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.     

Bicomponent nanofibers from core–shell nozzle in gas jet spinning process

This work evaluates the use of a core–shell nozzle assembly in conjunction with gas jet spinning technique for production of bicomponent nanofibers from an immiscible polymer pair of polyvinylpyrrolidone (PVP) and poly(vinyl acetate) (PVAc) with three morphological forms—interpenetrating network (IPN), core–shell, and bilobal structurers—by varying the sets of miscible solvents offering different affinity for the polymers. Such fiber structures have strong potential in drug delivery and wound dressing applications. Solutions of PVP and PVAc in respective single solvents metered through a core–shell nozzle assembly meet at the exit of the nozzle and a liquid jet is initiated upon contact with a turbulent gas jet. The gas jet stretches the liquid jet into nanofibers. The results indicate that miscible solvent pairs with low affinity for one of the polymer component yield core–shell morphology with distinct polymer interfaces, while the miscible solvent pairs with high affinity for both polymers produce IPN morphology. Also, interchanging core and shell solutions does not alter the IPN morphology. Finally, bilobal nanofiber structures result from spinning of polymer solutions in miscible solvents with low affinity for the second polymer using a nonconcentric core–shell nozzle assembly. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48901.     

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.     

Ionic liquid mediated synthesis of silica/polystyrene core–shell composite nanospheres by radical dispersion polymerization

This report describes the novel preparation of silica/polystyrene (SiO₂/PS) core–shell composite nanospheres by in situ radical dispersion polymerization in an ionic liquid (IL). Silica nanoparticles were first surface modified by the silane coupling agent methacryloxypropyltrimethoxysilane (MPTMS), which is capable of copolymerizing with styrene and provided a reactive CC bond. Transmission electron microscopy (TEM) revealed core–shell morphology with smooth surfaces. X-ray photoelectron spectroscopy (XPS) analysis demonstrated that almost all of the SiO₂ nanoparticles were encapsulated by the polymer. The composite particles were also analyzed by FT-IR spectroscopy and thermogravimetric analysis (TGA). In principle, this simple and environmentally-friendly synthetic procedure can be employed to prepare other inorganic oxide-containing polymer composites.     

Fabrication and properties of polysilsesquioxane-based trilayer core–shell structure latex coatings with fluorinated polyacrylate and silica nanocomposite as the shell layer

Polysilsesquioxanes (PSQ)-based core–shell fluorinated polyacrylate/silica hybrid latex coatings were synthesized with PSQ latex particles as the seeds, and methyl methacrylate, butyl acrylate, 3-(trimethoxysilyl) propyl methacrylate (MPS)-modified SiO₂ nanoparticles (NPs), 1H,1H,2H,2H-perfluorooctyl methacrylate (PFOMA) as the shell monomers by emulsifier-free miniemulsion polymerization. The results of Fourier transform IR spectroscopy, transmission electron microscopy, and dynamic light scattering suggested the obtained hybrid particles emerged with trilayer core–shell pattern. Contact angle analysis, x-ray photoelectron spectroscopy, and atom force microscopy results indicated that the hybrid film containing SiO₂ NPs showed higher hydrophobicity, lower surface free energy and water absorption, in comparison with the control system (without SiO₂ NPs). Compared with the control system, the hybrid latex film containing SiO₂ NPs in the fluorinated polyacrylate shell layer showed the higher content of fluorine atoms and a rougher morphology on the film surface. Additionally, thermogravimetric analysis demonstrated the enhanced thermostability of PSQ-based nanosilica composite fluorinated polyacrylate latex film.     

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.     

Preparation of PVDF/PVP core–shell nanofibers mats via homogeneous electrospinning

The polyvinylpyrrolidone (PVP)/poly(vinylidene fluoride) (PVDF) core–shell nanofiber mats with superhydrophobic surface have been prepared via electrospinning its homogeneous blending solutions, and the formation of the core–shell structure was achieved by the thermal induced phase separation assisted with the low surface tension of PVDF. The electrospinnability of the blending solutions was also investigated by varying the blending ratio of the PVP and PVDF, and it enhanced with the increase of PVP content. SEM and TEM results showed that the fibers size was varied in the range of 100 nm–600 nm with smooth surface and core–shell structure. The composition of the shell layer was determined by the XPS analysis, and further confirmed by water contact angle (WCA) testing. As the fraction of PVDF exceeding PVP in the electrospinning solutions, the nanofiber mats showed superhydrophobic property with the WCA above 120°. It indicated that the PVDF was concentrated in the shell layer of the fibers. X-Ray diffraction (XRD) and attenuated total reflection infrared spectroscopy (ATR-IR) analysis indicated that the PVDF was aggregated with the β-phase crystallite as dominant crystallite. The nanofiber mats with the gas breathability and watertightness ability due to the porous structure and superhydrophobic would be potential applied in wound healing.     

Preparation and characterization of silica sol/fluoroacrylate core–shell nanocomposite emulsion

The silica sol/fluoroacrylate core?Cshell nanocomposite emulsion was successfully synthesized via traditional emulsion polymerization through grafting of KH-570 onto silica particles. Comparing the performance of the polyacrylate copolymer, the fluorinated polyacrylate copolymer and the silica sol/fluoroacrylate core?Cshell nanocomposite emulsion, we can come to a conclusion that the silica sol/fluoroacrylate core?Cshell nanocomposite emulsion presents significantly excellent performance in all aspects. The products were characterized by Fourier transform infrared (FTIR), photon correlation spectroscopy (PCS), transmission electron microscopy (TEM), thermogravimetry (TGA), Contact angle and UV?Cvis analyses techniques. The chemical structure of polyacrylate copolymer, fluorinated polyacrylate copolymer and silica sol/fluoroacrylate nanocomposite were detected by FTIR. The size and stability of emulsion latex particles were determined by PCS technique. TEM analysis confirmed that the resultant latex particle has the core?Cshell structure, obviously. The water absorption and contact angle data also showed that the silica sol/fluoroacrylate nanocomposite film has good hydrophobic performance. TGA analysis indicated the weight loss of the silica sol/fluoroacrylate nanocomposite film begins at around 350?°C which testifies its good thermal stability. The UV?Cvis spectroscopy analysis showed that the silica sol/fluoroacrylate nanocomposite film possess UV?Cvis shielding effect when the added volume amount of KH570 modified silica sol is up to 5?mL. Therefore, the excellent properties of hydrophobicity, thermodynamics and resistance to ultraviolet provide the silica sol/fluoroacrylate nanocomposite film with potential applications in variety fields. In addition, the formation mechanism of core?Cshell structure silica sol/fluoroacrylate nanocomposite latex particles was speculated.     

Synthesis of size controlled phase pure KNbO3 fine particles via a solid-state route from a core–shell structured precursor

From a core–shell structured precursor, comprising Nb₂O₅ core enveloped by KHCO₃ in an equimolar proportion, phase pure KNbO₃ (KN) fine particles were obtained by calcining in air at 600 °C for 1 h. Disintegrating the large agglomerated particles of KHCO₃ prior to the precursor preparation enabled the micronization of the KN particle size down to 240 nm, close to that of the starting Nb₂O₅, due to increased mixing homogeneity and consequent thorough enveloping of individual Nb₂O₅ particles. Based on these findings, together with the known coupling diffusion mechanism of potassium and oxygen into Nb₂O₅, it was concluded that the core–shell particles in the precursor serve as a separated reaction space to complete the formation of KN without appreciable coalescence or local sintering, as far as the firing temperature is low enough like those employed in the present study. Superiority of KHCO₃ over K₂CO₃ or KNO₃ as a potassium source was also discussed.     

Mass production of three-dimensional hierarchical microfibers constructed from silicon–carbon core–shell architectures with high-performance lithium storage

In this work, a facile approach is reported to mass produce highly porous fibers constructed from silicon–carbon core–shell structures. The C–Si microfibers are prepared using a modified electrospinning deposition method (ESD), and subsequent calcination of the carbon shells. Benefited from the step of vacuum drying, the unnecessary solvent left in the precursor will volatilize, resulting in the uniform three-dimensional hierarchical microfibers constructed from silicon–carbon core–shell architectures. The uniform covering layers of carbon formed by decomposition of polymer contribute to the improvement of conductivity and alleviation of volume change. The pores in the microfibers are helpful for the diffusion of electrolyte. When evaluated as an anode material for lithium-ion batteries, the C–Si microfibers exhibit improved reversibility and cycling performance compared with the commercial Si nanoparticles. A high capacity of 860 mAh g⁻¹ can be retained after 200 cycles at a current rate of 0.3 C. The rate capability of the C–Si microfibers is also improved. The special structure is believed to offer better structural stability upon prolonged cycling and to improve the conductivity of the material. This simple strategy using the modified ESD method could also be applied to prepare other porous energy materials.     

Improved cyclability of lithium–sulfur battery cathode using encapsulated sulfur in hollow carbon nanofiber@nitrogen-doped porous carbon core–shell composite

Hollow carbon nanofiber@nitrogen-doped porous carbon (HCNF@NPC) core–shell composite, which was carbonized from HCNF@polyaniline, was prepared as an improved high conductive carbon matrix for encapsulating sulfur as a cathode composite material for lithium–sulfur batteries. The prepared HCNF@NPC-S composite with high sulfur content of 77.5 wt.% showed an obvious core–shell structure with an NPC layer coating on the surface of the HCNFs and sulfur homogeneously distributed in the coating layer. This material exhibited much better electrochemical performance than the HCNF-S composite, delivered initial discharge capacity of 1170 mAh g⁻¹, and maintains 590 mAh g⁻¹ after 200 cycles at the current density of 837.5 mA g⁻¹ (0.5 C). The significantly improved electrochemical performance of the HCNF@NPC-S composite was attributed to the synergetic effect between HCNF cores, which provided electronic conduction pathways and worked as mechanical support, and the NPC shells with relatively high surface area and pore volume, which could trap sulfur/polysulfides and provide Li⁺ conductive pathways.     

Synthesis and characterization of local clay–titanium dioxide core–shell extender pigments

A simple chemical technique has been used to prepare core–shell extender pigments based on Nigerian indigenous clays as core and titanium dioxide as shell. The prepared core–shell extender pigments were characterized using X-ray fluorescence and scanning electron microscopy. The physico-chemical properties of these extender pigments were also evaluated according to ASTM measurements. The study showed that the prepared core–shell pigments were nontoxic and environmentally friendly. They are of low cost and can be incorporated in semi-gloss paints, paper, rubber, and plastic composites without much effect on the volume. The characteristics of these pigments showed that they combine the properties of both their precursors, and have the potential to overcome their disadvantages, e.g., low hiding power of clays and photochemical activity of titanium dioxide.     

Synthesis and characterization of fluorine-containing poly-styrene-acrylate latex with core–shell structure using a reactive surfactant

Fluorine-containing poly-styrene-acrylate (PSA) latex with core–shell structure was successfully synthesized by seeded semicontinuous emulsion polymerization using fluorine monomer Actyflon-G₀₄ and reactive emulsifier DNS-86. The chemical composition, morphology of latex, and surface composition of the latex film were characterized by Fourier transform infrared spectra, transmission electron microscopy, and X-ray photoelectron spectroscopy, respectively. The stability properties of latex were tested by Ca²⁺, centrifugal and mechanical stability tests, and the latex film was studied by water contact angle, water absorption ratio, and thermo-gravimetric analysis. The results show that fluorine-containing PSA latex particles with crosslinked core and crosslinked shell structure have excellent stability properties, and the film of latex has excellent water repellency, thermal stability, and chemical resistance properties when the amount of fluorine monomer was only 8.0 wt%.     

Synthesis of porous silicon nitride using silica/carbon composite derived from phenol–resorcinol–formaldehyde gel

Mesoporous silicon nitride (Si₃N₄), which is one of the most promising structural materials for applications in high-temperature filtration, was synthesized from the carbothermal reduction and nitridation of a pyrolyzed silica-containing phenol-resorcinol-formaldehyde (PRF) gel. The PRF gel was synthesized by combining sol–gel and polymerization of phenol, resorcinol and formaldehyde using sodium carbonate as a catalyst. Silica was incorporated into the gel by addition of 3-aminopropyl trimethoxysilane (APTMS) as a silica precursor. After aging and being freeze-dried, the silica/PRF composite was pyrolyzed under nitrogen gas to convert it into porous silica/carbon composite. The combination of phenol-formaldehyde (PF) and resorcinol-formaldehyde (RF) gels into PRF gel, allows further enhancement in porosity of the silica/carbon composite via pre-calcination in the range of 400–500 °C, since carbon derived from PF gel and that from RF gel have different thermal stability. The final product obtained after final calcination to remove residual carbon has a surface area as high as 194 m²/g, which is significantly much higher than the conventional Si₃N₄ granules. Specific surface area of the product is affected by molar ratio of phenol-to-resorcinol, molar ratio of silica-to-carbon, and the pre-calcination temperature.     

Synthesis of multifunctional core–shell toughening agent with light stability and its application in polycarbonate

A light stabilizer compound of 2-(2′-propionyloxy-5′-methylphenyl) benzotriazole (AMB) was synthesized by the esterification of the 2-(2′-hydroxy-5′-methylphenyl) benzotriazole with acryloyl chloride (AC), and the AMB was then copolymerized with the methyl methacrylate (MMA), butyl acrylate (BA), and silicone monomers (D4) to prepare the silicone light toughener of poly(D4-MMA-BA-AMB). Effects of the AMB monomer on the conversion and polymerization stability and the toughening and photostabilizing effects of the poly(D4-MMA-BA-AMB) on the polycarbonate (PC) were studied. The prepared multifunctional toughening agent was characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, thermogravimetric analyzer, transmission electron microscopy, dynamic light scattering analyzer, and ultraviolet absorption spectroscopy. Results show that the prepared poly(D4-MMA-BA-AMB) toughening agent possessed core–shell structure and could effectively absorb the ultraviolet rays. Although the addition of the poly(D4-MMA-BA-AMB) toughening agent had a negative effect on the tensile strength of the PC, it could greatly improve the low-temperature notched impact strength, toughness performance, and yellowness performance of PC products after UV irradiation. Compared with the silicone toughening agent, the toughening agent of the poly(D4-MMA-BA-AMB) had better anti-ultraviolet property for the PC/poly(D4-MMA-BA-AMB) composite. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48747.     

Overcoming the quality–quantity tradeoff in dispersion and printing of carbon nanotubes by a repetitive dispersion–extraction process

Dispersion-printing processes are essential for the fabrication of various devices using carbon nanotubes (CNTs). Insufficient dispersion results in CNT aggregates, while excessive dispersion results in the shortening of individual CNTs. To overcome this tradeoff, we propose here a repetitive dispersion–extraction process for CNTs. Long-duration ultrasonication (for 100 min) produced an aqueous dispersion of CNTs with sodium dodecylbenzene sulfonate with a high yield of 64%, but with short CNT lengths (a few μm), and poor conductivity in the printed films (∼450 S cm⁻¹). Short-duration ultrasonication (for 3 min) yielded a CNT dispersion with a very small yield of 2.4%, but with long CNTs (up to 20–40 μm), and improved conductivity in the printed films (2200 S cm⁻¹). The remaining sediment was used for the next cycle after the addition of the surfactant solution. 90% of the CNT aggregates were converted into conductive CNT films within 13 cycles (i.e., within 39 min), demonstrating the improved conductivity and reduced energy/time requirements for ultrasonication. CNT lines with conductivities of 1400–2300 S cm⁻¹ without doping and sub-100 μm width, and uniform CNT films with 80% optical transmittance and 50 Ω/sq sheet resistance with nitric acid doping were obtained on polyethylene terephthalate films.     

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 highly durable and reusable superabsorbent core–shell particles

Superabsorbent core–shell particles were synthesized via a two-step process. A silica core was prepared by co-condensation of tetraethyl orthosilicate and vinyl triethoxysilane. The vinyl-functionalized silica particles were then polymerized with acrylamide monomer via free-radical polymerization to yield silica-polyacrylamide (PAM) hybrid particles. The crosslinking density and porosity of PAM on the hybrid particles were controlled by adjusting the concentration of the crosslinker, n,n′-methylenebisacrylamide (MBA). The structure of core–shell particles was confirmed by scanning and transmission electron microscopy techniques. The hybrid particles with 3.0%MBA could absorb water up to 70 g/g. These hybrid particles also removed 80% of methylene blue from solution within 24 h and this efficacy was maintained for seven cycles. The weight remaining of the hybrid particles after nine cycles was higher than that of pure PAM after three cycles indicating the high durability and reusability of the core–shell particles. POLYM. ENG. SCI., 60: 306–313, 2019. © 2019 Society of Plastics Engineers     

Synthesis of fluorine-containing latexes with core–shell structure by UV-initiated microemulsion polymerization

A core–shell structure of fluorine-containing polyacrylate latex was synthesized by UV-initiated two-stage microemulsion polymerization from styrene (St) and hexafluorobutyl acrylate (HFA) in the presence of Irgacure 2959 as hydrophilic photoinitiator at room temperature. The first polymerization stage took 12 min and the second stage took 10 min. The conversions of the first and the second polymerization stages were about 60 and 85 %, respectively. Fourier transform infrared (FTIR) spectra, transmission electron microscopy (TEM), dynamic light scattering (DLS), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and contact angle analysis were used to characterize the properties of latexes and their films. The DLS analysis results indicated that the size of the fluorine-containing nanoparticle is about 20 nm. The TEM photos showed that the particles have core–shell structure and some of the cores are located in the center and the others deviate from the center of particles. From the FTIR and XPS results, we can infer that the fluorine monomer could be introduced into the copolymer and the fluorine-containing polyacrylate mainly occupies the shell part. The TGA results indicated that the fluorine-containing polyacrylate copolymers exhibited higher thermal stability than that of the fluorine-free one. The contact angle analysis results showed that fluorine monomers make the film surface more hydrophobic.     

Preparation and characterization of novel polyethylene/carbon nanotubes nanocomposites with core–shell structure

Preparation of novel polyethylene/carbon nanotubes (CNTs) nanocomposites with core–shell structure was presented. The method involved in situ ethylene polymerization in which nanotube surface was treated with Grignard Agent, followed by reacting with active transition metal compound, TiCl₄. The multiwalled carbon nanotubes (MWCNTs) supported catalysts polymerize ethylene to form polymer nanocomposite. MWCNTs were homogeneously dispersed within polymer matrix, and as expected, the resultant nanocomposites featured core–shell structure which was confirmed by HRTEM. For the nanocomposite, the microscopic examination of the cryogenically fractured surface not only ensured a good distribution of carbon nano-particles in the PE matrix but also revealed the ductile-like fracture. The Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were employed for the study of covalent sidewall functionalization and chemical bonding environment of MWCNTs, also indicated effective immobilization of titanium catalyst on the MWCNTs surface. The crystalline properties, dielectric property and thermal stability of the nanocomposites were determined by WAXD, impedance analyzer and TGA. The dielectric result showed a slight decline of the dielectric constant of the nanocomposites with increase of the polymerization time, and lower dielectric loss was also observed.