elsevier editorial system(tm) for construction & … · elsevier editorial system(tm) for...
TRANSCRIPT
Elsevier Editorial System(tm) for
Construction & Building Materials
Manuscript Draft
Manuscript Number:
Title: Effect of palm oil clinker powder characteristics on setting and
hardened properties of cement
Article Type: Research Paper
Keywords: Palm oil clinker powder, Setting time, Water consistency,
Compressive strength, Soundness.
Corresponding Author: Mr. Mohammad Razaul Karim, Mr.
Corresponding Author's Institution: University of Malaya
First Author: Mohammad Razaul Karim, Mr.
Order of Authors: Mohammad Razaul Karim, Mr.; Hashim Abdul Razak, Prof.;
Sumiani Yusoff, Prof.
Abstract: The characteristics of waste material play an important role
in setting and hardened properties of cement, which are a significant
consideration for introducing a new supplementary cementitious material.
This study aims to investigate the effect of palm oil clinker powder
(POCP) characteristics on setting and hardened properties of cement. The
characteristics of POCP were determined using XRF, FTIR, XRD, particle
size analyzer, TOC analyzer and SEM. The setting and hardened properties,
loss of ignition, air content were measured according to ASTM standards.
The characterization results confirm that POCP consists of a mixture of
inorganic oxides and a small fraction of organic carbon, particles are
porous in nature and irregular in shape, and it contains the quartz and
cristobalite phases of SiO2. POCP delay the initial rate of hydration
reaction, absorb more water, insignificant change of soundness and
decrease in compressive strength of blended cement compared with OPC.
However, the value of setting time, water demand and soundness are at the
limit of ASTM standard up to 60% replacement level. The water for normal
consistency, setting time, soundness, and compressive strength result of
POCP contained cement compared with the data which are available in the
literature of common waste materials. POCP shows the performance like
siliceous porous material.
Suggested Reviewers: Zainal Arifin Ahmad
School of Materials & Mineral Resources Engineering, Universiti Sains
Malaysia, 14300 Nibong Tebal, Penang, Malaysia.
A.A. Raheem
Civil Engineering Department, Ladoke Akintola University of Technology,
Ogbomoso, Nigeria
L. Turanli
Department of Civil Engineering, Middle East Technical University, 06531
Ankara, Turkey
Hossein Noorvand
Housing Research Centre, University Putra Malaysia, 43400 Serdang,
Selangor, Malaysia
Bashar S. Mohammed
Department of Civil Engineering, Universiti Teknologi PETRONAS, Bandar
Sri Iskandar, 31750 Tronoh, Perak Darul Ridzuan, Malaysia
Date: 20-11-2016
To,
Editor-in-Chief
Construction and Building Materials
The international journal
Subject: Paper submission
Dear Sir,
With reference to the above subject, it is stated that the paper having title “Effect of
palm oil clinker powder characteristics on setting and hardened
properties of cement” is being sent through online submission. It is affirmed that
this paper has not been published previously, it is not under consideration for publication
elsewhere and, if accepted, it will not be published elsewhere in substantially the same
form, in English or in any other language, without the written consent of the publisher.
Looking forward to your prompt response.
Thanking in anticipation.
With best wishes
Mohammad Razaul Karim
Department of Civil Engineering
University of Malaya
50603, Kuala Lumpur
MALAYSIA
E-mail: [email protected]
Tel : +60149116568
Cover Letter
Effect of palm oil clinker powder characteristics on setting and hardened
properties of cement
Mohammad Razaul Karim1, Hashim Abdul Razak
1, S. Yusoff
1, F. I. Chowdhury
2.
Department of Civil Engineering2, Center for Ionics University of Malaya, Department of Physics
2, University of
Malaya, 50603 Kuala Lumpur, Malaysia
Abstract
The characteristics of waste material play an important role in setting and hardened properties of
cement, which are a significant consideration for introducing a new supplementary cementitious
material. This study aims to investigate the effect of palm oil clinker powder (POCP)
characteristics on setting and hardened properties of cement. The characteristics of POCP were
determined using XRF, FTIR, XRD, particle size analyzer, TOC analyzer and SEM. The setting
and hardened properties, loss of ignition, air content were measured according to ASTM
standards. The characterization results confirm that POCP consists of a mixture of inorganic
oxides and a small fraction of organic carbon, particles are porous in nature and irregular in
shape, and it contains the quartz and cristobalite phases of SiO2. POCP delay the initial rate of
hydration reaction, absorb more water, insignificant change of soundness and decrease in
compressive strength of blended cement compared with OPC. However, the value of setting
time, water demand and soundness are at the limit of ASTM standard up to 60% replacement
level. The water for normal consistency, setting time, soundness, and compressive strength result
of POCP contained cement compared with the data which are available in the literature of
common waste materials. POCP shows the performance like siliceous porous material.
Keywords: Palm oil clinker powder, Setting time, Water consistency, Compressive strength,
Soundness.
*ManuscriptClick here to view linked References
1. Introduction
The setting and hardened properties of cement are an important consideration for using wastes as
supplementary cementitious material. However, the incorporation of waste as supplementary
material in cement-based applications affect the setting time, expansion and hardened properties
of the concrete or cement mortar. The effect of supplementary materials on setting and hardened
performance of concrete, cement paste as well as mortar largely depends on its’ characteristics.
Palm oil clinker is a waste material which is significantly discarded from palm oil mills [1, 2]. In
contemporary practice, this waste is dumped in open land or land field site that causes of the
environmental pollution [3]. On the other hand, the challenge for the cement industries is to
enlarge the production without increasing the environmental pollution [4-6]. The viability for
using of this waste in self-compacting concrete [3], light weight concrete [7], normal concrete [8]
and porous concrete [9] has been verified in recent studies. The feasibility of palm oil clinker
powder (POCP) waste for using in cement-based applications significantly depend on its’
characteristics influence on the setting and hardened properties of the cement which is rarely
evaluated.
Previous studies found that the palm oil clinker (POC) consists with a number of inorganic
oxides [10]. The content of inorganic oxides in POC is increased through burning process in
boiler section of a palm oil mill. The burning system enrich the suitability for using POC in
cement-based applications rather than municipal solid waste [11]. The ladle slag [12], basic
oxygen furnace steel slag [13], palm oil fuel ash, rice husk ash [14], sewage sludge ash [15],
coal bottom and fly ashes also produce through the burning system. Although, all these wastes
were obtained through burning route, but have a lot of characteristic differences. This is mainly
due to the type of raw materials used as well as the burning condition. Previous studies found
that the setting and hardened behaviour of the blended cement is influenced by the characteristics
of baggage ash, MSWI bottom ash, POFA, zeolitic tuff, perlite, steel making slag, pumic ash,
volcanic ash, corn cob ash and coal mining waste [11, 16-23].
The water demand for normal consistency depends on the chemical structure, specific surface
area and porosity of the cement admixtures [24]. The analysis of the results, for other wastes
available in literature found that the water demand varied based on several factors. The water
demand increased in the blended cement as a result of the large particle size [16-18, 20, 25],
hygroscopic nature [16, 17] and microspores [26-28], amorphisity [25, 29], chemical
composition [29, 30] and Ca+2
, Pb+2
, Cd+2
and Cu+2
ions containing minerals [11] in the
supplementary materials. Moreover, it decreased in the blended cement by the reason of dilution
factor [19, 22], mineralogical and chemical composition [21] of the adding materials. The water
demand of the activated coal mining waste blended cement increased up to 10% replacement
level because of the high absorption of water molecules by the active fine particles and reduced
with increasing of the replacement level for the effect of the heavy metals content in activated
mining coal waste [23].
The setting behaviour of concrete or mortar or cement paste is controlled by adding the gypsum
(CaSO4.2H2O) as well as the tricalcium aluminate (C3A) content in the cement. The function of
gypsum is to delay of the hydration reaction by forming ettringite with the active phases of
clinker as shows in the reaction.
3 CaO.Al2O3 + 3 (CaSO4.2H2O) +26 H2O 3 CaO.Al2O3. 3CaSO4.32 H2O
The early reaction rate of cement depends on the ionic species (Ca+2
, SO4-2
, OH-1
and CO3-2
) and
are available to make barrier over the grains of the aluminate and ferrite phases. The availability
and activity of these ions govern by few factors such as allocation of Al2O3 in the clinker phases,
the particle size, the quality and quantity of the gypsum. Besides that, the setting time of the
blended cement influence with the particle size, specific surface area and mineralogical structure
of the admixtures [24]. Literature survey found that the setting time increased in blended cement
is due to the fact of bigger particle size [27], high porosity [27], hygroscopic nature [16, 17], low
lime content [22], mineralogical composition [18], amorphous mineral content [25, 29], high
content of the Ca+2
, Pb+2
, Cd+2
and Cu+2
ions [11] in supplementary materials. Moreover, the
dilution effect also plays an important role on the rate of hydration reaction [16, 17, 20, 21, 31].
A few properties including active lime content [32, 33], ultrafine particle size [31],
pseudomorphic layer [30] of the supplementary materials accelerate the rate of hydration
reaction. Previous study found that the setting time of the zeolitic tuff blended cement increased
up to 10%, and decreased at higher replacement level was due to the diffusion-controlled effect
[26]. The setting time as higher up to 10% replacement level of OPC by coal mining waste which
was the reflect of the greater fineness of the supplementary material. Raising the percentage of
activated coal waste from 10% to 20% in the blended cements delay the initial setting time
slightly which were due to low concentrations of heavy metals such as cadmium and nickel in
coal ash [23].
The effect of the supplementary material on the volume change of concrete or mortar is
important consideration for developing new blended cement. The sound cement will not expand
at the time of drying and has no chance to develop a crack in the concrete. The expansion is
caused by the excessive amount of the active free lime (CaO) or magnesia (MgO) or SO3 [18].
Previous study found that the soundness of the granulated blast furnace slag (GBFS) blended
cement increased with the increasing replacement levels for its’ mineralogical composition [29],
whereas, the activated coal mining wastes did not interfere of the volume stability of the blended
cement [23].
The mineralogical features of the clinker, pozzolanic reactions, particle size, reactive SiO2 ratio
and water demand of the cement mixtures are accountable for the compressive strength of the
cement which is a function of hardening part [24]. The porous nature of the siliceous waste
materials causes for increasing of the water demand which ultimately leads to decrease the
compressive strength [34]. The compressive strength decreases with rising replacement levels
which is due to the dilution effect [20] as well as chemical and mineralogical composition [30,
32] of the supplementary materials. The steel slag contain dicalciumsilicate (C2S),
tricalciumsilicate (C3S) and tricalcium aluminate (C3A) phases, but the content is low compared
with OPC clinker which takes part in hydration reaction [35, 36] and develop compressive
strength. The reactive SiO2 of wastes react with liberated Ca+2
ions in cement-based system to
form C-S-H gel [34] which develop compressive strength significantly at later age [25]. The palm
oil fuel ash (POFA) is another form of waste of palm oil mill which shows the pozzolonic
activity [37, 38]. The porosity of the supplementary materials increases the air content or
porosity of the concrete or mortar matrix that causes of the reduction of the compressive
strength [27]. The 28 days compressive strength were higher at 10% replacement level, whereas,
90 days compressive strength was almost similar with OPC which is the effect of the weak
pozzolanic activity of activated coal mining waste [23]. Previous study also found that the low
compressive strength at early age in siliceous wastes blended cement was due to the lack of
sufficient portlandite (CH) for react with available reactive SiO2 in the reaction medium [26].
Finally, it is clear that the fine, active, nonporous particles of the supplementary materials can
develop the density of the interfacial transition zone among the aggregate and paste which
ultimately leads to strength development.
The characteristics of supplementary materials play a vital responsibility in the setting and
hardening behaviour of the blended cement. The feasibility of POCP as a supplementary
cementitious material largely depends on these properties of blended cement. The effect of the
characteristics of POCP on the setting and hardening properties of the cement will be explored in
this study.
2. Materials and Methods
2.1 Characterization
The palm oil clinker (POC) was obtained from a palm oil mill, positioned in Dengkil in Kuala
Lumpur, Malaysia. The ordinary Portland cement (CEM I 42.5N) was taken from a local cement
industry for this study. Initially, the large size chunks of POC were crushed using a jaw crusher.
The smaller pieces after crushing were then grinding in a ball mill to produce palm oil clinker
powder (POCP). POCP contained 1% to 2 % of moisture, which removed through oven dried for
half an hour at a temperature of 100±2ºC for 30 minutes. The photographs of bulk quantity of
POC and a large chunk are depicted in Fig.1.
Fig. 1 Photographs of (a) bulk quantity and (b) a large chunk of POC
The specific gravity of cement and POCP were measured according to the ASTM C 188 method
[39] and the insoluble residue (IR) and loss of ignition (LOI) using ASTM C 114 method [40].
Fineness of raw material along with blended cement were determined by Blaine apparatus
according to standard ASTM C209 and the residue by ASTM C 430, respectively [41, 42]. The
total organic carbon (TOC) was determined using TOC analyzer of “Shimizu Corporation”. The
chemical composition of POCP and OPC were tested using XRF spectrometer (Epsilon-5). The
XRD (Empyrean) and FTIR (Perkin Elmer Frontier) were used for mineralogical composition
investigation. The Phenom tabletop SEM along with Pro Suite software was used for
morphological analysis of POCP. Acceleration voltage used was 10 kV. The Malvern particle
size analyzer was utilized for the particle size determination.
2.2 Blended Cement Composition and Preparation
The blended cement was prepared in a control mixing ball mill to guarantee homogeneity by
running 1 hour with 150 RPM. The blended cements were prepared with the replace of OPC by
(a) (b)
the 10%, 20%, 30%, 40%, 50% and 60% of POCP and the resulting blended cements were
designated as POCP10, POCP20, POCP30, POCP40, POCP50 and POCP60, respectively.
2.3 Water Demand, Setting Time and Volume Stability
The setting behaviour and water consistency of the pastes were resolved according to ASTM
C187 [43]and ASTM C191 [44],respectively by using a Vicate apparatus. The flow of mortar
was determined using a flow table. The Le chatelier moulds were used for soundness
determination according to the standard method of ASTMC1437 [45].
2.4 Mortar Preparation and Compressive Strength Test
The water to cement (W/C) and cement to sand(C/S) ratio were 0.40 and 0.50, respectively. The
sand was used in the study is specially graded silica sand. The mixed portion of the sand of
grade16/30, 8/16, 30/60 and 50/100 in the ratio of 7:5:4:4 was used in this experiment. The four
groups of silica sands were mixed at first. After one minute, OPC or POCP blended cement was
put into the mixture, followed by 1 min of mixing. Mixing water was then added to the mix, and
mixing was continued for 2 min, after which the required amount of super plasticiser (SP) was
added. Then after, the mixing was continued for 2 min and finally the mould was filled with
fresh mixed at two layers. Flow of mortar mixtures was maintaining 170±10 mm. The specimens
were put in a room for 24 hours with room temperature (25 ± 3ºC) with 65 ± 5% humidity. After
24 hours of casting, the specimens were demoulded and then cured in water with room
temperature (27 ± 3ºC) with 65 ± 18% humidity. Flexural test was performed using a mortar
beam of size 40 mm x 40 mm x 160 mm. The air content of mortar mixture was determined
according to ASTM standard C173 [46].The average of the three cubic specimen results with 50
mm X50 mm X 50 mm size was taken for a sample. Compressive strength was measured using
an ELE testing machine press with a capacity of 2000 kN, and loading rate of 0.5 kN/s.
3. Results and Discussions
3.1 Characteristics of Raw Materials
The characteristics of POCP and OPC are presented in Table 1. The specific surface area (SSA)
and specific gravity of OPC were 434 m2/kg and 3.14 g/cm
3, respectively. The residue on 90µ
sieve was 1.22%. The chemical composition of OPC is a mixture of inorganic oxides. The main
phases can be calculated according to the Brogue equation. The Al2O3/Fe2O3 ratio of Portland
cement was 2.55 which are ≥ 0.64. The tricalcium silicate/alite (C3S), dicalcium silicate/belite
(C2S), tricalciumaluminate/aluminate (C3A) and tetracalcium alumino ferrite/ ferrite (C4AF) are
57.21%, 16.65%, 9.88% and 6.87%, respectively in the cement used. The summation of C3S and
C2S was 73.86 %. The specific surface area and specific gravity of POCP was 401m2/kg and
2.54 g/cm3, respectively. The residue in 90µ sieve was 0.72%. The POCP consists of mixture of
inorganic oxides and 3.45% of organic carbon. The chemical composition of POCP depends on
the feeding ratio of palm oil shell and fibre as well as burning condition in the boiler. The
ASTM C 618 standard method was used to categorize fly ash as a C or F. The result of the
chemical composition, moistures and loss of ignition confirm that POCP is belonging to class F
of fly ash.
Table 1 Properties of OPC and POCP
Chemical composition
(%)
OPC POCP Class F fly ash
ASTM C-618
requirements
Class C fly ash
ASTM C-618
requirements
SiO2 21.34 59.21 N/A N/A
Al2O3 5.13 5.56 N/A N/A
Fe2O3 2.98 6.90 N/A N/A
SiO2 + Al2O3 + Fe2O3 29.45 71.67 >70 >50
CaO 64.56 5.23 N/A N/A
MgO 1.13 3.45 N/A N/A
SO3 2.41 2.31 <5.0 <5.0
Alkali (Na2O
equivalent)
0.12 16.23 N/A N/A
P2O5 0.03 0.03 N/A N/A
TiO2 0.01 0.14 N/A N/A
TOC -- 3.45 N/A N/A
Moisture 0.52 0.23 <3.0 <3.0
Loss of ignition (LOI) 1.35 4.10 6 6
Insoluble residue (IR) 0.65 36.23 N/A N/A
One of the significant factors of supplementary materials is particle size, which influences on the
setting behaviour of paste and compressive strength of mortar. The particle size of POCP and
OPC are represented in Fig. 2. The particle size of OPC of this experiment is almost similar with
POCP.
Fig. 2 Particle size of OPC and POCP
The micrograph of POCP is shown in Fig. 3.The POCP particles are irregular in shape with a
micro porous cellular structure. The pores are marked as ‘A’ and the network type fibre as ‘B’ in
Fig. 3. This is the effect of the unburned carbon of POCP. TOC analysis found that POCP
contain 3.45% organic carbon.This organic carbon is the result of incomplete burning of lignin,
cellulose fibre of palm oil shell. Previous study found that oil palm shell and POFA also
contained the organic carbon [47] which are responsible for porous structure.
0
10
20
30
40
50
60
70
80
90
100
0.01 0.1 1 10 100 1000
Cum
mula
tive
Pas
sing (
%)
Particle Size (µm)
POCP OPC
Fig. 3 Micrograph of POCP
Fig. 4 XRD pattern of POCP with baseline and peak searching results
A
B A
A
B
B
The XRD pattern of POCP is shown in Fig. 4. The POCP consist with the major minerals, i.e.
quartz and cristobalite at 2θ angles of 26.87° and 20.45°, respectively. A number of other peaks
were also observed in XRD patterns, but the intensity was low. The peaks with lower intensity
were not depicted in the pattern. An amorphisity hump was observed at the 2θ angles from 5° to
35° which is an indication of amorphous phase content in POCP [37, 38].
0 500 1000 1500 2000 2500 3000 3500 4000 4500
75
80
85
90
95
100
Tra
nsm
itta
nce
(%
)
Wave number (cm-1)
Organic matter
Si-O (asymmetric band )
H-O-H (deforming band)
Si-O ( vibration bands)
Fig.5 FTIR analysis of POCP
The quartz and cristobalite minerals contained in POCP are also identified by the FTIR data.
The peak of organic carbon was observed at around 3000 cm-1
in FTIR spectra. The quartz is one
of the significant minerals and invariably present in POCP. The presence of quartz in the samples
can be explained by two bands centered at 1008 cm−1
and 779 cm−1
assigned to stretching and
bending vibrations (Si-O) in the SiO4, which are due to the presence of the crystalline
mineralogical phases.
3.2 POCP Containing Cement Properties
The incorporation of a supplementary material effects on the chemical composition as well as
physical properties of cement which ultimately influence the setting and hardened properties
[48]. The chemical and physical properties of POCP blended cement up to 60% replacement
levels are depicted in the Table 2 and 3, respectively. The percentage of the CaO, Al2O3 and
Fe2O3 oxides decreased, whereas SiO2, K2O and MgO increased with the replacement level of
OPC by POCP. This fact is mainly due to the chemical composition difference between OPC and
POCP which is presented in the Table 1.
Table 2 Chemical composition of POCP blended cements
Cement CaO (%) SiO2 (%) Al2O3 (%) Fe2O3 (%) K2O (%) MgO (%)
POCP 10 58.62 25.12 5.17 3.37 1.73 1.36
POCP 20 52.69 28.91 5.22 3.76 3.34 1.59
POCP 30 46.76 32.70 5.26 4.16 4.95 1.83
POCP 40 40.82 36.49 5.30 4.55 6.56 2.05
POCP 50 34.90 40.27 5.34 4.94 8.17 2.29
POCP 60 28.96 44.06 5.39 5.333 9.78 2.52
Table 3 Physical properties of POCP blended cements
Cement SSA
(m2/kg)
Residue on
90 µ (%)
LOI (%) W C (%) Soundness
(mm)
IR (%)
POCP 10 430 1.15 1.63 27.67 ≤1 4.20
POCP 20 429 1.07 1.90 29.16 ≤1 7.76
POCP 30 426 0.99 2.18 33.53 ≤1 11.32
POCP 40 422 0.91 2.45 35.89 ≤1 14.88
POCP 50 419 0.86 2.72 37.14 ≤1 18.44
POCP60 418 0.80 3.0 39.21 ≤1 22.0
The specific surface area and residue on 90 µ sieve were not significantly varied with the
replacement level of OPC by POCP. The LOI and IR increase in replacement level, which is
due to the high organic carbon content and SiO2, respectively in POCP compare to OPC. The
quantity of water for normal consistency of blended cement depends on the chemical
composition, fineness and porosity of the supplementary materials [16-18, 20, 25]. Water
demand increases with replacement level of OPC by POCP. The water for normal consistency of
POCP10, POCP20, POCP30, POCP40, POCP50 and POCP60 were 105.3%, 113.3 %, 121.1%,
129.7 %, 134.2 % and 141.7% of OPC, respectively. Normal consistency of water is a physical
observation of the early state of hydration. An initial flocculation of cement particle takes place
quickly after adding water. The water demand is related to the physical features and chemical
composition of POCP. SEM observation in Fig. 3 found that POCP was irregular in shape, size
and have a lot of micro pores. Moreover, TOC and FTIR results confirmed that the organic
carbon was present in POCP. Both of the properties are responsible for the high water in blended
cement. Previous studies found that the higher water demand in fly ash, POFA, blended was due
to porosity or both porosity and organic carbon content [11].
Fig. 6 Relative water demand of wastes blended cement at 20% replacement level
The water demand of the different wastes blended cement at 20% replacement level is presented
in the Fig. 6. The dotted line indicates the water demand of control sample (OPC). The range of
relative water demand in blended cements is from 89% to 132% of OPC. The higher water
demand in siliceous waste, i.e. baggage ash, MSWI bottom ash, POFA, zeolitic tuff and POCP
blended cements is mainly due to porous nature of their particles[11, 16, 17, 26, 27]. The water
demand in dolomite and calcite dolomite blended cement paste are higher than other wastes due
to the combine effect of chemical composition and large porosity [18]. The difference of the
water demand among the perlite, steelmaking slag, pumic ash and volcanic ash blended cement
and OPC is less than 5%. The absorption by particle of these wastes and dilution effect are
almost similar at 20% replacement [19-21]. The corn cob ash and coal mining waste absorb less
water owing to the fact of fine particles, stable mineralogical composition [22, 23]. The water
demand of POCP is placed in the range of other siliceous waste materials.
124
89 89
130
108 109 103
128
96 96 97 106
132 121
-10
10
30
50
70
90
110
130
150 R
elat
ive
Wat
er C
on
sist
ency
(%
)
Name of the Wastes
3.3 Setting Behaviour
The setting time is an importance properties as well as the requirement of different international
standards for using cement in concrete. The setting time of OPC and POCP blended cement paste
are presented in Fig. 6. Figure 6 shows that the initial (IST) and final setting time (FST)
increases with addition of POCP. The active phases, i.e. C3S and C3A decrease in blended
cement and the existence of porous POCP particles among OPC particles slow the early reaction
rate of hardening [26, 27].
Fig. 7Effect of POCP on setting behaviour
Fig. 8 Relative initial setting time of waste blended cements at 20% replacement level
The Fig. 8 shows that the initial setting time (IST) of all the waste blended cement is higher than
OPC except dolomite and calcite dolomite. The horizontal dotted line indicates the IST for OPC
paste. The relative initial setting time of waste blended cement pastes at 20% replacement level
is in the range from 89% to 171% of the OPC which is due to dilution effect [16, 17, 20, 21, 31].
The variation of initial setting time among the different wastes i.e. baggage ash, coal mining
waste, corn cob ash, MSWI bottom ash, POFA, perlite, metallurgical slag, steelmaking slag,
volcanic ash, pumic ash, zeolitic tuff and POCP blended cement pastes is as a result of the fact
of the difference in the particle size, chemical and mineralogical composition, amorphisity ,
heavy metal content [11, 16, 17, 19-23, 26, 27, 30]. The initial hydration reaction rate accelerates in
the dolomite blended cement which is the result of reactive crystalline structure of minerals [18].
112 106
204
92
123 120 127
171
109 115 112 107 89
110
0
50
100
150
200
250 R
elat
ive
Init
ial S
etti
ng
Tim
e (%
)
Name of the Wastes
Fig. 9Relative final setting time of waste blended cements at 20% replacement
The relative final setting time (FST) of waste blended cements at 20% replacement level are in
the range of 93% to 170% of the OPC. The FST of the baggage ash, corn cob ash, MSWI bottom
ash, POFA, perlite, activated rice husk ash, metallurgical slag, steelmaking slag, volcanic ash,
pumic ash and POCP blended cement are higher than OPC. The major reasons behind the higher
FST are the porous nature of wastes and the dilution effect [16, 17, 20, 21, 31]. The difference in
the particle size, chemical and mineralogical composition, amorphisity, heavy metal content
among these wastes are responsible for variations in FST [11, 16, 19-23, 26, 27]. The coal
mining waste, dolomite, zeolitic tuff and calcite dolomite accelerate the final setting time. The
active chemical and mineralogical composition and fine particle of these wastes are responsible
to accelerate the reaction rate [18, 23, 26]. From the analysis of the IST and FST of the various
waste blended cements in Fig 8 and 9, if IST accelerate in that case FST also increase similarly.
Similar tread is also for decreasing of setting time.
3.4 Volume Stability
160
94
170
93
130 130 116 120 123
113 109 103 93 93
112
10
30
50
70
90
110
130
150
170
190 R
elat
ive
Fin
al S
etti
ng
Tim
e (%
)
Wastes
The CaO, MgO and SO3 play an important role for expansion of the concretes [24]. The volume
expansion of the OPC and POCP blended cement are less than 1mm. The volume stability of
POCP blended cement up to 60% replacement levels of OPC is less as compared with the ASTM
standard value of 10 mm. When this un-hydrated free lime come in contact with water/moisture
and become hydrated lime as a result the volume increase. This expansion causes the stress
concentration in the concrete and when these stress overcome the tensile strength of concrete
then cracks start to propagate. The volume expansion of POCP blended cement pastes were
higher than OPC which may be due to excessive amount of MgO in POCP blended cement
shown in Table 2 [34].
Fig. 10 Volume expansion of POC powder blended cement pastes
The variation of the volume expansion in the waste blended cements is as a result of the
differences of the active CaO, MgO and SO3 in the supplementary materials [18, 21-23, 30].
Although, the expansion of waste blended cements is slightly higher than OPC, but place below
100
400
50
140 100
50 50
168
0
50
100
150
200
250
300
350
400
450
Rel
ativ
e So
un
dn
ess
(%)
Name of the Wastes
the requirement of the ASTM standardized, i.e. 10 mm. The higher expansion is in corn cob ash
blended cement due to the excess free lime [22].
3.5 Harden Properties
The compressive strength of mortar is significant consideration to introduce a new
supplementary cementitious material in cement-based applications. Therefore, the compressive
strength of POCP blended cement mortars are revealed in Fig.10. It deduces from Fig.10 that the
compressive strength of the POCP blended cement mortars increase with the reaction time
(curing age), but, reduce with the replacement levels of OPC by POCP.
Fig. 11Effect of POCP on compressive strength
Adding material has two type effects on blended cement, (i) nucleation effect and (ii) packing
effect. The packing effect is a physical interaction in which small particle place inside of cement
particle and increase overall matrix density, which ultemately leads to increase the compressive
strength, but this effect largely depends on particle size and porosity of supplementary material.
The POCP particles are porous in nature and negatively contribution in strength development.
0
10
20
30
40
50
60
70
80
90
1 10 100 1000
Co
mp
ress
ive
stre
ngth
(M
Pa)
Curing age ( days)
POCP 10 POCP 20 POCP 30 POCP 40 POCP 50 POCP 60
The nucleation effect arises when the small particles are dispersed in the blended cement and
take part in cement hydration. These effects are responsible for increase in later age strength. The
reactivity of SiO2 of supplementary material depends on the active surface area. Researchers also
observed that the compressive strengths decreased with replacement level of OPC using wastes
which was due to the lower content active phase C2S, C3S and C3A [49, 50].
Fig. 12 Relation among relative compressive strength (28 days), replacement levels and relative
LOI.
The Fig. 12 shows that the relative compressive strength of POCP blended decrease with
increasing the loss of ignition (LOI) in blended cement. The LOI enhances with increasing the
replacement level of OPC by POCP because POCP contain 3.45 % of TOC. The relative
compressive strength at 28 days of POCP10, POCP20, POCP30, POCP40, POCP 50 and
POCP60 mortars were 83.83%, 79.69%, 67.80%, 58.97%, 48.10% and 37.72%, respectively of
the OPC mortar. In addition, the relative LOI content in POCP10, POCP20, POCP30, POCP40,
POCP 50 and POCP60 mortars were 106.53%, 124.18%, 142.48%, 160.13%, 177.78% and
0
50
100
150
200
250
0
10
20
30
40
50
60
70
80
90
10 20 30 40 50 60
Rel
ativ
e LO
I (%
)
Rel
ativ
e co
mp
ress
ive
stre
ngt
h (
%)
Replacement Level (%)
Relative compressive strength (%) Relative LOI (%)
196.07%, respectively of the OPC. Previous studies also found that the LOI of cement had
negative effect on the compressive strength development [51].
Fig. 13 Relation among relative compressive strength (28 days), replacement levels and relative
air content.
The relative compressive strength variation with the relative air content of mortars is presented
Fig. 13. The relative air content in POCP10, POCP20, POCP30, POCP40, POCP 50 and
POCP60 mortars were133.92%, 173.21%, 212.50%, 251.79%, 292.85% and 330.36%,
respectively of the OPC mortar. This clearly indicates that the strength loss in POCP mortars is
due to the increase of the porosity. Former studies found that the organic carbon of fly ash
negatively influences the air entrainment in concrete [52, 53]. The content of alkali metal oxides
increases in POCP blended cement with the increasing the replacement level, because of the
higher content of alkali metal oxides in POCP. Furthermore, the air content decrease in POCP
mortar is due to the increasing of the alkali metals and decreasing of the lignin based organic
materials [51]. Previous researches were found that grounded POFA, natural pozzolan with nano
0
50
100
150
200
250
300
350
0
10
20
30
40
50
60
70
80
90
10 20 30 40 50 60
Rel
ativ
e A
ir C
on
ten
t (%
)
Rel
ativ
e C
om
pre
ssiv
e St
ren
gth
(%
)
Replecement Level (%)
Relative compressive strength (%) Relative Air Content (%)
SiO2 as well as slag was increased the density of the matrix as result compressive strength was
developed [54, 55].
The relative flexural strength of POCP10, POCP20, POCP30, POCP40, POCP50 and POCP60
cements were 93%, 88%, 71%, 70% and 64%, respectively of the OPC. The flexural strength
value decreases with the replacement level. The flexural strength of POCP40 is almost similar
than POCP50. The effectiveness of POCP particles depends on the bonding energy between
aggregate with paste. This bonding energy reduces with replacement level of OPC with POCP.
The variation of flexural strength at different replacement level is an indication of the interaction
of POCP in paste. Moreover, the irregular shape porous and fibrous nature of POCP also
responsible for the effectiveness in paste-aggregate interface.
Fig. 14 Relative compressive strength of waste blended cements at 20% replacement
184
70 73 74 80 91
76 89 90.4
80
122
100
80
0
50
100
150
200
Rel
ativ
e C
om
pre
ssiv
e st
ren
gth
(%
)
Name of the wastes
The compressive strength at 28 days of curing of the waste blended cement of 20% replacement
level is presented in the Fig.14. The compressive strength is lower for most of the wastes blended
cement which is mainly due to the dilution effect. The other factors such as particle size,
amorphisity, organic matter content, chemical and mineralogical composition in supplementary
materials also effects on the compressive strength [11, 18-21, 27, 30, 31]. The compressive
strength of blended cement is higher than OPC which is the result of the high amorphous
SiO2content in the baggage ash [16, 17]. The chemical composition and excess lime in the
zeolitic tuff and calcite dolomite are responsible for the higher compressive strength [18, 26].
4. Conclusions
This work presents a research performed on the effect of the characteristics of POCP on the
setting and hardened properties of blended cement. The following conclusions drawn from the
finding in experiments and literature:
1. The characterization results confirm that POCP consist in inorganic oxides and a small
portion of organic carbon. The particles are irregular in shape and porous in nature. The
quartz and cristobalite are the most intense peaks of SiO2 were observed in the XRD
pattern.
2. The water for normal consistency of POCP10, POCP20, POCP30, POCP40, POCP50 and
POCP60 were 105.3%, 113.3%, 121.1%, 129.7%, 134.2% and 141.7% of OPC,
respectively which is due to the high porosity in POCP particle.
3. The setting time of POCP blended cement increases with the replacement level, which is
due to dilution effect. Previous data analysis also found the similar result of the baggage
ash, coal mining waste, corn cob ash, MSWI bottom ash, POFA, perlite, metallurgical
slag, steelmaking slag, volcanic ash, pumic ash and zeolitic tuff blended cement pastes.
The coal mining waste, dolomite, zeolitic tuff and calcite dolomite accelerate the final
setting time, which is due to the active chemical and mineralogical composition and fine
particles.
4. The expansion of POCP blended cement is placed within the range of 0.19-0.53 mm
which is significantly lower than the standard limit of 10 mm. The variation of the
volume expansion in the waste blended cements is due to the differences of the active
CaO, MgO and SO3in the supplementary materials.
5. The compressive and flexural strength of POCP blended decreases with replacement
levels of OPC. The relative compressive strength at 28 days of POCP10, POCP20,
POCP30, POCP40, POCP 50 and POCP60 mortars were 83.83%, 79.69%, 67.80%,
58.97%, 48.10% and 37.72%, respectively of OPC mortar. The compressive strength of
POCP blended cement decrease with increasing the LOI in cement as well as air content
in fresh mortars. The compressive strength is lower in most of wastes blended cement
which is mainly due to dilution effect. The compressive strength of blended cement is
higher in few waste than OPC which is the result of the high amorphous SiO2 content,
chemical composition and excess lime in the zeolitic tuff.
Acknowledgements
This research work has been carried out under the research grant
UM.C/625/1/HIR/MOHE/ENG/56 sponsored by the Ministry of Higher Education (MOE),
Malaysia and Project Number: PG256-2015B sponsored by University of Malaya.
References
1. Siew, H.S., T.T. Kok, and T.L. Keat, Oil Palm Biomass As A Sustainable Energy Source:
A Malaysian Case Study. 2008.
2. Garcia-Nunez, J.A., et al., Evolution of palm oil mills into bio-refineries: Literature
review on current and potential uses of residual biomass and effluents. Resources,
Conservation and Recycling, 2016. 110: p. 99-114.
3. Kanadasan, J. and H.A. Razak, Mix design for self-compacting palm oil clinker concrete
based on particle packing. Materials & Design, 2014. 56: p. 9-19.
4. Coskun, M., Fundamental pollutants in the European Union (EU) countries and their
effects on Turkey. Procedia-Social and Behavioral Sciences, 2011. 19: p. 467-473.
5. Snels, M., et al., Carbon dioxide opacity of the Venus׳ atmosphere. Planetary and Space
Science, 2014. 103: p. 347-354.
6. Hasanbeigi, A., Emerging Energy-efficiency and CO2 Emission-reduction Technologies
for Cement and Concrete Production. 2013.
7. Mohammed, B.S., W. Foo, and M. Abdullahi, Flexural strength of palm oil clinker
concrete beams. Materials & Design, 2014. 53: p. 325-331.
8. Abutaha, F., H.A. Razak, and J. Kanadasan, Effect of palm oil clinker (POC) aggregates
on fresh and hardened properties of concrete. Construction and Building Materials, 2016.
112: p. 416-423.
9. Ibrahim, H.A. and H.A. Razak, Effect of palm oil clinker incorporation on properties of
pervious concrete. Construction and Building Materials, 2016. 115: p. 70-77.
10. Karim, M.R., H. Hashim, and H.A. Razak, Thermal activation effect on palm oil clinker
properties and their influence on strength development in cement mortar. Construction
and Building Materials, 2016. 125: p. 670-678.
11. Li, X.-G., et al., Utilization of municipal solid waste incineration bottom ash in blended
cement. Journal of Cleaner Production, 2012. 32: p. 96-100.
12. Serjun, V.Z., et al., Recycling of ladle slag in cement composites: Environmental impacts.
Waste Management, 2015. 43: p. 376-385.
13. Zhang, T., et al., Preparation of high performance blended cements and reclamation of
iron concentrate from basic oxygen furnace steel slag. Resources, Conservation and
Recycling, 2011. 56(1): p. 48-55.
14. Rukzon, S. and P. Chindaprasirt, Use of disposed waste ash from landfills to replace
Portland cement. Waste Management & Research, 2009.
15. Pavlík, Z., et al., Energy-efficient thermal treatment of sewage sludge for its application
in blended cements. Journal of Cleaner Production, 2016. 112: p. 409-419.
16. Ganesan, K., K. Rajagopal, and K. Thangavel, Evaluation of bagasse ash as
supplementary cementitious material. Cement and concrete composites, 2007. 29(6): p.
515-524.
17. Singh, N., V. Singh, and S. Rai, Hydration of bagasse ash-blended portland cement.
Cement and Concrete Research, 2000. 30(9): p. 1485-1488.
18. Yılmaz, B. and N. Ediz, The use of raw and calcined diatomite in cement production.
Cement and Concrete Composites, 2008. 30(3): p. 202-211.
19. Hossain, K.M.A., Blended cement using volcanic ash and pumice. Cement and Concrete
Research, 2003. 33(10): p. 1601-1605.
20. Erdem, T., et al., Use of perlite as a pozzolanic addition in producing blended cements.
Cement and Concrete Composites, 2007. 29(1): p. 13-21.
21. Kourounis, S., et al., Properties and hydration of blended cements with steelmaking slag.
Cement and Concrete Research, 2007. 37(6): p. 815-822.
22. Adesanya, D. and A. Raheem, Development of corn cob ash blended cement.
Construction and Building Materials, 2009. 23(1): p. 347-352.
23. Frías, M., et al., Effect of activated coal mining wastes on the properties of blended
cement. Cement and Concrete Composites, 2012. 34(5): p. 678-683.
24. Lea, F.M., The chemistry of cement and concrete. 1970.
25. Turanli, L., B. Uzal, and F. Bektas, Effect of material characteristics on the properties of
blended cements containing high volumes of natural pozzolans. Cement and Concrete
Research, 2004. 34(12): p. 2277-2282.
26. Yılmaz, B., et al., Properties of zeolitic tuff (clinoptilolite) blended Portland cement.
Building and Environment, 2007. 42(11): p. 3808-3815.
27. Tangchirapat, W., et al., Use of waste ash from palm oil industry in concrete. Waste
Management, 2007. 27(1): p. 81-88.
28. Ghofrani, M., et al., Fiber-cement composite using rice stalk fiber and rice husk ash:
Mechanical and physical properties. Journal of Composite Materials, 2015. 49(26): p.
3317-3322.
29. Öner, M., K. Erdoğdu, and A. Günlü, Effect of components fineness on strength of blast
furnace slag cement. Cement and Concrete Research, 2003. 33(4): p. 463-469.
30. Rai, A., et al., Metallurgical slag as a component in blended cement. Construction and
Building Materials, 2002. 16(8): p. 489-494.
31. Asavapisit, S. and N. Ruengrit, The role of RHA-blended cement in stabilizing metal-
containing wastes. Cement and Concrete Composites, 2005. 27(7): p. 782-787.
32. García, R., et al., The pozzolanic properties of paper sludge waste. Construction and
Building Materials, 2008. 22(7): p. 1484-1490.
33. Aruntaş, H.Y., et al., Utilization of waste marble dust as an additive in cement
production. Materials & Design, 2010. 31(8): p. 4039-4042.
34. Kocak, Y. and S. Nas, The effect of using fly ash on the strength and hydration
characteristics of blended cements. Construction and Building Materials, 2014. 73: p. 25-
32.
35. Wang, Q., P. Yan, and J. Feng, A discussion on improving hydration activity of steel slag
by altering its mineral compositions. Journal of hazardous materials, 2011. 186(2): p.
1070-1075.
36. Siddique, R. and R. Bennacer, Use of iron and steel industry by-product (GGBS) in
cement paste and mortar. Resources, Conservation and recycling, 2012. 69: p. 29-34.
37. Noorvand, H., et al., Physical and chemical characteristics of unground palm oil fuel ash
cement mortars with nanosilica. Construction and Building Materials, 2013. 48: p. 1104-
1113.
38. Chandara, C., et al., Heat of hydration of blended cement containing treated ground palm
oil fuel ash. Construction and Building Materials, 2012. 27(1): p. 78-81.
39. Standard, A., C118: Standard Test Method for Density of Hydraulic Cement. Annual
Book of ASTM Standards. 2009.
40. Standard, A., C114: Standard Test Methods for Chemical Analysis of Hydraulic Cement.
Annual Book of ASTM Standards. 2013.
41. Standard, A., C-209: Standard Test Methods for Fineness of Hydraulic Cement by Air-
Permeability Apparatus. Annual Book of ASTM Standards. 2011.
42. Standard, A., C204: Standard Test Methods for Fineness of Hydraulic Cement by Air-
Permeability Apparatus.Annual Book of ASTM Standards. 2011.
43. Standard, A., C187: Standard test methods for normal consistency of hydraulic cement.
Annual Book of ASTM Standards. 2004.
44. Standard, A., C191: Standard test methods for setting time of hydraulic cement by Vicat
needle. Annual Book of ASTM Standards. 2008.
45. Standard, A., C 151: Autoclave Expansion of Portland Cement. Annual book of ASTM
standards. 2000.
46. Cl73, A., Standard Test Method for Air Content of Freshly Mixed Concrete by the
Volumetric Method. Annual book of ASTM standards, ASTM, West Conshohocken,
Pennsylvania, 2012.
47. Islam, M., M. Beg, and M. Mina, Fibre surface modifications through different
treatments with the help of design expert software for natural fibre-based biocomposites.
Journal of Composite Materials, 2014. 48(15): p. 1887-1899.
48. Kirgiz, M.S., Effects of Blended-Cement Paste Chemical Composition Changes on Some
Strength Gains of Blended-Mortars. The Scientific World Journal, 2014. 2014.
49. Segui, P., et al., Characterization of wastepaper sludge ash for its valorization as a
component of hydraulic binders. Applied Clay Science, 2012. 57: p. 79-85.
50. Conesa, J.A., A. Gálvez, and A. Fullana, Decomposition of paper wastes in presence of
ceramics and cement raw material. Chemosphere, 2008. 72(2): p. 306-311.
51. Nagi, M., Evaluating air-entraining admixtures for highway concrete. Vol. 578. 2007:
Transportation Research Board.
52. Hill, R.L., et al., An examination of fly ash carbon and its interactions with air entraining
agent. Cement and Concrete Research, 1997. 27(2): p. 193-204.
53. Hill, R. and K. Folliard, The impact of fly ash on air-entrained concrete. Concrete
InFocus, 2006. 5(3): p. 71-72.
54. Mo, L., et al., Deformation and mechanical properties of quaternary blended cements
containing ground granulated blast furnace slag, fly ash and magnesia. Cement and
Concrete Research, 2015. 71: p. 7-13.
55. Tangpagasit, J., et al., Packing effect and pozzolanic reaction of fly ash in mortar.
Cement and Concrete Research, 2005. 35(6): p. 1145-1151.