ht-acm xp - sgf · ht-acm xp . the combination of . processing & performance for...

ZEON EUROPE GmbH ZEON CHEMICALS EUROPE LTD.

HT-ACM XP The Combination of

Processing & Performance for High-Temperature

Oil Resistant Hose Applications Peter Abraham,

European Technical Service Manager, Zeon Europe GmbH

SGF Meeting, Malmö, Sweden , 11th APRIL 2013


Polymer Selection – Market Demand

• Automotive Industry & Governmental Regulations – Environmental / Emission / Economy / Maintenance demands – Increased demands on elastomeric materials

• fluid and heat-resistance requirements

– Materials based on older technology no longer appropriate – Fuel efficient engine technology

• more demanding elastomeric applications • need for cost-effective solutions without sacrificing performance

• Automotive hose requiring heat & oil resistance • historically met with a variety polymers • dependent upon the required level of heat resistance • resistance to common fuels & combustion by-products is a limiting

factor for many elastomers


Temperature Resistance

Low Medium High Ultra High

100 – 135°C 135 – 160°C 160 – 180°C 180 – 220°C

Typical Elastomer CPE, CSM, NBR, ECO, CR, NBR/PVC AEM, ACM HT-ACM, (HT-AEM) FKM, VMQ, FVMQ

Relative Elastomer Cost 1X 1.5X 1.6X >4X

Application Commodity and specialty elastomers for oil and fuel resistance hoses

AEM is prevalent in the cold side and lower temperature hot side turbocharger hose segment. One reason is its processing performance influenced by high filler extension & ethylene content.

Temperature range for air management applications used in high-performance engines in passenger cars

(Diesel & gasoline turbo systems)

Temperature range for air management applications used mainly in heavy truck/equipment engines (diesel turbo systems)

Hose materials used in applications requiring resistance to : Hydrocarbon or Synthetic Oil & Grease


• Working temperature resistance between 135 and 160°C – AEM and ACM are used – Historically, AEM dominates this

segment of the hose market

• Good Extrusion processing performance

• Can compound AEM materials more

economically while still maintaining a satisfactory level of performance.

Hose materials - MEDIUM Temperature Segment


Medium

135 – 160°C

Typical Elastomer AEM , ACM

Relative Elastomer Cost 1.5X

Application AEM dominates the cold side and lower temperature turbocharger hose segment due to fast extrusion speeds & high filler / plasticiser loadings


Hose materials - HIGH Temperature Segment

• Working temperature resistance between 160 and 180°C

– Primary focus for air management components

• Diesel or Gasoline turbocharger systems • High-performance passenger car engines

• Segment devoid of a cost effective material

until advent of high-temperature Polyacrylate (HT-ACM)

– Use of higher cost elastomers such as

FKM, VMQ, or FVMQ required

– HT-ACM became a lower-cost alternative


High

160 – 180°C

Typical Elastomer HT-ACM, (HT-AEM )

Relative Elastomer Cost 1.6X

Application Temperature range for air management applications used in high-performance engines in passenger cars

(Diesel & gasoline turbo systems)


• ACM elastomers are used in applications where heat and oil resistance is critical

• Many improvements have been made to ACM elastomers with respect to: – Vulcanization characteristics – Monomer/polymer construction

• Focus of ACM technology developments: – Low & High-temperature performance – Fluid resistance – Processing characteristics

• Automotive manufacturers want best materials – Cost versus performance benefits important

Review of ACM Elastomers


Acrylic Elastomers in Hose

• Acrylic elastomers are used extensively for hoses that must function:

– under long-term exposure to temperatures between 150 and 180°C – intermittent exposure to temperatures between 190 and 200°C – in contact with various types of oils ; fuels & combustion by-products

• ACM - acrylic monomers only – Monomers: Ethyl Acrylate (EA), Butyl Acrylate (BA), and /or Methoxy

Ethyl Acrylate (MEA) – Wide variety of grades for a range of high performance applications – Characteristics dependent on both monomer & cure site combinations.

•AEM - ethylene and acrylic monomers

– Monomers: Ethylene and methyl acrylate (MA)


Turbocharger Application • In recent years, many efforts made to improve engine fuel efficiency :

– engine downsizing – direct fuel injection systems – Turbocharger technology : fuel-efficient power generation ; less waste of

unconsumed fuel energy • Turbochargers of the 1980s vs. today

– Very different : improved materials ; refined design ; smarter sensors etc • Improved efficiency requires → hose constructions with Extreme Thermal resistance

– heat generation – unique combustion by-products

• HT-ACM is now well established as a material of choice for turbo charger hose operating between 160 to 180°C


Turbocharged Engine

Intercooler

Turbo Charger

Engine

Hot Exhaust Duct

Charge Intake Duct

Hot Side Charge Air Duct

Cold Side Charge Air Duct

Typical HyTemp® AR212HR & XP Application Areas

HyTemp® AR212HR - Proven history of success in Turbo Charger applications HyTemp® AR212XP - Improved extrusion processing characteristics & dynamic performance


• HyTemp® AR212HR – Much success has been realized with this grade in HT Hose applications. – Desirable to further improve processability & properties – via continued product

development & improvement

• Performance benefits offered by HyTemp® AR212XP compared to “HR “ – Specifically designed for enhanced extrusion processing

• faster rates ; lower die swell

– Improved hose surface finish – Improved tear resistance – Improved dynamic performance – Improved economics > higher filler extension @ equivalent hardness

• AEM - past processing advantages over ACM may no longer exist with XP introduction

HyTemp® AR212XP


ACM-212 HR ACM-212XP

• Extruded at 3.5m/min

• ACM-212XP compounds have been extruded at rates > 8 m/min without loss of dimensional stability or evidence of scorching

• This extrusion rate is equivalent to, or may even exceed, the rates reported by manufacturers using AEM extrusion compounds

• ACM-212XP superior surface finish provides for excellent strike through between the liner & cover enhancing adhesion to textile reinforcement and dynamic fatigue performance

• Extruded at 6.0m/min

HT-ACM Extrusion Processing


AEM vs. ACM Technology

•AEM and Ethylene content : – Provides for high tensile strength at room temperature ; lower at Service temperatures – Aids with extrusion processing : rate & surface appearance – Higher filler and plasticizer loadings that are possible in some AEM compounds – generally not possible in HT applications – HT-AEM technology introduced to compete with HT-ACM – Ethylene content has negative impact on temperature & oil resistance – Limits temperature resistance to a lower range than that of HT-ACM – Consequently AEM more common in medium temperature hose segment at lower temperatures : 135 to 160°C


Experimental


HT-ACM vs. HT-AEM for HT Hose

• Experimental investigation • Three different compounds were mixed and tested using

standard laboratory methods and procedures.

1. HT-ACM - HyTemp® AR212HR (ACM-212HR) 2. HT-ACM - HyTemp® AR212XP (ACM-212XP) 3. HT-AEM - Vamac® Ultra HT (AEM-3038)

• The HT-AEM and HT-ACM recipes used in this study were obtained from their respective companies’ technical literature and are based upon actual formulations used for turbocharger hose constructions.


ACM-212HR ACM-212XP AEM-3038 HyTemp AR212HR 100.00 HyTemp AR212XP 100.00 HT-AEM 100.00 N550 (FEF Carbon Black) 55.00 55.00 45.00 Vanox CDPA 2.00 2.00 2.00 Stearic Acid 1.00 1.00 1.50 Vanfre VAM 0.50 0.50 1.00 Paraplex G-50 1.50 1.50 2.00 Diak #1 0.50 0.50 1.25 Rhenogran XLA-60 2.00 2.00 Vulcofac ACT 55 1.00 DPG 2.00 TOTAL 162.50 162.50 155.75 Slab Press Cure, min/°C 6/190 6/190 6/190 Button Press Cure, min/°C 8/190 8/190 8/190 Post Cure, hrs/°C 4/175 4/175 4/175 MDR-2000 Rheometer, 30M/190ºC, 100 cpm, 0.5°arc ML, (dN·m) 1.24 1.47 0.45 MH, (dN·m) 8.47 8.02 8.70 Ts2, (min) 0.70 1.30 1.00 T'90, (min) 4.60 13.4 10.7

Compounds


34.7 36.2

31.9

6.7

8.9 8.1

0.0

2.0

4.0

6.0

8.0

10.0

12.0

14.0

0.0

5.0

10.0

15.0

20.0

25.0

30.0

35.0

40.0

ACM-212HR ACM-212XP AEM-3038

Tim

e (m

in)

Torq

ue (

MU

)

Mooney Scorch (ML1+30/125°C) Min Viscosity and Ts5 Scorch Time

Minimum Viscosity T5, (min)

Mooney viscosity characteristics of the compounds are similar and offer similar degrees of scorch safety.


SAE J 2236 – Heat Resistance

• Automotive standard SAE J 2236 defines an elastomer compound’s upper thermal aging limit: – retention of at least 50% original elongation – retention of at least 50% original tensile strength – after 1008 hours of heat aging

• Using this definition – Both HyTemp® HT-ACM based compounds can readily be

described as 175°C + resistant – The HT-AEM compound does not have the thermal aging

stability to retain the compound’s physical strength or flexibility at this operating temperature


0102030405060708090

100


Ret

enti

on, %

SAE J 2236 - Upper Thermal Aging Limit Property Retention After Air Aging for 1008 Hrs at 175°C

Elongation Retention Tensile Retention SAE J 2236 Minimum


50

55

60

65

70

75

80

0 168 336 504 672 840 1008 1176

Shor

e A

Aging Time, Hrs

Air Aged Hardness (Shore A), 175°C

0.001.002.003.004.005.006.00

0 168 336 504 672 840 1008 1176

MPa

Aging Time, Hrs

Air Aged 100% Modulus (MPa), 175°C

0

100

200

300

400

500

0 168 336 504 672 840 1008 1176

%

Aging Time, Hrs

Air Aged Ultimate Elongation (%), 175°C

0.0

5.0

10.0

15.0

20.0

25.0

0 168 336 504 672 840 1008 1176

MPa

Aging Time, Hrs

Air Aged Ultimate Tensile Strength (MPa), 175°C

ACM-212XP AEM-3038

Heat Resistance @ 175°C


-30

-20

-10

0

10

20

30

ΔShA (pts) ΔTb (%) Δeb (%) ΔV (%) ΔWght (%)

Chan

ge

Aged Fluid Immersion, DIESEL/RME [95/5], 46Hrs/23°C

-60-40-20

020406080


Chan

ge

Aged Fluid Immersion, IRM 903, 70Hrs/150°C

-20

-10

0

10

20

30


Chan

geAged Fluid Immersion, LUBRIZOL OS206304, 94Hrs/175°C

ACM-212XP AEM-3038

• HyTemp® ACM are Polar Elastomers and therefore have excellent resistance to many of the non-polar fluids found in automotive applications. – Standard Engine oils – Semi and fully synthetic engine

oils – Hydraulic oils – Transmission fluids – Petroleum based lubricants and

greases – Diesel and bio-diesel fuels – Aliphatic hydrocarbons

• Ethylene in AEM results in a less

polar, less hydrocarbon fluid resistant elastomer compared to HT-ACM

Fluid Resistance


0.0

10.0

20.0

30.0

40.0

50.0

60.0

Initial 168 Hrs 504 Hrs

N/m

m

Air Aged Tear Strength (N/mm), ASTM Die C, 175°C


0.0

2.0

4.0

6.0

8.0

10.0

12.0

Initial 168 Hrs 1008 Hrs

N/m

m

Air Aged Tear Strength (N/mm), DIN Trouser, 175°C• Resistance to tearing is a critical hose characteristic & together with stable ultimate % elongation, gives an indication as to the fatigue resistance of a material over the hose’s lifespan.

• The ACM-212XP Elastomer was specifically designed to have higher tear strength than ACM-212HR

• With improved Tear strength coupled with high initial & stable % Elongation it is well suited to hose subjected to dynamic impulse during service.

• AEM-3038 demonstrates good tear resistance. However, long term (1000Hrs@175C) DIN tear resistance reduces in combination with reduced % Elongation under the same conditions

Tear Strength & Dynamic Flex


The break in the AEM-3038 specimen occurred outside of the specimen’s flexing area.

Greater than 441000

Greater than 441000

050000

100000150000200000250000300000350000400000450000500000

ACM-212XP AEM-3038

Cyc

les

Flex Fatigue Performance DeMattia Test (Un-Pierced), 150ºC, Cycles to Failure

Specimen 1 Specimen 2 Specimen 3


Exhaust Gas Recirculation - EGR


Exhaust Gas Recirculation (EGR)

• Increasing regulations to reduce emissions of CO2 and nitrogen oxides (NOx).

• EGR - technology to lower NOx emissions from diesel engines. – A proportion of the exhaust gases are returned to the cylinder via the intake manifold. – Combustion temperature lowers which reduces the formation of (NOx).

• Exhaust gases must be cooled before recirculation for EGR to be effective

– Diesel fuel + combustion → corrosive gases containing sulfur and nitrogen – Cooling + appropriate engine conditions → sulfuric acid & other highly corrosive species

• Limits lifespan of parts and materials → RAISES COSTS

• OEMs have developed their own unique mixtures of corrosive chemicals and test

methods – Unfortunately, there is not a standard fluid used by all OEMs – Testing of compounds based on HyTemp HT-ACM elastomers indicates that resistance to

corrosive EGR fluids is not a factor when considering HT-ACM for use in HT Turbo Hose.


-10

-5

0

5

10

15

20

Tb Δ, % Eb Δ, % SHa Δ, pts Wt Δ, %

Chan

ge

Fluid Aged Property Change, VW Solution A, 500H/100°C

AR212HR HT-AEM

-10

-5

0

5

10

15

20


Chan

ge

Fluid Aged Property Change, VW Solution B, 500H/100°C

AR212HR HT-AEM

Specification / Main Applications Solution ID Components Structure Solution

Concentration, % Comments

Solution A Sulphuric Acid H2SO4 1.800 Solution pH : 1 Immersion for 500H/100°C

Solution B Acetic Acid C2H4O2 1.250Solution pH : 2.5 Immersion for 500H/100°C

Air Induction Systems - TDI & HT-TDI

Sulphuric Acid & Acetic Acid - Duration : 500 Hrs @ 100C

ACID CONDENSATE Testing VW Fluids and method


-6-4-202468

1012


Chan

ge

Fluid Aged Property Change, Fiat Fluid & Method

AR212HR HT-AEM

Specification / Main Applications Solution ID Components Structure Solution

Concentration, % Comments

Distilled Water H2O 90.7Formic Acid CH2O2 0.06Nitric Acid HNO3 0.18Acetic Acid C2H4O2 0.06Ethyl Alcohol C2H6O 9.0

9.02139: Air Induction Systems - TDI & HT-TDI

Immersion for 70H/120°C followed by dryout for 24H/120°C

Fiat Solution

Aqueous combination of Acids & Alcohol : 70 Hrs @ 120C & dryout 24 Hrs @ 120C

ACID CONDENSATE Testing FIAT Fluid and method


Summary


Summary •Polyacrylate elastomer compounds are ideal for the fabrication of seals and gaskets

– for the sealing of hydrocarbon-based lubricants

•Polyacrylate elastomer compounds are ideal for the fabrication of hoses

– for the conveying of hydrocarbon based lubricants ; extremely Hot air saturated with petroleum-based lubricants & fuels and in the presence of Acid Condensates generated by EGR technology

•Recent scientific developments in polyacrylate chemistry have improved ACM performance, particularly high temperature characteristics with the advent of HT-ACM grades such as :

– HyTemp® AR212XP


– High Temperature performance in the range 160 to 180C • Peak performance 190 to 200C

– Suited to applications such as HT Turbocharger Hose – Enhanced extrusion ; Improved tear & dynamic performance – Increased extrusion rates & hose surface finish – Lower die swell > Improved dimensional control – Lower Cost - Higher filler loading @ equivalent hardness compared to “HR”

– Improved long term Heat ageing performance & non-polar fluid resistance compared to AEM

– Competitive alternative to AEM in Hose applications requiring heat resistance in the range 150 to 160C

– Past processing advantages of AEM vs ACM may no longer exist with the introduction of XP

Benefits - HyTemp® AR212XP

Thank you for your attention

Any Questions ?

Zeon Europe GmbH, Hansaallee 249, 40549 Düsseldorf, Germany Tel +49 (0)211 52670 ; Fax +49 (0)211 5267 160 ; www.zeon.eu

The information contained herein is believed to be reliable, but no representations, guarantees or

warranties of any kind are made as to its accuracy, suitability for particular applications or the results to be obtained there from. The information is based on laboratory work with small-scale equipment and does not necessarily indicate end product performance. Because of the variations in methods, conditions and equipment used commercially in processing these materials, no warranties or guarantees are made as to the suitability of the products for the application disclosed. Full-scale testing and end product performance are the responsibility of the user. Zeon Europe GmbH shall not be liable for and the customer assumes all risk and liability of any use or handling of any material beyond Zeon Europe GmbH direct control. The SELLER MAKES NO WARRANTIES, EXPRESS OR IMPLIED, INCLUDING, BUT NOT LIMITED TO, THE IMPLIED WARRANTIES OF MERCHANTABILITY AND FITNESS FOR A PARTICULAR PURPOSE. Nothing contained herein is to be considered as permission, recommendation, nor as an inducement to practice any patented invention without permission of the patent owner.

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