DISPERSION AND TENSILE BEHAVIOR OF POLYPROPYLENE/MONTMORILLONITE NANOCOMPOSITES PRODUCED VIA MELT INTERCALATION

Most of the anicles on polymer nanocomposites focus on the importance of chemistry used to modify the surfaceof the clay, usually montmorillonite (MMT), and characterization of the nano-scale structure obtained. The role andimportance of processing were also discussed recently. However, few papers concerning the correlation between morphologyof MMT and mechanical properties were published. In order to understand the tensile behavior of PP/Montmorillonite(MMT) nanocomposites better, and to further improve the reinforcement efficiency, we first prepared the PP nanocompositesvia direct melt intercalation using conventional twin-screw extrusion. The dispersion and tensile property of the compositeswere then investigated by SEM, XRD, TEM and a video-controlled tensile set-up. The macroscopic and microscopicdispersion of MMT in PP matrix was verified by XRD and TEM, combined with SEM. The tensile properties were obtainedby video-controlled tensile set-up, which gives true stress-strain curve. It was found that a partly intercalated and partlyexfoliated structure (also called incomplete exfoliation) existed in the system. Though the tensile strength of PPnanocomposites is not much improved in engineering stress-strain curves, more than 20% increase of true stress was found ina true stress-strain experiment at high true strain, which indicates that only oriented silicate layers can have a big effect ontensile properties. Not only orientation of silicate platelets but also the degree of exfoliation is a key factor to determine thereinforcement efficiency. The reinforcement efficiency of MMT has been discussed based on the "continuum" Halpin-Tsaiequations. A good agreement was found between experimental data and theoretical prediction by changing N value (number of platelets per stack) which corresponding to different state of the dispersion of MMT in PP matrix.     

Structure and Properties of β-Polypropylene Reinforced by Polypropylene Fiber and Polyamide Fiber

Matrix/fiber composites of β-form isotactic polypropylene(iPP) matrix and α-iPP or PA6 fibers were prepared by laminating technique under different preparation temperatures. The mechanical properties and interfacial morphologies of these composites were studied by tensile test, optical microscopy and scanning electron microscopy, respectively. The experimental results show that the tensile yield load and tensile modulus of β-iPP/PA6 matrix/fiber systems increased significantly at the expense of elongation at break. These mechanical properties show essentially no dependence on the sample preparation temperature. On the other hand, the mechanical properties of iPP matrix/fiber single polymer composites depend strongly on the sample preparation temperature. At low sample preparation temperature, e.g., 172 ℃, the solid α-iPP fiber induces α-iPP crystallization, leading to the formation of α-iPP transcrystalline layer around the fiber. This results in a remarkable increment of the tensile yield load and tensile modulus. The elongation at break is also much better than that of the iPP/PA6 matrix/fiber system. It reflects a better interfacial adhesion of the single polymer composite compared with the iPP/PA6 composite. At higher sample preparation temperature, e.g., 174 ℃ or 176 ℃, the partial surface melting of the oriented fiber allows interdiffusion of iPP molecular chains in the molten fiber and matrix melt. The penetration of matrix chains into the molten iPP fiber results in some iPP molecular chains being included partially in the recrystallized fiber and the induced β-transcrystalline layers. This kind of configuration leads to an improvement of interfacial adhesion between the fiber and matrix, which causes a simultaneous increase of the tensile yield load, tensile modulus and elongation at break of β-iPP.     

Effect of clay modification on the structure and mechanical properties of polyamide-6 nanocomposites

Polyamide-6 nanocomposites were prepared from a new phosphonium organoclay obtained at pilot scale in supercritical carbon dioxide (scCO₂) and a commercially available ammonium modified-silicate. The composites were homogenised by twin-screw extrusion, then specimens for testing were prepared by injection moulding. The clay content of the composites was varied from 0 to 7 vol.% in 7 steps. The clays were characterised in detail; they differed in their surface coverage and gallery structure, while their particle size was similar and their surface energy differed only slightly. X-ray diffraction, electronic microscopy and rheology were used for the characterisation of composite structure. Different gallery structure of the clays led to dissimilar extent of exfoliation. The phosphonium organoclay exfoliated better in PA than the silicate treated with the ammonium salt in spite of its smaller surface coverage. The nanocomposites showed the usual complex structure: besides individual platelets and intercalated stacks, large particles were also present and the development of a silicate network could be shown at large clay contents. Quantitative determination of the extent of reinforcement revealed two determining factors: contact surface and strength of interaction. The first increases with exfoliation, but the latter decreases as an effect of organophilisation. The extent of exfoliation was also estimated quantitatively, and the calculation confirmed the results of qualitative evaluation showing larger extent of exfoliation for the scCO₂-prepared phosphonium clay.     

Effects of surface modification of fumed silica on interfacial structures and mechanical properties of poly(vinyl chloride) composites

Poly(vinyl chloride) (PVC)-based composites were prepared by blending PVC with nano-SiO₂ particles, which were treated with dimethyl dichlorosilane (DMCS), γ-methylacryloxypropyl trimethoxy silane (KH570). The dispersion and interfacial compatibility of nano-SiO₂ particles in PVC matrix was characterized by SEM, which indicated that DDS had a better dispersion and compatibility than UTS but worse than KHS. The mechanical properties, processability and effective interfacial interaction of nano-SiO₂/PVC composites were studied. The nano-SiO₂ particles treated with KH570 or DMCS significantly reinforced and toughened the PVC composites. The maximum impact strength of PVC composites was achieved at a weight ratio of nano-SiO₂/PVC:4/100. The tensile yield stress increased with increasing the content of treated inorganic particles. The incorporation of untreated nano-SiO₂ particles adversely affected the tensile strength of the composite. Although the equilibrium torques of all nano-SiO₂/PVC composites were higher than that of pure PVC, the surface treatments did reduce the equilibrium torque. The interfacial interaction parameter, B, and interfacial immobility parameter, b, calculated respectively from tensile yield stress and loss module of nano-SiO₂/PVC composites, were employed to quantitatively characterize the effective interfacial interaction between the nano-SiO₂ particles and PVC matrix. It was demonstrated that the nano-SiO₂ particles treated with KH570 had stronger effective interface interaction with PVC matrix than those treated with DMCS, which also had stronger effective interface interaction than the untreated nano-SiO₂ particles.     

Approaches for Making High Performance Polymer Materials from Commodity Polymers

A brief surrey of ongoing research work done for improving and enhancing the properties of commodity polymers by the author and author’s colleagues is given in this paper. A series of high performance polymers and polymer nanomaterials were successfully prepared through irradiation and stress-induced reactions of polymers and hydrogen bonding. The methods proposed are viable, easy in operation, clean and efficient. 1. The effect of irradiation source (UV light, electron beam, γ-ray and micr…     

Cold‐drawn induced microstructure in PVC‐bentonite nanocomposites

The mechanical properties and cold drawn‐induced micro and nanostructure of polyvinyl chloride (PVC)‐bentonite nanocomposites have been investigated. Molded sheets with 5 wt% concentration of bentonite and two processing additives were melt extruded and two‐roll‐milled processed. The flame retardant additive promoted polymer intercalation whereas a pigment dispersant promoted clay exfoliation, the polymer matrix showed isotropic orientation. The intercalated nanocomposite exhibited nanoplates oriented with their planes parallel to the molded sheet surface and the Young's modulus and yield stress were significantly enhanced relative to neat PVC. The strain at fracture (～144%) was slightly reduced relative to the matrix (～167%). Cold drawing induced molecular chain orientation along the tensile axis and preserved the orientation of the intercalated nanoclays. The fracture mechanism, as investigated via scanning electron microscopy (SEM) revealed plastic fracture mechanism (similar to neat PVC). On the other hand, the exfoliated nanocomposite did not show any improvement in mechanical properties but rather a significant decay of strain at fracture (～44%). The fractured region, as examined by SEM, exhibited microvoid morphology. Analysis of the fractured region showed PVC macromolecules oriented along the tensile axis but no preferred orientation of the nanoclays. The limited strain at fracture found for this material appears to be associated with the initially randomly oriented nanoclays being unable to orient under the tensile deformation. The nanoclays would act as stress concentrators leading to rapid material's failure due to loss of adhesion with the polymer matrix. The results suggest that exfoliated nanoclays could play a detrimental role when the nanocomposite is subjected to large deformations at temperatures well within the glassy regime. Copyright © 2009 John Wiley & Sons, Ltd.     

Estimation of interphase thickness and properties in PP/layered silicate nanocomposites

Nanocomposites were prepared from sodium montmorillonite (NaMMT) and organoclays (OMMT) with different particle sizes as a function of silicate content. Composite structure was characterized by various methods including X-ray diffraction (XRD), scanning electron microscopy (SEM) and rheology. Model calculations were carried out to estimate the thickness and yield stress of the interphase forming in the composites. The results proved the formation of an interphase, but the determination of interphase properties was hampered by several factors. First of all, the particle size of the filler changed quite considerably in PP/OMMT composites in spite of earlier observations and expectations. Particle characteristics changed even further when a relatively small amount (5 vol.%) of functionalized polymer (MAPP) was added to the composite. As a consequence, the estimation of the contact surface between the silicate and the polymer became extremely difficult. In spite of the uncertainties overall values of interphase properties were obtained using the results of all composites prepared. The prediction for the average thickness of the interphase is 0.23 μm and we obtained 51.2 MPa for interphase yield stress, but this estimate neglects the different interactions developing in composites containing the uncoated and the modified silicate, respectively.     

Surface characteristics of layered silicates: Influence on the properties of clay/polymer nanocomposites

A sodium montmorillonite and six organophilic montmorillonites coated with different surfactants were characterized in various ways in the study. Particle and surface characteristics were determined by nitrogen adsorption and inverse gas chromatography, respectively. The gallery structure of organophilic montmorillonite, the orientation of surfactants in the galleries, and surface coverage were estimated by X-ray diffraction measurements and model calculations. The effect of organophilization on the properties of polypropylene/clay composites was determined by the measurement of tensile properties. The results showed that the surface energy of uncoated layered silicates is large; thus, the forces keeping the layers together are very strong. The long chain surfactants used for the coating of montmorillonite orientate more or less parallel to the surface and usually cover the platelets in a single layer in commercial silicates. Surplus surfactant is not located in the galleries, but among the particles, and might influence the properties of composites negatively. Organophilization leads to the drastic decrease of surface free energy. Surface tension of all coated clays is practically the same, irrespective of the type of the surfactant used for treatment. Low surface energy leads to weaker forces between the layers, which might facilitate exfoliation. This effect can be further enhanced by the use of surfactants with two long aliphatic chains, one of which orientates vertically to the surface, leading to larger gallery distance. Polymer/silicate interaction also decreases as an effect of decreasing surface tension proved by the decrease of tensile yield stress of polypropylene/montmorillonite composites. Besides surface tension, the exfoliation of layered silicates is influenced by several other factors as well, like gallery distance, mutual solubility of the components, competitive adsorption, or possible chemical reactions.     

聚丙烯多相体系中β晶的研究进展

综述了近年来聚丙烯(PP)基多相体系,如PP/弹性体(橡胶)、PP/聚乙烯(PE)、PP/对苯二甲酸乙二脂(PET)、PP/聚酰胺(PA)等共混体系和PP/CaCO3、PP/滑石粉、PP/蒙脱土(MMT)以及PP与其它无机物的复合体系中聚丙烯β晶的研究进展,阐述了在这些聚丙烯基共混和复合体系中影响聚丙烯β晶生成的因素、聚丙烯β晶的生成机理以及聚丙烯β晶对多相体系结构和性能的影响,并对富含β晶的聚丙烯(PP)基多相体系的研究和应用的发展趋势进行了展望。     

Dielectric,magnetic and mechanical properties of ferrite composites

The dielectric and magnetic properties of carbonyl—iron (CI) and nickel zinc ferrite polymer composites were studied with respect to the ferrite particulate content and microwave frequency. From the experimental data and using empirical models that relate the composite dielectric and magnetic properties, the respective dielectric and magnetic properties of the neat fillers were estimated. The tensile properties of the particulate composites comprising CI were shown to follow qualitatively Mooney's equation for the elastic modulus. The tensile strength of an elastomeric polyurethane and PVC composites containing CI increased with particulate content, while the elongation to break decreased with filler content. SEM micrographs of tensile fracture surfaces indicated that somewhat better adhesion is obtained in the case of the polyurethane-based composites compared to the PVC ones.     

The Effect of Degradation and Stabilization on the Mechanical Properties of Polymers Using Polypropylene Blends as the Main Example

Degradation can result from a variety of chemical, physical and mechanical mechanisms, most of them involving a reduction of molecular weight and thus a decrease in the mechanical performance of the degraded polymer. A clear understanding and control of these mechanisms is absolutely essential: without stabilization some polymers (e.g. PVC, polyolefins) would not survive their processing undamaged. In this paper an overview of the different degradation mechanisms, their effect on molecular chains, and the methods used to characterize the extent of degradation will be given. Subsequently we establish some fundamental relationships between the microstructure and the mechanical performance (of thermoplastic polymers) using differently aged and stabilized polypropylene (PP) - EPR compounds. In particular we investigate the influence of two types of heat stabilizers (phenolic antioxidants and hindered amine stabilizer HAS) on the degradation behaviour of test specimens thermally aged at 120 and 135°C respectively. From an investigation of the changes with aging time in structure and low-strain properties (yield stress, strain at yield, tensile modulus) and from the differences in the evolution of the fracture properties a molecular model of the chain scission mechanisms and of inter-lamellar connectivity (through tie-chain molecules) has been established, which allowed an explanation of the gradual change of the dominant deformation mechanism from cold drawing to crazing and brittle fracture.     

Mechanical and Rheological Behavior of Unvulcanized and Dynamically Vulcanized i-PP/EPDM Blends

The mechanical and rheological behavior of dynamically vulcanized PP/EPDM blends is examined and compared with those of unvulcanized blends. The effect of blend ratio and dynamic vulcanization of EPDM rubber on tensile properties and flow are investigated. The mechanical properties of the blends are strongly influenced by the blend ratio. With the increasing of EPDM content the value of yield stress in a solid state decreases with the elastomer volume fractions less than 0.45 for the unvulcanized blends. For the dynamically vulcanized blends the interval of EPDM content, at which the yield peak is seen, is rather limited below 0.25 elastomer volume fractions. It is shown that dynamic vulcanization changes the deformational behavior of PP/EPDM blends. The rheological properties of dynamically vulcanized blends depending on the ratio of the components may be similar to the properties of polymer composites containing the highly disperse structuring filler. The distinction between the rheological behavior of unvulcanized and dynamically vulcanized blends is related to differences of their structures and viscoelastic characteristics of unvulcanized and vulcanized EPDM phase.     

聚丙烯/硫酸钡复合体系的界面相互作用与流变性质和结晶行为的关系

制备了一系列具有不同界面状态的聚丙烯 (PP) 硫酸钡 (BaSO4)复合体 .PP BaSO4的界面分别用硅烷、硬脂酸、马来酸酐接枝聚丙烯 (PP g MAH)改性 .研究表明 ,填充体系的熔体粘度和熔体弹性均高于基体 .以硅烷和PP g MAH进行界面改性后 ,PP BaSO4的界面相互作用加强 ,导致复合体系中的熔体粘度和熔体弹性进一步提高 ,同时BaSO4对PP的成核活性提高 .填料用硬脂酸处理后 ,硬脂酸能够在填料粒子表面上形成一个包覆层 ,使粒子与PP的亲和性改善 .同时该包覆层具有润滑作用 ,使得复合体系的熔体粘度和熔体弹性下降 ,并使得该体系中BaSO4的成核活性低于硅烷和处理的体系 .本文探讨了由复合体系的熔体粘度定量比较填充复合体系中聚合物 填料界面相互作用的方法 ,讨论了界面改性对复合体系流变性质和结晶行为影响的机理     

Characterization and thermal degradation of polypropylene-montmorillonite nanocomposites

Polypropylene (PP)-montmorillonite nanocomposites have been prepared using isotactic PP homopolymers with different rheological properties, and a maleic anhydride grafted PP. Morphology and structure of the composites were investigated by using X-ray techniques (WAXD, SAXS) and transmission electron microscopy (TEM). The absence of pristine clusters of the clay and the presence of intercalated and exfoliated structures were shown for all the investigated samples. The nanocomposite prepared by using maleic anhydride grafted PP showed a widespread exfoliation. The thermal behaviour and degradation have been studied by means of differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The incorporation of the montmorillonite improves the thermal stability in air atmosphere of all the investigated PPs, thanks to a physical barrier effect of the silicate layers.     

Oscillatory shear-accelerated exfoliation of graphite in polypropylene melt during injection molding

In this study, good dispersion status of graphite in a nonpolar, intractable polymer, i.e. polypropylene (PP), was realized in melt processing by using a specific dynamic packing injection molding (DPIM) technique. The exfoliation extent of graphite increased remarkably from the skin zone to the core zone of the molded part, as confirmed by combination of WAXD, SEM and TEM analyses, indicating an accelerated exfoliation occurred during the DPIM processing. This phenomenon is due to decreased melt flow channel and increased melt viscosity as the solidification takes place from the wall into the center, which leads to greatly increased shear force. The good dispersion of graphite results in obvious reinforcements of both tensile strength and impact strength by adding moderate amount of graphite. The present study proposes a promising route for realizing the large-scale fabrication of structural parts of polymer/exfoliated-graphite nanocomposites with excellent mechanical properties.     

Variations in the mechanical properties of end products from mixed plastics

From well selected polymers, using an experimental plan methodology, we show the different influences (nature, processing conditions, composition) on the properties of end products from mixed plastics such as strain and stress at rupture, flexural modulus, impact strength and extrusion flow rate. From models, it is possible to adjust necessary formulations to obtain a good quality level and, eventually, an improvement of poor properties. Mixed plastics can be considered as a polyethylene matrix containing other polymers such as polypropylene (PP), polystyrene (PS) or poly(vinyl chloride) (PVC). Poly(ethylene terephthalate) (PET) is neglected in this study. Properties such as strain at rupture or impact strength are drasticly affected by the level of polypropylene, polystyrene or poly(vinyl chloride): 5 or 10% nullify these properties. Other properties such as stress at rupture, flexural modulus or extrusion flow rate highly depend on the relative ratio of polymers. To improve the poor properties or to obtain a good level in a property, it is necessary to add well adapted compatibilizers or to dope the mixed plastics material by one of the polymers.     

Surface tension and mechanical properties in polyolefin composites

Polyolefin composites were prepared with CaCO₃ fillers of different specific surface area. The fillers were surface treated with stearic acid between 0 and 100% surface coverage. As an effect of the treatment, surface tension of the fillers and also polymer/filler interaction decreased. The relation between interfacial interaction and mechanical properties of the composites was analysed by the equation developed earlier to describe the composition dependence of the tensile yield stress. The characteristics of the interphase were calculated, its yield stress decreases and thickness increases with increasing surface coverage. Reversible work of adhesion can be successfully related to the tensile yield stress, but a more complicated correlation exists between the thickness of the interphase and the strength of the interaction than assumed earlier. Other mechanical properties also change with the surface treatment; modulus and strength decrease and extensibility increases with decreasing polymer/filler interaction.     

The β-nucleated ternary composites of polypropylene/nano-CaCO3/short poly(ethylene-terephthalate) fiber

A serial of β-nucleated polypropylene (β-PP)/nano-calcium carbonate (nano-CaCO₃)/ short poly(ethylene-terephthalate) (PET) fiber composites were prepared using extrusion blending. Maleic anhydride grafted PP (PP-g-MA) was used to modify the compatibility. The relationships among components, structure, and properties of the PP composites were studied. The results show that adding nano-CaCO₃ improved the mechanical properties of the materials. Adding PET fiber increased the rigidity and toughness but the tensile strength decreased. PP-g-MA modified the compatibility of the components of the composites. Both PET fiber and nano-CaCO₃ had nucleation effect on the PP crystallization and slightly induced the formation of β crystals. Ternary β-PP/nano-CaCO₃/PET fiber composites contained high β-crystal content, and the compatibilizer exhibited synergy effect with β nucleating agent to further increase the β-crystal content in the blends. Mo’s method could satisfactorily describe the nonisothermal crystallization behavior of ternary composites, whereas Jeziorny and Ozawa methods failed to do the same ideally.     

Comparative analysis of nanocomposites based on polypropylene and different montmorillonites

Nanocomposites of polypropylene (PP) were prepared by melt mixing using maleic anhydride modified polypropylene (PPg) and different organophilic montmorillonites (OMMT). The selected organo-modified clays differ in their initial particle size, amount and type of surfactant and/or their cation-exchange capacity. All composites have 80, 15 and 5 wt% of PP, PPg and OMMT, respectively. The materials were characterized using TGA, XRD, SEM and rotational rheometry. Cloisite 15A, Cloisite 93A, Nanomer I44 and a bentonite modified with octadecylammonium (B18) display intercalation and exfoliation after mixing and annealing and produce nanocomposites with different degrees of ‘solid-like’ rheological behavior. The composites based in Cloisite 15A and Nanomer I44, which use the same intercalant, show very similar phase structure and rheological response, regardless of the origin and initial characteristics of the clays. These nanocomposites are the most affected by the thermal history during rheological characterization in the molten state. On the other hand, Cloisite 10A and Cloisite 30B display collapse of the silicate layers after compounding with no evidence of exfoliation.     

Effect of ionizing radiation on physicochemical and mechanical properties of commercial monolayer and multilayer semirigid plastics packaging materials

Tensile testing, overall migration tests and sensory tests were used to evaluate the effects of gamma irradiation (5–60 kGy) on six commercial semirigid packaging materials. The monolayer and multilayer materials in sheet or bottle form were: polystyrene (PS), polypropylene (PP), polyvinyl chloride/high-density polyethylene (PVC/HDPE), polyethylene terepthalate (PET), HDPE/polyamide (HDPE/PA) and HDPE. In terms of mechanical strength, PET was the most radiation-resistant material, while the HDPE monolayer and multilayer showed some degradation after 60 kGy. PS was slightly affected after 30 kGy, whereas PP was severly degraded and became very brittle. Generally, there was no change in overall migration at lower doses; at higher doses migration from PP tended to increase, while migration from HDPE/PVC tended to decrease. Odor and taste transfer as well as discoloration were observed with most plastics, especially at higher doses, and it is concluded that these tests are a sensitive and important quality control tool for evaluating irradiated packaging materials.