Compression and Recovery Behaviour of Polyamide-6 Based Foams
Compression and Recovery Behaviour of Polyamide-6 Based Foams
Compression and Recovery Behaviour of Polyamide-6 Based Foams
SUMMARY
This paper presents experimentally determined compression sets and compression behaviour of two closed-cell,
crosslinked foam materials; ZOTEK N B50 (Nylon 6) and ZOTEK N A30 (nylon/polyolefin alloy). This work
forms the basis of future investigations into the post-impact behaviour of these foams.
Compression set performance was measured at 25.0, 37.5 and 50.0% strain at nine temperatures ranging from
-5 to 90 °C. Compression tests at constant strain rates were conducted at four temperatures between 23 to 90 °C.
Finally compression tests at 23 °C were repeated at four strain rates between 0.3 and 550 hr-1 to determine strain
rate dependency. The Nagy and Williams-Landel-Ferry scaling factor for strain rate and temperature were applied
to the experimental results and equations were derived which allowed the performance of the two polyamide
based foams to be interpolated over the strain rate and temperature range of study. The required material
properties of interest of the base polymers have been assessed and are presented and discussed in relation to the
performance of the foam materials.
Keywords: Cellular solid, Polyamide, Nylon-6, Polyolefin, Compression set, Stress-strain, Scanning
electron microscope, Glass transition temperature, Strain rate, Foam
and no predictive interpretation of the Figure 1. (a) Tensile test specimen of base materials, (b) Stress-strain behaviour of
foam performance outside of the range N B50 and N A30 base polymer
of these measurements is available.
(a)
Literature does contain studies on
recovery rates after loading for
crosslinked, closed-cell foams.
Strain gauges 1 & 2
Mills and Gilchrist22 investigated 3rd strain gauge fitted at
fitted to each side of
the recovery rates of low density 90° to strain gauges 1
polymer sample
polyethylene (LDPE) and ethylene & 2 for Poisson’s ratio
vinyl acetate copolymer (EVA) foams measurement
on completion of 7 day creep tests.
Their work shows that at relatively high
strains, the majority of the gas in the
cells escapes. For low density foams,
viscoelastic recovery is hindered by
the pressure drop in the cells, making
recovery a slow process. This study
does not investigate the permeability
of cell walls to air but it is a likely
contributing factor to the recovery of
the foams studied in this work. (b)
to a fixed strain (25.0, 37.5 and 50.0% Figure 2. Compression set results of N B50 and N A30 at temperatures between
of original thickness) and acclimatised -5 °C and 90 °C at c.s. 50.0%
at experimental temperature (-5, 10,
23, 30, 40, 50, 60, 70 and 90 °C) for a
duration of 22 hours.
do − dr
c.s. = x100
do
(1)
temperature studied. The results show Figure 3. Comparison of experimental compression set data at 30 and 1440
that N B50 has a lower recovery rate minutes with empirical curve fit- N A30
than the N A30 across all measured
temperatures. A wider spread of data
is also noticeable with respect to
temperature for N A30. This would
suggest that the N A30 recovery is
more sensitive to temperature than
that of N B50. In addition, the results
indicate that neither material returns to
a zero compression set state (i.e. full
recovery) after 24 h. This is expected,
given the short timescale and the closed
cell nature of these materials.
c.s. (%) = a ln(t) + b Table 3. Coefficients of logarithmic empirical fitting to compression set data for
(30 < t < 1440) (2) ZOTEK N B50
Test Compressive Strain Compressive Strain Compressive Strain
where t is the recovery time in minutes Temperature = 25.0% = 37.5% = 50.0%
and ‘a’ and ‘b’ are temperature (°C) a b a b a b
dependent coefficients as presented
-5 -0.934 16.511 -0.812 21.246 -1.208 32.092
in Table 3.
10 -1.340 18.744 -0.619 19.596 -1.497 35.509
The same conditions are applied to the 23 -1.004 18.339 -0.870 25.699 -1.323 32.884
lower density, N A30 foam material, 30 -0.936 20.644 -1.242 25.410 -1.798 36.023
and results showed a similar pattern 40 -1.224 19.359 -1.827 31.347 -1.855 32.000
to those as previously reported 25. 50 -1.275 22.352 -1.662 31.238 -3.314 44.367
Eq. (2) can therefore apply to N A30 60 -1.266 22.138 -1.431 29.447 -1.745 33.623
foam with the temperature-dependent
70 -1.050 19.644 -1.200 27.012 -2.334 37.426
coefficients given in Table 4. In both
90 -1.360 21.431 -1.591 29.680 -1.265 32.904
cases the data, when plotted, exhibits
a high logarithmic dependency as a
Table 4. Coefficients of logarithmic empirical fitting to compression set data for
function of recovery time.
ZOTEK N A30
Test Compressive Strain Compressive Strain Compressive Strain
Eq. (3) predicts the compression set as Temperature = 25.0% = 37.5% = 50.0%
a function of recovery time at a specific (°C) a b a b a b
temperature. Although Figure 2 would
-5 -0.373 4.997 -0.578 8.857 -0.900 11.986
indicate a very limited temperature
effect on the compression set behaviour 10 -0.632 7.583 -0.660 8.439 -0.460 8.268
for N B50, it shows a definite upward 23 -0.961 10.221 -0.827 13.612 -1.093 14.743
trend for N A30, indicating that a 30 -1.448 16.435 -1.063 13.043 -1.629 20.955
temperature dependent function is 40 -1.101 11.524 -1.279 15.559 -1.137 16.649
required. A surface modelling package, 50 -1.215 14.100 -1.417 18.000 -1.548 22.333
3D table curve26, was used to derive a 60 -1.082 11.427 -1.098 16.148 -1.447 20.754
surface fit. Equation (3) uses a 3rd order
70 -1.282 14.067 -1.392 19.370 -1.434 22.969
polynomial for temperature which
90 -1.326 16.911 -1.598 24.060 -1.731 30.159
includes a logarithmic time component.
This function is an empirical surface tube of length 300 mm was positioned dampened the temperature fluctuations
fit which predicts the compression over the sample and located on a of the heating jacket. Temperature was
set performance of these foams as a preinstalled base cap. A second 50 mm monitored and controlled by the use
function of both temperature and time. aluminium disc and rod arrangement of thermocouples; one on the foam
was placed in the tube and held above sample and one in the brass tube. Once
c.s. (%) = a + b T + c T2 + d T3 + the foam sample by the upper jaw of the thermal equilibrium had been achieved,
e ln(t) (-5 < T < 90, 30 < t < 1440) universal testing machine. The brass the sample was left to condition for a
(3) tube was capped using a second brass further 2 hours.
plate. A heating jacket was wrapped
where t is the recovery time in minutes,
around the assembly and set to the Compressive loading was applied
T is the recovery temperature in oC
required temperature (see Figure 4). to the sample at a constant strain
and ‘a’ to ‘e’ are the foam dependent
constant coefficients presented in The brass tube served as a heat sink and rate of 0.01 s-1 until a strain of 80%
Tables 5 and 6 for N B50 and N A30,
respectively.
Table 5. Coefficients of surface fitting to compression set data at various
temperatures N B50
Compression set at any given time
Compressive Coefficient
for N B50 is almost independent
Strain a b c d e
of temperature but for N A30 the
compression set increases as the 25.0% 17.7925 8.2464 x 10 -2
-1.0413 x 10 -4
-5.7929 x 10-6 -1.1572
temperature rise as shown in Figure 3. 37.5% 23.5808 1.1710 x 10-1 -1.5032 x 10-5 -8.9340 x 10-6 -1.2686
50.0% 35.7303 4.2558 x 10-2 -2.0852 x 10-3 -1.7781 x 10 -5 -1.7773
3.3 Compression Testing
The compressive stress-strain Table 6. Coefficients of surface fitting to compression set data at various
temperatures N A30
performance of the foam is a
characteristic of its energy-absorbing Compressive Coefficient
Strain a b c d e
capabilities, and can be determined by
the methods described in BS3386-127. 25.0% 9.1989 1.8785 x 10-1 -4.0553 x10-3 3.0341 x 10-5 -1.0598
It should be noted that the level of 37.5% 11.4089 8.2848 x 10-2 -4.2795 x 10-4 8.1484 x 10-6 -1.0745
accuracy for force and displacement 50.0% 13.5568 1.0628 x 10-1
-2.0541 x10 -4
8.0655 x 10-6 -1.2642
used in this study far exceeds those
specified in the standard. Further
to this, BS3386-1 does not include Figure 4. High temperature compression test set up
investigation at varying strain rates or
environmental temperature. This study
used BS3386-1 as a guide and develops
the method to study the effect of these
parameters.
was reached. Compression in the Figure 5. Experimental and fitted stress-strain curves over the temperature range
sample was measured using a LVDT 50 °C to 90 °C. (a) N B50 (b) N A 30
branched from the loading arm (see
Figure 4). Both load and compressive
displacement were logged using a
Vishay Measurements Group System
5100 (data logger) set at 10Hz sample
rate. The foams were tested at four
different temperatures of 23, 50, 70
and 90 °C.
−C ( T − Tr )
L(T) = EXP 1
C2 + ( T − Tr )
(4)
In order to improve the scaling for low Table 8. Variance in elastic Young’s modulus at different strain rate at 23 °C
stiffness foams, the Nagy equation N B50 N A30
was modified to include an additional
Strain Rate Elastic Modulus Strain Rate Elastic Modulus E*
strain-dependent term as follows: (hr-1) E* (MPa) (hr-1) (MPa)
0.3044 6.52 0.308 0.97
n(ε )
3.020 7.79 3.050 1.29
ε
σ(ε) = A(ε)σ 0 54.64 10.08 30.5 2.04
ε
o
(9) 540.7 10.81 305.0 2.78
A(e) = 1.3 − 0.42ε N A30
1 N B50
(10)
4. SCANNING ELECTRON
MICROSCOPY STUDY OF
FOAM
The reliability of Eq. (3) can be
supported to some extent through
the analysis of Scanning Electron
Microscope (SEM) images of the
foam structure before and after
testing to investigate any potential
damage. Since SEM operates at low
pressure and high energy levels,
initial tests were conducted at
prolonged exposure to determine
any detrimental effects; none were
observed. Nonetheless, the SEM
images shown represent a small part
of the total bulk foam structure and 4.1 SEM Images Experimental 4.2 Interpretation and
the extent of any damage observed
Procedure Discussion of SEM Images
may not be representative of the
whole sample. Samples were cut Compression set samples for 50% SEM images of N A30 and N
using a surgical knife. initial compressive strains were B50 at 50% strain are presented
selected from the extremes of the in Figure 9a,c,d and f for each
As reported by Mills and Gilchrist22 temperature range. For comparative of the compression set samples at
and discussed in Section 3.1, recovery purposes, an uncompressed sample both high (90 °C) and low (-5 °C)
would be slowed by loss of gas (zero compression) was also analysed temperature. Figures 9b and 9e
pressure within the foam cells and as a control. show control samples which have
plastic damage in the cell walls. experienced no compression testing.
While diffusion of the gas through Three 10 mm X 10 mm X 5 mm (5 mm Figure 9a-f reveals no obvious
the cell window membranes is one in direction of observation) test pieces damage in the form of burst cells.
mechanism, it may also be expected were cut, from each of the compression These images represent the extremes
that, depending on strain levels and set samples. The magnification settings of test temperature and compressive
polymer matrix, evidence of ruptured are approximately 200x and 100x strain for the compression set tests.
cell walls could also be observed in for the N B50 and N A30 images, Assuming these to be representative
the SEM images. respectively. of the foam structure, it is reasonable
Figure 8. Experimental and fitted stress over the strain range 0.05 to 0.8 at 23 °C for the strain rates studied (a, b and c) N
A30, (d) N B50
to assume no observable rupture of the Figure 10a-d shows SEM images the base polymer mechanical properties
cell windows would have been caused of the samples which have been presented in Figure 1b.
by the application of the lower strain compressed to 80% of the initial
levels and intermediate temperatures thickness during the compression
5. DISCUSSION
of the other compression set tests. tests for both foams. N B50 sample
images show significant plastic damage The compression set data show that
Figure 9a shows slightly more resulting, in some cases, in rupture over a 24 hour period neither of the
buckling and wrinkling within the of the cell windows, Figure 10a foam materials returned to its original
polymer film than is observed in the and 10b. This characteristic is also thickness. This is expected behaviour
control, Figure 9b. It is therefore evident in the N A30 sample images of closed cell polymer foams, and
possible that the N B50 foam will not with increased plastic damage but no suggests that mechanisms of plastic
recover its original thickness as some observed bursting cell wall. These damage due to cell wall buckling
plastic damage may have occurred due images confirm that the base polymer and gas loss through diffusion have
to buckling in which the material has of N A30 foam has greater ductility contributed to irrecoverable set in
significantly exceeded the elastic limit than that of the more brittle N B50 the bulk cellular structure. SEM
of the polymer. polymer base, a result also indicated by images have identified that there is no
Figure 9. SEM results- 50% compression set tests (a) N B50 at 90 °C, (b) N B50 Figure 10. SEM results- 80%
no compression at 23 °C, (c) N B50 at -5 °C, (d) N A30 at 90 °C, (e) N A30 no compression set tests (a) N B50 at
compression at 23 °C, (f) N A30 at -5 °C 90 °C, (b) N B50 at -5 °C, (c) N A30 at
90 °C, (d) N A30 at -5 °C
consistent cell window rupture evident cell wall rupture which suggests that at
within the structure of the materials at strains greater than 50% compression
strain up to 50%, but there are cell wall cell walls did fail by this mechanism.
buckling effects visible in a number This contributed to a reduction in the
of the high strain samples. This is mechanical performance of the bulk
indicative of plastic damage caused foam. There is no evidence in this
by the initial compressive stage of study to suggest that the foam material
the compression set test contributing will not continue to recover beyond
to irrecoverable strain. Furthermore, 24 hours since the base polymers are
the same behaviour was observed viscoelastic. It is reasonable to assume
when additional N A30 samples that, the foam would recover to, and
were compressed to 80%. However, then plateau, at some lower level of
in N B50 samples under the same compression set, but that time frame
compression there was evidence of far exceeds the limits of this study.
Theoretically on application of the for N B50 over the strain rate range Although, this theory has not been
empirical Eq. (3), and assuming no studied, as shown in Table 8. investigated in this work, it may be
plastic damage occurs, it could be applicable using the developed Eq. (6)
predicted that the time required for The manufacturing process of these and (8) for each material. It should be
the material to achieve a near zero foams incorporates a process by noted that this must be supported with
compression set is measured in years. which the polymer base material is additional experimentation.
crosslinked9. It is reported8 that the
Literature reports that the Tg of level of crosslinking vastly reduces
6. CONCLUSIONS
Nylon is approximately 50 °C11,12. It the change in elastic modulus that can
is noteworthy that on or around the occur over the Tg region. It is postulated In this paper, time and temperature
Tg region, the mechanical properties that the crosslinking characteristic dependent predictive functions have
of a polymer exhibited discontinuity may have limited the change observed been developed to approximate
in performance particularly in elastic in elastic modulus to approximately the compression set and recovery
modulus. Compression set results show 200% over the ranges studied. This performance of two types of closed cell
anomalies at or around a temperature is beneficial in creating a consistent crosslinked polyamide-6 based foams.
of 50 °C; compressive stress-strain performance of such materials when These equations are limited to the
data on the same foam indicate a local operating at or above the Tg region, ranges studied, and any extrapolation
maximum around this point. where otherwise performance may beyond these limits would need to be
be highly variable. The sensitivity to supported by further experimentation.
At temperatures near Tg the modulus compressive performance based on
of elasticity is sensitive to strain rate. the level of crosslinking may vary The Nagy constitutive equation and
In order to investigate this further, it depending on the polymer type. WLF scaling factor have been applied
would be necessary to measure the to derive accurate strain rate and
change in the elastic modulus as a In addition to crosslinking, this temperature dependent functions for
function of strain rate at a constant investigation has found that cell both foams. The coefficients for the
temperature. This experimentation structure, polymer volume and the scaling equations are dependent on
was carried out at four different strain effect of gas pressure on these the temperature and strain rates and
rates, as discussed in Section 3. Over characteristics were also governing they are determined in this study for
the strain rate range studied, the elastic factors when predicting stress-strain two foams.
modulus increases by approximately performance of low density foams.
100% and 200% for the N B50 and N This investigation found that the
A30 foams, respectively. From SEM studies, it was observed that
performance of low density foams
at all temperatures samples compressed
was sensitive to temperature. WLF
up to 50% strain do not show cell walls
Stress-strain data were fitted as a temperature shifting factors do not
rupture. This confirms that all results
function of strain rate using Nagy take into account the effect of the gas
for the 50% or less compression set
constitutive equation30 for both N A30 pressure-temperature dependency
tests are unaffected by temperature
and N B50. The fit for N B50 was found within the cell. In low density foam,
and therefore supports the application
to be good. However, the fit for N A30 the cell gas pressure can account for
approximately 75% of the material’s of empirical equation (Eq. 3).
was not so good. Nagy’s constitutive
equation has been modified by performance. For this reason any
including a strain dependent coefficient describing equation must include an SEM images of the N A30 foam
and the fit was much improved. additional term, based on the ideal gas samples show no significant damage
law, which accounts for the effect of in the form of cell wall rupture; even
The modulus of elasticity and stress temperature on the gas within the cell. after 80% compression strain is
at particular strain values are sensitive This then allows for the prediction of achieved. However, buckling of the
to temperatures close to the glass the combined behaviour of the polymer cell walls is evident. SEM images of
transition30. Since polyamides are and gas within the cells, thus giving an the N B50 foam samples show evidence
thermoplastics, literature indicates accurate determination of bulk material of cell wall rupture (approximately
that the modulus of elasticity of the stress-strain properties without the 10%) when 80% compression strain
base polymer, and foams made from need for additional experimentation. is achieved. This is consistent with
this polymer, may vary by 3 orders differences in the ductility of the base
of magnitude dependent upon either As stated by Zhang et al.28, the Nagy polymers.
change in temperature and or strain and WLF equations can be linked
rate2. This study found that the elastic to derive a combined strain rate and Both experimental and direct
modulus tripled for N A30 and doubled temperature equation for each material. measurement has determined that for
the base polymers, the Tg is 48 ± 3 °C. 8. Ashby M.F. and Jones D.R.H., Isocyanate in Humid Aging and
This value is in agreement within the Engineering Materials 2 – An Durability of Molded seating Foam,
ranges given in literature for Nylon 6. Introduction to Microsctructures, Journal of Cellular Plastics 35
Processing & Design, 2nd edition, (1999) 492.
Butterworth and Heinemann, 1998. 20. BS EN ISO 1856, 2001
Acknowledgements 9. www.zotefoams.com, Date of Incorporating Amendments No
Access February 2011 1, Flexible Cellular Polymeric
The authors would like to acknowledge Materials – Determination of
10. BS 2782-3 METHODS 320A
the financial support from EPSRC for Compression Set.
TO 320F, 1976 Incorporating
project CASE/CNA/06/29 and from Amendment No.1 Plastics Part 3, 21. ASTM D395-03,2008 Standard
Zotefoams plc. Many thanks go to the Mechanical Properties - Methods Test Methods for Rubber Property
technical staff at Zotefoams plc for the 320A to 320F, Tensile Strength, Compression Set
supply of the samples and to Richard Elongation and Elastic Modulus. 22. N.J. Mills and A. Gilchrist, Creep
Giddens and Colin Bradsell for their 11. Greco R., Nicodemo L. and and Recovery of Polyolefin Foams
technical expertise. In addition our Nicolais L., The Glass Transition – Deformation Mechanisms,
thanks also go to Bryan Ruby and of Nylon 6, Macromolecules, 9(4) Journal of Cellular Plastics, 33
Trevor Nell for the manufacture of the (1976) 686-687. (1997) 264-292.
compression test fixtures. 12. Mills N.J., Plastics Microstructure, 23. BS EN ISO 1923,1995
Properties and Applications, Cellular Plastics and Rubbers
Edward Arnold, 1986. – Determination of Linear
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