FUNCTIONALIZED FLUOROPOLYMERS

FOR AUTOMOTIVE APPLICATIONS

Automotive Energy Storage Systems

ITB Group

March 2016

Agenda

AGC Overview

Adhesive ETFE

Chemical Resistance of ETFE

Conductive Fluoropolymers

New Adhesive Fluoropolymers

New Heat Resistant ETFE

Global Operations

World’s #1 glass manufacturer

Approximately 51,500 employees

US $13 billion net sales

200 consolidated subsidiaries in 30

countries

Global Sales #1 global

supplier of flat

and auto

glass

Largest global

glass supplier

to:

NISSAN

HONDA

TOYOTA

World’s #1

supplier of

ETFE

Global Product Reach

25% Chemicals

and Other

25% Electronics

25% Glass

AGC Chemicals Group – Global Network

• Headquarters – Tokyo

• Factories – Chiba and Kashima

• Sales offices – Tokyo, Osaka, Fukuoka, Nagoya

• R&D – Yokohama

• 9 other divisions

AGC Chemicals Japan

• AGC Chemicals Trading Co. Ltd. – Shanghai, China

• P.T. Asahimas Chemical – Jakarta, Indonesia

• AGC Chemicals Co. Ltd. – Bangkok, Thailand

• AGC Chemicals Asia Pacific Pte. Ltd. – Singapore

AGC Chemicals Asia

• Head Office and Production Plant – Thornton Cleveleys, UK

• Commercial Center – Amsterdam, The Netherlands

AGC Chemicals Europe

• Head Office and Technical Center – Exton, Pa., USA

• Production Plant – Thorndale, Pa., USA

AGC Chemicals Americas, Inc.

U.S. Locations

Manufacturing Plant

Field Sales

Warehouses

Head Office

Proven Track Record in Automotive

Fuel Line Requirements for ETFE

• Long term durability

• Fuel and chemical resistance

• CE5, CE10, CM15, CE22, CM30, CE85, E100

• Bio fuels

• auto-oxidized fuels

• Low permeation

• Euro4, Euro5, Euro6

• LEVII, PZEV, LEVIII

• Static dissipating

• Processability

• Formability

• Oligomer protection

• Cost reduction

The Role of Fluoropolymers

Functionalized for a range of requirements:

• Adhesion to dissimilar materials

• Chemical and permeation resistance

• Conductivity

• Flexible processing parameters

• High temperature performance

Adhesive ETFE

O

C

C

O

O

PA12 ETFE

+ N

H

H

N

C

C

O

O

260~330deg.C

Imide bond formation

• Heat stable

• Fuel and chemically stable

• Excellent durability

amine terminated

PA and AH-ETFE were mixed by Laboplastomill at 260 deg.C

for 3 minutes.

The blended sample was treated by hexafluoroisopropanol.

85

90

95

100

16501700175018001850190019502000

Tra

nsm

ita

nce

(%

)

Wavenumber (recip.cm)

PA12

AH-ETFE

PA+ETFEAdhesive-ETFE

Imide

Adhesive ETFE

Observation of imide bond at the interface

30

40

50

60

250 260 270 280 290 300 310 320 330

Pee

l stre

ngth

(N/c

m)

Temperature of co-extrusion die (deg. C)

AH-2000 ETFE/3030JI6L PA12

Other 2-layer tube system

Blister

Adhesive ETFE

AH-ETFE shows excellent peel strength over a wide

range of processing temperatures

0.75mm outer layer / 0.25mm inner layer

8mm OD / 6mm ID hose

12

Soaked at 60 deg.C Filled at 60 deg.C

0

10

20

30

40

50

60

0 1000 2000 3000 4000 5000 6000 7000 8000

Pe

el str

eng

th (N

/cm

)

Soaked time (hrs)

0

10

20

30

40

50

60

0 1000 2000 3000 4000 5000 6000 7000 8000

Filled time (hrs)

CM15

Fuel-C

CE10

Chemical Resistance of ETFE

0.75mm outer layer / 0.25mm inner layer

8mm OD / 6mm ID hose

Peel strength of non-conductive type tube remains above

40 N/cm even after for 7500 hrs of fuel exposure

Conductive type tube impossible to peel after 7500 hrs

Permeation rate of AH-ETFE decreases with increasing

ethanol content in fuel

E100

Measurement: cup method

T 60 deg C

Fuel C + 2% water

Chemical Resistance of ETFE

0

0.5

1

1.5

2

2.5

3

0 10 20 30 40 50 60 70 80 90 100

pe

rme

atio

n r

ate

(g

*mm

/m2*d

ay)

ethanol content (volume %)

FFV

E100

CE10

0.75mm PA12 /0.25mm thick AH-ETFE

8mm OD /6mm ID

Chemical soak at 23 deg C for 2 hrs

Dried at 80 deg C for 72 hrs

AH-ETFE exhibits physical property retention in a

variety of process fluids

Chemical Resistance of ETFE

Property Initial Value

Tube length 200 mm

Tensile strength 900 N

Elongation at break 368%

Impact strength 7.2 MPa

Burst pressure 7.4 MPa

1

10

100

1000

10000

100000

1000000

10000000

100000000

2 4 6 8 10 12 14 16

Re

sis

tivity (

ohm

*cm

)

Carbon Load (%)

Resistivity in C-88AP ETFE

Carbon A

Carbon B

Conductive & Anti-Static Compounds

Conductivity is a function of:

• resin

• carbon

• many other variables

Extremely stable conductivity

• Resistant to shear process

• Minimized losses over time

1.00E+00

1.00E+01

1.00E+02

1.00E+03

1.00E+04

1.00E+05

1.00E+06

1.00E+01 1.00E+02 1.00E+03

log

Re

sis

tivity (

oh

m*c

m)

Shear rate (cm-1)

T = 320 °C

Other ETFE

conductives

AGCCA ETFE

conductives

Conductive & Anti-Static Compounds

Polymer Melt T (°C) Comments

LH-8000 ETFE 180 Adhesion to lower melt T plastics

PE, PP, PET, TPEs, etc.

AH-ETFE 230 - 260 Adhesive ETFE, especially for co-extrusion

with polyamides

EA-2000 PFA 300 Adhesive PFA, for co-extrusion with higher

melt T materials or metal lamination

Molding temperature of adhesive fluoropolymers

200 °C

LH-8000 ETFE

250 °C 300 °C 350 °C

AH-ETFE

EA-2000 PFA

Partially

fluorinated

Perfluorinated

Range of Adhesive Fluoropolymers

Property Method Units LH-8000 ETFE AH-ETFE

Melt Flow Rate

ASTM D3159

(235

deg.C*2.16k

g)

g/10min

4.8 -

ASTM D3159

(265 deg.C*5kg) 37.1 -

ASTM D3159

(297

deg.C*5kg)

78.6 24

Specific Gravity ASTM D792 - 1.75 1.78

Melt T DSC deg. C 180 230 - 260

Tensile Strength ASTM D638 MPa 44 49

Elongation ASTM D638 % 417 420

Flexural Modulus ASTM D790 MPa 959 790

Izod ASTM D259 - N/B N/B

LH-8000: Low Melting Adhesive ETFE

HF generation after 1 hour at process temperature.

5

50

500

200 220 240 260 280

HF

ge

ne

rati

on

(μg

/g-p

oly

me

r)

Temperature (deg. C)

PVDF

LH-8000

Processing Window

LH-8000 Processing

Processing window & thermal stability

Processing T is far lower than decomposition T

Td : Decomposition temperature

200 265ºC

180ºC 225ºC

240ºC

ETFE LH-8000

LH-8000 Processing

HDPE

LH-8000 ETFE

Co-extruded HDPE & LH-8000 ETFE composite tube, 8mm OD

Tie layer**

LH-8000 Processing

Tie layer, eg:

• Admer™ by Mitsui Chemicals

• IGETABOND™ by Sumitomo Chemicals

Property Units Method EA-2000 PFA P-63P PFA

Melt Flow Rate g/10min ASTM D-3307 10~25 7~18

Specific Gravity - ASTM D-792 2.13 2.12

Tensile Strength MPa ASTM D-638 36 32

Tensile Elongation % ASTM D-638 330 410

Flexural Modulus MPa ASTM D-790 580 628

MIT cycles 1.0X105 2.5X104

Melting Point ℃ DSC 298 305~315

Initial Decomposition

Temperature ℃ TGA 490 500

Dielectric Constant - ASTM D-150

@1GHz 2.1 2.1

Dielectric Tangent - ASTM D-150

@1GHz <0.002 <0.002

EA-2000 Adhesive PFA

Can be easily processed by co-extrusion, extrusion lamination,

heat lamination, etc.

Cost reduction by eliminating secondary processes like etching

Adhesive property with Al foil

Adhesive property with PI

EA-2000 Processing

General Copper Foil Rz=7.0～8.0μm

Low-Profiled Copper Foil Rz=2.5～3.5μm

Profile-Free Copper Foil Rz=1.0～1.5μm

Copper Foil No surface treatment Rz < 1.0μm

• Adhesion strength on Cu foil, processed via hot press

EA-2000 Processing

Surface Roughness Adhesion Strength

Rz (micron) Ra (micron N/cm

General Cu foil 7.2 1.45 13

Low-profiled Cu foil 3 0.25 11

Profile-free Cu foil 1.2 0.19 12

Cu foil

no surface treatment 0.9 0.13 12

Re-Inventing ETFE

MIL W 81822 Type A

Introducing new grade: C-88AXM-HT ETFE • Aimed at automotive standard LV112 (Class F)

• C-88AXM-HT is almost 20% less dense than FEP

• Performs well at temperatures up to 200 °C

• Full range of color concentrates available

C-88AXM-HT ETFE Standard ETFE

5% weight loss 395 °C 380 °C

10% weight loss 405 °C 390 °C

MIT (no. cycles) 26,500 16,400

Tensile Elongation (%) 550 496

Tensile Strength (MPa) 52 52

Standard ETFE

Ultra Heat Resistant C-88AXM-HT ETFE

Pre-aged 3 hours @ 225 °C before coiling

6 hours @ 225 ° C after coiling

Re-Inventing ETFE

THANK YOU!

Katie Sprick

Product & Development Engineer

AGC Chemicals Americas, Inc.

Katie.Sprick@us.agc.com

610.423.4350