Forced assembly by multilayer coextrusion to create oriented graphene reinforced polymer nanocomposites

A potential advantage of platelet-like nanofillers as nanocomposite reinforcements is the possibility of achieving two-dimensional stiffening through planar orientation of the platelets. The ability to achieve improved properties through in-plane orientation of the platelets is a challenge and, here, we present the first results of using forced assembly to orient graphene nanoplatelets in poly(methyl methacrylate)/polystyrene (PMMA/PS) and PMMA/PMMA multilayer films produced through multilayer coextrusion. The films exhibited a multilayer structure made of alternating layers of polymer and polymer containing graphene as evidenced by electron microscopy. Significant single layer reinforcement of 118% at a concentration of 2 wt % graphene was achieved—higher than previously reported reinforcement for randomly dispersed graphene. The large reinforcement is attributed to the planar orientation of the graphene in the individual polymer layers. Anisotropy of the stiffening was also observed and attributed to imperfect planar orientation of the graphene lateral to the extrusion flow.     

Enhanced thermal conductivity of PLA‐based nanocomposites by incorporation of graphite nanoplatelets functionalized by tannic acid

Enhancing thermal conductivity of polymeric nanocomposites remains a great challenge because of the poor compatibility between nanofillers and the polymeric matrix and the aggregation effect of nanofillers. We report the enhanced thermal conductivity of poly(lactic acid) (PLA)‐based nanocomposites by incorporation of graphite nanoplatelets functionalized by tannic acid. Graphite nanoplatelets (GNPs) were noncovalently functionalized with tannic acid (TA) by van der Waals forces and π–π interaction without perturbing the conjugated sp² network, thus preserving the high thermal conductivity of GNPs. PLA‐based nanocomposites with different contents of TA‐functionalized GNPs (TA‐GNPs) were prepared and characterized, and the influences of TA‐GNPs content on the morphologies, mechanical properties, and thermal properties of the composites were investigated in detail. TA‐GNPs remarkably improved the thermal conductivity of PLA up to 0.77 W/(m K), showing its high potential as a thermally conductive filler for polymer‐based nanocomposites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46397.     

A novel method for industrial manufacturing of thermoplastic multilayer films: Processing,microstructure, and properties

This article reports a facile approach for industrial‐scale manufacturing of multilayer coextrusion‐blown films by developing a novel rotation homogenization distribution (RHD) method. Materials in this unique process are subjected to a flow field combining both shear circulation and pressure flow. In RHD, circumferential shear causes a laminar flow, where the stable interface between layers can be obtained, and assigns melt evenly to the entire circumferential direction. This equipment has been used to prepare multilayer low‐density polyethylene (LDPE) films under various shear rates by altering the mandrel rotation speed. The effects of mandrel rotation speed on the microstructure, morphology, and properties of bilayer LDPE films were investigated. Multilayer LDPE films with superior interfacial stability and uniform layer distribution, which differ from the multiple melt channels in conventional multilayer coextrusion blown facilities, were successfully fabricated using the proposed equipment. Evident enhancements were observed in thermal shrinkage and mechanical properties of the multilayer films, especially in the transverse direction. © 2018 Society of Plastics Engineers POLYM. ENG. SCI., 59:E339–E349, 2019. © 2018 Society of Plastics Engineers     

Photodegradation of multilayer films based on PET copolymers

An investigation was conducted on the effects of photodegradation of multilayer films based on PET copolymers. The films were composed by different layers with PET, PET/PEN, and PET/PEI copolymers with a total thickness of 23 μm. The films produced by coextrusion followed by a biaxial orientation in an industrial equipment were exposed to the ultraviolet radiation in the laboratory for periods of up to 600 h. The samples were investigated by FTIR‐ATR, UV/visible spectroscopy, fluorescence spectroscopy, size exclusion chromatography, mechanical properties, and scanning electron microscopy. The results showed that the photooxidation is concentrated at the surface layers and that coextruded films were more sensitive to the UV radiation effects. The deterioration in mechanical properties with exposure and the fracture behavior were shown to be consistent with the amount of degradation that occurred in the films. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Melt processing of poly(L‐lactic acid) in the presence of organomodified anionic or cationic clays

Poly(L ‐lactic acid) (PLA) films are in use for various types of food packaging; however, a wider range of applications would be possible if the barrier properties of these films could be improved. To make such improvements, combinations of PLA with two nanofillers, laurate‐intercalated Mg‐Al layered double hydroxide (LDH‐C₁₂) and a cationic organomodified montmorillonite (MMT) clay (Cloisite® 30B), were investigated. The dispersion of these fillers in PLA by melt processing was explored using two methods, either by mixing the nanofillers with PLA granulate immediately before extrusion or by preparation and subsequent dilution of PLA‐nanofiller masterbatches. After melt processing of these materials, PLA molecular weight, thermal stability, film transparency, morphology, and permeability characteristics were determined. Direct addition of LDH‐C₁₂ drastically reduced the PLA molecular weight. Although this reduction in molecular weight was still very significant, it was less when a PLA/LDH‐C₁₂ masterbatch was processed. In contrast, there was no significant reduction in PLA molecular weight when processing with Cloisite® 30B. However, film transparency was compromised when either LDH or MMT nanofillers were used. Evidence from DSC analyses showed a significant increase in heat of fusion when LDH‐C₁₂ was dispersed in PLA compared with Cloisite® 30B, likely indicating a difference in nucleating properties. Complementary optical purity analyses suggested that racemization as a result of processing could influence the PLA crystallinity as determined by DSC in certain cases. A reduction in thermal stability when incorporating LDH‐C₁₂ could be a direct result of PLA molecular weight reduction. XRD and TEM analyses showed that both Cloisite® 30B‐ and LDH‐C₁₂‐based PLA composites yielded exfoliated and intercalated morphologies, but nanofiller agglomeration was also seen when LDH‐C₁₂ was used. PLA/Cloisite® 30B nanocomposite films exhibited significant enhancement in oxygen and water vapor barrier properties, but no such improvement was found in PLA/LDH‐C₁₂ nanocomposite films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚乳酸／功能化石墨烯纳米复合薄膜的制备与性能

以十八烷基胺修饰氧化石墨烯(GO–ODA)为纳米填料,通过溶液铸膜法制备了聚乳酸(PLA)／GO–ODA纳米复合薄膜。用傅立叶变换红外光谱和扫描电子显微镜对GO–ODA及纳米复合薄膜的化学结构及形貌进行了表征,并对纳米复合薄膜的拉伸性能、热稳定性和透氧率进行了测试。结果表明,GO–ODA与PLA具有良好的相容性,可均匀分散于PLA基体中,对PLA膜起到增韧增强的效果,同时GO–ODA的加入使PLA的热稳定性和氧气阻隔性均有所提高。     

Micromechanics of nanocomposites: comparison of tensile and compressive elastic moduli, and prediction of effects of incomplete exfoliation and imperfect alignment on modulus

This paper addresses three important aspects, neglected in all previous literature, of the micromechanics of nanocomposites reinforced by platelet-shaped fillers. (a) A model was developed to predict the buckling of platelets in reinforced materials under compressive loading. This model predicts a critical strain above which platelet buckling, and hence a reduction in the compressive modulus relative to the tensile modulus, would be expected to occur. It was used to show that compressive modulus should not be reduced relative to tensile modulus in a typical polypropylene nanocomposite. (b) A model was developed to account for the reduction of the reinforcement efficiency of clay platelets of high aspect ratio in a polymer matrix as a result of the incomplete exfoliation of platelets into ‘pseudoparticle’ stacks containing polymer layers sandwiched between successive clay platelet layers rather than into individual perfectly exfoliated and well-dispersed platelets. It was shown that incomplete exfoliation has a very significant detrimental effect on the reinforcement efficiency. (c) A model was also developed for the reduction of the reinforcement efficiency as a result of the deviation of the platelet orientation from perfect biaxial in-plane. It was shown that the deviation of the platelet orientation from perfect biaxial in-plane also has a very significant detrimental effect on the reinforcement efficiency.     

Incorporation of lead phthalocyanine into periodic nanolayered assemblies for advanced optical systems

Periodically structured polymeric materials can lead to the next generation of electro‐optic and nonlinear optical devices for applications in information technology. Layer‐multiplying melt coextrusion is an attractive method for fabricating periodic structures with thousands of alternating polymer microlayers or nanolayers. Many advanced applications for periodic polymeric structures would be enabled by locating a photoactive dye in one or both layers. However, it is anticipated that due to the thinness of the individual layers and the relatively low molecular weight of many dyes, a substantial fraction of the dye will diffuse from the doped layers into the undoped layers during melt coextrusion. In the present study, we demonstrate two methods for confining the activity of a photoactive dye, lead phthalocyanine, to the doped layers. Polycarbonate containing lead phthalocyanine was coextruded with undoped polyester as an assembly of 128 alternating 86 nm‐thick layers. Using the absorption spectra, we demonstrated that a high concentration of the monomer form persisted in the polycarbonate layers, whereas the lead form was converted to the less active lead‐free form in the polyester layers. Thus, the active monomer form of PbPc(β‐CP)₄ was maintained selectively in the polycarbonate layers. In the second approach, the coextrusion process was altered so that the alternating polycarbonate and polyester layers were separated by a thin layer of a barrier polymer. The barrier layer prevented diffusion of the dye during melt coextrusion and the dye remained selectively in the polycarbonate layers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermoformable high oxygen barrier multilayer EVOH/LDPE film/foam

The effect of the number of layers on oxygen transmission and thermoformability of novel multilayer film/foam materials was investigated. Ethylene-vinyl alcohol copolymer/low-density polyethylene multilayered film/foam composites having 16, 32, and 64 alternating layers were developed using continuous multilayer coextrusion process, and the morphology, density, oxygen transmission, and mechanical properties of the as-extruded film/foams were characterized. Tensile properties of the film/foams at elevated temperatures were used to optimize thermoforming conditions. Uniaxial orientation was discovered as an efficient approach to evaluate the potential for thermoforming. Oxygen transmission showed a strong correlation with the thickness reduction which could be used as an indicator for barrier properties of the packaging materials. Film/foam materials with 32 layers demonstrated optimum performance with low oxygen transmission along with high drawing capability. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48903.     

Crystal structure and orientation of uniaxially and biaxially oriented PLA and PP nanoclay composite films

Cast films of poly(lactic acid) (PLA) and polypropylene (PP) with 2.5 and 5 wt % organo modified nanoclay were prepared and then uniaxially and biaxially hot drawn at T = 90 and 155°C, respectively, using a biaxial stretcher. The orientation of PLA and PP crystal unit cells, alignment of clay platelets, as well as the extent of intercalation and exfoliation were studied using wide angle X‐ray diffraction (WAXD). The measurement of d‐spacing of the 001 plane (normal to platelets plane) of the clay tactoids indicated the intercalation of the silicate layers for the PLA nanocomposite films, whereas the PP nanofilled films showed only dispersion of the nanoparticles (i.e., neither intercalation nor exfoliation were observed). The intercalation level of the clay platelets in PLA was almost identical for the uniaxially and biaxially drawn films. Our finding showed that the crystallite unit cell alignments are appreciably dependent on uniaxial and biaxial stretching. Moreover, the incorporation of clay to some extent influenced the orientation of the crystal unit cell axes (a, b, and c) of the oriented films. The silicate layers revealed a much higher orientation into the flow direction in the uniaxially stretched films compared to the biaxially drawn samples. In addition, the orientation of the 001 plane of nanoclays was significantly greater in the PLA compared to the PP nanoclay composite films probably due to a better intercalation and stress transfer in the former. Morphological pictograms illustrating the effects of uniaxial and biaxial stretching on the clay orientation are proposed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Nanoindentation analysis of 3D printed poly(lactic acid)-based composites reinforced with graphene and multiwall carbon nanotubes

Influences of different nanocomposite loadings in poly(lactic acid) (PLA) matrix on resulting hardness and elasticity were examined in nanoindentation experiments. The following study was focused on the nanomechanical properties of PLA reinforced with graphene nanoplatelets (GNPs) and multiwall carbon nanotubes (MWCNTs) by using Berkovich type pyramidal nanoindenter. A masterbatch strategy was developed to disperse GNP and MWCNT into PLA by melt blending. Young's modulus and nanohardness of as-prepared nanocomposites were characterized as a function of the graphene and carbon nanotubes loading. The nanoindentation analysis reveals that these carbon nanofillers improve the mechanical stability of the nanocomposites GNP/PLA, MWCNT/PLA, and GNP/MWCNT/PLA. That improvement of mechanical properties strongly depends on the fillers content. It was found that the best mechanical performance was achieved for the compound having 6 wt % graphene and 6 wt % MWCNTs in the PLA matrix. The received values for nanohardness and Young's modulus are among the highest reported for PLA-based nanocomposites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47260.     

Melt rheological investigation of polylactide‐nanographite platelets biopolymer composites

This study is an analytical investigation of processability of biopolymer‐carbon based nanofiller composites primarily through rheological investigation of samples. The composites were fabricated via dry mixing and melt‐blending of biodegradable polylactide (PLA) and nanographite platelets (NGP) in a Brabender twin screw extruder. A range of different nanofiller contents (1, 3, 5, 7, and 10 wt %) were studied for NGP containing composites. The morphology was studied with X‐ray diffraction and transmission electron microscopy techniques and showed poor dispersion, with agglomerates, tactoids, and exfoliated layers present. Mechanical properties showed an optimum at 3 wt % filler. Results showed that the composites exhibited higher elastic and viscous moduli than neat PLA. The rheological percolation threshold predicted by changes in slope (α) as well as liquid–solid transition theory of samples was found around 3 wt % through the change from liquid‐like behavior to pseudo‐solid‐like behavior at terminal region during dynamic oscillatory measurements. NGP nanofillers were found to enhance the viscoelastic and mechanical properties of PLA at low concentrations; however, an efficient dispersion of nanofillers within polymer by melt intercalation method of mixing was not achieved. POLYM. ENG. SCI., 54:175–188, 2014. © 2013 Society of Plastics Engineers     

Morphological and thermal properties of photodegradable biocomposite films

Biocomposites containing ultraviolet (UV) radiation absorbing inorganic nanofillers are of great interest in food packaging applications. The biodegradable polylactide (PLA) composite films were prepared by solvent casting method by incorporating 1 wt % of titanium dioxide (TiO₂) and Ag‐TiO₂ (silver nanoparticles decorated TiO₂) nanoparticles to impart the photodegradable properties. The films were exposed to UV radiation for different time periods and morphology of the composite films before and after UV exposure were investigated. The results showed that homogenous filler distribution was achieved in the case of Ag‐TiO₂ nanoparticles. The thermal properties and thermomechanical stability of the composite film containing Ag‐TiO₂ nanoparticles were found to be much higher than those of neat PLA and PLA/TiO₂ composite films. The scanning electron microscopy and X‐ray diffraction studies revealed that the photodegradability of PLA matrix was significantly improved in the presence of Ag‐TiO₂ nanoparticles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Photoactivity of Poly(lactic acid) nanocomposites modulated by TiO2 nanofillers

Photoactivity of poly(lactic acid) (PLA) nanocomposites is of great interest for rational design of products for either short‐term/single‐use or long‐term/durable applications. We prepared PLA/TiO₂ nanocomposite films through a solution mixing/film casting method. Results showed that photodegradability/photostability of PLA could be well modulated by selecting appropriate TiO₂ nanofillers. TiO₂ nanoparticles and nanowires were characterized using X‐ray diffraction, UV–Vis–NIR spectrophotometer, and scanning electron microscopy. Changes in color, weight, structure, thermal stability, and phase transitions of PLA and nanocomposite films before and after UV irradiation were evaluated to study photoactivity characteristics. Pure PLA exhibited moderate photodegradability, but the photodegradability and photostability of PLA nanocomposites (PNA) were significantly enhanced by NanoActive (NA) TiO₂ nanoparticles and A type TiO₂ nanowires, respectively. Pure PLA had a weight loss of 27% after 38 days of UV irradiation. The weight loss of photodegradable (PD) PNA (PNA = PLA with 1% NA TiO₂) reached 38%, whereas that of photostable (PS) nanocomposites (P3AW) (P3AW = PLA with 3% A type TiO₂ nanowire) was only 5%. PD PLA exhibited characteristic peaks of carboxylic acid OH stretching and C?C double bond after UV irradiation in Fourier‐transform infrared spectra, whereas spectra of PS PLA remained almost the same. Thermal decomposition temperatures, glass transition temperatures, and melting temperatures of PD PLAs decreased dramatically after UV irradiation, but no obvious changes were observed for those of PS PLAs. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40241.     

Microlayer coextrusion as a route to innovative blend structures

Nanolayer and microlayer coextrusion is a method for combining two or three polymers as hundreds or thousands of alternating layers with individual layers as thin as tens of nanometers. The possibility for utilizing microlayer coextrusion as a tool for creating microplatelets of high aspect ration was explored. Polypropylene (PP) was combined with polyamide‐66 (PA66) in microlayers. A high volume fraction of PA66 microplatelets dispersed in PP was achieved by injection molding the microlayered materials at a temperature intermediate between the melting points of the two constituents. The difference in melting temperatures provided a broad processing window of about 60°C in which the PP layers melted to form the matrix whereas the PA66 layers remained in the solid state as dispersed microplatelets of high aspect ration. The resulting material had significantly improved oxygen barrier properties. An enhancement of 4–5 times over the barrier of the conventional melt blend resulted from increased tortuosity of the diffusion pathway.     

Facile fabrication of highly flexible poly(lactic acid) film using alternate multilayers of poly[(butylene adipate)‐co‐terephthalate]

Poly(lactic acid) (PLA) and poly[(butylene adipate)‐co‐terephthalate] (PBAT) are both commonly used biodegradable polymers. In this study, co‐extrusion of PLA and PBAT was used to create alternately multilayered films in order to obtain high‐flexibility PLA film. The incorporation of PBAT provides enhanced flexibility to PLA and the effect is more distinct in the PLA/PBAT multilayer film as the number of layers increases. Through differential scanning calorimetric and wide‐angle X‐ray scattering analyses, the crystallinity of PLA is shown to decrease more in the multilayer film than in the blended film. Transparency is also enhanced in the multilayer film. The fabrication of alternate multilayered film by co‐extrusion of PLA and PBAT shows a new method of preparing a flexible, transparent and fully biodegradable film, which is impossible through a blending process. © 2014 Society of Chemical Industry     

Comprehensive experimental study of a starch/polyesteramide coextrusion

A comprehensive study of the three‐layer film coextrusion was performed. Plasticized wheat starch (PWS) was chosen as the film central layer, and poly(ester amide) (PEA) was used as the surface outer layers. Single‐screw extruders and a standard feedblock attached to a flat coat‐hanger die were used to prepare the three‐layer films. The layer deformation and interfacial instability phenomena, inherent to multilayer flows, were thoroughly investigated. The effect of process variables, such as viscosity ratio, extrusion rate, layer thickness, and die geometry, were studied. Encapsulation of the central layer by the skin layers readily occurred at the edges of coextruded films. The stability of PEA/PWS/PEA coextrusion flows was closely related to the shear stress at the interface. Increasing global volumetric flow rates and the die gap geometry seemed to promote instabilities. Finally, the existence of instabilities at the interface increased the adhesion strength of multilayered products, due to mechanical interlocking between adjacent layers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2586–2600, 2002     

Coextrusion and biaxial orientation of multi-microlayer films

In this study, the multi-microlayer films (MMFs) prepared by the coextrusion of the corresponding polymers using a feed block design are reported. The alternating layers of the linear low-density poly(ethylene) and ethylene vinyl alcohol polymers are used to produce the 3-layered and 100-layered MMFs with the total thickness of around 640 μm. The MMFs are going through biaxial orientation and heat treatment which can change the morphologies and physical properties and reduce the thickness of the films to several micrometers. The differences in crystallinity, melting temperature, interface physical properties, tensile strength, and water vapor transmission rate of the MMFs are fully investigated. The intermolecular interaction of the 100-layered MMFs is much higher than that of the 3-layered MMFs possibly due to the tightly bonded layers which lead to the disappearance of the interface layers following by orientation. The MMFs are successfully prepared by coextrusion following by biaxial orientation and heat treatment of two or more different kinds of polymers with very different intrinsic properties. This MMFs exhibit excellent compatibility, mechanical property and water resistance characteristics which have potential uses in the composite materials for food and electronic packaging applications.     

Development of a melt‐extrudable biobased soy flour/polyethylene blend for multilayer film applications

Monolayer and multilayer films from biobased linear low‐density polyethylene and milled soy flour were produced through cast film coextrusion processes using conventional thermoplastic processing equipment. Films containing 10 and 20% by weight of soy flour milled to maximum particle sizes of 8, 11, and 22 µm were extruded and characterized as a packaging film material. Water resistance, tensile properties, and gas permeability were measured on each film and analyzed with respects to the soy particle size, soy loading, and layer configuration in the multilayer film structure. Mechanical properties results indicated that ultimate elongation of the soy‐containing films decreased by as much as 14% compared to the control, while tensile strength and maximum load testing did not reveal any identifiable trends. Monolayer soy‐containing film showed high moisture sensitivity, as measured by contact angle and absorption testing, while the multilayer films demonstrated a more hydrophobic nature as indicated by higher contact angle measurements. This increase in hydrophobic properties is due to protective polyolefin skin layers, which are more hydrophobic. Oxygen transmission rates of the multilayer films decreased by 38% due to the presence of soy flour as compared to the control that did not contain any soy flour. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40707.     

Effects of facile amine‐functionalization on the physical properties of epoxy/graphene nanoplatelets nanocomposites

Graphene nanoplatelets (GNPs) have excellent thermal, electrical, and mechanical properties. The incorporation of GNPs into a polymer can remarkably enhance the thermal and mechanical properties of the polymer especially when GNPs are well dispersed in the polymer matrix with strong interfacial bonding. Therefore, in this study, GNPs were amine‐functionalized by covalently bonding 4,4′‐methylene dianiline onto their surfaces via a facile synthetic route. The amine‐functionalization was confirmed by FTIR spectroscopy and TGA. Epoxy/GNPs nanocomposites were prepared and their curing behavior, thermomechanical properties and impact strength were investigated. The amine‐functionalization increased curing rate, storage modulus, thermal dimensional stability, and impact strength of the nanocomposites. The SEM images for the fracture surface of the nanocomposite with amine‐functionalized GNPs showed a smooth and ductile failure‐like surface, resulted from the improved interfacial bonding between GNPs and the epoxy matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42269.