Polymerization-Induced Hierarchical Hybrid Particles from Siloxane Emulsification Endowing Polyurethane Composite Coating with Superhydrophobicity, Thermal Insulation, and Fluorescence.

Hierarchically structural particles (HSPs) are highly regarded as favorable nanomaterials for superhydrophobic coating due to their special multiscale structure and surface physicochemical properties. However, most of the superhydrophobic coatings constructed from HSPs are monofunctional, constraining their broader applications. Moreover, traditional methods for constructing HSPs mostly rely on complicated chemical routes and template removal. Herein, we propose an innovative strategy (one-pot method) for producing multifunctional hierarchical hybrid particles (HHPs). Polysilsesquioxane (PSQ), generated from hydrolysis condensation of methyltriethoxylsilane, is used as the sole stabilizer to anchor on the surface of styrene and short fluoroalkyl compound tridecafluorooctyl acrylate comonomers droplets, forming a mesoporous PSQ shell. Subsequently, the comonomers inside of the shell perform restricted polymerization to generate the HHP due to the driving of the mesoporous capillary force. The HHP is then mixed with waterborne polyurethane (WPU) to develop a robust nanocomposite coating (WPU-HHP). Through the deliberate design of the HHP components, the WPU-HHP coating has thermal insulation, photoluminescence properties, and the ability to achieve a wettability transition during abrasion. Our research has achieved the integration of multifunctionality in one waterborne hybrid system, broadening the application areas of nanocomposite coatings.

Shape-Tunable Hollow Polysiloxane Nanoparticles Based on a Surfactant-Free Soft Templating Method and Their Application as a Drug Carrier.

A surfactant-free soft-templating method has been used to prepare polysiloxane hollow nanoparticles with a controllable shape. This method is simple and has the potential for large-scale preparation. For the first time, we successfully obtained hollow polysiloxane nanoparticles with different shapes, including eccentric hollow polysiloxane microspheres (EHPM), apple-like hollow polysiloxane microparticles (AHPM), and bowl-like hollow polysiloxane microparticles (BHPM), by simply changing the solvent. In this method, the hydrolyzed methyltriethoxysilane (MTES) not only stabilizes the system as a surfactant but also acts as a reactant for subsequent reactions, so no additional surfactant is needed. In addition, the formation mechanism of hollow polysiloxane microparticles with different shapes is also proposed: that is, MTES hydrolyzed under acidic conditions to form a surfactant, which changes the system from suspension to a stable oil-in-water emulsion. Then, under alkaline conditions, the hydrolyzed MTES polycondenses and nucleates at the oil-water interface. At the same time, with the process of polycondensation, the hydrolyzed MTES will migrate to the nucleation site driven by surface tension, thus forming an eccentric core/shell (solvent/polysiloxane) structure. Due to the different forces between hydrolyzed MTES and different solvents, the deviation degree of hollow in microspheres is different, thus forming particles with various morphologies. This synthesis method provides a new idea for the preparation of shapeable anisotropic hollow structures. Finally, we use AHPM to study the application of the drug load. The results show that the prepared hollow polysiloxane particles have a good drug loading capacity and release performance. It can be predicted that the shape-tunable hollow polysiloxane particles prepared by this method have broad application prospects in the field of drug delivery.

Surface Tension-Induced Eccentric Hollow Polysiloxane Microspheres in a Surfactant-Free System and Their Applications as a Nanoreactor and Nanomotor.

Eccentric hollow polysiloxane microspheres (EHPMs) have attracted significant attention due to their potential in energy storage, drug delivery, and heterogeneous catalysis applications. However, their preparation pathways are often particularly complex. Therefore, it is critical to find a simple method for preparing EHPMs. In this study, a surfactant-free emulsification method is proposed to prepare EHPM. Under acidic conditions, methyl triethoxysilane (MTES) is hydrolyzed at the oil-water interface, with the hydrolyzed MTES demonstrating amphiphilic properties, and it could be anchored on the xylene surface to form an oil-in-water emulsion. The solution, when adjusted to alkaline, nucleated from a point at the oil-water interface. Driven by the surface tension, the hydrolyzed MTES migrated to the nucleation site with decreasing hydrophilicity. As a result, an EHPM formed. This process provides a simple, low cost, and environmentally friendly strategy for the preparation of EHPM, which demonstrated potential in catalytic and nanomotor applications.

Tough, Photoluminescent, Self-Healing Waterborne Polyurethane Elastomers Resulting from Synergistic Action of Multiple Dynamic Bonds.

Polymers that integrate multiple functions into one system broaden the application range of materials, but it remains a great challenge to obtain polymer materials with simultaneously high strength, high toughness, and high self-healing rate. In this work, we prepared waterborne polyurethane (WPU) elastomers using Schiff bases containing disulfide and acylhydrazone bonds (PD) as chain extenders. Acylhydrazone forming a hydrogen bond not only acts as a physical cross-linking point, which promotes the microphase separation of polyurethane to increase the thermal stability, tensile strength, and toughness of the elastomer, but also serves as a "clip" to integrate various dynamic bonds together to synergistically reduce the activation energy of the polymer chain movement and endow the molecular chain with faster fluidity. Therefore, WPU-PD exhibits excellent mechanical properties at room temperature, such as a tensile strength and a fracture energy of 25.91 MPa and 121.66 kJ m-2, respectively, and a high self-healing efficiency of 93.7% in a short time under moderate heating conditions. In addition, the photoluminescence property of WPU-PD enables us to track its self-healing process by monitoring change of the fluorescence intensity at the cracks, which helps to avoid the accumulation of cracks and improve the reliability of the elastomer. This self-healing polyurethane has a great potential application value in optical anticounterfeiting, flexible electronics devices, functional automobile protective films, and so on.

Multifunctional Waterborne Polyurethane Microreactor-Based Approach to Fluorocarbon Composite Latex Coatings with Double Self-Healing and Excellent Synergistic Performances.

In this article, chlorotrifluoroethylene (CTFE)-based fluorocarbon composite latexes and their coatings are successfully fabricated by an environmentally friendly preparation method based on a new multifunctional waterborne polyurethane (MFWPU) dispersion. It is worth noting that the MFWPU acts as the sole system stabilizer as well as microreactor and simultaneously endows the composite coating with excellent double self-healing performance and adhesion. Moreover, the introduction of a dynamic disulfide bond in the polyurethane dispersion entrusts the coating with excellent scratch self-healing performance. Simultaneously, carbon-carbon double bonds in the polyurethane dispersion increase the compatibility between the core polymer and shell polymer. The fluorine-containing chain segments can be distributed in the coating evenly during the self-assembly film-forming process of composite particles so that the original element composition of the worn coating surface can restore the original element composition after heating, and the coating presents a regeneration ability, which further and verifies the usefulness of the double self-healing model of the coating. Afterward, efficient recovery and durability, which are two contradictory properties of scratch self-healing polymers, are optimized to obtain a composite coating with excellent comprehensive performance. The research results regarding the composite system may provide a valuable reference for the structural design and application of waterborne fluorocarbon functional coatings in the future.

Room Temperature Preparation of Two-Dimensional Black Phosphorus@Metal Organic Framework Heterojunctions and Their Efficient Overall Water-Splitting Electrocatalytic Reactions.

Black phosphorus/two-dimensional (2D) metal-organic framework (BP@MOF) heterojunctions were synthesized via templated growth of 2D MOF-Fe/Co nanoplatelets on the surface of exfoliated BP nanosheets at room temperature. Because Fe3+ and Co2+ ions were absorbed onto the BP surface through coordination with the lone pair electrons of 2D BP, the BP@MOF heterojunction had an intimate interface with strong interactions. Electrochemical oxygen and hydrogen evolution reactions were studied using BP@MOF as the electrocatalyst. High activity of the overall water splitting in 1.0 M KOH was observed under a current density of 10 mA cm-2. The corresponding overpotentials for HER and OER were as low as 180 and 246 mV, respectively. Meanwhile, the BP@MOF exhibited good environmental stability and long-term electrocatalytic activity for OER and HER, owing to the encapsulation of BP nanosheets by the 2D MOF-Fe/Co. Through this study, a unique hybrid 2D nanomaterial is discovered for the efficient electrolytic splitting of water.

Effects of oppositely charged moieties on the self-assembly and biophysicochemical properties of polyurethane micelles.

Gemini quaternary ammonium (GQA), a type of cationic surfactant, exhibits excellent micellization ability and acts as a cell internalization promoter to increase the permeability of the cell membrane. GQA is sensitive to ionic solutions, which disturb its stabilization and leads to the rapid degradation of its polymer micelles due to its unique hydrophilic N+ structure. However, the effect of negatively charged moieties in the polymer chains of GQA on its action in polymer micelles, typically with regard to its micellization and biological performance, remains unclear. In this work, a series of polyurethane micelles containing various ratios of oppositely charged moieties was prepared. We found that the interchain electrostatic interaction severely undermines the function of the GQA surfactant and hinders the self-assembly and stabilization of polyurethane micelles. Specifically, a hydrophilic corona with a longer length cannot completely overcome this effect. By regulating the ratio of oppositely charged moieties, micelles exhibited tunable biological properties, such as biocompatibility, cytotoxicity, cell internalization, and phagocytosis by macrophages. Based on our results, a moderate molecular weight of mPEG (Mn = 1900) and a slight positive surface potential (∼10 mV) are the best surface parameters for the comprehensive performance of the studied nanoplatforms. This study provides a further understanding of the electrostatic interaction effect on the properties of the cationic GQA, offering rational guidance for the design and fabrication of GQA polymer micelles.

Effect of the disulfide bond and polyethylene glycol on the degradation and biophysicochemical properties of polyurethane micelles.

The disulfide bond has emerged as a promising redox-sensitive switch for smart polymeric micelles, due to its properties of rapid response to the reductive environment and spatiotemporally-controlled therapeutic agent delivery. However, the dilemma of multifunctional nanomedicine is that the more intelligent the functionalities integrated into a system, the vaguer the understanding of the structure and interaction between the multi-functional moieties becomes. To better understand the interaction between the disulfide bond and methoxy polyethylene glycol (mPEG), and their effects on the biophysicochemical characterization of micelles, we developed a series of polyurethane micelles containing various densities of disulfide bonds and bearing different molecular weights of mPEG. In this work, we found that the critical factor determining the degradation rate of polymer micelles was the hydrophobic/hydrophilic ratio of broken polymer segments triggered by disulfide bond breaking. The higher density of the disulfide bond and longer mPEG chain accelerate the degradation process due to the disproportionate hydrophobic/hydrophilic ratio of the broken chain, which is the key factor to determine the micellization and stabilization of polymer micelles. This work provides a fundamental understanding of the interaction between the complex functional groups and a new insight into the mechanism of the micelle degradation process, offering guidance on the rational design and fabrication of multifunctional nanoformulations.

Capillary Action-Inspired Nanoengineering of Spheres-on-Sphere Microspheres with Hollow Core and Hierarchical Shell.

The current syntheses of spheres-on-sphere (SOS) microsphere, which possesses both hollow cavity and hierarchical structure, mainly rely on complicated routes and template removal. In this study, a one pot nanoengineering strategy inspired by the automatic transport behavior of water in plants is successfully developed to fabricate SOS microsphere in tandem with a traditional soft template method in the preparation of hollow structure. Amphiphilic siloxane oligomers generated in situ from methyltriethoxylsilane (MTES) under acidic conditions are anchored on the surface of soft template St monomer droplets, sequentially completing hydrolysis-polycondensation and forming a mesoporous polysilsesquioxane (PSQ) shell. Then, the St monomers located in cavity migrate outward under the combined action of capillary force stemming from mesoporous and osmotic pressure generating from inside-outside of the PSQ shell and polymerize on the outside of the hollow PSQ shell, in which residual siloxane oligomers further anchor on the polystyrene (PS) surface to reduce the surface energy of the system, finally resulting in the successful formation of SOS particles. To reduce thermal insulation coefficient of the material, the PS phase in SOS particles is removed to obtain the particles with multiscale hollow structure (SOS-MH), which have more hollow cavities to encapsulate more air. The presence of a much hollow structure in SOS-MH particles enables the thermal conductivity of polyacrylonitrile (PAN)/SOS-MH composite fibrous membranes (0.0307 W m-1 K-1) to decrease by about 40% compared to that of pure PAN fibrous films (0.0520 W m-1 K-1) at the same thickness of 1 mm, and the material also has moisture resistance due to the existence of a hierarchical shell.

Facile Synthesis of Two-Dimensional Iron/Cobalt Metal-Organic Framework for Efficient Oxygen Evolution Electrocatalysis.

A facile synthesis is reported of two-dimensional (2D) bimetallic (Fe/Co=1:2) metal-organic frameworks (MOF, ca. 2.2 nm thick) via simple stirring of the reaction mixture of Fe/Co salts and 1,4-benzene dicarboxylic acid (1,4-BDC) in the presence of triethylamine and water at room temperature. The mechanism of the 2D, rather than bulk, MOF was revealed by studying the role of each component in the reaction mixture. It was found that these 2D MOF-Fe/Co(1:2) exhibited excellent electrocatalytic activity for the oxygen evolution reaction (OER) under basic conditions. The electrocatalytic mechanism was disclosed via both experimental results and density functional theory (DFT) calculation. The 2D morphology and co-doping of Fe/Co contributed to the superior OER performance of the 2D MOF-Fe/Co(1:2). The simple and efficient synthetic method is suitable for the mass production and future commercialization of functional 2D MOF with low cost and high yield.

Hollow mesoporous silica with a hierarchical shell from in situ synergistic soft-hard double templates.

Traditional methods for the construction of hollow particles with a hierarchical shell mainly rely on complicated chemical routes and removal of the templates. Herein, hollow mesoporous silica particles with a sphere-on-sphere (SOS) structure were successfully synthesized via a one-pot method using a novel "in situ synergistic soft-hard double template" strategy, that is, styrene (St) droplets as a soft template and in situ polymerized PS nano-domains as a hard template. The pre-hydrolysate derived from the silica precursor methyltriethoxysilane could anchor on the surface of the St droplets due to its amphiphilicity and then continue hydrolysis-condensation to form the mesoporous silica shell (MSS). Subsequently, MSS was used as a nanoreactor, and some of the in situ polymerized PS chains in the nanoreactor migrated to the outer surface of MSS due to the action of strong capillary force in the mesoporous channels, while some of the siloxane oligomers migrated to the surface due to their apparent interfacial activity, resulting in the hierarchical appearance of SOS. Furthermore, other intriguing hollow silica particles with a hollow sphere-on-sphere (HOS) structure were obtained by calcining the obtained SOS particles. The application of the as-prepared SOS and HOS particles showed their potential in the superhydrophobicity and detoxification fields, respectively.

Highly Stable Reduced Graphene Oxide Wrapped Black Phosphorus Heterostructure with Superior Photocatalytic Performance under Visible Light.

Metal-free photocatalysts with excellent visible-light absorption and highly efficient photocatalytic activity are attractive in the field of photocatalysis owing to their environmental friendliness. Black phosphorus (BP) shows a great potential in photoelectric conversion and photocatalysis due to its tunable band gap and two-dimensional structure. In this work, a stabilized metal-free photocatalyst, reduced graphene oxide (rGO)-wrapped BP heterostructure, was prepared by assembling BP and GO nanosheets in aqueous solution followed by partial reduction and lyophilization. The surface tension of the partially reduced GO during lyophilization could make rGO nanosheets tightly wrap on both surfaces of exfoliated BP nanosheets. This wrapped heterostructure with tight bonding between rGO and BP nanosheets led to a high photocatalytic activity, owing to the rapid transfer of the photogenerated electron-hole pairs at the rGO/BP heterojunction and the high stability of rGO protecting BP from oxygen attack. This work not only provided a general method to prepare the sandwiched heterojunction based on GO with good interface binding capability but also constructed a highly active, stable, metal-free photocatalyst based on BP.

A novel approach toward Snowman-like polymer/SiO2 hybrid nanoparticles via gas-driving.

For the first time, we report an interesting transition from conventional core-shell polymer/SiO2 particles to self-stable snowman-like particles, which can be achieved by adding a low-boiling point oil-soluble monomer because the volatile monomer not only plays a lubrication role, but also acts as a gas "motor" to drive the silica precursor polycondensate migration.

Dispersity control and anti-corrosive performance of graphene oxide modified by functionalized nanosilica in waterborne polyurethane.

Graphene oxide (GO) is expected to be used in the field of waterborne polyurethane (WPU) anti-corrosive coatings due to its excellent barrier property, but the poor dispersibility of GO limits its application. The hydrophilic modification of GO, although improving its dispersity, will greatly reduce its anti-corrosive property. Here, a new method is provided to avoid seeking an appropriate modifier blindly. Via the interaction between the epoxy group and amine group, the aminated GO (NGO) can be modified by (3-glycidyloxypropyl) trimethoxysilane (KH560) functionalized-silica (f-SiO2) nanoparticles, while the f-SiO2 is affected by KH560 due to its relatively hydrophobic alkyl side chain. Consequently, the hydrophobicity of the f-SiO2 modified NGO (f-SGO) can be regulated just by adjusting the amount of KH560, thereby achieving the balance of excellent dispersibility and anti-corrosive performance of the f-SGO nanosheets in the WPU. The electrochemical impedance and potentiodynamic polarization results showed that the anti-corrosive performance of the WPU hybrid was greatly improved by adding the appropriate amount of f-SGO. This research provides a new idea for GO application in waterborne coatings.

A Robust, Tough and Multifunctional Polyurethane/Tannic Acid Hydrogel Fabricated by Physical-Chemical Dual Crosslinking.

Commonly synthetic polyethylene glycol polyurethane (PEG-PU) hydrogels possess poor mechanical properties, such as robustness and toughness, which limits their load-bearing application. Hence, it remains a challenge to prepare PEG-PU hydrogels with excellent mechanical properties. Herein, a novel double-crosslinked (DC) PEG-PU hydrogel was fabricated by combining chemical with physical crosslinking, where trimethylolpropane (TMP) was used as the first chemical crosslinker and polyphenol compound tannic acid (TA) was introduced into the single crosslinked PU network by simple immersion process. The second physical crosslinking was formed by numerous hydrogen bonds between urethane groups of PU and phenol hydroxyl groups in TA, which can endow PEG-PU hydrogel with good mechanical properties, self-recovery and a self-healing capability. The research results indicated that as little as a 30 mg·mL-1 TA solution enhanced the tensile strength and fracture energy of PEG-PU hydrogel from 0.27 to 2.2 MPa, 2.0 to 9.6 KJ·m-2, respectively. Moreover, the DC PEG-PU hydrogel possessed good adhesiveness to diverse substrates because of TA abundant catechol groups. This work shows a simple and versatile method to prepare a multifunctional DC single network PEG-PU hydrogel with excellent mechanical properties, and is expected to facilitate developments in the biomedical field.

Facile fabrication, morphology control, and modification of polymeric yolk-shell microspheres.

The fabrication and functionalization of polymeric yolk-shell microspheres (YSMs), possessing a hollow shell and a movable core, is interesting but challenging in materials science. Here we report the facile fabrication, morphology control, and fluorescent modification of polymeric YSMs, which have a spherical core of poly(vinylidene fluoride) (PVDF) and a hollow shell of poly(styrene-co-glycidyl methacrylate). First, flower-like microspheres with core-shell structures are synthesized via seeded surface nucleation in an emulsion polymerization of styrene, glycidyl methacrylate, and divinylbenzene by using PVDF microparticles as seeds. Both the feed ratio and the polymerization time are considered to manipulate the core-shell structures of the composite microparticles, which obviously influences the morphology of the YSMs obtained from the subsequent treatment of solvent etching to remove the seed. The hollow volume of the polymeric YSMs is easily adjusted by changing the etching time at different temperatures. Meanwhile, we realized three-dimensionally confined crystallization of PVDF in different morphologies of YSMs. Furthermore, YSMs with the same or different functional groups, inside and outside of the hollow shell, respectively, are chemically modified by the reaction of glycidyl groups on the shell with 2,2'-(ethylenedioxy) bis-ethylamine. Thus, strong fluorescence of the YSMs is observed by subsequent labeling with functional fluorescent groups.

How Chain Intermixing Dictates the Polymorphism of PVDF in Poly(vinylidene fluoride)/Polymethylmethacrylate Binary System during Recrystallization: A Comparative Study on Core⁻Shell Particles and Latex Blend.

In the past few decades, Poly(vinylidene fluoride)/Polymethylmethacrylate (PVDF/PMMA) binary blend has attracted substantial attention in the scientific community due to possible intriguing mechanical, optical and ferroelectric properties that are closely related to its multiple crystal structures/phases. However, the effect of PMMA phase on the polymorphism of PVDF, especially the relationship between miscibility and polymorphism, remains an open question and is not yet fully understood. In this work, three series of particle blends with varied levels of miscibility between PVDF and PMMA were prepared via seeded emulsion polymerization: PVDF⁻PMMA core⁻shell particle (PVDF@PMMA) with high miscibility; PVDF/PMMA latex blend with modest miscibility; and PVDF@c⁻PMMA (crosslinked PMMA) core⁻shell particle with negligible miscibility. The difference in miscibility, and the corresponding morphology and polymorphism were systematically studied to correlate the PMMA/PVDF miscibility with PVDF polymorphism. It is of interest to observe that the formation of polar ß/γ phase during melt crystallization could be governed in two ways: dipole⁻dipole interaction and fast crystallization. For PVDF@PMMA and PVDF/PMMA systems, in which fast crystallization was unlikely triggered, higher content of ß/γ phase, and intense suppression of crystallization temperature and capacity were observed in PVDF@PMMA, because high miscibility favored a higher intensity of overall dipole⁻dipole interaction and a longer interaction time. For PVDF@c⁻PMMA system, after a complete coverage of PVDF seeds by PMMA shells, nearly pure ß/γ phase was obtained owing to the fast homogeneous nucleation. This is the first report that high miscibility between PVDF and PMMA could favor the formation of ß/γ phase.

Intriguing Morphology Evolution from Noncrosslinked Poly(tert-butyl acrylate) Seeds with Polar Functional Groups in Soap-Free Emulsion Polymerization of Styrene.

Herein, we demonstrate a facile approach to prepare anisotropic poly(tert-butyl acrylate)/polystyrene (PtBA/PS) composite particles with controllable morphologies by soap-free seeded emulsion polymerization (SSEP). In the first step, noncrosslinked PtBA seeds with self-stabilizing polar functional groups (e.g., ester groups and radicals) are synthesized by soap-free emulsion polymerization. During the subsequent SSEP of styrene (St), PS bulges are nucleated on the PtBA seeds due to the microphase separation confined in the latex particles. The morphology evolution of PtBA/PS composite particles is tailored by varying the monomer/seed feed ratio, polymerization time, and polymerization temperature. Many intriguing morphologies, including hamburger-like, litchi-like, mushroom-like, strawberry-like, bowl-like, and snowman-like, have been acquired for PtBA/PS composite particles. The polar groups on the PtBA seed surface greatly influence the formation and further merging of PS/St bulges during the polymerization. A possible formation mechanism is proposed on the basis of experimental results. These complex composite particles are promising for applications in superhydrophobic coatings.

Self-Assembled Colloidal Particle Clusters from In Situ Pickering-Like Emulsion Polymerization via Single Electron Transfer Mechanism.

A simple route is reported to synthesize colloidal particle clusters (CPCs) from self-assembly of in situ poly(vinylidene fluoride)/poly(styrene-co-tert-butyl acrylate) [PVDF/P(St-co-tBA)] Janus particles through one-pot seeded emulsion single electron transfer radical polymerization. In the in situ Pickering-like emulsion polymerization, the tBA/St/PVDF feed ratio and polymerization temperature are important for the formation of well-defined CPCs. When the tBA/St/PVDF feed ratio is 0.75 g/2.5 g/0.5 g and the reaction temperature is 35 °C, relatively uniform raspberry-like CPCs are obtained. The hydrophobicity of the P(St-co-tBA) domains and the affinity of PVDF to the aqueous environment are considered to be the driving force for the self-assembly of the in situ formed PVDF/P(St-co-tBA) Janus particles. The resultant raspberry-like CPCs with PVDF particles protruding outward may be promising for superhydrophobic smart coatings.

Nonspherical nanoparticles with controlled morphologies via seeded surface-initiated single electron transfer radical polymerization in soap-free emulsion.

This work reports a facile novel approach to prepare asymmetric poly(vinylidene fluoride)/polystyrene (PVDF/PS) composite latex particles with controllable morphologies using one-step soap-free seeded emulsion polymerization, i.e., surface-initiated single electron transfer radical polymerization (SET-RP) of styrene (St) at the surface of PVDF seed particles. It was observed that the morphology was influenced mainly by the St/PVDF feed ratio, the polymerization temperature, and the length of the catalyst Cu(0) wire (Φ 1.00 mm). When the feed ratio was St/PVDF = 5.0 g/1.0 g, snowman-like Janus particles were exclusively obtained. Raspberry-like and popcorn-like composite particles were observed at a higher reaction temperature or a shorter length of the catalyst wire. The reaction kinetics plots demonstrated some unique features. The formation of nonspherical composite nanoparticles can be ascribed to the surface nucleation of PS bulges following the SET-RP.