CEMENTand CONCRETERESEARCH. Vol. 2, pp. 633-636, 1972. Pergamon Press, Inc.

DISCUSSION

DISCUSSION OF THE PAPER"MORPHOLOGYAND SURFACEPROPERTIESOF HYDRATED

TRICALCIUM SILICATE PASTE" BY M. COLLEPARDI AND B. MARCHESEl
by
R. L. Berger, J. F. Young and F. V. Lawrence
Departments of Civil, Ceramic and Metallurgical Engineering
University of Illinois
Urbana, Illinois 61801

The recent paper by Collepardi and Marchese showed morphological changes

of calcium s i l i c a t e hydrate gel (C-S-H gel) in the presence of calcium chlor-
ide, We f e l t that some of our recent work with admixtures would be of i n t e r -
est and may add some f u r t h e r insight into the two structures.

Table l
Admixtures Studied for Their Influence
C-S-H Gel Morphology

Observed C-S-H Morphology Analyzed Admixture 1 percent by

in hydrated C3S by weight of C3S

Type I TEM none, AgN03, Cu(N02)2, CaF2, FeS04,

7H20, Mandelic Acid, CaSO4-2H20, Sali-
cylic Acid, ZnO, Fe(N03)3, AI2F6

SEM none, CaSO4.2H20, Ca(Cl04)2

Ca propionate

Type I I TEM CaCl2, LiCl, LiOH

SEM CaCl2, Cu(SCN)2, Ca maleate

633
 634 Vol. 2, No. 5
DISCUSSION

FIG. 1
Type I morphology. TEM and SEM showing C-S-H gel in hydrated C3S
with and without CaCl2.
A. TEM of carbon replica of C3S, l.O w/s 15 days, (15,000x)
B. SEM of C3S, 0.4 w/s, hydrated 15 days (15,000x)
C. TEM of carbon replica of C3S with l percent CaCl2, hydrated 15 days
(I5,O00x)
D. SEM of C3S with l percent CaCl2, 0.4 w/s, hydrated 5 days (15,000x)

The use of transmitted electron microscopy (TEM) of u l t r a s o n i c a l l y dis-

persed samples has the advantage of d i r e c t l y viewing the p a r t i c l e s . However,
this technique had the disadvantage that the spatial relationship of the p a r t i -
cles to one another and the topography produced by various morphologies is
lost. One can use a carbon replica technique with TEM2 or scanning electron-
Vol. 2, No. 5 635
DISCUSSION

.' >

. • '%

FIG. 2
TEM of carbon replicas of C3S with l percent of various admixtures
hydrated at l.O w/s for 15 days
Type I morphology. A. FeSO4.7H20 (15,000x) B. Mandelic Acid
(I5,O00x)
Type II morphology. A. LiCl (12,000x) D. LiOH (15,000x)

microscopy (SEM)3 to view the surface topography of fractured or cut surfaces.

The influence of 18 admixtures on the morphology of C-S-H gel is given in
Table I. Under these conditions two distinct morphologies are developed in
the C-S-H gel which forms on the outer surface of tricalcium silicate (C3S)
particles. These correspond to those shown by Collepardi and Marchese.l

Type I consists of the rolled sheet or acicular projections from C3S grains
and is common to most admixtures studied (see Fig. l ) . The different admixtures
636 Vol. 2, No. 5
DISCUSSION

do have some influence on the si.ze and, to soBm extent, on the shape of the
acicular C-S-H (see Fig. 2), however the overall morphological shape is un-
changed.
Type II as shown in Figs. l and 2 consists of sheets which have numerous
concavities or a pseudo "h~neycomb" structure. This type morphology is gen-
erally associated with admixtures which cause an acceleration of the hydrat-
ion. We have not observed any other distinct morphological types.

The higher nitrogen surface areas in C3S samples with calcium chloride
is undoubtedly related to the difference in morphology of the C-S-H, as noted
by Collepardi and MarcheseI as well as by Skalny and Odler,4 and may be simply
a consequence of the changes in external surface to volume ratio for the two
morphologies. Surface areas determined by water adsorption for both systems
4
are approximately equal. Thus, the morphological change probably does not
signify a significant change in the basic structure of the gel.

The significance of C-S-H gel morphologies which are well developed in

the capillary void space to strength and other engineering properties is yet
unclear. The gel products growing into the capillary voids do not contribute
strength to the system but rather, the gel at points of contact between cement
grains is important to strength generation. Further research is needed to un-
equivocally establish the relationship between the structure in the points of
contact and engineering properties.

References
I. M. Collepardi and B. Marchese, Cement and Concrete Res., 2, 57 (1972).
2. L. E. Copeland, E. Bandor, T. N. Chang and C. H. Weise, J'. P. C. A. Res.
Devl. Labs., 2, 61 (1967).
3. S. Chatterji and J. W. Jeffery, Nature, 209, 1233 (1966).
4. J. Skalny and I. Odler, J. Am. Ceramic Soc., 54, 362 (1971).