Computational Fluid Dynamics modeling of micromixing performance in presence of microparticles in a tubular sonoreactor

This paper reports the results of CFD modeling for evaluating micromixing efficiency in presence of polymeric microparticles in a continuous tubular sonoreactor. The studied tubular sonoreactor was equipped with four 1.7 MHz ultrasound transducers and micromixing efficiency was analyzed using Villermaux/Dushman reaction. The main objective of this study is to illustrate the simultaneous effects of 1.7 MHz ultrasound waves and polymeric microparticles on micromixing performance from the fluid dynamics point of view. In order to model the presence of these microparticles, the Eulerian multiphase model was applied based on kinetic theory of granular flow. The dynamic mesh method was used to model the vibration of 1.7 MHz piezoelectric transducers. CFD modeling results indicate the positive effects of the presence of microparticles on micromixing efficiency and more efficient velocity distribution inside the sonoreactor. This was interpreted as the ability of high frequency ultrasound waves (1.7 MHz) to move and disperse the microparticles.     

平行与交叉双声束声场中的声化学反应研究

给描述超声空化效应动力学过程的Noltingk-Napprias方程增加了一个表征外界随机微扰的修正项,通过对这个方程的解发现,声场施加微扰后,可使空化的空化泡数量增加。在此理论基础上,设想采用交叉双声束声场实现对声场施加微扰。实验结果证实,采用交叉双声束声场后声场中的声化学产额(分别以溶液pH值改变,电导率改变表征)较平行双声束声场增加约11%~13%不等。这一结果对于声化学反应器提高声化学产额有意义。     

Prediction of the Characteristics of a New Sonochemical Reactor Using an Expert Model

Artificial neural network (ANN) models were developed to estimate the characteristics of a novel high-frequency sonoreactor. Mean residence time and ultrasound dissipated power were considered to evaluate the performance of this sonoreactor. These parameters were calculated from predicted tracer concentration and temperature variation by ANN models. The best network configurations were determined as two layers network including 10 and 12 neurons in hidden layer for the concentration and temperature prediction, respectively. For both networks Levenberg–Marquardt was the best training algorithm with average absolute relative error (AARE) below than 2%. The estimated characteristics were in good agreements with experimental data. Also, sensitivity analyses were done to find the relative importance of each input variable in networks training.     

Quasistatic and dynamic properties of 1–3 composites made by soft molding

The development of the soft mold process allows for the preparation of fine scale 1–3 composites with PZT rods of different size, shape and spacing, which can be used as ultrasonic transducers for frequencies ⩾5 MHz. [Gebhardt, S., Schönecker, A., Steinhausen, R., Hauke, T., Seifert, W. & Beige, H., Fine scale 1-3 composites fabricated by the soft mold process: preparation and modeling. Ferroelectrics, 241 (2000) 67]. By this method, composites with a square, hexagonal and non regular arrangement of PZT rods of different shape have been fabricated and characterized by measuring their quasistatic and dynamic properties. The experimental results were compared with data from finite element method (FEM) modeling and analytical solutions. The vibrational characteristics of the composites were strongly influenced by the rod geometry and the rod arrangement. To evaluate the 1–3 composite performance, modal analysis and modeling of the impedance spectrum were carried out using the FEM package ANSYS.     

Determination of reversible and irreversible contributions to the polarization and strain response of soft PZT using the partial unloading method

Experimental work is aimed at systematically investigating the non-linear ferroelectric and ferroelastic behavior of a commercially available soft lead zirconate titanate (PZT) material. The fast partial unloading method is used to measure the material properties of unpoled soft PZT under pure electric field and of initially pre-poled soft PZT under compressive stress loading. In the first experiment using unpoled PZT, the evolution of piezoelectric constants and dielectric permittivity is determined as a function of electric field. It is found that the piezoelectric constants and dielectric permittivity depend on the electric field history. The results are used to separate the reversible strain and polarization from the irreversible ones caused by domain switching. In the second experiment using initially pre-poled PZT, it is found that the strain response is significantly dependent on the stress loading rate. The elastic moduli and piezoelectric coefficients are evaluated with respect to the compressive stress history. The measured longitudinal and transverse irreversible strains change significantly during both loading and unloading processes. An attempt is made to discuss the use of irreversible strain and irreversible polarization as internal variables for constitutive modeling. This investigation provides valuable information for modeling to predict the performance and for improving the reliability of piezoelectric devices.     

Electrophoretic Deposition of Lead Zirconate Titanate Ceramics

Electrophoretic deposition (EPD) of submicrometer lead zirconate titanate (PZT) powders in ethanol was conducted to form thick green PZT films up to 160 μm thick. The PZT colloid stability, as a function of pH, was studied by zeta-potential measurement. The electrical condition of the suspension was quantified by conductivity measurement at various pH values. The effect of different applied current densities on the deposition mass was investigated. A kinetic model for the constant-current-density EPD process, taking into account the particle concentration variation, was also examined, based on the experimental results obtained in the present work. An empirical relationship between the kinetic constant and the applied current density has been proposed.     

The influence of chemical passivation on the PZT/Pt electrode interface

It has been recognized that the interdiffusion of atomic species between a PZT film and the Pt bottom electrode leads to the gradual degradation of a PZT capacitor. In order to prevent this interdiffusion, experimental studies on chemical passivation to the bottom electrode surface were carried out by the sulfurization method. It was observed that a sulfur layer was built up on the Pt substrate with small grains, which resulted in a structural change at the Pt surface. Atomic force microscopy (AFM) showed that the film roughness of the Pt surface was increased by sulfur treatment. Pb(Zr_0.5Ti_0.5)O₃(PZT) thin films were prepared on a Pt/Ti/SiO₂Si bottom electrode by spin-coating techniques. The microstructure and the preferred orientation of the PZT films were shown to depend on the sulfur-treated electrode. The PZT capacitor on a clean Pt electrode was confirmed to be ferroelectric with Pr=17.7 μC/cm² and Ec=65 kV/cm from the P-E hysteresis curves. The fatigue behavior of a PZT film capacitor prepared on a sulfur-treated one was observed to be relaxed, but the absolute value of Pr was paid off.     

Etude de l'oxydation du pentachlorophénol dans différentes géométries de réacteurs à ultrasons de haute fréquence

The determination of the key geometric parameters used for high-frequency sonoreactor modeling has been studied. The methodology allowing the characterization of the different reactors built in our laboratory has been defined. The methods are: calorimetry, determination of the residence time distributions, the observation of the chemiluminescence of luminol and the degradations of a prototype molecule: pentachlorophenol. After characterization of the studied reactors, it seems that volumetric power, with equivalent emitting system, is the major parameter of the reactor's performance.     

Thermodynamics of Ferroelectric Solid Solutions with Morphotropic Phase Boundaries

A thermodynamic analysis is presented for the diffusionless phase diagrams of ferroelectric solid solutions that display a morphotropic phase boundary (MPB) separating adjacent tetragonal and rhombohedral phases. Equations are developed for the shape of the MPB, the locations of triple and tricritical points, and for the line along which the anisotropy of polarization vanishes. The appearance of lower symmetry orthorhombic and monoclinic phases is considered and the topologies of energy surfaces in the region of the phase diagram where these phases may stabilize are illustrated. The theory is applied to the solid solution of lead zirconate with lead titanate (PZT) and relationships between polar anisotropy and the transformation strain, dielectric susceptibility and piezoelectric properties, are discussed. The analysis is used to reproduce phase boundary lines for solid solutions of lead titanate with lead magnesium niobate (PMN‐PT) and lead zinc niobate (PZN‐PT) and composition–temperature diagrams along isopleths in the ternary system PMN‐PZT are estimated. The anisotropies of polarization in solid solutions based on lead titanate and barium titanate are contrasted. The results provide a thermodynamic framework useful for guiding experimental investigations of ferroelectric solid solutions and for generating energy functions used in constitutive modeling and phase field simulations of microstructure and properties.     

Effects of thermal strain on electric properties of lead zirconate titanate thin films upon LaNiO3 coated base metal plates

Electric properties for ferroelectric lead zirconate titanate (PZT50/50, 45/55, 40/60, 30/70) thin films on base metal plates with different thermal expansion coefficient (TEC) were calculated by a phenomenological model. Results show that when the TEC of substrates increases, dielectric constant, tunability and piezoelectric coefficient d₃₃ of all PZT thin films with tetragonal phase are decreased due to the larger compressive thermal strain. PZT50/50 thin films deposited on smaller TEC substrates can achieve higher dielectric constant, tunability and d₃₃. The computed dielectric constant of PZT50/50 thin films is in accordance with the measured results from sol-gel experimental process, and the trend of dielectric constant of PZT films adjacent to morphotropic phase boundary (MPB) derived from some references also agrees with that from calculation. These results suggest that higher tunability and d₃₃ of PZT films can be obtained by choosing smaller TEC substrates.     

Voltage effect of corona poling on characteristics of PbZrxTi1−xO3 (PZT) film

The paper investigates the voltage effect of corona poling on the characteristics of PbZr_xTi_1−xO₃ (PZT) thin film. Purchased PZT powder and lab-made PZT solution were mixed together as sol-gel that was spin-coated on titanium (Ti) substrate. X-ray diffractometer (XRD), scanning electron microscopy (SEM), impedance analyzer were utilized to measure the orientation and dielectric characteristics of films for comparison. The experimental results indicated that the poling voltage would not affect the orientation of crystallization, microstructure and grain size of PZT film surface. However, the higher applied poling voltage would result in better charge storage capacity and energy transfer efficiency of the film.     

Thermal and dielectric behavior of flexible polycarbonate/lead zirconate titanate composite system

Polycarbonate (PC)/Lead Zirconate Titanate (PZT) composites were prepared using solution mixing method followed by hot pressing. The volume fraction of PZT particles was varied from 0 to 27.5%. SEM showed good dispersion of PZT in the PC matrix. XRD confirmed the perovskite structure of PZT and amorphous structure of polycarbonate. The dielectric constant of the composites measured at 1 kHz, increased ～3.5‐fold compared with pure PC. The modified Lichtenecker equation agreed well with the experimental data. There was no dispersion in the dielectric constant of the composites for the frequency range of 1 kHz to 10 MHz. However, at frequencies higher than 10 MHz significant drop in dielectric constant was observed. The dissipation factor of the composites was found below 0.02. However, above 1 MHz, an abrupt increment in the dissipation factor was observed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39913.     

Effects of microwave heating on dielectric and piezoelectric properties of PZT ceramic tapes

Commercial lead zirconate titanate (PZT) perovskite powders were used to fabricate ceramic tape and then sintered by microwave and conventional methods. Both dielectric and piezoelectric properties of PZT ceramic tapes were studied in terms of sintering process. X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM) show the PZT perovskite phase with smaller grain size and dense microstructure can be obtained at a lower sintering temperature by microwave process. It was also observed that shrinkage ratio and bulk density of the tapes sintered at 800 °C were obtained about 19% and 7.46 g/cm³ by the microwave heating method, respectively, that is corresponding to those values of sintered PZT tapes at 950 °C by conventional process. Moreover, the dielectric constant and maximum permittivity are increased about 30% as compared with conventional processing method. The experimental results demonstrated that the characteristics of the PZT tapes could be significantly improved by microwave heating method. These results demonstrate that such a simple approach can upswing the piezoelectric and dielectric properties of these tapes by using microwave process with a short heating time.     

Using microparticles to enhance micromixing in a high frequency continuous flow sonoreactor

In this paper, an experimental study was conducted to investigate the effect of high frequency ultrasound wave on micromixing efficiency in the presence of polymeric microparticles in a tubular sonoreactor. The size and volume fraction of polymeric microparticles were varied and the micromixing efficiency was studied by adopting the Dushman reaction coupled with a neutralization reaction. In addition, the effect of flow rate and liquid viscosity on the segregation index was studied. The experimental results showed that the movement and dispersion of the polymeric microparticles by ultrasound wave could improve the micromixing efficiency. The results showed that the size of the polymeric microparticles has great effect on mixing. Moreover, it was found that in the presence of these microparticles, segregation index decreases significantly and their effect reduces with increase in the solution viscosity. The presented results show that using high frequency ultrasound waves in the range of MHz and in the presence of microparticles can promise to reach an efficient micromixing in tubular sonoreactors.     

Piezoelectric properties and damping behavior of highly loaded PZT/polyurethane particulate composites

In this study, using a solution casting process, thermoplastic polyurethane elastomer (TPU) composites containing different contents of lead zirconate titanate (PZT) ferroelectric particles were produced. The damping treatment of composites at high volume of fillers was investigated. SEM micrographs showed that PZT particles had a proper distribution in the PU matrix. Differential scanning calorimetry (DSC) thermograms indicates that melting enthalpy decreases by raising PZT filler content. The results of the dynamic mechanical thermal analysis (DMTA) proved that the magnitude of loss factor (tan δ) strongly depends on PZT content, and it decreased from 0.51 to 0.27 as PZT content increased. The value of E₀ increases to 0.32 GPa in the composite reinforced with 50 v% of PZT. The role of PZT on the acoustic behavior of TPU was measured using the acoustic absorption coefficient (a). The results showed that as PZT content increased from 0 to 50%, the acoustic absorption coefficient reached 0.25 at 6000 Hz frequency. The composites of PZT/PU with 0–3 connectivity were poled, and the optimal poling conditions that could be applied without sample breakdown were studied. Moreover, we prepared composites containing 70 vol% PZT particles by modifying the particles. Modification of PZT particles caused a decrease in both d₃₃ and g₃₃ constants of the PZT/PU composites.     

Enhanced dielectric and ferroelectric properties induced by Ag @ Pb(Zr,Ti)O3 in poly(vinyl alcohol) matrix composites: A solution casting approach

The present research work focused on the dielectric and electrical properties of silver (Ag) doped Pb(Zr,Ti)O₃ (PZT) particles embedded in a matrix of poly(vinyl alcohol) (PVA) via solution casting technique. The structural analysis confirmed the presence of Ag particles and the microstructural study revealed that both Ag and PZT particles were successfully homogenized over the polymer matrix. The Ag–PZT–PVA composites showed enhanced dielectric properties over a wide range of frequency and the dielectric constant value of such composites was significantly increased to 366 (100 Hz) at 1.1 wt % filler loading. The percolation threshold of the Ag–PZT–PVA composites was found to be 0.9 wt %. The experimental result well fitted to the percolation theory. The enhancement of dielectric constant of the resulting composite systems might be attributed to the increment of conductivity of the interlayer between PZT and PVA due to the presence of Ag particles, which improved the space charge polarization and Maxwell–Wagner–Sillars (MWS) polarization effects. Furthermore, the remnant polarization of the unpoled Ag–PZT–PVA composites (2P_r ～1.48 µC/cm² for 1.1.wt % of Ag–PZT) has also improved, which is favorable for enhanced ferroelectric properties of the composites. The present findings of the composites might be exploited in the potential application of high performance energy storage devices. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45583.     

Novel forming of columnar lead zirconate titanate structures

The present study is focused on the processing of columnar lead zirconate titanate (PZT) structures on Ti/Pt-coated silicon substrates using electrohydrodynamic deposition. It was found that the as-deposited PZT structure is highly dependent on the concentration of the sprayed precursor, which is believed to be the characteristic of electrohydrodynamic deposition. 0.01, 0.03, 0.06, 0.12, 0.3 and 0.6 M PZT sols were used to prepare as-deposited structures. Columnar PZT structures, which are important for the processing of 1-3 composites, were obtained with the 0.6 M sol. As-deposited and heat-treated columnar PZT structures were investigated using scanning electron microscopy and X-ray diffraction. The development of the PZT columns was studied by observing the cross-section of the structures deposited over different time sprays, revealing a three-stage growth process for these structures. The affect of substrate temperature on the columnar structure was also analysed by studying the density of the columns. Finally, a 1-3 composite was produced by infiltrating photoresists into the columnar PZT structures and the relative permittivity and dissipation factor of such composite were measured as 105 and 0.021. Modelling the structures as a PZT and a polymer capacitor connected in parallel in the PZT/polymer composite suggests that the relative permittivity of PZT columnar material is approximately 154.     

(SrZrO_3)_(10)(SrTiO_3)_(90)缓冲层对PZT结晶及性能的影响

采用Sol-gel法制备了PbZr0.52Ti0.48O3 (PZT)薄膜,并研究了(SrZrO3)10(SrTiO3)90((SZO)10(STO)90)缓冲层对PZT薄膜结晶和性能的影响.X射线衍射(XRD)结果表明:(SZO)10(STO)90缓冲层对PZT薄膜结晶有取向诱导作用,由(SZO)10(STO)90诱导的PZT薄膜有很强的(111)择优取向,缓冲层将PZT薄膜的取向度α由45.0%提高到了90.1%以上;PZT的(111)择优取向提高了薄膜的电性能,使剩余极化强度Pr从26.8 μC/cm2增大到38.8 μC/cm2.     

Performance improvement of piezoelectric‐rubber by particle formation of linear aggregates

We investigate the piezoelectric response of piezoelectric‐rubber consisting of lead zirconate titanate (PZT) particles and silicon rubber prepared by holding it at 100°C for 60 min. Two types of piezoelectric‐rubber were used; one was mixed with PZT particles forming linear aggregates, and the other was mixed with PZT particles forming a random dispersion. The piezoelectric‐rubber whose PZT particles were aligned normal to the rubber surface had much higher piezoelectric effect than the type of piezoelectric‐rubber whose PZT particles were randomly dispersed. The reason for this is that force applied on the former is directly transmitted to PZT particles and the electric charges generated from PZT particles had higher mobility because of the aligned PZT particles, which were connected with each other. As a result, the formation of linear aggregates of PZT particles in rubber was effective in enhancing piezoelectric properties of piezoelectric‐rubber. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39862.     

Tailoring the Magnetoelectric Properties of Pb(Zr,Ti)O3 Film Deposited on Amorphous Metglas Foil by Laser Annealing

This study demonstrates the modulation of off‐resonance magnetoelectric (ME) response of the Pb(Zr,Ti)O₃ (PZT)/ Metglas (FeBSi) bilayered composite by laser annealing. A continuous‐wave 532 nm Nd:YAG laser with varying fluences (210–390 J/mm²) was utilized to anneal the 2 μm thick PZT film deposited using granule spray in vacuum (GSV) technique on magnetostrictive amorphous Metglas foil. It was found that the dielectric and ferroelectric properties of the PZT film are strongly affected by the exposure to laser fluence. The ME voltage coefficient of PZT/Metglas increased with the fluence up to 345 J/mm², reaching a high value of 880 mV/cm·Oe. The electrical and ME properties were correlated with the changes observed in crystallinity and grain size of the PZT film as well as with the alterations in microstructure and magnetic behavior of Metglas. Our results demonstrate that enhanced ME coupling can be realized in PZT/Metglas film composites by controlling the laser fluence.