Research and Development Laboratories

of the

Portland Cement Association

RESEARCH DEPARTMENT
Bulletin 87

Carbonation of Hydrated
Portland Cement

By
G. J. Verbeck

February, 1958

Chicago

Authorized Reprint from

ASTM Special Technical Publication No. 205
 AuthorizedReprintfromthe Copyrighted
Cementand Concrete
S@.ial TechnicalPublicat{oe No. 205
Publishedby the
AMERICAN SOCIETY FOR TES’HNG MATERIAL~
1958

CARBONATION OF HYDRATED PORTLAND CEMENT

BY GEORGE VERBECK1

SYNOPSIS

Existing experimental and physiochemical evidence regarding carbonation

of the constituents of portland cement is reviewed and indicates that sub-
stantially all of the constituents of cement are subject to ultimate carbonation
under ideal conditions.
Humidity during exposure to carbon dioxide appears to bea major factor
influencing the shrinkage directly produced by carbonation. Concentration of
carbon dioxide and size of specimen also have important effects, possibly
produced by indirect changes in humidity within the specimen. Increased
subsequent volume stability to moisture change was obtained by prior car-
bonation.
The influence of high-pressure steam curing procedures (temperatures and
duration) on some physical properties of cement pastes containing siliceous
additions is presented. The amount of water vapor adsorbed at 36 per cent rela-
tive humidity is a measure of the amount and nature of the hydration product
and is influenced by siliceous additions and decreased during curing at ele-
vated temperatures. This fundamental characteristic of the hydration product
is closely related to the elastic modulus, water-loss shrinkage, carbonation
shrinkage, degree of carbonation, and water permeability of the paste.
The strict physiochemical significance of the phenolphthalein color test for
estimating depth of penetration by carbon dioxide gas is questioned.
—

The reaction between carbon dioxide technology and theory of water-loss

gas and hardened portland-cement shrinkage, and an understanding of
pastes, mortars, and concretes is of con- carbonation may aid him in separating
siderable practical and theoretical in- the two causes of shrinkage for more
terest. The slow shrinkage of concrete effective study.
products in service over a long period of An understanding of carbonation in-
time may be explained by this reaction volves both the process and effects of
and may be greatly diminished by in- carbonation, Many factors, such as the
tentional precarbonation. Intentional relative humidity during exposure to
carbonation may also improve the carbon dioxide, carbon dioxide concen-
strength and hardness and reduce the tration, and specimen size are of con-
permeability of concrete products. The siderable importance to both the rate
research worker is interested also in the and degree to which carbonation occurs.
The magnitude of the shirnkage that is
lManager, Applied Research Section, Port-
land Cement Asen., Chicago, Ill. directly produced during carbonation and
17
18 VERBECK ON CARBONATION OF HYDRATED PORTLAND CEMENT
the volume stability of the carbonated
product are of particular concern. The
volume stability and susceptibility to
carbonation of high-pressure steam-cured
products, with and without siliceous
additions, have been found to be very
dependent upon the temperature and
pressure to which the hydrating paste
was exposed and to the duration of this
exposure.
The present report is based on two
separate laboratory studies. One is a
specific study of various factors that
influence the drying and carbonation
shrinkages of mortars cured at normal
temperature. These results should be
qualitatively applicable to concretes.
The other study concerns the effects of
various high-pressure steam curing pro-
cedureson several of the physical proper-
ties of pastes, including carbonation
shrinkage.
The use of pastes and mortars permits
the fabrication of small specimens from
which better observations of the details
of the mechanism of carbonation can be
made than would be possible with the
larger size specimens required for con-
crete.
The research on which this repor~ is
based has not been completed. Subse-
quent reports will more fully describe
the detailed findings,
CHEMICAL PRODUCTS OF CARBONATION
It is important to consider the suscep-
tibility of the various hydrated compo-
nents of ~ortland cement to carbonation
L
in the presence of water, and the degree
of carbonation they attain when exposed
to carbon dioxide at various concentra-
tions or pressures. Although it might be
assumed that only the calcium hydroxide
liberated during the hydration of tri-
calcium silicate in the cement might be
susceptible to carbonation, S. L. Meyers
(1)2has demonstrated that all four of the
major potential calculated compounds in
portland cement will at least partially
carbonate when exposed to carbon
dioxide at high pressure. His failure to
attain complete carbonation in tests
with the separate compounds can per-
haps be attributed to the low porosity of
his specimens and incomplete hydration
of the compounds during the period of
test, The greatest degree of carbonation,
which he calculated as 93 per cent, was
obtained with a neat cement paste of
relatively high porosity (water-cement
ratio, 0.60).
Other investigators, Yoshida (z),
Weberand Mathei (3), and Shideler (4),
have reported on carbonation of pastes
concretes, orconcrete block in which the
amount of carbon dioxide taken up by the
cement is considerably in execss of the
amount that could react solely with the
calcium hydroxide liberated during the
hydration of the calcium silicates.
Steinour (5) has recently studied existing
experimental evidence combined with
physiochemical analysis and has con-
cluded that complete carbonation of port-
land cement (to calcium carbonate and
hydrous silica, alumina and ferric oxide)
is chemically possible even at the low
concentration (low partial pressure) of
carbon dioxide in normal outdoor at-
mosphere, about 0.03 per cent or 0.0003
atmos pressure.
Alkalies:
In hydrated cement pastes the major
materials dissolved in the liquid within
the paste and subject to carbonation are
the alkali hydroxides (sodium and po-
tassium react similarly) and calcium
hydroxide. At advanced stages of hy-
dration with most cements the con-
centration of alkalies in the paste liquid
may be in the range of 0,5 to 1.0 N.
When a solution of sodium hydroxide is
2The boldface numbers in parentheses refer
to the list of references appended to this paper,
see p. 36.
 VERBECK ON CARBONATIONOF HYDRATED PORTLAND CEMENT 19

brought to equilibrium with a carbon the fraction present in the paste liquid,
dioxide atmosphere, the sodium con- although predominately bicarbonate,
stituent can be considered to be a would be negligible because of the low
mixture of sodium carbonate and sodium volubility of calcium compared to the
bicarbonate, the relative quantities at bulk solid calcium carbonate in equi-
equilibrium being a function of the COZ librium with this solution.
pressure and the concentration of alkali
Magnesia and Gy@wn:
ion (6). For example, at the C02 pres-
sure of normal air, 0,0003 atmos, a Steinour (5) has indicated that the
solution containing 1.0 N sodium ion ultimate equilibrium product of MgO in
will be approximately12 per cent as the normal air (C02 pressure about 0.0003
bicarbonate and 88percent as the car- atmos) may be the hydroxide rather
bonate. In a pure COZ atmosphere at than carbonate but at 1 atmos COZ pres-
normal pressure (COZ pressure equal to sure the ultimate product will be the
1 atmos), this solution of 1,0 N sodium carbonate. Gypsum should not car-
ion would be almost 100 per cent as the bonate.
bicarbonate. This change in state of
carbonation should be considered in MORTAR STUDIES
estimating the degree of ultimate car-
Eject of Relative Humidity on Carbona-
bonation attained by study of pastes
tion:
subjected to various COZ pressures.
For the present purpose, it is con- The moisture content (relative humid-
sidered highly probable that the car- ity) of hydrated paste has a considera-
bonates and bicarbonates of sodium and ble and important influence on the rate
potassium hydroxide exist entirely in and ultimate extent of carbonation. An
the aqueous phase (the evaporable understanding of this aspect is valuable
water) within the hydrated cement paste. in the interpretation of various observa-
Complex alkali-calcium carbonate salts tions regarding carbonation and also
have been reported (7), but these pre- because of its theoretical implications.
sumably precipitate only at high con- The apparent relationship between
centrations, higher than perhaps nor- relative humidity and carbonation can
mally occur in hydrated paste. be influenced by specimen size, if the
carbonation proceeds at a relatively
Calcium Compounds: rapid rate, This effect, to be discussed
The situation with calcium hydroxide more fully later, is brought about by
is markedlv different. Even at the low release of moisture within the specimen
pressure o; C02 in the normal atmos- by carbonation. If the specimen is small
phere, the calcium in the liquid phase is or if carbonation proceeds slowly, (low
present predominately as the bicar- concentration of COJ this moisture can
bonate-approximately 97.5 per cent. At diffuse out of the specimen, thereby
higher C02 pressures, the fraction of maintaining the internal relative hu-
bicarbonate in the liquid becomes still midity of the specimen approximately in
more predominant over the carbonate. equilibrium with the external controlled
The solid in equilibrium
. with the cal- humidity, For the purpose of demonstrat-
cium bicarbonate solution at C02 ing the importance of relative humidity
pressures below 15 atmos is calcium on carbonation, results obtained using
carbonate. Considering the total amount small mortar prisms will be considered.
of calcium in a hydrated cement paste, Mortar specimens, 1 by 1 by 11* in.
20 VERBECK ON CARBONATION OF HYDRATED PORTLAND CEMENT

were prepared using a laboratory blend Table I shows some of the results ob-
of equal parts of four ASTM type I tained. This and all subsequent length
cements3 and a siliceous sand from Eau and weight change data herein reported
Claire, Wis. The ratio of cement to sand are based on the average of two speci-
was 1:4.08 and the net water-cement mens unless otherwise noted. This
ratio was 0.54. All specimens were moist information isalsoshown in Fig. 1 where
cured for 7 days at 73 F. After 7 days, it may be seen that during the period in
companion specimens were subjected which the specimens were exposed to
to storage in air freed of C02 (hereafter COZ-free air, substantial shrinkage oc-
referred to as C02-free air) at 100, 75, curred with those specimens exposed to
50, or 25 per cent relative humidity at reduced humidity levels, a normal ex-
73 F. These exposures were continued pectation. However, the relatively small

TABLE I.—EFFECT OF RELATIVE HUMIDITY ON WATER LOSS

AND CARBONATION SHRINKAGE.
lbylb .1~-in. mortar prisms.
Lengthand WeightChangeat RelativeHumidityShown

100~0 RH 7S7. RH 50%RH 257. lW

Length Change, per cent

During COz-freeair drying (52 days). +0.004 –0.045 –0.075 –0.079
During subsequent COZ(FIO days) expo-
sure . . . . . . . . . . . . . . . . . . . . . –0.002 –0.050 –0.092 –0.001

Total . . . . . . . . . . . . . . . . . . . . . . . . . . . . +0.002 –0.095 –0.167 –0.080

During simultaneous drying and C02
expOsure(112 days) . . . . . . . . . . –0.002 –0.077 –0.118 –0.120

Weight Change, per cent

During COj-free air drying. . . –0.93 –4.05 –5.20 –6.30
During subsequent COZexposure. +1.13 +3.85 +3.95 +0.65
——. —.— .— ——
Total, . . . . . . . . . . . . . . . . . . . . . . . . . +0.20 –0.20 –1.25 –5.65

until all specimens had reached apparent 1 I I

‘o’”’ r
equilibrium, both as to weight and o
length, at these various relative humid-
ity levels. After moisture equilibrium --0.04 -
had been reached, which required ap- ~ _ o OG
proximately 52 days, the specimens were ~ _ ““”~
exposed to carbon dioxide at 1 atmos ~- “
pressure, maintained at the same rela- ~ -”. I” -
tive humidity as before, until apparent 0-0.12 -
equilibrium was again attained (an addi- ~ - 0, 14 -
tional 60 days). Some of the specimens ~ -o, ,~
and Subsequent
showed substantial shrinkage, due to
-0.18 - Corbonot,on
carbonation, and simultaneously in-
I I I
creased in weight. 100 75 50 25 0
Relot,ve Humidity, per cent
8Standard Specifications for Portland Ce-
ment (C 150- 56), 1956Supplement to Book of FIG. I.—Effect of Relative Humidity on
ASTM Standards, Part 3, p, 1. Water-Loss and Carbonation Shrinkage,
 VERBECK ON CARBONATION OF HYDRATED PORTLAND CEMENT
difference in shrinkage between 50 and
25 per cent relative humidity perhaps
has theoretical significance, The lower
solid line in Fig. 1 shows the total
shrinkage of these same specimens as
determined after their subsequent ex-
posure to carbon dioxide at 1 atmos
pressure at the same relative humidity
at which they were previously exposed
to drying with COz-free air. The total
combined shrinkage is observed to be
substantially greater for the specimen
maintained at 50 per cent relative
humidity than at the others. No signifi-
cant shrinkage was produced in those
specimens exposed to C02 at either 100
or 25 per cent relative humidity. That
portion of the shrinkage attributable to
carbonation is shown by the dashed
Iinein the figure.
The lack of carbonation shrinkage at
100 per cent relative humidity is ex-
plainable in terms of the diffusion of
carbon dioxide. Carbon dioxide gas will
diffuse readily into adried paste because
its pores are relatively empty and react
rapidly with the large exposed internal
surface under the proper conditions.
However, if the pores of the paste are
filled with water, such asatlOO per cent
relative humidity, this gaseous diffusion
cannot occur, and the gas must first
dissolve in the liquid in the pores and
then slowly diffuse inwards. It improba-
ble that this slow process combined with
the counter-diffusion of calcium ion to-
wards the surface causes the precipita-
tion of calcium carbonate in the surface
pores (clogging) .This mechanism would
account for the lack of significant shrink-
age under high humidity conditions. As
the moisture content of the specimen is
reduced by partial drying, the capillary
pores within the paste become emptied
and more susceptible to penetration of
carbon dioxide by gaseous diffusion and
less susceptible to pore clogging by
precipitation of carbonate.
21
The failure of the specimens exposed
to carbon dioxide at 25 per cent relative
humidity to shrink significantly is per-
haps due to thelowmoisture content of
the paste. It is evident that water is
required for carbonation to occur. At
25 per cent relative humidity, the rela-
tively normal “free” water, the capillary
water, within the paste has been removed
by evaporation, and the remaining water
“adsorbed” on the gel surface may be-
have differently in this catalytic role.
The adequacy of this explanation is
under study. Alternative explanations
may involve study of the exact nature
of this presumed surface-adsorbed water,
the role of increased alkali concentration
(upon drying), and the precipitation of
mixed alkali-calcium carbonate hy-
drates—matters which are not entirely
clear at the present time.
As will be discussed subsequently, this
interesting relationship between car-
bonation shrinkage and relative humid-
ity is revealed only under these somewhat
ideal conditions using small specimens.
With larger specimens, variations may
occur in the relative humidity or moisture
content of various portions of the speci-
men, these variations resulting from
imperfect drying, movement of alkali
ions during drying, and insufficiently
rapid outward diffusion of the water
released during carbonation. Accord-
ingly, with larger specimens the results
obtained may be ambiguous. Future
work will include specimens of still
smaller dimensions (diffusion distance
less than ~ in.) at slower rates of car-
bonation (lower COZ pressures). Un-
der such conditions, the specificity of the
relative humidity—carbonation rela-
tionship may be more pronounced than
presently revealed.
Sequence of DYyiw and Carbonation:
In the tests previously discussed, the
specimens were first dried to equilibrium
22 VERBECK ON CARBONATIONOF HYDRATED PORTI.AND CEMENT

at various relative humidities and then drying with subsequent carbonation at

subjected to carbonation while main- 50 per cent relative humidity produced
tained at these humidities until ap- greater shrinkage than carbonation and
parent equilibrium was again attained, simultaneous drying to 50 per cent
In another group of tests, similar speci- relative humidity presumably because in
mens after the same initial curing the latter circumstance much of the
period, were subjected to simultaneous carbonation occurred when the relative
drying and carbonation by exposure to humidity within the specimen was higher
carbon dioxide (1 atmos pressure) main- than 50 per cent.
tained at the various relative humidities.
A portion of the results obtained are
shown in Table I and in Fig. 2 in com-
‘0”02~
o
parison with previous results.
--0.02
~ -
The relationship shown in Fig. 2 for
simultaneous drying and carbonation
differs considerably from the other curves ?-0.06
%
shown. It is inherent in this procedure Z -0.08 -
of simultaneous drying and carbonation 6
= -0.10 -
that the average relative humidity within s
yc -0.12
the specimen during carbonation will be
higher (because it is still drying) than
the surrounding controlled atmosphere. ‘O. 16 - ?Ow/hg cwd Simultaneous
Subsequent
For those specimens subjected to the -0. IS - Carbonation Corbonotion

drying and subsequent carbonation ~.

procedure, it is interesting that the
shrinkage during carbonation at 75 and
50 per cent relative humidity
–0.050 and –0.092 respectively,
though the weight gains on carbonation
were almost identical (Table I).
The question arises as to whether this
difference means that carbonation at 75
per cent relative humidity gives a prod-
uct of fundamentally less shrinkage, or
whether the difference would be elim-
inated if the specimen carbonated
75 per cent relative humidity were now
dried to equilibrium at 50 per cent rela-
tive humidity. The results shown by the
dashed line in Fig. 2 for the shrinkage
during simultaneous drying and car-
bonation (carbonation at high humidity
but ultimately dried to 50 per cent rela-
tive humidity) seem to demonstrate
that the carbonated product at high
humidities has inherently less shrinkage
even at the same humidity level. That is,
100 75 50
Relative Humidity, per cent
FIG. 2.—Effect of Sequence of Drying and
were Carbonation on Shrinkage.
al-
E$ect oj Specimen Size:
It has been previously mentioned that
specimen size has a considerable in-
fluence on the nature of the results ob-
tained. Various factors appear to be
involved. These factors include the dis-
at tance the water vapor released by car-
bonation must diffuse to reach the outer
boundary of the specimen, the paste
porosity and hence the rate of water
vapor and carbon dioxide diffusion, and
the carbon dioxide pressure. Some in-
formation on this matter has been ob-
tained in the current study.
The previously discussed mortar
specimens were 1 by l-in. in cross-section
and represented a more ideal condition
for reaction than 2 by 2-in. and 3 by 3-in,
 VERBECK ON CARBONATIONOF HYDRATED PORTLAND CEMENT 23

cross-section specimens of similar mortar creep due to internal stresses caused by

treated in exactly the same way. The differential shrinkage (moisture gra-
larger specimens (and most concretes) dients) during drying. This observation,
would represent a composite effect, each with carbonate-free specimens, appears
portion of the specimen shrinking and to have considerable theoretical signifi-
carbonating according to relationships cance.
somewhat as shown in Fig. 1. Under The different carbonation shrinkages

TABLE II,—EFFECTOF SPECIMENSIZE ON WATER-LOSSAND CARBONATIONSHRINKAGES

AT DIFFERENT RELATIVEHUMIDITIES.
,
ShrinkageFor RelativeHumiditymd SpecimenSizeShown,per cent
I
100~0 RH 75% RH 50% RH 25% RH

1 by 2 by 3 by 1 by 2 by 3 by 1 by 2 by 3 by 1 by 2 by 3 by
1 in. 2 in. 3 in. 1 in. 2 in. 3 in. 1 in. 2 in. 3 in. 1 in. 2 in. 3 in.
— — _ _ _ _ _ _ _ _ _
Durr:: ~~;
+0. 004 –0.002 +0.004 -0.045 -0,053 -0.052 -0.075 -O.O82 -0.075 -0.079 -0.084 -0.081
D;r%Y&b-
sequent
C02 expo.
. . . . . . –0.002 +0.003 0.000 –o .050 –0.048 -0.037 -0.092 -0.091 -0,067 -0.001 -(). 060 -o,080
sure
. — — — . . . _ _ _
Total, ,,.. +0.002 +0.001 +0.004 –0.09s –0.101 -0.089 -0.167 -0.173 -0.142 –0.080 -0.144 -0.161

drying conditions, the outer portion of

the specimen might carbonate and
shrink as completely as was previously
observed at50per centrelative humidity
while the center of the specimen would
carbonate under higher humidity con-
ditions, If a specimen was dried to the
stage at which the outer portion was at
25 per cent relative humidity while the
center was at 50 per cent relative
humidity, carbonation could begin at
the center and proceed outwards, propa-
gated by the water released by the in-
ternal carbonation. The results obtained
using specimens of similar mortar butof
various dimensions, revealed some of the
complexity of the situation. Such re-
suits are shown in Table II and Fig, 3.
It may be noted that the ultimate
water-loss shrinkages for the different —
size mortar specimens are in substantial 100 75 50 25 0
Relative Humidity, percent
agreement. This indicates that in a
FIG. 3. —Effect of Specimen Size on water-
COz-free drying atmosphere there is Loss and Carbonation Shrinkage at Different
only a relatively small effect, if any, of Relative Humidities.
24 VERBECK ON CARBONATIONOF HYDRATED PORTLAND CEMENT
observed at the various humidities as a
function of specimen size demonstrate
the difficulties of establishing the funda-
mental relationships involved. It maybe
noted that the carbonation shrinkages of
the various size specimens are approxi-
mately similar for carbonation at rela-
tive humidities above approximately
75 per cent. Considerable variation is
observed at 25 per cent relative humid-
ity. The small 1 by l-in. cross-section
specimens did not shrink and gained only
0.65 per cent in weight. The 2 by 2-in.
cross-section specimens shrank signifi-
cantly but not as much as at 50 per
cent relative humidity, whereas the3by
3-in. cross-section specimens had a
shrinkage greater at 25 per cent than at
any higher relative humidity.
It is believed that theobservedvaria-
tions in carbonation shrinkage are pro-
duced by variations in the average
humidity within the specimen during
carbonation. For example, at 25 per cent
relative humidity all of the specimens
were brought to length and weight
equilibrium with COz-free air prior to
exposure to carbon dioxide. This equi-
librium required considerable time and
the length of time depended upon the
size of the specimen, 52 days for the
smallest and 115 days for the largest
specimens. Although the 1 by l-in.
cross-section specimen did not show
carbonation shrinkage at the 25 per
cent humidity level there was evidence
of some carbonation—the specimen
gained 0.65 per cent in weight during the
subsequent carbon dioxide exposure.
Carbonation reactions are usually con-
sidered to release water, calcium hy-
droxide forming calcium carbonate, and
this released water would tend to in-
crease the internal humidity of the
specimen if the water were not able to
diffuse outward with sufficient rapidity
In the case of the 1 by 1 by 1Ii-in. speci-
men, this water presumably diffused rap-
idly enough to keep the major portion of
the specimen at approximately 25 per cent
relative humidity. In the case of the
larger 3 by 3-in, cross-section specimen,
the moisture released during the initial
stages of carbonation may have been
more completely retained by the speci-
men, keeping the internal humidity at a
higher level and hence promoting further
carbonation and release of additional
moisture.
It is the present purpose to demon-
strate the relatively large effect of
specimen size on carbonation and the
shrinkage produced by carbonation
under certain conditions. Because of the
differences that occur, a wide variety of
“conclusions” could be drawn regarding
carbonation if the effect of specimen size
and COZ concentration were unknown.
As will be discussed later, lower con-
centrations of carbon dioxide should
produce a less rapid reaction and hence
should evolve water at a lower rate.
At low concentrations of carbon di-
oxide, the apparent effects of specimen
size therefore may be considerably less
pronounced than in the present case.
Obviously, future work must investi-
gate these aspects in greater detail. The
practical engineering study of shrinkage
must be concerned with relatively large
cross-sections of concrete. The net re-
sult of carbonation of large cross-sec-
tions appears to be a composite of dif-
ferent effects occurring in various
portions of the specimen.
Weight Changes During Carbonation:
Carbonation of calcium hydroxide
should release 1 mole of water (18 g) per
mole of carbon dioxide (44 g) reacted.
However, the simple analysis of weight
changes cannot be an entirely satis-
factory basis for estimating extent of
carbonation. Whether the water re-
leased by internal carbonation actually
diffuses out of the specimen and whether
 VERBECK ON CARBONATIONOF ~YDRATED PORTLAND CEMENT 25

there have been changes in the water
vapor adsorption capacity of the paste
(alteration of normal gel products and
replacement byhydrous silica, etc.) must
be considered. The chemical determina-
tion of the actual COZ contents of the
specimens would be most satisfactory,
but such data are not yet available for
these specimens. In other tests to be
discussed subsequently, the COZ content
was determined, Inthese additional tests,
for those pastes containing no siliceous
addition, it was found that the water
released per mole of carbon dioxide could
leased per mole of COZ reacted, to permit
estimation of the degree of carbonation
attained. It will be assumed that all of
the CaO originally present in the ce-
ment, except for that present as CaS04 ,
will form the carbonate, and that all of
the alkalies form the bicarbonate. The
MgO will be presumed to be unhydrated
and uncarbonated. The degree of car-
bonation calculated on this basis for
various size specimens exposed under
100 ~

TABLE 111.—ESTIMATED PER CENT

OF ULTIMATE
FLUENCED
CARBONATION AS IN-
BY RELATIVE HUMIDITY
AND SPECIMEN SIZE.
0
al
-’Operce=’.H-
:80
Assuming that 1 mole COl released lmole HZO, z
.-E 60 -
Estimated Per Cent of 5
Ultimate Carbonation ‘S
at Relative Humidity
Indicated ; 40 -
Size of Specimen, in. al
u
I
100707570 50’% 25Y. $
RH RH RH RH ---- -- ----- ------ ___
l—l—l—l— v~a 20 - 100 per cent RH
lbylbyll>~ . . . . . . . . . . . 18 75 77 13
2by2byll>~, ..,,,,,,.. 5 78 93 47 .-?
3by3byll)~ . .,, .,..... 2 72 86 68 1 I
20
,,, 0 I 2 3
Minimum Specimen Dimension, in,
vary from O to 1 mole of water, closely J?IG. 4.—Effect of Specimen Size and Relative
approximating 1 mole water released Humidity on Per Cent of Ultimate Carbonation.
during most of the carbonation period
but approaching O moles of water re- various humidity conditions are shown
leased during the advanced stages (Fig. in Table III and Fig. 4.
8). It is probable that during the early Figure 4 shows that many of the speci-
stages of carbonation the previously mens were substantially carbonated and
hydrated calcium compounds are car- also that specimen size had a pronounced
bonating. Since they are composed of effect on the degree of carbonation par-
the equivalent of calcium hydroxide ticularly at 100 and 25 per cent relative
they have the water to lose during car- humidity.
bonation. During the advanced stages of For the 1 by 1 by 11~-in, specimens at
carbonation, the unhydrated clinker 25 and 100 per cent relative humidity, it
residue may carbonate. Being unhy - is most interesting that substantial
drated, water cannot be lost directly, carbonation occurred, 13 and 18 per
any liquid phase present in the paste cent of ultimate, while these specimens
simply acting as a catalyst for the reac- showed negligible length change, – 0.001
tion. For the present purpose it will be and –0.002 respectively (Table II),
presumed that a mole of water is re- entirely out of keeping with the 0.060
26 VERBECK ON CARBONATIONOF HYDRATED PORTLAND CEMENT

per cent shrinkage caused by 47 per cent Mortar prisms 1 by 1 by 11* in, of
carbonation (2 by 2-in., 25 per cent composition similar to those previously
relative humidity) and the 0.092 per discussed were prepared. After 7 days of
cent shrinkage at 77 per cent carbona- moist curing, these specimens were
tion (1 by l-in., 50 per cent relative subjected to C02-free air storage at 50
humidity), It impossible that these low per cent relative humidity until ap- t
degrees of carbonation, 13 and 18 per parent equilibrium was reached. At !
cent, represent carbonation of the ~hat time; companion specimens were
alkalies, the “free” Ca(OH)z released exposed to carbonation at 50 per cent
during hydration of tricalcium silicate, relative humidity in room air (0.03 per
and the original free lime in the cement. cent C02), and in COz-air mixtures, at
Under this condition the carbonation atmospheric pressure, of 1, 5, 25 and
would affect only the ‘ffree” materials 100 per cent C02 content. Weight and
in the paste and not attack the funda-
mental structure of the calcium silicate
gel hydrate or other gels. Assuming the 0
minimum case in which tricalcium sili-
-0.02
cate upon hydration produces one mole
of “free” calcium hydroxide and hy- -0,04
drated dicalcium silicate gel, it is cal-
culated that 19.9 per cent of ultimate -0.06

carbonation represents the carbonation -0.08 -

of only these “free” materials. These
hydroxides might be drawn from the -0.10 - 100% cot
hydration product and precipitated in + 3.76%
-0.12
. ..—
the capillary paste pores without ex- 0 20 40 60 80 100 120 140
pansion and without attacking the Doys
fundamental structure of the calcium FIG. 5.—Effect of Concentration of Carbon
silicate gel and producing shrinkage. If Dioxide Gas on Carbonation Shrinkage and
Weight Gain, 50 per cent Relative Humidity.
one assumes that the calcium silicate
hydrate produced is in composition
3Ca0” 2Si0.z” *H.zO (8) the degree of length change measurements were made
carbonation attainable from only alkali frequently during this exposure.
and “free” Ca(OH)2 would be greater The results shown in Fig. 5 demon-
than 20 per cent and carbonation to that strate that both the shrinkage and weight
degree without shrinkage could be gain due to carbonation increase signifi-
anticipated on this premise. cantly as the concentration of carbon
dioxide increases. The higher concentra-
Efect oj Concentration oj CarbomDioxide tions produced shrinkage more rapidly.
Gas: The observed differences in shrinkage
All of the above results of carbonation were established within the first 50 days
shrinkage were obtained by exposure of of exposure. Further exposure produced
the mortar specimens to pure carbon only a slow increase in shrinkage of
dioxide gas of atmospheric pressure at comparable amount for the various
the various selected relative humidities. carbon dioxide concentrations. It is
However, some information was obtained apparent that the various specimens are
for exposures to various concentrations approaching some sort of practical
of carbon dioxide gas. equilibrium conditions that are de-
 VERBECK ON CARFJONATIONOF HYDRATED PORTLAND CEMENT
pendent upon the concentration of
carbon dioxide.
Thetheoretical studies of Steinour (5)
have indicated that under ideal condi-
tions it is chemically possible for almost
complete carbonation of portland cement
even in normal air of 0.03 per cent COZ
content. Although it is possible that the
specimens subjected to the different car-
bon dioxide concentrations will even-
tually reach a similar almost complete
stage of carbonation it would appear
more likely that some practical factor,
chemical or physical, has impeded or
prevented the attainment of true chemi-
cal equilibrium’. Humidity may be the
factor which apparently prevents the
attainment of true chemical equilibrium.
The present results can be inter-
preted to indicate that the “true” humid-
ity-carbonation relationship has a pro-
nounced maximum at some relative
humidity higher than 50 per cent and
shows only modest carbonation at a
relative humidity of 50 per cent or below.
This ideal relationship would only be
approached with very thin specimens
(short diffusion distance) or very low
C02 concentrations (slow internal evolu-
tion of water). In the present case, Fig.
5, even though the external relative
humidity was maintained at 50 per cent,
the use of a high concentration of car-
bon dioxide increased the internal humid-
ity (because of the high rate of reaction
and evolution of water within the speci-
men) into the range of pronounced
carbonation and shrinkage. With lower
concentrations of COZ the internal
humidity did not increase sufficiently
above the external atmosphere controlled
at 50 per cent relative humidity to pro-
duce pronounced carbonation and4hrink-
age. With thin specimens at the proper
relative humidity (somewhat above 50
percent), carbonation inroomair(O.03
per cent C02) would therefore be ex-
27
pected to produce as great a shrinkage
as high concentrations of COZ.
E~ect of Carbonation on Subsequent
Volume Stability:
Hydrated portland-cement paste and
hence mortars and concretes ;harme in
length when their moisture cond$ions
are changed in the absence of carbon
dioxide. When hydrated paste is sub-
jected first to wetting and then to drying
in normal air the shrinkage observed
represents a combination of both the
normal water-loss shrinkage and car-
bonation shrinkage. Because of the low
concentration of carbon dioxide in nor-
mal air, the rate of carbonation is low,
and irreversible carbonation shrinkage
is observed over many cycles of wetting
and drying as additional increments of
the paste are carbonated during the
drying portions of the cycles.
Accordingly, a specimen subjected to
alternate wetting and drying will show a
greater length change over the whole
sequence of cycles if during drying it is
exposed to normal air containing carbon
dioxide than if exposed to carbon di-
oxide - free air. However, it is interesting
to determine whether rwior carbonation
increases the subsequent volume sta-
bility of the hydrated paste to moisture
change. It might conceivably be ad-
vantageous for the concrete products
manufacturer to carbonate the product
at some suitable time during the latter
stages of curing, thereby not only elim-
inating long-time shrinkage due to
carbonation during actual service but
perhaps further enhancing the quality of
the material by reducing the nor-real
water-loss shrinkage of the product by
this precarbonation, Shideler (4) has
indicated that a precarbonated product
showed about half of the length change
of a similar but uncarbonated product
when subsequently exposed to alternate
cycles of wetting and drying. However,
28 VERBECK ON CARBONATIONOF HYDRATED PORTLAND CEMENT

in these tests the drying portion of the
cycle involved exposure to normal air at
50 per cent relative humidity which may
have somewhat complicated the inter-
pretation of the results.
Some information regarding the rela-
tive volume stability to moisture change
of carbonated and uncarbonated mortars
is available from the present series of
tests. After an initial ?-day moist curing,
mortar specimens were stored in C02-
free atmospheresat 100, 75, 50, and 25
per cent relative humidity. After equi-
wetting. It may be noted that carbona-
tion improved the volume stability of
these specimens, the expansion on wet-
ting of carbonated specimens ranging
from 96 to 52 per cent of the expansion
of the uncarbonated specimens, Shown in
this table are the estimated degrees of
carbonation of the specimens. It may be
noted that the increased volume sta-
bility caused by carbonation is not di-
rectly related to the amount of carbona-
tion of the various specimens, and this
matter is being investigated further.

TABLE IV.—RELATIVE VOLUME STABILITY OF CARBONATED AND UNCAR-

BONATED MORTARS I’REV1OUSLY DRIED OR CARBONATED AT DIFFERENT
RELATIVE HUMIDITIES.
1 by 1 by 11~-in. mortar prisms.

I1
Ioo% RH
I
1
7S% RFI
I
!
5070 RH
I
25%RH

Length Change, per cent (second wetting)

Uncarbonated specimens. . . .. . +0.050 +0.044 +0.038 +0.046
Carbonated s~ecimens. . +0.048 +0.028 +0.021 +0.024
Relation of length change, of carbonated
to uncarbonated specimens. per cent 96 64 55 52
Carbonation (estimated), per cent. . 18 75 77 13

librium had been attained, half of these PASTE STUDIES

specimens were exposed to carbonation
High-PYessuYeSteam Cwing:
at these same humidities. Information
on these specimens has been previously High-pressure steam curing normally
discussed and reported in Table I. The improves the volume stability of con-
remaining half of the specimens were crete products. The mechanism by which
kept in the various C02-free atmospheres this improvement is accomplished ap-
until all the specimens exposed to car- pears related to alterations in the chemi-
bon dioxide had attained equilibrium. cal nature of the cement hydration prod-
At that time, 112 days, both sets of uct and the physical state of this product,
specimens, those carbonated and un- whether of very high surface area (gel
carbonated, at the various humidity like) and hence of high volume change
levels, were subjected to alternate wet- characteristics or of low surface area and
ting in water and drying in C02-free air hence more stable.
at 50 per cent relative humidity. Some laboratory observations tended
The expansions observed during the to show that the typical high-pressure
second wetting cycle of the various steam-cured product was relatively im-
specimens are shown in Table IV. These mune to carbonation, and experiments
values represent the difference between were made in this connection.
equilibrium lengths during the air dry- An experimental program designed to
ing portion of the cycle (50 per cent reveal the influence of high-pressure
relative humidity) and the subsequent steam curing on the properties of the
 TABLE V.—RESULTS OF TESTS OF PASTES CONTAINING SILICEOUS ADDITIONS AND SUBJECTED TO VARIOIJS
HIGH-PRESSURE STEAM CURING PROCEDURES.
Tam Net Water Ad- Weight Water Ad-
Average Modulus of sorption at length Change Actual Per Cent
pera- Weight ,engtb Change
[ncrease of Ulti- sorption at
Hours at Fly Ash, ;pecimen Elasticity {6 per cent on Drying, Loss on I Carbonation 202 COn-
ture, 1Carbon mte Car $per cent RHb
Temperature per cent Weight .t 5 days, psia Hat 5 days per cent hying, g per cent tent, g after Carbon-
deg ation, g bonation
Fahr t 5 days, per centb ation, per cent

73 Continuous 0 362.5 2.27 X 106 6.22 –0.302 35.8 –O. 125 48.0 76.0 56 6.14
73 Continuous 10 362.5 2.00 5.80 –0.304 44.8 –0.290 58.0 88.4 70 5.58
73 Continuous 20 357.5 1.93 5.09 –0.284 45.5 –0.298 54.5 81.8 74 5.61
73 Continuous 30 351.5 1.73 4.67 –0.264 50.5 –0.398 50.5 73.5 74 5.52
212 3 0 360.0 1.84 5.43 –0.164 46.8 –O. 189 59.0 83.7 62 5.71
212 3 10 360.5 1.68 5.40 –0.170 50.5 –0.337 62.5 86.1 68 6.11
212 3 20 353.5 1.86 5.44 –0.219 48.3 –0.413 61.5 81.0 73 6.56
212 3 30 348.5 1.92 5.12 (–0.223)’ 47.0 –0.497 57.5 73.9 75 6.78
212 24 0 358.5 1.88 5.54 –0.115 49.3 –0.200 59.2 81.0 60 5.53
212 24 10 359.5 1.92 5.59 –0.122 52.0 –0.343 64.0 83.9 67 6.25
212 24 20 356.5 2.15 5.35 –0.158 48.5 –0.398 61.8 81.5 74 6.74
212 24 30 353.5 2.06 5.03 –0.152 48.5 –0.553 57.5 73.6 75 6.78
325 3 0 361.0 1.57 2.91 –0.056 56.5 –0.291 69.0 85.1 63 —
325 3 10 359.0 1.52 3.21 –0.068 62.0 –0.363 59.2 65.0 52 5.42
325 3 20 354.5 1.65 3.62 –0.092 73.8 –0.413 61.2 70.1 64 5.82
325 3 30 358.5 1.72 3.95 –0.135 67.5 (–0.431)’ 60.2 67.9 69 6.39
325 24 0 358.0 1.22 0.44 –0.005 70.0 –0.007 7.8 8.5 6 0.76
325 24 10 361.5 1.17 0.41 –0.006 76.5 –0.003 5.0 7.8 6 0.80
325 24 20 358.5 1.16 2.08 –0.042 73.8 –0.227 46.8 49.9 45 4.14
325 24 30 360.5 1.83 3.92 –0.088 67.5 (–0.431)’ 57.2 62.5 63 6.50
420 3 0 355.5 1.16 0.53 –0.003 69.5 –0.005 8.0 12.5 9 0.79
420 3 10 355.5 1.16 0.54 –0.004 73.5 –0.013 10.0 14.9 12 1.12
420 3 20 352.0 0.65 2.44 –0.035 74.5 –o. 195 37.5 40.5 37 3.66
420 3 30 355.5 1.85 4.69 –0.046 69.0 –0.473 48.0 51.3 52 5.47
420 24 0 358.5 1.14 0.43 –0.004 67.5 –0.006 8.0 11.9 9 0.72
420 24 10 357.5 1.14 0.34 –0.005 72.0 –0.006 6.5 12.0 10 0.75
420 24 20 359.0 0.60 0.88 –0.008 80.5 –0.080 23.2 21.8 20 2.16
420 24 30 351.5 1.35 2.88 –0.018 74.5 –0.387 45.2 41.2 42 4.68

“ Sonic method.
6Per cent of total water held per unit of cement at 36 per cent relative humidity minus per cent nonevaporable water per unit of cement in equi-
librium with ice at COZ temperature.
c One specimen only.
 -.
30 VERBECK ON CARBONATIONOF HYDRATED PORTLAND CEMENT

product is under way at the present time this time, the water permeability, non-
which includes some aspects, that di- evaporable water content, and water
rectly concern the matter of carbona- vapor adsorption at 36 per cent relative
tion. Because of the general nature and humidity were determined using com-
interest of the results obtained to date, panion specimens.
some of the results are reported at this After the specimens had attained
time. equilibrium at 50 per cent relative
Companion neat cement paste speci- humidity, they were all exposed to car-
mens (1 by 1 by 1Ii in.) containing O, bon dioxide gas at 1 atmos pressure at
10, 20and30 per cent fly ash were pre- 50 per cent relative humidity, length
pared with a water to cement plus fly and weight changes being recorded dur-
ash ratio of 0.40 by weight. A siliceous ing these exposures. After equilibrium
was attained in the carbon dioxide
$ exposure, the COZ and water content of
,&
u
‘E. 7~ th; various specimens were determined
f Oper cent 1 chemically and the nonevaporable water
10per cent

h’
-- .- content and vapor adsorption (36 per
cent relative humidity) again measured.
. . . ..----””6
.... The CO, content was determined by
f“ ‘..<3Oper cent
30per cent ~% F& Ash acid digestion of the paste sample, the
20per cent ‘% evolved COZ being dried and absorbed
“x% on soda-lime which was weighed.
20per cent The results obtained proved very in-
F& Ash
\\ I structive, and that portion of the in-
formation available “at this time and
directly pertinent to the problem of
carbonation is shown in Table V.
The amount of water vapor adsorbed
Continuous 24 hr 24hr 24 hr
at 36 per cent relative humidity is a
FIG. 6.—Effect of Fly Ash Additions on
Amount of Hydration Gel (as Evaluated by measure of the amount and physical
Water Sorption) Produced with Pastes Exposed character of the products of hydration
to Different Curing Temperatures. (9). For normally cured pastes the
hydration product is primarily colloidal
addition is a necessary adjunct for high- or gel-like and is highly adsorptive. For
-pressure steam-cured products. After such pastes, the water vapor adsorption
one day of moist curing, companion of the paste increases as hydration pro-
specimens were subjected to different ceeds, However, for pastes subjected to
moist or steam curing conditions as high-pressure steam curing, the nature
follows : of the hydration product is altered from
Continuous curing at 73 F, the colloidal type toward a product that
3 or 24 hr exposure at 212 F, is more microcrystalline and hence less
3 or 24 hr exposure at 325 F, and adsorptive (lower surface area). It is
3 or 24 hr exposure at 420 F. interesting to observe the relationships
After such treatment, all specimens that exist between this fundamental
were stored in water until the age of measure of the hydration products, the
about 5 to 6 days, at which time they water adsorption at 36 per cent relative
were all exposed to drying in C02-free humidity, and the temperature at which
air at 50 per cent relative humidity. At the paste was cured for the mixes con-
 V13RBEcK ON UARBONATION OF HYDRATED PORTLAND CEMENT 31

I I I I I I 1 I 1 I 1 i

(b)

5 -0.1 325 and 420F

u
za 73 F
h
z -0.2 A
0 t

A ● *

2/2
A
0
“~i

100

90
t

e al

z so
/
b —n ./ ‘: <
● E
/0
● : 40 /. Equilibrium’
\
/ not Fully
z
30 Attoined ?
z /1
a!
v 20 “/’
k /
(c) a (d)
10 ~
\
1 I I I I I
01234567 ‘01234567

Per cent Water Vapor Sorption at 36 per cent Relative Humidity

FIG. T.—Relationships Between Water Vapor Sorptions and Other Characteristics of High-
Pressure Steam-Cured Pastes,

taining different amounts of fly ash cured at 73F, at the age of about six
addition. days, additions of fly ash progressively
Such relationships for the specimens reduced the water vapor adsorption
cured continuously at 73F or subjected values. For those specimens exposed toa
to 24hr of curing at 212, 325, or 420F period ofcuring atelevated temperatures,
meshown in Fig. 6. For those specimens particularly 24 hr at either 325 or 420 F,
32 VERBECK ON CARBONATIONOF HYDRATED PORTLAND CEMENT

the situation was reversed. Pastes with between the modulus of elasticity and
O or 10 per cent fly ash showed an al- the sorption values, Specimens contain-
most negligible vapor adsorption. Addi- ing large quantities of colloidal gel (high
tionsof20and30 percent fly ash under adsorptions) had high elastic moduli.
these. exposures increased the observed Figure 7(c) shows that the drying
surface adsorption values. At high- shrinkage (first cycle of drying) is also
pressure steam-curing temperatures, the a general function of the amount of
siliceous addition was required for the colloidal product present. The carbona-
paste to retain a portion of the hydration tion shrinkages (Fig. 7(b)) appear more

80 I
- Oper cent Fly Ash

60 -

40 -

m
.E- 20
s

50
~ 80 1
20per cent Fly Ash
g
E
“: 60
$

$0
40 -

20 -

0
0 20 40 60 80 0 20 40 60 80 100
Actual C02 m Specimens, g Actual C02 in Specimens, g
FIG. 8.—Effect of Siliceous Additions on Water Released During Carbonation.

product as colloidal gel, The results in- complex and seem to be a function of the
dicate that a long exposure at high tem- amount of colloidal hydration product
perature could be expected to convert (as measured by water sorption) and
most of the colloidal gel to coarser ma- of the curing temperature. The degree
terial even in the presence of substan- of carbonation of the various specimens
tial amounts of siliceous materials. is also related to the amount of colloidal
Figure 7 demonstrates that many of product present. This is shown in Fig.
the physical properties of these pastes 7(d) .
are related in a general way to the The general conclusion to be reached
amount of colloidal hydration product from these resultsat the present time is
present in the various specimens. Fig- that high-pressure steam curing reduces
ure 7(a) shows a general relationship the amount of colloidal hydration prod-
 VERBECK ON CARBONATION OF HYDRATED
uct of the cement, the amount actually
produced depending upon the time and
temperature history of the cycle and pre-
sumably upon the characteristics of the
cement and siliceous addition. Siliceous
additions increase the amount of colloidal
product for pastes cured at high tem-
~eratures.
. direct
Pastes containing only small amounts
of colloidal product (low water adsorp-
tions) show low water-loss shrinkages,
carbonation shrinkages, and moduli of
elasticity, and carbonate to onlya small
degree. Subsequent studies will deter-
mine whether these pastes having low
water adsorptions would show increased
carbonation and carbonation shrinkage
when tested at a relative humidity higher
than the 50 per cent used in these tests.
Pastes containing large amounts of
colloidal products have improved modu-
lus of elasticity (presumed improved
strength), increased shrinkage upon
drying, will carbonate to a relatively
high degree, and hence shrink more due to
carbonation.
The water permeability of these pastes
follows a similar pattern. The paste
with the greatest amount of colloidal
product (73 F,O percent fly ash) hada
permeability coefficient of about 1 X
10–12 cm per sec. The pastes with the
smallest amount of colloidal product
(325F, 24hr 10 per cent fly ash and
420F, 24 hr 10 per cent fly ash) aver-
aged about 1 X 10–6 cm per see, a ten
miliionfold change.
WateY Loss Dunkg Carbonation:
These paste data permit study of an-
other interesting point regarding car-
bonation. The carbonation of hydrated
calcium compounds in cement might be
expected to release 1 mole of water per
mole of carbon dioxide combined.
Since the amount of calcium in cement is
very predominant over the alkalies and
magnesia (which possess somewhat dif-
PORTLAND CEMENT 33
ferent stoichiometry when carbonated at
1 atmos COZ pressure), we can for sim-
plicity assume a 1:1 mole ratio of water
released to carbon dioxide reacted.
The observed weight change of the
specimens during carbonation and actual
weight of carbon dioxide reacted (by
specimen analysis) shown in
Table V, can be used to determine the
validity of this premise. Figure 8 shows
the relationships obtained between
these factors for the specimens contain-
ing different amounts of flyash. It may
be noted that for pastes containing no
fly ash, approximately 70 g of COZ were
reacted under the theoretical conditions,
with the release of 1 mole of water per
mole of COZ . Carbonation in excess of
this amount resulted in a rapidly re-
duced release of water. The slope of the
line beyond this point actually indi-
cates a high adsorption of water with
progressive carbonation. However, the
relationships for those specimens con-
taining 20 and 30 per cent fly ash were
completely reversed. For the lower de-
grees of carbonation (actual COZ gains
up to about 40 to 50 g), water was
neither gained or lost as the COz reacted.
However, water was lost during more
advanced stages of carbonation.
Further tests and study are required
regarding this matter which has con-
siderable theoretical significance, but for
the present purpose it is primarily in-
cluded to demonstrate that the amount
of water released during carbonation is
variable and in these tests ranged from
O to 1 mole of water per mole of COZ
combined.
EJect oj Carbonation on Amoud of
Hydration Gel:
It was previously mentioned that the
water vapor adsorption measurements at
36 per cent relative humidity indicated
the amount and character of the col-
loidal gel product within the various
34 VERBECK ON CARBONATIONOF HYDRATED PORTLAND CEMENT

specimens. The adsorption characteris- and presumably uncarbonated paste.

t.icsof the various paste specimens were This red zone usually extends to within
determined before the specimens were ~ to & in. of the outer specimen surface)
dried (age about 5 days) and after the colorless zone indicating “car-
carbonation (age about 125 days). As bonated” paste, that is, paste in which
may be seen in Table V the water vapor the hydroxyl ion was presumably re-
sorptions at 36 per cent relative humid- placed with insoluble, less alkaline,
ity were practically always somewhat carbonate. Numerous conclusions have
higher after carbonation of the speci- been drawn from such tests, but it has
mens. been recently demonstrated (12) that
extensive carbonation can occur well in-
G02 Pressure, Atmospheres side the carbonation interface indicated
I I 1 1 I I by the phenolphthalein color test.
o. It is the present purpose to demon-
strate the lack of strict physiochemical

‘::s
significance of the phenolphthalein color
test and indicate that any colorless zone
is difficult to explain even for completely
carbonated (at COZ pressure in normal
air) cement pastes, unless other altera-
tions have also occurred.
In Fig. 9 is shown the pH calculated
................>.< .
.....-.< .............. .. ...... for various solutions as a function of the
9 .
‘z. . ..” pressure of carbon dioxide with which
.; 10 -, “#’.: Phenolphtholein 1 the solution is in equilibrium (s). The
.“
“End - Point” curves shown are those for water, for
z II
PH 8.0- Colorless solutions containing calcium ion, for
I 12 - PH 9.8- Red -1
solutions containing both calcium and a
+———’——J-4 -3 -2 -1 0 +1 low concentration of potassium ion, and
I_Oglo C02 Pressure, Atmospheres for a 1.0 N solution of potassium ion.
This latter concentration of potassium
FIG, 9.—Effect of Solution Composition on
Equilibrium pH at Different COZ Pressures. ion is well within expectation in the
liquid in partially dried cement paste
prepared with cement of commonly oc-
PHENOLPHTHALEIN COLOR TEST
curring alkali contents. The data repre-
A phenolphthalek color test k fre- sent complete attainment of equilibrium
quently used to estimate the depth of at the COZ pressures shown. In addition,
penetration of carbon dioxide in various the figure includes the pH at which the
types of portland cement specimens color change of phenolphthalein occurs.
A standard procedure has been to
(10, 11). At a pH of 8.0 this indicator is colorless.
fracture the concrete specimen, apply With increasing pH (higher alkalinity)
phenolphthalein indicator to the frac- the color becomes increasingly red with
tured face and determine the depth from maximum color development at a pH of
the specimen surface that was demarked about 9.8. In clear aqueous solution, the
by the red-white color change of the pink color is detectable slightly above
specimen. Usually the central core of pH 8.0. It is difficult to determine the
the specimen has been observed to red- exact pH at which color would be ob-
den the indicator, indicating high basicity served against the color of portland ce-
 VERBECK ON CARBONATION OF HYDRATED
ment but this would presumably be pH
9.0 to 9.5.
The figure demonstrates that lime,
carbonated to equilibrium with even the
low COZ content of normal air, should
show a slight tinge of color under ideal
conditions but a color perhaps not de-
tectable on hydrated cement paste. How-
ever, since all cements contain sodium
and potassium compounds, soluble in the
paste liquid, it is difficult to understand
how the phenolphthalein can remain
colorless when in contact with cement
paste completely carbonated to equilib-
rium with normal air. A saturated paste
made with a cement of 0.50 Na20 equiva-
lent would have an alkali ion concen-
tration of about 0.5 to 1.0 N. The exact
concentration would depend upon the
water-cement ratio of the paste and the
degree of hydration and alkali release of
the cement. Partial air drying of this
paste could easily increase these con-
centrations by a factor of two or three.
The resulting alkali ion concentrations
even when fully carbonated in normal
air should show high pH and hence a red
phenolphthalein color test. Since color-
less zones are frequently observed around
the periphery of specimens subjected to
thephenolphthalein test, these consider-
ations suggest that the occurrence of this
colorless zone maybe also related to the
leaching of alkalies from the surface region
of the specimen in addition to the depth
to which some very high degree of car-
bonation has occurred.
SUMMARY AND CONCLUSIONS
Carbonation of hydrated portland-ce-
ment pastes may result in improved
strength, and hardness, and reduced
permeability. Irreversible shrinkages and
weight gains occur on carbonation, and
the carbonated product maypossessim-
proved volume stability to subsequent
moisture change.
The present paper primarily concerns
PORTLAND CEMENT 35
these length and weight changes of mor-
tars and pastes during carbonation, Al-
though the experimental work contained
in thepaper has not been completed, the
nature of the results obtained to date
warrant presentation because of their
practical and theoretical significance and
as an aid to other investigators.
Experimental and physiochemical ev-
idence regarding carbonation of the con-
stituentsof portland cement is reviewed.
This evidence indicates that substan-
tially all of the constituents of cement
are subject to ultimate carbonation and
that the exact nature of the carbonated
product depends upon the pressure of
carbon dioxide to which the constituents
are exposed.
Experimental results indicate that
carbonation proceeds slowly and pro-
duces little direct shrinkage at relative
humidities of 100 and 25 per cent. Under
specific conditions, maximum carbona-
tion shrinkage is observed at about 50
per cent relative humidity. The sequence
of drying and carbonation also has an
important effect on shrinkage.
The size of specimen is an important
factor during the process of carbonation
under the conditions of the tests de-
scribed. Larger specimens carbonate and
shrink considerably when exposed at 25
per cent relative humidity, presumably
because of the failure of specimens to
maintain equilibrium with this external
humidity during the process.
Concentration of carbon dioxide in the
exposure atmosphere can also have a
considerable influence on carbonation,
presumably an indirect result of its effect
on internal humidity.
In these tests, the prior carbonation
improved the volume stability of mor-
tars to subsequent moisture changes.
The influence of various high-pressure
steam curing procedures (temperatures
and durations) on various physical prop-
erties of cement pastes containing sili-
36 VERBECK ON CARBONATIONOF HYDRATED PORTLAND CEMENT

ceous additions are presented. The readily apparent physiochemical baski

amount of water vapor adsorbed at 36 and presumably indicates a combined
per cent relative humidity is a measure net effect of extensive carbonation and
of the amount and nature of the hydra- leaching of alkalies.
tionproductand isinfluencedby siliceous In the general aspect, this work indi-
additions and decreases during curing at cates that many factors influence the
elevated temperatures. This fundamental process and effects of carbonation and
characteristic of the hydration product that future studies should be conducted
appears to be closely related to the elas- with these in mind.
tic modulus, water-loss shrinkage, car-
bonation shrinkage, degree of carbona- Acknowledgments:
tion, and water permeability of the paste.
Paste of low sorption properties (crystal- The experimental work reported in
line) have low water-loss shrinkages and this paper represents the combined effort
do not carbonate significantly, but tend of Eduards Venters, Paul Klieger, Robert
Landgren, Albert Tucek, and the author.
to have reduced moduli of elasticity and
presumably reduced strength. Specimens The careful work of P, S. Limaye of the
of high elastic modulus contain signifi- Associated Cement Co., Ltd., Bombay,
cant quantities of hydration gel and India working in our laboratories during
hence shrink due to changes in moisture the initial phase of the tests of high-
condition and are susceptible to carbona- -pressure steam-cured pastes is greatly
tion. appreciated.
Physiochemical calculations form a A more complete presentation of the
basis for evaluation of the phenolphtha- results of these various tests reported and
lein color test frequently used to estimate other tests at present under way, will be
penetration of carbon dioxide in concrete. made in subsequent reports on this proj-
It appears that this color test has no ect.

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