Enhanced mechanical and thermal properties of rigid polyurethane foam composites containing graphene nanosheets and carbon nanotubes

The comparative study of rigid polyurethane foam (RPUF) nanocomposites based on graphene nanosheets (GNSs) and carbon nanotubes (CNTs) has been reported. A GNS content of 0.3 wt% in polyol turns to be optimal for its foamability with the isocyanate component, as verified by rheology measurements. Scanning electron microscopy and transmission electron microscopy observations reveal a homogeneous dispersion of GNSs and CNTs in the RPUF nanocomposites. Only 0.3 wt% loading of GNSs and CNTs led to 36% and 25% improvement respectively in the compressive modulus of the RPUF nanocomposites. Meanwhile, 16 °C and 14 °C improvements in the glass transition temperature confirm the important role of both the nanofillers in the heat resistance of RPUF nanocomposites. These results additionally indicate that GNSs work more effectively than CNTs in mechanical property and heat resistance enhancement of the RPUF nanocomposites. The superiority of GNSs over CNTs can be attributed to their wrinkled surface structure, unique two‐dimensional geometrical morphology and higher specific surface area, which results in stronger interaction and restriction of segmental motion at the interface between the GNSs and the RPUF matrix. In addition, changes in the thermal conductivity of the nanocomposites are negligible, indicating that incorporation of GNSs and CNTs will not hinder the application of RPUF nanocomposites as thermal insulators. On the contrary, the enhancement in mechanical properties and heat resistance will undoubtedly expand the application range of polyurethane foam materials. Copyright © 2012 Society of Chemical Industry     

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.     

Thermal and mechanical behavior of poly(vinyl butyral)‐modified novolac epoxy/multiwalled carbon nanotube nanocomposites

The effects of poly(vinyl butyral) (PVB) and acid‐functionalized multiwalled carbon nanotube modification on the thermal and mechanical properties of novolac epoxy nanocomposites were investigated. The nanocomposite containing 1.5 wt % PVB and 0.1 wt % functionalized carbon nanotubes showed an increment of about 15°C in the peak degradation temperature compared to the neat novolac epoxy. The glass‐transition temperature of the novolac epoxy decreased with increasing PVB content but increased with an increase in the functionalized carbon nanotube concentration. The nanocomposites showed a lower tensile strength compared to the neat novolac epoxy; however, the elongation at break improved gradually with increasing PVB content. Maximum elongation and impact strength values of 7.4% and 17.0 kJ/m² were achieved in the nanocomposite containing 1.5 wt % PVB and 0.25 wt % functionalized carbon nanotubes. The fractured surface morphology was examined with field emission scanning electron microscopy, and correlated with the mechanical properties. The functionalized carbon nanotubes showed preferential accumulation in the PVB phase beyond 0.25 wt % loading. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43333.     

Mechanical,electrical, and thermal properties of graphene nanosheet/aluminum nitride composites

Graphene nanosheet (GNS)/aluminum nitride (AlN) composites were prepared by hot-pressing and effects of GNSs on their microstructural, mechanical, thermal, and electrical properties were investigated. At 1.49 vol% GNSs content, the fracture toughness (5.09 MPa m^1/2) and flexural strength (441 MPa) of the composite were significantly increased by 30.17% and 17.28%, respectively, compared to monolithic AlN. The electrical conductivity of the composites was effectively enhanced with the addition of GNSs, and showed a typical percolation behavior with a low percolation threshold of 2.50±0.4 vol%. The thermal conductivity of the composites decreased with the addition of GNSs.     

Study of surface‐functionalized nano‐SiO2/polybenzoxazine composites

A series of the surface‐functionalized nano‐SiO₂/polybenzoxazine (PBOZ) composites was produced, and an attempt was made to improve the toughness of PBOZ material, without sacrificing other mechanical and thermal properties. A benzoxazine functional silane coupling agent was synthesized to modify the surface of nano‐SiO₂ particles, which were then mixed with benzoxazine monomers to produce the nano‐SiO₂‐PBOZ nanocomposites. The notched impact strength and the bending strength of the nano‐SiO₂‐PBOZ nanocomposites increase 40% and 50%, respectively, only with the addition of 3 wt % nano‐SiO₂. At the same load of nano‐SiO₂, the nano‐SiO₂‐PBOZ nanocomposites exhibit the highest storage modulus and glass‐transition temperature by dynamic viscoelastic analysis. Moreover, the thermal stability of the SiO₂/PBOZ nanocomposites was enhanced, as explored by the thermogravimetric analysis. The 5% weight loss temperatures increased with the nano‐SiO₂ content and were from 368°C (of the neat PBOZ) to 379°C or 405°C (of the neat PBOZ) to 426°C in air or nitrogen with additional 3 wt % nano‐SiO₂. The weight residue of the same nanocomposite was as high as 50% in nitrogen at 800°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Bio‐based polymer nanocomposites based on layered silicates having a reactive and renewable intercalant

Soybean oil‐based polymer nanocomposites were synthesized from acrylated epoxidized soybean oil (AESO) combined with styrene monomer and montmorillonite (MMT) clay by using in situ free radical polymerization reaction. Special attention was paid to the modification of MMT clay, which was carried out by methacryl‐functionalized and quaternized derivative of methyl oleate intercalant. It was synthesized from olive oil triglyceride, as a renewable intercalant. The resultant nanocomposites were characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effect of increased nanofiller loading in thermal and mechanical properties of the nanocomposites was investigated by thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The nanocomposites exhibited improved thermal and dynamic mechanical properties compared with neat acrylated epoxidized soybean oil based polymer matrix. The desired exfoliated nanocomposite structure was achieved when the OrgMMT loading was 1 and 2 wt % whereas partially exfoliated nanocomposite was obtained in 3 wt % loading. It was found that about 400 and 500% increments in storage modulus at glass transition and rubbery regions, respectively were achieved at 2 wt % clay loading compared to neat polymer matrix while the lowest thermal degradation rate was gained by introducing 3 wt % clay loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2031–2041, 2013     

Effects of graphene nanosheets on the dielectric,mechanical, thermal properties,and rheological behaviors of poly(arylene ether nitriles)

Poly(arylene ether nitriles) (PEN) containing various contents of graphene nanosheets (GNs) was prepared via solution‐casting method and investigated for their dielectric, mechanical, thermal, and rheological properties. For PEN/GNs nanocomposite with 5 wt % GNs, the dielectric constant was increased to 9.0 compared with that of neat PEN (3.1) and dielectric losses of all nanocomposites were in the range of 0.019–0.023 at 1 kHz. The tensile modulus and strength were increased about 6 and 14% with 0.5% GNs, respectively. The fracture surfaces of the all PEN/GNs nanocomposites revealed that GNs had good adhesion to PEN matrix. The thermal properties of the nanocomposites showed significant increase with increasing GN loading. For 5 wt % GNs‐reinforced PEN nanocomposite, the temperatures corresponding to a weight loss of 5 wt % (T_d5%) and 30 wt % (T_d30%) increased by about 20 and 13°C, respectively. Rheological properties of the PEN nanocomposites showed a sudden change with the GN fraction and the percolation threshold was about 1 wt % of GNs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Poly(ether ether ketone)/wrapped graphite nanosheets with poly(ether sulfone) composites: Preparation,mechanical properties,and tribological behavior

Antiwear composites with extraordinary tribological performances and good mechanical/thermal properties were developed by the dispersion of poly(ether sulfone) (PES) wrapped graphite nanosheets (GNSs) inside a poly(ether ether ketone) (PEEK) matrix via melt blending. The tribological behaviors and the mechanical/thermal properties of the composites were carefully investigated. Compared with pure PEEK and PEEK/GNS composites, the PEEK/wrapped GNS composites exhibited considerable enhancements in those performances; these were attributed to the eliminated layer of PES; this elimination not only eliminated the GNS aggregation inside the PEEK matrix for homogeneous distribution inside the PEEK matrix but also enhanced the interfacial adhesion between the PEEK and wrapped GNSs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41728.     

Reinforcing effect of amine-functionalized and carboxylated porous graphene on toughness,thermal stability,and electrical conductivity of epoxy-based nanocomposites

Epoxy-based nanocomposites reinforced with nonfunctionalized porous graphene (NPG), carboxylated porous graphene (CNPG), and amine-functionalized porous graphene (ANPG) were investigated with regard to mechanical properties, thermal stability, and electrical conductivity. Nanomaterials were added to the epoxy matrix in varying contents of 0.5, 1, and 2 wt %. Generally, mechanical properties were improved as a result of introducing nanomaterials into the epoxy resin. However, the amelioration of toughness was only observed in functionalized NPGs/epoxy nanocomposites. Field emission scanning electron microscopy images showed that functionalized nanomaterials induced a rougher fracture surface compared to the neat epoxy. Dynamic mechanical analysis along with differential scanning calorimetry confirmed an increment in the glass-transition temperature (T_g) of the reinforced nanocomposites. Also, they proved that functionalization made the epoxy network tougher and more flexible. The electrical conductivity and thermal stability of the epoxy resin were also improved when loaded with nanomaterials. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47475.     

Rectorite/thermoplastic polyurethane nanocomposites. II. Improvement of thermal and oil‐resistant properties

Organ‐rectorite/thermoplastic polyurethane (OREC/TPUR) nanocomposites were synthesized via melt intercalation. The dynamic mechanical properties by dynamic mechanical analysis (DMA), thermal and oil‐resistant properties were investigated. The results show that the storage modulus (E′), loss modulus (E″), and glass‐transition temperature (T_g) of the nanocomposites have an increase to some extent than those of pure TPUR. The thermal stability of nanocomposites was also studied in detail by thermal gravity analysis (TGA), which was higher than that of pristine TPUR matrix when the content of organic REC is at 2 wt %, and the decomposition temperature at 10% weight loss of OREC/TPUR is greatly increased up to 330°C from 315°C. Oil uptake of the composites is also significantly reduced in comparison with TPUR matrix, which is ascribed to the good barrier effect of nanosheets of OREC. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1165–1169, 2005     

Effect of the filler structure of carbon nanomaterials on the electrical,thermal, and rheological properties of epoxy composites

Carbon nanotubes (CNTs) and graphene nanosheets (GNSs) were used as fillers in epoxy composites with the aim of increasing the electrical and thermal conductivities of the composites. The filling of pristine CNTs produced the highest electrical conductivity (σ), whereas a high CNT functionalization and the two‐dimensional planar structure of GNSs were promising for improving the thermal conductivity. A combination of CNTs and GNSs exploited the advantages of both. When the CNT fraction was larger than 50 wt %, a higher σ was obtained. When a small amount of functionalized CNTs was added to the GNSs, the thermal conductivity was also increased. The rheological measurements revealed the lowest complex viscosity for the GNS filling and showed the exciting advantages of an easy processing. As a result, the mixed filling also exhibited a much lower viscosity than the pure CNT fillings. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 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.     

Interfacial crystallization of low‐crystallinity elastomer incorporated by multi‐walled carbon nanotubes: Mechanical reinforcement,structural evolution and enhanced thermal stability

In this paper, we report interfacial crystallization in olefin block copolymer (OBC) with low crystallinity incorporated by multi‐walled carbon nanotubes (MWCNTs). A hybrid shish‐kebab (HSK) superstructure in nanocomposites is observed that MWCNTs act as central shish and OBC crystals grow perpendicular to the nanotubes axis. The mechanical properties of nanocomposites are significantly improved with incorporation of MWCNTs. The most ideal reinforcing and toughening effect is both observed in nanocomposites with MWCNTs content of 1 wt % that can increase tensile strength by 122% as well as elongation at break by 36%. Efficient load transfer are confirmed with in‐situ Raman spectra that G’ band of MWCNTs in OBC matrix exhibit a downshifting trend and symmetric broadening of line shape which reveals additional macroscale strain from axial extension of MWCNTs in nanocomposites, thus suggesting a certain load is carried by HSK superstructure. The structural evolution of OBC and nanocomposites are investigated by in‐situ wide‐angle X‐Ray Diffraction (WAXD). The Herman's orientation factor of nanocomposites with 2 wt % MWCNTs incorporation is lower than that of neat matrix at mall and intermediate strains, indicating a heterogeneous stress distribution and low compliance of HSK superstructure, which is consistent with in‐situ Raman results. Moreover, the nanocomposites presents significantly enhanced thermal stability. The onset decomposition temperature of nanocomposites with 3 wt % MWCNTs can be 60.2°C higher than that of neat OBC. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42368.     

Polyethylene Nanocomposites with Ni,Co, and Fe Carbon-Based Magnetic Fillers

In the present study, the effect of Ni, Co, and Fe carbon-based magnetic fillers (Ni-C, Co-C, and Fe-C) was investigated on the magnetic, mechanical, thermal, and morphological properties of polyethylene nanocomposites. The in situ polymerization technique was used to prepare nanocomposites of polyethylene from the ethylene monomer introducing small amounts of filler ranging from 1 to 2 wt.%. The metal-carbonized fillers were obtained by pyrolysis of wood sawdust activated by Ni, Co, or Fe salts. X-ray diffraction showed that the fillers were of nanometric size. Thermogravimetric analysis was executed to investigate the thermal strength of the materials as well as to calculate the metal content in the carbon-based fillers. The onset degradation temperature showed an enhancement of 17°C, whereas the maximum degradation temperatures increased 4°C with the introduction of the filler. Differential scanning calorimetry indicated an improvement of 3°C in crystallization temperature, whereas the melting temperature remained unchanged compared to neat polyethylene. The filler was shown to increase the modulus of elasticity of the nanocomposites. The addition of 1.0 wt.% of the metal-carbonized material in the diamagnetic polymer matrix resulted in a thermoplastic nanocomposite with ferromagnetic behavior. POLYM. ENG. SCI., 60:988–995, 2020. © 2020 Society of Plastics Engineers     

Synthesis,characterization, and thermo mechanical properties of siloxane‐modified epoxy‐based nano composite

In this study, polymer hybrid composites were synthesized by sol‐gel process. 3‐Amino‐propyltrimethoxysilane [APTMS)/γ‐Glycidoxypropyl trimethoxy‐silane (GPTMS); (4, 4′‐Methylene‐dianiline (DDM)] and 1,4‐Bis(trimethoxysilylethyl) benzene (BTB) were added to DGEBA type epoxy resin for anticipated to exhibit excellent thermal stability. Boron trifluoride monoethylamine (BF₃MEA) was used as catalyst. The structure of nanocomposites was characterized by attenuated total reflectance (ATR) and solid‐state ²⁹Si NMR which suggest EP‐APTMS‐BTB/EP‐GPTMS‐BTB possesses T³; T¹–T⁰, and T¹ structures when the BTB content was lower than 10 wt % and higher 20 wt %, respectively. BF₃MEA was proved to be an effective catalyst for the sol‐gel reaction of APTMS, but it could not promote for GPTMS. From TEM microphotographs, EP‐APTMS‐BTB (10 wt %) possesses a dense inorganic structure (particle size around 5–15 nm) compare with the loose inorganic structure of EP‐GPTM‐/BTB (10 wt %). DSC, TGA were use to analyze the thermal properties of the nanocomposites and DMA was used to analyze the dynamic mechanical properties of hybrid composites. The T_gs of all nanocomposites decreased with the increasing BTB content. A system with BTB content lower than 10 wt % showed good dynamic mechanical property and thermal stability (Td₅ increased from 336°C to 371°C, char yield increased from 27.4 to 30.2%). The structure of inorganic network affects the Td₅ and dynamic mechanical properties of composite. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40984.     

Mechanical,thermal, and conductivity performances of novel thermoplastic natural rubber/graphene nanoplates/polyaniline composites

Conventional polymer blending has a shortcoming in conductivity characteristic. This research addresses the preparation of conductive thermoplastic natural rubber (TPNR) blends with graphene nanoplates (GNPs)/polyaniline (PANI) through melt blending using an internal mixer. The effect of PANI content (10, 20, 30, and 40 wt %) on the mechanical and thermal properties, thermal and electrical conductivities, and morphology observation of the TPNR/GNPs/PANI nanocomposites was investigated. The results showed that the tensile and impact properties as well as thermal conductivity of nanocomposite had improved with the incorporation of 3 wt % of GNPs and 20 wt % of PANI as compared to neat TPNR and reduced with further increase of the PANI content. It was observed that the GNPs and PANI acted as a critical component to improve the thermal stability and electrical conductivity of the TPNR/GNPs/PANI nanocomposites. The most improved conductivity of 5.22 E-5 S/cm was observed at 3 wt % GNPs and 40 wt % PANI. Variable-pressure scanning electron microscopy micrograph revealed the good interaction and distribution of GNPs and PANI within TPNR matrix at PANI loadings lower than 30 wt %. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48873.     

Synthesis of Methylacryloypropyl-POSS/Poly(fluorine-acrylate) Core-Shell Nanocomposites and Effect on Thermal Properties of Materials

Core-shell nanocomposites were prepared from acrylates, fluorine- containing methacrylate monomers and methylacryloypropyl polyhedral oligomeric silsesquioxanes (MAP-POSS) by emulsion polymerization. The properties of latex and nanocomposites were characterized by FTIR, NMR, TEM, laser particle diameter analyzer, DMA and TGA. The results showed that the particle diameter of composite latexes was about 33.5 nm, dynamic mechanical loss peak temperature T_p of the nanocomposites had the best high value at 99.6°C when 7 wt.% MAP-POSS was added, which is 7.8°C higher than the pure polyacrylates. MAP-POSS could increase the thermal stability of materials, the initial thermal decomposition temperature increases about 34°C.     

Effect of vinyl acetate content on the mechanical and thermal properties of ethylene vinyl acetate/MgAl layered double hydroxide nanocomposites

Ethylene vinyl acetate (EVA)/Mg‐Al layered double hydroxide (LDH) nanocomposites using EVA of different vinyl acetate contents (EVA‐18 and EVA‐45) have been prepared by solution blending method. X‐ray diffraction and transmission electron microscopic studies of nanocomposites clearly indicate the formation of exfoliated/intercalated structure for EVA‐18 and completely delaminated structure for EVA‐45. Though EVA‐18 nanocomposites do not show significant improvement in mechanical properties, EVA‐45 nanocomposites with 5 wt % DS‐LDH content results in tensile strength and elongation at break to be 25% and 7.5% higher compared to neat EVA‐45. The data from thermogravimetric analysis show that the nanocomposites of EVA‐18 and EVA‐45 have ≈10°C higher thermal decomposition temperature compared to neat EVA. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology,deformation behavior and thermomechanical properties of polypropylene/maleic anhydride grafted polypropylene/layered silicate nanocomposites

Nanocomposites polypropylene (PP) with 3 and 7 wt % of clay were prepared by melt mixing. Four types of maleic anhydride grafted PP (MAPP) in broad range of MA groups content (0.3–4 wt %) and molecular weights (MW) were used as polar compatibilizers. The effect of the MAPP kind on both the clay dispersion and miscibility with PP was studied. The mixed intercalated/exfoliated morphologies of nanocomposites in the presence of all studied compatibilizers were revealed by XRD and TEM. The oligomer compatibilizer with 4 wt % of MA groups increases the intercalation ability of polymer into clay galleries but this one has limited miscibility with PP and worsens crystalline structure of polymer matrix. The MAPPs with 0.3–1.3% of MA are characterized by the lower intercalation ability but well cocrystallize with PP. Maximum reinforcing effect is attained using high MW MAPP with 0.6% MA and for nanocomposite with 7 wt % (3.8 vol %) of clay it averages almost 1.7 times relative to neat PP and 1.3 times relative to noncompatibilized composite. Dynamic storage moduli of nanocomposites compatibilized by MAPPs with 0.3–1.3% of MA containing 7 wt % of clay increase up to 1.4–1.5 around 30–75°C and over the whole temperature range remain higher compared with both neat PP and uncompatibilized composite. On the contrary, the oligomer MAPP with 4 wt % of MA groups decreases the thermal–mechanical stability of nanocomposite at high temperature compared with both PP and uncompatibilized composites. The study of nanocomposites flammability showed that creating complex composites containing both layered silicate and relatively small amount of magnesium hydroxide can be a successful approach to reduce the combustibility of PP‐based nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Facile fabrication of polyethylene/silver nanoparticle nanocomposites with silver nanoparticles traps and holds early antibacterial effect

Antibacterial polyethylene (PE)/silver nanoparticle (AgNP) nanocomposites containing AgNPs at concentrations of 5 × 10^?5, 5 × 10^?4, and 5 × 10^?3 wt % were fabricated and tested. Transmission electron microscopy revealed an even dispersion of surface AgNPs in the PE/AgNP nanocomposites. No AgNP agglomeration was observed. The tensile strength, elongation at break, and Young's modulus of these PE/AgNP nanocomposites were similar to those of neat PE. Differential scanning calorimetry demonstrated that the PE/AgNP nanocomposites and neat PE had similar melting and crystallization temperatures of 126 ± 0.5 and 109 ± 0.6°C, respectively. The heats of fusion of the PE/AgNP nanocomposites containing AgNPs at concentrations of 5 × 10^?5 and 5 × 10^?4 and of 5 × 10^?3 wt % were lower than those of neat PE by 5 and 7%, respectively. These PE/AgNP nanocomposites were immersed in shaking liquid cultures of the potential pathogenic bacteria Escherichia coli, Bacillus subtilis, and Salmonella typhimurium in the lag phase. The results show that the growth rates of all of the tested bacteria were restricted effectively after 1.5, 3, and 6 h of cultivation, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43331.