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.

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.

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.

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%.

Influence of polymer dispersants on dispersion stability of nano-TiO_2 aqueous suspension and its application in inner wall latex paint

The effects of SN5040 and polyethylene glycol（PEG） individually and in combination on the dispersion stability of nano-TiO2 aqueous suspension were investigated by ultraviolet-visible absorption spectroscopy. The adsorption mechanism of these dispersants was detected by zeta potential, isothermal absorption and FTIR analysis. It is found that SN5040 is superior for stabilizing nano-TiO2 in aqueous suspension to PEG in basic region, and the optimum mass fraction of SN5040 addition is 3%. In the case of NaCl addition, the optimum value increases with .the increase of NaCl concentration in the solution. When the mixture of SN5040 and PEG is employed, the antagonism appears preponderant. When SN5040 and PEG are added sequentially, the synergistic reaction takes place. The synergistic reaction can be attributed to the mechanism that PEG adsorption decreases the electronic repulsion between SN5040 molecules, which results in the increase of SN5040 adsorption density. PEG is adsorbed by the interaction with the pre-adsorbed SN5040 layer. Furthermore, the modified inner wall latex paint with well dispersed nano-YiO2 suspension is endowed with excellent ultraviolet absorption and antibacterial properties.

Influences of Polypropylene Fiber and SBR Polymer Latex on Abrasion Resistance of Cement Mortar

Influences of polypropylene （PP） fiber and styrene-butadiene rubber （SBR） polymer latex on the strength performance, abrasion resistance of cement mortar were studied. The experimental results show that the flexural strength, brittleness index （σF/σC） and abrasion resistance can be improved significantly by the addition of PP fiber and SBR polymer latex. The relationship between the flexural strength and abrasion resistance was analyzed, showing a good linear relationship between them. The reinforced mechanism of PP fiber and SBR polymer latex on cement mortar was analyzed by some microscopic tests. The test results show that the addition of SBR polymer latex has no significant influence on the cement hydration after 7 d curing. Adding SBR polymer latex into cement mortar can form a polymer transition layer in the interfaces of PP fiber and cement hydrates, which improves the bonding properties between the PP fiber and cement mortar matrix effectively.

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.

HIGH SOLIDS-CONTENT NANOSIZE POLYMER LATEXES MADE BY A MODIFIED EMULSION COPOLYMERIZATION

Polymer nanoparticles were prepared in the methyl methacrylate (MMA)/buty lmethacrylate (BA) emulsion copolymerization process by a modified microemulsion copolymerization method. 2-Hydroxyethyl methacrylate(HEMA), acrylate (AA) and methyl acrylate (MAA) were used as reactive cosurfactants. With this process high polymer: surfactant weight ratios (40:1 or greater),relatively concentrated (~30wt. %) latexes and small (~60nm) particle diameters were obtained.Properties of the latexes were characterized by TEM, DSC, dynamic light scattering, and IR spectroscopy.

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.

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.

改性干粉型聚合物水泥砂浆试验研究

本文研究两种不同的可再分散乳胶粉(醋酸乙烯-乙烯共聚物和醋酸乙烯/叔碳酸乙烯酯共聚物)对干粉型聚合物水泥砂浆力学性能、粘结强度、吸水率、干燥收缩的性能影响。结果表明,可再分散乳胶粉的掺量、类型对聚合物水泥砂浆的性能影响较大,力学性能较普通水泥砂浆有明显的提升和改善。可再分散乳胶粉的加入虽然降低了砂浆的抗压强度,但显著提高了抗折强度和折压比,改善了砂浆的柔韧性和抗裂能力;砂浆的干燥收缩、粘结强度和吸水率等性能均有较为明显的改善。

水玻璃种类对聚合物改性碱激发矿渣性能的影响

从水化过程、力学性能、收缩性能等方面系统研究了2种水玻璃对苯丙乳液(SA乳液)改性碱激发矿渣(AAS)性能的影响及其作用机理,以期指导SA乳液在AAS中的应用.结果表明:钾水玻璃(PWG)加速矿渣水化进程的能力强于钠水玻璃(SWG);SA乳液不影响AAS的水化进程,不会阻碍水化硅酸钙/水化硅铝酸钙的生成,但会抑制水滑石的生成;SA乳液显著降低了AAS的抗压强度,并且对PWG激发AAS的影响强于SWG激发AAS;AAS的抗折强度随着SA乳液掺量的增加呈先增大后减小的趋势,在SWG与PWG激发AAS中,SA乳液的最佳掺量分别为2.5%与5.0%;PWG激发AAS在14d内的总变形量高于SWG激发AAS,SA乳液可显著降低硬化浆体的总收缩量.

The Current Progress and Challenges of Carbonized Polymer Dot-Based Room-Temperature Phosphorescent Materials

Carbonized polymer dots(CPDs)as one type of carbon dots have attracted widespread attention in recent years.The proposal of the“shell–core”structure of CPDs leads to further thinking about the association between their special structures and luminescent properties.In recent years,great progress has been made in the field of CPD-based room-temperature phosphorescent materials.This review pays particular attention to how the special“core–shell”structure of CPDs influences the activation of roomtemperature phosphorescence(RTP).The strategies and vital factors to activate RTP for CPD-based materials in both solid state and water were reviewed in detail to elaborate on the effect of the special structure on RTP generation.Furthermore,some perspectives on the current challenges were also provided to guide the further development of CPD-based room-temperature phosphorescent materials.

Preparation of Styrene-acrylate Latex Used in Ultralow VOC Building Internal Wall Coating

Styrene-acrylate latex with high glass transition temperature （T）, low minimum film forming temperature（MFT） and good stability was prepared via core-shell emulsion polymerization. With semicontinuous process, high conversion rate of monomer and low gel rate were achieved. The weight ratio of core monomer to shell monomer was approximately 1.35. It is found that many factors such as emulsifiers, initiators, reaction temperature, pH value and polymerization technology have influences on the permormance of styrene-acrylate latex. The prepared latex was characterized by TEM and FTIR. The obtained latex with T of 20.57 ℃, MFT or5.0 ℃, and good stability, had good stability of film forming.

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.

Polymer-virus core-shell structures prepared via co-assembly and template synthesis methods

Bionanoparticles(BNPs),consisting of virus and virus-like assemblies,have attracted much attention in the biomedical field for their applications such as imaging and targeted drug delivery,owing to their well-defined structures and well-controlled chemistries.BNPs-based core-shell structures provide a unique system for the investigation of biological interactions such as protein-protein and protein-carbohydrate interactions.However,it is still a challenge to prepare the BNPs-based core-shell structures.Herein,we describe(i) co-assembly method and(ii) template synthesis method in the development of polymer-BNPs core-shell structures.These two methods can be divided into three different systems.In system A,different polymers including poly(2-vinylpyridine)(P2VP),poly(4-vinylpyridine)(P4VP) and poly(ε-caprolactone)-block-poly(2-vinylpyridine)(PCL-b-P2VP) can form a raspberry-like structure with BNPs.In system B,polystyrene(PS) spheres end capped with free amine and BNPs can form a core-shell structure.In System C,layer-by-layer(LBL) method is used to prepare positive charged PS particles,which can be used as a template to form the core-shell structures with BNPs.These two methods may open a new way for preparing novel protein-based functional materials for potential applications in the biomedical field.

大粒径聚丁二烯胶乳制备工艺对ABS树脂性能影响

一步法和附聚法是工业上生产大粒径聚丁二烯胶乳(PBL)的主要方法。采用一步法、高分子附聚法和醋酸附聚法制备出一系列具有300 nm粒径的PBL胶乳,并通过相同的接枝、掺混和加工流程以获得相应工艺的丙烯腈-丁二烯-苯乙烯(ABS)树脂,系统地研究了乳胶粒子构建方式对ABS树脂性能的影响。研究表明,三种工艺制备出的ABS树脂力学性能相当,但一步法胶乳制备的ABS树脂断裂伸长率明显优于其他二者,其数值达到35.41%。高分子附聚法制备的ABS树脂在三者之中具有最佳的白度值,为54.8%。三种方法构建的PBL粒子本质区别在于粒子内部结合程度不同,其中一步法的粒子结合程度最高,高分子附聚法的次之,而醋酸附聚法的最低。本研究对于ABS树脂工艺路线改造升级和工业产品质量提升具有一定的指导意义。

聚合物乳胶粉改性碳纤维增强混凝土的配合比设计

为提高碳纤维在混凝土中的分散性,利用可再分散聚合物乳胶粉与短切碳纤维对混凝土进行复合改性,运用正交试验方法,基于L_(9)(4^(3))正交试验表,设计两批18(2×9)组聚合物乳胶粉-碳纤维复合改性混凝土(PMCFRC)的坍落度、28d抗压强度及纤维分散性检测试验。第1批正交试验研究了水灰比、聚合物掺量、碳纤维掺量对PMCFRC性能的影响,第2批正交试验研究了分散剂种类、分散剂掺量、减水剂掺量对PMCFRC性能的影响,获得PMCFRC的坍落度、抗压强度、电阻率等基本参数,并利用极差和方差分析方法,研究各因素的主次顺序,分析其是否影响显著,基于此寻找出PMCFRC最优配合比。结果表明:第1批正交试验中,对于坍落度、电阻率以及电阻率变动系数,碳纤维掺量为显著因素;对于28d抗压强度,水灰比为显著因素;第2批正交试验中,对于坍落度和28d抗压强度,减水剂掺量为显著因素;对于电阻率和电阻率变动系数,分散剂掺量为显著因素。PMCFRC最佳配合比为:水灰比0.49,聚合物掺量12%,碳纤维掺量0.3%,砂率34%,分散剂选用羟乙基纤维素,分散剂掺量0.4%,减水剂掺量1.2%,消泡剂掺量0.3%。

可再分散乳胶粉与PE纤维对喷射混凝土性能的影响

研究了可再分散丙烯酸酯-苯乙烯共聚物乳胶粉(PRAS)和聚乙烯纤维(PE纤维)对喷射混凝土力学性能和抗冻性能的影响。结果表明:复掺适量PRAS和PE纤维能够显著提高喷射混凝土的抗压强度和抗折强度,降低冻融循环后的质量损失率和提高相对动弹性模量;当PRAS掺量为0.4%、PE纤维体积掺量为1.0%时,喷射混凝土的力学性能和抗冻性能最佳。