CEMENT and CONCRETE RESEARCH. Vol. 20, pp. 398-406. 1990. Printed in the USA.

0008-8846-90. $3.00+00. Copyright (c) 1990 Pergamon Press plc.

EFFECT OF BLAINE FINENESS REVERSAL

ON STRENGTH AND HYDRATION OF CEMENT

Shondeep L. Sarkar
Faculty of Applied Sciences
University of Sherbrooke
Sherbrooke, Qc, Canada

0~d~zed)
(Received May 19. 1990)

ABSTRACT

This experiment investigates the effect of Blaine fineness reversal on the

strength of mortar made from two cements and determining the factors
influencing their strength development patterns. Types I0 and 30 cement
mortars and their reversed Blaine fineness counterparts were prepared, with
focus on their heat evolution, compressive strength, SEM examination, and
XRD analysis. Results indicate that cement fineness and the presence of
alkali sulfates play dominant roles in the strength development pattern.

INTRODUCTION

Extensive experimentation with different types and brands of cement in the

autho='s laboratory has u n c o n d i t i o n a l l y confirmed the exceptional
suitability of a type 30 (ASTM Type III) cement from a particular kiln for
high-strength concrete application (i). When the proper mixing sequence and
composition are used, concrete containing this cement can attain 28-d
compressive strengths of 140 MPa. In addition, such concretes display
consistent hlgh-strength development from early age onward.

In contrast, a Type I0 (ASTM Type I) produced in the same kiln with

identical raw-meal size proved unsuitable for hlgh-strength concrete.

It should be noted, however, that the t~ cements differ somewhat in terms

of raw meal composltlon/proportlonlng
instance, the raw meal for the Type I0
shale, and 0.5% iron oxide, whereas
limestone and 1% shale. Iron oxide
burnability (2).
and production parameters. For
is composed of 96.9% limestone, 2.6%
the Type 30 name meal contains 99%
is added to the Type I0 to improve

Furthermore, the clinker production rate also varies: 35 t/h for Type 30
compared to 40 t/h for Type i0. Type I0 has a lower Blaine fineness than
Type 30 (about 320 m2/kg to 480 m2/kg). In addition, the Type I0 is
produced using a i:i mixture of coke and coal in contrast to a 2:1 ratio
used for the Type 30. These differences have been shown to impact on the
mlcrostructure of the two clinkers (3).

398
Vol. 20. No. 3 Fineness, Alkali Sulfate, Hydration, S~ength 399

This experiment focused on studying the effect of Blaine fineness reversal

on the strength of these two cements and determining the factors influencing
their strength development patterns. To do so, samples of both types were
prepared to the each others' specifications: grinding and gypsum content.
Samples with reversed Blaine fineness are identified by a suffixed "R":
Type fOR and Type 30R.

EXPERIMENTAL RESULTS

The chemical analysis results, given in Table I, reveal only slight

differences in the compmosition of the sample cements, except for free lime,
Fe203, and SO 3. In light of the preceding section, however, such exceptions

TABLE I

Analytical results

Cement Type SiO 2 AI203 Fe203 Ca0 MgO SO 3 Free

lime

i0 21.35 4.57 2.14 62.86 2.84 2.38 0.83

30 21.09 4.36 1.75 63.69 3.03 3.26 1.09

10R 21.76 4.45 2.14 63~36 2.81 3.20 0.53

30R 21.75 4.36 1.89 64.46 2.90 2.32 1.48

are not surprising since mlnor variations in the composition/proportioning

and production parameters can result in different mineralogical compositions
(see Table 2): the Type 30 can have as much as 9% more C3S and 6% less C2S
than Type i0. C3A and C4AF contents, in contrast, show less discrepancy
(<1%).
TABLE 2

Mineralogical composition (%)

Cement type C3S C2S C3A C4AF

I0 51 23 8.3 6.1

30 58 17 8.6 5.3

IOR 50 24 8.2 6.5

30R 59 18 8.4 5.8

As indicated in Table 3, the 1-day compressive strength of the Type 30 is

more than twice that of the Type i0, with 28-day compressive strength
following the same trend. Blaine fineness reversal of the Type I0,
400 S.L. Sarkar Vol. 20, No. 3

resulting in Type IOR, increases the early compressive strength (10.3 MPa
compared to 16.1MPa) to a level that still falls short of that recorded for
Type 30. The Type IOR does, however, show marked improvement in 28-day
strength.

TABLE 3

Compressive strength of mortars (MPa)

Cement 1 day 3 days 7 days 28 days

Type I0 10.3 20.0 25.9 32.7

Type 30 22.8 33.3 39.3 45.0

Type IOR 16.1 29.1 34.7 46.0

Type 30R 9.5 19.4 26.9 36.7

When prepared according to Type i0 specifications, the Type 30 (noted 30R)

yields the lowest 1-day strength, displaying a 28-day compressive strength
slightly above that of Type i0, but significantly lower than that of types
10R and 30.

Heat of hydration studies performed on the four samples (see Figs. 1 and 2)
clearly indicate that the highest first peak, corresponding to the addition
of water to the cement, occurs in Type 30, followed by type 10R (Table 4).
Type 10R displays the highest second peak and greatest cumulative heat,
contrasting with Type 30R, which performs least well in these two areas.
The second peak maxima in the more coarsely ground cements, Types I0 and
30R, occur later than in the other two samples.

TABLE 4

Heat of hydration results

Cement type Blaine Amplitude Amplitude Time Cumulative

ripeness Ist peak 2nd peak 2nd peak heat
(mZ/kg) (cal/g/h) (cal/g/h) (h) (cal/g)
i

i0 337 1.9 2.65* 9.0 36.5

30 492 3.4 3.45* 7.0 48.0

1OR 480 2.5 3.8 7.5 48.5

30R 318 1.5 2.1 9.0 32.0
* with shoulder

Microstructural examination of Type I0 clinkers has revealed the presence of

appreciable amounts of alkali sulfate in the matrlx (3), which is of some
significance and can be traced to the greater coke content of the fuel used
to produce the Type 30 clinker. Chemical analysis showed that the coke
contained 5.7% sulfur as compared to 2.1% in the coal.
Vol. 20, No. 3 Fineness, Alkali Sulfate, Hydration, Surengxh 401

4. 50

TIOR 4O
,3
T
WR) ~ / ~ ~ 50o
O

Figure I. Heat ,q

of hydration of 2O
Type I0 and Type
1OR cements
I0

0 : I I I I I I I I I I I I I I I I I . L 1

0 8 16 24
TIME, HOURS

4 50
T30
4O
3
T50
3O

Figure 2. Neat
of hydration of
Type 30 and Type
30R cements I
I0

0 0
0 8 16 24
TIME, HOURS

As a result, free alkali sulfates formed in the Type 30 clinker (Fig. 3),
whereas XRD and EMP analysis has confirmed the substitution of alkalis in
the lattices of the C3A and C2S eontalned in the Type I0 clinker.

SEM examination and ~ D analysis of the Types I0 and 30 cement pastes

(water/cementitlous ratio of ~ 5 0 ) were carried out at 9 and 15 hours, and 7
and 9 hours, respectively, corresponding to the maximum rate of heat
evolution for the second peak and the adjoining shoulders on the heat of
hydration curves of these two cements.

XRDA, backed by SEM, revealed the formation of calcium monosulfate (Fig. 4)

prior to the appearance of the second peak, in addition to fibrous Type I
C-S-H (Fig. 5). As evidenced in Figure 6, an outer hydrate layer,
persisting in the 15-hour sample, had formed around some of the grains.
XRDA indicated a decrease in unhydrated cement between 9 and 15 hours.
In the Type 30 cement, however, the shoulder on the second peak represents a
conversion of AFt to AFm, as determined by ~ D . The outer layer, present at
7 hours (Fig. 7), was no longer visible at 9 hours (Fig. 8) even around the
coarse particles. Well-crystalllzed CH appears concurrently in the samples
in the shoulder reglon (Fig. 9).
402 S.L. Sarkar Vot. 20, No. 3

Figure 3. Show-
ing distribution
of alkali sul-
fate (O) in Type
30 clinker

Figure 4. Cal-
cium monosul-
fate plates in
Type i0 cement
paste at 9 h

Figure 5.
Fibrous Type I
C-S-H in Type i0
cement paste at
9 h
Vol.20,No. 3 Fin~ess,AlkaliSulfate,Hydration,Su,ength 403

Figure 6. Outer
hydrated layer
in the same
sample at 15 h

Figure 7. Outer
hydrated layer
in Type 30
cement paste at
7h

Figure 8.
Fibrous Type I
C-S-H, but no
outer hydrated
layer in Type 30
cement paste at
9h
404 S.L. Sarkar Vol. 20, No. 3

Figure 9. Well
formed CH
crystals

DISCUSSION

As early as 1951, Newklrk (4) correlated alkali and sulfur trioxide content
to alkali sulfate behavior: a preponderance of S03 was linked to alkali
sulfate formation In the clinker, while a higher alkali content corresponds
to substitution of these compounds in the C3A and C2S lattices. A higher
sulfur content in the fuel accounts for the formation of K2SO 4 in the Type
30 clinker; the alkalies in the Type I0 have been stabilized in the C3A and
C2S lattices.

Numerous authors (5) have reported that the presence of alkali sulfates can
enhance early strength development at the expense of final strength. This
Type 30 cement, however, contradicts these findings, since its strength
development remains high and consistent throughout, suggesting that its fine
particle size carries on the initial strength enhancement due to the alkali
sulfates.

This is borne out by the Type i0, which, when finely ground (Type 1OR),
loses its early strength development while displaying high 28-d strength.
Conversely, the coarsely ground Type 30R exhibits significantly lower
initial strength than Type 30, which may be linked to retarded reactivity
caused by alkali sulfate grains adhering to the cement, thereby impeding the
development of high early strength.

The dynamic role alkali sulfates can play in early hydration was
demonstrated by another experiment involving Types I0 and 30 clinkers ground
to the same flneness, although the quantity of heat initially liberated
differed greatly (Fig. I0). According to Smith and Matthews (6), the first
peak represents the alkalies in solution, together with cement wetting and
the hydration of free llme. Given the identical particle size of the Type
I0 and 30 clinkers, it is evident that alkali sulfates in the type 30
contribute significantly in generating such a high degree of heat, Its
slightly higher free llme content notwithstanding.
This is clearly reflected in the heat of hydration results for the four
cement samples tested. The Type 30 yields the highest first peak,
indicating rapid reaction caused by alkal~ sulfates, contrasting with the
lower heat liberated by the Type IOR, despite their identical fineness.
Vol. 20, No. 3 Fineness. Alkali-Sulfate, Hydration. S~ength 405

30

3l
21 20
Figure i0. Heat
of hydration
curves for Type
I0 and Type 30 IO
clinkers

0
0 8 16 24
TIME , Hours

Since the Type IOR cement contains less but more finely ground C3$ (see
Table 2) and generates the highest second peak, it would indicate that
cement particle size o u t w e i g h s C3S content in importance to the hydration
reaction. The delayed second-peak maxima in the coarser-ground cements (i0
and 30R) confirms that alite reacts more rapidly in finer cements, since
this peak r e p r e s e n t s C3S hydration, of which C-S-H and CH are the main
products (7).

The appearance of shoulders on the hydration curves for Types I0 and 30, but
not those of their reversed Blaine fineness counterparts remains
unexplained. The second-peak shoulder is conventionally attributed to
conversion of AFt to AFm.

SEM examination and XRD analysis show, however , that this shoulder
represents continued cement hydration; in the Type 30, AFm formation is,
however, partly responsible for the appearance of an adjoining third peak.
The development of the outer hydration layer may temporarily inhibit the
hydration process, thereby limiting heat evolution until the grains resume
activity. This phase of lower heat evolution, which is very short in Type
30 cement (as compared to Type i0), is directly related to particle size.

CONCLUSIONS

Tests on a Type I0 and a Type 30 cement produced in the same kiln from very
similar raw materials with identical fineness were carried out to study the
effect of reversal of Blaine fineness on the strength development pattern
and early hydration characteristics. The fuel used to produce the Type 30
cement was richer in sulfur, giving rise to the presence of alkali sulfates
in the clinker.

The compressive strength of the Type 30 cement is high from i to 28 days,

corresponding to the presence of alkali sulfates and cement fineness. The
former enhances early strength, while the latter confers late strength,
findings confirmed by Blaine fineness reversal. When ground to the same
fineness, Type i0 fails to achieve similar high early strength, although its
28-day strength shows significant improvement.
406 S.L. Sarkar Vol. 20, No. 3

Comparison of the calorimetry results reveals that the first peak, partly
attributable to the presence of alkali sulfates, is highest in Type 30.
Types IOR and 30, more finely ground than the other samples, exhibit the
most pronounced second peaks, representing continued C3S hydration. SEM
examination and XRD analysis, however, reveal that the hydration kinetics of
Types I0 and 30 are different in the second peak region.

These tests have demonstrated that cement fineness and the presence of
alkali sulfates play dominant roles in the strength development pattern.

REFERENCES

i. Altcin, P.C., Laplante, P. and B~dard, C., ACI SP-87, 51, 1985.

2. Bye, G.C., Portland Cement, Composition~ Production and Properties ,

Pergamon Press, Oxford, 1983.

3. Sarkar, S.L., Influence of raw meal composition, fineness and fuel on

clinker mlcrostructure and cement quality, Unpublished report, 1989.

4. Newkirk, T.F., J. Res. Nat. Bur. Stds., 349, 1951.

5. Locher, F.W., Zem. Kalk-Gips, 26, 53, 1975.

6. Smith, M.A. and Matthews, J.D., Cem. Concr. Res., ~, 45, 1974.

7. Skalny, J., Jawed, I. and Taylor, H.F.W., World Cem. Tech., ~(9), 183,
1978.

8. Pratt, P.L., Proc. E n ~ . Found. Conf., Henniker, Ed. G. Frohnsdorff,

107, 1985.