Thermal behavior of hydrostatically extruded polycarbonate and high-impact polystyrene

Effects of hydrostatic extrusion on the thermal properties of polycarbonate (PC) and of high-impact polystyrene (HIPS) were studied using differential scanning calorimeter (DSC) measurements. A glass transition temperature (T_g) and a peak temperature were determined from the DSC curves for both PC and HIPS extrudates. The T_g values of the PC extrudates, with a percentage reduction in area, R, from 40 to 50%, change appreciably from the value for the as–received PC. The results of the hydrostatic extrusion of the PC billets suggest that a two stage deformation process of molecular chains may be involved. Shear-banding is observed for HIPS extrudates with R = 30 to 60%; this fact indicates that a sub-glass transition (β-transition) occurs at temperatures below T_g. It is suggested that the molecular chains of the HIPS extrudate with R = 70% are oriented in the direction of hydrostatic extrusion. The deformation mechanism of molecular chains caused by the hydrostatic extrusion is discussed.     

Dynamic mechanical properties and morphology of polypropylene/maleated polypropylene blends

The dynamic mechanical properties of both homopolypropylene (PPVC)/Maleated Poly-propylene (PP-g-MA) and ethylene-propylene block copolymer (PPSC)/Maleated Poly-propylene (PP-g-MA) blends have been studied by using a dynamic mechanical thermal analyzer (PL-DMTA MKII) over a wide temperature range, covering a frequency zone from 0.3 to 30 Hz. With increasing content of PP-g-MA, α relaxation of both blends gradually shift to a lower temperature and the apparent activation energy ΔE_α increases. In PPVC/PP-g-MA blends, β relaxation shifts to a higher temperature as the content of PP-g-MA increases from 0 to 20 wt % and then change unobviously for further varying content of PP-g-MA from 20 to 35 wt %. On the contrary, in the PPSC/PP-g-MA blends β₁ relaxation, the apparent activation energy ΔE_β1 and β₂ relaxation are almost unchanged with blend composition, while ΔE_β2 increases with an increase of PP-g-MA content. In the composition range studied, storage modulus É value for PPSC/PP-g-MA blends decreases progressively between β₂ and α relaxation with increasing temperature, but in the region the increment for PPVC/PP-g-MA blends is independent of temperature. The flexural properties of PPVC/PP-g-MA blend show more obvious improvement on PP than one of PPSC/PP-g-MA blends. Scanning electron micrographs of fracture surfaces of the blends clearly demonstrate two-phase morphology, viz. the discrete particles homogeneously disperse in the continous phase, the main difference in the morphology between both blends is that the interaction between the particles and the continuous phase is stronger for for PPVC/PP-g-MA than for PPSC/PP-g-MA blend. By the correlation of the morphology with dynamic and mechanical properties of the blends, the variation of the relaxation behavior and mechanical properties with the componenet structure, blend composition, vibration frequency, and as well as the features observed in these variation are reasonably interpreted. © 1996 John Wiley & Sons, Inc.     

Understanding the viscoelastic properties of extruded polypropylene wood plastic composites

The main goal of this study was to analyze the effect of process additives, that is, maleated polypropylene (MAPP), and a nucleating agent on the viscoelastic properties of different types of extruded polypropylene (PP) wood plastic composites manufactured from either a PP homopolymer, a high crystallinity PP, or a PP impact copolymer using dynamic mechanical thermal analysis. The wood plastic composites were manufactured using 60% pine wood flour and 40% PP on a Davis‐Standard Woodtruder?. Dynamic mechanical thermal properties, polymer damping peaks (tan δ), storage modulus (E′), and loss modulus (E″) were measured using a dynamic mechanical thermal analyzer. To analyze the effect of the frequency on the dynamic mechanical properties of the various composites, DMA tests were performed over a temperature range of ?20 to 100°C, at four different frequencies (1, 5, 10, and 25 Hz) and at a heating rate of 5°C/min. From these results, the activation energy of the various composites was measured using an Arrhenius relationship to investigate the effect of MAPP and the nucleating agent on the measurement of the interphase between the wood and plastic of the extruded PP wood plastic composites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1638–1644, 2003     

Mechanical properties and morphology of polypropylene composites. Talc-filled,elastomer-modified polypropylene

The balance of impact strength and rigidity of polypropylene can be significantly improved by physical blending of the polypropylene with a talc filler and a variety of elastomer types. Unsaturated elastomers were found to be effective impact strength improvers in 70/15/15 percent PP/elastomer/talc composites, whereas saturated elastomers gave rise to a high stiffness of such compounds. This is attributed primarily to different tendencies of the elastomers to coat the filler surface. Studies on a wider range of compositions, using a butadienestyrene-butadiene (SBS) block copolymer and a ethylene-propylene-diene (EPDM) terpolymer as representatives of the two elastomer classes, indicated that at high stiffness levels (flexural modulus > 1.6 GN/m²), the composites with SBS show the best balance of properties, whereas at higher impact levels EPDM leads to a higher rigidity and impact strength. On the basis of morphological studies such differences can be explained qualitatively, in spite of the complex structure of these composites.     

Isothermal crystallization of isotactic polypropylene blended with low molecular weight atactic polypropylene. Part I. Thermal properties and morphology development

The thermal properties and morphology development of isotactic polypropylene (iPP) homopolymer and blended with low molecules weigh atactic polypropylene (aPP) at different isothermal crystallization temperature were studied with differential scanning calorimeter and wide-angle X-ray scattering. The results of DSC show that aPP is local miscible with iPP in the amorphous region and presented a phase transition temperature at T_c=120 °C. However, below this transition temperature, imperfect α-form crystal were obtained and leading to two endotherms. While, above this transition temperature, more perfect α- and γ-form crystals were formed which only a single endotherm was observed. In addition, the results of WAXD indicate that the contents of the γ-form of iPP remarkably depend both on the aPP content and isothermal crystallization temperature. Pure iPP crystallized was characterized by the appearance of α- and γ-forms coexisting. Moreover, the highest intensity of second peak, i.e. the (0 0 8) of γ-form coexisting with (0 4 0) of α-form, and crystallinity were obtained for blended with 20% of aPP, the γ-form content almost disappeared for iPP/aPP blended with 50% aPP content. Therefore, detailed analysis of the WAXD patterns indicates that at small amount aPP lead to increasing the crystallinity of iPP blend, at larger amount aPP, while decreases crystallinity of iPP blends with increasing aPP content. On the other hand, the normalized crystallinity of iPP molecules increases with increasing aPP content. These results describe that the diluent aPP molecular promotes growth rate of iPP because the diluent aPP molecular increases the mobility of iPP and reduces the entanglement between iPP molecules during crystallization.     

Thermal and mechanical properties of a polypropylene nanocomposite

An experimental polypropylene (PP) nanocomposite, containing approximately 4 wt % of an organophilic montmorillonite clay, was prepared and characterized, and its properties were compared with those of talc‐filled (20–40 wt %) compositions. Weight reduction, with maintained or even improved flexural and tensile moduli, especially at temperatures up to 70°C, was a major driving force behind this work. By a comparison with the analytical data from a nylon 6 (PA‐6) nanocomposite, it was found that the PP nanocomposite contained well‐dispersed, intercalated clay particles; however, X‐ray diffraction, transmission electron microscopy, dynamic mechanical analysis, and permeability measurements confirmed that exfoliation of the clay in PP was largely absent. The increased glass‐transition temperature (T_g) of a PA‐6 nanocomposite, which possessed fully exfoliated particles, indicated the molecular character of the matrix–particle interaction, whereas the PP nanocomposite exhibited simple matrix–filler interactions with no increase in T_g. The PP nanocomposite exhibited a weight reduction of approximately 12% in comparison with the 20% talc‐filled PP, while maintaining comparable stiffness. Undoubtedly, considerable advantages may be available if a fully exfoliated PP nanocomposite is fabricated; however, with the materials available, a combination of talc, or alternative reinforcements, and nanocomposite filler particles may provide optimum performance. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1639–1647, 2003     

PP/木粉复合材料的热性能

以聚丙烯(PP)/木粉(WF)复合材料(WPC)为对象,研究了WF及马来酸酐接枝聚丙烯(PP-g-MAH)含量对WPC热性能的影响。PP和WF的熔融热焓分别为75.84 J/g和189.50 J/g,而w(WF)为10%,20%,30%,40%,50%的WPC的熔融热焓分别为54.99,40.37,38.66,27.34,22.09 J/g,加入PP-g-MAH后,WPC熔融热焓值有所提高。所有WPC在200～750℃的热分解都是分两步完成的,WF含量越高,两步分解现象越明显,第一步失重率越大;WPC每步分解的起始分解温度及峰值温度均有所提高,WPC对热更稳定。     

Dynamic mechanical properties and morphology of polypropylene block copolymers and polypropylene/elastomer blends

The relation between the dynamic mechanical properties and the morphology of polypropylene (PP) block copolymers and polypropylene/elastomer blends was studied by dynamic mechanical analysis (DMA), light- and electron microscopy. The latter techniques contributed to an improvement in assignments of relaxation transitions in the DMA spectra. It was established that PP block copolymers had multiphase structure since the ethylene/propylene rubber phase (EPR) formed in the copolymerization contained polyethylene (PE) domains. An identical morphology was found in the case of PP/polyolefin thermoplastic rubber (TPO) blends. Impact modification of PP by styrene/butadiene block copolymers led to a multiphase structure, too, due to the polystyrene (PS) domains aggregated in the soft rubbery polybutadiene phase. In the semicrystalline polyolefinic and in the amorphous styrene/butadienebased thermoplastic rubbers, PE crystallites and PS do mains acted as nodes of the physical network structure, respectively. PP/EPDM/TPO ternary blends developed for replacing high-density PE showed very high dispersion of the modifiers as compared to that of PP block copolymers. This fine dispersion of the impact modifier is a basic regulating factor of impact energy dissipation in the form of shear yielding and crazing.     

Tensile properties and morphology of blends of polyethylene and polypropylene

The tensile behavior of blends of linear polyethylene (PE) and isotactic polypropylene (PP) was examined in relation to their morphology. Yield stress increases monotonically with increasing PP content, while true ultimate strength is much lower in all blends than in the pure polymers as a result of early fracture. The blends fail at low elongation because of their two-phase structure, consisting of interpenetrating networks or of islands of PE in a PP matrix, as shown by scanning electron microscopy of fracture surfaces and transmission electron microscopy of thin films. While spherulites in PP are very large (～100 μm in diameter), addition of 10% or more of PE drastically reduces their average size. This, together with the profusion of intercrystalline links introduced by PE, may be associated with maximization of tensile modulus in blends containing ～80% PP. Introduction of special nucleating agents to PP reduces average spherulite size and is accompanied by slight improvements in modulus. Thin films of blends strained in the electron microscope neck and fibrillate in their PE regions, but fracture cleanly with little fibrillation in areas of PP.     

Thermal and rheological properties of maleated polypropylene modified asphalt

Modified asphalts using polymeric additives, such as isotactic polypropylene (iPP) and maleated polypropylene (MPP), for asphalt binders were prepared and characterized for potential usages in pavement construction. The differential scanning calorimetry (DSC) studies show that most of the crystallinity of iPP remains intact in the asphalt binders, but MPP exhibits more interaction with the asphalt due to the increase of the amorphous region of MPP. The phase distributions and rheological properties of the modified asphalts were examined by scanning electron microscope (SEM) and dynamic shear rheometer (DSR), respectively. The images of SEM show that the MPP‐rich phase is larger than the iPP‐rich phase in asphalt blends, which contributes to more dispersion of the polymer into the asphalt phase in the asphalt/MPP blend. From the rheological studies, the asphalt blends containing iPP exhibit higher viscosity in terms of higher temperature to get Newtonian behavior and have a higher performance grade for rutting resistance at high temperature and frequency. POLYM. ENG. SCI., 45:1152–1158, 2005. © 2005 Society of Plastics Engineers     

Thermal properties of nickel powder filled polypropylene composites

The thermal properties of nickel powder filled polypropylene composites were measured over a range of filler concentrations. The thermal conductivities increased with filler concentration. Data were compared with predictions by theoretical models for two phase systems. The equation of Cheng-Vachon gave reasonable agreement with measurements. A TGA (thermogravimetric) study of the composites showed that the presence of nickel powder increases the thermal stability of polymer through an increase in activation energy to a maximum at a critical filler concentration, beyond which the stability decreased. The Vicat softening point of the composites was also increased in the presence of Ni powder.     

Crystalline morphology of polypropylene and rubber-modified polypropylene

The crystalline morphology of injection-molded polypropylene (PP), its relationship with crazing, and the effects of various impact modifiers on the morphology, crystallization, and fusion of PP have been studied. The highly oriented skin layer of an injection-molded tensile bar after deformation was found to be free from crazing in contrast to the heavy craze density in the randomly oriented spherulitic core zone. Reasons for the difficulty in craze nucleation in a preoriented zone are given in light of Argon's theory of craze initiation. Addition of a rubbery phase results in an irregular texture of spherulite, smaller spherulitic diameter, and decrease in the degree of undercooling, but no appreciable change in heats of fusion and crystallization other than a trivial volume effect. The rubbery phase is not pushed by the melt–solid interface to relocate to the interspherulitic boundaries. Rather, it is engulfed by the growing melt–solid interface, leaving behind a random spatial distribution of rubber particles in the PP matrix.     

A study of the morphology and physical properties of polypropylene films

Data are presented showing that rapidly quenched polypropylene films contain a paracrystalline phase in addition to crystalline and amorphous phases. The density of the paracrystalline phase was found to vary between 0.8890 and 0.9080 g./cm.³. Other data show that the density of quenched polypropylene films increases during aging, the increase being a linear function of the logarithm of the film age. The physical properties of the films, secant modulus, impact strength, and coefficient of friction, were found to vary not only with crystallinity, i.e., composition-dependent density, but also to vary during aging when the density was increasing with little change in crystallinity. An example of this dependence is the increase in secant modulus of 10.9 × 10⁶ psi/g./cm.³ during aging and only 3.7 × 10⁶ psi/g./cm.³ as the crystallinity increased. Because of the three phases and the density–time change, it is possible to have films with the same density and different physical properties and, conversely, films with the same physical properties and different densities.     

Nanocomposites of silica reinforced polypropylene: Correlation between morphology and properties

Polypropylene/fumed hydrophilic silica nanocomposites were prepared via melt mixing method using a single‐screw extruder. Comparative study with and without compatibilizing copolymer agent (maleic anhydride grafted polypropylene: PP‐g‐AM) was conducted. The obtained results were interpreted in terms of silica nanoparticle–silica nanoparticle and silica nanoparticle‐polymer interactions. These results have shown that the addition of nanofillers improves the properties of the nanocomposites. From transmission electron microscopy, it was found that agglomerations of silica particles into the PP matrix increased in average size with increasing silica contents, except in presence of the copolymer. Storage modulus values of the nanocomposites measured by dynamic mechanical thermal analysis were sensitive to the microstructure of the nanocomposites. Higher silica contents resulted in higher storage modulus, revealing that the material became stiffer. By adding the compatibilizer, a further increase of storage modulus was observed due to the finer dispersion of the filler in the matrix and the increased interfacial adhesion. Crystallization rates were found to increase with the increase of silica nanoparticles as well as PP‐g‐MA content. In addition, silica nanoparticles and the compatibilizing agent present centers of germination and nucleation of crystallites. Thus, the use of the coupling agent resulted in a further enhancement of mechanical properties of the nanocomposites due to the reduction of silica agglomeration. POLYM. ENG. SCI., 54:2187–2196, 2014. © 2013 Society of Plastics Engineers     

Thermal and flammability properties of polypropylene/carbon nanotube nanocomposites

The thermal and flammability properties of polypropylene/multi-walled carbon nanotube, (PP/MWNT) nanocomposites were measured with the MWNT content varied from 0.5 to 4% by mass. Dispersion of MWNTs in these nanocomposites was characterized by SEM and optical microscopy. Flammability properties were measured with a cone calorimeter in air and a gasification device in a nitrogen atmosphere. A significant reduction in the peak heat release rate was observed; the greatest reduction was obtained with a MWNT content of 1% by mass. Since the addition of carbon black powder to PP did not reduce the heat release rate as much as with the PP/MWNT nanocomposites, the size and shape of carbon particles appear to be important for effectively reducing the flammability of PP. The radiative ignition delay time of a nanocomposite having less than 2% by mass of MWNT was shorter than that of PP due to an increase in the radiation in-depth absorption coefficient by the addition of carbon nanotubes. The effects of residual iron particles and of defects in the MWNTs on the heat release rate of the nanocomposite were not significant. The flame retardant performance was achieved through the formation of a relatively uniform network-structured floccule layer covering the entire sample surface without any cracks or gaps. This layer re-emitted much of the incident radiation back into the gas phase from its hot surface and thus reduced the transmitted flux to the receding PP layers below it, slowing the PP pyrolysis rate. To gain insight into this phenomena, thermal conductivities of the nanocomposites were measured as a function of temperature while the thermal conductivity of the nanocomposite increases with an increase in MWNT content, the effect being particularly large above 160 °C, this increase is not as dramatic as the increase in electrical conductivity, however.     

Mechanical properties and morphology of polypropylene composites II. Effect of polar components in talc-filled polypropylene

Using the concept of filler coating, a study has been made of the morphology and mechanical properties of polypropylene/talc/elastomer composites with a series of polar components as added elastomers. Both impact strength and stiffness of the blends were better than those of polypropylene homopolymer. Most of the polar components showed a considerable amount of filler coating, as evidenced by morphological studies. However, the impact strength of the composites was generally lower than that of similar blends with non-polar elastomers, probably owing to (a) the high glass transition temperatures of the polar components, (b) the poor dispersion of some of the elastomeric phases, and (c) a reduced affinity of the elastomers for polypropylene.     

Morphological studies on extruded films and filaments of polypropylene

In the present work, an attempt has been made to study the development of morphology during extrusion and uniaxial stretching of polypropylene (PP) films and filaments at corresponding conditions. Dies for extrusion of films and filaments were designed to achieve similar extrusion velocity and shear rates. Orientation in films and fibers of PP produced from these dies was determined by birefringence and wide-angle X-ray diffraction (WAXD). The degree of crystallinity was determined by density and WAXD. The superstructure developed during extrusion was studied in films by small-angle light scattering. It was inferred that films and fibers prepared under similar conditions would produce similar morphology. Hence, films can be characterized by optical techniques when it is difficult to study fibers. © 1994 John Wiley & Sons, Inc.     

Thermal conductivity of extruded polyethylene

The thermal conductivity of extruded polyethylene has been measured between 220 and 360K by a direct comparative method. For the material with the highest extrusion ratio the conductivity parallel to the extrusion direction, κ_∥, is 72 mW/cm K at room temperature and more or less constant over the complete temperature range. Between the same temperatures the conductivity perpendicular to the extrusion direction decreases with increasing T by about 50% with the anisotropy in the most highly extruded sample almost 30 at room temperature. The results on κ_∥ cannot be explained by the Takayanagi model used in our earlier papers and further modifications to the model are required.     

Transport properties and their correlation with the morphology of thermally conditioned polypropylene

Time-lag and static sorption experiments were employed to measure permeability, diffusivity and solubility constants of He, A, and CF₄ in polypropylene films cooled at various rates from the melt and subsequently annealed at varying temperatures near the melting point. While solubility constants in films annealed above 90°C showed the normal variation with the amorphous content of the polymer, solubility constants for all unannealed, quenched films were remarkably constant and independent of the rate of cooling. In fact, all quenched films appeared to have the same amorphous content (ca. 41%). The remaining material is believed to be a mixture of monoclinic and hexagonal crystallinity, the volume ratio of the two being a function of the rate of quenching, and changing on annealing, in favor of the more stable, monoclinic form; the transition occurring rather sharply at 90°C. X-ray diffraction provided supporting evidence for the presence of the hexagonal crystals. The diffusion behavior in crystalline polypropylene is normal and Fickian but instead of the usual decline with increasing crystallinity, diffusivities showed definite enhancement in the case of the annealed films, i.e., the expected monotonic decline of D with increasing crystallinity is not observed. This behavior is attributed to a reduction in diffusional impedance through formation of defects in existing crystallites, as the lamellae thicken, in a manner similar to that observed on annealing of polyethylene single crystals. The apparent activation energies of diffusion were essentially constant and independent of thermal history. This suggests that in a highly crystalline polymer diffusion is not so much impeded by the restricted mobility of chain segments but rather by the extremely small dimensions of the available diffusive pathways. In support of the argument that the transport properties of polypropylene are controlled at a level of microstructure well below the characteristic dimensions of spherulities, it was observed that bulk-crystallized polypropylene has a spherulitic structure whose size and texture do not change significantly on annealing.