Interfacial reinforcement of core-shell HMX@energetic polymer composites featuring enhanced thermal and safety performance

The weak interface interaction and solid-solid phase transition have long been a conundrum for 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane(HMX)-based polymer-bonded explosives(PBX).A two-step strategy that involves the pretreatment of HMX to endow—OH groups on the surface via polyalcohol bonding agent modification and in situ coating with nitrate ester-containing polymer,was proposed to address the problem.Two types of energetic polyether—glycidyl azide polymer(GAP)and nitrate modified GAP(GNP)were grafted onto HMX crystal based on isocyanate addition reaction bridged through neutral polymeric bonding agent(NPBA)layer.The morphology and structure of the HMX-based composites were characterized in detail and the core-shell structure was validated.The grafted polymers obviously enhanced the adhesion force between HMX crystals and fluoropolymer(F2314)binder.Due to the interfacial reinforcement among the components,the two HMX-based composites exhibited a remarkable increment of phase transition peak temperature by 10.2°C and 19.6°C with no more than 1.5%shell content,respectively.Furthermore,the impact and friction sensitivity of the composites decreased significantly as a result of the barrier produced by the grafted polymers.These findings will enhance the future prospects for the interface design of energetic composites aiming to solve the weak interface and safety concerns.

Preparation of Self-crosslinked Fluorocarbon Polymer Emulsion with Core-shell Structure by the Method of Soap-free Emulsion Polymerization

Using methyl methacrylate （MMA）, butyl acrylate（BA） and hexafluorobutyl acrylate（HFBA） as main raw materials, we prepared self-crosslinked fluorocarbon polymer emulsion with core-shell structure via soap-free emulsion polymerization when the conception of particle design and polymer morphology was adopted. Moreover, the influence of mole ratio of BA to MAA, pH value on the oligomer was studied. And the effects of the added amount of oligomer, self-crosslinked monomer and HFBA, mass ratio of BA to MMA, reaction temperature and the initiator on the polymerization technology and the performance of the product, were investigated and optimized. The structure and performance of the fluorocarbon polymer emulsion were characterized and tested with FTIR, TEM, MFT and contact angle and water absorption of the latex film. The experimental results show that the optimal conditions for preparing fluorocarbon polymer emulsion are as follows： for preparing the oligomer, tool ratio of BA to MAA is equal to 1.0 ： 1.60, and pH value is controlled within the range of 8.0 and 9.0; for preparing fluorocarbon polymer emulsion, the added amount of oligmer[P（BA/MANa）] is 6%; mass ratio of BA to MMA is 40 ＂ 60; the added amount of self-crosslinked monomer is 2%, the added amount of HFBA is 15 %; reaction temperature is 80 ℃; the mixture of potassium persulfate and sodium bisulfite is used as the initiator. The film-forming stability of the fluorocarbon polymer emul- sion and the performance of the latex film, which is prepared with the soap-free emulsion polymerization, are better than that prepared with the conventional emulsion polymerization.

NARROW-DISPERSED CROSSLINKED CORE-SHELL POLYMER MICROSPHERES PREPARED BY SURFACE-INITIATED ATOM TRANSFER RADICAL POLYMERIZATION

Grafting of polystyrene with narrowly dispersed polymer microspheres through surface-initiated atom transferradical polymerization(ATRP)was investigated.Polydivinylbenzene(PDVB)microspheres were prepared by dispersionpolymerization with poly(N-vinyl pyrrolidone)(PVP)as stabilizer.The surfaces of PDVB microspheres werechloromethylated by chloromethyl methyl ether in the presence of zinc chloride as catalyst to form chloromethylbenzeneinitiating core sites for subsequent ATRP grafting of styrene using CuCl/bpy as catalytic system.Polystyrene was found to begrafted not only from the particle surfaces but also from within a thin shell layer,resulting in the formation of particles sizeincreased from 2.38-2.58 μm,which can further grow to 2.93 μm during secondary grafting polymerization of styrene.Thisdemonstrates that grafting polymerization proceeds through a typical ATRP procedure with living nature.All of the preparedmicrospheres have narrow particle size distribution with coefficient of variation around 10%.

MICRON CORE-SHELL PARTICLES PREPARED BY GRAFTING POLYMERIZATION OF METHYL METHACRYLATE FROM NARROW DISPERSE SURFACE OF CHLOROMETHYLATED POLYDIVINYLBENZENE VIA ATRP

Grafting of poly(methyl methacrylate)from narrow disperse polymer particles by surface-initiated atom transferradical polymerization(ATRP)was investigated.Polydivinylbenzene(PDVB)particles were prepared by dispersionpolymerization with poly(N-vinyl pyrrolidone)(PVP)as the stabilizer.Chloromethylated PDVB was used as initiating coresites for subsequent ATRP of methyl methacrylate with CuBr/bpy as catalyst system.It was found that poly(methylmethacrylate)was grafted not only from the particle surfaces but also from within a thin shell layer,leading to particles sizeincreases from 2.38-3.00 μm with a core-shell structure particles.The grafted core-shell particles were characterized withFTIR,SEM,DSC.

Carbon nanotube-hyperbranched polymer core-shell nanowires with highly accessible redox-active sites for fast-charge organic lithium batteries

Organic electrode materials are promising for lithium-ion batteries(LIBs) because of their environmental friendliness and structural diversity.However,they always suffer from limited capacity,poor cycling stability,and rate performance.Herein,hexaazatrinaphthalene-based azo-linked hyperbranched polymer(HAHP) is designed and synthesized as a cathode for LIBs.However,the densely stacked morphology lowers the chance of the active sites participating in the redox reaction.To address this issue,the singlewalled carbon nanotube(SWCNT) template is used to induce the growth of nanosized HAHP on the surface of SWCNTs.The HAHP@SWCNT nanocomposites have porous structures and highly accessible active sites.Moreover,the strong π-π interaction between HAHP and highly conductive SWCNTs effectively endows the HAHP@SWCNT nanocomposites with improved cycling stability and fast charge-discharge rates.As a result,the HAHP@SWCNT nanocomposite cathode shows a high specific capacity(320.4 mA h g^(-1)at 100 mA g^(-1)),excellent cycling stability(800 cycles;290 mA h g^(-1)at 100 mA g^(-1),capacity retained 91%) and outstanding rate performance(235 mA h g^(-1)at 2000 mA g^(-1),76% capacity retention versus 50 mA g^(-1)).This work provides a strategy to combine the macromolecular structural design and micromorphology control of electrode materials for obtaining organic polymer cathodes for high-performance LIBs.

Synthesis of core-shell structured polymers with inserted thioether from a multi-functional scaffold

The synthesis of a thioether inserted, core-shell structured polymer from the scaffold of hyperbranched polyglycerol (PG) was described. PG was first allyl functionalized, and in the presence of AlBN, the allyl groups further underwent radical addition to thiol compounds, thus thiol functional polyethylene oxide monomether (MPEO) were grafted onto PG. Similarly, 2-mercaptoethylammonium chloride was introduced onto PG via thiol addition, and the residual amino groups were further quaternized with decyl bromide, leading to an amphiphilic core-shell structure polymer. (c) 2007 De Cheng Wan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Synthesis and Characterization of Fluorine-containing Polyacrylate Emulsion with Core-Shell Structure

A fluorine-containing polyacrylate copolymer emulsion was synthesized by a seed emulsion polymerization method, in which methyl methacrylate （MMA） and butyl acrylate （BA） were used as main monomers and hexafluorobutyl methacrylate （HFMA） as fluorine-containing monomer. The structure and properties were characterized by Fourier transform infrared spectrum （FT-IR）, transmission electron microscopy （TEM）, particle size analysis, X-ray photoelectron spectroscopy （XPS）, contact angle （CA）, differential scanning calorimetry （DSC） and thermogravimetry （TG） analysis. The FTIR and TEM results showed that HFMA was effectively involved in the emulsion copolymerization, and the formed emulsion particles had a core-shell structure and a narrow particle size distribution. XPS and CA analysis revealed that a gradient concentration of fluorine existed in the depth profile of fluorine-containing emulsion film which was richer in fluorine and more hydrophobic in one side. DSC and TG analysis also showed that a clear core-shell structure existed in the fluorine-containing emulsion particles, and their film showed higher thermal stability than that of fluorine-free emulsion.

Phase Transition of Poly（acrylic acid-co-N-isopropylacrylamide） Core-shell Nanogels

A series of poly（acrylic acid） macromolecular chain transfer agents with different molecular weights were synthesized by reversible addition-fragmentation chain transfer （RAFT） poly- merization and characterized by 1^H NMR and gel permeation chromatography. Multiresponsive core-shell nanogels were prepared by dispersion polymerization of N-isopropylacrylamide in water using these poly（potassium acrylate） macro-RAFT agents as the electrostcric stabilizer. The size of the nanogels decreases with the amount of the macro-RAFT agent, indicating that the surface area occupied by per polyelectrolyte group is a critical parameter for stabilizing the nanogels. The volume phase transition and the zeta potentials of the nanogels in aqueous solutions were studied by dynamic light scattering and zetasizer analyzer, respectively.

THE PREPARATION AND CHARACTERIZATION OF SBR/PS CORE-SHELL PARTICLES BY GAMMA IRRADIATION

A kind of core(SBR)-shell(PS)particles was synthesized by using SBR latex and grafting with St under gammairradiation.The influences of absorbed dose and dose rate on the grafting yield of PS on SBR seed latex have beeninvestigated.Results show there was a transition layer which contained the SBR/PS graft copolymer between the SBR coreand PS shell.Dynamic laser scattering(DLS)and differential scanning calorimetry(DSC)results confirm the existence ofgrafted polystyrene,and transmission electron microscope(TEM)observation verifies the core-shell structure of SBR-g-PSlatex.Such SBR/PS core-shell latex could be processed easily to ultrafine rubber powders by using spray drying andexpected to be used as an impact modifier for PS.

In-situ self-templated preparation of porous core-shell Fe_(1-x)S@N,S co-doped carbon architecture for highly efficient oxygen reduction reaction

Transition metal compound(TMC)/carbon hybrids,as prospering electrocatalyst,have attracted great attention in the field of oxygen reduction reaction(ORR).Their morphology,structure and composition often play a crucial role in determining the ORR performance.In this work,we for the first time report the successful fabrication of porous core-shell Fe_(1-x)S@N,S co-doped carbon(Fe_(1-x)S@NSC-t,t represents etching time)by a novel in-situ self-template induced strategy using Fe3O4 nanospheres and pyrrole as sacrificial self-template.The post-polymerization of pyrrole can be accomplished by the Fe^(3+)released through the etching of Fe_(3)O_(4) by HCl acid.Thus,the etching time has a significant effect on the morphology,structure,composition a nd ORR performance of Fe_(1-x)S@NSC-t.Based on the cha racterizations,we find Fe_(1-x)S@NSC-24 can realize effective and balanced combination of Fe_(1-x)S and NSC,possessing porous core-shell architecture,optimized structure defect,specific surface area and doped heteroatoms configurations(especially for pyridinic N,graphitic N and Fe-N structure).These features thus lead to outstanding catalytic activity and cycling stability towards ORR.Our work provides a good guidance on the design of TMC/carbon-based electrodes with unique stable morphology and optimized structure and composition.

Functional monodisperse microspheres fabricated by solvothermal precipitation co-polymerization

Simultaneous achievement in high solid content and high microsphere yield is deemed a challenge in the fabrication of monodisperse microspheres by precipitation polymerization.We herein demonstrate that micro-sized monodisperse poly(methacrylic monomer-divinylbenzene)microspheres containing epoxy,lauyl,carboxyl and hydroxyl functions can be fabricated by solvothermal precipitation copolymerization at 20%(mass)monomer loading with over 94%microsphere yield.The morphology and porosity of the obtained particles can be readily tuned by cosolvent-acetonitrile binary solvents.Addition of a small amount of cosolvent that has similar solubility parameter to that of the functional monomer can significantly improve the monodispersity of the obtained microspheres.When tetrahydrofuran was used as the co-solvent,the surface area of the highly porous microspheres achieved higher than 400 m^(2)·g^(-1).Solvothermal precipitation co-polymerization can be expected in scale-up fabrication of various monodisperse functional microspheres free of any surfactant and additive.

Preparation of Core-shell Structured Particles and Their Nucleation in Polyester:I. Preparation of Monodisperse SiO_2/PS Core-shell Composite Particles

To enhance the nucleation and crystallization properties of polyester (e.g., polyethylene terephthalate, PET), core-shell structured particles are used to improve these properties by controlling the inorganic dispersion properties in the polymers. In the paper, monodisperse particles of silica/polystyrene (PS) are prepared with both dispersion and emulsion polymerization techniques. The monodisperse silicon dioxide particles are first prepared with the seed growth method and modified by the coupling agents. Silica is properly modified with KH-570, and its size deviation is 3.0% or so. The modified silica then reacts with the mixture of ethanol, water medium, and monomer of styrene under dispersion polymerization. Results show that the dispersion polymerization technique is more suitable for monodisperse core-shell SiO2/PS particles than that of the emulsion. The morphology and molecular structure of the core-shell particles are investigated with the transmission electron microscope (TEM), and fourier transform infra-red spectroscopy (FTIR). The results show that the modified silica particles are successfully encapsulated with polystyrene. The average number of silica particles encapsulated into each polystyrene sphere decreases when the size of silica particles increases from 50 nm to 600 nm, and will approach one when the silica is greater than 380nm in size. The mass ratio for silica/PS particles in emulsion polymerization is 4.7/1, lower than that of 6.8/1 for dispersion polymerization, which is the first reported optimized data for preparing the similar monodisperse composite particles. Thus, the PS shell in the former is thinner than that in the latter.

Manufacturing of Surface Nanostructured Fibers Featuring an Antibacterial Effect by Magnetic Field Transportation of Magnetite@Silver Core-Shell Nanoparticles

Magnetic core-shell nanoparticles of type Fe3O4@Ag were synthesized in gram scale following a combined co-precipitation phase-transfer method and afterwards, processed to nanoparticle polymer (polypropylene and polyamide) composites. These composites were used as sheath material for the fabrication of core-sheath fibers. During the melt spinning process, a magnetic field was applied around the roving, whereby the particles move in the still liquid sheath polymer towards the surface. The produced fiber materials were investigated by AFM showing a nanostructuring of the surface, which was indirectly confirmed by determination of a slight surface tension lowering. Nanoparticle movement was shown by cross-section SEM and EDX measurements. The antibacterial activity of the spun fibers was proven by contacting them with Escherichia coli. A long-term stability of this effect was observable by carrying out a standard washability test. In contrast to previous works this new approach uses no deposition technique to introduce surface changes. It rather applies a magnetic force to move appropriately equipped nanoparticles from the inside of the fiber to the surface. This leads in only one step to a strong superficial anchoring of the particles resulting in a unique combination of long-term stable antibacterial and improved anti-soiling effects.

Controlled Synthesis of PCL/PVP Copolymer by RAFT Method and Its HydrophUic Block-Dependent MiceUar Behaviors

A range of poly（ε-caprolactone）/poly（N-vinyl-2-pyrrolidone） amphiphilic block copolymers with well-defined hydrophilic chain length were synthesized by the living/controlled reversible addition fragmentation chain transfer polymerization method. The composition and struc- ture of the targeted resultants were characterized with 1H NMR, 13C NMR, FT-IR spec- troscopy and gel permeation chromatography. The various block copolymers were success- fully employed to fabricate the spherical micelle with core-shell morphological structure. The poly（N-vinyl-2-pyrrolidone） block-dependent characteristics of the copolymeric micelles were investigated by fluorescence spectroscopy, dynamic light scattering, and transmission electron microscopy. The solubilization of the hydrophobic ibuprofen as a model drug in the micelle solution was also explored. It was found that the drug loading contents are related to the micellar morphology structure determined by hydrophilic chain length in the copolymer.

3D core-shell nanofibers framework and functional ceramic nanoparticles synergistically reinforced composite polymer electrolytes for high-performance all-solid-state lithium metal battery

Satisfactory ionic conductivity,excellent mechanical stability,and high-temperature resistance are the prerequisites for the safe application of solid polymer electrolytes(SPEs)in all-solid-state lithium metal batteries(ASSLMBs).In this study,a novel poly(m-phenylene isophthalamide)(PMIA)-core/poly(ethylene oxide)(PEO)-shell nanofiber membrane and the functional Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)ceramic nanopar-ticle are simultaneously introduced into the PEO-based SPEs to prepare composite polymer electrolytes(CPEs).The core PMIA layer of composite nanofibers can greatly improve the mechanical strength and thermal stability of the CPEs,while the shell PEO layer can provide the 3D continuous transport channels for lithium ions.In addition,the introduction of functional LLZTO nanoparticle not only reduces the crys-tallinity of PEO,but also promotes the dissociation of lithium salts and releases more Li^(+)ions through its interaction with the Lewis acid-base of anions,thereby overall improving the transport of lithium ions.Consequently,the optimized CPEs present high ionic conductivity of 1.38×10^(−4)S/cm at 30℃,signifi-cantly improved mechanical strength(8.5 MPa),remarkable thermal stability(without obvious shrinkage at 150℃),and conspicuous Li dendrites blocking ability(>1800 h).The CPEs also both have good com-patibility and cyclic stability with LiFePO_(4)(>2000 cycles)and high-voltage LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)(>500 cycles)cathodes.In addition,even at low temperature(40℃),the assembled LiFePO4/CPEs/Li bat-tery still can cycle stably.The novel design can provide an effective way to exploit high-performance solid-state electrolytes.

Poly(methyl methacrylate)/Poly(N-isopropylacrylamide) Core-Shell Particles Prepared by Seeded Precipitation Polymerization: Unusual Morphology and Thermo-sensitivity of Zeta Potential

Poly（methyl methacrylate）/poly（N-isopropylacrylamide） （PMMA/PNIPAM） core-shell particles were synthesized by seeded precipitation polymerization of N-isopropylacrylamide （NIPAM） in the presence of PMMA seed particles. The anionic potassium persulfate was used as initiator, and acrylic acid as functional comonomer. It was shown that the weight ratio of the PNIPAM shell to the PMMA core can be greatly increased through continuous addition of NIPAM monomer at a relatively slow rate. PMMA/PNIPAM particles with different shell thickness were obtained by varying the amount of charged NIPAM monomers. These particles exhibited unique nonspherical core-shell morphology. PMMA core was partially coated by dense hair-like or antler-like PNIPAM shell depending on the shell thickness. The measurement of these particles＇ zeta potential at different temperatures showed that the absolute value of zeta potential unusually decreased as the particle size decreased with temperature.

Preparation and characterization of cross-linked β-cyclodextrin polymer/Fe_3O_4 composite nanoparticles with core-shell structures

Cross-linkedβ-cyclodextrin polymer/Fe3O4 composite nanoparticles with core-shell structures were prepared via cross linking reaction on the surface of carboxymethylβ-cyclodextrin（CM-β-CD） modified Fe3O4 nanoparticles inβ-cyclodextrin alkaline solution by using epichlorohydrin as crosslinking agent.The morphology,structure and magnetic properties of the prepared composite nanoparticles were investigated by transmission electron microscopy（TEM）,Fourier transform infrared（FTIR） spectrometry,X-ray diffraction（XRD） measurement,thermogravimetric analysis（TGA） and Vibrating sample magnetometry （VSM）,respectively.

Superior Anodic Lithium Storage in Core–Shell Heterostructures Composed of Carbon Nanotubes and Schiff-Base Covalent Organic Frameworks

Covalent organic frameworks(COFs)after undergoing the superlithiation process promise high-capacity anodes while suffering from sluggish reaction kinetics and low electrochemical utilization of redox-active sites.Herein,integrating carbon nanotubes(CNTs)with imine-linked covalent organic frameworks(COFs)was rationally executed by in-situ Schiff-base condensation between 1,1′-biphenyl]-3,3′,5,5′-tetracarbaldehyde and 1,4-diaminobenzene in the presence of CNTs to produce core–shell heterostructured composites(CNT@COF).Accordingly,the redox-active shell of COF nanoparticles around one-dimensional conductive CNTs synergistically creates robust three-dimensional hybrid architectures with high specific surface area,thus promoting electron transport and affording abundant active functional groups accessible for electrochemical utilization throughout the whole electrode.Remarkably,upon the full activation with a superlithiation process,the as-fabricated CNT@COF anode achieves a specific capacity of 2324 mAh g^(−1),which is the highest specific capacity among organic electrode materials reported so far.Meanwhile,the superior rate capability and excellent cycling stability are also obtained.The redox reaction mechanisms for the COF moiety were further revealed by Fourier-transform infrared spectroscopy in conjunction with X-ray photoelectron spectroscopy,involving the reversible redox reactions between lithium ions and C=N groups and gradual electrochemical activation of the unsaturated C=C bonds within COFs.

3D Graphene Nanosheets Crosslinked Core-Shell FeS_(2)@N,S Co-Doped Porous Carbon for Improved Lithium/Sodium Storage Performance

Transition metal sulfides(TMS)hold great promise as anode materials for Li^(+)/Na^(+)storage.However,their practical application still faces several challenges,such as inadequate electrical conductivity,substantial volume changes and a propensity for agglomeration.To tackle these challenges,a 3D composite structure composed of graphene nanosheets crosslinked core−shell FeS_(2)@N,S co−doped porous carbon(FeS_(2)@NSC/GNs)is created by combining self−template polymerization with the graphene encapsulation technique.Systematic characterization and analysis demonstrate the effectiveness of the self−template polymerization strategy in generating a porous core−shell structure,which facilitates the uniform dispersion and optimal contact of the FeS_(2) core within the carbon shell.Concurrently,the integration of graphene,alongside the porous carbon shell,introduces a sophisticated dual−protection mechanism against volume expansion and undesirable FeS_(2) aggregation.Furthermore,the resulting 3D architecture enables efficient electron/ion transport and provides abundant sites for Li^(+)/Na^(+)storage.Leveraging these inherent benefits,the FeS_(2)@NSC/GNs composite exhibits significantly improved lithium/sodium storage performance in comparison to the counterparts.Evidently,our proposed approach offers valuable guidance for the construction of advanced anodes for lithium/sodium−ion batteries.

INTERACTION OF ANTIGEN AND ANTIBODY ON CORE-SHELL POLYMERIC MICROSPHERES

Monodispersed microspheres with polystyrene as the core and poly（acrylamide-co-N-acryloxysuccinirnide） as the shell were synthesized by a two-step surfactant-free emulsion copolymerization.The core-shell morphology of the microspheres was shown by scanning electron microscopy and transmission electron microscopy.Rabbit immunoglobulin G （as antigen） was covalently coupled onto the microspheres by the reaction between succinimide-activated ester groups on the shell of the microspheres and amino groups of the antigen molecules.The size of particles was characterized by dynamic light scattering technique and was found to vary upon bioconjugation and interaction with proteins.The binding process was shown to be specific to goat anti-rabbit immunoglobulin G（as antibody） and reversible upon the addition of free antigen into the system.