Differential Scanning Calorimetry Study of Ordinary

Portland Cements Mixed with fly Ash and Slag

A.E.Al-Salami1, M.A.Ahmed2, A.Al-Hajry3 and S.Taha3
1Department of Science, Teachers College, P.O.Box (249), Abha, Saudi Arabia
2 Department of Physics, Faculty of Science, Cairo University, Giza, Egypt
3 Department of Physics, King Khalid University, P.O.Box (9003), Abha, Saudi Arabia
Abstract. The study of the thermal behavior (DSC) of hydration products in ordinary Portland cement (OPC), as a function of
water cement ratios (W/C) (0.2, 0.25, 0.4), and the partial substitution of (35 % fly ash), (35 % slag) and (35 % fly ash + 35 %
slag) to the OPC system by weight separately was carried out. It was found that the additive materials (pozzlans) increase its
durability when added to the OPC. The most important effects in the cement paste microstructure are the changes in pore
structure produced by the reduction in the grain size caused by the pozzlanic reactions. The study revealed that the changes in all
the thermal parameters depend on the variation of W/C ratios.
The systematic changes in the activation energy through all systems occur at (0.3) W/C in the phase (C-H) and (0.35) W/C in the
phase (C-S-H). This means that at these ratios of W/C the two phases (C-H) and (C-S-H) further accelerated the process of
cement hydration reactions, and at the same time the addition to OPC system may provide enough space for hydration products to
be distributed uniformly.

INTRODUCTION
The use of replacement materials in ordinary Portland cement (OPC) has gained much attention in recent years.
Given the world with respect to cement demand and the cost of energy, not only will blends with materials such as
granulated blast furnace slag and fly ash be used, but other options will also become available to satisfy these needs.
In blended cements, the replacement material may take part in the hydration reaction and also contribute to the
hydration product.
Two groups of cement replacements are commonly recognized, Pozzlands and latently hydraulic materials [1, 2].
The first group reacts with the C-H produced during the cement hydration, while the second has itself hydraulic
characteristics, but its hydration needs activation, for example, by the presence of the hydration products [e.g. (C-H)]
or other additives [3, 4]. The effect of secondary materials enhanced the cementations properties and the hydration in
OPC system when substituted partially by fly ash or slag [5, 6].
The successful replacement material for OPC relies on satisfying three main objectives, namely economic
advantage, environmental benefit and technology improvement. When waste materials are used, the first and second
considerations may act together, and they are then shared by manufacturers and ecologists, but the technological
factors must not be ignored. Failure of materials to comply with any of the three factors can reduce the
attractiveness of the replacement materials.
Slag cement has many advantages such as higher later strength, good durability and chemical stability. The fly
ash has disadvantages, such as lower strength, higher water requirement and bad resistance carbonation [7]. But the
incorporation of fly ash in OPC system can reduce the alkalinity of poor solution; efforts have been made to apply
fly ash to improve the durability of glass fiber reinforced cement [8]. So, it is good method to partially substitute
OPC by slag and fly ash in producing complex cement.
There is less information in the literature about the hydration of the different anhydrous cement phases in the
presence of slag and the fly ash [1-3, 9].
The present paper is a part of a progressing research program tending to determine the thermal properties,
activation energy and durability of the OPC containing (35% fly ash), (35% slag), and (35% fly ash + 35% slag)
each separately. The research reported herein provides information for the effect of admixture on the hydration
process for the two phases C-S-H and C-H, by using the differential scanning Calorimetry (DSC).

CP748, Modern Trends in Physics Research, edited by Lotfia El Nadi

2005 American Institute of Physics 0-7354-0233-7/05/$22.50

182

EXPERIMENTAL TECHNIQUES
Materials used in this work were ordinary Portland cement (OPC), fly ash, granulated blast- furnace slag. The
chemical analysis of these materials are given in Table (1)
TABLE (1) Chemical Analysis of the Used Sample
Sample code

Si02

TiO2

OPC

18.19

0.28

Fly ash
slag

A12 O3 Fe2O3
4.23

2.62

49.49

37.75

7.96

38.60

13.20

3.53

FeO

MgO

0.16

1.6

Na20

K20

P202

H20

S03

61.71 1 9.67

0.25

0.61

0.68

Ca 0

5.36

Cl

2.44

1.24

2.02

0.54

0.4

33.76

1.33

0.66

0.55

0.0007

The dry mixes were prepared from ordinary Portland cement (OPC) +35% fly ash, opc+35%slag and ope
+35%fly ash +35%slag The mixes were homogenized for one hour in a laboratory agate ballmill. Cement and water
were continuously and vigorously mixed using ordinary gauging trowels on a steel plate for three minutes with the
standard water of consistency (10).
The hydration was stopped by pulverized lOgm sample of representative sample in beaker containing methanol
acetone mixture, then mechanically stirred for one hour. The mixture was filtered through a gooch crucible, and
washed with ether. The solid was then dried at 100C for one hour to complete evaporation of alcohol. The hardened
paste was put into an airtight container for analysis. The differential scanning meter (DSC-50) performed the phase
composition.

RESULTS AND DISCUSSION

The DSC thermograms of hydrated OPC is shown in figure (1) at various water cement ratio (,2, ,25,..,4) w/c.
There are three endothermic peaks located at 91-101C, 429-434C and 643-689 C.

DSC
mW
j.i 1111

a: w/c = 0.20.

nnr

nnr

?nnni

mnnr
Temp (C)

FIGURE 1. The DSC Thermo grams-for the OPC system at different water cement (W/C) ratios

183

0.5
0.6

eg (e.V)

Time (min)

Heat (J/mg)

Peak (C)

Height (mw/mg)

The first exothermic peak is mainly due to the calcium silicate hydrate (CSH), the second exothermic peak
located at 429 - 434C is due to the dehydration of Ca (OH) 2, and the third exothermic peak at 643 689C, is due
to the carbonation of Ca CO3 and its crystalline form.
In ordinary Portland cement (OPC) there are four major phases: tricalcium silicate (C3S), dicalcium silicate ( C2S), tricalcium aluminates (C3A) and tetracalcium aluminoferrite (C4 AF). Both C3S and -C2S react with water
to form calcium silicate hydrate (C-S-H) and calcium hydroxide (C-H) as their principal hydration products [11].
The mean feature of the thermo grams is the decrease in the peak area of (C-S-H) which may be due to partial
decomposition of this phase as the water cement ratio (w/c) increases. It is also clear that the endothermic peak of
the (C-H) phase increases with increase the w/c ratio up to 0.35 ratios; the increase in the (C-H) pack area is a result
of recrystallization of the amorphous part of Ca (OH) 2.
Evidently, the endothermic peak area of CaCO3 changes according to the change in the peak area of C-H. It is
mainly dependent on the variation of w/c in the opc system. This may be due to the physical chemical process
connected with the increase of w/c ratio in the opc system, which accelerate, or retardate Ca (OH) 2 carbonation
kinetics. This was indicated by a partial decrease or increase in the Ca (OH) 2 content, which tends to the variation
of the Ca CO3 in the opc system. [12,13].

FIGURE 2. Variation of heat transformation H, peak height, peak position, time of formation and activation
energy for the phase (C-S-H) in the OPC system with the W/C ratio

184

PEopc2

HIopc2

434

1.2
1.1

Height ( mW/mg)

Peak (C)

432

430

428

1.0
0.9
0.8
0.7
0.6

426
0.20

0.25

0.30

0.35

0.5

0.40

0.20

W/C

0.25

0.30

0.35

0.40

W/C

HEopc2

TIMopc2
22.5

0.07

22.4
0.06

Time (min)

HEAT(j/mg)

22.3
0.05

22.2
22.1

0.04

22.0
0.03

21.9
0.20

0.25

0.30

0.35

0.40

0.20

0.25

W/C

0.30

0.35

0.40

W/C

EG opc2

6 .5

Eg (e.v)

6 .0

5 .5

5 .0

4 .5
0 .2 0

0 .2 5

0 .3 0

0 .3 5

0 .4 0

W /C

FIGURE 3. Variation of heat transformation H, peak height, peak position, time of formation and activation energy for the
phase (C-H) in the OPC system with the W/C ratio

The changes in the thermal parameters with the w/c ratios are shown in Figs (2, 3) for both (C-S-H) and (C-H)
phases in the OPC systems, the thermal parameters included the heat of transformation (enthalpy) (J mg-1), the peak
height (mW gm-1), the peak position (oC), the time (min) for the formation the hydrate phase during the DSC cycle
and the activation energy.
The activation energy for the two phases (C-S-H) and (C-H) can be calculated by using the equation:
ln (T) = G - Eg / RT
(1)
Where the value of (T) can be directly deduced from the DSC curve in units of length (cm or mm). According
to equation (1) and by plotting the relation between ln (T) and 1/T (K)-1, the activation energy Eg can be
calculated. In fact equation (1) can be considered as a modified from Kissinger's equation [14, 15].

185

The critical changes in the thermal parameters in the ope system for the two phases (C-S-H) and (C-H) occurs at
0.3- .35 w/c ratios, but the critical variation in the activation energies for the phases (C-S-H) and (C-H) occurs at w/c
= 0.3 ratio.
The values of Eg at different w/c ratios for the two phases (C-S-H) and (C-H) were estimated and tabulated in
table (2)
TABLE (2) : Values of the activation energy (eV) for Two phases (C-S-H) and (C-H)
\.
W/c
^^^
0.20
Phase ^^^
C-S-H
C-H

7.23

5.98

0.25

0.30

0.35

0.40

6.2
6.10

3.99
4.69

1.66
5.35

0.94
6.51

The results of the DSC measurements demonstrate that the increase of the w/c ratios in the ope systems is
associated with considerable change in the thermal characteristic and activation energy of the hydration products of
(C-S-H) and (C-H), The variation in the hydration products are mainly depending on the w/c ratios in the OPC
system, so the rearrangement water is obviously due to the different pore size distribution within the OPC system
and the resultant differences in capillary pressure and that is effected on the hydration mechanism. The difference in
pore size distribution and capillary forces are not generated by different size in the hydration products, but rather by
the difference in w/c ratio or water filled porosity within the OPC system. [16].
In the case of w/c > 0.35 the hydration products of (C-S-H) and (C-H) decrease while the CaCO3 increases due
to the chemical shrinkage effect (creation of porosity). The preferential of water from regions of high porosity (high
w/c ratio) to regions of low porosity has several implications for the hydration products of the ope system.
The results for the production of large empty pores (at high w/c ratio) could substantially decrease both the
strength and the durability of the final hydration product [13].
Figure (4) shows the DSC thermograms of the system (opc-i- 35% fly ash) at a different w/c ratios (0.20 to 0.40
in step of 0.05)
DSC

mW
40.00

a: w/c = 0.20.
b: w/c = 0.25
c: w/c = 0.30
20.00

d:^wfc= 0.35
eiw/cXo.40 7

0.00

-20.00
0.00

200.00

400.00

600.00

Temp [c]

FIGURE 4. The DSC thermo grams for the (OPC + 35% Fly ash) system at different water cement (W/C) ratios.

186

The figure show the existence of three endothermic peaks which appeared in the thermograms of OPC system
Fig. (1), but at different temperature values i.e. (C-S-H) at (95-100C), (C-H) at (430- 435C) and CaCO3 at (648 688C).
The effect of fly ash on the OPC system is the improvement of the hydration product of the two phases (C-S-H)
and (C-H). This to decrease the endothermic peak of CaCO3 especially at the w/c =0.40. The fly ash reduces the
concentration of hydroxyl ions (OH) and CO2 emission from the production of cement clinker. Therefore, pozzolana
addition increases the resistance of the hardened cement pastes towards carbon dioxide attack. [17-19]. The decrease
in the peak area of (C-H) phase at w/c = 0.40 is a result of amorphous of the crystallization part of Ca (OH) 2 [12].
The effect of fly ash on the system (OPC + 35% fly ash) plays an important role in the variation of the thermal
properties and activation energy for the two phases (C-S-H) and (C-H) in this system.
The activation energy values at different w/c ratios for the two phases (C-S-H) and (C-H) in the system (OPC +
35% fly ash) were calculated as in the case of OPC system [14,15] and the results are tabulated in table (3).
TABLE (3)

W/c
0.20

0.25

0.30

0.35

0.40

6.92
6.20

6.40
4.46

4.96
5.51

5.83
5.31

6.52
7.02

Phase
C-S-H
C-H

The changes of the thermal parameters and the activation energy in the two phases (C-S-H) and (C-H) for the
system (OPC + 35% fly ash), mainly depend on the physical effect of fly ash in this system during the hydration
mechanism. The use of fly ash in this system led to the increase of the packing density and specific surface area,
while it decreased the air content and reduced the chemical shrinkage effect (at higher w/c ratios). The effects of fly
ash leading to the change in the microstructure in this system (changes in pore solution, refinement of the pore
structure and their effects are also extended to the thermal properties and activation energy) [13, 19-20].
The DSC thermograms for the system (OPC + 35% slag) at different w/c ratios (0.20 to 0.40 in step of 0.05) were
measured.
Three endothermic peaks similar to figure 4 were observed for (C-S-H) at ~ (93-99), (C-H) at ~ (425-433C)
and Ca CO3 at ~ (653-696C). The peak area of the two phases (C-S-H) and (C-H), increased up to w/c ratio = 0.30
and is accompanied by small changes at a higher w/c > 0.30. This is due to the Pozzlaanic (slag) related effect,
which consumed the free lime librated from the hydration of OPC forming addition of (C-S-H). This suggests that
the growth in the hydration mechanism is more related to the physical effect than to the chemical one (hydration or
action of Pozzlaanic) [11]. Also, the peak area of CaCO3 doesn't change during the cement hydration. This is due to
the slag effect on the system (OPC + 35% slag) which decreases the accelerated Ca (OH) 2 carbonation kinetics [2].
The variation of the thermal properties and activation energy for the two phases (C-S-H) and (C-H) in the system
(OPC + 35% slag) developed a critical variation in the thermal properties in the two phases (C-S-H) and (C-H)
observed at w/c ratio = 0.3 and this variations mainly depend on the physical effect of the slag in this system during
the hydration mechanism [11].
The activation energies for the two phases (C-S-H) and (C-H) for this system were calculated as in the case of the
OPC system at different w/c ratios [14, 15], the results are tabulated in table (4).
TABLE (4)
W/c
0.20

0.25

0.30

0.35

0.40

C-S-H

6.86

9.97

2.79

6.40

8.48

C-H

5.29

4.50

5.73

6.41

5.60

Phase

187

The critical variations in the activation energy for both C-S-H and C-H was clearly observed at w/c ratio= 0.30.
The change in the activation energy depends on the variation in the micro structure of the system (OPC + 35% slag,
the activity of the slag with OPC increased in the alkaline environment, this is of great advantage to decrease Ca
(OH) 2 during the hydration products of OPC. This in turn accelerated the process of cement hydration reaction. At
the same time, slag may provide enough space for hydration products to be distributed uniformly (i.e.) refines the
pore microstructure of the system (OPC + 35% slag). [1,2] So the use of slag in this system improved the
workability and other physical properties such as permeability and resistance to alkali silica reactivity. A number of
peaks were observed in the DSC thermograms for the system (OPC + 0.35 fly + 0.35 slag) at different w/c ratio (0.2,
0.25, ........ 0.40). The identification of these peaks is given in figure (5). There are three endothermic major peaks
C-S-H at (88-96 C), C-H at (430-439 C) and Ca CO3 at (652-699C) differing slightly than figure (4).

DSC

40.00-

a: w/c = 0.20
b: w/c = 0.25
c: w/c = 0.30
d: w/c = 0.35
e: w/c = 0.4

20.00

0.00

-20.0C

0.00

200.00

400.00
Ternc (C

600.00

FIGURE 5. The DSC Thermograms for the (OPC + 35% Fly Ash + 35% Slag) System at different Water Cement (W/C) Ratios.

From the figure (5) at the w/c ratio = 0.20, the peak height for both C-S-H and C-H and C-H phases is small. This
is related to the hydration process in the system, which produced the two phases of (C-S-H) and (C-H), but the
Pozzolana consumed these phases at the same time of production during the hydration process, with a much lower
rate [21]. The degree of hydration in the two phases (C-S-H) is accelerated with increasing the w/c ratio in the
system (OPC + 35% fly ash + 35% slag), but the degree of hydration is accompanied by a very small change at the
w/c ratios 0.3 and 0.35 and this is due to the pozzlana effect on the mechanism of hydration process. This effect can
be viewed as a heterogeneous nucleation for the increase of the hydration products, where C-H is a product of C-S-H
hydration and it is removed by the pozzlana reaction. Also, the slag in this complex system is also believed to
consume C-H to form C-S-H in the initially water - filled space, and therefore C-S-H hydration is similarly
increased [7, 21].
The changes in the thermal properties and activation energies, (as in the case of OPC, OPC + 35% fly ash and
ope + 35% slag) for the two phases C-S-H and C-H in the complex system (OPC + 35% fly ash + 35% slag) at
different w/c ratio were measured.

188

The activation energy values for this system were calculated for the two phases C-S-H and C-H at different w/c
ratio, by the same method in the other systems [14, 15] and the results obtained are tabulated in table (5).
TABLE (5)
W/c
Phase
C-S-H
C-H

0.20
8.67
3.43

0.25
8.96
5.91

0.30

0.35

0.40

6.61
7.30

8.90
6.14

7.35
6.50

The results showed that the critical changes in the thermal properties and activation energies for both C-S-H and
C-H phase occurs in the range (0.30 - 0.35) w/c ratios. The variation in the thermal properties depends on the
refinement of the hydration process by the minerals admixture in this complex system [21]. But the activation energy
depends on the morphology of C-S-H and C-H phases. These phases varies in their morphologies according to the
chemical composition of the system, this variation leads to changes in the pore microstructure in the system. So the
effect of the minerals admixture (35% fly ash + 35% slag) to the opc changes the fibrillar morphology in the opc
system to foil like morphology in this complex system (21).
The activation energies of the OPC and OPC mixed with minerals admixture (35% fly ash, 35% slag) were
studied at different w/c ratio for the two phases C-S-H and C-H. The dependence of the activation energy on the
additive to the OPC system is shown as a phase diagram in figure (6, 7).
W/c = 0.2
W/c = 0.25
W/c = 0.3
W/c = 0.35
W/c = 0.4

FIGURE 6. Phase Diagram for the Variation of the Activation Energy in the Phase (C-S-H) with the additive Pozlana (Fly Ash.
Slag, Fly Ash + Slag) to the OPC System.

The activation energy mechanism in the system depends on the charge transfer and the mean distance traveled by
the cations before being recombined again [22], this process depends on the changes in the pore microstructure
which are related to the effect of the minerals admixture (fly ash and slag) and the w/c ratios in these systems.

189

W/c = 0.2
W/c = 0.25
W/c = 0.3
W/c = 0.35
W/c = 0.4

FIGURE 7. Phase Diagram for the Variation of the Activation Energy in the Phase (C-H) with the additive Pozlana (Fly Ash.
Slag, Fly Ash + Slag) to the OPC System

CONCLUSION
One may conclude that the addition of minerals admixture (fly ash + slag) to the OPC matrix improved pore
microstructure, hydration properties, workability and corrosion inhibitor. This is because of the filling effect and the
effect of mutual complement of superiority supply.
The effect of water cement ratio (w/c) in the blended cement paste played an important role to increased the
hydration of the clinker phases, and it must be considered as an additional factor involving the physical presence of
the replacement materials as well as their chemical influence.
The proper consideration of the pore microstructure and capillary forces can lead to the optimization of the finer
pores microstructure which was reached at the w/c ratios 0.3 and 0.35. These ratios are considered to be the
optimum ratios for reducing the porosity.

REFERENCES
1- Huwen wan. Zhoughe Shui, Zongshou Lin ,Cement and Concrete Research 34, 133 (2004).
2- Menendez. G., Bonavetti. V., Irassar E.F, Cement & Concnete Composites 25, 61(2003).
3- Qian Jueshi, Shi Caijum, Wang Zhi, Cement and Concrete Research 31, 1121 (2001).
4- Poon. C.S., Kou. Sc., Lam, L., Lin. Z.S, Cement and Concrete Research 31, 873 (2001).
5- Isaia, G.C. Gastaldini, A.L.G. Moraes, R. Cement & Concrete Compositxes .25, 69 (2003).
6- Kearsley. E.P., Wainwright. P.J, Cement and Concrete Research. 31, 105 (2001)..
7- Dongxu. Li., Shen Jinlin, Chen Yimin, Cheng Lin, Wu Xuequan Cement and Concrete Research .30, 1381 (2000.).
8- Ya Mei Zhang, Wei Sun, Han Dong Yan , Cement and Concrete Composities .22, 445 (2000).
9- Escalante. J.I., Gomez. L.Y., Johal. K.K., Mendoza. G., Mancha. H.., Mendez, J., Cement and Concrete Research .31, 1430 (2001 )
10- ASTM Standards, Standard Test Methode for normal Consistency of Hydraulic Cement. ASTM C 187-83, 195 (1983).
11- Heikal. M.., Morsy. M. S., El- Didamony. H., Technology (Italia). No. 795, 422 (2001).
12- Morsy. M.S., Galal. A.F. and Abo-El-Enein. S.A.., Cement and Concrete Research. 38, 8. 1157 (1998).
13- Bentz. D.P., Hansen. K.K., Cement and Concerete Research. 30, 1157 (2000)
14- Kissinger. H. E., Anal. Chem. 29, 1702 (1957).
15- Rysava. N., Spasov. T., and Tich. L., J. Thermal Analysis. 32, 1015 (1987).
16- Coussot. P., Gauthier. C., Nadji. D., Borgotti. J.C., Vie. P., Bertrand. F., A cad. Sci IIB (Paris). 327, 1151 (1999).
17- Ehteshan. S. and Rasheeduzzafar. H., Cement Concrete ACI Materials Journal. 91, 3, 264 May June (1994).
18- Saad Morsy. M., Abo El-Enein. S.A. and Hanna. G.B. Cement and Concerete Research. 27, 9, 1307 (1997).
19- Bouzoubaa. N., Zhang. M.H., Malhotra. V.M., Cement and Concrete Research 31, 1393 (2001).
20- Isaia. G.C., Gastaldini. A.L. G., Moraes. R., Cement & Concrete Composites. 25, 69 (2003).
21- Escalante. J.I., Garacia and Sharp. J.H., Cement and Concrete Research, 28,9, 1259 (1998).
22- El-Kabbnny. F., Taha. S., J. Phys. Chem. Solid. 68, 3, 449 (1997).

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