Full Paper

Dart Impact Testing of Polyethylene Film:

Mechanical Interpretation and Model

Yury V. Kissin

A physical model of dart impact tests of film manufactured from semi-crystalline polyethyl-
ene resins is developed. The models treat the dart impact tests as a special case of the standard
high-speed stress/strain measurement performed on a polymer sample with a linearly
changing cross section. They describe the dart
impact strength as a complex function of the
parameters that characterize the stress-strain
curve of the resin: stresses and strains at the
yield, necking and breaking points. The models
correctly predict the range of the dart impact
strength (ASTM D1709, ISO 7765) and are suit-
able for semi-quantitative characterization and
ranking of linear low density polyethylene
resins for film applications.

Introduction publications of different LLDPE-manufacturing companies

End-use tests of blown and cast film manufactured from
such resins as low-density polyethylene (LDPE), linear
low-density polyethylene (ethylene/a-olefin copolymers,
LLDPE), and poly(but-1-ene) (PB) usually include a dart
impact test (dart drop test) and a tear test.[1–5] The results
of these two tests are used in industry to grade the resins,
determine their range of applications and price, and to
compare polymerization catalysts and processes. In the
case of LLDPE resins, both the dart impact strength (DIS)
and the tear strength of a resin are affected by numerous
factors, such as the type of the a-olefin comonomer,
copolymer composition, average molecular weight, com-
positional homogeneity of the copolymer, the type of
catalyst and co-catalyst used for the LLDPE synthesis,
etc.[5–10]
Although general information on mechanical properties
of polyethylene resins is readily available in commercial
Y. V. Kissin
Rutgers – The State University of New Jersey, Department of
Chemistry and Chemical Biology, 610 Taylor Rd., Piscataway,
New Jersey 08854-8087, USA
E-mail: ykissin@rci.rutgers.edu
(see examples in ref.[6–10]), various subtle effects of the
resin structure on the end-use film properties (the effects
that are often paramount for the successful applications of
the resins) are relatively poorly understood. A better
understanding is hindered by the physical complexity of
these seemingly straightforward tests and also by an
interaction of various structural factors of the polymers
that affect the test results.
This article presents a mechanical model of the dart
impact test of plastic film. The model interprets the DIS
value of film in terms of the basic mechanical properties
(measured in standard stress/stain tests) of the resins used
for the film manufacture. The model is also useful for a
quantitative prediction of DIS values of different poly-
ethylene resins.
Phenomenological Description of
Dart Impact Test
The procedure of the dart impact test according to ASTM
D1709-04 and ISO 7765 is simple;[11] see Figure 1. A dart
with a rounded tip (the curvature radius of
16 mm) and a
thin long stem with cylindrical metal weights on it is

Macromol. Mater. Eng. 2008, 293, 66–77

66 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/mame.200700262
Dart Impact Testing of Polyethylene Film: Mechanical Interpretation and Model
Figure 1. Three stages of a dart impact test of semi-crystalline plastic film.
dropped from a height of 660 mm perpendicularly to the
surface of a piece of thin polymer film fastened between
two rings 127 mm (500 ) in diameter. The mass of the dart
can be varied over a wide range by changing the weights
on the stem. The film is usually tested about 20 times at
different dart weights until its partial or complete rupture
occurs. A special protocol[11] for varying the dart weight
and calculating the ratio of film failure to survival
incidents gives the average dart mass needed to break
the film – the DIS value. Test results for different grades of
polyethylene film vary over a wide range, from
50–70 to
>1 000 g. The second ASTM test, ASTM D4272, uses a
heavier dart and measures the loss of kinetic energy of the
dart breaking the film by comparing the time of the dart
fall in the test and the time of its free fall in the absence of
any film.
Mechanical processes occurring during the dart impact
test can be clearly seen during testing of high-quality
LLDPE films. Figure 1 shows schematics of various stages
of the test. The dart approaches the film at a speed V0 of

3.6 m  s1. The central part of the film, 22–25 mm in
diameter, clings to the round surface of the dart and
remains undamaged and unstretched during the test. In
the first stage of the test, the dart bends the film until the
stress at the circumference of the central (undamaged)
area exceeds the yield stress of the polymer. After that, the
area around the undamaged area begins to stretch and
elongate (Stage 2 in Figure 1). The work of stretching
decreases the kinetic energy of the dart and its speed
rapidly decreases (see the quantitative estimation below).
If the kinetic energy of the dart exceeds the work needed to
break the film, the dart makes a round hole in the test
sample and falls through carrying with it the central
undamaged part of the film clinging to its surface (Stage 3).
The break line is usually located very close to the
circumference of the undamaged film area. If the kinetic
energy of the dart is insufficient to break the film, the dart
stops inside the cavity of the stretched film (Stage 2). In
the case of film manufactured from high-quality resins, the
depth of the cavity can reach 35–40 mm.
Macromol. Mater. Eng. 2008, 293, 66–77
ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Film stretching dur-
ing the dart impact
tests is accompanied
by strong orientation
of the polymer. Record-
ing polarized infrared
spectra of the stretched
area for several sam-
ples after the test give
the dichroic ratio for
the 720 cm1 band,
Ak/A?
0.33 (in the
absence of orientation,
this ratio is equal to 1).
The decrease of the dichroic ratio signifies strong orienta-
tion of polyethylene molecules in the direction of the film
stretching. Such orientation phenomena are typical for
standard tensile tests of plastics, and the dichroism of the
film after the dart impact tests is comparable to that
achieved in manual stretching of the same film at a high
speed.[12]
The dart impact test differs from the standard tensile
test in two ways:
1. The stretching speed during the dart impact test varies;
it is very high in the beginning and decreases to zero at
the end if the dart mass is insufficient to break the film.
Stretching of the film at the final moment of the test,
immediately before film failure (if the dart mass is
slightly higher than the DIS value) proceeds at a
relatively low speed.
2. Due to the geometrical design of the test, the cross
section of the stretched polymer continuously increases
as the film stretching progresses. This subject is treated
below.
These considerations provided the basis for the develop-
ment of the quantitative physical model of dart impact
tests.
Experimental Part
A number of commercial LLDPE film and resin samples were
studied. DIS values for several grades of film were taken from the
commercial literature. Dart impact tests of several film samples
were performed on blown film 25–38 mm (1–1.5 mil) in thickness
according to the standard procedure.[11] Mechanical measure-
ments were made on an Instron Universal Testing Machine Model
1122 at stretching speeds of 21.2 mm  s1 (5000  min1) and
8.5 mm  s1 (2000  min1). LLDPE samples for the mechanical
testing were prepared with the aim of imitating conditions typical
for the film manufacture, rapid extrusion of a resin melt followed
by a rapid cooling. The samples were prepared using a Tinius &
Olsen Melt Index Tester at 190 8C at an extrusion speed of
10–12 mm  s1, and the molten rods exiting the die of the
www.mme-journal.de 67
 Y. V. Kissin

elliptical rather that a round shape is that the original film is

slightly oriented, which results in different mechanical para-
meters in the machine direction and the transverse direction
during the film manufacture.[12] The average diameter of the
undamaged area is practically independent of the dart mass and
of the damage the dart does to the film, as the data for one
ethylene/hex-1-ene LLDPE resin demonstrate (Table 1). Similar
results were produced with other types of 25–38 mm films
prepared from ethylene/but-1-ene (ExxonMobil), ethylene/hex-1-
ene (ExxonMobil), ethylene/oct-1-ene (Dow Chemical), and
ethylene/4-methylpent-1-ene (Mitsui) resins: the d value ranges
from 22.5 to 24.1 mm. The d value of 23.0 mm was used in all
subsequent estimations of DIS.

Figure 2. Preparation and fastening of LLDPE samples for stress/ Simple Model
strain measurements.
A simple model of the dart impact test is based on the
apparatus were immediately cooled in a water/isopropyl alcohol following geometrical and physical considerations:
bath. The density of the liquid in the bath was adjusted to make
the extrudate weightless and thus to prevent its sagging. A special 1. The DIS value of the film, m (g), is defined as the
technique was developed to prevent the test samples from maximum dart mass the film can sustain without
slipping out of the jaws of the testing machine. This slipping
breaking, it is equal to the minimum mass needed to
occurs due to strain hardening of the polymers. Special sample
break the film.
pre-drawing, holders, and knotting were used that ensured a
slipless operation (Figure 2). 2. The idealized geometry of a film sample is shown in
Polarization IR spectra of LLDPE film after dart impact tests Figure 3a. Three parameters describe the sample: its
were recorded with a Perkin-Elmer 1600 FTIR spectrophotometer thickness t (mm), the diameter of the test area D (mm),
equipped with a Harrick wire-grid IR polarizer. and the diameter of the central undamaged (cling) area
of the film, d (mm) (see above).
3. At the beginning of the test, the stretching starts at the
Experimental Estimation of circumference of the cling area (Stage 1 in Figure 1); the
the Undamaged Region in the Film initial cross section of the stretching material is
Smin ¼ p  d  t. As the film stretching progresses, the
The size of the undamaged (unstretched) film area (diameter d),
cross section of the stretched zone of the film increases
which clings to the dart and is broken away from the sample when
in a linear manner. When the stretching proceeds to a
the film fails (Figure 1), was estimated in dart impact experiments
with several LLDPE films. Films of various origins were tested with distance l (assigned to the unstretched film before the
widely varying dart weights, from very small (barely sufficient to test), the cross section of the film undergoing the
initiate film stretching) to very large, exceeding the DIS of the yielding is Sl ¼ p  (d þ 2  l)  t. The maximum stretching
films. The tests showed that the undamaged area has an elliptical cross section (never achieved in real dart impact tests) is
shape with an axis ratio of
1.10–1.20. A possible reason for the Smax ¼ p  D  t.
4. Tensile properties of LLDPE can be adequately described
Table 1. Effect of dart test parameters on the value of the by the idealized standard stress-strain curve; see
undamaged zone for LLDPE resin (ExxonMobil ethylene/hex-1- Figure 3-B. The curve is defined by six parameters:
ene resin NTA-101, d ¼ 0.917 g  cm3, I2 ¼ 1.0 g  10 min1) yield stress sy, yield stain ey, necking stress sn, necking
stain en, breaking (tensile) stress sbr, and breaking strain
Dart mass Film condition d ebr. All the stresses are calculated with respect to the
cross section of the original sample. Typical stress
g mm
values for LLDPE resins are sy
sn
0.9–1.5 kG  mm2,
80 not broken 23/25 sy/sn
1.05–1.2, sbr
2.0–3.0 kG  mm2. All strains are
100 half-broken 23/25 the ratios of the sample length at a particular stage of
stretching to the original sample length. (The simple
120 failed 23/26
model does not take into account the dependence of
160 failed 22/25 each of these parameters on the stretching speed; this
240 failed 20/23 dependence is accounted for in the second model
280 failed 22/25 described below.)

Macromol. Mater. Eng. 2008, 293, 66–77

68 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/mame.200700262
Dart Impact Testing of Polyethylene Film: Mechanical Interpretation and Model
Figure 3. a) geometry of dart impact testing; b) idealized stress-strain curve of a polymer
sample.
These assumptions provide the basis for the quantitative
definition of DIS of film. The film breaks when the stress in
the smallest cross section, Smin, reaches the breaking stress
of the material, sbr. The breaking force Fbr at this point is:
Fbr ¼ s br Smin ¼ s br pdt
The same force Fbr is applied to all cross sections of the
sample. The maximum distance the stretching zone
propagates along the film radius [L in the original
film (L < D), X in the stretched film after stress relaxation,
X/L ¼ en] is defined as:
Fbr ¼ s y pðd þ 2LÞt ¼ s br pdt
That is, at the moment of the film failure, the yield stress
sy is achieved at the distance L from the undamaged
zone, where the cross sectional area is SL ¼ p (d þ 2L)t.
Equation (2) gives the following expressions for L and for X:
L ¼ ðs br  s y Þ  d=2  s y and
X ¼ "n ðs br  s y Þ  d=2  s y
According to the above-given definition, the mass of a
dart sufficient for the film rupture, m, is determined by the
expression which equates the kinetic energy of the dart
immediately before the impact and the total work of film
stretching and breaking, Wtotal:
mV 2 =2 ¼ Wtotal
where V
3.6 m  s1.
Macromol. Mater. Eng. 2008, 293, 66–77
ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
It is convenient to separate the
Wtotal term in Equation (4), the work
required to strain/stretch the film to
the breaking point, into four parts:
1. Wyield, the work of elastic stretch-
ing (Figure 3b) to the yield point in
all cross sections from Smin to SL.
2. Welast, the work of elastic stretch-
ing in all cross sections from SL to
Smax.
3. Wneck, the work of necking; that is,
stretching/orientation of the film
material from l ¼ 0 to l ¼ L.
4. Wstr-hard, the work of strain-
hardening, additional stretching
of the oriented part of the sample
to the point when the stress in the
smallest cross section reaches sbr:
Wtotal ¼ Wyield þ Welast þ Wneck þ Wstrhard (5)
Figure 3b shows three components of the total work
required to break the film for a polymer sample with a
(1) constant cross section. The appendix contains equations
for the four components of Wtotal for a film with a linearly
increasing cross section shown in Figure 3a: Wyield in
Equation (2A), Welast in Equation (4A), Wneck in Equation
(6A), and Wstr-hard in Equation (8A). The combination of
these equations and Equation (4) allows the calculation
of DIS (the m value) for a resin with given mechanical
parameters. If all stresses have units of kG  mm2 and the
dart speed V has the units m  s1, the dart mass m is
(2) calculated in g when Wtotal in Equation (5) is multiplied
by 9.81 m  s2.
The second dart impact test, ASTM D4272,[11] measures
the loss of kinetic energy, DE, of the dart breaking the film
by comparing the time of the dart fall in the test and the
time of its fall in the absence of the film. When all the s
values are expressed in kG  mm2, all cross sections
in mm2, and all distances in mm, the DE value for a given
film can be estimated as DE ¼ 9.81  103  Wtotal (J).
(3)
Model Calculations of DIS
The simple model of the dart impact test has three obvious
shortcomings:
1. The model does not take into account a large decrease in
the stretching speed of the polymer from the first
(4) moment (V
3.6 m  s1) to the end, when V
0, and its
effect on the mechanical properties of resins (this effect
is discussed below).
www.mme-journal.de 69
 Y. V. Kissin

2. The model does not take into account that all LLDPE film Table 2. Effects of test parameters on DIS value of 25 mm (1 mil)
film. Resin parameters: sy ¼ 1.1 kG  mm2, sn ¼ 1.0 kG  mm2,
materials produced by the film-blowing method
sbr ¼ 2.0 kG  mm2, ey ¼ 1.2, en ¼ 6, en ¼ 8.
are partially oriented,[12] which results in noticeable
differences in the mechanical properties between Test parameters DIS
the machine direction and the transverse direction of
the film. Mechanical measurements of extruded, com- D d mcalc
pletely nonoriented resin samples (see the Experimen-
tal Part) do not reflect this difference. mm mm g
3. The model assumes that no deformation/stretching
100 23 241
occurs in the film area clinging to the surface of the dart.
125 23 244
Nevertheless, the simple model of the dart impact test 150 23 246
reveals several important features of the test and the 127 20 186
effects of the resins’ mechanical properties on the DIS 127 23 244
values. For example, the following parameters were exper-
127 26 410
imentally determined as typical for ethylene/hex-1-ene
LLDPE resins (from the tensile tests of several resins): mechanical properties of LLDPE resins. It has been known
sy
1.3 kG  mm2, ey
1.2, sn
1.2 kG  mm2, en
6.0, for a long time that, due to relatively slow relaxation
sbr
2.3 kG  mm2, ebr
7.5. The DIS estimation for a phenomena, all mechanical parameters of polymers
25 mm (1 mil) film prepared from such a resin gives depend on the deformation rate.[13] We measured
m
255 g and X (the length of the oriented sleeve, see these dependencies experimentally for several ethylene/
Figure 1) of
53 mm. Both these estimations have the hex-1-ene LLDPE resins prepared both with Ti-based
correct order of magnitude when compared to experimen- Ziegler-Natta polymerization catalysts (compositionally
tal data: the experimentally measured DIS values for these nonuniform resins) and with metallocene catalysts (com-
LLDPE film grades range from 150 to 200 g. The energy of positionally nonuniform resins)[5] in the range of the
the falling dart is spent in the following way:
1.5% for deformation speed V from 0.5 to 150 cm  min1. In most
stretching the film to the yield point (Wyield in Figure 3b); cases, the dependencies between the test parameter, s or e,

5.5% for elastic deformation of the nonoriented part of and V can be represented by simple empirical relationships
the film, Welast;
76% for orientation of the film (Wneck in using as a standard a particular value at the deformation
Figure 3b); and
17% for overcoming the resin’s strain- speed Vstand of 2000  min1 ¼ 50.8 cm  min1:
hardening (Wstr-hard in Figure 3b). sy ¼ sstand þ k  (sy)  log(V/Vstand), the slope k(sy)
0.14
y
A series of DIS estimates were calculated to determine (the literature data for LDPE[13] give practically the same
the parameters of the test and mechanical properties of slope);
LLDPE resins that affect the model calculations.
s n ðVÞ ¼ s stand
n þ kðs n Þ logðV=V stand Þ;
(6)
Effects of Test Parameters the slope kðs n Þ
0:11

Table2liststheeffectsofthefilmdiameterDandthesizeofthe
undamaged area on DIS. A variation of D over a wide rangehas
virtually no effect on the calculated test results provided that
D  d. The size of the undamaged area, d, strongly affects
the m values. However, the above-reported experimental
results show that this parameter is mostly independent of
the resin properties. According to the model, the m values
are proportional to the film thickness t, [see Equation (2A),
(4A), (6A), and (8A) in the Appendix]. However, the simple
physical model does not take into account the effects of
the film thickness on the molecular orientation and on the
concentration of defects in polymer crystals.
Second Model of Dart Impact Test
The principal goal of the model improvement is to account
for the effect of the stretching speed variation on the
"n ðVÞ ¼ "y ðVÞ ¼ "stand
n  "stand
y þ kð"n  "y Þ
 logðV=V stand Þ; the slope kð"n  "y Þ (7)

0:5  0:6; depending on LLDPE
whereas ey, sbr, and ebr values practically do not depend
on V.
As discussed in the previous section, the fractions of the
energy of the falling dart spent on stretching the film to
the yield point (Wyield in Figure 3b),
1.5–2.0%, and on the
elastic deformation of the unstretched part of the film,
Welast,
5.5–6.0%, are insignificant compared to the
fractions of the dart energy spent on stretching/orienta-
tion of the film, Wneck
75%, and on strain-hardening of
the oriented film, Wstr-hard
15%. Because the sbr and the
ebr values practically do not depend on V, the only two
effects of the stretching speed on the mechanical proper-

Macromol. Mater. Eng. 2008, 293, 66–77

70 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/mame.200700262
Dart Impact Testing of Polyethylene Film: Mechanical Interpretation and Model

ties of the resins that were considered are those on the sn

and the en values. These effects can be quite significant.
Unfortunately, the highest stretching speed achieved with
the standard testing equipment,
2 cm  s1, is much lower
than the initial stretching speed in the dart impact test,

360 cm  s1. Nevertheless, even the simple linear depen-
dence in Equation (6) extrapolated to V ¼ V0
3.6 m  s1
exp
gives sn(V0)
sn þ 0.18, and a similar extrapolation of
the en  ey value gives (en  ey)(V0)
(en  ey)exp þ 1.5, i.e.,
the same resin, when stretched at a very high speed, is
noticeably stiffer and its necking strain is noticeably
higher.

Deceleration of Dart During the Test

The falling dart decelerates rapidly during the dart impact
Figure 4. Decrease of dart speed as a function of deformed
test: its starting speed, V0
3.6 m  s1, is reduced to the polymer zone l for four different sbr/sn ratios.
final speed VL
0 in a fraction of a second. The general
expression for the dart speed as a function of the length of
the film subjected to stretching, l (see Figure 3a), is
those on sn [Equation (6)] and en [Equation (7)], and the
Vl ¼ V0  al t. The acceleration value al decreases linearly
only term in Equation (5) requiring this correction is Wneck.
with l from a0 ¼ F0/m ¼ sn p dt/m to the abr value at the
The derivation of the modified Wneck expression, Wcorr neck , is
film breaking point, abr ¼ a0  (sbr/sn):
also presented in the Appendix.
The absence of direct stress/strain measurements at
a1 ¼ a0  ð1 þ 2l=dÞ (8)
very high speeds (a very difficult experimental task) makes
the estimation of the dart speed correction somewhat
where l increases from 0 to L, see Equation (3). If we assume
speculative. As a first approximation, the following
that the dart decelerates to a complete halt at l ¼ L [i.e.,
assumptions were made:
VL ¼ 0], the initial deceleration a0 is:

1. The linear correlation between sn and the stretching

a0 ¼ ðV02 =dÞ=½ðs br =s n Þ  ðs br =s n  1Þ
If one takes into account that the length of the dart
travel is described by the standard expression: l ¼ V0 t  al
t2, the expression for the rate Vl as a function of l (by
eliminating t) is:
(9)
velocity V in Equation (6) was extrapolated to V ¼ V0.
2. The son value for each resin was calculated as
exp
son ¼ sn þ ks log(V0/Vexp) where Vexp is the stretching
speed used in the experiments and the slope ks
0.11.
3. The sVn value as a function of V vas presented as:

V1 ¼ ½V02  2a0 lð1 þ 2l=dÞ0:5 ¼ V0 f1  2l=d s Vn ¼ s on þ ks  logðV=V0 Þ (11)

0:5
(10)
 ð1 þ 2  l=dÞ=½ðs br =s n Þ  ðs br =s n  1Þg
4. Due to high uncertainty of extrapolating Equation (7) to
Figure 4 gives several examples of the relative dart V ¼ V0, the principal effect of the stretching speed on the
speed Vl/V0 as a function of the length l of the film en value was assumed to be the lengthening of the
subjected to stretching/necking. The calculations were en  ey gap due to the increase of the sn value and the
carried out for five sbr/sn ratios typical for LLDPE film of corresponding decrease of the ebr value (see Figure 3b).
various types. It is obvious that the final states of the dart The modulus of strain-hardening, Ms-h ¼ (sbr  sn)/
impact test, immediately before the film rupture, proceed (ebr  en), was assumed to be unchanged:
at quite low speeds.
ð"n  "y ÞV ¼ ½s on þ ks logðV=V0 Þ  s n =Msh (12)

Effect of Dart Deceleration on DIS

The introduction of these semi-empirical corrections
The only two effects examined in a more precise model for the effect of the decreasing stretching speed on the sVn
of the dart impact test are two effects of the dart speed, and the (en  ey)V values [see Equation (9A) in the

Macromol. Mater. Eng. 2008, 293, 66–77

ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.mme-journal.de 71
 Y. V. Kissin

Table 3. Comparison of energy distribution in a dart impact test
according to two models.
Wyield Welast Wneck Wstr-hard
initial model
1.5%
5.5%
76%
17%
improved model
2%
6%
74%
18%
Appendix] slightly modifies the estimated DIS values. For
example, the estimated m value for a high-quality
ethylene/hex-1-ene LLDPE resin decreases from
255 to

240 g, and X (the length of the oriented sleeve, see
Figure 1) increases from
53 to
57 mm. The differences in
the energy distribution of the falling dart are also
relatively small, as shown in Table 3.
Model Analysis: Effects of
Mechanical Properties of the Resins
It follows from Equation (2A), (4A), (6A), (8A), and (9A) in
the Appendix that all six parameters which determine the
shape of the stress-strain curve affect the DIS values
(m values) in a complex way due to their contributions to
different terms in Equation (5). Computational results for
25 mm (1 mil) film, presented in Table 4, demonstrate the
predicted effects of LLDPE mechanical properties (see
Figure 3b) on the DIS values calculated with the second
model:
1. A pronounced yield threshold sy/sn >1, which is typical
for many LLDPE resins (assuming the same values of sn,
sbr, ey, en, and ebr), is detrimental to DIS, although the
effect is not large in the typical range of the sy/sn ratio,
1.05–1.10.
2. The Young modulus of an unstretched resin has
virtually no effect on DIS.
3. An increase of the resistance to orientation (a propor-
tional increase of the yield stress and the necking stress)
produces a strong decrease in DIS. This trend partially
explains why soft, easily deformed resins with a
homogeneous compositional distribution exhibit super-
ior DIS properties.
4. An increase of the orientation potential of a resin (an
increase in en) does not affect DIS.
5. An increase in the tensile strength sbr greatly improves
the DIS value by allowing the orientation zone in the
film to propagate further. An increase in the strain-
hardening properties of a resin (a parallel increase of the
sbr and ebr) produces a similar effect.
Mechanical Properties of LLDPE Resins and
Predictions of DIS for Different Resins
Experimental stress/strain curves of several LLDPE resins
of a different origin and composition were measured and
the data were used for the estimation of their DIS values
with the second model. Several examples of these
estimates and their comparison with experimentally
measured DIS values for films made from these resins
provide an explanation for the well known differences in
the DIS values between film produced from different LLDPE
grades.

Table 4. Effects of LLDPE mechanical properties (see Figure 3b) on DIS values; calculations with the second model.

Effect of yield threshold sy/sn

(sn ¼ 1.0 kG  mm2, sbr ¼ 2.5 kG  mm2, ey ¼ 1.2, en ¼ 5, ebr ¼ 7)
sy/sn 1.02 1.05 1.10 1.15
m/g 330 318 296 273
Effect of Young modulus MYoung ¼ sy/(ey  1)
sy/(ey  1) 7.3 5.5 4.5 3.4
m/g 293 296 299 304
Effect of resistance to orientation (proportional increase of yield stress and necking stress) (sy/sn ¼ 1.1)
sn/(kG  mm2) 0.8 1.0 1.2 1.4
m/g 500 296 217 152
Effect of increase of orientation potential
en 4.0 6.0 8.0
m/g 298 294 289
Effect of increase of tensile strength
sbr/(kG  mm2) 2.0 2.5 3.0
m/g 203 372 764

Macromol. Mater. Eng. 2008, 293, 66–77

72 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/mame.200700262
Dart Impact Testing of Polyethylene Film: Mechanical Interpretation and Model

Ethylene/But-1-ene vs.
Ethylene/Hex-1-ene Copolymers
LLDPE film manufactured from ethylene/but-1-ene copo-
lymers is inferior in DIS compared to film manufactured
from ethylene/hex-1-ene copolymers of the same compo-
sition and crystallinity. The average dart impact strength
of 25 mm blown film made from ethylene/but-1-ene
copolymers is 80–120 g, whereas this parameter for blown
film from common ethylene/hex-1-ene copolymers is
150–200 g[2,6–10] and it can reach 400–500 g for grades
of ethylene/hex-1-ene copolymers prepared with special
types of heterogeneous Ziegler-Natta catalysts.[14] Table 5
lists mechanical properties of several resins of these types.
The model gives reasonable predictions of the DIS values.
The two ethylene/but-1-ene resins and the ethylene/hex-
1-ene resin (MJA-42) are produced with the same catalyst;
they are similar in density, the degree of crystallinity, and
molecular weight. The resins have similar yield and neck-
ing parameters, but they noticeably differ in tensile pro-
perties: the ethylene/but-1-ene copolymers have a
30%
lower breaking stress. The results in Table 5 can be
interpreted in the following way:
1. The work required to start a neck, Wyield, and to stretch
elastically the undeformed part of the film, Welast, is
practically the same for both types of film (their yield
parameters sy and ey are similar).
2. The film from the ethylene/but-1-ene resins breaks
easier than the film from the ethylene/hex-1-ene resin
mostly because the breaking stress sbr of the former
resins is lower. As a result, the work of necking/
orientation, Wneck, for them is two times lower.
3. The work required to overcome strain hardening,
Wstr-hard, is also lower by a factor of 1.5–2 for the
ethylene/but-1-ene copolymers.
The last two lines in Table 5 compare the results for two
ethylene/hex-1-ene copolymers, one (NTA 261) produced
with a standard catalyst composition and another (NTX
095, ‘‘super-strength resin’’) produced with a modified
catalyst system.[14] The two resins are identical in most
of their tensile parameters; the significantly higher DIS
value for the second material is entirely due to a
20%
higher sbr value and, respectively, higher Wneck and
Wstr-hard contributions to Wtotal.
Effect of Copolymer Composition
DIS values of all ethylene/a-olefin copolymers of a similar
average molecular weight significantly increase as the
a-olefin content in them increases, and their density and
crystallinity respectively decrease.[1,2,5–8] The data in
Table 6 provide a tentative explanation of this effect. As
the but-1-ene content in the copolymer increases from

3.5 to 4.4%, all the s values of the material decrease while
all the e values remain essentially the same. Paradoxically,
the mechanically weaker resin has a higher DIS value (the
Wneck and Wstr-hard values are higher) because the lower sy
value of the material allows the resin to stretch further
(and to absorb more of the dart energy) before the stress in
the smallest cross section of the film reaches sbr. A still
further increase in the but-1-ene content to
5.5 mol-%
(a difficult task if the resins are produced in gas-phase
fluidized-bed reactors) decreases all the s values even
more but the DIS value remains approximately the same.
The same effect is characteristic for ethylene/hex-1-ene
copolymers. An increase of the hex-1-ene content from 2.3
to 3.2 mol-% and a respective decrease in density from
0.923 to 0.917 g  cm3 result in a significant decrease of all
three s values of the resins. This change leads to an
increase of the model-predicted mcalc value from
230 to

290 g (the mexp values are
200 and
230 g, respec-
tively). A medium-density ethylene/hex-1-ene resin con-
taining 1.8 mol-% of hex-1-ene (0.928 g  cm3 density) has
mechanical properties that are still higher than those for
the resin containing 2.3 mol-% of hex-1-ene, and the
predicted mcalc value for it is also high,
270 g. However,
the experimentally measured mexp value for the medium-
density film is significantly lower,
180 g. This difference

Table 5. Mechanical properties and estimated DIS (for 25 mm film) of compositionally nonuniform ethylene/a-olefin copolymers.

Resina) Typeb) Density Mechanical properties Estimated DIS Exp. DIS

g  cmS3 sy ey sn en sbr ebr mcalc Wyield Welast Wneck Wstr-hard mexp

S2 S2 S2
kG  mm kG mm kG mm g kG  mm kG  mm kG  mm kG  mm g

E/B LL 1001 0.918 1.01 1.27 0.94 6.4 1.53 9.9 160 2 8 67 29 100
E/B MJA-42 0.918 1.03 1.36 0.98 5.1 1.56 8.9 105 2 14 39 14 120
E/H NTA 261 0.918 1.20 1.45 1.04 5.7 2.39 8.7 320 7 23 136 43 200
E/H NTX 095 0.917 1.24 1.40 1.05 5.3 2.94 8.7 640 12 25 229 157 580

a) b)
E/B: ethylene/but-1-ene resins, E/H: ethylene/hex-1-ene copolymers; Resins: Dow/Union Carbide UC 7047, LL 1001; ExxonMobil
Chemical Co. MJA-42, NTA 261, NTX-095.

Macromol. Mater. Eng. 2008, 293, 66–77

ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.mme-journal.de 73
 Y. V. Kissin

Table 6. Effect of copolymer composition (resin density) on mechanical properties and estimated DIS (for 25 mm film) of compositionally
nonuniform ethylene/but-1-ene copolymers.

Density CBa) Mechanical properties Estimated DIS Exp. DIS

S3
g  cm mol-% sy ey sn en sbr ebr mcalc Wyield Welast Wneck Wstr-hard mexp

kG  mmS2 kG  mmS2 kG  mmS2 g kG  mm kG  mm kG  mm kG  mm g

0.921
3.5 1.32 1.14 1.07 5.7 1.91 8.9 145 1 5 62 27 120
0.917
4.4 0.96 1.33 0.89 5.4 1.75 8.9 240 4 12 87 56 280
0.910
5.5 0.64 1.53 0.60 5.8 1.35 8.9 235 6 15 82 53 230

a)
But-1-ene content in copolymer.

is probably caused by significant molecular orientation of
the original film,[12] which is not accounted for in the DIS
models.
Compositionally Uniform vs. Compositionally
Nonuniform Copolymers
LLDPE resins with improved compositional homogeneity
are produced with conventional catalysts in high-pressure
reactors (when the residence time is very short), in solution
processes at high temperatures, or with metallocene
catalysts. Table 7 lists mechanical properties of several
resins of this type and compares their estimated (for 25 mm
film) and experimentally measured DIS values. The first
three lines give the properties of the resins produced with
metallocene catalysts. A comparison with the data in
Table 5 and in Figure 5 shows that, overall, composition-
ally uniform resins produced with metallocene catalysts
are ‘‘softer’’ and more easily stretched (their sy and sn
values are lower). However, their necking range is typically
shorter (en
4.5 vs. 5.5), and the strain-hardening range,
ebr  en, is higher, indicating that the resins of this type
exhibit more expressed rubber-like properties in the orien-
ted state. The high DIS values (both experimentally
determined and predicted by the model) for such materials
are mostly due to their strain-hardening properties: the
Wstr-hard component of the Wtotal value for them is
significantly higher than for the copolymers of the same
type lacking compositional homogeneity.
Deficiencies of DIS Models
The models described in this report have several short-
comings. The first obvious deficiency is the assumption
that the d value for all types of film is the same. As Table 2
shows, this test parameter has a significant influence on
DIS. Ideally, this problem can be corrected by the experi-
mental measurement of the d value for particular film, but
this requires the synthesis of a large quantity of a polymer
(at least 300–400 g) and the preparation of film; a difficult
task in exploratory research when the amount of a pro-
duced polymer is usually measured in a few grams. In
contrast, the mechanical test described above requires
merely 5–6 g of a polymer. Another deficiency of
the models stems from the mechanism of film breaking.
The models describe a ‘‘perfect’’film break, which takes
place along the circumference of the cling zone (Figure 1).
In reality, such a break is regularly observed only for
compositionally homogeneous resins, which produce
non-oriented films. Most other types of fabricated LLDPE
film are partially oriented in the process of their manu-
facture.[12] When a dart impacts such films, it often
produces one or two cracks stretched in the machine
direction of the films, tangentially to the cling zone. The

Table 7. Mechanical properties and estimated DIS (for 25 mm film) of compositionally uniform ethylene/a-olefin copolymers.

Resina) Typeb) Density Mechanical properties Estimated DIS Exp. DIS

g cmS3 sy ey sn en sbr ebr mcalc Wyield Welast Wneck Wstr-hard mexp

S2 S2 S2
kG mm kG mm kG mm g kG  mm kG  mm kG  mm kG  mm g

E/H EM 0.917 1.14 1.93 1.02 4.6 3.04 7.8 830 33 57 263 197
E/H EM 0.916 1.03 1.80 1.00 4.4 2.76 8.1 720 26 44 200 204 >800
E/MP Mitsui 0.914 0.96 1.46 0.89 4.3 2.33 7.6 460 11 11 136 131 >800
E/O D-2045 0.920 1.01 1.15 0.97 5.9 2.20 9.5 420 3 7 161 108 290

a) b)
E/H: ethylene/hex-1-ene copolymers, MP: ethylene/4-methylpent-1-ene copolymers, E/O: ethylene/oct-1-ene copolymers; Resins:
D-2047: Dowlex 2047, Dow Chemical Co; EM: ExxonMobil Chemical Co. experimental resins; Mitsui 1520 L resin.

Macromol. Mater. Eng. 2008, 293, 66–77

74 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/mame.200700262
Dart Impact Testing of Polyethylene Film: Mechanical Interpretation and Model
Figure 5. Stress-strain curves for ethylene/hex-1-ene copolymers
of the same crystallinity (density): a) compositionally nonuniform
resin; b) compositionally uniform resin.
formation of the cracks (observed visually) qualifies such
tests as a failure, although no complete breaking of the
films really occurs. The degree of orientation (and the
probability of partial film cracking) increases with
decreasing the comonomer content and increasing the
film crystallinity (density). This phenomenon apparently
explains the discrepancies between high DIS predictions
for medium-density films and relatively low experimental
DIS values. The proposed models are poorly suited for
predicting DIS values for such strongly oriented films.
The third problem is related to the temperature regime
during the measurements. Stretching of polymers, both
semi-crystalline and amorphous, always results in a tem-
perature increase. The increase depends on the heat
transfer rate, which is higher for thin films used for dart
impact tests than for 2–3 mm thick rods used for tensile
measurements. The heating manifests itself, for example,
in a gradual decrease of the necking stress at the end of
the necking stage. This problem was partially corrected in
the study by calculating sn values from the stretching force
immediately after the end of the yielding stage. However,
the temperature effects on the breaking stress and strain,
sbr and ebr, could not be accounted for.
As a result, the DIS models of LLDPE resins are not
suitable for precise quantitative predictions as such. The
most that the models can do is to predict the range of
the DIS values and to rank mechanical properties of resins
for film application on the basis of their tensile tests. The
models also provide information on the relative signifi-
cance of different mechanical parameters affecting the
dart impact tests.
Conclusion
1. Physical models of dart impact tests of plastic film were
developed for film manufactured from semi-crystalline
Macromol. Mater. Eng. 2008, 293, 66–77
ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
polyethylene resins. The models treat dart impact tests
ASTM D1709 and D4272 (ISO 7765) as special cases of a
standard high-speed stress/strain measurement per-
formed on a polymer sample with a linearly changing
cross section. The models describe the DIS value for a
particular film as a complex function of the six
parameters that characterize the stress-strain curve of
the resin: stresses and strains at the yield, the necking,
and the breaking points. The simple model assumes
that these parameters do not depend on the rate of
straining whereas the improved model calculates the
change of the dart speed and takes into account the
effect of the stretching speed on several mechanical
parameters of polyethylene resins. The ASTM D4272
tests are carried out at more uniform dart speeds and
the correction for the speed change can be omitted.
2. Comparisons of experimental and calculated DIS values
for several resins showed that the models correctly
predict the DIS ranges for different LLDPE film and are
suitable for a semi-quantitative characterization and
ranking of the resins for film application.
3. The models allow the evaluation of the relative
significance of several mechanical features of poly-
ethylene resins for their dart impact behavior of their
film. They explain such commonly known effects as
differences between the film manufactured from
ethylene/but-1-ene and ethylene/hex-1-ene copoly-
mers, the effects of the copolymer composition on
the film properties, and differences between polyethy-
lene film produced from compositionally uniform and
nonuniform ethylene/a-olefin copolymers.
Appendix: Derivation of
Components of Wtotal
The geometry of the film sample is shown in Figure 3a. The
three parameters describing the sample are thickness t
(mm), diameter D (127 mm), and the diameter of the
undamaged part of the film, d (mm). Mechanical properties
of LLDPE resins are represented by the idealized stress-
strain curve in Figure 3b. Its six parameters are: yield stress
sy, yield stain ey, necking stress sn, necking stain en,
breaking (tensile) stress sbr, and breaking strain ebr. All
stresses are calculated with respect to the original cross
section of a sample, and all strains are the ratios of the
sample length at a particular stage of stretching and
the original sample length. The simple model does not
take into account the dependence of each of these
parameters on the stretching speed.
The film stretching starts at the circumference of the
undamaged (cling) zone, Smin ¼ pdt. All distances in
partially stretched film are assigned to the distances in
the original film. This formalism is the same as that used
www.mme-journal.de 75

in standard tensile tests where all the s values are
calculated with respect to the original cross section of a
specimen. The distances are shown in Figure 4a. As the film
stretching progresses, the necking zone shifts to the
periphery of the film and its cross section linearly
increases. When the stretching proceeds to an arbitrary
distance l, the cross section of the film undergoing the
yielding becomes Sl ¼ p(d þ 2l) t.
The total work Wtotal of film stretching to the breaking
point is divided into four parts [Equation (5)], Wtotal ¼
Wyield þ Welast þ Wneck þ Wstr-hard. For every element of
the film cross section l, l þ dl [with the cross section area
Sl ¼ (d þ 2l) t], the work of deformation Wi is the product
of the force Fi ¼ si  Sl and the distance (ei  1) dl.
Estimation of Wyield
Every element at a distance l, l þ dl with l varying from 0 to
L is stretched to the yielding point. The force Fy increases
linearly from 0 to sySl ¼ sy p(d þ 2l) t, and the average
force Fav
y is equal to 0.5 sy p (d þ 2l) t. The distance of the
application of this force is (ey  1) dl, and the elemental
work spent at yielding of this element is:
dWyield ðlÞ ¼ 0:5s y Sl ð"y  1Þdl
(1A)
¼ 0:5s y pðd þ 2lÞtð"y  1Þdl
The integration of Equation (1A) for the total distance at
which complete yielding is achieved, from l ¼ 0 to l ¼ L
(L ¼ (sbr  sy)  d/2sy, gives:
Wyield ¼ 0:5pts y ð"y  1ÞLðd þ LÞ
(2A)
¼ 0:125pd2 ts y ð"y  1Þ½ðs br =s y Þ2  1
Estimation of Welast
Every element at a distance l, l þ dl with l from L to
0.5(D  d) is elastically strained below the yielding point.
The average force Fav el is constant, 0.5sySL, but the strain
decreases linearly from ey  1 at l ¼ L to (ey 1)SL/Smax at
l ¼ 0.5(D  d); therefore, eel(l) ¼ ey SL/Sl. The elemental work
of elastic straining of this element is:
dWelast ðlÞ ¼ 0:5s y ð"y  1ÞðS2L =Smax Þdl (3A)
The integration of Equation (3A) for the distance from
l ¼ L to l ¼ 0.5(D  d) gives:
Welast ¼ 0:25s y ð"y  1ÞSL ðd þ 2LÞ ln½D=ðd þ 2LÞ
(4A)
¼ 0:25pts y ð"y  1Þðd þ 2LÞ2 ln½D=ðd þ 2LÞ
Macromol. Mater. Eng. 2008, 293, 66–77
76 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Y. V. Kissin
Estimation of Wneck
Every element at a distance l, l þ dl with l from 0 to L is
stretched/oriented until its strain reaches en. The force Fy
increases linearly from snSmin to snSl where Smin ¼ pd and
Sl ¼ p(d þ 2l)t. The distance of the application of this force
is (en  ey)dl, and the elemental work spent at stretching of
this element is:
dWneck ðlÞ ¼ ps n ð"n  "y Þtðd þ 2lÞdl (5A)
The integration of Equation (6A) for the total distance at
which complete necking is achieved, from l ¼ 0 to l ¼ L,
gives:
Wneck ¼ ps n ð"n  "y ÞtLðd þ LÞ
¼ 0:25ps n ð"n  "y Þd2 t½ðs br =s y Þ2  1 (6A)
Estimation of Wstr-hard
Wstr-hard is the work of strain-hardening of every element
at a distance l, l þ dl with l from 0 to L (see Figure 3a). The
straining is different for each element, it is the highest,
ebr  en, at l ¼ 0 and it is zero at l ¼ L. The dependence is
linear and es-h(l) ¼ (ebr  en)(1  l/L). The stress in the
element also depends on l, it is the highest, sbr, at l ¼ 0
and it is sn at l ¼ L. The dependence is also linear and
ss-h(l) ¼ sn þ (sbr  sn)(1  l/L).
Taking into account that the force of strain-hardening,
Fsh, is ssh(l)Sl and that the distance is esh(l) dl, the elemental
work of strain-hardening of the element l, l þ dl is:
dWstrhard ðlÞ ¼ ptð"br  "n Þð1  l=LÞ½s n
(7A)
þ ðs br  s n Þð1  l=LÞðd þ 2lÞdl
The integration of Equation (8A) for the total distance at
which the strain-hardening occurs, from l ¼ 0 to l ¼ L, gives:
Wstrhard ¼ ð1=6Þptð"br  "n ÞL½ðdð2s br þ s n Þ
(8A)
þ Lðs br þ s n Þ
Substitution of Equation (2A), (4A), (6A), and (8A) into
Equation (5) (as components of Wtotal) allows the estima-
tion of the dart mass m with Equation (4).
Estimation of Wcorr
neck
The Wneck term in Equation (5) is the only term that
requires a correction to account for the effect of the dart
speed V (which rapidly decreases during the test, see
Figure 4) on the tensile properties of LLDPE resins.
The starting point in the derivation is Equation (5A), but
DOI: 10.1002/mame.200700262
Dart Impact Testing of Polyethylene Film: Mechanical Interpretation and Model
both the sn value and en  ey value in it depend on the
stretching speed V according to empirical Equation (11)
and (12):
corr
dWneck ðlÞ ¼ps Vn ð"n  "y ÞV tðd þ 2lÞdl
¼p½s on þ ks logðV=V0 Þf½s on þ ks logðV=V0 Þ
 s n =Msh gtðd þ 2lÞdl
(9A)
where ks
0.11. If the dependence between V and the
parameter l is defined by Equation (10), the integration of
the combination of Equation (9A) and Equation (10) is
difficult. However, the dependencies between log(V/V0)
and l in Figure 4 can be adequately represented by simple
empirical exponential expressions, log(V/V0) ¼ –a exp(bl),
where parameters a and b depend on the sbr/sn ratio:
a
0.41  0.15(sbr/sn), b
0.28 þ 21.5 exp[2.8(sbr/sn)].
The analytical integration of the combination of Equation
(9A) and this exponential expression for log(V/V0) is
cumbersome but a numerical integration of these two
equations is easily achieved with any computational
program, such as Mathematica.
Received: August 24, 2007; Revised: October 15, 2007; Accepted:
October 18, 2007; DOI: 10.1002/mame.200700262
Keywords: dart impact test; film properties; impact resistance;
LLDPE; polyethylene (PE); stress-strain curves
Macromol. Mater. Eng. 2008, 293, 66–77
ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
[1] D. E. James, ‘‘Encyclopedia of Polymer Science and Engineer-
ing’’, 2nd Edition, J. Wiley & Sons, New York 1987, Vol. 6,
p. 429.
[2] Y. V. Kissin, ‘‘Kirk-Othmer Encyclopedia of Chemical Tech-
nology’’, J. Wiley & Sons, New York 1996, Vol. 17, pp. 756,
819.
[3] A. M. Chatterjee, ‘‘Handbook of Plastic Materials and Tech-
nology’’, I. Rubin, Ed., J. Wiley & Sons, New York 1990, Chapter
83.
[4] A. M. Chatterjee, ‘‘Encyclopedia of Polymer Science and Engin-
eering’’, 2nd Ed., J. Wiley & Sons, Inc., New York 1985, Vol. 2, p.
590.
[5] B. A. Krentsel, Y. V. Kissin, V. I. Kleiner, S. S. Stotskaya, ‘‘Poly-
mers and Copolymers of Higher a-Olefins’’, Hanser Publishers,
New York 1997, Chapter 8.
[6] ExxonMobil Chemical Company: http://www.exxonmobil-
chemical.com/public Products/Polyethylene.
[7] Dow Chemical Company: http://dow.com/polyolefins/na/
product family/lldpe.
[8] Lyondell http://Lyondell.com/Lyondell/Products/polymers/
LinearLowDensityPolythylene.
[9] L. M. Sherman, Plastics Technology Online, October 2000 and
January 2002.
[10] Chemical Week, September 16, 2001.
[11] ASTM D1709-04 A (ISO 7765-1) and D4272 90 (ISO 7765-2),
Standard Test Methods for Impact Resistance of Plastic Film by
the Free-Falling Dart Method.
[12] Y. V. Kissin, J. Polym. Sci., Polym. Phys. Ed. 1972, 30, 1165.
[13] S. Strella, ‘‘Engineering Design for Plastics’’, E. Baer, Ed., Rein-
hold Publ. Corp., New York 1964, Chapter 12.
[14] V. J. Crotty, V. Firdaus, R. O. Hagerty, in: SPE Polyolefins VIII
International Conference, Houston, Texas 1993, p. 192.
www.mme-journal.de 77