Silicylacrylate copolymer core–shell emulsion for humidity coatings

Using silicylacrylate (SPMA: 3-(trimethoxysilyl)propyl methacrylate) and acrylic acid as functional monomers, silicylacrylate copolymer core–shell emulsion (SiA-CSE) was prepared by emulsion polymerization. The relationships between stability of SiA-CSE and contents of SPMA, emulsifier, initiator and copolymerization temperature were investigated. Moreover, the structure of SiA-CSE was characterized by FTIR, TEM and TGA techniques. The SiA-CSE was applied to prepare the silicylacrylate copolymer humidity coatings (SiA-CSE-C) by compositing with pigments and porous fillers. Based on measuring the basic performance of copolymer emulsion film and SiA-CSE coatings, the humidifying function of SiA-CSE coatings was investigated. In conclusion, SPMA could improve the adhesion of SiA-CSE film and water resistance of the coatings. The obtained coatings showed excellent humidity-sensitivity and humidity retention, which could be used as the interior walls coatings in the building.     

Comparison of film properties for crosslinked core–shell latexes

Thermosetting acrylic latexes were synthesized using butyl acrylate (BA), methyl methacrylate (MMA), 2-hydroxyethyl methacrylate (HEMA), and methacrylic acid (MAA) via seeded two-stage process. A 2-level factorial experimental design was employed to investigate the effect of hydroxyl (core phase), carboxylate (shell phase) groups, and type of surfactant (Triton X200, Tergitol XJ) on the mechanical properties of thermosetting latexes. Eight latexes with varying concentration of HEMA, MAA and two types of surfactants were synthesized and crosslinked with three crosslinkers. Latex functionality for crosslinking was located in the core only, the shell only, and both the core–shell with varying concentrations. Melamine-formaldehyde (hexamethoxymethyl melamine) resin was employed to crosslink hydroxyl functionalities in the core. Carboxylic acid groups in the shell were crosslinked with zinc ammonium carbonate. HDI isocyanurate (Desmodur N3300A) were used to crosslink with hydroxyl or carboxyl functional groups in core and shell. The mechanical properties of coatings were evaluated in terms of tensile properties, cross-hatch adhesion, pencil hardness, and impact resistance. Design of experiment (DOE) was utilized to investigate the effect of variables on mechanical properties of crosslinked thermoset films.     

Waterborne polyurethane-acrylic copolymers crosslinked core–shell nanoparticles for humidity-sensitive coatings

A novel crosslinked core–shell emulsion of waterborne polyurethane-acrylic copolymers (PUA) was successfully synthesized by emulsion polymerization. The average particle size of the PUA particle was approximately 130 nm and its core–shell morphology was proved with transmission electron microscopy (TEM) and dynamic light scattering (DLS), whose structure was also confirmed by FT-IR and TGA. PUA was applied to prepare the humidity controlling coatings (PUA-C) by compositing with pigments and porous fillers. The structure and properties of humidity controlling coatings were investigated, with particular attention to the effects of the humidity controlling. The surface morphology of the PUA-C was observed by scanning electron microscope (SEM). The humidity controlling coatings showed excellent properties of humidity sensitivity and humidity retention.     

Construction of site-specific core–shell structured nanocomposite for pH-controlled drug delivery

In this study, a pH-controlled core–shell structured site-specific magnetic nanocomposite for drug delivery was reported. Superparamagnetic Fe₃O₄ nanoparticles were selected to build its core for magnetic guiding purpose and mesoporous silica molecular sieve MCM-41 was chosen to construct its outer shell. The MCM-41 outer shell has highly ordered hexagonal tunnels therefore would offered enough cargo space for drug molecules. An organic ligand N1-(5H-cyclopenta[1,2-b:5,4-b′]dipyridin-5-ylidene)benzene-1,4-diamine (denoted as Dafo-Ph-NH₂) was linked to the molecular sieve outer shell. There are two nitrogen atoms at the end of the ligand which are able to donate their lone pair electrons. Acidic drug molecules therefore can be bound to the ligand via weak acid–base reaction. Those drug molecules can be release in low pH solution since the H⁺ in the solution will compete with the ligand. The final composite was analyzed by electron microscope images, XRD, IR spectra, thermogravimetry and N₂ adsorption/desorption. Its bio-compatibility was evaluated by MTT using L929 fibroblast cell line. Our Dafo-MCM-41@Fe₃O₄ composite shows pH-controlled and site-specific smart release properties for aspirin in vitro.     

Dynamic mechanical study on multilayer core–shell latex for damping applications

Multilayer core–shell poly (styrene-butyl acrylate) latex particles were synthesized via semi-continuous emulsion polymerization, and the process was monitored by a dynamic laser scattering (DLS). The layers of the latex particles were designed to have progressively decreasing glass transition temperatures (T_g) from the core (layer 1) to the outmost shell (layer 4), which was achieved by varying the mass ratio of butyl acrylate (BA) to styrene (St) in the synthesis of each layer. Divinylbenzene (DVB) was added as the crosslinking agent in each layer except for the outmost layer in order to ensure that a continuous film can be formed at room temperature. The damping properties of the formed films as well as the influences of synthesis variables, including the content of DVB added in the internal layers (i.e., layers 1, 2, and 3), the total mass ratio and sequence between layers 3 and 4, and the T_g of each layer were studied by dynamic mechanical analysis (DMA). The results showed that four-layer core–shell latex particles with proper DVB content in each layer exhibited the best damping properties, with a broad effective damping range (tan δ > 0.3) ranging from −12.0 °C to 97.2 °C. The widening of the damping peak can be explained by the formation of a gradient IPN structure in latex particles. Furthermore, the morphology of the formed films was studied by AFM in tapping mode.     

Synthesis and optical limiting effects in ZrO2 and ZrO2@SiO2 core–shell nanostructures

ZrO₂ nanoparticles were synthesized by the chemical precipitation method and coated with silica through seeded polymerization technique to form core–shell type ZrO₂@SiO₂ nanostructures. The structural, morphological and silica coating formation of the bare and silica coated particles were studied using Transmission electron microscopy, X-ray diffraction and Fourier Transform Infrared Spectroscopy. Thermogravimetric analysis and Zeta potential measurements were performed to check the thermal and dispersion stability of the nanostructures. The optical limiting performance of these nanostructures was studied using open-aperture Z-scan technique in which nanosecond laser pulses at 532 nm have been used for optical excitation. Both bare and silica coated ZrO₂ nanoparticles exhibited good optical limiting behavior due to excited state absorption, arising from effective three photon absorption. It is observed that the optical nonlinearity is enhanced in core shell structures as compared with the bare particles.     

Soft core–hard shell latex particles for mechanically strong VOC-free polymer films

Polymer films cast from aqueous polymer dispersions typically suffer from an inherent lack of mechanical strength when compared to their solvent-borne counterparts. This drawback can be overcome by the use nanostructured hybrid particles that contain both a hard and soft phase. In this work, we demonstrate the use latex particles consisting of a soft core with a multilobed hard shell synthesized by seeded semicontinuous emulsion polymerization with the aim of maximizing the interconnectivity of the hard phase in the resulting polymer film, thus generating films with improved mechanical properties. Films with a minimum film formation temperature (MFFT) close to that of the soft phase are formed while obtaining a Young's modulus up to 4.5 times higher that of a standard homogeneous latex particle. The effect of annealing temperature on film morphology is also investigated, clearly demonstrating that a marked difference in mechanical properties is observed when a percolating network of the hard phase within the film is obtained. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47608.     

Carbon nanotube-gelatin-hydroxyapatite nanohybrids with multilayer core–shell structure for mimicking natural bone

We attempted to mimic collagen fibrils bearing apatite crystals in natural bone, using gelatin, carboxylic acid functionalized carbon nanotubes (f-CNTs), and hydroxyapatite (HA). Gelatin molecules were covalently grafted on the surface of f-CNTs by the formation of amide linkages. HA crystals were then assembled onto the gelatin-grafted f-CNTs in a highly concentrated CaP solution, resulting a multilayered core–shell structure, consisting of a f-CNT core and gelatin-HA shells (as a fibrous multilayered f-CNT/Gel/HA nanohybrid), and in a similar formation to the collagen fibers of natural bone. The tensile strength, elastic modulus, and elongation rate of the new hybrid material were significantly improved compared to both pure (f-CNT free) gelatin and a mixture of f-CNT and gelatin, by 4.6–8.8, 9–10, and 28–42 times, respectively. Cell viability studies of the f-CNT/Gel/HA nanohybrid also suggest a higher degree of biocompatibility compared to pure gelatin.     

Multi-walled carbon nanotube-supported Ni@Pd core–shell electrocatalyst for direct formate fuel cells

Journal of Applied Electrochemistry - In the present work, Ni@Pd core–shell nanoparticles are successfully deposited on multi-walled carbon nanotubes as support and investigated their...     

Preparation of core–shell impact modifier particles for PVC with nanometric shell thickness through seeded emulsion polymerization

The improvement in toughness of rigid polymers like poly(vinyl chloride) (PVC) has been of great interest for developing their applications. This could be provided by designing impact modifiers which could be blended with the polymeric matrix. Here, core–shell type impact modifier particles with different glass transition temperatures of the shell and specifically, with nanometric shell thickness were prepared through seeded emulsion polymerization. The core consisted of polybutadiene particles and the shell was made of poly(methylmethacrylate-co-butyl acrylate) that was grafted onto the surface of the seed particles. The polymerization reaction was optimized and the resulting latex particles were well characterized by several techniques such as DSC, DLS, SEM, and TEM. It was found that the core–shell particles have diameters of about 350–360 nm, including the shell with thickness of almost 20–30 nm and glass transition temperatures ranging between 70 and 120 °C. The prepared particles were blended with PVC and the corresponding impact strengths of the moldings were measured by means of Izod impact test. The impact results revealed that by decreasing T _g of the shell in impact modifier particles, the impact resistance of the molded sheets increased remarkably. Also the brittle–ductile transition temperatures (BDTT) of the prepared blends were studied and an increase in BDTT was found with lowering T _g of the shell.     

Synthesis of superhydrophobic core–shell mesoporous silica nanoparticles

Mesoporous silica nanoparticles (MSNPs) have been used in variety of applications due to their morphology and porous structure. This work reports the one-pot synthesis of ultrahydrophobic MSNPs using N-cetyl-n,n,n trimethyl ammonium bromide as a cationic surfactant template and ethanol (EtOH) as a cosolvent to form mesopores in the MSNPs. The effects of EtOH on the size and the pore structure of the MSNPs were studied by scanning electron microscopy and transmission electron microscopy. The results show that an addition of EtOH led to an enlargement of the MSNPs and a change in pore structure from a lamellar structure to a radially oriented structure. Co-condensation with two different types of fluoroalkyl silanes; trimethyl(fluoromethyl)silane, and trichloro(1H,1H,2H,2H-perfluorooctyl)silane provided low surface energy MSNPs with a core–shell structure. An assembly on the surface of these F-MSNPs generated nanostructure surface roughness rendering an improvement in surface wettability with water contact angle of 158.6°, which is a characteristic of oleophobic and ultrahydrophobic material.     

Gelatin shells strengthen polyvinyl alcohol core–shell nanofibers

In this study, polyvinyl alcohol (PVA) and gelatin are coaxially electrospun into core–shell nanofibers to derive mechanical strength from PVA and bioactivity from gelatin. The core–shell nanofibers with PVA in the core and gelatin in the shell display an increased Young's modulus, improved tensile strength, and reduced plastic deformation than PVA nanofibers. When the order of gelatin and PVA is reversed in the core–shell nanofibers, however, the mechanical strengthening effects disappear. It thus suggests that the bioactive yet mechanically weak gelatin shell improves the molecular alignment of PVA in the core and transforms the weak, plastic PVA into a strong, elastic PVA. The use of a gelatin shell as a biological coating and a protecting barrier to strengthen the core in electrospinning presents a new strategy for fabricating advanced composite nanofibers.     

Crosslinked polyurethane–epoxy hybrid emulsion with core–shell structure

An epoxy resin was used to prepare crosslinked polyurethane hybrid emulsion through the blocked NCO prepolymer mixing process. Due to their hydrophobicity, the amine chain extender, blocked –NCO, and epoxy are located inside the emulsion particles. Thus, the crosslinking reaction occurs mostly in the interior of the particles. In this way, the crosslinking density of the resin is increased without the use of solidifying agents or heating during film formation, and the stability of the emulsions remains uninfluenced. The effects of the type of amine chain extender and the type, dosage, and addition mode of the epoxy resin were studied in terms of mechanical properties and swelling properties in water and toluene of the cast films. Additionally, the stability of the single-pack hybrid emulsion was studied. The results showed that the sample prepared with diethylene triamine had good stability, chemical resistance, and high mechanical strength. The modulus and water resistance of the films increased with the epoxy resin content, which could reach 20 wt%. The type of amine chain extender affected the stability of the emulsions significantly. The molar ratio of NH/NCO at 1:1 led to the best film performance. The optimal temperature of the chain-extension reaction was approximately 80°C. The hybrid emulsions could be stored for at least 6 months without apparent performance changes.     

Morphology tailoring and enhanced electrochemical properties of Cd–Zn co-doped NiO nanorods for high performance supercapacitor

A systematic approach has been introduced to synthesize Cd–Zn co-doped NiO nanostructures with different ratios such as Cd_0.07Zn_0.03NiO, Cd_0.05Zn_0.05NiO, Cd_0.03Zn_0.07NiO and Cd_0.01Zn_0.09NiO for supercapacitor applications. The XRD studies has confirmed the phase purity with average crystallite size of 40 nm. The SEM characterization has shown that the morphology of nanostructures was tuned from particles to nano-rods structure with increasing the at. % concentration of Zn doping. Optical properties revealed that band gap and recombination rate have strong co-relation with specific capacitance. The CV results have confirmed the pseudocapacitive nature of the as prepared nanostructures and maximum specific capacitance (1485.19 Fg^-1) was measured for Cd_0.03Zn_0.07NiO which is superior than numerous reported values of NiO. The GCD results of Cd_0.03Zn_0.07NiO performed at 1 A/g scan rate, exhibited excellent charging-discharging ability with high cyclic retention of 82.8%. High capacitance and superior stability of Cd_0.03Zn_0.07NiO material indicate it as a potential candidate for supercapacitor applications.     

Preparation of the stable core–shell latex particles containing organic-siloxane in the shell

In this study, the latex particles with a polyacrylate core and a polydimethylsiloxane shell via 3-(methacryloxypropyl)-trimethoxysilane as the space arm to link the core and shell have been prepared by semi continuous seeded emulsion polymerization. And several key polymerization reaction conditions such as the emulsifier concentration, 3-(methacryloxypropyl)-trimethoxysilane dosages, feeding sequence and the acrylates/siloxanes ratio were detailedly discussed. Then, the optimal condition to prepare stable core/shell particles was selected and a proper preparation process has been established. The as-synthesized particles were characterized by TEM and XPS. The clear core/shell structure of the particles could be observed through analysis TEM. In addition, the results of XPS analyses manifested that siloxanes had been grafted on the surface of the polyacrylate particles and they distributed on the outmost layer of the particles. Finally, the surface hydrophobicity of the film formed by latex particles was investigated by the water absorption ratio measurement. The results indicated the developed latex particle provided with a fair water-repellency property.     

Synthesis and characterization of thermosensitive core–shell polymeric nanoparticles

Thermosensitive core–shell nanoparticles were synthesized by semicontinuous heterophase polymerization of styrene, followed by a seeded polymerization for forming a shell of poly(N-isopropyl acrylamide) (PNIPAM). Nanoparticles characterization by scanning transmission electronic microscopy showed core–shell morphology with average particle diameters around 40 nm. An inverse dependence of the particle size with temperature in the range 20–55 °C was identified by quasielastic light scattering measurements. As was expected for core–shell particles with PNIPAM as the shell, a volume phase transition near 32 °C was detected. In spite of thermosensitive properties of core–shell nanoparticles synthesized here, the volume percentage loss values were not so high, probably due to their relatively low content of PNIPAM.     

Enhanced electrocatalytic activity and stability of PdCo@Pt core–shell nanoparticles for oxygen reduction reaction

The carbon-supported PdCo@Pt core–shell nanoparticles for an oxygen reduction reaction (ORR) were prepared via a two-step process at room temperature. The as-prepared PdCo@Pt/C with an average particle size of ~3.5 nm exhibited a well-defined nanostructure consisting of Pd-rich core and Pt shell formed by displacing Co core with Pt. Compared to pure Pt, PdCo@Pt/C showed a higher current density in the kinetic controlled region and more positive half-wave potential for the ORR. In a cycling stability test of the PdCo@Pt/C electrocatalyst, no remarkable activity loss was seen.