Research ArticleInteractions between PhosphoricTannic Acid andDifferent Forms of FeOOH

Lefu Mei1 Libing Liao1 Zise Wang2 and Chunchun Xu3

1School of Material Sciences and Technology China University of Geosciences Beijing 100083 China2China Science and Technology Museum Beijing 100029 China3School of Material Sciences and Technology Beijing University of Chemical Technology Beijing 100029 China

Correspondence should be addressed to Lefu Mei mlfcugbeducn and Libing Liao claylcugbeducn

Received 23 July 2014 Accepted 17 September 2014

Academic Editor Zhaohui Li

Copyright copy 2015 Lefu Mei et alThis is an open access article distributed under the Creative Commons Attribution License whichpermits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Alpha beta gamma and delta hydroxyl ferric oxides (FeOOH) as the most common rust layers on iron surface play differentroles in iron preservation Using modern surface analysis technologies such as X-ray diffraction (XRD) infrared spectra (IR) X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) we studied the interactions between these fourtypes of synthetic FeOOH and phosphoric and tannic acid of different concentrations and proportions A 3 tannic acid + 10phosphoric acid + FeOOHwas themost suitable formula for rust stabilizer and its reaction productsweremade up of iron phosphateand chelate of iron and tannin This research provided technical basis in distinguishing FeOOH and selecting rust layer stabilizerfor the preservation of iron especially iron cultural relics

1 Introduction

Structure and composition of corrosion products on iron aretwo important factors of causing its further corrosion apartfrom environmental factors iron components and defect andinclusion in iron There are two types of rust layers a looseouter rust layer and a dense inner rust layer The former wascomposed of 120572-FeOOH 120574-FeOOHmagnetite (Fe

3O4) H2O

and amorphous ferric oxyhydroxide (FeOx(OH)3minus2x x = 0-1)

while the latter was composed mainly of Fe3O4with a little

120572-FeOOH [1 2] The 120573-FeOOH is a typical product of FeCl3

hydrolysis whereas 120572-FeOOH is that of Fe(NO3)3hydrolysis

and under specific conditions these hydrolytic products maytransform to 120572-Fe

2O3[3ndash5] The 120575-FeOOH is a type of

amorphous hydroxyl oxide rust layer on ironmaterial surface[6] forming a compact rust layer that enhances corrosionresistance of the steel [7]

The underlying corrosion of carbon steel was dependenton the inherent properties of the rust layers formed underdifferent conditions such as composition and structure with120573-FeOOH exerting significant influence among all the ironoxides [8] In terms of reaction with Fe(OH)

2to produce

Fe3O4 the following order was observed 120573-FeOOH gt 120572-

FeOOH≫ 120574-FeOOH [9]Rust converters are chemical formulations that can be

applied to corroded surfaces causing their passivation andelimination of possible further attack after the application ofa coating [10] To reduce the effects of hydroxyl ferric oxideon steel preservation surface stabilizing treatment of rustlayer has been widely used in the steel anticorrosion fieldBy employing a processing method of a chemical conversionfilm the hydroxyl oxide rust layer on the iron may undertakea chemical conversion and form porous membrane bar-rier with good ventilation property and water permeability[11] The excellent atmospheric corrosion resistance of thephosphoric Dhar pillar iron was attributed to the formationof a protective passive film on the surface [12] Chemicalconversion film as inoxidizing coating of metal reduceschemical activity of the metal and increases thermodynamicstability of steel in environmental medium In addition thesurface productsmay also play a certain role inmetal isolationfrom environmental medium Chemical conversion filmssuch as thin layer exquisite crystallization and porosity maybe combined with sealing materials Accordingly industrial

Hindawi Publishing CorporationAdvances in Materials Science and EngineeringVolume 2015 Article ID 250836 10 pageshttpdxdoiorg1011552015250836

2 Advances in Materials Science and Engineering

anticorrosion methods provide research foundation for sur-face stabilizing treatment of iron relics

The chromate salt passivation treatmentmethod [13] is aneffective chemical conversion technology In spite of a goodcorrosion prevention effect its use is limited by environmen-tal regulations due to high toxicity and carcinogenicity ofhexavalent chromium [14ndash16]

Phosphate covering by forming a phosphate film onmetals using phosphoric acid or zinc phosphate manganesephosphate or iron phosphate solution possessesmany advan-tages such as anticorrosion wear-resisting antifrictionincreasing lubricity and promoting base adhesion betweencoating and metal [17] Phosphorus processing therefore iswidely applied in processing steel parts especially coatinglayer process [18] Separately pretreatment of reinforcedsteel surface with tannic acid based rust converter prior tothe application of zinc rich coating improved the corrosionresistance appreciably [19 20]

As one of metal surface treatment methods tanninshave potential application prospects with low toxicity lowpollution low usage volume and even color with excellentcorrosion-resistant performance [21] Tannins as corrosioninhibitors were applied both in solvent and waterbornepretreatment formulations [22] These formulations couldbe applied on partially rusted substrates reducing the effortneeded for cleaning the surface by methods which proved tobe expensive and are not applicable in many situations [21]Thus combination of phosphoric acid and tannic acid mayprovide a synergistic effect on corrosion resistance of ironcultural relics

In this study X-ray diffraction (XRD) infrared spec-troscopy (IR) X-ray photoelectron spectrometry (XPS) andtransmission electron microscopy (TEM) were used to char-acterize the four types of FeOOH as well as to investigate theinteractions betweenFeOOHandmixed solutions containingdifferent concentrations and proportions of phosphoric acidand tannic acid in order to provide technical basis to distin-guish these types of FeOOH and enable rust layer stabilizerselection for preservation of steel especially for iron culturalrelics

2 Experimental Details

21 Preparation of 120572- 120573- 120574- and 120575-FeOOH Rust analysesrevealed the presence of crystalline magnetite (Fe

3minusxO4) 120572-Fe2O3(haematite) goethite (120572-FeOOH) lepidocrocite (120574-

FeOOH) akaganeite (120573-FeOOH) and amorphous 120575-FeOOHphases [12] Thus the four FeOOH polymorphs were pre-pared to investigate their effects on iron rust

The 120572-FeOOH was prepared using a solution containing40 g of FeSO

4and 8 g of NaOH per liter of deionized (DI)

water The temperature was adjusted to 50∘C and pH to 13with 10wt NaOH The solution was fluxed with oxygen for8 hThe precipitates were washedwith 10 portions of DI wateruntil the filtrate became neutral in pH before being dried at100∘C

The 120574-FeOOH was prepared using a solution made of60 g of FeCl

2sdot4H2O in 1 L of DI water Meanwhile 84 g of

urotropine and 21 g of NaNO2each were dissolved in 300mL

of DI water After the FeCl2sdot4H2O solution was mixed with

urotropine solution NaNO2was added into the mixture

under constant stir at room temperature The mixture washeated to 60∘C under constant stir for 3 h The precipitateswere washed with hot water and dried at 60∘C

The 120573-FeOOHwas prepared using a 02M FeCl3solution

heated to 60∘C for 5 h Then small quantities of 3175mMEDTA and ammonia were added The precipitates werewashed with DI water until no Clminus was detected before beingdried at 70∘C for 24 h

The 120575-FeOOHwas prepared using a solutionmade of 40 gFeSO4and 8 g NaOH per liter of DI water A 10wt NaOH

solutionwas added dropwise till abundant brown precipitateswere formed at room temperature Then small quantities ofEDTA were added before the precipitates were filtered out

22 Test on the Influence of 120573-FeOOH and 120574-FeOOH onIron Rusting Archaize iron was used as the experimentalmaterial It had a composition of (wt) 417C 059 Si032Mn 0087 S and 0017P The samples were cutinto coupons each with a dimension of 15mm times 15mm times3mm A corrosion cell with a dimension of 10mm times10mm times 05mm was cut in the middle (Figure 1) Oneg synthetic 120573-FeOOH powder and one g synthetic 120574-FeOOH powder were added into separate cells The FeOOHpowder was pressed with a glass slide A drop of eachof the following corrosion media was added to the cor-responding cell each day Monday through Friday for 10months 001molLNO

3

minus 001molLClminus 001molLHSO4

minusand 001molLClminus+001molLHSO

4

minus At the end of theexperiment the specimens were encapsulated into epoxyresin The resin was carefully ground till the rust layer andiron clearly appeared Observation of propagation of rustunder the influence of NO

3

minus Clminus HSO4

minus and Clminus+HSO4

minus

was made using scanning electron microscope (SEM)

23 Interactions between FeOOH and Phosphoric AcidTannicAcid To each test tube 2 g of 120573-FeOOH 120574-FeOOH or 120575-FeOOHwas addedThen 20mL of tannic acid + phosphoricacid solution of different concentrations was added (Table 1)The tubes were sealed and shaken for varying amounts oftime and then were allowed left aside for a while to ensurecomplete reaction inside At the end of reaction the productswere filtered washed with DI water repeatedly and dried at50∘C

24 Characterization of FeOOH Phase identification wasconducted using an XRD-6000 X-ray diffractometer (Shi-madzu Japan)with aCuK120572 radiation (120582 = 15418 A) at 40 kVand 30mA a scanning speed of 5∘min and a scan range of3ndash90∘ FTIR spectra were acquired on a Bruker VECTOR 22infrared spectrometer at a resolution of 2 cmminus1 and a scanrange of 4000ndash400 cmminus1 with a KBr pressing method Themorphology of FeOOH was characterized by a TEM Powersamples were added to anhydrous ethanol and ultrasonicatedfor 30 minutes A little drip of suspension was put onto acopper mesh and dried naturally before TEM observation

Advances in Materials Science and Engineering 3

10mm

15m

m3mm

05mm FeOOH powder

Figure 1 Test device for the study of iron corrosion in the presenceof different types of FeOOH

Table 1 The combinations of tannic acidphosphoric acid (wt)

Number Tannic acidphosphoric acid Labeling1 3 tannic acid + 10 phosphoric acid 3T-10P2 3 tannic acid + 20 phosphoric acid 3T-20P3 3 tannic acid + 30 phosphoric acid 3T-30P4 5 tannic acid + 10 phosphoric acid 5T-10P5 5 tannic acid + 20 phosphoric acid 5T-20P6 5 tannic acid + 30 phosphoric acid 5T-30P

The elemental composition and valence state of elementswere investigated by XPS (British VGrsquos MCROLAB MK IIX-ray photoelectron spectroscopy) Magnesium was used asX-ray photon source with a power of 160W The energyanalyser was set at 50 eV The focusing voltage was 3 kV Anargon pressure of 1 times 10minus4 Pa and a vacuum pressure of 05 times10minus6 Pa were used for sputtering The angle between Ar+ ionssputtering gun and sample surfacewas 45∘ Scan started 5minafter Ar+ ions sputtering

3 Results and Discussion

31 Microstructures and Structures of FeOOH FTIR spectraof the samples prepared in the present work showed typicalfeatures of 120572- 120573- 120574- and 120575-FeOOH (Figure 2) The FTIRbands recorded at 1628 cmminus1 were ascribed to the ndashOHstretching vibration whereas the bands at 883 and 795 cmminus1were ascribed to the ndashOH bending modes in 120572-FeOOH [23]bands at 847 and 696 cmminus1 were ascribed to the ndashOHbendingmodes in 120573-FeOOH [24] nearby bands at 1020 and 750 cmminus1were the bending vibration of ndashOHmodes in 120574-FeOOH [12]and bands at 1120 and 975 cmminus1 were the bending vibration ofOHmodes in 120575-FeOOH [25]The four types of FeOOHwerealso confirmed by XRD analyses (Figure 3) Under the TEMobservation the120572-FeOOHwas granular120573-FeOOHappearedas rod-shaped while 120574-FeOOH looked like fine needles and120575-FeOOH was irregularly cotton-like (Figure 4) Differenttypes of corrosion products would cause different degreesof iron corrosion As 120572-FeOOH is relatively stable it mayattribute to nondetrimental rust On the other hand the club-shaped 120573-FeOOH and fine needle-like 120574-FeOOH had loosetexture that could store large amounts of moisture resultingin more iron corrosion

120572-FeOOH120573-FeOOH

120574-FeOOH120575-FeOOH

883

795

847

696

1020

750

1120

97516

28

2500 2250 5002000 1750 1500 1250 1000 750Wavenumber (cmminus1)

Tran

smitt

ance

()

Figure 2 FTIR spectra of different forms of FeOOH e 120572-FeOOH998771 120573-FeOOH ◼ 120574-FeOOHX 120575-FeOOH

32 Influence of 120573-FeOOH and 120574-FeOOH on Corrosion ofArchaeological Iron Corrosion morphologies of the surfacebetween cast iron and 120573-FeOOH or 120574-FeOOH under theaction of different ions NO

3

minus Clminus HSO4

minus and Clminus+HSO4

minus

were illustrated in Figure 5 FeOOH was sandwiched inbetween epoxide resin on top and cast iron on bottom Theboundaries were marked with white lines to help delineatethe rust surface

The surface between 120574-FeOOH and cast iron variedsignificantly with different types of ions The surface wasrelatively flat when NO

3

minus was used (Figure 5(a)) Similar toNO3

minus a clear 120574-FeOOH layer could be seen under the actionof Clminus (Figure 5(c)) When HSO

4

minus was added the interfacebecame fuzzy (Figure 5(e)) indicating that HSO

4

minus could leadto more serious corrosion The interface became more irreg-ular under the influence of Clminus+HSO

4

minus (Figure 5(g)) Morecorrosion of the cast iron was observed when the freshlyformed rust layer was connected to 120574-FeOOH layer In thepresence of Clminus and SO

4

2minus green rust would form which hadlittle protection on iron and was just an intermediate Fe(II)-Fe(III) hydroxyl-salt via which ferrous hydroxide Fe(OH)

2

usually oxidizes into different ferric oxyhydroxides [26]The change in surface morphology of 120573-FeOOH was

similar to that of 120574-FeOOH When NO3

minus was added thesurface was relatively flat (Figure 5(b))The surface corrosionbecame more serious as the anion was changed from Clminus toHSO4

minus (Figures 5(d) and 5(f))When Clminus+HSO4

minus was actingon 120573-FeOOH corrosion of the interface was so serious that itconnected to the original 120573-FeOOH layers (Figure 5(h))

The above observations showed that when either 120574-FeOOH or 120573-FeOOH adhered to iron surface it was unableto prevent different anions from reaching the iron surfaceIn another word the two hydroxy-oxide rust layers werenot strong enough to provide a good protection and preventiron from further corrosionWith relatively loose textures 120574-FeOOH and 120573-FeOOH not only failed to stop anions from

4 Advances in Materials Science and Engineering

Inte

nsity

(cps

)

20 30 40 50 60 70 80 90

0

40

80

120

160

120573-FeOOH

2120579 (∘)

120572-FeOOH (goethite)

(a)In

tens

ity (c

ps)

0

200

400

600

800

1000

10 20 30 40 50 60 70 80

120573-FeOOH (akaganeite)

2120579 (∘)

(b)

Inte

nsity

(cps

)

10 20 30 40 50 60 70 80 900

100

200

300

120574-FeOOH (lepidocrocite)

2120579 (∘)

(c)

Inte

nsity

(cou

nts)

10 20 30 40 50 60 70 800

50

100

150

200

250

120575-FeOOH (amorphous)

2120579 (∘)

(d)

Figure 3 X-ray diffraction patterns of different forms of FeOOHX 120572-FeOOH 998787 120573-FeOOH e 120574-FeOOH ◼ 120575-FeOOH

corroding the iron but also became a storage area for anionsand moisture resulting in strong adsorption Meanwhile itslowed down the evaporation rate of moisture and extendedthe corrosion cycle of moisture thus promoting corrosiveions acting on the cast iron

Moreover among the common anions in atmospherethat would cause corrosion NO

3

minus had the weakest corrosionpower on cast iron The corrosive power increased progres-sively following the order Clminus+HSO

4

minusgtHSO

4gt Clminus Under

the combined action of Clminus and HSO4

minus the corrosion of castiron was much more serious than any other ions used aloneindicating synergistic activities between Clminus and HSO

4

minus 120573-FeOOH was produced exclusively in the presence of Clminus [27]which had weaker iron protection and resulted in more iron

rusting The corrosion product of cast iron in contact withthe FeCl

2solution over 138 days was made up of three layers

120572-FeOOH Fe3O4 and a little 120573-FeOOH in the inner layer 120574-

FeOOH in the middle layer and 120572-FeOOH in the outer layer[28]

33 Interactions between FeOOH and Different Combinationsof Phosphoric AcidTannic Acid Different states and colors ofreaction products after filtrating drying and grinding weredocumented in Table 2 The yellow powder and tannic acidwere identical in material phases and composition suggest-ing that the yellow powder was excess tannins As tannic aciddissolves 120574-FeOOH and higher concentrations of tannic acidspeeded up the dissolution [29] it is suggested that FeOOH

Advances in Materials Science and Engineering 5

120572-FeOOH

100nm

(a)

(a)

120573-FeOOH

100nm

(b)

(b)

120574-FeOOH

100nm

(c)

(c)

(d)

120575-FeOOH

100nm

(d)

Figure 4 TEM images of different forms of FeOOH

Table 2 The state and color of reaction products

Phosphoric acidtannic acid 120573-FeOOH 120574-FeOOH 120575-FeOOH3T-10P Gray powder Gray powder Gray powder3T-20P Gray powder Yellow powder Less product blue-gray3T-30P Less product beige Yellow powder Yellow powder5T-10P Gray powder Blue-gray yellow Blue-gray powder5T-20P Gray powder Yellow powder Blue-gray powder5T-30P Less product beige Less product blue-gray Yellow powder

was completely dissolved Thus these proportions were notsuitable as a choice of rust stabilizer formula due to accumu-lation of residual tannic acid after reaction In addition forsome combinations the reaction products were very limitedindicating that most of the FeOOH was dissolved under theaction of phosphoric acidtannic acid Only a small amountof FeOOH was involved in chemical transformation Thusthese combinations were also undesirable for rust stabilizerformula

At the same time according to protection standards ofcultural relics protection materials must be close to originalartifacts to the maximum extent Among the combinationsin Table 2 only the product of the 3T-10P namely 3 tannicacid + 10 phosphoric acid and FeOOH was gray similarto the color of steel materials suggesting that 3 tannicacid + 10 phosphoric acid was the most suitable formulafor rust stabilizer Previous studies showed that conventionalanticorrosive paints or the painting schemes applied on steelpreviously treatedwith a primer formulatedwith pine tanninsextend the duration of painting schemes more than 50relative to the case without this chemical treatment [30]

The XRD pattern of reaction products of 120573- 120574- and 120575-FeOOH and 3T-10P was presented in Figure 6 A crystallinephosphate was the major product and it matched the XRDpatterns of Fe

3P6O2well In contrast the major constituents

of the scale onDelhi iron pillar were crystalline iron hydrogenphosphate hydrate (FePO

4sdotH3PO4sdot4H2O) as well as 120572- 120574-

and 120575-FeOOH and magnetite [30] or crystalline phosphateFe2(PO4)(OH) [7] No phases related to tannic acid were

identified suggesting that the transformation products oftannic acid and FeOOH were amorphous

The transformation products from the reaction of tannicacidphosphoric acid and FeOOHwere further characterizedby XPS The reaction products between 120573-FeOOH and 3T-10P were mainly Fe C P and O (Figure 7) The bindingenergy of Fe2p

32was 71242 eV confirming the presence of

Fe3+ in the productThe binding energy of C1s can be decom-posed to 28507 28689 and 28850 eV with the former corre-sponding to carbon and the combination of the latter two cor-responding to standard spectral peaks of carboxide in tannicacidThe binding energy of O1s was 53195 eV correspondingtoCndashOH in tannic acid In addition the peak at 13364 eVwas

6 Advances in Materials Science and Engineering

(a)

200120583m

120574-FeOOHiron

(a)

(b)

200120583m

120573-FeOOHiron

(b)

(c)

100120583m

120574-FeOOHiron

(c)

(d)

100120583m

120573-FeOOHiron

(d)

(e)

200120583m

120574-FeOOHiron

(e)

(f)

100120583m120573-FeOOHiron

(f)

(g)

100120583m120574-FeOOHiron

(g)

(h)

200120583m120573-FeOOHiron

(h)

Figure 5 SEM images of rust powdercast iron interface with the effects of NO3

minus ((a) and (b)) Clminus ((c) and (d)) HSO4

minus ((e) and (f)) andClminus+HSO

4

minus ((g) and (h))

originated from P2p confirming the presence of phosphateThe peaks of Fe2p

32in Fe3+ generally lie between 71020

and 71105 eV However the binding energy of Fe2p32

in thisstudy was 71242 eV resulting in a chemical shift of morethan 1 eV Such a shift may suggest a change in chemical

environment of the elements thus indicating formation ofa new chemical bond between Fe3+ and other substancesDue to the presence of tannic acid it may suggest the for-mation of chelate between iron and tannin [31] as illustratedin Scheme 1

Advances in Materials Science and Engineering 7

10 20 30 40 50 60 70

0

500

1000

1500

2000

2500

3000

3500

Inte

nsity

(cps

)

2120579 (∘)

120575-FeOOH3T-10P

120574-FeOOH3T-10P

120573-FeOOH3T-10P

Fe3P6O2

Figure 6 XRD patterns of the products formed from the reaction of FeOOH and 3T-10P

730 720 710 700 690

8000

9000

10000

11000

12000

13000

14000

Inte

nsity

(cps

)

Binding energy (eV)

120573-FeOOH3T-10P

71242Fe3+

Fe2p

(a)

Inte

nsity

(cps

)

294 292 290 288 286 284 282

2000

3000

4000

5000

6000

7000

8000

9000

10000

Binding energy (eV)

120573-FeOOH3T-10P

28850

28507

28689

C1sC

CndashOH

OndashC=O

(b)

538 536 534 532 530 5280

5000

10000

15000

20000

25000

30000

Inte

nsity

(cps

)

Binding energy (eV)

120573-FeOOH3P-10T53195O1s CndashOH

(c)

Inte

nsity

(cps

)

138 136 134 132 1301000

1500

2000

2500

3000

3500

4000

4500

Binding energy (eV)

120573-FeOOH3T-10P

13364P2p P5+

(d)

Figure 7 XPS spectra of the products formed from the reaction of 120573-FeOOH and 3T-10P

8 Advances in Materials Science and Engineering

730 720 710 700 690

7500

8000

8500

9000

9500

10000

10500

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P

Fe3+

Fe2p

71205

(a)

292 290 288 286 284 2820

2000

4000

6000

8000

10000

12000

14000

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P

28642

28490

28850

C1s C

CndashOH

OndashC=O

(b)

528 530 532 534 5360

5000

10000

15000

20000

25000

30000

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P53258

O1sCndashOH

(c)

138 136 134 132

1000120014001600180020002200240026002800

800

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P13399

P2p P5+

(d)

Figure 8 XPS spectra of the products formed from the reaction of 120574-FeOOH and 3T-10P

ROH

OH

OH

R

OO

O

Fe3+Fe3+ ++ 3H3+

Scheme 1 Single-chelate complex ion body

Thus it was speculated that the reaction products of 120573-FeOOH and 3T-10P were made up of iron phosphate andchelate of iron and tannin

The results of XPS analyses of the reaction productsgenerated by 120574-FeOOHand 3T-10P and by 120575-FeOOHand 3T-10P were illustrated in Figures 8 and 9 The composition ofthese two products was similar to the reaction products of 120573-FeOOH and 3T-10P that is was made mainly of Fe C P andO and having about the same peak positions Therefore thereaction products were mainly made of iron phosphate andchelate of iron and tannin

The structures of iron phosphate and chelate of iron andtannin are relatively stable If acting as chemical conversionlayer the cast iron may develop strong corrosion resistancecapacity Meanwhile the layer can enhance bonding betweenthe coating and the substrate These favorable physical andchemical properties could meet the need of coating andsealing treatment for iron artifact However the mechanismsof tannic acidphosphoric acid rust conversion may needfurther study

4 Conclusions

(1) When cast iron was covered by 120573-FeOOH and 120574-FeOOH corrosion the rust layer was porous and nottight enough to provide a good protection againstcorrosion by NO

3

minus Clminus HSO4

minus and Clminus+HSO4

minus(2) Among common anions tested NO

3

minus had the weak-est corrosive power on cast ironThe corrosion powerincreased in the following sequence Clminus HSO

4

minus andClminus+HSO

4

minus Meanwhile synergistic corrosion couldbe enhanced when both Clminus andHSO

4

minus were present

Advances in Materials Science and Engineering 9

730 720 710 700 6907000

7500

8000

8500

9000

9500

10000

10500In

tens

ity (c

ps)

71293Fe3+

120575-FeOOH3T-10P

Binding energy (eV)

(a)

290 288 286 284 2820

2000

4000

6000

8000

10000

12000

14000

Inte

nsity

(cps

)

28503

28659

28873

C1s C 120575-FeOOH3T-10P

Binding energy (eV)

CndashOH

OndashC=O

(b)

536 534 532 530 5280

5000

10000

15000

20000

25000

Inte

nsity

(cps

)

53061

O1sOHminus

Binding energy (eV)

(c)

137 136 135 134 133 132 131

8001000120014001600180020002200240026002800

Inte

nsity

(cps

)

13410P2p 120575-FeOOH3T-10PP5+

Binding energy (eV)

(d)

Figure 9 XPS spectra of the products formed from the reaction of 120575-FeOOH and 3T-10P

(3) Analyses of the reaction products between FeOOHand different combinations of phosphoric acidtannicacid showed that 3 tannic acid + 10 phosphoricacid was the most suitable formula as rust stabilizer

(4) The reaction products between120573-FeOOH 120574-FeOOHor 120575-FeOOH and 3T-10P were made up of ironphosphate and chelate of iron and tannin

Conflict of Interests

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

Acknowledgments

This present work was supported by the National NaturalScience Foundation of China (Grants nos 51202226 and51172216) and the Fundamental Research Funds for theCentral Universities (Grant no 2652013043)

References

[1] W Xu K Daub X Zhang J J Noel D W Shoesmith and JC Wren ldquoOxide formation and conversion on carbon steel inmildly basic solutionsrdquo Electrochimica Acta vol 54 no 24 pp5727ndash5738 2009

[2] X Liu G Qiu A Yan Z Wang and X Li ldquoHydrothermal syn-thesis and characterization of 120572-FeOOH and 120572-Fe

2O3uniform

nanocrystallinesrdquo Journal of Alloys andCompounds vol 433 no1-2 pp 216ndash220 2007

[3] H Abdel-Samad and P R Watson ldquoAn XPS study of theadsorption of lead on goethite (120572-FeOOH)rdquo Applied SurfaceScience vol 136 no 1-2 pp 46ndash54 1998

[4] C-J Jia L-D Sun Z-G Yan et al ldquoSingle-crystalline iron oxidenanotubesrdquoAngewandte Chemie vol 44 no 28 pp 4328ndash43332005

[5] M Zic M Ristic and S Music ldquoThe effect of temperature onthe crystallization of 120572-Fe

2O3particles from dense 120573-FeOOH

suspensionsrdquo Materials Chemistry and Physics vol 120 no 1pp 160ndash166 2010

10 Advances in Materials Science and Engineering

[6] A Jagminas K Mazeika E Juska J Reklaitis and D Bal-trunas ldquoElectrochemical fabrication and characterization oflepidocrocite (120574-FeOOH) nanowire arraysrdquo Applied SurfaceScience vol 256 no 12 pp 3993ndash3996 2010

[7] P Dillmann R Balasubramaniam and G Beranger ldquoChar-acterization of protective rust on ancient Indian iron usingmicroprobe analysesrdquo Corrosion Science vol 44 no 10 pp2231ndash2242 2002

[8] H Tanaka J Wakatsuki K Kandori T Ishikawa and TNakayama ldquoRole of zinc compounds on the formation mor-phology and adsorption characteristics of 120573-FeOOH rustsrdquoCorrosion Science vol 52 no 9 pp 2973ndash2978 2010

[9] T Ishikawa M Kumagai A Yasukawa K Kandori TNakayama and F Yuse ldquoInfluences of metal ions on theformation of 120574-FeOOH andmagnetite rustsrdquoCorrosion Sciencevol 44 no 5 pp 1073ndash1086 2002

[10] A Collazo X R Novoa C Perez and B Puga ldquoThe corrosionprotection mechanism of rust converters an electrochemicalimpedance spectroscopy studyrdquo Electrochimica Acta vol 55 no21 pp 6156ndash6162 2010

[11] M Zic M Ristic and S Music ldquoPrecipitation of 120572-Fe2O3

from dense 120573-FeOOH suspensions with added ammoniumamidosulfonaterdquo Journal of Molecular Structure vol 924-926pp 235ndash242 2009

[12] C Q Cheng J Zhao T S Cao Q Q Fu M K Lei and DW Deng ldquoFacile chromaticity approach for the inspection ofpassive films on austenitic stainless steelrdquoCorrosion Science vol70 pp 235ndash242 2013

[13] A I Munoz J G Anton J L Guinon and V P HerranzldquoInhibition effect of chromate on the passivation and pittingcorrosion of a duplex stainless steel in LiBr solutions usingelectrochemical techniquesrdquo Corrosion Science vol 49 no 8pp 3200ndash3225 2007

[14] S Powell ldquoEvaluation of alternative corrosion inhibitors tochromate for use in organic coatings using scanning referenceelectrode techniquerdquo Surface Engineering vol 16 no 2 pp 169ndash175 2000

[15] B J Basu A Srinivasan J Manasa and V K W GripsldquoImproved corrosion protection of aluminium alloy AA 2024by sol-gel hybrid coatings after surface pretreatment by silani-sationrdquo Surface Engineering vol 28 no 4 pp 294ndash299 2012

[16] Z Liu D Yan Y Dong Y Yang Z Chu and Z ZhangldquoThe effect of modified epoxy sealing on the electrochemicalcorrosion behaviour of reactive plasma-sprayed TiN coatingsrdquoCorrosion Science vol 75 pp 220ndash227 2013

[17] A M Simoes J Torres R Picciochi and J C S FernandesldquoCorrosion inhibition at galvanized steel cut edges by phosphatepigmentsrdquo Electrochimica Acta vol 54 no 15 pp 3857ndash38652009

[18] B Gruss ldquoIron phosphatingrdquoMetal Finishing vol 108 no 11-12pp 33ndash37 2010

[19] D Singh and S Yadav ldquoRole of tannic acid based rust converteron formation of passive film on zinc rich coating exposedin simulated concrete pore solutionrdquo Surface and CoatingsTechnology vol 202 no 8 pp 1526ndash1542 2008

[20] B Qian B Hou and M Zheng ldquoThe inhibition effect oftannic acid on mild steel corrosion in seawater wetdry cyclicconditionsrdquo Corrosion Science vol 72 pp 1ndash9 2013

[21] A Ostovari S M Hoseinieh M Peikari S R Shadizadehand S J Hashemi ldquoCorrosion inhibition of mild steel in 1M HCl solution by henna extract a comparative study of the

inhibition by henna and its constituents (Lawsone Gallic acid120572-d-Glucose and Tannic acid)rdquo Corrosion Science vol 51 no 9pp 1935ndash1949 2009

[22] K W Tan M J Kassim and C W Oo ldquoPossible improvementof catechin as corrosion inhibitor in acidic mediumrdquo CorrosionScience vol 65 pp 152ndash162 2012

[23] B Yuan J Xu X Li and M-L Fu ldquoPreparation of Si-Al120572-FeOOH catalyst from an iron-containing waste and surface-catalytic oxidation of methylene blue at neutral pH value in thepresence of H

2O2rdquo Chemical Engineering Journal vol 226 pp

181ndash188 2013[24] S Bashir R W McCabe C Boxall M S Leaver and D Mobbs

ldquoSynthesis of 120572- and120573-FeOOH iron oxide nanoparticles in non-ionic surfactant mediumrdquo Journal of Nanoparticle Research vol11 no 3 pp 701ndash706 2009

[25] L Carlson and U Schwertmann ldquoNatural occurrence of ferox-yhite (120575rsquo-FeOOH)rdquo Clays amp Clay Minerals vol 28 no 4 pp272ndash280 1980

[26] Z Wang C Xu and X Dong ldquoLocalized corrosion andphase transformation of simulated archaeological ironrdquoChineseJournal of Chemical Engineering vol 16 no 2 pp 299ndash3052008

[27] C Remazeilles and P Refait ldquoOn the formation of 120573-FeOOH(akaganeite) in chloride-containing environmentsrdquo CorrosionScience vol 49 no 2 pp 844ndash857 2007

[28] Z Wang C Xu X Cao and B Xu ldquoThe Morphology phasecomposition and effect of corrosion product on simulatedarchaeological ironrdquo Chinese Journal of Chemical Engineeringvol 15 no 3 pp 433ndash438 2007

[29] S Nasrazadani ldquoThe application of infrared spectroscopy toa study of phosphoric and tannic acids interactions withmagnetite (Fe

3O4) goethite (120572-FeOOH) and lepidocrocite (120574-

FeOOH)rdquo Corrosion Science vol 39 no 10-11 pp 1845ndash18591997

[30] R Balasubramaniam ldquoOn the corrosion resistance of the Delhiiron pillarrdquo Corrosion Science vol 42 no 12 pp 2103ndash21292000

[31] AM Al-Mayouf ldquoInhibitors for chemical cleaning of iron withtannic acidrdquo Desalination vol 121 no 2 pp 173ndash182 1999

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CeramicsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CompositesJournal of

NanoparticlesJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Biomaterials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

MetallurgyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BioMed Research International

MaterialsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Nano

materials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal ofNanomaterials

Advances in Materials Science and Engineering 3

10mm

15m

m3mm

05mm FeOOH powder

Figure 1 Test device for the study of iron corrosion in the presenceof different types of FeOOH

Table 1 The combinations of tannic acidphosphoric acid (wt)

Number Tannic acidphosphoric acid Labeling1 3 tannic acid + 10 phosphoric acid 3T-10P2 3 tannic acid + 20 phosphoric acid 3T-20P3 3 tannic acid + 30 phosphoric acid 3T-30P4 5 tannic acid + 10 phosphoric acid 5T-10P5 5 tannic acid + 20 phosphoric acid 5T-20P6 5 tannic acid + 30 phosphoric acid 5T-30P

The elemental composition and valence state of elementswere investigated by XPS (British VGrsquos MCROLAB MK IIX-ray photoelectron spectroscopy) Magnesium was used asX-ray photon source with a power of 160W The energyanalyser was set at 50 eV The focusing voltage was 3 kV Anargon pressure of 1 times 10minus4 Pa and a vacuum pressure of 05 times10minus6 Pa were used for sputtering The angle between Ar+ ionssputtering gun and sample surfacewas 45∘ Scan started 5minafter Ar+ ions sputtering

3 Results and Discussion

31 Microstructures and Structures of FeOOH FTIR spectraof the samples prepared in the present work showed typicalfeatures of 120572- 120573- 120574- and 120575-FeOOH (Figure 2) The FTIRbands recorded at 1628 cmminus1 were ascribed to the ndashOHstretching vibration whereas the bands at 883 and 795 cmminus1were ascribed to the ndashOH bending modes in 120572-FeOOH [23]bands at 847 and 696 cmminus1 were ascribed to the ndashOHbendingmodes in 120573-FeOOH [24] nearby bands at 1020 and 750 cmminus1were the bending vibration of ndashOHmodes in 120574-FeOOH [12]and bands at 1120 and 975 cmminus1 were the bending vibration ofOHmodes in 120575-FeOOH [25]The four types of FeOOHwerealso confirmed by XRD analyses (Figure 3) Under the TEMobservation the120572-FeOOHwas granular120573-FeOOHappearedas rod-shaped while 120574-FeOOH looked like fine needles and120575-FeOOH was irregularly cotton-like (Figure 4) Differenttypes of corrosion products would cause different degreesof iron corrosion As 120572-FeOOH is relatively stable it mayattribute to nondetrimental rust On the other hand the club-shaped 120573-FeOOH and fine needle-like 120574-FeOOH had loosetexture that could store large amounts of moisture resultingin more iron corrosion

120572-FeOOH120573-FeOOH

120574-FeOOH120575-FeOOH

883

795

847

696

1020

750

1120

97516

28

2500 2250 5002000 1750 1500 1250 1000 750Wavenumber (cmminus1)

Tran

smitt

ance

()

Figure 2 FTIR spectra of different forms of FeOOH e 120572-FeOOH998771 120573-FeOOH ◼ 120574-FeOOHX 120575-FeOOH

32 Influence of 120573-FeOOH and 120574-FeOOH on Corrosion ofArchaeological Iron Corrosion morphologies of the surfacebetween cast iron and 120573-FeOOH or 120574-FeOOH under theaction of different ions NO

3

minus Clminus HSO4

minus and Clminus+HSO4

minus

were illustrated in Figure 5 FeOOH was sandwiched inbetween epoxide resin on top and cast iron on bottom Theboundaries were marked with white lines to help delineatethe rust surface

The surface between 120574-FeOOH and cast iron variedsignificantly with different types of ions The surface wasrelatively flat when NO

3

minus was used (Figure 5(a)) Similar toNO3

minus a clear 120574-FeOOH layer could be seen under the actionof Clminus (Figure 5(c)) When HSO

4

minus was added the interfacebecame fuzzy (Figure 5(e)) indicating that HSO

4

minus could leadto more serious corrosion The interface became more irreg-ular under the influence of Clminus+HSO

4

minus (Figure 5(g)) Morecorrosion of the cast iron was observed when the freshlyformed rust layer was connected to 120574-FeOOH layer In thepresence of Clminus and SO

4

2minus green rust would form which hadlittle protection on iron and was just an intermediate Fe(II)-Fe(III) hydroxyl-salt via which ferrous hydroxide Fe(OH)

2

usually oxidizes into different ferric oxyhydroxides [26]The change in surface morphology of 120573-FeOOH was

similar to that of 120574-FeOOH When NO3

minus was added thesurface was relatively flat (Figure 5(b))The surface corrosionbecame more serious as the anion was changed from Clminus toHSO4

minus (Figures 5(d) and 5(f))When Clminus+HSO4

minus was actingon 120573-FeOOH corrosion of the interface was so serious that itconnected to the original 120573-FeOOH layers (Figure 5(h))

The above observations showed that when either 120574-FeOOH or 120573-FeOOH adhered to iron surface it was unableto prevent different anions from reaching the iron surfaceIn another word the two hydroxy-oxide rust layers werenot strong enough to provide a good protection and preventiron from further corrosionWith relatively loose textures 120574-FeOOH and 120573-FeOOH not only failed to stop anions from

4 Advances in Materials Science and Engineering

Inte

nsity

(cps

)

20 30 40 50 60 70 80 90

0

40

80

120

160

120573-FeOOH

2120579 (∘)

120572-FeOOH (goethite)

(a)In

tens

ity (c

ps)

0

200

400

600

800

1000

10 20 30 40 50 60 70 80

120573-FeOOH (akaganeite)

2120579 (∘)

(b)

Inte

nsity

(cps

)

10 20 30 40 50 60 70 80 900

100

200

300

120574-FeOOH (lepidocrocite)

2120579 (∘)

(c)

Inte

nsity

(cou

nts)

10 20 30 40 50 60 70 800

50

100

150

200

250

120575-FeOOH (amorphous)

2120579 (∘)

(d)

Figure 3 X-ray diffraction patterns of different forms of FeOOHX 120572-FeOOH 998787 120573-FeOOH e 120574-FeOOH ◼ 120575-FeOOH

corroding the iron but also became a storage area for anionsand moisture resulting in strong adsorption Meanwhile itslowed down the evaporation rate of moisture and extendedthe corrosion cycle of moisture thus promoting corrosiveions acting on the cast iron

Moreover among the common anions in atmospherethat would cause corrosion NO

3

minus had the weakest corrosionpower on cast iron The corrosive power increased progres-sively following the order Clminus+HSO

4

minusgtHSO

4gt Clminus Under

the combined action of Clminus and HSO4

minus the corrosion of castiron was much more serious than any other ions used aloneindicating synergistic activities between Clminus and HSO

4

minus 120573-FeOOH was produced exclusively in the presence of Clminus [27]which had weaker iron protection and resulted in more iron

rusting The corrosion product of cast iron in contact withthe FeCl

2solution over 138 days was made up of three layers

120572-FeOOH Fe3O4 and a little 120573-FeOOH in the inner layer 120574-

FeOOH in the middle layer and 120572-FeOOH in the outer layer[28]

33 Interactions between FeOOH and Different Combinationsof Phosphoric AcidTannic Acid Different states and colors ofreaction products after filtrating drying and grinding weredocumented in Table 2 The yellow powder and tannic acidwere identical in material phases and composition suggest-ing that the yellow powder was excess tannins As tannic aciddissolves 120574-FeOOH and higher concentrations of tannic acidspeeded up the dissolution [29] it is suggested that FeOOH

Advances in Materials Science and Engineering 5

120572-FeOOH

100nm

(a)

(a)

120573-FeOOH

100nm

(b)

(b)

120574-FeOOH

100nm

(c)

(c)

(d)

120575-FeOOH

100nm

(d)

Figure 4 TEM images of different forms of FeOOH

Table 2 The state and color of reaction products

Phosphoric acidtannic acid 120573-FeOOH 120574-FeOOH 120575-FeOOH3T-10P Gray powder Gray powder Gray powder3T-20P Gray powder Yellow powder Less product blue-gray3T-30P Less product beige Yellow powder Yellow powder5T-10P Gray powder Blue-gray yellow Blue-gray powder5T-20P Gray powder Yellow powder Blue-gray powder5T-30P Less product beige Less product blue-gray Yellow powder

was completely dissolved Thus these proportions were notsuitable as a choice of rust stabilizer formula due to accumu-lation of residual tannic acid after reaction In addition forsome combinations the reaction products were very limitedindicating that most of the FeOOH was dissolved under theaction of phosphoric acidtannic acid Only a small amountof FeOOH was involved in chemical transformation Thusthese combinations were also undesirable for rust stabilizerformula

At the same time according to protection standards ofcultural relics protection materials must be close to originalartifacts to the maximum extent Among the combinationsin Table 2 only the product of the 3T-10P namely 3 tannicacid + 10 phosphoric acid and FeOOH was gray similarto the color of steel materials suggesting that 3 tannicacid + 10 phosphoric acid was the most suitable formulafor rust stabilizer Previous studies showed that conventionalanticorrosive paints or the painting schemes applied on steelpreviously treatedwith a primer formulatedwith pine tanninsextend the duration of painting schemes more than 50relative to the case without this chemical treatment [30]

The XRD pattern of reaction products of 120573- 120574- and 120575-FeOOH and 3T-10P was presented in Figure 6 A crystallinephosphate was the major product and it matched the XRDpatterns of Fe

3P6O2well In contrast the major constituents

of the scale onDelhi iron pillar were crystalline iron hydrogenphosphate hydrate (FePO

4sdotH3PO4sdot4H2O) as well as 120572- 120574-

and 120575-FeOOH and magnetite [30] or crystalline phosphateFe2(PO4)(OH) [7] No phases related to tannic acid were

identified suggesting that the transformation products oftannic acid and FeOOH were amorphous

The transformation products from the reaction of tannicacidphosphoric acid and FeOOHwere further characterizedby XPS The reaction products between 120573-FeOOH and 3T-10P were mainly Fe C P and O (Figure 7) The bindingenergy of Fe2p

32was 71242 eV confirming the presence of

Fe3+ in the productThe binding energy of C1s can be decom-posed to 28507 28689 and 28850 eV with the former corre-sponding to carbon and the combination of the latter two cor-responding to standard spectral peaks of carboxide in tannicacidThe binding energy of O1s was 53195 eV correspondingtoCndashOH in tannic acid In addition the peak at 13364 eVwas

6 Advances in Materials Science and Engineering

(a)

200120583m

120574-FeOOHiron

(a)

(b)

200120583m

120573-FeOOHiron

(b)

(c)

100120583m

120574-FeOOHiron

(c)

(d)

100120583m

120573-FeOOHiron

(d)

(e)

200120583m

120574-FeOOHiron

(e)

(f)

100120583m120573-FeOOHiron

(f)

(g)

100120583m120574-FeOOHiron

(g)

(h)

200120583m120573-FeOOHiron

(h)

Figure 5 SEM images of rust powdercast iron interface with the effects of NO3

minus ((a) and (b)) Clminus ((c) and (d)) HSO4

minus ((e) and (f)) andClminus+HSO

4

minus ((g) and (h))

originated from P2p confirming the presence of phosphateThe peaks of Fe2p

32in Fe3+ generally lie between 71020

and 71105 eV However the binding energy of Fe2p32

in thisstudy was 71242 eV resulting in a chemical shift of morethan 1 eV Such a shift may suggest a change in chemical

environment of the elements thus indicating formation ofa new chemical bond between Fe3+ and other substancesDue to the presence of tannic acid it may suggest the for-mation of chelate between iron and tannin [31] as illustratedin Scheme 1

Advances in Materials Science and Engineering 7

10 20 30 40 50 60 70

0

500

1000

1500

2000

2500

3000

3500

Inte

nsity

(cps

)

2120579 (∘)

120575-FeOOH3T-10P

120574-FeOOH3T-10P

120573-FeOOH3T-10P

Fe3P6O2

Figure 6 XRD patterns of the products formed from the reaction of FeOOH and 3T-10P

730 720 710 700 690

8000

9000

10000

11000

12000

13000

14000

Inte

nsity

(cps

)

Binding energy (eV)

120573-FeOOH3T-10P

71242Fe3+

Fe2p

(a)

Inte

nsity

(cps

)

294 292 290 288 286 284 282

2000

3000

4000

5000

6000

7000

8000

9000

10000

Binding energy (eV)

120573-FeOOH3T-10P

28850

28507

28689

C1sC

CndashOH

OndashC=O

(b)

538 536 534 532 530 5280

5000

10000

15000

20000

25000

30000

Inte

nsity

(cps

)

Binding energy (eV)

120573-FeOOH3P-10T53195O1s CndashOH

(c)

Inte

nsity

(cps

)

138 136 134 132 1301000

1500

2000

2500

3000

3500

4000

4500

Binding energy (eV)

120573-FeOOH3T-10P

13364P2p P5+

(d)

Figure 7 XPS spectra of the products formed from the reaction of 120573-FeOOH and 3T-10P

8 Advances in Materials Science and Engineering

730 720 710 700 690

7500

8000

8500

9000

9500

10000

10500

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P

Fe3+

Fe2p

71205

(a)

292 290 288 286 284 2820

2000

4000

6000

8000

10000

12000

14000

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P

28642

28490

28850

C1s C

CndashOH

OndashC=O

(b)

528 530 532 534 5360

5000

10000

15000

20000

25000

30000

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P53258

O1sCndashOH

(c)

138 136 134 132

1000120014001600180020002200240026002800

800

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P13399

P2p P5+

(d)

Figure 8 XPS spectra of the products formed from the reaction of 120574-FeOOH and 3T-10P

ROH

OH

OH

R

OO

O

Fe3+Fe3+ ++ 3H3+

Scheme 1 Single-chelate complex ion body

Thus it was speculated that the reaction products of 120573-FeOOH and 3T-10P were made up of iron phosphate andchelate of iron and tannin

The results of XPS analyses of the reaction productsgenerated by 120574-FeOOHand 3T-10P and by 120575-FeOOHand 3T-10P were illustrated in Figures 8 and 9 The composition ofthese two products was similar to the reaction products of 120573-FeOOH and 3T-10P that is was made mainly of Fe C P andO and having about the same peak positions Therefore thereaction products were mainly made of iron phosphate andchelate of iron and tannin

The structures of iron phosphate and chelate of iron andtannin are relatively stable If acting as chemical conversionlayer the cast iron may develop strong corrosion resistancecapacity Meanwhile the layer can enhance bonding betweenthe coating and the substrate These favorable physical andchemical properties could meet the need of coating andsealing treatment for iron artifact However the mechanismsof tannic acidphosphoric acid rust conversion may needfurther study

4 Conclusions

(1) When cast iron was covered by 120573-FeOOH and 120574-FeOOH corrosion the rust layer was porous and nottight enough to provide a good protection againstcorrosion by NO

3

minus Clminus HSO4

minus and Clminus+HSO4

minus(2) Among common anions tested NO

3

minus had the weak-est corrosive power on cast ironThe corrosion powerincreased in the following sequence Clminus HSO

4

minus andClminus+HSO

4

minus Meanwhile synergistic corrosion couldbe enhanced when both Clminus andHSO

4

minus were present

Advances in Materials Science and Engineering 9

730 720 710 700 6907000

7500

8000

8500

9000

9500

10000

10500In

tens

ity (c

ps)

71293Fe3+

120575-FeOOH3T-10P

Binding energy (eV)

(a)

290 288 286 284 2820

2000

4000

6000

8000

10000

12000

14000

Inte

nsity

(cps

)

28503

28659

28873

C1s C 120575-FeOOH3T-10P

Binding energy (eV)

CndashOH

OndashC=O

(b)

536 534 532 530 5280

5000

10000

15000

20000

25000

Inte

nsity

(cps

)

53061

O1sOHminus

Binding energy (eV)

(c)

137 136 135 134 133 132 131

8001000120014001600180020002200240026002800

Inte

nsity

(cps

)

13410P2p 120575-FeOOH3T-10PP5+

Binding energy (eV)

(d)

Figure 9 XPS spectra of the products formed from the reaction of 120575-FeOOH and 3T-10P

(3) Analyses of the reaction products between FeOOHand different combinations of phosphoric acidtannicacid showed that 3 tannic acid + 10 phosphoricacid was the most suitable formula as rust stabilizer

(4) The reaction products between120573-FeOOH 120574-FeOOHor 120575-FeOOH and 3T-10P were made up of ironphosphate and chelate of iron and tannin

Conflict of Interests

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

Acknowledgments

This present work was supported by the National NaturalScience Foundation of China (Grants nos 51202226 and51172216) and the Fundamental Research Funds for theCentral Universities (Grant no 2652013043)

References

[1] W Xu K Daub X Zhang J J Noel D W Shoesmith and JC Wren ldquoOxide formation and conversion on carbon steel inmildly basic solutionsrdquo Electrochimica Acta vol 54 no 24 pp5727ndash5738 2009

[2] X Liu G Qiu A Yan Z Wang and X Li ldquoHydrothermal syn-thesis and characterization of 120572-FeOOH and 120572-Fe

2O3uniform

nanocrystallinesrdquo Journal of Alloys andCompounds vol 433 no1-2 pp 216ndash220 2007

[3] H Abdel-Samad and P R Watson ldquoAn XPS study of theadsorption of lead on goethite (120572-FeOOH)rdquo Applied SurfaceScience vol 136 no 1-2 pp 46ndash54 1998

[4] C-J Jia L-D Sun Z-G Yan et al ldquoSingle-crystalline iron oxidenanotubesrdquoAngewandte Chemie vol 44 no 28 pp 4328ndash43332005

[5] M Zic M Ristic and S Music ldquoThe effect of temperature onthe crystallization of 120572-Fe

2O3particles from dense 120573-FeOOH

suspensionsrdquo Materials Chemistry and Physics vol 120 no 1pp 160ndash166 2010

10 Advances in Materials Science and Engineering

[6] A Jagminas K Mazeika E Juska J Reklaitis and D Bal-trunas ldquoElectrochemical fabrication and characterization oflepidocrocite (120574-FeOOH) nanowire arraysrdquo Applied SurfaceScience vol 256 no 12 pp 3993ndash3996 2010

[7] P Dillmann R Balasubramaniam and G Beranger ldquoChar-acterization of protective rust on ancient Indian iron usingmicroprobe analysesrdquo Corrosion Science vol 44 no 10 pp2231ndash2242 2002

[8] H Tanaka J Wakatsuki K Kandori T Ishikawa and TNakayama ldquoRole of zinc compounds on the formation mor-phology and adsorption characteristics of 120573-FeOOH rustsrdquoCorrosion Science vol 52 no 9 pp 2973ndash2978 2010

[9] T Ishikawa M Kumagai A Yasukawa K Kandori TNakayama and F Yuse ldquoInfluences of metal ions on theformation of 120574-FeOOH andmagnetite rustsrdquoCorrosion Sciencevol 44 no 5 pp 1073ndash1086 2002

[10] A Collazo X R Novoa C Perez and B Puga ldquoThe corrosionprotection mechanism of rust converters an electrochemicalimpedance spectroscopy studyrdquo Electrochimica Acta vol 55 no21 pp 6156ndash6162 2010

[11] M Zic M Ristic and S Music ldquoPrecipitation of 120572-Fe2O3

from dense 120573-FeOOH suspensions with added ammoniumamidosulfonaterdquo Journal of Molecular Structure vol 924-926pp 235ndash242 2009

[12] C Q Cheng J Zhao T S Cao Q Q Fu M K Lei and DW Deng ldquoFacile chromaticity approach for the inspection ofpassive films on austenitic stainless steelrdquoCorrosion Science vol70 pp 235ndash242 2013

[13] A I Munoz J G Anton J L Guinon and V P HerranzldquoInhibition effect of chromate on the passivation and pittingcorrosion of a duplex stainless steel in LiBr solutions usingelectrochemical techniquesrdquo Corrosion Science vol 49 no 8pp 3200ndash3225 2007

[14] S Powell ldquoEvaluation of alternative corrosion inhibitors tochromate for use in organic coatings using scanning referenceelectrode techniquerdquo Surface Engineering vol 16 no 2 pp 169ndash175 2000

[15] B J Basu A Srinivasan J Manasa and V K W GripsldquoImproved corrosion protection of aluminium alloy AA 2024by sol-gel hybrid coatings after surface pretreatment by silani-sationrdquo Surface Engineering vol 28 no 4 pp 294ndash299 2012

[16] Z Liu D Yan Y Dong Y Yang Z Chu and Z ZhangldquoThe effect of modified epoxy sealing on the electrochemicalcorrosion behaviour of reactive plasma-sprayed TiN coatingsrdquoCorrosion Science vol 75 pp 220ndash227 2013

[17] A M Simoes J Torres R Picciochi and J C S FernandesldquoCorrosion inhibition at galvanized steel cut edges by phosphatepigmentsrdquo Electrochimica Acta vol 54 no 15 pp 3857ndash38652009

[18] B Gruss ldquoIron phosphatingrdquoMetal Finishing vol 108 no 11-12pp 33ndash37 2010

[19] D Singh and S Yadav ldquoRole of tannic acid based rust converteron formation of passive film on zinc rich coating exposedin simulated concrete pore solutionrdquo Surface and CoatingsTechnology vol 202 no 8 pp 1526ndash1542 2008

[20] B Qian B Hou and M Zheng ldquoThe inhibition effect oftannic acid on mild steel corrosion in seawater wetdry cyclicconditionsrdquo Corrosion Science vol 72 pp 1ndash9 2013

[21] A Ostovari S M Hoseinieh M Peikari S R Shadizadehand S J Hashemi ldquoCorrosion inhibition of mild steel in 1M HCl solution by henna extract a comparative study of the

inhibition by henna and its constituents (Lawsone Gallic acid120572-d-Glucose and Tannic acid)rdquo Corrosion Science vol 51 no 9pp 1935ndash1949 2009

[22] K W Tan M J Kassim and C W Oo ldquoPossible improvementof catechin as corrosion inhibitor in acidic mediumrdquo CorrosionScience vol 65 pp 152ndash162 2012

[23] B Yuan J Xu X Li and M-L Fu ldquoPreparation of Si-Al120572-FeOOH catalyst from an iron-containing waste and surface-catalytic oxidation of methylene blue at neutral pH value in thepresence of H

2O2rdquo Chemical Engineering Journal vol 226 pp

181ndash188 2013[24] S Bashir R W McCabe C Boxall M S Leaver and D Mobbs

ldquoSynthesis of 120572- and120573-FeOOH iron oxide nanoparticles in non-ionic surfactant mediumrdquo Journal of Nanoparticle Research vol11 no 3 pp 701ndash706 2009

[25] L Carlson and U Schwertmann ldquoNatural occurrence of ferox-yhite (120575rsquo-FeOOH)rdquo Clays amp Clay Minerals vol 28 no 4 pp272ndash280 1980

[26] Z Wang C Xu and X Dong ldquoLocalized corrosion andphase transformation of simulated archaeological ironrdquoChineseJournal of Chemical Engineering vol 16 no 2 pp 299ndash3052008

[27] C Remazeilles and P Refait ldquoOn the formation of 120573-FeOOH(akaganeite) in chloride-containing environmentsrdquo CorrosionScience vol 49 no 2 pp 844ndash857 2007

[28] Z Wang C Xu X Cao and B Xu ldquoThe Morphology phasecomposition and effect of corrosion product on simulatedarchaeological ironrdquo Chinese Journal of Chemical Engineeringvol 15 no 3 pp 433ndash438 2007

[29] S Nasrazadani ldquoThe application of infrared spectroscopy toa study of phosphoric and tannic acids interactions withmagnetite (Fe

3O4) goethite (120572-FeOOH) and lepidocrocite (120574-

FeOOH)rdquo Corrosion Science vol 39 no 10-11 pp 1845ndash18591997

[30] R Balasubramaniam ldquoOn the corrosion resistance of the Delhiiron pillarrdquo Corrosion Science vol 42 no 12 pp 2103ndash21292000

[31] AM Al-Mayouf ldquoInhibitors for chemical cleaning of iron withtannic acidrdquo Desalination vol 121 no 2 pp 173ndash182 1999

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CeramicsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CompositesJournal of

NanoparticlesJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Biomaterials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

MetallurgyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BioMed Research International

MaterialsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Nano

materials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal ofNanomaterials

4 Advances in Materials Science and Engineering

Inte

nsity

(cps

)

20 30 40 50 60 70 80 90

0

40

80

120

160

120573-FeOOH

2120579 (∘)

120572-FeOOH (goethite)

(a)In

tens

ity (c

ps)

0

200

400

600

800

1000

10 20 30 40 50 60 70 80

120573-FeOOH (akaganeite)

2120579 (∘)

(b)

Inte

nsity

(cps

)

10 20 30 40 50 60 70 80 900

100

200

300

120574-FeOOH (lepidocrocite)

2120579 (∘)

(c)

Inte

nsity

(cou

nts)

10 20 30 40 50 60 70 800

50

100

150

200

250

120575-FeOOH (amorphous)

2120579 (∘)

(d)

Figure 3 X-ray diffraction patterns of different forms of FeOOHX 120572-FeOOH 998787 120573-FeOOH e 120574-FeOOH ◼ 120575-FeOOH

corroding the iron but also became a storage area for anionsand moisture resulting in strong adsorption Meanwhile itslowed down the evaporation rate of moisture and extendedthe corrosion cycle of moisture thus promoting corrosiveions acting on the cast iron

Moreover among the common anions in atmospherethat would cause corrosion NO

3

minus had the weakest corrosionpower on cast iron The corrosive power increased progres-sively following the order Clminus+HSO

4

minusgtHSO

4gt Clminus Under

the combined action of Clminus and HSO4

minus the corrosion of castiron was much more serious than any other ions used aloneindicating synergistic activities between Clminus and HSO

4

minus 120573-FeOOH was produced exclusively in the presence of Clminus [27]which had weaker iron protection and resulted in more iron

rusting The corrosion product of cast iron in contact withthe FeCl

2solution over 138 days was made up of three layers

120572-FeOOH Fe3O4 and a little 120573-FeOOH in the inner layer 120574-

FeOOH in the middle layer and 120572-FeOOH in the outer layer[28]

33 Interactions between FeOOH and Different Combinationsof Phosphoric AcidTannic Acid Different states and colors ofreaction products after filtrating drying and grinding weredocumented in Table 2 The yellow powder and tannic acidwere identical in material phases and composition suggest-ing that the yellow powder was excess tannins As tannic aciddissolves 120574-FeOOH and higher concentrations of tannic acidspeeded up the dissolution [29] it is suggested that FeOOH

Advances in Materials Science and Engineering 5

120572-FeOOH

100nm

(a)

(a)

120573-FeOOH

100nm

(b)

(b)

120574-FeOOH

100nm

(c)

(c)

(d)

120575-FeOOH

100nm

(d)

Figure 4 TEM images of different forms of FeOOH

Table 2 The state and color of reaction products

Phosphoric acidtannic acid 120573-FeOOH 120574-FeOOH 120575-FeOOH3T-10P Gray powder Gray powder Gray powder3T-20P Gray powder Yellow powder Less product blue-gray3T-30P Less product beige Yellow powder Yellow powder5T-10P Gray powder Blue-gray yellow Blue-gray powder5T-20P Gray powder Yellow powder Blue-gray powder5T-30P Less product beige Less product blue-gray Yellow powder

was completely dissolved Thus these proportions were notsuitable as a choice of rust stabilizer formula due to accumu-lation of residual tannic acid after reaction In addition forsome combinations the reaction products were very limitedindicating that most of the FeOOH was dissolved under theaction of phosphoric acidtannic acid Only a small amountof FeOOH was involved in chemical transformation Thusthese combinations were also undesirable for rust stabilizerformula

At the same time according to protection standards ofcultural relics protection materials must be close to originalartifacts to the maximum extent Among the combinationsin Table 2 only the product of the 3T-10P namely 3 tannicacid + 10 phosphoric acid and FeOOH was gray similarto the color of steel materials suggesting that 3 tannicacid + 10 phosphoric acid was the most suitable formulafor rust stabilizer Previous studies showed that conventionalanticorrosive paints or the painting schemes applied on steelpreviously treatedwith a primer formulatedwith pine tanninsextend the duration of painting schemes more than 50relative to the case without this chemical treatment [30]

The XRD pattern of reaction products of 120573- 120574- and 120575-FeOOH and 3T-10P was presented in Figure 6 A crystallinephosphate was the major product and it matched the XRDpatterns of Fe

3P6O2well In contrast the major constituents

of the scale onDelhi iron pillar were crystalline iron hydrogenphosphate hydrate (FePO

4sdotH3PO4sdot4H2O) as well as 120572- 120574-

and 120575-FeOOH and magnetite [30] or crystalline phosphateFe2(PO4)(OH) [7] No phases related to tannic acid were

identified suggesting that the transformation products oftannic acid and FeOOH were amorphous

The transformation products from the reaction of tannicacidphosphoric acid and FeOOHwere further characterizedby XPS The reaction products between 120573-FeOOH and 3T-10P were mainly Fe C P and O (Figure 7) The bindingenergy of Fe2p

32was 71242 eV confirming the presence of

Fe3+ in the productThe binding energy of C1s can be decom-posed to 28507 28689 and 28850 eV with the former corre-sponding to carbon and the combination of the latter two cor-responding to standard spectral peaks of carboxide in tannicacidThe binding energy of O1s was 53195 eV correspondingtoCndashOH in tannic acid In addition the peak at 13364 eVwas

6 Advances in Materials Science and Engineering

(a)

200120583m

120574-FeOOHiron

(a)

(b)

200120583m

120573-FeOOHiron

(b)

(c)

100120583m

120574-FeOOHiron

(c)

(d)

100120583m

120573-FeOOHiron

(d)

(e)

200120583m

120574-FeOOHiron

(e)

(f)

100120583m120573-FeOOHiron

(f)

(g)

100120583m120574-FeOOHiron

(g)

(h)

200120583m120573-FeOOHiron

(h)

Figure 5 SEM images of rust powdercast iron interface with the effects of NO3

minus ((a) and (b)) Clminus ((c) and (d)) HSO4

minus ((e) and (f)) andClminus+HSO

4

minus ((g) and (h))

originated from P2p confirming the presence of phosphateThe peaks of Fe2p

32in Fe3+ generally lie between 71020

and 71105 eV However the binding energy of Fe2p32

in thisstudy was 71242 eV resulting in a chemical shift of morethan 1 eV Such a shift may suggest a change in chemical

environment of the elements thus indicating formation ofa new chemical bond between Fe3+ and other substancesDue to the presence of tannic acid it may suggest the for-mation of chelate between iron and tannin [31] as illustratedin Scheme 1

Advances in Materials Science and Engineering 7

10 20 30 40 50 60 70

0

500

1000

1500

2000

2500

3000

3500

Inte

nsity

(cps

)

2120579 (∘)

120575-FeOOH3T-10P

120574-FeOOH3T-10P

120573-FeOOH3T-10P

Fe3P6O2

Figure 6 XRD patterns of the products formed from the reaction of FeOOH and 3T-10P

730 720 710 700 690

8000

9000

10000

11000

12000

13000

14000

Inte

nsity

(cps

)

Binding energy (eV)

120573-FeOOH3T-10P

71242Fe3+

Fe2p

(a)

Inte

nsity

(cps

)

294 292 290 288 286 284 282

2000

3000

4000

5000

6000

7000

8000

9000

10000

Binding energy (eV)

120573-FeOOH3T-10P

28850

28507

28689

C1sC

CndashOH

OndashC=O

(b)

538 536 534 532 530 5280

5000

10000

15000

20000

25000

30000

Inte

nsity

(cps

)

Binding energy (eV)

120573-FeOOH3P-10T53195O1s CndashOH

(c)

Inte

nsity

(cps

)

138 136 134 132 1301000

1500

2000

2500

3000

3500

4000

4500

Binding energy (eV)

120573-FeOOH3T-10P

13364P2p P5+

(d)

Figure 7 XPS spectra of the products formed from the reaction of 120573-FeOOH and 3T-10P

8 Advances in Materials Science and Engineering

730 720 710 700 690

7500

8000

8500

9000

9500

10000

10500

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P

Fe3+

Fe2p

71205

(a)

292 290 288 286 284 2820

2000

4000

6000

8000

10000

12000

14000

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P

28642

28490

28850

C1s C

CndashOH

OndashC=O

(b)

528 530 532 534 5360

5000

10000

15000

20000

25000

30000

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P53258

O1sCndashOH

(c)

138 136 134 132

1000120014001600180020002200240026002800

800

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P13399

P2p P5+

(d)

Figure 8 XPS spectra of the products formed from the reaction of 120574-FeOOH and 3T-10P

ROH

OH

OH

R

OO

O

Fe3+Fe3+ ++ 3H3+

Scheme 1 Single-chelate complex ion body

Thus it was speculated that the reaction products of 120573-FeOOH and 3T-10P were made up of iron phosphate andchelate of iron and tannin

The results of XPS analyses of the reaction productsgenerated by 120574-FeOOHand 3T-10P and by 120575-FeOOHand 3T-10P were illustrated in Figures 8 and 9 The composition ofthese two products was similar to the reaction products of 120573-FeOOH and 3T-10P that is was made mainly of Fe C P andO and having about the same peak positions Therefore thereaction products were mainly made of iron phosphate andchelate of iron and tannin

The structures of iron phosphate and chelate of iron andtannin are relatively stable If acting as chemical conversionlayer the cast iron may develop strong corrosion resistancecapacity Meanwhile the layer can enhance bonding betweenthe coating and the substrate These favorable physical andchemical properties could meet the need of coating andsealing treatment for iron artifact However the mechanismsof tannic acidphosphoric acid rust conversion may needfurther study

4 Conclusions

(1) When cast iron was covered by 120573-FeOOH and 120574-FeOOH corrosion the rust layer was porous and nottight enough to provide a good protection againstcorrosion by NO

3

minus Clminus HSO4

minus and Clminus+HSO4

minus(2) Among common anions tested NO

3

minus had the weak-est corrosive power on cast ironThe corrosion powerincreased in the following sequence Clminus HSO

4

minus andClminus+HSO

4

minus Meanwhile synergistic corrosion couldbe enhanced when both Clminus andHSO

4

minus were present

Advances in Materials Science and Engineering 9

730 720 710 700 6907000

7500

8000

8500

9000

9500

10000

10500In

tens

ity (c

ps)

71293Fe3+

120575-FeOOH3T-10P

Binding energy (eV)

(a)

290 288 286 284 2820

2000

4000

6000

8000

10000

12000

14000

Inte

nsity

(cps

)

28503

28659

28873

C1s C 120575-FeOOH3T-10P

Binding energy (eV)

CndashOH

OndashC=O

(b)

536 534 532 530 5280

5000

10000

15000

20000

25000

Inte

nsity

(cps

)

53061

O1sOHminus

Binding energy (eV)

(c)

137 136 135 134 133 132 131

8001000120014001600180020002200240026002800

Inte

nsity

(cps

)

13410P2p 120575-FeOOH3T-10PP5+

Binding energy (eV)

(d)

Figure 9 XPS spectra of the products formed from the reaction of 120575-FeOOH and 3T-10P

(3) Analyses of the reaction products between FeOOHand different combinations of phosphoric acidtannicacid showed that 3 tannic acid + 10 phosphoricacid was the most suitable formula as rust stabilizer

(4) The reaction products between120573-FeOOH 120574-FeOOHor 120575-FeOOH and 3T-10P were made up of ironphosphate and chelate of iron and tannin

Conflict of Interests

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

Acknowledgments

This present work was supported by the National NaturalScience Foundation of China (Grants nos 51202226 and51172216) and the Fundamental Research Funds for theCentral Universities (Grant no 2652013043)

References

[1] W Xu K Daub X Zhang J J Noel D W Shoesmith and JC Wren ldquoOxide formation and conversion on carbon steel inmildly basic solutionsrdquo Electrochimica Acta vol 54 no 24 pp5727ndash5738 2009

[2] X Liu G Qiu A Yan Z Wang and X Li ldquoHydrothermal syn-thesis and characterization of 120572-FeOOH and 120572-Fe

2O3uniform

nanocrystallinesrdquo Journal of Alloys andCompounds vol 433 no1-2 pp 216ndash220 2007

[3] H Abdel-Samad and P R Watson ldquoAn XPS study of theadsorption of lead on goethite (120572-FeOOH)rdquo Applied SurfaceScience vol 136 no 1-2 pp 46ndash54 1998

[4] C-J Jia L-D Sun Z-G Yan et al ldquoSingle-crystalline iron oxidenanotubesrdquoAngewandte Chemie vol 44 no 28 pp 4328ndash43332005

[5] M Zic M Ristic and S Music ldquoThe effect of temperature onthe crystallization of 120572-Fe

2O3particles from dense 120573-FeOOH

suspensionsrdquo Materials Chemistry and Physics vol 120 no 1pp 160ndash166 2010

10 Advances in Materials Science and Engineering

[6] A Jagminas K Mazeika E Juska J Reklaitis and D Bal-trunas ldquoElectrochemical fabrication and characterization oflepidocrocite (120574-FeOOH) nanowire arraysrdquo Applied SurfaceScience vol 256 no 12 pp 3993ndash3996 2010

[7] P Dillmann R Balasubramaniam and G Beranger ldquoChar-acterization of protective rust on ancient Indian iron usingmicroprobe analysesrdquo Corrosion Science vol 44 no 10 pp2231ndash2242 2002

[8] H Tanaka J Wakatsuki K Kandori T Ishikawa and TNakayama ldquoRole of zinc compounds on the formation mor-phology and adsorption characteristics of 120573-FeOOH rustsrdquoCorrosion Science vol 52 no 9 pp 2973ndash2978 2010

[9] T Ishikawa M Kumagai A Yasukawa K Kandori TNakayama and F Yuse ldquoInfluences of metal ions on theformation of 120574-FeOOH andmagnetite rustsrdquoCorrosion Sciencevol 44 no 5 pp 1073ndash1086 2002

[10] A Collazo X R Novoa C Perez and B Puga ldquoThe corrosionprotection mechanism of rust converters an electrochemicalimpedance spectroscopy studyrdquo Electrochimica Acta vol 55 no21 pp 6156ndash6162 2010

[11] M Zic M Ristic and S Music ldquoPrecipitation of 120572-Fe2O3

from dense 120573-FeOOH suspensions with added ammoniumamidosulfonaterdquo Journal of Molecular Structure vol 924-926pp 235ndash242 2009

[12] C Q Cheng J Zhao T S Cao Q Q Fu M K Lei and DW Deng ldquoFacile chromaticity approach for the inspection ofpassive films on austenitic stainless steelrdquoCorrosion Science vol70 pp 235ndash242 2013

[13] A I Munoz J G Anton J L Guinon and V P HerranzldquoInhibition effect of chromate on the passivation and pittingcorrosion of a duplex stainless steel in LiBr solutions usingelectrochemical techniquesrdquo Corrosion Science vol 49 no 8pp 3200ndash3225 2007

[14] S Powell ldquoEvaluation of alternative corrosion inhibitors tochromate for use in organic coatings using scanning referenceelectrode techniquerdquo Surface Engineering vol 16 no 2 pp 169ndash175 2000

[15] B J Basu A Srinivasan J Manasa and V K W GripsldquoImproved corrosion protection of aluminium alloy AA 2024by sol-gel hybrid coatings after surface pretreatment by silani-sationrdquo Surface Engineering vol 28 no 4 pp 294ndash299 2012

[16] Z Liu D Yan Y Dong Y Yang Z Chu and Z ZhangldquoThe effect of modified epoxy sealing on the electrochemicalcorrosion behaviour of reactive plasma-sprayed TiN coatingsrdquoCorrosion Science vol 75 pp 220ndash227 2013

[17] A M Simoes J Torres R Picciochi and J C S FernandesldquoCorrosion inhibition at galvanized steel cut edges by phosphatepigmentsrdquo Electrochimica Acta vol 54 no 15 pp 3857ndash38652009

[18] B Gruss ldquoIron phosphatingrdquoMetal Finishing vol 108 no 11-12pp 33ndash37 2010

[19] D Singh and S Yadav ldquoRole of tannic acid based rust converteron formation of passive film on zinc rich coating exposedin simulated concrete pore solutionrdquo Surface and CoatingsTechnology vol 202 no 8 pp 1526ndash1542 2008

[20] B Qian B Hou and M Zheng ldquoThe inhibition effect oftannic acid on mild steel corrosion in seawater wetdry cyclicconditionsrdquo Corrosion Science vol 72 pp 1ndash9 2013

[21] A Ostovari S M Hoseinieh M Peikari S R Shadizadehand S J Hashemi ldquoCorrosion inhibition of mild steel in 1M HCl solution by henna extract a comparative study of the

inhibition by henna and its constituents (Lawsone Gallic acid120572-d-Glucose and Tannic acid)rdquo Corrosion Science vol 51 no 9pp 1935ndash1949 2009

[22] K W Tan M J Kassim and C W Oo ldquoPossible improvementof catechin as corrosion inhibitor in acidic mediumrdquo CorrosionScience vol 65 pp 152ndash162 2012

[23] B Yuan J Xu X Li and M-L Fu ldquoPreparation of Si-Al120572-FeOOH catalyst from an iron-containing waste and surface-catalytic oxidation of methylene blue at neutral pH value in thepresence of H

2O2rdquo Chemical Engineering Journal vol 226 pp

181ndash188 2013[24] S Bashir R W McCabe C Boxall M S Leaver and D Mobbs

ldquoSynthesis of 120572- and120573-FeOOH iron oxide nanoparticles in non-ionic surfactant mediumrdquo Journal of Nanoparticle Research vol11 no 3 pp 701ndash706 2009

[25] L Carlson and U Schwertmann ldquoNatural occurrence of ferox-yhite (120575rsquo-FeOOH)rdquo Clays amp Clay Minerals vol 28 no 4 pp272ndash280 1980

[26] Z Wang C Xu and X Dong ldquoLocalized corrosion andphase transformation of simulated archaeological ironrdquoChineseJournal of Chemical Engineering vol 16 no 2 pp 299ndash3052008

[27] C Remazeilles and P Refait ldquoOn the formation of 120573-FeOOH(akaganeite) in chloride-containing environmentsrdquo CorrosionScience vol 49 no 2 pp 844ndash857 2007

[28] Z Wang C Xu X Cao and B Xu ldquoThe Morphology phasecomposition and effect of corrosion product on simulatedarchaeological ironrdquo Chinese Journal of Chemical Engineeringvol 15 no 3 pp 433ndash438 2007

[29] S Nasrazadani ldquoThe application of infrared spectroscopy toa study of phosphoric and tannic acids interactions withmagnetite (Fe

3O4) goethite (120572-FeOOH) and lepidocrocite (120574-

FeOOH)rdquo Corrosion Science vol 39 no 10-11 pp 1845ndash18591997

[30] R Balasubramaniam ldquoOn the corrosion resistance of the Delhiiron pillarrdquo Corrosion Science vol 42 no 12 pp 2103ndash21292000

[31] AM Al-Mayouf ldquoInhibitors for chemical cleaning of iron withtannic acidrdquo Desalination vol 121 no 2 pp 173ndash182 1999

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CeramicsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CompositesJournal of

NanoparticlesJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Biomaterials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

MetallurgyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BioMed Research International

MaterialsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Nano

materials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal ofNanomaterials

Advances in Materials Science and Engineering 5

120572-FeOOH

100nm

(a)

(a)

120573-FeOOH

100nm

(b)

(b)

120574-FeOOH

100nm

(c)

(c)

(d)

120575-FeOOH

100nm

(d)

Figure 4 TEM images of different forms of FeOOH

Table 2 The state and color of reaction products

Phosphoric acidtannic acid 120573-FeOOH 120574-FeOOH 120575-FeOOH3T-10P Gray powder Gray powder Gray powder3T-20P Gray powder Yellow powder Less product blue-gray3T-30P Less product beige Yellow powder Yellow powder5T-10P Gray powder Blue-gray yellow Blue-gray powder5T-20P Gray powder Yellow powder Blue-gray powder5T-30P Less product beige Less product blue-gray Yellow powder

was completely dissolved Thus these proportions were notsuitable as a choice of rust stabilizer formula due to accumu-lation of residual tannic acid after reaction In addition forsome combinations the reaction products were very limitedindicating that most of the FeOOH was dissolved under theaction of phosphoric acidtannic acid Only a small amountof FeOOH was involved in chemical transformation Thusthese combinations were also undesirable for rust stabilizerformula

At the same time according to protection standards ofcultural relics protection materials must be close to originalartifacts to the maximum extent Among the combinationsin Table 2 only the product of the 3T-10P namely 3 tannicacid + 10 phosphoric acid and FeOOH was gray similarto the color of steel materials suggesting that 3 tannicacid + 10 phosphoric acid was the most suitable formulafor rust stabilizer Previous studies showed that conventionalanticorrosive paints or the painting schemes applied on steelpreviously treatedwith a primer formulatedwith pine tanninsextend the duration of painting schemes more than 50relative to the case without this chemical treatment [30]

The XRD pattern of reaction products of 120573- 120574- and 120575-FeOOH and 3T-10P was presented in Figure 6 A crystallinephosphate was the major product and it matched the XRDpatterns of Fe

3P6O2well In contrast the major constituents

of the scale onDelhi iron pillar were crystalline iron hydrogenphosphate hydrate (FePO

4sdotH3PO4sdot4H2O) as well as 120572- 120574-

and 120575-FeOOH and magnetite [30] or crystalline phosphateFe2(PO4)(OH) [7] No phases related to tannic acid were

identified suggesting that the transformation products oftannic acid and FeOOH were amorphous

The transformation products from the reaction of tannicacidphosphoric acid and FeOOHwere further characterizedby XPS The reaction products between 120573-FeOOH and 3T-10P were mainly Fe C P and O (Figure 7) The bindingenergy of Fe2p

32was 71242 eV confirming the presence of

Fe3+ in the productThe binding energy of C1s can be decom-posed to 28507 28689 and 28850 eV with the former corre-sponding to carbon and the combination of the latter two cor-responding to standard spectral peaks of carboxide in tannicacidThe binding energy of O1s was 53195 eV correspondingtoCndashOH in tannic acid In addition the peak at 13364 eVwas

6 Advances in Materials Science and Engineering

(a)

200120583m

120574-FeOOHiron

(a)

(b)

200120583m

120573-FeOOHiron

(b)

(c)

100120583m

120574-FeOOHiron

(c)

(d)

100120583m

120573-FeOOHiron

(d)

(e)

200120583m

120574-FeOOHiron

(e)

(f)

100120583m120573-FeOOHiron

(f)

(g)

100120583m120574-FeOOHiron

(g)

(h)

200120583m120573-FeOOHiron

(h)

Figure 5 SEM images of rust powdercast iron interface with the effects of NO3

minus ((a) and (b)) Clminus ((c) and (d)) HSO4

minus ((e) and (f)) andClminus+HSO

4

minus ((g) and (h))

originated from P2p confirming the presence of phosphateThe peaks of Fe2p

32in Fe3+ generally lie between 71020

and 71105 eV However the binding energy of Fe2p32

in thisstudy was 71242 eV resulting in a chemical shift of morethan 1 eV Such a shift may suggest a change in chemical

environment of the elements thus indicating formation ofa new chemical bond between Fe3+ and other substancesDue to the presence of tannic acid it may suggest the for-mation of chelate between iron and tannin [31] as illustratedin Scheme 1

Advances in Materials Science and Engineering 7

10 20 30 40 50 60 70

0

500

1000

1500

2000

2500

3000

3500

Inte

nsity

(cps

)

2120579 (∘)

120575-FeOOH3T-10P

120574-FeOOH3T-10P

120573-FeOOH3T-10P

Fe3P6O2

Figure 6 XRD patterns of the products formed from the reaction of FeOOH and 3T-10P

730 720 710 700 690

8000

9000

10000

11000

12000

13000

14000

Inte

nsity

(cps

)

Binding energy (eV)

120573-FeOOH3T-10P

71242Fe3+

Fe2p

(a)

Inte

nsity

(cps

)

294 292 290 288 286 284 282

2000

3000

4000

5000

6000

7000

8000

9000

10000

Binding energy (eV)

120573-FeOOH3T-10P

28850

28507

28689

C1sC

CndashOH

OndashC=O

(b)

538 536 534 532 530 5280

5000

10000

15000

20000

25000

30000

Inte

nsity

(cps

)

Binding energy (eV)

120573-FeOOH3P-10T53195O1s CndashOH

(c)

Inte

nsity

(cps

)

138 136 134 132 1301000

1500

2000

2500

3000

3500

4000

4500

Binding energy (eV)

120573-FeOOH3T-10P

13364P2p P5+

(d)

Figure 7 XPS spectra of the products formed from the reaction of 120573-FeOOH and 3T-10P

8 Advances in Materials Science and Engineering

730 720 710 700 690

7500

8000

8500

9000

9500

10000

10500

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P

Fe3+

Fe2p

71205

(a)

292 290 288 286 284 2820

2000

4000

6000

8000

10000

12000

14000

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P

28642

28490

28850

C1s C

CndashOH

OndashC=O

(b)

528 530 532 534 5360

5000

10000

15000

20000

25000

30000

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P53258

O1sCndashOH

(c)

138 136 134 132

1000120014001600180020002200240026002800

800

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P13399

P2p P5+

(d)

Figure 8 XPS spectra of the products formed from the reaction of 120574-FeOOH and 3T-10P

ROH

OH

OH

R

OO

O

Fe3+Fe3+ ++ 3H3+

Scheme 1 Single-chelate complex ion body

Thus it was speculated that the reaction products of 120573-FeOOH and 3T-10P were made up of iron phosphate andchelate of iron and tannin

The results of XPS analyses of the reaction productsgenerated by 120574-FeOOHand 3T-10P and by 120575-FeOOHand 3T-10P were illustrated in Figures 8 and 9 The composition ofthese two products was similar to the reaction products of 120573-FeOOH and 3T-10P that is was made mainly of Fe C P andO and having about the same peak positions Therefore thereaction products were mainly made of iron phosphate andchelate of iron and tannin

The structures of iron phosphate and chelate of iron andtannin are relatively stable If acting as chemical conversionlayer the cast iron may develop strong corrosion resistancecapacity Meanwhile the layer can enhance bonding betweenthe coating and the substrate These favorable physical andchemical properties could meet the need of coating andsealing treatment for iron artifact However the mechanismsof tannic acidphosphoric acid rust conversion may needfurther study

4 Conclusions

(1) When cast iron was covered by 120573-FeOOH and 120574-FeOOH corrosion the rust layer was porous and nottight enough to provide a good protection againstcorrosion by NO

3

minus Clminus HSO4

minus and Clminus+HSO4

minus(2) Among common anions tested NO

3

minus had the weak-est corrosive power on cast ironThe corrosion powerincreased in the following sequence Clminus HSO

4

minus andClminus+HSO

4

minus Meanwhile synergistic corrosion couldbe enhanced when both Clminus andHSO

4

minus were present

Advances in Materials Science and Engineering 9

730 720 710 700 6907000

7500

8000

8500

9000

9500

10000

10500In

tens

ity (c

ps)

71293Fe3+

120575-FeOOH3T-10P

Binding energy (eV)

(a)

290 288 286 284 2820

2000

4000

6000

8000

10000

12000

14000

Inte

nsity

(cps

)

28503

28659

28873

C1s C 120575-FeOOH3T-10P

Binding energy (eV)

CndashOH

OndashC=O

(b)

536 534 532 530 5280

5000

10000

15000

20000

25000

Inte

nsity

(cps

)

53061

O1sOHminus

Binding energy (eV)

(c)

137 136 135 134 133 132 131

8001000120014001600180020002200240026002800

Inte

nsity

(cps

)

13410P2p 120575-FeOOH3T-10PP5+

Binding energy (eV)

(d)

Figure 9 XPS spectra of the products formed from the reaction of 120575-FeOOH and 3T-10P

(3) Analyses of the reaction products between FeOOHand different combinations of phosphoric acidtannicacid showed that 3 tannic acid + 10 phosphoricacid was the most suitable formula as rust stabilizer

(4) The reaction products between120573-FeOOH 120574-FeOOHor 120575-FeOOH and 3T-10P were made up of ironphosphate and chelate of iron and tannin

Conflict of Interests

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

Acknowledgments

This present work was supported by the National NaturalScience Foundation of China (Grants nos 51202226 and51172216) and the Fundamental Research Funds for theCentral Universities (Grant no 2652013043)

References

[1] W Xu K Daub X Zhang J J Noel D W Shoesmith and JC Wren ldquoOxide formation and conversion on carbon steel inmildly basic solutionsrdquo Electrochimica Acta vol 54 no 24 pp5727ndash5738 2009

[2] X Liu G Qiu A Yan Z Wang and X Li ldquoHydrothermal syn-thesis and characterization of 120572-FeOOH and 120572-Fe

2O3uniform

nanocrystallinesrdquo Journal of Alloys andCompounds vol 433 no1-2 pp 216ndash220 2007

[3] H Abdel-Samad and P R Watson ldquoAn XPS study of theadsorption of lead on goethite (120572-FeOOH)rdquo Applied SurfaceScience vol 136 no 1-2 pp 46ndash54 1998

[4] C-J Jia L-D Sun Z-G Yan et al ldquoSingle-crystalline iron oxidenanotubesrdquoAngewandte Chemie vol 44 no 28 pp 4328ndash43332005

[5] M Zic M Ristic and S Music ldquoThe effect of temperature onthe crystallization of 120572-Fe

2O3particles from dense 120573-FeOOH

suspensionsrdquo Materials Chemistry and Physics vol 120 no 1pp 160ndash166 2010

10 Advances in Materials Science and Engineering

[6] A Jagminas K Mazeika E Juska J Reklaitis and D Bal-trunas ldquoElectrochemical fabrication and characterization oflepidocrocite (120574-FeOOH) nanowire arraysrdquo Applied SurfaceScience vol 256 no 12 pp 3993ndash3996 2010

[7] P Dillmann R Balasubramaniam and G Beranger ldquoChar-acterization of protective rust on ancient Indian iron usingmicroprobe analysesrdquo Corrosion Science vol 44 no 10 pp2231ndash2242 2002

[8] H Tanaka J Wakatsuki K Kandori T Ishikawa and TNakayama ldquoRole of zinc compounds on the formation mor-phology and adsorption characteristics of 120573-FeOOH rustsrdquoCorrosion Science vol 52 no 9 pp 2973ndash2978 2010

[9] T Ishikawa M Kumagai A Yasukawa K Kandori TNakayama and F Yuse ldquoInfluences of metal ions on theformation of 120574-FeOOH andmagnetite rustsrdquoCorrosion Sciencevol 44 no 5 pp 1073ndash1086 2002

[10] A Collazo X R Novoa C Perez and B Puga ldquoThe corrosionprotection mechanism of rust converters an electrochemicalimpedance spectroscopy studyrdquo Electrochimica Acta vol 55 no21 pp 6156ndash6162 2010

[11] M Zic M Ristic and S Music ldquoPrecipitation of 120572-Fe2O3

from dense 120573-FeOOH suspensions with added ammoniumamidosulfonaterdquo Journal of Molecular Structure vol 924-926pp 235ndash242 2009

[12] C Q Cheng J Zhao T S Cao Q Q Fu M K Lei and DW Deng ldquoFacile chromaticity approach for the inspection ofpassive films on austenitic stainless steelrdquoCorrosion Science vol70 pp 235ndash242 2013

[13] A I Munoz J G Anton J L Guinon and V P HerranzldquoInhibition effect of chromate on the passivation and pittingcorrosion of a duplex stainless steel in LiBr solutions usingelectrochemical techniquesrdquo Corrosion Science vol 49 no 8pp 3200ndash3225 2007

[14] S Powell ldquoEvaluation of alternative corrosion inhibitors tochromate for use in organic coatings using scanning referenceelectrode techniquerdquo Surface Engineering vol 16 no 2 pp 169ndash175 2000

[15] B J Basu A Srinivasan J Manasa and V K W GripsldquoImproved corrosion protection of aluminium alloy AA 2024by sol-gel hybrid coatings after surface pretreatment by silani-sationrdquo Surface Engineering vol 28 no 4 pp 294ndash299 2012

[16] Z Liu D Yan Y Dong Y Yang Z Chu and Z ZhangldquoThe effect of modified epoxy sealing on the electrochemicalcorrosion behaviour of reactive plasma-sprayed TiN coatingsrdquoCorrosion Science vol 75 pp 220ndash227 2013

[17] A M Simoes J Torres R Picciochi and J C S FernandesldquoCorrosion inhibition at galvanized steel cut edges by phosphatepigmentsrdquo Electrochimica Acta vol 54 no 15 pp 3857ndash38652009

[18] B Gruss ldquoIron phosphatingrdquoMetal Finishing vol 108 no 11-12pp 33ndash37 2010

[19] D Singh and S Yadav ldquoRole of tannic acid based rust converteron formation of passive film on zinc rich coating exposedin simulated concrete pore solutionrdquo Surface and CoatingsTechnology vol 202 no 8 pp 1526ndash1542 2008

[20] B Qian B Hou and M Zheng ldquoThe inhibition effect oftannic acid on mild steel corrosion in seawater wetdry cyclicconditionsrdquo Corrosion Science vol 72 pp 1ndash9 2013

[21] A Ostovari S M Hoseinieh M Peikari S R Shadizadehand S J Hashemi ldquoCorrosion inhibition of mild steel in 1M HCl solution by henna extract a comparative study of the

inhibition by henna and its constituents (Lawsone Gallic acid120572-d-Glucose and Tannic acid)rdquo Corrosion Science vol 51 no 9pp 1935ndash1949 2009

[22] K W Tan M J Kassim and C W Oo ldquoPossible improvementof catechin as corrosion inhibitor in acidic mediumrdquo CorrosionScience vol 65 pp 152ndash162 2012

[23] B Yuan J Xu X Li and M-L Fu ldquoPreparation of Si-Al120572-FeOOH catalyst from an iron-containing waste and surface-catalytic oxidation of methylene blue at neutral pH value in thepresence of H

2O2rdquo Chemical Engineering Journal vol 226 pp

181ndash188 2013[24] S Bashir R W McCabe C Boxall M S Leaver and D Mobbs

ldquoSynthesis of 120572- and120573-FeOOH iron oxide nanoparticles in non-ionic surfactant mediumrdquo Journal of Nanoparticle Research vol11 no 3 pp 701ndash706 2009

[25] L Carlson and U Schwertmann ldquoNatural occurrence of ferox-yhite (120575rsquo-FeOOH)rdquo Clays amp Clay Minerals vol 28 no 4 pp272ndash280 1980

[26] Z Wang C Xu and X Dong ldquoLocalized corrosion andphase transformation of simulated archaeological ironrdquoChineseJournal of Chemical Engineering vol 16 no 2 pp 299ndash3052008

[27] C Remazeilles and P Refait ldquoOn the formation of 120573-FeOOH(akaganeite) in chloride-containing environmentsrdquo CorrosionScience vol 49 no 2 pp 844ndash857 2007

[28] Z Wang C Xu X Cao and B Xu ldquoThe Morphology phasecomposition and effect of corrosion product on simulatedarchaeological ironrdquo Chinese Journal of Chemical Engineeringvol 15 no 3 pp 433ndash438 2007

[29] S Nasrazadani ldquoThe application of infrared spectroscopy toa study of phosphoric and tannic acids interactions withmagnetite (Fe

3O4) goethite (120572-FeOOH) and lepidocrocite (120574-

FeOOH)rdquo Corrosion Science vol 39 no 10-11 pp 1845ndash18591997

[30] R Balasubramaniam ldquoOn the corrosion resistance of the Delhiiron pillarrdquo Corrosion Science vol 42 no 12 pp 2103ndash21292000

[31] AM Al-Mayouf ldquoInhibitors for chemical cleaning of iron withtannic acidrdquo Desalination vol 121 no 2 pp 173ndash182 1999

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CeramicsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CompositesJournal of

NanoparticlesJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Biomaterials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

MetallurgyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BioMed Research International

MaterialsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Nano

materials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal ofNanomaterials

6 Advances in Materials Science and Engineering

(a)

200120583m

120574-FeOOHiron

(a)

(b)

200120583m

120573-FeOOHiron

(b)

(c)

100120583m

120574-FeOOHiron

(c)

(d)

100120583m

120573-FeOOHiron

(d)

(e)

200120583m

120574-FeOOHiron

(e)

(f)

100120583m120573-FeOOHiron

(f)

(g)

100120583m120574-FeOOHiron

(g)

(h)

200120583m120573-FeOOHiron

(h)

Figure 5 SEM images of rust powdercast iron interface with the effects of NO3

minus ((a) and (b)) Clminus ((c) and (d)) HSO4

minus ((e) and (f)) andClminus+HSO

4

minus ((g) and (h))

originated from P2p confirming the presence of phosphateThe peaks of Fe2p

32in Fe3+ generally lie between 71020

and 71105 eV However the binding energy of Fe2p32

in thisstudy was 71242 eV resulting in a chemical shift of morethan 1 eV Such a shift may suggest a change in chemical

environment of the elements thus indicating formation ofa new chemical bond between Fe3+ and other substancesDue to the presence of tannic acid it may suggest the for-mation of chelate between iron and tannin [31] as illustratedin Scheme 1

Advances in Materials Science and Engineering 7

10 20 30 40 50 60 70

0

500

1000

1500

2000

2500

3000

3500

Inte

nsity

(cps

)

2120579 (∘)

120575-FeOOH3T-10P

120574-FeOOH3T-10P

120573-FeOOH3T-10P

Fe3P6O2

Figure 6 XRD patterns of the products formed from the reaction of FeOOH and 3T-10P

730 720 710 700 690

8000

9000

10000

11000

12000

13000

14000

Inte

nsity

(cps

)

Binding energy (eV)

120573-FeOOH3T-10P

71242Fe3+

Fe2p

(a)

Inte

nsity

(cps

)

294 292 290 288 286 284 282

2000

3000

4000

5000

6000

7000

8000

9000

10000

Binding energy (eV)

120573-FeOOH3T-10P

28850

28507

28689

C1sC

CndashOH

OndashC=O

(b)

538 536 534 532 530 5280

5000

10000

15000

20000

25000

30000

Inte

nsity

(cps

)

Binding energy (eV)

120573-FeOOH3P-10T53195O1s CndashOH

(c)

Inte

nsity

(cps

)

138 136 134 132 1301000

1500

2000

2500

3000

3500

4000

4500

Binding energy (eV)

120573-FeOOH3T-10P

13364P2p P5+

(d)

Figure 7 XPS spectra of the products formed from the reaction of 120573-FeOOH and 3T-10P

8 Advances in Materials Science and Engineering

730 720 710 700 690

7500

8000

8500

9000

9500

10000

10500

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P

Fe3+

Fe2p

71205

(a)

292 290 288 286 284 2820

2000

4000

6000

8000

10000

12000

14000

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P

28642

28490

28850

C1s C

CndashOH

OndashC=O

(b)

528 530 532 534 5360

5000

10000

15000

20000

25000

30000

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P53258

O1sCndashOH

(c)

138 136 134 132

1000120014001600180020002200240026002800

800

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P13399

P2p P5+

(d)

Figure 8 XPS spectra of the products formed from the reaction of 120574-FeOOH and 3T-10P

ROH

OH

OH

R

OO

O

Fe3+Fe3+ ++ 3H3+

Scheme 1 Single-chelate complex ion body

Thus it was speculated that the reaction products of 120573-FeOOH and 3T-10P were made up of iron phosphate andchelate of iron and tannin

The results of XPS analyses of the reaction productsgenerated by 120574-FeOOHand 3T-10P and by 120575-FeOOHand 3T-10P were illustrated in Figures 8 and 9 The composition ofthese two products was similar to the reaction products of 120573-FeOOH and 3T-10P that is was made mainly of Fe C P andO and having about the same peak positions Therefore thereaction products were mainly made of iron phosphate andchelate of iron and tannin

The structures of iron phosphate and chelate of iron andtannin are relatively stable If acting as chemical conversionlayer the cast iron may develop strong corrosion resistancecapacity Meanwhile the layer can enhance bonding betweenthe coating and the substrate These favorable physical andchemical properties could meet the need of coating andsealing treatment for iron artifact However the mechanismsof tannic acidphosphoric acid rust conversion may needfurther study

4 Conclusions

(1) When cast iron was covered by 120573-FeOOH and 120574-FeOOH corrosion the rust layer was porous and nottight enough to provide a good protection againstcorrosion by NO

3

minus Clminus HSO4

minus and Clminus+HSO4

minus(2) Among common anions tested NO

3

minus had the weak-est corrosive power on cast ironThe corrosion powerincreased in the following sequence Clminus HSO

4

minus andClminus+HSO

4

minus Meanwhile synergistic corrosion couldbe enhanced when both Clminus andHSO

4

minus were present

Advances in Materials Science and Engineering 9

730 720 710 700 6907000

7500

8000

8500

9000

9500

10000

10500In

tens

ity (c

ps)

71293Fe3+

120575-FeOOH3T-10P

Binding energy (eV)

(a)

290 288 286 284 2820

2000

4000

6000

8000

10000

12000

14000

Inte

nsity

(cps

)

28503

28659

28873

C1s C 120575-FeOOH3T-10P

Binding energy (eV)

CndashOH

OndashC=O

(b)

536 534 532 530 5280

5000

10000

15000

20000

25000

Inte

nsity

(cps

)

53061

O1sOHminus

Binding energy (eV)

(c)

137 136 135 134 133 132 131

8001000120014001600180020002200240026002800

Inte

nsity

(cps

)

13410P2p 120575-FeOOH3T-10PP5+

Binding energy (eV)

(d)

Figure 9 XPS spectra of the products formed from the reaction of 120575-FeOOH and 3T-10P

(3) Analyses of the reaction products between FeOOHand different combinations of phosphoric acidtannicacid showed that 3 tannic acid + 10 phosphoricacid was the most suitable formula as rust stabilizer

(4) The reaction products between120573-FeOOH 120574-FeOOHor 120575-FeOOH and 3T-10P were made up of ironphosphate and chelate of iron and tannin

Conflict of Interests

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

Acknowledgments

This present work was supported by the National NaturalScience Foundation of China (Grants nos 51202226 and51172216) and the Fundamental Research Funds for theCentral Universities (Grant no 2652013043)

References

[1] W Xu K Daub X Zhang J J Noel D W Shoesmith and JC Wren ldquoOxide formation and conversion on carbon steel inmildly basic solutionsrdquo Electrochimica Acta vol 54 no 24 pp5727ndash5738 2009

[2] X Liu G Qiu A Yan Z Wang and X Li ldquoHydrothermal syn-thesis and characterization of 120572-FeOOH and 120572-Fe

2O3uniform

nanocrystallinesrdquo Journal of Alloys andCompounds vol 433 no1-2 pp 216ndash220 2007

[3] H Abdel-Samad and P R Watson ldquoAn XPS study of theadsorption of lead on goethite (120572-FeOOH)rdquo Applied SurfaceScience vol 136 no 1-2 pp 46ndash54 1998

[4] C-J Jia L-D Sun Z-G Yan et al ldquoSingle-crystalline iron oxidenanotubesrdquoAngewandte Chemie vol 44 no 28 pp 4328ndash43332005

[5] M Zic M Ristic and S Music ldquoThe effect of temperature onthe crystallization of 120572-Fe

2O3particles from dense 120573-FeOOH

suspensionsrdquo Materials Chemistry and Physics vol 120 no 1pp 160ndash166 2010

10 Advances in Materials Science and Engineering

[6] A Jagminas K Mazeika E Juska J Reklaitis and D Bal-trunas ldquoElectrochemical fabrication and characterization oflepidocrocite (120574-FeOOH) nanowire arraysrdquo Applied SurfaceScience vol 256 no 12 pp 3993ndash3996 2010

[7] P Dillmann R Balasubramaniam and G Beranger ldquoChar-acterization of protective rust on ancient Indian iron usingmicroprobe analysesrdquo Corrosion Science vol 44 no 10 pp2231ndash2242 2002

[8] H Tanaka J Wakatsuki K Kandori T Ishikawa and TNakayama ldquoRole of zinc compounds on the formation mor-phology and adsorption characteristics of 120573-FeOOH rustsrdquoCorrosion Science vol 52 no 9 pp 2973ndash2978 2010

[9] T Ishikawa M Kumagai A Yasukawa K Kandori TNakayama and F Yuse ldquoInfluences of metal ions on theformation of 120574-FeOOH andmagnetite rustsrdquoCorrosion Sciencevol 44 no 5 pp 1073ndash1086 2002

[10] A Collazo X R Novoa C Perez and B Puga ldquoThe corrosionprotection mechanism of rust converters an electrochemicalimpedance spectroscopy studyrdquo Electrochimica Acta vol 55 no21 pp 6156ndash6162 2010

[11] M Zic M Ristic and S Music ldquoPrecipitation of 120572-Fe2O3

from dense 120573-FeOOH suspensions with added ammoniumamidosulfonaterdquo Journal of Molecular Structure vol 924-926pp 235ndash242 2009

[12] C Q Cheng J Zhao T S Cao Q Q Fu M K Lei and DW Deng ldquoFacile chromaticity approach for the inspection ofpassive films on austenitic stainless steelrdquoCorrosion Science vol70 pp 235ndash242 2013

[13] A I Munoz J G Anton J L Guinon and V P HerranzldquoInhibition effect of chromate on the passivation and pittingcorrosion of a duplex stainless steel in LiBr solutions usingelectrochemical techniquesrdquo Corrosion Science vol 49 no 8pp 3200ndash3225 2007

[14] S Powell ldquoEvaluation of alternative corrosion inhibitors tochromate for use in organic coatings using scanning referenceelectrode techniquerdquo Surface Engineering vol 16 no 2 pp 169ndash175 2000

[15] B J Basu A Srinivasan J Manasa and V K W GripsldquoImproved corrosion protection of aluminium alloy AA 2024by sol-gel hybrid coatings after surface pretreatment by silani-sationrdquo Surface Engineering vol 28 no 4 pp 294ndash299 2012

[16] Z Liu D Yan Y Dong Y Yang Z Chu and Z ZhangldquoThe effect of modified epoxy sealing on the electrochemicalcorrosion behaviour of reactive plasma-sprayed TiN coatingsrdquoCorrosion Science vol 75 pp 220ndash227 2013

[17] A M Simoes J Torres R Picciochi and J C S FernandesldquoCorrosion inhibition at galvanized steel cut edges by phosphatepigmentsrdquo Electrochimica Acta vol 54 no 15 pp 3857ndash38652009

[18] B Gruss ldquoIron phosphatingrdquoMetal Finishing vol 108 no 11-12pp 33ndash37 2010

[19] D Singh and S Yadav ldquoRole of tannic acid based rust converteron formation of passive film on zinc rich coating exposedin simulated concrete pore solutionrdquo Surface and CoatingsTechnology vol 202 no 8 pp 1526ndash1542 2008

[20] B Qian B Hou and M Zheng ldquoThe inhibition effect oftannic acid on mild steel corrosion in seawater wetdry cyclicconditionsrdquo Corrosion Science vol 72 pp 1ndash9 2013

[21] A Ostovari S M Hoseinieh M Peikari S R Shadizadehand S J Hashemi ldquoCorrosion inhibition of mild steel in 1M HCl solution by henna extract a comparative study of the

inhibition by henna and its constituents (Lawsone Gallic acid120572-d-Glucose and Tannic acid)rdquo Corrosion Science vol 51 no 9pp 1935ndash1949 2009

[22] K W Tan M J Kassim and C W Oo ldquoPossible improvementof catechin as corrosion inhibitor in acidic mediumrdquo CorrosionScience vol 65 pp 152ndash162 2012

[23] B Yuan J Xu X Li and M-L Fu ldquoPreparation of Si-Al120572-FeOOH catalyst from an iron-containing waste and surface-catalytic oxidation of methylene blue at neutral pH value in thepresence of H

2O2rdquo Chemical Engineering Journal vol 226 pp

181ndash188 2013[24] S Bashir R W McCabe C Boxall M S Leaver and D Mobbs

ldquoSynthesis of 120572- and120573-FeOOH iron oxide nanoparticles in non-ionic surfactant mediumrdquo Journal of Nanoparticle Research vol11 no 3 pp 701ndash706 2009

[25] L Carlson and U Schwertmann ldquoNatural occurrence of ferox-yhite (120575rsquo-FeOOH)rdquo Clays amp Clay Minerals vol 28 no 4 pp272ndash280 1980

[26] Z Wang C Xu and X Dong ldquoLocalized corrosion andphase transformation of simulated archaeological ironrdquoChineseJournal of Chemical Engineering vol 16 no 2 pp 299ndash3052008

[27] C Remazeilles and P Refait ldquoOn the formation of 120573-FeOOH(akaganeite) in chloride-containing environmentsrdquo CorrosionScience vol 49 no 2 pp 844ndash857 2007

[28] Z Wang C Xu X Cao and B Xu ldquoThe Morphology phasecomposition and effect of corrosion product on simulatedarchaeological ironrdquo Chinese Journal of Chemical Engineeringvol 15 no 3 pp 433ndash438 2007

[29] S Nasrazadani ldquoThe application of infrared spectroscopy toa study of phosphoric and tannic acids interactions withmagnetite (Fe

3O4) goethite (120572-FeOOH) and lepidocrocite (120574-

FeOOH)rdquo Corrosion Science vol 39 no 10-11 pp 1845ndash18591997

[30] R Balasubramaniam ldquoOn the corrosion resistance of the Delhiiron pillarrdquo Corrosion Science vol 42 no 12 pp 2103ndash21292000

[31] AM Al-Mayouf ldquoInhibitors for chemical cleaning of iron withtannic acidrdquo Desalination vol 121 no 2 pp 173ndash182 1999

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CeramicsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CompositesJournal of

NanoparticlesJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Biomaterials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

MetallurgyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BioMed Research International

MaterialsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Nano

materials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal ofNanomaterials

Advances in Materials Science and Engineering 7

10 20 30 40 50 60 70

0

500

1000

1500

2000

2500

3000

3500

Inte

nsity

(cps

)

2120579 (∘)

120575-FeOOH3T-10P

120574-FeOOH3T-10P

120573-FeOOH3T-10P

Fe3P6O2

Figure 6 XRD patterns of the products formed from the reaction of FeOOH and 3T-10P

730 720 710 700 690

8000

9000

10000

11000

12000

13000

14000

Inte

nsity

(cps

)

Binding energy (eV)

120573-FeOOH3T-10P

71242Fe3+

Fe2p

(a)

Inte

nsity

(cps

)

294 292 290 288 286 284 282

2000

3000

4000

5000

6000

7000

8000

9000

10000

Binding energy (eV)

120573-FeOOH3T-10P

28850

28507

28689

C1sC

CndashOH

OndashC=O

(b)

538 536 534 532 530 5280

5000

10000

15000

20000

25000

30000

Inte

nsity

(cps

)

Binding energy (eV)

120573-FeOOH3P-10T53195O1s CndashOH

(c)

Inte

nsity

(cps

)

138 136 134 132 1301000

1500

2000

2500

3000

3500

4000

4500

Binding energy (eV)

120573-FeOOH3T-10P

13364P2p P5+

(d)

Figure 7 XPS spectra of the products formed from the reaction of 120573-FeOOH and 3T-10P

8 Advances in Materials Science and Engineering

730 720 710 700 690

7500

8000

8500

9000

9500

10000

10500

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P

Fe3+

Fe2p

71205

(a)

292 290 288 286 284 2820

2000

4000

6000

8000

10000

12000

14000

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P

28642

28490

28850

C1s C

CndashOH

OndashC=O

(b)

528 530 532 534 5360

5000

10000

15000

20000

25000

30000

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P53258

O1sCndashOH

(c)

138 136 134 132

1000120014001600180020002200240026002800

800

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P13399

P2p P5+

(d)

Figure 8 XPS spectra of the products formed from the reaction of 120574-FeOOH and 3T-10P

ROH

OH

OH

R

OO

O

Fe3+Fe3+ ++ 3H3+

Scheme 1 Single-chelate complex ion body

Thus it was speculated that the reaction products of 120573-FeOOH and 3T-10P were made up of iron phosphate andchelate of iron and tannin

The results of XPS analyses of the reaction productsgenerated by 120574-FeOOHand 3T-10P and by 120575-FeOOHand 3T-10P were illustrated in Figures 8 and 9 The composition ofthese two products was similar to the reaction products of 120573-FeOOH and 3T-10P that is was made mainly of Fe C P andO and having about the same peak positions Therefore thereaction products were mainly made of iron phosphate andchelate of iron and tannin

The structures of iron phosphate and chelate of iron andtannin are relatively stable If acting as chemical conversionlayer the cast iron may develop strong corrosion resistancecapacity Meanwhile the layer can enhance bonding betweenthe coating and the substrate These favorable physical andchemical properties could meet the need of coating andsealing treatment for iron artifact However the mechanismsof tannic acidphosphoric acid rust conversion may needfurther study

4 Conclusions

(1) When cast iron was covered by 120573-FeOOH and 120574-FeOOH corrosion the rust layer was porous and nottight enough to provide a good protection againstcorrosion by NO

3

minus Clminus HSO4

minus and Clminus+HSO4

minus(2) Among common anions tested NO

3

minus had the weak-est corrosive power on cast ironThe corrosion powerincreased in the following sequence Clminus HSO

4

minus andClminus+HSO

4

minus Meanwhile synergistic corrosion couldbe enhanced when both Clminus andHSO

4

minus were present

Advances in Materials Science and Engineering 9

730 720 710 700 6907000

7500

8000

8500

9000

9500

10000

10500In

tens

ity (c

ps)

71293Fe3+

120575-FeOOH3T-10P

Binding energy (eV)

(a)

290 288 286 284 2820

2000

4000

6000

8000

10000

12000

14000

Inte

nsity

(cps

)

28503

28659

28873

C1s C 120575-FeOOH3T-10P

Binding energy (eV)

CndashOH

OndashC=O

(b)

536 534 532 530 5280

5000

10000

15000

20000

25000

Inte

nsity

(cps

)

53061

O1sOHminus

Binding energy (eV)

(c)

137 136 135 134 133 132 131

8001000120014001600180020002200240026002800

Inte

nsity

(cps

)

13410P2p 120575-FeOOH3T-10PP5+

Binding energy (eV)

(d)

Figure 9 XPS spectra of the products formed from the reaction of 120575-FeOOH and 3T-10P

(3) Analyses of the reaction products between FeOOHand different combinations of phosphoric acidtannicacid showed that 3 tannic acid + 10 phosphoricacid was the most suitable formula as rust stabilizer

(4) The reaction products between120573-FeOOH 120574-FeOOHor 120575-FeOOH and 3T-10P were made up of ironphosphate and chelate of iron and tannin

Conflict of Interests

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

Acknowledgments

This present work was supported by the National NaturalScience Foundation of China (Grants nos 51202226 and51172216) and the Fundamental Research Funds for theCentral Universities (Grant no 2652013043)

References

[1] W Xu K Daub X Zhang J J Noel D W Shoesmith and JC Wren ldquoOxide formation and conversion on carbon steel inmildly basic solutionsrdquo Electrochimica Acta vol 54 no 24 pp5727ndash5738 2009

[2] X Liu G Qiu A Yan Z Wang and X Li ldquoHydrothermal syn-thesis and characterization of 120572-FeOOH and 120572-Fe

2O3uniform

nanocrystallinesrdquo Journal of Alloys andCompounds vol 433 no1-2 pp 216ndash220 2007

[3] H Abdel-Samad and P R Watson ldquoAn XPS study of theadsorption of lead on goethite (120572-FeOOH)rdquo Applied SurfaceScience vol 136 no 1-2 pp 46ndash54 1998

[4] C-J Jia L-D Sun Z-G Yan et al ldquoSingle-crystalline iron oxidenanotubesrdquoAngewandte Chemie vol 44 no 28 pp 4328ndash43332005

[5] M Zic M Ristic and S Music ldquoThe effect of temperature onthe crystallization of 120572-Fe

2O3particles from dense 120573-FeOOH

suspensionsrdquo Materials Chemistry and Physics vol 120 no 1pp 160ndash166 2010

10 Advances in Materials Science and Engineering

[6] A Jagminas K Mazeika E Juska J Reklaitis and D Bal-trunas ldquoElectrochemical fabrication and characterization oflepidocrocite (120574-FeOOH) nanowire arraysrdquo Applied SurfaceScience vol 256 no 12 pp 3993ndash3996 2010

[7] P Dillmann R Balasubramaniam and G Beranger ldquoChar-acterization of protective rust on ancient Indian iron usingmicroprobe analysesrdquo Corrosion Science vol 44 no 10 pp2231ndash2242 2002

[8] H Tanaka J Wakatsuki K Kandori T Ishikawa and TNakayama ldquoRole of zinc compounds on the formation mor-phology and adsorption characteristics of 120573-FeOOH rustsrdquoCorrosion Science vol 52 no 9 pp 2973ndash2978 2010

[9] T Ishikawa M Kumagai A Yasukawa K Kandori TNakayama and F Yuse ldquoInfluences of metal ions on theformation of 120574-FeOOH andmagnetite rustsrdquoCorrosion Sciencevol 44 no 5 pp 1073ndash1086 2002

[10] A Collazo X R Novoa C Perez and B Puga ldquoThe corrosionprotection mechanism of rust converters an electrochemicalimpedance spectroscopy studyrdquo Electrochimica Acta vol 55 no21 pp 6156ndash6162 2010

[11] M Zic M Ristic and S Music ldquoPrecipitation of 120572-Fe2O3

from dense 120573-FeOOH suspensions with added ammoniumamidosulfonaterdquo Journal of Molecular Structure vol 924-926pp 235ndash242 2009

[12] C Q Cheng J Zhao T S Cao Q Q Fu M K Lei and DW Deng ldquoFacile chromaticity approach for the inspection ofpassive films on austenitic stainless steelrdquoCorrosion Science vol70 pp 235ndash242 2013

[13] A I Munoz J G Anton J L Guinon and V P HerranzldquoInhibition effect of chromate on the passivation and pittingcorrosion of a duplex stainless steel in LiBr solutions usingelectrochemical techniquesrdquo Corrosion Science vol 49 no 8pp 3200ndash3225 2007

[14] S Powell ldquoEvaluation of alternative corrosion inhibitors tochromate for use in organic coatings using scanning referenceelectrode techniquerdquo Surface Engineering vol 16 no 2 pp 169ndash175 2000

[15] B J Basu A Srinivasan J Manasa and V K W GripsldquoImproved corrosion protection of aluminium alloy AA 2024by sol-gel hybrid coatings after surface pretreatment by silani-sationrdquo Surface Engineering vol 28 no 4 pp 294ndash299 2012

[16] Z Liu D Yan Y Dong Y Yang Z Chu and Z ZhangldquoThe effect of modified epoxy sealing on the electrochemicalcorrosion behaviour of reactive plasma-sprayed TiN coatingsrdquoCorrosion Science vol 75 pp 220ndash227 2013

[17] A M Simoes J Torres R Picciochi and J C S FernandesldquoCorrosion inhibition at galvanized steel cut edges by phosphatepigmentsrdquo Electrochimica Acta vol 54 no 15 pp 3857ndash38652009

[18] B Gruss ldquoIron phosphatingrdquoMetal Finishing vol 108 no 11-12pp 33ndash37 2010

[19] D Singh and S Yadav ldquoRole of tannic acid based rust converteron formation of passive film on zinc rich coating exposedin simulated concrete pore solutionrdquo Surface and CoatingsTechnology vol 202 no 8 pp 1526ndash1542 2008

[20] B Qian B Hou and M Zheng ldquoThe inhibition effect oftannic acid on mild steel corrosion in seawater wetdry cyclicconditionsrdquo Corrosion Science vol 72 pp 1ndash9 2013

[21] A Ostovari S M Hoseinieh M Peikari S R Shadizadehand S J Hashemi ldquoCorrosion inhibition of mild steel in 1M HCl solution by henna extract a comparative study of the

inhibition by henna and its constituents (Lawsone Gallic acid120572-d-Glucose and Tannic acid)rdquo Corrosion Science vol 51 no 9pp 1935ndash1949 2009

[22] K W Tan M J Kassim and C W Oo ldquoPossible improvementof catechin as corrosion inhibitor in acidic mediumrdquo CorrosionScience vol 65 pp 152ndash162 2012

[23] B Yuan J Xu X Li and M-L Fu ldquoPreparation of Si-Al120572-FeOOH catalyst from an iron-containing waste and surface-catalytic oxidation of methylene blue at neutral pH value in thepresence of H

2O2rdquo Chemical Engineering Journal vol 226 pp

181ndash188 2013[24] S Bashir R W McCabe C Boxall M S Leaver and D Mobbs

ldquoSynthesis of 120572- and120573-FeOOH iron oxide nanoparticles in non-ionic surfactant mediumrdquo Journal of Nanoparticle Research vol11 no 3 pp 701ndash706 2009

[25] L Carlson and U Schwertmann ldquoNatural occurrence of ferox-yhite (120575rsquo-FeOOH)rdquo Clays amp Clay Minerals vol 28 no 4 pp272ndash280 1980

[26] Z Wang C Xu and X Dong ldquoLocalized corrosion andphase transformation of simulated archaeological ironrdquoChineseJournal of Chemical Engineering vol 16 no 2 pp 299ndash3052008

[27] C Remazeilles and P Refait ldquoOn the formation of 120573-FeOOH(akaganeite) in chloride-containing environmentsrdquo CorrosionScience vol 49 no 2 pp 844ndash857 2007

[28] Z Wang C Xu X Cao and B Xu ldquoThe Morphology phasecomposition and effect of corrosion product on simulatedarchaeological ironrdquo Chinese Journal of Chemical Engineeringvol 15 no 3 pp 433ndash438 2007

[29] S Nasrazadani ldquoThe application of infrared spectroscopy toa study of phosphoric and tannic acids interactions withmagnetite (Fe

3O4) goethite (120572-FeOOH) and lepidocrocite (120574-

FeOOH)rdquo Corrosion Science vol 39 no 10-11 pp 1845ndash18591997

[30] R Balasubramaniam ldquoOn the corrosion resistance of the Delhiiron pillarrdquo Corrosion Science vol 42 no 12 pp 2103ndash21292000

[31] AM Al-Mayouf ldquoInhibitors for chemical cleaning of iron withtannic acidrdquo Desalination vol 121 no 2 pp 173ndash182 1999

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CeramicsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CompositesJournal of

NanoparticlesJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Biomaterials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

MetallurgyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BioMed Research International

MaterialsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Nano

materials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal ofNanomaterials

8 Advances in Materials Science and Engineering

730 720 710 700 690

7500

8000

8500

9000

9500

10000

10500

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P

Fe3+

Fe2p

71205

(a)

292 290 288 286 284 2820

2000

4000

6000

8000

10000

12000

14000

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P

28642

28490

28850

C1s C

CndashOH

OndashC=O

(b)

528 530 532 534 5360

5000

10000

15000

20000

25000

30000

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P53258

O1sCndashOH

(c)

138 136 134 132

1000120014001600180020002200240026002800

800

Inte

nsity

(cps

)

Binding energy (eV)

120574-FeOOH3T-10P13399

P2p P5+

(d)

Figure 8 XPS spectra of the products formed from the reaction of 120574-FeOOH and 3T-10P

ROH

OH

OH

R

OO

O

Fe3+Fe3+ ++ 3H3+

Scheme 1 Single-chelate complex ion body

Thus it was speculated that the reaction products of 120573-FeOOH and 3T-10P were made up of iron phosphate andchelate of iron and tannin

The results of XPS analyses of the reaction productsgenerated by 120574-FeOOHand 3T-10P and by 120575-FeOOHand 3T-10P were illustrated in Figures 8 and 9 The composition ofthese two products was similar to the reaction products of 120573-FeOOH and 3T-10P that is was made mainly of Fe C P andO and having about the same peak positions Therefore thereaction products were mainly made of iron phosphate andchelate of iron and tannin

The structures of iron phosphate and chelate of iron andtannin are relatively stable If acting as chemical conversionlayer the cast iron may develop strong corrosion resistancecapacity Meanwhile the layer can enhance bonding betweenthe coating and the substrate These favorable physical andchemical properties could meet the need of coating andsealing treatment for iron artifact However the mechanismsof tannic acidphosphoric acid rust conversion may needfurther study

4 Conclusions

(1) When cast iron was covered by 120573-FeOOH and 120574-FeOOH corrosion the rust layer was porous and nottight enough to provide a good protection againstcorrosion by NO

3

minus Clminus HSO4

minus and Clminus+HSO4

minus(2) Among common anions tested NO

3

minus had the weak-est corrosive power on cast ironThe corrosion powerincreased in the following sequence Clminus HSO

4

minus andClminus+HSO

4

minus Meanwhile synergistic corrosion couldbe enhanced when both Clminus andHSO

4

minus were present

Advances in Materials Science and Engineering 9

730 720 710 700 6907000

7500

8000

8500

9000

9500

10000

10500In

tens

ity (c

ps)

71293Fe3+

120575-FeOOH3T-10P

Binding energy (eV)

(a)

290 288 286 284 2820

2000

4000

6000

8000

10000

12000

14000

Inte

nsity

(cps

)

28503

28659

28873

C1s C 120575-FeOOH3T-10P

Binding energy (eV)

CndashOH

OndashC=O

(b)

536 534 532 530 5280

5000

10000

15000

20000

25000

Inte

nsity

(cps

)

53061

O1sOHminus

Binding energy (eV)

(c)

137 136 135 134 133 132 131

8001000120014001600180020002200240026002800

Inte

nsity

(cps

)

13410P2p 120575-FeOOH3T-10PP5+

Binding energy (eV)

(d)

Figure 9 XPS spectra of the products formed from the reaction of 120575-FeOOH and 3T-10P

(3) Analyses of the reaction products between FeOOHand different combinations of phosphoric acidtannicacid showed that 3 tannic acid + 10 phosphoricacid was the most suitable formula as rust stabilizer

(4) The reaction products between120573-FeOOH 120574-FeOOHor 120575-FeOOH and 3T-10P were made up of ironphosphate and chelate of iron and tannin

Conflict of Interests

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

Acknowledgments

This present work was supported by the National NaturalScience Foundation of China (Grants nos 51202226 and51172216) and the Fundamental Research Funds for theCentral Universities (Grant no 2652013043)

References

[1] W Xu K Daub X Zhang J J Noel D W Shoesmith and JC Wren ldquoOxide formation and conversion on carbon steel inmildly basic solutionsrdquo Electrochimica Acta vol 54 no 24 pp5727ndash5738 2009

[2] X Liu G Qiu A Yan Z Wang and X Li ldquoHydrothermal syn-thesis and characterization of 120572-FeOOH and 120572-Fe

2O3uniform

nanocrystallinesrdquo Journal of Alloys andCompounds vol 433 no1-2 pp 216ndash220 2007

[3] H Abdel-Samad and P R Watson ldquoAn XPS study of theadsorption of lead on goethite (120572-FeOOH)rdquo Applied SurfaceScience vol 136 no 1-2 pp 46ndash54 1998

[4] C-J Jia L-D Sun Z-G Yan et al ldquoSingle-crystalline iron oxidenanotubesrdquoAngewandte Chemie vol 44 no 28 pp 4328ndash43332005

[5] M Zic M Ristic and S Music ldquoThe effect of temperature onthe crystallization of 120572-Fe

2O3particles from dense 120573-FeOOH

suspensionsrdquo Materials Chemistry and Physics vol 120 no 1pp 160ndash166 2010

10 Advances in Materials Science and Engineering

[6] A Jagminas K Mazeika E Juska J Reklaitis and D Bal-trunas ldquoElectrochemical fabrication and characterization oflepidocrocite (120574-FeOOH) nanowire arraysrdquo Applied SurfaceScience vol 256 no 12 pp 3993ndash3996 2010

[7] P Dillmann R Balasubramaniam and G Beranger ldquoChar-acterization of protective rust on ancient Indian iron usingmicroprobe analysesrdquo Corrosion Science vol 44 no 10 pp2231ndash2242 2002

[8] H Tanaka J Wakatsuki K Kandori T Ishikawa and TNakayama ldquoRole of zinc compounds on the formation mor-phology and adsorption characteristics of 120573-FeOOH rustsrdquoCorrosion Science vol 52 no 9 pp 2973ndash2978 2010

[9] T Ishikawa M Kumagai A Yasukawa K Kandori TNakayama and F Yuse ldquoInfluences of metal ions on theformation of 120574-FeOOH andmagnetite rustsrdquoCorrosion Sciencevol 44 no 5 pp 1073ndash1086 2002

[10] A Collazo X R Novoa C Perez and B Puga ldquoThe corrosionprotection mechanism of rust converters an electrochemicalimpedance spectroscopy studyrdquo Electrochimica Acta vol 55 no21 pp 6156ndash6162 2010

[11] M Zic M Ristic and S Music ldquoPrecipitation of 120572-Fe2O3

from dense 120573-FeOOH suspensions with added ammoniumamidosulfonaterdquo Journal of Molecular Structure vol 924-926pp 235ndash242 2009

[12] C Q Cheng J Zhao T S Cao Q Q Fu M K Lei and DW Deng ldquoFacile chromaticity approach for the inspection ofpassive films on austenitic stainless steelrdquoCorrosion Science vol70 pp 235ndash242 2013

[13] A I Munoz J G Anton J L Guinon and V P HerranzldquoInhibition effect of chromate on the passivation and pittingcorrosion of a duplex stainless steel in LiBr solutions usingelectrochemical techniquesrdquo Corrosion Science vol 49 no 8pp 3200ndash3225 2007

[14] S Powell ldquoEvaluation of alternative corrosion inhibitors tochromate for use in organic coatings using scanning referenceelectrode techniquerdquo Surface Engineering vol 16 no 2 pp 169ndash175 2000

[15] B J Basu A Srinivasan J Manasa and V K W GripsldquoImproved corrosion protection of aluminium alloy AA 2024by sol-gel hybrid coatings after surface pretreatment by silani-sationrdquo Surface Engineering vol 28 no 4 pp 294ndash299 2012

[16] Z Liu D Yan Y Dong Y Yang Z Chu and Z ZhangldquoThe effect of modified epoxy sealing on the electrochemicalcorrosion behaviour of reactive plasma-sprayed TiN coatingsrdquoCorrosion Science vol 75 pp 220ndash227 2013

[17] A M Simoes J Torres R Picciochi and J C S FernandesldquoCorrosion inhibition at galvanized steel cut edges by phosphatepigmentsrdquo Electrochimica Acta vol 54 no 15 pp 3857ndash38652009

[18] B Gruss ldquoIron phosphatingrdquoMetal Finishing vol 108 no 11-12pp 33ndash37 2010

[19] D Singh and S Yadav ldquoRole of tannic acid based rust converteron formation of passive film on zinc rich coating exposedin simulated concrete pore solutionrdquo Surface and CoatingsTechnology vol 202 no 8 pp 1526ndash1542 2008

[20] B Qian B Hou and M Zheng ldquoThe inhibition effect oftannic acid on mild steel corrosion in seawater wetdry cyclicconditionsrdquo Corrosion Science vol 72 pp 1ndash9 2013

[21] A Ostovari S M Hoseinieh M Peikari S R Shadizadehand S J Hashemi ldquoCorrosion inhibition of mild steel in 1M HCl solution by henna extract a comparative study of the

inhibition by henna and its constituents (Lawsone Gallic acid120572-d-Glucose and Tannic acid)rdquo Corrosion Science vol 51 no 9pp 1935ndash1949 2009

[22] K W Tan M J Kassim and C W Oo ldquoPossible improvementof catechin as corrosion inhibitor in acidic mediumrdquo CorrosionScience vol 65 pp 152ndash162 2012

[23] B Yuan J Xu X Li and M-L Fu ldquoPreparation of Si-Al120572-FeOOH catalyst from an iron-containing waste and surface-catalytic oxidation of methylene blue at neutral pH value in thepresence of H

2O2rdquo Chemical Engineering Journal vol 226 pp

181ndash188 2013[24] S Bashir R W McCabe C Boxall M S Leaver and D Mobbs

ldquoSynthesis of 120572- and120573-FeOOH iron oxide nanoparticles in non-ionic surfactant mediumrdquo Journal of Nanoparticle Research vol11 no 3 pp 701ndash706 2009

[25] L Carlson and U Schwertmann ldquoNatural occurrence of ferox-yhite (120575rsquo-FeOOH)rdquo Clays amp Clay Minerals vol 28 no 4 pp272ndash280 1980

[26] Z Wang C Xu and X Dong ldquoLocalized corrosion andphase transformation of simulated archaeological ironrdquoChineseJournal of Chemical Engineering vol 16 no 2 pp 299ndash3052008

[27] C Remazeilles and P Refait ldquoOn the formation of 120573-FeOOH(akaganeite) in chloride-containing environmentsrdquo CorrosionScience vol 49 no 2 pp 844ndash857 2007

[28] Z Wang C Xu X Cao and B Xu ldquoThe Morphology phasecomposition and effect of corrosion product on simulatedarchaeological ironrdquo Chinese Journal of Chemical Engineeringvol 15 no 3 pp 433ndash438 2007

[29] S Nasrazadani ldquoThe application of infrared spectroscopy toa study of phosphoric and tannic acids interactions withmagnetite (Fe

3O4) goethite (120572-FeOOH) and lepidocrocite (120574-

FeOOH)rdquo Corrosion Science vol 39 no 10-11 pp 1845ndash18591997

[30] R Balasubramaniam ldquoOn the corrosion resistance of the Delhiiron pillarrdquo Corrosion Science vol 42 no 12 pp 2103ndash21292000

[31] AM Al-Mayouf ldquoInhibitors for chemical cleaning of iron withtannic acidrdquo Desalination vol 121 no 2 pp 173ndash182 1999

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CeramicsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CompositesJournal of

NanoparticlesJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Biomaterials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

MetallurgyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BioMed Research International

MaterialsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Nano

materials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal ofNanomaterials

Advances in Materials Science and Engineering 9

730 720 710 700 6907000

7500

8000

8500

9000

9500

10000

10500In

tens

ity (c

ps)

71293Fe3+

120575-FeOOH3T-10P

Binding energy (eV)

(a)

290 288 286 284 2820

2000

4000

6000

8000

10000

12000

14000

Inte

nsity

(cps

)

28503

28659

28873

C1s C 120575-FeOOH3T-10P

Binding energy (eV)

CndashOH

OndashC=O

(b)

536 534 532 530 5280

5000

10000

15000

20000

25000

Inte

nsity

(cps

)

53061

O1sOHminus

Binding energy (eV)

(c)

137 136 135 134 133 132 131

8001000120014001600180020002200240026002800

Inte

nsity

(cps

)

13410P2p 120575-FeOOH3T-10PP5+

Binding energy (eV)

(d)

Figure 9 XPS spectra of the products formed from the reaction of 120575-FeOOH and 3T-10P

(3) Analyses of the reaction products between FeOOHand different combinations of phosphoric acidtannicacid showed that 3 tannic acid + 10 phosphoricacid was the most suitable formula as rust stabilizer

(4) The reaction products between120573-FeOOH 120574-FeOOHor 120575-FeOOH and 3T-10P were made up of ironphosphate and chelate of iron and tannin

Conflict of Interests

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

Acknowledgments

This present work was supported by the National NaturalScience Foundation of China (Grants nos 51202226 and51172216) and the Fundamental Research Funds for theCentral Universities (Grant no 2652013043)

References

[1] W Xu K Daub X Zhang J J Noel D W Shoesmith and JC Wren ldquoOxide formation and conversion on carbon steel inmildly basic solutionsrdquo Electrochimica Acta vol 54 no 24 pp5727ndash5738 2009

[2] X Liu G Qiu A Yan Z Wang and X Li ldquoHydrothermal syn-thesis and characterization of 120572-FeOOH and 120572-Fe

2O3uniform

nanocrystallinesrdquo Journal of Alloys andCompounds vol 433 no1-2 pp 216ndash220 2007

[3] H Abdel-Samad and P R Watson ldquoAn XPS study of theadsorption of lead on goethite (120572-FeOOH)rdquo Applied SurfaceScience vol 136 no 1-2 pp 46ndash54 1998

[4] C-J Jia L-D Sun Z-G Yan et al ldquoSingle-crystalline iron oxidenanotubesrdquoAngewandte Chemie vol 44 no 28 pp 4328ndash43332005

[5] M Zic M Ristic and S Music ldquoThe effect of temperature onthe crystallization of 120572-Fe

2O3particles from dense 120573-FeOOH

suspensionsrdquo Materials Chemistry and Physics vol 120 no 1pp 160ndash166 2010

10 Advances in Materials Science and Engineering

[6] A Jagminas K Mazeika E Juska J Reklaitis and D Bal-trunas ldquoElectrochemical fabrication and characterization oflepidocrocite (120574-FeOOH) nanowire arraysrdquo Applied SurfaceScience vol 256 no 12 pp 3993ndash3996 2010

[7] P Dillmann R Balasubramaniam and G Beranger ldquoChar-acterization of protective rust on ancient Indian iron usingmicroprobe analysesrdquo Corrosion Science vol 44 no 10 pp2231ndash2242 2002

[8] H Tanaka J Wakatsuki K Kandori T Ishikawa and TNakayama ldquoRole of zinc compounds on the formation mor-phology and adsorption characteristics of 120573-FeOOH rustsrdquoCorrosion Science vol 52 no 9 pp 2973ndash2978 2010

[9] T Ishikawa M Kumagai A Yasukawa K Kandori TNakayama and F Yuse ldquoInfluences of metal ions on theformation of 120574-FeOOH andmagnetite rustsrdquoCorrosion Sciencevol 44 no 5 pp 1073ndash1086 2002

[10] A Collazo X R Novoa C Perez and B Puga ldquoThe corrosionprotection mechanism of rust converters an electrochemicalimpedance spectroscopy studyrdquo Electrochimica Acta vol 55 no21 pp 6156ndash6162 2010

[11] M Zic M Ristic and S Music ldquoPrecipitation of 120572-Fe2O3

from dense 120573-FeOOH suspensions with added ammoniumamidosulfonaterdquo Journal of Molecular Structure vol 924-926pp 235ndash242 2009

[12] C Q Cheng J Zhao T S Cao Q Q Fu M K Lei and DW Deng ldquoFacile chromaticity approach for the inspection ofpassive films on austenitic stainless steelrdquoCorrosion Science vol70 pp 235ndash242 2013

[13] A I Munoz J G Anton J L Guinon and V P HerranzldquoInhibition effect of chromate on the passivation and pittingcorrosion of a duplex stainless steel in LiBr solutions usingelectrochemical techniquesrdquo Corrosion Science vol 49 no 8pp 3200ndash3225 2007

[14] S Powell ldquoEvaluation of alternative corrosion inhibitors tochromate for use in organic coatings using scanning referenceelectrode techniquerdquo Surface Engineering vol 16 no 2 pp 169ndash175 2000

[15] B J Basu A Srinivasan J Manasa and V K W GripsldquoImproved corrosion protection of aluminium alloy AA 2024by sol-gel hybrid coatings after surface pretreatment by silani-sationrdquo Surface Engineering vol 28 no 4 pp 294ndash299 2012

[16] Z Liu D Yan Y Dong Y Yang Z Chu and Z ZhangldquoThe effect of modified epoxy sealing on the electrochemicalcorrosion behaviour of reactive plasma-sprayed TiN coatingsrdquoCorrosion Science vol 75 pp 220ndash227 2013

[17] A M Simoes J Torres R Picciochi and J C S FernandesldquoCorrosion inhibition at galvanized steel cut edges by phosphatepigmentsrdquo Electrochimica Acta vol 54 no 15 pp 3857ndash38652009

[18] B Gruss ldquoIron phosphatingrdquoMetal Finishing vol 108 no 11-12pp 33ndash37 2010

[19] D Singh and S Yadav ldquoRole of tannic acid based rust converteron formation of passive film on zinc rich coating exposedin simulated concrete pore solutionrdquo Surface and CoatingsTechnology vol 202 no 8 pp 1526ndash1542 2008

[20] B Qian B Hou and M Zheng ldquoThe inhibition effect oftannic acid on mild steel corrosion in seawater wetdry cyclicconditionsrdquo Corrosion Science vol 72 pp 1ndash9 2013

[21] A Ostovari S M Hoseinieh M Peikari S R Shadizadehand S J Hashemi ldquoCorrosion inhibition of mild steel in 1M HCl solution by henna extract a comparative study of the

inhibition by henna and its constituents (Lawsone Gallic acid120572-d-Glucose and Tannic acid)rdquo Corrosion Science vol 51 no 9pp 1935ndash1949 2009

[22] K W Tan M J Kassim and C W Oo ldquoPossible improvementof catechin as corrosion inhibitor in acidic mediumrdquo CorrosionScience vol 65 pp 152ndash162 2012

[23] B Yuan J Xu X Li and M-L Fu ldquoPreparation of Si-Al120572-FeOOH catalyst from an iron-containing waste and surface-catalytic oxidation of methylene blue at neutral pH value in thepresence of H

2O2rdquo Chemical Engineering Journal vol 226 pp

181ndash188 2013[24] S Bashir R W McCabe C Boxall M S Leaver and D Mobbs

ldquoSynthesis of 120572- and120573-FeOOH iron oxide nanoparticles in non-ionic surfactant mediumrdquo Journal of Nanoparticle Research vol11 no 3 pp 701ndash706 2009

[25] L Carlson and U Schwertmann ldquoNatural occurrence of ferox-yhite (120575rsquo-FeOOH)rdquo Clays amp Clay Minerals vol 28 no 4 pp272ndash280 1980

[26] Z Wang C Xu and X Dong ldquoLocalized corrosion andphase transformation of simulated archaeological ironrdquoChineseJournal of Chemical Engineering vol 16 no 2 pp 299ndash3052008

[27] C Remazeilles and P Refait ldquoOn the formation of 120573-FeOOH(akaganeite) in chloride-containing environmentsrdquo CorrosionScience vol 49 no 2 pp 844ndash857 2007

[28] Z Wang C Xu X Cao and B Xu ldquoThe Morphology phasecomposition and effect of corrosion product on simulatedarchaeological ironrdquo Chinese Journal of Chemical Engineeringvol 15 no 3 pp 433ndash438 2007

[29] S Nasrazadani ldquoThe application of infrared spectroscopy toa study of phosphoric and tannic acids interactions withmagnetite (Fe

3O4) goethite (120572-FeOOH) and lepidocrocite (120574-

FeOOH)rdquo Corrosion Science vol 39 no 10-11 pp 1845ndash18591997

[30] R Balasubramaniam ldquoOn the corrosion resistance of the Delhiiron pillarrdquo Corrosion Science vol 42 no 12 pp 2103ndash21292000

[31] AM Al-Mayouf ldquoInhibitors for chemical cleaning of iron withtannic acidrdquo Desalination vol 121 no 2 pp 173ndash182 1999

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CeramicsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CompositesJournal of

NanoparticlesJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Biomaterials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

MetallurgyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BioMed Research International

MaterialsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Nano

materials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal ofNanomaterials

10 Advances in Materials Science and Engineering

[6] A Jagminas K Mazeika E Juska J Reklaitis and D Bal-trunas ldquoElectrochemical fabrication and characterization oflepidocrocite (120574-FeOOH) nanowire arraysrdquo Applied SurfaceScience vol 256 no 12 pp 3993ndash3996 2010

[7] P Dillmann R Balasubramaniam and G Beranger ldquoChar-acterization of protective rust on ancient Indian iron usingmicroprobe analysesrdquo Corrosion Science vol 44 no 10 pp2231ndash2242 2002

[8] H Tanaka J Wakatsuki K Kandori T Ishikawa and TNakayama ldquoRole of zinc compounds on the formation mor-phology and adsorption characteristics of 120573-FeOOH rustsrdquoCorrosion Science vol 52 no 9 pp 2973ndash2978 2010

[9] T Ishikawa M Kumagai A Yasukawa K Kandori TNakayama and F Yuse ldquoInfluences of metal ions on theformation of 120574-FeOOH andmagnetite rustsrdquoCorrosion Sciencevol 44 no 5 pp 1073ndash1086 2002

[10] A Collazo X R Novoa C Perez and B Puga ldquoThe corrosionprotection mechanism of rust converters an electrochemicalimpedance spectroscopy studyrdquo Electrochimica Acta vol 55 no21 pp 6156ndash6162 2010

[11] M Zic M Ristic and S Music ldquoPrecipitation of 120572-Fe2O3

from dense 120573-FeOOH suspensions with added ammoniumamidosulfonaterdquo Journal of Molecular Structure vol 924-926pp 235ndash242 2009

[12] C Q Cheng J Zhao T S Cao Q Q Fu M K Lei and DW Deng ldquoFacile chromaticity approach for the inspection ofpassive films on austenitic stainless steelrdquoCorrosion Science vol70 pp 235ndash242 2013

[13] A I Munoz J G Anton J L Guinon and V P HerranzldquoInhibition effect of chromate on the passivation and pittingcorrosion of a duplex stainless steel in LiBr solutions usingelectrochemical techniquesrdquo Corrosion Science vol 49 no 8pp 3200ndash3225 2007

[14] S Powell ldquoEvaluation of alternative corrosion inhibitors tochromate for use in organic coatings using scanning referenceelectrode techniquerdquo Surface Engineering vol 16 no 2 pp 169ndash175 2000

[15] B J Basu A Srinivasan J Manasa and V K W GripsldquoImproved corrosion protection of aluminium alloy AA 2024by sol-gel hybrid coatings after surface pretreatment by silani-sationrdquo Surface Engineering vol 28 no 4 pp 294ndash299 2012

[16] Z Liu D Yan Y Dong Y Yang Z Chu and Z ZhangldquoThe effect of modified epoxy sealing on the electrochemicalcorrosion behaviour of reactive plasma-sprayed TiN coatingsrdquoCorrosion Science vol 75 pp 220ndash227 2013

[17] A M Simoes J Torres R Picciochi and J C S FernandesldquoCorrosion inhibition at galvanized steel cut edges by phosphatepigmentsrdquo Electrochimica Acta vol 54 no 15 pp 3857ndash38652009

[18] B Gruss ldquoIron phosphatingrdquoMetal Finishing vol 108 no 11-12pp 33ndash37 2010

[19] D Singh and S Yadav ldquoRole of tannic acid based rust converteron formation of passive film on zinc rich coating exposedin simulated concrete pore solutionrdquo Surface and CoatingsTechnology vol 202 no 8 pp 1526ndash1542 2008

[20] B Qian B Hou and M Zheng ldquoThe inhibition effect oftannic acid on mild steel corrosion in seawater wetdry cyclicconditionsrdquo Corrosion Science vol 72 pp 1ndash9 2013

[21] A Ostovari S M Hoseinieh M Peikari S R Shadizadehand S J Hashemi ldquoCorrosion inhibition of mild steel in 1M HCl solution by henna extract a comparative study of the

inhibition by henna and its constituents (Lawsone Gallic acid120572-d-Glucose and Tannic acid)rdquo Corrosion Science vol 51 no 9pp 1935ndash1949 2009

[22] K W Tan M J Kassim and C W Oo ldquoPossible improvementof catechin as corrosion inhibitor in acidic mediumrdquo CorrosionScience vol 65 pp 152ndash162 2012

[23] B Yuan J Xu X Li and M-L Fu ldquoPreparation of Si-Al120572-FeOOH catalyst from an iron-containing waste and surface-catalytic oxidation of methylene blue at neutral pH value in thepresence of H

2O2rdquo Chemical Engineering Journal vol 226 pp

181ndash188 2013[24] S Bashir R W McCabe C Boxall M S Leaver and D Mobbs

ldquoSynthesis of 120572- and120573-FeOOH iron oxide nanoparticles in non-ionic surfactant mediumrdquo Journal of Nanoparticle Research vol11 no 3 pp 701ndash706 2009

[25] L Carlson and U Schwertmann ldquoNatural occurrence of ferox-yhite (120575rsquo-FeOOH)rdquo Clays amp Clay Minerals vol 28 no 4 pp272ndash280 1980

[26] Z Wang C Xu and X Dong ldquoLocalized corrosion andphase transformation of simulated archaeological ironrdquoChineseJournal of Chemical Engineering vol 16 no 2 pp 299ndash3052008

[27] C Remazeilles and P Refait ldquoOn the formation of 120573-FeOOH(akaganeite) in chloride-containing environmentsrdquo CorrosionScience vol 49 no 2 pp 844ndash857 2007

[28] Z Wang C Xu X Cao and B Xu ldquoThe Morphology phasecomposition and effect of corrosion product on simulatedarchaeological ironrdquo Chinese Journal of Chemical Engineeringvol 15 no 3 pp 433ndash438 2007

[29] S Nasrazadani ldquoThe application of infrared spectroscopy toa study of phosphoric and tannic acids interactions withmagnetite (Fe

3O4) goethite (120572-FeOOH) and lepidocrocite (120574-

FeOOH)rdquo Corrosion Science vol 39 no 10-11 pp 1845ndash18591997

[30] R Balasubramaniam ldquoOn the corrosion resistance of the Delhiiron pillarrdquo Corrosion Science vol 42 no 12 pp 2103ndash21292000

[31] AM Al-Mayouf ldquoInhibitors for chemical cleaning of iron withtannic acidrdquo Desalination vol 121 no 2 pp 173ndash182 1999

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CeramicsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CompositesJournal of

NanoparticlesJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Biomaterials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

MetallurgyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BioMed Research International

MaterialsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Nano

materials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal ofNanomaterials

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CeramicsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CompositesJournal of

NanoparticlesJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Biomaterials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

MetallurgyJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BioMed Research International

MaterialsJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Nano

materials

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal ofNanomaterials