Universal Polyamide Overmold Thermoplastic Elastomer

Krishna Venkataswamy and Jiren Gu

GLS Corporation, 833 Ridgeview Drive, McHenry, IL 60050

ABSTRACT

Overmolding of thermoplastic elastomers (TPEs) for consumer applications has been driven by the escalating
market trends in enhanced ergonomic feel, touch, grippability, aesthetics and cushioning against impact,
vibration isolation and insulation. Polyamide (i.e. nylon) is preferred plastic in many high end applications due to
its crystalline structure and high melting temperature. Achieving TPE adhesion to polyamide with varied base
chemistries is well regarded to be difficult. An Universal polyamide overmolding TPE technology has been
developed by inventing novel compatibilization technology. These TPEs overcome the limitations of traditional
polyamide overmolding TPEs exhibiting wider processing windows for overmolding over a variety of polyamides.
They exhibit Universal bonding to every type of polyamide tested, unlike the earlier technologies which were
very sensitive to the type of polyamide.

INTRODUCTION

In the last decade, overmolding thermoplastic elastomers (TPEs) onto rigid substrates has been a
exploding trend in product differentiation in various consumer applications(1). Overmolding
eliminates the need for adhesives and primers to bond TPEs to rigid substrates. Design,
functionality, asthetics, performance needs and value addition have opened the rigid substrate
selection from commodity plastics to various engineering thermoplastics and their alloys. This
demand has propelled the development of novel thermoplastic elastomers that will bond to
various rigid substrates. Customer demands for robust overmolding elastomers have increased
with global manufacturing vendors with various degrees of sophistication both in equipment,
accessories and facilities.

The current paper emphasizes the science behind the adhesion principles of a soft thermoplastic
elastomer onto a rigid substrate. Overmolding TPEs onto polyamide (often referred to as “Nylon”)
as a rigid substrate is well regarded to be difficult. A novel TPE platform technology has been
developed which has outstanding overmolding performance onto a variety of polyamide
chemistries especially in insert molding which is a litmus test for overmolding. The TPE family
has adhesion on any type of polyamide tested in the study, including undried materials, making
them truly Universal polyamide overmold TPEs.

BACKGROUND

ADHESION MECHANISM

Adhesion principles between thermoplastic elastomer and the rigid substrate are governed by
three very important molecular factors which are the foundation of science behind good adhesive
behavior.

1. Surface energy match between the thermoplastic elastomers and the rigid thermoplastic
substrate.
2. Wetting and flow behavior of the soft thermoplastic elastomer and
3. Molecular interaction between the thermoplastic elastomer and the rigid thermoplastic.

Matching the surface energy of the known thermoplastic elastomers chemistries with various
rigid thermoplastics is illustrated in Figure 1. Novel developments in thermoplastic elastomers
have been driven by application demands that far exceed the TPE chemistry material selection
Page 1 of 11
space illustrated in this figure. Polyamides represent the highest polarity in Figure 1. The current
paper offers a novel robust TPE material selection for overmolding on to Polyamide.

Another important variable is wettability of TPE on substrate surface. For specific interactions to
occur between the TPE and the substrate, both have to come in intimate contact to each other on
a molecular level and wet out the surface. The wet out characteristic is determined by the
rheology of the TPEs as shown in Figure 2. Over molding compounds have relatively low
viscosity. Furthermore, they are shear -sensitive and exhibit shear thinning behavior. The
viscosity is in the lower end of the spectrum as shown in the figure 2 in high shear rate regimes.
This helps TPE flow and fill thin walled sections commonly encountered in over molding.

TPE chemistry and the type of engineering plastic play a critical role in influencing wettability. In
addition the diffusion, viscoelastic properties of the elastomer have an influence on the adhesion
properties as well.

The interface of the TPE and rigid substrate plays a vital role in determining not only the bond
strength, but also the type failure; i.e. cohesive (C) or adhesive (A). The cohesive mechanism is
generally regarded as the preferred mode of failure for indication of good bond strength.
However, a weak TPE with marginal bond strength can create an illusion of good bonding. In
some instances, good bonding exists even in the mechanism of adhesive failure.

Three types of mechanisms at the interface can facilitate bonding of the soft thermoplastic
elastomer and the rigid substrate i.e. mechanical interlock, chemical compatibility and specific
reaction or interaction at the interface. In order for any of these interactions to occur, molecular
level interaction is necessary between the polymeric components of the thermoplastic elastomers
and the rigid substrate. Especially in insert molding, the hot thermoplastic elastomers should be
capable of melting a few nanometers of the rigid surface. This implies efficient heat transfer
between the molten TPE to the rigid substrate.

ADHESION MEASUREMENT OF THE OVERMOLD TPE

The bond strength between the TPE and the engineering plastic can be measured by performing
o
a “90 Peel Test”. We have modified ASTM D903 method for plastics to evaluate the adhesion of
soft TPE onto rigid thermoplastic. A schematic diagram of this test procedure is shown in Figure
3. The testing is done on a molded substrate with a TPE skin insert molded on it. 25 mm wide
strip of TPE is cut and pulled at 90o to the substrate using an Instron tensile tester. The substrate
is locked in its place on a moving plate in order to maintain the 90o angle while the elastomer is
being pulled. The adhesion strength is measured by the force required to pull the elastomer from
the substrate and is reported as an average over 50 mm of pulling. The adhesion is categorized
based on adhesive failure (A)- if no TPE residue is left on the substrate or cohesive failure (C)- if
the failure is in TPE.

POLYAMIDE TYPE

Polyamides are a family of semi-crystalline engineering polymers with variations in chemistries,

melting point and crystallinity. It is more difficult for a TPE to form a melt bond with a semi-
crystalline polymer, such as polyamide, than with an amorphous polymer like polycarbonate.
There are various types of polyamides, such as Nylon 6, Nylon 66, Nylon 12, Nylon 6, 12 and
their copolymers.

Nylon crystallinity has a major role in bond strength. Nylon 66 has the highest melt temperature,
o
i.e. 265 C which would require a TPE with good, high temperature melt stability. Bonding of TPE
with a particular polyamide chemistry is also affected by the additives packages, such as heat
stabilizers, glass fibers, flow modifiers, impact modifiers and pigments. As an example, most
TPEs do not bond effectively to heat stabilized grade polyamide 6 (HS).

Page 2 of 11
AGING OF NYLON

Nylon is extremely hygroscopic and it also goes through post molding crystallization. Both of
these factors adversely affect bonding with a TPE.

For these reasons, it is often required to over mold TPE immediately after molding the nylon
substrate. This manufacturing practice reduces operational efficiency and flexibility.

NYLON MOLDING PROCESS

Bonding is also affected by mold design and nylon molding conditions. Conditions that would
increase nylon crystallinity adversely affect the TPE bonding.

There has been a technical and a market need for a TPE which can bond to different types of
polyamide chemistries from various sources which includes variables such as polyamide
chemistries, additive packages, moisture content, post molding aging history and processing
conditions.

NYLON OVERMOLDING TECHNOLOGIES

Relying on the presence of the polyamide structure in the TPE composition to generate a strong
(2)
bond when the molten blend comes into contact with a nylon substrate, US patents 5,843,577
(3)
and 5,750,268 disclose TPE blends for nylon overmold. However, TPEs based on this
technology can only be reliably used in two-shot over molding and very often do not work
universally on different polyamides.

NEW POLYAMIDE OVERMOLD TECHNOLOGY

We have developed a universal polyamide OM TPE technology platform(4). Specific TPE grades
were evaluated with different types of polyamides with various aging conditions. The material
properties data of 60A (I), 60 A (II) and 75A of Universal TPEs are presented in Table 1. 60 A
(II) is the latest development based on the technology platform to improve the adhesion behavior
over 60 A(1) for certain specific polyamides.

The adhesion between TPE and polyamide was measured by the force required to pull the
elastomer from the substrate. The data is reported as average force over 2 inch (5.08mm) of
pulling at speed of 2"/min (5.08mm/min).

Universal polyamide overmold TPEs exhibit exceptional bond strength on different polyamide
substrates. Table 2 summerizes the data of different polyamide systems; polyamide 6,
polyamide 66, glass filled, fiber reinforced , impact modified and heat stabilized. Also included
are the nylons at three aging conditions. As seen in Table 2, chemistry, types and aging have no
effect on bonding strength. These novel TPEs have no flow marks and showed fast cycle times,
which are important commercial considerations.

Page 3 of 11
COMPARISON WITH OTHER COMMERCIAL NYLON OVERMOLD TECHNOLOGIES

The novel universal nylon overmolding TPEs are compared with several commercial nylon
overmolding TPEs. Insert molding at three barrel temperatures was employed. Actual melt
temperature is about 5oC(10oF) lower than barrel setup. Three universal polyamide overmolding
TPEs are comparatively evaluated with two commercial SEBS nylon OM TPEs and two
commercial TPVs. They are designated as below:

Universal Polyamide OM TPEs: 60A (I), 60A (II) and 75A (III),
Commercial SEBS based TPE: 55A (III) and 65A (IV),
Commercial EPDM based TPE: 50A (V) and 70A (VI).

INSERT MOLDING

Insert molding data is reported in Table 3 and Figures 4 through 9. Insert molding is the most
severe test for the TPE as it has to bond to a cold substrate. It is apparent that the new universal
polyamide overmold TPEs can be processed at lower temperatures and have a strong adhesion
with various types of nylon substrates. Other advantages include fast setup, good mold release
and a wide processing window. Other commercial TPEs do not perform well in comparison, to
various polyamide types considered in this study.

TWO-SHOT MOLDING

Data is reported in Table 4. All TPEs provide bonding as two molten surfaces come together.
Universal polyamide TPEs can be processed at the lowest temperature and have the highest
bond strength in two-shot molding compared to other commercially available TPEs.

SUMMERY

Universal overmold TPEs provide excellent bonding on various types of polyamide substrates for
insert molding application. This new technology provides a universal nylon overmold solution for
polyamides and offer superior performance over other commercially available TPEs.

REFERENCES

1. Krishna Venkataswarmy, Rajesh Varma and Walter Ripple, Rubber World, Vol. 227, No. 3,
December, 2002.

2. Trazollah Ouhadi and Jacques Horrion, U.S. patent 5,843,577.

3. Mace Jean-Michel and Jacques Moerenhout, U.S. patent 5,750,268.

4. Jiren Gu and Krishna Venkataswamy, “Block Copolymer Compositions for Overmolding any
type of polyamide,US patent filed , March 2004

Page 4 of 11
 Table 1: Material properties of 60A and 75A TPE.

60A (I) 60A (II) 75A (III)

Hardness, A 60 60 75
Tensile MPa (psi) 3.54 (514) 2.75 (400) 3.36 (488)
Elongation, % 450 395 280

Table 2: Universal polyamide OM with different types of polyamides and aging conditions.

No Nylon Type Nylon description TPE Aging Peel,

Hardness condition N/mm / lb
/ in
1 Capron 8333GHI Glass and impact 60A(1) Aging A 3.7 / 21
2 Capron 8333GHI Glass and impact 60A(1) Aging B 3.2 / 20
3 Capron 8333GHI Glass and impact 60A(1) Aging C 3.3 / 19
4 Capron Glass, impact and heat 60A(1) Aging A 3.2 / 20
8333GHIHS stabilized
5 Capron Glass, impact and heat 75A Aging A 3.0 / 17
8333GHIHS stabilized
6 Ultramid B3ZG6 Glass and impact 60A(1) Aging A 3.2 / 18
7 Zytel 70G33L Glass 60A(1) Aging A 3.9 / 22
8 Zytel 408AHS Heat stabilized and flow 60A(1) Aging A 3.7 / 21
aid
9 Zytel 409AHS Heat stabilized and flow 60A(1) Aging A 3.2 / 20
aid

Aging A: nylon substrate conditioned at room temperature and humidity for 4 weeks before TPE
overmolding.

Aging B: nylon substrate conditioned (1) at room condition for 4 weeks, (2) immersion in water
for 24 hours and (3) dry 12 hour at room condition before TPE overmolding.

Aging C: nylon substrate conditioned (1) at room condition for 4 weeks, (2) immersion in water
for 24 hours and (3) dry with tissue paper immediately before TPE overmolding.

Molding condition:
Barrel temperature (from feed and nozzle) C (F):182, 249, 260, 260 (360, 480, 500, 500F)
Injection speed: 5.08 mm/min
TPE thickness: 1.5 mm.

Page 5 of 11
 Tabel 3: Inserting molding comparison.

Capron 8333GHI
N/mm 60A-I 60A-II 75A-III 55A-IV 65A-V 50A-VI 70A-VII
(lb/in)
260C/500F 3.7 / 21 N/A 3.2 / 18 No No No No
276C/530F 3.7 / 21 3.7 / 21 3.2 / 18 2.1 / 12 No No No
288C/550F N/A N/A N/A 2.5 / 14 2.5 / 14 No No

Capron 8333GHIHS
N/mm 60A-I 60A-II 75A-III 55A-IV 65A-IV 50A-VI 70A-VII
(lb/in)
260C/500F 3.9 / 22 N/A 3.3 / 19 No No No No
276C/530F 3.5 / 20 N/A 3.3 / 19 No No No No
288C/550F N/A N/A N/A 2.5 / 14 2.6 / 15 No No

Ultramid B3ZG6
N/mm 60A-I 60A-II 75A-III 55A-IV 65A-IV 50A-VI 70A-VII
(lb/in)
260C/500F 3.0 / 17 3.3 / 19 3.2 / 18 No No No No
276C/530F 3.2 / 18 3.3 / 19 3.2 / 18 No No No No
288C/550F 3.3 / 19 N/A 3.0 / 17 2.1 / 12 2.1 / 12 No No

Zytel 70G33L
N/mm 60A-I 60A-II 75A-III 55A-IV 65A-IV 50A-VI 70A-VII
(lb/in)
260C/500F 3.7 / 21 N/A 3.3 / 19 No No No No
276C/530F 3.7 / 21 3.7 / 21 3.3 / 19 2.3 / 13 No No No
288C/550F N/A N/A N/A 2.1 / 12 2.5 / 14 No No

Zytel 408HS
N/mm 60A-I 60A-II 75A-III 55A-IV 65A-IV 50A-VI 70A-VII
(lb/in)
260C/500F 3.0 / 17 N/A 3.2 / 18 No No No No
276C/530F 3.2 / 18 4 / 23 3.0 / 17 No No No No
288C/550F N/A N/A N/A 2.5 / 14 2.5 / 14 No No

Zytel 409AHS
N/mm 60A-I 60A-II 75A-III 55A-IV 65A-IV 50A-VI 70A-VII
(lb/in)
260C/500F 3.2 / 18 N/A 3.0 / 17 No No No No
276C/530F 3.3 / 19 4.2 / 24 2.8/ 16 No No No No
288C/550F N/A N/A N/A 2.1 / 12 2.1 / 12 No No

Page 6 of 11
 Table 4: Two-shot molding comparison

TPE 60A-I 75A-III 55A-IV 65A-IV 50A-VI 70A-VII

Barrel temp C/F 260/500 260/500 288/550 288/550 288/550 288/550
Peel Values
N/mm or Pli
Capron 4.2 / 24 3.5 / 20 3.3 / 19 3.0 / 17 2.3 / 13 3.0 / 17
8333GHI
Capron 4.0 / 23 3.9 / 22 2.8 / 16 3.0 / 17 2.3 / 13 3.2 / 18
8333GHIHS
Zytel 70G33L 4.2 / 24 3.3 / 19 2.8 / 16 3.3 / 18 1.9 / 11 3.3 / 19
Zytel 408AHS 4.0 / 23 4.0 / 23 3.5 / 20 3.7 / 21 1.9 / 11 3.9 / 22
Zytel 409AHS 4.2 / 24 4.0 / 23 3.2 / 18 3.3 / 19 1.6 / 9 3.3 / 19

Surface
Engineering Energy (mN/m) Elastomers
Plastics
46
Polyamide 6,6 Coplyamide
ABS 43 TPU
Polycarbonate 40 Copolyester
Acrylic 37
Polystyrene 34 Styrenic-TPE
31 TPV
Polypropylene
metallocenes
Polyethylene 28

Figure1. Surface energy match of various thermoplastic elastomers with rigid thermoplastics

Page 7 of 11
Figure 2. Rheological behavior of the thermoplastic elastomer which are shear sensitive. Shaded
area represents rheological range most suitable for overmolding.

Figure 3. Schematic Diagram of the peel test.

Page 8 of 11
 Capron 8333GHI
4
3.5
3
Peel force, N/mm

2.5
260C
2
1.5 276C

1 288C
0.5
0

65A-V
55A-IV
60A-I

50A-VI
60A-II

75A-III

70A-VII
TPE Grade

Figure4. Adhesion comparison of commercially available TPEs and TPVs with Universal TPEs:
Capron 8333 GHI

Capron 8333GHIHS
4
3.5
3
Peel force, N/mm

2.5
260C
2
1.5 276C
1 288C
0.5
0
55A-IV

65A-IV
60A-I

75A-III

50A-VI

70A-VII

TPE Grade

Figure 5. Adhesion comparison of commercially available TPEs and TPVs with Universal TPEs:
Capron 8333 GHIHS.

Page 9 of 11
 Zytel 70G33L
4
3.5
Peel force, N/mm

3
2.5
260C
2
1.5 276C
1 288C
0.5
0

55A-IV

65A-IV
60A-II

75A-III
60A-I

50A-VI

70A-VII
TPE Grade

Figure 6. Adhesion comparison of commercially available TPEs and TPVs with Universal TPEs:
Zytel 70G33L.

Zytel 408HS
4
3.5
Peel force, N/mm

3
2.5
260C
2
1.5 276C
1 288C
0.5
0
55A-IV

65A-IV
60A-I

60A-II

75A-III

50A-VI

70A-VII

TPE Grade

Figure 7. Adhesion comparison of commercially available TPEs and TPVs with Universal TPEs:
Zytel 408AHS.

Page 10 of 11
 Zytel 409AHS
4.5
4
Peel force, N/mm 3.5
3
2.5
260C
2
1.5 276C
1 288C
0.5
0

55A-IV

65A-IV
60A-I

60A-II

75A-III

50A-VI

70A-VII
TPE Grade

Figure 8. Adhesion comparison of commercially available TPEs and TPVs with Universal TPEs:
Zytel 409AHS.

Ultramid B3ZG6
3.5
3
Peel force, N/mm

2.5
2 260C
1.5 276C
1
288C
0.5
0
60A-II
60A-I

75A-III

70A-VII
50A-VI
55A-IV

65A-IV

TPE Grade

Figure 9. Adhesion comparison of commercially available TPEs and TPVs with Universal TPEs:
Ultramid B3ZG6.

Page 11 of 11