Researches, Publications and Achievements

2007-2011

Department ofMacromolecular Science and Engineering

Kyoto Institute of Technology

1Contents
Functional Polymer Design Laboratory

3

Polymer Photonics Laboratory

10

Polymer Physics Laboratory

14

Polymer Molecular Engineering Laboratory

23

Fibrous Material Science Laboratory

33

Polymer Mechanics Laboratory

38

Textile Engineering Design Laboratory

44

Condensed Matter Physics Laboratory

502

Functional Polymer Design Laboratory
Naoto TSUTSUMI, Dr., Prof.
Wataru SAKAI, Dr., Associate Prof.
Kenji KINASHI, Dr., Assistant Prof.
I. Researches
Tsutsumi’s laboratory focuses on the interaction between light, photon and matter. We have 5 main research
themes as follows.

Individual Research Contents
1) For information technology, photorefractive (PR) polymers have been developed. PR polymers are thepromising materials for the next generation three
dimensional (3D) holographic display and volume
holographic memory system. Photorefractive effects are
based on the refractive indices modulation shifted to theinterfered light pattern in the PR polymers possessing
photoconductivity and 2nd order optical nonlinearity(NLO). Periodic space charge field created by thephoto-generated charge carriers induces the Pockels effectthrough NLO chromophore in the PR polymers, andPockels effect, nonlinear refractive index modulation, is
induced by these periodic space charge fields. Dynamic

Reconstructed hologram image ofcoins using photorefractive polymer.

holographic imaging can be produced using PR polymers.
Our research objectives are the real-time 3 D holographic display with video-rate using PR polymers.

32) Related to the information technology, ferroelectric polymer
devices are developing. Fast ferrolectric switching up to 100
kHzisachievedforpoly(vinylidene

trifluoroethylene)(P(VDF-TrFE) copolymer) thin film.
3) For fabrication of structures by light or photon, laser lithography
based on two photons absorption (TPA) is used. Laser source is afemtosecond Ti-Sapphire laser. Micron scale and sub micronscale 3D structures can be fabricated in the samples using TPA
20 μm

under a microscope with a high NA object lens. Lithographic
photopolymers is used to fabricate 2D or 3D structures. Silver
micron structures can be fabricated using photo-reduction ofsilver ion by TPA technique. Fabrication of photonic crystals andlight cloaking materials (metamaterials) using TPA are ourcurrent objective.
4) For manipulation of light or photon, organic dye laser devices

CLSM images of three dimensionallyfabricated Ag structures.
Naoto Tsutsumi, Kazuya Nagata and
Wataru Sakai, “Two-photon laser
fabrication of three-dimensional silver
microstructures with submicron scale
linewidth”, Appl. Phys. A 103,
421–426 (2011).

have been developed. Organic distributed feedback (DFB) anddistributed Bragg reflection (DBR) lasers have been fabricated using an organic waveguide polymer.

Slope efficiency

100

(a)

2500

4.7 %

2000

Active layer 3.4 m/Intermediate
Active layer 1.7 m/Intermediate
Active layer 1.7 m

1500

80

1000

60

500

2.2 %

40
20
0
0.0

0
0.35
0.28
0.21
0.14
0.07

0.9 %

0.5

1.0
1.5
2.0
Pump energy (J)

2.5

3.0
560

570

580
590
600
Wavelength (nm)

610

Pu
m
p
(m
en
J/c
e
m 2 rgy/pulse)

Emission energy (nJ)120

Emission intensity (a. u.)

Low threshold down to nJ or pJ and high slope efficiency in the order of tens % are current objective.

Slope efficiency and threshold for polymer laser.
N. Tsutsumi and M. Shinobu, “All organic DFB Laser Enhanced by Intermediate High Refractive Index Polymer Layer”,
Appl. Phys. B 105(4), 839-845 (2011).

5) Related to the environment, photosensitized reaction and photosensitized biodegradability of polymers
have been investigated using direct measurement of an electron spin resonance (ESR) spectroscopy andspin trapped method based on ESR spectroscopy. Radical species are assigned from ESR signals, fromwhich the reaction mechanism can be modeled. Simulation technique also supports the evaluation ofreaction mechanism.

4II. Publications and Achievements(a) Original papers
2007
1)

Naoto Tsutsumi and Arata Fujihara, “Self-assembled Spontaneous Structures Induced by a Pulsed
Laser on a Surface of Azobenzene Polymer Film”, J. Appl. Phys. 101, 033110 (5 pages) (2007).

2)

Naoto Tsutsumi, Shinya Yoda and Wataru Sakai, “Infrared spectra and ferroelectricity of ultrathin
films of vinylidene fluoride and trifluoroethylene copolymer”, Polym. Int’l. 56, 1254-1260 (2007).

3)

Minoru Nagata, Ryosuke Sugiura, Wataru Sakai, and Naoto Tsutsumi,“Synthesis and Characterizationof Biodegradable Network Poly(ethylene glycol) Films with Elastomeric Properties”, J. Appl. Polym.
Sci. 106 (5) 2885-2891 (2007).

4)

Naoto Tsutsumi and Masayuki Otsuji,“Crystalline Structures, Surface Morphology and FerroelectricResponse in Ultra-thin Film of Vinylidene Fluoride and Trifluoroethylene Copolymer”, J. Appl. Phys.
102, 104101 (4 pages) (2007).

2008
5)

N. Tsutsumi, Y. Kono, M. Oya, W. Sakai and M. Nagata, “Recent development of biodegradable
network polyesters obtained from renewable natural resources”, Clean 36(8), 682-686 (2008).

6)

N. Tsutsumi, A. Fujihara, K. Nagata, “Fabrication of laser induced periodic surface structure forgeometrical engineering”, Thin Solid Films 517, 1487-1492 (2008).

7)

N. Tsutusmi and Y. Ikegami, “Second-oeder optical nonlinearities from χ(2) gratings induced byholographic all-optical poling”, Optics Commun. 281, 5905-5909 (2008).

8)

N. Tsutsumi and H. Kasaba, “Effect of molecular weight of poly(N-vinyl carbazole) on
photorefractive performances”, J. Appl. Phys. 104, 073102 (2008).

9)

M. Nagata, T. Tanabe, W. Sakai, and N. Tsutsumi, “Preparation and properties of biodegradable
network poly(ester-carbonate) elastomers”, Polymer 49, 1506-1511 (2008).

10) N. Tsutsumi, Y. Ito, and W. Sakai, “Effect of sensitizer on photorefractive nonlinear optics inpoly(N-vinylcarbazole) based polymer composites”, Chem. Phys. 344, 189-194 (2008).
11) N. Tsutsumi and M. Takeuchi, “All-plastic organic dye laser with distributed feedback resonatorstructure”, Thin Solid Films 516, 2783-2787 (2008).
12) N. Tsutsumi and M. Takeuchi, “Ti-sapphire femtosecond pulse pumped laser emission from all-plastic
organic waveguide with distributed feedback resonator”, Optics Commun. 281, 2179-2183 (2008).

200913) Naoto Tsutsumi and Takashi Ishibashi, “Organic Dye Lasers with Distributed Bragg Reflector Gratingand Distributed Feedback Resonator”, Optics Express 17 (24), 21698-21703 (2009).
14) Naoto Tsutsumi and Wataru Miyazaki, “Photorefractive Performance of Polycarbazoylethylacrylate
Composites with Photoconductive Plasticizer”, J. Appl. Phys. 106, 083113 (2009).
15) Naoto Tsutsumi, Tomohiro Yamaoka, “Ferroelectric Properties of Ultrathin Films of Nylon 11”, Thin
Solid Films 518, 814-818 (2009).
16) T. Yamao, T. Inoue, Y. Okuda, T. Ishibashi, S. Hotta and N. Tsutsumi, “Gain-narrowed emissions fromoligomer crystals assisted by interference exposure”, Synth. Met. 159, 889-892 (2009).
5201117) N. Tsutsumi and M. Shinobu, “All Organic DFB Laser Enhanced by Intermediate High Refractive
Index Polymer Layer”, Appl. Phys. B 105(4), 839-845 (2011).
18) Y. Makino, T. Hinode, A. Okada, T. Yamao, N. Tsutsumi, S. Hotta, “Spectrally-Narrowed Emissions
from a Layered Organic Transistor Equipped with a Diffraction Grating”, Phys. Procedia 14, 177–181(2011).
19) N. Tsutsumi, K. Kinashi, and W. Sakai, “Strategy for high performance photorefractive polymer
composites”, (Polymer Photonics, and Novel Optical Technologies edited by Y. Kawabe and M.
Kawase, 6-10, PWC publishing (2011)).
20) A. Nonomura, W. Sakai, K. Kinashi, and N. Tsutsumi, “Photorefractive performance ofpolycarbazoylethylacrylate composite”, (Polymer Photonics, and Novel Optical Technologies edited
by Y. Kawabe and M. Kawase, 91-95, PWC publishing (2011)).
21) Naoto Tsutsumi, Akihito Dohi, Asato Nonomura, and Wataru Sakai, “Enhanced performance ofphotorefractive poly(N-vinyl carbazole) composites”, J. Polym. Sci. Part B: Polym. Phys. 49, 414-420(2011).
22) Naoto Tsutsumi, Kazuya Nagata and Wataru Sakai, “Two-photon laser fabrication of
three-dimensional silver microstructures with submicron scale linewidth”, Appl. Phys. A 103, 421–426(2011).
23) Naoto Tsutsumi and Hitoshi Nishida, “Tunable Distributed Feedback Lasing with Low Threshold andHigh Slope Efficiency from Electroluminescent Conjugated Polymer Waveguide”, Optics Commun.
284, 3365–3368 (2011).

201224) Naoto Tsutsumi and Yuki Nagano, “Off-axis quasi-phase matched second-order optical nonlinearity
from χ(2) gratings induced by holographic all-optical poling”, J. Opt. Soc. Am. B, 29(1), 23-28 (2012).

(b) Books
20101) W. Sakai and N. Tsutsumi, “Photodegradation and radiation degradation”

in “Poly(lactic acid)

Synthesis, structures, properties, processing, and applications” edited by R. Auras et al., Chap. 24,
413-422, Wiley (2010).
2) N. Tsutsumi, W. Sakai, “Fundamental Polymer Science (in Japanese)”, Saiensu-sha (2010).

20111) N. Tsutsumi, “Polymeric Photorefractive Materials (in Japanese)”, 【CSJ Current Review 07】in “New
Function and Property Based on Polymer-Light Interaction”, Part II Chap. 11, 118-123 Kagakudojin(2011).
2) N. Tsutsumi, “Development of Fast Organic Photorefractive Polymers for Advanced OpticalCommunication Technology (in Japanese)”, in “Advanced Photonics Polymer: Materials andApplications”, Chap 2, Section 6, 55-60, cmc books (2011).

6

(c) Reviews and Reports
2007
N. Tsutsumi, “”Fabrication on New Organic Optical Devices with the Structures controlled in the
Dimension of Nanometer Scale (in Japanese)”, Function & Materials 27(3), 5-10 (2007).

2008
1) N. Tsutsumi, “Formation of Laser-induced Structure (in Japanese)”, Function & Materials 28(2), 35-42(2008).
2) N. Tsutsumi, “Organic Laser Devices with Organic Waveguide (in Japanese)”, Expected Materials for
the Future 8(8), 48-53 (2008).
3) W. Sakai, “Electron Spin Science & Technology for Polymer Materials - Application of Electron Spin
Resonance Measurement - (in Japanese)”, High Polymers, Japan (Kobunshi) 57 (1), 27-30 (2008).

2009
N. Tsutsumi, “Organic Laser Devices (in Japanese)”, Material Stage 9(8), 3-5 (2009).

2012
N. Tsutsumi, “Organic Photorefractive Polymeric Materials (in Japanese)”, Expected Materials for the
Future 12(1), 39-44 (2012).

(d) Awards(e) Invited Lectures
2007
1)

N. Tsutsumi, “Hologram Recording and Polymer (in Japanese)”, Kobunshi Doyukai, Society ofPolymer Science, Japan, January 22, 2007 (2007).

2)

N. Tsutsumi, “Fabrication of Laser Induced Periodic Structures and Geometrical Engineering”,
Chemical Society, Japan, March 25, 2008.

3)

N. Tsutsumi, W. Sakai, M. Nagta, “Recent Development of Biodegradable Network Polyesters
Obtained from Renewable Natural Resources”, The 234th ACS National Meeting, Boston, MA, USA,
August, 21, 2007.

4)

N. Tsutsumi, “Crystalline Structure, Surface Morphology, and Ferroelectric Response of Ultra-thinVinylidene Fluoride and Trifluoroethylene Copolymers”, The 2nd International Symposium on
Polymer Science, NIST, MD, USA, December 10-12, 2007.

5)

N. Tsutsumi, “Fabrication of Laser Induced Periodic Structures and Geometrical Engineering”, 2ndInternational Symposium on the Manipulation of Advanced Smart Materials (ISMASM2008),
Yumebutai, Awaji, May 27-29, 2008.

2010
1)

N. Tsutsumi, K. Kinashi, W. Sakai, “Strategy for High Performance Photorefractive Polymer
Composites”, 11th Chitose International Forum on Photonics Science & Technology (CIF’11), Chitose,
October 14-15, 2010.

2)

N. Tsutsumi, K. Kinashi, W. Sakai, “Strategy for High Performance Photorefractive Polymer
7Composites and Their Applications to Optical Devices”, The 4th International Symposium on Polymer
Materials Science, NIST, MD, USA, October 28-29, 2010.

2011
1)

N. Tsutsumi, “Photorefractive Polymers - Now and Future -“, Polymer Optical Circuit Meetings,
Osaka University, March 8, 2011.

2)

N. Tsutsumi, “Development of Fast Organic Photorefractive Polymers for Advanced OpticalCommunication Technology (in Japanese)”, Photonics Polymer Meetings, Keio University, June 6,
2011.

3)

N. Tsutsumi, K. Kinashi, W. Sakai, “Photorefractive Polymers for Dynamic Holographic Display”, 1stIntenational Conference on Advanced Photonic Polymers (ICAPP2011), Yokohama, December 1-2,
2011.

2012
N. Tsutsumi, K. Kinashi, A. Nonomura, W. Sakai, “Quickly Updatable Hologram Images with High
Performance Photorefractive Polymer Composites”, SPIE Photonics West, San Francisco, CA, USA,
January 23-25, 2012.

(f) Patents
2007
1)

N. Tsutsumi, M. Urata, K. Iwai, “High molecular weight carbazole contained polymers”, Japanese
Patent Appl. No. 2007－228568.

2)

N. Tsutsumi, Y. Shimizu, “Photorefractive materials and their production methods as well ashologram”, Japanese Patent No. 3973964.

2009
N. Tsutsumi, M. Urata, “Photorefractive Composites”, Japanese Patent Appl. No. 2009－032004.

2011
N. Tsutsumi, K. Kinashi, Y. Kawabe, J. Nishide, Y. Sasabe, “3 Dimensional holographic displaying
system and display devices”, Japanese Patent Application No. 2011－259704.

(g) Funds and Financial Supports
2007
N. Tsutsumi, Grant-in-Aid for Scientific Research, Exploratory Research 19655081, “Direct
Observation of Temporal Change in Nano-meter Scale Polymer Aggregated Structures Using
Two-photon Excited STED Microscopy”.

2008
N. Tsutsumi, Grant-in-Aid for Scientific Research, Exploratory Research 19655081, “Direct
Observation of Temporal Change in Nano-meter Scale Polymer Aggregated Structures Using
Two-photon Excited STED Microscopy”.

2009
N. Tsutsumi, N. Moriya, Strategic Promotion of Innovative Research and Development (SPIRE),
8

200903001, Japan Science and Technology Agency (JST), “Development of Fast Organic
Photorefractive Polymers for Advanced Optical Communication Technology”.

2010
N. Tsutsumi, N. Moriya, Strategic Promotion of Innovative Research and Development (SPIRE),
200903001, Japan Science and Technology Agency (JST), “Development of Fast Organic
Photorefractive Polymers for Advanced Optical Communication Technology”.

2011
N. Tsutsumi, N. Moriya, Strategic Promotion of Innovative Research and Development (SPIRE),
200903001, Japan Science and Technology Agency (JST), “Development of Fast Organic
Photorefractive Polymers for Advanced Optical Communication Technology”.

9Polymer Photonics Laboratory
Akira ITAYA, Dr., Prof.
Shinjiro MACHIDA, Dr., Associate Prof.
I. Researches
In our laboratory, we are studying photophysical properties of organic materials in nanoscale region
and trying to realize novel functional organic or polymer materials by controlling the nanostructure
affecting photophysical properties. The key words for our research are "nano" and "photonics".
Representative research projects are as follows.
1) Synthesis and characterization of thermosensitive polymers with photofunctional dye2) Synthesis and micellar characterization of amphiphilic triblock copolymers with crystalline core3) Transient absorption spectroscopy of organic nanoparticles prepared by laser ablation
4) Nanoscale environments of polymers probed by single molecule spectroscopy5) Single molecule spectroscopy of charge-transfer (CT) complexes and CT nanocrystals
6) Synthesis and photophysical properties of fluorescent dyes with bulky substituents
7) Transient electric birefringence of polymer solutions and dispersions

10II. Publications and Achievements(a) Original papers
20071) S. Machida*, H.Nakata, K. Yamada, and A. Itaya, “Morphological change of a diblock copolymer
film induced by selective doping of a photoactive chromophore”, J. Polym. Sci. Part B: Polym.
Phys., 45(3), 368-375 (2007).
2) T. Konishi*, K. Kurashiki, A. Itaya, S. Aiba, M. Iwamoto, and Y. Fujii, “Preparation of chitin andchitosan layers by pulsed laser deposition”, Chitin and Chitosan Research,13 (1), 1-8 (2007).
3) S. Fukuma, K. Irie, T. Ikegami, S. Masuo, S. Machida, N. Tanaka, and A. Itaya*, “Photophysicaland photoconductive properties of a carbazolyl derivative with a mesogen group of
alkoxycyanobiphenyl in mesophases”, J. Photochem. Photobiol. A: Chemistry, 189 (1), 55-64(2007).
4) S. Masuo*, A. Masuhara, T. Akashi, M. Muranushi, S. Machida, H. Kasai, H. Nakanishi, H. Oikawa,
and A. Itaya*, “Photon antibunching in the emission from a single organic dye nanocrystal”, Jpn. J.
Appl. Phys., 46 (12), L268-L270 (2007).
Introduced by “RESEACH HIGHLIGHTS” Nature Photonics, 1, 253 (2007).
5) Z. Wang, S. Masuo, S. Machida, and A. Itaya*, ”Site-selective doping of dyes intopolystyrene-block-poly(4-vinylpyridine) diblock copolymer films and selective laser ablation of thedye-doped films” Jpn. J. Appl. Phys., 46 (11), 7569-7576 (2007).
2008
1) S. Machida*, T. Sugihara, S. Masuo, and A. Itaya, “Photoluminescence properties of dye-doped
polymer multilayer films with periodic structure”, Thin Solid Films, 516 (9), 2382-2386 (2008).
2) S. Machida*, T. Wakamatsu, S. Masuo, H. Jinnai, and A. Itaya, “Morphology and photophysicalproperties of polymer thin films dispersed with dye nanoparticle”, Thin Solid Films, 516 (9),2615-2619 (2008).
3) S. Masuo, T. Tanaka, S. Machida, and A. Itaya, “Influence of Molecular Weight and Conformationon Single-Photon Emission from Isolated Conjugated Polymer Chains”, Appl. Phys. Lett., 92(23),233114 (3 pages) (2008).
4) S. Masuo, T. Endo, Y. Yamane, S. Machida, and A. Itaya*, “Fluorescence Properties of Individual
Charge-transfer Complexes in Polymer Films Revealed by Single Molecule Fluorescence
Spectroscopy”, Chem. Lett., 37(9), 916-917 (2008).
5) K. Kuwamura, T. Ikegami, S. Masuo, S. Machida, N. Tanaka, and A. Itaya*, “Anomalous excimer
formation of a pyrenyl derivative having a mesogen group of alkoxycyanobiphenyl in its smectic
mesophase”, J. Photochem. Photobiol. A: Chemistry, 200, 232-238 (2008).
20091) S. Masuo*, T. Tanaka, T. Murakami, A. Masuhara, S. Machida, H. Kasai, H. Oikawa, and A. Itaya*,“Single-Photon Emission from a Single Nanoparticle Consisting of a Single Conjugated Polymer
Chain”, Synthetic Metals, 159(9-10), 805-808 (2009).
2) S. Masuo, Y. Yamane, T. Endo, S. Machida, and A. Itaya*, “Fluorescence Dynamics of Individual
11

Charge-Transfer Complexes in Polymer Films Revealed by Single Molecule Fluorescence
Spectroscopy”, J. Phys. Chem. C, 113(27), 11590-11596 (2009).
3) S. Masuo, H. Naiki, S. Machida, and A. Itaya, “Photon Statistics in Enhanced Fluorescence from aSingle CdSe/ZnS Quantum Dot in the Vicinity of Silver Nanoparticles”, Appl. Phys. Lett., 95(19),193106 (3 pages) (2009).
Cited in “Virtual Journal of Nanoscale Science & Technology, 20 (21). OPTICAL PROPERTIESAND QUANTUM OPTICS” November 16, 20092010
1) A. Itaya*, T. Murakami, N. Yokoi, S. Masuo, and S. Machida, “Laser Ablation of Micro-Sized
Organic Dye Particles in Solvents with Limited Solubility for the Dye: Formation of aSupersaturated Solution”, Chem. Lett., 39(3), 215-217 (2010).
2) S. Masuo*, N. Nishi, M. Hosugi, S. Machida, and A. Itaya, “Dependence of Single-photon
Emission from Single Conjugated Polymer Chains on Their Spatial Size as Determined by Photon
Correlation Measurements in Fluid Solution”, Chem. Lett., 39(7), 780-782 (2010).
2011
H. Naiki, S. Masuo*, S. Machida, and A. Itaya*, “Single-Photon Emission Behavior of Isolated
CdSe/ZnS Quantum Dots Interacting with the Localized Surface Plasmon Resonance of Silver
Nanoparticles”, J. Phys. Chem. C, 115(47), 23299-23304 (2011).
2012
S. Masuo, Y. Yamane, S. Machida, and A. Itaya*, “Fluorescence behavior of individual
charge-transfer complexes revealed by single-molecule fluorescence spectroscopy: influence of thehost polymer matrix”, J. Photochem. Photobiol. A: Chemistry, 227, 65-70 (2012).
Online publication complete: 6-DEC-2011, DOI information: 10.1016/j.jphotochem.2011.11.005(b) Books
1) A. Itaya, S. Machida, and S. Masuo, "Formation of Nanosize Morphology of Dye-Doped
Copolymer Films and Evaluation of Organic Dye Nanocrystals Using a Laser”, In “MolecularNano Dynamics” Vol. 1: Spectroscopic Methods and Nanostructures, pp.203-224, (ed. by H.
Fukumura, M. Irie, Y. Iwasawa, H. Masuhara, K. Uosaki), Wiley-VCH, Weinheim (2009)2) S. Masuo, A. Itaya, and S. Machida, “Fabrication of Single-Photon Source using Nano-sizing ofConjugated Polymers (in Japanese)”, In “Control of Super-Hierarchical Structures and Innovative
Functions of Next-Generation Conjugated Polymers”, pp.434-440, (Contributor, K. Akagi), CMC
Publisher (2009).
3) S. Machida, "Photo-Hole Burning –Frequency Domain Optical Memory (in Japanese)", In"Subject-Book of Photochemistry" (ed. by S. Ito, M. Sisido, K. Horie, T. Majima), Asakura Shoten(in press).
4) A. Itaya, “Excimer and Exciplex (in Japanese)”, In "Subject-Book of Photochemistry" (ed. by S. Ito,
M. Sisido, K. Horie, T. Majima), Asakura Shoten (in press).

12

(c) Reviews and Reports
2008
S. Masuo and A. Itaya, “Antibunching Emission from a Single Organic Dye Nanocrystal (inJapanese)”, Optics, 37, 472-474 (2008).
2011
S. Masuo, H. Naiki, T. Tanaka, S. Machida, and A. Itaya, ”Photon Antibunching Behavior of a
System Consisting of Nano-sized Fluorophore and Metal Nanostructure (in Japanese)”, MolecularElectronics and Bioelectronics, 22, 127-132 (2011).
(d) Awards(e) Invited Lectures(f) Patents(g) Funds and Financial Supports
2007-2008
S. Masuo, A. Itaya, and S. Machida, Grant-in-Aid for Scientific Research on Priority Areas, #446,“Fabrication of Single-Photon Source using Nano-sizing of Conjugated Polymers”
2007-2010
A. Itaya, Joint Research with Nissan Chemical Industries Limited,“Studies on Photo- andElectronic-Functional Polymeric and Organic Materials”
2009-2011
A. Itaya and S. Masuo, Grant-in-Aid for Scientific Research, Scientific Research (C) 21550012,“Studies on Isolated Charge-Transfer Complexes and Charge-Transfer Complexes Nanocrystals
using Single Molecule Fluorescence Spectroscopy”

13Polymer Physics Laboratory
Shu HOTTA, Dr., Prof.
Takeshi YAMAO, Dr., Associate Prof.
I. Researches
We are currently developing a novel series of organic semiconductors. We term these
semiconductors “thiophene/phenylene co-oligomers (TPCOs).” The TPCOs comprise
thiophenes and phenylenes (benzenes) that are widely used as raw materials of dyes andpharmaceutical agents. These TPCOs exhibit a number of unique and interesting
optoelectronic and semiconducting characteristics. We mention them as below.
(i)

Various molecular backbones bent, zigzag, pseudo-straight, a bird’s wing, etc. canreadily be shaped. These variations result from appropriately arranging thepentagonal thiophenes and hexagonal phenylenes in the molecule (see Fig. 1).
Non-straight molecules produce a peculiar crystallographic structure where themolecular long axes stand nearly upright against the bottom crystal plane. This
crystal structure is responsible for high-performance electronic and photonic
characteristics of the TPCOs. Examples include high carrier mobility (~1 cm2/Vs）
and spectrally-narrowed emissions (SNEs), e.g. amplified spontaneous emission(ASE), laser oscillation, stimulated resonant Raman scattering, etc.

(ii)

Regarding the industrial applications, it will be highly advantageous that theemission colors can subtly be tuned. This can readily be achieved by changing thetotal ring number of thiophenes and phenylenes and their arrangement in a molecule.
These compounds are accessible via organosynthetic routes such as Suzuki coupling

Fig. 1. Various thiophene/phenylene co-oligomers (TPCOs) and their molecular shapes (bent, zigzag,
pseudo-straight, a bird’s wing, etc.).

14

and Grignard coupling. Thus the TPCOs are
attractive and promising in both the basic
research and technological aspects.
(iii)

Another advantage lies in that the TPCO
molecules can be chemically-modified at either
molecular terminal. This is particularly usefulin controlling polarity of the semiconductor (i.e.
either the p-type or the n-type). To this end weuse e.g. alkyl and methoxy groups for the

50 mFig. 2. Fluorescence micrograph of a
BP1T crystal grown in a liquid phase.

p-type materials and fluorine, trifluoromethylgroups, cyano groups, etc. for the n-type. Both types of materials are indispensable
constituents of the semiconductor devices.
We also developed growth methods of thin single crystals of TPCOs and other organic
semiconductors. As an example Fig. 2 shows a micrograph of a hexagon single crystal of
BP1T. The contrast between glaring edge emissions and complete darkness inside the crystal
reflects the exceedingly effective optical confinement in the crystal. Superior ability of this
optical confinement is one of attractive characteristics of the TPCOs and makes their crystals
an excellent candidate for a material of organic light-emitting devices and laser media.
II. Publications and Achievements(a) Original papers
20071) S. Hotta, M. Goto, and R. Azumi, “Peculiar Crystal Structure of a Thiophene/Phenylene
Co-Oligomer of 2,5-Bis(4'-methoxybiphenyl-4-yl)thiophene,” Chem. Lett. 36, 270–271 (2007).
2) K. Yamane, H. Yanagi, A. Sawamoto, and S. Hotta, “Ambipolar Organic Light Emitting Field
Effect Transistors with Modified Asymmetric Electrodes,” Appl. Phys. Lett. 90, 162108/3 pages(2007).
3) T. Yamao, T. Ohira, S. Ota, and S. Hotta, “Polarized Measurements of Spectrally Narrowed
Emissions from a Single Crystal of a Thiophene/Phenylene Co-Oligomer,” J. Appl. Phys. 101,
083517/5 pages (2007).
4) T. Katagiri, S. Ota, T. Ohira, T. Yamao, and S. Hotta, “Synthesis of Thiophene/Phenylene
Co-Oligomers. V. Functionalization at Molecular Terminals toward Optoelectronic Device
Applications,” J. Heterocyclic Chem. 44, 853–862 (2007).
5) S. Fujiwara, K. Bando, Y. Masumoto, F. Sasaki, S. Kobayashi, S. Haraichi, and S. Hotta, “Laser
Oscillations of Whispering Gallery Modes in Thiophene/Phenylene Co-Oligomer Microrings,”
Appl. Phys. Lett. 91, 021104/3 pages (2007).
6) T. Yamao, T. Miki, H. Akagami, Y. Nishimoto, S. Ota, and S. Hotta, “Direct Formation of Thin
Single Crystals of Organic Semiconductors onto a Substrate,” Chem. Mater. 19, 3748–3753(2007).

15

7) F. Sasaki, S. Kobayashi, S. Haraichi, S. Fujiwara, K. Bando, Y. Masumoto, and S. Hotta,“Microdisk and Microring Lasers of Thiophene-Phenylene Co-Oligomers Embedded in Si/SiO2
Substrates,” Adv. Mater. 19, 3653–3655 (2007).
8) T. Yamao, Y. Taniguchi, K. Yamamoto, T. Miki, S. Ota, S. Hotta, M. Goto, and R. Azumi,“Anisotropic Refractive Indices of Organic Crystals of Thiophene/Phenylene Co-Oligomers
Determined by Microspectroscopic Measurements,” Jpn. J. Appl. Phys. 46, 7478–7482 (2007).
9) T. Yamao, K. Yamamoto, Y. Taniguchi, and S. Hotta, “Spectrally Narrowed Emissions Occurring
near an Interface between a Single Crystal Thiophene/Phenylene Co-Oligomer and a Glass
Substrate,” Appl. Phys. Lett. 91, 201117/3 pages (2007).
2008
1) K. Bando, T. Nakamura, S. Fujiwara, Y. Masumoto, F. Sasaki, S. Kobayashi, Y. Shimoi, and S.
Hotta, “Optical Selection Rule for the Lower Davydov Excitons in Co-Oligomer Single Crystals,”
Phys. Rev. B 77, 045205/6 pages (2008).
2) T. Shimada, S. Hotta, and H. Yanagi, “Energy-Transferred Photoluminescence fromThiophene/Phenylene Oligomer Thin Films,” J. Lumin. 128, 457–461 (2008).
3) T. Yamao, S. Ota, T. Miki, S. Hotta, and R. Azumi, “Improved Sublimation Growth of Single
Crystals of Thiophene/Phenylene Co-Oligomers,” Thin Solid Films 516, 2527–2531 (2008).
4) T. Hiramatsu, T. Shimada, S. Hotta, and H. Yanagi, “Photoluminescence Dynamics ofThiophene/Phenylene Co-Oligomer Thin Films Based on Förster Energy Transfer,” Thin Solid
Films 516, 2700–2703 (2008).
5) K. Yamane, A. Sawamoto, S. Hotta, and H. Yanagi, “Organic Heterojunction Ambipolar Field
Effect Transistors with Asymmetric Source and Drain Electrodes,” Thin Solid Films 516,
2758–2761 (2008).
6) K. Yamane, H. Yanagi, and S. Hotta, “Ambipolar Field Effect Transistors with Heterojunction ofOrganic Semiconductors,” Thin Solid Films 516, 3157–3161 (2008).
7) T. Yamao, K. Yamamoto, Y. Taniguchi, T. Miki, and S. Hotta, “Laser Oscillation in a Highly
Anisotropic Organic Crystal with a Refractive Index of 4.0,” J. Appl. Phys. 103, 093115/4 pages(2008).
8) T. Yamao, Y. Taniguchi, K. Yamamoto, T. Miki, T. Ohira, and S. Hotta, “Polarized Emissions fromSingle Crystals of Thiophene/Phenylene Co-Oligomers Measured by Microspectroscopy,” Jpn. J.
Appl. Phys. 47, 4719–4723 (2008).
9) T. Yamao, K. Yamamoto, T. Miki, H. Akagami, Y. Nishimoto, and S. Hotta, “Polarized Laser
Oscillation from Polygon Crystals of Thiophene/Phenylene Co-Oligomers Grown by Liquid-Phase
Growth,” Phys. Status Solidi C 5, 3194–3196 (2008).
10) T. Yamao, Y. Shimizu, K. Terasaki, and S. Hotta, “Organic Light-Emitting Field-Effect Transistors
Operated by Alternating-Current Gate Voltages,” Adv. Mater. 20, 4109–4112 (2008).
20091) T. Hiramatsu, N. Matsuoka, H. Yanagi, F. Sasaki, and S. Hotta, “Gain-Narrowed Emissions ofThiophene/Phenylene Co-Oligomer Single Crystals,” Phys. Stat. Solidi C 6, 338–341 (2009).
2) T. Yamao, H. Kuriki, T. Miki, and S. Hotta, “A Field-Effect Transistor Based upon
Thiophene/Phenylene Co-Oligomer Nanomolecules Combined with a Composite Polymer Gate
Insulator,” J. Nanosci. Nanotechnol. 9, 165–168 (2009).
3) S. Hotta, Y. Shimizu, T. Yamao, M. Goto, and R. Azumi, “Crystal Structure and FET

16

Characteristics
ofann-TypeThiophene/Phenylene
Co-Oligomerof
1,4-Bis{5-[4-(trifluoromethyl)phenyl]thiophen-2-yl}benzene,” Chem. Lett. 38, 294–295 (2009).
4) T. Yamao, K. Yamamoto, and S. Hotta, “A High Optical-Gain Organic Crystal Comprising
Thiophene/Phenylene Co-Oligomer Nanomolecules,” J. Nanosci. Nanotechnol. 9, 2582–2585(2009).
5) T. Yamao, K. Yamamoto, T. Inoue, Y. Okuda, Y. Taniguchi, and S. Hotta, “Refractive Indexalong the Molecular Long Axis of an Orthorhombic Thiophene/Phenylene Co-Oligomer Crystal,”
Jpn. J. Appl. Phys. 48, 04C174/4 pages (2009).
6) T. Shimada, S. Tomita, S. Hotta, S. Hayashi, and H. Yanagi, “Photoluminescence fromDonor-Acceptor Molecular Systems via Long Distance Energy Transfer Mediated by Surface
Plasmon,” Jpn. J. Appl. Phys. 48, 042001/4 pages (2009).
7) T. Yamao, T. Inoue, Y. Okuda, T. Ishibashi, S. Hotta, and N. Tsutsumi, “Gain-Narrowed
Emissions from Oligomer Crystals Assisted by Interference Exposure,” Synth. Met. 159, 889–892(2009).
8) S. Z. Bisri, T. Takenobu, Y. Yomogida, H. Shimotani, T. Yamao, S. Hotta and Y. Iwasa, “High
Mobility and Luminescent Efficiency in Organic Single-Crystal Light-Emitting Transistors,” Adv.
Funct. Mater. 19, 1728–1735 (2009).
9) T. Yamao, K. Juri, A. Kamoi, and S. Hotta, “Field-Effect Transistors Based on Organic Single
Crystals Grown by an Improved Vapor Phase Method,” Org. Electron. 10, 1241–1247 (2009).
10) T. Yamao, H. Akagami, Y. Nishimoto, S. Hotta, and Y. Yoshida, “Improved Device Performance ofOrganic Crystal Field-Effect Transistors Fabricated on Friction-Transferred Substrates,” J.
Nanosci. Nanotechnol. 9, 6271–6276 (2009).
11) T. Yamao, T. Sakaguchi, K. Juri, H. Doi, A. Kamoi, N. Suganuma, and S. Hotta, “Improvementsof Morphologies and Emission Characteristics of Highly Purified Organic Oligomer
Semiconductors,” Thin Solid Films 518, 489–492 (2009).
20101) S. Hotta, Y. Sakurai, Y. Okuda, T. Miki, K. Matsunaga, F. Hirato, T. Yamao, and H. Jinnai,“Grating-Assisted Spectrally-Narrowed Emissions from an Organic Slab Crystal Excited with a
Mercury Lamp,” J. Nanosci. Nanotechnol. 10, 440–447 (2010).
2) Y. Ido, Y. Masumoto, F. Sasaki, M. Mori, S. Haraichi, and S. Hotta, “Reduced Lasing Thresholdin Thiophene/Phenylene Co-Oligomer Crystalline Microdisks,” Appl. Phys. Express 3, 012702/3
pages (2010).
3) T. Yamao, Y. Shimizu, H. Kuriki, T. Katagiri, and S. Hotta, “Improved Field-Effect Transistor
Characteristics of an n-Type Semiconducting Thiophene/Phenylene Co-Oligomer,” Jpn. J. Appl.
Phys. 49, 01AB01/4 pages (2010).
4) Y. Shigee, H. Yanagi, K. Terasaki, T. Yamao, and S. Hotta, “Organic Light-Emitting Field-EffectTransistor with Channel Waveguide Structure,” Jpn. J. Appl. Phys. 49, 01AB09/4 pages (2010).
5) N. Matsuoka, T. Hiramatsu, H. Yanagi, F. Sasaki, and S. Hotta, “Characterization ofGain-Narrowed Emission from Biphenyl-Capped Thiophene Single Crystals,” Jpn. J. Appl. Phys.
49, 01AD05/4 pages (2010).
6) T. Yamao, K. Terasaki, Y. Shimizu, and S. Hotta, “Organic-Crystal Light-Emitting Field-EffectTransistors Driven by Square-Wave Gate Voltages,” J. Nanosci. Nanotechnol. 10, 1017–1020(2010).

17

7) A. Saeki, S. Seki, Y. Shimizu, T. Yamao, and S. Hotta, “Photogeneration of Charge Carrier
Correlated with Amplified Spontaneous Emission in Single Crystals of a Thiophene/Phenylene
Co-Oligomer,” J. Chem. Phys. 132, 134509/7 pages (2010).
8) T. Yamao, Y. Nishimoto, K. Terasaki, H. Akagami, T. Katagiri, S. Hotta, M. Goto, R. Azumi, M.
Inoue, M. Ichikawa, and Y. Taniguchi, “Single-Crystal Growth and Charge Transport Propertiesof an Alternating Co-Oligomer Composed of Thiophene and Phenylene Rings,” Jpn. J. Appl. Phys.
49, 04DK20/4 pages (2010).
9) N. Matsuoka, T. Hiramatsu, H. Yanagi, F. Sasaki, and S. Hotta, “Amplified Pulse Emissions with
Variable Delay Times in Vibronic Transition Bands of Thiophene/Phenylene Co-Oligomer Single
Crystals,” Jpn. J. Appl. Phys. 49, 052401/4 pages (2010).
10) F. Sasaki, M. Mori, S. Haraichi, Y. Ido, Y. Masumoto, and S. Hotta, “Microdisk Lasers and Field
Effect Transistors of Thiophene/Phenylene Co-Oligomers by Using High Temperature Deposition
Method,” Org. Electron. 11, 1192–1198 (2010).
11) K. Sawabe, T. Takenobu, S. Z. Bisri, T. Yamao, S. Hotta, and Y. Iwasa, “High Current Densities ina Highly Photoluminescent Organic Single-Crystal Light-Emitting Transistor,” Appl. Phys. Lett.
97, 043307/3 pages (2010).
12) T. Yamao, K. Juri, T. Sakaguchi, Y. Sakurai, H. Kuriki, A. Kamoi, and S. Hotta, “Melt Molding of
Uniaxially-Oriented Crystal Domains onto a Substrate,” Jpn. J. Appl. Phys. 49, 08JG06/4 pages(2010).
13) T. Yamao, Y. Sakurai, K. Terasaki, Y. Shimizu, H. Jinnai, and S. Hotta, “Current-Injected
Spectrally-Narrowed Emissions from an Organic Transistor,” Adv. Mater. 22, 3708–3712 (2010).
14) Y. Yomogida, T. Takenobu, H. Shimotani, K. Sawabe, S. Z. Bisri, T. Yamao, S. Hotta, and Y. Iwasa,“Green Light Emission from the Edges of Organic Single-Crystal Transistors,” Appl. Phys. Lett.
97, 173301/3 pages (2010).
15) K. H. K. Chan, T. Yamao, M. Kotaki, and S. Hotta, “Unique Structural Features and Electrical
Properties of Electrospun Conjugated Polymer Poly(3-hexylthiophene) (P3HT) Fibers,” Synth.
Met. 160, 2587–2595 (2010).
2011
1) T. Katagiri, Y. Shimizu, K. Terasaki, T. Yamao, and S. Hotta, “Light-Emitting Field-EffectTransistors Made of Single Crystals of an Ambipolar Thiophene/Phenylene Co-Oligomer,” Org.
Electron. 12, 8–14 (2011).
2) H. Yanagi, Y. Marutani, F. Sasaki, Y. Makino, T. Yamao, and S. Hotta, “Prethreshold Lasing with
Time-Delayed Pulse Emission from a Single Crystal of Thiophene/Phenylene Co-Oligomer,” Appl.
Phys. Express 4, 062601/3 pages (2011).
3) S. Z. Bisri, T. Takenobu, K. Sawabe, S. Tsuda, Y. Yomogida, T. Yamao, S. Hotta, C. Adachi, and Y.
Iwasa, “p-i-n Homojunction in Organic Light-Emitting Transistors,” Adv. Mater. 23, 2753–2758(2011).
4) Y. Makino, T. Hinode, A. Okada, T. Yamao, N. Tsutsumi, and S. Hotta, “Spectrally-Narrowed
Emissions from a Layered Organic Transistor Equipped with a Diffraction Grating,” Physics
Procedia, 14, 177–181 (2011).
5) Y. Inada, T. Yamao, M. Inada, T. Itami, and S. Hotta, “Giant Organic Single-Crystals of a
Thiophene/Phenylene Co-Oligomer toward Device Applications,” Synth. Met. 161, 1869–1877(2011).

18

6) K. Kajiwara, K. Terasaki, T. Yamao, and S. Hotta, “Light-Emitting Field-Effect Transistors
Consisting of Bilayer-Crystal Organic Semiconductors,” Adv. Funct. Mater. 21, 2854–2860(2011).
7) T. Yamao, Y. Okuda, Y. Makino, and S. Hotta, “Dispersion of the Refractive Indices of
Thiophene/Phenylene Co-Oligomer Single Crystals,” J. Appl. Phys. 110, 053113/7 pages (2011).
8) K. Bando, S. Kumeta, F. Sasaki, and S. Hotta, “Energy Dispersions of Anisotropic Refractive
Indices of Thiophene/Phenylene Co-Oligomer Crystals,” Jpn. J. Appl. Phys. 50, 101603/5 pages(2011).
2012
1) T. Sengoku, T. Yamao, and S. Hotta, “Organic Light-Emitting Diodes Based on Layered Films of
Thiophene/Phenylene Co-Oligomers,” J. Non-Cryst. Solids, in press.
2) A. Okada, Y. Fukaya, S. Hotta, and T. Yamao, “Light-Emitting Field-Effect Transistors Having
Metal Electrodes Modified with an Organic Thin Film,” Jpn. J. Appl. Phys., in press.
(b) Books
2007
S. Hotta, “Organic Transistors (in Japanese),” 46 pages, ED Research (2007).
2008
T. Yamao and S. Hotta, in “Frontiers of Photofunctional Polymeric Materials (in Japanese),” pp.
174–186, (ed. by K. Ichimura), CMC Publishing (2008).
2009
S. Hotta and T. Yamao, in “Control of Super-Hierarchical Structures and Innovative Functions of
Next-Generation Conjugated Polymers (in Japanese),” pp. 358–365, (ed. by K. Akagi), CMC
Publishing (2009).
20101) S. Hotta, in “Organic Semiconductor Device – From Fundamentals to the Latest Materials andDevices (in Japanese),” pp. 171–175, pp. 299–300, (ed. by 142 Committee of Japan Society for
the Promotion of Science), Ohmsha (2010).
2) T. Yamao, in “Organic Semiconductor Device – From Fundamentals to the Latest Materials andDevices (in Japanese),” pp. 202–206, (ed. by 142 Committee of Japan Society for the Promotionof Science), Ohmsha (2010).
2011
T. Yamao and T. Horiguchi, in “Development of Highly Efficient Two-Photon Absorption
Materials and their Applications (in Japanese),” pp. 85–89, (ed. by T. Watanabe), CMC Publishing(2011).
(c) Reviews and Reports
2008
S. Hotta, T. Katagiri, T. Yamao, K. Shimizu, H. Yanagi, M. Ichikawa, and Y. Taniguchi,“Development

andElectronicandPhotonic

19

Characteristics

ofThiophene/Phenylene

Co-Oligomers,” Int. J. Polym. Mater. 57, 515–531 (2008).
2011
S. Hotta and T. Yamao, “The Thiophene/Phenylene Co-Oligomers: Exotic Molecular
Semiconductors Integrating High-Performance Electronic and Optical Functionalities,” J. Mater.
Chem. 21, 1295–1304 (2011).
(d) Awards(e) Invited Lectures
20091) T. Yamao, K. Terasaki, Y. Shimizu, and S. Hotta, “Light Emission from Organic Field-EffectTransistors Enhanced by Alternating-Current Gate Voltages,” IMR Workshop on Organic Light
Emitting Devices, Japan (2009).
2) H. Yanagi, F. Sasaki, and S. Hotta, “Light Amplification by Stimulated Resonant Raman
Scattering in Organic Solids,” IMR Workshop on Organic Light Emitting Devices, Japan (2009).
3) S. Z. Bisri, Y. Yomogida, S. Tsuda, T. Takenobu, T. Yamao, C. Adachi, S. Hotta, and Y. Iwasa,“Optoelectronic Properties of Organic Single-Crystals Ambipolar Light-Emitting Transistor,” IMR
Workshop on Organic Light Emitting Devices, Japan (2009).
20101) T. Yamao, “Electrically-Excited Spectrally-Narrowed Emissions from an Organic Crystal on a
Transistor Devices,” the International Conference on Science and Technology of Synthetic Metals
2010 (ICSM 2010), Japan (2010).
2) S.

Hotta,“The

Thiophene/Phenylene

Co-Oligomers:

High-Performance

Molecular

Semiconductors Integrating Electronic and Optical Functionalities,” 2010 International Chemical
Congress of Pacific Basin Societies (PACIFICHEM 2010), U. S. A. (2010).
(f) Patents
2007
S. Bando, T. Katagiri, M. Miyata, M. Suzuki, H. Kitayama, S. Hotta, and T. Yamao,“(Thiopene/Phenylene) Co-Oligomer,” Japanese Patent Appl. No. 2007-285196, Publication No.
JP,2009-114074,A.
2008
1) S. Hotta, T. Yamao, H. Jinnai, Y. Sakurai, K. Matsunaga, T. Miki, and F. Hirato, “Organic Optical
Device, Method of Manufacturing the Same, and Method of Manufacturing Amplified or
Narrowed Light,” Japanese Patent Appl. No. 2008-175782, Publication No. JP,2010-015874,A.
2) S. Bando, T. Katagiri, M. Miyata, M. Suzuki, S. Hotta, and T. Yamao, “(Thiophene/Phenylene)
Cooligomer, Method for Producing the Same, and Organic Semiconductor Material andLight-Emitting Material Containing the Same,” Japanese Patent Appl. No. 2008-188486,
Publication No. JP,2010-024191,A.

20

3) T. Katagiri, S. Bando, M. Miyata, M. Suzuki, S. Hotta, and T. Yamao, “(Thiophene/Phenylene)
Cooligomer, Method for Producing the Same, and Organic Semiconductor Material andLight-Emitting Material Containing the Same,” Japanese Patent Appl. No. 2008-216781,
Publication No. JP,2010-053045,A.
4) S. Bando, T. Katagiri, M. Miyata, M. Suzuki, S. Hotta, and T. Yamao, “(Thiophene/Phenylene)
Cooligomer, Production Method thereof and Organic Semiconductor Material and Luminescent
Material Containing the Cooligomer,” Japanese Patent Appl. No. 2008-278300, Publication No.
JP,2009-155318,A.
2009
T. Yamao, Y. Shimizu, K. Terasaki, and S. Hotta, “Method and Device for Driving Light-Emitting
Device,” PCT Int. Appl. No. PCT/JP2009/052092.
20101) H. Kanbara, N. Koshobu, J. Kobayashi, T. Yamao, and S. Hotta, “Electrooptic Waveguide andElectrooptic Element Using the Same,” Japanese Patent Appl. No. 2010-186649.
2) S. Hotta, T. Yamao, K. Terasaki, A. Okada, and K. Kajiwara, “Light-Emitting Transistor Including
Organic Laminate,” Japanese Patent Appl. No. 2010-248628, Publication No. JP,2011-187924,A.
2011
T. Yamao, S. Hotta, Y. Sakurai, Y. Makino, K. Terasaki, and A. Okada, “Light-Emitting
Transistor,” PCT Int. Appl. No. PTC/JP2011/052760.
(g) Funds and Financial Supports
2007
S. Hotta, Grant-in-Aid for Scientific Research on Priority Areas “Super-Hierarchical Structures,”No. 17067009, “Ultimate Performance of Hybridized Conjugated Polymers with Super-Controlled
Sizes and Molecular Shapes,” The Ministry of Education, Culture, Sports, Science andTechnology.
20081) S. Hotta, Grant-in-Aid for Scientific Research on Priority Areas “Super-Hierarchical Structures,”No. 17067009, “Ultimate Performance of Hybridized Conjugated Polymers with Super-Controlled
Sizes and Molecular Shapes,” The Ministry of Education, Culture, Sports, Science andTechnology.
2) T. Yamao, Grant-in-Aid for Exploratory Research, No. 20655041, “Linearly Polarized and Single
Mode Laser Oscillations from Hexagonal Organic Single Crystals,” The Ministry of Education,
Culture, Sports, Science and Technology.
20091) T. Yamao, Grant-in-Aid for Challenging Exploratory Research, No. 20655041, “Linearly Polarized
and Single Mode Laser Oscillations from Hexagonal Organic Single Crystals,” The Ministry of
Education, Culture, Sports, Science and Technology.
2) T. Yamao Grant for Basic Science Research Projects, “Current-Excited Laser Oscillations from21

Organic Crystal Devices,” The Sumitomo Foundation.
20101) S. Hotta, Grant-in-Aid for Scientific Research (B), No. 22350082, “Development of Oligomer
Semiconductor Laser Devices Based on Crystal Engineering,” The Ministry of Education, Culture,
Sports, Science and Technology.
2) T. Yamao, Grant for Basic Science Research Projects, “Current-Excited Laser Oscillations from
Organic Crystal Devices,” The Sumitomo Foundation.
3) T.

Yamao,

Research

Grant,“Understandingof

Current-Induced

Light-Emissions

by

Alternating-Current Voltage Application to Gate Electrodes of Organic Field-Effect Transistors,”
The Mazda Foundation.
20111) S. Hotta, Grant-in-Aid for Scientific Research (B), No. 22350082, “Development of Oligomer
Semiconductor Laser Devices Based on Crystal Engineering,” The Ministry of Education, Culture,
Sports, Science and Technology.
2) T. Yamao, Grant-in-Aid for Scientific Research (C), No. 23550208, “Fabrication andUnderstanding of Solid State Lasers Based on Layered Organic Crystals with a p-n Junction,” The
Ministry of Education, Culture, Sports, Science and Technology.
3) T.

Yamao,

Research

Grant,“Understandingof

Current-Induced

Light-Emissions

by

Alternating-Current Voltage Application to Gate Electrodes of Organic Field-Effect Transistors,”
The Mazda Foundation.
4) T. Yamao, Research Grant, “Development of a Phase-Resolved Measurement System for Current
and Emission of Organic Light-Emitting Transistors Operated by Alternating-Current Gate
Voltages,” The Murata Science Foundation.
20121) T. Yamao, Grant-in-Aid for Scientific Research (C), No. 23550208, “Fabrication andUnderstanding of Solid State Lasers Based on Layered Organic Crystals with a p-n Junction,” The
Ministry of Education, Culture, Sports, Science and Technology.
2) T. Yamao, Research Grant, “Development of a Phase-Resolved Measurement System for Current
and Emission of Organic Light-Emitting Transistors Operated by Alternating-Current Gate
Voltages,” The Murata Science Foundation.

22

Polymer Molecular Engineering Laboratory
Qui. TRAN-CONG-MIYATA, Dr., Prof.
Tomohisa NORISUYE, Dr., Associate Prof.

I. Researches
The main aim of researches in our Polymer Molecular Engineering (PME) Lab is designing
polymer materials with novel physical properties using chemical reactions and is also developing
novel characterization methods for polymers engineering and science. The final goal is constructing
polymers with novel properties which have ever been challenged and achieved before.

Designing

polymers are mainly based on conventional methods such as sol-gel techniques andphoto-polymerization. The characterization methods cover the broad range of structure analysis forpolymers ranging from transparent to visible light to translucent and completely turbid. As the mainpart of materials characterization, structure analysis are studied using both real space experimental
techniques such as microscopy (phase-contrast, interference, reflection, fluorescence, laser-scanningconfocal microscopy) and measurements using reciprocal space (light scattering, ultrasonics scatteringand interferometry). The most recent achievements of our group are summarized as follows:
1.

Controlling Morphologies of Polymer Mixtures by Photochemical Reactions
Ordered structures in Nature are naturally created by the spontaneous competition processes

among many antagonistic driving forces over a very long period of time.

These competition

processes occur at various length scales ranging from a few millimeters to few hundred thousand
kilometers over a large range of time scales, leading to a wide variety of hierarchical structures. In
the laboratory scales, in order to generate and control morphology of polymeric materials, we havecoupled various photochemical reactions to the phase separation process of polymer mixtures.
Reactions performed in these experiments are either photo-cross-link using photodimerization ofanthracene derivatives or photoisomerization of stilbene and azobenzene.

By taking advantages ofthese competing interactions during phase separation, intermediate periodic morphologies can begenerated and stabilized by irradiation with UV light. So far, as illustrated in Fig. 1, the following
morphologies were generated with this “competing interactions strategy”: bi-continuous
morphologies, tri-continuous morphologies, spatially graded continuous morphologies, hexagonalphases, hierarchical morphologies, three-dimensional (3D) salami structures etc.
As for practical application, we were successful in selectively dispersing nanofillers such as
multi-walled carbon nanotubes (MWCNTs) in a minor component of a polymer blend with continuous
morphology by reaction-induced phase separation. These experimental results clearly reveal the
insulating-conducting transition phenomena in synthetic polymers drivable by phase separation andalso open a new route to design and produce conducting materials using the composites of synthetic
polymers and nanofillers such as carbon nanotubes. An example for a 3D networks of CTNs inpolymers is illustrated in Figure 2.

23

ss

Spatially Graded Morphology[1]“Bagel-like” Morphology [ 4]Hexagonal Phase[3]Graded Spinodal Structure[2]Hierarchical Morphology[5]Fig.1. Various hierarchical and co-continuous morphologies resulting fromthe competitions between photochemical reactions and phase separation.

Fig. 2. MWCNTs networks in a polymer
composite imaged by reflection mode oflaser-scanning confocal microscopy.

2.

Newer Characterization Methods for Polymer Materialsa) in situ Monitoring the Local Deformation of Polymer Films in the Nanometer Scales
For most polymeric systems, inducing a chemical reaction between polymer chains in thebulk state often generates a local strain field, leading to a local deformation. This local strain field
could critically affect the physical properties of the reacting polymer materials. Depending upon the
distance from the glass transition temperature, this local (microscopic) strain field would relax
instantaneously or persist over a long period of time.

We have developed a Mach-Zehnderinterferometric (MZI) system shown in Fig. 3 to in situ monitor this reaction-induced elastic strain andits relaxation process in a photo-reactive polymers.

The 2D (planar) deformation in the nanometerscales observed for a photocured polymer is illustrated in Fig. 3 during the course of irradiation.
24

Fig. 2.

Block diagram of the Mach-Zehnder interferometer.

Fig. 3. Imaging the 2D deformation obtained
from the Mach-Zehnder interferometric data.

b) Dynamic Ultrasound Scattering (DSS) Method
Since characterization method using light would be unavailable for turbid samples, particularly
for multi-phase polymer materials, ultrasound becomes an indispensible tool to characterize thesephase-separated samples. The concept and the apparatus of the DSS method are illustrated in Fig. 4.
25

Unlike light scattering, it is able to obtain, besides the scattering intensity, the phase information withthis DSS scattering techniques. This important information enables us to additionally obtain the
dynamics of the system as a function of position in the sample.

As an example, by the DSS

techniques, the cooperative motions of micron-sized particles in the presence of long-rangedhydrodynamic interactions in aqueous suspensions can be evaluated to elucidate not only the particle
size but also their distribution using the data of velocity field.

As shown in Fig. 5, we havedemonstrated that the complicated dynamics of particles spontaneously undergoing sedimentation andfloating can be successfully distinguished and visualized by using the phase-mode dynamic ultrasoundtechniques .

Fig. 4. Instrumentation and the concept of observing fluctuations
by dynamic ultrasound scattering (DSS).

Fig. 5. Multi-directional monitoring (left) and imaging (right) of particles spontaneously
undergoing floating and sedimentation in a suspension liquid using the phase-mode dynamic
ultrasound scattering (DSS).

26

II. Publications and Achievements(a) Original papers
20071) Hironobu Hori, Osamu Urakawa, Okimichi Yano, Qui Tran-Cong-Miyata, “Phase Separation of
Binary Polymer Mixtures Under an Electric Field”, Macromolecules, 40, 389 – 394 (2007).
2) X.-A. Trinh, J. Fukuda, Y. Adachi, H. Nakanishi, T. Norisuye and Q. Tran-Cong-Miyata, “Effects ofElastic Deformation on Phase Separation of a Polymer Blend Driven by a Reversible
Photo-Cross-Linking Reaction”, Macromolecules, 40, 5566-5574 (2007).
3) Y. Takata, T. Norisuye, S. Hirayama, T. Takemori, Q. Tran-Cong-Miyata and S. Nomura, “DLS andAFM Studies on the Cluster Evolution of Organically Modified Silica Gels Catalyzed by a Super
Strong Acid”, Macromolecules, 40, 3773-3778 (2007).
4) T. Nakanishi, T. Norisuye, H. Sato, Q. Tran-Cong-Miyata, S. Nomura and T. Sugimoto, “Studies on
Microscopic

Structureof

Sol-GelDerivedNanohybrids

Containing

Heteropolyacid”,

Macromolecules, 40, 4165-4172 (2007).
5) H. Sato, T. Norisuye, T. Takemori, Q. Tran-Cong-Miyata and S. Nomura, “Effects of Solvent on
Microstructure and Proton Conductivity of Organic-Inorganic Hybrid Membranes”, Polymer, 48,
5681-5687 (2007)
6) A. Masunaga, Soh Ishino, H. Nakanishi, Q. Tran-Cong-Miyata,“Phase Separation Kinetics andMorphology of Light-Induced Interpenatrating Polymer Networks (IPNs) Confined in theMicrometer Scales (in Japanese)”, Japanese J. Polym. Sci. Tech. (Kobunshi Ronbunshu), 64, 294 300 (2007).
2008
1) H. Nakanishi, M. Satoh, Q. Tran-Cong-Miyata, “Hexagonal Phase Induced by a Reversible
Photo-cross-link Reaction in a Polymer Mixture”, Phys. Rev. E Rapid Commun., 77, 020801(R)(2008).
2) T. Norisuye, Y. Ikezawa, T. Takemori, Q. Tran-Cong-Miyata and S. Nomura, “Studies on Structural
Characterization of Organic-Inorganic Proton Conductive Membranes (in Japanese)”, Japanese J.
Polym. Sci. Tech. (Kobunshi Ronbunshu), 65, 716 - 729 (2008).
3) M. Kohyama, T. Norisuye, Q. Tran-Cong-Miyata, “High Frequency Dynamic Ultrasound Scatteringfrom Microsphere Suspensions”, Polymer J., 40, 398-399 (2008).
20091) Q. Tran-Cong-Miyata, D.-T. Van-Pham, K. Noma, T. Norisuye , H. Nakanishi, “The roles ofReaction Inhomogeneity in Phase Separation Kinetics and Morphology of Reacting Polymer
Blends”, Chinese J. Polym. Sci., 26, 23-36 (2009).
2) D.-T. Van-Pham, K. Sorioka, T. Norisuye, Q. Tran-Cong-Miyata, “Physical Aging of
Photo-Crosslinked Poly(ethyl acrylate) Observed in the Nanometer Scales by Mach-ZehnderInterferometry”, Polymer J., 41, 260-265 (2009)
3) Mariko Kohyama, Tomohisa. Norisuye, Qui Tran-Cong-Miyata, “Dynamics of Microsphere
Suspensions Probed by High Frequency Dynamic Ultrasound Scattering", Macromolecules, 42,27

752-759 (2009)4) Kosuke Murata, Tasuku Murata, Hideyuki Nakanishi, Tomohisa Norisuye and Qui
Tran-Cong-Miyata* “Effects of Light-Driven Regularity on the Physical Properties of Multiphase
Polymers”, Macromol. Mater. Eng., 294, 163-168 (2009).
5) A. Nagao, M. Kohyama, T. Norisuye, Q. Tran-Cong-Miyata, “Simultaneous Observation andAnalysis of Sedimentation and Floating Motions of Microspheres Investigated by Phase
Mode-Dynamic Ultrasound Scattering”, J. Appl. Phys., 105, 023526 (2009).
6) M. Fukuoka, H. Nakanishi, T. Norisuye, Q. Tran-Cong-Miyata, “Light Scattering Study on theMode-Selection Process in Reversible Phase Separation of a Photoreactive Polymer Mixture”,
J. Phys. Chem. B, 113, 14950-14956 (2009)20101) R.R. Nigmatullin, K. Fukao, H. Nakanishi, Q. Tran-Cong-Miyata, D. Tahara and K. Fukao,“Application of New Treatment Methods for Reading of Random Sequences: a Quantitative
Description of Aging Phenomena in Polymer Glasses”, Commun. Nonlinear Sci. Numer. Simul., 15,
1286-1307 (2010)2) D.T. Van-Pham, X.-A. Trinh, H. Nakanishi, Q. Tran-Cong-Miyata, “Design and Morphology
Control of Polymer Nanocomposites Using Light-Driven Phase Separation Phenomena”, Adv. Nat.
Sci. Nanosci. Nanotech., 1, 013002 (2010).
3) Daisuke Fujiki, Chuanming Jing, Dan-Thuy Van-Pham, Hideyuki Nakanishi, Tomohisa Norisuye
and Qui Tran-Cong-Miyata, “Polymer Materials with Spatially Graded Morphologies: Preparation,
Characterization and Utilization”, Adv. Nat. Sci., 1, 043003 (2010).
2011
1) T. Norisuye, S. Sasa, K. Takeda, M. Kohyama, Q. Tran-Cong-Miyata, “Simultaneous Evaluation of
Ultrasound Velocity, Attenuation and Density Polymer Solutions Observed by Multi-echo
Ultrasound by Multi-echo Ultrasound Spectroscopy”, Ultrasonics, 51, 215-222 (2011).
2) D.-T. Van-Pham, K. Sorioka, T. Norisuye and Q. Tran-Cong-Miyata, “Formation and Relaxation of
the Elastic Strain Generated by Photocuring in Polymer Blends Monitored by Mach-ZehnderInterferometry”, Polymer, 52, 739-745 (2011)3) K. Kinohira, D.-T. Van-Pham, A. Hirose, T. Norisuye, Q. Tran-Cong-Miyata, “ Phase Separation ofPolymer Mixtures Driven by Photochemical Reactions: Complexity and Fascination”, Current
Opinion in Solid State and Materials Science, 15, 254-261 (2011)4) K.-M. Nie, C.-M. Jing, H. Nakanishi, T. Norisuye, Q. Tran-Cong-Miyata, “Photoreaction-induced
Phase Separation and Morphology Control in Ternary IPNs Blends Involving 3D Spherical
Dendrimer”, Soft Matter, 7, 10556-10560 (2011)(b) Books
20091) Q. Tran-Cong-Miyata and H. Nakanishi, “Pattern Formation Induced by Chemical Reactions in
Polymeric Systems (in Japanese)” in “Handbook of Self-Organization”, T. Kunitake, M.
28

Shimomura, T. Yamaguchi Eds., NTS Publishing Company, Tokyo, pp. 249-252 (2009).
2) H. Nakanishi, T. Norisuye and Q. Tran-Cong-Miyata,“Morphosynthesis in Polymeric Systems
Using Photochemical Reactions” in “Molecular Nano Dynamics” Vol. I, H. Fukumura et al. Eds.,
Chapter 10, Wiley-VCH, Weinheim, pp. 173-186 (2009).
3) Q. Tran-Cong-Miyata and H. Nakanishi, “Phase Separation and Morphology of Polymer Mixtures
Driven by Light” in “Polymers, Liquids and Colloids in Electric Fields”, Y. Tsori and U. Steiner
Eds., Chapter 6, World Scientific, London, pp. 171 – 195 (2009).
20101) I. R. Epstein, John A. Pojman and Q. Tran-Cong-Miyata, “What is Nonlinear Dynamics and How
Does it Relate to Polymers?”, in “Nonlinear Dynamics with Polymers: Fundamentals, Methods andApplications”, J.A. Pojman and Q. Tran-Cong-Miyata Eds., Chapter 2, Wiley-VCH, Weinheim, pp.
5- 19 (2010).
2) H. Nakanishi, D. Fujiki, D.-T. Van-Pham and Q. Tran-Cong-Miyata, “Reaction-Induced Phase
Separation of Polymeric Systems under Stationary Nonequilibrium Conditions” in “Nonlinear
Dynamics with Polymers: Fundamentals, Methods and Applications”, J.A. Pojman and Q.
Tran-Cong-Miyata Eds., Chapter 6, Wiley-VCH, Weinheim, pp. 276-290 (2010).
(c) Reviews and Reports
2009
H. Nakanishi and Q. Tran-Cong-Miyata,“Light-Induced Self-Ordering Phenomena in Polymer
Mixtures (in Japanese)”, Kobunshi High Polymers, Japan ( published by the Society of Polymer
Science, Japan), Vol. 58 (No.7), 465-468 (2009).
(d) Awards
2010
D.-T. Van-Pham, T. Kinohira, Y. Arao, T. Norisuye and Q. Tran-Cong-Miyata, “Studies on Elastic
Strain and Its Relaxation Behavior in Photo-Cross-Linked Polymeric Systems Observed by
Mach-Zehnder Interferometry”, Students Poster Awards, International Symposium on Polymer
Physics, Ji-Nan, Shangdong, China, June 6-10 (2010).
(e) Invited Lectures
2007
1) Q. Tran-Cong-Miyata,“Reaction-Induced Elastic Deformation and Its Influence on Thermodynamic
Instabilities of Polymer Networks”, Lecture at the Cargèse Summer School on “Morphogenesis
through the Interplay of Nonlinear Chemical Instabilities and Elastic Active Media”, Institutd’Études Scientifiques de Cargèse, Corsica, France, July 2-14, 2007.
2) Q. Tran-Cong-Miyata, “How far Can We Control Morphology of Polymer Blends by Using
Chemical Reactions ?”, Invited talk at “The Second International Symposium on Polymer
Materials Science”, National Institute of Standards and Technology, Gaithersburg, Maryland,

29

U.S.A., December 10-11, 2007.
2008
1) Q. Tran-Cong-Miyata, “Co-continuous Morphology Resulting from Competing Interactions in
Reacting Polymer Blends and Its Practical Implication”, Invited Talk at the Materials Research
Science and Engineering Center (MRSEC), Northwestern University, April 4 (2008), Illinois, USA.
2) Q. Tran-Cong-Miyata, “Competing Interactions and Pattern Selection Driven by Chemical
Reactions in Polymer Mixtures”, Invited Talk at The 235th American Chemical Society, Division ofPolymer Materials Science (PMSE), April 6-10 (2008), New Orleans, U.S.A.
2009
Q. Tran-Cong-Miyata, “Co-continuous Morphologies of Polymer Blends: Generation, Design andApplication”, Invited Talk at The 5th JSPS Seminar on Asia-Africa Science Platform Program on
Neo-Fiber Technology, July 20-23 (2009), Ha-Noi University of Technology, Ha-Noi, Viet-Nam.
20101) Q. Tran-Cong-Miyata, “Polymers with Spatially Graded Continuous Morphology Generated by
Phase Separation under Spatially Non-uniform Conditions”, Invited Talk at the International
Symposium on Polymer Physics (PP-2010), June 6-10, 2010 Ji’nan, China.
2) Q. Tran-Cong-Miyata, "Light-Induced Phase Separation in Polymer Mixtures as a
Pattern-Formation Process: Complexity and Fascination", Invited Talk at the “Non-linear
Dynamics and Self-Organization in Chemical Systems”, 18 – 20, October (2010) – Centre deRecherche Paul Pascal, Bordeaux, France.
3) Q. Tran-Cong-Miyata, “Some Recent Findings in Phase Separation of Reacting Polymer Mixtures”,
Invited Talk at The 4th International Symposium on Polymer Materials Science, National Instituteof Technology (NIST), Gaithersburg, Maryland, USA, October 28-29 (2010).
20111) Q. Tran-Cong-Miyata, “Phase Separation of Photo-reactive Polymer Mixtures:Complexity andFascination”, High Polymer Research Group Conference “Stimuli Responsive and Reactive
Polymer Systems”, Pott Shrigley, United Kingdom, April 17-21 (2011).
2) T. Norisuye, "Dynamics of microsphere suspensions observed by ultrasound technique", Tokai
Polymer Student Forum, sponsored by The Society of Polymer Science, Tokai Branch, Japan,
Nagoya, March 5th (2011).
3) T. Norisuye, "Dynamics of Microspheres Suspension Observed by Dynamic Ultrasound Scattering",
56th Symposium on Acoustics and Physics, Kyoto, July 28 (2011)4) T. Norisuye, "Dynamics of microsphere suspensions by dynamic ultrasound scattering method",The 23rd Workshop of Scattering Techniques, Tokyo, Nov. 11-12 (2011)(f) Patents
20071) Q. Tran-Cong-Miyata, H. Nakanishi, M. Satoh, “Novel Fabrication Methods of Multiphase
Polymeric Materials”, Japanese Patent Appl. No. 2007-191648 , assigned to Kyoto Institute of30

Technology (Aug. 2007).
2) Q. Tran-Cong-Miyata, S. Ishino, H. Nakanishi, E. Ueda, “A Novel Fabrication Methods ofMultiphase Polymeric Materials Using Computer-Assisted Irradiation Method”, Japanese PatentAppl. No. 2007-238641 , assigned to Kyoto Institute of Technology (Aug. 2007).
2009
T. Norisuye, “Dynamic ultrasound scattering apparatus and the characterizing methods for
microsphere suspensions”, Japanese Patent Appl. No. 2009-114873 (2009), assigned to Kyoto
Institute of Technology (2009).
g) Research Funds and Financial Supports
20071) Q. Tran-Cong-Miyata (Principal Investigator) and T. Norisuye, Grants-in-Aid for Scientific
Research on Priority Area “Soft Matter Physics”, Ministry of Education (MONKASHO), Japan No.
19031018, “Phase Separation Dynamics of Polymer Mixtures Temporally and Spatially Driven by
Photochemical Reactions and Its Application to Materials Designing”
2) T. Norisuye, Grants-in-Aid for Young Scientists (Type B), Ministry of Education (MONKASHO),Japan No.18750190, "Studies on the bubble dynamics in viscoelastic polymer solutions by meansof dynamics ultrasound scattering method".
3) T. Norisuye, Japan Regional Innovation Strategy program by the Excellence, 10-007,"Non-destructive analysis of soft matter by means of novel ultrasound techniques"
2008
1) Qui Tran-Cong-Miyata (Principal Investigator) and Tomohisa Norisuye, Grant-in-Aid for Scientific
Research on Priority Area “Soft Matter Physics”, Ministry of Education (MONKASHO), Japan No.
19031018, “Phase Separation Dynamics of Polymer Mixtures Temporally and Spatially Driven by
Photochemical Reactions and Its Application to Materials Designing”
2) Qui Tran-Cong-Miyata, Grant-in-Aid for Scientific Research (Type B), Ministry of Education(MONKASHO), Japan No.20350107, “Novel Design of Multi-Components Polymers with
Co-continuous Morphologies and Controlling Dispersion of Multi-walled Carbon Nanotubes”.
3) T. Norisuye, Grants-in-Aid for Young Scientists (Type B), Ministry of Education (MONKASHO),Japan No. 20750178, "Novel techniques and its applications for microspheres by means ofdynamics ultrasound scattering method".
20091) Qui Tran-Cong-Miyata (Principal Investigator) and Tomohisa Norisuye, Grant-in-Aid for Scientific
Research on Priority Area “Soft Matter Physics”, Ministry of Education (MONKASHO), Japan, No.
21015018, “Phase Separation Dynamics of Polymer Mixtures Temporally and Spatially Driven by
Photochemical Reactions and Its Application to Materials Designing2) Qui Tran-Cong-Miyata, Grant-in-Aid for Scientific Research (Type B), Ministry of Education(MONKASHO), Japan No.20350107, “Novel Design of Multi-Components Polymers with
Co-continuous Morphologies and Controlling Dispersion of Multi-walled Carbon Nanotubes”.
313) T. Norisuye, Grants-in-Aid for Young Scientists (Type B), Ministry of Education (MONKASHO),Japan No. 20750178, "Novel techniques and its applications for microspheres by means ofdynamics ultrasound scattering method".
20101) Qui Tran-Cong-Miyata (Principal Investigator) and Tomohisa Norisuye, Grant-in-Aid for Scientific
Research on Priority Area “Soft Matter Physics”, Ministry of Education (MONKASHO), Japan, No.
21015018, “Phase Separation Behavior of Polymer Mixtures Under Stationary Non-Uniform
Experimental Conditions Driven by Computer-Assisted Irradiation Method”
2) Qui Tran-Cong-Miyata, Grant-in-Aid for Scientific Research (Type B), Ministry of Education(MONKASHO), Japan No.20350107, “Novel Design of Multi-Components Polymers with
Co-continuous Morphologies and Controlling Dispersion of Multi-walled Carbon Nanotubes”.
3) T. Norisuye, Grants-in-Aid for Young Scientists (Type B) 22750205, "Dynamics UltrasoundScattering analysis for sub micron particles in the presence of the acoustic radiation field".
20111) Q. Tran-Cong-Miyata, Grant-in-Aid for Scientific Research (Type C), Ministry of Education(MONKASHO), Japan No. 23550241, “Designing Polymer Materials with Programmable Surfaces
Constructed by Spatially Graded Morphology Generated by Photochemical Reactions”
2) T. Norisuye, Grants-in-Aid for Young Scientists (Type B), Ministry of Education (MONKASHO),Japan, No. 22750205, "Dynamics Ultrasound Scattering analysis for sub micron particles in thepresence of the acoustic radiation field".

32Fibrous Material Science Laboratory
Takashi ITOH, Dr., Prof.
Susumu FUJIWARA, Dr., Associate Prof.
Masato HASHIMOTO, Dr., Assistant Prof.
I. Researches
Polymer crystals usually take imperfect structures because polymer chains are long enough. In
general, the so-called crystalline polymers exhibit complex and hierarchical structures on the basis ofsuch imperfect crystals. Polymer solids therefore form various higher-order structures and have a wide
range of physical and chemical properties. In this laboratory, we systematically study the relationshipbetween the structures of polymer solids and their physical properties by utilizing experimental
methods, such as various electron microscopes, X-ray analysis, optical microscopes, optical scattering,
infrared absorption, electric measurement, mechanical measurement, thermal analysis and computer
simulation. The main research themes are as follows.
1.

Phase transition in polymer crystals
Various experimental methods such as electron microscopes, X-ray analysis, infrared absorption,

electric measurement, mechanical measurement and thermal analysis are used to study the reversible
crystal phase transition and the irreversible crystal phase transition. We believe that the investigationof the mechanisms of such phase transitions will provide a hint to the development of new materials
with desired properties.
2. Crystal growth of polymers
Various experimental methods such as optical microscopes and atomic force microscopes are used
to study the effect of thermal history on polymer crystal growth from the melt, the microscopic growthmechanisms of single polymer crystals and the numerical quantification of polymer crystal
morphologies through image processing. We also investigate the melt memory effect on polymer
spherulites and mechanism of cavitation in the polymer melt (Figs.1 and 2).

Fig.1. Cross-polarized optical micrograph of

Fig.2. Optical micrograph of cavities with theisotactic polystyrene spherulites in a sample

viscous fingering in atactic polystyrene melt.

partially sandwiching gold coating.
33

3. Structure formation of polymers and amphiphilic molecules
Computer simulations are carried out to study the structure formation of polymers and amphiphilicmolecules. In particular, structure formations of an isolated single polymer chain (Fig. 3), isolated
short chain molecules and a single polymer chain in solution as well as the spontaneous micelleformation and mesophase formation in amphiphilic solution (Fig. 4) are investigated. Moreover, we
aim at exploring the universal self-organizing properties in nature through the clarification of themechanisms of structure formation in soft matter systems such as polymeric and amphiphilic systems.

Fig.3. Computer simulation for structure

Fig.4. Computer simulation for spontaneous

formation of an isolated single polymer

micelle formation and mesophase formation inchain.

amphiphilic solution.

II. Publications and Achievements(a) Original papers
20071) Thuy-Trang Hua, T. Itoh, Jian-An HOU, S. Fujiwara and M. Hashimoto, “Freezing ofHigh-Temperature Phase in Vinylidene Fluoride/Trifluoroethylene Copolymer Crystals on
Vacuum-Evaporated Metal Surfaces”, Jpn. J. Appl. Phys., 46, L1170-L1172 (2007).
2) Thuy-Trang Hua, T. Itoh, S. Fujiwara and M. Hashimoto, “Superlattice Epitaxy of Vinylidene
Fluoride/Trifluoroethylene Copolymer Crystals on Highly Oriented Pyrolytic Graphite”, J. Phys.
Soc. Jpn. 76, 124604 (2007).
3) H. Fukumura, S. Matsui, H. Harima, T. Takahashi, T. Itoh, K. Kisoda, M. Tamada, Y. Noguchi and
M. Miyayama, “Observation of phonons in multiferroic BiFeO3 single crystals by Raman
scattering”, J. Phys.: Condens. Matter, 19, 365224 (2007).
4) S. Fujiwara, T. Itoh, M. Hashimoto and Y. Tamura, “Molecular dynamics simulation of micelleformation in amphiphilic solution”, Mol. Simul. 33, 115-119 (2007).
20091) Y. Okubo, S. Mori, K. Yamamoto, D. Hamada, H. Kohno, K. Fujiwara, M. Hashimoto, K. Ikeuchi
and N. Tomita, “Mechanical Interaction between Vitamin E-Containing Ultrahigh Molecular

34

Weight Polyethylene and Co-28Cr-6Mo Alloy in Water”, J. Biomech. Sci. Eng. 4, 166-173 (2009).
2) S. Fujiwara, M. Hashimoto and T. Itoh, “Molecular Dynamics Simulations for Structure Formationof Polymers and Self-Assembly of Amphiphilic Molecules (in Japanese)”, Kobunshi Ronbunshu 66,
396-405 (2009).
3) T. Takahashi, T. Itoh, S. Fujiwara and M. Hashimoto, “Novel Primary Dispersion in Viscoelastic
Behavior of Ferroelectric Nylon 6”, Polymer J. 41, 354-355 (2009).
4) S. Fujiwara, T. Itoh, M. Hashimoto and R. Horiuchi, “Molecular dynamics simulation ofamphiphilic molecules in solution: Micelle formation and dynamic coexistence”, J. Chem. Phys.
130, 144901 (2009).
20101) H. Nakamura, A. Ito, S. Saito, Y. Tamura, S. Fujiwara, N. Ohno and S. Kajita, “Comparison with
Surfaces of Diamond and Graphite for Adsorption of Hydrogen Solution”, Plasma Fusion Res. 5,
S2072 (2010).
2) Y. Tamura, S. Fujiwara and H. Nakamura, “Haptization of molecular dynamics simulation withthermal display”, Plasma Fusion Res. 5, S2107 (2010).
3) S. Fujiwara, T. Itoh, M. Hashimoto, H. Nakamura and Y. Tamura, “Effect of Molecular Rigidity on
Micelle Formation in Amphiphilic Solution”, Plasma Fusion Res. 5, S2114 (2010).
4) K. Sogo, Y. Kishikawa, S. Ohnishi, T. Yamamoto, S. Fujiwara and K. M. Aoki, “Correlated
Anomalous Diffusion - Random walk and Langevin equation -”, J. Math. Phys. 51, 033302 (2010).
20111) M. Segawa, H. Kuromitsu and T. Itoh, “Change in Surface Morphology of Polyvinyl Chloride
Extracorporeal Circulation Pump Tube Caused by Roller-pump Stress (in Japanese)”, Transactionsof Japanese Society for Medical and Biological Engineering, 49, 544-550 (2011).
2) R. Shirasaki, Y. Yoshikai, H. J. Qian, S. Fujiwara, Y. Tamura and H. Nakamura, “Dissipative
Particle Dynamics Simulation of Phase Behavior in Bolaamphiphilic Solution”, Plasma Fusion Res.
6, 2401116 (2011).
3) Y. Tamura, K. Ukita, N. Mizuguchi and S. Fujiwara, “Design Support System with Haptic Feedback
and Real-Time Interference Function”, Plasma Fusion Res. 6, 2406061 (2011).
4) S. Fujiwara, T. Itoh, M. Hashimoto, Y. Tamura, H. Nakamura and R. Horiuchi, “Molecular
Dynamics Simulation of Micellar Shape Change in Amphiphilic Solution”, Plasma Fusion Res. 6,2401040 (2011).
5) Y. Tamura, S. Fujiwara, T. Umetani and H. Nakamura, “Bracelet shaped thermal display for
representing numerical data”, J. Electron. Mater. 40, 823-829 (2011).
6) S. Fujiwara, D. Funaoka, T. Itoh and M. Hashimoto, “Molecular dynamics simulation for phasebehavior of amphiphilic solution”, Comput. Phys. Commun. 182, 192-194 (2011).
(b) Books
2008
S. Fujiwara, in “At Home in the Universe (in Japanese)”, pp. 191-371, (translation of “At Home in35

the Universe” written by S. Kauffman), Chikuma Shobo (2008).
(c) Reviews and Reports
2007
S. Fujiwara, M. Hashimoto, T. Itoh and Y. Tamura, “Molecular Dynamics Simulation of Micelle
Formation in Amphiphilic Solution: Identification of Micellar Shape”, Annual Report of National
Institute for Fusion Science, April 2006 - March 2007, p. 367 (2007).
2008
1) S. Fujiwara, M. Hashimoto, T. Itoh and R. Horiuchi, “Molecular Dynamics Simulation ofAmphiphilic Molecules in Solution: Mesophase Formation”, Annual Report of National Institutefor Fusion Science, April 2007 - March 2008, p. 359 (2008).
2) S. Fujiwara, “Capillarity and Wetting Phenomena: Drops, Bubbles, Pearls, Waves (in Japanese)”,(book review) BUTSURI 63, 965-966 (2008).
2009
S. Fujiwara, M. Hashimoto, T. Itoh and R. Horiuchi, “Molecular Dynamics Simulation of Micelle
Formation in Amphiphilic solution: Dynamic Coexistence of Micellar Shapes”, Annual Report ofNational Institute for Fusion Science, April 2008 - March 2009, p. 319 (2009).
20101) S. Fujiwara, T. Itoh, M. Hashimoto, H. Nakamura, R. Horiuchi and Y. Tamura, “Dynamics
Simulation of Micelle Formation in Amphiphilic solution: Effect of Molecular Rigidity”, Annual
Report of National Institute for Fusion Science, April 2009 - March 2010, p. 346 (2010).
2) S. Fujiwara, “Large-Scale Molecular Simulation of Higher-Order Structure Formation by
Amphiphilic Molecules”, Activity Report 2009, Supercomputer Center, MDCL ISSP University ofTokyo, p. 211 (2010).
20111) S. Fujiwara, T. Itoh, M. Hashimoto, H. Nakamura, R. Horiuchi and Y. Tamura, “Molecular
Dynamics Simulation of Micellar Shape Change in Amphiphilic Solution: Effect of Molecular
Rigidity”, Annual Report of National Institute for Fusion Science, April 2010 - March 2011, p. 389(2011).
2) S. Fujiwara, R. Maruyama, T. Itoh, M. Hashimoto and R. Horiuchi, “Molecular Dynamics
Simulation of Melting Process in n-Nonane Ultrathin Films”, Annual Report of National Institutefor Fusion Science, April 2010 - March 2011, p. 390 (2011).
3) S. Fujiwara, “Molecular Simulation of Higher-Order Structure Formation by Amphiphilic
Molecules”, Activity Report 2010, Supercomputer Center, MDCL ISSP University of Tokyo, p. 203(2011).
(d) Awards

36

(e) Invited Lectures
2007
S. Fujiwara, “Structure and Formation Dynamics of Polymer Crystals (in Japanese)”, 12th Annual
Meeting of the Research Group on Computational Polymer Science, The Society of Polymer
Science, Japan (2007).
2008
1) S. Fujiwara, “Molecular Dynamics Simulation of Ordering Processes in Polymer Systems (inJapanese)”, Joint Symposium of the fieds 9 and 12, 2008 Autumn Meeting of the Physical Societyof Japan (2008).
2) S. Fujiwara, “Molecular Dynamics Simulations for Structure Formation of Polymers andSelf-Assembly of Amphiphilic Molecules (in Japanese)”, 2nd Public Symposium of theGrant-in-Aid for Scientific Research on Priority Area “Soft Matter Physics” (No. 463) 2006-2010,
Ministry of Education, Culture, Sports, Science and Technology of Japan (2008).
2011
S. Fujiwara, “Molecular Dynamics Study on Structure Formation of Polymers and Self-Assemblyof Amphiphilic Molecules (in Japanese)”, Joint Seminar of the Theoretical Groups, Tokyo
University of Pharmacy and Life Sciences (2011).
(f) Patents(g) Funds and Financial Supports
2007
S. Fujiwara, Grant-in-Aid for Scientific Research on Priority Area “Soft Matter Physics”, Public
Participation Research 19031019, “Theoretical and Simulational Study of Soft Matter Interfaces”.
2008
S. Fujiwara, Grant-in-Aid for Scientific Research on Priority Area “Soft Matter Physics”, Public
Participation Research 19031019, “Theoretical and Simulational Study of Soft Matter Interfaces”.
2010
S. Fujiwara, Grant-in-Aid for Scientific Research, Scientific Research (C) 22540419,“Investigation of the Mechanisms of Surface Melting and Surface Freezing of n-Alkane Uultrathin
Films by Large-Scale Molecular Simulation”.
20111) T. Itoh, Research Grant, Mitsuboshi Belting Ltd.
2) S. Fujiwara, Grant-in-Aid for Scientific Research, Scientific Research (C) 22540419, “Investigationof the Mechanisms of Surface Melting and Surface Freezing of n-Alkane Uultrathin Films by
Large-Scale Molecular Simulation”.

37

Polymer Mechanics Laboratory
Masaoki TAKAHASHI, Dr., Prof.
Yukihiro NISHIKAWA, Dr., Associate Prof.
I. Researches
1. Structure-Rheology Relationships
The objectives of this field of research are:1) To clarify relationships between structure and rheology in polymer alloys and blends, and
2) To clarify relationships among structure, rheology and functionality in polymer composites.
The following investigations have been made for each objective.
1) Relationships between structure and viscoelasticity in immiscible polymer blendsExperimental observation of droplet-phase deformation was made under external step-shear strains,and shape recovery of the droplet due to the interfacial tension was analyzed. The interface tensor, or
the anisotropy of interface under the strain, was calculated from the observed droplet shape (flatellipsoid, rod-like, dumbbell and spheroid). Based on the Doi-Ohta theory, this calculation of theinterface tensor enabled us to predict the stress tensor for the deformed interface. The predicted stressagreed with experimental data fairly well for polymer blends with small and large interfacial tensions
and with narrow and broad distribution of droplet size. This way of predicting the stress tensor fromthe observed shape of interface has been extended to polymer blends with bicontinuous(co-continuous) structure. 3D images of deformed interface of bicontinuous structure have been
observed, utilizing a high-contrast X-ray CT developed by Nishikawa et al. The interface and stresstensors are now in the process of calculation from the observed 3D images.
In the Doi-Ohta theory, only the Laplace pressure term was considered and the interface velocity term
was neglected in calculating the stress tensor for the interface. We calculated the interface velocity
term in the step-strain test and evaluated the effect of the term. Inclusion of this term resulted in better
agreement of the prediction with experimental data in the final stage of stress relaxation.
From observation of two deformed droplets at a short distance, we found coalescence of the droplets
under large step shear strains. Hydrodynamic interactions between deformed droplets were analyzed
and the coalescence was explained from the predicted matrix flows between and around the droplets.
2) Relationships among structure, viscoelasticity and functionality in polymer (blend) composites
When fillers are mixed into binary polymer blend melts, the fillers are localized in one phase of thepolymer blend. We found that nanocarbons are localized in a polymer phase with lower interfacial
energy between nanocarbon and polymer component. There are a few exceptions for polymer blendswith very different chain-flexibility. Flexible polymers such as high density polyethylene andpolypropylene can adsorb onto rough surfaces of carbon black and rough ends of carbon nanofibers(VGCFs) without great loss of entropy (entropy penalty). Polymer blends with bicontinuous structure
were found to be good templates for network formation of nanocarbons, zirconia, alumina and silver
particles. In immiscible polymer blends, bicontinuous structure usually appears when i) the interfacial
tension between polymer components is small, ii) the viscosity of the components is comparable and38iii) the composition is around 50:50. By utilizing the bicontinuous structure as a template forpercolation network, the critical fraction of filler for percolation can be reduced to half (or smaller
than that in a favorable case), compared with the fraction in a composite with a single polymer matrix(either component). Network formation of fillers results in appearance of plateau region in the storage
modulus at low frequencies. In case of conductive fillers, network formation enhances electricaland/or thermal conductivity. Localization of nanocarbons at the interface of bicontinuous structure will
be an ultimate technique to enhance the electrical conductivity, and this method is under investigation.
2. 3D Microscopy and 3D Image Analyses
In order to understand the relationship between the mechanical properties and the structures inpolymeric systems, the structural analysis is the other end of the research field as well as therheological studies. For this purpose, we propose the concept of three-dimensional (3D) microscopy(3D-scopy). In 3D-scopy, the 3D image of the microscopic structure of the material is obtained bysomehow, such as confocal microscopy, transmission electron microtomography, and X-ray
computerized tomography (CT), and then the 3D image is subjected to the 3D image analysis. Since
the 3D image includes all structural aspects in a given spatial resolution, 3D-scopy can be an ultimate
structural analysis method. Recently, we concentrate ourselves to the researches on X-ray CT. X-ray
CT has been considered to be inappropriate in polymer science since most of polymers are transparent
to X-rays. However, we developed a high-contrast X-ray CT and concluded that X-ray CT has asufficient contrast-performance to resolve the difference of the polymer species. Now X-ray CT is an
emerging research tool in polymer science. Studies on X-ray CT consist of the development and theapplication of X-ray CT.
Development of X-ray CT includes the theoretical study of reconstruction method, developing thereconstruction software, the technical design of the X-ray CT hardware, and studies on the sample
preparations. As the theoretical study, we proposed a novel reconstruction technique based on Monte
Carlo method, which is completely different from the standard reconstruction method, filtered
back-projection (FBP), and has a lot of advantages to FBP. We also develop new X-ray CT apparatusesin collaboration with several companies in order to achieve high spatial resolutions.
Thus developed X-ray CT is applied to many polymer systems, such as, the binary and ternary
polymer blends, the glass-fiber or carbon-fiber or cellulose-fiber composites, the form materials, andso on. The X-ray CT is applicable to the opaque samples which is one of the big advantages of X-ray
CT in comparison to light scattering and confocal microscopy. Typical applications are PS/PMMA
blends and composites. Polymer foams are also an important topic for X-ray CT. The buckling of thefoam cells under compression was three-dimensionally observed by X-ray CT for the first time. The
phase-separation structures in ternary polymer blends were systematically surveyed by X-ray CT, anda lot of new morphologies were discovered.
Generally, 3D-scopy provides the 3D images of the objects. The analysis of the 3D images is also
important research field. At this moment, we can perform network analysis, particle analysis, distanceanalysis, and orientation analysis in 3D. Other analysis techniques are still under investigation.

39

II. Publications and Achievements(a) Original papers
20071) M. Takahashi, P. H. P. Macaubas, K. Okamoto, H. Jinnai and Y. Nishikawa, “Stress Prediction for
Polymer Blends with Various Shapes of Droplet Phase”, Polymer, 48, 2371-2379 (2007).
2) M. Takahashi, S. Osawa, H. Jinnai, H. Yamane and H. Shiomi, “Dispersion State of Zirconium
Oxide Particles in Polymer Blends and Viscoelastic Behavior of the Composites”, J. Soc. Rheology,
Japan, 35, 1-9 (2007).
3) P. H. P. Macaubas, H. Kawamoto, M. Takahashi, K. Okamoto, and T. Takigawa, “Shape andStructure Recovery of an LCP Droplet under a Large Step Strain: Observation and StressCalculation”, Rheol. Acta, 46, 921-932 (2007).
4) M. Takahashi and K. Okamoto, “Retraction of Rod-like and Spheroidal Droplets and Stress
Relaxation after Step Shear Strain in Polymer Blends”, J. Soc. Rheology, Japan, 35, 199-205(2007).
5) M. Takahashi, “Study on Structure-Rheology Relationships in Multiphase Polymeric Systems”, J.
Soc. Rheology, Japan, 35, 235-244 (2007).
6) T. Hashimoto, Y. Nishikawa, K. Tsutsumi, “Identification of the Voided Double-Gyroid-Channel:
A New Morphology in Block Copolymers”, Macromolecules, 40, 1066-1072 (2007).
7) S. Koizumi, Y. Yamane, S. Kuroki, I. Ando, Y. Nishikawa, H. Jinnai, “Three-dimensional
Observation of Phase-separated Poly(methyl methacrylate)/Poly(styrene-ran-4-bromostyrene)
Blends by 3D NMR Microscopy with X-ray Microscopy”, J. Appl. Polym. Sci., 103(1), 470-475(2007).
8) H. Saito, K. Kanamori, K. Nakanishi, K. Hirao, Y. Nishikawa, H. Jinnai, “Three-dimensional
Observation of Macroporous Silica Gels and the Study on Structural Formation Mechanism”,
Colloid. Surface A, 300, 245-252 (2007).
2008
1) K. Okamoto and M. Takahashi, “Effects of Interface Velocity on the Stress Tensor in Immiscible
Polymer Blends: Retraction of Spheroidal Droplets and Stress Relaxation”, J. Soc. Rheology,
Japan, 36, 43-49 (2008).
2) K. Okamoto, K. Iwase, M. Ishikawa, M. Takahashi, “Effects of Droplet Size and Volume Fraction
on Relaxation Modulus of Immiscible Polymer Blends: Inclusion of Interface Velocity Term”, J.
Soc. Rheology, Japan, 36, 117-123 (2008).
3) K. Okamoto S. Iwatsuki, M. Ishikawa and M. Takahashi, “Hydrodynamic Interaction andCoalescence of Two Droplets under Large Step Shear Strains”, Polymer, 49, 2014-2017 (2008).
4) K. Okamoto and M. Takahashi, “Shear and Normal Stress Relaxation in Polymer Blends: StressPredictions from Interface Velocity and Laplace Pressure Terms”, Rheol. Acta, 47, 797-805(2008).
2009
K. Okamoto, M. Yamaguchi, M. Takahashi, “Hydrodynamic Interaction Model for two Droplets40

under Large step Shear Strains”, J. Soc. Rheology, Japan, 37, 121-128 (2009).
20111) Y. Nishikawa, N. Ohta, Y. Komasu, M. Takahashi, “Application of High-contrast X-ray
Computerized Tomography to Carbon Fiber/Polymer Composites (in Japanese)”, J. Soc. Mat. Sci.,
Japan, 60(1), 29-34 (2011).
2) Y. Nishikawa, S. Baba, M. Takahashi, “Optimization of X-ray Computerized Tomography for
Polymer Materials”, Intl. J. Polym. Mat., in press.
(b) Books
2011
Y. Nishikawa and M. Takahashi, “Observation of Polymer Materials by using X-ray Computerized
Tomography (in Japanese)” in “Pastics Age Encyclopedia shinpo-hen 2012” pp. 105-110, Plastics
Age Co. Ltd. (2011).
(c) Reviews and Reports
2007
M. Takahashi, H. Okumura, J. Matsubayashi, Y. Nishikawa, “Flow Induced Orientation of
Microphase Separated Structure and Rheology in Block Copolymers (in Japanese)”, Annual
Report of the Research Institute for Chemical Fibers, Japan, 64, 77-86 (2007).
20081) M. Takahashi, “Structure and Rheology of Multiphase Polymeric Systems (in Japanese)”,Chemical Engineering, 53, 24-29 (2008).
2) M. Takahashi, “Progress in 10 years: Fundamental Properties of Polymer Melts (in Japanese)”, J.
Japan Society of Polymer Processing (Seikei Kakou), 20, 527-532 (2008).
3) M. Takahashi, K. Kimura, T. Sudo and S. Osawa, “Dispersion Control of Particles Utilizing Phase
Separated Structure of Polymer Blends (in Japanese)”, Annual Report of the Research Institute for
Chemical Fibers, Japan, 65, 66-72 (2008).
2009
M. Takahashi, K. Okamoto and P. H. P. Macaubas, “Prediction of Stress Tensor Resulting from
Deformed Interface in Polymer Blends and Comparison with Experimental Data (in Japanese)”,Annual Report of the Research Institute for Chemical Fibers, Japan, 66, 75-81 (2009).
20101) M. Takahashi, Y. Nishikawa, N. Mukai, R. Ishikawa and K. Kimura, “High-performing
Electromagnetic-Wave Absorber: Network Formation of Nanocarbons Utilizing Selective
Adsorption of Polymer Chains and Phase Separated Structure (in Japanese)”, Annual Report of the
Research Institute for Chemical Fibers, Japan, 67, 78-85 (2010).
2) Y. Nishikawa and M. Takahashi, “Electrical Conductivity, Mechanical Property, and Structure in
Carbon Nano-fiber/Polymer Composites (in Japanese)”, Chemical Engineering, 55(9), 665-669(2010).
4120111) M. Takahashi and Y. Nishikawa, “3D Structure Observation by X-ray CT (in Japanese)”, J.
Adhesion Soc. Japan (Adhesion), 47(11), 453-459 (2011).
2) M. Takahashi, Y. Nishikawa, H. Hatakeyama and H. Taniyama, “3D Structure Observation by
X-ray CT and Rheology for Polymer Blends with Bicontinuous Structure (in Japanese)”, Annual
Report of the Research Institute for Chemical Fibers, Japan, 68, 77-84 (2011).
(d) Awards
2007
M. Takahashi, The SRJ Award (The Society of Rheology, Japan), “Study on Structure-Rheology
Relationships in Multiphase Polymeric Systems”.
(e) Invited Lectures
2007
M. Takahashi, “Study on Structure-Rheology Relationships in Multiphase Polymeric Systems(Award Lecture)”, 34th Annual Meeting of the Society of Rheology, Japan (2007).
2010
M. Takahashi, “Viscoelasticity of Copolymers and Polymer Blends with Bicontinuous and Other
Structures”, ISSP International Workshop on Soft Matter Physics, University of Tokyo, Aug. 9-13
(2010)(f) Patents
20111) Y. Nishikawa, “Image Reconstruction Method, Image Reconstruction Apparatus, Image
Reconstruction Program, Computerized Tomography Apparatus”, US Patent No. 8090182.
2) Y. Nishikawa, “Image Reconstruction Method, Image Reconstruction Apparatus, Image
Reconstruction Program,

Computerized Tomography Apparatus”, Chinese

PatentNo.

ZL200780038491.7.
3) T. Kishi, Y. Nishikawa, “Image Reconstruction Method and Image Reconstruction Apparatus”,
Japanese Patent Publication No. 2010-99535.
4) T. Kishi, Y. Nishikawa, “Image Reconstruction Method and Image Reconstruction Apparatus”,
Japanese Patent Appl. No. 2011-088493.
(g) Funds and Financial Supports
2007
M. Takahashi, Grant-in-Aid for Scientific Research, Scientific Research (B) 18350119, “Invention
of Electromagnetic-wave Absorbing Composites Utilizing Bicontinuous Polymer Structure andPercolation of Nano-carbons”.

42

2009
1) Y. Nishikawa, Grant-in-Aid for Challenging Exploratory Research (B) 21750219, “Developmentof Spindle Method for X-ray Computerized Tomography with Nanometer-scale Spatial
Resolution.”2) S. Baba, Y. Nishikawa, JST Chiiki-niizu Sokuougata, “Development of X-ray Computerized
Tomography for Electric Devices.”20101)

M. Saigan, Y. Nishikawa, JST A-STEP Feasibility Study AS2211139F, “Metal Artifact Reductionof Dental X-ray Computerized Tomography.”2)

M. Takahashi, KIT-KANEKA Comprehensive Cooperation Research Project (2010-2011).

43

Textile Engineering Design Laboratory
Ryuichi AKIYAMA, Dr., Prof.
Katsufumi TANAKA, Dr., Associate Prof.
Haruki KOBAYASHI, Dr., Assistant Prof.
I. ResearchesPhysical Properties of Liquid Crystals (Figs.1, 2)Sensory Test for Textile Products (Fig.3)

The Electro-Rheological Effect of Nano- Suspensions (Figs.4, 5)

Structure and Physical Properties of Liquid Crystalline Polymers, Nano-Particles andNano-Fibers in Polymers

Mechanical Properties of Nanofiller-Dispersed Materials (Figs.6, 7)

Physical Properties of Liquid Crystals and Sensory Test for Textile Products

Fig.1 SEM micrograph ofa mat of nano-fibers

Fig.2 Polarized optical
micrograph of a particle
network developed froma mixture of 8CB/HEMA
after UV curing.

Fig.3 Sensory Test for
Textile Products.

The Electro-Rheological Effect of Nano- Suspensions

Fig.4 The ER effectFig.5 A chain-like microstructure
under an electric field.

The electro-rheological effect (the ER effect) is the reversible rheological responses of fluids only
by application and removal of an external electric field. The mechanical output can be controlled
simply by desirable information as electrical signals superposed upon the electric field (Fig.4). The
nano-suspension composed of polarizable nano-particles and insulating oil is known to show the ER
effect. Microstructures such as chain-like one or ring-like one are closely related to the ER effect(Fig.5). The physical properties of such ER nano-susupensions and composites are studied in relation
to the microstructures developed under electric and/or shear fields.
44

Mechanical Properties of Nanofiller-Dispersed Materials
Objective:
Our goal is to improve mechanical properties of polymer materials by adding nano-fillers.
Approach:· To quantify the mechanical properties, various types of mechanical tests (tensile, bending,compressive, fracture toughness, fatigue, wear, and so on) are being conducted.
· Statistical analyses are being performed on the data of mechanical tests.
· Morphological changes are being assessed using x-ray techniques and optical and electricalmicroscopies.

Fig. 6 Schematic illustrations of surfacenotched
specimenfor
SAXS
measurements (a), changes of shape of
specimen during tensile deformation (b),and geometry of time-resolved SAXS
measurements
duringtensiledeformation (c).

Fig. 7 Integrated intensity Q (circle)
and load of film (broken line) versus
extension of film for neat PET film (a),CB (2 wt %)/PET composite film (b),MWCNT-I (1 wt %)/PET composite film(c) and MWCNT-II (2 wt %)/PET
composite film (d).
(Figures 6 and 7 are cited from J. Appl.

Polym. Sci., 106, 152-160 (2007).)45

II. Publications and Achievements(a) Original papers
20071) K. Tanaka, T. Morina, Y. Tanabe, and R. Akiyama, “Concentration dependences of dielectric
properties at 105 Hz and 106 Hz for aqueous solutions of hydroxypropyl cellulose”, Liq. Cryst., 34,
1019-1028 (2007).
2) K. Tanaka, H. Nakahori, K. Katayama, and R. Akiyama, “Linear viscoelastic properties ofelectro-rheological nano-suspension confined to narrow gap between electrodes”, Colloid Polym.
Sci., 285, 1201-1211 (2007).
3) H. Kobayashi, M. Shioya, T. Tanaka, T. Irisawa, S. Sakurai and K. Yamamoto, “A Comparative
Study of Fracture Behavior between Carbon Black/PET and Multi-Walled Carbon Nanotube/PET
Composite Films”, J. Appl. Polym. Sci., 106, 152-160 (2007).
4) H. Kobayashi, M. Shioya, T. Tanaka and T. Irisawa., “Synchrotron Radiation Small-angle X-ray
Scattering Study on Fracture Process of Carbon Nanotube/Poly(ethylene terephthalate) Composite
Films”, Comp. Sci. Tech., 67, 3209-3218, (2007).
5) H. Kobayashi, M. Shioya, J. Yamashita and T. Hirano, “Formation Mechanism of Pores Containedin PVDF-based Carbon Films Derived through Chemical and High-temperature Heat-treatments”,
Sen-i Gakkaishi, 63, 152-158, (2007).
2008
1) K. Tanaka, Y. Tanabe, T. Morina, and R. Akiyama, “In-situ monitoring of a film preparation process
for hydroxypropyl cellulose cast from isotropic aqueous solution using microdielectrometry”, Liq.
Cryst., 35, 253–264 (2008).
2) K. Tanaka, Y. Tanabe, and R. Akiyama, “Microdielectrometric monitoring of film preparation
process with oriented domains for hydroxypropyl cellulose cast from isotropic aqueous solution
under the sinusoidal electric field with large amplitude”, Liq. Cryst., 35, 937-951 (2008).
3) K. Kitano, M. Chino, K. Tanaka, and R. Akiyama, “Electro-optical properties of liquid crystal –Polyacrylonitrile fiber composites”, Liq. Cryst., 35, 1225-1235 (2008).
20091) K. Tanaka, N. Sezaki, H. Nakahori, and R. Akiyama, “Apparent yield stresses and microstructuresof electro-rheological nano-suspensions under no external electric fields”, Nihon Reoroji Gakkaishi,
37, 17-23 (2009).
2) S. Kutsumizu,, K. Hosoyama, M. Yamada, K. Tanaka, R. Akiyama, S. Sakurai, and E. Funai,“Smectic C to cubic phase transition of 4'-n-docosyloxy-3'-nitrobiphenyl- 4-carboxylic acid
(ANBC-22) and AC electric field effect”, J. Phys. Chem. B, 113, 640-646 (2009).
3) K. Fujihira, T. Irisawa, H. Kobayashi and M. Shioya, “Specimen geometry dependent effects ofvapor grown carbon fibers on fracture toughness of polyamide 6”, International Journal of
Polymer and Technologies, 1, 35-41, (2009).
20101) K. Tanaka, N. Nakagawa, and R. Akiyama, “Flow behavior and microstructure developed between
46

parallel plate electrodes for electro-rheological nano-suspensions under no external electric fields”,
Nihon Reoroji Gakkaishi, 38, 93-97 (2010).
2) T. Irisawa, H. Kobayashi, K. Fujihira, M. Shioya and J. Kaneko, “A method to determine wear rates
of fibers and its application to polymeric fibers added with inorganic fillers”, Wear, 268, 1148-1156,(2010).
2011
1) K. Tanaka, T. Hira, R. Fukui, N. Nakagawa, R. Akiyama, M. Nakano, K. Yoshida and T. Tsujita,“Development and flow evaluation of electro-rheological nano-suspensions”, Colloid. Polym. Sci.,
289, 855-862 (2011).
2) K. Tanaka, T. Araki, T. Nozaki, R. Tanaka, H. Kobayashi and R. Akiyama, ”The effects of carbon
nano-fibre on the liquid crystalline behaviour and cholesteric pitch of aqueous solutions ofhydroxypropyl cellulose”, Liq. Cryst, in press.
(b) Books(c) Reviews and Reports
2007
M. Shioya, H. Kobayashi, T. Tanaka, T. Irisawa, S. Sakurai and K. Yamamoto, “Detection of crazes
in CNT/PET composites under tensile deformation”, Photon Factory Activity Report, (High Energy
Accelerator Research Organization (KEK), Institute of Materials Structure Science (IMSS)), 24 (B),148 (2007)..
2008
M. Shioya, H. Kobayashi, T. Irisawa, T. Suei, K. Fujihira, S. Sakurai and K. Yamamoto, “Fracture
toughness of PET fibers, PET films and CNT/PET composite films”, Photon Factory Activity
Report, (High Energy Accelerator Research Organization (KEK), Institute of Materials Structure
Science (IMSS)), 25(B), 118 (2008).
2009
K. Tanaka, and R. Akiyama, “Electrically induced microstructures in micro- and nano-suspensions
and related physical properties”, Polym. J., 41, 1019-1026 (2009).
2010
K. Tanaka, and R. Akiyama, “Preparation and Electrical Orientation for Cast Films via Liquid
Crystalline Phase (in Japanese)”, Ekisyo (Liquid Crystals), 14, 169-174 (2010).
(d) Awards
2008
H. Kobayashi, The Paper Award (The Society of Fiber Science and Technology, Japan), “Formation
Mechanism of Pores Contained in PVDF-based Carbon Films Derived through Chemical andHigh-temperature Heat-treatments”.

47

(e) Invited Lectures
20071) K. Tanaka, Y. Tanabe, and R. Akiyama, “Yield behavior of electro-rheological nano- and microsuspensions, and their microstructures”, The 27th regular meeting of Division of Electro-Rheology,
The Society of Rheology, Japan, (2007).
2) K. Tanaka, Y. Tanabe, and R. Akiyama, “Film preparation of liquid crystalline polymers underelectric fields”, Tokai Branch, The Society of Fiber Science, Japan, (2007).
2008
K. Tanaka, Y. Tanabe, and R. Akiyama, In-situ monitoring of a film preparation process for a liquid
crystalline polymer cast from isotropic solution under electric fields, Hokuriku Branch, The Societyof Fiber Science, Japan, (2008).
2009
K. Tanaka, R. Akiyama, and M. Nakano, “Flow behavior and microstructure of electro-rheologicalnano-suspensions before and after yielding”, Proc. of 6th International Conference on Flow
Dynamics, 132-133 (2009).
(f) Patents
20071) Y. Nakatsuka, S. Kiyohara, M. Tan, K. Ikeda, K. Tanaka, R. Akiyama, ”Composite material sheet
and production method thereof”, Japanese Patent Application No. 2006-163909, Japanese Patent
Publication No. 2007-332224.
2) Y. Nakatsuka, S. Kiyohara, M. Tan, K. Ikeda, K. Tanaka, R. Akiyama, "Composite material sheet
and production method thereof", Eur. Pat. Appl. (2007), EP 1867464 A1 20071219.
3) Y. Nakatsuka, S. Kiyohara, M. Tan, K. Ikeda, K. Tanaka, R. Akiyama, "Dispersion and redispersion
methods for dispersoids as well as crush method for aggregated dispersoids, and devices thereof",
Eur. Pat. Appl. (2007), EP 1870156 A1 20071226.
4) R. Akiyama, K. Tanaka, "Fiber-liquid crystal complex for display element and its manufacture",
Japanese Patent Application No. 2007-017694, Japanese Patent Publication No. 2008-185690.
2008
Y. Nakatsuka, S. Kiyohara, M. Tan, K. Ikeda, K. Tanaka, R. Akiyama, "Dispersion and redispersion
methods for dispersoids as well as crush method for aggregated dispersoids, and devices thereof",Japanese Patent Application No. 2006-172642, Japanese Patent Publication No. 2008-000686.
2010
T. Hiraku, M. Okada, Y. Nakamura, K. Tanaka, “Microchip and bubble-separation method thereof”,
Japanese Patent No. 4646125.

48

(g) Funds and Financial Supports
20071) K. Tanaka (a member of researchers), Project for Creation of Fiber Science and Technology for the
21st Century – Development of Neo-Fiber Technology, MEXT University R& D Expenditure.
(2007-2011).
2) K. Tanaka, KIT-NITTO Comprehensive Cooperation Research Project (2007-2008).
2009
K. Tanaka, The Cooperative Research Program of the Institute of Fluid Science, Tohoku University(2009-2011).
2010
K. Tanaka, KIT-KANEKA Comprehensive Cooperation Research Project (2010-2011).

49

Condensed Matter Physics Laboratory
Yasuo SARUYAMA, Dr., Prof.
Haruhiko YAO, Dr., Associate Prof.
I. Researches
Research interests of this laboratory include phase diagram and transition of state of soft matterssuch as polymers, liquid crystals, lipids, biomaterials. Further attention is paid to slow dynamics ofthe soft matters.

Since the soft matters are composed of molecules with complex structures, they

exhibit various types of molecular packing from the three dimensionally ordered crystals to the glasses
without long range order depending on temperature, pressure, mixing ratio, concentration of thesolution and so on. It is notable that the macroscopic properties such as heat capacity, density,
relaxation time, degree of birefringence etc. depend on the history of the material significantly. In thesoft matters large amplitude molecular motions, for example change in the molecular shape andexchange of the molecular positions, play important roles on the material properties.

These

molecular motions are highly cooperative and their correlation times are often very long as typicallyobserved in the glass transition. The soft matters are useful as functional materials because of thewide variety of the molecular packing, the flexible macroscopic properties and the characteristic slow
dynamics. In order to optimize the material functions it is important to understand the origins of thestructures, the properties and the dynamics.
In the research of this laboratory much effort is made for development of original instruments
for highly accurate experiments.

Various instruments with much higher performance thancommercial instruments have been developed in this laboratory. New concepts and models for thephenomena and the properties are proposed based on the reliable experimental data.

Some

instruments are introduced below.
1. High sensitivity differential scanning calorimeter (DSC).
The sensitivity of this DSC is as one thousand times as that of commercial instruments. This
DSC has been applied to measurement of heat capacity of human stratum corneum and construction of
the phase diagram of mixed systems of lipids and cholesterol. The former was carried out with one
sheet (ca. 10m) of the sample to avoid artifacts due to stacking of thin samples. The heat oftransition of the latter was very small and could not be detected with a commercial instrument.
2. An instrument for temperature modulated dielectric measurement.
This instrument was developed to study the kinetics of the response of the relaxation time toquick temperature change around the glass transition of polymers.

This relaxation of dynamics is a

new type of relaxation proposed and confirmed firstly in the world.
3. Ultra high pressure ac calorimeter.
This instrument enables highly accurate calorimetry under 1GPa hydrostatic pressure. It has
been applied to solid state phase transitions of polytetrafluoroethylene (PTFE). It was found that thephase transitions accompany long tails of heat capacity around the transition temperatures. The
shape of the tail was clearly observed.

Application of this instrument is expanding to denaturation of50

proteins.
4. An instrument for simultaneous measurement of the heat capacity and the volume expansion
coefficient.
It is known that the volume and enthalpy changes induced by a temperature jump around theglass transition exhibit delay. This instrument utilizes temperature modulation technique to study the
kinetics of the volume and enthalpy responses.

Disagreement between the temperatures ofcharacteristic stepwise change in the volume expansion coefficient and the heat capacity was found.
A model to explain the disagreement was proposed.

II. Publications and Achievements(a) Original papers
20071) K. Takegawa, K. Fukao, Y. Saruyama, “Aging effects on the thermal expansion coefficient and theheat capacity of glassy polystyrene studied with simultaneous measurement using temperature
modulation technique”, Thermochim. Acta, 461. 67-71 (2007).
2) K. Takekoshi, K. Ema, H. Yao, Y. Takanishi, H. Takezoe, “Quasi two-dimensional Ising criticalbehavior of de Vries liquid crystals observed in the heat capacity and dielectric response”, Phys.
Rev. E 75(3), 031704(2007).
2008
1) J.-L. Garden, J. Richard, Y. Saruyama, “Entropy production in TMDSC”, J. Therm. Anal. Cal., 94,
585-590 (2008)
2) K. Ema, Y. Sasaki, H. Yao, C.C. Huang, “Study of dielectric dispersion in non-layer-shrinkage
liquid crystal compounds”, Ferroelectrics, 364, 7-12(2008).
2009
K. Saito, T. Nakamoto, M. Sorai, H.Yao, K. Ema, K. Takekoshi, S. Kutsumizu, “Thermodynamic
symptom of coexistence of two aggregation modes in the Im3m cubic phase formed inthermotropic mesogen, ANBC(n)”, Chem. Phys. Lett. 469(1), 157-160 (2009).
20101) Yuji Sasaki, Kenji Ema, Haruhiko Yao, “Static and dynamic critical behaviours in de Vries liquid
crystals”, Liquid Crystals, 37(5), 571-577 (2010).
2) Y. Sasaki, K. Aihara, K. Ema, H. Yao, CC Huang, “Critical Behavior at the SmC(alpha)*-SmC*
Phase Transition Studied by High Sensitivity DSC”, Ferroelectrics, 395, 60-65(2010).
2011
1) Takashi Odagaki, Hideaki Katoh, Yasuo Saruyama, “Linear and Non-linear Dielectric Response of
a Model Glass Former”, J. Phys. Soc. Japan, 80, 1-4 (2011)
2) Naoki Koyabu, Haruhiko Yao, Yasuo Saruyama, Heat Capacity Relaxation during Annealing ofPoly(ethylene oxide) Crystals, Netsu Sokutei, (in press)
3) Y. Sasaki, Y. Setoguchi, H. Nagayama,

H. Yao, H. Takezoe, K. Ema, “Calorimetric studies on

isotropic-B(4) phase transition in the mixture of bent-shaped and rod-like molecules”, Physica E,51

43(3), 779-781(2010).
4) Y. Sasaki, H. Nagayama, F. Araoka, H. Yao, H. Takezoe, K. Ema, “Distinctive Thermal Behavior
and Nanoscale Phase Separation in the Heterogeneous Liquid-Crystal B(4) Matrix of Bent-Core
Molecules”, Phys. Rev. Lett., 107(23), 237802(2011).
(b) Books
2007
Koji Fukao, Satoshi Fujii, Yasuo Saruyama, Naoki Tsurutani, “Structure Formation and Glass
Transition in Oriented Poly(Ethylene Terephthalate)” in “Lecture Notes in Physics 714” pp. 97-116,(ed. by G. Reiter, G. R. Strobl), Springer (2007).
2010
1) Y. Saruyama, in “Handbook of Calorimetry and Thermal Analysis 2nd ed.” pp. 150-151, 158-159,
262, (ed. by Japan Society of Calorimetry and Thermal Analysis, A member of the Editorial Board),
Maruzen (2010).
2) H. Yao, in “Handbook of Calorimetry and Thermal Analysis 2nd ed.” pp. 70-72, 307, (ed. by Japan
Society of Calorimetry and Thermal Analysis), Maruzen (2010).
(c) Reviews and Reports
20081) Yasuo Saruyama, Koji Fukao, “Glass Transition and Glass Dynamics in Polymers (in Japanese)”,Netsu Sokutei, 35, 26-35 (2008).
2) Kenji Ema, Haruhiko Yao, “Critical behavior of de Vries Smectic A-C phase transition viewed fromprecise calorimetric and dielectric measurements (in Japanese)”, Ekisho, 12, 195-201 (2008).
2010
Yasuo Saruuyama, “New Technique of Thermal Analysis with Temperature Modulated DSC (inJapanese)”, J. Materials Life Society, 22, 43-47 (2010)2011
Yasuo Saruyama, “Basic Studies on Temperature Modulated DSC and Temperature Modulation
Method and their Application to Slow Dynamics (in Japanese)”, Netsu Sokutei, 38, 86-92 (2011)(d) Awards
2010
Yasuo Saruyama, JSCTA Award (The Japan Society of Calorimetry and Thermal Analysis), “BasicStudies on Temperature Modulated DSC and Temperature Modulation Method and their
Application to Slow Dynamics”(e) Invited Lectures
2009
Yasuo Saruyama, “Application of the Temperature Modulation Method to Polymers” 11th Japan 52

Belgium Symposium on Polymer Science, Tokyo Tech Front, Royal-Blue Hall, Nov. 8 - 11, 20092010
Yasuo Saruyama, “Basic Studies on Temperature Modulated DSC and Temperature Modulation
Method and their Application to Slow Dynamics (Award Lecture)(in Japanese)”, 46th Japanese
Conference on Calorimetry and Thermal Analysis (2010)(f) Patents(g) Funds and Financial Supports
2007
Haruhiko Yao, Grant-in-Aid for Scientific Research, Scientific Research(C) 18570148,“Development of an ultra-high-pressure AC nanocalorimeter and its application to the studies on
the pressure dependence of heat capacity in protein”.
2008
Yasuo Saruyama, Grant-in-Aid for Scientific Research, Challenging Exploratory Research21654059, “Direct Confirmation of Dynamic Heterogeneity with Temperature Modulated X-ray

Diffraction”.

53