Indian Journal of Engineering & Materials Sciences

Vol. 19, December 2012, pp. 421-426

Usage of molasses in concrete as a water reducing and retarding admixture

Hasan Yildirim* & Baris Altun
Material Science Division, Faculty of Civil Engineering,
Istanbul Technical University, 34469, Maslak, Istanbul, Turkey
Received 5 July 2011; accepted 28 September 2012

Molasses is a by-product material like lignosulphonate, which is obtained from paper and sugar industries. Molasses
shows plasticizing effect in concrete. In this study a comparison is made between molasses with 40% purity grade and
lignosulphonate with respect to the improvements in properties of concrete. Three molasses obtained from different sugar
factories are used in this study at two admixture dosages, such as 0.4% and 0.7% of cement dosage. Two types of concretes
are prepared with two cement dosages, such as 270 and 320 kg/m3, respectively. The workability and setting times are
determined at the fresh state and both compressive and flexural strength properties are measured on hardened concretes.
Furthermore, durability properties are compared by using capillary and sulphate resistance tests. Molasses can be used as a
Type D, if initial and final setting times and compressive strengths at 35 and 125 days which are measured in this work, are
considered, and can be used as Type A because of reducing the dosage of admixture, in concrete in accordance with ASTM
C 494 standard.

Keywords: Molasses, Water reducing, Retarding admixture, Lignosulphate

Molasses is a by-product of sugar industry, which
uses beet in the production. Like lignosulphonate,
which is a by-product of paper industry, molasses also
shows plasticizing properties in concrete.
Furthermore, due to the existence of sugar in
molasses, it exhibits retarding effect in fresh concrete.
Molasses has been used in many industries as raw
material, like animal food industry, in the production
of alcohol, ferment and glycerin1-3. In Turkey there
are 27 sugar factories, which process sugar beet to
obtain sugar. At the end of various refining processes
a dark-brown syrup, which is called molasses is
obtained in sugar industry. Molasses consist of 50%
sucrose, 30% of other sugars (ash and nitrous
materials) and 20% water approximately. About 4-8%
of beet remains as molasses after the process. The
composition of molasses differs depending on the
source it has been obtained, such as from reed or beet.
Reed molasses, which have invert sugar, has lower
nitrogenous material than molasses of beet4.
Pigments of molasses are surfactants and
electronegative colloids that contain unsaturated
groups, hydroxyl groups, and carboxyl groups.
Pigments of beet molasses contain 63.1-81.3%
products of alkaline hydrolysis of inverted sugar, 4.0-
18.3% melanoidins, and 9.5-17.8% caramels5. These
____________
*Corresponding author (E-mail: yildirimhasan63@hotmail.com)
components have an important effect on the
plasticizing property of molasses.
Although the number of studies on the usage of
molasses in concrete is limited, there are some studies
about the effect of sugar on the properties of concrete.
Addition of sugar in concrete in small amounts delays
the hydration reaction of cement6-8. The concretes
made with sugar addition show strength reduction at
early ages, but their later age strengths might be
higher9,10. For example, sucrose, which has five
members ring, is classified as non-reducing sugar and
may retard the initial setting of cement from 1000 to
8000 min and final setting from 1400 to 15000 min7,8.
Although there is divergence of opinion among
researchers as to what cause the retardation effect, the
most commonly accepted opinion is its calcium
binding and complexing ability9,11. Sucrose is produced
from agricultural plants of reed and beet. Haworth
formulation of the sucrose (α-D-glukopiranozido-β-D-
fruktofuralozid) is given in Fig. 112.
Fig. 1—Haworth formulation of sucrose
422 INDIAN J ENG. MATER. SCI., DECEMBER 2012

Experimental Procedure the molasses were 51.2% and 47.3% and 48.4% for
Materials Konya, Bor and Susurluk molasses, respectively.
Cement
Mix design
Ordinary Portland cement (OPC) was used for the
Fourteen series of concretes were prepared. Two
concretes. The properties of CEM I 42.5 are given in
different cement dosages were used in the concretes,
Table 1a-1c. The tests were carried out according to
such as 270 kg/m3 and 320 kg/m3. A series of concretes
the EN 196 standard.
without admixture were produced as control mixtures.
Aggregates Two different admixture ratios, 0.4 and 0.7% of the
Crushed limestone with maximum aggregate size of cement by weight, were used in the production of
16 mm was used as coarse aggregate. Sea sand and admixture concretes. Lignosulphonate-based plasticizer
crushed stone sand were used as fine aggregates. The and Konya molasses were used as admixtures for the
grading of the aggregate mixture is presented in Table 2. concretes having cement dosage of 270 kg/m3. Three
types of the molasses with 40% purity grade and
Admixture
lignosulphonate were used with two different dosages in
A lignosulphonate-based water reducer (ASTM C 494
the concretes having the dosage of 320 kg/m3. 270 and
Type A) and molasses from three different sources, such
320 kg/m3 cement dosages were selected in the
as Konya, Susurluk and Bor sugar factories of Turkey,
experiments because they are the most common dosages
were used as plasticizer admixture. All three of molasses-
used in the production of C25 and C30 classes. Constant
based and lignosulphonate-based admixtures were
slump values were aimed. Water content was changed
including 40% efficient material by weight. Density of the
according to workability. The mixing proportions of the
lignosulphonate and molasses-based admixtures were
concretes are shown in Table 3. The code of concrete
1.19 g/dm3 and 1.20 g/dm3, respectively. Sucrose ratios of
Table 1c—Chemical composition of cement
Table 1a—The physical properties and chemical analysis of cement
Component %
Density (g/cm3) 3.18 SiO2 21.50
Specific surface area (blaine) (cm2/g) 3030 Insoluble residue 0.21
Initial setting time (h:min) 3:00 Al2O3 5.61
Final setting time (h:min) 3:45 Fe2O3 2.95
Le Chatelier opening (mm) 1.0 CaO 63.72
MgO 1.66
Table 1b—Norm compressive strength of cement
SO3 2.96
Age (day) Compressive strength (MPa) Cl- 0.01
Ignition loss 0.37
1 14.9
Table 2—Grading of the aggregate mixture
2 27.6
7 44.4 Sieve size (mm) 16 8 4 2 1 0,5 0,25
28 56,2 Passed (%) 100 84 60 40 34 19 5
Table 3—Mixing proportions of the concretes
3
Concrete code Cement Water (kg/m ) Aggregate Water reducing Admixture Admixture Slump Base of admixture
(kg/m3) (kg/m3) capacity (%) (%) (kg) (cm)
270C00 277 245 1804 0 0,0 0,00 16 Control specimen
270L04 269 235 1801 4 0,4 1,08 14 Lignosulphonate
270K04 276 224 1835 9 0,4 1,10 15 Konya molasses
270L07 269 218 1846 11 0,7 1,89 15 Lignosulphonate
270K07 272 214 1827 13 0,7 1,90 17 Konya molasses
320C00 325 241 1766 0 0,0 1,00 13 Control specimen
320L04 323 215 1791 11 0,4 1,29 15 Lignosulphonate
320K04 325 229 1784 5 0,4 1,30 15 Konya molasses
320B04 324 228 1791 5 0,4 1,30 15 Bor molasses
320S04 323 224 1790 7 0,4 1,29 14 Susurluk molasses
320L07 323 209 1815 13 0,7 2,26 16 Lignosulphonate
320K07 324 222 1788 8 0,7 2,27 15 Konya molasses
320B07 325 216 1791 10 0,7 2,27 16 Bor molasses
320S07 321 223 1791 7 0,7 2,25 14 Susurluk molasses
 YILDIRIM & ALTUN: USAGE OF MOLASSES IN CONCRETE
indicates the dosage, the type of admixture (L:
lignosulphonate; B: Bor, K: Konya, S: Susurluk
molasses) and the usage ratio of admixture,
respectively. As an example 270L04 shows; the
concrete produced with cement dosage of 270 kg/m3
and with lignosulphonate dosage of 0.4%. Water
reducing capacity, which is shown in the fourth
column of the Table 3, is the ratio of reduced water to
the initial water for the admixtured mixtures at the
same workability.
Figure 2 shows that for the concrete of 320 dosages
LBA reduces more water than MBA. However, for
the concrete of 270 dosages MBA is better water
reducer than LBA. Because of water requirement (5%
limit), all of mixtures with molasses conformed to the
EN 932-2 and ASTM C494.
Test procedure
Prismatic specimens with the dimensions of
7×7×28 cm and cube specimens with the dimensions
of 7×7×7 cm were prepared for the tests. Compressive
strength, flexural strength, ultrasonic pulse velocity
and according to DIN 52617 standard method,
capillarity tests were carried out on the specimens at
35 and 125 days. Vicat setting time tests were also
applied on the pastes, which were including the
admixtures. All the concrete specimens were cured in
23±2°C lime saturated water during 35 days after
casting. After 35 days some of the specimens were
transferred into 10% Na2SO4 solution (by weight) and
stored there up to 125 days. According to ASTM C
1012, standard test method for length change of
hydraulic-cement mortars exposed to a sulphate
solution, sulphate attack test takes longer time with
sulphate solution with 5% concentration. In this study,
solution concentration was determined as 10% to
decrease the test time. The pH value of solution was
kept constant at 9.5~11.5.
Fig. 2—Water reducing capacities
423
Results and Discussion
Fresh properties
For the same workability, water reducing capacity
of the molasses-based admixture (MBA) is higher
than the lignosulphonate-based admixture (LBA) for
270 kg/m3 dosage concrete. Konya MBA reduces
9-13% water when LBA 4-11% for 270 content
concretes at the admixture dosage ratios of 0.4 and
0.7, respectively. However, for the concretes with the
cement dosage of 320 kg/m3, MBAs are not as
efficient as those for the lower dosage concretes. It is
known that when aggregate concentration decreased,
increase in cement dosage increases the compressive
strength less than high aggregate concentration.
MBAs at 0.4% dosage reduced the water 5-7%
when LBA 11% for the same workability of 320 kg
cement contents. The higher ratios of admixtures have
caused the higher water reducing as expected. When
the admixtures are used as 0.7%, the water reductions
of admixtures are 7-10% and 13% for MBAs and LBA,
respectively. Test results show that the molasses are
different from each other for water reducing capacity.
Setting times of the cement pastes, which were
produced with dosages of 0.4% and 0.7% for four types
of admixtures, are given in Table 4. Paste codes
indicate the type of the admixture and the dosage
respectively. Normal consistency water of the cement
was taken into consideration in preparation of the
pastes for setting time test. Setting times tests were
applied by vicat needle apparatus in accordance with
ASTM C191. All the admixtures, which were used in
the concrete mixtures, cause the retardation on setting
times. Setting times are getting longer with increase of
admixture ratio in cement paste. Retardations in setting
times of concretes having sucrose are well known8,9,12-
16
. The same retardation effect is expected from
molasses due to its sucrose content. Molasses-based
admixtures are delaying final setting times up to 16:30
h while control paste has only 5 h.
424 INDIAN J ENG. MATER. SCI., DECEMBER 2012

Hardened concrete properties than MBA for the concretes of 320 dosages. This
Strength results could be the cause for strength loss of MBA concretes
Compressive strength test results are given in according to LBA concretes. The compressive
Fig. 3. All the concretes having admixture except 320 strengths are not changed significantly at 125 days
dosages and 0.4% MBA has higher compressive with respect of 35 days test results for 320 dosages
strengths than the control specimens for 35 days. with 0.4% usage MBA concrete mixtures. They are
Increase in compressive strength is due to decreasing showing the same trend with the results of 35 days
of w/c ratios of the concretes with admixture. The water cure.
usage of MBA causes to decrease of compressive Flexural strength test results are shown in Fig. 4.
strengths with respect of LBA for 320 dosage All the concrete mixtures produced with admixtures
concretes. As mentioned above, molasses does not have higher flexural strengths than the control
decrease the w/c ratio for 320 kg/m3 dosage concrete specimens. Concretes with MBA have also displayed
as much as 270 kg/m3 one especially at the lower higher strengths than the specimens with LBA. As a
usage dosage. Additionally, LBA is more effective difference from the compressive strength test results,
flexural strengths at 125 day for water cure showed
Table 4—Setting times of the pastes increase with respect to 35 day test results.
Paste Code Initial setting (h:m) Final setting (h:m)
Sulphate attack
Control 3:15 5:00
L04 3:40 6:00
The strengths of concretes stored in sulphate
K04 10:00 16:10 solution are given in Figs 3 and 4. It seems that the
B04 8:30 16:30 compressive strengths do not show any deterioration
S04 9:45 15:30 in 125 day storage period in sulphate solution.
L07 5:10 9:30 Similarly, it was reported that any damage has not
K07 12:00 16:30 been observed at the end of 19 weeks storage time in
B07 11:50 16:30 sulphate solutions16-18. When the flexural strengths are
S07 11:50 15:30 considered even sulphate solution-stored specimens
exhibited higher strengths than those of water-cured
specimens for the same period of time. This behavior
may be due to the filling effect of sulphate salts in the
pores before ettringite formation.
When the ultrasonic pulse velocities, which are
presented in Fig. 5 are studied, it is seen that there is
not a significant difference between the admixtured-
concretes and control specimens.

Capillary results
Coefficients of capillary of the concretes are given
Fig. 3—Compressive strength test results in Fig. 6. The coefficients of the control specimens

Fig. 4—Flexural strength test results Fig. 5—Ultrasonic pulse velocity test results
 YILDIRIM & ALTUN: USAGE OF MOLASSES IN CONCRETE
Fig. 6—Capillary test results
Fig. 7—Coefficient of capillarity and setting times for 270 dosage
concrete
are much greater than the admixture-concrete
specimens as shown in Fig. 6. Although usage of
water reducing admixtures decreases the capillary due
to lower w/c ratio, the reduction in capillary is higher
for the molasses added concretes than those of
lignosulphonate concretes. The coefficients of the
capillary for MBA concretes are 40-45% lower than
those of control mixtures while 10-14% lower for
LBA concretes.
The relations of coefficients of capillary with
setting times are given in Figs 7 and 8, for 270 and
320-dosage concretes, respectively. It seems that for
admixture added concretes longer the setting time,
lower the coefficient of capillary. The decrease of
capillaries with increase in setting times can be due to
the slow hydration process and formation of more
homogeneous internal structure, hence modification
of capillary pores in MBA concretes.
Conclusions
The following conclusions can be drawn from this
study:
(i) Usage of molasses as a plasticizer in concrete is
satisfying the ASTM C494-98 standard for
water reduction criteria.
425
Fig. 8—Coefficient of capillarity and setting times for 320
dosages concrete
(ii) Molasses can be used as a Type D and by
reducing the dosage of admixture it can be used
as Type A in concrete in accordance with ASTM
C 494 standard.
(iii) Usage of lignosulphonate and molasses-based
plasticizers causes to reduction of the coefficient
of capillary due to increase in setting times as
well as decrease in w/c ratios.
(iv) Molasses-based plasticizers are more effective
on reducing of capillary coefficient than
lignosulphonate-based plasticizers.
(v) Some strength difference among samples is far
from the w/c development trend. In this study,
molasses with 40% purity grade was used to
prevent the other interaction. 0.7% is high
amount and molasses, which is used to obtain
this amount, can cause to harmful effects like air
entrainment. To prevent decrease of the strength
because of these effects, using of some
chemicals in producing of molasses can be
effective.
(vi) Molasses are effective on retarding of setting
times. The high retarding effect should be taken
into consideration for molasses concretes.
(vii) Molasses added concretes do not show any
different behavior than lignosolphonate
concretes in sulphate solution for 125 days
storing time.
(viii) According to these results, it’s clear that
molasses has water reducing and retarding effect
on concrete. To use molasses as water reducing
and retarding admixture, some additives like
triethylamine, can be added to molasses.
References
1 Gorgulu F, Beet Paste and Molasses in Feeding Animals
(Guven Press, Ankara), 1967, (in Turkish).
2 Leblebici M J & Kavas M F, Handbook of Quality Control
Laboratory, (Turkey Sugar Factories Co. Analytical Branch
Press, Ankara) 2000), (in Turkish).
426 INDIAN J ENG. MATER. SCI., DECEMBER 2012
3 Akakinci M, Bozok O & Gokdag C, Technology of Sugar
(Turkey Sugar Factories Co. Analytical Branch Press,
Ankara), 1955, (in Turkish).
4 Gorgulu F, Beet Paste and Molasses in Feeding Animals
(Guven Press, Ankara), 1967, (in Turkish)
5 Bolobova A B & Kondrashchenko V I, Appl Biochem
Microbiol, 36 (3) (2000) 243-253.
6 Neville A M, Properties of Concrete, (Pearson Education Asia
Pte. Ltd., London), 2000.
7 Thomas N L & Birchall J D, Cem Concr Res, 13 (1983)
830-842.
8 Bruere G M, Nature, 212 (1966) 502-503.
9 Gambhir M L, Concrete technology, 2nd ed (Tata Mc Graw-
Hill, New Delhi), 1995.
10 Joisel A, Admixtures for Cement, Special Publ, (1973)
11 Juenger M C G & Jennings H M, Cem Concr Res, 32 (3)
(2002) 393-399.
12 Berg J M, Tymoczko J L & Stryer L, Biochemistry, 6th ed,
Ch.11 (W H Freeman and Company, New York, USA), 2007.
13 Luke K & Luke G, Adv Cem Res, 12(1) (2000) 9-18.
14 Jumadurdiyev A, Ozkul M H, Saglam A R & Parlak N, Cem
Concr Res, 35 (2005) 874-882
15 Gao X J, Yang Y Z & Deng H W, Constr Build Mater, 25
(2011): 3782–3789
16 Skalny J P, Marchland J & Odler I, Sulphate Attack on
concrete, Modern Concrete Technology, Ser 10 (Spon Press,
New York), 2002,
17 Ouyang C, Naani A & Chang W F, Cem Concr Res, 18 (1988)
699-703
18 Atahan H N, Pekmezci B Y, Uyan M & Yıldırım H, Effects of
Sulphates on the Durability of OPC and Sulphate Resistance
Cement Concretes, 5th Nat Congress on Concrete, Istanbul,
2003, pp. 411-419, (in Turkish).