polyaniline nanocomposite thin films prepared by aerosol …ajase-bd.weebly.com/uploads/1/3/4/5/13455174/ajase_8.3.pdf · 2019-11-23 · films prepared by aerosol assisted dielectric

Asian Journal of Applied Science and Engineering ISSN 2305-915X(p); 2307-9584(e)

Asian Business Consortium | AJASE ● Aug 2014 ● Vol 3 ● Issue 8 Page 25

Characteristic of Silver\ polyaniline nanocomposite

thin films prepared by aerosol assisted dielectric

barrier discharge plasma jet polymerization

Hammad R. Humud1, Ahmad Kudhair Abass

2, Zahraa Wheeb

3

1Department of Physics, College of Science, University of Baghdad, Iraq

2,3Department of Physics, College of Science, University of Waist, Iraq

ARTICLE INFO ABSTRACT Volume 3 Number 4/2014 Issue 8 DOI: 10.15590/ajase/ Received: Sep 07, 2014 Accepted: Sep 12, 2014 Revised: Sep 14, 2014 Published: Sep 19, 2014 E-mail for correspondence: [email protected]

Silver polyanilinenano composite thin films deposited on glass substrates by in-situ aerosol assisted plasma polymerization at atmospheric pressure and room temperature, from aniline monomer in the presence of different concentrations of Ag nanoparticles. The silver nanoparticle with 50nm average particles size was prepared in our laboratory by electrical exploding weir method. Metal polymer nanocomposite thin films were characterized by UV-VIS, XRD, FTIR, AFM and SEM the optical studies show that the energy band gap will be different according to the silver polyaniline concentration. The XRD pattern indicates that the synthesized Ag-polyaniline nanocomposite is amorphous. FTIR reveals the presence of silver nanoparticle embedded into polyaniline.AFM and SEM surface images show that the silver nanoparticle impeded homogenously inside the polyaniline matrices. It can be concluded that it can be preparedAg\ polyanilinenano composite thin films by aerosol assisted dielectric barrier discharge DBD plasma jet polymerization and control the optical energy band gap irregulars by controlling the experiment variables. Key words: Silver polyanilinenano composite, aerosol assisted plasma polymerization, plasma jet

Source of Support: Nil, Conflict of Interest: Declared.

How to Cite: Humud HR, Abass AK and Wheeb Z. 2014. Characteristic of Silver\ polyaniline nanocomposite thin films prepared by aerosol assisted dielectric barrier discharge plasma jet polymerization Asian Journal of Applied

Science and Engineering, 3, 25-33.

This article is is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License. Attribution-NonCommercial (CC BY-NC) license lets others remix, tweak, and build upon work non-commercially, and although the new works must also acknowledge & be non-commercial.

INTRODUCTION

n several last year plasma polymers containing small metal, particles have been intensively studied due to their novel physical properties and promising application. I

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In this respect the structure and essential characteristic of films obtained by plasma polymerization of the polyaniline silver nanocomposite by the aerosol assisted plasma jet at atmospheric pressure. Polymers are insulators, but a new class of polymers was synthesized two and half decades ago that can conduct electric current. Plasma is often done by means of a dielectric barrier discharge (DBD). This is mostly worked out through a parallel plate electrode system. At least one of the electrode surfaces is covered with a dielectric. A carrier gas is brought between the two electrodes to be ionized for creating the discharge. Commonly used carrier gasses are inert gasses like helium, argon and nitrogen. The layer that is deposited originates from a precursor that is injected into plasma. Different precursor systems can be used: gasses, liquid vapors, and aerosols. Most often gasses and/or aerosols are used. This work deals with the atmospheric plasma jet deposition technique using aerosols. Plasma can split up molecular particles. Only elements and components with a low molecular weight can be utilized as gas precursor in plasma depositing applications. As there are much more liquid than gaseous precursors available, the number of possible material is clearly higher when working with aerosol precursors. Various nanoparticles and monomer systems can be simultaneously applied in aerosol form during plasma treatment. So working with aerosol precursors offers more flexibility. Different techniques can be used for aerosol production: ultrasonic piezoelectric technology and nozzles. Nozzles are the most stable system in case of constant production. Important parameters are the distribution of the drop size and the average drop diameter. The smaller the drop size, the higher the interaction precursor-plasma (Van Hove, 2007). In this work special nozzle was used to generate an aerosol. One of the main challenges in preparation high-performancenano metal particle/polymer composite thin films is achieving homogeneous dispersion of the nanoparticles in a polymer matrix. This criterion is vital because good dispersion of the individual nanoparticles in a polymer matrix is the basis for obtaining promising material properties (E.P. Giannelis, 1996). There are, three most widely techniques for preparation metal nanocomposite these techniques are; solution blending, in-situ polymerization and melt compounding method. For the solution blending method, nanoparticles are usually dispersed in a solvent, mixed with polymer and then the composites can be recovered by precipitating or casting a film (M. Lebron-Colon, etal, 2010;Chen Chen, 2011). The choice of solvent used is made based on the solubility of the polymer, and ultra-sonication was usually involved (X. Zhan et al, 2003;H.G. Jeon et al, 1998; C.R. Tseng et al, 2001). Limitation of this method is due to the large volume of organic solvent that is usually involved, which is costly and maybe environmentally hazardous. In-situ polymerization it is a developing technique for composite thin films preparation. The method starts by dispersing nanoparticle in monomer followed by polymerizing the monomers (M. Moniruzzaman and K.I. Winey2006; J.W. Yang et al, 2004). The in-situ polymerization process it can enable] covalent bonding between the polymer macromolecules and the nanoparticle surfaces (L. Jin et al, 1998; A.A. Koval'chuk et al, 2008). The melt blending process generally involves the melting of polymer pellets to form a viscous liquid. The nanoparticles are dispersed into the polymer matrix by high shear rate combined with diffusion at high temperature (Z.J. Jiaet al, 1999; K.F. Fu et al, 2001; M.H. Liuet al, 2009). The problem with this method is that good dispersion is usually hard to obtain. Nanocomposites formed by metal nanoparticles (NPs) dispersed in electrically conducting polymers, such as polyaniline or polythiophene, have received much attention. These hybrid nano-materials are expected to display several synergistic properties between the polymer and the metal nanoparticles, making them potential candidates for application in several



fields such as catalysis, biosensors, memory devices, sensors, photovoltaic devices and solar cells. The synthesis of homogeneous and reproducible metal nanoparticles/conducting polymers nanocomposite samples is not insignificant, and efforts have been done to the development of novel and versatile synthetic routes to this material. In this work, the in-situ polymerization process was used to prepare Agpolyanilinenanocomposite thin films. Selected polyaniline among different conducting polymers because of its simple synthesis procedure, good environmental and thermal stability, low-costprice, high conductivity and which also exhibits good electrical, optical, magnetic and chemical properties (T.X. Liu et al, 2004; C.M. Gupta and S.S. Umare, 1992).The motivation behind this investigation is to study the characteristic change in optical properties of polyaniline when silver nanoparticles are embedded in it. Here polyaniline plays the role of a dielectric medium. Silver nanoparticles are of current importance because of its easy preparation process and unique optical, electrical and thermal properties. These nanoparticles are best suited for application in surface plasmon optics, photonics, photography, surface enhanced Raman scattering, catalysis, data storage, etc. Improvement of conductivity of polyaniline will be very good as silver is a good conductor (R.C. Jinet al. 2001). Hence the synthesis of polyaniline–silver nanoparticle composite is receiving wide attention.

EXPERIMENTAL WORK

Silver polyanilinenano composite has been prepared for the first time by aerosol assisted plasma polymerization. Thin films were prepared by dielectric barrier discharge plasma jet (Hammad R. Humudet al. 2014).The thin films were deposited on glass substrates. Pure aniline monomer obtained from the Chemical Department our Collage was used as the organic precursor and thesilver nanoparticle prepared in our laboratory by electrical exploding weir method with average particle size 50 nm (Hammad R. Humudet al. 2014). Figure(1) schematic diagram for the non-equilibrium atmospheric pressure plasma Silver polyaniline nanocomposite thin films preparation. Argon gas with flow rate of of 1 L/min passes through the nebuliserthat contains a mixture of silver nanoparticles and aniline. The mixture convert to aerosol, this aerosol was guided by the Ar gas to the plasma jet. the plasma was ignited by using an electric source at a fixed frequency of 28.0 kHzand 7.5 kvoltpeak to peak. The plasma was generated downstream to the substrate that was positioned atsuitable distance from the plasma torch end(the end of the plasma tube). The film deposition was carried out for 5min under 1l/min gas flow rateand a known substratedistancefrom

the plasma torch endat roomtemperature. The substrate moved on the x and y direction mechanically for the purpose of obtaining a homogeneous films thickness a long the substrate area.

Figure (1): Schematic diagram for non-

equilibrium atmospheric pressure

(DBD) plasma polymerization

experimental set-up



The Film thickness was measured using an optical interferometer, method. A double –beam UV-VIS-NIR 210A Spectrophotometer was used to measure the absorption of Silver polyaniline nanocomposite thin films which deposited at different conditions in the range of (200-1200) nm. The background correction was taken for each scan. The absorption data with films thickness can be used to calculate absorption coefficients of the films at different Wave length,which have been used to determine the energy band gap Eg.FT-IR spectra were recorded by using solid KBr discs and testing all samples by Shimadzu Co. FT-IR 8000 series Fourier transform, infrared spectrophotometer from a wavelength range 400–4000 cm-1 under identical conditions .The morphological surface analysis is carried out by AFM and SEMmicroscope. The structure is analyzed by X-ray diffractometer system.The source of radiation isCu- kα with wavelength λ =1.5406Å. The scanning angle 2θ is varied in the range of 10 – 80 degree with speed of 5 deg/min.

RESULTS AND DISCUSSION

A. FTIR analysis: The FTIR spectra ofpolyaniline as pure and silverpolyanilinenanocompositethin filmsprepared by aerosol assisted dielectric barrier discharge plasmajet with different silver aniline weight mixing ratioshown in Figure (2).

a

b

c Figure (2): FT-IR spectra a for pure polyaniline thin films, b and c for silver polyanilinenano

composite where silver concentration 10%and 4% respectively

The FTIR absorption bands for polyaniline and silverpolyanilinenanocomposite thin films are given in table 1. Table (1)and Figures(3) show some vibration bands at 3440, 2920, 1629,



1347.7,and 1153.3 etc. These values arecharacteristic of polyaniline chain and are in agreement with theoretical predictions(R.Kostie, 1992). It is clear from the table that there is a shift in N–H stretching and C–N stretching bands in the silverpolyanilinenanocomposite thin films. Thisshift is an indication that silver nanoparticlescause a modification inthe structure of the plasma polymerized aniline samples.

Table 1: FT- I R common band and peaks forpurepolyaniline, and silver polyanilinenano composite for 10 and 4% silver concentrations

B - Optical energy bandgap The optical energy band gap values (Egopt) for silver polyanilinenano composite thin films have been determined by plotting the relations of (αhυ)2 versus hυ(eV) for direct energy gap transition as shown in Figure (3). This figure shows the Egfor silver polyanilinenano composite thin films deposited on a glass substrate at silver aniline weight concentration (10%, 8%, 6% and 4%) at room temperature. Increasing the percentage of the weight of the silver in the nanocomposite thin films lead to decreases the optical energy gap from 2.68 eV for 4% silver concentration to 2.35 eV for 10% concentration, where energy band gap for a pure polyaniline prepared by plasma polymerization was 2.7eV.The optical band gap values were falling within the semiconductor region of Eg (K. Gupta et al, 2010).The reduction in the optical band gap is probably due to the modification of the polymer structure. Improvement of conductivity of silver polyanilinenano composite will also be because the

silver is a good conductor. The addition of metal to polymer induces a structural ordering of the polymers. There are signatures supporting these changes in the FTIR and UV- Vis spectra, so the optical band gaps vary with silver concentration.

Figur (3):The varaition of (αhʋ) 2 with photon

energy (hʋ) for the silver polyanilinenano

composite thin films deposited at room temperature and different silver nano particle concentration



C: Structural characterization Figure (3) shows the x-ray diffraction pattern of the as-deposited 10% silver polyanilinenano composite thin films. From the x-ray diffraction pattern it is clearly indicated that the thin films have an amorphous structure. Plasma polymer has short chains of building units and a high degree of cross-linking. Plasma polymers are usually amorphous in nature, where made of short chains of monomers characterized by a high degree of cross-linking and dangling bonds.

Figure (4): XRD patternfor 10% silver polyaniline thin films.

D: Surface morphology The surface morphology of the pure polyaniline and 10% silver polyanilinenano composite films were examined by AFM. The surface roughness of plasma polymerized pure polyaniline thin films 2.3 Å and for 10% silver polyanilne thin films was 4.4 Å. The low surface roughness of plasma polymerized silver polyanilinenano composite confirms that the technique of plasma polymerization can be employed to produce extremely smooth films with very small surface roughness when compared to films prepared by other techniques. It is clear that the silver nanoparticles are uniformly distributed within the scanning area. Figures (5a and b) represent the 3-D and 2-D AFM photos of the pure polyaniline thin films surface and c shows the granuality distribution chart. The average diameters of clusters are 103 nm. Figures (6 a and b) represent the 3-D and 2-D AFM photos of the 10% silver polyaniline thin films surface and c shows the granularity distribution chart. The average diameter of clusters was 100nm. Figure 7(a, b and c) shows the TEM images for the 4%, 8% and 10% silver/polyanilinenano composite, respectively. As shown in TEM images the silver particles black spots are nearly spherical shaped and uniformly dispersed in the polyaniline matrix. The surface partials distribution density of Ag nanoparticles dispersed in the polyaniline matrix increased with increasing silver concentration. The formation of relatively large particles with higher surface particles distribution density in the case of l0% silver polyanilinenano composite could be attributed to the silver migration and agglomeration. The migration and agglomeration of silver particles might be driven by the instability of silver atoms due to their high surface free energy (A. Choudhury, 2009).From Figure 7(c)it note that increasing of silver particles concentration cause presence of micro-cracking in the l0% silver polyanilinenano composite thin films.



Figure 5: AFM photographs of plasma polymerized pure aniline thin films surface; a) 3D

view, b) 2 D view, and c) the granularity distribution chart

Figure 6: AFM photographs of plasma polymerized 10% silver polyanilinenano composite

thin films surface; a) 3D view, b) 2 D view, and c) the granularity distribution chart



Figure 7: TEM images for a) 4%, b) 8% and c) 10% silver/polyanilinenanocomposite.

This arises from different thermal expansion coefficient between polyaniline and silver particles. From this, it can conclude that there is a limit for the silver concentration over these limits the silver polyanilinenano composite thin films loses its important physical properties due to the appearance of micro-crack.

CONCLUSIONS

The technique of plasma polymerization can be employed to produce extremely smooth silver polyanilinenano composite thin films with very small surface roughness when compared to films prepared by other techniques. The silver particles are uniformly distributed in the polyaniline matrix. Increasing the weight percentage of the silver in the nanocomposite thin films lead to decreases the optical energy bandgap,and modifies the polymer structure. There is a limit for the silver concentration where over this limits the silver polyanilinenano composite thin films loses its important physical properties due to the appearance of micro-crack.

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A.A. Koval'chuk, A.N. Shchegolikhin, V.G. Shevchenko, P.M. Nedorezova, A.N. Klyamkina, A.M. Aladyshev, Macromolecules, 41 (2008) 3149-3156.

C.M. Gupta, S.S. Umare, Macromolecules 25 (1992) 138. Chen Chen, The Manufacture of Polymer Nanocomposite Materials Using Supercritical Carbon

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polyaniline nanocomposite thin films prepared by aerosol …ajase-bd.weebly.com/uploads/1/3/4/5/13455174/ajase_8.3.pdf · 2019-11-23 · films prepared by aerosol assisted dielectric