Polymer Bonding 2006

Duesseldorf, Germany 20-21 February 2006

Comparisons and Contrasts in Rubber-Metal Bonding using

Eight Polymer Types
R. J. Del Vecchio, Technical Consulting Services
Fuquay-Varina, NC, USA and Ernest Ferro Jr, Corry Rubber Corp., Corry, PA, USA
BIOGRAPHICAL NOTE
Mr. Del Vecchio was first involved with rubber technology as a graduate student in 1965, and entered the
rubber industry in 1969. His career included positions with DuPont, B F Goodrich, United Technologies, Lord
Corporation, and Barry Controls; in 1990 he went into fulltime consulting for rubber applications, processing,
product development, Quality Control, etc. He also instructs in and is the author of a book on Design of
Experiments methodology, has written two texts on rubber technology and contributed to several others, and
regularly publishes technical articles on various aspects of rubber technology, rubber bonding in particular.
His client list includes large and small rubber companies, large corporations specifying and/or buying rubber
products, and legal firms who make use of his capability as an Expert Witness.
ABSTRACT
A set of rubber compounds from eight different polymer families were formulated to approximately equal
hardness and tested for original and heat-aged bond strengths, as well as bond robustness to aggressive
environmental attack. Comparisons and contrasts in processing, physical, and bonding properties of the
materials are made.

Introduction:
Bond studies often center on a single compound, or perhaps just a few related compounds. (See references
1-5) However, one question becomes how very different compounds, based on different polymers, might
compare in bonding capacity. Since compounds of significantly different hardness and modulus can be
expected to display contrasting bond strengths, the test recipes would need to be adjusted to fall within a
reasonably narrow range of hardness. This will make the comparisons more valid and simplify the analysis.
Eight families of polymers were chosen, which included:
1. Natural Rubber (NR)
2. Styrene-butadiene rubber (SBR)
3. Polychloroprene rubber (CR)
4. Ethylene-propylene-diene rubber (EPDM)
5. Nitrile rubber (NBR)
6. Silicone rubber (Si)
7. Fluorocarbon rubber (FKM)
8. Millable urethane rubber (AU)
All formulations were adjusted by filler and plasticizer levels towards a target hardness of 65 Shore A. As an
additional facet of the experiment, three of the polymers were readjusted to softer hardness range of 45-50
Durometer. The descriptions of the formulae are provided in Table 1 below (detailed formulae are available
in the Appendix.)
Test properties for evaluation were chosen to include original hardness, tensile properties, heat aging
resistance, and compression set, followed by original bond strength, heat aged bond strength, and
resistance by stressed specimens to extended exposure to a hot salt spray environment. Tensile testing was
performed per ASTM D412. All bond tests were based on the ASTM D429 Method F specimen (the buffer
specimen, Figure 1), using a sample size of three. For all numerical data the median is reported and used
for analysis, the same practice required by ASTM for tensile testing. The amount of total elongation the
specimen withstood prior to bond failure was also recorded; this is not part of the normal test procedure, but
considered to be a possible response of interest, assuming any correlations with other properties could be
detected.

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Polymer Bonding 2006

Duesseldorf, Germany 20-21 February 2006

Figure 1- ASTM D429 Method F Specimen Drawing

Elastomer

Discussion:

Table 1- Compound Descriptions

Polymer
NR
SBR
CR
EPDM
NBR
Si
FKM
AU

A blend of natural and synthetic polyisoprene, reinforced primarily with

N300 series black, using an EV cure system. RHC 57.3%
Oil&N339 black extended polymer, conventional sulfur cure. RHC 39.5%
W-type polychloroprene, reinforced with a 700 series black. RHC 49.6%
Oil extended polymer, extended with 600 series black, EV cure system.
RHC 25.8%
Medium ACN polymer, extended with medium particle blacks, combination
of ester plasticizers, semi-EV cure system. RHC 37.7%
Blend of VMQ bases, peroxide cured
Cure incorporated fluorocarbon base, moderate reinforcement by Thermal
black. RHC 76.3%
Millable polyester urethane, reinforced with medium level of 600 series
black, sulfur cure system. RHC 71.9%

The comparison of Rheometer responses and basic physical properties of the eight primary compounds is
provided in Table 2.

Table 2- Rheometer & Physical Property Comparison

Polymer
NR
SBR
CR
EPDM NBR
Si
FKM
AU
ML, dNm
2.26
1.70
1.33
3.00
0.69
0.74
1.03
0.19
TS1 sec
136
188
222
356
141
73
265
144
TC90 sec
421
414
665
819
302
439
772
327
MH, dNm
16.92 14.44 20.40
9.06
13.71 22.60 13.31 16.52
Durometer
63.5
66.8
64.3
64.7
65.5
68.4
62.6
67.5
M100 MPa
3.0
2.6
4.5
1.9
3.1
2.5
2.3
3.3
Tensile Str.
25.1
15.9
16.2
12.5
10.7
7.1
10.3
18.6
Elongation%
501
468
218
687
373
329
425
481
Comp. Set%
13.4
21.8
9
29.3
20.1
13.4
49
44.9
22 hr/temp
70
70
100
100
100
150
150
70
Temp C
NOTE: Compression Set temperatures were adjusted to common use for each polymer
2

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Polymer Bonding 2006

Duesseldorf, Germany 20-21 February 2006

The low and high levels of each property are shown in Table 3. The range of hardness is reasonably limited,
62.6 to 68.4 Shore A, close to the target of 653. Other properties display considerably more variation, with
the Rheometer minimum viscosity covering more than an order of magnitude (0.19 to 3 dNm).

Table 3- Property Ranges

ML, dNm
TS1, sec
TC90, sec
MH, dNm
Durometer
M100
Tensile
Elongation
Comp. Set

Low
0.19
72.6
302
9.06
62.6
1.9
7.1
218
9

High
3
356
819
22.6
68.4
4.5
25.1
687
49

These broad variations in original properties, even at similar hardness levels, is only to be expected, given
the contrasts in both the base polymers and the particular compounding methods applied to each of them.
The wide range of 100% tensile moduli is noteworthy, since it demonstrates the lack of good correlation
between hardness and stiffness, which engineers tend to find surprising. [Note: Compression Set and Heat
Aging comparisons are difficult to evaluate when the test temperatures are not the same; but it is less valid to
compare exotic polymers to conventional ones at the same low test temperature than it is to compare them
using temperatures that are reasonably comparable in aggressive tendencies for the different polymers.]
Heat aging is commonly used as a baseline criterion for long term aging. Contrasts between the compounds
were expected, and the data in Table 4 demonstrate that expectation was fulfilled.

Table 4- Heat Aging Comparisons, % Change (70 hrs)

Polymer
Durometer
(points)
M100 MPa
Tensile Str.
Elongation
Temp C

NR

SBR

CR

EPDM

NBR

Si

FKM

AU

6.6

6.7

3.2

4.8

9.6

2.8

2.7

9.5

21.4
-4.1
-9.8
70

59.3
1
-25.4
70

12.1
8.1
7.23
100

60.3
4.8
-32.5
100

156
18.3
-55.5
100

16
-12.8
-19.2
150

30.7
9.52
-27.8
150

80.5
4.8
-29.5
70

In general, the compounds were affected by heat aging in the anticipated ways, that is, hardness and
modulus increased, while elongation decreased (with the exception of the polychloroprene compound). The
NBR formula contained a moderate loading of a volatile ester plasticizer, which led to its having the most
severe heat aging effects. (See Reference Table I for formulation details)
The key data in this study are the bond strengths, which are shown in Table 5 below.
The broad range of these results is not surprising, nor is the range of different levels of specimen elongation
at break. The heat aging can also be seen to have contrasting effects on the bonds, ranging from the
substantial lowering seen in the NBR specimens, to the dramatic increase of the FKM specimens.
The lack of change in the silicone strength demonstrates the robustness of that polymer and its bonding
system even when aged at 150C; in stark contrast, the near-doubling of bond strength of the fluorocarbon
specimens is due to the heat aging exposure becoming in effect a postcure process that produced beneficial
effect in the compound. (Note that while heat aging effects on the FKM compound reduced its Elongation,
there was an opposite effect on the bonded specimens.)

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Polymer Bonding 2006

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Table 5- Bond Properties (ASTM D-429 Method F)

Polymer
Orig Strength
% Elongation
Heat Age pct
chng- Strength
Heat Age pct
chng- Elong
Salt Spray Life,
days

NR
4.80
124.4

SBR
5.75
147.4

CR
4.34
83.6

EPDM
1.66
57

NBR
5.78
129.9

Si
3.21
90.6

FKM
2.97
97.2

AU
4.77
116

3.3%

-4.3%

38.0%

30.9%

-1.5%

-1.8%

86.3%

25.3%

-5.4%

-10.6%

18.1%

10.0%

-16.7%

-17.0%

52.4%

-2.7%

33+

33+

Appearance of the failed bond surfaces from their original testing reveals some interesting contrasts. (See
Figure 2) The NR, SBR, CR, NBR, and Si all display large measures of cohesive failure in the rubber, with a
pattern of torn material that indicates the initial rupture was in or near the center area and then propagated
outwards. This is normally interpreted as demonstrating that an excellent bond has been achieved.

Figure 2- Typical Specimens of Torn Bonds

The FKM and AU specimens both display less torn rubber. In the case of the urethane this does not appear
to reflect anything about the bond strength, since it failed at a reasonably high level of force, but for the FKM
rubber it could be considered to imply less ideal bonding. The EPDM specimens all showed very little
remaining rubber at the bond interface, and the lowest bond strength as well, so the conclusion that this
combination of compound and adhesive did not produce high strength bonds is well supported.
After heat aging, the FKM bond strength increased, as noted above, and the mode of failure of the
specimens changed to leave substantially more torn rubber on the metal surface. This confirms that the heat
aging in effect postcured the material and improved its properties. None of the other specimens from testing
after heat aging changed in appearance.
The accelerated environmental test did not provide as graduated a series of material contrasts as was
hoped. In essence, the various elastomers fell into four groups, which were the very short term failures (NR
& EPDM), the short term failures (Si & AU), the medium term failures (CR & NBR), and the long term
survivors (SBR & FKM).
The strength of rubber-metal bonds might be expected to correlate with some basic properties of the
compound, and bond robustness might be expected to correlate with resistance to heat aging. This was not
observed. Figure 3 is an exemplar of the possible relationships investigated, and demonstrates the lack of
correlation between compound Tensile Strength and Bond Strength. None of the other measured properties,
such as Tensile Modulus (M-100), original Elongation, changes from Heat Aging of either tensile specimens
or bonded specimens, etc, showed any correlation with Salt Spray Life. [It must be noted that no primer
coats were used in this experiment, and prior work (see reference 5) has demonstrated that use of a primer
makes bonds more robust to environmental testing.]

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Polymer Bonding 2006

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Figure 3- X vs Y Correlation Chart

Tensile vs Bond Strength

6.0

NBR

SBR

5.0

NR

AU

Bond

CR

4.0
3.0

Si

FKM

2.0
EPDM

1.0
6.0

8.0

10.0

12.0

14.0

16.0

18.0

20.0

22.0

24.0

26.0

Tensile (MPa)

Conclusions:
These eight compounds, varying widely in polymer type and formulation details, demonstrate no major
commonality in bonding characteristics. This illustrates the principle that rubber-metal bonding is a complex
function of compound chemistry, adhesive system, and substrate characteristics, and not readily predictable
when dissimilar formulations are under consideration.

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Polymer Bonding 2006

Duesseldorf, Germany 20-21 February 2006

Reference Table I Formulations

NR
SIR-10
Polyisoprene
SKI-3
Zinc Oxide
Stearic Acid

5.00
1.00

Stearic Acid
Antozite 67P

1.00
3.00

Proaid 9831

1.75

3.00

StanPlas 105

5.00

10.00

N-762 Black

AgeRite
Resin D
Antozite 67P
Nocheck
4607 Wax
N-339
Carbon Black
N-650
Carbon Black
Sulfur
Vanax A
BBTS
Proaid 9802
Total phr

1.00

Nocheck
4607 Wax
N-650
Carbon Black
Sulfur

CR
Neoprene W
Agerite
Stalite S
Stearic Acid
Stan
Mag
Bar
Sundex 790

3.00
3.00

ZBED
BBTS

0.20
1.55

50.00

Proaid 9802

2.00

10.00

Total phr

0.51
1.55
1.55
3.00
186.36

NBR
Nysyn 33-5

100.00

50.00
50.00

Stearic Acid

1.00

Zinc Oxide

5.00

Agerite
Superflex
Solid G
N-762 Black
N-550 Black
Sulfur
Altax
Methyl Tuads
Santogard
PVI
DOP
Merrol 3810
Total phr

1.33

85.00
25.00
0.75
0.50
1.50
0.20

SBR
SBR-1847
Zinc Oxide

Si
Silastic NPC940
Silastic NPC980
Varox DBPH50
Ultramarine
Blue
Thermax
Total phr

225.00
5.00

2.25

NoCheck
4607 Wax
Zinc Oxide
Vulkacit
CRV/LG
Total phr

100.00
2.00
1.00
5.56

EPDM
Keltan 5531 200.00
Stearic Acid
1.00

20.00

Sunpar 150
N-650
Black
Zinc Oxide

65.00

Sulfur

0.45

2.00

Vanax A

0.40

5.00
1.25

Santocure
TMTM

0.45
0.60

201.81

Total phr

20.00
160.00
5.00

387.90

253.00

FKM
Fluorel FC- 100.00
2123
N-990 Black
25.00

EU
Millathane
E-76
SIR-10

1.00

Maglite D

3.00

0.50

Calcium
Hydroxide

3.00

Zinc
Stearate
N-650
Black

25.00
75.00

0.00
103.00

Total phr

131.00

Altax
MBT
Sulfur
Thanecure
Total phr

96.00
4.00
0.50
30.00

4.00
2.00
1.50
1.00
139.00

35.00
10.00
265.28

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Polymer Bonding 2006

Duesseldorf, Germany 20-21 February 2006

REFERENCES
1. Del Vecchio, R. J., and Halladay, J. R., Rubber-Metal Bonding Studies Using Designed Experiments.
152nd Meeting of the Rubber Division ACS. October, 1997.
2. Del Vecchio, R. J., "Factors Affecting Rubber to Metal Bond Strength and Failure Mode" delivered
12/7/98, Rubber Bonding Conference, Frankfurt, Germany
3. Halladay, J. R. and Krakowski, F. J., The Effect of Cure System on Natural Rubber Bonding. 156th
Meeting of the Rubber Division ACS. September, 1999.
4. Del Vecchio, R. J., " Compounding Effects on Physical Properties and Rubber-Metal Bonding " delivered
6/12/02, Rubber Chemicals, Compounding, & Mixing Conference, Munich, Germany
5. Del Vecchio, R. J., and Ferro Ernest, Strength vs Durability of Rubber-Metal Bonds: Factor Effects from
Processing & Chemistry delivered 27 April 2004, Polymer Bonding Conference, Munich, Germany
ACKNOWLEDGEMENTS
We wish to acknowledge the technical support provided in this work by Lord Corporation, Erie, PA, through
the graces of Brady Hultmann. We also wish to thank Jason Christianson, our hardworking technician, for all
his efforts in mixing, molding, and testing the required specimens.

APPENDIX
Technical Details
Metal PreparationAll buffers were grit blasted and then solvent wiped using a clean cloth saturated with Acetone.
Primer useNone Used
Adhesive applicationUndiluted Chemlok 8560S used on NR, SBR, CR, and EPDM, applied by spraying. A dry topcoat of .6 to .1
mils, average obtained .82 mils. Metals were warmed to 70C prior to spraying.
Undiluted Chemlok 608 used on Si, applied by brushing a thin coat on unpreheated metals.
Undiluted Chemlok 5150 used with FKM, applied by brushing a thin coat on unpreheated metals.
TyPly BN diluted 2:1 TyPly BN:Methanol used for PU, applied to metals by brushing. Metals were at room
temperature.
Molding10 Cavity transfer mold, conventional hydraulic press Mold conditions listed below.
NR, SBR, CR, NBR, EPDM, PU, SI cured at a temperature of 160C, using a cure time Tc90 + 10.
FKM cured at mold temperature of 170C, also using a cure time Tc90 + 10 (for that temperature).
Standard physical testingPerformed as per ASTM D2240 (Durometer hardness), D412 (Tensile properties), D395 (Compression set),
and D624 (Tear strength, Die C).
Heat aging test conditionsASTM D473
Salt spray exposureAccording to ASTM B117, 35C, 95% humidity, 5% salt, pH 6.5-7.2, parts were stressed 30% in tension.
Pull TestingPerformed according to ASTM Method D429 on a Tensometer T-10 machine, 50.8 mm/minute.

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