CEMENT and CONCRETERESEARCH. Vol. 4, pp. 69-76, 1974. Pergamon Press, Inc.

Printed in the United States.

CARBONATION

OF HYDRATED

CALCIUM

SILICATES

J. N o r m a n M a y c o c k and Jan Skalny

Martin Marietta Laboratories
Baltimore, Maryland ZlgZ7

(Communicated by L. E. Copeland)
(Received Aug. 28, 1973)
ABSTRACT

Mass spectrometric-thermogravimetric
a n a l y s e s h a v e been c o m p l e t e d on d e c o m p o s i n g c a l c i u m s ~ ! i c a t e h y d r a t e s p r o d u c e d in t he
p r e s e n c e of g a s e o u s CO 2 and CO~- i o n s . T h e s e dat a c l e a r l y show
a s t r u c t u r e d e v o l u t i o n of w a t e r d u r i n g d e c o m p o s i t i o n of t he c a l c i u m s i l i c a t e h y d r a t e s . T h e e v o l u t i o n of CO 2 is c o m p l e x . M o s t
of it c o m e s f r o m t h e d e c o m p o s i t i o n of CaCO 3, but p e a k s a s s o c i a t e d w i t h two o t h e r p r o c e s s e s a r e o b s e r v e d at t e m p e r a t u r e s l o w e r
t h a n t he CaCO 3 d e c o m p o s i t i o n t e m p e r a t u r e .
One of t h e s e m a y be
a t t r i b u t e d to s u r f a c e d e s o r p t i o n of CO 2, and t he o t h e r to d e c o m p o s i t i o n of t h e m i n e r a l s c a w t i t e , C a 7 S i 6 O z l H 6. CO 3, f o r m e d d u r ing h y d r a t i o n . B e c a u s e CO 2 and H 2 0 a r e e v o l v e d s i m u l t a n e o u s l y ,
i s o t h e r m a l d e c o m p o s i t i o n d a t a m u s t be i n t e r p r e t e d w i t h c a u t i o n if
m e a n i n g f u l a c t i v a t i o n e n e r g i e s a r e to be d e r i v e d .

M a s s e n s p e k t r o und - t h e r m o g r a v i m e t r i s che A n a l y s en w u r d e n d u r c h g e f ~ h r t an z e r f a l l e n d e n K a l z i u m s i l i k a t - I - I y d r a t e n , die in G e g e n w a r t

y o n g a s f o r m l g e m CO 2 und CO~- I o n e n h e r g e s t e l l t w o r d e n w a r e n .
Die B i l d u n g yon W a s s e r e r f o l g t m i t d e u t l i c h u n g l e l c h f o r m l g e r
G e s c h w i n d i g k e i t . Die B i l dung von CO 2 i s t ei n k o m p l i z i e r t e r r o t gang. D a, s m e i s t e CO 2 i s t Z e r f a l l s p r g d u k t des CaCO 3, a b e r
B i l d u n g s t o s s e w u r d e n a u c h b e o b a c h t e t bei T e m p e r a t u r e n u n t e r h a l b
tier C a C O 3 Z e r f a l l s t e m p e r a t u r und m u s s e n auf a n d e r e P r o z e s s e
z u r ~ c k g e h e n . E i n e r d i e s e r P r o z e s s e s o l l t e A b s t o s s u n g yon CO 2
y o n d e r M a t e r i a l o b e r f l ~ " c h e s e i n , d e r a n d e r e Z e r f a l l des M i n e r a l s
S c a w t i t e , C a _ S i 6 0 2 1 H L . COB , d a s w ~ h r e n d d e r H y d r a t i o n g e b i l d e t
w i r d . Da C(J Z und HZ~5 g l e [ c h z e i t i g g e b i l d e t w e r d e n , m u s s m a n
m i t V o r s i c h t v o r g e h e n , w e n n m a n aus M e s s e r g e b n i s s e n ~ e r
i s o t h e r m e n Z e r f a l l die E n e r g i e a u s t a u s c h v o r g ~ n g e a b l e i t e n w i l l .
II

69

I1

70

Vol. 4, No. l
CARBONATION, CALCIUM SILICATE HYDRATES, MASS SPECTROSCOPY,THERMOGRAVIMETRY
Introduction
T h e hydration of clinker minerals is a difficult process to describe

with precision by chemical s y m b o l i s m .

This is especially true w h e n the

possible reactions between C3S and H 2 0 are considered---liquid state reactions, solid state reactions and heterogeneous reactions m a y
viding a variety of products,

all occur pro-

such as Ca(OH) 2 in solution or as a precipitate,

and calcium silicate hydrates (CSH) of various chemical structures and stabilities.
If C O 2 also is involved in the reactions, either in gaseous f o r m or as
an admixture in the f o r m of C O ~ creased still further.

ions, the complexity of the s y s t e m is in-

Nevertheless,

C O 2 additions are of great interest f r o m

both scientific and technological viewpoints.

The use of C O 2 gas to produce

accelerated curing of cementitious systems is increasing, and has been extensively discussed (i-5), as has the addition of COZ~ - ions in the f o r m of the
alkali carbonates (6-11).

M o s t of the studies reported have been concerned

primarily with the effects of such additions on the morphology,

hydration

rates and mechanical properties of the c e m e n t paste.

However,

detailed discussions of the specific chemical reactions re-

suiting f r o m the addition of C O p or C O

ions are infrequent, primarily be-

cause it is convenient to a s s u m e that their only m a j o r effect is to greatly enhance the rate of formation of C a C O 3.

That carbonate formation is facilitated

is certainly true -- but the type of carbonate f o r m e d often is not crystalline

calcite.

Cole and K r o o n e (IZ) w e r e the first to investigate in detail both the

physical and chemical effects of carbonation.

Their study w a s a consequence

of the fact that the quantity of calcite detected by X - r a y diffraction and

differential thermal analysis (DTA) m e t h o d s w a s always far less than would
be a s s u m e d present on the basis of a m o u n t of C O 2 recoverable f r o m the
samples (13). Cole and K r o o n e (12) used D T A ,

thermogravimetric

(TG) and

X - r a y diffraction m e t h o d s to s h o w that the greater part of the C O Z taken up by

samples of m o r t a r and calcium silicate hydrate is not held as well crystallized calcite, but as poorly crystallized vaterite, aragonite and calcite. T h e y
analyzed their X - r a y results to identify the presence of such CO2-containing
silicate minerals as scav~ite ( C a 7 S i 6 0 2 1 H 6.CO3),
and tilleyite (Ca 5 [Si207] [ C O 3] Z).
could not be present in large amounts.

spurrite

Ca5(SiO4) 2 C O 3

Their data s h o w e d that these minerals

Due to their limited sensitivity, h o w -

ever, the X - r a y data do not exclude the possibility that poorly crystallized or
amorphous

silicate minerals containing C O Z could also be f o r m e d under

Vol. 4, No. l
71
CARBONATION, CALCIUM SILICATE HYDRATES, MASS SPECTROSCOPY, THERMOGRAVIMETRY
carbonating conditions.

This w o r k confirmed that there w a s insufficient

C a ( O H ) 2 present to account for all the C O 2 taken up by the m o r t a r in the f o r m

of C a C O 3, so that there m u s t also be carbonation of the hydrated silicate
minerals to m e e t the C a O deficiency.
T h e incomplete accounting of the sinks for C O 2 p r o m p t e d the present
investigation.

To clarify the situation, however, requires that C O Z detection

techniques be available.

A s s u m i n g that both C O 2 produced as a consequence

of the thermal decomposition of CO3-containing minerals, and adsorbed C O 2

will be liberated if a carbonated s a m p l e is heated to I000C at an appropriate
heating rate, then one of the m o s t sensitive w a y s of detecting this C O 2 will be
via m a s s

spectrometry (MS).

simultaneous T G - M S

This paper reports therefore, the results of

analyses of the decomposition of silicious minerals

hydrated in the presence of either C O 2 gas or C O

ion admixtures.

Experimental
Materials.
C 3 S having a surface area of ca. 3500 c m Z / g

(as m e a s u r e d by the

Blaine method), and a free C a O content of 0.06%, w a s used ~n this study.

Hydrated samples w e r e prepared by mixing C3S with 0.5 parts by weight of
distilled water containing either 0 or 5% of K z C O 3.
6 days at 3 5 C and 1 0 0 % relative humidity (RH).

S a m p l e s w e r e cured for

F o r comparison, a C3S

m o r t a r s a m p l e hydrated under gaseous carbonation for 81 rain at 50% R H w a s

kindly supplied by J.F. Young, University of Illinois.
The s a m p l e s of K z C O 3 ,

C a C O 3 and Ca(OH)2 used as controls for M S

analysis w e r e of Fisher reagent grade quality.

Analztical Technique.
T h e simultaneous T G - M S

analysis w a s p e r f o r m e d by m e a n s of a

Mettler T h e r m o a n a l y z e r i m a t e d to a Balzers Quadrupole M a s s Spectrometer

QMC

101, with the spectrometer probe installed in the cold trap cell location

on the T h e r m o a n a l y z e r .
Typically, 50-100 m g of s a m p l e w a s placed in the tg cup of the
t h e r m o a n a l y z e r and the T G - M S

unit evacuated to -10 -5 Torr.

The sample

w a s then heated at 15C rain "I in a continuously p u m p e d v a c u u m .

to 50 w e r e scanned every 20C.

Masses

U n d e r the experimental conditions employed,

the cracking patterns of H z O and C O 2 were:

72
Vol. 4, No. l
CARBONATION, CALCIUM SILICATE HYDRATES, MASS SPECTROSCOPY,THERMOGRAVIMETRY
H20

: - m/e

18 -

I00.00

17 -

27.01

16 2 -

CO 2 : m/e

44 -

I00.00

28 -

8.85

3.07

16

8.04

0. i0

12 -

5.80

T o achieve high sensitivity on the C O 2 - 44 peak, the top of the

H20

- 18 p e a k w a s lost. H o w e v e r ,

ing range.

Therefore,

refer to the m / e
peak.
m/e

the H 2 0

- 17 p e a k w a s within the record-

in the following discussion of H 2 0

evolution, the data

- 17 p e a k only, this being 2 7 % of the height of the m / e

Conclusions related to the m / e

- 18

= 17 p e a k are equally valid for the

= 18 peak.
Results and Discussion
All T O

analyses of hydrated C 3 S exhibited a pattern typical of (i) a

weight loss associated with dehydration of c a l c i u m silicate hydrates,

(ii) de-

hydration of C a ( O H ) 2 and (iii) a m i n o r weight loss due to decarbonization of

traces of C a C O 3 f o r m e d b y C O z a d s o r b e d during hydration.
Figure 1 [s a plot of the intensity of the - O H and C O 2 M S

peaks for a

six hour hydrated s a m p l e of p u r e C3S.

T h e s e data s h o w several well-defined

evolution peaks for both H z O

The H20

and C O z.

data s h o w that dehydration of

TEMPERATURE(% x 10-2)

FIG.

T e m p e r a t u r e profile of the evolution of H z O (Curve A) and C O z

(Curve B) f r o m a s a m p l e 9f 6 hour hydrated C ~ S undergoing a
heating rate of 1 5 C rain - at a p r e s s u r e of -I~ -5 Torr.

Vol. 4, No. l
73
CARBONATION, CALCIUM SILICATE HYDRATES, MASS SPECTROSCOPY, THERMOGRAVIMETRY
the calcium silicate hydrates involves at least two distinct processes below
2 0 0 C in v a c u u m

(10 .5 Tort), closely followed at Z Z 5 o c by a sharp but short

lived evolution before the m a i n Ca(OH)z decomposition occurs at -350C.

It

is unlikely that the sharp peak at 2 2 5 C is related to further decomposition of

s o m e calcium silicate hydrate component.

It s e e m s m o r e

likely to be associ-

ated with poorly crystallized Ca(OH)z, which has been observed m a n y times
using differential thermal analysis.

T h e two m i n o r H 2 0 evolution peaks at

825 and 9 0 0 C coincide with phase changes in C 3 S

under these experimental

conditions and probably represent the evolution of trapped H z O during reorganization of the C 3 S lattice.
T h e C O z evolution profile shows the expected peak centered at 5 0 0 C
associated with the decomposition of C a C O 3.
normally observed during D T A
vacuo.

This temperature is lower than

because the decomposition is occurring in

This interpretation has been validated by d e c o m p o s i n g pure C a C O 3

under the s a m e experimental conditions.

O n the C O z evolution profile there

are unexpected peaks centered at 1 0 0 C and 300C.

It is possible that the

peak at 1 0 0 C could be caused by desorption of adsorbed surface C O z, but the

origin of the peak at 3 0 0 C is unknown.
S a m p l e s of C 3 S hydrated with 5% K z C O 3 w e r e also studied.
C O z evolution profile for this material is s h o w n in Figure Z.

A HzO

The H z O

evolu-

tion profile is essentially similar to that for pure C3S, although three distinct
peaks are evident for the dehydration of the calcium silicate hydrates.

The

C O p evolution profile again shows the decomposition of C a C O 3 at 500C, but

this time it is followed by a peak centered at 6 5 0 C due to the decomposition
of the remaining K z C O 3.

T w o low temperature peaks at I00 and Z 5 0 C are

again evident.
Analysis of the C 3 S s a m p l e hydrated under gaseous carbonation is
s h o w n in Fig. 3.

Note specifically that the type of evolution pattern associa-

ted with the generation of carbonation products, C O z sources, is not simply

due to C a C O 3 decomposition.

C O Z evolution f r o m C a C O 3 at 500oc is apparent,

but significant evolution at -675C f r o m other sources also is clearly evident.

In all cases w h e r e the gas evolution has been indicated, e.g. H z O
f r o m C a ( O H ) z , and C O z f r o m C a C O 3 or K z C O 3 ,

control experiments using

pure chemicals have been p e r f o r m e d under identifical conditions to provide

validity for the statements.

This procedure w a s necessary because d e c o m p o -

sitions under v a c u u m can occur at temperatures significantly lower than those

observed during conventional D T A

of hydrated c e m e n t minerals under n o r m a l

74
Vol. 4, No. l
CARBONATION, CALCIUMSILICATE HYDRATES,MASSSPECTROSCOPY,THERMOGRAVIMETRY

2
B

I
8

TEMPERATURE(% x 10-2)

FIG.

T e m p e r a t u r e profile of the evolution of H 2 0 ( C u r v e A) and C O 2

(Curve B) f r o m a sample of 6 hour hydr.ated C3S containing 5%
K z C O 3. The heating rate is 15C rain -I and the pressure
~10 - 5 T o r r .

FIG.

T e m p e r a t u r e profile of the
evolution of C O 2 f r o m a m o r t a r
s a m p l e of C3S l~ydrated under
gaseous carbonation. T h e heating rate is 15C min-I and the
pressure -10 -5 Torr.

=~
"-

TEMPERATURE(C x I0 -2)

Vol. 4, No. 1
75
CARBONATION, CALCIUM SILICATE HYDRATES, MASS SPECTROSCOPY,THERMOGRAVIMETRY
atmospheric

pressure.

T h e f a c t t h a t e v o l u t i o n o f b o t h Hp.O a n d COP. c a n o c c u r
o v e r a w i d e r a n g e of t e m p e r a t u r e s
exercised

when decomposition

kinetics.

Clearly,

associated

curves

so derived

for calcium

alone.

by comparing

Ca(OH)p. a n d t h a t f o r m e d

of calcium

silicate

the results

silicate

by the hydration

hydration

Ca(OH)P., if t h e a n a l y s i s
But during isothermal
cium silicates,

silicate

hydrates.

of c a l c i u m

a r e in a g r e e m e n t

decomposition

much lower values

product

(15).

of p u r e

Recently,

it

of C a ( O H ) 2 f o r m e d

with studies of pure

thermal

of t h e a c t i v a t i o n

analysis

d a t a (14).

from hydrated

cal-

energy for decomposition

This difference

may exist be-

in t h e s a m e t e m p e r a t u r e

tions of the calcium

sources

s o f a r in F i g s .

It is quite possible

i s d u e to t h e d e s o r p t i o n

of COP. a d s o r b e d

silicate

hyd r a t e s .

Gaze and Robertson

the two dimensional

on t h e s u r f a c e
Inferences

silicates

was dismissed

not as sensitive

have suggested

a s MS a n a l y s i s

of X - r a y

(1P., 13).

A likely possibility
the mineral
the phase

scawtite,
CSH(A).

For

t h a t t h e COp w a s a b s o r b e d

data,

of c a r b o n a t e d

calcium

although this technique

1 4 0 C to 3 0 0 C (18).

is

of s p u r r i t e ,

temperature

Ca5(SiO4)p. C O 3 , a s it

is 7 9 0 C (17).

is t h a t t h e COP. e v o l u t i o n p e a k a t 3 0 0 C is d u e to

This conclusion

s l i g h t COP. c o n t a m i n a t i o n

into

compound which slowly re-

C a 7 S i 6 O p . 1 H 6. C O 3 , w h i c h i s b e l i e v e d to b e s i m i l a r

has been observed

the availability

posi-

It i s a l s o u n l i k e l y t h a t t h e COP.

a t 3 0 0 C is f r o m t h e d e c o m p o s i t i o n

has been shown that its decomposition

o r in i n t e r l a y e r

o f COP. e v o l u t i o n f r o m

The potential occurrence

on the basis

at 100oc

in t h e p a s t (1P., 13, 16).

l a t t i c e to g i v e a n i n t e r s t i t i a l

COP. on h e a t i n g (16).

1 a n d P. a r e t h o s e f o r

that the peak centered

other than CaCO 3 have been presented

example,

from

producing

a s c a n b e s e e n in F i g . 1.

COP. a t l o w t e m p e r a t u r e .

scawtite

e n e r g y of d e -

silicates.

of Ca(OH)p. f o r m e d

T h e t w o MS p e a k s u n i d e n t i f i e d

source

are not

This point can be

of the decomposition

c a u s e of t h e c o n f u s i n g i n f l u e n c e of COP. g e n e r a t i o n

leased

hydrate

any activation

is based upon differential

are obtained for this hydration

region,

decomposition

of s t u d i e s of t h e d e c o m p o s i t i o n

h a s b e e n s h o w n (6) t h a t t h e e n e r g e t i c s
during calcium

Thus,

caution must be

is not uniquely the energy of the process

Hp.O in t h e d e c o m p o s i t i o n
illustrated

that considerable

are used to derive

weight loss curves

w i t h t h e l o s s of w a t e r

composition

indicates

simultaneously

to form

is b a s e d ,

primarily,

in t h e C a O - S i O z - H p . O

had occurred
Inspection

on t h e f a c t t h a t
system

and that its stability range

of Figs.

o f COP. o r CO23 - is i n c r e a s e d ,

to

in w h i c h
extends

1 a n d P. a l s o s h o w s t h a t , w h e n
t h e COP. e v o l u t i o n p e a k a t 3 0 0 C

76
CARBONATION, CALCIUM SILICATE HYDRATES,MASS SPECTROSCOPY,THERMOGRAVIMETRY
increases.

If this hypothesis is correct, then unless C O 2 is rigorously ex-

cluded f r o m the atmosphere during hydration, scawtite will be present as a

hydration product.
A c k n o w l e d ~ ements
The authors would like to thank C. Gorzynski for performing the
mass

spectrometric analyses.
References

i.

W.A. Klemm

and R.L. Berger, Cern. and Con. Res., 2,567,(197Z).

Z.

R.L. B e r g e r and W . A . Klernrn, Cern. and Con. Res., Z, 647(197Z).

3.

Z. S a u m a n ,

Cern. and Con. Res. , i, 645, (1971).

4.

Z. S a u m a n ,

Cern. and Con. Res., Z, 541, (197Z).

5.

Z. S a u m a n and V. Lach, Cern. and Con. Res., 2,435(197Z).

6.

J.N. M a y c o c k and J. Skalny, T h e r m o c h i m i c a

7.

H.N. Stein, J. Appl. C h e m . ,

8.

E . M . M . G . Niel, Chemistry of Cement,

47Z, Tokyo , (1968).

9.

S. Brunauer, J.Skalny, l. Odler and M. Yudenfreund,

3, 779, (1973).

Acta(in press).

Ii, 474, (1961).

Proc. 5th Intl. S y m p . , Vol. II,
Cem.

and Con. Res.,

I0. H. Mori, K. Minegishi, T. Ohita and T. Akiba, S e m e n t o Gijutsu

Z4, 48, (1970).

Nernpo,

II. :[.Skalny, J. C. Phillip and D.S. Cahn, Cern. and Con. Res. , 3, zg, (19731
IZ. W . F . Cole and B. Kroone, J. A m .

Conc. Inst., 31___,1275, (1960).

13. B. K r o o n e and F.A. Blakey, / . A m .

Conc. Inst., 3.1, 497, (1959).

14. N. G. Dave and S.K. Chopra, J. A m e r .

Ceram.

Soc. 4__~9,575, (1966).

15. R.S. Mikhail, S. Bruanuer and L.E. Copeland, J. Colloid Interface Sci. ,

Zl, 394, (1966).

16. R. G a z e and R.H.S. Robertson,

Mag.

of Concrete. Res., 7, March, (1956).

17. F.P. Glasser, Cern. and Con. Res., 3, 23, (1973).

18. R.I. Harker, Mineral Mag.

3_~4, Z32, (1965).