Performance of flame retardancy silk modified with water‐soluble vinyl phosphoamide

In this article, a water‐soluble flame retardant monomer dimethyl(methacryloyloxyethyl)phosphoramidate (DMMEPN) was synthesized and applied onto silk fabric via graft copolymerization technique initiated with potassium persulfate (KPS). The results of attenuated total reflection infrared spectroscopy (ATR), scanning electron microscope (SEM) and energy dispersive X‐ray spectroscopy (EDS) indicated that DMMEPN was successfully grafted onto silk fiber surface. X‐ray diffraction (XRD) patterns showed that grafting process didn't change the crystalline structure of silk fibers and the reaction mainly occurred at the amorphous region of silk fibers. DMMEPN grafted silk fabric exhibited self‐extinguish property when ignited with a candle like fire with LOI of 32.38% and could pass vertical flammability test with char length of 42 mm. Thermal gravimetric analysis showed that grafted silk fibers had different thermal decomposition mode with control silk fibers and tended to produce more char after combustion. This article also investigated the physical properties like whiteness index, hygroscopicity, and tensile strength of grafted silk fabrics. The results showed that physical properties had some loss but had no negative effect on final uses. Laundering durability test demonstrated treated silk fabrics still showed flame retardancy after enduring 30 hand wash cycles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Microencapsulation of APP‐I and influence of microencapsulated APP‐I on microstructure and flame retardancy of PP/APP‐I/PER composites

In this article, the microencapsulated ammonium polyphosphate crystalline with form I (APP‐I) coated with melamine‐formaldehyde (MF) was prepared by in situ polymerization. Results of Fourier transform infrared spectra (FTIR), thermogravimetry (TG) energy dispersive spectroscopy (EDS), and scanning electron microscopy (SEM) demonstrate that APP‐I is successfully microencapsulated with MF. Compared with APP‐I, the microencapsulated APP‐I with MF (MFAPP‐I) is of much smaller spheroidal particle size and lower solubility in water. In this study, the polypropylene (PP)/APP‐I/penpaerythritol (PER) and PP/MFAPP‐I/PER composites are prepared, and flame retardancy, thermal stability, and microstructure of corresponding composites are carefully investigated by limiting oxygen index (LOI), UL‐94 testing, TG, EDS, and SEM. Experimental results show that PP/MFAPP‐I/PER composites have advantages over PP/APP‐I/PER composites in terms of flame retardant properties and water resistance. Results of TG, SEM, and EDS show that the microencapsulated APP‐I with MF resin is conducive to increase the amount of residual yield and improve thermal stability of PP/MFAPP‐I/PER composites and the compatibility and dispersion of MFAPP‐I. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Copolymerization of ethylene/5‐ethylidene‐2‐norbornene with bis (2‐phenylindenyl) zirconium dichloride catalyst: I. Optimization of the operating conditions by response surface methodology

In this study, the copolymerization of ethylene with nonconjugated diene (5‐ethylidene‐2‐norbornene) was carried out with a bis(2‐PhInd) ZrCl₂ metallocene catalyst. Some polymerization factors that were considered affective on the catalyst activity, including comonomer content in the feed, ethylene pressure, and polymerization temperature, were investigated via response surface methodology to determine the optimum polymerization conditions. We found that the comonomer content in the feedstock had no enormous effect on the catalyst activity depression. Also, the polymerization temperature increment through the scrutinized range decreased the copolymerization activity. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of the carbon black structure on the stability and efficiency of the conductive network in polyethylene composites

Composites of high‐density polyethylene (HDPE) with different kinds of carbon black (CB) were prepared through melt blending. The influence of the CB structure on the stability and efficiency of the conductive network in HDPE/CB composites were mainly investigated. Scanning electron microscopy was used to observe the morphology of the CB primary aggregates. The relationship between the temperature‐resistivity behaviors of the composites and the crystallization behaviors of the matrix were also investigated. High‐structure CB built an effective conductive network at a low filler content compared to the low‐structure one because of its branched morphology. Therefore, the composite containing high‐structure CB revealed a lower percolation threshold. The composite containing low‐structure CB obtained a stronger positive temperature coefficient (PTC) intensity because the cluster network was fragile and easily damaged during matrix melting. The reproducibility of the results of PTC effect of the composite containing high‐structure CB was better than that of the composite containing a low‐structure one. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of stable luminescent poly(methyl methacrylate)–europium complex nanospheres and application in the detection of hydrogen peroxide with the biocatalytic growth of gold nanoparticles

A simple and effective solvent swelling method was developed for the preparation of poly(methyl methacrylate) (PMMA)/europium (Eu) complex hybrid nanospheres. Transmission electron microscopy and dynamic light scattering results indicate that the as‐prepared PMMA–Eu nanoparticles had a spherical morphology, with a narrow particle size distribution ranging from 100–200 nm. The PMMA–Eu nanospheres exhibited strong red emissions with a maximum peak at 612 nm under UV excitation, and the luminescence lifetime of the Eu complex was enhanced after it was swollen into PMMA nanospheres. Furthermore, the luminescence intensity of the PMMA–Eu nanospheres was very stable in various severe media, including aqueous solutions with various pHs, 1 mM Ca²⁺, 1 mM Fe²⁺, 1 mM Cu²⁺, 0.1M phosphate‐buffered saline solution, 1 mM citric acid solution, 1 mM lysine, and 1 mM glutamic acid. After the nanospheres were incubated at various temperatures for 1 h, the luminescence properties remained stable when the temperature was less than 40°C yet decreased slightly between 40 and 60°C and decreased rapidly at higher temperatures. These luminescent nanospheres were successfully applied in the luminescence‐sensing assay of hydrogen peroxide and exhibited a high sensitivity and broad linear concentration range. Because of their unique luminescence properties, the as‐synthesized PMMA–Eu nanospheres are expected to have great potential for use as luminescent labels or probes for long‐time imaging and analysis in which severe media situations are present. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of anionic ion exchange latex particles via heteroaggregation

To prepare relatively large negatively charged polymer particles in a size range from 0.3 μm to 0.5 μm, having high surface charge densities, the heteroaggregation of small (50–100 nm), highly charged (185 and 421 μeq/g) anionic polystyrene particles onto the surface of larger (317–466 nm) poly(vinylbenzyl choride)‐based cationic (10, 614, and 830 μeq/g) particles was carried out. As a result, particles with different surface charges, having a core‐shell structure, were successfully prepared. First, aggregated particles were formed via heteroaggregation of the lowest surface charge density anionic particles (185 μeq/g) with the lowest surface charge density cationic particles (10 μeq/g). However, the anionic particles in the shell layer desorbed with time owing to the relatively weak interaction between the two particles. Second, aggregated particles comprised of the highest surface charge density cationic (830 μeq/g) and anionic latex particles (421 μeq/g) were formed. However, to prepare a stable system, an excess of the small anionic particles was required, leaving a large number of small particles present in the aqueous phase, which proved difficult to remove. Finally, aggregated particles were formed by heteroaggregation of cationic particles with an intermediate surface charge density (614 μeq/g) with the highest surface charge anionic particles (421 μeq/g). As a result, not only were core‐shell particles formed, but few free small anionic particles remained in the aqueous phase. In this article, the preparation and characterization of each of these aggregates are discussed in terms of particle size, morphology, and extent of incorporation of the functional groups. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of functionalized lignin beads from oak wood alkaline lignin

Alkaline lignin extracted from oak wood cooperage wastes was chemically modified to prepare beads by suspension polymerization on water without the use of organic solvents. These beads were macroporous and swelled in hydrophilic solvents. They were functionalized under microwaves to be used as scavenging agents in winery applications. The beads prepared by this approach have the advantage of being more acceptable by winemakers than synthetic polymer supports previously reported. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013     

高剪切应力对苯乙烯-乙烯/丁烯-苯乙烯三嵌段聚合物马来酸酐化反应的影响

通过提高双螺杆挤出机螺杆转速的应力引发方法,研究了高剪切应力下马来酸酐(MAH)与苯乙烯-乙烯/丁烯-苯乙烯三嵌段聚合物(SEBS)的官能化反应。结果表明,随着双螺杆挤出机螺杆转速的提高,官能化产物的接枝率和熔体流动速率明显增大。高剪切应力的作用引起大分子链断链,形成大分子自由基,从而引发SEBS的接枝反应。通过提高螺杆转速可有效地抑制交联副反应,制得接枝率较高(质量分数0.79%～0.89%)、熔体流动速率适宜(1.859～4.398 g/min)和凝胶含量较低(质量分数不大于0.32%)的官能化产物。同时,由应力诱导引发所得官能化产物SEBS-g-MAH对尼龙(PA 66)的增韧效果较好,其共混物的悬臂梁缺口冲击强度能达到约94 kJ/m2,较纯PA 66提高30余倍,而其拉伸和弯曲强度的下降并不剧烈。     

Sizing removal and functionalization of the carbon fiber surface studied by combined TOF SIMS and XPS

Time-of-flight secondary ion mass spectrometry (TOF SIMS) and X-ray photoelectron spectroscopy (XPS) have been jointly used to study a two-step surface processing of AS4 carbon fiber: extraction of sizing in CH₂Cl₂ and functionalization with trimellitic anhydride. The combined information on molecular specificity obtained with TOF SIMS and quantification obtained with XPS allows us to follow qualitatively and quantitatively the changes in functional groups on the carbon surface. The results show that the sizing on AS4 contains at least four different compounds. These compounds can be extracted in CH₂Cl₂ and the elimination is almost complete for silicone. The functionalization of AS4 with trimellitic anhydride has been realized. The reaction takes place between the amine groups on the carbon fiber and the two types of functional groups in trimellitic anhydride.     

Time-of-flight SIMS and in-situ XPS study of O2 and O2-N2 post-discharge microwave plasma-modified high-density polyethylene and hexatriacontane surfaces

The O₂ and O₂-N₂ ([N₂] < 15%) post-discharge microwave plasma modifications of high-density polyethylene (HDPE) and hexatriacontane (HTC) surfaces have been studied as a function of the distance from the discharge and the gas composition. They are compared in terms of the in-situ XPS O/C ratios and C 1s components, and the ex-situ ToF-SIMS O^-/CH^- ratios and relative intensities of series of peaks. The results on the effect of the distance from the discharge showed a clear correlation between the in-situ XPS results and the O₂ post-discharge modeling, exhibiting the double role of oxygen atoms: functionalization initialization by creating radicals (which react with molecular oxygen) and degradation due to the energy released by the oxygen atom recombination process. Specific in-situ XPS and ex-situ ToF-SIMS signatures of this in-situ degradation related to the oxygen atom recombination process were exhibited. When N₂ was introduced in the plasma gas, the in-situ XPS results and the ex-situ ToF-SIMS results were very different. The in-situ functionalization decreased as a function of the N₂ addition and the ex-situ functionalization exhibited a high maximum for the 5% N₂-95% O₂ post-discharge plasma and then decreased. Despite the absence of a complete O₂-N₂ post-discharge modeling, it can be assumed that there is also a maximum of the oxygen atom content for the 5% N₂-95% O₂ post-discharge. Thanks to the in-situ XPS and ex-situ ToF-SIMS specific signatures, it was also shown that this maximum corresponds to a low in-situ degradation effect. Nitrogen introduction could influence the role of oxygen atoms in such a way that there is a decrease in oxygen atom recombination processes (thus in degradation) for small N₂ addition and even a decrease in oxygen functionalization initialization for further N₂ incorporation in the plasma gas. No nitrogen was observed in the in-situ XPS results, whereas some ex-situ ToF-SIMS nitrogen-containing ions were observed for the O₂ and O₂-N₂ post-discharge. However, their relative intensities followed the variation in oxidation and not the variation in N₂ concentration in the plasma gas. They could be related to a post-treatment functionalization effect. Differences observed between HDPE and HTC are explained in terms of their structural differences (desorption of low molecular weight oxygen-containing fragments for HTC).