実験報告書様式（トライアルユース）（ ※本報告書は英語で記述してください。ただし、産業利用課題として採択されている方は日本語で記述していただいても結構です。 ）Experimental Report

承認日 Date of Approval 2015/7/8
承認者 Approver Kaoru Shibata
提出日 Date of Report 2015/7/8

課題番号 Project No.

装置責任者 Name of Instrument scientist

2014B0181

Kaoru Shibata

実験課題名 Title of experiment

装置名 Name of Instrument/（BL No.）

Selective solvation of Nafion in 1-Propanol/Water solution

BL-02

実験責任者名 Name of principal investigator

実施日 Date of Experiment

Makoto Yamaguchi

April 24-26, 2015

所属 Affiliation
Fuel Cell Cutting-edge Research Center
試料、実験方法、利用の結果得られた主なデータ、考察、結論等を、記述して下さい。（適宜、図表添付のこと）
Please report your samples, experimental method and results, discussion and conclusions. Please add figures andtables for better explanation.
1. 試料 Name of sample(s) and chemical formula, or compositions including physical form.
Nafion (2.2wt%) dispersed in 1-C3H7OD/D2O (23/77 v/v). The solution looks colorless and transparent,indicating Nafion particles are uniformly dispersed. 1-C3H7OD/D2O (23/77 v/v) solution without Nafion wasalso prepared for comparison.

Chemical structure of Nafion

2. 実験方法及び結果 （実験がうまくいかなかった場合、その理由を記述してください。）
Experimental method and results.

If you failed to conduct experiment as planned, please describe reasons.

Experimental method
Measurement cells were made of two cylindrical quartz cells (thickness 0.5mm) with different diameter (13.4and 14mm). The sample solution was carefully poured into the small gap between the two cells to avoid bubble
formation. The quartz cell was placed in an aluminum cell for measurement.
Sample measurements were performed at 300 and 285K. Incident energy of neutron was selected by thechoppers and kinetic energies of the scattered neutrons were detected with the high-resolution mode. The energy
range of the scattered neutrons was -400 to 600 μeV, which was covered by combinations of elevenaccumulation steps performed by shifting 30 ~ 35 μeV the energy range. Energy resolution was 3.6 μeV. Total
accumulation time for one sample was about 5.5 hours. Actually we prepared other two samples with different
composition but found that Nafion was not uniformly dispersed in them. We had to work with only one Nafion
sample and its solvent as another one and thus we tried to measure them at two different temperatures. A blankcell was also measured as the background data.

2. 実験方法及び結果（つづき） Experimental method and results (continued)
Results
The measured S(Q,E) data were binned from 0.2 ~ 1.6 ± 0.075 Å-1 in 0.2 Å-1 steps and 1.725 ±0.05Å-1. Thus
obtained S(E) data were analyzed by using 1D peak fitting of DAVE program (version 2.3). The measured S(E)data were deconvoluted with the dataset of the blank cell (± 20 μeV) and one (Q ≥ 1.0 Å-1) or two (Q ≤ 0.8 Å-1)
Lorentzian curves and a linear background. χ2 values of the fittings were 1.5 ~ 3.7.
For data with Q ≥ 1.0 Å-1 gamma values of the Lorentzians plotted against Q2 show steady increase at up to ~ 2.5
and then become constant which are typical for jump diffusion model, regardless of the presence of Nafion in thesamples. The gamma values at 300K are much larger than those at 285K as expected. However, while the Nafion
solution showed slightly larger gamma values than those of the solvent at 285K, this trend is opposite at 300K.
Diffusion coefficients and mean residence times were estimated from these data based on the jump diffusion
model and they are summarized in the table. The diffusion coefficients were about half of the measured value of~ 6.0 × 10-10 in 1-propanol/water mixture with or without salt (Hawlicka and Grabowski, J. Phys. Chem. 96,1554(1992)).
At Q ≤ 0.8 Å-1 two Lorentzians were necessary to fit each S(E) profile. One of the two gamma values is verysmall and decreases towards smaller Q, while another is about ten times larger and increases towards smaller Q.
At this moment we have not given any interpretation for those two gamma values yet.

D / m2 s-1

τ0 / sNafion 285K

2.0 × 10-10

1.0 × 10-11

Solvent 285K

2.0 × 10-10

1.2 × 10-11

Nafion 300K

3.1 × 10-10

5.5 × 10-12

Solvent 300K

3.1 × 10-10

4.5 × 10-12