Effects of mixing protocols on impact modified poly(lactic acid) layered silicate nanocomposites

Poly(lactic acid)/2 wt % organomodified montmorillonite (PLA/OMMT) was toughened by an ethylene‐methyl acrylate‐glycidyl methacrylate (E‐MA‐GMA) rubber. The ternary nanocomposites were prepared by melt compounding in a twin screw extruder using four different addition protocols of the components of the nanocomposite and varying the rubber content in the range of 5–20 wt %. It was found that both clay dispersion and morphology were influenced by the blending method as detected by X‐ray diffraction (XRD) and observed by TEM and scanning electron microscopy (SEM). The XRD results, which were also confirmed by TEM observations, demonstrated that the OMMT dispersed better in PLA than in E‐MA‐GMA. All formulations exhibited intercalated/partially exfoliated structure with the best clay dispersion achieved when the clay was first mixed with PLA before the rubber was added. According to SEM, the blends were immiscible and exhibited fine dispersion of the rubber in the PLA with differences in the mean particle sizes that depended on the addition order. Balanced stiffness‐toughness was observed at 10 wt % rubber content in the compounds without significant sacrifice of the strength. High impact toughness was attained when PLA was first mixed with the clay before the rubber was added, and the highest tensile toughness was obtained when PLA was first compounded with the rubber, and then clay was incorporated into the mixture. Thermal characterization by DSC confirmed the immiscibility of the blends, but in general, the thermal parameters and the degree of crystallinity of the PLA were not affected by the preparation procedure. Both the clay and the rubber decreased the crystallization temperature of the PLA by acting as nucleating agents. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41518.     

Study on adhesion strength,thermal creep resistance,and light transmittance of ethylene‐polypropylene copolymer grafted with silane for photovoltaic application

We investigated the possibility of using PP as an encapsulant in a photovoltaic module. PP is inexpensive but shows low adhesion strength to glass (and silicon wafer) due to its nonpolar nature as well as opacity due to its crystalline nature. We resolved these problems by employing metallocene catalyzed ethylene‐propylene copolymer (EPR) and a nucleating agent to increase the transparency. Five EPRs having various propylene/ethylene ratios were investigated. EPRs having higher propylene content showed higher adhesion strength to the glass substrate. However, it is not appropriate to use EPRs with higher propylene content because they show low processability in calendaring processing. We therefore used a blend of two EPRs. The blend of the two EPRs showed somewhat low transparency. When the nucleating agent was incorporated in the blend, the transparency was remarkably increased. The adhesion strength to the glass plate was enhanced by a silane coupling agent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43464.     

Correlation between the fracture toughness and β‐crystal fraction in a β‐nucleated propylene‐based propylene–ethylene random copolymer

Propylene‐based propylene–ethylene random copolymer (PPR) has been widely used in the production of hot‐water pipes. To further improve its toughness and thermal resistance, β‐nucleating agents (β‐NAs) are frequently incorporated. In this study, PPR containing 5.6 mol % ethylene units was modified by two kinds of β‐NAs, that is, calcium pimelate and N,N′‐dicyclohexylterephthalamide. The notched Izod impact strength of PPR increased with the addition of the β‐NAs. Drastically different toughening effects were found between the two β‐NAs. The structure of PPR with and without a β‐NA was investigated by calorimetry, X‐ray diffraction, and thermomechanical analysis. The results indicated that the relative fraction of β crystals (k_β) in the injection‐molded specimens was determined by the type and content of β‐NA. The relationship between k_β and the impact toughness was summarized. A critical value for k_β (0.68) was identified for the brittle–ductile transition of PPR. PPR with β‐NA having a k_β greater than 0.68 displayed a higher impact strength than the other mixtures. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42930.     

Effect of nucleating agents on the crystallization of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)

The effect of nucleating agents on the crystallization behavior of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) was studied. A differential scanning calorimeter was used to monitor the energy of the crystallization process from the melt and melting behavior. During the crystallization process from the melt, nucleating agent led to an increase in crystallization temperature (T_c) of PHBV compared with that for plain PHBV (without nucleating agent). The melting temperature of PHBV changed little with addition of nucleating agent. However, the areas of two melting peaks changed considerably with added nucleating agent. During isothermal crystallization, dependence of the relative degree of crystallization on time was described by the Avrami equation. The addition of nucleating agent caused an increase in the overall crystallization rate of PHBV, but did not influence the mechanism of nucleation and growth of the PHB crystals. The equilibrium melting temperature of PHBV was determined as 187°C. Analysis of kinetic data according to nucleation theories showed that the increase in crystallization rate of PHBV in the composite is due to the decrease in surface energy of the extremity surface. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2145–2152, 2002     

Spinning and characterizations of polypropylene/alkylphosphonic acid treated montmorillonite nanocomposite fiber

Fine and well‐dispersed clay was prepared via the in situ conversion of the dodecylamine intercalant inside the clay gallery to dodecylamino dimethylene diphosphonic acid (DDD), using a Mannich reaction, so as to create a repulsive force that delaminated the clay platelets. The clay structure and morphology were characterized by X‐ray diffraction (XRD), Scanning electron microscopy (SEM), and Transmission electron microscopy (TEM) analysis, which revealed changes in the multilayer stacks. XRD analysis showed that the interlayer spacing was largely expanded by the presence of DDD. SEM and TEM images revealed that DDD containing clay (PMMT), but not that without DDD, exhibited transparency, indicating the extremely fine and well‐dispersed clay. Polypropylene/PMMT nanocomposites containing 2, 4, 6, 8, and 10 wt % PMMT were prepared by melt extrusion. The obtained compounds were each spun into a monofilament fiber using a small scale spinning machine and then characterized by XRD, Differential scanning calorimetry (DSC), and Thermogravimetric analysis (TGA), plus the sonic modulus was evaluated. The XRD results revealed an increase in the β crystallinity peak in fibers loaded with 2–10 wt % PMMT, indicating that PMMT particles were capable of acting as a β‐form nucleating agent. However, only minimal changes in the thermal behavior (T_c) were observed due to the tested samples containing insufficient PMMT content. The mechanical properties, in terms of the tensile strength and sonic modulus value (E), of the polypropylene nanocomposite fibers were higher than those of virgin PP fibers, presumably due to the reinforcement effect of the filled PMMT nanoparticles. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of porous membranes by selective decomposition of adamantane unit in ABA‐type triblock copolymer

The mechanism of pore formation by selective decomposition of adamantane unit in an ABA‐type triblock copolymer derived from 4,4‐(hexafluoroisopropylidene)diphthalic anhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) and poly(2‐methyl‐2‐adamantylmethacrylate) (PMAdMA) was investigated on this basis. This study aims to developing a novel method of material design for high‐precision gas separation membranes and application to electric devices by improving dielectric constant. Scanning electron microscopy images showed that the membrane structure changed considerably after heating; the difference increased with the increase in adamantane content. Interestingly, the internal structure of Block(36 mol%6FDA‐TeMPD/64 mol%PMAdMA) membrane was almost unchanged although its surface structure was changed. These results suggest that the mechanism of formation of porous membrane involves the decomposition of adamantane unit from surface. In addition, more adamantane units inside the membrane were discharged to the surface of the membrane through a path formed by decomposed adamantane units. POLYM. ENG. SCI., 56:1191–1200, 2016. © 2016 Society of Plastics Engineers     

The Nucleating Effect of Montmorillonite on Crystallization of PET/Montmorillonite Nanocomposite

Poly(ethylene terephthalate) (PET)/montmorillonite (MMT) nanocomposites were prepared by solution intercalation method. The clay was organo-modified with intercalation agent of cetyltrimetylammonium chloride (CMC). XRD showed that the layers of MMT were intercalated by CMC. Four nanocomposites with organoclay contents of 1, 5, 10, and 15 wt% were prepared by solution blending. XRD showed that the interlayer spacing of organoclay in the nanocomposites depends on the amount of organoclay. The nucleating effect of organoclay is investigated using differential scanning calorimetry (DSC) analysis. Clay behaves as a nucleating agent and enhances the crystallization rate of PET. Maximum enhancement in crystallization rate for the nanocomposites was observed in blends containing ca. 10 wt% of clay in the range of 1–15 wt%. According to transmission electron microscopy (TEM), the organoclay particle was highly dispersed in the PET matrix without a large agglomeration of particles for low organoclay content (5 wt%). Agglomerated structure did form in the PET matrix at 15 wt% organoclay content.     

Preparation and properties of polypropylene/org-attapulgite nanocomposites

Polypropylene (PP)/org-attapulgite (ATP) nanocomposites were prepared by melt blending in a mixer apparatus. Org-attapulgite was attained by silane coupling agent modification first and then graft-polymerization with butyl acrylate. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to assess the clay morphology and the dispersion of the org-attapulgite, respectively. The changes of crystalline structure for PP nanocomposites were characterized by X-ray diffraction (XRD). The mechanical properties of PP/attapulgite nanocomposites were studied through tensile and impact tests. The thermal and dynamic mechanical properties were characterized by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The strength and stiffness of PP/org-ATP nanocomposites were both improved significantly in the presence of organic attapulgite. In addition, the incorporation of org-ATP also gave rise to an increase of the storage modulus and the changes of the glass transition temperature for PP composites. TEM and XRD results revealed the addition of attapulgite did not change the crystal structure of PP, however org-attapulgite acted as nucleating agents for the crystallization of PP.     

The Use of Ethylene/Propylene Copolymers as Compatibilizers for Recycled Polyolefin Blends

Compatibilizing effects of ethylene/propylene (EPR) diblock copolymers on the morphology and mechanical properties of immiscible blends produced from recycled low‐density polyethylene (PE‐LD) and high‐density polyethylene (PE‐HD) with 20 wt.‐% of recycled poly(propylene) (PP) were investigated. Two different EPR block copolymers which differ in ethylene monomer unit content were applied to act as interfacial agents. The morphology of the studied blends was observed by scanning‐ (SEM) and transmission electron microscopy (TEM). It was found that both EPR copolymers were efficient in reducing the size of the dispersed phase and improving adhesion between PE and PP phases. Addition of 10 wt.‐% of EPR caused the formation of the interfacial layer surrounding dispersed PP particles with the occurrence of PE‐LD lamellae interpenetration into the layer. Tensile properties (elongation at yield, yield stress, elongation at break, Young's modulus) and notched impact strength were measured as a function of blend composition and chemical structure of EPR. It was found that the EPR with a higher content of ethylene monomer units was a more efficient compatibilizer, especially for the modification of PE‐LD/PP 80/20 blend. Notched impact strength and ductility were greatly improved due to the morphological changes and increased interfacial adhesion as a result of the EPR localization between the phases. No significant improvements of mechanical properties for recycled PE‐HD/PP 80/20 blend were observed by the addition of selected block copolymers.     

汽车用高流动性共聚聚丙烯的结构与性能

采用溶剂萃取分离的方法将汽车用高流动性共聚聚丙烯分成以乙丙橡胶为主要成分的可溶物和以等规聚丙烯为主的不溶物2个级分。用红外光谱,核磁共振碳谱、凝胶渗透色谱、偏光显微镜、原子力显微镜等测试手段,分析研究了各级分的链结构、聚集态结构,相态结构等,并与国外试样进行比较。结果表明：开发的汽乍用高流动性共聚聚丙烯中乙烯含量,橡胶含量以及橡胶中乙烯含量均较高,且乙烯在分子链上的分布均匀、合理,有效地提高了产品的抗冲击性能;不溶物立构规整性好、结晶度高．保持了材料的良好刚性。     

Improving mechanical performance of injection molded PLA by controlling crystallinity

Currently, use of poly(lactic acid) (PLA) for injection molded articles is limited for commercial applications because PLA has a slow crystallization rate when compared with many other thermoplastics as well as standard injection molding cycle times. The overall crystallization rate and final crystallinity of PLA were controlled by the addition of physical nucleating agents as well as optimization of injection molding processing conditions. Talc and ethylene bis‐stearamide (EBS) nucleating agents both showed dramatic increases in crystallization rate and final crystalline content as indicated by isothermal and nonisothermal crystallization measurements. Isothermal crystallization half‐times were found to decrease nearly 65‐fold by the addition of only 2% talc. Process changes also had a significant effect on the final crystallinity of molded neat PLA, which was shown to increase from 5 to 42%. The combination of nucleating agents and process optimization not only resulted in an increase in final injection molded crystallinity level, but also allowed for a decreased processing time. An increase of over 30°C in the heat distortion temperature and improved strength and modulus by upwards of 25% were achieved through these material and process changes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synergistic effects of 4A zeolite on the flame‐retardant properties and thermal stability of an efficient halogen‐free flame‐retardant EVA composite

The synergistic effects of 4A zeolite (4A) on the thermal degradation, flame retardancy, and char formation of an efficient halogen‐free flame‐retardant ethylene‐vinyl acetate copolymer composite (EVA/IFR) were investigated by limited oxygen index (LOI), vertical burning test (UL‐94), cone calorimeter test (CCT), digital photography, scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), laser Raman spectroscopy (LRS) and thermogravimetric analytical (TGA) methods. It was found that a small amount of 4A clearly improved the LOI value of the EVA/IFR composite and reinforced the fire retardant performance with a great reduction in the combustion parameters of the EVA/IFR system from the CCT test. The entire composites passed the UL‐94 V‐0 rating test. The TGA and integral procedure decomposition temperature (IDPT) results showed that 4A enhanced the thermal stability of the EVA/IFR system and increased the char residue content effectively. The morphological structures observed by digital and SEM imaging revealed that 4A could promote EVA/IFR to form a more continuous and compact intumescent char layer. The LRS and EDS results demonstrated that by introduction of 4A into the EVA/IFR system, a more graphite structure was formed with increase phosphorus content in the char residue. POLYM. ENG. SCI., 56:380–387, 2016. © 2016 Society of Plastics Engineers     

Polypropylene/linear low‐density polyethylene blends: Morphology,crystal structure,optical, and mechanical properties

The morphology, crystal structure, crystallization behavior, optical, and mechanical properties of isotactic polypropylene (iPP) blended with metallocene linear low‐density polyethylene (mLLDPE) and Ziegler–Natta linear low‐density polyethylene (zLLDPE), with and without nucleating agents, were investigated. The correlation between the structures and optical properties was investigated. The addition of linear low‐density polyethylenes (LLDPEs), nucleating agents, and poly(ethylene‐co‐octene) (POE) had little influence on the crystal form of the iPP. The growth along the b axis was favorable in the presence of nucleating agents and LLDPEs. The LLDPEs led to much finer crystal morphologies, and the nucleating agents further prohibited spherulite formation; consequently, light scattering from the bulk crystalline structure was reduced. In all blends, biphase morphology was observed, and POE could improve the adhesion between the iPP and mLLDPE. After blending with LLDPEs, the haze and stiffness decreased, and the gloss increased. mLLDPE enhanced the toughness whereas zLLDPE had a slight influence on it. The nucleating agents decreased the haze, increased the gloss more, and ameliorated the stiffness; however, they changed the toughness little. POE increased the toughness of the blend significantly, accompanied by a much lower haze, higher gloss, and almost the same stiffness. When the concentration of 1,3 : 2,4‐bis(3,4‐dimethyl‐benzylidene sorbitol) exceeded 0.25 wt %, the optical properties and mechanical properties leveled off. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

成核剂对增韧聚丙烯力学性能的影响

主要研究成核剂种类及用量对乙烯－辛烯共聚物（POE）增韧聚丙烯（PP）力学性能的影响。研究表明：随着成核剂NA1的加入,PP／POE共混物的透明性、冲击强度、弯曲强度、拉伸屈服强度均明显提高,研制的改性PP的透明性、韧性和刚性得到了平衡。     

Mechanical and thermal properties of high‐density polyethylene toughened with glass beads

Glass beads were used to improve the mechanical and thermal properties of high‐density polyethylene (HDPE). HDPE/glass‐bead blends were prepared in a Brabender‐like apparatus, and this was followed by press molding. Static tensile measurements showed that the modulus of the HDPE/glass‐bead blends increased considerably with increasing glass‐bead content, whereas the yield stress remained roughly unchanged at first and then decreased slowly with increasing glass‐bead content. Izod impact tests at room temperature revealed that the impact strength changed very slowly with increasing glass‐bead content up to a critical value; thereafter, it increased sharply with increasing glass‐bead content. That is, the Izod impact strength of the blends underwent a sharp transition with increasing glass‐bead content. It was calculated that the critical interparticle distance for the HDPE/glass‐bead blends at room temperature (25°C) was 2.5 μm. Scanning electron microscopy observations indicated that the high impact strength of the HDPE/glass‐bead blends resulted from the deformation of the HDPE matrix. Dynamic mechanical analyses and thermogravimetric measurements implied that the heat resistance and heat stability of the blends tended to increase considerably with increasing glass‐bead content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2102–2107, 2003     

Titanium Dioxide and Gamma Irradiation Induced Changes in the Structural,Morphology, and Mechanical Behavior of Ethylene Vinyl Acetate Copolymer

Some composites were prepared depending on ethylene vinyl acetate (EVA) copolymer with 18% VA content and titanium dioxide (TiO₂). These composites were prepared in the ratios of 100/0, 90/10, 80/20, 70/30, and 60/40 by melt mixing method. Gamma radiation at differing doses was applied on pure EVA and composites to investigate the impact on modification of composites. Gel percentage and the Charlesby‐Pinner equation were used to confirm crosslinking increases. X‐Ray diffraction measurement (XRD), scanning electron microscope (SEM), and mechanical testing were all used to investigate the varying effects of the different processes on the structure, morphology, and mechanical behavior of EVA. It was observed that the addition of TiO₂ and gamma irradiation both have a significant effect on the structure and, therefore, the composites' surface morphology. Notable changes of the lattice structure were revealed by the XRD results for both unirradiated and irradiated composites, which were also confirmed by examination of the samples' surface morphology. It was found that the presence and amount of TiO₂ along with the irradiation process has a significant influence upon the EVA's mechanical behavior. When compared with the pure EVA, the results demonstrated a significant enhancement in the mechanical parameters of both unirradiated and irradiated composites, except elongation at break. The mechanical results were in line with gel content analysis. The reliability of gamma radiation as an applied method for controlling long‐term properties is clearly demonstrated. J. VINYL ADDIT. TECHNOL., 26:224–235, 2020. © 2019 Society of Plastics Engineers     

Mechanical properties and structural characteristics of dynamically photocrosslinked PP/EPDM blends

The mechanical properties and crystal morphological structures of dynamically photocrosslinked polypropylene (PP)/ethylene‐propylene‐diene terpolymer (EPDM) blends have been studied by mechanical tests, wide‐angle X‐ray diffraction (WAXD), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). Dynamically photocrosslinking of PP/EPDM blends can improve the mechanical propertiess considerably, especially the notched Izod impact strength at low temperature. Data obtained from mechanical tests show that the notched Izod impact strength of a dynamically photocrosslinked sample with 30% EPDM at ?20°C is about six times that of an uncrosslinked sample with the same EPDM component. The results from the WAXD, SEM, and DSC measurements reveal the enhanced mechanism of impact strength for the dynamically photocrosslinked PP/EPDM blends as follows: (i) the β‐type crystal structure of PP is formed and the interplanar distance of β‐type crystal increases slightly with an increase in the EPDM component; (ii) the droplet size of the EPDM phase in the photocrosslinked PP/EPDM blends is obviously reduced and the droplet number is increased with an increase in the EPDM component during the dynamical photocrosslinking process; (iii) the graft copolymer of PP‐g‐EPDM is formed at the interface between PP and EPDM components. All the above changes from the crystal morphological structures are favorable for increasing the compatibility and enhancing the toughness of PP/EPDM blends at low temperatures.     

Influence of apple flavor absorption on physical and mechanical properties of poly(ethylene terephthalate) films

Poly(ethylene terephthalate) (PET) films (280‐μm film thickness), which are used in food packaging, were immersed into 160‐ and 320‐ppm apple flavor solution for 14, 28, and 56 days at 5, 25, and 40°C, respectively. At the end of this period, the changes in the PET films were investigated by measuring the mechanical and physical properties. The mechanical properties were determined by examining changes in the Young's modulus. The changes in the physical properties were investigated by Fourier transform IR spectroscopy and scanning electron microscopy (SEM). The formation of microcracks in the structure of PET films was observed by SEM. According to the results of those investigations, the apple flavor affects PET films, even at very low concentrations and temperatures. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1802–1807, 2006     

Irbesartan‐loaded electrospun nanofibers‐based PVP K90 for the drug dissolution improvement: Fabrication,in vitro performance assessment,and in vivo evaluation

Irbesartan with a low bioavailability is known as a poorly water‐soluble drug. The purpose of this investigation is the improvement of physicochemical properties (such as solubility and dissolution rate) of Irbesartan using electrospun nanofibers‐based solid dispersion preparation. Nanofibers were prepared using certain weight ratios of the drug and polyvinylpyrrolidone K90 (PVP K90). Then, dissolution studies were carried out. Moreover, selected samples were examined by many different tests such as Fourier transform infra red (FTIR), differential scanning calorimetry (DSC), X‐ray diffraction (XRD), high‐performance liquid chromatography (HPLC), and scanning electron microscopy (SEM). Though solubility and dissolution rate of all Irbesartan‐PVP nanofibers improved, but the best result was obtained through of ENSD5 (3% (w/v) : 7% (w/v)). In sink condition approximately 97% of this sample was released during 60 min. The drug content was among the different batches from 40.55 ± 1.01 to 245.32 ± 1.77 μg/mL. The maximum saturation solubility was belonged to this sample. According to the results of the thermal analysis and FTIR spectroscopy, there is no chemical reaction between drug and carrier, also samples has not changed during the process. Amorphous structure for nanofibers was confirmed by DSC thermograms and XRD diffractograms and morphological structure of samples were observed by SEM images. Ultimately, in vivo studies were performed in healthy grey rabbits and the results were satisfactory. The drug–polymer nanofibers showed an increase in relative bioavailability than the plain Irbesartan suspension. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42212.     

Synthesis and characterization of poly(ethylene terephthalate) nanocomposites with organoclay

Poly(ethylene terephthalate) (PET)/montmorillonite (MMT) nanocomposites were prepared by solution intercalation method. The clay was organo‐modified with the intercalation agent cetylpyridinium chloride (CPC). Wide‐angle X‐ray diffraction (XRD) showed that the layers of MMT were intercalated by CPC. Four nanocomposites with organoclay contents of 1, 5, 10, and 15 wt % were prepared by solution blending. XRD showed that the interlayer spacing of organoclay in the nanocomposites depends on the amount of organoclay present. According to the results of differential scanning calorimetry (DSC) analysis, clay behaves as a nucleating agent and enhances the crystallization rate of PET. The maximum enhancement of crystallization rate for the nanocomposites was observed in those containing about 10 wt % organoclay within the studied range of 1–15 wt %. From thermogravimetric analysis (TGA), we found that the thermal stability of the nanocomposites was enhanced by the addition of 1–15 wt % organoclay. These nanocomposites showed high levels of dispersion without agglomeration of particles at low organoclay content (5 wt %). An agglomerated structure did form in the PET matrix at 15 wt % organoclay. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 140–145, 2004