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Physical and chemical studies on cement containing sugarcane molasses

Article  in  Journal of Thermal Analysis and Calorimetry · October 2014

DOI: 10.1007/s10973-014-3947-4

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J Therm Anal Calorim (2014) 118:83–91
DOI 10.1007/s10973-014-3947-4
Physical and chemical studies on cement containing sugarcane
molasses
LI Weifeng • MA Suhua • Zhang Shengbiao •
Shen Xiaodong
Received: 16 January 2014 / Accepted: 11 June 2014 / Published online: 24 July 2014
Ó Akadémiai Kiadó, Budapest, Hungary 2014
Abstract Molasses is generally used as a grinding aid in
cement and as a water reducer and retarder in concrete. In
China, the output primarily consists of sugarcane molasses.
In this paper, the effects of sugarcane molasses on the
physical performance and hydration chemistry of conven-
tional Portland cement were investigated. The setting
times, the normal consistency of cement pastes, the com-
pressive strengths and fluidities of the mortars were
respectively determined according to Chinese Standard
GB/T 1346, GB/T17671 and GB/T 2419. The effect of
molasses on the hydration kinetics of cement was investi-
gated using a calorimeter. The hydration products and pore
size distribution of the cement pastes were analysed by
X-ray powder diffraction, differential scanning calorimetry
and a mercury injection apparatus. The results show that a
small amount of sugarcane molasses retards the setting and
hardening of cement paste and increases the fluidity of
cement mortar, while excess molasses accelerates the set-
ting and hardening. Molasses improves significantly the
compressive strength at 3d due to the decrease of porosity.
The addition of 1.0 % molasses accelerates the formation
of ettringite, prevents the second hydration of aluminate
phase and delays the hydration of C3S.
Keywords Sugarcane molasses
Physical properties

Hydration
L. Weifeng
M. Suhua (&)
Z. Shengbiao
S. Xiaodong
College of Material Science and Engineering, Nanjing
University of Technology, No5 Xinmofan Road, Gulou district,
Nanjing 210009, China
e-mail: yc982@163.com
S. Xiaodong
State Key Laboratory of Materials-Oriented Chemical
Engineering, Nanjing 210009, Jiangsu, China
Introduction
Molasses is a viscous by-product of the refining of sugar-
cane, grapes, or sugar beets into sugar. The composition of
molasses is variable and is dependent on the peculiarity of
the raw materials and the manufacturing conditions.
Molasses can be used as fodder for livestock and as
retarding admixture, water-reducing admixture and grind-
ing aid for construction materials. In Western countries, the
majority of molasses has been used as fodder without
adverse environment problems. However, in China,
molasses has been extensively employed as a grinding aid
and a water-reducing and retarding admixture in cement
and concrete [1, 2]. Xiaojian Gao et al. utilised beet
molasses as a grinding aid and proposed that the addition of
0.01–0.05 % beet molasses by cement weight could
improve the particle size distribution, which results in the
strength development of blended cement [3]. Amanmyrat
suggested that beet molasses could significantly increase
both initial and final setting times, slightly increase the
strength of concrete at all ages, with the exception of
concrete at an early age, and exhibit no adverse effects on
durability properties over an extended period (900 days)
[4]. Some researchers have provided different explanations
regarding the retarding mechanism. The retarding action is
generally attributed to the adsorption of molasses on the
surfaces of hydrating cement particles and/or hydration
products [5].
In China, the majority of cement plants use a grinding
aid to increase production or to improve the early strength
of cement. Consequently, the adaptability of cement to
superplasticiser has deteriorated. The use of a grinding aid
causes an increase in fine particles, which accelerates the
hydration of cement. A specific amount of superplasticiser
is adsorbed on the hydrated products to reduce its action.
123
84 L. Weifeng et al.

Table 1 The chemical compositions of cement measured by X-Ray Fluorescence(XRF) mass%

LOI CaO SiO2 Al2O3 Fe2O3 MgO S03 K2O Na2O TiO2 P2O5 MnO Sum

2.67 56.37 24.38 7.20 3.48 1.21 2.82 0.81 0.12 0.32 0.09 0.07 99.54

Thus, a retarding agent is necessary to delay the hydration 350 30

Water requirement of normal consistency/%

Initial setting time
of cement. The sugar in molasses is an effective retarder. Finial setting time
Water requirement of normal consistency
Hence, a detailed investigation of the influence of sugar- 300
cane molasses on the physical properties and hydration 29
kinetics of cement is required. The setting time, fluidity, 250

Setting time/min
development of mechanical strength, hydration kinetics
and microstructure of cement both with and without sug- 200 28
arcane molasses were analysed. The required amount of
150
sugarcane molasses was proposed. The results are
helpful for improving the adaptability of cement to 27
100
superplasticiser.
50
26
0 0.01% 0.02% 0.03% 0.04% 0.05% 1%
Experimental Dosages of sugarcane molasses/%

Fig. 1 Effect of molasses on setting time and water requirement of

Materials normal consistency

Raw materials
The materials used in the experiments included conven-
tional Portland cement without a grinding aid, standard
sand and sugarcane molasses. The chemical composition of
the cement, which was obtained from the Yangzhou Ya-
dong Cement Co., Ltd., is shown in Table 1. The surface
area of the cement is 360 m2 kg-1. The standard sand
(Chinese Standard GB/T17671) was obtained from the
China ISO Standard Sand Co., Ltd.
Paste and mortar
AB, Sweden, at 20 °C). The hydration products and pore
size distribution of the cement pastes were analysed by
X-ray powder diffraction (Japan Rigaku International
Corporation SmartLab x; working condition: 40 kV,
30 mA, Cu Ka); differential scanning calorimetry (DSC)
(NETZSCH STA-449C equipment, a heating rate of 10 °C/
min from 50 to 527 °C under N2 atmosphere), and with
mercury injection apparatus (Quanta chrome Pore Master
GT60). The compressive strengths and fluidities of the
mortars were measured according to Chinese Standards
GB/T17671 and GB/T 2419.

Pastes were prepared with cement and water. A water-to-

cement ratio of 0.29 was used to investigate the effect of
molasses on setting times, hydrated products and pore
distribution. A water-to-cement ratio of 0.5 was used to
investigate the hydration kinetics of cement. Mortars were
prepared with standard sand in accordance with Chinese
Standard GB/T17671 for compressive strength and fluidity.
Cement/sand/water mass ratios of 1:3.0:0.5, respectively,
were employed.
Test
The setting times and the normal consistency of cement
pastes were determined in accordance with Chinese Stan-
dard GB/T 1346 using a Vicat apparatus. The effect of
molasses on the hydration kinetics of cement was investi-
gated using a calorimeter (TAM Air from Thermometric
Results and discussion
Normal consistency and setting times for cement pastes
The required amounts of water and setting times for the
cement pastes are shown in Fig. 1. Sugarcane molasses
influences the amount of water that is required to achieve a
normal consistency for cement. The amount of required
water increases with a small addition of molasses. How-
ever, the amount of required water decreases significantly,
if the amount of molasses added is 1.0 % by mass of
cement. Molasses increases the water requirement due to
the development of cement particle fineness and specific
surface when beet molasses is used as a grinding aid in the
amount of 0.02 or 0.03 % by mass of cement [3]. In this
study, molasses dissolved in solution was directly added to

123
Physical and chemical studies on cement 85

220 0 min
70
3d
30 min 65 28d
Fluidity of cement mortars/mm

60 min 60

Compressive strength/MPa
90 min
200 55
50
45
180 40
35
29.6
30
25
160
20
15
10
140 5
0 0.01 % 0.02 % 0.03 % 0.04 % 0.05 %
0
0.00 0.01 0.02 0.03 0.04 0.05
Dosages of sugarcane molasses/%
Dosages of sugarcane molasses/%
Fig. 2 Effect of molasses on fluidity of cement mortars
Fig. 3 Changes of compressive strength with molasses dosage

the cement. Ashworth showed that sugar can be used as a
surface-active agent to improve the workability of concrete
[6]. For sugar dosages of 0.03 and 0.06 %, the required
amount of water decreased by 4 and 5 %, respectively [7].
As sugarcane molasses contains a high percentage of sugar,
the reduction in required water is partly attributed to the
water-reducing effect of sugar.
As shown in Fig. 1, the initial and final setting times
were delayed by \1.0 % molasses for the cement; this
result was most likely attributed to the sugar in sugarcane
molasses. Numerous types of sugar, such as sucrose and
glucose, have been reported to be excellent retarders [8].
The retarding effect of beet molasses exhibited a significant
improvement in setting times [3]. But when the amount of
molasses added reaches to 1.0 %, the setting times of
cement paste are shortened. It may be correlated with the
electrochemistry change caused by molasses. Singh and
Yang showed that the zeta potential of hydrating cement is
changed from positive to negative due to sugar [9, 10].
Fluidity of cement mortars
sugar bonded to the aluminate phase in cement by com-
plexing or chelating and promoted the dissolution of ions
from the hydrating calcium-silicate phase [11]. Thomas
and Birchall also revealed high calcium and hydroxide ion
concentrations and silicon, aluminate and iron concentra-
tions that were 500 times higher for cement pastes with
50 mM sucrose compared with neat cement pastes [12–14].
Sugar enables ions to coexist in solution at higher con-
centrations without precipitation. In this paper, the increase
in required water may be ascribed to rapid dissolution of
the cement with molasses. Molasses does not reduce the
amount of free water. Hence, it improves the fluidity of
cement mortar.
For equivalent hydration times, the fluidities of cement
mortars decrease slightly when the addition of sugarcane
molasses achieves saturation. With an increase in hydration
time, the saturated amount of sugarcane molasses is
enhanced. This finding demonstrated that the reaction of
sugarcane molasses with hydrated products resulted in the
consumption of molasses during hydration. This topic
requires further investigation.

The fluidities of cement mortars are shown in Fig. 2. For
the same water-to-cement ratio, cement mortars with sug-
arcane molasses show higher fluidities compared with the
blank cement mortar at any hydration time. For Portland
cement without an admixture, the fluidity of the cement
mortar should decrease with an increase in the required
water for a normal consistency of cement paste. However,
a significant difference in fluidities has been demonstrated
in this paper due to the addition of molasses. Although a
small amount of sugarcane molasses increases the fluidity
of cement mortars, it increases the required water for a
normal consistency of cement paste. Young proposed that
Compressive strengths of cement mortars
The compressive strengths of mortars prepared with dif-
ferent amounts of sugarcane molasses are shown in Fig. 3.
Mortars with sugarcane molasses yield higher strengths
compared with the blank mortars at an age of 3d. The
compressive strengths of mortars increase with the amount
of sugarcane molasses. In particular, an approximate 12 %
increase in compressive strength was obtained for the mortar
that contained 0.04 % molasses compared with the blank
mortar. As previously discussed, Amanmyrat suggested that
beet molasses can improve the early strength of concrete due

123
86 L. Weifeng et al.

2.6 increase the surface areas of cement pastes cured at 40 °C in

2.4
(a) Blank
Molasses0.01 % the hydration range of 0.55–0.80 due to a variation in the
2.2 Molasses0.02 %
2.0 Molasses0.03 %
microstructure of C–S–H [5].
1.8 Molasses0.04 %
Heat flow/mW g–1

Molasses0.05 %
1.6 Molasses0.1 % Hydration kinetics
1.4 Molasses1 %

1.2
The heat flow curves and cumulative heat curves for
1.0
0.8 cement pastes are shown in Fig. 4. The heat flow curve
0.6 reflects the hydration rate of cement. The hydration of
0.4 cement involves several distinct and transient processes
0.2
[16]. These processes generally fall within the following
0.0
0 10 20 30 40 50 60 70 categories: (1) the dissolution of molecular species from
Hydration time/h cement particle surfaces, (2) the diffusion of these species
within an aqueous solution or near solid surfaces, (3) the
13 (b) Blank
precipitation or nucleation of hydration products in solu-
12 Molasses0.01 %

11
Molasses0.05 % tion or on solid surfaces, and (4) the growth of disordered
Molasses1 %
10 or crystalline hydration products. Regarding the heat flow
curves for cement pastes, the first peak is ascribed to the
Heat flow/mW g–1

9
8
dissolution of ions from solid surfaces and the formation of
7
6
ettringite (AFt), the second peak is attributed to the
5 hydration of alite, and the shoulder on the second peak is
4 attributed to the second hydration of the aluminate phase to
3 form the monosulphoaluminate phase. Regarding the effect
2
1
of sugarcane molasses on the hydration kinetics of cement
0 paste, sugarcane molasses prolongs the duration of the
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 induction period, in particular 1.0 % molasses (Fig. 4a).
Hydration time/h
The second exothermic peak did not appear after the
cement paste with 1.0 % sugarcane molasses had been
250 (c) hydrated for 3d. Hence, sugarcane molasses significantly
inhibits the hydration of alite and the second hydration of
200 Blank aluminate phase. Young proposed that sugar retards
Cumulative heat/J g–1

150
100
50
0 of sugarcane molasses hinders the wetting of cement par-
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
Hydration time/h
Fig. 4 Effect of molasses on exothermic heat of cement hydration
to a more uniform and dense structure of concrete with beet
molasses under prolonged hardening [4]. In addition, the
early strength of concrete with molasses was higher com-
pared with concrete that contained an effective retarder due
to the chloride contained in molasses [15]. At an age of
28 days, slight increases were obtained for the mortars with
0.03, 0.04 or 0.05 % molasses. However, the compressive
strengths decreased for mortars with 0.01 or 0.02 % sugar
molasses. Juenger and Jennings proposed that sugar can
Molasses0.01 %
Molasses0.02 % hydration due to an increase in the solubility of ions from
Molasses0.03 %
Molasses0.04 %
cement particles and their subsequent adsorption on port-
Molasses0.05 % landite (CH) and hydrated calcium silicate (C–S–H) to
Molasses0.1 %
Molasses1 % prevent their growth [4].
To investigate the effect of sugarcane molasses on the
initial hydration of cement, the initial heat flow was mea-
sured by internal mixing (Fig. 4b). Increasing the dosages
ticles by water. Although a small amount of molasses does
not change the hydration kinetics of cement, it enhances the
maximum rate of liberation heat. When 1.0 % molasses is
added, the maximum rate of liberation heat decreases and
endures longer compared with blank cement. It may be
ascribed that excess molasses promotes the nucleation and
growth of AFt. A small amount of molasses could promote
the dissolution of cement. During deceleration, the hydra-
tion rate is higher for cement with 1.0 % molasses com-
pared with the hydration rate of the other samples. The
cumulative heat reflects the hydration degree (Fig. 4c).
Within 3d of hydration, the hydration degrees of the cement
pastes with molasses are low compared with the blank

123
Physical and chemical studies on cement 87

(a) P CaSO4
2H2O, unhydrated C3A, C3S, C2S and Ferrite for

Intensity/a.u.
D2-cement without molasses
E1-cement with 0.01 % molasses
E3-cement with 0.02 % molasses 40000 cement hydrated for 1 h. At 3 h, Ca(OH)2 has begun to
F2-cement with 0.03 % molasses form due to the hydration of Alite for the cement pastes,
G1-cement with 0.04 % molasses 30000
H1-cement with 0.05 % molasses except for the cement pastes with 0.1 and 1.0 % molasses,
A-cement with 0.1 % molasses
B-cement with 1.0 % molasses 20000 while it did not form until 28d for cement pastes with
1.0 % sugarcane molasses. Hence, excess sugarcane
10000
E F
molasses significantly delays the hydration of C3S at the
E
0
early time. This finding is consistent with the heat flow.
E1
D2 To clarify the effect of molasses on the hydration of C3A
F2
E3
and Ferrite phases, the characteristic peaks of AFt,
A G1
H1 CaSO4
2H2O, C3A and Ferrite were selected. The peaks for
A

6
B cement hydrated at 1, 5 h and 1d are just shown in Fig. 6.
8 10 12 14 16 18 20
2θ /° At 30 min, 1, 3 and 5 h of hydration, the peak intensity of
AFt is higher for the cement paste with 1.0 % molasses,
18000
(b) while the peaks intensities of C3A and Ferrite are lower,
AB Intensity/a.u. 16000
14000 compared to the remaining pastes (see Fig. 6a, b).
AB 12000 CaSO4
2H2O is almost depleted for the cement with 1.0 %
AB 10000 molasses, which was hydrated at 5 h(see Fig. 6b). This
8000
result demonstrates that sugarcane molasses can accelerate
A 6000
A A B
AB
4000
the reaction of C3A, ferrite and CaSO4
2H2O at an early
B
2000 hydration time and presents evidence for the more cumu-
0 lative heat of the cement paste with 1.0 % molasses prior to
D2
S CF E1 5 h of hydration. These results correspond with the results
B E3
F2 of L.M. Meyer and M. Bishop [17, 18]. At hydration of 1d
G1

A
H1 (see Fig. 6(c)), the peak intensities of AFt, C3A and Ferrite
B
20 22 24 26 28 30 32 34 36 38 40 42 44
are higher for the cement paste with 1.0 % molasses
2θ /° compared with the other pastes. It can be concluded that
CaSO4
2H2O is consumed in the range of 5–24 h for the
Fig. 5 X-ray diffractograms of the selected windows of cements
hydrated at 3d. The main reflection peaks of C3A(C), ferrite (F), alite
cement pastes, except for the cement paste with 1.0 %
(A), belite(B), ettringite(E), silicate oxide(S) and portlandite (P) are molasses. Subsequently, the left C3A reacts with AFt to
labelled form monosulphoaluminate (AFm). An amount of 1.0 %
molasses prevents the left C3A from reacting with AFt.
cement paste at any time, except for the cement paste with Some C3A remains even though the cement with 1.0 %
1.0 % molasses. Prior to 2.5 h of hydration, the cumulative molasses was hydrated for 28d.
heat of the cement paste with 1.0 % molasses is signifi- The result from the DSC further proves the affect of
cantly higher, compared to the remaining pastes. The molasses on the hydration of conventional Portland cement
experimental evidence indirectly demonstrates that a small (see Fig. 7). Two peaks in the range of 50–300 °C were
amount of molasses could accelerate the dissolution of observed in DSC curves for cements hydrated for 3d. The
aluminate phase, and excess molasses could accelerate the first endothermic peak at about 100 °C is ascribed to the
nucleation and growth of AFt. dehydration of C–S–H and AFt, and the second endother-
mic peak at about 430 °C is attributed to the dehydration of
Phase compositions of cement pastes Ca(OH)2. There is no endothermic peak at about 430 °C
for the cement paste with 1.0 % molasses. It agrees with
The phase compositions of cement pastes were analysed by the result form XRD. Hence, the endothermic peak at about
X-ray powder diffraction. The cements with and without 100 °C just belongs to the dehydration of AFt for the
molasses were hydrated respectively for 30 min, 1, 3, 5, cement paste with 1.0 % molasses. And the content of AFt
24 h, 3 and 28d. Figure 5 just shows the XRD patterns for is more, compared to the other pastes.
cement pastes hydrated at 3d. At 30 min, AFt has formed According to the previous statement, sugar absorbs on
for the cement paste with 1.0 % sugarcane molasses, and the surface of C3A. When a small amount of molasses is
CaSO4
2H2O has been consumed at 5 h. With the ongoing added, molasses is unable to prevent the hydration of C3A
hydration, the main phase compositions consist of AFt, due to bonding to the aluminate phase by complexing or

123
88 L. Weifeng et al.

(a)
1.6×104 1×104
Molasses1 % +1h Molasses1 % +1h
Molasses0.1 % +1h
Molasses0.05 % +1h C3A Molasses0.1 % +1h
Molasses0.05 % +1h
Ferrite
Molasses0.03 % +1h
9×103 Molasses0.03 % +1h
1.4×104 Molasses0.01 % +1h Molasses0.01 % +1h
Blank +1h
Blank +1h
Intensity/a.u.

Intensity/a.u.
8×103
1.2×104

7×103
1.0×104

6×103

8.0×103
33.0 33.1 33.2 33.3 33.4 33.5 11.9 12.0 12.1 12.2 12.3
2θ /°
2θ /°
3.0×104 13000
2.8×104
Molasses1 % +1h
CaSO4 • 2H2O Molasses1 % +1h

2.6×104
Molasses0.1 % +1h
Molasses0.05 % +1h 12000
Molasses0.1 % +1h
Molasses0.05 % +1h
AFt
Molasses0.03 % +1h Molasses0.03 % +1h
2.4×104 Molasses0.01 % +1h Molasses0.01 % +1h
2.2×104 Blank +1h 11000 Blank +1h
Intensity/a.u.

Intensity/a.u.
2.0×104
10000
1.8×104
1.6×104
9000
1.4×104
1.2×104
8000
1.0×104
8.0×103 7000
6.0×103

11.4 11.5 11.6 11.7 11.8 8.90 8.95 9.00 9.05 9.10 9.15 9.20
2θ /° 2θ /°

(b) Molasses1 % + 5h 10000

Molasses1 % + 5h
1.6×104 Molasses0.1 % + 5h
Molasses0.1 % + 5h Ferrite
Molasses0.05 % + 5h
Molasses0.03 % + 5h
C3A 9500
Molasses0.05 % + 5h
Molasses0.03 % + 5h
Molasses0.01 % + 5h 9000
1.4×104 Molasses0.01 % + 5h
Blank + 5h
Blank + 5h
Intensity/a.u.

Intensity/a.u.

8500

4
1.2×10 8000

7500
1.0×104
7000

6500
8.0×103

7000
33.0 33.1 33.2 33.3 33.4 33.5 11.9 12.0 12.1 12.2 12.3
2θ /° 2θ /°

2.2×104
Molasses1 % + 5h

2.0×104
Molasses1 % + 5h
Molasses0.1 % + 5h CaSO4 • 2H2O 1.6×104 Molasses0.1 % + 5h AFt
Molasses0.05 % + 5h Molasses0.05 % + 5h
Molasses0.03 % + 5h Molasses0.03 % + 5h
1.8×104
Molasses0.01 % + 5h 1.4×104 Molasses0.01 % + 5h
Blank + 5h Blank + 5h
1.6×104
Intensity/a.u.

Intensity/a.u.

1.2×104
1.4×104

1.2×104
1.0×104
1.0×104

8.0×103 8.0×103

6.0×103
6.0×103
11.4 11.5 11.6 11.7 11.8 8.8 8.9 9.0 9.1 9.2 9.3
2θ /° 2θ /°

Fig. 6 The characteristic peaks of AFt, C3A, Ferrite and CaSO4
2H2O for cements hydrated at 1, 5 h and 1d

123
Physical and chemical studies on cement 89

(c)
5500 5000
Molasses1 % +1d Molasses1 % +1d
4800
Molasses0.1 % +1d

5000
Molasses0.1 % +1d
Molasses0.05 % +1d C3A 4600
4400
Molasses0.05 % +1d
Molasses0.03 % +1d Molasses0.03 % +1d

4500
Molasses0.01 % +1d
Blank +1d
4200
4000
Molasses0.01 % +1d
Blank +1d
Ferrite

Intensity/a.u.
3800
Intensity/a.u.

3600
4000
3400
3200
3500 3000
2800
2600
3000
2400
2200
2500 2000
33.0 33.1 33.2 33.3 33.4 33.5 11.9 12.0 12.1 12.2 12.3 12.4 12.5
2θ /° 2θ /°
10000
Molasses1 % +1d Molasses1 % +1d
3200
Molasses0.1 % +1d Molasses0.1 % +1d
9000
Molasses0.05 % +1d Molasses0.05 % +1d
3000 Molasses0.03 % +1d
Molasses0.01 % +1d
CaSO42H2O 8000
Molasses0.03 % +1d
Molasses0.01 % +1d AFt
Blank +1d Blank +1d
2800
Intensity/a.u.

Intensity/a.u.
7000

2600
6000

2400
5000

2200 4000

2000 3000

11.3 11.4 11.5 11.6 11.7 11.8 11.9 8.90 8.95 9.00 9.05 9.10 9.15 9.20 9.25 9.30
2θ /° 2θ /°

Fig. 6 continued

0.20 amount of sugar to achieve an equivalent retardation,

0.15
which suggests that sugar adsorbs on aluminates [20].
Exo

0.10

0.05 Pore porosity and distribution of cement pastes

0.00
DSC/mW mg–1 Endo

Blank + 3d
–0.05 Molasses0.01 % + 3d The pore size distribution and cumulative pore volumes of
Molasses0.03 % + 3d
–0.10 Molasses0.05 % + 3d cement hydrated at 3d are shown in Fig. 8. The pore sizes
Molasses1 % + 3d
–0.15
of the cement pastes with molasses are smaller compared
–0.20
with the pore sizes of the frank cement paste. The corre-
sponding cumulative pore volumes also decrease. These
–0.25
results suggest that the addition of molasses effectively
–0.30
300 350 400 450 500 550 600 650 700 750 800 decreases the pore porosity and improves the density of
Temperature/K cement paste. The decreased pore diameter is favourable to
Fig. 7 DSC curves for cements hydrated for 3d
strength development (as shown in Sect. 3.3) and the
durability improvement of cements and concretes [21]. The
chelating. Garci Juenger and Jennings suggested that sugar reduction in pore size is due to the gradual filling of large
generally absorbs to the surfaces of hydrating cement pores, which is caused by hydration reactions and the
particles and/or the surfaces of hydration products [5]. packing effect. According to these results, a small amount
Benjamin J. Smith proposed that sucrose is stable in of molasses can improve the packing effect for initial
alkaline cement slurries and exhibits selective adsorption times, but does not increase the amount of hydrated pro-
on hydrating silicate surfaces, but not on aluminate sur- ducts. Thus, the higher strengths of the previous concretes
faces in cement [19]. Ramachandran et al. noted that can be attributed to the more uniform and dense structures
cement that contains high aluminates requires a greater formed under prolonged hardening.

123
90 L. Weifeng et al.

(a) and does not form until 28d for the cement paste with
0.30
Blank + 3d 1.0 % molasses.
Molasses0.01 % + 3d
Molasses0.03 % + 3d
A small amount of sugarcane molasses enhances the
0.25
Molasses0.04 % + 3d compressive strength of cement mortar at 3d, which is
Molasses0.05 % + 3d
Molasses0.1 % + 3d
ascribed to the notion that a small amount of molasses
0.20
lowers the porosity and pore size for obtaining a denser
–dV/d(log D)

0.15
structure for cement pastes compared with blank cement
paste.
0.10
Acknowledgements The authors are grateful for the financial sup-
port of the National Natural Science Foundation of China (51202109),
0.05
and the Program for Changjiang Scholars and Innovative Research
Team in University (IRT1146). The support by the facilities of the
0.00 Modern Analysis and Testing Centre at NJTECH, where the detailed
0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.090.1
microstructural analyses were performed, is also acknowledged.
Pore diameter/μm
(b)
0.10
Blank + 3d
Molasses0.01 % + 3d
Molasses0.03 % + 3d
References
Accumlative pore volume/cm3 g–1

0.08
0.06
0.04
0.02
0.00
0.01 0.1
Pore diameter/μm
Fig. 8 Pore size distribution and cumulative volumes for cements
hydrated at 3d
Conclusions
A small amount of sugarcane molasses increases the
required amount of water for the normal consistency of
cement paste and the fluidity of cement mortar. A small
amount of molasses can be used as a retarder in cement to
retard the setting time of cement paste. However, 1.0 %
molasses reduces the required amount of water and accel-
erates the setting and hardening of cement pastes.
The duration of the induction period is prolonged due to
an increased amount of molasses. A small amount of
sugarcane molasses could accelerate the dissolution of
aluminate phase, and excess molasses could promote
nucleation and growth of AFt at the initial time. The for-
mation of AFt from the hydration of C3A and Ferrite is
accelerated by 1.0 % molasses before 5 h. But the second
hydration of C3A and Ferrite is prevented significantly,
since the hydration of 1d for the cement paste with 1.0 %
molasses. At the same time, the hydration of C3S is delayed
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