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     

Subsurface mechanical properties of polyurethane/organoclay nanocomposite thin films studied by nanoindentation

A series of the exfoliated or intercalated PU/organoclay nanocomposite thin films were prepared by in situ polymerization of polyol/organoclay mixture, chain extender and diisocyanate. The surface mechanical properties of the PU/organoclay nanocomposite films were investigated by means of nanoindentation. The results show that the hardness, elastic modulus and scratch resistant of the nanocomposites dramatically improved with the incorporation of organoclay. This improvement was dependent on the clay content as well as the formation structure of clay in the PU matrix. At 3% clay content, the hardness and elastic modulus of intercalated nanocomposites increased by approximately 16% and 44%, respectively, compare to pure PU. For exfoliated nanocomposite, the improvements in these properties were about 3.5 and 1.6 times higher than the intercalated ones. The exfoliated PU nanocomposites also had greater hardness and showed better scratch resistance compared to the intercalated ones.     

Thermal,mechanical, and barrier properties of polyethylene/surlyn/organoclay nanocomposites blown films prepared by different mixing methods

(Low‐density polyethylene) (LDPE)/clay nanocomposites were prepared by melt blending in a twin‐screw extruder by using different mixing methods. Zinc‐neutralized carboxylate ionomer was used as a compatibilizer. Blown films of the nanocomposites were then prepared. The effect of mixing method on the clay dispersion and properties of the nanocomposites was evaluated by wide‐angle X‐ray diffraction analysis, mechanical properties, thermal properties, and barrier properties. The structure and properties of nanocomposites containing different amounts of nanoclay prepared by selected mixing techniques were also investigated. It was found that melt compounding of Surlyn/clay masterbatch with pure LDPE and Surlyn (two‐step‐a method) results in better dispersion and intercalation of the nanofillers than melt mixing of LDPE/Surlyn/clay masterbatch with pure LDPE and surlyn (two‐step‐b method) and direct mixing of LDPE with clay. The films containing ionomer have good barrier properties. A wide‐angle X‐ray diffraction pattern indicates that intercalation of polymer chains into the clay galleries decreases by increasing the clay content. Barrier properties and tensile modulus of the films were improved by increasing the clay content. In addition, tensile strength increased in the machine direction, but it decreased in the transverse direction by increasing the clay content. DSC results showed that increasing the clay content does not show significant change in the melting and crystallization temperatures. The results of thermogravimetric analysis showed that the thermal stability of the nanocomposites decreased by increasing the clay content more than 1 wt%. J. VINYL ADDIT. TECHNOL., 21:60–69, 2015. © 2014 Society of Plastics Engineers     

Synthesis and characterization of HDPE/N-MWNT nanocomposite films

In this work, a series of nitrogen-doped multi-walled carbon nanotubes (N-MWCNTs) with several weight percentages (0.1, 0.4, 0.8, and 1.0 wt.%) were synthesized by catalytic chemical vapor deposition (CCVD) technique. The N-MWCNTs were first characterized and then dispersed in high-density polyethylene (HDPE) polymer matrix to form a nanocomposite. The HDPE/N-MWCNT nanocomposite films were prepared by melt mixing and hot pressing; a good dispersion in the matrix and a good N-MWCNT-polymer interfacial adhesion have been verified by scanning electron microscopy (SEM). Raman spectroscopy measurements have been performed on prepared samples to confirm the presence and nature of N-MWNTs in HDPE matrix. The X-ray diffraction (XRD) analysis demonstrated that the crystalline structure of HDPE matrix was not affected by the incorporation of the N-MWNTs.     

Rheological properties of a new rubbery nanocomposite: Polyepichlorohydrin/organoclay nanocomposites

Nanocomposites of organophilic montmorillonite clay (OMMT) and polyepichlorohydrin (PECH) were intercalated by a solvent‐casting method using dichloromethane as a solvent. The intercalation of PECH segments in the interlayers of the clay was confirmed by X‐ray diffraction, and the intercalation spacing was calculated. The increase in the onset temperature of the thermal degradation indicated the enhancement of thermal stability of PECH due to intercalation. Rheological properties of the PECH/OMMT nanocomposites were investigated using a rotational rheometer in a steady shear mode. The steady shear viscosity increased with the clay loading, and the shear thinning viscosity data were fitted well with the Carreau model. From the normalized shear viscosity analysis, a critical shear rate that is a crossover from a Newtonian plateau to a shear thinning region was found to approximately equal the inverse of the characteristic time of the nanocomposites. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3735–3739, 2002     

Preparation of HDPE/UHMWPE/MMWPE blends by two-step processing way and properties of blown films

Summary Blends of high density polyethylene (HDPE) and ultra high molecular weight polyethylene (UHMWPE) were prepared by two-step processing way. Middle molecular weight polyethylene (MMWPE) as a fluidity modifier and compatilizer was added into UHMWPE in the first step, and then modified UHMWPE and HDPE were blending extruded to prepare the HDPE/UHMWPE/MMWPE blends used for blown films. The mechanical test of the blown films revealed that when the content of MMWPE in modified UHMWPE was 40wt% and the content of UHMWPE in the blends was 20 wt%, the film had the optimal mechanical properties. The tensile strength and tear strength of the film increased by 50% and 21%, respectively, compared with those of pure HDPE film. Rheological curves indicated that the melt torque and the apparent viscosity of the HDPE/UHMWPE/MMWPE blends made by two-step processing way both greatly reduced than other blends. The results from DSC suggested that the blends by two-step processing way may form more stable and perfect co-crystallization. PLM (polarized light microscopy) and SEM micrographs revealed that two-step processing way can improve the surface morphology of the films and make the dispersion of UHMWPE particles in HDPE increase.     

Investigation of thermal,rheological, and physical properties of amorphous poly(ethylene terephthalate)/organoclay nanocomposite films

Thermal, rheological, and physical properties of amorphous poly(ethylene terephthalate) (PET)/organoclay nanocomposite films which were successfully prepared with melt processing method using a PET/organoclay masterbatch were studied in detail. Structural and physical properties of the films were characterized by the UV–Vis spectroscopy, XRD and SEM analysis, DSC, DMA, and rheological tests and gas permeability measurements. Cold‐crystallization behavior of the samples was analyzed by the DSC and DMA methods. Aspect ratio of the organoclay layers were determined with the Nielsen and Halpin‐Tsai models based on the gas permeability and DMA data, respectively. It was found that the organoclay reduced the nonisothermal cold‐crystallization rate of PET chains by restricting the segmental motion of the polymer in the solid state. On the other hand, the organoclay enhanced the nonisothermal melt‐crystallization of PET due to the nucleation effect. Aspect ratio (A_f) of the clay layers were found to be about 20 by using the gas permeability and DMA data. Aspect ratio value was also confirmed by the analysis of SEM images of the samples. A physical model for the sample microstructure was offered that the stacks with the thickness of 20–30 nm and the lateral size of 400–600 nm, probably consisting of 5–8 layers, were uniformly dispersed in the PET structure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Ferroelectric properties of PZT/BFO multilayer thin films prepared using the sol-gel method

In this study, Pb(Zr_0.52Ti_0.48)O₃/BiFeO₃ [PZT/BFO] multilayer thin films were fabricated using the spin-coating method on a Pt(200 nm)/Ti(10 nm)/SiO₂(100 nm)/p-Si(100) substrate alternately using BFO and PZT metal alkoxide solutions. The coating-and-heating procedure was repeated several times to form the multilayer thin films. All PZT/BFO multilayer thin films show a void-free, uniform grain structure without the presence of rosette structures. The relative dielectric constant and dielectric loss of the six-coated PZT/BFO [PZT/BFO-6] thin film were approximately 405 and 0.03%, respectively. As the number of coatings increased, the remanent polarization and coercive field increased. The values for the BFO-6 multilayer thin film were 41.3 C/cm² and 15.1 MV/cm, respectively. The leakage current density of the BFO-6 multilayer thin film at 5 V was 2.52 × 10^-7 A/cm².     

Thermal and barrier properties of EVOH/EFG nanocomposite films for packaging applications: Effect of the mixing method

Ethylene‐vinyl alcohol copolymer (EVOH)/exfoliated graphite (EFG) nanocomposite films were prepared by precoating EFG on the EVOH surface and conducting a successive melt‐extrusion process. Their physical properties were strongly dependent on the EFG content and the mixing method, which strongly affected the morphology and surface properties of the nanocomposite films. The hydrophobicity and water resistance property of EVOH increased by incorporating hydrophobic EFG and their effects were more pronounced in the precoating method, which is related to good dispersion of EFG in EVOH and an enhanced crystalline structure. The incorporation of EFG into EVOH by the precoating method more effectively diminished the dependence of the relative humidity on the oxygen transmission rate of pure EVOH and increased the oxygen barrier properties of EVOH at a high relative humidity. The incorporation of EFG into EVOH by the precoating method also induced relatively more enhanced thermal stability. These results suggest the feasibility of the application of moisture‐sensitive EVOH resin for food packaging films. POLYM. COMPOS., 37:1744–1753, 2016. © 2014 Society of Plastics Engineers     

Mechanical,thermal, barrier,and rheological properties of poly(ether‐block‐amide) elastomer/organoclay nanocomposite prepared by melt blending

Polyether block amide (PEBA) elastomer‐organoclay nanocomposites were prepared by a melt mixing technique. The X‐ray diffraction and transmission electron microscope analysis indicated that the nanocomposite formed a partially exfoliated nanostructure in which the organoclay was dispersed uniformly throughout the matrix at the nanometer scale. The effect of organoclay on the melting temperature (T_m), glass transition temperature (T_g), crystallization temperature (T_c), and heat of fusion (ΔH_m) of the PEBA was determined by differential scanning calorimetry. Enhanced mechanical properties of the nanocomposites were observed from tensile and dynamic mechanical analysis. Thermal gravimetric analysis showed that the clay nanoparticles caused an increase in the thermal stability of the PEBA. Measurement of oxygen permeability and the degree of swelling in ASTM #3 oil indicated that the gas barrier properties and solvent resistance were greatly improved by the clay nanoparticles. Melt rheological studies revealed that the nanocomposites exhibited strong shear thinning behavior and a percolated network of the clay particles was formed. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

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     

Effect of organoclay on the morphology,mechanical, and thermal properties of polyimide/organoclay nanocomposite foams

A series of polyimide (PI)/organoclay nanocomposite foams containing different contents of organoclay were prepared by the monomer in situ intercalative polymerization. The effect of organoclay on the chemical structure, morphology, mechanical, and thermal properties of the nanocomposite foams was studied. Fourier transform infrared spectra showed that the hydrogen bonds between organoclay and the polymer matrix were formed. X‐ray diffraction and transmission electron microscope results indicated that the organoclay were well dispersed in the PI matrix. The compressive strength and tensile strength of the nanocomposite foams enhanced significantly, especially for the nanocomposite foam containing 4 wt% organoclay, increasing by 15% and 9%, respectively, compared with these of the neat PI foam, and the presence of the organoclay in the PI foam improved apparently the cellular structure of the nanocomposite foams. Besides, thermogravimetric analysis revealed that the addition of organoclay improved the thermal stability of the nanocomposite foams strongly, and dynamic mechanical analysis indicated that the incorporation of organoclay significantly influenced the storage modulus of the nanocomposite foams. POLYM. COMPOS., 35:2311–2317, 2014. © 2014 Society of Plastics Engineers     

Preparation and properties of HDPE/CaCO3/OMMT ternary nanocomposite

A series of binary composites based on HDPE (high density polyethylene) and nanoinorganic particles such as nano‐CaCO₃ and OMMT (organic montmorillonite) were prepared. Their properties including tensile, impact strength, and some thermal properties were tested. The results showed that binary composite has partial improvement in mechanical properties compared with pure HDPE. A ternary composite nano‐CaCO₃/OMMT/HDPE was prepared and characterized. It was found that the mechanical and thermodynamic properties of this ternary composite have been enhanced greatly compared with both pure HDPE and binary composites. The tensile strength, Young's modulus, flexural strength, elastic modulus, and impact strength of nano‐CaCO₃/OMMT/HDPE were increased 124.6%, 302.7%, 73.86%, 58.97%, and 27.25%, respectively. The DMA test results showed that the mechanical properties of ternary composite were increased because of the limitation on the movement of HDPE due to inorganic particles. The synergistic effect introduced by nanoparticles may play an important role in all these processes. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Physico-mechanical,rheological and gas barrier properties of organoclay and inorganic phyllosilicate reinforced thermoplastic films

Insertion of 2:1 organo-modified phyllosilicate tactoids into rheologically tough thermoplastics has extraordinary potential candidate in oxygen permeability and microstructural toughening. Herein, two commercially abundant clays have been taken for improvement of the thermoplastic's gas barrier property in reasonably low loading. The cause of low loading has been accounted to the usage of maleated polyethylene (MA-g-PE) during the melt mixing tenure. The optimized nanocomposite compression molded film has been tested against uniaxial stretching, which showed a negligible change in the residual permanent set with sacrificing the elongation at break feature. Moreover, nanoindentation was also performed to get the hardness of the sample surface. The flow behavior of the nanocomposites showed thixotropic likely with increasing the frequency. Oxygen transmission rate (OTR) has significantly decreased for tallow amine-modified nanoclay system (cloisite 15A) in comparison to cloisite Na⁺ providing 'tortoise path' formation inside the matrix. Thus, hitherto, the work could demonstrate and provide the information of comparative studies between organo-clay and simple phyllosilicates, which could be remediation of the loopholes in mechanical toughening and gas barrier lineaments.     

Curing and barrier properties of NBR/organo-clay nanocomposite

Organo-montmorillonite/NBR nanocomposites were prepared by a melt intercalation process. The characteristics of NBR nanocomposites were characterized by oscillating-disk rheometer, water-vapour transmission and transmission electron microscopy (TEM). Changes in cure characteristics resulting from changes in clay content and the addition of silane coupling agent were investigated. The study confirmed that organo-montmorillonite/NBR nanocomposites cure characteristics, viz minimum torque, maximum torque, scorch time and curing time, change according to the change in clay content and the addition of silane coupling agent. Of the water-vapour transport properties, the clay content and silane content are the dominating factors in determining the individual water-vapour permeability of these NBR nanocomposites. TEM analysis provided clear evidence for the homogeneous dispersion of clay in the NBR matrix without regard to increases in clay content. Copyright © 2004 Society of Chemical Industry     

Photoelectrochemical properties of hematite thin films grown via a two-step electrochemical deposition method

In this study, Fe₂O₃ thin films were deposited via one-step and two-step electrochemical deposition methods. The one-step method used a constant growth potential, and the two-step method used two continuous growth potentials during the deposition. The morphological, electrical, and structural properties of the thin films and the relationships of each property with the photoelectrochemical properties of the thin films from the two methods were analyzed and compared. We determined that the samples grown by the two-step method have better photoelectrochemical properties than those grown by the one-step method. In this study, we attempted to determine the optimum growth potentials for the one-step and two-step methods and the growth durations of the first and second stages in the two-step method in terms of the photoelectrochemical properties. The sample formed at ?0.05 V for 30 s in the first step and ?0.25 V for 2 min 30 s in the second step in the two-step method has the highest photocurrent density value of 0.28 mA/cm² (at 0.5 V vs. SCE), which is higher than that of the samples grown by the one-step method.     

HDPE/LLDPE/POE薄膜性能的研究

采用线型低密度聚乙烯（LLDPE）和热塑性弹性体乙烯-辛烯共聚物（POE）对高密度聚乙烯（HDPE）薄膜进行改性,研究了LLDPE和POE对共混体系薄膜力学性能、加工性能的影响,探讨了LLDPE增强HDPE的机理。结果表明,加入一定量LLDPE,使HDPE／LLDPE薄膜的拉伸强度较纯HDPE薄膜有所增加,而单位冲击破损质量则有所下降。当w（LLDPE）为15％时,HDPE／LLDPE薄膜的拉伸强度提高21．6％,薄膜的单位冲击破损质量降低23．0％。在HDPE／LLDPE/POE三元体系中,当w（POE）,w（LLDPE）分别为10％,15％时,薄膜的拉伸强度、单位冲击破损质量、断裂伸长率比纯HDPE薄膜分别提高2．3％,113％。36．0％,综合性能良好。