Photon Factory Activity Report 2004 #22 Part B (2005)
Materials Science

15A/2003G241

Structure and Re-orientation in the First Stage for Polyamide/Iodine Complex.
[II] Change of Structures on Iodine Doping and Termination.
1Akio KAWAGUCHI, Naoki TSURUTANI2, Hideki MIYAJI2
1KURRI, Kumatori, Osaka 590-0494, Japan
2
Faculty of Science, Kyoto Univ., Kitashirakawa, Sakyo-ku, Kyoto 606-8502, Japan

Introduction®
Polyamide-6 (PA6, Nylon -6) is a popular hydrophilicpolymer with high crystallinity, and it also shows orderedstructures even in coordinated structures with guestmolecules or ions. "Polyamide-6/iodine complex" can beprepared by easy and rapid operation using an aqueous
solution containing polyiodide ions at room
temperature.[1-3]
As one of interesting behaviors for the complex
structure, rapid formation of the complex is reported; thecomplex structures are formed rapidly in a few
seconds.[4] However, the initial structure observed in thefirst stage shows different spacing of intercalated
structures from essential one shown in ordinary stablestructure.[5] In this work, in-situ observation for the
doubly oriented film of PA6 was achieved using anenclosing housing.[6]Experiments

Results
The spacing of 1.56nm which is ordinarily and stably
observed for the complex did not appear in the first stageof complex but was observed after rinsing by water. At
the same time, another structure rose or vanished throughoperation.
Iodine-doping
andrinsing
suggestcomplication in preparation for the complex and moreinvestigation has been required.
0 min.
3
4
5
7
10
20
30
40

pouring
1000(Kapton)
900

20 Å
800
700
600
500
400
300
200

140 Å40 Å

100

Sample preparation : Doubly-oriented PA-6 film:
5PA6 used was a commercial polymer (MW=4.2x10 ) anda melt-pressed film was quenched in ice water. The film
was drawn three times to be a "doubly-oriented" film. (χ~25%) This film (0.15 mm in thickness) was cut to be astrip which could be set in a quartz capillary of 2.0 mm indiameter.

0012342 theta (deg.)

5678rinsing
10000 min.
2819900
800
700

15.6 Å !

600
500

Pouring system : housing, dispenser pump, solution:
For the process of "iodine-doping", an aqueous solutionof I2-KI (0.4N) was used.
Scheme of the housing vessel has been reported.[5]Remote-controlled operation of a dispenser pumpintroduced the 0.4N I2-KI solution and rinsing water intoa capillary holding the filmy sample; regular rotation of
the pump introduced the solution from the capillarybottom as a suction pump and reverse rotation led
distilled water which was reserved in a tube connected at
the capillary head. Each flow was synchronized to start oftime-sliced measurement.
Beam, detector, layout:
As an incident, a monochromatized beam (λ = 0.15nm) on BL-15A was used and diffraction profile wasmeasured with an 1-dim PSPC.[7] The detector was set todetect diffraction along the meridian; the line detector
was arranged normal to the chain axis in this experiment.
Camera length was 510mm and exposure time was set as
1min. for each shot. For each sequence of observation,
20-45 shots were taken continuously.

174

Users' Report

400300

12 Å200130 Å40 Å

100
00

1

2

342 theta (deg.)

56

78Figures: Diffraction profiles of in-situ observation onpouring solution (upper) and on rinsing with water (lower).

Acknowledgements
The authors express great thanks to Dr. Sugimoto andProf. Wakabayashi of Osaka University for theirconscientious and kind help and guidance.
References[1] H. Arimoto,et.al., J. Polym. Sci., A3, 317 (1965).
[2] A. Kawaguchi. Polymer, 33, 3981(1992).
[3] A. Kawaguchi., Sens. Act. B. 73, 174 (2001).
[4] A. Kawaguchi, et.al., SPring-8 User Exp. Rep. 5, 354 (2000).
[5] A. Kawaguchi, et.al., Polym. Prep. Jpn., 50, 2000 (2001).
[6] A. Kawaguchi, et.al., PF Activity Rep. 2003, 172 (2004).
[7] http://pfwww.kek.jp/users_info/station_spec/bl15/bl15a.html* akawagch@rri.kyoto-u.ac.jp