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The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)

The 7th International Conference on Sensors ASIASENSE 2015


Surabaya, 4-6 October 2015

CORROSION AND FAILURE ANALYSIS

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
CODE: CF
Modification of carbon paste electrode with Schiff base for the detection of lead, cadmium and zinc ions
Kisan Koirala, Jose H. Santos, Ai L. Tan, Mohammad A. Ali, Aminul H. Mirza
Department of Chemistry, University Brunei Darussalam, Tungku Link, Gadong BE1410, Brunei Darussalam
Abstract: A sensor was constructed by modifying carbon paste electrode for the determination of lead, cadmium and
zinc ions using square wave anodic stripping voltammetry. The modified electrode was prepared by inserting
homogeneous mixture of 2-hydroxy-acetophenonethiosemicarbazone, graphite powder and mineral oil. A comparison
between the modified and unmodified electrodes is presented. Various important parameters controlling the
performance of the sensor were investigated and optimized. Electrochemical behavior of modified electrode was
characterized by cyclic voltammetry. The sensor exhibited linear behavior in the range of 0.25-12.5 mg L-1 for lead and
cadmium and 0.50-10.0 mg L-1 for zinc at accumulation time of 70 s. The limit of detection was calculated as 11.23 g
L-1, 13.27 g L-1 and 16.38 g L-1 for lead, cadmium and zinc, respectively. It is inexpensive, portable and
environmentally friendly and was successfully used for the determination of trace amount of lead, cadmium and zinc in
lab waste samples. The results obtained were compared with inductively coupled plasma atomic emission spectroscopy.
Keywords: Chemically modified electrodes; anodic stripping voltammetry; Schiff base; heavy metals; electrochemical
sensor
Corresponding author: Kisan Koirala, E-mail: 12h1251@ubd.edu.bn, Tel. +673-246-3001 Ext. 2620, Fax. +6732461502
1. Introduction
Lead (Pb), cadmium (Cd), and zinc (Zn) are toxic and hazardous pollutants in the environment due to their nonbiodegradability and persistence. They enter the environment through industrial waste, automobiles, atmospheric
deposition (both dry and wet), landfill runoff, and acid mine drainage. Pb causes health problems, such as digestive,
neurological, cardiac, and mental troubles [1, 2]. Cd causes nausea, vomiting, diarrhea, and cramps and long term
exposures cause high blood pressure and destruction of red blood cells [3, 4]. Likewise, Zn causes dizziness, chest pain,
trouble breathing, fever, chills and jaundice [5, 6].
Due to these severe effects in human health, researchers are focused to develop highly sensitive methods for the
detection of heavy metals. Several analytical techniques such as atomic fluorescence spectrometry (AFS) [7], atomic
absorption spectrometry (AAS) [8, 9], inductively coupled plasma optical emission spectroscopy (ICP-OES) [10],
neutron activation analysis (NAA) [5] and inductively coupled plasma mass spectrometry (ICP-MS) [11] are in practice
for detecting heavy metals. But these sophisticated instruments are expensive to operate and maintain with limited life
span. Moreover, these techniques require time-consuming manipulation steps, skilled manpower and are unsuitable for
in situ measurements.
Anodic stripping voltammetry (ASV) is the most widely used form of stripping analysis for trace metal
concentration [12-26] as it has shown various advantages such as rapid, accuracy, good selectivity and sensitivity. This
technique provides accurate measurements at the parts per billion (ppb) concentration levels and does not require
complex and expensive instrumentation. In addition, square wave anodic stripping voltammetry (SWASV) allows
minimizing the interference due to dissolved oxygen, and its use therefore eliminates the need for the time-consuming
sample de-aeration [12].
Over the past few decades, carbon pastes electrodes (CPE) are used for the fabrication of various electrometric
sensors for analytical purposes. They are prepared by homogenous mixing of carbonaceous material and liquid binder.
Recently, to improve the sensitivity, selectivity, detection limit and other features of CPE, chemically modified CPE
have been introduced. CPE are modified by various materials such as appropriate ligands, ion exchangers,
functionalized nanoparticles [27-30]. Selectivity and sensitivity of these modified CPE depends on the properties of the
modifier materials used.
Previously, we have synthesized and characterized 2-hydroxyl-acetophenonethiosemicarbazone (Fig. 1) which is
newly synthesized Schiff base capable to form complexes with target ions [31]. The binding of metal with Schiff base
contains a number of passive accumulating processes, which may include adsorption, ion exchange, coordination,
complexation, chelation and micro-precipitation [32]. Schiff base may be used as a modifier in the electrodes for the
preconcentration of metal ions [33].
In this study, we have modified CPE with 2-hydroxy-acetophenonethiosemicarbazone and applied for the
determination of Pb2+, Cd2+ and Zn2+ ions using SWASV.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015

OH
S
N
H

NH

NH2

CH3
Fig. 1 Chemical structure of 2-hydroxy-acetophenonethiosemicarbazone

2. Materials and Methods


2.1. Chemicals and reagents
Pb, Cd, Zn and potassium nitrate were purchased from Merck. Potassium dihydrogen phosphate (Fluka), potassium
hydrogen phosphate (Fluka), sodium hydroxide (GCE) and hydrochloric acid (Sigma-Aldrich) were purchased as
analytical grade and used without further purification. The CPE was prepared using graphite powder (< 20 m, SigmaAldrich) and mineral oil (Sigma-Aldrich). The phosphate buffer solution (PBS) was prepared from a mixture of
potassium dihydrogen phosphate and potassium hydrogen phosphate and adjusting to the required pH value with
hydrochloric acid (0.1 M) or sodium hydroxide (0.1 M). Stock standard solutions of all metal ions (100 mg L-1) were
prepared and preserved at 4 C when not in use. All the aqueous solutions were prepared by double distilled water at
room temperature.
2.2. Preparations of modified and unmodified electrodes
The modifier, 2-hydroxy-acetophenonethiosemicarbazone, was prepared in accordance to the method described in
the literature [31]. Briefly, 2-hydroxyacetophenonethiosemicarbazone was prepared by dissolving thiosemicarbazide
(1.22 g) in a 1:1 mixture of boiling absolute ethanol (10 mL) and dicholoromethane (10 mL). The resulting colorless
solution turned yellow when a solution of 2-hydroxyacetophenone (1.2 mL) in hot methanol (24 mL) was added. After
the addition of a few drops of 10% HCl, the reaction mixture was heated under reflux for 3 h to obtain a yellow solution
which was left to cool at room temperature.
Modified carbon paste electrode was prepared by homogenously mixing 2.25 gm (75%, w/w) of graphite powder
with 0.45 gm (15%, w/w) of modifier in a Petri dish for 5 min. Subsequently, 0.3 gm (10%, w/w) of mineral oil was
added and hand mixed for 10 min to obtain a fine paste. The homogenized paste was inserted into the carbon rod having
3 mm diameter and 7.3 cm length. The electrical connection was provided by a copper wire connected to the paste in
the inner hole of the rod. The prepared modified CPE was dried overnight at room temperature before use. The surface
of the sensing end was smoothed on a glass surface and rinsed carefully with double distilled water. Prior to the
electrochemical measurement, cyclic voltammetry was run for electrochemical activation of the electrode in the range
of -1.0 V to +1.5 V using scan rate of 100 mV s-1. Unmodified CPE was prepared by following the same procedure but
without modifier.
2.3. Cyclic voltammetry (CV)
All electrochemical measurements were performed in voltammetrical analyzer using eDAQ system consisting of an
ED-401 potentiostat connected to an e-corder and the graphs were plotted in eChem version 2.1.5. Measurements were
performed at room temperature in a conventional three-electrode cell comprising of silver/silver chloride as reference
electrode, platinum wire as counter electrode and the modified electrode as the working electrode. The volume of the
voltammetric cell for CV was approximately 10 mL. All the CV measurements were measured at the potential range
from -1.0 V to +1.5 V at a scan rate of 100 mV s-1.
2.4. Anodic stripping voltammetry (ASV)
ASV is one of the most sensitive electrochemical techniques applied for measuring trace metals. In this study,
SWASV was applied for analyzing Pb2+, Cd2+ and Zn2+ ions using the following steps: (a) preconcentration step, where
metals were preconcentrated by various deposition potential for 70 sec in a magnetic stirred solution and (b) stripping
step, where accumulated metals are stripped back to solution and SWASV were recorded. Nitrogen gas was purged in
to the system for 5 minutes before starting the experiment. One of the main features of SWASV is electrochemical
cleaning of electrodes and surface regeneration. A fixed potential of +0.8 V for 60 sec was applied to clean the
electrode surface for Pb2+ and Cd2+ ions and +1.2 V for 60 sec was applied to clean electrode surface for Zn2+ ions.
Blank tests were performed after each measurement of samples to remove any potential for carryover between samples.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
2.5. Analysis of real samples
In order to demonstrate the applicability and reliability of the proposed sensor, lab waste samples from inorganic
laboratory were collected and diluted twice. Those samples contain unknown concentration of metal ions and they were
evaluated by standard calibration curves. Inductively coupled plasma atomic emission spectroscopy (ICP-AES, iCap
6000) was used to measure the concentration of metal ions in real samples. The results obtained from ICP-AES were
compared with those obtained from modified CPE.
3. Results and discussion
3.1. Cyclic voltammetry
CV measurement was performed to characterize the electrode-electrolyte system in the presence and absence of
modifier. CV for modified and unmodified electrodes in 0.1 M HCl solution is shown in Fig 2. Unmodified CPE
showed flat surface whereas modified CPE showed small anodic current and cathodic current at -0.2 V and -0.5 V,
respectively.
3.2. Sensor response
Preliminary experiments were performed to study the behavior of modified CPE on metal ions. Fig 3 shows
SWASV in a solution containing 5 mg L-1 concentration of Pb2+, Cd2+ and Zn2+ ions in unmodified and modified CPE.
Modified CPE showed three distinct peaks at -0.50, -0.76 and -1.02 V vs silver/silver chloride corresponding to the
oxidation of Pb2+, Cd2+ and Zn2+ ions at the electrode surface, respectively. Metals ions were accumulated by reduction
at the electrode surface at deposition potential of -1.5 V. The reduced metal ions were then oxidized in the stripping step
and SWASV peaks were recorded. The response of the CPE in absence of ligand does not show any well defined peaks.
The modified CPE exhibited good repeatability, with relative standard deviations (RSD) of 1.85%, 5.37% and 5.53%
for Pb2+, Cd2+ and Zn2+ ions, respectively for three successive runs.
3.3. Effects of pH
The influence of pH on electrochemical responses of Pb2+, Cd2+ and Zn2+ ions were studied in PBS at pH range from
1 to 5 is shown in Fig 4. All solutions contained fixed concentration of standard at 10 mg L-1 Pb2+, Cd2+ and Zn2+ ions.
The highest peak currents for all the metal ions under study were observed at pH 1. Therefore, pH 1 was used in further
studies. Reduction of peak current as the pH became more basic was probably due to the formation of lead hydroxide,
cadmium hydroxide or zinc hydroxide, which depleted the cations existence as free ions, and thus less free cations were
available at the binding sites of the modifier of CPE [34].
3.4. Effect of deposition time
The dependence of the anodic peak current on the deposition time was studied. Fig 5 shows the effect of varying
deposition time vs peak current in a solution containing 10 mg L-1 of Pb2+, Cd2+ and Zn2+ ions in the range of 5-80 sec.
The stripping peak current increases linearly with increasing deposition time suggesting more metal ions deposition on
the modified electrode surface. However, when the deposition time was beyond 70 s, the stripping current became
almost constant, indicating that the amount to metal ions on the electrode surface achieves saturation or equilibrium.
Hence, 70 s was used for further studies.
3.5. Determination of Pb2+, Cd2+ and Zn2+
The analytical performance of the modified electrode was investigated by individual analysis of Pb2+, Cd2+ and Zn2+
ions under optimized experimental conditions. The peak current increased with increasing metal ions concentration. Fig
6 shows SWASV response of the modified electrode towards various concentrations of standard solutions in the range
of 0.25 mg L-1 to 12.5 mg L-1 for Pb2+ and Cd2+ ions, and 0.50 mg L-1 to 10.0 mg L-1 for Zn2+ at accumulation time of 70
s.
The limit of detection (LOD) is defined as 3/m, where is standard deviation of lowest analyte concentration
signals and m is slope of the calibration graph. Standard deviation was estimated by six replicate determinations of the
least concentration signals. LOD was calculated as 11.23 g L-1, 13.27 g L-1 and 16.38 g L-1 for Pb2+, Cd2+ and Zn2+
ions, respectively.
3.6. Sample analysis
The analytical performance of the developed sensor was evaluated by measuring Pb2+, Cd2+ and Zn2+ ions in lab
wastes samples. The results obtained from modified CPE were compared with inductively coupled plasma atomic
emission spectroscopy (ICP-AES). The results of these measurements are shown in Table 1.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015

60

Unmodified CPE
Modified CPE

I / A

40

20

-20
-1.5

-1

-0.5

0.5

1.5

E/V

Fig. 2 CV of carbon paste electrode with and without modifier in 0.1 M HCl as supporting electrolyte (100mV s-1 scan
rate).

120
Unmodified CPE
Modified CPE

100

Cd2+
Pb2+

I / A

80
60
40

Zn2+

20
0
-1.2

-1

-0.8
E/V

-0.6

-0.4

Fig. 3 SWASV of 5 mg L-1 of Pb2+, Cd2+ and Zn2+ ions with and without modifier. Conditions: potential applied -1.5 V,
0.1 M HCl supporting electrolyte, deposition time 70 s, scan rate 75 mV s-1, square wave frequency 15 Hz, step
potential 5 mV, square wave amplitude 25 mV and resting time 10 s.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
300
lead

250

Cadmium

I / A

200

Zinc

150
100
50
0
0

pH
Fig. 4 Effects of pH on stripping current for 10 mg L-1 Pb2+, Cd2+ and Zn2+ ions. Conditions: potential applied -0.9 V for
Cd2+, Pb2+ ions and -1.5 V and Zn2+ ions, deposition time 70 s, scanrate 75 mV s-1, square wave frequency 15 Hz, step
potential 5 mV, square wave amplitude 25 mV and resting time 10 s.

Current (A)

350

Lead

300

Cadmium

250

Zinc

200
150
100
50
0
0

20

40
60
Deposition time (sec)

80

100

Fig. 5 SWASV peaks for 10 mg L-1 of Pb2+, Cd2+ and Zn2+ ions at various depositions time. Conditions: potential
applied -0.9 V for Pb2+ and Cd2+ ions whereas -1.5 V for Zn2+ ions, PBS at pH 1 as supporting electrolyte, deposition
time 70 s, scan-rate 75 mV s-1, square-wave frequency 15 Hz, step potential 5 mV, square wave amplitude 25 mV and
resting time 10 s.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015

300

400

Current, I / A

300
250

300

250

200

200

0
0

5
10
Lead conc. / mg L-1

150

I / A

I / A

100

200

300
y = 21.85x - 10.89
R = 0.980

y = 27.122x - 23.081
R = 0.9871

Current, I / A

350

15

200

100

150

10

15

Cadmium conc. / mg L-1

100

100

50

50
0

-1.2

-1

-0.8

-0.6

-0.4

-0.2

-1

-0.8

-0.6

E/ V

-0.4

-0.2

E/V

(a) Lead

(b) Cadmium
200
Current, I / A

200

160

I / A

120

150

y = 14.598x - 1.3413
R = 0.9938

100
50
0
0

80

4
6
8
Zinc conc. / mg L-1

10

12

40

0
-1.2

-1

-0.8
E/ V

-0.6

-0.4

(c) Zinc
Fig. 6 Calibration curve for (a) lead, (b) cadmium and (c) zinc at pH 1 at modified CPE. Condition applied: potential
from -0.9 V to +0.3 V, deposition time 70 sec, scan rate 75 mV s-1, square-wave frequency 15 Hz, step potential 5 mV,
square-wave amplitude 25 mV and rest time 10 s.

Table 1. Comparison of results obtained from modified CPE and ICP-AES methods (n = 3).
Sample
Metal of detection
Modified-CPE (mg L-1)
ICP-AES (mg L-1)
Pb2+
2.69 0.54
Lab waste 1
Cd2+
7.08 1.09
2+
Zn
2.01 0.88
Pb2+
3.72 0.95
2+
Lab waste 2
Cd
4.76 0.38
Zn2+
3.46 0.52
*ICP-AES: Inductively coupled plasma atomic emission spectroscopy

2.52 0.46
6.45 0.88
1.34 0.49
3.56 0.57
5.00 0.45
3.27 0.32

4. Conclusions
A chemically modified CPE with Schiff base was constructed for the determination of Pb2+, Cd2+ and Zn2+ ions
using SWASV. The sensor response was influenced by measurement conditions such as pH and deposition time.
Contamination on the electrode surface can be removed by electrochemical cleaning. The sensor was successfully used
for the determination of metal ions content in lab waste samples. This sensor has a simple design, uses inexpensive
materials and requires a short measurement time for analysis of metal ions in aqueous solutions.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
Acknowledgements
We would like to acknowledge graduate research scholarship office, University of Brunei Darussalam (UBD) for
financial support.
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Surabaya, 4-6 October 2015
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The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
CODE: CF
Failure Analysis of Secondary Superheater Inlet Boiler Tube of Fossil Power Plant in Indonesia
Cukup Mulyana1), Sulthoni Akbar2), Bambang Soegijono2), Tri Wibowo3), M Rizka Putra B4)
1

Electrical Engineering Study Programme, Padjadjaran University, Jatinangor 45363,


Indonesia
2
Material Science, Faculty of Mathematics and Natural Sciences, University of Indonesia, Salemba 10430,
Indonesia
3
Balai Besar Teknologi Kekuatan Struktur, Badan Pengkajian dan Penerapan Teknologi, Serpong 10340,
Indonesia
4
Physics Study Programme, Padjadjaran University, Jatinangor 45363,
Indonesia
Abstract. There has been a premature failure of secondary super heater inlet tube boiler of the steam power plant in
Indonesia, this caused the plant stop operating. The damage is in the boiler tube number 47, crack propagated quickly
stopped in thicker welded connection. The tube originally was straight and become totally bent in 90 after failure. The
study of failure analysis has been conducted. Plant operational and pipes data, chronological record before accident has
been collected. Further observation and serial test the chemical composition, high temperature tensile, hardness, SEM
EDX, and metallographic test have been completed. From the spectrometer analysis the chemical composition of
material is low carbon steel SA 213 T22. From visual observation the ruptured tube is the edge thinning, fish mouth and
shaped knifelike. The mechanism of failure start with bulging, wall tube thinning following with the increasing of hoop
stress exceeding the plastic limits, finally bursting. Circumferential hoop stress caused crack in radial direction followed
by longitudinal stress caused crack along the axis, thermal compression stress bent the tube 90.From the data analysis
the boiler pipes failed premature in the form of short term overheating at temperature> 890C. From the fault tree
analysis fire impingement and the flow fluid pattern is not following procedure are the most possible event. The fire
impingement because of abnormal burning process (excess fuel or oxygen) and other undefined process parameters.
Keyword : Boiler tube; short-term overheat; violent rupture; Fault Tree Analysis
Corresponding author: Cukup Mulyana, E-mail: c.mulyana55@yahoo.com, Tel. +62-81573208420
1. Introduction
Boiler is main facility for generating steam and rotates turbine converting mechanical energy to electrical energy
in power plant. The fluid is flown in a great number of tubes. The heat from combustion process in the burner is
radiated and convected to the tube change the water into super heated steam.
The failure is in tube number 47 swelling and bursting. The crack propagate rapidly and it stop at the weld joint of a
thicker tube. The tube geometry change from horizontal bent tube 90.
From the historical data this tube is failed in 2005 and replace with the new one, and fail again in 2014, considering
the time life of the tube it is classified as premature failure. The specification of tube material is low carbon steel SA213 T22. This material has relatively high thermal resistance and corrosion. The operation temperature of tube is 505 C
Initial observation start after the all system is shutdown, the rupture sample was cut to be observed in laboratory.
The chronological data and the temperature change per minute during failure process is taken from site and control
room. From the first observation the failure is predicted because of local heating and short term overheat.
Finding the root cause of the failure the sample ruptured is observed and serial tested is conducted in laboratory.
The objective of the research are determining the mechanism of ruptured tube, the root cause of tube failure number
47 in superheater inlet boiler, finding other contributed factors of the failure and giving recommendation to avoid the
similar failure in the future through inspection procedure, maintenance, and operation procedure.
2. Method and Experiment
First the observation were focused on the operational data of boiler, the historical data of failure tube, the
chronology of failure process and the record of temperature fluctuation, all data are taken from the control room. The
data of ruptured tube is observed directly from the field, the foto macro of the ruptured tube is taken. The mechanical
properties of material strenght, hardness is tested in laboratory, the chemical composition is also tested by spectrometer,
while the microstructure of material is observed by optical mycroscope. The fracture mode, and deposit of corrosion in
the failure tube is observed by SEM /EDX. All the data were analyzed, from the the all the facts it try to find the
relation of all evident and classified the major or the minor cause that afect the tube ruptured. Finally the root cause of
the filler was constructed by fault tree analysis. The recommendation is given to the company in order to avoid the
similar failure in the future.

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3. Result and Discussion


The damage occur in tube number 47 in superheater inlet which the position is shown in Fig. 1.

Fig.. 1. Superheater tube scheme inside the boiler.

(a)

(b)

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3
4
2
5
1

(c)
Fig. 2.The rupture tube condition (a) Before cutting (b) After cutting (c) Crack propagation.

From Figure 2 (a) it can be shown originally the tube is a straight line, after ruptured the tube bent 90 and push far
from it position. After the ruptured tube is cut, from the photo macro the profile of ruptured tube is thin lips or fish
mouth shape, it indicated that there is local heating in a short periods, or short term overheating. In the bent position the
wall tube become thinner drastically, the tube is bulging, swelling finally bursting. The stress on the wall tube increased
more than its plastic limit rapidly, this caused the tube ruptured. Mechanism of crack is indicated in Figure 2(c).
Starting from the thinnest part of the failure tube, because of the increasing of the hoop stress the crack propagate
horizontally, indicated by arrow 1, and 2.After that, the crack propagate along the tube axis to the right arrow 3 and to
the left arrow 4 and stop at the joint weld of at thicker tube, and turn to the right arrow 5.
3.1. Chemical Composition Test
Using spectrometer the Chemical composition of the ruptured tube is in table 1. Specimen A is for the thin tube,
and specimen C is for the thick one.

Number
Atom
Specimen A
The Contain Specimen C
of Atom (%) SA 213 T22
standart

TABLE 1. Chemical composition test result


1
2
3
4
5
6
7
C
Si
S
P
Mn
Ni
Cr
0.09682 0.28996 0.003 0.0088 0.48196 0.02595 2.02072
0.09878 0.28622 0.0019 0.0066 0.47604 0.0251 1.99294

0.15 max 0.5 max 0.025 max 0.025 max 0.3 - 0.6

8
Mo
0.94014
0.96575

1.9 - 2.6 0.87 - 1.13

9
Fe
96.0519
96.0473
-

Refer to standard, the specimen A and C is ferritic low carbon steel SA-213 T22.
3.2. Mechanism of Crack
Stress equation (1) explained the crack mechanism of the ruptured tube:
= + +
=

(1)

+ ET

Where P is internal pressure inside the tube, D is Outer Diameter, t is tube thickness, is linear thermal coefficient
of expansion, E is Young Modulus and T is difference of temperature. The ishoop stress work in circumferential
direction of the tube because of internal pressure. Due to the bulging process, the thickness of wall tube decreased, the
hoop stress exceed Yield Strength (YS) of material that cause fracture in the tube as the direction is shown by arrow
number 1 and 2. is longitudinal stress which is stress along the axis, and it is thermal stress caused by extreme
temperature increase in short term. Thermal stress is compressive stress it cause the tube bend to 90 angle.

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Metallography test is conducted in 3 points, such as the edge of un-deformed
un deformed thin tube, the edge of fractured tube
which is undergo depletion and the edge of deformed thick tube as shown in Fig. 2(a),
(a), (b), (c). The result of
metallography test is shown by Fig. 3 (a), (b), (c). In the figure 3 (a), grain boundaries is circular symmetry
symmetry-formed.
(a)

Titik A

(b)

Titik B

(c)

Titik C

Fig. 3.Metallography
Metallography test sample spot (a) The edge of thin tube (b) The edge of fracture tube (c) The edge of thick tube
tube.
Titik B

(a)

(b)

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(c)

Fig. 4.Metallography
Metallography test result (a) The edge of thin tube (b) The edge of fracture tube (c) The edge of tthick tube.
From the result of metallography test above, the micro voids do not exist, which means the creep phenomena in this
failure do not exist as well. However there are significant differences in the microstructure between ruptured spot and
the spot which is far from ruptured spot as shown in the figure 3 (B and C is ruptured spot, while A is spot which is far
from ruptured spot). In the ruptured spot there are martensite and bainite alloy which indicate the heating up to austenite
phase and followed by rapid cooling rate. While at the spot which is far from ruptured spot the only exist phase are
ferrite and pearlite alloy.
Hardness level gradation which is related with several tube spot could be seen in Fig. 5.
Sample A

Sample B

Sample C

Fig. 5. Hardness test specimen


specimen for sample A, B, C as function of distance
distance.

From Brinell test, hardness level change as function of distance for each the hardness of specimen is further shown
by Fig. 6

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Fig. 6. The hardness Brinel of specimen A,B,C as a function point test


test.
For sample A has constant hardness value which has average 151,72 HB, indicates there is no temperature eeffect in
that spot. Consistence with the metallographic
metallograph test in figure 4(a), the grain boundary is homogenously circle. While the
hardness of sample B and C is increase as function of distance. Getting closer to ruptured sspot then the hardness is
increase, as shown in curve B, C in figure 6. This is accordance with metallographic test result where the particle shape
and flatten to stress direction.. It indicates that occur enormous stress exceed maximum
maximu plastic range due to extreme
temperature increase in spot B and C.
The SEM image of frucure area is shown in Fig.
Fig 7.

Fig. 7. The crack propagation pattern of the ruptured tube fram SEM image.
The yellow line enclose pattern
ern of crack propagation with intergranular pattern,, while at the outside of the yelow
line the pattern of crack is trans ganular. The
he proporsion of trans granular is highher than inter granular pattern. Its
mean the stress increase
rease very rapidly due to the extreem temperture in short period of time and bursting the tube.
Metallography and hardness information above indicate that the tube has undergone
undergone local heating over austenite
temperature (T > 890 C) which the tube enter the
the austenite phase, when cooling process martensite phase and bainite
phase will exist as illustrated in the graphic below:
The vertical line in the Fig. 7 is the time of cooling process after more than 3 hours. The period of time accordance
with the chronological data of the temperature decrement during shut down process. From
rom metallographic test in figure
4(b) and 4(c), the spherodized and austenite (A) is form. It indicated the temperature is reached the austenite
temperature, and during the cooling process
proce the phase of martensite (M), bainite (B), ferrite (F)
(F), pearlite (P) is formed.

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Fig. 7. Isothermal Cooling Curve for medium carbon steel. The cooling rate difference will result different
microstructure and hardness value from Martensite (M), bainite
bainite (B), ferrite (F), pearlite (P) structure
3.3. Fault Tree analysis
The failure root and other contributive factor is determined by fault tree analysis (FTA), using binary logic gate
AND and OR all possible evident is evaluated.

Fig. 8. Fault Tree Analysis (FTA) for determining the root cause of the ruptured super heater inlet boiler tube
tube.
TheAND logic gate FTA in Figure 8 express one event only can exist if two or more preceding event are
simultaneously happened, while the OR
OR logic gate expresss one event only can exist if at least one event from two or
more preceding event are happened.. From first investigation the ruptured tube exist because of the damage mechanism
in the boiler and the pressurized tube exceed the operation pressure. The possible
ible preceding event of damage
mechanism is swelling and bulging, there is no indication of corrosion. From metallographic test the existence of
martensite, and bainite indicate austenite temperature is exceeded,the possible evident of the bulging and burs
bursting tube
is because of short term overheat. There
here are three possible event preceding the short term over heat, the blockage due to
corrosion, fire impingement and the flow fluid pattern that is not following procedure. F
From the data analysis fire

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impingement and the flow fluid pattern is not following procedure are the most possible event. From further analysis the
fire impingement can be exist if there is uncontrollable burning process or the excessive heat occur because of excessive
fuel and oxygen and other undefined process parameters. To determine the failure root precisely, it still need more
information data tube investigated.
4. Conclusion
The failure cause of tube number 47 in superheater inlet boiler is short term overheat. with the temperature > 890
C. Failure mechanism started with bulging, wall-tube thinning, the increasing of hoop stress exceed plastic limit finally
bursting. The crack propagation started in radial direction because of hoop stress, following in the axial direction
because of longitudinal stress. Bending process cause by thermal stress compression due to the extreme temperature in
short period of time. From FTA fire impingement and the flow fluid pattern is not following procedure are the most
possible event. The fire impingement because of abnormal burning process (excess fuel or oxygen) and other undefined
process parameters.
Acknowledgements
We would like to say thank to PT. Indonesia Power which allow us to investigate the root cause of the ruptured
tube number 47 in super heater inlet boiler unit 2 Suralaya Indonesia,and to BPPT that helped us in laboratory sample
test during the investigation. With their contribution, this research can be finished.
References
[1] ASM Handbook Volume 11: Failure Analysis and Prevention; 2002
[2] Viswanathan, Ramaswamy. 1989. Damage Mechanism and Life Assessment of High-Temperature Components.
USA: ASM International
[3] Dieter, E. George. 1988. Mechanical Metallurgy, SI Metric ed. Singapore: McGraw Hill Book Co
[4] French, N Metallurgical Failures in Fossil Fired Boiler, John Wiley and Sons. Inc
[5] Purwono, Sari. 2010. Data Operasional Boiler Unit 2 Juni 2010limited. PT. Indonesia Power UBP Suralaya

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CODE: CF
Investigation of Corrosion Protection of Rebar Steel using Organic Inhibitor in Simulated Pore Solution
Arini Nikitasari1), Efendi Mabruri1)
1

Research Center for Metallurgy and Material, Indonesian Institute of Sciences, Serpong 15313, Indonesia

Abstract: Rebar steel embedded in concrete is naturally protected against corrosion by passive layer formed on the
steel surface by the high alkalinity of the concrete. Corrosion in concrete rebar steel can initiate only when passive layer
is destroyed due to the ingress of chloride or carbonation of concrete. Aim of this paper is to investigate on the
performance of organic inhibitor dimethylethaneamine (DMEA) in protecting rebar steel from carbonates and chlorides
induced corrosion in concrete. Rebar steel specimen immersed in three kinds of solution : simulated pore solution
mixed with seawater, simulated pore solution mixed with sodium chloride as the sources of chloride, simulated pore
solution mixed with seawater, sodium chloride, sodium carbonate, and bicarbonate as the source of carbonate to corrode
the rebar steel. DMEA was added in the solution with various concentration (0,1 M; 0,3 M; 0,6 M). The performance of
the organic inhibitor was evaluated by corrosion measurement system for 20 days. The results give information about
corrosion rate and corrosion prevention ability of the analysed organic inhibitor.
Keywords: Simulated concrete pore solution, rebar steel; organic inhibitor; DMEA; carbonation; corrosion
measurement system.
Corresponding author: Arini Nikitasari, E-mail : arini_nikitasari@yahoo.com, Tel. 085286244363
1. Introduction
Reinforced concrete is widely used for building materials and plays a significant role in economic development.
However, the premature degradation of reinforced concrete structures due to the reinforcing steel corrosion has become
a serious problem in modern society, which results in a huge economic loss [1]. Steel reinforcement embedded in
concrete is naturally protected against corrosion by a thin iron oxide layer that is formed on the steel surface by the high
alkalinity of the concrete [2]. Corrosion can initiate only when passivity is destroyed. This occurs in two ways:
carbonation of concrete, the reaction of atmospheric CO2 with cement paste, that lowers pH and causes general
corrosion; the presence of chlorides at the steel surface in concentration higher than a critical threshold, generally
considered in the range of 0.4-1% by cement weight. Chlorides may be added to concrete in the mix water or in the
aggregates, even if nowadays it is restricted by standards; chlorides can also penetrate from outside, in highway
viaducts where de-icing salts are used, or in marine structures [3].
When steel in concrete corrodes, the cross section of the reinforcing bar becomes smaller, thus reducing the load
carrying capacity of the reinforced concrete member. The volume of corrosion products exerts pressure on the concrete
resulting in spalling of the concrete cover and directly exposing the steel to the corrosive agents. This lead to the loss of
a structures load carrying capacity and to the need for repairs [4]. In an attempt to minimize the effect of rebar
corrosion, various procedures are frequently employed, such as cathodic protection, the use of inhibitors, and the
application of coatings to the external concrete surface or to the reinforcing steel bars [5]. Among available methods,
corrosion inhibitors seem to be attractive because of their low cost and easy handling, compared with other preventive
methods [6].
Corrosion inhibitors is a chemical compound which when added in adequate amounts to concrete can prevent
corrosion of embedded steel and has no adverse effect on the properties of concrete. Nowadays corrosion inhibitor
presents an easily implemented solution to the growing problem of corrosion of reinforcing steel in concrete. However,
to be considered viable, these additives should not only prevent or delay the onset of corrosion they must not have any
detrimental effect on the properties of concrete itself such as strength, setting time, workability and durability. It must
be clarified that corrosion inhibitors do not totally stop corrosion but rather increase the time to the onset of corrosion
and reduce its eventual rate [7]. The effect of organic corrosion inhibitor, N,N dimethylaminoethanol (DMEA) on the
corrosion of steel due to chloride ingress and carbonation was experimentally investigated in this paper.
The long time necessary for chlorides and carbonate to penetrate the concrete cover can be avoided by testing the
steel in simulated pore solution, which is mainly consistes of saturated calcium hydroxide, sodium hydroxide, and
potassium hydroxide with the pH ~13.5 [8]. This paper illustrates the results of 20 days investigation on the inhibitive
effectiveness of organic commercial corrosion inhibitors in preventing carbonation and chlorides induced corrosion.
Corrosion was monitored by rebar potential and corrosion rate measurements. Visual observation at the end of exposure
was carried out. Results are discussed in terms of ability of the corrosion inhibitors to prevent corrosion occurence or to
decrease corrosion rate, once corrosion started.

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2. Experimental
2.1. Materials
Corrugated steel bars with the composition is given in Table 1 were used for the experiments. Prior to the
experiment the reinforcing steel electrodes were cleaned in HCl : H2O (1:1) with hexamethylentetramine solutions and
degreased in acetone. Rebar steel as specimen cut to size 1 cm and mounted with resin so the exposed area of the
reinforcing steel electrodes was 1.23 cm2. The mounted rebar steel then abraded with abrasive paper from 80 cw till
1000 cw. The specimen immersed in the test solution for 20 days.
Table 1. Chemical Composition of Rebar Steel
Komposisi Kimia (%)
C
Si
Mn
P
S
Fe
0,37
0,23
0,54
0,03
0,04
Bal
2.2. Solution test
There are three kinds of solution test used in this experiment : simulated pore solution mixed with seawater;
simulated pore solution mixed with 3.5 %wt sodium chloride; simulated pore solution mixed with seawater, sodium
chloride, sodium carbonate, and bicarbonate. Table 2 shows the chemical composition of simulated pore solution.
DMEA was added with various concentration (0.1 M, 0.3 M, 0.6 M) into solution test. A series of solution test is given
in Table 3.
Table 2. Chemical Composition of Simulated Pore Solution [8]
Unsur
Mol/liter
0,1
NaOH
0,3
KOH
0,03
Ca(OH)2
0,02
CaSO4.H2O

No
1
2
3
4
5
6
7
8
9
10
11
12

Table 3. Series of Solution Test


Solution Test
Simulated Pore Solution + Seawater
Simulated Pore Solution + Seawater
Simulated Pore Solution + Seawater
Simulated Pore Solution + Seawater
Simulated Pore Solution + Seawater + 0.3 M NaHCO3 + 0.015 Na2CO3
Simulated Pore Solution + Seawater + 0.3 M NaHCO3 + 0.015 Na2CO3
Simulated Pore Solution + Seawater + 0.3 M NaHCO3 + 0.015 Na2CO3
Simulated Pore Solution + Seawater + 0.3 M NaHCO3 + 0.015 Na2CO3
Simulated Pore Solution + NaCl 3.5 % + 0.3 M NaHCO3 + 0.015 Na2CO3
Simulated Pore Solution + NaCl 3.5 % + 0.3 M NaHCO3 + 0.015 Na2CO3
Simulated Pore Solution + NaCl 3.5 % + 0.3 M NaHCO3 + 0.015 Na2CO3
Simulated Pore Solution + NaCl 3.5 % + 0.3 M NaHCO3 + 0.015 Na2CO3

DMEA
0.1 M
0.3 M
0.6 M
0.1 M
0.3 M
0.6 M
0.1 M
0.3 M
0.6 M

2.3. Measurement Technique


Corrosion potential and corrosion rate measurement in this experiment based on ASTM G-5 standard.
Measurement was done everyday for 20 days using Gamry Instruments G750 Series. Measurement techniques of
corrosion potential and corrosion rate using Tafel polarization in potential range -200 mV to 200 mV from OCP (Open
Circuit Potential) with 1.5 mV/s scan rate.There are three kinds of electrodes used for this measurement techniques such
as Fig.1, counter electrode was grafit, reference electrode was SCE (Saturated Calomel Electrode), and working
electrode was mounted rebar steel specimen.

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Fig. 1. Three Electrodes Scheme [9]

3. Results and discussion


3.1. Corrosion behaviour
Corrosion behaviour of rebar steel in three kinds of test solution (simulated pore solution (SPS) mixed with
seawater, SPS mixed with seawater and carbonate, and SPS mixed with sodium chloride and carbonate) has been
investigated by polarization study. The evolution of corrosion potential (Ecorr) and corrosion current density (Icorr) with
time for simulated pore solution (SPS) mixed with seawater with different concentration of inhibitor is given in Fig.2.
Based on Fig. 2, it can be observed that the addition of DMEA results in a reduction of the corrosion current density. On
the other hand, the presence of DMEA produces a shift of Ecorr towards more negatif values with respect to the solution
without DMEA. Fig. 3 shows the evolution of corrosion rate (icorr) with time of rebar steel in simulated pore solution
mixed with seawater at different DMEA concentration. It can be observed that the increase of DMEA concentration
produces a reduction of the corrosion rate, supporting the registered reduction of the corrosion current density. From
Fig.3, corrosion rate in solution without inhibitor rises drastically from 4 mpy at 1st day to 20 mpy at approximately 20
days of experiment time. Corrosion rate with inhibitor also rises but lower than without inhibitor, so DMEA is effective
to inhibit corrosion of rebar steel in seawater environment and the best performance for inhibiting corrosion is DMEA
with concentration 0.6 M. Corrosion rate for DMEA concentration 0.1 M increases dramatically at last day
measurement, this is suggest that DMEA 0.1 M has been depleted in the 20th day, so for better performance DMEA
should use in higher concentration than 0.1 M.
In Fig. 4, the evolution with time of Ecorr and Icorr of steels submerged in simulated pore solution mixed with
seawater and carbonate without DMEA and with 0.1 M, 0.3 M, and 0.6 M of DMEA is presented. The trend of Ecorr
with 0.3 M and 0.6 M DMEA is more positif while 0.1 M of DMEA is more negatif value than without DMEA. Based
on Fig. 4, DMEA with concentration 0.6 M produces a slight decrease in the corrosion current density, the addition of
DMEA in lower concentration (0.1 M and 0.3 M) results in a higher corrosion current density.
Fig. 5 shows the evolution corrosion rate with time of rebar steel in simulated pore solution mixed with seawater
and carbonate at different DMEA concentration. The trend of corrosion rate in accordance with corrosion current
density trend. Only DMEA with concentration 0.6 M can slightly reduce corrosion rate compared with without DMEA.
The addition of DMEA with concentration 0.1 M and 0.3 M does not reduce the corrosion rate. DMEA with
concentration 0.1 M and 0.3 M can inhibit corrosion in seawater and carbonate environment only untill 5th day. This
result indicate that DMEA with concentration 0.1M-0.6 M is not effective to retard the corrosion on rebar steel of
concrete in seawater and carbonate environtment.
Fig. 6 shows the evolution of Ecorr and Icorr with time for simulated pore solution mixed with sodium chloride and
carbonate with different DMEA concentration. It is appreciated again that the addition of DMEA decrease Ecorr and Icorr.

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Fig. 2. Evolution of Ecorr and Icorr vs. time in simulated pore solution mixed with seawater with different
DMEA concentration.

Fig. 3. Evolution of icorr vs. time in simulated pore solution mixed with seawater with different DMEA
concentration.

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Fig. 4. Evolution of Ecorr and Icorr vs. time in simulated pore solution mixed with seawater and carbonate with
different DMEA concentration.

Fig. 5. Evolution of icorr vs. time in simulated pore solution mixed with seawater and carbonate with different
DMEA concentration.

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Fig. 6. Evolution of Ecorr and Icorr vs. time in simulated pore solution mixed with sodium chloride and
carbonate with different DMEA concentration.

Fig. 7. Evolution of icorr vs. time in simulated pore solution mixed with sodium chloride and carbonate with different
DMEA concentration.

In Fig. 7, the evolution of corrosion rate with time of rebar steel submerged in simulated pore solution mixed with
sodium chloride and carbonate of different DMEA concentration is plotted. As can be seen in Fig.7, the higher DMEA
concentration the lower corrosion rate and the lowest corrosion rate is DMEA 0.6M. It is clearly observed how the
coorosion level is reduced in solution incorporating DMEA.Based on the evolution of icorr in Fig. 3, Fig. 5, and Fig. 7,
the most corrosive environtment is seawater.

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3.2. Inhibitor efficiency
Inhibitor efficiency is effectiveness percentage of inhibitor to inhibit corrosion process. Inhibitor efficiency
calculated based on Eq.1. Inhibitor efficiency calculation based on average 20 days corrosion rate measurement, shown
in Table.4. As can be seen in Table.4, the best inhibitor efficiency for all test solution is DMEA with concentration
0.6M. For seawater and carbonate environtment, the addition of DMEA even increases the corrosion rate, so DMEA
should not use in this environment. The highest inhibitor efficiency of DMEA (61%) is corrosion rate of rebar steel in
sodium chloride and carbonate environment with 0.6 M DMEA concentration. Inhibitor efficiency in sodium chloride
and carbonate environtment increases with increasing DMEA concentration. It is evident that DMEA effective to inhibit
corrosion process by forming a stable interfacial layer on steel surface which is able to keep the interface in a passive
state.
Inhibitor Efficiency (%) =

Corrosion Rate without inhibitor-Corrosion Inhibitor with inhibitor


x 100
Corrosion rate without inhibitor

(1)

Tabel 4. Inhibitor efficiency DMEA in all variation solution test


SPS + Seawater

SPS + Seawater + Carbonate

SPS + NaCl + Carbonate

DMEA
Concentration

Corrosion Rate

Inhibitor Corrosion Rate


Efficiency

Inhibitor Corrosion Rate Inhibitor


Efficiency
Efficiency

0,1 M

12.13
6.53

46%

4.45
6.72

-51%

6.07
5.54

9%

0,3 M

7.42

39%

5.22

-17%

4.16

31%

0,6 M

4.94

59%

3.76

16%

2.33

62%

3.3. Visual observations


Fig.8 shows visual observation of rebar steel in the test solution without DMEA and with 0.6 M DMEA
concentration. It can be observed that without DMEA in seawater solution test, the corrosion product clearly visible and
more dense than corrosion product with DMEA. With DMEA 0.6 M, the largest corrosion product exists on
thespecimen in seawater test solution. This visual obsevation appropriate with corrosion rate measurement that the most
aggressive environtment is seawater.

(a)

(b)

(c)

(d)

Fig. 8. Photographs of specimen after 20 days in simulated pore solution mixed with (a) seawater wihout DMEA (b)
seawater with 0.6 M DMEA (c) seawater and carbonate with 0.6 M DMEA (d) sodium chloride and carbonate with 0.6
M DMEA.
4. Conclusions
The evolution of corrosion current density and corrosion rate for 20 days measurement decrease with increasing
DMEA concentration. The best performance of DMEA concentration is 0.6 M for all three kinds of test solution.
DMEA is more effective used in seawater and combination of sodium chloride and carbonate environtment, for
combination of seawater and carbonate environtment DMEA with concentration 0.1M-0.6 M is not effective. The higest
inhibitor efficiency is DMEA 0.6 M in sodium chloride and carbonate environtment.
Acknowledgements
This work was supported by Resesarch Center for Metallurgy and Materials, Indonesian Institute of Sciences. The
authors are thankful to the earth science deputy of Indonesian Institute of Sciences for financial support for this research
by 2015 excellence programme.

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References
[1] M. Pandiarajan, P. Prabhakar, S. Rajendran. Corrosion behaviour of mild steel in simulated concrete pore solution
prepared in rain water, well water and sea water. Eur. Chem. Bull, 1(2012) No.7,p. 238-240.
[2] Linhua Jiang, Guohong huang, Jinxia Xu, Yeran Zhu, Lili Mo. Influence of chloride salt type on threshold level of
reinforcement corrosion in simulated concrete pore solutions. Construction and Building Materials, 30(2012),p.
516-521.
[3] M. Ormellese, M. Berra, F. Bolzoni, T. Pastore. Corrosion inhibitors for chlorides induced corrosion in reinforced
concrete structures. Cement and Concrete Research, 36 (2005), p. 536-547.
[4] I.L. Kondratova, P. Montes, T.W. Bremner. Natural marine exposure results for reinforced concrete slabs with
corrosion inhibitors. Cement and Concrete Composite, 25 (2003) p. 483-490.
[5] M. B. Valcarce, C. Lopez, and M. Vazquez. The role of chloride, nitrite and carbonate ions on carbon steel
passivity studied in simulating concrete pore solutions. Journal of The Electrochemical Society, 159(2012), No.5,
p.244-251.
[6] B. Elsener. Corrosion inhibitors for steel in concrete. State of the Art Report, EFC Publications, vol 35, (2001).
[7] E. Rakanta, Th. Zafeiropoulou, G. Batis. Corrosion protection of steel with dmea-based organic inhibitor.
Construction and Building Materials, 44 (2013), p. 507-513.
[8] Amir Poursaee. Corrosion of steel bars in saturated ca(oh)2 and concrete pore solution. Concrete Research
Letters,1 (2010), No.3.
[9] P. Garces, P. Saura, E. Zornoza, C. Andrade. Influence of ph on the nitrite corrosion inhibition of reinforcing steel
in simulated concrete pore solution. Corrosion Science,53 (2011), p. 3991-4000.

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CODE: CF
Synergistic Effect of Triazine and Potassium Iodide as Corrosion Inhibitors for Carbon Steel in 0.5M HCl
Aqueous Solution
Andi Rustandi1), Freddy Valensky1), Johny Wahyuadi Soedarsono1), M. Akbar Barrinaya1)
1

Departemen Teknik Metalurgi dan Material, Universitas Indonesia, Depok, 16424, Indonesia

Abstract. The effects of Triazine (C6H15N3) and its synergistic effect with Potassium Iodide (KI) on the corrosion of
mild steel in 0.5 M HCl was investigated using polarization and electrochemical impedance (EIS) methods at 301o K. .
The effect of KI addition on Triazine inhibitors can increase the efficiency 88.72% become 94.23%. The synergistic
effect of different concentrations of Triazine and KI was determined by calculating the synergism parameters, which
showed that a cooperative mechanism exists between the iodide anion and Triazine cations. The inhibitors act as mixed
type with predominant cathodic effect. The inhibitors were adsorbed on the mild steel surface according to the
Langmuir adsorption isotherm. The Triazine characterization was verified by using FTIR.
Keywords: HCl; Corrosion inhibitors; Adsorption; Triazine; Potassium Iodide.
Corresponding author : Andi Rustandi, E-mail: rustandi@metal.ui.ac.id or rustandia@gmail.com, Tel. +62-812-97427324.
1. Introduction
Numerous systems in the petroleum industry have corrosion problems. One of them is Acidizing of oil and gas
wells[1]. Acidizing is an oil reservoir stimulation technique for increasing well productivity. M.A. Migahed et al.[3]
have studied the using of triazine for corrosion inhibition of Tubing steel during acidization of oil and gas wells. The
type of triazine used was 6-methyl-5-[m-nitro styryl]-3-mercapto-1,2,4-triazine with resulting 86.7% efficiency by
using 300 ppm of the inhibitor. Synergistic inhibition is an effective means to improve the inhibitive force of the
inhibitor, to decrease the amount of usage and to diversify the application of the inhibitor in acidic media. Many
investigations in regard to synergistic inhibition have been carried out and are being investigated. Orubite Okorosaye et
al. have studied the synergistic Inhibition effect of iodide ions and extract of nypa fruticans on the corrosion of mild
steel iron in 0.1 and 0.5M HCl solution. The inhibition efficiency was enhanced by the addition of iodide ions because
of synergistic effects [4]. The use of organic compounds containing oxygen, sulfur and nitrogen synergized with KI to
reduce corrosion attack on steel has been studied [510].
The aim of this work is to investigate and report the influence of the new synthesized compound namely hexahydro1,3.5-trimethyl-1,3,5-triazine synergized with addition of KI (iodide ions) as the corrosion inhibitor for mild steel in
0.5M HCl solution by using electrochemical techniques such as polarization measurement and Electrochemical
Impedance Spectroscopy (EIS).
2. Experimental work
The solution (0.5M HCl) was prepared by dilution of analytical grade 32% HCl with double distilled water. The
working electrode was mild steel in a rectangular shape. The working solution was 0.5M HCl. A mild steel with the
same chemical composition was mounted in Teflon with an exposed surface area of 1 cm2 was used in all
electrochemical measurements. The specimens were cleaned according to ASTM standard G1-03. Measurements were
undertaken in stagnant non-aerated 0.5M HCl acid solutions in the presence and absence of triazine 300 ppm and KI
ppm alone and concentrations of different triazine (100300 ppm) in combination with 75 ppm KI at 301 K.
3. Results and discussion
Electrochemical measurements were conducted by using Metrohm Autolab Instruments Poten-tiostat/Galvanostat
PGSTAT302N with NOVA 1.10 software. The cell contained three electrodes; the mild steel as working, carbon as
counter electrode and Ag/AgCl reference electrodes. Fig.1 shows that the addition of triazine reduces anodic dissolution
and also reduce the hydrogen evolution reaction, which indicates that triazine is a mixed-type inhibitor and controls
both the anodic and cathodic reactions.

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Fig. 1. Polarization Curve of Carbon Steel in 0. M HCl at Various Concentrations


Concentrations.
The decrease in icorr with increasingg concentration shows the efficiency of the corrosion inhibitor is enhanced. The
triazine does not shift the Ecorr values significantly, suggesting that they behave as mixed type inhibitors. Anodic or
cathodic type inhibitor only can be happened if Ecorr.inh is shifted more than 85 mV againts Ecorr.uninh.
The Nyquist plots for mild steel in the presence and absence of different concentrations of Triazine alone and in
combination with KI are shown in Fig.2.

Fig. 2. Nquist Plot of HCl 0.5M Solution at Various Inhibitor Concentrations.


In 0.5 M HCl solution with the presence of triazine and its combination with KI showed that with higher
concentration of triazin and KI then the impedance values increased significantly. This revealed that with triaz
triazin and KI
addition would enhance its inhibition performance on carbon steel.
Adsorption isotherm has been calculated on the mild steel surface to investigate the mechanism of corrosion
inhibition in the presence of 75 ppm KI. The plot of C/ against C in Fig.3 yields a straight line, and this supports the
assumption that the adsorption of triazine in the present of KI on a mild steel surface in 0.5M HCl solution obeys the
Langmuir adsorption isotherm.

Fig. 3. Adsorption isotherms for mild steel in 1.0 M HCl in different concentrations
concentrations.

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Values of G up to -20
20 kJ mol-1
mol 1 are consistent with the electrostatic interaction between charged inhibitor
molecules and the charged metal surface (physisorption), whereas those around 40 kJ mol
mol-1 or lower are associated
with chemisorption, which involves charge sharing or transfer from organic molecules to form a coordinate
coordinate-type
bond[5]. The calculated G values indicated that the adsorption mechanisms were a combination of physisorption
and chemisorption[10].
3.1. Synergistic inhibition effect of iodide ions
Halide ions facilitate the adsorption of organic inhibitors in acidic media by forming intermediate bridges between
positively charged inhibitor molecules and the metal surface[10]. The synergistic effect of the halide ions was reported
to increase in the order of I- > Br- > Cl-. As can be seen from the % for solutions with KI exhibit higher values
compared to solutions without KI. This reflects that KI has a synergistic effect on the corrosion process of mild steel in
0,5M HCl solution, this can be explained that the inhibitor molecules which had been protonated by H+ are then
adsorbed by columbic attraction (electrostatics) to the metal surface which have been negatively charged by iodide ion.
Stabilization of the adsorbed iodide ions with the inhibitor leads to greater surface coverage and thereby greater
inhibition [5]. The synergism parameters (S1) value is 1,78 were calculated using the relationship given by Aramaki and
Hackerman [5, 6]. Generally, values of S1 < 1 imply that antagonistic behavior prevails, which may lead to competitive
adsorption, whereas S1 > 1 indicates a synergistic effect. The iodide ions enhance the stability of the inhibitor on the
metal surface by a adsorption mechanism, which may be either be competitive or cooperative. The values of S1 are
larger than
an one, a cooperative mechanism existed between the iodide anion and triazine cations, where the addition of
KI enhances the inhibition performance of the triazine in 0,5M HCl solution, as confirmed earlier by electrochemical
measurements.
3.2. Triazine characterization
cterization by FTIR
Fig. 4 shows the FTIR spectra of the synthesized triazine. The absorption bands appear at 3338 cm-1 correspond to
the C-H bond, 2139 cm-1 correspond to the CN
C
bond and the peak at 1635 cm-1 is assigned to the bending of C=N
bond.

Fig. 4. FTIR of the synthesized Triazine.


4.

Conclusions
Triazine performs inhibition of the corrosion of mild steel in 0.5M HCl solution. Potentiodynamic polarization
studies showed that the triazine is a mixed-type
mixed
inhibitor. The effect of KI addition KI on triazine inhibitors increase the
efficiency from 88.72% up to 94.23%. The adsorption of triazine with the presence and absence of KI on the metal
surface in 0.5M HCl obeys the Langmuir adsorption isotherm. A combination of both physisorption and chemis
chemisorption
0
of the inhibitor molecules on the mild steel surface was proposed based on the G ads value. The synergism parameter
suggests that triazine in the presence of KI would inhibit the corrosion of mild steel in HCl, and there is a cooperative
mechanism between the iodide anion and triazine cation.
References
[1] Allen, T.O, Robert, A.P, Production Operations, Well Completion, Workover and stimulation
stimulation.1979
[2] Doherty, Henry L., Acidizing Fundamentals,
Fundamentals, Society of Petroleum Engineering, New York, 1979.
[3] M.A.Migahed and I.F.Nassar.,Corrosion
Corrosion Inhibition of Tubing Steel During Acidization of Oil and Gas Wells
Wells,
Electrochimica Acta 53 (2008) 28772882.
2877
[4] Orubite Okorosaye K, Jack I.R, Ochei M, Akaranta O., Synergistic of Potassium Iodide on Corrosion Inhibition of
Mild
ild Steel in HCl Medium by Extract of Nypa Fruticans Wurmb,
Wurmb, J. Appl. Sci. Environ. Manage Vol. 11 (2007)
27 31.

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Ahmed Y. Musa, Abu Bakar Mohamad, Abdul Amir H. Kadhum, Mohd Sobri Takriff, Lim Tien Tien. Synergistic
effect of potassium iodide with phthalazone on the corrosion inhibition of mild steel in 1.0 M HCl, Corrosion
Science 53 (2011) 36723677.
[6] Shyamala R. Krishnamurthy and Meenakshi H. N. Parameswaran Synergistic Effect of Iodide Ion and 4-Hydroxy
Coumarin on the Corrosion Inhibition of Mild Steel in Hydrochloric Acid. Hindawi Publishing Corporation
(2013), Article ID 184787.
[7] L. LARABI, Y. HAREK, M. TRAISNEL and A. MANSRI Synergistic influence of poly (4-vinylpyridine) and
potassium iodide on inhibition of corrosion of mild steel in 1M HCl. Journal of Applied Electrochemistry 34
(2004) 833839, 2004.
[8] Sudhish K. Shukla, Ashish K. Singh, Lutendo C. Murulana, Mwadham M. Kabanda and Eno E. Ebenso. Inhibitive
Effect of Azorubine Dye on the Corrosion of Mild Steel in Hydrochloric Acid Medium and Synergistic Iodide
Additive. Int. J. Electrochem. Sci., 7 (2012) 5057 5068.
[9] Ahmed A. Farag , M.A. Hegazy, Synergistic inhibition effect of potassium iodide and novel Schiff baseson X65
steel corrosion in 0.5 M H2SO4 Corrosion Science 74 (2013) 168177.
[10] Bei Qian a,b, Jing Wang a, Meng Zheng , Synergistic effect of polyaspartic acid and iodide ion on corrosion
inhibition of mild steel in H2SO4. Corrosion Science 74 (2013) 168177.
[5]

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CODE: CF
Sarang Semut (Myrmecodia Pendans) extract as a green corrosion inhibitor for material API 5L Grade B in 1 M
H2SO4 solution
Atria Pradityana1), Sulistijono2), Abdullah Shahab1)
1

Department of Mechanical Engineering, Institut Tekonologi Sepuluh Nopember, Surabaya 60111, Indonesia
Department of Materials and Metallurgical Engineering, Institut Tekonologi Sepuluh Nopember, Surabaya 60111,
Indonesia

Abstract. Corrosion is a change process of materials characteristic due to the influence of or the reaction with the
surrounding environment. One way of corrosion control is by adding the corrosion inhibitor. The purpose of this study
is to analyze the influence of Sarang Semut plant extract (Myrmecodia pendans) as the organic inhibitor of acid
solution. This study uses the material of API 5L Grade B while the used corrosive media is the solution of 1 M H2SO4.
The concentration of Sarang Semut extract which is used in this study ranges to 0 until 5000 mg/L (the multiple of 1000
mg/L). From the result of the experiment, the optimal inhibition efficiency occurs if there is a concentration addition as
much as 5000 mg/L. The mechanism of adsorption in this system follows the Freundlich adsorption.
Keywords: sarang semut; inhibitor; H2SO4; Freundlich
Corresponding author: Atria Pradityana, E-mail: atriapradityana@gmail.com, Tel. +62-821-41080460
1. Introduction
One way to prevent the occurrence of corrosion is by adding the inhibitor. Corrosion inhibitor is a compound in the
small numbers but it can be able to inhibit the metal corrosion reaction with the environment. It can be said that the
inhibitor build a protective layer on the metal surface with the reaction between the solution and the corroded metal
surface. With the addition of inhibitor in the environment, the corrosion rate will be reduced.
The use of plants as the corrosion inhibitor can be proven by the contained phytochemical molecule in which the
structures of the electrochemistry and the molecular are similar to the inhibitor molecule of the conventional organic
[1]. The basic mechanism of inhibitor is actually done by adsorbing the ions or molecules on the surface of the metal in
which the inhibitor is able to control the electrochemical reaction (anodic and cathodic) and to create a thin layer (film
forming) to inhibit the corrosion process.
Sarang Semut (Myrmecodia pendans) is one kind of plant which content has been well-known [2] to be used as the
inhibitor by several researchers [3]. These plant can be applied as an organic inhibitor for the pipe material which uses
carbon steel API 5L Grade B with the inhibitor concentration of 0-500 mg/L in the acid media. This has been proven
by the previous research conducted by Atria [4]. The result of that research shows that the inhibition efficiency is still
fewer than 50% so that the produced efficiency can be said as not maximum.
In this study, it is conducted in environment of 1M H2SO4. The material used is API 5L Grade B. However, the
range of the inhibitor concentration is higher than the previous research which is 0-5000 mg/L (the multiple of 1000
mg/L). It is expected that by increasing the inhibitor concentration, the efficiency of inhibition that is occurred will
increase as well.
2.
Experimental
2.1. The specimen preparation
The weight loss experiment. This experiment uses the steel of API 5L Grade B which is trimmed into the
dimension of 2 x 2 x 3 mm for one each specimen. The specimens are sanded so that the corrosion products are gone
then the top of the specimens are drill. The drill result will be used as the place of the yarn winding so that specimens
can be hung on the dyeing process. Before the specimen experiment is done, the initial weight should be calculated.
2.2. The solution preparation
The used solution is H2SO4 98%. The process of making H2SO4 1M is done by mixing the solution of H2SO4 98%
as much as 54.64 ml with the aquades until volume reaches to 1000 mL.
2.3. The inhibitor preparation
Sarang Semut is extracted by using maceration method. The process of maceration uses ethanol 80%. This is
followed with a process of evaporation by using a rotary evaporator. This process aims to separate the solution with its
extract. The remaceration of the Sarang Semut dreg will be done as if the needed targeted amount of extract is still not
fulfilled yet.

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2.4. The Weight Loss Experiment
The method of weight loss is also known as the method of losing weight. The method of corrosion measurement is
the method that often used because the method is easy to be done and the used tool is also simple. The metal experiment
will be placed in a particular environment for a certain time so that it can be corroded. The metal experiment is
commonly called as coupons. Coupon is a metal plate that is placed in the system and made to be corroded to determine
the rate of corrosion through the weight reduction. In this study, it is used the concentration addition of 1000, 2000,
3000, 4000, 5000 mg/L with the immersion process for 72 hours. After the immersion process is complete, the next step
is pickling process which is done by using 5M HCL for cleaning the corrosion then it is washed by using the soapy
water.
2.5. The Method of Electrochemical Impedance Spectroscopy
Electrochemical Impedance Spectroscopy is a method which is used to analyze the response of a corroded
electrode to a potential signal of AC as the frequency function. This method is used to determine the mechanism of
inhibition. The wave of AC at the low amplitude of 10 in the frequency range of 0,01 Hz to 1000 Hz. Principally, the
EIS is used to determine the electrochemical kinetic parameters which relate to the electric elements such as the
resistance, R, capacitance, C, and inductance, L.
2.6. The FTIR experiment
FTIR experiment is conducted to determine the mechanism of inhibition that occurs in the steel of API 5L Grade
B after being added with the inhibitor. By doing FTIR experiment, the peak or curve wave will be resulted with the
various intensities and the functional groups contained in a material. In this study, FTIR experiment is done in the
specimen weight loss with the concentration of 5000 ppm (the highest efficiency) and without inhibitor.
3. Results and discussion
3.1. The Weight Loss
From the Table 1, it can be seen that the concentration increases by the time the more inhibitor is mixed into the
solution. Besides, the more increasing the inhibitor concentration, the more decreasing the corrosion rate and the more
increasing the inhibition efficiency will be. The lowest corrosion rate occurs when there is an addition of inhibitor
concentration of 5000 mg/L, ie 647.676 mpy with the inhibition efficiency of 56.56%.
Table 1. The rate of corrosion occurs during being added by the inhibitor of Sarang Semut.
Concentration of inhibitor (mg/L)
Corrosion rate (mpy)
Efficiency of inhibition (%)
1702,634
0
1527,695
10,27
1000
1192,390
29,97
2000
1066,409
37,37
3000
944,718
44,51
4000
869,747
48,92
5000
3.2. The Electrochemical Impedance Spectroscopy (EIS)
This experiment is used to determine the mechanism of inhibition through the parameter of equivalent circuit
electrochemical. The equivalent circuit is obtained by fitting the graph of EIS. From the Figure 1, it can be seen that the
yield curve of fitting is similar to the actual electrochemical curve. The samples which are conducted by EIS only the
ones that have the highest inhibition efficiency. So, concentration used is 0 and 5000 mg/L.
Based on the circuit in Figure 2, at the beginning of the series there is existed a resistance of solution (Rs). Rs
happens at the beginning of the series due to the fact that EIS can detect any resistances formed between the electrolyte
solution and the samples of steel. The Table 2 shows the results of the parameters that are formed such as the values of
Rs, Rp, Rct, and Cdl. The value of y Rct at concentration of 0 mg/L is as much as 10,66 while the concentration of
5000 mg/L generates a value of 15,75 . This shows that if the inhibitor is added to the solution, the value of Rct will
increase. The Rct value is associated with the move of electron in which if the electron moves faster, the resistance will
decrease and the corrosion rate will increase. On the other hand, if the electron moves slower, the resistance will be
greater and the corrosion rate will decrease. The high rate of Rct at 5000 mg/L indicates that the resistance is greater
than the resistance at 0 mg/L. Thus, the thin layers on the metal-solution interface froms as the protection. These layers
cause the movement of ions from the electrolyte to the metal become inhibited. The more the passive layers formed, the
more rate of the Rct value and the fewer the value of the CPE will be.

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Fig. 1.. The result of fitting nyquist plot by using NOVA software

Fig. 2.. the equivalent circuit of the Nyquist plot in Nova software
Table 2.. the data of equivalent circuit result in Steel of API 5L Grade B
Concentration of inhibitor
Rp ()
Rs ()
Rct ()
Cdl (F)
Efisiensi inhibisi (%)
(mg/L)
10.761
35.679
10.66
84.692
0
15.998
35.679
15.75
53.257
23.32
5000
3.3. The Mechanism of Isotherm Adsorption
Isotherm adsorption can provide the information about the interaction between the inhibitor and the surface of the
metal when the metal immersed in the electrolyte solution which has been mixed with the inhibitor. The absorption of
organic inhibitor in the metal surface with the solution can occur because of the substitution absorption process be
between
the organic molecules in the solution and the water molecules on the surface of the metal. The efficiency inhibitor is
associated with the fraction of the surface which is covered by the adsorption of the inhibitor molecule. The fraction of
the covered
ed surface is obtained from the data of the weight loss method. In determining the adsorption process, the
value of surface coverage () is used in which the value varies according to the addition of the Sarang Semut extract
concentration. The degree of surface
rface coverage is calculated by using the followings:
= IE% / 100

(1)

By using the adsorption isotherm, the corrosion adsorption process can be understood. The adjustment of the value
is used with the common types of adsorption isotherms such as Langmuir and Freundlich. The Langmuir is associated
with the phenomenon of monolayer while Freundlich. Langmuir is associated with multi-layers.
multi layers. Below is the equation
of Langmuir (2) and Freundlich (3) adsorption isotherm which are used and for calculating
calculating the value kads is by using
this equation (4):
=

(2)

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=
=
where :
C
kads
T
R

(3)

exp

(4)

= Concentration of inhibitor (mg/L)


= Constant of adsorption
= Temperature (K)
= Constant of ideal gas (8.314 J/mol K)
= Free standart energy adsorption (kJ/mol)

Concentration of
inhibitor (mg/L)
0
1000
2000
3000
4000
5000

Table 3. The calculation data of surface coverage for adsorption graph


Corrosion
Efficiency of
Surface
C/
Log C
rate (mpy)
inhibition (%)
coverage ()
1702,634
1527,695
10,27
0,103
9732,730
3,000
1192,390
29,97
0,300
6673,806
3,301
1066,409
37,37
0,374
8028,454
3,477
944,718
44,51
0,445
8985,868
3,602
869,747
48,92
0,489
10221,284
3,699

Log (/1-)

Langmuir Adsorption
12000.000

y = 0.3289x + 7741.7
R = 0.135

10000.000

C/

8000.000

Langmuir
Adsorption

6000.000
4000.000

Linear (Langmuir
Adsorption)

2000.000
0.000
0

1000

2000

3000

4000

5000

C
Fig. 3. The graph of Langmuir adsorption

6000

-0,941
-0,369
-0,224
-0,096
-0,019

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Freundlich Adsorption

Log (/1-)

0.200
0.000
0.000
-0.200

y = 1.3023x - 4.778
R = 0.9606

1.000

2.000

3.000

4.000

Freundlich Adsorption

Linear (Freundlich
Adsorption)

-0.400
-0.600
-0.800
-1.000

Log C
Fig. 4. The graph of Freundlich adsorption

It can be seen from the figures 3 and 4, the value of R2 for the Langmuir Adsorption is only 0.135 while the value
of R for the Freundlich Adsorption is 0.960. The value of R2 in Figure 3 shows that the line obtained by R2 <1 so that it
can be said that the adsorption of Sarang Semut molecules in the steel surface of API 5L Grade B does not follow the
model of Langmuir adsorption. Therefore, the Freundlich adsorption model is conducted. The value of R2 in figure 4 is
0.960 and it can be concluded that Freundlich isotherms gives the best correlation that fit with the experimental data.
The straight line that is formed produces a linear correlation coefficient. In this case, it explains that the inhibition is
caused by the absorption of organic compounds on the surface of the metal and its adsorption mechanism follows the
Freundlich. Thus, it is understood that the inhibitor forms the multilayers. By using the (3) and (4) equation, the value
of free energy adsorption is obtained as (
) so that later it can be known what type of adsorption occurs on the
metal surface due to the addition of Sarang Semut extract inhibitor (Myrmecodia pendans). From the linear equation in
Figure 4, Kads value is obtained as 1.302 so that the value of non adsorption energy of (
) can be calculated. The
value of free energy adsorption (
) is obtained as -12.11 kJ/mol. The value of free energy adsorption which is more
than -20 kJ/mol explains the process of physical adsorption on metal surfaces. Whereas if the value results less than -40
kJ/mol, then adsorption that occurs on the surface of the metal is a chemical adsorption in which this adsorption
involves the transfer or the sharing of the molecule in the inhibitor which is chemically on process[7]. In this
experiment, the result of calculation for
is more than -20 kJ/mol so that it can be said that the isotherm of
adsorption mechanism is physics or physio. The adsorption mechanism in physics can be categorized as weak because
the adsorption process is reversible. The negative sign explains that the absorption Sarang Semut extract on the metal
surface is done spontaneously; moreover, the negative sign also indicates the stability. The greater the negative value of

, the higher the adsorption energy will be.


2

4. Conclusions
By adding the concentration of Sarang Semut extract as the inhibitor in H2SO4 1 M, the rate of corrosion will
decrease. The highest inhibition efficiency occurs if there is an concentration addition of 5000 mg/L which is 48.92%.
The adsorption mechanism follows the Freundlich Adsorption Isothermad with the value of
as much as -12.11
kJ/mol. This means that the type of adsorption which occurs is the physiosorption.
References
[1]. Umoren, S.A, Eduok, U.M., Solomon, M. M., Udoh, A.P. Corrosion inhibition by leaves and steams extracts of
Sida Acuta for mild steel in 1M H2SO4 solutions investigated bv chemical and spectroscopic techniques. Arabian
Journal of Chemistry, (2011).
[2]. Mekonnen Engida Adam, Kasim, Novy S., T.A Yeshitila, Ismadji, Suryadi. Extraction, identification and
quantitative HPLC analysis of flavonoids from sarang semut (Myrmecodia pendans). Industrial Crops and
Products. NACE International. Corrosion Costs and Preventive Strategies in the United States.(2011).

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[3]. Pradityana. A, Sulistijono, Shahab.A. Effectiveness of Myrmecodia Pendans Extract as Eco-Friendly Corrosion
Inhibitor for Material API 5L Grade B in 3,5% NaCl Solution. Trans Tech Publications, Switzerland. Advanced
Material Research Vol. 789 pp 484-491. (2013).
[4]. Pradityana. A, Sulistijono, Shahab.A. The Influence of Adding Bio Inhibitor Sarang Semut (Myrmecodia
Pendans) to Carbon Steel API 5L Grade B in Solution of HCl 1 M. Trans Tech Publications, Switzerland.
Advanced Materials Research Vol. 1123 pp 187-191. (2015).
[5]. Pradityana. A, Sulistijono, Shahab.A. Application of Myrmecodia Pendans Extract as a Green Corrosion Inhibitor
for Mild Steel in 3,5% NaCl. Trans Tech Publications, Switzerland.. Applied Mechanics and Materials Vol. 493pp
684-690. (2014)
[6]. Pradityana. A, Sulistijono, Shahab.A. Eco-Friendly Green Inhibitor of Mild Steel in 3,5% NaCl Solution by
Sarang Semut (Myrmecodia Pendans) Extract. Published by the AIP Publishing. American Institute of Physics
1617, 161. (2014).
[7]. Taleb Ibrahim. The Effect of Thyme Leaves Extraction Corrosiob of Mild Steel in HCl. Progress in Organic
Coating 75 (456-462). (2012).

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CODE: CF
Myrmecodia Pendans (Sarang Semut) Extract as Corrosion Inhibitor of Mild Steel in 0,5 M H2SO4 Solution
Atria Pradityana1), Sulistijono2), Abdullah Shahab1), Subowo1)
1

Department of Mechanical Engineering, Institut Tekonologi Sepuluh Nopember, Surabaya 60111, Indonesia
Department of Materials and Metallurgical Engineering, Institut Tekonologi Sepuluh Nopember, Surabaya 60111,
Indonesia

Abstract. Inhibitor is a substance that is added to the corroded media to inhibit the corrosion rate. The organic
inhibitors more develop than the anorganic ones because they are environmentally friendly. The organic compounds can
be adsorbed by the metal surface and block the active surface to reduce the corrosion rate. In this research, the used pipe
of API 5L Grade B with 0,5 M H2SO4 solution as the corrosion media. The variation concentration of extract sarang
semut used is 0 - 500 mg/L (multiple of 100 mg/L). The extraction method used is maceration. In this research, several
experiments are used such as weight loss experiment, EIS, and FTIR. The highest efficiency occurs at the addition of
400 mg/L of inhibitor. From the result, it shows that with the addition of sarang semut inhibitor, it is able to reduce the
corrosion rate by forming a thin layer on the metal surface.
Keywords: organic inhibitor; Myrmecodia pendans; acid solutions
Corresponding author: Atria Pradityana, E-mail: atriapradityana@gmail.com, Tel. +62-821-41080460
1. Introduction
Corrosion is a material degradation caused by its chemical reaction with other material and the environment [1].
This process often occurs in the industry of oil and gas. In the industrial field, carbon steel is a type of material that is
commonly used in various applications. One of those types of carbon steel which is often used in the industrial field is
API 5L steel grade B. The API 5L steel is one of the steels used in the applications of water transport, oil, and natural
gas. One of the problems that often occur in the distribution process of crude oil is the existence of sediment called as
the crust (scale). The crust is the result of mineral precipitation which is derived from the water formation produced
along with the oil and gas [2]. This type of steel is easily to be corroded in acidic solution environment. In fact,
corrosion cannot be prevented but its speed can be controlled by the addition of inhibitor. Inhibitor is a substance which
is capable of inhibiting or reducing the rate of metal corrosion with the environment [1]. It can also be said that the
inhibitor form a protective layer on the metal surface by the reacting between the solution and the corroded metal
surface [3].
In this case, there are many researches done to find a new source of the corrosion inhibitor which sources are mainly
from the natural materials. Natural materials are chosen as the alternative because of their characteristics which are safe,
easily available, biodegradable, cheap, and eco-environment [4,5,6].
The organic material used as the inhibitor can prevent the material oxidation reaction of the contained antioxidant
element through a certain mechanism. Antioxidant is defined as a compound that is able to delay, slow down, and
prevent the oxidation process [5]. The antioxidant works by donating the electron to the oxidantcompounds so that the
activity of antioxidant compound can be inhibited. One of the organic materials which contains the antioxidant is
Sarang Semut plant [7]. The result of Sarang Semut extract has previously been analyzed showing that it contains the
flavonoid as the antioxidant which can be used in the process of green inhibitor making [8-11].
It has been previously studied that Sarang Semut (Myrmecodia pendans) can be applied as the organic inhibitor for
the pipe material which is the API 5L carbon steel Grade B with the inhibitor concentration of 0-500 mg/L in acidic
media of 1M HCl and 1M H2SO4 by doing immersion method [9]. From the previous study, it has not been obtained the
optimum efficiency in the application of Sarang Semut in an acidic environment. In this research, it will be conducted
the experiment of Sarang Semut inhibition for the carbon steel material of API 5L Grade B with the same variation of
inhibitor concentration which is 0-500 mg/L but that the concentration of the electrolyte solution media is diluted into
0,5 M H2SO4 by using immersion method. So, it is expected to produce the inhibition efficiency optimum in acidic
media.
2. Experimental
2.1. The preparation of inhibitor
Myrmecodia Pendans (MP), the epiphytic plant, is derived from Irian Jaya through various processes so that the
Sarang Semut extract is obtained in the form of powder. The extraction method which is used to obtain the MP extract
is by doing maceration. The powder of MP is immersed for 1x24 in 80% ethanol and then it is filtered to obtain the MP
extract in liquid form. The immersing and filtering are done 3 times [9]. After being filtered, the solution is evaporated
by using a evaporator rotary engine so that the bias extract of MP can be used as the bio inhibitor.

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2.2. The preparation of specimen


For the experiment of Electrochemical Impedance Spectroscopy, the API 5L Grade B is cut into the dimension of
10 x 10 x 3 mm and then it is soldered to connect the specimen with 20 cm of copper wire. Next, the specimen is
molded by using the epoxy resin and the mold of shock pipe with the diameter of 2.3 cm. After the molding dries, the
specimen parts of which are not covered by resin (exposed) is smoothed by using the rubbing paper (sandpaper) grade
120, 320, 400, 600, 800, 1000. As for the specimen of weight loss experiment, the API 5L carbon steel Grade B is cut
into the dimension of 20 x 20 x 3 mm and then the top is drilled (where rope is hang) with a diameter of 4 mm. Then,
the specimen is smoothed by using a rubbing paper to smooth the surface and to eliminate the corrosion products
previously [12]. In each weight loss specimen, it should be done the measurement of the specimen initial weight.
2.3. The preparation of solution
The solution which is used is 98% H2SO4. To get 1000 ml of 0,5 M H2SO4, 27.32 ml of 98% H2SO4 solution is
added to aquades untill the volume reaches to 1000 ml of beaker glass.
2.4. The Weight Loss Experiment
The weight loss experiment or well known as the weight reduction method is a method conducted to determine the
amount of corrosion rate (mpy) of a material based on the reduction of initial weight and final weight. In this method, a
sample with a certain weight will be dipped in a solution or a particular environment at several different times [12]. In
this study, the weight loss experiment will be done with concentrations of 0, 100, 200, 300, 400, and 500 mg/L in
corrosive media of 0,5 M H2SO4 for 72 hours.
2.5. The Method of Electrochemical Impedance Spectroscopy
Electrochemical Impedance Spectroscopy method is a experimental method found in potentiostat tool that applies
the polarization principle to determine the mechanism of corrosion on metal. The EIS experiment is performed by using
Nova software consisting of the working electrode, the reference electrode, and the auxiliary electrode. Electrochemical
Impedance Spectroscopy is a method for analyzing the response of the corroded electrode to the AC potential signal as
the function of frequency. In principle, the EIS is used to determine the electrochemical kinetic parameter related to the
electrical elements such as resistance R, capacitance C, and inductance L. The experiment of EIS is only done for the
specimen resulted from the weight loss experiment which inhibitor efficiency is the highest and the specimen without
the addition of inhibitor.
3. Results and discussion
3.1. The Weight Loss
Based on the data of immersion on the API 5L steel Grade B with the variation of concentration, the lowest
corrosion rate is at a concentration of 400 mg/L. When a metal is not given the inhibitor, the rate of corrosion will occur
more quickly. This is because along with the addition of inhibitor concentration in solution, the inhibitor will behave as
a protector on the metal. The highest inhibition efficiency is 57.35%. The result can be seen in Table 1.
Table 1. The efficiency of inhibition produced during the addition of Sarang Semut inhibitor
Concentration of inhibitor (mg/L)
Corrosion rate (mpy)
Efficiency of inhibition (%)
706,787
0
471,848
33,24
100
374,94
46,95
200
402,921
42,99
300
301,434
57,35
400
361,461
48,86
500
3.2. The Electrochemical Impedance Spectroscopy (EIS)
To determine the mechanism of Sarang Semut inhibition, the curve of the EIS result is modeled through an
equivalent circuit. The equivalent is used to determine the type of impedance that occurs when the system is being
tested by selecting the type of circuit element that is sutable with the system. The option of the circuit element types
such as Rs, Rp, CPE-Constant Phase element, etc. Rs is the resistance of the solution, Rp is used to simulate the
polarization resistance on metal, and CPE is an argument value of constant phase element. Then, it is done by seeking
the equivalent of circuit to determine the types of impedance during electrochemical cells work. The equivalent of
circuit used can be seen in Fig. 1. The Nyquist plots that have been fitted can be seen in Fig. 2.

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Fig. 1.. Equivalent of circuit used for Nyquist plot fitting


Based on the formed circuit, it shows that the reaction which occurs in the system is begun by the resistance
solution (Rs). Thiss is caused by the fact if the API 5L steel is dipped in the electrolyte solution of 0,5 M H2SO4, the EIS
will detect the H2SO4 solution and produce the resistance solution (Rs). It can be seen from Table 2, the Rct value at
concentration of 0 mg/L is 9.4266 , for the concentration of 400 mg/L is 16 186 . This shows that by giving the
inhibitor addition of Sarang Semut extract, the value of Rct increases. Rct is related to the electron transfer, the faster
the electrons move, the smaller the resistance and the quicker the corrosion rate will be. The high value of Rct at
inhibitor concentration of 400 mg/L shows that the transfer resistance at this concentration has a greater resistance than
the value Rct at 0 mg/L. Therefore, it is formed a thin layer on the
th metal-solution
solution surface as protection. This layer
causes the movement of ion from the electrolyte to the metal inhibitor. The more the passive layers formed, the higher
the Rct value and the smaller the CPE value will be.

Fig. 2. The result of nyquist plot fitting


Table 2. The parameter data resulted by equivalent circuit
Concentration of inhibitor (mg/L)

Rp (.cm2)

Rs (.cm2)

Rct (.cm2)

Cdl (F/cm2)

%EI

0
400

22.122
28.744

12.696
12.558

9.426
16.186

75.491
71.512

0
41.764

3.3. The Mechanism of Isotherm


rm Adsorption
In this experiment, the adsorption mechanism is an experimental method used to determine the interaction between
the Sarang Semut inhibitor and the surface of the API 5L steel Grade B. When the metal is immersed in the electrolyte
solution and
d given with the addition of inhibitor, the material surface will always be covered by the dipoles of water
molecule which are adsorbed. Thus, the adsorption of inhibitor molecules in the electrolyte solution is a process of
quasi substitution. The inhibitor
or efficiency is associated with the fraction of the surface which is covered by the
adsorption of the inhibitor molecule. The surface fraction which is covered (surface coverage) is obtained from the data
of weight loss experiment method. The value of surface
surface coverage () can be calculated by using this following equation:

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= IE% / 100

(1)

There are several equation models of isotherm adsorption, yet, the most often used is the Langmuir and Freundlich
models. These two have a difference which is the Langmuir is for showing the formed monolayer while the Freundlich
is for showing the multilayers. Below are the isotherm adsorption equations of Langmuir (2) and Freundlich (3) that are
used, while for calculating the value of kads is by using the equation (4):

(2)

=
=

(3)

exp

(4)

Where :
C
= Concentration of inhibitor (mg/L)
kads
= Constant of adsorption
T
= Temperature (K)
R
= Constant of ideal gas (8.314 J/mol K)

= Free standart energy adsorption (kJ/mol)

Table 3. The calculation data of surface coverage forming the graphs of Langmuir and Freundlich adsorptions
Concentration of
Corrosion rate
Efficiency of
Surface
C/
Log C
Log (/1-)
inhibitor (mg/L)
(mpy)
inhibition (%)
coverage ()
706,787
0
471,848
33,24
0,332
300,839
2,000
-0,303
100
374,94
46,95
0,470
425,972
2,301
-0,053
200
402,921
42,99
0,430
697,795
2,477
-0,123
300
301,434
57,35
0,574
697,453
2,602
0,129
400
361,461
48,86
0,489
1023,362
2,699
-0,020
500
Fig. 3 shows the Langmuir graph with the equation of y = 1.716x + 114.1 with the value of R = 0.938 whereas
Figure 4 shows the Freundlich graph with equation of y = 0.468x 1.206 with the value of R = 0.675. In the graph of
Langmuir, the R value is almost close to 1 or the exact is 0.938. This indicates that the model of the inhibitor molecule
adsorption on the material surface follows the Langmuir adsorption model. Because it follows the Langmuir model, the
formed protective layer is the monolayer. Besides for knowing the type of layer formed, it can also determine the type
of adsorption mechanism that occurs by calculating the free energy adsorption (
). This value can be calculated by
using the equations (2) and (4).
From the linear equation in Figure 3, the value Kads is obtained as much as 8.76 kJ / mol so that the value of
(
) generated is -28.76 kJ / mol. Based on El-Haddads research [3], it states that if the value of (
) is > -20
kJ / mol, the adsorption occurs in physics. If (
) is < -40 kJ / mol, the adsorption occurs in physics. If -20 kJ / mol
< (
) <-40 kJ / mol, the adsorption occurrs in the mixture of physics and chemistry. Because the value of (
)
is generated as much as -28.76 kJ / mol, the adsorption process happens is a mixed adsorption. The more negative the
value of (
), the higher the energy adsorption occurs. The negative sign in the value of (
) indicates that the
absorption process of Sarang Semut extract as a corrosion inhibitor on the metal surface takes place spontaneously and
steadily.

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Langmuir Adsorption
1200.000

y = 1.7165x + 114.13
R = 0.9388

C/

1000.000
800.000

Langmuir
Adsorption

600.000

Linear (Langmuir
Adsorption)

400.000
200.000
0.000
0

200

400

600

C
Fig. 3. The graph of Langmuir adsorption

Log (/1-)

Freundlich Adsorption
0.200
0.150
0.100
0.050
0.000
-0.0500.000
-0.100
-0.150
-0.200
-0.250
-0.300
-0.350

y = 0.4688x - 1.2065
R = 0.6754
Freundlich Adsorption

1.000

2.000

3.000

Linear (Freundlich
Adsorption)

Log C
Fig. 4. The graph of Freundlich adsorption

4. Conclusions
The highest inhibition efficiency occurs if the corrosion rate is at the lowest. In this study, the highest inhibition
efficiency occurs when the addition concentration is 400 mg/L which is 57.35%. The model of adsorption equation
follows the Langmuir adsorption isotherm. The value of
resulted is -28.76 kJ / mol. This means that the type of
adsorption which occurs is the mixed adsorption.
References
[1]. Jones, Deny. Principles and Prevention of Corrosion. New York : Macmillan Publishing Company. 1992
[2]. Halimatuddahliana. Pencegahan Korosi Dan Scale Pada Proses Produksi Minyak Bumi. Teknik Kimia USU.
2003
[3]. El-Haddad, M. N. Chitosan as a green inhibitor for copper corrosion in acidic medium. International Journal
of Biological Macromolecules Vol. 55, pp.142 149. (2013)
[4]. Roberge, P. R. Handbook of Corrosion Engineering: Mc Graw-Hill. New York. 2000
[5]. V. S. Sastri. Green Corrosion Inhibitors: Theory and Practice. USA: John Wiley &Sons. 2011

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
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[6].

Ostovari, A. Corrosion inhibition of mild steel in 1 M HCl solution by henna extract: A comparative study of the
inhibition by henna and its constituents (Lawsone,Gallic acid, a-D-Glucose and Tannic acid). Corrosion Science.
(2009)
[7]. Mekonnen Engida Adam, Kasim, Novy S., T.A Yeshitila, Ismadji, Suryadi. 2011. Extraction, identification and
quantitative HPLC analysis of flavonoids from sarang semut (Myrmecodia pendans). Industrial Crops and
Products. NACE International. Corrosion Costs and Preventive Strategies in the United States.(2011).
[8]. Pradityana. A, Sulistijono, Shahab.A. Effectiveness of Myrmecodia Pendans Extract as Eco-Friendly Corrosion
Inhibitor for Material API 5L Grade B in 3,5% NaCl Solution. Trans Tech Publications, Switzerland. Advanced
Material Research Vol. 789 pp 484-491. (2013).
[9]. Pradityana. A, Sulistijono, Shahab.A. The Influence of Adding Bio Inhibitor Sarang Semut (Myrmecodia
Pendans) to Carbon Steel API 5L Grade B in Solution of HCl 1 M. Trans Tech Publications, Switzerland.
Advanced Materials Research Vol. 1123 pp 187-191. (2015).
[10]. Pradityana. A, Sulistijono, Shahab.A. Application of Myrmecodia Pendans Extract as a Green Corrosion
Inhibitor for Mild Steel in 3,5% NaCl. Trans Tech Publications, Switzerland.. Applied Mechanics and Materials
Vol. 493pp 684-690. (2014)
[11]. Pradityana. A, Sulistijono, Shahab.A. Eco-Friendly Green Inhibitor of Mild Steel in 3,5% NaCl Solution by
Sarang Semut (Myrmecodia Pendans) Extract. Published by the AIP Publishing. American Institute of Physics
1617, 161. (2014).
[12]. ASM Handbook Vol 13A. Corrosion : Fundamentals, Testing, and Protection. USA : ASM International. 2003

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CODE: CF
Study of Mechanical and Thermal Resistance of Dissimilar Metal Weld With Filler Tgs 90.S Bg And Tgs 30.8 L
CukupMulyana1), Aswad H. Saad1), Mariah K1), Otong Nurhilal1), Makmur Arafat1), Aditya Permana P1)
1

Department of Physics, Padjadjaran University, Jl. Raya Bandung-Sumedang km.21 Jatinangor, Sumedang, Indonesia.

Abstract. Boiler is the most frequent component failed in the power plants. Observations at several plants in Indonesia
showed that the failure generally occurs at tube in the superheater outlet header, which tube is the welding between
austenitic and ferritic material which called as dissimilar metal weld (DMW). Most failures occurred in the junction
between ferritic and filler. However, the same failure occurs at the same point quickly after replacing the DMW. After
observing this problem, indicates that the cause of premature and recured failure is not due to carbon diffusion in high
temperature, difference of expansion coefficient, or low hardness rate. The significant fault is estimated due to
unsuitable filler with the previous one and have to be determined the suitable filler to increase the reliability. A study
has been conducted by using two different types of filler material that is used to join austinetic and ferritic. Studies
cover aspects of mechanical resistance and thermal resistance with high temperature tensile stress test, accelerated creep
test and also chemical composition test of the filler as both filler is unknown. From the test results of the chemical
composition, the first filler is a TGS 90.S BG with mechanical resistance of 430 MPa at an operational temperature of
550oC, while for the second filler is a TGS 30.8 L with mechanical resistance of 460 MPa at the same operational
temperature. Thermal resistance of both materials was tested with accelerated creep test and compared based on the
lifetime of the material. Calculation of lifespan material performed using Larson-Miller method and obtained for TGS
90.S BG material is estimated at 18 years, whereas for TGS 30.8 L material has a longer lifetime more than 100 years.
Keyword : Dissimilar metal weld; Filler; Ultimate tensile strength; Accelerated creep; Larson-Miller Parameter
Corresponding author: Cukup Mulyana, E-mail: c.mulyana55@yahoo.com, Tel. +62-81573208420
1. Introduction
Dissimilar metal weld (DMW) is commonly used in power plant for reducing cost. DMW is the tube made from
two joined and different metal by welding it. Low carbon stell ferritic SA-213 T22 and stainless steel SA-213 TP304H
is commonly used as DMW in power plant and refinery. In the power plant DMW used as boiler tube to deliver steam
to the turbine. Most of failure in boiler tube is in DMW tube. After DMW is replace with the new one, and the plant
operate, the same premature failure hapenned again. After conducting complete check in the tube, it indicates that the
significant cause is not come from high tepperature of carbon difussion, or from the difference of expansion coefficient,
or the decreasing of hardness of material because of high temperature, if the fault comes from those three causes, it
should affect entire structure of tube and there would be another failure in different point. Based on checking, the most
significant cause is using unsuitable filler from previous filler. It occures as in practice there are many choices of filler
and most technical worker do not test the mechanical and thermal properties of the filler before.
The goal of this research is analyzing the quality of different filler used in electric power plant Indonesia Power
UBP Suralaya. Mechanical and thermal resistant of DMW filler are tested and analysis the result is recommended
management in plant.
Dissimilar metal weld is joined pipe made from two different material by welding it. In this case, DMW is welding
between austenitic SA 213 TP-304H and ferritic SA 213 T-22 in boiler tube. Filler is required to join the different
properties of metal as the difference would affect to the tube structure in long term use. The suitable filler material
would increase the reliability of DMW.
In DMW, it is required to pay attention on durability from the two metals, such as mechanical and thermal
resistance of material. It can be observed from the response of material toward external force, internal pressure tube and
heat exposure in a long periode of time. The mechanical resistance of the tube is related with the internal pressure,
thickness of the tubes, and other forces act on the tube. The internal pressure contibuted hoop stress and longitudinal
stress. If the stress exceed the UTS of material the tube will ruptured. The thermal resistance of material parameters is
durability of meterial if it is exposed in high temperature for a long period. The thermal resistance of material can be
observed in laboratory by accelerated creep test. Using the Larson Miller methods the life time or remaining life of
material can be predicted.
Hoop stress is the circular direction stress in the pipe due to pressure from fluid which through the pipe which has
two times of internal longitude stress value[3]. Hoop stress direction (H) in the pipe with certain internal diameter (d)
and certain thickness (t) is perpendicular toward internal longitude stress (L) direction and is circular toward pipe
surface as illustrated in Fig 1.

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Fig 1. Stress vector of hoop stress (H) and longitude stress (L) in the pipe
Hoop Stress is formulated as below.
=

...............(1)

Where is hoop stress due to the pressure, P is internal pressure tube, d is outer diameter of tube and t is thickness.
While Larson-Miller Parameter (LMP) is the parameter introduced by Larson-Miller for measuring lifetime of material
by combining parameter of time and temperature[4]. LMP is formulated as below.
LMP = (TC + 273)(C + logt )x10 ......(2)
Where LMP is Larson Miller Parameter, T is temperature, C is Larson-Miller coefficient and tr is rupture time.
Another parameter, Ultimate Tensile Stress (UTS) is the maximum stress which could be held by specimen before it get
failure. UTS depends on temperature of specimen.
The DMW works in high temperature and pressure. Along this duty, microstructural change is occured and cause the
depletion of DMW. It increase the hoop stress and approach the UTS. If the UTS is exceeded by hoop stress, the failure
will occured and become a serious problem.
2. Method and Experiment
In the power plant, there are two filler used to weld the dissimilar metal made of austenitic and ferritic. The new
DMW is analyzed by serial testing to determine the mechanical durability and thermal durability of the DMW. First the
chemical composition is tested using spectrometer, it is needed to determine the type of filler. Next step, the high
temperature tensile stress is tested, the temperature ranging from 300C to 6850C. The ultimate tensile stress is observed,
the result is compared with the high temperature tensile stress from austenitic and ferritic material. The characteristics
curve UTS versus temperature describe mechanical property of material. Finally the accelerated creep test is conducted.
There are seven sample prepared for the test for each filler, the accelerated test done in the range temperature of 5400C
to 5800C and the pressure is rangging from 222 MPa to 282 MPa. The stress, temperature and fructure time are
observed. By making the Larson Miller curve the life time of DMW for a certain filler are predicted. Before it, the
coeficient of Larson Miller for each filler are determined as the standard of Larson-Miller coefficient for both filler are
unidentified. The predicting life time is reflected by thermal resistant for each filler.
3. Result and Discussion
3.1. Chemical Composition of Filler
From chemical composition test shown at Table 1. the filler is identified as ER 309Si, while the other is ER 308H,
this refer to[1].
Table 1. Chemical Composition of Filler ER 309Si and ER 308H

3.2. High Temperature Tensile Test


The test is conducted for ten different temperature varies from room temperature to 700C, and the test is done for
DMW with filler TGS 30.8 L and filler TGS 90.S BG. The test is conducted as well to the base metal as the pipe

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material, which are T 22 and TP 304H. The data for high temperature tensile stress or ultimate tensile stress (UTS) of
ferritic and austenitic is referred to Cukup Mulyana[2] as shown in Fig 2.

Fig 2. UTS versus temperature for DMW with filler TGS 30.8L, TGS 90.S BG, SA-213 T22 and SA-213 TP304H
From Fig 2, the result show that UTS of TGS 30.8L filler has the close result with TP 304H base metal, while UTS
of TGS 90.S BG has the close result with T 22 base metal. However, the close UTS result between base metal and filler
do not indicate the suitable filler for certain base metal as the most suitable filler is selected from the highest thermal
resistance. In this case, the most suitable filler is TGS 30.8L. From the curve gradient of DMW with filler TGS 90.S BG
the UTS is decreasing rapidly after temperature of 5500C, it is mean when DMW tube is operated higher than 550C the
mechanical durability drop abruptly. This filler should be used only at temperature operation below 550C, if the
temperature fluctuate due to the low quality of fuel or combustion processes, the control temperature should be tight in
order to ensure the temperature below 550C. Different with DMW with filler TGS 30.8L the gradient of curve remain
constant between 550C to 650C, it means the mechanical durability of DMW with this filler is stable to fluctuated
temperature and has mechanical resistant better than TGS 90.S BG.
3.3. Accelerated Creep Test
Accelerated creep test was done for DMW with filler type TGS 30.8 L and TGS 90.S BG. For predicting the live
of the tube it is needed at least five sample to be tested, there are seven samples of test as shown in Fig 3. After the
accelerated creep test is conducted, the Larson Miller coefficient of TGS 30.8 L is determined, in the stress of 272 MPa
with two different temperature 550C and 580C and two different time fracture. Substituting this to equation 2 the
coefficient Larson Miller is 14.3. For DMW with filler TGS 90.S BG the coefficient Larson Miller is calculated at the
stress 226 MPa with different temperature 565C and 580C, following thw same procedure the coefficient LarsonMiller 24.6. Using these coefficient the Larson Miller Parameter is calculated.
There are four creep curves are shown in Fig 3,for base metal austenitic, base metal ferritic, DMW with filler TGS
90.S BG and DMW with filler TGS 30.8 L. By using operation steam pressure 166.01 kg/cm2 and converted to hoop
stress in equation 1[5],with the safety factor 1.6, the hoop stress is 71.94 MPa. The life time of the tube is predicting in
the operational temperature of steam 5400C. For DMW tube with filler TGS 90.S BG the PLM is 19.14 and for DMW
tube with filler TGS 30.8 L, the PLM is 24.23. Substituting the PLM to equation 2 the life time of the DMW tube with
filler TGS 90.S BG is18 years, and DMW tube with filler TGS 30.8 L is more than 100 years. The Larson-Miller curve
for DMW for these tested material is shown in Fig 3.

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Fig 3. The Larson-Miller curve for DMW with filler TGS 90.S BG, TGS 30.8 L, T 22 and TP304H in operation stress
71.4 MPa, and operating temperature 540C.
In the operation pressure of 71.4 MPa and temperature 540C, the life time of DMW with filler TGS 30.L is much
longer than DMW with the filler TGS 90.S BG. Comparing with the mechanical resistant from high temperature tensile
stress test, DMW with filler TGS 30.8 L is more stable in the range temperature 550C to 650C than DMW with the
filler TGS 90.S BG. This result consistence with thermal resistant from accelerated creep test.
4. Summary
From this research, it can be conclude that Larson-Miller coefficient of TGS 90.S BG is 24.6, and 14.3 for TGS
30.8 L. The mechanical resistance of DMW tube with filler TGS 90.S BG decrease rapidly after temperature 5500C at
UTS 430 MPa. Otherwise, from accelerated creep test the thermal resistance of this material shown by lifetime
prediction about 18 years.
For DMW tube with filler TGS 30.8 L, the mechanical durability is stable between temperature 550oC to 650C. It
shown by constant UTS at 460 MPa. the thermal durability of this material is greater than TGS 90.S BG as it has longer
prediction of lifetime, which is more than 100 years.
In the operation temperature 540C and operation pressure 166.09 MPa, it is recommended to choose DMW with
filler TGS 30.8 L because this filler has better performance in mechanical resistant and thermal resistant.
Acknowledgements
We would like to say thank you to PT. Indonesia Power UBP Suralaya which allow us to take the data of DMW
from boiler tube unit 3 in 2013. And then to BPPT that helped us in accelerated creep test and high temperature tensile
test. With their contribution, this research can be finished.
References
[1] ESAB. Handbook Stainless August 2011: Stainless Stell Welding, Welding Consumables For Joining And Cladding
Stainless Steels And Nickel-Base Alloys. Sweden: ESAB. 2011
[2] Mulyana, Cukup. Taufik, Ahmad. Yodi, Agus. Siregar, Rustam. 2013. Quantification of Microstructure
Deformation from Austenitic and Ferritic Material for Predicting Remaining Life of Boiler Tube in Fossil Power
Plant. American Institute of Physics
[3] Viswanathan, Ramaswamy. 1989. Damage Mechanism and Life Assessment of High-Temperature Components.
USA: ASM International
[4] Dieter, E. George. 1988. Mechanical Metallurgy, SI Metric ed. Singapore: McGraw Hill Book Co
[5] Purwono, Sari. 2010. Data Operasional Boiler Unit 3 Juni 2010 limited. PT. Indonesia Power UBP Suralaya

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CODE: CF
Oil Heater Tube Root Cause Analysis (RCA) and Remaining Life Assessment (RLA) of Oil Heater 25F-1,
LOC-I
Cukup Mulyana 1), Ahmad Taufik 2), M Farhan Yusuf 3) , Otong Nurhilal 3), Muhamad Ridwan Hamdani 3)
1

Electrical Engineering Study Program , UniversitasPadjadjaran, Jatinangor 45363, Indonesia


PT. AT Sollution, Jakarta, Indonesia
3
Department of Physics, UniversitasPadjadjaran, Jatinangor 45363, Indonesia
2

Abstract: The root cause analysis and remaining life assesment of the ruptured oil heater convection tube 25F1, LOC-1, Refinary Plant have been done. From metallography analysis, hardness test, finite element analysis
stress and high temperature tensile stress test, it can be proven that the convection tube number 4 at row 2 of oil
heater 25-F1, LOC-1 got extreme heat of more than 890 C. Therefore, the phase of material changes to
austenite and the ruptured tube is medium carbon steel A-106B. This tube rupture is preceded by bulging caused
by local heating in a very short period. From the fault tree analysis (FTA), the cause of failure strongly
estimated because of short term overheating due to fire impingement, supported by field observation data of oil
leak tube in row 1, column 1. From the labolatory test and data analysis other contributed factors of failure are
local corrosion (crevice), the friction between tube and its support caused by a very long time thermal
contraction/expansion, and the decrease of flow rate when at 70% of shutdown in 22F-1, which in turn, make
the absorption process and transfer of heat by oil at the wall tube disturbed.
Key words : Root cause analysis; fault tree analysis;integrity assessment; corrosion.
Corresponding author: CukupMulyana, E-mail: c.mulyana55@yahoo.com, Tel. +62-81573208420
1. Introduction
Lube Oil Complex (LOC-1) is one of refinery plant facilities producing lube oil. One of the unit in LOC-1 is
heater unit 25F-1 used for heating oil from 250oC to 300oC flows in unit 22F-1 and used as heat exchanger in
unit 26F-1. Heater unit 25F-1 was built in 1974, after 38 years operation, in December2012 this unit turned
around. During the shutdown process of 22F-1 unit, the leakage is happened in the heater tube convection
section. The failure tube is detected by black smoke out from the heater and indicated the oil tube is leak
because of the heater tube is ruptured. Initial inspection was done after all system completely shutdown, from
visual inspection it is shown that one of 6Outside Diameter (OD) tube, row 2 number 4 on convection section
is ruptured (Fig 1.). The Ultrasonic Testing (UT) inspection give information there is thinning of tube wall
thickness until 20%-30% from the initial condition because of corrosion and erosion. There is no bulging tube
around the location of ruptured one, it is initial indication that the ruptured tube experienced local heating or
short term overheating or stress ruptured. The ruptured tube is replased with the new one, the hydro test was
done and the heater is operated again. When hydro test was done there is a leakage of in the no 1 row 1 tube.
The leakage is happened in at a clock tube position in supported segment. Visual inspection indicated the
ruptured because of external corrosion (crevice or friction). Avoiding the same failure in the future the ruptured
tube is observed in laboratory, mechanical, chemical composition, metallographic, Scanning Electron
Microscope(SEM) and Energy Dispersive Spectrometry (EDS) test were conducted for determining the root
cause and other contributing factor. The goal of the research is determining the root cause of the failure and
other contributed factor for 6 OD tube of convection section heater 25F-1 LOC-I.
2. Experimental
First, the 6OD ruptured tube was investigate by visual inspection. The Piping and Instrumentation
Diagram (P&ID), Process Flow Diagram (PFD) is studied and operation parameter design of 25F-1 LOC-I is
reviewed. Site visit and measurement temperature of output oil heater are conducted using infrared
thermograph. The specimen is prepared the chemical composition of failure tube is inspected by spectrometer.
The microstructure of tube material is investigated by metallographic test.
The hardness of the tube is tested,
and the SEM and fractographyc test is done for knowing the crack propagation. The EDS test is conducted to
determine the corrosion product of internal and external heater tube. The bulging process and the tube pressure

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is predicted by finite element method. Using abacus the simulation of bulging process and pressure distribution
of failure tube were shown. Finally, the damage mechanism of failure, root cause of the problem, and other
contributing factors are determined.
3. Result and discussion
The operation parameter of failure heater tube are: the material is medium carbon steel American Standard
Testing and Material (ASTM) A-106 Grade B.The tube OD is 6.625 inch with35,000 psi Specified Minimum
Yield Strength (SMYS) and 50,000 psi Ultimate Tensile Strength (UTS) at the room temperature. The inlet
operation pressure is 6.328 Kg/cm2.g and 4.219 Kg/cm2.g at the outlet.The maximum temperature in the design
of the tube is 399oC with 370oC creep threshold temperature. Maximum Allowable Stress at the maximum
operation temperature is 100 Kg/cm2.g, and the nominal pipeline thickness is 0.280 inch/7mm. The minimum
actual pipeline thickness (as measured) 6mm. The Corrosion Allowance (CA) is 0.5 inch, and the fluid tube
product is Hydrocarbon (HC).
3.1 Field Finding
Location of the ruptured lube oil heater tube is in row 2, column 4. The leakage is also found in row
1column 4 after hydro test is done. Fig 1. shows the location of the bulging and it followed with ruptured.
From the observation there are two contributed factors of the rupture, first is the friction between failure tube
and its support when the thermal expansion/ contraction happened for a long time, second is the decreasing of
flow rate when the 70% shutdown process of unit 22F-1is done.

Fig 1. Location of the rupture tube.


3.2 Laboratory Test Result and Analysis
3.2.1. Visual Observation
The specimen of the ruptured tube shown in Fig 2, while the condition of other tube below the ruptured one
is in Fig 3

Fig 2. Segment of rupture tube.


The wall of ruptured tube undergone the extreme thinning process before it ruptured. Sample test is taken at
point A and B at the location of tearing part, and point C location of the crack shown in Fig 2. There is plastic
deformation at the ruptured part. The shape of rupture is thin lips surface or fish mouth surface which indicated
there is a localized short term over heat because the yield strength is decrease rapidly due to the exposed of high
temperature.

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In Fig 3. the plastic deformation is not observed, but there are internal corrosion/fouling and external
corrosion/scaling cause the thinner process of wall tube.

Fig 3. The tube condition below the rupture tube.


The chemical composition of tube material shown in Table 1.
Table 1.The chemical composition of tube convection heater 25F-1.
Element Raptured ASTM A 106
Tube
Gr B
Wt (%)
Wt (%)
0.255
Max 0.3
C
0.1766
Min 0.10
Si
0.0236
Max 0.035
Si
0.0135
Max 0.035
P
1.038
Max 0.15
Mn
0.1572
Max 0.4
Ni
0.0536
Max 0.4
Cr
0.0281
Max 0.15
Mo
0.0029
Min 0.08
V
0.1532
Max 0.4
Cu
98.06
Balanced
Fe
From table 1 the design specification of material tube 25F-1 LOC-I is ASTM A106 Grade B. The
metallographic, microstructure and hardness of ruptured tube are in Fig 4. The microstructure and hardness test
are taken simultaneously in order to know the relation between the change of microstructure and the hardness as
a function the distance. The sample test is taken in 7 points starting from the thinnest wall to the thicker one
(point 1, 2, 3, 4, 5, 6, and7), the point 0 is located in one of the edge of the fractured. From the hardness test, the
hardness of material is decreasing away from the ruptured point. From the microstructure test grain size of
material increase away from the ruptured point, this result is consistence with the theory. The material stress is
related with the hardness of material. The ruptured pipe get higher stress.

Fig 4. The gradation of microstructure and hardness as a function of distance away from ruptured surface.

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From metallographic image in Fig 4. micro voids is not shown its mean long term creep is not occur, but
austenitic, bainite , perlite and ferrite is shown in the image. It indicate the ruptured tube undergoes local heating
with temperature over the austenite phase temperature >890oC where the ferrite in medium carbon steel is
change to austenite and form martensite and bainite when the cooling occur as shown in the isothermal cooling
curve in Fig 5.

Fig 5. Isothermal cooling curve for medium carbon steel.


From the result of microstructure test, show the inner part is relatively cooler than outside part so the
elongated grain microstructure when the manufacture of extrusion tube is seen clearly, compare with outer part
which is relatively equiaxed grains due to affection of convection heat in Fig 6.

Fig 6. Microstructure from inner and outer part of rusted tube.


3.3 SEM test and fractography
For studying the damage mechanism of tube material in the micro shape, test and observation of fracture
propagation pattern have been conducted by using Scanning Electron Microscope (SEM) with 10,000 times
magnification. SEM test plan is shown in the Fig 7. From the SEM test on the fracture surface (point A1) is
observed the high plastic deformation (elongated grains upward) which indicates the metal exposure of high
temperature, with T > 890oC. Fracture propagation indication is transgranular shown in Fig 8.

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Fig 7. SEM laboratory Test Plan.

Fig 8. SEM image shows fracture surface of rupture pipe.


3.4 EDAX/EDS Corrosion Product Test
To see the composition product of corrosion and oxidation product occurred in the tube, the Energy
Dispersive Spectrometry (EDS) analysis has been conducted.

Fig 9. SEM photo and chemical composition corrosion product of the ruptured tube surface (sample No.
A1)

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Fig 10. SEM photo and chemical composition corrosion product of the internal surface of the ruptured tube
(sample No. A2).

Fig 11. SEM photo and chemical composition product of the outer surface rupture tube (sample No. A3).

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Fig 12. SEM photo and chemical composition corrosion product of the surface tube (sample No.B2). From the
EDS spectrum the internal corrosion product are FeO, SO3, and ZrO2.

Fig 13. SEM photo and product corrosion of external surface tube (sample No B2). From the EDS spectrum the
product corrosion of external tube are Al2O3, SiO2, MoO3, FeO, SO3 and ZrO2.
3.5 Stress Rupture Test
Studying the rupture phenomena high temperature tensile stress test with the range temperature 350oC750oC has been conducted. The UTS versus temperature is in Fig 13.

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Fig 13. The UTS of material A-106B versus operation temperature.


Operation pressure of oil tube heater is 6.328 kg/cm2.g, assuming the pipe burst at the thickness of 2 mm,
outer diameter of pipe is 6 inch. By using hoop stress, internal stress of pipe is resulted as 38.8 MPa. The stress
value is extrapolated and resulted the temperature in that pressure is 850oC.
3.6 FEM Analysis (Abaqus)
To understand the bulging process related with stress distribution and estimate the failure temperature,
modeling and simulation with finite element by using Abaqus software has been conducted. The result is shown
in the Fig 14.

Fig 14. Tension contour profile for 6 inches OD tube material ASTM A106B which undergo plastic deformation
(bulging/swelling) right before rupture.
The thickness of wall tube is designed thinner close to the rupture point. At the thickness of 2mm the hoop
stress on the wall tube is 38.8 MPa.
3.6.1. Root Cause (Failure) Analysis: Damage mechanism and Failure Mode
Damage mechanism and failure mode could be described as followed. By observing microstructure
improvement which change from ferrite and perlite phase into martensite and bainite alloy (Fig 4) is observed
that the tube has undergone local heating over T = 890oC or above austinization temperature for medium carbon
steel (see Fig 5). This condition is also supported by the experiment in high temperature tensile test laboratory
which show that UTS decrease significantly above 850oC, so the hoop stress which occur when the tube wall
swell (which is calculated by finite element-see Fig 14) is equal or exceed UTS in that high temperature. It
causes tube undergo creep-rupture failure or bursting due to operating stress which exceed UTS of A106B
material. From regression equation above could be estimated that operating stress, which is 38.8 MPa is more
than UTS, so the operating temperature at that time is more than 850oC.

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3.6.2. Root Cause (Failure) Analysis: Main Problem and Other Considerable Cause

Fig 15. FTA of the rupture tube


From Fig 15. using AND and OR logic gate, shows that the tube burst only occur if there are pressure
and damage mechanism. The damage mechanism could be as corrosion, or swelling. Tube swelling could be
occurred due to long term overheat or short term overheat. From laboratory test and visual inspection as
described before could be determined that the cause of pipe swelling is due to short term overheat. Then, could
be identified that the cause of short term overheating is due to fire impingement, tube blocking due to fouling,
tube leaking in the upstream tube.
4. Conclusion
Based on research, could be concluded as that from metallography analysis, hardness value, stress analysis
with finite element, and high temperature tensile test, prove that convection tube number 4 row 2 from 25F-1,
LOC-I undergo extreme heating locally over 890oC or entering the austenite phase of medium carbon steel
material, A-106B. The convection tube number 4 in row 2 burst and begin with swelling due to short term
overheat that is possibly caused by fire impigment. Then, another factor which is contributed to tube failure is
the fraction between tube and support due to long term contraction or thermal expansion, and flowrate which
decrease when 70% shutdown at 22F-1 is done, so the heat transfer process and heat absorption from tube wall
by oil get slow.
5. References
[1] API Standard 530., Calculation of Heater Tube Thickness in Petroleum Refineries, 5th Ed, Washington,
DC. American Petroleum Institute, 2003.
[2] API Standard 571, Damage Mechanism Affecting Fixed Equipment in Refinery Industry. Washington, DC.
American Petroleum Institute, 2003.
[3] ASTM E-112, Standard Test Methods for Determining Average Grain Size, ASTM International, 2004.
[4] Metals Handbook, 9th Edition, Volume 11, Failure Analysis and Preventio, 1986.

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[5] R. Viswanathan, Damage Mechanism and Life Assessment of High Temperature Components, ASM
International, Metal Parks, Ohio 1995.
[6] Charlie R. Brooks and Ashok Choudhury, Metallurgical Failure Analysis, McGraw Hill, Inc, 1993.
[7] P&ID dan PFD, Oil Heater 25F1, LOC- I, Pertamina UP-IV, Cilacap.
[8] Laporan Kronologis Tube Leak 25F-1 dari Man Pro II ,2012.
[9] Procedure Startup-Shutdown, Oil Heater 25F-1, LOC-I, Pertamina UP-IV, Cilacap.
[10] Report Insitu Metallografi dan Kekerasan pada 25F-1 di Area LOC-1 (B2TKSBPPT), (2012).
[11] Design and Operation Specification Oil Heater 25F1, LOC-I, Pertamina UP-IV, Cilacap

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CODE: CF
Analysis of Eco-Friendly Mixture in Inhibitor
Tubagus Noor Rohmannudin, Vania Mitha Pratiwi, Yuslinur Firma, Sulistijono
Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia
Abstract: Corrosion inhibitor is a substance that able to prevent or reduce corrosion rate in metals due to its
surrounding factors. The extract of Myrmecodia Pendans or known as ant plants, and Piper Or-natum, or known as
celebes pepper are organic substances that could be used as organic inhibitor. The purpose of this research is to analyse
the effect of ant plants and celebes pepper extracts in inhib-itor on corrosion rate of API 5L Grade B Steel in a 3.5%
NaCl environment. In this research, FTIR testing is conducted to determine the characteristic of ant plants and celebes
pepper. It is also used to determine whether the inhibitor is absorbable on the surface of API 5L Grade B Steel. While to
test the effectiveness of the inhibitor, weight loss testing, dynamic-potential polarisation, and electrochem-ical
impedance spectroscopy are conducted. Based on the conducted research, there is a decreasing in corrosion rate which
is caused by the addition of the organic inhibitor in the 3.5% NaCl environ-ment. And the greatest reduction occurred
with a mixtureture consisting concentration of 50mg / l ant plant extract and 50 mg / l of extract of celebes pepper.
While the inhibition mechanism that occurred is a weak physical absorption.
Keywords: Eco-friendly; ant plant; celebes pepper; corrosion rate; API 5L Grade B; adsorption
Corresponding author: Sulistijono, E-mail: ssulistijono@mat-eng.its.ac.id, Tel. +62-31-5997026, Fax. +62-31-5997026
1. Introduction
Corrosion is a degradation of material which is caused by chemical reaction to another materials or to the
environments. Corrosion is consid-ered as an adverse process because it causes over expenses to the maintenance
budget, ob-struction in a process, and is a high risk in work safety. The presence of corrosion will cause the degradation
of material properties. As ex-plained in ASTM Handbook Volume 13, 2003, that corrosion factors which will affected
this reaction are gas content and dissolved solids, material selection, temperature factor, and re-ductor bacteria.
Basically, corrosion is unavoid-able but its rate could be controlled, on of it is by applying inhibitor. Inhibitor is a
substance that able to prevent or reduce corrosion rate in metals due to its surrounding factors. By the addition of
inhibitors in an environment, corro-sion rate will be reduced.
Therefore, research on finding a new source of corrosion inhibitor, is widely con-ducted, especially from natural
resources. Wild plants are chosen to be the alternative because they are safe, eco-friendly, biodegradable, and cheap
substances. Besides they are also easy to obtain compared to other alternative resources. Organic materials which are to
be used as in-hibitors, are able to prevent and decrease oxi-dation reaction that happens in the metallic body, by having
an anti-oxidant substance work through a specific mechanism. That anti-oxidant substance is a compound that could
delay, reduce, and prevent oxidation process from happening.
Ant plants (Myrmecodia Pendans) are considered to be one of natural resources that could be used as eco-friendly
bio inhibitor. Based on the research conducted by Atria and team, those plants could be considered as one of the wild
plants that could be applied as al-ternative inhibitors to control corrosion rate of API 5L Grade B Steel. Beside that,
celebes pepper (Piper Ornatum) is also considered as the research object, because it contains alka-loids, flavanoids, and
tannins, which are effec-tive as anti-oxidant substances. Therefore, in this research, a mixtureture of ant plants extract
and celebes pepper extract is done, as a purpose to analyse the effectiveness of a mixtureed ant plants and celebes
pepper inhibitor on carbon steel in a 3.5% NaCl environment.
Such, the composition of ant plants cel-ebes pepper extract mixtureture in this research, are : 100% AP; 75% AP :
25% CP; 50% AP : 50% CP; 25% AP : 75% CP and 100% CP. To determine the ant plants and celebes pepper
characteristics are by conducting a Fourier Transform Infra Red (FTIR) Testing. While, to determine the corrosion rate
and efficiency on the mixtureed inhibitor are by conducting dy-namic-potential polarisation, weight loss, and
Electrochemical Impedance Spectroscopy (EIS) testings. Material that is used in this re-search is API 5L Grade B
Carbon Steel. The result from this experiment is expected to be considered and produced as an eco-friendly, natural
inhibitor. Therefore, it could be used as an application in oil and gas industry, especially in Indonesia.
2. Experimental
2.1. Inhibitor preparations
The extraction method used to get the plants extract is through maceration process. Ant plants and celebes pepper
that have been powdered are each sunk into a 70% ethanol fluid separately. Every day in three whole days, the

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powdered solution are filtered until the plants extracts are obtained. The obtained results are concentrated using a
rotary evaporator, to separate the solvent and the extracted substance. Thus, a solid extract of each plant is obtained to
be used as corrosion inhibitors.
2.2. Specimen preparations
To conduct the weight loss testing, the API 5L Grade B Steel is cut off into a 10x10x3mm dimension object. Then,
the upper surface of the cut off steel is drilled to make 3mm diameter hole to hold up the steel as it is immersed. The
specimen is cleaned beforehand. After that, pickling is conducted by a 1M HCL solution to dispose corrosion residual
on the specimen. As for the EIS and dynamic-potential polarisation testings, the specimen preparation could be
conducted similar to the weight loss testing, by cutting the steel off into a 10x10x3mm dimension object. Then it is
welded to a copper wire. The welded part of steel is then moulded by resin proxy and a PVC pipe mould. After the
moulding process, the uncovered part of the specimen is then polished by sandpaper of grade 120, 320, 400, 600, 800,
1000 until the surface is even.
2.3. Solution preparations
The solution used in this experiment is a 3.5% NaCl solution. To obtain a 1000ml of 3.5% NaCl solution, 35.24
gram of NaCl solids are first measured, then added by aqua fluid until it reached 1000ml volume in a beaker glass. Then
the solution is stirred using magnetic stirrer to obtain a homogenous 3.5% NaCl solution.
2.4. FTIR testing on ant plants and celebes pepper extracts
The FTIR test conducted to Ant Plants and Celebes Pepper, are used to analyse the functional groups and chemical
bondings in every sample. The spectroscopy method used in FTIR testing is absorption. Which is basically done by the
absorbance of infrared radiation.
2.5. Weight loss testing
The weight loss test is a measuring method of corrosion rate (mpy) in a material by counting the difference between
initial weight and after weight of the following material. In this experiment, immersion of a 0 mg/l, 100 mg/l, 200 mg/l,
300 mg/l, 400 mg/l, and 500 mg/l celebes pepper inhibitor, is conducted for 30 days in a 3.5% NaCl solution. The after
weight data of the test is taken in every sixth multiple of the NaCl solution. After that, the weight loss test for the
mixtureed inhibitor of ant plants and celebes pepper, is conducted. This testing is conducted in a high effectivity
concentration multiplied by each fractions, those are 100% AP; 75% AP : 25% CP; 50% AP : 50% CP; 25% AP : 75%
CP and 100% CP.
2.6. Electrochemical impedance spectroscopy testing
Electrochemical Impedance Spectroscopy is a method to analyse the respond of a corroded electrode to an AC
potential signal as a function of frequency. This method is used to determine an inhibition mechanism between a metal
and an inhibitor, whether it is kinetically controlled by transfer of load or mass transfer. The lowest amplitude of an AC
wave is 10Mv in a 0.1-1,000,000 Hz frequency. In this experiment an EIS testing will be conducted by a 0 ppm
concentration, 100 pp, ant plants, 100 ppm celebes pepper, and mixtureed inhibitor of ant plants and celebes pepper,
from the result of weight loss test in a 3.5% NaCl media. Basically, EIS is used to determine the electrochemical kinetic
parameter, in which is related to electrical elements such as resistor R, capacitor C, and inductor L.
2.7. Dynamic-potential polarisation testing
Polarisation is a phenomenon where potential deviation happens from its equilibrium state. By this polarisation
method, corrosion rate could be obtained by determining current density that is occurred from the result of a
polarisation curve (potential difference level) as a function of the number of current used to the determination of the
corrosion rate. The higher the current density is, then the better the corrosion that takes place. And vice versa. This
testing is conducted in a 0 ppm, 100 ppm of ant plants, 100 ppm of celebes pepper, and mixtureed inhibitor of ant plants
and celebes pepper.
3. Results and discussion
3.1. Test result of FTIR to ant plantss extract and celebes pepper
Figs. 1 and 2 show the FTIR test result in ant plants extract and celebes pepper
.

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Fig. 1. Ant plantss FTIR Spectrum

Fig. 2. Celebes peppers FTIR Spectrum


Based on the spectrum obtained from the FTIR test, we can analyse the functional group and the chemical bond that
contained in the test sample. The functional groups found in the Ant plants Extract and celebes pepper are : C-H, C-O,
C=C, N-H, NO2 dan O-H. Which these compounds are identified as flavonoid and tripernoid group of compound. An
organic inhibitor is expected to be adsorbed to the metal surface so that the metal will be protected from the incoming
corrosion attack from its surroundings. The compound that fits the requirement as the organic inhibitor should contain a
hydrocarbon group which is hydrophobic and one of its chains end should be hydrophilic. These compound groups are
: N, O, OH, S dan NH2. This chain bond will be the barrier that protects the metal from its corrosive surrounding.
Hence, the ant plantss extract and celebes pepper will make an excellent organic inhibitor.

Corrosion Rate
(mpy)

3.2. Weight loss test results


The weight loss test results obtained will be used to calculate the rate of corrosion in Natrium Chloride 3.5%, with
different amount of inhibitor concentration, which are : 0 mg/l, 100 mg/L, 200 mg/L, 300 mg/L, 400 mg/L, and 500
mg/L of celebes pepper extract. The results are shown in diagram three.
6.
4.5

144 Jam
144 Jam
288 Jam
288 Jam
432 Jam

3.
1.5
0.
0

125

250

375

500

625

Inhibitor Concentration (ppm)


Fig. 3. The effect of inhibitor concentration to corrosion rate with celebes peppers extract as the inhibitor in 3.5% of
NaCl solution

Inhibitor efficiency (%)

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90.
67.5

144 Jam
144 Jam
288 Jam
288 Jam
432 Jam

45.
22.5
0.
0

125

250

375

500

625

inhibitor concentration (ppm)

Fig. 4. The effect of inhibitors concentration to inhibitors efficiency (celebes peppers extract) in 3.5% of NaCl
solution
Diagram three and four show that there are fluctuate reduction of corrosion rate, and fluctuate rise in inhibitor
efficiency for every increase in inhibitors concentration from 0 mg/l and 500 mg/l, in every submersion. In which is
one of the indication from the organic inhibitors performance that work by absorbing on the metal surface to protect it
from the corrosive 3.5% NaCl solution. Hence, it reduces the corrosion rate, and raise the inhibitor efficiency as well.
Another information is that the celebes peppers extract inhibitor works best at 400 mg/l of concentration, with 82.38%
of efficiency and 0.669 mpy of corrosion rate. Meanwhile at 100 mg/l is the most effective performance with 51.29% of
effectiveness, in 576 hours of submersion. Because with only 100 ppm, the celebes peppers extract already shows the
significant increase of efficiency compared to metal without inhibitor at all.
According to the research by Sazsa, it explained that there are significant increase of efficiency at 100 ppm of ant
plants extract as the inhibitor, with 73,57% at 720 hours of submersion. Therefore, it can be concluded that the best
concentration mixture of ant plantss extract and celebes peppers extract are at 100 ppm for each and multiplied by
determined fraction. These weight loss test is implemented at various amount of inhibitor concentrations. They are : 0
mg/l, 100 mg/l of AN, 75 mg/l of AN + 25 mg/l of RB, 50 mg/l of AN + 50 mg/l of RB, 25 mg/l of AN + 75 mg/l of
RB , and 100 mg/l of RB.
Tables 1 and 2 show the corrosion rate and the inhibitor efficiency of ant plants extract and Celebes peppers
extract mixture. The biggest corrosion rate is at 4.293 mpy at 144 hours of submersion time and 0 ppm of inhibitor.
Meanwhile the slowest corrosion rate is at 1.388 mpy at 720 hours of submersion time and the mixture of 50 ppm of ant
plants + 50 ppm Celebes pepper as inhibitor with the highest efficiency of 64.09%.
Figs. 5 and 6 show the fluctuating reduction of corrosion rate and fluctuate increase in inhibitor efficiency for every
inhibitors mixture from 0 ppm, 100 ppm of ant plants, 75 ppm AP + 25 ppm CP, 50 ppm AP + 50 ppm CP, 25 ppm
AP + 75 ppm CP, and 100 ppm CP in every submersion time, which is one of the indication from the organic
inhibitors performance that work by absorbing on the metal surface to protect it from the corrosive 3.5% NaCl
solution. Hence, it reduces the corrosion rate, and raise the inhibitor efficiency as well. Using double regression from
test result data, we can obtain the linear formula of corrosion rate in this inhibitor mixture:

Z = 0.0202376X + 0.02053535Y 0.3516061


constraint : X + Y = 100
where :
Z is corrosion rate (mpy)
X is concentration of ant plantss extract (mg/l)
Y is concentration of celebes peppers extract (mg/l)

(1)

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Table 1. The relation of inhibitor concentration, time, and corrosion rate of API 5L Grade B steel in 3.5% solution of
NaCl environment using the mixture of ant plants extract and celebes peppers extract as inhibitor.
Concentration (ppm)

Submersion timing (hours)

SS

144

SM

288

432

576

720

Corrosion rate (mpy)


0

4.293

4.015

3.980

3.990

3.865

100

2.015

1.846

1.747

1.743

1.497

75

25

2.157

1.797

1.714

1.874

1.555

50

50

2.135

1.830

1.583

1.680

1.388

75

25

2.309

1.988

1.855

1.988

1.743

100

2.255

2.135

1.975

1.977

1.649

Table 2. The relation of inhibitor concentration, time, and inhibitor efficiency of API 5L Grade B steel in 3.5% solution
of NaCl environment using the mixture of ant plants extract and celebes peppers extract as inhibitor.
Concentration (ppm)

Submersion timing (hours)

SS

144

SM

288

432

576

720

Efficiency (%)
0

100

53.04

53.00

53.11

56.40

61.27

75

25

49.74

55.22

53.99

53.13

59.75

50

50

50.74

54.40

57.50

57.97

64.09

25

75

46.19

50.47

50.19

50.27

54.90

100

47.46

46.81

46.97

50.54

57.32

corrosion rate
(mpy)

5.
3.75

144 Jam
144 Jam
288 Jam
288 Jam
432 Jam

2.5
1.25
0.
0

inhibitor concentration(ppm)

Fig. 5. The effect of inhibitor concentration to corrosion rate with ant plant and Celebes peppers extract mixture at
3.5% solution of NaCl

inhibitor efficiency
(%)

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70.
52.5

144 jam
144 jam
288 jam
288 jam
432 jam

35.
17.5
0.
0

inhibitor concentration (ppm)

Fig. 6. The effect of inhibitor concentration to inhibitor efficiency with ant plant and Celebes peppers extract mixture
at 3.5% solution of NaCl
3.3. Dynamic-potential polarisation test result
Dynamic-potential Polarisation test is implemented to figure the corrosion rate of metal by developed current
density.

0 ppm
100 ppm SS
100 ppm SM
50 ppm SS + 50 ppm SM

Fig. 6. The combination of E polarisation curve versus Log I in API 5L Grade B steel in each of inhibitor concentration
The graphic above shows that Celebes pepper and ant plantss extract mixture could move the corrosion potential to
positive from -987.42 mV to -970,34 mV at 100 ppm of ant plants and -982.91 mV at 50 ppm AP + 50 ppm CP.
Meanwhile at 100 ppm of CP addition moved the corrosion potential to negative at -991.94 mV. Reviewed from the
corrosion potential movement that shows the insertion of the inhibitor to the mixtureed inhibitor. This kind of inhibitor
protects the metal by forming a thin (passive) layer which is hydrophobic, as the adsorption of inhibitor ion by the metal
surface. This layer separate the metal from its corrosive surrounding. Therefore, it hampers the corrosion rate of metal.
Table 3. Dynamic-potential Polarisation test result of API 5L Grade B steel
Concentration
(ppm)

Beta Cathodic
(mV)

Beta Anodic
(mV)

Icorr (A/cm2)

Ecorr (mV)

CR (mpy)

% EI

197.500

0.126

60.369

-987.42

27.584

100 SS

125.070

68.954

10.945

-970.34

100 SM

149.260

85.289

14.600

-991.94

6.67

75.81

50 SS + 50 SM

128.840

70.757

10.401

-982.91

4.75

82.77

5.001

81.86

Table 3 shows that the highest corrosion rate occurred at 0 ppm of concentration with 27.584 mpy. Meanwhile the
lowest corrosion rate occurred at 50 ppm of AP + 50 ppm of CP with 4.75 mpy and inhibitors efficiency of 82.77%.
Furthermore the corrosion rate and inhibitor concentration at 100 ppm of AP are 5.001 mpy and 81.86% and at 100 ppm
of CP are 6.67 mpy and 75.81%. Hence, the addition of inhibitor can reduce corrosion rate thanks to the adsorption of

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ant plants and Celebes pepperss extract in metal surface. Moreover the mixtureing of ant plants and Celebes pepper as
inhibitor can reduce the corrosion rate more than using each extract with the same concentration alone.
3.4. Electrochemical impedance spectroscopy
pectroscopy (EIS)
(EIS test result
This test is implemented to figure the mechanism of a material inhibition through the electrochemical parameters in
equivalent circuit produced by graphic fitting of EIS result.

0 ppm
100 ppm SS
100 ppm SM
50 ppm SS + 50 ppm SM

Fig. 7. EIS fitting result of API 5L Grade B. Steel with inhibitor


inhibitor concentration of 0 mg/l, 100 mg/l of AP, 100 mg/l of
CP, and 50 mg/l of AP + 50 mg/l of CP

Fig. 8. Equivalent Circuit in 3.5% of NaCl solution


In equivalent circuit shown in Fig. 8 we can obtain the elements with their values.
Table 4. The Ant plants and Celebes Pepper mixture as inhibitor Equivalent Circuit test at 3.5% of NaCl
solution In High Frequency at Metal Surface
Inhibitor Concentration (ppm)

Rs (ohm)

Cdl (F)

Rct (ohm)

0 ppm

-62.986

10.797

55.552

100 ppm SS

-65.032

8.719

69.689

100 ppm SM

-65.216

8.471

71.445

50 ppm SS + 50 ppm SM

-61.296

8.079

75.480

Table 4 shows that the double layered capacitance (dlc) is inversely proportional to capacity transfer resistance
(CTR). CTR value is the measurement of electron transfer at the metal
metal surface that inversely proportional to corrosion
current, which has the same value as metal resistance. Therefore, the higher the CTR the lower the corrosion rate. The
existence of CTR value is caused by the barrier that formed by inhibitor adsorption which
which is given to the metal
surroundings. The highest CTR value obtained at 50 ppm of AP + 50 ppm of CP of inhibitor concentration with 75.48
ohm. And the lower CTR value obtained at no inhibitor concentration which is 55.552 ohm.

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3.5. Langmuir isotherm
Langmuir Isotherm is a method to determine the type of adsorption that occurs to inhibitor and metal. This
adsorption process is bounded by surface coverage formed by a monomolecular layer, so that the metal surface will be
protected from its corrosive surrounding. The adsorption of organic inhibitor in the metal surface towards the
environment occurs because of the interaction in the form of substitutional adsorption between the organic inhibitor or
water molecule in the metal surface. This adsorption result covers the metal surface. Surface Coverage is closely related
to inhibitor efficiency, meanwhile the determination of the adsorption type in Langmuir isotherm is based on the free
energy of the adsorption. The value of adsorption free energy that occurs in inhibitor addition as shown in Table 5.
Based on Table 5 we can determine the type of adsorption that occurs at the inhibitor by analysing the adsorption
free energy that take place. Moreover, the adsorption free energy that less than -20 kJ/mol indicates the occurrence of
physical adsorption on the metal surface. Meanwhile if the adsorption free energy value exceeded -40kJ/mol it indicates
the occurrence of chemical adsorption by involving transfer or sharing from inhibitor molecule to th metal surface to
form a coordinate bonding. However, the result of this test indicates that the adsorption that take place at the inhibitor
and the metal is physical adsorption. It is proved by the free energy value that less than -20kJ/mol. The mechanism of
this physical adsorption is reversible, which is explain why the adsorption that take places are weak.
Table 5. Value of adsorption free energy in various concentration of inhibitor addition at API 5L Grade B steel
Inhibitor concentration
(ppm)

Inhibitor efficiency (%)

Surface Coverage degree,

Adsorption of free energy, G0ads


(kJ/mol)

0 ppm

100 ppm SS

61.27

0.6127

11.087

75 ppm SS + 25 ppm SM

59.75

0.5975

10.929

50 ppm SS + 50 ppm SM

64.09

0.6409

11.386

25 ppm SS + 75 ppm SM

54.90

0.5490

10.438

100 ppm SM

57.32

0.5732

10.681

4. Conclusions
Based on the research which is implemented to the API 5L Grade B steel with various inhibitor concentration with
bread-fruit leaf as the inhibitor in corrosive media 1M H2SO4 and 3.5% of NaCl solution, we can conclude that: the Ant
plants and Celebes pepper ex-tract can be used as corrosion inhibitor for API 5L Grade B steel at 3.5% NaCl solution
surroundings. Mixing two different inhibitors can re-duce the corrosion rate and raise the in-hibitor efficiency at 3.5%
NaCl solution environment. The corrosion rate and effi-ciency at 100 ppm ant plants concentra-tion are 1.497 mpy and
61.27%. Mean-while the corrosion rate and efficiency at 100 ppm of Celebes pepper are 1.649 mpy and 57.32%.
Furthermore, mixing two with 50 ppm of concentration each are resulting in 1.388 mpy of corrosion rate and 64.09% of
efficiency . The inhibition mechanism of each type of inhibitor to the surface of API 5L Grade B steel are take place
because of the ad-sorption of the inhibitor to the metal sur-face, whether by physical adsorption or the forming of
passive layer forming.

References
[1] Jones, Denny A. 1992. Principles and Prevention of Corrosion. Toronto : Maxwell Macmillan Canada.
[2] Roberge, Pierre R. (2000). Handbook of Corrosion Engi-neering. New York: Mc Graw-Hill Book Company.
[3] ASM Handbook Volume 13A. 2005. Corrosion: Materi-als. USA ASTM International
[4] Fontana, Mars G., 1986. Corrosion Engineering 3rdEdition. Houston: Mc Graw-Hill Book Company.
[5] Atria, Pradityana., Sulistijono, Abdullah Shahab. 2013. Effectiveness of Myrmecodia pendans Extract as EcoFriendly Corrosion Inhibitor for material API 5L Grade B in NaCl 3.5% Solution. Advanced Material Research
[6] Thretewey, K.R., Chamberlain, J. 1995. Corrosion for Science and Engineering 2nd Edn. Longman (UK).
[7] Lathifah, Q.A., 2008. Uji efektivitas ekstrak Kasar Sen-yawa Antibakteri pada Buah Belimbing Wuluh (Aver-rhoa
blimbi L.) dengan variasi pelarut. Universitas Islam Negeri Malang (UIN) Malang.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
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[8] Nabilla, Sasza Chyntara. 2014. Aplikasi Ekstrak Sarang Semut Sebagai Inhibitor Korosi pada baja API 5L Grade B
dan AISI 1010 di Lingkungan 3.5% NaCl. Surabaya
[9] Rahayu, Kusumastuti. 2012. Pengaruh Ekstrak Buah Mengkudu (Morinda Citrifolia) Sebagai Green Inhibitor
Corrosion pada Baja Karbon di Lingkungan NaCl 3.5%. Depok.
[10] Uhlig, H. H. (2000). Uhlig's Corrosion Handbook (2nd ed.). New York: Wiley & Sons, Inc.
[11] Taleb Ibrahim, dkk. 2012. The Effect of Thyme Leaves Extraction Corrosiob of Mild Steel in HCl. Progress in
Organic Coating 75 (456-462).

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CODE: CF
The Analysis Of Mixture Of Myrmecodia Pendans And Piper Ornatum As A Green Corrosion Inhibitor On The
Corrosion Rate Of Api 5l Grade B Steel In H2so4 1m Solution
Vania Mitha Pratiwi, Tubagus Noor Rohmannudin, Jimmy Sapang Paembonan, Sulistijono
Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia
Abstract: The analysis of the mixture of Myrmecodia pendans and Piper ornatum in H2SO4 1M solution have been
studied by weight loss, EIS, Polarization and FTIR. The Myrmecodia pendans and Piper ornatum chosen because they
contain antioxidants that can inhibit the corrosion rate. The specimens used in this study is API 5L Grade B steel in
H2SO4 1M solution. The composition used in this study was 100% SS : 0% SM, 75% SS : 25% SM, 50% SS : 50% SM,
25% SS : 75 % SM dan 0% SS : 100% SM. FTIR testing result shows that passive layer formed by O, H and N bonds.
In weight loss method shows the highest efficiency at 50% SS : 50% SM mix composition with 52,43%. Polarization
testing shows the corrosion rate decreased drastically with the addition of 50% SS : 50% SM mix composition., i.e.
from 36,32 mpy to 7,93 mpy due to passive layer formed on the steel surface. EIS results show resistance solution (Rs),
charge transfer resistance (Rct) and CPE. The adsorption free energy value of the mixture of Myrmecodia pendans and
Piper ornatum is -10,02 kJ/mol and its a physical adsorption.
Keywords: Carbon steel; mixture inhibitor; Myrmecodia pendans; piper ornatum, H2SO4.
Corresponding author: Sulistijono, E-mail: ssulistijono@mat-eng.its.ac.id, Tel. +62-31-5997026, Fax. +62-31-5997026
1. Introduction
Carbon steel is a material commonly used in various applications. For example, in the world of industrial, the carbon
steel which is often used API 5L grade B steel. API 5L grade B steel used in transportation applications of oil, water and
natural gas. The problem that often occurs in the distribution of crude oil is called the crust formation of deposits
(scale). The crust is soluble ions in water such as calcium, carbonate, and sulfate[6]. Anthouse plant (Myrmecodia
pendans) is one of plant that could be applied as organic inhibitor because of its high inhibiting efficiency at 90,36% at
500 ppm concentration[2]. Besides that, red pepper vine (Piper ornatum) also could be applied as corrosion bioinhibitor.
Red pepper vine extract contains natural antioxindants such as alkaloid, flavonoid, tannin, saponin, terpenoid, and
phenols[5]. Based on research results above, anthouse extract (Myrmecodia pendans) and red pepper vine extract (Piper
ornatum) are mixed to be analyzed as steel organic inhibitor in H2SO4 1 M environment.
Specimen used in this research is API 5L Grade B steel in H2SO4 1 M environment. While mixture composition in
this research are 0% SS : 0% SM, 100% SS : 0% SM, 75% SS : 25% SM, 50% SS : 50% SM, 25% SS : 75% SM dan
0% SS : 100% SM, SS for anthouse extract and SM for red pepper vine extract. To analyze the characterization of
anthouse plant and red pepper vine, Fourier Transform Infra Red (FTIR) is performed. Then, to obtain corrosion rate
and inhibitor efficiency of the anthouse plant red pepper vine mixture, Electrochemical Impedance Spectroscopy
(EIS), Polarization and weight loss test are used. The result of this research is hoped to be applied in industrial world as
corrosion inhibitor alternative which is environmentally friendly.
2. Experimental
2.1. Inhibitor preparation
Anthouse plant and red pepper vine leaves are dried then powdered. Extraction method applied to anthouse plant
and red pepper vine leaves is maceration. Red pepper vine powder dipped in 70% ethanol solution for 3-24 hours [7].
Anthouse powder dipped in 80% ethanol for 3 24 hours [11]. The dipping result is filtered as liquid. This liquid,
which is mixture of solvent and plant extract, is evaporated with rotary evaporator to obtain the plant extract.

2.2. Specimen preparation


Specimen used is API 5L Grade B stell with composition (0,26%C, 1,2%Mn, 0,03% P, 0,03%S, 0,04% Ti). For
weight loss test, the specimen is cut in 20 20 3 mm dimension then sanded with sandpaper, after that drilled on the
upper central portion which then pickled to remove the corrosion product. Before dipped into electrolyte solution,
specimen is pondered to obtain the initial weight. For EIS and polarization test the same specimen is used. The

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specimen is cut in 10 x 10 x 3 mm dimension, then connected to 10 cm long copper wire, then moulded with epoxy
resin. The resin uncovered parts of specimen is sanded to obtain a smooth surface.
2.3. Solution preparation
Solution used is H2SO4 98%. To obtain 1000 mL of H2SO4 1 M, 54,4 mL H2SO4 98% solution is taken, then
diluted with aquades until the volume is 1000 mL in beaker glass.
2.4. Weight loss test
Weight loss test is a test done to obtain corrosion rate in mpy by find the delta of the twice weight loss test, the first
one is weight loss test for single inhibitor of red pepper vine extract to obtain efficient inhibitor concentration. Weight
loss test of red pepper vine single inhibitor done with inhibitor concentration variation of 0, 1000, 2000, 3000, 4000,
5000 mg/L in H2SO4 1 M media for 36 hours, with sample taking once in every 6 hours. For weight loss test of mixed
inhibitor of anthouse and red pepper vine extract done with variation of inhibitor mixture Ratio of 0% SS (anthouse
plant) : 0% SM (red pepper vine), 100% SS : 0% SM, 75% SS : 25% SM, 50% SS : 50% SM, 25% SS : 75% SM dan
0% SS : 100% SM.
2.5. Polarization test
Polarization test is a test done to obtain corrosion rate value based on potential difference and electrical current. This
polarization test used Autolab PGSTAT128N and processed with NOVA software. In this research specimen that will
be tested are specimen without inhibitor (0 mg/L), specimen with 1000 mg/L red pepper vine inhibitor, specimen 4000
mg/L anthouse inhibitor and specimen with inhibitor concentration Ratio of 50% SS : 50% SM.
2.6. Electrochemical impedance spectroscopy (EIS) test
Electrochemical Impedance Spectroscopy test is a test aimed for obtain the corrosion mechanism happened on a
metal surface. EIS test is also performed by Autolab tool and processed by NOVA software. The result obtained is
Nyquist curve that processed to obtain the solution resistance (Rs), charge transfer resistance (Rct) and CPE. In this
research the specimens those tested by EIS test are specimen without inhibitor (0 mg/L), specimen with 1000 mg/L red
pepper vine inhibitor, specimen 4000 mg/L anthouse inhibitor and specimen with inhibitor concentration Ratio of 50%
SS : 50% SM.
2.7. FTIR test
FTIR test is a quatitative test of a sample that showed by peaks. The result of FTIR test is intensity and frequency,
intensity showed the the quantity of compound in a specimen and the frequency showed the compound type inside the
specimen. In this research, FTIR test used to find the functional group of O, N, and S that located in extract of anthouse
plant and red pepper vine and the bound that could be adsorbed on the specimen surface.
2.8. Spectrometer test
Spectrometer test is a test performed to obtain the chemical composition of a material. This test is done in Office of
Industrial Research and Standardization, Surabaya. This test is done with JIS G 1253 standard. Specimen used is API
5L Grade B steel with dimension of 20x30x4 mm.
3. Results and Discussion
3.1. Weight loss test
The corrosion rate and inhibitor efficiency of anthouse and red pepper vine single extract in H2SO4 1M can be seen
in Figs. 1-4.
In Fig. 1, it is seen that corrosion rate is decresed as the red pepper vine inhibitor concentration is increased. The
lowest corrosion rate is in 5000 mg/L concentration, that is 836,04 mpy. The highest delta of corrosion rate decrease
happened at 1000 mg/L addition, valued at 5117,68 mpy to 2402,72 mpy. Therefore, could be summarized that addition
of 1000 mg/L is the most efficient point economically and from inhibitor addition side.

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6 h o u rs
1 2 h o u rs
1 8 h o u rs
2 4 h o u rs
3 0 h o u rs
3 6 h o u rs

Corrosion Rate (mpy)

5000
4000
3000
2000
1000
0
0

1000

2000

3000

4000

5000

In h ib ito r C o n c e n tr a tio n ( m g /L )

Fig. 1. The Influence of Red Pepper Vine Extract Concentration Influence to Corrosion Rate of API 5L Grade B Steel.

Inhibitor Efficiency (%)

100
80

6 h o u rs
1 2 h o u rs
1 8 h o u rs
2 4 h o u rs
3 0 h o u rs
3 6 h o u rs

60
40
20
0
0

1000

2000

3000

4000

5000

I n h ib it o r C o n c e n t r a t io n ( m g / L )

Fig. 2. The Influence of Red Pepper Vine Extract Inhibitor Concentration to Inhibitor Efficiency on API 5L Grade B
Steel
6 h o u rs
1 2 h o u rs
1 8 h o u rs
2 4 h o u rs
3 0 h o u rs
3 6 h o u rs

5500

Corrosion Rate (mpy)

5000
4500
4000
3500
3000
2500
2000
0

In h ib it o r C o n c e n t r a tio n R a t io ( % )

Fig. 3. The Influence of Anthouse Plant and Red Pepper Vine Mixture Inhibitor Concentration Ratio to Corrosion Rate
of API 5L Grade B Steel.
Notes :
0 : Inhibitor Concentration Ratio 0% SS : 0% SM
1 : Inhibitor Concentration Ratio 100% SS : 0% SM
2 : Inhibitor Concentration Ratio 75% SS : 25% SM
3 : Inhibitor Concentration Ratio 50% SS : 50% SM
4 : Inhibitor Concentration Ratio 25% SS : 75% SM
5 : Inhibitor Concentration Ratio 0% SS : 100% SM

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60

Inhibitor Efficiency (%)

50
40

6 h o u rs
1 2 h o u rs
1 8 h o u rs
2 4 h o u rs
3 0 h o u rs
3 6 h o u rs

30
20
10
0
0

In h ib ito r C o n c e n tr a tio n R a tio ( % )

Fig. 4. The Influence of Anthouse Plant and Red Pepper Vine Mixture Inhibitor Concentration Ratio to Inhibitor
Efficiency of API 5L Grade B Steel
Notes :
0 : Inhibitor Concentration Ratio 0% SS : 0% SM
1 : Inhibitor Concentration Ratio 100% SS : 0% SM
2 : Inhibitor Concentration Ratio 75% SS : 25% SM
3 : Inhibitor Concentration Ratio 50% SS : 50% SM
4 : Inhibitor Concentration Ratio 25% SS : 75% SM
5 : Inhibitor Concentration Ratio 0% SS : 100% SM
In Fig. 2, it is shown the relation between red pepper vine inhibitor concentration addition to inhibitor efficiency.
The highest efficiency happened on inhibitor addition of 5000 mg/L as 83,66%. It is seen that the highest delta of
efficiency increase happened at inhibitor addition of 1000 mg/L. Therefore, this condition is regarded as the most
efficient, from the economic side or from inhibitor concentration addition side. So, the concentration of 1000 mg/L used
as 100% condition for anthouse plant and red pepper vine extract mixing. For anthouse concentration used is 4000
mg/L[10]. Below is a graph that showed the relationship of corrosion rate and inhibitor efficiency to mixing condition of
0% SS : 0% SM, 100% SS : 0% SM, 75% SS : 25% SM, 50% SS : 50% SM, 25% SS : 75% SM dan 0% SS : 100%
SM.
In Fig. 3, it is seen that the highest corrosion rate is in the condition of inhibitor corrosion ratio of 0% SS : 0% SM,
scored at 5118,468 mpy and the lowest corrosion rate is in the condition of inhibitor corrosion ratio of 50% SS : 50%
SM, measured at 2086,169 mpy. The influence of anthouse plant and red pepper vine mixture inhibitor concentration
ratio to inhibitor efficiency can be seen in Fig. 4. It shows that the highest efficiency is in inhibitor concentration ratio
of 50% SS : 50% SM, at 52,43%.
To analyze the correlation between corrosion rate and anthouse plant and red pepper vine extract mixture
composition, on API 5 L Grade B steel in H2SO4 1 M environment , double lineary regression method is used. From
the obtained result of weight loss test of anthouse plant and red pepper vine inhibitor mixture then processed with
double lineary regression, a equation is obtained which showed the relationship of corrosion rate to anthouse plant and
red pepper vine extract mixture composition on API 5 L Grade B steel in H2SO4 1 M:
Z = 24,42X + 25,47Y
where :
Z = corrosion rate (mpy)
X = % of anthouse extract composition
Y = % of red pepper vine extract composition
Note that the above equation only be in effect if X + Y = 100%.

(1)

3.2. Polarization test results


The result of polarization test without inhibitor addition (0 mg/L), specimen with inhibitor red pepper vine of 1000
mg/L added, specimen with inhibitor addition of 4000 mg/L of anthouse and specimen with mixture concentration ratio
of 50% SS (anthouse) : 50% SM (red pepper vine) could be seen in Fig. 5.

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Fig. 5. Polarization Curve of E versus log (i) of API 5L Grade B Steel.


In Fig. 5, it is shown that the trend of corrosion rate decrease trend by inhibitor addition is the result of the shift of
anodic and cathodic line. Also seen that the lowest corrosion rate is in the mixture of 50% SS : 50% SM.

Concentration
(mg/L)

Table 1.Result of Polarization Test of API 5L Grade B Steel


Ecorr (mV) Icorr (A/cm2)
Beta cathodic
Beta anodic
(mV)
(mV)

CR (mpy)

EI (%)

-448,75

3125,80

84,08

276,92

36,32

4000
mg/L Anthouse
Plant
1000
mg/L Red
Pepper Vine
50% SS : 50%
SM

-413,84

1138,90

51,00

107,76

13,23

63,73

-426,40

952,11

58,98

259,82

11,06

69,55

-420,62

682,78

39,19

112,10

7,93

78,16

In Table 1 above seen that the lowest corrosion rate is in the inhibitor addition condition of 50% SS : 50% SM that
is valued at 7,93 mpy. On the inhibitor addition of anthouse plant of 4000 mg/L the corrosion rate is 13,23 mpy and on
the inhibitor addition of red pepper vine of 1000 mg/L the corrosion rate is 11,06 mpy. Beside that the score of icorr also
decreased, this is showed that inhibitor molecule adsorbtion process is happened on the surface of API 5L Grade B steel
so the anodic and cathodic reactions are inhibited [11]. While the highest efficiency in this polarization test is in the
inhibition addition of 50% SS : 50% SM with the efficiency scored at 78,16%.
The score of beta cathodic and beta anodic on inhibitor addition is significantly decreased if compared with no
inhibitor addition. This remarks that anthouse plant and red pepper vine mixture inhibitor could be used as cathodic and
anodic inhibitor [4].
3.3. Electrochemical impedance spectroscopy test (EIS) results
EIS test results on specimens without addition of inhibitors (0 mg/L), the specimen with the inhibitor addition of red
pepper vine of 1000 mg/L, specimens with the inhibitor addition of anthouse plant of 4000 mg/L and specimens with a
mixture of 50% SS: 50% SM can seen in Fig. 6.
Fig. 6 shows that the diameters of curve experienced magnification on the specimen with the addition of inhibitors
when compared with the specimen without addition of inhibitors. The largest diameters magnification is on the
specimen with the addition of inhibitor mixture of 50% SS : 50% SM. The curve is not semicircular, this is caused by
the irregularities of the specimens used (rough) [11]. Roughness of a surface of the specimen will make the very large
potential difference on the surface of the specimen [8].

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Fig. 6. The fitting results of Nyquist plot on EIS test

Fig. 7. The Equivalent circuit of fitting result of Nyquist plot on NOVA software.
Fig. 7 shows the equivalent circuit that explaine about types impedance formed on the surface of the API 5L Grade B
steel. It appears that there are resistance solution (Rs), polarization resistance (Rp) and Constant Phase elment (CPE). In
the picture 7 it can be seen that the first reaction that occurs in the system is the emergence of resistance solution (Rs),
where this resistance solution caused by solution that happened on standard electrode and working electrode. In the
equivalent circuit also contained by Constant Phase Element (CPE). CPE is an empirical impedance associated with the
frequency dispersion associated with irregularities in the surface of the specimen [3]. This indicates that the specimens
used for EIS test is uneven so that arose CPE. Polarization resistance (Rp) is equal to the charge transfer resistance
(Rct). Rct arising from metal surfaces interact with the electrolyte solution resulting in dissolution of atoms on a metal
surface.
Table 2. The fitting results of Nyquist plot on API 5L Grade B Steel
Inhibitor
concentration(mg/L)
0
4000 mg/L Anthouse
plant
1000 mg/L red pepper
vine
50% SS : 50% SM

Rs ()

Rct ()

CPE

EI (%)

-62,39

64,57

1,0065

-69,49

71,29

1,0069

9,42 %

-66,65

70,16

1,0067

7,96 %

-66,84

79,12

1,0065

18,39 %

Table 2 shows that the highest efficiency is on inhibitor addition of 50% SS : 50% SM i.e. 18,39 %. On the inhibitor
addition of anthouse plant of 4000 mg/L generate 9,42% of efficiency and on the inhibitor addition of red pepper vine
of 1000 mg/L gemerate 7,96% of efficiency. The inhibitor efficiency result is different with the result of Weight loss
test, this is caused by the difference of experiment time[9]. While the Rct score is increased as the inhibitor addition , this
caused by passivation forming on the API 5L Grade B steel surface, that originated from the bond of Fe with the group
of O, C, and H that presents in anthouse plant and red pepper vine extract [11].
3.4. FTIR test results
The result of red pepper vine FTIR test in the form of FTIR spectrum and the analysis of functional group and
compound can be seen in the following.
Fig. 8 shows the result of FTIR spectrum of red pepper vine that illustrates the relation of wavenumber and
transmittance. In the Picture 8 different main wavenumber results are shown, there are 915,48, 1032,15, 1223,54,
1372,63, 1454,71, 1511,60, 1632,78, 2358,28, 2852,26, 2922,49, and 3353.10 cm-1. Below is the table of functional
groups analysis of red pepper vine.

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Fig. 8. FTIR Spectrum of Red Pepper Vine

Table 3. Analysis of Functional Groups and Compounds as the Result of Red Pepper Vine FTIR Analysis.
No.
Wavenumber (cm-1)
Bond Type
Functional Groups
1

915,48

O-H

Carboxylic acid

1032,15

C-N

Aliphatic Amine

1223,54

C-O

Alcohol, carboxylic acid, ester, ether

1372,63

1454,71

1511,60

N-O

Nitrocompounds

1632,78

C=C

Alkenes

2358,28

Triple

2852,26

10

2922,49

11

3353,10

C-H

C-H
N-H
O-H

Alkane

Alkanes
Amines, amides
Alcohols, phenols

Fig. 9. FTIR Spectrum of Passivation Layer on API 5L Grade B Steel


In Table 3, it is shown that the wavenumber 915,48 cm-1 having O-H bond with the functional group of carboxylic
acid, while the wavenumber 1032,15 having C-N bond that is functional group of aliphatic amine. Wavenumber
1223,54 cm-1 have C-O bond that assumed having the functional group of alcohol, carboxylic acid, ester, and ether. The
bond of C-H presents in wavenumber 1372,63 cm-1, 1454,71 cm-1 dan 2922,39 cm-1 with alkane functional group. In
wavenumber 1511,60 cm-1 nitrogen compound is assumed with N-O bond and in wavenumber 1632,78 cm-1 the double
bond between C and C or C=C is present with functional group of alkene. In wavenumber 2358,26 cm-1 the triple bond
or aromatic ring is present, but the type of compound or functional group that composing the form of bond is unknown,
but this bond will produce electron that functions as facilitator of charge transfer from inhibitor to metal surface [11].
In wavenumber 3353,10 cm-1 two bond forms, the first one is N-H of amine or amide functional group and the second

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one is O-H with alcohol or phenol functional group. The bonds that present in red pepper vine such as O-H, C-N, C-O,
C-H, N-O, C=C and N-H is associated to flavonoid which is one type of antioxidant [1].
Fig 9 shows the result of FTIR spectrum of passivation layer on API 5L Grade B steel that depicts the relationship
of wavenumber and transmittance. The different wavenumbers shown in Picture 9 are 506,34, 518,74, 552,41, 572,41,
585,62, 600,79, 668,73, 1079,03, 1559,39, 2159,08, 2341,46, 2358,48, 3281,27 and 3319,26 cm-1. The following is the
result of functional group analysis of red pepper vine extract on the Table 4.
Table 4. Analysis of Functional Groups and Compounds as the Result of Passivation Layer on API 5L Grade B Steel
FTIR Analysis
No.
Wavenumber (cm-1)
Bond Type
Functional Group
1
506.34
2
518.74
3
552.41
C-Br
Bromide
4
572.41
5
585.62
6
600.79
7
668.73
C-Br
Alkyl halide
8
1079.03
C-N
Aliphatic amine
9
1559.39
N-O
Nitrous compound
10
2159.08
Alkenes
CC
11
2341.46
Triple
12
2358.48
N-H
Amine, amide
13
3281.27
O-H
Alcohol, phenol
N-H
Amine, amide
14
3319.26
O-H
Alcohol, phenol
In Table 4, it is shown that C-Br bond is formed as bromide functional group of wavenumber 506,34, 518,74,
552,41, 572,41, 585,62, and 600,79 cm-1. In the wavenumber 668,73 cm-1, C-Br also formed but the functional group is
alkyl halide. In the wavenumber 1079,03 cm-1 C-N bond formed with functional group of amine aliphatic. In the
wavenuber 1559,39 cm-1 nitrous compound is formed with N-O bond, while in wavenumber 2159,08 cm-1 triple bond of
C is formed as alkene. In the wavenumber 2341,46 and 2358,48 cm-1 triple bond or aromatic ring is formed but the
compound is unknown, same as what happened with the FTIR of red pepper vine. In the wavenumber 3281,27 and
3319,26 cm-1, both wavenumber forms N-H and O-H with the functional group of N-H is amine and amide, while the
functional group of O-H is alcohol and phenol. The results above shows that adsorbtion had been happened from the
mixing of anthouse plant and red pepper vine inhibitor on the surface of API 5L Grade B steel. While the adsorbed
bonds are C-N, N-O, N-H, O-H, and the unknown triple bond which is forming the electron. Those bonds are
identified as flavonoids which functioned as antioxidant to protect the metal surface.
3.5. Spectrometer test results
The result of spectrometer test of the API 5L Grade B steel can be seen in Table 5.
Based on Table 5, it could be concluded that API 5L Grade B steel is a low carbon steel because of the C content
that below 0,3%. Beside the carbon another elements that present are Si, Mn, P, S, Cu, Ni, Cr, Mo, and Al. Elements
like Ni, Mn, Cr, and Mo are the elements that could make a metal become corrosion resistant. But the content
percentage of those elements in API 5L Grade B steel is very small, so the steel is still prone to corrosion. Then, API
5L Grade B steel needs a system of corrosion protection, one of them is inhibitor.
4. Conclusions
After various experiments and analysis done to red pepper vine and anthouse plant inhibitor mixture, could be
summarized that: The mixing of anthouse plant and red pepper vine inhibitor extract could be used as green corrosion
inhibitor. Efficiency of 4000 mg/L anthouse plant single inhibitor reached 49,5% with corrosion rate measured
2584,731 mpy, efficiency of 1000 mg/L red pepper vine single inhibitor reached 50,74% with corrosion rate measured
2521,446 mpy and efficiency of 50% SS : 50% SM mixture is 52,43% with corrosion rate measured 2086,169 mpy.
This proved that mixed inhibitor is more effective than single inhibitor. Inhibition mechanism of mixture inhibitor of
anthouse plant and red pepper vine is physical adsorbtion and passivation layer forming on metal surface.

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Table 5. Analysis of Spectrometer Test Result of API 5L Grade B Steel
Element
Chemical Composition (%)
C

0,19526

Si

0,18809

Mn
P

0,37488
0,01538

0,01252

Cu

0,01259

Ni

0,02316

Cr

0,04622

Mo

0,00913

Al
Fe

0,00122
99,122

References
[1] Akbar, Hendra. 2010. Isolasi Dan Identifikasi Golongan Flavonoid Daun Dandang Gendis (Clinacanthus Nutans)
Berpotensi Sebagai Antioksidan. Departemen Metalurgi dan Material FT UI: Depok.
[2] Atria, Pradityana., Sulistijono, Abdullah Shahab. 2013. Effectiveness of Myrmecodia Pendans Extract as EcoFriendly Corrosion Inhibitor for Material API 5L Grade B in 3,5% NaCl Solution. Departemen Material dan
Metalurgi FTI ITS: Surabaya.
[3] Brug, G.J., Eeden, Van Den, Sluyters-Rehbach, Sluyters. 1984. The Analysis of Electrode Impedances
Complicated by The Presence of a Constant Phase Element. Departement of Chemistry, University of Utrecht:
Utrecht.
[4] Darmawan, Oki. 2012. Studi Green Corrosion Inhibitor Ekstrak Daun Bayam Merah (Amaranthus gangeticus)
Pada Baja Karbon Rendah dalam Larutan 1M HCl dengan Metode Polarisasi Dan EIS. Departemen Metalurgi
dan Material FT UI: Depok.
[5] Firman Wicaksono, Desie Suci, Beta Herilla, Diama Lyrawati. 2010. Inovasi Terapi Kombinasi Ekstrak Daun
Salam (Eugenia Polyantha) dan Sirih Merah (Piper Crocatum) terhadap Peningkatan Aktivitas Fas/Fas-L pada
Regresi Pertumbuhan Kanker Serviks Secara In Vitro. Fakultas Kedokteran Universitas Brawijaya: Malang.
[6] Halimatuddahliana. 2003. Pencegahan Korosi Dan Scale Pada Proses Produksi Minyak Bumi. Teknik Kimia
USU: Medan.
[7] Harborne, J. B. 1987. Metode Fitokimia: Penuntun Cara Modern: Menganalisis Tumbuhan, Diterjemahkan oleh
Kosasih Padmawinata. Institut Teknologi Bandung: Bandung.
[8] Ichwani, Rizky. 2014. Pengaruh Kekasaran Permukaan Terhadap Laju Korosi Baja API 5L dalam Larutan Asam,
Basa, dan Garam. Fakultas Teknik Universitas Brawijaya: Malang.
[9] Nadhir, Fathan, Sulistijono. 2014. Pemanfaatan Bio Inhibitor Daun Sukun Terhadap Laju Korosi Pada Baja Api
5L Grade B Di Lingkungan 3,5 % NaCl Dan 1 M H2SO4. Departemen Material dan Metalurgi FTI ITS:
Surabaya.
[10] Putri, Illiyyin, Sulistijono. 2014. Pengaruh Konsentrasi Inhibitor Ekstrak Sarang Semut terhadap Laju Korosi
Baja API 5L Grade B dalam Media H2SO4 1 M. Departemen Material dan Metalurgi FTI ITS: Surabaya.
[11] Sasza, Sulistijono. 2014. Aplikasi Sarang Semut (Myrmecodia Pendans) Sebagai Inhibitor Korosi pada Baja API
5L Grade B Dan AISI 1010 Dalam Media 3,5% NaCl. Departemen Material dan Metalurgi FTI ITS: Surabaya.

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CODE: CF
Effect of Paracetamol Addition to Protection Performance of Peanut Shell based inhibitor on API 5L Carbon
Steel in Acid and Neutral Environment
Budi Agung Kurniawan1), Sigit Tri Wicaksono1), Vania Mitha Pratiwi1), Tubagus Noor1) and Zahra Karima1)
1

Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia

Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia

Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia

Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia

Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia
Abstract: One of method to control internal corrosion in pipelines is by using inhibitor. Recently, green inhibitor
becomes major topics in corrosion prevention because of the existence of antioxidant to react with corrosive agent.
Study on paracetamol addition in Peanut Shell inhibitor has been performed. Phenolic content inside paracetamol might
act as anticorrosion agent as well as in green inhibitor. The purpose of this study is to observe the role of paracetamol in
peanut shell based inhibitor in prevention of corrosion on carbon steel. Concentration of paracetamol added was 1000,
1500, 2000 and 2500 ppm to 500 ppm peanut shell inhibitor. Electrochemical and weight loss tests at pH 5 and 7 were
performed to observe corrosion performance. FTIR and XRD tests were performed as well in order to investigate the
existence of inhibitor on steel surfaces. Results of weight loss tests showed that the highest inhibitor efficiency was
obtained at 2000 ppm total concentration. While electrochemical test result showed slight lower efficiency, with
extremely high corrosion rate results. According to theoretical calculation, inhibition mechanism of this mixed inhibitor
was physisorption, which has no chemical reaction between inhibitor and steel surface.
Keywords: corrosion; inhibitor; paracetamol; peanut shell; efficiency
Corresponding author: Budi Agung Kurniawan, E-mail: agung_bak@mat-eng.its.ac.id, Tel. +62-31-5997026 Fax. +6231-5997026
1. Introduction
Corrosion inhibitor is a chemical substance which added to a particular corrosive environment that might reduce the
rate of corrosion which attack a metal. Green inhibitor becomes great issues because the ability of antioxidant in it to
inhibit corrosion. One green inhibitor that already explored is peanut shell. Peanut (Arachis hypogeal L) is one source
of food in Indonesia, and produced on a large scale, covering 1.25 tons of peanut per day. Waste generated from the
peanut industry is in the form of peanut shells, Utilized limited as fodder, whereas peanut shells contain compounds
which is antioxidants [2]. In addition some inorganic inhibitor-containing antioxidants is ascorbic acid (C6H8O6) or
commonly known as Vitamin C supplements, (acetaminophen) on paracetamol and aspirin hydrocarbon group. This
research studied the effect of paracetamol addition in corrosion protection of peanut shell based inhibitor. Whether
paracetamol existence increasing protection synergistically in reducing the corrosion rate of a metal.
2. Experimental
Steel API 5L is used in this study, cut into rectangular shape with a size of 20 x 20. Steel surface cleaned by
pickling, with immersion in 0.5 M HCl for 10 minutes and then cleaned using an alkaline solution. Peanut shells
cleaned first from dirt / mud using water. Then dried in the sun exposure for 3 days and then crushed using a blender
after peanut shell powder soaked in 96% ethanol solvent. Soaking carried out for 30 days, then filtered and dried at
room temperature for 2 days. Peanut shell extract concentration of 500 ppm is used. For paracetamol, concentration
used as much as 0.66 grams (inhibitor concentration of 500 ppm), 1.317 gram (inhibitor concentration of 1000 ppm),
1.97 grams (inhibitor concentration of 1500 ppm) and 2.63 grams (inhibitor concentration of 2000 ppm). After that
peanut shell extract were mixed into each drug concentration of paracetamol. Corrosion media used were CH3COOH
and NaCl to represent pH 5 and pH 7. After the mixing inhibitors that have been made previously to each chamber.

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Testing is used to determine weight loss corrosion rate (mpy)
(mpy) of a steel by reducing the initial weight and final weight.
The duration of immersion were 10, 20, and 30 days with variable concentrations of 0, 1000, 1500, 2000 and 2500
ppm. XRD test was performed to analyze the corrosion products formed on the surface of the specimen. FTIR is used to
determine the functional groups contained in the inhibitor as well as knowing the compounds contained in the surface
layer of the sample results of immersion.
Table 1. Chemical composition of API 5L Grade B carbon steel
Grade C (Max) Mn (Max) P (Max) S (Max) Si (Max)
B
0,28
1,20
0,030
0,030
0.19
3. Results and Discussion
Weight loss testing was used to determine the rate of corrosion of a steel by reducing the init
initial weight and final
weight and determine the effect of the inhibitor on the rate of corrosion.
7.393

corosion rate (mpy)

8
6.115

4.314

4.475

6
5

2500 ppm

3.106
4.021

4.628

2000 ppm

1500 ppm

0.056 0.468
0 ppm
0.136 0.551
1000 ppm
0.398
0.021
1500 ppm
0.084 0.244
2000 ppm

2
1
0

1000 ppm
0 ppm

2500 ppm

10

20

30

days of immersion

Fig. 1. Weight loss results at pH 5, with various concentration of inhibitor


inhibitor.
8.098

10
corosion rate (mpy)

6.052

6.199

2500 ppm
2.89

6
4

3.26
2.0523.483
3.072
3.56
2.9111.445

3.644
3.162

0 ppm
1000 ppm
1500 ppm
2000 ppm
2500 ppm

1.619
0.426

2
0
10

20

30

2000 ppm
1500 ppm
1000 ppm
0 ppm

days of immersion

Fig. 2. Weight loss results at pH 7, with various concentration of inhibitor


inhibitor.

At pH 5 can be seen in Fig. 1 inhibitor had the lowest corrosion rate on day 20 of immersion with 2,000 ppm
inhibitor with corrosion rate of 0.021 mpy. While at pH 7 showed on Fig. 2, inhibitors work optimally as well as on the
day 20 of immersion with the addition of 2,000 ppm inhibitor with corrosion rate of 0.426 mpy
mpy.

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3.1. Isothermal Adsorption Calculation
Isothermal adsorption Calculation is one method to detect the inhibiton mechanism through calculation, based on
corrosion rate of specimen. Both Langmuir and Freundlich were used in these calculations.
3.1.1 pH 5 (Langmuir Theory)
=
=

ln(55.5
(

(1)
(2)

(3)

According to Eqs. (1), (2) and (3), it is therefore obtained:


= 0.945398
.
=
(

= 8.314

298

= 0.006925739
ln(55.5 0.006925739) = 2.368 kJ/mol

The result of 2,368 kJ / mol indicates that the inhibitor works by physisorption. Physisorption is one of the
adsorption mechanism with the characteristics of weak bonds that are reversible.
3.1.2. pH 5 (Freundlich Theory)
=

=
=

(4)

ln(55.5

0.945398 =
2500
Kads = 0.000378259
= 8.314
298 ln(55.5 0.000378259) = 9.572 k J/mol
Results of 9572 kJ / mol indicates that the inhibitor works by physisorption. Hence, it can be said that both these
theories supporting the mechanism of inhibition of inhibitors are physisorption.
3.1.3. pH 7 (Langmuir Theory)
=

ln(55.5
=
(

=
= 0.504504504
.
=
(

= 8.314

298

= 0.000509091

ln(55.5 0.000509091) = 8.836 kJ/mol

The value of 8.836 kJ/mol indicated that inhibitor worked with physisorption mechanism.
3.1.4. pH 7 (Freundlich Theory)
=
=

ln(55.5

0.504504504 =
2000
Kads = 0.000252252
= 8.314
298 ln(55.5 0.000252252) = 10.576 k J/mol
Results 10 576 kJ / mol indicates that the inhibitors work by physisorption. So it can be said that both these theories
supporting the mechanism of inhibition of inhibitors are physisorption.

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XRD test results of samples at pH 7 showed only Fe. There is no existence of corrosion product such as FeCl3 etc.
This might caused by the corrosion products FeCl3 soluble in the electrolyte. While XRD test results for samples at pH
5, FeOOH compounds detected in 2 = 45.07 and 45.17 which is the product of corrosion of the sample. Beside
FeOOH, FeCO3 was found on samples surfaces, as showed on Fig. 3 below.

Fig. 3. X Ray Diffraction result at (a) pH 5 and (b) pH 7


Results of Fourier Transform Infrared Spectroscopy FTIR testing is presented on Fig. 4 below. The data showed the
presence of O-H group on each inhibitor that is wavenumber 3295.03 cm-1 for mixed inhibitor, 3265.25 cm-1 on
paracetamol and 1410.03 cm-1 on inhibitor peanut shell. The presence of O-H groups indicates that the densest
antioxidants on each inhibitor.

Fig. 4. FTIR test result of (a) paracetamol (b) peanut shell extract (c) mixed inhibitor.
FTIR result of immersed API 5L steel showed several compounds containing nitrogen, indicating reaction came from
inhibitor, such as bond N-H which detected at peak 3328.86 for test results of samples at pH 7 and for pH 5 there are
clusters N-H were detected in peak 3276.2, as seen on Fig. 5. This peak is not detected on FTIR API 5L steel sampe
without inhibitor. Hence, it can be said that there is a reaction among inhibitor either at pH 5 and pH 7.

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Fig. 5. FTIR result of specimen under immersion at (a) pH 7 (b) pH 5 and (c) API 5L Grade B original.
3.2. Discussion
According to weight loss test result, the presence of inhibitor decreased corrosion rate of API 5L Grade B steel. The
best concentration obtained was 2000 ppm (500 ppm peanut shell + 1500 ppm paracetamol), at 20 days of immersion.
After 20 days, corrosion rate increased again. This showed that the performance of inhibitor was decreased, or it can be
said that the lifetime of inhibitor performance was 20 days.
The Langmuir and Freundlich adsorption isotherm calculation result explained the inhibition mechanism which was
physisorption. Molecules in adsorption physically not bind strongly to surfaces and usually occurs through a process
that is fast occurrence, easy to be replaced with another molecule. Based on XRD results there are corrosion product
found on steel surface, which are FeOOH and FeCO3 at pH 5. There is no corrosion product detected at pH 7, this might
caused the solubility of corrosion product in the electrolyte. The compound or the passive layer is very thin and does
not adhere well to the sample, so that might be damaged during sampling of very large chamber. According to FTIR
tests for inhibitors of the peanut shell extract and the paracetamol, detected peak explaining that the inhibitor contains
antioxidants which contain of O-H bond. FTIR results of immersed samples at pH 5 and pH 7 showed a derivatives of
amine groups (NH+). The existence of this group derived from the hydrolysis reaction of inhibitor paracetamol [3]. At
pH 5 solution, FTIR results showed a peak group containing NH+ and O-H. This group of compounds obtained from
C6H7NO or p-aminophenol. FTIR testing result on steel surface at pH 7 detected group NH+. The group has positive
ions, which tend to bind with negative ion (such as chloride) which in electrolyte solution forms Amino Acid
hydrochloride (NH2CHClCOOH)[4].
4. Conclusion
1. The addition of paracetamol into peanut shell based inhibitor decreased the corrosion rate of API 5L steel in an
environment of pH 5 and pH 7 with the most optimum results within 20 days of immersion and 2000 ppm with an
efficiency of respectively 99.82% and 94%.
2. The mechanism of inhibition mixed inhibitor peanut shell extract and the paracetamol is form a layer on steel
surface by physisorption mechanism. But the layer formed is very weak; hence it is easy to separate.
Acknowledgements
Author would like to thank to Ministry of Research, Technology and Higher Education for financial support through
Research Grant awarded on 2015
References
[1] Raja, Pandian Bothi, & Mathur Gopalakrishnan Sethuraman, Natural Product as Corrosion Inhibitor for Metals
in Corrosive Media A Review, ScienceDirect Journal, Materials Letters 62 (2008) 113116.
[2] Wee, Isolation and Identification of antioksidan from peanut shells and the relationship between structure and
antioxydants activity, Food and science biotechnology, Korea (2007).
[3] T. Koizumi, W. I. Higuchi, Analysis of data on drug release from emulsions II, J. Pharm. Sci. 57 (1968) 87-92.
[4] H. Ashassi-Sorkhabi, M. R. Majidi, and K. Seyyedi, Investigation of inhibition effect of some amino acids
against steel corrosion in HCl solution, Applied Surface Science, vol. 225, no. 14, pp, (2004) 176185.

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CODE: CF
Corrosion Behaviour of Cathodically Protected Rebars Steel in Simulated Concrete Pore Solution
1)

Moch. Syaiful Anwar , Efendi Mabruri1


1

Research Center for Metallurgy and Materials, Indonesian Institute of Sciences, South of Tangerang 15314, Indonesia

Abstract: Corrosion behaviour of cathodically protected rebars steel was observed in simulated concrete pore solution..
In The previous study, zinc alloy and aluminium alloy are commonly used to sacrificial anode system for protection of
steel in concrete. The use of pure zinc anode for the above purpose is limited. This study has been carried out with a
view to analyse the use of pure zinc anode for the cathodic protection of steel in simulated concrete pore solution and
pH 13. The electrochemical measurement was performed on cathodically protected rebars steel as working electrode,
Saturated Colomel Electrode (SCE) as reference electrode and graphite as counter electrode to evaluate open circuit
potential for 2 hours, corrosion potential and corrosion rate behaviour after 2 hours. The The relationships between the
protection potential with time, corrosion potential and corrosion rate after 2 hours, sacrificial anode life, discharge
currents, and capacity of sacrificial anodes were found. According to the results obtained, The best selection of
sacrificial anode was pure Zn anode with resistor of 600 Ohm.
Keywords: Cathodic protection; sacrificial zinc anode; electrochemical; potentiodynamic; corrosion; simulated
concrete pore solution
Corresponding author: Moch. Syaiful Anwar, E-mail: moch026@lipi.go.id, Tel. 081357308827
1. Introduction
Reinforcing steel bar (rebars) embedded in concrete is normally prevented from corrosion by the formation of the
passive film on the surface of the steel produced by high alkalinity environment of the concrete. However this
preventative action breakdown in the presence of chloride and carbonation. Once the breakdown has accured,
atmospheric oxygen and water which may already be present will produce corrosion of steel in reinfroced concrete
[1,2]. The corrosion of steel in concrete is a macro/micro galvanic electrochemical process. Macro-cell circuit is
considered to be a corrosion circuit that occur between anode (the site where chloride ion comes in contact with the
steel) and cathode (the rebar located, where there is little or no chlorides) at a certain distance from each other.
Conversely, micro-cell circuit is considered to be a circuit with an anode and cathode at very close distance that can
even treated as a negliglible distance [3] .
There are many ways to slow down the corrosion process, however cathodic protection (CP), implemented either as
an impressed current or as a sacrificial anode system, is the only technology that has proven to stop corrosion in existing
reinforced concrete structures, regardless of the chloride content in the concrete [4]. One relatively recent variation of
the CP technique is cathodic prevention (CPrev) for new reinforced concrete structures [5]. CPrev delays the onset of
corrosion by polarizing the still passive steel reinforcement to a more negative potential at which corrosion is less likely
to initiate. Since the rebars are in a passive state, the required applied current is much smaller than that normally needed
for CP. Although this technique requires a system similar to that used for CP, in contrast to CP, CPrev is usually applied
early in the service life of the structure, before the initiation of corrosion. CPrev may be an attractive method to protect
new marine reinforced concrete substructures (MRCS) using simple sacrificial submerged anodes, which are
economical and easy to replace [6].
In the previous study, zinc alloy and aluminium alloy are commonly used to sacrificial anode system for protection
of steel in concrete. The use of pure zinc anode for the above purpose is limited. This study has been carried out with a
view to analyse the use of pure zinc anode for the cathodic prevention of steel in concrete.
2. Experimental
2.1 Materials and preparation
Reinforcing steel bar (rebar) with diameter 13 mm and length 95 mm was immersed in the 500 ml HCl solution +
3,5 g hexaminetetramine to remove corrosion product in the surface of rebar, washed with distilled water, rinsed with
ethanol and dried. Then, the bottom of rebar was cover with epoxy resin for unexposed area. The simulated concrete
pore solution was prepared to this study. Then, rebar was exposed in the the simulated concrete pore solution. The total
area of rebar exposed is 34.73 cm. The chemical composition of rebar and of simulated concrete pore solution is shown
in Table 1 and Table 2.
The pure zinc anode as sacrificial anode was prepared by casting process. It is then conducted cold rolling process
resulted length 78 mm, width 42 mm and thickness 1 mm. Preparing of surfaces of pure zinc anode includes grinding
using abrasive paper # 240 and then washed with distilled water rinsed with ethanol and dried. Before testing, pure zinc
anode was weighed using digital balance type Ohaus AR 2140, Max Cap. 210 g, readibility 0.1 mg, USA.

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Table1. Chemical composition of Rebar


Chemical composition (%)
C
Si
Mn
P
0.37
0.23
0.54
0.03

S
0.04

Fe
Bal.

Table 2. Chemical composition of simulated concrete pore solution


Mol/liter
NaOH

0.1

KOH

0.3

Ca(OH)2

0.03

CaSO4.H2O

0.02

Each specimen of anode (pure zinc) and cathode (rebar) electrically connected by one end of copper wire. Sacrificial
anode electrode with required protected rebar sample, saturated calomel electrode (SCE) as reference electrode and
graphite electrode as auxiliary electrode were immersed in the 1 litre of simulated concrete pore solution. For addition,
the resistor also electrically connected in this circuit. Record the open circuit potential each 3 minutes for 2 hours. The
sacrificial anode electrode removed after 2 hours, the sacrificial anode electrode cleaned, washed with distilled water.
After rinsing with ethanol, it was dried and then re-weighted. Then, corrosion rate of protected rebar was determined by
Tafel fitting the data in the region of 250 mV from OCP. Open circuit potential and corrosion rate were measured by
Gamry G 750 series instrument.
2.2 Calculation of current output of sacrificial anode
The current output of sacrificial anode is calculated from the following equation:
( )=


(96500)

(1)

where:
Wt = atomic weight of the metal or alloy (sacrificial anodes), Wt Zn = 65.41 g/mol.
I = current in Ampere;
t = time duration of current flow in sec;
n = valance electron of the metal or alloy;
2.3 Calculation of anode life and capacity of anode
The sacrificial anode capacity of a galvanic anode is calculated from the following equation:
=
where:
AC = Anode capacity (A.hr/kg)
AL = anode Life (year);
AL = mass of sacrificial anode/ consumption rate;
Consumption rate = weight loss / time (kg/hr);
I = discharged current (Ampere);
AW = anode weight (Kg);
UF = utilization factor = 0.9; [7]
3. Result and Discussion
3.1 Cathodic protection polarization

(2)

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Fig. 1 and Table 3 represent the relationship between open circuit potential and time. The protection potential for
steel in concrete when using saturated calomel electrode is -800 mV to -900 mV where corrosion does not initiate or
propagate; potential of -900 mV to -1100 mV on cathodically protected reinforcement can occur risk of hidrogen
embrittlement; and potential of -1100 mV to more negatively on cathodically protected rebar can occur loss of adhesion
between rebar and concrete [5].
The open circuit potential (OCP) in Fig. 1 show that protected rebar with pure Zn sacrificial anode having more
negative potential compare with nonprotected rebar without Zn.
The potential of -1394 mV at the end of 2 hours (Table 3) was found on the rebar when protected with pure Zn
anode. It is indicate that pure Zn anode can not applied sacrificial anode because the steel can occur risk of hidrogen
embrittlement and loss of adhesion between rebar and concrete.
The potential of rebar becoming more positive value when a number of resistor was added in the electrochemical
circuit. These resistor can resist electron that flow from Zn to rebar depend on value of resistor. Fig. 1 and Table 3 show
that the potential of -851.6 mV at the end of 2 h was found on rebar when rebar applied Zn anode and resitor of 600 .
It is indicate that pure Zn anode+ resistor of 600 can protected rebar from corrosion. Fig. 1 and Table 3 also show
that the lower value of resistor could result more negative potential value of rebar.

Fig. 1. Open Circuit Potential vs. Time for sacrificial cathodic protection system.
Table 3. Result from open circuit potential graph
Open Circuit Potential
Minimum

Maximum

End of 2 hr

(mV vs. SCE)

(mV vs. SCE)

(mV vs. SCE)

Without Zn

-535.7

-433.4

-433.4

Zn

-1401

-1394

-1394

Zn+200

-1073

-1000

-1065

Zn+400

-950.3

-869.9

-944.9

Zn+600

-872.9

-804.2

-851.6

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3.2 Current output anode life and anode capacity of sacrificial anode
The current output of sacrificial anode is calculated from equation 1. Table 4 shows current output of pure Zn
sacrificial anode with and without resistor. Table 4 show that the pure Zn anode without resistor exhibit having higher
current output than pure Zn anode with resistor. It is indicate that rebar can occur hidrogen embrittlement and loss of
adhesion between rebar and concrete because pure Zn anode without resistor can flow higher current output to rebar.
Anode life of pure Zn anode without resistor also shows lower value of 1484.64 hours than that all. The higher anode
life of 6188.42 hours was found on the pure Zn with resistor of 400 but it having risk of hidrogen embrittlement
because of potential of -944.9 mV at the end of 2 hours shown on Table 3. The best selection of sacrificial anode used
in this work was pure Zn anode with resistor of 600 because it having protection potential of -851.6 mV at the end of
2 hours (Table 3), anode life of 5909 hours and anode capacity of 911.1 A.hr.kg-1 (Table 4).
Table 4. Current output, anode life and anode capacity of pure Zn anode with and without resistor
Current Output, I
(A)
Without Resistor

Anode Life

Anode Capacity
A.hr.kg-1

hr
0.0117

1484.64

912.28

Resistor 200

0.00311

5469.89

909.35

Resistor 400

0.00274

6188.42

908.79

Resistor 600

0.00287

5909

911.1

3.3 Potentiodynamic polarization studies


Potentiodynamic polarization plot of unprotected rebar and protected rebar with and without resistor in the simulated
concrete pore solution is shown in Fig. 2. The polarization test used three-electrode consists the specimens as working
electrode, graphite as auxiliary electrode and Saturated Calomel Electrode (SCE) as reference electrode.
The overlays of polarization curve shows there are a passive region on all of sample. The polarization curve of rebar
with Zn shows more negative potential corrosion and more high corrosion rate than that all. It is possible that high
electron that flow from pure Zn anode to rebar could result exceesive electron released by rebar.
In general, potential corrosion (Ecorr) shift to more positive value with increasing value of resisitor. The potential
corrosion of rebar with Zn+600 was around -800 mV with corrosion rate 0.016 mmpy (Fig. 3).

Fig. 2. E - log I plot of unprotected rebar and protected rebar with and without resistor in the simulated concrete pore
solution.

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4.61

0.059

0.047

0.022

0.016

Fig. 3. Corrosion rate resulted from E - log I plot


4. Conclusions
According to the results of present study, the following can be concluded that it is not possible to employ pure zinc
as sacrificial anode for rebar bacause it can occur hidrogen embrittlement and loss of adhesion between rebar and
concrete. It can be solved by addition resistor in the electrochemical circuit of cathodic protection system depending on
value of resistor. The performance of Zn anodes is strongly influenced by value of resistor. The best selection of
sacrificial anode was pure Zn anode with resistor of 600 Ohm.
Acknowledgements
The author wish to acknowledge for financial support of the present study from LIPI and also expresses thanks for
technical support from technicians.
Reference
[1]
BS 7361. Cathodic protection. British Standard; Part 1; 1991.
[2]
Andrade, C., and Alonso, C. On-site measurements of corrosion rate of reinforcements. Construction and
Building Materials, 15, 141-145, 2001.
[3]
Maruya, T., Takeda, H., Horiguchi, K., Koyama, S., Hsu, K.L. Simulation of steel corrosion in concrete based on
the model of macro-cell corrosion circuit. Journal of Advance Concrete Technology, Vol. 5 No. 3, p. 343-362,
2007.
[4]
Federal Highway Administration's (FHWA). Memorandum to Regional Federal Highway Administrators. April
23, 1982.
[5]
Pedeferri P. Cathodic protection and cathodic prevention. Construction and Building Materials. 1996;10:391
402.
[6]
Francisco J. Presuel, S.C. Kranc, Alberto A. Sags. Modeling and Measurements of Cathodic Prevention
Distribution in Partially Submerged Reinforced Concrete. NACE, ISBN: 02258, 2002.
[7]
Chukwuka I. N., Udeme O., Uzoma O. and Chizoba C. N. Effect of Sacrificial Anode Power Dissipation on Its
Anode Life, Report, 2010.

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INNOVATIVE MATERIAL

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CODE: IM
Effect of Temperature and H2O2 Addition on Recovery of Metals from Lithium Ion Batteries Using Metabolic
Citric Acid
Himawan T.B.M. Petrus1), Hendrik Setiawan1), Widi Astuti2) and Wiratni1)
Chemical Engineering Department, Engineering Faculty, Gadjah Mada University, Yogyakarta, Indonesia
2
Indonesian Institute of Science, Tanjung Bintang, Lampung, Indonesia
1

Abstract: Increasing usage of lithium ion batteries spawns new problems to the environment as LIB contains heavy
metals which are albeit undegradable and harmful materials, are valuable for human industries. In recycling of LIB,
hazardous inorganic acids are commonly used as leaching agent. For safer substitution, organic acid such as metabolic
citric acid (MCA) produced via Aspergillus Nigger sp. is used as leaching agent with hydrogen peroxide as reductor in
the leaching process. The experiment concludes that MCA provides better recovery of valuable metals than inorganic
acid. Rise of temperature increase the recovery rate of metals and H2O2 addition increase the recovery in order of three.
Keywords: LIB; recovery: Aspergillus; MCA; leaching
Corresponding author: Himawan T.B.M. Petrus, E-mail: bayupetrus@chemeng.ugm.ac.id
1. Introduction
The increasing of demand for portable electronic appliances such as laptops, mobile phones and mp3 players has
since increase the need for portable power source. Lithium-ion batteries (LIB) have since been used to fulfill this need.
But, with the increase of its application, LIB waste has become a concern for the environment. As example, in USA and
Europe, about 8 billion unit of batteries are consumed per year (Bernardes et al., 2004). The disposal of spent LIB
nowadays is done by landfills which will inevitable contaminate soil from the leakage of heavy metal in LIB.
LIB is a rechargeable battery that despite its name, does not contain metallic lithium. It uses material like LiXMA2
as cathode and graphite as anode. As electrolyte, organic liquid that contains toxic chemical such as LiClO4, LiBF6 and
LiPF6 is used (Xu et al. 2007). Usually, LIB contains heavy metals, organic chemicals and plastics in the proportion of
5-20% Co, 5-10% Ni, 5-7% Li, 15% organic chemicals and 7% plastics, these values vary depending on the
manufacturer (Shin et al., 2005). Lithium as one of the main constituent of LIB has many industrial application. In
addition, cobalt which is abundant in LIB is a relatively expensive material. In order to recover those metals from spent
LIB, many methods have been explored. The most popular method is using hydrometallurgical process. However, biohydrometallurgical process is slowly replacing the aforementioned process due to its higher efficiency, lower cost and
few industrial requirements (Mishra et al., 2007).
Conventional methods of leaching of spent LIBs to recover valuable metals include several physical and chemical
steps which involves crushing, dismantling, sieving, acid leaching, solvent extraction, chemical precipitation and
electrochemistry (Chen et al., 2011). In hydrometallurgical process of acid leaching, strong acids are used as leachant
and are able to recover more than 99% of lithium and cobalt. But, this process release toxic and harmful side product
such as Cl2, SO3 and NOx that will threat the environment (Li et al. 2009). As an alternative, organic acid such as citric
acid is used as leachant. Li et al. have studied the use of citric acid as leachant in the recovery of cobalt and lithium. The
result is citric acid has the capability to recover more than 90% of Co and approximately 100 % of Li using hydrogen
peroxide as catalyst. Hydrogen peroxide (H2O2) act as reductor in the reaction, otherwise a higher concentration of acid
solution is needed for the leaching process. This hydrometallurgical process is found to be simple, environmentally
friendly and adequate for the recovery of valuable metals from LIBs.
In the study of bioleaching, there are many kinds of bacteria that have been researched, these examples include
Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans, also fungi of the Aspergillus and Penicillium Genera
have been used (Aung and Ting, 2005). Mechanism of bioleaching itself havent been determined conclusively, the
potentially involved reaction in the bioleaching reaction proposed by Schinner and Borgstaller (1989) and Bosshard et.
Al (1996) are acidolysis, complexiolysis, redoxolysis and bioaccumulation. When being compared to bacterial leaching,
fungal leaching has more benefits in experiment, which are its ability to grow in alkaline condition, generally faster
leaching phases with shorter lag phase and the ability to excrete metabolic waste such as organic acids to form complex
with metal ions and thus reducing the toxicity of the solid metal waste. (Burgstaller and Schinner, 1993; Castro et. Al
2000).
In producing citric acid needed for industrial use, Aspergillus niger remains the main industrial producer. Strains
that are capable of overproducing citric acid have been bred to satisfy the need of various fermentation process. The
usual yield from this strains usually exceed 70% of the theoretical yield on carbon source (Papagianni, 2007). The
amount of citric acid produced by Aspergillus niger is closely tied with these aspects : the pH of culture medium,
buffering capacity of medium, carbon source, the amount of heacy metals and trace elements in the medium, balances
of nitrogen and phosphates, temperature of the medium, pre-culture period and inoculum used, resistance of

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microorganism to the metal in leaching reaction, both physical and chemical state of the solid residue, liquid-solid ratio
and leaching period (Xu and Ting, 2004; Burgstaller and Schinner, 1993).
This study is expected to determine the effect of temperature and addition of H2O2 as reductor to the leaching
process in order to optimize the recovery of valuable metals from spent LIB using the citric acid provided by the
metabolism of Aspergillus Niger and dubbed metabolic citric acid (MCA). This process will be one of the innovation in
bio-hydrometallurgical process and will have an important role in preserving the environment.
2. Material and method
2.1. Materials and reagents
Spent LIBs from laptop were collected from local vendors and treated with salt water for 2 hours to remove the
residual charge. They were then dismantled from its plastic and steel shell using plier. Anode and the cathode of the
batteries were then separated after the batteries coil was cut using knife. Metal-rich material from the cathode was
scratched from the aluminium foil, powderized using spatula and calcinated at 700C for 4 hours at heating rate of 5C/
minute to remove the residual carbon. The powder was then analyzed for its Li, Co, Mn, and Ni content
Citric acid that was used as reagent in the leaching process were obtained from the metabolism of Aspergillus niger.
The concentration metabolic citric acid (MCA) were first optimized by finding the optimum production condition.
2.2. Citric acid production
Aspergilus nigger were bred in inorganic solution with composition : 0.025% MgSO4.7H2O, 0.25% (NH4)2CO3,
0.25% KH2PO4. The solution is then mixed with 0.06 mg ZnCl2 and 1.3 mg FeCl3 or Fe2SO4 per liter solution. The pH
of resulting medium was regulated between 3.0 to 4.0.The optimum incubation time for aspergillus nigger sp. was 5
days at temperature of 30-35C. As carbon source, corn starch was used in 5% (w/v) solution and as additional catalyst
is 3% (v/v) of methanol.The citric acid produced was the separated from the bacteria and the medium. The yield of
citric acid was measured to be 230 g/ kg starch with concentration of 0.05 M.
2.3. Leaching using MCA
The leaching process were conducted using 1% w/t of pulp concentration using MCA produced using Aspergillus
niger with the concentration of 0.05 M. the experiment were done in a flask and samples are extracted within 5, 15, 30,
60, 120, 240 and 480 minutes. The temperature of the leaching process is varied at 20C and 60C in order to examine
the effect of temperature to the process. Respectively, the concentration of H2O2 added were also varied at 0% and 2%
volume. Similar experiment were also conducted using H2SO4, the most common leachant and commercially produced
citric acid, as differential.
3. Result and discussion
3.1. Effect of temperature and H2O2 in leaching with MCA
The result for the experiment in temperature variation in 0% volume H2O2 solution in Fig. 1 shows that in leaching
using MCA, all element can be extracted except Al. In accordance with the rising of temperature, the rate of leaching is
risen in the order of two and the recovery of Li and Co is enhanced in case of solution of 0% H2O2. Mn and Ni on the
other hand has optimum recovery time at 30 minutes and in the case of Mn, the recovery sharply declines after 30
minutes. This decline makes the recovery of Mn go down sharply from about 25.40% to 3.48%. It can be hypothesized
that the chemical bond from chelating mechanism in the leaching process grows weaker over time for heavier metals
such as Mn and Ni. The rise of temperature does not affect the maximum recovery of metals except for Mn which
shows that MCA can be used in the temperature range of 20C to 60C and shows no chemical instability at said
temperature.
In Fig 2., the leaching was done using solution with 2% H2O2. The maximum recovery of metals in 2% solution
H2O2 are approximately three times of the leaching with 0% H2O2 for the all leaching temperature. Al remains virtually
unleached with the addition of H2O2 in the solution. For the first 5 minute of leaching process, it was observed that with
the increase of temperature, rate of leaching increased with the order of three. The maximum recovery of Mn and Ni are
also observed in 5 minute of leaching time. But, the increase of temperature in this experiment contributes to the
decrease the maximum recovery of all element except Li which experience an increase of 5% in recovery. the recovery
of Mn go down from 77.84% at 20to a meager 5.63% at 60C after 480 minutes, recovery of Ni go down from 83.97%
to 64.72% and the recovery of Co decrease from 24.91% to 11.28% with the increase of 40 of the temperature. It
shows that the presence of H2O2 amplify the hindering of the leaching process using MCA with increasing temperature
although the maximum recovery is still about 2 times the leaching process that uses 0% volume of H2O2.

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40

100

Recovery (%)

Recovery (%)

80
60

20

40
20
0

0
0
Li 20C
Al 20C
Ni 60C

100

200
300
400
Time (minutes)
Co 20C
Mn 20C
Li 60C
Co 60C
Al 60C

500

600
Ni 20C
Mn 60C

Fig 1. Recovery of Metals at Varied Temperature for 0%


Volume of H2O2 with MCA as Leachant

0
Li 20C
Al 20C
Ni 60C

200
400
Time (minutes)
Co 20C
Mn 20C
Li 60C
Co 60C
Al 60C

600
Ni 20C
Mn 60C

Fig 2. Recovery of Metals at Varied Temperature for


2% Volume of H2O2 with MCA as Leachant

3.2. Effect of temperature in comparison with other acid


To justify the use of MCA in leaching of spent LIB, there is a need to study its ability compared to other acid. From
Fig. 3 which used citric acid as leachant and Fig. 4 that used sulfuric acid as leachant, when compared with Fig. 1
shows that for all elements, MCA provide relatively better recovery for Li, Mn and Ni at lower temperature for the
same concentration of acid. The recovery of Co however remains almost the same for all type of acid.
For citric acid, the recovery of metals at higher temperature shows the same behavior except for the recovery of Ni
when using MCA is better while the recovery at 20C is about the same. The recovery of Co, Mn and Ni when using
citric acid as leachants are 5.15%, 8.31%,and 4.01% respectively. As comparison, the recovery when using MCA are
2.53%, 3.48% and 29.72% for Co, Mn and Ni, while the recovery of Li for both citric acid and MCA are about the same
at 20.14% and 21.53%.
When compared to sulfuric acid, the recovery of metal by sulfuric acid are relatively more stable, there is no
significant increase or decrease to the resulting recovery after 480 minute, whereas MCA experience a sharp decline in
the recovery of Mn at higher temperature. This difference instability is possibly because of a difference in the leaching
reaction between MCA and sulfuric acid. According to Zhu et al. (2012) the reaction for leaching using sulfuric acid is
a redox reaction of the cathode material which can be represented by :
2 LiCOO2(s) + 3 H2SO4(aq) + H2O2(aq)

2 CoSO4(aq) + Li2SO4(aq) + 4 H2O(g) + O2(g)

The ionic reaction provide a better stability in the leaching reaction than the possible complex-forming chelation
reaction that occurs when using MCA as leachant due to higher bond energy formed when the reaction occurs.

(1)

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40

Recovery (%)

Recovery (%)

40

20

20

0
0

100

Li 20C
Al 20C
Ni 60C

200
300
400
500
600
Time (minutes)
Co 20C
Mn 20C
Ni 20C
Li 60C
Co 60C
Mn 60C
Al 60C

Fig 3. Recovery of Metals at Varied Temperature for 0%


Volume of H2O2 with Citric Acid as Leachant

0
Li 20C
Al 20C
Ni 60C

100

200
300
400
Time (minutes)
Co 20C
Li 60C
Al 60C

Mn 20C
Co 60C

500

600
Ni 20C
Mn 60C

Fig 4. Recovery of Metals at Varied Temperature for


0% Volume of H2O2 with Sulfuric Acid as Leachant

3.3. Effect of H2O2 addition in comparison with other acid


Fig 5. and Fig. 6 shows the experiment done in 2% volume H2O2 solution of citric acid and sulfuric acid
respectively. For Fig 5. which shows the leaching kinetics of LIB using citric acid as leachant with 2% volume of H2O2
when compared to leaching using the same amount of H2O2 as described in Fig. 2, at lower temperature the recovery of
metals for both acid are almost the same with MCA with an increase in order of three and MCA shows a slightly better
recovery. But, at higher temperature, citric acid has worse performance at the recovery of Ni which is only 8.33%
compared to 64.72% when using MCA which is 8 times the recovery. But, the recovery of Mn shows an opposed trend
where citric acid has better performance at 22..92% compared to 5.63% when using MCA which is 4 times better.
The recovery of sulfuric acid when 2% volume of H2O2 added shows increase of recovery at about twice the amount
and the increase in temperature only shows an insignificant increase like when leaching without using H2O2. But the
resulting recovery is only about half the recovery of MCA using 2% volume H2O2 at 20. At 60C, the resulting
recovery of Mn for MCA was worse than that of using sulfuric acid at only 5.62% compared to 42.93% of that of MCA.
This phenomena shows that while the redox reaction which occurs in the leaching process using sulfuric acid gives a
more stable recovery and can be amplified with the addition of H2O2 as reductor, the impact to the recovery when MCA
is mixed with H2O2 is much greater. This is due to the two stage reaction which are the reduction of metals that extract
metals from the solid reagent followed by the forming of metal complex which bound the metal ion to the solution.
From this, we can conclude that while the leaching reaction using chelation mechanism is more vigorous than redox
reaction and shows higher recovery, the chelation mechanism cannot extract metals form pulp material readily and need
redactor such as H2O2 for the reaction.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
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Surabaya, 4-6 October 2015

100

80

80

Recovery (%)

Recovery (%)

100

60
40

60
40
20

20

0
0
0
Li 20C
Al 20C
Ni 60C

100

200
300
400
500
600
Time (minutes)
Co 20C
Mn 20C
Ni 20C
Li 60C
Co 60C
Mn 60C
Al 60C

Fig 5. Recovery of Metals at Varied Temperature for 2%


Volume of H2O2 with Citric Acid as Leachant

0
Li 20C
Al 20C
Ni 60C

100

200

300
400
Time (minutes)

Co 20C
Li 60C
Al 60C

500

Mn 20C
Co 60C

600
Ni 20C
Mn 60C

Fig 6. Recovery of Metals at Varied Temperature for 2%


Volume of H2O2 with Sulfuric Acid as Leachant

4.

Conclusion
The result of the experiment indicated that the use of MCA provide the better recovery of metals except Al in
comparison with other acid with the same concentration in low temperature because of its chelating mechanism. The
increase in temperature increase the rate on maximum recovery of metals in the 0% solution and in the case of Mn and
Ni the optimum recovery was obtained at 30 minutes. But, the resulting recovery after 480 minutes of leaching process
decrease. For the addition of H2O2, it increased the maximum recovery in order of three in the first 5 minute because
H2O2 act as reductor to make the metals easier to be leached by MCA.
In comparison with other acid, MCA perform better at low temperature and with the addition of H2O2. This is best
described when pitted against inorganic acid which in this case is H2SO4, the recovery of MCA for all metals is about
two times that of H2SO4 even with the addition of H2O2 as redactor. But, this did not hold true for higher temperature as
the recovery of heavier metals such as Mn, Ni and Co, decrease with the increase of temperature for MCA but is
relative ly the same when using sulfuric acid. When compared to another organic acid, MCA perform better than its
counterpart except for the recovery of heavier metals
The result of the experiment shows that Metabolic Citric Acid (MCA) can be used as leachant for the recovery of
valuable metals form spent Lithium-Ion Batteries (LIBs). The performance of MCA in the leaching process are also
comparable to that of another organic and inorganic acids. The usage of MCA however is a cheaper and more
environmentally-friendly option.
Acknowledgements
This research was funded by Indonesian Directorate-General of Higher Education and Indonesian Institute of
Science. This research was also supported by Kyushu University and Gadjah Mada University.
References
[1] K.M.M. Aung and Y.P. Ting, Bioleaching of Spent Fluid Catalytic Cracking Catalyst Using Aspergillus Niger,
Bioethanol (2005), No. 116, 159-170
[2] A.M., Bernardes, D.C.R. Espinosa, and J.A.S Tenioro, Recycling of Batteries : A Worldwide Overview Compared
to Brazillian Situation, Journal of Power Sources (2004), No.130, 291-298
[3] P.B. Bosshard, R. Bachofen, and H. Brandl, Metal Leaching of Fly Ash From Municipal Waste Incineration by
Aspergillus niger, Environmental Science and Technology (1996), No. 30, 3066-3070
[4] W. Burgstaller, and F. Schinner, Minireview: Leaching of Metal with Fungi, Biotechnology (1993), No. 27, 91116

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
[5] I.M. Castro, J.L.R. Fietto, R.X. Vieria, M.J.M. Tropia, L.M.M. Campos, E.B. Paniago, and R.L. Branado,
Bioleaching of Zinc and Nickel From Silicates Using Aspergillus niger culture, Hydrometallurgy (2000), No. 57,
93-99
[6] L. Chen, X. Tang., Y. Zhang., L. Li., Z. Zeng, and Y. Zhang, Process for the Recovery of Cobalt Oxalate From
Spent Lithium-Ion Batteries, Hydrometallurgy (2011), No. 108, 80-86.
[7] L. Li., J. Ge, F. Wu, R. Chen, S. Chen, and B. Wu, Recovery of Cobalt and Lithium From Spent Lithium Ion
Batteries Using Organic Citric Acid as Leachant, Journal of Hazardous Material (2010), No.176, 288-293
[8] D. Mishra, D.J. Kim, D.E. Ralph, J.G. Ahn, and Y.H. Rhee, Bioleaching of Metals from Spent Lithium Ion
Secondary Batteries Using Acidithiobacillus Ferooxidans, Waste Management (2007), No.28, 333-338
[9] M. Papagianni, Advances in Citric Acid Fermentation by Aspergillus Niger: Biochemical Aspects, Membrane
Transport and Modelling, Biotechnology Advances (2007), No.25, 244-263
[10] F. Schinner and W. Burgstaller, Extraction of Zinc from Industrial Waste by Penicillium sp., Applied and
Environmental Microbiology (1989), No. 55, 1153-1156
[11] S.M. Shin., N.H. Kim, J.S. Sohn, D.H. Yang, and Y.H. Kim, Development of a Metal Recovery Process From LiIon Battery Waste, Hydrometallurgy (2005), No.79, 172-181
[12] J. Xu, H.R. Thomas, R.W. Francis, K.R. Lum, J. Wang, and B. Liang, A Review of Process and Technologies For
The Recycling of Lithium Ion Secondary Batteries, Journal of Power Sources (2008), No.177, 512-527
[13] T.J. Xu and Y.P. Ting, Optimisation on Bioleaching of Incinerator Fly Ash by Aspergillus niger Use of Central
Composite Design, Enzyme and Microbial Technology (2004), No. 35, 444-454
[14] S. Zhu, W. He, G. Li, X. Zhou, X. Zhang, and J. Huang, Recovery of Co and Li From Spent Lithium-Ion Batteries
by Combination Method of Acid Leaching and Chemical Precipitation, Transactions of Nonferrous Metals Society
of China (2012), No. 22, 2274-2281

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The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
CODE: IM
Novel Dye-Sensitized Solar Cell (DSSC) using TiO2 - nano SiO2 Extracted from Sidoarjo Mud Vulcano
Photoanode
Rizky Nanda Puspitasari1), Herny Ariesta Budiarti1), Sekartedjo1), Doty Dewi Risanti1)
1

Department of Engineering Physics, Institut Tekonologi Sepuluh Nopember, Surabaya, 60111, Indonesia.

Abstract: Sidoarjo mud vulcano has several compound, such as SiO2, Al2O3, Fe2O3, etc. It is known that SiO2 addition
can be employed as partial barrier of charge recombination and extending light path in DSSC. Therefore in this research
SiO2 and TiO2 (Anatase, Rutile) mixture with ratio 7.5% : 92.5% was used. The efficiency of the DSSC that used SiO2
extracted from Sidoarjo mud vulcano is 0.002%, with JSC and VOC is 0.056 mA.cm-2 and 77.85 mV, respectively. This
result is five times higher than DSSC using SiO2 from tetraethyl ortosilicate (TEOS) as a mixture, which has efficiency
of 0.0003% with JSC and VOC is 0.016 mA.cm-2 and 42.1 mV, respectively. It is likely that the addition of SiO2,
particularly that from Sidoarjo mud volcano extract, would increase the adsorption of dye on it and thus leading to the
higher photocurrent.
Keywords: Sidoarjo mud vulcano; SiO2; DSSC; photoanode.
Corresponding author: Rizky Nanda Puspitasari, E-mail: rizkikynanda@gmail.com
1.

Introduction
Sidoarjo mud vulcano was a disaster occured at Mei 28th 2006 in Sidoarjo, East Java. Sidoarjo mud vulcano
contains several coumpounds, such as SiO2, K2O, CaO, Al2O3, MnO, TiO2, and Fe2O3 [1]. Among those compounds,
silica is the largest (55%). One attempt to extract silica nanoparticles with high purity is by using co-precipitation
method under pH solution 7, 4, and 1 has been reported to achieve purity of 96,9wt% - 98.5wt% [2]. Addition of SiO2
in TiO2 has been known to enhance photocatalytic process [3], enlarge surface area and pore structure [4], and improve
dye absorption [5] .
Titania Dioxide (TiO2) nanoparticles was known to use as photoanode of Dye Sensitized Solar Cell (DSSC)
because of its intrinsically stable and unique physicochemical properties [6]. Power conversion efficiency of DSSC
TiO2-based with N-719 dye under solar simulation ( air mass 1.5 global, intensity IS = 1000 W cm-2 ) could achieve
11% [7].
It is known that diffusion becomes the major mechanism for electron transport through the fotoanode film. Thus, it
is essential for an efficient DSSC that the electron diffusion through the fotoanode film should be significantly faster
than the electron recombination with oxidized species adsorbed on the fotoanode surface or in the electrolyte. In order
to retard interfacial recombination, one of the valid approaches is to coat TiO2 particles with inorganic compound
layers such as SiO2 [6]. Addition of SiO2 in DSSC decreases the amount of agglomerations in the composite film, act
as a partial barrier layer, and increase the adhesion. By addition of SiO2 in photoanode of DSSC, its efficiency raises
to about ~45% [6]. In this paper, we introduced a simple way of SiO2/TiO2 composite paste containing various amount
of SiO2 nanoparticles obtained from tetraethyl ortosilicate (TEOS) and Sidoarjo volcanic mud.
2.

Experimental
SiO2 nanoparticles were obtained from extracted Sidoarjo mud vulcano and tetraethylorthosilicate (TEOS). SiO2
nanoparticles was extracted from Sidoarjo mud vulcano by using co-precipitation method [2]. Sidoarjo mud volcano
was soaked in HCl solution for 24 hours to remove the dirt. Rinse the Sidoarjo mud vulcano using distilled water then
dried it and ground in 250 mesh. 10 gr Sidoarjo mud vulcano and 60 ml NaOH (7 M) were put into beaker then stirred
for an hour at 70oC. 250 ml distilled water then added to the solution and the results was sieved. 2 M HCl solution was
subsequently added to the filtrate under vigorous stirring until the pH of solution reaches 7. White precipitation formed
was rinsed using distilled water, and dried at 80oC for 24 hours.
SiO2 nanoparticles from TEOS was processed through modified Stber method [8,9]. There were 2 solutions in this
method. The first solution contains 9 ml ammonia 28%, 16.25 ml ethanol 98%, and 24.75 ml demineralized water. This
solution was stirred for 5 minutes. The second solution contains 4.5 ml TEOS and 45.5 ml ethanol 98%. The second
solution then poured into the first solution and stirred for a minute. After one minute, the stirring speed was reduced to
1/3 former speed and the solution left was further stirred for 2 more hours to complete reaction. SiO2 nanoparticles
were obtained through centrifuge at 6000 rpm for 5 minutes and followed by rinsing it using ethanol. This process was
repeated 3 times and finally the obtained SiO2 was dried at 80oC.
TiO2 nanoparticles was obtained using co-precipitation method [10-12]. 10 ml TiCl3 (15%, MERCK), 4.7 ml
distilled water, and 0.3 ml HCl 37% was stirred for 3 minutes in 45oC. After 3 minutes, 20 ml HCl 37% was added

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
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under rigorous stirring. As the color of the solution became purple, 50 ml NH4OH 25% was added under stirring until
the solutions color became darker. Ammonia solution was added continuously until white color precipitate was
obtained. The resulting suspension was maintained at room temperature for a while then filtered and rinsed using
distilled water. Anatase and rutile TiO2 was obtained from calcination the white precipitate at 300oC for 4 hours and at
1000oC for 7 hours, respectively [12,13]. The crystal structure of the SiO2 and TiO2 nanoparticles was checked by
powder X-ray diffraction (XRD) using a Phillips Xpert MPD (40 kV, 30 mA) with Cu K radiation ( = 0.154 nm).
Diffraction pattern were collected for 15-60o (2) with step size of 0.01. The average crystall size was examined
through Scherrers equation [14]. FT-IR spectra of the SiO2 nanoparticles, anatase and rutileTiO2 were measured using
Thermo Scientific Nicolet iS10.
To fabricate composite paste for photoanode DSSC SiO2 and TiO2 powder were mixed. Composite of silica (SiO2)
and titania (TiO2) powder with ratio 7.5%:92.5% and 10%:90% was used for photoanode. Titania (TiO2) powder
contains of anatase and rutile with ratio 90%:10% [10,15]. The composite paste was prepared by grounding 2.5 g
composite powder in agate mortar for a while, then distilled water of 0.7 ml, 0.1 ml stabilizer CH3COOH, and 0.1 ml
Triton X-100 was added to make the paste [16]. The composite paste was coated in TCO glass by using doctor blade
technique. Furthermore, TCO glass coated by composite paste was heated for 2 minutes at 225oC using hotplate. For
dye loading, the photoanodes were immersed in the solution of natural dye of Garcinia mangostana pericarp extract
for 12 hours [11]. The electrolyte used was a redox ( I-/I3- ) gel electrolyte. DSSC performance was determined by
measuring Incident Photon to Conversion Energy (IPCE) [17] and current (I) and voltage (V) produced by DSSC at
various resistance under the sunlight at peak time (12 PM).
3. Results and Discussion
3.1. Nanoparticles and Particle Size
According to Fig. 1, SiO2 extracted from Sidoarjo mud vulcano had peak in 2 = 24.968o as indicative of the
presence of amorphous SiO2, on The other hand, SiO2 synthesized from TEOS had peak in 2 = 23.046o. Additional
peaks were observed and attributed to -Fe2O3 and -Al2O3 in 2 = 31.786o and 2 = 45.556o, respectively. By using
Scherrers equation [14] the average crystal size of SiO2 extracted from mud and TEOS was 0.73 nm and 1.82 nm,
respectively.
600

SiO2 mud extract

550

Intensity

400

Al2O3

SiO2

450

SiO2 TEOS

a-Fe2O3

500

350
300
250
200
150
100
50

15

20

25

30

35

40

45

50

55

60

65

2Theta

Fig. 1. XRD pattern of SiO2 extracted from Sidoarjo mud vulcano and SiO2 synthesized from TEOS
The composites SiO2/TiO2 nanoparticles were also examined by using XRD (Fig. 2). The results indicates that
almost all the diffraction peaks are assigned to anatase TiO2 (JCPDS No. 21-1272) and rutile TiO2 (JCPDS No. 211276). The primary peak of anatase at 2 of about 25 is overshadowed by the primary peak of SiO2 resulting in a
lower intensity and a rather broaden peak. This broader peak leads to a larger crystal size of anatase (1 0 1), i.e. 69.07
nm, whilst rutile crystalline size (1 1 0) is 20.06 nm.

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nc-TiO2/SiO2 MUD EXTRACT

2500

nc-TiO2/SiO2 TEOS
Anatase TiO2
Rutile TiO2
R(211)

R(110)

2000

R(002)

R(210)

A (105)
A (211)

A (200)

A (004)

SiO2

A (213)
A (204)

R(200)

500

R(310)

R(111)

R(220)

R(101)

1000

A(101)

Intensity

1500

0
15

20

25

30

35

40

45

50

55

60

65

2Theta

Fig. 2. XRD Pattern of SiO2/TiO2 nanocomposite powders with ratio SiO2 and TiO2 7.5%:92.5%. The pure anatase and
rutile spectras were given for comparison [10].
Fig. 3 illustrates the FT-IR spectra of the nano-composite of TiO2/SiO2. It could be seen the broad band covers the
range around 3201.32 cm-1 to 3267.60 cm-1 which is ascribed to H-O-H stretching due to absorbed water. The broad
band 1631.66 cm-1 to 1636.97 cm-1 is H-O-H bending of water and bending vibration of Ti-OH [11,18,19] . Band at
2974.14 cm-1 and broad band in 1425.86 cm-1 to 1432.19 cm-1 indicate C-H stretching. The broad band of 1042.74 cm-1
to 1050.19 cm-1 is ascribed to in-plane Si-O stretching, and the band of 1100.32 cm-1 was Si-O stretching in
perpendicular mode [18,19]. All of these bands appear in all studied samples.
nc-TiO2/SiO2 MUD EXTRACT 92,5%:7,5%
nc-TiO2/SiO2 MUD EXTRACT 90%:10%

1100,32
1042,74

1432,19

90%:10%

1050,19

1636,97

1425,86

1631,66

1634,83

3201.32
2974.14

3255.39

% Transmittance

3267.60

nc-TiO2/SiO2 TEOS

4000 3750 3500 3250 3000 2750 2500 2250 2000 1750 1500 1250 1000 750 500
-1

Wavenumbers (cm )
Fig. 3. FT-IR spectra for nano-composite of TiO2/SiO2 extracted from mud and synthesized from TEOS

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3.2. DSSC Performance


IPCE curve of the DSSC studied is shown in Fig. 4. This curve represents electron transfer process from dye to the
semiconductor and from oxidized I- to dye [20]. The larger the IPCE value, the more effective electron transfer takes
place. As IPCE value reaches 100%, it indicates that all photon is absorbed by the dye and converted to current [21].
According to the IPCE results in the wavelength range of 400 nm 700 nm the highest IPCE value obtained is at 430
nm (2.604%), this value is far greater than TiO2 without SiO2 [22]. It is known that ~430 nm is in accord with the
wavelength of absorption of anthocyanin from mangosteen pericarp extract [10]. However, the highest IPCE was only
obtained for nano-composite with ratio of 92.5%:7.5%. For ratio 90:10% the IPCE values drop to similar level as pure
TiO2 [13], which could be the effect of SiO2 nature of being insulator. It is interesting to note from this results that the
addition of small amount of SiO2 has led to more effective electron transfer from dye.
0,4
3,0
0,3
IPCE (%)

2,7
2,4
2,1

0,2

0,1

1,8

IPCE (%)

90:10 (TEOS)
90:10 (Extraction)

1,5

0,0
350 400 450 500 550 600 650 700 750

1,2

wavelength (nm)

0,9

92.5:7.5 (E)

0,6
0,3

90:10 (E/T)
0,0
400

450

500

550

600

650

700

Wavelength (nm)
Fig. 4. IPCE value of studied DSSCs.

Fig. 5 presents the I-V characteristics of each solar cells consisting of TiO2/SiO2. The calculated data from I-V
profile are summarized in Table 1. It can be seen that nanocomposite TiO2/SiO2 from mud extract with ratio
92.5%:7.5% has the highest both VOC and ISC at 77.85 mV and 14 A, respectively. DSSC that employs TiO2/SiO2
with ratio 92.5%:7.5% has relatively high JSC than TiO2/SiO2 with ratio 90:10, because the right amount of SiO2 is
important to enhance the performance of DSSC [15].
Table 1. Photovoltaic performance of DSSCs with photoanode consisting of TiO2/SiO2
DSSC
Ratio
VOC (mV) ISC (A)
JSC (mA cm-2) PMAX (mW) FF (%)
TiO2
192
6.5
0.026
0.4000
32.051
TiO2/SiO2 mud extract
92.5:7.5
77.85
14
0.056
0.2977
27.315
TiO2/SiO2 TEOS
92.5:7.5
42.1
4
0.016
0.0492
29.228
TiO2/SiO2 mud extract
90:10
62
1.7
0.007
0.0288
27..362
TiO2/SiO2 TEOS
90:10
76
2.1
0.008
0.0507
31.748

(%)
0.0027
0.0020
0.0003
0.0002
0.0003

The power efficiency (PMAX) of DSSC with nano-composite photoanode TiO2/SiO2 mud extract with ratio
92.5%:7.5% was the highest than the other nano-composites, due to the higher current density. The best efficiency of
nano-composite photoanode is 0.0020% achieved by cells using TiO2/SiO2 mud extract which shows a comparable
results to that of pure TiO2 photoanode.
It is clear that the presence of SiO2 in photoanode of DSSC leads to the higher current density due to the role of
SiO2 as a potential barrier layer. SiO2 is an insulator having band gap of 8-9 eV, it can work as partial barrier around
TiO2 particle accordingly [15]. Furthermore, the recombination of electron in TiO2 film and I3- electrolyte can be
prevented by SiO2. SiO2 that extracted from Sidoarjo mud vulcano has higher current density than SiO2 synthesized

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
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from TEOS. This evidence is likely due to the present of -Al2O3 and -Fe2O3 in extracted SiO2, since the presence of
Fe2O3 in DSSC is known to increase conductivity of sample, fast electron-transport, and short electron life-time [2325]. While, the presence of Al2O3 is known to reduce charge recombination rate between the photoanode and dye [26].
Further investigation is still underway.
0,07
Bare TiO2 NP

0,06

nc-TiO2/SiO2 mud extract 92.5%:7.5%


nc-TiO2/SiO2 TEOS
92.5%:7.5%

-2

JSC (mA cm )

0,05

nc-TiO2/SiO2 mud extract 90%:10%


nc-TiO2/SiO2 TEOS
90%:10%

0,04

0,03

0,02

0,01

0,00
0

50

100

150

200

V (mV)
Fig. 5. Photocurrent density-voltage curve of DSSC with TiO2, TiO2/SiO2 mud extract, and TiO2/SiO2 TEOS for
various ratio.
4.

Conclusions
SiO2 extracted from Sidoarjo mud volcano can be extracted easily and mixed in such a way to be applied as DSSC
photoanode. The TiO2/SiO2 nano-composite showed enhanced performance in comparison with TiO2 nanoparticle
which increases the photocurrent. It is likely that the addition of SiO2, particularly that from Sidoarjo mud volcano
extract, would increase the adsorption of dye on it. However, this depends on the composition, the more SiO2 in the
photoanode would decrease the efficiency accordingly.
5.

Acknowledgements
The authors woud like to thank to Directorate of Higher Education Ministry of Research Technology and Higher
Education for suporting this work under Penelitian Unggulan Tinggi scheme contract number:
003246.136/IT2.11/PN.08/2015
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dye-sensitized solar cells based on P25, Electrochimica Acta, 81(2012), p.246-253.
R. A. Wahyuono, Dye-sensitized solar cells (DSSC) fabrication with TiO2 and ZnO nanoparticle for high conversion
efficiency [Thesis], Institut Teknologi Sepuluh November, Indonesia.
R. A. Wahyuono and D. D. Risanti, Quasi-solid state DSSC performance enhancement by bilayer mesophorous TiO2
structure modification, Advance Material Research, 789(2013), p.93-96.
B. J. Saikia and G. Parthasarathy, Fourier transform infrared spectocospic characterization of kaoline from Assam and
Meghalaya, Northeastern India, J. Mod. Phys, 1(2010), p.206-210.
L. Vaculkov, E. Plevov, S. Vallov, and I. Koutnk, Characterization and differentiation of kaolinities from selected
Czech deposits using infrared spectroscopy and differential thermal analysis, Acta Geodyn. Geomater., 8(2011), p.59-67.
K. Hara, T. Horiguchi, T. Kinoshita, K. Sayama, H. Sugihara, and H. Arakawa, Highly eficient photon-to-electron conversion
with mercuurochrome-sensitized nanophorous oxide semiconductor solar cells, Solar Energy Materials & Solar Cells,
64(200), p.115-134.
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Cells, 92(2008), p.374-384.
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Ektraksi Lumpur Sidoarjo sebagai Inhibitor Korosi dan Partikel Scattering pada DSSC (Dye-sensitized Solar Cells), [in]
Prosiding Pertemuan Ilmiah XXIX HFI Jateng & DIY, 25 April 2015, ISSN: 0853-0823.
M. Cavas, R. K. Gupta, A. A. Al-Ghamdi, Z. H. Gafer, and F. El-Tantawy, Preparation and characterization of dye sensitized
solar cell based on nanostructured Fe2O3, Materials Letters, 105(2013), p.106-109.
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nanostructures by Fe2O3 for enhanced-performance of dye-sensitized solar cell, Material Science in Semiconductor
Processing, 31(2015), p.363-371.
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TiO2 electrodes og dye-sensitized solar cells, Thin Solid Films, 520(2012), p.1745-1750.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
CODE: IM
The Characterization of Mangosteen Pericarp Dye for ZnO-based Dye Sensitized Solar Cells
Robert Mahendra1), Ridho Hantoro1), Doty Dewi Risanti1)
1

Department of Engineering Physics, Institut Tekonologi Sepuluh Nopember, Surabaya 60111, Indonesia

Abstract: The mangosteen tree is a tropical evergreen indigeneous to southern Asia. Its fruits pericarp is known to
contain anthocyanin pigment which could be bound to the surface of a porous semiconductor film offering the highest
efficiency compared to other natural dye for dye sensitized solar cell. The dyes from mangosteen pericarps taken from
various regions in Java were investigated as sensitizers in the ZnO-based DSSC. The absorptance spectra of the dyes
and dye-loaded semiconductor-working electrode were obtained by UV-Vis spectroscopy. In addition, the Fourier
Transform Infrared spectroscopy was used to determine the characteristic functionalities of the dye molecules. Our
result indicated that mangosteen pericarp from Tasikmalaya achieved the highest efficiency (0.020%) amongst the
studied dyes which was attributed to the absence of additional bands between 1100-400 cm-1 in FTIR spectrum.
Keywords: Garcinia mangostana; absorbance; anthocyanin; efficiency
Corresponding author: Robert Mahendra, E-mail: bob.mahendra7@gmail.com
1. Introduction
Natural dyes have been developed for being used as a substitute of Ruthenium complexes in the Dye Sensitized
Solar Cells (DSSC). Among natural dyes, there exists three main families of compounds have been exploited as
sensitizer, namely chlorophylls [1], anthocyanins [1], and betalains[2]. The former have inherent limitations as
sensitizers owing to weak absorption of green wavelengths, the lattest mostly contains in plants that cannot be
cultivated in tropical countries. Anthocyanins, on the other hand, are a very large group of red-blue plant pigments,
which can be found naturally in all higher plants. They are responsible for the colloration of flowers, fruits, fruit juice,
wines, leaves, stems, bulbs, roots, etc [3]. One of cyanin pigmen in anthocyanins that plays an important role in the
process of light absorption is cyanidin 3-O--glucoside [4].
Among many studied plants, mangosteen (Garcinia mangostana L.) pericarp is known to contain almost 51%
anthocyanins [5]. Another research states that mangosteen fruits dark purple pericarps is rich in bioactive secondary
metabolites including anthocyanins, oligomeric proanthocyanins, and xanthones [6]. Mangosteen is a tropical tree and
cultivated for centuries in Indonesia, especially in Java. Based on [7], the conversion efficiency of DSSC for
mangosteen could reach 0.30% higher than the DSSC sensitized by other natural dyes. However, the stability and
reproducibility of this dye may depend on the fruits variant, season, and the soil condition. In this work, the natural
dyes extracted from mangosteen pericarp taken from various region in Java were investigated. The absorption spectra of
these extracts were studied. The performance of the DSSCs employing the studied dyes fabricated on ZnO films was
tested and analyzed.
2. Experimental
The mangosteen pericarps were collected from Tasikmalaya, Ponorogo, Purwakarta, and Blitar. The natural dye
anthocyanin resources were extracted by using ethanol. The dyes extracted were obtained by drying at 60oC in oven for
56 hours. Dried raw dye materials were crushed in a juice mixer. Each of finely ground powder (10 g) was soaked in
100 ml ethanol 96%. The mixture was continuously stirred at 5060oC for 30 min. The mixture was cooled for 20
minutes and stored in a dark glass bottle for a week. The solid sediments were filtered out and the filtrate were used as
photosensitizer [7]. Each extracts were investigated by UV-Vis and FTIR. The amount of anthocyanin concentration in
each mangosteen pericarp was determined through equation (1) using the absorption vaules at pH 1 and pH 4.5 [8].

where :
A

MW
DF
l

: (A520 nm A700 nm)pH 1 (A520 nm A700 nm)pH 4.5


: extinction coefficient (29600 molar, in L x mol1 x cm1)
: molecular weight (449.2 g/mol)
: dilution factor
: pathlength (1 cm)

(1)

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
Details of hybrid ZnO synthesis can be found at [9]. For DSSC assembly, ZnO-coated FTO glass were rinsed with
ethanol and dried. ZnO-coated FTO glass was dipped into dye solution for 12 hours, cleaned with demineralized water
and then dried in air. The dyed photoelectrode and a Pt-coated counter electrode were assembled to form a DSSC by
sandwiching a redox (I/I3) gel electrolyte. DSSCs performance were determined by measuring the current (I) and
voltage (V) produced by DSSC under sunlight and also by measuring photocurrent action spectra or Incident Photon to
Conversion Energy (IPCE) which were fully explained in [9].
3. Results and discussion
3.1. Absorption spectra
The UV-Vis absorbtion spectra for the dyes and dye-loaded semiconductor-working electrode taken from
Tasikmalaya, Ponorogo, Purwakarta, and Blitar are showed in Figure 1. It is seen that the light absorption peak of the
respective dyes are located in the range of 432-462 nm, 436.5-457 nm, 443-459 nm, 407.5-452.5 nm, respectively.
Anthocyanin that contains cyanidin is known to have absorption peak at range of 490-550 nm [10], while the absorption
peak of cyanidin-3-glucoside itself lies in the range of 275-280 nm dan 520-523 nm [8, 11]. However, this cyanidin
peak does not appear in our studied dye due to extraction condition used (pH 5.8) (Fig. 1a). According to [12], at pH 59 anthocyanin degrades and therefore losses its absorption peak at the aforementioned wavelength. On the other hand,
the temperature used for extracting dyes was 60C, this may also cause the degradation of anthocyanin pigment.
According to Fig. 1b, the absorption peak of dye-loaded semiconductor situates in the range of 386-395.5 nm, while
absorption peak of dyes is at 407.5-462 nm. Since absorption peak of ZnO is around 380 nm, it means as the
semiconductor was loaded by the dye the absorption peaks shifts indicating that the dye has properly attached on the
surface of ZnO [13].

2,5

3.0

3,0

Tasikmalaya
Ponorogo
Purwakarta
Blitar

2,5

TASIKMALAYA
PONOROGO
PURWAKARTA
BLITAR

TASIKMALAYA
PONOROGO
PURWAKARTA
BLITAR

2.5

Absorbansi

3,0

2.0

1.5

2,0

Absorbance

Absorbance

2,0

1,5

1.0

0.50

380

390

400

410

420

430

440

450

Panjang Gelombang (nm)

1,5

0.40

0.35

0.30

0.25

1,0

1,0

0.45

0.20

0.15
500

520

540

560

580

600

0,5

0,5

0,0
350

0,0
400

450

500

550

Wave length (nm)

(a)

600

650

700

400

450

500

550

600

650

700

Wave length (nm)

(b)

Fig. 1. Light absorption spectra of (a) dyes and (b) dye-loaded semiconductor taken from Tasikmalaya, Ponorogo,
Purwakarta, and Blitar
Fig. 2 shows the determination of bandgap from dyes and dye-loaded semiconductor by using equation (2) of fitting
procedure for absorption spectra [14].

(v ) hv B ( hv Egap ) m

(2)

where Egap, B, m, dan h are bandgap, a constant, index (1/2, 3/2, 2, and 3), and photon energy, respectively. While
(hv) is absorption coeficient that defined by Beer-Lambeerts Law as:

(v )

2,303 Abs ( )
d

(3)

where d and Abs are film thickness and film absorbance, respectively. The result shows that the smallest bandgap for
dye and dye-loaded semiconductor is obtained for mangosteen pericarp procured from Tasikmalaya.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015

Tasikmalaya
Ponorogo
Purwakarta
Blitar

500

Tasikmalaya
Ponorogo
Purwakarta
Blitar

600

500

400
400
2

(Alp.hv)

(Alp.hv)

300

200

300

200

100

100

0
2,20 2,25 2,30 2,35 2,40 2,45 2,50 2,55 2,60 2,65 2,70 2,75 2,80

2,60 2,65 2,70 2,75 2,80 2,85 2,90 2,95 3,00 3,05 3,10 3,15 3,20 3,25 3,30 3,35 3,40

Energy/hv

Energy/hv

(a)

(b)

Fig. 2. The determination of bandgap energy of (a) dyes and (b) dye-loaded semiconductor collected from Tasikmalaya,
Ponorogo, Purwakarta, and Blitar

Transmittance (a.u.)

100

Tasikmalaya
Ponorogo
Purwakarta
Blitar
C-OH

H-bond

120

aliphatic hydrogen

140

C=C of benzene ring

3.2. IR spectra
Dye needs to have specific functional groups for them to be effectively adsorbed onto photoelectrode. In the
functional groups of chlorophyll dye and anthocyanin dye, esters, hydroxyl groups (-OH), and carbonyl groups (-CO)
bound with ZnO [2]. Carbonyl and hydroxyl group will be easily bound with ZnO, leading to the improved efficiency
by faster light harvesting that occurred from dye molecule to ZnO. Alcohol and ester groups lying at 1050-1200 cm-1
are ineffectual, while O-H stretching at 3200-3600 cm-1 is more valuable. The non-crystalinity may be appeared at 6501000 cm-1 that caused sharpness reduction in overall spectrum [15].
Fig. 3 shows the FTIR spectra of all studied dye extracted at pH5.8.All studied dyes reveal O-H stretching band that
is observed at 3600-3000 cm-1 as indicative of the presence of anthocyanin. C=O stretching vibration is visible at 17001600 cm-1 and C-O-C stretching vibration is at 1200 cm-1. For more detail, Table 1 shows the transmission pattern of
anthocyanin extracted that be compared with standard.

Bound
type

80

60

40
C-H

20

0
4500

4000

3500

3000

2500

2000

1500

1000

Table 1 Anthocyanin extracted of mangosteen pericarp wave


band compared to standard [16]

500

C-OH
(ethanol)
C-O-C
C-H
C=O
Aliphatic
hydrogen
OH
group

Transmiss
ion peak
at
Tasikmala
ya (cm-1)

Transmiss
ion peak
at
Ponorogo
(cm-1)

Transmissio
n peak at
Purwakarta
(cm-1)

Transmissio
n peak at
Blitar (cm-1)

1060.00

1078.24

1093.67

1064.74

1170.00
1402.00
1629.97

1157.33
1404.22
1635.69

1153.47
1458.23
1608.69

1093.67
1510.31
1649.19

1188.90
1456.30
1614.47

2934.98

2962.76

2899.11

2931.90

3429.00

3435.34

3375.54

3315.42

3392.90

Transmis
sion peak
standard
(cm-1)

-1

Wave band (cm )

Figure 3. FTIR spectra of mangosteen pericarp taken


from Tasikmalaya, Ponorogo, Purwakarta, and Blitar
3.3. Calculation of anthocyanin pigment concentration
According to equation (1), the amount of anthocyanin pigment is shown in Fig. 4. One of the factors affecting the
color of anthocyanin is pH. Acidic (methoxy groups) can make the anthocyanin becomes red, whereas alcanity
(hydroxy groups) causes its color change into blue and becomes unstable. Besides, the pigment concentration,
copigmentation, the amount of hydroxy and methoxy also affect the color of anthocyanin [17]. At pH 1, anthocyanin is
in the form of oxanium, which represents the amount of its anthocyanin and a little of nuisancs compounds. While at pH
4.5, anthocyanin is in the form of hemiketal, suggesting the degradation of colored anthocyanin into colorless. This
change causes represents the amount of nuisance compounds [11].

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015

88,777

Anthocyanin content (mg/g)

80

74,513

60

41,885

39,153

40

20

0
Tasikmalaya

Ponorogo

Purwakarta

Blitar

Plantation of Origin

Fig. 4. Anthocyanin content of studied dyes according to their origin.


3.4. DSSC performance
DSSCs performance was determined by measuring the current (I) and voltage (V) produced by DSSC under direct
sunlight measured at 10.00-14.00 WIB. I-V curve is shown in Fig. 5. In general the highest Voc value was obtained of
mangosteen pericarp from Tasikmalaya for both ZnO used. Although the dye was extracted at pH 5.8, the mangosteen
pericarp taken from Tasikmalaya results in better efficiency among the studied dyes (Table 2). This results is in
accordance with the IPCE spectra (Fig. 6). The highest IPCE value obtained from the mangosteen pericarp taken from
Tasikmalaya, 0.037 % (mixture) and 0.042 % (bilayer). This may indicate that dye from mangosteen pericarp originated
from Tasikmalaya is well adsorbed into ZnO. It is noted that although the amount of anthocyanin in mangosteen
pericarp originated from Blitar is the highest, it does not lead to higher efficiency. All studied dyes show the presence
of C-O-H band in Fig. 3 among which dye using pericarp from Tasikmalaya does not have this feature showing that the
C-O-H bond in this mangosteen pericarp was more reacted and consumed. Consequently, the concentration of dye is
expected to be higher for pericarp from Tasikmalaya than others, probably because of a higher solubility. Another
feature affecting the dye is the acidity of the extract which likely influences the solubility of the dye [18].

TASIKMALAYA
PONOROGO
PURWAKARTA
BLITAR

20

30

TASIKMALAYA
PONOROGO
PURWAKARTA
BLITAR

25

Current (A)

Current (A)

15

10

20

15

10
5

5
0
0

50

100

150

200

Voltage (mV)

250

300

350

0
0

100

200

300

400

Voltage (mV)

(a)

(b)

Fig. 5. I-V curve of mangosteen pericarp taken from Tasikmalaya, Ponorogo, Purwakarta, and Blitar using method of
(a) mixer and (b) bilayer.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015

Hybrid method
Mixer

Bilayer

Table 2. Photelectrochemical parameter of DSSCs


ZnO variation
Regions
FF (%)
Voc (mV)
Tasikmalaya
0.222
367.0
Ponorogo
0.243
301.5
Nanoflower : Nanotree
Purwakarta
0.241
263.5
Blitar
0.311
216.5
Tasikmalaya
0.242
379.5
Ponorogo
0.296
264.1
Nanorod : Nanoflower
Purwakarta
0.208
405.4
Blitar
0.198
367.7

Isc (A)
22.8
16.9
14.7
14.9
32.2
23.5
19.8
18.3

Eff (%)
0.012
0.008
0.006
0.007
0.020
0.012
0.011
0.009

0.05

0.040

NANOFLOWER+NANOTREE (MIXTURE)

NANOROD+NANOFLOWER (BILAYER)

0.035

0.04

IPCE (%)

IPCE (%)

0.030
0.025
0.020

TASIKMALAYA
PONOROGO
PURWAKARTA
BLITAR

0.015
0.010

0.03

TASIKMALAYA
PONOROGO
PURWAKARTA
BLITAR

0.02

0.01

0.005
0.00

0.000
350

400

450

500

550

600

Panjang
Gelombang
Wave length
(nm) (nm)

650

700

350

400

450

500

550

600

650

700

Panjang
Gelombang
Wave length
(nm) (nm)

(a)
(b)
Fig. 6. The photocurrent spectra of mangosteen pericarp taken from Tasikmalaya, Ponorogo, Purwakarta, and Biltar
using method of (a) mixer and (b) bilayer.
4.

Conclusion
Natural dye extracted from mangosteen pericarp collected from various regions have been examined and tested onto
two type ZnO photoanodes. The dye originated from Tasikmalaya offers the highest efficiency and IPCE among other
studied dyes. Under this condition more anthocyanin was consumed in ethanol solution leading to an increase in
anthocyanin solubility.
Acknowledgements
This research was partially funded through Strategis Nasional Research Scheme from Directorate of Higher
Education Ministry of Research and Higher Education under contract number 07555.28/IT2.7/PN.01.00/2014.
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The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
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The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015

CODE: IM
The Design of Spectroscopic Ellipsometry for Measuring the Dielectric Constant and the Thickness of Graphene
on SiO2/Silicon Substrate Using Single Wavelength Light Source
Kiki Megasari, Edi Suharyadi, Rinto Anugraha, Kamsul Abraha, Iman Santoso*
Departmen Fisika, Universitas Gadjah Mada, Sekip Utara BLS 21 Yogyakarta, Indonesia, 55281
Abstract: The measurement system for determining dielectric constant and thickness of graphene on SiO2/Silicon
substrate using ellipsometry technique has been developed. The basic principle that used in spectroscopic ellipsometry
(SE) is to analyze the changes in the phase difference and the amplitude ratio between p- and s- polarized
reflected light. In this work, the SE configuration that been used is Rotating Analyzer Ellipsometry (RAE) with He-Ne
laser (wavelength = 632,5 nm) employed as a light source. Using numerical Newton-Raphson inversion method we
obtained the dielectric constant and the thickness of graphene on SiO2/Si substrate at three different angle of incidences
(60,62, and 64) as follows: =-10.2272 - 9.9276i with thickness of 0.355 nm , =-11.1858 - 5.7758i with
thickness of 0.355 nm, and =-13.7523 - 0.7546i with thickness of 0.355 nm. The results have not been agreed with
the reference values. The discrepancy may come from the additional optical component (beam splitter) that we used on
top of our basic RAE configuration.
Keyword: Dielectric constant; spectroscopic ellipsometry; Newton Raphson; graphene
Corresponding author: Iman Santoso, Email: iman.santoso@ugm.ac.id
1. Introduction
The characterization of nanostructure material had been studied through many detection methods. One of the
methods that widely used is Spectroscopic Ellipsometry (SE). SE allows us to measure the change of phase difference
and amplitude ratio between p- and s-polarized reflected light which make its polarization to be elliptic. The SE
widely used for extracting the dielectric constant and the thickness of thin film of the materials. SE measurement has an
advantage compare to other techniques like direct reflectivity measurements because it gives both the real and
imaginary parts of the dielectric constant together without doing Kramers-Kronig transformation. Moreover, in case of
very thin film, the change in phase of polarized light is very sensitive toward the existence of thin film with thickness
up to 0.01 nm. Therefore the measurement of thin film using SE system will yield more accurate and reliable data [1,2].
These facts make SE an ideal method for analyzing systems like graphene on a substrate. Graphene, two dimensional
material composed of carbon atoms that form a monolayer hexagonal honeycomb structure, has attracted great number
researchers to study it until now. Typical properties of graphene include Dirac Fermion, electron ballistic transport,
quantum Hall effect, and chiral tunneling [3,4]. Kravets et al [5] has conducted initial study of optical properties of
graphene and the thickness of the layers on the SiO2/Si substrate using SE. Other studies on graphene using the SE has
been done to investigate the substrate effect on many-body interactions[6], the disorder induced change of the manybody interactions[7] and the nature of free standing graphene multilayer epitaxial graphene on C-face [8]. However,
those studies utilize commercial SE systems (for instance SENTECH and WOOLLAM) which are very expensive
instrument. Therefore developing the low-cost yet sensitive ellipsometer independently should be conducted in order to
characterize the nanostructure materials without losing its capabilities and without spending too much cost.
2. Research Method
The schematic design of SE measurement system is shown in Figure 1. In this work we use the Rotating Analyzer
Ellipsometry (RAE) configuration which is simpler mode as compared to others [1]. This system consist of He-Ne laser
(Newport, wavelength = 632.8 nm) as a source of electromagnetic waves in the form of linear polarization, polarizer,
analyzer (Newport, 10LP-Vis-B), beam splitter, sample holder and two detectors (Sanwa laser power meter, LP1).
Polarizer is set at an angle of 45 which is intended to obtain the same intensity of p- and s-polarized light. Beam
Splitter (NBS newport) is used to split a laser beam into two parts with the same intensity. The first detector is used to
capture the intensity of laser reflected from the beam splitter (in microwatt), while the second detector is used for
capturing the intensity of laser beam transmitted from the beam splitter. The intensity from first detector is used to
normalize the intensity from second detector. The sample holder can be rotated around 360. This tool is used to vary
the angle of incidence. Analyzer is used to rotate the polarization angle of the reflected laser light.

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Fig. 1. Ellipsometry set up at Laboratory of Material Physics and Instrumentation, Universitas Gadjah Mada that consist
of (1) He-Ne laser, (2) polarizer, (3) beam splitter, (4) laser power meter, (5) turning table, (6) sample holder, (7)
semple, (8) analyzer, and (9) laser power meter.
We use gold (purchased from goodfellow), silicon (Si) wafer (purchased from Cree), and graphene on SiO2 /Si
substrate (purchased from graphene supermarket) for SE measurement.
In RAE configuration, the polarizer angle polarizer and the incident angle are fixed at, 45o and 60 to 64 with the
lapse of 2, respectively, while the analyzer angle is varied from 0 to 180 for every 5o.The intensity as function of
analyzer angle is described by [1]:

I (t ) I 0 1 cos 2t sin 2t .
By using Fourier analysis, one can obtain the Fourier coefficients a0 , a1 , and

(1)

b1 which are related to the values of

I0, , and

, respectively.
The and are related to phase difference and amplitude ratio through following relation[1]:
tan

tan P , cos
1
1 2

(2)

From the and value, the dielectric constant will be extracted using pseudo functions formulas for bulk
material[1]. As for thin film one has to model the p- and s- polarized reflected light using Fresnel equation [1]. The
dielectric constant can be extracted by using inversion methods employing numerical Newton Raphson method.
3. Results and Discussion
3.1. The SE measurements of gold (Au) with the angle of incidences of 60, 62, and 64

intensity

0.5

0.4

0.3

gold (60 deg)


gold (62 deg)
gold (64 deg)

0.2
0

50

100
angle of analyzer (deg)

150

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Fig. 2. Measurement of intensity versus analyzer angle for gold (Au) with incidence angles of 60, 62 and 64.
Psi and delta values of the experimental results in Fig. 2 are determined by firstly calculating the Fourier coefficient.
The dielectric constant then can be extracted through mathematical inversion method employing numerical Newton
Raphson method.
Tabel. 1. The measurement results of samples of gold (Au) on the angle of incidence (60-64)
Incidence
dielectric constant
Refractive indexs
psi ( ) delta ( )
angle
60
51.2664
116.742
-4.3511 + 2.7073i
0.6219 + 2.1767i
62

51.0721

111.1057

-4.3929 + 2.5203i

0.5795 + 2.1746i

64

51.4278

104.4579

-4.1858 + 2.4922i

0.5856 + 2.1281i

From Table I, it can be inferred that dielectric constant obtained from this measurement is not in accordance with the
reference (i.e. -10.5618 - i1.2769). Therefore, it needs to be corrected to some parameters in order to obtain the
expected results. The correction can be done by using calibration equation as described by Equations (3) and (4) to
determine the correlation between the alpha and beta values on the calculation of the value of alpha and beta
experimental results (correction I). This calibration procedure yields to calibration constants () and shifted angle
analyzer (As) [1]:

I ( t ) I o 1 cos 2 ( t As ) sin 2 ( t As )

1 cos 2 As
sin 2 A

s

Tabel 2. Correction I parameters

sin 2 As
cos 2 As

Incidence
angle
60

Calibration
constant
0.7266

As
14.28

62

0.6649

16.29

64

0.5950

20.37

(3)

(4)

3.2. The SE measurements of silicon (Si) with the angle of incidences of 60, 62, and 64

intensity

0.20

0.15

0.10

Si (60 deg)
Si (62 deg)
Si (64 deg)
0

50

100
angle of analyzer (deg)

150

Fig. 3. Measurement of intensity versus analyzer angle for silicon (Si) with incidence angles of 60, 62 and
64.

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Using the same method as described in measurement of gold, one can obtain the intensity versus analyzer angle as
shown in Fig. 3. The dielectric constant that is extracted using pseudo function and numerical Newton-Raphson method
can be seen in Table 3. The results are not in accordance with the reference value (i.e. 13 - i0) and requires the
correction. Using the same procedure described previously (correction I), one can obtained the corrected dielectric
constant as shown in Table 4.
Tabel 3. Results without correction for silicon
Incidence
angle

Silikon
psi ( )

delta ( )

dielectric constant ( )
Pseudo function
Newton Raphson

60

34.6094

123.4464

-3.8729 - 5.3016i

-3.8726 - 5.3014i

62
64

35.6625
33.3764

115.0956
118.1516

-4.1022 - 4.2338i
-4.4883 - 6.7671i

-4.1024 - 4.2337i
-4.4881 - 6.7671i

Tabel 4. Corrected results for silicon using correction I procedure


Incidence
angle

Silikon
psi ( )

delta ( )

60

19.9172

127.4375

62
64

21.5065
6.0066

111.4897
124.9054

dielectric constant ( )
Pseudo function
Newton Raphson
2.7474 - i4.714

2.7461 i4.7155

1.4253 - i4.5493
4.867 - i1.4613

1.4276 i4.5493
4.8635 i1.4599

3.3. The SE measurements of SiO2 on Silicon Substrate with the angle of incidences of 60, 62, and 64

SiO2 (60 deg)


SiO2 (62 deg)
SiO2 (64 deg)

0.25

intensity

0.20

0.15

0.10

50

100
angle of analyzer (deg)

150

Fig. 4. Measurement of intensity versus analyzer angle for SiO2 on silicon substrate with incidence angles of
60, 62 and 64.
Using the same method as described in measurement of gold, one can obtain the intensity versus analyzer angle as
shown in figure 4. The dielectric constant that is extracted using numerical Newton-Raphson method can be seen in
Table 5. The results are not in accordance with the reference value (i.e. 2.2 - i0) and requires the correction. Using the
same procedure described previously (correction I), one can obtain the corrected dielectric constant, shown in Table 6.

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Incidence
angle

Tabel 5. Results without correction for SiO2 on Silicon


SiO2
dielectric constant (
Thickness
~
(nm)
)
psi
delta ( )

( )
60

32.7687

112.6615

-2.1077 - 3.7117i

300

62
64

31.7115
29.5046

111.0617
109.0641

-2.1926 - 4.4726i
-1.7559 - 5.4660i

300
300

Tabel 6. Corrected results for SiO2 on Silicon using correction I procedure.


Incidence
SiO2
dielectric constant (
Thickness
~)
angle
(nm)

psi
delta ( )

( )
60

21.5023

102.8337

1.0410 - 3.0339i

300

62
64

17.0888
7.8384

94.5946
39.6014

1.9143 - 2.7912i
3.4969 - 1.1581i

300
300

3.4. The SE measurements of Graphene on SiO2 /Silicon Substrate with the angle of incidences of 60, 62, and
64

0.24

G/SiO2 (60 deg)


G/SiO2 (62 deg)
G/SiO2 (64 deg)

0.22

intensity

0.20
0.18
0.16
0.14
0.12
0.10

50

100
angle of analyzer (deg)

150

Fig. 5. Measurement of intensity versus analyzer angle for Graphene on SiO2/silicon substrate with incidence
angles of 60, 62 and 64.
Using the same method as described in measurement of gold, one can obtain the intensity versus analyzer angle as
shown in Figure 5. The dielectric constant that is extracted using numerical Newton-Raphson method can be seen in
Table 7. The results are not in accordance with the reference value (i.e. 5 i8) and requires the correction. Using the
same procedure described previously (correction I), one can obtain the corrected dielectric constant, shown in Table 8.
Tabel 7. Results without correction for graphene on SiO2/Silicon substrate
Incidence
SiO2
dielectric constant (
Thickness
~
angle
(nm)
)
psi
delta ( )

( )
60

34.7869

107.5258

-4.6883 -25.8730i

0.355

62
64

33.3171
31.9800

104.5615
100.5430

-6.3927 -23.9010i
-8.0736 -22.8704i

0.355
0.355

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Tabel 8. Corrected results for graphene on SiO2/Silicon substrate using correction I procedure
Incidence
SiO2
dielectric constant (
Thickness
~
angle
(nm)
)
psi
delta ( )

( )
60

26.2919

98.0701

-10.2272 - 9.9276i

0.355

62
64

23.2047
21.1641

87.7290
66.1570

-11.1858 - 5.7758i
-13.7523 - 0.7546i

0.355
0.355

It can be seen that the overall dielectric constant results, either without correction or with correction, are not in
accordance with the reference. This discrepancy may come from the fact that we use additional optical component
(beam splitter) on top of our basic RAE configuration. Thus it is necessary to include Jones matrix of beam splitter in
calculating the expression for the intensity of the reflected light as a function of analyzer angle.
4.

Conclusion
In conclusion, we have developed the home-made SE measurement system which is able to determine the dielectric
constant and the thickness of nanostructured material (i.e.graphene on SiO2/Si substrate) even though the results have
not been approached the reference values. The discrepancy may come from the additional optical component (beam
splitter) that we used on top of our basic RAE configuration.
Acknowledgements
We would like to express our gratitude to Universitas Gadjah Mada Yogyakarta in supporting this work through
PUPT research grant.
References
[1] Fujiwara, H., 2007, Spectroscopic Ellipsometry Principles and Applications, John Wiley & Sons, Ltd.
[2] Verbruggen, M. H. W and de Nijs, 1992, Analysis of spectroscopic ellipsometric measurements, Computer Physics
Communications 69, 201-214.
[3] Novoselov, K.S., Geim, A.K., Morozov, S.V., Jiang, D., Zhang, Y., Dubonnos, S. V., Grigorieva, I. V., Firsov. A.
A., 2004, Electric Field Effect in Atomically Thin Carbon Films. Science 306, 666
[4] Castro Neto, A.H., Guinea, F., Novoselov, K.S., and Geim, A.K., 2009, The Electronic Properties of Graphene,
Reviews of Modern Physics, Volume 81, 109.
[5] Kravets, V,G., Grigoren, A.N., Nair, R.R., Blake, P. Anissimora, S., Novoselov, K.S., and Geim, A.K., 2010,
Spectroscopic Ellipsometry of Graphene and an Excitonic-Shifted van Hove Peak in Absorption, Phys. Rev. B81,
155413.
[6] Gogoi, P. K., Santoso, I., Saha, S., Wang, S., Castro Neto, A. H., Loh, K. P., Venkatesan, T., Rusydi, A., 2012,
Optical Conductivity Study of screening of many-body effects in graphene interfaces, Europhys. Lett. 99, 67009.
[7] Santoso, I., Singh, R.S., Gogoi, P.K., Asmara, T.C., Wei, D., Wee, A.T.S, Pereira, V.M., and Rusydi, A., 2014,
Tunable Optical Absorption and Interaction in Graphene via Oxygen Plasma, Phys. Rev. B 89, 075134.
[8] Iman Santoso, Wong Swee Liang, Pranjal Kumar Gogoi, Teguh Citra Asmara, Han Huang, Wei Chen, Andrew
Thye Seen Wee, Andrivo Rusydi., 2014, Optical Conductivity of Quasifreestanding Graphene Films on the Carbon
Face of SiC, Europhys. Lett.108 (3), 37009.

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CODE: IM
Investigation of Magnetic Properties of Copper Ferrite (CuFe2O4) Nanoparticles Encapsulated by Polyethylene
Glycol (PEG-4000) and Silica (SiO2)
Muh Pauzan1), Edi Suharyadi1)
Department of Physics, Universitas Gadjah Mada, Yogyakarta 55281, Indonesia

Abstract: CuFe2O4 magnetic nanoparticles have been synthesized by coprecipitation method. Polyethylene glycol
(PEG-4000) and silica was used to encapsulate the nanoparticles. The obtained results from XRD confirm that CuFe2O4
has inverse spinel structure with presence of other phases. After encapsulation of PEG and silica, CuFe2O4 show that
FTIR spectra has shifts of absorption bands and form a new absorption band of Fe-O. In magnetic studies,
magnetization (H=15 kOe) of CuFe2O4 is 5.9 emu/g, after encapsulation with PEG and silica, M increases from 10.8 to
14.1 emu/g and from 11.0 to 24.5 emu/g respectively. Coercivity (Hc) of CuFe2O4 is 125.0 Oe, Hc decreases to 45.8 Oe
and 45.6 Oe after PEG and silica encapsulation respectively.
Key words: CuFe2O4; polyethylene glycol; silica; magnetization; coercivity
Corresponding author: Edi Suharyadi, E-mail: esuharyadi@ugm.ac.id, Tel. +62-274-545-185
1. Introduction
In the last few decades, research about magnetic nanoparticles have been took a great attention due to their physical
properties that different from bulk. One kind of magnetic nanoparticles is CuFe2O4. The nanoparticles have emerged as
a new generation of catalysts owing to their large surface area, easy dispersion in several solvents and more remarkably,
their efficient recovery from the reaction medium by magnetic separation [1]. Research about CuFe2O4 nanoparticles
has been focused on the catalytic processes, their applications in other fields are not developed yet. Therefore its
needed to analyze the CuFe2O4 potency in other fields. One technique is encapsulation on the nanoparticles surface. It
is important because encapsulation has advantages when CuFe2O4 nanoparticles interact with the environment.
Advantages of the encapsulation are to prevent the agglomeration in solution, to chain ligand or biomolecules, to
enhance the thermal stability of the nanoparticles, and to decrease poisonous effects in physiological medium.
Researchers are used to using polymer molecules or other compatible substances to encapsulate magnetic
nanoparticles [2]. The substances that are used to encapsulate magnetic nanoparticles are polyethylene glycol (PEG),
alginate, polyester synthetic, silica (SiO2), chitosan, polyvinyl alcohol (PVA) and Aurum [3]. Chitosan has shortage
such long time encapsulation [4], PVA need many processes [3], and Aurum is very expensive.
Compared to the others, silica and PEG have many advantages of encapsulation processes. Silica encapsulated
nanoparticles is easy to be dispersed in solution, shield the nanoparticles from washing in acidic conditions, easier to
activate the nanoparticles, and bring out the surface with functional groups due to silanol groups of silica. Afterwards
the surface of silica is inert therefore it would not give the negative effects while the magnetic nanoparticles are in
biological systems [5,6]. Precursors are compounds that used for encapsulation process, precursor of silica has some
kinds such as tetra ethyl ortho silicate (TEOS) and sodium silicate (Na2SiO3). TEOS and sodium silicate are nonmagnetic substances (except ferrimagnetic/ferromagnetic properties). TEOS has poisonous properties and expensive
[7], whereas sodium silicate has lesser poisonous properties, inexpensive, and easier to be obtained than TEOS. Sodium
silicate is precursor with simple encapsulation process and its process in the room temperature.
It is important to do encapsulation of CuFe2O4 nanoparticles because encapsulation has a function to functionalize
the nanoparticles so that CuFe2O4 applicable for some fields. PEG-4000 and sodium silicate precursor are used to
encapsulate CuFe2O4 nanoparticles. In this research CuFe2O4 nanoparticles would be synthesized by coprecipitation
method. The aim of this research is to investigate the crystallographic information (crystal structure, crystallite size and
lattice parameter) and magnetic properties of CuFe2O4 before and after encapsulation with PEG-4000 and silica. PEG
and silica have paramagnetic and diamagnetic properties respectively. Therefore, PEG and silica would affect the
magnetic properties of CuFe2O4.
2. Experimental
CuFe2O4 is synthesized by coprecipitation method, the compunds are: HCl, CuCl2.2H2O, FeCl3.6H2O, deionized
water, aceton, and NaOH. FeCl3.6H2O is prepared 2.650 g, CuCl2.2H2O 0.754 g, and NaOH 19.99 g. CuCl2.2H2O
dissolved in 7 ml deionized water while FeCl3.6H2O in 14 ml. 100 ml deionized water mixed with NaOH until
homogenous. CuCl2.2H2O and FeCl3.6H2O solutions mixed then 3.37 ml HCl added. This solution is dropped into the
NaOH solution at 50oC and stirred at 450 rpm. After 120 minutes the solution washed 6 times by deionized water,
afterwards heating the precipitate at 90oC for 165 minutes CuFe2O4 powder obtained.
Encapsulation with PEG: PEG added into 10 ml deionized water and stirred until homogenous, 0.5 CuFe2O4 added
into the solution and stirred for 60 minutes. Solution separated from the precipitate by using pipette. The precipitate is

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saved at the room temperature until dry. This experiment was carried out for 6 samples with variation concentration of
PEG such as: 80%, 75%, 66%, 50%, 33% and 25% labeled as P1, P2, P3, P4, P5, and P6 respectively.
Encapsulation with silica: Precursor of sodium silicate Na2SiO3 added into 15 ml deionized water and stirred until
homogenous, 0.6 g CuFe2O4 added into the solution and stirred for 300 minutes. The solution washed by deionized
water for 5 times. The precipitate is saved at the room temperature until dry. This experiment was carried out for 6
samples with variation concentration of Na2SiO3 such as: 50%, 30%, 20%, 15%, 10% and 5% labeled as S1, S2, S3, S4,
S5, and S6 respectively.
The CuFe2O4 nanoparticles characterized by X-Ray diffractometer (XRD), Fourier Transform Infrared spectroscopy
(FTIR), and Vibrating Sample Magnetometer (VSM). After encapsulation by PEG and silica, the samples characterized
by XRD, FTIR, and VSM.
3. Results and discussion
3.1 PEG-4000 encapsulation on CuFe2O4
3.1.1. Characterization by XRD
The XRD pattern of CuFe2O4 and PEG encapsulated CuFe2O4 as shown in figure 1.

Fig. 1. XRD pattern of CuFe2O4(a) and PEG encapsulated CuFe2O4(b)


Figure 1 shows that new peaks are formed for the PEG encapsulated CuFe2O4, the peaks are at 2 = 22.30 , 25.64
and 43.27o. At 2 = 43.27 is a new peak at (400), indicates that after encapsulation with PEG the crystallinity of The
CuFe2O4 is higher. At 2 = 22.30 is FeO(OH)/goethite, and at 2 = 25.64 is FeO(OH)/lepidocrocite. The
phases are formed because Fe3+ ions that fill tetrahedral and half of octahedral site chain with hydroxyl groups of PEG
on the surface of The CuFe2O4. By using match software, all of the high intensity peaks are indexed and refined as
inverse spinel structure with Fd-3m space group.
Diameter (t), lattice parameter (a), and intensity is calculated by using Origin8 software and Scherrer formula and
equation of Brags law to calculate the diameter (t), and lattice parameter (a). The results are showed in the table 1
below.
Table 1 Diameter, lattice parameter and deviation of a before and after encapsulation with PEG-4000.
Sample

Diameter t (nm)

Lattice parameter

CuFe2O4

5.00.1

0.8390.001

CuFe2O4 +PEG-4000

8.80.2

0.8400.001

(nm)

As shown in table 1, diameter after encapsulation is bigger than the diameter of CuFe2O4. This indicates that PEG
chain with CuFe2O4 on its surface. Reduced intensity after encapsulation indicates that PEG on the CuFe2O4s surface is
chained, PEG is non crystalline structure (amorf) so that its reduced the intensity of diffraction.
Deviation of lattice parameter of PEG encapsulated CuFe2O4 is bigger than that of The CuFe2O4. The value is
affected by hydroxyl group of PEG that substituted O2- ions on the surface of The CuFe2O4. Percentage of ferrite phase
(CuFe2O4) increase after encapsulation, besides the presence of other phase hematite and CuO decrease. Decreasing
amount of hematit and CuO phase indicates that PEG could diminish oxidation reaction on CuFe2O4.

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3.1.2. Analysis of absorption bands by FTIR
CuFe2O4 nanoparticles are analyzed their absorption bands before and after encapsulation by PEG. The absorption
bands analyzed by FTIR as shown in figure 2.

Fig. 2. Functional groups of CuFe2O4(a), PEG-4000(b) and CuFe2O4+PEG-4000(c).


CuFe2O4 (fig.2.a)has absorption bands that indicate OH, Fe3+- O2- and Cu2+-O2- chain, as shown in figure 3
absorption bands at ~ 1627.92 cm-1 and 3410.15 cm-1 refers to OH (hydroxyl) vibration. This indicates that CuFe2O4
nanoparticles absorbs water, furthmore the surface of CuFe2O4 is reactive to hydroxyl group of water molecules. The
absorption bands at ~ 601.79 cm-1 and 362.62 cm-1 refers to stretching vibration of Fe-O octahedral and Fe-O
tetrahedral respectively.
FTIR spectra of PEG-4000 (fig.2.b)has absorption bands refer to -OH, H-C-H, C-O, C-O-C, and C-C functional
group. Absorption band at ~ 3348.72 refer to OH vibration. Absorption band at 2877.79 cm-1 refer to CH chain, and
absorption band at ~ 1103.28 cm-1 refer to C-O-C vibration. Besides absorption bands at ~ 1056.99 cm-1, 956.69 cm-1
and 840.96 cm-1 refers to C-C vibration. The presence of some functional groups that refers to PEG indicates that all
kinds of PEG chains is identified.
FTIR spectra for PEG encapsulated CuFe2O4 (fig.2.c) has shift of absorption bands and forms new absorption band
compared with PEG and CuFe2O4 spectra. The absorption bands at range 3410.153448.72 cm-1 are hydroxyl (-OH)
vibrations. After encapsulation, the wave number at hydroxyl vibration is 3425.58 cm-1 that smaller compared with
hydroxyl group of PEG. The shift means hydroxyl group is not free anymore but chain with CuFe2O4 nanoparticles. The
same thing happen to OH bending. The new absorption band formed after encapsulation at 447.49 cm-1 indicates that
Fe3+ ions in octahedral site absorb the hydroxyl functional group. This affects vibration of Cu2+ atoms in octahedral site
with the shift wave number from 362.62 cm-1 become 354.90 cm-1. Absorption band at ~ 601.79 cm-1 is asimetric
stretching vibration in tetrahedral site. At the wave number ~ 354.90 cm-1 and 447.49 cm-1 is asimetric stretching
vibration in octahedral site. Both the shifts of wave number at -OH, H-C-H, C-O, C-O-C, C-C functional group of PEG
and new functional group Fe-Ooctahedral formed at ~ 447.49 cm-1 indicate that PEG succesfully encapsulate CuFe2O4
nanoparticles.
3.1.3. Analysis of magnetic properties by VSM
From the hysteresis loops could be obtained the magnetization at H=15 kOe and coercivity ( ) as shown in table 2.
Table 2
and magnetization at H=15 kOe of CuFe2O4 and CuFe2O4+PEG
No

Sample

1
2
3
4
5
6
7

P1
P2
P3
P4
P5
P6
M

PEG-4000
concentration (%)
80
75
66
50
33
25
0

Magnetization at
H=15 kOe (emu/g)
10.8
10.1
13.0
13.5
13.4
14.1
5.9

Coercivity
45.8
45.6
48.1
45.5
47.0
49.2
125.0

(Oe)

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Table 2 shows that magnetization at H=15 kOe for CuFe2O4 (sample M) is smaller than PEG encapsulated CuFe2O4
samples. Hysteresis loops (at figure 4) of M sample inclined to saturation whereas PEG encapsulated CuFe2O4 samples
are not saturation yet.
Amount of CuFe2O4 phase before encapsulation is 69.94% (ferrimagnetic phase), 15.37% hematit (antiferromagnetic
phase), and 14.68% CuO (antiferromagnetic phase). The amount 30.06% of antiferromagnetic phase affects magnetic
respon of the sample that is not too reactive to external magnetic fields. After encapsulation the amount of CuFe2O4
increase to 78.13%, hematit and CuO decrease to 12.04% and 5.54% respectively. Increase amount of ferrimagnetic
phase (CuFe2O4) affects the samples much more reactive to the magnetic fields. Honestly after encapsulation is formed
FeO(OH) and FeO(OH) that are antiferromagnetic and paramagnetic phase respectively. But the amount of
those phase is little so that their presence is not affect to the magnetic properties of samples.
Magnetization at H=15 kOe increase with the decrease concentration of PEG. PEG has paramagnetic properties, so
that the increasing concentration of PEG causes the magnetization (at H=15 kOe) decrease. Saturation magnetization of
CuFe2O4 bulk is 33.4 emu/g, whereas the
of CuFe2O4 nanoparticles is 80% of that bulk. The smaller
of the
nanoparticles caused by spin canting formed on the surface of nanoparticles.
The coercivity estimated at the single domain, so that the coercivity of CuFe2O4 (diameter 5.0 nm) should smaller
than that of CuFe2O4+PEG (diameter 8.8 nm). But the hysteresis loop of CuFe2O4 inclined to saturation whereas PEG
encapsulated CuFe2O4 samples are not saturation yet. So comparing the
is not appropriate. Besides decreasing
diameter of nanoparticles decreaseing anisotropy energy. Therefore before encapsulation the CuFe2O4 nanoparticles is
easier to magnetized compare with PEG encapsulated CuFe2O4.
3.2 Silica (SiO2) encapsulation on CuFe2O4
3.2.1. Characterization by XRD
The XRD pattern of CuFe2O4 and silica encapsulated CuFe2O4 is shown in figure 3.

Fig. 3. XRD pattern of CuFe2O4(a) and silica encapsulated CuFe2O4(b).


As shown in figure 3, after silica encapsulation the sample has a diffraction peak that shift at (311) and has higher
intensity as well. Besides new peak at (222) formed because encapsulation process needs 5 hours at 450 rpm. Therefore
the process causes silane groups (SiO) of silica substitute O2- on CuFe2O4 surface. Besides atomic structure that is not
arranged before encapsulation become arranged well so that new peak formed at (222). The SiO substitutes O2- causes
shift of diffraction peak at (311).
Full width at half maximum (FWHM), and intensity is calculated by using Origin8 software, Scherrer formula and
equation of Brags law to calculate the diameter (t), and lattice parameter (a). The results are shown in the table 3.
Table 3 Diameter, lattice parameter and deviation of a before and after encapsulation with silica.
Sample

Diameter t (nm)

CuFe2O4
CuFe2O4 +SiO2

5.00.1
19.90.5

Lattice parameter
(nm)
0.8390.001
0.8200.001

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As shown in table 3, diameter after encapsulation is bigger than the diameter of CuFe2O4. This indicates that silica
chain with CuFe2O4 on its surface. Increasing intensity after encapsulation indicates that silica contributes raising the
crystallinity of CuFe2O4.
Deviation of lattice parameter of silica encapsulated CuFe2O4 is bigger than that of The CuFe2O4. The value is
affected by silane group of silica that substituted O2- ions on the surface of CuFe2O4. Percentage of ferrite phase
(CuFe2O4) decrease after encapsulation, besides the presence of other phase hematite and CuO decrease. Decreasing
amount of hematit and CuO phase indicates that silica could diminish oxidation reaction on CuFe2O4.
Decreasing amount of CuFe2O4 (ferromagnetic properties), hematit and CuO have antiferromagnetic properties, and
after encapsulation formed SiO2 that has diamagnetic properties. Investigation about magnetic properties discussed
later.
3.2.2. Analysis of Absorption Bands by FTIR
CuFe2O4 nanoparticles are analyzed their absorption bands before and after encapsulation by silica. The absorption
bands analyzed by FTIR is shown in figure 4.

Fig. 4. Absorption bands of CuFe2O4(a), SiO2(b) and CuFe2O4+ SiO2(c)


As shown in figure 4, previously descripted that CuFe2O4 (Fig.4.a) has absorption bands indicating OH, Fe3+- O2and Cu2+-O2- chain. FTIR spectra of silica (fig.4.b) has absorption bands. Absorption bands at ~ 794.67 cm-1, 1087.85
cm-1 and 2337.72 cm-1 refer to Si-O-Si vibration. Absorption band at ~ 964.41 cm-1 refer to Si-O vibration. The presence
of some functional groups Si-O-Si and Si-O that refers to silica indicates that all kinds of silica chains is identified.
FTIR spectra for silica encapsulated CuFe2O4 (fig.4.c) has shift of absorption bands and forms new absorption band
compared with silica and CuFe2O4 spectra. After encapsulation, the absorption band at hydroxyl vibration is 3448.72
cm-1 that bigger compared with OH group of CuFe2O4. The shift means silica chain with CuFe2O4 nanoparticles so that
it affects vibration OH of CuFe2O4. The same thing happen to OH bending and Si-O-Si stretching. Silica chain with
CuFe2O4 affects vibration of Fe3+ atoms in octahedral site with the shift wave number from 362.62 cm-1 become 354.90
cm-1. Besides Fe3+ atoms in tetrahedral site with the shift absorption band from 601.79 cm-1 become 570.93 cm-1. The
shift of absorption band at -OH bending, Si-O-Si, and Si-O of silica, both the shifts of wave number at Fe-O octahedral
and Fe-O tetrahedral as well, indicate that silica succesfully encapsulate CuFe2O4 nanoparticles.
3.2.3. Analysis of magnetic properties by VSM
From the hysteresis loops could be obtained the magnetization at H=15 kOe and coercivity ( ) as shown in table 4
below. As shown in the table 4, magnetization at H=15 kOe for CuFe2O4 (sample M) is smaller than silica encapsulated
CuFe2O4 samples. Hysteresis loops (at figure 9) of M sample inclined to saturation whereas silica encapsulated
CuFe2O4 samples are not saturation yet.
Amount of CuFe2O4 phase before encapsulation is 69.94% (ferrimagnetic phase), 15.37% hematit (antiferromagnetic
phase), and 14.68% CuO (antiferromagnetic phase). The amount 30.06% of antiferromagnetic phase affects magnetic
respon of the sample that is not too reactive to external magnetic fields. After encapsulation the amount of CuFe2O4
decrease to 40.33%, hematit and CuO decrease to 3.80% and 53.42% and formed new phase SiO2 52.46% (diamagnetic
phase).

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Table 4
No

Sample

1
2
3
4
5
6
7

S1
S2
S3
S4
S5
S6
M

and magnetization at H=15 kOe of CuFe2O4 and CuFe2O4+ Na2SiO3


Na2SiO3
concentration (%)
80
75
66
50
33
25
0

Magnetization at
H=15 kOe (emu/g)
6.0
24.5
21.1
15.9
9.5
11.3
5.9

Coercivity

(Oe)

45.0
45.6
45.6
43.6
47.2
45.0
125.0

Magnetization at H=15 kOe for S1, S5, and S6 samples decrease with the increase concentration of silica. Silica has
diamagnetic properties, so that the increasing concentration of silica causes the magnetization (at H=15 kOe) decrease.
For S2, S3, and S4 samples the magnetization increase with increase amount of silica. This is caused by their hysteresis
loops that is not saturated yet compared with S1, S5, and S6 that inclined to saturation.
Coercivity inclined to constant with increasing Na2SiO3 concentration. But coercivity of sample before
encapsulation is bigger than that of silica encapsulated CuFe2O4. The small coercivity of the samples after encapsulation
caused by increasing the crystallinity of CuFe2O4, and decreasing amount of hematite and CuO. Although SiO2 formed
after encapsulation, but its contribution to the coercivity is not significant because SiO2 has diamagnetic properties.
Diamagnetic material has no permanent magnetic moment. Coercivity for samples encapsulated by silica inclined to
constant, because the presence of SiO2 (diamagnetic) on CuFe2O4 is not much influence the coercivity. Diamagnetic has
little reaction while magnetic fields applied, but ferromagnetic (CuFe2O4) is very reactive to the fields.
The coercivity of CuFe2O4 (diameter 5.0 nm) should smaller than that of CuFe2O4+SiO2 (diameter 19.9 nm). But the
hysteresis loop of CuFe2O4 inclined to saturation whereas silica encapsulated CuFe2O4 samples are not saturation yet.
So comparing the
is not appropriate. Besides decreasing diameter of nanoparticles decreaseing anisotropy energy.
Therefore before encapsulation the CuFe2O4 nanoparticles is easier to magnetized compare with silica encapsulated
CuFe2O4.
4. Conclusions
Encapsulation with PEG-4000 and silica could increase the diameter of CuFe2O4 from 5.0 nm (before encapsulation)
become 8.8 nm and 19.9 nm respectively. Encapsulation with PEG and silica could diminish oxidation reaction on
CuFe2O4 surface as well. Increase amount of PEG causes decrease magnetization (at H=15 kOe) of CuFe2O4+PEG.
PEG could increase homogeneity of crystal structure of the samples. Therefore coercivity before encapsulation is 125.0
Oe, become at range 45.5-49.2 Oe after encapsulation. Increase amount of silica causes decrease magnetization (at
H=15 kOe) of CuFe2O4+SiO2. But this is not allowed by S2, S3, and S4 samples. Coercivity before silica encapsulation
is 125.0 Oe, become at range 45.0-47.2 Oe after encapsulation.
Acknowledgements
The authors wish to thank to Nano-Fabrication of Nagoya University, Culture, Sports, Science, and Technology
(MEXT) Nano-Project Platform, Japan, 2012-2017, and Research grant competence (HIKOM) Directorate of General
Higher Education (DIKTI), 2015-2016.
References
[1] A.S. Kumar, B. Thulasiram, S. Laxmi, Bala., V.S. Rawat, and B. Sreedhar, Magnetic CuFe2O4 nanoparticles: a
retrievable catalyst for oxidative amidation of aldehydes with amine hydrochloride salts, Tetrahedron, (2014),
No.70, p.6059-6067.
[2] J. Yang, P. Zou, L. Yang, J. Cao, Y. Sun, D. Han, S. Yang, Z. Wang, G. Chen, B. Wang, and X. Kong, A
comprehensive study on the synthesis and paramagnetic properties of PEG-coated Fe3O4 nanoparticles, Applied
surface science, (2014), No.303, p.425-432.
[3] M. Rahimi, P. Kameli, M. Ranjbar, and H. Salamati, The effect of polyvinyl alcohol (PVA) coating on structural,
magnetic properties and spin dynamic of Ni0,3Zn0,7Fe2O4 ferrite nanoparticles, Journal of Magnetism and Magnetic
Materials, (2013), No.347, p.139-145.
[4] V. Bansal, P.K. Sharma, N. Sharma, O.P. Pal, and R. Malviya, 2011, Application of chitosan and chitosan
derivatives in drug delivery, Advances in Biological Research, (2001), No.5, p.28-37.
[5] T. Ahmad, I. Rhee, S. Hong, Y. Chang, and J. Lee, Silica-coated iron-oxide nanoparticles synthesized as a T2
contrast agent for magnetic resonance imaging by using the reverse micelle method, Journal of Korean Physical
Society, (2010), No.57, p.1545-1549.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
[6] M. Anbarasu, M. Anandan, E. Chinnasamy, V. Gopinath, K. Balamurugan, Synthesis and characterization of
polyethylene glycol (PEG) coated Fe3O4 nanoparticles by chemical co-precipitation method for biomedical
applications, Molecular and biomolecular spectroscopy, (2015), No.135, p.536-539.
[7] E.R. Essien, O.A. Olaniyi, L.A. Adams, and R.O. Shaibu, Sol-Gel-Derived porous silica: economic synthesis and
characterization, Journal of Minerals and Mterials Characterization and Engineering, (2012), No.11, p.976-981.
[8] R. Boll, and H.R. Hilzinger, comparison of amorphous materials, ferrites, and permalloys, IEEE TRANSACTIONS
ON MAGNETICS, (1983), No.19, p.5.

CODE: IM
Synthesis, Characterization, X-ray Structure and Biological Activities of Schiff Bases Derived from
4-dimethylaminobenzaldehyde with 4-aminoantipyrine toward Cu (II) and Co (II) Ions
Rashd. M. El-Ferjani 1, Musa Ahmad 1, Farah Wahida Binti Harun1, Bohari Mohd.Yamin2, Bulgasem Y Bulgasem1
1

Faculty of Science and Technology Universiti Sains Islam Malaysia


71800 Nilai, Negeri Sembilan DK
2
School of Chemical Sciences and food Technology-UniversitiKebangsaan Malaysia,43600Bangi, Selangor D.E.,
Malaysia
Abstract: Schiff base complexes of Cu (II) and Co (II) ions derived from 4-dimethyl- aminobenzaldehyde and 4aminoantipyrine were prepared and investigated by using elemental analysis, 1H-NMR spectrum, infrared, and
electronic spectra. The elemental analysis (C, H and N) showed the formation of 1:1 [M: L] complexes. The infrared
spectral data of the obtained complexes displayed the proper coordination sites of the present Schiff bases toward the
metal ions.The X-ray crystallographic studies showed that the compound L crystallized in monoclinic system with
space group of C2/c and the unit cell dimensions are a= 17.7916, b= 6.8610, c= 29.7199, =90.000 = 101.326 =
90.000., Z = 8 and V = 3557.20 3. The electronic absorption spectral data of the same complexes showed the proper
electronic transitions and the expected chemical structures. The Schiff bases and its complexes have been screened for
antibacterial activity against three strains of pathogenic bacteria such as Bacillus cereus, Pseudomonus aeruginosa and
Bacillus subtilis. The Schiff bases and its complexes have also been screened for antifungal activity against three types
of Candida species included C. glabrata ATCC2001 , C.tropicalis ATCC750 and C. parapsilosis ATCC22019.
Keywords: 4-dimethylaminobenzaldehyde; 4-aminoantipyrine; Schiff bases complexes; antibacterial activity.
Corresponding author: Rashd Mohamed Hassan Ali, E-mail: did3010@yahoo.com, Tel. 0060123749042
1. Introduction
Schiff bases, products of the reaction of primary amines and carbonyl compounds, are involved in many metabolic
processes. Salicyliden- and 2-hydroxynaphthylideneamines have been the subject of particular interest because some of
their complexes are found in nature and biological activities have been recorded for the synthesized ones.1 Many metal
complexes have powerful antimicrobial activities and are already in common day-to-day use in medicinal field such as
silver bandages for treatment of burns, zinc antiseptic creams, bismuth drugs for the treatment of ulcers and metal
clusters as anti-HIV drugs2. The potential for further development of metal-based drugs and treatments as an
antimicrobial agent is enormous and also of great importance with the evolution of drug-resistant bacteria and threats
from a range of viral diseases3,4.
This paper describes the synthesis of a new Schiff base complexes of Cu (II) and Co (II) ions derived from 4dimethyl- aminobenzaldehyde and 4-aminoantipyrine and its metal complexes. Spectral and magnetic studies were used
to characterize the structure of the complexes. The elemental analysis, IR, 1 H-NMR, electronic absorption spectral and
X-ray were obtained to determine the structure of the ligand. All of the synthesized compounds were evaluated for their
antimicrobial activities against gram-positive and gramnegative bacteria and antifungal activity against.
2. Experimental
2.1. Chemicals and reagents
All chemicals and reagents used in this investigation were laboratory pure (BDH or Aldrich) including, 4dimethylaminobenzaldehyde, 4-aminoantipyrine, Cu(CH3COO)2.H2O, NaOH, [Co (C2H3O2)2.4H2O], C2H5OH, CH3OH
and DMOS .
2.2. Preparation of Schiff bases
Schiff bases of amino acids were prepared as follows: NaOH (10 mmol, 0.4 g) was dissolved in methanol (30 cm3)
and 4-aminoantipyrine (10 mmol) was added. The mixture was stirred magnetically at room temperature. When the
mixture becomes homogeneous, a 4-dimethylaminobenzaldehyde solution (10 mmol, 1.49 g) in ethanol (20 cm3). After
2 minutes the solution is evaporated to 20% of its original volume and 1cm3 of acetic acid was added immediately.
After 2 hours yellow crystals appeared. The crystals were filtered and washed with ethanol and recrystallized from hot
methanol to give yellow crystals with a yield of 75 to 85 %.
2.3. Preparation of the Schiff base complex
Complex of Schiff base of 4-aminoantipyrine were synthesized by mixing 50 cm3 of methanol containing NaOH (20
mmol, 0.8 g), 4-aminoantipyrine (20 mmol) with 50 cm3 of methanol solvent in a flask and stirred at room temperature.
A solution 4-dimethylaminobenzaldehyde (20 mmol, 2.98 g) in (50 cm3) was added ethanol in the solution. After 2
minutes, the solid metal salt [10 mmol, Cu (CH3 COO) 2.H2O or [Co (C2H3O2) 2.4H2O] and the mixture was

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magnetically stirred for 3 hours. The volume of solution was reduced 75% by evaporation and the residue was left to
stand overnight. The products obtained were filtered and recrystallized from methanol / ethanol (50%).
2.4. Determination of the antifungal activity using the agar well diffusion method
Five Candida species were selected to use for susceptibility to Schiff bases complexes using well diffusion method
as described by (Bauer et al., 1966) all strains of Candida species included C.albicans ATCC 1405, C. glabrata
ATCC2001 ,C. Krusei ATCC 6258 , C.tropicalis ATCC750 and C. parapsilosis ATCC22019 were cultured on
sabouraud dextrose agar (SDA) plates and incubated at 37 C for 24 h aerobically to check for purity colonies, then
were inoculated into sabouraud dextrose broth (SDB, Oxoid CM147) for overnight culture.Then one sterile swab was
dipped into the suspension of Candida 104 and rolled separately on the surface of plate containing sabouraud dextrose
agar SDA (Oxoid) the plates were dried in laminar hood at ambient temperature for 15 min, then wells of 6 mm were
made using cork borer and 20 L of SDA agar was pipetted to cover the base of the well to avoid leaking of Schiff
bases and Schiff bases complexes. 150 L Schiff bases and Schiff bases complexes were added to each well and the
plates were incubated at 37 C for 24 h aerobically, after 24 h the growth inhibition zone diameter around each well
was measured by ruler and recorded.
2.5. Determination of the antibacteria activity using the agar well diffusion method
Three pathogenic bacteria were selected to use for susceptibility to Schiff bases complexes using well diffusion
method as described by (Bauer et al., 1966) all strains of pathogenic bacteria included Bacillus subtilis, Bacillus cereus
and P. aeruginosa were cultured on nutrient agar (NA) plates and incubated at 37 C for 24 h aerobically to check for
purity colonies, then were inoculated into nutrient broth (NB) for overnight culture. Then one sterile swab was dipped
into the suspension of bacteria 104 and rolled separately on the surface of plate containing nutrient agar (Oxoid) the
plates were dried in laminar hood at ambient temperature for 15 min, then wells of 6 mm were made using cork borer
and 20 L of nutrient agar was pipetted to cover the base of the well to avoid leaking of schiff bases and Schiff
bases complexes. 150 L Schiff bases and Schiff bases complexes were added to each well and the plates were
incubated at 37 C for 24 h aerobically, after 24 h the growth inhibition zone diameter around each well was measured
by ruler and recorded.
3. Results and Discussion
3.1. Microanalysis
The elemental analysis data of the Schiff base complexes Tables (1) show the formation of 1:1 [M: L] ratio. It is
found that the theoretical values are in a good agreement with the found ones. The purity of the Schiff base complexes
were tested by TLC technique and (C, H and N) elemental analyses.
Table 1. Elemental analysis data of Schiff bases and their complexes
Schiff bases Complexes C%
H%
N%
M.Wt
Ligand(L)

71.83
71.83

6.63
6.63

16.75
16.75

49.33 4.93 11.51


50.13 4.12 11.63
48.09 5.21 11.22
[Co L (Cl)2(H2O)2]
48.00 5.20 11.20
Bold= Experimental values
[Cu L (Cl)2] H2O

334
486.50
499

3.2. Infrared Spectra


The infrared spectra of these complexes show a broad band at 3292,3466 cm-1 due to the presence of water
molecules5. The absorption bands at 1647-1615 cm-1 are assigned to the existence of (C=N) group of the azomethine.
The changing of this group to lower frequency indicates the effect of this group by complexation6. The other
complexation site, which can take part in coordination is the (C=O) group, the strong evidence of sharing this group can
be seen from the position of the band at 1586 cm-1 in the spectrum of free Ligand which may be attributed to (C=O) of
carbonyl group. The shifting of this band to higher and lower frequency in the spectra of the complexes suggesting the
participation of (C=O) group in coordination with the metal ion through the oxygen atom of carbonyl group of 4aminoantipyrine.[14] New bands at 464-632 and 628-522 cm-1 which are not present in the free Schiff base due to
(M-O) and (MN) vibrations. This concerned a good evidence for sharing of the oxygen and nitrogen atoms in
complexation7,8.
3.3. Electronic Spectra
The electronic spectrum of Cu (II)- complex, the spectrum displays bands in the range 280-517 nm (35714-19342
cm-1) due to charge transfer and 2T2g 2Eg transitions, suggest a square planar geometry. The electronic spectrum of
Co(II)-L Schiff base complex of the type [Co L(H2O)2(Cl)2] shows two bands at 320 and 515nm (10667and 17167cm-1).

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The first band is due to 4T1g (F) 4T2g (F) transition and the second one is assigned to 4T1g (F) 4T1g (P) transition.
These data suggest the presence of an octahedral geometry.
Table2. Infrared assignments (cm-1) and electronic absorption (nm, cm-1)
Of Schiff bases complexes
max
(M(M(OH)
cmLigand/Complexes
(C=N) (COO-)
(NH2) nm
O)
N)
(H2O)
1
Ligand (L)

3172

1613

1586

3097

[Cu L (Cl)2] H2O

3466

1615

1610

464

628

2914

[Co L(H2O)2(Cl)2]

3292

1647

1529

632

522

2914
2806

343
362
280
517

29155
27624
33670
19342

320 10667
515 17167

Expected
geometry
square
planar
octahedral

Also, the 1H-NMR spectrum of the ligand showed the following characteristic chemical shifts (DMSO as a solvent):
the singlet signal for Ligand at 9.41 ppm attribution of the protons of the azomethyne proton (CH=N-) and shows
aromatic benzene rings at 6.7-7.6 ppm rang and peak at 2.97 ppm attribution of the (CH3)2N and peak at 2.49 ppm
attribution of the (CH3) proton.
3.4. X-ray crystallographic study of the compound L
The X-ray investigation of the compound showed that the compound L crystallized in monoclinic system with space
group of C2/c and the unit cell dimensions are a= 17.7916, b= 6.8610, c= 29.7199, =90.000 = 101.326 = 90.000.,
Z = 8 and V = 3557.20 3.
Fig. 1 shows the molecular structure with the numbering scheme of the compound, the molecule is discrete and the
asymmetric unit consist two molecules. The phenyl rings in each molecule (C1C6) and (C21C26) make a dihedral
angle of 56.4(7) and 56.4(8) with the pyrazol heterocyclic ring, respectively. The bond lengths and angles are in normal
ranges and comparable to those in N, N-bis(2,3,4-trimethoxybenzaldiimine)-1, 4-diaminocyclohexane9 (Table 3) .
Both molecules showed the presence of C12H12.O1 and C32H32.O2 intramolecular hydrogen bond, as a
result a pseudo-six membered O1.H12/C12/N3/C8/C7and O2.H32 /C32/N7/C28/C27 rings are formed (Table 3).
In the crystal structure, the molecules are linked by C10H10AO1 and C32H32O2 intermolecular hydrogen
bonds to form dimers. (Fig.2).

Fig. 1. ORTEP diagram of the L drawn at 50% probability displacement ellipsoids. The dashed line indicates the
intramolecular hydrogen bond.

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Table 3. Selected Bond Lengths () and Bond Angles () for Compound L
Compound l?
Bond
Dist.
Angle
()
O1-C7
1.237(17)
N2-N1-C7
112.1(9)
O2-C27
1.256(18)
N2-N1-C6
117.2(10)
N1-N2
1.415(17)
C7-N1-C6
121.9(12)
N1-C7
1.438(16)
C9-N2-N1
101.5(10)
N1-C6
1.488(11)
C9-N2-C11
127.5(10)
N2-C9
1.349(14)
N1-N2-C11
114.6(9)
N2-C11
1.431(18)
C12-N3-C8
123.4(12)
N3-C12
1.279(17)
C16-N4-C20
124.4(17)
N3-C8
1.389(13)
C16-N4-C19
121.4(17)
N4-C16
1.317(19)
C20-N4-C19
113.8(12)
N7-C32
1.19(2)
C27-N5-N6
107.3(10)

Compound
L

Table 4. Hydrogen Bond Lengths () and Bond Angles () for Compound L


DH..A
DH
H..A
D..A
DH..A Symmetry code
C12H12.O1
0.93
2.38
3.059(15)
130
C32H32O2
0.93
2.25
2.97(2)
133
C10H10AO1 0.96
2.48
3.360(15)
153
x,-1+y,z
C20H20CO1 0.96
2.56
3.491(19)
164
-1/2+x,1/2+y,z

Fig. 2. Molecular packing of L viewed down the b axis. Dashed lines denote CH.O intermolecular hydrogen
bonds.

3.5. Antifungal Activity of L,Co(II) and Cu(II)-L complexes


The results of antifungal activity are shown in Table 5. Investigated Schiff base complexes exhibited good activity
against three types of fungal: C.glabrata, C.Tropicals, C.Parapislosis. Complexes derived from L showed the highest
inhibitory effect against examined fungal. In general the inhibition zones of the complexes were increased with
increasing their concentrations. The highest inhibition zone was obtained by complex Co2+ against C.glabrata where the
minimum inhibition zone obtained by complex Co2+ against C.Tropicals.
3.6. Antibacterial Activity of L, Co(II) and Cu(II)-L complexes
The results of antibacterial activity are shown in Table 6. Investigated Schiff base complexes exhibited good activity
against three types of bacteria: Bacillus cereus, Pseudomonus aeruginosa and Bacillus subtilis. Complexes derived
from L showed the highest inhibitory effect against examined bacteria. In general the inhibition zones of the complexes
were increased with increasing their concentrations. The highest inhibition zone was obtained by L.Co against Bacillus
subtilis where the minimum inhibition zone obtained by L against Bacillus cereus .

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Table 5. Effect of L, Co(II) and Cu(II)-L


Cu(II) complexes on growth of pathogenic Candida species by well diffusion
method.
Ligand/Complexes Concentration C.glabrata C.Tropicals C.Parapislosis
20mg/ml
11
8
6
Ligand (L)
10mg/ml
9
5
5

[Co L(H2O)2(Cl)2]

[Cu L (Cl)2] H2O

5mg/ml

20mg/ml

24

12

11

10mg/ml

18

5mg/ml
20mg/ml

12
12

5
10

5
9

10mg/ml

5mg/ml

Table 6. Diameter of inhibition zone for antibacterial screening of L,Cu(II) and Co(II)-L
Co(II) co
complexes. Inhibition zone
diameter in mm
Ligand/Complexes Concentration Paeruginosa Bacillus subtilis Bacillus cereus
Ligand (L)

[Co L(H2O)2(Cl)2]

[Cu L (Cl)2] H2O

H3C

5mg/ml
10mg/ml

10
13

11
13

8
10

20mg/ml

15

15

12

5mg/ml

10

12

10mg/ml

24

23

23

20mg/ml
5mg/ml

25
20

27
16

26
13

10mg/ml

22

24

18

20mg/ml

24

25

20

CH3
N

N
N

Co

H2O
H2O

Cl

CH3

Cl
N

CH

Fig. 3. Suggested structure of Co(II)and Cu(II) complexes.


complexes

4. Conclusion
From the previous data [elemental analysis, molar conductance measurements, infrared, electronic absorption,1H
NMR and X-ray]
ray] we can propose the following chemical formulae for the synthesized Schiff base complexes. The in
vitro investigation of the synthesized complex revealed that all the complexes showed very good results against the
selected micro
o organisms under investigation.
investigation

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References
[1] I. akyan, N.Gndz, and T.Gndz, Synthesis and Characterization of Manganese(III) Complexes of Schiff
Bases Derived From Amino Acids and 2-Hydroxy-1-naphthaldehyde. Synth. React. Inorg. Met.-Org.Chem, 31 (
2001),No.7,p. 1175-1187.
[2] A. N. El-Tajoury, M. M. El-ajaily, A A. Maihub, and Ben Geweirif, N-Salicylideneaminoacidato Complexes of
Divalent Transition Metal Ions from the Cysteine Pure and applied Journal, Sebha University, 5( 2006),No.
1,p.108-123.
[3] S.Sarkar and K. Dey Synthesis and spectroscopic characterization of some transition metal complexes of a new
hexadentate N2S2O2 Schiff base ligand. Spectrochimica Acta Part A 62 (2005), p.383-393.
[4] Y. Sato, H. Miyasaka, N. Matsumoto, and H. Okawa, Synthese, Structures and Magnetic Properties of the
Tricyanoethenolate Adducts of Quadridentate Schiff Base Manganese(III) Complexes, Inorg. Chim. Acta 247 (
1996), p.57-63.
[5] D. Heinert, and A. E. Martell, Pyridoxine and Pyridoxal Analogs. V. Syntheses and Infrared Spectra of Schiff
Bases. J. Am. Chem. Soc, 84, ( 1962), p.3257-3263.
[6] H. Keypour, M. Shayesteh, A. Sharifi-Rad, S. Salehzadeh, H. Khavasi and L.Valencia, Synthesis and
characterization of copper(II) and cobalt (II) complexes with two new potentially hexadentate Schiff base ligands.
X-ray crystal structure determination of one copper(II) complex. Journal of Organomettalic Chemistry. 693(2008),
p.3179-3187.
[7] J .Parekh, P. Inamdhar, R. Nair, S. Baluja and S. Chanda, Synthesis and antibacterial activity of some Schiff bases
derived from 4-aminobenzoicacid, J.Serb Chem. Soc. 70(2005),No . 10, p. 1155-1161.
[8] M. M. Abd-Elzaher, Spectroscopic characterization of some tetradentate Schiff bases and their complexes with
nickel, copper and zinc Journal of the Chinese Chemical Society, 48 ( 2001),p. 153-158.
[9] M. S. Islam, and M. Masiruddin,. Preparation and characterization of some complexes of
chromium (III),
cobalt (III) and rhodium (III) ions containing 1, 4, 8, 12-tetra-azacyclopentadecane J. Bangladesh Chem.
Soc.,6(1993).No. 1,p.25.

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The 7th International Conference on Sensors ASIASENSE 2015
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CODE: IM
Immobilization of aniline in chitosan film for an optical detection of Hydroxymethylfurfural (HMF).
Mashri Ahmad Yahia 1, Musa Ahmad 1, Che Wan Z. che 1, Lee Y. H 2
Faculty of Science and Technology Universiti Sains Islamic Malaysia,
71800 Nilai, Negeri Sembilan DK
2
School of Chemical Science and Food Technology, Faculty of Science and Technology. Universiti Kebangsaan
Malaysia, 43600 Bangi, Selangor, Malaysia
1

Abstract: An optical sensor based on the immobilized aniline in a chitosan film is described for the detection of
Hydroxymethylfurfural (HMF). The film was prepared by depositing a chitosan solution containing aniline onto filter
paper via spin coating technique. The optimum volume ratio of aniline to chitosan was 1.5:2.5 (v/v) respectively. The
absorption intensities of the reagent were measured at a wavelength range of 250 to 500 nm before and after reaction
with the HMF. The optimum absorption response was obtained at pH3.0 and aniline concentration of 8 10-3 M .The
relative standard deviation (RSD) of reproducibility was 1.9% when concentration of aniline 8 10-3 M was used .The
photostability was found to be good with RSD value of 1.5 %.The method could be applied for HMF quantitative
determination in the concentration range of 1.0 10-3 _ 6.0 10-3.
Keyword: Optical sensor; aniline; Chitosan; Hydroxymethylfurfural; UV- Visible spectrophotometric; pH.
Corresponding author: Mashri Ahmad Yahia, Email : mshre71@yahoo.com
1. Introduction
Hydroxymethylfurfural (HMF) is a cyclic aldehyde produced as a result of sugar degradation [1]. The presence of
simple sugars (glucose and fructose) and various acids in honey is said to be a favorable condition for HMF production.
HMF and its congener compounds spontaneously form in carbohydrate-containing foods formed through Maillard
reactions (i.e., the non-enzymatic browning reaction) or through the acid-catalyzed dehydration of hexoses. [2]
Chitosan is a natural biopolymer product found in the exoskeleton of crustaceans, in fungal cell walls, and other biology
materials. The biodegradability, nontoxicity, biocompatibility, high mechanical strength, good adhesion, and
susceptibility of chitosan to chemical modification from reactive amino and hydroxyl functional groups make this
compound a promising matrix for enzyme immobilization [3]. Chitosan surfaces are transparent in UV and visible
regions. Thus, it should have minimal effect on most optical detection methods. Furthermore, chitosan is safe, abundant,
and inexpensive.
As the most promising organic-conducting polymer, polyaniline (PANI) has wide applications, such as in
rechargeable batteries, corrosion protection of metals, gas-separation membranes, and molecular sensors [4]. PANI
bears good environmental, thermal, and chemical stability, as well as remarkable electrical and optical properties, facile
redox, and pH-switching behaviour [5]. PANI can be rapidly switched with the addition of acids (protonation) and
bases (deprotonation). An acid-doped PANI yields conducting emeraldine salt, which can be dedoped to form the
insulator emeraldine base [6]. The electrical conductivity of PANI is enhanced by a simple change in pH conditions.
Recently, conducting polymers, such as PANI, have been considered for applications in microelectronics. The
combination of tunable chemical properties with the electronic properties of conducting polymer has a tremendous
impact on the development of new sensors. The use of conducting polymers in sensors has recently been reviewed [7].
However, the solubility and mechanical properties of PANI have limitations [8]. The incorporation of PANI into
flexible matrix could result in good processability and electrical conductivity with chemical stability toward dopants,
thermal stability, and insolubility under readily accessible conditions [9]. Chitosan has gained growing interest in the
preparation of semi-interpenetrating chitosan/polyaniline [10,12] because of its excellent film-forming ability, good
adhesion, biocompatibility, and high mechanical strength.
This paper describes the use of a chitosan film for the development of an optical sensor. The aniline was
immobilized in chitosan film prepared through spin coating method with a filter paper used as supporting material.
HMF was determined using color reagent aniline, which interacts with the nitrogen group to produce reactions that are
confirmed through azomethine group color products [13]. As shown in the equation below, these colored pigments can
be monitored spectrophotometrically.

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The 7th International Conference on Sensors ASIASENSE 2015
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Fig. 1. Chitosan-graft-aniline synthesized through the oxidative-radical graft copolymerization.

2. Experimental section
2.1. Materials
The materials used in this study were: chitosan (Aldrich; Mw 1.86105) and aniline (E. Merck); HMF (Sigma);
phosphate baffer (reinst), hydrochloric acid (HCl) 36%, ethanol 95% (Systerm); acetic acid (Ajax chemicals). All
chemicals were used without further purification.
2.2. Instrumentation and measurement procedure
All absorption measurements were condcuted using a UVvis spectrophotometer (model Varian-Cary win UV 50)
for spectrophotometric studies. The glass slide coated with aniline immobilized in a chitosan film was immersed in a
feltter paper containing phosphate buffer solution (pH 3), aniline (0.003 M), and HMF (0.003 M). Absorption studies
were recorded between 250 nm and 500 nm .
2.3. Construction of sensor
In this work, one type of chitosan was used for the sensor construction. Chitosan powder was mixed with a 0.1%
(v/v) HCl solution and stirred for 2 h. Chitosan solution (0.2%, w/v) was prepared by dissolving 2 g of chitosan powder
in 100 mL of HCL (0.1%, v/v). The viscous chitosan solution was stirred overnight at room temperature. Standard HMF
solution of 3 10-3 M was prepared by dissolving an adequate amount of 0.094 M in 25 ml deionized water. An aniline
standard stock solution of 3 10-3 M was prepared by dissolving the required amount of 0.00698 g in 25 mL deionized
water. Another chitosan solution (2%, w/v) was prepared by dissolving 2 g of chitosan powder in 100 mL of
hydrochloric acid (0.1%, v/v). The viscous chitosan solution was stirred overnight at room temperature. A
homogeneous stock solution of aniline/chitosan mixture was prepared by mixing 2.5 ml of a 2% (w/v) chitosan solution
and 1.5 ml of aniline solution in an eppendorf tube. The mixture was stirred gently for 45 min. The stock solution was

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The 7th International Conference on Sensors ASIASENSE 2015
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freshly prepared before the fabrication of the optical film. The formulation was changed accordingly when certain
experimental parameters were investigated. Initially, 4 ml and 0.5 ml pH 3 of the stock aniline /chitosan mixture was
pipetted into a filter paper and smeared gently over an area. This solution was dried at room temperature. The
immobilized aniline was kept at 4 C when not in use.
3. Results and discussion
A series of experiments were performed to optimize sensor response. HMF was used as a substrate to establish the
capability of the sensor in terms of optimal conditions, detection limit, dynamic range, and stability.
The response was monitored by determining the intensity of the color adduct produced, which is proportional to the
HMF concentration.
The mechanism of chitosan quinone adduct formation for aniline activity has been reported [14].
Fig. 2 shows the absorption spectra of aniline immobilized in a chitosan film. The UVvis spectrum of aniline, HMF,
and aniline with HMF showed three bands at 135.5 nm, 99.37 nm, and 179.17 nm, respectively. These bands were
assigned to -* and n-* transitions. The UVvis spectra of 3 10-3 M of the Schiff bases (Fig. 1) display similar
absorption spectra of the ligand, which were shifted to higher wavelengths. Findings include an increase or appearance
of the peak dye to n-* transition, which was confirmed by the azomethine group.

Fig. 2. UVvis absorption spectra of the solution aniline (310-3), (HMF,) (310-3) and HMF with aniline.
The effect of pH was also studied at different pH values in 3 10-3M phosphate buffer (Fig. 3) . In addition, pH was
an important factor during extraction and storage because of its relation to the stability and shelf life of the product
(Terrab et al., 2004). As previously reported [7], most bacteria and mold grow in neutral and mildly alkaline
environments. By contrast, yeasts require an acidic environment and do not grow in alkaline media. Therefore, the mean
pH of immobilization aniline, a reagent with HMF as an analyte, was 3.0 .The effect of a different amount of aniline
loading on sensor response was also examined.

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120

R % (500nm)

100
80
60
40
20
0
2

immobilization pH(aniline)
Fig. 3. The Effect of working pH on the absorbance of polyaniline upon reaction with (3 10-3) HMF solution.

As shown in Fig. 4, the optimum aniline loading was observed at a concentration of 0.008 M. Thus, 0.008 M was
subsequently used for further immobilization.
205
185

R % (500nm)

165
145
125
105
85
65
45
1

immobilization concentration

10-3

(aniline) M

0.1

Fig. 4. The effect of polyaniline concentration on the response of the method when the HMF concentration used
was fixed at 3 10-3 M with buffer solution of pH 3.0.

Fig. 5 shows the response curve of the sensor towards HMF in the concentration range of 0.0 to 0.008 M. The
reflectance signal increased drastically with increasing HMF concentrations at the initial study. The response slowly
leveled off at higher HMF concentrations and become saturated at 0.004 M HMF. Higher HMF concentration allowed
more reactions between the sensor and analyte molecules present in the adjacent phase. Thus, a higher signal was
observed. The reflectance signal ultimately plateaud because almost all immobilization sites have been fully occupied
by the analyte molecules. The inset shows the calibration curve obtained under optimised conditions. The relative
reflectance was a linear correlation (R2 = 0.9902) with HMF concentration in the concentration range of 0.004 M.

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The 7th International Conference on Sensors ASIASENSE 2015
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Fig. 5. The response curve of the method at different concentration of HMF. Inset is the
HMF solution.

linear dynamic range of the

The sensor shows good stability for at least 6 h with the calculated RSD value of 1.5% (Fig. 6). The reproducibility
of the immobilized aniline, which was conducted at a HMF concentration of 310-3 M, was also good with a calculated
RSD value of 1.96% (Fig. 7) .

70
60

R % (500nm)

50
40
30
20
10
0
0

30

60

90

120 150 180 210 240 270 300 330 360


Times (aniline) immobilzation

Fig. 6. The photostability of polyanilie against time.

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85

R % (500nm)

75
65
55
45
35
25
1

Number of Measurement
Fig. 7. The reproducibility of the reagent polyailine 310-3 forwards HMF analyte, in phosphate buffer (pH 3.0).
4. Conclusions
A favorable use of chitosan as a matrix for aniline immobilization in the development of an optical HMF sensor has
been described. The color intensity of the adduct increased proportionally with the increase of substrate concentration
after one day exposure to the substrate. The sensor permits good sensitivity, reproducibility, and the photostability. The
solution condition for operation was maintained at pH 3, and the concentration of the reagent was 4 10 -3 M. The
reproducibility study showed a good RSD value of 1.96%. The photostability response with RSD of 1.5% was used to
monitor the photobleaching process. Aniline was used as a solution and observed using HMF. The developed sensor has
a good potential in the quantitative determination of HMF in industrial settings.
References
[1] Ramirez, C.M.A., Gonz lez, N.S.A., Sauri, D.E., 2000. Effect of the temporary thermic419treatment of honey on
variation of the quality of the same during storage.420Apiacta 35 (4), 162170.
[2] B.Lopez, M. J. Latorre, M. I. Fernndez, M. A. Garca & C. Herreroa, Food Chemistry, 1996; 55, Issue 3, PP
281-287.
[3] G. Wang, J.J. Xu, H.Y. Chen, Z.H. Lu, Amperometric hydrogen peroxide biosensor with solgel/chitosan
network-like film as immobilization matrix, Biosens. Bioelectron. 18 (2003) 335343.
[4] Y. Miao, S.N. Tan, Amperometric hydrogen peroxide biosensor with silica solgel/chitosan film as
immobilization matrix, Anal. Chim. Acta 437 (2001) 8793.
[5] H. Yi. L.Q. Wu, J.J. Summer, J.B. Gillespie, G.F. Payne, W.E. Bently,Chitosan scaffolds for biomolecular
assembly: coupling nucleic acid probes for detecting hybridization, Biotech. Bioeng. 83 (6) (2003) 646652.
[6] Sengupta P. P. S., Barik S., Adhikari B.: Polyaniline as a gas-sensor material. Materials and Manufacturing
Processes, 21, 263270 (2006).
[7] Karami H., Mousavi M. F., Shamsipur M.: A new design for dry polyaniline rechargeable
batteries. Journal of
Power Sources, 117, 255259 (2003).
[8] Prokes J., Stejskal J.: Polyaniline prepared in the presence of various acids: 2. Thermal stability of conductivity.
Polymer Degradation and Stability, 86, 187195 (2004).
[9] Kang Y. Kim S. K. Lee C. Doping of polyaniline by thermal acid-base exchange
reaction. Materials Science
and Engineering: C, 24, 3941 (2004).
[10] Tiwari A. Gum arabic-graft-polyaniline: An electrically active redox biomaterial for sensor applications. Journal
of Macromolecular Science Part A: Pure and Applied Chemistry, 44, 735745 (2007).
[11] Lu. X. Tan. C. Y. Xu J. He C. Thermal degradation of electrical conductivity of polyacrylic acid doped
polyaniline: effect of molecular weight of the dopants. Synthetic Metals, 138, 429440 (2003).
[12] Shin S. R. Park S. J. Yoon S. G. Spinks G. M. Kim S. I. Kim S. J. Synthesis of conducting polyaniline in semiIPN based on chitosan. Synthetic Metals, 154,213216 (2005).
[13] Peniche C. Argelles-Monal W., Davidenko N. Sastre R. Gallardo A. Roman S. J. Self-curing membranes of
chitosan/PAA IPNs obtained by radical polymerization: preparation, characterization and interpolymer
complexation. Biomaterials, 20, 1869 1878 (1999).
[14] J.N. Rodriguez-Lopez, J.R. Ros, R. Cvaron, F. Garcia Canovas, Oxygen Michelis
constant for tyrosinase,
Biochem. J. 293 (1993) 859866.

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CODE: IM

Utilization of Industrial Waste in Indonesia as Filler for Low and High Calcium Fly Ash
based Geopolymer
1)

Partogi H Simatupang
4)
Imran

, Andrie Harmaji2), Astrid N Anggraini3), Ivindra Pane4), Bambang Sunendar5), Iswandi

Department of Civil Engineering, Faculty of Science and Engineering, University of Nusa Cendana,
Kupang 85000, Indonesia
2
Department of Materials Engineering, Faculty of Mechanical and Aerospace Engineering, Institut Teknologi Bandung,
Bandung 40132, Indonesia
3
Department of Geothermal Engineering, Faculty of Mining and Petroleum Engineering, Institut Teknologi Bandung,
Bandung 40132, Indonesia
4
Department of Civil Engineering, Faculty of Civil and Environmental Engineering, Institut Teknologi Bandung,
Bandung 40132, Indonesia
5
Department of Physics Engineering, Faculty of Industrial Technology, Institut Teknologi Bandung,
Bandung 40132, Indonesia
Abstract: Geopolymer was prepared by mixing fly ash and light aggregate with silica fume, electric arc furnace dust
(EAFD) slag, or red mud by addition of activator solution containing sodium hydroxide solution and waterglass to make
slurry by certain ratio of binder and filler. The aim for this research is to obtain high strength geopolymer based on
industrial waste. The difference in composition between binder-filler ratio affected the compressive strength and the
microscopic characteristics of resulting geopolymer. Compressive strength was observed after several days of curing
with the best result of obtained for high and low calcium fly ash based geopolymer were 60.27 MPa and 71.07 MPa,
respectively. The X-ray diffraction showed the appearance of characteristics peak of geopolymer, such as sodium
aluminum silicate hydrate and albite. The Fourier Transform Infrared spectroscopy confirmed the formation of siloxo
(Si-O-Si) and sialate (Si-O-Al) bonding which are typical functional groups of geopolymer.
Keywords: geopolymer; fly ash; alkali activator; macroscopic characteristics; microscopic characteristics.
Corresponding author: Partogi H. Simatupang, e-mail: simatupangpartogi@yahoo.com, Tel. +62-81-239-485-378

1. Introduction
Coal is the common material used in electric generator, metallurgy, and coal gasification industry [1]. Fly ash is one
of by-product produced from coal burning that piled in dump and could be toxic waste to surrounded environment. Fly
ash is a lightweight and fine particle material from exhaust boiler, it has pozzolanic properties that can be used for
Ordinary Portland Cement (OPC) based concrete to enhance its compressive strength.
The utilization of fly ashas binder will reduce the need of OPC and will affect the cement industry production, one
of the main source that contribute the green house gas emission in earth since it produce high CO2 emission [2]. OPC
based concrete also has limited lifetime because it consists of very high calcium oxide (CaO) that can cause cracks in
concrete. Geopolymer, the mixture of synthetic aluminosilicate material can solve this problem since it can be made
with zero-cement binder, has higher compressive strength, and better chemical attack resistance than OPC-based
concrete.
Fly ash has high alumina (Al2O3) and silica (SiO2) contents and can be used for main binder for geopolymer.
Generally fly ash is divided into two main class, low calcium (Class-F) and high calcium (Class-C). Filler from some
industrial waste such as silica fume, red mud, and EAFD slag can also be added to geopolymer to enhance its
compressive strength. The aim of this work is to determine the optimum binder-filler ratio using fly ash binder and
industrial waste filler (silica fume, red mud and EAFD slag) to produce geopolymer with high strength properties.
2. Methodology
2.1 Materials
In this work some industrial waste from different source were used as raw materials. Class-F fly ash was obtained
from Suralaya Coal Fired Power Plant in Banten, class-C fly ash was obtained from Batu Hijau Coal Fired Power Plant

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PT Newmont in Sumbawa, silica fume from PT Sika Indonesia, electric arc furnace dust (EAFD) slag from PT
Krakatau Steel in Banten, and red mud from by-product
by
of Tayan, West Borneo bauxite ore.
Class-F and class-C
C fly ash were used as the binder,
binder, while silica fume, EAFD slag, and red mud were used as filler.
The oxides composition of these materials is shown in Table 1. Cimalaka sand in saturated surface
surface-dry (SSD) was used
as fine aggregate for making mortar phase. Alkali activator solution contained
contained water glass (Na2SiO3) solution and
sodium hydroxide (NaOH, 12M) solution. The alkali activator was stored before was used in geopolymerization at least
4 hours before crystallization of sodium bicarbonate (Na2CO3) was occurred [3].
Table 1. The oxide composition of materials

2.2 Methods
Binder consists of class-C
C or class-F
class fly ash used were varied from 50-100
100 wt%. Filler consists of silica fume,
EAFD slag, or red mud was varied from 5-50
5 50 wt%. Alkali activator consists of sodium hydroxide 12M and sodium
silicate with 2:1 ratio.
The ratio of activator: fly ash: sand was 1:2:3 [4]. Geopolymer was made by mixing binder (class
(class-C or class-F fly
ash), filler (silica fume, EAFD slag, red mud), and alkali activator (sodium silicate and water glass) with H
HobartTM
mixer, resulting in slurry. The slurry was then poured into 50 mm x 50 mm x 50 mm mold in top of shaking table to
make it compact. After that the mold was cured under ambient (normal air) or dry (heating in 80C oven) condition for
several days, de-mold
mold the sample, and its tested for compressive strength by using Universal Testing Machine (UTM)
conformed to ASTM C-39.
The X-Ray Diffraction (XRD)
XRD) measurement was performed on Philips Diffractometer PW1710 with Cu as anode.
Resulting diffraction pattern
rn was compared to Joint Committee on Powder Diffraction Standards (JCPDS) to determine
compound found in samples. Fourier Transform Infrared (FTIR) was carried out using Prestige 21 Shimadzu to
determine the functional groups of resulting geopolymer.
3. Results and Discussion
3.1 Compressive Strength
The compressive strength result is shown in Figure 1. It shows that the higher percentage of filler (silica fume,
EAFD slag, or red mud) resulted in the decrease of the compressive strength of class-C
class C or class
class-F geopolymer, except
for red mud. The addition of 5% red mud has increased the compressive strength of class-F
class F fly ash geopolymer which is
71.07 MPa, this due to the high alumina (Al2O3) content in the red mud. The best compressive strength for class
class-C fly
ash based sample contains 100% class-C
class C fly ash (without filler) resulted in 60.27 MPa compressive strength.
Geopolymer resulted from dry curing method mainly has higher compressive strength than the ambient. The water from
sample obtained from dry curing evaporated and generated denser geopolymer.

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Fig. 1. Compression strength results of various composition of geopolymers after curing under ambient or dry
conditions.

3.2 Fourier Transform Infrared (FTIR) Results


Figure 2.a and 2.b show the FTIR
TIR results from class-C
class C fly ash based geopolymer and class
class-F fly ash based
geopolymer, respectively. It shows the appearance of some characteristic peaks such as bending vibration of Si
Si-O-Si at
470 cm-1, stretching Si-O-Si
Si and stretching Si-O-Al
Si
at 1031 cm-1 for class-C
C fly ash geopolymer and 1012 cm-1 for
class-F
F fly ash geopolymer, indicating the formation of sodium aluminum silicate hydrate in all samples. It can be
concluded that reaction between silica and alumina in fly ash has occured [5]. Broad peak
peak at 3500 cm-1 corresponds to
-1
stretching OH and peak at at 1800 cm from bending H-O-H,
H, originating from water content in geopolymer. FTIR
spectra of class-C
C fly ash geopolymer indicate higher peak of stretching O-C-O
O O (in 1440 cm-1) than Class-F fly ash
geopolymer.
eopolymer. These peaks show the formation of sodium bicarbonate. This may occur during the reaction of samples
with CO2 in air.
3.3 X-Ray Diffraction (XRD) Results
Figure 3.a and 3.b shows XRD difractograms of geopolymerization from class-C
class C fly ash based geopolymer and or
class-F
F fly ash based geopolymer, respectively. The diffractograms demonstrate that both geopolymerization shifted the
hump of XRD, showing that the product is more amorphous than fly ash [6]. The common mineral appeared in
geopolymer product
duct is sodium aluminum silicate hydrate, whereas this compound was not found in class
class-C and class-F
fly ash.
Sodium aluminum silicate hydrate has similar formula with geopolymer (Mn [-(SiO2)z--AlO2]n. wH2O), it can be
concluded that geopoymerization has occurred.
occurred. XRD results of different samples are displayed in Figure 3, showing

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that sodium aluminum silicate hydrate ([], JCPDS No. 380239), Pyrophyllite (#, JCPDS No. 461308), Quartz (x, JCPDS
No. 010649), and Albite (o, JCPDS No. 200572) have been formed in all geopolymer samples.
b

FAC+SF

Intensity (a.u)

FAC+ES

FAC+RM

4000

3500

3000

2500

2000

1500

1000

500

-1

Wavenumber (cm )

(a)
b

FAF+SF

Intensity (a.u)

FAF+ES

4000

FAF+RM

3500

3000

2500

2000

1500

1000

500

-1

Wavenumber (cm )

(b)
Fig. 2. FTIR spectra of (a) class-C fly ash based geopolymer (b) class-F fly ash based geopolymer.

(a)

(b)
Fig. 3. XRD Results (a) class-C fly ash based geopolymer (b) class-F fly ash based geopolymer.
4. Conclusions
Geopolymer were successfully prepared by mixing high calcium fly ash (class-C) or low calcium fly ash (class-F) as
binder and silica fume/EAFD slag/red mud as filler with alkali activator solution followed by ambient or dry curing.

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The best compressive strength for low and high calcium fly ash are 71.07 MPa and 60.27 MPa, respectively. XRD
shows some of significant mineral that commonly found on geopolymerization such as sodium aluminum silicate
hydrate and albite. FTIR shows the common bonding occurred in geopolymerization, such as siloxo and sialate.
Acknowledgements
This research was funded by Directorate General of Higher Education Indonesia through National Strategic
Competitive Research Grant. We also thank PT Newmont Nusa Tenggara (PTNNT) for providing Class-C fly ash and
PLTU Suralaya for providing Class-F fly ash.
References
[1] Olivia, M. and Nikraz, H.R., (2011) : Strength and water penetrability of fly ash geopolymer concrete, ARPN
journal of engineering and applied sciences, 6(7) : 70-78
[2] Muzek, M.N., Zelic, J., and Jozic, D., (2012) : Microstructural characteristics of geopolymers based on alkaliactivated fly ash, Chem. Biochem. Eng. Q., 26(2) : 89-95
[3] Hardjito, D., and Fung, S.S., (2010) : Fly Ash-Based Geopolymer Mortar Incorporating Bottom Ash, Modern
Applied Science, 4(1).
[4] Simatupang, P.H., Hanafi, R., Sunendar, B., Imran, I., and Pane, I., (2012) : The Study of Red Mud Addition
Influences in Metakaolinite-Based Geopolymer Characteristics, Journal of Advanced Materials Research, 450451, pp.281-285.
[5] Fernandez-Jimenez, A., Palomo A., and Revuelta, D., (2009) : Alkali Activation of Industrial by-products to
develop new earth-friendly cements, Proceedings of the 11th International Conference on Non-Conventional
Materials and Technologies (NOMAT), Bath, UK.
[6] Skavara, F., Jilek, T., and Kopecky, L., (2005) : Geopolymer Materials Based on Fly Ash,Ceramics-Silikaty,
49(3), 195-204.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015

CODE: IM
Synthesis of Novel Core-Shell Structured TiO2@SiO2: Investigations on the Use of SiO2 Extracted from Sidoarjo
Mud for Dye-Sensitized Solar Cells
Herny Ariesta Budiarti1), Rizky Nanda Puspitasari1), Sekartedjo1), Doty Dewi Risanti1)
1Department of Engineering Physics, Institut Teknologi Sepuluh Nopember, Surabaya 60111, Indonesia.
Abstract: In this work, we prepare TiO2@SiO2 core-shell which uses SiO2 from Sidoarjo mud extract and
embedded these particles in to TiO2 photoanode for dye-sensitized solar cells (DSSC). The as-prepared sampel
were characterized by x-ray powder diffraction (XRD) and fourier transform infrared spectroccopy (FTIR). XRD
and FTIR confirm the formation core-shell structure as indicated by a shoulder peak of SiO2 adjacent to TiO2 peak
and stretching mode (Si-O-Si) at ~1077 cm-1, respectively. The DSSC contained 10 wt% of TiO2@SiO2 from TEOS
can attain a relatively better efficiency of 0.0092% compared to all photoanode studied. The IPCE of this DSSC has
shown a broader absorption edge compared with that from mud extract. Possibility of the agglomeration and
incomplete coating is discussed.
Keywords: TiO2; SiO2; core-shell; Sidoarjo mud; photoanode, DSSC
Corresponding author: Herny Ariesta Budiarti, E-mail: ariesta.herny14@mhs.ep.its.ac.id
1. Introduction
Finding a new and more efficient way to suppress the recombination is of key issue to advance toward a more
efficient conversion of solar energy into electricity in photovoltaic cells. Nanoparticles with such a core-shell
architecture is beneficial to provide a number of advantages over conventional single nanoparticle. Coating thin SiO2
layers or forming SiO2 shells on TiO2 nanoparticles has been proposed in recent years as a promising alternative, since
the conduction band edge of SiO2 is negative compared to that of TiO2. The main reason actually lies in the fact that the
core/shell structure is able to scatter the light, hence increase light path and light harvesting and ultimately enhance
solar cell efficiency. Wang, et al. embedded a submicron SiO2@TiO2 core-shell particles to the DSSC photoanode. Due
to the strong light scattering effect of SiO2@TiO2 core-shell the efficiency increased from 3.5 % to 5.1%, almost 50%
better than without light scattering particles [1]. However, several researches reported futile results and most likely
were attributed to the incomplete coating of SiO2 onto TiO2 surface allowing the recombination to take place at the
exposure sites [24]. It is noted that the insulating nature of SiO2 at certain level may cause the drop in efficiency
efficiency [5].
Abundant availability of Sidoarjo mud volcano has led many researchers to seek possibility of utilizing it. Owing to
the fact that the mud is rich in SiO2, Al2O3 and Fe2O3, the mud is mostly used as as construction materials or as
adsorbent [68]. In this reseach we investigate the possibility of using SiO2 from Sidoarjo volcanic mud to coat the
TiO2 nanoparticles. It is known that the common source of SiO2 is tetraethyl orthosilicate/TEOS or Si(C2H5O)4. The
modified TiO2 photoanode is fabricated by embedding TiO2@SiO2 core-shell structure and its performance in the form
of Dye-Sensitized Solar Cells sensitized with natural dye is examined.
2. Experimental
2.1. Preparation of TiO2 nanoparticles
TiO2 nanoparticles ware synthesized using co-precipitation method, 10 ml TiCl3 was used after dilution in 20 ml
HCl 37%. Then, the ammonium 25% was added drop wise to titanium trichloride solution under continuous stirring
until the white precipitate was obtained. The resulting suspension was maintained at room temperature for 24 hours and
subsequently filtered and washed approximately 5 times with distilled water to remove the remaining ammonium and
chloride ions. The anatase TiO2 was obtained by annealing the white precipitate at 300C for 4 hours. The rutile TiO2
was obtained by annealing the precipitate at 1000C for 7 hours [9].
2.2. Preparation of SiO2 nanoparticles
SiO2 nanoparticles were prepared using the modified Stber method and also extracted from Sidoarjo mud [1], [10].
At first, 9 ml ammonia with a concentration of 28%, 16.25 ml ethanol, and 24.75 ml demineralized water ware added
into a breaker (solution A). Solution A was stirred vigorously for 5 min. In the meantime we mixed 4.5 ml tetraethyl
orthosilicate (TEOS) with 45.5 ml ethanol (solution B). Solution B was then quickly poured into solution A under a
constant high speed strirring. After 1 min, the stirring speed was reduced. At that time the breaker was sealed with
plastic wrap and left for two more hours. Finally, the SiO2 nanoparticles were collected by high-speed centrifugation,

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
and washed with ethanol. This process was repeated three times before drying the SiO2 nanoparticles at 80C.
On the other hand, the SiO2 nanoparticles were extracted from Sidoarjo mud using co-precipitation method. At first,
the Sidoarjo mud was dried and then grinded with mortar until 250 mesh. After that, the fine Sidoarjo mud were
immerse with HCl [2M] for 24 hours to remove the pollutant, then washed with distilled water, dried, and grinded again
until 250 mesh. 10 gr prepared Sidoarjo mud were dissolved in 60 ml NaOH [7M] while stirred for 1 hour at 70C.
Then, 250 ml distilled water was added and filtered with filter paper. The filtered solution was then added with HCl
[2M] until it achieved pH7 and the white precipitate was obtained. The resulting suspension was maintained at room
temperature for 24 hours and subsequently filtered and washed several times with distilled water for remove the acid,
alkali, and salt content, then dried for 24 hours at 80C.
2.3. Preparation of TiO2@SiO2 core-shell nanoparticles
TiO2@SiO2 core-shell nanoparticles (TEOS) were synthesized using sol-gel method, 0.1 g of rutile TiO2 were
dispersed into 30 ml ethanol. In the mean time, the mixed of 0.5 ml TEOS, 20 ml ethanol, 10 ml distilled water and 0.5
ml ammonia was added into colloidal solution. The mixture solution with TiO2 rutile content was stirred for 2 hours at
room temperature. After 2 hours, the precipitate was collected by centrifugation and washed with ethanol and water
several times. The as-obtained product was dried at 100C for 2 hours [11].
Similar method as applied to SiO2 extraction in Section 2.2 was used. For TiO2@SiO2 core-shell synthesis with
rulite addition was given prior to titration of HCl [10].
2.4. Preparation of the photoanode and assembling for DSSC
The photoanode pastes were prepared by dissolve 2 gr of photoanode powders in 0.7 ml distilled water. The powders
were grinded with mortar and added with 1 ml CH3COOH 98% and 0.1 ml Triton X-100. Before being used, the
transparent conducting oxide (TCO) glass pieces were washed with ethanol. A photoanode film was fabricated on the
TCO glass by using the doctor-blade technique followed by sintering at 225C for 2 min. After that, the the photoanode
film was immersed in approximately 15 ml of mangosteen dye solution for 12 hours [12].
The counter electrode was obtained by giving carbon (C) on TCO glass. The width of two electrodes was adjusted to
about 24 m for being filled by liquid electrolyte of iodine/triiodide (I-/I3-).
2.5. Characterization
The core-shell nanostructures were characterized by x-ray diffraction (XRD, Philips XPert MPD) using Cu-K
(=0.154056 nm) and fourier transform infrared spectroccopy (FTIR, Thermo Nicolet i510). The optical properties of
mangosteen dye was measured by UV-Vis absorpsion spectroscopy (UV1100). Photocurrent-voltage curves were
measured under direct irradiance of sun at daylight using the equivalent circuit. The light intensity was measured using
Pyranometer (Star Pyranometer 240-8101 Novalinx Corp.). The photocurrent action spectra or IPCE (Incident Photon
Conversion Efficiency) in visible light spectrum was obtained by adjusting wavelength of incident light under solar
simulator, i.e. series connection of halogen lamp (GR-150 Halogen Flood Light 150W) and monochromator (CT-10T,
JASCO). The value of incident light power was measured by using optical power meter (Thorlab S-120C).
3. Result and discussion
3.1. Microstructure
Figure 1 shows the XRD pattern of TiO2 and TiO2@SiO2 core-shell structure. For anatase and rutile TiO2 all
observed peaks are in good agreement with the standard spectrum (JCPDS 00-021-1272 and 00-021-1276). By using
Scherrer equation, the crystallite size of anatase and rutile TiO2 were determined and the values were about 15 nm and
69 nm, respectively. On the other hand, the XRD spectra of TiO2@SiO2 from TEOS and mud extract were marked by
shoulder peak around 2 = ~24 and the peak intensities of rutile TiO2 were weaker than bare rutile TiO2, which is
attributed to the present of SiO2 in an amorphous state around the rutile TiO2 [8,10]. The stronger this shoulder, the
more SiO2 attaches the TiO2 [1,14]. In addition, the TiO2@SiO2 from mud extract contains the supplementary peaks
which correspond to -Fe2O3 and -Al2O3.

R (110)

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
TiO2@SiO2 (mud extract)
TiO2@SiO2 (TEOS)
TiO2 (rutile)

R (310)

R (002)

R (220)

- Al2O3

R (201)

R (202)

R (111)

- Fe2O3

Intensity

R (101)

R (211)

TiO2 (anatase)

A(101)
A(200)

A(004)

15

20

25

30

35

40
o

45

A(211)

50

55

A(204)

60

65

2Theta

Fig. 1. XRD patterns of anatase and rutile TiO2, TiO2@SiO2 core-shell structure
3.2. Interfacial structure
Figure 2 shows FTIR patterns of TiO2, SiO2 and TiO2@SiO2 core-shell structure from TEOS and mud extract. The
band at 1077.25 and 1076.42 cm-1 attribute to the asymmetric stretching vibration of Si-O-Si bond, while other bands at
3267.29 and 1636.43 cm-1 correspond to H-O-H stretching (absorbed water) and H-O-H bending water, respectively.
Also the band at 1015.31 cm-1 attributes to Si-O stretching, band around 700 cm-1 is Si-O perpendicular and band at
1113 cm-1 corresponds to Si-O stretching (longitudinal mode). The band around 915 and 540 cm-1 indicates the OH
deformation linked to 2Al3-, and Fe-O (Fe2O3), Si-O-Al stretching, respectively, this result corresponds to the XRD
patterns which is contain a -Fe2O3 and -Al2O3 peak. This FTIR patterns shows that SiO2 nanoparticles were formed
corresponds to Si-O-Si bond, but the bond of Ti-O-Si which is supposed to be located at 933 cm-1 does not appear in
SiO2 shell made from TEOS and only sluggishly emerge in SiO2 shell made from mud extract [1316]. This may
indicate that SiO2 mud extract covers the TiO2 particles which is in agreement with Figure 1.
90

Transmittance (a.u.)

100

Transmittance (a.u.)

90
H-O-H

C-H

80

C-H
-OH

H-O-H

80

70

60

50

TiO2 @SiO2 (mud extract)


TiO2 @SiO2 (TEOS)

Ti-O-Si Si-O

Si-O

70

40

TiO2 rutile

Fe-O, Si-O-Al
30

Si-O

50

1000

Si-O

TiO2@SiO2 (mud extract)


TiO2@SiO2 (TEOS)

40

TiO2 rutile

Ti-O-Ti

30
3750

3500

3250

3000

2750

2500

2250

875

750

625

Wavenumbers (cm-1)

CO2

60

4000

Ti-O-Si

2000

1750

1500

1250

1000

750

500

Wavenumbers (cm-1)

Fig. 2. FTIR patterns of the prepared rutile TiO2 and TiO2@SiO2 core-shell structures.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
3.3. Performance of DSSC

0.12

TiO2 anatase

0.11

TiO2 anatase rutile (90:10)

0.10

TiO2NP/TiO2@SiO2 TEOS (92,5:7,5)

0.09

TiO2NP/TiO2@SiO2 mud extract (92,5:7,5)


TiO2NP/TiO2@SiO2 TEOS (90:10)

Jsc (mA/cm )

0.08

TiO2NP/TiO2@SiO2 mud extract(90:10)

0.07
0.06
0.05
0.04
0.03
0.02
0.01
0.00
0

25

50

75

100

125

150

175

200

225

250

V (mA)

Fig. 3. J-V curve of the DSSC with various photoanodes sensitized by mangosteen pericarp dye.

Tabel 1. Jsc, Voc, FF, and of the JSSC


Voc
Photoanode
Fraction(%)
Jsc (mA/cm-2)
(mV)
TiO2 anatase
100
192.0
0.026
TiO2 anatase : rutile
90:10
212.0
0.115
TiO2 anatase,rutile/ TiO2 rutile@SiO2 TEOS
92.5:7.5
125.0
0.018
TiO2 anatase,rutile/ TiO2 rutile@SiO2 TEOS
90:10
220.4
0.100
TiO2 anatase,rutile/ TiO2 rutile@SiO2 extraction
92.5:7.5
100.0
0.044
TiO2 anatase,rutile/ TiO2 rutile@SiO2 extraction
90:10
71.0
0.013

FF(%)

(%)

32.051
32.545
18.685
25.102
14.234
24.455

0.0027
0.0132
0.0007
0.0092
0.0011
0.0004

The J-V curve for studied DSSC is shown in Figure 3. The photovoltaic properties, including the open-circuit
voltage (Voc), the short-circuit current density (Jsc), the fill factor (FF), and the power conversion efficiency () are
tabulated in Table 1. It is shown that the DSSC with core-shell structures from TEOS precursor had Voc value better
than the DSSC with core-shell structures from mud extract. The DSSC which is added with 10wt% core-shell structures
from TEOS has the the highest Voc (220.4 mV) and its efficiency achieves 0.0092%. This value is 2.4 times larger than
that of DSSC with pure anatase photoanode. An increase of Voc implies that the charge recombination between injected
electron and I3- on the TiO2 and electrolyte interface decreases and this effect is determined by the presence of SiO2
surrounding the TiO2 [17]. Despite the absence of Ti-O-Si band in Figure 2 for the studied photoanodes, for the case of
SiO2 made from TEOS, it is not clear yet whether the SiO2 successfully covers the TiO2 or it only decorates the TiO2
surface as a loose particle, further investigations are needed to justify this. Whereas for SiO2 made from mud extract,
although according to FTIR and XRD results the SiO2 from mud extract is likely to coat the TiO2 particles, the
efficiency of DSSC does not improve noticeably. Aggregation of particles frequently is known to cause poor interfacial
contact and can be one of the reason leading to lower the efficiency [18].
The better efficiency of core-shell structure with the shell made from TEOS can be explained through the IPCE
curves (Figure 4) which is consistent with the J-V curve (Figure 3). It is seen that the spectrum of SiO2 from TEOS
(400-500 nm) is wider than that of mud extract (400-450 nm). It seems that SiO2 from TEOS allows more light being
absorbed by the dye attached on the nanoparticles and the higher interaction between TiO2 and the dye extract may lead
to a better charge transfer [19].

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
0.30

TEOS
Mud Extract
0.25

IPCE (%)

0.20

0.15

0.10

0.05

0.00
350

400

450

500

550

600

650

700

750

Wavelength (nm)

Fig. 4. IPCE spectra of the studied photoanodes with TiO2/core-shell fraction of 90:10 loaded with mangosteen pericarp
extract dye.
4.

Conclusions
The attempts to produce TiO2@SiO2 core-shell embedded in DSSC photoanode were undertaken. To this point our
results indicate that SiO2 from mud extract may coat the TiO2 better than SiO2 from TEOS as indicated by XRD and
FTIR. However, the efficiency of the DSSC incorporating the TiO2@SiO2 core-shell from mud extract is still below
that of from TEOS. Agglomeration of the coating agent and the imperfection of coating may be the reason. Further
investigation is needed to justify this.
Acknowledgements
The author would like to thank to Directorate of Higher Education Ministry of Research Technology and Higher
Education Republic of Indonesia for Supporting this work under Penelitian Unggulan Perguruan Tinggi scheme
contract number : 003246.136/IT2.11/PN.08/2015.
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Compressive Strength of Geopolymer Mortar, Adv. Mater. Res., vol. 626, pp. 224228, 2013.
[7] R. S. Mustopa and D. D. Risanti, Karakterisasi Sifat Fisis Lumpur Panas Sidoarjo dengan Aktivasi Kimia dan
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Abidin, and M. K. A. Mohamadiah, Adsorption of methyl orange from aqueous solution onto calcined Lapindo
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The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
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The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
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CODE: IM
Improved Strength Of Sugarcane Bagasse Fibers-Polypropylene Composite Using Alkali Treated Fibres
Juliana Anggono,1,*) Suwandi Sugondo,1) Hariyati Purwaningsih2), and Steven Henrico1)
1)

Department of Mechanical Engineering Petra Christian University, Surabaya 60236, Indonesia

2)

Department of Materials and Metallurgical Engineering, Sepuluh Nopember Institute of Technology, Surabaya
60111, Indonesia
Abstract: Sugarcane is one of the main agricultural products in Indonesia after palm oil, coconut, and rubber. Bagasse
fibres are produced from the milled sugarcane stalks. These fibres are considered as byproduct and has little value.
These natural fibres are strong, lightweight, and offer benefits in reductions in cost, CO2, less reliance on oil sources
and recyclability. They have been investigated and identified as potential reinforcement to replace synthetic fibres such
as glass and carbon fibres. In this present work, bagasse composites using polypropylene (PP) matrix were developed.
Alkali treatment using 14% v/v Ca(OH)2 was applied on bagasse fibres and the strength of the composites produced
was evaluated as the effects of the soaking time during alkali treatment, fiber length, and the quantity of bagasse fibres
used. Alkali treatment for 2, 4, and hours gave a composite strength in the range of 3.36-9.07 MPa, 4,84-11.3 MPa, and
7.0-14.72, respectively. The strength of composites which used untreated fibers in original length was in the range of
7.22-11.38 MPa with the highest strength obtained in the composites with 20/80 wt. % ratio of bagasse/PP. Those
strength data means that treated bagasse fibers with Ca(OH)2 was not effective in increasing strength of composite when
duration of alkali treatment was up to 4 hours. Two hours soaking time gave the lowest strength of the composite.
Adding the treated bagasse fibers to 25 wt. % to PP increased the strength of the composite and increase the fiber
content up to 30 wt. % reduced the composite strength. Fourier transform infrared spectroscopy (FTIR) and scanning
electron microscopy (SEM) were performed to study the structural change on the fiber surface after alkali treatment.
SEM was also used to evaluate the fracture surface of the composite after tensile testing.
Keywords: sugarcane bagasse; alkali treatment; calcium hydroxide; polypropylene.
Corresponding author: Juliana Anggono, E-mail: julianaa@petra.ac.id, Tel. +62-31-2983467
1. Introduction
Biocomposites made from polymers reinforced with natural fibers have been developed and manufactured.
Automotive sector is one of the growing market for components made from biocomposites. Those components
produced are mainly used for door panels, trunk lining, headliner panel, seat backs, rear parcel shelf (package trays),
and noise insulation panels. They offer weight reduction about 10%, energy saving in production of 80%, and cost
reduction of 5%. [1] The increase of consumers with green awareness to use natural fiber composites will also grow the
natural fiber composites market. The global natural fiber composites market has reached US$ 298,3 million in 2010
with compound annual growth rate (CAGR) of 15% from 2005. By 2016 the market is predicted to reach US$ 531,3
million with CAGR of 11% from 2010.[2] European countries is the top continent for consumption of natural fiber
composites and makes it the largest region for automotive applications. While North America is the biggest consumers
for building and construction applications made from wood fibers. The increasing demand for natural fiber composites
in China and India will make Asia as one emerging big market for those biocomposites.[3]
Natural fibers used for manucfacturing components in the automotive sector are non-wood fibers, such as flax,
kenaf, hemp, jute, and sisal. Research done by a team at Baylor University led by Prof. Walter Bradley has used coir
from the outer husks of coconuts to make trunk liners, floorboards, and car-door interior to replace poyester fibers that
commonly used in the automotive application. [4] Using similar approach of finding natural fibers for biocomposites
application, in this research work the potentials of bagasse fibers which are renewable resources and grow in Indonesia
were studied. Bagasse fibers is the fibrous residue which are obtained from milled sugarcane stalks that are harvested
from grass family plant named saccharum officinarum. The sugar production results in large amounts of bagasse which
is about 30-32% of the total cane weight.[5] It consists of fibres (48% including ash), water (50% moisture), and
relatively small amount of soluble solids (2%) - mostly sugar. [6] The fibre as similar with other lignocellulosic materials
consists mainly of cellulose (42,3%), pentosans (25,1%), lignin (24,7%), acetyl groups (3,7%), and ash (3,5%).[7] To
prepare and enable wide-scale acceptance and confidence of the commercial communities, a thorough and fundamental
of some major technical considerations must be addressed. Some of the limitations of natural fibers as reinforcement for
composites are related to the low strength properties, low interfacial adhesion between fibers surface and matrix, low
moisture repellance, limited processing temperature ( 200oC), and flame-retardant properties. To overcome the
limitations, various treatments can be applied to modify the fibers surface in order to improve the adhesion between
fibers and matrix which can result in improvement of mechanical properties of the end products. One of the treatments
is mercerization (alkaline treatment). Strong alkaline solution of NaOH is a common alkaline solution used in the

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treatment. However, NaOH is reactive and hazardous solution to handle. Other works have used different solution in the
pretreatment stage to prepare the bagasse fibers. Cerqueira, et al. reported an increase of 16% in tensile strength of
composite (22.3-23 MPa) compared to the strength of polypropylene when adding 5, 10, and 20% treated bagasse
fibers. The solution and the treatment steps used were pretreatment using 10% H2S solution followed by delignification
with 1% NaOH solution.[8] Leite et al. used Ca(OH)2 solution to neutralise sugarcane pulp before drying, grinding, and
forming the composite using phenolic resin. Highest tensile strength was found in the composite with 29% fibers with a
size of 80-170 mesh.[9] In this present study, calcium hydroxide or Ca(OH)2 was used as an alternative alkaline solution
to NaOH as it is less corrosive and less hazardous. [10] Soaking time during alkali treatment was varied from 2, 4, and 6
hours. The bagasse fibers were provided in various length, i.e. 3 cm, 5 cm, and as their original length. Composites were
prepared using wt. % ratios of bagasse fibers to PP fibers of 20/80, 25/75, and 30/70. The strength property of the
composites was evaluated by studying the effect of fiber length, alkali treatment, and the wt. % ratio. Structural
characterisations using SEM, EDAX analysis and FTIR both on the fiber surface and the fracture surface of composite
were performed.
2. Experimental
2.1. Materials Preparation
Bagasse fibers obtained was first neutralised using 70% ethanol for 1 hour. A ratio of bagasse weight (kg) to
volume of ethanol (litre) of 1:2,5 was used. The aim of neutralisation process was to prevent bagasse fermentation due
to the presence of bacteria which could cause fiber degradation and released unpleasant smell. The neutralised bagasse
was then oven dried at a temperature of 200oC for 30 seconds. After drying, the bagasse were soaked in alkaline
solution of calcium hydroxide, Ca(OH)2 14 v/v % for 2 hours, 4 hours, and 6 hours at temperature of 60o - 70oC. The
alkali treatment applied used a ratio of dried bagasse weight (g) to volume of Ca(OH)2 14 v/v% (ml) of 1:15 g/ml. After
treatment, fibers were then rinsed with distilled water. To ensure the fibers were already clean, pH of rinsed water was
monitored. Rinsing ended when pH of rinsed water reached pH=7. Oven drying at a temperature of 200oC for 30
seconds was done to remove absorbed water. Those steps were repeated to prepare bagasse fibers at various length of 3
cm, 5 cm, and as their original length.
PP fibers were available from a local carpet industry as waste with a length of 20 cm. To ensure a homogeneous
mixture with bagasse fibers, these PP fibers were cut into short fibers of 1 cm long.
2.2. Making Composite Samples
Table 1 shows the amount of bagasse and PP fibers prepared to make composite samples (60 g per sample) with
ratios bagasse fibers/PP in wt.%: 20/80, 25/75, and 30/70. Both fibers were mixed for 3 minutes in a mixing machine
using centrifugal blower. The mixture was formed into a sheet by a hot press machine using a pressure of 9,8 kPa at
temperature of 175oC for 3 minutes. Table 2 shows sample coding to identify condition of bagasse fibers used and
composition of each sample.
2.3. Tensile Test
Tensile test specimens were prepared from hot pressed composite sheet with specimen dimension conformed with
ASTM D 638M-03. Tensile test was performed using Instron DX model with an extension rate of 10 mm min-1.
2.4. Structural Characterisation
Structural characterisation using SEM (Scanning Electron Microscopy) was performed not only on fracture surface
of tensile tested samples but also on fiber surface after alkali treatment at various soaking time. Obtaining the
information about the structure change on fiber surface due to various duration of alkali treatment can help to
understand the tensile properties together with the observation on the fracture surface on tensile tested samples. SEM
machine used was FEI type Inspect S50 which was equipped with EDAX analysis. Characterisation on the fibers in
isolation was also done using FTIR (Thermo Scientific Nicolet model) to study the effect of calcium hydroxide
treatment on the chemical structure of the bagasse fibers.

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Table 1 Volume fraction and weight % ratio of
bagasse/PP

Table 2 Sample identification

Volume
Fraction
(%)

Weight % Ratio
of Bagasse/PP

Weight of
Bagasse
Fibers (g)

Weight of
Polypropylene
(g)

12,7

20/80

12

48

16,3

25/75

15

45

18,4

30/70

18

42

Sample Code

Weight % Ratio of
Bagasse/PP

Aix

20/80

Aiy

25/75

Aiz

30/70

Ajx

20/80

Ajy

25/75

Ajz

30/70

Akx

20/80

Aky

25/75

Akz

30/70

Bix

20/80

Biy

25/75

Biz

30/70

Bjx

20/80

Bjy

25/75

Bjz

30/70

Bkx

20/80

Bky

25/75

Bkz

30/70

Cix

20/80

Ciy

25/75

Ciz

30/70

Cjx

20/80

Cjy

25/75

Cjz

30/70

Ckx

20/80

Cky

25/75

Ckz

30/70

Length of
Bagasse Fiber
(cm)

Alkali Treatment
Soaking Time (hours)

original length

original length

original length

3. Results and discussion


3.1. Thickness
Composite thickness was measured from tensile test samples using micrometer before test was performed.
Thickness data were collected to understand the effect of pressure used during hotpressing on different conditions of
bagasse fibers mixed with PP. Fig.1 shows composite thickness from all samples. The range of thickness data obtained
was from 2,17-3,31 mm. The sample thickness increases with the increase of wt. % bagasse fibers in the composite.
Composites which contained 25 wt. % bagasse fibers (code Y) were thicker than composites contained 20 wt. %
bagasse fibers (code X). That thickness increment can be found in composites contained fibers treated for 2 and 4
hours. However, loading the composites up to 30 wt. % bagasse fibers which treated for 6 hours (code Z) results in
thickness reduction. Bagasse fibers in the composite provide a rigid architecture in the composite structure therefore
when the amount of bagasse fibers added to PP increases, thickness will be added. However, when soaking time during
alkali treatment was added up to 6 hours, the cleaning action on the fiber surface occurred in longer time leading to a
decrease in fiber diameter, increasing the aspect ratio and wetting area of PP on fiber surface which resulted in
reduction of thickness of the composites. Similar trend was found in previous work using NaOH solution to treat
bagasse fibers. [11]
5

18

thickness (mm)

Tensile Strength (MPa)

16

14
12

10
8

IX

IY

IZ

2 hours treatment

JX

JY

JZ

4 hours treatment

KX

KY

KZ

6 hours treatment

Fig. 1. Thickness of composite resulted from various


weight % ratio of bagasse/PP, length of bagasse fibers, and
soaking time

2
IX

IY
IZ
2 hours treatment

JX
JY
JZ
4 hours treatment

KX
KY
KZ
6 hours treatment

Fig. 2. Tensile strength of composite resulted from


various weight % ratio of bagasse/PP, length of bagasse
fibers, and soaking time

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3.2. Tensile Properties


Bagasse fiber provides a rigid architecture for the composite. During hotpressing at temperature 200oC, melted PP
fibers fill in the spaces available between the bagasse structure and wet the bagasse fibers and hence improving
composite strength. Looking at the chart in Fig. 2, most of the data show that the presence of bagasse in the composite
increases its strength up to 25 wt. % bagasse. The strength data obtained for composites with 25 wt. % fibers are 5.547.73 MPa (3 cm fibers), 5.1-11.3 MPa (5 cm fibers), and 8.3-11.84 MPa (original length fibers). Meanwhile the
composites with 20 wt. % bagasse fibers had data strength of 4.84-7.0 MPa (3 cm fibers), 8.51-9.7 MPa (5 cm fibers),
and 8.61-10.1 MPa (original length fibers). Loading the bagasse of original length up to 30 wt. %, the tensile strength
decreased (5.6-10.22 MPa) due to lacking PP to wet the bagasse. However, composites contained short bagasse fibers
(3-5 cm) which were treated for 6 hours show an increase in their strength when loaded up to 30 wt. %. Short fibers
could be easily wetted by PP then longer fibers when they were added up to 30 wt. %. The length of fibers from
original length group was measured. Their length was in the range of 3-24 cm with the majority of fibers present had a
length of 12-21 cm (70%).
Tensile strength of the composites was also affected by the duration of alkali treatment using Ca(OH)2. The
strength data range obtained for composites using fibers which were treated for 2 hours were 3.36-9.07 MPa. Their
strength were the lowest strength compared to composites using 4-hour treated (4.84-11.3 MPa) and 6-hour treated
fibers (7-14.72 MPa). The strength of composites using untreated bagasse fibers of original length was also evaluated
and their strength values obtained were 11.38 MPa, 7.38 MPa, and 7.22 MPa for a wt. % ratio of bagasse/PP 20/80,
25/75, and 30/70 respectively. These values show that treating the original length of bagasse fibers using Ca(OH)2 for
2-6 hours (sample code KX, KY, KZ) did not give significant change to the composite strength (the highest strength
was 11.48 MPa).
3.3. Structural Study on Fibers Surface
Structural study on the fibers surface is important to get a better understanding of structural change due to alkali
treatment on the fibers surface. The structural change on the surface determines the surface adhesive bonding of the
fibers which can improve the strength of the composites produced. Alkali treatment on the fibers caused weight loss due
to removal of wax, lignin, and hemicellulose from fiber surface. The weight loss calculated after completion of
neutralisation process in 70% ethanol was 15%. Fig. 3 shows the weight loss data in various soaking time during alkali
treatment. The data were calculated from the weight difference of oven dried fibers after neutralisation process (before
alkali treatment) and after alkali treatment. Though the weight loss increases with the addition of soaking time,
however in the first 2 hours of treatment, the fibers experienced a significant loss (25%) compared to the weight loss of
the same length of time from 2 hours to 4 hours (11%) and from 4 hours to 6 hours (10%). This was understood that
effective cleaning of fiber surface took place in the first 2 hours. FTIR tests in Fig. 4 and SEM images in Fig. 5 could
help to explain the findings.
50

46

weight loss (%)

45
40

no treatment

36

30

Absorbance (a.u)

35

2 hours treatment

25

4 hours treatment

25

6 hours treatment

20
15
10

soaking time (hours)

6
4000

3500

3000

2500

2000

1500

1000

500

wavenumber (cm-1)

Fig. 3. Weight loss data obtained in different


soaking time during alkali treatment

Fig. 4. FTIR Spectra of untreated and treated bagasse fibers

All treated fibers which soaked in different time were tested with FTIR to study the surface chemical structure. The
spectra was shown in Fig. 4 and they were compared with the FTIR spectra of untreated bagasse fibers for comparison.
As it is known that the components of bagasse include cellulose, hemicellulose, lignin, ash, and other components. The
cellulose and hemicellulose are hydrophilic, while lignin is hydrophobic.[12] The amount of each component varies
depending on the climate, soil condition, and the age of the crop. Comparing the spectra of treated and untreated fibers,
there were several absorption bands were not observed in treated fibers within the region from 2000 to 700 cm-1. The
CH stretch at 2893 cm-1 is identified in all fibers both untreated and treated. This band refers to polysaccharide which is
component of cellulose. [13] The band 1730 cm-1 indicates the C=O stretching of the acetyl groups of hemicellulose [14,15]
and was only noted in untreated fibers. This band was not observed in all treated fibers which indicating the removal of

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hemicellulose even in the 2 hours of treatment. The absorption band at 1250 cm-1 which is a lignin spectrum was not
appeared in treated bagasse fibers. Lignin is an amorphous phenolic macromolecule and has the least water sorption of
the natural fiber components. [16] The removal of lignin during treatment was favorable to improve interfacial bonding
between fibers and matrix. There were found absorption bands in the range of 1500-1400 and 872 cm-1 in spectrum of
treated fibers. Those bands indicated the presence of carbonate peaks on the fiber surface after treatment. SEM images
on the fiber surface after treatment observed the presence of bright particles deposited on the surface (Fig. 5 b)-d)).
Surface of untreated fiber in Fig. 5 a show no such particle. Those particles were from the Ca(OH)2 solution which
contained CaCO3 as indicated by XRD test. Cleaning of sugar cane fiber from lignin and hemicellulose is the main goal
of alkali treatment to improve the wetting ability of PP on the surface of sugarcane fiber.
Fig. 5 shows the effect of alkali treatment on bagasse fibers. They show a significant different on SEM images
between untreated and treated fibers. The untreated fiber was observed without fibrillation (Fig. 5 a) compared to the
surface structure of the treated ones. As lignins are the cementing components that bond cellulose fibers together,
therefore as they were removed during the treatment causing fibrillation of the fiber bundle to take place. The increase
of soaking time during the treatment causing the fibrillation more obvious (Fig. 5 c).

a)

b)

c)

d)

Fig. 5. SEM micrographs of bagasse fibers in different treatment a) untreated, b) 2 hours treatment, c) 4 hours
treatment, and d) 6 hours treatment.
3.4. Structural Study on Fracture Surface of Composite
Fracture surface of the composite samples after tensile test was characterised by SEM to study the fibers/matrix
bonding mechanism, fibers orientation and distribution, as well as fracture mechanism. Fig. 6 a) and b) are the SEM
images of the fracture surface of composite sample contained 20 wt. % of 5 cm length of 4 hours treated bagasse fibers.
Fig. 6 a) shows an area about 1x6,25 mm2 in the cross sectional surface has very few fibers in the PP matrix. This
observation shows that the fibers in that sample were not homogeneously distributed across the sample thickness. Small
void was also identified in the cross sectional area in Fig. 6 b). Most fibers in the PP matrix were in transversal direction
to the tensile stress. Fiber pull-out was observed in another sample using same length and amount of bagasse fibers (Fig.
7 a). The fibers used were experiencing 6 hours soaking in Ca(OH)2 solution. Void in the interfacial region between
fiber and PP matrix was evidenced in Fig. 7b). The strength obtained for this composite (JX 4 hours treatment) as

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shown in Fig. 2 was 9,7 MPa. The work of Cerqueira et al. (2011) using bagasse fibers
ibers pretreated with 10% H2S
solution
on followed by delignification with 1% NaOH solution mixed with PP resulted in composite strength of 22.3 MPa.
[8]
The carbonate deposit remained on the fibers surface after rinsing could be one of the obstacle for wetting thus
prevent to have good adhesion.
n. Fig. 8 a) and b) show fibers splitting and presence of voids in the structure.

Fibre
pullFew Fibres
present

voi

a)
b)
Fig. 6. SEM micrographs of fracture surface composite with 4 hours treated bagasse fibers (5
cm length and wt. % ratio bagasse/PP 20/80)

voi

voi
Fibre
pulla)
b)
Fig. 7. SEM micrographs of fracture surface composite with 6 hours treated bagasse fibers (5
cm length and wt. % ratio bagasse/PP 20/80)

voi
voi

a)
b)
Fig. 8. SEM micrographs of fracture surface composite with 6 hours treated bagasse fibers
fibers (3
cm length and wt. % ratio bagasse/PP 25/75)

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4.

Conclusion
Bagasse fibers which were alkali treated using Ca(OH)2 solution experienced a significant change on their surface
structure. Lignin and hemicellulose were removed from the fibers surface as evidenced by FTIR and fibrillation of
cellulose fibers was obvious with the increase of soaking time. Tensile strength of the composites produced from these
treated fibers reinforced PP using short fibers of 3 cm was lower than the strength obtained in the composites using
untreated original length fibers.
Acknowledgements
We thank Ms. Russava Istiani for her assistance with materials characterization.
References
[1] Balaji, B. Karthikeyan, and C. Sundar Raj, Bagasse fiber the future biocomposite material: a review, Inter.
Journal of Chem. Tech. Research, 7 (1) (2014), p 223.
[2] Lucintel Report (2010) on the Natural Fiber Composites Market Trend and Forecast 2011-2016: Trend, Forecast,
and Opportunity Analysis.
[3] Technologies and Products of Natural Fibre Composites CIP-EIP-ECO-Innovation-2008 ID:ECO/10/277331
[4] http://www.livescience.com/3180-car-parts-coconuts.html retrieved 13 September 2015
[5] S.C. Lee and M. Mariatti, Mater. Lett. 62(2008), p 2253
[6] http://www.fao.org/docrep/003/s8850e/s8850e03.htm, retrieved 13 September 2015
[7] G.J.M. Rocha, et al., Mass balance of pilot-scale pretreatment of sugarcane bagasse by steam explosion followed
by alkaline delignification. Bioresour. Technol. 111 (2012), p 447.
[8] E.F. Cerqueira, C.A.R.P. Baptista, and D.R. Mulinari, Mechanical behaviour of polypropylene reinforced
sugarcane bagasse fibers composites, Procedia Engineering 10 (2011), p. 2046.
[9] J.L. Leite et al., Characterisation of a phenolic resin and sugar cane pulp composite, Brazilian Journal of
Chemical Engineering, 21(2) (2004), p 253.
[10] Material Safety Data Sheet of calcium hydroxide: http://www.sciencelab.com/msds.php?msdsId=9927122
retrieved 1 August 2015.
[11] J. Anggono, S. Sugondo, and N. R. Habibi, Alkali treatment on sugarcane bagasse to improve properties of green
composite of sugarcane bagasse fibers-polypropylene. (D. Singh, & J. Salem, Eds.) Mechanical Properties and
Performance of Engineering Ceramics and Composites, IX (2014), p 139.
[12] X.F. Sun, R. C. Sun, and J.X. Sun, Acetylation of sugarcane bagasse using NBS as a catalyst under mild reaction
conditions for the production of oil sorption-active materials, Bioresource Technology 95(3) (2004), p 343.
[13] R.M. Rowell, R. A.Young, and J.K. Rowell, Paper and composites from agro-based resources, CRC Lewis
Publishers, Boca Raton RL (1997)
[14] J. Biagiotti, et al., A systematic investigation on the influence of the chemical treatment of natural fibers on
the properties of their polymer matrix composites, Polym Composite, 25(5) (2004), p 470.
[15] W. Liu, et al., J. Mater. Sci., 39 (2004), p 1051.

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CODE: IM
Synthesis of Porous Si-doped ZnO Thin Films Using Self-Assembly Mechanism Enhanced by Chitosan as
Coupling Agent
Rais Fiqriansyah1), Lia Asri2), Arie Wibowo3), Bambang Sunendar4)
1

Department of Materials Engineering, Faculty Mechanical and Aerospace Engineering, Institut Teknologi Bandung,
Bandung 40132, Indonesia, raisfat@gmail.com
2
Department of Engineering Physics, Faculty of Industrial Technology, Institut Teknologi Bandung, Bandung 40132,
Indonesia, tresna.asri@gmail.com
3
Department of Materials Engineering, Faculty Mechanical and Aerospace Engineering, Institut Teknologi Bandung,
Bandung 40132, Indonesia, arie.akfiny@gmail.com
4
Department of Engineering Physics, Faculty of Industrial Technology, Institut Teknologi Bandung, Bandung 40132,
Indonesia, purwa@tf.itb.ac.id
Abstract: Si-doped ZnO (SiZO) thin films, which is one of Transparent Conducting Oxides (TCOs) alternatives, have
been successfully synthesized. Synthesis process using self-assembly mechanism that involving sol-gel method and
immersion technique on soda-lime glass from a precusor solution containing zinc acetate dihydrate and silicon
tetraethoxide. The addition of chitosan concentration varied on 0,5;1;1,5 (% w/v) whilst the concentration of silicon are
used by 0,8% as dopant with indirect-drying method and multi-step calcination at 450 C. Based on morphology of thin
films that we have investigated, 1% w/v chitosan addition proven to optimize self-assembly mechanism which
generates porous film structure with layer-by-layer growth type. Furthermore, UV-VIS spectra showed that addition of
chitosan reduced electron trapping phenomenon and increase their transparency.
Keywords: Si-doped ZnO, chitosan, self-assembly, morphology, electron trapping.
Corresponding author: Rais Fiqriansyah, E-mail: raisfat@gmail.com , Tel. +62-813-73679873, Fax. +62-22-2508144
1. Introduction
Porous thin film based on zinc oxide (ZnO) has become a promising option for wide applications like sensors, solar
cell, flat display, UV laser, light-emitting diodes, and transparent display [1], due to its multiple properties such as
pyroelectric properties, piezoelectric, and semiconducting [2]. Nowadays, ZnO become priority because the high
abundance of ZnO in earth crust, nontoxicity, and posiibility to prepare highly-doped film with high free electron
density, and any other characteristics which can be fulfilled the requirement for Transparent Conducting Oxides (TCO)
[3]. It has been reported that in Si-doped Zinc Oxide (SiZO), silicon will occupy cation site and as the result, Si
doping in ZnO could adjust the properties of electronic and optical from ZnO. In addition, the advantage in Si-related
devices will be enhanced.
Since the first time reported [4], SiZO have been synthesized with various methods, for instance radio frequency
magnetron sputtering, spray pyrolysis, and pulsed laser deposition. One of the most disadvantages of SiZO thin film is
the high cost production until Sorar et al. [5] has successfully synthesized SiZO with lower production cost with sol-gel
technique and spin-coating, resulting in thin film with band gap 3.33 eV and high cristallinity (0.8% Si). One of the
disadvantages of this method is inefficiency in materials usage. Whilst, immersion deposition via self-assembly
mechanism offers better method than spin coating. This mechanism is induced by dipole-dipole interaction and noncovalent bond when thin film were formed [6], resulting in inter- and intra- molecular interaction lead to the formation
of a complex system [7].
In this work SiZO thin film has been successfully sythesized by sol-gel method with immersion deposition to get
porous thin film. Chitosan as coupling agent was employed to increase the interaction between glass substrate and
SiZO thin film. The morphologies and surface properties of resulting SiZO thin film were evaluated by using optical
microscope, scanning electron microscope (SEM), and energy dispersive spectroscopy (mapping EDS).The quality of
thin film related to type of thin film, where layer-by-layer growth type resulted high properties of doped ZnO thin films
[8, 9]. Porous structure on thin film has been reported to increase speific properties, such as sensivity for gas sensors
[10] and electron transport for solar cell [2].
2. Experimental
2.1. Materials
Zinc acetate dihydrate (ZnAc, Zn(CH3COO)2.2H2O, 98%), ethanol, silicon tetraethoxide (TEOS) and chitosan low
molecular weight were purchased from Sigma-Aldrich and used without further purification. Ammonium hydroxide
(NH4OH) was obtained from Merck.

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Fig. 1 Top view of thin films using various chitosan concentration. The bar denotes 200 um.
2.2. Preparation of the thin films
2.2.1. Colloidal solution preparation
Precusor solution used in this work composed of 1.756 gr zinc acetate dihydrate dissolved in 40 ml ethanol pro
analysis and stirred, after 20 minutes 40 ml methanol pro analysis was added, the solution was stirred for 25 minutes at
room temperature. During stirring, 0.0145 ml TEOS (Si(OC2H5)4, 99.999%. Aldrich) was added into solution. In order
to form colloidal solution, pH was adjusted to 8 or 9 by adding ammonium hydroxide (NH4OH, 25%).
2.2.2. Deposition of SiZO on glass substrate
The glass substrate was cleaned by immersion in detergent solution and alcohol at room temperature for 30 minutes
in Branson Ultrasonic Cleaner, subsequently the glass was dried under air. The colloidal solution was then deposited on
glass substrate by immersion method. Glass substrate was then immersed in chitosan solution just a moment and
subsequently immersed in colloid solution for 15 minutes. These steps were repeated once again to ensure the thin film
has been stick into glass substrate. Chitosan concentration was varied with 0.5;1;1.5 (%wt). Glass substrate with SiZO
deposition without chitosan layer was used as control.
Drying process was implemented after deposition done. Induction heat was used as drying process at around 100 C
to prevent agglomeration particles on thin films. Later, calcination was carried out with multi-step treatment to reach
450 C. In the first step, temperature reached 100 C and was held for 30 minutes. The next step, temperature was
increased to 200 C and was kept for 30 minutes, process entered the third step, when temperature reached 300 C and
also was held for 30 minutes. In the last step, calcination reached temperature at 450 C and after kept plateau, sample
was cooled down untill reach room temperature. The calcination was done in order to remove organic residues. Based
on literature, decomposition temperature of chitosan is 313.3 C [11], whereas ZnO was formed at 316.9 C [12].
2.3. Characterization
The samples were characterized with optical microscope, Nikon Omnimet in the 200 nm for scalebar. SEM and
mapping EDS were carried out using JEOL (JSM-35C). From optical microscope, different morphology graphics
achieved from three different chitosan concentrations which will lead on the optimum concentration. While, thin film
growth type can be seen from the samples using SEM. In addition, mapping EDS confirmed the porous structure of
thin film and proved SiZO thin film on glass substrate. While UV-Vis spectrofotometry Shimadzu UV-310PC showed
the effect by using coupling agent in optical properties.

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3. Result and Discussion


Fig. 1, shows the thin film morphology without using chitosan, demonstrating island-by-island growth type. This
type of thin film is not desired to achieve good properties of thin film. Thin film had layer-by-layer growth type was
formed by adding 1.5 % concentration of chitosan as coupling agent. Based on SEM characterization resulting thin film
is homogeneous with cracked trace in range 0.05-0.5 um length. Through crack type, it is clear that at first, thin film
formed one layer and then separated by crack. This phenomena also occured in 1% concentration of chitosan. Whilst,
on 1% wt , similar morphology was found as in the previous sample. But, thin film has successfully covered more area
than 1% wt. Although cracked trace was still exist in thin film like 1.5% wt, but the morphology at scale 1um showed
smaller porous and more homogeneous height than 1.5% wt. This morphology is similar with the work of Clatot et.al.
[13] and Santos et. al. [14].
Optical microscope images display that thin film prepared using chitosan 0.5% wt, show significant result with less
cracked trace and higher covered surface than chitosan 1%wt and 1.5 %wt. But unlike 1.5% and 1% where thin films
have homogeneous height of layer, in 0.5% wt, its morphology formed mountain-like with difference height. Therefore,
1.5% and 1% have layer-by-layer growth type meanwhile 0.5% chitosan has island-layer above on layer-by-layer
growth or known as mix growth type of thin film.

Fig. 2 SEM results on varied concentration of chitosan ( 0.5;1;1.5 (%wt)). The bar denotes 10 um (upper row) and 10
um (lower row).
Amine (-NH2) and hydroxyl (-OH), functional groups of chitosan chain, took a role bridge that can attach Si from
glass substrate with thin film particles through self-assembly mechanism. Higher concentration of chitosan means that
there will be higher amount of two functional molecules and more interaction would be formed so there are higher
chance for thin film to cover substrate uniformly. In contrast, based on Figure 1, when higher concentration of chitosan
applied, more area of substrate not covered due to more thin film peeled up. Another phenomena was found, when
concentration of chitosan was higher, there will be higher interaction of intermolecular on chitosan, it will cause the
function of chitosan as coupling agent less than lower concentration. This reason become rational answer for thin film at
1% could cover larger surface of glass substrate than higher concentration of chitosan.

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Fig. 3 EDS results for 1 % concentration of chitosan thin films with

Fig. 4 UV-Vis
Vis spectrofotometry of 0% wt and

scalebar denotes 50 um.

1% wt of chitosan
chitosan.

Thin film at 0.5% wt, which shows non homogeneous layer due to mix growth type of layer, might happen due to
the small amount of amine and hydroxyl
hydroxyl functions as coupling agent. When these functions not quite enough to attach
particles both on thin film and glass substrate, so self-assembly
self assembly mechanism was not going well. Homogeneous height of
thin film layers could be one of indicators for good self-assembly
self ssembly mechanism, Therefore, in 0.5% wt thin film is not
homogeneous as a result from not good self-assembly
self assembly mechanism. For some specific purposes, like optoelectronic
application or transparent conductive electrode, island layers which contained on mix growth
growth are not suitable enough
because electron trapping phenomena will occur and electrical properties will reduce.
From
rom morphology structure, mix growth type caused inhomogeneous nonporous thin film. While, on the largest
concentration of chitosan showed the thinnest film peeled-up
peeled up although it has porous structure. So for optimum
morphology and porous structure with less peeled-up
peeled up layers and homogeneous height of layer were on 1%
concentration of chitosan. Mapping EDS confirmed porous structure and SiZO elements
elements on thin film. Uv-Vis
spectrofotometry showed the difference between 0% wt (blue line) and 1% wt (green line) in transparency. And from
blue line, electron trapping phenomena can be noticed by red circle while it reduced when at 1% wt.
4.

Conclusion
Based
ased on morphology of thin films, although 1% concentration of chitosan had quite of layers that peeled
peeled-up and
cracked, the quality of this thin film showed the optimum condition with homogeneous height of layer compared to
chitosan 0.5% and 1.5% wt. Also by using chitosan 1% wt, could increased transparency for thin film.
References
[1] R. Chowdhury, P. Rees, S. Adhikari, F. Scarpa and S. Wilks, "Electronic Structures of Silicon doped ZnO,"
Physica, no. B405, 2010.
[2] I. Gonzalez-Valls and M. Lira-Cantu,
Cantu, "Vertically-aligned
"Vertically aligned nanostructures of ZnO for excitonic solar cells : a
review," Journal Energy & Environmental Science, vol. 2, pp. 19-34, 2009.
[3] K. Ellmer and A. Klein, "ZnO and Its Applications," in Transparent Conductive Zinc
inc Oxide : Basics and
Applications in Thin Film Solar Cells,
Cells ISBN 978-3-40-73612-7, 2008, pp. 1-33.
[4] P. P. Edwards, "Transparent Conducting Oxides (TCOs)," presentation, ISIS INNOVATION, 2013.
[5] I. Sorar, D. S. Hinczewski and F. Z. Tepehan, "Optical
"Opti and Structural properties of Si-doped
doped ZnO thin films,"
Journal Applied Surface Science, no. 257, pp. 7343 - 7349, 2011.
[6] J. Wang, Y. Qi, Z. Zhi, J. Guo, M. Li and Y. Zhang, "A self-assembly
self assembly mechanism for sol
sol-gel derived ZnO thin
films," Smart Materials
erials and Structure, vol. 16, pp. 2673-2679, 2007.
[7] A. Ulman and H. Khun, "Supramolecular Assemblies: Vision and Strategy," in Organic Thin Films and Surfaces:
Directions For The Nineties,, London, Academic Press, 1995, pp. 1-7.
1
[8] J. Boltz, "Sputtered
tered tin oxide and titanium oxide films as alternative transparent conductive oxides," in
Dissertation,, Aachen, Aachen University, 2011.

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[9] J. Lee, P. C.S., M. Kim and H. Kim, "Effects of Residual Stress on Electrical Properties," J. Am. Ceram. Soc., vol.
90, no. 1, pp. 1077-1080, 2007.
[10] T. Ishikara, M. Higuchi, T. Takagi, M. Ito and H. Nishiguchi, "Preparation of CuO thin films on porous BaTiO3 by
self-assembled multibilayer film formation and application as a CO2 sensor," J. Mater. Chem., vol. 8, no. 9, pp.
2037-2042, 1998.
[11] G. Cardenas and S. P. Miranda, "FTIR and TGA Studies of Chitosan Composite Films," 2004, vol. 49, no. N 4, pp.
291-295, J. Chil. Chem. Soc. .
[12] M. Singh, G. Palazzo, G. Romanazzi, G. P. Suranna, N. Ditaranto, C. D. Franco, M. V. Santacroce, M. Y. Mulla,
M. Magliulo, K. Manoli and L. Torsi, "Bio-sorbable, liquid electrolyte gated thin-film transistor based on solution
processed zinc oxide layer," Journal Social Chemistry, 2014.
[13] J. Clatot, G. Campet, A. Zeinert, C. Labrugere, M. Nistor and A. Rougier, "Low Temperature Si doped ZnO thin
films for transparent conducting oxides," Journal Solar Energy Materials and Solar Cell, vol. 95, no. 8, pp. 23572362, 2011.
[14] A. Santos and E. Santos, "High quality c-axis oriented ZnO thin-film obtained at very low pre-heating
temperature," Condensed Matter, 2006.

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CODE: IM
Purification of Silica Sand using Ultrasound Processes in Oxalic Acid Media
Bahang Surya Diwantara, P. N. Trisanti and Sumarno
Department of Chemical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111, Indonesia
Abstract: Silica sand can be used as raw material for several industries. According to the type of products require
different purity silica sand. There are several components that must be reduced, eg glass production requires sand with
maximum iron (Fe) of 0,003 and minimum silica (SiO2) of 99%. One method for purifying silica sand is the sonication
process in the media oxalic acid. This research aims to study sonication effect in purifying silica sand and obtain
optimum acid concentration and time of purification process for obtaining high purity silica sand. Solid products were
analyzed by using Scanning Electron Microscopy (SEM) and X-Ray Fluorescence (XRF), while liquid products were
analyzed by using UV-Vis spectrophotometer for silica sand purification in Rembang. XRF analysis results showed that
high purity silica sand was obtained from distilled water leaching media with 60 minutes sonication. Purity level
increased from 94.16 to 97.97%. Meanwhile, the smallest iron impurity level was obtained from 60 minutes sonication
by using oxalic acid of 1 g/L resulted 0.07% Fe content. Result of SEM analysis showed the presence of morphological
changes in silica sand before and after sonication process by either used distilled water or oxalic acid. UV-Vis
spectrophotometer analysis showed that the resulting solution of sonication contained Fe.
Keywords: silica sand; purification; sonication; Oxalic acid
Corresponding author: Sumarno, Email: onramus@chem-eng.its.ac.id
1. Introduction
Silica sand is one of mine materials found abundantly in Indonesia. The material can be found in some areas of
Indonesia especially in Java (Tuban and Rembang area), Sumatra (Bangka Belitung area), and Kalimantan
(Palangkaraya area). Silica sand is one of raw materials used in cement, glass, ceramic, sand blasting, light brick
industries, etc. Each of those industries has specific requirements of silica sand quality, therefore, there are many
attempt to remove impurity content of silica either chemically or physically. Sometimes the two methods are combined
to improve the quality of silica sand, where the level of suitability of the method depends on the mineral content and
distribution of iron in the silica sand. In its development, chemical method uses organic and inorganic acids. Sulfuric
acid and hydrochloric acid are most widely used but it nneeds high cost and leaves dangerous wastes for environment.
Consequently, their use is inacceptable. In addition, the inorganic acids easily contaminate minerals with sulfate and
chlor ions. Therefore, for a method that is more effective and environmentally friendly then washing with an organic
acid is preferred.
There are many studies that have been conducted with the purpose of elimination of iron from silica sand with
chemical methods to obtain the best process parameters with a small operating costs. One method used combines
chemical means by physical methods using ultrasound process. Ultrasound as auxiliary energy has been successfully
used in mining industry. This iron removal from silica surface method is found to be more effective compared to the
mechanical cleaning, therefore addition of ultrasound is expected to increase the rate of iron removal from silica sand.
[2]
Veglio, et al. (1999) conducted a research of iron removal to obtain high purity silica sand by using oxalic acid as
leaching media. The process of iron removal from silica sand depends on the size of silica sand to be extracted with
oxalic acid. The oxalic acid extracts the iron contained in silica sand. The smaller size of silica sand, the more iron
extracted by oxalic acid. His experiment showed that particle size of 20m is the optimum size for high-purity silica
after 3 hours leaching process [4].
Ultrasound can speed up leaching process time and lower use of reactants. Ultrasound forms cavitations bubbles
that damage and destroy metal ore quickly that particle size of the metal ore is reduced. Ultrasound also facilitates
leaching media to extract impurities to produce high purity metal ores. Swamy and Narayana (2001) stated this on their
metal ore purification experiments with ultrasound process.
Feihu, et al. (2010) conducted purification of silica sand by using ultrasound assisted with oxalic acid. In this
experiment, an increase in iron removal from silica sand with oxalic acid leaching media was noticed. The silica
purification process was influenced by several factors including temperature of ultrasound and concentration of acid
used. Sonication temperature affect leaching rate; the higher the temperature, the higher the leaching rate.
Some previous studies mentioned showed that environmentally friendly silica purification could use ultrasound
process by using acid. The ultrasound process accelerate rate of leaching and reduce the use of reactants. The time
required to reach levels that can be removed have not been reported clearly. The effect of sonication on surface, particle
form or size, and selectivity in leaching nee also further studied.

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2. Material and methods
This research was started by creating mixture of silica sand and solution (without or with oxalic acid) at ratio of 1:
10 (w/v) in reactor. Water bath temperature was then conditioned according to operating temperature. Once reaching
operating temperature, water bath was then put on a water bath reactor and sonication process was then carried out
based on time variable. After sonication process was completed, the reactor was released and sonication result was
chilled quickly, then silica sand and solution was separated. The silica sand of sonication result was then washed by
using distilled water, while the solution was centrifuged for 15 min, then filtrate and sediment of centrifugation result
was separated. The final result of sonication was analyzed by Scanning Electron Microscopy (SEM), X-Ray
Fluorescence (XRF) for solids and with UV-Vis Spectrophotometer for liquids.
9

4
8
1
5
6
3
2
10

7
3
2

4
1

7
11

8
9

3
2

4
1

7
10

11

8
9

12

Fig. 1. Experimental apparatus


1.
2.
3.
4.
5.
6.

Probe ultrasonic
Reactor
Water bath
ultrasonic generator
Thermostat
Termocouple

7.
8.
9.
10.
12.

Magnetic Stirrer
Cooling water inlet
Cooling water inlet outlet
Water inlet
power source

3. Results and discussion


Chemically, the characteristics of silica sand samples could be recognized in detail by using quantitative analysis
method by using X-Ray Fluorescence (XRF) described in Table III.1 below.
Table III.1 Results of silica sand from XRF anlaysis
Component
SiO2
Al2O3
CaO
Fe2O3
MgO
K 2O
Na2O
S
P 2O 5
TiO2
Cr2O3
MnO2
ZnO

(wt.%)
94,19
3,57
0,118
0,211
0,265
1,11
0,275
0,0793
0,0186
0,136
0,0146
0,066
0,028

3.1. Sonication Process


Sonication process aims to stretch the distance between molecules contained in matrix of silica sand particles. In
addition, this process is also for cleaning impurities both on silica sand surface and those contained in silica sand matrix
[1].

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The main variables that can be used in leaching system of sonication are: amplitude, frequency, wave operating
mode, contact time, sonication position toward reactor, distance between probe tip to sample as well as volume and
fluid conductivity used [1]. Focus of variable in this research was the effect of sonication time and concentration of
oxalic acid.
3.2. Effect of sonication time
Sonication time is a variable frequently included in optimization test, where the optimum value depends on the
operating conditions used such as the strength of ultrasonic waves, solvents, types of samples and analytes involved in
the process [1]. Optimum time in applied operating conditions of silica sand purification is essential in producing
desired products. Sonication process for various times and concentrations is shown in Fig. 2

Fig. 2. The profile of SiO2 content in Rembang silica sand particle processed in two oxalic acid concentration and for
various sonication duration
Fig. 2 shows that leaching rate increased sharply to 5 minutes and followed by a small increment. The maximum
SiO2 concentrations obtained after sonication time was about 20 minutes. This result agrees with the results reported by
Castro & Capote (2006) that sonication can increase the rate of leaching [1]. We see that sonication for 5 minutes lead
the SiO2 concentration achieved 96.5 % and became 97.97% after 20 minutes.
3.3. Effect of Oxalic Acid Concentration
Oxalic acid is a solvent of the impurities extracted from silica sand. The solvent ability is an important factor in
silica sand purification process for the ratio of solvent and analyte is very significant in leaching process. Composition
or ratio of oxalic acid to water determines the ability of the media to extracting the impurities from silica sand. This will
determine the quality of the desired products.

Fig. 3. The profile of Fe2O3 content in Rembang silica sand particle processed in two oxalic acid concentration and for
various sonication duration
Fig. 3 shows that in the first 5 minutes of sonication process, the leaching rate increased sharply. The use of distilled
water as leaching media produces smaller purity compared with the use of oxalic acid. However, with increasing
sonication time, the rate of Fe removal increased and decreased. This was due to the high alumina impurities contained
in the silica sand as shown in Figure 4 below.

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Fig. 4. The profile of Al2O2 content in Rembang silica sand particle processed in two oxalic acid concentration and for
various sonication duration
Fig. 4 shows that the rate of alumina concentration removal was inversely proportional to the rate of iron removal in
silica sand. In sonication process, while iron content was removed with high removal rate, alumina content remain high
and vice versa. This is why purification process of silica sand to the influence of sonication and oxalic acid
concentration does not have a trend (fluctuates). from XRF analysis, 60 minutes sonication with distilled water as
leaching media and oxalic acid of 1g/L produced 97.97% purity of silica sand with iron impurities and alumina of 0.11
and 0.98%, respectively. Meanwhile the use of oxalic acid of 1g /L produced 97.07 purity of silica sand with 0.07 iron
impurity and 1.98% alumina.
4. Conclusions
1. Sonication can be used for purification of silica sand with high purity. The highest purity of Silica sand obtained in
Rembang area was 98.47% with twice sonication process.
2. Based on X-Ray Fluorescence (XRF) analysis, 1 g/L of oxalic acid was the optimum concentration to produce
silica sand with the lowest impurities of Fe2O3.
3. Based on X-Ray Fluorescence (XRF) analysis, optimum sonication process to produce the lowest level of Al2O3
impurities was by using distilled water.
4. Based on X-Ray Fluorescence (XRF) analysis, optimum time of sonication to produce high-purity silica was 60
minutes sonication.
References
[1] Capote F.P & Castro M.D. 2006. Analytical Application of Ultrasound. Spain:Elsevier Science
[2] Feihu D., Jingsheng L., Xiaoxia L., & Zhang Z. 2010. Improvement of Iron Removal Silica Sand Using
Ultrasound Assisted Oxalic Acid. Cina:Elsevier Science.
[3] Swamy K.M. & Narayana K.L. 2001. Intensification of Leaching Process by Dual-Frequency Ultrasound.
India:Elsevier Science.
[4] Veglio F., Passariello B., & Abburuzzese, C. 1999. Iron Removal Process for High-Purity Silica Sand Production
by Oxalic Acid Leaching. Italy:American Chemical Society.

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CODE: IM
Fabrication of Bombyx mori silk fibroin/chitosan scaffold for tissue engineering
`
Untung Ari Wibowo1, Hermawan Judawisastra1, Anggraini Barlian2
1

Materials Science and Engineering Research Groups, Institut Teknologi Bandung, Bandung, 40132, Indonesia
School of Life Science and Technology, Institut Teknologi Bandung, Bandung, 40132, Indonesia

Abstract: Treatment of chronic wounds with an area more than 50% total body surface could not be fulfilled with skin
grafting techniques. Tissue engineering is introduced to overcome these problems. Scaffold with cellular structure
material and biocompatible material is needed in tissue engineering. Silk fibroin and chitosan had widely developed as
scaffold materials due to their biocompatibility. The material has been widely processed using traditional aqueous
dissolution such as LiBr or CaCl2/Et-OH/H2O which is complex and time consuming. This research studies silk fibroinchitosan scaffold fabrication using newly developed CaCl2/formic acid to dissolved silk that preserved faster processing
time. Silk fibroin scaffold was fabricated using salt leaching techniques with various addition of chitosan. Chemical
interaction of chitosan in the scaffold was detected by FTIR spectroscopy. Scaffold hydrophilicity was measured by
water contact angle testing and degree of swelling in water. Scaffold pore diameter and interconnectivity was examined
by means of Scanning Electron Microscopy (SEM). Silk fibroin scaffold with addition of chitosan for skin tissue
engineering application is successfully fabricated with open pore morphology, minimum contact angle of 67,6o and
maximum degree of swelling of 162.06%. The addition of chitosan up to 40wt% result in increasing pore diameter from
4.75 m to 5.93 m. The addition of chitosan up to 40wt% increased the scaffold wettability: decreasing the contact
angle from 80,0o to 76,6o and increasing the degree of swelling from 52% to 162%. This result indicates the potential of
the SF/CS as scaffold in skin tissue engineering, particularly in epidermal substitutes.
Keywords: CaCl2; chitosan; hydrophilicity; salt leaching; silk fibroin
Corresponding authors: Hermawan Judawisastra, Email: hermawan.judawisastra@material.itb.ac.id, Telp: 022250 4243, Fax: 022-253 4099
1. Introduction
Large full-thickness skin injury (e.g burns, diabetic ulcers, trauma, etc.) treatment is a clinical problem that
sufficient to be life-threatening. Time is life for patient because untreated wounds are at high risk of infection. The gold
standard today to cover large wounds are autologous skin grafting which harvest split/full-thickness skin from
uninjured areas and graft it onto wounds. However, the use of this method is limited due to few uninjured area left.
Maximum coverage area of autologous skin transplantation is up to 50% of total body surface area (TBSA) [1]. These
limitations could be reduced by reconstruct new autologous skin using tissue engineering techniques. In tissue
engineering scaffold with cellular structure maerials was needed to support cell growth, tissue reconstructions, and
nutrient migrations during new tissue reconstruction [2].
Scaffold materials should have several properties such as nontoxic, high strength, good biodegradability and good
biocompatibility to support cell adhesion, cell spreading, and proliferation [3]. Silk fibroin (SF) and chitosan (CS) are
excellent natural polymer for biomedical applications in term of biocompatibility and biodegradability. Silk fibroin,
natural fibrous protein in cocoons of Bombyx mori silkworm, had been traditionally used as medical suture due to its
high strength and biocompatibility. Chitosan is polysaccharide structurally similar to various Glycosaminoglycan
(GAGs) that are present in the extracellular matrix (ECM) of several human tissue. Some previous study showed that
the addition of chitosan introduced to improve physical properties and biocompatibility of silk fibroin scaffold due to its
mimic to ECM [4] [5].
The application of SF as tissue engineering scaffold have been widely studies with wide range material format such
as film [5], nanofiber [4], dan porous membranes [6]. The methods used to generate these material formats begin with 2
steps: SF dissolution in high concentration salt such as LiBr aqueous solutions and CaCl2/Et-OH/H2O solutions,
followed by dialysis to remove the salt. However, the process are relatively complex, time consuming and difficult to
handle due to environmental exposure [7]. In this study, direct SF dissolution method using CaCl2/Formic Acid
(CaCl2/FA) solution is introduced to produce SF scaffold. This technique allowing a simple operation and high
dissolution efficiency as previously described [8]. The porous scaffold is fabricated using salt leaching techniques. The
influence of CS addition on the morphology and physical properties of the SF scaffold will be investigated. Water
contact angle and degree of swelling will be utilized to evaluate the scaffold biocompatibility for tissue engineering
applications.
2. Materials and methods
2.1. Materials
Bombyx mori cocoons was purchased from Padepokan Dayang Sumbi, Bandung. Silk fibroin (SF) were prepared
with a degummed method by boiled for 30 min in 0.05 wt % NaHCO3 solution at 90oC twice, rinsed thoroughly with

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warm distilled water (40-60oC) and dried in fume hood overnight. Chitosan (CS) medical grade with 90% deacetylation
was purchased from PT. Biotech Surindo, Cirebon, West Java Province, Indonesia and used without further
purification. NaCl powder with particle size 60-600 m and Formic Acid (90%) were purchased from PT. Brataco
Chemica, Bandung.
2.2. Preparation of porous scaffold
Scaffold was fabricated by salt leaching methods. The degummed silk was directly dissolved in 8 wt%
CaCl2formic acid (FA) solution, chitosan was dissolved in FA at 25oC, and stirring for 3 hours. The SF/CS blend was
prepared by blending the solution by weight ratio of 100/0, 80/20, 60/40, then named as SF-100, SF-80, and SF-60
respectively. The solution then stirred 3 hours for homogenizing. Sodium chloride particulates as porogen were added
to polystyrene mold (90 mm). The SF/CS solution was added into the mold containing the porogen. The solution and
porogen ratio was adjusted 2/2 (w/v) constantly. The mold was placed in fume hood overnight at room temperature to
evaporate the solvent. After dried, the silk/porogen was immersed in 25% ethanol for 30 min to induce -sheet structure
and insolubility in aqueous solution. The silk/porogen then were immersed in demineralized water for 24 hours to
ensure all of the NaCl particles had leached from the matrixes. The water was changed four times a day. Finally, the
porous scaffolds were air-dried in fume hood overnight.
2.3. Degumming Process Observation
Degumming of raw silk is the removal process of sericin, glue-like protein coated the fibroin, which have been
known to cause inflammatory responses [9]. Removal of sericin can be investigated by weighting of silk before and
after degumming process. Initial weight of cocoons (Wi) were measured from fresh cocoon using 4 digit scale
analytical balances (Sartorius ENTRIS224-1S). After degumming process cocoons were weighed again, then called
final weight (Wf). Percentage of sericin loss was calculate as follows:
Sericin Loss (%)=

Wi -Wf
100
Wi

(1)

Scanning Electron Microscopy (SEM) was introduced to verify the removal of sericin.
2.4. Characterization of porous scaffold
Scaffold morphology was analyzed by SEM, JEOL JSM-6510LV. The average pore size were determined by
measuring 100 pores selected randomly from each sample using ImageJ, NIH, USA. Silk fibroin/chitosan scaffold
formation was confirmed with an ATR-FTIR spectrophotometer by Shimadzu IR Prestige-21. The amount of chitosan
in the scaffold was investigated by analyze the FTIR spectra. The spectra had been normalized to SF characteristic peak
at 1542 cm-1 as previously described [10].
Hydrophilicity of the scaffold were investigated by measurement of water contact angle and degree of swelling. The
higher water contact angle is directly related to lower hydrophilicity. Static contact angle between water and scaffold
was measured on dry SF/CS scaffold using contact angle meter, Tantec CAM-Plus, USA. Ultrapure water droplets were
used with a drop volume of 10 l (n=5). The swelling properties were obtained by measuring degree of swelling in
water. Dry scaffold was weighed (Wd). Scaffolds were immersed in distilled water for 24 h. After excess water was
removed, the wet weight of the scaffold (Ws) was determined. Measurements were conducted in triplicate. The degree
of swelling of the scaffold was calculated as follows:
Degree of Swelling (%)=

Ws -Wd
100
Ws

(2)

3. Results and discussion


3.1. Degumming process observation
Degumming process resulted in 29.1% of weight loss, which is in the range of sericin weight loss in the literature,
25-30% [11]. These weight loss was indicated the removal of sericin which confirmed by SEM micrograph of silk that
shown in Fig 3.1. As reported by previous studies, raw silk showed sericin coated over the fibroin filaments and
sticking some silk filaments together (Fig.3.1a). After degumming, silk filament separated to individual strand and
showed no presence of glue-like sericin (Fig.3.1b). It clearly confirms that silk fibroin used in this study was free of
sericin so that have good biocompatibility and will not induce inflammatory responses.

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(a)

(b)

Fig. 3.1. Scanning electron micrograph of (a) raw silk, showing presence of sericin [12] and (b) degummed silk,
showing fibroin
fib
filament with free of sericin.
3.2. Morphology analysis
Scaffold surface morphology from SEM examination is shown in Fig 3.2. Pore morphology on the surface of
scaffold shows open pore morphology but less interconnected. SF-100,
SF
SF-80, and SF-60
60 has irreg
irregular pore shapes and
varied pore depth. There may occurred due to partial dissolution of NaCl particles in the solvent so that the final shape
of the pore will follow the final shape of NaCl particles. Fig 3.3 shows image analysis result which is average ppore size
of SF scaffold with different CS concentration. With an increase in CS concentration, the pore size were larger.
Addition of CS up to 20wt% and 40wt% increase the pore size from 4.75 m to 8.00 m and 5.93 m, respectively. The
actual pore size in the SF/CS scaffold were smaller than the size of NaCl particles used in this study (60
(60-600 m).
These also reflecting the effect of partial dissolution of the surface of NaCl particles likely lead to reduce the final pore
size as same as result from previously
ously study [13],, since the NaCl particles was easily dissolved in the solvent.

Fig. 3.2. SEM image of silk fibroin scaffold with different chitosan concentration (a)
(a SF-100,
100, (b) SF
SF-80, and (c) SF-60.
Pore size is important scaffold parameter to consider, because it is known to influence the cellular infiltration, cell
cellto-cell
cell interaction, and transport of nutrients and metabolites. Previously studies reported that minimum pore size of
skin epithelial cell to well infiltrate and migrate was 3 m [14].. The average pore size of the sample in this studies SF
SF100, SF-80, and SF-60
60 are 4.75 m, 8.00 m, and 5.93 m respectively. This result indicates
indicates the potential of the SF/CS
as scaffold in skin tissue engineering, particularly in epidermal substitutes.

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14

Average Diameter (m)

12
10
8
6
4
2
0

SF-100

SF-80

SF-60

Fig. 3.3. Average diameter of SF/CS


scaffolds.
3.3. FTIR analysis
FTIR spectra of SF/CS scaffolds shows in Fig 3.4. This study was conducted to compare the amount oof CS content
in each sample. The normalized FTIR spectra showed characteristic peaks of chitosan, C-O-C
C C bond in CS backbone, at
1028 cm-1. Total absorbance for SF-60,
60, SF-80,
SF
and SF-100
100 were decreased respectively. From these result of FTIR
analysis confirmed
ed that the amount of CS on SF-100,
SF
SF-80, and SF-60
60 were increased respectively as proof of increase
in the addition of chitosan.

Fig. 3.4. FTIR spectra of SF/CS scaffolds.


3.4. Water Contact Angle
The contact angle of SF scaffold with different chitosan concentration are shown in Fig
Fig 3.4. The addition of 20wt%
and 40wt% chitosan decreased the water contact angle from 80o to 74.8o and 67.6o respectively. As the chitosan ratio
increased the water contact angle of the scaffold decreased, suggesting that the CS could enhanced hydrophili
hydrophilicity of
SF/CS scaffold. CS was well known materials with hydrophilic properties rather than SF which has hydrophobic
properties because of the high -sheet
sheet crystalline content [15].. Previous studies shows scaffold with SF/CS ra
ratio of 2/2
had water contact angle of 70o and would have good biocompatibility [16].. The hydrophilic character of the scaffold
implied that SF/CS scaffold had high wettability which suitable for tissue engineering applications.
3.5. Degree of swelling
The degree of swelling of SF/CS scaffold are shown in Fig. 3.4. The swelling ratios of pure silk fibroin scaffold was
52%. The addition of 20wt% and 40wt% chitosan increased the degree of swelling of silk fibroin up to 152% and
162% respectively.
espectively. The degree of swelling of the silk fibroin could be enhanced by the chitosan addition due to
excellent swelling properties of chitosan.
High content of -sheet
sheet crystalline in SF pretended SF hard to swell [15]. Previous
evious study shows the addition of 40 wt%
chitosan would increase SF degree of swelling from 40% to 150%.The degree of swelling is one of the important
properties in cell interaction with scaffold during tissue regeneration. SF/CS scaffold would well suppo
supported the cell
attachment and proliferation as the high degree of swelling. From the analysis of water contact angle and degree of
swelling investigation the scaffold was highly potential for tissue engineering applications.

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Water Contact Angle ( o )

80

60

40

20

0
SF-100

SF-80

SF-60

Fig. 3.5. Water contact angle of SF/CS scaffolds.

Degree of Swelling (%)

180

150

120

90

60

30

0
SF-100

SF-80

SF-60

Fig. 3.6. Degree of swelling of the SF/CS scaffolds.


4. Conclusions
Silk fibroin scaffold with addition of chitosan for skin tissue engineering application is successfully fabricated with
open pore morphology, minimum contact angle of 67.6o and maximum degree of swelling of 162%, but less
interconnected. The addition of chitosan up to 40 wt% result in increasing pore diameter from 4.75 m to 5.93 m. The
addition of chitosan up to 40wt% increased the scaffold wettability: decreasing scaffold contact angle from 80o to 76,6o
and increasing scaffold swelling ratio from 52% to 162%. This result indicates the potential of the SF/CS as scaffold in
skin tissue engineering, particularly in epidermal substitutes.
Bibliography
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cultured autologous keratinocytes combined to treat a severe injury of 93% of TBSA, Burns, vol. 26, pp. 644652, 2000.
[2] H. E. Koschwanez dan W. M. Reichert, Biomaterials Science (Third Edition) - An Introduction to Materials in
Medicine, Textured and Porous Materials, Canada, Academic Press - Elsevier, 2013, p. 321331.
[3] C. v. Blitterswijk, Tissue Engineering, Canada: Academic Press, 2008.
[4] K. S. S.-H. C. J.-P. C. Guo-Jyun Lai, Composite chitosan/silk fibroin nanofibers for modulation of osteogenic
differentiation and proliferation of human mesenchymal stem cells, Carbohydrate Polymers, vol. 111, p. 288
297, 2014.
[5] J. V. W. L. P. S. a. P. L. Witoo Luangbudnark, Properties and Biocompatibility of Chitosan and Silk Fibroin
Blend Films for Application in Skin Tissue Engineering, The Scientific World Journal, vol. 2012, pp. 1-10, 2012.
[6] O. J. L. M. C. L. B. M. M. H. W. J. Hyun Jung Park, Fabrication of 3D porous silk scaffolds by particulate
(salt/sucrose) leaching for bone tissue reconstruction, International Journal of Biological Macromolecules, 2015.
[7] Q. L. Feng Zhang, Silk dissolution and regeneration at the nanofibril scale, Journal of Materials Chemistry B,
vol. 2, no. 24, pp. 3879-3885, 2014.
[8] F. Z. H. W. J. M. Xiaoxiao Yue, A novel route to prepare dry-spun silk fibers from CaCl2formic acid solution,
Materials Letters, vol. 128, pp. 175-178, 2014.
[9] R. C. P. T. Y. X. W. M. L. K. Danielle N Rockwood, Materials fabrication from Bombyx morisilk fibroin,

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J. G. Hardy, L. M. Rmer dan T. R. Scheibel, Polymeric materials based on silk proteins, Polymer, vol. 49, no.
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H. C. H. I. C. U. Y. H. P. HAEYONG KWEON, Physical Properties of Silk Fibroin/Chitosan Blend Films,
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CODE: IM
Synthesis and Characterisation of Transparent Nano Ceramic MgAl2O4/Spinel for Orthodontic Bracket
Appliance
Edwina Maharani1), Zulia Hasratiningsih1), Nina Djustiana1), Deby Fajar Mardhian2), Bambang Sunendar
Purwasasmita2)
1
Departement of Dental Materials Sience and Technology, Faculty of Dentistry, Universitas Padjadjaran, Bandung
40132, Indonesia
2
Department of Engineering Physics, Faculty of Industrial Technology, Institut Teknologi Bandung, Bandung 40132,
Indonesia
Abstract: Orthodontic bracket is one of the orthodontic appliance components to support orthodontic wire. Due to
aesthetic reason, nowadays transparent ceramic brackets are developed. This brackets are relatively expensive because
Indonesia has not been able to make their own. One material that can be used as the base material is magnesium
aluminate (MgAl2O4) spinel which has good physical properties, especially transparency. Synthesis of spinel powder
has been done through sol-gel process. Precursors for this materialare magnesium chloride hexahydrate and aluminum
nitrate nonahydrate with 0.1M concentration. Both precursors were mixed and dried at 100C, crushed, then calcined at
1100C. Calcined powder were characterized using scanning electron microscopy(SEM) and x-ray diffraction
(XRD).Result showed the formation of spinel with the particle size of 100nm and some were agglomerated. The powder
then mixed with alkali activator solution consists of sodium hydroxide (NaOH) and sodium silicate (Na2SiO3) to form
paste, then sintered at 1450C to produce shiny solid specimensthrough geopolymerization.
Keywords: transparent ceramic; MgAl2O4 spinel; sol-gel; bracket; geopolymerization
Corresponding author: Edwina Maharani, e-mail:edwina.maharani@gmail.com, Tel. +62-81-220-289-07
1. Introduction
The role of orthodontic treatment all walks of life due to the universal nature of dental and jaw irregularities [1].
Orthodontic brackets are devices used to support wires that help align and straighten teeth [2]. Early versions of
orthodontic brackets are metal-based. These brackets are regarded as less aesthetically-pleasing and have generated
allergic reactions in some patients. The next generation brackets made from ceramics which are a more biocompatible
and inert cosmetic alternative [3].
Ceramic-based orthodontic brackets are generally composed of alumina or aluminum oxidein mono- or
polycrystaline forms. Alumina monocrystaline was the material used in the first production of transparent ceramic
bracket, processed by diamond-ground sapphire heated at high temperature. While alumina monocrystalin has good
transparent properties, its production process is expensive and challenging due to the extremely high temperature
requirement [4]. Alumina polycrystalline can be produced from various groups of material to increase mechanical,
thermal, chemical and optical properties. One of the best materials for producing transparent ceramics is magnesium
aluminate spinel (MgAl2O4) which has superior optical properties due to its cubic crystal structure [5].
For many industrial applications, nanosized materials present a clear advantage due to their unique optical,
electronic, or mechanical properties. One of the techniques for generating nanosized particles is known as the sol-gel
technique, a low temperature chemical process involving a conversion from a colloidal suspension phase (sol) into
continuous liquid phase (gel) [6]. This method is commonly used due to its thermal and mechanical stabilities, good
solubility, and flexibility for surface modifications. [7]. This process is capable of producing superior inorganic oxides
with superior hardness, optical transparency, chemical resistance, suitable porosity and thermal resistance at room
temperature. This method is also relatively simple and cheap to accomplish using standard equipment [8]. Factors that
can influence the particle size generated include pH and addition of dispersants [9].
Precursors for the production of sol include organic and inorganic metal compounds such as metal alcoxide, salts of
organic acids (acetate, lactate), metal organic (pentadionate), or inorganic salts (nitrate, chloride) [8]. MgAl2O4spinel
can be synthesized from the metallic salt aluminium nitrate nonahydrate and magnesium chloride hexahydratewith solgel process to form nano sized particles.
It is difficult to sinter highly pure magnesium aluminate spinelinto transparent ceramics due to its high melting point
(2,135o C) [10][11]. The high melting point, in addition, presented a challenge in choosing the proper mold for sintering
this material. There have recently been a lot of interests in the development of geopolymer material containing
inorganic materials such as silica or alumina. The process of geopolymerization can generate SiO4 dan AlO4 polymer
skeletons with tetrahedral bonding framework effectively at a relatively low temperature [12]. This process can be
accelerated in the production of ceramic spinel specimen by adding an activator, i.e., alumina or silica-containing
materials after addition of a strong base. Addition of the activator allows the geopolymerization process to occur at
room temperature, so sintering can be done without the use of a mold

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The objective of this study was to produce nanosized spinel powder using the sol-gel technique and to produce
dense ceramic via geopolymerization and sintering.
2. Methods
The precursors used to start the sol-gel process were aluminium nitrate nonahydrate (Al(NO3)3.9H2O) and
magnesium chloride hexahydrate (MgCl2.6H2O) dissolved into 0.1 M solution. Briefly, aluminium solution was
prepared with distilled water and sodium hydroxide (NaOH) was added to reach pH 5. Magnesium solution was
prepared similarly and was adjusted to pH 11. Chitosan was added to both solution.
The two precursor solutions were mixed at a ratio of Mg:Al=1:2 and stirred for 1 hour. The mixture was then heated
to dry in a 100 C oven. The remaining solid was ground to powder and subjected to calcination at 1100 C for 2 hours.
Following calcination, the materials were ground to a fine powder and subjected to X-Ray Diffraction (XRD) and
Scanning Electron Microscopy (SEM) analysis.
Powders collected from the calcination process was then further processed in two different methods: (1) chitosan
was added as a binding agent, and (2) a mixture of NaSi2O3 and NaOH 8 M at a volume ratio of 1:2 was added as an
activator. Each powder mixture was mixed to form a paste-like consistency, placed into a mold and pressed to remove
any pores. Molded products were allowed to dry at room temperature, then removed from the mold and sintered at a
temperature of 1450 C to form a dense and solid product.
3. Results and discussion
X-ray diffractogram showed the formation of spinel (MgAl2O4) (Fig.1).

Fig. 1. A Diffractogram from XRD Analysis of Mg-Al Powder (S = Spinel(MgAl2O4), P = Periclase(MgO), C =


Corundum(Al2O3)).
Results of the XRD analysis of the powders generated from the sol-gel process (Figure 1) showed the spinel phase
as the dominant crystalline structure at 88.1%. However, other crystalline structures such as periclase (MgO) and
corundum (Al2O3) were also present at 1.5% dan 10.4%, respectively. The graph in Figure 1 only showed one clear
peak of the corundumphase structure, although there were actually numerous smaller peaks which were overlain by the
larger the spinel phase peaks. The periclasedan corundumphases could possibly be produced during the sol-gel process
due to minor experimental deviations such asexcessive number rounding during the production of precursor solutions,
inaccuracies in the measurements of precursors and/or solvents, insufficient mixing of the precursor solutions that lead
to an incomplete chemical reaction.
SEM analysis showed the cubic crystal structure in various sizes (Fig. 2).
The electromicrograph obtained from the SEM analysis (figure 2) further demonstrated in more detail that rather
large (100 nm 2 m) spinels with a cubic crystal structure were formed. The size or particulates formed by the sol-gel
process could be influenced by several factors, including pH, dispersant, and mixing speed of the two precursosr
solutions.
Adjustment of pH of each precursor solution was conducted to allow slow condensation. However, the pH
difference between the two precursor solutions could also influence the speed of chemical reaction between the two
oxides. Since there was a large pH difference between the MgCl2 (pH 11) and Al(NO3)3 (pH 5), condensation occurred
too rapidly resulting in larger sized products.
Similarly, addition of chitosan as dispersant was also done to slow the growth of the particulate size by providing a
barrier that coated the particulates, preventing them from touching each other. Due to its high viscosity, addition of
chitosan had to be done slowly and mixing between the precursor solutions and chitosan must be done thoroughly.
Failure in sufficient mixing of the dispersant could result in incomplete coating of the particles. Concentration and
chitosan percentation needed as an effective dispersant in each of the two precursor solutions may differ. This may also
lead to the formation of larger than desired spinelpowder produced.

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Fig. 2.SEM Analysis at 10.000 x.


In the current study, the spinel powder was sintered at 1,450oC. The authors had previously attempted sintering of
the spinel powder without including an activator with poor result. Chitosan packed specimen sintered under this
condition failed to harden and the product was prone to break
brea under minimal pressure (Fig. 3).

Fig. 3. Sinterred samples without activator.


When an activator was added to thespinelpowder
the
powder before placing it into the mold, the condensation proceeded,
initiating the geopolymerization process prior to sintering. The geopolymerization process was additionally conducted
in anticipation of inadequate sintering temperature. Thus, even if the sintering process was not completed, Na2SiO3 with
a lower melting point (1088C), can bind the spinel powder to form the desired shape with sufficient hardness for use as
an orthodontic bracket material.
Post-sintering,
sintering, samples that were mixed with an activator maintained their shape and
and gained a shiny surface (Fig. 4).
This showed that added activator was capable of binding the spinel powder even though the product lack the desired
transparency. Sodium
m silicate with a melting point around 1088 C had already melted before 1450C. It was postulated
that melted sodium silicate acted as a binding agent for the spinel powder in this experiment.

Fig. 4. Sinterred samples with addition of activator.


4. Conclusions
Spinel powder has been synthesized through sol-gel
sol gel proscess using metal salt precursor, aluminium nitrate and
magnesium chloride. Magnesium aluminate spinel ceramic with shiny surface was formed htrough geopolymerization
process and sinterred at 1450 C though transparency has not been achieved.
Acknowledgements
This study was funded by Ministry of Reaserch, Technology and Higher Education Republic of Indonesia through
Padjadjaran University.
References
[1] C. Hasnu, P.S. Anindita; and N.W. Mariati.
Mariati. Kebutuhan perawatan ortodonsi berdasarkan index of orthodontic
treatment need di SMP Katolik Theodorus Kota Mobagu.
Mobagu Jurnal e-GIGI (eG).. Universitas Sam Ratulangi
Manado, 2013, p.99-100
[2] G. Singh, Textbook of Orthodontics,
Orthodontics Faridabad, Jaypee Brothers, 2007, p 338-341.
[3] A.J. Kumar, R. Duggal, and A.K. Mehrotra, Physical properties and clinical characteristics of ceramic brackets : a
comprehensive review, Kanpur, Trends in Biomaterials and Artificial Organs. 20 (2), 2007. p 1.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
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[4] J.S. Russle, Current products and practice aesthetic orthodontic brackets, Clarendon Way Leeds.Journal of
Orthodontics, 2005, p 156-157.
[5] M. Krishnan, B. Tiwari, S. Seema, N. Karla, P. Biswas, K. Rajeswari, et al, Transparent magnesium aluminate
spinel : a prospective biomaterial for esthetic orthodontic brackets, New York. Journal of Materials Science :
Material in Medicine, Springer, 2014, p 1-2.
[6] S. Ibrahem and H. Ibrahem, Synthesis and study the effect of H2O/TEOS ratio of the silika xerogel by sol-gel
method: International Archive of Applied Sciences and Tecnology, India, 2014, p 1.
[7] B.R. Fernandez, Sintesis nano partikel, Makalah, Program Studi Kimia Pascasarjana, Universitas Andalas.
Padang, 2011, p 5.
[8] Christian Alberchts Universitat, Basic Laboratory Material Science and Engeneering: Sol-Gel Technique. Kiel,
2011, p 2.
[9] C.A. Milea, C. Bogatu, and A. Duta, The influence of parameters in silika sol-gel process: Buletin of the
Transilvania University of Brasov, Series I: Engerneering Sciences, 4 (53), 2011, p 1.
[10] V.V. Dev,. Transparent ceramic : magnesium aluminate, Thesis. Sree Xhithirathirunal College of Engeneering,
Trivandrum, University of Kerla, 2008.
[11] R. Xu, W. Pang, and Q. Huo, Mern Inorganic Synthetic Chemistry, Amsterdam: Elsevier, 2011, p 445.
[12] J. Davidovits, Geopolymer Chemistry and Applications, 3rd edition. Saint Quentin, France : Institut Geopolymere,
2011, p 1-3.

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CODE: IM
Flexural Characteristics of Water Treated Gombong Bamboo (Gigantochloa Pseudoarundinacea)
Aditianto Ramelan1), Riska Rachmantyo1), Muhammad Kurnia Bijaksana1)
1

Department of Materials Engineering, Faculty of Mechanical and Aerospace Engineering, Bandung Institute of
Technology, Bandung 40132.
Abstract: Bamboo is one type of tropical plants they grew up to a 3000 m height above sea level. More than 1200
species are available worldwideandaround 143 species are available widespread in Indonesia such as in Sumatera, Java,
Bali and Nusa Tenggara island. In Indonesia bamboo are used widely as a construction material for making traditional
structures including houses.Bamboo can also be used to form a composite material with cement to achieve a specific
characteristic. As natural plants bamboo is easy to cultivate and to get and has relatively cheaper in price than other
construction materials that were produced using high technology. Naturally, bamboo can be easily attacked by a certain
moths unless treated prior to be used and also it can suffer from catching fire. The flexural strength of bamboo will
determine the strength of the built structure. In this research Gombong bamboo (Gigantochloa Pseudoarundinacea) was
used for observation to have more understanding on its properties. In order to avoid the moth attack, in practice bamboo
is usually treated by dipping or immersing it into water prior being used. An untreated bamboo has a flexural strength of
326.1 48.5 MPa whereas the water treated bamboo is 283.6 52.2 MPa with a subsequent Modulus of Elasticity of
54.2 9.8 GPa and 48.9 9.5 GPa. Hence it is clearly noted that the 2 months water treated bamboo has reduced its
mechanical properties. From the observation using a Scanning Electron Microscope it is shown that the water treated
bamboo has a different appearance, some cracks were seen on the cross sectional view. This might explain for the
mechanical properties reduction in the bamboo observed. Further study on this material should be undertaken.
Keywords: Gombong bamboo; water treated; flexural strength; SEM cross sectional view.
Corresponding author: AditiantoRamelan, Email: ramelan@material.itb.ac.id, Telephone : +62-22-2512457; +62-222502265, Fax : +62-22-2502265

1. Introduction
Indonesia as a tropical country has several types of plants that have a benefit for mankind, and one of them is
bamboo.Bamboo is one of plants that grow in tropical area such as Indonesia whether in a plateau up to mountainous
area up to 3000 m above sea level. Several types of bamboo are available in Indonesia. More than 1200 species are
available worldwide and 143 species can be found in Indonesia such as in Sumatera, Java, Bali and Nusa Tenggara
islands[1]. Characteristic of bamboo depends on its types, species and where it grew. Bamboo is used as construction
material, but it is easily attacked by moths or fire that reduces its strength. Bamboo that used in this observation is
bamboo Gombong or Gigantochloa Pseudoarundinacea. Gombong bamboo are distributed and used a lot in West
Java. To be able to use this type of bamboo information regarding its mechanical and physical properties is required.
This research is carried out to measure the bending strength of Gombong bamboo and the effect of dipping or
immersing in water.

Fig.1. Bambu Gombong (Gigantochloa Pseudoarundinacea) [2]


In its classification bamboo trees is a member of wooden grass family that has a faster life cycle compare to wood.
Table 1 showed the scientific classification of bamboo Gombong.

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Table1.Gombong bamboo classification [3]

Kingdom
Family
Subfamily
Tribe
Genus
Type Species

Gombong bamboo classification


Plantae / Plants
Gramineae / Grass Family
Bambusoideae
Bambuseae
Gigantochloa
Gigantochloa Pseudoarundinacea

Fig. 2. Bamboo stem (culm) and its parts [4]


Bamboo stem (culm) is in a form of cylinder, nodes and hollow as shown in Fig. 2. The diameter of bamboo stem
(culm) depends on the species and the environment where it grows varies between 0.5-20 cm. Every bamboo species
have different characteristic. The outer part or bamboo shell contain parenchyme tissue and transport tissue whereas the
inner side containing more fibers. Most of bamboo stem (culm) consist of 50% parenchyme tissue, 40% fiber and 10%
xylem and phloem [5] as shown in Fig. 3.

Fig. 3. Bamboo stem (culm) cross section [6]


Bamboo fiber orientation follow the length of bamboo stem (culm) indicates by sclerenchyme cells surrounding
vascular binding and separated by parenchyme tissue. Fiber length depends on the bamboo types and species with ratio
of length to width of 150:1 up to 250:1. Bamboo fiber determined its mechanical property. The species and bamboo
stem (culm) height relatively to the ground and fiber position on the stem (culm) will cause bamboo fiber is distributed
unevenly [5] as shown in Fig. 4. Gombong bamboo has a tensile strength of 128-192 MPa and elastic modulus around
20-29 GPa [1].

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Fig. 4..Uneven fiber distribution [7].


Bamboo consists of 50-70% cellulose, 20-30% hemicelluloses and 20-30% lignin and also a small part of resin,
tannin and inorganic salt depending on its types and species [5]. Cellulose in bamboo is in the form of polysaccharide
with the formula of C6H12O6 this make celluloseable to withstand to a tensile stress.The glucose molecule has a covalent
bond.Hemicelluloses are a matrix to cellulose its chemical structure is similar with cellulose but simpler and has a low
molecular weight.90% of hemicelluloses consist of silane that make bamboo has a hard wooden feature.Lignin is a
component that binds bamboo fibers. Cellulose and lignin act as a building component of the bamboo cell wall. Most of
cellulose, hemicelluloses and lignin have a hydroxyl group (OH) with a chemical structure shown in Fig. 5 that cause
bamboo easy to absorb and bind with water or water vapor.

Fig. 5. Chemical structure of Cellulose, hemicelluloses [8] and lignin [9]

2. Method
The observation is focused on the characterization of the bending property of Gombong bamboo that is treated by
and without water treatment. In general bamboo is very easy to be attacked by fungi and moths that will reduce its
mechanical property. To prevent the damage a conservation treatment has been carried out by a simple method i.e.
immersing in water or certain chemical compound and heating it to dry. This experiment is carried out by immersing
the Gombong bamboo to a water pond for 2 months as shown by Fig. 6.

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Fig. 6. Bamboo immersed in water for 2 months.


To increase the bamboo mechanical property for construction a drying process should be undertaken so that the
water content deceases. Drying is carried out in an atmospheric air for 2 months. Bamboo is then cut and sliced and
keeps at an open air but contact with water should be prevented. Other method of drying is using an oven at 130-1800C
for maximum one hour [10]. The drying temperature should be monitored to avoid the damage to bamboo structure and
property. The bending test specimen is in the shape of a rectangular with 250 mm x 10 mm x 10 mm as shown in Fig. 7.

Fig. 7. Bamboo specimen for bending test.


The bending test of specimen is carried out by using a universal testing machine Tensilon RTF-1310 with a loading
speed of 5 mm/min. The test is carried out until the specimen break or when a sudden decrease of loading occurs. The
bamboo stem (culm) has an asymmetrical position hence the test is carried out in different test position as shown in Fig.
8. The test is undertaken on:
a. Outer shell part (00from the outer bamboo shell).
b. Inner side part of bamboo stems (1800from outer shell).
c. Sideway part (900from outer shell).

Fig. 8. Illustration of various bending test bamboo specimen position.


3. Results and Discussion
The bending tests were carried out in three different positions for water and non water treated bamboo. The
different test position is based on the bamboo stem (culm) that experienced tensile load during the test. In Fig. 9 it is
shown that the average bending test result of the water treated bamboo is 283.6 52,1MPa with a modulus elasticity of
48.9 9,5 GPa which is lower than the non water treated bamboo i.e. 326.1 48.5 MPa with an elastic modulus of 54.2

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9.8 MPa. According to Liese the mechanical property is depending on the distribution of bamboo fibers. The outer
shell of bamboo has higher strength in compare with the inner shell part. Every bamboo species has a different
mechanical property [5].
.

Fig. 9. The bending strength of Gombong bamboo.


According to the distribution bamboo fibers, the outer shell will have the highest bending strength when experienced
tension. This is due the outer shell has a denser in compare with the inner side that has fewer fibers. But the bending
strength at the 900shows the highest i.e. for water treated bamboo is 327.8 53.3 MPa whereas non-water treated
is376.4 59.0 MPa. The bending strength at 900 is higher due to the maximum contribution of fiber distribution in outer
and inner shell. To observe the difference between the treated and non water treated Gombong bamboo a cross sectional
view using an SEM has been undertaken as can be seen from the following figures below.

Fig. 10. Cross sectional view of a non water treated Gombong bamboo (magnification 12 x).

Fig. 11. Cross sectional view of a water treated Gombong bamboo (magnification 12 x).

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Fig. 12. Cross sectional view of non water treated Gombong bamboo (magnification 75 x).

Fig. 13. Cross sectional view of a water treated Gombong bamboo (magnification 75 x).
Bamboo is built by several tissues and vessels. The tissue that builds a bamboo is the parenchyme, xylem, phloem
and vessel. Parenchyme tissue is a basic tissue of plants it consist of living cells. Xylem or wooden tissue vessel acting
as a supporting cell, vessel and fiber that transporting water and mineral salt that absorb by the root to all parts of the
plants supporting the plants body mechanically. Phloem is a complex tissue that exist in the stem (culm), root and the
leaves it transport food from leave to all part of a plants [5].
SEM observation at 12 x magnification showed that the cross sectional structure of water treated and non water
treated look the same as shown in figure 10 and 11.But at 75 x magnification the cross sectional section of the two has
shown a big difference.In figure 12 the cells and supporting tissue of the non water treated bamboo is still in its
position. In figure 13 several cracks were observed in the parenchyme tissue of water treated bamboo. The cracks
occurred due to the cell damage in the parenchyme hence it shrank. Xylem tissue, phloem tissue and vessel also shrank.
The shrinkage is caused by the living cells that support the tissue and vessels dissolve in water. The dissolved substance
caused the tissue to shrink hence decrease the mechanical property of bamboo. This is in accordance with the literature
mentioning that the decrease of parenchyme tissue in bamboo will decrease its strength [5]. The test showed that water
treated bamboo has the strength of 283.6 MPa lower than the untreated bamboo which is 326.1 MPa. Bamboo swells on
water absorption this is determined by the capability of parenchyme tissue to absorb water and followed by it
dissolution in water. The dissolve tissues are preferred by a kind of moths that leave the fine powder on surface and this
in effect reduce bamboo life time.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
4. Conclusions
The bending strength of non water treated Gombong bamboo is 326.1 48.5 MPa and 283.6 52.2 MPa treated
with a subsequent Modulus of Elasticity of 54.2 9.8 GPa and 48.9 9.5 GPa. The decrease of the bending strength is
caused by the damage of tissuesthat dissolve during 2 months water immersion. On water treated bamboo as seen by
SEM shrinkage has occurred on the tissue. It is recommend to meassure the tensile strength of Gombong bamboo on the
node and internode area.
Acknowledgments
Thanks to Dr. Fatmata Barrie during her 9 months post doctorate stay in ITB Bandung, Indonesia for the discussion
during undertaking the experiment.
References
[1]
Widjaja, E.A. 1995. Gigantochloa Pseudoarundinacea (Steudel) Plant Resources of South-East Asia No. 7:
Bamboo. Backhuys Publisher, Leiden, The Netherlands, pp. 116-118.
[2]
Gigantochloa Pseudoarundinacea. Available at : http://www.bambooweb.info/ShowBambooPictures2 Access
20 Januari 2015.
[3]
Gombong Bamboo Classification. Available at : http://proseanet.org/prosea Access 20 Januari 2015.
[4]
Bamboo stem and its parts. Available at http://www.bamboobotanicals.ca/html/about-bamboo/bamboo-growthhabits.html Access 10 Januari 2015.
[5]
W. Liese, 1985,. Anantomy and Properties of Bamboo. Institute of Wood Biology and Wood Preservation of the
Federal Research Centre for Forestry and Forest Product. Germany.
[6]
S. Sutnaun, et al, 2005, Macroscopic and Microscopic Gradient Structures of Bamboo Culms, Walailak J Sci &
Tech, Vol. 2(1), pp.81-97.
[7]
Fiber
distribution.
Available
at
:
http://static1.squarespace.com/static/53407b1de4b05fdb12d8f4a7/t/537ca69be4b00f10f364c5c1/1400678047013
/moso-transverse-surface.jpg Access 21 Januari 2015.
[8]
Chemical
structure
of
cellulose
and
hemicellulose.
Available
at
:
http://www.bio.miami.edu/dana/226/226F07_3.html Access 20 Januari 2015.
[9]
Chemical structure of lognin. Available at : http://www.namrata.co/dietary-fiber-and-its-significance/ Access 20
Januari 2015.
[10] W.
Schott,
2006,
Bamboo
Under
Microscope.
Available
at
:
http://www.powerfibers.com/bamboo_in_the_laboratory.pdf Access 7 Januari 2015

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
CODE: IM
Effect of Temperature Hydrothermal and Calcination on Electrochemical Performances of Li3V2(PO4)3 as
Cathode for Lithium Ion Batteries
Mochammad Karim Al Amin1), Lukman Noerochim1), Sulistijono1), Diah Susanti 1), Joko Triwibowo2)
Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia
2
Research Center for Physic, Lembaga Ilmu Pengetahuan Indonesia (LIPI-Fisika), Kawasan PUSPITEK Serpong
15314, Tanggerang Selatan, Indonesia
1

Abstract: Lithium ion batteries have many advantages such as high energy density, no memory effect, long time
cycleability and friendly environment. One type of cathode material that can be developed is Li3V2(PO4)3. In this study
Li3V2(PO4)3 has been synthesized via hydrothermal process at temperature 140,160, & 180 C followed with
calcination process at temperature 800 C. SEM images show that the morphology of Li3V2(PO4)3 has irregular flakes
with a size between 1-10 m. CV results show redox reaction occurs in the range between 3 V to 4.8 V with the highest
specific discharge capacity of 136 mAh/g for specimen with temperature hydrothermal and calcination are 180 C and
800 C. This result demonstrates that Li3V2(PO4)3 has a great potential as cathode material for lithium ion battery.
Keywords: Lithium Ion Battery; Cathode; Li3V2(PO4)3; Hydrothermal; Calcination.
1

Corresponding author : Lukman Noerochim, Email : lukman@mat-eng.its.ac.id, lukmanits@gmail.com. Tel. +62-85645988644 Ext. 0000, Fax. +62-31-5943645.

1. Introduction
Lithium Ion battery has three main components, namely the anode, cathode and electrolyte. Research on Lithium
Ion battery has been widely performed, and one type of cathode that is considered to be used is the Li3V2(PO4)3.
Election this cathode has a consideration that is due Li3V2(PO4)3 is a cathode which has a theoretical capacity of 197
mAh/g. Caixian Chang et al, 2008 conducted experiments and successfully obtained capacity 178 mAh/g, 173 mAh/g
and 172 mAh/g by using 0.1 C, 0.2 C and 0.5 C in the voltage range 3.0 Volt to 4.8 Volt, after 100 cycles capacity
cathode to 136 mAh/g, 132 mAh/g and 127 mAh/g [1]. The experiment using hydrothermal temperature variations of
160C for 2 hours and calcination temperature 700 C for 6 hours, the calcination process materials in a vacuum and
under flow Ar gas. The cathode also has some disadvantages such as low conductivity and work cycle that is still bad.
Research to improve the performance of the cathode Li3V2(PO4)3 continues to do, such as reducing and controlling the
particle size morphology. Also needed hydrothermal temperature variations which serves to reduce the size of the
particles. In the control process involves the calcination process that serves to form the stable phase, which leads to
particle growth and aggregation.
2. Methods
In the synthesis process of making cathode Li3V2(PO4)3 material primary or precursor which used was LiOH,
NH4VO3, NH4H2PO4 and glucose. For the composition of each precursor using a molar ratio of 3: 2: 3 (LiOH: NH4VO3:
NH4H2PO4) [3]. The research synthesis cathode Li3V2(PO4)3 is varied with temperature hydrothermal 140, 160 and 180
C for 3 hours. It also varied with temperature calcination 800 C for 6 hours, for calcination process material or
specimen in a vacuum and in a state with the inert gas by Ar. Li3V2(PO4)3 powder was analyzed with XRD
(PANalytical, Cu K_ radiation) was used to identify the phase and structure. For morphology was carried out using
SEM (FEI Inspect 250). Electrochemical performance were tested wih CR2016 coin cells between voltage range 3 4,8
V. The coin cells were fabricated with Li3V2(PO4)3 as the cathode, metalllic lithium as anode, 1 mol LiPF6 in mixed
diethyl carbonate/ethylene carbonate (1:1 in volume) solution as the electrolyte, and Celgard polypropylene as the
separator inside glove box system (Vigor) under Ar flow with adjustable rate. Li3V2(PO4)3 was mixing with glucose
(C6H12O6) for improve the conductiviy of cathode itself and calcined at vacuum horizontal funace with temperature 600
C for 3 hours under Ar flow with gas flow rate 1L/h. The cathode Li3V2(PO4)3 was fabricated on Al foil by coating
mixed slurry of 75 wt.% active material, 20 wt.% conductive black carbon and 5 wt.% polyvinylidene fluoride (PVDF)
binder and N-methylpyrrolidone (NMP) solvent was applied incremently while mixing on agate mortar. Cyclic
voltammetry was measured by an electrochemistry workstation (WonATech WBCS 2000) with sweep scan rate
0,1mV/s and potential range beetwen 3 V 4,8 V. The coin cells were tested Galvanostatic charged discharged on a
recycler battery system (WonATeCH WBCS 2000) with single rate 0,5 C until 25 cycles. Impedance of coin cells were
tested with electro impedance measurement (AutoLab) using 0,1 20000 Hz and potential 4V.

3. Results and discussion

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOM
(ICOMMET 2015)
th
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Surabaya, 4-6 October 2015

( 5 1 2)

( 4 2 0)
( 3 3 2)

(-2 3 3)

(-3 1 2)

(-1 1 4)
(1 1 4)
(1 3 1)

(2 2 0)

(121)

LiVP2O7

(-1 2 2)

(120)

(-1 1 1)

(020)

In the XRD test results show if at all variations of phase Li3V2(PO4)3 already formed corresponding with JCPDS
numbers 01-078-5405.
5405. On the precursor is also contained impurities LiVP2O7 corresponding with JCPDS number 00
00055-0625. XRD patterns indicate if the crystal Lithium Vanadium
Van
Phosphate Li3V2(PO4)3 with all variation is
monoclinic,
linic, according to the XRD curve analysis using PCPDFWIN Version 2.1 program by using JCPDS number 00
00055-0625. Fig. 1 shows XRD patterns of Li3V2(PO4)3.

(c)
o

Hydrothermal : 180 C
o

Intensity (a.u)

Calcination : 800 C

(b)
o

Hydrothermal : 160 C
o

Calcination : 800 C

(a)
o

Hydrothermal : 140 C
o

Calcination : 800 C

CJPDS 01-078-5405

10

20

30

40

50

60

2( )

Fig 1. XRD patterns of Li3V2(PO4)3


Found impurities on the XRD patterns with
w
phase LiVP2O7, this
his is due to the influence of the calcination
temperature, because by using the calcination temperature is less than or equal to 800 C
C can cause the formation phase
LiVP2O7 [4]. The highest peak at plane (1 2 1) for sample with variation
variation hydrotermal temperature 160 oC. From the
calculations have been done using Debye Scherrer equation for the plane (1 2 1) note the value of D for powder
Li3V2(PO4)3 with the hydrothermal temperature of 140 C at temperature calcination 800 C is 80.97 nm, the
hydrothermal temperature of 160 C at temperature calcination 800 C is 40.50 nm and hydrothermal temperature of
180 C at temperature calcination 800 C is 69.44 nm.
SEM test results for powder Li3V2(PO4)3 pada temperature hydrothermal 140, 160 and 180 C at calcination
temperature 800 C can seen in Fig. 2. In the Fig. 2 shown the test results of SEM with a magnification of 2500x then
enlarged back at 5000x magnification at a certain point. SEM results showed that with increasing temperature
hydrothermal
hermal then grain increasingly agglomerated.

(a)

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOM
(ICOMMET 2015)
th
The 7 International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015

(b)

(c)
Fig 2. SEM results on the powder Li3V2(PO4)3 with the temperature hydrothermal (a) 140 C, (b) 160C and (c) 180C
at a temperature calcination 800 C with magnification of 2500x and 5000x
Morphology of powder Li3V2(PO4)3 after hydrothermal process at a temperature of (a) 140 C, (b) 160 C and (c)
180 C at calcination temperature 800 C visible if the particle shape Li3V2(PO4)3 is flake-like
like irregularly, it this is also
similar to what
hat is done by Caixian Chang et al also indicate if the results of the testing SEM powder Li3V2(PO4)3 is
shaped flake-like [1].
Cyclic voltammetry testing is done on the variation of as much as 3 cycles, Cyclic voltammogram (CV) of the
Li3V2(PO4)3 materiall was carried out between 3.0 and 4.8V.
4.8V Every cycle there are four peaks oxidation and three peaks
reduction. Each peak value is almost the same that occurs between cycles 1, 2 and 3. In the oxidation peak occurs at
position ~ 3.61 V, ~ 3,71V, ~ 4,12V and 4,57V while the peaks reduction for the three peaks are be in a position ~
3,52V, ~ 3.62 and ~ 3.92 V can be seen in Fig. 3.
3
Cycle 3
Cycle 2
Cycle 1

0.10

Cycle 3
Cycle 2
Cycle 1

0.15

0.08
0.10

0.04

Current (A/gr)

Current (A/gr)

0.06

ard
Forw

0.02

0.00

-0.02

R e ve

OCV 3 V

rse

0.05

rd
Forwa

0.00

rse
Reve

-0.05

OCV 3,01 V

-0.04
-0.10

2.8

3.0

3.2

3.4

3.6

3.8

4.0

Voltage (V)

(a)

4.2

4.4

4.6

4.8

5.0

2.8

3.0

3.2

3.4

3.6

3.8

4.0

Voltage (V)

(b)

4.2

4.4

4.6

4.8

5.0

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
Cycle 3
Cycle 2
Cycle 1

0.25

0.20

Current (A/gr)

0.15

0.10

0.05

rd
Forwa

0.00

rse
Reve

-0.05

OCV 3 V
-0.10
2.8

3.0

3.2

3.4

3.6

3.8

4.0

4.2

4.4

4.6

4.8

5.0

Voltage (V)

(c)
Fig 3. The test results of samples CV Li3V2(PO4)3 (a) 140oC(800oC), (b) 160oC(800oC) dan (c) 180oC(800oC) with a
scan rate of 0.1 mV/s.
Peaks oxidation that occurs in ~ 3.61 V, ~ 3,71V, ~ 4,12V is due to the extraction of two lithium per unit in
accordance with the following equation [2]:
(

Li V (PO )

)
( .

(
)

( .

(
)

( .

+e

(1)

+e

(2)

For the fourth peak is at ~ 4.57 occurs because of an attempt to extract lithium third.
Three reduction peaks were observed in ~ 3,52V, ~ 3.62 and ~ 3.92 this happens because there is insertion two
lithium per unit according to the formula as mentioned below [2]:

Li V (PO )

(
)

( .

Li V (PO )

)
(
)

+e

( .

(3)
.

( .

(
)

+e

(4)

of the three variations of temperature hydrothermal at Cyclic voltammetry testing that has been done, the sample Figure
3 (c) is the sample with current the highest intensity so that the variation of hydrothermal 180 oC can be used as a
cathode in the battery. This can be seen from the peaks that form in Fig. 3 (c) shows the highest intensity and sharp.
Results of Cyclic voltammetry test can be influenced of XRD test. This is because the samples with variations
temperature hydrothermal 180 oC at temperature calcination 800 oC, the XRD results in Fig. 1 show fewer impurities.
The charge discharge test results on the cathode Li3V2(PO4)3 using variations of temperature hidrotermal 140, 160
and 180 oC at calcination temperature 800 oC is shown in Fig. 4. The test results demonstrate the stability of the cathode
Li3V2(PO4)3 for 25 cycles at 0.5 C between 3.0 V and 4.8 V.
(b)

(a)

5.0
5.0

4.8

4.8

4.6

4.6

4.4

Voltage (V)

4.2
4.0
3.8
3.6

Cycle 25
Cycle 20
Cycle 15
Cycle 10
Cycle 5
Cycle 1

3.4
3.2
3.0

Voltage (V)

4.4

4.2
4.0
3.8

Cycle 25
Cycle 20
Cycle 15
Cycle 10
Cycle 5
Cycle 1

3.6
3.4
3.2
3.0
2.8

2.8
-5

10

15

20

25

30

35

40

45

Unit CD Capacity (mAH/g)

50

55

60

-10

10

20

30

40

50

60

Unit CD Capacity (mAH/g)

70

80

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The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
(c)
5.0
4.8
4.6
4.4

Voltage (V)

4.2
4.0
3.8

Cycle 25
Cycle 20
Cycle 15
Cycle 10
Cycle 5
Cycle 1

3.6
3.4
3.2
3.0
2.8
0

20

40

60

80

Unit CD Capacity (mAH/g)

Fig 4. Charge-discharge curve for the cycle to 1, 5,10, 15, 20 and 25 (a) 140-800oC, (b) 160-800oC, and (c) 180-800 oC
In the hydrothermal temperature of 140 oC with calcination temperature 800 oC in the first cycle shows a capacity of
37.4 mAh/g, but after cycle 25 the capacity decreased to Rp 27.98 mAh / g, the percentage decrease in this variation of
25.18%. For a variety of hydrothermal temperature of 160 oC on the first cycle showed a capacity of 57 mAh/g after 25
cycles the capacity decreased to 41.79 mAh/g, so the percentage decrease of 27.76%. At temperatures of 180 oC
hydrothermal first cycle capacity of 73.14 mAh/g after 25 cycles the capacity decreased to 68.61 mAh/g, the percentage
decline of this variation of 6.19%. From this charge discharge test, samples that have high stability is sampled with
variations in hydrothermal temperature 180 oC. This is affected due to impurities in the hydrothermal temperature
variations 140 and 160 C more much, this is shown in the XRD testing so as to make the stability of these two
samples is reduced. In the CV test results also indicate variation hydrothermal temperature 180 oC has a higher intensity
than the other hydrothermal temperature variations, Cycling performance can be seen in Fig. 5.
o

180-800 C
o
160-800 C
o
140-800 C

75

Unit Discharge Capacty (mAh/g)

70
65
60
55
50
45
40
35
30
25
0

10

15

20

25

Cycle

Fig 5. Cycling performance test results with variations in temperature hydrothermal 140, 160 and 180 C at a
temperature of 800oC calcination
EIS testing at various hydrothermal temperatures 140, 160 and 180 oC at calcination temperature 800 oC can be seen
in Fig. 6. In the variation of hydrothermal temperature 140 oC Rct values obtained 472 , to the value of Rct at
temperature hydrothermal variation 160 oC is 270 , while for the variation of hydrothermal temperature 180 oC Rct
values obtained at 69 . This is consistent with the results of the Charge Discharge test with a small Rct value then
obtained a large capacity, such as in samples with variations of temperature hydrothermal 180 oC and calcination
temperature of 800 oC which has the smallest Rct value so has the value of the greatest discharge capacity compared
with variations of hydrothermal temperature 140 oC and 160 oC.

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The 7th International Conference on Sensors ASIASENSE 2015
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O

180-800 C
O
160-800 C
O
140-800 C

800

700

600

Z"(

500

472

400

300

270
200

69

100

0
0

50

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800

Z' (

Fig 6 Graph EIS semicircle and slope on the variation of hydrothermal temperature 140, 160 and 180 C at a
temperature of 800oC calcination
4. Conclusions
From this research, the highest capacity generated by the variation with hydrothermal temperature of 180 oC and
calcination temperature of 800 oC amounting 73.14 mAh/g and stability are best with a percentage decrease of 6.19%.
This is because the results of XRD at hydrothermal temperature 180 oC and calcination temperature of 800 oC has a high
intensity and have very little impurity peak. Besides, variations in hydrothermal temperature180 oC and temperature
calcination 800 oC at Cyclic voltammetry test also showed high current intensity and the small density between cycle,
where to position redox four peaks oxidation at position ~3.61 V, ~ 3.71V, ~ 4.12V and ~ 4.57V while the reduction for
the three peaks are in the position of ~ 3.52V, ~ 3.62V and ~ 3.92 V. This indicates that the sample of 180 C / 800 C
has a high conductivity. So that the process of intercalation and Li + ion deintercalation running perfectly.
Acknowledgements
Author would like to thank to Ministry of Research Technology and Higher Education who awarding a scholarship
fun Freshgraduate 2013. Center for the Study Materials Nuclear Industry-National Nuclear Energy Agency (PTBIN BATAN) which have given a coin battery assembly and Indonesian Institute of Science-Physics (LIPI Fisika) who has
helped in testing the electrochemical battery performance coin. And do not forge to Lukman Noerochim, Ph.D as the
author's thesis supervisor.
References
[1] Caixian Chang, Jiangfeng Xiang, Xixi Shi, Xiaoyan Han, Liangjie Yuan, Jutang Sun, (2008), Hydrothermal
synthesis of carbon-coated lithium vanadium phosphate, Electrochimica Acta 54 623627 .
[2] K.Nathiya, D.Bhuvaneswari, Gangulibabu, N.Kalaiselvi, (2012), Combustion synthesized nanocrystalline
Li3V2(PO4)3 /C cathode for lithium-ion batteries. Materials Research Bulletin 47 (2012) 43004304
[3] Lu-LuZhang, GangPeng, GanLiang, Peng-ChangZhang, Zhao-HuiWang, Yan Jiang ,Yun-HuiHuang, Hao Lin,
(2012), Controllable synthesis of spherical Li3V2(PO4)3 /C cathode material and its electrochemical performance
Electrochimica Acta 90 (2013) 433439
[4] Shengkui Zhong, Wei Chen, Ling Wu and Jiequn Liu. (2012) A PEG-assisted rheological phase reaction synthesis
of LiFePO4 as cathode material for lithium ion cells Ionics (2012) 18:523527

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
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CODE: IM
Effect of Temperature hydrothermal on Electrochemical Performance of Fe2O3 as Anode for Lithium Ion
Batteries
Eriek Aristya Pradana Putra1, Lukman Noerochim1, Sulistijono1, Diah Susanti1 , Achmad Subhan2
1

Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia
2
Research Center of Physics, Indonesian Institute of Science Physics (LIPI Fisika), Puspiptek, Serpong, Indonesia
Abstract: Fe2O3 is one of the best candidates that can be applied as an anode for lithium ion batteries because of a large
theoretical capacity 1005 mAh/g, wide availability, low production cost and environmentally friendly. In this study has
been successfully synthesized Fe2O3 using hydrothermal method by adding glycine at 9 mmol with variation of
hydrothermal temperature of 140, 160 and 180 C for 10 hrs. SEM images show that the morphology of Fe2O3 is nanoellipses with sizes between 90-200 nm. The highest specific discharge capacity of 634 mAh/g is obtained for specimens
with the addition of glycine by 9 mmol and hydrothermal temperature of 160 C. This result demonstrates that Fe2O3
has a high potential as anode material for lithium ion battery.
Keywords: Fe2O3, temperature hydrothermal, lithium-ion batteries.
Corresponding author : Lukman Noerochim, Email : lukman@mat-eng.its.ac.id, lukmanits@gmail.com. Tel. +62-85645988644 Ext. 0000, Fax. +62-31-5943645.
1. Introduction
Research on batteries has been carried out to produce a battery that has high energy capacity and capable of being
used in a long time. Lithium ion batteries have become a concern because energy density, voltage output and good
flexibility so that it can be used as a rechargeable power source for electronic devices. Material which at large used as
the anode is graphite, because have a cheaper price, a longer life time and environmentally friendly, but the concern that
the energy capacity of the graphite is relatively low, at only about 372 mAh / g. Between the choice of anode material
one that promise the use of metal oxide, where there are several advantages that include large capacity, wide availability
and environmentally friendly [1]. Fe2O3 eligible to be used as the anode because its existence is also abundant,
inexpensive, easy processing and stable processes in chemical conditions. Despite of those intriguing features, Fe2O3
still suffers from poor cyclability due to the drastic volume variation and severe destruction of the electrode upon
electrochemical cycling. In addition, the low conductivity of Fe2O3 also causes performance degradation, especially
when charging and discharging at high current densities. Research to improve the performance of the anode Fe2O3
especially in terms of upgrading cycle continues, one of them with the synthesis of the morphology Fe2O3. [2]. Various
structures have been synthesized to improve the ability of Fe2O3 such as nanowires , nanoroads [3][6], nanoflakes ,
hollow spheres [4], flower and ellipse [1]. In this paper carried synthesis of Fe2O3 by addition of glycine 9 mmol and
variations temperature hydrothermal. Glycine is one type of amino acid where the addition is expected to be a control
hydrolisis so, are expected to set up a nano particle morphology and will improve the performance of the anode Fe2O3
[1]. while hydrothermal process is one method used in the synthesis of nano-structure material processing. High and
low temperatures in the hydrothermal process will affect the rate of nucleation of crystal growth. In this paper used
hydrothermal temperature range between 140oC, 160oC and 180 oC. This variation was conducted to determine the
effect of hydrothermal temperature on the growth of crystals on the anode Fe2O3. Crystallinity of the material obtained
during testing lows at hydrothermal temperature of 160 C it can be seen on the peak produced when testing XRD.
Irreversible capacity is obtained when a given temperature hydrothermal 160 C with the addition of 9 mmol glycin of
634 mAh / g. Small crystal size and homogeneous morphology which makes diffusion of the Li+ ion, the better thus
increasing the capacity of lithium ion batteries. When testing the charge/discharge by giving the C-rate variation with
load current of 1 / 3C to 3C visible if the reduction in capacity was obtained sample, but still be able to maintain the
current loading capacity when given different.
2. Experimental
The nano particle Fe2O3 was synthesized by hydrothermal method. Reagents involved in the synthesis including iron
(III) chloride hexahydrate (FeCl36H2O), glycine and ammonia (NH3H2O). In brief, 6 mmol FeCl36H2O and 9 mmol
glycine were putted into 45 mL of deionized water under stirring to form a homogeneous solution. Subsequently, 15 mL
NH3H2O was introduced into the above homogeneous solution under continuous stirring. After stirring for another 30
min, the total solution was transferred into a Teflon-lined stainless steel autoclave. After being cooled down naturally to
room temperature, the obtained red precipitate was separated by centrifugation, then washed with deionized water and
several times and dried at 60 C in air.Fe2O3 powder precursor was analyzed with XRD (PANalytical, Cu K_ radiation)
was used to identify the phase and structure. Morphology was carried out using SEM (FEI Inspect 250).

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
Electrochemical performance were tested wih CR2016 coin cells between voltage range 3,3 4,5 V. The coin cells
were fabricated with Fe2O3 as, metalllic lithium, 1 mol LiPF6 in mixed diethyl carbonate/ethylene carbonate (1:1 in
volume) solution as the electrolyte, and Celgard polypropylene as the separator inside glove box system (Vigor) under
Ar flow with adjustable rate.Fe2O3 was mixing with glucose (C6H12O6) for improve the conductiviy of anode. The anode
Fe2O3 was fabricated on Al foil by coating mixed slurry of 75 wt.% active material, 20 wt.% conductive black carbon
and 5 wt.% polyvinylidene fluoride (PVDF) binder and N-methylpyrrolidone (NMP) solvent was applied incremently
while mixing on agate mortar. Cyclic voltammetry was measured by an electrochemistry workstation (WonATech
WBCS 2000) with sweep scan rate 0,1mV/s and potential range beetwen 3,3 V 4,5 V.. The coin cells were tested
Galvanostatic charged discharged on a recycler battery system (WonATeCH WBCS 2000) with various C rates, 0,3
C untill extreme rates 2C with 5 cycles for each various rates and single rate 0,5 C until 40 cycles. Impedance of coin
cells were tested with electro impedance measurement (AutoLab) using 0,1 20000 Hz and potential 4V.
3. Results and discussion
XRD results on the sample with the addition of 9 mmol glycine at 140 C temperature variation, 160 C and 180 C
shown in Fig. 1. There the results shown if all diffraction peaks indexed as Fe2O3 iron oxide (hematite) with
rhombohedral crystal system in the space group R-3c, it is standard JCPDS Based 033-0664.

Fig 1. XRD pattern powders of Fe2O3

Fig 1. XRD pattern powders of Fe2O3.


No found any impurities at XRD patterns and highest peak at 104. That can be reported as most crystallin powders.
Product Fe2O3 formed on hidrothermal temperature of 140, 160 and 180C, Calculating of crystal size was carried out
using Debye Scherrer equation.
Table 1 Data XRD results Variation 9 mmol Glycine In plane 1 0 4
Hydrothermal

FWHM

Cos

D(A)

D
(nm)

T= 140 oC

1,541

0,00204

33,285

0,1171

0,958

708,20

70,82

T= 160 C

1,541

0,00233

33,295

0,1338

0,958

619,87

61,99

T= 180 oC

1,541

0,00233

33,203

0,1338

0,958

619,75

61,97

XRD results data is based on Table 1 it can be seen the difference 2 and FWHM values for each sample. FWHM
value with the addition of 9 mmol glycine at hydrothermal temperature of 140 oC at 0.1171 with a crystal size of 70.81
nm, hydrothermal temperature of 160 oC at 0.1338 with crystal ukurann 61.99 nm and hydrothermal temperature of 180
o
C at 0.1338 with 61.97 nm crystal size.
In observation using the SEM FEI Inspect S50 morphology Fe2O3 synthesized by adding glycine as much as 9 mmol
with hydrothermal temperature variation of 140 C, 160 C and 180 C for 10 hours is shown in Fig. 4.9.with SEM

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25.000x magnification, which does not look very significant difference from the third sample. Discrepancies began to
appear when carried 40.000x magnification. At a temperature of 140 C hydrothermal structures that resemble the
nanoparticles are formed as shown in Fig. 2

(a)

(b)

(c)

(d)

(e)

(f)

Fig 2. Fe2O3 structure with variation 9 mmol glycine in (A) hydrothermal temperature of 140 oC Magnification 20.000x
(B) The temperature of 140 C hydrothermal 40.000x Magnification (C) hydrothermal temperature of 160 oC
Magnification 20.000x (D) hydrothermal temperature of 160 oC Magnification 40.000x (E ) hydrothermal temperature
of 180 oC Magnification 20.000x (F).

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Fig 3. Voltammograms chart of sample with temperature hidrothermal 140, 160, 180 oC
Variations of 9 mmol Glycine
The existence of one peaks oxidationat a voltage of 4.0V and4.1 V, which suggests that a process of de-intercalation
on a series of coin battery. irreversible capacity owned hydrothermal heating the sample at, 160 C and 180 C. The
resulting capacity of, 634 mAh/g and 401 mAh/g. However, the resulting capacity is lower when compared with the
Fe2O3 specific capacity reaches 1005 mAh /g [10]. However, the heating capacity obtained in the hydrothermal 160 oC
and 180 oC still exceeds the theoretical specific capacity of graphite, which only reached 372 mAh / g [11] .
In the first cycle peak reduction shown sample with hydrothermal heating of 140 C, 160 C, 180 C where the peak
reduction obtained by, 0,522V, 0,564V , 0.583V. While the oxidation process is at a potential third sample of 1,65 V,
1.72 V , 1.69 V. In Figure 3 seen in case of a potential major shift in the cycle to two to three samples. The dominant
factor affecting caused the formation of a layer of solid-electrolyte interface or SEI irreversible decomposition of the
electrolyte which is common in most of the transition metal oxides used as the anode [7] These things are capable of
influencing the peak reduction at the second cycle in which the potential value becomes 0,963V, 0,894V and 0,952V
whereas oxidation peak becomes , 1,737V, 1,77V and 1,838V.
Based on the results results can be seen if temperature hydrothermal 160 oC provide excellent performance which
earned irreversible capacity high enough to reach 634 mAh / g, but decreased to 500 mAh / g in the second cycle
compared to 180 oC hydrothermal temperature variation which reaches 410 mAh / g with a decrease in the second cycle
to 333 mAh / g. Based on the results of SEM morphology formed in the sample with a temperature of 160 oC resemble
nanoparticles and looks homogeneous. Homogeneity and nano-size particles create a larger surface area so that the
diffusion path of Li + is better.
From Fig. 4 looks if the reduction in capacity caused by the provision of the current load of 1/3 to 3C. when the
temperature is 140 kapastitas deterioration occurs by 84%, to 160 C temperature variation capacity reduction of 94%
and a temperature of 180oC for 86%. Fe2O3 with hydrothermal heating 140 oC able to maintain the reduction in
capacity for a given load current, far better than the two other samples. This is reinforced by the results of XRD where
the sample has a high crystallinity. Fe2O3 crystal lattice capable of storing six ion Li per formula unit with the
mechanism of intercalation / de-intercalation of lithium ion according to the equation Fe2O3 + 6Li 3Li2O + 2Fe [2]
Only the loss of capacity occurs after a given high current loading. Factors contributing to reduced capacity after
pembeban current variation is irreversible reactions of Fe0 to Fe 3+ and lithium-diffusion process is low.
4. Conclusions
Based on the research that has been done, it can be concluded that the making of Fe2O3 as the anode material of
lithium ion batteries by using a hydrothermal method has been successfully performed. Hydrothermal given temperature
variation gives the characteristics and different electrochemical performance. XRD test results on all samples showed a
match with JCPDS No. 033-0664 where all diffraction peaks indexed as Fe2O3 ferric iron oxide (hematite). In testing
the CV obtained the best oxidation current peak intensity of 0,482 A / g and when the reduction amounted to 0.212 A/g
when hydrothermal temperature of 160 C with 9 mmol glycin composition. The redox potential position obtained by
0,583V when 1,69V current reduction and oxidation. This shows if the sample conductivity possessed excellent 9 mmol
glycine. Best irreversible capacity is obtained at a temperature of 160 C with the addition of 9 mmol glycin of 634
mAh / g. Small crystal size and morphology which makes homogeneous diffusion of the Li + ion, the better thus
increasing the capacity of lithium ion batteries. Currently testing the charge / discharge by giving the C-rate variation
with load current of 1/3C to 3C visible if the reduction in capacity was obtained sample hydrothermal temperature of
160 C with a composition of 9 mmol of 94%, this shows the low kristalitas affect the ability of the sample to maintain
capacity when given the load current varies.

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hidrothermal 140 C
hidrothermal 160 C
hidrothermal 180 C
1/3C
0.5C

225

1/3C
200

0.5C

Capacity (mAh/g))

175
150

1C
125

1.5C
100

2C
2.5C
3C

75
50
0

10

20

30

40

50

Cycle

Fig. 4 cycle numbergraph of charge testing - sample discharge Fe2O3 to 45 cylces

Acknowledgements
Authorwould like to thank to Indonesian Institute of Science-Physics(LIPI Fisika) who has helped in testing the
electrochemical battery performance coin. And do not forget to Lukman Noerochim, Ph.D as the author's thesis
supervisor.
References
[1] Xia Wang, Ying Xiao, Changwen Hu, Minhua Cao "A dual strategy for improving lithium storage performance, a
case of Fe2O3." Materials Research Bulletin, (2014). 162169.
[2] Zhi Liu, Junhua Mia, Yuan Yang, Jia Li, Xiu li Tan "Synthesis, characterization and electrochemical properties of
three-dimensionally ordered macroporous a-Fe2O3." Materials Science and Engineering, (2012).. 16121617.
[3] Y.M. Lin, P.R. Abel, A. Heller, C.B. Mullins, a-Fe2O3 nanorods as anode material for lithium ion batteries, J.
Phys. Chem. Lett. 2 (2011) 28852891
[4] B.
Wang,
J.S.
Chen,
H.B.
Wu,
Z.Y.
Wang,
X.W.
Lou,
Quasiemulsion-templated
formation
of
a-Fe2O3
hollow
spheres
with
enhanced
lithium
storage
properties, J. Am. Chem. Soc. 133 (2011) 1714617148.
[5] Jingjing Z, Yifan S, Yu Y, Tao H, Aishui Y, Lysine-assisted hydrothermal synthesis of hierarchically porous
Fe2O3 microspheres as anode materials for lithium-ion, batteriesJournal of Power Sources 222 (2013) 59-65
[6] Hao Liu, Guoxiu Wang, Jinsoo Park, Jiazhao Wang, Huakun Liu, Chao Zhang (2009). "Electrochemical
performance of a-Fe2O3 nanorods as anode material for lithium-ion cells." Electrochimica Acta,hal. 17331736.
[7] Mohd Faiz Hassana, Zaiping Guo, Zhixin Chen, Huakun Liu (2011). "a-Fe2O3 as an anode material with capacity
rise and high rate capability for lithium-ion batteries." Materials Research Bulletin, hal 858864.
[8] Ooi, K., Feng,Q.,Miyai,Y., KanohH., 1992),Lithium Li+Extraction/InsertionwithSpinel-TypeLithium Manganese
OxidesCharacterization of Redox-TypeandIon-Exchange- TypeSites. Langmuir, Vol.8, hal. 18 -61.
[9] Ying Wang 2012). Design of Nanostructured Materials for Advanced Lithium Ion Batteries. Sydney : University
of Technology.
[10] Huang Lihong , Chen Yungui, (2013), Successful Hydrothermal Synthesis of -Fe2O3 Hexagonal Microplatelets and Its Application in Li-Ion Battery, Rare Metal Materials and Engineering 42(10): 2014-2018.
[11] Hongyu Wang, Masaki Yoshio, "Carbon-coated natural graphite prepared by thermal vapor decomposition
process, a candidate anode material for lithium-ion battery", Journal of Power Sources 93 (2001) 123-129.

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The 7th International Conference on Sensors ASIASENSE 2015
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CODE : IM
Synthesis and Electrochemical Performance of LiV3O8 via Reaction Hydrothermal and Various Temperature
Calcination for Cathode Materials of Lithium Ion Batteries
Edith Setia Ginanjar1, Lukman Noerochim1, Sulistijono1, Diah Susanti1 , Bambang Prihandoko2
1

Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia
2
Research Center of Physics, Indonesian Institute of Science Physics (LIPI Fisika), Puspiptek, Serpong, Indonesia
Abstract - Lithium vanadium oxide (LiV3O8) has been successfully synthesized by hydrothermal method followed by
calcination via the reaction of Lithium hydroxide (LiOH) and ammonium metavanade (NH4VO3).The precursors were
heated at temperature 200oC and then calcinated in 400oC, 450oC, and 500oC. The characterization byXRD and SEM
is indicated that LiV3O8 micro-rod have been obtained by this method. The cyclic voltammetry (CV) result showed that
redox reaction occur in potential range between 2.42 V - 3.57 V for the reduction reaction and oxidation reaction in
potential range between 2.01 V- 3.69 V.The highest result was obtained for sample 200oC-500oC with specific
discharge capacity of 131 mA/g. The result showed that LiV3O8 has a promising candidate as a cathode material for
lithium ion batteries.
Keywords : LiV3O8, Cathode, Hydrothermal, Calcination, Lithium Ion Battery
Corresponding author : Lukman Noerochim, Email : lukman@mat-eng.its.ac.id, lukmanits@gmail.com. Tel. +62-85645988644 Ext. 0000, Fax. +62-31-5943645.
1. Introduction
Rechargeable lithium ion battery has become energy storage and transfer system electrochemical, which being
developed. Many research was done to fulfill market demand for batteries in future. The development of lithium ion
batteries have been widely used to replace a wide range of other battery types in use in the field of communications,
computers, electronic equipment, power tools, and transportation. Significant development of lithium ion batteries
evident from the many innovations made in materials, design, and safety factors of the battery. Lithium vanadium oxide
(LiV3O8) has been widely researched as a cathode in lithium ion batteries, because of the high capacity, high energy
density, making an easy, low cost, and has a long cycleability. There have been many studies conducted to improve the
performance of LiV3O8 such as the addition of doping, coating, and morphological modifications[1]. LiV3O8 has a layer
structure consisting of two basic structural units, ie VO6 and VO5 octahedra are distorted into trigonal bipyramids.
These structures into place for lithium ion, but in general lihium ions occupy octahedral structure. Lithium ion
contained in the octahedral structure is connected to the layer LiV3O8 by strong ionic bonds[2].
In the present work, we synthesized micro-rod LiV3O8 via reaction hydrothermal at temperature 200oC and various temperature
calcination (400oC, 450oC, and 500oC). The as-synthesized samples 200oC (500oC) exhibit both good capacity and cycling ability.
These sample had initial discharge 138 mAh /g at range voltage of 2.0 - 4,0 V. This sample also has a percentage decrease in
specific capacity of 20.93% at current densities C / 3 (after a given load up to 3C) and has a coulombic efficiencies above 90% in
each cycle (with variations C). LiV3O8 has great potential as an electrode material for lithium ion batteries.
2. Methods
LiOH and NH4VO3 (V/Li = 2/1.00, mol) was mixed in 60ml demineralization water under magnetic stiring and kept in a
temperature 80oC for 30 minutes, then transparent solution was obtained. Then the resultan mixture was transferred to a 120mL
autoclave and kept in a furnace at 200oC for 12 hours. The resulting solution was heated in 80oC for 12 hours to produce dry brown
solid. The as-obtained materials was calcined at 400oC, 450oC, and 500oC in furnace for 12 hours.
LiV3O8powder was analyzed with XRD (PANalytical, Cu K radiation) was used to identify the phase and
structure. Morphology was carried out using SEM (FEI Inspect 250). LiV3O8was mixing with glucose (C6H12O6) for
improve the conductiviy of cathode itself and calcined at vacuum horizontal funace with temperature 600oC for 3 hours
under Ag flow with gas flow rate 1L/h. The cathode LiV3O8was fabricated on Al foil by coating mixed slurry of 75
wt.% active material, 20 wt.% conductive black carbon and 5 wt.% polyvinylidene fluoride (PVDF) binder and Nmethylpyrrolidone (NMP) solvent was applied incremently while mixing on agate mortar. Electrochemical performance
were tested wih CR2032 coin cells between voltage range 2,0 4,0 V. The coin cells were fabricated with LiV3O8as the
cathode, metalllic lithium as anode, 1 mol LiPF6 in mixed diethyl carbonate/ethylene carbonate (1:1 in volume) solution
as the electrolyte, and Celgard polypropylene as the separator inside glove box system (Vigor) under Ag flow with
adjustable rate. Cyclic voltammetry was measured by an electrochemistry workstation (WonATech WBCS 2000) with
sweep scan rate 0,1mV/s and potential range beetwen 2,0 V 4,0 V. The coin cells were tested Galvanostatic charged
discharged on a recycler battery system (WonATeCH WBCS 2000) with various C rates, C/3 untill 3C with 5 cycles

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for each various rates and then back to rate C/3. Impedance of coin cells were tested with electro impedance
measurement (AutoLab) using 0,1 20000 Hz and potential 4V.
3. Results and discussion
Fig. 1 shows x-ray diffractogram of LiV3O8 synthesized via reaction hydrothermal and various temperature
calcination. It can be found that at sample 200oC (450oC) formed a single phase LiV3O8 according to JCPDS 01-0721193 with layered monoclinic structure . In sample 200oC (400oC) and 200oC (500oC) are all composed of two phases,
the main phase is LiV3O8 and LiVO3.In hydrothermal process LiOH when the react with NH4VO3 could form LiVO3
[3]. The different of cystallinity in each sample of LiV3O8 can be seen in the intensity obtained in fig. 1. Table 1 are
listed crystal sized in plane (1 0 0) by using Debye Schrerrers equation. The parameters is similar to the previous
reports [1, 3, 4, 5]. It can be obtained that crystal size in sample LiV3O8 at 200oC (400oC) is 79.7372 nm, at 200oC
(450oC) is 95.7707 nm, and at 200oC (500oC) is 79.7300 nm. The larger size on its cystal size leading to relatively long
diffusion paths for the lithium ions inserting between these planes.
In the results obtained in sample XRD LiV3O8 with the variation of calcination temperature (400oC, 450oC and
500oC) showed that the intensity of the decline that occurred in the samples 200oC (500oC) this causes the crystallinity
which formed lower when compared with the samples 200oC (450oC). This can occur because of the impurity phase is
formed in the samples 200oC (500oC).

Fig 1. XRD patterns powders of LiV3O8

Fig 2. Cystal size graph powders of LiV3O8

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Calcination (oC)
400
450
500

D ()
797,3728
957,7070
797,3005

Table 1. Crystal size of LiV3O8


D (nm)
2 (o)
( o)
79,7372
14,033
7,0165
95,7707
14,0781
7,03905
79,7300
13,9527
6,97635

FWHM (o)
0,1004
0,0836
0,1004

FWHM (rad)
0,001752
0,005255
0,001459

The morphologies of the LiV3O8 synthesized with various temperature calcination is shown in fig. 3 The sample was
enlagre with magnification 3500x then in view with magnification 15000x back at some point. It can be seen that
various tempereture calcination has caused greatly on its morphology and crystallinity.
At Fig 3. the picture (a) the calcination temperature 400oC visible form of particle morphology LiV3O8 irregular and
agglomerated, has a low intensity on the plane (1 0 0) when compared with the samples 200oC (450oC) indicated that a
low crystallinity formed in this morphology 5m-6m length and diameter of 200nm-300nm. At the calcination
temperature 450oC (Fig 3. (b)) which is derived morphology, increasingly shaping rod that agglomerated with 8m10m long with a diameter of 400nm-600nm.
According to the results of the XRD (Table 1) shows FWHM at 450oC calcination is smaller when compared with
the calcination temperature 400oC, this suggests the crystal size of the variation 450oC better when compared with the
variation in the temperature 400oC, due to the morphology of LiV3O8 started forming rod with irregular and
agglomerated. At 500oC variation (Fig 3. (c)) morphology of rod LiV3O8 getting bigger and homogeneous, this
morphology has a length of 7m - 9m with a diameter of 200nm-600nm. With increasing calcination temperature, it
will enlarge the particle size and uniform shape[1].

Fig 3. SEM powders of LiV3O8

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Fig. 4 shows CV curves of LiV3O8 synthesis via hydrothermal and various temperature calcination is used to
determine the reaction reduction and oxidation (redox) that occur in lithium ion batteries. Redox reaction shows process
intercalation and de-intercalation lithium ions in the electrode surface. Anodic and cathodic peak differences that occur
as well as differences in CV forms indicate differences of electrochemical properties[3]. The third sample showed four
peaks oxidation (~ 2,49V, ~ 3,00V, ~ 3,52V, and ~ 3,65V) and four peak reduction (~ 2,36V, ~ 3,43V, ~ 2,41V, and ~
3,59V). Peaks are formed is caused by phase transformation Li1 + xV3O8 (x = 0.1 to 3)[1]. Reduction in peak ~ ~ 2,36V
and 2,41V indicate the intercalation of Li+ ions into the tetrahedral with two phase transitions of Li3V3O8 to Li4V3O8. At
the peak of ~ 2,01V indicated on the last step of the process is the inclusion of Li + in the phase Li4V3O8 [4].
Cycle 1
Cycle 2
Cycle 3
Cycle 4

0.04

(a)

0.03

0.04

Cycle 1
Cycle 2
Cycle 3
Cycle 4

(b)

0.15

Cycle 1
Cycle 2
Cycle 3
Cycle 4

(c)

0.03

0.02

0.10

-0.02

erse
Rev

-0.03

Current (A/g)

0.00

war
d

0.01

OCV 2,46V

For

Current (A/g)

d
Fo r
war

0.00

OCV 3,06V

-0.01

-0.01

0.05

0.00

ard
rw
Fo

OCV 2,87V

-0.02

erse
Re v

-0.03

-0.04

-0.05

Reverse

-0.04

2.0

2.5

3.0

3.5

-0.10

4.0

2.0

2.5

Voltage (V)

3.0

3.5

4.0

2.0

2.5

3.0

Voltage (V)

3.5

4.0

Voltage (V)

Fig 4. CV cathode LiV3O8


In the CV results obtained in powder LiV3O8 with temperature Hydrothermal 200oC at 400oC calcination
temperature variations, 450oC and 500oCshowed that with an increase in intensity that occur from calcination
temperature of 400oC-500oC. This shows the addition ofcalcination temperature can improve the diffusion of the Li+
ions during the process. intercalation / de-intercalation. This is consistent with results in the can on the SEM, the SEM
morphology seen in the samples 200oC (500oC) increasingly homogeneous.
Initial capacity is obtained on the sample 200oC (400oC), 200oC (450oC), and 200oC (500oC) are125 mAh/g, 98.5
mAh/g, and 138 mAh/g, it is still lower than the capacity of teoritical LiV3O8 which can be up to 280 mAh /g which can
accommodate three ion Li+[2]. This could be caused by the loss of capacity due to damage to the structure of the active
material during the process of intercalation / de-intercalation of Li+ ion [6]. In the samples 200oC (500oC) has the
highest capacity in comparison with 200oC (400oC) and 200oC (450oC), this result corresponding with the result from
CV. CV results for samples 200oC (500oC) has a are better when compared with the calcination temperature 400oC and
450oC.
For the stability of each cycle to LiV3O8 with temperature hydrothermal calcination temperature 400oC, 450oC and
500oC in the variation of C can be seen in figure 5 and 6. At fig. 5 shows the results of discharge will be undertaken on
the variation of the current density C/3; C/2; 1C; 1,5C; 2C; 2,5C; 3C; C/2; and C/3. At fig 6 the picture shown good
stability discharge results on samples 200oC (500oC) of 125.33 mAh/g, at current densities C/3 and 99.10 mAh/g at
current densities C/3 (after loading current density carried through 3C ). This result shows sample 200oC (500oC)
specific capacity loss of 20.93%. When compared with the samples 200oC (400oC) and 200oC (450oC) the specific
capacity loss of up to 21.96% and 21.26%. The coulombic efficiency values of the samples 200oC (500oC) is more
stable and has a value efficiency above 90% for each cycle.
C/3
C/2
1C
1,5C
2C
2,5C
3C

(a)

4.0

3.5

C/3
C/2
1C
1,5C
2C
2,5C
3C

(b)

4.0

Voltase (V vs. Li/Li )

2.5

2.0

3.0

2.5

2.0

1.5
0

20

40

60

80

100

Kapasitas Spesifik (mAh/g)

120

140

3.5
+

3.0

C/3
C/2
1C
1,5C
2C
2.5C
3C

(c)

4.0

Voltase (V vs. Li/Li )

3.5

Voltase (V vs. Li/Li )

Current (A/g)

0.02

0.01

3.0

2.5

2.0

1.5

1.5

20

40

60

80

100

Kapasitas Spesifik (mAh/g)

Fig 5. Polarization charge/discharge cathode LiV3O8

20

40

60

80

100

Kapasitas Spesifik (mAh/g)

120

140

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Fig 6.C-rates cathode LiV3O8


At Fig 7 shows that the samples 200oC (500oC) has Rct value is smaller when compared with the value of Rct on
samples with calcination temperature of 400oC and 450oC. In the samples 200oC (500oC) hasRct value of 260.19 , on
samples with calcination temperature calcination 400oC and 450oC respectively Rct has a value of 152.65 , and 188.46
.At fig.8 the picture is shown a graph of the shown bode plot of Z absolute value (| Z |) against the response of the
frequency. In the samples 200oC (500oC) has a value o | Z | is smaller, amounting to 156.77 when compared with the
calcination temperature 400oC and 450oC which has value | Z | of 225.43 and 173.60 , this is in corresponding with
can result in the graph Nyquist plot where the samples 200oC (500oC) also has the smallest value Rct. It can be seen also
from the curve obtained from the results of cyclic voltammetry and charge / discharge.Pada samples 200oC (500oC) has
a current intensity and a higher specific capacity calcination temperature between 400oC and 450oC. Has the smallest
crystal size obtained in XRD results and a more homogeneous morphology (obtained from SEM) in the samples 200oC
(500oC) when compared with the samples at 400oC and 450oC calcination makes the samples 200oC (500oC) has a high
current intensity and capacity greater specific. By having a crystal size is getting smaller it will shorten the distance of
diffusion of ions Li +, so that the value of Rct and | Z | is the smallest in the sample 200oC (500oC) will make the
intensity of the current is higher and has a capacity spesidik most great, this shows sifak improved electrochemical[5].
From the results that have been obtained, with the addition of calcination temperature can improve the electrochemical
properties of the cathode LiV3O8.

Fig 7. Nyquist plot LiV3O8

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Fig 8.Bode plot LiV3O8


4. Conclusions
LiV3O8 for lithium ion battery cathode application has been successfully synthesized by the method of hydrothermal and
calcination. The results may indicate that the hydrothermal and calcination temperature increases will give effect to the morphology
and size of the crystals that will affect the electrochemical performance of the battery. The electrochemical performance sample
200oC (500oC) has the most excellent electrochemical performance. SEM morphology results in the form of rod and homogeneous,
making these samples had initial discharge voltage range of 2.0 - 4,0V at 138 mAh /g. This sample also has a percentage decrease in
the specific capacity of 20.93% at current densities C / 3 (after a given load up to 3C) and has a coulombic efficiencies above 90% in
each cycle (with variations C). Small crystal size and morphology which makes homogeneous diffusion of the Li + ion is getting
shorter and increase capacity and stabilize the cycle of lithium ion batteries. From the results obtained show LiV3O8 has great
potential as an electrode material for lithium ion batteries.
Acknowledgements
Author gratefully acknowledge the financial and facility support from Ministry of Research, Technology and Higher Education
Republic of Indonesia through Fresh graduate ITS scholarship program 2013, Institute Teknologi Surabaya, and Research Center for
Physic Lembaga Ilmi Pengetahuan Indonesia (LIPI-Fisika).
References
[1] Qiao, Y.Q., Wang, X.L., Zhou, J.P., Zhang, J., Gu, C.D., Tu, J.P, (2011), Sysnthesis and Electrochemical
Performance of Rod-Like LiV3O8 Cathode Materials for Rechargeable Lithium Batteries. Journal of Power
Source, 198 (2012) 287-293.
[2] Kim, Kyungho., Park, Su Han., Kwon, Tae Hyung.,Ahn, Hyungkeun., Eo, Yang Dam., Lee, Man-Jong, (2012),
Reaction Sequence and Electrochemical Properties Of Lithium Vanadium Oxide Cathode Materials Synthesized
Via a Hydrothermal Reaction. Ceramics International, 39 (2013) 1623-1629..
[3] McGraw-Hill, (2004) Handbook of Batteries, third edition eds.Linden, David, Reddy, Thomas B., The McGrawHill Companies, New York
[4] K. West, B. Zachau-Chrisliansen, S. Skaarup, Y. Saidi, J. Barker, I.I. Olsen, Comparison of LiV3O8 Cathode
materials Prepared by Different Methods, J. Electrochem Soc., (1996), Vol 143, No 3.
[5] Pan, Anqiang., Liu, Jun., Zhang, Ji-Guang., Cao, Guozhong., Xu, Wu., Nie, Zimin., Jie, Xiao., Choi, Daiwon.,
Arey, Bruce W., Wang, Chongmin.,and Liang, Shuaquan, Template Free Synthesis of LiV3O8 Nanorods as a
Cathode Material for High-Rate Secondary Lithium Batteries. Journal of Material Chemistry, (2011) 21 11531161.
[6] H. Liu, Y. Wang, W Yang, H. Zhou, Large Capacity of LiV3O8 Cathode Material for Rechargeable Lithium
Based Batteries. Electrochemica Acta, (2010), 56 13920-1398.
[7] J. Xu, H. Zhang, T. Zhang, Q. Pan, Y. Gui, Influence of heat-treatment Temperature on Crystal Structure,
morphology and electrochemical properties of LiV3O8 prepared by Hydrothermal Reaction. J. Of Alloys and
Compounds 467, (2009), 327-331.
[8] Mo, Runwei., Du, Ying., Zhang, Naiqing., Rooney, David., Sun, Kening, (2014), Surface Modification of LiV3O8
Nanosheets Via Layer-By-Layer Self-Assembly for High-Performance Rechargeable Lithium Batteries. Journal
of Power Source 257 (2014) 319-324.
[9] Wang, Dunqiang., Cao, Liyun., Huang, Jianfeng., Wu, Jianpeng, (2011), Synthesis and Electrochemical
Properties of Submicron Sized Sheet-Like LiV3O8 Crystallites for Lithium Secondary Batteries. Material Letters
71, (2012) 48-50.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015

CODE : IM
Effect of Calcination Temperature and Acidity on Electrochemical Performance of LiMn2O4 synthesized by Sol
Gel Process as Cathode for Lithium Ion Battery
Imam Derajat Santoso Setiawan1, Lukman Noerochim1, Sulistijono1, Diah Susanti1 , Joko Triwibowo2, Evvy Kartini3
1

Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia
2
Research Center of Physics, Indonesian Institute of Science Physics (LIPI Fisika), Puspiptek, Serpong, Indonesia
3
Battery Integrated Laboratory, Research Center of Materials Nuclear Industry, National Nuclear Energy Agency
(PTBIN BATAN), Puspiptek, Serpong, Indonesia
Abstract: LiMn2O4 has been a promising candidate as cathode material in lithium ion batteries. In this study, LiMn2O4
was synthesized by sol gel method with LiNO3 and Mn(NO3)2.4H2O as precursor followed by calcination with
temperature variation 600o 800o C. Citric acid is added as a gelling agent and acidity regulator. XRD test reveals that
spinel LiMn2O4 is obtained with no impurity detected. Morphology was carried out by SEM shows spinel nanostructure
with range 48 68 nm. LiMn2O4 exhibits specific discharge capacit 38 mAh/g at 0.5 C. XRD test result show that the
low discharge capacity of LiMn2O4 could be a lost of Li in LiMn2O4 during carbon coating processes.Because, Li make
a chemical bond with carbon become Li2CO3 changes the primary cathode material to MnO and makes a low acidity on
cathode system as a result low discharge capacity.
Keywords: Lithium ion batteries; cathode; LiMn2O4; calcination temperature; acidity regulator
Corresponding author : Lukman Noerochim, Email : lukman@mat-eng.its.ac.id, lukmanits@gmail.com. Tel. +62-85645988644 Ext. 0000, Fax. +62-31-5943645.
1. Introduction
In recent years, lithium ion batteries are one source of energy that a majority on its application in instrument electronic equipment and also allow for the development of electric-powered vehicles of the future, which provides the
power and energy that ability can be developed in future research. Components in lithium ion batteries, among others,
the cathode, anode, separator and electrolyte. On the positive electrode material (cathode) which is commercialized in
lithium ion battery that is often used is LiCoO2 [1]. Where the LiCoO2 cathode type has many uses, among others, has a
fairly high toxicity where the use of Cobalt (Co) therein, can cause an explosion, the raw materials are quite
complicated to do the synthesis, and the price of basic materials are very expensive material. Alternative materials for
the electrode material such as Li (Ni, Mn, Co) O2, LiMn2O4, LiFePO4, Li2FeSiO4, and many others. From some of the
material for the positive electrode of the above, spinel LiMn2O4 material very interesting for further study because it has
a very significant advantage away from LiCoO2 material which in some cases, LiMn2O4 material has properties that are
non-toxic, safe and feedstock material highly abound. A simple method for the synthesis of LiMn2O4 spinel with results
excellent electrochemical characteristics, namely using sol - gel. The synthesis of sol - gel powder can produce a very
high degree of homogeneity by increasing the area of the surface area, which can affect the performance of the material,
when used in battery components. Synthesis method sol - gel has several advantages, such as the controller at the good
stoichiometric and produce particles with sub-micron sizes with a narrow particle size distribution, a relatively low
calcination temperature and shorter time in synthesis. [2]
2. Experimental
The nanoscaled LiMn2O4 (PN-LMO) sample was prepared by solgel method. In a typical of synthesis, 1 g Triton
X 100 (AppliChem.99%) was first dissolved in 20 mL ethanol at room temperature, and then citric acid was added
until the solution have a diffferent acidity,respectively. Citric acid have as chelating agent and pH adjuster [3]., at this
case using some various acidity start at 3 until 5 0,6330 g of LiNO3 (Merck >99%) and 4,5183 g Mn(NO3)2.4H2O
(Merck >99%) were added into the above solution under vigorous stirring. The asobtained solution was heated at 80 oC
overnight under stirring till the solution became a light-yellow gel. The gel was finally calcined in muffle furnace in air
with many variation at 600o - 700 oC for 12 hours. LiMn2O4 powder precursor was analyzed with XRD (PANalytical,
CuK_ radiation) was used to identify the phase and structure. Morphology was carried out using SEM (FEI Inspect
250). Electrochemical performance were tested wih CR2016 coin cells between voltage range 3,3 4,5 V. The coin
cells were fabricated with LiMn2O4 as the cathode, metalllic lithium as anode, 1 mol LiPF6 in mixed diethyl
carbonate/ethylene carbonate (1:1 in volume) solution as the electrolyte, and Celgard polypropylene as the separator
inside glove box system (Vigor) under Ar flow with adjustable rate. LiMn2O4 was mixing with glucose (C6H12O6) for
improve the conductiviy of cathode itself and calcined at vacuum horizontal funace with temperature 600 oC for 3 hours
under Ar flow with gas flow rate 1L/h. The cathode LiMn2O4 was fabricated on Al foil by coating mixed slurry of 75
wt.% active material, 20 wt.% conductive black carbon and 5 wt.% polyvinylidene fluoride (PVDF) binder and N-

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
methylpyrrolidone (NMP) solvent was applied incremently while mixing on agate mortar. Cyclic voltammetry was
measured by an electrochemistry workstation (WonATech WBCS 2000) with sweep scan rate 0,1mV/s and potential
range beetwen 3,3 V 4,5 V. The coin cells were tested Galvanostatic charged discharged on a recycler battery
system (WonATech WBCS 2000) with various C rates, 0,3 C untill extreme rates 20C with 5 cycles for each various
rates and single rate 0,5 C until 40 cycles. Impedance of coin cells were tested with electro impedance measurement
(AutoLab) using 0,1 20000 Hz and potential 4V.
3. Results and discussion
XRD testing found that the test sample in accordance with the JCPDS card number 01-073-6699 for powder
materials by variation of acidity LiMn2O4 3, 4 and 5 as well as the calcination temperature of 600 C, 700 C and 800
C. Based on the standard JCPDS 01-073-6699, said that the system of crystals formed from LiMn2O4 powder was
cubic with space group intended f3dm and its group space number is 227 [4]. Fig. 1 shows XRD patterns of LiMn2O4.
o

(111)

Tcalcine 800 C
LiMn O
(440)

(511)

(531)

(400)

(331)

(222)

(311)

(531)

(440)
(440)

(511)

pH 4

(531)

(511)

(331)

(400)

(331)

(400)

(222)

(311)
(222)

(111)

(311)

Intensity (a.u)

(111)

pH 5

pH 3

JCPDS No 073-6699

10

20

30

40

50

60

70

80

90

2
Fig 1. XRD patterns powders of LiMn2O4
No found any impurities at XRD patterns and found at sampel with pH 5 have a highest peak at (111). That can be
reported as most crystallin powders. Product LiMn2O4 formed on calcination temperature of 700 C, and with the
addition of citric acid as a gelling agent and acidity regulator, here citric acid also acts as a complexing agent, a
chemical that forms a bond with building a link between the ion Mn2+ and Li+ which will make it more stable when the
synthesis sol gel [4]. Calculating of crystal size was carried out using Debye Scherrer equation on Eq. 1 below.

(1)

And as result of calculation was taken at highest peak plane 111. From the above calculation D values obtained at
pH 3 at 48,142 nm, amounting to 68,7815 nm pH 4 and pH 5 nm amounted to 60,2028. Having obtained the value of
crystal size (D), the value of D on variation pH 4 to pH 5 have decrease due to changes in pH 4 to 5 morphological
changes in LiMn2O4, thus making the crystal size becomes smaller at a pH of 5. The higher the degree of acidity in the
synthesis sol - gel LiMn2O4 (5 <pH <10) then the result will be more stable product [5].
In the SEM results LiMn2O4 powder with a calcination temperature of 800 C and various pH 3, 4, and 5 holding time
of calcination for 12 hours at each variation with a magnification of 5000x then enlarged at 30000x magnification at a
certain point can be seen in Fig. 2. That explain, morphologies of LiMn2O4 powder are dominant hexagonal with
various particle size between 50 100 nm. By increasing the degree of acidity, the increasingly dominant particle
morphology hexagonal.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015

Fig 2. SEM images of LiMn2O4 with a calcination temperature of 800 C and various pH 3 (a), 4 (b), and 5 (c) holding
time for 12 hours at each variation with a magnification of 5000x then enlarged at 30000x (d), (e), and (f).
Cyclic voltammetry test results on CR2016 coin battery with LiMn2O4 cathode material with a calcination temperature
of 800 oC variation and pH 3, 4, and 5 can be seen in Fig. 3. In the graph voltamogram not begin at zero voltage point,
but at a voltage of 2,9 V. Because strung batteries have an initial voltage as a result of the diffusion process with a
cathode electrolyte LiPF6, called the Open Circuit Voltage (OCV). OCV measured to evaluate the actual redox
potential, by doing the charged / discharged on the coin cell with a constant current flow is stopped and the cell then left
the stage open circuit until the voltage changes prior to the charged or discharged repeatedly - again, it will form OCV
[6].
The existence of two peaks oxidation at a voltage of 4,0 V and 4,1 V, which suggests that a process of deintercalation on a series of coin battery CR 2016. Then also formed two peaks reduction at point voltage 3.9 V and 4.1
V, which indicates intercalation process. The first peak oxidation at 4.0 V formed by the removal of one half of the Li +
ions in the lattice oxidation LiMn2O4 with Eq. 2 below :

LiMn

Li

Mn O +

Li +

(2)

(release Li+ ion : 4,0 V)


On the next peak at 4.1 V Li ion release the rest of the lattice oxidation LiMn2O4 with Eq. 3 below:

Li

Mn O 2MnO +

(release Li+ ion remaining : 4,1 V)

Li +

(3)

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
st

1 Cycle
nd
2 Cycle
rd
3 Cycle

0.00005

Oxydation (De - intercalation)

Current (A/gr)

0.00004
4.1 V
4.0 V

0.00003
0.00002
OCV 2,9 V

0.00001
0.00000
LiMn2O4

-0.00001
3.9 V

-0.00002
2.8

3.0

3.2

3.4

(G7)
-1

Reduction (Intercalation)
3.6

3.8

Scan Rate 0.1 mVs


4.1 V

4.0

4.2

4.4

4.6

Voltage (V)

Fig 3. Voltamogram of sample with calcination temperature variation of 800 C and pH 3

4.6

4.4
4.4

4.2
st

3.8
3.6

4.0

Voltage (V)

4.0

Voltage (V)

4.2

1 cycle
th
6 cycle
st
21 cycle
th
26 cycle
th
36 cycle

3.4
3.2

st

1 cycle
th
6 cycle
st
21 cycle
th
26 cycle
th
36 cycle

3.8
3.6
3.4
3.2

LMO - 3

3.0

LMO - 4

3.0

10

15

20

25

2.8

30

Specific Charge - Discharge Capacity (mAh/gr)

10

15

20

25

30

35

40

45

Specific Charge - Discharge Capacity (mAh/gr)

(a)

(b)
4.6
4.4
4.2
4.0

Voltage (V)

st

1 cycle
th
6 cycle
st
21 cycle
th
26 cycle
th
36 cycle

3.8
3.6
3.4
3.2

LMO - 5

3.0
2.8
5

10

15

20

25

30

Specific Charge - Discharge Capacity (mAh/gr)

(c)
Fig.4 Polarization graph of charge discharge test using the same current (0,5 C) to 40th cycles where the sample (a) -3
LMO, (b) LMO-4, and (c) LMO-5

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
2 peak voltage with the highest intensity shows that the insertion and extraction of lithium ions occurs in two stages.
The first peak voltage, about 4,0 V, lithium ion associated abolition of half of the tetrahedral sites, where there is
interaction Li-Li. The second voltage peaks were observed at around 4,1 V lithium ion is due to the elimination of other
tetrahedral sites, where the lithium ions do not have interaction Li-Li [6].
Galvanostatic charge discharge test on LMO - 5 with a calcination temperature of 800 C and pH 5. In early
testing charge - discharge the coin cell battery with LiMn2O4 cathode material was tested by the same C - rates (0,5 C)
but repeatedly to 40th cycles. So that will be obtained in each respective polarization graph. This polarization chart to
find out how the behavior of the battery after the same current saddled with a long cycle. Fig. 4 shows the results of a
sample chart polarization LMO - 5.
Results of testing charge - discharge with the same current to 40 cycles of 3 samples tested (LMO -3, LMO - 4, and
LMO - 5), the most stable graphics with displacement cycles are not too change the shape of the chart pattern and which
has a high specific capacity value is in the sample LMO - 4. In first cycle at 38,25 mAh/g to 40th cycles of 36 mAh / g.
This indicates that the sample LMO - 4 this behavior rather than giving the same load, until 40th cycles has not changed
too much from the value of its own capacity, and even remain stable. This is because, on a sample of LMO - 4 is the
provision that the maximum variation calcination temperature of 800 C and also the optimum degree of acidity (pH 5)
has the XRD results with the most excellent level of crystallinity, is shown at the top with a high intensity. In the SEM
test results also showed the sample LMO 4 hexagonal morphology increasingly assertive. On the results of cyclic
voltammetry graph redox reactions that form on the sample LMO - 4 looks more stable when repeated until 3rd cycles.
Thus, the sample with calcination temperature of 800 oC and the degree of acidity (pH 5) have the results chart the best
polarization among other comparative samples cycle number graph, which is the result of plotting the specific capacity
with the number of cycles performed. Fig. 5 is the number of graphic cycles were performed.

LMO - 3
LMO - 4
LMO - 5

40

Specific Discharge Capacity (mAh/gr)

38
36
34
32
30
28
26
24
2

8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40

Cycles Number

Fig. 5 Cycle number graph of charge testing - sample discharge LMO -3, 4, and 5 to 40th cycles
From the graph cycle number Figure 5 above, indicates that the sample LMO - 4 has a value of the highest specific
capacity and stability of the best among the other samples. This further reinforces the results of which revealed the
polarization graph in Fig. 4, no significant changes were significant in the chart polarization and cycle number that
remained stable until 40th cycles. And this result reinforces rather than testing XRD that the higher the level of
crystallinity of the material the more better the stability of the rated capacity.
From the graph of variation C - rates Fig. 7 above, indicates that the sample LMO - 4 has a specific value of the
highest capacity among other samples. This further reinforces the results of which revealed the polarization graph in
Figure 4, no significant changes were significant in the chart polarization and cycle performance remains stable until C the largest rates 3C. And this result further strengthens rather than testing XRD that the higher the level of crystallinity
of the material it will be better the stability of the rated capacity.
After testing charge - discharge with C rates variation up to a maximum of 3C turns off the charts visits, capacity
reduction obtained is not too significant reduction. Then the CR2016 coin battery with LiMn2O4 cathode given load
currents greater, among others, 0,5 C, 1C, 4C, 8C, 12C, 16C, and 20C goal with given loading with high rates is viewed
in terms of battery performance power with extreme current load if the battery is still able to receive a large load
without losing all of its capacity and no damage to the cell.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
LMO - 3
LMO - 4
LMO - 5

42

Specific Discharge Capacity (mAh/gr)

40

0.3

0.5

38

0.3

0.5 C

1C

36

1.5 C

34

2C
2.5 C

32
30

0.3 C

0.5 C 1 C

1.5 C

0.3 C

0.5 C 1 C

1.5 C

2C

2.5 C

3C
3C

0.5 C0.3 C

28
26

2C

2.5 C 3 C

0.5 C 0.3 C

24
22
20
3

12

15

18

21

24

27

30

33

36

39

42

45

Cycle Numbers

Fig. 7 Graph of charge discharge test using a variation C - 0.3 C rates; 0.2 C; 1 C; 2 C; 3 C; 0.5 C and 0.3 C.
4. Conclusions
Results from this resesarch that has been successfully synthesized by the method of sol - gel LiMn2O4 cathode
materials. And the result is the optimum variation of pH 5 and 800 oC calcination temperature variations. Referring to
the XRD test results have the most excellent crystallinity and no impurities, with the smallest size for the calculation of
Debye Scherrer equation is 60,2028 nm, which is the variation of calcination temperature of 800 C and pH 5. For
SEM, the degree of acidity (pH) 5 has a grain size that most large but increasingly dominant in the direction of the
hexagonal. On this sample testing of cyclic voltammetry has the highest intensity. In the greatest degree of acidity
voltamogram results graphed remain stable until 3rd cycles. In the charge-discharge test results stable trend and the
value of the highest specific capacity is at a pH of 5. The charge-discharge capacity value obtained for 38,59 mAh / g.
Then, given the extreme loading to 20C, the rated capacity is 19,7 mAh / g. The value of low capacity due to the
element of Li on separate LiMn2O4 and degrading form Li2CO3 acidity in the system and cause a drop in capacity is far
below the value of the capacity of the theory.
Acknowledgements
Author would like to thank to Ministry of Research Technology and Higher Education who awarding a scholarship
fund Fresh Graduate 2013. Center for the Study Materials Nuclear Industry - National Nuclear Energy Agency (PTBIN
- BATAN) which have given a battery coin assembly and Indonesian Institute of Science - Physics (LIPI Fisika) who
has helped in testing the electrochemical performance battery coin. And honorable Lukman Noerochim, Ph.D as the
author's advisor.
References
[1] D, Guymond., J.M Tarascon, (1991), J Electroschem Soc.130) 2864.
[2] Hmankiewicz, B, (2013), Journal Electroschem Society, 14026.
[3] Yang, Ze., Yan Jiang., Heng - Hui Xu., Yun-Hui Huang, (2013), High Performance Porous Nanoscaled
Limn2o4 Prepared by Polymer Assisted Sol Gel Method, Journal Electrochemical Elsevier.
[4] Ooi, K., Feng, Q., Miyai, Y., Kanoh H., 1992), Lithium Li+ Extraction/Insertion with Spinel-Type Lithium
Manganese Oxides Characterization of Redox-Type and Ion-Exchange- Type Sites. Langmuir, Vol. 8, hal. 18 61.
[5] Hwang, B.J., R, Santhanam., D,G, Liu, (2001), Effect of Various Synthetic Parameters On Purity of LiMn2O4
Spinel Synthesized by A Sol Gel Method at Low Temperature, Journal Electrochemical Elsevier.
[6] Osaka, Tetsuya dan Ogumi, Zempachi, (2011), Nanoscale Technology for Advanced Lithium Batteries, Springer
Science and Business Media, 11 November 2013, hal. 281.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015

CODE: IM
Effect of Temperature Hydrothermal on Electrochemical Performance of Fe3O4 as anode for Lithium Ion
Batteries
Dika Anggara1, Lukman Noerochim1, Sulistijono1, Diah Susanti1 , Achmad Subhan2, Sudaryanto3
1

Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia
2
Research Center of Physics, Indonesian Institute of Science Physics (LIPI Fisika), Puspiptek, Serpong, Indonesia
3
Battery Integrated Laboratory, Research Center of Materials Nuclear Industry, National Nuclear Energy Agency
(PTBIN BATAN), Puspiptek, Serpong, Indonesia
Abstract: Graphite anode which has a specific capacity of 372 mAh/g is generally used in commercial lithium ion
batteries. In this study, graphite be replaced with carbon-coated magnetite (Fe3O4/C) that has advantages like large
theoretical specific capacity of 926 mAh/g, environmental friendly, and low cost production. The synthesis of Fe3O4/C
is carried out by hydrothermal method with reacting FeCl3 and Hexamethylenetetramine (HMT) at temperature
variation of 160oC, 170oC and 180oC. The following process is heated by calcination at temperature variations 450, 500
and 550C. XRD and SEM results show that the as-prepared Fe3O4 powder has a single phase of Fe3O4 and morphology
like micro-flowers with size between 2.7-3.6m. CV test results show redox reaction occurs in the voltage range
between 0.21-0.854V and 1.68-1.81V. The highest irreversible discharge capacity is obtained 1033 mAh/g for specimen
with temperature hydrothermal of 180oC and temperature calcination of 550oC. This result shows that Fe3O4 has a high
potential as anode material for lithium ion battery.
Keywords: Anode, Fe3O4, carbon, hydrothermal, lithium ion batteries
Corresponding author : Lukman Noerochim, Email : lukman@mat-eng.its.ac.id, lukmanits@gmail.com. Tel. +62-85645988644, Fax. +62-31-5943645.
1. Introduction
Since the early 1990s, rechargeable lithium-ion batteries have been widely used as power sources for various
portable electronic devices such as cellular phones, digital cameras, laptop computers and MP3 players [1]. For new
generations of rechargeable lithium batteries, they applied not only to modern consumer electronics but also especially
to hybrid electric vehicles and clean energy storage. The challenges are, naturally, to achieve higher specific energy
density, higher specific power density, longer cycle life and lower cost. These demands create strong motivations
behind the research and development of novel electrode materials with improved electrochemical performance for
lithium-ion batteries. Transition metal oxides represent a new type of anode materials for lithium-ion batteries [2].
These metal oxides with interstitial-free structure can react with Li via the conversion reaction of MOx
+2xLi=M+xLi2O, which has been shown to exhibit larger rechargeable capacity, making them promising anode
materials for new generations of lithium-ion batteries. Among transition metal oxides, Magnetite (Fe3O4) is one of most
attractive materials on economic and eco-friendly. However, its application in practical batteries is hindered due to its
poor cycling stability resulting from large volume expansion occurring during cycling and low rate performance arising
from kinetic limitations [3]. In this study, a new kind of Fe3O4/carbon nanocomposite with flower-like micro
hierarchical structure is prepared by controlled thermal decomposition of the iron alkoxide precursor in inert
atmosphere. This specific configuration results in micrometer-sized particles.
2. Experimental
In a typical synthesis, 0.4 g of FeCl36H2O and 1.0 g of HMT were added to 60mL of ethylene glycol under
magnetic stirring to give a cloudy solution. The resultant mixture was transferred to a 90mL Teflon-lined autoclave,
then sealed and heated at 160C,170C and 180C for 6 h. After the reaction was cooled to room temperature, a green
alkoxide precursor was obtained. The product was harvested by centrifugation and washed with alcohol several times
before drying at 60C in an oven overnight. Afterwards the green powder was heated to 550C at a rate of 5C/min and
maintained at this temperature for 3 h under the nitrogen flow to obtain the black powder. Fe3O4 powder was analyzed
with XRD (PANalytical, Cu K_ radiation) was used to identify the phase and structure. Morphology was carried out
using SEM (FEI Inspect 250). To evaluate the electrochemical performance, coin-type half cells were assembled using
the as-prepared product as anode material for lithium-ion battery. The working electrodes were prepared by dispersing
in N-methyl-2-pyrrolidone (NMP) a blend of as-obtained active material, acetylene black, and polyvinylidene difluoride
(PVDF) at the weight percent ratio of 75:15:10. The slurry was then pasted onto a copper foil and dried in vacuum at
120C for 3 hours. Electrochemical performance were tested with CR2016 coin cells between voltage range 0 3,0 V.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
Surabaya, 4-6 October 2015
Fe3O4 was mixing with glucose (C6H12O6) for improve the conductiviy of cathode itself and calcined at vacuum
horizontal funace with temperature 600oC for 3 hours under Ar flow with gas flow rate 1L/h. Cyclic voltammetry was
measured by an electrochemistry workstation (WonATech WBCS 2000) with sweep scan rate 0,1mV/s and potential
range beetwen 0 3,0 V. The coin cells were tested Galvanostatic charged discharged on a recycler battery system
(WonATeCH WBCS 2000) with various C rates, 0,3 C untill rates 5C with 5 cycles for each various rates.
Impedance of coin cells were tested with electro impedance measurement (AutoLab) using 0,1 20000 Hz and
potential 4V.

( 311)

3. Results and discussion


XRD testing found that the test sample in accordance with the JCPDS card number 01-71-6337 for powder materials
by variation hydrothermal temperature of Fe3O4 160C, 170C and 180C as well as the calcination temperature of
550C. Based on the standard JCPDS 01-71-6337, said that the system of crystals formed from Fe3O4 powder was cubic
with space group intended fd-3m and its group space number is 227 [4]. Fig. 1 shows XRD patterns of Fe3O4 with
variation of hydrothermal temperature.

Intensity (a.u)

( 440)

( 511)

( 400)

( 220)

o
Calcination 550 C

a
JCPDS 71-6337
20

30

40

50

60

70

80

90

Fig 1. XRD patterns powders of Fe3O4 (a) H160, (b) H170 and (c) H180
No found any impurities at XRD patterns and found at sampel with hydrothermal 180C have a highest peak at
plane (3 1 1). That can be reported as most crystallin powders. Calculating of crystal size was carried out using Debye
Scherrer equation.
=

(1)

And as result of calculation was taken at highest peak plane (3 1 1). From the above calculation D values obtained
H160 amounting to 24.79 nm, H170 around 24.79 nm and H180 amounted to 82.59 nm. Figure 2 show the SEM results
of Fe3O4 powder with a hydrothermal temperature 160C, 170C and 180C at calcination temperature 550C. Each
variation with a magnification of 35000x then enlarged back at 50000x magnification at a certain point. That explain,
morphologies of Fe3O4 powder with various particle size between 700 nm 3 m. By increasing the degree of
temperature, the increasingly dominant particle morphology.
Cyclic voltammetry test results on CR2016 coin battery with Fe3O4 can be seen in Figure 3. Samples showed a
reduction peak between voltage range 0.78 to 0.85 V. The presence of reduction peak in voltage range 0.78 to 0.85 V
indicated of intercalation process on circuit CR2016 coin battery. Reduction peaks that occur in the potential range of
0.85 V relating to the phase transformation of LixFe3O4 [5,6]. While oxidation peak has been formed at 1.77 to 1.81 V
show the reversible oxidation from Fe0 to Fe3+. The other highest peak at 0.5 V is possible the decrease of Fe3+ and Fe2+
to Fe0.

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(a)

(d)

(b)

(e)

(c)

(f)

Fig 2. SEM images of Fe3O4 with a calcination temperature of 550C and various temperature hydrothermal (a) H160,
(b) H170 and (c) H180 with magnification of 35000x then enlarged at 50000x fig. (d), (e) and (f).

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0.2

0.1

0.1

0.0

-0.1

Cycle 1
Cycle 2
Cycle 3

Cycle 3

-0.2

Current (A/g)

0.0

Cycle 2

-0.1

Cycle 3

-0.2

-0.3

0.2
-0.4
0.0

0.5

1.0

Cycle 1
Cycle 2
Cycle 3

Cycle 2

Cycle 1
-0.3

1.5

2.0

2.5

3.0
0.1

3.5

0.0

0.5

Cycle 1

1.0

1.5

2.0

2.5

3.0

Voltage (V)

Current (A/g)

Voltage (V)
0.0

-0.1

Cycle 3
-0.2

Cycle 1
Cycle 2
Cycle 3

Cycle 2
-0.3

Cycle 1

-0.4
-0.5
0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Voltage (V)

Fig 3. Voltammograms chart of sample (a) H160, (b) H170 and (c) H180
500

0.3C
0.5C

450

H160
H170
H180

400

Capacity (mAh/g)

Current (A/g)

0.2

350
300

1C

250

1,5C

200

2C
3C

150

4C

5C

100
50
0
0

10

15

20

25

30

35

40

45

Cycle number

Fig.4 Graph of the test charge - discharge using a variation Crates - 0.3C, 0.5C, 1C, 1.5C, 2C, 3C and 4C
Charge - discharge test with variation C-rates was conducted to determine the ability of the battery while received
different currents loaded, whether change significantly capacity or not. Figure 4 shows a graph of the test result of
charge discharge with variations C-rates. From Fig. 4 can be seen that H180 are the the most stable sample.
Percentage of decrease capacity from these samples between 0,3C to 4C reaches 75% lower than H160 which amounted
to 96% and H170 until 97.5%.

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400

H160
H170
H180

350
300

150

198

86

200

73

Z'' ( )

250

100
50
0
0

50

100

150

200

250

300

350

400

Z' ( )

Fig. 5 EIS Nyquist plot graphs of sample H160, H170 and H180
Fig. 5 show the Nyquist plot graphs from sample Fe3O4 which variation hydrothermal treatment. Value of the
impedance obtained for the presence of lithium ion intercalation process that occurs between interfaces on the Fe3O4
material and LiPF6 electrolyte solution. The shape of the graph obtained EIS are semicircle shape and slope. From the
test results can be strengthen of galvanostatic charge-discharge, comparison of XRD test results as well as the crystal
size calculation using the Debye Scherrer equation and the morphology sample from SEM test. From the results of
plotting the graph it can be seen that sample H180 has value of Rct (Resistive Capacitive Transfer) around 198,
sample H160 only reached 86 and sample H170 the value is 73. Whereas the sample H180 has highest value of Rct
(Resistive Capacitive Transfer) however it still has highest capacity. This is due to result of all test, sample H180 the
most dominant all the others.
4. Conclusions
Variations of hydrothermal temperature and calcination on synthesis anode Fe3O4 give effect different at
electrochemical performance and the characteristics. XRD test results on all samples showed a match with JCPDS Card
No. (71-6337) magnetite with the highest intensity diffraction peak is owned at sample H180 with calcination
temperature 550C. Results of SEM test, showing the morphology of Fe3O4 on sample H160 shaped like a flower with a
particle size between 2-3m and agglomeration occurs in other variations. Results of CV test, obtained anodic and
cathodic peak intensity and mutual coincides highest at sample H180 with calcination temperature 550C which showed
improvements in the conductivity of the sample with increasing temperature hydrothermal and calcination. The result of
charge / discharge, showing that sample H180 combination calcination at 550C calcination has the highest capacity
value with the lowest percentage of the reduction in capacity by 75%. While variations H170 and H160 reaches 99%.
Thereby increasing the temperature hydrothermal and calcination can improve the characteristics and performance of
electrochemical anode Fe3O4.
Acknowledgements
Author would like to thank the Graduate Institute of Technology Surabaya on awarding a scholarship fund
Freshgraduate 2013. And the Center for the Study Materials Nuclear Industry - National Nuclear Energy Agency
(PTBIN - BATAN) which have given a coin battery assembly and Indonesian Institute of Science - Physics (LIPI
Fisika) who has helped in testing the electrochemical battery performance coin. And do not forget to Lukman
Noerochim, Ph.D as the author's thesis supervisor.
References
[1] K. Ozawa, Solid State Ionics 69 (1994) 212221.
[2] P. Poizot, S. Laruelle, S. Grugeon, L. Dupont, J.M. Tarascon, Nature 407 (2000) 496499.
[3] S. Mitra, P. Poizot, A. Finke, J.M. Tarascon, Adv. Funct. Mater. 16 (2006) 22812287
[4] Michael E. Fleet, (1981) Acta Crystallographica Section B, vol. 37, 917-920
[5] L. Wang, Y. Yu, P.C. Chen, D.W. Zhang, C.H. Chen, J. Power Sources 183 (2008), 717723
[6] Y. He, L. Huang, J.S. Cai, X.M. Zheng, S.G. Sun, Electrochim. Acta 55 (2010), 11401144.

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CODE: IM
Effect of Al and C Antioxidant on Porosity, Strength and Oxidation Resistance of Alumina-Magnesia Spinel
Refractory
Ridho K. Fadhil1) and Akhmad A. Korda1)
1

Department of Metallurgical Engineering, Institut Teknologi Bandung, Bandung 40132, Indonesia

Abstract: Effect of aluminum and graphite antioxidant on porosity, compressive strength and oxidation resistance of
alumina-magnesia spinel refractory was investigated. In this study aluminum powder and graphite as antioxidant as well
as the type of binder and sintering temperature were varied in alumina spinel refractory. Refractories without the
addition of graphite and with the addition of graphite and the addition of 3% and 5% of aluminum metal powder were
sintered at seven different sintering temperatures of 200, 400, 800, 1000, 1200, 1300, 1400 and 1500C with a holding
time of 6 hours. Characterization of phases formed in the refractory was conducted by using TGA-DTA, X-ray
diffraction and SEM/EDS. The results show that the highest compressive strength was achieved at sintering temperature
of 1500C. The use of aluminum antioxidant can prevent the oxidation of the graphite thus increasing the oxidation
resistance and increase the cold crushing strength of the refractories.
Keywords: aluminum antioxidant; graphite antioxidant; alumina-magnesia spinel refractory; strength, oxidation
resistance
Corresponding author: Akhmad A. Korda, E-mail: akhmad@mining.itb.ac.id, Tel. +62222502239, Fax. +62222504209
1. Introduction
Refractory plays an important role in iron and steel making, where 45% of total consumption of the refractories in
the world comes from the iron and steel industry. By 2016, consumption of the refractories in the iron and steel industry
is estimated to reach 60% of the total consumption of refractories [1]. Besides withstand high temperature, refractory
also need withstand thermal shock and corrosion-erosion caused by hot molten metal and slag. One of the applications
of refractories in the manufacture of iron and steel is a slide gate on a ladle filled with molten steel for continuous
casting process. Alumina-magnesia spinel (MgAl2O4) is a refractory used for slide gate thanks to the low thermal
expansion properties, a high melting temperature, chemically stable and resistant to corrosion [2-4]. The addition of
graphite which has high thermal conductivity and non-wetting ability to molten metal and slag is expected to increase
the strength of the spinel refractory for slide gate application. However, graphite is oxidized easily at low temperatures
that can lead to pores and reduce the strength of the refractory. To prevent oxidation of the graphite, it is necessary to
add antioxidants such as metals (Al, Si, Mg), metal alloys, carbides, or borides.
In this study, the effect of Al and C antioxidants to the compressive strength and porosity of the spinel refractory
would be studied. Spinel refractory using phenolic resins as a binder with the addition of antioxidants will be compared
with the refractory without the addition of antioxidants with alumina cement as a binder. The sintering temperature will
be varied and phase change during sintering will be studied as well. In addition, the effect of Al antioxidant addition to
oxidation resistance of alumina-magnesia spinel refractories will be investigated.
2. Materials and Experimental Procedure
The raw material of alumina-magnesia spinel used in this study is a powder with an aggregate distribution of -45m6 mm. Table 1 shows the composition of the powder alumina-magnesia spinel. Table 2 shows the composition of
antioxidants and binders used for the refractory samples. The refractory samples without the addition of anti-oxidants
using alumina cement as binder while the samples with the addition of anti-oxidants using phenolic resins as a binder.
Once all of the materials were mixed well, each samples were aged for 24 hours at room temperature and followed by a
tempering process at temperatures of 200C for 24 hours. The aging process was carried out before compaction for the
refractory with phenolic resin binder. Meanwhile for the refractory with alumina cement binder, aging was carried out
after compaction to avoid trapped air which can lead to cracking when tempering. The compaction was carried out
using a uniaxial pressing with a pressure of 5 tons. Samples has a cylindrical shape with an average diameter of 1.5 mm
and an average height of 1.6 mm. After the tempering process, the samples were then sintered for 6 hours at
temperatures of 200, 400, 800, 1000, 1200, 1300 and 1500C.

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Tabel 1. Composition of alumina
spinel raw materials
Compounds
%wt
Al2O3
86
MgO
9.5
CaO
0.14
SiO2
0.06
Na2O
0.15
Fe2O3
0.06
Fe Magnetic
0.005

Table 2. Composition of antioxidants and binders used for the


refractory samples
Alumina-magnesia spinel refractory sample
Sample
Al antioxidant
C antioxidant
No
Binder
(%wt)
(%wt)
1
none
none
Alumina cement
2
none
8.5
Phenolic resin
3
3
8.5
Phenolic resin
4
5
8.5
Phenolic resin

The phase transformation of the alumina-magnesia spinel refractory samples were investigated using DTA-TGA.
The investigated samples was the aged refractory samples with the addition of 3% Al antioxidant. Sintered refractory
also characterized using XRD to determine the compounds formed and to explain the results of the DTA-TGA. SEMEDS examination was also carried out to determine the composition of the elements of the refractory. Apparent porosity
of sintered samples were tested according to ASTM C 380-79 for sample no. 1, 3 and 4. Crushing test was conducted at
room temperature using a universal testing machine for sample no. 1, 3 and 4. Oxidation resistance test was conducted
on samples without the addition of antioxidant Al and with the addition of antioxidant Al (3 and 5 %wt). Oxidation
resistance testing was conducted at a temperature of 1100C for 4 hours for sample no 2-4.
3. Results and Discussion
3.1 Characterization of the materials
Thermal characterization is conducted to observe the changes of the organic phase, graphite and antioxidants
contained in the spinel refractory materials during the process of drying and sintering. Figure 1 shows the results of the
DTA-TGA test on the spinel refractory being studied.
5

5
Al reacts with CO gas into
Al2O3 and C

TG

DTA

DTA
Resin
decomposition

TG (wt %)

Al oxidized to Al2O3,
Al melted

Graphite oxidized

TG

0
0

100

200

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

0
1500

-1

-1

-2

-2

-3

Temperature (C)

Heat Flow (V)

-3

Figure 1. DTA-TGA curve for spinel refractory with the addition of 3% aluminum antioxidant
From the DTA-TGA test results shown in Fig. 1, the changes in thermal conditions and weight during temperature
increase can be explained in several stages as follows:
1. At a temperature range of 100 to 300C the release of water vapor, decomposition of phenolic resin binder, release
hydroxyl groups and lighter compounds such as CO, CO2, CH4 [5], it is seen in the TGA curve test results were
marked by a the weight reduction of samples as well as the process which tends exothermic.
2. At a temperature range of 200 to 700C a process of oxidation of the metal Al antioxidant to form the oxide of
Al2O3, it is shown on the TGA curve which observed a significant weight gain, as well as the process which tends
exothermic. In addition, at a temperature of about 660C, aluminum metal melt and then reacts with carbon
originating from refractory or residues of phenolic resin binder to form Al4C3.
3. At temperatures range of 700 to 1000C shows that the weight gain that occurs not as significant at a temperature
range of 200 to 700C, this is due to the start of the oxidation of the carbon contained in the refractories. Carbon
oxidation by oxygen entering through the pores of refractories occur significantly in the temperature range 900 1000C shown by the decline of the TGA curve.

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4.

At temperatures above 1000C, oxidation of the graphite will continue to occur and produce a more stable CO gas
than CO2. In addition, it was observed a change in heat flow occurs significantly at temperatures around 1100C.
This may occur as a result of the accumulation of a phase change, such as the formation of oxidation of Al into
Al2O3, melting aluminum, graphite oxidation, reduction of CO gas by the molten aluminum into Al oxide and solid
carbon.

X-ray diffraction (XRD) testing then performed on the samples to support the DTA-TGA test results. The testing
was conducted on specimens sintered at temperatures of 200, 1000, and 1400C in atmospheric conditions. The XRD
analysis aims to determine the phase change in the refractory material before or after heated in the furnace. Fig. 2 shows
the XRD test results of the three combustion temperature. At temperatures 200C, indicated that Al and carbon are still
evident observed and oxide Al2O3 is formed, but after heated at a temperature of 1000 and 1400C, Al peak disappeared
and the peaks of Al2O3 is becoming increasingly evident. This indicates that the metal Al is oxidized to Al2O3. At
temperatures 1400C, carbon peak can not be detected. This may be caused by XRD tests performed on the sample
surface only, while graphite on the surface of the sample have been oxidized easily.
3000
200C

1000C

Al2O3

1400C

2500

Al2O3
2000

Count

Spinel

Al 2 O3

Al2O3

Spinel

Al2O3

Spinel

Al2 O3

Spinel

Al 2O3

Al2O3

Al2 O3

1400C
1500

Spinel

Spinel Al2O3 C

Spinel

Al2O3

Spinel

Al

Al2 O3

Al2O3

Al2O3
Al 2O3

Al2O3

Al 2O3

Al2O3
Al 2O3

1000C

1000
Spinel

Al2O3

Spinel

500

Spinel

Al2O3 C

Spinel

Al2O3

Al

Al 2 O3

Al 2O3

Al2O3

200C

0
10

20

30

40

50

60

70

80

90

2Theta
Fig. 2. X-ray diffractogram of the investigated refractory samples at temperature of 200, 1000 and 1400C

C = 22.05%
O = 36.05%
Mg = 5.25%
Al = 36.65%

Fig. 3 shows the results of SEMEDS examination conducted on a


sample of refractory with the addition of
5% Al and sintered at temperature of
1300C for 6 hours. In this figure,
oxides and graphite are detected in the
sintered
alumina-magnesia
spinel
refractory surface. It is identified that it
contains elements of Al, C, and O,
which is expected as Al2O3 and graphite
which have not been oxidized. These
results support the XRD test results.
The oxide can prevent the oxidation of
graphite with a mechanism as
previously described.

Fig. 3. SEM-EDS of refractory with the addition of 5% Al and


sintered at temperature of 1300C for 6 hours.
3.2 Effect of binders and antioxidants on the compressive strength of refractories
Alumina-magnesia spinel refractories using alumina cement as the binder will be strengthened at low and high
temperature. After the alumina cement is mixed with water, CA on the cement will become gel, and then form crystals
that provide strength to the material. The cement undergo hydration process that produces hydrate compounds that
provide strength at low temperatures. The hydrate phases include CAH10 (formed at temperatures 20C), C2AH8,

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C3AH6 and AH3 (20 - 35C). C3AH6 and AH3 are stable hydrate compounds, while the other compounds would be
stable with increasing temperature. Cement is then binding the particles in the matrix before further heating [5].
Fig. 4 shows the results of the compressive test of the alumina-magnesia spinel refractory samples without the
addition of aluminum. In the temperature range 200 - 400C, the change in compressive strength does not occur
significantly. The average of compressive strength after heated at a temperature 200C was 8.18 MPa while after heated
at a temperature 400C was 8.10 MPa. Increased refractory strength was obtained after the hydration of the cement
alumina phases that form stable hydrates.
45

Cold compressive strength (MPa)

Without antioxidants
40

With 3% Al antioxidant

35

With 5% Al antioxidant

30
25
20
15
10
5
0
200

400

800

1000

1200

1300

1500

Temperatur (C)

Fig. 4. Effect of sintering temperature on the compressive strength of the alumina-magnesia spinel refractories
After sintering at 800C, the compressive strength of refractory samples has decreased to 6.04 MPa. This is due to
dehydration of alumina cement. When the dehydration process takes place there will be a decrease in strength due to the
rupture of hydraulic bond. C12A7 is a mineral that is first formed after dehydration (500-700C), but this phase is not a
strong phase, CA strong phase will be formed in the temperature range 800-900C [5]. While at a temperature of
1000C, compressive strength did not change significantly due to ceramic bond and CA phases of alumina cement is
still unformed. At a temperature of 1300C, ceramic bonds as a result of sintering begins to form thus providing an
increase in the compressive strength from 6.04 MPa to 29.75 MPa. After sintered at a temperature of 1500C, the
compressive strength continued to increase and reached 40.42 MPa due to the formation of the neck or the connection
between the particles become more complete.
Compressive strength test results for samples of refractory with the addition of 3% and 5% of antioxidant Al has the
same pattern in the temperature range of 200 to 1200 C. In the temperature range 200 - 400C decreased strength,
compressive strength then increased in the temperature range of 400 - 1000C. The compressive strength increased
significantly in the range of 1000 - 1200C. However, differences occur in the temperature range 1200 - 1300C, where
3% of samples with the addition of antioxidants decreased strength, while samples with 5% addition of antioxidants did
not experience significant changes in strength. The compressive strength of the two samples continue to increase in the
temperature range between 1300 to 1500C.
Phenolic resins require heat during the curing so that makes it stable at high temperatures. This is the reason why the
the refractory samples with the addition of 3% and 5% Al antioxidants have fairly good strength after sintered at
temperatures 200C. The compressive strength the refractory is decreased in the range of 200 - 400C caused by the
decomposition of the binder component hydrocarbons into carbon-free and gases such as H2, CH4, CO, and CO2.
Decomposition of the binder also causes the formation of pores in the the refractory so that the porosity increasing [6].
Compressive strength decreases in the temperature range of 400 - 800C occur as a result of the disappearance of the
organic bond. The compressive strength was later increased at temperatures above 800C related to the formation of
Al2O3 and joints between ceramic particles. Al2O3 formation will fill the pores previously formed after binder
decomposition and oxidation of graphite. Al2O3 phase formed will increase the density of the sample and help improve
the compressive strength. Significant increases occurred in the temperature range 1000-1500C also be caused by the
formation of particles bonding ceramic sintering results. Al2O3 phase formed will increase the sample density and
compressive strength. Significant increase in strength that occurs at the temperature range of 1000 - 1500C is caused
by the formation of ceramic particles bond.

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The compressive strength of refractory sample using alumina cement as a binder (without the addition of
antioxidants and graphite) was higher than the samples using phenolic resin binder (with the addition of antioxidants).
This is due to the strengthening mechanism in the samples using alumina cement binder was supported by the presence
of CA-phase formed from the hydrolysis reaction and the joints between the ceramic particles after sintering. While the
mechanism of strengthening of refractory samples using a phenolic resin binder are only provided by the bonding
strength of the ceramic particles after sintering.
3.3 Effect of porosity on compressive strength of refractories
Fig. 5 shows that the porosity of the refractory with alumina cement binder tend to be similar to the temperature
1000C. Porosity of the refractory is decreased in temperature range of 1000 - 1300C and then increase at the
temperature of 1400C. The increase in porosity is caused by dehydration of alumina cement binder that causes the
formation of micro-cracking and increase the porosity [7]. Porosity of the refractory using phenolic resins as a binder
for the temperature range 200 - 800C can not be obtained due to sample experience cracks and spalling. Meanwhile,
the the refractory porosity increases in the temperature range 1000 - 1400C due to oxidation of the graphite. In the
temperature range 1400 - 1600C, the refractory the porosity is decreased due to sintering process. From the Figure 5 it
appears that at high temperature, the porosity does not significantly affect the compressive strength of the refractory.
From the previous studies [7,8], it is known that the porosity in the refractory do not always have a clear relationship
with the compressive strength, this is due to other factors that also affect the compressive strength of the refractory such
phases formed or the formation of pores.
40

Without antioxidants

Apparent Porosity (%)

35

With 3% Al antioxidant

30

With 5% Al antioxidant

25
20
15
10
5
0
400

800

1000

1200

1300

1400

1500

Temperatur (C)

Fig. 5. Apparent porosity of the spinel refractories for various sintering temperature.
3.4 Effect of antioxidants on the oxidation resistant of the refractories
Graphite in alumina-magnesia spinel refractory affect in improving the resistance to the slag attack thanks to its nonwetting character [9]. However graphite can be easily oxidized in a relatively low temperature (above 600C) which is
causes the formation of pores in refractory so that the slag can penetrate into the refractory structure. Figure 6 shows
samples of refractory (without the addition of antioxidants and with the addition of Al) which is oxidized at
temperatures of 1000C for 4 hours. The spinel refractory sample before oxidation has a darker appearance because it
contains graphite. After the refractory samples were oxidized, the appearance of the samples changed into brighter. In
the figure it is shown that after oxidation the sample with the addition of 5% Al antioxidant appear darker than the
sample without the addition of antioxidant or with the addition of 3% Al antioxidant. These observations indicate that
the graphite that were lost during oxidation is reduced with the increasing number of Al antioxidants.

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without
oxidation

oxidized
(sample 1)

oxidized
(sample 2)

0% Al
addition

3% Al
addition

5% Al
addition

Fig. 5. Alumina-magnesia spinel refractories after being oxidized at 1000C for 4 hours.
4.

Conclusions
Refractory alumina spinel using phenolic resin binder has a higher compressive strength than using alumina cement
as a binder at a low sintering temperature. At the sintering temperature above 200C, compressive strength refractories
using alumina cement binder higher than refractories using phenolic resin binder. The higher the sintering temperature,
the higher the compressive strength of the refractory. The compressive strength of refractory using alumina cement
binder is more influenced by the formation of CA phase of alumina cement, while for the refractories with phenolic
resin binder, which were added graphite and aluminum, are influenced by the properties of thermoset phenolic resin and
the formation of Al2O3 phase. The addition of 5% Al gives a better compressive strength compared with the addition of
3% Al. The addition of aluminum can improve the resistance to oxidation of refractory alumina-magnesia spinel.
References
[1] E. D. Guire, Freedonia: World refractory demand to grow annually 3.4 percent through 2016,
http://ceramics.org/ceramic-tech-today/freedonia-world-refractory-demand-to-grow-annually-34-percent-through2016-3
[2] M.A. Sainz, A.D. Mazzoni, E.F. Aglietti, A. Caballero, Mater. Chem. Phys. Vol. 86 (2004) 399
[3] G. Banerjee, P. Bajoria, S. Kumar, S.K Shrivastava, J. Chaudhuri, Slide gate refractories recent trends, Tehran
International Conference on Refractories, 4-6 May 2004
[4] M. A. L. Braulio, M. Rigaud, A. Buhr, C. Parr, V. C. Pandolfelli, Spinel-containing alumina-based refractory
castables, Ceramic International 37, (2011), 1705-1724
[5] H. Efendy, Study of Antioxidations in Refractories MgO-C Monolith with Tar-Resin Binder [Dissertation] (in
Indonesian], Bandung Institute of Technology, Bandung, 2008
[6] S. Irie and J. James, Phenolic resin for refractories, Phenolic Resins: A Century of Progress, L. Pilato (ed), (2010),
503-515
[7] J. Soro, A. Smith and C. Gault, Thermomechanical Characteristics of Calcium Aluminate Cement and Sand Tapes
Prepared by Tape Casting, Journal of the European Ceramic Society 26, (2006), 3799-3807
[8] I. A. Altun, Effect of temperature on the mechanical properties of self-flowing low cement refractory concrete,
Cement and Concrete Research 31, (2001), 1233-1237
[9] W. da Silveira and G. Falk, Production of MgO-X Refractory Material with Cellular Matrix by Colloidal
Processing, Low Carbon Economy, (2012), 83-91

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CODE: IM
Relationship between acidity and crystallinity of mesoporous aluminosilicates synthesized from kaolin bangkabelitung
Desy Tri Kusumaningtyas1, Afifah Rosidah1, Sugeng Triwahyono2, Aishah Abdul Jalil2, Didik Prasetyoko1
1

Department of Chemistry, Institut Tekonologi Sepuluh Nopember, Surabaya 60111, Indonesia


Ibnu Sina Institute for Fundamental Science Studies, Universiti Teknologi Malaysia,
Skudai, Johor Bahru 81310, Malaysia

Abstract: Mesoporous Na-ZSM-5 catalysts have been synthesized from kaolin Bangka Belitung and colloidal silicate
as aluminium and silicon source. Mesoporous H-ZSM-5 catalysts were obtained via ion exchange and calcination of
mesoporous Na-ZSM-5. The catalysts were characterized by using X-ray diffraction, N2 adsorption-desorption and
pyridine adsorption techniques. The influence of crystallinity has been studied to the number of mesoporous and the
Brnsted-Lewis acid site from H-ZSM-5 catalysts. Characterization results of N2 adsorption-desorption showed that
crystallinity of ZSM-5 was increased but mesoporous phase was decreased as aging time increased. Characterization by
pyridine adsorption showed that the higher crystallinity, the number of Lewis acid was decreased. The highest
mesoporous surface area and Lewis acid sites was obtained by sample which have a lowest crystallinity, i.e 255.78 m2/g
and 0.2732 mmol/g, respectively.
Keywords: H-ZSM-5; crystallinity; mesoporous; acidity
Corresponding author: Desy Tri Kusumaningtyas, E-mail: desytri.k@gmail.com, Tel. +62-85-257555752
1. Introduction
Zeolites are microporous crystalline aluminosilicate materials well known for their catalytic and adsorptive activity
and selectivity. They also posses high surface area, high thermal and chemical stability and as such they have found
application in a great number of processes ranging from petrochemical industry to environmental separations [1,2]. The
activity of zeolites is determined by their intrinsic acidity, of both Lewis and Brnsted nature, or by active species
(mostly metal ions or oxides) that can be introduced into the zeolite structure. However, the sole microporosity of
zeolites, which plays a crucial role in their shape selectivity, can also be their biggest drawback [3,4]. Molecules with
diameters larger than the framework pore openings are restricted from entering and approaching the active sites. This
imposes significant limitations in terms of the range of reactions that can be efficiently catalyzed.
Introduction of mesopores into originally microporous zeolitic structures is one approach to obtaining the best of
both worlds, i.e. creating materials with lower diffusion restrictions, which are able to host larger molecular species,
while still retaining desired acidity of the active sites within the structure [4,5]. Such microporous/mesoporrous zeolites
are called hierarchical, a term which designates a zeolitic material with at least one additional level of porosity besides
the intrinsic micropore system. The development of mesopority can be achieved by both synthetic and post-synthetic
routes [6-8].
Hierarchical synthesis of ZSM-5 has been developed from kaolin as a source of silica and alumina, silicalite seed is
added as to induced of ZSM-5 structure and CTABr for mesostructure [9]. Hierarchical ZSM-5 synthesized with
temperature aging at 70C for 6, 12, and 24 hours. The results showed that the longer of aging time, the crystallinity of
ZSM-5 was increased, but the area and volume of mesoporous tends to decrease. Furthermore, in this paper we will
describe the relationship between acidity and crystallinity of mesoporous ZSM-5 synthesized from kaolin bangkabelitung.
2. Research method
2.1 Materials
The raw material of Kaolin were obtained from Bangka Belitung (Al4(Si4O10)(OH)8, 47% SiO2 dan 22% Al2O3),
sodium hydroxide (NaOH, pelet), LUDOX (SiO2, Aldrich, 30%) and cetyltrimethylammoniumbromide (CTABr,
C19H42BrN, Applichem, 99%).
2.2 Methods
2.2.1 Synthesis of Mesoporous ZSM-5
The mesoporous ZSM-5 has been synthesized [9]. It has been synthesized by hydrothermal method with two stages
of crystallization. The mesoporous ZSM-5 were synthesized in a starting aluminosilicate gel with the components of 10
Na2O : 100 SiO2 : 2 Al2O3 : 1800 H2O with a various aging time, i.e 6,12,24 h at 70C, namely : A-6-70, A-12-70 and

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
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A-24-70. In those study, the cationic surfactant was added for meso-structure and seed silicalite to induced MFI
structure.
2.2.2 Ion Exchange
Na-ZSM-5 mesoporous weighed as much as 1.0 gram then inserted into the three-neck-flask size 50mL, then, added
0.5 M ammonium acetate at 50mL. Subsequently, the mixture located within the round flask connected with reflux and
heated to a temperature of 80C, stirring for 3 hours at a speed of 500 rpm. Once completed, the mixture is filtered in a
round flask with filter paper to obtain a precipitate. The precipitate is roasted prior to dry and then calcined at 550 C
for 10 hours to obtain H-ZSM-5.
2.3 Characterization
2.3.1 X-ray Diffraction
The crystallinity of ZSM-5 mesoporous samples was checked by X-ray diffraction. Power X-ray diffraction patterns
were recorded on Phillips Xpert MPD at room temperature using CuK radiation (0.154 nm) from 5 to 50 2 in a 0.02
steps with 1 s per step.
2.3.2 N2 Adsorption
Nitrogen adsorption isotherms were measured at 77 K after pretreatment at 673 K for 4 h under vacuum. The total
surface area was determined by the BET method, the total pore volume was obtained as the amount of nitrogen
adsorbed at p/p0 0.99, and the t-pot method was used to distinguish micropores from mesopores.
2.3.3 Surface Acidity Analysis
Surface acidity analysis performed using pyridine adsorption. Samples of 20 mg pellets made first and then placed
on the sample holder and inserted into Instruments for adsorption N2 and heated at 400C for 4 hours. After that, the
temperature drops until it reaches 30C then put in 1 mL pyridine. Types of Brnsted acid sites determined using
molecular pyridine as a base. Pyridine will be absorbed at room temperature for one hour in a vacuum, followed by
desorption at 150C for three hours. Sample holder taken from the instruments to be analyzed using infrared
spectroscopy were recorded at room temperature in the 1600-1400 cm-1.
The amount of the Brnsted acid or Lewis calculated by the following equation[10]:
The amount of acid site
where :
Lewis acid coefficient (k)
Brnsted acid coefficient (k)
B
L
g

mmol
g

BxL
kxg

x10-3

(1)

= 1.42 cm.mmol-1
= 1.88 cm.mmol-1
= peak area of Lewis or Brnsted acid bond (cm-1)
= area of disk sample (cm2)
= weigh of disk sample (g)

3. Results and discussion


The isotherms of the nitrogen adsorption-desorption of mesoporous samples are shown in Fig.1. However, the
mesoporous area, pore diameter and mesoporous volume are shown in Table 1. All the isotherms showed type IV
adsorption. The isotherms also showed that the longer of aging time, the area and volume of mesoporous tends to
decrease.
XRD patterns, presented in Fig. 2, shows that all the investigated samples preserved their MFI structure. However,
the aging time influence the degree of crystallinity in the mesopore samples. The variations in crystallinity of the ZSM5 mesopore (Table 3) was calculated based on the relative intensities of the reflection at 23 2, taking the crystallinity
of the ZSM-5 commercial to be 100%. The results indicate that the degree of crystallinity decreases with increasing
mesopority.
The acidity aimed to determine the amount of Lewis and Brnsted acid sites of the samples. Surface acidity analysis
performed using pyridine adsorption and analyzed by infrared spectroscopy. Lewis and Brnsted acid sites can be
known if there is a peak between 1440-1460 cm-1 and 1545-1600 cm-1. The acidity of the sample H-ZSM-5 mesoporous
shown in Fig. 3. All samples have Lewis acid sites (peak appears at wave number 1442) and Brnsted acid sites (peak
appears at wave number 1550). Table 4 shows the amount of the Lewis acid and Brnsted acid sites of those samples.
Lewis acid number of the samples A-6-70 is higher than others. Characterization by pyridine adsorption showed that the
higher crystallinity, the number of Lewis acid was decreased, but the number of Brnsted acid was increased

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Table 2. Textural properties of mesoporous ZSM-5

b
a

SBET

Smeso

(m /g)

(m /g)

Vmeso
(cm3g-1)

Dmeso
(nm)

A-6-70

816.96

255.78

0.31

3.84

A-12-70

709.45

120.86

0.22

3.83

A-24-70

696.64

88.48

0.18

3.84

Sample

Fig 1. N2 adsorption-desorption Isotherms of samples


a. A-6-70, b. A-12-70, c. A-24-70

Intensity (cps)

Table 3. The content of intensity and crystallinity of the samples

a
b

2 ()

Sample

2tetha

Intensity

Crystallinity (%)

ZSM-5 commercial
A-6-70
A-12-70
A-24-70

23,14
23,04
23,04
23,04

1813
218.68
423.44
501.95

100

Fig. 2. XRD patterns of the samples a. A-6-70, b. A-12-70, c. A-24-70

Table 4. The amount of Lewis and Brnsted acid


Amount of
Lewis acid
(mmol/g)

Amount of
Brnsted
acid
(mmol/g)

Sample

Surface
area
(m2/g)

Crystallin
ity (%)

A-6-70

255.78

12.06

0.27322

0.20612

A-12-70

120.86

23.36

0.19075

0.18898

A-24-70

88.48

27.69

0.08713

0.30956

12.06
23.36
27.69

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Absorbance (%)

a
Wave number (cm-1)

Fig. 3. FTIR-Pyr Spectra : a. A-6-70, b. A-12-70, c. A-24-70.


4. Conclusions
Mesoporous ZSM-5 has been successfully synthesized from kaolin Bangka Belitung and colloidal silicate as
aluminium and silicon source. Characterization using XRD results showed that the degree of crystallinity decreases
with increasing mesopority. Nitrogen adsorption-desorption results showed that the longer of aging time, the area and
volume of mesoporous tends to decrease. Characterization by pyridine adsorption showed that the higher crystallinity,
the number of Lewis acid was decreased. The highest mesoporous surface area and Lewis acid sites was obtained by
sample which have a lowest crystallinity, i.e 255.78 m2/g and 0.2732 mmol/g, respectively
Advice on this research needs to be done to the application of mesoporous ZSM-5, so it can be learned catalytic
activity.
Acknowledgment
The Authors would like to acknowledge the Ministry of Research and Higher Education, Indonesia, under PUPT
research grant No. 003246.18/IT2.11/PN.08/2015
References
[1] W. Vermeiren, J.P. Gilson, Top. Catal. 52 (2009) 11311161.
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[5] J. Perez-Ramirez, C.H. Christensen, K. Egeblad, C.H. Christensend, J.C. Groenef, Chem. Soc. Rev. 37 (2008)
25302542.
[6] F.S. Xiao, L. Wang, C. Yin, K. Lin, Y. Di, J. Li, R. Xu, D.S. Su, R. Schlogl, T. Yokoi, T. Tatsumi, Angew. Chem.
Int. Ed. 45 (2006) 30903093.
[7] J. Zhao, Z. Hua, Z. Liu, Y. Li, L. Guo, W. Bu, X. Cui, M. Ruan, H. Chen, J. Shi, Chem. Commun. 48 (2009)
75787580.
[8] R. Chal, T. Cacciaguerra, S. van Donk, C. Grardin, Chem. Commun. 46 (2010)78407842
[9] Hamid, Abdul (2015), Synthesis Of Mesoporous ZSM-5 From Kaolin And Colloidal Silica With Two Step
Crystallization : Influence Of Temperature And Aging Time
[10] Emeis, C.A. Journal of Catalys 141 (1993) 347-354.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
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CODE: IM
Preparation and Characterization of CaO/H-ZSM-5 as Solid Base Catalyst
Amalia Putri Purnamasari1), Suprapto1), Meiske S. Sangi2), Didik Prasetyoko1)
1

Department of Chemistry, Institut Teknologi Sepuluh Nopember, Surabaya 60111, Indonesia


Department of Chemistry, University of Sam Ratulangi, Kampus Unsrat, Bahu, Manado 95115

Abstract: The use of alkaline catalysts such as calcium oxide (CaO) in the conversion of waste vegetable oils into
biodiesel has been a lot of attention. In this research, mesoporous H-ZSM-5 was used as a support of CaO to expand the
surface active sites and improve its catalytic activity. Several variation of loading CaO were performed to determine the
influence of loading CaO in the catalytic activity. Synthesized solids were characterized using X-ray diffraction
techniques (XRD) for phase identification, infrared spectroscopy (FTIR) to identify functional groups, adsorptiondesorption of nitrogen to determine the surface area, pore volume and pore size of solids, and also base strength test
using Hammet indicators. The characterization from infrared spectroscopy (FTIR) results showed that CaO/H-ZSM-5
solids have functional groups characteristics of both CaO and mesoporous H-ZSM-5 which appeared in the absorption
band ~550 cm-1 and 480 cm-1.
Keywords: CaO/H-ZSM-5; impregnation; characterization
Corresponding author: Amalia Putri Purnamasari, E-mail: amaliaputripurnamasari@gmail.com, Tel. +62-857-85781991
1. Introduction
The fuel consumption constantly rising from year to year. This is obvious because lately in Indonesia often scarcity
of fuel oil (BBM), and even Indonesia has become the importer of petroleum. Therefore, it is necessary to develop
alternative fuel sources. Biodiesel is a liquid fuel that recently studied as an alternative fuel because it has several
advantages compared with diesel.
It is mainly produced through the transesterification reaction of vegetable oils, which is a natural source of
renewable and sustainable (Kansedo et al., 2009). In the transesterification of vegetable oils, a triglyceride reacts with
an alcohol in the presence of a strong acid or base, producing a mixture of fatty acids alkyl esters and glycerol
(Schuchardt dkk., 1998). Transesterification reaction can take place without using a catalyst, but it requires special
conditions such that relatively long reaction time, high temperatures and pressures. Catalysts which have been used in
the transesterification reaction is homogeneous and heterogeneous catalysts. However, the use of heterogeneous
catalysts is more favorable than the homogeneous catalyst, because it is more environmentally friendly and easily
separated from the product. Heterogeneous catalysts have been studied have a relatively high catalytic activity, but
requires phase synthesis is complex and time-consuming. Thus the need for further research to look for heterogeneous
catalysts are an ideal, inexpensive, environmentally friendly in nature, and is effective for the transesterification
reaction (Zabeti et al., 2010).
Among the heterogeneous catalysts studied, CaO has been considered a promising heterogeneous base catalyst for
biodiesel production (Yan et al., 2008). Alkali oxides CaO not only has a high alkalinity and activity, but also not
soluble in methanol solvent medium in which the transesterification reaction (Demirbas, 2007). To increase the catalytic
activity, some research on supporting CaO material with a large surface area such as silica, alumina and zeolite.
Material support sustain good dispersion of the metal oxide so as to increase the surface area of the active site. Samart
et al. (2010) have done synthesis catalyst CaO/mesoporous silica by impregnation method. Mesoporous silica has a
surface area and large pore volume and has a uniform pore size. Calcium acetate which has been impregnated in the
mesoporous silica solids, distributed evenly on the surface of silica and filled the pores.
Referring to the previous studies, this research will be conducted synthesis of CaO/H-ZSM-5 mesoporous using
impregnation method with a variety of loading Ca 20%, 30%, 40% and 50% (w/w). Then it will be studied the
characteristics of CaO/H-ZSM-5 synthesized mesoporous each variation Ca loading and catalytic activity for the
transesterification reaction.
2. Experimentals
2.1 Preparation of Catalyst
Hierarchical H-ZSM-5 supported calcium oxide was prepared using impregnation method with 50 wt.% CaO
loading. 6.3 g calcium acetate monohydrate was dissolved in 20 ml distilled water. 2 g H-ZSM-5 was added in calcium
acetate solution and the mixture was stirred at 80 C for 40 min. The obtained slurry was dried at 105 C for 12 h in an
oven. Prior to the reaction, CaO/H-ZSM-5 was calcined at 800 C for 2 h. The same steps carried out for loading Ca
20%, 30%, and 40%.

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2.2 Characterization of Catalyst
2.2.1 X-ray Diffraction
The resulting solids were characterized using X-ray diffraction (XRD) techniques using CuK radiation at a
wavelength = 1.541 ,5 voltage of 40 kV and current of 30 mA to the angle range 2 = 5-70 .
2.2.2 Infrared Spectroscopy
The solids were characterized by infrared spectroscopy (Shimadzu 8400S) to determine the bond that is formed in
wave numbers 400-4000 cm-1. Sample preparation carried with KBr pellet method that is the product mixed with KBr to
the sample composition 1% of the total mixture.
2.2.3 N2 Adsorption-Desorption
Prior to the analysis of nitrogen adsorption-desorption, the samples (each as much as 0.05 grams) vacuum for 2
hours at 300 C. Furthermore, flowed and adsorbed N2 gas at very low temperature (77 K) under vacuum pressure. The
surface area of the material being analyzed measured by the number of molecules deposited in monolayer. Specific
surface area (SBET) calculated by the BET equation.
3. Results and Discussion
3.1 X-ray Diffraction
Technique of X-ray diffraction is used for phase identification of samples CaO/H-ZSM-5 that has been synthesized.
Results of XRD diffractogram at 2 () = 5-70 sample shown in Fig 1. shows the XRD pattern of samples CaO peaks at
2 () = 32.21; 37,38; 53.87; 64.15 and 67.37 which are characteristic crystalline peaks CaO thermal decomposition of
calcium acetate. CaO XRD pattern is similar to the results that have been reported by Musumeci et al. (2007).

Fig 1. XRD Patterns of the Samples a. 20% CaO/H-ZSM-5, b. 30% CaO/H-ZSM-5, c. 40% CaO/H-ZSM-5,
d. 50% CaO/H-ZSM-5.
Peaks in the XRD pattern of samples of mesoporous ZSM-5 and CaO appeared on all samples CaO/H-ZSM-5
indicates that the sample contains CaO crystals and ZSM-5. However, in a sample of 20% CaO/H-ZSM-5, 30% CaO/H-

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ZSM-5, 40% CaO/H-ZSM-5 and 50% CaO/H-ZSM-5 shows the difference in intensity peaks of XRD patterns. The
XRD pattern shows higher overall loading Ca on the sample CaO/H-ZSM-5, CaO higher peak intensity and peak
reverse the lower ZSM-5. Similar thing happened on the research that has been reported by Pasupulety et al. (2013) that
the higher loading of Ca on Al2O3 CaO hence the higher peak intensity. XRD peak intensity corresponding to the
concentration of CaO and H-ZSM-5 in the sample. High concentrations will also result in high peak intensity in the
difractogram.
2.2.2 Infrared Spectroscopy
Characterization by FTIR spectroscopy aimed to the identification of functional groups on the solid samples have
been obtained. Fig 2. is the result of the infrared spectra of the sample 30% CaO/H-ZSM-5.

Fig 2. Infrared Spectra of Sample 30% CaO/H-ZSM-5.


Absorption band at 795 cm-1 is a tetrahedral internal structure that is not sensitive and sensitive external
tetrahendral experiencing symmetric stretch vibration. Absorption band at 548 cm-1 is a tape that shows the
characteristics of the ring unit 5 in Pentasil structure such as ZSM-5 zeolite. CaO samples showed OH band at wave
number of about 3600 cm-1, CH band at 2300-2900 cm-1, CO band in the area around 1400 cm-1, 1700 cm-1 and 875 cm1
, as well as on the absorption band of CaO the area around 400 cm-1. This is according to research conducted by
Granados et al. (2007). Meanwhile, sample of 30% CaO/H-ZSM-5 show specific bands which is a combination of the
peak sample ZSM-5 and CaO. Vibration hydroxyl group is indicated by the peak at wave number of about 3600 cm-1,
which is 3635 cm-1 in a sample of 30% CaO/H-ZSM-5.
2.2.3 N2 Adsorption-Desorption
Nitrogen adsorption-desorption isotherms are physical adsorption are used to determine the pore distribution and
surface area of a solid (Haber et al., 1995). Fig 3. shows a graph of adsorption-desorption isotherms of N2 solid CaO
impregnated ZSM-5 with a variation of Ca loading of 20%, 30%, 40% and 50% (w/w). Graph adsorption-desorption
isotherms of samples CaO/H-ZSM-5 shows the hysteresis loop in the middle area which is identical to the type of
adsorption-desorption isotherms of type IV are the type of adsorption of mesoporous solids, which has a size of 2-50
nm pore diameter.
Based on the graph it can be seen that the pressure P/P0 < 0.1 gas teradsorp very little and not full yet monolayer
area. Then when the relative pressure is increased to more than 0.1 began to occur monolayer adsorption of gas
saturated but still a little adsorbed gas. When the pressure is increased again until the P/P0 = 0.5 multilayer adsorption is
taking place, but the amount of adsorbed gas is not very much can be seen from the graph that do not increase in
sharply. At P/P0 0.7 start an interaction of molecules that adsorbed gas in the pore walls facing each other. Isothermal
curve at the pressure rises sharply due to the amount of gas that a very large adsorbed at higher pressure is increased
when the P/P0 = 1. In this pressure causes gas molecules fulfill the pore. The presence of pores on the surface of the
solids will cause capillary condensation phenomenon. Capillary condensation that causes the hysteresis loop (Adamson
and Gast, 1997). Hysteresis loop occurs when pressure is relatively lowered for gas desorption, the amount of N2 gas on
the surface of the sample is still more, so that the amount of gas desorbed less than adsorbed.
Results of the analysis of surface area and pore structure by nitrogen adsorption-desorption is shown in Table 1.
From the table, it can be seen that the impregnation of CaO in the sample mesoporous ZSM-5 effect on the total surface
area. CaO impregnation process on mesoporous ZSM-5 led to the total surface area is reduced due to the solid CaO
distributed on the surface of mesoporous ZSM-5. Increased loading Ca are impregnated in the mesoporous ZSM-5
decreased surface area mesoporous. These results are consistent with research conducted by Albuquerque et al. (2006)
that CaO be uniformly dispersed in SBA-15 so the higher loading of Ca causes a drastic decrease in surface area.

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Fig 3. N2 adsorption-desorption isotherms a. 20% CaO/H-ZSM-5, b. 30% CaO/H-ZSM-5, c. 40% CaO/H-ZSM-5,


d. 50% CaO/H-ZSM-5.

Table 1. Analysis Surface Area, Pore Volume and Pore Diameter of Sample CaO/H-ZSM-5.
Sample
Specific surface area
Pore Volume
Pore diameter
(m/g)
(cc/g)
(nm)
20% CaO/H-ZSM-5
96,792
0,1706
3,843
30% CaO/H-ZSM-5
89,743
0,1823
3,827
40% CaO/H-ZSM-5
62,130
0,1727
3,820
50% CaO/H-ZSM-5
36,702
0,4669
3,419
4.

Conclusions
Preparation and characterization of CaO/H-ZSM-5 has been studied using XRD, FTIR and N2 adsorptiondesorption. From the results obtained that the loading effect of the addition of Ca increase the intensity of X-ray
diffraction patterns and decrease specific surface area and pore diameter.
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14281431.

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from sunflower oil by using activated calcium oxide, Applied Catalysis B: Environmental, Vol. 73, Hal. 31726.
[10] Haber, J. Block, J.H. dan Delmon B. (1995), Manual of Methods and Procedures for Catalyst Characterization,
Pure and Applied Chemistry, Vol. 67, Hal 1257-1306.
[11] Adamson, A.W dan Gast, A.P. (1997), Physical Chemistry of Surfaces, 6nd edition, John Wiley &Sons Inc, New
York.
[12] Albuquerque , M.C.G., Jimenez-Urbistonde, I., Santamara-Gonzalez, J., Merida-Robles, J.M., Moreno-Tost, R.,
Rodrguez-Castellon, E., Jimenez-Lopez, A., Azevedo, D.C.S., Cavalcante Jr, C.L. dan Maireles-Torres, P. (2008).
CaO Supported on Mesoporous Silicas as Basic Catalysts for Transesterification Reactions, Applied Catalyst A
General, Vol. 334, Hal. 3543.

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CODE: IM
Synthesis Of Sodalite From Natural Kaolin Bangka Belitung And Its Application For Removal Of Heavy Metals
Lukluim Mantsuro1), Ratna Ediati1), Didik Prasetyoko1)
1

Department of Chemistry, Faculty of Mathematics and Science, Institut Teknologi Sepuluh Nopember, Surabaya
60111, Indonesia.
Abstract: The effect of leaching and crystallization time in the synthesis of sodalite from kaolin without calcinations
was reported in this research. The synthesis of sodalite was performed using leaching residue from kaolin. Sodalite was
synthesized using reactant molar ratio : 3 Na2O : 1,5 SiO2 : Al2O3 : 128 H2O at 100oC with various of crystallization
time i.e. 1, 2, 3, 6, 9, 12, 24, 36, and 48h. The products were characterized by Fourier Transform Infrared Spectroscopy
(FTIR), X-ray Difraction (XRD) and Scanning Electron MicroscopyEnergy Dispersive X-ray (SEM-EDX) techniques.
The XRD and FTIR spectroscopy showed that the early phase of sodalite was formed at crystallization time 3h. Pure
sodalite was formed at crystallization time 12, 24, 36, 48h. Crystallinity and particle size of sodalite increase as
increasing of crystallization time. Sodalite with crystallization time at 6 and 24h were applied for adsorption of Pb2+ ion,
and compared with sodalite standart.
Keywords: natural kaolin; sodalite; leaching; crystallization time; adsorption of ion Pb2+
Corresponding author: Lukluim Mantsuro, E-mail: lukluim@gmail.com
1. Introduction
Kaolin is an important material that is used in industrial applications, (Murray and Keller, 1993).The presence of
impurities, particularly iron and titanium bearing materials, imparts color to kaolin. During weathering or hydrothermal
alteration, significant levels of iron oxides can be deposited that leave a concentrated kaolinitic clay unusable for
industrial application. Therefore, several chemical methods have been applied to kaolin beneficiation in order to reduce
these contaminants (Veglio et al., 1996; Ambikadevi and Lalithambika, 2000; Lee et al., 2006, 2007).
Most of these investigations have indicated that the kaolinite is more soluble in sulphuric than in hydrochloric acid.
Again, under similar condition of acid treatment, but after amorphization by heating or grinding, all or substantially all
the alumina of the kaolinite is soluble. The shielding of aluminum cation by the siliconoxygen network and the presence
of AlOSi bonds results in low solubility of kaolinite in acids (Mako et al.,2006).
Kaolinite is the main component of kaolin. The material is formed mainly by the decomposition of feldspar, granite,
and aluminum silicate, or generally by weathering process. Kaolinite structure [Si2Al2O5(OH)4] consist of a tertrahedral
silica sheet alternating with an octahedral alumina sheet (Brigatti et al., 2013). The usage of kaolinite as the source of
alumina and silica in the zeolite synthesis has been reported previously by Barrer (1974).
Zeolite are porous material with a three-dimensional framework structure of crystalline aluminosilicate that forms
uniformly sized pores and commonly referred as molecular sieves (Theo, 2007). The empirical formula for zeolite is
M2/nO.Al2O3.ySiO2.wH2O, where y is 2-200, n is the cation valence, w represents the water contained in the
intracrystalline channel of zeolite (Flanigen., 2010). The frameworks are composed of [SiO4]4- and [AlO4]5- tetrahedra,
which corner-share to form different open structure. The tetrahedral are linked together to form cages connected by pore
opening of defined size; depending on the structure type, the pore size range from approximately 0.3-1 nm (Szcostak,
1989).
Sodalite are crystalline microporous tectosilicate with the general composition of Na8[AlSiO4]6(X)2, where X is a
monovalent guest anion (Ocanto et al., 2008; Hassan, 1984). Framework structure sodalites consist of a six-membered
ring aperture with a pore size of 2.8 . Because of the small pore size and high ion exchange capacity, sodalite has
attracted considerable attentions for their potential applications such as optical material (Arieli et al., 2004), waste
management (Buhl et al., 2003), hydrogen storage (Buhl et al., 2005), hydrogen separation (Julbe et al., 2003), and
catalyst support (Ogura et al., 2008).
One application sodalite is the adsorption of heavy metals. Heavy metals in relatively high amounts in the
environment comes from industrial processes or waste oil processing that contaminates the water. One of the heavy
metal is Pb(II). Pb(II) is a waste which has a relatively high toxicity to humans, animals and plants and can not be
described by the environment (Liu et al., 2008). Pb impact on animals and plants is causing damage and death. As to the
human cause anemia, brain damage, mental retardation, anorexia (Somerset et al., 2008). Therefore, we need a process
for the removal of Pb (II) which pollute the environment. One method that is used for the removal of Pb (II) is the
adsorption method. Adsorption method has good efficiency, lower costs and easier implementation. The material
usually used as adsorbent is activated carbon. This material weaknesses that have low adsorption capacity. One material
that has a good adsorption capacity for adsorption Pb (II) is sodalite (Yu et al., 2014).

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The 7th International Conference on Sensors ASIASENSE 2015
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In this research, sodalite had been synthesized from leaching residue kaolin without calcinations step via
hydrothermal synthesis method. The effects of crystallization time on crystalline product and application sodalie for
adsorption of heavy metals were studied.
2. Research method
2.1 Materials
Natural kaolin from Bangka Belitung was used as aluminum and silica source.
2.2 Experimental
Leaching kaolin with sulfuric acid. First, 10.0 g of the kaolin was dissolved in 100 mL of 1.5 mol L-1 H2SO4
aqueous solution, and subsequently the temperature was elevated to 80 0C and stirred for 2 h. The mixture was filtered
and washed with aquademin, then dried in an oven at a temperature of 1000C for 24 h. The synthesis of sodalite was
performed using leaching residue from kaolin. Sodalite was sintesized using same procedure with in this experiment.
The molar composition to synthesized sodalite was 3 Na2O : 1,5 SiO2 : Al2O3 : 128 H2O. Sodium hidroksida and
aquadest were mixed into polypropilen bottle and stirred until sodium aluminat soluble, 3 g kaolin was added and
stirred vigorously, sodium aluminate was added and stirred for 24 hours at room temperature. Hydrothermal reaction at
100 C, filtered, washed with aquadest until pH under 9 and dried for 24 hours at temperature 100 C. This procedure
was same used by crystallization time at 1, 2, 3, 6, 9, 12, 24 hours.
2.3 Characterization
All samples were characterization by powder X-ray diffraction (XRD) and IR-spectroscopy. X-ray data were
collected on a X-ray Diffraction Phillips Expert with CuK radiation ( = 1,54056 ), voltage 40 kV, 30 mA and 2 =
5-50. The infrared spectra were recorded on (SHIMADZU) using KBr technique in the wavelength range of 400-4000
cm-1. Samples with crystallization time 24 hour was characterization by Scanning electron microscope (SEM) images
operated at an acceleration voltage of 20.00 kV and work distance of 8.5 mm. Compositional analysis were performed
using energy-dispersive X-ray analyzer attached to the microscope (SEM-EDX) for Si, Al, Na.
3. Results and discussion
3.1 XRD and FTIR Analysis
Fig 1. (1A-B) shows the pattern of kaolin before and after leaching treatment. Fig 1. (1C-D) shows the pattern of the
synthesis product obtained at the crystallization times 1, 2 hours where is raw kaolinite is dominant. Kaolinite is
identified by its characteristic X-ray diffraction peaks at 12.34 and 24.64 (Zhao et al., 2004). It shows that kaolinite
was not dissolved in the alkaline solution. Fig.1 (1D-H) at synthesis product obtained at 3, 6, 9, 12 hours shows that the
raw kaolinite had dissolved and obtained new phases such as zeolite A (LTA) and sodalite had already formed as
indicated by broad diffraction peak at 2 angle of 13.91 and 42.70. Fig.1 (1I) shows that the kaolinite peak are
negligible after reaction 24 hours and obtained sodalite. The peaks sodalite at 2 angle are 13.91, 24.26, 31.51,
34.61 and 42.70.
Fig 1. (2A-B) shows the FTIR spectra of kaolin before and after leaching treatment. Fig 1. (2C-D) shows the FTIR
spectra of the synthesis product obtained at the crystallization times 1, 2 hours where raw kaolinite is dominant. The
characteristic broad band kaolinite are 1116, 1006 cm-1 belong to Si-O stretching, the peak 912 cm-1 belong to inner OH
bending, the broad band at 792 and 754 cm-1 assign to vibrasi Si-O-Si stretching, the peak 538 cm-1 assign to Al-O
deformation and finally, 468 and 428 cm-1 broad band are adapted to the deformation vibration of Si-O. Its shows
suitable with characteristic X-ray diffraction. Fix.1 (2D-H) At the crystallization times 3, 6, 9, 12 hours shows that
characteristic broad band from kaolinite was decreased and appear new broad band such as zeolite A at 468 cm-1 belong
to bending vibration of T-O bond (T = Si or Al) (Rayalu et al., 2005) and sodalite was formed as indicated broad band
at 694 and 657 cm-1 are due to the symmetric stretch (T-O-T) (Yao et al., 2006). Fig. 1(2I) shows that sodalite was
formed. In the IR spectrum of the sodalite sample, the broad band at approximately 990 cm-1 is assigned to asymmetric
stretch (T-O-T), the adsorptions between 694 and 657 cm-1 are due to the symmetric stretch (T-O-T), the band at 459
cm-1 arise from the bending vibration of O-T-O, and the characteristic band at 424 cm-1 appears as single four
membered ring (S4R) of the sodalite unit.

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(2)

(1)

Fig. 1. XRD pattern and FTIR spectra of kaolin leaching (A) before, (B) after; sodalite sample at hydrothermal time
(C) 1 h, (D) 2 h, (E) 3 h, (F) 6 h, (G) 9, (H) 12 h, (I) 24 h.
The hydrothermal transformation of kaolinite after contacting the alkaline solutions indicates that there are two
major processes involved the dissolution of kaolinite releasing Si and Al and the precipitation of sodalite (Rios et al,
2009). During the hydrothermal transformation of kaolinite, the amorphous phase transforming to zeolite LTA, which
transformed to sodalite (Barnes et al., 1999; Choi et al., 2005). Transformation zeolite A into sodalite crystals and found
that transformation takes place by the dissolution of zeolite A followed by supersaturation of the liquid phase with
aluminosilicate species and nucleation of sodalite.
Optimum crystallization times condition is required to synthesis sodalite. Crystallization time strongly affect the
nucleation and crystal growth. Increase in time will increase both crystal growth rate and nucleation rate (Zhdanov and
Samulevich, 1980). Crystallinity will increase with longer crystallization time. As a result, the maximum synthesis time
of 24 hour was selected to synthesis sodalite.
3.2 SEM-EDX Analysis
Crystallinity has been estimated by taking the sum total of the relative intensities of characteristic peaks sample
divided to sum total of the relative intensities of characteristic peaks standart (Rayalu et al., 2005). Crystallinity of the
sodalite samples were calculated using eq. (1).
Crystallinity =

x 100

(1)

The crystallite sizes of the sodalite samples (dXRD) were calculated by the Scherers equation using the line
broadening of the 211 diffraction peak (eq. 2) (Hiyoshi, 2012). The (dXRD) values suggested that these samples were
composed of nano-sized crystals.
dXRD =

is wave length of X-ray used (0.154 nm), B is full width at half maximum 2 1 1 difraction peak after substaction of
line broadening due to the apparatus, is Bragg angle.

(2)

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Table 1. Physicochemical property kaolin
Sampel
% Crystallinity
O:Al:Si:Fe
KA (before)
6.44
83.00:9.54:7.30:0.15
KA (after)
22.69
90.65:5.45:3.89
Fig.2 Energy dispersive X-ray was used to detect quantifying the silica, aluminium, sodium and iron contain for
kaolin before leaching. Than after leaching, quantifying without iron contain. The molar composition ratio Si/Al are
0.68 and 2.69 to kaolin before and after leaching respectively (Table 1).
Energy dispersive X-ray was used to detect quantifying the silica, aluminium and sodium contain for sodalit.
Table 2. Crystallinity sodalite
Sampel
% Crystallinity
SOD 3
6.44
SOD 6
22.69
SOD 9
32.18
SOD 12
40.44
SOD 24
52.72
Kaolin before
leaching

Kaolin after
leaching

Fig.2. SEM and EDX image of kaolin leaching (A) before, (B) after.
Fig.3 shows SEM images of the sodalite samples. The SEM image of the sodalite samples showed individual
submicron crystal with size 100 nm. The crystal size of the sample SOD 24 was smaller than sample SOD 6. It was
suitable with crystallite sizes from (dXRD) values (Table 2).
The synthesis of the best products are tested for Pb 2+ ion adsorption using the batch method. The amount adsorption
of Pb resulted from sodalite crystallization time for 24 h and standart sodalite were 97,22 and 106,07 mg/g (Wahyuni,
2015). Sodalite is a highly efficient adsorbent for metal ions removal from aqueous solution, which exhibits much
higher adsorption capacity than other low-cost adsorbents.

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SOD 6

SOD 24

Fig. 3. SEM image of sodalite sample at hydrothermal time (A) 6 h, (B) 24 h.

4. Conclusions
Leaching strongly effect kaolin to reduce these contaminants. Crystallization time strongly affect to synthesis of
sodalite. The maximum synthesis time of 24 hour was selected to synthesis sodalite. Crystallinity will increase with
longer crystallization time and particle size be smaller. sodalite is a highly efficient adsorbent for metal ions removal
from aqueous solution.
References
[1] Ambikadevi, V.R., Lalithambika, M., 2000. Effect of organic acids on ferric iron removal from iron-stained
kaolinite. Appl. Clay Sci. 16, p.133145.
[2] Arieli, D., Vaughan, D.E.W., Goldfarb, D., Journal of the American Chemical Society 126 (2004), p.57765788.
[3] Barnes, M.C., Addai-Mensah, J., Gerson, A.R., Microporous Mesoporous Materials 31 (1999b), p.287302.
[4] Breck, D., New York: John Wiley & Sons Inc, (1974).
[5] Brigatti, M.F., Galan, E., Theng, B.K., Developments in Clay Science Elsevier 5A (2013), p.2181.
[6] Buhl, J.C., Gesing, T.M., Kerkamm, I., Gurris, C., Microporous and Mesoporous Materials 65 (2003), p.145153.
[7] Buhl, J.C., Gesing, T.M., Rscher, C.H., Microporous and Mesoporous Materials 80 (2005), p.5763.
[8] Choi, S., Amistadi, M.K., Chorover, J., Geochim.Cosmochim. Acta 69( 2005a), p.44254436.
[9] . Mak, Z. Senkr, J. Kristf, V. Vgvlgyi, Surface modification of mechanochemically activated kaolinites by
selective leaching, J. Colloid Interface Sci. 294 (2006),p.362370.
[10] Flanigen, E.M., Robert, W.B., Stephen, T.W., Wiley-VCH Verlag Gmbh & Co.KGaA (2010),p.1-26.
[11] Hiyoshi, N., Applied Catalyst A: General 419-420 (2012),p.164-169.
[12] Julbe, A., Fairusseng, D., Jalibert, J.C., Mirodatos, C., Guizard, C., Catalyst Today 56 (1-3) (2000),p.199-209.
[13] Lee, S., Tran, T., Park, Y., Kim, S., Kim, M., 2006. Study on the kinetics of iron oxide leaching by oxalic acid. Int.
J. Miner. Process. 80,p.144152.
[14] Lee, S., Tran, T., Jung, B., Kim, S., Kim, M., 2007. Dissolution of iron oxide using oxalic acid. Hydrometallurgy
87,p.9199.
[15] Murray, H.H., Keller, W.D., 1993. Kaolins, kaolins, and kaolins. In: Murray, H.H., Bundy, W., Harvey, C. (Eds.),
Kaolin Genesis and Utilization. The Clay Minerals Society, Boulder, CO, pp. 124.
[16] Ogura, M., Morozumi, K., Elangovan, S.P., Okubo, T., Applied Catalysis B: Environmental 77 (2008), p.294299.
[17] Rayalu, S. S., Udhoji, J. S., Meshram, S. U., naidu, R. R., Devotta, S., Current Science 89 (12) (2005).
[18] Rios, C.A., Williams, C.D., Fullen, M.A., Applied Clay Science 42 (2009), p.446-454.
[19] Szostak, R., Van Nostrand Reinhold, New York (1989).
[20] Veglio, F., Passariello, B., Toro, L., Marabini, A.M., 1996. Development of a bleaching process for a kaolin of
industrial interest by oxalic, ascorbic and sulphuric acids; preliminary study using statistical methods of
experimental design. Ind. Eng. Chem. Res. 35, p.16801687.
[21] Wahyuni, tri., synthesis of sodalite using kaolin directly . [Thesis] (in Indonesia), ITS, Surabaya, 2015, p.63.
[22] Yao, J., dan Wang, H., NSTI-Nanotec (2006).
[23] Zhao, H., Deng, Y., Harsh, J.B., Flury, M., Boyle, J.S., Clays Clay Minerals 52 (2004), p.113.

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CODE: IM
Synthesis and Characterization of Sodalite from Natural Kaolin Bangka Belitung: The Effect of Alkalinity
Meyga Evi Ferama Sari1), Suprapto1), Didik Prasetyoko1)
1
Department of Chemistry, Faculty of Mathematics and Science, Institut Teknologi Sepuluh Nopember, Surabaya
60111, Indonesia.
Abstract: Direct synthesis of sodalite from natural kaolin was successfully synthesized in this study. Sodalite was
synthesized by hydrothermal methods with the molar ratio composition of the corresponding synthesis sodalite xNa2O :
2SiO2 : Al2O3 : 128H2O. The variation (x) of the molar ratio of alkalinity was 7, 8, 9, and 10. The method of sodalite
synthesis was done by mixing of demineralized water and NaOH with vigorous stirring, added 3 g kaolin and sodium
aluminosilikat, continued by stirring for 6 hours at room temperature. Finally, the mixture was crystallized at 100 C for
24 hours. The solid resulted was separated by filtration, washed with demineralized water and dried for 24 hours at
temperature 100 C. The products were characterisized by X-ray diffraction. Based on XRD analysis showed that
synthesis of sodalite with molar ratio of alkalinity 9 has the highest crytalinity with 298.10 nm in particle size.
Keywords: sodalite; alkalinity; direct synthesis; natural kaolin
Corresponding author: Meyga Evi Ferama Sari, E-mail: meyga.efs@gmail.com, Tel. +62-82142494447
1. Introduction
Zeolite are porous material with a three-dimensional framework structure of crystalline aluminosilicate that forms
uniformly sized pores and commonly referred as molecular sieves. The empirical formula for zeolite is
M2/nO.Al2O3.ySiO2.wH2O, where y is 2-200, n is the cation valence, w represents the water contained in the
intracrystalline channel of zeolite [1]. The frameworks are composed of [SiO4]4- and [AlO4]5- tetrahedra, which cornershare to form different open structure. The tetrahedral are linked together to form cages connected by pore opening of
defined size; depending on the structure type, the pore size range from approximately 0.3-1 nm [2]. Zeolite have high
thermal, mechanical and chemical stability, therefore they have widely been used as catalysts, adsorbents, and
ionexchangers [3].
Sodalite is kind of zeolite and its framework structure consists of a six-membered ring aperture with a pore size of
2.8 . Because of the [4]. Sodalite is crystalline microporous tectosilicate with the general composition of
Na8[AlSiO4]6(X)2, where X is a monovalent guest anion [5]. Because of the small pore size and high ion exchange
capacity, sodalite has attracted considerable attentions for their potential applications such as optical material [6], waste
management [7], hydrogen storage [8], hydrogen separation [9], and catalyst support [10].
Some natural mineral materials have been used to synthesize sodalite. For instance, nano-sized sodalite crystals have
been obtained by solid-solid transformation of Al2O3 pillared clay in the alkaline solution [11, 12]. Interstratified illitesmectite [13], perlite [14], and coal fly ash [15, 16] have been converted to micro-sized sodalite crystals or spheres
through alkaline hydrothermal treatment. Natural kaolin Bangka Belitung Indonesia can be used to synthesis sodalite
because consist of high kaolinite.
Kaolinite is the main component of kaolin. The material is formed mainly by the decomposition of feldspar, granite,
and aluminum silicate, or generally by weathering process. Kaolinite structure [Si2Al2O5(OH)4] consist of a tertrahedral
silica sheet alternating with an octahedral alumina sheet [17]. The usage of kaolinite as the source of alumina and silica
in the zeolite synthesis has been reported previously [18].
There are two different methods to activation kaolinite: conventional hydrothermal synthesis and alkaline
calcinations followed hydrothermal reaction. Conventional hydrothermal two major chemical process involved in the
reaction between kaolinite and alkaline solution : dissolution of kaolinite, releasing Si and Al, followed by formation of
zeolitic material [19]. The dissolution of kaolinite is favoured at high NaOH concentrations, which revealed by the
occurance of sodalite and cancrinite [19]. Kaolinite is usually converted to a more reactive phase (metakaolinite) by
heating above the dehydroxylation temperature between 450 and 600 C. The product most commonly obtained was
zeolite LTA [19].
In this research, sodalite had been synthesized from natural kaolin without calcinations step via hydrothermal
synthesis method. The effects of alkali concentration on the final crystalline product were studied.
2. Research method
2.1 Materials
Natural kaolin from Bangka Belitung was used as aluminum and silica source.

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2.2 Experimental
Sodalite was sintesized using same procedure with in this experiment. The molar composition to synthesized
sodalite was xNa2O : 2SiO2 : Al2O3 : 128H2O. Sodium hydroxide was used as alkaline source and x notation was the
variation of molar ratio of alkalinity (7, 8, 9, and 10). Sodium hydroxide and demineralized water were mixed into
polypropilen bottle and stirred until sodium aluminat soluble, 3 g kaolin was added and stirred vigorously, sodium
aluminate was added and stirred for 6 hours at room temperature. After that, the mixture was crystallized at 100 C for
24 hours hydrothermal reaction at 100 C. The product was filtered, washed with demineralized water until pH under 9
and dried for 24 hours at temperature 100 C.
2.3 Characterization
All samples were characterization by powder X-ray diffraction (XRD). X-ray data were collected on a X-ray
Diffraction PANalitical XPert diffraction with CuK radiation ( = 1,54060 ), voltage 40 kV, 30 mA and 2 = 5-50.
3. Results and discussion
XRD analysis is used to identify the crystalline phase, crystal structure and crystallinity of the sample. The
diffractograms of the synthesized products are shown as Figure 1. The main peaks of sodalite at 2 angle are 14.16,
24.65, 31.99, 35.13 and 43.39. Based on the diffractograms, all of the products have the main peaks of sodalite, so it
indicates that all of them are sodalite.

Intensity

S10

S9

S8

S7
2

Fig. 1. XRD patern of the synthesized products with molar ratio of NaOH: 7 (S7), 8 (S8), 9 (S9), and 10 (S10).
The investigation of the crystallinity of sodalite samples were based on XRD measurement. Crystallinity has been
estimated by taking the total of the relative intensities of characteristic peaks sample divided to sum total of the relative
intensities of characteristic peaks standard [20]. Crystallinity of the sodalite samples were calculated using equation (1).
The partcles size of the sodalite samples (dXRD) were calculated by the Scherers equation (2) using the line broadening
of the 211 diffraction peak [21]. The 211 peak was choosen because it has the highest relative intensity than the other

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characteristic peaks of sodalite. So, it can be considered to represent the particle size of the sample. B value of each
sodalite was calculated from the 211 peak diffraction using Gaussian Fit in Origin soffware.

Crystallinity (%) =

x 100

(1)

dXRD =

(2)

is wave length of X-ray used (0.154060 nm), B is full width at half maximum 211 difraction peak after substaction
of line broadening due to the apparatus, is Bragg angle.
Table 1 shows the crytallinity and particles size of sodalite samples. The crystallinity of sodalite samples increases
with increasing molar ratio of NaOH at first, and reaches a maximum at 9. Higher alkalinity promotes the autolysis of
zeolite (sodalite) produced imperfectly, thus decreases the relative crystallinity of zeolite [22]. Increasing OH
concentration could reduce the polymerization of silicate species, but could speed up the gelation and polymerization of
the aluminate and silicate anions in the solution [23]. The higher crystallinity causes the larger particle size. That is
way, sodalite sample with the highest crystallinity (S9), has the largest particles than the others.
Table 1. Crytallinity (%) and particle size of sodalite standard and samples
Peaks (2)

Sample

Total

Crystallinity
(%)

Particle Size
(nm)

14.16

24.65

31.99

35.13

43.39

S-standard

1323.14

1968.75

751.2

740.23

445.49

5228.81

100

S7

683.92

966.47

380.87

392.77

277.79

2701.82

51.67

209.28

S8

816.29

897.81

382.35

400.1

269.9

2766.45

52.91

274.35

S9

1053.71

1232.92

471.2

446.1

304.63

3508.56

67.10

298.10

S10

712.91

1037.72

449.86

461.31

340.47

3002.27

57.42

293.48

4. Conclussions
Alkalinity affect to synthesis of sodalite, but in this study, the affect is not significant. Based on XRD analysis
showed that synthesis of sodalite with molar ratio of alkalinity 9 has the highest crytallinity and the largest particle size
(298.10 nm). The suggestion for this work needs to be done in advance research with higher or extreme variation of the
molar ratio of alkalinity, so the affect of alkalinity can be shown signifcantly.
Acknowledgement
This work was supported by the author like to acknowledge the Ministry of Research and Higher Education,
Indonesia, under PUPT research grant No. 003246.18/IT2.11/PN.08/2015.
Refferences
[1] E.M. Flanigen, W.B. Robert, T.W. Stephen, Zeolite in Industrial Separation and Catalys, In: Kulprathipanja, S.
(Ed.)., Introduction. Wiley-VCH Verlag Gmbh & Co.KGaA, p.1-26
[2] R. Szcostak, Molecular Sieves: Principles of Synthesis and Identification, Van Nostrand Reinhold Catalysis
Series, Van Nostrand Reinhold, New York,1989.
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CODE : IM
Leaching of Alumina from Red Mud of Bintan to Synthesis Mesoporous Alumina
Eka Putra Ramdhani1), Futri Wulandari1), Dian Permana1), Hartati2), Ratna Ediati1), Suprapto1), Didik Prasetyoko1)
1

Department of Chemistry, Faculty of Science, Institut Tekonologi Sepuluh Nopember, Surabaya 60111, Indonesia
Department of Chemistry, Faculty of Science and Technology, Airlangga University Surabaya 60111, Indonesia

Abstract: Alumina was leached from red mud by hidrometalurgy methode. Residu of each step was characterized by
X-ray diffraction (XRD), X-ray flourence (XRF), scanning electron microscopy -energy dispersive x-ray analysis
(EDX). Alumina from red mud was produced after neutralization process and was characterized by XRD and SEMEDX. Alumina was leached from red mud for 52.80% by weight. In this study, sol-gel method was used to synthesize
mesoporous alumina with a variation of the solid-solid ratio of CTAB/GM-Al. Mesoporous alumina was characterized
by XRD, SEM-EDX, transmission electron microscopy (TEM), and N2 adsorption-desorption. Mesoporous alumina has
an amorphous structure with aggregate appearance like wormhole. Increased concentration of CTAB/GM-Al decreased
the surface area and pore volume of alumina. The highest surface area and pore volume were obtained in solid-solid
ratio CTAB/GM-Al of 1.57 (AMC-1) i.e. 241 m2/g and 0,107 cm3/g, respectively.
Keywords : Mesoporous alumina; red mud; hidrometalurgy; sol gel
Corresponding author : Eka Putra Ramdhani, E-mail: denni_yata@yahoo.com, Tel. +628117017020
1. Introduction
Red mud is a reddish brown colored solid waste product produced in huge amounts from Aluminum industries. The
production of 1 ton of alumina generates between 1 and 1.5 tons of red mud [1]. Globally, there are about 4 billion tons
based upon its current rate production [2]. For solid waste, red mud will be found in the form of wet or dry mud which
is collected in a pond. The red mud produced from these industries is generally stockpiled in open yard, which leads
serious problem in soil, air and water because its highly caustic in nature [3]. Many strategies have been investigated for
improved management of red mud though no cost-effective methods have been implemented.
The characteristic of red mud is essentially to know before working on red mud for any use. Red mud comprises
Fe2O3 (48-54%), Al2O3 (17-20%), SiO2 (4-6%), TiO2 (3-4%), Na2O (3-5%) and CaO (1-2%) depending on the country
of origin [4]. The recovery of a significant quantity of valuable components from the red mud is difficult, as they are
locked up in complex mineral phases which are very fine grained and quite alkaline. Recovery of alumina from red mud
can be done through several methods such as the addition of MgO + Na2CO3 through sintering process [5], mild hydrochemical processes [6], the addition of acid (HCl, H2SO4, and HNO3) [7], hydrothermal processes [1], and the process
of reduction sintering [8]. The researches included recovery of important elements such as Fe, Al, Na and rare earth
elements like Sc, Y, La, Ti and V [9]. As known that red mud contains high value of aluminum more than 15%
depending on source of origin. Therefore, red mud can be source of aluminum to manufacture mesoporous alumina.
Mesoporous Al2O3 has excellent properties such as highly uniform channels, large surface area and narrow pore size
distribution. It has been widely used as adsorbents, catalysts supports, ceramics, heat insulating materials, and
reinforcements for composite materials [10]. Because of such excellent properties, many attempts have been made to
prepare mesoporous alumina by using different methods, such as evaporation- induced self-assembly (EISA) [11], hard
or soft template self- assembly [12] etc. Some expensive aluminum alcoxide or inorganic salts as aluminum sources
were used in the mentioned methods. However, among these synthesis routes, the processes were either complicated or
uneconomical, which limits large-scale application in industry.
In our experiment system, were move the impurity elements completely by making AlCl3 solution convert to
NaAlO2 solution. Furthermore, to the best of our knowledge, mesoporous Al2O3 was succeed synthesized from kaolin
using CTAB as template [13], but no reports are available about synthesis of mesoporous alumina from red mud using
CTAB as template at room temperature to date. Here in we present an accessible route for the synthesis of mesoporous
alumina from Red Mud We used leachate of Red Mud as Al resource, CTAB as template, synthesized mesoporous
alumina at room temperature.
2. Research method
2.1 Materials
The raw material powders of Red Mud were obtained from Bintan Island of Indonesia, its chemical composition was
(mass%): SiO2, 20.21; Al2O3, 28,87; Fe2O3, 44.66; TiO2, 3.03; CaO, 0.28; K2O, 0.37; P2O5, 0.51; V2O5, 0.07; Cr2O3,
0.101; NiO 0.62; ZrO2, 1.3 and ignition loss, 20.59. cetyltrimethylammonium bromide (CTAB), sodium hydroxide
(analytical grade), chloride acid (analytical grade), De-ionized water.

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2.2 Procedure
100 gr Red Mud was watered and stirred at low speed to remove some Fe2O3 contain by of gravitational principle.
50 gr solids from top layer was collected and treated in 6N HCl solution (solid/liquid ratio 1:5, g/ml) at 90 C for 2 h
with stirring. The obtained suspension was filtered and the filtrate was collected as Al source for synthesis of
mesoporous alumina. NaOH solution (5N) was dropped into filtrate from previous procedure with vigorous stirring
until AlCl3 tranformed into NaAlO2 completely. Some impurity elements (Fe3+, Mg2+, etc.) formed precipitates that
could be removed by filtering, and then NaAlO2 solution was obtained. Subsequently, HCl solution (6N) was added to
the NaAlO2 solution with magnetic stirring until the pH was 7. The precipitate was collected and washed with deionized
water. 1 g CTAB was pre-dissolved in 50 ml of deionized water at 60 C. The moist solid obtained was mixed with
CTAB solution with vigorous stirring for 1h. After that, the suspension was aged for 72 h at room temperature. The
final white products were recovered by filtration, washed with deionized water, and dried at 120 C. Then the assynthesized samples were calcined at 550 C for 6 h.
2.3 Characterization
Powder X-ray diffraction pattern was collected on Phillips Expert with CuK radiation ( = 1.54056 ), voltage 40
kV, 30 mA and 2 = 5-50. The surface area (calculated by BET method), pore size distribution (calculated by BJH
method) and pore volume were obtained at -196 C using a Quantachrome Instrument. Solids were characterization by
Scanning electron microscope (SEM) images operated at an acceleration voltage of 20.00 kV and work distance of 9
mm. Compositional analysis were performed using energy-dispersive X-ray analyzer attached to the microscope (SEMEDX) for Al, Fe, Si, Na, O, Br. Transmission electron microscopy (TEM) images were obtained on a JEOL JEM 1400
(UGM Yogyakarta - Indonesia).

Intensity (cps)

3. Results and discussion


3.1. Measurenment of composition of Bintan red mud
Measurenment of compound composition of Bintan red mud used XRF and the results are presented in Table 1.
Based on XRF result, the major compound composition are Fe2O3 (44.659%); Al2O3 (28.870%); SiO2 (20.209%) and
TiO2 (3.026). Several publication provide detailed information on characterization of red muds like [14] who reported
composition of red mud from Tayan, West Kalimantan.

f
ee
d
c
b
a
a
2 ()

Fig. 1. X-ray patterns of (a) quartz, (b) anatase, (c) boehmite, (d) gibbsite, (e) hemattite and (f) red mud.
Several researches have been studied about characterization of phase and element analysis in red mud, but data
analysis for red mud composition which obtaining is not uniform. It is caused by the different composition of red mud
each other places [15]. Fig. 1 shows that red mud comprises mineral in phase hematite (Fe2O3), gibbsite (Al(OH)3),
boehmite (-AlO(OH)), anatase (TiO2) dan quartz (SiO2). This result similar to [16] where diffraction peak of hematite
at 2 : 26, 40, 47, 58 and 64; gibbsite at 2 : 20 and 24; boehmite at = 18, 33, 45 and 58; anatase at 2 :
28 and 55; quartz at 2 = 21, 26 and 50.
3.2. Leaching of Red mud
3.2.1. Desilication Process
Desilication process using hydrocloric acid was aimed to soluble of Al2O3 in red mud solid. According to [17]
reaction in this process are below :

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Al2O3.2SiO2.2H2O (s) + 3HCl (l) 2AlCl3 (l) + 2SiO2 (s) + 5H2O (aq)
Fe2O3 (s) + 6HCl (l) 2FeCl3 (l) + 3H2O(aq)
2TiO2 (s) + 8HCl 2TiCl4 (l) + 4H2O(aq)
Fig. 2 shows that residue (RSD-1) has quartz phase at 2 : 20 and 26. In addition, Table 1 shows that contain of
SiO2 in residue is 38.85 %wt. Several other elements in red mud are Fe, Al, Ti, Zr and P.

Oxide
Residue (%wt)

Al2O3
27.90

Table 1. XRF data of Residue (RSD-1)


Fe2O3
SiO2
TiO2
20.56
38.85
8.36

K2O
1.45

ZrO2
2.89

450
400

Intensitas

350
300
250
200
150
100
50
0
0

10

20

30

40

50

Fig. 2. XRD pattern of Residue (RSD-1).


3.2.2. Separation of Fe2O3 and Other Impurities from Red mud
Filtrate was obtained from previous process then add NaOH 5N solution, simultaniously. In this process, AlCl3 was
converted into NaAlO2. According to [17], reaction in this process are below :
AlCl3 (l) + FeCl3 (l) + 6NaOH (l) Al(OH)3 (l) + 6NaCl (l) + Fe(OH)3 (s)
1200

Intensitas

1000

800

600

400

200

0
0

10

20

30

40

50

Fig. 3. XRD pattern of Residue (RSD-2).


Residue was obtained then denoted as RSD-2. It was characterized by XRD and XRF to know about its phase and
composition. XRD pattern of RSD-2 (Fig. 3) shows the peaks at 2 : 18, 20, 32, 40 and 45 which indicated that
RSD-2 has halite phase (NaCl) at 2 : 32 and 45. In other hand, the peak of Fe(OH)3 is not obtained which means
Fe(OH)3 in amorf [18]. XRF result indicated that other impurities are not obtained in RSD-2. The high concentration of
Cl in RSD-2 show high concentration of NaCl from residue.

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Oxide
Residue (%wt)

Table 2. XRF data of Residue (RSD-2)


Fe2O3
SiO2
TiO2
K 2O
81.80
-

Al2O3
-

ZrO2
-

Cl
18.20

3.2.3. Formation of Salt Alumina


The next stage is the process of neutralizing of Al(OH)3 which obtained from previous process and then added HCl
6N simultaniously to obtain NaAlO2. The precipitate formed from this process is a white alumina salt. According to
[16], a reaction that occurs in this process as follows:
Al(OH)3 (l) + 2NaOH (l) + HCl (l) NaAlO2 (s) + NaCl (l) + 3H2O (aq)
Alumina salt (GM-Al) was washed with distilled water and separated by Buchner funnel. GM
GM-Al obtained were then
characterized by XRD to determine the phase and the SEM-EDX to know the morphology and composition were
contained in the GM-Al. Based on the characterization by XRD (Fig. 4) shows that GM-Al is an amorphous solid. This
is demonstrated by acts of the characteristic peaks in the XRD pattern of GM-Al.
450
400

Intensitas

350
300
250
200
150
100
50
0

10

20

30

40

50

Fig. 4. XRD pattern of GM-Al.


Fig. 5 shows morphology of GM-Al
Al by SEM where GM-Al has an irregular shape and there are no pores on the
surface of solids.

Fig. 5. Morphology of GM-Al.


Fig. 6 displays the GM-Al spectra which showed the characteristic peaks elements contained in the GM-Al. These
spectra indicate that the content of the elements contained in the GM-Al is oxygen, aluminum
aluminum, sodium, and chlorine.
Based on Table 4, it can be seen that the element oxygen and aluminum in GM-Al amounted to 64.94 %wt and 26.40
%wt.

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Fig. 6. EDX spectra of GM-Al


Table 4. EDX data of GM-Al.
Elements

Al

Cl

Na

Weight (%)

64.94

26.40

6.62

2.04

Atom (%)

76.40

18.42

3.52

1.67

3.3. Synthesis of Mesoporous Alumina


3.3.1. XRD Analysis
The XRD diagram of red mud is shown as Fig. 7(a). It can be known that the main mineral phases of red mud are
Dicalcium Silicate (Ca2SiO4), Calcite (CaCO3), Perovskite Oxide (CaTiO3), Magnetite (Fe3O4) and Hematite (Fe2O3),
etc. Fig. 7(b) shows XRD patterns of Al2O3 precursor and calcined samples obtained at 550 C. No diffraction peaks
were detected in XRD patterns in samples with various CTAB concentrations. It indicated that mesoporous was
obtained in samples with various CTAB concentrations. The absence of diffraction lines characteristic to an ordered
oxide phase was in accord with a mesostructure with amorphous framework walls.

Fig. 7. XRD pattern of (a) red mud and (b) as-synthesized and calcined samples.
GM-Al used in wet conditions to synthesis mesoporous alumina, this is due to the dry conditions GM-Al and CTAB
are not mixed perfectly. There was characteristic peak of CTAB at 2 : 21 for sample of mesoporous alumina using dry
GM-Al (Fig. 8). It indicated that CTAB was still presence by calcination process.

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a
2
Fig. 8. XRD patterns of synthesized materials using (a) wet dan (b) dry GM-Al.
3.3.2. BET and Pore Sizes Analysis
Adsorption parameters such as the BET specific surface area, total pore volume and pore size, calculated from
nitrogen adsorption data, where summarized in Table 5. The surface areas for all samples were decreased with the
increase of CTAB/GM-Al from 1.57 to 7.85. When the CTAB/GM-Al ratio was increased to 7,85, surface area were
decreased from 241 to 216 m2/g. However when the CTAB/GM-Al ratio was increased to 7.85, pore volume of
synthesized materials were decreased to 0.048 cm3/g and mesopore volume decreased from 61.452 to 6.114 m2/g. On
the basis of the experimental fact that no significant change in the average pore size was observed in the CTAB/GM-Al
ratio range from 1.572 to 7.85. Under assumption that the size of CTAB micelles is fixed, the d-spacing should be
reduced with increasing the CTAB/GM-Al ratio because of the increase in the number density of micelles [19].
There were mesopore distribution for all samples could be observed in Fig. 9. The N2 adsorption-desorption
isotherms for all samples are typical type IV isotherms, no significant difference in hysteresis loop observed, which
supported that the prepared alumina has similar and monodisperse pore structure. At the relative pressure (P/P0) range
from 0.4 to 0.6, the nitrogen-adsorption was saturated and this saturation pressure was not influenced by the
CTAB/GM-Al ratio, which means that the prepared alumina particles have mesopores and no significant change in the
average pore size occur as the CTAB/GM-Al ratio changes (Fig. 10). Moreover, due to the present of CTAB in the
reaction media during the gel formation, CTAB micelles have incorporated within the gel and thereby facilitate the
process of template formation.

Samples
AMC-1
AMC-3
AMC-5

Table 5. Porous properties of mesoporous alumina


CTAB/Al
dBJH (nm)
SBET (m2/g)
Smeso (m2/g)
Ratio
1,57
3.820
241
61.452
4,71
3.822
223
37.645
7,85
3.817
216
24,717

Fig. 9. N2 Adsorption-Desorption
Isoterms of Samples

Vp (cm3/g)
0.107
0.056
0.048

Fig. 10. Pore Size Distribution of Samples


Obtained by BJH Method

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3.3.3. TEM Analysis


Fig. 11 presented TEM micrographs of obtained mesoporous alumina sample of AMC-3
AMC 3 with CTAB/
CTAB/GM-Al ratio of
4.71 and it was aggregated by nanometer particles. Therefore, the pores of AMC-3
AMC 3 were typical worm
worm-hole framework
structures without apparent order in the pore arrangement [20],
[ ], in good agreement with the absence of peak in the XRD
patterns (Fig.7b).

Fig. 11. TEM image of AMC-3.

3.3.4. SEM-EDX Analysis


SEM images and energy-dispersive
ve X-ray
X ray analysis for mesoporous alumina samples were shown in Fig. 11.
According to the images, the morphologies of the mesoporous alumina changed slightly along with increasing
CTAB/GM-Al ratio.

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Fig. 12. SEM images of mesoporous alumina samples : a) AMC-1, b) AMC-3 and c) AMC-5
Results obtained by XRD were confirmed with those of SEM. This technique was used to determine the morphology
and the particle size. Fig. 12 compares the SEM-EDX images of the AMC-1, AMC-3, and AMC-5 samples. Images of
all sample consist of amorphous aggregates of alumina. However, increasing the CTAB/GM-Al ratio from 1.57 to 7.85
not resulted a crystalline alumina, and there were wide range particle size in samples. Its boundary between the particles
could be clearly observed by SEM. EDX spectrum results show that the samples composed of elements that are used as
precursors, namely Fe, Si, Al, O, and Br. This indicates that there are no other elements that are formed during the
synthesis process. In addition, low composition of Fe and Si in as-synthesized material confirmed that those material
were succeed removed by extraction methods. There were few Br in samples indicated that not all CTAB were removed
during calcination at 550 C.
5. Conclusions
In conclusion, red mud can be used as a potential source of raw material in the manufacture of alumina mesoporous
material that is based on the results of XRF that red mud contains 28.87% by weight alumina. Synthesis of mesoporous
alumina from red mud has been successfully carried out by sol-gel method at room temperature. Alumina has an
amorphous structure and shape of the particles form irregular clumps with a wormhole-like appearance (wormhole).
The increase in the weight ratio of CTAB / GM-Al decrease the surface area and pore volume of mesoporous alumina
but there are no significant changes to the pore size distribution of alumina. The surface area and pore volume of the
largest obtained in the weight ratio of CTAB/GM-Al 1.57 (AMC-1) are 241 m2/g and 0.107 cm3/g.
Acknowledgements
The authors would like to acknowledge the Ministry of Research and Higher Education, Indonesia, under PUPT
research grant No. 003246.18/IT2.11/PN.08/2015.
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at room temperature, Materials Letters, (2013), No. 91, p.136-138.
[14] Aziz, M, Karakterisasi Mineral Ampas Serta Evaluasinya Untuk Pembuatan Material Geopolimer Bangunan,
Journal of Waste Management Technology, (2012), 15.
[15] H. Nath, P. Sahoo, and A. Sahoo, Characterization of Red Mud Treated Under High Temperature Fluidization,
Powder Technology, (2015), No. 269, p.233-239.
[16] W. Liang, S.J. Couperthwaite, G. Kaur, C. Yan, D.W. Johnstone, and G.J. Millar, Effect of Strong Acids on Red
Mud Structural and Fluoride AdsorptionProperties, J. Colloid and Interface Science, (2014), No. 423, p.158165.
[17] Vogel, Quantitative inorganic analysis, Revisied by G. Svehla, Prentice Hall, 1996, p.7.
[18] S.K. Kwon, K. Kimijama, K. Kanie, A. Muramatsu, S. Suzuki, E. Matsubara, and Y. Waseda, Effect of Silicate
Ions on Conversion of Ferric Hydroxideto -FeOOH and -Fe2O3, Materials Transactions, (2005), 46.2, p.155158.
[19] J.H. Kim, K.Y. Jung, K.Y. Park, and S.B. Cho, Characterization of mesoporous alumina particles prepared by
spray pyrolysis of Al(NO3)2.9H2O precursor: Effect of CTAB and urea, J. Micro and Meso Mat, (2010), No. 128,
p.85-90.
[20] S.A. Bagshaw, and T.J. Pinnavaia, Mesoporous Alumina Molecular Sieves, Angew Chem Int, (1996), No. 35,
p.1102 1105.

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CODE: IM

Analysis of Microstructure and Phase Change of -TiAl Alloy as High Temperature Resistance Material
Dyka Rahayu Meyla Sari1), Hariyati Purwaningsih2), Rochman Rochiem2), Diah Susanti2)
1

Department of Materials Science and Engineering, National Taiwan University of Science and Technology

Department of Materials and Metallurgical Engineering, Faculty of Technology Industry, Sepuluh Nopember Institut
of Technology (ITS) Jl. Arief Rahman Hakim, Surabaya 60111
Abstract: Intermetallic -TiAl alloys have been attracted much attention in recent time due the striking properties of
being good in thermal stability, high oxidation resistance, low density and excellent strength in high temperature. This
alloy is a strong candidate for high temperature applications. However, the used of the intermetallic TiAl alloy is
limited as the oxidation rate is high. One of the applications of TiAl alloy is for turbine blade. The application under
thermal cyclic associated with high temperature oxidation and most common fatalities are cracking and scalling. In this
study, the -TiAl alloy with composition of Ti-64wt%Al has been successfully synthesized by mechanical alloying
process using Modification Horizontal Ball Mill for 10 hours at 400 rpm followed by annealing at 900oC for 30 minute.
Thermal cyclic testing using an oxygen acetylene burner as simulation applications of -TiAl alloys at high
temperatures were conducted at temperature of 8000C for 1 hour and cooled to room temperature and let stand for 30
minutes per cycle. To identify the phase transformation of the compound and observe the morphology XRD and SEM
analyses were done respectively. EDAX analysis was used to understand the chemical composition. Thermal cyclic
tests up to cycle-5 formed Al2O3, TiO2 and Al2TiO5 phases.
Keywords: TiAl alloy, oxidation of TiAl, high temperature resistance alloy, thermal cyclic
Corresponding author: Hariyati Purwaningsih, E-mail: hariyati@mat-eng.its.ac.id
1. Introduction
Science and technology become important recently to enhance the life quality. The demands for effective and
efficient technology increase frequently year by year. The recent requirement for effective and efficient technology has
led to the materials technology to be innovative. Some of the industries such as aerospace and automobile applications
require high temperature resistance materials [1-5]. For example, turbine blade in aero-engine under high temperature
operation up to 1200oC with high stress require materials with high temperature strength, toughness, creep resistance,
thermal fatigue resistance, and hot corrosion [6].
Intermetallic TiAl materials are receiving attentions for potential high temperature applications [7, 8]. One of the
most attractive one is intermetallic TiAl alloys in recent time [7, 9, 10]. It shows comparative properties with nickel
based alloy while its density is much lower than nickel alloy [11-14]. The weight savings and excellent mechanical
properties at high temperature has become attractive structure for machine parts and enhancing the efficiencies of
engines. This alloy is a good candidate as substitute material for gas turbine in aero-engine [15]. However, insufficient
oxidation resistance in high temperature application upper 700oC is still a major debate [16, 17].
TiAl alloy with good thermal properties are synthesized by is melting method [18], the drawbacks associated with
complex process due to the high difference melting point of aluminum and titanium, and high temperature processing.
In order to tackle these problems, a mechanical alloying technique with low temperature and simple process was used in
this study [8, 19].
In this present work, intermetallic TiAl alloy has been successfully synthesized using mechanical alloying
technique followed by annealing process. In addition, X-ray diffraction (XRD) and scanning electron microscopy
(SEM) have been used to characterize the phase composition and morphology of the TiAl alloy, respectively. The
crystallinity of the TiAl alloy was acquired to understand the crystallinity of the powder. For thermal cyclic tests,
XRD and SEM have been used again to characterize the TiAl alloy after it was burned in oxy-acetylene burner for 5
cycles.
2. Experimental
Intermetallic TiAl alloy with composition of Ti64%wt-Al was used as a sample in this experiment. The substrate
was made by mechanical alloying process using Modification Horizontal Ball Mill. Thermal cyclic tests were acquired
using oxygen acetylene burner at 800oC.

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2.1 Synthesis
-TiAl alloy was prepared by mechanical method using Modification Horizontal Ball Mill as a milling process. To
produce TiAl alloy, the precursors of Al and Ti were 36wt% aluminum oxide
ox (Al2O3, 99%, Merck) and 64wt% titanium
oxide (TiO2, 99%, Merck), respectively. Ti and Al precursors were put into stainless steel vial (small chamber) under
argon atmosphere at Ball Powder Ratio (BPR) 10:1 [20]. Ethanol was used as a solvent during the milling process.
Mechanical alloying processes were performed at 400rpm for 10h. TiAl alloy particles then die pressed to form disk
using manual compaction machine at 3000psi. The disk was then annealed at 900oC for 30 minutes through argon
atmosphere using Carbolite Vacuum Furnace. The phase composition and surface morphologies of as received milling
and as-prepared
prepared TiAl alloy were examined using XRD and SEM.
2.2 Thermal Cyclic Test
Thermal cyclic tests of TiAl alloy were performed using oxy-acetylene
acetylene burner. The disk was heated at 800oC for 1h,
then cooled until it reached room temperature and let stand for 30 minutes for each cycle. The crystallography structures
were obtained using XRD (Pan Analytical-MPD
Analytical
System) with an operating voltage
age of 30 kV, operating current of
10mA, diffraction 2 angle of 20 - 80, and scan rate of 1 s-1 to identified the phase change as the result of thermal
cyclic. Micrograph of the surface morphologies were acquired using SEM/EDX FEI InspectS
3. Results and Discussion
3.1. Results
3.1.1. Synthesize
XRD analysis of mixed precursors and as-milled
as
of Ti64%wt-Al
Al powder is shown in Fig. 11. The figure shows that
the patterns of precursors and as-milled
milled sample have no significant difference. For mixed precursors
precursors, the XRD pattern
has diffraction peaks at 38.47, 44.73, and 65.13o related to the aluminum (JCPDF#04-0787)
0787) and some peaks at 35.09,
40.17, 53.00, 62.94, 70.66, 76.21, and 77.36 corresponding to the titanium (JCPDF#44-1294).
(JCPDF#44 1294). The XRD results suggest
that mechanical
chanical alloying process at 400 rpm for 10 h cannot achieve TiAl
TiAl phase. Since crystal size related with the
crystallinity, single peak analysis were acquired for further investigation. Single peak analysis shows that mechanical
alloying process has influenced
uenced to the crystal size of titanium and aluminum powders.
Table 1 shows the calculation for crystal size of Titanium and Aluminum in Ti64%wt-Al
Al powder after milled using
Modification Horizontal Ball Mill at 400 rpm for 10 h. FWHM number of titanium powder
powder before and after milled is
from 0.116 to 0.132, respectively. However, for aluminum powder show the opposite trend with titanium, FWHM
number of aluminum powder is decreased. Crystal size of titanium before mechanical milling was 994.936 then
decreased to 811.768 for the milled powder. For aluminum, the crystal size show increased from 559.8 to 601.62
after the process. The increasing crystal size of aluminum in this system is due to the agglomeration process dduring
mechanical alloying [6]. Under
er long milling time (10 hours) at 400 rpm, the crystal size of titanium is decreased
however the -TiAl phase cannot be approached.

Fig. 1. XRD pattern of Ti64%wt-Al


Ti64%wt
and Ti before and after mechanical alloying 400 rpm for 10h
In order to get the -TiAl phase, a disk from as-milled
as milled powder was annealed using vacuum furnace. The annealed
sample then named as-prepared
prepared specimen. The annealing process was performed at 900oC for 30 minutes. Fig. 2 shows
the XRD spectra of as-milled
milled powder and as-prepared
as prepared TiAl bulk alloy. From Figure 2 shows that after annealed at
900oC for 30 minutes, peaks at 21.83, 31.84,
31.84, 38.99, 44.20, 45.58, 65.55, 79.70, and 83.38o associated with -TiAl
(JCPDF#05-0678)
0678) were observed. This result suggests that annealing process successful to form -TiAl. However, two
tiny peaks at 41.20 and 77.99o related with 2-Ti3Al phase (JCPDF#14-0451)
0451) appeared as a second phase of TiAl alloy.

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Previous study named Ti3Al phase as supersaturated Ti(Al) solid solution [8]. This phase appear as the result of
inhomogeneous sample then leads to the presence of second phase. During the annealing process, aluminum compound
was melted then react with titanium surface. Finally,
Finally, the melted aluminum is diffused to the titanium surfaces to form TiAl. In summary, mechanical alloying process by using Modification Horizontal Ball Mill followed by annealing at
900oC for 30 minutes successful to form -TiAl and Ti3Al as second phase.
Table 1. Correlation of FWHM value and crystal size before and after
after mechanical milling for 10h at 400 rpm
Sample
Phase
Cos
FWHM
D
()
As-received
Ti
0,939
0,116
994,9
Ti64%wt-Al powder
Al
0,944
0,174
559,8
As-milled Ti64%wt-Al powder at 400
rpm for 10h

Ti
Al

0.939
0,944

0,132
0,164

811,8
601,6

Fig. 2. XRD pattern


attern of as-milled
as
and as-annealed Ti64%wt-Al
Al powder
powder.

(a)

(b)

Fig. 3. SEM image of Ti-Al


Al powder (a) before and (b) after mechanical milling for 10h at 400 rpm.
Surface morphologies of TiAl alloy were acquired using Secondary
Secondary Electron Microscope. Fig. 3a shows the
morphology of Ti-Al
Al powder before mechanical milling. From Figure 3a, two kinds of shapes were captured. The first
shape is a thin shape with smooth surfaces (Type I) and another one shown as a faced shape with rough surfaces (Type
II). The average
rage particle size sizes of Type I and II are 3119m
3119
and 134m,
m, respectively. The image suggested that
the thin smooth surface is related with aluminum and the faced shapes associated with titanium. As
As-milled powder of
TiAl powder is shown in Fig. 3b. As-milled
milled powder dominated by the small irregular shapes which covering the bigger
particles. The average particle size for Type I and Type II after milling process are 75m and 1225m, respectively.
It is seems that titanium particles covered by irregular small flakes of aluminum. The variation of particle shapes
indicated that milled powder is inhomogeneous.
3.1.2. Thermal Cyclic Test
Thermal cyclic test of the -TiAl alloy synthesized by mechanical alloying process followed by annealing were
conducted at 800oC to understand the thermal properties of TiAl alloy as a candidate of high temperature materials.

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Fig. 4. XRD pattern of disk surface (a) before thermal cyclic and (b) after cycle
cycle-1.
Fig. 4 shows the XRD pattern of TiAl alloy before and after thermal
thermal cyclic. The phase analysis using XRD
confirm that the thermal cyclic test results with the presence of some new phases. The detail of peaks appear at the first
cycle are listed. Peaks at 27.43, 36.08, 41.23, 54.31, and 56.62o according to the rutil TiO2 (JCPDF#86
(JCPDF#86-0147), Al2TiO5
phase at 26.54, 33.73, 42.08, 47.82, 50.81, and 62.66 associate with (JCPDF#81-0030),
0030), and ccorondum Al2O3 at 25.83,
35.57, 38.11, 43.8053.12, 58.21 and 68.88o related with (JCPDF#85-1337) were observed as shown in Fig. 5. -TiAl
also
o still can be seen as the base alloy, however the peak is less sharp than before thermal cyclic test.
The XRD pattern of TiAl alloy sample after cycle-5
cycle confirm that the presence of -TiAl
TiAl is less that cycle-3 due to
the reaction of specimen with oxygen to form oxides. Peaks of TiO2, Al2O3, and Al2TiO5 are still observed and the
intensity of Al2TiO5 peak is higher than in the cycle-3.
cycle Some new phase like SiO2 and Mg(SiO3) also observed at the
sample surface. These two phases are appeared as the results of
of the reactivity of silica stone which used as a based
(place to put the sample) during the thermal cyclic test.

(a)

(b)

Porous

Fig. 5. Visual image of specimen (a) before thermal cyclic test (b) after cycle
cycle-3.
Visual analysis of as-prepared bulk specimen show that the sample surface contain of black dot which associ
associate with
pores as seen in Fig. 5a. Moreover, the sample surface after thermal cyclic test up to cycle 3 is shown in Fig. 5b. The
image shows that the shape and color change due to the burning process during the test. The sample surface changes to
the irregular rough surface and covering by white layer in the outer surface.
Detailed surface morphology analyses were performed using SEM. Fig. 6 shows the SEM image of as
as-prepared bulk
sample before thermal cyclic test. The bulk was polished using abrasive papers. As-prepared
As prepared bulk sample shows bright
and dark areas. The bright area related with the dense of TiAl alloy while the dark area associate with the pores.
Fig. 7 shows the SEM images
ages of TiAl bulk sample after thermal cyclic test for cyclic-1
cyclic 1 and cycle
cycle-5. There are two
areas observed, some areas with smooth surface (marked 1) and some block spots (marked 2) are detected at the sample
surface. For deeper investigation of these two areas, EDAX analyses have been acquired.
Table 3 shows the EDAX results of bulk sample after thermal cyclic test for cycle 1. There are two spots as
mentioned before, spot 1 and spot 2. From the table it can be seen that these two areas does not represent the chemical
composition of Al2O3, TiO2 or Al2TiO5.5 These results suggests that the oxides at the sample surface are mixed oxides
which consistent with the XRD results. Figure 7b shows the magnification of bulk surface after cycle 5. The image
shows that the oxides are growing up with the increasing of the cycles test and covering the specimen surface. Some
pores also detected at the formed oxides which indicates that the oxides are discontinuous.

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Porous

Fig. 6. Sample surface before thermal cyclic test.

(a)

(b)
1
2

Fig. 7. SEM image of specimen surface after thermal cyclic test for (a) cycle-1 and (b) cycle-5
Table 3. EDAX at sample surface after cycle
Tab
Ti
Al
O
Area
Oxides
(at%)
(at%)
(at%)
1

01,83

34,79

63,37

Mixed oxides

05,53

27,16

67,30

Mixed oxides

3.2. Discussion
Mechanical alloying technique followed by annealing process has been successful to synthesize -TiAl alloy with
Ti3Al as second phase (Figure 2). This second phase appears as a result of short annealing process (30 minute). During
the shortt annealing time suggests that Ti and Al have limited time for diffuse process then generate the second phase.
Another possible explanation is due to the inhomogeneous sample from mechanical milling process. Previous study
named Ti3Al phase as supersaturated
ed Ti(Al) solid solution [21].
The particle size of Ti-Al
Al powder before and after mechanical
mechanical milling show different size. For aluminum shows that
after mechanical milling the average particle size and standard deviation decreased significantly from 3119
3119m to
75m.
m. This result shows that mechanical milling process effective to reduce particle
particle size of aluminum. However the
titanium shows only slightly change of average particle size and standard deviation from 134
134m to 1225m after
mechanical milling. The big standard deviation value of milled titanium powder suggests that some of the partic
particles are
very big and some of them are smaller. This result might be due to the agglomeration of titanium and aluminum. During
the mechanical alloying process most of the aluminum break up and attach in the titanium surface the agglomerate to
form big particle.
Thermal cyclic test at 800oC up to cycle 5 shows the existence of some peaks main oxides such as Al2O3, TiO2 or
Al2TiO5 (Figure 4). Previous works on the thermal test of -TiAl/Ti3Al also confirm the presence of corondum Al2O3
and rutil TiO2 as oxide products [22].. The Al2O3 phase has a characteristic
eristic as passive layer which protect the base
material when the Al2O3 layer is formed continuously and fully covering the samples [23,, 24]. However, the -TiAl
peak after thermal cyclic is less sharp than before thermal cyclic test due to the oxides layer in the surface of base TiAl
alloy.

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From the XRD pattern shows that thermal cyclic test over one hour result to the formation of another phase related
with aluminum and titanium, the phase is Al2TiO5. Previous study mentioned that the product from the reaction of TiO2
and Al2O3 in high temperature is Al2TiO5 [25]. Although, more detail of thermodynamic analysis is needed to
understand the characteristic and formation mechanism of the Al2TiO5 phase.
SEM analysis shows that the bulk sample has some pores. The presence of the pores suggested the unperfected of
dye pressed process and short holding time for annealing process causing limited time for aluminum to melt and fill all
of the pores. Porous at the sample seems effect to the oxidation process since the color of surface sample changes a lot
before and after thermal cyclic test from silver to white (figure 5). During thermal test, aluminum and titanium reacts
with oxygen to form oxides. At the first stage, oxygen gasses absorbed at the metal surface then dissociated to form
atom component before arrange a chemical bond with metal surface, at this case TiAl.
Visual analysis shows that after thermal cyclic test the bulk sample shape was degraded become irregular shape and
covering by the white layer. Detail surface morphology analysis of TiAl alloy after thermal cyclic using SEM image
shows that some of the oxides appear in the sample surface with porous structure. The EDAX analysis confirms that the
oxides are the mixed oxides. This result consistent with the XRD result which is shows some oxides in the sample
surface. The formations of mixed oxides at the surfaces of TiAl alloys have been observed frequently in previous
studies [7, 22, 26]. However the combinations of mixed oxides (aluminum oxides and rutile) have been reported to
reduce the protective properties at high temperature [5, 27]. Thus porous and mixed oxides in the sample surface
suggest that the oxides are discontinuous and might not protect the base metal perfectly. In the future work some of the
coatings as protective layers are important to be applied. In summary, thermal cyclic test shows that TiAl alloy prepared
by mechanical alloying followed by annealing process ended with the presence of some oxides.
4. Conclusions
-TiAl alloy has been successfully synthesized by using mechanical milling technique at 400 rpm for 10h followed
by annealing process at 900oC for 30 minutes. However Ti3Al phase appears as a second phase. Thermal cyclic test
resulted with the presence mixed oxides of Al2O3 and TiO2 on the sample surface. Another phase of Al2TiO5 also
appears as the effect of thermal cyclic test at high temperature. The oxides structures are porous which suggest the
discontinuous oxide layer.
Acknowledgements
The authors acknowledge the financial support from the Hibah Penelitian Laboratorium Dana PNBP 2012.
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The 7th International Conference on Sensors ASIASENSE 2015
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CODE: IM
Effect of Spray Distance on TGO growth in YSZ/YSZ-Al2O3 Thermal Barrier Coatings
Widyastuti1), Rokaya1), Chaizin N1), Ratna TA1), Parindra K1), Rindang Fajarin1)
1)

Material Physics Laboratory, Department of Materials and Metallurgical Engineering, Sepuluh Nopember Institute of
Technology, Surabaya 60111, Indonesia
Abstract: Thermal barrier coatings (TBC) comprising of YSZ-Al2O3/YSZ as top coat (TC) and MCrAlY alloy as bond
coat (BC) have been used in rocket nozzle wall. The TBC layer was deposited by flame spray (FS) technology. Coating
products of FS depend on the spray distance, number of pass, feed rate and powder composition. Al2O3/YSZ composite
layer was influence on growth of Thermally Grown Oxide (TGO) layer after thermal test. Morphologies and phase
compositions of the TGO layer was examined by scanning electron microscopy (SEM) equipped with energy dispersive
spectrometer (EDS). Based on TGA, Oxidation for TGO formation is start from 850oC. High melt coated particle
percentage, optimum density, low porosity and higher adhesion strength (23.54Mpa) of TBC was reached in spray
distance 150 mm with 1 pass.
Keywords: Thermal Barrier Coating; Al2O3/YSZ; Thermally Grown Oxide (TGO); spray distance; pass
Corresponding author: Widyastuti, E-mail: wiwid@mat-eng.its.ac.id, Tel. +6281310605693
1. Introduction
Nozzle is extensively used for rocket propulsion and work in high temperature around 800o-2000oC [1]. Thermal
Barrier Coating (TBC) have been applied as protective coating on hot section of nozzle from the extreme temperatures
in the gas. The parts in a nozzle RX 550 are made up of steel (S45C or AISI 4340) which was coated by inserted
graphite as TBC. The total weight of rocket increased with inserted graphite and become next problem. One alternative
material to substitute inserted graphite is mullite (Al2O3.SiO2). Moreover mullite formed uncompletely and secondary
phase as Kyanite(Al2O3.SiO2) and Andalusite (Al2SiO5) formed instead [2]. Widyastuti, 2014 used nickel-based
superalloys which coated by YSZ-Al2O3/YSZ as alternative material. Thermal barrier coatings (TBC) consist of three
layers; the prevalent outer layer is yttria-stabilized zirconia (YSZ), acting as the thermal barrier coating, an oxidation
resistant bond coat, consisting of a metallic alloy like NiCrAlY and a nickel-based superalloy substrate. The
compositions of Al2O3 for YSZ-Al2O3/YZS are 5, 15 and 30wt% with variations of feed rate are 8, 14 and 20 g/min.
The Al2O3 compositions influence the thermal stability of TBC systems against the non-isothermal oxidation. it has
been obtained that sample with 15% Al2O3/YSZ and feedrate 14 g/min tend to be more stable than another and has
highest adhesion strength (10 MPa). [3]. However, when these TBC are exposed to elevated temperatures, their thermal
resistance becomes decrease because of spallation. In this study, a combination among spray distance, pass and
feedrate of flame spray are observed to optimize thermal resistance of YSZ-Al2O3/YZS. Rajasekaran, 2011 reported
that low spray distance will decrease porosity because total percentage of melted powder are increase [4]. Numbers of
pass influence the crack propagation and formation of porosity. Jungi Yao report that TBC which high number of pass
has higher oxidation resistance and spallation [5]
2. Methodology
The YSZ powder (Metco 204NS Sulzer Metco, USA) c.a 71.88 m was used as top coat with Al2O3 powder Al2O3 c.a 37.7 m (Merck, Germany). Bondcoat is NiCrAlY powder (Amdry 962 Sulzer Metco, USA) with
composition Ni = bal., Cr = 21-23%, Al = 9-11%, Y = 0.8-1.2% and median size at 87.98 m was applied to prepare
on nickel-based superalloy (Hastelloy X Haynes Int, USA). Before flame spray process, the 30wt% Al2O3 and YSZ
powder were mixed together in ball mill. Before the Hastelloy X substrate was deposited by the powder, some grit
blasting was done to the substrate. The coating process was conducted using flame spray (Flame Powder Spray Gun
5PII) with spray parameters as shown in Table 1. Where the feed rate of the top coat varied by 14, 17 and 20 g / min.
The process began by depositing bond coat layer on a substrate and then Al2O3/YSZ and outer layer of 8YSZ.
The microstructure of the TBC was examined by Scanning Electron Microscopy (SEM EDX FEI S50, Japan)
equipped with energy dispersive spectrometer. The X-Ray Diffractomer (XRD XPert PANanalytical, UK) was used to
investigate the phases of TBC systems and the adhesion strength of TBC was calculated by Pull Off Test using Portable
Adhesive Tester Type II. The non-isothermal oxidation tests of the samples were prepared using a Thermogravimetry
Equipment (TGA/DSC1 Mettler Toledo, Switzerland). The heating rate was 10oC/min at 1100oC, and then the heated
samples were slowly cooled until the room temperature, under the chamber of TGA equipment condition. Another
thermal tests were conducted using thermal torch of oxyacetylene flame for 25 second, the damage of ceramics layer on
top coat was investigated to determine the resistance of TBC againts the direct penetration of oxyacetylene torch.

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Layer

Composition

Top coat

YSZ

Interlayer

YSZ 30wt%
Al2O3

Bond coat

NiCrAlY

Table 1. Spray parameter


Number
Spray distance
of pass
(mm)

Feed Rate
(g/min)

Thickness
(m)

200

20

230

1, 2, 3
1, 2, 3
1, 2, 3
1

100
150
200
200

20
20
20
20

120

3. Result and Discussion


TBC coating systems must have a combination of properties to be effective such high resistance to spallation and
phase stability. These properties are critical properties for nozzle application. Spallation resistance depends on micro
structural of TBC. Fig 1. Describe crossectional three layer of TBC

Topcoat (YSZ)

Al2O3 /YSZ

Bondcoat
Substrate

Fig 1. Microstructure of crossectional TBC YSZ-Al2O3/YSZ with spray distance(a) 100 mm, 1 pass, (b) 100 mm,2
pass, (c) 100 mm,3 pass, (d) 150 mm, 1 pass, (e) 150 mm,2 pass,, (f) 150 mm, 3 pass, (g) 200 mm, 1 pass,
(h) 200 mm, 2 pass, (i) 200 mm, 3 pass,
Fig. 1 describes that the white line is TGO of YSZ/Al2O3 area between the bondcoat and topcoat. Layer with rough
and uneven area is topcoat. Topcoat was composed with several conditions of melted, semi melted and unmelted spalts,
which were characteristics of flame spraying deposition [6]. Spray distance significantly influence the condition of
melted powder. If spray distance is far, the melted powder didnt have enough time to cover area of substrate without
solidification. Fig 1.shown that crossectional morphology of TBC for spray distance 100mm (fig 1(a), (b), (c)) is denser
than morphology of TBC with spray distance 200 (fig 1(f), (g), (h)). Porosity size which was found in (fig 1(f), (g), (h))
are bigger than others. These porosities initiate spallation of TBC and decrease mechanical properties of TBC. Bonding
between bodcoat (NiCrAlY) and substrate Hastelloy (nickel based) is successful because there were minimum
porosities in this area. TGO formation observed by EDS shown in Fig 2.

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(a)

(b)
Fig 2. SEM-EDS results TBC YSZ-30Wt%Al2O3/YSZ with spray distance 100mm/1 pass (a) before thermal oxidation,
(b) after thermal oxidation.
Fig. 2 shows the results of SEM 5000X magnification and EDX on the area between top coat and bond coat for 30%
Al2O3/YSZ with spray distance 100mm/1pass before and after the thermal oxidation test. Fig 3. SEM/EDAX for 30%
Al2O3/YSZ with spray distance 200mm/3pass. If compared to the as-flame sprayed structure (before and after oxidation
test), the width of the TGO became larger and followed by the crack. After measured, the width of TGO(fig 2) turned
from 2.24 m into 6.52 m and the crack width 1.74 m. For Fig, the width of TGO growth from 35.72 m into 8.18
m and crack width 2.37 m. In a study conducted by Jackson et al report that the critical limit of the width of TGO
before TBC failure was 3-10 m[7]. Fig 3 shown TGO growth for spray distance 200mm/3 pass.
Table 2 describes TGO growth in YSZ-30%Al2O3/YSZ according SEM-EDS Analysis. Sample with porosity on the
surface would be easier for oxygen to enter and oxidized the TGO region. Spray distance influence the TGO growth and
crack formation. Higher spray distance equal with increasing of crack formation and decrease spallation resistance.
However, is dependent on the mechanical properties of all three layers of TBC (Bondcoat, TGO and Topcoat
interaction). TGO growth until critical thickness has advantages to barrier oxygen penetration. Before oxidation test, the
thickness of TGO is under critical limit and growth after oxidation test. Overgrowth of TGO initiate crack between
bondcoat and topcoat.

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(a)
Fig 3. SEM-EDS results TBC YSZ-30Wt%Al2O3/YSZ with spray distance 200mm/3pass (a) before thermal
oxidation , (b) after thermal oxidation

(b)
Fig 3. SEM-EDS results TBC YSZ-30Wt%Al2O3/YSZ with spray distance 200mm/3pass (a) before thermal
oxidation , (b) after thermal oxidation.

Table 2.TGO and crack of YSZ-30%Al2O3/YSZ before and after the thermal test
Sample
Before oxidation test
After oxidation test
TGO (m) Crack m) TGO (m)
Crack m)
100 mm/1 pass
2.24
6.52
1.74
100 mm/2 pass
2.24
6.61
1.53
100 mm/3 pass
2.26
6.75
1.79
150 mm/1 pass
2.28
4.57
1.02
150 mm/2 pass
2.30
4.93
1.10
150 mm/3 pass
2.35
5.67
1.09
200 mm/1 pass
4.05
7.47
2.36
200 mm/2 pass
4.21
7.63
2.49
200 mm/3 pass
5.72
8.18
2.73

The results of non-isothermal TGA tests shown in Fig. 4. YSZ-30Wt%Al2O3/YSZ was heated from 0oC until
1000oC. TGA result shown a significant change in slope occurs in the temperature range 850-1000oC, which indicated

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that the oxides formation began experiencing, other words TGO slowly began to growth. Based on fig 4. YSZ30Wt%Al2O3/YSZ with spray
pray distance 150mm/1 pass more stable than other sample coating followed by 100mm/1pass.
This result was supported by Fig 1(d). Microstructure of YSZ-30Wt%Al
YSZ
2O3/YSZ 150mm/1 pass was denser than
others.

Fig. 4. TGA result YSZ-30Wt%Al2O3/YSZ

Fig. 4. TGA result YSZ-30Wt%Al2O3/YSZ.


Complexities of microstructure increase with increasing number of pass. Oxide inclusion formed at interlayer of
TBC. This oxide decrease adhesive strength of TBC and initiate spallation [6]. The bondcoat layer oof TBC must have a
high compliance to minimize the coefficient of thermal expansion (CTE) mismatch stress between the top TBC layer
and substrate. Crack was contributed by development of large stresses in the TGO layer. Adhesive test was conduct to
observe interlayer adhesives strength of TBC. The average of adhesive of YSZ-30Wt%Al2O3/YSZ is 18,63 Mpa. This
value is normal range between adhesive strength of metal (30
30 Mpa) and ceramics (15Mpa) [6]. The optimum adhesives
strength of TBC (23.54
23.54 Mpa) and low porosity
por
(11,83%) was reached in spray distance 150 mm/1 pass
pass. Near spray
distance produce high energy impact and increase particle deformation at interlayer bonding. Short dwelling time made
powder melt homogeneously and decrease porosity on coating surface[4].
surface[ Spesimen TBC with spray distance 100mm
has lower adhesive strength (19.45Mpa) than TBC with spray distance 150mm (23.54MPa). This phenomenon has
indicate that sample which closer to flame not only received more heat but also maximized coefficient of tthermal
expansion (CTE) mismatch stress between the top TBC layer and substrate. Okazaki report that thermal stress in one
significant factor that contribute to decrease adhesive strength of specimens [8]. The Increasing of thermal resistance of
TBC is expected
cted to reduce the growth TGO layer under TGO thickness limit and adjust the spray distance and number
of pass.
4. Conclusions
The YSZ-30Wt%Al2O3/YSZ -coatings
coatings have been deposited on overlay NiCrAlY bond
bond-coated Hastelloy-X
substrates using flame spray. The optimum
ptimum adhesives strength of TBC (23.54
23.54 Mpa) and low porosity (11,83%) was
reached in spray distance 150 mm/1 pass.
pass Near spray distance produce high energy impact and increase particle
deformation at interlayer bonding. Complexities of microstructure increase
increase with increasing number of pass The
Increasing of thermal resistance of TBC is expected to reduce the growth TGO layer under TGO thickness limit and
adjust the spray distance.
References
[1] George Sutton,(2001). Rocket Propulsion Elements 7th ed. Chichester:
Chichester: John Wiley & Sons
Sons.
[2] Widyastuti, Mariani, L., Ridwan, S., & Putrawan, M. A. (2014). Al2O3SiO2 Coating by Flame Spray for Thermal
Barrier Coating Application. Applied Mechanics and Materials,
Materials 493, 691-696.
[3] Widyastuti, Parindra K , Lilis Mariani , Hosta A and Sulistijono, (2015) Analysis of YSZ
YSZ-Al2O3/YSZ Flame
Sprayed Thermal Barrier Coating to Thermal Resistance, Advanced Materials Research Vol 1112 pp 338
338-344
[4] Rajasekaran, B., G. Mauer, dan R. Vaben (2011). Enhanced Characteristics of HVOF
HVOF-sprayed MCrAlY Bond
Coats for TBC Applications ASM International JTTEE5 20:12091216.
1216. DOI: 10.1007/s11666
10.1007/s11666-011-9668-3
[5] Yunqi Yao (2013). Influence of Al2O3/YSZ micro-laminated
laminated coatings on high temperature oxidation and
spallation resistance of MCrAlY alloys
[6] ____. (2004). ASM Handbook of Thermal Spray. ASM Internasional.

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[7] Jackson, R.D., M.P. Taylor, H.E. Evans, X.H. Li. (2011). Oxidation Study of An EBPVD MCrAlY Thermal
Barrier Coating System. Oxidation of Metals 76.
[8] Okazaki, Masakazu., Satoshi Yamagishi, Yasuhiro Yamazaki, Kazuhiro Ogawa, Hiroyuki Waki, Masayuki Arai.
(2013). Adhesion Strength of Ceramic Top Coat in Thermal Barrier Coatings Subjected to Thermal Cycles:
Effects of Thermal Cycle Testing Method and Environment. International Journal of Fatigue 53 3339.

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CODE: IM
Characteristics of Indonesian Bamboo: Gigantochloa atroviolacea and Bambusa vulgaris schard
Hosta Ardhyananta, Fakhreza Abdul, Moh. Farid, Sigit Tri Wicaksono, Alvian Toto Wibisono
Department of Materials and Metallurgical Engineering, Institut Tekonologi Sepuluh Nopember, Surabaya 60111,
Indonesia
Abstract: Characteristics of Indonesian bamboo species (Gigantochloa atroviolacea and Bambusa vulgaris schard)
were studied. Bamboos physiological and fiber characteristics were examined. The physiological characteristics was
observed by visual. The bamboo fiber characteristics was examined from the extraced fiber from bamboo culm. The
fiber was extracted by mechanical and chemical treatment (alkaline solution) for delignification. The results showed
that each bamboo species has its own specific properties. The Gigantochloa atroviolacea showed higher culm thickness
than Bambusa vulgaris schard. Gigantochloa atroviolacea had higher fiber density than Bambusa vulgaris schard. The
fiber tensile strength of Gigantochloa atroviolacea was higher than Bambusa vulgaris schard. The fiber of
Gigantochloa atroviolacea showed higher Youngs Modulus and Elongation at break than Bambusa vulgaris schard.
The bamboo properties correspond to the hidroksil group. The Gigantochloa atroviolacea showed strong hydrogen
bonding. Thermogravimetric analysis (TGA) showed that Gigantochloa atroviolacea had better thermal stability than
Bambusa vulgaris schard.
Keywords: Bamboo; Gigantochloa atroviolacea; Bambusa vulgaris schard; Tensile Properties; Thermal Properties.
Corresponding author: Hosta Ardhyananta, E-mail: hostaa@mat-eng.its.ac.id, Tel. +62-31-5997026, Fax. +62-315997026
1. Introduction
Bamboo is an interesting plant. It has many advantages over other woody plant. Bamboo can grow in a short time. It
reaches maturity within four to five years. Bamboo can grow to very high in height and very large in diameter. Bamboo
easily grows in tropical and subtropical zone (warm and humid condition). It is easily to find in natural forests. Bamboo
has been used for construction material (scaffolding, house, roof, bridge), handicrafts, furniture, musical instruments,
fiber, paper making, board making, carbon, food and fuel [1-3].
Bamboo has an interesting characteristics. Bamboo tree grows very fast. It starts at bamboos shoot bud . Bamboos
shoot bud appears at rhizome (underground). This bud grows upright and radial which is followed by emerging branch
and leaf. Bamboo shows high biomass fuel, high wear resistance, high strength, light weight, renewable and
inexpensive material. Bamboos culm is consisted of lignin matrix and cellulose fiber and considered as polymer
composite. Natural fiber is an important component for paper making and construction material. Bamboo shows highly
potential ecomaterial [4-7].
Indonesia has a wide variety of Bamboo species. However, the study of its bamboo species is very limited. This
study investigated two Indonesian Bamboo species (Gigantochloa atroviolacea and Bambusa vulgaris schard). Its
physiological characteristics, tensile properties and thermal properties were examined. These species widely grow in
Indonesia..
2. Experimental
2.1. Material
Bamboo tree (Gigantochloa atroviolacea and Bambusa vulgaris schard) which is choosed in this study was around
four years old, around 12 m height and growth in the same area. The bamboo culm specimen was prepared by
mechanical processes (sawing and grinding). Sodium hydroxide and ethanol was obtained from LIPI (Indonesia) and
used as-received. Toluene was obtained from Smart (Indonesia) and used as-received.
Bamboo culm specimen which is without nodes was cut (sawing) from the bamboo tree. Then, the culm was cut into
smaller pieces (around 80 mm). Bamboo fiber was extracted from the bamboo culm. It was prepared by mechanical and
chemical processes. Mechanical process has been done by pressing the bamboo culm several times until its fiber
separated. Chemical process has been done by alkaline solution. Bamboo culm was immersed in the alkaline solution (1
M NaOH and 70 % ethanol) at 50 Cfor 12 h, filtrated and washed by distilled water several times. Then, the bamboo
fiber dried in an oven at 60 Cfor 12 h

2.2. Characterization

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Tensile test on the bamboo was done at strain rate of 5 mm/sec. Fourier Transform Infra Red (FTIR) spectra was
done in the range of 4000-500 cm-1 using Nicolet iS10. The morphology examination was done using Olympus optical
microscope and Scanning Electron
ctron Microscope (SEM) (FEI Inspect S50) at 20 kV. Thermogravimetric analysis (TGA)
was conducted at heating rate 10 C/min
C/min under nitrogen flow.
3. Results and discussion
3.1. Physiological Characteristic
Fig. 1 presents the appearance of bamboo tree (Gigantochloa
(
atroviolacea and Bambusa vulgaris schard
schard). The tree
consists of leaf, branch, partition, node, culm and rhizome. The tree shows small size branch. Gigantochloa
atroviolacea has a dark green colour. Bambusa vulgaris schard has a bright yellow colour. Fi
Fig. 2 presents the
appearance of bamboo culm cross-section.
section. The culm was a hollow cylinder. The Gigantochloa atroviolacea showed
higher outside diameter and culm thickness than Bambusa vulgaris schard (Table 1).

(a) Gigantochloa atroviolacea

(b) Bambusa vulgaris


aris schard

Fig. 1. Photograph of bamboo tree.

(a) Gigantochloa atroviolacea

(b) Bambusa vulgaris schard

Fig. 2. Photograph of bamboo culm cross-section.

Bamboo species
Gigantochloa atroviolacea
Bambusa vulgaris schard

Table 1. Bamboo culm characteristics


Inside Diameter (mm) Outside Diameter (mm)
27 2
44 1
21 2
35 2

Culm
ulm Thickness (mm)
8.5
7

Fig. 3 presents the optical image of bamboo culm cross-section.


cross section. The microstructure consists of matrix (bright
region) and fiber (dot and dark region)
region) [5]. This is showing that bamboo is a biocomposite material. Gigantochloa
atroviolacea shows higher fiber density compared to Bambusa vulgaris schard.. By calculating the dark region,
Gigantochloa atroviolacea has 50 % fiber. Meanwhile, Bambusa vulgaris schard has 46 % fiber. Fig. 4 presents
schematic structure of bamboo.

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(a) Gigantochloa atroviolacea

(b) Bambusa vulgaris schard

Fig. 3. Optical image of bamboo culm cross-section.

A-A
leaf

fiber
partition
branch

epidermis
(outer skin)

matrix

endodermis
(inner skin)

inside diameter
culm

outside diameter
node
ground
rhizome

Fig. 4. Schematic structure of bamboo.

3.2. Fiber Characteristic


Bamboos fiber showed high contribution to the strength. Therefore, the study of fiber characteristics is necessary to
be done. Fig. 5 presents the bamboo fiber after mechanical and chemical treatment. These treatment have been done to
remove matrix from fiber (delignification). The fiber shows long and continuous shape.

Fig. 5. Photograph of bamboo fiber.


Fig. 6 presents IR spectra of bamboo fiber after mechanical and chemical treatment. After mechanical treatment,
cellulose fiber structure was observed at 1018 cm-1 as C-O-C pyranose ring. Lignin matrix structure was observed at
1618 cm-1 as C=C aromatic ring. O-H bond was observed at broad peak 3258 cm-1 [8]. After chemical treatment, the
peak at 1618 cm-1 was reduced. This corresponds to the removal of lignin (delignification). Meanwhile, C-O-C bond
and O-H bond were remained. This corresponds to strong cellulose pyranose ring and hydrogen bonding.

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after chemical treatment
after mechanical treatment

(a) Gigantochloa atroviolacea

(b) Bambusa vulgaris schard


Fig. 6. IR spectra of bamboo fiber.

Table
able 2. presents the tensile properties of bamboo fiber. The fiber tensile strength of Gigantochloa atroviolacea was
higher than Bambusa vulgaris schard. The fiber of Gigantochloa atroviolacea showed higher Youngs Modulus and
Elongation at break than Bambusa
usa vulgaris schard. The properties correspond to the typical cellulose fiber and
hydrogen bonding.
Table 2. Tensile properties of bamboo fiber after chemical treatment
Bamboo species
Tensile Strength (MPa) Youngs Modulus (GPa)
Elongation (%)
Gigantochloa atroviolacea
65 5
12 2
0.5 0.1
Bambusa vulgaris schard
49 4
53
0.5 0.1
Fig. 7. presents SEM image of bamboo fiber after mechanical and chemical treatment. The morphology of the fiber
shows long and continuous shape. The fiber is in the form of bundles. Gigantochloa atroviolacea fiber have a diameter
of around 15 m. Bambusa vulgaris schard fiber have a diameter of around 18 m.
m. After mechanical treatment, the
fiber bundles show rough surface showing the presence of matrix. After chemical treatment, the fiber bundles show
smooth surface showing the removal of the matrix.
Table 3. presents the TGA analysis of bamboo fiber. Thermogravimetric analysis showed that Gigantochloa
atroviolacea had better thermal stability than Bambusa vulgaris schard.
schard. The bamboo fiber is thermally stable until 296
C for Gigantochloa atroviolacea and 292 C for Bambusa vulgaris schard.. This is due to typical fiber and its hydrogen
bonding.

After mechanical treatment

After chemical treatment


(a) Gigantochloa atroviolacea

After mechanical treatment

After chemical treatment


(b) Bambusa vulgaris schard

Fig. 7. SEM image of bamboo fiber.


Table 3. TGA analysis of bamboo fiber after chemical treatment

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Bamboo species
Gigantochloa atroviolacea
Bambusa vulgaris schard

T5 (C)
296
292

T10 (C)
311
302

Weight residue (%)


29
27

4. Conclusions
Two Indonesian bamboo species (Gigantochloa atroviolacea and Bambusa vulgaris schard) were studied.
Gigantochloa atroviolacea showed dark green appearance. Bambusa vulgaris schard showed bright yellow appearance.
The Gigantochloa atroviolacea showed higher culm outside diameter and thickness than Bambusa vulgaris schard.
Bamboos microstructure showed mantrix and fiber corresponding to biocomposite material. Gigantochloa atroviolacea
had higher fiber density than Bambusa vulgaris schard. Bamboo fiber has been extracted by mechanical and chemical
treatment using alkaline solution for matrix removing. Bamboo fiber showed strong pyranose ring and hydrogen
bonding. Each fiber has its own typical properties. The fiber was in the form of bundles. Gigantochloa atroviolacea
fiber has tensile strength, Youngs Modulus, elongation at break and thermal stability higher than Bambusa vulgaris
schard. The bamboo fiber was thermally stable until 292 C.
Acknowledgements
The authors are thankful to Institut Teknologi Sepuluh Nopember (ITS) Surabaya, Indonesia for the research fund.
References
[1] J.M.O. Scurlock, D.C. Dayton, and B. Hames, Bamboo: an overlooked biomass resource?, Biomass and
Bioenergy, 19(2000), p.229
[2] A.A. Ahmad, and B.H. Hameed, Effect of preparation conditions of activated carbon from bamboo waste for real
textile wastewater, Journal of Hazardous Materials, 173(2010), p.487
[3] H. Kinoshita, K. Kaizu, M. Fukuda, H. Tokunaga, K. Koga, and K. Ikeda, Development of green composite
consists of woodchips, bamboo fibers and biodegradable adhesive, Composite: Part B, 40(2009), p.607
[4] J. Tong, R.D. Arnell, and L.-Q. Ren, Dry sliding wear behavior of bamboo, Wear, 221(1998), p.37
[5] S. Amada, Y. Ichikawa, T. Munekata, Y. Nagase, and H. Shimizu, Fiber texture and mechanical graded structure
of bamboo, Composite: Part B, 28B(1997), p.13
[6] F. Nogata, and H. Takahashi, Intelligent functionally graded material: bamboo, Composite Engineering,
5(1995),No 7, p.743
[7] H. Ardhyananta, F. Abdul, Widyastuti, Sulistijono, A. Hassan, and D. Kurniawan, Tensile and thermal properties
of Bambusa arundinacea and Dendrocalamus asper culm fiber, Advanced Materials Research, 845(2014), p.237
[8] J.X. Sun, X.F. Sun, H. Zhao, and R.C. Sun, Isolation and characterization of cellulose from sugarcane bagasse,
Polymer Degradation and Stability, 84(2004), p. 331

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CODE: IM
Doping Effect of CaO on the Ferroelectric and Dielectric Properties in PbTiO3 Synthesized by Mechanical
Alloying Method
Rindang Fajarin1), Widyastuti1), Hariyati Purwaningsih1), Malik AB2), and Venorita Permanasari1)
1

Department of Materials and Metallurgical Engineering, Sepuluh Nopember Institute of Technology (ITS), Surabaya
60111 Indonesia
2
Department of Physics, Sepuluh Nopember Institute of Technology (ITS), Surabaya 60111 Indonesia
Abstract: PbTiO3 is one of the perovskite materials having advanced appications. In this research, PbTiO3 is
synthesized by mechanical alloying method with various doping concentrations of CaO at various sintering
temperatures. PbO and TiO2 powders are milled for 2 hours, and then sintered for 2 hours at 1000oC. The CaO
concentration of 0.2; 0.3; and 0.4 mol are added in the mechanical alloying process for 2 hours. The resulting powders
are formed into pellets and sintered for 3 hours at temperatures of 700 oC, 800 oC, and 900 oC. From the X-ray
Diffraction (XRD) patterns, it is found that PbTiO3 has been formed with tetragonal structure and peak shift is observed
indicating that the CaO has been doped successfully into the PbTiO3. Scanning Electron Microscopy (SEM) results
show that the grains are increased with the increase of sintering temperatures and decreased with the increase of CaO.
The dielectric properties measured by LCR meter have shown that the dielectric constant is decreased for 0.4 mol of
CaO doped in PbTiO3. The ferroelectric properties have shown that the polarization remanent is increased with the
increase of CaO and sintering temperatures. In addition, the coercive field is decreased with the increase of CaO and
sintering temperatures.
Keywords: CaO doping; dielectric; ferroelectric; mechanical alloying; perovskite
Corresponding author: Rindang Fajarin, E-mail: fajar@mat-eng.its.ac.id, Tel. +62-31-5997026, Fax. +62-31-5997026
1. Introduction
Perovskite is one of oxide materials that has important application in electronic, because of its ferroelectric,
piezoelectric, and magnetic properties. So far, BaTiO3, Pb(ZrTi)O3 (PZT) and PbTiO3 are the interesting ferroelectric
materials for nonvolatile memory devices (NVRAM), microsensor and microactuator. Ferroelectric thin films such as
PbTiO3, Pb(ZrxTi1-x)O3 (PZT), Ba1-xSrxTiO3 (BST), BaTiO3, Pb1-xSrxTiO3 (PST) and Pb1-xCaxTiO3 have simple structure
and high density for memory device applications and the micro waves are not disruptive. [1]
Among the perovskite materials, PbTiO3 is more applicable than Pb(ZrTi)O3 (PZT) or BaTiO3 because of high
temperature curie and low dielectric constant. However, PbTiO3 is easy to break because of low density. PbTiO3 can be
substituted by Ca2+ in order to increase the ferroelectric and dielectric properties. (Pb,Ca)TiO3 can be used for
ferroelectric memory device (NVRAM) and pyroelectric devices because of its high dielectric constant.
This research investigates the doping effect of CaO and the sintering temperature in PbTiO3 related to the
ferroelectric and dielectric properties synthesized by mechanical alloying method.
2. Experimental
Fig. 1 shows the flow chart of the present research about the doping effect of CaO and the sintering temperature
related to the ferroelectric and dielectric properties of PbTiO3 synthesized by mechanical alloying method.
3. Result and discussion
3.1. Characterization of PbTiO3
XRD results show that PbTiO3 has been formed 100%, it is proved from the three highest peaks 31.9015; 31.9788;
and 57.6024 which match with ICDD pattern numbers of 01-072-4723; 01-085-1749 and 01-076-9122. The phase of
PbTiO3 has tetragonal structure.
Fig. 2 shows the XRD pattern of PbTiO3 indicating that it has been formed 100% PbTiO3. This result is consistent
with the former research [2] in which PbTiO3 phase will be formed in the sintering temperature of 850oC for 60
minutes.
3.2. Doping Effect of CaO in PbTiO3
XRD results with various CaO doping concentrations of 0.2; 0.3; and 0.4 mol sintered at 700oC are shown in Fig. 3.
In Fig. 3, PbTiO3 with doping of 0.2 mol indicates that the peaks of the XRD result are match with ICDD pattern no.
01-071-4815 and 01-070-4258, and all the peaks are PbTiO3 with tetragonal structure, the three highest peaks are
31.480; 32.4164 and 39.2436.

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PbTiO3 with the doping of 0.3 mol shows that almost the peaks are PbTiO3, with the three highest peaks are match
in ICDD pattern no. 01-075-0438 and 01-072-4723 and the structure is tetragonal, but there is one peak that it shows
TiO2 at peak of 14.48 and relevant with ICDD pattern no. 01-076-1266. PbTiO3 with the doping of 0.4 mol CaO shows
that all of the peaks are PbTiO3 and match in ICDD pattern no. 01-070-4258 and 01-074-3459, the three highest peaks
are 31.5087; 32.4179 dan 22.7913 and all of them have tetragonal structure. In addition, the peak of TiO2 in CaO
doping 0.3 mol at sintering 700oC indicates that TiO2 is not bonded with PbO to make a new compound PbTiO3, this is
might be caused by less homogenous when milling process of PbO and TiO2.
Start
Literature Study
Raw Materials
TiO2 Powder
Merck

PbO Powder
Merck

Mechanical Alloying(Planetary Ball Mill)


PbTiO3
V = 300 rpm;t=2 h ;BPR=6:1
Pellet
D = 14mm;
t=3mm; P=300MPa
o

Sintering T = 1000 C for 2 h


PbTiO3 Powder
Adding dopant of CaO : 0.2; 0.3; 0.4 mol
Mechanical Alloying(Planetary Ball Mill)
CaO-doped PbTiO3
V = 300 rpm;t=2 h ;BPR=6:1
Pellet
D = 14mm;
t=1.7mm; P=200MPa
o

Sintering T = 700; 800; 900 C


for 3 h
XRD

SEM

Dielektric

Ferroelektric

Results and Discussion


Conclusions
Finish

Figure. 1. Flow Chart of the Research


Fig..
1. Flow Chart of the Research.

Fig. 2. XRD of the non-doped PbTiO3.

Relative Intensity (a.u)

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Fig.. 3. XRD patterns of CaO-doped PbTiO3 with


concentration of (a) 0 mol (b) 0.2 mol (c) 0.3 mol and
(d) 0.4 mol, sintered at 700oC.
Table 1 shows the XRD analysis of the FWHM, crystal size, and microstrain of the CaO
CaO-doped PbTiO3 sintered at
700oC. It is found that the FWHM becomes wider with the increase of CaO concentration indicating the the cchange of
lattice parameters. This may be the sign of defect due to the substitution by Ca, and thus it makes microstrain.
Tabel 1. XRD
D analysis result of 2 position, FWHM, crystal size
and microstrain of the non-doped
non
PbTiO3 and CaO-doped PbTiO3
with concentrations of 0.2;0.3;0.4 mol sintered at 7000C.
Material Doping
2
FWHM
D

CaO
Position
(nm)
(mol)
0
31.9015
0.1224
74.05
1.7x10-3
PbTiO3
0.2
31.4820
0.1171
78.05
1.6 x10-3
PbTiO3
0.3
31.5755
0.1428
61.78
2.1 x10-3
PbTiO3
0.4
31.5087
0.1840
46.65
2.7 x10-3
PbTiO3

The XRD results with the various doping concentrations of CaO 0.2; 0.3; and 0.4 mol sintered in 800oC are shown
in Figure 4. For the 0.2 mol doped-CaO,
CaO, the three highest peaks are in 31.4673, 32.3941, and 22.7520 in which match
with the ICDD pattern no. 01-070-4258.
4258. For the 0.3 mol doped-CaO,
doped CaO, the three highest peaks are 31.4663, 32.4493, and
39.2100 in which match with thee ICDD pattern no. 01-076-8809
01
and 01-070-0747.
0747. As for the 0.4 mol doped
doped-CaO, the
three highest peaks are 31.4960, 31.4117, and 32.3632 in which match in ICDD pattern no. 01
01-070-4258 and 01-0743462. According to XRD analysis, there is no second phase was found, all of them have PbTiO3 phase. These results are
in agreement with former research of Nagarbawadi [3] where PbTiO3 is synthesized by solid state reaction of PbCO3
and TiO2 with the various Ca concentrations of 5, 10, 15, and 25% sintered in 850oC forr 4 hours. The XRD analyses
show that the crystalline phase of the sampel is perovskite tetragonal.
According to XRD analysis, the resulting powders are formed 100% PbTiO3. This shows that the Ca
Ca-doping does
not change the crystalline structure of PbTiO3. This indicates the successful doping process, where Pb ion is substituted
by Ca ion in the PbTiO3 crystal.
Table 2 shows the XRD analysis of the FWHM, crystal size, and microstrain of the CaO
CaO-doped PbTiO3 sintered at
800oC. It is found that the FWHM becomes
becomes wider with the increase of CaO concentration indicating the the change of
lattice parameters. This might be the sign that PbTiO3 is doped by Ca, and thus it makes microstrain.

Relative Intensity (a.u)

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Fig. 4. XRD patterns of CaO-doped


CaO
PbTiO3 with
concentration of (a) 0 mol (b) 0.2 mol (c) 0.3 mol and (d)
0.4 mol, sintered at 800oC.

Table 2. XRD analysis result of 2 position, FWHM, crystal size and microstrain
of the non-doped
doped PbTiO3 and CaO-doped PbTiO3 with concentrations of 0.2;0.3;0.4
mol sintered at 8000C.
Material
Doping
Posisi 2
FWHM
D (nm)

CaO
(mol)
0
31.9015
0.1224
74.05
1.7x10--3
PbTiO3
0.2
31.4673
0.1004
94.96
1.3 x10--3
PbTiO3
0.3
31.4663
0.1004
94.96
1.3 x10--3
PbTiO3
0.4
31.4960
0.1015
93.61
1.36 x10-3
PbTiO3
Fig. 5 shows the CaO-doped
doped PbTiO
PbTi 3 with various mol 0.2, 0.3, and 0.4 mol sintered at 900oC. XRD analyses
indicate that all of the peaks are PbTiO3 with tetragonal structure; it is equal when sintered in 800oC or 700oC at 0.2 and
0.4 mol. In the CaO doping of 0.2 mol, the three highest peaks,
peaks, 31.5060, 32.4134, and 22.7798, match with the ICDD
pattern no. 01-070-4258.
4258. In the CaO doping of 0.3 mol, the three highest peaks, 31.4537, 32.3561, and 22.7178, match
with the ICDD pattern no. 01-074-3462,
3462, 01-072-4724,
01
and 01-070-4258. Whereas in thee CaO doping of 0.4 mol, the
three highest peaks, 32.4318, 32.0396, and 22.7492, match with the ICDD pattern no. 01-076
01 076-8809 and 01-072-4724.
According to XRD analysis, there is no second phase is found, 100% PbTiO3. It shows that the Ca
Ca-doping does not
change
ange the crystalline structure of PbTiO3 and it is considered that the doping process is success.
Table 3 shows the XRD analysis of the FWHM, crystal size, and microstrain of the CaO
CaO-doped PbTiO3 sintered at
900oC. It is found that FWHM becomes wider with the increase of CaO concentration indicating the change of the
lattice parameter in the crystal. This result is similar with the behavior of CaO-doped
CaO
PbTiO3 sintered at 800oC.
According to the XRD analyses, the CaO-doped
CaO
PbTiO3 has perovskite tetragonal structure.
tructure. Based on Tables 2 and
3, there are peak shifts of 2 between PbTiO3 with no doping and the Cao-doped PbTiO3. This indicates that there is a
substitution of Ca in the crystalline structure. The shift in the microstrain also indicates that there is defect in the CaOdoped PbTiO3. The substitution of Pb2+ by Ca2+ ions is occurred because the atomic radius of Ca and Pb atom is almost
the same (less than 15%), in which the Ca2+ is 0.099 nm and Pb2+ is 0.112 nm.

Relative Intensity (a.u)

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Fig. 5. XRD patterns of CaO-doped


CaO
PbTiO3 with
concentration of (a) 0 mol (b) 0.2 mol (c) 0.3 mol and
(d) 0.4 mol, sintered at 900oC.
Table 3. XRD analysis result of 2 position, FWHM, crystal size
and microstrain of the non-doped
non
PbTiO3 and CaO-doped PbTiO3
with concentrations of 0.2;0.3;0.4 mol sintered at 9000C.
Doping
Materia
Posisi
CaO
FWHM D (nm)

l
2
(mol)
0
31.9015 0.1224 74.05 1.7x10-3
PbTiO3
0.2
31.5060 0.1506 58.16 2.1 x10-3
PbTiO3
0.3
31.4537 0.1171 78.05 1.6 x10-3
PbTiO3
0.4
32.4318 0.1004 95.19 1.3x10-3
PbTiO3
3.3. SEM Analysis
The purpose of SEM is to investigate the particle morphology of the non-doped
non doped and CaO
CaO-doped PbTiO3 samples
using SEM FEI Inspect S50.

Fig. 6. Morphology of the CaO-doped


CaO
PbTiO3 sintered in
900oC with CaO concentrations of (a) 0 mol (b) 0.2 mol (c)
(c
0.3 mol and (d) 0.4 mol, in optimized 6000.
6000

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The SEM analysis is shown in the Figure 6. It shows the size of the PbTiO3 particle in the various CaO
concentrations of 0, 0.2, 0.3, and 0.4 mol sintered at 900oC. The partice size of PbTiO3 with 0.2 mol doped CaO
sintered at 900oC is around 4.311 m up to 6.264 m; in the 0.3 mol doped CaO, the particle size is around 3.044 m up
to 4.743 m; and as for the 0.4 mol doped CaO, it is around 2.903 m up to 5.683 m. The grain size decreases by the
amount of doped CaO in PbTiO3. These results are consistent with the former research [3]. Figure 6(b) shows that the
cube structure, which might be due to the effect of less compaction of the pellet sample. In this case, the air might be
trapped which make the given pressure is not optimal.
3.4. Dielectric Properties
The dielectric measurement is conducted using LCR metre Fluke and Philips the T&M Alliance PM 6303A. This
measurement was held at Physics Science Instrumental & Electronic Laboratory in ITS Surabaya. The frequency was
1 kHz. From this, we can get the dielectric constant and the conductivity of the sample.
3.4.1 Dielectric Constant
From the digital LCR meter, we can get capacitancy data. In order to get dielectric constanta, we use the following
equation (1) :
=

(1)

Dielectric Constant

where K is dielectric constant, C is capaitancy (F), A is sample area (m2), d is sample thickness (m) dan o is dielectric
constant permitivity at vacuum (8.85x10-12 Farad.m-1). Figure 7 shows the dielectric constant sintered at 800oC and
900oC in the doped CaO of 0.2 and 0.3 mol. The constanta dielectric is maximum in the doped CaO of 0.3 mol for the
sintering temperature at 800oC, that is 23.5. The dielectric constant increases with the increase of CaO concentration up
to the doping of 0.3 mol. This is relevant with the previous research [1] in which the dielctric constant increases with
the increase of Ca concentration in 1kHz frequency.

Doping of CaO (mol)

Fig. 7. Doping dependence of the dielectric constant


of the CaO-doped PbTiO3 sintered at various
temperatures.
As for the 0.4 mol doped CaO, the dielctric constant decreases. It is in agreement with the previous research [4],
which explains that there is a tendency of decreasing in the dielectric constant for the 0.4 mol doped CaO. This may be
due to the phase changing from tetragonal to pseudocubic in the 0.4 mol CaO-doped PbTiO3.
3.4.2. Conductivity Analysis
From the digital LCR meter, the data is Z (impedancy). In order to to get the conductivity, we use the equation (2)
and (3) :
=
=

(2)
1

(3)

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Conductivity (10-8 S/cm)

where is resistivity (ohm.cm), Z is impedancy (ohm), A is sample area (cm2), d is sample thickess (cm), and is
conductivity (S/cm).

Doping of CaO (mol)

Fig. 8. Doping dependence of the conductivity of the


CaO-doped PbTiO3 sintered at various temperatures.
Fig. 8 shows the doping dependence of conductivity in the CaO-doped PbTiO3. It is found that the lowest
conductivity is the PbTiO3 with CaO doping of 0.2 mol sintered at 800oC; that is 0.587x x10-6 ohm/m, and the highest
conductivity is the PbTiO3 with CaO doping of 0.3 mol sintered at 900oC; that is 1.35x10-6 ohm/m. The conductivity
tends to decrease in the PbTiO3 with CaO doping of 0.4 mol. It has similar behavior with the dielctric constant. The
conductivity range of this sample is in the order of 10-8 S/cm showing that the CaO-doped PbTiO3 is semiconductorlike. This result is relevant with the range of semiconductor material from 10-8 up to 103 S/cm [6].
3.5. Ferroelectric Proeperties
Ferroelectric properties were tested using hysteresis curve by the Sawyer-Tower circuit and oscilloscope. From the
oscilloscope, the data is volts/div in x-axis and y-axis. It is used to get the Vx and Vy from each sample, then Vx and Vy is
used to get the remanen polarization and coercive electricity area using the equation (4) and (5).
=
=

(4)
(5)

where Pr is remanent polarization (Coulomb/m2), Ec is coercive electricity area (V/m), Vy is voltage in y-axis (volt), Vx
is voltage in x-axis (volt), d is sample thickness (m), and o is permittivity in vacuum (8.85x10-12 F/m) [6].
Fig. 9 shows the doping dependence of the remanent polarization and the coercivity of the CaO-doped PbTiO3
sintered at 900oC. It is found that the remanent polarization (Pr) increases from 4.43x10-11 C/m2 in the doping of 0.2 mol
up to 5.73x10-11 C/m2 in the doping of 0.4 mol. The coercive electricity area (Ec) tends to decrease with the increase of
CaO and it is consistent with the previous research [5]. From these samples, Pr increases and the Ec decreses with the
increase of CaO and it is in agreement with the previous research [7], in which the ferroelectric properties will be better
if the Pr is high and the Ec is low.
4. CONCLUSIONS
It is concluded that CaO-doped PbTiO3 increases the dielectric properties. The dielectric constant of the non-doped
PbTiO3 is 20.1 and it reaches 23.5 in the doping of 0.3 mol CaO. The conductivity is also increased from 1.04x10-8
mho/cm up to 1.36x10-8 mho/cm. The doping of CaO in PbTiO3 also increases the ferroelectric properties in which it
reaches the maximum in the doping of 0.3 mol. The remanent polarization (Pr) of PbTiO3 with no doping is 3.54x10-11
C/m2 and the coercive electricity area (Ec) is 3.33x102 V/m. Due to the CaO doping, the values of Pr and Ec increase up
to 4.6910-11 C/m2 and 5.65102 V/m, respectively.

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Doping of CaO (mol)

Fig. 9. Doping dependence of the Remanent Polarization


(Pr) and the Coercive Electricity Area (Ec) of the CaOdoped PbTiO3 sintered at 900 oC.
Acknowledgements
The authors thanks to the Departement of Research, Technology, and Education of Indonesia for the financial
support, and to all Materials and Metallurgical Engineering Departement ITS.
References
[1] A. K. S. Chauhan , Vinay Gupta, and Sreenivas, Dielectric and Piezoelectric Properties of Sol-Gel Derived Ca
Doped PbTiO3, Material Science and Engineering B 130 (2006). 81-88.
[2] F. Nugroho, Pengaruh Waktu Milling dan Temperatur Sintering pada Pembentukan PbTiO3 dengan Metode
Mechanical Alloying, Tugas Akhir Jurusan Teknik Material dan Metalurgi FTI-ITS (2013).
[3] M. A, Nagarbawadi, Jangadi P. S. 2014. TheInfluence of Calcium Doping on Structral and Electrical Properties of
Ferroelectric Lead Titanite Ceramic IOSR Journal of Applied Physics. 2278-4861.Volume 6, Issue 3 Ver. II
(2014), PP 15-19.
[4] F.M Pontes, D.S.L Pontes, E.R.Leite, E.Longo, Influence of Ca Conentration on the Electric, Morphological, and
Structural Properties of (Pb,Ca)TiO3 Thin Films, Journal of Applied Physics Volume 91 Number 10 (2002).
[5] C. Kittel, Introduction to Solid State Physics 6th Edition. 1986.
[6] A. Fuad , M. Diantoro, R. Anggraini, Sintesa Bahan Ferroelektrik BaBi4Ti4O15 dan Karakterisasi Sifat Struktur
dan Listriknya, Simposium Fisika Nasional ke 23 ISBN 978-979-98010-6-7 (2010).
[7] W. Sakamoto , A. Iwata, T. Yogo, Ferroelectric Properties of Chemically Synthesized Perovskite BiFeO3-PbTiO3
Thin Films, Journal of Applied Physics 104. 104106 (2008).

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CODE : IM
Characterization of Polymer Membrane with Inorganic Adsorbent Lithium Manganese Oxide for Lithium
Recovery from Lumpur Sidoarjo
Lukman Noerochim1), Sheila Pramusiwi R1), Diah Susanti1) , and Amien Widodo2)
1

Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia
2
Department of Geophysical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111, Indonesia
Abstract: Adsorption method with lithium manganese oxide containing polymer membrane was selected for extraction
lithium from geothermal fluid of Lumpur Sidoarjo. Lithium manganese oxide has high selectivity toward lithium
adsorption as inorganic asorbent. Polymer membranes reservoir are prepared from polypropylene (Kimtech(R)),
polyester non-woven, and PVDF (Polyvinyllidene difluoride) with fiber glass. Physical characterization, water
diffussion and morphology of the membrane were systematically investigated. Polymeric PVDF membrane with 10:90
of FG shows the best result for the extraction of lithium from Lumpur Sidoarjo. It shows that the water uptake reaches
61.95%, and tensile strength 139.594MPa. ICP result also shows the lithium content of 3.55 ppm (mg/L). This indicates
that membranes PVDF 10:90 with 5% FG can adsorb lithium 60.68%. Therefore, PVDF 10:90 with 5% FG has a big
potential as a membrane for lithium extraction.
Keywords: Polymer Membrane; Adsorption; Extraction of Lithium; Sidoarjo Mud
Corresponding author : Lukman Noerochim, Email : lukman@mat-eng.its.ac.id, lukmanits@gmail.com. Tel. +62-85645988644, Fax. +62-31-5943645.
1. Introduction
Advanced technology demands various innovations which have the advantage of previous technology. For example,
smart phone or other portable gadget need battery technology as a power source. And one of the most important
component is a lithium-ion battery [1]. Today the amount consumed globally Lithium related to batteries has increased
more than 20% per year over the last few years [2]. Lithium is known as the lightest metal and has been used for many
commercial products due to its electrochemical reactivity and other unique properties. Lithium compounds and
minerals have attracted for many application such as in ceramics industry, glass, aluminum, lubrication, and
pharmaceutical industry [3].
Lithium source in nature deposit in three kind of resources, namely minerals, brine and the third and still in the
research ie. geothermal fluid. Various methods are used by researchers to obtain a high lithium levels. Including by way
of ion exchange resins, electrochemical, and coprecipitation but some of them require a high cost and the results are not
always in line with expectations. In recent years, it was developed new technique using adsorption extraction method
that utilizes lithium polymer membranes with inorganic adsorbents are considered to be an easier method than other
methods. The use of such methods normally used for the separation, purification, and concentration both on a small
scale in the laboratory and large scale industries. This is because the membrane technology is more economical than the
conventional technology. The advanced engineering of membrane technology is an continously process, simple, can be
combined with other equipment, and non-destructive nature.
In this study will be carried out the extraction process by using various polymer membranes reservoir in adsorption
methods with adsorbent inorganic spinel lithium -mangan. The source of lithium is extracted from the hot mud in
Lumpur Sidoarjo. In this research will be focused on the fabrication and characterization of polymeric membranes
prepared by PVDF with the appropriate fiber glass as filler. Polymer membrane (melt blow propylene) is Kimtech
(commercial) and non-woven polyester are used as comparison data.
2. Experimental procedures
2.1. Preparation of lumpur sidoarjo
The separation between fluid and sediment in the mud is performed by centrifuging process. centrifuge tube is
inserted into the machine with speed is set at 2500 rpm for 20 min. then the fluid of mud is poured into the separated
glass bottle.
2.2. Preparation of pvdf membrane
PVDF membrane is prepared using nips (non-solvent induced phase separation) by immersion precipitation method.
polyvinylidenedifluoride (pvdf) dissolved in a solvent such as n-methylpyrolydinone (nmp) with a ratio of 10:90 and
15:85, and with the addition of fiberglass variation of 5% and 15%. the polymer solution was dissolved and stirred with
a magnetic stirrer until a homogeneous for 3 hrs. then it was poured onto a glass plate, and waited for about 5 min. then

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the prepared membrane was immersed into a bath of non-solvent containing the distilled water and soaked for 24 hrs.
NIPS process itself can be divided into three specific techniques namely the method of water-casting of polymer
solution, precipitation from the vapor phase and immersion precipitation [4]. The three kinds of such techniques,
immersion precipitation is the most efficient method.
Non solvent

Solvent

support

Polimer + Solvent
non-solvent

Fig. 1. Mechanism of NIPS


2.3. Physical characterization
Scanning Electron Microscope (SEM) was conducted to observe the morphology of of the membrane by Phillips
SEM-type engines of FEI Inspect S550. Tensile test was conducted to determine the strength of the membrane.
Membrane for tensile test specimens are cut to the size of 50 mm x 15mm x thickness (mm). Dimensional tensile test is
tailored to ASTM D882.
3. Results and discussion
The mechanism of phase separation of polymer PVDF membrane formation in the process by using a solution of
NMP solvent. Phase separation of the polymer solution can be determined by monitoring the formation of the freezing
point of the polymer solution. The freezing point of the polymer solution is a condition where if the amount of nonsolvent solution is added to the polymer solution, there will be changes in the nature of the solution. Usually a color
change of the solution from transparent to white misty. In this study, the variations of PVDF composition and also the
addition of fiberglass as shown in Table 1.
Table 1. Variation of PVDF membrane
Membrane

Composition
PVDF+NMP

15:85
PVDF
10:90

Composition
fiberglass
5%
15%
5%
15%

During experimental process there is a membrane which failed to form so it can not be used that PVDF membrane
with a ratio of 10:90 without adding fibergelas. Where the membrane can not be formed even the immersion process is
carried out in a non-solvent of more than 1 day. The prepared membranes is very soft and easily torn.
3.1. Water Uptake Test Results
Water uptake test is to determine the ability of the membrane to absorb water. The percentage of water uptake can
be calculated by the following equation.
=

Table 2. Water uptake results of Kimtech and polyester membrane


Weight Weight
%
Average
No.
Membrane
(Dry)
(Wet)
Water
water
(gram)
(gram)
uptake
uptake
KIMTECH
1
0.2278 1.5880
597.10 595.255
%
2
0.2308 1.6004
593.41
POLIESTER
1
1.6529 7.1018
329.65
337.15%
2
1.640
7.2932
344.70

(1)

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Table 3. Water uptake of PVDF membrane


Weight of Dry Weight of Wet
% Water
Membrane
Membrane
Membrane
uptake
(gram)
(gram)
PVDf 10:90 w/o FG

t2

PVDf 10:90 5%FG

PVDf 10:90 15% FG

PVDf 15:85 tanpa FG

PVDf 15:85 5% FG

PVDf 15:85 15% FG

No.

1.3667
1.3174
2.574
2.5761
4.7687
4.9738
1.2554
1.8098
3.5504
3.8334

2.2515
2.0969
3.8838
3.6202
5.2345
5.4378
2.2627
2.6438
4.8556
4.8376

700

(a)

(b)
% water uptake

% water uptake

61.955
45.71
46.49
63.16
36.76

70
60

600
500
400
300
200

50
40
30
20
10

100
0
KIMTEX 1

64.74
59.17
50.89
40.53
46.58
46.4
80.24
46.08
36.76
26.2

Average of
water uptake
(%)

0
POLIESTER 1

60

(c)
% water uptake

50

PVDF 10 : 90 5% FG

40

PVDF 10 : 90 15% FG

30
PVDF15 : 85

20
PVDF15 : 85 5% FG

10
PVDF 15 : 85 15% FG

0
0

24

48

72

96

120

Time (hour)

Fig. 2. Water uptake of Kimtech dan poliester membrane (a), water uptake of PVDF membrane, and water uptake for
120 hrs (c).

Fig. 2 (a) and 2 (b) show the water up take ability of PVDF membrane. While Figure 2 (c) shows water uptake test
PVDF membranes for 120 hrs. It shows the best value occurs in the first 24 hrs. High yield occurs ould be the pores in
the membrane. The higher the value, the more pores in the membrane [5]. The water will fill the existing pores in the
membrane. The high water uptake indicates that there are many pores in the membrane so that the more water in the
membrane. Water as a medium for the transfer of ions, can enhance in the process of extraction of lithium ions. The
addition of fiberglass in membrane affects on the amount of water that can be absorbed by the membrane.

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(a)

(b)
(c)

Figure 3. SEM images of Kimtech (a), polietylene (b) and PVDF membrane (c).
Figure 3 show that the morphology of the membrane Kimtech and non-woven polyesters are smooth surface of

Fig. 3. SEM images of Kimtech (a), polietylene (b) and PVDF membrane (c).

Fig. 3 show that the morphology of the membrane Kimtech and non-woven polyesters are smooth surface of each
individual fibers. Only the density of the membrane looks diminished. This is in contrast to PVDF membranes that can
be seen in figure 4. In Figure 4 shows the big changes in morphology of PVDF membrane, which initially has big pores
becomes more solid. Figure 4 also shows the similar condition PVDF membrane after experiencing a first cycle and
sixth cycle membranes undergo changes in morphology. And tend to be degraded as shown in Figure 4 . Figure 4
shows that the pored membrane begin to experience degradation. It also occurs in other membrane types, ranging
degraded in cycle 1 and cycle 6 shown in Fig. 4.

(a)

(b)

Stress (N/mm2)

Fig. 4. SEM image of PVDF membrane with 10:90 15% FG (a) before first cycle, and (b) after 6 cycles.

150
135
120
105
90
75
60
45
30
15
0

PVDF 10:90 5% FG
PVDF 10:90 15% FG
PVDF 15:85
PVDF 15:85 5% FG
PVDF 15:85 15%FG

Strain (mm)

Fig. 5. Tensile test of PVDF membrane


The tensile test shows that the membrane which has the highest is 15% FG 10:90 PVDF. The addition of fiberglass
also affects the tensile strength can be differences with the membrane without the addition of fiberglass.

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3.2. ICP Testing Results


ICP test is to determine how much lithium can be adsorbed using existing membrane and compared the results
between using a commercialized membrane and as prepared membrane.

No.

Table 4. ICP test results


Membrane types
Lithium (ppm )

1.
2.
3.
4.
5.
6.
7.

Kimtex
Poliester
PVDf 10:90 5%FG
PVDf 10:90 15% FG
PVDf 15:85 tanpa FG
PVDf 15:85 5% FG
PVDf 15:85 15% FG

7.83
38.9
3.55
2.19
9.53
16.4
12.7

The higher lithium content in the mud is possible to leak (fouling) and due process of acid treatment is less than
perfect cause all adsorbent Lithium in spite of adsorbennya. So that the adsorption and desorption process causes the
content of Lithium counted in ICP test. In addition to these reasons can also be due to the leaks in the membrane. ICP
test results are supposed to be below the value of the content of the Sidoarjo Mud such as 10:90 PVDF membrane 5%
FG with 3.55 ppm (mg / L). It can adsorb lithium 60.68% of the mud and PVDF 10:90 15 % FG 2.19 ppm (mg / L),
which means it can adsorb approximately 37.43% Lithium.
4. Conclusions
Characterization of polymeric membranes for 5% PVDF membrane 10:90 FG is the best results due to meeting with
the requirements of membranes for the extraction of lithium from Sidoarjo mudflow. Here are the requirements:
Have a good hydrophilic character is shown from the test results of water uptake
The pore size is small, shown from testing SEM and ICP test
mechanical strength of the membrane is used to support the adsorbent is shown from the results of tensile testing
chemical resistance against aqueous HCl, can be seen through the results of SEM
References
[1] Qiao, Y.Q., Wang, X.L., Zhou, J.P., Zhang, J., Gu, C.D., Tu, J.P, (2011), Sysnthesis and Electrochemical
Performance of Rod-Like LiV3O8 Cathode Materials for Rechargeable Lithium Batteries. Journal of Power
Source, 198 (2012) 287-293.
[2] Kim, Kyungho., Park, Su Han., Kwon, Tae Hyung.,Ahn, Hyungkeun., Eo, Yang Dam., Lee, Man-Jong, (2012),
Reaction Sequence and Electrochemical Properties Of Lithium Vanadium Oxide Cathode Materials Synthesized
Via a Hydrothermal Reaction. Ceramics International, 39 (2013) 1623-1629..
[3] McGraw-Hill, (2004) Handbook of Batteries, third edition eds.Linden, David, Reddy, Thomas B., The McGrawHill Companies, New York
[4] K. West, B. Zachau-Chrisliansen, S. Skaarup, Y. Saidi, J. Barker, I.I. Olsen, Comparison of LiV3O8 Cathode
materials Prepared by Different Methods, J. Electrochem Soc., (1996), Vol 143, No 3.
[5] Pan, Anqiang., Liu, Jun., Zhang, Ji-Guang., Cao, Guozhong., Xu, Wu., Nie, Zimin., Jie, Xiao., Choi, Daiwon.,
Arey, Bruce W., Wang, Chongmin.,and Liang, Shuaquan, Template Free Synthesis of LiV3O8 Nanorods as a
Cathode Material for High-Rate Secondary Lithium Batteries. Journal of Material Chemistry, (2011) 21 11531161.
[6] H. Liu, Y. Wang, W Yang, H. Zhou, Large Capacity of LiV3O8 Cathode Material for Rechargeable Lithium
Based Batteries. Electrochemica Acta, (2010), 56 13920-1398.
[7] J. Xu, H. Zhang, T. Zhang, Q. Pan, Y. Gui, Influence of heat-treatment Temperature on Crystal Structure,
morphology and electrochemical properties of LiV3O8 prepared by Hydrothermal Reaction. J. Of Alloys and
Compounds 467, (2009), 327-331.
[8] Mo, Runwei., Du, Ying., Zhang, Naiqing., Rooney, David., Sun, Kening, (2014), Surface Modification of LiV3O8
Nanosheets Via Layer-By-Layer Self-Assembly for High-Performance Rechargeable Lithium Batteries. Journal
of Power Source 257 (2014) 319-324.
[9] Wang, Dunqiang., Cao, Liyun., Huang, Jianfeng., Wu, Jianpeng, (2011), Synthesis and Electrochemical
Properties of Submicron Sized Sheet-Like LiV3O8 Crystallites for Lithium Secondary Batteries. Material Letters
71, (2012) 48-50.

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CODE: IM
Surface treatment of ostheosyntesis plates by steel slag-ball blasting and electropolishing
Suyitno1), U.A. Salim1), N.A.P. Rochman1), Puntodewo2)
1

Center for Innovation of Medical Equipments and Devices (CIMEDs)


Dept. of Mechanical Engineering Gadjah Mada University, Yogyakarta Indonesia
2
Department of Orthopaedics and Traumatology
Sardjito Hospital, Gadjah Mada University, Yogyakarta Indonesia
Abstract: Ostheosyntesis plates of AISI 316 L is used for orthopedics implant to joint fracture of a long bones. The
ostheosyntesis plates undergo cyclic loading during appliacation due to body movement. The cyclic loading leads to
fatigue fracture in which a component is failure at a very low stress under the ultimate strength. The mechanical
properties on the surface of the ostheosyntesis plates are able to be improved to delay the formation of initial crack on
the surface. In this paper, the use of steel slag balls for improving metal properties through surface mechanical
treatment is demonstrated. The effect of a so-called steel slag ball blasting treatment on surface microhardness and
roughness of 316L stainless steel is discussed. The treatment is followed by electropolishing treatment. The treatment
was conducted with various processing time. The result indicates an increasing surface microhardness due to the steel
slag ball blasting treatment. A harder surface is yielded by the treatment with a longer duration. The treatment also
creates defects and gouged regions on the sample surfaces, which consequently modify the roughness. The
electropolishing treatment leads to a finer surface with increasing duration of treatment. In conclusion, the steel slag ball
blasting treatment is potential for improving the mechanical properties and the electropolishing treatment is beneficial
for removing the the roughing surface of the slag ball blasting treatment.
Keywords: slag ball blasting; small dynamics compression plate; electropolishing; microhardness; AISI 316 L
Corresponding author: Suyitno, E-mail: suyitno@ugm.ac.id
1. Introduction
Ostheosyntesis plate of AISI 316 L is widely used in Indonesia It has been used for a long time, however, the fatigue
and single cycle strength of the plates were consistently lower than those manufactured in Europe. The possible reason
is the plates are made from a lower quality stainless steel. Than those from AISI 316LVM which is medical grade
stainless steel (Dewo et al., 2012).
An improvement is needed to reduce the possibility of fracture due to cyclic loading during application. The cyclic
loading leads to fatigue fracture in which a component is failure at a very low stress under the ultimate strength.
Osteosynthesis plates should have a high strength with respect to fatigue, in order to withstand cyclic loading conditions
produced by muscle contractions and body weight, before healing process of the bone is complete (Schneider et
al.,2001; Niinomi et al.,2001; Tudor-Locke and Bassett, 2004). It also needs a smoth surface to avoid the formation of
initial crack on surface.
Sandblasting is a surface treatment using abrasive media that is impacted with sufficient pressure on the material
surface. Research on the sandblasting have been done [1-9]. The materials have been treated using sandblasting is pure
Titanium [1-3] and 316 L stainless steel [4-6]. Abrasive media used in the study was 750 m in diameter of Al2O3 [4],
200-300 m SiO2 [2] and 0.208 mm of silica sand [5]. Pressure used during the process of sandblasting is 350 kPa [4],
300 Psi [2] and 8 kg/cm2 [5].
Sandblasting treatment is carried out with the aim to improve the surface in order to obtain a spesific surface
morphology and improved mechanical properties. Sandblasting applications are mostly on the surface of metallic
materials that are used in industrial manufacturing, aerospace, automotive and biomaterials.
Sandblasting will affect the microstructure of the material [2,4,5]. The process of sandblasting reduces the grain size on
surface [2,4,5]. The process of sandblasting increases the surface hardness of materials exposed to treatment [2,4,5].
This process produces nanocrystalline layer that directly impact an increase in hardness value.
The steel slag balls blasting treatment has suscesfully impoved mechanical properties and bioactivity of stainless
steel based biomedical implants [Arifvianto et al., 2010]. The slag-ball is a product of atomising slag in the steel
making. The balls are formed through the newly developed slag atomizing technology (SAT). The SAT transforms the
molten slag from the furnace into a spherical shape slag particles with diameter of 0.1 4.5 mm through atomization
[Cha and Sadrpour, 2006]. The slag balls have been used mainly as the additional component of cement [Monshi and
Asgarani, 1999; Kouronis et al., 2007] and the abrasive blasting materials for cleaning up metals from dusts and rust
[Kambham et al., 2007]. This abbrasive media has specific characteristic that could be suitable for improvement of
surface quality of products.
The steel slag balls are potential to be used as the blasting particles for the surface mechanical treatment.

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Nevertheless, the treatment leads to a rough surface which is not suitable for osteosynthesis plate. The rough surface
due to steel slag ball treatment is able to be removed by polishing. Combination of blasting treatment (sa
(sand and slagball) and electropolishing have been reported. The blasting treatments tend to harden, roughen and remove surface, and
electropolishing treatment remove the rough surface and hard surface. The utilization of steel slag balls as the blasting
particles
ticles in surface mechanical treatment and combined with electropolishing treatment on osteosynthesis plates has
never been reported.Optimizing both treatment is needed to achieve a smot and hard surface.
The application of steel slag balls blasting treatment
treatm
on the medical device product will be investigated. The treatment
is combined with electropplishing treatment to remove the rough surface. A small dynamics compression plate that is
applied in fixing small bone fracture is used. In this study, the investigate is focused on the effect of duration of
treatment on small dynamics compression plate of AISI 316 L. Microstructural observation
observation, hardness and surface
roughness teasting will be performed and reported.
2. Materials and Methods
Samples were Small Dynamics
ynamics Compression Plate of AISI 316L with a dimension of 100 x 12 x 4 mm. The detail
sample shape is shown in Fig. 1. The sample chemical compositions (%wt) are 0.0316 C, 0.4360 Si, 0.0002 S, 0.0202 P,
1.2369 Mn, 10.9653 Ni, 24.3038 Cr, 1.7477 Mo, 0.8637 Cu, 0.0354 W, 0.0134 Ti, 0.0130 Sn, 0.0110 Al, 0.0015 Ca,
0.0362 Zn, and 60.28 Fe.

Fig. 1. Small Narrow Dynamic Compression Plate.Specimen and the location of microhardness testing,
The slag-ball-blasting
blasting was carried out by impacting the slag ball particles
particles toward the sample surface till 10 minutes.
The particles diameter is 0,6 - 1 mm, entrained in 6 7 kg/cm2 pressurized air flow prior to impact the sample surface
and 10 cm of sample to nozzle tip distant.
distant
The slag-ball compositions (in wt.. pct)
pct are 20.83 Fe, 3.35 FeO, 26.06 Fe2O3, 12.69 SiO2, 40.30 CaO and 2.20
Al2O3. The physical properties of the slag ball are 739.8 HVC of hardness, 2.3 kg/l of specific gravity and 323 kg/cm2
of compression strength. The blasting machine was equipped with three compressors (SWAN SVU
SVU-201) of 1 HP of
electric motor power, 85 liter of vessel volume capacity and 9 kg/cm2 of maximum air pressure. A blaster gun of 12
mm in nozzle diameter was used for spraying the slag-ball.
slag
The equipment used in the electropolishing process is the DC power supply with a maximum output of 2x100A.
Specimens that have been steel slag-ball
ball blasted were further processed with electropolishing with 9.5 volts of voltage,
1 cm of distance, and 10 and 20 minutes of duration. Anode and cathode material were stainless steel AISI 316L.
Electrolyte solution consisted of 96% mass fraction of sulfuric acid and 85% mass fraction of phosphoric acid with a
ratio of 1:1.
The microhardness distribution at the samples sectional area was measured using a microhardness
microhardness tester (Buehler,
USA). The measurement was conducted from a point close to the surface down into the bulk of the samples with an
indenting load of 4.9 N. The microhardness tests were conducted in two sections: the surface of the SDCP and the hhole
of the SDCP.
The samples were cut laterally after the treatment to expose its cross-sectional
cross sectional area at which the microstructure
observation and the microhardness measurement were conducted (fig. 2). The samples microstructure was observed
using Olympus microscope while the microhardness was measured using Buehler microhardness tester with an
indenting load of 500 kg. The specimen microhardness is indicated by Vickers Hardness Number (Hv).
The specimen surface roughness and its cross sectional surface profiles
profiles were measured and observed, respectively,

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using Surfcom 120A contact stylus profilometer (Advanced Metrology System, UK). The roughness was measured at
five different locations on the surface to obtain the average of arithmetic medium value (Ra) of the distance travelled by
the stylus. The surface morphology of the specimens and steel slag balls was observed using a scanning electron
microscope (SEM; JSM-6510LV,
6510LV, JEOL Ltd., Japan).
3. Results and Discussion
3.1. Microhardness on the surface
The microhardness (Hv).distribution across the specimen sectional area is shown in Fig. 2. The steel slag ball
blasting treatment enhance the subsurface microhardness. The steel slag ball blasting treatment in this study for 10 min
increases the Hv at a depth of 0.1 mm from
fro m 1.7 GPa to 2.5 GPa. The Hv decreases by the distance from the surface and
approaches the value of the unblasted specimen. By measuring the depth with Hv greater than that of the bulk or
unblasted specimen, the thickness of the hard surface layer can be determined.
determined. In this study, a hard surface layer with
0.5 mm thickness can be produced by the steel slag ball blasting treatment for 10 min..

Fig. 2. Microhardness distribution at the specimen subsurface before and after the steel slag balls blasting an
and
electropolishing treatment.
The electropolishing of the steel slag ball treatment-processed
treatment
specimen results in a lower microhardness than the
former processing. The steel slag ball blasting for 10 minutes followed by electropolishing for 10 and 20 minut
minutes
reduces the subsurface microhardness at a depth of 0.1 mm from 2.7 GPa to 1.9
1.9 GPa and 1.6 GPa, respectively. In
general, the electropolishing reduces the subsurface microhardness of the steel slag ball treatment -processed surface.
The duration of steel
el slag ball treatment influences the magnitude of the resulting subsurface microhardness (Hv). The

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electropolishing removed the hard surface produced by the steel slag ball treatment. The effect of steel slag ball
blasting treatment The implication is that
that the electropolishing treatment on the hard surface due to steel slag ball
blasting treatment should be carefully done to avoid the reomoval of the hard surface.
3.2. Surface roughness on the plate
Fig. 3 shows the modification of the average roughness (Ra) and the maximum value of peak
peak-to-valley height (Rmax)
of AISI 316L surface due to the steel slag ball blasting and electropolising treatment.
treatment

Fig. 3. The surface modification: a. Ra and b. by electropolishing The surface roughness evolution of the
specimen during the steel salag--ball
ball blasting treatment and electropolishing: a. Ra and b. Rmax..

The steel slag ball blasting of AISI 316L for 10 minutes reduces Ra from 1.71 m to 0.4
0.4 m and Rmax from 9.58
m to 1.34 m. The effect of electropolishing
polishing on surface roughness is shown in Fig. 3. In general, the electropolishing
reduces the roughness of the as-received
received and steel slag ball blasting-processed
processed surface. However, the initial surface
roughness of the specimens clearly influences their final
final roughness after 20 minutes of the treatment. Meanwhile, the
electropolishing of the as-received
received specimen reduces Ra from 3.51 m to 1.71 m and Rmax from 19.90 m to

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9.58 m. The electropolishing of the steel slag ball blasting-processed
blasting processed specimen results in a smoother surface than the
former processing. A relatively quick roughness reduction of the as-received
as received specimen occur
occurs during the first 2.5
minutes of steel slag ball blasting treatment,
treatment, however further reduction is not observed after this period; indicating the
saturation of surface roughness in steel slag ball blasting treatment.
treatment. On the other hand, the roughness satura
saturation is not
seen during the steel slag ball blasting treatment of electropolished treatment specimen.
3.3. Microhardness on the holes
The microhardness distributions across the sample sectional areas with various distance from the upper surface for
10 min in the hole of SDCP are shown in Figs. 4. The treatment slag-ball-blasting
blasting treatment improve microhardness on
the hole surface. The microhardness gradually decreases and approaches the values for the control sample (1.5 GPa) as
increasing distance from the surface. The microhadrness on the hole surface is highest on a distance that is close to the
upper surface of NDCP, and decreases as increasing distance from the upper surface.

Fig. 4. Microhardness distributions in the hole with various distance from


om the upper surface for duration of 10 minute
3.4. SEM
The specimen surface morphology modified by the steel slag-ball
slag ball blasting and electropolishing treatment is shown
in Fig. 5. The impacts of the steel slag particles during the blasting treatment create
create a rough surface (Fig. 5a and b).The
rough surfaces are modified by electropolishing treatment (Fig. 5c and d). Further increasing duration of the
electropolishing treatment, the rough surface is removed (Fig. 5e and f).
The steel slag-ball blasting treatment
ment with a longer duration prior to electropolishing treatment results in a smoother
surface than that with a shorter duration. Further observation on the steel slag-ball
slag ball processed surfaces, there is no
indication that the steel slag-balls
balls are not embedded
embedded on the surface. The clear surface features observed on the surface
are debris, cracks and tracks of material flow during the first 5 and 10 min of treatment (Fig. 5a and b).
The use of steel slag balls as the blasting particles in surface mechanical treatment
treatment of SDCP is introduced in this
study. The effect of a so-called
called steel slag ball blasting treatment on microhardnes of SDCP is investigated. The principle
of steel slag ball blasting treatment is similar to that of the sandblasting or shot peening. The
The slag balls are blasted onto
the sample so that a microstructural and morphological evolution on the sample surface occur during the treatment. The
surface microhardness enhancement after the slag ball blasting treatment is attributed by the modification of sample
microstructure at the corresponding location. The higher microhardness value corresponds to the smaller indented area
at the sample after Vickers hardness testing. The indenter is unable to produce a severe deformation and a larger
indented area on a fine grains sample. In addition to the grain refinement, the presence of compressive residual stress
likely contributes to the microhardness enhancement.
The microhardness enhancement during the slag ball blasting treatment is time-dependent.
time dependent. A longe
longer duration of slag
ball blasting produces a harder surface. The sample receives impact load from the slag balls until the nanocrystallites
are formed completely and exists in a large number.add any kind of pagination anywhere in the paper.

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a.

b.

c.

d.

e..
f.
Fig. 5. Surface morphology of the specimen after the steel slag-ball
slag ball blasting treatment for: 5 min (a) and 10 min
(b), followed by electropolishing treatment for: 10 min (c and d) and 20 min (e and f).
4. Conclusions
The increasing
g surface microhardness is due to the slag ball blasting treatment. A harder surface is yielded by the
treatment with a longer duration of treatment. The slag ball blasting creates defects and gouged regions on the sample
surfaces. The effect of treatment on the hardness is prominent till a distant of 0,3 mm from the surface. This treatment is
potential for improvement of the surface mechanical properties of SDCP.
References
[1] A. Piatelli, A. Scarano, M. Piatelli, L. Calabrese, Direct bone formation on sand-blasted
lasted titanium impants: an
experimental study, Great Britain,
n, 1995.
[2] X.P. Jiang, X.Y. Wang, J.X. Li, D.Y. Li, C.S. Man, M.J. Shepard, Zhai, Enhancement
ment of fatigue and corrosion
properties of pure Ti by sandblasting,
andblasting, Mater. Sci. Eng. A, vol. 429, pp 3035, 2006.

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The 7th International Conference on Sensors ASIASENSE 2015
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[3] C.N. Elias, Y. Oshida, J.H.C. Lima, C.A. Muller, Relationship between surface properties (roughness,
wettability and morphology) of titanium and dental implant removal torque, J. Mech. Beh. Biomed. Mat., vol.1,
pp 234 242, 2008.
[4] M. Multigner, E. Frutos, J.L. Gonzlez, J.A. Jimnez, P. Marn, and J. Ibez, Influence of the sandblasting on
the subsurface microstructure of 316LVM stainless steel: Implications on the magnetic and mechanical
properties, Mater. Sci. Eng. A, vol. 29, pp 1357-1360, 2009.
[5] B. Arifvianto, Suyitno, M. Mahardika, The effect of sandblasting and surface mechanical attrition treatment on
surface roughness, wettability, and microhardness of AISI 316L, International Conference on Fracture and
Strength of Solids, Kuala Lumpur, Malaysia, 2010.
[6] B. Arifvianto, Suyitno, M. Mahardika, P. Dewo, P.T. Iswanto, U.A. Salim, Effects of surface mechanical
attrition treatment (SMAT) on microhardness, surface roughness and wettability of AISI 316L, Mat. Chem. and
Phys., vol. 125, pp 418-426, 2011.
[7] L. Wang, and D.Y. Li, Mechanical electrochemical and tribological properties of nanocrystalline surface of brass
produced by sandblasting and annealing, Surf. and Coat. Tech., vol. 167, pp 188196, 2003.
[8] M. Umemoto, K. Tsuchiya, Formation of nanocrystallization structure in steels by air blast shot peening, Mater.
Trans., vol. 44, pp 1488-1493, 2003.
[9] S. Cha, H. Sadrpour, Proc. Global Slag Conf. Exhibition, 2006, 4.1.
[10] A. Monshi, M.K. Asgarani, Cement Concrete Res. 29 (1999) 1373.
[11] S. Kourounis, S. Tsivilis, P.E. Tsakiridis, G.D. Papadimitriou, Z. Tsibouki, Cement Concrete Res. 37 (2007) 815.
[12] K. Kambham, S. Sangameswaran, S.R. Datar, B. Kura, J. Cleaner. Product. 15 (2007) 465.
[13] Arifvianto, Suyitno, K.A. Wibisono, M. Mahardika, Surface & Coatings Technology, 210 (2012) 176182

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CODE: IM
Novel Approaches to The Development of Dental Filler {CH-CaCO3-(C-HA)-MMA} from Bio Waste Recycle
Fanny Leestiana1), Yuli Setiyorini 1), Rochman Rochiem1), Sungging Pintowantoro1), Budi Agung Kurniawan1)
1

Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia
Abstract: In order to avoid the toxicity and discomfort of patient from the toxic/allergic dental filler material, this
study focus on the novel approaches to the development of dental filler based on chitosan (C), calcium carbonate
(CaCO3), and carbonate-hydroxyapatite (C-HA) from bio waste recycle which combine with methyl methacrylate
(MMA), respectively. The effect of ratio composition was investigated into several characterizations and analysis. The
morphologies were revealed the dense structure for all the samples. Moreover, chemical composition and phase
analysis were measured, respectively, was shown correlated results between control and all the dental filler materials.
The dental fillers were depicted a good thermal properties, particullary for G5050 and G7525 were performed thermal
conductivity approximately 0.86W/mK at 46C. The hardness value was measured at 88.04 VHN. All the dental filler
materials were exhibited the inhibition zone 1mm. In general, these dental filler materials are promising can be used
in dental materials application.
Keywords: chitosan; calcium carbonate; carbonate-hydroxyapatite; MMA; dental filler
Corresponding author: Yuli Setiyorini, E-mail: yulisetiyorini@yahoo.com, Tel. +62-31-5997026, Fax. +62-31-5997026

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CODE: IM
The Effect of Inorganic Fillers on Mechanical Properties of HDDA/TPA Photopolymer Nanocomposite Prepared
by Digital Light Processor RP Machine
Sigit Tri Wicaksono1), Shih-Hsuan Chiu2) and Kun-Ting Chen2)
1

Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia
2
Department of Materials Science and Engineering, National Taiwan University of Science and Technology, Taiwan,
ROC.
Abstract: The acrylate-based photopolymer consists of Tetra-functional Polyester Acrylate (TPA) and Hexanediol
Diacrylate (HDDA) has been successfully composited with nano barium titanate (BaTiO3) and nanoclay prepared by a
digital light RP machine. tensile strength and hardness of samples were characterized by Universal Tensile Machine
JIA701 and Hardness Shore D tester respectively. The morphology changes of the samples were also investigated by
using the JEOL JSM-6390LV scanning electron microscopy (SEM). The results show that the modulus elasticity and
hardness increase as the filler loading increases up to 2 phr.
Keywords: photopolymer, nanocomposite, dielectric constant
Corresponding author: Sigit Tri Wicaksono, E-mail: sigit@mat-eng.its.ac.id, Tel. +62-31-5997026, Fax. +62-315997026
1. Introduction
The most concerned todays issues regarding to materials manufacturing are the energy saving and environmental
problems. Polymer-based composite manufacturing via melting or via solvent mixing usualy produce volatile
compound as side reaction and high cost output. Recently, the development of low temperature and low time consuming
processing of manufacture have been developed for the last several years via rapid prototying system.
Photopolymer/clay nanocomposites have been developed by Fawn et al. [1] and Decker et al. [2] based on acrylate
(radically initiated photopolymer) and epoxy (cationic initiated photopolymer) systems. These nanocomposites show
some improvements in both thermal and mechanical properties without any significant change in the
photopolymerization rate in comparison to the pristine polymer. In our previous researches [3-5], we used TPA
(Tetrafunctional Polyacrylate) mixed with HDDA (Hexanediol Diacrylate) as a matrix and a small amount of nano
silica, and carbon black as the fillers. The liquid composites were cured from liquid to solid by a digital light processor
RP machine through layer by layer process to form the desired prototypes. The tensile strength and hardness of HDDATPA/Inorganic (silica, nano caly and carbon black) nanocomposites increased approximately by 50% to 60% compared
to the pristine HDDA-TPA. These fillers have successfully improved the feasibility of the HDDA/TPA photopolymer to
be applied in Rapid Prototyping System to manufacture the prototype products.
In this research, we further investigate the morphology and mechanical properties of photopolymer/barium titanate
and clay as the effect of BaTiO3 and clay filler loading in order to make it feasible to be applied in related applications.
2. Experimental
Tetra function Polyester Acrylate (TPA) and 1,6-Hexanediol Di-acrylate (HDDA) were mixed with a ratio of 50:50
for about 30 minutes at 1000 rpm. After BaTiO3 and clay filler being added, they were re-stirred for about 24 hours at
1000 rpm. The liquid photopolymer/BaTiO3 nanocomposite was cured into a solid part layer by layer with 100 micron
of layer thickness by using a digital light rapid prototyping (DLRP) Machine. The DLRP machine is a computercontrolled machine designed to adjust several curing processes parameters such as an area of light (masking), timing,
and depth of penetration of digital light exposed into the liquid precursor to cure the precursor into a solid
part/prototype as schematically described on the previous study.[3-5]. A few percent of photo initiator was added to
catalyze photo-curing reaction when introduced under visible light to form the solid part of photopolymer/BaTiO3 and
clay nanocomposite.
3. Results and discussion
Generally, the addition of inorganic filler materials into a polymer matrix will increase its hardness. In our previous
researches [3,4], the hardness of photopolymer was increased significantly by adding a few amount of SiO2 and carbon
black together with dispersant agent in an appropriate ratio. In this research, it was consistent with the previous results
that the maximum hardness was achieved by the sample with 2phr of BaTiO3. But, compared to the sample with clay
filler, the sample with BaTiO3 filler has lower hardness value as shown on Fig. 1. This indicates that the bounding

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(ICOMMET 2015)
th
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Surabaya, 4-6 October 2015
tendencies of clay filler within photopolymer matrix (possibly intercalated, exfoliated or flocculated as reported by
Fawn et al. [1])
]) is stronger than that of BaTiO3 filler.

Fig. 1. Hardness as function of filler loading


Fig. 2 shows the effectt of filler loading on the tensile strength and modulus elasticity of photopolymer/BaTiO3
nanocomposite. Generally, there are no significant improvements on tensile strength and elastic modulus of samples
with BaTiO3 and clay fillers. But, compared to the sample with clay filler, the elastic modulus of sample with BaTiO3
is higher. It means that sample with BaTiO3 filler is more stiff than that of sample with clay filler. The stiffness of
sample with BaTiO3 filler may be caused by the formation of agglomeration
agglomeration of BaTiO3 filler within photopolymer
matrix as shown on figure 3. It is quite different compared to our previous result, [2] that indicate the sample with clay
loading which possibly forms flocculated, intercalated or exfoliated clay structure within photopolymer and make the
composite more elastic when subjected to tensile test.

Fig. 2. Tensile Strenght and Modulus Elasticity as function of filler loading


loading.

Fig. 3. Agglomeration of BaTiO3 within photopolymer matrix.

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4. Conclusions
Effect of fillers (nano barium titanate and nano clay) on mechanical properties of HDDA/TPA photo-cured
polymer prepared by a digital light processor RP machine was studied. The modulus elasticity and hardness was
increased by increasing the fillers. The maximum increment of its mechanical properties was obtained by filler loading
of 2 phr. It indicates that the optimum filler loading is 2phr.
References
[1] Fawn MU, Webster DC, Davuluri SP, Wong SC. European Polym. J. 2006. 42, 2596-2605.
[2] Decker C, Keller L, Zahouily K, Benfarhi S. J. Polym. 2005, 46, 3275-3284.
[3] Shih-Hsuan Chiu, DC Wu. J. Appl. Polym. Sci. 2007, 107, 6-10.
[4] Shih-Hsuan Chiu, Sigit Tri W, Kun-Ting Chen, Sheng-Hong Pong. J. Sci Eng Compos Mater, 2014, 21(2), 205210
[5] Shih-Hsuan Chiu, Sigit Tri W, Kun-Ting Chen, Chiu-Yen Chen, Sheng-Hong Pong. Rapid Prototyping Journal,
2015.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
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CODE: IM
Hybrid-Fibre Composite for Sound Absorption Materials: Improvement of Sound Absorption Coefficient and
Mechanical Properties of Bamboo-Bagasse Reinforced Composite Gypsum
Mohammad Farid1),, Wawan Aries Widodo 2), Muhammad Agung Sahid3), Alldi Nurisiyantoro 4)
1,3,4

Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia
2
Department of Mechanical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111, Indonesia
Abstract: The purpose of this research is to develop a bamboo and bagasse fiber reinforced composite material that
can be applied to sound absorption material at low frequency. The study was conducted to assess the effect of the
combination of natural fibers of the composite gypsum to the compression strength and flexural strength, and sound
absorption coefficient of the composite material.The aim was to gain an optimal bending strength and compression
strength based on the composition of fibers. Hand lay up method was applied in manufacturing of the specimen.
Methods of testing were in accordance to ASTM D790 , ASTM E1050, ASTM D695 standards. The use of hybrid
fiber composites improve the sound absorption coefficient at low frequency to meet ISO 11654 standard, the flexural
properties, and the compression properties of gypsum composite.
Keywords: composite; natural fiber; gypsum, mechanical properties; sound- absorbing- material
Corresponding author: Mohammad Farid, E-mail: mofaredo@gmail.com, Tel. +6287853227060

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
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CODE: IM
Microwave Assisted in Synthesis Carbonated-Hydroxyapatite from Bovine : Influenced by Power Input and
Time Radiation
Sungging Pintowantoro1), Yuli Setiyorini1)
1

Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia
Abstract: : Microwave assisted for synthesis organic was become potential alternative to producing hydroxyapatite due
to in efficiency. The significant parameter are the power input and time of radiation. Moreover in the microwave
radiation, the effect of hot spot inhomogenity and selective heating are play important role to boost the organic reaction
rate [1]. This study was investigated the influence of power input and time radiation of synthesis hydroxyapatite from
bovine using microwave. The experiment was conducted in variation of power input (900 Watt and 720 Watt) and time
of radiation (90 minute and 75 minute), respectively. The results was depicted in variation of morphologies. The XRD
results were shown difference of compound, the hydroxyapatite has completely formed at 900 Watt both in 90 minute
and 75 minute. The ratio of Ca/P was indicated close to human body at 900 Watt in approximately 1.65 and 1.68,
meanwhile the ratio of Ca/P from 720 Watt was revealed approximately 1.61 and 1.62.
Keywords: bovine; carbonated-hydroxyapatite; microwave; power input; time radiation
Corresponding author: Yuli Setiyorini, E-mail: yulisetiyorini@yahoo.com, Tel. +62-31-5997026, Fax. +62-31-5997026

Fig. 1. SEM images of hydroxyapatite at: a. 90 minute (900W), b. 75 minute (900W), c. 90 minute (720W), and d.
75 minute (720W).

References
[1] C. O. Kappe and D. Dallinger, Nature Reviews Drug Discovery, 5, (2006) 51-63

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
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CODE: IM
Friendly Environment Chitosan Production using Microwave Radiation
Yuli Setiyorini1), Sungging Pintowantoro1)
1

Department of Materials and Metallurgical Engineering, Institut Teknologi Sepuluh Nopember, Surabaya 60111,
Indonesia
Abstract: In this study present of synthesis chitosan from waste prawn using radiation of microwave. The radiation
processing offers a clean one-step method for the formation of low molecular weight polysaccharides [1]. The detail
experimental demonstrated that variation of power microwave was affected the chitosan resulted in molecular weight,
viscosity and density. Microwave radiation was produced the powder chitosan with degree of deacetylation (DD)
achieve 77% using power 900Watt. The 900 Watt of power was resulted the chitosan with molecular weight, viscosity
and density approximately 47.93; 1.04g/cm3 and 1.314 g/cm3, respectively. In contrast, reduction of power radiation to
720 Watt was resulted chitosan with reducing of moleular weight, viscosity and density. Moreover, 720 Watt was
resulted chitosan with degree of deacetylation (DD) approximately 79%. Non-hygrocopis chitosan was depicted in both
900 Watt and 720 Watt from the FTIR analysis. The TGA/DSC analysis was illustrated of decomposition at different
temperatre between 900 Watt and 720 Watt (Figure 1).
Keywords: chitosan; microwave; power inpu; prawn shell
Corresponding author: Yuli Setiyorini, E-mail: yulisetiyorini@yahoo.com, Tel. +62-31-5997026, Fax. +62-31-5997026

Figure 1. TGA/DSC of chitosan microwave radiation assisted in 720W and 900W.

References
[1] W.S. Choi, K. J. Ahn, D. W. Lee, M. W. Byun and H. J. Park, Degradation Stability, 78, (2002) 533-538

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
The 7th International Conference on Sensors ASIASENSE 2015
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CODE: IM
Nanomaterial Titanium Dioxide synthesized from Sol-Gel Process for CO Gas Sensor Application
Hariyati Purwaningsih1), Ika Silviana Widianti2), Della Dewi R.1), Malik Anjelh B.3), Mas Irfan P. Hidayat 1)
1

Department of Materials and Metallurgical Engineering, Institute of Technology of Sepuluh Nopember (ITS)
Surabaya, Indonesia
2
Department of Material Science and Engineering, National Cheng Kung University, Tainan 701, Taiwan, ROC
3
Department of Physics, Institute of Technology of Sepuluh Nopember (ITS) Surabaya, Indonesia

Abstract: Titanium dioxide (TiO2) gas sensors were fabricated via sol-gel method from a starting TiO2 powder
dissolved in sulfide acid (H2SO4). The influence of acidity (pH) during synthesis and concentration of CO gas was
studied. Sol-gel method was used with following steps such as submersion and continued by stirring for 2.5 hours 700
rpm at 200C. After drying at 3500C for 2 hours, nanosensors were prepared in a form of circular tablets by pressing the
nanopowder at the pressure of 200 MPa and sintered at 900C for 1 hour. Morphological properties of nanopowders
were investigated by Scanning Electron Microscope (SEM), Transmission Electron Microscope ( TEM), X-ray
Diffraction (XRD), BrunauerEmmettTeller, adsorption isotherms BET analyzer. Nanosized titanium dioxide
morphology had a shape of spherical and stable phase of anatase. These spherical particles had been generated and
connected with each other. Sensitivity on gas sensor prototype was observed by potentiostat. Sensitivity values were got
from tests operated on 100C and variations in volume of CO gas such as 5L, 12.5L, 25L. The best response was TiO2
pH 3 sintered at 900C and had porous size of 50.83 nm.
Keywords: titanium dioxide (TiO2); sol-gel method; sintering; sensitivity value; CO gas
Corresponding author: Hariyati Purwaningsih, E-mail: hariyati@mat-eng.its.ac.id
1. Introduction
The need for real time gas composition measurements to help monitor and control the efficiency of many industrial
processes has sparked research interest in metal-oxide semiconductor gas sensors due to their inherent stability and
ability to operate in high temperature harsh environments [1]. Oxygen ions, adsorbed on the oxide particles, create a
surface depletion layer and increase the resistance of the sensor. Presence of a reducing gas lowers the resistance of the
sensors by reacting with the adsorbed oxygen ions and reducing the depletion layer conduction barrier. Structural and
chemical modifications on tin oxide (SnO2) have enabled commercially available sensors able to operate between 200
and 400C [2,3]. TiO2 sensors use the same sensing mechanism as SnO2; however they are operational up to 600C and
have the potential to be the material of choice near this temperature.
The sensitivity of oxide-based gas sensors is determined by a distinctive change of their resistance in the presence of
gases. The addition of dopants to metal oxide semiconductors is the most common route of obtaining selective gas
sensors. Sensors that are based on semiconductor oxides are generally of low cost and of high stability, even in
corrosive environments. The disadvantages are a lack of sensitivity to dilute gasses, the lack of long-term stability under
fluctuating environments, and the yield of signals from interfering gases. The factors controlling the sensing
characteristics of gas sensors are considered to be the electronic structure, microstructure, and surface structure of the
sensor materials [4].
Application of metal oxide (MOx) semiconductor as gas sensors were found not limited to explosive gas sensing.
Developing gas sensor so that it could be implicated better started to be considered, one of them is pollutant gas
sensing. Sensors made of metal oxide semiconductor are well known because of their fast responses. TiO2 is one of the
most promising gas-sensing materials due to its high temperature stability, harsh environment tolerance, and catalytic
properties [5]. Titanium dioxide likely used as gas sensor to sense and measure CO gas and H2 gas. Metal oxide sensor
production by using chemistry synthesis resulted in an irregular shape was once implicated to almost nanostructures of
metal oxide sensor. Sol-gel method is one of few choices because of it is particularly suited for the control at the
nanoscale of shape, size, and composition of metal oxides, which are the keystones of a wide spectrum of applications
ranging from energy storage and conversion, to sensing, and to the general fields of catalysis, optics, and electronics [6].
As gas sensing application, selectivity, sensitivity, and durability were important properties to be considered. To
improve those properties, microstructure controlled, higher surface areas in mesoporous are more effective because the
amount of interacted gas molecules with semiconductor can be increased through this way [3]. Furthermore, studies of
acid variation on phase and crystal size of ceramic material TiO2were aimed to anatase phase development and decrease
crystal size so that more defects will be occurred [4]. Generally, the defects related to adsorption ability of the surface

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of the material toward an oxygen atom, causing ionization of the atom and yielding positive charge carrier [5]. Then
both of them will react with a gas used as subject.
This study will be mainly discussed in ceramic material TiO2 made through sol-gel method and has different in
acidity. Sulfide acid (H2SO4) is used as solvent. The sensitivity values before and after being exposed in CO gas will be
measured at the amount of gas 5L, 12.5L, and 25L at 100 C.
2. Experimental Details
The synthesis procedure involved the following steps: (1) TiO2 gel formation, (2) drying of the gel, (3) annealing of
TiO2 xerogel powder at 350C for 2 hours, (4) pressed TiO2 at 200 bar pressure, and (5) sintering the bulk TiO2 at
900oC. Solgel synthesis of TiO2 gel was carried out using titanium dioxide powder (Merck) as a precursor and sulfuric
acid solution (H2SO4) as a solvent. Sol-gel method process is started by immersing 4 grams TiO2 powder in 24 mL
H2SO4 aqueous solution until acidity (pH) at 1, 3 and 5. After 4 days immersion in H2SO4, the solution made of TiO2
and H2SO4 is stirred at 200C for 2.5 hours at 700 rpm. The gel are washed in distilled water to neutralize acidity until
pH = 7. The washed gel is dried at 350C for 2 hours. Drying product is grinded to obtained fine powders. The fine
powders were compacted at 200 MPa and converted into circular pellets of 14 mm diameter and 2-3 mm thickness.
Pellets ceramic were sintered at 900C for 1 hour. Sintered pellet were characterized to identified phase changed and
morphological properties of nanosized titanium dioxide.
X-Ray Diffraction data were collected in the 2 regions of 5-90o with a scan rate of 0.02o/second on PanAnalytical
MPD-System diffractometer with a thetatheta geometry and a Cu K radiation ( = 0.154056 nm). The average
crystallite size and strain were estimated by WilliamsonHall method and determined from a convolution based full
pattern fitting using the HighScore Plus software package. Peaks were fitted using a simplified integral breadth method
to account for both strain and crystallite size effects. Scanning electron microscope (SEM) images were obtained on a
Inspect S FEI. Transmission electron microscopy (TEM) experiments were performed on a JEOL JEM-200CX operated
at 160 kV. Physisorption isotherms were measured with a Micromeritics system at 77 K. Before the measurements, all
samples were degassed at 120 C under vacuum for 12 h. The pore volumes and pore size distributions were derived
from the adsorption branches of isotherms using the BarrettJoynerHalenda (BJH) model. The specific surface areas
Sp (m2/g) were estimated via the BET method.
Gas sensing properties were measured under room condition (humid range 3060%) using a static test system made
by potensiostat dynamic which included a test chamber (about 18 L in volume) and a data acquisition/processing
system. The resistances of sensors were measured via direct current bridge method. The operating temperature of a gas
sensor was adjusted at 100oC. Sensor response in this paper is defined as S = R0/Rt, where R0 and Rt are the resistance
of the sensor in air and in tested gas, respectively. The response and recovery time were expressed as the time taken for
the sensor output to reach 90% of its saturation after applying or switching off the gas in a step function.
3. Results and Discussions
3.1 Structure and Morphologi
The sol-gel process may be described as formation of an oxide network through polycondensation reactions of a
molecular precursor in a liquid. The idea behind sol-gel synthesis is to dissolve the compound in a liquid in order to
bring it back as a solid in a controlled manner. Multi component compounds may be prepared with a controlled
stoichiometry by mixing sols of different compounds. The sol-gel method prevents the problems with co-precipitation,
which may be inhomogeneous, be a gelation reaction.
In this study, the interaction between sulfide acid (H2SO4) and TiO2 during sol-gel process may be explained using
chemical reaction. The following reaction could be proposed:
TiO2(s)+2H2SO4(l) Ti(SO4)2(s)+2H2O(l).......(1)
TiO2(s)+2H2SO4(l)+H2O(l) Ti(SO4)2(s)+3H2O(l)(2)
Ti(SO4)2 (s) + 2H2O(l) TiO2(s) + H2SO4(g) + OH-(g)(3)
To determine chemical composition of the prepared nanosized titania powder, first presented XRD patterns of the
samples prepared by sol-gel reaction as shown in Fig. 1. All peaks correspond well to anatase-TiO2 (ICDD card No. 00021-1272). No other crystal phase is detected, indicating the high purity of the raw powders and final products as shown
in equation 1-3. One can see that both samples have similar XRD patterns such as location, intensity and breadth,
suggesting that the samples exhibit the same crystal phase. They also have tetragonal crystal structure and chemical
formula titanium dioxide (TiO2). The other three acidity variations have same results, single phase anatase
corresponding to ICDD card No. 00-021-1272. Automatically, they have tetragonal crystal structure as well as pure
titanium dioxide (raw materials). Various pH during sol-gel reaction does not induced phase changed anatase-titanium
dioxide.
Figure 3 shows the x-ray diffraction for nanosized titanium dioxide after sintering at 900oC various pH. All peaks
correspond to the anatase, there is no other phase and crystal structure after sintering 900oC. Sintering up to 900oC did
not induce phase transformation anataserutile or anatasebrookite.

The 2nd International Conference on Materials and Metallurgical Technology 2015 (ICOMMET 2015)
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Fig 1. X-ray diffraction pattern of comparison TiO2 powder (a) raw material, (b) pH 1, (c) pH 3, dan (d) pH 5

Fig 2. X-ray diffraction pattern of TiO2 powder synthesized at various (a)pH 1, (b)pH 3, and (c)pH 5 after sintered at
900C
Crystallite sizes were determined from the full width at half maximum of the (101) peak according to the Scherrer
equations (equation 6). B is a value of FWHM in radians. D is crystal size in nm, is wavelength of Cu-K = 1,54056
A, and is angle position of (101) peaks, is microstrain values.

B (radian) =
B (radian) = 4
D (A)
=

anatase
anatase
anatase

25.26
25.29
25.44

0.244
0.167
0.201

..(4)

(5)
,

..(6)

Table1. XRD calculation of TiO2 after sintered at 900C


Variation
Phase
2
FWHM B
D
Of Acidity
(rad)
(nm)
pH 1
pH 3
pH 5

0.0019
0.00109
0.004004

74.9438
130.8367
97.7404

(103
)
2.12
1.21
1.61

Owing to the samples were annealed at the same temperature and time, the different acidity (pH) reaction may affect
crystallization of TiO2 to some extent. Sintering process has been no affected TiO2 phase with acidity variation 1, 3, and
5. Thus samples which are sintered at 900C have single phase anatase with tetragonal crystal structure, and chemical

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Surabaya, 4-6 October 2015
formula TiO2 corresponding to PDF #00-021-1272. There are no significant differences found in characterization results
on these three variations. Matching process with PDF card #00-021-1272, it is proven that the matching is right after
lattice parameter of all samples are calculated by using CellCalc Ver. 1.51, in where the samples have tetragonal
structure (a=bc). Even have same structures, TiO2 crystal size decrease after sintered at 900C.
(a)

(b)

(c)

(d)

Fig 3. Thypical morphology of TiO2 powder resulted from (a) raw material-Me