Effects of compatibilizers on the physico‐mechanical and foaming properties of polyproylene/wood‐fiber composites

Polypropylene (PP)/wood‐fiber (WF) composites were prepared by intermeshing co‐rotating twin screw extruder, and microcellular closed cell PP/WF composite foams were prepared by using pressure‐quenched batch process method. The effect of various compatibilizers on the mechanical properties, morphology, crystallinity, rheological properties, and foamability of PP/WF composites were investigated. The results showed that PP/WF composite with addition of PP‐g‐MA as compatibilizer had the highest tensile strength, stiffness, and crystallinity, after foaming, it showed highest relative density and cell density, as well as the smallest cell size. Higher crystallinity of PP/WF composites, showed higher stiffness and higher relative density. J. VINYL ADDIT. TECHNOL., 19:250–257, 2013. © 2013 Society of Plastics Engineers     

Effect of single‐mineral filler and hybrid‐mineral filler additives on the properties of polypropylene composites

The present study was carried out to determine the filler characteristics and to investigate the effects of three types of mineral fillers (CaCO₃, silica, and mica) and filler loadings (10–40 wt%) on the properties of polypropylene (PP) composites. The characteristics of the particulate fillers, such as mean particle size, particle size distribution, aspect ratio, shape, and degree of crystallinity were identified. In terms of mechanical properties, for all of the filled PP composites, Young's modulus increased, whereas tensile strength and strain at break decreased as the filler loading increased. However, 10 wt% of mica in a PP composite showed a tensile strength comparable with that of unfilled PP. Greater tensile strength of mica/PP composites compared to that of the other composites was observed because of lower percentages of voids and a higher aspect ratio of the filler. Mica/PP also exhibited a lower coefficient of thermal expansion (CTE) compared to that of the other composites. This difference was due to a lower degree of crystallinity of the filler and the CTE value of the mica filler. Scanning electron microscopy was used to examine the structure of fracture surfaces, and there was a gradual change in tensile fracture behavior from ductile to brittle as the filler loading increased. The nucleating ability of the fillers was studied with differential scanning calorimetry, and a drop in crystallinity of the composites was observed with the addition of mineral filler. Studies on the hybridization effect of different (silica and mica) filler ratios on the properties of PP hybrid composites showed that the addition of mica to silica‐PP composites enhanced their tensile strength and modulus. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Dynamic crystallization of polypropylene and wood‐based composites

Thermoplastic composites made of an isotactic polypropylene (iPP) matrix and woodflour (WF) were prepared by melt‐blending, using twin‐screw extrusion and injection molding. Up to 20 wt % of the composite was composed of WF. The incorporation of an interfacial agent made of an ethylene/methacrylic acid copolymer to iPP and WF, PP/WF, binary blends causes a compatibilization effect that becomes evident due to a reduction in the crystallization temperature of PP. In both the binary composites and the compatibilized or ternary composites, the PP adopts an α or monoclinic structure when crystallization occurs from the melt under dynamic conditions at cooling rates between 1 and 20°C min^?1. On the other hand, X‐ray diffraction analysis using synchrotron radiation of the injection‐molded samples demonstrates the existence of a β or trigonal form in the binary as well as the ternary PP/WF composites. They reach k_β levels between 0.18 and 0.25, which can be interpreted as the co‐operation between a reduction of the crystallization rate and the shear effect induced during the injection. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 6028–6036, 2006     

Thermal and dynamic mechanical characterization of polypropylene‐woodflour composites

The performance of wood particle/polypropylene (PP) composites with modified compatibilities was compared. Woodflour modification was performed by esterification with maleic anhydride (MAN) and a non‐commercial maleic anhydride‐polypropylene copolymer (PPMAN) was selected as compatibilizing agent. The thermogravimetric analysis indicates that the onset of thermal degradation of treated woodflour occurs at lower temperature than that of the untreated one, and the same behavior was found in the corresponding composites. Differential scanning calorimetry indicated that both woodflours acted as nucleating agents for PP, while only treated woodflour induced PP crystallization in β‐phase in the composites. X‐ray diffractometry demonstrated that the crystallization in β‐phase was a shear‐induced phenomenon favored by the chemical modification of the woodflour surface. Dynamic mechanical studies suggested that composite properties decreased at concentrations higher than 40 wt% of woodflour and that the overall performance of MAN‐treated woodflour composites was lower than that of the composites where a compatibilizing agent was added.     

Performance of long glass fiber‐reinforced polypropylene composites at different injection temperature

Long glass fiber‐reinforced polypropylene composites were prepared using self‐designed impregnation device. Effects of the different injection temperature on mechanical properties, crystallization, thermal, and dynamic mechanical properties of long glass fiber‐reinforced polypropylene composites were discussed. The differential scanning calorimetry (DSC) results indicate that the melting peak temperature of PP/LGF composites gradually reduced, however, the crystallinity of PP/LGF composites gradually increased with increasing injection temperature. Thermo‐gravimetric analyzer (TGA) results demonstrate that with increasing injection temperature, the temperature of the PP/LGF composites melt increased, the viscosity of the PP/LGF composites melt lowered, the mold filling of the PP/LGF composites melt was easy, the shear force of glass fiber was relatively low, which made the residual length of glass fiber in products increase. Dynamic thermal mechanical analyzer (DMA) results show that the storage modulus of PP/LGF composites is the highest while the injection temperature is at 290°C, and the peak value of tan σ of PP /LGF composites at 290°C is minimal, which indicates that the mechanical properties of PP /LGF composites at 290°C is the best. What' more, the injection temperature at 290°C significantly ameliorated “glass fiber rich skin” of products of glass fiber‐reinforced composites. J. VINYL ADDIT. TECHNOL., 24:233–238, 2018. © 2016 Society of Plastics Engineers     

Thermal and crystallization behavior of cotton—Polypropylene commingled composite systems

Techniques like thermogravimetric analysis, differential scanning calorimetry, and polarized optical microscopy were used to study the thermal and crystallization behavior of cotton‐polypropylene (PP) commingled composite system. Thermal analysis was used to understand the structure‐property relationship and also to quantify the amount of moisture and volatiles, which causes the deterioration of the composite performance. Thermal stability of the composite was found be intermediate between that of PP and cotton fibers. Presence of treated reinforcements had increased the crystallinity of PP. Also, fibers act as heterogeneous nucleants and favor the early crystallization of PP in the composites. The crystallization and onset crystallization temperature values were increased by the presence of cotton fibers. The theories of heterogeneous nucleation and crystal growth kinetics were used to explain the growth of transcrystalline layer (TCL) of PP on cotton fibers. The interfacial free energy difference for nucleation of PP on fiber was found to be smaller compared with that in the bulk PP. This favors the formation and growth of TCL. The thickness of TCL and radius of the spherulites increase with the increase in the crystallization temperature. Fiber surface roughness and thermal stresses facilitate the growth of transcrystallinity on cotton fiber. POLYM. COMPOS., 31:1487–1494, 2010. © 2009 Society of Plastics Engineers     

Effects of the accelerated freeze‐thaw cycling on physical and mechanical properties of wood flour‐recycled thermoplastic composites

This study investigated durability performance of wood‐plastic composites (WPCs) that were exposed to accelerated cycling of water immersion followed by freeze thaw (FT). The WPCs used in this study were made of high‐density polyethylene (HDPE) or polypropylene (PP) with radiata pine (Pinus radiata) wood flour using hot‐press molding. These two types of plastics included both recycled and virgin forms in the formulation. In the experiments, surface color, flexural properties, and dimensional stability properties (water absorption and thickness swelling) were measured for the FT cycled composites and the control samples. Interface microstructures and thermal properties of the composites were also investigated. The results show that the water absorption and the thickness swelling of the composites increased with the FT weathering. In the meantime, the flexural strength and stiffness decreased. Scanning electron microscopy (SEM) images of the fractured surfaces confirmed a loss of interface bonding between the wood flour and the polymer matrix. Differential scanning calorimetry (DSC) showed a decrease in crystallization enthalpy and crystallinity of the wood flour‐plastic composites as compared with the neat PP and HDPE samples. The crystallinity of the FT cycled composites using the virgin plastics (vPP and vHDPE) increased; however, the composites with the recycled plastics decreased in comparison with corresponding control samples. In general, the properties of the composites were degraded significantly after the accelerated FT cycling. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Prediction of viscoelastic behavior of interphase in polypropylene‐chopped rice husk composites for β‐relaxation domain

The effect of chopped rice husk (CRH) content on viscoelastic properties and crystallinity of polypropylene (PP) composites was investigated. Composites containing 0, 20, and 40 part per hundred plastics (php) of CRH into PP were prepared by twin‐screw extruder, with maleic anhydride‐grafted PP as the coupling agent. The viscoelastic behavior and the crystallinity of these composites have been studied by dynamic mechanical analysis as well as differential scanning calorimetry, respectively. By the incorporation of CRH into PP, the storage modulus (E′) was found to be increased progressively, whereas the mechanical loss factor (tan δ) decreased in a nonlinear manner. A self‐consistent analysis was proposed for the prediction of viscoelastic response of the interphase between PP matrix and CRH particles. A three‐phase model was applied in a reverse mode, and the viscoelastic behavior of the interphase was extracted and compared with the unfilled matrix. Differential scanning calorimetry results indicated that CRH influences crystallization temperature as well as the degree of crystallinity of the composites. An entrapped polymer within CRH filler and PP matrix was detected by scanning electron microscope, which can be attributed to the interfacial layer with a good adhesion between the main components. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Novel intercalated nanocomposites of polypropylene/organic‐rectorite/polyethylene‐octene elastomer: Rheology,crystallization kinetics,and thermal properties

The melt blending method was applied to prepare ternary composites of polypropylene (PP)/organic‐rectorite (OREC)/polyethylene‐octene elastomer (POE) at constant content of 2 phr (parts per hundred PP) of OREC and 5, 10, 15 phr of POE (named PRE25, PRE210, and PRE215, separately) via twin‐screw extruder. At the same time the binary composites of OREC/PP at 2 phr loading of OREC, named PR2 were prepared in order to investigate effects of OREC and POE on rheology and crystallization properties of composites. The rheology was characterized on capillary rheometer, nonisothermal crystallization kinetics on differential scanning calorimetry (DSC), and thermal stability properties on thermogravimetric analysis (TG). It is found that melting PR2 and PRE systems conform to the law of Non‐Newton and shear‐thinning behavior is observed for both systems. The apparent viscosity of the melt decreases with the increase of POE loadings. The crystallization halftime (t_1/2) of PRE is shorter, the rate constant Zc larger, which indicates OREC and POE has the heterogeneous nucleation effect and the crystallization rate of PP was increased. The enthalpy of PRE is lower than that of PR2 and pure PP at the same conditions, which shows that the relative crystallinity of PRE composites are reduced. TG curves show that the ternary systems have higher thermal stability in contrast with pure PP. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1915–1921, 2005     

Quiescent crystallization of natural fibers–polypropylene composites

The effect of natural fibers (vetiver grass and rossells) on quiescent crystallization of polypropylene (PP) composites was analyzed in this study. Also, equilibrium melting temperature (T) of the composites was elucidated. Natural fiber‐PP composites showed lower T when compared to neat PP. Thermal analysis was performed via differential scanning calorimeter to study the crystallization kinetics. Natural fiber‐PP composites exhibited higher rate of crystallization than that of neat PP. Furthermore, spherulitic growth rate and transcrystallinity of the composites were investigated under a polarized light optical microscope. It was found that the growth rates of the composites were lower than that of neat PP. The spherulitic growth rates combined with the crystallization rates were used to calculate number of effective nuclei. It was shown that the number of effective nuclei of the composites was higher than that of neat PP. This suggested that natural fibers could act as a nucleating agent in the composite. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Investigation on β‐polypropylene/PP‐g‐MAH/ surface‐treated calcium carbonate composites

β‐Polypropylene composites containing calcium carbonate treated by titanate coupling agent (T‐CaCO₃) and maleic anhydride grafted PP (PP‐g‐MAH) were prepared by melt compounding. The crystallization, morphology and mechanical properties of the composites were investigated by means of differential scanning calorimetry, wide‐angle X‐ray diffraction, polarized light microscopy, scanning electron microscopy and mechanical tests. It is found that both T‐CaCO₃ and NT‐C are able to induce the formation of β‐phase, and NT‐C greatly increases the β content and decreases the spherulitic size of PP. PP‐g‐MAH facilitates the formation of β‐form PP and improves the compatibility between T‐CaCO₃ and PP. Izod notched impact strength of β‐PP/T‐CaCO₃ composite is higher than that of PP/T‐CaCO₃ composite, indicating the synergistic toughening effect of T‐CaCO₃ and β‐PP. Incorporation of PP‐g‐MAH into β‐PP/T‐CaCO₃ composite further increases the content of β‐crystal PP and improves the impact strength and tensile strength when T‐CaCO₃ concentration is below 5 wt%. The nonisothermal crystallization kinetics of β‐PP composites is well described by Jeziorny's and Mo's methods. It is found that NT‐C and T‐CaCO₃ accelerate the crystallization rate of PP but the influence of PP‐g‐MAH on crystallization rate of β‐PP composite is marginal. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Influence of m‐isopropenyl‐α,α‐dimethylbenzyl isocyanate grafted polypropylene on the interfacial interaction of wood‐flour/polypropylene composites

In this article, the effects of m‐isopropenyl‐α,α‐dimethylbenzyl isocyanate grafted polypropylene (m‐TMI‐PP) on the interfacial interaction of wood‐flour/polypropylene (WF/PP) were investigated by means of scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetry, dynamic rheological analysis, and mechanical properties tests. The experimental results demonstrated that m‐TMI‐PP greatly improved the interfacial interaction between WF and PP. According to the DSC results, m‐TMI‐PP made the crystallization temperature and the crystallization degree of PP in WF/m‐TMI‐PP/PP decrease when compared with WF/PP composite without m‐TMI‐PP, but it was still higher than pure PP. These results demonstrated that WF presented the nucleate effect for the crystallization of PP and m‐TMI‐PP improved the interfacial adhesive, which restrained the mobility of PP chain. The rheological analysis indicated that the complex viscosity, storage, and loss modular of WF/PP composite increased, and the tan δ decreased with the addition of m‐TMI‐PP. This was attributed to the strong improvement effects of m‐TMI‐PP on the interfacial interaction of the composites, and was further confirmed by the mechanical properties tests and SEM analysis of the composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The effect of poly[styrene‐b‐(ethylene‐co‐butylene)‐ b‐styrene] on dielectric,thermal, and morphological characteristics of polypropylene/silica nanocomposites

The effect of poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS) copolymer on the thermal and dielectric properties of polypropylene (PP)—nanosilica (NS) composites in relation with morphological aspects revealed by atomic force microscopy (AFM) was investigated in this article. SEBS hindered the crystallization process of PP in PP/NS composites, leading to a smaller degree of crystallinity and lower perfection of crystalline structure. Broader lamellar thickness distribution was obtained in nanocomposites containing SEBS. Almost two times higher dielectric loss as compared to PP reference and two relaxation processes were detected in ε_r ^′′(f) curves of nanocomposites. The first peak, in the same frequency domain as for the references, was assigned to α‐relaxation of polymer components together with interfacial polarization. The relaxation time follows the Arrhenius law with an activation energy of 80–90 kJ/mol. For the second process, the temperature dependence of the relaxation times obeyed the VFT equation. The dielectric changes following the incorporation of SEBS support its tendency to hinder the motional processes in PP, in accordance with DSC results. A smooth transition from a phase rich in SEBS to one containing mainly PP was detected in the AFM image of the composite with the larger amount of SEBS, emphasizing the good compatibility at the PP/SEBS interface. POLYM. ENG. SCI., 53:2081–2092, 2013. © 2013 Society of Plastics Engineers     

Preparation of nano poly(phenylsilsesquioxane) spheres(nano‐PPSQ) and study of the thermal stability and crystallization behavior of PP/nano‐PPSQ composites

The preparation of nano poly(phenylsilsesquioxane) particles (nano‐PPSQ) and the influence of nano‐PPSQ on the thermal stability and crystallization of polypropylene (PP) were studied. The morphology and thermal stability of PP/nano‐PPSQ composites were characterized by scanning electron microscopy (SEM) and the thermogravimetric analysis (TGA). The SEM result showed that the particles were well dispersed in the PP matrix. The TGA results of the PP/nano‐PPSQ composites indicated that the incorporation of nano‐PPSQ can improve the thermal stability of PP. The crystallization behavior and kinetics of PP/nano‐PPSQ composite were studied by X‐ray diffraction (XRD) and differential scanning calorimetry (DSC). The XRD revealed that the addition of nano‐PPSQ influences the crystallinity and crystal size of PP. The Avrami, Ozawa, and combined Avrami/Ozawa (Mo method) equations were applied to describe the crystallization kinetics and estimate the kinetic parameters of mathematical models under the nonisothermal crystallization of PP and PP/nano‐PPSQ composites. The results show that nano‐PPSQ influences the crystallization temperature and rate. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of thermal conductivity and heat transfer on crystallization,structure, and morphology of polypropylene containing different fillers

The crystallization behavior, structure, and morphology developed was investigated for polypropylene containing different fillers such as silica, calcium carbonate, talc, mica, graphite, etc. by using compression‐molded samples prepared at several cooling rates. It was observed that the crystallinity obtained for any given composition depended on the thermal conductivity of the filler and the PP composite containing it as well as the cooling rate to which it was subjected. These composites exhibited skin‐core type of morphology and the skin layer thickness was found to depend not only on the cooling rate but also on the type of filler, its thermal conductivity, etc. These various experimental findings were discussed in light of the phenomenological model described in our earlier work, which correlates thermal conductivity and degree of crystallinity for various compositions of PP containing additives. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 615–623, 2004     

Mechanical properties and morphology of polypropylene‐calcium carbonate nanocomposites prepared by dynamic packing injection molding

In this article, dynamic packing injection molding (DPIM) technology was used to prepare injection samples of Polypropylene‐Calcium Carbonate (PP/CaCO₃) nanocomposites. Through DPIM, the mechanical properties of PP/nano‐CaCO₃ samples were improved significantly. Compared with conventional injection molding (CIM), the enhancement of the tensile strength and impact strength of the samples molded by DPIM was 39 and 144%, respectively. In addition, the tensile strength and impact strength of the PP/nano‐CaCO₃ composites molded by DPIM increase by 21 and 514%, respectively compared with those of pure PP through CIM. According to the SEM, WAXD, DSC measurement, it could be found that a much better dispersion of nano‐CaCO₃ in samples was achieved by DPIM. Moreover, γcrystal is found in the shear layer of the DPIM samples. The crystallinity of PP matrix in DPIM sample increases by 22.76% compared with that of conventional sample. The improvement of mechanical properties of PP/nano‐CaCO₃ composites prepared by DPIM attributes to the even distribution of nano‐CaCO₃ particles and the morphology change of PP matrix under the influence of dynamic shear stress. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Study on poly(propylene)/ammonium polyphosphate composites modified by ethylene‐1‐octene copolymer grafted with glycidyl methacrylate

The compatibilization effect of ethylene‐1‐octene copolymer grafted with glycidyl methacrylate (POE‐g‐GMA) as an interface compatibilizer on the mechanical and combustion properties, and the morphology and structures of the cross sections of ammonium polyphosphate (APP)–filled poly(propylene) (PP) were investigated by thermogravimetry, dynamic mechanical analysis, and differential scanning calorimetry. The results indicated that the toughness of the PP/APP composites increased rapidly with adding POE‐g‐GMA; the dynamic mechanical spectra revealed that the increase of the toughness was closely related to the peaks of loss modulus (E″) and mechanical loss (tan δ). The improvement of the dispersion of APP in the PP matrix was attributed to the addition of POE‐g‐GMA; it was found that the interfacial adhesion between the filler and matrix was enhanced when the grafting material was added to the composites. Under such circumstances, the ratio of char formation was increased when the PP composites were heated, although the content of flame retardant was not changed, so the flame retardance of the material was improved. The addition of POE‐g‐GMA increased the rate of crystallization. At the same time, the degree of crystallinity and the temperature at the beginning of crystallization were decreased, although exerting little influence on the melt behavior of the crystallization of the composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 412–419, 2004     

Fabrication and properties of nano‐ZnO/glass‐fiber‐reinforced polypropylene composites

Polypropylene (PP) is widely used in many fields, such as automobiles, medical devices, office equipment, pipe, and architecture. However, its high brittle transformation temperature, low mechanical strength, dyeing properties, antistatic properties, and poor impact resistance, considerably limit its further applications. Nano‐ZnO treated by KH550 coupling agent and glass fibers (GFs) were introduced in order to improve the mechanical performance and flowability of PP in this research. The crystallization behavior and microstructure of nano‐ZnO/GFs/PP hybrid composites were analyzed by differential scanning calorimetry, transmission electron microscopy, and scanning electron microscopy. The effect of crystallization behavior on the mechanical properties of the nanocomposites was investigated and analyzed. The results indicated that nano‐ZnO surface‐coupled by KH550 could be uniformly dispersed in the PP matrix. The incorporation of nano‐ZnO and GFs resulted in increases of the crystallization temperature and crystallization rate of PP and a decrease of the crystallization degree. The introduction of nano‐ZnO and GFs also enhanced the tensile strength and impact toughness of the hybrid composites and improved their fluidity. Composites containing 2% of nano‐ZnO and 40% of GFs possessed the optimum mechanical properties. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

微波辐照对聚丙烯/纳米TiO2复合材料性能的影响

采用熔融共混法制备了聚丙烯（PP）/纳米TiO2复合材料,通过力学性能测试、红外光谱、偏光显微镜、扫面电子显微镜和透射电子显微镜等分析手段研究了微波辐照对PP/纳米TiO2复合材料性能的影响。结果表明,母粒经过微波辐照之后,PP/纳米TiO2复合材料的拉伸强度和屈服强度基本保持不变,断裂伸长率大幅度提高;结晶度提高近20 %,晶粒尺寸变大,但结晶速率并没有改变;红外分析表明,在PP/纳米TiO2复合材料中引入了极性基团,改善了两相的相容性,使复合材料的力学性能提高。     

Crystallization kinetics of polypropylene composites filled with nano calcium carbonate modified with maleic anhydride

The subject of this study was the crystallization behavior and thermal properties of polypropylene (PP)/maleic anhydride (MAH) modified nano calcium carbonate (nano‐CaCO₃) composites. In this study, 5 wt % nano‐CaCO₃ modified with different contents of MAH was filled into a PP matrix. X‐ray diffraction and differential scanning calorimetry were used to characterize the crystal morphology and crystallization kinetics of a series of composites. The results demonstrate that the nano‐CaCO₃ modified with MAH had an important effect on the thermal and morphological properties of the nanocomposites. The Avrami exponent of the pure PP was an integer, but those of the composites were not integers, but the crystallization rate constant decreased as the content of MAH in the nano‐CaCO₃ filler increased in isothermal crystallization. In nonisothermal crystallization, the kinetic parameter F(T) and the degree of crystallinity of pure PP were compared with those of the PP composites filled with nano‐CaCO₃. We suggest that heterogeneous nucleation existed in the PP composites and that the transformation and retention of the β‐form crystal into the α‐form crystal took place in the composite system and the β‐form crystal had a higher nucleation rate and growth process than the α‐form crystal in the PP composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011