Photodegradation of some low‐density polyethylene–montmorillonite nanocomposites containing an oligomeric compatibilizer

The photo‐oxidation behavior at the exposed surfaces of maleated low‐density polyethylene [LDPE poly(ethylene‐co‐butylacrylate‐co‐maleic anhydride) (PEBAMA)] and montmorillonite (MMT) composites was studied using attenuated total reflection Fourier transform infrared spectroscopy, X‐ray diffraction (XRD), transmission electron microscopy (TEM), and mechanical testing. Two different MMT clays were used with the maleated polyethylene, an unmodified clay, MMT, and an organically modified montmorillonite (OMMT) clay which was significantly exfoliated in the composite. The morphologies of sample films were examined by XRD and TEM. The results were explained in terms of the effect of the compatibilizing agent PEBAMA on the clay dispersion. It was found that the OMMT particles were exfoliated in the polymer matrix in the presence of the PEBAMA, whereas the MMT clay particles were agglomerated in this matrix. Both mechanical and spectroscopic analyses showed that the rates of photo oxidative degradation of the LDPE‐PEBAMA–OMMT were higher than those for LDPE and LDPE‐PEBAMA–MMT. The acceleration of the photo‐oxidative degradation for LDPE‐PEBAMA–OMMT is attributed to the effects of the compatibilizer and the organic modifier in the composite. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40788.     

Influence of morphology on photo‐degradation of low density polyethylene films

The effect of the morphology on photo‐degradation was investigated for low‐density polyethylene materials. For this purpose, films with different degrees of crystallinity and different degrees of orientation were prepared. For all the films, photodegradation was promoted at 336K for 12 days using a weather meter. The following results were obtained. There existed an induction period before degradation or chain scission. The induction period was longer for stretched films than for un‐stretched ones. Also, the rate of degradation became lower for stretched films. However, both the induction period and the rate of degradation hardly changed with heat‐treatment condition, that is, the degree of crystallinity. In the induction period, the density changed in a complicated manner. This complicated change must be due to the change in the molecular aggregation state of the amorphous phase. The rheological and GPC measurements indicated that photo‐degradation causes the lowering of molecular weight and the increase in higher molecular weight fraction, and consequently the broadening of molecular weight distribution. The lowering of molecular weight may be caused by chain scission and the increase in higher molecular weight fraction by the formation of crosslinks.     

Influence of Processing Conditions on the Properties of Polystyrene (PS)/organomontmorillonite (OMMT) Nanocomposites Prepared via Solvent Blending Method

A series of polystyrene (PS)/organomontmorillonite (OMMT) clay nanocomposites was prepared by effectively dispersing the inorganic nanolayers of OMMT clay in the organic PS matrix via the solvent blending method using xylene as a solvent. The resulting samples were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The XRD and TEM results show that the intercalation/exfoliation of OMMT can be divided into solvent swelling and layer breaking processes and is affected by several reaction parameters such as nanofiller loading, refluxing temperature, and refluxing time. TGA data show that the PS/OMMT nanocomposites have significant enhanced thermal stability. When 50% weight loss is selected as a point of comparison, the thermal decomposition temperature of PS/OMMT nanocomposite with 7 wt% of OMMT is 15°C higher than that of pure PS. The glass transition temperature (T_g) of PS/OMMT nanocomposites is about 5.0–6.2°C higher than that of pure PS. The water uptake capacity of PS/OMMT nanocomposites is negligible when compared with pure PS.     

Synergistic effects of zinc oxide in montmorillonite flame‐retardant polystyrene nanocomposites

In this study, two‐dimensional organic montmorillonite (OMMT) and one‐dimensional needlelike ZnO were used as flame retardants of polystyrene (PS). Polystyrene/organic montmorillonite (PMT) and polystyrene/organic montmorillonite/zinc oxide nanocomposites (PMZs) with different weight ratios were prepared by melt intercalation. Information on the morphologies and structures of the PS nanocomposites was obtained with Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. The results indicate that a mixed exfoliated–intercalated structure was observed in the PMT and PMZs. Dynamic mechanical thermal analysis showed that both the storage modulus and glass‐transition temperature values of the PMT and PMZs were significantly improved compared with those of the neat PS. The mechanical property tests showed that the bending modulus values of both PM5 (PS/OMMT weight ratio = 95:5) and PMZs increased compared with that of pristine PS. PMZ1 (PS/OMMT/ZnO weight ratio = 94:5:1) provided no decrease in the tensile strength in comparison with PS. A synergistic effect was observed between OMMT and ZnO; this resulted in improvements in the flame retardancy and dynamic mechanical properties in the PMZs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43047.     

不同结构聚苯乙烯/蒙脱土复合材料的熔体流动行为研究

分别将聚苯乙烯树脂(PS)与钠基蒙脱土(Na-MMT)和有机化蒙脱土(OMMT)通过熔融复合制备纳米黏土改性的复合材料。通过X射线衍射(XRD)对复合材料的微观结构进行了分析,采用HAAKE流变仪和熔体流动速率仪研究了复合材料的熔体流动行为。结果表明,Na-MMT在与PS熔融复合前后,其片层间距没有发生变化,PS分子链没有插入蒙脱土片层之间,所形成的是一种填充型复合材料。OMMT在熔融复合后,片层间距显著增大,与PS分子链形成了插层复合结构。蒙脱土含量相同时,PS/Na-MMT复合体系的熔体流动性能比PS/OMMT体系更好。研究认为,熔融复合过程中PS分子链的断链和2种复合材料结构上的差异是影响2种材料流动性能的主要因素。     

Mechanical properties of polystyrene‐montmorillonite nanocomposites—Prepared by melt intercalation

A series of polymer‐clay nanocomposite (PCN) materials, consisting of thermoplastic polystyrene (PS) sample and dispersing inorganic organoclay platelets, were successfully prepared. First, organoclay was prepared by performing cationic exchange reactions between the sodium ions existing in the interlayer region of the clay mineral and intercalation agent, followed by dispersing the organophilic clay into a PS basis through the melt intercalation approach performed by a twin‐screw mixing method. The as‐prepared PCN materials in the form of a pellet subsequently characterized using the powder X‐ray diffraction (XRD) and the transmission electron microscopy (TEM). In this study, it is found that the wear resistance of PS to be effectively enhanced by the incorporation of low loading organophilic clay platelets. The surface morphological image for the neat PS and PS‐clay after a wear resistance test has also been compared and identified by the scanning electron microscopy (SEM). Furthermore, the effect of organoclay on three other different measurement types of mechanical properties for as‐prepared PCN materials, e.g., flexural tests, impact tests, and micron‐nano indenter tests were performed and compared. Generally, PCN materials exhibited an obvious enhancement of mechanical properties of neat polymer by an incorporated low loading of organophilic clay platelets into a polystyrene matrix used for the evaluation of mechanical properties as‐prepared samples. For example, mechanical strength (excepting flexural strength) almost remain same beyond 3 wt % clay loading in PS, whereas much detrimental effect being observed in the wear loss in case of PCNs with 5 wt % clay than 3 wt %. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Photostabilization of styrene–ethylene–butylene–styrene block copolymer by hindered phenol and phosphite antioxidants

The photostabilization of poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS), by hindered phenols and their combination with phosphite antioxidants has been studied by using a variety of spectroscopic methods including FTIR, UV, and luminescence spectroscopy coupled with crosslinking and hydroperoxide analysis. The addition of a hindered phenol was found to photostabilize the SEBS in terms of the inhibition of discoloration, and the formation of hydroperoxides, acetophenone, and oxidation products, as well as chain scission and disaggregation of the styrene units. Strong synergism was found with combinations of a hindered phenol and phosphite antioxidant, especially with an increase in the phosphite concentration. Residual titanium traces present as impurities in the material were found to play an important role in the photo‐oxidation of SEBS. Molecular weight appeared to be a determining factor in the proportion of chain scission/crosslinking reactions that occured. Nevertheless, the addition of antioxidants and the reduction of titanium content also proved satisfactory in stabilizing the low‐molecular‐weight material. J. VINYL. ADDIT. TECHNOL. 12:2–7, 2006. © 2006 Society of Plastics Engineers     

Preparation and rheological characterization of intercalated polystyrene/organophilic montmorillonite nanocomposite

Polystyrene (PS)/organophilic montmorillonite (OMMT) clay nanocomposites were prepared by a solvent casting method using chloroform as a cosolvent. Intercalation of the OMMT in the PS matrix was achieved as revealed by X‐ray diffraction. The IR spectra of the products indicated that the OMMT is homogeneously dispersed in the PS matrix. A thermogravimetric analysis (TGA) showed that the onset temperature increases linearly with the clay content. The glass‐transition temperature of the PS, examined using differential scanning calorimetry, had a trend similar to that from the TGA. The rheological properties of the PS/OMMT nanocomposites were also investigated via a rotational rheometer with a parallel plate geometry, and they exhibited sharper shear thinning and increased storage and loss modulus with clay content. Furthermore, the shear viscosity obtained from the steady shear experiment was well correlated with the complex viscosity obtained from the oscillatory experiment via the Cox and Merz relation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2106–2112, 2003     

Effect of polymer chain scission on photodegradation behavior of polystyrene/multi‐wall carbon nanotube composite

To clarify an effect of polymer chain scission on a polystyrene (PS)/multi‐wall carbon nanotube (MWNT) composite photodegradation, a relationship between the change of molecular weight and photodegradation behavior was studied. The MWNT loading brought about severe PS chain scission and led to the increase of the low molecular weight (less than 10⁵) fraction. The increase of the fraction was not proportional to the loading amount and showed the minimum at the 2% loading. The strange behavior was due to a rheological effect bringing about a decrease of shear stress in the composite preparation. An unsaturated end group was produced by the chain scission and became the photodegradation initiator leading to auto‐oxidation and crosslink reactions. The MWNT scavenged radical species and worked as an antioxidant. The coexistence of the unsaturated end group and MWNT made the photodegradation behavior complicated. However, the MWNT radical scavenging ability was considerably poor, and the MWNT had little ability to inhibit the photodegradation initiation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40362.     

Cover Picture: Macromol. Mater. Eng. 8/2005

Summary: Poly(butylene succinate‐co‐adipate) (PBSA) and organically modified montmorillonite (OMMT) nanocomposites of three different compositions were prepared by melt‐extrusion in a batch mixer. The structure of the nanocomposites was studied using X‐ray diffraction (XRD) and transmission electron microscopy (TEM) that revealed a coexistence of exfoliated and intercalated silicate layers dispersed in the PBSA matrix, regardless of the silicate loading. The degree of crystallinity of PBSA decreases with the addition of OMMT platelets. Dynamic mechanical analysis revealed remarkable increase in flexural storage modulus when compared with that of neat PBSA. Tensile property measurements exhibit substantial increase in stiffness with simultaneous increase in elongation at break of nanocomposites as compared to that of neat PBSA. The effect of clay loading on the melt‐state linear viscoelastic behavior of mixed intercalated/exfoliated nanocomposites was also investigated.

Elongation at break of compression molded annealed samples of neat PBSA and various PBSACNs.     

Artificial weathering effect on the structure and properties of polypropylene/polyamide‐6 blends compatibilized with PP‐g‐MA

The degradation of uncompatibilized and compatibilized PP/PA‐6 (70/30 wt %) with PP‐g‐MA under accelerated UV light was investigated using Fourier Transform Infrared Spectroscopy (FTIR) spectroscopy, melt flow index (MFI) tester, tensile test, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). FTIR analysis of the structure of the compatibilized and uncompatibilized blends after exposure to UV light showed the formation of photoproducts corresponding to both components. The MFI and mechanical results obtained revealed that photooxidation started primarily in PA‐6 rather than PP. In addition, the uncompatibilized blends exhibited a higher degradation rate compared to neat polymers for long exposure time, and the addition of PP‐g‐MA increased slightly their ageing rate in accordance with TGA data. Further, DSC analysis showed an increase in the crystallinity index and a decrease in the melting temperature of PP and PA‐6 after UV exposure either as neat polymers or as blend components. SEM micrographs of the cryo‐fractured surfaces of the samples illustrated the formation of cracks and fractures after UV irradiation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41722.     

Antipolyelectrolyte superabsorbing nanocomposites: Synthesis and properties

Novel polyampholytic superabsorbing nanocomposites based on the zwitterionic sulfobetaine monomer [3‐(methacrylamido)propyl)]dimethyl(3‐sulfopropyl)ammonium hydroxide were synthesized through in situ polymerization in aqueous solution with different contents of an organo‐modified clay (OMMT, Cloisite 30B). Structural and thermomechanical properties of hydrogels were characterized by FT‐IR, XRD, and DMTA, respectively. Swollen gel strength of hydrogels was determined by a rheological method. Storage modulus of the hydrogels was considerably improved in comparison with its the clay‐free counterpart. The nanocomposite hydrogel containing 15% OMMT possessed the highest gel strength. The glass transition temperature was increased from 58.4 to 67.0°C for the clay‐free and nanocomposite hydrogel containing 8% OMMT, respectively. The swelling behavior of the hydrogel in various salt solutions was investigated. Antipolyelectrolyte behavior was observed with enhancement of concentration of mono‐ and multivalent salts. Swelling in the various pH media was nearly pH‐independent over a wide range of pH. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Crystallization behavior of poly(p‐dioxanone)‐PU/montmorillonite nanocomposites prepared by chain‐extending reaction

Organo‐modified montmorillonites and poly(p‐dioxanone) (PPDO) diol prepolymers were used to prepare Poly(p‐dioxanone)‐PU/organic montmorillonite (PPDO‐PU/OMMT) nanocomposites by chain‐extending reaction. The crystallization behavior and spherulitic morphology of PPDO‐PU/OMMT nanocomposites were investigated by WXRD, differential scanning calorimetry, and polarized optical microscopy. The results show that the regularity of the chain structure plays a dominant role during the crystallization process rather than that of OMMT content and its dispersion status in PPDO matrix. With similar molecular weight and same OMMT content, PPDO‐PU/OMMT nanocomposite, which derived from lower molecular weight PPDO prepolymer, exhibits lower crystallization rate, melting point, and crystallinity. The influence of the clay content on the crystallization behavior highly depends on its dispersing state. The nucleating effect of OMMT can be only observed at high loading percentage. For the nanocomposites with low clay loading percentage, the retarding effect of exfoliated platelets on the chain‐ordering into crystal lamellae became the key factor. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical and rheological properties of PP/SEBS/OMMT ternary composites

The microstructure and mechanical properties of polypropylene (PP)/OMMT binary nanocomposites and PP/styrene‐6‐(ethylene‐co‐butylenes)‐6‐styrene triblock copolymer (SEBS)/OMMT ternary nanocomposites were investigated using X‐ray diffraction (XRD), transmission electron microscopy (TEM), and rheology and electromechanical testing machine. The results show that the organoclay layers are mainly intercalated and partially exfoliated in the PP‐based nanocomposites. The additions of SEBS and OMMT have no significant effect on the crystallization behavior of PP. At the same time, it can be concluded that the polymer chains of PP and SEBS have intercalated into the organoclay layers and increase the gallery distance after blending process based on the analytical results from TEM, XRD, and rheology, which result in the form of a percolated nanostructure in the PP‐based nanocomposites. The results of mechanical properties show that SEBS filler greatly improve the notched impact strength of PP, but with the sacrifice of strength and stiffness. OMMT can improve the strength and stiffness of PP and slightly enhance the notched impact strength of PP/PP‐g‐MA. In comparison with neat PP, PP/OMMT, and PP/SEBS binary composites, notched impact toughness of the PP/SEBS/OMMT ternary composites significantly increase. Moreover, the stiffness and strength of PP/SEBS/OMMT ternary nanocomposites are slightly enhanced when compared with neat PP. It is believed that the synergistic effect of both SEBS elastomer and OMMT nanoparticles account for the balanced mechanical performance of the ternary nanocomposites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

New approach for preparation of dry natural rubber nanocomposites through acid‐free co‐coagulation: Effect of organoclay content

Natural rubber (NR) vulcanizates exhibit good mechanical properties compared to vulcanizates of synthetic rubbers. Incorporation of a conventional filler at higher loadings to NR enhances its modulus, while reduction in tensile strength and elongation. This paper presents a new strategy for development of a NR‐clay nanocomposite with enhanced mechanical properties by incorporation of lower loadings (2–8 phr) of cetyl trimethyl ammonium bromide modified montmorillonite clay (OMMT‐C) under acid‐free environment. The effect of OMMT‐C loading on cure characteristics, rubber‐filler interactions, crosslink density, dynamic mechanical thermal properties, and mechanical properties were evaluated. Incorporation of OMMT‐C accelerated the vulcanization process and enhanced mechanical properties. X‐ray diffraction analysis and scanning electron microscopy images revealed that the formation of intercalated clay structures at lower OMMT‐C loadings, and clay aggregates at higher loadings. A nanocomposite at OMMT‐C loading of 2 phr exhibited the best balanced mechanical properties, and was associated with highest crosslink density and rubber–filler interactions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46502.     

Fracture behaviour of poly[ethylene–(vinyl alcohol)]/organo‐clay composites

BACKGROUND: Ethylene–(vinyl alcohol) (EVOH) copolymer/organo‐modified montmorillonite (OMMT) composites were investigated. Composites with two different percentages by weight of OMMT were prepared using a melt‐extrusion procedure in a twin‐screw extruder, using EVOH as matrix. Films made of EVOH and EVOH/OMMT composites were prepared in a cast‐film extrusion line. RESULTS: The mechanical properties were evaluated by tensile tests and the fracture behaviour was analysed using the essential‐work‐of‐fracture (EWF) method. Fracture characterization was carried out for the two main processing directions: melt flow direction and transverse direction. Fractographic observations were made using scanning electron microscopy. CONCLUSION: The tensile test results indicated good compatibility between EVOH and OMMT. In addition, the fracture tests showed the influence of the clay particle arrangement on the fracture behaviour, showing an increase in the specific essential work of fracture, w_e, which was attributed to the EVOH–OMMT interaction. The plastic term, βw_p, showed different trends depending on the test direction, explained by the size of the plastic zone and the restrictions to the EVOH plastic flow promoted by the clay particles. In this sense, the EWF method is shown to be a very useful tool for the analysis of structure–property relationships in polymer–organo‐clay composites. Copyright © 2009 Society of Chemical Industry     

Photochemistry of low‐density polyethylene–montmorillonite composites

Photo‐oxidation at the exposed surfaces of low‐density polyethylene/montmorillonite composites was analyzed with attenuated total reflection/Fourier transform infrared spectroscopy. It was found that the clay particles were dispersed but not exfoliated in the polymer matrix. The extent of oxidative degradation of the low‐density polyethylene matrix was slightly greater when montmorillonite was present and was greatest for the blend of low‐density polyethylene and organically modified montmorillonite. The Fourier transform infrared measurements demonstrated that the rate of photo‐oxidation in the bulk was lower than that observed at the surface, but the oxidation chemistry was similar at the surface and in the bulk. The distribution of the photo‐oxidation products was somewhat modified in the presence of montmorillonite and organically modified montmorillonite in comparison with pure low‐density polyethylene, with the yield of acidic products higher and the yield of double bonds lower. These observations were attributed to a slightly higher yield of radicals and some modification of the quantum yield for the processes leading to the formation of double bonds when the clay filler was present. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The Effect of γ‐Irradiation on the Structure and Properties of Poly(propylene)/Clay Nanocomposites

The oxidative degradation of PP/OMMT nanocomposites under γ‐irradiation was studied. Changes in structure and properties resulting from γ‐exposure in the range 0–100 kGy were investigated. The results were analyzed by comparing the influence of PP‐g‐MA and pristine OMMT on the oxidation kinetics of neat PP. γ‐Irradiation in the presence of air strongly degraded the properties of PP materials, particularly for radiation doses above 20 kGy. The rate of oxidative degradation of PP/OMMT/PP‐g‐MA nanocomposites was much faster than that of neat PP. This suggests that PP‐g‐MA and pristine OMMT components behave as oxidation catalysts, leading to the formation of free radicals in the polymer matrix.

     

Effect of montmorillonite on properties of styrene–butadiene–styrene copolymer modified bitumen

Clay/styrene–butadiene–styrene (SBS) modified bitumen composites were prepared by melt blending with different contents of sodium montmorillonite (Na‐MMT) and organophilic montmorillonite (OMMT). The structures of clay/SBS modified bitumen composites were characterized by XRD. The XRD results showed that Na‐MMT/SBS modified bitumen composites may form an intercalated structure, whereas the OMMT/SBS modified bitumen composites may form an exfoliated structure. Effects of MMT on physical properties, dynamic rheological behaviors, and aging properties of SBS modified bitumen were investigated. The addition of Na‐MMT and OMMT increases both the softening point and viscosity of SBS modified bitumens and the clay/SBS modified bitumens exhibited higher complex modulus, lower phase angle. The high‐temperature storage stability can also be improved by clay with a proper amount added. Furthermore, clay/SBS modified bitumen composites showed better resistance to aging than SBS modified bitumen, which was ascribed to barrier of the intercalated or exfoliated structure to oxygen, reducing efficiently the oxidation of bitumen, and the degradation of SBS. POLYM. ENG. SCI., 47:1289–1295, 2007. © 2007 Society of Plastics Engineers