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Optimal conditions of porous ceramic

membrane synthesis based on alkali activated
blast furnace slag using Taguchi method

Article in Ceramics International · July 2017

DOI: 10.1016/j.ceramint.2017.07.197

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 Ceramics International 43 (2017) 14369–14379

Contents lists available at ScienceDirect

Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Optimal conditions of porous ceramic membrane synthesis based on alkali MARK

activated blast furnace slag using Taguchi method
⁎
Farzaneh Mohammadi, Toraj Mohammadi
Research and Technology Centre of Membrane Processes, Faculty of Chemical, Petroleum and Gas Engineering, Iran University of Science and Technology
(IUST), Narmak, Tehran, Iran

A R T I C L E I N F O A BS T RAC T

Keywords: The main purpose of this research is to synthesize porous ceramic membrane based on alkali-activated blast
Porous ceramic membrane furnace slag and achieve optimal synthesis conditions for removing over 90% petroleum compounds and flux in
Alkali activated blast furnace slag the range of microfiltration (MF) and ultrafiltration (UF). The method applied for membrane synthesis is
Taguchi method simple, environmentally friendly, and economical. The blast furnace slag as the main starting material was used
to fabricate these free sintering and self-supported ceramic membranes. The L9 orthogonal array of the Taguchi
method was employed to determine the optimum conditions of three controlling factors, i.e. hydraulic pressing
pressure, alkali-activated blast furnace slag drying time, and pressing time in three levels. Morphology and
filtration performance of the synthesized membranes were characterized via SEM images using Image-j
software, total porosity determination, and pore size study using bubble point method. Cross-flow filtration of
75 ppm gas oil in water emulsion was performed and COD analysis of permeate was then monitored.
Distribution of synthesis parameters and their influences on the membrane fabrication process were
investigated using analysis of variance (ANOVA). According to the results, drying time and hydraulic pressing
pressure were known as the most effective parameters on COD and permeation flux. Two optimal membranes
for COD removal and permeation flux were identified in hydraulic pressing pressure, drying time and pressing
time of (400 bar, 6 h, 5 min) and (225 bar, 8 h, 30 min), respectively. COD optimal UF membrane with an
average pore size of 0.07 µm and 100% removal of gas oil and permeation flux optimal MF membrane with an
average pore size of 0.66 µm and pure water permeation flux of 1960 kg/m2 h were introduced.

1. Introduction glassy materials are utilized to fabricate ceramic membranes. Due to

In recent decades, due to depletion of surface and ground water
resources, waste water treatment has attracted a lot of attention.
Because of obvious technical and economic feasibilities in the field of
water desalination and waste water treatment, membrane technology
has been associated with many promising improvements in reducing
energy consumption. Membrane processes such as micro, ultra and
nanofiltration (MF, UF, and NF) are widely used in water and waste-
water treatment [1,2].
In both ultra and microfiltration processes, porous membranes are
used. Porous membranes in structure and performance behave almost
like a general filter. These membranes have a hollow solid structure of
interconnected and randomly oriented pore network [3]. Therefore,
separation mechanism in porous membranes is as functions of pore
size and pore size distribution. Porous membranes are mainly made
from polymeric and/or ceramic materials [3,4].
Inorganic materials such as alumina, titania, zirconia and/or some
the high cost of starting materials for synthesis, fabrication process
complexity and also low membrane surface area per unit volume,
ceramic membranes are recognized as more expensive membranes
[5,6]. However, they have many features in comparison with polymeric
membranes including chemical and thermal stability, long term dur-
ability, long working life and high mechanical strength [5,7,8].
Generally, to prepare ceramic membranes, a thin ceramic layer is
coated on a porous ceramic support by applying methods such as sol-
gel and chemical vapor deposition (CVD) [5,9]. Micro-porous supports
which provide mechanical strength, are made from powder oxides via
extrusion, tape casting or slip casting [7,10,11].
Most methods for fabricating ceramic membranes require heat
treatment. High-temperature processing and sintering increase energy
consumption and production cost. This subject is not desirable from an
economic point of view. Thus, achieving low-cost starting materials and
simple and economical methods to synthesize ceramic membranes is
the goal of many researchers.

⁎
Corresponding author.
E-mail address: torajmohammadi@iust.ac.ir (T. Mohammadi).

http://dx.doi.org/10.1016/j.ceramint.2017.07.197
Received 11 June 2017; Received in revised form 27 July 2017; Accepted 27 July 2017
Available online 29 July 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
F. Mohammadi, T. Mohammadi
In order to achieve this purpose, fabrication of ceramic membranes
using various waste materials such as fly ash [12–14], glass [15] and
rice husk [16], has been investigated by many researchers in recent
years.
In this research, blast furnace slag (BFS) was used as a low-cost
[17,18] and environmentally friendly [18,19] starting material to
reduce starting material cost for fabrication of a porous ceramic
membrane. Also, alkali activation of BFS without any heat treatment
requirement [20–22] was used as a simple and economical method to
diminish complexity and fabrication cost of porous ceramic membrane.
The alkali activation mechanism is composed of two continuous
reactions of disintegration and condensation. As the consequence of
alkali activation of BFS in alkaline media, the structure of BFS is
destructed resulting in the generation of gel-like hydration products
such as amorphous calcium (aluminium) silicate hydrate (C(A)SH)
[23–26]. The structure of C (A) SH with negative charge is composed of
AlO4 and SiO4 tetrahedral joined periodically by sharing all bridge
oxygen atoms [24,27–29]. The presence of positively-charged species
such as Ca2+ and Na+ ions in an alkaline medium causes the
neutralization of negative charge of C(A)SH structure.
This study utilized the Taguchi's L9 orthogonal array to determine
the optimal synthesis conditions for porous ceramic membranes via
alkali activation of BFS. The effects of parameters on performance and
morphology of the optimum membranes were also discussed, in details.
2. Materials and methods
2.1. Materials
The main synthesis material was water quenched-blast furnace slag
(Esfahan Steel Company-Iran) with a Blaine fineness of 3000 (cm2/gr).
Detailed chemical composition and some physical properties of this
material were reported in our previous work [30]. Alkali activation
solution was prepared using sodium hydroxide pellets (NaOH, Merck
98%) and distilled water.
2.2. Description of alkali-activated ceramic membrane preparation
2.2.1. Alkali activation of blast furnace slag
Alkali-activated BFS (AABFS) was prepared via mixing the BFS
powder with the alkaline solution. The mixing formula was prepared by
adding activator (NaOH pellets) to distilled water, at a water to slag
ratio (W/S) of 0.2 and an activator to slag ratio (A/S) of 0.04. To obtain
a uniform alkali activated powder, mixing was continued for 5 min.
2.2.2. Ceramic membrane synthesis using hydraulic pressing
Design of experiments (DOE) indicates synthesis conditions in each
test. So, the synthesis powder (alkali activated blast furnace slag) was
prepared based on the DOE by Taguchi method. For this purpose, 1 g
of the synthesis powder in each trial is poured into the stainless steel
mold with an inner diameter of 1.2 cm. Then, the steel mold was
pressed by hydraulic pressing machine. The schematic of a hydraulic
pressing machine is shown in Fig. 1. All stages of synthesis and testing
are conducted at 24 ± 1 °C.
2.3. Design of experiments based on Taguchi method
2.3.1. Description of quality characteristics
To achieve appropriate optimization of quality characteristics,
Taguchi recommends three routes, as follows:
• The larger the better
• The smaller the better
• The nominal the best
Selection of each category depends on the desirable quality
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Ceramics International 43 (2017) 14369–14379
Fig. 1. Schematic of the hydraulic pressing machine.
characteristics [31,32]. For high permeation flux and COD removal,
the criterion of the larger the better was chosen and its corresponding
calculations was done using the following equation:
n
S/Nlarger the better = −10log (1/n ∑ 1/y 2i ) (1)
i=1
Where yi is the response (here, permeation flux and COD removal) and
n is the number of the experiments in a trial; the unit of signal-to-noise
ratio (S/N) is decibel (dB). Design and analysis of the Taguchi
experiments were performed using MINITAB 17 software.
2.3.2. Definition of effective factors and their levels
In this work, three factors with three levels were chosen. The factors
including hydraulic pressing pressure, AABFS drying time and pressing
time were defined as effective parameters on synthesis. The factors and
their levels are presented in Table 1.
2.3.3. Selection of standard orthogonal array
To design the experiments and achieve the optimum synthesis
conditions leading to the best removal, the Taguchi experimental
design was used. This method reduces the number of experiments
and also saves energy and synthesis materials. In fact, Taguchi is a type
of fractional factorial design that uses standard orthogonal array (OA)
to estimate how various process parameters simultaneously affect the
performance characteristic [31]. In this paper, the L9 OA was used for
the three parameters and their three levels.
2.3.4. Analysis of variance (ANOVA)
Analysis of variance (ANOVA) was performed on the results to
determine the relative percent influence of the synthesis parameters in
discrete terms [31,33,34]. Actually, in this study, ANOVA identifies the
parameters that have significant effects on the porous ceramic mem-
brane quality characteristics. The technique calculates the variance to
indirectly analyze the results. In fact, the method separates the total
variability into the percent contribution of each factor [31,33]. In
ANOVA, quantities such as sums of squares (SS), degrees of freedom
(DOF), mean square (MS), associated F-test of significance (F) and
percent contribution (P%) can be computed as follows [31,33,35,36]:
Table 1
Parameters and their values in the design of experiments.
Designation Parameter Levels
1 2 3
A
B
Pressing pressure (bar)
Pressing time (min)
225
5
300
15
400
30
C Drying time (h) 3 6 8
F. Mohammadi, T. Mohammadi
Valve K2
Retentate Stream
Recycle Stream
Valve K1
Feed Tank
Pump
Fig. 2. Scheme of the filtration setup.
⎛ KA ⎞ Germany) at a rate of 8000 rpm for 20 min was used to obtain the
SSA = ⎜∑ A 2i /n A i⎟ − T 2/ N
⎝ i=1 ⎠ (2)
where KA is the number of the levels of parameter A, nAi is the number
of all experiments at level i of parameter A, Ai is the sum of all
experiments of level i of parameter A and T is the sum of all
experiments. Also, the sum of squared error (SSe) is given by:
SSe = SST − (SSA + SSB + …)
where SST is the total sum of squares of all observations and computed
using the following equations:
N
SST = ∑i=1 y2i − T 2 /N
where yi is the observation of i. Mean square (MS) is computed by
dividing the SS by the DOF. DOF, F-ratio and (P %) are calculated as
follows:
DOFA = KA − 1
FA = MSA / MSe
(P%) = ssA − (DOF × MSe ) / SST × 100
where MSe is the error variance.
2.4. Characterization of synthesized membranes (analytical methods
and filtration experiments)
The morphology and microstructural characteristics of surface and
cross section of the prepared membranes were investigated using
scanning electron microscopy (SEM) photographs (TESCAN-VEGA-II
SBH Series), total porosity determination and pore size study. The
prepared membrane performance in separation of gas oil from water
was evaluated by synthetic waste water filtration of 75 ppm commercial
gas oil (Tehran refinery, Iran) – in – distilled water and rejection
determination using chemical oxygen demand (COD) measurement.
2.4.1. Preparation of synthetic waste water as feed
In order to obtain a stable emulsion of water and gas oil, a
surfactant (Tween 80, Merck) was used with a volume ratio of 10:4
gas oil: surfactant. The O/W emulsion was prepared by gradual
dissolving of the surfactant in distilled water 10 min before addition
of gas oil. Finally, a blender (T 25 Digital, 3000–25,000 rpm, IKA
Ceramics International 43 (2017) 14369–14379
Membrane Cell
Pressure Gauge
Permeate Tank
synthetic waste water with desirable particle size for MF and UF.
2.4.2. Experimental set-up and permeation flux determination
A schema of the experimental setup for filtration is presented in
Fig. 2. In the setup, the synthetic waste water was pumped from the
feed tank into the membrane module (stainless steel 316, with an inner
(3) diameter of 1.2 cm) by a centrifugal pump (Pedrollo, PKM 60 hard
Italy). The required pressure (0.1–3 bar) was adjusted using two valves
K1 and K2. The setup operates in a cross flow mode and it returns a part
of the feed as retentate to the feed tank. To reduce the feed temperature
and set it at 30 °C, the setup was equipped with a bypass flow (after the
(4)
outlet of the pump) and a cooling water circulator into the feed tank.
The following equation was used for permeation flux calculation:
J = m / (A × t ) (8)
2 2
where J (kg/m h) is permeation flux, A (m ) is effective membrane
(5)
area, and t (h) is filtration time.
(6)
2.4.3. Chemical oxygen demand (COD) measurement and rejection
(7)
calculation
Chemical oxygen demand (COD) values of feed and permeate were
determined using a COD analyzer (PALINTEST 7100, UK) according to
the standard ASTM D 1252.
The prepared membranes performance in the field of gas oil
separation from water was evaluated using COD rejection as calculated
by the following equation:
R(%) = (1 − C p / Cf ) (9)
−1 −1
where Cp is permeate COD (mg L ) and Cf is feed COD (mg L ).
2.4.4. Total porosity determination
The total porosity of the prepared membranes (Ɛ) was calculated via
the Archimedes method using distilled water as wetting liquid after
24 h soaking time. In this method, the following equation was used for
(Ɛ) calculation:
Ɛ = (Wet weight − Dry weight) / (Water density × A × L) (10)
2
where A (mm ) is membrane area, and L (mm) is membrane thickness.
In this equation, units of weight and density are g and g/mm3,
respectively.
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F. Mohammadi, T. Mohammadi Ceramics International 43 (2017) 14369–14379

2.4.5. Pore size study using SEM images and bubble point method Table 3
The average pore diameter of the prepared membranes was Effects of parameters and their levels on COD removal and permeation flux according to
the Delta values.
estimated using the bubble point method and the SEM micrographs
[37,38]. For calculation of the average pore diameter (ds) using the Response table for COD removal means Response table for permeation flux
SEM micrographs, Image-J software (version 1.44) was used as the means
image analyzer. The following equation was used for ds calculation:
Level Pressing Pressing Drying Level Pressing Pressing Drying
⎡ n n ⎤0.5 pressure time time pressure time time
ds = ⎢∑ nidi2 / ∑ ni ⎥ (bar) (min) (h) (bar) (min) (h)
⎣ i =1 i =1 ⎦ (11)
1 51.47 79.78 77.08 1 184.90 52.90 51.80
In which, n is the number of pores and di (µm) is pore diameter of 2 73.04 60.91 78.45 2 95.23 126.08 66.62
ith pore. For more exact investigation purpose, the SEM micrographs 3 89.23 73.05 58.22 3 38.18 139.34 199.89
were taken from three different points of the membrane surfaces. Delta 37.76 18.87 20.23 Delta 146.72 86.44 148.09
The bubble point method was conducted according to the standard Rank 1 2 3 Rank 2 3 1
ASTM F316-03. In this method, average pore diameter of the prepared
membranes was calculated using the following equation and the
intersection pressure points of the wet line with ½ dry line [37]:
investigate the performance of the membrane prepared by alkali
rp(m) = (2Ɣ /∆P)Cos θ (12) activation of BFS, permeation flux and COD removal were chosen as
quality characteristics (responses) in terms of permeation and separa-
where rp is the radius of capillary pores (m), Δp is applied pressure
tion [31,32].
difference (N/m2), Ɣ is liquid-gas interfacial tension and θ is contact
Table 3 shows the impact of parameters and their levels based on
angle of the liquid and membrane surface (θ = 0). Ɣ is assumed 0.073
the Delta parameter which is the absolute value of the average response
(N/m) for air and water.
characteristics at the low level subtracted from the high level [33]. This
table as an output of Minitab 17 indicates which level of a factor is
3. Results and discussion related to the higher or the lower response characteristic values.
According to Table 3, pressing pressure and drying time with Delta
3.1. Optimum alkali activation formula (A/S ratio of 0.04 and W/S parameters of 37.76 and 148.09 have the biggest impacts on COD
ratio of 0.2) removal and permeation flux, respectively. Indeed, changes in pressing
pressure and drying time result in the most changes on Delta
According to the obtained results from our previous work, the parameter. On the other hand, among the levels of these two
ceramic support with A/S ratio of 0.04 and W/S ratio of 0.4 has less parameters, pressing pressure of 400 bar and drying time of 8 h cause
porosity [30]. Furthermore, the researchers showed that the less the maximum changes in COD removal and permeation flux, respec-
amount of water leads to the higher porosity of AABFS [23,28,30]. tively. Also, pressing time with minimum changes on COD removal and
So, the porosity of AABFS increases by reducing W/S ratio from 0.4 to permeation flux is considered as the least effective factor on the
0.2 at fixed A/S ratio of 0.04. In addition, reducing the amount of water response. This parameter has the minimum Delta parameter value in
at a constant amount of NaOH enhances alkalinity resulting in the both COD removal and permeation flux.
production of more alkali activated products such as calcium silicate
hydrate. The decline continues until the geopolymeric slurry is not 3.2.2. ANOVA results
formed. In fact, W/S ratio of 0.2 has a border limit between AABFS In order to specify effective synthesis parameters and determine
powder and formation of the geopolymeric slurry. In this work, for percentage contribution of each factor in the response, an analysis of
synthesis of the membranes, alkali activation continues to some extent variance (ANOVA) was carried out. The results of this statistical
that the BFS keeps its powdery state and does not form a slurry. analysis are illustrated in Table 4 for the COD removal data and
Table 5 for permeation flux data. In both tables, the error value is not
3.2. Analysis of Taguchi experimental design significant, it is 6.555% and 6.418% for the membrane optimized from
the COD removal point of view and for the membrane optimized from
3.2.1. Taguchi method results permeation flux point of view, respectively. The error value indicates
The obtained results (permeation flux, COD removal and, total how much error is the result of uncontrollable factors. If this value is
porosity) of each membrane as well as the corresponding mean and S/ below 50%, the error of experiments is not significant in the results
N ratios of each trial are presented in Table 2. In this research, to [34,35,39].

Table 2
Results of quality characteristics and corresponding mean and S/N ratios for each experiment.

Membrane no. Process parameter Pure water flux Permeation flux S/N Mean COD removal S/N Mean Porosity (%)
(kg/m2 h bar) (%)
Pressing Pressing time Drying (kg/
pressure (bar) (min) time (h) m2 h bar)

1 225 5 3 150.378 61.067 −3.0566 70.617 63.60 36.0691 63.600 58.397

2 225 15 6 231.409 120.126 −0.9237 117.351 55.52 34.8890 55.520 59.198
3 225 30 8 890.848 209.130 −7.8166 366.737 35.30 30.9555 53.300 65.971
4 300 5 6 131.760 40.008 −5.5819 57.357 83.82 38.4670 83.820 56.410
5 300 15 8 404.732 201.419 −1.2902 202.216 47.43 33.5211 47.430 61.780
6 300 30 3 52.686 25.212 −1.6324 26.126 87.86 38.8758 87.860 45.850
7 400 5 8 60.558 31.089 −1.0217 30.720 91.92 39.2682 91.920 53.390
8 400 15 3 131.530 44.131 −4.7147 58.665 79.78 38.0379 79.780 53.800
9 400 30 6 51.097 23.912 −1.8263 25.159 96.00 39.6454 96.000 50.800

Note: In this table, the number of membranes and runs are the same.

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F. Mohammadi, T. Mohammadi Ceramics International 43 (2017) 14369–14379

Table 4
ANOVA results of the COD removal.

Factor Degree of freedom Sum of sqrs. Variance F-ratio Pure sum Percent (%)

Pressing pressure (bar) 2 2153.126 1076.563 8.847 1909.764 58.001

Pressing time (min) 2 548.785 274.392 2.255 305.423 14.783
Drying time(h) 2 766.946 383.473 3.151 523.584 20.660
Error 2 243.361 121.680 – – 6.555
Total 8 3712.219 – – – 100

Table 5
ANOVA results of the permeation flux data.

Factor Degree of freedom Sum of sqrs. Variance F-ratio Pure sum Percent (%)

Pressing pressure (bar) 2 14,238.725 7119.363 4.967 11,371.926 31.877

Pressing time (min) 2 9107.336 4553.668 3.177 6240.537 20.389
Drying time (h) 2 18,453.892 9226.946 6.437 15,587.093 41.315
Error 2 2866.799 1433.399 – – 6.418
Total 8 44,666.752 – – – 100

percentage contribution of each factor for COD removal and permea-

tion flux, respectively. In accordance with Fig. 3(A), among the
synthesis parameters studied, pressing pressure shows the strongest
influence on the COD removal data, followed by drying time and
pressing time. Also, Fig. 3(B) presents that drying time has the most
significant effect on the permeation flux. Pressing pressure and
pressing time are in the second and third rank, respectively. Thus,
the two parameters of pressing pressure and drying time have crucial
roles on both COD removal and permeation flux.

3.2.3. Identification and confirmation of the optimum results

Fig. 3. Contribution of the effective parameters on (A) COD removal and (B) permeation
flux.
The F-ratio parameter indicates the importance of synthesis para-
meters in terms of quality. If a quantitative assessment is favorable,
percentage contribution (P%) is used. Fig. 3(A) and (B) display the
obtained from Taguchi
After identification of the optimum conditions, the responses are
predicted by the Taguchi method. In this method, the predicted results
should be confirmed by running a new experiment. Put differently, the
new experiment is to verify the prediction data with experimental
conclusions. Table 6 presents the Taguchi prediction results for the
optimum membranes from COD removal and permeation flux points of
view. In accordance with the Taguchi prediction, the membrane
synthesized at pressing pressure of 400 bar, for 5 min pressing time
and 6 h drying time, indicates 100% COD removal. This value is almost
the same as the experimental result. The membrane identified as the
optimum membrane from permeation flux point of view is accidentally
in the DOE. According to Table 2, practical mean of permeation flux
obtained from the filtration experiment for this optimum membrane is
366.7 (kg/m2 h bar). The mean is almost close to the predicted one
(311.9 kg/m2 h bar). Therefore, the two membranes were nominated
as the optimal membranes from COD removal and permeation flux
points of view. Hence, to characterize these membranes, a morpholo-
gical investigation was conducted via the SEM micrographs (see
Section 3.3.3). Also, pore size of the optimal membranes was deter-
mined via two methods of bubble point and Image-J software for
permeation flux optimized membrane and COD removal optimized
membrane, respectively (see section 3.3.4).

Table 6
The results of Taguchi prediction for COD removal and permeation flux optimum membranes.

Membrane Pressing pressure Pressing time (min) Drying time (h) Mean of permeation flux Mean of COD removal
(bar) (kg/m2 h bar) (%)

Membrane optimized from COD removal 400 5 6 – 100% COD removal

Point of view
Membrane optimized from permeation flux 225 30 8 311.9 –
point of view

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F. Mohammadi, T. Mohammadi
Fig. 4. Effect of pressing pressure and drying time on COD removal (above) and permeation flux (below).
3.3. Performance and morphology analysis
3.3.1. Effects of synthesis parameters on COD removal and
permeation flux
As mentioned, pressing time has the minimum effect on COD
removal and permeation flux in comparison with pressing pressure and
drying time. Therefore, pressing pressure and drying time as the most
effective parameters were simultaneously investigated, regardless of
pressing time. In other words, in these situations, the fractional
factorial design was converted to a full factorial design with 2
parameters in 3 levels.
According to Table 2, in runs No. 1, 4 and 7 at a certain drying time
(5 min), with enhancement of pressing pressure and drying time from
225 to 400 bar and 3–8 h, respectively, permeation flux decreases and
COD removal increases. But in runs No. 2, 5 and 8, despite increasing
pressing pressure, drying time initially increases from 6 to 8 h and then
reduces to 3 h and this causes permeation flux increases at first
followed by decreasing. At this state, COD removal shows a reverse
trend. Finally, by increasing pressing pressure and decreasing drying
time in runs No. 3, 6 and 9, permeation flux decreases greatly and
reaches the lowest level, while COD removal increases significantly.
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Ceramics International 43 (2017) 14369–14379
These can be due to two main reasons including (1) porosity and pore
size reduction by increasing pressing pressure; and (2) particle size
enhancement of alkali activated powder by increasing drying time and
progress of activation reaction in an alkaline environment that causes
the bigger particles of AABFS powder stick together in pressing
machine and consequently porosity and pore size of the membrane
increase.
In experiments No. 1, 4 and 7, the effect of pressing pressure is
greater than that of drying time. As observed, increasing drying time,
permeation flux and COD of permeate decrease by increasing pressing
pressure. However, in experiments No. 2, 5 and 8, (at a certain drying
time of 15 min) effect of drying time is more than that of pressing
pressure. This causes initial enhancement and later decline of permea-
tion flux, when drying time increases from 6 to 8 h and then reduces to
3 h. Therefore, in runs No. 3, 6 and 9 (at a certain drying time of
30 min), increasing pressing pressure and decreasing drying time
simultaneously lead to the highest COD removal and the lowest
permeation flux compared to the other experiments.
These manners are due to co-current or counter current effects of
pressing pressure and drying time on the responses [31,33]. According
to the results, there is a direct relationship between pressing pressure
F. Mohammadi, T. Mohammadi
Fig. 5. Surface (panels A-D) and cross section (panels E and F) SEM images of some samples selected from Table 2: (A) membrane No. 1; (B) membrane No. 7; (C) membrane No. 2; (D)
membrane No. 8; (E) membrane No. 1; (F) membrane No. 8.
and COD removal. It means that by increasing pressing pressure, COD
removal increases. However, the relationship between COD removal
and drying time is indirect until pressing pressure is below 400 bar. At
pressing pressure of 400 bar, drying time has no significant effect on
COD removal and permeation flux. At this level, the impact of pressing
pressure overcomes the impact of drying time. More study, in this case,
was carried out as presented in the next sections (through SEM images
and interactive study).
Also, Fig. 4 illustrates effects of pressing pressure and drying time
on COD removal and permeation flux. As clearly observed, high
pressing pressure and short drying time cause that the amounts of
COD removal and permeation flux reach the highest and the lowest
values, respectively.
3.3.2. General investigation of SEM images
Fig. 5 illustrates SEM micrographs of surface of some samples such
as membranes No. 1 and 7 at 500× magnification and membranes No.
2 and 8 at 20k× magnification, and also SEM micrographs of cross-
section of membranes No.1 and 8. Synthesis conditions of these
selected membranes are explained in Table 2. Investigation of the
SEM images shows that the samples with longer drying time (hydration
with less intensity) and lower pressing pressure, have more porosity
and larger pore size. In addition, the results of filtration indicate that
permeation flux and COD removal of these samples are overall better
than those of the other prepared membranes. The SEM micrographs at
20k× magnification (from each 9 prepared membranes) show that
hydrated compounds (CSH) are formed in all the 9 prepared mem-
branes. Depending on the synthesis conditions, these compounds are
formed in different nano-scale dimensions with different intensities.
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Ceramics International 43 (2017) 14369–14379
The CSH structures are often formed in the capillary pores [23,28,40].
According to the SEM micrographs, formation of this structure in
capillary pores of the membranes is the reason for increasing selectivity
of the prepared membranes. Also, investigation of the cross-section
micrographs of all 9 membranes indicates that these membranes have
single layer cross section structure and are completely amorphous (as
observed in Fig. 5). The SEM images at 500× magnification show that
there are some splits-like cracks in the surface of membranes caused by
alkali activation of BFS. Based on the results of other researchers, alkali
activation in cement samples prepared from the slags causes micro-
scopic cracks in surface [23,41].
3.3.3. Morphological investigation of the two optimum membranes
using SEM micrographs
Surface SEM micrographs of the membranes optimized from COD
removal and permeation flux points of view are presented in Figs. 6 and
7 at two magnifications of 300× and 50k×, respectively.
As observed in the micrographs taken from surface of the two
optimum membranes in magnification of 300×, the permeation flux
optimum membrane has more porous surface and larger pores in
comparison with the COD removal optimum membrane. This is due to
the fact that the permeation flux optimum membrane was pressed at
225 bar, while the COD removal optimum membrane was pressed at
400 bar. Thus, the permeation flux optimum membrane with higher
porosity exhibits higher permeation flux (as observed in Fig. 6).
Furthermore, comparison of the SEM images at 50k× magnification
(Fig. 7) shows that there are some differences in intensity, formation
content of hydrated compounds, and size of the nanoscale plates of
these compounds. In the permeation flux optimum membrane, drying
F. Mohammadi, T. Mohammadi Ceramics International 43 (2017) 14369–14379

Fig. 6. Surface SEM images of the optimum membranes at 300× magnification: (right) permeation flux optimum membrane and (left) COD removal optimum membrane.

time of 8 h causes that AABFS powder loses some part of the water greater area. However, in this case, the structure does not have enough
existed in its structure. As a result, hydration process proceeds at a time to be converted to a hydrated gel. Accordingly, smaller initial
slower rate resulting in the formation of hydrated products in shape of seeds are present in the structure. The initial seeds are as formation
cross plates with smaller areas. However, during 8 h drying, the sites for the hydrated compounds [23,28,41]. Thus, the content of
structure has enough time to be more prone to transformation from hydrated compounds in the COD removal optimum membrane is less,
dissolution condition to hydrated gel condition [18,23,42,43].
Therefore, after 8 h drying, more amount of those small plates 18
Wet
(hydrated compounds) is generated. Moreover, after 8 h drying, 16
Dry
agglomeration of the alkali activated powder particles causes that the 14 1/2 Dry
larger particles of alkali activated powder push together in the pressing 12
Flow (ml/min)

machine. As a consequence, a more porous structure is formed with 10

8
larger pore size. Thus, the permeation flux optimum membrane shows
6
higher permeation flux and lower COD removal in comparison with the
4
COD removal optimum membrane. However, the SEM image of the
2
COD removal optimum membrane at 50k× magnification indicates that
0
the shorter drying time (6 h) the more water content in the structure in 0 0.5 1 1.5 2 2.5
comparison with the permeation flux optimum membrane. More water Pressure (bar)

content facilitates the progress of hydration process leading to the Fig. 8. Flow-pressure curve for the permeation flux optimum membrane resulted from
formation of the hydrated compounds in shape of cross plates with a the bubble point test.

Fig. 7. Surface SEM images of the optimum membranes at 50k× magnification: (right) permeation flux optimum membrane and (left) COD removal optimum membrane.

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F. Mohammadi, T. Mohammadi Ceramics International 43 (2017) 14369–14379

Fig. 9. Interaction plot of pressing pressure and drying time on the COD removal.

while the size of cross plates is larger. The SEM micrographs show that
these cross plates are formed in the pores. This causes that the COD
removal optimum membrane indicates higher COD removal in com-
parison with the permeation flux optimum membrane. In addition, due
to the shorter drying time for the COD removal optimum membrane,
the AABFS powder has smaller particle size. In fact, smaller size
improves the better agglomeration of particles. As a result, the COD
removal optimum membrane with less porosity and smaller pore size
shows higher COD removal and less permeation flux.
3.3.4. Pore size investigation of the two optimal membranes
To characterize pore size of the two optimum membranes, bubble
point method and SEM micrographs were used. The reason for the
selection of the bubble point method is the fact that only this method is
able to determine membrane pore size with a maximum pore diameter
of 0.1 µm according to the standard ASTM F-316. Due to low
permeation flux of the COD removal optimum membrane with a pore
size in the range of UF (limited area with pore size from 0.001 to
0.1 µm) [3], there is no possibility to use of the bubble point method for

Fig. 10. The SEM photographs of the prepared membranes at 400 bar pressing pressure.

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F. Mohammadi, T. Mohammadi
pore size characterization of this optimum membrane. This method can
only determine the maximum pore diameter of the COD removal
optimum membrane. Hence, the average pore diameter of the COD
removal optimum membrane was calculated using the Image-J soft-
ware and the SEM images visualized from three different points of the
membrane structure and 700 pores. Considering the software results,
the average pore diameter of the COD removal optimum membrane is
0.07 µm. From the bubble point results, the maximum pore diameter of
0.29 µm for this membrane was measured. As a result, the COD
removal optimum membrane with an average pore diameter of
0.07 µm and pure water permeation flux of 106 kg/m2 h is in the UF
limited range. According to Fig. 8, the cross point of wet and semi-dry
curves is at pressure of 2.2 bar. This point presents the pressure of
mean pore diameter for the permeation flux optimum membrane.
Therefore, the permeation flux optimum membrane with a mean pore
diameter of 0.66 µm and maximum pore diameter of 2.43 µm is in the
range of MF. Pure water permeation flux of 1960 kg/m2 h also
indicates that this membrane is a MF type.
3.4. Interactive study (using interaction plot and SEM images)
To study the interaction between two synthesis parameters of
drying time and pressing pressure on the response (COD removal),
interaction matrix was plotted (as observed in Fig. 9). This plot
indicates that there is no interaction between pressing pressure and
drying time when pressing pressure is 225 bar and over since the plot
lines are parallel. However, there are some interactions between the
two above parameters (pressing pressure and drying time) at pressing
pressure of 400 bar when drying time is 3 and 6 h, since the plot lines
cut off each other. Investigation of the COD removal results at the cross
point illustrates that pressing pressure values ≥ 300 bar are better
when drying time is 6 h shorter. In other words, at these pressing
pressure and drying time levels, COD removal is higher in comparison
with the other levels. In addition, the less difference in slope at pressing
pressure of 400 bar indicates drying time has no significant effect on
COD removal at this pressure (400 bar). It is due to the fact that
pressing pressure overcomes drying time. This minimizes the effect of
drying time [33,36,44].
Fig. 10 depicts the SEM micrograph of the membrane prepared at
pressing pressure of 400 bar at two magnifications of 300× and 50k×.
As clearly observed, despite differences between drying time levels, the
membranes prepared at pressing pressure of 400 bar have the same
porosity and pore size. This is due to the fact that drying time has the
least effect on the response, at this pressing pressure. The content of
formed hydrated compounds such as calcium silicate hydrate (CSH) is
about the same for the three synthesized membranes.
4. Conclusion
According to the obtained results from this research, porous
ceramic membranes could be synthesized via alkali activation of blast
furnace slag which is a by-product of the steel industry. Optimum
synthesis conditions were determined by Taguchi method. In this
method, the results of permeation flux and COD removal were used to
optimize the synthesized membranes from COD and flux points of
view. Two parameters of pressing pressure and drying time of alkali
activated powder were introduced as the most effective parameters on
the membrane synthesis. So that, pressing pressure and drying time
impact on COD removal and permeation flux data through influencing
on pore size and porosity of the membranes and intensity and
formation content of hydrated compounds (such as CSH), respectively.
In accordance with the Taguchi analysis, among the specified levels,
pressing pressure of 400 bar and drying time of 8 h were identified as
the most effective levels in the COD removal and permeation flux slope
differences, respectively. Finally, two optimum membranes from COD
removal and permeation flux points of view were synthesized at
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Ceramics International 43 (2017) 14369–14379
pressing pressure, drying time and pressing time: (400 bar, 6 h,
5 min) and (225 bar, 8 h, 30 min), respectively. From COD point of
view, the optimized membrane exhibited 100% COD removal. Pure
water permeation flux of the membrane optimized from flux point of
view was 1960 (kg/m2 h). According to the results, the COD removal
optimum membrane was in the range of UF, while the permeation flux
optimum membrane was in the range of MF.
Acknowledgment
The authors would like to thank Iran National Science Foundation
(INSF) (940110) for supporting the research.
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