The influence of creep on cake solid volume fraction during filtration of core–shell particles

The solid volume fraction vs. pressure relationship used in conventional filtration models is determined by measuring the cake solid volume fraction after consolidation. However, some cakes creep during consolidation, so the solid volume fraction increases at constant pressure. Thus, the conventional method for determining the solid volume fraction vs. pressure relationship cannot be used for materials with significant creep. Cake creep has been observed when core–shell particles with hard poly(styrene) cores and water-swollen poly(acrylic acid) shells are filtered. The Terzaghi–Voigt combined model has been fitted to data obtained during consolidation to determine the transition point where creep begins to be dominating for cake compression. The solid volume fraction increases by 17–35% after the transition point, particularly in the case of particles with thick poly(acrylic acid) shells and thus a high initial water content. Hence, the solid volume fraction can increase significantly during cake creep and if the solid volume fraction vs. pressure relationship that controls the initial stages of filtration is to be determined then the filtration experiments must be stopped before creep dominates. This can be done by measuring the liquid pressure at the interface between piston and sample, and stop the experiment when the liquid pressure is lower than 5% of the applied pressure.     

Preparation of polyacrylate–polysiloxane core–shell latex particles

Crosslinked polymer seed latexes of butyl acrylate, methyl methacrylate and methacrylic acid were synthesized with ethylene glycol dimethacrylate as a crosslinking agent in a first step. Three different processes of seeded emulsion polymerization were used to prepare an outlayer of polysiloxane on the above seed latex particles: (A) direct anionic polymerization of D₄ (octamethyl tetracyclosiloxane) catalyzed by potassium hydroxide; (B) direct cationic polymerization of D₄ onto the seed catalyzed by dodecylbenzene sulfonic acid; (C) a vinyl-containing polysiloxane prepared by copolymerization of D₄ and vinyl septamethyl tetracyclosiloxane was added before the D₄ cationic polymerization. Characterization by transmission electron microscopy showed that only process C provided satisfactory results. Film hardness was measured, and the latex film from process C demonstrated the lowest hardness of all the films. The mechanism of polymerization is discussed.     

Preparation and characterization of emulsifier-free core–shell interpenetrating polymer network-fluorinated polyacrylate latex particles

The emulsifier-free core–shell interpenetrating polymer network (IPN) fluorinated polyacrylate latex particles with fluorine rich in shell were prepared by emulsifier-free seeded emulsion polymerization with water as the reaction medium. The fluorinated copolymer could be fixed on the particle surface due to the formation of interpenetrating polymer network. The resultant core–shell particles were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS) analysis, Fourier transform infrared (FTIR) spectrometry, X-ray photoelectron spectroscopy (XPS) analysis and thermogravimetric analysis (TGA). The core–shell particles possessed very narrow monomodal particle size distributions. XPS analysis of the latex film displayed that perfluoroalkyl groups had the tendency to enrich at surface and there was a gradient concentration of fluorine in the structure of the latex film from the film–air interface to the film–glass interface. In addition, compared with the latex film of crosslinked polyacrylate prepared under the same condition, the emulsifier-free core–shell IPN-fluorinated polyacrylate latex film showed better thermal stability, higher contact angle and lower water uptake.     

A facile synthesis of highly water-soluble, core–shell organo-silica nanoparticles with controllable size via sol–gel process

A series of highly water-soluble organo-silica nanoparticles, ranging from 2 to 10 nm in diameter, were synthesized by the cohydrolysis and copolycondensation reactions. ω-methoxy(polyethyleneoxy)propyltrimethoxysilane (PEG6-9) and hydroxymethyltriethoxysilane (HMTEOS) mixtures were catalyzed by sodium hydroxide in the presence of surfactant benzethonium chloride (BTC) with various ratios of PEG6-9/HMTEOS at room temperature. The synthesized organo-silica nanoparticles possess a core–shell structure with a core of organo-silica resulting from HMTEOS and a monolayer shell of PEG6-9. The chemo-physical characteristics of the particles were studied by gel permeation chromatography (GPC), Fourier transform infrared (FTIR) spectroscopy, ²⁹Si nuclear magnetic resonance (NMR), dynamic light scattering (DLS), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The molecular weight and particle size of the particles increased with increasing HMTEOS molar ratios. The richest HMTEOS composition for the water-soluble particles was found to be HMTEOS:PEG6-9 = 80:20, where the particles had a 6 nm diameter core and a 0.8 nm thick shell. We propose that these water-soluble organo-silica nanoparticles will be suitable for biomedical applications.     

Scattering properties of core–shell particles in plastic matrices

Blending submicron rubber particles with plastics can enhance the mechanical strength of the composite material. However, the difference in refractive index between the particle and matrix scatters light, making the material more opaque. We consider the possibility of reducing a particle's scattering cross section by adding coatings. We find that adding coatings can reduce the amount of scattering by changing the effective dielectric contrast between the particle and the matrix. We also found that, when the refractive index of the particle is very close to that of the matrix the order of the layers can have significant effects on the transmitted light. Such effects may be useful for engineering the optical properties of particle‐doped plastics. Resonant effects akin to those found in antireflection coatings on planar surfaces are difficult to obtain and rarely provide a significant reduction in scattering. We discuss theoretical models that can qualitatively explain some of our results. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3534–3548, 2005     

On the multiple crystallization behavior of PTFE in PMMA/PTFE nanocomposites from core–shell nanoparticles

The peculiar thermal behavior of four PTFE/PMMA (Polymethylmethacrylate) core–shell nanoparticle samples, marked DV2M1, DV2M2, DV2M4, and DV2M6, was studied by combined differential scanning calorimetry and thermogravimetric analysis. The melting process of the PTFE in the various samples, subjected to annealing and thermal treatments, does not change. In contrast, a complex fractionated crystallization‐type behavior for the PTFE component was observed. The nanocomposite produced by the PMMA shell fluidification features a perfect dispersion of the nanometric PTFE cores. In these conditions, only one crystallization exotherm at very high undercooling is observed, possibly deriving from the homogeneous nucleation mechanism. In contrast, when high temperature thermal treatments cause the decomposition with partial loss of the PMMA shell and allows some cores to get in contact and merge, a crystallization process structured into several components is observed. This behavior indicates that different nucleation mechanisms are active, possibly involving the participation of distinct types of active nuclei with distinct crystallization efficiencies. Finally, when the PMMA shell amount is substantially reduced by the thermal degradation, only the expected crystallization process at moderate undercooling (310 °C) is observed, corresponding to the bulk crystallization induced by the most efficient heterogeneous nuclei. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 548–554, 2010     

Morphological analysis of bead–string shaped and core–shell attapulgite@polystyrene (ATP@PS) particles via emulsion polymerization

A convenient method for the preparation of bead–string shaped and core–shell attapulgite@polystyrene (ATP@PS) composite particles through emulsion polymerization from needle‐shaped attapulgite is reported. The pretreatment of attapulgite with cetyltrimethylammonium bromide (CTAB) in ultrasonic is essential for successful encapsulation and for creating strong interfacial interaction between attapulgite and polystyrene (PS). The different morphologies of the ATP@PS particles, bead–string shaped and core–shell shaped, obtained with different amounts of styrene charges, were characterized by transmission electron microscopy (TEM). Encapsulation mechanisms of the two morphologies were also developed. Copyright © 2007 John Wiley & Sons, Ltd.     

Solid mechanochemical preparation of core‐shell SiO2 particles and their improvement on the mechanical properties of PVC composites

In this article, a solid mechanochemical route to prepare core‐shell structured particles was introduced. X‐ray photoelectron spectrum, transmission electron microscope and dissolving experimental results indicated the formation of [(inorganic particle)/(elastomer)] core‐shell structured particles. The thermal stable experiments showed that untreated SiO₂ can cause dehydrochlorination of poly(vinyl chloride) (PVC) and discoloration of PVC/SiO₂ composites and the formation of core‐shell structured SiO₂ particles will improve the thermal stability of PVC/SiO₂ composites. The mechanical properties and rheological results showed that the formation of core‐shell structured SiO₂ particles can both improve the mechanical and processing properties of PVC/SiO₂ composite. ACR in PVC/(SiO₂‐PMMA‐ACR) composites acted not only as toughener for PVC matrix but also as cushion breaker if the content of ACR is enough. Meanwhile compared with other SiO₂ particles the formation of core‐shell structured SiO₂ particles can decrease the apparent viscosity, increase the critical shear rate and improve the appearance of extrudes of PVC/SiO₂ composites. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 938–948, 2008     

Synthesis of gold–poly(methyl methacrylate) core–shell nanoparticles by surface‐confined atom transfer radical polymerization at elevated temperature

Surface‐confined atom transfer radical polymerization was used to prepare gold nanoparticle–poly(methyl methacrylate) core–shell particles at elevated temperature. First, gold nanoparticles were prepared by the one‐pot borohydride reduction of tetrachloroaurate in the presence of 11‐mercapto‐1‐undecanol (MUD). MUD‐capped gold nanoparticles were then exchanged with 3‐mercaptopropyltrimethoxysilane (MPS) to prepare a self‐assembled monolayer (SAM) of MPS on the gold nanoparticle surfaces and subsequently hydrolyzed with hydrochloric acid. The extent of exchange of MUD with MPS was determined by NMR. The resulting crosslinked silica‐primer layer stabilized the SAM of MPS and was allowed to react with the initiator [(chloromethyl)phenylethyl] trimethoxysilane. Atom transfer radical polymerization was conducted on the Cl‐terminated gold nanoparticles with the CuCl/2,2′‐bipyridyl catalyst system at elevated temperature. The rates of polymerization with the initiator‐modified gold nanoparticles exhibited first‐order kinetics with respect to the monomer, and the number‐average molecular weight of the cleaved graft polymer increased linearly with the monomer conversion. The presence of the polymer on the gold nanoparticle surface was identified by Fourier transform infrared spectroscopy and transmission electron microscopy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3631–3642, 2005     

Fabrication of novel core–shell PLGA and alginate fiber for dual‐drug delivery system

Biodegradable fibers for the controlled delivery of anti‐inflammatory agent dexamethasone were developed and studied. Mono and core–shell structure fiber are prepared by wet‐spinning solutions of hydrophobic poly (lactide‐co‐glycolide) and hydrophilic alginic acid shell. The two model drugs, dexamethasone and dexamethasone‐21‐phosphate, were entrapped in core and shell, respectively. These fibers were characterized in terms of morphology, diameters, mechanical properties, in vitro degradation, and drug release. The optical microscopy and scanning electron microscopy photos revealed directly that fibers possessed core–shell structure. The release of dexamethasone and dexamethasone‐21‐phosphate was investigated, and the results showed that alginate shell retarded dexamethasone release significantly in both early and late stages. The core–shell structure fiber release shows a two stage release of dexamethasone and dexamethasone‐21‐phosphate with distinctly different release rates, and minimal initial burst release is observed. The results indicated that the prepared fibers are efficient carrier for both types of dexamethasone. Copyright © 2016 John Wiley & Sons, Ltd.     

Core–shell column Tanaka characterization and additional tests using active pharmaceutical ingredients

In the last decade, core–shell particles have gained more and more attention in fast liquid chromatography separations due to their comparable performance with fully porous sub‐2 μm particles and their significantly lower back pressure. Core–shell particles are made of a solid core surrounded by a shell of classic fully porous material. To embrace the developed core–shell column market and use these columns in pharmaceutical analytical applications, 17 core–shell C₁₈ columns purchased from various vendors with various dimensions (50 mm × 2.1 mm to 100 mm × 3 mm) and particle sizes (1.6–2.7 μm) were characterized using Tanaka test protocols. Furthermore, four selected active pharmaceutical ingredients were chosen as test probes to investigate the batch to batch reproducibility for core–shell columns of particle size 2.6–2.7 μm, with dimension of 100 × 3 mm and columns of particle size 1.6 μm, with dimension 100 × 2.1 mm under isocratic elution. Columns of particle size 2.6–2.7 μm were also tested under gradient elution conditions. To confirm the claimed comparable efficiency of 2.6 μm core–shell particles as sub‐2 μm fully porous particles, column performances of the selected core–shell columns were compared with BEH C₁₈, 1.7 μm, a fully porous column material as well.     

Preparation and application of a novel core–shell‐particle‐supported zirconocene catalyst

The use of functional groups bearing silica/poly(styrene‐co‐4‐vinylpyridine) core–shell particles as a support for a zirconocene catalyst in ethylene polymerization was studied. Several factors affecting the behavior of the supported catalyst and the properties of the resulting polymer, such as time, temperature, Al/N (molar ratio), and Al/Zr (molar ratio), were examined. The conditions of the supported catalyst preparation were more important than those of the ethylene polymerization. The state of the supported catalyst itself played a decisive role in both the catalytic behavior of the supported catalyst and the properties of polyethylene (PE). IR and X‐ray photoelectron spectroscopy were used to follow the formation of the supports. The formation of cationic active species is hypothesized, and the performance of the core–shell‐particle‐supported zirconocene catalyst is discussed as well. The bulk density of the PE formed was higher than that of the polymer obtained from homogeneous and polymer‐supported Cp₂ZrCl₂/methylaluminoxane catalyst systems. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2085–2092, 2001     

Synthesis of polymer particles possessing radical initiating sites on the surface by emulsion copolymerization and construction of core–shell structures by a photoinduced atom transfer radical polymerization approach

The crosslinked polystyrene particles possessing photofunctional N,N‐diethyldithiocarbamate groups on their surface were prepared by free‐radical emulsion copolymerization of a mixture of styrene, divinylbenzene and 4‐vinylbenzyl N,N‐diethyldithiocarbamate with redox system as an initiator under UV irradiation. In this copolymerization, the inimer 4‐vinylbenzyl N,N‐diethyldithiocarbamate acted the formation of hyperbranched structures by living radical photopolymerization. The particle sizes (number‐average particle diameter = 214–523 nm) were controlled by varying the feed amount of surfactant and size distributions were relatively narrow. Subsequently, core–shell particles were synthesized by photoinduced atom transfer radical polymerization approach of methyl methacrylate initiated by photofunctional polystyrene particles as a macroinitiator. Such core–shell particles were stabilized sterically by grafted chains in organic solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1771–1777, 2007     

Preparation and characterization of core–shell polymer particles with protonizable shells prepared by oxyanionic polymerization

A series of polystyrene (PS)/poly(vinyl acetate) (PVAc) crosslinked particles (240, 210, or 90 nm) with different concentrations of PS (75, 50, or 25 wt %) were prepared by soap‐free emulsion polymerization. Based on the crosslinked polymer particles, three series of monodisperse core–shell particles with pH‐sensitive poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) shells were synthesized by oxyanionic polymerization. During the oxyanionic polymerization, the acetate groups of PVAc were hydrolyzed, and the hydroxyl groups that formed on the surfaces of the particles, acting as initiators, were transferred to ? O^?K⁺ by DMSO^?K⁺ (where DMSO is dimethyl sulfoxide) at the same time; then, ? O^?K⁺ initiated the polymerization of 2‐(dimethylamino)ethyl methacrylate. ¹H NMR and Fourier transform infrared studies confirmed the existence of PDMAEMA shells, and the contents of PDMAEMA were measured by elemental analysis. Because the PDMAEMA chain could be protonated at a low pH, these core–shell particles could adsorb negatively charged modified magnetite particles, and at higher pHs, the magnetite particles could be released again; this process was reversible. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6081–6088, 2004     

Rapid determination of parabens in seafood sauces by high‐performance liquid chromatography: A practical comparison of core–shell particles and sub‐2 μm fully porous particles

In this work, the chromatographic performance of superficially porous particles (Halo core–shell C₁₈ column, 50 mm × 2.1 mm, 2.7 μm) was compared with that of sub‐2 μm fully porous particles (Acquity BEH C₁₈, 50 mm × 2.1 mm, 1.7 μm). Four parabens, methylparaben, ethylparaben, propylparaben, and butylparaben, were used as representative compounds for calculating the plate heights in a wide flow rate range and analyzed on the basis of the Van Deemter and Knox equations. Theoretical Poppe plots were constructed for each column to compare their kinetic performance. Both phases gave similar minimum plate heights when using nonreduced coordinates. Meanwhile, the flat C‐term of the core–shell column provided the possibilities for applying high flow rates without significant loss in efficiency. The low backpressure of core–shell particles allowed this kind of column, especially compatible with conventional high‐performance liquid chromatography systems. Based on these factors, a simple high‐performance liquid chromatography method was established and validated for the determination of parabens in various seafood sauces using the Halo core–shell C₁₈ column for separation.     

The toughness amplification map of poly(vinyl chloride) and its cellulose acetate‐compatibilized starch alloys containing core/shell rubber particles: Possible transition to super‐toughening

Toughening amplification of the neat poly(vinyl chloride) (PVC) and its reinforced version containing 25 phr of the cellulose acetate (CA)‐compatibilized starch using methyl methacrylate‐butadiene‐styrene (MBS) core–shell particles was studied. The room temperature measured impact strength of the PVC showed mild increase up to 10 wt % with the addition of MBS particles. Then, the toughness enhanced discontinuously to super‐tough plateau regime. The room temperature measured impact strength of PVC containing 20 phr of MBS particles, however, was reduced by as much as 95% when it was filled with 25 phr of the CA‐compatibilized starch. In addition, the brittle–ductile transition (BDT) of the toughened PVC increased from 0 to 60 °C because of its reinforcement, even though the matrix number density of the core/shell particles remained almost constant. The decline in the impact strength and the rise in the BDT of the hybrid PVC system were attributed to the decrease in the shear deformable matrix and shear deformation propagation rate despite the increase in the process zone size. Maximum impact strength of the hybrid system at 60 °C (its BDT) increased to about 25% of the toughened PVC at its BDT (0 °C). The toughness amplification correlation of the toughened and hybrid PVC systems with their process zones fractional stress volumes under the impact load showed three regimes: quasi‐tough, transition, and super‐tough, which were superimposable on literature data regarding hybrid nylon 66 systems. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Gold‐loading magnetic core–shell organic/inorganic nanocomposites: facile preparation and multiple properties

Magnetic composite nanospheres (MCS) were first prepared via mini‐emulsion polymerization. Subsequently, the hybrid core–shell nanospheres were used as carriers to support gold nanoparticles. The as‐prepared gold‐loading magnetic composite nanospheres (Au‐MCS) had a hydrophobic core embed with γ‐Fe₃O₄ and a hydrophilic shell loaded by gold nanoparticles. Both the content of γ‐Fe₃O₄ and the size of gold nanoparticles could be controlled in our experiments, which resulted in fabricating various materials. On one hand, the Au‐MCS could be used as a T₂ contrast agent with a relaxivity coefficient of 362 mg^?1 ml S^?1 for magnetic resonance imaging. On the other hand, the Au‐MCS exhibited tunable optical‐absorption property over a wavelength range from 530 nm to 800 nm, which attributed to a secondary growth of gold nanoparticles. In addition, dynamic light scattering results of particle sizing and Zeta potential measurements revealed that Au‐MCS had a good stability in an aqueous solution, which would be helpful for further applications. Finally, it showed that the Au‐MCS were efficient catalysts for reductions of hydrophobic nitrobenzene and hydrophilic 4‐nitrophenol that could be reused by a magnetic separation process. Copyright © 2014 John Wiley & Sons, Ltd.     

Rapid determination of polycyclic aromatic hydrocarbons in rainwater by liquid–liquid microextraction and LC with core‐shell particles column and fluorescence detection

Liquid–liquid microextraction coupled to LC with fluorescence detection for the determination of Environmental Protection Agency's 16 priority pollutant polycyclic aromatic hydrocarbons in rainwater has been developed. The optimization of the extraction method has involved several parameters, including the comparison between an ultrasonic bath and a magnetic stirrer as extractant apparatus, the choice of the extractant solvent, and the optimization of the extraction time. Liquid–liquid microextraction gave good results in terms of recoveries (from 73.6 to 102.8% in rainwater) and repeatability, with a very simple procedure and low solvent consumption. The reported chromatographic method uses a Core‐Shell technology column, with particle size <3 μm instead of classical 5‐μm particles column. The resulting backpressure was below 300 bar, allowing the use of a conventional HPLC system rather than the more expensive ultrahigh performance LC (UHPLC). An average decrease of 59% in run time and 75% in eluent consumption has been obtained, compared to classical HPLC methods, keeping good separation, sensitivity, and repeatability. The proposed conditions were successfully applied to the determinations of polycyclic aromatic hydrocarbons in genuine rainwater samples.     

A facile preparation method for synthesis of silica sulfuric acid/poly(o‐methoxyaniline) core–shell nanocomposite

A new nanocomposite of poly(o‐methoxyaniline) (POMA) is introduced by overlayer formation of POMA on silica. The key appealing feature of the synthesis is the role of silica sulfuric acid (SSA) both as solid acid dopant and template in overlayer self‐assembly of POMA on silica surface. Hereon siloxide group (Si―O^?) of silica surface is replaced with dopant anion of SSA (≡Si―O―SO₃^?), which leads to formation of a overlayer of POMA on the silica surface. The composite particles are spherical in the nanoscale range of 50 nm without application of any external template (no‐template synthesis). Nanocomposite was fully characterized by various instrumentation methods: Fourier transform infrared (FT‐IR), ultraviolet–visible (UV–vis), thermogravimetric analysis (TGA), diffrential thermal analysis (DTA), elemental analysis (CHNS), energy dispersive X‐ray (EDX), X‐ray photoelectron spectroscopy (XPS) and X‐ray difraction (XRD). Based on XPS and CHNS results, it is demonstrated that the doping level of POMA is as high as 50% and for the first time the ratio of 4:2:2 is obtained for ―NH― (amine): ―HN^.+― (polarons): ?HN⁺― (bipolarons), respectively. In fact, bipolarons may also coexist with polarons with a 1:1 ratio of them. Moreover, the synthesis benefits from the perspective of green chemistry which is preparation under solid‐state (solvent‐free) condition. Copyright © 2015 John Wiley & Sons, Ltd.     

Development and validation of a generic high‐performance liquid chromatography for the simultaneous separation and determination of six cough ingredients: Robustness study on core–shell particles

A generally applicable high‐performance liquid chromatographic method for the qualitative and quantitative determination of pharmaceutical preparations containing phenylephrine hydrochloride, paracetamol, ephedrine hydrochloride, guaifenesin, doxylamine succinate, and dextromethorphan hydrobromide is developed. Optimization of chromatographic conditions was performed for the gradient elution using different buffer pH values, flow rates and two C₁₈ stationary phases. The method was developed using a Kinetex® C₁₈ column as a core–shell stationary phase with a gradient profile using buffer pH 5.0 and acetonitrile at 2.0 mL/min flow rate. Detection was carried out at 220 nm and linear calibrations were obtained for all components within the studied ranges. The method was fully validated in agreement with ICH guidelines. The proposed method is specific, accurate and precise (RSD% < 3%). Limits of detection are lower than 2.0 μg/mL. Qualitative and quantitative responses were evaluated using experimental design to assist the method robustness. The method was proved to be highly robust against 10% change in buffer pH and flow rate (RSD% < 10%), however, the flow rate may significantly influence the quantitative responses of phenylephrine, paracetamol, and doxylamine (RSD% > 10%). Satisfactory results were obtained for commercial combinations analyses. Statistical comparison between the proposed chromatographic and official methods revealed no significant difference.