Poly(methyl methacrylate)‐grafted cellulose nanocrystals: One‐step synthesis,nanocomposite preparation,and characterization

Cellulose nanocrystals (CNCs) are ideal reinforcing agents for polymer nanocomposites because they are lightweight and nano‐sized with a large aspect ratio and high elastic modulus. To overcome the poor compatibility of hydrophilic CNCs in non‐polar composite matrices, we grafted poly(methyl methacrylate) (PMMA) from the surface of CNCs using an aqueous, one‐pot, free radical polymerization method with ceric ammonium nitrate as the initiator. The hybrid nanoparticles were characterized by CP/MAS NMR, X‐ray photoelectron spectroscopy, infrared spectroscopy, contact angle, thermogravimetric analysis, X‐ray diffraction, and atomic force microscopy. Spectroscopy demonstrates that 0.11 g/g (11 wt %) PMMA is grafted from the CNC surface, giving PMMA‐g‐CNCs, which are similar in size and crystallinity to unmodified CNCs but have an onset of thermal degradation 45 °C lower. Nanocomposites were prepared by compounding unmodified CNCs and PMMA‐g‐CNCs (0.0025–0.02 g/g (0.25–2 wt %) loading) with PMMA using melt mixing and wet ball milling. CNCs improved the performance of melt‐mixed nanocomposites at 0.02 g/g (2 wt %) loading compared to the PMMA control, while lower loadings of CNCs and all loadings of PMMA‐g‐CNCs did not. The difference in Young's modulus between unmodified CNC and polymer‐grafted CNC composites was generally insignificant. Overall, ball‐milled composites had inferior mechanical and rheological properties compared to melt‐mixed composites. Scanning electron microscopy showed aggregation in the samples with CNCs, but more pronounced aggregation with PMMA‐g‐CNCs. Despite improving interfacial compatibility between the nanoparticles and the matrix, the effect of PMMA‐g‐CNC aggregation and decreased thermal stability dominated the composite performance.     

Sorption of propylene and propane in polyurethane membranes containing silver nanoparticles

The preparation of a facilitated transport membrane of polyurethane (PU) containing silver nanoparticles is reported. The propylene and propane sorption was investigated aiming at the selective separation from C3s mixtures. The silver particles were photogenerated in situ into the polyurethane matrix using UV light radiation and silver triflate (AgCF₃SO₃) as precursor. The morphological properties of these membranes (PUAg) reveled great dispersion of silver particles, which size was smaller than 110 nm. The propylene solubility in PUAg resulted more than four times superior to the one for the pure PU membrane, revealing the high affinity between silver and propylene. Flory–Huggins theory was more accurate to describe the propylene sorption behavior in PUAg than Henry's model. The ideal solubility selectivity of PUAg membrane resulted 24.4, indicating that there is a good potential for an industrial application aiming at the separation of propylene/propane. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42916.     

Dissipative particle dynamics studies on the interfacial tension of A/B homopolymer blends and the effect of Janus nanorods

Janus nanorods are used as a novel rigid compatibilizer to improve the interfacial tension of incompatible A/B homopolymer blends. Dissipative particle dynamics (DPD) methods are preformed to explore the effect of Janus nanorods on the interfacial tension. The results show that Janus nanorods are a good compatibilizer only when the appropriate length is chosen, which is different from the traditional coil compatibilizer (surfactants and block copolymers). The length of the Janus nanorods can significantly influence their orientation through the competition between the entropic and enthalpic effects. The shorter Janus nanorods preferring “standing” have a better efficiency in improving the interfacial tension than the longer ones preferring “lying.” If we can control the orientation of the longer Janus nanorods, they are still a good compatibilizer. This simulation work can widen the application of Janus nanoparticles. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44098.     

Conducting polymerized high‐internal‐phase emulsion/single‐walled carbon nanotube nanocomposite foams: Effect of the aqueous‐phase surfactant type on the morphology and conductivity

Poly(styrene‐co‐divinylbenzene)/single‐walled carbon nanotubes (SWCNTs) polymerized high‐internal‐phase emulsion (polyHIPE) nanocomposite foams were successfully synthesized with various types of aqueous‐phase surfactants. The effects of anionic, cationic, nonionic, and mixed surfactants on the morphology and electrical conductivity of the resulting nanocomposite foams were investigated. The use of an anionic surfactant, sodium dodecylbenzesulfonate (SDBS), did not completely result in the typical polyHIPE nanocomposite foam microstructure because of the partial instability of the high‐internal‐phase emulsion. The nanocomposite foams synthesized by nonionic surfactants, that is, Pluronic F127 and Triton X‐100, and the cationic/anionic mixture, cetyltrimethylammonium bromide/SDBS, exhibited the proper morphology, but the resulting nanocomposite foams were electrically insulators. Interestingly, the use of a Gemini‐like surfactant, sodium dioctylsulfosuccinate (SDOSS), significantly improved both the typical morphology and electrical properties of the resulting nanocomposite foams because of the probable stronger interactions of SDOSS molecules with SWCNTs. The typical morphology of the nanocomposite foam synthesized with the SDOSS/F127 mixed surfactant was significantly improved, but the electrical conductivity decreased to some extent compared with the SDOSS‐synthesized nanocomposite foams. This behavior was attributed to an increase in the tunneling length of the electrons between adjacent SWCNTs. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43883.     

Influence of TiO2 nanoparticles on nonisothermal crystallization of PP in a wide range of cooling rates analyzed by fast scanning DSC

The influence of titanium dioxide (TiO₂) nanoparticles on the crystallization behavior of polypropylene was investigated by conventional differential scanning calorimetry (DSC) and fast scanning DSC measurements. The data obtained from both methods were estimated for the first time using the Lauritzen‐Hoffmann equation to analyze the behavior over a wide cooling range under nonisothermal conditions. This provides more reliable values of nucleation parameters (K_g) and surface free energy (σ_e). The variation of the effective energy (ΔE) was determined with the Kissinger method. Regardless of the cooling rate, both K_g and σ_e indicate the role of titania as a nucleating agent enhances the crystallization rate. However, the ΔE denotes that TiO₂ acts as an obstacle to the mobility of chain segments at cooling rates below 150 °C/s, while, in contrast, the presence of titania enhances the chain mobility at cooling rates above 150 °C/s. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43944.     

Thin film composite forward osmosis membranes with poly(2‐hydroxyethyl methacrylate) grafted nano‐TiO2 as additive in substrate

The poly(2‐hydroxyethyl methacrylate) grafted titanium dioxide nanoparticles were synthesized and added to the substrate of flat‐sheet thin film composite forward osmosis (TFC‐FO) membranes. The hydrophilicity of substrate was improved, which was advantageous to enhance the water flux of TFC‐FO membranes. The membranes containing a 3 wt % TiO₂‐PHEMA in the substrate exhibited a finger‐like structure combined with sponge‐like structure, while those with lower or without TiO₂‐PHEMA content showed fully finger‐like structures. As for FO performance, the TFC‐FO membranes with 3 wt % TiO₂‐PHEMA content achieved the highest water flux of 42.8 LMH and 24.2 LMH against the DI water using 2M NaCl as the draw solution tested under the active layer against draw solution (AL‐DS) mode and active layer against feed solution (AL‐FS) mode, respectively. It was proven that the hydrophilic property of membrane substrates was a strong factor influencing the water flux in FO tests. Furthermore, the structural parameter was remarkably decreased with an increase of TiO₂‐PHEMA content in membrane substrate, indicating the reducing of internal concentration polarization. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43719.     

Effect of protein adsorption on cell uptake and blood clearance of methoxy poly(ethylene glycol)‐poly(caprolactone) nanoparticles

The interactions between nanoparticles and cells or tissues are frequently mediated by different biomolecules adsorbed onto the surface of nanoparticles. In this study, several methoxy poly(ethylene glycol)‐poly(ε‐caprolactone) (mPEG‐PCL) copolymers with various mPEG/PCL ratios were synthesized and used to produce three types of mPEG‐PCL nanoparticles. The protein‐adsorption behavior of nanoparticles was assessed using fetal‐bovine‐serum (FBS) as a model protein. The cell uptake of nanoparticles at different nanoparticle doses as well as various culture periods was examined by measuring their endocytosis rate related to Hela cells cultured in FBS‐free and FBS‐contained media. The blood clearance of nanoparticles was evaluated using Kunming mice to see the differences in circulation durations of nanoparticles. Results suggest that that FBS is able to significantly regulate the cell uptake of nanoparticles in vitro, and on the other hand, the size and mPEG/PCL molar ratio of mPEG/PCL nanoparticles are closely correlated to their blood clearance. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42884.     

Spider Silk-CBD-Cellulose Nanocrystal Composites: Mechanism of Assembly

The fabrication of cellulose-spider silk bio-nanocomposites comprised of cellulose nanocrystals (CNCs) and recombinant spider silk protein fused to a cellulose binding domain (CBD) is described. Silk-CBD successfully binds cellulose, and unlike recombinant silk alone, silk-CBD self-assembles into microfibrils even in the absence of CNCs. Silk-CBD-CNC composite sponges and films show changes in internal structure and CNC alignment related to the addition of silk-CBD. The silk-CBD sponges exhibit improved thermal and structural characteristics in comparison to control recombinant spider silk sponges. The glass transition temperature (Tg) of the silk-CBD sponge was higher than the control silk sponge and similar to native dragline spider silk fibers. Gel filtration analysis, dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and cryo-transmission electron microscopy (TEM) indicated that silk-CBD, but not the recombinant silk control, formed a nematic liquid crystalline phase similar to that observed in native spider silk during the silk spinning process. Silk-CBD microfibrils spontaneously formed in solution upon ultrasonication. We suggest a model for silk-CBD assembly that implicates CBD in the central role of driving the dimerization of spider silk monomers, a process essential to the molecular assembly of spider-silk nanofibers and silk-CNC composites.     

基于低共熔溶剂电沉积铁纳米晶体：过电位、氢键给体对形貌的影响

系统研究铁在3种低共熔溶剂中的电沉积行为以及过电位和氢键给体对铁沉积物形貌的影响。结果表明,在DES1和DES2中,过电位对铁沉积物形貌没有明显影响,但在DES3中过电位对铁纳米粒子的形貌有显著影响。此外,研究结果还证实了氢键给体的种类对铁沉积物的形成有着密切的联系:尿素氢键给体有助于片状网络结构铁膜的形成;乙二醇氢键给体有助于准球形铁纳米粒子的形成;而乙二醇和丙二酸氢键给体的协同作用有助于空心球和类毛线球状等纳米粒子的形成。