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>10nm >100nm <1nm 3-10nm
Crystal Structure
Random coil (溶液中での形
態)
Incident X-ray
Diffracted/Scattering X-ray
Transmitted X-ray
2θ =数度~数十度
Material SAXS
WAXD SAXS
サイズd が大きい程、散乱角度θが小さい
2θ
d = λ/ (2sin θ) a b
c Phase separated structure
USAXS
Crystal-amorphous two phase structure
Application of X-ray Diffraction to Soft Matter Characterization
1. X-ray Emission and Instumentation
特性X線 陰極-陽極間に高電圧を印加し,陰極(フィラメント)から飛び出した電子が陽極(回転対陰極,ターゲット)に衝突して連続X線が発生する.陽極に衝突した電子が内殻(K殻)の電子を弾き飛ばした後に,外殻(L殻,M殻)の電子が空軌道へ遷移する際に放出されるのが特性X線である.
フィラメント:タングステン ターゲット:銅 L→K殻遷移:Ka線(Cu: 1.5418Å), M →K殻:Kb線. Niフィルタまたはモノクロメータ(グラファイト単結晶)で単色化
2
SPring-8放射光のエネルギーと明るさ
偏向電磁石
太陽の1億倍 の明るさ!
特徴��
�●連続波長��(赤外線〜硬X線)��●極めて明るい�
� (高輝度性)��実験室装置の1億倍�
�●真っ直ぐな光�� (高指向性)�
�(100m先で2.4mm� �の拡がり)��●偏光特性�
�●短パルス光
アンジュレータ
2014/05/16
4
イメージインテンシファイヤー + CCDカメラ (II+CCD)
FlatPanel detector DSC
ca. 2m
Flatpanel + (II+CCD)を用いたSR XRDシステム
DSC X-rays
FlatPanel detector II+CCD
Vacuum path Beamstop
WAXD: q=8~25nm-1
SAXS: q=0.06~2nm-1
5秒ごとの時間分割測定が可能
検出器の特性比較
IP II + CCD Flat Panel
検出面 Flat ひずみあり Flat
Pixel Size 100 µm角 112 ~ 170 mm角(レンズに依存)
50 mm角
Area 3000×3000 1344×1024 1056×1056
Dynamic Range 106(16000) 10000 5000
Frame Rate 90 s
(照射時間を含む) 1.6 s(S/N重視)
100 ms(速度重視) 350 ms
etc ・強度線形性は16383カウントまで ・感度はCCDの1/3 ・静的測定、広角測定、長時間X線照射
・球面検出器のためひずみ補正が必要 ・感度が高い ・時間分割測定、小角測定
・感度がCCDの1/5(エネルギーに大きく依存) ・小角測定との同時測定用
Imaging Plate (IP)
Imaging Intensifier (II + CCD)
Flat Panel (FP)
Pilatu3X 1M Pilatu3S 1M Eiger 1M II + CCD
Modules 2 x 5 2 x 5 1 x 2 1
Count rates 10 Mcts/sec/pixel (100K cps)
10 Mcts/sec/pixel (100K cps)
2 Mcts/sec/pixel (20K cps)
Frame rates 600 Hz (0.7ms照射) 25 Hz (38ms照射)
3000 Hz (照射時間依存) 15 Hz
Readout time 0.95 ms 2 ms 0.003 ms c.a. 70 ms
Pixel size 172 x 172 (µm2) 172 x 172 (µm2) 75 x 75 (µm2) 126(µm2), IIに依存
Sensitive area 168.7 x 179.4 (mm2) 77.2 x 79.9 (mm2) 64.5 x 84.6 (mm2)
ROI readout YES NO Un known YES
WAXD Pattern
配向試料 Random Orientation
2θ 2θ
X-ray
Debye Ring
Sample
2D Detector (IP, II-CCD, Pilatus)
1D Detector Angle Scanning
7
2θ
サンプル位置 検出器位置
L
x
pixel
Intensity
散乱プロファイル
標準試料の反射ピーク位置 からカメラ長を算出
ここで、dは面間隔、nは次数、λは波長を示す。
)2tan(Pixel
θΔ=L
)sin(2 θλ dn = (1)
I(pixel) vs pixelからのI(q) vs qへの変換
(2) )nm( 2)sin(4 1−==dnq π
λθπ
(3) Pixel
2Pixel Δ
=Δ d
nq πd (nm)
コラーゲン 65.300
ベヘン酸銀 05.853
CeO2 00.314
Scattering Vector and Camera Length
PFA-Cy PFMA-Cy X = 1 for y =1,2
X = 2 for y =4,6,8,10
X = 1 for y =1,2
X = 2 for y =4,6,8 200
250
300
350
400
0 2 4 6 8 10Num ber of C F
2
PFMA-Tg
PFMA-Tm
PFA-Tg
PFA-Tm
• K. Honda et al.,Chem.Lett., 34, 1024 (2005).
• K. Honda et al., J. Phys. Conf. Ser., 100, 12035 (2008).
• K. Honda et al., Macromolecules, 38, 5699 (2005).
• K. Honda et al., Macromolecules, 43,454(2010).
gSV=7.43mN m-1
PFFA
Structural Origin of Hydrophobicity?
2. Example of WAXD 2.1 Characterization of fluoropolymer
PFA-Cy – Powder XRD–
Rf groups : perpendicular lamella
Lamellar structure : parallel to
the surface
> Both of the orientation and order of Rf groups and lamellar structure were increased by annealing
0.5 nm!
4 sinq π θλ
=
0 5 10 15 20 25
Intensity/a.u.
q/nm-1
PFA-C10
8PFA-C
6PFA-C
4
2
1
PFA-C
PFA-C
PFA-C
Lamellar structure
Hexagonal packing!
フルオロアルキル鎖を有する側鎖型高分子の精密構造解析
Poly(FAVE8) カチオン重合 Poly(FA-C8) ラジカル重合
Tm= 29.5 °C Tm= 79.0 °C
0.1
1
10
100
1000
0 0.5 1 1.5 2 2.5 3
Inte
grat
ed in
tens
ity /
a.u.
0.1
1
10
100
1000
0 0.5 1 1.5 2 2.5 3
Inte
grat
ed in
tens
ity /
a.u.
q / nm-1
1
2
3 4 5
1
2 3 5
Poly(FAVE8)
Poly(FA-C8)
Fig. 2 WAXD intensity profiles for poly(FAVE8) and poly(FA-C8) and the corresponding electron density distribution in z direction, calculated with the Fourier reconstruction method
0 0.2 0.4 0.6 0.8 1
Sheet1
PFA-C8
FAVE8
Ele
ctro
n de
nsity
/ a.
u.
z/d
( ) ( )∑∑==
==N
h
ih
N
h
zqiih zqeFeeFz
100
100 cosφφρ
( )qIFor hh 0000,0 == πφ
層法線方向の電子密度分布:エーテル結合とエステル結合の差異
ODP
RF
DP
CO O
RF
2.2 Crystallinity
Contribution of scattering from amorphous and crystalline phases are the same
110 110 200 200
110 110 200 200c
a a
Q I Q IQ I Q I Q I
χ +=+ +Crystallinity of PE
(110)
(200) 非晶ハロー
I:Peak area Q:Calibration Factor including atomic scattering factor, polarization coefficient, Debye-Waller temperature factor
Polyethylrene
イメージインテンシファイヤー + CCDカメラ (II+CCD)
FlatPanel detector DSC
ca. 2m
2.3 Temperature dependent WAXD Principle of Measurement
DSC X-rays
FlatPanel detector II+CCD
Vacuum path Beamstop
WAXD: q=8~25nm-1
SAXS: q=0.06~2nm-1
5秒ごとの時間分割測定が可能
2014/05/16 14
Sample
DSC装置 開口角 約30° TC
Al dish
Heater
Thin Sl film or Kapton film
Space
X-ray
DSC for XRD
16
Inte
nsity
/ a.
u
15 20
2θ / deg
25
WAXD profile
0.2 0.4 q /nm-1
SAXS profile DSC thermogram
60
80
100
120
140
160
温度
/ ℃
熱量 (W/g)
0 -0.1 (110)
I(q)q
2 a.
u.
(010)
(100)
(201)
II型
HT相
DSC/WAXD/SAXS同時測定による結晶相転移の追跡(増永ら)
(200)
吸熱
Tm
波長 1.5Å、カメラ長 広角 32mm、小角 2170mm 温度 30-200℃、1℃/min
-(CH2CF2)x-ran-(CF2CHF)y- X:Y = 0.82:0.18
2014/05/16
17
(A) (B) (C)
HT相
II型
非晶相
長周期
ラメラ厚さ
L / n
m
dc / nm
Intensity
x 0.1
昇温過程におけるPVDF/TrFEランダム共重合体の 高次構造変化(田代、増永ら)
長周期
結晶型
ラメラ厚さ
18
melt
PVDF/TrFEランダム共重合体の相転移過程における ナノ、メソ構造モデルの変化(増永ら)
A B C
28
4
31
10 13
(nm)
ラメラ構造 38
SAXS
II form (monoclinic) HT phase (hexagonal)
a=5.4Å
b=1.01Å
a=5.9Å 結晶構造
WAXD
40 90 130 155 oC DSC
反強誘電相 常誘電相
温度領域
誘電性 常誘電相
フルオロオクチル側鎖を有するポリマーのWAXD/DSC同時測定結果
CF2 CF CH2 CH
On
CH2 CF2 CF32 7
Cl
1. 5 4. 0 8. 0 12. 0 16. 0 20. 0 24. 0 28. 0 32. 0 35. 0+002Thet a[ deg]
0
2000000
4000000
6000000
8000000
10000000
12000000
14000000
16000000
18000000
20000000
22000000
24000000
26000000
28000000
3000000030726237
Inte
nsit
y[cp
s]
Fr om: 1 To: 34 St ep: 1
0. 0
5. 0
10. 0
15. 0
20. 0
25. 0
30. 0
35. 0
40. 0
45. 0
50. 051. 1+00
Time
/min
- 3. 5- 3. 0- 2. 5- 2. 0- 1. 5- 1. 0- 0. 50. 00. 6+00 Heat Fl ow/ mW
- 1. 0- 0. 8- 0. 6- 0. 4- 0. 20. 00. 20. 40. 60. 81. 0+00 Humi di t y( %)
- 10. 80. 010. 020. 030. 040. 050. 060. 072. 6+00 Temper at ur e/ C
TEMP
DSC青:DSC信号 赤:温度
WAXDプロファイル
Figure 1. DSC curve and corresponding WAXD intensity profiles for 11BCD40 in second heating and cooling cycle.
11BCD40
融解ピーク
結晶化ピーク
20
2D Detector
Stretching direction�
Meridian�
Equator
q = 4π sinθλ
2.4 in situ WAXD under Deformation
PEの結晶系 :斜方晶a
b
a=0.493 nmb=0.740 nmc=0.253 nm
na=nb=1.51nc=1.58(光軸 )Δn=nc-na=0.07
PEの屈折率 : ..
..
*
αβ
γβ
abc
球晶の中心
屈折率楕円体
ラメラ結晶のねじれ
球晶の成長方向
明暗 暗山 谷
単結晶に対応するラメラ結晶が高分子の基
本構造
ポリエチレンの場合この面をフィルム面上から観察したときにac面が膜面に平行になったときΔnが最
大
ポリエチレンの消光リングの生ずる理由�
集光型μBeam X-ray Diffraction 装置
FZP in He
Sample
WAXS detector
SAXS detector
FZP: 200µm
Beam Stop
Detector Sample
308 mm
Slit:30µm OSA: 50µm
13000 mm
0.96µm
derivation
Pinhole: 60µm
集光型マイクロビームシステムとSAXS/WAXS測定システムを組み合わせ構築
1 µmの位置分解能で3~30 nm、0.8~0.3 nmの階層構造評価が可能
Specification of µBeam SAXS/WAXS apparatus
バックグランド(寄生散乱)の低いµBeam SAXS/WAXS測定が可能
6 x 8 µm 1.2 x 109 ph/s/µm2 qmin < 0.06 nm-1
波長:0.1 nm カメラ距離:1800 mm at BL03XU in SPring-8
一軸延伸ポリプロピレン(厚さ20µm)のSAXS/WAXS散乱パターン。 X線照射時間:2秒
27 27
Huang, P.; Cheng, S. Z. D. et al. Macromolecules 2001, 34, 6649. Li, D.; Xia, Y. N. et al. Adv. Mater. 2004, 16, 1151. Honda, K.; Takahara, A. et al. SoK MaLer 2010, 6, 870. Wu, H; Su, Z. et al. Macromolecules 2007, 40, 4244.
Methods for Genera3ng 1D Polymer Nanostructures
Characteriza3on of Polymer Nanorod
Self-‐Assembly of Block Copolymers Electrospinning
Nanoimprint Lithography
Template Infiltra3on
Polymer Film
AAO
28 28 Steinhart, M. et al. Phys. Rev. LeL. 2006, 97, 027801.
Polymers in Cylindrical Nanopores
Background
Shin, K.; Russell, T. P. et al. Nat. Mater. 2007, 6, 961.
Shin, K.; Russell, T. P. et al. Science 2004, 306, 76.
Enhanced Mobility
Amorphous
Specific Orienta3on Reduced Crystallinity Polymorphic Behavior
Semi-‐Crystalline
Novel Morphologies
Block Copolymers
29
Materials and Methods Polymer: iPS: IsotacVc Polystyrene, Mn = 120.5 k, Mw/Mn = 1.16
AAO Templates:
Crystal Structure: Trigonal Unit Cell: Space Group R3C, a = b = 2.19 nm,c = 0.665 nm
Nanopore: High-‐Surface Energy
(350 mN/m) Capillary Force Polymer Melts:
Low-‐Surface Energy (38 mN/m)
Melt-‐we_ng: 533 K for 8 h. Crystalliza3on: 443 K for 40 h.
The AAO templates were fabricated via a two-‐step anodiza3on.
Steps of Preparing Polymer Nanomaterials
30
Fabrica3on Procedures for AAO Templates
Masuda, H. et al. Science 1995, 268, 1466. Xu, T. T. et al. Langmuir 2003, 19, 1443.
Al
Using two-‐step anodiza3on to fabricate AAO templates.
AAO Templates
AAO: Anodic Aluminum Oxide
Second Anodiza3on
Removing Alumina
First Anodiza3on
Coat Protec3ve Layer
Strip-‐off Aluminum
Dissolving Barrier Layer
Removing Protec3ve Layer AAO Templates
31
Beam Size: 2.9 μm × 3.5 μm as half-‐width ; Wavelength: 0.082656 nm Step: 5 µm
X-‐ray Microdiffrac3on Setup BL40XU
Microbeam System
Op3cal micrographs of a thin slice of iPS nanorod arrays/bulk in the Micro-‐XRD measurement.
Diffrac3on Instruments
Transmission Electron Microscopy
32
SEM Images of AAO Templates and iPS Nanorod
300 nm 65 nm
SEM Images of AAO Templates
Op3cal Micrographs And SEM Images of iPS Nanorods
300 nm 65 nm
Top View
Side View
iPS Nanorods
Bulk Polymer Film
Selected Area Electron Diffrac3on of iPS Nanorod
The [001] zone of iPS single crystal
C
a
b
200nm
300nm iPS Nanorod
Trigonal Unit cell a=b=2.19nm c=0.665nm
Na6a, G.; Corradini, P.Macromol. Chem.,16,77( 1955).
Selected Area Electron Diffrac3on
a*
300 420
210
120 240
110
220
240
120
420
210
220
110 030
030
34
-25 µm 5 µm 10 µm 15 µm 20 µm 50 µm 75 µm 100 µmc
d Rod Axis
a*b*[110] (220)
Rod Axis
a*b*
(220)[100]
(300)
2D X-‐ray Microdiffrac3on pakerns
Two Dimensional X-‐ray Microdiffrac3on
Nanorod Array
AAO
Bulk
[100]
Bulk
Splay
Smaller RodLarger Rod
[110]or
[100]
[110]or
[100]
65nm Nanorod
300nm Nanorod
iPS crystals developed in (a) larger nanorods of 300 nm diameter and (b) smaller nanorods of 65 nm
300nm 65nm
35
Micro-‐XRD 1-‐D Curves Crystallinity
The crystallinity at different posi3ons is almost the same.
Op3cal Microscopy
4 8 12 16 20
q (nm-1)
Inte
nsity
(a.u
.)
(410)(211)(110) (220)(300) (330)
110
-30-20
0
20
40
60
90100
30
70
-10
80
50
10
0 10 20 30 40 50-30-20-10
0102030405060708090
100110
Pos
ition
(µm
)
Crystallinity (%)
Nano
Bulk
0 10 20 30 40 50-30-20-10
0102030405060708090
100110
Pos
ition
(µm
)
Crystallinity (%)
Nano
Bulk
4 8 12 16 20
Inte
nsity
(a.u
.)
(410)(211)
(110) (220)(300) (330)
q (nm-1)
110
-30-20
0
20
40
60
90100
30
70
-10
80
50
10
The crystallinity increase from the top to the bokom of nanorods.
Crystallinity of 300 nm and 65nm Nanorod
300nm
65nm
36
X-‐ray Microdiffrac3on Azimuthal intensity distribu3on
1. At the bokom of both nanorods, crystal grows along either [110] or [100] direc3on. 2. On the top of nanorods, [100] direc3on is preferred growth direc3on in bigger nanorods. While in smaller
nanorods, either [110] direc3on or [100] direc3on could be growth direc3on.
0 20 40 60 80 100 120
0102030405060708090
100110
FWHM (0)
Pos
ition
(µm
)
65 nm
300 nm
0 20 40 60 80 100 120
0102030405060708090
100110
FWHM (0)
Pos
ition
(µm
)65 nm
300 nm
-180 -90 0 90 180
φ (degree)
Inte
vsity
(a.u
.)
105
110
-30-20
0
20
40
60
90100
30
70
-10
80
50
15
-180 -90 0 90 180 φ (degree)
Inte
vsity
(a.u
.)
105
110
-30-20
0
20
40
60
90100
30
70
-10
80
50
15
-180 -90 0 90 180
Inte
vsity
(a.u
.)φ (degree)
105
110
-30-20
0
20
40
60
90100
30
70
-10
80
50
15
-180 -90 0 90 180
Inte
vsity
(a.u
.)
φ (degree)
105
110
-30-20
0
20
40
60
90100
30
70
-10
80
50
15
37
Conclusions
1. Crystallinity a. The crystallinity of iPS in larger nanopores (300nm) is the
same as that of bulk. b. Gradient distributed iPS crystallites formed in smaller
nanorods (65nm) owing to the crystallizaVon iniVated by the bulk. The crystallinity decreased from boLom to top of the nanorod.
2. Orienta3on a. The c-‐axis of iPS crystals in nanorods is perpendicular to the
rod axis due to cylindrical confinement. b. At the boLom of 300nm and 65nm nanorods, crystals grow
either with the [110] or with the [100] direcVon. On the upper part of nanorods, the [100] direcVon is the preferred growth direcVon of bigger nanorods(300nm). In smaller nanorods (65nm), either the [110] or the [100] direcVon could be the preferred growth direcVon along the nanorod.
Large Pore
Smalle Pore
Bulk
Smaller Rod
[110]or
[100]
AAO [100]
Bulk
Splay
Larger Rod
[110]or
[100]