Synthesis and structural, morphological, compositional, optical and electrical properties of DBSA-doped PPy–WO3 nanocomposites

Progress in Organic Coatings 87 (2015) 88–94

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Synthesis and structural, morphological, compositional, optical and electrical properties of DBSA-doped PPy–WO3 nanocomposites A.T. Mane a , S.T. Navale a , R.S. Mane b,c , Mu. Naushad c , V.B. Patil a,∗ a b c

Functional Materials Research Laboratory, School of Physical Sciences, Solapur University, Solapur 413255, Maharastra, India School of Physical Sciences, Swami Ramanand Teerth Marathwada University, Nanded 431606, India Advanced Materials Research Chair, Department of Chemistry, College of Science, Bld#5, King Saud University, Riyadh, Saudi Arabia

a r t i c l e

i n f o

Article history: Received 16 December 2014 Received in revised form 29 April 2015 Accepted 12 May 2015 Keywords: DBSA-doped PPy–WO3 nanocomposites XRD SEM XPS UV–vis spectroscopy dc Electrical conductivity

a b s t r a c t Synthesis of DBSA-doped PPy–WO3 (organic–inorganic) nanocomposites, using a novel approach, has been proposed, and further envisaged for their structural, compositional, morphological, optical and electrical properties. DBSA-doped PPy–WO3 nanocomposites demonstrate superior above mentioned properties than their counterparts i.e. either PPy or WO3 . The XRD spectra of nanocomposites supported to conclude that both i.e. PPy and DBSA have no impact on the crystallinity of WO3 nanoparticles. The chemical structure of DBSA-doped PPy–WO3 nanocomposites have been elucidated using FTIR spectra. The morphologies and surface roughnesses of the DBSA-doped PPy–WO3 nanocomposites were confirmed using scanning electron microscope and atomic force microscope images, respectively. Interconnected type morphology and 13 nm average surface roughness were confirmed for DBSA doped PPy–WO3 hybrid nanocomposites. The EDX and XPS analyses evidence that, the formation of DBSA doped PPy–WO3 hybrid nanocomposites without any elemental impurities. The absorption peak of DBSA-doped PPy–WO3 nanocomposites shift towards the lower wavelength side as compared to the PPy–WO3 (50%) hybrid nanocomposites. Anionically charged sulfonate group which is supposed to stabilize doped state of the DBSA-PPy–WO3 nanocomposites, may be responsible for this shift. The dc electrical conductivity of DBSA-doped PPy–WO3 nanocomposites increases as the content of DBSA is increased from 10 to 50% this could be accounted for by the generation of conduction path through the PPy–WO3 nanocomposites as DBSA has anionic surfactant nature by preventing an agglomeration of functional material. © 2015 Elsevier B.V. All rights reserved.

1. Introduction Organic–inorganic nanocomposites (hybrid) are a fascinating class of materials, not only due to their fundamental properties but also for a number of practical applications [1–4]. Recently, nanocomposites have been studied extensively because of their potential applications in variety fields compared to corresponding pure organic and inorganic materials. Nanocomposites often exhibit unusual physical and chemical properties as compared to their bulk counterparts depending upon their sizes, shapes and stabilizing agents. The basic idea behind nanocomposites is to blend organic and inorganic materials into nanocomposites with molecular level control over interfaces, structures, and morphologies etc. [5,6]. These nanocomposites based on combination of organic and inorganic materials demonstrate several advantages over organic materials such as flexibility, light-weight, and good-moldability

∗ Corresponding author. Tel.: +91 2172744770x202; fax: +91 2172744770. E-mail address: [email protected] (V.B. Patil). http://dx.doi.org/10.1016/j.porgcoat.2015.05.007 0300-9440/© 2015 Elsevier B.V. All rights reserved.

and inorganic materials hold heat stability, high strength, and chemical resistance [7]. Depending upon the nature of association between the organic and inorganic components, nanocomposites are divided into two groups; one where the inorganic material is embedded into organic matrix, i.e. inorganic–in-organic composite [8] and the second, the organic polymer is confined into an inorganic material i.e. organic–in-inorganic composite [9]. These features of organic–inorganic nanocomposites help in designing various devices related to optics [10], electronics [11], gas sensors [12], mechanics [13] and photoconductors [14] etc. In this context, we are successfully synthesized inorganic–inorganic composites where inorganic component is WO3 nanoparticles which is well-embedded within the organic component i.e. polypyrrole (PPy). In juxtrapose to this, we used DBSA as a dopent to modify the structural and the chemical properties of composites. Various sulfonic acids such as camphor sulfonic acid (CSA), dodecyl benzene sulfonic acid (DBSA), and ␤-naphthalene sulfonic acid (NSA) have been considered as dopents in literature [15]. Among available organic materials, PPy has attracted much interest because of its structural flexibility, excellent conductivity,

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chemical stability against atmospheric conditions, room temperature operation, easy synthesis process, efficient luminescence, structural flexibility and potential for semiconducting and even metallic behavior etc. [16–19]. Whereas the inorganic counterpart tungsten oxide (WO3 ) is a transition metal oxide with useful properties, including high structural flexibility [20], switchable optical properties [21], catalytic behavior [22], electrochromic [23] and gas-sensing properties etc.[24,25]. Synthesis of organic–inorganic nanocomposites, where polypyrrole (PPy) as an organic material obtained using chemical polymerization method and tungsten oxide (WO3 ) as an inorganic material prepared from sol-gel method, has been explored. First of all, WO3 nanoparticles were added in PPy matrix in 0.5:1 ratio in order to prepare PPy–WO3 nanocomposites then the dopent dodecyl benzene sulfonic acid (DBSA) was added in PPy–WO3 nanocomposite matrix in different

N

state synthesis method was used for synthesis of DBSA-doped PPy–WO3 nanocomposites. The 10–50 wt.% of DBSA was added in the PPy–WO3 (50%) nanocomposite matrix. The prepared DBSAdoped PPy–WO3 nanocomposite powder was dissolved in m-cresol solvent and stirred for about 10 h at room temperature to get DBSA-doped PPy–WO3 casting solution and deposited onto glass substrate (10 × 10 mm2 ) using drop casting method and dried at room temperature. Fig. 1 shows proposed schematic for DBSAdoped PPy–WO3 nanocomposite product. 2.3. Reaction mechanism The proposed reaction mechanism of formation of DBSA-doped PPy–WO3 nanocomposites is shown bellow (details discussed later).

O

N WO3

N

89

Na

N

+

AN

O S

CH2

CH3 11

O

NA

WO3 AN

NA

n

n

PPy-WO3 nanocomposite

weight percentages (10–50 wt.%). Drop casting technique was used for obtaining nanocomposite films onto a glass substrate using m-cresol solvent. The structural, morphological, compositional, optical and electrical properties of DBSA-doped PPy–WO3 nanocomposites were carried out using X-ray diffraction (XRD), Fourier-transform infrared analysis (FTIR), scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), UV–vis spectra and two-probe dc electrical resistivity measurements, respectively. To the best of our knowledge and literature survey, this is the first where synthesis of DBSA-doped PPy–WO3 nanocomposites is investigated. 2. Experimental details 2.1. Chemicals Dodecyl benzene sulfonic acid (DBSA) [C18 H29 NaO3 S] (AR grade, Aldrich Chem.), pyrrole [C4 H4 NH] (AR grade, Aldrich Chem.), tungsten hexachloride (WCl6 ) (AR grade, Aldrich Chem.), ammonium persulfate [(NH4 )2 S2 O8 ] (AR grade, Sd Fine Chem.), methanol [CH3 OH] (AR grade, Sd Fine Chem.) and m-cresol (3-methylphenol, 3-hydroxy toluene) (AR grade, Sd Fine Chem.) procured commercially and used without further purification. 2.2. Synthesis of DBSA modified PPy–WO3 hybrid nanocomposites Chemical oxidative polymerization method was used for PPy synthesis where pyrrole acts as a monomer and ammonium persulfate as an oxidizing agent [26] and for WO3 nanoparticles synthesis, cost-effective sol–gel method was adopted [27]. The PPy–WO3 (50%) nanocomposites were obtained by adding WO3 nanoparticles in PPy matrix in 0.5:1 ratio. The PPy and WO3 were powder grinded with a smooth agate mortar for 3 h so as to obtain a homogeneous mixture of PPy–WO3 (50%) nanocomposite [28]. Solid

DBSA

DBSA doped PPy-WO3

2.4. Characterizations and measurements The crystal structure of DBSA-doped PPy–WO3 nanocomposites were determined by powder X-ray diffractometer (Rigaku, Ultima ˚ in 2 range with the scan IV, Cu K␤/40 kV/40 mA,  = 1.5406 A) range 10–80◦ . For chemical analysis FTIR (model: Perkin Elmer 100) measurement was used in the frequency range of 500–3500 cm−1 . SEM (Model: MIRA3 TESCAN, USA, operating at 15 kV) was used to investigate the surface morphology of DBSA-doped PPy–WO3 (10–50%) nanocomposites. XPS (VG, Multilab 2000, Thermo VG, Scientific UK) was used for the elemental analysis. The 2D and 3D AFM images of composite were obtained to investigate the surface roughness (SPA-300 HV). The thicknesses of the nanocomposite films were measured using Ambios XP-1 thickness profilometer. The absorption spectra of the PPy–WO3 (10–50%) nanocomposites were measured using a double-beam spectrophotometer Shimadzu UV-100 over 200–1100 nm wavelength range. Custom fabricated two-probe technique was used to investigate the dc electrical conductivity of DBSA-doped PPy–WO3 nanocomposites in the temperature range 313–473 K. 3. Results and discussion 3.1. Structural analysis Powder XRD patterns of (Fig. 2(A)) of the DBSA-doped PPy–WO3 nanocomposites (10–50 wt.%) were recorded by varying diffraction angle (2) in the range of 10–90◦ . It is seen that all the diffraction peaks of the spectra are in excellent agreement with the powder diffraction file no. 71-0131 belong to orthorhombic WO3 with lat˚ b = 7.57 A˚ and c = 7.754 A. ˚ There is tice parameters of a = 7.341 A, no noticeable peak of impurities, indicating no additional phase or chain agreement has been introduced into the nanocomposites. The sharp and well-defined peaks of DBSA-doped PPy–WO3 nanocomposites orients along (0 0 2), (0 2 0) and (2 0 0) planes. Moreover, the

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Fig. 1. Proposed schematic formation of DBSA-doped PPy–WO3 nanocomposites film.

Table 1 Shifting of the main IR peaks of PPy–WO3 (50%) hybrid nanocomposites and DBSA doped PPy–WO3 (DPW) hybrid nanocomposites. Assignments

PPy–WO3 (cm−1 )

DBSA doped PPy–WO3 (cm−1 )

C H wagging

613 667 727 921 1047 1201 1302 1459 1559 1706

618 687 786 927 1041 1209 1319 1464 1559 1714

C H plane deformation N C stretching C H in and out plane deformation Asymmetric stretching vibration Pyrrole ring stretching Bending motion of N H

3.2. Chemical structure analysis FTIR spectroscopy is based on the idea of the interference of radiation between two beams to results interferogram. FTIR spectra obtained using KBr pellets in the range of 500–3500 cm−1 for DBSAdoped PPy–WO3 nanocomposites (10–50%) are shown in Fig. 2B. There is shift in the main IR peaks of 10–50% DBSA-doped PPy–WO3 nanocomposite with respect to PPy–WO3 (50%) nanocomposite [12]. Shifting of the main IR peaks of PPy–WO3 (50%) nanocomposites and DBSA-doped PPy–WO3 (DPW) nanocomposites is given in the Table 1. The shift in peak position indicates loss in molecular order and conjugation after modification of PPy with DBSA and WO3 . Due to chemical interactions between PPy with DBSA and WO3 there may be change in the PPy active sites. The FTIR results confirm the formation of DBSA-doped PPy–WO3 nanocomposites. Fig. 2. (A) X-ray diffraction pattern of DBSA-doped PPy–WO3 (10–50%) nanocomposites, (B) FTIR spectrum of DBSA-doped PPy–WO3 (10–50%) nanocomposites.

DBSA-doped PPy–WO3 nanocomposites demonstrates prominent diffraction peaks of WO3 , indicating that the PPy and DBSA have no influence on its crystallinity. This suggests a uniform dispersion of the WO3 nanoparticles in the DBSA-doped PPy–WO3 hybrid nanocomposites without serious agglomeration [29].

3.3. Morphological analysis Fig. 3(A–E) shows the SEM images of the DBSA-doped PPy–WO3 (10–50%) nanocomposites. DBSA-doped PPy–WO3 nanocomposites show interconnected crystallites in addition to porous morphology [Fig. 3(A and B)] but, the porosity of nanocomposites decreases with increase in the wt.% of DBSA [Fig. 3(C–E)]. Thus, from the morphological analysis point of view it is concluded that the

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Fig. 3. SEM images of DBSA-doped PPy–WO3 nanocomposites with a loading of (A) 10% (B) 20% (C) 30% (D) 40% (E) 50%.

morphology of DBSA-doped PPy–WO3 nanocomposites is changed to flat or dense with increase in the wt.% of DBSA. Moreover, free WO3 nanoparticles are not seen i.e. all the WO3 nanoparticles are well-covered within the PPy and DBSA matrix, suggesting the capability of the present method to fabricate well-dispersed nanoparticles.

in good contact with each other. The micrograph also shows a high degree of porosity with conglomerated-type crystallites; separated by irregular voids. Rough surface consists of tiny globules with RMS surface roughness of 13 nm is confirmed from the 3D AFM image of DBSA-doped PPy–WO3 (20%) nanocomposite. 3.5. Chemical composition analysis

3.4. Surface topography The 2D and 3D AFM micrographs of the 20% DBSA-doped PPy–WO3 nanocomposite are shown in Fig. 4(A and B). The 2D AFM image of the surface exhibited spherical granular which are

The chemical composition of the DBSA-doped PPy–WO3 nanocomposites was examined by EDS spectrum [Fig. 5(A)]. The elements present in the material with their at.% and wt.% are shown as the inset. The table depicts the presence of C, N, O, S

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Fig. 5. (A) EDX spectrum of DBSA doped PPy–WO3 nanocomposite, (B) Wide range XPS spectrum of DBSA doped PPy–WO3 nanocomposite.

Fig. 4. (A) 2-D (B) 3-D AFM images of DBSA-doped PPy–WO3 nanocomposite.

and W. The elements C, N and O are from organic component PPy, S from dopent DBSA and W from inorganic component WO3 . The absence of any other peaks except those due to C, N, O, S and W approves the formation of DBSA-doped PPy–WO3 nanocomposite without any elemental impurities. The chemical states were investigated by XPS. In the case of XPS, electrons are liberated from the specimen as a result of a photoemission process. An electron is ejected from an atomic energy level of material by incidence of an X-ray photon, and its energy is analyzed by the sensitive spectrometer. The survey spectrum between binding energy vs. counts/sec. of DBSA-doped PPy–WO3 nanocomposites is shown in Fig. 5(B). The binding energy peak for O1s located at binding energy 531.96 eV indicates the presence of oxygen and is most corresponds to O2− [30]. The binding energy peaks of N1s and C1s are located at 400.18 eV (N C) and 285.09 eV (C C), respectively, which are well-agreed with earlier reported values of PPy [31]. The presence of S2p peak is due to dopent DBSA which is at 168.72 eV. The W 4f5 peak is found at 37.84 eV and the W 4f7

peak is at 35.46 eV. The splitting of the 4f doublet of W is found to be 2.38 eV, indicating the energy position of this doublet equivalent to the W6+ oxidation state [32]. Furthermore, the start binding energy, end binding energy, height counts, FWHM, area and at.% of present elements are summarized in Table 2. From survey table, it is seen that the at.% of elements present in the DBSA-doped PPy–WO3 nanocomposites are closely match to that of the at.% present in the EDX analysis. Thus, the compositional analysis is supporting for the formation of DBSA -doped PPy–WO3 nanocomposite. 3.6. Optical study The effect of addition of DBSA in PPy–WO3 (50%) nanocomposites was studied with the help of UV–vis spectroscopy. Fig. 6 shows the UV–vis spectrum of 20% DBSA doped PPy–WO3 nanocomposite. The UV–vis spectra of 20% DBSA-doped PPy–WO3 nanocomposite shows main absorption peak at 300 nm. While the absorption peak of PPy–WO3 (50%) hybrid nanocomposite located at 338 nm [28] is also shown as inset, supporting for absorption peak shift towards the lower wavelength side as compared to the PPy–WO3 (50%) nanocomposites. This shift in the absorption peak to lower wavelength region may be assigned to the large chain structure of

Table 2 Survey table of DBSA doped PPy–WO3 hybrid nanocomposites. Name

Start BE

Peak BE

End BE

Height counts

FWHM (eV)

C1s O1s N1s S2p W4f5 W4f7

290.44 538.58 405.69 172.05 39.32 36.83

285.09 531.96 400.18 168.72 37.84 35.46

281.3 529 398.79 166.47 36.87 33.95

37,494.39 33,802.32 964.87 5119.1 1501.7 2269.06

1.85 2.15 2.01 2.53 0.61 1.19

Area (P) CPS (eV) 80,277.66 97,158.3 3542.63 13,123.93 1467.57 2797.26

Area (N)

At.%

44,164.85 18,667.37 1093.73 4283.66 0 275.57

62.50 26.26 1.6 5.25 2.00 2.39

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93

Fig. 6. UV–visible spectra of DBSA-doped PPy–WO3 nanocomposite.

the PPy matrix that changes from complex conjugation structure i.e. quinoid form to almost no conjugation structure i.e. benzoid form.

3.7. Temperature dependent dc electrical conductivity study The Fig. 7(A) shows the variation of dc electrical conductivity (log ) with the reciprocal of temperature (1000/T) of DBSA-doped PPy–WO3 (10–50%) nanocomposites. DBSA-doped PPy–WO3 nanocomposites follow temperature dependence of conductivity and satisfy Arrhenius relation,  (T ) = 0 exp

 −E  a

kT

(1)

where Ea is the activation energy,  0 is the pre-exponential factor, K is Boltzmann constant and T is the absolute temperature. Also from Fig. 7(A), it is clearly observed that the dc electrical conductivity of DBSA-doped PPy–WO3 nanocomposites increases linearly with increase in the temperature, this can be successfully explained on the basis of electron hopping process. As the temperature increases from 313 to 423 K, the polymer chain acquires faster internal modes in which bond rotations produce segmental motion. This causes hopping intra-chain and inter-chain-ion movements and accordingly, the conductivity of the polymer becomes high [33]. Moreover, as the temperature increases, the forbidden energy gap between valence band and conduction band is reduce significantly and provide easiness for electrons to hope from valence band to conduction band and hence gives higher dc conductivity. As the wt.% of DBSA is increased from 10 to 50%, dc electrical conductivity (log ) of PPy–WO3 nanocomposites increases at room temperature [Fig. 7(B)]. Because DBSA is an anionic surfactant, could provide conduction path through the PPy–WO3 nanocomposites and prevent agglomeration of functional material resulting in the increase of electrical conductivity of PPy–WO3 nanocomposites at room temperature. The similar type of phenomenon was observed in camphor sulfonic acid-doped polyaniline–tin oxide nanocomposites [34]. In addition, the formation of polarons or bipolarons in the PPy–WO3 nanocomposites takes place with the delocalization effect of doping process thus, enhancing the conductivity of DBSA-doped PPy–WO3 nanocomposites [35–37]. The variation of conductivity with composition is shown in Fig. 7(C) where with increase of the wt.% of DBSA, conductivity increases which could be due to an ionic dopent DBSA which, generally, adds protons in N sites in the PPy matrix, and thereby, increases the number of carriers resulting in increase of electrical conductivity [37].

Fig. 7. (A) Electrical conductivity of DBSA-doped PPy–WO3 (10–50%) nanocomposite, (B) Variation of log  with composition. (C) Variation of conductivity () with composition.

4. Conclusions The DBSA-doped PPy–WO3 nanocomposite films were successfully prepared on glass substrate using m-cresol as a solvent by cost-effective drop-casting technique. Nanocomposites have exhibited different physical and chemical properties as compared to their bulk counterparts. The morphology of DBSA-doped PPy–WO3 nanocomposites is turned to flat/dense with increase in the wt.% of DBSA. XRD patterns demonstrate prominent

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diffraction peaks of WO3 nanoparticles indicating that the PPy and DBSA have no influence on the crystallinity of WO3 . This also supports for an uniform dispersion of the WO3 nanoparticles in the DBSA-doped PPy–WO3 nanocomposites. From FTIR study it is confirmed that DBSA-doped PPy–WO3 nanocomposite shows the shift in peak positions as compared with PPy–WO3 nanocomposites indicates the loss in molecular order and conjugation after modification of PPy with DBSA and WO3 . AFM image confirms spherical granular crystallites which are in good contact with each other with RMS surface roughness of 13 nm. The compositional analysis has evidenced the formation of DBSA-doped PPy–WO3 nanocomposites. UV–vis spectrum indicates that PPy matrix changes from large conjugations to almost no conjugations. From variation of dc electrical conductivity with temperature implies the formation of polarons or bipolarons in the PPy–WO3 nanocomposites with the delocalization effect of doping process thus enhancing the conductivity of DBSA-doped PPy–WO3 nanocomposites. Thus, DBSA-doped PPy–WO3 nanocomposite is a new and unaccustomed material and can open novel opportunities in variety of applications such as fuel cell, optical memory, gas sensing, energy storage systems, nanophotoelectric devices, reading–writing–erasing devices, microelectronics, flat panel displays, antibacterial coatings, military technologies, catalysis, environmental monitoring etc. Acknowledgment Dr. V. B. Patil would like to thank DAE-BRNS, for financial support through the scheme no. 2010/37P/45/BRNS/1442. References [1] M. Laus, O. Francescangeli, F. Sandrolini, New hybrid nanocomposites based on an organophilic clay and poly(styrene-b-butadiene) copolymers, J. Mater. Res. 12 (1997) 3134. [2] P. Couvreur, C. Vauthier, Polyalkylcyanoacrylate nanoparticles as drug carrier: present state perspectives, J. Controlled Release 17 (1991) 187. [3] I.N. Lews, Chemical catalysis by colloids and clusters, Chem. Rev. 93 (1993) 2693. [4] G.D. Khuspe, S.T. Navale, D.K. Bandgar, R.D. Sakhare, M.A. Chougule, SnO2 nanoparticles-modified polyaniline films as highly selective, sensitive, reproducible and stable ammonia sensors, Electron. Mater. Lett. 10 (1) (2014) 191–197. [5] G.A. Ozin, Nanochemistry: synthesis in diminishing dimensions, Adv. Mater. 4 (1992) 612. [6] M.J. MacLachlan, I. Manners, G.A. Ozin, New (inter) faces: polymers and inorganic materials, Adv. Mater. 12 (2000) 675. [7] C. Sanchez, B. Julian, P. Belleville, M. Popall, Applications of hybrid organic–inorganic nanocomposite, J. Mater. Chem. 15 (2005) 3559. [8] R. Gangopadhyay, A. De, Conducting polymer nanocomposites: a brief overview, Chem. Mater. 12 (2000) 608. [9] C.O. Oriakhi, Polymer nanocomposition approach to advanced materials, J. Chem. Educ. 77 (2000) 1138. [10] F. Yakuphanoglu, Photovoltaic properties of hybrid organic/inorganic semiconductor photodiode, Synth. Metals 157 (2007) 859. [11] W.E. Mahmoud aleed, M. Hafez, N.A. El-Aal, F. El Tantawy, The effect of nanoscale vanadium pentoxide on the electrical and mechanical properties of poly(vinyl alcohol), J. Polym. Int. 57 (2008) 35. [12] A.T. Mane, S.T. Navale, S. Sen, D.K. Aswal, S.K. Gupta, V.B. Patil, Nitrogen dioxide (NO2 ) sensing performance of p-polypyrrole/n-tungsten oxide hybrid nanocomposites at room temperature, Org. Elect. 16 (2015) 195.

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