Recent advancement in Denka ER for automotive application

Recent advancement in Denka ER for automotive application

October 25th, 2017Akron Ohio, USA

<Hose Manufacturers Conference>

Toshiaki MIYAUCHIDenka Co.LtdChiba PlantPolymer Research Dept.

Confidential

1. Overview about Denka ER・Features and applications・Manufacturing process・Classifications and properties

2. Recent advancement in automotive application

3. Summary

Contents

DENKA ERElastomer Copolymerized from Ethylene Vinyl Aceteate and Acrylic Esters


１．Overview about Denka ER●Ethylene - Vinyl acetate – Acrylate based polymer, developed

by Denka’s own technology, with excellent heat and oil resistance.

●Endure over 175℃ environment and covers the range between ACM and FKM. Excellent resistance against combined attack of heat and oil.

●Mainly used for automotive and industrial applications.

・No double bond → Weather and heat resistance.・Acrylate monomer units → Cold/Oil resistance balance

-( -CH2-CH2-) l -( -CH2-CH-) m-( -CH2-CH-) n-( R) -｜｜｜

O C=O XO=C-R O-R

ethylene vinyl acetate acrylate cure site

Suitable for parts inside engine compartment


●Monomer composition of Denka ER

Chemical structure and advantages

(for particular grades)

5DENKA ERElastomer Copolymerized from Ethylene Vinyl Aceteate and Acrylic Esters

Typical applications

Intercooler hose for turbo charger

Engine cover gasketAutomatic fluid hose

●Denka ER 8401 product


Shape ： Bale Package ： 25kg paper bag

Manufacturing process of Denka ER

●Manufacturing flow


MonomerEmulsifier

Other ingredients

Monomer removal

ER latex

Coagulation Washing Drying Packing ER rubber

Polymerization stage

Finishing stage

Manufacturing process of Denka ER

a) Epoxy cure site type Ｘ＝

b) Carboxyl cure site type Ｘ＝ＣＯＯＨ

-( -CH2-CH2-) l -( -CH2-CH-) m-( -CH2-CH-) n-( R) -｜｜｜

O C=O XO=C-R O-R

ethylene vinyl acetate acrylate cure site


Classification and properties

●Cure site types

9

Properties and applications●Comparison between Epoxy and Carboxyl cure site types

Cure sites Epoxy cure site type Carboxyl cure site type(Grades) (ER-8401, ER-7300, ANX series) (A413, A403, A322, ERX series)

Scorch time Very good Fair ~ GoodCuring speed / torque Slow / Low Fast / HighTensile strength 12~15MPa 9~11MPa

Heat resistance(Permanent temp)

175℃ > 180℃

Compression set Fair Good ~ Very goodMoldings and Applications

Extrusion ExtrusionInjection

Turbo charger hoseATF hose

Turbo charger hoseATF hoseEngine cover gasketO rings

2-1. Development of new grade ER A322 with improved dynamical performances

2-2. New developments of high heat resistantgrade for future application

2. Recent advancements of Denka ER in turbocharger hoses


・Processability(Storage stability, tackiness, extrusion, etc.)

・Mechanical properties(Heat resistance, oil resistance, acid resistance, dynamical properties, etc.)

High surrounding temperature (Heat resistance)

Exposed by oil and acid mists(Oil and acid resistance)

Applied under dynamical condition(Fatigue resistance)

① Applied conditions and requirements in turbocharger

② Requirements to polymers

11

2. Recent advancements of Denka ER

Goal: Development of new polymers which can meet the requirements.

＜ Grade lineup for turbocharger hoses＞

A322

A413

ANX series Epoxy type

Carboxyl type

Standard ER grade

Higher heat resistance

⇒Advanced grade of A413

・Higher tensile strength・Better heat and oil resistance・Enhanced dynamic properties

HT-ER series

⇒Special grades for future

・Outstanding heat resistance compared to ACM/AEM

・Good dynamic properties

Newly developed ER

Carboxyl type

Carboxyl type

Denka filler additive

Denka Black

・Special carbon blackbased from acetylene gas for better heat resistance

Alternative for FKM/VMQ


Enhanced heat resistance

Higher mechanical properties

Acrylate esters Cross linking site (COOH)

Following improvements have been achieved by optimization of monomer compositions of A413:①Higher tensile and tear strengths②Better retentions of properties during aging (Heat resistance)③Higher fatigue resistance (DeMattia)

2-1. Development of new grade ER A322

13

Monomer unitsGrade : A413, A322

Properties influenced by monomersMechanicalproperties

Heatresistance

Cold resistance

Oil resistance

Acrylate esters ✓ ✓ ✓ ✓

Cross linking site ✓ ✓

Ethylene ✓ ✓ ✓

―Ethylene

◆Comparison with standard A413

14

Properties Unit StandardA413

New gradeA322

Mechanicalproperties

TB MPa 11.4 12.4

EB % 220 270

Tensile product(TB×EB) MPa・% 2500 3350

TR(Trouser) N/mm 2.9 3.6

Heat resistanceat

175℃×504h

TB MPa 8.8 10.2

EB % 207 215

Cold resistance Tg ℃ -32 -28

24%↑

A322 shows higher mechanical properties than A413

34%↑

Mechanical properties of A322

15

Fatigue resistance of A322

A322 shows outstanding flexural resistance

Temp. Unit A413 A322

DeMattia forCrack appearance

23℃ ×103cycles 1,200 >2,000

100℃ ×103cycles 700 >1,300Doubled

DeMattia test condition (ref ISO132)⇒300cycles/min

Test piece: 26×155×6mmwithout notch

2-1. Development of new grade ER A322 with improved dynamical performance

2-2. New developments of high heat resistantgrade (HT-ER series) for future application

2. Recent advancements of Denka ER in turbocharger hoses


＜ Grade lineup for turbocharger hoses＞

A322

A413

ANX series Epoxy type

Carboxyl type

Standard ER grade

Higher heat resistance

⇒Advanced grade of A413

・Higher tensile strength・Better heat and oil resistance・Enhanced dynamic properties

HT-ER series

⇒Special grades for future

・Outstanding heat resistance compared to ACM/AEM

・Good dynamic properties

Newly developed ER

Carboxyl type

Carboxyl type

Denka filler additive

Denka Black

・Special carbon blackbased from acetylene gas for better heat resistance

Alternative for FKM/VMQ


Enhanced heat resistance

Higher mechanical properties

Recombination / Autoxidation ⇔ Degradation

18

Heat Ageing → Elimination of tertiary hydrogen atom (-H) → Generation of radicals

→ Recombination or Autoxidation reaction → Degradation

△

-H

●Thermal degradation mechanism of polymer

HN

R R

Recombination

Autoxidation

(⊿HS > 0, ⊿Mo > 0, ⊿EB < 0)

2-2. Development of HT-ER

19

O

HO

O

Carbon black

ER polymer

OH

Cross linking & hardening by reactions between functional groups

Less reactivity of CB ⇒ Less thermal degradation of ER

Typical properties

Primary particle

Structure growth

Functional groups on surface

OOHOH

HO

O

High atmosphere temp.

OOR

●Thermal degradation arise from carbon blacks2-2. Development of HT-ER

20

①Development of new polymer (HT-ERseries)

A413 HT-ER

Monomercomposition

Acrylate ester ✓ ✓Ethylene ✓ ✓Cure site ✓ ✓

New structure ✓

Introduction of new structure

②Development of new formulation with new filler

Carbon blackN550

Acetylene black(Denka Black)

Average particle size[nm] 43 35Surface area（N2SA）[m2/g] 42 69Iodine adsorption value(IA)[mg/g] 44 93Surface reactivity index（N2SA/IA） 0.95 0.74DBP absorption[ml/100g] 115 160

Application of new carbon black with less surface reactivity

2-2. Development of HT-ER

◆Comparison with standard A413 and effects of Denka Black

21

Properties Unit A413 HT-ER

Carbon black N550 N550 DenkaBlack

Mechanicalproperties

M100 MPa 3.4 3.0 2.8

TB MPa 11.3 10.1 9.8

EB % 262 350 523

Heat resistanceat

190℃×504h

M100 MPa ― 3.8 3.2

TB MPa 6.3 4.0 3.5

EB % 34 133 195

Cold resistance Tg ℃ -32 -28 -25

HT-ER and Denka Black shows higher heat resistance

Mechanical properties of HT-ER

Formulation

Polymer 100Carbon black 50Stearic acid 1Antioxidant 2

Liquid paraffin 1Stearylamine 0.3

Diak#1 0.4XLA-60 0.8

0

100

200

300

400

500

600

700

0 100 200 300 400 500 600

EB (%

)

Aging time at 190℃ (h)

HT-ER+Denka BlackHT-ER + N550A413+N550

◆Retention of elongation at break (EB) at 190℃

22HT-ER and Denka Black improve the EB retention

Heat resistance of HT-ER

+200h

23

Fatigue resistance of HT-ER

HT-ER shows outstanding dynamic performance

Test temp Unit A413 A322 HT-ER

Crackappearance 100℃ ×103cycles 700 1,300 >2,000

Crack growing(2mm→break) RT ×103cycles 10 20 260

Increase

Test condition of DeMattia test:⇒ISO132, 300cycles/min, without notch, 26×155×6mm of test piece

１．New grade A322・A322 achieved enhanced mechanical properties including tensile strength, tear strength, and high temperature resistance compared to standard A413.

・A322 demonstrates considerably higher fatigue resistance than standard A413.

２．HT-ER and Denka Black・HT-ER itself and HT-ER/Denka-Black combination achieved excellent high temperature resistances andfatigue resistances compared to any other ER grades.

・HT-ER is expected to be an alternative for FKM/VMQ in some parts of turbocharger hose application.

Summary

Thank you very much for your kind attention.

Toshiaki MIYAUCHI 宮内俊明

Denka Co.,Ltd. Chiba Plant Polymer Research Dept. 6 Goi-Minami-Kaigan, Ichihara, Chiba, 290-8588 JapanTel.: +81-(0)436-26-3220 / Fax: +81-(0)436-26-3320E-Mail: [email protected]

Recent advancement in Denka ER for automotive application

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