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Because they maintain excellent strength and toughness during exposure to hot, aggressive
automotive fluids and to hot air whether humid or dry, high performance polyamides (HPPA) can
make durable, functional components for automotive thermal management and other demanding
applications. This paper reviews the basic chemistry of polyamides and demonstrates how the
HPPA family differs from standard nylon. It focuses on semi-aromatic HPPA polymers known as
polyphthalamides (PPA).
Under-the-hood applications have shown particularly Polymers consist of repeating units of monomers
high growth. Typical examples include air intake (individual molecules) that combine to form a long chain.
manifolds, rocker covers, radiator end tanks, fuel rails, The polymers may consist of a single type of molecule
electrical connectors and others. Polyamides have had (known as a homopolymer) or may be combinations of
great success in those areas due to their excellent balance of more than one molecule (known as a copolymer).
oil resistance, thermal stability, mechanical strength,
toughness and other desirable properties. A major class of polymers known as thermoplastics
may be remelted, as opposed to thermosets, which form
In recent years, temperatures in the engine irreversible crosslinks between polymer chains. Within the
compartment have been rising because of reduced space thermoplastics category, there are amorphous and
and more powerful engines. The temperature resistance of crystalline polymers. Amorphous polymers have random
plastics parts has consequently become even more critical. orientation of their polymer chains, whereas crystalline
Weight reduction also continues being an issue to help polymers form highly ordered crystal structures within an
reduce fuel consumption. These factors can be expected to amorphous matrix (Figure 1). The term semi-crystalline
lead to increased use of polymers with higher temperature polymers is used for polymers containing both crystalline
performance such as PPAs. and amorphous regions.
The resistance of PPA’s to antifreeze is another factor As a general rule, amorphous polymers have
in their favor. In an investigation of the effect of antifreeze advantages of transparency and toughness. Semi-
solutions on polyamides in 1995, Garrett and Owens (Ref. crystalline polymers have advantages in chemical resistance
7) concluded that the performance of semi-aromatic PPA is and temperature performance. These are general statements
superior to that of aliphatic polyamides such as nylon 6 or however, and the designer must consult product-specific
nylon 66. We have extended their study by measuring the literature and test data for specific properties.
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POLYAMIDE PRODUCT FAMILY
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Table I shows properties typical of glass-reinforced
composites of the polyamides we have discussed. In
general, the PPAs have higher glass transition temperatures,
higher melt points and higher deflection temperatures2 than
the aliphatic PA66 and PA46. Also, the PPAs pick up less
moisture so moisture exposure has a smaller effect on
properties. Note however, there are differences in key
properties within the PPA family, these translate into
different performance (see references 5 and 11).
DTUL @ % H2O,
Grade
1.8MPa 24 hrs
ASTM D5336 defines a polyphthalamide (PPA) as “a Polymer Tg (C) Tm (C) (C) 2mm
polyamide in which the residues of terephthalic acid or PA6T/DT (PPA) 140 300 264 0.5% A
isophthalic acid or a combination of the two comprise at PA6T/6I/66 (PPA) 125 312 278 0.5% B
PA6T/66 (PPA) 90 310 285 0.5% C
least 55 molar percent of the dicarboxylic acid portion of PA 46 80 295 290 1.5% D
the repeating structural units in the polymer chain” (ASTM, PA 66 65 263 252 1.2% E
2003). Referring back to Figure 3, this means that a portion
of the acid segment is replaced with an aromatic Test Method DMA ISO 11357-1/-3 ISO 75f ISO 62
component, terephthalic acid (TPA) and/or isophthalic acid
(IPA).
3
Figure 5: Chemical structures of three common PPAs: PA6T/66, PA6TDT, and PA6T/6I/66.
Shown in Figure 6 is the flex modulus4 of various the glass fibers that reinforce a structure between the
polyamides as a function of temperature. These are all crystalline regions and maintain significant properties
typical 30-35% glass-reinforced commercially available above the Tg. PA46 has interesting properties due to its
grades. The drop in flex modulus corresponds to the glass relatively high flex modulus at the very highest of
transition temperature (Tg), when the amorphous region of temperatures. This is due to its higher level of crystallinity.
the semi-crystalline polymer matrix becomes mobile. It is However, referring back to Table I, PA46 picks up a
significant amount of moisture relative to PPA, and this
reduces its performance in many real-life conditions where
4
Flex (flexural) modulus, defined by ISO 178, is an approximation to humidity or aqueous chemicals are present. The
Young's modulus of a test specimen under a flexural (bending) load.
4
significance of that was reported for coolant systems in The chemistry of automotive coolants is quite
reference 7. complex, typically with an ethylene glycol / water mixture
as a base. Corrosion inhibitors are added to the ethylene
glycol. Conventional antifreezes have used inorganic
corrosion inhibitors such as silicates but these tend to
degrade quickly over time. Today, most of the current
corrosion inhibitor technology is based on organic acid
technology (OAT) or hybrid organic acid technology
(HOAT). The organic acids used today have better stability,
allowing for much longer time between changing of engine
coolant, hence the term "long-life coolants" or "extended
life coolants" (Ref. 17 and 18).
Creep, also known as deformation under constant The coolants chosen were both long-life formulations:
load, is one of the most important mechanical properties to Valvoline Zerex® G05, a hybrid organic acid technology
characterize long-term performance of a plastic under load (HOAT) coolant herein referred to as "Zerex® G05" and
(Ref. 3). Materials with low creep retain their original Prestone® Extended Life 5/150, a Dex-Cool® approved
dimensions longer than materials with high creep. Shown formulation based on organic acid technology (OAT),
in Figure 7 is the creep inferred from accelerated testing herein referred to as "Dex-Cool®". Both coolants were
via dynamic mechanical analysis (DMA) (Ref. 8). tested as a 50/50 mix with water.
Measurements were taken on a specimen under flexural
load of 28 MPa at 150C. Results indicate that the percent The test protocol was ISO 527, measuring stress at
total strain of PPA6T/DT is about 50-75% that of break 6 and tensile modulus7 on 4mm thick test specimens
PA6T/66, PA6T/6I/66 and PA66 under the same after immersion in the solution at 130°C. Test
conditions. These results are consistent with the flexural measurements were performed at 23°C. Results are shown
modulus values at 150C shown in Figure 6. in Figures 8 and 9.
5
Figure 10: Stress at break comparison in Zerex® and Dex-
cool® LLC for 35% GR PPA (PA6T/DT).
Figure 8: Stress at break for 30-35% GR polyamides
exposed to 50% Zerex® LLC at 130°C.
Higher glass levels will help maintain an additional
buffer of performance. After 5000 hrs in Dex-cool®, a
PA6T/DT with 45% GR maintained almost 20% higher
tensile modulus compared to 35% GR, as indicated in
Figure 11.
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APPLICATION OF PPA IN AUTOMOTIVE
CONCLUDING REMARKS
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feature flexibility and potential for cost reduction. Creep Behavior," Journal of Thermal Analysis and
Furthermore, polyphthalamides represent a class of Calorimetry, vol. 69, pages 37-52, 2002.
polymers, differing in the polymer backbone and
consequently showing differences in performance. We've 9. Kohan, M., "Nylon Plastics Handbook," Hanser
demonstrated these performance differences through data, Publishers, New York, 631 pages, 1995.
and demonstrated the commercial viability of PPA in
thermal management applications through successful case 10. Kohan, M., S. Mestemacher, R. Pagilagan and K.
studies. Redmond, "Polyamides," Ullmann’s Encyclopedia of
Industrial Chemistry, John Wiley & Sons, 2003.
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Learning Center, http://www.plastics-car.com, 2004. Polymer Science: "The Macrogalleria: A
Cyberwonderland of Polymer Fun",
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D5336-03, 5 pages, 2003. 16. Weber, J., "Polyamides, General", Kirk-Othmer
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for Engine Coolant / Antifreeze with Improved 18. Wilson, T., "A Comparison of Various Polymers in
Thermal Stability Properties," SAE Technical Paper Select Organic Acid Technology (OAT) Coolants,"
Series #2001-01-1182, 7 pages, 2001. SAE Technical Paper Series #2000-01-1095, 17 pages,
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5. Ferrito, S., "An Analytical Approach Toward
Monitoring Degradation in Engineering Thermoplastic 19. Zimmerman J., “Polyamides”, Encyclopedia of
Materials Used for Electrical Applications," Annu. Polymer Science & Engineering, Wiley-Interscience,
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KEY WORDS