Crystallization of PP in PP/Ni composites and its correlation with tensile properties

The effect of nickel (Ni) powder on crystallization of polypropylene (PP) in PP/Ni composites is studied through differential scanning calorimetry (DSC) and wide-angle X-ray diffraction techniques. Interpretation of crystallization exotherm peaks in terms of nucleation and growth rates of crystallization, crystallite size distribution, and crystallinity indicated differences in the morphology of PP in all the composites. Crystallinity and tensile behavior decreased on nickel addition. There is a good qualitative agreement in the crystallinity determined by X-ray diffraction and DSC exotherms, and the variation in both cases, with the volume percent of filler is similar. An attempt has been made to correlate the various tensile properties with the crystallization parameters such as the crystallinity and crystallite size distribution.     

Nonisothermal crystallization kinetics of polypropylene‐layered double hydroxide composites: Correlation with morphology

In this work the effect of nanofiller on nonisothermal crystallization behavior of composites based on polypropylene (PP) was investigated by differential scanning calorimetry. The materials were prepared by melt mixing. Both an alkyl sulfonate salt modified layered double hydroxide (LDH) and an unmodified LDH were used as nanofillers and both PP and PP/polypropylene grafted with maleic anhydride (PP‐g‐MA) blend were used as matrices. The morphology of composites was investigated by X‐ray diffraction and transmission electron microscopy. No exfoliation was noticed in all prepared composites, but the hybrid materials showed an intercalated structure. The thermal properties and crystallization behavior were studied by conventional differential scanning calorimetry. In particular, the kinetic crystallization parameters were obtained using the modified Avrami equation for a nonisothermal process, whereas the activation energy of the global crystallization process was estimated using the Kissinger equation. The Avrami parameters suggest a significant effect on the crystallization of PP for the composites containing both the organically modified LDH and PP‐g‐MA. The results indicate a complex crystallization process of PP and evidence that the crystallization process can not be only explained by intercalation phenomenon, but the constrain effect ofpolymer chains on the filler surface and/or betweenthe filler clusters should play a significant role. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Interfacial enhancement by shish-calabash crystal structure in polypropylene/inorganic whisker composites

The polymer matrix structure and the interface are strongly influenced by filler in semi-crystalline polymer composites because the fillers have the potential to nucleate the polymer crystallization. The structure of the nucleated crystalline polymer on filler is of particular interest and is a key to the interfacial enhancement. In this work, whiskers, with a large length/diameter ratio and with a diameter (0.2-2 μm) much larger than that of carbon nanotubes but much smaller than that of common fibers, were used to nucleate crystal morphology in polypropylene (PP)/whisker composites. The crystal morphology, interfacial adhesion and tensile properties of the composites were carefully investigated. A kind of peculiar shish-calabash crystallization morphology, with whisker serves as shish and PP spherulites serves as calabash, was observed for the first time in the thin film via PLM and in the injection molded bars by SEM. The formation mechanism of this shish-calabash structure was attributed to be that only a few nuclei could be induced on the whisker surface, which develop into large PP spherulites without hindrance, and finally stringed by the whisker, forming the shish-calabash structure. As a result, a significant improvement of interfacial interaction and tensile properties has been achieved.     

聚丙烯基复合材料的结晶行为

综述了3类聚丙烯(PP)基复合材料体系包括PP/无机物体系、PP/有机物体系和PP／聚合物体系的结晶行为。阐述了PP基体的结晶结构以及结晶动力学特征,包括添加物对PP的结晶温度、结晶速率及结晶度等的影响;分析了结晶行为对复合材料力学性能的影响。复合材料界面对基体聚合物取向结晶形态及结晶行为的影响等还需进一步研究。     

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     

Crosslinkable polypropylene composites made by the introduction of silane moieties

Silane‐crosslinkable polypropylene (PP) composites containing calcium carbonate (CaCO₃) as a filler have been investigated. The melt grafting of vinyl trimethoxysilane to PP with dicumyl peroxide (DCP) as a radical initiator is demonstrated. The thermal and mechanical properties of the crosslinkable products are also discussed. The results show that two reactions, that is, silane grafting and PP degradation, take place in parallel. The extents of silane grafting and PP degradation strongly depend on the reaction temperature, grafting formulation, and amount of the filler in the systems. Increasing the DCP concentration (up to 0.05 wt %) leads to an increase in the grafting degree. However, when the concentration of radicals is over a certain degree, the dominant reaction is PP chain scission. This results in a drastic decrease in the polymer viscosity. In systems containing both silane and CaCO₃, the viscosity of the polymer is higher than that of a grafted sample without CaCO₃ addition; in other words, the effect of the filler on the polymer viscosity compensates for the effect caused by PP degradation. Differential scanning calorimetry results show that the crystallization starts earlier for grafted samples. The percentage of the crystallinity of grafted PP is higher than that of the pure polymer. The incorporated silane does not have a strong effect on the mobility of the PP chains, as revealed by dynamic mechanical analysis. In comparison with ungrafted composites, the silane‐crosslinkable products show higher tensile stress and modulus. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1476–1483, 2005     

Polymer nanocomposite powders and melt spun fibers filled with silica nanoparticles

Nanocomposite powders from polypropylene filled with surface modified and unmodified fumed silica have been prepared from polymer solution to achieve improved mixing and have been forwarded to fiber melt spinning. The surface of the fumed silica was modified with dodecyl alkoxy silanes. Crystallization velocity and viscosity of the PP nanocomposites thereof were determined to ensure good melt spinning processing conditions for all composite compositions. Upon addition of untreated filler particles, a shear thinning and an increased crystallization velocity of the polymer melt was found, while only minor changes were detected in the presence of surface modified fumed silica particles. The composites and the polymer fibers made from these powder composites by melt spinning were mainly characterized by optical microscopy (OM), scanning electron microscopy (SEM), mechanical measurements, differential scanning calorimetry (DSC), and solid‐state NMR. The unmodified fumed silica was found to have a strong influence on the mechanical fiber properties, while the surface modified silica only a small one. Fibers were additionally characterized with respect to the uniformity, the PP crystallinity, moisture absorption, and the water contact angle. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 218–227, 2007     

Crystallization of different polypropylene matrices in the presence of wood fillers

The increasing global energy crisis and ecological risks in recent years have led to the interest in lignocellulosic fillers reinforced polymer composites. In this study, the nucleation ability of pine wood in polypropylene (PP) matrices was studied by differential scanning calorimetry. PPs with different melt flow index values (in range 3.2–25 g/10 min.) were used as the polymer matrix. Moreover, a new technique of wood treatment using γ‐irradiation was used. The experimental results clearly show that the nucleation activity of the wood particles is strongly dependent on the rheological parameter (e.g., MFI) of PP matrix. The composites containing PP matrix with lower MFI exhibited higher degree of crystal conversion, lower half‐times of crystallization, and higher crystallization temperatures. Moreover, the applied γ‐irradiation of wood resulted in a negative effect on the crystallization rate of PP matrix and a distinct deterioration of the nucleation ability of wood surface. The interesting differences in nucleation activity of wood have been interpreted in the context of polymer chains length and relaxation times during crystallization. This article will spotlight the nucleating efficiency of filler, which is critical in polymer processing e.g., optimization of injection molding cycle time of composite materials. POLYM. COMPOS., 36:1813–1818, 2015. © 2014 Society of Plastics Engineers     

Complex modification effect of linseed cake as an agricultural waste filler used in high density polyethylene composites

Linseed cake (LC) is a by-product of agricultural industry which does not have any large-scale industrial applications. The possibilities of its utilization as filler with plasticizing ability for high density polyethylene (HDPE)-based composites have been investigated. Composites containing 5, 10, 20 and 30 wt% of the waste filler have been prepared using a melt mixing method. The influence of the LC on the mechanical and thermomechanical properties of the composites, as well as their water absorption and morphology, have been evaluated by the following methods: static tensile test, impact strength assessment using Dynstat method, hardness measurements, differential scanning calorimetry, dynamic mechanical thermal analysis, scanning electron microscopy observations, measurements of Vicat’s softening temperature and water uptake test. Application of different measuring techniques allows for describing complex modification effects of the composites’ properties changes induced by the presence of lignocellulosic filler with high oil content. The results of the study proved a pronounced influence of LC on high density polyethylene-based composites, especially a plasticizing effect of crude linseed oil contained by the waste filler particles. LC also has been assumed to affect the polymeric matrix crystallization process. It was found that complex modification of polyethylene results from simultaneously occurring different phenomena including: plasticization of the HDPE by linseed oil, improved crystallinity of the semicrystalline matrix, presence of the rigid lignocellulosic particles dispersed in polymer and accumulation of the oil in the interfacial regions.     

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     

Effects of interfacial adhesion on properties of polypropylene/Wollastonite composites

Wollastonite reinforced polypropylene (PP/CaSiO₃) composites were prepared by melt extrusion. A silane coupling agent and a maleic anhydride grafted PP (PP‐g‐MA) were used to increase the interfacial adhesion between the filler and the matrix. The increased adhesion observed by scanning electron microscopy (SEM) resulted in improved mechanical properties. A model was applied to describe the relationship between the interfacial adhesion and tensile properties of PP/CaSiO₃ composites. There is stronger interfacial adhesion between silane‐treated CaSiO₃ and polymer matrix containing PP‐g‐MA as a modifier. Results of dynamic mechanical thermal analysis (DMTA) showed that stronger interfacial adhesion led to higher storage modulus. The influence of CaSiO₃ particles on the crystallization of PP was studied by using differential scanning calorimetry (DSC). The introduction of CaSiO₃ particles does not affect the crystallization temperature and crystallinity of PP matrix significantly. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of talc genesis and particle surface on the crystallization kinetics of polypropylene/talc composites

Talc is a laminar silicate, considered as an excellent nucleating agent for polypropylene (PP) crystallization. However, properties of PP/talc composites depend on the morphology, size, and surface of mineral particles. In this sense, talc from several ores, having different morphology, imparts specific characteristics on these materials. Also, taking into account that PP‐talc adhesion is not necessarily good due to the apolar character of PP, talc surface has been modified in order to increase this parameter. In this work, the effects of talc genesis, geomorphologic aspects, and particle surface characteristics on crystallization of PP/talc composites are analyzed. Isothermal crystallization of PP/talc composites was studied by using differential scanning calorimetry, based on Avrami model. The final crystalline morphology of talc‐filled PP was analyzed by means optical microscopy. The results show that the blocky talc morphology favors even more the crystallization compared to the platy one, at the same particle size. Taking into account the surface treatment studied in this work, the talc surface is made hydrophobic and the particle delamination is favored. As a consequence, so‐modified talc is very effective in increasing the crystallization temperature of PP and the nuclei number that grow during the crystallization with respect to the untreated talc. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

PP复合材料耐刮擦性能的研究

通过多指刮擦试验机对聚丙烯(PP)及其复合材料进行了系统的刮擦实验测试,采用光学显微镜观察了材料的刮擦损伤形貌,以研究PP及其复合材料的耐刮擦性能及损伤机理;通过差示扫描量热仪(DSC)测试了材料的结晶度,研究了耐刮擦助剂和磷酸盐成核剂对材料力学性能、结晶性能和耐刮擦性能的影响,以探讨材料力学性能、结晶性能与耐刮擦性能之间的关系。     

Characterization of PP/Mg(OH)2 and PP/Nanoclay Composites with Supercritical CO2 (scCO2)

In this article, supercritical carbon dioxide (scCO₂) is used to form a high density microcellular foam structure to reduce the polymer use and facilitate dispersion of Mg(OH)₂ and Nanoclay fillers. A twin-screw extruder system was used to predistribute the inorganic filler from the PP polymer, resulting composite PP/filler pellets. This followed by the use of a single-screw extruder wherein supercritical carbon dioxide is introduced in the formulation. Finally the resulting foam PP/filler/CO₂ pellets are injection molded into test samples. The structure and properties of the composites are characterized using a scanning electron microscopy (SEM), Differential scanning calorimetry (DSC), and density measurements. Furthermore, PP/Clay/Mg(OH)₂ polymer composites are subjected to examinations to obtain their yield and tensile strengths, elasticity modulus, % elongation, Izod impact strength, hardness, Heat deflection temperature (HDT), Vicat softening point and Melt flow index (MFI).     

Influence of polyamide 6 as a charring agent on the flame retardancy,thermal, and mechanical properties of polypropylene composites

In this work, polyamide 6 (PA6) as a charring agent has been used in combination with thermoplastic polyurethane (TPU)‐microencapsulated ammonium polyphosphate (MTAPP) forming intumescent flame retardants (IFRs) which applies in polypropylene (PP). The effects of the IFRs on the flame retardancy, morphology of char layers, water resistance, thermal properties and mechanical properties of flame‐retardant PP composites are investigated by limiting oxygen index (LOI), UL‐94 test, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and mechanical properties test. The results show that the PP/MTAPP/PA6 composites exhibit much better flame‐retardant performances than the PP/MTAPP composites. The higher LOI values and UL‐94 V‐2 of the PP/MTAPP composites with suitable amount of PA6 are obtained, which is attributed to the thick and compact char layer structure evidenced by SEM. The results from TGA and DSC demonstrate that the introduction of PA6 into PP/MTAPP composites has a great effect on the thermal stability and crystallization behaviors of the composites. Furthermore, the mechanical properties of PP/MTAPP/PA6 composites are also improved greatly due to the presence of PA6 as a charring agent. POLYM. ENG. SCI., 55:1355–1360, 2015. © 2015 Society of Plastics Engineers     

Polypropylene and potato starch biocomposites: Physicomechanical and thermal properties

To determine the possibility of using starch as biodegradable filler in the thermoplastic polymer matrix, starch‐filled polypropylene (PP) composites were prepared by extrusion of PP resin with 5, 10, 15, and 20 wt % of potato starch in corotating twin‐screw extruder. The extruded strands were cut into pellets and injection molded to make test specimens. These specimens were tested for physicomechanical properties such as tensile and flexural properties, Izod impact strength, density, and water absorption. These PP composites were further characterized by melt flow index (MFI), vicat softening point (VSP), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) techniques. It was found that, with increase in starch content, tensile modulus, flexural strength, and flexural modulus of the PP composites increased along with the increase in moisture, water absorption, and density, while retaining the VSP; but, tensile strength and elongation, impact strength, hardness, and MFI of the PP composites also decreased. DSC analysis of the PP composite revealed the reduction in melting temperature, heat of fusion, and percentage of crystallization of PP with increase in starch content. Similarly, TGA traces display enhanced thermal degradability for PP as starch content increases. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚丙烯/n-SiO2复合材料的制备与性能研究

采用熔融共混法制备了PP/纳米SiO2复合材料,并通过力学性能测试、DSC分析以及材料断面形貌分析等手段,对增强增韧效果进行了研究。结果表明,加入纳米SiO2能提高了PP的结晶速率,使结晶度增大。当纳米SiO2的质量分数为2%时可使PP/nSiO2复合材料的缺口冲击强度提高2倍,拉伸强度稍微下降。     

Changes in morphology and properties by grafting reaction in PP/EOR/CaCO3 ternary composites

The phase morphology and mechanical properties of polypropylene (PP) composites containing ethylene–octene elastomer (EOR) and calcium carbonate (CaCO₃) filler were investigated by comparing the toughening effect of unmodified EOR with EOR grafted with maleic anhydride (EOR–MA). EORs of various MA contents were prepared by free‐radical grafting of MA onto the EOR backbone using a reactive extrusion process. The composite morphology was directly explored by scanning electron microscopy technique and indirectly explored by differential scanning calorimetry and dynamic mechanical analysis. Separate dispersion of the elastomer and filler particles was achieved by using unmodified EOR. Modification of EOR by maleic anhydride grafting resulted in encapsulation of the filler particles. The mechanical properties of the composites were found to depend mainly on composite morphology and composition and, to a lesser degree, on maleic anhydride concentration. The results of this study showed that when composites contained an equal or higher amount of elastomer relative to filler, a composite with a separate dispersion structure was preferred. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3557–3562, 2003     

Influence of stearic acid treatment of filler particles on the structure and properties of ternary‐phase polypropylene composites

In this study, ternary‐phase polypropylene (PP) composites containing an ethylene–octene copolymer (EOR) and calcium carbonate (CaCO₃) were investigated. Particular consideration was given to the influence of stearic acid treatment of the filler on the phase morphology and mechanical properties of the composites. In composites containing an uncoated filler, a separate dispersion of the elastomer and filler particles in the PP matrix was observed. The use of filler treated with stearic acid had no effect either on the dispersion or the interaction of the filler and the polymer components. However, the surface‐treated filler was found to promote the β‐hexagonal crystallization of PP and gave a composite with lower T_{c onset} and T_c values. As a consequence, differences in mechanical properties, in particular, impact strength, were exhibited in which calcium carbonate with stearic acid treatment was apparently more effective in increasing the impact strength of the composites in comparison with the composites containing the uncoated filler. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3445–3454, 1999     

Non-isothermal crystallization kinetics of calcium carbonate-filled β-crystalline phase polypropylene composites

The non-isothermal crystallization behaviour of high purity β-phase and α-phase polypropylene (PP) and their calcium carbonate-filled composites was investigated by means of differential scanning calorimetry. High purity β-PP polymer was prepared by adding an effective β-nucleator consisting of equal amounts of pimelic acid and calcium stearate. The crystallization temperature and crystallization rate coefficient of pure β-PP polymer were considerably higher than those of the α-PP polymer. This was due to the β-PP polymer containing nucleating agents, which act as nuclei for β-spherulites. The calcium carbonate content had little or no effect on the crystallization rate coefficient and Ozawa exponent of the β-phase PP in the composites. On the other hand, the crystallization temperature, crystallization rate coefficient and Ozawa exponent of the α-phase PP composites depended on the calcium carbonate loading. The effect of calcium carbonate additions on the crystallization of α-PP and β-PP is discussed. ©1997 SCI