European Polymer Journal 40 (2004) 679684

www.elsevier.com/locate/europolj

Tensile behaviour of isotactic polypropylene modied

by specic nucleation and active llers
Ji
r Kotek *, Ivan Kelnar, Josef Baldrian, Miroslav Raab
Department of Polymer Networks and Mechanical Properties, Institute of Macromolecular Chemistry,
Academy of Sciences of the Czech Republic, Heyrovsky Sq. 2, 162 06 Prague 6, Czech Republic
Received 4 November 2003; received in revised form 4 December 2003; accepted 6 December 2003

Abstract
Commercial-grade polypropylene was modied with a specic nucleation agent based on an amide of dicarboxylic
acid, which promotes crystallization predominantly in the b-phase. The resulting material was used as a matrix for
composites containing 10%, 20%, and 30% (by weight) of dierent calcium carbonate llers. These llers diered in
particle size and surface treatment. The b-phase content, morphology and tensile mechanical properties were investigated. A distinct b-nucleation activity was found with surface-treated llers; nevertheless, to obtain sti and reasonably
ductile composite materials, a matrix containing a critical nucleant concentration (0.03 wt%) was necessary.

2004 Elsevier Ltd. All rights reserved.
Keywords: Polypropylene; b-Phase; CaCO3 ller; Tensile properties

1. Introduction
Filled polypropylenes are important commercial
materials widely used in large quantities in dierent
application segments [1]. Addition of llers to polypropylene enhances many of its mechanical and thermal
characteristics, including stiness, creep resistance, heat
deection temperature and shrinkage. On the other
hand, the presence of llers usually deteriorates strength
and toughness.
Isotactic polypropylene (PP) itself is a polymorphic
material, which can crystallize in three dierent crystalline phases, namely monoclinic (a), hexagonal (b) and
triclinic (c).
Commercial grades of PP crystallize under standard
conditions as the a-phase, but in some cases this can be
accompanied by a lower amount of the hexagonal bphase. It has been reported [15] that the toughness of bphase is considerably higher than that of the a-phase. At

the same time, there is only a small loss in stiness. Since

the formation of the b-phase can be promoted by adding
suitable nucleation agents at concentrations lower than
0.1 wt%, the tough b-PP is of considerable scientic and
commercial interest [58].
In the present work, the possibilities of the preparation of lled b-PP composites are studied. The goal was
to check whether the higher ductility of the b-PP can
compensate the well-known detrimental eect of ller on
the failure behaviour. Materials lled with dierent
types of calcium carbonate, similar to those based on
conventional a-polypropylene were prepared. The eects
of the addition of selected llers on morphology, bphase content and resulting tensile mechanical properties are reported.

2. Experimental
2.1. Materials and specimens

Corresponding author. Tel.: +420-296-809-384; fax: +420296-809-410.

E-mail address: kotek@imc.cas.cz (J. Kotek).

Isotactic polypropylene homopolymer Mosten

52.412 (Chemopetrol, Czech Republic) was used as a

0014-3057/$ - see front matter
2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2003.12.004

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J. Kotek et al. / European Polymer Journal 40 (2004) 679684

starting material throughout this study. To obtain a

material rich in the b-phase, the polymer was modied
with a selective b-nucleant NJ-Star NU-100 (RIKA,
UK), N,N0 -dicyclohexylnaphthalene-2,6-dicarboxamide.
Based on our previous study [2], two concentrations of
the nucleant were chosen: 0.03 and 0.1 wt%. The nucleant was premixed with a polypropylene powder and
compounded with neat polypropylene pellets using a
corotative twin screw extruder. The extrudates were then
pelletized.
The following particulate llers were used:
Calcium carbonate, average particle size
1.3 lm
(C1); Kalcimat KO-M/1, supplied by TT service,
Czech Republic.
Stearate-coated calcium carbonate, average particle
size
1.3 lm (C2). This ller is the C1 ller with surface modication.
Stearate-coated precipitated calcium carbonate, average particle size
0.075 lm (C3); Winnol S, supplied by ICI, UK.
The composites were prepared by mixing the starting
and b-nucleated polypropylenes with 10, 20 and 30 wt%
of the individual llers in the chamber of a Brabender
Plasti-Corder at 200 C and 60 rpm for 10 min. The
material removed from the chamber was immediately
compression-moulded to form 1-mm thick plates. Strips
cut from these plates were used for preparation of dogbone specimens. The specimens of the type 1BA
(according to the ISO 527 standard) with cross-section
of 5 2 mm2 and a gauge length of 25 mm were prepared
in a laboratory micro-injection moulding machine
(DSM, Netherlands). The injection-moulding process
was optimized in order to obtain samples rich in bmodication. The barrel temperature was 210 C, the
selected optimum temperature of the mould was 90 C.
2.2. Sample characterization and testing
The structure was assessed by scanning electron
microscopy and X-ray diraction. Wide-angle X-ray
scattering (WAXS) was performed in a transmission
mode. A powder diractometer HZG (Prazisionmechanik Freiberg, Germany) using Cu Ka radiation monochromatized with a b-lter was used for the
measurements. The relative amount of the b-form in the
crystalline phase was characterized by the ratio K. Its
value was assessed from intensities of crystalline reections of a- and b-phase using the following relation [9]:
K Ib =Ia1 Ia2 Ia3 Ib ;

where Ib is the integral intensity of 300 reection of the

b-phase, and Ia1 , Ia2 and Ia3 are the integral intensities of

the 110, 040, and 130 reections of the a-phase,

respectively.
Supermolecular morphology was assessed by scanning electron microscopy. Cross-sections of the injection-moulded specimens perpendicular to the long axes
were cut in liquid nitrogen using a glass knife. The
crystalline morphology was then visualized by permanganic etching [10].
Tensile tests were performed using an Instron 5800
tensile tester at room temperature and a cross-head
speed of 20 mm/min. The following mechanical characteristics were derived from the stressstrain curves:
Young modulus E, yield stress ry and strain at break eb .
Reported values are averages of 10 individual measurements. Corresponding variation coecients did not
exceed 10%, 5% and 35%, respectively.

3. Results and discussion

3.1. Unlled polypropylene
Cavity lling during injection moulding is a very
complex process that strongly inuences the b-phase
content and results in the so-called skin-core morphology of the moulding. It has been reported by Varga that
pure b-iPP cannot be produced by injection moulding
[2]. While the core of the mouldings is rich in the bphase, the skin consists of nearly pure a-modication.
The smaller is the cross-section of injection-moulded
specimen, the more signicant are the eects of processing conditions on the resulting average b-phase
content. In Table 1 is shown the inuence of mould
temperature on the average b-phase content in the
material nucleated by 0.03 wt% of the nucleating agent.
It is demonstrated that with increasing mould temperature the b-phase portion in the material increases as a
consequence of decreasing thickness of the skin, which is
poor in b-modication. Because of a strong eect of the
injection moulding conditions on the b-phase content,
the value of K was determined also on the compressionmoulded sheets. In this case no b-phase occurs in the
non-nucleated material and the critically nucleated
material contains pure b-phase.

Table 1
The eect of mould temperature on fraction K of the b-crystallites within the crystalline phase in injection-moulded specimens
Mould temperature (C)

K (%)

60
70
80
90

51
53
56
61

J. Kotek et al. / European Polymer Journal 40 (2004) 679684

The eects of the nucleant concentration on the bphase content K as well as on the crystallinity and selected mechanical properties are summarized in Table 2.
As reported in our previous work [5], the content of 0.03
wt% of the used b-nucleant represents a critical concentration for obtaining a material containing predominantly the crystalline b-phase. With further increasing
the nucleant concentration, the b-phase content increases but very slightly.
It can be seen that the addition of 0.03 wt% of the
nucleant leads to a marked increase in the b-phase
content from 10% (non-nucleated polymer) to 61%. The
presence of the b-phase in non-nucleated material
obviously reects the low thickness of the injectionmoulded specimens and, consequently, a relatively
pronounced skin eect. For the highest nucleant concentration (0.1 wt%), the value of K increases to 65%. The
yield stress drops from 35 MPa for the non-modied
material to 28 MPa for the critical nucleant concentration and for higher nucleant content remains virtually
identical. The corresponding dependence of the Young
modulus has a similar trend. The strain-at-break values
pass through a distinct maximum at the critical nucleant
content. This maximum indicates an optimum structural
arrangement for the development of plastic deformation
[5]. As revealed by SEM, the spherulitic structure of the
non-modied material consists of a-spherulites with an
average diameter of 20 lm (Fig. 1). While the critically

681

nucleated material contains well developed b-spherulites, the supercritically nucleated PP shows bundle-like
morphology without distinctly developed spherulites
(Fig. 2). The dierence in supermolecular morphology
can explain the dierent mechanical behaviour of these
two materials that contain almost the same b-phase
portion. We can suggest that the presence of developed
b-spherulites is favourable to higher plasticity and
toughness.
3.2. Polypropylene composites
The dependences of the fraction K of the b-crystallites within the crystalline phase on the nucleant concentration for materials lled by 10 wt% of the
individual ller are plotted in Fig. 3. Virtually identical
dependences were obtained also for higher applied ller
contents (20 and 30 wt%). It can be seen that not only
the presence of the specic b-nucleant, but also the
distinct b-nucleation activity of the inorganic llers as
well as the injection-moulding process inuence the bphase content in the resulting material. The nucleation
eects are much more pronounced for stearate-coated
precipitated calcium carbonate (C3) than for the micromilled llers, both coated and uncoated (C1, C2).

Table 2
The eect of nucleant concentration (NC) on fraction K of the
b-crystallites within the crystalline phase, overall crystallinity Xc
and selected mechanical characteristics (Young modulus E,
yield stress ry , strain at break eb )
NC
(wt%)

K
(%)

Xc
(%)

0
0.03
0.10

10
61
65

57
57
59

E
(MPa)
1600 130
1440 100
1490 120

Injection-moulded specimens.

ry
(MPa)
36.7 1.2
28.0 0.5
28.5 0.7

eb
(%)
176 45
428 77
218 68

Fig. 1. Supermolecular structure of non-nucleated polypropylene.

Fig. 2. Supermolecular structure of critically (left) and supercritically (right) nucleated polypropylenes.

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J. Kotek et al. / European Polymer Journal 40 (2004) 679684

Table 3
The eect of nucleant and/or ller on the b-phase content in
compression-moulded sheets

100
90
80
70

K [%]

60
50
40

unfilled
C1 filler
C2 filler
C3 filler

30
20
10
0
0.00

0.02

0.04

0.06

0.08

0.10

Nucleant concentration [wt%]

Fig. 3. Typical dependences of the fraction K of the b-crystallites within the crystalline phase on the nucleant concentration.
Materials lled by 10 wt% of individual ller. Corresponding
dependences for higher ller loading (20 and 30 wt%) are virtually identical.

Obviously, substantially lower particle size and, consequently, a much higher interface area plays a decisive
role in the nucleation activity. The situation is similar to
the eect of the specic nucleating agent: Once a critical
nucleant concentration is reached, a b-phase saturation
level occurs and further addition of the nucleant has
only a minor eect [5]. At the same time, the ller type
plays a crucial role.
The addition of llers to non-nucleated polypropylene increases the b-phase content K from 10% to
25%
for C1 and C2 llers and to about 50% for the C3 ller.
On the other hand, the addition of inorganic llers to the
critically nucleated b-polypropylene matrix slightly decreases the b-phase content from 61% to 50%, 54% and
56% for llers C1, C2 and C3, respectively. Further increase in the nucleant concentration to supercritical
values does not change the situation signicantly; nevertheless, the K values are higher by few percents. The
eect of surface treatment on the ller nucleation
activity is pronounced in the case of compressionmoulded sheets. While the modication of non-nucleated polypropylene by the untreated C1 ller leads
virtually to the same K value as in injection-moulded
specimens (
25%), the application of stearate coating
(C2 ller) increases the b-phase content in compressionmoulded sheets to 63%. The b-nucleation activity of
stearate coated calcium carbonate has been reported
[12]. Nucleated compression-moulded sheets contain
pure b-modication (Table 3).
The eects of the specic nucleant and llers on the
resulting mechanical behaviour of injection-moulded
specimens are jointly presented in Fig. 4. The tensile
properties reect both the properties of the polypropylene matrix and the presence of the ller. Thus, the

NC (wt%)

Filler

Filler content (wt%)

K (%)

0
0.03
0
0
0.03
0.03

C1
C2
C2
C3

20
20
20
20

0
100
25
63
100
100

tensile moduli of composites with non-nucleated matrix

are higher than those with nucleated matrix. In all cases,
the moduli increase with increasing ller content. On the
other hand, the yield stress of non-nucleated polypropylene signicantly decreases with increasing ller
loading. This behaviour can be ascribed to poor adhesion between the polymer matrix and the ller, which
allows debonding at the onset of plastic deformation.
The dierences between individual llers reect interface
properties, particle size, particle agglomeration and the
b-phase nucleation eect. The low level of yield stress of
materials with matrices modied with a specic nucleant
is not markedly inuenced by the ller addition. Only
the highest used ller concentration causes a certain
depression in the yield stress.
All the samples investigated in the present study
show cold-drawing after reaching the yield point. The
extent of plastic deformation characterized by strain at
break is then very sensitive to composition and morphology of the composites. As shown in Fig. 4, the three
types of the calcium carbonate llers have distinctly
dierent eects. The materials with non-nucleated matrix show low values of strain-at-break. The steep decrease in this characteristic caused by the incorporation
of the lowest amount of C1 ller (10 wt%) indicates
debonding at the interface during the tensile deformation. Obviously, relatively large particles with low
interfacial adhesion act as structural heterogeneities.
The distinctly higher strain-at-break of the sample containing the same amount of C2 ller with the same
particle size reects the surface treatment that suppresses
particle aggregation. Even higher strain-at-break for the
material with C3 ller could be explained by smaller
particle size and a signicantly higher b-phase content.
The aggregation of ller particles at higher ller contents
(20 and 30 wt%) overshadows the dierences between
individual llers. Indeed, very ne particles of C3 ller
are dicult to disperse and the agglomerates then behave as large single particles.
As already reported, at a critical nucleant content
(0.03 wt%), maxima in toughness and deformability
occur [5]. Correspondingly, also the critically nucleated
lled polypropylenes show distinctly higher values of
strain-at-break than the other studied composites. With

J. Kotek et al. / European Polymer Journal 40 (2004) 679684

Critically-nucleated PP

2400

2200

2200

2200

2000
1800
1600
1400

C1 filler
C2 filler

1200

C3 filler
0

10
20
Filler content [wt%]

2000
1800
1600
1400

C1 filler
C2 filler

1200

C3 filler

1000

30

10
20
Filler content [wt%]

30

C3 filler
30

25

10
20
Filler content [wt%]

C3 filler
30

25

200
100

10
20
Filler content [wt%]

C 3 filler
0

30

30

10
20
Filler content [wt.%]

C 2 filler
C 3 filler

35

30

25

30

10
20
Filler content [wt%]

500
C1 filler
C2 filler

400

C3 filler
300
200
100

C 2 filler

1200

20

30

10
20
Filler content [wt%]

Strain-at-break [%]

Strain-at-break [%]

C3 filler

C 1 filler

1400

C 1 filler

C2 filler

500
C1 filler
C2 filler

300

1600

40

35

20

30

500
400

1800

C1 filler
Yield stress [MPa]

35

2000

1000

40
C1 filler
C2 filler

Yield stress [MPa]

Yield stress [MPa]

40

20

Young modulus [MPa]

2400

1000

Strain-at-break [%]

Supercritically-nucleated PP

2400
Young modulus [MPa]

Young modulus [MPa]

Non-nucleated PP

683

C1 filler
C2 filler

400

C3 filler

300
200
100

0
0

10
20
Filler content [wt%]

30

10
20
Filler content [wt%]

30

Fig. 4. The eects of nucleation and ller loading on the tensile mechanical behaviour of injection-moulded specimens.

500

unfilled
C1 filler
C2 filler
C3 filler

400

Strain-at-break [%]

increasing ller loading, the strain-at-break decreases,

especially for the untreated C1 ller. Materials lled
with the surface-treated llers (C2, C3) maintain high
strain-at-break up to 20 wt% loading. At a ller content
of 30 wt%, the strain-at-break further decreases, but its
values are comparable with corresponding values of neat
non-nucleated polypropylene. Surprisingly, materials
lled with the nest C3 ller show a systematically lower
drawability than corresponding materials with C2 ller.
This suggests aggregation of C3 particles as directly
indicated by scanning electron microscopy.
Composites with supercritically nucleated matrices
display similar behaviour, but with lower strain-at-break
values. Generally, the strain-at-break can serve as a
sensitive indication of the presence of structural aws
within the material. The interaction of structural defects
with the propagating neck shoulder during solid-state
drawing has been discussed [11].
The eect of nucleant concentration on the strain-atbreak of samples lled with 20 wt% of individual llers is
plotted in Fig. 5. This gure shows that for obtaining a
material with high ductility, not only the presence of the

300

200

100

0
0.00

0.02

0.04

0.06

0.08

0.10

Nucleant concentration [wt%]

Fig. 5. The eect of the nucleant concentration on the strainat-break values of injection-moulded specimens lled with 20
wt% of the individual llers.

b-phase, but also its particular morphological arrangement is necessary. Indeed, the samples containing 20
wt% of stearate-coated precipitated calcium carbonate

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J. Kotek et al. / European Polymer Journal 40 (2004) 679684

(C3 ller) show a very little dierence in the b-phase

content (50% for non-nucleated PP and 56% for critically nucleated PP) but a great dierence in strainat-break values (80% for original polypropylene and
260% for critically nucleated sample). Thus, the results
of the present work have shown that macroscopic
mechanical properties could not be explained solely by
the composition of the materials but all the levels of the
structure hierarchy must be taken into account.

more pronounced with uncoated ller and increases with

increasing ller content.

Acknowledgements
This work was supported by the Czech Science

(Projects 106/02/P027 and 106/01/
FoundationGA CR
0601).

4. Conclusions
References
Following conclusions can be drawn from the results
of this study:
Addition of a small amount of a specic b-nucleant
(N,N0 -dicyclohexylnaphthalene-2,6-dicarboxamide) to isotactic polypropylene induces predominant formation of
the crystalline b-phase in injection-moulded, but especially
in compression-moulded specimens. To obtain a material
with high drawability, not only the presence of the b-phase,
but also its supermolecular arrangement plays a decisive
role.
Combination of specic b-nucleation and inorganic
llers can lead to materials with higher ductility and
higher modulus than neat isotactic polypropylene. To
reach this goal, a critical nucleant concentration (0.03
wt%) and 20 wt% of stearate-coated calcium carbonate
should be used. These results indicate a synergism of
surface coating, which suppresses ller agglomeration,
and the optimum matrix morphology formed by the
critical nucleation.
Calcium carbonate llers together with processing
conditions can initiate the formation of certain amount
of the crystalline b-phase. A stearate-coated ller with
very ne particles exhibits the highest b-nucleation
activity.
Samples containing 20 wt% of stearate-coated precipitated calcium carbonate (C3 ller), both with and
without the nucleant, show very little dierence in the bphase content (50% for non-nucleated polypropylene
and 56% for critically nucleated polypropylene), but
great dierence in strain-at-break values (80% for nonnucleated polypropylene and 260% for critically nucleated sample). Again, these results show that not only the
presence of the b-phase itself, but also its particular
morphological arrangement is necessary to reach high
ductility.
A favourable eect of the b-phase on plasticity is
suppressed by the presence of llers. Low interfacial
adhesion and particle agglomeration initiate crack formation. The corresponding decrease in strain-at-break is

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