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The Atomic Energy Organization of Iran (AEOI) A-10-1-20-a7ae28d

The Atomic Energy Organization of Iran (AEOI) A-10-1-20-a7ae28d

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Published by Constitutionalist
Atomic Energy Organization of Iran - AEOI Iran's Nuclear Program - Reports in Persian with some English. Note: Sources are from Western Publications. They have much of what they need from Western sources to create nuclear terror.
Atomic Energy Organization of Iran - AEOI Iran's Nuclear Program - Reports in Persian with some English. Note: Sources are from Western Publications. They have much of what they need from Western sources to create nuclear terror.

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Categories:Types, Research
Published by: Constitutionalist on Aug 07, 2012
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07/03/2013

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J. of Nuclear Sci. and Tech.
 -
No. 50, pp. 80-84, 2010
Polymethylmethacrylate/Silver Nanocomposite Prepared by
γ
-Ray
A. Akhavan
1
, N. Sheikh*
2
, R. Beteshobabrud
2
 
1- Chemistry Department, Tarbiat Modares University, P.O. Box: 14155-4838, Tehran - Iran2- Radiation Applications Research School, Nuclear Science and Technology Research Institute, AEOI, P.O. Box: 11365-3486, Tehran - Iran
Abstract:
Polymethylmethacrylate-silver (PMMA/Ag) nanocomposite is synthesized by irradiating thesolution of silver ions in methylmethacrylate monomer by
γ
-ray. In this method, polymerization of themethylmethacrylate monomer and the silver ion reduction occurred simultaneously. Optical properties of the PMMA/Ag solutions are investigated using UV-Vis spectroscopy. The structural characterizations of the PMMA/Ag nanocomposite are determined by FTIR spectroscopy XRD, and SEM measurements. TheSEM image shows that the Ag nanoparticles disperse in the PMMA matrix with a relatively uniformdistribution. The antibacterial studies show that the PMMA/Ag nanocomposite is antibacterial against E.coli, as a model for gram-negative bacteria.
 Keywords:
 Polymethylmethacrylate, Silver, Nanocomposite,
γ
-Ray
1-Introduction
Metal-polymer nanocomposites haveattracted considerable amount of interests inrecent years. They have a wide range of applications in nonlinear optical materials [1],conductive composites [2] and nanoscaleelectronics [3]. In general, metal polymernanocomposites are prepared by homogenizingpolymer and nanometer metal powder [4],post-heating or calcining metal ion containingpolymers [5 and 6], migrating the vapor of 
particles of noble metals into polymer matrices[7], and reducing metal ions in polymer gels [8].
 PMMA/Ag nanocomposites are speciallyused in medical and dental devices for theirantibacterial effects which are due to thepresence of silver nanoparticles [9, 10]. It hasbeen shown that morphology, particle sizedistribution, stability and properties of silvernanoparticles as well as correspondingnanocomposites are strongly dependent on themethod of preparation and specificexperimental conditions. Many routes havebeen reported to synthesis silver nanoparticlesin PMMA [11, 12]. In these methods, thepolymerization of organic monomer isperformed initially and then the silver ions,dispersed in the polymer matrix, are reduced tozerovalent state by a reducing agent or by heattreatment. This, results in a wide distributionand poor dispersion of metal particles in thepolymer matrix.
*email: nasheikh@aeoi.org.ir
Recently, the radiochemical method has beenreported to synthesize metal polymernanocomposites due to its unique advantages.In this method the reduction of metal ions andpolymerization of monomer can be carried outsimultaneously under the normal pressure atroom temperature without using excessivereduction of agents. This matter inducesformation of homogenously dispersed metalnanoparticles in polymer matrix. Althoughseveral papers have been published on theradiation-induced synthesis of metal polymernanocomposites [13, 14], to our knowledge,there is no any report on the use of 
γ
-irradiationto produce PMMA/Ag nanocomposite. In thispaper, we employed
γ
-irradiation to producePMMA/Ag nanocomposite in which thereduction of silver ions and the polymerizationof methyl- methacrylate monomer occursimultaneously at an appropriate applied doseof 
γ
-ray.
2- Experimental
 2-1 Materials and method 
All chemicals were of analytical gradeprovided by Merck Company. Distilled waterfor sample preparation made by GFL Co. waterpurification system. Gamma irradiation was
performed in
60
Co radiation facility, Gammacell-220, with a dose rate of 18.6Gy/min calibrated byFricke dosimeter.
 
Data of Receive: 1387/11/8 Data of Admission: 1388/6/19
 
 
 
 2-2 Preparation and characterization
Methyl-methacrylate monomer was distilledunder the vacuum to remove inhibitors. Then,the homogenous solution containing methyl-methacrylate monomer, isopropanol andAgNO
3
(0.1M) with 4:2:1 volume ratio wasprepared in a glass vial with 20ml volume,purged with nitrogen for 20min to removeoxygen, and then exposed to 5kGy
γ
-ray(4hours and 48minutes, irradiation time) atroom temperature. After the irradiation, atransparent, greenish, gel like material wasobtained which was dried in the vacuumedoven and then characterized. A neat PMMAcomposite without Ag NPs was also preparedfor the comparison. The FT-IR spectra of thesamples, prepared in KBr pellets, were obtainedusing a Bruker IFS 45 spectrophotometer in the400-4000cm
-1
range. The X-ray diffraction(XRD) pattern of the sample was recorded by aHolland Philips Xpert X-ray diffractometer(CuKa). Scanning electron microscopy (SEM)image of product was taken on a Philips XL30microscope. The UV–Vis spectrum of thediluted solution of PMMA/Ag was recordedusing a Novaspec III Biochrom Ltd,spectrophotometer from 330 to 800nm.
 2-3 Antibacterial studies
To examine the antibacterial effect of prepared PMMA/Ag nanocomposite on Gramnegative bacteria, E.coli ATCC 25922 werecultured on LB agar plates supplemented withspecimens, with a total surface area of 4cm
2
.Sample free LB plates, cultured under the sameconditions, were used as a controlling systemcontrol. The plates were incubated for 24hoursat 37
º
C then the number of colonies wascounted.
3- Results and Discussion
PMMA/Ag nanocomposite is simplyprepared by irradiating the solution containingsilver ions, isopropyl alcohol andmethylmethacrylate monomer. The radiolysisof monomer solution results in the formation of radicals, which then initiate the polymerizationof MMA to form polymer chains. On the otherhand, the homodispersed silver ions arereduced to silver atoms by reductive particlessuch as solvated electrons and isopropylradicals in the solution.Then these silver atoms undergo furthergrowing to progressively larger clusters leadingto formation of nanometer silver particles [15].As the polymerization of MMA is quicker thanthe reduction of silver ions the viscosity of thereaction system, resulting from the formation of polymer chains, increases. This effect as wellas the availability of carboxylate functionalgroups of PMMA with a high affinity for theAg
+
can limit the aggregation of silver particlesand make them dispersed in polymer matrixhomogeneously (scheme 1).The possible physicochemical interactionbetween the silver nanoparticles and PMMAwas tested by FT-IR. It is known that the shiftof the peaks toward the lower wave numbers inthe FT-IR spectrum is an indicator of thechemical bonding of surfactant onto thenanoparticle surface [16]. The spectra of theneat PMMA and the PMMA/Ag composite areshown in Fig. 1. As can be seen all thecharacteristic absorption peaks of standardPMMA including: the sharp absorption at1728cm
-1
(C=O groups), the peaks at 1147 and1193cm
-1
(C–H deformations), and 1244 and1272cm
-1
peaks (C–C–O stretch coupled withC–O stretch), are observed in neat and PMMAstabilized Ag nanoparticles indicating theoccurrence of MMA polymerization by
γ
-ray.
Scheme 1
. A proposal mechanism for the formation of PMMA/Ag nanocomposite.
 
CH
3
CCH
2
COCH
3
OCH
3
CCH
2
COCH
3
OnH
2
Oe
aq
HOH++OHCH
3
CHCH
3
OHCH
3
CCH
3
OHH
2
OAge
aq
+Ag
0
AgCH
3
CCH
3
OAg
0
HnAg
0
Ag
2
Ag
n
AgNPsCH
3
CCH
2
COCH
3
OnAgNPsCH
3
CCH
2
COCH
3
OCH
3
CCOOCH
3
n+++++++AgNPsCH
3
CCH
3
OH
gamma raygamma ray
H
3
O+H
2
+...
 
Polymethylmethacrylate/Silver Nanocomposite
. . .
 
Fig. 1.
FT-IR spectrum of the a) neat PMMA b)PMMA/Ag nanocomposite.
 In addition, there are no noticeable shifts inthe peaks (in terms of wave numbers) betweenthe neat PMMA and the PMMA stabilized Agnanoparticles, demonstrating that theinteraction between the Ag nanoparticles andthe PMMA probably occurs through a weak physical force rather than a strong chemicalbonding [16]. This observation may alsoindicate that most of the PMMA molecules
areeither physically linked to the nanoparticles or arepresent without any contact with thenanoparticles. Further information is needed toprobe the essence of the physicochemicalinteraction between PMMA and silvernanoparticles.
 UV-Vis absorption spectra are quite sensitiveto the formation of Ag NPs because theposition of the surface plasmon absorption peak depends on their particle diameters and shapes[17]. Therefore UV-Vis absorption spectra of the neat PMMA and PMMA/Ag were obtained(Fig. 2). In comparison to neat PMMA, thePMMA/Ag composite shows an absorptionband at about 428nm, which is consistent withthe established absorbance wavelength of silvernanoparticles [9].To determine the size and distribution of thesilver nanoparticles, scanning electronmicroscopy was performed. The SEMmicrograph of PMMA/Ag composite (Fig. 3)indicates that Ag particles with mean size of 90±14.4nm disperse in the PMMA matrix witha relatively uniform distribution. This confirmsthat when reduction of silver ions and thepolymerization of monomer take placesimultaneously during irradiation, the silvernanoparticles are homogeneously dispersed inthe polymer matrix.
Fig. 2.
UV-Vis absorption spectra of neat PMMA andPMMA/Ag nanocomposite.
 
Fig. 3.
SEM microgragh of PMMA/Ag nanocompositeand size distribution of the Ag nanoparticles.
To carry out further investigation of the sizeand structure of the silver nanoparticles inPMMA matrix, the XRD patterns of thePMMA and the PMMA/Ag composite are alsoobtained (Fig. 4). The PMMA/Ag compositedisplays a typical amorphous PMMA patternand does not show any diffraction peak relatingto crystal structure of Ag. This may be
100.095.0 90.085.080.075.070.065.0 60.055.050.04000 3000 2000 1500 1000 500
WAVENUMBER CM
-1
 
   T   R   A   N   S   M   I   T   T   A   N   C   E   (   %   )
05101520253068 75 86 96 105 116
Size (nm)
   F  r  e  q  u  e  n  c  y   (   %   )
330 430 530 630 730
b
   A   b  s  o  r   b  a  n  c  e
Wavelength (nm)

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