Computational study of core‐shell droplet formation in coaxial electrohydrodynamic atomization process

In this study, a computational fluid dynamic (CFD) model was developed to simulate the liquid cone‐jet and core‐shell droplet formation in the Coaxial Electrohydrodynamic Atomization (CEHDA) process. Validation experiments were conducted using poly(lactic acid) (PLA) and poly(lactic‐co‐glycolic acid) (PLGA) solutions as core and shell materials, respectively. Good agreement was obtained between experimental results and simulation predictions in terms of both particle size and core‐shell structure. Investigation of interfacial tension between core and shell fluids showed that a stable compound cone‐jet and droplet can be easily formed using miscible or partially miscible liquids compared with immiscible liquids with higher interfacial tension. It was also found that the nozzle tip configuration has significant effects on droplet production due to differences in fluid motion. The results also showed that the productivity of the CEHDA process, that is, slow production of core‐shell microparticles due to low flow rates, could be enhanced using optimal cone‐shaped nozzle configuration. Overall, this computational model provided a means of designing and optimizing CEHDA processes for large‐scale core‐shell microparticle fabrication in pharmaceutical application, such as selections of materials and nozzle configuration. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4259–4276, 2016     

Influence of electric field interference on double nozzles electrospinning

The low production rate of electrospinning process may limit the industrial use of single needle system. To meet high yield requirement and uniform fibers, a bottom‐up multiple jets electrospinning nozzle was designed, each nozzle can emit 6–18 jets. The influence of electric field interference on jet path, membrane shape, and fiber morphology were investigated. Experiment finds that electrical field strength in the closer part of two nozzles is weakened because of electric field interference when the distance between two nozzles is 30 mm, making the jet hard to emit in this section, and closer part of electrospun fiber webs has fewer fibers. The spinning in far side part of two nozzles is similar to that of single nozzle. While in middle part of one nozzle, the jet path is short, elongation of jets smaller, the formed fibers thicker, solvent evaporation less sufficient. When the distance of two nozzles is increased to 50 mm, influence of electric field interference is weaker, the electrospun fiber web and average diameter of fibers are almost the same as that of single nozzle electrospinning. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

An Electrospray Method Using a Multi‐Capillary Nozzle Emitter

A multi‐capillary nozzle emitter consisting of one metal plate with capillary nozzles and a ring type counter electrode was used as a multi‐electrospray atomizer. The number of capillary nozzles, flow rate of the liquid and the interval between the capillary nozzles were changed, and the droplet diameter and the voltage required for a steady cone‐jet mode were measured. For the multi‐capillary nozzle emitter, the interaction between the capillary nozzles is the important factor for obtaining fine droplets of uniform size. These fine droplets are obtained when there is only a small interaction between the capillary nozzles, and the equations obtained from the single capillary nozzle case are also applicable for the multi‐capillary nozzle emitter. When the number of capillary nozzles decreases (a situation which is not good for obtaining a large amount of droplets) or the interval between the capillary nozzles increases, the interaction between the capillary nozzles can be reduced. As the number of capillary nozzles increase, a higher voltage is required to obtain a fine droplet of uniform size.     

Double‐nozzle air‐jet electrospinning for nanofiber fabrication

A novel double‐nozzle air‐jet electrospinning apparatus was developed to fabricate nanofibers on a large scale. The distribution of the electric field at different nozzle distances was simulated to analyze the jet path, productivity, and deposition area of nanofiber webs and the nanofiber morphology. Our experiments showed that the bubbles usually ruptured intermittently on the top surface of the two nozzles and the jets traveled in a straight path with a high initial velocity. A continuous and even thickness of the nanofiber webs were obtained when the nozzle distances was less than 55 mm. At nozzle distances of 55 mm, the received fibers were thin with the lowest standard deviation. Experimental parameters involving the applied voltage, collecting distance, and air flow rate were also investigated to analyze the nanofiber morphology at a nozzle distance of 55 mm. The results show that the nanofibers presented a finer and thinner diameter at an applied voltage of 36 kV, a collecting distance of 18 cm, and an air flow rate of 800 mL/min. The nanofiber production of this setup increased to nearly 70 times that with a single‐needle electrospinning setup. On the basis of the principle of this air‐jet electrospinning setup, various arrangements of multinozzle electrospinning setups could be designed for higher throughput of nanofibers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40040.     

Facile synthesis of Pd@Pt octahedra supported on carbon for electrocatalytic applications

Due to the scarcity of Pt, it is highly desirable to construct core‐shell structures with ultrathin Pt shells while maintaining their high electrocatalytic activities. However, it is necessary to preferentially synthesize a core with a specific structure before further formation of core‐shell catalysts with specific morphologies. This prerequisite greatly increases the complexity of the synthesis process. This article describes a synthetic method of core‐shell Pd@Pt octahedra catalysts from Pd nanocubes, truncated nanocubes or truncated octahedra. The formation of octahedral core‐shell structures involves two key factors: (1) the oxidative etching process of Pd atoms at the corner sites; (2) the different reduction rates between Pt and Pd precursors. This mechanism can be extended to synthesize carbon‐supported sub‐8 nm Pd@Pt octahedra from commercial Pd/C catalysts. The derived carbon‐supported Pd@Pt octahedra catalysts performed comparable activity and durability for methanol oxidation reaction with state‐of‐art PtRu/C catalysts. This synthetic method provides an innovative path for large‐scale production of well‐controlled catalysts. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2528–2534, 2017     

Effect of chemical inhomogeneity on domains and ferroelectric properties of Fe‐modified 0.77Bi0.5Na0.5TiO3–0.23SrTiO3

Lead‐free 0.77(Bi_0.5Na_0.5)TiO₃–0.23Sr(Ti_1?xFe_x)O₃ (x = 0, 0.04) (BNT–23STF_x) was prepared using a conventional solid‐state reaction route. The effects of Fe‐modification on the chemical homogeneity from a μm scale perspective, the core‐shell domains structures, and the ferroelectric properties were investigated. The chemical homogeneity was analyzed using energy dispersive X‐ray mapping in scanning transmission electron microscopy mode, and the field‐dependent behaviors of strain and polarization were obtained to determine the ferroelectric properties. Substituting Fe³⁺ for Ti⁴⁺ resulted in completely different electrical behavior and properties, despite similar XRD patterns and microstructures. The Fe‐substitution promoted the mobility of Sr²⁺ ions in the BNT phase and, as a consequence, the chemical homogeneity increased and the core‐domains collapsed. Extending the ceramic processing, such as milling time and sintering time, affected domain distribution and compositional inhomogeneity, which led to a gradual transformation from ferroelectric to relaxor.     

Needleless electrospinning. I. A comparison of cylinder and disk nozzles

In this study, we demonstrated the needleless electrospinning of poly(vinyl alcohol) (PVA) nanofibers with two nozzles, a rotating disk and a cylinder, and examined the effect of the nozzle shape on the electrospinning process and resultant fiber morphology. The disk nozzle needed a relatively low applied voltage to initiate fiber formation, and the fibers were mainly formed on the top disk edge. Also, the PVA concentration had little influence on the disk electrospinning process (up to 11 wt %). In comparison, the cylinder electrospinning showed a higher dependence on the applied voltage and polymer concentration. The fibers were initiated from the cylinder ends first and then from the entire cylinder surface only if the applied voltage were increased to a certain level. With the same polymer solution, the critical voltage needed to generate nanofibers from the disk nozzle was lower than that needed to generate nanofibers from the cylinder. Both electrospinning systems could produce uniform nanofibers, but the fibers produced from the disk nozzle were finer than those from the cylinder when the operating conditions were the same. A thin disk (8 cm in diameter and 2 mm thick) could produce nanofibers at a rate similar to that of a cylinder of the same diameter but 100 times wider (i.e., 20 cm long). Finite element analysis of electric field profiles of the nozzles revealed a concentrated electric field on the disk edge. For the cylinder nozzle, an uneven distribution of the electric field intensity profile along the nozzle surface was observed. The field lines were mainly concentrated on the cylinder ends, with a much lower electric field intensity formed in the middle surface area. At the same applied voltage, the electric field intensity on the disk edge was much higher than that on the cylinder end. These differences in the electric field intensity profiles could explain the differences in the fiber fineness and rate of the nanofibers produced from these two nozzles. These findings will benefit the design and further development of large‐scale electrospinning systems for the mass production of nanofibers for advanced applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A method for scale‐up of co‐electrospun nanofibers via flat core‐shell structure spinneret

An approach to the scale‐up of co‐electrospinning via a flat core‐shell structure spinneret has been developed in this study. The spinneret with a flat surface involves shell‐holes and core‐needles. Electric field simulation reveals that the flat core‐shell spinneret configuration creates a more uniform electric field gradient. Experimental study shows that in comparison with the conventional needle co‐electrospinning, core‐shell nanofibers produced by this new designed setup are finer and of better morphology. Composite nanofibers with special morphologies can be fabricated by modifying the structure of this spinneret. The production rate of the core‐shell nanofibers can be enhanced by increasing the hole and needle number of the spinneret. This novel design is expected to provide a promising method towards the massive production of core‐shell nanofibers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41027.     

CuO‐added KNbO3‐BaZrO3 lead‐free piezoelectric ceramics with low loss and large electric field‐induced strain

CuO‐added (1‐x)KNbO₃‐x mol%BaZrO₃ ceramics with 0.0≤x≤7.0 were sintered at 960°C. Large double polarization vs electric field (P‐E) and sprout‐shaped strain vs electric field (S‐E) hysteresis curves were obtained from the specimens with x≤2.0. They exhibited large polarizing electric fields (E_P) owing to the presence of a large number of defect dipoles (P_Ds) that formed between Cu²⁺ ions and oxygen vacancies. Small double P‐E hysteresis curves were observed for the specimens with x≥3.0 with reduced E_P because of the decreased number of P_Ds and the presence of a polymorphic phase structure containing both orthorhombic and pseudocubic structures. In particular, the specimen with x=5.0 exhibited a large strain of 0.16% at 8.0 kV/mm with a small E_P of 1.2 kV/mm and good fatigue property: this specimen maintained a strain of 0.13% at 6.0 kV/mm after 10⁶ cycles of 3.0 kV/mm.     

Large Electrostrain in K(Nb1−xMnx)O3 Lead‐Free Piezoelectric Ceramics

K(Nb_1?xMn_x)O₃ (KN_1?xM_x) ceramics with 0.005 ≤ x ≤ 0.015 were sintered at 1020°C through a normal sintering process without the formation of a liquid phase. They exhibited double polarization versus electric field (P–E) hysteresis and sprout‐shaped strain versus electric field (S–E) curves owing to the presence of a defect dipole (P_D), which was formed between the acceptor Mn³⁺ ion and the oxygen vacancy. Moreover, the aging process was not required to develop the P_D. The KN_1?xM_x ceramics exhibited a large strain of ~0.2% at 6.0 kV/mm. For the KN_0.985M_0.015 ceramic, this large strain was maintained after 10⁴ cycles of an electric field of 6.0 kV/mm. This ceramic also maintained a double hysteresis curve at 200°C. Therefore, the KN_0.985M_0.015 ceramic has a large electric field‐induced strain, along with good thermal and fatigue properties for multilayer piezoelectric actuators.     

Synthesis of sub‐micrometer core–shell rubber particles with 1,2‐azobisisobutyronitrile as initiator and deformation mechanisms of modified polystyrene under various conditions

BACKGROUND: Sub‐micrometer core‐shell polybutadiene‐graft‐polystyrene (PB‐g‐PS) copolymers with various ratios of polybutadiene (PB) core to polystyrene (PS) shell were synthesized by emulsion grafting polymerization with 1,2‐azobisisobutyronitrile (AIBN) as initiator. These graft copolymers were blended with PS to prepare PS/PB‐g‐PS with a rubber content of 20 wt%. The mechanical properties, morphologies of the core‐shell rubber particles and deformation mechanisms under various conditions were investigated. RESULTS: Infrared spectroscopic analysis confirmed that PS could be grafted onto the PB rubber particles. The experimental results showed that a specimen with a ‘cluster’ dispersion state of rubber particles in the PS matrix displayed better mechanical properties. Transmission electron micrographs suggested that crazing only occurred from rubber particles and extended in a bridge‐like manner to neighboring rubber particles parallel to the equatorial plane at a high speed for failure specimens, while the interaction between crazing and shear yielding stabilized the growing crazes at a low speed in tensile tests. CONCLUSION: AIBN can be used as an initiator in the graft polymerization of styrene onto PB. The dispersion of rubber particles in a ‘cluster’ state leads to better impact resistance. The deformation mechanism in impact tests was multi‐crazing, and crazing and shear yielding absorbed the energy in tensile experiments. Copyright © 2009 Society of Chemical Industry     

Improved dispersion of carbon nanotubes in poly(vinylidene fluoride) composites by hybrids with core–shell structure

Core–shell structure hybrids of carbon nanotubes (CNTs)/BaTiO₃ (H‐CNT‐BT) and commercial multi‐wall CNTs are respectively incorporated into poly(vinylidene fluoride) (PVDF) for preparing the composites near the percolation thresholds. A comprehensive investigation for CNT's dispersion and composite's conductivity is conducted between H‐CNT‐BT/PVDF and CNT/PVDF at different depths vertical to the injection's direction. Gradual increases of the conductivity in two composites are observed from the out‐layer to the core part which infers an inhomogeneous CNT's dispersion in the interior of composites due to their migration under flow during the injection. However, the use of H‐CNT‐BT fillers with core–shell structure enables to reduce this inhomogeneous dispersion in the composite. Furthermore, the conductive network of CNTs in H‐CNT‐BT/PVDF is less sensitive to the thermal treatment than the one in CNT/PVDF composite, which infers the core–shell structure of hybrids can ameliorate the sensitivity of the conductive network. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45693.     

Preparation and characterization of core‐shell polystyrene/polyaniline/Pd composites and their catalytic properties for the reduction of 4‐nitrophenol

Herein, polystyrene/polyaniline/Pd (PS/PANI/Pd) core‐shell composite catalysts were prepared by a facile swelling‐diffusion‐interfacial polymerization method. PS microparticles were firstly prepared by dispersion polymerization and were swollen by aniline monomer without any surface modification. H₂PdCl₄ acid was used as palladium precursor. The was adsorbed on the surface of aniline‐swollen PS microparticles because of the electrostatic attraction between and anilinium positive ions protonated by H⁺, which was diffused from the aniline‐swollen PS microparticles. Then HCl solution was added to control the diffusion rate of anilinium positive ions and ammonium persulfate (APS) was used to polymerize the anilinium ions to get PANI shell. Due to the redox activity between PANI and Pd ions, Pd nanoparticles can be in situ formed on the surfaces of PS. Therefore, the core‐shell PS/PANI/Pd composite catalysts were obtained. The morphology and structure of the obtained composites was characterized by TEM, FT‐IR and EDX. Results showed that the products presented excellent catalytic properties for the reduction of 4‐nitrophenol (4‐NP) to 4‐aminophenol (4‐AP) in the presence of NaBH₄ by virtue of the interaction between Pd nanoparticles and conducive PANI shell. The catalytic reaction obeyed the pseudo‐first‐order reaction equations and the reaction rate constants were also calculated in this article. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44812.     

Simultaneous enhancements of mechanical properties and hydrophilic properties of polypropylene via nano‐silicon dioxide modified by polydopamine

This study is focused on the development of high‐performance composite materials based on nano silicon dioxide (nano‐SiO₂) modified by polydopamine (PDA). A facile one‐step method was developed to synthesize core–shell structured SiO₂@polydopamine (PDA) nanospheres. During the synthesis, a PDA shell was simultaneously coated on the SiO₂ nanospheres to form the core–shell nanostructure which was blended with polypropylene (PP) and β nucleating agent (β‐NA) to enhance both mechanical and hydrophilic properties. Nano‐SiO₂ particles modified by PDA (SiO₂@polydopamine) influence the crystallization of PP seriously. The results indicated that when 1%wt SiO₂@polydopamine was added, the impact strength of composite reached the maximum value 12.60k J/m² increasing 137% compared with PP, the bending strength and bending modulus decreased slightly reaching 41.85 MPa, and 2192 MPa, respectively, the composite possessed hydrophilic performance with the water contact angle of 88.32°. β nucleating agent was used in all formulations, the synergistic effect toward mechanical properties with SiO₂@polydopamine was studied. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45004.     

Kinetic Modeling of Reactive Absorption of Carbon Dioxide in a Spray Dryer

A semi‐empirical kinetic correlation was obtained through a shrinking core model assumption for reactive absorption of CO₂ with NaOH solution by applying response surface method analogy in a laboratory‐scale spray‐dryer absorber. The effect of approach temperature, absorbent concentration, nozzle diameter, and L/G ratio on the kinetic coefficient was studied and the optimum operating conditions to reach the maximum absorption were determined.     

Statistical Optimization of the Biodiesel Production Process Using a Magnetic Core‐Mesoporous Shell KOH/Fe3O4@γ‐Al2O3 Nanocatalyst

A magnetic core‐mesoporous shell KOH/Fe₃O₄@γ‐Al₂O₃ nanocatalyst was synthesized using the Fe₃O₄@γ‐Al₂O₃ core‐shell structure as support and KOH as active component. The prepared samples were characterized by X‐ray diffraction (XRD), field‐emission scanning electron microscopy (FE‐SEM), energy‐dispersive X‐ray spectroscopy (EDS), Fourier transform infrared (FTIR), Brunauer‐Emmett‐Teller (BET), and vibrating sample magnetometry (VSM) techniques. Transesterification of canola oil to methyl esters (biodiesel) in the presence of the magnetic core‐mesoporous shell KOH/Fe₃O₄@γ‐Al₂O₃ nanocatalyst was investigated. Response surface methodology (RSM) based on the Box‐Behnken design (BBD) was employed to optimize the influence of important operating variables on the yield of biodiesel. A biodiesel yield of 97.4 % was achieved under optimum reaction conditions. There was an excellent agreement between experimental and predicted results.     

Dynamic viscoelasticity and phenomenological model of electrorheological elastomers

Electrorheological elastomers (EREs) present a tunable viscoelasticity with the application of an electric field. For their application, it is necessary to investigate the viscoelasticity of the EREs under various loading conditions and establish an accurate constitutive model. In this study, anisotropic silicone‐rubber‐based EREs with 30 vol % TiO₂–urea core–shell particles were prepared under an orientation electric field. We evaluated their viscoelasticities by testing their shear stress–shear strain hysteresis loops under various electric fields, frequencies, and strain amplitudes. On the basis of the experimental data, a nonlinear, revised Bouc–Wen phenomenological model was established, and the parameters in the model were identified. The results indicate that the revised model could accurately describe the viscoelastic properties of the EREs within a low frequency. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45407.     

Nanospace‐confined synthesis of coconut‐like SnS/C nanospheres for high‐rate and stable lithium‐ion batteries

Coconut‐like monocrystalline SnS/C nanospheres are developed as anode materials for lithium‐ion batteries by a micro‐evaporation‐plating strategy in confined nanospaces, achieving reversible capacities as high as 936 mAh g^?1 at 0.1 A g^?1 after 50 cycles and 830 mAh g^?1 at 0.5 A g^?1 for another 250 cycles. The remarkably improved electrochemical performances can be mainly attributed to their unique structural features, which can perfectly combine the advantages of the face‐to‐face contact of core/shell nanostructure and enough internal void space of yolk/shell nanostructure, and therefore well‐addressing the pivotal issues related to SnS low conductivity, sluggish reaction kinetics, and serious structure pulverization during the lithiation/delithiation process. The evolutionary process of the nanospheres is clearly elucidated based on experimental results and a multiscale kinetic simulation combining the microscopic reaction‐diffusion equation and the mesoscopic theory of crystal growth. Furthermore, a LiMn₂O₄//SnS/C full cell is assembled, likewise exhibiting excellent electrochemical performance. © 2018 American Institute of Chemical Engineers AIChE J, 64: 1965–1974, 2018     

Formation process of core‐shell microparticles by solute migration during drying of homogenous composite droplets

Particle formation process during spray drying profoundly impacts particle morphology and microstructure. This study experimentally investigated the formation of core‐shell‐structured microparticles by one‐step drying of composite droplets made of Eudragit^® RS (a polycationic acrylic polymer in nanoparticle form) and silica sol. The formation of an incipient surface shell was monitored using single droplet drying technique, and the freshly formed shell was recovered for subsequent analyses. Adding silica to RS precursor increased the shell formation time and altered the properties of the incipient shell from water‐dispersible to nondispersible. The incipient shell formed from RS/silica droplets with mass ratios of 1.5%:1.5% and 0.5%:2.5% showed ingredient segregation with a preferential accumulation of RS, similar to the shell region of dried microparticles. After shell formation, excess silica sol in the liquid phase could flow inward, producing a dense core. This mobility‐governed solute migration would be useful for constructing core‐shell microparticles using other precursor systems. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3297–3310, 2017     

Relationship between structure and properties in high‐performance PA6/SEBS‐g‐MA/(PPO/PS) blends: The role of PPO and PS

This work aimed at studying the role of poly(phenylene oxide) (PPO) and polystyrene (PS) in toughening polyamide‐6 (PA6)/styrene‐ethylene‐butadiene‐styrene block copolymer grafted with maleic anhydride (SEBS‐g‐MA) blends. The effects of weight ratio and content of PPO/PS on the morphology and mechanical behaviors of PA6/SEBS‐g‐MA/(PPO/PS) blends were studied by scanning electron microscope and mechanical tests. Driving by the interfacial tension and the spreading coefficient, the “core–shell” particles formed by PPO/PS (core) and SEBS‐g‐MA (shell) played the key role in toughening the PA6 blends. As PS improved the distribution of the “core–shell” particles due to its low viscosity, and PPO guaranteed the entanglement density of the PPO/PS phase, the 3/1 weight ratio of PPO/PS supplied the blends optimal mechanical properties. Within certain range, the increased content of PPO/PS could supply more efficient toughening particles and bring better mechanical properties. Thus, by adjusting the weight ratio and content of PPO and PS, the PA6/SEBS‐g‐MA/(PPO/PS) blends with excellent impact strength, high tensile strength, and good heat deflection temperature were obtained. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45281.