Polymers, Volume 6, Issue 11 (November 2014) – 11 articles , Pages 2720-2895

Thermally reduced graphite oxide (TRGO), containing only four single carbon layers on average, was combined with ammonium polyphosphate (APP) and magnesium hydroxide (MH), respectively, in polypropylene (PP). The nanoparticle’s influence on different flame-retarding systems and possible synergisms in pyrolysis, reaction to small flame, fire behavior and mechanical properties were determined. TRGO has a positive effect on the yield stress, which is decreased by both flame-retardants and acts as a synergist with regard to Young’s modulus. The applicability and effects of TRGO as an adjuvant in combination with conventional flame-retardants depends strongly on the particular flame-retardancy mechanism. In the intumescent system, even small concentrations of TRGO change the viscosity of the pyrolysing melt crucially. In case of oxygen index (OI) and UL 94 test, the addition of increasing amounts of TRGO to PP/APP had a negative impact on the oxygen index and the UL 94 classification. Nevertheless, systems with only low amounts (≤1 wt%) of TRGO achieved V-0 classification in the UL 94 test and high oxygen indices (>31 vol%). TRGO strengthens the residue structure of MH and therefore functions as a strong synergist in terms of OI and UL 94 classification (from HB to V-0). Full article

Photochemically mediated reversible-deactivation radical polymerization of methyl methacrylate was successfully performed using 50–400 ppm of various copper compounds such as CuSO₄·5H₂O, copper acetate, copper triflate and copper acetylacetonate as catalysts. The copper catalysts were reduced in situ by irradiation at wavelengths of 366–546 nm, without using any additional reducing agent. Bromopropionitrile was used as an initiator. The effects of various solvents and the concentration and structure of ligands were investigated. Well-defined polymers were obtained when at least 100 or 200 ppm of any catalyst complexed with excess tris(2-pyridylmethyl)amine as a ligand was used in dimethyl sulfoxide as a solvent. Full article

The generation of nano-microstructured surfaces is a current challenge in polymer science. The fabrication of such surfaces has been accomplished mainly following two different alternatives i.e., by adapting techniques, such as molding (embossing) or nano/microimprinting, or by developing novel techniques including laser ablation, soft lithography or laser scanning. Surface instabilities have been recently highlighted as a promising alternative to induce surface features. In particular, wrinkles have been extensively explored for this purpose. Herein, we describe the preparation of wrinkled interfaces by confining a photosensitive monomeric mixture composed of monofunctional monomer and a crosslinking agent within a substrate and a cover. The wrinkle characteristics can be controlled by the monomer mixture and the experimental conditions employed for the photopolymerization. More interestingly, incorporation within the material of a functional copolymer allowed us to vary the surface chemical composition while maintaining the surface structure. For that purpose we incorporated either a fluorinated copolymer that enhanced the surface hydrophobicity of the wrinkled interface or an acrylic acid containing copolymer that increased the hydrophilicity of the wrinkled surface. Finally, the role of the hydrophobicity on the bacterial surface adhesion will be tested by using Staphylococcus aureus. Full article

Water-based polymer nanoparticle dispersions (solar paint) offer the prospect of addressing two of the main challenges associated with printing large area organic photovoltaic devices; namely, how to control the nanoscale architecture of the active layer and eliminate the need for hazardous organic solvents during device fabrication. In this paper, we review progress in the field of nanoparticulate organic photovoltaic (NPOPV) devices and future prospects for large-scale manufacturing of solar cells based on this technology. Full article

Magnesium phosphate cement (MPC) has been proven to be a very good repair material for deteriorated concrete structures. It has excellent adhesion performance, leading to high bonding strength with old concrete substrates. This paper presents an experimental study into the properties of MPC binder as the matrix of carbon fiber sheets to form fiber-reinforced inorganic polymer (FRIP) composites. The physical and mechanical performance of the fresh mixed and the hardened MPC paste, the bond strength of carbon fiber sheets in the MPC matrix, the tensile strength of the carbon FRIP composites and the microstructure of the MPC matrix and fiber-reinforced MPC composites were investigated. The test results showed that the improved MPC binder is well suited for developing FRIP composites, which can be a promising alternative to externally-bonded fiber-reinforced polymer (FRP) composites for the strengthening of concrete structures. Through the present study, an in-depth understanding of the behavior of fiber-reinforced inorganic MPC composites has been achieved. Full article

Electrorheological (ER) and magnetorheological (MR) suspensions undergo a reverse phase transition from a liquid-like to solid-like state in response to an external electric or magnetic field, respectively. This paper briefly reviews various types of electro- or magneto-responsive materials from either polymeric or inorganic and hybrid composite materials. The fabrication strategies for ER/MR candidates and their ER/MR characteristics (particularly for ER fluids) are also included. Full article

Bulk heterojunction (BHJ) organic photovoltaic (OPV) promise low cost solar energy and have caused an explosive increase in investigations during the last decade. Control over the 3D morphology of BHJ blend films in various length scales is one of the pillars accounting for the significant advance of OPV performance recently. In this contribution, we focus on the strategy of incorporating an additive into BHJ blend films as a morphological control agent, i.e., ternary blend system. This strategy has shown to be effective in tailoring the morphology of BHJ through different inter- and intra-molecular interactions. We systematically review the morphological observations and associated mechanisms with respect to various kinds of additives, i.e., polymers, small molecules and inorganic nanoparticles. We organize the effects of morphological control (compatibilization, stabilization, etc.) and provide general guidelines for rational molecular design for additives toward high efficiency and high stability organic solar cells. Full article

This study investigates chemical grafting with fatty acid chlorides as a method for the surface modification of hydrophilic web materials. The resulting changes in the water repellence and barrier properties were studied. For this purpose, different grades of polyvinyl alcohol (PVOH) were coated on regenerated cellulose films (“cellophane”) and paper and then grafted with fatty acid chlorides. The PVOH grades varied in their degree of hydrolysis and average molecular weight. The surface was esterified with two fatty acid chlorides, palmitoyl (C16) and stearoyl chloride (C18), by chemical grafting. The chemical grafting resulted in water-repellent surfaces and reduced water vapor transmission rates by a factor of almost 19. The impact of the surface modification was greater for a higher degree of hydrolysis of the polyvinyl alcohol and for shorter fatty acid chains. Although the water vapor barrier for palmitoyl-grafted PVOH was higher than for stearoyl-grafted PVOH, the contact angle with water was lower. Additionally, it was shown that a higher degree of hydrolysis led to higher water vapor barrier improvement factors after grafting. Furthermore, the oxygen permeability decreased after grafting significantly, due to the fact that the grafting protects the PVOH against humidity when the humidity is applied on the grafted side. It can be concluded that the carbon chain length of the fatty acid chlorides is the limiting factor for water vapor adsorption, but the grafting density is the bottleneck for water diffusing in the polymer. Full article

The miscibility and phase behavior of poly(4-vinylphenol) (PVPh) with poly(vinyl methyl ketone) (PVMK) was investigated by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). It was shown that all blends of PVPh/PVMK are totally miscible. A DSC study showed the apparition of a single glass transition (T_g) over their entire composition range. When the amount of PVPh exceeds 50% in blends, the obtained T_gs are found to be significantly higher than those observed for each individual component of the mixture, indicating that these blends are capable of forming interpolymer complexes. FTIR analysis revealed the existence of preferential specific interactions via hydrogen bonding between the hydroxyl and carbonyl groups, which intensified when the amount of PVPh was increased in blends. Furthermore, the quantitative FTIR study carried out for PVPh/PVMK blends was also performed for the vinylphenol (VPh) and vinyl methyl ketone (VMK) functional groups. These results were also established by scanning electron microscopy study (SEM). Full article

Coupling reactions were performed to gauge the effect of the inclusion of a radical trap on the success of coupling reactions of monohalogenated polystyrene (PSX) chains in atom transfer radical coupling (ATRC) type reactions. The effect of both the specific radical trap chosen and the structure of the polymer chain end were evaluated by the extent of dimerization observed in a series of analogous coupling reactions. The commonly used radical trap 2-methyl-2-nitrosopropane (MNP) showed the highest amounts of dimerization for PSX (X = Br, Cl) compared to coupling reactions performed in its absence or with a different radical trap. A dinitroxide coupling agent was also studied with the extent of coupling nearly matching the effectiveness of MNP in RTA (Radical trap-assisted)-ATRC reactions, while N-nitroso and electron rich nitroso coupling agents were the least effective. (2,2,6,6-Tetramethyl-piperin-l-yl)oxyl-capped PS (PS-TEMPO), prepared by NMP, was subjected to a coupling sequence conceptually similar to RTA-ATRC, but dimerization was not observed regardless of the choice of radical trap. Kinetic experiments were performed to observe rate changes on the coupling reaction of PSBr as a result of the inclusion of MNP, with substantial rate enhancements found in the RTA-ATRC coupling sequence compared to traditional ATRC. Full article

Proton exchange membranes (PEMs) are a key component of a proton exchange membrane fuel cell. Sulfonated polyimides (SPIs) were doped by protic ionic liquid (PIL) to prepare composite PEMs with substantially improved conductivity. SPIs were synthesized from diamine, 2,2-bis[4-(4-amino-phenoxy)phenyl]propane (BAPP), sulfonated diamine, 4,4'-diamino diphenyl ether-2,2'-disulfonic acid (ODADS) and aromatic anhydride. BAPP improved the mechanical and thermal properties of SPIs, while ODADS enhanced conductivity. A PIL, 1-vinylimidazolium trifluoromethane-sulfonate ([VIm][OTf]), was utilized. [VIm][OTf] offered better conductivity, which can be attributed to its vinyl chemical structure attached to an imidazolium ring that contributed to ionomer-PIL interactions. We prepared sulfonated polyimide/ionic liquid (SPI/IL) composite PEMs using 50 wt% [VIm][OTf] with a conductivity of 7.17 mS/cm at 100 °C, and in an anhydrous condition, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride (DSDA) was used in the synthesis of SPIs, leading to several hundred-times improvement in conductivity compared to pristine SPIs. Full article