Toughening and reinforcing polypropylene with core–shell structured fillers

An elastomer/rigid particle filler with core–shell structure was prepared by twin‐screw extruder according to an encapulation model. It was used to toughen and reinforce polypropylene (PP). An original idea of a one‐step processing method was adopted in creating PP/polyoctene–ethylene/talc ternary composites. The rheological behavior of PP was changed and the mechanical properties were improved. SEM observation showed that the core–shell structured filler dispersed better in copolypropylene than in homopolypropylene. Two reasons were proposed and proved by the rheology test and SEM observation. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2397–2403, 1999     

Toughening of polypropylene with crystallizable poly(ethylene oxide)

A crystallizable polymer, poly(ethylene oxide) (PEO), was used as new modifier to tailor the toughness of isotactic polypropylene (iPP). An optimum performance was achieved at a medium PEO content of 15 wt% where the toughness was enhanced by 300%, while the strength only decreased slightly. To elucidate the origin of toughening in the iPP/PEO blends, various crystallographic and morphological experiments including X‐ray diffraction, electron microscopy and calorimetry were adopted to explore the dependences of polymorphic composition and crystallized morphology on PEO content. When the PEO content is less than 15 wt%, the dispersed PEO cannot crystallize, and these non‐crystalline PEO microspheres are embedded in both α‐ and β‐form iPP spherulites, which is mainly responsible for the toughening. In contrast, when the PEO content is higher than 15 wt%, the PEO phase becomes crystallizable, and significant phase segregation takes place, resulting in a marked deterioration in mechanical properties. Copyright © 2011 Society of Chemical Industry     

Preparation and mechanical properties of high‐performance short ramie fiber‐reinforced polypropylene composites

Short ramie fiber (RF) was used to reinforce the polypropylene (PP). The composites were prepared in a twin‐screw extruder followed by injection molding. The experimental results showed that both the strength and the modulus of the composites increase considerably with increasing RF content. The tensile strength and flexural strength are as high as 67 and 80 MPa by the incorporation of ramie up to 30 wt %. To the best of our knowledge, this is one of the best results for short natural fiber‐reinforced PP composites. However, the preparation method in this study is more simple and economic. This short RF‐reinforced PP composites extend the application field for short‐nature fiber‐reinforced PP composites. Morphological analysis revealed that it is the high aspect ratio of the fiber and good interfacial compatibility that result in the high performance of the composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Toughening of isotactic polypropylene with CaCO3 particles

The mechanisms of deformation and fracture of isotactic polypropylene filled with CaCO₃ particles were studied. Three types of particles with average diameters of 0.07, 0.7, and 3.5 μm were used at filler volume fraction from 0.05 to 0.30. The experiments included slow tensile tests, notched Izod impact tests with varying notch depths, and fracture resistance tests using double-cantilever-beam sample configurations. In slow tension, addition of fillers increased the modulus and decreased the yield stress independently of filler type. The strain at break increased with initial incorporation of fillers but decreased at higher loadings. The 0.7 μm diameter particles improved Izod impact energy up to four times that of the unfilled matrix. The other particles had either adverse or no effect on the impact toughness. The toughening mechanisms at work were plastic deformation of interparticle ligaments following particle-matrix debonding with additional contribution coming from crack deflection toughening. The failure of the 0.07 and 3.5 μm diameter particles to toughen the matrix was attributed to poor dispersion.     

Isothermal crystallization behavior of metallocene‐catalyzed isotactic polypropylene

Isothermal crystallization behavior of isotactic polypropylene (iPP) synthesized using metallocene catalyst was investigated in this work. The isotacticity of the polypropylene was characterized by ¹³C‐NMR spectroscopy. It was found that the melting temperature (T_m) of the iPP is 123.51°C and the crystallization temperature (T_c) is 93°C. The iPP synthesized in this work did not show a general increase of T_m with an increase of crystallization temperature T_c, due to the short crystallization time of 20 min and low molecular weight (number average molecular weight = 6,300). The iPP showed a tendency of increasing heat of fusion (ΔH_f) with decreasing crystallization temperature. All the spherulites of iPP samples showed negative birefringence. For the iPP sample crystallized at the highest T_c (= 123°C, just below T_m), the spherulite showed a pronounced Maltese Cross and a continuous sheaf‐like texture aligning radially, which suggests that R‐lamellaes are dominant in this spherulite. The crystalline structure of the iPP was also investigated by X‐ray diffraction. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 231–237, 2005     

Mechanical properties and superstructure of isotactic polypropylene fibers prepared by continuous vibrating zone‐drawing

A continuous vibrating zone‐drawing (CVZD) was applied to study the effect of vibration on the mechanical properties and superstructure of isotactic polypropylene fibers. The CVZD treatment was a new drawing method by which the fiber was continuously drawn at a rate of 0.5 m/min under vibration using the specially designed apparatus. The CVZD treatment was carried out in five steps at a drawing temperature of 150°C and a frequency of 100 Hz, and applied tensions increased step by step with processing in the range of 14.8 to 207 MPa. The obtained fiber had a birefringence of 0.0373, crystallinity of 62.4%, tensile modulus of 17.6 GPa, and tensile strength of 1.11 GPa. These values are higher than those of the continuous zone‐drawn isotactic polypropylene fiber previous reported. The vibration added to the fibers during the zone‐drawing was effective in developing amorphous orientation and improving the mechanical properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 600–608, 2001     

Rheological properties of calcium silicate‐filled isotactic polypropylene

The melt rheological behavior of calcium silicate‐filled isotactic polypropylene, with filler volume contents of 0–17.8%, was determined at 493 K. The composites followed the power law in shear stress versus shear rate variations and were shear thinning. Initially, apparent melt viscosity decreased until a critical filler volume content of 8.5% was reached. However, on further increase in calcium silicate concentration, apparent melt viscosity increased. Melt elasticity also showed an initial decrease until 8.5% filler content was reached and then an increase beyond this filler content. Surface treatment of calcium silicate with a titanate coupling agent, LICA 38, modified the rheological properties because of the plasticizing/lubricating effect of LICA 38. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1511–1518, 2003     

Further study on double‐melting endotherms of isotactic polypropylene

The origins of the single‐ and double‐melting endotherms of isotactic polypropylene crystallized at different temperatures were studied carefully by differential scanning calorimetry, wide‐angle X‐ray diffraction, and small‐angle X‐ray scattering. The experimental data show that spontaneous crystallization occurs when the crystallization temperature is lower than 117°C; thus the lamellae formed are imperfect. At a lower heating rate, the recrystallization or reorganization of these imperfect lamellae leads to double endotherms. On the other hand, when the crystallization temperature is higher than 136°C, two major kinds of lamellae with different thickness are developed during the isothermal process, which also results in the double‐melting endotherms. In the intermediate temperature range the lamellae formed are perfect, and there is only a single peak in the distribution of lamellar thickness. This explains the origin of the single‐melting endotherm. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 163–170, 2000     

Biaxial self‐reinforcement of isotactic polypropylene prepared in uniaxial oscillating stress field by injection molding. I. Processing conditions and mechanical properties

This research explores the longitudinal and latitudinal mechanical properties of injection‐molded isotactic polypropylene (iPP) prepared in a uniaxial oscillating stress field by oscillating packing injection molding (OPIM). The methods, processing conditions, and mechanical test results for iPP by conventional injection molding (CIM) and OPIM are described. The mechanical properties in the flow direction (MD) and transverse direction (TD) of the OPIM moldings indicate three types of self‐reinforced iPP moldings. The pronounced biaxially self‐reinforced iPP specimens exhibit a 55–70% increase of the tensile strength and more than a fourfold increase of the impact strength in the MD, together with more than a 40% increase of the tensile strength and a 30–40% increase of the impact strength in the TD. The OPIM moldings show different stress–strain behavior in the MD and TD. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1906–1910, 2000     

The effect of fiber concentration on mechanical and thermal properties of fiber‐reinforced polypropylene composites

A novel composite material consisting of polypropylene (PP) fibers in a random poly(propylene‐co‐ethylene) (PPE) matrix was prepared and its properties were evaluated. The thermal and mechanical properties of PP–PPE composites were studied by dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) with reference to the fiber concentration. Although, by increasing PP fiber concentration in PPE, no significant difference was found in melting and crystallization temperatures of the PPE, the storage, and the tensile and flexural modulus of the composites increased linearly with fiber concentrations up to 50%, 1.5, 1.0, 1.3 GPa, respectively, which was approximately four times higher than that for the pure PPE. There is a shift in glass transition temperature of the composite with increasing fiber concentration in the composite and the damping peak became flatter, which indicates the effectiveness of fiber–matrix interaction. A higher concentration of long fibers (>50% w/w) resulted in fiber packing problems, difficulty in dispersion, and an increase in void content, which led to a reduction in modulus. Cox–Krenchel and Haplin–Tsai equations were used to predict tensile modulus of random fiber‐reinforced composites. A Cole–Cole analysis was performed to understand the phase behavior of the composites. A master curve was constructed based on time–temperature superposition (TTS) by using data over the temperature range from −50 to 90°C, which allowed for the prediction of very long and short time behavior of the composite. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2260–2272, 2005     

Mechanical behavior of agro‐residue‐reinforced polypropylene composites

In this research, fully environment‐friendly, sustainable and biodegradable composites were fabricated, using wheat straw and rice husk as reinforcements for thermoplastics, as an alternative to wood fibers. Mechanical properties including tensile, flexural, and impact strength properties were examined as a function of the amount of fiber and coupling agent used. In the sample preparation, three levels of fiber loading (30, 40, and 50 wt %) and two levels of coupling agent content (0 and 2 wt %) were used. As the percentage of fiber loading increased, flexural and tensile properties increased significantly. Notched Izod results showed a decrease in strength as the percentage of fiber increases. With addition of 50% fiber, the impact strengths decreased to 16.3, 14.4, and 16.4 J/m respectively, for wheat straw‐, rice husk‐, and poplar‐filled composites. In general, presence of coupling agent had a great effect on the mechanical strength properties. Wheat straw‐ and rice husk‐filled composites showed an increase in the tensile and flexural properties with the incorporation of the coupling agent. From these results, we can conclude that wheat straw and rice husk fibers can be potentially suitable raw materials for manufacturing biocomposite products. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Kudzu fiber‐reinforced polypropylene composite

Kudzu fiber‐reinforced polypropylene composites were prepared, and their mechanical and thermal properties were determined. To enhance the adhesion between the kudzu fiber and the polypropylene matrix, maleic anhydride‐grafted polypropylene (MAPP) was used as a compatibilizer. A continuous improvement in both tensile modulus and tensile strength was observed up to a MAPP concentration of 35 wt %. Increases of 24 and 54% were obtained for tensile modulus and tensile strength, respectively. Scanning electron microscopy (SEM) showed improved dispersion and adhesion with MAPP. Fourier transform infrared (FTIR) spectroscopy showed an increase in hydrogen bonding with an increase in MAPP content. Differential scanning calorimetry (DSC) analysis indicated little change in the melting temperature of the composites with changes in MAPP content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1961–1969, 2002     

Self‐interference flow of an isotactic polypropylene melt in a cavity during injection molding. II. Morphology and crystallinity

This article is principally concerned with the morphology and crystallinity of isotactic polypropylene (iPP) parts molded by injection molding, during which a self‐interference flow (SIF) occurs for the melt in the cavity. Scanning electron microscopy shows that a transverse flow takes place in SIF samples. Wide‐angle X‐ray diffraction and differential scanning calorimetry show that SIF moldings exhibit a γ phase, in addition to α and β phases, and high crystallinity. Meanwhile, the results for iPP moldings made by the conventional flow process, that is, conventional injection molding, are reported for comparison. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2791–2796, 2003     

Three‐dimensional thermorheological behavior of isotactic polypropylene across glass transition temperature

The aim of this work was to determine the three‐dimensional thermorheological behavior of isotactic polypropylene (i‐PP) in the region of its glass transition temperature (T_g) by a master curve. The i‐PP is a widespread polymer with a T_g ～ 0°C. Dynamic mechanical analysis (DMA) at varying frequencies and temperatures and bulk tests at varying temperatures and times are carried out to obtain the relaxation spectra. Traditionally, the combination of time and temperature is done for thermorheological simple material by the creation of a master curve based on the Arrhenius or William–Landel–Ferry (WLF) equation. This investigation shows that these equations do not fit the behavior across the glass transition of i‐PP. Instead, a new arc tangent function is derived. Additionally, it can be shown that the shifting factors differ from shear to bulk load. Therefore, the mode of mechanical stress seems to have an influence on the thermorheological behavior. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 877–880, 2004     

Effect of polystyrenes with different architectures on the β‐nucleating efficiency and toughening of isotactic polypropylene

The effect of polystyrenes (PSs) with different architectures (three‐arm star‐shaped polystyrene (sPS), comb‐like branched polystyrene (cPS) and linear polystyrene) on their β‐nucleating efficiency for isotactic polypropylene (iPP) during crystallization and final impact and the tensile properties of iPP/PS blends were investigated by dynamic rheological measurements, SEM, DSC, polarized optical microscopy, wide angle X‐ray diffraction and mechanical property measurements. The results show that the architecture of PS has marked influence on its dispersibility in iPP and β‐nucleating efficiency. For iPP/cPS blend, plenty of short side chains reduce the probability of cPS chain entanglements, facilitating the interdiffusion between iPP and cPS chains. A favorable interfacial interaction results in good dispersibility, high β nucleating efficiency and an excellent toughening effect of cPS on iPP. However, the relatively high chain entanglement degree of sPS may not be in favor of chain diffusion between iPP and sPS and therefore relatively poor dispersibility and toughening effect are obtained. The elongation at break and impact strength of iPP were dramatically improved, especially with the addition of 1 wt% cPS. The toughening mechanism of PS on iPP is the dissipated energy caused by cavitation and the β‐nucleating effect of PS. © 2018 Society of Chemical Industry     

Melt rheology of polypropylene reinforced with polyaniline‐coated short glass fibers

This research deals with the melt rheology of isotactic polypropylene (iPP) reinforced with short glass fibers (SGF) coated with electrically conductive polyaniline (PAn). Composites containing 10, 20, and 30 wt % PAn‐SGF were studied. Moreover, a composite of 30 wt % PAn‐SGF was also prepared with a blend of iPP and PP‐grafted‐maleic anhydride (iPP/PP‐gMA). The composites showed linear viscoelastic regime at small strain amplitudes. The onset of nonlinearity decreased as the concentration of filler increased. The time‐temperature superposition principle applied to all composites. The filler increased the shear moduli (G′, G″) and the complex viscosity η*. Steady‐state shear experiments showed yield stress for the composites with 20 and 30 wt % PAn‐SGF. Strikingly, the 10 wt % composite showed higher steady state viscosity than the 20 wt %. Rheo‐optics showed that shear induced disorder of microfibers at a concentration of 10 wt %. However, at 20 wt % concentration shear aligned the microfibers along the flow axis, this would explain the anomalous steady state viscosity values. The viscosity exhibited a shear thinning behavior at high shear rates for all composites. Creep experiments showed that the filler induced greater strain recovery in the composites and that the amount of strain recovery increased as the PAn‐SGF concentration increased. However, the enhancement of strain recovery (as well as shear viscosity) was more significant when using the iPP/PP‐gMA blend, suggesting greater adhesion between this matrix and the filler PAn‐SGF. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

固相氯化法氯化等规聚丙烯结构分析

借助ＤＳＣ,ＩＲ,＾１Ｈ－ＮＭＲ方法对搅拌式固相氯化制备的氯化等规聚丙烯的宏观氯原子分布和微观氯原子分布进行了分析。结果表明,搅拌式固相氯化法能够迅速破坏等规聚丙烯的结晶,从而得到宏观氯原子分布均匀的ＣＩＰＰ。此方法制备的ＣＩＰＰ主要为等丙烯分子链上的仲氢原子被取代的产物。     

Crystallization behavior and crystallization kinetic studies of isotactic polypropylene modified by long‐chain branching polypropylene

In this article, we discuss the crystallization behavior and crystallization kinetics of isotactic polypropylene (iPP) modified by long‐chain‐branching (LCB) high‐melt‐strength iPP over a wide composition range, that is, LCB‐iPP from 10 to 50 wt %. Over the entire range we investigated, the presence of LCB‐iPP accelerated crystallization in both the isothermal crystallization process and nonisothermal crystallization process, even when the LCB‐iPP content was as low as 10%, and both crystallization processes were enhanced more significantly as the LCB‐iPP content increased. Hoffman–Lauritzen theory analysis revealed that the fold‐free energy decreased effectively with the occurrence of the LCB structure, although the growth rate of spherulites was depressed, as shown by polarized optical microscopy. Meanwhile, the regime III–regime II transition temperature was about 15° higher for all of the LCB‐iPP compositions than that of iPP because the LCB structure reduced the mobility of the polypropylene chains. Furthermore, the γ‐form crystal structure was favored by LCB compared to the β form, which was supported by wide‐angle X‐ray diffraction. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

In situ microfibrillar‐reinforced composites of isotactic polypropylene/recycled poly(ethylene terephthalate) system and effect of compatibilizer

Recycled poly(ethylene terephthalate) from waste bottles (hereafter, rPET) was used as an reinforcing material for isotactic polypropylene (iPP) based on the concept of in situ microfibrillar‐reinforced composites (iMFCs). Microfibers of rPET were successfully generated during melt‐extrusion and subsequent drawing and preserved in the final injection‐molded specimens. The effects of draw ratio, initial size of ground rPET flakes, and rPET content on morphological appearance of the extrudates and the as‐formed rPET fibers and mechanical properties of the as‐prepared iMFCs were investigated. The results showed that diameters of the as‐formed rPET fibers decreased with increasing draw ratio, and the initial size of ground rPET flakes did not affect the final diameters of the as‐formed rPET fibers nor the mechanical properties of the as‐prepared iMFCs. Flexural modulus, tensile modulus, and tensile strength of iPP/rPET iMFCs were improved by the presence of rPET microfibers and further improvement could be achieved by the addition of maleic anhydride‐grafted iPP (PP‐g‐MA), which was used as the compatibilizer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1173–1181, 2006     

On the overdrawing of melt‐spun isotactic polypropylene tapes

The morphology and mechanical properties of melt‐spun and post‐drawn isotactic polypropylene (iPP) tapes have been studied in order to examine their dependence on the post‐draw ratio applied. Special attention is focused on the characterization of the so‐called overdrawing behavior of the tapes; at a certain draw ratio, a change of the optical appearance of the tape from transparent to opaque is observed. Overdrawing is accompanied with changes in the mechanical properties, surface, and morphology of the tapes. For post‐draw ratios without overdrawing, and for highly overdrawn tapes, the variation in the mechanical properties measured is very small, but for slightly overdrawn tapes, a large scattering of mechanical properties has been measured. In the latter case, this behavior is related to the start of internal delamination of the tapes during post drawing. It is shown that strongly overdrawn tapes have excellent mechanical properties, in particular, high specific stiffness and strength. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2920–2931, 2007