Graphene films receive tremendous attention due to their ultrahigh electrical and thermal conductivities, which show great application prospects in modern electronic devices. However, the brittleness and low strength of graphene films largely limit their use in advanced applications. And the preparation processes of graphene films reported so far are also not completely green. In this work, a novel strong and green graphene composite film with outstanding electromagnetic interference shielding effectiveness (EMI SE), electrical and thermal conductivities was successfully fabricated by using nanofibrillated cellulose (NFC) as dispersing agent and mechanical compression. In this way, graphene nanosheets (GNs) were not only efficiently dispersed in the aqueous solution but also linked together by NFC to enhance mechanical strength of the prepared films. Simultaneously, mechanical compression could powerfully induce strong alignment and increase the contact area of the GNs. As a result, the optimum electrical and thermal conductivities of the obtained films reached up to 988.2 S cm–1 and 240.5 W m–1 K–1, respectively, along with a high tensile strength of 61 MPa and a superior EMI SE of 43 dB with only ≈13 μm in thickness. Even more, the resultant films revealed excellent flame resistance. And the NFC can be removed by burning the films, resulting in complete graphene films with much higher electrical and thermal conductivities. The manufacturing route in our study is facile, cost-effective and completely green for the preparation of strong and highly conductive graphene-based thin films.Keywords: Electrical conductivity; Electromagnetic interference shielding; Graphene; Nanofibrillated cellulose; Thermal conductivity;

It is still a challenge to fabricate polymer-based composites with excellent thermal conductive property because of the well-known difficulties such as insufficient conductive pathways and inefficient filler–filler contact. To address this issue, a synergistic segregated double network by using two fillers with different dimensions has been designed and prepared by taking graphene nanoplates (GNPs) and multiwalled carbon nanotubes (MWCNT) in polystyrene for example. In this structure, GNPs form the segregated network to largely increase the filler–filler contact areas while MWCNT are embedded within the network to improve the network-density. The segregated network and the randomly dispersed hybrid network by using GNPs and MWCNT together were also prepared for comparison. It was found that the thermal conductivity of segregated double network can achieve almost 1.8-fold as high as that of the randomly dispersed hybrid network, and 2.2-fold as that of the segregated network. Meanwhile, much higher synergistic efficiency (f) of 2 can be obtained, even greater than that of other synergistic systems reported previously. The excellent thermal conductive property and higher f are ascribed to the unique effect of segregated double network: (1) extensive GNPs–GNPs contact areas via overlapped interconnections within segregated GNPs network; (2) efficient synergistic effect between MWCNT network and GNPs network based on bridge effect as well as increasing the network-density.Keywords: graphene nanoplates; multiwalled carbon nanotubes; segregated double network; synergy; thermal conductivity;

In this work, the effect of dioctadecyl dimethyl ammonium chloride (DDAC, a kind of alkyl ammonium salt) on polar β phase content and the diameter of electrospun PVDF nanofibers was investigated for the first time. Our experimental results show that the diameter of the electrospun PVDF nanofiber could be largely reduced and the content of polar β phase also become dominant immediately by just adding a little amount of DDAC. When the mass fraction of DDAC reached 4%, the content of polar β phase increased by about 39.1% compared with PVDF nanofibers without DDAC. Besides, the crystallinity of PVDF nanofibers also increased with the addition of DDAC. Based on the results, the possible mechanism of cooperative effect between electrospinning and DDAC on fiber diameter and formation of β phase in PVDF was discussed.

In this article, hybrid fillers with different dimensions, namely, 2-dimensional (2-D) expanded graphite (EG) and 1-dimensional (1-D) multi-walled carbon nanotubes (CNTs), were added to aromatic nylon MXD6 matrix via melt-blending, to enhance its thermal and electrical conductivity as well as electromagnetic interference shielding effectiveness (EMI SE). For ternary composites of MXD6/EG/CNTs, the electrical conductivity reaches up nine orders of magnitude higher compared to that of the neat MXD6 sample, which turned the polymer-based composites from an insulator to a conductor, and the thermal conductivity has been enhanced by 477% compared with that of neat MXD6 sample. Meanwhile, the EMI SE of ternary composite reaches ~50 dB at the overall filler loading of only 18 wt%. This work can provide guidance for the preparation of polymer composites with excellent thermal and electrical conductivity via using hybrid filler.

With the extensive use of portable and wearable electronic devices, ultrathin electromagnetic interference (EMI) shielding materials with excellent thermal management are increasingly desirable. In this study, ultrathin and highly aligned reduced graphene oxide (RGO)/cellulose nanofiber (CNF) composite films with excellent EMI shielding performance and strong anisotropy of thermal conductivity were fabricated by vacuum-assisted filtration followed by hydroiodic acid (HI) reduction. The obtained 50 wt% RGO/CNF composite films, which are only ≈23 μm in thickness, possess the remarkable electrical conductivity of ≈4057.3 S m−1 and outstanding EMI shielding effectiveness (SE) of ≈26.2 dB owning to the uniform dispersion and self-alignment into the layered structure of RGO. In addition, the RGO/CNF composite films with 50 wt% RGO loadings possess high in-plane thermal conductivity (K ≈ 7.3 W m−1 K−1) and, unexpectedly, very low cross-plane thermal conductivity (K⊥ ≈ 0.13 W m−1 K−1), resulting in strong anisotropy of the thermal conductivity (K/K⊥ ≈ 56). Thus, these ultrathin RGO/CNF composite films have great application potential as effective lightweight shielding materials against electromagnetic microwaves and heat, especially in flexible portable electronic devices and wearable devices.

The thermal conductivity of expanded graphite (EG)/polymer composites is investigated in terms of polymer chain structures. The EG/polyphenylene sulfide (PPS) composite with a backbone of benzene rings shows the continuous highest thermal conductivity and the fastest rate of enhanced ratio at the same content. Then it is followed by EG/syndiotactic polystyrene (sPS) composites with side groups of regularly arranged benzene rings. The last are the EG/amorphous polystyrene (aPS) composites with side groups of randomly arranged benzene rings. Our results show that the chain structures of polymer matrices have a great influence on the interaction and crystallization of EG/polymer composites, which leads to the different thermal behavior. More precisely, the strong π–π interaction between EG and polymer, the nucleation of crystal at the interface of EG/polymer and the relatively rich EG content in the amorphous phase are benefits to the enhancement of thermal conductivity. These factors are proved to be extremely important for the design of high thermally conductive composites in the fields of science and engineering.

It has been demonstrated that introducing another non-conductive particle into conductive filler filled composites could result in a better conductivity due to a volume exclusion effect. It was also reported that combining electrically conductive fillers with different geometric shapes and aspect ratio together could enhance the electrical conductivity due to the synergistic effect. To further explore these two effects on the electrical property enhancement, we firstly encapsulated neat silica (SiO2) with graphene oxide (GO) through electrostatic self-assembly to render SiO2 with surface conductivity. Then neat SiO2 or SiO2@GO together with multi-walled carbon nanotubes (MWCNT) were mixed with polystyrene (PS) to prepare conductive composites. In this way, the volume exclusion effect in the PS/MWCNT/SiO2 system and combined effect of volume exclusion and synergy in the PS/MWCNT/SiO2@rGO system could be investigated and compared. An obvious increased conductivity was observed only in the transition composition region for the PS/MWCNT/SiO2 system compared with the PS/MWCNT system. However, a largely enhanced conductivity was achieved through the composition region for the PS/MWCNT/SiO2@rGO system compared with the PS/MWCNT/SiO2 system and PS/MWCNT, accompanied by great enhancement of the electromagnetic interference (EMI) shielding effectiveness. Given the SEM characterization and rheological properties, we attributed this obvious enhanced electrical property to both a volume exclusion effect and a synergistic effect.

In recent decades, great efforts have been devoted to prepare materials with enhanced thermal conductivity due to the growing interest in thermal conductive materials. Herein, we illustrate a facile strategy to improve the thermal conductivity of polyvinylidene fluoride/expanded graphite (PVDF/EG) composites by pre-treatment of EG via ball milling. Before incorporating EG into PVDF via conventional melt processing, EG powders were treated by shear-force-dominated ball milling. In this way, the loose and porous vermicular structure of EG could be effectively destroyed and exfoliated to graphite nanosheets (GNSs). As a result, the PVDF/GNSs composites show improved thermal conductivity owing to their larger specific surface area. With the filler content fixed at 15 wt%, the thermal conductivity of treated PVDF/GNSs composites can reach 1.29 W m−1 K−1, 42.5% higher than that of PVDF/EG (0.90 W m−1 K−1). Moreover, the electromagnetic interference (EMI) shielding property and tensile strength of PVDF/CNSs composites are also remarkably improved. Our work proves to be a simple and easily industrialized method for EG treatment which has great potential for improving the thermal conductivity of polymer composites in lighting devices and electromagnetic shielding applications.

Barium titanate (BT) particles coated with different thickness of polydopamine (PDA) layers were incorporated into polyvinylidene fluoride (PVDF) to investigate influence of PDA coating layers on dielectric properties of composites. It is found that PDA coating layers not only effectively improved the interfacial interaction between BT particles and matrix but also significantly affected dielectric properties. PVDF composites loaded with modified BT exhibits superior dielectric properties in comparison with unmodified BT. Interfacial polarization is substantially suppressed because the catechol groups of PDA are able to constrain the mobility of nomadic charge carriers and ionizable hydroxyl groups on surface of BT particles. As a result, dependency of dielectric constant on frequency attenuates and tan δ is lowered to below 0.050 (1 kHz). The effect of suppression on tan δ tends to be more prominent as the thickness of PDA coating layer increases. The tan δ derived from ionic relaxation polarization is also constrained due to the chelation of PDA catechol groups with migrated cations. The as-prepared composites possess high dielectric constant and ultralow tan δ, making them promising for the industrial application as embedded capacitors.

Solvent-induced mechanical instability in a cross-linked poly(styrene-block-dimethylsiloxane) (PS-PDMS) film attached to a rigid substrate was systematically investigated. Through swelling with appropriate solvent vapor, a unique network of folds could be constructed successfully without the wrinkle-to-fold transition. Instead, small holes resulting from the mesostructural organization of PS-PDMS formed as nuclei to induce formation and growth of invaginated folds resembling creases which then constructed a network of invaginated folds. A complete network of sharp folds could be obtained after the two edges of a valley were combined into a sharp fold. The morphology and kinetics were closely related to the solvent solubility parameter and saturated vapor pressure. We varied the ratio between a relatively good solvent vapor and a poor solvent vapor, and so produced a slower dynamic process to precisely control the surface morphology. Poorly ordered cylinders with varied sizes resulting from strong cross-linking and spatial restrictions imposed by the network of folds could be obtained.

Graphene with polydopamine (PDA) coating layer which displays promoted dispersibility in organic solvent was prepared through self-polymerization of dopamine onto graphene oxide (GO) and subsequent chemical reduction. The PDA coated reduced GO (RDGO) is homogeneously incorporated into poly(vinylidene fluoride) (PVDF) matrix, which exhibit a percolation threshold at 0.643 wt%. The dielectric constant of PVDF with 0.70 wt% RDGO increases to 176, about 17 times of neat PVDF. Importantly, the loss tangent is suppressed to 0.337 due to reduction of the concentration and mobility of ionizable carboxylic groups by PDA. The enhancement of dielectric constant probably rises from duplex interfacial polarization induced by graphene–semiconductor interface, and semiconductor–insulator interface. The composites displays advantages in excellent dielectric properties and good flexibility and processability guaranteed by low loading of RDGO, which is suitable for the development of dielectric materials for energy storage.

•Nano-scale wrinkle patterns are fabricated in ultrathin polymer films.•The formation of wrinkle patterns is systematically investigated.•This approach shows good applicability in three representative polymer films.•Ordered surface patterns are generated by using nano-patterned silicon template.This paper presents an efficient and simple processing method for the fabrication and regulation of nano-scale wrinkle patterns. The stiff film is created through cross-linking the surface of ultrathin polymer film within twenty nanometers by using the hyperthermal hydrogen induced cross-linking (HHIC) method, and then the bilayer is heated above the glass transition temperature of the polymer before quenched to room temperature. In this way, wrinkle patterns with wavelength ranging from 150 to 300 nm are prepared. And a morphology transition between the pattern of single points (convex bumps) and the pattern of ridges (labyrinth) is observed. The formation of wrinkle patterns is systematically investigated as functions of the thickness of original ultrathin film, the time of HHIC treatment, the annealing temperature and the chemical structure of polymers. Furthermore, nano-patterned silicon wafer is used as a template to create multiscale, anisotropic wrinkle patterns.

Poly(butylene succinate) (PBS)/graphene oxide (GO) nanocomposites were fabricated via in situ polymerization with very low GO content (from 0.03 to 0.5 wt%). The microstructures of the nanocomposites were characterized with Raman spectroscopy, fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), sedimentation experiments and atomic force microscopy (AFM). The results showed that PBS chains have been successfully grafted onto GO sheets during in-situ polymerization, accompanied by the thermo-reduction from GO to graphene. The grafted GO displayed a great nucleating effect on PBS crystallization, resulting in largely improved crystallization temperature and decreased spherules size. A simultaneous enhancement in tensile strength and elongation was achieved for PBS/GO nanocomposites fiber. Meanwhile, increase in hydrolytic degradation rate was also observed for these nanohybrids. Our result indicates that using very low content GO is a simple way to achieve good dispersion yet with remarkable property enhancement for polymer/GO nanocomposites.

In this article, we systematically studied the self-assembly of poly(styrene-block-dimethylsiloxane) (PS-b-PDMS) on a poly(dimethylsiloxane) (PDMS) substrate with nanoscale channels. The channeled PDMS substrate was achieved by a simple replica molding method. To decrease the effect that the subsequent solvent treatments had in distorting the soft PDMS substrate, a simple UV/O3 treatment was provided before the self-assembly, resulting in a relatively stable, harder and hydrophilic silicon oxide (SiO2) layer on the channeled PDMS surface. Ultimately, the isotropic SiO2 nanopatterns with spherical and long cylindrical morphologies were successfully fabricated by the self-assembly of two kinds of PS-b-PDMS on the PDMS substrate with nanoscale channels, respectively. In particular, we demonstrated that the introduction of isotropic SiO2 patterns is an effective approach to greatly enhance anisotropic wetting rather than that of the anisotropic structure with channels.

Poly(bisphenol A carbonate) (BPA-PC) was post-polymerized by solid-state polymerization (SSP) after supercritical CO2-induced crystallization in low molecular weight particles prepolymerized via melt transesterification reaction. The effects of the crystallization conditions on melting behavior and SSP of BPA-PC were investigated with differential scanning calorimetry (DSC), Ubbelohde viscosity method and gel permeation chromatography (GPC). The reaction kinetics of the SSP of crystallized prepolymers was studied as a function of reaction temperatures for various reaction periods. As a result, the viscosity average molecular weight of BPA-PC particles (2 mm) increased from 1.9 × 104 g/mol to 2.8 × 104 g/mol after SSP. More importantly, the significantly enhanced thermal stability and mechanical properties of solid-state polymerized BPA-PC, compared with those of melt transesterification polymerized BPA-PC with the same molecular weight, can be ascribed to the substantial avoidance of undergoing high temperature during polymerization. Our work provides a useful method to obtain practical product of BPA-PC with high quality and high molecular weight.

The relationship between microphase structure and mechanical response of the binary blends consisting of polystyrene-block-polyisoprene-block-polystyrene copolymer and low molecular weight polystyrene has been investigated. Low molecular weight polystyrene was chosen to obtain uniformly solubilized nano-blends without macrophase separation. The specimens were solution-cast by adding different amounts of homo-polystyrene to acquire different microphase structures. Small angle X-ray scattering (SAXS), transmission electron microscopy (TEM) and atom force microscopy (AFM) have been used to study the microdomain and grain structure. It is observed that the structural changes in d-spacing and grain size on account of different amounts of polystyrene alter the mechanical behavior in both monotonic tensile and cyclic tests. The elastic and the Mullins effects are strongly sensitive to the changes in d-spacing and grain sizes. Moreover, the sample with bi-continuous structure shows the largest tensile strength and Mullins effect. In addition, the Mooneye-Rivlin phenomenological model was used to evaluate and explore the relationship between the polymer topological networks and the rubber elasticity of these styrenic nano-blends.

In the present work, a series of thermoplastic polyurethane (TPU)/microfibrillated cellulose (MFC) nanocomposites were successfully synthesized via in situ polymerization. TPU was covalently grafted onto the MFC by particular association with the hard segments, as evidenced by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The adequate dispersion and network structure of MFC in the TPU matrix and the strong interfacial interaction through covalent grafting and hydrogen bonding between MFC and TPU resulted in significantly improved mechanical properties and thermostability of the prepared nanocomposites. The tensile strength and elongation-at-break of the nanocomposite containing only 1 wt % MFC were increased by 4.5-fold and 1.8-fold compared with that of neat TPU, respectively. It was also very interesting to find that the glass transition temperature (Tg) of TPU was decreased significantly with the introduction of MFC, indicating potential for low-temperature resistance applications. Most importantly, compared with TPU nanocomposites reinforced with other nanofillers, the TPU/MFC nanocomposites prepared in this work exhibited excellent transparency and higher reinforcing efficiency.Keywords: covalent grafting; high strength; high toughness; microfibrillated cellulose; thermoplastic polyurethane;

Dispersion of graphene nanosheets (GNs) in a polymer matrix as mono layers was an important step towards fabricating high performance polymer/GNs nanocomposites. However, the insoluble and infusible properties of poly (tetrafluoroethylene) (PTFE) made the incorporation of nanofillers in PTFE matrix difficult. In this paper, a novel method based on poly (tetrafluoroethylene) (PTFE) latex that assured the fine dispersion of GNs in PTFE matrix was developed. PTFE latex was first modified by polyethylenimine (PEI) to create the positive charges on the surface of the PTFE particles, and then assembled with negatively charged graphene oxide sheets directly in water through electrostatic interaction, followed with chemical reduction, cold briquetting and hot sintering. Nanocomposites with controllable content and uniformly distributed GNs in PTFE matrix were prepared. The electrostatic coupling interactions improved the dispersion of GNs and facilitated the formation of filler networks in the PTFE matrix. Both the mechanical and wear performance of PTFE/GNs nanocomposites were greatly improved. PTFE/GNs nanocomposites also exhibited excellent electrical properties with a percolation threshold as low as 0.5 wt% and an electrical conductivity of 1.4 S/m at only 2 wt% graphene loadings. The new method agrees well with the latex technical process in PTFE bulk industrial manufacture and paves the way for an environmentally benign process for the bulk production of high quality polymer–graphene nanocomposites.

In this work, a poly(styrene-b-isoprene-b-styrene) thermoplastic elastomer was processed via a novel processing technique, dynamic-packing injection molding (DPIM). The shear cessation time is variable during DPIM, and a conventional injection-molded sample (C-sample) was prepared for comparison. For the dynamic-packing injection-molded sample (D-sample) with a short cessation time, a high Young’s modulus was obtained but with no significant enhancement of the break strength relative to the C-sample. However, a significant improvement of the break strength was achieved for the D-sample with longer cessation time. The mechanical performance of both the C-sample and D-samples was interpreted from the contribution of polyisoprene (PI, as the matrix) and polystyrene (PS, as a dispersed phase) segments. It is proposed that a short cessation time (strong shear) can induce the formation of a stretched PI network, while prolonged cessation time (more relaxation) could result in the segregation of PS and PI microdomains and the formation of a perfect parallel orientation of the PS cylinder in a hexagonal lattice.

Inspired by the photoprotection, radical scavenging of melanin together with versatile adhesive ability of mussel proteins, polydopamine (PDA) nanoparticles were successfully prepared and incorporated into environmentally friendly polymer, poly(propylene carbonate) (PPC) via solvent blending. The prepared composites exhibited excellent thermal stability in air and nitrogen atmosphere and extraordinary mechanical properties. The composites displayed eminent increase of temperature at 5% weight loss (T5%) by 30–100 K with 0.3 wt%–2.0 wt% loadings, meanwhile, the tensile strength and Young’s modulus were significantly improved from 11.5 MPa and 553.7 MPa to 40.5 MPa and 2411.2 MPa, respectively. The kinetic calculation indicated that improvement of T5% is presumably derived from suppressing chain-end unzipping. The glass transition temperature (Tg) of the PPC/PDA composites increased by 8–10 K. This is probably due to hydrogen bonding interaction since the abundant proton donors along PDA chains would interact with proton acceptors like C=O and C-O-C in PPC which would cause restriction of segmental motion of PPC chains.

Two-dimensional graphene and graphene-based materials have attracted tremendous interest, hence much attention has been drawn to exploring and applying their exceptional characteristics and properties. Integration of graphene sheets into macroscopic fibers is a very important way for their application and has received increasing interest. In this study, neat and macroscopic graphene fibers were continuously spun from graphene oxide (GO) suspensions followed by chemical reduction. By varying wet-spinning conditions, a series of graphene fibers were prepared, then, the structural features, mechanical and electrical performances of the fibers were investigated. We found the orientation of graphene sheets, the interaction between inter-fiber graphene sheets and the defects in the fibers have a pronounced effect on the properties of the fibers. Graphene fibers with excellent mechanical and electrical properties will yield great advances in high-tech applications. These findings provide guidance for the future production of high performance graphene fibers.

A simple and effective method to add large amounts of expanded graphite (EG) to poly (phenylene sulfide) (PPS) was developed. Before conventional melt processing, solid-state PPS and EG powders were mixed using high-speed rotation. In this way, the loose and porous vermicular structure of EG could be effectively destroyed and partly exfoliated, which made EG easy to be adsorbed on the surface of the PPS powders. This was extraordinarily helpful to achieve good dispersions of EG during the subsequent melt mixing even at high loading, which was difficult to achieve by conventional direct melt mixing. As a result of the good dispersions and strong interactions, the EG/PPS composites prepared showed a dramatically improved thermal conductivity (15.8 Wm−1K−1) and electrical conductivity (125.3 Sm−1) as the addition of EG reached 60 wt%.

Water droplets or films which are formed according to surface wettability show different effects on surface transparency. The effects of surface wettability on transparency in different water conditions are worth investigating because the surface usually suffers from the variable environmental water conditions. Herein, superhydrophobic and superhydrophilic surfaces, with negligible differences of physical structure but great differences of chemical composition, are used to investigate for the first time the relationship between surface wettability and transparency in four water conditions, including ambient condition, liquid water, boiling water steam, and ambient conditions after freezing at −4°C for 1 week. The transparency of the superhydrophobic surface is only about 5% lower in 550 nm light wavelength than that of the superhydrophilic surface in ambient conditions, but it is about 24% lower than that of the superhydrophilic surface in liquid water. When the surfaces are exposed to boiling water steam and ambient conditions after freezing at −4°C for 1 week, the superhydrophobic surface also shows lower transparency than the superhydrophilic surface because of increased fogging. However, the transparency shows little difference when the fog evaporates completely. The relationship revealed between surface wettability and transparency in different water conditions will be beneficial in choosing suitable wettability surfaces to satisfy the needed transparency in actual applications.

Two kinds of poly(vinyl alcohol) (PVA)-silica composites were prepared with different methods. One composite was prepared by directly mixing PVA with 80 nm silica nano-particles which were made from tetraethoxysilane (TEOS). The another was obtained by the mixing PVA and hydrolyzed TEOS in the presence of acid-catalyst. The properties of the two PVA/silica hybrids were characterized by means of scanning electron microscopy (SEM), UV-Visible spectroscopy, solubility tests, limiting oxygen index (LOI) test, tensile test and dynamical mechanical analysis (DMA), respectively. The results indicate that PVA-TEOS composites (PT for short) display more transparency than PVA-silica nano-particles hybrids (PS for short). At the same time, The PT composites presented more excellent performance than PS in water resistance, fire resistance and mechanical properties. Moreover, the Tg of PT increased with increasing TEOS content, while that of PS decreased.

Controlling the interface interaction of polymer/filler is essential for the fabrication of high-performance polymer composites. In this work, a core–shell structured hybrid (SiO2–GO) was prepared and introduced into an epoxy polymer matrix as a new filler. The incorporation of the hybrid optimized the modulus, strength and fracture toughness of the composites simultaneously. The ultrathin GO shells coated on silica surfaces were regarded as the main reason for the enhancement. Located at the silica-epoxy interface, GO served as an unconventional coupling agent of the silica filler, which effectively enhanced the interfacial interaction of the epoxy/SiO2–GO composites, and thus greatly improved the mechanical properties of the epoxy resin. We believe this new and effective approach that using GO as a novel fillers surface modifier may open a novel interface design strategy for developing high performance composites.Keywords: core−shell structure; epoxy; graphene oxide; interfacial enhancement;

The mechanical responses including monotonic and cyclic tensile responses have been investigated on a microphase-separated poly (styrene-isoprene-styrene) triblock copolymer (SIS). The specimens were injection-molded by using different melt temperatures to acquire different microphase structures. As a result of temperature-dependent segregation driving force, the specimens with reduced microphase separation can be obtained by increasing processing melt temperature from 180 °C to 240 °C. On the basis of stress-strain behavior, Young's modulus was found to increase with increasing PS domain continuity in the order of disorder state to disordered spheres to body-cubic-centered (BCC) spheres to oriented cylinders morphology. Meanwhile, cyclic hysteresis decreases with reduced microphase separation and with decreasing the applied predetermined maximum tensile strain. In addition, the Mooney–Rivlin phenomenological approach was used to evaluate and explore the relationship between the polymer topological networks and the rubber elasticity of thermoplastic elastomers.Graphical abstract

The introduction of graphene into a polymer matrix can markedly improve its mechanical properties and electrical conductivity. We report herein a novel strategy to fabricate polyester/reduced graphene oxide composites via simultaneous dispersion and thermo-reduction of graphene oxide (GO) during in situ melt polycondensation. The pristine graphite was first oxidized using a strong oxidant acid to prepare GO, and then GO sheets were dispersed into ethylene glycol (EG), where a homogeneous dispersion of GO in EG was obtained with ultrasonication. Finally polyester/reduced graphene oxide composites were prepared via in situpolymerization of terephthalic acid (PTA) and ethylene glycol containing well dispersed GO. Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and sedimentation experiments have been used to characterize the prepared composites. It is demonstrated that poly(ethylene terephthalate) (PET) chains may have been sucessfully grafted onto GO sheets during polymerization, accompanied by the thermo-reduction from GO to graphene. The TGA and XPS results showed that the content of grafted PET polymer was about to 60–80%, which indicates a homogeneous dispersion of GO sheets in the PET matrix, as demonstrated by SEM. Furthermore, a significant improvement in tensile strength and elongation at break of PET has been achieved. Therefore, our work provides a new way for the preparation of polyester/reduced graphene oxide composites and functionalization of graphene.

We herein provide an effective method to fabricate a transparent superamphiphobic coating with superhydrophobicity and near-superoleophobicity, the finished coating also shows improved stability under various measurements. To do this, a transparent superhydrophobic coating was first prepared with polydimethylsiloxane (PDMS) and hydrophobic silicon dioxide (SiO2) nanoparticles. Then the coating was sintered to degrade the PDMS into SiO2 before it was further oxidized into silanol (Si–OH). Finally, the coating was treated with 1H, 1H, 2H, 2H-Perfluorooctyl-trichlorosilane (PFTS). The PFTS treated coating shows transparency, superhydrophobicity with a water contact angle of 152.7 ± 2.1° and near-superoleophobicity with a diiodomethane contact angle of 140.7 ± 3.2°. The droplets of water and diiodomethane can simultaneously slide off the surface with a sliding angle of less than 6°. Moreover, the PFTS treated coating shows a higher stability than the PDMS/SiO2 coating fabricated by spin coating under various environmental conditions. The PFTS treated coating also shows quite good stability under high temperature environment. The superamphiphobic properties, transparency and improved stability of the PFTS treated coating are systemically discussed and the results show that the finished coating may be appropriate for many outdoor applications.

In this Article, the morphological evolution in the blend thin film of polystyrene (PS)/poly(ε-caprolactone) (PCL) was investigated via mainly AFM. It was found that an enriched two-layer structure with PS at the upper layer and PCL at the bottom layer was formed during spinning coating. By changing the solution concentration, different kinds of crystal morphologies, such as finger-like, dendritic, and spherulitic-like, could be obtained at the bottom PCL layer. These different initial states led to the morphological evolution processes to be quite different from each other, so the phase separation, dewetting, and crystalline morphology of PS/PCL blend films as a function of time were studied. It was interesting to find that the morphological evolution of PS at the upper layer was largely dependent on the film thickness. For the ultrathin (15 nm) blend film, a liquid–solid/liquid–liquid dewetting–wetting process was observed, forming ribbons that rupture into discrete circular PS islands on voronoi finger-like PCL crystal. For the thick (30 nm) blend film, the liquid–liquid dewetting of the upper PS layer from the underlying adsorbed PCL layer was found, forming interconnected rim structures that rupture into discrete circular PS islands embedded in the single lamellar PCL dendritic crystal due to Rayleigh instability. For the thicker (60 nm) blend film, a two-step liquid–liquid dewetting process with regular holes decorated with dendritic PCL crystal at early annealing stage and small holes decorated with spherulite-like PCL crystal among the early dewetting holes at later annealing stage was observed. The mechanism of this unusual morphological evolution process was discussed on the basis of the entropy effect and annealing-induced phase separation.

Thin films of an amorphous polymer, polystyrene (PS), and a crystalline polymer, poly(ε-caprolactone) (PCL), blend were prepared by spin coating a toluene solution. Surface chemical compositions of the blend films were measured by X-ray photoelectron spectroscopy (XPS), and the surface and interface topographical changes were followed by atomic force microscopy (AFM). By changing the PS concentration and keeping the PCL concentration of the solution at 1 wt %, a great variety of morphologies were constructed. The results show that the morphology of the blend films can be divided into three regions with increasing PS concentration. In region I, PS island domains are embedded in PCL crystals when the PS concentration is lower than 0.3 wt % and the size of the PS island increases with increasing PS concentration. In region II, holes with different sizes surrounded by a low rim are obtained when the concentration of PS is between 0.35 and 0.5 wt %. After selectively washing the PS domains, we studied the interface morphology of PS/PCL and found that the upper PS-rich layer extended into the bottom PCL layer, forming a trench surrounding the holes. In region III, an enriched two-layer structure with the PS-rich layer on top of the blend films and the PCL-rich crystal layer underneath is obtained when the concentration of PS is higher than 0.5 wt %. Last, the formation mechanism of the different surface and interface morphologies is further discussed in terms of the vertical phase separation to a layered structure, followed by liquid−liquid dewetting and crystallization processes during spin coating.

•The coupling and competition of phase separation and crystallization is studied.•Transition of lamellae orientation from edge-on to flat-on is achieved with increasing Mw of PS.•Transition from nucleation-controlled faceted habits to diffusion-limited dendrites is found.•A simple method is proposed to control the crystal structure of thin polymer films.The morphology and lamellar orientations in the thin blend films (∼30 nm) of poly(ε-caprolactone) (PCL) and different molar mass of polystyrene(PS) were investigated by atomic force microscopy (AFM). The influence of PS molar mass on the PCL crystal structures was studied. The results show that both fibrous edge-on and flat-on microcrystal can be obtained when low molar mass PS (LPS with Mw = 3.7k and 7.5k) is added into the thin PCL films, while only flat-on crystal is constructed for the films blending with high molar mass PS (HPS with Mw = 15.5k and 54k and 106k). The different crystal morphology formation is explained based on the competition between phase separation and crystallization. For the LPS/PCL blend films, it is the homogeneous nucleation crystallization of PCL at the films surface that leads to the formation of fibrous edge-on together with several isolated and faceted flat-on crystals. While for the HPS/PCL blend films, it is the first vertical phase separation followed by the heterogeneous nucleation of PCL at polymer/substrate interface process that results in the morphology of flat-on PCL crystal decorated by PS domain island or dewetting hollows on the top.Different molar mass of PS is introduced into thin PCL films to study the effects of PS molar mass on the crystal morphology and lamellar orientation of PCL on mica substrate. Both fibrous edge-on and flat-on microcrystal morphology can be obtained for the LPS/PCL blend films, while only flat-on crystal structure is constructed in the blend films of HPS/PCL.Figure optionsDownload full-size imageDownload high-quality image (126 K)Download as PowerPoint slide

The introduction of graphene into a polymer matrix can markedly improve its mechanical properties and electrical conductivity. We report herein a novel strategy to fabricate polyester/reduced graphene oxide composites via simultaneous dispersion and thermo-reduction of graphene oxide (GO) during in situ melt polycondensation. The pristine graphite was first oxidized using a strong oxidant acid to prepare GO, and then GO sheets were dispersed into ethylene glycol (EG), where a homogeneous dispersion of GO in EG was obtained with ultrasonication. Finally polyester/reduced graphene oxide composites were prepared via in situpolymerization of terephthalic acid (PTA) and ethylene glycol containing well dispersed GO. Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and sedimentation experiments have been used to characterize the prepared composites. It is demonstrated that poly(ethylene terephthalate) (PET) chains may have been sucessfully grafted onto GO sheets during polymerization, accompanied by the thermo-reduction from GO to graphene. The TGA and XPS results showed that the content of grafted PET polymer was about to 60–80%, which indicates a homogeneous dispersion of GO sheets in the PET matrix, as demonstrated by SEM. Furthermore, a significant improvement in tensile strength and elongation at break of PET has been achieved. Therefore, our work provides a new way for the preparation of polyester/reduced graphene oxide composites and functionalization of graphene.

With the extensive use of portable and wearable electronic devices, ultrathin electromagnetic interference (EMI) shielding materials with excellent thermal management are increasingly desirable. In this study, ultrathin and highly aligned reduced graphene oxide (RGO)/cellulose nanofiber (CNF) composite films with excellent EMI shielding performance and strong anisotropy of thermal conductivity were fabricated by vacuum-assisted filtration followed by hydroiodic acid (HI) reduction. The obtained 50 wt% RGO/CNF composite films, which are only ≈23 μm in thickness, possess the remarkable electrical conductivity of ≈4057.3 S m−1 and outstanding EMI shielding effectiveness (SE) of ≈26.2 dB owning to the uniform dispersion and self-alignment into the layered structure of RGO. In addition, the RGO/CNF composite films with 50 wt% RGO loadings possess high in-plane thermal conductivity (K ≈ 7.3 W m−1 K−1) and, unexpectedly, very low cross-plane thermal conductivity (K⊥ ≈ 0.13 W m−1 K−1), resulting in strong anisotropy of the thermal conductivity (K/K⊥ ≈ 56). Thus, these ultrathin RGO/CNF composite films have great application potential as effective lightweight shielding materials against electromagnetic microwaves and heat, especially in flexible portable electronic devices and wearable devices.