Polymerization compounding of HDPE/Kevlar composites. I. Morphology and mechanical properties

The aim of this work is to perform the polymerization compounding to improve the properties of Kevlar/PE composites. The approach consists in involving the surface of a reinforcement in a polymerization process of a polymer to be used either as a matrix in the final composite or as a special surface treatment to enhance solid/polymer interface properties in the composite. The polymerization compounding process is illustrated here with the polyaramid fibers as reinforcements and polyethylene as a matrix. The number of active sites on the fiber surface, initially insufficient to anchor the catalyst, were increased by a hydrolysis reaction prior to the polymerization. The anchored catalyst was subsequently used to conduct the Ziegler–Natta polymerization reaction of ethylene. The modified fibers were incorporated into the polyethylene resin to produce composites at fiber concentrations as high as 15 wt%. The morphology of the fibers and the composites was tested using electron microscopy. Finally, the mechanical properties of the composites (in impact and tensile tests) were measured to characterize the properties of model composites. Polym. Compos. 27:129–137, 2006. © 2006 Society of Plastics Engineers.     

Composite magnetic particles: 2. Encapsulation of iron oxide by surfactant-free emulsion polymerization

This is a second paper in the series concerning the synthesis and characterization of composite polymeric particles with encapsulated magnetic iron oxide and bearing reactive β-diketone groups on the surface. Composite particles have been prepared by two-step method in which first step requires preparation of the iron oxide nano-particles and during second step iron oxide was encapsulated into formed poly(styrene/acetoacetoxyethyl methacrylate) (PS-AAEM) particles directly during polymerization process. It has been found that the modification of the iron oxide nano-particle surface with sodium oleate improves significantly the encapsulation during polymerization process. This procedure gives a possibility to obtain composite particles with raspberry morphology and both the particle size and iron oxide content can be varied. Change of monomer to iron oxide ratio gives a possibility to change effectively the morphology of hybrid particles, however, polydispersity of composite particles increases at higher content of magnetic particles in the system. Variation of AAEM concentration in reaction mixture at constant iron oxide particles concentration gives a possibility to control the particle size of formed hybrid microspheres. Composite particles were characterized by dynamic light scattering and electron microscopy (SEM) with respect to their particle size and morphology of the surface layer. X-ray diffraction (XRD) and magnetization measurements indicate presence of maghemite (γ-Fe₂O₃) in composite particles.     

Investigation for surface morphology variation of monodisperse polymer particle

Monodisperse polymer particles composed of polystyrene (PS) and poly(1,6‐hexanedioldiacrylate) were prepared via one‐step seeded polymerization using PS as seed particles. For the study, the effects of the molecular weight of seed polymer particles, the ratio of the absorbed hexanediol dimethacrylate (HDDA) to the seed polymer particles (swelling ratio), and the seeded polymerization rate on the surface morphology of poly(St‐HDDA) particles were investigated. It was observed that the crater‐shaped defect was at the surface of poly(St‐HDDA) particles, independent of the molecular weight of seed polymer, and swelling ratio. But its surface morphology could be controlled by changing the rate of the seeded polymerization. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2385–2394, 2007     

Morphological architecture of poly(p-oxybenzoyl) by modification of oligomer end-group

Influence of oligomer end-group on morphology of poly(4-oxybenzoyl) (POB) was examined by polymerizations of 4-acyloxybenzoic acids having different acyl groups. Polymerizations of 4-propionyloxybenzoic acid, 4-hexanoyloxybenzoic acid, 4-octanoyloxybenzoic acid and 4-decanoyloxybenzoic acid in liquid paraffin at 320 °C yielded needle-like or pillar-like POB crystals via crystallization of oligomers. On the other hand, the polymerization of 4-perfluorooctanoyloxybenzoic acid (FOBA) afforded microspheres having needle-like crystals on the surfaces. At an initial stage in the polymerization, microspheres having smooth surface were formed via liquid-liquid phase separation of oligomers prepared from FOBA owing to the low miscibility of perfluorooctanoyl end-group. Thereby the phase-separation behaviour of oligomers changed from liquid-liquid phase separation to crystallization at a middle stage in the polymerization and then needle-like crystals were formed on the surface of the microspheres. Chemical structure of the oligomer end-group affected significantly the phase-separation behaviour of oligomers and ultimately the morphology of POB.     

Polymer particles with a pomegranate-like internal structure via micro-dispersive polymerization in a geometrically confined reaction space I. Experimental study

The synthesis of micron-sized polymer particles with a core-shell pomegranate-like morphology is presented. The proposed polymerization technique takes advantage of a reaction-induced micro-phase separation within a suspended organic liquid droplet containing monomer, a chemical initiator, a steric stabilizer, and a poor solvent for the polymer. With an increase in monomer conversion, the monomer droplet suspended in a continuous aqueous medium is transformed first into a micro-capsule with a thick pericellular membrane, and eventually into a polymer particle packed with 300-500 nm polymer sub-particles. The experimentally observed evolution of particle morphology indicates that the reaction pathway is strongly influenced by micro-phase separation and transport phenomena. In the first stage of polymerization, a pseudo-homogeneous polymerization takes place at the droplet surface, followed by a starved macro-dispersive polymerization in the inner region where polymer precipitates out from the solvent phase as nano-sized sub-particles.     

Wettability of conducting polymers: From superhydrophilicity to superoleophobicity

The review reports most of the works realized in the field of the surface wettability based on conducting polymers. The surface wettability is highly depending on the intrinsic hydrophobicity of materials and the roughness geometry. Conducting polymers have unique properties allowing to tune the surface wettability, for example, by reversibly incorporating various hydrophobic/hydrophilic doping ions, by changing the nature of the polymerizable core or by functionalization with various hydrophobic/hydrophilic substituents. Conducting polymers are obtained by monomer oxidation using various strategies such as the chemical oxidative polymerization in solution, the electrochemical polymerization on conductive substrates or the vapor-phase polymerization, leading to have an easy control of the surface morphology at micro- or a nanoscale with a surface wettability going from superhydrophilicity to superoleophobicity.     

Controlling the morphology of polyurethane/polystyrene interpenetrating polymer networks for enhanced blood compatibility

Polyurethane (PU)/polystyrene (PS) IPNs were simultaneously synthesized at 80°C, controlling the reaction kinetics to change the morphology. Polymerization kinetics of styrene was controlled by the content of initiator, and that of polyurethane by the catalyst concentration. The effect of the initiator and the catalyst on the polymerization rate was analyzed by NMR spectroscopy and FTIR. Gelation time was also measured by using the advanced rheometric expansion system (ARES). Samples with sea‐and‐island morphology were obtained, when the polymerization rate of PS was relatively slow, and the phase separation time was long. When the polymerization rate of PS was relatively fast, and the phase separation time was short, cocontinuous morphology was obtained. The degree of phase separation and surface roughness decreased, as the rate of PU network formation was increased, and the phase‐continuity was increased. The in vitro blood‐compatibility tests showed that the surface roughness was an important factor on the adsorption of fibrinogens and platelets. A large amount of fibrinogens and platelets were adsorbed on the relatively rough surface of samples showing sea‐island morphology. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 379–387, 2002; DOI 10.1002/app.10358     

Atomic force microscopy and contact angle studies of polymerizable gemini surfactant admicelles on mica

Atomic force microscopy (AFM) was used to directly observe and characterize a polymer‐modified mica surface prepared using a polymerizable gemini surfactant. Normal tapping mode and contact mode AFM were used to image the treated mica surface morphologies in air and liquid environments, respectively. The root mean square (RMS) roughness of mica surfaces before and after surface modification and polymerization was analyzed from these scans. To determine the effect of styrene adsolubilization on the surfactant‐modified mica, AFM measurements of the modified mica were made at various styrene concentrations. Contact angle measurements were also made to further characterize the nature of the surfactant‐modified mica surface. The surface morphology and surface hydrophilicity were observed to be different for the modified mica after polymerization. In addition, the polymerized surface maintained its morphology after washing/desorption studies demonstrating the stability of the polymerized surfactant film. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The morphology evolution of polyethylene produced in the presence of a Ziegler-type catalyst anchored on the surface of multi-walled carbon nanotubes

Data are presented on the evolution of the morphology of polyethylene (PE) formed via in situ polymerization with different polymer yield over a Ziegler-type titanium-magnesium catalyst anchored on the CNT surface. Individual polymer microparticles are formed on the CNT surface at the initial polymerization stage (the yield of 2.5–10 g PE/g CNT) with the formation of PE/CNT composites having a shish-kebab structure. As the polymer yield increases above 10 g PE per g CNT, the size of microparticles increases and the CNT surface gets totally covered with the polymer. We have found also a great effect produced by the morphology of initial CNT particle aggregates of individual nanotubes on the morphology of macroparticles in PE/CNT composites and the uniformity of CNTs distribution in PE/CNT composites. In the case of CNT samples with a loose structure of macroparticles (aggregates of entangled nanotubes), it is possible to obtain a homogeneous distribution of nanotubes in the polymer matrix of composites and increase the electrical conductivity of composites by 1–8 orders of magnitude by varying the CNT content in the composites from 0.9 to 2.8 wt%.     

Encapsulation of nano Disperse Red 60 via modified miniemulsion polymerization. I. Preparation and characterization

Nanocolorant, nano Disperse Red 60, was successfully prepared via modified miniemulsion polymerization process. Transmission electron microscopy was employed to determine the droplet and particle sizes. The effects of the speed and the time of homogenization, the surfactant nature and its amount, the presence of dye, the initiator nature, and the presence of a crosslinker on the morphology and particle size of nanocolorant were studied. UV–vis absorption spectra of nanocolorant with respect to the commercial corresponding dye showed a hypsochromic shift confirming the decrease in particle size. Fourier transform infrared spectra proved the chemical composition of nanocolorant particles assisting the incorporation of the dye within the polystyrene particles. The monomer conversion, surface tension, and apparent sedimentation stability also were measured. The relative electrical conductivity of the suspension was used for determining the polymerization mechanism. The kinetic polymerization was investigated using a pseudofirst-order and it is found that the rate constant of polymerization equals 0.01358 min⁻¹. Zeta potential measurements were employed for miniemulsion which showed that it has good stability at all range of pH. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Morphology of high surface area polypyrrole structures

In this study pyrrole was electropolymerized into polymers having three types of morphology. In the first case, convoluted tubes and dendrites were deposited on filled polymeric and roughened electrodes. Secondly, free-standing fractals were formed, radiating from central anodes. In some instances the polymers were grown across filter papers located at the base of the anode and at the surface of the solvent. In the third instance, high surface area fibrillar forms were obtained by in-situ polymerization within coated, γ-alumina isoporous membrane hosts, followed by leaching in alkali. In all cases the morphology of these products is described by optical and scanning electron microscopy.     

Effect of molecular weight on the surface morphology of crosslinked polymer particles in the RITP-dispersion polymerization

The RITP (reverse iodine transfer polymerization)-dispersion polymerization of methyl methacrylate (MMA) was conducted and the molecular weight and SEM images of them were investigated to propose the mechanism of the formation of surface morphology in crosslinked polymers. The morphology of the crosslinked particles varied depending on the sorts and contents of the crosslinking agents and iodine. As the iodine content increased under the same content of the crosslinking agent, the average molecular weight of the polymers [uncrosslinked portion of the polymers] decreased and the surface roughness simultaneously reduced. On the other hand, as the contents of the crosslinking agent increased, the molecular weight of polymers reduced and the surface morphology changed from smooth to rough in the absence of iodine. On the other hand, was the molecular weight was barely changed and the solubility increased upon iodine. Thus the mechanism of the formation of crosslinked polymers in the RITP-dispersion polymerization was proposed as the following; when crosslinking agent and iodine were simultaneously involved, the low molecular weight of polymers were first formed due to the effect of iodine and then the crosslinking was taking place, resulting in that iodine was a critical factor in controlling the molecular weight, particle size, solubility and the surface morphology in the crosslinked polymer particles.     

烯烃聚合过程的分形演化及其生长模型

The surface morphology of Ti-Mg supported catalyst and the polyethylene particles are studied using scanning electron microscope(SEM) technology.The results show that either the catalyst‘s surface or polymer particle‘s surface is irregular and has fractal characteristics,which can be described by fractal parameter.The more interesting discovery is that the surface fractal dimension values of the polymer particles vary periodically with the polymerization time.We call this phenomenon fractal evolution,which can be divided into the “revolution“ stage and the “evolution“ stage,And then we present polymerization fractal growing model(PFGM),and successfully describe and /or predict the whole evolving process of the polyethylene particle morphology under the different slurry polymerization(including pre-polymerization) conditions without H2.     

Study on preparation and process of poly(MMA-St) thermally expandable core-shell microspheres

Thermally expandable microspheres were synthesized by the suspension polymerization of methyl methacrylate (MMA) and styrene (St) in the presence of paraffin blowing agents. The effect of the monomer composition, the initiator, the blowing agent, the polymerization temperature on the morphology and structure of microspheres were studied. The results showed that AIBN initiated the water phase polymerization of MMA to form secondary polymer particles adsorbed on the surface of the microspheres. MMA diffused from the oil phase to the water phase, which accelerated the phase separation and facilitated the formation of core-shell microspheres. However, LPO could not initiate the water phase polymerization, the phase separation was slow and there was an intermediate state with a porous surface. When the boiling point of the blowing agent was lower than the polymerization temperature, the microspheres were porous and there were a large number of holes on the surface.     

Kinetics of heterogeneous polymerization of vinylidene chloride. I. Mechanism and modeling

The similarities and differences between the heterogeneous polymerization of vinylidene chloride (VDC) and vinyl chloride (VC) were compared and analyzed. The effect of the poly(vinylidene chloride)(PVDC) crystal morphology on the kinetics of VDC polymerization was discussed. Based on the assumption that polymerization occurs in the monomer phase and on the edges of the PVDC lamellar crystals, a mechanism of VDC polymerization is proposed and then a kinetic model for VDC bulk/suspension polymerization is developed according to the elementary reactions. The model can be used to predict polymerization rate and conversion. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2576‐2581, 2004     

成膜温度对漆膜表面形态的影响

采用种子乳液法合成了核壳结构苯丙乳液，用原子力显微镜(AFM)对不同成膜温度漆膜表面形态，尤其是乳化剂在漆膜表面的分布进行了研究。发现控制乳液的成膜温度略高于Tg，可以得到粒子排列整齐的均一膜，膜的耐水性等性能更好。     

酸浓度和聚合周期对DBSA掺杂PANI结构性能的影响

采用循环伏安法在镀金PET膜上聚合得到了十二烷基苯磺酸(DBSA)掺杂的聚苯胺(PANI)膜,通过对比不同条件下所得PANI膜的红外光谱、微观形貌、循环伏安特性、X射线衍射谱图和紫外-可见光-近红外反射光谱,研究了DBSA浓度和聚合时间对PANI结构和性能的影响。结果表明,DBSA可以通过电化学聚合过程掺入PANI分子链,由于长链烷基的增容作用,PANI呈纤维状。电化学聚合过程中,随DBSA浓度增大,PANI成核速率增加,易形成片状致密结构,造成PANI膜结晶度升高、离子空间位阻变大,且膜的光谱反射率逐渐降低。随聚合时间的增加,PANI表面形貌逐渐变差,出现团簇现象,成核速率逐渐增加,PANI纤维横向生长形成带状。     

表面改性对聚丙烯/微米氢氧化镁复合材料性能的影响

研究了表面处理剂（钛酸酯和硅烷偶联剂）和原位聚合方法对聚丙烯/微米氢氧化镁（MH）复合材料的力学性能及流变性能的影响。采用DSC、SEM和毛细管流变仪对PP/MH（80/20）复合材料的性能进行了研究。结果表明：原位聚合改性后的微米MH与PP基体间的界面黏结力得到了加强,复合材料的冲击强度较填充未改性MH的复合材料提高了26.4 ％。在PP基体中添加聚合物包覆改性微米MH粒子的复合材料熔体流动速率较纯PP上升了64 ％。在相同剪切速率下,填充聚合物包覆改性MH的复合材料熔体表观黏度明显低于填充未改性微米MH的复合材料,表明聚合物包覆改性后的MH降低了其对PP熔体流动的阻碍作用,改善了PP/MH复合材料的流动性能。     

Morphology of latex particles formed by poly(methyl methacrylate)-seeded emulsion polymerization of styrene

Poly(methyl methacrylate)–polystyrene composite particle latexes were prepared by poly(methyl methacrylate)-seeded emulsion polymerization of styrene employing batch, swelling-batch, and semibatch methods. The changes in particle morphology taking place during the polymerization reaction were followed by electron microscopy. Anchoring effect exerted by ionic terminal groups introduced by ionic initiator was found to be the main factor in controlling the particle morphology. The polymer particles obtained by oil-soluble hydrophobic initiators such as azobisisobutyronitrile and 4,4′-azobis-(4-cyanovaleric acid) gave the inverted core-shell morphology. Water-soluble hydrophilic initiator, K₂S₂O₈, also gave the inverted core-shell morphology. However, in this case the occurrence of the halfmoonlike, the sandwichlike, and the core-shell morphologies were also observed depending upon the polymerization conditions. The distribution of terminal ? SO groups on the surface area of polystyrene particles could be controlled by initiator concentration and polymerization temperature. Viscosity of polymerization loci dictated the movement of polymer molecules, thus causing the unevenness of particle shape and phase separation at high viscosity state. Viscosity was controlled by the styrene/poly(methyl methacrylate) ratio, the addition of a chain transfer agent or a solvent which is common to polystyrene and poly(methyl methacrylate).     

Fabrication of two sites hydrophobicity on cotton surface – a fluoropolymerization approach

Cotton fabric on both surfaces was coated with polymerization of fluoromonomer followed by adsorption of fluorosurfactant by a new technique admicellar polymerization to obtain durable hydrophobicity. Water repellence properties were determined in terms of simple drop test contact angles. The coating on cotton fabric exhibited the right water contact angle of 137.23° and left contact angle 138.35° (an average value of 137.79°). However, the durability of the coatings was decreased after simple home laundering with a decrease in water contact angle value. The surface morphology was evaluated by scanning electron microscopy before and after polymerization. Beside this chemical composition on the cotton, the surface was evaluated by EDS analysis to determine the number of fluorine moieties deposited on the cotton surface by this technique.