Wissenschaftlicher
Arbeitskreis der
UniversitätsProfessoren der
Kunststofftechnik
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Zeitschrift Kunststofftechnik
Journal of Plastics Technology
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
archival, peer-reviewed online Journal of the Scientific Alliance of Polymer Technology
archivierte, peer-rezensierte Internetzeitschrift des Wissenschaftlichen Arbeitskreises Kunststofftechnik (WAK)
www.plasticseng.com, www.kunststofftech.com
handed in/eingereicht:
accepted/angenommen:
02.12.2008
14.02.2009
PhD. Maria Pilar Villanueva1, Dr. Luis Cabedo1, Dr. José María Lagarón2, Prof. Dr.
Enrique Giménez1
1
Area of Materials, Department of Industrial Systems Engineering and Design,
University Jaume I, Campus Riu Sec, 12071 Castellón, Spain
2
Novel Materials and Nanotechnology, Institute of Agrochemistry and Food Technology
(IATA-CSIC), Apdo. Correos 73, Burjassot 46100, Spain
Development of Novel LDPE Clay
Nanocomposites
LDPE composites/nanocomposites based on kaolinite and montmorillonite were prepared by melt
mixing the polymer with two novel commercial masterbatches containing these two different clays. The
morphological study showed that kaolinitic clay achieved a higher degree of dispersion/exfoliation
compared to montmorillonite. Kaolinite based nanocomposites presented also better thermal,
mechanical and oxygen barrier properties with respect to the sample with montmorillonite.
Entwicklung neuartiger LDPE-Nanocomposites
mit Tonmineralien
LDPE-Verbundwerkstoffe /-Nanocomposites auf Basis Kaolinit und Montmorillonit wurden
durch Mischen des Polymers mit zwei neuartigen kommerziellen Masterbatches, die diese
zwei verschiedene Tonmineralien enthalten, hergestellt. Gegenüber den Proben mit
Montmorillonit zeigten kaolinitbasierte Nanocomposites bessere thermische, mechanische
und Sauerstoffbarriereeigenschaften.
© Carl Hanser Verlag
Zeitschrift Kunststofftechnik / Journal of Plastics Technology 5 (2009) 3
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
Novel LDPE Clay Nanocomposites
Development of Novel LDPE Clay
Nanocomposites
M.P. Villanueva, L. Cabedo, J.M. Lagarón, E. Giménez
1
INTRODUCTION
Polyethylene (PE) is one of the most consumed polyolefin in the world and its
interest in the field of nanocomposites has increased in the last years due to the
improvements that may be obtained with low contents of layered silicates
(clays). The research in polyethylene nanocomposites obtained by the melt
processing method is a new approach to fabricate PE nanocomposites by the
conventional polymer processing techniques that are currently being used in the
industry [1-4].
The limitation of polyethylene is that does not have any polar group in its
backbone and is one of the most hydrophobic polymers, so the complete
exfoliation of clays (such as montmorillonite or kaolinite) in a polyolefinic matrix
in principle is not possible even by using organomodified clays. In order to solve
this problem many authors have attempted to use different polyolefinic
oligomers as compatibilizers having polar groups in the backbone [1,2,5-10].
Among all the compatibilizers used, one of the most commonly used in
polyethylene nanocomposites is the polyethylene grafted with maleic anhydride.
It has been reported that the content of polar functional groups in the oligomers
affects the miscibility with the neat polyethylene, and the final properties depend
on the type and content of compatibilizer added. The drawback of the use of
compatibilizers is the increment in the price of the final compound and also the
decrements in some of the original properties of neat polymer.
At present, the main efforts in polyethylene nanocomposites have been focused
on the development of polymer-clay nanocomposites with montmorillonitic
clays. In this work, our efforts are centered on the comparative development of
nanocomposites based on two different commercial masterbatches containing
montmorillonite and kaolinite. The use of kaolinites in polymeric nanocomposites was reported in matrices such as EVOH [11], nylon 6 [12,13] or
biodegradable polyesters [14,15]. However to the best of our knowledge, there
are not reports about the dispersion of a kaolinitic clay in a polyolefinic matrix.
Commercial masterbatches have been used previously to develop polyethylene
nanocomposites but in all the cases the masterbatches were based on
montmorillonitic [16,17]. This work reports for the first time the development and
characterization of polyethylene nanocomposites containing novel commercial
masterbatches based on montmorillonite and kaolinite. The morphology and
properties of kaolinite nanocomposite prepared by means of a kaolinite
Journal of Plastics Technology 5 (2009) 3
183
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
Novel LDPE Clay Nanocomposites
masterbatch will be compared with montmorillonite nanocomposite prepared by
the same method. The kaolinitic clay used to prepare the masterbatch was also
used to directly melt mix it with polyethylene in order to study the differences in
the morphology depending on the method used to add the clay: powder or
masterbatch.
Morphology of nanocomposites was analyzed by means of wide angle X-ray
scattering (WAXS), scanning electron microscopy (SEM) and transmission
electron microscopy (TEM). Mechanical, thermal and barrier properties were
also studied.
2
EXPERIMENTAL
2.1
Materials
The matrix used was a low density polyethylene supplied by Repsol YPF (LDPE,
Alcudia®PE-015) with a density of 0.92 g/cm3 and a melt flow index of 1g/10min.
A proprietary kaolinite masterbatch (MB-K, Nanobioter®D240B) and a
proprietary montmorillonite masterbatch (MB-MMT, Nanobioter®AE435) were
kindly supplied by NanoBioMatters, S.L. (Valencia, Spain). Both masterbatches
were prepared by the same method but no further details of their preparation
and composition were disclosed by the manufacturer. A natural kaolinite (K,
NanoBioter® D0) was also supplied as a powder in order to prepare
nanocomposites by direct melt mixing with polyethylene.
2.2
Preparation of polymer/clay nanocomposites
Nanocomposites were prepared by melt mixing the polyethylene and the
desired amount of the masterbatch (or clay) in an internal mixer (HaakeRheomix). Masterbatches were diluted into neat LDPE to achieve nanocomposites with approximately 7wt.-% of clay content (so-called LDPE/ MBMMT and LDPE/MB-K through the test). The nanocomposite prepared by melt
mixing the polyethylene with a 7wt.-% of kaolinite is cited in the test as LDPE/K.
Prior to mixing, the kaolinitic clay and the masterbatches were dried at 80ºC,
under vacuum for 24h, to remove moisture.
The samples were processed at a temperature of 140ºC and a rotor speed of
100 rpm for three minutes (none of the samples surpassed the temperature of
160ºC during the processing). A sample of LDPE was processed in the mixer at
the same conditions.
Sheets (~0.8mm of thickness) and films (~200µm of thickness) were prepared
at 150ºC by compression molding. These hot-pressed sheets and films were
quenched in water and were used to carry out the characterization of the
samples.
Journal of Plastics Technology 5 (2009) 3
184
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
2.3
Novel LDPE Clay Nanocomposites
Characterization techniques
Wide angle X-ray scattering experiments (WAXS) were performed using a
Bruker AXS D4 Endeavour diffractometer. Radial scans of intensity versus
scattering angle (2θ) were recorded at room temperature in the range 2-30º
(step size= 0.02º (2θ), scanning rate = 8s/step) with identical setting of the
instrument by using filtered CuKα radiation (λ = 1.54Å), an operating voltage of
40kV, and a filament current of 30mA. To calculate the clays d-spacing, Bragg´s
law (λ= 2d sinθ) was applied.
Scanning electron microscopy (SEM) experiments were developed to see the
dispersion of clay and to observe the adhesion to the polymer matrix. The
equipment used was a LEO 440i. A piece of a sheet from each sample was
cryofractured in liquid nitrogen. The samples were previously coated by
sputtering with Au-Pd and finally a conductive wire of colloidal Ag was applied.
The morphology of the sample LDPE/MB-K was also observed by transmission
electron microscopy (TEM) in a Jeol 1011. The sample was inserted in an
epoxy resin and was cut in ultrafine sections with an ultramicrotome.
Differential scanning calorimetry (DSC) experiments were recorded using a
Perkin-Elmer DSC7 calorimeter on approximately 10mg of material using argon
as the purging gas. The thermal program applied for all the samples was a
heating between 50ºC and 160ºC at 10ºC/min. Melting temperatures (Tm) and
melting enthalpies (ΔHm, normalized for the polymer content in the
nanocomposites) were calculated from the second heating step. Crystallization
temperatures (Tc) and crystallization enthalpies (ΔHc, normalized for the
polymer content in the nanocomposites) were also calculated in the cooling step
to see the effect of clay in the crystallization process.
Thermogravimetric analysis (TGA) were carried out in a TGA/SDTA 851e
Metter-Toledo at a heating scan of 10ºC/min from 25ºC to 900ºC. Experiments
were made in air atmosphere.
Tensile tests were performed using a universal testing machine (Instron 4469)
at a crosshead speed of 10mm/min at room temperature. Tests were carried out
according to ASTM D638 using films prepared by compression moulding of
approximately 200m of thickness.
Oxygen permeability of the sheets was measured with an Oxtran permeability
apparatus (OXTRAN 100A equipped with a DL-200 Data Logger, Mocon Inc.,
Minneapolis, MN) at 25ºC and 80% relative humidity provided by the
incorporated gas bubblers and monitored by a hygrometer.
Journal of Plastics Technology 5 (2009) 3
185
Novel LDPE Clay Nanocomposites
3
RESULTS AND DISCUSSION
3.1
Morphology
WAXS pattern of the montmorillonitic masterbatch MB-MMT is given in Figure
1. The (001) diffraction peak of the MMT is located at 6.4º (2θ), which is the
position of montmorillonite in its natural state (basal spacing of 1.4nm). When
the masterbatch based on this clay is compounded with LDPE, the diffraction
peak of MMT is observed at the same position, thus indicating that there is not
intercalation of polyethylene chains in the interlaminar region of the clay. The
lower intensity of the (001) peak in the sample LDPE/MB-MMT with respect to
the clay could be due to a worst stacking of the clay layers that are forming the
big aggregates dispersed in the polymer.
Figure 2 represents the diffraction pattern of the masterbatch based on kaolinite. The diffraction peak located at 12.4º (2θ) can be associated to the basal
diffraction (001) of the kaolinite, which corresponds to a d-spacing of 0.72nm.
Similar diffractograms were obtained for the systems LDPE/K and LDPE/MB-K
which means that kaolinite maintains its ordered structure after being mixed
with LDPE in form of powder or masterbatch. The diffraction peak around 9º(2θ)
belongs to illite, i.e. a residual mineral component of the kaolinitic clay used.
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
Figure 1: WAXS patterns of the montmorillonite masterbatch and the
LDPE/MB-MMT composite
Journal of Plastics Technology 5 (2009) 3
186
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
Novel LDPE Clay Nanocomposites
Figure 2: WAXS patterns of the kaolinite masterbatch, the LDPE/MB-K and the
LDPE/K composites
WAXS analysis of all the samples indicated mainly the presence of aggregated
structures. The affinity polyethylene-clay and the level of clay dispersion need to
be analyzed by means of other techniques such as the electron microscopy.
The dispersion of both types of clay into polyethylene was investigated by
scanning electron microscopy (SEM). The MMT masterbatch is badly dispersed
in LDPE due to the poor affinity between this highly polar clay and the
polyethylene. Figure 3 shows an aggregated/immiscible structure where the
MMT is distributed in big clusters of several micrometers (even more than
20m) as it is indicated by some circles.
The based kaolinite masterbatch is homogeneously dispersed in small tactoids
with thicknesses in the order of nanometers (<<1µm) and a high aspect ratio
(length/thickness) confirming that a nanocomposite is obtained (Figure 4). The
state of clay dispersion of kaolinite in the sample LDPE/MB-K is also compared
with the sample LDPE/K, composed of a kaolinitc clay added as a powder.
When the kaolinite is added as a powder directly to the molten polyethylene, an
aggregated/immiscible morphology is obtained (Figure 5), as in conventional
composites or microcomposites (see microaggregates of several µm indicated
by circles).
Journal of Plastics Technology 5 (2009) 3
187
Novel LDPE Clay Nanocomposites
Figure 3: SEM image of LDPE/MB-MMT (500x, scale 20m)
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
Figure 4: SEM image of LDPE/MB-K (10Kx, scale 1m)
Journal of Plastics Technology 5 (2009) 3
188
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
Novel LDPE Clay Nanocomposites
Figure 5: SEM image LDPE/K (500x, scale 20µm)
The morphology of the system LDPE/MB-K was also observed by transmission
electron microscopy (TEM). Figure 6 shows TEM pictures obtained at different
magnifications. Figure 6a shows an aggregated sctructure where small kaolinite
tactoids are homogeneously dispersed in the nanometer range. However,
intercalated structures (Figure 6b) and some delaminated clay layers around
the aggregates (Figure 6c) were also observed in this sample. The length of the
clay tactoids (L) was estimated to be between 150 and 250nm while the
thickness (T) varies in the wide range of 30-200nm.
Journal of Plastics Technology 5 (2009) 3
189
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
Novel LDPE Clay Nanocomposites
Figure 6: TEM pictures of the LDPE/MB-K nanocomposite:
a) 15K, scale 2000nm; b) 300K, scale 100nm; c) 100K, scale 200nm
3.2
Thermal properties
The melting and crystallization temperatures and the corresponding enthalpies
were calculated by DSC in order to determine the effect of the two clays in the
final crystallinity of the polyethylene (Table 1). In this study, the melting
temperature (Tm) of the LDPE matrix was not affected by the incorporation of
any of the clays. However, the values of crystallization temperature (Tc), and
enthalpies (ΔHf and ΔHc) showed dependence with the clay type and the
method used to add the filler (powder or masterbatch).
Journal of Plastics Technology 5 (2009) 3
190
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
Sample
Novel LDPE Clay Nanocomposites
Tm
ΔHm
Tc
ΔHc
(ºC)
(J/g)
(ºC)
(J/g)
LDPE
107.0
103.0
89.9
90.2
LDPE/K
106.3
102.9
91.3
86.3
LDPE/MB-K
106.7
107.8
91.6
91.8
LDPE/MB-MMT
106.3
99.9
90.3
86.6
Table 1:
Crystallization parameters calculated by DSC
The addition of montmorillonite induced a decrease of the melting and
crystallization enthalpies which may indicate that the big aggregates of clay
reduced the mobility of polymeric chains and therefore hinders the
crystallization of polyethylene chains. Kaolinite, added as a powder or as
masterbatch, increments slightly the crystallization temperature (Tc) possibly
caused by a nucleating effect of the kaolinite layers which show higher affinity to
polyethylene than montmorillonite. In the case of the kaolinite masterbatch, the
nanometric dispersion of the clay and the higher affinity between this clay and
the polymer support the increment in the enthalpies respect to neat polyethylene [11,15]. However, if the kaolinite is added directly as a powder, the
system behaves as a conventional composite, i.e. the enthalpies decrease with
respect to polyethylene.
The thermo-oxidative degradation of the filled samples was seen to be affected
by the level of clay dispersion. The TGA curves represented in Figure 7 show a
higher increment in the degradation temperature of the LDPE/MB-K nanocomposite. It is observed that with better clay dispersion, the temperature at
which the degradation starts is higher. The temperature at which 10% of the
total mass has been loss (T0.1) is higher for the system LDPE/MB-K
(nanocomposite) than for LDPE/MB-MMT and LDPE/K (microcomposites).
Table 2 shows the values of degradation temperatures, calculated as the
temperature at which 50% of the initial mass is lost, where it is showed that the
degradation is delayed 45ºC in LDPE/MB-K respect to neat LDPE. The
retardant effect in the degradation is attributed to the creation of a tortuous path
resulting from the clay dispersion slowing the diffusion of the oxidizing
substances in the material and to the formation of a carbonaceous protective
layer that acts as an insulator and slows the release of the volatile products
generated by the decomposition.
Journal of Plastics Technology 5 (2009) 3
191
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
Figure 7:
TGA curves of nanocomposites (air)
Sample
LDPE
LDPE/K
LDPE/MB-K
LDPE/MB-MMT
Table 2:
Novel LDPE Clay Nanocomposites
T0.1 (ºC)
T0.5 (ºC)
Residue (%)
343.6
376.3
0.74
357.6
400.6
5.96
364.6
421.6
5.60
348.3
409.3
4.55
Degradation temperatures of nanocomposites in air
The better dispersion of kaolinite obtained in the system LDPE/MB-K may help
to create a more consistent and stable layer, which is better for the heat barrier,
the barrier to oxygen and the barrier to volatile products from the degradation.
The same effect in the thermo-oxidative behaviour was reported previously
[4,18,19].
Journal of Plastics Technology 5 (2009) 3
192
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
3.3
Novel LDPE Clay Nanocomposites
Mechanical properties
Mechanical properties also showed the influence of dispersion level and clay
nature on the final properties of nanocomposites (Figure 8). Elastic modulus
(E), stress at break (σb) and elongation at break (εb) were calculated and
summarized in Table 3. The stress and deformation of the two yield points
observed are represented in Table 4.
Figure 8:
Stress-strain curves for pure polyethylene and its composites
containing 7% of clay.
Sample
LDPE
LDPE/K
LDPE/MB-K
LDPE/MB-MMT
Table 3:
E
σb
εb
(MPa)
(MPa)
(%)
109 (±12)
9.4 (±1.3)
353(±103)
144 (±6)
9.9 (±0.6)
301 (±82)
178 (±13)
11.1 (±0.3)
334 (±36)
220 (±5)
7.5 (±1.1)
56 (±13)
Mechanical parameters: elastic modulus (E), stress at break (σb) and
elongation at break (εb).
Journal of Plastics Technology 5 (2009) 3
193
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
Sample
Novel LDPE Clay Nanocomposites
1st yield
2nd yield
σ (MPa)
ε (%)
σ (MPa)
ε (%)
LDPE
6.1 (±0.1)
12.5 (±0.3)
7.9 (±0.2)
77 (±5)
LDPE/K
7.2 (±0.2)
11.5 (±0.7)
8.7 (±0.2)
55 (±10)
LDPE/MB-K
8.1 (±0.1)
13.5 (±0.8)
9.6 (±0.5)
65 (±15)
LDPE/MB-MMT
8.0 (±0.1)
11.5 (±0.2)
----
----
Table 4:
Stress and deformation at yield points
According to the elastic modulus values, there is an increase in the stiffness in
all the studied systems. Particularly, the composite containing montmorillonite
increases dramatically the elastic modulus but the balance of the tensile
properties is negative; there is a high reduction in the elongation at break as a
result of the micrometric aggregates that are acting as stress concentration
points during the deformation of the sample. On the other hand, there is a
reduction in the stress at break as the aggregates caused the breaking of the
tensile bars before the neck formation (second yield point). Decrements in the
tensile strength were reported previously and were correlated to the low
interphase interactions between polymer and clay [20]. However, the
nanocomposite LDPE/MB-K showed a better performance in the mechanical
properties compared to the system formed by the direct addition of kaolinite
powder or by the addition of montmorillonite masterbatch. LDPE/MB-K presents
a 63% of increment in the elastic modulus, moreover the increments in the yield
stress and the stress at break also indicate the reinforcing effect and the good
adhesion between polyethylene and kaolinite, which is in good agreement with
the results observed in the clay dispersion.
The new system LDPE/MB-K, based on a commercial kaolinite masterbatch,
presents a good balance in mechanical properties compared to the results
reported in previous studies about polyethylene nanocomposites, where the
improvements obtained were justified by the incorporation of montmorillonitic
clays and a high content of compatibilizer [17,21].
3.4
Oxygen permeability
Figure 9 shows the values of oxygen permeability for neat LDPE and for
composites with kaolinite and montmorillonite clays. The addition of both clays
in the commercial masterbatch form decreases the permeability to oxygen
Journal of Plastics Technology 5 (2009) 3
194
Novel LDPE Clay Nanocomposites
respect to unfilled LDPE, due to an increment in the tortuosity of the diffusion
path caused by the clay aggregates. The best oxygen barrier performance is
exerted by LDPE/MB-K, which shows a reduction in permeability of 31%, due to
the higher aspect ratio obtained. However, the increment in barrier with
montmorillonite is lower, only 20% respect to LDPE, most likely due to the
poorer dispersion observed in this sample.
These results indicate that the polymer-clay affinity, the dispersion of the clay
and the aspect ratio of the clay particles (aggregates) dispersed in the
polymeric matrix play an important role in improving the barrier properties.
Higher improvements in oxygen barrier were reported in polyethylene
nanocomposites formed by montmorillonites and compatibilizers due to the
higher clay aspect ratio obtained [20, 22, 23]. However, this work is presenting
an attempt to improve the barrier of polyethylene by means of a novel
masterbatch based on kaolinite without the addition of compatibilizers.
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
Figure 9: Permeability to oxygen
Journal of Plastics Technology 5 (2009) 3
195
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
4
Novel LDPE Clay Nanocomposites
CONCLUSIONS
This study demonstrates that the final properties of polyethylene-clay
nanocomposites are strongly dependent on the level of the dispersion and the
size of the clay aggregates. The final properties depend on the type of clay
used (kaolinite or montmorillonite) and on the method use to add the nanoclay
(powder or masterbatch). Although, a high degree of exfoliation is not obtained
in any of the cases, the kaolinite (a cheap and abundant mineral in nature),
seems to be a potential filler to improve mechanical properties (stiffness),
thermo-oxidative degradation and oxygen barrier of polyethylene, when it is
added in the form of a novel commercial masterbatch. The similar masterbatch
of montmorillonite does not show a good affinity with LDPE.
The nanocomposite formed by the incorporation of the masterbatch based on
kaolinite presents better balance in the final properties compared to the results
obtained previously with the addition of montmorillonites and high contents of
compatibilizers.
5
ACKNOWLEDGEMENTS
This study has been financially support by the project MEC MAT2006-10261C03-02. Authors would like to acknowledge to NanoBioMatters, S.L for
supplying the clay masterbatches. Authors would like to thank to SCIC of
University Jaume I and to Raquel Oliver and José Ortega for the experimental
support. Finally, M.P. Villanueva would like to thank to Generalitat Valenciana
for the FPI research grant awarded.
Journal of Plastics Technology 5 (2009) 3
196
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
6
[1]
[2]
[3]
Novel LDPE Clay Nanocomposites
References
Gopakumar, T.G;
Lee, J.A.;
Kontopoulou, M.;
Parent, J.S.
Influence of clay exfoliation on the physical
properties of montmorillonite/polyethylene
composites
Jacquelot, E;
Espuche, E;
Gerard, J.F.;
et al.
Morphology and gas barrier properties of
polyethylene-based nanocomposites
Liang, G.D.;
Xu, J.T.;
Bao, S.P.;
Xu, W.B.;
Polyethylene maleic anhydride grafted
polyethylene organic-montmorillonite
nanocomposites. I. Preparation,
microstructure, and mechanical properties
Polymer 43 (2002) p.5483
Journal of Polymer Science- Part B: Polymer
Physics 44 (2006) p.431
Journal of Applied Polymer and Science 91
(2004) 3974
[4]
Durmus, A.;
Woo, M.;
Kasgoz, A.;
et al.
Intercalated linear low density polyethylene
(LLDPE)/clay nanocomposites prepared
with oxidized polyethylene as a new type
compatibilizer: Structural, mechanical and
barrier properties
European Polymer Journal 43 (2007)
p.3737
[5]
[6]
[7]
Yang, H.M.;
Song, Y.H.;
Xu, B.;
Zheng, Q.;
Preparation of exfoliated low-density
polyethylene/montmorillonite
nanocomposites through melt extrusion
Morawiec, J.;
Pawlak, A.;
Slouf, M.;
et al.
Preparation and properties of compatibilized
LDPE/organomodified montmorillonite
nanocomposites
Lee, J.H.;
Jung, D.;
Hong, C.E.;
et al.
Properties of polyethylene-layered silicate
nanocomposites prepared by melt
intercalation with PP-g-MA compatibilizer
Chemical Research in Chinese Universities
22 (2006) p.383
European Polymer Journal 41 (2005)
p.1115
Composites Science and Technology 65
(2005) p.1996
Journal of Plastics Technology 5 (2009) 3
197
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
[8]
Hotta, S.;
Paul, D.R.
Novel LDPE Clay Nanocomposites
Nanocomposites formed from linear low
density polyethylene and organoclays
Polymer 45 (2004) p.7639
[9]
Shah, R.K.;
Krishnaswamy, R.K.;
Takahashi, S.;
Paul, D.R.
Blown films of nanocomposites prepared
from low density polyethylene and a sodium
ionomer of poly(ethylene-co-methacrylic
acid)
Polymer 47 (2006) 6187
[10]
Chrissopoulou, K.;
Altintzi, I.;
Anastasiadis, S.H.;
et al.
Controlling the miscibility of
polyethylene/layered silicate
nanocomposites by altering the polymer
surface interactions
Polymer 46 (2005) p.12440
[11]
[12]
[13]
[14]
[15]
Cabedo, L.;
Gimenez, E.;
Lagaron, J.M.;
et al.
Development of EVOH-kaolinite
nanocomposites
Itagaki, T.;
Matsumura, A.;
Kato, M.;
et al.
Preparation of kaolinite-nylon 6 composites
by blemdimg nylon6 and kaolinite-nylon6
intercalation compound
Matsumura, A.;
Komori, Y.;
Itagaki, T.;
et al.
Preparation of a kaolinite-nylon 6
intercaltion compound
Cabedo, L.;
Feijoo, J.L.;
Villanueva, M.P.;
et al.
Optimization of biodegradable
nanocomposites based on aPLA/PCL
blends for food packaging applications
Polymer 45 (2004) p.5233
Journal of Materials Science Letters 20
(2001) p.1483
Bulletin of the Chemical Society of Japan 74
(2001) p.1153
Macromolecular Symposia 233 (2006)
p.191
Sanchez-Garcia, M.D.; Morphology and barrier properties of
Gimenez, E.;
nanobiocomposites of poly(3Lagaron, J.M.
hydrixybutyrate) and layered silicates
Journal of Applied Polymer Science 108
(2008) p.2787
Journal of Plastics Technology 5 (2009) 3
198
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
[16]
Krook, M.;
Gallstedt, M.;
Hedenqvist, M.S.;
Novel LDPE Clay Nanocomposites
A study on montmorillonite/polyethylene
nanocomposites extrusion-coated
paperboard
Packaging Technology and Science 18
(2005) p.11
[17]
[18]
La Mantia, F.P.;
Dintcheva, N.T.;
Filippone, G .;
Acierno, D.
Structure and dynamics of polyethylene/clay
films
Stoeffler, K.;
Lafleur, P.G.;
Denault, J.
Effect of intercalating agents on clay
dispersion and thermal properties in
polyethylene/montmorillonite
nanocomposites
Journal of Applied Polymer Science 102
(2006) p.4749
Polymer Engineering and Science 48
(2008) p.1449
[19]
[20]
[21]
[22]
[23]
Zanetti, M.;
Bracco, P.;
Costa, L.
Thermal degradation behavior of PE/clay
nanocomposites
Zhong, Y.;
Janes, D.;
Zheng, Y.;
et al.
Mechanical and oxygen barrier properties of
organoclay-polyethylene nanocomposite
films
Kato, M.;
Okamoto, H.;
Hasegawa, N.;
et al.
Preparation and properties of polyethyleneclay hybrids
De Abreu, D.A.P.;
Losada, P.P.;
Angulo, I.;
Cruz, J.M.
Development of new polyolefin films with
nanoclays for application in food packaging
Arunvisut, S.;
Phummanee, S.;
Somwangthanaroj, A.
Effect of clay on mechanical and gas barrier
properties of blown film LDPE/clay
nanocomposites
Polymer Degradation and Stability 85
(2004) p.657
Polymer Engineering and Science 47
(2007) p.2239
Polymer Engineering and Science 43
(2003) p.1312
European Polymer Journal 43 (2007)
p.2229
Journal of Applied Polymer Science 106
(2007) p.2210
Journal of Plastics Technology 5 (2009) 3
199
© 2009 Carl Hanser Verlag, München
www.kunststofftech.com
Nicht zur Verwendung in Intranet- und Internet-Angeboten sowie elektronischen Verteilern.
Villanueva, Giménez et al.
Novel LDPE Clay Nanocomposites
Keywords:
polyethylene nanocomposite, clay masterbatches, kaolinite, thermal properties,
mechanical properties, oxygen barrier
Stichworte:
Polyethylen-Nanocomposites,
Ton-Masterbatches,
Kaolinit,
Eigenschaften, mechanische Eigenschaften, Sauerstoffbarriere
Author/Autor:
PhD. Maria Pilar Villanueva
Prof. Dr. Enrique Giménez
Department of Industrial Systems Engineering and Design
University Jaume I
Campus Riu Sec 12071 Castellón, Spain
Editor/Herausgeber:
Europe/Europa
Prof. Dr.-Ing. Dr. h.c. G. W. Ehrenstein, verantwortlich
Lehrstuhl für Kunststofftechnik
Universität Erlangen-Nürnberg
Am Weichselgarten 9
91058 Erlangen
Deutschland
Phone: +49/(0)9131/85 - 29703
Fax.:
+49/(0)9131/85 - 29709
E-Mail: [email protected]
Publisher/Verlag:
Carl-Hanser-Verlag
Jürgen Harth
Ltg. Online-Services & E-Commerce,
Fachbuchanzeigen und Elektronische Lizenzen
Kolbergerstrasse 22
81679 Muenchen
Phone.: 089/99 830 - 300
Fax: 089/99 830 - 156
E-mail: [email protected]
Journal of Plastics Technology 5 (2009) 3
thermische
E-Mail: [email protected]
Website: www.uji.es
Phone.: +34 964728212
Fax: +34 964728170
The Americas/Amerikas
Prof. Dr. Tim A. Osswald,
responsible
Polymer Engineering Center,
Director
University of Wisconsin-Madison
1513 University Avenue
Madison, WI 53706
USA
Phone: +1/608 263 9538
Fax.:
+1/608 265 2316
E-Mail: [email protected]
Editorial Board/Beirat:
Professoren des Wissenschaftlichen
Arbeitskreises Kunststofftechnik/
Professors of the Scientific Alliance
of Polymer Technology
200