Securely anchored Prussian blue nanocrystals on the surface of porous PAAm sphere for high and selective cesium removal.

Prussian blue (PB) has been well known as a pigment crystal to selectively sequestrate the radioactive cesium ion released from aqueous solutions owing to PB cage size similar to the cesium ion. Because the small size of PB is hard to deal with, the adsorbents containing PB have been prepared in the form of composites causing low sequestration efficiency of cesium. In this study, securely anchored PB nanocrystals on the surface of millimeter-sized porous polyacrylamide (PAAm) spheres (PB@PAAm) have been prepared by the crystallization of PB on the Fe3+ adsorbed PAAm. The securely anchored PB nanocrystals have been demonstrated to be selective and efficient adsorbents for sequestration of the radioactive cesium. The well-interconnected-spherical pores and millimeter-sized diameter of the PB@PAAm adsorbents facilitated permeation of Cs+ into the adsorbent and ease of handling respectively. Especially the well-interconnected-spherical pores allowed that PB@PAAm showed 90% of its maximum Cs+ adsorption capacity within 30 min. The PB@PAAm showed an outstanding Cs+ capture ability of 374 mg/g, high removal efficiency of 85% even at low concentration of Cs+ (10 ng/L), and superior selectivity of Cs+ against interference ions of Na+, K+, Mg2+, and Ca2+.

Highly Durable and Thermally Conductive Shell-Coated Phase-Change Capsule as a Thermal Energy Battery.

Robust and thermally conductive phase-change capsules (PCCs) can be effectively used as dispersoids for heat transfer fluids (HTFs) to utilize waste heat. Here, we demonstrate PCCs encapsulated with a cross-linked poly(2-hydroxyethyl methacrylate) shell that showed high durability and low thermal hysteresis for effective heat uptake and release. The circulation system was manufactured by mimicking the 4th Generation District Heating (4GDH) system to confirm the heat delivery efficiencies of PCC-dispersed slurries (PCSs) as the HTFs. The enthalpy change of water after it received heat from the PCS improved by up to 41.1% on increasing the amount of PCCs in the PCS. Furthermore, a high PCC recovery of 92 wt % was achieved after 1500 cycles, which accompanied a phase transition. The PCC developed by us can thus enable effective storage/delivery of waste heat-driven energy for zero-energy buildings and a 4GDH system, as well as thermal management of electronics.

Core/shell hybrid fiber with aminated PAN and Fe2O3 as a high-capacity adsorbent for phosphate ions.

APANF@Fe2O3, a phosphate adsorbent, was synthesized in two steps: the immobilization of an amine group onto polyacrylonitrile fiber (PANF) and the adsorption of an iron ion on aminated PANF (APANF). The amination degree of the PANF was adjusted considering its mechanical properties. The Fe2O3 on the surface of the APANF played a role as a phosphate-grasping layer via a ligand-exchange reaction. The APANF@Fe2O3 showed a considerable PO43- adsorption amount of ca. 6 mmol/g at a low pH region (ca. 2-7) and 3 mmol/g at a high pH region (ca. 8-12). The adsorption data were interpreted with various kinetic and isotherm models. The Langmuir model was more suitable than the Freundlich and Redlich-Peterson models to fit the experimental data of the phosphate adsorption on the APANF@Fe2O3 and the pseudo-second-order model was better matched than the pseudo-first-order and Elovich's models. The results of this study demonstrate that the surface of the fibrous adsorbent was homogenous and the phosphate adsorption behavior of the APANF@Fe2O3 followed a simultaneous chemisorption process into the Fe2O3 layer.

Understanding Uniform, Fast, and Scalable Buoyancy-Driven Macro-Sized Drop Generations.

Generating uniform drops with fast production rate and tunable volume in a high-throughput way is important in various academic and industrial disciplines. In this study, we propose a strategy to produce milliscale drop in a size-tunable way and model its formation processes. The size of generated drops is uniform (<1% of the standard deviation) and tunable by controlling the flow rate, the pore diameter in membrane, and the surface hydrophobicity of membranes in the dripping regime. Also, their production rates range from ca. 0.1-2.1 Hz. The drop formation is successfully investigated by our five-force balance model. On hydrophobic membranes, the range of the dripping regime for uniform drops is wider (from ca. 5.7 to 10.4 mm) than that on hydrophilic membranes (from ca. 3.8 to 7.0 mm). Also, in the dripping regime in hydrophilic membranes, the production rates of the drop are faster than those of the hydrophobic membrane.

Switchable electrorheological activity of polyacrylonitrile microspheres by thermal treatment: from negative to positive.

The study focuses on the effect of thermal deformation degree of polyacrylonitrile (PAN) particles on the electrorheological (ER) properties of their suspensions. The heat-treated PAN particles are manufactured as ER materials using a thermocatalytic processes. The molecular structures of ER materials are analyzed to confirm a stabilization or a carbonization degree. We categorized the prepared ER particles into three basic types according to their deformation degree: Thermal dried PAN, stabilized PAN, and pre-carbonized PAN. The raw, stabilized, and pre-carbonized PAN particle-dispersed suspensions showed positive ER properties. The ER properties are enhanced as the heat-treatment temperature increases due to improved dielectric property. However, the thermal dried PAN particle ER suspensions showed negative ER behavior though the particles have higher conductivity and dielectric constants than those of the host fluid, which is contrary to the conduction model. XRD results indicate that the ER materials could show contradictory ER behavior even if they have the same molecular structures due to their crystallinity. This discovery is expected to boost the development of both positive ER and negative ER suspensions based on carbonaceous ER materials.

Arsenic(V) removal using an amine-doped acrylic ion exchange fiber: Kinetic, equilibrium, and regeneration studies.

This study investigates As(V) removal from aqueous solutions using a novel amine-doped acrylic ion exchange fiber. The amine doping reaction was confirmed using FT-IR, and the surface of the fiber was characterized using FEG-SEM. The synthesis process was completed within 60min using an AlCl3·6H2O catalyst at 100°C, and the resulting in a fiber with an ion exchange capacity of 7.5meq/g. The removal efficiency of the A-60 fiber was affected by the solution pH, and the efficiency was optimum at pH 3.04. As(V) adsorption on the fiber was rapid in the first 20min and reached equilibrium in 60min. As(V) removal followed pseudo-first-order kinetics, and the Redlich-Peterson adsorption isotherm model provided the best fit of the equilibrium data. The fiber has an As(V) adsorption capacity (qe) of 205.32±3.57mg/g, which is considerably higher than literature values and commercial adsorbents. The removal efficiency of the fiber was above 83% of the initial value after nine regeneration cycles.

CeO2-covered nanofiber for highly efficient removal of phosphorus from aqueous solution.

The lowering phosphorus concentration of lakes or rivers using adsorbents has been considered to be the most effective way to prevent water eutrophication. However, the development of an adsorbent is still challenging because conventional adsorbents have not shown a sufficient phosphorus adsorption capacity (0.3-2.0mmol/g) to treat industrial, agricultural or domestic wastewater at a large scale. Herein, a novel and effective strategy to remove phosphorus efficiently with a CeO2-covered nanofiber is shown. The CeO2-covered nanofiber was synthesized through (1) amine group immobilization onto an electrospun polyacrylonitrile nanofiber and (2) adsorption of Ce(3+) on it. The CeO2-covered nanofiber played a role in catching phosphate ions in an aqueous solution by the oxidation, reduction, and ion-exchange of adsorbed Ce(3+) on the nanofiber from CeO2 to CePO4, and enabled remarkable phosphate adsorption capacity of the nanofiber (ca. 17.0mmol/g) at the range of ca. pH 2-6. Our strategy might be the most feasible method to efficiently lower the phosphorus concentration in lakes or rivers owing to the easy and inexpensive preparation of CeO2-covered nanofiber at an industrial scale, with a high phosphate adsorption capacity.

Line-patterning of polyaniline coated MWCNT on stepped substrates using DC electric field.

Printing electronic components on a chip edge and a stepped substrate with functional inks are an attractive approach for achieving flexible and inexpensive circuits for applications such as flexible displays and large-area chemo/bio/radioactivity sensors. However, it is still challenging because a sufficient cover of the 100 µm high step at the chip edge with a high-resolution pattern is the hardest part of the layer assembling by inkjet printing. Herein, we present a simple and effective strategy to generate electrically conductive line-patterns on stepped substrates by applying the DC electric field. On the surface of flat polyimide substrate, the fine line-pattern (less than 850 nm in line width) is achieved with a polyaniline coated MWCNT dispersed ink. Furthermore, 9.9 µm of line width is successfully patterned on the high stepped poly(dimethylsiloxane) substrate, higher than 100 µm, by printing only 1 time.

Hierarchically porous aminosilica monolith as a CO2 adsorbent.

A facile strategy is successfully developed for the centimeter-scale preparation of hierarchically porous aminosilica monolith as a CO2 adsorbent just by simple processes of solvent-evaporation-induced coating, self-assembly, and concentration of tetraethyl orthosilicate sol on the surface of a polymer foam template without any adhesive composite material or hydrothermal treatment. (3-Aminopropyl) trimethoxysilane is immobilized on the surface of silica monolith via a gas-phase procedure. The silica frameworks of the monolith mimic those of the polymer foam template at the macroscale, and the frameworks are composed of the SBA-15 structure at the nanoscale. The hierarchically porous structure demonstrates improved properties over the single-mode porous component, with the macroporous framework ensuring mechanical stability and good mass transport properties, while the smaller pores provide the functionality for CO2 adsorption.

The mixing effect of amine and carboxyl groups on electrorheological properties and its analysis by in situ FT-IR under an electric field.

Herein, the mixing effect of amine and carboxyl groups on electrorheological (ER) properties has been presented with the chitosan and alginic acid dispersed suspensions. Chitosan (for the amine group) and alginic acid (for the carboxyl group) are used to investigate the mixing effect of the amine and carboxyl groups on ER properties with the control of their mixing ratio in the silicone oil. The surface-chemical structure of the mixture of the chitosan and alginic acid particles in the silicone oil is demonstrated by in situ Fourier transform infrared (FT-IR) spectroscopy at various electric fields for the first time. This study focuses on whether the mixture of chemical groups in the ER fluid can promote ER properties or not, and in situ FT-IR analysis of the interface between ER particles in the silicone oil at various DC electric fields. The ER fluids exhibited the increase of the yield stress values with the increase of the counter group addition up to the weight ratio of 50 : 50 (chitosan : alginic acid). A noteworthy result is that the mixing effect of the amine and carboxyl groups resulting in enhanced ER properties is clearly proved. In the in situ FT-IR study, the complex form of amine and carboxyl groups of particles in the ER fluid was confirmed under the electric field.

Cu²âº sequestration by amine-functionalized silica nanotubes.

A novel method for Cu(2+) sequestration in Cu(2+) aqueous solution has been demonstrated using amine-functionalized double-walled silica nanotubes (DWSNTs). Herein, the precipitation method and the adsorption method are combined to remove Cu(2+) in the Cu(2+) aqueous solution. Primary (1°), secondary (2°), tertiary (3°), di-, tri-amines are immobilized on the surface of DWSNT as the adsorption site. The results show that the Cu(2+) adsorption amount on the amine-functionalized DWSNTs is in the following order: tri-amine>di-amine>1° amine>2° amine>3° amine. The complexed Cu(2+)s with the amine-functionalized DWSNTs become Cu(OH)2 crystals due to the reaction with OH(-)s dissociated from water. Thus, the amine-functionalized DWSNTs show the superior sequestration capacity of Cu(2+) in the Cu(2+) aqueous solution owing to the Cu(OH)2 crystals growth on them. FT-IR, FEG-SEM, HR-TEM, and XRD studies demonstrate the mechanism of the Cu(2+) adsorption and the Cu(OH)2 crystals growth. The crystallization-technique of the heavy metal ion on the amine-functionalized DWSNTs is also expected to have potential applications such as the facile synthesis of nano- and microparticles, and the metal catalyst supporter.

Amines immobilized double-walled silica nanotubes for CO2 capture.

Novel silica support has been required for high amine loading and good CO2 molecule diffusion into its pores to increase the performance of CO2 adsorbents. Herein, amine groups supported on double-walled silica nanotubes (DWSNTs) have been prepared via the immobilization of various aminosilanes (primary, secondary, tertiary, di-, and tri-aminosilanes) on DWSNT, and found to be a very effective adsorbent for CO2 capture. Amine groups immobilized DWSNTs captured CO2 reversibly in a temperature swing process at various adsorption temperatures (25°C, 50°C, 75°C, and 100°C). The amines on modified DWSNTs showed high CO2 capture capacity in the order of tri-, di-, primary, secondary, and tertiary amines. The CO2 capture capacity of all aminosilanes immobilized DWSNTs decreased linearly with the increase of the adsorption temperature. We expect that DWSNT would be able to inspire researchers to use it not only as a support for CO2 capture but also as a promising candidate for various applications.

Positive and negative electrorheological response of alginate salts dispersed suspensions under electric field.

Electrorheological (ER) effects of alginic acid and alginate salts (Na(+) alginate, NH(4)(+) alginate, and Ca(2+) alginate) dispersed suspensions were investigated under DC electric fields. A noteworthy result is that the Ca(2+) alginate dispersed suspension showed negative electrorheological effects under electric fields while the other suspensions exhibited positive electrorheological effects. It is the first time that the negative ER effect is obtained with the biomacromolecule. Interestingly, at the DC electric fields, the electromigration of particles to two electrodes was observed in the negative ER fluid, while the particles-bridges formed between two electrodes in the case of the positive ER fluid. In conclusion, the specific salt type of biomacromolecules could be suitable ER particles for negative ER suspension. We believe that our study can present a new way for the development of the biocompatible and eco-friendly negative ER fluids.

Removal of Cu(II) and Cr(VI) ions from aqueous solution using chelating fiber packed column: equilibrium and kinetic studies.

Herein, we demonstrate the adsorption process system with the diethylenetriamne coupled polyacrylonitrile fiber for the removal of Cu(II) and Cr(VI) ions in the aqueous solution. The synthesized chelating fiber showed a high adsorption capacity of 11.4 mequiv/g. Interestingly, the crystal growth of copper ions on the chelating fiber was observed during the adsorption process. The chelating fiber packed column showed the high performance of the removal of Cu(II) in the aqueous solution due to the distinct characteristic of the crystal growth of metal ions on the chelating fiber. After Cu(II) adsorption on the chelating fiber, the color of the fiber changed to light blue from yellow. The isotherm parameter n of 1.991 was obtained with Freundlich isotherm model for the adsorption equilibrium study which indicates that Cu(II) adsorption on the chelating fiber is very favorable due to n>1. The pseudo-first-order and pseudo-second-order model equations were used for the kinetic study.

Primary, secondary, and tertiary amines for CO2 capture: designing for mesoporous CO2 adsorbents.

CO(2) emissions, from fossil-fuel-burning power plants, the breathing, etc., influence the global worming on large scale and the man's work efficiency on small scale. The reversible capture of CO(2) is a prominent feature of CO(2) organic-inorganic hybrid adsorbent to sequester CO(2). Herein, (3-aminopropyl) trimethoxysilane (APTMS), [3-(methylamino)propyl] trimethoxysilane (MAPTMS), and [3-(diethylamino) propyl] trimethoxysilane (DEAPTMS) are immobilized on highly ordered mesoporous silicas (SBA-15) to catch CO(2) as primary, secondary, and tertiary aminosilica adsorbents. X-ray photoelectron spectroscopy was used to analyze the immobilized APTMS, MAPTMS, and DEAPTMS on the SBA-15. We report an interesting discovery that the CO(2) adsorption and desorption on the adsorbent depend on the amine type of the aminosilica adsorbent. The adsorbed CO(2) was easily desorbed from the adsorbent with the low energy consumption in the order of tertiary, secondary, and primary amino-adsorbents while the adsorption amount and the bonding-affinity increased in the reverse order. The effectiveness of amino-functionalized (1(o), 2(o), and 3(o) amines) SBA-15s as a CO(2) capturing agent was investigated in terms of adsorption capacity, adsorption-desorption kinetics, and thermodynamics. This work demonstrates apt amine types to catch CO(2) and regenerate the adsorbent, which may open new avenues to designing "CO(2) basket".

Gelation of chitin and chitosan dispersed suspensions under electric field: effect of degree of deacetylation.

Herein, the effect of the degree of deacetylation (DD) on the gelation of the chitosan dispersed suspension as an electrorheological (ER) fluid under an electric field is presented. The fluids were prepared by dispersing the chitin and the chitosan particles having various DDs into silicone oil, and they were evaluated under various electric fields. The alignment of chitosan particles in the fluid was also observed using an optical microscope under the electric field. The formed fibrous structure between electrodes are though to continue to the viscosity increase, because an attempt to move one electrode relative to the order would be hindered by the drag of the dangling fibrils. A noteworthy result is that the region of the frequency for gel state of the ER fluids increased in the order of chitosan DD 99.3, 93.4, 73.2, 83.8, and 87.3% under electric fields while the modulus of the fluids increased in the reverse order. This order was well-matched with the result of dielectric constants and yield stresses of ER fluids. The study of influence of DD on the gelation of the chitosan dispersed suspension under an electric field shows the relevance of the chemical composition of the heteropolysaccharide (chitin-chitosan copolymer) to the rheological and electric properties of ER suspensions.

Influence of particle size on shear behavior of amine-group-immobilized polyacrylonitrile dispersed suspension under electric field.

Different-sized particles dispersed electrorheological (ER) fluids were fabricated with poly(acryloamidino diethylenediamine) to observe the influence of the particle size on ER behaviors. The fine particles dispersed ER suspension showed stable shear stress under a DC electric field. On the other hand, the rough particles dispersed suspension showed trembling shear stress which is divided into four regions in a plot of shear stress against shear rate. Our suggested spring-damper model equation treated the wide range of shear rate and specific (trembling) behaviors of shear stress in ER fluids. In this study, we successfully obtained various ER fluids showing different behaviors just by changing the size of particles in the ER fluids. All of the curves of the shear stress plotted against shear rate were fitted well by our spring-damper model.