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POLYMER
TESTING
Polymer Testing 26 (2007) 927936
www.elsevier.com/locate/polytest

Test Method

Evaluation of scratch resistance in multiphase PP blends


Thomas Kocha, Doris Machlb,
a

Institute of Materials Science and Technology, Vienna University of Technology, FavoritenstraX e 9-11, A-1040 Vienna, Austria
b
Borealis GmbH, PO R&D, St.-Peter-StraX e, A-4021 Linz, Austria
Received 29 April 2007; accepted 15 June 2007

Abstract
A study on scratch deformation behavior of multiphase PP/EPR/PE materials with different polymer composition was
made by combining microscopic and macroscopic examination. The addition of PE to the PP/EPR blend leads to an
improvement of scratch resistance. No strong correlation was found between micro- and macro-scratch experiments on the
injection molded specimens, but when PE was added a reduction of the remaining deformation after scratching was found
at both scales. The visibility of the scratches, which should be the most important parameter in daily use, is affected by the
depth, the pile-up and the roughness of the scratch; the surface hardness does not play a role for the investigated polymers.
r 2007 Elsevier Ltd. All rights reserved.
Keywords: Polypropylene; Polyethylene; Ethylene/propylene copolymer; Blend; Scratch resistance; Micro-hardness

1. Introduction
Thermoplastic polyolens such as polypropylene
are being increasingly used as structural materials
due to the good strengthtoughness combination,
low cost and ease of fabrication. Low gloss,
aesthetical appeal and low susceptibility to mechanical damage (e.g., good scratch resistance (SR)) are
getting more and more relevant, especially in the
automotive industry.
The scratching phenomenon on the polymer
surface tends to be one of the key issues in this
respect. This topic has been the subject of numerous
research efforts in the past few years, both by
research institutions and manufacturing industries.
The different papers have established a series of
correlations between certain scratch parameters and
Corresponding author.

E-mail address: doris.machl@borealisgroup.com (D. Machl).


0142-9418/$ - see front matter r 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymertesting.2007.06.006

material response. In most papers, the focus is on


scratch morphology and damage mechanisms. The
most extensive work on this topic has been by
Briscoe et al. [1]. The concept of scratch mapping
was proposeda test procedure to map the scratch
response under different conditions by varying
contact load and contact strains. However, scratch
maps do not provide all the information needed to
evaluate damage under all conditions, and the
scratch hardness, which is stated to be related to
scratch width, is typically the only measurement
used to evaluate scratch resistance. Nevertheless, the
fact that the scratch behavior is greatly dependent
on experimental conditions (applied load, scratch
speed, tip geometry, testing temperature, etc.)
makes fundamental understanding of scratch behavior even more difcult. Several researchers have
also attempted to relate the variation of modulus,
toughness and hardness of the material to a scratch
resistance rating.

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The most challenging task within scratch analysis


is the consideration of surface morphology variations. These variations are mainly caused by processing and incorporation of different llers and
polymers in bulk materials for improved scratch
performance. Injection molding as a key manufacturing process is known to induce a skin-core
morphology in the molded parts. Due to the dissimilarity in the morphology, the skin layer is expected to have different scratch response to the core.
In recent years, the focus has not only been on
qualitative measurement methods as several quantitative methods to assess scratch visibility in PP
materials have been published. Kody and Martin [2]
developed a method using reected polarized light
microscopy to quantitatively characterize the light
scattered from scratches in PP blends. A similar
method was also used for different mineral lled PP
materials [3,4]. Xiang et al. [5] studied the scratching
behavior of PP, using optical microscopy and SEM
to characterize the subsurface damage. Recent
publications mentioned AFM and SEM methods
to get quantication of scratch damage in PP
material [610]. Since it is believed that scratch
resistance and scratch visibility are closely related to
surface hardness, a lot of tests can be found in the
literature concerning both issues [11]. The conclusions in such papers are confusing because some
state that there is a clear correlation of standard
indentation hardness tests with scratch visibility [4],
while others cannot see a correlation at all [3].
In this paper, we would like to highlight different
scratch resistance evaluation tools in multiphase PP
blends. The goal of this recent study is to properly
understand the scratch resistance of a multiphase
structure composed of PP matrix, rubber particles
(EPR) and a polyethylene phase. The design of
multiphase PP material with improved scratch
resistance is still an ongoing challenge in industry.
Each phase, and the interactions between them, are
expected to inuence the properties (also near the
surface) of the material. Transmission electron

microscopy will show the morphology of the


investigated materials. The scratch experiments
were done at the macro- and micro-scale because
it is interesting to look for similarities and differences between the results of those tests, especially in
the case of injection molded specimens which show
a morphology gradient from the skin to the core.
The deformation induced by the scratches was
characterized by scanning electron microscopy
(SEM), atomic force microscopy (AFM) and optical
microscopy.
These techniques gave additional results to the
visibility measurements (DL) via the Erichsen cross
hatch cutter test which is mainly used in the
automotive industry. Furthermore, different hardness measurements were conducted to look for
possible correlations to the scratch behavior.
2. Experimental
2.1. Materials
The thermoplastic olen (TPO) materials studied
in this research were injection molded blends of
isotactic polypropylene with about 20 wt% ethylene/propylene copolymer (EPR) and, optionally,
about 10 wt% polyethylene (PE). The types of PE
used were PE-LD, PE-LLD and PE-HD. Some
polymer characteristics are listed in Table 1 below.
Tests for exural modulus (Flex. Mod.) and
notched impact strength (NIS) were done according
to ISO 178 and ISO 179-1/1eA, respectively. The
polymer plaques for the micro-scratch and hardness measurements had dimensions of 60 mm 
60 mm  2 mm. They were produced by injection
molding and used without further treatment.
2.2. Microscopy
The morphology of the blends was studied via
transmission electron microscopy (TEM) at FELMI/ZFE in Graz. The samples were taken from the

Table 1
Used TPOs
Polymer blend

1
2
3
4

PP/EPR
PP/EPR/LDPE
PP/EPR/LLDPE
PP/EPR/HDPE

MFR (1901/
2.16 kg) (g/10 min)

Flex. Mod.
(MPa)

NIS (23 1C)


(kJ/m2)

NIS (20 1C)


(kJ/m2)

6.9
6.1
6.1
6.2

1088
972
965
1069

6.6
8.8
11.3
9.2

2
3.4
3
3.1

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middle of the injection molded specimens and


stained with RuO4 to distinguish between amorphous and crystalline parts. Ultramicrotomy cutting
was done after the staining to take advantage
of the hardening effect and the slides were taken
parallel to the machine-normal plane to see the
orientation of the elastomer particles. Details
of the method are described in a paper by Poelt
et al. [12].
2.3. Hardness testing
Due to the strong inuence of the indentation size
and depth, which was found in earlier work [13], we
measured surface hardness in different tests with
different indenter geometries. For the ball indentation hardness test, a round steel ball 5 mm in
diameter was used. The test procedure is given in
ISO 2039. The Shore D hardness test was performed
according to ISO 868. In this test, the indenter has a
301 cone with a 0.1 mm radius spherical tip. For
these macro-hardness test methods, the samples
have to be stacked to achieve the required specimen
thickness. The micro-hardness measurements were
done by instrumented indentation testing which
allows the determination of indentation hardness
HIT and indentation modulus EIT. These tests were
carried out with a constant indentation depth rate,
the maximum indentation of 2 mm being reached in
20 s; the load was held constant at this depth for 30 s
and then unloaded. The chosen indentation depth is
large enough to get a characteristic response from
the material, because the volume under the indenter
inuencing the result is nearly a half sphere having a
radius of about seven times the indentation depth.
In this volume, we will have a representative
amount of inclusions and matrix material. HIT
and EIT were calculated according to [14,15]. The
latter reference is a test standard developed for
metallic materials but it can be applied to polymeric
materials.

Fig. 1. Scratch experiments (a) parallel (J) and (b) perpendicular


(?) to the ow direction.

Fig. 2. Parameters describing the geometry of the microscratches.

In addition to the nano-indentor scratch tests, the


Erichsen cross hatch cutter method, which is well
established in the industry, was used for comparison
purposes. This apparatus consists of a scratching
device for cutting a cross hatch (40  40 mm) onto
the polymer surface. The instrument is equipped
with an ISO tip (0.75 mm) and dened speed
(normally 10 mm/s). The cutting force is adjustable
between 1 and 10 N. In our experiments 10 N was
taken as cutting force due to the requirements in the
automotive industry. The scratch evaluation is
carried out by measuring the DL values with a
spectral photometer. This measurement corresponds to the difference in brightness of the cut
and uncut polymer surface (DL44: strong visibility
of scratch; DLo1: signicantly lower visibility of
scratch).

2.4. Scratch tests

2.5. Atomic force microscopy

The micro-scratch tests were performed with a


Nano Indenter XP, MTS Systems, applying a constant normal load of 10 mN. The scratch velocity
was 50 mm/s. A standard Berkovich diamond
indenter was used which was moved edge forward
through the material. These experiments were done
parallel and perpendicular to the injection molding
direction (Fig. 1).

To evaluate the geometry of the scratches, AFM


measurements were done with a PSIA XE100
device. The measurements were carried out 24 h
after scratching in semi-contact mode on a 45 
45 mm2 scan region at a resolution of 256  256
pixels. From the cross proles, different parameters
can be extracted which describe the geometry of the
scratches (Fig. 2).

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T. Koch, D. Machl / Polymer Testing 26 (2007) 927936

3. Results and discussion


3.1. Morphology
All the blends contain particles with an EPR/
PE coreshell structure. The morphology varies
with the blend composition. Fig. 3 shows the
micrographs taken from the core region of
the polymer blends 14. While HDPE blends
(d) showed the high crystalline PE inclusion
(lamellae can be seen very clearly) together
with coarser particles, PE-LLD-blends (c) showed

a more homogenous distribution with smaller


particles.
A clear gradient of particle distribution from the
skin to the core layer could be seen in all polymer
blends. A picture of the skin layer of blend 1
(030 mm) and subsurface layer (30100 mm) is given
as an example in Figs. 4a and b, respectively. In the
skin layer a strong elongation of the elastomeric
phase can be observed, in the subsurface layer
the orientation of the particles is still present, but
much weaker. The present morphology follows the
observations in [16].

Fig. 3. TEM micrographs in magnications of 26,000 and 52,000 (the black bar in the pictures represent on the upper pictures 500 nm and
underneath 200 nm) of PP/EPR/PE blends: (a) blend 1, (b) blend 2, (c) blend 3 and (d) blend 4.

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A typical cross-section of a macro-scratch is


shown in Fig. 5a. A strong pile-up at the edges
of the scratch can be seen. For the base material
blend 1, the smallest scratch width d1 but the highest
scratch depth h1 and pile-up h2 were observed. From
the smallest scratch width it follows that blend 1 has
the highest scratch hardness Hs which can be
calculated from the applied load F and the width
d1 [13]:
Hs

Fig. 4. (a) Skin layer (030 mm) and (b) subsurface layer
(100130 mm) of the polymer blend 1.

3.2. Scratch deformation behavior


The results of the visibility measurements via
Erichsen cross hatch cutter test are listed in the last
column of Table 2. Blend 1 shows the highest DL
values representing the best visibility of the
scratches. That means that the base polymer blend 1
had the worst macroscopic scratch resistance. The
PE modied blends are much better in this respect
but among the different PE materials used in
polymer blends 24 only relatively small differences
were observed.

4F
.
pd 21

(1)

Adding polyethylenes to the base material blend 1


leads to a decrease of scratch hardness. Among
these PP/EPR/PE materials, blends 24, the blend
containing PE-HD shows the highest scratch hardness, as was expected.
Remembering that the visibility is the most
important parameter characterizing the scratch
resistance of a polymer in service, it is obvious that
the scratch hardness is not the dominating material
property. In the PE containing blends, the pile-up
and the scratch depth h1 is reduced (Fig. 5b), which
should inuence the visibility. Moreover, it is
known that the deformation in the scratch ground
inuences the visibility [2]. To evaluate this, SEM
investigations of the scratches were done.
Fig. 6 shows the deformations induced in the
macro-scratch test. Parabolic scratch tracks were
formed in all materials, but there are some obvious
differences. The base material, blend 1, shows the
most irregularly deformed surface. Intense plastic
features with underlaying shear bands can be
observed, and the roughness is high. There is no
signicant difference between the materials containing low-density polyethylene; the surfaces in both
blends are smoother than in blend 1. Blend 4, which
contains high-density polyethylene, shows only
shear bands. In [8] the near-surface deformation
processes under scratches in polypropylene blends
are described as the formation of periodic shearband structures.
The micro-scratching tests were done for different
reasons. First we wanted to check if it is really
possible to correlate micro-scratch behavior with
macroscopic behavior. This is expected to be
especially a problem in injection molded parts
where a strong gradient in morphology can be
found. The second reason was that in daily use
polymer parts are often subjected to slight wear, for
example scratching by sand or dust, which inuences only the immediate surface regions.

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Table 2
Parameters evaluated for the different PP/EPR/PE blends
Material

Blend
Blend
Blend
Blend

1
2
3
4

Macro-scratching

Micro-scratching

Visibility, DL

h1 (mm)

h2 (mm)

d (mm)

h1 (mm)

h2 (mm)

d (mm)

35
26
29
26

19
14
16
13

411
434
425
422

0.996
0.969
0.656
0.564

0.386
0.190
0.027
0.042

20
18
17
21

1.7
0.9
0.8
0.7

Fig. 5. Characteristic parameters of the scratches induced by macro-scratch experiments; load 10 mN, velocity 10 mm/s.

Typical AFM pictures of the remaining microscratches are shown in Fig. 7. Whereas the blends
1 and 2 show strong pile-up at the edges of the
scratch there was nearly no pile-up observed for
the blends 3 and 4. The strong difference between
the materials containing low-density polyethylene,
blends 2 and 3, are a little bit surprising because
their behavior was comparable in the macro-scratch
experiments. This could be due to a difference of
the morphology in the very outermost layer of these
specimens.
From the cross proles of the micro-scratches
(Fig. 8) a recovery parameter can be calculated in

the following way:


recovery

h1;L  h1;U
 100%,
h1;L

(2)

where h1,L is the indentation depth during scratching and h1,U is the indentation depth after unloading.
The surfaces of the blends 1 and 2 show recovery
values of 78%, while for the blends 3 and 4 this
value reaches 83%. The difference in the recovery
behavior is relatively small, so we think that in these
materials the inuence of the recovery behavior on
the scratch geometry is not the dominating factor.

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Fig. 6. Scratch deformation by the macro-scratch experiments: blend 1 (a), blend 2 (b), blend 3 (c) and blend 4 (d).

Fig. 7. AFM pictures of the scratches in polymer blend 1 (a), polymer blend 2 (b), polymer blend 3 (c) and polymer blend 4 (d).

Nevertheless, it can be seen that the blends with the


higher recovery values show smaller pile-up. However, linking both things together seems to be
speculative.

Although the scratches were done with the


Berkovich diamond indenter in parallel and perpendicular ow directions, only the pictures in ow
direction are shown. Due to the orientations at the

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surface, there was a large difference between the


appearances of the scratches performed parallel or
perpendicular to the ow direction. Whereas the
parallel scratches show well-dened geometries, the
perpendicular scratches have a too high noise level
to distinguish between scratch and noise. The noise
behavior could be mainly inuenced by the amount
and size of the elongated rubber particles in the
surface region, which should dominate the deformation at the micron scale.

Fig. 8. Scratch proles of the two limits in the scratch


deformation behavior of the investigated materials: polymer 1
(a) and polymer 3 (b).

3.3. Hardness measurements


In addition to the above measured parameters to
characterize scratch deformation resistance, surface
hardness is often described as a parameter which
inuences a materials resistance to scratch. The
hardness was measured by ball indentation hardness, Shore D and micro-hardness measurements
with a nano-indenter. The results of the indentation
hardness (HIT) and indentation modulus (EIT)
together with conventional macro-hardness measurements are listed in Table 3. In all cases, blend 1
shows the highest hardness values, whereas blends 2
and 3 show the lowest values due to the softening
effect induced by the added low-density PE component. The ball indentation and micro-hardness tests
as well as the scratch hardness values, calculated
from the scratch width, allow also to distinguish
between the polymers 1 and 4; addition of PE-HD
leads to lower hardness values of material blend 4
compared to blend 1. A good correlation (as
expected) between modulus and indentation hardness was observed. This behavior was also observed
earlier in PP/EPR polymer blends and PP/EPR/PEHD blends [4].
It can be seen that the ratio of indentation
hardness and modulus, H/E, which is described in
the literature as a plasticity parameter describing the
ductility of a material [17], does not correlate with
the determined topography of the micro-scratches.
Whereas H/E helps to classify the scratch behavior
of different material classes such as between metals
and polymers [18], it fails in the case of very similar
materials.
One can note that Shore hardness does not seem
to be suitable for distinguishing between the
materials as it does not show signicant differences.
Due to the relevance of the injection molding
process in the automotive industry, an additional study of specimen hardness was done over
the entire cross-section of an injection molded

Table 3
Ball indentation, Shore, micro- and scratch hardness of the studied blends
Material

Blend
Blend
Blend
Blend

1
2
3
4

BIH (MPa)

38
31
32
36

Shore D

59
57
58
59

Micro-hardness
HIT (MPa)

EIT (MPa)

H/E

49
41
40
43

904
647
654
755

0.054
0.063
0.061
0.057

Hs (MPa)

DL

75.4
67.6
70.5
71.5

1.73
0.93
0.83
0.73

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Fig. 9. Cross-sectional indentation hardness vs. distance to the surface for the different polymers.

60  60  2 mm3 specimen. The study of KargerKoscsis and Csikai [16] showed a few years ago
differences in the skin-core distribution of EPR
particles in injection molded specimens. We wanted
to check if we can also nd differences in the
distribution of micro-hardness over cross-section
between the studied blends. This would help further
to conclude on relevant issues about subsurface
hardness.
Fig. 9 presents the cross-sectional hardness values
of the materials. The black spots represent the
material hardness in the ow direction and the white
spots reect the across ow data. The rst position
is at a distance of 30 mm from the surface; this
relatively large distance is needed to meet the
requirements on a non-edge-inuenced indentation
and we could not reduce the indentation size for the
reasons given earlier. In the near-surface regions (up
to a distance of 60 mm) the behavior of polymers 2,
3, and 4 is comparable. The hardness values of
blend 1 are higher. In the middle region of the plates
(0.5 and 1 mm from the surface) the micro-hardness
values show the same relations between the materials as the ball indentation hardness values, irrespec-

tive of the absolute level of the values. This is the


case because in the ball indentation test we had
indentation depths between 220 and 260 mm, so that
the material response came from a half sphere with
a radius of approximately 1.51.8 mm. Hence, the
ball indentation hardness is strongly inuenced by
the properties of the core of the injection molded
2 mm thick plates.
4. Conclusions
The inuence of addition of different polyethylenes to a heterophasic PP/EPR copolymer on the
scratch behavior was investigated. From these
investigations the following results can be deduced:
1. The addition of PE leads to a reduced visibility of
the scratches produced by a macroscopic scratch
test, which means better behavior during daily
use of these materials.
2. The PE containing blends show a reduced scratch
depth and pile-up after the macro-scratch experiments. In these materials, the roughness in the
scratch ground is reduced also.

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3. The hardness does not dominate the scratch


behavior in this class of materials. The PP/EPR
base material, which has the highest hardness,
shows the worst scratch behavior in the macroscopic and in the microscopic scratch experiments.
4. Addition of PE-HD and PE-LLD reduces
signicantly the pile-up behavior during microscratching. Additionally, the recovery increases
in these materials. The reason for that, especially
the differences between the PE-LD and PE-LLD
containing blends, is not fully clear yet. To
resolve this, a more detailed investigation of the
morphology of the surface, including determination of the orientations, has to be done, but this is
beyond the scope of the present work.
5. There is no strong correlation between the microscratch experiments on the surface of the injection molded specimens and the macroscopic
scratch tests. Nevertheless, the higher plastic
deformability of the base PP/EPR blend, resulting in a stronger pile-up, was found at both scales
of scratching.
Acknowledgements
The authors would like to thank Dr. Elisabeth
Ingolic (Center for Electron Microscopy Graz,
Austria) for the excellent TEM images.
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