2022/3/25

Surface and Interface of Polymers「膜工学春季講演会」膜工学サロン（ZOOM）
2022/3/29
サロン D(16:10~17:50)

AirSurface
BulkPolymer

Interface

量子ビームから捉える薄膜・界面の相互作用Interaction
Bulk ・・・・Polymer chain VS Polymer chain
Surface ・・・・Polymer chain VS Air (or none)
Interface ・・・・Polymer chain VS Other polymer chainor Solvents

神戸大学 大学院 工学研究科
松本 拓也

Mobility Up or Down
Tg Up or Down

Asymmetric chemical interaction+ physical factor

1

Synchrotron Radiation

Synchrotron Radiation

BL03XU• X-ray beam

2

• Neutron beam

J-PARC MLF@Tokai

Neutron beam

X-ray beam
• detect the differenceof densities• no electric charge• distinguish isotopes (nucleus)• sensitive to atomic and molecular structure• high transmittance• detect hydrogen and deuterium
Polymer VS water
http://www.spring8.or.jp/e/

BL16 SOFIA• Beam Intensity : 100,000,000 times (vs X-ray beam @Lab.)• Beam Divergence : 0.00086°(0.01°@Lab.)• One measurement : < 1sec (30 min @Lab.)in situ or operand measurements• SAXS, WAXD, XAFS, IR, CT,,,, etc.
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Outlines

Neutron Reflectivity (NR)

1. 水をはじく高分子とはじかない高分子の界面Interference of light+
Neutron beam

Incident
Beam

Reflected
Beam

Layer
Substrate

Scattering vector : q = 4𝛑sin𝜽/𝝺2. 水を吸う高分子の内部構造

Scattering
Vector (q)Incident
Intensity (Ii)

Scattering length density (SLD)𝝆

Reflection
Intensity (Ir)𝑏

For example,,,𝜽

3. 高分子の接着界面に発生する応力

𝑁 𝜌𝑀

Film
Substrate

ρ(H2O) = -0.2210-4 nm-2
ρ(D2O) = 6.3310-4 nm-2

Reflectivity : R(q) = Ir/Iiρ(polymer) = 1~2  10-4 nm-2

Bragg’s Law : nλ＝2dsinθ

5

Neutron Reflectivity (NR)
Advantage of NR

6This Work

3

Synthesized

Neutron beam
• distinguish isotopes (nucleus)• high transmittance• detect hydrogen and deuteriumnO

Poly(4-Trifluoromethylphenylmethacrylate)(P(CF3))

OCF3• Neutron beam from substrate
Interface between polymer and water
Solvent

Volume fraction of mixture
from the contrast of SLDs
For example,,,Substrate

Poly(4-Pentafluorosulfanylphenylmethacrylate)(P(SF5))

ρ(layer) = ρ(polymer)polymer+ ρ(D2O) D2O

Layer
Incident
Beam

Poly(4-Methylphenyl methacrylate)(P(CH3))• Distribution of absorption components

ReflectedBeam

Spin-coating

Concluded….

Water

Thin filmPolymer

7

Surfaceproperties

Poly(4-Phenyl methacrylate)(P(H))

Fluorine-containing
functional groups(-SF5, -CF3)

Affect?
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Contact angle

NR profiles

Table The water and ethylene glycol contact angles andsurface free energy values of four spin-coated films.

SampleWater
contact angle

EthyleneGlycol
contact angle

Surfacefreeenergy

deg.

deg.

mJ/m2
15.0

P(SF5)

102

85

P(CF3)

96

73

22.4

P(CH3)

92

68

24.7

P(H)

8157

29.0

Higher fluorine contentin a side chain

P(CF3), P(SF5) Double-layer model P(H), P(CH3)WeakerLower

Triple-layer modelD2O or D2O/H2O

D2O or D2O/H2O

Polymer bulk

Polymer bulk

Adsorbed layer
SiO2Adsorbed layer
SiO2Top surface layer(c)
Si9(c)
Si10

Neutron Reflectivity (NR)Conclusions

Advantage of NR

Neutron beam
• distinguish isotopes (nucleus)• high transmittance• detect hydrogen and deuterium• Neutron beam from substrate• Distribution of absorption components

Interface between polymer and water

Hydrophobicity

Solvent

Interaction with water

Volume fraction of mixture
from the contrast of SLDs
For example,,,ρ(layer) = ρ(polymer)polymer+ ρ(D2O) D2O

Layer
Incident
Beam

Water content in top surface region
Top surface layer
Water

Water

Water

Polymer

Polymer

Polymer

Substrate

Reflected
Beam

Concluded….

air

11

Substrate1232022/3/25

Introduction

NR @ J-PARC
D2 O
DMobility
Polarity
C2 polymer

Identification
Bas de Bruin, et.al., Organometallics, 29, 28232826(2010)▶ Measurement condition (@25 ºC)

Poly(acetic acid)100

Interaction
with water
Water
Side chains

80
60
40

Anti-icing effects

13SLD profiles
SLD (104 nm-2)

C1-PAA40

76543210-20020406080

SLD (104 nm-2)

Distance from Si (nm)
5C2-PAA4054332120-20020406080

80120

160C2-PAA80

1Distance from Si (nm)40

C1-PAA80

Distance from Si (nm)40100 -10 076543210-20 020246810

Volume fraction ofD2 O

1214Time (h)Fig. Program of humidity change at 25 ºC.

161814• 15/
15Poly(substituted methylene)
Water adsorption layer

C1-PAAHigh swelling

20 40 60 80 100 120

Distance from Si (nm)C2-PAA100

654321010 20 30 40 50 60 -20 0

Distance from Si (nm)Dry
WetMolar fraction of carboxyl side chain

C2-PAA
20 40 60 80 100 120

Distance from Si (nm)Fig. SLD profiles of C1-PAA and C2-PAA spin-coated films under 10%RH and 90%RH.

Thickness(90%RH) D O

Conclusions

C1-PAA60

76543210
100 -20 0

Wet200

Biocompatibility

Wet(@90%RH)

Dry(@10%RH)

Hygroscopicity

O

Water-soluble polymer
Paper/disposable diaper
PaintsAdhesiveDry(10%RH)

Keep
Measurement

Gradation••••Humidity (%RH)

HOH

Side chain densityPolyacrylic acidn

Hygroscopicity

Neutron reflectivity
Poly(substituted methylene)
C1 polymer

Vinyl polymer

Shape of
SLD profiles

15

Different swelling properties

Different swelling behavior
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X-ray Diffraction Stress Measurement

Introduction
Adhesion

After curing
Epoxy resin

Epoxy resin

Parallelto the surface

Material

Residual stressMechanical properties
Insulation

Industrial products

Deformation Detachment

Metal

AlternativeVehicle
Aircraftsin2ψ method
Ψ=60°

Reliability

1

𝜀

ψ=40°
ψ=30°
ψ=2.6°

it.PP/EP
Laminate film

ψ=60°
ψ=50°
ψ=40°

ψ=30°
ψ=2.6°9.5
10 8.59.0
9.5
102θ (deg.)2θ (deg.)
Fig. X-ray diffraction profiles of it.PP/it.PP reinforced with glass fiber film (left)
and it.PP/EP film (right) at different azimuth angles at α=2.0°.
8.5

9.0

Tensile stress

19

Residual strain εψ (%)ψ=50°

Intensity (a.u.)

Intensity (a.u.)

ψ=60°

Peak shift

Residual stress𝜈 𝜎sin2𝜓𝐸

𝜈
𝜎
𝐸

18

Residual Stress0.7it.PP
laminate film

Surfaceνs：Poisson’s ratio of adherend
Et：Elastic modulus of adherend
σr：Residual stress
ε ：Residual strain

sin2ψ172θ Profiles of Laminated it.PP
Peak shiftΨ=30°

sin2ψ method

Residual stressmeasurementPolymer

・Low cost・Light weight

Ψ=90°

FailureDefects
Residual strain εψ

X-ray diffraction

Thermal expansion
coefficient mismatch

1𝜀0.6

𝜈 𝜎
𝑠𝑖𝑛 𝜓𝐸𝜈
𝜎𝐸

0.5

Compressive 1.9 MPa

0.4
0.3

00.2

0.4
0.6
0.8
sin2ψ
Fig. Relationship between the residual strain of the it.PP/EP film
and sin2ψ. α

Epoxy resin
it.PP

Compressivestress

Glass fiber
reinforced it.PP205

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Thickness Dependence of Residual Stress
5.0

Residual stress (MPa)𝑥0ln 0.99𝜇1
𝑠𝑖𝑛𝛼

1
sin 2𝜃

Conclusions
 Reflection method

𝛼X-rayμ: Linear absorption coefficient (/cm)-5.0Compressive
Stressconcentration-10.0

 Dependence of it.PP thickness

EP
-15.0

0it.PP

100

200

300

400

500

Stressconcentration

600

X-ray penetration depth x (μm)
Fig. Relationship between residual stresses of it.PP/EP sheetswith 240 s plasma treatment and X-ray penetration depth.

21

Summary

22

Acknowledgements

Measurements with Synchrotron Radiation
What?

How?

西野 孝 教授

Observation of undetectable structure and interaction

謝 イチクン
冨岡 美里
細見 亮介

1. 水をはじく高分子とはじかない高分子の界面
2． 水を吸う高分子の内部構造

KEK 山田 悟史 准教授
瀬戸 秀紀 教授
防衛大 根本 文也 助教

3． 高分子の接着界面に発生する応力23246