Enhanced β‐crystal formation of isotactic polypropylene under the combined effects of acid‐corroded glass fiber and preshear

The acid‐corroded glass fiber (GF)/isotactic polypropylene (iPP) composite was injection molded by mixing–injection molding (MIM). Through this method, preshear can be imposed on melt during mix–plasticization process. The crystalline structure across the thickness direction of the injection‐molded bars was investigated by wide‐angle X‐ray diffraction and differential scanning calorimetry (DSC). It was unexpectedly found that, in core region, the acid‐corroded GF/iPP sample has the highest content of β‐form crystals, followed by uncorroded GF/iPP and neat iPP. Additionally, the crystalline morphology was investigated by polarized optical microscopy (POM) and scanning electron microscopy, and the results showed that β‐transcrystallization is preferably present in the acid‐corroded GF/iPP system. Confirmed by POM and DSC, the acid‐corroded GF shows strong β‐nucleation ability to iPP under static condition. Combined with the main features of MIM, three β‐nucleation origins in the acid‐corroded GF/iPP system under injection molding condition are proposed: (1) precursors induced by preshear in the barrel, (2) row‐nuclei induced by local shear, and (3) the acid‐corroded GF nuclei. POLYM. COMPOS. 34:1250–1260, 2013. © 2013 Society of Plastics Engineers     

Gas-assisted Injection Molded Polypropylene/Glass Fiber Composite: Foaming Structure and Tensile Strength

Tensile strength of isotactic polypropylene (iPP)/glass fiber (GF) composites and neat iPP molded respectively by gas-assisted injection molding (GAIM) was examined. For comparison, tensile strength of the counterparts, which were molded by conventional injection molding (CIM) under the same processing conditions but without gas penetration, was also examined. Tensile strength of the CIM parts steadily increases with the increase of the GF content. For neat iPP molded by GAIM, as the gas pressure increases the tensile strength increases. However, for the iPP/GF composites, the tensile strength generally decreases when the gas pressure increases. And, at a given content of GF, tensile strength of the parts molded by GAIM is unexpectedly lower than that of the counterparts molded by CIM. At a given gas pressure, the higher the fiber content, the lower the tensile strength. In addition, scanning electron microscope (SEM) results show that foaming structure should be responsible for the poor tensile strength of the composites molded by GAIM. The poor adhesion between the glass fibers and the matrix and the unique properties of the gas used in GAIM process are the substantial factors in the formation of foaming structure.     

两种羧酸盐成核剂的制备及其对聚丙烯的成核效果研究

合成了两种具有相似化学结构的聚丙烯（iPP）α晶型成核剂二环［2.2.1］庚⁃5⁃烯⁃2,3⁃二羧酸钠（NA₁）和二环［2.2.1］庚烷⁃2,3⁃二羧酸钠（NA₂）,研究了其在iPP中的成核效果。首先,利用差示扫描量热仪（DSC）和偏光显微镜（PLM）分别考察了两种成核剂对iPP结晶行为的影响。结果表明,当NA₁和NA₂的含量为0.3 %（质量分数,下同）时,iPP的结晶峰值温度分别提升了14.5 ℃和16.0 ℃。同时,两种成核剂都能够明显细化iPP球晶尺寸。其次,利用广角X射线衍射仪（WXAD）对成核iPP进行了表征,两种成核剂都诱导iPP产生了α晶型,说明均为α晶型成核剂。然后,对成核iPP的力学性能进行了表征。结果表明,随着两种成核剂用量的增加,iPP的拉伸强度和弯曲模量呈现先升高后平稳的趋势。当NA₁和NA₂含量为0.05 %时,成核iPP的拉伸强度较纯iPP分别提升了4.6 %和8.6 %,弯曲模量分别提升了8.2 %和21.7 %;冲击强度基本保持不变。     

Structural,elastic and thermal properties of titanium dioxide filled isotactic polypropylene

Titanium dioxide (TiO₂)-filled isotactic polypropylene (iPP) composites with various contents of TiO₂ were prepared by a locally fabricated extrusion molding machine. The extrudates were melt-pressed at 180 °C and produced as plane sheets of nearly equal thickness by rapid cooling. X-ray diffraction studies reveal a decrease of crystallinity and crystallites size as well as a change of α-, β- and γ-crystalline phases of the neat iPP to the α-form due to filler inclusion. Scanning electron micrographs taken on the fractured surface of the samples show increasing amount of voids with increasing filler content. Tensile strength, elongation-at-break (%) and glass transition temperature of the samples are found to decrease considerably with the increase in TiO₂ content, whereas microhardness decreases slightly with the filler content.     

Morphology of polypropylene/silica nano‐ and microcomposites

The aim of this study was to compare the effects of different silica grades on the structure and morphology of isotactic polypropylene (iPP)/silica composites to better understand their structure–property relationships. Isotactic polypropylene composites with 2, 4, 6, 8 vol % of added silica fillers differing in particle size (micro‐ vs. nanosilica) and surface modification (untreated vs. treated surface) were prepared by nonisothermal compression molding and characterized by different methods. The addition of all silica fillers grades to the iPP matrix significantly influenced the spherulitic morphology, while phase characteristics of the iPP matrix seemed to be unaffected. Surface modification of silica fillers exhibited stronger effects on spherulite size than size of silica particles. Nonpolar silica particles, more miscible or compatible with iPP chains than polar silica particles, enabled better spherulitic growth. The spherulite sizes tended to reach equal values at 8 vol % of added silicas showing that spherulite size became independent of filler concentration and surface modification above optimum filler concentration. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effects of EPDM and wollastonite on structure of isotactic polypropylene blends and composites

Polypropylene blends and composites with 5, 10, and 15 vol % of EPDM and 2, 4, and 6 vol % of untreated and treated wollastonite filler were examined by applying different techniques. Elastomeric ethylene/propylene/diene terpolymer (EPDM) component and wollastonite influenced the crystallization process of isotactic polypropylene (iPP) matrix in different ways. The nucleation of hexagonal β‐iPP, the increase of overall degree of crystallinity, and crystallite size of iPP were more strongly affected by wollastonite than the addition of EPDM was. Both ingredients also differently influenced the orientation of α‐form crystals in iPP matrix. Wollastonite increased the number of a*‐axis‐oriented α‐iPP lamellae plan parallel to the sample surface, whereas the addition of EPDM reoriented the lamellae. The orientation parameters of ternary composites exhibited intermediate values between those for binary systems because of the effects of both components. EPDM elastomer considerably affected well‐developed spherulitization of iPP, increasing the spherulite size. Contrary to EPDM, because of nucleating ability or crystal habit, wollastonite caused significantly smaller iPP spherulites. Small spherulites in ternary iPP/EPDM/wollastonite composites indicated that the wollastonite filler (even in smallest amounts) exclusively determined the morphology of ternary composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4072–4081, 2004     

Effects of nano‐ and micro‐fillers and processing parameters on injection‐molded microcellular composites

The effects of submicron core‐shell rubber (CSR) particles, nanoclay fillers, and molding parameters on the mechanical properties and cell structure of injection‐molded microcellular polyamide‐6 (PA6) composites were studied. The experimental results of PA6 nanocomposites with 5.0 and 7.5 wt% nanoclay loadings and of CSR‐modified PA6 composites with 0.5 and 3.1 wt% CSR loadings were compared to their neat resin counterparts. This study found that nanoclay was more efficient in promoting a smaller cell size, larger cell density, and higher tensile strength for microcellular injection molding parts. A higher nanoclay loading led to more brittle behavior for microcellular parts. It was found that a proper amount of CSR particles could be added to the microcellular injection‐molded PA6 to reduce the cell size, increase the cell density, and enhance the toughness of the molded part. However, CSR particles were less effective cell nucleation agents as compared to nanoclay for producing desirable cell structures, and a higher CSR loading was found to have diminishing effects on the process and on the properties of the parts. POLYM. ENG. SCI., 45:773–788, 2005. © 2005 Society of Plastics Engineers     

Preparation and balanced mechanical properties of solid and foamed isotactic polypropylene/SEBS composites

This study presents a self-designed foaming apparatus and routes to manufacture foamed isotactic polypropylene (iPP) blends with uniform and dense cells, using styrene-ethylene-butadiene-styrene (SEBS) block copolymer as toughening additive. The addition of SEBS can clearly enhance the impact strength of solid iPP, iPP blends with a 20 wt% SEBS has obtained high notched impact strength of 75 kJ/m², which is ca. 16 times larger than that of neat iPP. Relatively fine microcellular iPP-SEBS foams with the average cell size of several micrometers, and the cell density of 10⁹ cells/cm³ were fabricated using a batch foaming procedure. Moreover, using our self-designed mold and compression foaming method, iPP-SEBS foams with balanced mechanical properties were produced. With the increasing of SEBS, tensile strength and flexural strength were slightly decreased, but the impact strength was increased clearly. The balanced mechanical properties between stiffness and toughness were achieved after compression foaming.     

Hierarchic structure and mechanical property of glass fiber reinforced isotactic polypropylene composites molded by multiflow vibration injection molding

Maleic anhydride‐grafted polypropylene (Ma‐PP) and β nucleation agents (β‐NA) were used to modify the glass fiber (GF)/isotactic polypropylene (iPP) composite. The interface adhesion, degree of orientation, and crystalline morphologies of the PP/GF composites molded by multiflow vibrate‐injection molding (MFVIM) and conventional injection molding (CIM) were studied by polarized light microscopy (PLM), scanning electronic microscopy (SEM), and X‐ray measurements. Results prove that the interface adhesion was improved by the Ma‐PP; γ crystal was generated by the MFVIM due to the instant high pressure and shear during the multiflow; and a hierarchical structure which has a strengthened skin and a toughened core was formed. As a result, the final PP/GF/β‐NA composite has a 60% increase in tensile strength and 80% improvement in impact strength compare with the CIM pure PP/GF composite. Based on the observations, a modified model is proposed to interpret the strengthening and toughening mechanism. Our work paves the way to obtain high‐performance GF/iPP composites. POLYM. COMPOS., 38:2707–2717, 2017. © 2015 Society of Plastics Engineers     

结晶特性对微发泡聚丙烯材料发泡行为的影响

以化学发泡注塑成型技术为主线,在二次开模条件下制备微发泡PP材料;通过DSC、XRD技术分析了结晶特性对微发泡聚丙烯材料发泡行为的影响。结果表明:结晶特性对气泡的成核、长大和定型过程具有明显的影响;添加滑石粉的改性PP材料结晶特性较差,发泡质量明显降低,泡孔直径和泡孔密度分别为36.98μm、3.29×107个/cm3;添加云母粉的改性PP材料具有合适的结晶温度和结晶度,发泡质量较理想,泡孔直径和泡孔密度分别为22.09μm、4.76×108个/cm3;能够获得泡孔细小、均匀的微发泡PP材料。     

Mechanical and rheological properties of silica-reinforced polypropylene/m-EPR blends

Rheological and mechanical properties (tensile and impact properties) as well as the mechanical profiles of ternary isotactic polypropylene/silica/elastomer (iPP/SiO₂/m-EPR metallocene catalyzed ethylene-propylene rubber) composites were investigated and discussed. The effects of two metallocene ethylene-propylene-based elastomers (m-EPR) differing in molecular weight/viscosity and their content on iPP/silica composites with different silica types differing in size (nano- vs. micro-) and surface properties (untreated vs. treated) were investigated. The two m-EPR elastomers were added to iPP/SiO₂ 96/4 composites as possible impact modifier and compatibilizer at the same time in 5, 10, 15, and 20 vol% per hundred volume parts of composites. The effects of different silica fillers and two m-EPR rubbers were discussed within the context of structure-morphology-mechanical property relationships of these iPP/SiO₂/m-EPR composites. Tensile and impact strength properties were mainly influenced by combined competetive effects of stiff filler and tough m-EPR elastomer so sinergistic effect was also observed. The ductility of these composites was affected additionally by spherulite size of the iPP matrix due to the difference in nucleation abilities of silica fillers enabled by prevailing separated morphology observed in iPP/SiO₂/m-EPR composites.     

Orientation in composite of polypropylene and talc

X-ray diffraction and microscopical investigation of test samples prepared by injection molding from composites of isotactic polypropylene with talc revealed a preferred orientation of the talc and polypropylene matrix. Contrary to the situation in polypropylene alone, the preferred orientation in polypropylene–talc composites survived melting and a new crystallization. Crystallization rate measurements confirmed the nucleation activity of talc for polypropylene crystallization.     

The crystallization of polypropylene in multiwall carbon nanotube‐based composites

The crystallization process of isotactic polypropylene (iPP) was studied under both dynamic and isothermal conditions for a series of multiwall carbon nanotube (MWCNT) composites with nanotube concentrations between 0.1 and 1.0% by weight. The nucleation activity of the nanofillers was confirmed for both dynamic and isothermal crystallization, and was shown to be composition dependent. The effect of the nanofiller on the crystallization of iPP was discussed using the temperature coefficients obtained to determine the interfacial free energy and free energy of nucleation. The basal interfacial free energy decreased with respect to that of neat iPP by up to 15% for as little as 0.1% MWCNT, subsequently decreasing linearly with increasing nanotube concentration. This behavior is in line with the crystallization behavior of iPP with conventional nucleating agents. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Phenolic rigid organic filler/isotactic polypropylene composites. I. Preparation

A novel phenolic rigid organic filler (KT) was melt-mixed with an isotactic polypropylene (iPP) to prepare a series of PP/KT composites, with or without maleic anhydride grafted polypropylene (MAPP) as compatilizer. The evolution of filler morphology during melt-mixing and melt-pressure processes was monitored by scanning electron microscope (SEM) and polarized optical microscope (POM). The influences of shear force, pressure time, filler content and MAPP concentration on the final filler dispersion were studied. We found that this rigid organic filler readily melted and dispersed homogenously into the iPP matrix through a fission-fusion process during the melt-mixing process. Thus a balanced dispersion, which was closely related to shear force and MAPP concentration, can be achieved. During the meltpressure process, parts of the filler particles combined gradually through a coalescence process. However, the incorporation of MAPP can effectively inhibit the tendency to coalesce and refine the filler particles sizes into nanoscale. Thus, a series of PP/KT composites with controllable filler particles size and narrow size distribution can be obtained just by adjusting process conditions and MAPP concentration. In addition, due to the in-situ formation mechanism, the filler phase possessed a typical solid true-spherical shape.     

Phenolic rigid organic filler/isotactic polypropylene composites. I. Preparation

A novel phenolic rigid organic filler (KT) was melt-mixed with an isotactic polypropylene (iPP) to prepare a series of PP/KT composites, with or without maleic anhydride grafted polypropylene (MAPP) as compatilizer. The evolution of filler morphology during melt-mixing and melt-pressure processes was monitored by scanning electron microscope (SEM) and polarized optical microscope (POM). The influences of shear force, pressure time, filler content and MAPP concentration on the final filler dispersion were studied. We found that this rigid organic filler readily melted and dispersed homogenously into the iPP matrix through a fission-fusion process during the melt-mixing process. Thus a balanced dispersion, which was closely related to shear force and MAPP concentration, can be achieved. During the melt-pressure process, parts of the filler particles combined gradually through a coalescence process. However, the incorporation of MAPP can effectively inhibit the tendency to coalesce and refine the filler particles sizes into nanoscale. Thus, a series of PP/KT composites with controllable filler particles size and narrow size distribution can be obtained just by adjusting process conditions and MAPP concentration. In addition, due to the in-situ formation mechanism, the filler phase possessed a typical solid true-spherical shape.     

Structural,mechanical and thermal studies of double‐molded isotactic polypropylene nanocomposites with multiwalled carbon nanotubes

Nanocomposites of isotactic polypropylene (iPP) and multiwalled carbon nanotubes (MWCNTs) with various contents of MWCNTs were fabricated by double molding techniques. X‐ray diffraction measurements reveal a development of α‐crystal with lamellar stacks having a long period of 150 Å in the neat iPP that increases to 165 Å in 2 wt % MWCNTs‐loaded composites, indicating that MWCNTs enhance crystallization of iPP as a nucleating factor. Mechanical properties, such as tensile strength, flexural strength, Young's modulus, tangent modulus, and microhardness are found to increase with increasing MWCNTs content. Thermal analyses represent an increase of crystallization and melting temperatures and a decrease of thermal stability of the composites with increasing MWCNTs. Changes in structural, mechanical, and thermal properties of the composites due to the addition of MWCNTs are elaborately discussed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Calorimetric study of nanocomposites of multiwalled carbon nanotubes and isotactic polypropylene polymer

Modulated differential scanning calorimetry (MDSC) was used to measure the complex specific heat of the crystallization and melting transitions of nanocomposites of isotactic polypropylene (iPP) and carbon nanotubes (CNT) as function of CNT weight percent and temperature scan rate. In the last few years, great attention has been paid to the preparation of iPP/CNT nanocomposites due to their unique thermal and structural properties and potential applications. As the CNT content increases from 0 to 1 wt %, heterogeneous crystal nucleation scales with the CNT surface area. Above 1 wt %, nucleation appears to saturate with the crystallization temperature, reaching ～8 K above that of the neat polymer. Heating scans reveal a complex, two‐step, melting process with a small specific heat peak, first observed ～8 K below a much larger peak for the neat iPP. For iPP/CNT samples, these two features rapidly shift to higher temperatures with increasing ?_w and then plateau at ～3 K above that in neat iPP for ?_w ≥ 1 wt %. Scan rates affect dramatically differently the neat iPP and its nanocomposites. Transition temperatures shift nonlinearly, while the total transition enthalpy diverges between cooling and heating cycles with decreasing scan rates. These results are interpreted as the CNTs acting as nucleation sites for iPP crystal formation, randomly pinning a crystal structure different than in the neat iPP and indicating complex transition dynamics. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effects of processing conditions on foaming behaviors of polyetherimide (PEI) and PEI/polypropylene blends in microcellular injection molding process

Foaming behaviors of both neat polyetherimide (PEI) and PEI/polypropylene (PP) blends were studied in this article in microcellular injection molding (Mucell) process. The study mainly focused on the comparison of two materials' foaming behaviors under different processing conditions which took a critical effect on the morphologies of foams. The results indicated that the different characteristics of PEI and PEI/PP blends, such as melt strength, gas dissolvability, and solubility, induced different nucleation ability of PEI and PEI/PP blends. The addition of PP could obviously improve the cell density and reduce the cell size. With the processing conditions changing, the morphologies of PEI/PP altered more variously, and their distribution of cell density was wider. This suggested that foaming behaviors of PEI/PP blends was more flexible to be controlled by the processing conditions than neat PEI. The effects of shot size, gas injection, and injection rate on foam morphologies were studied in detail. Shot size determined the weight reduction of samples and affected the cell density and size significantly. Gas dosing time and dosing rate determined the gas ratio which effected on foam morphologies of the PEI and PEI/PP foams. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41443.     

Crystallization behaviors in the isotactic polypropylene/graphene composites

Crystallization behaviors and kinetics of iPP in an in-situ prepared isotactic polypropylene/graphene (iPP/G) composites were studied in this paper. In samples used in this study, the graphene fillers were well dispersed, and the interfacial adhesion exhibited enhanced features between graphene and iPP components. The thermal stability of the composites was improved by about 100 °C compared to the pristine iPP. It was found that the crystallization morphology, crystallization rate and kinetics of the iPP/G composites were significantly influenced by the presence of graphene. The nucleation and epitaxial growth of iPP on the graphene surface were observed and studied in detail. It was observed that the nucleation of iPP favored to occur at the wrinkles and edges due to the good match of the lattice parameters and the weak spatial hindrance compared to the smooth surface. Numerous nuclei epitaxially formed and the size of the crystals was very small. The schematic diagram was also proposed for the nucleation and growth process of iPP on the graphene surface in the iPP/G composites. Meanwhile, the overall crystallization kinetics and crystals growth were analyzed through Avrami equation. The obtained Avrami index n decreased with the graphene loadings and was close to 2 for the iPP/G composites, which implied that the growth of iPP in the composites was in two-dimension. And this was caused by the structure of graphene and the spatial confinement effect of graphene platelets in the iPP/G composites.     

Crystallization,mechanical properties and thermal stability of cockleshell-derived CaCO<Subscript>3</Subscript> filled polypropylene

This study discusses the potential of utilizing waste cockleshell derived-CaCO₃ (CS) as filler in polypropylene (PP). Mineral fillers were prepared from cockleshell-derived CaCO₃ and used to fill polypropylene. The composites were prepared by melt blending and fabricated by injection and compression molding techniques. The effects of filler on crystal structure, crystallization and thermal degradation characteristics of filled polypropylene composites were elucidated. The cockleshell filler promoted the formation of the β-crystalline phase in PP, which improved the rigidity and toughness of the composites. However, stearic acid treatments on the filler would significantly affect the nucleation process and therefore hindered crystallization. Acceleration in thermal degradation of PP was also noted with increasing filler loading.