Polymer-Plastics Technology and Engineering, 46: 985–990, 2007

Copyright # Taylor & Francis Group, LLC

ISSN: 0360-2559 print/1525-6111 online
DOI: 10.1080/03602550701519449

Study on the Crystallization Properties of

Polypropylene/Montmorillonite Composites
Ge Mingliang
College of Industrial Equipment and Control Engineering, South China University of Technology,
Guangzhou, China and College of Material Science and Engineering, South China University of
Technology, Guangzhou, China

Jia Demin
College of Material Science and Engineering, South China University of Technology,
Guangzhou, China

Xu Weibing
College of Chemical Engineering, Hefei University of Technology, Hefei, China

strongly dependent on the morphology formed and the

The crystalline size of polypropylene (PP) filled with montmor- extent of crystallization, studies related to the crystalliza-
illonite (MMT) was studied by X-ray diffraction (XRD). The tion process of PP are of great importance in polymer pro-
isothermal crystallization behavior of polypropylene was studied cessing. Properties of PP were often improved by fillers[1–8]
by means of differential scanning calorimetry (DSC). The Avrami (for example CaCO3, mica, talc, glass fiber, and so on).
equation was used to describe the isothermal crystalline kinetics
of PP/MMT composites. The result showed that the addition of Montmorillonite is a kind of layered silicates that is attract-
MMT decreased the crystalline size Lhkl of the polymer. MMT ing great attention owing to its outstanding reinforcement
was used as nucleating agent during isothermal crystallization for most polymers and its potential in the preparation of
process of polypropylene. The addition of montmorillonite polymer=layered silicate composites[9–13]. Of considerable
decreased the crystallization time of the polypropylene and the melt importance to prepare polymer=layered silicates compo-
point was raised. The value of Avrami exponent n was related with
the crystallization temperature. The value of Avrami pre-index sites is how to disperse the layered silicates in the polymers
factor k of PP/MMT composite was decreased with increasing because these layered silicates affect the crystallization
crystallization temperature. The value of half crystallization time process of the polymers, so some workers have studied
t1/2 of PP/MMT composite was less than that of PP at a given the crystallization process of polymer=montmorillonite
crystallization temperature, signifying that montmorillonite composites[14–17].
acted as nucleating agent, accelerated the overall crystallization
process. In this article, PP=montmorillonite(PP=MMT) compo-
sites were studied. The microcrystalline dimensions Lhkl
Keywords Isothermal crystallization kinetics; Montmorillonite; of the PP=MMT composite were investigated by XRD.
Polypropylene The isothermal crystallization process of PP was researched
by DSC and the crystallization kinetic parameters of PP
1. INTRODUCTION and PP=MMT composite were calculated. The degree of
Polypropylene (PP) is a kind of crystallization plastic crystallization and melt point were also acquired.
which has light density, facile fluid, and favorable process
property and is often processed through extrusion, injec-
tion, and moulding, so PP is widely applied in areas such 2. EXPERIMENTAL
as agriculture, automobile, machined, and electric. Owing
2.1. Materials
to the fact that the resulting physical properties are
Montmorillonite (MMT) with a cation-exchange capacity
(CEC) value of 100 mmol=100 g was provided by Qings-hua
Address correspondence to Ge Mingliang, College of Industrial
Equipment and Control Engineering, South China University of Chemistry Agent Factory in Lin’an, Zhejiang province
Technology, Guangzhou 510640, China. Tel.: þ 8602087113374; and Polypropylene (PP), 045, was purchased from An’qing
E-mail: gml@scut.edu.cn Petrochemical Co., Anhui province (China).

985
986 G. MINGLIANG ET AL.

2.2. Sample Preparation

PP and MMT (3 wt %) were dry blended prior to
melt-blending on an twin-roller blender (SK160B) until
the mixture were evenly mixed, then the mixture was taken
out and molded on a compression molding machine
(QLB400
400
2) at the following condition: 180C
molding temperature, 10 MPa pressure, 10 min molding
time, subsequently allowed to cool at 7.5 MPa pressure
down to room temperature.

2.3. X-ray Diffiraction (XRD)

X-ray diffraction (XRD) analysis was carried out in
order to study the crystalline size of PP and PP=MMT
composite. Rigaku- D=max-cB rotating anode X-ray
diffractometer (Rigaku, Japan) was employed with Cu FIG. 1. X-ray diffraction curves of PP=MMT composite. a, PP; b,
Ka radiation (k ¼ 0.15418 nm) at room temperature by PP=MMT (3 wt %).
using graphite-filter. The X-ray generator was set to
40 kV at 100 mA and The XRD patterns were scanned in
2h ranges from 5 to 60 at a rate of 2 min 1. where Lhkl is the microcrystalline dimension (nm), h is an
angle of incidence, k is the wavelength of X-ray
(k ¼ 0.154 nm), b0 is the full width half maxima, FWHM
2.4. Differential Scanning Calorimetry (DSC)
(in radians of theta). The calculated result is shown in
A Perkin Elmer DSC-2 was used to monitor the crystal-
Table 1.
lization behavior of PP and PP=MMT composite. A poly-
As shown in Table 1, the crystalline size Lhkl of
mer sample (4  6 mg) was weighed accurately, sealed in an
PP=MMT is less than that of PP except for L111. The result
aluminium pan, and placed in the DSC cell which had been
indicated the addition of montmorillonite could reduce the
set at the starting temperature (200C). The sample reached
crystalline size of PP.
this starting temperature within 1 min of loading. The cell
was continuously purged with nitrogen. The sample was
held at the starting temperature for a desired time (5 min), 3.2. Effect of the Crystallization Temperature and
and then cooled quickly to crystallization temperature Montmorillonite on the Isothermal
(Tc, 126, 127, 128, 129C) for a desired time (15 20 min). Crystallization Behavior of PP
The peak crystallization time and the heat of fusion Figure 2 shows the isothermal crystallizing DSC curves
were recorded. Immediately after complete crystallization of PP and the PP=MMT composites. The DSC curves indi-
at Tc, the sample was heated without prior cooling at cated that, the crystallization peaks obviously widened and
a constant scanning rate of 20C min–1 to observe its shifted to right region as the crystallization temperature
melting behavior. The melting temperature (Tm) and the increased. With the crystallization temperature increasing,
heat of melting process were measured by the supplied the crystallization rate decreased and crystallization time
software. increased. The reason was that the macromolecular chain
moved more easily in higher crystallization temperature
3. RESULTS AND DISCUSSION and polymer chain was difficult to arrange orderly, result-
ing in the prolonging of the crystallization time. At the
3.1. Effect of the Montmorillonite on the Crystal same crystallization temperature, the DSC curve of PP
Structure of PP was compared with that of PP=MMT composites. It was
The X-ray diffraction patterns of PP=MMT composite found that the shapes and position of crystallization peaks
with neat PP are shown in Fig. 1. As seen from Fig. 1, of PP were different from those of PP=MMT composite.
the diffraction peaks of PP do not shift. There is no distinct The position of the crystallization peaks of PP=MMT
difference between PP and PP=MMT composite, both of
them are a-phase crystallite. The addition of montmoril-
lonite did not affect the crystal structure of the PP matrix TABLE 1
in this case. According to the Debye-Sherrer equation[18], The crystalline size Lhkl of PP and PP=MMT composites
the crystalline size of PP(Lhkl) can be calculated: Sample L110 L040 L130 L111 L041
0:90k PP 9.88 10.30 10.32 10.36 10.37
Lhkl ¼ ð1Þ PP=MMT 7.21 9.56 9.25 12.24 9.99
ðb0cos hÞ
 CRYSTALLIZATION PROPERTIES OF POLYPROPYLENE COMPOSITES 987

FIG. 2. Isothermal crystallizing DSC curves of PP and PP=MMT (3 wt%).

composites appeared earlier than that of PP. This Figure 3 shows the relative degree of crystallinity, Xt, as a
illuminated that the addition of montmorillonite leaded function of crystallization time at various crystallization
to advance crystallization of PP. It is obvious that mont- temperatures. As we know, the Avrami theory has been
morillonite acted as nuclear agent during the crystallizing widely and successfully used for the interpretation of iso-
process of PP. On the other hand, the width of the crystal- thermal crystallization processes[20]. The Avrami equation is:
lization peaks of PP=MMT composites was narrower than
1  Xt ¼ exp ðktn Þ ð3Þ
that of PP. The fact that the montmorillonite increased the
crystallization rate of PP visibly showed that the crystalli- where n is the exponent of Avrami which describe the type
zation of PP=MMT composites mainly began with a het- of nucleation and growth dimension; the parameter k is a
erogenous nucleation during crystallization process. This growth rate constant involving both nucleation and growth
result was consistent with Qi Zongneng’s study[19]. rate which is related to the crystallization temperature. Then
make Eq. (3) logarithmic operation:
3.3. Effect of the Montmorillonite on the Isothermal
Crystallization Kinetics of PP lnðlnð1  Xt ÞÞ ¼ lnk þ nlnt ð4Þ
At the definite crystallization temperature, the relative According to Eq. (4), it is clear that ln( ln(1  Xt)) is in
degree of crystallization Xt was calculated by the following linear relation with lnt, n, and lnk were known by the linear
equation: slope and intercept, respectively.
R Figure 4 shows the plot of ln( ln(1  Xt)) versus lnt for
Xt 0 ðdHc=dtÞdt
Xt ¼ ¼ R1 ð2Þ PP and PP=MMT composite at various crystallization tem-
X1 0 ðdHc=dtÞdt peratures. The values of n and k are shown in Table 2.
where Xt is the relative degree of crystallization, t is the According to the Avrami equation, the half crystallization
crystallization time, X1 is the relative degree of crystalliza- time was calculated:
tion at the end of crystallization, t0 and t1 are the crystal-
lization time at the start and the end of crystallization, t1=2 ¼ ½ðln2Þ=k1=n ð5Þ
respectively, dHc=dt is the rate of heat flow. With a time
integral of isothermal crystallizing DSC cures, the relation
of Xt with the crystallization time can be gained. The values of t1=2 were shown in Table 2.

FIG. 3. Plots of Xt versus t for crystallization of PP and PP=MMT.

988 G. MINGLIANG ET AL.

FIG. 4. Plots of ln( ln(1  Xt)) versus lnt for crystallization of Pure PP and PP=MMT (3 wt%).

According to Fig. 4, it is well known that the linear of PP after adding montmorillonite, but the nucleation
relation of ln( ln(1  Xt)) versus lnt was perfect during of montmorillonite was weakened and the crystallization
the crystallization processes, it was feasible to describe rate dropped with the crystallization temperature increa-
the isothermal crystallization kinetics of PP and PP=MMT sing. The value of t1=2 increased with increasing crystal-
MMT composites by the Avrami equation. According to lization temperatures for the PP=MMT composites. At a
the received data, the values of n varied from 1.5 to 2.5. given crystallization temperature, the value of t1=2 of the
The value of n of PP was 2.41 when the crystallization tem- PP=MMT composites was less than that of PP. It showed
perature was 129C, but when crystallization temperature that the montmorillonite acted as nucleating agent,
varied from 126 to 128C, the values of nof PP which increased the crystallization rate of PP.
hardly change were 1.8 approximately. On the one hand,
the value of n of PP=MMT composites was 1.69 when 3.4. Effect of the Montmorillonite on the Melting Point
the crystallization temperature was 126C and was very and the Crystallinity of PP
close to that of PP at the crystallization temperature from
Figure 5 showed the melting DSC curves of PP and
126 to 128C. On the other hand, when the crystallization
PP=MMT composites. The melting point (Tm), at various
temperature varied from 127 to 129C, the values of n of
crystallization temperature was measured according to
PP=MMT composites were close to that of PP at 129C.
the high peak of melting DSC curve and shown in
It showed that the addition of montmorillonite and the
Table 3. As seen from Table 3, the crystallization tem-
increasing of crystallization temperature had the similar
perature hardly affected the melting point of neat PP
effect on the value of n of the polymer. With the crystalliza-
and its melting points were approximately 162.7C at
tion temperature increasing, the values of k of PP did not
the various crystallization temperature. But the melting
vary evidently but the values of k of the PP=MMT compo-
point of the PP=MMT composites was related with the
sites decreased. This fact indicated that the crystallization
crystallization temperature. The melting point of the
temperature remarkably affected the crystallization process
PP=MMT composites crystallized at 126C was higher
than that at 127C. In addition, the melting point of
the PP=MMT composites crystallized at 127C, which
TABLE 2 was close to that at 128C. This indicated that the crys-
The crystallization parameters of pure PP and PP=MMT tallization temperature influenced on the melting point of
composites calculated from avrami equation the PP=MMT composites at definite crystallization tem-
Tc k
10 2 t1=2 perature rang. The melting point of PP=MMT compo-
Sample (C) n (min n) (min) sites was higher than that of neat PP at the same
crystallization temperature, the reason was that mont-
PP 126 1.86 6.79 3.49
morillonite could attract polymer molecular chains.
127 1.69 9.77 3.19
The degree of crystallization was calculated from the
128 1.99 6.71 3.23
heating DSC curves, the equation is shown as:[21]
129 2.41 1.17 5.44
PP=MMT 126 1.69 65 1.04 DH
Xc ¼
100% ð6Þ
127 2.10 35 1.39 ð1  uÞDH0
128 2.33 21 1.66 where Xc is the degree of crystallization; DH is the enthalpy
129 2.13 7 2.92 at a certain crystallization process; DH0 is the enthalpy
 CRYSTALLIZATION PROPERTIES OF POLYPROPYLENE COMPOSITES 989

FIG. 5. Heating DSC curves of PP and PP=MMT (3 wt%).

when PP entirely crystallize, its value is 187.7 J=g[22]. u is those of of PP. The addition of MMT leaded to the accel-
the weight percentage of montmorillonite. The values of eration of the crystallization rate of PP. So MMT was a
Xc of the neat PP and the PP=MMT composite were shown nucleation agent for PP, and the crystallization of PP=
in Table 3. According to Table 3, the values of Xc of the MMT composites mainly began with a heterogenous
neat PP was maximum at 127C, but the values of Xc of nucleation during the isothermal crystallization. At the
the PP=MMT composite was decreased with the crystalli- same crystallization temperature, because montmorillonite
zation temperature increasing because the interaction absorbed polymer molecular chains, the melting point of
between montmorillonite and polymer was lessened when PP=MMT composites was higher than that of neat PP.
crystallization temperature increased. At the same crystal- The degree of crystallization of the neat PP was less than
lization temperature, the value of Xc of the neat PP was less that of the PP=MMT composites at the same crystalliza-
than that of the PP=MMT composites, the reason was tion temperature. Montmorillonite attracted polymer chain
possibly that montmorillonite acted as nucleating agent and acted as nucleation agent so that the ratio of crystalli-
and attracted the polymer chain so that the ratio of crystal- zation of the PP matrix increased.
lization of the molecular chain increased. In addition, the
crystallization temperature at the maximal Xc of neat PP
is 127C but that of PP=MMT composites is 126C. This REFERENCES
showed that the addition of montmorillonite could reduce 1. Quazi, R.T.; Bhattacharya, S.N.; Kosior, E. The effect of dispersed
the optimum crystallization temperature of polymer. paint particles on the mechanical properties of rubber toughened
polypropylene composites. J. Mater. Sci. 1999, 34, 607–614.
2. Ito, T.; Suganuma, T.; Wakashima, K. Glass fiber=polypropylene
4. CONCLUSION composite laminates with negative coefficients of thermal expansion.
J. Mater. Sci. Lett. 1999, 18, 1363–1365.
The X-ray diffraction of PP and PP=MMT composites 3. Alonso, M.; Velasco, J.I.; de saja, J.A. Constrained crystallization and
showed that the addition of montmorillonite does not activity of filler in surface modified talc polypropylene composites. J.
affect the crystal structure of the PP matrix. The microcrys- Eur. Polymer 1997, 33 (3), 255–262.
talline dimension Lhkl of PP=MMT composites is less than 4. Tang, L.; Fang, Z.; Wang, J. Polypropylene toughened by thermoplas-
that of PP. The addition of montmorillonite could reduce tics polyurethane elastomer on-situ polymerized on the surface of talc.
Chin. Plast. 2000, 14 (11), 71–75.
the microcrystalline dimension of PP. Differential scan- 5. Rong, M.; Zhang, M.Q.; Zheng, Y.X. et al. Structure-property
ning calorimetry (DSC) reveal the shape and position of relationships of irradiation grafted nano-inorganic particle filled
crystallization peak of PP=MMT composites differ from polypropylene composites. Polymer 2001, 42, 167–183.
6. Rong, M.Z.; Zhang, M.Q.; Zheng, Y.X. et al. Improvement of tensile
properties of nano-SiO2=PP composites in relation to percolation
TABLE 3
mechanism. Polymer 2001, 43, 3301–3304.
The crystallization parameters of PP and PP=MMT 7. Chan, C-M.; Wu, J.; Li, J.-x. et al. Polypropylene=calcium carbonate
composites nanocomposites. Polymer 2002, 43, 2981–2992.
8. Saujanya, C.; Radhakrishnan, S. Structure development and crystalli-
Tc (C) Tm (C) Xc DH (J=g) zation behaviour of PP=nanoparticulate composite. Polymer 2001, 42,
PP 126 162.7 58.4 109.7 6723–6731.
9. Kaempfer, D.; Thomann, R.; Mulhaupt, R. Melt compounding of
127 162.6 62.6 117.4
syndiotactic polypropylene nanocomposites containing organophilic
128 162.9 51.1 96.5 layered silicates and in situ formed core=shell nanoparticles. Polymer
PP=MMT 126 177.5 75.1 134.3 2002, 43, 2909–2916.
127 165.7 65.5 119.3 10. Kurokawa, Y.; Yasuda, H.; Kashiwagi, M. et al. Structure and
properties of a montmorillonite=polypropylene nanocomposite. J.
128 165.9 55.1 98.6 Mater. Sci. Lett. 1997, 16, 1670–1672.
990 G. MINGLIANG ET AL.

11. Liu, X.; Wu, Q. PP=clay nanocomposites prepared by grafting-melt 17. Xu, W.B.; Ge, M.L.; He, P.S. Nonisothermal crystallization kinetics
intercalation. Polymer 2001, 42, 10013–10019. of polypropylene=montmorillonite nanocomposites. J. Polymer Sci.
12. Nam, P.H.; Maiti, P.; Okamoto, M. et al. A hierarchical structure and B. Polymer Phys., 2002, 40 (5), 408–414.
properties of intercalated polypropylene=clay nanocomposites. Poly- 18. Sakintuna, B.; Yurum, Y. Preparation and characterization of meso-
mer 2001, 42, 9633–9640. porous carbons using a Turkish natural zeolitic template=furfuryl
13. Zongneng, L.J.; ke.Y.Q. et al. Study on intercalation and exfoliation alcohol system. Microporous and Mesoporous Materials 2006,
behavior of organoclays in epoxy resin. J. Polymer Sci. B Polymer 93 (1–3), 304–312.
Phys. 2001, 39 (4), 115–120. 19. Ma, J.; Qi, Z.; Li, G. et al. Isothermal crystallization kinetics of poly-
14. Weibing, X.; Mingliang, G.; Pingsheng, H. Nonisothermal crystalliza- propylene=montmorillonite nanocomposites. Acta Polymerica Sinica
tion kinetics of polypropylene=montmorillonite nanocomposite. J. 2001, 5, 589–593.
Appl. Polymer Sci. 2001, 28 (9), 2281–2289. 20. Grady, B.P.; Genetti, W.B.; Lamirand, R.J. et al. An investigation of
15. Weibing, X.; Mingliang, G.; Pingsheng, H. Preparation and property heat transfer effects in isothermal crystallization studies of low-density
of polypropylene=montmorillonite nanocomposites. Chin. Plast. 2000, polyethylene. Polymer Eng. Sci. 2001, 41 (5), 820–829.
14 (11), 27–31. 21. Turi, E.A. Thermal Characterization of Polymeric Materials, Academ-
16. Francisco, J.; Rodriguez, M.-; Burger, C. et al. Time-resolved shear ic Press: New York, 1981.
behavior of end-tethered nylon 6-clay nanocomposites followed by 22. Lambrigger, M. Non-isothermal polymer crystallization kinetics and
non-isothermal crystallization. Polymer 2001, 42, 9015–9023. avrami master curves. Polymer Eng. Sci. 1998, 38 (4), 610–615.