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.

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.

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.

Mechanical Behavior of Polyurethane Polymer Materials under Triaxial Cyclic Loading:A Particle Flow Code Approach

Polyurethane polymer grouting materials were studied with conventional triaxial tests via the particle flow code in two dimensions（PFC^（2D）） method, and the simulation results agreed with the experimental data. The particle flow code method can simulate the mechanical properties of the polymer. The triaxial cyclic loading tests of the polymer material under different confining pressures were carried out via PFC^（2D） to analyze its mechanical performance. The PFC^（2D） simulation results show that the value of the elastic modulus of the polymer decreases slowly at first and fluctuated within a narrow range near the value of the peak strength; the cumulative plastic strain increases slowly at first and then increases rapidly; the peak strength and elastic modulus of polymer increase with the confining pressure; the PFC^（2D） method can be used to quantitatively evaluate the damage behavior of the polymer material and estimate the fatigue life of the materials under fatigue load based on the number and the location of micro-cracks. Thus, the PFC^（2D） method is an effective tool to study polymers.

Polybutylacrylate/poly(methyl methacrylate) Core-Shell Elastic Particles as Epoxy Resin Toughener: Part I Design and Preparation

Polybutylacrylate (PBA)/poly(methyl methacrylate) (PMMA) core-shell elastic particles (CSEP), whose rubbery core diameter ranged from 0.08 μm to 1.38μm, were synthesized by using conventional emulsion polymerization, multi-step emulsion polymerization, and soapless polymerization. Allyl methacylate (ALMA) and ethylene glycol dimethacrylate (EGDMA) were selected as crosslinking reagents for core polymerization. Methacrylic acid (MAA) was used as functional co-monomer with methyl methacrylate as shell component. The content of vinyl groups in PBA rubbery core increased with the amount of crosslinking reagents. The core-shell ratio affected great on the morphology of the complex particles. Furthermore, the amounts of carboxyl on the surface of core-shell particles, copolymerized with acrylic acid, were determined by potentiometric titration. Results showed that methylacrylic acid was distributed mostly on the surface of particles.

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.

TOUGHENING OF POLYCARBONATE WITH PBA-PMMA CORE-SHELL PARTICLES

The miscibility,mechanical properties,morphology and toughening mechanism of PC/PBA-PMMA blends wereinvestigated.The dynamic mechanical results show that PC/PBA-PMMA blend has good miscibility and strong interfacialadhesion.The Izod impact strength of blend PC/PBA-PMMA with 4%(volume fraction)PBA-PMMA core-shell modifier is16 times higher than that of pure PC.The core-shell volume fraction and thickness of the PMMA shell have effect on thetoughness of PC/PBA-PMMA blends.As PMMA volume fraction increases,the toughness of PC/PBA-PMMA blendincreases,and reaches a maximum value at 30% volume fraction of PMMA or so.The tensile properties of PC/PBA-PMMAblend with a minimum amount of PBA-PMMA modifier show that brittle-tough transition has no significant variance incomparison with that of pure PC.The scanning electron microscopic(SEM)observation indicates that the tougheningmechanism of the blend with the pseudo-ductile matrix modified by small core-shell latex polymer particles is the synergeticeffect of cavitation and shear yielding of the matrix.

Synthesis of Molecularly Imprinted Polymer Particles by Suspension Polymerization in Silicon Oil

Molecularly imprinted polymers using 2,4-dichlorophenoxyacetic acid （2,4-D） as templates were prepared by suspension polymerization in silicon oil. The polymer particles exhibited regular shape in the micro-scale range. The adsorbing experiments indicated that the imprinted polymer particles possessed higher affinity to 2,4-D than the non-imprinted polymer particles.

The Effect of Cyclodextrins in Polymer Particles Synthesis

The free radical polymerization of styrene in water in the presence of β-cyclodextrin (β-CD) is described. It is found that β-CD could greatly accelerate the polymerization, enhance the final conversion of monomer. The particle-size distribution of the final polymer is also improved than that without β-CD in the system.

Polybutylacrylate/poly (methyl methacrylate) Core-Shell Elastic Particles as Epoxy Resin Toughener: Part Ⅱ Toughness on DGEBA/DDM system

Mechanlcal properties of epoxy resin were investigated by adding core-shell elastic particles (CSEP). The results indicated that optimized core-shell ratio was 60/40 and the loading volume of CSEP was 10 phr (per hundred parts of epoxy resin by weight). The impact strength of modified systems increased apparently with the decrease of core sizes. However, the shearing strength changed gently with the particle sizes. CSEP with lightly crosslinked rubbery core showed more effectiveness on toughness than others. With solution blending, CSEP could be dispersed in epoxy matrix well, and the morphologies of dispersed rubber domains were controlled perfectly by CSEP whose structure was predesigned. A cavitation-shearing band toughness mechanism was observed from the SEM micrographs of fracture surface. It also was found that the deforming temperature (DT) of modified epoxy did not decline apparently.

Controlling Shell Thickness of PS/SiO_2 Core-Shell Particles and Their Crystallization into 3-D Ordered Thin Film

PS/SiO2 particles with core-shell structure were synthesized by coating silica on surface of polystyrene(PS) colloidal particles.The reaction parameters,such as initial tetraethyl orthosilicate(TEOS) concentration,water concentration and reaction temperature,have been investigated to control the thickness of silica shells.The shell thickness was prepositional to the square root of the initial concentration of TEOS and first increased with increasing water concentration,reached a maximum at about 2.0 mol/L and then started decreasing beyond that concentration.It was also found that the shell thickness decreased firstly with the reaction temperature added,then tended to a constant.The so-synthesized PS/SiO2 core-shell particles were directly crystallized into 3-D ordered thin film,then sintered at 570℃ into the ordered macroporous thin film.Compared with the conditional method,the present approach avoids repeatedly filling the precursor in the templetes and save time more.

Optimized high performance liquid chromatography–ultraviolet detection method using core-shell particles for the therapeutic monitoring of methotrexate

Methotrexate （MTX） is an antineoplastic drug, and due to its high toxicity, the therapeutic drug mon- itoring is strictly conducted in the clinical practice. The chemometric optimization and validation of a high performance liquid chromatography （HPLC） method using core-shell particles is presented for the determination of MTX in plasma during therapeutic monitoring. Experimental design and response surface methodology （RSM） were applied for the optimization of the chromatographic system and the analyte extraction step. A Poroshel1120 EC-C18 （3.0 mm × 75 mm, 2.7 μm） column was used to obtain a fast and efficient separation in a complete run time of 4 min. The optimum conditions for the chroma- tographic system resulted in a mobile phase consisting of acetic acid/sodium acetate buffer solution （85.0 mM, pH =4.00） and 11.2% of acetonitrile at a flow rate of 0.4 mL/min. Selectivity, linearity, accuracy and precision were demonstrated in a range of 0.10-6.0 μM of MTX. The application of the optimized method required only 150μL of patient plasma and a low consumption of solvent to provide rapid re- sults.

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.

Review:Progress in Core-shell Rubber Particles for Efficiently Toughening Resins

Core-shell toughening particles are structured composite particles consisting of generally two different components, one at the center as a rubbery elastic core and surrounding by the second as a glassy inelastic shell. The design, preparation, and application of core-shell polymer particles have been briefly reviewed. Morphological characteristics of the core-shell particles by transmission electron microscopy(TEM) and scanning electron microscopy(SEM) are focused. The vital factors that are useful to control core-shell morphology and toughening properties including core-shell monomer species, polymerization conditions, cross-linking reagents, synthetic method, and post-processing techniques are analyzed. Distinguished properties are mainly considered as the most desirable features that endow core-shell polymer particles with various applicabilities, particularly as effectively toughening components in brittle epoxy resin and polylactide that are substrate of copper clad laminate widely used in the modern electronic world and environmentally friendly materials that are useful as packaging films, disposable tableware, biomedical equipment, and new energy vehicles.

Friction and Wear of Polymer Composites Filled by Nano-Particles: A Review

Composites formed by adding nano-scale particles to a polymer matrix results in improving electrical, mechanical, and thermal properties of the composite. Good tribological properties can be obtained for polymers filled with nano-scale fillers compared to that filled with micro-scale particles. The friction and wear resistance of these composites is found to increase with increasing filler concentration. It is also possible to use multi-functional fillers to develop high performance composites which cannot be achieved by using a single filler.

Investigation of the performance of a pilot-scale barrel atmospheric plasma system for plasma activation of polymer particles

This study reports the development and performance of a pilot-scale barrel atmospheric plasma reactor for the atmospheric plasma activation treatment of polymer particles. The polymer particles treated included acrylonitrile butadiene styrene(ABS) and polypropylene(PP). These particles had diameters in the range of 3–5 mm. The initial studies were carried out using a laboratory-scale barrel reactor designed to treat polymer particle batch sizes of 20 g. A pilot-scale reactor that could treat 500 g particle batch sizes was then developed to facilitate pre-industrial-scale treatments. The effect of operating pulse density modulation(PDM) in the range 10%–100% and plasma treatment time on the level of activation of the treated polymers were then investigated. ABS revealed a larger decrease in water contact angle compared with PP after plasma treatment under the same conditions. The optimal treatment time of ABS(400 g of polymer particles) in the pilot-scale reactor was 15 min. The plasma-activated polymer particles were used to fabricate dog-bone polymer parts through injection molding.Mechanical testing of the resulting dog-bone polymer parts revealed a 10.5% increase in tensile strength compared with those fabricated using non-activated polymer particles.

Degradation of Diclofenac in Molecularly Imprinted Polymer Submicron Particles by UV Light Irradiation and HCl Acid Treatment

A new molecularly imprinted polymer (MIP) was synthesized by precipitation polymerization using diclofenac (DFC) as a template. Binding characteristics of the MIP particles were evaluated by equilibrium binding experiments. DFC-MIP aqueous suspension and non-imprinted polymer (NIP) suspension were exposed to monochromatic UV light (253.7 nm) from low-pressure mercury lamps. UV-visible spectrophotometry (especially absorbance at 276 nm) showed that the DFC inside MIP particles degraded completely. After DFC-MIP suspension exposure to UV light the particles were completely regenerated after washing with water at least six times. The regenerated MIP particles rebounded considerable amount of DFC (approximately 88% removal of 44 ppm DFC). The stability of DFC was examined in the presence of various concentrations of hydrochloric acid (0.025 to 125 mM). Experimental results showed that degradation of DFC was efficient, depending on the acid concentration as well as the treatment time. However, there was no re-binding of DFC by the MIP particles after HCl treatment (and DDW washing) when exposed to DFC for 24 hours.

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.

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.

Electrorheological Properties of Suspensions of PAn-PEO-PAn Triblock Copolymer Particles

The PAn-PEO-PAn triblock copolymer with the PEG chain length of 400 was synthesized by chemical oxidation copolymerization of aniline and α,ω-bis（p-aminophenyl）poly（ethylene glycol）and characterized by FT-IR and TEM.The experimental results show that the copolymer particles are of μtypical core-shell structure after the self-assembly process in water.Its conductivity is much lower than that of the pure PAn.The suspension containing 20 vol% PAn-PEO-PAn tiblock copolymer in silicone oil exhibits.a typical electrorheological （ER） effect in DC electric field.while it shows a lower leakage current density than that of the pure PAn-based ER fluids.Therefore,the PEO shell hinders the electric hop among PANI chains and decreases the current density of ER fluids in an external electric field.at the same time the interface polarity improves the ER effects.