Studies on Localized Corrosion and Desalination Treatment of Simulated Cast Iron Artifacts

Ouyang Weizhen and Xu Chunchun

A simulated occluded cell was utilized to study the localized corrosion in seawatcr and desalination
treatment in alkaline solution of simulated cast iron artifacts. After the simulated occluded cell
galvanostatic test, high acidity and enrichment in chloride ions in the occluded cell were
demonstrated as a result of an autocatalytic process. In addition, scanning electron microscopy
(SEM and energy dispersive !"ray analysis (E#! indicated the degree of the localized corrosion
and the enrichment in chloride ions. An investigation was also made of the chemical changes within
the occluded cell during the desalination treatment$ the results showed that the p% values and the
amount of chloride ion removed from the occluded cell increased with the treatment time. &he
decrease in chloride of the corroded surface of the specimen was confirmed 'y E#!. &he research
appeared to prove that the simulated occluded cell is capa'le of providing useful information on the
localized corrosion and desalination treatment of simulated cast iron artifacts.
INTRODUCTION
Nowadays the storage of cast iron artifacts recoered from marine sites has receied e!tensie
attention" One of the most serious #ro$lems facing conserators and conseration scientists is how
to sta$ilize iron artifacts against further corrosion under faoura$le enironmental conditions" The
ingress of chloride ions is of #articular concern $ecause they are aggressie and can #romote
corrosion %&' ()" Since they hae deleterious effects on corrosion #erformance' chloride ions must
$e remoed %*+" Therefore' it is worthwhile inestigating the mechanism of localized corrosion and
desalination treatment of cast iron artifacts"
The localized corrosion of cast iron artifacts is a com#le! electrochemical #rocess' with the anodic
and cath,odic reactions occurring at s#atially se#arate #oints %-+" During corrosion' the iron,
containing #hases are corroded $ut the gra#hite remains as an interlin.ed three,dimensional
networ. which retains the original sha#e of the artifact %&+" It has $een agreed that the solution
within the gra#hitized region of corroded marine cast iron is essentially a ferrous chloride solution'
with a concentration of & / or greater and #0 -"1 %2+" Local acidification and chloride ion
enrichment could $e e!#lained $y the model deelo#ed $y Turgoose %3+" which was in some ways
similar to creice or #itting corrosion on iron e!#osed to a solution containing chloride ions" Within
these occluded caities' the #resence of chloride ions indeed contri$utes to a corrosion cycle 456"
The autocatalytic #rocess is a feature common to the localized corrosion of cast iron artifacts in
seawater" Detailed studies of the autocatalytic #rocess will certainly hel# in understanding the
localized corrosion #rocess" To date' there hae $een no direct techni7ues to measure either the #0
alues or the chloride concentration in the #ore solution"
On the other hand' the remoal of chloride ions is a$solutely essential for the conseration of iron
artifacts" The #rinci#al aim of any treatment of archaeological iron of marine origin is to eliminate
chloride from the corrosion #roducts" It this is done successfully' the deelo#ment of the corrosion
#rocess due to chloride ceases and the rate of corrosion is reduced to a more managea$le leel'
where conentional methods to counter corrosion can o#erate efficiently" When artifacts are soa.ed
in a treatment solution' the hydro!ide ions diffuse into the corrosion #roduct reacting with chloride,
containing com#ounds to #roduce free chlonde ions' and then chloride ions diffuse out from the
#ores of high chloride ion concentration into the treatment solution %1)" The chloride ion diffusion
tends to $e releant to the #rocesses occurring in solution,filled #ores" At #resent' there is no
consensus as to the o#timum treatment and one reason for this a##ears to $e that there is no relia$le
method of assessing the ongoing #rocess during treatment" Conse7uently' a thorough .nowledge of
the chloride ion migration in occluded #ores during the treatment is essential if desalination
methods are to $e carried out successfully"
It would $e of great #ractical interest to hae a #hysical model which ena$led the study of the
microsco#ic mechanism of the localized corrosion of cast iron artifacts and chlonde ion migration
during corrosion and desalination" The method using a simulated occluded cell is a conenient way
to reeal the chemical changes within an occluded cell' and has $een confirmed $y many
researchers %8+' including /ars 9" :ontana and /arcel ;our$ai!" <!#erimental data' com$ined with
the #hysical descri#tion of the localized corrosion #rocess' should #roe useful for deelo#ing more
ersatile' #henomenological corrosion #rediction and conseration for cast iron artifacts"
In this #a#er' it is intended to inestigate the changes of chemical states within the occluded cells of
simulated cast iron artifacts in *"2 wt= NaCl solution and ("2 wt= NaO0 solution $y use of a
simulated occluded cell" In addition' scanning electron microsco#y 4S</6 and energy dis#ersie X,
ray analysis 4<DX6 were ado#ted to analyse corrosion mor#hology and com#onents"
EXPERIMENTAL DESIGN
The s#ecimens were made of grey cast iron to simulate cast iron artifacts" A simulated occluded cell
a##aratus was used in the study of localized corrosion and desalination treatment" 4A full
descri#tion of the simulated occluded cell is #roided in the A##endi!"6
A simulated occluded cell galanostatic test was carried out in *"2 wt= NaCl solution' which was
the medium to simulate seawater corrosion" The glass container was filled with the solution and its
#0 was ad>usted to 5' though seawater is normally in the range 1"(,5"1" At room tem#erature' the
solution was in>ected into the occluded cell" An anodic current density of
& mA,cm
(
was a##lied to the occluded s#ecimen to simulate the cou#le current in and out of the
occluded cell" The chloride ion concentration and #0 in the simulated occluded cell were monitored
at arious time interals" During desalination treatment the simulated occluded cell' after -1 hours
of galanostatic tests' was immersed in a glass container containing ("2 wt= sodium hydro!ide"
The #0 alues and the chloride contents in the occluded cell at different time interals were
monitored in order to determine the #rogress of chloride ion release" Details of the e!#erimental
#rocedures are descri$ed in the A##endi!" S#ecimens after tests were #hotogra#hed $y S</ and
analysed $y <DX"
RESULTS AND DISCUSSION
After the simulated occluded cell galanostatic tests' the #0 alues in the occluded solution oer
time under & mA,cm
,(
anodic current density are shown in :igure &" It can $e seen that the #0
dro##ed shar#ly within the first hour from 5 to 2"31' then tended to decrease gradually" After 5(
hours of accelerated corrosion' the #0 alue dro##ed to *"13"
The reason for this was that localized corrosion too. #lace inside the occluded cell" The localized
corrosion inside the occluded cell resulted from the esta$lishment of differential o!ygen cells and
was continued $y the stimulation of the autocatalytic #rocess which #romoted local acidification
and chloride ion enrichment" Local acidification that occurred inside the occluded cell inoled
dissolution of the anode and hydrolysis of the dissoled metal ions" Cations dissoled from the
anode
Figure 1 (all in p% in the occluded cell with time with a ) mA"cm
"*
current density passing
through the specimen.
found difficulty in diffusing outwards $ecause of the greater immo$ility of the solution in the
occluded cell com#ared to the $ul. solution" In conse7uence' their concentrations increased" The
accumulation and hydro,lysis of :e
(?
resulted in local acidification in the occluded cell" The
hydrolysis reactions are gien $elow %3+@
The generation of free acid lowered the #0 alue and' inersely' the increase in acidity accelerated
localized corrosion" The effect in the occluded cell of acidification causing accelerated localized
corrosion actiity is called the Aautocatalytic effectA %&B+" As anodic current #asses through the
occluded s#ecimens' the autocatalytic #rocess continues at a steady rate in the occluded cell' and the
#0 alue gradually decreases"
On the other hand' chloride ions migrated inward from the $ul. solution simultaneously with local
acidification" :igure ( is re#resentatie of the 7uantity of chloride ion migration in the occluded cell
at arious time interals under & mA,cm
,(
anodic current density" It was found that the chloride ion
migration increased in a linear relationshi# with the increase of time"
As noted #reiously' dissolution of the anode resulted in an increase in :e
(?
ion concentration" In
order to $alance the e!cess #ositie charge #roduced in the occluded cell' negatie chloride ions
hae to migrate inwards from the $ul. solution to maintain electrical neutrality %5+' which causes
chloride ion enrichment in the occluded cell" /oreoer' the autocatalytic #rocess
.ee#s chloride ions migrating inwards' and therefore chloride ion concentration increases with time"
As long as the cast iron s#ecimen is corroding and #roducing :e
(?
ions' chloride ions will diffuse in
and concentrate in the occluded cell"
As a result of the autocatalytic #rocess inside the occluded cell' the acidity, 4ia hydrolysis6 and
chloride concentration 4ia migration6 increased with time" The relationshi# $etween #0 and
chloride ion concentration m the occluded cell at & mA"cm
,(
current density is #resented in :igure *"
It is eident that the #0 alue in the occluded cell dro##ed ra#idly from 5 to $elow 2' and thereafter
decreased linearly' indicating that the decrease in the #0 alue was accom#anied $y an increase in
chloride ion concentration"
Figure 3 +elationship 'etween p% value and the chloride ion concentration in the occluded cell.
Cased on the results a$oe' the #0 alue $elow 2 was #ro#ortional to the chloride ion
concentration" The following em#irical e7uation was deried@
#0 D 3"1(,("5& %Cl
,
+ E D B"88&B
where %Cl
,
+ was the chloride ion concentration in the simulated occluded cell and E" was the
confidence in the fitting e7uation"
S</ microgra#hs of s#ecimens after galanic testing tor (- and -1 hours at & mA,cm
,(
anodic
current density,are #resented in :igure -" As can $e o$sered' the surface #atterns differed from one
another" :igure -a e!hi$ited a rust laer with a uniform' adherent and con,
Figure 4 SEM micrographs of cast iron under an anodic current density of ) mA.,m
"*
for (a *-
hours and (' -. nours/$(c and (d show the detailed surface morphology of sample -'
tinuous structure" In contrast' :igure -$ demonstrated a more seere attac. on the rust layer" The
insolu$le structure' and micro,caities and crac.s' can $e clearly o$sered in :igures -c and -d"
The more seere attac. on the rust layer in :igure -$ was attri$uted to the autocatalytic effect'
which #romoted acidity and chloride ion concentration' thus accelerating the dissolution of cast iron
with longer e!#osure time" The insolu$le structure m :igure -c' which was fla.e,li.e' indicated that
the residual gra#hite formed a three,dimensional networ." In addition' micro,caities and crac.s
could $e seen in :igure -d" The formation of these micro,caities and crac.s was ealuated in
relation to the acid #roduced and the formation of the solid #roducts' which could gie rise to local
stresses and cause dissolution of other corrosion #roducts' there$y chemically assisting the
#ro#agation of crac.s and aiding the disintegration of the rust layers %&&+" The general conclusion
was that the autocatalytic effect e!erts a greater influence on the sam#le after the -1,hour test than
on the sam#le after the (-,hour test"
In order to o$tain a $etter understanding ot outward diffusion of chloride ions' the simulated
occluded cell is also used in the desalination treatment" /onitoring the #0 in the occluded cell oer
time #roides more details during chloride remoal' which is shown in :igure 2" The #0 alue in
the occluded cell rises gradually with the s7uare root of the treatment time"
The reason tor the increase in the #0 alue is the increase m hydro!ide ion concentration in the
occluded cell" The inward flow of the hydro!ide ions is due to the concentration gradient $etween
inside and outside oF the occluded cell" In general' the high mo$ility of hydro!ide ions and their
concentration in the treatment solution maintain the inward diffusion of hydro!ide ions' thus the #0
alue increases gradually oer time"
As a result of the ingress of hydro!ide ions' chloride ions diffuse outwards from the occluded cell
into the washing solution" After immersion' the amount of chloride ion remoed from the occluded
cell increased with the s7uare root of time as shown in :igure 3" It can also $e seen that the results
are diided into two stages"
It is generally acce#ted that two ste#s might occur when a marine iron artifact is soa.ed in the
treatment solution %1+" One is the reaction of dissolution of the A:eOClA to #roduce free chloride
ionsG the other is the moement of the chloride ions from their #oint of #roduction inside the
corrosion #roduct to the $ul. wash solution" After galanic testing for -1 hours at & mA"cm
,(
anodic
current density' the s#ecimen released :e
(?
ions into the occluded solution" It has $een re#orted that
chloride ions #resent in the iron corrosion #roducts are tra##ed within the lattice structure of the
arious iron o!yhydro!idesG among them' ferric o!ychloride 4:eOCl6 is the dominant chloride,
containing corrosion #roduct on cast iron %&(H&-I" In the case of the galanic test' :eOCl' which is
not sta$le m air' may $e #resent as an intermediate #hase during the corrosion #rocess due to lac. of
o!ygen in the occluded cell and $e conerted to J,:eOO0 once e!#osed to air" North has #ro#osed
Figure 5 +elationship 'etween p% in the occluded cell and the s0uare root of the treatment time.
Figure 6 &he amount of chloride ion removed as a function of the s0uare roof of the treatment
time.
the mechanism $y which chlorides in the corrosion #roducts are conerted to free chloride ions
during chloride remoal" The reaction is gien $y %&2+@
The hydro!ide ions diffuse into the occluded cell and react with chloride,containing com#ounds to
#roduce free chloride ions" Then the chloride ions migrate outwards $ecause of the concentration
gradients $etween inside and outside of the occluded cell' and the remoal of chloride should $e
achieed"
The data in :igure 3 indicate that there may $e two stages inoled in the washing" The initial stage
is controlled $y the reaction ot dissolution of the :eOCl and in turn this is controlled $y the outward
diffusion of chloride ions" In stage I" it is due to the ra#id ingress ot hydro!ide ions in the occluded
cell' which allows the dissolution of the :eOCl' and the more chloride ions #resent in the occluded
solution the more chloride ions can $e trans#orted" Thus' the amount of chloride ion remoed
ra#idly increases" In stage II' the amount of chloride ions remoed increases gradually $ecause of
the decrease in the concentration gradients ot hydro!ide ions $etween inside and outside of the
occluded cell" The reaction of dissolution of the :eOCl may not $e a significant factor in
determining chloride release rate" The outward diffusion of chloride ions may then #lay an
im#ortant role in the washing" As the rate,controlling #rocess is generally outward diffusion ot
chloride ions in the washing method' the rate of chloride ion release from the occluded cell into the
wash solution follows the diffusion law %1+" According to this law' the diffusion e7uation #redicts
that the amount of chloride ion remoed aries linearly with the s7uare root of the treatment time"
Such a line is shown in :igure 3' and the agreement $etween theory and e!#eriment indicates that
diffusion is the rate,controlling #rocess in stage II"
The release rate of chloride ions can $e o$tained $y analysis of chloride ion remoal data measured
in the occluded solution' which has seldom $een used in the literature" The chloride ion e!traction
rate at a s#ecific time is defined $y the instantaneous slo#e at that time' which is the deriatie of
the amount of chloride ions remoed from the occluded cell with res#ect to time %*+" :igure 5 is a
#lot of the chloride ion e!traction rate as a function of treatment time"
Figure 7 &he chloride ion e1traction rate from the occluded cell with treatment time.
It was tound that the chloride ion e!traction rate decreased ra#idly at the $eginning and then $ecame
almost sta$le' with a minor decrease with the increase of washing time" Cy monitoring the amount
of chloride ion e!tracted and constructing a gra#h from this information' the chloride ion e!traction
rate can $e used to ealuate the effectieness of different treatment solutions $y using the same
occluded cell" /oreoer' the chloride ion e!traction rate as a guide to the #rogress of the treatment
can #roide a signal to change the treatment solution when the cure leels out into a #lateau
region" 0aing achieed an understanding of the #rocess of chloride remoal' it can $e a##lied to
increase the desalination efficiency"
X,ray energy dis#ersie s#ectrometry 4<DX6 of sam#les $efore and atter the 5(,hour desalination
treatment is shown in :igure 1" :igure 1a shows the chemical com#osition of the s#ecimen after the
-1,hour galanic test at & mA,cm
,(
anodic current density and :igure 1$ is the <DX analysis of the
corroded s#ecimen atter the 5(,hour desalination treatment which followed the a##lication of a &
mA,cm
,(
anodic current density for -1 hours" The #resence of :e" /n' Si' ;' S and Cl could $e
o$sered" Com#aring these two #ictures" :igure 1a was rich in chloride and :igure 1$ was low in
chloride"
Figure 8 ,hemical composition of specimens 'efore and after the treatment analysed 'y E#!. (a
E#! analysis of the cast iron with ) mA.cm
"*
applied anodic current density for -. hours, (' E#!
analysis of the corroded specimen after 2*"hour desalination treatment.
The <DX analysis in :igure 1a #roided eidence that the chloride ion enrichment was the result of
the autocatalytic #rocess inside the occluded cell" :igure 1$ #roided intormation that the decrease
in chloride was due to the diffusion of the chloride ions from the occluded cell to the washing
solution during the treatment"
CONCLUSIONS
A simulated occluded cell was used to study the localized corrosion and the desalination treatment
of simulated cast iron artifacts" It is a conenient method to reeal the chemical changes within an
occluded cell' which can not only study the mechanism ot the localized corrosion of cast iron' $ut
can also inestigate chloride ion migration in and out of the occluded cell during localized corrosion
and desalination treatment"
In the #resent wor.' the changes of chemical state for localized corrosion of simulated cast iron
artifacts in *"2 wt= NaCl solution were studied" It was found that as an anodic current was #assed
through the cell' the #0 alue inside the cell initially fell 7uic.ly and then decreased gradually"
/eanwhile' the chloride ions migrated into the occluded cell" The 7uantity of chloride ion migration
increased with the time that the current was flowing" The results of the S</ analysis showed
acceleration of dissolution of cast iron with the time of a##lication of the anodic current' and <DX
analysis indicated the enrichment in chloride ion"
A study was made of the chemical changes within the simulated occluded cell after the 5(,hour
desalination treatment which was a##lied to sam#les that had first $een corroded at & mA,cm
,(
anodic current density for -1 hours" During chloride remoal' the #0 alue in the occluded cell
gradually increased oer time" In addition' the amount ot chloride ions remoed from the occluded
cell increased with the treatment time" The chloride ion e!traction rate initially decreased ra#idly
and then $ecame almost sta$le with the washing time" :urthermore' the <DX analysis disclosed the
change of com#osition ot chlonde after the treatment"
It is eident that the simulated occluded cell could hel# in understanding the degree of localized
corrosion and the #rogress of the treatment of cast iron artifacts' there$y ena$ling their safe and
effectie #reseration"
ACKNOWLEDGEMENTS
The authors would li.e to than. the National Key Technologies ELD ;rogram of the &Bth :ie,
Mear ;lan ;eriod for financial su##ort 4Contract No" (BB&CA1B2CB&6" This wor. was also
su##orted $y the State Key La$oratory for /etallic Corrosion and ;rotection" Than.s are also
e!tended to Dr L"S" Selwyn for her .ind hel#"
APPENDIX: EXPERIMENTAL
A simulated galanostatic occluded cell a##aratus %&3+' as shown in :igure 8' was ado#ted to study
the localized corrosion"
Figure 9 Schematic diagram of the simulated occluded cell/ ) 'ulk specimen, * occluded
specimen. 3 simulated occluded cell. - magnetic stirrer.
As can $e seen' the simulated occluded cell made of hard glass was in the centre of a glass
container' the effectie olume of which was &"2 mL" The cell was se#arated from the $ul. solution
$y a glass tu$e 4&"2 1 &2 mm6' which was filled with filter,#a#er scra#s to retard diffusion and
conection $etween the occluded and the $ul. solutions" The s#ecimen was inserted into the cell
through a ru$$er sto##er" The outer end of the s#ecimen was connected to the #ositie terminal of a
set of $atteries' the negatie terminal of which was connected to the e!ternal $ul. s#ecimen of
gra#hite"
The s#ecimens used were grey cast iron to simulate cast iron artifacts' so the corrosion #rocess
would $e similar in soine ways to that o$sered in the field" The chemical com#osition of
s#ecimens 4wt=6 was@ C *"BB' Si &"1-' /n B"1(' ; B"B81' S B"B18" The surfaces of the s#ecimens
were wet,#olished with silicon car$ide #a#er to grade &BBB" The sam#les were then rinsed with
deionized water' degreased with C;,grade acetone 4#ro#anone6 and stored in a desiccator filled with
nitrogen until they were ready for testing" The e!#osed area of each s#ecimen was (2 mm
(
' and the
remaining surface was shielded with silicone #aste" The e!#osed area ratio $etween the occluded
and $ul. s#ecimen was a$out &@&BB" NaCl 4AE grade6 and deionized water were used to ma.e u# a
*"2 wt= solution' which was the medium to simulate seawater corrosion" The glass container was
tilled with ( L of the solution and its #0 was ad>usted to 5" At room tem#erature' a$out &"2 mL of
the $ul. solution was in>ected into the occluded cell" An anodic current density of & mA"cm
,(
was
a##lied to the occluded s#ecimens to simulate the cou#le currents in and out of the occluded cell ia
resistances" After arious time interals the tests were sto##ed' and the occluded solution was
remoed for analysis" The #0 alue of the occluded solution was recorded with a #0 meter 4#0s,(2
ty#e6 at am$ient tem#erature" The chloride ion concentration was o$tained with a /etrohm 4model
52& Titrino6 #otentiometric titrator"
The desalination treatment was conducted in ("2 wt= NaO0 solution" After a -1,hour galanic test
at & mA"cm
,(
anodic current density' the simulated occluded cell was immersed m a glass container
containing the sodium hydro!ide" The outer end of the s#ecimen was directly connected to the
e!ternal $ul. s#ecimen of gra#hite" The #0 alues and the chloride ion contents in the occluded cell
at different time interals were monitored"
After e!#osure in the simulated occluded cell galanostatic tests at & mA"cm
,(
anodic current
density for -1 hours and the su$se7uent desalination treatment for 5( hours' s#ecimens were rinsed
in deionized water and then dried in hot air and stored in a container filled with nitrogen" The
microstructural characterizations of the sam#les were #erformed with a Cam$ridge 4model S(2B,
/K*6 scanning electron microsco#e' fitted with a Lin. 4model AN,&BBBB6 energy dis#ersie
s#ectrometer"
E<:<E<NC<S
& North" N"A"" and /acLeod" I"D"" ACorrosion oF metalsA' in ,onservation of Marine
Archaeological 4'5ects, ed" C" ;earson' Cutterworths" London 4&8156 31,81"
( Dalard" :"" 9our$eyre' M"" and Degrigny" C' AChloride remoal from archaeological cast iron $y
#ulsating currentA' Studies in ,onseivation -5 4(BB(6 &&5,&(&"
* Selwyn' L"S"" /cKmnon" W"E"" and Argyro#oulous' N"' A/odels tor chloride ion diffusion in
archaeological ironO' Stadia in ,onservation -3 4(BB&6 &B8,&(B"
- Wal.er" E"" AThe corrosion and #reseration of iron anti7uesA' 6ournal of ,hemical Education
284&&6 4&81(6 8-*"
2 North" N"A"' OCorrosion #roducts on marine ironA" Studies in ,onservation (5 4&81(6 52,1*"
3 Turgoose" S"" AThe corrosion ot archaeological iron during $urial and treatmentA' Studies in
,onseivation *B 4&8126 &*H&1"
5 Selwyn" L"S"" Sirois' ;")"' and Argyro#oulous' N"' AThe corrosion of e!caated archaeological iron
with details on wee#ing and a.aganPiteA" Studies in Conseration -- 4&8886 (&5H(*("
1 North" N"A"" and ;earson" C AWashing methods for chloride remoal trom marine iron artifactsO"
Studies in ,onservation (* 4&8516 &5-,&13"
8 Quo" )"" >in" Q"" Sun" &C" Xu" M"" :eng" X"" AAccelerating eRect and cntical #0 alue ot occluded
cell corrosion within #its' creices' or stress corrosion crac.sA" ,orrosion --416 4&8116 2*8H2-*"
&B Wei' IS"" Sin" M"" Lin" K"" Lin" M"" CaF" M"" Chen" X"" Shi" /" )ian" C &he &heory and Application
ot Metal ,orrosion. Chemical Industry ;ress" Cei>ing 4&81-6 &2B"
&& Turgoose' S"" O;ost,e!caation changes in iron anti7uitiesA" Studies in ,onservation (5 4&81(6
85,&B&"
&( North" N"A"' and ;earson" C" AAl.aline suliite reduction treatment ot manne ironA' in I,4M
,ommittee for (,onservation -th &riennial Meeting. Nenice 4&8526 52,&*' *,& to 52 &* *,&-"
&* North" N"A"" and ;earson" C AThermal decom#osition oF :eOCl and marine cast iron corrosion
#roductsA" Studies in ,onservation (( 4&8556 &-3,&25"
&- 9il$erg" /"E"' and Seeley" N"T"" AThe identity of com#ounds containing chloride ions m marine
iron corrosion #roducts@ a critical reiewA" Studies in ,onservation (3 4&81&6 2BH23"
&2 North" N"A"" and ;earson" C AInestigations into methods for consering iron relics recoered
from the seaA' m ,onsen"atiou in Archaeology and the Applied Arts. IUC" London 4&8526 &5*,&1&"
&3 Xu" C :u" X"" and Liu' M"' OChemical changes within occluded corrosion cell of mild steel in
NaCl solutionA' 6ournal of ,hemical Industry and Engineering 2B4-6 4&8886 (21,(3("
AUTHORS
OVMAN9 W<IQ0<N com#leted his masterAs degree in corrosion and #rotection from Cei>ing
Vniersity of Chemical Technolog6
&
in &883" 0e studied for a doctorate in (4&B(" 0e is an associate
#rofessor and his research focuses on the corrosion and conseration #ro$lems related to cast iron"
Address/ 7ei5ing 8niversity of ,hemical &echnology. )9 7cisanhuau East +oad, 7ei5ing ):::*;,
<+. ,hina. Email/ ouyangwz=grad.'uct.edu.cn
Xu C0VNC0VN has an engineering degree 4&83-6 from Cei>ing Vniersity ot Chemical Technology"
She is a #rofessor at the Vniersity and Nice,Secretary 9eneral and Director' Chinese Society of
Corrosion and ;rotection 4CSC;6" She has conducted research in corrosion science" Address as for
4uyang. Email/ chunchun1u=*>3.net
Rsum H 8ne cellule ferm?e simul?e a ?t? utilis?e pour ?tudier la corrosion localis?e dans l@eau
de mer et le traitement de dessalement en solution alcaline pour des o'5ets eu foute simul?s. AprAs
un test galvauostati0ue de Ba cellule, on a pu o'server, comme r?sultat d@un processus
autocatalyti0ue, une forte acidit? et un enrichissement en ions chlorure dans la cellule. <ar
ailleurs, les analyses au ME7CE#S indi0uaient le niveau de corrosion localis?e et l@enrichissement
eu ions chlorure. 8ne investigation a ?galement ?t? men?e sur les changements chimi0ues D
l@int?rieur de la cellule ferm?e pendant le traitement de dessalement$ les r?sidtats montrent 0ue les
valeurs du p% et la 0uantit? d@ions chlorure ?limin?s de la cellule augmentaient avec la dur?e du
traitement. Ea diminution de la 0uantit? d@ions chlorure D la surface corrod?e de l@?chantillon a ?t?
confirm?e par E#S. Ea recherche sem'le prouver 0ue la cellule ferm?e simul?e est eu mesure de
fournir des informations utiles sur Ba corrosion localis?e et sur le traitement de dessalement
d@o'5ets en fonte.
Zusammenfassung H Eine Simulation einer EinschluFzclle wurde verwendet, um die lokale
Gorrosion in Meerwasser und die Entsalzung durch die 7ehandlung mit alkalischeu EHsungen au
Schmiedeeisen zu untersuchen. IemJF einem galvanostatischen &est konnte ein holier p%"Kert und
eine Anreicherung von ,hloridionen in der Eiuschlusszelle 'eo'achtet werden, welche auf
autokatalytisclie <rozesse zurLckgefLhrt werden. #as AusmaF der Gorrosion und der
,hloridanreicherung wurden durch 8ntersuchungen mit %ilfe der +astcrclektronenmikroskopie I
energiedispersiveu +Hutgenmikroaualyse (+EMCE#! 'estJtigt. Keitere 8ntersuchungen 'etrafen
die chemischen I eranderungen in der Einschlusszelle wJhrend der Entsalzung. #a'ei stiegen der
p%"Kert und der Irad der ,hlorident5ernung mit der 7ehandlungsdauer. Eetzteres wurde mit E#!
'estJtigt. #ie 8ntersuchungen legen nahe, dass anhand der simulierten Eiuschlusszelle nLtzliche
Informationen L'er lokale Gorrosionen und Entsalzungseffektc an Schmiedeeisen gewonnen werden
kHnnen.
Resumen H Se empleM una simulaciMn de c?lula cerrada con el fin de estudiar, tanto la corrosiMn
localizada por efecto del agua de mar, como los tratamientos de desalinizaciMu en disoluciones
alcalinas para artefactos simulados de hierro fundido. SegNn mostrM el test, en la c?lula
galvanoestOtica cerrada se manifestM una elevada acidez y un enri0uecimiento de iones cloruro,
todo ello resultado del proceso autocatalPtico. Adicioualmente, micrografPas o'tenidas por
microscopPa electrMnica de 'arrido (SEM y energPa dispersiva de rayos ! (E#S mostraron el
grado de corrosiMn localizada y el aumento de iones cloruro. Se realizM ademOs una investigaciMn
so're los cam'ios 0uPmicos ocurridos en el interior de la c?lula cerrada durante el tratamiento de
desalinizaciMn$ los resultados mostraron 0ue los valores del p% y la cantidad de iones cloruro
eliminados aumenta'an cu el transcurso del tratamiento. Ea disminuciMn de los cloruros en la
superficie corroPda de las muestras se confirmM mediante E#S. Ea investigaciMn parece pro'ar 0ue
la c?lula cerrada simulada es capaz de suministrar informaciMn muy Ntil so're corrosiMn
localizada y tratamientos de desalinizaciMn en o'5etos simulados de hierro fundido.