Multilayer coextrusion of graphene polymer nanocomposites with enhanced structural organization and properties

A potential advantage of platelet‐like nanofillers as nanocomposite reinforcements is the possibility of achieving two‐dimensional (2D) stiffening through planar orientation of the platelets. Forced assembly by multilayer coextrusion, which enables the in‐plane orientation of platelet‐like fillers in alternating layers, was used in this work to produce poly(lactic acid) (PLA)/graphene multilayer films. These films exhibited a multilayer structure made of alternating layers of neat PLA and PLA containing graphite nanoplatelets (GNPs). Electron microscopy revealed information on the orientation of the individual GNPs. X‐ray diffraction results indicated that the thickness of the individual GNPs was reduced during the multilayer coextrusion process. A significant reinforcement of 120% at an overall GNP loading of 1 wt % in PLA was achieved. This high effective reinforcement was attributed to the high degree of planar alignment, improved dispersion and exfoliation and increased aspect ratio of the GNPs in the composite layers after multilayer coextrusion. Improved water vapor barrier properties were also achieved as a result of the highly organized 2D nanofillers in the multilayer films. These industrial scalable multilayer nanocomposite films open up possibilities for lightweight and strong packaging materials for food and industrial applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46041.     

Kevlar-functionalized graphene nanoribbon for polymer reinforcement

Multiwalled carbon nanotubes (MWCNTs) have been widely used as reinforcement fillers in past decades. However, the reinforcement effect has been greatly hindered by the limited available interface area (AIA) with polymer matrices for polymer composites. Successively, the method of oxidative unzipping MWCNTs into graphene nanoribbons (GNRs) was demonstrated to be the effective way for addressing the inherent drawback of MWCNTs. However, the GNRs are easy to agglomerate in polymer matrix even at relatively low loading amount. In this paper, we found that the functionalization of GNRs with Kevlar^® can significantly improve the dispersion state of GNRs in polymer matrix. Consequently, Kevlar^®-functionalized graphene nanoribbons (KGNRs) were successfully prepared through non-covalent functionalization of π–π stacking interaction between the aromatic area of Kevlar^® and the graphitic surface of GNRs. As-prepared KGNRs were characterized by FT-IR, TGA, XRD and TEM measurements. Poly(vinyl chloride) (PVC) and poly(methyl methacrylate) (PMMA) were selected as model polymers to investigate the reinforcement effect of KGNRs. The KGNRs could be well dispersed in PVC and PMMA matrices at relatively high loading level. Meantime, the ultimate tensile strengths and Young's modulus of KGNRs/PVC and KGNRs/PMMA composite films were significantly improved. Based on the observations above, KGNRs hold great promise in many potential applications in the future.     

Investigation of the crystalline structure of PVDF in PVDF/PMMA/graphene polymer blend nanocomposites

In this work, we report the preparation of poly(vinylidene fluoride)/poly methylmethacrylate (PVDF/PMMA)/graphene polymer blend nanocomposites via synthesis of PMMA/graphene as a masterbatch through in situ polymerization. The PMMA/graphene masterbatch compounded with PVDF by solution mixing in different ratios. The compounding was followed by solution casting to form polymer blend nanocomposites. Solution cast films were subjected to thermal treatments at three different temperatures. The crystalline structure of thermally treated samples was studied with X‐ray diffraction spectroscopy and Differential Scanning Calorimetric (DSC) analysis. Results indicated PMMA chains persuade the β crystalline form in PVDF but cannot stabilize them in elevated temperature; however, graphene sheets due to restricting effect on TT conformation chains are able to stabilize them. DSC data revealed the graphene sheets can increase the crystallinity of PVDF and also act as nucleating agents. Transmission Electron Microscopy demonstrated coexistence of the different stacking orders of graphene sheets in both masterbatch and polymer blend nanocomposite. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Poly(methyl methacrylate) nanocomposite reinforced with graphene,graphene oxide,and graphite: a review

Poly(methyl methacrylate) (PMMA) is an important transparent thermoplastic polymer having appropriate strength, chemical, weathering, heat, and UV resistance. However, essential properties of this versatile polymer need to be enhanced for high-tech applications. Graphene has opened up a new vista for developing functional polymeric nanocomposite. Therefore, reinforcement of PMMA with graphene and related nanofiller has been focused in literature. This review basically highlights the fundamentals and characteristics of the significant classes of PMMA/graphene, PMMA/graphene oxide, and PMMA/graphite nanocomposite. Recent developments in the applications of PMMA/graphene-based nanofiller nanocomposite in biomedical, sensor, supercapacitor, flame retardant, and electromagnetic interference shielding materials were also comprehended.     

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.     

Physical properties of polyethylene/silicate nanocomposite blown films

Maleated polyethylene/silicate nanocomposite and maleated polyethylene/SiO₂ blown films were prepared by melt extrusion. The silicate and SiO₂ significantly affected the physical properties of the films. The former films showed higher tensile strength than the latter films. This high reinforcement effect seemed to be attributable to the strong interaction between the matrix and silicate as well as the uniform dispersion of silicate layers in the polymer matrix. The addition of silicate beyond a certain content gave a worse Elmendorf tear strength than SiO₂. The silicate did not increase the falling dart impact strength at all. The worst Elmendorf strength apparently originated from the orientation of anisotropic silicate rather than the orientation of lamellae of the polymer matrix, and the silicate made the films more brittle. The well‐dispersed silicate layers in the polymer matrix gave almost the same optical properties as the pure polymer despite the increase in the silicate content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2131–2136, 2003     

In-plane lattice thermal conductivities of multilayer graphene films

The in-plane lattice thermal conductivities of a single layer and multilayer graphene films are investigated using nonequilibrium molecular dynamics simulations. It is found the thermal conductivity of a single layer graphene is higher than that of multilayer graphene. Increasing the bonding strength between neighboring layers will reduce the in-plane thermal conductivity for multilayer graphene films. The constraints from the neighboring layer play the role of impeding phonon transport along the in-plane direction in multilayer graphene films. This observation implies the thermal conductivity of a single layer graphene will be reduced in practical applications once it is bonded on a substrate.     

Thermomechanical properties of chemically modified graphene/poly(methyl methacrylate) composites made by in situ polymerization

The morphology and thermomechanical properties of composites of poly(methyl methacrylate) (PMMA) and chemically modified graphene (CMG) fillers were investigated. For composites made by in situ polymerization, large shifts in the glass transition temperature were observed with loadings as low as 0.05 wt.% for both chemically-reduced graphene oxide (RG-O) and graphene oxide (G-O)-filled composites. The elastic modulus of the composites improved by as much as 28% at just 1 wt.% loading. Mori–Tanaka theory was used to quantify dispersion, suggesting platelet aspect ratios greater than 100 at low loadings and a lower quality of dispersion at higher loadings. Fracture strength increased for G-O/PMMA composites but decreased for RG-O/PMMA composites. Wide angle X-ray scattering suggested an exfoliated morphology of both types of CMG fillers dispersed in the PMMA matrix, while transmission electron microscopy revealed that the platelets adopt a wrinkled morphology when dispersed in the matrix. Both techniques suggested similar exfoliation and dispersion of both types of CMG filler. Structural characterization of the resulting composites using gel permeation chromatography and solid state nuclear magnetic resonance showed no change in the polymer structure with increased loading of CMG filler.     

Preparation and colorimetric characterization of polymeric nanophotonic structures

A spin‐casting machine was designed and fabricated for preparation of multilayer polymer films from parent polymer solutions together with a polymeric dispersion of nanoparticles. The dispersion consists of polystyrene (PS)‐based core coated with a poly(methyl methacrylate‐co‐butyl acrylate) shell. Multilayer structure of such films was confirmed using a scanning electron microscope A sandwiched dispersed nanoparticles cast from the spin‐casting machine assumed a near to hexagonal arrangement. This structure affected the optical properties of the cast films. The films were characterized using colorimetric methods such as spectrophotometric and goniospectrophotometric techniques. Moreover, a dispersion of styrene‐based nanoparticles is sandwiched between PS and poly(methyl methacrylate) layers. The multilayer sandwiched films illustrated a greenish color shift attributed to the formation of hexagonal structures. The dispersion of styrene‐based nanoparticles within this sandwich restricts the observation of some wavelengths, which could be attributed to changes in the refractive indices of such samples. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

多层光干涉彩虹膜研究

研究了影响多层光干涉彩虹膜的彩虹效果、彩虹的色彩的均匀性和层间的粘合强度等因素。并通过树脂选择、树脂改性、不同折光指数的树脂的复配，成功地制备了LLDPE／PS、LLDPE EAA／PS和PMMA／PBT PET共挤多层光干涉彩虹膜。     

Synthesis of transfer-free graphene films on dielectric substrates with controllable thickness via an in-situ co-deposition method for electrochromic devices

The solutions and polymer supported materials in graphene transfer process would introduce lots of containments, defects and wrinkles, which weakens the performance of graphene. Herein, an in-situ co-deposition method is carried out to obtain transfer-free graphene films with controllable thickness on several dielectric substrates. The amorphous carbon (carbon source) and copper (catalyst) are co-deposited on dielectric substrates. Followed by an in-situ annealing process, the amorphous carbon is transformed to few-layer graphene. High co-deposition temperature could promote the decomposition of Cu(acac)₂ precursors, leading to the controllable thickness of amorphous carbon layer in Cu@C films. Finally, 3-, 5-, 8- and 10- layers graphene films with transmittance of up to 93.5% and square resistance of 0.8 kΩ·sq^?1 are obtained and a high-performance electrochromic device is fabricated using 3 layers graphene films as electrodes. The “color” and “bleach” time of the electrochromic device is 16.6 s and 6.8 s with the transmittance of 26.8% and 79.7% separately. This method paves an alternative way for the batch production of transfer-free graphene film as electrode materials.     

Highly filled multilayer thermoplastic/graphene conducting composite structures with high strength and thermal stability for electromagnetic interference shielding applications

Polyvinyl chloride (PVC)/graphene and poly(methyl methacrylate) (PMMA)/graphene nanocomposites were made by solution casting technique with graphene weight fractions of 1, 5, 10, 15, and 20%. Multilayer structures of the composites were made by hot compression technique to study their electromagnetic interference shielding effectiveness (EMI SE). Tensile strength, hardness, and storage modulus of the nanocomposites were studied in relation with graphene weight fraction. There has been a substantial increase in the electrical conductivity and EMI SE of the composites with 15–20% filler loading. Differential thermal analysis of the composites shows improved thermal stability with an increase in graphene loading. PMMA/graphene composites have better thermal stability, whereas PVC/graphene composites have superior mechanical properties. About 2 mm thick multilayer structures of PMMA/graphene and PVC/graphene composites show a maximum EMI SE of 21 dB and 31 dB, respectively, in the X band at 20 wt % graphene loading. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47792.     

Gas permeation in miscible homopolymer–copolymer blends. I. Poly(methyl methacrylate) and styrene/acrylonitrile copolymers

Gas transport properties in homogeneous blends of PMMA with each of two SAN random copolymers, containing 13.5 and 28% by weight of acrylonitrile respectively, have been measured at 35°C for He, H₂, O₂, N₂, Ar, CH₄, and CO₂. For all cases, the permeability and diffusion coefficients are higher than that expected from the semilogarthmic additivity rule. On the other hand, the solubility coefficients and the ideal gas separation factors follow this rule well. These results for PMMA/SAN blends differ from those observed recently for other miscible blend systems; however, they agree well with recent theories proposed to describe gas sorption and permeation behavior in polymer mixtures. The composition dependence of gas transport properties observed in PMMA/SAN blends is attributed to the very weak net interactions between PMMA and SAN produced by repulsions between styrene and acrylonitrile units in the SAN random copolymers. Gas transport properties in phase-separated PMMA/SAN blends have also been studied. The phase-separated blends show sorption and permeation properties very similar to the corresponding homogeneous blends which can be explained by an isotropic, interconnected, two-phase model proposed by Kraus and Rollmann. Gas permeabilities for the solution cast PMMA films used here are compared with melt-extruded specimens used previously, and the differences are attributed to molecular orientation.     

Thermal Expansion of Thin Diblock Copolymer Films

The thermal expansion of thin films of symmetric diblock copolymers of polystyrene (PS) and poly(methyl methácrylate) (PMMA) was investigated by X-ray reflectivity. The confinement of the copolymer to the substrate, coupled with the multilayering of the copolymer where PS and PMMA layers are oriented parallel to the substrate, gives rise to unusual thermal expansion characteristics. The total thickness of the film increases as 3α_L, where α_L is the linear thermal expansion coefficient of the copolymer. Unlike homopolymer films, the thermal expansion of an ordered block copolymer film results in an excessive stretching of the copolymer chains at the interface between the PS and PMMA layers. This excess stretching is a result of the confinement of the junction points of the copolymer chains to the interfaces and the suppression of the lateral expansion of the copolymer. When the stretching of the chains becomes too high, relaxation occurs by transporting copolymer chains to the surface. This is evidenced by a reduction in the period of the multilayer. After the copolymer chains have relaxed, the change in the multilayer period with temperature closely follows α_L.     

Reinforcement in melt-processed polymer–graphene composites at extremely low graphene loading level

We have prepared polymer nanocomposites reinforced with exfoliated graphene layers solely via melt blending. For this study polyethylene terephthalate (PET) was chosen as the polymer matrix due to its myriad of current and potential applications. PET and PET/graphene nanocomposites were melt compounded on an internal mixer and the resulting materials were compression molded into films. Transmission electron microscopy and scanning electron microscopy revealed that the graphene flakes were randomly orientated and well dispersed inside the polymer matrix. The PET/graphene nanocomposites were found to be characterized by superior mechanical properties as opposed to the neat PET. Thus, at a nanofiller load as low as 0.07 wt%, the novel materials presented an increase in the elastic modulus higher than 10% and an enhancement in the tensile strength of more than 40% compared to pristine PET. The improvements in the tensile strength were directly correlated to changes in elongation at break and indirectly correlated to the fracture initiation area. The enhancements observed in the mechanical properties of polymer/graphene nanocomposites achieved at low exfoliated graphene loadings and manufactured exclusively via melt mixing may open the door to industrial manufacturing of economical novel materials with superior stiffness, strength and ductility.     

Relationship between electrical and thermal conductivity in graphene-based transparent and conducting thin films

We measured and modeled the electrical, optical and thermal properties of transparent and conducting thin films based on graphene and graphitic platelets. Thermal conductivity of our films decreases with increasing electrical conductivity. Our experiments indicate that, for sufficiently large platelets, the influence factor in controlling the thermal conductivity is represented by the junctions between neighboring graphene platelets. The thickness of such junctions is determined by the average number of graphene layers (N) forming each platelet. The fact that both the thermal and electrical properties depend on N allows us to establish a model that leads to a theoretical relationship between the thermal and electrical conductivity in our samples, which is general enough to be applied to a large class of graphene-based thin films.     

The effect of confined crystallization on high-density poly(ethylene) lamellar morphology

High-density polyethylene (HDPE) was co-extruded against high glassy transition temperature (Tg) polycarbonate (PC) to fabricate multilayer films. Melt and recrystallization experiments were conducted on these extruded films to study the effects of isothermal recrystallization temperature and layer thickness on HDPE lamellae orientation. WAXS and AFM were used to demonstrate lamellar morphology of HDPE layers. We report that HDPE lamellae show twisted morphology in 30 nm thin layers after confined crystallization at a high temperature (128 °C). It may be the first time that anyone has created such twisted lamellar morphology with HDPE in such a thin layer. Similar twisted morphology of HDPE was also observed when HDPE was coextruded with another high Tg glassy polymer, polysulfone (PSF). Interestingly, the twisted HDPE lamellar morphology associated with an increased crystallinity improves both the oxygen and water vapor barrier properties of the multilayer films.     

Multilayered graphene films prepared at moderate temperatures using energetic physical vapour deposition

Carbon films were energetically deposited onto copper and nickel foil using a filtered cathodic vacuum arc deposition system. Raman spectroscopy, scanning electron microscopy, transmission electron microscopy and UV–visible spectroscopy showed that graphene films of uniform thickness with up to 10 layers can be deposited onto copper foil at moderate temperatures of 750 °C. The resulting films, which can be prepared at high deposition rates, were comparable to graphene films grown at 1050 °C using chemical vapour deposition (CVD). This difference in growth temperature is attributed to dynamic annealing which occurs as the film grows from the energetic carbon flux. In the case of nickel substrates, it was found that graphene films can also be prepared at moderate substrate temperatures. However much higher carbon doses were required, indicating that the growth mode differs between substrates as observed in CVD grown graphene. The films deposited onto nickel were also highly non uniform in thickness, indicating that the grain structure of the nickel substrate influenced the growth of graphene layers.     

Mechanical responses of a polymer graphene-sheet nano-sandwich

The interfacial mechanics and reinforcement by the graphene sheets in polymer matrix nanocomposites are important to their understanding. However, the methods available for their investigation remain a challenge. Here we report on a novel study in which the mechanical responses of a nano-sandwich model structure made of a single graphene sheet sandwiched between ultrathin polymer layers are determined using a nano-bubble inflation method. The stress-strain behavior of the graphene nano-sandwich shows that significant reinforcement is obtained at small strains and that the method also provides a measurement of the interfacial shear strength. In addition, the study provides data related to internal stresses that develop between the graphene layer and the polymer sandwich faces.     

Structural colors from TiO2/SiO2 multilayer flakes prepared by sol-gel process

Preparation of TiO₂/SiO₂ multilayer flakes and their application to decorative powders were investigated. In contrast to conventional products prepared through the multicoating of core platelets, the coreless TiO₂/SiO₂ multilayer flakes were prepared by detaching multilayer films from their substrates. These flakes exhibited structural colors, when the optical path length of both the TiO₂ and SiO₂ layers are adjusted to be one fourth of the wavelength of visible light. A multicoating of more than five layers resulted in the propagation of cracks, which prevented the preparation of thick flakes. Paint films fabricated using the multilayer flakes and acrylic resins showed reflectance spectra that were comparable with those obtained for multicoatings on substrates.