Industrial Utilization of SPring-8in Polymer Fields

１．Introduction - Why now SR Beams for Polymers ?

２．Examples of Industrial Uses of SPring-8 for Polymer Studies(1) Observing curing reactions inside a polymer-modified cement

water-proofing coating material.(2) Nanostructure of polarizer films consisting of PVA and iodine.(3) Nanosurface structure of polyimide films for liquid crystal alignment

in LCD.

３．Summary - Not only wider utilization but also higher-quality utilization.

Kazuyuki HORIE (JASRI/SPring-8)

Spring-8 – Diamond Joint Workshop in Kobe (Aug. 26, 2009)

Challenges in Polymer Science＜Polymer Science in the Past＞

Description of universality that polymers consist of macromolecules connected with flexible covalent bonds

・Shape and size of chain molecules

・polymerization reactions・variety in many levels＜Polymer Science now and in future ＞

Description of features of polymers that have ordered structure in nanoscales. Controlled syntheses & precisionpolymerization

Molecular and higher-order structure in nanoscales

Physical properties & Functions

-- photonic, electronic, biomedical, environmental, …

Nobel prizes in synthetic polymer fields（year）1926-30 H.Staudinger Establishment of polymer concept

（1953)1940-50 P.J.Flory Bases of modern polymer chemistry

（1974).1953-55 K.Ziegler-G.Natta Polymerization with coordination

catalysts（1963)1970-80 P.G. de Gennes Phase transition theory in

polymers and liquid crystals （1991)

1964-70 R.B.Merrifield Peptide syntheses in solid states（1984)

1976 Shirakawa-MacDiarmid-Heeger Conducting plastics（2000)

As an object of materials science, reasearch trends expand from structural to functional polymers.

Creation of New Polymers with Specialty or Functions

＜Role of SPring-8＞

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Change in Number of Experiments at SPring-8 for Polymer & Organic Thin Film Fields ○: Proposals from Industry

◎Bulk polymersCrystalline polymers, phase-separated polymers, rubbers, composites◎FilmsPolymer films, organic thin films

◎Fibers◎SoftmattersPolymer solutions, gels, dispersion systems, biopolymers, supramolecules, liquid crystals

year

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Pulk polymers

Films

Fibers

Softmatters

Proposals from industry

Percentage of polymer study in total experiments is about 6 % (2003~06) to 10 % (2007~ ) .

However, there has been so far no BL specified to polymer research at SPring-8.

民間企業における分野別の実施課題数

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（ 利用期間）

（ 件）

OT: その他

ME: 製薬・ 生活用品

MA: 素材(金属・ 高分子・ 建材) (工業触媒)

EN: 環境・ エネルギー(環境触媒、 燃料電池)

EL: エレクト ロニクス

History of Industrial Utilization at SPring-8 at Public BLs

Start of 1st Industrial Use BL(19B2) (2001~), Trial Use Project（2003A～2005A）

Priority Industrial UseProgram （2007～）

2nd IUBL(14B2) (2007B~)3rd IUBL(46XU) (2008A~)

Experiments by industrial users have increased and become about 20% of total experiments.

Number of applicants still increases, i.e., about 30% of applicants are still rejected due to limited beam time.

Half-year research term

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ber o

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Others

Medicine, health care, cosmetics

Materials (metals, polymers), catalyst

Environmental, energy

Electronics

Strategic Activation Program forAdvanced Facilities（2005B～2006）

第二実験ハッチ

GISAXS

WAXD&GIXD, XR

SAXS

薄膜構造物性用 高精度小角・広角散乱同

時測定用

標準化試料ユニット

キネマティックマウント

sample

X-rays WAXD

sample

第一実験ハッチ

Contract Beamline of Industry-Academia Consortium for Advanced Softmaterial Research （FSBL - ＢＬ０３ＸＵ） (Start in Feb. 2010)

Hutch 1 Hutch 2

Hutch 2: Simultaneous SAXS/WAXS measurements also with DSC, IR, Raman techniques, time-resolved & in-situ measurements of various polymer processeswith microbeams.

Hutch 1: Evaluation of thin film surface structure (GIXD, GISAXS, XR), wide-angle precise diffraction measurements.

◎ FSBL Consortium consists of 19 chemical corporate groups.

◎ Every corporate group has industry and academia members. Administration Committee of the Consortium is responsible for the management of the beamline.

General Features of SR Beams and their UsesSR Beams

Ultra-bright

Highly directional

High energy

Spectrally continuous

Linearly or circularly polarized

Typical UtilizationDiffractometry of very small samples,Rapid measurements (time-resolved, during reaction, process)

Microbeam Measurements and ImagingGrazing incidence (GI) XD & SAXS

（surface, films）XPS inside samplesInner-orbital excitation of heavy atoms

X-ray absorption (XAFS）Choice of optimal energy conditionEffect of anomalous dispersion

(X-ray detects buried structure inside

materials.)

Magnetic Properties （MCD)

P(E/VAc) Polymer emulsion

Alumina cement

Mixing

Cement hydrates with water in emulsion, forming water-proofing tough coating at a construction site.

Observing Cement Hydration in Polymer-modified Cement Water-proofing Coating Materials

Detecting reactions in buried insides（１）

セメントの水和反応は温度変化の試験から見ると急激に温度上昇があり、どの時点で反応があるかを観察する必要がある

SR beam is needed for high resolution, rapid measurements during reactions

Ozeki Chemical Industry Co., Ltd.

Water-proofing coating is important at underground construction sites.

Hydration reactions of cement are exothermic, temperature rises, and the reactions inside should be monitored as a function oftemperature and humidity.

Detecting reactions in buried insides （２） K. Miyashita, Ozeki Chemical Industry

CA： CaO・Al2O3C2AH8：2CaO・Al2O3・

8H2OC3AH6：3CaO・Al2O3・

6H2O

Ozeki Chemical Ind. Co. Ltd.: A pioneer of this field, capitalized at 60 million yen, 95 employees.

◎Realizing a precise method of designing materials and processes suitable for each temperature and humidity in construction environments.

◎Use of their materials in major facilitied in Japan & Overseas; Roppongi hills, Shanghai World Financial Center, Tokyo Nerima Tunnel etc.

Hydration Reactions in Polymer-Cement Water-proofing Coating

X-ray

Sample sandwiched between glass plates

r. t.

975 min

15min

Angle (2θ)r. t.

Reaction time (min)

BL19B2

M. Kotera, I. Matsuda, K. Miyashita, SPring-8 Research Frontier, 2004, p. 131

Absorption of Iodine into Drawn PVA Films in KI/I2 Solution

Crystalline regionAmorphous region

dmax

? dmin - amorphous or crystalline ?

SAXS patterns for PVA films, (a) drawn in Pure water, (b) drawn in KI/I2 solution

（b）

（a）

T. Miyazaki, S. Sakurai et al., Polymer, 46 7436 (2005)

BL40B2

Nitto Denko Co., Ltd.Observing nanostructure of polarizer films with SAXS/WAXS (1)

- Lamellar thickness

Correlation function γ(x) for meridional slice of a 2D SAXS pattern

Double network modelby Miyasaka

BL40B2

Observing nanostructure of polarizer films with SAXS/WAXS (2)

Absorption of Iodine into Drawn PVA Films in KI/I2 SolutionT. Miyazaki, Nitto Denko Co.

WAXS patterns for PVA films, (a) drawn in Pure water, (b) drawn in KI/I2 solution

Azimuthally integrated intensity propile for a 2D WAXS pattern

Crystallinity index vs. draw ratio

T. Miyazaki, S. Sakurai et al., Polymer, 46 7436 (2005)

Observing nanostructure of polarizer films with SAXS/WAXS (3)

Crystalline regionAmorphous region

dmax- Lamellar thickness

dmin-amorphous thickness

Double network model by Miyasaka (Adv. Poly. Sci., 91, 108 (1993)

A new model by Miyazaki et al. (Macromol. 40, 8277 (2007)

1. The increase in dmin with increasing DR up to 4 in KI/I2 solution suggests the PVA-iodine complexs are formed in amorphous regions in PVA films.

2. The increase in crystalline thickness for DR>4 drawn in KI/I2 solution should be attributed to the stress-induced crystallization.

3. Further, simultaneous SAXS/WAXS measurements of PVA films during drawing in water clarified the mechanism of strain-induced crystallization taking place in the interfibrillar extended amorphous regions, and proposed a new model for nanostructure of drawn PVA films.

T. Miyazaki, S. Sakurai et al., Polymer, 46 7436 (2005); Macromolecules, 39, 2921 (2006); 40, 8277 (2007)

(a) drawn in Pure water, (b) drawn in KI/I2 solution

（a）

（a）

（a）

（b）

（b）

（b）

GIXD for Surface Evaluation of Rubbed Polyimide Films for Liquid Crystal Display

LC aligning film (polyimide coated on electrode)

Rubbing the surface with a cotton cloth

Surface of PI film is grooved.

LC molecules can be aligned.

Relating nanosurface structure to functions (1)Nissan Chemical Industries, Ltd.

LC aligning film

(Rubbed

polyimide, PI)

Polarizer

Transparent electrode

Liquid crystal

LC aligning power of the film is controlled by rubbing the film surface.

Samples

GIXD Measurements X-ray energy：10keV Incident angle (αi)：

0.12°(surface sensitive)0.16°(bulk sensitive)

Beamline：SPring8 BL19B2

What is the origin of LC aligning power ?

NN

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OO

O

NN

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OO

O O O

SP-PI4

SP-PI1

Relationship between LC Aligning Power and Nanosurface Structure

液晶配向力　予測される結晶性SP-PI1 　　○ 　　　　○SP-PI2 　　△ 　　　　△SP-PI3 　　◎　 　　　　○SP-PI4 　　× 　　　　×

回折面

iα

Bθ2

面内回

iα入射X線（αi ：入射角）

◎GIXD(grazing incidence X-ray diffraction) is sensitive to scattering from sample surface (~ 8nm)

Relating nanosurface structure to functions (2) What happens by rubbing the surface ?

T. Sakai, Nissan Chem. Industries, Ltd.

Diffraction planes

LC align. power Supposed crystallinity

GIXD Measurements of LC Aligning Polyimide Films

SP-PI3

SP-PI3

SP-PI4

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SP-PI4

LC aligningpower depends on surface crystallinity.BL19B2

Relating nanosurface structure to functions (3) T. Sakai, Nissan Chem. Industries

A film with good LC align. Power A film with poor LC align. PowerBulk-sensitive

Surface-sensitive

Rub Direc. // q

Rub Direc. ppd q

Scattering angle (2θ)

Bulk-sensitive

Surface-sensitive

Rub Direc. // q

Rub Direc. ppd q

Scattering angle (2θ)T. Sakai, Kino Zairyo (Functions & Materials) 27(2) 69 (2007); Spring-8 Research Frontiers 2007,

p. 152 (2007).

Summary 1: Reasons of Good Results in Industrial Utilization of SPring-8

１．Stable SR beams of a world top level are constantly supplied.

○Ultra-bright, ○Highly directional, ○ Top-up operation.

２． R & D people in industries have been trying to find out new nano-scale techniquesfor solving their problems.

○ Action (giving information) of people in Analytical & Evaluation Technology Division to people in R & D Division is important.

３． Technical staffs in JASRI Industrial Application Division have been supporting industrial users in sample preparation, measurements at SPring-8, and sometimes alsoin analyzing the data.

○ Financial support from Government on number of staffs for promoting industrial uses. (Trial Use Program, Strategic Activation Program)

○ A change In professional morals of BL technical staffs has been needed.

４．The quality of research has been improved by industry-academia collaboration.

○Industry: consideration based on basic theories, Use of new techniques, Improvement in data analyses.

○Academia： Finding new basic subjects from the discussion with industry, Advances of technology in SR measurements.

XD, SAXSCrystalline polymersFibers

XD + SAXS, GI, MB, Time-resolved, Imaging○ Crystalline polymers, Fibers → Dynamics○ Nanosurface & buried interface in Polymer films, Organic devices.○Higher-order structure (phase-separated polymers, composites)○ Gels, Micelles, cell membranes◎ Towards not only wider utilization, but also

more advanced quality of utilization。

*e.g. Industry-Academia Consortium for Advanced Softmaterial Research (FSBL) consisting of 19 chemical corporate groups including academic members. (BL03XU)

Summary 2: Challenges in Industrial Utilization at SPring-8 --- Towards More Advanced Quality of utilization

◎ Trails of wider utilization In polymer fields

1. Good subjects are brought about by active participation of R & D people.

2. Closer collaboration between industry and academia(*) and closer international collaboration between SR facilities in the world.

3. Bring up young scientists in SR fields.

SR people

Evaluation Technology people

R & D people