Post on 05-Jan-2022
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
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
DENKA ERElastomer Copolymerized from Ethylene Vinyl Aceteate and Acrylic Esters
●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
DENKA ERElastomer Copolymerized from Ethylene Vinyl Aceteate and Acrylic Esters
Shape : Bale Package : 25kg paper bag
Manufacturing process of Denka ER
●Manufacturing flow
DENKA ERElastomer Copolymerized from Ethylene Vinyl Aceteate and Acrylic Esters
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
DENKA ERElastomer Copolymerized from Ethylene Vinyl Aceteate and Acrylic Esters
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
DENKA ERElastomer Copolymerized from Ethylene Vinyl Aceteate and Acrylic Esters
・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
2. Recent advancements of Denka ER
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
DENKA ERElastomer Copolymerized from Ethylene Vinyl Aceteate and Acrylic Esters
< 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
2. Recent advancements of Denka ER
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: toshiaki-miyauchi@denka.co.jp