IEICES
Intellectual Exchange and Innovation Conference on
Engineering & Sciences (IEICES)
15 October, 2015
Kyushu University, Fukuoka, Japan
CONFERENCE PROGRAM AND PROCEEDINGS
IEICES
Intellectual Exchange and Innovation Conference on
Engineering & Sciences (IEICES)
15 October, 2015
Kyushu University, Fukuoka, Japan
CONFERENCE PROGRAM AND PROCEEDINGS
I
IEICES
CONFERENCE PROGRAM
AND PROCEEDINGS
WELCOME MESSAGE
Welcome to IEICES!
On behalf of the IEICES 2015 organizing
committee, it is my great pleasure to welcome
you to the Intellectual Exchange and Innovation
Conference on Engineering & Sciences (IEICES),
which is being held on 15th October, 2015 at
Kyushu University, Japan. The conference
brings together academics, researchers and
students to share the latest developments and
research in the fields of materials, energy and
environmental engineering & sciences. The
organizing committee has developed an exciting
program to give participants an opportunity to
present their academic works, concepts and
new discoveries. Moreover, participants will
have a chance to get to know one another
closely.
Before I close, I would like to thank each of your
for participating our conference and bringing
your expertise to our gathering.
Osama Eljamal
IEICES Chairman
GENERAL INFO
The first session of
Intellectual Exchange and
Innovation Conference on
Engineering & Sciences
(IEICES) is organized by
Interdisciplinary Graduate
School of Engineering
Sciences (IGSES) and the
PhD students of IEI Program
of Kyushu University. The
participants work on
different subjects including
applied science for
electronics & materials,
molecular & material
sciences, advanced energy
engineering science, energy
& environmental
engineering, and earth
system science technology,
etc. The participants will
have an opportunity to
present their academic
works, concepts and new
discoveries as well as they
will have a chance to
exchange their ideas and
develop their works.
Venue
3rd Floor
Administrative Building
Chikushi Campus
Kyushu University
6-1 Kasuga-koen, Kasuga,
Fukuoka, 816-8580, Japan
II
COMMITTEES
Conference Honorary Chairman Prof. Akira Harata
Conference Chairman Associate Prof. Osama Eljamal
Conference Coordinator Ahmad Syahrin Idris
Conference Organizing Committee Ahmed Mohamed Elsayed Khalil
Ding Dong
Mahmoud Ramadan Abusrea
Moses Kibunja Kamita
Muhammad Hamid Mahmood
Nik Mohd Izual Nik Ibrahim
Qi Shi-Chao
Ruan Hongcheng
Tarek Naem Dief
Wang Zhengxing
Zhang Lu
III
Technical Program
Time Thursday, 15 October 2015
9:00-10:00 Registration
10:00-10:10 Opening Remarks, Prof. Akira Harata
10:10-10:40 Invited Speaker (1) Prof. Kazuo Arakawa
10:40-11:10 Invited Speaker (2) Prof. Shigeo Yoshida
11:10-11:20 Photo Session & Break
11:20-11:35 1 Mahmoud Abusrea
11:35-11:50 2 Moses Kamita
11:50-12:05 3 Hongcheng Ruan
12:05-12:20 4 Tarek Dief
12:20-12:35 5 Ahmed Khalil
12:35-12:50 6 Nik Mohd Izual Nik Ibrahim
12:50-13:05 7 Muhammad Hamid Mahmood
13:05-14:00 Lunch
14:00-14:15 8 Zhengxing Wang
14:15-14:30 9 Awang Idris
14:30-14:45 10 Waled Daoud
14:45-15:00 11 Abdelrahman Zkria Mohamed
15:00-15:15 12 Mohamed Egiza
15:15-15:30 Break
15:30-15:45 13 Ahmed Lotfy Elrefai
15:45-16:00 14 Ahmad Syahrin Idris
16:00-16:15 15 Ding Dong
16:15-16:30 16 Shi-Chao Qi
16:30-16:45 17 Lu Zhang
16:45-16:55 Closing Remarks, Prof. Seigi Mizuno
16:55-17:00 Best Presenter & Awards
IV
INVITED SPEAKERS
Prof. Kazuo Arakawa Professor / Renewable Energy Center, Research Institute for Applied Mechanics, Kyushu University
Biography 2001-present: Associate professor at Research Institute for Applied Mechanics RIAM, Kyushu
University 1988-1989: Visiting researcher, University of Washington, USA.
1982: Research Associate, RIAM, Kyushu University
1982: D.Eng. from Osaka University
Membership in Academic Society
The Japanese Society for Experimental Mechanics (JSEM)
The Society of Materials Science, Japan
The Japan Society for Composite Materials
The Japanese Society for Non-Destructive Inspection
The Japan Society of Mechanical Engineers
Society for Experimental Mechanics
Presentation title Effect of time derivative of contact area on dynamic friction
Presentation Abstract: This study investigated dynamic friction during oblique impact of a golf ball by evaluating the ball’s angular velocity, contact force, and the contact area between the ball and target. The effect of the contact area on the angular velocities was evaluated, and the results indicated that the contact area plays an important role in dynamic friction. In this study, the dynamic friction force F was given by F= μN+μη.dA/dt, where μ is the coefficient of friction, N is the contact force, dA/dt is the time derivative of the contact area A, and η is a coefficient associated with the contact area.
Prof. Shigeo Yoshida Professor / Renewable Energy Center, Research Institute for Applied Mechanics, Kyushu University
Biography
Shigeo Yoshida, born in Fukushima, in 1967.
Working at Kyushu University since 2013, as a professor in Research Institute for Applied Mechanics
University Received B.E. Degree in Engineering Faculty of Kyoto University in 1990
Doctor of Engineering in Ashikaga Institute of Technology in 2007.
Industry Worked in Fuji Heavy Industries (SUBARU) since 1990, as an aerodynamic engineer for aircrafts and
wind turbines and transferred to Hitachi in 2012. .
Member of JSME, JSFM, JSES (Director 2008-2010),
JWEA (Director 2010-)
TSJ and a registered expert of IEC.
Best Technology Award (JSES, 2007)
Best Paper Award (JSES 2007, JWEA 2009)
Best Poster Award (Renewable Energy 2006)
Poster Award (JWEA, 2007, 2007, 2008, 2010)
Research Fundamental design, aerodynamics, control and safety of wind turbines Wind farm performance, fatigue mitigation, layout optimization Downwind rotor and tower shadow model
V
CONTENTS
CFRP ADHESIVE JOINTS AND STRUCTURES FOR OFFSHORE WIND-LENS TURBINE M R Abusrea, Shiyi Jiang, Dingding Chen, Kazuo Arakawa
1
IMMUNOSUPPRESSION BY COLON CANCER CELLS, MEDIATED BY TUMOR-SECRETED SOLUBLE FACTORS Moses K. Kamita, Arihiro Kano, Shindo Mitsuru
3
CATALYTIC PERFORMANCE OF AG-COATED ZEOLITE FOR SOOT OXIDATION Honcheng Ruan, Maiko Nishibori
5
ATTITUDE AND ALTITUDE STABILIZATION OF OUTDOOR TETHERED QUAD-ROTOR Tarek N. Dief, Shigeo Yoshida
7
DIFFERENT NANOSCALE ZERO VALENT IRONS FOR NITRATE-POLLUTED WATER REMEDIATION Ahmed M. E. Khalil, Osama Eljamal, Nobuhiro Matsunaga
9
WAVE-STRUCTURE INTERACTION USING FREE SURFACE LATTICE BOLTZMANN METHOD (FSLBM) Nik Mohd, Changhong Hu, Xuhui Li
11
STUDY ON DESICCANT AIR-CONDITIONING SYSTEM FOR AGRICULTURAL PRODUCT STORAGE IN PAKISTAN Muhammad H. Mahmood, Muhammad Sultan, Takahiko Miyazaki, Shigeru Koyama
13
THE INVESTIGATION OF THE COLORIMETRY TO MEASURE THE DEPOSITION THICKNESS ON THE PLASMA-FACING WALL IN QUEST Zhengxing Wang, Takahiro Shimoji, Kazuaki Hanada, Naoaki Yoshida, etc
15
NUMERICAL STUDIES OF NATURAL VENTILATION OF BUILDING WITH LEEWARD OPENINGS A. Idris, B. P. Huynh, Z. Abdullah
17
STATISTICAL EVALUATION OF COMPRESSION INDEX CORRELATIONS Waled A. Daoud, Kiyonobu Kasama, Naser M. Saleh, Abdelazim M. Negm
19
HETROJUNCTION DIODE OF NITROGEN-DOPED ULTRANANOCRYSTALLINE DIAMOND FILMS PREPARED BY COAXIAL ARC PLASMA DEPOSITION Abdelrahman Zkria, Tsuyoshi Yoshitake
21
ULTRANANOCRYSTALLINE DIAMOND/AMORPHOUS CARBON COMPOSITE FILMS SYNTHESIS ON CEMENTED CARBIDE SUBSTRATE BY COAXIAL ARC PLASMA DEPOSITION Mohamed Egiza, Hiroshi Naragino, Aki Tominaga, Kouki Murasawa, Hidenobu Gonda, etc
23
ORTHOGONAL FLUXGATE GRADIOMETER SENSOR AND ITS APPLICATION IN PARTICLE DETECTION Ahmed Lotfy Elrefai, Ichiro Sasada
25
DRY ETCHING OF GERMANIUM WAVEGUIDES BY USING CHF3 INDUCTIVELY COUPLED PLASMA Ahmad Syahrin Idris, Haisong Jiang, Kiichi Hamamoto
27
SUPPRESSING NEW GRAPHENE NUCLEI GENERATION BY HYDROGEN SWEEPING Ding Dong, Hiroki Ago
29
A HIGHLY ACTIVE Ni/ZSM-5 CATALYST FOR DEEP HYDROGENATION OF ARENES Shi-Chao Qi, Lu Zhang, Jun-ichiro Hayashi
31
THE ACCELERATED SOLVENT EXTRACTION OF XINYU COKING COAL AND ITS EXTRACTION MECHANISM Lu Zhang, Shi-Chao Qi, Koyo Norinaga
33
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
1
CFRP ADHESIVE JOINTS AND STRUCTURES FOR OFFSHORE
WIND-LENS TURBINE
M R Abusrea1, Shiyi Jiang1 , Dingding Chen2, and Kazuo Arakawa3. 1 Interdisciplinary Graduate School of Engineering Science, Kyushu University, Fukuoka, Japan
([email protected]) 2 National University of Defense Technology, China,
3 Research Institute for Applied Mechanics, Kyushu University, Fukuoka, Japan
Abstract: Novel wind-lens turbine designs can augment power output. Vacuum-assisted resin transfer molding (VARTM) is
used to form large and complex structures from a carbon fiber reinforced polymer (CFRP) composite. Typically, wind-lens
turbine structures are fabricated in segments, and then bonded to form the final structure. This paper introduces five new
adhesive joints, divided into two groups: one is constructed between dry carbon and CFRP fabrics, and the other is
constructed with two dry carbon fibers. All joints and CFRP fabrics were made in our laboratory using VARTM
manufacturing techniques. Specimens were prepared for tensile testing to measure joint performance. The results showed
that the second group of joints achieved a higher tensile strength than the first group. On the other hand, the tensile fracture
behavior of the two groups showed the same pattern of crack originating near the joint ends followed by crack propagation.
1. Introduction
Composite materials have high stiffness-to-weight
and strength-to-weight ratios, and have been used
for many applications including aerospace,
automotive, and wind turbine structures [1]. The
wind-lens, a curved ring around the turbine blades,
is manufactured from six identical parts joined
together to form the final structure. Consequently,
its performance depends not only on material
properties but also on the joining technique.
Bonded joints have mechanical advantages over
bolted joints because fibers are not cut, and stresses
are transmitted more homogenously [2].
This paper introduces various adhesive bonded
joints, made of carbon fiber reinforced polymer
(CFRP), for use in offshore wind-lens structures.
The main objective of this work was to develop
high-strength joint applicable to offshore wind-lens
structures. The strengths of five joints were
assessed. All joints and CFRP material tested in
this study were made using a technique developed
from the vacuum-assisted resin transfer molding
(VARTM) process.
2. Experimental work
The composite material was CFRP, consisting of
a carbon fabric (TENAX STS; 504 g m–2)
hardened with a resin (XNR6815/XNH6815). Four
unidirectional carbon fabric sheets were stacked
and molded together to form plates with an average
thickness of 2 mm [1]. All CFRP fabrics were
produced using VARTM, a variation of resin
transfer molding (RTM) in which a solid mold with
a flexible tape-sealed vacuum bag is used to replace
the closed mold. In the VARTM process,
reinforcements are stacked on a solid mold, which
is treated with mold releasing agent and covered
with a peel ply and distribution medium. They are
enclosed together with an inlet and a vent in a
vacuum bag and sealed with gum tape (see Fig. 1).
Joint strengths were evaluated via tensile testing
using standardized test specimens [1]. Fig. 2 shows
the dimensions of the specimens; the total length
was 250 mm and the width was 10 mm. Pairs of
GFRP tabs were used to reduce the stress when
holding each specimen.
The strength of the original CFRP was measured,
and used as a reference for the strength of
subsequent joints. Five joint types were tested,
divided into two groups. One was constructed using
dry carbon fabrics and CFRP. In this group, the
CFRP half of the joint was manufactured first, and
then re-molded again with dry carbon fabric. Fig. 3
shows types 1 and 2 of the first joint group. The left
half of both joints was a stepped CFRP portion that
had been molded, and the right side represents a
dry carbon fabric. We used these to investigate the
effects of the number of steps connected to dry
carbon fabrics, and therefore the major difference
between the two joints is the number of CFRP steps.
The second group was constructed with two dry
carbon fiber halves; thus, the whole joint was made
in a single step. Fig. 4 shows types 3, 4, and 5 of
the second joint group. These joints were named
laminated joint-1, laminated joint-2, and multi-
overlapped joint, respectively.
Fig. 1. A schematic view of the VARTM process
used in this work
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
2
Joint
Tab
35 mm 50 mm
250 mm
40 or 80 mm
2 mm2 mm
Fig. 2. The standard specimen dimensions used for
tensile testing
Mold
Distribution medium Vacuum bag
Carbon fiber
80 mm
(a)Peel Ply
(b)
CFRP
CFRP
Fig. 3. Joint group 1: (a) staircase joint-1, and (b)
staircase joint-2.
40 mm
(c)
(b)
(a)
Fig. 4. Joint group 2: (a) laminated joint-1, (b)
laminated joint-2, and (d) multi-overlapped joint.
3. Results and discussions
Figure 5 shows the tensile strengths of the five
joints, and the original CFRP. A tensile load of
34 kN was recorded for the CFRP. The lowest joint
tensile strength recorded was for staircase joint-1,
with a measured strength of 8.8 kN (26% joining
efficiency). However, the strength of the other
staircase joint, staircase joint-2, was significantly
higher (14.3 kN; 42% joining efficiency).
This behavior can be attributed to two factors.
First, resin residue on the CFRP surface before
joining can act as an insulator. Second, the absence
of overlap contact in these joints reduces the
contact area, resulting in a weaker joint [3]. On the
other hand, staircase joint-2 achieved a much
higher strength than joint-1. This is attributed to the
three fiber layers in that joint type that contact the
CFRP part, three times more than the number of
layers in joint-1. Hence, joining dry carbon fabrics
together resulted in generally higher strengths. The
laminated joint-1 had a tensile strength similar to
that of staircase joint-2, with a measured strength
of 14.7 kN. This can be attributed to the absence of
overlap contact between the two halves in
laminated joint-1, which reduces the strength and
promotes crack propagation near the joint ends.
The introduction of overlap areas not only
increases the contact area, but also increases joint
thickness. On the other hand, the remaining two
joints were much stronger than the previous four
joints. Laminated joint-2 and the multi-overlapped
joint had tensile strengths of 26.8 kN (79%) and
28.8 kN (85%), respectively. These two joints
performed similarly, with the major difference
being the greater thickness of the multi-overlapped
joint-2, which could be the reason for the higher
observed strength. Löbel et al. [9] constructed
CFRP joints based on stainless pins, which resulted
in a high joining efficiency of 83%. However, the
metal-to-carbon fiber contact caused galvanic
corrosion of the carbon fabrics, weakening the
structure over time [4].
0
5
10
15
20
25
30
35
40
Ten
sile
str
ength
, kN
8.8
14.3 14.7
26.828.8
34
Sta
ircas
e
join
t-1
Sta
ircas
e join
t-2
Lam
inat
ed
join
t-1
Lam
inat
ed
join
t-2
Multi-
ove
rlap
ped
join
t
Join
tless
CFR
P
Fig. 5. Tensile strengths of the joints and the
original CFRP material.
4. Conclusion
Five adhesive joints were designed using
manufacturing process developed from the
VARTM process. The tensile test results showed
low strength when one half of the joint is CFRP
fabrics, which was the case for the first two
developed joints. On the other hand, the last two
joints, laminated joint-2 and multi-overlapped joint,
showed higher tensile strength. However, joining
techniques that use dry carbon fibers are still
limited for simple shapes, so there are some
difficulties for applying these techniques for
complex curved shapes like wind blades and lens as
well.
References [1] Chen DD, Arakawa K, Jiang SY. Novel joints
developed from partially un-moulded carbon-fibre-
reinforced laminates. Journal of Composite
Materials, 2015, Vol. 49(14) 1777–1786
[2] Banea MD, Da Silva LF. Adhesively bonded joints
in composite material: an overview. J Mater Des
Appl 2009;223:1–18.
[3] LÖbel T., Kolesnikov B, Scheffler S, et al.
Enhanced tensile strength of composite joints by
using staple-like pins: working principles and
experimental validation. Compos Struct 2013; 106:
453–460.
[4] Wen-Xue W., Yoshiro T., Terutake M. Galvanic
corrosion-resistant carbon fiber metal laminates.
16th Int. conf. on composite materials.
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
3
IMMUNOSUPPRESSION BY COLON CANCER CELLS, MEDIATED
BY TUMOR-SECRETED SOLUBLE FACTORS
Moses K. Kamita1, Arihiro Kano2, Shindo Mitsuru2
1Molecular and Material Science, IGSES, Kyushu University - 2Institute for Material Chemistry and Engineering, Kyushu University
Abstract: In this study, soluble factors secreted by colon cancer cells (CT26) are being investigated. Conditioned medium
from cultured CT26 cancer cells was collected and analyzed for the presence of immunosuppressive compound. The
presence of the active compound in the samples was constantly monitored by measuring the suppression of IFN-γ expression
by ELISA using splenocytes from a normal mouse. Suppressive activity in CT26 conditioned medium was shown to be
mediated by a soluble factor(s) that is less than 10kDa. After fractionation with HPLC, suppression of IFN-γ expression was
detected in the two different fractions. Further processing of the fractions is needed for the identification of the specific
compounds that are responsible for the suppression of tumor immunity.
1. Introduction
The immune system works by distinguishing
self from non-self and eliminates the non-self. IFN-
γ is a pleiotropic cytokine that is produced
primarily by T-cells upon antigen stimulation, and
works as an antiviral, as well as an antiparasitic
agent in the body. It also inhibits the proliferation
of several normal and transformed cells. The
production of interferon-gamma (IFN-γ) in
splenocyte culture and its suppression by the
conditioned medium of tumor cells have previously
been reported1.
Effective tumor immunotherapy is hindered by
a number of obstacles such as the ability of tumor
cells to create a tolerant microenvironment,
activation of negative regulatory checkpoints in the
tumor microenvironment and the secretion of
immunosuppressive cytokines and soluble
inhibitory factors2. Additionally, tumor-associated
changes in myelopoiesis that lead to the excessive
accumulation of immature myeloid cells in the
tumor are thought to play a critical role tumor-
associated immunosuppression3,4. Although this
tumor-associated immunosuppression is thought to
be driven by soluble factors that are expressed by
cancer cells, their identity and mode of action
remain largely unknown.
Overexpression of different pro-inflammatory
cytokines in tumor conditions have been shown to
result in an elevated growth of tumors, as well as
other metastatic diseases. In addition, reports have
indicated that blocking these cytokines results in
significant reduction in the rate of tumor growth5,6
Tumor cells also secrete high amounts of pro-
inflammatory cytokines that have the potential to
induce a local pro-inflammatory microenvironment.
Although these observations are in agreement with
the reports that chronic inflammation plays a role in
tumor development and progression, there are no
much details on the link between these two
observations.
CT26 cells are murine colon tumor cells that
were developed through exposure of BALB/c mice
to N-nitroso-N-methylurethane resulting in a cell
line that is easily implanted and readily metastasize
7. The CT26 model in BALB/c mice has provided a
syngeneic test system for developing, as well as
testing different immunotherapeutic concepts8.
Using CT26 cells, this study aimed to identify the
soluble factor(s) that suppress the immune response
against tumor development. Suppression of IFN-γ
production in a splenocyte assay was used as an
indicator of the presence of active factors.
2. Material and Methods
Cell Culture. Murine colon tumor CT26 cells
were purchased from American Type Culture
Collection (ATCC) (Manassas, VA, USA), and
maintained with D-MEM (Wako Pure Chemical
Industries, Ltd., Osaka, Japan) supplemented with
5% heat- inactivated horse serum in a 5% CO2
atmosphere at 37°C. Balb/c mice were purchased
from Kyudo Co. Ltd. (Tosu, Japan) and all animal
experiments were carried out according to the
guidelines for the proper conduct of animal
experiments published by the Science Council of
Japan. All experimental protocols were approved
by the Ethics Committee and the Animal Care and
Use Committee of Kyushu University. Splenocytes
were prepared from a spleen of a normal mouse
and seeded at one million cells per well in a 96-
well culture plate (Thermo Fisher Science Inc.,
USA), stimulated with lipopolysaccharide and
cultured for 24 hours with or without 10% of the
test samples.
Conditioned Media Collection and
Processing: The tumor cells were cultured to sub-
confluence, and the medium changed to serum free
media. After two days, the medium was recovered
and filtered through a 10kDa filter. The filtrate was
separated using a C18 Sepak column and the
resulting sample fractionated using HPLC. The
presence of the active compound in the samples
was constantly monitored by measuring the
suppression of IFN-γ expression in a splenocyte
assay.
Enzyme-linked Immunosorbent Assay
(ELISA): Quantification of IFN-γ in conditioned
media and fractionated samples was performed by
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
4
ELISA (R&D Systems, USA), according to the
manufacturer’s instructions.
3. Results
In this study, the splenocyte assay was used to
study the soluble factors that are secreted by CT26
cells for their immunosuppressive activity. The
immunosuppressive activity of the conditioned
media was compared with that of 10kDa filtrate
and the fraction obtained from Sepak column
separation (Fig. 1). Higher activity was recorded in
the Sepak column sample compared with whole
media and 10K filtrate probably due to the
concentration of the active compounds after
separation.
Fig. 1: IFN-γ suppression in the presence of 10% of the
indicated samples. Splenocytes from a normal mouse were
incubated for 24hrs stimulated by LPS. Splenocytes stimulated
with LPS in the absence of the samples acted as the positive control (PC) while splenocytes with no stimulation and no
sample acted as the negative control (NC).
Further processing of the fraction after Sepak
column through fractionation by HPLC resulted in
the separation of the active compound into 11
fractions collected after every 5 minutes. A
splenocyte assay on the activity of the fractions
indicated the active compound(s) to be in fraction
number 2, and 5 eluted between 15-20 and 35-40
minutes respectively (Fig.2).
Fig. 2: IFN-γ suppression in the presence of 10% of the
indicated fractions. Splenocytes from a normal mouse were
incubated for 24hrs stimulated by LPS. Splenocytes stimulated with LPS in the absence of the samples acted as the positive
control (PC) while splenocytes with no stimulation and no
sample acted as the negative control (NC).
4. Discussion
Various soluble factors have been reported in
association with their role in suppressing the
immune response against the tumor. These factors
include IL-10, TGF-β, galectin-1, gangliosides,
PGE2, G-CSF, and M-CSF among others2. Here,
the immunosuppressive factor(s) from CT26 cells
that is responsible for this activity is a 10kDa
molecule. The presence of activity in two separate
fractions is an indication that more than one factor
is involved in this activity. Although different
factors use different mechanisms in different cancer
models to suppress the immune system, most of the
immunosuppressive factors suppress the immunity
through the myeloid-derived suppressor cells
(MDSC) by enhancing their proliferation. Small
factors such as PGE2 that can pass through the 10K
filter could be involved in the observed activity.
However, further analysis is needed to confirm the
identity of the compounds.
5. Conclusion
Use of splenocytes isolated from normal mouse
facilitated the detection of immunosuppressive
factors secreted by tumor cells. Further processing
of the fractions is needed for the identification of
the specific compounds that are responsible for the
suppression of tumor immunity. This identification
will pave way for the elucidation of the
mechanisms through which tumors evade the
immune response. In addition, the information may
be help in the development of tumor therapy.
6. References
1. Kano, A. Tumor cell secretion of soluble
factor(s) for specific immunosuppression. Sci.
Rep. 5, 8913 (2015).
2. Rabinovich, G. A., Gabrilovich, D. &
Sotomayor, E. M. Immunosuppressive
strategies that are mediated by tumor cells.
Annu. Rev. Immunol. 25, 267–96 (2007).
3. Gabrilovich, D. I. & Nagaraj, S. Myeloid-
derived suppressor cells as regulators of the
immune system. Nat. Rev. Immunol. 9, 162–74
(2009).
4. Ugel, S. et al. Immune tolerance to tumor
antigens occurs in a specialized environment of
the spleen. Cell Rep. 2, 628–39 (2012).
5. Voronov, E. et al. IL-1 is required for tumor
invasiveness and angiogenesis. Proc. Natl. Acad.
Sci. U. S. A. 100, 2645–50 (2003).
6. Apte, R. N. & Voronov, E. Interleukin-1--a
major pleiotropic cytokine in tumor-host
interactions. Semin. Cancer Biol. 12, 277–90
(2002).
7. Griswold, D. P. & Corbett, T. H. A colon tumor
model for anticancer agent evaluation. Cancer
36, 2441–4 (1975).
8. Castle, J. C. et al. Immunomic, genomic and
transcriptomic characterization of CT26
colorectal carcinoma. BMC Genomics 15, 190 (2014).
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
5
CATALYTIC PERFORMANCE OF AG-COATED ZEOLITE
FOR SOOT OXIDATION
Honcheng Ruan1, Maiko Nishibori1
1Department of Molecular and Material Sciences, Interdisciplinary Graduate School of Engineering Sciences, Kyushu
University, Kasuka, Fukuoka 816-8580, Japan; E-Mail:ruanhongcheng@126.com
Abstract: Ag-coated zeolite catalyst (Ag/HSZ890HOA) mixed with candle soot (CS) for 1, 10, 30 and 60 min, exhibited T
max (temperature according to highest peak of DTA curves) value of 494, 485,425 and 376/492 oC for T0-1, T0-10, T0-30, T0-60,
respectively. Interesting, catalyst mixing with CS for 60 min showed two T max peaks on differential thermal analysis (DTA)
curves.
1. Introduction
Environmental issues are harmful aspects on
human activity on the biophysical environment.
Some environmental issues are belong to air
pollution, such as Ozone depletion, Global
warming, Acid rain, Photochemical smog and PM
2.5 issue. Diesel particulate matter (PM) consists
principally of combustion generated carbonaceous
materials (soot) on which some organic compounds
have become adsorbed [1]. The research of
corresponding catalyst on PM oxidation become
more and more important.
2. Experimental
Ag-doped catalysts (4.5%) were prepared by
ordinary impregnation of HSZ891HOA, with an
aqueous solution of the nitrate salt, AgNO3. Ag-
coated zeolite catalyst (Ag/HSZ890HOA) and
candle soot (CS) were mixed by mixing machine
instead of mortar for 1, 10, 30 and 60 min, as
showed in Fig. 1. The products mixed with CS for
1, 10, 30 and 60 min were denoted as T0-1, T0-10, T0-
30, T 0-60.
Thermogravimetry (TG) and differential thermal
analysis (DTA) measurement were carried out for
catalytic oxidation of CS. The morphologies of the
products were analyzed by scanning electron
microscope (SEM).
3. Results and Discussion
Surface morphologies of catalysts mixing with CS
for different time (1, 10, 30 and 60 min) were
showed in Fig. 2. There just be one exothermic
peak corresponding to a weight loss step on TG
curves with mix time 1 and 10 min, another one
peak appeared with the increasing mix time
gradually. Therefore, an obvious double-shoulder
peak appeared on catalyst DTA curves after mixing
60 min. Tmax of DTA curves for catalyst
Ag/HSZ890HOA are listed in Table 1.
SEM images (Fig. 2) showed that the number
of broken catalyst particles increased obviously as
the increasing mix time from 1 min to 60 min.
Table 1
T max of DTA curves for Ag/HSZ890HOA catalyst with
different mix time.
Mix time
/ min
1
10
30
60
T max / oC
494
485
425
376/492
Fig. 1. TG and DTA curves of candle soot with
Ag/HSZ890HOA catalysts in different mix time with mix
machine (a-d) 1-60min.
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
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Fig. 2. SEM images of candle soot with Ag/HSZ890HOA
catalysts in different mix time with mix machine (a-d) 1-60min.
4. Conclusion
Ag-coated zeolite catalyst (Ag/HSZ890HOA)
shows a good catalytic performance. However, a
further study about the principle based on two
peaks on DTA curves need to be done.
5. References
[1] Cheol-B Lima, Hisahiro Einagab, "Yoshihiko Sadaokac, Yasutake Teraokab, Preliminary study on catalytic combustion-type sensor for the detection of diesel particulate matter", Sens. Actuators, B: Chemical, 160, 463-470 (2011).
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
7
ATTITUDE AND ALTITUDE STABILIZATION OF
OUTDOOR TETHERED QUAD-ROTOR
Tarek N.Dief1, Shigeo Yoshida2
1 Department of Earth System Science and Engineering
Kyushu University,[email protected] 2 Research Institute for Applied Mechanics
Kyushu University, [email protected]
Abstract: This paper presents an overview of the most effective ideas for the Quad-rotor project. The concept of
modelling using different methods is presented. The modelling part discussed the nonlinear model, and the
concept of linearization using small disturbance theory. Parameter identifications part explained the most
important parameters that affect the system stability and tried to get suitable solutions for these problems and
identify some parameters experimentally. The control part incorporates different classical schemes such as PD
and PID controllers to stabilize the Quad-rotor. The difference between the indoor and outdoor controller is
presented from the mathematical and the experimental techniques.
1. Introduction
Nowadays, automatic flying of intelligent vehicles
moving in space represents a huge field of
applications. The rapid development of the
microcontroller affects all control’s applications
which mean new control theory, new researches,
and new challenges. The applications of the
hovering aerial vehicles open the door for
researchers to present better controllers to achieve
more aggressive missions. Nonlinear control
theories and applications are the target of the
researchers to present or develop more controllers
which were very difficult to be implemented using
the old microcontrollers. Using the nonlinear model
will cancel the assumptions which we make during
the control design process; so we will deal directly
with the nonlinear model.
A lot of application for the Quad-rotor has been
applied especially for the outdoor flights. Civilian
application for the UAV includes atmospheric
analysis, mapping, maintenance inspection,
photography for natural disaster, etc…
2. System Identification and Control Design:
a. System Identification:
In the Quad-rotor model, we were dealing with a
fixed model and now we found a problem with the
parameters variation, so we need model can make
the update of the parameters real time by knowing
the history of the plant input also from the system
output data.
Placket’s model: This way depends on the least-
squares fitting. The concept of this model depends
on minimizing the square difference between the
predicted output from the calculation and
between the real data from the sensor data as
shown in equation (1):
Mean square error = (1)
And the following curves show the system open
loop transfer function parameters and plotting them
online.
Where, the system parameters are shown in
equation (2):
21
21
*2*11
*1*0
)(
)(
ZaZa
ZbZb
zU
zY (2)
Fig.1 system parameter b0 with time
Fig.2 system parameter a1, a2 with time
Also neural network is applied to make the system
identification for the system parameters (time series
prediction); also this algorithm is better from the
Placket’s model. Also the initial values have no
effect on the system parameters unlike the
Placket’s model.
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
8
Also applying the neural network is very important
in our application as the outdoor flights will have a
high disturbance due to the disturbance flow from
different directions. So we can make estimation for
the disturbance by modelling the system.
Fig.3 system response for the actual and estimated
data with time
b. Control design:
A PID controller was implemented because its
proportional gain aspect decreases the system time
to obtain desired state; its integral gain reduces the
steady state error, and the derivative gain will
increase the stability of the system. For our
problem, it becomes a SISO system and we have
the controller equation:
t
idpc edtKeKeKG
0
. (3)
After using (SISOTOOL) package in Matlab and
choosing the best gains to our system, it can be
used in the real model. These gains are for the
linear model so it is needed to use these gains with
the nonlinear model and compare between the
response between the linear and non-linear model
and tune it if necessary.
Fig.4 Block diagram of the Quad-rotor model
and controller.
Fig.5 Time response of the roll angle.
3. Conclusion
This paper presents the control design of outdoor
Quad-rotor. This controller is different for the
indoor Quad-rotors. The effect of wind and the
interaction between the wind and rotor flow
generate forces can disturb the system which mean
instability. Using different kind of system
identifications has advantages and disadvantages,
so due to your application and the hardware which
you are using will make you chose the suitable
algorithm. The classical control is used to due to its
simplicity in implementation and easier in tuning.
4. References
[1] Deif, T., Kassem, A., El Baioumi, G., Modeling and
Attitude Stabilization of Indoor Quad Rotor, (2014) International Review of Aerospace Engineering (IREASE), 7(2), pp. 43-47.
[2] Seul Jung, "A Position-Based Force Control Approach to a Quad-rotor System," Ubiquitous Robots and Ambient Intelligence (URAI), 2012 9th International Conference on , vol., no., pp.373,377, 26-28 Nov. 2012
[3] Etkin, B.: Dynamics of Flight. Stability and Control,
2nd edn. Wiley, New York (1982).
[4] Tarek N. Dief, Mohamed Abdelhady, Shigeo
Yoshida,”Attitude and altitude stabilization of quad
rotor using paramter estimation and self-tuning
controller”, AIAA Atmospheric Flight Mechanics
conference, doi: 10.2514/6.2015-2392.
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
9
DIFFERENT NANOSCALE ZERO VALENT IRONS FOR NITRATE-
POLLUTED WATER REMEDIATION
Ahmed M. E. Khalil, Osama Eljamal, Nobuhiro Matsunaga
Earth System Science and Technology (ESST), Interdisciplinary Graduate School of Engineering Sciences (IGSES), Kyushu
University, Co-author’s email: [email protected]
Abstract: In this study, four nanoscale zero valent iron (NZVI) types were characterized and compared for nitrate removal
from water. Through batch experiments, it was observed that old-purchased iron (OP-NZVI) had very low nitrate removal
efficiency (10%) for more than 8 hours. Treated iron (T-NZVI) removed approximately half of nitrate concentration within 3
hours. Synthesized iron (S-NZVI) successfully reduced the whole amount of nitrate in one hour. Meanwhile, the improved
iron (I-NZVI) removed the same amount within 20 minutes, which indicated the highest performance among other NZVIs.
1. Introduction
Nitrate is a well-known hazardous contaminant in
groundwater resulting from agricultural runoff,
domestic wastewaters, etc. It can be reduced to
nitrite causing methemoglobinemia, liver damage,
cancer, and so forth [1]. Attributed to high cost
effectiveness and reactivity, NZVI had proven its
high efficacy and efficiency in nitrate
decontamination from wastewater [2, 3]. However,
NZVI’s reactivity decreases through aging [4],
which requires a certain treatment to decrease the
thick passive shell layer of iron (I, II)
oxides/hydroxides. This study investigates the
effect of optimized treatment process on old-
purchased NZVI and compares nitrate removal
kinetics between OP-NZVI, T-NZVI, S-NZVI and
I-NZVI.
2. Materials and Methods
Ferric chloride, sodium borohydride and ethanol
were purchased for NZVI synthesis. Sodium nitrate
was used to prepare a reactant stock solution, while
pH buffer solution, hydrochloric acid and sodium
hydroxide were used for pH adjustment. Nano iron
powder was purchased a year ago. Anhydrous
copper chloride was used to enhance NZVI.
To produce T-NZVI, The surface of OP-NZVI
was washed using 0.1 N HCl solution (10 g iron
per 250 mL acidic solution) in 300 mL conical
glass flask [5]. The resulting slurry was washed
with ethanol then filtered using vacuum filter.
The S-NZVI was prepared according to the
following reduction method:
.
In this study, the synthesis conditions were
optimized based on previous research work [6].
Sodium borohydride (NaBH4, 98%, 1.1472 M)
was introduced into anhydrous ferric chloride
(FeCl3, 0.1434 M) using a roller pump (flow rate 1
L/h) with a volumetric ratio of 1:1 in 500 mL four-
neck glass flask. Anoxic condition was kept by
continuous flow of nitrogen gas. The reaction
mixture was stirred at 250 rpm and maintained at
25 ± 0.5 oC. After reduction, the jet-black iron
nanoparticles were vacuum-filtered and washed
with deionized (DI) water (>100 ml/g) and
anhydrous ethanol three times each. Finally, the
slurry was vacuum-filtered and used immediately
in batch experiments.
The batch experiments were anaerobically
carried out in 500 mL four-neck glass flask using
100 mg/L of nitrate solution and 2 g/L of NZVI as
shown in Fig. 1. The resulting mixture was kept at
25 ± 0.5 oC using water bath. At specific given time
intervals, 5 mL of solution sample were withdrawn
and filtered through a 0.22 μm membrane for
analysis of nitrate, nitrite, ammonium, ferrous, total
iron and total nitrogen. The off-gas was absorbed
by 100 mL acidic solution for analysis of ammonia
gas. 50 mg of CuCl2 was added in one of
experiments to enhance nitrate removal (the used
iron is denoted as I-NZVI).
Fig. 1. Schematic layout of batch experiment.
Concentrations of nitrogen compounds in
solution samples were analysed by UV–vis
spectrophotometer. To characterize NZVI, a
transmission electron microscopy (TEM), particle
size analyser, Brunauer–Emmett–Teller (BET)
specific surface area (SSA) analyser, X-ray
diffractometer (XRD) were used to determine
morphology, particle size, SSA and crystallinity,
respectively.
3. Results TABLE I
CHARACTERIZATION OF NZVIS
Property BET-SSA
(m2/g)
Mean aggregate size
(nm)
Particle size range (nm)
OP-NZVI 16.3 1388 70-100
TNZVI 15.2 950 50-70
SNZVI 61.1 50 20-50
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
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Fig. 2. TEM images of (A) OP-NZVI and (B) S-
NZVI at resolutions of 100 and 50 nm.
Fig. 3. XRD pattern of (A) OP-NZVI, (B) S-NZVI
and (C) spent I-NZVI.
Fig. 4. Nitrate removal kinetics of NZVIs.
4. Illustrations
Fig. 5. Effect of CuCl2 addition on nitrate removal
by NZVI.
5. Conclusion
This study distinguished the differences among
four types of NZVI, and succeeded to increase
nitrate removal efficiency by treatment of OP-
NZVI, using freshly-prepared NZVI synthesized
under optimized conditions, or enhancing nitrate
removal using NZVI with addition of other
contaminant via electrocatalytic reactions.
6. References [1] A. Kapoor, T. Viraraghavan, “Nitrate removal from
drinking water-review,” J. Environ. Eng., 123(4),
371-380 (1997).
[2] Y.-H. Hwang, D.-G. Kim, H.-S. Shin, “Mechanism
study of nitrate reduction by nano zero valent iron,” J.
Hazard. Mat., 185(2), 1513-1521 (2011).
[3] D. O’Carroll, B. Sleep, M. Krol, H. Boparai, C.
Kocur, “Nanoscale zero valent iron and bimetallic
particles for contaminated site remediation,” Advan.
Wat. Res., 51, 104-122 (2013).
[4] http://www.nanoiron.cz/en/news/136-nzvi-slurry-
ageing-behavior, viewed on 1/5/2015.
[5] J. Luo, G. Song,J. Liu, G. Qian, Z. P. Xu,
“Mechanism of enhanced nitrate reduction via micro-
electrolysis at the powdered zero-valent
iron/activated carbon interface,” J. Colloid. Inter. Sc.,
435, 21-25 (2014).
[6] Y.-H. Hwang, D.-G. Kim, H.-S. Shin, “Effects of
synthesis conditions on the characteristics and
reactivity of nano scale zero valent iron,” App. Cat.
B: Environmental, 105 (1), 144-150 (2011).
A B
0
500
1000
1500
2000
2500
3000
3500
4000
4500
0 20 40 60 80
Inte
nsi
ty (
Co
unts
per
sec
ond
)
2 Theta (degrees)
0
200
400
600
800
1000
1200
0 20 40 60 80
Inte
nsi
ty (C
PS)
2 Theta (degrees)
Fe0
100 nm
Fe0
Fe0
CuFe2O4.Fe3
O4
Fe0
FeOOH
Stimulated
Corrosion
Electrocatalytic
effect
Reduction
Cu2+
50 nm
Fe0
CuFe2O4.Fe3
O4
Fe0
Fe3O
4
Fe3O4
A
C
B
100 nm
50 nm
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
11
WAVE-STRUCTURE INTERACTION USING FREE SURFACE
LATTICE BOLTZMANN METHOD (FSLBM)
Nik Mohd1, Changhong Hu2, Xuhui Li3
1,3Interdisciplinary Graduate School of Engineering Science, Kyushu University 2Research Institute for Applied Mechanics (RIAM), Kyushu University
E-mail: [email protected], [email protected], [email protected]
Abstract: In the present study, we have developed the free surface LBM (FSLBM) algorithm for wave-structure interaction
flow problem. Standard Single Relaxation Time (SRT) approximation with the Bhatnagar-Gross-Krook (BGK) collision
model were used. In addition, a Smagorinsky Large Eddie Simulation (LES) Model was implemented in order to capture
turbulent structure in the flow. From the results, a good agreement was yielded with the published results and it provided a
validation benchmark to qualitatively verify the proposed approach.
1. Introduction
The lattice Boltzmann method (LBM) has become
an efficient method for modelling and simulating
complex fluid flows. Several advantages have
shown to be promising with algorithm operations,
data locality and computational parallelism [1]. On
the other hand, free surface flow problems have
been widely used in interdisciplinary research such
as in civil engineering and ocean engineering. For
instance, in the wave impact on offshore structure,
dam breaking, flood waves and others[2]. In this
paper, we present the progress of development of
interaction water wave by implementing the
FSLBM approach.
2. Lattice Boltzmann Method
2.1 LBM Basic
The evolution of the LBM method is described by
lattice Boltzmann equation (LBE) with the standard
lattice BGK approximation model. This is given by
[3]
(1)
(2)
. At each time , the particle
distribution function is located at the
lattice node, x at respective lattice velocity, ,
dimensionless relaxation time. Equilibrium
particle distribution function, is given by
(3)
which consider a lattice-dependent constant,
The macroscopic values for density and velocity of
particle distribution function is defined by
(4)
2.2 LES Smagorinsky Model
Naturally, free surface flows usually occur at very
high Reynolds numbers. In the lattice Boltzmann
framework, the dimensionless relaxation time is
defined by [2]
(5)
the quadratic equation is obtained as
(6)
Simplification modified relaxation rate, as
(7)
3. Free surface LBM algorithm
By using FSLBM algorithm proposed by [4], two
values will considered to calculate the fluid fraction
as given by
(8)
For an interface cell at x the mass balance with a
neighbor at is given by [5]
(9)
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
12
the mass for next step can be calculated by adding
to the current mass for interface cells from the mass
exchange for all directions is defined as
(10)
The corresponding free surface boundary
conditions will be constructed by [4]
(11)
4. Numerical Results
Several numerical simulations were conducted for
wave-structure interaction at a high Reynolds
number which implemented the D2Q9 LBM model.
The present numerical results were compared with
an observed experiment and published numerical
simulation by [1]. This study used the original
configuration of tank size with 45cm x 58cm which
was reported by [6].The computation with domain
mesh 464 x 360 was referred to the parameter
setting as indicated by [1]. As can be seen from the
results, in the early stage, the jet evolved slowly
and started to increase gradually to achieve a
similar pattern with the previous study in [1]. A
limitation to the present study is that it did not
consider the gate movement and surface tension
effect. Nevertheless, the overall results indicated a
qualitatively comparable result with the previous
study.
5.Conclusion
In this study, a free surface lattice Boltzmann
method (FSLBM) model has been developed to
study wave-structure interaction problems.
Extension of this work should be considered with
Multi-Relaxation Time (MRT) in order to reduce
the spurious oscillation. This is a preliminary study
using obstacle block. In the future study, we plan to
model wave maker algorithm to generate effective
water wave.
6. References [1] Christian F.Janssen, Stephan T.Grilli, Manfred
Krafczyk, “On enhanced non-linear free surface flow
simulations with a hybrid LBM-VOF model,”
Computers and Mathematics with Applications, 65,
211-229 (2013).
[2] Christian F.Janssen, Manfred Krafczyk, “Free
surface flow simulations on GPGPUs using the
LBM”, Computers and Mathematics with
Applications, 61, 3549-3563 (2011).
[3] Z. Guo, C. Shu, “Lattice Boltzmann Method and its
Applications in Engineering”, ISBN 978-981-4508-
29-2, (World Scientific Publishing, 2013).
[4] N. Thurey, “Physical based Animation of Free
Surface Flows with the Lattice Boltzmann Method”
Phd thesis, Universitat Erlangen-Nurnberg, 2013.
[5] C. van Trigt, “Free surface with lattice Boltzmann
with enhanced bubble model”, Computers and
Mathematics with Applications, 67, 331-339 (2014).
[6] A. Kolke, E.Walhorn, B.Hubner, D.Dinkler, “Strong
Couple analysis of fluid-Structure Interaction with
Free Surface Flow, “Proc.Appl.Math.Mech” 4, 338-
339(2004).
Fig.1. Breaking dam with an obstacle: experimental results of [1], hybrid LBM-VOF-PLIC Model
[1] compared to present numerical results LBM-LES
(a) t=0.16s (b) t=0.24s (c) t=0.32s (d)
t=0.50s
(e) t=0.16s (f) t=0.24s (g) t=0.32s (h) t=0.50s
(i) t=0.16s (j) t=0.24s (k) t=0.32s (l) t=0.50s
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
13
STUDY ON DESICCANT AIR-CONDITIONING SYSTEM FOR
AGRICULTURAL PRODUCT STORAGE IN PAKISTAN
Muhammad H. Mahmood1,*, Muhammad Sultan1, Takahiko Miyazaki2, Shigeru Koyama2
1Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, Japan 2Faculty of Engineering Sciences, Kyushu University, Japan
*Email: [email protected]
Abstract: The present study provides the basic understanding of desiccant air-conditioning (AC) system for storage of
agricultural products of Pakistan. In this regard, the study provides the ideal growth zones for various agricultural products.
The desiccant air-conditioning applicability has been determined for three different climatic conditions (A, B, C) in order to
achieve the sensible and latent load of AC for the studied products. It is determined that desiccant wheel perform higher
dehumidification under climatic condition ‘A; because of the maximum ambient air relative humidity. Consequently, higher
heat energy is required in climatic condition ‘A’ to regenerate the desiccant wheel. It has been concluded that the desiccant
AC system can be effectively used for agricultural product storage in many regions of Pakistan.
1. Introduction
1.1 Background of products storage
Pakistan is an agriculture based country, blessed
with fertile land and four seasons. A huge amount
of fruits and/or vegetables in Pakistan is affected
due to post-harvest losses, which are about 30-35%
and sometimes even more. These loses are mainly
due to the mechanical damage, physiological
deterioration, and attack of insects and pests
The agricultural products after the harvesting
act like living organism and perform respiration,
transpiration, ripening processes. Furthermore,
these products contain high moisture contents and
may spoil within few days after the harvest.
Therefore, their shelf or storage life can be
increased by retarding the physiological, bio- and
chemical changes through control of temperature
and relative humidity in the cold storage structure.
1.2 Motivation of the study
The temperature of the cold storage is the most
important factor to maintain the quality of the
product because the physiological and biological
reactions in products which are directly dependant
on it. The relative humidity of the storage space is
also crucial in controlling the loss of moisture
contents from the products and to keep them in
good physical and biological appearance [1].
The mechanical refrigeration and/or air-
conditioning systems are being used in cold
storages for preservation/storage of agricultural
products. Besides from other disadvantages of
mechanical refrigeration system like environmental
degradation, high energy requirements etc., it
cannot be used for on farm storage of many tropical
fruits and vegetables such as banana, tomatoes,
oranges, mangoes, and other leafy vegetables
because of chilling injury and discoloration [2].
The standalone evaporative coolers also cannot be
used in tropical climatic conditions because of
higher relative humidity. On the other hand, the
desiccant air conditioning (DAC) system has ability
to deal the sensible and latent load of air
conditioning distinctly which gives opportunity to
use this system for storage of agricultural products
efficiently. Therefore, a particular DAC system is
proposed in the present study for on-farm pre-
cooling or short term storage of tomatoes, sweet-
potatoes, watermelon and pears.
2. Ideal storage zone
The tomatoes, sweet-potatoes, watermelon and
pears belong to same compatible storage
temperature and relative humidity group. The
recommended temperature and relative humidity is
18-21°C and 85-90% respectively. The
approximate transit and storage life of these
products are given in Table I [4]. The ideal storage
zone for preservation of tomatoes, sweetpotatoes,
watermelons and pears is shown in Fig. 1. The
ideal DAC cycle is also drawn on the figure in
order to study the system compatibility for the
recommended storage conditions.
3. Proposed DAC system
A typical desiccant wheel based DAC system is
proposed for the preservation of fruits and
vegetables as shown in Fig. 2. Psychrometric
model [5] is used to analyse the desiccant wheel
performance under three different climatic
conditions (A, B, C) of the Pakistan with low
regeneration temperature (~40°C). The
representative values of temperature and relative
humidity of the climatic condition (A, B, C) are
given in Table II [4]. The indirect evaporative
cooler (IEC) is used to provide the conditioned
supply air to the cold storage structure
TABLE I
STORAGE LIFE OF THE STUDIED AGRICULTURAL PRODUCTS [4].
Products Storage life [weeks]
Tomatoes 1-3
Sweetpotatoes 16-28
Watermelons 2-3
Pears (ripening) 1-3
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
14
TABLE II
CLIMATIC CONDITIONS FOR DESIGNING THE DAC SYSTEM [4]
Climatic
conditions type
Temperature [°C] Relative humidity
[%]
A 24 80
B 28 60
C 32 50
Ideal storage zone for storage of tomatoes, sweetpotatoes, watermelons and pears
,
15
Dry bulb temeprature [ C]
20 25 30 35 40
5
0
Hu
mid
ity r
atio
[g/k
gD
A]
15
10
Fig. 1. The ideal storage zone and DAC cycle.
IEC
Fig. 2. The proposed DAC system [3].
4. Results and Discussion
The ideal DAC cycle for the climatic condition (A)
is drawn on the psychrometric chart as shown in
Fig. I. The inlet air at relative humidity 80% and
temperature 24°C passes through the desiccant
wheel. The desiccant wheel dehumidifies the air up
to 11.96 g/kgDA and increases its temperature as
35.08°C. This air is then entered to the heat
exchanger for sensible cooling.
0
1
2
3
4
5
6
7
8
40 50 60 70 80
Deh
um
idif
icat
ion [
g/k
gD
A]
Regeneration Temperature [ C]
A
B
C
Fig. 3. Effect of regeneration temperature on
desiccant dehumidification.
0
5
10
15
20
25
30
35
40 50 60 70 80
Hea
t in
pu
t [k
W]
Regeneration temperature [ C]
A
B
C
Fig. 4. Energy required to dehumidify the desiccant
wheel under different climatic conditions.
Finally, the air is passed through IEC to supply the
sensibly conditioned supply air to the products. The
DAC system operates in similar fashion for other
climatic conditions (B, C). Therefore DAC cycle
for only climatic condition (A) is represented in Fig.
1 to avoid the misunderstanding.
Analysis showed that the desiccant
dehumidification capacity increases with increasing
regeneration temperature as shown in Fig. 3.
Furthermore, desiccant wheel under climatic
condition A performs higher dehumidification than
other climatic conditions. It is because of higher
outdoor air relative humidity. On the other hand,
higher heat energy is required to regenerate the
desiccant wheel under climatic condition A than
the other studied conditions as shown Fig. 4.
5. Conclusion
The DAC system can achieve the thermal
conditions required for agricultural products
storage in Pakistan at different prevailing climatic
conditions. However, its applicability in dry
climatic areas is limited.
5. References [1] lal Basediya, Amrat, D. V. K. Samuel, and Vimala
Beera. “Evaporative cooling system for storage of
fruits and vegetables-a review.” Journal of food
science and technology 50.3 (2013): 429-442.
[2] Vala, K. V., F. Saiyed, and D. C. Joshi. “Evaporative
Cooled Storage Structures: An Indian Scenario.”
Trends in post harvest technology (2014).
[3] Miyazaki T, Oda T, Ito M, Kawasaki N, and Nikai I.
“The possibility of the energy cost savings by the
electricity driven desiccant system with a high
performance evaporative cooler.” Int symp innov
mater process energy syst (2010).
[4] Kitinoja, Lisa, and Adel A. Kader. “Small-scale
postharvest handling practices: a manual for
horticultural crops.” UC, Davis, postharvest
technology research and information center, (2002).
[5] Beccali, M, Butera, F, Guanella, R, and Adhikari, R.
S. “Simplified models for the performance evaluation
of desiccant wheel dehumidification.” International
Journal of Energy Research, 27.1 (2003): 17-29.
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
15
THE INVESTIGATION OF THE COLORIMETRY TO MEASURE THE
DEPOSITION THICKNESS ON THE PLASMA-FACING WALL IN
QUEST
Zhengxing Wang1, Takahiro Shimoji1, Kazuaki Hanada2, Naoaki Yoshida2, Mitsuki Miyamoto3, Hideki Zushi2, Hiroshi Idei2,
Kazuo Nakamura2, Akihide Fujisawa2, Yoshihiko Nagashima2, Makoto Hasegawa2, Shoji Kawasaki2, Aki Higashijima2,
Hisatoshi Nakashima2, Akira Kawaguchi2, Tadashi Fujiwara2, Kuniaki Araki2, Osamu Mitarai4, Atsushi Fukuyama5, Yuichi
Takase6, Kenji Matsumoto7, and Quest Group.
1Department of Advanced Energy Engineering Sciences, Interdisciplinary Graduate School of Engineering Sciences, Kyushu
University, kasuga, Fukuoka 816-8580, Japan [email protected] 2Research Institute for Applied Mechanics, Kyushu University, Kasuga, Fukuoka 816-8580, Japan, 3Department of Material
Science, Shimane University, Matsue, Shimane 690-8504, Japan, 4Institute of Industrial Science and Technology Research,
Tokai University, Kumamoto 862-8652, Japan, 5Department of Nuclear Engineering, Kyoto University, Kyoto 606-8501,
Japan, 6Graduate School of Frontier Sciences, University of Tokyo, Kashiwa, Chiba 277-8561, Japan, 7HONDA R&D Co.,
Ltd. Automobile R&D Center, Haga, Tochigi 321-3393, Japan
Abstract: A convenient innovative method named colorimetry is tried to be applied to the Kyushu
University Experiment with Steady-state Spherical Tokamak (QUEST) tokamak to measure the film thickness of deposition
on the plasma-facing wall. The colorimeter can measure the reflectivity of R-color, G-color and B-color in the same time.
The reflectivity is related with the film thickness and complex refractive index of deposition. In this paper, the result of
thickness of the deposition measured with colorimeter is compared with that from the reflectivity measured with ellipsometer.
They agree quite well with each other. The result shows that it is feasible to apply colorimeter to the measurement of film
thickness of deposition. This lays the foundation for the further study of application of colorimetry to the QUEST tokamak.
1. Introduction
For a future nuclear fusion reactor, the
characteristics of the plasma-facing wall including
the information of the deposition are studied for
understanding those such as tritium storage or the
hydrogen recycling [1]. The deposition thickness is
usually measured with TEM and ellipsometer. But
these two heavy devices are very difficult to be
applied to the actual plasma-facing wall directly.
Because of the convenience, the colorimetry can
measure the deposition thickness on the actual
plasma-facing wall easily. About the measurement of deposition thickness
the colorimetry is in good agreement with the
ellipsometry for a-C:H (amorphous hydrogenated
carbon) dominant deposition in TEXTOR [2]. But
for the metal first wall and divertor in ITER, the
deposition will contain metals and will not a-C:H
dominant any more. And for QUEST the first wall
is stainless steel and the divertor and limiter are
tungsten. After several campaigns the deposition
has been formed on the plasma-facing wall. The
main ingredient is the mixture of carbon and metal.
It is necessary to study the feasibility of the
colorimetry on measuring the metal-containing
deposition thickness.
2. The colorimeter
1. Measuring data RGB (Red, Green, Blue)
reflectivity.
2. Response range: R (590~720 nm), G
(480~600 nm), B (400~540nm).
Maximum sensitivity: R (615nm), G (540nm), B
(465nm). The sensitivity versus wavelength is
Gaussian distribution.
3. Sensor diameter: 8.1 mm.
4. Diameter of the integrating sphere: 47 mm.
5. Light source: white LED.
6. The reflectivity of light is output as RGB
values (0~1023).
(1)
(2)
(3)
3. The principle of measurement with the
colorimeter
Fig. 1. The principle of measurement of deposition
thickness with colorimeter
2
~
21
~
10
~
0 sinsinsin ininin (4)
1
~
111 cos2
ind
(5)
1
~
10
~
0
1
~
10
~
0s1
coscos
coscos
inin
ininr
1
~
00
~
1
1
~
00
~
1p1
coscos
coscos
inin
ininr
(6)
2
~
21
~
1
2
~
21
~
12
coscos
coscos
inin
ininr s
2
~
11
~
2
2
~
11
~
22
coscos
coscos
inin
ininr p
(7)
1
1
2
,2,1
2
,2,1
,s1
i
psps
i
psps
perr
errr
(8)
2
2
352
)615(
0RRI
R
eI
2
2
202
)540(
0GGI
G
eI
2
2
222
)465(
0BBI
B
eI
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
16
pspsp rrR ,,,s (9)
2
R ps RR
(10)
According to the equations from (4) to (10), if
the incident angle i0 and the complex refractive
index of support n2 have been known (For QUEST,
the support is stainless steel) and it is in the air, so
there is
),(R 11
_
dnf (11)
The colorimeter can measure the reflectivity R.
If the complex refractive index of deposition en1
has been known, then the deposition thickness d1
could be derived.
4. The measurement of complex refractive index
of deposition on the QUEST wall with samples
Fig. 2. The samples on the first wall of QUEST
Fig. 3. The T1, T2, T3, T4 and B15 measured with
TEM.
These samples could be measured with
ellipsometer and TEM so that the complex
refractive index of deposition could be studied.
Fig. 4. The measurement principle of the complex
refractive index of deposition with ellipsometry.
ipisi
ipip
i
isis eEEeEE
~~
, (12)
rprsi
rprp
i
rsrs eEEeEE
~~
, (13)
~
~
))()((
/
/Etan
s
pi
isip
rsrpi
r
re
EE
Ee isiprsrp
(14)
According to the equations from (4) to (9), and then
there is
),()(tan 1
~
12
~
1 dnfnfe e
i (15)
The Ψ and Δ could be measured with
ellipsometer directly. The n1 is the deposition’s
complex refractive index which contains two
parameters, refractive n1 and extinction coefficient
k1. The ne is the sample’s complex refractive index.
If the d1 has been measured with TEM, then the n1
could be derived.
5. The complex refractive index of the samples
and the deposition of T1, T2, T3, T4 and B15
The three maximum sensitive wavelengths of
RGB colorimeter have been chosen to calculate the
complex refractive index of deposition.
Fig. 5. The complex refractive index of the 21
samples and the deposition of T1, T2, T3, T4 and
B15
6. Conclusion
From the distribution of complex refractive
index of 21 samples, it is presented that on the
plasma-facing wall of QUEST there are three
regions in which the optical characteristic of
deposition is different. In the upper side and lower
side, we need do more experiment of TEM to get
more complex refractive index of deposition, so
that we can get right complex refractive index
which could be applied to the colorimetry.
7. References [1] K. Hanada, “Particle balance in long duration RF
driven plasmas on QUEST”,Journal of Nuclear
Materials, 463, 1084-1086 (2015).
[2] P. Wienhold, “Colorimetry of interference colours to
investigate thickness changes of protective coatings
in TEXTOR”, Nuclear Instruments and Methods in
Physics Research Section B: Beam Interactions with
Materials and Atoms, 94, 503 (1994).
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
17
NUMERICAL STUDIES OF NATURAL VENTILATION OF BUILDING
WITH LEEWARD OPENINGS
A. Idris1, B. P. Huynh2, Z. Abdullah3
1Universiti Kuala Lumpur Malaysian Spanish Institute, Kulim Hi-Tech Park, 09000 Kulim, Kedah Malaysia
[email protected] 2, 3Faculty of Engineering & IT, University of Technology, Sydney NSW 2007Australia
Abstract: Ventilation is a process of changing air in an enclosed space. Air should continuously be withdrawn and replaced
by fresh air from a clean external source to maintain internal good air quality, which may referred to air quality within and
around the building structures. In this work, computational simulation is performed on a real-sized box-room with
dimensions 5 m x 5 m x 5 m. Two opening of the total area 4 m2 are differently arranged, resulting in 4 configurations to be
investigated. A logarithmic wind profile upwind of the building is employed. A commercial Computational Fluid Dynamics
(CFD) software package CFD-ACE of ESI group is used. A Reynolds Average Navier Stokes (RANS) turbulence model &
LES turbulence model are used to predict the air’s flow rate and air flow pattern. The governing equations for large eddy
motion were obtained by filtering the Navier-Stokes and continuity equations.
1. Introduction
Natural ventilation is the process of supplying and
removing air through an indoor space without using
mechanical systems. In developed countries, most
of the buildings are responsible for 1/3 of all energy
consumption e.g. in US, about 30% of total energy
consumption is used in non-domestic buildings,
and of that fraction about 30% is used in heating
and cooling [1], [2], [3].
Single-sided ventilation has fewer adaptive
comfort hours than two-sided ventilation and
produces much less ventilation volume [4] is used
when there is non-availability of other choice.
The reliable methods of getting information
about the air flow and pressure distribution around
and inside the building are through full scale
measurements [5], scale model testing using wind
tunnel [6] and computational fluid dynamics (CFD)
[7, 8].
The common CFD techniques are direct
numerical simulation (DNS), large-eddy simulation
(LES) and Reynolds averaged Navier-Stokes
(RANS) equation with turbulence models. Each
technique handles turbulence in different ways [9,
10]. Among those techniques, RANS is widely
used by most CFD software [11], however, LES
should be more suitable than the RANS approach
to study highly three-dimensional or separated
flows, especially those in which the gradient
transport hypothesis, and consequently one and
two-equation models of turbulence, fails [12]. It
was introduced by Dearsdoff in the early 1970s
[13] for meteorological applications.
The present investigation is focused on the
application of three dimensional RANS and LES
modeling on wind driven natural ventilation of
double openings at single-sided buildings.
2. Methodology
This study involves 4 configurations models of
leeward double opening (Figure 1). The dimensions
of the building-like models are 5 m x 5 m x 5 m.
The computational domain constructed had a height
of 4H, width of 9H and length of 13H (H=5m),
sufficiently large to avoid disturbance of air flow
around the building [14]. A logarithmic wind
profile upwind of the building is employed.
The commercial software package CFD-ACE
from the ESI group is used for the computation.
2. Result & Discussion
The present results is about the study of the flow
patterns and air flow rate using RANS and LES
scheme when modelling wind driven natural
ventilation in buildings. The velocity components
have been determined, along streamwise and
vertical direction, respectively. LES is used to
compare with RANS as LES is produced more
precise results but more time-consuming method
[15].
Figure 1 shows the air flow pattern inside the
building. The opening is marked as A and B, where
the air enters the building through the lower
opening A and comes out through the upper
opening B. If the level of the opening is at the same
height, the air will enter through the lower area and
come out through the upper area of both openings.
Table 1 shows numerical values of air flow rate
of simulation that being performed at University of
Technology, Sydney. Each configuration gives
different flow rate and it is found that the highest
flow rate occurs at configuration a(iv) for RANS
and a(ii) for LES, whereas the lowest flow rate
occurred at configuration a(i) for both RANS and
LES.
4. Conclusion
In this recent study, RANS and LES approaches
have been applied to wind driven natural
ventilation in a cubic building. Both RANS & LES
scheme give almost the same air flow rate with the
difference between 4-8%. The location &
arrangement of opening influences the air flow rate
and air flow pattern.
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
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Table 1. Numerical values of airflow rate
Opening
Configuration
Air flow rate (m3/s)
RANS LES
a(i) 6.63 x 10-1 6.09 x 10-1
a(ii) 6.91 x 10-3 7.46 x 10-3
a(iii) 6.52 x 10-1 7.10 x 10-1
a(iv) 7.45 x 10-1 7.15 x 10-1
Configuration 2D-Airflow Pattern
a(i)
a(ii)
a(iii)
a(iv)
Figure 1 Double Opening on Leeward Wall
5. References [1] P. F. Linden, "The fluid mechanics of natural
ventilation," Annual Review of Fluid
Mechanics, vol. 31, pp. 201-238, 1999.
[2] QUT High‐Density Liveability Guide (2009,
28 March).
Thermal Comfort and Natural Ventilation.
Available:
http://www.highdensityliveability.org.au/pdf/1
_Thermal%20Comfort_23sep09.pdf
[3] J. Morrissey, T. Moore, and R. E. Horne,
"Affordable passive solar design in a temperate
climate: An experiment in residential building
orientation," Renewable Energy, vol. 36, pp.
568-577, 2// 2011.
[4] Y. Wei, Z. Guo-qiang, W. Xiao, L. Jing, and X.
San-xian, "Potential model for single-sided
naturally ventilated buildings in China," Solar
Energy, vol. 84, pp. 1595-1600, 9// 2010.
[5] M. M. Eftekhari, L. D. Marjanovic, and D. J.
Pinnock, "Air flow distribution in and around a
single-sided naturally ventilated room,"
Building and Environment, vol. 38, pp. 389-
397, 3// 2003.
[6] T. S. Larsen and P. Heiselberg, "Single-sided
natural ventilation driven by wind pressure and
temperature difference," Energy and Buildings,
vol. 40, pp. 1031-1040, // 2008.
[7] G. Gan, "Effective depth of fresh air
distribution in rooms with single-sided natural
ventilation," Energy and Buildings, vol. 31, pp.
65-73, 1// 2000.
[8] K. Visagavel and P. S. S. Srinivasan, "Analysis
of single side ventilated and cross ventilated
rooms by varying the width of the window
opening using CFD," Solar Energy, vol. 83, pp.
2-5, 1// 2009.
[9] Q. Chen, "Ventilation performance prediction
for buildings: A method overview and recent
applications," Building and Environment, vol.
44, pp. 848-858, 4// 2009.
[10] Q. Chen and L. Glicksman. Application of
computational fluid dynamics for indoor air
quality studies. Available:
http://www.accessengineeringlibrary.com/mgh
pdf/0071450076_ar059.pdf.
[11] V. Yakhot, S. A. Orszag, S. Thangam, T. B.
Gatski, and C. G. Speziale, "Development of
turbulence models for shear flows by a double
expansion technique," Physics of Fluids A:
Fluid Dynamics (1989-1993), vol. 4, pp. 1510-
1520, 1992.
[12] U. Piomelli, "Large-eddy simulation:
achievements and challenges," Progress in
Aerospace Sciences, vol. 35, pp. 335-362, 5//
1999.
[13] J. W. Deardorff, "A numerical study of three-
dimensional turbulent channel flow at large
Reynolds numbers," Journal of Fluid
Mechanics, vol. 41, pp. 453-480, 1970.
[14] Y. Jiang, D. Alexander, H. Jenkins, R. Arthur,
and Q. Chen, "Natural ventilation in buildings:
measurement in a wind tunnel and numerical
simulation with large-eddy simulation,"
Journal of Wind Engineering and Industrial
Aerodynamics, vol. 91, pp. 331-353, 2// 2003.
[15] G. Evola and V. Popov, "Computational
analysis of wind driven natural ventilation in
buildings," Energy and Buildings, vol. 38, pp.
491-501, 5// 2006.
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
19
STATISTICAL EVALUATION OF COMPRESSION INDEX
CORRELATIONS
Waled A. Daoud1, Kiyonobu Kasama2, Naser M. Saleh3, Abdelazim M. Negm4
1 PhD Student, Egypt-Japan University of Science and Technology, Alexandria, Egypt (email: [email protected]) 2 Associate Professor, Civil and Structural Engineering Division, Faculty of Engineering, Kyushu University, Japan
3 Associate Professor, Civil Engineering Department, Faculty of Engineering at Shoubra, Cairo, Egypt 4 Environmental Engineering Department Head, Egypt-Japan University of Science and Technology, Alexandria, Egypt
Abstract: Primary consolidation of cohesive soil can significantly affect the serviceability of overlying structures and its
amount is calculated using the compression index (Cc). Determination of Cc is complex and time consuming that raised the
need for using empirical correlations with simpler tests. Development of these correlations started as early as the 1940s and
new correlations still being developed. Most of these correlations were derived using data fitting with site-specific measured
values and was evaluated using simple statistics. Better statistical evaluation may reduce the correlation deviation. ATIC
method in-line with other evaluation measures was used to evaluate 92 compression index correlations using measured data
from Egypt, UAE, Iraq, and Indonesia. For the studied data, each statistical measure ranks the correlations differently,
especially for the best correlation. The advantages and shortcoming of each statistical measure were briefly introduced.
1. Introduction
Soil compressibility can significantly affect the
serviceability of the overlying structures [1]. For
cohesive soil; primary consolidation has the most
significant effect that is estimated using
compression index (Cc). Determination of Cc is
complex and time consuming that made empirical
correlations more important. Many correlations
were developed to estimate Cc for different soil
conditions as early as the 1940s and new
correlations still being developed [2].
Most of these correlations were derived from
data fitting of measurements at specific site
conditions that may cause large deviation if used
for other sites [3]. Better statistical evaluation may
reduce the overall deviation of the geotechnical
parameter and enhance the overall assessment.
Many researchers attempt to evaluate Cc
correlations using statistical measures for decades.
Giasi et al. [4] evaluated 32 correlations using both
ranking distance (RD) and Ranking Index (RI).
Yoon et al. [5] evaluated 15 correlations using
correlation coefficient (R) and K-factor. Rani and
Rao [6] evaluated 12 correlations using The mean
absolute difference (MAD). Onyejekwe et al. [7]
evaluate 18 correlations using the root mean square
of error (RMSE), K-factor, RD, and RI. Lee et al.
[2] used determination coefficient (R2) and mean
absolute difference (MAD) to evaluate 29
correlation.
Most of the commonly used statistical
evaluation measures had shortcomings that it
considers position conformity or trend conformity
separately. This shortcoming may cause
misjudgement of the correlation. This paper
evaluates 92 Cc correlations using commonly used
statistical measures and Amended Theil Inequality
Coefficient (ATIC) method as presented by Song et
al. [8]. ATIC method has the advantage that it takes
into account both position and trend conformities in
the overall evaluation process.
2. Used Data
Subsurface investigation reports were collected
from Egypt, UAE, Iraq, and Indonesia and entered
into customized geotechnical database. Data for
this study was collected with the condition that the
sample has all needed parameters to insure
consistency and accuracy of the evaluation process.
Table 1 shows descriptive statistical measures for
the used soil properties. TABLE I
DESCRIPTIVE STATISTICS OF THE USED SOIL PROPERTIES
Property Range Mean Std. Dev.
Initial Voids Ratio 0.32 - 4.35 1.58 0.84 Bulk Density (t/m3) 1.04 - 2.29 1.61 0.31
Water Content (%) 11.9 - 168.12 57.15 31.09
Liquid Limit (%) 17.1 - 166.2 62.68 25.22 Plasticity Index (%) 2.48 - 113.9 30.71 17.84
Compression Index 0.07 - 1.66 0.57 0.3
3. Used Correlations
Several correlations were developed to correlate the
Cc with field state and intrinsic properties as in
Table II. Total of 92 correlations were considered
in this study. TABLE II
CORRELATIONS WITH SINGLE SOIL PROPERTY
Cor.
ID Formula
Cor
. ID Formula
C01 C47
C02 C48
C03 C49
C04 C50
C05 C51
C06 C52
C07 C53
C08 C54
C09 C55
C10 C56
C11 C57
C12 C58
C13 C59
C14 C60
C15 C61
C16 C62
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
20
C17 C63
C18 C64
C19 C65
C20 C66 C21 C67
C22 C68
C23 C69
C24 C70
C25 C71
C26 C72
C27 C73
C28 C74
C29 [9] C75
C30 C76
C31 C77
C32 C78
C33 C79
C34 C80
C35 C81
C36 C82
C37 C83
C38 C84
C39 C85
C40 C86
C41 C87
C42 C88
C43 C89
C44 C90
C45 C91
C46 C92
Where e: voids ratio, n: porosity, : dry density (g/cm3), LL: liquid limit,
IP: plasticity index, WC: natural water content, and GS: specific gravity
4. Correlations Evaluation
Current correlation evaluation measures consider
position and trend conformities separately that may
lead to misjudgment and wrong selection. The
ATIC method as proposed by Song et al. [8] has
the advantage that it considers both position and
trend conformities.
Table IV shows the 5 top-most and bottom-most
ranked correlations based on ATIC method using
the procedure given in [8]; R2 and MAD values
based on the equations given in [2]; RMSE value
based on the equation given in [7]; and RI and RD
values based on the procedures given in [4]. TABLE V
THE 5 TOP-MOST AND BOTTOM-MOST RANKED CORRELATIONS
Rank ATIC R2 MAD RMSE RI RD
5 T
op
-
Most
1 C22 C29 C60 C60 C67 C02 2 C80 C79 C29 C67 C20 C34 3 C43 C10 C33 C17 C23 C35
4 C10 C02 C10 C33 C64 C49 5 C50 C04 C17 C64 C92 C27
5 B
ott
om
-
Mo
st
88 C03 C71 C62 C03 C11 C45
89 C14 C55 C83 C14 C03 C14
90 C13 C56 C14 C62 C14 C13 91 C62 C53 C13 C13 C62 C83 92 C15 C54 C15 C15 C13 C15
5. Conclusion
Total of 92 compression index correlations were
evaluated using commonly used statistical
measures in-line with ATIC method. The results
show that each statistical measure gave different
ranking for the correlations. ATIC method has the
advantage of considering position and trend
conformity in the evaluation process. R2 has the
shortcoming that it considers only the trend of the
values without considering their relative position.
MAD and RMSE values have the shortcoming that
they evaluate only the values’ position around the
average. The RI considers only the position of the
data. The RD is biased for the odd ratios between
the correlated and observed values.
Acknowledgments
Waled A. Daoud would is thankful to the Egyptian
Ministry of Higher Education (MoHE) and EJUST
for funding his PhD studies and special thanks to
Kyushu University for offering the tools and
equipment needed for the research.
References [1] J. E. Bowles, Foundation Analysis and Design,
5th ed., vol. 20, no. 3. McGraw-Hill, 1997.
[2] C. Lee, S.-J. Hong, D. Kim, and W. Lee,
“Assessment of compression index of Busan
and Incheon Clays with sedimentation state,”
Mar. Georesources Geotechnol., vol. 33, no. 1,
pp. 23–32, 2015.
[3] B. A. McCabe, B. B. Sheil, M. M. Long, F. J.
Buggy, and E. R. Farrell, “Empirical
correlations for the compression index of Irish
soft soils,” Proc. ICE-Geotechnical Eng., vol.
167, no. 6, pp. 510–517, 2014.
[4] C. I. Giasi, C. Cherubini, and F. Paccapelo,
“Evaluation of compression index of remoulded
clays by means of Atterberg limits,” Bull. Eng.
Geol. Environ., vol. 62, no. 4, pp. 333–340,
2003.
[5] G. L. Yoon, B. T. Kim, and S. S. Jeon,
“Empirical correlations of compression index
for marine clay from regression analysis,” Can.
Geotech. J., vol. 41, no. 6, pp. 1213–1221, 2004.
[6] C. S. Rani and K. M. Rao, “Statistical
evaluation of compression index equations,” Int.
J. Civ. Eng. Technol., vol. 4, no. 2, pp. 104–117,
2013.
[7] S. Onyejekwe, X. Kang, and L. Ge,
“Assessment of empirical equations for the
compression index of fine-grained soils in
Missouri,” Bull. Eng. Geol. Environ., 2014.
[8] J. Song, L. Wei, and Y. Ming, “A method for
simulation model validation based on Theil’s
inequality coefficient and principal component
analysis,” in AsiaSim 2013, Springer, 2013, pp.
126–135.
[9] B. Tiwari and B. Ajmera, “New correlation
equations for compression index of remolded
clays,” J. Geotech. Geoenvironmental Eng., vol.
138, no. 6, pp. 757–762, 2011.
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
21
HETROJUNCTION DIODE OF NITROGEN-DOPED
ULTRANANOCRYSTALLINE DIAMOND FILMS PREPARED BY
COAXIAL ARC PLASMA DEPOSITION
Abdelrahman Zkria1,2, Tsuyoshi Yoshitake1
1Department of Applied Science for Electronics and Materials, Kyushu University, Kasuga, Fukuoka 816-8580, Japan
E-mail: [email protected] 2Physics Department, Aswan University, Aswan 81528, Egypt,
Abstract: Nitrogenated ultrananocrystalline diamond/hydrogenated amorphous carbon composite films were prepared in
atmospheres of nitrogen and hydrogen mixed gases, by coaxial arc plasma deposition method. Effect of nitrogen
incorporated to the films was electrically investigated. The nitrogen-doped films possesses n-type semiconductor, it was
confirmed by studying the heterojunction of the film with p-Si. I-V curve of the junction exhibited a high rectifying action in
room temperature. The obtained results confirm that the Nitrogen-doped ultrananocrystalline diamond/hydrogenated
amorphous carbon composite film is a good candidate material for the electronic device applications.
1. Introduction
Diamond like carbon (DLC) materials have been
of considerable interest to many researchers in
recent years, mainly due to their amorphous nature
which opens up a possibility of incorporating of
other elements such Si, F, P, Ag and N1,2) which
upgrades its application in the field of
semiconductor technology. However, the high-
density defects and complex structure negatively
effect on the doping process; accordingly limit their
applications on the electronic devices.
On the other hand, semiconducting
ultrananocrystalline diamond/hydrogenated
amorphous carbon composite (UNCD/a-C:H) films
have a specific structure, wherein a large number of
diamond crystallites of less than 10 nm diameter
are embedded into an a-C:H matrix. These films
are applicable to biomedical, mechanical and
electronics applications3,4) because of their
advantageous features including their unique
optical and electrical properties. It has been
experimentally proved that the UNCD/a-C:H films,
prepared by pulsed laser deposition (PLD)5) and
coaxial arc plasma deposition6) possess large
optical absorption coefficients. This property
mainly attributed to the UNCD grain boundaries7).
UNCD/a-C:H films attract many researchers due
to the possibility of realizing n-type and p-type
conduction by Nitrogen and Boron doping,
respectively8,9). Concerning nitrogen-incorporated
UNCD, Bhattacharyya etal10) have reported that
UNCD films can be doped with nitrogen to achieve
a conductivity of 143 S/cm by chemical vapor
deposition (CVD) method. In our group, we
succeed to grow nitrogen-doped UNCD by PLD
method11), and it is experimentally proved that the
electrical conductivity of the film is enhanced with
increasing nitrogen contents, the enhancement of
conductivity with nitrogen doping was attributed to
the change of structure properties of films for both,
CVD12), and PLD8,11) methods.
In this letter, we report heterojunction diodes
comprising nitrogen-doped UNCD/a-C:H and p-
type Si and fabricated by coaxial arc plasma
deposition method. The heterojunction performance was evaluated based on current–
voltage (I–V) measured in dark at room
temperature.
2. Experimental details
UNCD/a-C:H films were deposited on p-type Si
(100) substrates at a substrate temperature of 550
ºC in a nitrogen and hydrogen mixed gas
atmosphere of 53.3 Pa by coaxial arc plasma
deposition (CAPD) with a coaxial arc plasma gun
equipped with a graphite target6). The CAPD
apparatus was evacuated down to a base pressure
of less than 10Pa using a turbo molecular pump,
and then hydrogen and nitrogen gas was fed into
the apparatus at a total inflow rate of 10 sccm.
Heterojunction was formed by depositing nitrogen
doped UNCD and p-type Si by radio frequency
(RF) sputtering. Pd electrode was deposited on
both sides for ohmic contact.
3. Results and Discussion
Formation of diamond grains by CAPD compared
with that by CVD has the following major
differences: (i) lower substrate temperatures, (ii)
much higher deposition rates, and (iii) no
requirement of substrate pretreatment using
diamond powder
Fig. 1. Schematic of coaxial arc plasma
deposition (CAPD) system.
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
22
From these differences, the formation mechanism
by CAPD should be greatly different from that by
CVD. Schematic of coaxial arc plasma deposition
(CAPD) system is shown in Fig.1. UNCD/a-C:H
films have electrically insulating properties In
contrast, 3 at. % nitrogen content UNCD/a-C: H
films deposited of hydrogen and nitrogen gases are
electrically conductive.
Fig.2. (a) Top view microscope image of the diode
(b). Schematic diagram of heterojunction
In order to illustrate the conduction type of
nitrogen-doped UNCD/a-C:H films, heterojunction
diodes have been manufactured by depositing films
on p-type Si substrates, as shown in Fig. 2. To
provide better understanding of these
heterojunction properties, dark IV curves of the
diodes measured in dark at room temperature, as
shown in Fig.3. I–V curve exhibited a rectifying
action similar to that of conventional p-n
heterojunctions with a rectification ratio of more
than 104 for bias voltage of ± 1 V.
−2 −1 0 1 2 3
0
1
2
3
4
5
Cu
rre
nt (m
A)
Voltage (V)
−5 −4 −3 −2 −1 0 1 2 3 4 510
−9
10−8
10−7
10−6
10−5
10−4
10−3
10−2
10−6
10−5
10−4
10−3
10−2
10−1
100
101
Curr
ent (A
)
Curr
ent density (
A/c
m2)
Voltage (V)
Fig. 3. Current-Voltage characteristics of the
heterojunction diode. Inset is linear scale.
These results evidently confirm that nitrogen-doped
UNCD/a-C:H possesses n-type conduction and
easily forms junction with p-type semiconductor
4. Conclusion
3 at. % nitrogen-doped UNCD/a-C:H film
deposited by CAPD method possessed n-type
conduction, Heterojunction diodes composed of n-
type UNCD/a-C:H and p-type Si showed a typical
rectifying action with a high rectification ratio of
~104 at bias voltage of ± 1 V. The obtained results
suggest n-UNCD/a-C:H as a promising candidate
to be applied in electronic and optoelectronic
devices
5. References 1. T. Yokota, T. Terai, T. Kobayashi, T. Meguro, M.
Iwaki, Surf. & Coatings Tech.201, 8048–8051
(2007).
2. S.F.Ahmed, D.Banerjee, K. Chattopadhyay, Vac.
84, 837–842 (2010).
3. S. Srinivasan, J. Hiller, B. Kabius, O. Auciello,
Appl. Phys. Lett. 90, 134,101, (2007).
4. Williams, Semicond. Sci. Technol. 21, R49
(2006).
5. K. Hanada, T. Nishiyama, T. Yoshitake, and K.
Nagayama: J. Nanomater, 901241 (2009).
6. K. Hanada, T. Yoshida, Y. Nakagawa, and T.
Yoshitake: Jpn. J. Appl. Phys. 49, 125503 (2010).
7. T. Yoshitake, A. Nagano, M. Itakura, N. Kuwano,
T. Hara, and K.Nagayama: Jpn. J. Appl. Phys. 46,
L936 (2007).
8. S. Al-Riyami, S. Ohmagari, and T. Yoshitake,
Appl. Phys. Express 3, 115102 (2010).
9. S. Ohmagari and T. Yoshitake, Jpn. J. Appl. Phys.
51, 090123 (2012).
10. Bhattacharyya, O. Auciello, J. Birell, J.A. Carlisle,
L.A. Curtiss, A.N. Goyette, D.M. Gruen, A.R.
Krauss, J. Schlueter, T. Sumant, P. Zapol, Appl.
Phys. Lett. 79, 1441 (2001).
11. S. Al-Riyami, S. Ohmagari, T. Yoshitake:
Diamond Relat. Mater.19, 510–513 (2010)
12. J. Birrell, J.E. Gerbi, O. Auciello, J.M. Gibson,
D.M. Gruen, J.A. Carlisle, Appl. Phys.Lett. 93, 9
(2003).
13. Williams, M. Nesladek, M. Daenen, S.
Michaelson, A. Hoffman, E. Osawa, K.Haenen,
R.B. Jackman, Diamond Relat. Mater. 17, 1080
(2008).
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
23
ULTRANANOCRYSTALLINE DIAMOND/AMORPHOUS CARBON
COMPOSITE FILMS SYNTHESIS ON CEMENTED CARBIDE
SUBSTRATE BY COAXIAL ARC PLASMA DEPOSITION
Mohamed Egiza1, 2, Hiroshi Naragino2, Aki Tominaga2, Kouki Murasawa3, Hidenobu Gonda3, Masatoshi Sakurai3, and
Tsuyoshi Yoshitake2 1 Mechanical Engineering Department, Kafrelsheikh University, Kafrelsheikh, 33516, Egypt, [email protected]
2 Department of Applied Science for Electronics and Materials, Kyushu University, Japan, 3 OSG Corp., Japan
Abstract: Ultrananocrystalline diamond/amorphous carbon composite films, wherein a larger number of diamond grains
with diameters of less than 10 nm are embedded in an amorphous carbon matrix, were deposited on cemented carbide (WC-
6wt.% Co) substrates by using coaxial arc plasma deposition at different repetition rates and deposition temperatures. The
hardness and Young’s modulus were measured by nanoindentation. The film deposited at a repetition rate of 1 Hz and room
temperature exhibited the maximum hardness of 51 GPa and modulus of 520 GPa. This implies that catalytic effects of Co in
the WC-Co substrates, which induce the graphitization of the films, can be suppressed by the low deposition temperature,
since the catalytic effects are enhanced with increasing temperature.
Key words: Nanodiamond, Hard coating, Coaxial arc plasma deposition, CAPD, Nanoindentation, Cutting tools
1. Introduction
Hard coating can give functions such as enhanced
hardness, chemically stable surface, and thermal
protection to mechanical tools, particularly
lengthen the lifetime of the tools. Cathodic arc
discharge has ever been employed for the
deposition of sp3-rich amorphous carbon film
coatings [1], since this method can provide highly
energetic carbon ions, which is indispensable for
the formation of sp3 bonds, onto substrates [2- 4].
In addition to the merits of cathodic arc
discharge, coaxial arc plasma deposition (CAPD)
has the following distinctive feature: a coaxial arc
plasma gun is equipped with an anodic cylinder
that can bunch ions ejected from a cathodic
graphite rod located inside the cylinder. Owing to
this structure, a supersaturated condition with
highly energetic ions can be realized, which is
desired for the growth of ultrananocrystalline
diamond (UNCD) crystallites [5]. CAPD can form
ultrananocrystalline diamond/amorphous carbon
composite (UNCD/a-C) films without the pre-
treatment of substrates with diamond powder [6]. A
high hardness of UNCD/a-C films are attributed to
the coexistence UNCD grains and sp3-rich a-C [7].
Cemented carbide (WC-6wt.% Co), which is a
typical cutting tool substance, contains Co that
induce graphitization of diamond. Since the
substrate temperature is increased, the catalytic
effects of Co is enhanced [8-10], polycrystalline
diamond coating by chemical vapour deposition is
made after the preferential etching of the Co.
CAPD make possible the deposition of UNCD/a-
C:H films at low temperature without the pre-
treatment of substrates. The process and condition
of deposition are completely different between
CAPD and CVD.
In this study, the validity of employing CAPD
for UNCD/a-C coating is investigated, and the
influences of cemented carbide substrates on the
film growth and mechanical properties were mainly
discussed.
2. Experimental procedures
UNCD/a-C films with thicknesses of 2-3 µm were
deposited on cemented carbide plate substrates with
dimensions of 10 mm diameter and 4 mm thickness
by CAPD with a graphite target. As shown in Fig. 1,
the film was not peeled off. The main conditions of
samples are summarized in Table 1. The films
surfaces were observed by scanning electron
microscopy. The hardness and Young’s modulus of
the films were measured by nanoindentation.
Fig.1. Optical images of (a) uncoated and (b)
UNCD/a-C-coated cemented carbide plate
substrates.
TABLE I
Typical preparation conditions.
sample 1 sample 2 sample 3
Substrate Temp. [℃] 550 RT RT
Repetition Rate [Hz] 5 5 1
3. Results and discussion
Fig.2 shows the X-ray diffraction pattern of the
films. Diffraction rings due to diamond-111 and
220 are observed, which evidently indicates the
formation of UNCD grains in the films.
Whereas the film (sample 1) deposited at 550
C and 5 Hz exhibited 17.3 GPa hardness, films
deposited on Si substrates at the same conditions
exhibited approximately 30 GPa. This reduction in
hardness should be attributed to the catalytic effects
of Co containing in the cemented carbide [8-10].
(a) (b)
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
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The film deposited at room temperature and 5 Hz
(sample 2) exhibited 31.8 GPa hardness and 294
GPa Young’s modulus. At the low substrate
temperature, as shown in Fig. 3, the hardness and
Young’s modulus are obviously enhanced, which
implies that graphitization due to the Co catalytic
effects are suppressed at the low substrate
temperature.
Figure 4 shows typical SEM images of the film
surfaces. The films deposited at 550 C (sample 1)
obviously comprises large grains as compared with
those of sample 2, which might come from the
graphitization.
Fig. 2. XRD pattern of typical UNCD/a-C film.
Fig.3. Comparison in hardness and Young’s
modules among samples.
Fig. 4. SEM images of film surface of (a) sample 1
and (b) sample 2.
The film deposited at room temperature and 1
Hz (sample 3) exhibits 51.3 GPa hardness and 520
GPa Young’s modulus. Both hardness and modules
are evidently enhanced with decreasing repetition
rate of discharge from 5 to 1 Hz. The long interval
time 1 s at 1 Hz is advantageous from the
viewpoints of cooling. In other words, an increase
in the effective substrate temperature might be
suppressed at 1 Hz owing to the long interval time,
since highly energetic species are arrived at the
substrate and the effective temperature on the
substrate surface should temporally be increased.
4. Conclusion
UNCD/a-C films were deposited on cemented
carbide substrates containing Co by CAPD. It was
found that the low temperature growth is effective
for suppressing the graphitization due to the Co
catalytic effects and CAPD, that makes the low
temperature growth possible, is a promising
method for the hard coating applications of
UNCD/a-C on cemented carbide.
Acknowledgments
This work was partially supported by Osawa
Scientific Studies and Grants Foundation.
References [1] M.Chhowalla et al., “Stationary carbon cathodic arc:
Plasma and film characterization,”J. Appl. Phys., 79,
2237-2244 (1996).
[2] D.Liu et al., “Filtered pulsed carbon cathodic arc:
plasma and amorphous carbon properties,”J. Appl.
Phys., 95, 7624-7631 (2004).
[3] J.J.Cuomo et al., “Vapor deposition processes for
amorphous carbon films with sp3 fractions
approaching diamond,”J. Appl. Phys., 70, 1706-1711
(1991).
[4] M.Chhowalla et al., “Influence of ion energy and
substrate temperature on the optical and electronic
properties of tetrahedral amorphous carbon (ta-C)
films,”J. Appl. Phys., 81, 139-145 (1997).
[5] K. Hanada et al., “Time-Resolved Spectroscopic
Observation of Deposition Processes of
Ultrananocrystalline Diamond/Amorphous Carbon
Composite Films by Using a Coaxial Arc Plasma
Gun,” Jpn. J. Appl. Phys., 49, 08JF09 (2010).
[6] K. Hanada et al., “Formation of
Ultarananocrystalline Diamond/Amorphous Carbon
Composite Films in Vacuum Using Coaxial Plasma
Gun,” Jpn. J. Appl. Phys., 49, 125503 (2010).
[7] Nevin N. Naguib et al., “Enhanced nucleation
smoothness and conformality of ultrananocrystalline
diamond (UNCD) ultrathin films via tungsten
interlayers,” Chem. Phys. Lett., 430, 345-350 (2006).
[8] Mario Lessiak et al., “Diamond coatings on hardmetal
substrates with CVD coatings as intermediate
layers,” Surface& Coatings Tech., 230,119-123
(2013).
[9] R. Haubner et al., “On the formation of diamond
coatings on WC/Co hard metal tools,” Ref. Metal.
&Hard Matt., 14, 111-118 (1996).
[10] R. Haubner et al., “Behaviour of Co binder
phase during diamond deposition on WC-Co
substrate,” Diamond Rel. Mat., 2, 910-917
(1993).
(a) (b)
1µm 1µm
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
25
ORTHOGONAL FLUXGATE GRADIOMETER SENSOR AND ITS
APPLICATION IN PARTICLE DETECTION
Ahmed Lotfy Elrefai1, Ichiro Sasada2
1 Applied Science for Electronics and Materials, kyushu University, Kasuga, Japan, [email protected] 2 Applied Science for Electronics and Materials, kyushu University, Kasuga, Japan
Abstract: A novel method for constructing an integrated gradiometer and magnetometer is proposed based on Fundamental
Mode Orthogonal Fluxgate (FM-OFG) operation. In the integrated sensor construction, the summation of both sensor head
outputs is used for the magnetometer operation and the subtraction of them is used for the gradiometer operation. The
baseline separation distance between the sensor heads is adjustable. The sensor heads pair can be configured either axially
or in parallel. Experiments were conducted with axial configuration of 5 cm baseline to show the selective detection
capability to gradient and homogeneous magnetic field. The sensing system presented can be used to measure the average
and the gradient of input magnetic field and its interesting applications are the gradiometric sensing of magnetic field
distribution anomalies in relatively large homogenous magnetic field interference.
1. Introduction
The gradiometer is a sensor to detect the gradient
of the magnetic field. There are two methods to
make the gradiometer. One method is electronic;
where two identical magnetometers are used and
the gradient is obtained by subtracting one
magnetometer’s output from the other’s. However,
an obvious drawback with the electronic
gradiometer is that two complete magnetometers
are needed and that a wide dynamic range with a
good linearity is needed for the high resolution
measurement. The other method uses a single
sensor head and is able to obtain the difference of
magnetic fields at two specific points. A common
structure of this type of gradiometer heads uses two
pickup coils wound on a single core [1]. The
system becomes compact and can be built with a
single driving and detection electronic set, however
the base line is fixed and making a good balance
between two pickup coils to suppress uniform
magnetic field is not easy.
So in order to build a gradiometer having
positive aspects of both methods, we propose a new
method for building a gradiometer based on the
fundamental mode orthogonal fluxgate (FM-OFG)
mechanism as shown in Fig. 1 [2]. The proposed
FM-OFG gradiometer is composed of two identical
sensor heads having hairpin-shaped amorphous
wire core with a pickup coil wound around it. The
pickup coils of the two heads are connected in
counter series; thus allowing the differentiation of
the signal on the sensor head level. The proposed
configuration allows the gradiometer to have the
advantage of a flexible baseline while minimizing
the used electronics set and also allowing more
amplification of the measured signal. The
developed gradiometer heads show high
suppression ratio of uniform magnetic field noise
and has high sensitivity to magnetic field gradients;
which demonstrates the sensor capability of being
implemented in various applications for
measurement of small magnetic field gradients.
One of the applications for the FM-OFG
gradiometer is the detection of magnetic particles
in unshielded environment.[3] The developed
prototype particle detection system offers size, cost
and weight reduction as compared to existing
particle detection systems. The system has been
investigated numerically to optimize various design
parameters of the system. Experimental setup has
been developed to evaluate some of the
numerically predicted results. Steel balls were
successfully detected down to the diameter of 50
µm.
Fig. 1. Schematic sensor circuit
2. Experimental Setup
An illustration of the sensor construction is shown
in Fig. 1. The gradiometer head is composed of two
FM-OFG heads of length 30 mm. Each sensor head
has amorphous wire core of 120 µm diameter. A
pick up coil wound on each core, where the pickup
coils of both heads are connected in counter series.
The excitation current is applied to the amorphous
wire core of both heads in series. Figure 2 shows
the fabricated gradiometer head. The excitation
current has 40 mA dc bias current and 100 kHz ac
current of 12 mA root-mean-square, which
establishes the fundamental mode operation.
Fig. 2. FM-OFG gradiometer with plastic
protection cover
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
26
The experimental setup of the magnetic particle
detection system is realized based on the
considerations taken from the results of the system
numerical analysis. The two heads of the
gradiometer are fixated in parallel configuration
with an 8 mm separation baseline, which is the
minimum baseline considering that each sensor
head is placed inside a plastic casing of radius 4
mm for protection of the pickup coil and the
amorphous wire core. The plastic casing of the
sensor head also limits the minimum lift-off to 5
mm with a 1 mm clearance between the moving
particle and the sensor case. Magnetic particle
samples are prepared using steel balls of diameters
160 μm, 120 μm, 70 μm and 50 μm in order to
evaluate the detection system performance. The
particles are pre-magnetized using a neodymium
magnet and then placed on the rotating table for the
gradiometer to measure the remnant magnetization.
For a particle to be detectable, the magnitude of the
output signal should be higher the sensor noise
level taken to be 0.5 nT/m at 1 Hz from Fig. 3. To
maximize the amplitude of the measured flux
gradient, the particles are placed on the rotating
table such that they pass at 2.5 mm to the inner side
from the tip of each sensor head. The output signal
of the sensor electronic circuit is amplified 400
times and passed on low pass filter of 20 Hz cutoff
frequency and High pass filter of 2 Hz cutoff
frequency.
3. Results and Discussion
The application of magnetic particle detection
using FM-OFG gradiometer is affected by various
design parameters. Hence, numerical analysis of
the system using finite element method (FEM) has
been conducted to determine the optimized values
to be used in the construction of the experimental
setup. In Fig. 3, the picked up magnetic field
gradient by the gradiometer is shown for the
variation of the particle position for x, y, and z
dipole moment directions. For the x direction
dipole moment, the maximum amplitude of the
measured signal is around a quarter of that of the y
and z direction dipole moments. Hence, to improve
detection capability of the sensor, it will be more
convenient to pre-magnetize the sample particles in
Fig. 3 Gradiometer output [T/m] vs. particle
position
y or z directions. At midway of particle movement,
i.e. the particle is situated at midpoint of the
baseline separation distance; the y direction dipole
achieves the maximum signal amplitude, while the
z dipole induces equal axial flux in the same
direction to both heads; which leads to omission of
the axial flux density gradient.
Experimental results from the detection system
prototype are shown in Fig. 4. The 160 μm and 120
μm particles show the y direction magnetization
dipole waveform pattern, while the 70 μm and 50
μm particles are showing the z direction one. At the
specified lift-off distance, i.e. 5 mm, the 50 μm
particle was detectable at a peak output value of 4
nT/m and a signal to noise ratio of 5, which is
comparable to recently reported results for a
superconducting quantum interference device
(SQUID) detection system with magnetic shielding,
where a 50 μm particle was detected with signal to
noise ratio of 10 at 3 mm lift-off distance.
Fig. 4. Gradiometer output [T/m] for steel balls of
diameters 160 µm, 120 μm, 70 μm and 50 μm
4. Conclusions
New magnetic particle detection system in
unshielded environment was proposed using FM-
OFG gradiometer in which differentiation is taken
at sensor head level. Numerical analysis was
conducted to demonstrate the system output and
determine the optimum values for the system
design parameters. The developed experimental
system successfully detected a 50 μm steel ball in
unshielded environment with signal to noise ratio
of 5. The proposed detection system has potential
of detecting smaller particles. In addition, the
developed particle detection system can also be
used for magnetic nanoparticles (MNP) detection
for liquid phase Immunoassay applications.
5. References [1] M. Janosek et al, “Single-core fluxgate gradiometer
with simultaneous gradient and homogeneous feedback
operation,” J. Appl. Phys., 111, 07E328 (2012).
[2] I. Sasada and S. Harada, “Fundamental mode
orthogonal fluxgate gradiometer,” IEEE Trans. On
Magn., 50, 4007404 (2014).
[3] A. L. Elrefai and I. Sasada, “Magnetic particle
detection in unshielded environment using orthogonal
fluxgate gradiometer,” J. Appl. Phys., 117, 17C114
(2015).
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
27
DRY ETCHING OF GERMANIUM WAVEGUIDES BY USING
CHF3 INDUCTIVELY COUPLED PLASMA
A. S. Idris*, H. Jiang, and K. Hamamoto
Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, 6-1, Kasuga-Koen, Kasuga, Fukuoka
816-8580, Japan.
*E-mail: [email protected]
Abstract: A dry etching procedure to etch germanium in a CHF3 inductively coupled plasma (ICP) using a polymer based
photoresist mask was developed to obtain a high selectivity ratio as well as to obtain a near vertical anisotropic sidewall etch profile.
In this study, a sidewall angle of 85° with an etch rate of 190 nm/min was obtained through optimization of the ICP bias power to
fabricate germanium waveguide structures with no under-cut.
1. Introduction
The integration of optoelectronics and electronics that
are compatible with existing Si based complementary
metal-oxide-semiconductor (CMOS) technology is a
much highly desired objective. Numerous concepts
have been investigated such as in hybrid photonic
integration of III-V devices and monolithic Si photonic
integration. Although hybrid III-V devices integration
has made tremendous progress in recent years, there
are still difficulties integrating it into the standard
CMOS flow such as incompatibility in the fabrication
and bonding procedures and temperatures. Monolithic
Ge-based photonics has been touted as one of the most
promising options in order to realize active and passive
optical functionalities in Si CMOS-compatible
photonic circuitry [1]. Reports have been published
concerning the implementation of Ge-based devices
showing efficient optical modulation and photo
detection within the telecommunication wavelength
range and although despite being an indirect bandgap
semiconductor, the direct bandgap optical properties of
Ge have also been extensively reported for use in
active optical devices [1].
Majority of the Ge devices reported however, tend
to make use of a oxide or metal hard mask during the
fabrication process due to the faster etching rate of a
polymeric photoresist mask compared to Ge [2].
Removal of the hard mask can be done through plasma
processing. However, exposure to further plasma
processing may lead to additional damage to the
structures surface and sidewall and can lead to greater
loss [3]. In this study, a novel dry etching fabrication
process for Ge was developed and optimized using a
polymeric mask to produce a selective etching recipe
and near vertical sidewall.
2. Experiment
N-type Ge wafers with a (110) crystal orientation were
used throughout the development process. Firstly, the
wafers were cleaned in warm butanol followed by
warm isopropyl alcohol and blow dried in N2 gas. A
polymer based photoresist; 23CP by Tokyo Ohka
Kogyo Co. Ltd was used as the photoresist mask and
spin coated onto the Ge surface. The samples were then
baked on a hotplate at 90°C for 90 seconds. The
waveguide structures were defined by lithography
technique, developed using a photoresist developer and
post exposure baked again on a hot plate at 90°C for 60
seconds before being etched in the ICP for 60 seconds
with the same operating conditions (chamber pressure
of 1.5x10-4 Torr, RF bias power of 50 W, CHF3 flow
rate of 10 sccm), except for the ICP bias power which
was varied from 800 W to 1400 W. Finally, the
residual photoresist was removed using the photoresist
remover and rinsed in warm isopropanol.
3. Results and discussion
Two figures of merit were considered in the fabrication
of the Ge waveguide structure. The first figure of merit
is the selectivity of the etching ratio between Ge versus
the photoresist. This first figure of merit is interwoven
with the etch rate for Ge and photoresist. The second
figure of merit is that the sidewall angle should be
vertical with minimal under etching of the waveguide
structure. An overview of the etching process is given
in Figure 1.
Fig. 1. Schematic overview of the ICP process,
(a) photoresist on Ge (b) CF2 passivation layer
(c) etching process (d) final etch profile and
sidewall angle Ɵ definition.
There are two competing phases that occur during
the etch process. One is where a passivation layer is
deposited onto the photoresist and Ge surface and
another is where the photoresist and Ge material is
etched. CHF3 is reported to dissociate into a number of
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
28
different neutral and ionic radicals by electron impact
dissociation during the ICP process and as seen in
Table 1 [4].
Table 1. Electron impact dissociation of CHF3 and
corresponding threshold energies
Reaction Threshold
energy (eV)
CHF3 + e CF2 + HF (1) 2.43
CHF3 + e CF3 + H (2) 4.52
CHF3 + e CHF2 + F (3) 4.90
CF3 + e CF2 + F (4) 3.83
CF2 + e CF + F (5) 5.35
As seen in Table 1, the lowest threshold energy is
exhibited by the dissociation of CHF3 into CF2 gas
which is a polymeric precursor. Clustering of CF2 then
subsequently leads to its deposition onto the etching
surface as a passivation layer. The passivation layer
helps to protect the photoresist and enables greater
selectivity.
Using the optimized dry etching conditions, Ge is
etched at a rate of 190 nm/min while the photoresist is
etched at a rate of 35 nm/min giving a selectivity ratio
of 5:1 (Ge: photoresist).
In order to produce a vertical sidewall angle with
no under etching, both physical bombarding as well as
chemical reactions must be optimized during the
etching process. The main components for physical
etching are the F radicals produced by the further
dissociation of CHF3 which reacts with Ge to produce
GeF4 gas that can be pumped out from the ICP
chamber.
HF has been reported to readily etch Ge [5] and the
HF produced by the CHF3 dissociation provides the
chemical reaction component of the etching mechanism.
Fig. 2. SEM images of Ge fabricated with ICP bias
power and corresponding sidewall angle Ɵ
(a) 800 W (50°) (b) 1000 W (55°)
(c) 1200 W (85°) (d) 1400 W (70°).
The vertical angle of the sidewall can be optimized
by varying the ICP bias power as shown in Figure 2.
Fig. 3. Change in sidewall angle, Ɵ due to
applied ICP bias power.
The sidewall angle increases to near vertical when
applying an ICP bias power of 1200 W leading to an
optimized equilibrium between the physical and
chemical etching components as shown in Figure 3.
Below 1200 W of ICP bias power, the sidewall angle is
bevelled while at ICP bias power of 1400 W, under
etching is evident leading to narrowing of the
waveguide structure and a sloping sidewall.
The photoresist mask can then be easily removed
after etching using the photoresist remover and cleaned
in warm isopropanol.
4. Conclusion
Dry etching conditions to fabricate germanium
waveguide using a polymer photoresist mask has been
developed and optimized to produce a highly selective
etch and near vertical sidewall angle. The results
obtained may provide a simpler low damage dry
etching procedure for fabrication of germanium
waveguides and optical devices.
Acknowledgements
The authors would like to acknowledge Profs. D. Wang
and H. Nakashima of Kyushu University for their
useful discussion and advice.
References
[1] J. Michel, et al "An Electrically Pumped Ge-on-Si Laser",
OFC/NFOEC, PDP5A.6 (2012)
[2] A. Malik, et . al, "Germanium-on-Silicon Mid-Infrared
Arrayed Waveguide Grating Multiplexers", Photonics
Tech. Lett. IEEE, 25, 1805-1808 (2013)
[3] J. Cardenas, et al, "Low loss etchless silicon photonic
waveguides", Optics Express, 17, 4752-4757 (2009)
[4] M. Goto, et al "Cross Section Measurements for Electron-
Impact Dissociation of CHF3 into Neutral and Ionic
Radicals", Jpn. J. Appl. Phys., 33, 3602-3607 (1994).
[5] B. Schwartz, H. Robbins "Chemical Etching of
Germanium in Solutions of HF, HNO3, H2O, and
HC2H3O2", J. Electrochem. Soc., 111, 196-201 (1964).
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
29
SUPPRESSING NEW GRAPHENE NUCLEI GENERATION BY
HYDROGEN SWEEPING
Ding Dong1, Hiroki Ago2
1 Graduate School of Engineering Sciences, Kyushu University 2 Institute for Materials Chemistry and Engineering (IMCE) and Graduate School of Engineering Sciences,
Kyushu University, Fukuoka 816-8580, Japan
Abstract: New graphene nuclei continually appear during CVD process when using Cu as catalyst could be the main issue
to get large domain graphene. Here we reported a facile way to suppress new graphene nuclei generation by introducing H2
by interval time. Finally, we found new graphene nuclei could be effectively suppressed by this method.
1. Introduction
Recently, there are many reports about decreasing
the graphene density methods when using copper
catalyst, such as mild oxidation copper in Argon
gas [1-3], copper pre-treatment [4], liquid
Copper[5], removing carbon impurities on copper
[6, 7],Argon pulse[8] and “Vapour Trapping”
structure[9-11].All of above methods were
demonstrated to be useful to suppress the graphene
density.
Actually, in order to get millimetre, even centimetre
size single graphene domain, at least several hours
needed for CVD reaction. However, even people
could get much lower graphene density in the
beginning, we will show that, there is still high
possibility that new graphene domain will appear
as reaction time grows. The new appearance
graphene domains not only increase the graphene
density, but lower or even broken the possibility to
grow large graphene single domain, especially
when the new graphene domain appeared near the
previous existing graphene domain. Thus how to
suppress or avoiding new graphene nuclei
generation and still maintain graphene density as
low as beginning during the graphene growing is
extremely significate and crucial to get large
enough graphene single crystalline domain.
Unfortunately, this is usually neglected in most of
papers, which mainly focusing on the graphene
density on fixing time. There is paper noticed about
this but without any resolution [12].In this paper,
we first show the relationship between the
graphene density and reaction time. Then we
propose a facile method to suppress new graphene
nuclei appear when prolong the reaction time.
2. Main text
Copper mild oxidation in Argon gas (including
microscale Oxygen) [1-3] or directly heating in air
was verified very helpful to suppress graphene
nucleation density [8]. After oxidation and
reduction, the Cu atoms of active Cu crystal
boundaries rearrange into less active structure, and
thus the graphene nucleation density can be well
decreased after Cu surface oxidation [13, 14]. Thus
before our CVD experiment, we heat our copper at
200℃ to oxidize copper surface in air. After pre-
oxidation in air, we load Cu foil to our CVD
chamber to grow graphene. Before introducing
methane to CVD system, we anneal copper in 5%
hydrogen that diluted in Argon gas as long as 20
min to remove the copper oxide layer at 1070℃.
Then we pump in 2% hydrogen and 15 ppm
methane (all diluted in Argon gas) for graphene
growth at the same temperature. After reaction, we
oxidize the copper again at 200℃ for 30s in order
to visualize the graphene domain directly [15]
For growth times of 30min (Fig.1a), 60min (Fig.1b),
and 90min (Fig.1c), the maximum diagonal
distances for the graphene domains are∼556,
∼1056, and∼1600 um, respectively. This largely
linear time dependence indicates that the growth
velocity of the edge is constant and the increase in
a linear dimension of a growing crystallite is
simply proportional to the diffusion rate of the
active carbon which is constant at a fixed
temperature [16, 17]. That means the graphene
domain diameter is proportional to reaction time. If
we assume that the largest graphene domain
generates at the beginning we could get single
graphene domain occurrence time distribution. Fig
1(d-f) shows that there is always new graphene
domain generation during CVD reaction period. If
we look into Fig.1d, we could found that more than
half of the graphene nucleate in the first 10 min,
which means the main graphene nucleation process
prefer gathering at the beginning. Nevertheless,
new graphene domain still will appear continuously
in the following reaction time. That indicate even
people could get satisfied graphene density at
particular time, there is extremely high possibility
that new graphene domain will come out if needing
increasing reaction time to make graphene bigger.
The biggest disadvantage is the new occurrence
smaller graphene domain may ruin the previous
larger single crystalline graphene domain, making
it poly-crystallization.
The overall growth processes for Cu-based
graphene could be divided into three main steps
that described in Fig.2a step 1-3. (1) CH4
dissociates and is chemically adsorbed on the Cu
surface to form the active carbon species (CHx<4) s,
where “s” signifies “ surface-adsorbed” to
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
30
distinguish it from a gaseous molecule. The exact
nature of the active carbon species has not been
well-defined and we used carbon monomers (C) to
represent all types of active carbon species in
Figure 2a. (2) From recent research, the carbon Cu
interaction is weak and the desorption rate of active
carbon species is comparable to its mobility on the
Cu surface above 870 ℃ .Under the growth
conditions described in this paper, the temperature
is 1070 ℃, suggesting that the movement of active
carbon species on the Cu surface is dominated by
diffusion and desorption. (3) When active carbon
reaches a critical supersaturation point, graphene
domains nucleate. Once the graphene nuclei are
formed, most of the active carbon species will be
captured and consumed in the growth of graphene,
reducing the probability that new graphene nuclei
will be formed in the nearby area of the Cu catalyst.
Because graphene nuclei won’t takes place until the
concentration of active carbon species reaches to
supersaturation level [20, 21], we could put off or
even avoiding new nuclei generation if these far
away from the existing graphene domain active
carbon atoms could be swept away. Hydrogen had
demonstrated to a dual role during graphene
synthesis [22]: an activator of the surface bound
carbon that is necessary for monolayer growth and
an etching reagent that controls the size and
morphology of the graphene domains. Thus we
could utilize hydrogen to etch the free active
carbon atoms away (see Fig.2a step 4).After H2
“sweeping” for short time, CH4 gas will be re-
introduced and the previous graphene could regrow.
In order to verify above idea, we only shut off CH4
gas for 10 minutes every 30 min interval during
graphene synthesis section, only keeping Hydrogen
and Argon gas on. Fig.2 b-d shows the SEM
images when total reaction time is 60 min, 90 min,
and 120 min respectively (excluding hydrogen
sweeping time),and hydrogen sweeping time is one,
two and three respectively.Fig.2e-g are the
corresponding graphene domains occurrence
distribution. It is obviously that most of graphene
domains only generate at the first 30 min. This
means by H2 sweeping, new graphene nuclei is
successfully suppressed.
Fig.1
Fig.2
4. Conclusion
In this paper we utilize H2 to etching the
redundancy active carbon in Cu surface and
successfully supressed new graphene nuclei
generation. This method is easy to complete.
5. References [1] |Zhou H, Yu WJ, Liu L, Cheng R, Chen Y, Huang X, et al. Chemical vapour deposition growth
of large single crystals of monolayer and bilayer graphene. Nature communications.
2013;4:2096.
[2] Li J, Wang X-Y, Liu X-R, Jin Z, Wang D, Wan L-J. Facile growth of centimeter-sized single-
crystal graphene on copper foil at atmospheric pressure. J Mater Chem C. 2015;3(15):3530-5.
[3] Gan L, Luo Z. Turning off Hydrogen To Realize Seeded Growth of Subcentimeter Single-
Crystal Graphene Grains on Copper. Acs Nano. 2013;7(10):9480-8.
[4] ZhengYan, Jian Lin, Peng Z, Sun Z, YuZhu, Li L, et al. Toward the Synthesis of Wafer-Scale
Single-Crystal Graphene on Copper Foils. Acs Nano. 2012;6(10):9110–7.
[5] Wu YA, Fan Y, Speller S, Creeth GL, Sadowski JT, He K, et al. Large Single Crystals of
Graphene on Melted Copper Using Chemical Vapor Deposition. Acs Nano. 2012;6(6): 5010–7.
[6] Magnuson CW, Kong X, Ji H, Tan C, Li H, Piner R, et al. Copper oxide as a “self-cleaning” substrate for graphene growth. J Mater Res. 2014;29(03):403-9.
[7] Strudwick AJ, Weber NE, Schwab MG, Kettner M, Weitz RT, Wünsch JR, et al. Chemical
Vapor Deposition of High Quality Graphene Films from Carbon Dioxide Atmospheres. Acs
Nano. 2014;9(1):31-42.
[8] Eres G, Regmi M, Rouleau CM, Chen J, Ivanov IN, Puretzky AA, et al. Cooperative Island
Growth of Large-Area Single-Crystal Graphene on Copper Using Chemical Vapor Deposition.
ASC NANO. 2014;8(6):5657–69.
[9] Wang C, Chen W, Han C, Wang G, Tang B, Tang C, et al. Growth of millimeter-size single
crystal graphene on Cu foils by circumfluence chemical vapor deposition. Sci Rep. 2014;4:4537.
[10] Shi YG, Wang D, Zhang JC, Zhang P, Shi XF, Hao Y. Fabrication of single-crystal few-layer
graphene domains on copper by modified low-pressure chemical vapor deposition.
Crystengcomm. 2014;16(32):7558. [11] Zhang Y, Zhang L, Kim P, Ge M, Li Z, Zhou C. Vapor trapping growth of single-crystalline
graphene flowers: synthesis, morphology, and electronic properties. Nano Lett.
2012;12(6):2810-6.
[12] Wang Z-J, Weinberg G, Zhang Q, Lunkenbein T, Klein-Hoffmann A, Kurnatowska M, et al.
Direct Observation of Graphene Growth and Associated Copper Substrate Dynamics by in Situ
Scanning Electron Microscopy. Acs Nano. 2015;9(2):1506-19.
[13] Hao Y, Bharathi MS, Wang L, Liu Y, Chen H, Nie S, et al. The role of surface oxygen in the
growth of large single-crystal graphene on copper. Science. 2013;342(6159):720-3.
[14] Miley HA. Copper Oxide Films. J Am Chem Soc. 1937;59(12):2626-9.
[15] Wang H, Wang G, Bao P, Yang S, Zhu W, Xie X, et al. Controllable synthesis of submillimeter
single-crystal monolayer graphene domains on copper foils by suppressing nucleation. J Am Chem Soc. 2012;134(8):3627-30.
[16] Kidambi PR, Bayer BC, Blume R, Wang ZJ, Baehtz C, Weatherup RS, et al. Observing
graphene grow: catalyst-graphene interactions during scalable graphene growth on
polycrystalline copper. Nano Lett. 2013;13(10):4769-78.
[17] Mohsin A, Liu L, Liu P, Deng W, Ivanov IN, Li G, et al. Synthesis of Millimeter-Size Hexagon-
Shaped Graphene Single Crystals on Resolidified Copper. Acs Nano. 2013;7(10):8924-31.
[18] Guo W, Wu B, Li Y, Wang L, Chen J, Chen B, et al. Governing Rule for Dynamic Formation of
Grain Boundaries in Grown Graphene. Acs Nano. 2015.
[19] Nguyen VL, Lee YH. Towards Wafer-Scale Monocrystalline Graphene Growth and
Characterization. Small. 2015.
[20] Kim H, Mattevi C, Calvo MR, Oberg JC, Artiglia L, Agnoli S, et al. Activation Energy Paths for
Graphene Nucleation and Growth on Cu. Acs Nano. 2012;6(4):3614-23. [21] Zhang X, Li H, Ding F. Self-assembly of carbon atoms on transition metal surfaces--chemical
vapor deposition growth mechanism of graphene. Adv Mater. 2014;26(31):5488-95.
[22] Vlassiouk I, Regmi M, Fulvio P, Dai S, Datskos P, Eres G, et al. Role of Hydrogen in
Chemical Vapor Deposition Growth of Large Single-Crystal Graphene. Acs Nano. 2011;5(7):6069–76.
A HIGHLY ACTIVE Ni/ZSM-5 CATALYST FOR DEEP
HYDROGENATION OF ARENES
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
31
Shi-Chao Qi, Lu Zhang, Jun-ichiro Hayashi
Applied Science for Electronics and Materials, Kyushu University. [email protected]
Abstract: A highly dispersive supported nickel catalyst was in situ prepared by decomposing nickel tetracarbonyl onto ZSM-
5 zeolite, respectively. Unexpectedly, amorphous nickel was formed onto ZSM-5. Strong interaction between supported
nickel and the support is proved. Catalytic hydrogenations of arenes, i.e. durene, anthracene, phenanthrene and the heavy
mixture as by-products derived from methanol-to-gasoline conversion, over the catalysts were examined. Ni/ZSM-5 shows a
dramatic activity for deep hydrogenation of arenes and complete saturation of arenes can be achieved over the catalyst.
1. Introduction
Risk of petroleum shortage has been stimulating
development of coal to oil technologies, including
direct coal liquefaction (DCL) and indirect coal
liquefaction (IDCL), but the high concentration of
arenes in the liquids from DCL and IDCL confines
the application of them as clean fuels [1-3]. For
instance, methanol-to-gasoline conversion (MTG)
is an important IDCL process, but it normally
produces substantial amount of a heavy mixture
(HM), which mainly consists of unsaturated species,
especially polymethylbenzenes (PMBs). Deep
hydrogenation of such arenes, either PMBs or
condensed arenes (CAs), has thus been a major
technical subject [4,5]. None of the catalytic hydrogenation of arenes,
reported so far, has reached full hydrogenation of
CAs or PMBs. Conventional methods of catalyst
preparation, such as impregnation, co-precipitation,
sol-gel, and in situ reduction, were investigated
extensively. However, those methods are relatively
tedious and neither noble nor non-noble metallic
catalysts developed so far could completely
hydrogenate CAs and PMBs with high yields. A
key to preparation to a highly active catalyst is to
perform metals loading and reduction below a
threshold temperature for avoiding the decrease in
specific surface area of metals. Metal carbonyls
(MCs) usually decompose at relatively low
temperature into metals directly and are therefore
ideal precursors of highly active metal particles,
which can be used to catalyst preparation processes
much simpler than conventional ones. Supported
catalysts were prepared through the decomposition
of MCs in 1980s. However, preparation of
supported metallic catalysts using MCs was not
developed since most MCs volatilize rapidly long
before decomposition. In the present work, using
nickel tetracarbonyl (NTC) for nickel has
successfully developed to in situ prepare supported
nickel catalysts for deep hydrogenation of arenes.
2. Main text
NTC was synthesized by reacting active nickel
powder with CO under 8.0 MPa at 100 oC in a 100
mL stainless steel and magnetically stirred
autoclave. Diethyl ether, ZSM-5 zeolite, and NTC
were put into the autoclave. After replacing air
inside the autoclave with nitrogen, the mixture in
the autoclave was slowly stirred for 1 h at room
temperature to sufficiently impregnate NTC into
the support. Then the autoclave was heated to 100 oC and kept at the temperature for 1 h with rapid
agitation to allow in situ decomposition of NTC
over the support. After cooling the autoclave, CO
in the autoclave was released followed by
subsequent heating and cooling process mentioned
above to decompose NTC as exhaustively as
possible. Then the reaction mixture was taken out
from the autoclave and filtrated under nitrogen
protection to obtain the supported catalyst.
Catalysis procedures were carried out as
follows: THF (20 mL), catalyst (0.5 g), and
substrate (arene 5 mmol or HM 1.0 g) were fed into
the autoclave. After replacing air in the autoclave
and being pressurized with hydrogen to 5.0 MPa at
room temperature, the autoclave was heated up to
an indicated temperature within 20 min and kept at
the temperature for a prescribed period of time
followed by cooling the autoclave rapidly. The
reaction mixture was taken out from the autoclave
and filtrated. The filtrate was analyzed with gas
chromatograph/mass spectrometry (GC/MS).
As Fig. 1 displays, a number of spherical metal
particles with diameter less than 100 nm adhere to
the surface of three supports. In Fig. 2, nickel
species are supported onto ZSM-5. The nickel
supported onto ZSM-5 does not show as the shape
of crystals as the former two, but equably and
amorphously disperses onto ZSM-5, which results
from the restriction of the inner channels of ZSM-5
and the interaction between nickel and the support.
The SAED of Ni/ZSM-5 shows a diffraction
pattern of amorphous state as well.
In order to further confirm the catalytic activity
of Ni/ZSM-5 towards PMBs, durene was
hydrogenated over Ni/ZSM-5 at different
temperatures for 24 h to analyze the conversion of
Fig. 1. SEM and HREM image of the Ni/ZSM-5.
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
32
Fig. 2. HREM image of the Ni/ZSM-5.
durene (Fig. 3). The complete conversion is
observed during the temperature interval from 120 oC to 180 oC, and a conversion jump, from 15% to
96%, could be observed from 80 oC to 100 oC,
which indicates the activation temperature for
durene is relatively low due to the high activity of
Ni/ZSM-5. Nuclear magnetic resonance was used
to ascertain the molecular structure of the
hydrogenation product: 1H, δ= 0.838, 0.854; 2H,
δ= 1.272, 1.284, 1.333, 1.363 and 3H, δ= 1.598,
1.603, which indicate the protons of methyl,
methylene and methylidyne, respectively.
Corresponding with the ratio of three kinds of
protons in 1,2,4,5-tetramethylcyclohexane, the area
integrals of these peaks are respectively 3.08, 1.06
and 1.00.
60 80 100 120 140 160 1800
20
40
60
80
100
Reaction temperature (oC)
Co
nv
ers
ion
(%
)
Fig. 3. Reaction temperature profile of conversion
from catalytic hydrogenation of durene over
Ni/ZSM-5 and 1H NMR spectrum of hydrogenated
durene.
Anthracene and penanthrene were hydrogenated
over the catalyst for 24 h at 180 oC. The anthracene
perhydride almost accounts for the whole
compositions of products. Deep hydrogenation of
phenanthrene is difficult due to its steric
configuration. A high catalytic activity of Ni/ZSM-
5 is further certified by perhydrophenanthrene yield
of 25.8 mol%, and the yield of two-ring
hydrogenation products also reaches 63%. The
outstanding catalytic activity of Ni/ZSM-5 is
attributed to the following two reasons, the
amorphous state of nickel loaded inside ZSM-5 and
the strong interaction between nickel and the
support. The amorphous dispersion of nickel
greatly increases the opportunity of interaction
between substrates and the catalyst, meanwhile the
synergistic effect between nickel and acidic support
creates an electron-deficient surface, which
substantially increases the activity of metal-loaded
and promotes the π bond cracking of arenes.
As shown in Fig. 4, main components in HM are
arenes, especially PMBs. The PMBs are extremely
difficult to be saturated; meanwhile the blended
arenes would restrain mutual activity to be
hydrogenated due to the competitive adsorption
over active sites. The extremely high activity of
Ni/ZSM-5 for hydrogenation successfully
overcomes the difficulties. As Fig. 4 (HHM
denotes hydrogenated HM) exhibit, all the arenes in
HM were catalytically hydrogenated to saturated
species over Ni/ZSM-5 at 180 oC for 20 h.
6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0
12 3
56 7 9 11
1415
16 17 19
20
2223 26
29
30
31
3233 37
38 40 41 4243
0
17
34
51
68
85
0
20
40
60
80
100
46 47
48
50
11.5 12.0
61
12.5
67
13.0 13.5 14.0 14.5 15.0 15.5 16.0 16.5
5960
63
64
65
6870
71 72 75 77 78 80 81 83 86 89 91 93 94 95 9899
101103
104 106 109 11158 69 85
17.0 17.5
113 123
5653
Retention time (min)19.5 20.0 20.5 21.0 21.5 22.0
197
145
0
0.04
0.08
0.12
0.16
0.20
144148149
151
158
160
162163
166
167
170171
173
176179
181184
187
189 192193
195 198
141
18.0 18.5
22.5 23.0 23.5 24.0 24.519.0
19.5 20.0 20.5 21.0 21.5 22.0 22.5 23.0 23.5 24.0 24.519.00
16
32
48
54
80
0
20
40
60
80
100
HHM
HHM
HHM
12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0 18.5
6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0
HM
HM
HM
0
6
12
18
24
30
Rela
tive a
bu
nd
an
ce (
%)
14
5 8 10 12 13 15 16 18 21 24 25 27
28
30 31 3234
35
3536
36 37 38 39 424341
44
45 49 5051
52
52
54
55
57 62 63 64
66
67 68 73 74 75 76 77 798284 8788 90 92 96 97
100
102 105
105
107108 110 112
114
115
116
117
119
118120
120
121
122 124 127
125
126128
129
130
131
132
133
134135
136 137
138
139
140
142
143
146
147 150
152
153154
155
156
157
159
161
164
165168
169 172
174 175177
178
180
182
183185186 188
190191194
196
199200
201
202
203
204
205
206
207
208
209211
210212
213
215
214
218216
217219
220221
222
223 226
224225
227
228229
230
231234
231233
232
236
235
237238
240239
241
243242
244
Fig. 4. Total chromatograms of the HM and HHM
(the numbers in red and blue color denote arenes
and alkanes respectively).
3. Conclusion
In summary, with adopting nickel tetracarbonyl as
precursor, a highly dispersive and dramatically
active nickel-loaded catalyst Ni/ZSM-5 for the
deep hydrogenation of arenes could be in situ
prepared. The nickel supported onto ZSM-5 does
not show as the shape of crystal, but equably and
amorphously disperses onto ZSM-5. The catalyst
distinctly facilitate the complete hydrogenation of
condensed arenes and polymethylbenzenes. Heavy
by-products derived from MTG are completely
saturated as well.
4. References [1] Longwell, J. P.; Rubin, E. S.; Wilson, J., Coal:
Energy for the future. Prog. Energy Combust. Sci.
1995, 21, 269-360.
[2] Cayan, F. N.; Zhi, M.; Pakalapati, S. R.; Celik, I.; Wu,
N. Q.; Gemmen, R., Effects of coal syngas impurities
on anodes of solid oxide fuel cells. J. Power Sources
2008, 185, 595-602.
[3] Breysse, M.; Djega, M. G.; Pessayre, S., Deep
desulfurization: reactions, catalysts and technological
challenges. Catal. Today 2003, 4, 129-138.
[4] Schulz, H.; Böhringer, W.; Waller, P.; Ousmanov. F.,
Gas oil deep hydrodesulfurization: refractory
compounds and retarded kinetics. Catal. Today 1999,
49, 87-97.
[5] Tsoskounoglou, M.; Ayerides, G.; Tritopoulou, E.,
The end of cheap oil: current status and prospects.
Energy Policy 1990, 88, 109.
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
33
THE ACCELERATED SOLVENT EXTRACTION OF
XINYU COKING COAL AND ITS EXTRACTION MECHANISM
Lu Zhang, Shi-Chao Qi, Koyo Norinaga
Applied Science for Electronics and Materials, Kyushu University. [email protected]
Abstract: Coking coal from Xinyu of Shanxi Province is extracted under elevated temperature and pressure via Accelerated
Solvent and Soxhlet Extraction. Analyzing their GC/MS results, we explore the two extraction methods’ impact on the
dissolution behavior of small molecules in coal and investigate the mechanism of the extraction.
1. Introduction
Destroying the hydrogen bonds amid coal
molecules, VDW and weak complexing forces,
solvent extraction frees the solvable molecues in
coal [1]. Traditional methods of extraction under
ordinary pressure were time-wasted, solvents-
exhausted and tedious but with bad efficiency. The
Accelerated Solvent Extraction improves the speed
and effeciency of the extraction, and decreases the
solvent cost, meanwhile separates the solid from
liquid phase because the reduced surface tension of
solvent, enhanced infiltration capacity and
accelerated equilibrium process are generated from
solvent heated and forced. In this article, coking
coal from Xinyu of Shanxi Province is extracted
under elevated temperature and pressure via
Accelerated Solvent and Soxhlet Extraction.
Analyzing their GC/MS results, we explore the two
extraction methods’ impact on the dissolution
behavior of small molecules in coal and investigate
the mechanism of the extraction.
2. Main text
Coal sample is coking coal after taken off the
minerals , comes from Xinyu Preparation Plant of
Shanxi Province. It was then pulverized to around
150 mesh. TABLE I shows the proximate and
ultimate analyses of the coal sample.
TABLE I THE PROXIMATE, ULTIMATE ANALYSIS OF COAL
SAMPLE
Proximate analysis/ w%
Mad Ad Vdaf FCdaf
0.69 10.13 22.18 77.82
Ultimate analysis/ w%
Cdaf Hdaf Odaf Ndaf St,d
89.08 4.63 1.99 1.72 2.30
Weigh air dried basis coal sample about 2g. Put
it in the soxhlet extractor after parceled with filter
paper. Use 1-propanol solvent to extract it 90
minutes at the boiling point temperature. The
extracts were refined by rotary evaporation and
analyzed by GC/MS. The residues were washed,
suction filtered, dried in turn and analyzed by FTIR.
Accelerated solvent extraction: Packed by 450 nm
PTFE and filter paper respectively, the samples (2
g) were extracted in a 22 mL extraction pool under
the pressure of 80 bar and 100 oC. The extraction
was cycled for 2 times after static extraction for 15
min. With referring to the extract, the extraction
rates (daf, w%) are calculated as follows: 3.85% for
accelerated solvent extraction and 3.41% for
Soxhlet extraction, respectively.
As shown in Fig. 1 and 2, there are 37 compound
categories detected in the soluble substances via
accelerated solvent extraction, including 17 alkanes,
13 aromatics, 3 oxy-compounds and elemental
surfur. There are also 37 compound categories
detected in the soluble substances via Soxhlet
extraction, including 14 alkanes, 22 compounds
containing oxygen or nitrogen, 1 thioether, and no
aromatics and sulfides detected in it.
2.1 Alkanes
There are 17 alkanes from C11 to C27 in the solub
le substances via accelerated solvent extraction and
14 alkanes from C20 to C33 in the soluble substance
s via Soxhlet extraction distributing continuously.
Despite similar number of compounds, the two solu
ble substances belong to two different series obviou
sly due to the different numbers of carbon atoms co
ntaining in the compounds. The former belongs to a
lkanes of low carbon and the second one is defined
as high carbon. As one kind of small molecules in
coal, n-alkanes exist as three states, free state,
micropores and network embedded states [2-4]. As
for micropores embedded states, mid- and high-
carbon n-alkanes usually embedded into relative
large micropores due to their big sizes, and low-
carbon n-alkanes usually embedded into relative
small micropores. Based on their own permeability,
solvents are easy to enter the relative large
micropores under ordinary pressure of Soxhlet
extraction, whereas the solvents also enter the small
micopores under the pressure above 80 bar. The
diffusing impetus of soluble substances comes from
the concentration gradient, which is provided by
the circulation flow of solvent in Soxhlet extraction.
As a result, accelerated solvent extraction only
improves the rate of solvent penetration, but does
not benefit the diffusing rate of soluble substances.
2.2 Aromatics
There are 13 aromatics, including derivatives of
benzene, naphthalene and anthracene, in the soluble
substances via accelerated solvent extraction,
whereas no aromatics are detected in the soluble
Intellectual Exchange and Innovation Conference on Engineering & Sciences (IEICES) Oct 15th, 2015
34
substances via Soxhlet extraction. Aromatics are
always embedded in the relative small micropores
[5], thus such derivatives are not dissolved via
Soxhlet extraction. The mechanism of dissolving
benzothiophene series is similar with mentioned
above.
2.3 Oxy- and nitrogen-compounds
Three oxy-compounds, including only one ester,
are detected in the soluble substances via
accelerated solvent extraction. However, there are
22 oxy- or nitrogen-compounds, including 6 acids
and 9 esters, detected after Soxhlet extraction. Most
of them are long chain aliphatic acids or esters,
which are obviously embedded in the relative large
micropores.
According to the FTIR spectra in Fig. 3, there is
no obvious difference about residues' structure
characteristics of functional group of two kinds
extraction. The reason is that both the extraction
rate are low, which is not enough to affect the
functional group distribution of the residues.
10. 00 15. 00 20. 00 25. 00 30. 00 35. 000
100
20
40
60
80
Ret ent i on Ti me/ mi n
Relative Abundence/%
Fig. 1. TIC of soluble substances of Accelerated
Solvent Extraction.
10. 00 15. 00 20. 00 25. 00 30. 00 35. 000
100
20
40
60
80
Ret ent i on Ti me/ mi n
Relative Abundence/%
Fig. 2. TIC of soluble substances of Soxhlet
Extraction.
1000 4000 2000 3000
1
2
Fig. 3 FTIR spectra of residues.
3. Conclusion
The extractants from ASE mainly contain materials
of molecular weight from 142 to 296, i.e. mid- or
high-carbon n-alkanes, aromatics and thiophene
series, while the extractants from SE contain
materials of molecular weight from 228 to 426, i.e.
mid- or high-carbon n-alkanes, and aliphatic
hydrocarbons (or esters) of long carbon chains.
Because of the limited time, the solvent in SE only
enters the relative large micropores. However, the
solvent in ASE can enter both relative large and
small micropores simultaneously. The advantage of
ASE is to improve the permeability and permeation
rate of solvents, but it makes little contribution to
diffusion rate of solvents. The intrinsic reasons for
the different results of the two extraction methods
are the different molecular weights of the materials
embedded in the two kinds of micropores.
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1990, 4: 107
[2] Qin Z H, Wei X Y, Jiang C, J. China Univers. Mining
Technol., 2005, 34: 579
[3] Qin Z H, Jiang C, Sun Hao, J. China Univers. Mining
Technol., 2005, 34: 707
[4] Qin Z H, Gong T, Li X S, J. China Univers. Mining
Technol., 2008, 37: 443
[5] Qin Z H, Hou C L, Zhang D, J. China Univers.
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