Fracture behaviors of silane‐cured metallocene‐catalyzed polyethylene thermoplastic vulcanizate

Silane moisture‐cured metallocene‐catalyzed polyethylene (mPE) blend to form a novel thermoplastic vulcanizate (TPV) has been prepared. Metallocene polyethylenes with two different levels of comonomer contents were grafted with various amounts of vinyltriethoxy silane. As a result, tensile strength varies slightly with increasing the levels of silane concentrations, at all test temperatures. Tear strength generally decreases with reduced energy dissipation, at higher degrees of cure. “Threshold” fracture energy is roughly proportional to the reciprocal square root of Young's modulus. By relating tensile strength to tear strength, it was found that the corrected average depth of flaw is in the range of 29.3 ± 7.2 μm, which successfully confirms the extension of Rivlin and Thomas's theory for conventional elastomers to TPVs under an elaborate treatment, due to the limitation of the theory. Cutting strength of mPE TPVs gives an intermediate value when compared with that of crystalline plastics and conventional elastomers, which further signifies the importance of crystalline yielding even in the nanofracture zone of deformation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2207–2218, 2005     

Phenylethynyl terminated oligoimides derived from 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride and their adhesive properties

A series of phenylethynyl terminated oligoimides based on 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA), m-phenylene diamine (m-PDA) or/and 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (6FAPB) with calculated molecular weight of 5000 g mol⁻¹ were synthesized. The effect of molecular structure on solubility and melt viscosity of oligoimides as well as the thermal properties of cured polyimide resins was investigated. Experimental results indicated that the oligoimides have good solubility in strong polar solvents to afford homogeneous solutions with the solid content as high as 50 wt%. The oligoimides exhibited better solubility and lower minimum melt viscosity at relatively lower temperature with the incorporation of flexible 6FAPB. These oligoimides could be thermally cured at 320-380 °C to give thermosetted resins. The cured resins have good thermal stability with the glass transition temperatures of 278-329 °C and the onset decomposition temperatures higher than 500 °C. Adhesive properties of polyimides adhered to stainless steel at various conditions were evaluated by lap shear strength test. It was found that the LSS at room temperature increased with the molar ratio of 6FAPB increasing. The polyimides with combination of rigid and flexible structures exhibited good adhesive properties. With the increasing of curing temperature, the lap shear strength of polyimides at elevated temperature maintained at a high level due to the formation of strong bond.     

Compatibilisation effect of PP-g-MA copolymer on iPP/SiO2 nanocomposites prepared by melt mixing

In the present study, a series of iPP/SiO₂ nanocomposites, containing 1, 2.5, 5, 7.5, 10 and 15 wt% SiO₂ nanoparticles, were prepared by melt mixing in a twin screw co-rotating extruder. Poly(propylene-g-maleic anhydride) copolymer (PP-g-MA) containing 0.6 wt% maleic anhydride content was added to all nanocomposites at three different concentrations, 1, 2.5 and 5 wt%, based on silica content. Mechanical properties such as tensile strength at break and Young’s modulus were found to increase and to be mainly affected by the content of silica nanoparticles as well as by the copolymer content. For the tensile strength at break as well as for yield point, a maximum was observed, corresponding to the samples containing 2.5-5 wt% SiO₂. At higher concentrations, large nanosilica agglomerates are formed that have as a result a decrease in tensile strength. Young’s modulus increases almost linearly on the addition of SiO₂, and takes values up to 60% higher than that of neat iPP. Higher concentrations of PP-g-MA resulted in a further enhancement of mechanical properties due to silica agglomerate reduction. This finding was verified from SEM and TEM micrographs. Evidently the surface silica hydroxyl groups of SiO₂ nanoparticles react with maleic anhydride groups of PP-g-MA and lead to a finer dispersion of individual SiO₂ nanoparticles in the iPP matrix. The enhanced adhesion in the interface of the two materials, as a result of the mentioned reaction, has been studied and proved by using several equations. The increased Vicat point of all nanocomposites, by increasing the PP-g-MA content, can also be mentioned as a positive effect.     

Allylic monomers as reactive plasticizers of polyphenylene oxide. Part III – Rheological and mechanical properties

The chemorheology of blends of diallyl ortho-phthalate (DAOP) as reactive plasticizer of polyphenylene oxide (PPO) were monitored during their cure with either dicumyl peroxide (DCP) or tert-butyl hydroperoxide (TBHP), and their mechanical properties and morphology were studied. The steady shear and dynamic rheology behaviour was consistent with chemical gelation of DAOP in blends with low concentrations of PPO but the gelation behaviour at higher PPO concentrations was more complex. Dynamic mechanical thermal analysis of the blends of PPO:DAOP cured with either DCP or TBHP indicated a two phase structure. For PPO:DAOP/DCP, the lowest transition (between 150 °C and 200 °C) was attributed to a DAOP-rich phase and its T_g was higher than that for pure DAOP/DCP due to the presence of PPO in the DAOP-rich phase. The smaller damping shoulder near 250 °C was caused by a PPO-rich phase with a T_g that was lower than pristine PPO due to the presence of unpolymerized or polymerized DAOP. In contrast, the glass transition region of the PPO:DAOP/TBHP system was very broad due to an overlap of the transitions for DAOP-rich and PPO-rich phases caused by higher levels of unpolymerized DAOP. SEM observations of the blends revealed a two phase morphology with PPO-rich particles in a poly-DAOP matrix for blends with ?30 wt% PPO, a co-continuous morphology for blends with 40 wt% PPO, and a phase inverted morphology with more than 50 wt% PPO. These SEM observations agree with studies of the swelling, disintegration or dissolution of matrix of the blends in solvent.     

Mechanical properties and thermal analysis of low‐density polyethylene + polypropylene blends with dialkyl peroxide

Polypropylene + low density polyethylene (PP + LDPE) blends involving 0, 25, 50, 75 and 100 wt% of PP with dialkyl peroxide (DAP) were prepared by melt blending in a single‐screw extruder. The effects of adding dialkyl peroxide on mechanical and thermal properties of PP + LDPE blends have been studied. It was found that at lower concentrations of peroxide (e.g., 0–0.08 wt% of dialkyl peroxide) LDPE component is cross‐linked and Polypropylene (PP) is degraded in all compositions of PP + LDPE blends. Mechanical properties (Tensile strength at break, at yield and elongation at break), Melt flow index (MFI), hardness, Scanning Electron Microscope (SEM) and thermal analyses (DSC) of these blends were examined. Because of serious degradation or cross‐linking the mechanical properties and the crystallinty (%) of those products were decreased as a result of increasing peroxide content. Copyright © 2009 John Wiley & Sons, Ltd.     

Influence of surface modification of fillers and polymer on flammability and tensile behaviour of polypropylene-composites

An intumescent system consisting of ammonium polyphosphate (APP) as an acid source and blowing agent, pentaerythritol (PER) as a carbonific agent and natural zeolite (clinoptilolite, Gördes II) as a synergistic agent was used in this study to enhance flame retardancy of polypropylene (FR-PP). Zeolite was incorporated into flame retardant formulation at four different concentrations (1, 2, 5, and 10 wt%) to investigate synergism with the flame retardant materials. Filler content was fixed at 30 wt% of total amounts of flame retardant PP composites. Zeolite and APP were treated with two different coupling agents namely, 3-(trimethoxysilyl)-1-propanethiol and (3-aminopropyl)-triethoxysilane for investigation of the influence of surface treatments on mechanical properties and flame retardant performance of composites. Maleic anhydride grafted polypropylene (MAPP) was used for making polypropylene hydrophilic. Flammability of FR-PP composites was measured by the determination of limiting oxygen index (LOI). The LOI values reached to a maximum value of 41% for mercapto silane treated APP:PER (2:1) PP composite containing 5 wt% zeolite. The tensile strength of composites was increased by the addition of MAPP and elongation at break of composites was increased with silane treatments.     

Thermal, ozone and gamma ageing of styrene butadiene rubber and poly(ethylene-co-vinyl acetate) blends

Ageing behaviour of SBR/EVA blends due to the effects of heat, ozone, and gamma radiation was studied with reference to blend ratio, three crosslinking systems (sulfur, peroxide and mixed) and a compatibiliser (SEBS-g-MA). It was found that an increase in the EVA content of the blends enhanced the ageing characteristics. Among the different crosslinking systems, a peroxide cured system exhibited the best retention of properties even after severe ageing. Tensile strength of peroxide cured SBR/EVA blends increased slightly after ageing for three days at 70 °C due to continued crosslinking, whereas tensile strength of all blends decreased on ageing at 100 °C. Compatibilisation with SEBS-g-MA improved the thermal, gamma and water ageing resistance of SBR/EVA blends.     

Morphology and properties of nanostructured materials based on polypropylene/poly(butylene succinate) blend and organoclay

Nanostructured materials based on organically modified montmorillonite (OMMT) and polypropylene (PP)/poly(butylene succinate) (PBS) blend were prepared via melt-mixing of PP, PBS, and OMMT in a batch mixer. The weight ratio of PP and PBS was 70:30, and the OMMT loading varied from 0.5 to 5 wt%. The surface morphologies of unmodified and OMMT-modified blend were studied by field-emission scanning electron microscopy. Results showed that the particle size of the dispersed PBS phase was significantly reduced with the addition of a small amount of OMMT (1.5 wt%). Upon the addition of 5 wt% of OMMT, the domain size of the dispersed PBS phase changed significantly from the unmodified blend, and a homogeneous dispersion of very fine particles of PBS was observed. The degree of dispersion of silicate layers in the blend matrix was characterized by X-ray diffraction and transmission electron microscopy. The improved adhesion between the phases and the fine morphology of the dispersed phase contributed to the significant improvement in the properties and thermal stability of the final nanocomposite materials. On the basis of these results, we describe a general understanding of how the morphology is related to the final properties of OMMT-incorporated PP/PBS blend.     

Studies on the blends of cardanol-based epoxidized novolac resin and CTPB

Cardanol-based novolac-type phenolic resins were synthesized with different mole ratios of cardanol-to-formaldehyde, viz., 1:0.6, 1:0.7, and 1:0.8. These novolac resins were epoxidized with molar excess of epichlorohydrin at 120 °C in basic medium. The epoxidized novolac resins were, separately, blended with different weight ratios of carboxyl-terminated polybutadiene liquid rubber ranging between 0-25 wt% with an interval of 5 wt%. All the blends were cured at 150 °C with 40 wt% polyamide. The formation of various products during the curing of blend samples has been studied by Fourier-transform infra-red spectroscopic analysis. The tensile strength and elongation-at-break of the cured samples increased up to 15 wt% in the blend and decreased thereafter. This blend sample was also found to be most thermally stable system. The blend morphology, studied by scanning electron microscopy analysis, was finally correlated with the structural and property changes in the blends.     

Photopolymerization and toughening performance in polypropylene of hyperbranched polyurethane acrylate

A novel UV-curable hyperbranched polyurethane acrylate (HUA) was synthesized and found to polymerize rapidly in the presence of 5 wt.% benzophenone in N₂ under UV exposure. The photopolymerization kinetics of HUA was studied by differential photocalorimetry (DPC). Its toughening effect for polypropylene (PP) was investigated by tensile and impact tests of the UV irradiated PP/HUA blends. The morphological structures and thermal behavior were determined by polarized optical microscopy, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). The obtained results demonstrate that (1) the maximum photopolymerization rate increases with raising temperature up to 140 °C, whereas decreases at above 150 °C. The activation energy of 19 kJ mol⁻¹ for the photopolymerization was obtained at below 140 °C from the Arrhenius plot, while it is negative at above 150 °C. (2) The incorporation of 5 wt.% HUA greatly improved the notched impact strength of PP matrix with a slight improvement in the tensile strength and without obvious decline in breaking elongation. These results correlate well with SEM observation. (3) During the UV irradiation of PP/HUA blends, PP can be crosslinked/grafted with the cured HUA particles, resulting in the increase of the impact strength of PP matrix. (4) The cured HUA particles in the PP/HUA blends act as heterogeneous nucleation agent for PP, which results in the decrease of spherulite size and less perfection of PP crystals.     

Effect of a novel charring-foaming agent on flame retardancy and thermal degradation of intumescent flame retardant polypropylene

A new triazine polymer was synthesized by using cyanuric chloride, ethanolamine and ethylenediamine as raw materials. It is used both as a charring agent and as a foaming agent in intumescent flame retardants, designated as charring-foaming agent (CFA). Effect of CFA on flame retardancy, thermal degradation and mechanical properties of intumescent flame retardant polypropylene (PP) system (IFR-PP system) has been investigated. The results demonstrated that the intumescent flame retardant (IFR) consisting of CFA, APP and Zeolite 4A is very effective in flame retardancy of PP. It was found that when the weight ratio of CFA to APP is 1:2, that is, the components of the IFR are 64 wt% APP, 32 wt% CFA and 4 wt% Zeolite 4A, the IFR presents the most effective flame retardancy in PP systems. LOI value of IFR-PP reaches 37.0, when the IFR loading is 25 wt% in PP. It was also found that when the IFR loading is only 18 wt% in PP, the flame retardancy of IFR-PP can still pass V-0 rating, and its LOI value reaches 30.2. TGA data obtained in pure nitrogen demonstrated that CFA has a good ability of char formation itself, and CFA shows a high initial temperature of the thermal degradation. The char residue of CFA can reach 35.7 wt% at 700 °C. APP could effectively promote the char formation of the APP-CFA system. The char residue reaches 39.7 wt% at 700 °C, while it is 19.5% based on calculation. The IFR can change the thermal degradation behaviour of PP, enhance T_max of the decomposition peak of PP, and promote PP to form char, based upon the results of the calculation and the experiment. This is attributed to the fact that endothermic reactions took place in IFR charring process and the char layer formed by IFR prevented heat from transferring into inside of IFR-PP system. TGA results further explained the effective flame retardancy of the IFR containing CFA.     

Understanding the role of nanosilica particle surfaces in the thermal degradation of nanosilica-poly(methyl methacrylate) solution-blended nanocomposites: From low to high silica concentration

Nanocomposites of poly(methyl methacrylate) and 12 nm silica particles have been prepared by a casting procedure which allows the homogeneous dispersion of up to 35 wt% of silica. Twelve nanocomposites with compositions ranging from 1 to 35 wt% have been prepared and studied by Scanning Electron Microscopy, Fourier Transform Infrared Spectroscopy, Differential Scanning Calorimetry, Thermogravimetric Analysis and Isothermal Chemiluminescence. Thermal stability increases outstandingly as soon as 1 wt% of silica is added to PMMA. This effect is well-known but had not been explained up to now. Of the two main processes which initiate degradation in PMMA, radical formation at labile chain ends and random chain scission, it is the former which disappears in composites with 3 wt% of silica. The origin of the thermal stabilization in these polymer composites is thus the blocking of the PMMA chain end by the silica particle. At the same time, viscous flow decreases progressively, and composites with 20 wt% of silica or over are dimensionally stable even if heated at 300 °C for several hours. The concomitant decrease of viscous flow and increase of low temperature thermal stability shift the temperature range of application of these composites strongly, and the understanding of the silica surface role allows envisaging the control of the behaviour.     

动态固化聚丙烯/环氧树脂共混物的研究

将动态硫化技术应用于热塑性树脂 热固性树脂体系 ,制备了动态固化聚丙烯 (PP) 环氧树脂共混物 .研究了动态固化PP 环氧树脂共混物中两组分的相容性、力学性能、热性能和动态力学性能 .实验结果表明 ,马来酸酐接枝的聚丙烯 (PP g MAH)作为PP和环氧树脂体系的增容剂 ,使分散相环氧树脂颗粒变细 ,增加了两组分的界面作用力 ,改善了共混物的力学性能 .与PP相比 ,动态固化PP 环氧树脂共混物具有较高的强度和模量 ,含 5 %环氧树脂的共混物拉伸强度和弯曲模量分别提高了 30 %和 5 0 % ,冲击强度增加了 15 % ,但断裂伸长率却明显降低 .继续增加环氧树脂的含量 ,共混物的拉伸强度和弯曲模量增加缓慢 ,冲击强度无明显变化 ,断裂伸长率进一步降低 .动态力学性能分析 (DMTA)表明动态固化PP 环氧树脂共混物是两相结构 ,具有较高的储能模量 (E′)     

Effect of silica nanoparticles on solid state polymerization of poly(ethylene terephthalate)

In the present study, the effect of silica nanoparticles, on the solid state polycondensation (SSP) kinetics of poly(ethylene terephthalate) (PET) is thoroughly investigated. At silica concentrations less than 1 wt% and reaction temperatures between 200 and 230 °C higher intrinsic viscosity (IV) values were measured, compared to neat PET at all reaction times. However, with 1 wt% of nanosilica (n-SiO₂), the IV increase of the nanocomposites was similar to that of neat PET and a further increase to 5 wt% n-SiO₂ resulted in significantly lower IV values. A simple kinetic model was also employed to predict the time evolution of IV, as well as the carboxyl and hydroxyl content during SSP. The kinetic parameters of the transesterification and esterification reactions were estimated at different temperatures with or without the addition of n-SiO₂. The activation energies of both reactions were determined together with the concentration of inactive end-groups. From the experimental measurements and the theoretical simulation results it was proved that n-SiO₂ in small amounts (less than 1 wt%) enhances both the esterification and transesterification reactions at all studied temperatures acting as a co-catalyst. However, as the amount of nanosilica increases a number of inactive hydroxyl groups were estimated corresponding to participation of these groups in side reactions with the nanosilica particles. These side reactions lead initially to branched PET chains and eventually (5 wt% n-SiO₂ concentration) to crosslinked structures.     

Morphology, flexural, and thermal properties of sepiolite modified epoxy resins with different curing agents

A bisphenol A-based epoxy resin was modified with 5 wt% organically modified sepiolite (Pangel B40) and thermally cured using two different curing agents: an aliphatic diamine (Jeffamine D230, D230) and a cycloaliphatic diamine (3DCM). The morphology of the cured materials was established by scanning and transmission electron microscopy analysis. The thermal stability, thermo-mechanical properties, and flexural behaviour of the sepiolite-modified matrices were evaluated and compared with the corresponding neat matrix. The initial thermal decomposition temperature did not change with the addition of sepiolite. The flexural modulus of the epoxy matrix slightly increases by the incorporation of the organophilic sepiolite. The flexural strength of the sepiolite modified resin cured with D230 increased by a 10% while the sepiolite modified resin cured with 3DCM resulted in a lower flexural strength compared with the unmodified resin. The reduced flexural strength was attributed to the stress concentrations caused by the sepiolite modifier, which rendered the resins more brittle.     

Enhanced adhesion of polypropylene to copper substrates

Varying concentrations of maleic anhydride (MAH) were grafted onto three types of polypropylene (PP) in the presence of dicumyl peroxide (DCP). Pull-off adhesive strength from a copper substrate, tensile Young's modulus, and tensile strain-at-break were determined and SEM observations made as a function of the MAH concentration for each PP. One of the PPs plus 3 wt% MAH provides a high value of the adhesive strength along with the Young modulus and the strain-at-break sufficient for the use as a coating for copper wires and cables.     

Influence of chemical surface modification of cellulose nanowhiskers on thermal,mechanical, and barrier properties of poly(lactide) based bionanocomposites

In the aim of producing fully organic bionanocomposite based on poly(lactide) (PLA), cellulose nanowhiskers (CNW) were grafted by n-octadecyl-isocyanate (CNW-ICN) applying an in situ surface grafting method. The compatibilizing effect of the long aliphatic grafted chain was investigated by thermal, mechanical and permeability analysis of solvent cast nanocomposite films. The grafted CNW-ICN could be successfully dispersed in the polymer matrix. The gained compatibility brought about a nucleating effect, decreasing the half time of isothermal crystallization from 25 min for the neat PLA to 8.4 min for the nanocomposite including 2.5 wt% CNW-ICN, e.g., tensile strength was improved by 10 MPa for the same 2.5 wt% CNW-ICN/PLA composite. Mechanical reinforcement was also effective in the rubbery state of PLA and increased the tensile modulus of the rubbery plateau providing thereby thermal resistance to the polymer. Oxygen barrier properties did not change significantly upon the inclusion of CNW-ICN, even when the quantity of CNW-ICN was increased to 15 wt%. More interestingly, the water vapour permeability of the CNW-ICN nanocomposite was always lower than the one of ungrafted CNW composites, which led to the conclusion that the hydrophobic surface graft and improved compatibility could counteract the effect of inclusion of hydrophilic structures in the matrix on water vapour transport. In conclusion, the surface grafting of CNW with isocyanates might be an easy and versatile tool for designing fully organic bionanocomposites with tailored properties.     

Phenylethynylnaphthalic endcapped imide oligomers with reduced cure temperatures

A series of 4-(2-phenylethynyl)-1,8-naphthalic anhydride (PENA) endcapped imide oligomers with different chemical backbones and calculated number average molecular weights (Calc’d M_n) were successfully synthesized and characterized. The PENA-endcapped imide oligomers were mixtures of mono- and double-endcapped imide oligomers with polymerization degree (P_n) of 1-5 and number average molecular weights (M_n) of 2515-3851 g/mol. determined by GPC. Study on effect of chemical structures on the curing behaviors of two model compounds: PENA-m based on PENA and PEPA-m derived from 4-phenylethynylphthalic anhydride (PEPA) revealed that PENA-m showed the cure temperature of 50 °C lower than PEPA-m and the activity energy of thermal curing reaction for PENA-m was also lower than that of PEPA-m. The PENA-endcapped imide oligomers could be melt at temperatures of >250 °C with the minimum melt viscosity of 1.2-230 Pa s at 275-301 °C and the widen melt processing windows, along with 10-40 °C lower cure temperature than the PEPA-endcapped analogue.The PENA-endcapped imide oligomers could be thermally cured at 350 °C/1 h to afford the thermally cured polyimides with good combined thermal and mechanical properties including T_g of 344-397 °C (DMA), T_d of 443-513 °C, tensile strength of as high as 54.7 MPa, flexural strength of as high as 126.1 MPa and modulus of as high as 2.3 GPa, respectively.     

Total luminescence intensity (TLI) offers superior early oxidation detection in unstabilised polyethylene but is no better than FT-IR for stabilised polyolefins

In an earlier study, we have shown that chemiluminescence (CL) and the total luminescence intensity (TLI) method are highly sensitive to oxidation in degradable PE. In this study, stabilised PE and PP were characterised with CL in an inert (TLI) and in an oxygen atmosphere (CL-OIT) and the results were compared to those obtained by the commonly used techniques, FT-IR (carbonyl index (CI)) and thermal analysis (DSC-OIT). PE was aged at a low temperature (80 °C) and PP was aged at temperatures between 60 and 120 °C. Non-Arrhenius behaviour was observed in the oxidation of PP. This showed the importance of aging at a low temperature to obtain realistic results. TLI and CI of stabilised PP and most of the stabilised PE gave comparable results with the same sensitivity for oxidation detection. This was in contrast to our previous results for degradable PE. However, TLI of unstabilised PE showed earlier oxidation detection than CI, which agreed with our earlier results. TLI of PE had a higher sensitivity than CL-OIT, and both TLI and CI of PP were sufficiently sensitive to detect the effect of aging at different temperatures, whereas DSC-OIT was not.     

The effect of Zn, Al layered double hydroxide on thermal decomposition of poly(vinyl chloride)

Poly(vinyl chloride)/layered double hydroxide (LDH) composite was prepared by mixing 4 wt% Zn₂Al-CO₃-LDH with PVC and fluxing at 180 °C. The thermal decomposition behaviour of the LDH + PVC composite in air and nitrogen environments was systematically investigated. We found that mixing Zn₂Al-CO₃-LDH into PVC facilitates dehydrochlorination from ca. 300 to 270 °C but reduces the reaction extent to leave more chlorine on the polyene backbones both in air and N₂. We have also found that at 400-550 °C, both in air and N₂, LDH assists the formation of char-like materials and decreases the release of volatile hydrocarbons. From 550 to 800 °C, the char-like materials are mostly retained in N₂ while they are almost completely thermo-oxidized (burned) in air. Thus, addition of Zn₂Al-CO₃-LDH to PVC does not increase the thermal stability, but does promote charring to retard the generation of flame. The influence of LDH on PVC thermal properties has been also addressed mechanically.