ACM AEM KARŞILAŞTIRMASI AR212 AEM CFX.pdf

8/10/2019 ACM AEM KARILATIRMASI AR212 AEM CFX.pdf

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High-Performance HT-ACM Elastomers forAutomotive Molded and Extruded

Applications

By

Andy Anderson, Paul Manley PhD*, John Moore ZCLPPeter Abraham, Ivan Burczak, Jeff Dickerhoof ZCEL

Yoshiaki Aimura, Hirofumi Masuda Zeon Corporation

Presented at the 170thmeeting of the

Rubber Division, American Chemical Society

Cincinnati, OH

October 10-12, 2006

ISSN: 1547-1977

*Speaker

Zeon Chemicals L.P., 4111 Bells Lane, Louisville, KY 40211 Phone: 877-ASK ZEON, Fax: 502-775-2055

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 onlaboratory 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 applications disclosed. Full-scale testing and end product performance are the responsibility of the user. Zeon Chemicals L.P. shall not be liable for and the customer assumes all risk and liability of any use or handling of anymaterial beyond the direct control of Zeon Chemicals L.P. The SELLER MAKES NO WARRANTIES, EXPRESS OR IMPLIED, INCLUDING, BUT NOT LIMITED TO, THE I MPLIED WARRANTIES OR MERCHANTABILITY AND FITNESS FOR APARTICULAR 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.

301PA2006ACSIL


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ABSTRACTACM (polyacrylic) elastomers have undergone continuous development to enhance long-

term performance, resulting in an important position in the manufacture ofheat and oil resistantgaskets and seals. Four years ago, Zeon Corporation introduced a new family of heat and oil

resistant ACM polymers known throughout the industry as AR12, AR14, and AR22. The

superiority of these new elastomers over traditional ACM elastomers has been successfully

demonstrated in many under-hood automotive applications, including valve cover gaskets, oilpan gaskets, rocker cover gaskets, and seals.

With the continuing trend toward a smaller, more crowded engine bay, operatingtemperatures are on the rise, resulting in greater demands being placed on the under-hood

components. The more severe conditions require the use of elastomers with significantly

improved heat and fluid resistance. The elastomer choices that service this higher temperaturerange and that can be easily processed are limited and costly.

In recent years, the use of high-performance turbo diesel engines has grown rapidly.

Auto manufacturers have expressed a desire to replace expensive, over-engineered elastomer

components hot side TDI hose with lower-cost components providing acceptableperformance. To meet this industry demand, Zeon Chemicals has developed an extrusion

version of AR12. The objective of this paper is to demonstrate the heat resistance of the latestHigh-Temperature ACM (HT-ACM), which can be used for low-durometer molding andextrusion (Turbo Diesel Injection hose) applications.

INTRODUCTIONPolyacrylate polymers are known as specialty elastomers, which are classified as high-

temperature and oil resistant elastomers. The ASTM D2000 and SAE J200 designation for

polyacrylic polymer is ACM (Acrylic Co-Monomer). The majority of end uses for ACM

polymers are in applications where high-temperature and oil resistance is required. Six yearsago the Zeon Group introduced the first of a range of new ACM elastomers (HT-ACM) with a

unique functional cure site1,2,3

. Since then the range has been expanded to four grades, with

additional grades under development. These elastomers offer significant improvements in long-term high-temperature resistance and their use and superiority in a number of demanding

automotive applications including valve cover gaskets, oil pan gaskets, rocker cover gaskets, and

various seals have already been successfully demonstrated. These applications, where sealing

force retention for >160,000 kilometers is a typical expectation, require the excellent long-termhigh-temperature performance, excellent compression set, compressive stress relaxation (CSR)

resistance, and stable modulus that these elastomers provide. Development of the latest of these

HT-ACM elastomers, HyTemp

AR212HR, has focused on enhanced extrusion specificprocessing characteristics--this has expanded the use of HT-ACM to applications such as hoses,

tubes, and air ducts.

OBJECTIVEThis paper describes the continuous development of Zeon HT-ACM elastomers and

associated materials and will demonstrate the latest grades ability to meet the high-temperature

performance requirements of applications like (High Temperature) HT-TDI hose and air ductsused in charged air systems. Benefits include longer scorch times for extrusion processing

combined with economical and flexible curing characteristics, which offer significant cost

benefits compared to current high-temperature solutions. Excellent long-term heat and fluidresistance characterize all Zeon HT-ACM elastomers.


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EXPERIMENTAL

PROCEDUREMixing and Curing- The ACM compound formulation was based on meeting the VW

standard for TDI hoses TL526.34. All compound masterbatches were prepared in a 1600 cc

Farrell internal mixer with high rotor speeds. All ingredients, except for curatives, were chargedusing an upside-down mixing technique. After incorporation of fillers (approximately four

minutes) the masterbatch was discharged at a temperature of 170C. This masterbatch was then

transferred to a cool 20-cm two-roll mill, sheeted to approximately three millimeters thickness,

and allowed to rest for one hour. After the rest period, the compound masterbatch was thenplaced back onto the mill, allowed to form a smooth rolling bank, and curatives were added.

Test articles prepared from this final compound were compression molded at 190C for eight

minutes and post cured in a forced air convection oven for four hours at 177C.Rheological Properties- Mooney viscosity and Mooney scorch measurements were

conducted according to ASTM D1646 at 100 and 125C respectively. Cure characteristics were

determined using a Rheometer 100S at 190C, 3 arc, with 30-minute run time. The test wasconducted according to ASTM D2084.

Vulcanized Evaluation- Tensile strength, elongation, and hardness values were obtained

according to ASTM D412 and D2240. The tensile and elongation data was collected using aUnited model E-VI-60 six-station tensile test instrument, while the hardness data was collected

using a Zwick hardness tester. Air oven aged physical properties were obtained according to

ASTM D573 and were evaluated on the United tester. Compression set was determined using the

PV 3307 and VDA 675 218 (VW compression set).

BACKGROUND

The HT-ACM elastomers were primarily designed to be fast curing for injection moldingprocesses and have been used successfully in many molded applications. The cure system used

for optimal heat resistance results in typical scorch times for these compounds in the range of 4

to 8 minutes at 120C. Hose manufacturers require safer processing characteristics combined

with high throughput for economical production. This led to the development of the latest HT-ACM elastomer and specialized curative systems, which can be used for both molding and

extrusion applications. A new protection system has also been developed to further enhance

high-temperature aging performance to meet demanding high-temperature specifications.

COMPOUND DEVELOPMENT

The series of ACM compounds were designed to evaluate cure systems as well as antioxidantssystems. These four ACM compounds will be compared against similar standard AEM

compounds. All the compounds were compounded to equal hardness (60 durometer).

Compounds 1 through 4 were based on HyTemp AR212HR. Compound 1 was based on the

new protection package along with the extrusion cure system, and the compound is designated as

HT ACM EX. Compound 2 evaluated the standard antioxidant package using the extrusion curepackage, which is referred to as HT ACM EXAO. Compound 3 was similar to the firstcompound except the molding cure system was evaluated. This compound is referred to as HT

ACM M. Compound 4 is similar to compound 3 except for the antioxidant. This compound

contained the standard antioxidant package and will be referred to as HT ACM MAO.

The four ACM compounds could be compared against themselves for heat resistance. There areother acrylate elastomers in the marketplace, and these have found homes in extrusion

applications. It was a natural comparison for the ACM compounds to be evaluated against AEM

compounds used for similar applications. Compound 5 was based on Vamac G and will be


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designated AEM-G. Compound 6 was based on Vamac GLS and will be designated AEM-GLS.Compounds 7 and 8 were based on Vamac GXF. Compound 8 was a slightly modified version

of compound 7. The compounds will be referred to AEM-GXF and AEM GXF M respectively.

The AEM recipes can be seen in Figure 1.The rheological properties of the compounds can be seen in Figure 2. The scorch times (tS5) for

the HT-ACMs range from 7 to 16 minutes. The scorch time of the AEM compounds range from

6 to 14 minutes. This could be considered acceptable for both molding and extrusion operations.

All the compounds had T90s less than 20 minutes @ 180C which fits in with most extrusioncapabilities.

All the compounds were in the target hardness range of 55 to 65 Shore A. The tensile strengthsof the AEMs were higher than that of the HT-ACMs when measured at room temperature

(23C). The tensile strength of the HT-ACM based compounds was slightly higher than the

AEM compounds when the test was performed at operating temperature of 150C. The ultimateelongations of the AEM compounds were higher than that of the HT-ACM compounds when

measured at room temperature, however the elongation of the HT-ACMs was higher at elevated

temperature. The results can be seen in Figures 3 through 5.Compression set properties were evaluated under different conditions. The test temperature was

175C and the test specimens were plied discs. Time intervals evaluated were 24, 168, and 504hours. A noticeable pattern appears in the HT-ACMs (Figure 6). The compounds with the

standard AO had lower compression set than that of the compounds with the extrusion AOpackage. The molded compounds had lower compression set than the extrusion compounds as

expected. The AEM GF based compounds had higher compression set than the ones based on

AEM-G and GLS.VW-type compression set was tested 24 hours @ 175C. The compression set of the HT-ACM

molded compounds was less than the extruded compounds as expected. One could observe a

similar trend in the values associated with the antioxidant package used as noted above. Thecompression set values of all the extrusion HT-ACM compounds were very much lower than the

limits seen in various automotive specifications of 80% max. The compression set of the HT-

ACMs was equal to or better than the AEM based compounds. The results can be viewed inFigure 7.Air oven aging was performed at three different temperatures: 175C (1000 hours), 190C (168

hours), and 200C (168 hours). A comparison of actual tensile values can be seen in Figure 8.

The tensile strengths of the HT-ACM compounds after aging were compound dependent; thiswas noticed after observing the different aging times/ temperatures. The compounds containing

the new AO package had higher tensile strengths than the ones with the standard AO package. A

large difference in tensile values between the AEM and HT-ACMs noted in the originals hasnow been minimized after aging. This should translate into higher percent tensile loss for the

AEM compounds. In other words, the tensile strength of the HT-ACM compounds is similar to

that of the AEM compounds after aging. Data can be seen in Figure 8.

Higher elongation values were observed in the compounds with the standard AO package thanwith the new AO package in both cure systems. Basically the standard AO package gives better

(lower) change in percent elongation. Elongation values of the HT-ACM compounds were

higher than the values of the AEM compounds after aging at all three conditions: 175C(1000hours), 190C (168 hours), and 200C (168 hours)). Higher elongation values after aging

result in lower elongation loss and better flexibility for the HT-ACM based compounds. The

percent elongation data can be seen in Figure 9, while the change in properties at the differenttemperatures can be seen in Figures 10 through 12

All of the compounds were aged in two European motor oils, Lubrizol OS 206304 and Shell

Helix Ultra. The samples were aged 94 hours @175C and 168 hours @ 190C in the above


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mentioned oil respectively. This was an unusual temperature--the typical test temperature usedin testing is 150C. These test conditions are considered severe (oils cannot take the heat for

extended periods of time). Under these severe test conditions the HT-ACM based compounds

exhibited lower property change than did the AEM based compounds. The property changes canbe viewed in Figures 13 and 14.

The compounds were exposed to a mixture of diesel oil and RME (Rapeseed oil Methyl

Ester [European biodiesel]). The first mixture was composed of a low sulfur diesel fuel from

Texaco at 95% blended with 5% RME. The second diesel fuel mixture evaluated was Diesel RefFuel: ISO 1817 Type F Fluid 95% / RME 5%. This is a very aggressive fuel mixture. The test

time/temperature duration for the fuel mixtures immersion was 46 hours @ 23C. The effect of

the fuel exposure on the compounds can be seen in Figure 15. All four of the HT-ACM basedcompounds exhibited excellent resistance to the low sulfur/RME mixture. The HT-ACM based

compounds exhibited lower property change than did all the AEM based compounds

The diesel fuel mixture, which contained ISO 1817 Type F fluid/RME, was moreaggressive toward the rubber compounds. The compounds exhibited larger change in hardness,

tensile strength, percent elongation, and weight. Despite the more aggressive nature of this fluid,

the HT-ACM based compounds exhibited lower property change than did all the AEM basedcompounds. The effect of the fuel exposure on the compounds can be seen in Figure 16.

The physical and chemical properties of the HT-ACMs compounds have been discussed. Anapplication which requires the heat resistance of the HT-ACMs is Turbo Diesel Injection hose

(TDI).

HIGH-TEMPERATURE HOSE APPLICATIONSThe automotive industry continues to develop new high-performance engines to meet

both environmental and low maintenance requirements. Diesel engine technology, with increased

injection pressures, generates more heat. The general trend continues to be higher engine bay

temperatures, and automotive fluids and oils, which are more aggressive toward elastomercomponents. HT-ACM elastomers continue to offer the improved long-term heat and fluid

resistance that is required. Efforts by the automotive industry to maximize cost / performance

benefits in material selection are leading to the replacement of more expensive solutions such asfluoroelastomers, silicones, and fluorosilicones with new more cost effective alternatives. One

such example includes HT-ACM in charged air systems, specifically Hot Side TDI charged air

hoses. Zeon HT-ACM hose components also readily operate at lower temperatures in areas suchas transmission (TOC) and engine oil cooler (EOC) hose applications.

Car producers recently have investigated HT-ACM for continuous service at 175C/185C with peaks to 190C/200C in the hot side HT TDI area of charged air systems. As noted,

due to the temperatures involved, the incumbent materials have traditionally been FKM, VMQ,

and FVMQ. Until the recent introduction of HT-ACM elastomers, there had been no cost-effective alternative material available which could bridge the gap between the standard ACM

and AEM hoses operating at 150C /160C and these higher temperatures. In some cases, metalshielding is required to protect the lower-temperature standard hoses. The introduction of HT-ACM hoses can eliminate the need for such shielding, thus providing weight, space, and cost

savings, while also potentially reducing noise, vibration, and harshness (NVH). Of course at

temperatures above 200C the fluoroelastomers and silicones will continue to be required and insome cases where extreme temperatures are encountered, metal air ducts are employed.


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HT-ACM PERFORMANCEThere are several key properties of a TDI hose. These include, but are not limited to, the

following:

Compound must be extrudable at Hardness: 50 to 65 Shore A

Excellent Heat Resistance

Continuous Operating Conditions

175C to 185CPeak Operating Conditions

190C to 200C

Good Tear ResistanceExcellent Oil Resistance

Excellent Diesel Fuel Resistance

HEAT RESISTANCE

Classifying the performance of elastomeric compounds, test data is typically presented in

terms of percent loss of a particular property. In both standard ACM and HT-ACM compounds,retention of elongation at break and tensile strength are considered as two of the most relevant

properties in assessing heat resistance performance. The SAE J2236 document4

(Standardmethod for determining continuous upper temperature resistance of elastomers) defines the

continuous use temperature of a material as being related to the retention of more than 50% thevalue of an original property at the given test temperature.

The heat resistance of the HT-ACM AR212HT was measured using the SAE J2236 as a

guideline4. Air oven aging was conducted at three different temperatures, 150C, 175C, and

190C. Tensile loss vs. time was plotted for the 190C and 175 C agings. Figures 18 and 20

represent this data. Figures 19 and 21 represent the plot of % elongation loss plotted against

time. In each of the two test temperatures, elongation was the first property to lose 50% of itsoriginal value. The percent elongation retention/loss is the property that determines the heat

resistance by using this method. Figure 22 shows a plot of % elongation change at 150C. This

compound was tested to 2000 hours and the compound still retained ~90% of its originalelongation. The curve was then extrapolated to 50 % loss and is shown in Figure 23.

The time to 50% loss was calculated for each of the 3 temperatures. The log of time vs

log 1/T (K absolute temperature) was plotted, resulting a line. A line was developed and the

correlation ratio calculated. The R2 value was > .99, which is an indication of a good fit. Theplot was changed to a more user-friendly plot and can be seen in Figure 24.

TEAR RESISTANCEThe typical tear resistance test that is used is the trouser tear against the grain using DIN

53507A method. The test specimens were oven aged 168 hours @ 175C and 72 hours @200C.

The results were plotted and can be viewed in Figure 25. Most of the TDI specifications specify

tear values above 2 kNM. The compound based on the HT-ACM212HR met this requirement.

OIL AND FUEL RESISTANCE

Resistance to automotive engine oils and fuels is important in many automotive hoseapplications. HT-ACM compounds offer excellent resistance to a range of fully and semi-

synthetic engine oils; diesel and diesel/bio-diesel fuel blends. It should be noted that ACM

elastomers are not resistant to gasoline fuel. Figures 26 and 27 show the excellent performanceof HT-ACM AR212HR hose compound in the reference oil, Cecilia 20 (C20) and engine oils,

Shell Helix Plus and Castrol SLX. The performance offered by the HT-ACM elastomers enables


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their use in a whole range of hose applications where these and other similar lubricants may beencountered.

The diesel fuel resistance can be seen in Figure 28. The fuels that were used in this evaluation of

the HT-ACM AR212HR were standard diesel and a mixture of Diesel/5%RME (95/5). The testtime and temperature used was 48 hours @23C. Minimal change in physical properties was

observed after the samples had been exposed to the different fuels/mixtures.

FUNCTIONAL PERFORMANCESpecifications for HT-TDI hoses calling for the use of HT-ACM have already been or are

in the process of being introduced by many European car manufacturers. Hoses developed and

now in production with HyTempAR212HR have satisfied the dynamic impulse performance

requirements of many of these specifications at the typical expected operating temperatures of

170C to 180C with peaks up to 190C.

Table I identifies some of these specifications Introduced (I), Draft (D), and revision ofexisting (E) to accommodate HT-ACM.

The SAE definition of heat resistance does not mean that the compound cannot function

above this temperature. For example the HT-ACM is rated @ 175C by this definition, howevercompounds based on this polymer have functioned quite well at 180C with intermittent

temperature spikes to 200C. It should be noted that this is a guideline to a functional absolutetemperature.

SUMMARY & CONCLUSIONSA new HT-ACM elastomer, new curative and protection system has been developed

providing both long-term high-temperature performance and excellent processing characteristicsfor extrusion operations. Applications for this new elastomer include extruded HT TDI hose and

air ducts. The Volkswagen Group were the first to introduce the new class of HT-ACM TDI

Hoses in 2004 with the requirements specified in the VW TL 526.34 standard5. Other car

producers have followed with a similar approach. A fundamental change in philosophy wasadopted by VW with respect to the HT hoses, being much softer (55 to 65 Shore A) compared to

the well-established standard (70 Shore A) TDI hoses. These HT hoses are expected to perform

continuously at 175C /185C and intermittently to temperatures as high as 190C / 200C. Theywere introduced to compensate for the performance deficiencies of standard ACM and/ or AEM

TDI Hoses (150C to 160C) and provide a more cost-effective alternative to the more expensive

current high-temperature solutions such as FKM, VMQ, and FVMQ hoses. These softer hosesalso offer benefits in reduced noise, improved vibration characteristics, and enhanced flexibility

during aging in service.

Benefits of the new HT-ACM elastomer can be summarized as:

HT-ACMs yield higher retention of property than AEM compounds

The new antioxidant package present in the HT-ACM gives better tensile strength afteraging, and should only be used when trying to meet a specification which has minimum

tensile values like VW for extruded products.

Excellent long-term aging characteristics minimal property changes. Temperature range 30C to 175C* with peaks to 190C /200C.

Enhanced scorch behavior and excellent extrusion characteristics.

Upgrade vs. AEM and standard ACM hoses operating at 150C /160C.

Cost effective alternative to present high-cost TDI solutions.

Wide range of hose hardness can be extruded: 50 to 80 Shore A.

Excellent oil & diesel fuel resistance.

Suitable for molded and extrusion applications.* SAE definition


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ACKNOWLEGEMENTS

The author would like to thank Zeon Corporation, Zeon Chemicals L.P., and Zeon Europe

GmbH for their permission to publish this paper and their support and contributions to it.

REFERENCES1. I. Kubota, et al., Paper 126, Improved Heat & Compression Set Resistance Polyacrylate

Elastomers; Part A , Polymer Development, ACS , Cincinnati, OH, 2000

2. P. Manley, et al., Paper 127, Improved Heat & Compression Set Resistance Polyacrylate

Elastomers; Part B - Applications in Engine and Automatic Transmission Fluids Requiring LowCompressive Stress Relaxation ACS, Cincinnati, OH, 2000

3. I. Kubota, et al., Paper 32, Improved Low-Temperature Properties Polyacrylate Elastomers,

ACS, Cleveland, OH, 20014 SAE J2236 Standard method for determining continuous upper temperature resistance of

elastomers

5. Volkswagen AG, TL 526.34, September 2005 Charge Air Hoses Made of High-Temperature ACM Elastomer


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AEM Recipes

AEM-G AEM-GLS AEM GXF AEM GXF H

AEM G 100.00

AEM GLS 100.00

AEM GXF 100.00 100.00

N772 50.00 50.00 50.00 50.00

Stearic Acid 1.50 1.50 1.50 1.50

AO 445 2.00 2.00 2.00 2.00

Process aid VAM 1.00 1.00 1.00 1.00

Process Aid 18 D 0.50 0.50 0.50

TP759 5.00 5.00 5.00 5.00Subtotal 160.00 160.00 160.00 159.50

Cure system

DOTG 4.00 4.00 4.00 4.00

HDC 1.50 1.50 1.50 1.50

TOTAL 165.50 165.50 165.50 165.00

Figure 1

Original Properties

0000

10101010

20202020

30303030

40404040

50505050

60606060

70707070

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

AEMG

AEMG

AEMG

AEMG

AEMGLS

AEMGLS

AEMGLS

AEMGLS

AEMGXF

AEMGXF

AEMGXF

AEMGXF

AEMGXFM

AEMGXFM

AEMGXFM

AEMGXFM

Property

Property

Property

Property

Hardness A, (pts) 3 sec delayHardness A, (pts) 3 sec delayHardness A, (pts) 3 sec delayHardness A, (pts) 3 sec delay

Figure 3

Rheological Properties

HT ACM -EX HT-ACM EXA HT-ACM M HT-ACM-MA AEM-G AEM-GLS AEM GXF AEM GXF HT

Mooney Scorch ML @,120C,

Minimum Viscosit 30.0 32.0 29.0 30.0 16.0 16.0 15.0 16.0

T5, (min) 11.3 7.3 15.1 12.6 8.2 6.6 13.1 11.3

T10, (min) 14.0 8.5 18.3 15.3 10.3 8.5 18.4 15.5

MDR-2000 Rheometer,180C,

ML, (lbfin) 1.0 1.0 0.9 1.0 0.2 0.2 0.2 0.2

MH, (lbfin) 4.8 4.9 6.4 6.5 8.5 7.7 7.4 8.0

Ts2, (min) 1.9 1.5 2.0 1.7 2.0 1.0 2.0 1.7

T'90, (min) 18.6 18.4 12.7 11.4 6.2 5.0 9.6 8.7

Figure 2


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Original PropertiesTensile MPa

0000

2222

4444

6666

8888

10101010

12121212

14141414

16161616

18181818

20202020

HT-ACME

HT-ACME

HT-ACME

HT-ACME

HT-ACM-EXA

HT-ACM-EXA

HT-ACM-EXA

HT-ACM-EXA

HT-ACM-

HT-ACM-

HT-ACM-

HT-ACM-

HT-ACM-MA

HT-ACM-MA

HT-ACM-MA

HT-ACM-MA

AEM

AEM

AEM

AEM

AEMGL

AEMGL

AEMGL

AEMGL

AEMGX

AEMGX

AEMGX

AEMGX

AEMGXF

AEMGXF

AEMGXF

AEMGXF

MPMPa

MPa

MP

0000

1111

2222

3333

4444

5555

6666

7777

8888

9999

10101010

23C23C23C23 C 1 50 C150C150C150C

Figure 4

Original Properties

0000

50505050

100100100100

150150150150

200200200200

250250250250

300300300300

350350350350

400400400400

450450450450

500500500500

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACM-EXA

O

HT-ACM-EXA

O

HT-ACM-EXA

O

HT-ACM-EXA

O

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

AEMG

AEMG

AEMG

AEMG

AEMGLS

AEMGLS

AEMGLS

AEMGLS

AEMGXF

AEMGXF

AEMGXF

AEMGXF

AEMGXFM

AEMGXFM

AEMGXFM

AEMGXFM

Percent

Percent

Percent

Percent

50505050

70707070

90909090

110110110110

130130130130

150150150150

170170170170

190190190190

210210210210

230230230230

250250250250

23C23C23C23C 150C150C150C150C

Fi ure 5

ASTM Compression set

Plied Disc@ 175C

0000

10101010

20202020

30303030

40404040

50505050

60606060

70707070

80808080

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

AEMG

AEMG

AEMG

AEMG

AEMGLS

AEMGLS

AEMGLS

AEMGLS

AEMGXF

AEMGXF

AEMGXF

AEMGXF

AEMGXFM

AEMGXFM

AEMGXFM

AEMGXFM

P

roperty

Property

Property

P

roperty

24 hours24 hours24 hours24 hours 168 hours168 hours168 hours168 hours 504 hours504 hours504 hours504 hours

Fi ure 6


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VW Compression set

24 hours @ 175C

0000

10101010

20202020

30303030

40404040

50505050

60606060

70707070

80808080

90909090

100100100100

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

AEMG

AEMG

AEMG

AEMG

AEMGLS

AEMGLS

AEMGLS

AEMGLS

AEMGXF

AEMGXF

AEMGXF

AEMGXF

AEMGXFM

AEMGXFM

AEMGXFM

AEMGXFM

P

roperty

P

roperty

P

roperty

P

roperty

24 hours24 hours24 hours24 hours

Figure 7

Air Oven Aging

Tensile values after aging

Figure 8

0000

2222

4444

6666

8888

10101010

12121212

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACM-EXA

O

HT-ACM-EXA

O

HT-ACM-EXA

O

HT-ACM-EXA

O

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

AEMG

AEMG

AEMG

AEMG

AEMGLS

AEMGLS

AEMGLS

AEMGLS

AEMGXF

AEMGXF

AEMGXF

AEMGXF

AEMGXFM

AEMGXFM

AEMGXFM

AEMGXFM

Property

Property

Property

Property

MPa 168 h 190MPa 168 h 190MPa 168 h 190MPa 168 h 190 MPa 168h 200MPa 168h 200MPa 168h 200MPa 168h 200

MPa 1008h 175MPa 1008h 175MPa 1008h 175MPa 1008h 175

Air Oven Aging

% Elongation after aging

0000

50505050

100100100100

150150150150

200200200200

250250250250

300300300300

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

AEMG

AEMG

AEMG

AEMG

AEMGLS

AEMGLS

AEMGLS

AEMGLS

AEMGXF

AEMGXF

AEMGXF

AEMGXF

AEMGXFM

AEMGXFM

AEMGXFM

AEMGXFM

Propert

Property

Property

Propert

Elong 168 h 190Elong 168 h 190Elong 168 h 190Elong 168 h 190 Elong 168 h 200Elong 168 h 200Elong 168 h 200Elong 168 h 200

Elong 1008h 175Elong 1008h 175Elong 1008h 175Elong 1008h 175

Figure 9


12/19

- 12 -

Air Oven Aging

1008 hours @ 175C Property Change

-100-100-100-100

-90-90-90-90

-80-80-80-80

-70-70-70-70

-60-60-60-60

-50-50-50-50

-40-40-40-40

-30-30-30-30

-20-20-20-20

-10-10-10-10

0000

10101010

20202020

30303030

HT-ACM

EX

HT-ACM

EX

HT-ACM

EX

HT-ACM

EX

HT-ACM

-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM

-EXAO

HT-ACM

-M

HT-ACM

-M

HT-ACM

-M

HT-ACM

-M

HT-ACM

-MAO

HT-ACM

-MAO

HT-ACM

-MAO

HT-ACM

-MAO

AEMG

AEM

G

AEM

G

AEMG

AEMGLS

AEMGLS

AEMGLS

AEMGLS

AEMGXF

AEM

GXF

AEM

GXF

AEMGXF

AEMGXFM

AEM

GXFM

AEM

GXFM

AEMGXFM

Propert

Propert

Propert

Propert

Hardness changeHardness changeHardness changeHardness change Tensile Change, (%)Tensile Change, (%)Tensile Change, (%)Tensile Change, (%)

Elongation Change, (%)Elongation Change, (%)Elongation Change, (%)Elongation Change, (%)

Fi ure 12

Air Oven Aging


-70-70-70-70

-60-60-60-60

-50-50-50-50

-40-40-40-40

-30-30-30-30

-20-20-20-20

-10-10-10-10

0000

10101010

20202020

30303030

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

AEMG

AEMG

AEMG

AEMG

AEMGLS

AEMGLS

AEMGLS

AEMGLS

AEMGXF

AEMGXF

AEMGXF

AEMGXF

AEMGXFM

AEMGXFM

AEMGXFM

AEMGXFM

Property

Property

Property

Property



Fi ure 10

Air Oven Aging


-70-70-70-70

-60-60-60-60

-50-50-50-50

-40-40-40-40

-30-30-30-30

-20-20-20-20

-10-10-10-10

0000

10101010

20202020

30303030

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

AEMG

AEMG

AEMG

AEMG

AEMGLS

AEMGLS

AEMGLS

AEMGLS

AEMGXF

AEMGXF

AEMGXF

AEMGXF

AEMGXFM

AEMGXFM

AEMGXFM

AEMGXFM

Hardness A, changeHardness A, changeHardness A, changeHardness A, change Tensile Change, (%)Tensile Change, (%)Tensile Change, (%)Tensile Change, (%)


Fi ure 11


13/19

- 13 -

LUBRISOL OSLUBRISOL OSLUBRISOL OSLUBRISOL OS 206304 Oil Aging206304 Oil Aging206304 Oil Aging206304 Oil Aging


-40-40-40-40

-30-30-30-30

-20-20-20-20

-10-10-10-10

0000

10101010

20202020

30303030

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

AEMG

AEMG

AEMG

AEMG

AEMGLS

AEMGLS

AEMGLS

AEMGLS

AEMGXF

AEMGXF

AEMGXF

AEMGXF

AEMGXFM

AEMGXFM

AEMGXFM

AEMGXFM

P

roperty

P

roperty

P

roperty

P

roperty


Elongation Change, (%)Elongation Change, (%)Elongation Change, (%)Elongation Change, (%) Wt ChangeWt ChangeWt ChangeWt Change

Figure 13

Shell Helix Ultra Oil AgingOil AgingOil AgingOil Aging

168hrs @ 190168hrs @ 190168hrs @ 190168hrs @ 190C Property ChangeC Property ChangeC Property ChangeC Property Change

-40-40-40-40

-30-30-30-30

-20-20-20-20

-10-10-10-10

0000

10101010

20202020

30303030

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

AEMG

AEMG

AEMG

AEMG

AEMGLS

AEMGLS

AEMGLS

AEMGLS

AEMGXF

AEMGXF

AEMGXF

AEMGXF

AEMGXFM

AEMGXFM

AEMGXFM

AEMGXFM

Property

Property

Property

Property



Figure 14

-70-70-70-70

-60-60-60-60

-50-50-50-50

-40-40-40-40

-30-30-30-30

-20-20-20-20

-10-10-10-10

0000

10101010

20202020

30303030

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

AEMG

AEMG

AEMG

AEMG

AEMGLS

AEMGLS

AEMGLS

AEMGLS

AEMGXF

AEMGXF

AEMGXF

AEMGXF

AEMGXFM

AEMGXFM

AEMGXFM

AEMGXFM

Pr

operty

Pr

operty

Pr

operty

Pr

operty



Fi ure 15

Diesel Fuel - TEXACO LOW SULFUR 95% / RME 5%46hrs @ 23C Property Change


14/19

- 14 -

Diesel Ref Fuel: ISO 1817 Type F Fluid 95% / RME 5%46hrs @ 23C Property Change

-70-70-70-70

-60-60-60-60

-50-50-50-50

-40-40-40-40

-30-30-30-30

-20-20-20-20

-10-10-10-10

0000

10101010

20202020

30303030

40404040

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACMEX

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-EXAO

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-M

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

HT-ACM-MAO

AEMG

AEMG

AEMG

AEMG

AEMGLS

AEMGLS

AEMGLS

AEMGLS

AEMGXF

AEMGXF

AEMGXF

AEMGXF

AEMGXFM

AEMGXFM

AEMGXFM

AEMGXFM

Property

Property

Property

Property



Fi ure 16

Scorch Safety / Rheology

Extrusion Processing

0000

5555

10101010

15151515

20202020

ACM 212Mollding AR212HR - Ext Cure

Minutes

Scorch Ts 10Scorch Ts 10Scorch Ts 10Scorch Ts 10

Safe Processing characteristicsMinutes@ 120C

MDR @ 180C

0

1

2

3

4

5

6

7

8

0 5 10 15 20 25 30

time (mins)

torque

(lbs-in

AR212HR AR22

Combined with Fast safe cureFor Steam Autoclaves

Figure 17

Tensile Change

190C

-50-50-50-50

-40-40-40-40

-30-30-30-30

-20-20-20-20

-10-10-10-10

0000

10101010

0000 100100100100 200200200200 300300300300 400400400400

Hours

Percent

Chang

HT-ACM AR212HRHT-ACM AR212HRHT-ACM AR212HRHT-ACM AR212HR

Figure 18


15/19

- 15 -

% Elongation Change

190C

-50-50-50-50

-40-40-40-40

-30-30-30-30

-20-20-20-20

-10-10-10-10

0000

10101010

0000 200200200200 400400400400

Hours

PercentChang


Fi ure 19

Tensile Change

175C

-50-50-50-50

-40-40-40-40

-30-30-30-30

-20-20-20-20

-10-10-10-10

0000

10101010

0000 168168168168 336336336336 504504504504 672672672672 840840840840 100100100100

8888

Hours

PercentChang


Figure 20

% Elongation Change

175C

-50

-40

-30

-20

-10

0

10

0 168 336 504 672 840 1008

Hours

PercentChang

e

HT-ACM AR212HR

Figure 21


16/19

- 16 -

% Elongation Change

150C

-50

-40

-30

-20

-10

0

10

0 504 1008 1512 2016

Hours

Perce

ntChange

HT-ACM AR212HR

Figure 22

% Elongation Change

150C

-50

-40

-30

-20

-10

0

10

0 504 1008 1512 2016 2520 3024 3528 4032

Hours

PercentChange

HT-ACM AR212HR HT-ACM AR212HR Trend

Figure 23

Heat Resistance

Heat resistance

150

155

160

165

170

175

180

1008 1512 2016 2520 3024 3528 4032

Hours

TempC

HT-ACM AR212HR

SAE J2236 Heat Resistance definition : Less than 50% property loss

Figure 24


17/19

- 17 -

Tear Resistance Trouser DIN 53507A

0

1

2

3

4

5

6

Tear

23C 175C (168h) 200C (72h)

kN

\m

Figure 25

O il R e s i s t a n c e

1 6 8 H o u r s @ 1 7 5 C

- 3 0- 2 5- 2 0- 1 5- 1 0

- 505

1 0

Har

dnes

s

Tens

ileE/

B

Volume

Weigh

t

O S 2 0 6 3 0 4 C 2 0 S L X H e l i x P l u s

Points&PercentChange

F i g u r e 2 6

O il R e s i s t a n c e

5 0 4 H o u r s @ 1 6 0 C

- 3 0- 2 5- 2 0- 1 5- 1 0

- 505

1 0

Hard

ness

Tens

ileE/B

Volume

Weigh

t

C 2 0 S L X H e l i x P l u s

Points&Percen

tChange

F i g u r e 2 7


18/19

- 18 -

D ie s e l F u e l R e s i s t a n c e

4 8 H o u r s @ 2 3 C

- 5 0

- 4 0

- 3 0

- 2 0

- 1 0

0

1 0

2 0

Hard

ness

Tens

ileE/B

Volume

Weigh

t

D i e s e l D i e s e l / R M E : 9 5 /5 %

Points&Percent

Change

F i g u r e 2 8

New TDI Hose Specifications

based on HT-ACM

VW: TL 526.34

GME : 14027 Draft May 2006

PSA: B21 5505 / Class 175C

Renault: 39-06-204 / D

Fiat: 9.02132 / 01 / E

Ford : WSD M96D30A&A2 (Development Basis)

DCX: DBL 6251.34 (Development Basis)

Table I

Zeon HT-ACM Hose Compound

Typical Property Range

Original Properties

Tensile 10 to 11.5 MPa

Elongation > 250 %

Hardness (ShA) 55-65 pts

Low Temperature -30C to -35C

Compression Set

168 hou rs @ 175C 30 to 35%

504 hou rs @ 175C 45 to 55%

Aged Properties (1 week at 190C)

Tensile 0 to -5%

Elongation 200%

Hardness (ShA) 62 pts (58 orig.)

Low Temperature No Change

Fluid Resistance

Engine Oil -Volume change < + 10%

Diesel & Diesel/RME < + 15%

Hardness Change 10 to + 5

Table II


19/19

19

Properties vs. Specification

HT ACM AR212HR Performance

Table III

Documents

ACM AEM KARŞILAŞTIRMASI AR212 AEM CFX.pdf