Use of waste gypsum to replace natural gypsum as set retarders in portland cement

Chea Chandara
a
, Khairun Azizi Mohd Azizli
a
, Zainal Arin Ahmad
a,
*
, Etsuo Sakai
b
a
School of Materials & Mineral Resources Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
b
Tokyo Institute of Technology, Graduate School of Science and Engineering, Department of Metallurgy and Ceramic Science,
2-12-1 Meguro-ku, Ookayama, Meguro-ku, Tokyo 152-8552, Japan
a r t i c l e i n f o
Article history:
Accepted 24 November 2008
Available online 7 January 2009
a b s t r a c t
The present study is focused on clarifying the inuence of waste gypsum (WG) in replacing natural gyp-
sum (NG) in the production of ordinary Portland cement (OPC). WG taken from slip casting moulds in a
ceramic factory was formed from the hydration of plaster of paris. Clinker and 35 wt% of WG was
ground in a laboratory ball mill to produce cement waste gypsum (CMWG). The same procedure was
repeated with NG to substitute WG to prepare cement natural gypsum (CMNG). The properties of NG
and WG were investigated via X-ray Diffraction (XRD), X-ray uorescence (XRF) and differential scanning
calorimetry (DSC)/thermogravimetric (TG) to evaluate the properties of CMNG and CMWG. The mechan-
ical properties of cement were tested in terms of setting time, exural and compressive strength. The XRD
result of NG revealed the presence of dihydrate while WG contained dihydrate and hemihydrate. The
content of dihydrate and hemihydrates were obtained via DSC/TG, and the results showed that WG
and NG contained 12.45% and 1.61% of hemihydrate, respectively. Furthermore, CMWG was found to
set faster than CMNG, an average of 15.29% and 13.67% faster for the initial and nal setting times,
respectively. This was due to the presence of hemihydrate in WG. However, the values obtained for ex-
ural and compressive strength were relatively the same for CMNG and CMWG. Therefore, this result pro-
vides evidence that WG can be used as an alternative material to NG in the production of OPC.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
The setting behaviour of cement is mainly due to the reaction of
tricalcium aluminate (C
3
A), 3CaO Al
2
O
3
. The reaction of pure C
3
A
with water leads to immediate stiffening of the paste, known as
ash set. Thus, gypsum is added to the cement clinker during the
grinding of Portland cement to retard the rapid reaction between
C
3
A and water (Neville, 2002). The amount of gypsum used in clin-
ker varies from 3 to 5 wt%, depending on its purity (Potgieter et al.,
2004). Gypsum consists of various amounts of CaSO
4
2H
2
O (dihy-
drate), CaSO
4
.0.5H
2
O (hemihydrate) and CaSO
4
(anhydrite). The ra-
tios in which these calcium sulfate forms occur in the gypsum can
have a profound effect on the setting behaviour of the cement, be-
cause their respective solubilities in water are signicantly differ-
ent from one another (Strydom and Potgieter, 1999). Typically,
natural gypsum (NG) is used as setting retarder. However, due to
environmental concerns and the lack of natural deposits of gyp-
sum, various gypsumby-products, such as phosphor-, citro-, desul-
pho-, boro- and FGD gypsum, are used as setting retarders to
replace the natural gypsum (Papageorgiou et al., 2005; Kavas
et al., 2005; Ozkul, 2000; Tzouvalas et al., 2004). Besides, there
are other gypsum products such as plasterboard, wallboard, dry-
wall and slip casting mould (in ceramic production), obtained from
the hydration of plaster of paris (POP), which can be considered as
gypsum by-products too because they have similar chemical com-
positions to NG.
When gypsum (CaSO
4
2H
2
O) is heated to 150
0
C, it will lose
three-fourths of its water to formcalciumsulfate hemihydrate (Ca-
SO
4
0.5H
2
O) as shown in Equation 1 (Ramachandran et al., 2002);
and when it is ground into a powder form, it is referred to as POP.
In the production of plasterboard, wallboard, drywall and slip cast-
ing mould, POP is mixed with water to produce these products.
When it is mixed with water, it is converted into gypsum, Equation
2, which is called waste gypsum (WG) (Kotz et al., 2003).
CaSO
4
2H
2
O ! CaSO
4
0:5H
2
O 1:5H
2
O 1
CaSO
4
0:5H
2
O 1:5H
2
O ! CaSO
4
2H
2
O 2
It is important to note that different types of WG contain differ-
ent amounts of dihydrate, hemihydrate and anhydrite. This is due
to the difference in the amount of water which is attached to hemi-
hydrates after the product has been used. Normally, WG is found to
have a mixture of hemihydrate and dihydrate. For instance, slip
casting mould in ceramic factories is considered a waste due to
its low absorption rate, once 80% of hemihydrates have been con-
verted into dihydrates.
0956-053X/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.wasman.2008.11.014
* Corresponding author. Tel.: +6045996128; fax: +6045941011.
E-mail address: [email protected] (Z.A. Ahmad).
Waste Management 29 (2009) 16751679
Contents lists available at ScienceDirect
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j our nal homepage: www. el sevi er . com/ l ocat e/ wasman
According to Gypsum Recycling International (2008), 80 million
tons of plasterboard, wallboard and drywall are produced every
year, and approximately 15 million tons of WG is being sent to
landlls yearly. This amount excludes the WG that comes from slip
casting moulds in ceramic factories. WG in itself is not dangerous,
but when it is mixed with organic waste and is exposed to rain in
an anaerobic environment, tests have shown that hydrogen sulde
gasses can evolve. Hydrogen sulde gas is a dangerous gas that in
high concentration is lethal, and in low concentration gives a rot-
ten egg smell. Therefore, it is important to recycle or reuse gypsum
to protect the health and well being of mankind against environ-
mental pollution.
2. Research signicance
The effect of WG as set retarders in OPC to replace NG has been
studied. WG fromslip casting moulds in ceramic factories had been
chosen as a representative of other WG products such as plaster-
board, wallboard and drywall to replace NG. The WG was investi-
gated to quantify the amounts of dihydrate, hemihydrates and
anhydrite, because they are associated with the performance of
the cement produced. Most importantly, this work highlights one
of the possible ways to solve an environmental problem. Moreover,
this research was conducted to overcome the shortage of NG
deposits by reusing WG.
3. Experimental program
The clinker (CL) and NG used in the cement preparation were
obtained from a Malaysian cement factory. WG, which is the waste
material from slip casting moulds, was obtained from a ceramic
factory. The chemical composition of the raw materials was ana-
lyzed via PL 9800 Simultaneous XRF; the results are shown in Table
1. CL was ground in a laboratory steel ball mill with 35 wt% of NG
for 90 min to produce cement natural gypsum (CMNG). The same
procedure was repeated for WG with a grinding duration of
120 min to produce cement waste gypsum (CMWG). Both cements
must have a surface area in the range of 36003900 cm
2
/g. The
proportions of the raw materials to prepare CMNG and CMWG
are given in Table 2. The experimental procedure was designed
to achieve two main goals: the rst one is to investigate the prop-
Table 1
Chemical composition of materials used.
Component Chemical analysis (wt%)
Clinker Natural gypsum Waste gypsum
SiO
2
21.304 1.90 0.93
CaO 65.746 35 37
Al
2
O
3
6.107 0.63 0.16
Fe
2
O
3
3.829 0.28 0.17
MgO 1.626 0.97
K
2
O 0.838 0.13 0.03
SO
3
0.74 41 42
NiO 0.02 0.02
SrO 0.09 0.13
Free lime 0.782
LOI 20.4 18
Table 2
Proportions of Mixture CL with NG and WG.
Symbol CM97NG CM96NG CM95NG CM97WG CM96WG CM95WG
CL (%) 97 96 95 97 96 95
NG (%) 3 4 5
WG (%) 3 4 5
Fig. 1. DSC/Tg curves of natural gypsum.
1676 C. Chandara et al. / Waste Management 29 (2009) 16751679
erties of raw materials such as NG and WG and the second is to
investigate the setting time, exural strength and compressive
strength of CMWG compared to CMNG.
4. Tests details
The chemical composition of raw materials was obtained from
the APL 9800 Simultaneous XRF while the phase was analyzed
using X-Ray Diffraction (XRD), Siemens D5000. The contents of
dihydrate and hemihydrate were estimated from the weight losses
measured of corresponding peaks of DSC/TG curves followed by
the reactions of dehydration of dihydrate (gypsum) to hemihy-
drates, Equation 1, and dehydration of hemihydrates to anhydrite
(as in Equation 3).
CaSO
4
0:5H
2
O ! CaSO
4
0:5H
2
O 3
The mechanical properties of cement samples were tested
for setting time, exural strength and compressive strength. A
400 g cement sample was mixed with a suitable amount of water
to give a paste of standard consistency. European Standard
EN196-3 was used as a standard to evaluate the setting time. The
mortars were casted by mixing cement with specied sand and
water, at a ratio of 1:3:0.5 into three prismatic specimens 40 mm
x 40 mm 160 mm and compacted in accordance with European
Standard EN 196-1. The sample was tested at the ages of 2, 7 and
28 days. The results of exural and compressive strengths were
the average of the three measurements and six measurements,
respectively. All samples followed the standard to avoid any exper-
imental errors. The nal result was an average of three sets of mea-
surement for each type of gypsum.
5. Results and discussion
5.1. Raw materials (WG and NG)
Fig. 1 shows DSC/TG curves for NG, where the rst peak be-
tween 110 and 170
o
C was due to the dehydration of dihydrate
to hemihydrate; the weight losses are the weight of 1.5H
2
O.
According to Equation 1, the content of dihydrate could be calcu-
lated. The second peak between 170 and 190
o
C was the dehydra-
tion of hemihydrate to anhydrite; the weight losses presented the
weight of 0.5H
2
O, thus the content of hemihydrates could be deter-
mined by using Equation 3. The DSC/TG curves of WG was similar
those of NG, as shown in Fig. 2, where the dehydration peak of
dihydrate occurred between 110 and 160
o
C and the dehydration
peak of hemihydrates was between 160 and 180
o
C. Table 3 gives
a summary of dihydrate, hemihydrates and anhydrite in NG and
WG. Hemihydrate was found to be higher (12.46%) in WG as com-
pared to NG (1.61%) because certain amounts of POP (hemihy-
drates) in WG had not absorbed the water to form dihydrate
during the hydration process of slip casting.
According to the results of chemical composition of WG and NG
in Table 1, WG and NG had similar chemical compositions with
minor differences in the values of loss on ignition (LOI). The value
of LOI presented the loss of combined water in a particular gyp-
sum. The difference in the values of LOI signied that both gyp-
sums consisted of different types of calcium sulfate such as
dihydrate (CaSO
4
2H
2
O), hemihydrate (CaSO
4
0.5H
2
O) and anhy-
drite (CaSO
4
). WG had a lower value of LOI compared to NG, indi-
cating a higher amount of hemihydrate as compared to NG. This
result further conrms the result obtained by DSC/TG. The pres-
ence of impurities was insignicant in the gypsum for the value
was 2.79% and 2.30% for NG and WG, respectively.
XRD results presented in Fig. 3 further conrmed the existence
of a higher amount of hemihydrate in WG as compared to NG. The
diffraction peak of WG matches the reference pattern of POP
Fig. 2. DSC/Tg curves of waste gypsum.
Table 3
The amount of dihydrate, hemihydrate and anhydrite in NG and WG.
Components Natural gypsum (%) Waste gypsum (%)
Dihydrate 91.28 80.90
Hemihydrate 1.61 12.45
Anhydrite 4.32 4.34
Other impurities 2.79 2.30
C. Chandara et al. / Waste Management 29 (2009) 16751679 1677
(hemihydrate) at 2h = 14.76, 25.54 and 29.76 and dihydrate at
2h = 11.68, 20.84, 23.48 and 29.23. For NG, the entire peak matches
the reference pattern of dihydrate. This result is in agreement with
the DSC/TG analysis, which conrms the presence of hemihydrate
in WG; it had not converted to gypsum (dihydrate) during the
hydration process of slip casting. Papageorgiou et al. (2005) re-
ported that the existence of hemihydrate decreases the setting
time of cement. Thus, it can be estimated that CMWG produced
in this work would set faster than CMNG.
5.2. Mechanical properties of cement
Table 4 shows the effects of WG and NG on the quantity of
water required giving a paste of standard consistency and also
the initial and nal setting times of the cement produced. There
was no signicant difference in the water required to produce
CMNG and CMWG. However, CMNG poses both higher initial set-
ting time and nal setting time as compared to CMWG. The aver-
age value of the initial and nal setting times in CMNG was
137.33 and 170.67 min, respectively, while in CMWG, it was
116.33 and 147.33 min, respectively. Briey, CMNG set more
slowly than CMWG, an average of 15.29% and 13.67% for initial set-
ting time and nal setting time, respectively. The result afrmed
the nding of Papageorgiou et al. (2005) who stated that the pres-
ence of hemihydrate decreases the setting time of cement.
The results of compressive strength in Table 5 show that the
average values of CMNG were 18.93, 33.77 and 50.91 MPa for the
ages of 2 days, 7 days and 28 days, respectively. CMWG had aver-
age values of 18.22, 33.75 and 52.26 MPa for the ages of 2 days, 7
days and 28 days, respectively. Thus, there was a minor difference
which can be considered as elimination between the result of the
compressive strength of CMNG and CMWG. However, the opti-
mum gypsum content, which gives the maximum compressive
strength at the age of 28 days, was 3 wt% of gypsum for CMWG
and 4 wt% of gypsum for CMNG, which is in agreement with the
content of gypsum used in cement plants. The difference in opti-
mum values of gypsum used in CMNG and CMWG are conrmed
to be associated with the amount of hemihydrates.
As for exural strength in Table 5, the average values of CMNG
were 4.02, 6.26 and 7.06 MPa at the ages of 2 days, 7 days and 28
days, respectively. Also, CMWG had average values 3.95, 6.24 and
Fig. 3. XRD patterns of natural gypsum and waste gypsum.
Table 4
Effect of WG and NG content on the initial and nal setting time of cement
Sample Water/Cement
(%)
Initial setting time
(minutes)
Final setting time
(minutes)
CM97NG 26.25 138 169
CM96NG 26.50 140 174
CM95NG 26.50 134 169
Average 26.42 137.33 170.67
CM97WG 26.25 98 125
CM96WG 26.25 125 164
CM95WG 26.00 126 153
Average 26.17 116.33 147.33
Table 5
Effect of WG and NG content on the compressive and exural strength.
Sample Compressive Strength (MPa) Flexural Strength (MPa) Surface Area (cm
2
/g)
2 Days 7 Days 28 Days 2 Days 7 Days 28 Days
CM97NG 16.05 0.4 31.43 0.5 49.2 1.3 3.59 0.1 5.78 0.3 6.30 0.3 3816
CM96NG 18.92 0.2 33.83 0.4 52.82 1.1 4.08 0.1 6.38 0.3 7.07 0.4 3637
CM95NG 21.82 0.4 36.05 1.2 50.7 0.8 4.39 0.1 6.62 0.4 7.81 0.1 3691
Average 18.93 33.77 50.91 4.02 6.26 7.06 3714.67
CM97WG 18.45 0.8 37.15 1.9 53.25 2 3.96 0.1 6.49 0.4 7.51 0.2 3785
CM96WG 18.95 0.1 32.13 0.6 51.75 1 4.17 0.1 6.37 0.1 7.16 0.1 3948
CM95WG 17.25 0.1 31.98 0.1 51.77 0.2 3.71 0.2 5.87 1.3 7.79 0.4 3785
Average 18.22 33.75 52.26 3.95 6.24 7.49 3839.33
1678 C. Chandara et al. / Waste Management 29 (2009) 16751679
7.49 MPa at the ages of 2 days, 7 days and 28 days, respectively.
This showed that there was little difference in the values of exural
strength and compressive strength between CMNG and CMWG.
Thus, it is clear that the presence of hemihydrate contained in
WG accelerated the setting of the cement, but did not have a neg-
ative effect on the strength of cement (Papageorgiou et al., 2005).
Moreover, it is worth noting that 4 wt% of gypsum in CMNG and
CMWG established similar properties, thus demonstrating that
WG can be used as an alternative material to replace NG in cement
plants.
6. Conclusion
The present work has revealed the difference in properties of
WG and NG that affect the mechanical properties of CMNG and
CMWG. The presence of hemihydrate in WG was found to play
an important role in decreasing the setting time of CMWG. The set-
ting time of CMWG was decreased by 15.29% and 13.67% for initial
and nal setting times, respectively, without sacricing the
mechanical performance. Thus, for other WG products such as
plasterboard, wallboard and drywall, proper control of the content
of hemihydrate in WG is required before use as a replacement for
NG.
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