CaCO3 Film of Aragonite Crystal Structure Controlled by Electro-deposition

Process in Synthesized S.W. Solution

*M. H. Lee

1), S. H. Lee

1), I. H. Choi

1), J. Kang

1) and J. M. Park

1)

1) Division of Marine Engineering, Korea Maritime & Ocean University, Busan, Korea

*leemh@kmou.ac.kr

Keywords: Electro-deposition Process, Calcium Carbonate, Calcite, Aragonite

Calcium carbonate(CaCO3) is an abundant mineral in nature; approximately 5 % of the earth’s crust consists of it.

It is an important building material in living organisms as bones, teeth and shells; moreover it has some valuable

applications in industry. However, the formation of uniform and control crystalline form of calcium carbonate by

simple and efficient methods remains a challenging task despite several decades of research efforts. In general,

calcium carbonate appears in nature in three crystal structures; calcite, aragonite, vaterite. Calcite is the most

thermos dynamically stable form followed by aragonite and vaterite. Recently, interest in aragonite has increased

substantially. Its needle-like crystals with high aspect ratio are used as fillers for the improvement of mechanical

properties of paper and polymer materials. Also aragonite has a uniform needle-like morphology and is found to be

more functional for the intention of forming the second form of the material because of its unstable thermodynamic

structure. Additionally, aragonite is also a biomedical food material, because it is denser than calcite and can be

integrated and resolved. However, aragonite is formed under a much narrower range of physic-chemical conditions

and is easily transformed into calcite by varying different parameters such as concentration of dissolved species,

temperature of the solution or pressure.

This study focuses on producing aragonite by increasing Mg2+

concentrations. It has been shown that the Mg2+

inhibits calcium carbonate deposition and when it is added in the solution at high concentration, aragonite is the

preferential crystalline form present on the substrate whereas calcite is predominant at low Mg2+

concentration. This

paper aims to study the formation of films as well as the nucleation-growth process of deposition in synthesized

solutions combining NaHCO3, CaCl2 and MgCl2 by electro-deposition process.

Electrodeposits CaCO3 films were formed by an electro-deposition technique on steel substrates in synthesized sea

water and distilled water solutions containing NaHCO3, CaCl2 and MgCl2 with different ratios respectively. The

current density of cathode substrate was 5A/cm2 by rectifier for an electro-deposition time of 24 hrs. In addition, the

influence of the concentration of Mg2+

, times to electrodeposits, and anode were investigated by Scanning Electron

Microscopy (SEM) and X-Ray Diffraction (XRD) respectively.

From experimental results, only calcite crystals were found in the solution containing no Mg2+

. This showed that

calcite crystals transform to become aragonite crystals when Mg2+

increases. X-Ray Diffraction (XRD) was used to

confirm that these precipitates are needle-like aragonite (Fig. 1)

References:

1) B. Aziz and D. Gebauer, Cryst. Eng. Comm., 13, 4641-4645 (2011).

2) Stearn, C.W. and R.L. Carroll, The Record of Life. New York: Wiley and Sons(1989)

3) M.H. Lee, Fourth International Symposium on Biomimetic Materials Processing., 4,94(2004)

Fig.1 Potential and morphology of CaCO3 films formed at various synthesized solutions

Charactersitcs of Water Thermal Plasmas as Radical Source

*T. Watanabe, Y. Ozeki, T. Matsuo, and M. Tanaka Kyushu University, Fukuoka, Japan *watanabe@chem-eng.kyushu-u.ac.jp

Keywords: thermal plasmas, arc fluctuation, high-speed visualization

Water plasma is a kind of thermal plasma directly generated from water. Large amount of H, O, and OH radicals

in the water plasma leads to the generation of hydrogen-rich gas from the decomposition of organic wastes. Therefore,

water plasma system is expected to be a biomass gasification device with high concentration of hydrogen compared

to conventional gasification methods. Decomposition mechanism of D-glucose in water plasma should be revealed

for the utilization of water plasma as a gasification device, because biomass is mainly composed of D-glucose. In this

study, aqueous glucose solution was decomposed by water

plasmas at atmospheric pressure. The arc fluctuation was also

visualaized to invesitaged the arc characteristics. The

evaluation of the fluctuation effect on the decomposition

process was discussed.

Water plasma was generated at discharge region by heating

and ionization of steam that is produced by evaporation of

water from the reservoirs. Simultaneously, the anode is cooled

by the water evaporation, thus the torch can be operated in the

absence of plasma supporting gas, cooling-controlled system,

and pressure-controlled devices. D-glucose solution was

introduced into the torch with a controlled feed rate after

adjusting solution concentration. The system was operated at

atmospheric pressure with arc currents of 6–9.5 A and the

voltage from 90 to 140 V.

D-glucose solution was decomposed through water

plasma and converted into gaseous products at downstream of

plasma where temperature was less than 1000 K. The products

was quickly quenched in the reaction tube and separated into

gaseous phase (4.5 wt%), liquid phase (93.0 wt%), and solid

phase (2.5 wt%). The composition of the produced gas from

1.0 mol% D-glucose decomposition as a function of arc

current is presented in Fig. 1. The major compositions of the

produced gas were H2, CO, and CO2. The decomposition rate

of D-glucose was estimated around 99%. The carbon

components derived from D-glucose were finally converted

into CO and CO2. The high concentration (56 mol%) of H2

gas was obtained because carbon compounds reacted with OH

radical and H radicals reacted with each other.

The arc temperature was measured by combination of

band-pass filters with a high-speed video camera. The high-

speed images of the plasma arc were recorded with a frame

rate of 2.0 × 105 s-1 and a shutter speed of 4.5 μs. The

wavelengths of the bandpass filter at 486 nm and 656 nm were

selected for hydrogen emission lines. The plasma temperature

was determined from the Boltzmann plot based on the

synchronized high-speed images through two bandpass

filetes. The voltage waveform and the synchronized snapshots

of arc temperature distributions are shown in Fig. 2. The

highest temperature of arc reached 9000 K. The periodic saw

tooth shape of the voltage waveform gives the the arc

frequency of 29 kHz through the Fast Fourier Transform

(FFT). This frequency is sufficiently fast, therefore the arc

fluctuation is negligible during the water plasma

decomposition process.

Fig. 1 Mole fractions of gas species in gaseous product.

Fig. 2 Measurement of (a) waveform of arc voltage and (b) arc

temperature fluctuation at D-glucose concentration of 1 mol%.

Application of Ozone Micro-nano Bubbles Water for Industrial Materials and

Environmental Conservation

*K. Sano1)2), Y. Umeda2) , K. Tashiro2), and H. Honma2) 1) Department of Symbiotic Design, Kanto Gakuin University, Yokohama, Japan, 2) Materials and Surface Engineering Research Institute, Kanto Gakuin University, Odawara, Kanagawa, Japan *keisano@kanto-gakuin.ac.jp

Keywords: Ozone, Micro-nano bubbles, Water, Surface treatment, Polypropylene, Paintability, Wash, Used clothes

In order to induce adhesion of electroless CuNiP deposition to polyimide film substrate, surface modification of

PI film with an aqueous dispersion of ozone micro-nano bubbles was already succeeded 1). This method should be

provided an environment friendly and improved many processes for industrial materials using low concentration

ozone treatment 2). Authors are studying application of ozone micro-nano bubbles water for industrial processes. As a

problem in the production and use of automotive polymer composite parts, the total reductions of VOC (volatile

organic compounds) odor which is given a bad influence on natural environments and human health are required in

late years.

A lot of polypropylene (PP) parts are used for automobile.

However, some surface treatments are carried out for PP parts

because PP has a low paintability. The treatments are expensive

and bad in natural environments. For example, a chlorinated

polyolefin primer is coated on PP bumper as previous treatment

for color top painting.

The washing method of PP bumper in the micro-nano ozone

bubbles water was studied by authors. The primer can be

removed by this method. Fig.1 shows varying of paintability of

PP surface with time of washing in micro-nano ozone bubbles

water without heating. The adhesion of urethane color paint on

PP was estimated by method of JIS K 5600-5-6 3). The PP surface

was improved and the painted film was not peeled off by the

washing of six minutes. This is considered that weak boundary

layer was removed and hydroperoxide groups were occurred on

PP surface by washing.

The recovered fiber felts using used clothes are used for

automobile as acoustic absorbent material in Japan. The odor of

used clothes cannot be completely eliminated by conventional

washing as a problem.

The washing method of used clothes in the micro-nano

ozone bubbles water was studied. Fig.2 shows varying of odor

from used cotton clothes with time of washing. The odor of

clothes was estimated by method of VDA 207 4). The odor of

clothes was decreased remarkably by the washing of five

minutes without heating. This washing method in micro-nano

ozone bubbles water is cheap and eco-friendly without using a

detergent.

Furthermore, the results of decomposition and

detoxification of VOC by micro-nano ozone bubbles water will

be explained in this presentation.

References 1) Y. Nishimura, S. Watanabe, K. Tashiro, Y. Umeda, H.

Honma and Y. Yamashita, Transactions of the IMF, 92,

52-58 (2014),

2) K. Sano, Engineering Materials, Japan, 64, 35-37 (2016).

3) JIS K 5600-5-6, Testing methods for paints, Part 5:

Mechanical property of film, Section 6: Adhesion test (Cross-cut test).

4) German Automobile Industrial Association, VDA 270, Odor tests.

0

2

4

6

8

10

0 1 2 3 4 5 6 7

Ozone ratio in water: 3.5 ppm

Substrate: Polypropylene

Urethane color paint on PP

Adhesi

on o

f pa

int

film

（re

lative

val

ue）

Washing time (min）

1

2

3

4

5

0 5 10 15 20 25 30

Od

or

(se

ns

ory

ev

alu

ati

on

)

Washing time (min)

Specimen: Used clothes 20 g

Ozone ratio in water: 3.5 ppm

Fig. 2 Washing time in ozone micro-nano bubbles water vs. odor of used clothes2).

Note how the caption is centered in the column. (8 point)

Fig. 1 Washing time in ozone micro-nano bubbles water vs. adhesion of paint film on PP substrate2).

Note how the caption is centered in the column. (8 point)

Green Technology for Agriculture: Development of CO2 and Nitrogen Oxide Recycling System Supported by NOx Removing Technique

M. YASUDA*1, A. DAIYASU, 1, S. YAMAUCHI2, M. ASANO3, H. ASANO3

1Department of Chemical Engineering, Osaka Prefecture University, 2 Tada Electric co. LTD, 3 Pollution Prevention Apparatus Laboratory Co., Ltd.

*E-mail: yasuda@chemeng.osakafu-u.ac.jp

Keywords: Environment friendly process, Zero emission, Nitorogen oxide, Carbon dioxide, CO2 agricultural application Abstract Agricultural productivity and yield have been increasing for many decades. This is because the food requirement for the ever-growing population of the world have been increasing. It is good news for us that elevated carbon dioxide (CO2) increases the productivity and water use efficiency of nearly all plants. Therefore, positive effects of CO2 on agriculture give great concerns for many researchers, farmers, farm managers and agricultural organization. High level of atmospheric CO2 enhances directly plant growth and gives environmental stresses on plant. These stresses result in the reduction of crop damage from insects and pathogenic diseases, the increment of the number of flower and fruit, and the enhancement of the sugar content of fruits and vegetables. CO2 exists in the Earth's atmosphere as a trace gas at a con centration of about 0.04 percent (400 ppm) by volume. The combustion of all carbon-based fuels, such as methane (natural gas), petroleum distillates and coal produces carbon dioxide and carbon dioxide is purified and compressed. Commercial production plant of CO2 requires large amounts of energy for the distillation, cooling and high-pressure compression. The exhaust gas from vehicle and combustion plant contains 10 vol% of CO2. Since the high purity and concentration of CO2 for the agricultural application does not required, the recycling of CO2 in the exhaust gas is green technology for us. However, the low removal efficiency and the high cost for the NOx elimination from the exhaust gas are recognized as a major problem. To overcome this problem, we develop smart and high efficiency NOx elimination process (CO2 and Nitrogen Oxide Recycling System). In our process, form 50 ppm to 1000ppm of NOx in the exhaust gas can completely remove using zeolite as an absorbent and the high concentration (from 10000 ppm to 100000ppm) of NOx desorbed by temperature swing adsorption technique (400oC) is absorbed in water. The final absorbing solution is up to 30wt% of HNO3. In this presentation, the oxidation reaction of nitrogen monoxide (see right figure), the NOx adsorption kinetics against ZSM-type and Y-type zeolite, and the NOx absorption behavior will be introduced.

Progress in Solution Plasma Processing *O. Takai Materials and Surface Engineering Research Institute, Kanto Gakuin University, Japan *takai@kanto-gakuin.ac.jp Keywords: Plasma, Solution, Nanoparticle, Surface Functionalization, Water Treatment Gas-phase plasma is used widely in many industrial fields, such as electronic device manufacturing processes, hard coating processes, and surface treatment processes. Solid-phase plasma has been used for surface plasmon resonance (SPR) spectroscopy and “plasmonics” is developing as a new research field. On the other hand, liquid-phase plasma is not well known, although it has been used sparingly in water treatment and electrical discharge machining. The fundamental properties of liquid-phase plasma have not been determined, including its generation techniques, its state, and activated chemical species in it. However, it would be reasonable to expect a higher reaction rate under lower-temperature conditions with greater chemical reaction variability, since the molecular density of the liquid phase is much higher than that of the gas phase. Therefore the development of studies on the liquid-phase plasma is very important from the viewpoints of a scientist and an engineer. Recently we have developed to induce glow discharges in cold solutions by using a newly developed pulsed power generator and named “solution plasma (SP)” because we can generate a variety of plasmas by choosing the combinations of solvents and solutes in solutions. It is important to generate the glow discharge in solutions, which realizes the formation of a new reaction field for material development at almost room temperature. We can make “cold plasma” in “cold solutions”. We are currently developing solution plasma processing (SPP) and can use aqueous and nonaqueous solutions, liquid nitrogen, supercritical fluids, etc. for SPP. This paper reports on the progress in SPP. The applications of SPP are syntheses of nanoparticles, surface modification, sterilization of bacteria, water treatment, etc. Nanoparticles of metals, alloys, oxides, nitrides and carbon are synthesized by SPP until now. Surface functionalization of carbon nanotubes and nanoballs is carried out by SPP too. The size of particles synthesized decreases these fifteen years by SPP. Nanoparticles which sizes are less than around 2 nm are called nanoclusters. We can synthesize nanoclusters by the reduction method by SP and sputtering of electrodes in SP. Metal nanoclusters show different properties from nanoparticles, and indicate insulating or semiconducting behaviors. Nanoclusters are very promising nanomaterials and SPP realizes the mass production of nanoclusters in liquid. This work was aided by MEXT-supported Program for the Strategic Research Foundation at Private Universities.

Effect of pH on BiOX (X=Cl, Br and I) synthesized by sonochemical

method for photocatalytic degradation of rhodamine B

P. Intaphong, and A. Phuruangrat Department of Materials Science and Technology, Faculty of Science, Prince of Songkla University, Hat Yai,

Songkhla 90112, Thailand boychemmju@gmail.com

Keywords : BiOX (X = Cl, Br and I), Photocatalyst, rhodamine B, Sonochemical method

BiOX (X = Cl, Br and I) photocatalysts were synthesized by sonochemical method. The effect of pH

of precursors on phase, morphologies and photocatalytic activities was studied in this research. The precursors

solution were prepared by mixed the Bi(NO3)35H2O and NaX (X = Cl, Br and I) solutions and followed

adjusted pH of precursors at pH 2-12 by 3 M NaOH solution. The BiOX (X = Cl, Br and I) photocatalysts were

characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron

microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), respectively. The results showed that they are

tetragonal structure of BiOX (X = Cl, Br and I) nanoplates. The photocatalytic activities of BiOX (X = Cl, Br

and I) photocatalysts were tested through the rhodamine B (RhB) degradation under visible-light radiation. It

found that the photocatalytic performance of degradation of RhB over BiOX (X = Cl, Br and I) were increased

from pH 2 to pH 8 within 120 min under visible light irradiation. Increasing the pH of precursor to 10, the

photocatalytic performance of degradation of RhB over BiOX (X = Cl, Br and I) were decreased at same

conditions.

References

1) X. Chang, M.A. Gondal, A.A. Al-Saadi, M.A. Ali, H. Shen, Q. Zhou, J. Zhang, M. Du, Y. Liu and G. Ji,

J. Colloid Interf. Sci., 377, 291-298(2012).

2) S. Wang, L. Wang, W. Ma, D.M. Johnson, Y. Fang, M.Jia and Y. Huang, Chem. Eng. J., 259, 410-

416(2015).

3) L. Lin, M. Huang, L. Long, Z. Sun, W. Zheng and D. Chen, Ceram. Int., 40 11493-11501(2014).

Fig. 1 Appearance after electroless NiP plating: (a) Untreated substrate, (b) Conventional method, (c) Atmospheric UV irradiation

(a) (b)

(c)Region of electroless NiP plating

Environmentally Conscious Pretreatment Process for Plating on PPS resin

*T. Nomura1)2)3), K. Tashiro2), Y. Umeda2), H. Honma2) and O. Takai1)2)1)Department of Industrial Chemistry, Graduate School of Engineering, Kanto Gakuin University, 2)Materials and Surface Engineering Research Institute, Kanto Gakuin University, 3)Shinkosya co., ltd. *t_nomura@shinkosya.co.jpKeywords: Atmospheric UV irradiation, PPS resin, Electroless NiP plating

Polyphenylene sulfide (PPS) is a heat-resistance material partially crystalline polymer with a simple chemical construction. The PPS has a high melting point of about 280 °C, outstanding chemical resistance and non-combustibility established by an industry flammability test without any flame retardant chemical. Furthermore, the PPS is widely used in the replacement of high-functional insulation and various metals from their properties. When the PPS is plated, surface roughening is treated with a mixed solution of nitric acid and hydrofluoric acid conventionally. However, the solution is difficult in waste water treatment. Also, the PPS resin no containing glass is difficult to plating. So the correspondence to these problems is demanded. Therefore we reported a formation technology of the plating film superior in adhesion strength for pretreatment of the insulation resin until now1)2).

In this study, we applied the atmospheric UV irradiation method for PPS resin and investigated the plating process for high adhesion strength.

PPS substrate was annealed at 80 °C for 1 h in order to relax the internal stress. The substrate was irradiated using ultraviolet (UV) irradiation equipment (KOL1-300S, KOTO Electric Co., LTD) in the atmosphere. After the atmospheric UV irradiation, the substrate was plated about 0.3 μm metal film by electroless NiP plating bath. After electroless NiP plating and electrolytic copper plating, samples were heated at 80 °C for 1 h in order to improve adhesion.

The condition of the deposited NiP film after electroless plating was visually observed. Wettability testing of the substrate after atmospheric UV irradiation and proceeding alkaline treatment was performed by water contact angle. Adhesion strength of the plated film to the substrate after electrolytic plating was measured by 90° peel test according to the JIS H 8630-2006 procedure with a pull speed of 50 mm min-1. Adhesion strength was measured using a STROGRAPH E2-L05. The measurement involved peeling the plated film from the substrate at three different locations for which the average was calculated. Surface morphologies of the untreated and the substrate after atmospheric UV irradiation were observed by SPM using AFM mode. Subsequently, FT-IR of the substrate before and after atmospheric UV irradiation was performed using the ATR method. Similarly, samples were confirmed the change of functional groups on the substrate before and after atmospheric UV irradiation by XPS. For samples prepared for FT-IR and XPS analysis, atmospheric UV irradiation time was 5 min, 10 min and 20 min.

As shown in Fig. 1, the high-quality electroless NiP plating was visually confirmed on the PPS resin by surface modification using atmospheric UV irradiation. Adhesion strength of about 0.9 kN m-1 was obtained for the treatment. The change in substrate morphology and roughness (Ra) using atmospheric UV irradiation was observed by SPM. The Ra of untreated PPS and PPS after atmospheric UV irradiation were almost no change, a smoothness of the substrate was maintained. Subsequently, we confirmed the increase in the adsorption of O-H, C=O and C-O groups increasing the UV irradiation time by FT-IR spectroscopy. In addition, as a result of analyzed by XPS, C-C and C-S bonds were confirmed in the untreated substrate, subsequently by UV irradiation we confirmed that C-C bonding peak decreased and the detection of C-O and COO bonding peaks due to the hydrophilic increased.

From the above results, the plating on PPS resin no containing glass was possible to applying the atmospheric UV irradiation method that is environmentally friendly.

Acknowledgement: This study was aided by “MEXT-supported Program for the Strategic Research Foundation at Private Universities”.

References: 1) M. Sugimoto and H. Honma, J. Surf. Finish. Soc. Jpn., 59, 294-298 (2008). 2) T. Nomura, H. Nakagawa, K. Tashiro, Y. Umeda, H. Honma and O. Takai, Trans. IMF, 94, 322-327 (2016).

Influences of Seed Layer on LCP Film on High-speed Signal

Transmission Characteristics

*T. Ishii1)2)3), M. Watanabe2), J. Noh2), H. Honma2), and O. Takai1)2) 1) Department of Materials and Surface Engineering, Kanto Gakuin University, Odawara, Kanagawa, Japan, 2) Materials and Surface Engineering Research Institute, Kanto Gakuin University, Odawara, Kanagawa, Japan, 3) Toppan Technical Research Institute, TOPPAN PRINTING CO., LTD., Kita-Katsushika, Saitama, Japan *tomoyuki_1.ishii@toppan.co.jp

Keywords : High-speed Signal Transmission, LCP, S Parameter, Electroless Copper Plating

For the signal circuits between processor unit and connected components inside of computing system,

acceleration of signal transmission speed is also demanded. To reduce the transmission loss of substrates for

semiconductor packages, the manufacturing process control must be considered, regarding such as roughness of

interface between resin film and backside of signal lines, dielectric loss tangent and impedance matching.

A liquid-crystal-polymer (LCP) film is emerging as a promising package substrate material because of excellent

low permittivity and low dielectric loss tangent in high frequency band. In our previous study, we developed

conducting layer formation processes which provide a good adhesion strength between LCP film and conducting

layer. UV irradiation was used for the pretreatment method of electroless copper plating, which creates modified

layer in nanometer scale including hydrophilic rough surface on LCP film. This treatment can achieve both a good

adhesion strength and smooth interface between conducting layer and LCP film simultaneously.

Regarding the modified layer states formed by UV

irradiation, it was found that Pd catalyst appears in the

layer and the structure of the resin is changed. Furthermore,

modified layer thickness becomes thicker with increasing

UV irradiation (Fig. 1). And the conductivity of copper

seed layer of the conducting layer differs in electroless

plating and sputtering. However, it was not verified how

the change of such interface state between modified layer

and seed layer influence on qualities of high-speed signal

transmission.

In this study, we produced some samples including

signal copper circuits with different thickness of modified

layer by changing UV irradiation condition and with

different conductivity seed layer using electroless plating

and sputtering, then measured S parameter (S21) of these

circuits.

A high-speed signal transmission line (microstrip line)

was fabricated on a glass epoxy substrate using a

subtractive method. The sample used in this experiment

consisted of LCP film (Vecstar-CTZ, 100 m thick,

Kuraray Co., Ltd.). The wiring length was 30 mm straight

line and the wiring width was designed so that the

characteristic impedance was 50 . The signal copper

circuits in which UV irradiation time was 1, 5, 10, 20 min

and seed layer was formed by electroless copper plating

was fabricated. According to S parameter measurements,

there was no difference at each modified layer thickness

until 40 GHz (Fig. 2). Since the skin depth of copper

wiring at 40 GHz is about 300 nm, it is considered that the

forming condition of the conducting layer has a greater

influence on the transmission characteristics than one of

the modified layer in up to 40 GHz. Considering that the

skin depth becomes shallower as the frequency becomes

higher, it is consider that S parameter is influenced at

modified layer condition at over 40 GHz.

-3

-2

-1

0

0 10 20 30 40

S21 [

dB

]

Frequency [GHz]

1 min5 min10 min20 min

UV irradiation time

Fig. 2 Results of S Parameter (S21) measurement

according to the UV irradiation time

100 nm 100 nm

Fig. 1 Cross sectional TEM images of modified layer

formed by each UV irradiation conditions

100 nm

(c) 20 min

(a) 5 min

Cu

LCP

Modified layer

(b) 10 min

Formation of Fine Metal Patterns using Photosensitive Metal Complex Film

on Polyimide Substrate

*Y. Suzuki1)2)3), Y. Horiuchi2), C.E.J.Cordonier2)3), J.H. Noh1)2), H. Honma1)2) and O. Takai1)2)

1) Department of Materials and Surface Engineering Graduate School of Engineering Kanto Gakuin University,

Odawara, Kanagawa, Japan, 2) Kanto Gakuin University, Materials & Surface Engineering Research Institute,

Odawara, Kanagawa, Japan, 3)JCU Co.Ltd., Ueno, Tokyo, Japan *ys.31550203@gmail.com

Keywords: electroless plating, photosensitive metal complex film, fine metal pattern, polyimide

Introduction

Recently, electronic devices such as mobile phones and medical devices require miniaturization and high

performance. Therefore it is necessary to improve the technique for forming fine circuits onto thin film substrate such

as polyimide and cyclo olefin polymer. In order to meet these requirements, dry process such as sputtering and vacuum

deposition and the semi-additive method have been used. We had proposed a selective plating technique to form fine

circuits on glass substrate1)2). In this method, fine pattern was formed by photolithography using a photosensitive metal

complex solution, it’s containing Ti and Cu. This technique could be expected to reduce the cost compared to the dry

process. In this study, fine metal patterns of copper with high electrical conductivity and low cost metal were formed

directly by selective electroless plating on polyimide film where patterning was performed using a photosensitive

metal complex solution to deposit the catalyst image.

Experimental

A photosensitive metal complex film was formed by spin-coating a photosensitive metal complex solution onto

polyimide film (DU PONT-TORAY Co.ltd Kapton-EN-A) then exposing to UV irradiation (Xe-Hg lamp USHIO INC.

USH-250BY/D-zl) through a photomask before developing in aqueous 2.0 wt.% tetramethylammonium hydroxide

solution for 30 s. After calcination at 350 °C for 1 hour, sintered substrate was reduced by sodium borohydride solution

before dipping palladium catalyst solution. Finally, fine metal patterns were formed by electroless copper plating.

Observation of the fine pattern was performed by laser microscopy (OLYMPUS Co.ltd LEXT-OLS-4000).

Furthermore, the surface elemental analysis was investigated by X-ray photoelectron spectroscopy (SHIMADZU

Co.ltd AXIS ULTRA DLD) analysis.

Results and Discussions

The fine patterns of photosensitive metal complex

film after developing was shown in Fig.1. Shown in

Fig.2, selective formation by copper plating of width

4 to 100 μm was formed onto this metal complex

film. Unfortunately, the pattern of width 2 µm was

not formed because of metal complex film of width

2 µm could not form. The problem can be solved by

optimizing exposure conditions, so the results of

further miniaturization will be reported at the

presentation. Surface elemental analysis of metal

complex film after calcination and polyimide film

was shown in Fig.3. Ti and Cu was confirmed on the

complex film after calcination. These metals were

affected as catalyst image.

References

1) Hitoshi Endo, Osamu Takai, Hideo Honma, Christopher E.

J. Cordonier, Mater. Sci. Tech. Jpn., 51, 6, (2014) 2) Christopher E. J. Cordonier, Hitoshi Endo, Takahiro Kagami,

Yohei Okabe, Mieko Ide, Shion Suzuki, and Hideo Honma ,

J. Electrochem. Soc. 161 D1-D6 (2014)

Fig.2 Fine metal patterns

Fig.1 Fine patterns of

metal complex film

100 μm

L/S 8 μm

4 μm

6 μm

2 μm 100 μm

L/S 8 μm

4 μm

6 μm

2 μm

1200 1000 800 600 400 200

Inte

nsi

ty

Binding Energy

complex film

PI film

O 1s

Ti 2p C 1s

Cu 2p N 1s

Fig.3 XPS survey spectrums of photosensitive

metal complex film and PI film

Flash Lamp Annealing Process for Metal Film on Resin by Electroless Plating

*Y. Miyazeki1)2), Y. Suzuki2) , Y. Horiuchi2), J. –H. Noh2), H. Honma2), and T. Arakawa1) 1) Graduate School of Engineering, Yokohama National University 2) Materials and Surface Engineering Research

Institute, Kanto Gakuin University *miyazeki-yusuke-tf@ynu.jp

Keywords: Resin, Electroless plating, Flash lamp annealing (FLA)

Forming metal thin films on resin by using

electroless plating has been widely used as important

surface treatment technology for the purpose of applying

to electromagnetic wave shields or printed wiring boards

and so on. Electroless plating, in comparison with dry

processes such as vacuum evaporation or sputtering, is a

low-cost process because it does not require any vacuum

equipment. In addition, it can be used to deposit

uniformly large-area metal films on various materials and

structures including 3D structures [1]. Annealing as a post

treatment after electroless plating is required to prevent

hydrogen embrittlement improve adhesion strength

between metal film and resin. However, a conventional

annealing method by using an electric furnace takes more

than an hour to anneal metal thin film completely. And, it

is difficult for the conventional method to anneal

sufficiently electroless-plated films on resin whose

heat-resistant temperature is relatively low such as

Cyclo-Olefin Polymer (COP) or ABS, because the

annealing temperature is subject to the heat-resistant

temperature of them.

In this study, our research group propose direct

formation of metal thin films on resin using electroless

plating and flash lamp annealing (FLA) process [2]. FLA

can anneal electroless-plated films at high temperature

(approximately 1000 °C) in a moment (less than 1 ms)

using a high-power pulse of a Xe lamp to improve adhesion strength

between metal film and resin and prevent hydrogen embrittlement

without causing thermal damage to resin. Therefore, the proposed

method can significantly reduce the sintering time as compared with

the conventional annealing process. we deposited approximately

200-nm-thick Ni-P films on resins such as 100-m- COP and

1.5-mm-ABS by using electroless plating, and applied FLA the

metal films. And then, we investigated characteristics of the Ni-P

films including surface morphologies and adhesion strengths

between the Ni-P films and the resin substrates. As shown in Fig. 1,

it was found that the values of adhesion strength between Ni-P films

and COP and ABS were 0.1-0.5 kN/m and 0.9-1.2 kN/m respectively.

They were comparable to the conventional annealing process of

more than one hour. As shown in Fig. 2, it was found that fine

structures like undulatus were formed on surfaces of Ni-P films after

FLA.

References :

1) F. Formanek et al., Appl. Phys. Lett. 88, 083110 (2006)

2) H. Wirth et al., Appl. Phys. Lett. 74, 979-981 (1999).

0.32

0.48

0.25 0.26

0.15 0.13 0.120.18 0.17

0

0.1

0.2

0.3

0.4

0.5

0.6

700 V 800 V 900 V 1000 V 1100 V 1200 V 1300 V 1400 V 1500 V

Ad

he

sio

n s

tre

ng

th（kN

/m）

Charging voltage（V）

(a)

0.931.02

1.111.03 1.09 0.99

1.131.16

0.99

0

0.2

0.4

0.6

0.8

1

1.2

1.4

700 V 800 V 900 V 1000 V 1100 V 1200 V 1300 V 1400 V 1500 V

Ad

he

sio

n s

tre

ng

th（k

N/m）

Charging voltage（V）

(b)

Fig. 1. Adhesion strength of Ni-P films on (a) COP and

(b)ABS as a function of charging voltage of FLA

Fig. 2. Surface morphology of a Ni-P film on

ABS after FLA which a charging volt is 1300 V

Study on the cushion device for press with friction force *T. Ito1), K.Matsui2) , and O. Takai3) 1) Kanto Gakuin University Department of integrated Engineering, 2) Kanto Gakuin University, 3) Materials&Surface Engineering Research Institute ,Kanto Gakuin University * itotaka@aida.co.jp Keywords: Press forming ,Cushion device ,Plastic working , Fully sheared cut edge

1. Introduction In order to achieve highly accurate press forming aiming at net shaping, forming method has been converted or the dedicated machine is used for the current pressed parts. In terms of the conversion of forming method, it is possible to improve the accuracy of forming and extend the tooling die life by improving the material for dies, the method of heat treatment, and the surface treatment technology and the process layout study with CAE. On the other hands, in terms of dedicating the press machine, it makes possible to achieve fully sheared cut edge and draw high tensile strength materials by utilizing cushion devices or other devices installed on the press machine, which are not possible with conventional forming methods. 2. Purpose of development and means Conventionally, there are pneumatic cushions and hydraulic cushions which are installed on press machines and the cushion device is equipped inside the press frame. It, therefore, deteriorates the press frame rigidity and sometimes causes winkles, cracks or insufficient forming accuracy due to the lack of the frame rigidity at press forming of materials with high tensile strength such as ultra-high tensile strength material. In addition, the location of cushion pins at die designing totally depends on the specification of cushion pins location on the press, and it could be one of the factors to impede the optimal die design. In order to locate cushion pins at the optimal points without deteriorating the rigidity of the press machine and the tooling die, the cushion device applying the friction force, which can be installed on the tooling die was developed. This cushion device does not use hydraulic pressure or pneumatic pressure, but it uses friction force as cushion force, which is generated by force-fitting the cushion pin equipped in the die into the pin holder. 3.Means to solve the problem This cushion device utilizes friction force generated by force-fitting the pin into the pin holder, therefore sliding heat is generated due to the friction between metals and this may cause galling, seizure or progress of the wear. The frictional force cushioning capability is calculated by the product of the surface pressure generated between the metals, the area where the surface pressure acts and the friction coefficient. The relationship between the interference margin δ and the generated surface pressure p in fitting is expressed by the following equation.

---（1） F = p × µ × (π×D1×L) ---（2）

δ：interference p：Emergent surface pressure ν1：Poisson’s ratio of the pin ν2：Poisson’s ratio of the hub E1：Young's modulus of the pin E2：Young's modulus of the hub D1：fitting diameter D2：hub outer diameter F ：Frictional force cushion capability L ：Fitting part length µ ：Coefficient of friction Cooling and lubrication are indispensable not to make the seizure occur. Oil grooves are installed on the cushion pin side and cooling is performed. The cushion pin is subjected to low temperature TiC as a surface treatment after lapping. 4. Discussion Since it is converted from the static friction to the dynamic friction after the start of its operation in the frictional force cushion, it should be considered at the dynamic friction status as the cushioning function. Since the frictional force calculated from the interference margin δ in the (1) & (2) equations above and the frictional force actually measured from the test can be determined to be the same value as the cushioning force at press working, it can be inferred that frictional force setting by controlling the volume of the interference margin is possible. As a result of conducting the stroke endurance test of 400,000 times in total in this testing device, it was possible to obtain a stable load and temperature transition at all times. Also, with respect to wear, abrasion of the inner diameter of the hub and the outer diameter of the cushion pin was not observed, so high durability and long life was demonstrated. It will be applied to various fields and further technological innovation will be promoted from now on. References: 1) Aida Press Research Group: Press wanted to know, Japan Machinist Company (1992).

Fig. 1 Basic way of thinking

Figure. 1 Superconductivity coil on Si wafer Figure. 2 After electroless copper plating Figure. 3 After electro copper plating

Abstract Guideline (Leave two lines for presentation number)

Fabrication of superconducting coils on Si wafer by plating method

*Y. Sakurahara1)2), J.H. Noh1)2), O. Takai2), H. Honma2), T. Motohiro3), T. Hioki3), M. Sasaki4),

H. Watanabe5), H. Doy5), and T. Arakawa1) 1) Graduate School of Engineering, Yokohama National University 2) Materials & Surface Engineering Research

Institute, Kanto Gakuin University 3) Institute of Innovation for future Society 4) Graduate school of Engineering,

Toyota Technological Institute 5) D-process Inc. *sakurahara-yusuke-hw@ynu.jp

Keywords: Superconducting coil, Plating method, Niobium nitride, SMES, MEMS

Our group pay attention to Superconducting Magnetic Energy Storage(SMES) for the realization of energy

conservation. This device can store energy by keeping direct current flowing through coiled superconducting wires.

The feature of this device is that efficiency of storage is high and high-speed energy transfer is possible.

Furthermore, it is expected to have high frequency energy transfer and long device’s service life since it is a

stationary device and does not utilize chemical reactions.

However, the SMES consists of the superconducting coil, a low-temperature container, a power converter, a

supervisory controller, a refrigerator, etc. There are many problems for miniaturizing. We are aiming to minimize it

by forming a metal film using sputtering and plating method on a trench structure of the coil shape fabricated on Si

wafer by Micro Electro Mechanical System(MEMS) technology. It is possible to form a seed layer uniformly by

electroless plating and then form a coil shape with high adhesion without defects by electro copper plating.

We fabricated grooves of the coil shape on Si wafers by using MEMS technology, and formed thin films of

niobium nitride(NbN) on the surfaces by sputtering. (Figure 1) Thereafter, we applied electroless cupper plating and

electro copper plating to fill the groove with metal. Forming seed layer by sputtering is difficult to uniformly form a

metal film inside of the trench, so we applied electroless plating. Finally, we flattened the surface by using Chemical

Mechanical Polishing(CMP), and fabricated the superconducting coil by stacking wafers while connecting them.

We used a tin(Sn) – palladium(Pd) two-step method for applying catalysts to cause chemical reaction of electroless

copper plating method. The result was shown as Figure. 2, and a copper thin film could be uniformly formed.

The optimum conditions of the current density for electroplating were increasing from 5 A/dm2 first, to 0.5 A/dm2,

1 A/dm2, 3 A/dm2. By the step type current application method, the copper crystal growth started at the bottom up,

and it prevented from occurring of voids.

As a result of actual survey at He temperature(14K), we confirm the superconductivity phenomenon, and it is

suggested that it could be used as the superconducting coil.

We realized that trace of electrodes, ununiformity of copper foil, level difference of surface at the center and

around the wafer adversely affected CMP processing. Therefore, we would like to improve electro plating

equipment and reduce steps on the wafer surface as much as possible.

In addition, we can confirm the superconductivity phenomenon at 14K, about 100 times superconducting induction

is confirmed compared with the conventional one, and it is expected to be applied to SMES. We think that it is

necessary to generate superconductivity at higher temperature. For that purpose, we consider that using

YBa2Cu3O7-6 oxide high temperature superconductor is benefit.

Solution Plasma with Nitrogen Stream for Plant Factory

*C. Terashima Photocatalysis International Research Center, Research Institute for Science & Technology, Tokyo University of

Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan *terashima@rs.tus.ac.jp

Keywords: Water, Plasma, Nitrogen fixation, Algae, Decomposition

Nitrogen fixation is an important process to create industrially useful nitrogen-compounds. Haber-Bosch synthesis

method is a well-known method for ammonia synthesis which generally requires high pressure and high temperature

(400-600°C and 20-40 MPa)[1]. Additionally, environmental load is concerned by using a large amount of hydrogen

gas as a raw material. Therefore new nitrogen fixation method is required to replace the conventional method. On

the other hand, solution plasma is non-equilibrium process established by co-operation of the different phases in a

solution. The generated electrons and highly active radicals can perform a high-speed response at normal

temperature, and the primary active species are hydrogen radicals [2]. In this study, ammonium and nitrate ions were

synthesized by nitrogen fixation and without using external H2

gas under normal temperature and normal pressure by solution

plasma processing method.

The experimental details are as follow. Electrodes were

inserted from both sides of the beaker full of KCl aqueous and

poured nitrogen gas from tip of its. Using bipolar pulsed

power supply, electrodes were applied a voltage and plasma

occurred in the solution.

As a result of measurement of plasma emission spectrum,

there is a strong nitrogen peak around 300-400 nm. Therefore

it is suggested that nitrogen dissociation is occurred by plasma.

Quantitative analysis of solution plasma treated water reveal

that ammonium and nitrate ions are present in the solution as

shown in Fig.1. So, successful nitrogen fixation can be made

by solution plasma processing method.

Moreover, the production of ammonium and nitrate ions by solution plasma processing method could further be

utilized in plant growth.

References 1) a) Fundamentals and Practice (Ed.: J.R. Jennings), Plemium, New York, 1991; b) K. Akira, L.J. Chiristiansen, I.

Dybkjacr, J.B. Hansen, H. Nielsen and Manufacture, Springer-Verlag, Heidelberg, 1995.

2) N. Saito, J. Hieda and O. Takai, Thin Solid Films, 518, 912 (2009).

Fig.1 Relationship of the

concentration of NH4 and NO3

on treatment time.

Bimetallic CuSn Nanostructures for Efficient Electrochemical CO2 Reduction

in Aqueous Electrolyte

* N. Roy

1), Y. Hirano

2), N. Suzuki

1), A. Fujishima

1), C. Terashima

1)

1)

Photocatalysis International Research Center, 2)

Department of Pure and Applied Chemistry, Tokyo University of

Science, Noda, Chiba, Japan, Email: nitu.iitg@gmail.com

Keywords : CO2 Reduction, Electrochemistry, Nanostructures, Alloy, Hybrid catalyst, Recycling carbon cycle is an important natural phenomenon which has tremendous effects on sustainability of the

living system of the Earth. However, CO2, one of the C1 members of carbon cycle, has increased a lot in last few

decades. Therefore, facile and efficient conversions of CO2 into chemical fuels using renewable energy/electricity

have attracted immense attention by the scientific community. Metallic cathode materials, specifically Ag, Cu, Au,

Bi, Sn and Zn have been on the focus for efficient and selective CO2 reduction.1 Few other metal oxides and carbon

based materials have also been utilized in recent years for CO2 reduction. Primary challenges in CO2 reduction deal

with selectivity, high overpotential and stability of the catalyst materials. Amongst different C1 reduction products

of CO2, CO is an important chemical because of its use as raw material in syngas which is used as synthetic

petroleum. However, CO is also known to poison the catalyst surface. This leads to increase the overpotential with

increased electrode corrosion. Therefore, strategies are perceived in this work to overcome the electrode corrosion

through designing a new hybrid catalyst that offers high stability with good selectivity in aqueous electrolyte.

Cu is known to be a potential candidate for electrochemical CO2 reduction due to several reasons.2 However,

product selectivity remains as major drawbacks. Product selectivity of Cu can be monitored through morphology

dependent nanostructuring. The morphology of the catalysts often changes upon electrolysis for longer time. On the

other hand, Sn is known to be catalytically active for CO2 reduction. Sn has a special characteristic that it doesn’t

adsorb CO which clues the catalytic activity can be improved through formation of CuSn alloy structures. A lower

Sn amount in the CuSn alloy is found to be suitable for the production of CO with good selectivity and Faradaic

efficiency compared to either Sn-rich or respective bare electrodes in aqueous electrolyte, respectively.

Table: Composition dependent product selectivity of CuSn electrodes for CO2 reduction towards

formation of CO and total Faradaic efficiency

Composition CO (mole) CH4 (mole) H2 (mole) Selectivity Total Faradaic efficiency

Cu 0.6 2.93 10.24 ~1:5:17 56.2%

Cu0.75Sn0.25 18.1 0 3.6 ~5:0:1 59.5%

Cu0.5Sn0.5 4.4 0 3.3 ~3:0:2 51.4%

Cu0.25Sn0.75 1.2 0 3.4 ~1:0:2 19.4%

Sn 0.1 0 2.3 ~1:0:23 ~10%

Table presented above shows the product selectivity and total Faradaic efficiency of different electrodes at -1.3

V vs RHE. Cu electrode produces a high amount of H2 and CH4 with minor amount of CO as mentioned in the Table.

Sn electrode exhibits a poor catalyst for CO production. This is due to the fact that CO didn’t adsorb on Sn surface

and thereby producing other reduction products such as formic acid. However, Cu0.75Sn0.25 hybrid electrode exhibits

good selectivity for the production of CO with its Faradaic efficiency reaches to 59.5%. On the other hand, total

Faradaic efficiency for the production of H2, CO and CH4 decreases with increase in Sn-content in the CuSn alloy

electrodes. This is due to the fact that, Sn-rich alloys are more suitable to produce other liquid products of CO2

reduction, rather than CO or CH4. These results further motivate us to investigate the details of composition

dependent product selectivity and stability with other hybrid alloy catalysts for reliable CO2 reduction applications

for the production of chemical fuels.

References :

1) Hori, Y. Electrochemical CO2 reduction on metal electrodes. Mod. Aspects Electrochem. 42, 89–189 (2008).

2) Kortlever, R., Shen, J., Schouten, K. J. P., Calle-Vallejo, F. & Koper, M. T. M. Catalysts and reaction pathways

for the electrochemical reduction of carbon dioxide. J. Phys. Chem. Lett. 6, 4073–4082 (2015).

Fabrication of mesoporous titania thin film on p-type semiconductor substrate toward efficient wastewater purification *N. Suzuki1), A. Okazaki2), C. Terashima1), K. Nakata1)3), K. Katsumata1) and A. Fujisima1) 1) Photocatalysis International Research Center, Tokyo University of Science, Noda, Chiba, Japan, 2) ORC Manufacturing Co., Ltd., 3) Graduate School of Science and Technology, Tokyo University of Science *suzuki.norihiro@rs.tus.ac.jp Keywords: surfactant-assisted sol-gel method, porous thin film, titania, photocatalyst, p-n heterojunction Mesoporous material, which has pores with 2 – 50 nm in diameter, has unique properties such as uniform pore size, large pore volume, high surface area, and so on. Owing to these, mesoporous materials have a potential to show superior efficiency on surface related phenomena like catalytic reaction. Titania (TiO2) is a well-known metal oxide n-type semiconductor. Though its band gap differs depending on the crystal phase, it is about 3.2 eV (387 nm) in anatase phase. When UV light with wavelength shorter than 387 nm is irradiated, electrons in the valence band are excited to the conduction band, creating holes and electrons in the valence band and the conduction band, respectively. Because the photo-generated holes show strong oxidation ability, they can decompose organic pollutants. Thus, titania works as photocatalyst under UV light. Besides its high photocatalytic efficiency, titania has high stability and good biocompatibility. Furthermore, because titanium is an abundant metal, the production cost of titania is very low. Therefore, titania is one of the most widely-used photocatalyst. To achieve an effective oxidation by photocatalysts, as many as photo-generated holes should react with organic pollutant. However, in the single titania, recombination of photo-carriers often occurs. This carrier recombination decreases the number of holes react with organic pollutants, leading the lowering photocatalytic properties. To suppress the carrier recombination, p-n heterojunction has been used. At hetero-interface, an energy gradient is created to match the energy level of both bulk, and this gradient is useful to promote photo-generated charge separation. Thus, we fabricated mesoporous titania thin film on the p-type semiconductor substrate, aiming to enhancing the photocatalytic activity. Mesoporous titania thin film was fabricated by surfactant-assisted sol-gel method as described in the previous papers1). The precursor solution containing amphipathic surfactant micelles and titania sol were spin-coated on the boron-doped Si or diamond substrate (p-type semiconductor). During the evaporation of solvent, surfactant micelles self-assembles and they act as organic template. After removal of the template by calcination, mesoporous titania thin film is obtained. Schematic image is shown in Fig. 1. The morphology of synthesized film was examined with SEM image. As shown in Fig. 2, very well ordered porous structure was obtained. Mesopores with around 20 nm in diameter was hexagonally packed. The structural change depending on the substrate did not observed. In the presentation, we would like to show the photocatalytic activity of prepared films and their potential for wastewater purification. References 1) X. Jiang, N. Suzuki et al., Eur. J. Inorg. Chem., 2013, 3286-3291 (2013); N. Suzuki et al., Chem. Lett., 44, 656-658 (2015).

Fig. 1. Fabrication process of mesoporous ceramics by surfactant-assisted sol-gel method.

Fig. 2. Top-view SEM image of mesoporous titania thin film fabricated on boron-doped (a) silicon and (b) diamond substrate

Synthesis of FeOOH by Solution Process and Their Photo-functional Property

*K. Katsumata1) 1)Photocatalysis International Research Center, Tokyo University of Science, Noda, Chiba, Japan *k.katsumata@rs.tus.ac.jp (Corresponding author)

Keywords: oxyhydroxide, solution process, photocatalyst, hydrogen production

Energy and environmental issues at a global level are serious topics1). It is indispensable to construct clean and

sustainable energy sources. In order to solve the issues, hydrogen attracts attention because of its high energy density.

In term of sustainable and clean energy, hydrogen must be produced using renewable energy sources such as solar

light. In this study, hydrogen production by FeOOH under Hg-Xe lamp is investigated. FeOOH has three

advantages: iron is one of the abundant elements, easy synthesis, and photo-response under visible light.

The FeOOH powder sample was synthesized by typical coprecipitation method2). 3 g of FeSO4・7H2O was

dissolved in 100 ml water under vigorous stirring. The pH was adjusted to 6.5 ±0.5 by using ammonia solution.

After that, the solution was heated at 80oC for 4 h in oven, and it was dried at 60oC for 24 h. Finally, brown powder

sample was obtained. The sample was characterized by XRD, SEM and TEM.Photo-functional property was

evaluated by H2 production from 10 vol% methanol solution under Hg-Xe lamp irradiation.

The XRD pattern of the sample corresponded to orthorhombic -FeOOH, and the typical needle like morphology

was observed from TEM and SEM images. The sample exhibited better H2 production rate under pH=2 solution

than commercial -FeOOH and TiO2 (Fig. 1(a)). Additionally, at low pH, H2 production rate increased. Fig. 1(b)

shows that O2 gas was consumed during H2 gas production, and the production rate of H2 gas decreased when the

amount of O2 was less than 1 mmol. We guess that FeOOH changes to Fe, FeO, or Fe3O4 by self-photoreduction,

and then, these iron materials generate H2 under acid condition. After the reaction, Fe3+ ions react O2 and FeOOH

was formed. Therefore, H2 generation rate became lower because F3+ change to FeOOH under non-oxygen condition.

Figure 1(c) shows H2 production from methanol, ethanol, 1-propanol, and hexanol. We suggest that FeOOH is a

good candidate for hydrogen production.

Fig. 1 Amount of gas production under light irradiation. (a): Amount of H2 gas production for 24 h under Hg-Xe lamp irradiation. (b): Time

courses of H2 gas production and O2 gas consumption. The reaction condition: sample (50 mg), light source (Hg-Xe lamp), reactant solution (4 ml

methanol and water 36 ml), initial gas (150 ml air). (c) Amount of H2 gas production using various alcohols (Methanol, Ethanol , 1-Propanol, and

Hexanol).

References:

1) A. Kudo and Y. Miseki, Chem.Soc. Rev., 38, 253 (2009).

2) S. Wang et al., Colloids Surf. A, 403, 29 (2012).

Applications of Photocatalysis in Biology *K. Nakata1)2), K. Yamatoya1), Y. Kanai3), T. Suzuki1)2), N. Suzuki2), K. Katsumata2), C. Terashima2), and A. Fujishima2) 1)Department of Applied Biological Science, Tokyo University of Science, 2)Photocatalysis International research Center, Tokyo University of Science, 3)Research Institute for Science and Technology, Tokyo University of Science *nakata@rs.tus.ac.jp Keywords: Photocatalysis, Rare Sugars, Spore Inactivation, Germination

Photocatalysts as photo-functional materials are able to convert photo energy to chemical one, thus the property gives wide range applications for environmental cleaning and resource production, such as air and water purification, sterilization, hydrogen evolution, and photoelectrochemical conversion. In this presentation, new applications in biological field are reported.

1) Production of rare sugars using photocatalysis. Rare sugars have much attention because of their potential candidates for new foods and drags. For example, D-Allose has strong suppressive effect against cancer cell proliferation, and D-Psicose shows much sweetness, high solubility, water-holding property, spreadability, resiliency and antioxidation. However, it is very hard to obtain those sugars, thus a common and facile new method to produce rare sugars is strongly requested. Our group recently reported that arabinose could be produced from the oxidative decomposition of glucose by titanium dioxide (TiO2) photocatalysis under ultra-violet (UV) light illumination. In this work, we examined decomposition of monosaccharides to produce rare sugars by using the TiO2 photocatalyst. Photocatalytic decomposition of galactose was performed with the TiO2 photocatalyst under UV illumination, resulting in production of lyxose which is a rare sugar. From the comparison of molecular structure between garactose and lyxose, α-carbon was selectively released. We further performed photocatalytic oxidative decomposition of mannose, gulose, and allose, which allows production of arabinose, xylose and ribose, respectively. Those reaction also showed regular molecular conversion by release of α-carbon. Those results suggested that photocatalytic oxidative decomposition is able to produce rare sugars.

2) Spore inactivation with visible light responsive photocatalyst WO3. Bacteria that cause serious food poisoning are known to sporulate under conditions of nutrient and water shortage. The resulting spores have much greater resistance to common sterilization methods, such as heating at 100 °C and exposure to various chemical agents. Because such bacteria cannot be inactivated with typical alcohol disinfectants, peroxyacetic acid (PAA) often is used, but PAA is a harmful agent that can seriously damage human health. Furthermore, concentrated hydrogen peroxide, which is also dangerous, must be used to prepare PAA. Thus, the development of a facile and safe sporicidal disinfectant is strongly required. In this study, we have developed an innovative sporicidal disinfection method that employs the combination of an aqueous ethanol solution, visible light irradiation, and a photocatalyst. We successfully produced a sporicidal disinfectant one hundred times as effective as commercially available PAA, while also resolving the hazards and odor problems associated with PAA.

3) Improvement of germination of seed using photocatalysis. In seed germination, reactive oxygen species (ROS) play an important role. On the other hand, photocatalysts generate ROS under light illumination. In this work, we examined the effect of TiO2 photocatalysis for the seed germination under light illumination. Germination rates of columbine, sunflower and crown daisy etc. after photocatalytic treatment were higher than those of control (Fig. 1). Thus, the seed germination was improved using photocatalyst. Germination rate of seeds after absorption of diphenyleneiodonium chloride (DPI) as an inhibitor of germination was significantly decreased than that of control, whereas germination rate of both treatment of DPI and TiO2 under UV illumination was increased than that of the only DPI treatment. DPI suppressed NADPH oxidase which makes superoxide anion in seed. Thus, these results indicated that superoxide anion is likely to improve seed germination.

Fig. 1 Seed germination of columbine after photocatalysis and control.

Detections of intermediates and estimations of parameters for discharge

plasma formed in aqueous solution by time-resolved emission spectroscopy

M. Banno and

*H. Yui

Tokyo University of Science, Tokyo, Japan *yui@rs.kagu.tus.ac.jp

Keywords: discharge plasma, solution, pulsed voltage, emission spectroscopy, optical diagnosis

Discharge plasma has been attracted attentions in many fields as a unique reaction field. In plasma, many

reactions, which difficultly occur under ambient condition, proceed effectively by collisions between highly reactive

species. When pulsed high voltage with a temporal duration of microseconds is applied to a gap between electrodes

confirmed in solution, glow-like discharge plasma generates 1)

. Because the components contained in the electrodes

and the surrounding solution are readily taken into the plasma, the plasma is said to be a “designable reaction field”.

In particular, when the pulsed discharge is performed in aqueous solution, the solvent water is taken into the plasma.

The water molecules are dissociated into hydrogen (·H) and hydroxyl (·OH) radicals by collisions with free

electrons. Since ·H and ·OH exhibit high reduction and oxidation activities, respectively, it is expected that the

discharge plasma formed in the aqueous solution is effectively applied for reduction and oxidation reactions for

material syntheses, sterilization, and degradation of organic compounds. Actually, by utilizing the plasma formed in

aqueous solution, unique nanomaterials have been successfully synthesized. For example, composite metal

nanoparticles are synthesized by utilizing two metal rods with different components 2)

. In addition, the nanoparticles

synthesized in the plasma formed in aqueous solution exhibit high dispersion stabilities in solution. As the origin of

the high dispersion stabilities, it is thought that ·OH attaches to the surfaces of the nanoparticles in the plasma. In

the aqueous solution, a part of the attaching OH groups are ionized. The repulsion between the ionized OH groups

may provide the dispersion stability. As mentioned above, the discharge plasma formed in the aqueous solution

supplies an effective reaction field for nanomaterial syntheses with interesting features.

To control the properties of products in the plasma reaction fields, such as compositions and sizes, it is essential

to arrange the physical properties of plasma, which are electron density, electron temperature, and temperatures of

reactive species. In particular, to apply the plasma to the syntheses of carbon nanomaterials, temperature is a crucial

parameter for controlling the molecular structures, namely the ratio between the sp2 and sp

3 bonds between the

carbon atoms 3)

. However, the temperatures of reaction intermediates existing in the glow-like discharge plasma

have not yet been examined.

In this study, we first estimated the temperatures of the radicals by applying

time-resolved optical emission spectroscopy. By the analyses of the emission

spectrum from the plasma, the temperatures of ·H and ·OH were successfully

measured as 5,000 and 4,000 K, respectively. It is also revealed that the temporal

evolutions of the radical temperatures correspond well with that of the electron

number density, as shown in Figure. It is concluded that time-resolved optical

emission spectroscopy is a powerful method to investigate the temperatures of

intermediates and the origins of the temperature fluctuations 4)

.

It is expected that the reaction schemes and the compositions of the products

formed in plasma highly depend on the gas composition in the plasma. Therefore, to

apply the plasma reaction field more effectively, it is essential to control the gas

composition in the plasma. However, by discharge in aqueous solution, plasma is

formed in a water vapor babble. In this study, we developed a gas injection system

by utilizing metal pipe electrodes. Several kinds of gases can be directly injected

into the plasma through the pipe electrodes. By the optical emission spectroscopy, emission bands from several

transient species deriving from the injected gas molecules are observed. From the result, we have successfully

developed the direct gas injection system for the discharge plasma formed in aqueous solution, for applications in

many fields in future 5)

.

References:

1) O. Takai, Pure Appl. Chem., 80, 2003-2011 (2008),

2) M. A. Bratescu, O. Takai and N. Saito, J. Alloys Compd., 562, 74-83 (2013).

3) Y. Yamaguchi and S. Maruyama, Chem. Phys. Lett., 286, 336-342 (1998),

4) M. Banno, K. Kanno, Y. Someya and H. Yui, Jpn. J. Appl. Phys., 54, 066101 (2015).

5) M. Banno, K. Kanno, H. Yui, RSC Adv., 6, 16030-16036 (2016).

Fig. 1. Delay time dependence of the electron number density (top) and

the first derivative for the ·OH temperagure (bottom).

Application of Ozone to Sterilization of Water Circulated

in Cooling System for Transformer

-Evaluation of Corrosion Rate for Heat Exchanger-

H. Fukui1), H. Nagao1), M.Nakatoge1), S.Yamauchi*1), M.Yasuda2)

1)Tada Electric CO.,LTD, 2) Osaka Prefecture University

*Yamauchi.Shiro@TadaElectric.co.jp

Keywords: cooling tower, Legionella, corrosion,

Cooling towers and other portions of cooling system networks provide a superb environment for microbiological

growth and fouling. Without proper microbiological control, organisms can form vast colonies that may lead to the

reduced energy transfer in condensers and heat exchangers. Especially, growth of pathogenic organisms such as

Legionella, including species that cause the fatalities of Legionellosis or Legionnaires' disease must be prevented.

An investigation pinpointed cooling towers used for air conditioning as the source of more than 100 illnesses1).

Bacterial growth can be reduced or prevented by ozone sterilization, effectively. Since ozone has high reactivity

against organic materials and metals, a metal corrosion proceeds severely. According to design of the practical plant,

the corrosion resistance up to 30 years is required.

In an underground substation, the cooling systems of water-cooled transformer composed of primary cooler (oil

cooler) and secondary cooler (cooling tower) are adopted in many cases. The primary cooler discharges heat of

insulating oil generated from the transformer by the primary cooling water. The secondary cooler discharges the

heat of primary cooling water removed into atmosphere with the evaporation of the secondary cooling water. In the

secondary cooling system, the ozone sterilization of the secondary cooling water is very important and the corrosion

of heat exchanger has to be prevented. The cooling tower are classified into two types for closed or open system of

the secondary cooling water. In closed system, the primary cooling water flows inside cooling tube and directly

cools by spraying the secondary cooling water outside cooling tube. Open system has other spray tower. After the

heat exchange in the the secondary cooler, the secondary cooling water is cooled on the spray tower. We reported

ozone sterilization and corrosion suppression in closed system in the previous symposium.2)

In this presentation, we examined ozone sterilization and ozone corrosion in open cooling system. For this

purpose, we used model heat exchanger in which 0.5ppm ozone containing water was flowed through inner part of

Cu pipe for three month. We verified that the corrosion resistance of the Cu pipe will maintain up to thirty years and

sufficient ozone sterilization was effective against micro-organisms including genus Legionella.

References

1) Surveillance Reports, U.S. Centers for Disease Control, 2009.

2) S. Yamauchi, H. Nagao, T. Fujita, M. Tsuboi, M. Yasuda, Proceedings of 22th Annual Conference on Ozone

Science and Technology in Japan, 2016, 26-29 (2013).

Biomimic Anti-stain Surface Treatment for Housing Wet Area *N. Isu1) 1)LIXIL Corp., Koutou, Tokyo, Japan * norifumi.isu@lixil.com Keywords: Biomimic, Anti-stain, Anti-bacterial, Ceramic, Environmental load reduction 1. Introduction The fundamental way of thinking on the human and the earth conscious manufacturing and some examples of its application were discussed. One of the biggest suffering at home is a cleaning around the bath room area where water is used. Much energy and resources are consumed for eliminating dirt or stain at home as well as buildings. Anti-stain surface treatments mimicking snail shell are applied to housing wet area (Table1), resulting in the decrease of the housekeeping energy. In this paper, ceramic tile and sanitary ware are reported. 2. Snail shell and ceramic tile The shell of snail is always clean on rainy days. Because many small grooves on the surface of the shell play a role like a rain gutter, the water film forms on the shell surface to prevent oily dirt. The dirt easily comes off with a little rain. Although ceramic tiles are originally hard to get dirty, it is necessary to be more hydrophilic than ordinary tiles for urban dirt including oil content like smoke. By coating with higher hydrophilic nanoparticles on ceramic tile (Fig. 1), the oil containing dirt is easily removed with rain alone. 3. Antibacterial sanitary ware The antibacterial treatment is necessary to keep hygiene environment around wet area. Silver is widely used as inorganic antibacterial agents, because of high activity, broad antibacterial spectra, durability and low toxicity for human. Ag is applied to the sanitary ware glaze as an antibacterial agent. The glaze is amorphous aluminosilicate with 0.08 wt% Ag. The HEXRD （High-Energy XRD）results showed that the radial distribution functions of glaze were nearly identical with or without Ag. The XAFS (X-ray absorption fine structure) spectrum of Ag-glaze were quite similar to that of AgNO3 aqueous solution (Fig. 1). This indicates that silver exist as monovalent cation in the glaze without forming crystal structure.

3300 3320 3340 3360 3380 3400e) AgO

d) Ag2O

c) AgNO3 aq

b) Ag-glaze

a) Ag

Energy [eV]

Nor

mal

ised

abs

orpt

ion

coef

ficie

nt

Fig. 1. Ag-LIII XAFS spectra by fluorescence mode. of a)Ag, b)Ag-glaze, c)AgNO3 aqueous solution, d)Ag2O and e)AgO.

Table 1. Anti-Stain Surface Treatments.

Fig.1. SEM photo of hydrophilic coating on ceramic tile.

Characterization of titanium peroxide nanoparticles as a novel radiosensitizer

Chiya NUMAKO(1,*), (1) Graduate school of Science, Chiba University, Yayoi 1-33, Inage, Chiba 263-8522,Japan

e-mail: numako@chiba-u.jp)

Titanium peroxide (TiOx) was developed to be a specific radical generator for radiation therapy of cancer in our investigation. It was observed that titanium oxide treated with H2O2 (TiOx) generated radical species and reduce the cancer cell with irradiation of X-rays. In order to elucidate the mechanism of the radical generation in TiOx, ESR and XAFS analyses was applied to the TiOx particle.

XAFS measurements in fluorescence and change electron yield mode for the TiOx and standard materials of titanium with known chemical composition and crystal structure, Ti metal, TiO2 minerals (Rutile and Anatase), Ti3+ aqueous solution, and BaTiO3, were performed for Ti K-edge at BL7C, 9A and 12C in Photon Factory, KEK. Incident beam was monochromatized with a Si(111) monochromator, made into 2 x 1 mm2 with slit and counted with Ion chamber for Io and Lytle type fluorescence detector for If. Several specimens for TiOx were prepared with irradiation from 0 Gy until 210 Gy in order to elucidate the effect of radiation on chemical and structural condition of TiOx.

ESR spectra of TiOx specimens indicated that some radical species were generated on TiOx and they were increased with X-ray irradiation. However, the radicals could not be identified only from ESR parameters.

The spectral shape of XANES for TiOx was resembled to that of Anatase roughly, however, the detailed spectral feature, especially at pre-edge peak, was different from those of others. It was considered that titanium in the TiOx is tetravalent from energy positions of Ti K-edge, and its crystanity is small as same as nano-porous TiO2 from disappearance fine structure of XANES spectra. EXAFS oscillation and Ti-Ti interaction in radial distribution curves of TiOx specimens were getting decreasing with irradiation so that Ti-Ti bond in TiOx was seemed to be destroyed and TiOx was alternated into amorphous with irradiation of X-rays. Due to fragmentation of crystal structure of TiOx, non-bonding electron might be increasing in the TiOx particles, exposed to water to contact with some dissolved chemical species, and generate radicals as a result.

TiO2Rutile

BaTiO3

TiCl3solution

TiH2

Nor

mal

ized

Abs

orpt

ion

Coe

ffici

ent

Energy / eV

TiO2Anatase

TiOxsuspension

TiOx Powder

0

0

0

0

0

0

0

0

1.2

Ti Metal

4900 4950 5000 5050 5100

Fig. 1 Ti K-XANES spectra for TiOx and Ti standard materials

TiO2

TiOx

irradiated

TiOx

Radiation

Ti

Ti

Ti

Ti

O

O

O

Ti

Ti

Ti

Ti

O

O

O

O

O···

·

Ti

TiTi

O

O

OTi

O· ·

··

·

· ·

·· ·

H2O2

core：TiO2surface ：TiOx

Ti-O bond s are destroyedby X-ray radiation

Fig. 2 Schematic illustration of alternation from TiOx to TiOx

Abstract Guideline (Leave two lines for presentation number)

Facile method to Surface modification of super aligned CNT sheets *S. Y. Moon1) 1) Korea Institue of Science and Technology(KIST), Wanju, Jeonbuk, Korea *moon.sookyoung@kist.re.kr Keywords (Maximum: 5keywors, 10 point): : CNT, functionaizaiton, interfacial bonding, Composite

Carbon nanotubes (CNTs) have been considered for many applications because of their extraordinary physical, chemical, and mechanical properties. Despite their many desirable properties, the hydrophobicity and chemical inertness of CNTs hinders their commercial utilization. To overcome these limitations, CNT surfaces were functionalized using either covalent (chemisorption) or non-covalent modification (physisorption). Covalent surface modification involves the direct incorporation of new elements or organic functionalities into the CNT sidewalls. But a major problem of both chemical and physical surface modifications remained the impurity onto the CNT surface and some impurity is difficult to remove in further processes or applications. Therefore, development of a better and more effective functionalization method remains a major challenge.In this study, we report a novel method to modify CNT surfaces using hydrogen and developed composite with epoxy resin. This method has been proven to be effective in terms of making functionalized CNT surface and improving interaction between CNT and polymer. Interactions between surface properties of the CNT and mechanical properties are discussed in relation to the hydrogen treatment conditions. Aligned MWCNT sheets established a simple and efficient synthesis method according to Inoue et al. 1),2) The MWCNT sheets exposure to hydrogen atmosphere at high temperature. The CNT/epoxy composites were processed hot-melt prepreg method with the B-stage un-cured epoxy resin, which consists of bisphenol-A type epoxy, novolac type epoxy, and an aromatic diamine curing agent. The surface changes of the CNTs according to hydrogen treatment conditions were investigated by XPS spectroscopy. As shown in Figure 1, hydrogen interaction led to a change in the C1s peak shape and position. For increasing reaction time, the C1s peak was shifted at higher and lower binding energy compared to the original samples. The binding energy shift of the main peak was in accordance with the chemical shift between sp2 and sp3 hybridized carbon species in MWCNT and due to attachment of hydrogen to the C–C bonds resulting in C–H bond formation. 3),4) The tensile tests of nanocomposites revealed an increase in elastic modulus and fracture strain with hydrogen treatment, suggesting that hydrogen treatment accomplished enhancing interaction between CNT and polymer. The elastic modulus of the control sample is 19.92 ± 3 GPa with 6 vol% of hydrogen treated CNT/epoxy composite. The fracture strain is 0.84% with hydrogen treatment which is remarkably increased than original samples at 0.5%.

References 1) Y. Inoue, K. Kakihata, Y. Hirono, T. Horie, A. Ishida, H. Appl. Phys. Lett., 92, 213113(2008) 2) Y. Inoue, Y. Suzuki, Y. Minami, J. Muramatsu, Y. Shimamura, K. Suzuki, A. Ghemes, M. Okada, S. Sakakibara, H. Mimura, K. Naito, Carbon 49, 2437–2443(2011) 3) T. I. T. Okpalugo, P. Papakonstantinou, H. Murphy, J. McLaughlin, N. M. D. Brown, Carbon 43, 153-161 (2005) 4) A. Nikitin, H. Ogasawara, D. Mann, R. Denecke, Z. Zhang, H. Dai, K. Cho, A. Nilsson, Phys. Rev. Lett. 95, 225507 (2005)

Fig.1 C1s XPS spectra of MWCNT sheet with various reaction time

[Abstract Guideline (Leave two lines for presentation number)] Microscale Patterning on Resin Substrates by Electroless Plating *Y. Horiuchi1), Y. Suzuki1)2) , T. Miyazeki1)3), C. E. J. Cordonier1), J.-H. NOH1)2), O. Takai1)2), and H. Honma1)2) 1)Materials and Surface Engineering Research Institute, Kanagawa, Japan, 2)Graduate School of Engineering, Yokohama National University, Kanagawa, Japan, 3)Graduate School of Engineering, Yokohama National University, Kanagawa, Japan *yoshio.horiuchi@gmail.com (Corresponding author, 10 point) Keywords : Electroless plating, Microscale patterning, Resin,

Plating on resins is generally applied with hex avalent chromium and permanganate as an etching solution for

improvement of adhesion strength between the resin and deposited metal. This conventional etching method, however, has high environmental impact, because it gives rise to waste fluid issues. Therefore, alternative methods with environmentally friendly process were reported, e.g. UV irradiation method and ozonized water treatment method. Accounts of selective electroless plating on UV irradiation modified polymer have been reported. In order to form metal patterns with line width of a several µm, the reaction of polyethylene naphthalate (PEN) film with collimated irradiation from a deep-ultraviolet emission boosted-super high-pressure mercury lamp was investigated. Next, with the fully-additive process, metal patterns of several µm line width were formed directly on the polymer substrate was evaluated.

Surface modification of polymer films was performed with UV irradiation, which resulted in selective nanometer scale etching. PEN (Q65HA developed by Teijin Du Pont Films Japan Ltd.) film was cut into 5 x 5 cm squares, then ultrasonically cleaned in methanol then dried at room temperature prior to UV exposure for 20 min. The films were exposed to collimate irradiation from a deep UV boost super high-pressure mercury lamp (USH-250BY/D-z1 developed by Ushio Inc.). For direct pattern formation, a fused quartz photomask was placed on top of the film. UV modified resin was plated according to the electroless copper plating procedure specified in Table 1. The electroless copper plating bath (PB-506 developed by JCU Co., Ltd.) was used a commercial formaldehyde (HCHO) based type. Deposited metal patterns were observed using a laser microscope (LEXT OLS4000 developed by Olympus Co.).

The increase in oxygen content after UV exposure then partial decrease after treatment in alkaline is concurrent with UV irradiation induced oxidative cleavage in the PEN substrate surface resulting in formation of low-molecular-weight (LWM) materials that was subsequently extracted in the alkaline solution to leave the hydrophilic oxygen enriched surface. The formed modified surface can be preferentially adsorbed to the electroless plating catalyst. Fig.1 shows microscope images of metal patterns formed using this technique. Variation between the copper patterns formed and the corresponding photomask could not be observed on the microscopic scale. (Fig. 1)

Table 1. Electroless copper plating procedure.

UV Irradiation������Alkaline treatment (NaOH)������

Conditioning treatment ������� ������� ���������� ������

������Catalyzing (PdCl2)������

Activation (NaH2PO2)������Electroless copper plating

��������������

Fig. 1. Electroless copper patterns (grid and honeycomb) with 5 µm of line width.

Stability Analysis of Seabed Pipeline using Movable Bed Hydraulic Model Test

*H.D Kim1), K.H Kim2) , H.M Bae2) 1) University of Delaware, Newark, Delaware, USA 2) Catholic Kwandong University *hdkim@udel.com

Keywords: Hydraulic Model Test, Seabed Pipeline, Stability Analysis, Movable bed

Pipelines are installed in marine environments for transporting gas and crude oil from offshore platforms,

and for the disposal of industrial and municipal waste water into the sea. The development in the offshore oil

industry in the past 30 years or so has led to tens of thousands of kilometers of pipeline networks laid in the North

Sea, in the Gulf of Mexico, and in many other places across the globe, and these networks have become “lifetimes”

of the oil industry. Not just oil, these pipelines are also crucial in thermal power plant. When pipeline is exposed to

direct flow action, when the seabed is erodible, scouring may occur around the pipes under the flow action and may

lead to suspended free spans of pipelines. The pipeline along the length of the suspended span may or may not sag in

the generated scour hole. In the case of a sagging pipeline, the pipeline may reach the bottom of the scour hole,

which may be followed by backfilling and eventual self-burial of the pipeline. (B. Sumer et al.). Given the scour

frequency and depth assessments and more, what are the implications for the probability of pipeline failure?

Complete failure if a scour occurs and scouring depth is greater than the distance from the sea bed to the top of the

pipes. Therefore, many scientists and engineers try to practice numerical model to see what could cause the failure

of the installation and try to avoid it from considering the scour frequency. However, usual assumptions were

explicit consideration of the possibility of pipeline failure for reasons other than scouring. Simple model

assumptions captured this effect numerically; however, before the installation based on numerical, movable bed

hydraulic model test is important to countermeasure further failure that has not been discovered by the numerical

model tests.

In this paper, stability of pipeline under ocean was analyzed by movable bed hydraulic model test. For the

hydraulic model experiment, two dimensional hydraulic model test from figure 1 with twenty five different cases

were conducted prior to actual sea observational data collected. Collar as shown in figure 2 weight is one thing that

is important to design stable pipeline; however, in actual bottom of ocean, scouring affects the pipeline that

considering it during the experiments was needed. It was found that material types of the pipeline is also important

to find out the stability as well as backfilling the collar length of certain percentage more were key points to find out

the stable design for the pipelines under the ocean

Fig. 1. Two dimensional wave flume

Fig. 2 Pipeline collar used for the experiment

References 1) J.W Fisher., and J.H.A Struik Guide to design criteria for bolted and riveted joints (1974)

2) W.S. Mossberg Wall Street J. Dec.2, B1 (1993)

3) C.R. Pennoni J. Profl. Issues in Engrg. Educ. And Pract., ASCE, 118(3), 221-233 (1992)

The Impact of Natural Disaster Risk on Housing Market in Miami Florida

*Sohn, J.1) and Kim, H.1) 1) University of Florida, Gainesville, Florida, U.S.A.

* juniksohn@ufl.edu

Keywords: natural disaster impact, flooding area, housing market, house price, hedonic price model

The evidence of rapidly changing climate is irrefutable and quite compelling. Also, the frequency of natural

disaster is increasing every passing year. The average number of annual natural disaster approximately doubled

per decade since the 1960s (Blaikie et al., 1994). Consequently, the US median disaster damage cost by hurricanes

from 1980 to 2010 is $1.8 billion (Muller, 2011). Florida has been consistently ranked top five states with

hurricane frequency. Meanwhile, coastal cities like Miami has developed into the core of tourism and business.

The property value of the waterfront increased, and population density also increased as the city grew. Waterfront

became an essential element of the development of coastal cities. Waterfront is geographically at the high risk of

inundation. Cities with high density and concentrated economic activities like Miami has a higher potential risk

of natural disaster damage (Pryce & Chen, 2011). However, a large proportion of the population is poorly

integrating with this risk, particularly on housing decisions as the probability of natural disasters is only a small

consideration (Bin & Kruse, 2006).

Although scientists and scholars agree on the pace and severity of climate change. There are a plethora of

studies on various aspects of climate change. However, researchers are divided on the impact of natural disaster

on the housing market. Literature provides two compelling schools of thought. Some scholars argue that the risk

of natural disaster lowers the house prices in the disaster risk areas (Bin & Kruse, 2006, Speyrer & Ragas, 1991),

and the other argument asserts that the disaster risk has no effect on housing market (Lamond, 2009). However,

most of the existing literature examined the impact of natural disaster on housing market in non-metropolitan

flooding areas in county level (Bin & Kruse, 2006, Bin & Landry, 2013, Bin & Polasky, 2004). Although natural

disaster risk impact on the housing market is different by the area, it influences house prices. Additionally, the

impact should be larger in developed areas. In this paper, we investigate the relationship between disaster risks

and house prices in Miami. The sample will be divided on the basis of FEMA's flood insurance rate maps (FIRMs)

which determines potential flood risks using a different combination of sea level rise, storm surge, tides, etc. We

will use hedonic pricing model to understand the direct and the indirect impact on the housing market with changes

in disaster risks.

References:

1) Bin, O., & Kruse, J. B. (2006). Real estate market response to coastal flood hazards. Natural Hazards Review,

7(4), 137–144.

2) Bin, O., & Landry, C. E. (2013). Changes in implicit flood risk premiums: Empirical evidence from the

housing market. Journal of Environmental Economics and Management, 65(3), 361–376.

3) Blaikie, P. M., Cannon, T., Davis, I., & Wisner, B. (1994). At risk: Natural hazards, people’s vulnerability,

and disasters. New York: Routledge.

4) Muller, G. (2011, June 29). Hurricane Season Could Cost Record Billions in Weather Damage.

Accuweather.com, Retrieved from http://www.accuweather.com/en/weather-news/wild-weather-costs-at-

least-23-1/51641

5) Pryce, G., & Chen, Y. (2011). Flood risk and the consequences for housing of a changing climate: An

international perspective. Risk Management, 13(4), 228-246.

Effect of Copper(II) ion on Adsorption of Lead(II) ion onto Natural and Modified Leonardite from Aqueous Solution *P. Pookmanee1)2), A. Wannawek1)2), S. Satienperakul1), R. Putharod1)2), and S.Phanichphant3) 1)Department of Chemistry, Faculty of Science, Maejo University, Chiang Mai, 50290, Thailand, 2)Nanoscience and Nanotechnology Research Laboratory (NNRL), Faculty of Science, Maejo University, Chiang Mai, 50290, Thailand, 3)Materials Science Research Center (MSRC), Faculty of Science, Chiang Mai University, Chiang Mai, 50200, Thailand *pusit@mju.ac.th Keywords: Leonardite, adsorption, modification, lead(II) ion, copper(II) ion

Leonardite is adsorbent for removing heavy metals from aqueous solution. In this research, modified leonardite was prepared by adding manganese from precipitation method. The chemical compositions and properties of natural and modified leonardite were characterized by X–ray diffraction (XRD), X–ray fluorescence spectrometry (XRF), Energy dispersive X–ray spectrometry (EDXS), Fourier transform infrared spectrometry (FTIR), Scanning electron microscopy (SEM) and Brunauer–Emmett–Teller analyzer (BET). The adsorption behavior of lead(II) ion and effect of copper(II) ion onto these adsorbents were studied. A batch system was applied to lead(II) ion adsorption processes. The final concentration of lead(II) ion was determined by atomic absorption spectroscopy (AAS). Langmuir adsorption model was concerned to express adsorption isotherms and maximum adsorption capacity.

The result of XRD showed that main mineral component of natural leonardite is quartz. The data of XRF and EDXS showed that silica was a major component of natural and modified leonardite. Alcoholic, carboxylic, carbonyl groups and siloxane were established in leonardite by FTIR. Leonardite has a sheet or a flat in shape, it was showed by SEM. BET data showed that the surface area of modified leonardite which modified by manganese was more than natural leonardite. Effective removal of lead(II) ions was indicated at pH 5.0 in 1 hr. Langmuir equation of adsorption experiment data was showed the maximum adsorption capacity. In this research, adsorption of lead(II) ion onto 10% manganese modified leonardite was the highest. However, adsorption of lead(II) ion onto leonardite decreased with rising concentration of copper(II) ion (Fig 1). The maximum adsorption capacity of lead (II) ion free copper (II) ion onto natural leonardite, 1%, 5% and 10% modified leonardite were 13.39, 16.13, 79.37 and 151.52 mg·g–1 respectively.

References 1) C. Lao, Z. Zeledón, X. Gamisans and M. Solé, Sep. Purif. Technol., 45, 79-85 (2005). 2) D. Tiwari., C. Laldanwngliana, C. H. Choi and S. M. Lee, Chem Eng J., 171, 958-966 (2011). 3) Y. Chammui, P. Sooksamiti, W. Naksata, S. Thiansem and O. A. Arqueropanyo, Chem Eng J., 240, 202-210 (2014).

Fig. 1. Effect of copper(II) ion on the maximum adsorption capacity of lead(II) ion onto natural leonardite, ● free copper(II) ion, ■ 10 ppm, ▲ 30 ppm and ♦ 50 ppm.

Advanced Packaging Solution for Next Generation IC Packaging

*Jong-Young PARK1)2)3), Young-Jae KIM2)3) , Joo-Hyong NOH1)2), Jae-Guen YANG3),

Osamu Takai1)2) and Hideo Honma1)2)

1)Department of Materials and Surface Engineering, Graduate School of Engineering, Kanto Gakuin University,

1162-2 Ogikubo, Odawara, 250-0042, Japan 2)Materials and Surface Engineering Research Institute, Kanto Gakuin University, 1162-2 Ogikubo, Odawara,

250-0042, Japan 3)Daeduck Electronics Co. Ltd., 335, Somanggongwon-ro, Siheung-si, Gyeonggi-do, 15106, Korea *jnsc2000@daeduck.com

Keywords : Cu-pillar, Pre-treatment, Plating, Packaging, FOWLP

The recent appearance of mobile application processor now plays an important role in the semiconductor industry.

Additionally, there have been endless demands for small form factor, thin profile, outstanding thermal, mechanical

properties and electrical performances in the field of IC packages for mobile application processors.

Molded Interconnect Substrate can provide very ideal and this solution in the mobile industry as it contains

multiple solution for the complicated requirement of the IC packages for application processors. Based on the

embedded pattern technology, this solution can provide high I/O count, fine pattern for small form factor, and stable

flip chip mounting methods. Other advantages of this solution include stable properties required for high-frequency

transmission and high thermal dissipation rate as it is only composed of Copper and Epoxy Mold Compound

materials.

The biggest advantage of MIS is the ability to achieve ultra-thin thickness by using glass-less material, where the

total thickness of a package can be less than 0.4mm. In addition, Cu-pillar for electrical connection between inner

and outer layers can be manufactured with photo lithography process followed by grinding process, which replaces

laser drilling process, and therefore reduce the production cost.

MIS technologies can be applied to various fields such as mobile application, sensor, auto-mobile, SiP(System In

Package), and there have been continuous demands for such technologies in the related areas.

Furthermore, direct formation of traces on top of the mold surface is possible, and it can be applied to Chip first

FOWLP(Fan Out Wafer Level Package) with I/O count less than 1000, along with its excellent degree of freedom in

the thickness of package and traces.

These core techniques for MIS technology can be divided into below major concepts.

First, Cu pillar electrolytic plating technology to electrically connect the inner and the outer layers using

photo-lithography method, instead of laser method. The shape of Cu pillar and the plating thickness tolerance

control are the key parameters. Second, Grinding technology to precisely grind the plated Cu pillars and applied

mold epoxy. And deposition of Cu layer on top of grinded mold surface to construct fine pattern traces.

The figure 1 illustrates the representative structure of advanced packaging solution.

Fig 1. Structure of applied advanced packaging solution

References:

1) In Lee and Kyoochun Lee, Business Horizons, 58, 431 (2015)

2) Young-Jae KIM, Jong-Young PARK, Kwan-sun YOON, Joo-Hyong NOH, Hideo HONMA and Osamu TAKAI,

Journal of Nanoscience and Nanotechnology, Vol. 16, 2016.11

Controlled drug release from pH-responsive polymeric micelles using amphiphilic block copolymer synthesized by mechanochemical solid-state polymerization and its Cytotoxicity *S. Kondo1) Gifu Pharmaceutical University, Gifu, Gifu, Japan, 2) College of Pharmaceutical Sciences, Matsuyama University, 3) Faculty of Human Welfare, Chubu Gakuin University

1), K. Tatematsu1), N. Doi1), Y. Sasai1), Y. Yamauchi2), and M. Kuzuya3)

*skondo@gifu-pu.ac.jpKeywords: pH-responsive polymeric micelles, amphiphilic block copolymer, cytotoxicity

It has been known that amphiphilic block copolymers consisting of a hydrophilic and a hydrophobic block can

form core-shell micelles in a selective solvent for one of the blocks due to the association of the insoluble block. The micelles formed are referred to as “polymeric micelles.” Polymeric micelles have attracted much attention in drug delivery systems because of their ability to solubilize hydrophobic molecules; nanoscale size; good thermodynamic solution stability; extended release of various drugs; and prevention of rapid clearance by the reticuloendothelial system. Recently, stimuli-responsive polymeric micelles have emerged as a novel controlled-release system in which drugs can be released by appropriate stimuli, such as temperature, pH and ultrasound. A pH-sensitive polymeric micelle is useful for targeting to tumor tissues, endosomes and lysosomes, because these sites are more acidic environment than other parts such as blood. We aimed to fabricate polymeric micelles which would break down into unimer under acidic conditions (Fig. 1).

In this study, we synthesized the amphiphilic block copolymer having basic hydrophobic chain and hydrophilic chain by mechanochemical solid-state polymerization. Two kinds of amphiphilic block copolymer were synthesized (Fig. 2). The polymeric micelles, Polymeric micelle I and II, were prepared by dialysis method from Polymer I and II, respectively. The number average particle diameter of Polymeric micelle I and II at pH 7.4 was about 150 and 87 nm, respectively. Polymeric micelle I was steeply broken down into unimer at pH 5 within 30 min. On the other hand, particle diameter of Polymeric micelle II gradually decreased and it took about 48 h to complete deformation of polymeric micelle. It was also confirmed that micellization and demicellization reversibly proceeded. To confirm the cellular uptake of polymeric micelle, the polymeric micelle incorporating fluorescent dye (fluorescein or DyLight 488) was prepared, and then it was applied to cancer cell line (HepG2). Strong fluorescence was exhibited after 12 h of incubation in both polymeric micelles. Preincubation with chloroquine before the treatment of polymeric micelle incorporating fluorescent dye suppressed the fluorescence intensity in both polymeric micelles. These results suggest that fluorescence dye was released from polymeric micelles into acidic organelles (endosomes and/or lysosomes). The polymeric micelle containing 5-fluorouracil (5FU), Polymeric micelle-5-FU I and II, were prepared by dialysis method with Polymer I and II, respectively. The cytotoxicity of Polymeric micelle-5-FU I and II against HepG2 cells was evaluated using a CCK-8 assay. It was shown that the Polymeric micelle-5-FU I and II were more cytotoxic to HepG2 cells than free 5-FU. Although Polymeric micelle-5-FU I showed the cytotoxicity to HepG2 at 24 h incubation, it took 48 h for Polymeric micelle-5-FU II to show the cytotoxicity. It might be ascribed to the slow deformation of Polymeric micelle II.

Development of EC device with diamond electrode

based on the analysis of generation mechanism for electrolytic ozone water

*A. Hara

1), C. Terashima

2), N.Suzuki

2), K. Nakata

1)2), K. Katsumata

2), T. Kondo

1)2), M. Yuasa

1)2)

and A. Fujishima2)

1)

Tokyo University of Science (2641, Yamazaki, Noda, Chiba, 278-8510, Japan) 2)

Research Institute for Science and Technology, Tokyo Univ. Sci. *7216658@ed.tus.ac.jp

Keywords : Boron-doped diamond, Electrochemical, Ozone.

Boron-doped diamond (BDD) electrode has

excellent chemical and physical stability with

high ozone generation efficiency1)

. Also, ozone

has attracted much attention in the fields of

sterilization, deodorization and decolorization

due to its high oxidation power and low

persistence. Furthermore, in the case of ozone

water, it is reported that the function of

sterilization and deodorization is faster than

ozone gas, because it produces active species such as hydroxyl radicals2)

. Ozone water is synthesized using the zero-gap type electrolytic cell constructed by inserting a solid electrolyte

membrane such as Nafion film between BDD electrode and counter electrode (Fig. 1(b)). This is a clean system that

can efficiently synthesize ozone water from only water. However, the deterioration factor of the cell have not been

revealed yet. Therefore, in this research, we aimed to clarify these and lead to improvements.

Firstly, in order to investigate the deterioration factor of the cell,

constant current electrolysis of 400 mA (HABF5001-B10,

Hokutodenko Co., Ltd.) as a durability test was conducted. After

conducting electrolysis in 15 mL of ultrapure water for 30 seconds, the

concentration of ozone water was measured by the dissolved ozone

meter (O3-3F, Kasahara Co., Ltd.) and it was repeated until the cell

voltage reached 50 V. And then, in order to investigate the degree of

deterioration of the Nafion film, an IR spectrum (FT/IR-6600, JASCO)

was measured.

From the results of the durability test shown in Fig. 2, it was

confirmed that the cell voltage reached 50 V in 28 measurements, and

the cell was durable about 14 minutes at 400 mA. Also, it was found

that it is possible to synthesize ozone water at a maximum of 2.11 ppm

in a short time. This is a sufficient amount of ozone water for

sterilization. However, as the cell voltage increases, the concentration

of ozone water decreases, and also, deterioration of the Nafion

membrane can be confirmed from the IR spectrum shown in Fig. 3.

Therefore, it is considered that the proton conductivity of the Nafion

membrane is lowered by electrolysis. Furthermore, when observing the

state of electrolysis, it was found that the reaction surface is only the

three-layer interface of BDD, Nafion and SUS. From the above, it is

considered that current concentrated locally and deterioration of the

Nafion film was promoted. Therefore, in the ozone water synthesis

using the zero-gap type electrolytic cell, it is necessary to suppress

deterioration of the Nafion membrane.

1) K. Arihara, C. Terashima, and A. Fujishima, Electrochem. Solid-State Lett, 9 (2006) D17–D20.

2) L. C. Cheng et. al., RSC Advances, 3 (2013) 5917–5925.

Fig. 1 (a) Design of the cell (b) Cross section of the cell

Fig. 2 Result of durability test

Fig.3 IR spectrum of Nafion film

Design of Flow Type Sensor Using TiO2 Ink Capable of Screen Printing

*K. Katagishi1), C. Terashima2), N.Suzuki2), I. Shitanda1)2), K. Nakata1)2), K. Katsumata2),

Y. Hoshi1), M. Itagaki1)2) and A. Fujishima2) 1)Tokyo University of Science (2641, Yamazaki, Noda, Chiba, 278-8510, Japan) 2)Research Institute for Science and Technology, Tokyo Univ. Sci. *7216621@ed.tus.ac.jp

Keywords : photocatalyst, electrochemical, screen-printing, sensor

Screen printing has been widely applied for the fabrication of electrochemical devices because a wide variety of

inks can be used to generate precise patterns with high reproducibility. And it is possible to print on objects of

various shapes, and the cost is low. In this study, we adopted a paper substrate. The paper-based electrochemical

devices are easy to use, require small volumes of reagents and sample, provide rapid analysis, and are readily

disposable. In addition, since the main component of the paper is cellulose fiber, it is possible to infiltrate the liquid

into the hydrophilic fiber without requiring an active pump or an external supply source1). TiO2, which is a

photocatalyst shows extremely strong oxidizing power by irradiation with ultraviolet light. If TiO2 ink can be

prepared and screen printed on a paper substrate, the reaction system which has proceeded with a complicated

reaction can proceed with a simple system and can be quantitatively determined at low cost. In this study, a reaction

part on which a TiO2 ink was printed was placed upstream, and a three electrode chip was placed downstream. We

have developed a device that detects the substance at photoreacted upstream on the electrode part.

The design of the cell in this study is shown

in Fig.1. TiO2 ink was prepared by adding 10

wt% of titanium dioxide nanoparticles (P-25,

Nippon Aerosil Co.,Ltd.) using EC vehicle

(200FTR, Nissin Kasei Co., Ltd.) or

polyvinylidene fluoride (PVdF) as a binder

and stirring for 30 minutes. This ink was

printed on a filter paper using a screen printing

machine (LS-150TV, New Long Industrial Co.,

Ltd.) and dried at 120 ℃ for 15 minutes. In

order to evaluate the printability of the printed

TiO2 ink, rheometer (MCRxx2, Anton Paar)

was used. And in order to confirm the photocatalytic activity, a methylene blue solution was used. The lower part of

the paper substrate was immersed in the solution, and then solution flows to the TiO2. Ultraviolet light of 50

mW/cm2 (MAX303, Asahi Spectroscopical Co., Ltd.) was used as a light source. Carbon ink was printed on the

working electrode and counter electrode, and Ag/AgCl ink was printed for the reference electrode.

TiO2 ink using EC vehicle and PVdF as a binder was prepared. As a result of screen printing using these inks, it

was confirmed that the ink using EC vehicle was printable. From the results of rheometer, it is considered that

viscosity is higher and decreased by increasing shear rate when EC vehicle is used. The prepared TiO2 ink was

printed using a screen printing machine, and a decomposition experiment of methylene blue was carried out by a

flow type. From the results of the experiments, by irradiating the TiO2 layer with ultraviolet light, the methylene

blue solution became transparent showing the decomposition. Therefore, it was confirmed that prepared TiO2 ink

produced has oxidizing power and photocatalytic activity by irradiation with ultraviolet light even when it was used

in flow system. Next, cyclic voltammetry was measured in 5 mM K4[Fe(CN6)] solution using three electrodes chip.

As a result, the redox peak of [Fe(CN6)]4- / [Fe(CN6)]3- appeared and it was confirmed that it functions as an

electrode. By using this TiO2 ink and three electrodes chip, it becomes possible to create a flow type sensor.

1) Martinez, A.W.; Phillips, S.T.; Whitesides, G.M. Carrilho, Anal. Chem. 82 (2010) 3–10.

TiO2

UV

flow

electrode

substance

paper

productOxRed

sensor

Fig. 1. Design of the cell

Dependence of Electrochromic Reaction Speed of Nanostructured InN films

on Conductive ITO Layer Thickness

Y. Shiina

1), H. Izumisawa

1),

*Y. Inoue

1)2), and O. Takai

3)

1) Graduate School of Engineering, Chiba Institute of Technology, Narashino, Japan,

2) Department of Advanced

Materials Science and Engineering, Chiba Institute of Technology, 3)

Kanto Gakuin University *inoue.yasushi@it-chiba.ac.jp

Keywords : glancing-angle deposition, indium nitride, adsorption-induced electrochromism

Indium nitride (InN) is one of the materials which exhibit an

adsorption-induced electrochromism (AiEC). As shown in Fig. 1,

the mechanism of AiEC has been revealed as a reversible Fermi-

level shift induced by alternation of surface adsorbates with

polarization in electrolyte solutions. Based on this mechanism, we

have succeeded to enhance the AiEC property by introducing

microvillus-like isolated nano-columnar (INC) structures into the

InN films by means of glancing-angle deposition (GLAD) 1-2)

.

AiEC reaction speed has been known to be much higher than

conventional electrochromic (EC) materials such as WO3, because

the AiEC reaction occurs only on the material surfaces, while an

intercalation of cations into solid crystals is necessary for the

conventional EC. There are some rate-control steps for AiEC;

supply of carrier electrons, diffusion of ions in the solution, and

formation of electric double layer. In this study, we investigate the

influence of the carrier-supplying layer thickness on the AiEC of

InN films with a pillar-like INC structure.

The INC-structured InN films were deposited by using a

vacuum evaporation system with a nitrogen radical source by

simultaneous irradiation of an evaporated indium flux and the

nitrogen radicals. We used ITO-coated glass plates (Geomatec, Co.

Ltd.) as substrates with the ITO thicknesses of 9, 90, 200, and 300

nm. The substrates were installed at the angles of 85° with respect

to the indium flux. Rotation of the substrate was kept at 20 rpm.

The films were characterized by XRD, SEM. The EC properties

were measured in a 0.01M Na2SO4 aqueous solution by using a

spectrophotometer.

Table 1 shows the electronic properties of the ITO layers.

The carrier mobility was independent of the ITO thickness, while

the concentration was quite small for the ITO layer with the

thickness of 9 nm, which is due to a decrease of oxygen vacancy

after deposition of the ITO layer. The sheet resistance is strongly

dependent of the ITO thickness. Figure 2 shows the XRD profiles

of the INC-structured InN films. All samples have a wurtzite

crystal structure with a strong (101) orientation.

Figure 3 shows the time dependences of the relative

transmittances for the INC-structured InN films. Qualitatively, the

color-change speed depends on the ITO thickness, i.e., the carrier

supplying speed. The speed at cathodic polarization was much

slower than that at anodic.

References 1) Y. Inoue, J. Matsui, H. Ishikawa, H. Tsuda and O. Takai: Thin

Solid Films 518, 1001-1005 (2010).

2) Y. Inoue, A. Yamaguchi, T. Fujihara, J. Yamazaki and O.

Takai: J. Electrochem. Soc. 154, J212-J216, (2007).

Table 1 Electronic properties of the ITO layer.

ITO

Thickness

[nm]

Carrier

Concent.

[/cm3]

Carrier

Mobility

[cm2/Vs]

Resistivity [Ωcm]

Sheet

Resistance

[Ω/sq]

300 12.8×1020 4.3×101 1.1×10-4 3.7

200 9.3×1020 5.0×101 1.3×10-4 6.6

90 10.5×1020 4.5×101 1.3×10-4 14.6

9 2.7×1020 4.3×101 5.3×10-4 61.5

Fig. 1 Schematic diagram of AiEC of InN.

Fig. 2 XRD profiles of the deposited InN films.

Fig. 3 Time dependences of the relative transmittances

for the INC-structured InN films on the ITO layers with various thicknesses. The dashed lines mean the

time point where 80% of color change finishes.

Abstract Guideline (Leave two lines for presentation number)

Preparation of Sulfamate Ni-Mn Plating for the heat resistant improvement

*G.Kanamori

1,2,3), K.Yasuda

3), M.Watanabe

1,2), H.Honma

2), O.Takai

1,2)

1)Graduate School of Engineering, Kanto Gakuin University

2) Material & Surface Engineering Research Institute,

Kanto Gakuin University, 3)

OGIC Technologies Co., Ltd., Kumamoto, Japan *ogic@ogic.ne.jp

Keywords: Ni plating, Internal Stress, MEMS

Recently, the sulfamate Ni plating solution is used for

electroforming and MEMS, because it is possible to use

the processing at low temperature and the high current

density. In the case of MEMS, it is important to manage

the internal stress of plating film in particularly. Generally,

sulfur-based compounds (ex; saccharin) are added to

control the compression stress. However the sulfur

brittleness is caused by Ni plating film after heat treatment

more than 200 degrees Celsius, which obtained from

plating solution including the sulfur-based compounds. In

other words, nickel sulfide is produced in the plating film

after heat treatment, which is caused sulfur brittleness.1)

Some researchers have studied Ni alloy plating film to

solve this problem. Especially Ni-Mn plating is expected

to prevent sulfur brittleness. Because sulfur combines

with Mn to form compound, which suppress to form

nickel sulfide. But it has never investigated any research.

So we investigated that properties of sulfamate Ni plating

film are affected by Mn compound.

According to the result of the Hull cell test, Ni-Mn

plating has to be evaluated under the 6A/dm2 because of

the dendrite. Mn content ratio is relative to Mn

concentration and current density. Compare Ni plating

and Ni-Mn plating film, the appearance of Ni-Mn plating is blacker than Ni plating. Mn content ratio decreased

slightly, when temperature value is up or pH value is down.

In case of internal stress test, Mn concentration is relative to the internal stress. When Mn concentration increase,

the internal stress trends to increase the tensile side significantly. In contrast with Mn concentration, the saccharin

tends to change compression stress.

The hardness was affected by heat treatments. In case of as plate, value of hardness shows about 550 Hv under all

conditions. However the sample of hardness about Mn 0 g/dm3 was decreased after heat treatment at 250℃. On the

other hand, the sample of hardness about Mn 1.0 g/dm3 and 5.0 g/dm

3 ware kept good value.

Figure 1 show that surface morphologies after hardness measurement for Ni-Mn plating obtained from each Mn

concentration. Compared with as plate and after heat treatment, As plate had a clear indentation shape. But an

indentation didn’t keep clearly after heat treatment without Mn content.

The decreasing of the hardness by heat treatment depends on sulfur brittleness, and we consider that sulfur

brittleness was suppressed by containing Mn.

Key points for preparation of abstract is as follows;

1. Mn content ratio depends on Mn concentration and current density.

2. Plating film form the dendrite, when current density exceeded 6.0 A/dm2.

3. The internal stress trends to change the tensile stress, when plating is including Mn.

4. Addition of the saccharin is necessary to keep compressive stress.

5. When plating is including Mn, the sulfur brittleness was suppressed.

References 1) H. Ise, Electroforming technology and application, p.141-152 (1996).

Figure 1 Surface morphologies after hardness

measurement for Ni-Mn plating obtained from each

Mn concentration

a) As plate,

b) After heat treatment (250℃×1 hr.),

c) Mn content ratio (wt%),

d) Current efficiency (%)

Figure1. IR spectrum of lacquer.

Protection of lacquer surface from UV irradiation using TiO2/SiO2 hybrid

photocatalyst

*T. Adachi

1), C. Terashima

2), K. Nakata

2), K. katsumata

2), N. Suzuki

2), T, Kondo

1)2), M, Yuasa

1)2),

and A. Fujishima2)

1) Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science,

Tokyo, Japan, 2) Photocatalysis International Research Center, Tokyo University of Science, Tokyo, Japan *7216602@ed.tus.ac.jp

Keywords: Photocatalysis, Lacquer, Self-cleaning,

TiO2 is photocatalyst material, which shows super-hydrophilic and oxidative decomposition properties by UV

irradiation. Water spreads out by forming a thin layer on TiO2 and carries away dust particles from surface. In

addition, organic compounds are decomposed by strong oxidation power1)

. Lacquer is natural paint based on

urushiol gathered from a lacquer tree. Due to its superior durability (acid, base, and water-resistance) and high

adhesion, the lacquer has been applied to various substrates including tableware for a long time. However, the

lacquer deteriorates and decreases in luster by UV irradiation2)

. In this work, the coating of TiO2/SiO2 composite

film on lacquer was conducted in order to absorb UV light, aiming to prevent deterioration and give the

self-cleaning properties. Self-cleaning effects was evaluated by water contact angle, and lacquer deterioration was

evaluated by IR spectrum under UV irradiation as well as an observation of its surface morphology by laser

microscope.

TiO2/SiO2 composite film was coated by dip coating or spray coating with SiO2 slurry and TiO2/SiO2 slurry

sequentially on lacquer substrates which were

pretreated by ozone. Samples were dried 100 °C for 1

h after coating. The decrement of water contact angle

was confirmed after 1 h UV. This was due to the

photo-induced hydrophilicity of TiO2 by UV

irradiation. Fig.1 shows the change of IR spectrum

with UV irradiation time, a peak around 1700 cm-1

increased and a peak around 1050 cm-1

changed by

keeping UV irradiation. This was because C=O bond

increased, and also changed into ester bond of

primary alcohol. Laser microscope observation revealed that the lacquer surface became rougher after UV

irradiation due to the degradation. As the surface became rough, the diffused reflectance light increased, causing the

decrease of the luster of the lacquer surface. Therefore, coating of TiO2/SiO2 composite film is needed to more

absorb UV irradiation and to protect the lacquer surface from UV light by photocatalytic effects.

References:

1) Sanjay S. Latthe, et al., Coatigs 2014. 4. 497-507．

2) Ogawa T, Urushi-no-Kgaku (Science of Lacquer) (in Japanese)

Fig. 1 Experimental equipment

Effect of Raw Material on Diamond Synthesis Using Microwave Assisted

Plasma In-Liquid Method

*Y. Sakurai1)2), Y. Harada1)2)3), K. Miyasaka1)2), C. Terashima2), N. Suzuki2), H. Uetsuka2)3),

K. Nakata1)2), K. Katsumata2), T. Kondo1)2), M. Yuasa1)2), and A. Fujishima2) 1)Tokyo University of Science, Noda, Chiba, Japan, 2)Photocatalysis International Research Center, Noda, Chiba,

Japan, 3)Asahi Diamond Industrial Co., Ltd. *7216636@ed.tus.ac.jp

Keywords : Diamond, Plasma in-liquid, Rapid synthesis,

Diamond has high chemical and physical stability. This material is used for a wide range of applications, such as

a cutting tool and an electrode (boron-doped diamond) and so on1). Microwave plasma chemical vapor deposition

(MPCVD) method is generally used for synthesis of diamond. However, this method provides a very small growth

rate. Microwave assisted plasma in-liquid method is a new method for efficient synthesis in solution using radio

frequency or microwave. By using this method, diamond is synthesized rapidly in previous work2). However, the

detailed of growth was not studied, such as raw material and synthesis condition. Thus, this research focuses on the

investigation of the effect of solvent on diamond synthesis by using this method. Experimental method and results

are given below.

Fig. 1 shows the schematic image of microwave assisted plasma in-liquid

machine. A mixture of methanol (M), ethanol (E) and tetrahydrofuran (THF) or

methyl acetate (MA) or benzene (B) was used as an organic solvent. 2.45 GHz

microwave (440 W) was irradiated from the generator, and conducted into the

reactor via the waveguide and the electrode. The mixture was adjusted so that the

ratio of C : H : O is nearly 17.2 : 66.7 : 16.1. Si wafer is used as a substrate. The

pressure in the reactor was set to 60 kPa. The distance between Si substrate and the

electrode was set to 1.0 mm. Under these conditions, it took 3 minutes for

deposition of diamond on Si substrate.

Table I shows the experimental results on diamond synthesis by changing of

solvent. Firstly, when ① M + B was used as solvent, diamond was not

synthesized. On this time characteristic peak of Si was obtained from Raman spectrum. Secondly, when ② M + E

+ MA was used as solvent, diamond was synthesized. However, the synthesized diamond did not form uniform film.

At last, when ③ M + E and ④ M + E + THF was used as solvent, diamond was synthesized as uniform film.

Comparing solution ③ with solution ④ from Raman spectrum, sp2 component was decreased at solution ④

compared with solution ③. Therefore, it can be said that the quality of diamond film can be improved by adding

THF to the mixture of M + E. The growth rates of diamond film from solution ③ and ④ were estimated as 95 μ

m/h and 135 μm/h, respectively. Thus, in

this work, diamond is synthesized rapidly by

adding THF.

When benzene was added to the mixture

of M + E, diamond was not synthesized. On

the other hand, when THF was added,

diamond was synthesized at the same

condition. From these results, we reveal that

solvent plays an important role for

improving the quality and synthesis rate of

diamond. At infrared region of optical

emission spectra, solution ④ had the most

stable intensity in 4 solution. It is said that

the intensity at infrared region is related to the temperature on the substrate. Therefore, it can be considered that the

quality was improved because of stabilization of temperature on the substrate. It is further needed to investigate the

mechanism of the quality improvement with changing solvent system.

References :

1) H. Toyota, S. Nomura et al., Diamond and Relat. Mater., 17 (2008) 1902,

Table I Diamond synthesis by changing solvent

2) Y. Harada, R. Hishinuma et al., Diamond and Relat. Mater., 63 (2016) 12-16.

Reduction of Carbon Dioxide using Ag-modified Diamond Photoelectrode

* Y. Hirano

1), N. Roy

2), H. Kuriyama

3), Y. Nakabayashi

2), C. Terashima

2), N. Suzuki

2), K.

Nakata1)2)

, K. Katsumata2)

, T. Kondo1)2)

, M. Yuasa1)2)

and A. Fujishima2)

1)

Graduate School of Science and Technology, Tokyo University of Science, Noda, Chiba, Japan, 2)

Photocatalysis

International Research Center, Tokyo University of Science, 3)

ORC MANUFACTURING CO., LTD. *7216661@ed.tus.ac.jp

Keywords : CO2 Reduction, Photoelectrochemistry, Boron-doped Diamond, Semiconductor

Recently, it is important to reduce atmospheric CO2 concentration because of global warming. CO2 is a very

stable molecule which has high energy barrier of −1.9 V vs. SHE for one electron reduction1)

. To reduce CO2, there

are various attempts under aqueous conditions but selective reduction with high efficiency is difficult.

Diamond is one of the materials with very high conduction

band position as shown in Fig.1. Light with high energy excites

electrons to the conduction band and these excited electrons have

high energy for selective photoreduction. Therefore, diamond is a

suitable material for photocatalytic or photoelectrochemical CO2

reduction. In this study, semiconductive lightly boron-doped

diamond (BDD) is found to have an effect on CO2 reduction with Ag,

which is known as electrocatalyst for CO2 reduction2)

, as a cocatalyst

using an excimer lamp of 222 nm.

BDD was synthesized by microwave plasma chemical vapor

deposition method with carbon source and boron source in the ratio

of 9 to1. Ag modified BDD (Ag-BDD) was fabricated by

electrodeposition method in 0.1 M AgNO3 aq. at −0.5 V for 1 min.

FESEM and XPS was used to investigate the deposition of Ag.

A two-compartment cell was used with 25 mM Na2SO4 aq. as

supporting electrolyte for both the working electrode and the counter electrode compartments, respectively. Both

compartments were firstly purged with N2 to remove the impurity gaseous species dissolved in the electrolyte and

then purged with CO2 for 30 min. Cyclic voltammetry was used to fix the bias potential. At −1.6 V vs. Ag/AgCl,

current density in CO2 saturated condition is found to increase compared to N2 saturated condition. It was

considered that CO2 reduced at −1.6 V vs. Ag/AgCl. Then, light of 222 nm was irradiated and bias potential of −1.6

V vs. Ag/AgCl was applied to BDD or Ag-BDD for 3 hours. In these conditions, CO and H2 were observed as the

primary gaseous product. Amount of them was analyzed

using gas chromatography. When BDD was used as a

working electrode, H2 was produced mainly and amount of

CO was small. However, Ag-BDD produced CO mainly and

its amount was higher than that of produced from BDD.

To investigate whether this CO was produced from CO2

reduction or other sources, isotopically labeled 13

CO2 was

used and analyzed using gas chromatography mass

spectroscopy. Fig.2 shows the results of this isotopic

experiment. It reveals that 86–96% of CO produced by

Ag-BDD was 13

CO, which was produced from

photoelectorochemical reduction of CO2 but not from other

sources. It was confirmed that Ag-BDD was effective for

photoelectrochemical reduction of CO2.

References :

1) Linghong Zhang, Di Zhu, Gilbert M. Nathanson and Robert J. Hamers, Angew. Chem. Int. Ed., 53, 9746–9750

(2014).

2) Kousuke Iizuka, Tomoaki Wato, Yugo Miseki, Kenji Saito and Akihiko Kudo, J. Am. Chem. Soc., 133,

20863–20868 (2011).

Fig.2. Result of Isotopic Experiment

Fig.1. Band Diagram of Diamond

Rapid synthesis and electrochemical characterization of diamond electrode using microwave assisted plasma in-liquid method *K. Miyasaka1)2), Y. Sakurai1)2), Y. Harada1)2)3), C. Terashima2), H. Uetsuka2)3), N. Suzuki2), K. Nakata1)2), K. Katsumata2), T. Kondo1)2), M. Yuasa1)2), and A. Fujishima2) 1) Tokyo University of Science, Noda, Chiba, Japan. 2)Photocatalysis International Research Center, Tokyo University of Science, Noda, Chiba, Japan. 3)Asahi Diamond Industrial. Co., Ltd., Ichihara, Chiba, Japan. *7213101@ed.tus.ac.jp Keywords : Boron doped diamond, Microwave assisted plasma in-liquid method, Electrochemistry Boron doped diamond (BDD) is useful for sensing and electrolysis applications because of its wide potential window1). Chemical vapor deposition method is used for synthesis BDD. However, this method has low growth rate. In the microwave assisted plasma in-liquid method, it is possible to synthesize diamond rapidly. Therefore, this research focuses on high speed synthesis of BDD using microwave assisted plasma in-liquid method. Electrochemical properties of BDD films were then investigated. Fig. 1 shows the schematic image of microwave assisted plasma in-liquid machine. A solution was prepared by adding boron oxide (1%, B/C) to a mixture of methanol, ethanol, methyl acetate, tetrahydrofuran or acetone. 2.45 GHz microwave (440 W) was irradiated from the generator, and conducted into the reactor via a waveguide. The mixture was adjusted so that the ratio of C: H: O is 17.2: 66.7: 16.1. Monocrystalline silicon was used as a substrate. The distance between the tip of the electrode and the substrate was set to 1.0 mm. The time for synthesis diamond was 5 minutes under 60 kPa. Fig. 2 shows Raman spectra of BDD films synthesized in different solvents. From the Raman spectra, it was revealed that boron was doped in the diamond structure, because a peak attribute to the optical phonon near 1280 cm-1 and a peak derived from the B-B bond of boron near 500 cm-1 were also confirmed. From this, BDD was obtained in all conditions using microwave assisted plasma in-liquid method. The boron concentration was calculated from the peak position around 500 cm-1. When Methyl acetate was added to the mixture, the boron doping amount was estimated to be as high as 9×1020 cm-3. Next, the growth rate was calculated from the film thickness measurement. When Acetone was added to the mixture, we succeeded in high speed synthesis with growth rate of 196 µm/h. But boron doping is thought to be smaller as revealed by the peak intensity near 500 cm-1. Therefore, boron could be doped at a high concentration when the growth rate was slow. Finally, the electrochemical properties of the diamond film were investigated using cyclic voltammetry (CV). Fig. 3 shows the results of CV in 0.1 M H2SO4. As results of analysis, BDD using this method showed a wide potential window as a characteristic of diamond electrode. From these results, we reveal that the microwave assisted plasma in-liquid method is useful method for making diamond electrode. It was found that the film growth rate and the doping amount depend on the solvent. Therefore, it is considered that BDD with the necessary concentration can be produced by selecting an appropriate solvent. References 1) K. Nakata, et al., Angew Chem. Int. Ed., 126 (2014) 890-893. 2) S. Nomura, J. Plasma Fusion Res., 89, 4 (2013) 199-206. 3) Y. Harada, et al., Diamond Relat. Mater., 63 (2016) 12-16.

Fig. 1 Microwave assisted plasma in-liquid equipment

Fig. 2 Raman spectra of BDD films synthesized in

different solvents

Fig. 3 Cyclic voltammetry of BDD films synthesized in

different solvents

Development of atmospheric pressure plasma jet processing for TiO2 film

synthesis using of peroxo titanic acid solution

*R. Tabei

1)2), C. Terashima

2), N. Suzuki

2), K. Nakata

1)2), K. Katsumata

2), K. Arimitsu

1)2), T.

Kondo1)2)

, Y. Makoto1)2)

, and A. Fujishima2)

1)

Tokyo University of Science, Noda, Chiba, Japan, 2)

Photocatalysis International Research Center *7216646@ed.tus.ac.jp

Keywords: atmospheric pressure plasma jet, photocatalysis, TiO2, new processing

TiO2 shows photocatalytic properties such as strong oxidizing

power and super-hydrophilicity under ultraviolet light, thus it has

self-cleaning properties. There are many methods of synthesizing

TiO2 films, for example, thermal spraying, dip coating and spray

coating. However, heat resistance is needed for the substrate in

thermal spraying. The film synthesized by dip coating or spray

coating is easy to peel off. Therefore, it is requested that the method

which is unnecessary high-temperature processing and enables the

film to have high durability. Generation of atmospheric pressure

plasma jet (APPJ) using dielectric barrier discharges was reported

by Engmann in 20051)

. APPJ is non-thermal equilibrium plasma

under normal pressure, thus plasma temperature is low, whereas

electron temperature is thousands of degrees. In this study, peroxo

titanic acid (PTA) solution was used as precursor of TiO2 film. PTA

solution is neutral, and stable aqueous solution2)

, thus it is easier to

handle than titanium alkoxide. In this study, PTA solution was

synthesized and delivered to APPJ to synthesize TiO2 film under

normal pressure and temperature.

PTA solution was prepared by TiCl4 solution, NH4OH solution

and H2O2 solution that was described in detail elsewhere2)

. Powder

which was obtained by drying PTA solution was analyzed by FT-IR

and XRD. FT-IR spectrum indicated O-O bond which was

attributed to the peroxo group. XRD patterns indicated PTA

crystallized above 250 C. These results suggested that PTA

solution was certainly prepared.

APPJ generator consisted of Pyrex tube (Inner diameter: 4 mm,

Outer diameter: 6 mm) and two tubular copper electrodes (Width:

10 mm) on it. He and Ar gases were flowed (He: 3 L/min, Ar: 300

mL/min) through the tube, and plasma was produced by applying

voltage from bipolar pulsed power supply (Voltage: 4 kV,

Frequency: 18.5 Hz, Pulse width: 1s). PTA solution was used as

the precursor and delivered to the plasma by bubbling He gas (500

mL/min). Si substrate was placed to the end of the plasma where

the film was synthesized (Fig. 1).

The film synthesized by APPJ in 5 min was white and circle (3

mm diameter). Leaser microscope and FE-SEM images were

shown in Fig. 2. Film quality was better when He and Ar mixed gas

was used than only He gas was used. The crystallinity of the film

was analyzed by XRD and plane of TiO2(B) was observed(Fig. 3).

Photocatalytic activity of the synthesized film was analyzed by

measurement of linear sweep voltammetry. The current density increased a little when the film was irradiated

simulated solar light. However, photocatalytic activity was not enough. Thus this process needs improvement.

References 1) M. Teschke et al., IEEE T. Plasma Sci., 33–2, 310–311 (2005).

2) H. Ichinose et al., J. Ceram. Soc. Jpn., 104-8, 715-718 (1996).

power supply

He, Ar gas

He gas

Si

PTA solution

cupper electrode

glass tube

Fig. 1. Experimental set up

Fig. 2. Leaser microscope images (a) He, (b) He +

Ar, FE-SEM images (c) He, (d) He +Ar

Fig. 3. XRD patterns

Study on High Photocatalytic Activity of Solution Plasma Treated TiO2 by Using Tube Electrode *S.Suzuki1)2),K.Honda1)2),C.Terashima2),N.Suzuki2),K.Nakata1)2),K.Katumata2),T.Kondo1)2), M.Yuasa1),and A.Fujishima1)2) 1)Tokyo University of Science, 2)Tokyo University of Science Photocatalysis International Research Center *7213057@ed.tus.ac.jp Keywords : TiO2, Solution Plasma, Oxygen Vacancies, Surface TiO2 is well known photocatalyst with high stability, biocompatible in nature, and safe material. However, its photocatalytic activity is generally limited in the ultra-violet region. Therefore, the development of highly active photocatalyst under visible light has been frequently conducted. In our laboratory, solution plasma method was used in the previous work to improve its photocatalytic activity under fluorescent lamp. In this study, we make experimental system using tube electrode and attempt to stabilize plasma, thereby expecting further high efficiency. In addition, structural analysis was conducted to clarify the factor for improving photocatalytic activity. The solution plasma equipment is shown in Fig. 1. The TiO2 sample used in this study was ST-01 obtained from Ishihara Sangyo (100% anatase, crystallite size : 7 nm, nominal specific surface area : 300 m2/g). TiO2 nanoparticles were dispersed in KCl aq. (300 µS/cm, 350 mL). Solution plasma treatment was conducted in N2 gas atmosphere. In the previous method, N2 gas was introduced from bottom of plasma. In contrast, N2 gas is introduced by using tube electrode in new method. Plasma was generated by pulse discharge (20 kHz, 1µs, 2kV). The color of the sample powder was changed from white to light gray by solution plasma treatment. We evaluated photocatalytic activity by decomposition of acetaldehyde (8000lx under fluorescent lamp, amount of sample : 0.1 g). Gas chromatography (GC) analysis was performed and the result is shown in Fig. 2. It is found that required process time become much shorter in the new method. Using tube electrode of N2 gas plasma becomes more stable. Therefore, treatment can be achieved more efficiently. We also researched the factor for improving photocatalytic activity. First, we examined wavelength-dependenth of photocatalytic activity and found that photocatalytic activity enhanced in ultra-violet region after plasma treatment. This result presents the prevention of recombination. Next, we conducted structural analysis with electron spin resonance (ESR) and x-ray diffraction (XRD). The result of XRD identified structural change in the bulk did not occur and anatase phase was retained. In ESR measurements, we clarified generating oxygen vacancies. Thus, it was suggested oxygen vacancies exists only on the surface. It is assumed that disorders on the surface become trapping sites for photogenerated carriers and prevent them from rapid recombination, promoting electron transfer and photocatalytic reactions1). In addition, the O2 molecules absorbed at oxygen species on surface produces more reactive oxygen vacancies2). Based on the above, it is considered that photocatalytic activity is improved by solution plasma treatment. References: 1) X. Chen, L. Liu, P. Y, Yu, S. S. Mao, Science, 331, 746 (2011), 2) J. T. Y. Jr, Surf. Sci. Rep, 603, 1608 (2009).

Fig. 1 Solution plasma equipment

Fig. 2 Photocatalytic activity evaluation

Fig.1 Wear curves of ABS resin surfaces by MSE test

Characteristics evaluation of the surface layer of UV reformed ABS resin

*Y. Nakabayashi1),2),Y. Umeda2),3), K. Tashiro2),3), H. Honma2) and H. Kouzai2),4) 1) Graduate School of Engineering, Kanto Gakuin University, Yokohama 236-8501, Japan, 2) Materials and Surface

Engineering Research Institute, Kanto Gakuin University, 3) Kanto Gakuin University Reserch advancement and

management organization, 4) College of Science and Engineering, Kanto Gakuin University, *nakapa@outlook.jp

Keywords : ABS resin, UV treatment, MSE test

1. Introduction ABS resin is widely applied as a substrate for products such as parts of automobiles and appliances. Generally,

plated ABS resin obtained the high adhesion strength by appropriately oxidizing on the resin surface. Conventional

method, extremely harmful Chromic acid etching has been used as a reforming for electroplating on ABS plastics.

Therefore, enviroment friendly modification process on the resin surface has been reported1)-2).

In this study, we evaluated the surface properties of ABS resin using UV reforming for plating pretreatment.

2. Experimental

The test sample was 20 mm or 50 mm squares cutting out the ABS resin (Mitsubishi Plastics, Inc., Hishiplate,

t = 3 mm) that was used. Atmospheric UV treatment using a low-pressure mercury lamp (Koto Electric Co., Ltd.

KOL1-300S) that was treated at 0-600 sec. Surface wettability was evaluated by water contact angle meter (Kyowa

Interface Science Co., Ltd. DMe-201). The measurement of the chemical luminescence (CL) intensity used

chemiluminescence analyzer (Tohoku Electronics Industry Co., Ltd., CLA-SF4) that was carried out for 5 min.

Surface functional groups were analyzed by Fourier transform infrared spectroscopy (JASCO, FT/IR4100). Depth of

UV reformed layer was observed by MSE test (Palmeso Co., Ltd. MSE-A).

Furthermore, adhesion strength after metal plating was evaluated with peel testing apparatus (Toyo Seiki

Seisaku-sho, Ltd. Strograph E2-L05).

3. Results and discussion

The water contact angle on the

ABS resin after modification showed

increased hydrophilicity upon over 30

sec of UV treatment. Oxidation of ABS

resin surface was confirmed by CL

measurement, and the peak of C=O

group increased with FT-IR spectra.

Fig.1 shows the wear curves of ABS

resin surfaces by MSE test. The erosion

rate and reforming depth of the ABS

resin surface were increased by UV

treatment. Furthermore, adhesion

strength of about 1.0 kN/m was

obtained for treatment of over 30 sec.

However, UV treatment time of 5 sec

was about 0.2-0.3 kN/m that not enough to

achieve good adhesion.

4. Conclusion

It was confirmed that the reforming depth increased by UV treatment. Although the reforming depth increases in

UV 5 sec, the wettability is not improved and the adhesion strength is low. Wettability and adhesion strength

improved with UV 30 sec or more.

Acknowledgements:

This study was aided by the MEXT-supported program for the Strategic Research Foundation at Private Universities.

References: 1) M. Sugimoto, et al., J. Surf. Finish. Soc. Jpn., Vol. 57, No.2 (2006)162-166.

2) K. Morri, S. Abe, J. Surf. Finish. Soc. Jpn., Vol. 59, No.5 (2008)299-304.

CN-terminated Graphene by Peeling Graphite via the Solution Plasma Process in Ionic Liquid and Water Mixture *T. Ueno1), S. Chae1), J. Hieda1), M. A. Bratescu1), N.Saito 1), 2) 1)Nagoya University , 2) JST-CREST *hiro@rd.numse.nagoya-u.ac.jp Keywords: Carbon Materials, CN-terminated Graphene, Peeling, Ion Liquid, Solution Plasma Process

Graphene is an attractive material due to its high levels of electrical, thermal, mechanical, electronic, and optical properties. Various applications of graphene materials have been reported, such as in solar cell, energy storage, fuel cells, capacitors, electronic devices, and sensor technology. An edge-functionalized graphene also has been researched to improve the dispersibility, as well as protection against oxidation, and giving functions. The functionalized graphenes dispersed in a liquid are useful for applications. Usually, graphene is fabricated by CVD method, reduction of graphene oxide, mechanical peeling of HOPG and graphite flakes, and electrochemical exfoliation of graphite rods. However, the limited scalability and high production costs are obstacles for broad applications. The immersion in a liquid also led to the reducing of the Van der Waals attraction due to the change of the surface tension. Ionic liquids have been successfully applied for the peeling and dispersing of the graphene sheet. Thus, various methods using the ionic liquids and ionic liquids mixtures have been employed for the exfoliation of graphite and dispersion of graphene combining mechanical, chemical, microwave, hydrothermal, electrochemical, and sonication techniques. Furthermore, we found a novel synthesis method for graphene sheets by peeling graphite electrodes in solution plasma1). In this study, we used the ion liquid 1-Ethyl-3-methylimidazolium dicyanamide (EMIM DCA) to enhance the peeling of graphite from graphene and to functionalize it by the Solution Plasma Process (SPP). The EMIM DCA is composed of cyano group. The activated cyan radical can be produced in plasma and efficiently react with carbon materials. Cyano-group is a useful functional group since it is stable and easily changes to other effective functional groups by organic chemistry. In this process, we synthesize CN-terminated graphene from graphite through SPP.

A mixture of 10% 1-Ethyl-3-methylimidazolium dicyanamide, EMIM DCA, and 90% distilled water was prepared. Then, the graphite flakes (<20 μm, synthetic; Sigma-Aldrich, Japan) were suspended in the mixture. The discharge was generated between a pair of tungsten electrodes. A bipolar–pulsed high voltage was applied to the tungsten electrodes by using a power supply with a repetition frequency of 100 kHz, and a pulse width of 1.0 μs. After discharging for 30 min, the exfoliated graphite powder was separated by vacuum filtration through a polytetrafluoroethylene (PTFE) membrane filter with a pore size of 0.1μm. The obtained material was purified by dialysis in distilled water to remove any remaining EMIM DCA, and then dried in an oven at 85oC for 12 h.

The samples obtained by solution plasma at 100 kHz with or without EMIM DCA are denominated as W/E_SP100, and W_SP100, respectively. For comparative research, the graphite was exfoliated by Ultrasonication (US) with an oscillating frequency of 38 kHz and a power of 0.1 kW for 30 min with or without EMIM DCA. The obtained samples with or without EMIM DCA are denominated as W/E_US and W_US, respectively. Furthermore, the material obtained by applying only the bipolar-pulsed high voltage which is lower than the breakdown voltage of solution plasma in EMIM DCA mixture was denominated as W/E_HV.

From the XRD measurement as shown in Figure1, it was observed that the intensity of 002 pattern corresponding to the layer structure of the graphite decreased after the SPP treatment, which means that peeling progressed. Furthermore, the few-layers structure was confirmed by the 2D band of the Raman spectrum as well as the morphological images from Transmission Electron Microscopy. X-ray photoelectron spectroscopy analysis confirmed that the synthesized few-layer graphene includes 7.7 at% nitrogen and IR spectrum shows the CN functional group. From these results, the exfoliation and the synthesis of CN-terminated graphene flakes were simultaneously conducted. References 1) H. Lee, M. A. Bratescu, T. Ueno, N. Saito, RSC Advances, 4 (93), 51758-51765 (2014).

Figure 2. (a) The ratio between the peak intensities at I26.5 (carbon (002)) and I28.3 (silicon (111)) for different samples.

Effective Characteristics of Calcareous Deposit Films on Steel Substrate

Prepared by Cathodic Current Process in Marine Environment

J. M. Park

1), I. H. Choi

1), S. H. Hwang

1), J. Kang

1) and

*M. H. Lee

1)

1) Division of Marine Engineering, Korea Maritime & Ocean University, Busan, Korea

*leemh@kmou.ac.kr

Keywords: Calcareous Deposits, Cathodic Current Process, Current Density, Calcium Carbonate, Magnesium

Hydroxide

Seawater is a conductive electrolyte, containing dissolved salts, gases, suspended organic and inorganic matter and

live organisms, and steel materials are well corroded by the chlorine ion contained in seawater. However, steel is

still the most common constructional material used in marine conditions, because of its low cost and excellent

mechanical properties. At present, as an anti-corrosion method, cathodic protection is widely recognized as the most

cost effective and technically appropriate corrosion prevention methodology for the submerged zones of offshore

structures, ships, and deep sea facilities. As a result of applying cathodic protection, the cathodic currents induce

dissolved oxygen reduction that generate hydroxyl ions at the very near polarized surface, increase the interfacial pH

and result in enhanced carbonate ions concentration, and precipitation of an inorganic layer whose principal

component is the calcium carbonate even when containing some magnesium. Depending on the potential,

magnesium hydroxide can also precipitate. This mixed deposit is generally called “calcareous deposits”. That is,

these calcareous deposit films such as CaCO3 and Mg(OH)2 are formed by the surface of the steel product. This

layer functions as a barrier against the corrosive environment, leading to a decrease in current demand. Hence, the

importance of calcareous deposits for the effective, efficient operation of marine cathodic protection systems is

generally recognized by engineers and scientists concerned with cathodic protection in submerged marine

environments. On the other hand, the general calcareous deposit film is a compound like ceramics. Therefore, there

may be some problems such as weaker adhesive power and the longer time of film formation uniting with the base

metal and van der walls force. Also calcareous deposit formation on a marine structure depends on a large number of

parameters including; potential, current, pH, temperature, pressure, sea water chemistry, flow, time. The quality of

the deposit is significantly influenced by these factors.

In this study, we tried to determine the optimal condition through applying the principle of cathodic current process

to form calcareous deposit film that is uniform and compact on steel substrate. The quantity of precipitates was

analyzed, and both the morphology, component and crystal structure were analyzed as well through SEM, EDS and

XRD. And based on previous analyses, the mechanism by which calcareous deposit film forms in various conditions

was determined. In addition, the taping test was performed to evaluate the adhesive properties, and the sacrificial

anode consumption rate test was performed to confirm the effect of the calcareous deposits.

References:

1) R. Lee and J. Ambrose, Corrosion Science., 44, 887-891 (1988),

2) J.M. Park and M.H. Lee, Kor.Inst.Surf. Eng., 49, 166-171(2016).

Acknowledgments

This work was supported by the New & Renewable Energy Core Technology Program of the Korea Institute of

Energy Technology Evaluation and Planning(KETEP) granted financial resource from the Ministry of Trade,

Industry & Energy, Republic of Korea (No.20143010021820)

Fig. 1. Observation appearance of steel substrate as the time passed. (1, 3 and 5 A/m2)

Formation of Ceramic Coating on Hot Dipped Aluminized Steel by Plasma

Electrolytic Oxidation Process

I. H. Choi

1), J. M. Park

1), S. H. Hwang

1), J. H. Park

1) and

*M. H. Lee

1)

1) Division of Marine Engineering, Korea Maritime & Ocean University, Busan, Korea

*leemh@kmou.ac.kr

Keywords: Plasma Electrolytic Oxidation (PEO), Hot Dipped Aluminized Steel (HDA), Ceramic coating, Steel

substrate

In the last several decades, the consumption of material by industry has increased and caused widespread

concerns about the need to use them in a more efficient way. For these reasons, development of surface treatment

technology that has excellent durability and is environmentally friendly has been actively studied. Plasma

electrolytic oxidation (PEO) has attracted increasing attention for the surface treatment of lightweight metals (such

as Al, Mg, Ti) to enhance their hardness, high wear and corrosion resistance. PEO is generally considered to be

process cost-effective, environmentally friendly and superior in terms of coating performance. Due to those unique

properties, PEO coating has been much used in mechanical, automobile, aerospace, medicine and electrical

industries in recent years. As is well known, steel is used widely in industry but its performances in terms of wear

and tear and corrosion are poor. Thus, a great deal of coating technology and plating has been applied to protect

steel placed in various extreme environments. For example, aluminum layers using conventional techniques such as

hot-dip aluminum (HDA) can play the role of a sacrificial anode for steel.

In this study, PEO process was used to form oxide coatings on Hot dipped aluminized steel. PEO coatings were

prepared using different processing conditions and different characterization parameters were applied. The positive

output of the power supply was connected to the sample immersed in the electrolyte serving as the working

electrode (anode) and the negative output was connected to the stainless steel electrolyte container acting as the

counter electrode (cathode). An aqueous electrolyte containing 5% KOH and other additives (pH 11) was used as

the electrolysis environment. Temperature of the electrolyte was maintained below 30℃ using a heat exchanger.

The coatings deposition was carried out at current densities that varied within 5–15 A/dm2 and at different power

frequencies that varied within 100-1500Hz. Different duty cycles were applied. The surface morphology and

cross-section structure of coating were investigated by Scanning Electron Microscope (SEM). The phase

composition and the elemental distribution were measured by energy-dispersive X-ray spectroscopy (EDS) and

X-ray diffraction (XRD). Potentiodynamic polarization test was performed to investigate the electrochemical

properties. Also, the micro-hardness values determined from Vickers indentations on the cross sections of the

coatings to confirm the mechanical properties.

Consequently, in accordance with decreasing duty cycle, it was shown that there is a tendency for the spark

voltage and maximum voltage to increase. At the low current, the cross-sectional micro-hardness increased with an

increase in the duty cycle while at the high current, the maximum micro-hardness value is obtained at the lower duty

cycle. Furthermore, when applying constant frequency and operation time, the spark voltage increases with a

decrease in duty cycle at both low and high current. Therefore, it is expected that the results presented here could be

utilized to better control the PEO process in order to produce coatings with the desired properties.

References:

1) V Dehnavi, BL Luan, DW Shoesmith, XY Liu, Surface and Coatings Technology, 226, 100-107 (2013)

2) R O Hussein, X Nie, D O Northwood, A Yerokhin, A Matthews, J. Phys. D: Appl. Phys. 43, 105203 (2010)

Fig. 2. Spark voltage characteristics on the Duty Cycle of PEO treatment

Fig. 1. Cross-sectional microhardness characteristics on the Duty Cycle of PEO treatment

Fig.1. AFM images of a) TPPS and

b) TPPS/chitosan films fabricated at pH 2

Chitosan Polycation Supramolecular as Template-assisted For Control

Aggregation of Meso-tetrakis (4-sulfonatophenyl) Porphyrin

*M. Tipplook1), J. Hieda1), T. Ueno1), 2), M. A. Bratescu1) and N. Saito1), 2) 1) Department of Material Science and Engineering, Graduate School of Engineering, Nagoya University, Furo-cho,

Chikusa-ku, Nagoya, 464-8603, Japan 2) CREST, JST, Furo-cho, Chikusa-ku, Nagoya, 464-8603, Japan *bird@rd.numse.nagoya-u.ac.jp

Keywords: Porphyrin, porphyrin/chitosan complexes, porphyrin aggregation, chitosan template, control aggregation

Supramolecular structures based on organized assemblies of macrocyclic chromophores have attracted

widespread interest as molecular devices with potential applications such as electronic and medical. These structures

may involve covalent links between the components or be stabilized by

weak interactions (electrostatic, polar, nonpolar and so on). Meso-tetrakis

(4-sulfonatophenyl) porphyrin (TPPS) have been used as suitable

chromophores for preparation of supramolecular systems. Chitosan, a

natural polysaccharide, has been found to be several useful applications

such as medical, food, agriculture. Chitosan is an interesting candidate for

the electrostatic self-assembly of macrocycles due to polycation ability. In

the present work, we designed complexes film between TPPS/chitosan by

using electrostatic interaction for control aggregation of TPPS. The thin

film of TPPS/chitosan complexes were prepared by addition of TPPS

powder to chitosan solution at pH2 and subsequent spin coating of green

miscible solution on substrate for thin film fabrication.

Absorption spectra of TPPS/chitosan solution showed three peaks at

422, 486, 700 nm assigned to J-aggregated macrocycles. Evident blue shifts

around 4-8 nm of complexes solution comparison with free TPPS solution

could be owing to strong interaction between macrocycles and chitosan. As

shown in Fig.1, AFM images presented that TPPS containing chitosan

consisted of variable sized roundish nanostructure; diameter around 10-50

nm. Chitosan polycation supramolecular was promoted potential to

controlled aggregation of TPPS.

References:

1) B. Liao, R. Liu and Y. Huang, polymer journal, 39, 1071-1077 (2007).

2) A. Synytsya, A. Synytsya, P. Blafková, J. Ederová, J. Spěvaček, P. Slepička, V. Král and Karel Volka,

Biomacromolecule, 10, 1067-1076 (2009).

Simple Method to Fabricate Ultra-high Sensitive Magnetic Sensor by Using Water-treatment Process *H. Tanaka1), S. Tanaka1), N. Kataoka1), R. Matsumoto2),3), and S. Kishida4) 1)National Institute of Technology, Yonago College, Yonago, Tottori, Japan, 2)National Institute for Materials Science, 3)Tsukuba University, 4) Tottori University *hitanaka@yonago-k.ac.jp Keywords: Bi2Sr2CaCu2Oy, high-temperature superconductor, water-treatment process, Josephson junction

Intrinsic Josephson junctions (IJJs) are one of the most attractive and applicable properties of high-temperature superconductors (HTSCs). Josephson junctions (JJs), which are composed of superconductor/insulator/superconductor sandwich structures, can be fabricated without the preparation of nanosized insulating layers. Here, the insulator thickness should be on the nanometer scale. Thin insulators are generally difficult to uniformly fabricate in HTSCs. Therefore, IJJs have great potential for application in HTSC devices, including ultra-high sensitive magnetic sensor so-called HTSC-SQUID, Q-bits for quantum computers, and THz oscillators and receivers.

Using a water-treatment process, we have successfully fabricated IJJ tunneling devices in Bi2Sr2CaCu2Oy (Bi-2212) high-temperature superconductor. To fabricate IJJ tunneling devices, it is necessary to flow an electrical current along c-axis direction which IJJ’s structures natively arrange1)-3). For an attainment of current pathway along c-axis direction, a surface of Bi-2212 single crystal was partially contacted with purified-water at room temperature for 0.5 - 10 h. By this treatment, an electrical property of the Bi-2212 single crystal between electrodes was deteriorated. Therefore, a current pathway was changed from ab-plane direction to c-axis direction. Actually, the annealed Bi-2212 single crystal showed clear voltage jumps, so call “Josephson junction property”, in current-voltage characteristics.

To investigate how the intrinsic Josephson junction tunneling device is formed by the new process, we carried out X-ray photoemission spectroscopy (XPS). The XPS result indicates that Cu ions in a new region were reduced. The new region does not show a superconducting property in R-T characteristics because of the high resistivity. Therefore, it is expected that the new region changes a current pathway. The change of a current pathway probably leads to an attainment of IJJ tunneling devices. Our novel process is important because it has great advantages in its technical simplicity and its economic efficiency.

References : 1) J. Fujita, T. Yoshitake, T. Satoh, S. Miura, H. Tsuge, and H. Igarashi: Appl. Phys. Lett. 59, 2445-2447 (1991). 2) H. B. Wang, Y. Aruga, T. Tachiki, Y. Mizugaki, J. Chen, K. Nakajima, T. Yamashita, and P. H. Wu: Appl. Phys. Lett. 74, 3693-3695 (1999). 3) S. -J. Kim, Yu. I. Latyshev, and T. Yamashita, Appl. Phys. Lett. 74, 1156 (1999).

Fig. 1. I-V characteristics of Bi-2212 high-temperature superconducting single crystal treaded by a water-soaking process at room temperature for 5h.