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Copyright 2013 Toray Industries, Inc. All Rights Reserved

NANOALLOY® Technology for High Performance CFRP

March 29, 2013 Workshop on Next Generation Transport Aircraft

Toray Industries, Inc. Ehime Plant Composite Materials Research Laboratories

Takayuki Fujiwara

Toray Proprietary


Target for mechanical properties

1)Relative values to conventional material :100

Flexural modulus1)

Frac

ture

toug

hnes

s(K

IC)1

)

50

80 100

100

150

Conventional epoxy

120

200

0

(2005)(1995)

Impact resistantresin

50

90

100

150

200

0100

Conventional CFRP

120

(2005)(1995)

0˚ Compression strength1)

Impact-resistantpregreg

110

Inte

rlam

inar

frac

ture

toug

hnes

s（G

Ic）

CFRP Epoxy resin

1. Introduction2

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B:Epoxy or thermoplastic (Tp)

MixingA: Epoxy(Ep) Bi-continuous structure

Sea-island structure

NANOALLOY® technology changes the compatible mixture into nano-scale phases during the cure.

CuringCompatible mixture

TEM image 100 nm

NANOALLOY® technology for epoxy1. Introduction

100 nmTEM imageTEM image 100 nmTEM image

One phase

Two phaseTem

pera

ture

A ratio0 1

One phase

Two phaseTem

pera

ture

A ratio0 1

Reaction-induced phase separation

Boundaryshifting

3

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Why “nano”?1. Introduction

273 10

6 fVn 9106 fVSA 16

23/1

fd

The interaction between matrix and domain

4

0° 90°Homogeneous dispersion between carbon fibers

Nanophase separation increases the interaction.

Carbon fiber (ϕ: 6 μm)Interlayer distance

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NANOALLOY® Map

Flexural modulus1)

Impact resistant resin applied epoxy/thermoplastic

NANOALLOY®Fr

actu

re to

ughn

ess(

KIC

)1)

100

100 115

150

200

Conventional epoxy

130

250

50

NANOALLOY® technology improves both fracture toughness and flexural modulus of epoxy resin.

1)Relative values to conventional epoxy :100

1. Introduction5

Epoxy resin

Impact resistant prepreg applied epoxy/thermoplastic

NANOALLOY® technology

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TEM image of cured resin

500nm

Properties Conventional epoxy Impact resistant epoxy

Flexural modulus1) 100 94Flexural deflection1) 100 113

Fracture toughness (KIc)1) 100 181Glass transition temperature (°C) 115 120

•The toughness is drastically improved with keeping other major properties.

•Thermoplastic is dispersed in cured resin as nano-scale domain (White dots in TEM image).

1) Relative values to conventional epoxy :1002) Cured condition : 135°C x 2hrs.3) KIc : Crack opening mode, Fracture toughness test

Cured resin properties2. Impact resistant prepreg applied epoxy/thermoplastic NANOALLOY® technology7

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Mechanism for impact resistance

1. “Thermoplastic domain” absorbs impact energy by “cavitation” effect.

2. “Spherical thermoplastic structure” absorbs impact energy by plastic deformation.

3. “Nano-scale dispersed” thermoplastic domain stops crack propagation by blocking out its route.

Thermoplastic domain

50nm

Crack Cavitation Crack wraps around domains

Toughened epoxy resin

8 2. Impact resistant prepreg applied epoxy/thermoplastic NANOALLOY® technology

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Charpy impact strength Standard-modulus CF(T700S)- prepreg

0

50

100

150

200

ConventionalCha

rpy

impa

ct s

treng

th[k

J/m

2 ]

FAW=150gsm, Wf=63% prepregTest method : JIS (3mm-t)

Total absorbed energy (laminate)

+ 79%

0

200

400

600

800

Cha

rpy

impa

ct s

treng

th[k

J/m

2 ]

+59%

Total absorbed energy (model pipe)

Conventional Impact resistant

FAW=150gsm, Wf=63% prepregPipe inner diameter=6.3mmf [+/-45˚ 3ply, 0˚ 3ply]

Energy before the max. load

Total absorbed energy +

Energy after the max. load

Load

→

Displacement →

ConventionalImage of charpy impact test chart

Impact resistant

Load

→

Displacement →6

Impact resistant properties of CFRP9

Impact resistant

2. Impact resistant prepreg applied epoxy/thermoplastic NANOALLOY® technology

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CFRP of standard-modulus CF (T700S)

Conventional Impact resistant

0ﾟ Tensile1)2)Strength 100 101

Modulus 100 101

90ﾟ Tensile strength1) 100 104

0ﾟ Compression strength1) 100 93

0ﾟ Flexural1)2)Strength 100 98

Modulus 100 93

0ﾟ Interlaminar shear strength1) 100 90

Inplane shear strength1) 100 96

Interlaminar fracture toughness（GIc） 100 245

Charpy impact strength1) 100 179

1) Relative values to conventional CFRP :1002) Normalized value in Vf = 60%

10

CFRP properties2. Impact resistant prepreg applied epoxy/thermoplastic NANOALLOY® technology

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Charpy impact strength Modelate-modulus CF(T800S) - prepreg

0

50

100

150

200

+61%

0

200

400

600

800

+39%

ConventionalCha

rpy

impa

ct s

treng

th[k

J/m

2 ]


Cha

rpy

impa

ct s

treng

th[k

J/m

2 ]


Conventional


FAW=150gsm, Wf=63% prepregPipe inner diameter=6.3mmf [+/-45˚ 3ply, 0˚ 3ply]

7


Impact resistant Impact resistant


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CFRP of intermidiate-modulus CF (T800S)

Conventional Impact Resistant


Modulus 100 101




Modulus 100 93





Mechanical properties of CFRP12



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Charpy impact strength High-modulus CF(M40J )- prepreg

0

50

100

150

200

Cha

rpy

impa

ct s

treng

th[k

J/m

2 ]


Conventional

+8%

0

200

400

600

800

ConventionalCha

rpy

impa

ct s

treng

th[k

J/m

2 ]


+18%


FAW=150gsm, Wf=63% prepregPipe inner diameter=6.3mmf [+/-45ﾟ 3ply, 0ﾟ 3ply]

8


•The charpy impact strength improvement is smaller than the result of T700S or T800S.

•The fracture of fiber is predominant rather than that of resin in interlayers.

Impact resistant Impact resistant


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CFRP of Hi-Modulus CF (M40J)

Conventional Impact Resistant


Modulus 100 100




Modulus 100 97





Mechanical properties of CFRP14



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1.E-11

1.E-10

1.E-09

1.E-08

1.E-07

1.E-06

1.E-05

100 200 300 400 500GIIc [J/m2]

Mode-IInterlaminar fracture toughness(GIc)(Double Cantilever Beam)

1.E-10

1.E-09

1.E-08

1.E-07

1.E-06

50 100 150 200 250GIc[J/m2] C

rack

ext

entio

n ra

teda

/dN

[m/c

ycle

]

Conventional CFRPImpact resistant CFRP

Mode-II Interlaminar fracture toughness (GIIc)(End Notched Flexure)

9

Cra

ck e

xten

tion

rate

da/d

N[m

/cyc

le]

*These experimental data are not guaranteed in all case.

Fatigue resistance properties of CFRP15

The crack propagation energy of impact resistant CFRP is significantly larger than the conventional CFRP.


Conventional CFRPImpact resistant CFRP

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16

Summary

NANOALLOY® technology led to the invention of a novel prepreg.

Impact resistant prepreg applied epoxy/thermoplastic NANOALLOY® technology• The impact-resistant prepreg is well-suited for damage-sensitive applications. • The impact-resistant prepreg achieved higher charpy impact strength by about

80% than the conventional prepreg.

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17

Thank you for your attention

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