Japan-Philippine Joint Workshop
on Materials for Safe andSustainable Society 2011

Shizuoka University, Hamamatsu, Japan
December 5, 2011

Supported by Japan Student Service Organizationand Shizuoka University

Proceedings of Japan-Philippine Joint Workshop
on Materials for Safe and Sustainable Society
2011
December 5, 2011

Shizuoka University, Hamamatsu, Shizuoka, Japan

Organized by
Division of Mechanics and Strength of Materials, Department of MechanicalEngineering, Shizuoka University
Sponsored by
Japan Student Service Organization, Japan
Shizuoka University, Japan

Outline of the Workshop
10:30-10:40
10:40-11:55
11:55-13:00
13:00-14:15

Opening Address (Prof. Tohgo)
Oral Presentation Session I
Lunch
Oral Presentation Session II

14:15-14:30
14:30-15:30
15:30-15:40
19:00-21:00

Coffee BreakOral Presentation Session III
Closing Address (Prof. Shimamura)
Banquet (Dinning Pub Irohanihoheto)

Program
Oral Presentation Session I (Chair Prof. Shimamura, Shizuoka University)
10:40-10:55
M.Kim, T.Fujii, K.Tohgo and Y.Shimamura(Shizuoka University)“Applicability of Non-linear Fracture Mechanics in Stress Corrosion Cracking Behaviorof Austenitic Stainless Steel” ······································································ 1
10:55-11:10
J.K.C.N.Agutaya and T.P.Tumolva(University of the Philippines-Diliman)“Non-isothermal Kinetic Parameters of Unsaturated Polyester Using Modified

Coats-Redfern Method” ············································································· 3
11:10-11:25
A.Kokobo, Y.Shimamura, S.Kamada, H.Masuda, H.Ishii, K.Tohgo, T.Fujii, T.Yagasaki
and M.Harada(Shizuoka University)“Development of Ultrasonic Torsion Fatigue Testing Machine” ························ 5i11:25-11:40
P.D.Ramoso and M.L.P.Dalida(University of the Philippines-Diliman)“Dip Coating of TiO2 Photocatalyst on Glass Raschig Rings for Flow Photocatalytic

Reactor Application” ················································································· 7
11:40-11:55
A.Yokoyama, T.Fujii, K.Tohgo, Y.Noda and Y.Shimamura(Shizuoka University)“Effect of Foil Thickness on Mechanical Property of Pure Copper Foil” ············· 9Oral Presentation Session II (Chair Prof. Tumolva, UPD)
13:00-13:15
K.Uematsu, H.Katogi, Y.Shimamura, K.Tohgo and T.Fujii(Shizuoka University)“Fatigue Property of Jute Monofilament” ··················································· 11
13:15-13:30
E.Belostrino, B.J.Uy, M.L.Lagura and T.P.Tumolva(University of the Philippines-Diliman)“Synthesis of Furfural from Pineapple Bagasse” ········································· 13
13:30-13:45
N.Urata, J.Shibata, T.Fujii, K.Tohgo and Y.Shimamura(Shizuoka University)“Fatigue Strength of a Paper-based Friction Material under Shear-Compressive

Loading”································································································ 15
13:45-14:00
B.J.Uy, E.Belostrino, M.L.Lagura, R.Guerrero, and T.P.Tumolva(University of the Philippines-Diliman)“Synthesis of Furfural from Coconut Shells” ··············································· 17ii

14:00-14:15
K.Nakazawa, T.Fujii, K.Tohgo, M.Ishikura and Y.Shimamura(Shizuoka University)“Evaluation of Mechanical Properties of PSZ-Ti Biocompatible Composite Fabricated by

MIM Method”························································································· 19

Oral Presentation Session I (Chair Prof. Fujii, Shizuoka University)
14:30-14:45
R.D.Guerrero and T.P.Tumolva(University of the Philippines-Diliman)“Evaluating Carbon Storage Potential in Furfural Synthesis” ······················· 21
14:45-15:00
M.Sakai, Y.Shimamura, N.Morisawa, K.Tohgo and T.Fujii(Shizuoka University)“Mechanical Property of Unidirectional MWNT Sheet/Epoxy Composites” ········ 23
15:00-15:15
J.Ortenero and T.P.Tumolva(University of the Philippines-Diliman)“Evaluating the Carbon Storage Potential of NFRP Using Water Hyacinth Fiber

Reinforcement”······················································································· 25
15:15-15:30
K.Oshima, Y.Shimamura, K.Tohgo, T.Fujii, M.Ishihara, Y.Inoue, J.Muramatsu(Shizuoka University)“Tensile Property of Carbon Nanotube Spun Yarn Reinforced Composite” ······· 27iii

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

Applicability of Non-linear Fracture Mechanics
in Stress Corrosion Cracking Behavior of Austenitic Stainless Steel
Minjung KIM*1, Tomoyuki FUFII*1, Keiichiro TOHGO*1 and Yoshinobu SHIMAMURA*1*1

Shizuoka University Department of Mechanical Engineering
3-5-1 Johoku Naka-ku, Hamamatsu, 432-8561.Japane-mail: kim@mechmat.eng.shizuoka.ac.jp

1. Introduction
Growth behavior of stress corrosion
cracking (SCC) is commonly evaluated bystress intensity factor. However, SCC initiates and propagates in plastic deformation
field. The effect of plastic deformation on
the SCC growth behavior is not clear.
This paper deals with the evaluation of
SCC growth rate taking account of plastic
deformation field. Two kinds of SCC growth
test in corrosion liquid were conducted and
SCC growth rate was arranged by stress intensity factor and equivalent stress intensity
factor, which was calculated from J integral.
The effect of plastic deformation on SCC
growth rate was evaluated by comparison
between stress intensity factor and equivalent stress intensity factor.

2. Experimental procedure
2.1 Material
Stainless-steel type 304 was used for
SCC growth test. solution heat treatment of1100 ℃ for 45 minutes and sensitization
treatment of 600℃ for 16 hours were conducted.
2-2 Test environment
SCC growth test was conducted in corrosive liquid which was 1% polythionic acidand adjusted to pH=3. The liquid exchanged
for new liquid every 48 hours.
2-3 Wedge opening loading test
Figure 1 shows the WOL (Wedge opening load) specimen. The load corresponds tothe stress intensity factor of 22, 30 and 40
MPam0.5 was applied, and the specimen was
immersed in the corrosive liquid. The crack
length was measured every 1 hour.
2-4 Four-point bending test
Figure 2 shows the four point bending
specimen. The specimen with shallow notch,
which is 0.5 mm deep, was used to investigate the single crack growth from the notch
root. Strain of 1% at the compressive surface
was applied and the specimen was also immersed in the corrosive liquid. The crack
length from the notch root was measured
every 1 hour.

3. Results and Discussion
Figure 3 shows SCC growth rate a function of stress intensity factor. The stress intensity factor of the WOL tests(1) and
four-point bending tests(2) was calculated byload and crack length. The SCC growthrate of the WOL tests increased with increasing stress intensity factor. On the other

Wire cut

Wire cut

Fig. 1 WOL specimen.

Fig. 2 Four-point-bending specimen

1Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

Fig. 3da/dt – K

Fig. 4 da/dt - KJ

hand, the crack growth rate of the four point
bending tests was almost constant irrespective stress intensity factor. The crack growthrate of the four point bending tests was about
ten times faster than that of the WOL tests
for the same stress intensity factor. It is considered that the effect of plastic deformationis neglected.
Figure 4 shows SCC growth rate a function of equivalent stress intensity factor. The
equivalent stress intensity factor was calculated as follows;(1)
K J = EJ
where E and J are the Young’s modulus andJ integral, respectively. The value of J integral was calculated by finite element analysis. In the WOL tests, the equivalent stressintensity factor is equal to the stress intensity
factor because of the small scale yielding
condition. The plots of SCC growth rate offour point bending tests shift rightward andFig. 1 WOL specimen.

the results of the point bending tests agrees
with those of the WOL tests. Because theequivalent stress intensity factor is the parameter taking account of plastic deformation. Therefore, the plastic deformation
affects the SCC growth rate, and it is valid toevaluate the SCC behavior based on J integral or effective stress intensity factor.

1.

2.

Reference
P. W. Holsberg, R. A. Hays, Development of Compliance Expression
for Deeply Flawed 1T-WOL Specimen, NAVAL SURFACE WARFARE CENTER CARDEROCKDIV BETHESDA, CAEDIVNSWC-TR-61-1999-20
H. Tada, P. C. Rice and G. Irwin, The
stress analysis of cracks handbook,
Del Research, pp.2-14, (1985).

Fig. 2 Four-point-bending specimen

2Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

Non-isothermal Kinetic Parameters of Unsaturated Polyester
Using Modified Coats-Redfern Method
Jonas Karl Christopher N. Agutaya* and Terence P. Tumolva
Department of Chemical Engineering, University of the Philippines
Diliman 1101 Quezon City, Philippines
TELEFAX: +63-2-929-6640
e-mail: jnagutaya@gmail.com

conversion function, which characterizes thereaction mechanism.

1. Introduction
Polyesters and epoxies are petrochemicals
that account for 95% of the thermoset composite
market with the former predominating in volume
by about ten-fold. The production of thesesynthetic thermosets is largely dependent on thestatus of the oil industry. With the current trendof increasing oil price, their production cost isbound to rise as well. Furthermore, global
environmental concerns, particularly nonbiodegradable landfill impact, have come up
regarding thermosets. These problems of limited
resource and disposal can be addressed by
improving the efficiency of the process andrecycling or by thermal decomposition,
respectively. These solutions require knowledge
on the mechanism function and, by extension,
the kinetic parameters of the material.

By variable separation and integration, Eq.
(1) becomes

The integral on the left-hand side of Eq. (2)has no exact analytical solution, but can beapproximated as follows: A  T0
AE exp ( − x ) E Q ( x ) (3)  ∫0 exp  −
dT =
Rβ
x
 RT β Q ( x) =x 4 + 18 x3 + 86 x 2 + 86 x
x 4 + 20 x 3 + 120 x 2 + 240 x + 120(4)Eqn. (3) and (4) are the fourth Senum andYang approximation as presented in [1].
Substituting Eq. (3) into Eq. (2) gives

Derivation of Objective Function

 AE  exp ( − x )g (α ) = 
Q ( x)
2
 Rβ  x

The dependence of the degree of conversion
α on the temperature T and the heating rate β canbe described by the following differential
equation:dα  A  E =   f (α ) exp  −dT  β  RT 

αwhere g(α) is the integral conversion function.

This study focuses on the application of an
improved iterative version of the Coats-Redfern
method to compute for the non-isothermal
kinetic parameters for orthophthalic unsaturated
polyester (ortho-UP) based on TGA data.

2.

dα A  T0
 E 
=   ∫ exp  −dT (2)0 f α( ) β  0 RT 

g (α ) ≡ ∫(5)

By taking the natural logarithm of both sides
and rearranging some terms, Eq. (6) can beobtained.

(1)

 g (α )  AR  E
  E ln  2  − ln Q 
= 0 (6)  − ln +  RT   E β  RT
 T 

where A is the pre-exponential factor, E is theactivation energy, and f(α) is the differential3Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

This will serve as the objective function inminimizing the sum of the squares of theresidual terms, Sres, which is expressed in thefollowing equation:  E b 
  g (α ) S res = ∑ ln  2 i  − ln Q 
 − a + Ti i =1 
  Ti   RTi  N

4. Conclusion
The iterative version of the Coats-Redfern
method coupled with the fourth Yang and
Senum approximations was not able to model
the behaviour of the heating rate with changes intemperature. Thus, the procedure produced
inaccurate values of the activation energy R and
the Arrhenius constant A.

2(7)

3. Results and Discussions

References
The TGA data used in the simulation was
taken from [3]. The Sres function was minimized
to give obtain the values of a and b for different
heating rates. From each of these parameters, theaverage values of E and R were calculated to be
55,045.24 J mol-1 and 3421.25 min-1,
respectively.

[1] E. Urbanovici, C. Popescu and E. Segal, J. of
Therm. Anal. and Cal. 58 (1999) 683-700.
[2] S. Ch. Turmanova, S. D. Genieva, A. S.
Dimitrova and L. T. Vlaev, eXPRESS
Polymer Letters 2 (2008) 133-146.
[3] T. Tumolva, M. Kubouchi, S. Aoki, and T.
Sakai (2011). “Evaluating the Carbon
Storage Potential of Furan Resin-Based
Green Composites”. 18th International
Conference on Composite Materials.

Fig. 1 shows the profile of the heating rate
as function of the inverse of temperature. The
plot shows a linear correspondence between thetwo variables.
2.9
2.7

ln q

2.5
2.3
2.1
1.9
1.7
1.5

1.55

1.65

1.75

1.85

1000/T (1/K)

Fig. 1. Heating rate profile based on the computed
kinetic parameters, E and A. Each line represents a
constant degree of conversion. (●) – 30%, (■) – 25%,(▲) – 20%, (♦) – 15%, and (+) – 10%.

Superimposing the curves in Fig. 1 with aplot based on experimental data shows asignificantly large deviation of the model. The
values showed an average percent deviation of
1410% when compared point-by-point with theexperimental data.

4

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

Development of Ultrasonic Torsion Fatigue Testing Machine
Akito KOKUBO1*, Yoshinobu SHIMAMURA1, Shingo KAMADA1, Hiroki MASUDA1,
Hitoshi ISHII2 , Keiichiro TOHGO1, Tomoyuki FUJII1, Tooru YAGASAKI3
and Masamichi HARADA3
1

Department of Mechanical Engineering, Shizuoka University
3-5-1 Johoku, Naka-ku, Hamamatsu, Shizuoka 432-8561, Japan
2
Professor Emeritus, Shizuoka University
3
Honda R&D Co., Ltd*e-mail: akokubo@mechmat.eng.shizuoka.ac.jp

1. Introduction
Recently, fatigue failure due to gigacycle(more than 107 cycles) loading have beenreported. It is necessary to investigate
gigacycle fatigue. However, the loading
frequency of conventional fatigue testingmachines is around 20Hz. It takes 19 months
to achieve gigacycle. Therefore, developing
a new method that can accelerate fatigue
testing is required.
In this study, we have developed anultrasonic torsional fatigue testing machine.
The cyclic frequency of the testing machineis around 20 kHz. So it takes only 14 hours
to achieve gigacycle and this machine
enables us to accelerate fatigue testing
considerably.

is amplified by decreasing the sectional areaof horn and specimen as shown in Fig.2.
Since generation of heat was remarkable
during test, duty time and pause time were
set to suppress temperature increase within
the allowable range (i.e. less than 100°C in
the case of steel). If the torsion amplitudefelt below a threshold, the test stopped.
①
⑨

⑧

②
⑪

⑩

④
⑤

2. Ultrasonic Torsion Fatigue Testing
MachineConfiguration of ultrasonic torsion
fatigue testing machine is shown in Fig.1.
The main components of the ultrasonictorsion fatigue testing machine are a signal
generator, a torsional oscillator, anamplifying horn and a specimen. A signal
generator generates electronic signal at theresonance frequency of the horn andspecimen. Torsional oscillator converts theelectronic
signalintoatorsional
displacement at the same frequency. Thus
cyclic loading can be applied to thespecimen due to resonation. Since thetorsional displacment generated by theoscillator is small, the torsional displacement

5①Torsional oscillator②Amplifying horn
③Specimen④Gap gauge⑤Output plate⑥Gap gauge amplifier⑦Oscilloscope⑧Signal generator⑨Electric power amplifier⑩Microscope⑪Personal computer③⑥⑦

Fig. 1 Ultrasonic torsion fatigue testing machine.

Shear stress
distribution
Torsion angle
distribution

Maximumshear stressFig. 2 Shear stress and torsion angle distribution.

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

3. New Testing Machine with
Automatic Control
The existing ultrasonic torsion fatigue
testing machine is controlled manually. Thus,
the testing machine cannot follow the changeof the resonance frequency caused by room
temperature change. Besides, maximum
shear stress applied by the testing machine isabout 800MPa. Higher shear stress isrequired to investigate the higher strength
steels.
To solve these problems, we are going todevelop a new ultrasonic torsion testingmachine. This testing machine adopts asignal generator that can automatically turnthe resonance frequency and can follow thechange of the resonance frequency.
Moreover, the torsional oscillator has higher
output and then be able to apply more than
1000MPa of shear stress to the specimen.

4. Application
With an ultrasonic torsion fatigue testingmachine, the maximum shear stress arises on
the surface of a specimen because of torsion.
It is suitable to investigate the effect of
surface treatment (i.e. carburizing or coating)on fatigue property.
Since the testing machine can apply
higher shear stress than 800MPa, it enables
us to conduct fatigue testing for higher
strength steels during short period.

5. Conclusion
We are going to develop a new testingmachine with automatic control.

6Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

Dip Coating of TiO2 Photocatalyst on Glass Raschig Rings for Flow
Photocatalytic Reactor Application
Patrick D. Ramoso and Maria Lourdes P. Dalida*
Department of Chemical Engineering, College of Engineering, University of the Philippines,
Diliman, Quezon City 1101, Philippines
TEL&FAX: +63-2-929-6640*
e-mail: mpdalida@up.edu.ph

1. Introduction
With the decreasing supply of cleanwater due to pollution from industrial
effluents, the challenge of developing anefficient wastewater treatment process has
been widely studied in the past years.
Photocatalysis has been extensively studied
for its application to the removal of organicand inorganic contaminants from water [1].
Many organic pollutants in water can becompletely decomposed at the surface ofUV-irradiated TiO2; these include alkanes,
haloalkanes, aliphatic alcohols, carboxylic
acids, alkenes, aromatics, haloaromatics,
polymers, surfactants, herbicides, pesticides
and dyes [2].
The
heterogeneous
photocatalytic
reaction starts with the excitation of the TiO2
catalyst by ultraviolet light with energies
greater than or equal to the band gap energy(Eph ≥ Ebg), leading to the generation ofmobile electrons (e- ) in the higher energy
conduction band (Ecb) and positive holes (h+)
in the lower energy valence band (Evb) [3].
(1)
photocatalyst → e − + h +The formation of the electron-hole pairs
leads to the generation of hydroxyl (∙OH)
radicals.
The adsorbed hydroxyl radicals are very
reactive and oxidize the adsorbed substrates(RXad) into mineral acids including carbon
dioxide and water:(2)• OH ad + RX ad → CO2 + H 2O
The recombination of the electron andelectron-hole is undesired and may lead towasted energy and process inefficiency [3].
The photocatalyst could either besuspended in a slurry or immobilized on a
support. Slurry systems require a
post-process separation such as filtration to
separate the catalyst. In an immobilized
system, there is continuous operation and no7

need for an additional separation process, but
it may be vulnerable to catalyst wash out [3].
The degradation of methylene blue inwater by Degussa P25 TiO2 in a batch slurry
reactor has been observed and optimized in aprevious study. The optimum parameters
were found to be 20.6 mg/L initial MB
concentration, pH 9.76 and catalyst loadingof 6.82 g/L, which resulted to adecolorization efficiency of 97.6% [4].
In this study, Degussa P25 TiO2
photocatalyst was immobilized on glass
Raschig rings using various dip-coating
media. The fabricated catalysts aresubsequently analyzed using an FTIR
spectrometer to characterize the catalyst.

2. Experimental
Degussa P25 TiO2 (25% rutile, 75%
anatase) were obtained as the photocatalyst
to be coated on a glass Raschig rings
approximately ¼ inch in diameter as support.
Various dip coating media listed in Table 1
were used to immobilize the TiO2.
Table 1.

Dip coating media

A
B
C

TiO2-water slurry (1 % wt.)
TiO2-water mixture with cornstarch
TiO2 mixture with silicone adhesive
as binder and paint thinner as dilutant
The prepared catalyst was subjected to
Fourier
Transform
Infrared(FTIR)
spectroscopy using a Thermo ScientificNicolet 6700 FT-IR spectrometer. Also
subjected to FTIR analysis are samples ofblank Raschig rings and Degussa P25 TiO2.

3. Results and Discussion
The resulting catalysts were observed to
be problematic in terms of the binding of theJapan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japancoating medium with the Raschig rings. For
catalyst A, the TiO2 could be removed fromthe Raschig ring by hand. For catalyst B, theproduct showed lumps, as opposed to thedesired film-like coating. In addition, thecalcined coat B product contained blackspots, indicating an incomplete degradationof cornstarch. For coat medium C, the TiO2
coating cracked and flaked out.
As a reference, the FTIR spectra of theblank Raschig ring sample and the Degussa
P25 TiO2 sample are provided in Fig. 1. Figs.
2, 3, and 4 show the FTIR spectra of the
product catalyst using coat medium A, B andC, respectively, with respect to the blank
Raschig ring sample, and the difference ofthe spectra.

Fig. 1. FTIR spectra of blank glass Raschig ringand Degussa P25 TiO2 samples

and 4) dropped, instead of an increase, as
seen in the blank Raschig ring sample. In
addition, the Degussa P25 TiO2 sample also
contained a peak on the same wave number.
It is thus suggested that some reaction took
place in catalyst fabrication that caused thematerial to have an opposing absorbancebehavior at the given wave number.
In Fig. 3, the peak at 2345 cm-1 loweredin magnitude compared to the blank sample,
but did not have an opposing behavior as
Figs. 2 and 4; however, this different
behavior may be attributed to its not being
calcined. Hence, calcination may be a causeof the opposite absorbance behavior.

4. Conclusions
The successful fabrication of a
dip-coated TiO2 photocatalyst onto glass
Raschig rings remains to be a challenge, as
the appropriate binder and coating conditions
would have to be improved in ensuring gooddispersion of catalyst and achieving afilmlike coating. The changing absorbancebehavior of the calcined photocatalyst issuggested to be caused by the calcination
process, brought about by the decompositionof organics present in the uncalcined
catalyst.

Acknowledgments
Fig. 2. FTIR spectra of calcined catalyst using
Coat A , blank Raschig ring, and their difference

The authors thank Adolph Bravo Jr.,
Ervin Cezar and Darlene Que for the
fabrication of TiO2-coated Raschig rings.
The authors would also like to express
their gratitude to Dr. Rizalinda de Leon for
the use of the FTIR in the UP Diliman
Chemical Engineering Laboratory and David
Gonzales and Jay R Adolacion for their help
in performing the FTIR analyses.

Fig. 3. FTIR spectra of uncalcined catalyst using
Coat B, blank Raschig ring, and their difference

References

Fig. 4. Wide FTIR spectra of calcined catalyst
using Coat C (silicone binder), blank glass
Raschig ring, and their difference

Of particular interest in spectra above isthe wave number at 2345 cm-1, as theabsorbance of the product A and C (Figs. 2

8[1] K. Nagaveni, G. Sivalingam, M.S. Hegde
and G. Madras, Appl. Catal. B. Environ.
Lett. 48 (2004) 83-93.
[2] A. Fujishima, X. Zhang and D.A. Tryk,
Surf. Sci. Rep. 63 (2008) 515-582.
[3] H. de Lasa, B. Serrano and M. Salaices,
2005. Photocatlytic Reaction
Engineering. USA: SpringerLink.
[4] Kounvong, K., Dalida, M.P., Bajamundi,
C.E., Hinode, H. (2011). Removal of
Color in Water Solution using TiO2
Photocatalyst. Unpublished manuscript.

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

Effect of Foil Thickness on Mechanical Property of Pure Copper Foil
Asuka Yokoyama*1, Tomoyuki Fujii*1, Keiichiro Tohgo*1,
Yasuhiro Noda*2 and Yoshinobu Shimamura*1*1

Shizuoka University Department of Mechanical Engineering
3-5-1 Johoku Naka-ku, Hamamatsu, 432-8561.Japan*2
Rengo Co., Ltde-mail: ayokoyama@mechmat.eng.shizuoka.ac.jp

1. Introduction

3. Results and Discussion

Pure copper foil is widely applied to theelectrical wiring in printed circuits, negative-electrode material in lithium-ion celland so on. It is important to evaluate themechanical properties of the copper foil because they are used in severe mechanical andelectrical loading. Many investigations of themechanical properties of copper foil werereported. It was noted that deformation andfracture behavior of the metallic foils weredifferent from those of bulk materials because of their unique micro-structure. It is
important to clarify the mechanical properties of the metallic foil to evaluate their integrity in service.
In this study, tensile tests of pure copper
foils were conducted to evaluate fracture
behavior and clarify the effect of foil thickness on the deformation and fracture behavior.

3.1 Stress-strain curves
Figure 1 shows nominal stress – strain
curves at each thickness. All specimens
showed large elastic deformation. The tensile
strength and strain at tensile strength decrease with decreasing foil thickness. Figure
2 shows the tensile strength as a function offoil thickness. The foil thickness is normalized by grain diameter. The tensile strength
was constant when the thickness was thicker
than grain diameter. However, tensile
strength goes down rapidly when the thickness was thinner than grain diameter.

2. Experimental procedure
2.1 Material
Cold rolling copper foils (99.96% copper) whose thickness is 5μm, 10μm, 50μm
and 2mm. The specimen shape was rectangle
for copper foil and dog-bone shape for copper sheet. The tensile detection was rolling
direction. The grain diameter of all specimens was set to about 20μm by heat treatment.
2.2 Tensile testingTensile tests were conducted at room
temperature and crosshead speed 0.5mm/min.
The elongation was measured by anon-contact extensometer. After the tensile
tests, fracture surface was observed by scanning electron microscope in order to investigate the fracture morphology.

9

3.2 Fracture morphology
Figures 3(a) and (b) shows the fracture
morphology of thickness of 10µm and 50µm,
respectively. The intergranular fracture occurred in thickness of 10µm. In the case of
5 µm, the same fracture morphology was
also observed. On the other hand, the chisel
point fracture occurred in thickness of 50µm.
This result agrees the fracture morphology ofcommon metallic materials.
The effect of foil thickness on tensile
strength is explained as follows: when the
thickness is thicker than foil thickness, thelocal necking occurs, and then chisel point
fracture occurs. The large plastic
deformation occurs and the tensile strength is high.
On the other hand, when the foil thickness isthinner than grain diameter, the intergranularfracture occurred. Therefore, the plastic deformation during tension is terminated andthe tensile strength is low.

4. Conclusion
The tensile tests for four kinds of thickness of copper foil were conducted in orderto evaluate their mechanical properties. The

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

Fig. 1 Stress – strain curves of copper foil.

Fig. 2 Tensile strength as a function of normalized thickness(a) Foil thickness of 50µm.

(b) Foil thickness of 10µm.
Fig. 2. Fracture morphology of copper foil.

conclusions obtained in this investigation aresummarized as follows.
1. The tensile strength and strain at tensile
strength decreased when the foil thickness was thinner than grain diameter.
2. The chisel point fracture occurred when
the foil thickness was thicker than grain
diameter. On the other hand, the intergranular fracture occurred when the foil
thickness was thinner than grain diameter.

Reference
1.

2.

H. Harada, Y. Z.Ssun, Y. Sakamoto, Y.
Marumo, L. Ruan. Slide-bending formation of thin metal sheet by using an
industrial robot, Transactions of the Japan Society of Mechanical Engineers, C,
Vol.73, No.734(2007), pp.2834-2840.
T. Sano, K. Toyama, H. Kimachi, T. Iai,
K. Tanaka and Y. Akiniwa. Evaluation

10

3.

of fracture strength by crack initiationand propagation on grain boundary inpolycrystals, Transactions of the Japan
Society of Mechanical Engineers, No.55(2006), pp.123-124.
B. Weiss, V. Groger, G. Khatibi, A. Kotas, P. Zimprich, R.Stickler, B. Zagar.
Characterization of mechanical andthermal properties of thin cu foils andwires, Sensors and actuators, A,
No.99(2002), pp.172-182.

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

Fatigue Property of Jute MonoFilament
Kazunori UEMATSU*, Yoshinobu SHIMAMURA
Hideaki KATOGI, Keiichiro TOHGO and Tomoyuki FUJII
Department of Mechanical Engineering, Shizuoka University
3-5-1 Johoku, Naka-ku, Hamamatsu, Shizuoka 432-8561, Japan*e-mail: kuematsu@mechmat.eng.shizuoka.ac.jp

1. Introduction

4．Tensile Test of Jute Filament

In recent years, with the growing interest inenvironmental issue, composite materials fromnatural sources have been developed. However,superior strength and fatigue properties arenecessary to alternate traditional load-bearing
structures. Therefore, fatigue strength ofnatural fiber reinforced composites should be
investigated. In order to elucidate the fatigue
property of the composites, it is necessary to
clarify fatigue property of natural fibers. In thisstudy the fatigue property of jute mono
filament was investigated.

Qausi-static tensile tests were conducted atroom temperature. The cross head speed was
1mm/min and the gauge length was 10mm.
Table 1 shows the mechanical properties.

2. Structure of Natural Fiber
Figure 1 shows a schematic of typical naturalelementary fiber. Open hole, called lumen,
exists in the center of an elementary fiber.
Microfibril (MF) is a bundle of cellulose,
which is bonded by hydrogen bonding,surrounds around cell walls. MF has an angle
to the axial direction, which determines theaxial stiffness. MFs are adhered byhemicelluloses and lignin. Monofilamentconsists of elementary fibers that are adheredby pectin.

Table1. Mechanical property
Tensile strength
[MPa]
448

Young modulus
[GPa]
16

5．Fatigue Test of Jute Filament
Fatigue testing was conducted at room
temperature. Loading frequency was 10Hz andthe gauge length was 10mm. The stress ratio is
0.1 and the maximum stress was 60 to 120% of
the tensile strength.
Figure 2 shows S-N diagram. The error bar
at 100 cycles is the standard deviation of thetensile strength.
Fatigue strength at 106 cycles was about
50% of the tensile strength. Therefore, fatigue
property of jute Monofilaments is considered tobe superior. Figure 3 shows the fracture portion
after fatigue testing. Splitting among
elementary fibers and pull out of secondary
wall in an elementary fiber were found.

3．Specimen

6．Conclusions

Alkaline treatment was performed forwashing jute yarns. Jute filaments wereextracted from the washed yarns. The diameterof a Monofilament was measured from two
perpendicular directions along the length. The
cross sectional area of a fractured portion was
estimated by elliptical approximation using theabove data.

11(1) Jute Monofilament has superior fatigue
property.
(2) Splitting between elementary fibers andpull out of secondary wall were found after
fatigue failure.

Reference(1)

M. M. Meyers, P.-Y. Chen, A.Y.-M. Lin
andY. Seki, Progress in Materials Science
53 (2008) pp.1-206

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

10μm

Fig.1

Structure of natural-fiber(1)

Fig.2

S-N diagram of jute filament

12

Fig.3 Jute filament after fatigue

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

Synthesis of Furfural from Pineapple Bagasse
Emmanuel Belostrino*, Billy Joe Uy, Mark Louis Lagura and Terence Tumolva
Department of Chemical Engineering, University of the Philippines
Diliman 1101 Quezon City, Philippines
TELEFAX: +632-929-6640*
e-mail: epbelostrino@upd.edu.ph

1. Introduction
Because of the continuous decline inreserves and increase of prices of fossil fuels,
significant amounts of research are done
globally to produce chemicals fromalternative renewable sources. Agricultural
waste materials prove to be a viable option
as a potential source of valuable organic
chemicals such as sugars, ethanol and basic
components of polymer resins.
Furfural is produced by the hydrolysis ofxylose-rich materials. It is an essential
chemical because of its use as a selective
solvent for the separation of saturated andunsaturated compounds in fuels. Moreover,
it is also used to derive other valuable
chemicals such as furfuryl alcohol, which is
the monomer for furan resins, which is abiothermoset.
Previous researches have been conducted
to determine the viability of producing
furfural through acid hydrolysis of different
agricultural residues such as corn cobs, ricehulls, sugar bagasse, and fruit shells [1].

In the Philippines, pineapple isconsidered as one of the country’s major
agricultural products, with an annual
production of approximately two million
metric tons. The xylose-rich pineapple
bagasse produced from juice manufacturing
plants is a potential viable source of raw
material in the synthesis of furfural. This
research is the first step in the study of thefeasibility of locally manufacturing furfuraland furfuryl alcohol in the Philippines.

2. Acid Hydrolysis of Pineapple
BagasseThe pineapple bagasse was crushed and0.1 g of the sample was placed inside a 10
mL reaction tube. 3.5 mL of 2 M H2SO4 wasthen added in the tube and was tightly
covered. Hydrolysis of the sample wascarried out in a 180 ºC oil bath. For each run,varying reaction times were observed (3 min,
6 min, 9 min, 12 min, 15 min).
After the desired reaction time, thereaction tube was cooled in a water bath andwas filtered. A few drops of hot water wasadded to wash the precipitate. 20 mL of
2,4-dinitro phenyl hydrazine solution wasadded to the furfural-containing filtrate. A
brown precipitate (furfural 2,4-dinitro phenyl
hydrazine) formed and was weighed [2]. The
furfural yield was then calculated. Two trials
were performed for each run.

3. Results and Discussion
Figure 2 shows the furfural yield of
pineapple bagasse as a function of hydrolysis
time. The results show that the yield
increases linearly with hydrolysis time (withR2 = 0.9779). For a hydrolysis period of 15
minutes, the maximum yield obtainable isabout 11.53%.

Fig. 1. Pineapple bagasse.

13

% furfural yield

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

12
11
10
9
8
7
6
0

5

10

15

hydrolysis time (min)Fig. 2. Furfural yield of pineapple bagasse afunction of hydrolysis time.

The effects of acid concentration andreaction temperature on the furfural yield arealso to be investigated in the next phase of
the project- this is to determine the mostideal conditions that would lead to maximum
furfural yield.

4. Conclusion
Pineapple bagasse is a viable raw
material for the production of furfural.
Increasing the hydrolysis time increases the
furfural yield. The yield can be further
maximized by varying the acid concentration
and reaction temperature to optimize thehydrolysis process.

References[1] H. Mansilla, J. Baeza, S. Urzua, G.
Maturana, J. Villaseñor and N. Duran,Acid-Catalyzed Hydrolysis of Rice Hull:
Evaluation of Furfural Production,
Bioresource Technology, 66 (1998)
189-193.
[2] A. Demirbas, Furfural Production from
Fruit
ShellsbyAcid-Catalyzed
Hydrolysis, Energy Sources, Part A, 28(2006) 157-165.

14

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

Fatigue Strengh of a Paper-based Friction Material
under Shear-Compressive Loading
Naoya URATA, Jun SHIBATA, Tomoyuki FUJII, Keiichiro TOHGO
and Yoshinobu SHIMAMURA
Dept. of Mechanical Engineering, Shizuoka University
3-5-1 Johoku, Naka-ku, Hamamatu, Shizuoka, 432-8561, Japane-mail: nurata@mechmat.eng.shizuoka.ac.jp

2.2 Shear-compressive test
The specimens were subjected to thecompressive load at an inclined angle ofas shown in Fig. 1. The stress Σ, resolved
shear stress σ, and compressive stress τ, aredefined in Fig. 1. The cyclic frequency was
10Hz and the sinusoidal load with the loading ratio of R=0.1 was applied. When thespecimens are not broken at 106 cycles, thefatigue test is terminated and this condition
is regarded as the fatigue strength for 106
cycles.
2.3 Cyclic compressive loading behavior
Compressive deformation tests were carried out in order to discuss the fatigue

15

3. Results and Disscusion
3.1 Fatigue strength
Figure 2 shows the relationship between
the stress range ∆Σ and the number of cycles
N. The fatigue strength decreases with increasing the number of cycles. With increasing inclined angle θ, the compressive stressbecomes dominant and then the fatigue
strength increases.
σ

P

θ
τ

Pτ

θ
P

σ

τP τ

P : Load
A : Area of friction paperθ : Loading direction
・StressΣ =P/A
・Normal stressσ =Σ sinθ
・Shear stressτ =Σ cosθFig.1Loading condition.
1000

τ/σ=0.27 (θ=75°)
τ/σ=0.58 (θ=60°)
τ/σ=0.87 (θ=49°)
τ/σ=1.00 (θ=45°)
τ/σ=1.60 (θ=32°)
τ/σ=3.49 (θ=16°)

100

∆Σ
MPa

2. Experimental Procedure
2.1 Material
A paper-based friction material is composed of aramid fibers and phenolic resin.
The material includes the aramid fiber of
70wt% and phenolic resin of 30wt%, and theporosity was 72.2%. The thickness was
0.5±0.02mm or 1.5±0.02mm. The materials
were prepared by bonding two sheets ofaluminum alloy on both surfaces.

strength. The tests were carried out under thepure compressive cyclic load with the stressratio of 0.1 and applied load rate of
0.1kN/min. The maximum load increased
stepwise by 1.0kN up to 10kN. The compressive load was repeated five times at thesame load level, and hysteresis loops of thefifth cycle were examined.

Stress,

1. Introduction
Paper-based friction materials are used
for clutch disc of an automatic transmission.
Paper-based friction materials are subject tocyclic shear-compressive loading under elevated temperature in oily environment. It is
important to clarify their fatigue properties
under the cyclic shear-compressive loading
to evaluate their remaining life in services.
This paper deals with the fatigue strength
under thecyclicshear-compressive
loading to evaluate their fatigue properties．
The influence of ratio between shear andcompressive stress on the fatigue strength
was evaluated.

10

1
100

101

102 103 104 105 106
Number of cycles, N cycle

107

Fig.2 S-N curves of the paper-based friction
material under shear-compressive loading.

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

3.2 Compressive Deformation Property
The hysteresis loops of cyclic deformation test under pure compressive load areshown in Fig. 3. With increasing stress level,
the hysteresis loop shifts to the high strain
direction and its gradient becomes steep.
For each hysteresis loop, the unloading
elastic modulus is defined as a slope of theunloading relation from the maximum stressand the strain range ∆ε are defined as therange between strain at maximum stress andat minimum stress. Figure 4 shows the
maximum strain ε0, strain range ∆ε, elastic
modulus E as functions of the maximum
compressive stress. the maximum strain andYoung's modulus increased with increasing
maximum compressive stress, while thestrain range remained as constant low value. These results are explained as follows:
the paper-based friction material is a porous
material with porosity of about 70%. The
porosity decreases with increasing compressive stress, and then the friction materials
become dense and the elastic modulus becomes high. Therefore, the gradient of thehysteresis loops becomes steep and the strain
range does not increase as compared with anincrease in the stress range. The reason why
the fatigue strength of the paper-based friction material is remarkably high under thecompressive-dominant stress condition is
attributed to their characteristics of the compressive cyclic deformation as mentioned
above.
4.Conclusion
The static fracture and fatigue tests of thepaper-based friction material were conductedunder the various shear-compressive loading
conditions, and the influence of loading
conditions on the static fracture strength,
fatigue strength and fracture surface
morphology were discussed. Furthermore,
the cyclic compressive deformation behavior
was examined to explain the fatigue strengthof the paper-based friction material undercompressive-dominant stress condition. The
conclusions obtained in this investigation aresummarized as follows.

16

1.

2.

The fatigue strength decreases withincreasing the number of cycles. The
fatigue strength is higher when thecompressive stress is more dominant.
In the pure compressive cyclic
deformation tests, when the stressrange increased the gradient of thehysteresis loops becomes steep and thestrain range does not increase.
Therefore, it is considered that thefatigue strength is remarkably highwhen the compressive stress isdominant.

Fig.3 Stress-strain hysteresis loopof compressive cyclic deformation.

Fig.4 Young’s modulus, maximum strain andstrain range as functions of compressive stress.

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

Synthesis of Furfural from Coconut Shells
Billy Joe Uy*, Emmanuel Belostrino, Mark Louis Lagura,
Rodel Guerrero, and Terence Tumolva

Department of Chemical Engineering, College of Engineering, University of the Philippines,
Diliman, Quezon City 1101, Philippines
TEL&FAX: +06-981-8500*
e-mail: byuy@upd.edu.ph

1. Introduction

monomer of biosynthetic furan resin),furfurylic alcohol and tetrahydrofuran (THF).

Coconut in the Philippines is popularly
known as the “Tree of Life” because of thewide array of products and by-products thatcan be derived from the tree. Some of theseproducts are coconut meat, oil, juice, husk,
shell, shell charcoal, leaves, husk, pith,inflorescence, trunk and roots. The coconut
shell is a treated as a byproduct in the
production of nut, copra and coconut oil. It iscurrently used as a shell charcoal fordomestic and commercial fuel. It is said that
there are more than 300 million coconut
trees in the Philippines that produces anannual average of 15 billion nuts. [3]Fig. 1. Crushed coconut shells.

Furfural is produced from the pentosan
fraction of the lignocellulosic materials thatare natural and abundant natural resource.
Pentosan from nonfood residues of foodcrops and wood wastes are first converted
into pentoses from monosaccharides by acidhydrolysis and further dehydration of these
pentoses will yield furfural. Furfural iscurrently used as a direct solvent inpetroleum refining and also in the productionof phenolic resins. Furfural is also an
important intermediate in the synthesis ofvaluable solvents such as furfuryl alcohol (a17Chemicals that are derived from nonfood agricultural residues like furfural areessential in obtaining a self-sustaining
industry. With the rapid consumption andcontinuous decline of the supply for fossil
fuels,
findingalternative
renewable
resources is vital in any industry.

2. Acid Hydrolysis Experiment for
Coconut Shells
The crushed air-dried sample of the shell
was placed inside a 5 mL test tube and wastightly sealed. 3.5 mL of 2M sulfuric acidwas then added before heating in an oil bathat 180°C. The hydrolysis time (3, 6, 9, 12
and 15 min) were varied to observe its effectto the furfural yield. The test tube was thenpromptly cooled in a water bath and the
product was filtered and then washed with
hot water.
Furfural was precipitated from thesolution by adding 2,4-dinitro phenyl
hydrazine solution. The brown precipitate(furfural 2,4-dinitro phenyl hydrazine) was
then filtered and weighed to compute for the
furfural yield.

3. Results and Discussion
A plot of the furfural yield with varyinghydrolysis time is shown in Figure 2. A trendline with an R2=0.6104 is obtained whichindicate the low level linearity of the points.
This can be due to the presence of errors andthe degree of violence of the reactions. It canbe seen however that the yield increases as
the hydrolysis time increases. The peak yield
was 12.4% from the 15 min hydrolysis time.

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

Furfural Yield
15%yield10
R² = 0.614
5
0
0

10
time (min)20

Fig. 2. Furfural Yield from Coconut shells withvarying hydrolysis time

Linearity of the data points can be
improved by having a better experiment
setup and by performing more trials per run.
Variables that may affect the yield of furfuralsuch as the temperature and acidconcentration should be investigated tofurther enhance the yield of furfural.

4. Conclusion
Coconut shells prove to be a suitable raw
material for the production of furfural thathas yielded a maximum value of 12.4%. An
increase in the hydrolysis time also showed
an increase in the yield of furfural.
Optimizationoftheprocess
andmanipulation of other variables could further
increase the yield of furfural synthesizedfrom coconut shells.

Reference[1] A. Demirbas, Furfural Production from
Fruit
ShellsbyAcid-Catalyzed
Hydrolysis, Energy Sources, Part A, 28(2006) 157-165.
[2] M. Kazemi, Furfural Production from
pisthachio green hulls as agriculturalresidues, October 2009.
[3] Philippine
Coconut
Authority,
Department
ofAgriculture(www.pca.da.gov.ph)18

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

Evaluation of Mechanical Properties of PSZ-Ti Biocompatible
Composite Fabricated by MIM Method
Kazufumi NAKAZAWA1*, Tomoyuki FUJI1, Keiichiro TOHGO1,
Masaki ISHIKURA2 and Yoshinobu SHIMAMURA1
1

Dept. of Mechanical Engineering, Shizuoka University
3-5-1 Johoku, Naka-ku, Hamamatu, Shizuoka, 432-8561, Japan
2

Nippon Kinzoku .Co.Ltd*e-mail: knakazawa@mechmat.eng.shizuoka.ac.jp

1. Introduction

debinding and sintering.

Partially stabilized zirconia(PSZ) andpure titanium(Ti) are expected as implantmaterials due to biocompatibility. However,homogeneous materials fabricated by PSZ or
Ti are insufficient to satisfy characteristics
required for medical use.
This paper deals with fabrication ofcomposites consisting of Ti and PSZ to derive their good characteristics of both materials. The composites were fabricated bymetal injection modeling. Indentation andthree-point bending tests were conducted toevaluate fracture toughness. The reaction
products were identified by X-ray diffraction
analysis.

2. Experimental procedure

100
12

80

PSZ/(PSZ+Ti) (vol%)
60
40
20

The fracture toughness was measured byindentation test and three-point bending test.
The cracks were introduced from the cornerof the indent, and the fracture toughness wascalculated by IF method when the Ti volume
fraction was less than 90%. On the other
hand, the fracture toughness was measured
by three-point bending test because no crack
was introduced by using the indentation tests
when the Ti volume fraction was more than90%.

3. Experimental results
3.1 Fracture toughness
Figure 1 shows the relationship between
the fracture toughness and the Ti volume
fraction. The fracture toughness decreased
with increasing of Ti volume fraction when
the Ti volume fraction was less than 90%.
On the other hand, the fracture toughness
increased with increasing of Ti volume fraction when the Ti content was more than 90%.

0Ti
TiO0.5Ti2ZrOPSZ(Tetragnal or cubic)

Solid:Three point bending test
Open:Indentation crack

100%PSZ

Intensity (arb.unit)

⋅m

9

6

50%PSZ
20%PSZ
10%PSZ
8%PSZ

3

5%PSZ

K

Fracture toughness

C,K IC (MPa0.5)

2.1 Fabrication method
PSZ powders with the grain size of 0.35
µm and pure Ti powders with the grain sizeof 24 µm were used as raw materials. These
powders were mixed in various volume ratios covering from 100% PSZ to 100% Ti atprescribed interval. The composites were
fabricated through the processes of forming,

2.2 Fracture toughness test

0
0

20

40
60
Ti/(PSZ+Ti) (vol%)

0%PSZ

80

20

100

30

40

50

60

70

80

2θ (degree)

Fig. 1 Fracture toughness as a function of Ti volume fraction.

19

Fig. 2 XRD patterns of the sintered materials.

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

3.2 Phase constitution of composites
Figure 2 shows the XRD patterns after
sintering. When the Ti volume fraction wasless than 90%, the oxide of titanium andother reaction products were formed after
sintering. The composites might be brittle
because of these reaction products. However,pure titanium remained after sintering when
the Ti volume fraction was more than 90%,
and the composites characterized by relatively high ductility.

20

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

Evaluating Carbon Storage Potential in Furfural Synthesis
Rodel D. Guerrero* and Terence P. Tumolva
Department of Chemical Engineering, University of the Philippines,
Diliman 1101 Quezon City, Philippines
TELEFAX: +6329296640*
e-mail: rodeldayagguerrero@gmail.com

1. Introduction
Mitigating the contribution of fossil fuelemissions to global warming has been and is
still a great environmental concern. Large
quantities of carbon dioxide, CO2, which isbelieved to be one of the key greenhousegases that promote climate change, is being
released into the atmosphere from the use offossil fuel in power generation and otherindustries. Thus, a large number of
researches have been already conducted forfinding out ways to reduce CO2 emissions.
Among the current trend in line with theaim of reducing carbon dioxide in theatmosphere is the production of bio-based
products, particularly polymers. Thesematerials are proven to beneficial given theirability to ‘fix’ the carbon content of thematerial, making them carbon neutral.
Bio-based polymers or bioplastics can either
be thermoplastic or thermosetting in nature,but in terms of tonnage, the bulk of plastics
produced are thermoplastics.
Thermoplastics are known to have low to
non-existent polymer chain interactions thus
making it readily vulnerable to reactions.
These plastics can be only used forshort-term applications, which is why
thermosets are preferred for long-life
applications. However, the production ofnon-biodegradable bio-based thermosets forapplications that require persistent materials
has been given little attention so far,although there is a demand for large amountsof these materials [3].
Polyfurfuryl alcohol (PFA) is abiosynthetic thermoset derived fromvegetable byproducts. Compared to othercommon resins, this highly stable polymer
offers a very significant improvement in the21

carbon storage potential of green composites
when used as a matrix. PFA is polymerizedfrom furfuryl alcohol derived from furfural,
which is manufactured from agriculturalresidues such as sugar cane, bagasse, oathulls, corn cobs and rice hulls.
Since carbon storage potential in termsof CO2 fixation is a key environmental
parameter evaluated in this study, certain
Life Cycle Analysis (LCA) principles areapplied on the material to serve as a guideand tool for the evaluation of carbon storage
potential. However, analyses of this kind aremainly concerned on the overall CO2
emission and not on the bio-based carbon
content of the material [1]. So in this paper, aquantification of the extent of carbon
fixation from the synthesis of furfuralderived from pineapple bagasse will be
investigated. As such, measurements of the
carbon dioxide released during the furfural’s
synthesis due to fossil fuel consumption forenergy supply will be calculated.

2. Carbon Balance
As a biosynthetic thermoset, it isstrongly believed that PFA has the capacity
to store carbon from biomass produced by
the utilization of atmospheric CO2 by plants
during photosynthesis. However, as with any
industrial process, the manufacture of thismaterial entails the use of energy, whichtranslates to CO2 emission that could easily
offset the effectiveness of furan to sequester
CO2 as stored bio-based carbon [1].
Therefore, it is also important to identify thedifferent pertinent flow streams of carbon
and the energy consumption throughout theentire production process of the monomer of
PFA which is furfural. This can be done bycalculating the net bio-based carbon contentor E(NB) of the material as well as theJapan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japanenergy generated during the process which
has its equivalent amount of CO2 emission
mainly due to the consumption of fossil fuels
to generate the energy.

3. Results and Discussion
The hydrolysis time for the synthesis offurfural from the pineapple bagasse
lasted for about 15 minutes.

Figure 1. Furfural synthesis set up.

Table 1. Carbon balance for furfuralproduction.
Items

Value

Unit

CO2 production

0.0050277

g

Fossil-based carbon equivalent, F

0.001371g

MW of furfuryl alcohol, C5H4O2

96.08

g/mol

Wt. furfural produced

0.01198g

Weight C in furfural

0.007481g

Bio-based carbon equivalent, B

0.007481g

0.008852g0.8451g/g

0.00611g

Total carbon content equivalent,
E(T) = F + B
Bio-based carbon content equivalent,E(B) = B/(F + B)
Net bio-based carbon content
equivalent, E(NB) = B – F

4. Conclusion
Carbon storage exhibited by thesynthesis of furfural was evaluated using theinformation obtained from carbon balance.
The potential of carbon sequestration
exhibited by the furfural synthesis for the
raw material- pineapple bagasse- proved to
be an environment-friendly process forwhich the carbon fixation of thepolymerization of such monomer would beof great interest in future researches.

22

Reference[1] T. Tumolva, M. Kubouchi, S. Aoki, and T.
Sakai (2011). “Evaluating the Carbon
Storage Potential of Furan Resin-Based
Green Composites”. 18th International
Conference on Composite Materials.
[2] Demirbas,
A.
(2006).
“Furfural
Production from Fruit Shells by
Acid-Catalyzed Hydrolysis.”[3] Steinbuchel,A.
(2005).
Non-biodegradable biopolymers fromrenewable resources: perspectives andimpacts. Science Direct[4] "IPCC Special Report Carbon Dioxide
Capture and Storage Summary for
Policymakers". Intergovernmental Panelon
ClimateChange.
Retrieved
2011-10-05.

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

Mechanical property of unidirectional MWNT sheet/epoxy composites
M. Sakai1*，Y. Shimamura1，N. Morisawa1，K. Tohgo1 and T. Fujii1
1

Department of Mechanical Engineering, Shizuoka University，
3-5-1 Johoku, Naka-ku, Hamamatsu, Shizuoka 432-8561, Japan*e-mail: msakai@mechmat.eng.shizuoka.ac.jp

Introduction

Figure 1 shows typical stress-strain curvesof resin, MWNT sheet and composite
specimens with different Vf. Table 1 shows
the average Young’s modulus and tensile
strength. Figure 2 shows a SEM image of afracture surface of a composite specimen
with Vf=13.7%.

Carbon nanotubes (CNT) have high specificstrength, stiffness, and low density, and are
anticipated to exceed the mechanicalproperties of carbon fibers, which is mainly
used for composite materials in aerospaceindustry. Therefore, CNTs attract attention invarious fields. In the field of composite,
CNTs are expected as high performance
reinforcement
materials,
andwidelyinvestigated for the last decade.
In this study, multi-walled carbon nanotube(MWNT) sheets developed by Inoue et al [1]were used as preform for making composites.
The mechanical properties were investigatedby tensile tests and SEM observation.

2.

180
150

Stress

90
60

[MPa]

120

30

Materials and Specimen

00

MWNT arrays were grown on a substrate bychemical vapor deposition (CVD method).
MWNT sheets are fabricated from the
MWNT array. Thickness and specific densityof MWNT sheets were about 15 µm and 0.4,
respectively. Bisphenol-A type epoxy resinwith high-temperature cure was used for
matrix.
The hand lay-up method was used tofabricate composites. Unidirectional MWNT
sheets were laid on a Teflon sheet and thenresin was impregnated. After curing,composite plate was cut into rectangularspecimens. Then, a specimen as glued onto apaper mount to fix the specimen. Fibervolume contents (Vf) of composites were
calculated by fiber mass contents that had
been measured by thermo gravimetricalanalysis.
The cross-head speed was 1mm/min atroom temperature. Displacement wasmeasuredbyusinganoncontact
extensometer.

3.

MWNT sheet
Resin(HT)Composite(Vf=5.0%)
Composite(Vf=13.7%)

σ

1.

0.01

0.02 0.03
Strain ε

0.04

0.05

Fig.1 Stress-strain curves.
Table.1 Mechanical properties.

Young'smodulus[GPa]Tensilestrength[MPa]

resin

MWNT
sheet

Composite(Vf=5.0%)

Composite(Vf=13.7%)

2.5

3.9

15.4

31.1

81.2

17.7

117.0

136.8

Vf=13.7%20µm

Fig.2 Fracture surface of composite (Vf =13.7%).

Results and Discussion

23

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, JapanThe enhancement of Young’s modulus andtensile strength were confirmed. In particular,
Young's modulus of composites with
Vf=13.7% was about 12 times as much asthat of resin. From thefractograph,
wettability of epoxy into MWNTs and wellalignment of CNTs in composite wereconfirmed.

4.

Conclusions

Using MWNT sheets as preform enables us
to enhance mechanical properties remarkably.
The further mechanical properties are
expected by increasing Vf.

References[1] Y. Inoue, K. Kakihata, Y. Hirono, T.
Horie, A. Ishida, and H. Mimura, APPLIEDPHYSICS LETTERS, 92 (2008), 213113

24

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

Evaluating the Carbon Storage Potential of NFRP
Using Water Hyacinth Fiber Reinforcement
Joseph Ortenero* and Terence Tumolva
Department of Chemical Engineering, University of the Philippines
Diliman 1101 Quezon City, Philippines
TELEFAX: +6329296640*
e-mail: josh_42786@yahoo.com

1. Introduction
The use of natural fiber as reinforcement
has significant advantages, among others are
in increasing mechanical properties, reducing
cost, biodegradability and especially therenewability and sustainability of thereinforcement. Currently, there is a greatabundance of research on natural fiberreinforced plastic (NFRP). However, most ofthese studies are focused on mechanicalproperty and thermal property evaluations
and only a small percentage is devoted to datacollection on environmental advantages in thearea of carbon sequestration with the use ofrenewable bio-based material. In this study, it
is attempted to develop a systematic approachto evaluating the carbon storage potential ofwater hyacinth reinforced composite. Figure
1 shows a sample of water hyacinth plant.

Water hyacinth was introduced as an
ornamental crop species in many countries
more than a century ago. Soon, it was
realized to be an invasive species due to theiradaptability to a wide type of fresh water
ecosystems and interference with humanactivities. However, it was recently realizedthat they could be sustainably managed intheir natural ecosystem and used asreinforcement in NFRP’s.

2. Carbon Balance
The effectiveness of water hyacinth fiber(WHF) in sequestering carbon was measured
in terms of equivalent carbon content. The
method adopted for evaluating carbon storage
potential was through the calculation of the
net bio-based carbon content of the material.
Net bio-based carbon content assessment is amore direct representation since it expresses
stored carbon in terms of carbon weightfraction within the material.

3. Result and Discussion

Fig. 1. Water hyacinth (Eichhornia crassipes) is
considered an invasive species, which invades
fresh water habitats and is listed along with someof the worst weeds.

25

Water hyacinth is low in lignin content(10%) and contains high amounts of cellulose(20%) and hemicelluloses (33%). The carbon
content of water hyacinth was estimatedbased on the average fraction of cellulose in
the fiber and the weight percent of carbon in
the cellulose. The calculation on net biobased carbon content was shown in Table 1.
The average cellulose content of water
hyacinth is around 25%. Carbon is in theorder of 52% of the cellulose fiber. Therefore,carbon safely sequestered by a water hyacinthJapan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

plant is 0.013 kg per kilogram of NFRP
composite considering 10% loading of WHF
in the NFRP composite. For the estimation ofcarbon content in orthophthalic unsaturated
polyester (ortho-UP), certain assumptions
were imposed to simplify calculations basedon a published C-NMR study on the
crosslinking of UP with styrene. The amountof carbon emission in the form of carbon
dioxide for the production of the polymer
matrix was based on a previously reported listof gross energy requirements for different
intermediates and plastics.

Table 1. Carbon balance for the fabrication ofwater hyacinth-reinforced NFRP
Items
Value
Unit
Wt. percent water hyacinth
10.0%
fibers in NFRP
Wt. water hyacinth fibers/kg
0.100
kg
NFRP
Wt. fraction cellulose in water
0.250
kg/kg
hyacinth fiber
Wt. percent C in cellulose
52.0%
Wt. C from abaca fibers
0.013
kg
Wt.UP resin matrix/kg NFRP
0.900
kg
Wt.C from ortho-UP
0.604
kg
Fossil based carbon equivalent
1.19
kg
Bio-based content in NFRP
10.0%
Bio-based carbon equivalent
0.013
kg
Total carbon content equivalent 1.203kg
Biobased carbon content
0.011
kg/kg
equivalent
Net biobased carbon content-1.177 kg
equivalent

4. Conclusion
Evaluation of carbon storage potential ofthermoset-based NFRP composite is vital forassessing the environmental impact of amaterial. The carbon storage potential of
NFRP can be easily increased by increasing
WHF content.

26

References[1] S Bolenz, H Omran, K Gierschner (1990)“Treatment of water hyacinth tissue toobtain useful products” Biowastes
33:263-274[2] T. Tumolva, M. Kubouchi, S. Aoki, T.
Sakai, “Evaluating the Carbon Storage
Potential of Furan Resin-Based Green
Composite”,
18th
International
Conference on Composite Materials

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

Tensile Property of Carbon Nanotube Spun Yarn Reinforced Composite
Kahori Oshima1, Yoshinobu Shimamura1, Keiichiro Tohgo1, Tomoyuki Fujii1,
Mikihisa Ishihara1, Yoku Inoue2 and Junichi Muramatsu2
1

2

Department of Mechanical Engineering, Shizuoka University,
3-5-1 Johoku Naka-ku, Hamamatsu, 432-8011, Japan

Department of Electrical and Electronic Engineering, Shizuoka University

1. Introduction
Carbon nanotubes (CNTs) are expected
to exceed the mechanical properties of
conventional carbon fibers, but growing
continuous CNTs have limitation so far.
Consequently, it is difficult to apply CNTs tostructural components. In order to solve thismatter, techniques of spinning have been
investigated. However, the basic mechanicalproperties of CNT spun yarn have not beenclarified.
In this study, tensile tests of CNT spunyarn were conducted and stress-strain curves
were obtained to investigate the mechanicalbehavior of CNT spun yarn. In addition,
CNT composite was fabricated by using thepultrusion technique, and tensile tests of
CNT composite were carried out.

2. MaterialsMultiwalledcarbonnanotubes(MWNTs) used in this study were grown on
a quartz glass plate with chemical vapor
deposition (CM-CVD method), using C2H2
and FeCl2 as a material and a catalyst,
respectively [1]. It was possible to draw out
MWNTs from array by Van der Waals’ force.
The MWNT length was around 1.2mm andthe diameter was 50nm. The spun yarn
diameter was about 45µm. Twist angle α isdefined as an angle of MWNT of outermost
layer to the longitudinal axis of a spun yarn.
Generally, it is known that properties of aspun yarn depend on the twist angle. In thisstudy, a spun yarn that the twist angle
α=25~30° was used. Room- temperature
curing epoxy was used for fabrication of
MWNT composite.

3. MWNT Composite
3.1 Fabrication of MWNT Composite
MWNT composites were fabricated by27

using the pultrusion technique. Figure 1
shows a schematic of pultrusion process of
MWNT composites. The advantages of thismethod are able to remove extra resin on a
MWNT bundle and also to form a cylindricalshape at the same time. In this study, 7 spunyarns were used because it was the effective
number of spun yarn for maximizing a
volume fraction; a hexagonal close-packed
structure is achieved. Loading tensile force
to MWNT composites while curing iseffective for getting specimens straight andfor restraining the expansion of yarn.
A die was made in a plastic board for thepultrusion, and an end of a MWNT bundle
was laced through the die. The MWNT
bundle was dipped into resin and thenplutluded. After that, a weight was attached
to an end of the bundle as dead load whilecuring. The diameter of MWNT composite
was about 120µm.

Fig.1 Pultrusion process of MWNT composite

3.2 Tensile Test
A MWNT composite specimen wasplaced on a U-shaped paper mount. The bothends of the specimen were glued withadhesive. The gauge length was 15mm. The
paper mount was cut in a half after the
specimen was fixed to a testing machine, andthen tensile tests were conducted. The tests
were carried out at room temperature andcross head speed was 1mm/min. Strain wasmeasured by using a non-contact

Japan-Philippine Joint Workshop on Materials for Safe and Sustainable Society 2011, Dec. 5, 2011, Hamamatsu, Shizuoka, Japan

extensometer.
Figure 2 shows a stress-strain curve of
MWNT composites and individual materials.
Maximum Young’s modulus of MWNT
composite was 56.2GPa and maximum
tensile strength was 432MPa. These values
were about 10 and 7 times as high as thoseof resin, respectively. Tensile behavior of
MWNT composite was more linear than thatof MWNT spun yarn. It implies that resin
was well impregnated into MWNT spunyarns. This means that tensile properties of
MWNT composites are dominated by thetensile properties of MWNTs.
450
Vf=15.6%
spun yarn
Rεsin

400
350
300

[MPa]

200
150

s

Strεss

250

100
50
0
0

0.5

1

1.5

2

Strain ε [%]

2.5

3

3.5

Fig.2 Stress-strain curve of MWNT composite andindividual materials

4. Conclusions
・ The pultrusion technique of spun yarn isan effective method for increasing a
volume fraction in fabrication of MWNT
composite.
・ Tensile properties of MWNT composites
are dominated by the tensile propertiesof MWNTs if resin is well impregnatedinto MWNT spun yarns.

Reference[1] Y. Inoue, K. Kakihata, Y. Hirono, T.

Horie, A. Ishida, and H. Mimura,
APPLIED PHYSICS LETTERS, 92(2008), 213113

28