VIII-Ⅱ-1. Project Research
Project 9PR9Project Research on Development of Scattering Spectrometers Utilizing Smalland Medium Class Neutron Source

M. Sugiyama
Research Reactor Institute, Kyoto University
Objectives and Allotted Research Subjects: Recently,
J-PARC has started to supply very intensive pulse neutron beam. This means that research with neutron is getting into new world. However, only with J-PARC, wecannot to sustain this new research world. Especially, it
is inevitable to check new idea, to analyze industrial
products and to educate new comers. For this purpose,
we think small-and/or medium class neutron sources arevery suitable. As a corollary, beam intensity from thesesize neutron sources is not so strong. Therefore, we face
what can we do and/or how can we do effective researchwith these neutron source. In order to answer these questions, we have started this research project with the following six allotted research subjects.
ARS-1: Nano-Scale Structure Measurements of Micelles
by Utilizing KUR-SANS. (K. Hara, T. Yanagino, T.
Miyazaki, S. Yoshioka, Y. Oba, N. Sato1 and M.
Sugiyama)
ARS-2: Evaluation of high-q data of KUR-SANS forquantitative analysis of precipitates in steels. (M. Ohnuma, Y. Oba, P.Kozikowsky and M. Sugiyama)
ARS-3: Development of Small-Angle Scattering Calculation Code (M.Sugiyama, and Y.Ueki)
ARS-4: Development of compact SANS monochromator for steel-related sample use of KUR-SANS (M. Hino,
Y. Oba, T.Oda, M. Sugiyama)
ARS-5: Dvelopment of sample cell for in-situ SANS
experiments using hydrogen absorbing materials. (K.
Mori, K. Iwase, Y. Oba, T. Ichida, T. Fukunaga, and M.
Sugiyama)
ARS-6: Small-angle Neutron Scattering Analysis of Radiation-Fabricated Thermoresponsive Binary Hydrogels.
(N. Sato, Y. Oba, M. Sugiyama)

ARS-2: Ohnuma et.al. evaluated KUR-SANS
data of steel. which is one of main targets of
KUR-SANS, with SANs data obtained with theother intensive neutron spectrometers. There
are some discrepancy in high q-region. The
reason is discussed in the report.
ARS-3: Sugiyama and Ueki are developing thedata analysis program. They developed the
SANS simulation of protein and also special
cage. Their simulation well reproduces the experimental results.
ARS-4: Hino et.al. developed a new monochromator for KUR-SANS. The monochromator supplies 4.8Å neutron suitable for structuralinvestigation of steel.
ARS-5: Mori et.al. developed sample cell for in-situ
SANS experiments using hydrogen absorbing materials

In situ experiment is inevitable to understandhydrogen behavior and distribution in thestorage material.
ARS-6:
Satoet.al.
studiedγ-radiation-fabricated thermo-responsive binary hydrogels. The structure and character ofthis new material have not been clarified somuch. Sato revealed the structure with
KUR-SANS.

Main Results and Contents of This Project:

ARS-1: Hara et.al. investigated nano-scale
structures of micelles with KUR-SANS. Withsodium oleate solution, they obatined very clear
SANS profile with KUR-SANS and confirm thatthe revealed structure well agrees with thatobtained by SAXS. This result indicates that
KUR-SANS (installed at medium class neutron
source) is also useful to this research filed.

採択課題番号 24P9
中小型中性子源を用いた散乱分光システムの開発（京大・原子炉）杉山正明

プロジェクトPR9-1

Nano-Scale Structure Measurements of Micelles by Utilizing KUR-SANS

K. Hara, T. Yanagino, T. Miyazaki, S. Yoshioka, Y. Oba1,
N. Sato1 and M. Sugiyama1
Department of Applied Quantum Physics and Nuclear
Engineering, Kyushu University
1
Division of Quantum Beam Material Science, Research
Reactor Institute, Kyoto University
INTRODUCTION: The authors have been investigating
the nano-structures of the hydrocolloids, such as hydrogels and surfactants, which are composed of dispersoid and water. By the alteration of the interactions between the ingredients, they often show drastic changes
in the nano-scale structures. In the present investigation,
the authors have examined the performance characteristics of the KUR-SANS system installed at Research
Reactor Institute, Kyoto University by investigatingsuch a nano-scale structure of a surfactant, sodium oleate (SO), in heavy water. By the present examination,
the KUR-SANS system has demonstrated a competentperformance to get the SANS profiles of such a surfactant.
EXPERIMENTS: The SANS experiments were performed with the KUR-SANS system installed at Kyoto
University Reactor, Kumatori, Japan. 30 mM sodium
oleate (SO) heavy-water solutions were prepared andwere sealed into quartz cells. The small angel neutron
scattering (SANS) profiles were observed for the 30mM
SO D2O solutions after having been left intact for 24hours at room temperature. Figure 1 shows the
2-dimentsional distribution of the scattered neutron intensity scattered from the SO solution observed by the
KUR-SANS system. Figure 2 shows the SANS profile
derived by integrating the 2D intensity distribution in
the same circumference. Figure 3 is the small angel
X-ray scattering (SAXS) profile of the SO solution observed with an SAXES optics installed at BL-10C of the
Photon Factory in High Energy Accelerator Research
Organization (KEK), Tsukuba, Japan for the comparison with the SANS profile.
RESULTS: The SANS profiles obtained with the
KUR-SANS system are in good quality as shown in
Fig. 2, which are the typical ones observed in many
micelles, indicating a competent performance of thesystem. The micellar structure in the SO could be confirmed by the SAXS profiles observed with the SAXES
system, which are also observed in many micellar
structures of surfactants.

Fig. 1

2D Intensity Distribution of Scattered
Neutron from 30mM Sodium Oleate in
D2O observed by KUR－SANS

Fig. 2A SANS Profile 30mM Sodium Oleate in
D2O observed by the KUR-SANS system.

Fig. 3

A SAXS Profile 30mM Sodium Oleatein D2O observed by the SAXES system.

採択課題番号 24P9-1 KUR-SANS を用いたハイドロコロイド分散系の中性子小角散乱観測（九大院工）原 一広、柳野 智、宮崎智博、吉岡 聰(京大原子炉）大場洋次郎、佐藤信浩、杉山正明

プロジェクトPR9-2

Evaluation of High-q Data of KUR-SANS for Quantitative Analysis ofPrecipitates in Steels

M. Ohnuma1, Y. Oba2, P.Kozikowsky1,3 and M. Sugiyama2
1

National Institute for Materials Science
Research Reactor Institute, Kyoto University
3
Warsaw University of Technology

2

INTRODUCTION: Due to the high demands of
SANS in the field of materials science, the role of SANS
installed in the medium scale or compact type neutron
source becomes important. The performance of SANS
instruments installed in compact source can never overcome the one in large-scale facilities, however, it cangive enough information in the focused q-range corresponding the target scale in real space. Our target q-range
for SANS in compact source is the range from 0.1 to 3
that corresponds to the range covered by laboratory
SAXS. Once the q-range is cover by SANS in KUR, it
bring much broader applications using the way for thecompositional analysis based on the contrast difference
between SANS and SAXS(1-3). For this purpose, we havemeasured same samples using different SANS instruments together with KUR-SANS.

high-q region. Judging from the same level of bothblue squares and red circles, it must attribute to a relatively high level of constant background. The levels of
the profiles measured perpendicular to the field arebasically same between those measured in KUR and
TAIKAN. However, the level measured in HANARO
is higher than others. This result suggests that the
SANS intensity may still depend on the field suggesting that the field of 0.6T is still smaller than the saturation field. It will be discussed by magnetic measurements and/or the comparison of SANS profiles inabsolute unit.
In conclusion, the statistic of the KUR-SANS profiles
have been drastically modified and almost reached forregular use. However, there are still some spaces for discussion, like possibility for making background lower
and validity of the applied field level.

EXPERIMENTS: The steels for tools, class SCM450(0.4wt%C) was used for the comparison among the threedifferent facilities, i.e. TAIKAN in J-PARC, HANARO-18m SANS (Korea) and KUR-SANS. For separating magnetic and nuclear component, different magnet
was used depends on the facilities. The field for 0.5 1.0
and 0.6T is used for TAIKAN, 18m SANS andKUR-SANS, respectively. Because all the fields arelarger than the saturation field of pure iron, the fields are
assumed to be enough for saturating the measured sample. Measurements have been performed using the monochromator for the wavelength of 0.47nm.
RESULTS: Figure 1 shows a SANS profile of

SCM450 tempered at 550ºC. The profile measured in
HANARO is in absolute scale and the others are
shifted for overlapping profiles parallel to the magnetic field. Data measured in KUR-SANS are shown inmarkers (circles(red) : parallel to the field (nuclear
component), squares(blue) : perpendicular to the field(sum of magnetic and nuclear component)). Compare
to the profiles obtained in 2011 in KUR-SANS, thestatistic has been modified drastically by the newly
developed monochromator. Nevertheless, there are thediscrepancy between profiles obtained by KUR-SANS
and TAIKAN (blue and red solid curves), especially in

採択課題番号 24P9-2

Fig.1 SANS profiles of SCM450 tempered at
550ºC measured using different SANS.
markers: KUR-SANS, solid curves: TAIKAN
and dotted curved HANARO.
colors indicates the direction of scatteringvectors, blue: perpendicular to the magnetic
field, red: parallel to the magnetic field

高 q 領域の SANS と SAXS を併用した鉄鋼中ナノ析出物の定量評価法（物材機構）大沼正人,Pawel Kozikowsky,（京大原子炉）大場洋次郎, 杉山正明

プロジェクトPR9-3Development of Small-Angle Scattering Calculation Code

M. Sugiyama and Y. Ueki
Research Reactor Institute, Kyoto University
INTRODUCTION: Small-angle scattering is a very
powerful tool to analyze the particle structure in solution.
This technique gives us the roughly estimation of sizeand shape of the particle. However, it is difficult to reveal the detailed structure from scattering profile. In
these days, we are developing several calculation andsimulation codes to overcome this problem. As a result,
SAS calculation program for protein has been almost
completed: the program calculates SAS profile (SAXS
and SANS) from PDB data considering surrounding water. So, as a next step, we are trying to apply this program
to analyze to another kind of particle, organic cage which
was developed by Fujita group in University of Tokyoand a promising material for use of drug delivery and soon. Here, we report the result of analysis of status of cage
material in solution.
EXPERIMENTS:
shown in Fig 1.

Cage material. The Solid line in Fig.3 shows
the calculated SAS profile with the ratio ofmonomer and dimer of 1:0.13. As you can see,the calculated profile well reproduce the experimental one except for the profile in thehigher q-region>0.3Ǻ-1. Therefore, we consider
the remaining chemicals after the formation
reaction. The candidates of remaining chemicals were Pd(OTf)2 and Ag(OTf) and we
re-calculated SAXS profile taking considerationof scattering from the remaining chemicals:
they are small molecules which increase theintensity in the higher q-region. The
re-calculated SAXS profile well reproduce theexperimental one.(Fig.4.)

The structure of Cage particle isFig. 1. Structure of Cage material. Cagecomposed with five-membered ring connecting by Pd.
The SAXS experiments were carried out at room temperature with a SAXS apparatus installed at BL45XU ofSPring8, Hyogo, Japan. (Measurement time is 10sec withconcentration of 1mg/ml)
RESULTS: Figure 2 shows SAXS profiles ofCage material. We also calculated SAXS profile
with atomic coordinates of Cage material by
our SAS program. However, the calculated
SAXS profile does not reproduce the observed
one. Here, we consider the aggregation of the

採択課題番号 24P9-3

Fig. 2 Observed SANS profile and simulated
ones.

RMC 法を用いた中性子小角散乱法による
粒径分布解析法の開発（京大・原子炉）杉山正明、大場洋次郎、上木祐太郎、（北大院工）古坂道弘

プロジェクトPR9-4Development of Compact SANS Monochromator for Steel-Related Sample
Use of KUR-SANS

M. Hino, Y. Oba, T. Oda1, M. Sugiyama
1

Research Reactor Institute, Kyoto University
Department of Nucl. Eng., Kyoto University

2

INTRODUCTION: Small angle neutron scattering(SANS) technique is very powerful to investigate ofstructure of complex material with size of 1-100 nm. The
scope of application is very wide and there are a lot ofinteresting sample with strong scattering intensity. A lotof researchers are interested in steel-related sample andthe scattering intensity is strong. Thus KUR-SANS [1]with 1MW reactor operation is still very useful andimportant to improve the instrument. There are two
monochromators in which average wavelength is 0.28
and 0.55 nm in the KUR-SANS [1,2]. The
monochromators are double reflection type as shown in
Fig.1 and they don’t change reflection angle depend on
wavelength. The d-spacings of these monochromators for0.28 and 0.55 nm are 7 and 14 nm, respectively. The
acceptable beam width of 8 mm is not large. Currently,
the monochromator for 0.55 nm is not so effective since
Cold Neutron Source (CNS) at KURRI does not operate.
These monochometers are not optimum for steel-related
sample since the required wavelength is longer than 0.42
nm to avoid Bragg diffraction from the crystal part of thesteel-related sample. The optimum average wavelength isabout 0.47 nm in which wavelength resolution of 20% in
FWHM. The d-spacing of required multilayer was 11.8
nm since the incident angle is 20 mrad. In this study, weshow the performance of new monochromator for
steel-related sample at KUR-SANS.

Fig.1 The photograph of monochromator and layout of thetwo set of NiC/Ti multilayer mirrors for KUR-SANS.
Here φis equal to 2θ.

EXPERIMENTS:The multilayer mirrors deposited on
both surface of silicon substrates in which size of
64x32x0.6 mm. They were fabricated by using ion beam
sputtering machine at KURRI. The reflectivity
measurement was carried out at CN-3 beam line.
RESULTS: Figure 2(a) shows comparison between
direct beam and reflected beam by new monochromatorwith collimated beam condition. The slit width anddivergent angle were 5 mm and 2.7 mrad, respectively.
The reflected beam well extracted from direct beam. The
wavelength of maximum intensity was estimated to be
0.48 nm and the resolution is 16 % in FWHM. In
Fig.2(b), the background level, in particular effect of λ/2 reflection, was dramatically reduced by using double
reflection configuration.

採択課題番号 24P9-4

Fig.2 in comparison of (a) Direct beam and measured
reflectivity of the monochromator, (b) reflectivities ofsingle and double reflection in the monochromator,
respectively.

REFERENCES:[1] M.Sugiyama, et al., JJAP, 33(1994) 6396.
[2] H.Sunohara, M.Hino, et al.,Physica B,
350(2004) 869.

2 次元集光デバイスと(偏極)小角散乱用
プロジェクト
小型モノクロメーターの開発（京大・原子炉）日野正裕、杉山正明、北口雅暁（京大・工）小田達郎、田崎誠司

Dvelopment of Sample Cell for In-situ SANS Experiments
Using Hydrogen Absorbing Materials

K. Mori, K. Iwase1, Y. Oba, T. Ichida2, T. Fukunaga and
M. Sugiyama
Research Reactor Institute, Kyoto University (KURRI)
1
Department of Materials and Engineering, Ibaraki University
2
Graduate School of Engineering, Kyoto University
INTRODUCTION: It is well known that Ti-Cr-V alloys are excellent hydrogen absorbing materials, together
with intermetallic compounds such as LaNi5 and Mg2Ni.
The Ti-Cr-V alloys exhibit an enormous maximum hydrogen storage capacity (i.e., with a H/M value of 2,
where H/M is the hydrogen-to-metal ratio); therefore,
these materials have attracted much attention as promising candidates for hydrogen storage applications such as
high-pressure metal hydride tanks in fuel-cell vehicles.
To characterize the hydrogenation properties by assessing the state of the surface of the powder particles in
the Ti-Cr-V alloy is very important. Although a variety
of investigations on the microstructure and morphologyof the Ti-Cr-V alloys by scanning electron microscopy(SEM) and transmission electron microscopy (TEM)
have been conducted in previously reported studies [1],sufficient information on the surfaces of particles in
Ti-Cr-V alloys subjected to hydrogenation is deficient.
On the other hand, small-angle neutron scattering(SANS) is widely recognized as a powerful tool for observing the particle-surfaces of industrial materials [2].
We expect that SANS can serve as an appropriate technique to obtain information on the particle-surfaces in thecase of Ti-Cr-V alloys as well.
In this work, we developed a sample cell for in-situ
SANS experiments (in-situ cell) with the SANS spectrometer of Kyoto University Research Reactor(KUR–SANS), and carried out preliminary in-situ SANS
experiments using Ti0.31Cr0.33V0.36 alloy.

of (Ti0.31Cr0.33V0.36)H0.7 was estimated to be 2.9, where q
is the magnitude of a scattering vector.
In conclusion, we could establish the in-situ SANS
technique for investigations of the hydrogen absorbing
materials. We expect that the in-situ technique is absolutely beneficial to any intermetallic compound such as
LaNi5.

Fig. 1. The view of the high-pressure stainless steel cellfor in-situ SANS experiments (in-situ cell), equippedwith the KUR–SANS at the CN–2 beam port in KUR.
100
6
4

Intensity / arb. unit

PR9-5

(Ti0.31Cr0.33V0.36)H0.7

2

10
6
4
2

1
6
4
2

EXPERIMENTS: The Ti0.31Cr0.33V0.36 alloy was prepared by arc-melting of a mixture consisting of Ti, Cr,
and V in appropriate molar proportions. In-situ SANS
experiments were carried out with the KUR–SANS installed at the CN–2 beam port of KUR [3]. The incident
neutron wavelength was 0.28 nm.
RESULTS: Figure 1 shows the in-situ cell developed,
which consists of a stainless steel body and two quartz
windows (each 5 mm in thickness). In the in-situ cell,
the Ti0.31Cr0.33V0.36 alloy was hydrogenated up to H/M =0.7 under a hydrogen atmosphere at around 1 MPa atroom temperature.
The in-situ SANS profile of(Ti0.31Cr0.33V0.36)H0.7 during absorption is shown in Fig. 2.
From the slope of the in-situ SANS profile in the q range
0.2–0.3 nm–1, the fractal dimension of the particle-surface

0.1
2

3

4

5

6

7 8 9

1

2

3

–1

q / nmFig. 2. In-site SANS profile of (Ti0.31Cr0.33V0.36)H0.7
during absorption at room temperature. The solid linein the q range 0.2–3.0 nm–1 indicates the results of theleast-squares fit obtained based on a power law.
REFERENCES:[1] E. Akiba et al., Intermetallics, 6 (1998) 461.
[2] R. A. Livingston, Cem. Concr. Res, 30 (2000) 1853.
[3] M. Sugiyama et al., Jpn. J. Appl. Phys., 186 (1994)
6396.

プロジェクト	 採択課題番号 24P9-5 	
 中性子小角散乱による Ti–Cr–V 水素吸蔵合金の表面観測（京大・原子炉）森	  一広、大場洋次郎、福永俊晴、杉山正明（京大院・工）市田智晴	
 （茨城大・工）岩瀬謙二	
 Small-Angle Neutron Scattering Analysis of Radiation-FabricatedThermoresponsive Binary Hydrogels

N. Sato, Y. Oba and M. Sugiyama
Research Reactor Institute, Kyoto University
INTRODUCTION: Hydrogels are now widely used as
useful biocompatible materials in a various fields of industry: medicine, food, hygiene products and othercommodities. As well as in such an applicational aspect,polymer gels have also been attracting much attention ina scientific aspect. Network structure composed of interconnected polymer chains shows unique properties
different from the original polymer and those propertiesare dependent on the gel characteristics such as crosslink
density, structural inhomogeneity, electrical charge, andhydrogen bonding. Thermoresponsive property is oneofthoseuniqueproperties.
Poly(N-isopropylacrylamide) (PNIPAm) in water showscoil-globule transition at ca. 34 °C. Inheriting thisproperty, PNIPAm hydrogel shows volume transition at
this temperature region: the gel is greatly shrinking whenheated around 34 °C. Therefore it is quite interesting tofabricate multi-component gels composed of thermoresponsive component and other common hydrogel
component.
Gel preparation utilizing ionizing radiation has a meritof high-quality gels. Radiation-prepared gels can beobtained only irradiating radiation such as -rays to thepolymer solution, which needs no additives such as
crosslinkers, reaction initiators, and catalysts.
In this study, we synthesized thermoresponsive porous
binary hydrogels consisting of a common polymer, poly
ethylene glycol (PEG) and PNIPAm by -ray irradiation.
We revealed the structural characteristics of those gelsbelow and above transition temperature employing
small-angle X-ray and neutron scattering (SAXS, SANS)
analysis.
In this report, the results of SANS experiments whichwere conducted at the Research Reactor Institute, Kyoto
University is described.
EXPERIMENTS: A 10-wt% aqueous solution of PEG(MW 20000) was sealed in a vial after the bubbling with
N2 and then irradiated with -rays of 60 kGy at a dose
rate of 1kGy/h. The obtained gels were purified by removing unreacted polymers with water rinsing several
times. The purified PEG gels were swollen in 10-wt%
NIPAm monomer aqueous solution. After removing
water at the gel surface, the gels were irradiated again
with -rays of 3 kGy at a dose rate of 1kGy/h. Then
final product gels were obtained after removing unreacted
NIPAm monomer and isolated PNIPAm chains. For the
porous gels preparation, silica micro particles (hyprecica,
200 nm and 1000 nm) were incorporated before PEG
gelation, which were decomposed by the hydrofluoric
acid treatment after PEG gelation.

SANS experiments were carried out at the KUR-SANS
facility. The neutron wavelength and the q-range were0.28 nm and 0.16–3.5 nm-1, respectively.
RESULTS: The SANS profile for the nonporous
PEG/PNIPAm binary hydrogel at 20 °C is shown in Figure 1.
2

10

Intensity (arb. unit)

PR9-6

-4

6
5
4
3
2

10

-5

6
5
4
3

10

-

2

3

4

5 6 78

10

0

2

3

4

-1

q (nm )

Fig 1. SANS profile of nonporous PEG/PNIPAm binary hydrogel at 20°C.
The gel is in the swollen state at this temperature. This
profile resembles that of swollen pure PEG gels, andtherefore the incorporated PNIPAm affects little binary
gel structure in the swollen state.
At 40°C, in contrast, a steep rise in the low-q region
appears for the binary gels. The slope of the rise for the
porous gels has the relationship of Iq-4 , which iswell-known equation Porod’s law.
These results suggest the following scheme. Whenthe temperature is lower than the transition temperature,
the binary gels were swollen and the chains of eachcomponent polymer cannot be indistinguishable. At thetemperature higher than the transition temperature, on theother hand, PNIPAm chains in the binary gels shrink
while the PEG chains does not change. Especially forthe porous gels, shrinking PNIPAm domains and PEG
matrix domains are definitely separated. Since the
Porod’s law shows the presence of clear interface of two
domains, it is indicated from this result that shrinking
PNIPAm domains are formed in the still swollen PEG
matrix and the borders of two domains appear at thehigher temperature especially in the porous binary gels.

採択課題番号 24P9-6中性子小角散乱による感熱応答性多成分系高分子ゲルの構造解析プロジェクト（京大・原子炉）佐藤信浩、杉山正明