Investigations on matrix network characteristics in NBR/silica nanocomposites: Resolving matrix bulk density and network molecular weight and their alterations due to filler‐curing agent interactions

Presence of filler in an elastomeric composite can affect curing characteristics due to possible interaction with curing agents. Alteration of the curing characteristics can change intrinsic properties of elastomer including its bulk density and swelling behavior. In this study, a series of acrylonitrile butadiene rubber (NBR) with various curing levels was prepared. From the experimental data the bulk density and network molecular weight (M_c,sw) were specified and a relationship was established between these parameters. In order to determine the swelling characteristics of NBR in presence of filler, another series of NBR/silica nanocomposites was prepared with various nanosilica loadings under a constant content of curing agents and curing conditions. With the use of the swelling data and applying the obtained relationship, the M_c,sw and bulk density of the filled NBR matrix were resolved. The M_c,sw values obtained by considering the influence of nanosilica on curing characteristics of NBR were compared with those obtained simply based on bulk density of raw rubber. This comparison confirmed that there are considerable differences between these values. With increasing nanosilica contents, and hence, increasing the negative impact of the filler on reducing curing degree of NBR, the bulk density of filled NBR matrix was decreased. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46170.     

Temperature dependency of gas barrier properties of biodegradable PP/PLA/nanoclay films: Experimental analyses with a molecular dynamics simulation approach

Polypropylene (PP)/poly(lactic acid) (PLA)/clay nanocomposite films with various compositions (PP‐rich and PLA‐rich) were prepared. Their structural and barrier properties against CO₂, O₂, and N₂ were investigated. The microstructure of the nanocomposites was studied by scanning electron microscopy, transmission electron microscopy, and wide angle X‐ray scattering. The PP‐rich with 75/25 composition revealed the best barrier properties against all the gases which could be justified according to its microstructure. Selectivity of O₂/N₂ and CO₂/N₂ was also measured. It was found that the addition of nanoclay as a gas barrier component reduced the permeability in both systems. The permselectivity was also reduced in the PP‐rich films while it was increased in the PLA‐rich system. Moreover, the temperature dependency of permeability, selectivity, and permselectivity for PP, PLA, and PP/PLA (75/25) samples was examined. The results showed that the temperature dependence of permeability obeyed an Arrhenius equation and order of activation energy of permeability for O₂, CO₂, and N₂ gases was found to be E_P < E_P/PLA < E_PLA. According to solubility measurements, the order of solubility coefficient for gases was as follows: CO₂ > O₂ > N₂. Finally, the molecular dynamics (MD) simulation was performed to estimate the diffusivity coefficients of the gases and showed that solubility increases with increasing temperature, which was in accordance with the experiments. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46665.     

Amide–acid functional SiO2 nanocomposites based on new semi‐crystalline poly(ether‐sulfone‐amide): thermal,combustion and mechanical studies

New amide–acid functional SiO₂ nanoparticle (FSNP)‐reinforced semi‐crystalline aliphatic–aromatic poly(ether‐sulfone‐amide) (PESA) was synthesized using a solution method in dimethylformamide. The surfaces of SiO₂ nanoparticles were functionalized with phthalic anhydride, and subsequently PESA was synthesized using direct polymerization with good yield and desired molar mass. PESA / SiO₂ nanocomposites (PSNCs) were prepared with three different contents of FSNP and the morphology and mechanical, thermal and combustion properties of the PSNCs were studied. The results of X‐ray diffraction, field‐emission scanning electron microscopy and transmission electron microscopy showed a uniform dispersion for FSNP in the PESA matrix. According to the results of mechanical tests, the tensile strength and the Young's modulus of PESA were enhanced by FSNP loading. Thermogravimetric analysis and derivative thermogravimetry results showed a substantial improvement in thermal properties of PESA. The temperature at 5% mass loss was increased from 371.7 to 395.8 °C for the PSNC containing 8 mass% of FSNP, as well as the char yield being enhanced greatly, which was about 30% higher than that of neat PESA. Significant improvements in combustion properties were observed for PSNCs from microscale combustion calorimetry. The peak heat release rate showed an obvious improvement and decreased by about 57% compared to that of neat PESA on 8 mass% loading of FSNP. © 2016 Society of Chemical Industry     

Graphene network enabled high speed electrical actuation of shape memory nanocomposite based on poly(vinyl acetate)

Here strong electroactive shape memory nanocomposites were prepared by incorporating graphene nanoplatelets into poly(vinyl acetate) (PVAc ) through the simple solvent mixing method. TEM and XRD revealed that well exfoliated graphene nanoplatelets formed a continuous network throughout the matrix with a large amount of interconnectedness. Dynamic mechanical analysis showed that the inclusion of graphene significantly improves both glassy and rubbery moduli of the matrix. Furthermore, the prepared nanocomposites demonstrated a marked electrical conductivity up to 24.7 S m^?1 and thereby surprisingly rapid electrical actuation behaviour exhibiting a 100% recovery ratio in 2.5 s. Moreover, PVAc and its nanocomposites displayed scratch self‐healing capability. This work demonstrates that the PVAc /graphene nanocomposites with high modulus and excellent electroactive shape memory performance can be a promising material in many applications such as sensors and fast deployable and actuating devices. © 2016 Society of Chemical Industry     

Optimizing the mechanical and physical properties of thermoplastic starch via tuning the molecular microstructure through co‐plasticization by sorbitol and glycerol

Nowadays, environmental hazards caused by plastic wastes are a major concern in academia and industry. Utilization of biodegradable polymers derived from renewable sources for replacing common petroleum‐based plastics is a potential solution for reducing the problem. In this regard, starch has become one of the most promising alternatives to non‐biodegradable polymers for depleting plastic waste thanks to its low expense, abundance, renewability and biodegradability. However, the main drawbacks of starch are its poor processability, weak mechanical properties and severe hydrophilicity. In this work, thermoplastic starch (TPS) samples have been prepared using glycerol and sorbitol as co‐plasticizers in a laboratory co‐rotating twin screw extruder. Based on the mechanical test results, glycerol caused higher elongation to break but had lower tensile strength and elastic modulus compared to sorbitol plasticized starch. Fourier transform infrared spectroscopy and DSC results indicated that the hydrogen bond interaction between starch chains and plasticizers could be improved by replacing glycerol by sorbitol, which resulted in higher resistance against retrogradation proved by XRD results. TGA illustrated that the higher the sorbitol to glycerol ratio was, the more stable was the TPS. Using a proper amount of plasticizers (42 wt% total plasticizer, sorbitol to glycerol ratio 2:1) led to the preparation of a TPS sample with optimized properties including enhanced mechanical properties, high thermal stability, strong hydrogen bond formation and high resistance against retrogradation. © 2017 Society of Chemical Industry     

Investigation on the morphological and mechanical properties of (polyamide 6)/(poly[styrene‐co‐acrylonitrile])/(poly[styrene‐b‐{ethylene‐co‐butylene}‐b‐styrene]) ternary blends

In this work, ternary polymer blends based on (polyamide 6)/(poly[styrene‐co‐acrylonitrile])/(poly[styrene‐b‐{ethylene‐co‐butylene}‐b‐styrene]) (SEBS) triblock copolymer and a varying concentration of the reactive (maleic anhydride)‐grafted SEBS were prepared by using a melt‐blending process. The effects of the material parameters (composition of ternary blends and SEBS/[{maleic anhydride}‐grafted SEBS] concentration ratio) and blending sequence on the morphological and mechanical properties of ternary blends were studied. Taguchi experimental design methodology was employed to design the experiments and select the material and processing parameters for the optimized mechanical properties. Tensile properties (Young's modulus and yield stress) and impact strength were considered as the response variables. It was demonstrated that there is a meaningful relationship between the composition of blends, processing parameters, observed phase structure, and obtained mechanical properties. The mechanical tests showed that the highest impact strength was achieved as the dispersion of the rubbery phase achieved an optimum size of about 1 μm. J. VINYL ADDIT. TECHNOL., 23:329–337, 2017. © 2015 Society of Plastics Engineers     

High‐performance carboxylate superplasticizers for concretes: Interplay between the polymerization temperature and properties

Polycarboxylate superplasticizers based on acrylic acid (AA) and maleic anhydride (MAn) were synthesized via free‐radical copolymerization with an ethylene glycol monomer and characterized. The copolymerization temperature (ranging from 50 to 90 °C) appeared to be the key operating factor governing the chemical structure of the superplasticizers. The chemical structures of the products were analyzed by gel permeation chromatography, whereas an optimized sample was further analyzed by Fourier transform infrared spectroscopy and ¹H‐NMR. Superplasticizers of the AA and MAn classes were then incorporated into concrete, and their performances were measured by slump and slump loss tests, where a large dependency of the microstructure on the synthesis temperature was recognized. The optimum temperatures were found to be 50 and 80 °C for the AA and MAn modifiers, respectively. At their own optimum temperatures, the AA and MAn superplasticizer revealed slump losses from 23 to 4 cm and 15 to 5 cm, respectively, after 45 min. The chemical structures of the plasticizers were patterned illustratively to speculate the performance of each superplasticizer according to changes that took place in the backbone length and side‐chain density. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44908.     

Chemical Functionalization of Graphene Oxide by Poly(styrene sulfonate) Using Atom Transfer Radical and Free Radical Polymerization: A Comparative Study

Poly(sodium styrenesulfonate)-functionalized graphene was prepared from graphene oxide, using atom transfer radical polymerization and free radical polymerization. In atom transfer radical polymerization route, the amine-functionalized GO was synthesized through hydroxyl group reaction of GO with 3-amino propyltriethoxysilane. Atom transfer radical polymerization initiator was grafted onto modified GO (GO-NH₂) by reaction of 2-bromo-2-methylpropionyl bromide with amine groups, then styrene sulfonate monomers were polymerized on the surface of GO sheets by in situ atom transfer radical polymerization. In free radical polymerization route, the poly(sodium 4-styrenesulfonate) chains were grafted on GO sheets in presence of Azobis-Isobutyronitrile as an initiator and styrene sulfonate monomer in water medium. The resulting modified GO was characterized using range of techniques. Thermal gravimetric analysis, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy results indicated the successful graft of polymer chains on GO sheets. Thermogravimetric analysis showed that the amount of grafted polymer was 22.5 and 31?wt% in the free radical polymerization and atom transfer radical polymerization methods, respectively. The thickness of polymer grafted on GO sheets was 2.1?nm (free radical polymerization method) and 6?nm (atom transfer radical polymerization method) that was measured by atomic force microscopy analysis. X-ray diffractometer and transmission electron microscopy indicated that after grafting of poly(sodium 4-styrenesulfonate), the modified GO sheets still retained isolated and exfoliated, and also the dispersibility was enhanced.     

A new blend of polymeric encapsulation of azithromycin by spray-drying with a pH responsive in drug release

The microencapsulation of macrolides with polymers has been reported to retard the release of the drug in oral cavity. However, these methods are unable to control drug release in gastrointestinal tract. The aim of the present study was to investigate the effect of formulation of a new polymeric encapsulation of azithromycin which is suitable for both masking and sustained release usage. Eudragit E100 and polyethylene glycol (PEG) 4000 were chosen as the barrier coatings. The spray drying technique was used to obtain the microcapsules containing azithromycin. To obtain the initial results, the effects of several parameters were evaluated. A 3:2:1 ratio of E100:PEG 4000:azithromycin at pH 6 gave the best coating condition. Thermogravimetric analysis and IR analysis data confirmed the encapsulation of azithromycin inside polymers. The encapsulated drug was released in different rates from the particles by changing the pH (1.7 and 7.4). An analysis of the kinetic release properties indicates that the release of the drug is a combination of swelling and diffusion mechanism. The synergistic cooperation between polymers and drug due to the existence of several hydrogen bonding is supposed to influence the pH-responsive property of the encapsulated drug. Moreover, the use of mixtures of E100 and PEG 4000 appears to offer a good balance between cost and efficiency.