Fluorinated ?-caprolactone: Synthesis and ring-opening polymerization of new α-fluoro-?-caprolactone monomer

Fluorinated polyester was synthesized from a novel α-fluoro-?-caprolactone monomer (α-FCL). The monomer was synthesized from commercially available cyclohexene oxide in three steps. Baeyer-Villiger reaction using 3-chloroperoxybenzoic acid of the corresponding 2-fluorocyclohexanone resulted in formation of two isomeric lactones α-and-?-fluoro-?-caprolactones in 1:1.2 molar ratio, respectively. Poly(α-fluoro-?-caprolactone) was synthesized by bulk ring-opening polymerization of α-fluoro-?-caprolactone monomer (α-FCL) catalyzed by stannous octanoate, Sn(Oct)₂ at 120 °C for 6 h. Relationships between reaction time, polymer yield, and molecular weight were established. The ring-opening polymerization of ?-fluoro-?-caprolactone (?-FCL) produce geminal fluorohydrin, which is not stable and it is subsequently dehydrofluorinated to give the corresponding aldehyde. Copolymerization of α-FCL with ?-caprolactone (?-CL) in various feed ratios was also investigated. Detail microstructure analyses of the copolymers were accomplished from ¹H, ¹³C and 2-D NMR data. Presence of fluorine atoms is expected to regulate the chemical and physical properties of the polyester.     

Preparation,characterization, and mechanical properties of poly(ε‐caprolactone)/polylactic acid blend composites

Mechanical properties of poly(ε‐caprolactone) (PCL) and polylactic acid (PLA) blend reinforced with Dura and Tenera palm press fibers were studied. Dicumyl peroxide (DCP) was used as compatibilizer in the blend composites. Fourier transforms infrared spectrophotometer (FTIR) and field emission scanning electron microscope (FESEM) was used to study the effect of treatment on the fibers and fiber/matrix adhesion respectively. The uncompatibilized blend composites exhibited higher Young's modulus than the compatibilized blend composites. Impact strength of compatibilized blend composites of Tenera fibers (FM) increased by 161% at 10 wt% fiber load more than the uncompatibilized blend composites at same fiber load. The Dura fibers (FN) enhanced impact strength by 133% at 10 wt% fiber load. Tensile strength increased by 40% for compatibilized FM blend composites. In conclusion, it was observed that DCP incorporation resulted in good interfacial adhesion as revealed by the FESEM micrographs and evidenced in the improved mechanical properties. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Cost-based admission control for Internet Commerce QoS enhancement

In many e-commerce systems, preserving Quality of Service (QoS) is crucial to keep a competitive edge. Poor QoS translates into poor system resource utilisation, customer dissatisfaction and profit loss. In this paper, a cost-based admission control (CBAC) approach is described which is a novel approach to preserve QoS in Internet Commerce systems. CBAC is a dynamic mechanism which uses a congestion control technique to maintain QoS while the system is online. Rather than rejecting customer requests in a high-load situation, a discount-charge model which is sensitive to system current load and navigational structure is used to encourage customers to postpone their requests. A scheduling mechanism with load forecasting is used to schedule user requests in more lightly loaded time periods. Experimental results showed that the use of CBAC at high load achieves higher profit, better utilisation of system resources and service times competitive with those which are achievable during lightly loaded periods. Throughput is sustained at reasonable levels and request failure at high load is dramatically reduced.     

Mechanical and thermal properties of calcium carbonate‐filled PP/LLDPE composite

Polymer blends typically are the most economical means to develop new resins for specific applications with the best cost/performance balance. In this paper, the mechanical properties, melting, glass transition, and crystallization behavoir of 80 phr polypropylene (PP) with varying weights of linear low density polyethylene (LLDPE) at 10, 20/ 20 wt % CaCO₃, 30, 40, and 50 phr were studied. A variety of physical properties such as tensile strength, impact strength, and flexural strength of these blends were evaluated. The compatibility of these composite was examined by differential scanning calorimetry (DSC) to estimate T_m and T_c, and by dynamic mechanical analysis (DMA) to estimate T_g. The fractographic analysis of these blends was examined by scanning electron microscopy (SEM). It has been confirmed that increasing the LLDPE content trends to decreases the tensile strength and flexural strength. However, increasing the LLDPE content led to increases in the impact strength of PP/LLDPE blends. It was also found that up to 40 phr the corresponding melting point (T_m) was not effected with increasing LLDPE content. Each compound has more than one T_g, which was informed that there is a brittle‐ductile transition in fracture nature of these blends, the amount of material plastically deformed on the failure surface seems to increase with the increasing the LLDPE content. And PP/LLDPE blends at temperature (23°C) showed a ductile fracture mode characterized by the co‐existence of a shear yielding process; whereas at lower temperature (−20°C) the fractured surfaces of specimens appear completely brittle. The specimens broke into two pieces with no evidence of stress whitening, permanent macroscopic deformation or yielding. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Novel toughened polylactic acid nanocomposite: Mechanical,thermal and morphological properties

The objective of the study is to develop a novel toughened polylactic acid (PLA) nanocomposite. The effects of linear low density polyethylene (LLDPE) and organophilic modified montmorillonite (MMT) on mechanical, thermal and morphological properties of PLA were investigated. LLDPE toughened PLA nanocomposites consisting of PLA/LLDPE blends, of composition 100/0 and 90/10 with MMT content of 2 phr and 4 phr were prepared. The Young’s and flexural modulus improved with increasing content of MMT indicating that MMT is effective in increasing stiffness of LLDPE toughened PLA nanocomposite even at low content. LLDPE improved the impact strength of PLA nanocomposites with a sacrifice of tensile and flexural strength. The tensile and flexural strength also decreased with increasing content of MMT in PLA/LLDPE nanocomposites. The impact strength and elongation at break of LLDPE toughened PLA nanocomposites also declined steadily with increasing loadings of MMT. The crystallization temperature and glass transition temperature dropped gradually while the thermal stability of PLA improved with addition of MMT in PLA/LLDPE nanocomposites. The storage modulus of PLA/LLDPE nanocomposites below glass transition temperature increased with increasing content of MMT. X-ray diffraction and transmission electron microscope studies revealed that an intercalated LLDPE toughened PLA nanocomposite was successfully prepared at 2 phr MMT content.     

Highly conductive graphene-based segregated composites prepared by particle templating

We use capillary-driven particle level templating and hot melt pressing to disperse few-layer graphene flakes within a polystyrene matrix to enhance the electrical conductivity of the polymer. The conducting pathways provided by the graphene located at the particle surfaces through contact of the bounding surfaces allow percolation at a loading of less than 0.01 % by volume. This method of distributing graphene within a matrix overcomes the need to disperse the sheet-like conducting fillers isotropically within the polymer, and can be scaled up easily.     

Elastomeric influence of natural rubber latex on cement mortar at high temperatures using thermal degradation analysis

The importance of thermal endurance in relation to finishes prone to elevated temperatures cannot be over emphasized. Inclusion of elastomeric substances into mortar aimed at improving performance properties may therefore pose a serious threat. This paper presents experimental findings regarding elastomeric influence of natural rubber latex (NRL) – a typical elastomer – on cement mortar. Hardened cement paste, NRL-films, cement–latex blends, control and modified mortars containing 10% and 20% latex/water ratios were prepared and cured for 6 months. Microstructural units of samples were observed through SEM followed by subjection to TGA within a temperature range; 25–900 °C. The results indicate that NRL degrades to about 5% (by weight) at temperatures between 350 and 430 °C. Eventually, NRL-modified mortar was significantly affected by the softening of NRL-films present in the co-matrix. However, the overall resistance of the modified systems to thermal degradation was surprisingly improved by the inclusion of the elastomer.     

Synthesis,characterisation and solution thermal behaviour of a family of poly (N-isopropyl acrylamide-co-N-hydroxymethyl acrylamide) copolymers

Thermo-responsive copolymers of poly (N-isopropyl acrylamide-co-N-hydroxymethyl acrylamide)p(NIPAAm-co-HMAAm) with a range of content of hydroxy groups have been synthesised by free radical polymerisation. The polymers were characterised by NMR, FTIR and GPC. A detailed study of the solution thermal properties showed that polymers with up to about 50 wt.% hydroxy monomer show lower critical solution temperature (LCST) properties in water. Polymers with higher hydroxy monomer content are fully soluble at all temperatures up to 100 °C. The effect of pH, salts and solvent additives on the solution thermal behaviour of the copolymers was investigated, showing that “salting-out” salts lowered the LCST and “salting-in” salts caused an initial increase in LCST at low concentrations, but reduced LCST at higher concentrations, in line with the Hoffmeister series. The LCST of any copolymer composition from this family in pure water can be predicted from the empirical equation; LCST = 0.015x² + 0.25x + 31.76, where x is the fraction of the hydroxy monomer. Due to differences in polarity and the length of the carbon chain, methanol and ethanol altered LCST of p(NIPAAm) and its hydroxyl copolymers in different manners, showing a transition from cononsolvency to cosolvency as the hydroxyl content of the copolymer increased. A more complex polyhydroxy compound, sucrose, had very little effect on LCST for either p(NIPAAm) or its hydroxyl copolymers.     

Solution thermal properties of a family of thermo-responsive N-isopropyl acrylamide-co-N-hydroxymethyl acrylamide copolymers - Aspects intrinsic to the polymers

A family of (N-isopropyl acrylamide-co-N-hydroxymethyl acrylamide) copolymers, p(NIPAAm-co-HMAAm), was synthesised and characterised with respect to solution thermal behaviour. A notable increase in cloud point (CP) was observed as the concentration of the polymer solutions was lowered, though the effect of concentration on CP of pure p(NIPAAm), was relatively small. In all cases, the elevation of CP was most evident at low concentration between 0.1 wt.% and 0.01 wt.%. Both at fixed and decreasing concentrations of p(NIPAAm) solutions, a direct relationship between molecular weight and CP was observed, where CP shifted to higher temperatures as the molecular weight increased. The polymer coil size in solution below the CP in the concentration range studied was between 4 and 11 nm for all the polymers in this study, irrespective of the concentration and of the fraction of hydroxy monomer incorporated, but increased dramatically above the CP. CPs obtained by Dynamic Light Scattering (DLS) were lower than those obtained by UV absorbance as the latter is less sensitive. Copolymer compositions with more than 13% hydroxy monomer showed no thermal hysteresis, in contrast to pure p(NIPAAm). The rate of heating/cooling had almost no effect on the CP values recorded.