Tailored dielectric and mechanical properties of noncovalently functionalized carbon nanotube/poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) nanocomposites

The preparation of high‐dielectric poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) (SEBS) composites containing functionalized single‐walled carbon nanotubes (f‐SWCNTs) noncovalently appended with dibutyltindilaurate are reported herein. Transmission electron microscopy and X‐ray photoelectron and Raman spectroscopy confirmed the noncovalent functionalization of the SWCNTs. The SEBS‐f‐SWCNT composites exhibited enhanced mechanical properties as well as a stable and high dielectric constant of approximately 1000 at 1 Hz with rather low dielectric loss at 2 wt% filler content. The significantly enhanced dielectric property originates from the noncovalent functionalization of the SWCNTs that ensures good dispersion of the f‐SWCNTs in the polymer matrix. The f‐SWCNTs also acted as a reinforcing filler, thereby enhancing the mechanical properties of the composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical and piezo‐resistive properties of styrene–butadiene–styrene copolymer covalently modified with graphene/styrene–butadiene–styrene composites

As novel piezoelectric materials, carbon‐reinforced polymer composites exhibit excellent piezoelectric properties and flexibility. In this study, we used a styrene–butadiene–styrene triblock copolymer covalently grafted with graphene (SBS‐g‐RGO) to prepare SBS‐g‐RGO/styrene–butadiene–styrene (SBS) composites to enhance the organic solubility of graphene sheets and its dispersion in composites. Once exfoliated from natural graphite, graphene oxide was chemically modified with 1,6‐hexanediamine to functionalize with amino groups (GO–NH₂), and this was followed by reduction with hydrazine [amine‐functionalized graphene oxide (RGO–NH₂)]. SBS‐g‐RGO was finally obtained by the reaction of RGO–NH₂ and maleic anhydride grafted SBS. After that, X‐ray diffraction, X‐ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, and other methods were applied to characterize SBS‐g‐RGO. The results indicate that the SBS molecules were grafted onto the graphene sheets by covalent bonds, and SBS‐g‐RGO was dispersed well. In addition, the mechanical and electrical conductivity properties of the SBS‐g‐RGO/SBS composites showed significant improvements because of the excellent interfacial interactions and homogeneous dispersion of SBS‐g‐RGO in SBS. Moreover, the composites exhibited remarkable piezo resistivity under vertical compression and great repeatability after 10 compression cycles; thus, the composites have the potential to be applied in sensor production. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46568.     

Effects of l‐aspartic acid and poly(butylene succinate) on thermal stability and mechanical properties of poly(propylene carbonate)

Poly(propylene carbonate) (PPC) was modified by l ‐aspartic acid (Asp) and poly(butylene succinate) (PBS). To assess the effects of Asp and PBS on the thermal stability, mechanical properties of PPC, different PPC/Asp, PPC/PBS, and PPC/PBS/Asp blends were prepared by twin‐screw extruder. The results indicated that the thermal stability improved with the Asp content increasing from 0.5 to 5%. With trace presence of 2% Asp, the degradation temperature of PPC was greatly increased upon extruding and the Yield strength and Young's modulus increased 62 and 849 times, respectively, at 20°C. The flexibility of PPC was effectively improved by blending with PBS, the PBS has no significant effect on the thermal stability of PPC until PBS up to enough amount. Besides the Asp additive in PPC/PBS blends not only improved the thermal stability PPC, but improved the interfacial compatibility of the blend. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42970.     

Nanostructured thermosetting epoxy systems modified with poly(isoprene‐b‐methyl metacrylate) diblock copolymer and polyisoprene‐grafted carbon nanotubes

Nanostructured thermosetting composites based on an epoxy matrix modified with poly(isoprene‐b‐methyl methacrylate) (PI‐b‐PMMA) block copolymer were prepared through PI block segregation. Morphological structures were examined by means of atomic microscopy force microscopy. As epoxy/pristine multi‐walled carbon nanotubes (MWCNT) systems were found to present big agglomerations, with a very poor dispersion of the nanofiller, epoxy/PI‐b‐PMMA/MWCNT systems were prepared by using polyisoprene‐grafted carbon nanotubes (PI‐g‐CNT) to enhance compatibility with the matrix and improve dispersion. It was found that the functionalization of MWCNT with grafted polyisoprene was not enough to totally disperse them into the epoxy matrix but an improvement of the dispersion of carbon nanotubes was achieved by nanostructuring epoxy matrix with PI‐b‐PMMA when compared with epoxy/MWCNT composites without nanostructuring. Nevertheless, some agglomerates were still present and the complete dispersion or confinement of nanotubes into desired domains was not achieved. Thermomechanical properties slightly increase with PI‐g‐CNT content for nanostructured samples, whereas for nonnanostructured epoxy/PI‐g‐CNT composites they appeared almost constant and even decreased for the highest nanofiller amount due to the presence of agglomerates. Compression properties slightly decreased with block copolymer content, while remained almost constant with nanofiller amount. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of polycarbonate/poly(acrylonitrile‐butadiene‐styrene)/mesoporous silica nanocomposite films and its rheological,mechanical, and sound absorption properties

The homogeneous polycarbonate/poly(acrylonitrile‐butadiene‐styrene) (PC/ABS) nanocomposite thin films were prepared by a facile solvent casting method using phenylene modified‐mesoporous silica materials as additives and dichloromethane as a solvent. The physicochemical analyses using small‐angle X‐ray scattering, nitrogen adsorption–desorption, solid‐state ¹³C and ²⁹Si nuclear magnetic resonance, and scanning electron microscope were investigated to provide clear physical and chemical properties for modified‐mesoporous materials and nanocomposite films. Tensile tests were performed at room temperature according to ASTM D638. Rheological properties were also analyzed to observe any variance of solid–liquid property. As a compatibilizer and a reinforcing filler, mesoporous (organo‐)silicas showed enhanced features in rheological and mechanical properties. The sound absorption coefficient was measured by the impedance tube up to 6400 Hz according to ISO 10534‐2. It was found that the PC/ABS nanocomposites containing mesoporous materials can be used as a sound‐proofing support material depending on fabrication process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45777.     

Electrical conductivity and tensile properties of block‐copolymer‐wrapped single‐walled carbon nanotube/poly(methyl methacrylate) composites

Poly(methyl methacrylate) (PMMA) composites containing raw or purified single‐walled carbon nanotubes (SWCNTs) are prepared by in situ polymerization and solution processing. The SWCNTs are purified by centrifugation in a Pluronic surfactant, which consists of polyethyleneoxide and polypropyleneoxide blocks. Both the effects of SWCNT purity and non‐covalent functionalization with Pluronic are evaluated. Electrical conductivity of PMMA increases by 7 orders of magnitude upon the integration of raw or purified SWCNTs. The best electrical properties are measured for composites made of purified SWCNTs and prepared by in situ polymerization. Strains at fracture of the SWCNT/PMMA composites are nearly identical to those of the neat matrix. A certain decrease in the work to fracture is measured, particularly for composites containing purified SWCNTs (?31.6%). Fractography and Raman maps indicate that SWCNT dispersion in the PMMA matrix improves upon the direct addition of Pluronic, while dispersion becomes more difficult in the case of purified SWCNTs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41547.     

Dynamic mechanical properties in blends of poly(styrene‐b‐isoprene‐b‐styrene) with aromatic hydrocarbon resin

The damping properties in blends of poly(styrene‐b‐isoprene‐b‐styrene) (SIS) and hydrogenated aromatic hydrocarbon (C₉) resin were investigated by dynamic mechanical analysis. SIS exhibited two independent peaks of loss factor (tan δ) corresponding to the glass transition of polyisoprene (PI) and polystyrene (PS) segments, respectively. The addition of hydrogenated C₉ resin had a positive impact on the damping of SIS. With the increasing softening point and content of the resin, the main tan δ peak shifted to higher temperatures and the useful damping temperature range was broadened. Addition of mica or PS was found to widen the effective damping range evidently in the high‐temperature region, especially when PS was mixed in the solid state. It was concluded that the dispersed PS domains played a role of reinforcing fillers at low temperatures and served as a polymer component with a tan δ peak due to its glass transition at the high temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4157–4164, 2006     

Synergistic effect of poly(ethylene glycol) and graphene oxides on the crystallization behavior of poly(l‐lactide)

In this article, we report the combined effects of poly(ethylene glycol) (PEG) and/or graphene oxides (GOs) on the crystallization behavior of poly(l ‐lactide) (PLLA) under different crystallization conditions, such as nonisothermal crystallization, isothermal crystallization, and annealing‐induced cold crystallization. Differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction, and polarized optical microscopy were used to study the crystallization kinetics and crystallinity to illustrate the effects of PEG and/or GOs on the crystallization behavior of PLLA. The results show that PEG functioned as a plasticizer and improved the chain mobility of /PLLA during crystallization and the GOs acted as efficient nucleation agents and accelerated the crystallization rate. Finally, both PEG and GOs improved the crystallization ability of PLLA. Importantly, the simultaneous addition of PEG and GOs led to a synergistic effect on the crystallization behavior of PLLA under all conditions. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3498–3508, 2013     

In situ fast polymerization of graphene nanosheets‐filled poly(methyl methacrylate) nanocomposites

A series of graphene nanosheets‐filled poly(methyl methacrylate) nanocomposites (GNS/PMMA) is successfully prepared by an in situ fast polymerization method with graphene weight fractions from 0.1 to 2.0 wt %. In situ polymerization is effective in well dispersing of GNS in matrixes and suitable for both low and high content of GNS. The synthesis processes of polymer composites could be simplified and fast by using industrial grade graphene. The GNS fillers are found to disperse homogeneously in the PMMA matrix. The maximum electrical conductivity of the composites achieves 0.57 S m^?1, with an extremely low percolation threshold of 0.3 wt %. The electrical conductivities are further predicted by percolation theory and found to agree well with the experimental results. The results indicate that the microstructures, thermal, electrical, and mechanical properties of PMMA polymer are significantly improved by adding a low amount of graphene nanosheets. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43423.     

Poly(styrene–maleic anhydride) functionalized graphene oxide

In this study, poly(styrene–maleic anhydride) functionalized graphene oxide (SMAFG) was fabricated with in situ polymerization. The sample was characterized with Raman spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, transmission electron microscopy, and ultraviolet–visible absorption. The results of the experiments show that the thermal stability of SMAFG was improved significantly, and it also possessed a good dispersion in N,N‐dimethylformamide, N,N‐dimethylacetamide, aniline, and certain organic solvents. The calculated Hildebrand parameter of SMAFG was 23.8 MPa^1/2. This new method will broaden the applications of graphene, and the experiment showed that it could effectively improve the strength of polyamide 6 (PA6) compared with the pure PA6 fiber. The tensile strength of the SMAFG/PA6 composite fiber improved 29%, and the Young's modulus improved 33%, so this kind of functionalized graphene oxide can be used in the preparation of polymeric composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41987.     

Polypropylene/silica micro‐ and nanocomposites modified with poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene)

The effects of different silica loadings and elastomeric content on interfacial properties, morphology and mechanical properties of polypropylene/silica 96/4 composites modified with 5, 10, 15, and 20 vol % of poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) SEBS added to total composite volume were investigated. Four silica fillers differing in size (nano‐ vs. micro‐) and in surface properties (untreated vs. treated) were chosen as fillers. Elastomer SEBS was added as impact modifier and compatibilizer at the same time. The morphology of ternary polymer composites revealed by light and scanning electron microscopies was compared with morphology predicted models based on interfacial properties. The results indicated that general morphology of composite systems was determined primarily by interfacial properties, whereas the spherulitic morphology of polypropylene matrix was a result of two competitive effects: nucleation effect of filler and solidification effect of elastomer. Tensile and impact strength properties were mainly influenced by combined competetive effects of stiff filler and tough SEBS elastomer. Spherulitic morphology of polypropylene matrix might affect some mechanical properties additionally. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41486.     

Preparation and properties of styrene‐butadiene rubber nanocomposites blended with carbon black‐graphene hybrid filler

Graphene has become an attractive reinforcing filler for rubber materials, but its dispersion in rubber is still a big challenge. In this work, a novel carbon black‐reduced graphene (CB‐RG) hybrid filler was fabricated and blended with styrene‐butadiene rubber (SBR) via simple two‐roll mill mixing. The prepared CB‐RG hybrids had a microstructure with small CB agglomerates adsorbed onto graphene surfaces. CB acted as a barrier preventing the RG sheets from restacking even after drying. Homogeneous dispersion of graphene sheets in SBR matrix was observed by the mechanical mixing method based on the application of the CB‐RG hybrid fillers. Dynamic mechanical analysis showed that Tg of the SBR/CB‐RG blend was higher than that of the SBR/CB blend indicating strong interfacial interactions between RG and SBR due to the high surface area of graphene and the π‐π interaction between SBR and graphene. The tensile properties of SBR/CB‐RG composites improved significantly and the volume resistivity decreased compared with the SBR/CB blends. The thermal stability of SBR composites filled with CB and CB‐RG showed slight difference. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41309.     

A facile synthesis of a novel three‐phase nanocomposite: Single‐wall carbon nanotube/silver nanohybrid fibers embedded in sulfonated polyaniline

A three‐phase water‐soluble nanocomposite of single wall carbon nanotube/silver nanoparticle hybrid fibers embedded in sulfonated polyaniline has been synthesized by a simple chemical solution mixing process. The nanocomposite has been characterized by high resolution electron microscopy, X‐ray diffractometry, FTIR spectroscopy, Raman spectroscopy, and thermogravimetric analysis. Optical and electrical characteristics of the nanocomposite have been determined by UV–vis absorption spectroscopy, photoluminescence spectroscopy, and four‐probe electrical conductivity measurement. A surface plasmon absorption band obtained around 460 nm indicates the presence of silver nanoparticles in the composite. The optical band gap calculation for sulfonated polyaniline vis‐a‐vis the nanocomposite supported the conductivity measurement. Over 1300 times increase in DC electrical conductivity has been observed for the three‐phase nanocomposite, with a filler loading of 20 wt %, at 306 K. This observation could be explained by Mott's variable range hopping model considering a three‐dimensional conduction. Such a nanocomposite has immense potential for use as a cathode material in lithium‐ion batteries and supercapacitors. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41692.     

Fluorescence turn‐on chemical sensor based on water‐soluble conjugated polymer/single‐walled carbon nanotube composite

A chemical sensor for methyl viologen (MV²⁺), based on a water‐soluble conjugated polymer/single‐walled carbon‐nanotube (SWNT) composite, was fabricated. Water‐soluble poly(m‐phenylene ethynylene) with sulfonic acid side‐chain groups (mPPE‐SO₃) was synthesized via a Pd‐catalyzed Sonogashira coupling reaction and used to prepare a highly stable mPPE‐SO₃/SWNT composite with strong π–π interactions in water. The relationship between the optical properties and sensing capability of the mPPE‐SO₃/SWNT composite in aqueous solution was investigated. The addition of MV²⁺ enhanced the fluorescence intensity of the mPPE‐SO₃/SWNT composite by inducing a conformational change of the polymer from a helical to a random‐coil structure. The water‐soluble mPPE‐SO₃/SWNT composite enabled highly sensitive fluorescence detection of MV²⁺ in aqueous solutions with no precipitation resulting from reaggregation of the SWNTs. This mPPE‐SO₃/SWNT composite sensor system is therefore an effective turn‐on chemical sensor for MV²⁺. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43301.     

Preparation and characterization of extruded nanocomposite based on polycarbonate/butadiene‐acrylonitrile‐styrene blend filled with multiwalled carbon nanotubes

Nanocomposites of polycarbonate/acrylonitrile‐butadiene‐styrene (PC/ABS) with multiwall carbon nanotubes (MWCNT) prepared by masterbatch dilution are investigated in this work. Melt compounding with twin screw extruder is followed by complete characterization of morphology, rheological‐, mechanical‐, and thermal‐properties of the nanocomposites. Light‐transmission‐ and scanning electron microscopy shows the preferential location of MWCNT in the PC. Nevertheless, relatively good dispersion in the whole matrix is achieved, what is corroborated with the specific mechanical energy. The study of viscoelastic properties of PC/ABS‐MWCNT shows the fluid–solid transition below 0.5 wt % MWCNT. Beyond this point the continuous nanofiller network is formed in the matrix promoting the reinforcement. Addition of 0.5 wt % MWCNT reduces ductility of PC/ABS and enhances Young's modulus by about 30% and yield stress by about 20%. Moreover, theoretical values of stiffness calculated within this work agree with the experimental data. Electrical conductivity, showing percolation at 2.0 wt % MWCNT, are influenced by processing temperature. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40271.     

Pressure‐crystallized piezoelectric structures in binary fullerene C70/poly(vinylidene fluoride) based composites

The effective fabrication of polar crystalline structures of poly (vinylidene fluoride) (PVDF), such as beta and gamma, is crucial to the development of piezoelectric polymer devices. In this study, we report the effect of pressure on binary fullerene C70/PVDF‐based composite with an overall good C70 dispersion, which was prepared by an easy physical and mechanical route. The C70/PVDF composites were crystallized in a piston‐cylinder high‐pressure apparatus, and the polymeric crystalline structures totally with extended‐chain piezoelectric beta‐ or gamma‐form lamellae were successfully achieved in the composite samples by varying temperature, pressure, crystallization time, and composite composition. The c‐axis thickness of the extended‐chain beta‐form lamellae of PVDF in the composites increased and decreased with the increase of the applied temperature and pressure, respectively, and it increased with the increase of crystallization time. Although C70 was found to be negative for the rapid formation of beta‐form PVDF crystals, it played an important role in the growth of a beta‐form PVDF nanowire with extended‐chain crystalline substructures. The template‐free formation of such piezoelectric nanowires was attributed to a C70‐induced self‐assembly of the polymer, driven by physical interactions at high pressure. The pressure‐crystallized C70/PVDF composites, self‐reinforced with unique one‐dimensional piezoelectric structures, may diversify niche applications in advanced functional polymeric devices. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1823–1833, 2013     

Graphene oxide reinforced chitosan/polyvinylpyrrolidone polymer bio‐nanocomposites

Bio‐nanocomposite films based on chitosan/polyvinylpyrrolidone (CS/PVP) and graphene oxide (GO) were processed using the casting/evaporation technique. It has been found that the three components of bio‐nanocomposites can be easily mixed in controlled conditions enabling the formation of thick films with high quality, smooth surface and good flexibility. Structural and morphological characterizations showed that the GO sheets are well dispersed in the CS/PVP blend forming strong interfacial interactions that provide an enhanced load transfer between polymer chains and GO sheets thus improving their properties. It has been found that the water resistance of the CS/PVP blend is improved, and the hydrolytic degradation is limited by addition of 0.75 and 2 wt % GO. The modulus, strength, elongation and toughness of the bio‐nanocomposites are together increased. Herein, the steps to form new bio‐nanocomposite films have been described, taking the advantage of the combination of CS, PVP and GO to design the aforementioned bio‐nanocomposite films, which allow to have extraordinary properties that would have promising applications as eventual packaging materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41042.     

Graphene nanosheets‐filled epoxy composites prepared by a fast dispersion method

Graphene nanosheets‐filled epoxy composites (GNS/Epoxy) were prepared at different filler loading levels from 0.25 to 3.00 wt %. A fast dispersion method as short as 5 min is employed to disperse GNS in epoxy matrix, which was enough for the homogeneous dispersion of GNS with the help of high ultrasonic frequency of 100 kHz and power of 200 W and high heat treatment temperature of 70 °C. The maximum electrical conductivity and thermal conductivity of the composites achieved 0.058 S m^?1 and 0.57 W m^?1 K^?1, respectively, with a low electrical percolation threshold of 1.50 wt %. The electrical conductivities were further predicted by percolation theory and found to agree well with the experimental results, which indicated that the graphene nanosheets dispersed very well in the matrix even at very short processing time. The results showed that the microstructures, thermal, electrical, and mechanical properties of epoxy polymer were significantly improved by adding a low amount of graphene nanosheets. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45152.     

Enhanced thermoelectric performance by alcoholic solvents effects in highly conductive benzenesulfonate‐doped poly(3,4‐ethylenedioxythiophene)/graphene composites

Benzenesulfonate‐doped poly(3,4‐ethylenedioxythiophene) (PEDOT‐Bzs)/graphene thermoelectric (TE) composites with various graphene filler contents were synthesized in five different kinds of solvents. Dodecylbenzenesulfonic acid (DBSA) was used to achieve good dispersion of graphene into the PEDOT matrix. Among the synthesized PEDOT materials, the one synthesized in methanol (PEDOT‐MeOH) had the highest electrical conductivity. X‐ray photoelectron spectroscopy (XPS) analysis showed almost the same charge carrier concentration for all PEDOT materials. However, the X‐ray diffraction (XRD) analysis highlighted the enhancement of PEDOT chain stacking by shorter‐chain alcoholic solvents, as a result of which the carrier mobility and electrical conductivity were increased. The electrical conductivity and the Seebeck coefficient of the PEDOT/graphene composites were significantly improved with increasing the graphene content, which strongly depended on increased carrier mobility. The thermal conductivity of the composites exhibited relatively small changes, attributed to phonon scattering effects. The maximum TE efficiency of the PEDOT‐MeOH/graphene composite with 75 wt % graphene showed a substantially improved value of 1.9 × 10^?2, higher than that of the other PEDOT/graphene composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42107.     

Preparation and properties of octadecylamine modified graphene oxide/styrene‐butadiene rubber composites through an improved melt compounding method

Octadecylamine modified graphene oxide/styrene‐butadiene rubber (GO‐ODA/SBR) composites are prepared by a novel and environmental‐friendly method called “Improved melt compounding”. A GO‐ODA/ethanol paste mixture is prepared firstly, and then blended with SBR by melt compounding. GO‐ODA sheets are uniformly dispersed in SBR as confirmed by scanning electron microscope, transmission electron microscopy, and X‐ray diffraction. The interfacial interaction between GO‐ODA and SBR is weaker than that between GO and SBR, which is proved by equilibrium swelling test and dynamic mechanical analysis. GO‐ODA/SBR show more pronounced “Payne effect” than GO/SBR composites, indicating enhanced filler networks resulted from the modification of GO with ODA. GO‐ODA/SBR composite has higher tensile strength and elongation at break than SBR and GO/SBR composite. The tensile strength and elongation at break for the composite with 5 parts GO‐ODA per hundred parts of rubber increase by 208% and 172% versus neat SBR, respectively. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42907.