CEMENTand CONCRETERESEARCH. Vol. 18, pp. 193-203, 1985.

Printed in the USA

0008-8846/88 $3.00+00. Copyright (c) 1988 Pergamon Press plc.

~ c R I C ACID ~ T A C K aN ~ ~ - AN ANAIXTICAL SIUDY

Satlsh C%m~ra, Ass. professor

Div. of Building Materials, ~ 1 ~ s University of Technology

(Communicated by D.M. Roy)

(Received April 21, 1987)

An analytical study of hydrod~orlc acid attack an ~ mortar prisms

is dane in this work. 4x4x16 cm mortar p r 4 ~ specimens ( ~ t sand
ratio 1:3) were ~ . ~ were put in mjdrochl~-Ic acid molutian.
After a ~rtaln period they were taken out and were then quita p o ~ s
on the surface. ~ m y %~re carefully cut. Very distinct layers were
visible an the cut mnTaos. ~ colour of the specimsns varied from
y~llaw an the ~ m~face to steel grey in the middle of the speci-
(ur-~,,,Ted). ~ ~ the ~ part a ~,.,wn ring w ~
noti~d. Different layers were analy~d by atomic a~orptian, S ~ and
~X. ~ m~m ~ ~r, ~ ~ with ~ y ~ ~in ~ti~s
made ~ ~u studied under S ~ - E D S and electran microscope. X-
ray lin~ analysis were done an ~ ~ m P l ~ and b ~ k ~ a t t e r ~
electrun image m i ~ ~ ~ . It %ms nut_Iced that the
u n ~ m ~ g d mortar was m ~ L ~ m ~ e d ~ a r i n g of ~ . ~ was rather h a ~
and ~ c t ~ d the ~ f ~ further damage. ~he calci~ ~ t i a n
~ecreased m x r ~ m i v e l y ~ the middle of the outer surface. ~he
cruxes=arian of silica ~ in the layers ~ t s i ~ the b r ~ n ring.

~ e r v e d here, an ~ ridl -~-~hous phase (',,u~.,,..,.m,rin~) f o l l o w ~ by' a

lighter ash colaur ~ phase, it is m ~ t pr~ably a silica

It is also h y p ~ that b e m ~ dimeolutlan, thmzl is a pamsibi-

lity of calci~ aklurk~ aluminatm h ~ r a ~ SiAl, Ca-AI-Si and Si-Fe
,:,-,,~. 1 , , v ~ fmmmtian. ~ g i w s rise to the ~ m n s i a n cracks in the

study h u g i ~ m a l i t - t l e b e t t e r urd~,~.ar~4,~j oE the pro~ss of

~ ~ a t e ~ k an the ~ mm~car.
~ ( ~

Sulphate ~ ~ ~ wwter ~ of am=zeta im m ~ t l y

urger ~ an.e~LUty of om,=,,t, I S , I / ~
att:ack l.ms ,,,or~ go m,:~ atXamtlon. Industril az~ ~z'owir~ fast
and ao is tl-~ pollut/on amd ,~4~ za/n. 'm.ls c a u m J mor~ d a ~ ~
~ and l'Jas~ m o 0 ~ ~ in s~-,*'~Lngtl~ a=Id rmi~cance

193
194 Vo]. 18, No. 2
S. Chandra

of concrete. I n t h i s paper the subject c~z~en for study is hydrochloric

acid as this is considered to be the simplest acid in the acid attack
group. ~ others hydrod~oric acid attack on ~ is referred to
in the works of ~ /6,7/ and Stecpoe /12/. In mc6t of the ~ r k s the
hydrochloric acid solution is analysed after the test and not the
concrete. It is difficult to analyse the concrete as it is brittle and
most of the phases present are not very well crystallized.

It has been tried to analyse Portland o m ~ n t mortar specimens after

acid attack by powder X-ray diffraction and I R ~ but no
significant information could be achieved due to the presence of
~ ~ ~ in the fL=L ~ and overlapping peaks in the second
case. In this paper analyses of the specimens done by atomic absorption
E ~ X , S~M-EDS & T~M are reported.

MATERIAIS AND MEn40OS

1:3 Portland c~m~nt (C3S^- 64%, C2S - 13%, C3A - 8%, C4AF - i0%,
specific surface - 337 m~/~) mortar ptH~-- were mmde with 0.50 water-
o m ~ n t ratio. ~ e _~e~_4 ~ s were stored under ~ater for 5 days and in a
climate rocm at 55% ~ and 20°C tGm~erature for 21 days.

Iniquenoe o f 15% h ~ o r i c acid was tested on t h u e tm~,~,~.

TABLE I

Before test 1 day 2 days 3 days 5 days

Apparent 4.1 16 26 36 4!
~rosity
in %

Apparent porosity at the portland cement mortar prism specimen after different
time under 15% HCT so]ution.

W,

Fig. I. Photograph of the cut section of a mortar prism a f t e r

I day in 15% HC] acid solution.
 Vol. 18, No. 2 195
HCI, MORTAR, ATTACK, ANALYSIS

Fig. 2. Photograph of 4x4x16 cm prism specimens after 5 days in

HCl solution.

TABLE I I

Combo Theorett- Zone 1 Zone Z Zone 3 Zone 4 1 Zone S

tion
of AA EDAX KA EDAX AA EDAX A~ EDAX EDAX
mor~i I°'
S|0z 77.6 64.44 59.64 GO.G0 51.93 83.01 71.20 82.90 70.SO 81.20 70.70

C,'0 14.5 13.84 12.60 10.30 11.40 9.20 9.80 4.30 3.65 4.26 3.52

Fe=O: 3.4 3.02 2.95 3.80 3.70 1.87 1.77 1.85 1.73 1.84 1.72

AIzO: 4.4 4.46 4.25 4.93 5.30 4.02 4.20 3.92 4.18 3.85 4.19
i
Ic1 0 0 9.29 11.7 10.15 10.15

Chemical analysis of portland cement m r t a r prism spectlen after attack with 15% HC1.
Zones sh~,m here refer to f i g . 2.

concentration of acid ~ms selected based ~ x m the wark of Rubetskaya et

al 191. All tl~ ~I,. t ~ specimm~ were put in acid solution t ~ y were
in a glass cm~ainer with a cover. ~ e ~ porosity was
measured at diffe~e~ intervals (Table I). After 5 days the _%pe~_J~ns
were severely a ~ , ~ d . ~%e physical ocrcliticn of the specimens is shown
~ ~ 1 1 y in Fig. 1. ~ e specimens were ~ t in N c t i ~ s . It is
seen that there are different layers in the a~maqed . specimens (Fig. 2).
~he material frcm different layers was taken out and was analysed by
atomic absorptiun, AA, (Table If). ~ e p r ~ - ~ were very brittle.
w~re 1-Trec~mt_~_ with e~m~y in ~ d e r to hold the shape and were
analysed by E~%X. Further X-ray llne analysis were duns on these
specimens by scanning the -~ple. by a line of 10 mm length and i m
thi~- for Fe/~, CaF~ and SiY~ using EDAX 711 made by Jeol, Japan.

(Fig. 3 ) . m . ~ r m ~ ~ L s r i n g ~Lre ~ by t~=k s c a ~

electrc~ image using S~M-EE6 made by Jeol, Japan (Fig. 4). ~ l~*ases
(zi~t grey, grey and dark grey) are ~ in t h ~ a ~ .
196 Vo]. 18, No. 2
S. Chandra

Fig. 3. Impregnated cut section of prism specimen after 5 days in

15% HCI solution showing different zones.

I) Undamaged mortar

2) Brown ring

3) Just after brown ring

4) A few mm inside the outer surface

5) The outer surface in contact with acid

~ e s e are analysed by EDAX. ~le ree~Its are shuwn in Fig. 5. A t h i n

section of t h u e ~ w u cut and studied unter TEM. ~ e micro-
graphs frum the irrer undisturbld z ~ , t b e ~ coloured zarm and the
cuter strcr~ly a l ~ zone are presemted in Fig. 6.

RES3LTS AND DISCU3SIaN

It is seen that after one day in the acid solutiun, a cavity is c r ~ a t ~

in the Portland ~ mortar specim~. ~ / s is on the border of
carbonated and not carbonated zcrms. It is expected that ~ to the
d~iticn of carbonates, a ~ is developed and the whole
~ t ~ layer ~ i n t e g r a ~ . It is seen that the acid attack
the apparent porosity of the p ~ specimen. ~ d s is ~ to
the reason that the acid reacts with the clinker minerals of ~ n t and
forms soluble salts mcmtly with calci~, which are subeequently leached
cut. ~he undemolved salts form a layer usually r~ferred to as a
'9~dru~de mixture". ~ e salts are c o n c e n t r a ~ on the surface of the
mortar and is s a m as a dark L ~ w n ring. ~ colour of the
specimen ~ f ~ m this brown ring to light yellow towards the
surface of the spec~-~n. ~he brown colour is of ferric ~ d e
~hereas the yellow colcur is of ferric chloride. It is expect__~_that on
the brown ring the ferric hydroxide has a higher concentration and the
VoI. 18, No. 2 197
HCI, MORTAR, ATTACK, ANALYSIS

Ct

i
C

! l
middle o{ 2.0 ¢rn outer
the specimen suwface

Fig. 4. X~ray line analysis diagrams for ClK~, AIKe, SiKe and CaKe using
10 mm long & I mm thick lines mad by EDAX 711.

ferric chlorlc~ has the lokms1: ~ o n . ~ e ,..,~.=,c~G..~,=tlcrl of

ferric hydrmdde 4~=aases with hrzease in the ferric dhloride towards
the outer surface of the p r ~ , ~t~L~ is in contact with the acid.

~he d~mLcal analysis results, dane by AA and E ~ X ~ w a deviati~

fram the ~ c a l values, calculat-~_ on the assumption that the sand
used is pure quarz sand. ~ d s may be ~ue to the 4~:~Ities i n t h e sand,
198 Vol. 18, No. 2
S. Chandra

"P'

., dm~

Fig. 5. Back scattered electron image micrographs taken near

the brown ring by SEM-EDS.

for e ~ D l e it is ~ with f ~ . Further E~%X has s h ~ n l o ~ r

values than AA. ~ d s may be a ~ to the fact that in AA the particular
salt 4. oampletely ~Lamolved, %#Jz~Bs the ~ anal~Ls is dane from
point to polnt ~ the mlnaral. Still t ~ ~ I- the _ - ~ -- ~ x ~ n
by the AA analysis. In zcns 2 C ~ u ~ ring) it is ~ that the cmmcm~-
tratian of alumini~ and L.-c,~ has ~ , the silica ~ t i o n
has decreased a little and the calcham starts d~creeming. ~ may be
~ua to the dlmolutlan of c a l c i ~ salts. In z ~ 3 ~ is adJac~t to
the b r i m ring, silica has ~ a little. ~ may be due to the
f~4-n on nanm~.uhle silica gels. Calc/um and i ~ n ~
Vol. 18, No. 2 199
HCI, MORTAR, ATTACK, ANALYSIS

a) light grey phase

b) grey phase

c) dark greyphase

Fig. 6. EDAXanalyses of
phases taken by back
scattered electron
image micrographs
200 Vol. 18, No. 2
S. Chandra

remarkably. ~ is due to the i_~ching of their soluble salts.

A/ln,~rLium has also ~ btrt rK~t very ~w~. In zone 4 silica and
iron b s c m ~ s t ~ y , aluminium decreases a little but calcium ccmtinues
to decrease substa~4-1 ]y. In zcme 5 the remzlts are more or less the
as in zcna 4. On the basis of theme results the ~ p r ~ can
be wall divided in 3 main z ~ m : (i) u n ~ m m ~ d zone i, (ii) the
~ or as called the ~ mixture zone; brown ring, zone
2 and 3 and (iii) the attacked z~ma; 4 & 5. ~ zone divlsion is quite
in ~ with the remote ~ by ~betekaya et al /9/. ~he X-
ray line dlagrmm (Fig. 4) are very much ~ t / v e and shows the
variation of silica, imp, a/,~nium, calcium and ~loride co~c~__ntra-
tion through out the ~ ~psoi~n. ~ curves are in good agreement
with tha arelyses done ~ AA and ~ X .

Fig. 3 shows that dllcrlde is present only up to the ~ ring. It did

not penatrate further. So the p r ~ will be attacked further only after
the dissolution of the ~ in the ~ ring. Further the
o~-~,~=tion of ii~, and al~minium in the brown ring is ~arked. The
calcium ~ t i ~ is hi~est in the inner part of the b r o ~ ring.
Dissolution ~ in the b~uwn ring area. Just after the brown ring
the ~ t i o n of calcium falls ~ y ckle to the lea~dng of the
soluble salts. ~he a/,~4nit~ cor~m~ration i n ~ a s e s st~a4]y towards
the b r i m ring and tben ~ stsadily. ~he irun cancentraticn has
more than the aluminit~ and decreased _~a~nly after the
brown ring. ~ of the peak of aluminium and iron is more or less
the ~ %~%ich is not very wide. ~ indicates that they are pz-esent
in a vary narrow t h i ~ of the rin~. ~ m s calcium is the dominating
o w r a wide t h i ~ r~ar the b~-,.~nring with silica as the
n~xt ~ and i n ~ and al,~nium in a narrow ranga.

;s in t ~ ~ e oZ the ~ ( ~ ) ~ 2 . 5 and in the acid

z m than z. ~ a ~ gradim~ is ~ , e i ~ ir~id~ the pr~ ~ speclm~n
due to the flow of H ~ and OH- ior~. It is ~ that the different
have a4~fer~nt ~lubility at different ~ values
/1,11,i0,13/. For e~--p1e the silic acid is the one least soluble at ~q
1 (outer surface of our ptH~). At ~ more than 2 the Fe(OH)~ is
ins~_~m4 least soluble and one might ~ o r e expect that this could be
zone 4 in our case. For p~ value 2-4 one might expect to find a zone
with i ~ , and silica inside this and for pH value more than 4 to find
L ~ + a],~-.4','d.t,D,. A z ~ m with all three hydrcv~des is to be found
furth~ inside the prism 0 = ~ n ring) ~ t ~ ~ is 4-7. Zt is
not car~Jln that the aolubility of the ~ are ~d,~:~n-
4~mt of ~m~h ~:her. ~lis fact dk~m not ~ roman that only a purely
mmctmnical mlxture of ~ inthe layer is involved. It is known
that .11 ~ ~ have stm=g ~ m = ~ . i o n ~ ~ and the
mlxtu~ ~ r a t h ~ be ~ as ~ sort of a ~ _ I o n
o ~ p o u ~ . Hazel et al /4/ n o t ~ that if a sLlicic acid-soluti~ was
with an FeCl 3 the remult in both the c a r e w ~ a solution whose
pH value w ~ l o ~ r than thl ~ I = . ~ Indicat~ that the
i=~ ~ cha, ged ~ with m ~ = , m f r ~ th, h y ~ y 1 ~ o u ~ to th,
~ / / c a ~ . ~ can fozm alumlnium silicate ~ a ~ l ~ or F-Si
(~/n~mite zi~m ~ ) . ~ ~ ~ to be ,t~ae in a l~
ran~ ~ 3.5 but the c c m p l ~ ~ y can n o t ~da~c a t a ~ ]=~loW
2.5.

ir[mt which are id~e~Lfled by ~ a ~ t ooloura: l i ~ t grly,

Vol. 18, No. 2 201
HCI, MORTAR, ATTACK, ANALYSIS

and dark grey. I~%X analyse~ (Fig. 5) ~on~ an these Rbasem show that
the light grey phase has calcit~ as the ~n~Inating Rhase with low iron
and silica. 1~e grey p m m e o~t-~ns the s a m ,-~-Yc of calci,~ but
silica is increased and h , ~ , i s found in ~ . In t ~ dark grey phase
calcium is sus'r.~'l,,'~ly ~ ~ r - ~ - ailiam is increased. ~ s all
the four Ca, A1, Fe and Sl are present n ~ r the h~uwn ring in
ai~f~ combinations, making three a~ferent phases. ~ e mlnero-
logical comfx~itian of these Dhases is difficult to assess in this
s~my.

S~em of the differm~ zcmes of the hy~Irodlloric acid treated mortar

specimen in the microscope by using polar!sed Zight (Fig. 7) show that
the a q ~ j a t e s themselves do not interact primarily. ~ can however
~ c z~Lcr~ ,'~-- to the high ~ w . h ~ of the pare water

will tams quite a long time at the t~oerature of the experiment. ~ s

the mineral aggregates are free from ___norrosian. ~%ree major zcr~s are
visible here: a) the irmer u r ~ n ~ zcr~, b) the ~ col(xn~d zcre
and c) the outer, m t ~ l y alter1~ zcl~. 1~e ~ u t ~ a z r b e d zone
m i ~ shows unaffected mortar. ~ e ~ g r e g a t u are malnly quartz
and feldspar. ~ clarifies the d i f f e i ~ e in the theoret/cal and
analysed v a l , ~ by AA and EDAX. ~he cal~,~t-~ v a l ~ s were an the
~ a n that t~e sand used is pure quartz sand, w h i ~ is not
cozrec~. ~he ~ colcured zcr~ is the L-mermcst part where the acid
has been reacting. In this zone, there is a precipitation of M~ and Fe
~ , giving a very ~ v k m~trix a m m 2 ~ the mineral grains. ~xLs
can also be a Fe-Si complex (I~ngsite) as mentioned before. Further
in this zone there is ~ o a tendency of forming rims ~ the
aggregates. ~ can be a l , ~ n i ~ silicat~ as d/scussed before or may
be calclum a l , ~ n i ~ silicates. ~xLs rim formation creates intense
swelling in the zone. ~he outer zone show no i ~ precipitate~ but
a r a 2 ~ all the aggregates a clearly visible rim net is formed. ~ d s
ccmsists of a czystalline substance since it is white in colour under
polarised light. Even the matrix is light coloured im oomparison to the
outer z a n ~ @-- to the higher content of the white phase. ~ d s increa-
ses further swelling in the zoos.

For orlm~atlon purposes ~ o r l c acid ~ s ~ with pure C3A

synthesized in the labara~x=7. After a certain t i m the supernat~4
liquid was decanted and solid was analysed by X-ray dlffractiun. It was
very ~ to note the peak of C3A.CaCI2.Z0H20. ~ d ~ mear~ that
CaCl 2 which is foz-.~ m m to the z-a~tlan of hy~u~,laric acid with
C a ( C ~ r~__~1_ with C3A to for~ ~ double salts. ~xLs proOFs- more
expanslon.

C~r~I~ICNS

~ o r i c acid attacks the clinker materials of Boztland

forming ~ soluble salts, ~>-tly with calcite, ~hich are submequently
l ~ h e d out. ~ e specimen loaees the b i ~ 4 ~ and its Rorasity is
increased. ~ d s way t ~ ~ of the -~id is ~ . ~ y
hy~rulysis is r ~ and e v e n ~ l l y Si, A1 and Fe gels are ~ .
mixture of these ~ ~ ~ in a layer emoting the
~ oancre~. ~ e ~ t l a n of Fe andAl is high in this
region. It is also possible that ~ F-S, A-S or S-A-S oam~lexmm are
f~. Besides this, indicaticms are r-c~_~ved for the lamination of
202 Vo]. 18, No. 2
S. Chandra

a) Inner undisturbed
zone

b) Brown coloured
zone

c) Outer strongly
altered zone

Fig. 7. Micrographs taken

by TM under polarised
l i g h t x 600
Vol. 18, No. 2 203
HCI, MORTAR, ATTACK, ANALYSIS

C~A~Cl 2 10 H ~ by t ~ action of CaC~2 and C3A. ~ i o n caused by the

f~mation of these salts gives rise to d A , ~ ~ ~ in
~ , ~hich fells apart.
~ m s the attack oE ~ c r i c acid on concrete is a physico-chemical
phenumsnmn and can be cate~mrized under A & C classification of
~et,ri=mtion of ~ by ~ i c e l ruction ~ by ~ / 8 / .
study has given a better u n ~ = . U m ~ of the ~ of
chloric acid att~c~ on the ~ mortar. ~ w ~ k is to be dane to
study the mineralogical ~ i t i c r e of different ~ p L ~ , ~ in
d4 ~ferent zones.

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