FRACTAL BEHAVIOR OF SPINODAL DECOMPOSITION IN POLYMER BLENDS

Fractal behaviour of ramified domains in the late stage of spinodal phase separation in a binary polymer blend of poly(vinyl acetate) with poly(methyl methacrylate) was investigated by optical microscopic method. In the late stage of the spinodal decomposition, the fractal dimension D is about 1.64. It implies that some anomalous properties of irregular structure probably may be explained by fractal concepts.

Dynamic mechanical analysis of binary and ternary polymer blends based on nylon copolymer/EPDM rubber and EPM grafted maleic anhydride compatibilizer

The dynamic mechanical properties such as storage modulus, loss modulus and damping properties of blends of nylon copolymer (PA6,66) with ethylene propylene diene (EPDM) rubber was investigated with special reference to the effect of blend ratio and compatibilisation over a temperature range –100°C to 150°C at different frequencies. The effect of change in the composition of the polymer blends on tanδ was studied to understand the extent of polymer miscibility and damping characteristics. The loss tangent curve of the blends exhibited two transition peaks, corresponding to the glass transition temperature (Tg) of individual components indicating incompatibility of the blend systems. The morphology of the blends has been examined by using scanning electron microscopy. The Arrhenius relationship was used to calculate the activation energy for the glass transition of the blends. Finally, attempts have been made to compare the experimental data with theoretical models.

Weld line behaviour of polymer blends with special reference to PP/HDPE, PP/PS and HDPE/LDPE blends

Department of Polymer Science and Rubber Technology, Cochin University of Science and Technology

Studies on the fracture behaviour of polymer blends with special reference to PP/HDPE and PS/HIPS blends

Investigations on the fracture behaviour of polymer blends is the topic of this thesis. The blends selected are PP/HDPE and PS/HIPS. PP/HDPE blend is chosen due to its commercial importance and PS/HIPS blend is selected to study the transition from brittle fracture to ductile fracture.PP/HDPE blends were prepared at different compositions by melt blending at 180°C and fracture failure process was investigated by conducting notch sensitivity test and tensile test at different strain rates. The effects of two types of modifiers (particulate and elastomer) on the fracture behaviour and notch sensitivity of PP/HDPE blends were studied. The modifiers used are calcium carbonate, a hard particulate filler commonly used in plastics and Ethylene Propylene Diene Monomer (EPDM). They were added in 2%, 4% and 6% by weight of the blends.The study shows that the mechanical properties of PP/HDPE blends can be optimized by selecting proper blend compositions. The selected modifiers are found to alter and improve the fracture behaviour and notch sensitivity of the blends. Particulate fillers like calcium carbonate can be used for making the mechanical behaviour more stable at the various blend compositions. The resistance to notch sensitivity of the blends is found to be marginally lower in the presence of calcium carbonate. The elastomeric modifier EPDM produces a better stability of the mechanical behaviour. A low concentration of EPDM is sufficient to effect such a change. EPDM significantly improves the resistance to notch sensitivity of the blends. The study shows that judicious selection of modifiers can improve the fracture behaviour and notch sensitivity of PP/HDPE blends and help these materials to be used for critical applications.For investigating the transition in fracture behaviour and failure modes, PS/HIPS blends were selected. The blends were prepared by melt mixing followed by injection moulding to prepare the specimens for conducting tensile, impact and flexure tests. These tests were used to simulate the various conditions which promote failure.The tensile behaviour of unnotched and notched PS/HIPS blend samples were evaluated at slow speeds. Tensile strengths and moduli were found to increase at the higher testing speed for all the blend combinations whereas maximum strain at break was found to decrease. For a particular speed of testing, the tensile strength and modulus show only a very slight decrease as HIPS content is increased up to about 40%. However, there is a drastic decrease on increasing the HIPS content thereafter.The maximum strain at break shows only a very slight change up to about 40% HIPS content and thereafter shows a remarkable increase. The notched specimens also follow a comparable trend even though the notch sensitivity is seen high for PS rich blends containing up to 40% HIPS. The notch sensitivity marginally decreases with increase in HIPS content. At the same time, it is found to increase with the increase in strain rate. It is observed that blends containing more than 40% HIPS fail in ductile mode.The impact characteristics of PSIHIPS blends studied were impact strength, the energy absorbed by the test specimen and impact toughness. Remarkable increase in impact strength is observed as HIPS content in the blend exceeds 40%. The energy absorbed by the test specimens and the impact toughness also show a comparable trend.Flexural testing which helps to characterize the load bearing capacity was conducted on PS/HIPS blend samples at the two different testing speeds of 5mmlmin and 10 mm/min. The flexural strength increases with increase in testing speed for all the blend compositions. At both the speeds, remarkable reduction in flexural strength is observed as HIPS content in the blend exceeds 40%. The flexural strain and flexural energy absorbed by the specimens are found to increase with increase in HIPS content. At both the testing speeds, brittle fracture is observed for PS rich blends whereas HIPS rich blends show ductile mode of failure.Photoelastic investigations were conducted on PS/HIPS blend samples to analyze their failure modes. A plane polariscope with a broad source of light was utilized for the study. The coloured isochromatic fringes formed indicate the presence of residual stress concentration in the blend samples. The coverage made by the fringes on the test specimens varies with the blend composition and it shows a reducing trend with the increase in HIPS content. This indicates that the presence of residual stress is a contributing factor leading to brittle fracture in PS rich blends and this tendency gradually falls with increase in HIPS content and leads to their ductile mode of failure.

Studies on polymer blends with special reference to NBR/PVC and CR/PVC blends

The study is undertaken on PVC blends because of their all-round importance-One of the most prominent needs of PVC in application end-use is permanent plasticizationlo. Butadiene-acrylonitrile rubber (NBR) has been utilized as permanent plasticizer for PVC since the 1940s for wire and cable insulation, food contact, and pondliners used for oil containment23'24. Also plasticized PVC has been added to vulcanizable nitrile rubber, to yield improved ozone, thermal ageing, and chemical resistance resulting in applications including fuel hose covers, gaskets, conveyor belt covers, and printing roll covers. This blend is miscible in the range of 23 to 45 per cent acrylonitrile content in the butadiene-acrylqnitrile copolymerzs. The first phase of the study was directed towards modification blends. These blends, in addition to the polymers, require a host of additives like curatives for the NBR phase and stabilizers for the PVC phase26of the existing PVC blends, especially NBR/PVC. The second phase of the study was directed towards the development of novel PVC based blends. Chloroprene rubber (polychloroprene) (CR) is structurally similar to PVC and hence is likely to form successful blends with PVC32.

Production of latex reclaim and its utilisation in polymer blends

The overall objective of the present study was to develop a novel and economic reclaiming process that does not adversely affect the quality of rubber and to investigate methods of utilising the reclaim. Since waste latex products represent a potential source of high quality rubber hydrocarbon, it was decided to develop a process based on such latex wastes. The study revealed that latex reclaim could replace raw natural rubber upto about 50 per cent of its weight without any serious deterioration in mechanical properties.

Design, synthesis and computational modelling of aromatic tweezer-molecules as models for chain-folding polymer blends

Novel 'tweezer-type' complexes that exploit the interactions between pi-electron-rich pyrenyl groups and pi-electron deficient diimide units have been designed and synthesised. The component molecules leading to complex formation were accessed readily from commercially available starting materials through short and efficient syntheses. Analysis of the resulting complexes, using the visible charge-transfer band, revealed association constants that increased sequentially from 130 to 11,000 M-1 as increasing numbers of pi-pi-stacking interactions were introduced into the systems. Computational modelling was used to analyse the structures of these complexes, revealing low-energy chain-folded conformations for both components, which readily allow close, multiple pi-pi-stacking and hydrogen bonding to be achieved. In this paper, we give details of our initial studies of these complexes and outline how their behaviour could provide a basis for designing self-healing polymer blends for use in adaptive coating systems. (C) 2008 Elsevier Ltd. All rights reserved.

Molecular recognition between functionalized gold nanoparticles and healable, supramolecular polymer blends – a route to property enhancement

A new, healable, supramolecular nanocomposite material has been developed and evaluated. The material comprises a blend of three components: a pyrene-functionalized polyamide, a polydiimide and pyrenefunctionalized gold nanoparticles (P-AuNPs). The polymeric components interact by forming well-defined p–p stacked complexes between p-electron rich pyrenyl residues and p-electron deficient polydiimide residues. Solution studies in the mixed solvent chloroform–hexafluoroisopropanol (6 : 1, v/v) show that mixing the three components (each of which is soluble in isolation), results in the precipitation of a supramolecular, polymer nanocomposite network. The precipitate thus formed can be re-dissolved on heating, with the thermoreversible dissolution/precipitation procedure repeatable over at least 5 cycles. Robust, self-supporting composite films containing up to 15 wt% P-AuNPs could be cast from 2,2,2- trichloroethanol. Addition of as little as 1.25 wt% P-AuNPs resulted in significantly enhanced mechanical properties compared to the supramolecular blend without nanoparticles. The nanocomposites showed a linear increase in both tensile moduli and ultimate tensile strength with increasing P-AuNP content. All compositions up to 10 wt% P-AuNPs exhibited essentially quantitative healing efficiencies. Control experiments on an analogous nanocomposite material containing dodecylamine-functionalized AuNPs (5 wt%) exhibited a tensile modulus approximately half that of the corresponding nanocomposite that incorporated 5 wt% pyrene functionalized-AuNPs, clearly demonstrating the importance of the designed interactions between the gold filler and the supramolecular polymer matrix.

Miscibility, crystallization κinetics and real-time small-Angle x-ray scattering investigation of the semicrystalline morphology in thermosetting polymer blends of epoxy resin and poly(ethylene oxide)

Thermosetting polymer blends of poly(ethylene oxide) (PEO) and bisphenol-A-type epoxy resin (ER) were prepared using 4,4′-methylenebis(3-chloro-2,6-diethylaniline) (MCDEA) as curing agent. The miscibility and crystallization behavior of MCDEA-cured ER/PEO blends were investigated by differential scanning calorimetry (DSC). The existence of a single composition-dependent glass transition temperature (Tg) indicates that PEO is completely miscible with MCDEA-cured ER in the melt and in the amorphous state over the entire composition range. Fourier-transform infrared (FTIR) investigations indicated hydrogen-bonding interaction between the hydroxyl groups of MCDEA-cured ER and the ether oxygens of PEO in the blends, which is an important driving force for the miscibility of the blends. The average strength of the hydrogen bond in the cured ER/PEO blends is higher than in the pure MCDEA-cured ER. Crystallization kinetics of PEO from the melt is strongly influenced by the blend composition and the crystallization temperature. At high conversion, the time dependence of the relative degree of crystallinity deviated from the Avrami equation. The addition of a non-crystallizable ER component into PEO causes a depression of both the overall crystallization rate and the melting temperature. The surface free energy of folding σe displays a minimum with variation of composition. The spherulitic morphology of PEO in the ER/PEO blends exhibits typical characteristics of miscible crystalline/amorphous blends, and the PEO spherulites in the blends are always completely volume-filling. Real-time small-angle X-ray scattering (SAXS) experiments reveal that the long period L increases drastically with increasing ER content at the same temperatures. The amorphous cured ER component segregates interlamellarly during the crystallization process of PEO because of the low chain mobility of the cured ER. A model describing the semicrystalline morphology of MCDEA-cured ER/PEO blends is proposed based on the SAXS results. The semicrystalline morphology is a stack of crystalline lamellae; the amorphous fraction of PEO, the branched ER chains and imperfect ER network are located between PEO lamellae.