research article the influence of aluminum tripolyphosphate...

Research ArticleThe Influence of Aluminum Tripolyphosphate onthe Protective Behavior of an Acrylic Water-Based PaintApplied to Rusty Steels

Dongdong Song Jin Gao Lin Shen Hongxia Wan and Xiaogang Li

Corrosion and Protection Center University of Science and Technology Beijing Beijing 100083 China

Correspondence should be addressed to Jin Gao gaojinustbeducn

Received 17 October 2014 Accepted 19 January 2015

Academic Editor Demeter Tzeli

Copyright copy 2015 Dongdong Song et alThis is an open access article distributed under theCreative CommonsAttribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

The protective performance in conditions of total immersion of an acrylic water-based paint applied to rusty steel has been studiedusing electrochemical techniques There was no rust blister crack or flake that occurred on coating after 500 h immersion Thedata obtained have enabled the protective mechanism to be proposedThe specific pigments utilized in the formulation of the paintstudied can release phosphates to form a protective layer on metal substrate which can impede the access of aggressive speciesto substrate surface The coatings performed electrochemical activity in the beginning of immersion then the layer formed andresistance of coating increased

1 Introduction

The corrosion of iron and its alloys gives rise to a yearlyloss of billions of dollars Approximately 90 of all metallicsurfaces are protected with organic coatings [1] on accountof their low cost the ease of application and their aestheticfunctionality Organic paints are generally made up of bindersystems anticorrosive pigments fillers solvents and variousadditives [2 3]The anticorrosive ability of coating films restswith metal surface treatment the type and concentration ofanticorrosive pigment the way of coating formation and soon [4ndash8]

Now government pays more and more attention to per-sonnel healthy and environmental protection So composi-tion of paints and their applications are facing more stringentrequirements However traditional paints are facing adversecondition because of those utilized volatile organic com-pounds (VOCs) as solvents and toxic chemical as anticorro-sive pigments Except for a good anticorrosive performanceexcellent quality paint shall be equipped with environmentalfriendliness and easy construction performance In order tobetter meet the requirements of industry development suchas aviation and shipbuilding low VOC nontoxic and poorsurface preparations are the development direction

However due to the environmental and safety issuesconsiderable research activities have conducted to enhancethe increasing demand to reduce volatile organic compounds(VOCs) and hazardous air pollutants emissions increasingthe efforts to formulate waterborne systems for use as coat-ings [9] The best known and most frequently applied non-toxic anticorrosive pigments are phosphate pigments Andzinc phosphate was themost important kind of the phosphatepigments before 2004 [10ndash12] But the pigments based zincphosphates were classified according to the European Direc-tive 200473EU as hazardous substances to the environmentin 2004 [13] As result of this fact the development of ldquozinc-freerdquo inhibitor which is low or zero content of zinc deals withthe manufacturers Aluminum tripolyphosphate is one of thebest choices [14ndash16]

Surface preparation is a key factor prior to painting andthe success of the protective coating system depends onits correct execution Traditional theory believes that poorsurface preparation followed by a good coating systemusuallybrings worse results than the use of low quality products on awell prepared surface Rusts and oxides on the metal surfaceinfluence negatively the behavior of a coating system [17 18]The cleaning work is usually very high cost operations andcontaminates the environment A conversion coating can

Hindawi Publishing CorporationJournal of ChemistryVolume 2015 Article ID 618971 10 pageshttpdxdoiorg1011552015618971

2 Journal of Chemistry

250120583m

(a)

250120583m

(b)

Figure 1 Micrographs of the studied painted samples before and after immersion test (a) The studied painted samples before immersion(b) The studied painted samples after immersion

meet the challenge It may be defined as one formed bya chemical reaction which converts the surface of a metalsubstrate into a compound which became part of the coating

Now our team has excogitated a new paint that employsnoncontaminating inhibitors water as solvent and can meetpoor surface preparation In order to better demonstrate theprotective function of coating the behavior of this acrylicwater-based paint applied to rusty steel is studied by electro-chemical techniques

2 Experimental

21 Samples The behavior of a new acrylic paint producedby our lab has been studied Table 1 gives the more importanttechnical characteristics of this paint Mild steel Q235 hasbeen employed as the metallic substratum The samplesstudied were rectangular test pieces of 100mm times 150mm times1mm The samples were abraded using SiC abrasive papersup to 240 grit washed in distilled water and acetone in turnand then dried in air After that samples sprayed a solution of35 NaCl for 15 days to be rusting Before painting floatingrust of sample was cleaned by SiC abrasive papers The paintwas then applied using a brush to a thickness of 130120583m andthe compared samples of epoxy antirust paint were 160 120583mThe shapes of scratches were 119883 for EIS and line for LEISAll scratches were made by utility knife for 10mm long and50120583m wide The distance between scratch and each edge ofsamples was more than 20mm

22 Electrochemical Measurements EIS measurements werecarried out in the solution of 35 wt NaCl with a PARSTAT2273 system over the frequency range from 105Hz to 10minus2Hzat open circuit potential with a 20mVpotential perturbationThe internal parallel capacitance of the measuring machinewas smaller than 5 pF A three-electrode arrangement wasused consisting of a saturated calomel electrode (SCE) as ref-erence electrode a platinum electrode as counter electrodeand the coated sample as theworking electrode For thework-ing electrode the exposing area was 314 cm2 which woulddecrease the magnitude of the measured impedance andavoid hitting the limit of the measurement instrumentation

Table 1 Technical sheet of studied paint from our lab

Product description Water-based acrylic primer

Intended uses For use at new steel structure andmaintenance and repair

Color GrayVolume solids 61 plusmn 2 (ISO 32331998)Typical film thickness 100 120583m dryMethod of application Airless spray brush roller

especially at moderate and high frequenciesThe Pt electrodeareawas nearly the size of theworking electrode about 4 cm2Fitting of the impedance spectra was made using ZsimpWinsoftware

TheLEISmeasurements were performed on coating spec-imens that immersed in 35 NaCl solution through a PARModel 370 Scanning Electrochemical Workstation Thus thetest solution for LEIS measurements was 0001MNaCl solu-tion The microprobe was stepped over a designated area ofthe electrode surface The scanning took the form of a rasterin 119909-119910 plane The step size was controlled to obtain a plotof 32 lines times 21 lines The AC disturbance signal was 100mVand the excitation frequency for impedance measurementswas fixed at 5 kHz All LEIS measurements were carried outat ambient temperature (sim22∘C) Each test was performed atleast twice to confirm the repeatability

3 Results and Discussion

31 Immersion Tests Figure 1 shows the corrosion microto-pography of a painted sample immersed in the solution of35 wt NaCl for 21 days As can be observed there was norust blister crack or flake that occurred on coating whichindicates that the coating has remarkable corrosion resistanceperformance

In Table 2 the comparison of the corrosion morphologybetween epoxy antirust paint and our paint in function ofthe time of exposure is representedThe result shows that thestudied coating achieved a good anticorrosive performanceAfter 24 hours exposure there was obvious rusting in scratch

Journal of Chemistry 3

Table 2 Immersion testing results for scratched coating samplesafter different stage

Epoxy antirust paint Studied paint

0 h

24 h

8 d

of epoxy antirust coating but no change in the studiedcoating The scratch of the studied coating still did not haveapparent rust in 8 days exposure however serious corrosionwas found in epoxy antirust coating sample and even blister

From the above results the studied coating shows thefunction of inhibition to 35NaCl solution after immersionParticularly compared to epoxy antirust coating it is easyto see that the studied coating is provided with self-healingability This will be discussed in detail in the followingsections

32 Electrochemical Impedance Spectroscopy Figure 2 showsthe EIS diagrams corresponding to tests made on paintedsamples after being subjected to tests of different periods ofduration The data obtained demonstrate that in the first12 h of immersion interesting changes have taken place TheNyquist diagrams of the system in 1 h consisted of half acapacitive reactance arc of high frequency and a low fre-quency of capacitive reactance arc After 2 h those turnedinto a single capacitive arch There was a considerabledecrease of the arch that appeared in the Nyquist diagramsof first 2 h and increase after 4 h In parallel a decreasewas observed in the modulus of the impedance in the Bodediagrams of first 2 h and increase after 4 hThis decrease in theimpedance suggests that during the first hours of immersionthere is an increase in the activity taking place in the systemin this period Figure 2(b) shows that the Nyquist diagramspresent a single capacitive arch and the arch increases contin-uously from 1 d to 21 d

Figure 3 shows the EIS diagrams corresponding to testsmade on samples of studied paint with scratch after beingsubjected to tests of different periods of durationTheNyquistdiagrams presented a single capacitive arch Being parallelto intact painted samples there was a considerable decreaseof the arch that appeared in the Nyquist diagrams first andincreased then By contrast the Nyquist diagrams of epoxyantirust coatings with scratch (Figure 4) presented a singlecapacitive arch too but it decreased over time It is easy tosee that the modulus of the samples of studied coating withscratch in the Bode diagrams was inferior to that of epoxyantirust paint in initiation But after 8 days of immersioninversion has happened Figure 5 shows the phenomenonobviously It is in accordance with the result of immersion

AlH2P3O10997888rarr Al3+ + 2H+ + P

3O10

5minus (1)

Fe2+ + Fe3+ + P3O10

5minus997888rarr Fe

2P3O10

(2)

P3O10

5minus+ 2H2O 997888rarr 3PO

4

3minus+ 4H+ (3)

119909 (Fe2+ Fe3+) + 119910PO4

3minus997888rarr Fe

119909(PO4)119910

(4)

In order to guarantee the poor surface preparation anda good anticorrosive performance of our paint many specificpigments are added in itThese specific pigments are chemicalactive so the modulus of coating is at a low levelThe specificpigment utilized in the formulation of the studied coating isaluminum triphosphate The mechanism of actuation of thiscompound has not been clearly established

In last decades phosphate-based pigments are frequentlyapplied in coatings to improve their corrosion resistance [19ndash22] When the water has penetrated into the coating thepigments based on phosphate anions can release phosphatesto form a protective layer on the metal substrate which canimpede the access of the aggressive species to the substratesurface [22 23] Particularly aluminum tripolyphosphatecould hydrolyze to produce H+ which could minimizethe hydroxyl production on the metal substrate and retardcathode disbanding to prolong the service life of organiccoatings [14]

At 1 h theNyquist diagrams of the systemconsisted of onehalf of capacitive arc at high frequencies and another half ofcapacitive arc at low frequencies The one at high frequenciescan be attributed to the reaction between water and the largeamount of aluminum triphosphate well dispersed in the coat-ing matrix The equivalent circuit shown in Figure 6(a) hasbeen selected to simulate the data of 1 h After 2 h of immer-sion as aluminum triphosphate continues to react withwaterdenser protective layer was formed which seal the conduitsfor water penetration and lead to an increase in barrierproperty of the coating As a result the Bode diagram of thesystem demonstrated only a single time constant as shown inFigure 2 For this reason the equivalent circuit of Figure 6(c)has been selected In the circuit 119877

119904represents the resistance

between the working electrode and the reference electrodegenerally associated with the ohm resistance of the elec-trolyte119862dl and 119877119905 are related to double-layer capacitance andcharge-transfer resistance of the chemically active pigments


15

10

05

00

15100500

1h2h4h

8h12hFitting

times104

minusZ i

mag

inar

y(Ω

middotcm2)

Zreal (ohmmiddotcm2)

times104

(a)

60

40

20

00

60402000

1d8d12d

14d21dFitting

minusZ i

mag

inar

y(Ω

middotcm2)


times104

times104

(b)

Frequency (Hz)

104

103

102

10minus2

100

102

104

1h2h4h

8h12hFitting

|Z|

(Ωmiddotcm

2)

(c)

Frequency (Hz)10

minus210

010

210

4

105

104

103

102

1d8d12d

14d21dFitting

|Z|

(Ωmiddotcm

2)

(d)

Figure 2 Impedance spectra of painted samples without scratch after different immersion time in 35 wt NaCl solution (a) Nyquist plotsfrom 1 h to 12 h (b) Nyquist plots from 1 d to 21 d (c) Bode plots from 1 h to 12 h and (d) Bode plots from 1 d to 21 d

respectively119876119888is related to the capacitance of the coating 119877

119888

is the resistance of the pores and is a measure of the porosityas a consequence of the degradation of the coating

Study of the evolution of the diagrams of EIS with time ofimmersion enables an analysis to bemade about the variationof the protective capacity of painted samples In our casefrom the fit of the experimental diagrams to the equivalentcircuit proposed the values of the capacity 119876

119888 and of the

resistance 119877119888 associated with the layer of paint have been

calculated (Table 3) Figure 7 presents the evolution of theseparameters during the first 24 h of exposure In this figure itcan be observed how as the time of exposure is increased theresistance of the coating decreased first and then increasedIt is due to the anticorrosive performance of aluminum

tripolyphosphate that the number of defects in the coatingdecreases as protective layer forms In the first 2 h of expo-sure the capacity of coating increased because the waterpenetrates into the coating and the conductivity of thecoating increases However aluminum triphosphate releasesphosphates to form a protective layer on the metal substrateto impede the access of the aggressive species and corrosionSo the conductivity is reduced and capacity is down

Figure 3 shows the EIS diagrams of our painted sampleswith scratch after being subjected to tests of different periodsof durationThe Nyquist diagrams present a single capacitiveloop all the time There is a considerable decrease of the archthat appears in the Nyquist diagrams first and increases thenReason for this phenomenon is that aluminum triphosphate


4

3

2

1

0

43210

0h8h24h

96h192hFitting

Zreal (Ωmiddotcm2)

minusZ i

mag

inar

y(Ω

middotcm2)

times104

times104

(a)

105

104

103

102

Frequency (Hz)10

minus210

010

210

4

0h8h24h

96h192hFitting

|Z|

(Ωmiddotcm

2)

(b)

Figure 3 Impedance spectra of painted samples with scratch after different immersion time in 35 wt NaCl solution (a) Nyquist plots and(b) Bode plots

60

40

20

00

60402000

0h8h24h

96h192hFitting

Zreal (Ωmiddotcm2)

minusZ i

mag

inar

y(Ω

middotcm2)

times104

times104

(a)

Frequency (Hz)10

minus210

010

210

4

105

104

103

102

0h8h24h

96h192hFitting

|Z|

(Ωmiddotcm

2)

(b)

Figure 4 Impedance spectra of epoxy antirust painted samples with scratch after different immersion time in 35 wt NaCl solution (a)Nyquist plots and (b) Bode plots

Table 3 Impedance value of painted samples without scratch calculated from EIS spectra

1 h 2 h 4 h 8 h 12 h 1 d119877119904(Ωsdotcm2) 2746 3576 2749 2469 2442 23641198840of 119876119888(Fsdotcmminus2sdots119899minus1) 326 times 10minus4 343 times 10minus4 285 times 10minus4 205 times 10minus4 173 times 10minus4 153 times 10minus4

119899 04926 06544 06686 06743 06837 07029119877119888(Ωsdotcm2) 158 times 104 4776 3818 7051 161 times 104 329 times 104


Studied coatingEpoxy antirust coating

3

2

1

0

3210

Zreal (Ωmiddotcm2)

minusZ i

mag

inar

y(Ω

middotcm2)

times104

times104

Figure 5 Impedance spectra of epoxy antirust painted samples and painted samples with scratch after 8-day immersion times in 35 wtNaCl solution

Rs

Cdl Qc

Rt Rc

(a)

Rs

Rc

Qdl

Qc

Rt

(b)

Rs

Rc

Qc

(c)

Rs

Rc

Qdl

Rt

Cc

(d)

Figure 6 Equivalent circuit representing the coating system

releases phosphates to form a protective layer on the metalsubstrate as the water enters from the defect In the begin-ning the reactions cause the decrease of arch of the Nyquistdiagrams and select the equivalent circuit of Figure 6(b)Along with immersion extension the protective layerbecomes compact and the arch increases For this reason theequivalent circuit of Figure 6(c) is selected (Table 4) Thereis a considerable increase of the capacity of the coating firstand then decrease Meanwhile the resistance of the coatingbehaves on the contrary (Figure 8)

For the epoxy antirust painted samples with scratchthe Nyquist diagrams present a single capacitive arch too

(Figure 4) But plots from Bode diagrams show two timeconstants and the low frequency impedance was reduced astime extends because the water and aggressive ions diffuseon the substratecoating interface So the equivalent circuitof Figure 6(d) is selected (Table 5)

33 Localised Electrochemical Impedance Mapping As indi-cated in the LEIS projection of epoxy antirust coating(Figure 9) in initial stage of immersion the impedance valueat the defect was much lower than that of the adjacent intactcoating because of corrosion of bare metal in defect When


40

30

20

10

00

Time (h)0 5 10 15 20 25

Y0

ofQ

c(Fmiddotcm

minus2middotsn

minus1)

times10minus4

(a)

Time (h)

4

3

2

1

00 5 10 15 20 25

Rc

(Ωmiddotcm

2)

times104

(b)

Figure 7 Time evolution of 119876119888and 119877

119888of painted samples without scratch values calculated from EIS spectra

30

20

10

00

Time (h)0 50 100 150 200

Y0

ofQ

c(Fmiddotcm

minus2middotsn

minus1)

times10minus4

(a)

Time (h)

6

4

2

0 50 100 150 200

Rc

(Ωmiddotcm

2)

times104

(b)


119888of painted samples with scratch values calculated from EIS spectra

Table 4 Impedance value of painted samples with scratch calculated from EIS spectra

0 h 8 h 24 h 96 h 192 h119877119904(Ωsdotcm2) 2435 3567 2864 2589 2591198840of 119876119888(Fsdotcmminus2sdots119899minus1) 191 times 10minus4 210 times 10minus4 175 times 10minus4 120 times 10minus4 104 times 10minus4

119899 07724 06473 07035 07698 07913119877119888(Ωsdotcm2) 483 times 104 202 times 104 262 times 104 330 times 104 373 times 104

Table 5 Impedance value of epoxy antirust painted samples with scratch calculated from EIS spectra

0 h 8 h 24 h 96 h 192 h119877119904(Ωsdotcm2) 2782 2964 3801 3829 3413119862119888(Fsdotcmminus2) 592 times 10minus7 409 times 10minus7 632 times 10minus7 990 times 10minus7 383 times 10minus7

119877119888(Ωsdotcm2) 2778 2831 3588 3339 26741198840of 119876dl (Fsdotcm

minus2sdots119899minus1) 652 times 10minus5 835 times 10minus5 6986 times 10minus5 717 times 10minus5 856 times 10minus5



24

68

1012

0

0

0

20

40

60

80

100

2

4

6

8

X (120583m)

Y(120583

m)

4h4h

0000

1250E + 04

2500E + 04

3750E + 04

5000E + 04

6250E + 04

7500E + 04

8750E + 04

1000E + 050 2 4 6 8 10 12

0

1

2

3

4

5

6

7

8

X (120583m)Y

(120583m

)times10

3

times103

times103

times103

times103

0 2 4 6 8 10 12

X (120583m) times103

0 2 4 6 8 10 12

X (120583m) times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

0000

1250E + 04

2500E + 04

3750E + 04

5000E + 04

6250E + 04

7500E + 04

8750E + 04

1000E + 05

140h77h

|Z|

(Ω)

Figure 9 Time dependence of LEIS profiles and their projections of epoxy antirust painted samples

the immersion time extended the impedance in the adjacentcoating decreases which is attributed to permeation of corro-sive solution from the defect and the resultant disbanding ofcoating as observed visually after test and there are manyblisters around the defect (Figure 11)

The present work (Figure 10) shows that in contrast tothe impedance results measured on epoxy antirust coatingthe impedance value at the defect was not lower than that ofthe adjacent intact coating of studied coating sample all of theimmersion time Corresponding to results of electrochemicalimpedance spectroscopy the impedance value of studiedcoating increased over time because the pigments based onphosphate anions can release phosphates to form a protectivelayer on the metal substrate which can impede the accessof the aggressive species to the substrate surface The resultsof LEIS show that the studied coatings presented better self-healing and anticorrosive feature

4 Conclusions

The behavior in conditions of total immersion of an acrylicwater-based paint applied to rusty steel has been studiedusing electrochemical techniques The set of data obtainedhas enabled a mechanism for the anticorrosive performanceof the coating

This coating had a good anticorrosive performance After21 days of total immersion there was no rust blister crackor flake that occurred on coating Compared to the epoxyantirust painted samples the studied coatings exhibited bet-ter self-healing and anticorrosive feature The electrochem-ical results show that the specific pigments utilized in theformulation of the paint studied caused the electrochemicalactivity of the coatingWhen thewater has penetrated into thecoating the pigments based on phosphate anions can releasephosphates to form a protective layer on the metal substrate


24

68

1012

0

01

12

13

14

15

16

17

6

7

8

9

10

11

234

65

87

X (120583m)

Y(120583

m)

4h

times103

times103

times103

|Z|

(Ω)

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

4h0 2 4 6 8 10 12

X (120583m) times103

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04

0 2 4 6 8 10 12

X (120583m)times10

3

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

77h0 2 4 6 8 10 12

X (120583m) times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

140h

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04

Figure 10 Time dependence of LEIS profiles and their projections of studied painted samples

(a) (b)

Figure 11 Micrographs of the epoxy antirust painted samples (a) and studied painted samples (b) with defect after immersion test


The layer prevents the access of water and corrosion reactionto protect substrate

Conflict of Interests

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

Acknowledgment

The authors wish to acknowledge the financial support ofthe National Natural Science Foundation of China (no51071027)

References

[1] K BartonProtection against Atmospheric Corrosion JohnWileyamp Sons New York NY USA 1976

[2] D El-Hamid G Blustein M Deya B del Amo and R Romag-noli ldquoThe anticorrosive performance of zinc-free non-toxic pig-ment for paintsrdquo Materials Chemistry and Physics vol 127 no1-2 pp 353ndash357 2011

[3] E Armelin M Martı F Liesa J I Iribarren and C AlemanldquoPartial replacement of metallic zinc dust in heavy duty pro-tective coatings by conducting polymerrdquo Progress in OrganicCoatings vol 69 no 1 pp 26ndash30 2010

[4] D Vesely A Kalendova and P Nemec ldquoProperties of organiccoatings depending on chemical composition and structure ofpigment particlesrdquo Surface and Coatings Technology vol 204no 12-13 pp 2032ndash2037 2010

[5] J Havlık A Kalendova andD Vesely ldquoElectrochemical chem-ical and barrier action of zinc dustanticorrosive pigments con-taining coatingsrdquo Journal of Physics and Chemistry of Solids vol68 no 5-6 pp 1101ndash1105 2007

[6] M Zubielewicz E Kaminska-Tarnawska and A KozłowskaldquoProtective properties of organic phosphate-pigmented coat-ings on phosphated steel substratesrdquo Progress in Organic Coat-ings vol 53 no 4 pp 276ndash285 2005

[7] P Mosner A Kalendova and L Koudelka ldquoThe effects of themode of preparation on the anticorrosion properties of Ca-Znand Mg-Zn borophosphatesrdquo Pigment amp Resin Technology vol32 no 3 pp 166ndash174 2003

[8] A Kalendova D Vesely and P Kalenda ldquoAnticorrosion pig-ment based on calcium titanate with a perovskite structurerdquoPigment and Resin Technology vol 36 no 3 pp 123ndash133 2007

[9] J-M Yeh C-T Yao C-F Hsieh et al ldquoPreparation char-acterization and electrochemical corrosion studies on envi-ronmentally friendly waterborne polyurethaneNa+-MMT claynanocomposite coatingsrdquo European Polymer Journal vol 44no 10 pp 3046ndash3056 2008

[10] A Kalendova and J Brodinova ldquoSpinel and rutile pigmentscontaining Mg Ca Zn and other cations for anticorrosivecoatingsrdquo Anti-Corrosion Methods and Materials vol 50 no 5pp 352ndash363 2003

[11] M Bethencourt F J BotanaMMarcos RM Osuna and JMSanchez-Amaya ldquoInhibitor properties of lsquogreenrsquo pigments forpaintsrdquo Progress in Organic Coatings vol 46 no 4 pp 280ndash2872003

[12] M C Deya G Blustein R Romagnoli and B del Amo ldquoTheinfluence of the anion type on the anticorrosive behaviour of

inorganic phosphatesrdquo Surface and Coatings Technology vol150 no 2-3 pp 133ndash142 2002

[13] H Kukackova A Vrastilova and A Kalendova ldquoNon-toxicanticorrosive pigments intended for applications in high-solidsand waterborne paintsrdquo Physics Procedia vol 44 pp 238ndash2462013

[14] X Lu Y Zuo X Zhao and Y Tang ldquoThe influence of aluminumtri-polyphosphate on the protective behavior of Mg-rich epoxycoating on AZ91D magnesium alloyrdquo Electrochimica Acta vol93 pp 53ndash64 2013

[15] S N Roselli B del Amo R O Carbonari A R Di Sarli andR Romagnoli ldquoPainting rusted steel the role of aluminumphosphosilicaterdquo Corrosion Science vol 74 pp 194ndash205 2013

[16] M Deya V F Vetere R Romagnoli and B del Amo ldquoAlu-minium tripolyphosphate pigments for anticorrosive paintsrdquoPigment amp Resin Technology vol 30 no 1 pp 13ndash24 2001

[17] D de la Fuente J Simancas andMMorcillo ldquoEffect of variableamounts of rust at the steelpaint interface on the behaviour ofanticorrosive paint systemsrdquo Progress in Organic Coatings vol46 no 4 pp 241ndash249 2003

[18] C I Elsner E Cavalcanti O Ferraz and A R Di SarlildquoEvaluation of the surface treatment effect on the anticorrosiveperformance of paint systems on steelrdquo Progress in OrganicCoatings vol 48 no 1 pp 50ndash62 2003

[19] P de Lima-Neto A P de Araujo W S Araujo and A NCorreia ldquoStudy of the anticorrosive behaviour of epoxy binderscontaining non-toxic inorganic corrosion inhibitor pigmentsrdquoProgress in Organic Coatings vol 62 no 3 pp 344ndash350 2008

[20] R Naderi andMM Attar ldquoElectrochemical study of protectivebehavior of organic coating pigmented with zinc aluminumpolyphosphate as a modified zinc phosphate at different pig-ment volume concentrationsrdquo Progress in Organic Coatings vol66 no 3 pp 314ndash320 2009

[21] C Deya G Blustein B Del Amo and R Romagnoli ldquoEvalua-tion of eco-friendly anticorrosive pigments for paints in serviceconditionsrdquo Progress in Organic Coatings vol 69 no 1 pp 1ndash62010

[22] R Naderi and M M Attar ldquoThe role of zinc aluminum phos-phate anticorrosive pigment in Protective Performance andcathodic disbondment of epoxy coatingrdquoCorrosion Science vol52 no 4 pp 1291ndash1296 2010

[23] M A Hernandez F Galliano and D Landolt ldquoMechanismof cathodic delamination control of zinc-aluminum phosphatepigment in waterborne coatingsrdquo Corrosion Science vol 46 no9 pp 2281ndash2300 2004

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250120583m

(a)

250120583m

(b)

Figure 1 Micrographs of the studied painted samples before and after immersion test (a) The studied painted samples before immersion(b) The studied painted samples after immersion

meet the challenge It may be defined as one formed bya chemical reaction which converts the surface of a metalsubstrate into a compound which became part of the coating

Now our team has excogitated a new paint that employsnoncontaminating inhibitors water as solvent and can meetpoor surface preparation In order to better demonstrate theprotective function of coating the behavior of this acrylicwater-based paint applied to rusty steel is studied by electro-chemical techniques

2 Experimental

21 Samples The behavior of a new acrylic paint producedby our lab has been studied Table 1 gives the more importanttechnical characteristics of this paint Mild steel Q235 hasbeen employed as the metallic substratum The samplesstudied were rectangular test pieces of 100mm times 150mm times1mm The samples were abraded using SiC abrasive papersup to 240 grit washed in distilled water and acetone in turnand then dried in air After that samples sprayed a solution of35 NaCl for 15 days to be rusting Before painting floatingrust of sample was cleaned by SiC abrasive papers The paintwas then applied using a brush to a thickness of 130120583m andthe compared samples of epoxy antirust paint were 160 120583mThe shapes of scratches were 119883 for EIS and line for LEISAll scratches were made by utility knife for 10mm long and50120583m wide The distance between scratch and each edge ofsamples was more than 20mm

22 Electrochemical Measurements EIS measurements werecarried out in the solution of 35 wt NaCl with a PARSTAT2273 system over the frequency range from 105Hz to 10minus2Hzat open circuit potential with a 20mVpotential perturbationThe internal parallel capacitance of the measuring machinewas smaller than 5 pF A three-electrode arrangement wasused consisting of a saturated calomel electrode (SCE) as ref-erence electrode a platinum electrode as counter electrodeand the coated sample as theworking electrode For thework-ing electrode the exposing area was 314 cm2 which woulddecrease the magnitude of the measured impedance andavoid hitting the limit of the measurement instrumentation

Table 1 Technical sheet of studied paint from our lab

Product description Water-based acrylic primer

Intended uses For use at new steel structure andmaintenance and repair

Color GrayVolume solids 61 plusmn 2 (ISO 32331998)Typical film thickness 100 120583m dryMethod of application Airless spray brush roller

especially at moderate and high frequenciesThe Pt electrodeareawas nearly the size of theworking electrode about 4 cm2Fitting of the impedance spectra was made using ZsimpWinsoftware

TheLEISmeasurements were performed on coating spec-imens that immersed in 35 NaCl solution through a PARModel 370 Scanning Electrochemical Workstation Thus thetest solution for LEIS measurements was 0001MNaCl solu-tion The microprobe was stepped over a designated area ofthe electrode surface The scanning took the form of a rasterin 119909-119910 plane The step size was controlled to obtain a plotof 32 lines times 21 lines The AC disturbance signal was 100mVand the excitation frequency for impedance measurementswas fixed at 5 kHz All LEIS measurements were carried outat ambient temperature (sim22∘C) Each test was performed atleast twice to confirm the repeatability

3 Results and Discussion

31 Immersion Tests Figure 1 shows the corrosion microto-pography of a painted sample immersed in the solution of35 wt NaCl for 21 days As can be observed there was norust blister crack or flake that occurred on coating whichindicates that the coating has remarkable corrosion resistanceperformance

In Table 2 the comparison of the corrosion morphologybetween epoxy antirust paint and our paint in function ofthe time of exposure is representedThe result shows that thestudied coating achieved a good anticorrosive performanceAfter 24 hours exposure there was obvious rusting in scratch




0 h

24 h

8 d





AlH2P3O10997888rarr Al3+ + 2H+ + P

3O10

5minus (1)

Fe2+ + Fe3+ + P3O10

5minus997888rarr Fe

2P3O10

(2)

P3O10


4

3minus+ 4H+ (3)

119909 (Fe2+ Fe3+) + 119910PO4

3minus997888rarr Fe

119909(PO4)119910

(4)







15

10

05

00

15100500

1h2h4h

8h12hFitting

times104

minusZ i

mag

inar

y(Ω

middotcm2)


times104

(a)

60

40

20

00

60402000

1d8d12d

14d21dFitting

minusZ i

mag

inar

y(Ω

middotcm2)


times104

times104

(b)

Frequency (Hz)

104

103

102

10minus2

100

102

104

1h2h4h

8h12hFitting

|Z|

(Ωmiddotcm

2)

(c)

Frequency (Hz)10

minus210

010

210

4

105

104

103

102

1d8d12d

14d21dFitting

|Z|

(Ωmiddotcm

2)

(d)



119888



119888 and of the






4

3

2

1

0

43210

0h8h24h

96h192hFitting

Zreal (Ωmiddotcm2)

minusZ i

mag

inar

y(Ω

middotcm2)

times104

times104

(a)

105

104

103

102

Frequency (Hz)10

minus210

010

210

4

0h8h24h

96h192hFitting

|Z|

(Ωmiddotcm

2)

(b)


60

40

20

00

60402000

0h8h24h

96h192hFitting

Zreal (Ωmiddotcm2)

minusZ i

mag

inar

y(Ω

middotcm2)

times104

times104

(a)

Frequency (Hz)10

minus210

010

210

4

105

104

103

102

0h8h24h

96h192hFitting

|Z|

(Ωmiddotcm

2)

(b)







3

2

1

0

3210

Zreal (Ωmiddotcm2)

minusZ i

mag

inar

y(Ω

middotcm2)

times104

times104


Rs

Cdl Qc

Rt Rc

(a)

Rs

Rc

Qdl

Qc

Rt

(b)

Rs

Rc

Qc

(c)

Rs

Rc

Qdl

Rt

Cc

(d)







40

30

20

10

00

Time (h)0 5 10 15 20 25

Y0

ofQ

c(Fmiddotcm

minus2middotsn

minus1)

times10minus4

(a)

Time (h)

4

3

2

1

00 5 10 15 20 25

Rc

(Ωmiddotcm

2)

times104

(b)



30

20

10

00

Time (h)0 50 100 150 200

Y0

ofQ

c(Fmiddotcm

minus2middotsn

minus1)

times10minus4

(a)

Time (h)

6

4

2

0 50 100 150 200

Rc

(Ωmiddotcm

2)

times104

(b)












24

68

1012

0

0

0

20

40

60

80

100

2

4

6

8

X (120583m)

Y(120583

m)

4h4h

0000

1250E + 04

2500E + 04

3750E + 04

5000E + 04

6250E + 04

7500E + 04

8750E + 04

1000E + 050 2 4 6 8 10 12

0

1

2

3

4

5

6

7

8

X (120583m)Y

(120583m

)times10

3

times103

times103

times103

times103

0 2 4 6 8 10 12

X (120583m) times103

0 2 4 6 8 10 12

X (120583m) times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

0000

1250E + 04

2500E + 04

3750E + 04

5000E + 04

6250E + 04

7500E + 04

8750E + 04

1000E + 05

140h77h

|Z|

(Ω)




4 Conclusions




24

68

1012

0

01

12

13

14

15

16

17

6

7

8

9

10

11

234

65

87

X (120583m)

Y(120583

m)

4h

times103

times103

times103

|Z|

(Ω)

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

4h0 2 4 6 8 10 12

X (120583m) times103

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04

0 2 4 6 8 10 12

X (120583m)times10

3

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

77h0 2 4 6 8 10 12

X (120583m) times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

140h

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04


(a) (b)






Acknowledgment


References


































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




0 h

24 h

8 d





AlH2P3O10997888rarr Al3+ + 2H+ + P

3O10

5minus (1)

Fe2+ + Fe3+ + P3O10

5minus997888rarr Fe

2P3O10

(2)

P3O10


4

3minus+ 4H+ (3)

119909 (Fe2+ Fe3+) + 119910PO4

3minus997888rarr Fe

119909(PO4)119910

(4)







15

10

05

00

15100500

1h2h4h

8h12hFitting

times104

minusZ i

mag

inar

y(Ω

middotcm2)


times104

(a)

60

40

20

00

60402000

1d8d12d

14d21dFitting

minusZ i

mag

inar

y(Ω

middotcm2)


times104

times104

(b)

Frequency (Hz)

104

103

102

10minus2

100

102

104

1h2h4h

8h12hFitting

|Z|

(Ωmiddotcm

2)

(c)

Frequency (Hz)10

minus210

010

210

4

105

104

103

102

1d8d12d

14d21dFitting

|Z|

(Ωmiddotcm

2)

(d)



119888



119888 and of the






4

3

2

1

0

43210

0h8h24h

96h192hFitting

Zreal (Ωmiddotcm2)

minusZ i

mag

inar

y(Ω

middotcm2)

times104

times104

(a)

105

104

103

102

Frequency (Hz)10

minus210

010

210

4

0h8h24h

96h192hFitting

|Z|

(Ωmiddotcm

2)

(b)


60

40

20

00

60402000

0h8h24h

96h192hFitting

Zreal (Ωmiddotcm2)

minusZ i

mag

inar

y(Ω

middotcm2)

times104

times104

(a)

Frequency (Hz)10

minus210

010

210

4

105

104

103

102

0h8h24h

96h192hFitting

|Z|

(Ωmiddotcm

2)

(b)







3

2

1

0

3210

Zreal (Ωmiddotcm2)

minusZ i

mag

inar

y(Ω

middotcm2)

times104

times104


Rs

Cdl Qc

Rt Rc

(a)

Rs

Rc

Qdl

Qc

Rt

(b)

Rs

Rc

Qc

(c)

Rs

Rc

Qdl

Rt

Cc

(d)







40

30

20

10

00

Time (h)0 5 10 15 20 25

Y0

ofQ

c(Fmiddotcm

minus2middotsn

minus1)

times10minus4

(a)

Time (h)

4

3

2

1

00 5 10 15 20 25

Rc

(Ωmiddotcm

2)

times104

(b)



30

20

10

00

Time (h)0 50 100 150 200

Y0

ofQ

c(Fmiddotcm

minus2middotsn

minus1)

times10minus4

(a)

Time (h)

6

4

2

0 50 100 150 200

Rc

(Ωmiddotcm

2)

times104

(b)












24

68

1012

0

0

0

20

40

60

80

100

2

4

6

8

X (120583m)

Y(120583

m)

4h4h

0000

1250E + 04

2500E + 04

3750E + 04

5000E + 04

6250E + 04

7500E + 04

8750E + 04

1000E + 050 2 4 6 8 10 12

0

1

2

3

4

5

6

7

8

X (120583m)Y

(120583m

)times10

3

times103

times103

times103

times103

0 2 4 6 8 10 12

X (120583m) times103

0 2 4 6 8 10 12

X (120583m) times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

0000

1250E + 04

2500E + 04

3750E + 04

5000E + 04

6250E + 04

7500E + 04

8750E + 04

1000E + 05

140h77h

|Z|

(Ω)




4 Conclusions




24

68

1012

0

01

12

13

14

15

16

17

6

7

8

9

10

11

234

65

87

X (120583m)

Y(120583

m)

4h

times103

times103

times103

|Z|

(Ω)

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

4h0 2 4 6 8 10 12

X (120583m) times103

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04

0 2 4 6 8 10 12

X (120583m)times10

3

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

77h0 2 4 6 8 10 12

X (120583m) times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

140h

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04


(a) (b)






Acknowledgment


References


































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


15

10

05

00

15100500

1h2h4h

8h12hFitting

times104

minusZ i

mag

inar

y(Ω

middotcm2)


times104

(a)

60

40

20

00

60402000

1d8d12d

14d21dFitting

minusZ i

mag

inar

y(Ω

middotcm2)


times104

times104

(b)

Frequency (Hz)

104

103

102

10minus2

100

102

104

1h2h4h

8h12hFitting

|Z|

(Ωmiddotcm

2)

(c)

Frequency (Hz)10

minus210

010

210

4

105

104

103

102

1d8d12d

14d21dFitting

|Z|

(Ωmiddotcm

2)

(d)



119888



119888 and of the






4

3

2

1

0

43210

0h8h24h

96h192hFitting

Zreal (Ωmiddotcm2)

minusZ i

mag

inar

y(Ω

middotcm2)

times104

times104

(a)

105

104

103

102

Frequency (Hz)10

minus210

010

210

4

0h8h24h

96h192hFitting

|Z|

(Ωmiddotcm

2)

(b)


60

40

20

00

60402000

0h8h24h

96h192hFitting

Zreal (Ωmiddotcm2)

minusZ i

mag

inar

y(Ω

middotcm2)

times104

times104

(a)

Frequency (Hz)10

minus210

010

210

4

105

104

103

102

0h8h24h

96h192hFitting

|Z|

(Ωmiddotcm

2)

(b)







3

2

1

0

3210

Zreal (Ωmiddotcm2)

minusZ i

mag

inar

y(Ω

middotcm2)

times104

times104


Rs

Cdl Qc

Rt Rc

(a)

Rs

Rc

Qdl

Qc

Rt

(b)

Rs

Rc

Qc

(c)

Rs

Rc

Qdl

Rt

Cc

(d)







40

30

20

10

00

Time (h)0 5 10 15 20 25

Y0

ofQ

c(Fmiddotcm

minus2middotsn

minus1)

times10minus4

(a)

Time (h)

4

3

2

1

00 5 10 15 20 25

Rc

(Ωmiddotcm

2)

times104

(b)



30

20

10

00

Time (h)0 50 100 150 200

Y0

ofQ

c(Fmiddotcm

minus2middotsn

minus1)

times10minus4

(a)

Time (h)

6

4

2

0 50 100 150 200

Rc

(Ωmiddotcm

2)

times104

(b)












24

68

1012

0

0

0

20

40

60

80

100

2

4

6

8

X (120583m)

Y(120583

m)

4h4h

0000

1250E + 04

2500E + 04

3750E + 04

5000E + 04

6250E + 04

7500E + 04

8750E + 04

1000E + 050 2 4 6 8 10 12

0

1

2

3

4

5

6

7

8

X (120583m)Y

(120583m

)times10

3

times103

times103

times103

times103

0 2 4 6 8 10 12

X (120583m) times103

0 2 4 6 8 10 12

X (120583m) times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

0000

1250E + 04

2500E + 04

3750E + 04

5000E + 04

6250E + 04

7500E + 04

8750E + 04

1000E + 05

140h77h

|Z|

(Ω)




4 Conclusions




24

68

1012

0

01

12

13

14

15

16

17

6

7

8

9

10

11

234

65

87

X (120583m)

Y(120583

m)

4h

times103

times103

times103

|Z|

(Ω)

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

4h0 2 4 6 8 10 12

X (120583m) times103

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04

0 2 4 6 8 10 12

X (120583m)times10

3

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

77h0 2 4 6 8 10 12

X (120583m) times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

140h

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04


(a) (b)






Acknowledgment


References


































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


4

3

2

1

0

43210

0h8h24h

96h192hFitting

Zreal (Ωmiddotcm2)

minusZ i

mag

inar

y(Ω

middotcm2)

times104

times104

(a)

105

104

103

102

Frequency (Hz)10

minus210

010

210

4

0h8h24h

96h192hFitting

|Z|

(Ωmiddotcm

2)

(b)


60

40

20

00

60402000

0h8h24h

96h192hFitting

Zreal (Ωmiddotcm2)

minusZ i

mag

inar

y(Ω

middotcm2)

times104

times104

(a)

Frequency (Hz)10

minus210

010

210

4

105

104

103

102

0h8h24h

96h192hFitting

|Z|

(Ωmiddotcm

2)

(b)







3

2

1

0

3210

Zreal (Ωmiddotcm2)

minusZ i

mag

inar

y(Ω

middotcm2)

times104

times104


Rs

Cdl Qc

Rt Rc

(a)

Rs

Rc

Qdl

Qc

Rt

(b)

Rs

Rc

Qc

(c)

Rs

Rc

Qdl

Rt

Cc

(d)







40

30

20

10

00

Time (h)0 5 10 15 20 25

Y0

ofQ

c(Fmiddotcm

minus2middotsn

minus1)

times10minus4

(a)

Time (h)

4

3

2

1

00 5 10 15 20 25

Rc

(Ωmiddotcm

2)

times104

(b)



30

20

10

00

Time (h)0 50 100 150 200

Y0

ofQ

c(Fmiddotcm

minus2middotsn

minus1)

times10minus4

(a)

Time (h)

6

4

2

0 50 100 150 200

Rc

(Ωmiddotcm

2)

times104

(b)












24

68

1012

0

0

0

20

40

60

80

100

2

4

6

8

X (120583m)

Y(120583

m)

4h4h

0000

1250E + 04

2500E + 04

3750E + 04

5000E + 04

6250E + 04

7500E + 04

8750E + 04

1000E + 050 2 4 6 8 10 12

0

1

2

3

4

5

6

7

8

X (120583m)Y

(120583m

)times10

3

times103

times103

times103

times103

0 2 4 6 8 10 12

X (120583m) times103

0 2 4 6 8 10 12

X (120583m) times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

0000

1250E + 04

2500E + 04

3750E + 04

5000E + 04

6250E + 04

7500E + 04

8750E + 04

1000E + 05

140h77h

|Z|

(Ω)




4 Conclusions




24

68

1012

0

01

12

13

14

15

16

17

6

7

8

9

10

11

234

65

87

X (120583m)

Y(120583

m)

4h

times103

times103

times103

|Z|

(Ω)

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

4h0 2 4 6 8 10 12

X (120583m) times103

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04

0 2 4 6 8 10 12

X (120583m)times10

3

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

77h0 2 4 6 8 10 12

X (120583m) times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

140h

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04


(a) (b)






Acknowledgment


References


































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



3

2

1

0

3210

Zreal (Ωmiddotcm2)

minusZ i

mag

inar

y(Ω

middotcm2)

times104

times104


Rs

Cdl Qc

Rt Rc

(a)

Rs

Rc

Qdl

Qc

Rt

(b)

Rs

Rc

Qc

(c)

Rs

Rc

Qdl

Rt

Cc

(d)







40

30

20

10

00

Time (h)0 5 10 15 20 25

Y0

ofQ

c(Fmiddotcm

minus2middotsn

minus1)

times10minus4

(a)

Time (h)

4

3

2

1

00 5 10 15 20 25

Rc

(Ωmiddotcm

2)

times104

(b)



30

20

10

00

Time (h)0 50 100 150 200

Y0

ofQ

c(Fmiddotcm

minus2middotsn

minus1)

times10minus4

(a)

Time (h)

6

4

2

0 50 100 150 200

Rc

(Ωmiddotcm

2)

times104

(b)












24

68

1012

0

0

0

20

40

60

80

100

2

4

6

8

X (120583m)

Y(120583

m)

4h4h

0000

1250E + 04

2500E + 04

3750E + 04

5000E + 04

6250E + 04

7500E + 04

8750E + 04

1000E + 050 2 4 6 8 10 12

0

1

2

3

4

5

6

7

8

X (120583m)Y

(120583m

)times10

3

times103

times103

times103

times103

0 2 4 6 8 10 12

X (120583m) times103

0 2 4 6 8 10 12

X (120583m) times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

0000

1250E + 04

2500E + 04

3750E + 04

5000E + 04

6250E + 04

7500E + 04

8750E + 04

1000E + 05

140h77h

|Z|

(Ω)




4 Conclusions




24

68

1012

0

01

12

13

14

15

16

17

6

7

8

9

10

11

234

65

87

X (120583m)

Y(120583

m)

4h

times103

times103

times103

|Z|

(Ω)

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

4h0 2 4 6 8 10 12

X (120583m) times103

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04

0 2 4 6 8 10 12

X (120583m)times10

3

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

77h0 2 4 6 8 10 12

X (120583m) times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

140h

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04


(a) (b)






Acknowledgment


References


































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


40

30

20

10

00

Time (h)0 5 10 15 20 25

Y0

ofQ

c(Fmiddotcm

minus2middotsn

minus1)

times10minus4

(a)

Time (h)

4

3

2

1

00 5 10 15 20 25

Rc

(Ωmiddotcm

2)

times104

(b)



30

20

10

00

Time (h)0 50 100 150 200

Y0

ofQ

c(Fmiddotcm

minus2middotsn

minus1)

times10minus4

(a)

Time (h)

6

4

2

0 50 100 150 200

Rc

(Ωmiddotcm

2)

times104

(b)












24

68

1012

0

0

0

20

40

60

80

100

2

4

6

8

X (120583m)

Y(120583

m)

4h4h

0000

1250E + 04

2500E + 04

3750E + 04

5000E + 04

6250E + 04

7500E + 04

8750E + 04

1000E + 050 2 4 6 8 10 12

0

1

2

3

4

5

6

7

8

X (120583m)Y

(120583m

)times10

3

times103

times103

times103

times103

0 2 4 6 8 10 12

X (120583m) times103

0 2 4 6 8 10 12

X (120583m) times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

0000

1250E + 04

2500E + 04

3750E + 04

5000E + 04

6250E + 04

7500E + 04

8750E + 04

1000E + 05

140h77h

|Z|

(Ω)




4 Conclusions




24

68

1012

0

01

12

13

14

15

16

17

6

7

8

9

10

11

234

65

87

X (120583m)

Y(120583

m)

4h

times103

times103

times103

|Z|

(Ω)

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

4h0 2 4 6 8 10 12

X (120583m) times103

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04

0 2 4 6 8 10 12

X (120583m)times10

3

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

77h0 2 4 6 8 10 12

X (120583m) times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

140h

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04


(a) (b)






Acknowledgment


References


































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


24

68

1012

0

0

0

20

40

60

80

100

2

4

6

8

X (120583m)

Y(120583

m)

4h4h

0000

1250E + 04

2500E + 04

3750E + 04

5000E + 04

6250E + 04

7500E + 04

8750E + 04

1000E + 050 2 4 6 8 10 12

0

1

2

3

4

5

6

7

8

X (120583m)Y

(120583m

)times10

3

times103

times103

times103

times103

0 2 4 6 8 10 12

X (120583m) times103

0 2 4 6 8 10 12

X (120583m) times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

0000

1250E + 04

2500E + 04

3750E + 04

5000E + 04

6250E + 04

7500E + 04

8750E + 04

1000E + 05

140h77h

|Z|

(Ω)




4 Conclusions




24

68

1012

0

01

12

13

14

15

16

17

6

7

8

9

10

11

234

65

87

X (120583m)

Y(120583

m)

4h

times103

times103

times103

|Z|

(Ω)

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

4h0 2 4 6 8 10 12

X (120583m) times103

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04

0 2 4 6 8 10 12

X (120583m)times10

3

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

77h0 2 4 6 8 10 12

X (120583m) times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

140h

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04


(a) (b)






Acknowledgment


References


































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


24

68

1012

0

01

12

13

14

15

16

17

6

7

8

9

10

11

234

65

87

X (120583m)

Y(120583

m)

4h

times103

times103

times103

|Z|

(Ω)

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

4h0 2 4 6 8 10 12

X (120583m) times103

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04

0 2 4 6 8 10 12

X (120583m)times10

3

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

77h0 2 4 6 8 10 12

X (120583m) times103

0

1

2

3

4

5

6

7

8

Y(120583

m)

times103

140h

6000

7375

8750

1013E + 04

1150E + 04

1288E + 04

1425E + 04

1563E + 04

1700E + 04


(a) (b)






Acknowledgment


References


































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





Acknowledgment


References


































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

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