Rheological properties and percolation in suspensions of multiwalled carbon nanotubes in polycarbonate

This paper is concerned with several issues related to the rheological behavior of polycarbonate/multiwalled carbon nanotube nanocomposites. The composites were prepared by diluting a masterbatch of 15 wt.% nanotubes using melt-mixing method, and the dispersion was analyzed by SEM, TEM, and AFM techniques. To understand the percolated structure, the nanocomposites were characterized via a set of rheological, electrical, and thermal conductivity measurements. The rheological measurements revealed that the structure and properties were temperature dependent; the percolation threshold was significantly lower at higher temperature suggesting stronger nanotube interactions. The nanotube networks were also sensitive to the steady shear deformation particularly at high temperature. Following preshearing, the elastic modulus decreased markedly suggesting that the nanotubes became more rigid. These results were analyzed using simple models for suspensions of rod-like particles. Finally, the rheological, electrical, and thermal conductivity percolation thresholds were compared. As expected, the rheological threshold was smaller than the thermal and electrical threshold.     

Rheological and electrical properties of EVA copolymer filled with bamboo charcoal

The electrical and rheological properties of an ethylene vinyl acetate (EVA) copolymer filled with bamboo charcoal were investigated. The composites were prepared by melt process in an internal batch mixer. Size distribution analysis showed that d₍₅₀₎ and d₍₉₀₎ values of the bamboo charcoal particles are 12.7 and 40 μm, respectively, with a mean diameter of 22 μm. Scanning electron microscopy proved that the particles of bamboo charcoal present a rectangular shape. The electrical percolation threshold was observed at 0.18 volume fraction (35 wt%) of bamboo. Beyond the percolation threshold, a considerable increase in electrical properties was observed up to a limit value of 10^-2 S/m. The rheological percolation was studied from different rheological models. As a result, the rheological percolation threshold was observed at 0.3 volume fraction (50 wt%) of bamboo charcoal contents. So, the electrical percolation occurs before the rheological percolation. This is principally due to the filler’s characteristics such as the specific surface area, the aspect ratio, and the surface properties. Finally, the bamboo charcoal confers high electrical properties to the EVA composite without inducing strong changes in its viscoelastic properties.     

Multiphysics of multifunctional nanofluids based on different oxides nanoparticles and glycerol fluid

Nanofluid (NF) materials consisting of glycerol (Gly) and different inorganic nano oxides (TiO₂, ZnO, Al₂O₃, and SiO₂ for the oxides concentration of 0.01 wt% to the weight of Gly base fluid) were prepared by a two-step method through ultrasonic cavitation process. These nanofluids were investigated by employing an X-ray diffractometer (XRD), ultraviolet–visible (UV–Vis) spectrophotometer, 20 Hz to 1 MHz frequency range dielectric relaxation spectroscopy (DRS), ultrasonic interferometer, and rotational viscometer. The multiphysics of these nanofluids includes structural and optical properties, dielectric permittivity, electrical conductivity, conductivity relaxation, ultrasound velocity, adiabatic compressibility, acoustic impedance, viscosity, density, thermal conductivity, and viscoacoustic relaxation were characterized. The XRD patterns identified monodispersed and stable suspensions of these different characteristic nanoparticles in the hydrogen-bonded 3D supramolecular structure of ultra-high viscous glycerol fluid which were supported by their UV–Vis absorbance analyses. The energy band gap values of the TiO₂ and ZnO containing nanofluids were found primarily ruled by the characteristic optical properties of these oxides nanomaterials. The complex dielectric and various electrical functions studied at 25 °C revealed that the suspension of different oxide nanoparticles in the glycerol fluid increased the static permittivity whereas reduced the direct current electrical conductivity which showed strong conductivity relaxation process dependence. The rheological measurements of the formulated nanofluids were performed over a shear rate range of 0.4–40 s⁻¹ at temperatures of 25–55 °C. The linear relationship between shear rate and shear stress and also the shear rate-independent viscosity revealed the Newtonian behaviour of these nanofluids. The shear viscosity non-linearly decreased with the increase of temperature and exhibited the Arrhenius behaviour for all different oxides containing Gly-based nanofluids. The acoustic parameters of the nanofluids were altered unevenly with types of nano oxides and inferred some structure-property correlations. The promising technologically useable properties of these nanofluids were expected to impact their potential applications in optoelectronics, UV-blocking, sensing, nanodielectrics, energy storing and electric insulation, heat transfer systems, and also in materials processing for the development of innovative soft condensed devices.     

Dielectric analysis of TiO2-based electrorheological suspensions

Dielectric behaviors of titanium dioxide (TiO₂)-based electrorheological (ER) suspensions with different particle concentrations and TiO₂ polymorphs were investigated in the frequency range of 40 Hz to 110 MHz. Two relaxations in kilohertz and megahertz frequency range were attributed to interface polarization between TiO₂ and silicone oil and ion pair polarization between dissociated counterions and fixed charges on TiO₂ surfaces, respectively. Dipolar coefficient D, which is related to the construction or structure of the colloid, changes after critical volume fraction $\phi _{\rm c} \approx $ 0.05, indicating that chain-like or network structures are formed by particles. Based on percolation model, the values of critical exponent suggest that particles may form two-dimensional percolation network. Furthermore, the effective dielectric mismatch parameter, $\beta _{\rm eff}$ , was calculated based on the obtained phase parameters. We found that rutile should have better ER activity than anatase. The main reason for weak ER activity of pure TiO₂ ER suspensions may due to poor conductivity properties of TiO₂ crystals.     

Experimental measurement of thermophysical properties of oxide-water nano-fluids down to ice-point

This paper presents the measurement of the thermal conductivity and the dynamic viscosity of Al₂O₃-water (1-4% particle volume fraction) and TiO₂-water (1-6% particle volume fraction) nano-fluids carried out at atmospheric pressure in the temperature range from 1 to 40 °C, which is particularly interesting for the application of nano-fluids as thermal medium in refrigeration and air-conditioning.The thermal conductivity measurement was performed by using a Transient Hot Disk TPS 2500S apparatus instrumented with a 7577 probe (2.001 mm in radius) having a maximum uncertainty (k = 2) lower than ±5.0% of the reading. The dynamic viscosity measurement and the rheological analysis were carried out by a rotating disc type rheometer Haake Mars II instrumented with a single cone probe (60 mm in diameter and 1° angle) having a maximum uncertainty (k = 2) lower than ±5.0% of the reading.The thermal conductivity measurements of the tested nano-fluids show a great sensitivity to particle volume fraction and temperature and a weak sensitivity to cluster average size: TiO₂-water and Al₂O₃-water nano-fluids show a thermal conductivity enhancement (with reference to pure water) from −2 to 16% and from −2 to 23% respectively.TiO₂-water and Al₂O₃-water nano-fluids exhibit a Newtonian behaviour in all the investigated ranges of temperature and nano-particle volume fraction. The relative viscosity shows a great sensitivity to particle volume fraction and cluster average size and no sensitivity to temperature: TiO₂-water and Al₂O₃-water nano-fluids show a dynamic viscosity increase with respect to pure water from 17 to 210% and from 15 to 150% respectively.Al₂O₃-water nano-fluid seems to be more promising as thermal medium than TiO₂-water nano-fluid, particularly at low thermal level (between ambient temperature and ice point) where TiO₂-water is not suitable showing worse performance than pure water.Present experimental measurements were compared both with available measurements carried out by different researchers and computational models for thermophysical properties of suspensions.     

Percolation in layered media — A conductivity approach

Long square-lattice and cubic-lattice samples consisting of many layers are simulated. Within each layer, the concentration of permeable bonds is constant whereas each layer has a different concentration chosen randomly from the interval between the percolation threshold and unit concentration. The conductivity of the random resistor network corresponding to this percolation model is calculated, both parallel and perpendicular to the layers, in both two and three dimensions. For the conductivity parallel to the layers, an effective medium calculation comes within 10% of the true conductivity. For the conductivity perpendicular to the layers, percolation theory is necessary.List of Symbols G Total Conductivity in units of the conductivity of one bond - L Length of sample in units of the length of one bond - n Width of sample in units of the length of one bond - N Number of layers - p Probability that a bond conduct - p _c Percolation threshold - R Resistivity in units of the resistivity of one bond - t Percolation conductivity exponent - v Percolation correlation length exponent - Correlation length in units of the length of one bond     

Facile aqueous synthesis and thermal insulating properties of low-density glass/TiO2 core/shell composite hollow spheres

Anatase TiO₂ shells assembled on hollow glass microspheres (HGM) with tunable morphologies were successfully prepared through a controllable chemical precipitation method with urea as the precipitator. Thus, glass/TiO₂ core/shell composite hollow spheres with low particle density (0.40 g/cm³) were fabricated. The phase structures, morphologies, particle sizes, shell thicknesses, and chemical compositions of the composite microspheres were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS). The morphology of the TiO₂ shell can be tailored by properly monitoring the reaction system component and parameters. The probable growth mechanism and fabrication process of the core/shell products involving the nucleation and oriented growth of TiO₂ nanocrystals on hollow glass microspheres was proposed. A low infrared radiation study revealed that the radiation properties of the products are greatly influenced by the unique product shell structures. A thermal conductivity study showed that the TiO₂/HGM possess low thermal conductivity that is similar to that of the pristine HGMs. This work provides an additional strategy to prepare low-density thermal insulating particles with tailored morphologies and properties.     

Visible light-driven photocatalysis of W,N co-doped TiO2

W, N co-doped TiO2 nanoparticles were synthesized by a sol-gel method. The prepared samples were characterized by X-ray diffraction （XRD）, field emission scanning electron microscopy （FE-SEM）, trans- mission electron microscopy （TEM）, Fourier transform infrared spectroscopy （FT-1R）, X-ray photoelectron spectroscopy （XPS） and diffuse reflectance spectrophotometry （DRS）. The results showed that the co- doped photocatalysts were essentially uniform spherical particles with the smallest particle size of 22.5 nm. Compared to un-doped TiO2, N-TiO2 and P-25, the absorption edge of the W, N co-doped TiO2 shifted to longer wavelength and its photocatalytic activity for degradation of methyl orange （MO） under Xe-lamp （350W） was higher.     

Newtonian,power law,and infinite shear flow characteristics of concentrated slurries using percolation theory concepts

There is a strong interest today in concentrated particulate-filled dispersion and slurries in both polymeric and Newtonian fluids. This paper reviews and extends theoretical approaches using percolation theory concepts to characterize the rheological behavior of fluids filled with particulate solids. First, a previously proposed limiting, zero shear viscosity model based on percolation theory concepts is reviewed. This model has been primarily tested with rigid fillers in a Newtonian carrier and polymeric fluids. Second, all Newtonian fluid-based slurries that have a high concentration of filler become pseudoplastic, shear-thinning slurries at some threshold shear rate. A new theory is reviewed and new data are evaluated that correlate the power law constant, n, to cluster formation of the fillers suspended in the fluids in shear flow. Slurry systems reported here cover a size range from 58 nm to 200 μm. Third, this cluster percolation-based rheological analysis is then extended to a newly proposed model for the calculation of the ratio of infinite shear, η_∞, to the zero shear viscosity, η₀. Using literature data, it is demonstrated that measurements of the viscosity ratio, η_∞/η₀, correlate with the power law through the use of an energy dissipation-based model for Bingham rheological fluids.     

TiO2-loaded activated carbon fiber: Hydrothermal synthesis,adsorption properties and photo catalytic activity under visible light irradiation

TiO₂-loaded activated carbon fibers (ACF) were prepared by a hydrothermal method. The samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectrometry and UV–vis diffuse reflectance spectra (DRS). SEM images showed that the TiO₂ nanoparticles were deposited on the surface of ACF, and the particle size and loading amount of TiO₂ were varied by changing the initial concentration of tetrabutyl titanate (TBOT). The results of an ash experiment showed that the loading amounts of TiO₂ were 18.4%, 43.3%, 52.5%, 75.1%, and 91.1% for initial concentrations of TBOT of 0.07, 014, 0.21, 0.28, and 0.35 mol/L, respectively. Physical interactions played an important role in the formation of TiO₂/ACF composite fibers that absorb UV and visible light. Compared with those of ACF, improved adsorption and photocatalytic activity toward Rhodamine B (RhB) were observed for TiO₂/ACF composite fiber. The Rhodamine B could be removed efficiently by TiO₂/ACF composite fibers, and the TiO₂ loading amount had a significant effect on the photocatalytic activity of TiO₂/ACF composite fibers.     

Electrical Response of Carbon Nanotube Reinforced Nanocomposites Under Static and Dynamic Loading

An experimental investigation was conducted to study the effect of quasi-static and dynamic compressive loading on the electrical response of multi-wall carbon nanotube (MWCNT) reinforced epoxy nanocomposites. An in-situ polymerization process using both a shear mixer and an ultrasonic processor were employed to fabricate the nanocomposite material. The fabrication process parameters and the optimum weight fraction of MWCNTs for generating a well-dispersed percolation network were first determined. Absolute resistance values were measured with a high-resolution four-point probe method for both quasi-static and dynamic loading. In addition to measuring the percentage change in electrical resistance, real-time damage was captured using high-speed photography. The real-time damage was correlated to both load and percentage change in resistance profiles. The experimental findings indicate that the bulk electrical resistance of the nanocomposites under both quasi-static and dynamic loading conditions initially decreased between 40%–60% during compression and then increased as damage initiated and propagated.     

A rheological criterion to determine the percolation threshold in polymer nano-composites

In this work, the effect of multi-walled carbon nanotube (CNT) and montmorillonite nanoclay on polymer chain dynamics is investigated around the percolation concentration for systems based on ethylene vinyl acetate (EVA) copolymer. Then, the results obtained are compared with literature data to determine if, regardless of particle characteristics, a universal rheological behavior can be detected at percolation. To do so, rheological analyses are performed under small amplitude oscillatory shear (SAOS), large amplitude oscillatory shear (LAOS), and transient shear step. SAOS data showed that, while the dynamics related to the Rouse relaxation time (τ _R) were not significantly influenced, the reptation relaxation time (τ _D) was strongly increased by the presence of nanoparticles. In step shear transient tests, the critical shear rate \( \left({\dot{\upgamma}}_{\mathrm{cr}}\right) \) for overshoot appearance was decreased due to chain confinement, and the formation of particle network strongly increased the level of stress overshoot. Particle networks increased significantly the nonlinear parameters (I ₃/I ₁ and Q ₀) obtained under LAOS and quantified by FT-rheology. In all measurements, due to the higher surface area associated to its size and density as well as hollow structure, CNT showed stronger effects compared to clay. Moreover, while the percolation concentration was different for CNT and clay, both systems showed similar behavior at percolation: a 0.5 scaling for G′ indicating a Rouse-dominated behavior.     

SiO2-coated pure anatase TiO2 catalysts for enhanced photo-oxidation of naphthalene and anthracene

Our current efforts reveal the preparation of SiO₂@TiO₂ nanocomposites having different thicknesses of silica shell and the relationship to photocatalytic activity (PCA) for the photo-oxidation of naphthalene and anthracene. The presence of SiO₂ coating over TiO₂ surface was demonstrated by FT-IR analysis, with peaks corresponding to SiOSi (1081 cm⁻¹) and SiOTi (950 cm⁻¹) bonds observed. High-resolution transmission electron microscopy analysis confirmed the presence of SiO₂ in the as-prepared nanocomposites and the amount of Si, Ti, and O was determined by energy dispersive X-ray spectroscopy analysis. Increasing the SiO₂ shell thickness increases the surface area of the nanocomposites (69–235 m²/g), which enhances naphthalene/anthracene adsorption. However, the observed PCA trend presents an inverse correlation to the adsorption studies, where the as-prepared samples possessing the highest surface areas exhibited the least PCA, while catalysts having lower surface areas (among silica coated samples) displayed the highest PCA in the degradation of naphthalene and anthracene to CO₂. Despite complete degradation of naphthalene and anthracene, incomplete mineralization occurred, ascribed to the formation of various intermediates, identified by GC–MS analysis.     

电流变液体黏性变化趋势的试验研究

以微观试验和流变性能试验为手段，分别研究零电场下和在电场作用下的电流变液体黏性变化规律．研究结果表明：零电场下电流变液体的黏性与Krieger-Dougherty公式具有很好的拟合效果，其中逾渗临界值强依赖于悬浮液体中固体颗粒的性质并随工作温度变化．在电场作用下，电流变悬浮液体的黏度随剪切速率的变化规律分为3个阶段：即呈线性的启动段、非线性的幂定律模型流动段和宾汉模型流动段．研究结果为电流变效应工程应用提供依据．     

Linear viscoelasticity of styrenic block copolymers–clay nanocomposites

In this work, the rheological behavior of block copolymers with different morphologies (lamellar, cylindrical, spherical, and disordered) and their clay-containing nanocomposites was studied using small amplitude oscillatory shear. The copolymers studied were one asymmetric starblock styrene–butadiene–styrene copolymer and four styrene–ethylene/butylenes–styrene copolymers with different molecular architectures, one of them being modified with maleic anhydride. The nanocomposites of those copolymers were prepared by adding organophilic clay using three different preparation techniques: melt mixing, solution casting, and a hybrid melt mixing–solution technique. The nanocomposites were characterized by X-ray diffraction and transmission electron microscopy, and their viscoelastic properties were evaluated and compared to the ones of the pure copolymers. The influence of copolymer morphology and presence of clay on the storage modulus (G′) curves was studied by the evaluation of the changes in the low frequency slope of log G′× logω (ω: frequency) curves upon variation of temperature and clay addition. This slope may be related to the degree of liquid- or solid-like behavior of a material. It was observed that at temperatures corresponding to the ordered state, the rheological behavior of the nanocomposites depended mainly on the viscoelasticity of each type of ordered phase and the variation of the slope due to the addition of clay was small. For temperatures corresponding to the disordered state, however, the rheological behavior of the copolymer nanocomposites was dictated mostly by the degree of clay dispersion: When the clay was well dispersed, a strong solid-like behavior corresponding to large G′ slope variations was observed.     

Suspensions of titania nanoparticle networks in nematic liquid crystals: rheology and microstructure

We study the influence of confinement on the rheology and structure of nematic liquid crystals (NLCs). NLCs get confined in networks of titania (TiO₂, primary particle size = 21 nm) nanoparticles in suspensions of TiO₂ and NLC, N-(4-methoxybenzylidene)-4-butylaniline (MBBA). Suspensions with TiO₂ nanoparticle volume fraction (?) of 0.006–0.017, form viscoelastic solids with low elastic modulus (G′) of 10¹ Pa–10² Pa and short relaxation times. Increase in TiO₂ nanoparticle ? leads to a rise in G′ with TiO₂ nanoparticles forming a percolating network at a critical volume fraction (? _c) = 0.023, and G′ of ~10³ Pa. TiO₂/MBBA NLC suspensions at and above ? _c = 0.023 show G′ ~ ω ^x?1 scaling, where ω is the angular frequency and the minimum in loss modulus (G′′) with ω. The effective noise temperature, x decreases and approaches 1 with the increase in the TiO₂ nanoparticle ? from 0.023–0.035, is indicative of an increase in the glassy dynamics. Through the polarized light microscopy and differential scanning calorimetry experiments, we propose that the progressive addition of TiO₂ nanoparticles introduces a quenched random disorder (QRD) in the NLC medium which disturbs the nematic order. This results in metastable TiO₂/MBBA NLC suspensions in which NLC domains get confined in the network of flocs of TiO₂ nanoparticles. We also show that the salient rheological signatures of soft glassy rheology develop only in the presence of NLC MBBA and are absent in the isotropic phase of MBBA.     

Laminar convective heat transfer of non-Newtonian nanofluids with constant wall temperature

Nanofluids are obtained by dispersing homogeneously nanoparticles into a base fluid. Nanofluids often exhibit higher heat transfer rate in comparison with the base fluid. In the present study, forced convection heat transfer under laminar flow conditions was investigated experimentally for three types of non-Newtonian nanofluids in a circular tube with constant wall temperature. CMC solution was used as the base fluid and γ-Al₂O₃, TiO₂ and CuO nanoparticles were homogeneously dispersed to create nanodispersions of different concentrations. Nanofluids as well as the base fluid show shear thinning (pseudoplastic) rheological behavior. Results show that the presence of nanoparticles increases the convective heat transfer of the nanodispersions in comparison with the base fluid. The convective heat transfer enhancement is more significant when both the Peclet number and the nanoparticle concentration are increased. The increase in convective heat transfer is higher than the increase caused by the augmentation of the effective thermal conductivity.     

Functionalized TiO2@ZrO2@Y2O3 ：Eu3＋ core-multishell microspheres and their photoluminescence properties

TiO2@ZrO2@Y2O3 ：Eu3＋ composite particles with a core-multishell structure were synthesized through the combination of a layer-by-layer （LBL） self-assembly method and a sol-gel process. The obtained sam- ples were characterized with scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, X-ray photoelectron spectroscopy （XPS）, X-ray diffraction （XRD）, and fluorescence spectropho- tometry. The results showed that the composite particles had a core-multishell structure, spherical morphology, and a narrow size distribution. The presence of a ZrO2 layer on the TiO2 core can effec- tively prevent the reaction between the TiO2 core and a Y203 shell; the temperature for the reaction between the TiO2 core and the Y203 shell in the TiO2@ZrO2@Y2O3 ：Eu core-multishell phosphor can be elevated by 300 ℃ compared to that for TiO2@ZrO2：Eu. Upon excitation of the core-multishell particles in the ultraviolet （254 nm）, the Eu3＋ ion in the Y2O3 ：Eu3＋ shell shows its characteristic red emission （611 nm, 5D0→7F2）, and the photoluminescence （PL） intensity of the phosphor with the core-multishell structure was obviously greater than that of the core-shell TiO2@Y2O3 ：Eu phosphor.     

Hydrodesulfurization catalyst prepared by urea-matrix combustion method

Co–Mo/γ-Al₂O₃–TiO₂ hydrodesulfurization (HDS) catalyst samples prepared by a urea matrix combustion (UMxC) method, were evaluated in a stainless tubular fixed-bed reactor, with thiophene, benzothiophene and dibenzothiophene in xylene as model feedstocks. The samples were pre-sulfurized using a cyclohexane solution of 3% CS₂ and then tested for the HDS reaction. The test results were compared with catalysts prepared by conventional methods involving sequential impregnation (SI) and co-impregnation (CI). The catalysts were characterized using X-ray diffraction (XRD), laser Raman spectroscopy (LRS), high resolution transmission electron microscopy (HRTEM) and N₂ physisorption, showing that the UMxC catalyst had higher pore volume and surface area than those prepared by the CI and SI methods. The UMxC method increased metal loading and avoided formation of inert phase, e.g., β-CoMoO₄, for the HDS reaction, suggesting that UMxC method is superior to the conventional impregnation techniques. TiO₂ promoter made particles on the catalyst surface closer and alleviated the interaction between molybdenum oxide and the support, and facilitated the formation of well-dispersed Co- and Mo-oxo species on catalyst surface, thus resulting in higher HDS catalytic activity than pure γ-Al₂O₃ support without modifiers. Consequently, the addition of TiO₂ obviously improved the HDS conversion of dibenzothiophene.     

Growths of mechanical elasticity and electrical conductance of graphene nanoplatelet/poly(lactic acid) composites under strong electric field: correlation with time evolution of higher order structure of graphene nanoplatelets

For a composite of poly(lactic acid) containing graphene nanoplatelets (GNPs) at a low concentration (0.34 vol%), this study examined growths of mechanical and electrical properties under an alternating current (AC) electric field, focusing on field-induced GNP structures governing those properties. The composite was subjected to the AC field (60 Hz) of various intensities E for various times t _E at 190 °C. A fraction of randomly oriented GNPs was aligned by the field and then connected into columns, as suggested from optical microscopy. This structural evolution led to qualitatively similar growths of low-frequency storage modulus and static electrical conductivity. The key quantity for understanding this growth was a time t _E* for occurrence of short circuit that detected formation of GNP columns conductively bridging the electrodes. The growths of both modulus and conductivity for various E were summarized as functions of a reduced variable, t _E/t _E*, confirming the growths commonly reflected the evolution of the GNP columns. However, the modulus grew fast and leveled off by t _E/t _E* ~ 1, whereas the conductivity kept growing gradually even at t _E/t _E* > 1. This difference was discussed in relation to the matrix chains and leftover GNPs out the column.