Poly(vinylidene fluoride)/polycarbonate blend-based nanocomposites with enhanced rigidity — Selective localization of carbon nanofillers and organoclay

Carbon nanotube (CNT), graphene nanoplatelet (GnP) and organo-montmorillonite (15 A) individually and simultaneously served as reinforcing fillers to prepare poly (vinylidene fluoride) (PVDF)/polycarbonate (PC) blend-based multicomponent nanocomposites. Scanning electron microscopy and transmission electron microscopy results confirmed the selective localization of individual and hybrid fillers within the PC domains. Some 15 A was located at the interface of PVDF/PC phases to modify the blend morphology. Addition of CNT led to the development of a quasi co-continuous PVDF-PC morphology. Differential scanning calorimetry results showed that 15 A, not CNT/GnP, facilitated PVDF crystallization in the composites. Among the fillers, 15 A alone induced β-form PVDF crystals, as revealed by the X-ray diffraction results, and consequently caused the complex crystallization and melting of PVDF. The rigidity (Young's and flexural moduli) of the PVDF/PC blend increased after the formation of various blend-based nanocomposites. The hybrid filler of CNT/15 A increased the Young's modulus by approximately 90% compared with that of the blend. Rheological property measurements confirmed the formation of a pseudo-network structure in the composites. Adding CNT increased the complex viscosity of the samples to a higher extent than did adding GnP, and the viscosity further increased with the co-existence of carbon nanofiller(s) and 15 A.     

Multiwalled carbon nanotubes reinforced poly (ether‐ketone) nanocomposites: Assessment of rheological,mechanical, and electromagnetic shielding properties

This study investigates the effect of multiwalled carbon nanotubes (MWCNTs) content on rheological, mechanical, and EMI shielding properties in Ka band (26.5‐40 GHz) of poly (ether‐ketone) [PEK] prepared by melt compounding using twin screw extruder. Transmission electron microscopy (TEM) and field emission gun scanning electron microscopy (FEG‐SEM) studies were adopted to identify dispersion of nanotubes in PEK matrix. TEM and SEM images showed uniform dispersion of MWCNTs in PEK/MWCNT composites even at loading of 5 wt%. The rheological studies showed that the material experiences viscous (fluid) to elastic (solid) transition at 1 wt% loading beyond which nanotubes form continuous network throughout the matrix which in turn promotes reinforcement. Additionally, Van‐Gurp Palmen plot (phase angle vs complex modulus) and values of damping factor further confirm that the material undergoes viscous to elastic transition at 1 wt% loading. This reinforcement effect of nanotubes is reflected in enhanced mechanical properties (flexural strength and flexural modulus). Flexural strength and flexural modulus of PEK showed an increment of 17% upon incorporation of 5 wt% of MWCNTs. Total shielding effectiveness (SE_T) of −38 dB with very high shielding effectiveness due to absorption (SE_A ~ −34 dB) was observed at 5 wt% loading of MWCNTs in PEK matrix in the frequency range of 26.5‐40 GHz (Ka band).     

Effect of halloysite nanotube on microstructure,rheological and mechanical properties of dynamically vulcanized PA6/NBR thermoplastic vulcanizates

Dynamically vulcanized thermoplastic vulcanizate (TPV) nanocomposites based on polyamide-6 (PA6) and acrylonitrile butadiene rubber (NBR) reinforced by halloysite nanotubes (HNT) were prepared via a direct melt mixing process. The effects of HNT on the physical, mechanical, and rheological properties of nanocomposites were investigated. The prepared PA6/NBR/HNT nanocomposites were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning colorimeter (DSC), dynamic mechanical thermal analysis (DMTA), and rheological measurements. The morphology study of prepared nanocomposites shows that the introduction of HNT into the PA6 phase causes a decrease in the size of NBR droplets. The mechanical measurements revealed that Young’s modulus of TPV nanocomposites increased with the HNT loading up to 54%. DMTA results show that the introduction of 10 wt% of HNT into the PA6/NBR TPV leads to a 30% increase in storage modulus. The rheological measurements revealed that the storage modulus of nanocomposites has an increase of more than 200% in the presence of 7 wt% of HNT loading. Analytical stiffness modeling of Young’s modulus of the TPV nanocomposites was investigated using Hui–Shia and Wu models. Both models have some deviations from experimental results and been modified to predict Young’s modulus of the nanocomposites containing HNT with more precisions. The viscosity behavior of TPV nanocomposites was studied using a Carruea–Yasuda model and showed that the yield stress of nanocomposites increases with higher HNT loadings, indicating the formation of a nanotube network along with NBR phase network.     

The synergistic reinforcing effects of halloysite nanotube particles and polyolefin elastomer-grafted-maleic anhydride compatibilizer on melt and solid viscoelastic properties of polylactic acid/ polyolefin elastomer blends

The effect of halloysite nanotube (HNTs) particles and polyolefin elastomer-graft-maleic anhydride (POE-g-MA) in the polylactic acid (PLA) and polyolefin elastomer (POE) blend with a constant weight percentage composition have been studied using the scanning electron microscopy, rheometry, dynamic mechanical thermal analysis (DMTA) as well as the thermogravimetric testing. Through these, it was found that the simultaneous presence of POE-g-MA and HNT significantly improves the melt and solid viscoelastic properties and thermal stability of PLA/POE. This improvement is attributed to the increased interactions and improved interfacial adhesion between the present components. The microscopic images of PLA/POE-g-MA/POE (80/8/12) blend containing 4 wt% HNT showed a microstructure similar to the interconnected morphology due to the enhanced compatibility and better dispersion of nanoparticles. The rheological behavior was significantly changed for the PLA/POE blend containing POE-g-MA and 4 wt% HNT. This dramatic increase in the rheological properties was consistent with the morphological results. Only one glass transition temperature was observed in the DMTA plot of PLA/POE-g-MA/POE blend, which was a sign of a homogeneous, fully compatible system. In addition, a very strong reinforcing effect of HNT particles was observed in the presence of POE-g-MA for the nanocomposites. Finally, the thermogravimetric analysis showed a completely different trend for thermal degradation of PLA/POE-g-MA/POE nanocomposite containing 4 wt% HNT, which could be an indication of microstructural development.     

Evident improvements in the rigidity,toughness, and electrical conductivity of PVDF/HDPE blend with selectively localized carbon nanotube

In this work, carbon nanotube (CNT) was used to fabricate poly(vinylidene fluoride) (PVDF)/high density polyethylene (HDPE) blend-based nanocomposites via a Haake mixer. Scanning electron microscopy confirmed that the CNT was mainly selectively located in the HDPE dispersed domains. Thermogravimetric analysis revealed that CNT addition improved the thermal stability of the blend (up to 61 °C increase at 3-phr CNT loading at 40 wt% loss) in air environment. Differential scanning calorimetry results revealed the enhanced nucleation of individual PVDF and HDPE upon crystallization in the composites; the presence of CNT inceased the stability of PVDF crystals. CNT addition increased the heat distortion temperature of the blend by up to 27 °C at 3-phr CNT loading. The complex viscosity and storage modulus increased due to the CNT pseudo-network formation in the reduce-sized HDPE phase of the composites. The rigidity of the blend was significantly improved after the addition of CNT. The impact strength of the blend increased by up to 66% after 2-phr CNT loading, and the electrical resistivity of the blend decreased by up to nine orders at 3-phr CNT loading due to the double percolation-like morphology formation.     

Mechanical and morphological properties of injection-molded rice husk polypropylene composites

In this work, the investigation of the physical, mechanical, and morphological properties of the rice husk flour/polypropylene composites was performed utilizing various filler loadings and coupling agent. Five levels of filler loading (35, 40, 45, 50, and 55 wt%) were designed. In addition, to help the interaction between fiber and polypropylene matrix, struktol coupling agent was added to the composites. All of tensile strength, Young's modulus, flexural strength, flexural modulus, and impact strength properties of the composites were carried out. Moreover, the 50 wt% filler-loaded composites had optimum tensile strength, flexural strength, and flexural modulus, whereas the 35 wt% of filler loading case was the best regarding Young's modulus, flexural strength, flexural modulus, and impact strength. Furthermore, the scanning electron microscope results demonstrate that as filler loading increases, more voids and fiber pullout occur.     

Effect of preheat and encapsulation of steel particles on the interaction with Bisphenol A composites

In this study, the mechanical and thermal behavior of the steel particles (SP) fabricated epoxy-based composites were investigated. The purpose of using SP was to find out their suitability and compatibility to be used as low-cost fillers for epoxy-based composites. A special steel-cast metal mold was used to fabricate the composites via self-casting method. The effect of SP concentration (10, 20, 30 and 40 wt%) on various properties of the epoxy/SP composites was explored. Another sample was prepared using the optimum loading with a special treatment using heat and encapsulation of the SP. Mechanical properties of the composites were analyzed through tensile, flexural and impact testing. Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) were used to examine the structural and morphological properties. In addition, thermal properties of the composites were analyzed with the thermogravimetric analyzer (TGA). Results indicated that the addition of PS into epoxy improved both tensile and flexural strength up to 98.5% and 147.6%, respectively, compared to the neat epoxy (NE). The decomposition temperature was raised nearly 18 °C for adding 30 wt% SP which was the maximum among all other composites. Results showed that 30 wt% of SP was the optimum loading for the better properties of the composites. In addition, the preheat treatment of the particles and the encapsulation process established a better interaction between the epoxy and the particles which resulted in the superior performance of the composites compared to the other samples. Overall, the improved mechanical and thermal properties of the SP-fabricated epoxy composites indicate that the epoxy/SP composite is a good candidate for structural and high temperature applications.     

Morphology,rheological and crystallization behavior in non-covalently functionalized carbon nanotube reinforced poly(butylene succinate) nanocomposites with low percolation threshold

Multi-walled carbon nanotubes (CNTs) were non-covalently functionalized by surface wrapping of poly(sodium 4-styrenesulfonate) (PSS) with the aid of ultrasound. The functionalized CNTs were incorporated into poly(butylene succinate) (PBS) through solution coagulation to fabricate CNTs filled PBS nanocomposites. The morphologies of the PBS/CNT nanocomposites were studied by scanning electron microscope (SEM) and transmission electron microscope (TEM), and the effect of loading of functionalized CNT on the rheological behavior, electrical conductivity and mechanical properties of the nanocomposites was investigated systemically. SEM observation indicates that functionalized CNTs dispersed in PBS matrix without obvious aggregation and showed good interfacial adhesion with the PBS phase. TEM observation reveals that a CNT network was formed when the loading of CNTs increased from 0.1 to 0.3 wt%. Rheological investigation indicates the formation of a CNT network with a percolation threshold of only 0.3 wt%. Significant improvement in electrical conductivity occurred at CNT loading of 0.3 wt%, with the value of electrical conductivity increasing by six orders of magnitude compared to neat PBS. Differential scanning calorimetry indicates that the melt crystallization temperature of PBS was improved by ∼14 °C with addition of only 0.05 wt% functionalized CNTs. Tensile tests indicate that both the yield strength and Young's modulus of PBS were apparently reinforced by incorporation of functionalized CNTs, while the elongation at break was reduced gradually.     

Preparation and characterization of glass fiber–reinforced polyethylene terephthalate/linear low density polyethylene (GF‐PET/LLDPE) composites

Polyethylene terephthalate (PET) was melt blended with linear low density polyethylene (LLDPE) and subsequently compounded with glass fibers (GF) as reinforcements at percentages ranging from 15 to 45 wt% of LLDPE and 5 to 30 wt% of GF. Thermal, morphological, and mechanical properties of the prepared composites were investigated. It was found that compounding PET/LLDPE blends with GF would be beneficial in producing composites that are thermally stable with good mechanical properties. For example, the impact strength of the composites containing 85/15 wt% (PET/LLDPE) at relatively high loading of GF, ie, from 15 to 30 wt%, was higher than that of the GF‐reinforced neat PET. When increasing the percentage of LLDPE in the composites, the impact strength increased with increasing GF content, and this was also better than that of GF‐reinforced PET whose impact strength drastically decreased upon increasing the GF%. The improvement in mechanical properties of the composite, we suggest, should be correlated with the morphologies of the composites where the visualized interface adhesion tended to be better at higher loadings of both LLDPE and GF.     

Study of mechanical and tribological properties of nylon 66‐titanium dioxide microcomposite

Nylon 66 microcomposites with various weight percentage of titanium dioxide (TiO₂) were prepared by a twin screw extruder and investigated for mechanical and tribological properties. Mechanical properties of the composite such as tensile strength/modulus, flexural strength/modulus, impact, and compressive strength first showed an increase up to 6 wt% TiO₂ followed by a decrease at higher filler loading. The value of heat deflection temperature increased with the increase in wt% of TiO₂. Sliding wear tests were performed on pin‐on‐disk equipment under different loads, sliding velocity, and sliding distance combinations. It was found that micro‐TiO₂‐Nylon 66 composite exhibited reduced wear and coefficient of friction up to 6 wt% TiO₂. Micro‐TiO₂ at 2 wt% was most effective in improving the tribological properties of plain nylon 66. The worn surfaces were examined by scanning electron microscopy to understand the wear mechanism. The optimal combination from 2 wt% to 6 wt% micro‐TiO₂‐Nylon 66 can be used depending upon the application requiring improvement in tribological or mechanical properties, respectively.     

Influence of flame retardant additives on the processing characteristics and physical properties of ABS

Antimony trioxide (Sb₂O₃) is a common additive in flame retardant formulations and a study has been made to determine the effects of adding different grades into ABS polymer either alone or with commercial brominated materials bis(Tribromophenoxy)ethane (BTBPE) or Tetrabromobisphenol A (TBBA). The results consider mechanical, microscopical and flame retardant properties, and the effects of different Sb₂O₃ grades with average particle sizes of 0.1μm, 0.52μm and 1.31μm. The Sb₂O₃ was added at 4wt% loadings and the bromines at 20wt% loadings. Additions of different grades of antimony trioxide showed that standard grades (0.52 and 1.31μm) had a detrimental effect on impact and flexural properties when added at a 4wt% loading. The use of a new sub‐micron particle size product (0.1μm) had little effect on impact properties and only a slight detrimental effect on the flexural modulus and flexural strength when added to the ABS. Additions of either of the two brominated materials also caused a large drop in impact properties when added at 20wt% loadings. The addition of TBBA BA‐59P into ABS caused an increase in both flexural modulus and flexural strength which was contrary to expectations. When formulated with 4wt% 1.31μm Sb₂O₃ these bromine containing compounds suffered a further reduction in impact energies. Using the 0.1μm material improved both impact and flexural properties but impact values were still below those of unfilled ABS. The addition of the 0.1μm grade resulted in improvements in fire resistance as measured by the UL‐94 properties.     

Hydrogen bonding interaction and crystallization behavior of poly (butylene succinate‐co‐butylene adipate)/thiodiphenol complexes

The poly (butylene succinate‐co‐butylene adipate) (PBSA)/thiodiphenol (TDP) complexes were prepared by melt blending. Intermolecular hydrogen bonding between carbonyl group of PBSA and hydroxyl group of TDP formed as verified by a combination FTIR and peak fitting technique. As a result, the crystallization temperature, melting temperature, crystallinity and crystallization rate of PBSA decreased with addition of TDP, implying impeded crystallization and reduced lamellar thickness. On the basis of Lauritzen–Hoffman analysis, the fold surface energy (σ_e) and work of chain folding (q) were increased by TDP incorporation. POM observation exhibited concentric ring‐banded spherulites for samples with 10 and 20 wt% TDP. A peculiar ring‐banded pattern with discrepant band spacing was obtained for the first time by addition of 30 wt% TDP, whose formation mechanism remains to be discussed. Copyright © 2016 John Wiley & Sons, Ltd.     

Study on the corrosion behavior of polymeric nanocomposite coatings containing halloysite nanotubes loaded with multicomponent inhibitor

In the present study, the halloysite nanotubes (HNTs) were loaded with a multicomponent inhibitor (LHNT) comprising mainly benzotriazole (BTA), sodium benzoate (SB), and lauric acid (LA) via the vacuum cycling method. The successful loading of the BTA + LA + SB inhibitor has been confirmed by the TGA, FTIR, and BET analyses. The TGA analysis has determined ～ 14% loading of the BTA + LA + SB into the HNTs. Moreover, UV–vis analysis shows that the time and pH-dependent have incremental release of the multicomponent inhibitor in various studied media. The composite coatings (LHNT COAT) were developed by reinforcing the 3 wt% of LHNTs into the epoxy matrix. The corrosion protection of the developed LHNT COAT was enhanced by 99.6% and 98.88% compared to the blank epoxy and unloaded HNT coatings, respectively. This improvement in the corrosion behavior can be attributed to the active release of the multicomponent inhibitor, as was also demonstrated by the electrochemical impedance spectroscopic (EIS) test. It is further predicted that the improved corrosion inhibition efficiency of LHNT COAT may be due to the formation of some components produced from the reaction of the inhibitor components or from the inhibitor reaction with the corrosive medium. The high corrosion resistance of LHNT COAT makes it attuned to several industrial applications.     

Preparation and properties of new flame retardant unsaturated polyester nanocomposites based on layered double hydroxides

The preparation of new layered double hydroxides/unsaturated polyester (LDH/UP) nanocomposites was performed and the effect of LDH on the resin properties was studied. Two different organo-LDHs have been prepared, adipate-LDH (A-LDH) and 2-methyl-2-propene-1-sulfonate-LDH (S-LDH); in order to evaluate the influence of these nanofillers, samples with two different concentrations were dispersed in the matrix. The physical, thermal, mechanical and fire reaction properties of nanocomposites were studied. Intercalated layered structures were observed for the different organo-LDH loadings (1 and 5 wt%). Mechanical properties studied under flexural tests show that incorporation of organo-LDH in the resin reduces the flexural strength of polyester resin while the flexural modulus is unchanged for the S-LDH/UP composites and increased with 1 wt% of A-LDH. Adding 1 wt% of A-LDH to the resin produces an important reduction on the flexural strength, but an increase of the flexural modulus. The study of fire reaction properties, using cone calorimeter, suggested a significant reduction in the UP flammability, by 46 and 32%, by incorporating 1 wt% of A-LDH and 5 wt% S-LDH, respectively. Mass loss curves show enhanced char formation with the different loads tested while the amount of evolved smoke remains quite unchanged.     

ELECTRICAL RESISTIVITY, CRYSTALLIZATION AND MECHENICAL PROPERTIES OF POLYPROPYLENE/MULTI-WALLED CARBON NANOTUBE/CALCIUM CARBONATE COMPOSITES PREPARED BY MELT MIXING

 Polypropylene (PP)/multi-walled carbon nanotube (MWCNT)/calcium carbonate (CaCO₃) composites are prepared by melt mixing using two types of CaCO₃ of different sizes. The electrical resistivities of the composites with the two types of CaCO₃ are all lower than those of the corresponding PP/MWCNT composites at various MWCNT loadings (1 wt%-5 wt%). The morphology of the composites is investigated by field emission scanning electron microscopy (FESEM). The crystallization behavior of PP in the composites is characterized by differential scanning calorimetry (DSC). The storage modulus, as measured by dynamic mechanical analysis (DMA), increases significantly by the presence of CaCO₃.     

Influence of degree of intercalation on the crystal growth kinetics of poly[(butylene succinate)-co-adipate] nanocomposites

The influence of the degree of intercalation of polymer chains in the two dimensional silicate galleries on the crystallization behavior of poly[(butylene succinate)-co-adipate] (PBSA) is being reported on. The nanocomposites were prepared by melt-blending of PBSA and organically modified montmorillonite (OMMT) in a batch-mixer. Two different types of commercially available OMMTs, with different extents of miscibility of organic modifiers with PBSA, were used, leading to highly delaminated and stacked/intercalated nanocomposite structures as revealed by X-ray diffraction (XRD) patterns and transmission electron microscopy (TEM) observations. The non-isothermal crystallization behavior of PBSA and the nanocomposite samples were studied by differential scanning calorimetry (DSC). Crystal growth kinetics studies showed that when silicate layers are highly delaminated into the PBSA matrix, nucleation behaviors decreased significantly, relative to the stacked/intercalated silicate layers. These observations indicate that the overall crystal growth kinetics retard in delaminated nanocomposites, opposed to increasing in the case of stacked/intercalated nanocomposites. Polarized optical microscopy (POM) observations and light scattering studies indicate that PBSA spherulites are fairly large and more perfectly grown in the case of delaminated nanocomposites, relative to the pure PBSA matrix. The effect of high levels of dispersion of silicate layers in the PBSA matrix on cold crystallization behavior was also studied.     

The effect of halloysite nanotubes and N,N'- ethylenebis (stearamide) on the properties of polylactide nanocomposites with amorphous matrix

Amorphous polylactide/halloysite nanotube (PLA/HNT) nanocomposites were prepared and examined. Neat HNT and HNT treated with N,N'- ethylenebis(stearamide) (EBS) were used as nanofillers. The role of HNT and/or EBS content on the cold crystallization of amorphous PLA matrix, HNT dispersion, as well as on the dynamic mechanical and optical properties of the materials was determined.The PLA/HNT-based nanocomposites contained well-distributed nanotubes and occasionally micron-sized aggregates, especially at high loading. HNT, EBS treated HNT and EBS influenced the cold crystallization of PLA, therefore the formation of the disorder α′ and the order α crystallographic forms of PLA.The nanocomposites exhibited increased stiffness and decreased transparency compared to the neat PLA. Due to the reinforcing effect and additional specific features of HNT, the addition of the nanofiller allows tuning of the properties of the nanocomposites with amorphous PLA matrix.     

Experimental investigation of the healing properties of the microvascular channels-based self-healing glass fibers/epoxy composites containing the three-part healant

In this study, the self-healing ability of the E-glass fibers/epoxy composites based on microvascular channels under flexural and tensile loading was investigated by a three-part healant. The fabrication of the microvascular channels was conducted through embedding the solid preforms and removing them. The epoxy resin and premix anhydride hardener-CuBr₂ (2-Methylimidazole) as the healing agents were used to study the self-healing ability of the composites at different healing times (4, 7 and 11 days) and various volume fractions for recovering the tensile (2.5, 4 and 8 vol%) and flexural (2, 3.2 and 3.7 vol%) strength. The optimum recovered tensile strength belonged to the composite containing the 4 vol% healant. The obtained healing efficiencies of this composite after 4, 7 and 11 days were 57, 68 and 69%, respectively. In the flexural test, the composite with the 3.2 vol% healant had the maximum healing efficiencies of 3, 46 and 44%, as compared with other composites. By using the field emission scanning electron microscopy and energy dispersed spectroscopy analysis, the healing ability of the composite was confirmed by this healing system.     

Cr-free Co-Cu/SBA-15 catalysts for hydrogenation of biomass-derivedα-,β-unsaturated aldehyde to alcohol

Cr-free bi-metallic SBA-15-supported Co–Cu catalysts were examined in the conversion of bio-mass-derived α-, β-unsaturated aldehyde (furfural) to value-added chemical furfuryl alcohol (FOL). Co–Cu/SBA-15 catalysts with a fixed Cu loading of 10 wt% and varying Co loadings (2.5, 5, and 10 wt%) were prepared by the impregnation method. The catalysts were characterized by X-ray dif-fraction, N2 sorption, H2 temperature-programmed reduction, scanning electron microscopy, ener-gy-dispersive X-ray spectroscopy, high-resolution transmission electron microscopy, CO chemi-sorption, and inductively coupled plasma mass spectrometry. The influence of different reaction parameters such as temperature, pressure, catalyst dosage, and furfural concentration on the cata-lyst performance was evaluated. Relative to catalysts supported on amorphous silica, the current SBA-15-supported Co–Cu catalysts displayed higher performance, attaining a furfural conversion of 99% and furfuryl alcohol selectivity of 80%. The catalytic reactions were conducted in a 100-mL autoclave at 170 °C and 2 MPa H2 pressure for 4 h.     

Effect of tungsten oxide loading on metathesis activity of ethene and 2-butene over WO<Subscript>3</Subscript>/SiO<Subscript>2</Subscript> catalysts

The metathesis of ethene and 2-butene to propene was studied over WO₃/SiO₂ catalysts with various WO₃ loadings (2, 4, 8, 12, 16, and 24 wt%). The 2-butene conversion and propene selectivity increased greatly with WO₃ loading increasing from 2 to 8 wt%, reached maximum at 8–12 wt% WO₃ loading, and then decreased when the WO₃ loading was higher than 12 wt%. From the above results and taking the economics into account, the optimal amount of WO₃ loading was ~8 wt%. The catalysts were characterized by physico-chemical and spectroscopic techniques to elucidate the effect of different tungsten oxide loadings on the metathesis reactivity of ethene and 2-butene. The characterization data indicated that three types of tungsten species (i.e., surface tetrahedral tungsten species, surface octahedral polytungstate species, and WO₃ crystallites) were present in the catalysts. It was found that WO₃ was not the active centers, and surface tetrahedral tungsten species might be more active than octahedral polytungstate species in metathesis reaction. The reduced form of tungsten species [W⁺⁴, W⁺⁵, and W^+(6−y) (0 < y < 1)] may be the suitable state of W species acting as metathesis active centers.