exhibited excellent thermal stability because, even at 1100 °C, the mass gain ratio of the encapsulated particle was less than 0.5%. Scalloped patterns of alumina were formed by the oxidation of Al, which was inlaid through and upon the alumina shell. The shell formation mechanism suggested that the α-Al₂O₃ shell resulted from the combination of the decomposition of surface Al(OH)₃ crystals and the oxidation of Al from the core.     

Control of release characteristics in pH‐sensitive poly(vinyl alcohol)/poly(acrylic acid) microcapsules containing chemically treated alumina core

The pH‐sensitive poly(vinyl alcohol)/poly(acrylic acid) hydrogel microcapsules containing vitamin B₁₂‐loaded Al₂O₃ core were prepared with a three‐step emulsion polymerization. Al₂O₃ was chemically treated with HCl or NaOH solutions at room temperature for 24 h to modify the binding properties with vitamin B₁₂. The colon‐targeted release characteristics of vitamin B₁₂ from the microcapsules were evaluated at different pHs. These microcapsules showed the faster and larger release of vitamin B₁₂ due to the high swelling of microcapsule shell as the pH was changed into more basic condition. However, these microcapsules showed the slower and less release of vitamin B₁₂ as the acid value of Al₂O₃ increased due to the strong binding interaction between Al₂O₃ core and vitamin B₁₂ even though the initial loading of vitamin B₁₂ was higher. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of Polyimide/Al2O3 nanocomposite film with good corona resistance

Polyimide/Al2O3 (PI/Al2O3) nanocomposite films based on pyromellitic dianhydride and 4,4′‐oxydianiline were fabricated by adding different proportions of nano‐Al₂O₃ inorganic particles via in situ polymerization. Microstructural analysis by scanning electron microscope (SEM) showed that the inorganic particles were homogenously dispersed in the PI matrix when mixed with appropriate amount of nano‐Al₂O₃. Fourier transform infrared spectroscopy and X‐ray diffraction analysis were also used to investigate the effect of nano‐Al₂O₃ on the polymerization process. The obtained composite films and pure film were characterized by thermogravimetry analysis, and the experimental results indicated that when comparing with pure film, the nanocomposite films displayed a better thermal stability than the pure one. Moreover, results also showed that the thermal stability of composite films steadily improved with increased content of nano‐Al₂O₃ particle. The electrical property test demonstrated that the composite films performed improving electrical breakdown strength and corona resistance. The microstructure changes of pure film and PI/Al₂O₃ nanocomposite films during corona aging have been analyzed by SEM. POLYM. COMPOS., 37:763–770, 2016. © 2014 Society of Plastics Engineers     

Development of poly(vinylcarbazole)/alumina nanocomposite coatings for corrosion protection of 316L stainless steel in 3.5% NaCl medium

Poly(vinylcarbazole) (PVK) and PVK‐alumina (Al₂O₃) nanocomposite coatings were electrochemically coated on 316 L stainless steel (SS) substrates for corrosion protection of 316 L SS in 3.5 weight (wt) % NaCl medium. The formation of PVK and incorporation of nanoalumina particles in PVK‐Al₂O₃ nanocomposite coatings were confirmed from attenuated total reflectance‐infrared spectroscopy (ATR‐IR). Thermal analysis (TG) results showed enhanced thermal stability for the composites relative to PVK. Incorporation of Al₂O₃ nanoparticles enhanced the micro hardness of PVK coated 316 L SS. The dispersion of alumina nanoparticles was examined via scanning electron microscope (SEM) and tunneling electron microscopy (TEM) and revealed distinct features. The influence of nanoparticles on the barrier properties of PVK and PVK‐Al₂O₃ nanocomposites was evaluated in aqueous 3.5 wt % NaCl by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) studies. The results proved that PVK nanocomposite coatings provided better protection for 316 L SS than PVK coatings. The drastic increase in impedance values is due to the high corrosion resistance offered by the PVK nanocomposite coatings that arises due to the interaction between Al₂O₃ nanoparticles and PVK. The highest corrosion protection shown by the 2 wt % nano Al₂O₃ incorporated PVK composite coatings proved enhanced corrosion resistance compared to PVK. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44937.     

Monodispersed and Stable Nano Copper(0) from Copper‐ Aluminium Hydrotalcite: Importance in C?C Couplings of Deactivated Aryl Chlorides

A simple one‐step approach for the preparation of highly monodispersed nano copper(0) stabilized on alumina [Cu(0)/Al₂O₃] by thermal reduction of copper‐aluminium hydrotalcite (Cu‐Al HT) under a hydrogen atmosphere is described. The transformation of Cu‐Al HT to Cu(0)/Al₂O₃ occurrs via dehydroxylation of divalent and trivalent metal hydroxides and decarboxylation of carbonate anions present in the interlayers of hydrotalcite, as confirmed by XPS, XANES, XRD and TEM analysis. Cu(0)/Al₂O₃ nano composites were used as an efficient catalyst in the C C coupling of deactivated aryl chlorides. The high efficiency and reusability exhibited by Cu(0)/Al₂O₃ outline its potential as an alternative over traditional noble metal‐based catalysts in C C coupling reactions.     

Corrosion- and wear-resistant properties of Ni–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composite coatings containing various forms of alumina

This article describes the effect of the addition of different phases of alumina particles on the properties of electrodeposited Ni–Al₂O₃ composite coatings. The corrosion- and wear-resistant properties of Ni–Al₂O₃ composite coatings electrodeposited from a nickel sulfamate bath containing (i) alpha-alumina particles (Ni–Al₂O₃-1), (ii) gamma-alumina particles (Ni–Al₂O₃-2), and (iii) mixture of alpha, gamma, and delta alumina particles (Ni–Al₂O₃-3) have been studied. The potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) studies showed superior corrosion resistance of Ni–Al₂O₃-2 composite coatings compared with other two coatings. The SEM images and EDAX spectra also corroborated well with the observed corrosion results. The pin-on-disk wear studies showed improved wear resistance of Ni–Al₂O₃-1 composite coating containing alpha alumina compared with other two coatings. The transfer of material from the pin onto the disk was evident from the optical microscopy images of the wear tracks and Raman spectra of the wear track. This study shows that the addition of pure gamma-alumina particles enhances the corrosion resistance, and that pure alpha-alumina particles enhance the wear resistance of Ni composite coatings to a greater extent.     

Phase evolution mechanism of non‐oxide bonded Al–Al2O3–MgO–ZrO2 composites at 1873 K in flowing nitrogen

In flowing nitrogen, non‐oxides such as Al₄O₄C, Al₂OC, Zr₂Al₃C₄, and MgAlON bonded Al₂O₃‐based composites were successfully prepared by a gaseous phase mass transfer pathway using aluminum, zirconia, alumina, and magnesia as raw materials at 1873 K, after an Al–AlN core‐shell structure was formed at 853 K. Resin bonded Al–Al₂O₃–MgO–ZrO₂ composites after sintering were characterized and analyzed by X‐ray diffraction (XRD), scanning electron microscope (SEM) and, energy dispersive spectrometer (EDS), and the influence of the MgO content on the sintered composites was studied. The results show that after sintering, the phase composition of the Al–Al₂O₃–ZrO₂ composite is Al₂O₃, Al₄O₄C, Al₂OC, and Zr₂Al₃C₄, while the phase composition of the Al–Al₂O₃–ZrO₂ composite with the addition of MgO 6 wt% and MgO 12 wt% is Al₂O₃, MgAlON, Al₄O₄C, Al₂OC, and Zr₂Al₃C₄ as well as Al₂O₃, MgAlON, Al₂OC, and Zr₂Al₃C₄, respectively. The addition of MgO changed the phase composition and distribution for the resin bonded Al–Al₂O₃–MgO–ZrO₂ system composites after sintering. When the added MgO content is equal to or more than 12 wt%, the Al₄O₄C in the resin bonded Al–Al₂O₃–MgO–ZrO₂ system composites is unable to exist in a stable phase.     

On the Mechanism of Low Temperature Oxidation for Aluminum Particles down to the Nano‐Scale

The oxidation of Al‐particles down to nano‐scale was investigated by TG, SEM and in‐situ X‐ray diffraction. Al particles are usually coated by a 2–4 nm layer of Al₂O₃ which can be derived from the degree of weight increase on complete oxidation by TG‐curves. The low temperature oxidation of Al particles occurs at least in two steps. The first step builds a layer of 6 to 10 nm thickness composed of crystallites of the same size independent on the initial particle size. This reaction is dominated by chemical kinetics and converts a substantial fraction of the particle if the particle sizes decrease below 1 μm, an effect carefully to be taken into account for nano‐particles because of safety reasons. The second step combines diffusion and chemical reaction and proceeds therefore slowly, the slower the bigger the particles are. The kinetic parameters of these two steps can be obtained by a model taking into account both reaction steps, chemical kinetics and diffusion for spherical particles when fitting it to TG‐curves. X‐ray diffraction shows that particles smaller than 1 μm build γ‐ and θ‐Al₂O₃ in the first step with nano‐crystalline structures which are then transformed to α‐Al₂O₃.     

Preparation of nano - coating powder CaF2@Al(OH)3 and its application in Al2O3/Ti(C,N) self-lubricating ceramic tool materials

Nano CaF₂ particles of different sizes were prepared by direct precipitation. The diameters of nano CaF₂ particles prepared in mixed solvent can reach 5–7 nm, and can be effectively dispersed. The surface of nano CaF₂ was modified and coated by heterogeneous nucleation method. A shell layer of Al(OH)₃ was coated on the surface of nano CaF₂, and the structure and coating mechanism of the coated powder were analyzed. Under varying preparation conditions, the surface morphology of CaF₂@Al(OH)₃ was analyzed using TEM and SEM. The results showed that the coating powder showed good dispersion in mixed solvents, and the particle size of the composite powder was about 20 nm. Self-lubricating ceramic tool materials were prepared by adding coating particles to the Al₂O₃/Ti(C,N) matrix. The coating powder shell and the matrix material melt during sintering, so that CaF₂ forms nanostructures in the particles. thereby improving the mechanical properties of the material. Cutting experiments show that the addition of coating particles can effectively reduce the temperature, cutting force and friction coefficient in the cutting process of the tool, thus improving the cutting performance of the tool material.     

Effect of Temperature on Structural and Optical Properties of Boehmite Nanostructure

The nanocrystalline boehmite, γ‐AlOOH, was synthesized by the hydrothermal method using AlCl₃·6H₂O and urea as precursors, and the effect of different annealing temperatures resulting in different phases of alumina (Al₂O₃) was obtained. The effects of different temperature on the phase and micrographs of the prepared γ‐AlOOH nanostructures were investigated. The obtained products were characterized by X‐ray powder diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy techniques. The XRD results show that with the increasing temperature, the transformation of boehmite into well‐crystallized α‐Al₂O₃ and the morphology from nanoplatelets with spindle‐like edges to vermicular structure take place. The crystallite size and lattice parameters were calculated by Rietveld refinement. The convincing evidence for the crystal phase of the as‐prepared and annealed samples was provided by FTIR spectra. The Raman spectra unveil the change in vibrational modes of the phase transition alumina.     

Lap shear strength and thermal stability of diglycidyl ether of bisphenol a/epoxy novolac adhesives with nanoreinforcing fillers

Nanoreinforcing fillers have shown outstanding mechanical properties and widely used as reinforcing materials associated to polymeric matrices for high performance applications. In this study, a series of multiwalled carbon nanotubes (MWCNTs)‐, nano‐Al₂O₃‐, nano‐SiO₂‐, and talc‐reinforced epoxy resin adhesives composites were developed. The influence of different types and contents of nanofillers on adhesion, elongation at break, and thermal stability (under air and nitrogen atmospheres) of diglycidyl ether of bisphenol A (DGEBA)/epoxy novolac adhesives was investigated. A simple and effective approach to prepare adhesives with uniform and suitable dispersion of nanofillers into epoxy matrix was found to be mechanical stirring combined with ultrasonication. Transmission electron microscopic and scanning electron microscopic investigations revealed that nanofillers were homogeneously dispersed in epoxy matrix at optimized nanofiller loadings. Adhesion strength was measured by lap shear strength test as a function of nano‐Al₂O₃ and MWCNTs loadings. The results indicated that the lap shear strength was significantly increased by about 50% and 70% with addition of MWCNTs and nano‐Al₂O₃ up to a certain level, respectively. The highest lap shear strength was reached at 1.5 wt % of nano‐Al₂O₃ loading. MWCNTs at all loadings (except 3 wt %) and nano‐Al₂O₃ have enhanced onset of degradation temperature and char yield of the adhesives. By combined incorporation of 0.75 wt % nano‐Al₂O₃ and 0.75 wt % MWCNTs into the epoxy novolac/DGEBA blend adhesives a synergistic effect was observed in the thermal stability of the adhesives at high temperatures (800°C). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40017.     

Mechanism of in-situ formation of spinel and its effect on the mechanical properties of Al2O3–C refractories

This work looked at the in-situ formation mechanism of magnesia alumina spinel in Al₂O₃–C refractories with magnesia addition at different firing temperatures. A comprehensive study on the mechanical properties of Al₂O₃–C refractories was performed in comparison to traditional analogs. The magnesia alumina spinel was in-situ formed at the firing temperature of 1150 °C in Al₂O₃–C refractories. With the increase of the firing temperature, the Al₂O₃ phase was gradually dissolved in spinel phase to form aluminum rich spinel phase, resulting in a decrease in its lattice constant due to the defects formation. The formed spinel phase was homogenously distributed and bonded well with corundum, improving the interfacial bond, load transferring capacity and crack propagation resistance. The formation of spinel phase also enhanced the sintering of the alumina matrix owing to the solid solution of alumina in the spinel. Therefore, the mechanical properties such as cold modulus of rupture and hot modulus of rupture in Al₂O₃–C refractories achieved a substantial enhancement compared with traditional refractories.     

Solidification of Al2O3–YAG eutectic composites with off-metastable eutectic composition from undercooled melt produced by melting Al2O3–YAP eutectics

It has been reported that solidification of the Al₂O₃–YAG equilibrium eutectic structure follows melting of the Al₂O₃–YAP metastable eutectic structure. Since the exothermic heat due to solidification was consumed by the endothermic heat due to melting, a fine and uniform eutectic structure was obtained. However, the composition of the Al₂O₃–YAG eutectic structure is restricted to the metastable eutectic composition. In this paper, Al₂O₃–YAG eutectic compacts with an off-metastable eutectic composition were prepared by the addition of Al₂O₃ particles to Al₂O₃–YAP eutectic particles with diameters less than 20 μm. In compositions ranging from 18.5 mol%Y₂O₃ to 13.5 mol%Y₂O₃, dense Al₂O₃–YAG eutectic compacts were formed without any Al₂O₃ segregation. The flexural strength and the fracture toughness remained almost unchanged with the increase in the Al₂O₃ phase. The addition of Al₂O₃ particles to the Al₂O₃–YAP eutectic particles enabled the matrix phase to change from the YAG phase to the Al₂O₃ phase.     

Enhanced thermal shock resistance of low-carbon Al2O3-C refractories with direct CVD synthesis of nano carbon decorated oxides

Novel low carbon Al₂O₃-C refractories were prepared through adopting chemical vapour deposition (CVD) synthesized nano carbon decorated Al₂O₃ powder. The phase compositions, microstructures, mechanical properties and thermal shock resistance of Al₂O₃-C refractories were characterized and evaluated. The results show that the morphologies of nano carbon composites are mainly dominated by the concentration of catalyst. Specifically, the growth of MWCNTs is preferred with a Ni²⁺ concentration at 0.1?mol/L, while higher concentrations e.g. 0.3?mol/L would stimulate the formation of nano-onion like carbon. With the introduction of nano carbon decorated Al₂O₃ additives, the residual strength after thermal shock can reach 12.4?MPa, which is much higher than the 2?wt% nano carbon black containing specimens (6.4?MPa). The enhanced thermal shock resistance should be attributed to that the nano onion-like carbon reduces the cohesion between the matrix and the Al₂O₃ particles and decreases the thermal expansion coefficient.