Applying vermiculite‐modified polypropylene film to flexible packaging material

This article presents a process for preparing organovermiculite by ball‐milling expanded vermiculite (EVMT) in water‐based ethylene vinyl acetate (EVA) latex. In this process, the vermiculite (VMT) is exfoliated to prepare a kind of EVMT/EVA modifying agent, in which EVA serves as both intercalating polymer into VMT and compatibilizer between VMT and polypropylene (PP). During melt blending between EVMT/EVA and PP, shear force exfoliates VMT sheets, dispersing them relatively well in the PP matrix. Compared with raw PP, EVMT‐modified cast polypropylene (CPP) are better when EVMT loading ranged from 0.5 to 1.0%, with improvement in both the strength and toughness of the EVMT/EVA‐modified CPP film. Specifically, tensile strength was increased by 44–54%, yield stress increased by 26%, stress at break increased by 37–43%, energy at break (toughness) increased by 29–34%, oxygen transmission rate decreased by 6.2–12.9%, the water vapor transmission rate was not significantly affected, the peel bond strength of laminated CPP film increased by 18–27%, and the processability and melt flow index (MFI) of EVMT/EVA/PP composites were improved as well. Increasing MFI attributes facilitated the processing and formation of EVMT/EVA/PP. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40954.     

Influence of nanovermiculites with a high aspect ratio and stretch orientation on the microstructure of polypropylene films

In this article, we present a process for preparing organovermiculites, which consist of expanded vermiculite (EVMT)–poly(vinyl alcohol) (PVOH) created by the mechanical ball‐milling of EVMT in a PVOH–water solution. We then discusses the influence of EVMT–PVOH on the barrier performance, crystallization behavior, thermal stability, and mechanical properties of modified blown polypropylene (PP) films. EVMT was intercalated and exfoliated by PVOH macromolecules to obtain a kind of hybrid EVMT–PVOH. PVOH served as both an intercalating agent into EVMT and a compatibilizer between EVMT and PP. Compared with the original (unmodified) PP, when the EVMT loading ranged from 0.1 to 2.0%, although the crystallinity decreased for most PP films, the thermal stability and mechanical properties all improved. Moreover, EVMT platelike particles with a high aspect ratio (ca. 550) dispersed in the PP matrix also improved the barrier properties of the modified PP films, which was in accordance with the Nielsen model. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42846.     

Ethylene vinyl acetate/Mg‐Al LDH nanocomposites by solution blending

Partially exfoliated ethylene vinyl acetate (EVA‐40, 40% vinyl acetate content)/layered double hydroxide (LDH) nanocomposites using organically modified layered double hydroxide (DS‐LDH) have been synthesized by solution intercalation method. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) studies of nanocomposites shows the formation of exfoliated LDH nanolayers in EVA‐40 matrix at lower DS‐LDH contents and partially intercalated/exfoliated EVA‐40/MgAl LDH nanocomposites at higher DS‐LDH contents. These EVA‐40/MgAl LDH nanocomposites demonstrate a significant improvement in tensile strength and elongation at break for 3 wt% of DS‐LDH filler loading compare to neat EVA‐40 matrix. Thermogravimetric analysis also shows that the thermal stability of the nanocomposites increases with DS‐LDH content in EVA‐40. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Nanocomposites formed from polypropylene/EVA blends

Rubber toughened polypropylene nanocomposites using two types of modified montmorillonite (organoclay) were explored with the objective of achieving an improved balance between stiffness and toughness. The effect of three blending sequences on microstructure and properties of the ternary nanocomposites was also investigated. A commercial grade of ethylene/vinyl acetate copolymer (EVA) containing 18 wt% of vinyl acetate was used as the impact modifier for polypropylene and an acrylic acid grafted polypropylene was used to compatibilize the systems studied. The toughened nanocomposites samples were prepared by melt compounding in a twin-screw extruder; the morphology and mechanical properties of the resulting materials were characterized by X-ray scattering, electron microscopy and tensile and impact testing. The results show that incorporation of EVA increases the toughness of the polypropylene but its stiffness decreased markedly due to the incorporation of the low modulus component. The addition of organoclay increased the modulus slightly for all the ternary nanocomposites with respect to the blend, but it remains lower than that of neat PP. Surprisingly, addition of organoclay to the blends promoted a drastic increase in the notched Izod impact strength and a considerable alteration of the shape of the dispersed EVA phase when the organoclay is located in this phase. Moreover, it was found that the blending sequence effects on the morphology and properties of the mixtures are dependent on the organoclay used.     

Effect of SiO2/EVA on the mechanical properties,permeability, and residual solvent of polypropylene packaging films

The surface of nano‐silica was modified by ethylene/vinyl acetate (EVA) emulsion and then blended with polypropylene (PP) to yield a nano‐silica/PP composite material. This composite was intended to enhance the mechanical properties of PP, improve its melting point and degree of crystallinity, reduce its oxygen permeability and water vapor permeability, decrease the adsorption of PP packaging films against organic solvents, and improve the films' performance for food safety. The experiments showed that the crystallinity of PP modified by nano‐silica increased, leading to enhanced mechanical and barrier properties, while its melting point rose. Meanwhile, the residual solvent value of the modified PP films was reduced by 10–90%. POLYM. COMPOS., 101–107, 2016. © 2014 Society of Plastics Engineers     

Morphology, rheology and dynamic mechanical properties of PP/EVA/clay nanocomposites

This paper reports on morphology, rheology and dynamic mechanical properties of polypropylene (PP)/ethylene vinyl acetate (EVA) copolymer/clay nanocomposite system prepared via a single step melt compounding process using a twin screw micro-compounder. Scanning electron microscopic (SEM) investigations revealed that the dispersed phase droplet size was reduced with incorporation of an organo-modified montmorillonite (OMMT). This reduction was more significant in presence of a maleated PP (PP-g-MAH) used as compatibilizer. Phase inversion in the compatibilized blends caused a further decrease in PP droplet size. The OMMT gallery spacing was higher in nanocomposites with EVA as matrix which could be attributed to higher tendency of OMMT nanoparticles towards EVA rather than PP. This enhanced tendency was confirmed by rheological analysis too. Transmission electron microscopy (TEM) results also showed that the majority of OMMT nanoparticles were localized on the interface and within EVA droplets. According to dynamic mechanical analysis, the compatibilized nanocomposites showed higher storage and loss moduli due to better dispersion of OMMT layers. The modulus enhancement of nanocomposites as a function of OMMT volume fraction was modeled by Halpin-Tsai’s-Nielsen expression of modulus for nanocomposites. The results of modeling suggested that the aspect ratio of the intercalated OMMT, in the form of Einstein coefficient (K _E), plays a determining role in the modulus enhancement of nanocomposites.     

Morphology and mechanical properties of heterophasic PP–EP/EVA/organoclay nanocomposites

The effect of vinyl acetat (VA) on the morphological, thermal stability, and mechanical properties of heterophasic polypropylene–(ethylene‐propylene) copolymer (PP–EP)/poly(ethylene vinyl acetate) (EVA)/organoclay nanocomposites was studied. Tailored organoclay C20A was selected to enhance the exfoliation of the clay platelets. Depending on the VA content, there were two morphological organoclay populations in the systems. Both populations were directly observed by scanning transmission electron microscopy and measured by wide‐angle X‐ray diffraction and small‐angle X‐ray scattering. The content of VA in EVA originated spherical and elongated morphologies in the resultant nanocomposites. High‐VA content led to a better intercalation of the organoclay platelets. Measurement of thermal properties suggested that higher VA decreases thermal stability in samples both with and without organoclay, although nanocomposites had higher thermal stability than samples without clay. The storage modulus increased both with nanoclay and VA content. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Morphology and chain mobility of reactive blend nanocomposites of PP‐EVA/Clay

Polypropylene (PP)‐ethylene vinyl acetate (EVA)/clay nanocomposites were prepared via reactive blending using dicumyl peroxide (DCP) as an initiator with the goal of enhancing the interaction between both phases and modified nanoclay. The effect of the reactive blending and clay incorporation strategies (direct and masterbatch) on the blend and nanostructure morphology, and chain mobility of nanocomposites were studied. The chemical analysis showed the chemical bonding of PP‐EVA, which helped to enhance the interaction in the nanocomposites. The nanocomposites obtained from the direct clay strategy presented a co‐continuous morphology of bordering intercalated and agglomerated nanoclay sheets, while the nanocomposites obtained from the masterbatch strategy showed that blend morphology change from droplet to co‐continuous with the increase of EVA concentration, with intercalated/exfoliated nanoclay sheets located in the EVA domains and at the interface. The dynamic mechanical and creep‐recovery results showed different behavior for the both strategies in terms of chain mobility and relaxation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40897.     

水辅助注塑PP/EVA共混物的相形态

通过扫描电镜(SEM)观察了水辅助注塑聚丙烯(PP)/乙烯-醋酸乙烯共聚物(EVA)共混物制品近浇口和远浇口处外表层、芯层和内表层的相形态.结果表明,分散相主要以层状分布在基体中,在两个观察位置外表层和内表层的层状分散相厚度比芯层的大,远浇口处外表层和内表层的分散相厚度比近浇口处对应层的大.从温度场和剪切场两个方面分析了分散相的形变过程.     

Investigation of oxygen barrier properties of organoclay/HDPE/EVA nanocomposite films prepared using a two-step solution method

In this article, oxygen barrier properties of nanocomposite films composed of organoclay (OC), high-density polyethylene (HDPE), and ethylene vinyl acetate (EVA) copolymer have been investigated. The nanocomposite films whose EVA forms a dominant fraction were prepared using the solution method. The dispersion of the OC in the HDPE/EVA blend was improved through taking two-step procedure in the preparation of nanocomposite. First, the OC and EVA were dissolved in chloroform. Then, the resulting product, after evaporating most of the solvent, along with HDPE was dissolved in xylene. The obtained nanocomposite films underwent a number of tests in order to examine their barrier properties including X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results showed that OC/HDPE/EVA nanocomposites are intercalated and partially exfoliated. Furthermore, from the TEM micrographs, the organoclay experimental aspect ratio was found. Also, the O₂ permeability through the films was evaluated, which showed that adding both OC and HDPE to EVA leads to a remarkable increase in the barrier properties of EVA films. Finally, by using the gas permeation results and existing permeation theories, the organoclay theoretical aspect ratio was predicted. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Preparation and morphological evolution of heterophasic PP‐EP/EVA/organoclay nanocomposites: Effect of the nanoclay organic modifier

A study is presented on the morphological effects caused by the nanoclay organic modifier and the nanoclay concentration. This was made under previously determined compatibility conditions of heterophasic polypropylene copolymers (PP‐EP)/poly(ethylene vinyl acetate) (EVA)/organoclay nanocomposites. The nanocomposites were prepared using the fluidity of the EVA phase to disperse the nanoclay platelets. Therefore, no additional compatibilizer was used to achieve the clay dispersion. Two organoclays were used with different characteristics and polarity of the substituent groups. Transmission electron microscopy and X‐ray diffraction results first indicated that two hydrogenated tallow modifiers are more effective than one to enhance nanoclay exfoliation. Thermogravimetric studies indicated a low probability of thermal degradation of the nanoclay modifiers and as a consequence of their effect on the layer–layer exfoliation. Molecular simulations were made with the purpose to study additional factors affecting exfoliation. The introduction of nanoclay, within the compatibility conditions of the PP‐EP/EVA system, was also studied. It was determined that the system preserved its original morphology and that the silicate layers were hosted by the EVA domains. The crystallization characteristics of the PP‐EP/EVA mixtures indicated a gradual evolution of the overall crystalline structures depending on the EVA content. In the case of the ternary nanocomposites PP‐EP/EVA/nanoclay, the β crystalline structure was partially formed, although it decreased with increasing nanoclay content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphological and mechanical properties of polypropylene [PP]/poly(ethylene vinyl acetate) [EVA] blends. I. Homopolymer PP/EVA systems

Morphological and mechanical properties of polypropylene [PP]/poly(ethylene vinyl acetate) [EVA] blends have been studied. Infrared results using thin films first indicated a transition toward compatibility between both components at concentrations above 40% EVA. The transition was verified with different experimental techniques and it was associated to morphological changes and mechanical properties. The PP/EVA blends were mechanically evaluated in terms of impact and tensile strength to determine the influence of blending on the performance properties of these materials. Agreement was found between the transition and the enhancement of both elongation at break and impact strength.     

Toughening and compatibilization of polypropylene/polyamide‐6 blends with a maleated–grafted ethylene‐co‐vinyl acetate

In this article, maleated–grafted ethylene‐co‐vinyl acetate (EVA‐g‐MA) was used as the interfacial modifier for polypropylene/polyamide‐6 (PP/PA6) blends, and effects of its concentration on the mechanical properties and the morphology of blends were investigated. It was found that the addition of EVA‐g‐MA improved the compatibility between PP and PA6 and resulted in a finer dispersion of dispersed PA6 phase. In comparison with uncompatibilized PP/PA6 blend, a significant reduction in the size of dispersed PA6 domain was observed. Toluene‐etched micrographs confirmed the formation of interfacial copolymers. Mechanical measurement revealed that the addition of EVA‐g‐MA markedly improved the impact toughness of PP/PA6 blend. Fractograph micrographs revealed that matrix shear yielding began to occur when EVA‐g‐MA concentration was increased upto 18 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99:3300–3307, 2006     

Rubber/LDH nanocomposites by solution blending

The rubber nanocomposites containing ethylene vinyl acetate (EVA) having 60 wt % of vinyl acetate content and organomodified layered double hydroxide (DS‐LDH) as nanofiller have been prepared by solution intercalation method and characterized. The XRD and TEM analysis demonstrate the formation of completely exfoliated EVA/DS‐LDH nanocomposites for 1 wt % filler loading followed by partially exfoliated structure for 5–8 wt % of DS‐LDH content. EVA/DS‐LDH nanocomposites show improved mechanical properties such as tensile strength (TS) and elongation at break (EB) in comparison with neat EVA. The maximum value of TS (5.1 MPa) is noted for 3 wt % of DS‐LDH content with respect to TS value of pure EVA (2.6 MPa). The data from thermogravimetric analysis show the improvement in thermal stability of the nanocomposites by ≈15°C with respect to neat EVA. Limiting oxygen index measurements show that the nanocomposites act as good flame retardant materials. Swelling property analysis shows improved solvent resistance behavior of the nanocomposites (1, 3, and 5 wt % DS‐LDH content) compared with neat EVA‐60. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Analysis of dynamic oscillatory rheological properties of PP/EVA/organo-modified LDH ternary hybrids based on generalized Newtonian fluid and generalized linear viscoelastic approaches

A comprehensive investigation was performed on single-step melt processed polypropylene (PP)/(ethylene vinyl acetate copolymer (EVA)/organo-modified layered double hydroxide (LDH) counterpart ternary hybrids to explore the effect of LDH loading on small-amplitude oscillatory shear (SAOS) rheological properties and to correlate the properties with microstructure. The rheological results were analyzed in detail from qualitative and quantitative perspectives. Using qualitative interoperation of storage modulus and complex viscosity alteration against LDH loading, and also quantitative analysis by viscosity models based on both the generalized Newtonian fluid (GNF) and generalized linear viscoelastic (GLVE) approaches, detailed predictions were carried out on the microstructure of samples and also partitioning of the organo-modified LDH particles and their intercalation and exfoliation extent within hybrids. By comparing the elasticity and relaxation spectrum of PP-rich/LDH with those of EVA-rich/LDH hybrids, it was predicted that organo-modified LDH platelets, in the case of PP-rich samples, have been located at the interface or within the EVA dispersed particles, while in the case of EVA-rich samples, they mainly localized within the matrix. In addition, the crossover frequency and slope of G′ and G″ curve at terminal region were correlated with the extent of intercalated and exfoliated structures of filler. The validity of these predictions on microstructure of the developed hybrids was confirmed visually using transmission electron microscope (TEM) micrographs.     

聚合物/层状硅酸盐纳米复合材料的制备研究

本文以聚丙烯和有机蒙脱土为原料，采用插层复合法制备聚合物／层状硅酸盐纳米复合材料，用透射电镜对复合材料的结构进行表征，测定了复合材料的力学性能，结果表明，用马来酸酐化聚丙烯作界面相容剂，聚丙烯大分子链分子插层进入到有机改性蒙脱土的硅酸盐片层中间，并且聚丙烯／蒙脱土纳米复合材料的力学性能有一定的提高。     

Synergistic effects of exfoliated LDH with some halogen‐free flame retardants in LDPE/EVA/HFMH/LDH nanocomposites

The synergistic effects of exfoliated layered double hydroxides (LDH) with some halogen‐free flame retardant (HFFR) additives, such as hyperfine magnesium hydroxide (HFMH), microencapsulated red phosphorus (MRP), and expandable graphite (EG), in the low‐density polyethylene/ethylene vinyl acetate copolymer/LDH (LDPE/EVA/LDH) nanocomposites have been studied by X‐ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermal analysis (TGA and DTG), mechanical properties, limiting oxygen index (LOI), and UL‐94 tests. The XRD results show that EVA as an excellent compatilizer can promote the exfoliation of LDH and homogeneous dispersion of HFMH in the LDPE/EVA/HFMH/LDH nanocomposites prepared by melt‐intercalation method. The TEM images demonstrate that the exfoliated LDH layers can act as synergistic compatilizer and dispersant to make the HFMH particles dispersed homogeneously in the LDPE matrix. The results from the mechanical, LOI, and UL‐94 tests show that the exfoliated LDH layers can also act as the nano‐enhanced and flame retardant synergistic agents and thus increase the tensile strength, LOI values, and UL‐94 rating of the nanocomposites. The morphological structures of charred residues observed by SEM give the positive evidence that the compact charred layers formed from the LDPE/EVA/HFMH/LDH nanocomposites with the exfoliated LDH layers play an important role in the enhancement of flame retardant and mechanical properties. The TGA and DTG data show that the exfoliated LDH layers as excellent flame retardant synergist of MRP or EG can apparently increase the thermal degradation temperature and the charred residues after burning. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Ethylene vinyl acetate copolymer nanocomposites based on (un)modified sepiolite: Flame retardancy,thermal, and mechanical properties

Flame retardant ethylene‐vinyl acetate (EVA) nanocomposites were prepared by melt blending using unmodified and modified sepiolite. Modification process of sepiolite was carried out by using 3‐aminopropyltrimethoxysilane in water/ethanol medium. Thermal, mechanical, and flame retardancy properties of the prepared nanocomposites were evaluated and compared with each other. X‐ray diffraction and scanning electron microscopy indicated that sepiolite fibers are well‐dispersed in EVA matrix. By the addition of (un)modified sepiolite, both flame retardancy and thermal stability characteristics first improved, and then deteriorated, indicating a direct relationship between these properties. It was also found that sepiolite protects carbonyl groups of EVA from further degradation. Most interestingly, a simultaneous increase in both ductility and toughness was observed in the prepared composites. Whatever the evaluated properties were, whether the mechanical, thermal, or flame retardancy, the improved properties were more remarkable when modified sepiolite was utilized. POLYM. COMPOS., 38:1302–1310, 2017. © 2015 Society of Plastics Engineers     

Effect of Clay Types on the Mechanical,Dynamic Mechanical and Morphological Properties of Polypropylene Nanocomposites

In the present investigation Polypropylene–Maleic anhydride grafted polypropylene–organically modified MMT (PP-MAPP-OMMT) nanocomposites were prepared by melt mixing in a twin screw extruder followed by injection molding. The effect of clay chemistry and compatibilizer on the properties of the nanocomposites has been studied. Sodium montmorillonite has been organically modified using quaternary and alkyl amine intercalants. A comparative account with commercial quaternary ammonium modified clays i.e Cloisite 20A, Cloisite 15A and Cloisite 30B has been presented. Storage modulus of PP matrix also increased in the nanocomposites, indicating an increase in the stiffness of the matrix polymer with the addition of organically modified nanoclays. The morphology of the nanocomposites has been examined using wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). Morphological findings revealed efficient dispersion of organically modified nanoclays within the PP matrix. MAPP compatibilized PP/Cloisite 15A nanocomposites displayed finely dispersed exfoliated nanomorphology as compared with other systems.     

Mechanical and oxygen barrier properties of organoclay-polyethylene nanocomposite films

An organically modified montmorillonite was compounded with ethylene vinyl acetate copolymer (EVA), low density polyethylene (LDPE), and high density polyethylene (HDPE) in a twin-screw extruder. The resulting organoclay-polyethylene nanocomposites were then blown into films. Tensile properties and oxygen permeability of these nanocomposite films were investigated to understand the effects of organoclay on different types of polyethylene. It was found that the clay enhancing effects are function of the matrix. The mechanical and oxygen barrier properties of clay/EVA systems increased with clay loading. Both the tensile modulus and oxygen barrier of EVA doubled at 5 wt% clay. Maleic anhydride grafted polyethylene (MAPE) usually is used as a compatibilizer for LDPE and HDPE-based nanocomposites. However, the MAPEs were found to weaken the oxygen barrier of the PEs, especially for HDPE. This is believed to be a result of less compactness caused by the large side groups and the increase in polarity of the MAPEs. Incorporating 5 wt% clay improves the oxygen barrier by 30% and the tensile modulus by 37% for the LDPE/MAPE system. Incorporation of clay does not enhance the properties of the HDPE-based systems, likely due to large domain structure and poor bonding. Halpin–Tsai equation and the tortuous path equation were used to model the tensile modulus and oxygen permeability of the clay/EVA nanocomposite films. POLYM. ENG. SCI., 47:1101–1107, 2007. © 2007 Society of Plastics Engineers