Research Article Chemical Polymerization Kinetics …downloads.hindawi.com/journals/ijps/2014/520910.pdfResearch Article Chemical Polymerization Kinetics of Poly-O-Phenylenediamine

Research ArticleChemical Polymerization Kinetics of Poly-O-Phenylenediamineand Characterization of the Obtained Polymer in AqueousHydrochloric Acid Solution Using K2Cr2O7 as Oxidizing Agent

S M Sayyah1 A B Khaliel1 Ahmed A Aboud2 and S M Mohamed1

1 Polymer Research Laboratory Chemistry Department Faculty of Science Beni-Suef University Beni-Suef 62514 Egypt2 Physics Department Faculty of Science Beni-Suef University Beni-Suef 62514 Egypt

Correspondence should be addressed to S M Sayyah smsayyahhotmailcom

Received 18 January 2014 Revised 25 March 2014 Accepted 29 April 2014 Published 12 June 2014

Academic Editor Yulin Deng

Copyright copy 2014 S M Sayyah et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

The oxidative chemical polymerization of o-phenylenediamine (OPDA) was studied in hydrochloric acid solution using potassiumdichromate as oxidant at 5∘C The effects of potassium dichromate hydrochloric acid and monomer concentrations on thepolymerization reaction were investigated The order of reaction with respect to potassium dichromate hydrochloric acid andmonomer concentration was found to be 1011 0954 and 1045 respectively Also the effect of temperature on the polymerizationrate was studied and the apparent activation energy of the polymerization reaction was found to be 63658 kJmol The obtainedpolymer was characterized using XPS IR UV-visible and elemental analysis The surface morphology of the obtained polymerswas characterized by X-ray diffraction and transmission electron microscopy (TEM) The TGA analysis was used to confirm theproposed structure and number of water molecules in each polymeric chain unit The ac conductivity (120590ac) of (POPDA) wasinvestigated as a function of frequency and temperature The ac conductivity was interpreted as a power law of frequency Thefrequency exponent (s) was found to be less than unity and decreased with the increase of temperature which confirms that thecorrelated barrier hopping model was the dominant charge transport mechanism

1 Introduction

Polyaniline as an electrically conductive polymer hasattracted considerable attention because of its excellentenvironmental stability in the electroconducting form andelectrical and optical properties [1 2] It has various potentialapplications in many high performance devices [3ndash9] Acommon feature of conducting polymer is conjugationof 120587-electrons extending over the length of the polymerbackbone [10] Polymerization of conducting polymermay be performed by chemical [11] or electrochemical[12] methods Various chemical oxidizing agents such aspotassium dichromate [13] potassium iodate [14] hydrogenperoxide [15] ferric chloride or ammonium persulphatewere used [16] The applications of polyaniline are limiteddue to its poor processability [17] which is true for mostconducting polymers Several studies have been done in order

to improve the solubility of polyaniline among them is usingfunctionalized protonic acids as dopant like p-toluene-sulphonic acid octyl-benzene-sulphonic acid dodecylbenzene-sulphonic acid [18] poly(styrene) sulphonic acid[19] and phosphoric acid esters [20] An alternative methodto obtain soluble conductive polymers is the polymerizationof aniline derivatives The studied aniline derivatives arealkyloxy hydroxy and chloroaniline and substitution atthe nitrogen atom was reported by Sayyah et al [21ndash24] toimprove the solubility of polyaniline The substituted groupof aniline affects not only the polymerization reaction butalso the properties of the polymer obtained The kinetics ofchemical polymerization of 3-methylaniline 3-chloroaniline3-hydroxyaniline 3-methoxyaniline and N-methyl anilinein hydrochloric acid solution using sodium dichromate asoxidant and characterization of the polymer obtained byIR UV-visible and elemental analysis X-ray diffraction

Hindawi Publishing CorporationInternational Journal of Polymer ScienceVolume 2014 Article ID 520910 16 pageshttpdxdoiorg1011552014520910

2 International Journal of Polymer Science

scanning electron microscopy TGA-DTA analysis and acconductivity have been investigated by Sayyah et al [25ndash28]

The present work intends to study the kinetics of theoxidative chemical polymerization of o-phenylenediamine inaqueous HCl medium and potassium dichromate as oxidantThe obtained polymer is characterized by XPS IR UV-visible TGA elemental analysis X-ray transmission electronmicroscopy (TEM) and ac conductivity measurements

2 Experimental

21Materials O-phenylenediaminewas provided byAldrichchemical Co (Germany) Concentrated hydrochloric acidpure grade product was provided by El-Nasr pharmaceuticalchemical Co Egypt Potassium dichromate was providedby Sigma-Aldrich chemical Co (Germany) Doubly distilledwater was used to prepare all the solutions needed in thekinetic studies

22 Oxidative Aqueous Polymerization of O-Phenylene-diamine Monomer The polymerization reaction was carriedout in a well-stoppered conical flask of 250mL capacityaddition of OPDA amount in 25mL HCl of known molaritywas followed by the addition of the required amount ofpotassium dichromate as oxidant in water (25mL) to thereaction mixture The orders of addition of substances werekept constant in all the performed experiments The stop-pered conical flasks were then placed in an automaticallycontrolled thermostat at the required temperatureThe flaskswere shaken (15 shakings10 s15min) by using an automaticshaker The flasks were filtrated using a Buchner funnel thenthe obtained polymer was washed with distilled water andfinally dried till constant weight in vacuum oven at 60∘C

23 Elemental Analysis Infrared andUltraviolet SpectroscopyThe carbon hydrogen and nitrogen contents of the preparedpolymer were carried out in the microanalytical laboratoryat Cairo University by using oxygen flask combustion and adosimat E415 titrator (Switzerland)

The infrared spectroscopic analysis of the preparedpolymer was carried out in the microanalytical laboratoryat Cairo University by using a Shimadzu FTIR-430 Jascospectrophotometer and KBr disc technique

The ultraviolet-visible absorption spectra of themonomer and the prepared polymer sample were measuredusing Shimadzu UV spectrophotometer (M 160 PC)at room temperature in the range 200ndash400 nm usingdimethylformamide as a solvent and reference

24 X-Ray Photoelectron Spectroscopy (XPS) An XPS spec-trum was obtained on XPS-thermo scientific spectrometerModel K-ALDH inCentral metallurgical research and devel-opment institute (CMRDI) Polymer was mounted on a stan-dard sample holder using double-sided adhesive tape Surveyand XPS spectra were obtained with Al K120572 monochromaticX-ray with the resolution of 07 eV

25 Thermal Gravimetric Analysis (TGA) Transmission Elec-tron Microscopy (TEM) and X-Ray Analysis Thermal gravi-metric analysis (TGA) of the polymer sample was performedusing a SHIMADZU DT-30 thermal analyzer The weightloss was measured from ambient temperature up to 600∘C atrate of 20∘Cmin to determine the rate of degradation of thepolymer

The X-ray diffractometer type Philips 1976 Model 1390was used to investigate the phase structure of the polymerpowder under the following condition which kept constantduring the analysis processes Cu X-ray tube scan speed =8min current = 30mA voltage = 40 kv and preset time =10 s

The inner cavity and wall thickness of the preparedpolymer were investigated using transmission electronmicroscopy (TEM) JEOL JEM-1200 EX ^ (Japan)

26 Conductivity Measurements The ac conductivity wasmeasured using Philips RCL bridge (digital and computer-ized) at a frequency range 01ndash100 kHz and over temperaturerange 30ndash80∘CThe temperature was controlled by the use ofa double wound electric oven

The ac conductivity 120590ac value was calculated using therelation

120590ac = 12057610158401015840

120596120576119900 (1)

where 120596 = 2120587119891 and 119891 is the applied frequency

3 Results and Discussion

31 Determination of the Optimum Polymerization Condi-tions To optimize the condition for polymerization of o-phenylenediamine the concentrations of potassium dichro-mate hydrochloric acid and monomer were investigatedwith keeping the total volume of the reaction mixtureconstant at 50mL

311 Effect of Potassium Dichromate Concentration Both ofthe monomer and HCl concentrations are fixed at 01Mwhile the oxidant concentrations were varied from 004 to05M at 5 plusmn 02∘C to investigate the optimum polymerizationcondition of K

2Cr2O7 The yield-time curve was represented

in Figure 1 from which it is clear that the obtained yieldincreased with the increase of K

2Cr2O7reaching maximum

value at 03M From the left part of the curve it is clearthat the polymer yield increases from 004M to 03M thendecreases from 03M to 05M This could be due to the factthat in the first part of the curve the produced initiator ionradical moieties activate the backbone and simultaneouslyproduced the o-phenylenediamine ion radical which takesplace immediately and therefore yield increases with theincrease of potassium dichromate concentration up to 03MBut in the second part of the curve the polymer yielddecreases with increasing K

2Cr2O7concentration may be

due to a high concentration of oxidant promote the formationof low molecular weight oxidation product and also degradethe product polymer which easily soluble in water [13]

International Journal of Polymer Science 3

00

04

08

12

0 02 04 06

Yiel

d (g

m)

K2Cr2O7 (mol)

Figure 1 Yield-K2

Cr2

O7

concentration effect on the aqueousoxidative polymerization of poly-o-phenylenediamine (POPDA)

0 02 04 0600

05

10

15

20

Yiel

d (g

m)

HCl (mol)

Figure 2 Yield-HCl concentration effect on the aqueous oxidativepolymerization of poly-o-phenylenediamine (POPDA)

312 Effect of HCl Concentration The effect of HCl concen-tration on the aqueous oxidative polymerization of OPDAwas investigated using constant concentration of K

2Cr2O7

at 03M and monomer concentration at 01M and usingdifferent concentration of HCl at 5 plusmn 02∘C The yield-timedata was represented in Figure 2 from which it is clear thatthe obtained yield increases in the acid concentration rangefrom 004 to 02 then decreases gradually up to 05M Thisbehavior may be due to at higher concentration of HCl thedegradation of the polymer in the early stages of the reactionwhich may be due to the hydrolysis of polyemeraldinechain [13]

313 Effect of O-Phenylenediamine Concentration The effectof monomer concentration on the polymerization efficiencywas investigated in the range ofmonomer concentration from002 to 05M and the data was represented in Figure 3 fromwhich it is clear that the optimum yield formation is obtainedat 01M of the monomer concentration

32 The Kinetic Study of the Polymerization Reaction

321 Effect of Potassium Dichromate Concentration Theaqueous polymerization of OPDA (01mol) was carried outin 25mL of HCl solution (02mol) in the presence of 25mLpotassium dichromate as oxidant of different molarities at5∘C for different time intervals The yield-time curves were

00

04

08

12

16

0 01 02 03 04 05

Yiel

d (g

m)

Monomer (mol)

Figure 3 Yield-monomer concentration effect on the aqueousoxidative polymerization of poly-o-phenylenediamine (POPDA)

plotted for different oxidant concentrations and the data aregraphically represented in Figure 4(a) The initial and overallreaction rates were determined using the following equation

Rate (119877119894) =

119875

119881 times119872 times 119905 (2)

where 119875 is the weight of the obtained polymer 119905 is the timein seconds119872 is the molecular weight of the monomer and119881 is the reaction volume in liter

The initial and overall reaction rates of the polymerizationreaction increase with the increase of oxidant concentrationin the range between 005 and 03molL The oxidant expo-nent was determined from the relation between logarithmof the initial rate of polymerization Log (119877

119894) and logarithm

of the oxidant concentration A straight line was obtainedwhich has a slope of 1011 as represented in Figure 4(b) Thismeans that the polymerization reaction of OPDA is a first-order reaction with respect to the oxidant

322 Effect of Hydrochloric Acid Concentration The poly-merization of OPDA (01mol) in 25mL of HCl with differentmolarities was carried out by addition of 25mL potassiumdichromate (03molL) as oxidant at 5∘C for different timeintervals The concentration of the monomer and oxidantwere kept constant during the study of HCl effect on thepolymerization reactionThe experiments were carried out asdescribed in Section 22 and the yield-time curve was plottedfor each acid concentration used The data are graphicallyrepresented in Figure 5(a) from which it is clear that boththe initial and overall reaction rates of the polymerizationreaction increase with the increasing of HCl concentrationsin the range between 005 and 02molL The HCl exponentdetermined from the slope of the straight line representedin Figure 5(b) was found to be 0954 which means that thepolymerization order with respect to the HCl concentrationis a first-order reaction

323 Effect of Monomer (OPDA) Concentration The aque-ous polymerization of OPDA was carried out in 25mL ofHCl solution (02molL) in the presence of 25mL potassiumdichromate (03molL) as oxidant at 5∘C for different timeintervalsThe yield-time curvewas plotted for eachmonomer


000204060810121416

2 7 12 17 22 27

Yiel

d (g

m)

005 g molL01 g molL

02 g molL03 g molL

Time (min)

(a)

1415161718192021222324

45 47 49 51 53 55

6+

Log(Ri)

6 + Log(oxidant)

(b)

Figure 4 (a) Yield-time curve for the effect of potassium dichromate concentration on the polymerization (POPDA) at different timeintervals (b) Double logarithmic plot of the initial rate and oxidant concentration of POPDA

00

02

04

06

08

10

12

14

16

Yiel

d (g

m)

005 g molL01 g molL

015 g molL02 g molL

2 7 12 17 22 27Time (min)

(a)

15

17

19

21

23

25

46 48 50 52 54

6+

Log(Ri)

6 + Log(HCl)

(b)

Figure 5 (a) Yield-time curve for the effect of HCl concentration on the aqueous oxidative polymerization of (POPDA) at different timeintervals (b) Double logarithmic plot of the initial rate and HCl concentration of POPDA

concentration used The data are graphically represented inFigure 6(a) The monomer exponent was determined fromthe slope of the straight line represented in Figure 6(b) forthe relation between log 119877

119894and logarithm of the monomer

concentrationThe slope of this linear relationship was foundto be 1045 This means that the polymerization reactionwith respect to the monomer concentration is a first-orderreaction

33 Calculation of the Thermodynamic Activation Parame-ters The polymerization of OPDA (01molL) in 25mL of02molL HCl in presence of 25mL potassium dichromate(03molL) as oxidant solution was carried out at 5 10 and15∘C for different time periods The yield-time curves weregraphically represented in Figure 7 from which it is clearthat both of the initial and overall reaction rates increase

with raising the reaction temperature The apparent acti-vation energy (119864a) of the aqueous polymerization reactionof o-phenylenediamine was calculated using the followingArrhenius equation

Log (119870) =minus119864119886

2303119877119879+ 119862 (3)

where 119870 is the rate 119877 is the universal gas constant 119879 is thereaction temperature and 119862 is constant

By plotting log 119877119894against 1119879 which gave a straight line

as shown in Figure 8 and from the slope we can calculatethe activation energy The apparent activation energy forthis system is 63658 kJmol The Enthalpy and entropy of


00

02

04

06

08

10

12

14

16

2 7 12 17 22 27

Yiel

d (g

m)

003 g molL005 g molL


Time (min)

(a)

15

17

19

21

23

25

46 48 50 52 546 + Log(monomer)

6+

Log(Ri)

(b)

Figure 6 (a) Conversion-monomermol concentration effect on the aqueous oxidative polymerization of (POPDA) at different time intervals(b) Double logarithmic plot of the initial rate and monomer concentration of POPDA

0

04

08

12

16

2

Yiel

d (g

m)

2 7 12 17 22 27Time (min)

5∘C

15∘C

10∘C

Figure 7 Yield-time curve for the effect of temperature on theaqueous oxidative polymerization of POPDA

1

12

14

16

000345 000349 000353 000357 000361

Log(

rate

)

1T (Kminus1)

Figure 8The relation between the logarithmof initial rate and (1119879)for aqueous oxidative polymerization of POPDA

02

04

06

08

000344 000348 000352 000356 00036 000364

1T (Kminus1)

log(K2T

)

Figure 9 The relation between log 1198702

119879 and 1119879 for poly-o-phenylenediamine (POPDA)

activation for the polymerization reaction can be calculatedby the calculation of119870

2from the following equation

Reaction Rate = 1198702[oxidant]1011[HCl]0954[monomer]1045

(4)

The values of 1198702at 5 10 and 15∘C were 6131 times 10minus6

1054 times 10minus5 and 1594 times 10minus5 respectively The enthalpy(Δ119867lowast) and entropy (Δ119878lowast) of activation associated with 119870

2

were calculated using Eyring equation

1198702= (

119877119879

119873ℎ) 119890Δ119878

lowast

119877

sdot 119890minusΔ119867

lowast

119877119879

(5)

where 1198702is the rate constant119873 is the Avogadrorsquos number 119877

is the universal gas constant and ℎ is planks constantBy dividing the above equation by119879 and taking its natural

logarithm we obtain the following equation

Ln(1198702119879) = ln( 119877

119873ℎ) +

Δ119878lowast

119877+minusΔ119867lowast

119877119879 (6)


Figure 9 shows the relation between 1198702119879 versus 1119879

which gives a linear relationship with (minusΔ119867lowast)119877 and inter-cept line (ln 119877119873ℎ + Δ119878lowast119877) from the slops and intercept thevalues of Δ119867lowast and Δ119878lowast were found to be 6148 kJmolminus1 and2995 Jmolminus1Kminus1 respectively

The intramolecular electron transfer steps for the oxida-tion reaction are endothermic as indicated by the value ofΔ119867lowast The contributions of Δ119867lowast and Δ119878lowast to the rate constant

seem to compensate each other This fact suggests that thefactors controlling Δ119867lowast must be closely related to those con-trolling Δ119878lowast Therefore the salvation state of the encountercompound could be important in determination of Δ119867lowastConsequently the relatively small enthalpy of activation canbe explained in terms of the formation of more solvatedcomplex

34 PolymerizationMechanism The aqueous oxidative poly-merization of o-phenylenediamine is described in the Exper-imental section and follows three steps [29]

The Initial Step Potassium dichromate in acidified aqueoussolution produces chromic acid as shown in

K2Cr2O7+H2O + 2H+ = 2K+ + 2H

2CO4 (7)

This reaction is controlled by the change in pH the orangered dichromate ions (Cr

2O7)2minus are in equilibrium with the

(HCrO4)minus in the range of pH-values between 2 and 6 but at

pH below 1 the main species is (H2CrO4) and the equilibria

can occur as follows

(HCrO4)minus

999445999468 (CrO4)2minus

+H+ K = 10minus59 (8)

(H2CrO4) 999445999468 (HCrO

4)minus

+H+ K = 41 (9)

2(HCrO4)minus

999445999468 (Cr2O7)2minus

+H2O K = 10

minus22

(10)

The chromic acid withdraws one electron from each proto-nated OPDA and probably forms a metastable complex asshown in (11)

2

NH2

Ph

Ph

N+

H3 + H2CrO4

Complex

O

O

H

H

H

H

N

N+

OH2

O+

H2

Cr(11)

The complex undergoes dissociation to form monomercation radical as shown in (12)

2

NH2

+∙

NH2 + H2CrO3 + H2OComplex(12)

Generally the initial step is rapid and may occur in shorttime 0ndash5min (autocatalytic reaction) no polymeric productis being obtained After 5min of the polymerization reactionthe polymeric products are obtained

Propagation Step This step involves the interaction betweenthe formed radical cation and the monomer to form a dimerradical cation In the case of Cr(VI) oxidation of the organiccompounds Cr(VI) is reduced to Cr(IV) first and then to


Table 1 Solubility of poly-o-phenylenediamine (POPDA) in differ-ent solvents at 20∘C

Solvent Solubility of (POPDA) in (gL)N-methyl-2-pyrrolidone Completely solubleDimethylformamide 2235Acetone 1679Methanol 1074Iso propanol 0879

Cr(III) [29] Transfer of two electrons from two monomerions radical by H

2CrO4produces para semidine salt along

with chromous acid H2Cr2O3(Cr(IV)) The intermediately

produced Cr(IV) oxidises para semidine to pernigranilinesalt (PS) at suitable low pH and the PS acts as a catalyst forconversion of OPDA to POPDA

2

NH2 NH2 NH2

+∙

NH2 + H2CrO3 + H2O

+∙

NH2 +∙

NH

Para semidine

+ H2CrO4 = (13)

NH2 NH2 NH2 NH2

+∙

N+∙

N+∙

NH2 + H2CrO3 + 6 H2 = H+∙

NH2 + 2 Cr+3 + 6 H2OPernigraniline salt

(14)

This reaction is followed by further reaction of the formeddimmer radical cations with monomer molecules to formtrimer radical cations and so on The degree of polymer-ization depends on different factors such as dichromate

concentration HCl concentration monomer concentrationand temperature By adding (7) (11) (12) (13) and (14)

2

NH2

+ K2Cr2O7 + 8H+= PS + 2K+

+ 2Cr3++ 7H2ON

+

H3 (15)

12OPDA + 5K2Cr2O7+ 34H+ = 6PS + 10Cr3+ + 10K+ + 35H

2O (16)

Termination Step Termination of the reaction occurs by theaddition of ammonium hydroxide solution in an equimolar

amount to HCl present in the reaction medium (till pH = 7)which leads to cessation of the redox reaction The reactioncould occur as follows

H H H

N N N

NH2 NH2 NH2 NH2

∙+

NH 2

(17)


Table 2 The XPS elemental analysis of poly-o-phenylenediamine (POPDA)

C N Cl O CrCalc Found Calc Found Calc Found Calc Found Calc Found5721 5611 2225 2189 705 694 318 302 1031 1011

35 Characterization of the Obtained Polymer

351 The Solubility The solubility of POPDA was investi-gated in N-methyl pyrrolidone dimethylformamide (DMF)acetone methanol iso propanol benzene hexane and chlo-roform The solubility values are listed in Table 1 The com-plete solubility was found in N-methyl pyrrolidone then inDMF2235 gL followed by acetone 167 gL then inmethanol1074 gL then followed by iso propanol 0879 gL at 20∘C butnot soluble in benzene hexane and chloroform

352 The Elemental Analysis The data obtained from ele-mental analysis using oxygen flask combustion and a dosi-mat E415 titrator shows that the found carbon content of(POPDA) is lower than the calculated value This is due tothe formation of chromium carbide during step of heatingand measuring process while the found values of nitrogenand hydrogen are 2091 and 437 respectively which are ingood agreement with the calculated one for the suggestedstructure present in Scheme 1 By measuring another sampleof the (POPDA) which was prepared by using ammoniumpersulfate as oxidant the found value of carbon is higher thansample which is prepared by using potassium dichromate asoxidant For more information about the chemical composi-tion of (POPDA) the XPS studywas conducted asmentionedunder point 352

353 X-Ray Photoelectron Spectroscopy(XPS) Characterization

(1) XPS Survey Elemental Composition X-ray photoelectronspectroscopy (XPS) is used to study the composition ofmaterials which detect elements starting from Li (119885 = 3)and higher elements Hydrogen (119885 = 1) and helium (119885 =2) cannot be detected due to the low probability of electronemission XPS survey begins from 0 to 1400 (eV) as shownin Figure 10 The XPS survey scan spectrum of the preparedpolymer shows the presence of C NO Cl andCrTheCl waspresent as doping anion in the prepared polymer Chromewas found due to the polymer prepared using potassiumdichromate as oxidant It is possible for chromium ion (Cr+3)to present between polymer chains as a sandwich-bondedC6H6ndashC6H6groups as shown in Scheme 1 and the usual

formation procedure is hydrolyzing the reactionmixturewithdilute acid which gives the cation (C

6H6)2Cr3+ [30 31]

The XPS elemental analysis of the prepared polymer isgiven in Table 2 The data shows that there is a good agree-ment with the calculated one for the suggested structurespresent in Scheme 1

(2) XPS Spectra of Poly(OPDA) Four main peaks wereobtained for C1s spectra of poly(OPDA) as shown inFigure 11(a) The sharp peak appearing at 28398 eV isattributed to CndashH (C

1) bond while the peak appearing at

28418 eV is attributed to CndashC (C2) bondThe peak appearing

at 28508 eV is assigned to CndashN (C3) bond while the peak

appearing at 28758 eV is attributed to CndashO or CndashN+ (C4)

bond [32ndash34]N1s Figure 11(b) shows the XPS N1s spectrum of

poly(OPDA) which has three distinct curves The first twopeaks are assigned to imine (ndashN=) at 39858 eV and amine(ndashNHndash) at 39923 eV Moreover the peak that appears at40058 eV is due to positively charged nitrogen atom (N+)

Two distinct oxygen species contribute to the oxygen1 s signals in the conducting polymers (Figure 11(c)) Thedistinct energy peaks at 53068 and 53312 eV could beattributed to Cr

2O3and CndashOH respectively

The Cl 2p spectrum of poly(OPDA) is shown inFigure 11(d) In order to estimate the anion Cl at the surfaceCl 2p peaks are fitted with a number of spin-orbit doublets(Cl 2p

12and Cl 2p

32) with the BE for the C12p

32peaks

at about 19736 19834 and 2001 eV The lowest and thehighest BE components are attributable to the ionic andcovalent chlorine species (Clminus and ndashCl) respectively Thechlorine species (Cllowast) with the intermediate appear at BE of19834 eV The lower BE value of the Cllowast species comparedto the Cl species suggests the presence of chloride anionin a more positive environment probably arising from anincrease in the number of positively charged nitrogen in thepolymer chain associated with the formation of polarons andbipolarons

The Cr spectrum of (POPDA) is shown in Figure 11(e)The main components corresponding to different chemicalchromium species were observed in the high-resolutionCr2p32

spectrums The first peak at 57618 eV plusmn 02 eV wasassigned toCr

2O3which is in agreementwithwhatwas found

by Chowdhury and Saha [13] and Stefanov et al [35] alsoindicated by a distinctO1s peak at 53068 eV typical for Cr

2O3

whichmay be adsorbed on polymer surface during chromousacid H

2Cr2O3oxidation process There is also a component

visible that corresponds to Cr2p12

at 58608 eV which wasattributed to Cr3+ This data reveal that chromium ion ispresent between benzene rings of polymeric chain as shownin Scheme 1

354The Infrared Spectroscopic Analysis of (OPDA)Monomerand Its Analogs Polymer The IR spectra of the OPDA andits polymer (POPDA) are represented in Figure 12 while theabsorption band values and their assignments are summa-rized in Table 3 The medium absorption band appearing at


NH

NH

N Nn

N N nNH

NH

NH2

NH2

NH2NH2

NH2

NH2NH2

NH2

Cr3+ Cr3+

Clminus

Clminus

H2O

H2O

H+

H+

Scheme 1 Structure of the prepared (POPDA)

0

01

02

03

04

025050075010001250

Cl 2p

N1s

C1s

O1s

Cr 2p

Binding energy (eV)

Cou

nts

s

times106

Figure 10 X-ray photoelectron spectroscopy (XPS) survey elemen-tal composition of poly-o-phenylenediamine (POPDA)

453 cmminus1 which could be attributed to bending deformationof NndashH group attached to benzene ring in case of monomerappears at 518 cmminus1 with slight shift in case of polymer Thebroad absorption band appearing at 778 cmminus1 in case ofmonomer which could be attributed to out of plane deforma-tion of CH for 12-disubstituted benzene appears at 748 cmminus1with slight shift in case of polymer A series of absorptionbands appear in the region from 924 to 1152 cmminus1 whichcould be attributed to the out of plane CndashH deformationof 12-disubistuition benzene ring in case of monomer and124 tri-substituted of benzene ring in case of polymer Thesharp absorption bands appear at 1336 cmminus1 in case of themonomer which could be attributed to symmetric stretchingvibration of CndashN appears at 1362 cmminus1 with slight shift incase of polymer The sharp absorption band appearing at1490 cmminus1 in case of the monomer may be attributed to C=Caromatic stretching vibration which appears at 1500 cmminus1with slight shift in case of polymer The sharp absorptionband appearing at 1630 cmminus1 in case of the monomer whichmay be attributed to C=C deformation of benzene ringappears at 1621 cmminus1 with slight shift in case of polymer Theshoulder absorption band appears at 3032 cmminus1 in case of themonomer which could be attributed to symmetric stretchingvibration of CndashH in aromatic ring and disappears in case ofpolymerThe triplet absorption bands appearing at 3190 3281and 3370 cmminus1 in case of monomer could be attributed toasymmetric stretching vibration for NH group but in case of

Table 3 Infrared absorption bands and their assignments of o-phenylene-diamine monomer (OPDA) and its analogs polymer(POPDA)

Wave number (cmminus1) Assignments(OPDA)Monomer

(POPDA)Polymer

453m mdash Bending deformation of NH in primaryaromatic aminesmdash 518m

748b mdash Out-of-plane bending deformation ofCH in 12 disubstituted in benzene ringmdash 761b

810s mdash Out-of-plane deformation showing14-disubistuition in the benzene ringmdash 833sh

924s mdash

Plane CndashH deformation of12-disubistuition of benzene ring

mdash 1044w

1056m mdash1117s mdashmdash 1133w

1152 mdash

1336s 1362sh Symmetric stretching vibration for CndashOor CndashN group

1490s 1500b Symmetric stretching vibration for CndashCaromatic

1590 s mdashStretching vibration of CndashN orcombination band for protonatedprimary aromatic amine

1630s 1621b NndashH deformation of secondary amine3032sh mdash Symmetric stretching vibration of NndashH3281s 3354m Asymmetric stretching vibration for NH

2930sh 3354b Asymmetric stretching vibration for CHgroup in aliphatic chain

3370s mdash Symmetric stretching vibration of =CndashHs sharp m medium w weak b broad sh shoulder

polymer a broad absorption band that appears at 3354 cmminus1could be attributed to asymmetric stretching vibration forNH group and OH group present in the polymer structure

355 The UV-Visible Spectroscopic Study of OPDA Monomerand Its Analogs Polymer The UV-visible spectra of OPDA


Binding energy (eV)

0

5000

10000

15000

20000

25000

30000

35000

40000

280285290295

C 1s CndashC

CndashH

CndashO

C=N

(a)

Binding energy (eV)

0

5000

10000

15000

20000

25000

391396401406411

N1s

ndashNHndash

N+

ndashN=

(b)

Binding energy (eV)

0

10000

20000

30000

40000

50000

60000

525530535

O1s CndashOH

(c)

Binding energy (eV)

2000

2500

3000

3500

4000

4500

5000

190195200205

Cl 1s

Clminus

ndashCl

Cllowast

(d)

Binding energy (eV)

10000

20000

30000

40000

570575580585590595

Cr2O3Cr 2p

Cr3+

(e)

Figure 11 X-ray photoelectron spectroscopy (XPS) spectra of (POPDA)

and its polymer are represented in Figure 13 the spectra showthe following absorption bands

(1) in case of monomer two absorption bands appear at120582max = 219 and 240 nm which may be attributed to 120587-120587lowast transition (E

2-band) of the benzene ring and the

120573-band (1198601g minus 1198612u)

(2) in case of polymer two absorption bands appear at120582max = 221 and 243 nm which may be attributed to120587-120587lowast transition showing a bathochromic shift Besidethese two bands broad absorption band appears inthe visible region at 120582max = 417 nm which may bedue to the high conjugation of the aromatic polymericchain

356 Thermal Gravimetric Analysis (TGA) of Poly O-Phe-nylenediamine Thermogravimetric analysis (TGA) for the

prepared polymer has been investigated and the TGA-curveis represented in Figure 14 The calculated and found datafor the prepared polymers are summarized in Table 4 Thethermal degradation steps are summarized as follows

(1) the first stage includes the loss of one water moleculein the temperature range between 295 and 1226∘Cthe weight loss of this step was found to be 321which is in a good agreement with the calculated one

(2) in the second stage in the temperature range between1226 and 2038∘C the weight loss was found to be665 which could be attributed to the loss of oneHCl molecule The calculated weight loss is in goodagreement with the found one

(3) in the third stage in the temperature range between2038 and 3203∘C the weight loss was found to be1179 which is attributed to the loss of four (NH

2)


400900140019002400290034003900

(a)

(b)

Wavenumber (cmminus1)

Figure 12 The infrared spectrum of o-phenylenediamine (OPDA) (a) and it analogous polymer (POPDA) (b)

20000 40000 60000 80000

Abs

(A)

(nm)

(B)

Figure 13 UV-visible spectra of o-phenylenediamine (OPDA) (A) and it analogous polymer (POPDA) (B)

groups The calculated weight loss for this stage isequal to 1211

(4) in the fourth stage in the temperature range between3203 and 4000∘C the weight loss was found to be1695 which could be attributed to the loss of onemolecule of C

6H3ndashNH The calculated weight loss of

this stage is equal to 1722

(5) in the fifth stage in the temperature range between4000 and 5234∘C the weight loss was found to be1378 which is attributed to the loss of onemoleculeof phenyl ringThe calculated weight loss of this stageis equal to 1419

(6) in the last stage above 52338∘C the remainingpolymer molecule was found to be 4762 includingthe metallic residue but the calculated one was foundto be 4646

357 The X-Ray Diffraction Analysis and Transmission Elec-tron Microscope The X-Ray diffraction patterns of the pre-pared polymer are represented in Figure 15 The figure showsthat the prepared poly o-phenylenediamine is completelyamorphous

Morphology of poly o-phenylenediamine was character-ized by transmission electron microscope Figure 16 shows


0

50

100

000 20000 40000 60000

Weight 1575 (mg)Start End Weight loss End

Start 3500End 5230WtLoss

1381


1692


11791


6652


3212 minus00506

minus0105

minus0191

minus0267

minus0218

minus0825mgminus60227

295∘C

60000∘C

Temperature (∘C)

TGA

()

Figure 14 The thermal gravimetric analysis (TGA) for (POPDA)

02468

10121416182022242628303234

4 14 24 34 44 54 64 74

Lin

(Cou

nts)

2120579

Figure 15 X-ray poly-o-phenylenediamine (POPDA)


100nm

Figure 16 The transmission electron microscope of POPDA

65 75 85 95 105 115 125 135 145

minus25

minus35

minus45

minus55

minus6

minus5

minus4

minus3

80∘C

70∘C

60∘C

50∘C

40∘C

30∘C

ln120590

ac(S

Mc

m)

ln (120596)

Figure 17 ac conductivity versus angular frequency for poly-o-phenylenediamine (POPDA) with frequency at different temperatures

Table 4 Thermogravimetric data of poly-o-phenylenediamine(POPDA)

Name Temperaturerange ∘C

Weight loss () The removedmoleculeCalc Found

Poly(POPDA)

295ndash1226 341 3212 H2O1226ndash2038 691 6652 HCl2038ndash3203 1211 11791 4NH2

3203ndash40000 1722 16952 C6H3ndashNH400ndash52340 1419 13778 C6H3

Remainingweight ()above 600

4617 4762 mdash

TEM image of poly o-phenylenediamine which nearly spher-ical or ellipsoidal particles with approximate diameter 60ndash120 nm either separated or linked with each other

36 ac Conductivity (120590ac) Figure 17 represent the variationin ac conductivity (120590ac) for (POPDA) as a function offrequency and temperature It is observed that the value

of ac conductivity increases with the increase of frequencyThis behavior is in good agreement with the random freeenergy model proposed by Dyre [36] According to thismodel conductance increases as a function of frequency inmany solids including polymers which can be explainedon the basis of any hopping model The rise in conductivityupon increasing the frequency and temperature is commonfor disordered conducting polymer As can be seen eachcurve displays a conductivity dispersion which is stronglydependent on frequency and shows weaker temperaturedependant

The recorded conductivity value at room temperatureof POPDA was found 00352 Scm which is higher thanconductivity of polyaniline-polyvinyl alcohol blends 105 times10minus5 S cmminus1 [37] and ac conductivity of HCl doped polyani-line synthesized by the interfacial polymerization technique62 times 10minus5 S cmminus1 [38] Also the ac conductivity of POPDAis higher than polyaniline loaded with 10 molybdenumtrioxide composites 0025 scm [39] but lower than thedetermined value of ac conductivity polyaniline preparedby K2Cr2O7as oxidant 1922 S cmminus1 Such difference could

be attributed to the different disorder of each compositesubstituted function group and different used dopant


015

017

019

021

023

025

027

029

031

033

035

300 310 320 330 340 350 360

s

T (K)

Figure 18 Frequency exponent (119904) versus temperature for poly-o-phenylenediamine (POPDA)

In general for amorphous conducting material disor-dered systems low mobility polymers and even crystallinematerials the ac conductivity (120590ac) as a function of frequencycan obey a power law with frequency [40] The ac conduc-tivity (120590ac) over a wide range of frequencies can be expressedas

120590ac (120596) = 119860120596119904

(18)

where 119860 is a complex constant and the index (119904) is frequencyexponent and 120596 is the angular frequency (120596 = 2120587119891)

Figure 17 shows the relation between Ln 120590ac and Ln 120596 atdifferent temperatures The value of (119904) at each temperaturehas been calculated from the slope of ln 120590(120596) versus ln (120596)plot As shown in Figure 18 the calculated values of (119904) for(POPDA) sample are less than unity The microscopic con-duction mechanisms of disordered systems are governed bytwo physical processes such as classical hopping or quantummechanical tunneling of charge carries over the potentialbarrier separating two energetically favorable centers in arandom distribution The exact nature of charge transportis mainly obtained experimentally from the temperaturevariation of exponent (s) [41] The temperature exponent(s)dependences for (POPDA) sample reveal that the frequencyexponent(s) decreases with the increase of temperature Thisbehavior is only observed in the correlated barrier hoppingmodel proposed by Elliott [42]

4 Conclusions

In the present work POPDA polymer incorporated withpotassium dichromate and HCl has been successfullyachieved The optimum yield formation of POPDA isobtained at 03M potassium dichromate 01M of themonomer and 02M hydrochloric acid concentrations Theinitial and overall rate of polymerization reaction increaseswith increasing the oxidant monomer and HCl concen-trations The exponent of oxidant monomer and HCl wasfound to be 1011 1045 and 0954 respectivelyThe chrome is

present between polymer chains as sandwich-bonded C6H6ndash

C6H6groups and the usual formation procedure hydrolyzes

the reaction mixture with dilute acid which gives the cation(C6H6)2Cr3+ The ac conductivity increases with the increase

of frequency and temperature The microscopic conductionmechanism of charge which carries over the potential barrierin polymer backbone is classical hopping model

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

References

[1] P C Wang L H Liu D A Mengistie et al ldquoTransparent elec-trodes based on conducting polymers for display applicationsrdquoDisplays vol 34 no 4 pp 301ndash314 2013

[2] M Jaymand ldquoRecent progress in chemical modification ofpolyanilinerdquo Progress in Polymer Science vol 38 no 9 pp 1287ndash1306 2013

[3] Q Ju Y Shi and Kan ldquoPerformance study of magne-sium-polyaniline rechargeable battery in 1-ethyl-3-meth-ylimidazolium ethyl sulfate electrolyterdquo Synthetic Metals vol178 pp 27ndash33 2013

[4] C Steffens A Manzoli J E Oliveira F L Leite D SCorrea and P S P Herrmann ldquoBio-inspired sensor for insectpheromone analysis based on polyaniline functionalized AFMcantilever sensorrdquo Sensors and Actuators B Chemical vol 191pp 643ndash649 2014

[5] L Wang E Hua M Liang et al ldquoGraphene sheets polyanilineand AuNPs based DNA sensor for electrochemical determina-tion of BCRABL fusion gene with functional hairpin proberdquoBiosensors and Bioelectronics vol 51 pp 201ndash207 2014

[6] V Talwar O Singh and R Singh ldquoZnO assisted polyanilinenanofibers and its application as ammonia gas sensorrdquo Sensorsand Actuators B vol 191 pp 276ndash282 2014

[7] Y Moon J yun and H Kim ldquoSynergetic improvementin electromagnetic interference shielding characteristics ofpolyaniline-coated graphite oxidegamma-Fe

2

O3

BaTiO3


nanocompositesrdquo Journal of Industrial and EngineeringChemistry vol 19 no 2 pp 493ndash497 2013

[8] G Gupta N Birbilis A B Cook and A S KhannaldquoPolyaniline-lignosulfonateepoxy coating for corrosion pro-tection of AA2024-T3rdquo Corrosion Science vol 67 pp 256ndash2672013

[9] R Karthikaiselvi and S Subhashini ldquoStudy of adsorption prop-erties and inhibition of mild steel corrosion in hydrochloricacid media by water soluble composite poly (vinyl alcohol-o-methoxy aniline)rdquo Journal of the Association of ArabUniversitiesfor Basic and Applied Sciences 2013

[10] X Martin and K Mullen ldquoDesigning p-conjugated polymersfor organic electronicsrdquo Progress in Polymer Science vol 38 no12 pp 1832ndash1908 2013

[11] K Gopodinova and L Terlemezyan ldquoConducting polymersprepared by oxidative polymerization polyanilinerdquo Progress inPolymer Science vol 23 no 8 pp 1443ndash1484 1998

[12] K Gurunathan A VMurugan RMarimuthu U P Mulik andD P Amalnerkar ldquoElectrochemically synthesised conductingpolymeric materials for applications towards technology inelectronics optoelectronics and energy storage devicesrdquo Mate-rials Chemistry and Physics vol 61 no 3 pp 173ndash191 1999

[13] P Chowdhury and B Saha ldquoPotassium dichromate initiatedpolymerization of anilinerdquo Indian Journal of Chemical Technol-ogy vol 12 pp 671ndash675 2005

[14] R Hirase T Shikata and M Shirai ldquoSelective formationof polyaniline on wool by chemical polymerization usingpotassium iodaterdquo Synthetic Metals vol 146 no 1 pp 73ndash772004

[15] K Gopalakrishnan M Elango and M Thamilsevan ldquoOpticalstudies on nano-structured conducting Polyaniline prepared bychemical oxidationmethodrdquoArchives of Physics Research vol 3no 4 pp 315ndash319 2012

[16] K Molapo P M Ndangili R F Ajayi et al ldquoElectronics ofconjugated polymers (I) polyanilinerdquo International Journal ofElectrochemical Science vol 7 pp 11859ndash11875 2012

[17] Y Cao P Smith and A Heeger ldquoCounter-ion induced proces-sibility of conducting polyaniline and of conducting polyblendsof polyaniline in bulk polymersrdquo Synthetic Metals vol 48 no 1pp 91ndash97 1992

[18] Y KangM Lee and S Rhee ldquoPolyaniline with surfactant coun-terions conducting polymer materials which are processible inthe conducting formrdquo Synthetic Metals vol 57 no 1 pp 3471ndash3482 1993

[19] Y Kang M Lee and S Rhee ldquoElectrochemical properties ofpolyaniline doped with poly(styrenesulfonic acid)rdquo SyntheticMetals vol 52 no 3 pp 319ndash328 1992

[20] A Pron J Laska J E Osterholm and P Smith ldquoProcessableconducting polymers obtained via protonation of polyanilinewith phosphoric acid estersrdquo Polymer vol 34 no 20 pp 4235ndash4240 1993

[21] SM SayyahHMAbd El-Salam and EM S Azzam ldquoSurfaceactivity of monomeric and polymeric (3-alkyloxy aniline)surfactantsrdquo International Journal of Polymeric Materials vol54 no 6 pp 541ndash555 2005

[22] S M Sayyah A A Bahgat and H M Abd El-SalamldquoKinetic studies of the aqueous oxidative polymerization of 3-hydroxyaniline and characterization of the polymer obtainedrdquoInternational Journal of Polymeric Materials vol 51 no 3 pp291ndash314 2002

[23] S M Sayyah A A Abd El-Khalek A A Bahgat and H AAbd El-Salam ldquoKinetic studies of the chemical polymerizationof substituted aniline in aqueous solutions and characterizationof the polymer obtained Part 1 3-Chloroanilinerdquo PolymerInternational vol 50 no 2 pp 197ndash206 2001

[24] S M Sayyah and H M Abd El-Salam ldquoAqueous oxidativepolymerization of N-methyle aniline in acid medium andcharacterization of the obtained polymerrdquo International Journalof Polymeric Materials vol 52 pp 1087ndash1111 2003

[25] S M Sayyah A A Abd El-Khalek A A Bahgat and HM Abd El-Salam ldquoKinetic studies of the polymerization ofsubstituted aniline in aqueous solutions and characterizationof the polymer obtained Part 2 3-methylanilinerdquo InternationalJournal of Polymeric Materials vol 49 no 1 pp 25ndash49 2001

[26] S M Sayyah H M Abd El-Salam and A A Bahgat ldquoAqueousoxidative polymerization of 3-methoxyaniline and characteri-zation of its polymerrdquo International Journal of Polymeric Mate-rials vol 51 no 10 pp 915ndash938 2002



[29] S M Sayyah and H Abd El Salam ldquoOxidative chemicalpolymerization of some 3-alkyloxyaniline surfactants and char-acterization of the obtained polymersrdquo International Journal ofPolymeric Materials and Polymeric Biomaterials vol 55 no 12pp 1075ndash1093 2006

[30] F Cotton and GWilkinsonAdvanced Inorganic Chemistry 3rdedition 1972

[31] H Zeiss P Whealty and H Winkler Benzoic Material Com-plexes Ronald Press 1966

[32] A Qaiser M Hyland and D Patterson ldquoEffects of variouspolymerization techniques on PANI deposition at the surfaceof cellulose ester microporous membranes XPS and electricalconductivity studiesrdquo Synthetic Metals vol 162 no 11-12 pp958ndash967 2012

[33] J Li X Qian L Wang and X An ldquoXPS characterization andpercolation behavior of polyaniline-coated conductive paperrdquoBioResources vol 5 no 2 pp 712ndash726 2010

[34] K Tan and B Tan ldquoThe chemical nature of the nitrogensin polypyrrole and polyaniline a comparative study by X-rayphotoelectron spectroscopyrdquo Journal of Chemical Physics vol94 no 8 article 5382 1991

[35] P Stefanov D Stoychev M Stoycheva and T Marinov ldquoXPSand SEM studies of chromium oxide films chemically formedon stainless steel 316 Lrdquo Materials Chemistry and Physics vol65 no 2 pp 212ndash215 2000

[36] J Dyre ldquoThe random free-energy barrier model for ac conduc-tion in disordered solidsrdquo Journal of Applied Physics vol 64 no5 article 2456 1988

[37] P Dutta S Biswas M Ghosh S K De and S Chatterjee ldquoThedc and ac conductivity of polyaniline-polyvinyl alcohol blendsrdquoSynthetic Metals vol 122 no 2 pp 455ndash461 2001

[38] P Chutia and A Kumar ldquoElectrical optical and dielectricproperties of HCl doped polyaniline nanorodsrdquo Physica B vol436 pp 200ndash207 2014


[39] K R Anilkumar A Parveen G R Badiger and M V NAmbika Prasad ldquoEffect of molybdenum trioxide (MoO

3

) onthe electrical conductivity of polyanilinerdquo Physica B CondensedMatter vol 404 no 12-13 pp 1664ndash1667 2009

[40] A Paphanassiou ldquoThe power law dependence of the acconductivity on frequency in amorphous solidsrdquo Journal ofPhysics D Applied Physics vol 35 no 17 article L88 2002

[41] A Dey S De A De and S K De ldquoCharacterization and dielec-tric properties of polyaniline-TiO

2

nanocompositesrdquoNanotech-nology vol 15 pp 1277ndash1283 2004

[42] S Elliott ldquoAc conduction in amorphous chalcogenide andpnictide semiconductorsrdquoAdvances in Physics vol 36 no 2 pp135ndash217

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of



CeramicsJournal of


CompositesJournal of

NanoparticlesJournal of



International Journal of

Biomaterials


NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014


CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research



MetallurgyJournal of


BioMed Research International

MaterialsJournal of


Nano

materials


Journal ofNanomaterials


scanning electron microscopy TGA-DTA analysis and acconductivity have been investigated by Sayyah et al [25ndash28]

The present work intends to study the kinetics of theoxidative chemical polymerization of o-phenylenediamine inaqueous HCl medium and potassium dichromate as oxidantThe obtained polymer is characterized by XPS IR UV-visible TGA elemental analysis X-ray transmission electronmicroscopy (TEM) and ac conductivity measurements

2 Experimental

21Materials O-phenylenediaminewas provided byAldrichchemical Co (Germany) Concentrated hydrochloric acidpure grade product was provided by El-Nasr pharmaceuticalchemical Co Egypt Potassium dichromate was providedby Sigma-Aldrich chemical Co (Germany) Doubly distilledwater was used to prepare all the solutions needed in thekinetic studies

22 Oxidative Aqueous Polymerization of O-Phenylene-diamine Monomer The polymerization reaction was carriedout in a well-stoppered conical flask of 250mL capacityaddition of OPDA amount in 25mL HCl of known molaritywas followed by the addition of the required amount ofpotassium dichromate as oxidant in water (25mL) to thereaction mixture The orders of addition of substances werekept constant in all the performed experiments The stop-pered conical flasks were then placed in an automaticallycontrolled thermostat at the required temperatureThe flaskswere shaken (15 shakings10 s15min) by using an automaticshaker The flasks were filtrated using a Buchner funnel thenthe obtained polymer was washed with distilled water andfinally dried till constant weight in vacuum oven at 60∘C

23 Elemental Analysis Infrared andUltraviolet SpectroscopyThe carbon hydrogen and nitrogen contents of the preparedpolymer were carried out in the microanalytical laboratoryat Cairo University by using oxygen flask combustion and adosimat E415 titrator (Switzerland)

The infrared spectroscopic analysis of the preparedpolymer was carried out in the microanalytical laboratoryat Cairo University by using a Shimadzu FTIR-430 Jascospectrophotometer and KBr disc technique

The ultraviolet-visible absorption spectra of themonomer and the prepared polymer sample were measuredusing Shimadzu UV spectrophotometer (M 160 PC)at room temperature in the range 200ndash400 nm usingdimethylformamide as a solvent and reference

24 X-Ray Photoelectron Spectroscopy (XPS) An XPS spec-trum was obtained on XPS-thermo scientific spectrometerModel K-ALDH inCentral metallurgical research and devel-opment institute (CMRDI) Polymer was mounted on a stan-dard sample holder using double-sided adhesive tape Surveyand XPS spectra were obtained with Al K120572 monochromaticX-ray with the resolution of 07 eV

25 Thermal Gravimetric Analysis (TGA) Transmission Elec-tron Microscopy (TEM) and X-Ray Analysis Thermal gravi-metric analysis (TGA) of the polymer sample was performedusing a SHIMADZU DT-30 thermal analyzer The weightloss was measured from ambient temperature up to 600∘C atrate of 20∘Cmin to determine the rate of degradation of thepolymer

The X-ray diffractometer type Philips 1976 Model 1390was used to investigate the phase structure of the polymerpowder under the following condition which kept constantduring the analysis processes Cu X-ray tube scan speed =8min current = 30mA voltage = 40 kv and preset time =10 s

The inner cavity and wall thickness of the preparedpolymer were investigated using transmission electronmicroscopy (TEM) JEOL JEM-1200 EX ^ (Japan)

26 Conductivity Measurements The ac conductivity wasmeasured using Philips RCL bridge (digital and computer-ized) at a frequency range 01ndash100 kHz and over temperaturerange 30ndash80∘CThe temperature was controlled by the use ofa double wound electric oven

The ac conductivity 120590ac value was calculated using therelation

120590ac = 12057610158401015840

120596120576119900 (1)

where 120596 = 2120587119891 and 119891 is the applied frequency

3 Results and Discussion

31 Determination of the Optimum Polymerization Condi-tions To optimize the condition for polymerization of o-phenylenediamine the concentrations of potassium dichro-mate hydrochloric acid and monomer were investigatedwith keeping the total volume of the reaction mixtureconstant at 50mL

311 Effect of Potassium Dichromate Concentration Both ofthe monomer and HCl concentrations are fixed at 01Mwhile the oxidant concentrations were varied from 004 to05M at 5 plusmn 02∘C to investigate the optimum polymerizationcondition of K

2Cr2O7 The yield-time curve was represented

in Figure 1 from which it is clear that the obtained yieldincreased with the increase of K

2Cr2O7reaching maximum

value at 03M From the left part of the curve it is clearthat the polymer yield increases from 004M to 03M thendecreases from 03M to 05M This could be due to the factthat in the first part of the curve the produced initiator ionradical moieties activate the backbone and simultaneouslyproduced the o-phenylenediamine ion radical which takesplace immediately and therefore yield increases with theincrease of potassium dichromate concentration up to 03MBut in the second part of the curve the polymer yielddecreases with increasing K

2Cr2O7concentration may be

due to a high concentration of oxidant promote the formationof low molecular weight oxidation product and also degradethe product polymer which easily soluble in water [13]


00

04

08

12

0 02 04 06

Yiel

d (g

m)

K2Cr2O7 (mol)

Figure 1 Yield-K2

Cr2

O7


0 02 04 0600

05

10

15

20

Yiel

d (g

m)

HCl (mol)



2Cr2O7





00

04

08

12

16

0 01 02 03 04 05

Yiel

d (g

m)

Monomer (mol)



Rate (119877119894) =

119875

119881 times119872 times 119905 (2)








000204060810121416

2 7 12 17 22 27

Yiel

d (g

m)

005 g molL01 g molL

02 g molL03 g molL

Time (min)

(a)

1415161718192021222324

45 47 49 51 53 55

6+

Log(Ri)

6 + Log(oxidant)

(b)


00

02

04

06

08

10

12

14

16

Yiel

d (g

m)

005 g molL01 g molL

015 g molL02 g molL

2 7 12 17 22 27Time (min)

(a)

15

17

19

21

23

25

46 48 50 52 54

6+

Log(Ri)

6 + Log(HCl)

(b)







Log (119870) =minus119864119886

2303119877119879+ 119862 (3)





00

02

04

06

08

10

12

14

16

2 7 12 17 22 27

Yiel

d (g

m)



Time (min)

(a)

15

17

19

21

23

25

46 48 50 52 546 + Log(monomer)

6+

Log(Ri)

(b)


0

04

08

12

16

2

Yiel

d (g

m)

2 7 12 17 22 27Time (min)

5∘C

15∘C

10∘C


1

12

14

16

000345 000349 000353 000357 000361

Log(

rate

)

1T (Kminus1)


02

04

06

08

000344 000348 000352 000356 00036 000364

1T (Kminus1)

log(K2T

)






(4)



2


1198702= (

119877119879

119873ℎ) 119890Δ119878

lowast

119877


lowast

119877119879

(5)




Ln(1198702119879) = ln( 119877

119873ℎ) +

Δ119878lowast


119877119879 (6)








K2Cr2O7+H2O + 2H+ = 2K+ + 2H

2CO4 (7)






(HCrO4)minus

999445999468 (CrO4)2minus

+H+ K = 10minus59 (8)

(H2CrO4) 999445999468 (HCrO

4)minus

+H+ K = 41 (9)

2(HCrO4)minus

999445999468 (Cr2O7)2minus

+H2O K = 10

minus22

(10)


2

NH2

Ph

Ph

N+

H3 + H2CrO4

Complex

O

O

H

H

H

H

N

N+

OH2

O+

H2

Cr(11)


2

NH2

+∙











2

NH2 NH2 NH2

+∙

NH2 + H2CrO3 + H2O

+∙

NH2 +∙

NH

Para semidine

+ H2CrO4 = (13)

NH2 NH2 NH2 NH2

+∙

N+∙

N+∙

NH2 + H2CrO3 + 6 H2 = H+∙


(14)



2

NH2

+ K2Cr2O7 + 8H+= PS + 2K+

+ 2Cr3++ 7H2ON

+

H3 (15)


2O (16)



H H H

N N N

NH2 NH2 NH2 NH2

∙+

NH 2

(17)










6H6)2Cr3+ [30 31]












12and Cl 2p


32peaks






2O3







NH

NH

N Nn

N N nNH

NH

NH2

NH2

NH2NH2

NH2

NH2NH2

NH2

Cr3+ Cr3+

Clminus

Clminus

H2O

H2O

H+

H+


0

01

02

03

04

025050075010001250

Cl 2p

N1s

C1s

O1s

Cr 2p

Binding energy (eV)

Cou

nts

s

times106





(POPDA)Polymer




924s mdash


mdash 1044w


1152 mdash










Binding energy (eV)

0

5000

10000

15000

20000

25000

30000

35000

40000

280285290295

C 1s CndashC

CndashH

CndashO

C=N

(a)

Binding energy (eV)

0

5000

10000

15000

20000

25000

391396401406411

N1s

ndashNHndash

N+

ndashN=

(b)

Binding energy (eV)

0

10000

20000

30000

40000

50000

60000

525530535

O1s CndashOH

(c)

Binding energy (eV)

2000

2500

3000

3500

4000

4500

5000

190195200205

Cl 1s

Clminus

ndashCl

Cllowast

(d)

Binding energy (eV)

10000

20000

30000

40000

570575580585590595

Cr2O3Cr 2p

Cr3+

(e)





120573-band (1198601g minus 1198612u)







2)


400900140019002400290034003900

(a)

(b)



20000 40000 60000 80000

Abs

(A)

(nm)

(B)











0

50

100

000 20000 40000 60000



1381


1692


11791


6652


3212 minus00506

minus0105

minus0191

minus0267

minus0218


295∘C

60000∘C

Temperature (∘C)

TGA

()


02468

10121416182022242628303234

4 14 24 34 44 54 64 74

Lin

(Cou

nts)

2120579



100nm


65 75 85 95 105 115 125 135 145

minus25

minus35

minus45

minus55

minus6

minus5

minus4

minus3

80∘C

70∘C

60∘C

50∘C

40∘C

30∘C

ln120590

ac(S

Mc

m)

ln (120596)





Poly(POPDA)




4617 4762 mdash







015

017

019

021

023

025

027

029

031

033

035

300 310 320 330 340 350 360

s

T (K)



120590ac (120596) = 119860120596119904

(18)



4 Conclusions








References








2

O3

BaTiO3




































3




2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




00

04

08

12

0 02 04 06

Yiel

d (g

m)

K2Cr2O7 (mol)

Figure 1 Yield-K2

Cr2

O7


0 02 04 0600

05

10

15

20

Yiel

d (g

m)

HCl (mol)



2Cr2O7





00

04

08

12

16

0 01 02 03 04 05

Yiel

d (g

m)

Monomer (mol)



Rate (119877119894) =

119875

119881 times119872 times 119905 (2)








000204060810121416

2 7 12 17 22 27

Yiel

d (g

m)

005 g molL01 g molL

02 g molL03 g molL

Time (min)

(a)

1415161718192021222324

45 47 49 51 53 55

6+

Log(Ri)

6 + Log(oxidant)

(b)


00

02

04

06

08

10

12

14

16

Yiel

d (g

m)

005 g molL01 g molL

015 g molL02 g molL

2 7 12 17 22 27Time (min)

(a)

15

17

19

21

23

25

46 48 50 52 54

6+

Log(Ri)

6 + Log(HCl)

(b)







Log (119870) =minus119864119886

2303119877119879+ 119862 (3)





00

02

04

06

08

10

12

14

16

2 7 12 17 22 27

Yiel

d (g

m)



Time (min)

(a)

15

17

19

21

23

25

46 48 50 52 546 + Log(monomer)

6+

Log(Ri)

(b)


0

04

08

12

16

2

Yiel

d (g

m)

2 7 12 17 22 27Time (min)

5∘C

15∘C

10∘C


1

12

14

16

000345 000349 000353 000357 000361

Log(

rate

)

1T (Kminus1)


02

04

06

08

000344 000348 000352 000356 00036 000364

1T (Kminus1)

log(K2T

)






(4)



2


1198702= (

119877119879

119873ℎ) 119890Δ119878

lowast

119877


lowast

119877119879

(5)




Ln(1198702119879) = ln( 119877

119873ℎ) +

Δ119878lowast


119877119879 (6)








K2Cr2O7+H2O + 2H+ = 2K+ + 2H

2CO4 (7)






(HCrO4)minus

999445999468 (CrO4)2minus

+H+ K = 10minus59 (8)

(H2CrO4) 999445999468 (HCrO

4)minus

+H+ K = 41 (9)

2(HCrO4)minus

999445999468 (Cr2O7)2minus

+H2O K = 10

minus22

(10)


2

NH2

Ph

Ph

N+

H3 + H2CrO4

Complex

O

O

H

H

H

H

N

N+

OH2

O+

H2

Cr(11)


2

NH2

+∙











2

NH2 NH2 NH2

+∙

NH2 + H2CrO3 + H2O

+∙

NH2 +∙

NH

Para semidine

+ H2CrO4 = (13)

NH2 NH2 NH2 NH2

+∙

N+∙

N+∙

NH2 + H2CrO3 + 6 H2 = H+∙


(14)



2

NH2

+ K2Cr2O7 + 8H+= PS + 2K+

+ 2Cr3++ 7H2ON

+

H3 (15)


2O (16)



H H H

N N N

NH2 NH2 NH2 NH2

∙+

NH 2

(17)










6H6)2Cr3+ [30 31]












12and Cl 2p


32peaks






2O3







NH

NH

N Nn

N N nNH

NH

NH2

NH2

NH2NH2

NH2

NH2NH2

NH2

Cr3+ Cr3+

Clminus

Clminus

H2O

H2O

H+

H+


0

01

02

03

04

025050075010001250

Cl 2p

N1s

C1s

O1s

Cr 2p

Binding energy (eV)

Cou

nts

s

times106





(POPDA)Polymer




924s mdash


mdash 1044w


1152 mdash










Binding energy (eV)

0

5000

10000

15000

20000

25000

30000

35000

40000

280285290295

C 1s CndashC

CndashH

CndashO

C=N

(a)

Binding energy (eV)

0

5000

10000

15000

20000

25000

391396401406411

N1s

ndashNHndash

N+

ndashN=

(b)

Binding energy (eV)

0

10000

20000

30000

40000

50000

60000

525530535

O1s CndashOH

(c)

Binding energy (eV)

2000

2500

3000

3500

4000

4500

5000

190195200205

Cl 1s

Clminus

ndashCl

Cllowast

(d)

Binding energy (eV)

10000

20000

30000

40000

570575580585590595

Cr2O3Cr 2p

Cr3+

(e)





120573-band (1198601g minus 1198612u)







2)


400900140019002400290034003900

(a)

(b)



20000 40000 60000 80000

Abs

(A)

(nm)

(B)











0

50

100

000 20000 40000 60000



1381


1692


11791


6652


3212 minus00506

minus0105

minus0191

minus0267

minus0218


295∘C

60000∘C

Temperature (∘C)

TGA

()


02468

10121416182022242628303234

4 14 24 34 44 54 64 74

Lin

(Cou

nts)

2120579



100nm


65 75 85 95 105 115 125 135 145

minus25

minus35

minus45

minus55

minus6

minus5

minus4

minus3

80∘C

70∘C

60∘C

50∘C

40∘C

30∘C

ln120590

ac(S

Mc

m)

ln (120596)





Poly(POPDA)




4617 4762 mdash







015

017

019

021

023

025

027

029

031

033

035

300 310 320 330 340 350 360

s

T (K)



120590ac (120596) = 119860120596119904

(18)



4 Conclusions








References








2

O3

BaTiO3




































3




2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




000204060810121416

2 7 12 17 22 27

Yiel

d (g

m)

005 g molL01 g molL

02 g molL03 g molL

Time (min)

(a)

1415161718192021222324

45 47 49 51 53 55

6+

Log(Ri)

6 + Log(oxidant)

(b)


00

02

04

06

08

10

12

14

16

Yiel

d (g

m)

005 g molL01 g molL

015 g molL02 g molL

2 7 12 17 22 27Time (min)

(a)

15

17

19

21

23

25

46 48 50 52 54

6+

Log(Ri)

6 + Log(HCl)

(b)







Log (119870) =minus119864119886

2303119877119879+ 119862 (3)





00

02

04

06

08

10

12

14

16

2 7 12 17 22 27

Yiel

d (g

m)



Time (min)

(a)

15

17

19

21

23

25

46 48 50 52 546 + Log(monomer)

6+

Log(Ri)

(b)


0

04

08

12

16

2

Yiel

d (g

m)

2 7 12 17 22 27Time (min)

5∘C

15∘C

10∘C


1

12

14

16

000345 000349 000353 000357 000361

Log(

rate

)

1T (Kminus1)


02

04

06

08

000344 000348 000352 000356 00036 000364

1T (Kminus1)

log(K2T

)






(4)



2


1198702= (

119877119879

119873ℎ) 119890Δ119878

lowast

119877


lowast

119877119879

(5)




Ln(1198702119879) = ln( 119877

119873ℎ) +

Δ119878lowast


119877119879 (6)








K2Cr2O7+H2O + 2H+ = 2K+ + 2H

2CO4 (7)






(HCrO4)minus

999445999468 (CrO4)2minus

+H+ K = 10minus59 (8)

(H2CrO4) 999445999468 (HCrO

4)minus

+H+ K = 41 (9)

2(HCrO4)minus

999445999468 (Cr2O7)2minus

+H2O K = 10

minus22

(10)


2

NH2

Ph

Ph

N+

H3 + H2CrO4

Complex

O

O

H

H

H

H

N

N+

OH2

O+

H2

Cr(11)


2

NH2

+∙











2

NH2 NH2 NH2

+∙

NH2 + H2CrO3 + H2O

+∙

NH2 +∙

NH

Para semidine

+ H2CrO4 = (13)

NH2 NH2 NH2 NH2

+∙

N+∙

N+∙

NH2 + H2CrO3 + 6 H2 = H+∙


(14)



2

NH2

+ K2Cr2O7 + 8H+= PS + 2K+

+ 2Cr3++ 7H2ON

+

H3 (15)


2O (16)



H H H

N N N

NH2 NH2 NH2 NH2

∙+

NH 2

(17)










6H6)2Cr3+ [30 31]












12and Cl 2p


32peaks






2O3







NH

NH

N Nn

N N nNH

NH

NH2

NH2

NH2NH2

NH2

NH2NH2

NH2

Cr3+ Cr3+

Clminus

Clminus

H2O

H2O

H+

H+


0

01

02

03

04

025050075010001250

Cl 2p

N1s

C1s

O1s

Cr 2p

Binding energy (eV)

Cou

nts

s

times106





(POPDA)Polymer




924s mdash


mdash 1044w


1152 mdash










Binding energy (eV)

0

5000

10000

15000

20000

25000

30000

35000

40000

280285290295

C 1s CndashC

CndashH

CndashO

C=N

(a)

Binding energy (eV)

0

5000

10000

15000

20000

25000

391396401406411

N1s

ndashNHndash

N+

ndashN=

(b)

Binding energy (eV)

0

10000

20000

30000

40000

50000

60000

525530535

O1s CndashOH

(c)

Binding energy (eV)

2000

2500

3000

3500

4000

4500

5000

190195200205

Cl 1s

Clminus

ndashCl

Cllowast

(d)

Binding energy (eV)

10000

20000

30000

40000

570575580585590595

Cr2O3Cr 2p

Cr3+

(e)





120573-band (1198601g minus 1198612u)







2)


400900140019002400290034003900

(a)

(b)



20000 40000 60000 80000

Abs

(A)

(nm)

(B)











0

50

100

000 20000 40000 60000



1381


1692


11791


6652


3212 minus00506

minus0105

minus0191

minus0267

minus0218


295∘C

60000∘C

Temperature (∘C)

TGA

()


02468

10121416182022242628303234

4 14 24 34 44 54 64 74

Lin

(Cou

nts)

2120579



100nm


65 75 85 95 105 115 125 135 145

minus25

minus35

minus45

minus55

minus6

minus5

minus4

minus3

80∘C

70∘C

60∘C

50∘C

40∘C

30∘C

ln120590

ac(S

Mc

m)

ln (120596)





Poly(POPDA)




4617 4762 mdash







015

017

019

021

023

025

027

029

031

033

035

300 310 320 330 340 350 360

s

T (K)



120590ac (120596) = 119860120596119904

(18)



4 Conclusions








References








2

O3

BaTiO3




































3




2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




00

02

04

06

08

10

12

14

16

2 7 12 17 22 27

Yiel

d (g

m)



Time (min)

(a)

15

17

19

21

23

25

46 48 50 52 546 + Log(monomer)

6+

Log(Ri)

(b)


0

04

08

12

16

2

Yiel

d (g

m)

2 7 12 17 22 27Time (min)

5∘C

15∘C

10∘C


1

12

14

16

000345 000349 000353 000357 000361

Log(

rate

)

1T (Kminus1)


02

04

06

08

000344 000348 000352 000356 00036 000364

1T (Kminus1)

log(K2T

)






(4)



2


1198702= (

119877119879

119873ℎ) 119890Δ119878

lowast

119877


lowast

119877119879

(5)




Ln(1198702119879) = ln( 119877

119873ℎ) +

Δ119878lowast


119877119879 (6)








K2Cr2O7+H2O + 2H+ = 2K+ + 2H

2CO4 (7)






(HCrO4)minus

999445999468 (CrO4)2minus

+H+ K = 10minus59 (8)

(H2CrO4) 999445999468 (HCrO

4)minus

+H+ K = 41 (9)

2(HCrO4)minus

999445999468 (Cr2O7)2minus

+H2O K = 10

minus22

(10)


2

NH2

Ph

Ph

N+

H3 + H2CrO4

Complex

O

O

H

H

H

H

N

N+

OH2

O+

H2

Cr(11)


2

NH2

+∙











2

NH2 NH2 NH2

+∙

NH2 + H2CrO3 + H2O

+∙

NH2 +∙

NH

Para semidine

+ H2CrO4 = (13)

NH2 NH2 NH2 NH2

+∙

N+∙

N+∙

NH2 + H2CrO3 + 6 H2 = H+∙


(14)



2

NH2

+ K2Cr2O7 + 8H+= PS + 2K+

+ 2Cr3++ 7H2ON

+

H3 (15)


2O (16)



H H H

N N N

NH2 NH2 NH2 NH2

∙+

NH 2

(17)










6H6)2Cr3+ [30 31]












12and Cl 2p


32peaks






2O3







NH

NH

N Nn

N N nNH

NH

NH2

NH2

NH2NH2

NH2

NH2NH2

NH2

Cr3+ Cr3+

Clminus

Clminus

H2O

H2O

H+

H+


0

01

02

03

04

025050075010001250

Cl 2p

N1s

C1s

O1s

Cr 2p

Binding energy (eV)

Cou

nts

s

times106





(POPDA)Polymer




924s mdash


mdash 1044w


1152 mdash










Binding energy (eV)

0

5000

10000

15000

20000

25000

30000

35000

40000

280285290295

C 1s CndashC

CndashH

CndashO

C=N

(a)

Binding energy (eV)

0

5000

10000

15000

20000

25000

391396401406411

N1s

ndashNHndash

N+

ndashN=

(b)

Binding energy (eV)

0

10000

20000

30000

40000

50000

60000

525530535

O1s CndashOH

(c)

Binding energy (eV)

2000

2500

3000

3500

4000

4500

5000

190195200205

Cl 1s

Clminus

ndashCl

Cllowast

(d)

Binding energy (eV)

10000

20000

30000

40000

570575580585590595

Cr2O3Cr 2p

Cr3+

(e)





120573-band (1198601g minus 1198612u)







2)


400900140019002400290034003900

(a)

(b)



20000 40000 60000 80000

Abs

(A)

(nm)

(B)











0

50

100

000 20000 40000 60000



1381


1692


11791


6652


3212 minus00506

minus0105

minus0191

minus0267

minus0218


295∘C

60000∘C

Temperature (∘C)

TGA

()


02468

10121416182022242628303234

4 14 24 34 44 54 64 74

Lin

(Cou

nts)

2120579



100nm


65 75 85 95 105 115 125 135 145

minus25

minus35

minus45

minus55

minus6

minus5

minus4

minus3

80∘C

70∘C

60∘C

50∘C

40∘C

30∘C

ln120590

ac(S

Mc

m)

ln (120596)





Poly(POPDA)




4617 4762 mdash







015

017

019

021

023

025

027

029

031

033

035

300 310 320 330 340 350 360

s

T (K)



120590ac (120596) = 119860120596119904

(18)



4 Conclusions








References








2

O3

BaTiO3




































3




2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials










K2Cr2O7+H2O + 2H+ = 2K+ + 2H

2CO4 (7)






(HCrO4)minus

999445999468 (CrO4)2minus

+H+ K = 10minus59 (8)

(H2CrO4) 999445999468 (HCrO

4)minus

+H+ K = 41 (9)

2(HCrO4)minus

999445999468 (Cr2O7)2minus

+H2O K = 10

minus22

(10)


2

NH2

Ph

Ph

N+

H3 + H2CrO4

Complex

O

O

H

H

H

H

N

N+

OH2

O+

H2

Cr(11)


2

NH2

+∙











2

NH2 NH2 NH2

+∙

NH2 + H2CrO3 + H2O

+∙

NH2 +∙

NH

Para semidine

+ H2CrO4 = (13)

NH2 NH2 NH2 NH2

+∙

N+∙

N+∙

NH2 + H2CrO3 + 6 H2 = H+∙


(14)



2

NH2

+ K2Cr2O7 + 8H+= PS + 2K+

+ 2Cr3++ 7H2ON

+

H3 (15)


2O (16)



H H H

N N N

NH2 NH2 NH2 NH2

∙+

NH 2

(17)










6H6)2Cr3+ [30 31]












12and Cl 2p


32peaks






2O3







NH

NH

N Nn

N N nNH

NH

NH2

NH2

NH2NH2

NH2

NH2NH2

NH2

Cr3+ Cr3+

Clminus

Clminus

H2O

H2O

H+

H+


0

01

02

03

04

025050075010001250

Cl 2p

N1s

C1s

O1s

Cr 2p

Binding energy (eV)

Cou

nts

s

times106





(POPDA)Polymer




924s mdash


mdash 1044w


1152 mdash










Binding energy (eV)

0

5000

10000

15000

20000

25000

30000

35000

40000

280285290295

C 1s CndashC

CndashH

CndashO

C=N

(a)

Binding energy (eV)

0

5000

10000

15000

20000

25000

391396401406411

N1s

ndashNHndash

N+

ndashN=

(b)

Binding energy (eV)

0

10000

20000

30000

40000

50000

60000

525530535

O1s CndashOH

(c)

Binding energy (eV)

2000

2500

3000

3500

4000

4500

5000

190195200205

Cl 1s

Clminus

ndashCl

Cllowast

(d)

Binding energy (eV)

10000

20000

30000

40000

570575580585590595

Cr2O3Cr 2p

Cr3+

(e)





120573-band (1198601g minus 1198612u)







2)


400900140019002400290034003900

(a)

(b)



20000 40000 60000 80000

Abs

(A)

(nm)

(B)











0

50

100

000 20000 40000 60000



1381


1692


11791


6652


3212 minus00506

minus0105

minus0191

minus0267

minus0218


295∘C

60000∘C

Temperature (∘C)

TGA

()


02468

10121416182022242628303234

4 14 24 34 44 54 64 74

Lin

(Cou

nts)

2120579



100nm


65 75 85 95 105 115 125 135 145

minus25

minus35

minus45

minus55

minus6

minus5

minus4

minus3

80∘C

70∘C

60∘C

50∘C

40∘C

30∘C

ln120590

ac(S

Mc

m)

ln (120596)





Poly(POPDA)




4617 4762 mdash







015

017

019

021

023

025

027

029

031

033

035

300 310 320 330 340 350 360

s

T (K)



120590ac (120596) = 119860120596119904

(18)



4 Conclusions








References








2

O3

BaTiO3




































3




2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials










2

NH2 NH2 NH2

+∙

NH2 + H2CrO3 + H2O

+∙

NH2 +∙

NH

Para semidine

+ H2CrO4 = (13)

NH2 NH2 NH2 NH2

+∙

N+∙

N+∙

NH2 + H2CrO3 + 6 H2 = H+∙


(14)



2

NH2

+ K2Cr2O7 + 8H+= PS + 2K+

+ 2Cr3++ 7H2ON

+

H3 (15)


2O (16)



H H H

N N N

NH2 NH2 NH2 NH2

∙+

NH 2

(17)










6H6)2Cr3+ [30 31]












12and Cl 2p


32peaks






2O3







NH

NH

N Nn

N N nNH

NH

NH2

NH2

NH2NH2

NH2

NH2NH2

NH2

Cr3+ Cr3+

Clminus

Clminus

H2O

H2O

H+

H+


0

01

02

03

04

025050075010001250

Cl 2p

N1s

C1s

O1s

Cr 2p

Binding energy (eV)

Cou

nts

s

times106





(POPDA)Polymer




924s mdash


mdash 1044w


1152 mdash










Binding energy (eV)

0

5000

10000

15000

20000

25000

30000

35000

40000

280285290295

C 1s CndashC

CndashH

CndashO

C=N

(a)

Binding energy (eV)

0

5000

10000

15000

20000

25000

391396401406411

N1s

ndashNHndash

N+

ndashN=

(b)

Binding energy (eV)

0

10000

20000

30000

40000

50000

60000

525530535

O1s CndashOH

(c)

Binding energy (eV)

2000

2500

3000

3500

4000

4500

5000

190195200205

Cl 1s

Clminus

ndashCl

Cllowast

(d)

Binding energy (eV)

10000

20000

30000

40000

570575580585590595

Cr2O3Cr 2p

Cr3+

(e)





120573-band (1198601g minus 1198612u)







2)


400900140019002400290034003900

(a)

(b)



20000 40000 60000 80000

Abs

(A)

(nm)

(B)











0

50

100

000 20000 40000 60000



1381


1692


11791


6652


3212 minus00506

minus0105

minus0191

minus0267

minus0218


295∘C

60000∘C

Temperature (∘C)

TGA

()


02468

10121416182022242628303234

4 14 24 34 44 54 64 74

Lin

(Cou

nts)

2120579



100nm


65 75 85 95 105 115 125 135 145

minus25

minus35

minus45

minus55

minus6

minus5

minus4

minus3

80∘C

70∘C

60∘C

50∘C

40∘C

30∘C

ln120590

ac(S

Mc

m)

ln (120596)





Poly(POPDA)




4617 4762 mdash







015

017

019

021

023

025

027

029

031

033

035

300 310 320 330 340 350 360

s

T (K)



120590ac (120596) = 119860120596119904

(18)



4 Conclusions








References








2

O3

BaTiO3




































3




2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials












6H6)2Cr3+ [30 31]












12and Cl 2p


32peaks






2O3







NH

NH

N Nn

N N nNH

NH

NH2

NH2

NH2NH2

NH2

NH2NH2

NH2

Cr3+ Cr3+

Clminus

Clminus

H2O

H2O

H+

H+


0

01

02

03

04

025050075010001250

Cl 2p

N1s

C1s

O1s

Cr 2p

Binding energy (eV)

Cou

nts

s

times106





(POPDA)Polymer




924s mdash


mdash 1044w


1152 mdash










Binding energy (eV)

0

5000

10000

15000

20000

25000

30000

35000

40000

280285290295

C 1s CndashC

CndashH

CndashO

C=N

(a)

Binding energy (eV)

0

5000

10000

15000

20000

25000

391396401406411

N1s

ndashNHndash

N+

ndashN=

(b)

Binding energy (eV)

0

10000

20000

30000

40000

50000

60000

525530535

O1s CndashOH

(c)

Binding energy (eV)

2000

2500

3000

3500

4000

4500

5000

190195200205

Cl 1s

Clminus

ndashCl

Cllowast

(d)

Binding energy (eV)

10000

20000

30000

40000

570575580585590595

Cr2O3Cr 2p

Cr3+

(e)





120573-band (1198601g minus 1198612u)







2)


400900140019002400290034003900

(a)

(b)



20000 40000 60000 80000

Abs

(A)

(nm)

(B)











0

50

100

000 20000 40000 60000



1381


1692


11791


6652


3212 minus00506

minus0105

minus0191

minus0267

minus0218


295∘C

60000∘C

Temperature (∘C)

TGA

()


02468

10121416182022242628303234

4 14 24 34 44 54 64 74

Lin

(Cou

nts)

2120579



100nm


65 75 85 95 105 115 125 135 145

minus25

minus35

minus45

minus55

minus6

minus5

minus4

minus3

80∘C

70∘C

60∘C

50∘C

40∘C

30∘C

ln120590

ac(S

Mc

m)

ln (120596)





Poly(POPDA)




4617 4762 mdash







015

017

019

021

023

025

027

029

031

033

035

300 310 320 330 340 350 360

s

T (K)



120590ac (120596) = 119860120596119904

(18)



4 Conclusions








References








2

O3

BaTiO3




































3




2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




NH

NH

N Nn

N N nNH

NH

NH2

NH2

NH2NH2

NH2

NH2NH2

NH2

Cr3+ Cr3+

Clminus

Clminus

H2O

H2O

H+

H+


0

01

02

03

04

025050075010001250

Cl 2p

N1s

C1s

O1s

Cr 2p

Binding energy (eV)

Cou

nts

s

times106





(POPDA)Polymer




924s mdash


mdash 1044w


1152 mdash










Binding energy (eV)

0

5000

10000

15000

20000

25000

30000

35000

40000

280285290295

C 1s CndashC

CndashH

CndashO

C=N

(a)

Binding energy (eV)

0

5000

10000

15000

20000

25000

391396401406411

N1s

ndashNHndash

N+

ndashN=

(b)

Binding energy (eV)

0

10000

20000

30000

40000

50000

60000

525530535

O1s CndashOH

(c)

Binding energy (eV)

2000

2500

3000

3500

4000

4500

5000

190195200205

Cl 1s

Clminus

ndashCl

Cllowast

(d)

Binding energy (eV)

10000

20000

30000

40000

570575580585590595

Cr2O3Cr 2p

Cr3+

(e)





120573-band (1198601g minus 1198612u)







2)


400900140019002400290034003900

(a)

(b)



20000 40000 60000 80000

Abs

(A)

(nm)

(B)











0

50

100

000 20000 40000 60000



1381


1692


11791


6652


3212 minus00506

minus0105

minus0191

minus0267

minus0218


295∘C

60000∘C

Temperature (∘C)

TGA

()


02468

10121416182022242628303234

4 14 24 34 44 54 64 74

Lin

(Cou

nts)

2120579



100nm


65 75 85 95 105 115 125 135 145

minus25

minus35

minus45

minus55

minus6

minus5

minus4

minus3

80∘C

70∘C

60∘C

50∘C

40∘C

30∘C

ln120590

ac(S

Mc

m)

ln (120596)





Poly(POPDA)




4617 4762 mdash







015

017

019

021

023

025

027

029

031

033

035

300 310 320 330 340 350 360

s

T (K)



120590ac (120596) = 119860120596119904

(18)



4 Conclusions








References








2

O3

BaTiO3




































3




2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




Binding energy (eV)

0

5000

10000

15000

20000

25000

30000

35000

40000

280285290295

C 1s CndashC

CndashH

CndashO

C=N

(a)

Binding energy (eV)

0

5000

10000

15000

20000

25000

391396401406411

N1s

ndashNHndash

N+

ndashN=

(b)

Binding energy (eV)

0

10000

20000

30000

40000

50000

60000

525530535

O1s CndashOH

(c)

Binding energy (eV)

2000

2500

3000

3500

4000

4500

5000

190195200205

Cl 1s

Clminus

ndashCl

Cllowast

(d)

Binding energy (eV)

10000

20000

30000

40000

570575580585590595

Cr2O3Cr 2p

Cr3+

(e)





120573-band (1198601g minus 1198612u)







2)


400900140019002400290034003900

(a)

(b)



20000 40000 60000 80000

Abs

(A)

(nm)

(B)











0

50

100

000 20000 40000 60000



1381


1692


11791


6652


3212 minus00506

minus0105

minus0191

minus0267

minus0218


295∘C

60000∘C

Temperature (∘C)

TGA

()


02468

10121416182022242628303234

4 14 24 34 44 54 64 74

Lin

(Cou

nts)

2120579



100nm


65 75 85 95 105 115 125 135 145

minus25

minus35

minus45

minus55

minus6

minus5

minus4

minus3

80∘C

70∘C

60∘C

50∘C

40∘C

30∘C

ln120590

ac(S

Mc

m)

ln (120596)





Poly(POPDA)




4617 4762 mdash







015

017

019

021

023

025

027

029

031

033

035

300 310 320 330 340 350 360

s

T (K)



120590ac (120596) = 119860120596119904

(18)



4 Conclusions








References








2

O3

BaTiO3




































3




2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




400900140019002400290034003900

(a)

(b)



20000 40000 60000 80000

Abs

(A)

(nm)

(B)











0

50

100

000 20000 40000 60000



1381


1692


11791


6652


3212 minus00506

minus0105

minus0191

minus0267

minus0218


295∘C

60000∘C

Temperature (∘C)

TGA

()


02468

10121416182022242628303234

4 14 24 34 44 54 64 74

Lin

(Cou

nts)

2120579



100nm


65 75 85 95 105 115 125 135 145

minus25

minus35

minus45

minus55

minus6

minus5

minus4

minus3

80∘C

70∘C

60∘C

50∘C

40∘C

30∘C

ln120590

ac(S

Mc

m)

ln (120596)





Poly(POPDA)




4617 4762 mdash







015

017

019

021

023

025

027

029

031

033

035

300 310 320 330 340 350 360

s

T (K)



120590ac (120596) = 119860120596119904

(18)



4 Conclusions








References








2

O3

BaTiO3




































3




2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




0

50

100

000 20000 40000 60000



1381


1692


11791


6652


3212 minus00506

minus0105

minus0191

minus0267

minus0218


295∘C

60000∘C

Temperature (∘C)

TGA

()


02468

10121416182022242628303234

4 14 24 34 44 54 64 74

Lin

(Cou

nts)

2120579



100nm


65 75 85 95 105 115 125 135 145

minus25

minus35

minus45

minus55

minus6

minus5

minus4

minus3

80∘C

70∘C

60∘C

50∘C

40∘C

30∘C

ln120590

ac(S

Mc

m)

ln (120596)





Poly(POPDA)




4617 4762 mdash







015

017

019

021

023

025

027

029

031

033

035

300 310 320 330 340 350 360

s

T (K)



120590ac (120596) = 119860120596119904

(18)



4 Conclusions








References








2

O3

BaTiO3




































3




2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




100nm


65 75 85 95 105 115 125 135 145

minus25

minus35

minus45

minus55

minus6

minus5

minus4

minus3

80∘C

70∘C

60∘C

50∘C

40∘C

30∘C

ln120590

ac(S

Mc

m)

ln (120596)





Poly(POPDA)




4617 4762 mdash







015

017

019

021

023

025

027

029

031

033

035

300 310 320 330 340 350 360

s

T (K)



120590ac (120596) = 119860120596119904

(18)



4 Conclusions








References








2

O3

BaTiO3




































3




2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




015

017

019

021

023

025

027

029

031

033

035

300 310 320 330 340 350 360

s

T (K)



120590ac (120596) = 119860120596119904

(18)



4 Conclusions








References








2

O3

BaTiO3




































3




2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials






































3




2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





3




2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials



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