Composites: Part B 38 (2007) 367–379

www.elsevier.com/locate/compositesb

The effect of silane treated- and untreated-talc on the mechanical

and physico-mechanical properties of poly(lactic acid)/newspaper
fibers/talc hybrid composites
M.S. Huda a, L.T. Drzal a, A.K. Mohanty b, M. Misra a,*

a
Composite Materials and Structures Center, 2100 Engineering Bldg. Michigan State University, East Lansing, MI 48824, USA
b
School of Packaging, 130 Packaging Bldg. Michigan State University, East Lansing, MI 48824, USA

Received 7 April 2006; accepted 16 June 2006

Available online 3 November 2006

Abstract

This paper evaluates the effect of the addition of silane treated- and untreated- talc as the fillers on the mechanical and physico-
mechanical properties of poly(lactic acid) (PLA)/recycled newspaper cellulose fibers (RNCF)/talc hybrid composites. For this purpose,
10 wt% of a talc with and without silane treatment were incorporated into PLA/RNCF (60 wt%/30 wt%) composites that were processed
by a micro-compounding and molding system. PLA is utilized is a bio-based polymer that made from dextrose, a derivative of corn. Talc
is also a natural product. The RNCF and talc hybrid reinforcements of PLA polymer matrix were targeted to design and engineer bio-
based composites of balanced properties with added advantages of cost benefits besides the eco-friendliness of all the components in the
composites. In this work, the flexural and impact properties of PLA/RNCF composites improved significantly with the addition of
10 wt% talc. The flexural and impact strength of these hybrid composites were found to be significantly higher than that made from either
PLA/RNCF. The hybrid composites showed improved properties such as flexural strength of 132 MPa and flexural modulus of
15.3 GPa, while the unhybridized PLA/RNCF based composites exhibited flexural strength and modulus values of 77 MPa and
6.7 GPa, respectively. The DMA storage modulus and the loss modulus of the PLA/RNCF hybrid composites were found to increase,
whereas the mechanical loss factor (tan delta) was found to decrease. The storage modulus increased with the addition of talc, because
the talc generated a stiffer interface in the polymer matrix. Differential scanning calorimetry (DSC) thermograms of neat PLA and of the
hybrid composites showed nearly the similar glass transition temperatures and melting temperatures. Scanning electron microscopy
(SEM) micrographs of the fracture surface of Notched Izod impact specimen of 10 wt% talc filled PLA/RNCF composite showed well
filler particle dispersion in the matrix and no large aggregates are present. The comparison data of mechanical properties among samples
filled with silane-treated- and untreated- talc fillers showed that the hybrid composites filled with silane treated talc displayed the better
mechanical prosperities relative to the other hybrid composites. Talc-filled RNCF-reinforced polypropylene (PP) hybrid composites were
also made in the same way that of PLA hybrid composites for a comparison. The PLA hybrid bio-based composites showed much
improvement in mechanical properties as compared to PP-based hybrid counterparts. This suggests that these PLA hybrid bio-based
composites have a potential to replace glass fibers in many applications that do not require very high load bearing capabilities and these
recycled newspaper cellulose fibers could be a good candidate reinforcement fiber of high performance hybrid biocomposites.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: A. Fibers; A. Thermoplastic resin; B. Thermomechanical; E. Extrusion

1. Introduction

Most paper in the U.S. is made from the natural fibers

found in wood called cellulose. Newspapers are one of the
*
Corresponding author. Tel.: +1 517 353 5466; fax: +1 517 432 1634. most collected materials in most community recycling
E-mail address: misraman@egr.msu.edu (M. Misra). programs [1]. It is increasingly recognized that recycled

1359-8368/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesb.2006.06.010
368 M.S. Huda et al. / Composites: Part B 38 (2007) 367–379
newspapers and used paper products constitute a valuable
source of fibers [1,2] as raw material for conversion into
high value composite materials, via dry processing methods,
especially since newspaper-reinforced plastic composites
can be process similarly to wood-based composites [2].
Research is being carried out on the potential use of cellu-
lose-based natural fibers as reinforcements for polymers,
since cellulose materials offer many advantages [1,2], such
as, low cost, biodegradability, abundant renewable source,
flexibility during processing, desirable fiber aspect ratio,
low density, and reduced wear of the processing machinery.
The mechanical properties of each specific natural fiber
reinforced composites may vary over a large range of values
because of the intrinsic variability of the properties of the
fibers. However, the incompatibility of the natural fibers
and the polymer matrix often reduce the potential of natu-
ral fibers to act as fillers and thus limit their usage. The
incorporation of talc as a filler in thermoplastics is a com-
mon practice in the plastics industry with the purpose of
reducing the production cost of molded products, but also
to improve the toughness, stiffness, and strength balance
[3–6]. This explains, in part, why this filler is widely used
in automobile and appliance applications [1,3,5–7]. How-
ever, the engineering community needs to improve the per-
formance of the composites through the more effective use
of available renewable resources. According to several
investigators [5–9], it is necessary to render the surfaces of
the mineral and polymer compatible, to optimize the rein-
forcing properties of minerals in plastics. Usually, coupling
agent acts by modifying the interfacial region between the
inorganic filler and the organic polymer to provide an
improved bonding between them. Coupling agents are
added to the surfaces of minerals [1,2,10,11] for improve-
ment of properties in fiber or particulate-filled composites
[12,13]. The most common used group of coupling agents
is the organofunctional silanes, which may be simplified
to the general formula of Y-M-OR, where Y is the organo-
functional group, M is the tetravalent base metal (Si or Zr)
and OR is a hydrolysable group (e.g. ethoxy for the silane-
based coupling agent). The surface modification of the filler
particles by silanes affects the rheology of the melt-filled
polymer by improving the dispersion of the particles
[10,12] and reducing the melt viscosity by acting as a lubri-
cant or surfactant. Further exploration on the efficacy of
hybrid fillers was done with the treatment of fillers with sur-
factants [8,9], which again yielded more promising results to
magnify the advantages of using hybrid fillers.
Recently, poly(lactic acid) (PLA) has attracted active
interest as a biodegradable material [14], since it is pro-
duced from lactic acid that can be generated by the biolog-
ical fermentation of renewable resources such as corn
starch [15]. Unfortunately, the physical properties of
PLA, such as brittleness, high rate of water permeation,
and water sensitivity make the PLA polymer unsuitable
for many packaging and appliance applications. However,
the properties of PLA can be changed by reinforcing it with
fibers, which enhances it’s mechanical and thermal stability
[16]. As such, PLA is finding increased use as a replacement
for petroleum-based polymers in the manufacture of pack-
aging materials and other products. Our earlier work on
biobased composites from recycled newspaper fibers
recommended its use as inexpensive biofibers for the pro-
duction of recycled newspaper cellulose fiber (RNCF)-rein-
forced plastic composites [17]. When the RNCF is used for
the manufacture of composites, it does not require exten-
sive preparation as well as this reduces the potential cost
of manufacturing [2]. These composites are similar to
wood-based composites [2,18,19] and have applications as
structural materials for the housing industry, such as load
bearing roof systems, sub flooring, and non-structural
products such as doors, furniture, and automotive parts.
The aim of this study was to develop talc filled RNCF-
reinforced PLA hybrid composites (PLA/Talc/RNCF:
60 wt%/10 wt%/30 wt%) by using a micro-compounding
and molding system and to study the mechanical and ther-
mal-mechanical properties of the resulting composites.
RNCF-reinforced polypropylene (PP) hybrid composites
were also processed with a recycled newspaper fiber con-
tent of 30 wt% and were compared to talc filled RNCF-
reinforced PLA hybrid composites. An investigation was
also carried out to determine the effect of silane treated-
and untreated-talc on the mechanical properties of the
PLA- and PP- based hybrid composites.
2. Materials and experimental procedures
2.1. Materials
Polypropylene (ProFax 6523, an injection molding
grade polypropylene with a melt flow index of 4.0 g/
10 min and weight average molecular weight of 470,000
with a polydispersity index of 5) was supplied by Basell
Polyolefins, Elkton, MD. Poly (lactic acid) (PLA; molecu-
lar weight, Mw: 220 kDa; Mn: 101 kDa) was obtained from
Biomer, Krailling, Germany (product name - Biomer L
9000). The recycled newspaper cellulose fibers (CreaMix
TC 1004) (RNCF) were supplied by CreaFill Fibers Corp.,
Chestertown, MD. The RNCF are reclaimed from newspa-
per/magazine or Kraft paper stock. TC 1004 fibers are sold
at less than $0.20/lb, a substantial cost savings over tradi-
tional reinforcements such as glass. The average length of
the recycled cellulose fibers was 850 lm and the average
width of fibers was 20 lm. The high cellulose content
(75% minimum) indicates that this is alpha cellulose with
maximum ash content of 23%. ‘‘Ash’’ is a combination of
carbon left after burning and any other organics/non-
organics (clays, inks lignin’s, tannin’s, extractives, etc.) that
are not volatilized after ignition. The moisture content of
the fibers was less than 5%. Three types of Talc (product
names - Silverline 002, Nicron 403 and Mistron CB) were
used as filler in our investigation. Luzenac America, Inc.
of Englewood, Colorado kindly supplied all talc samples.
The characteristics of the three types of talc are shown in
Table 1.
 M.S. Huda et al. / Composites: Part B 38 (2007) 367–379 369

Table 1 used to measure the flexural properties according to ASTM

Characteristics of the talc used in the present study D 790. System control and data analysis was performed
Talc 1 Talc 2 Talc 3 using Datum software.
Product name Silverline 002 Nicron 403 Mistron CB
Manufacturing company Luzenac Luzenac Luzenac 2.3.2. Dynamic mechanical analysis (DMA)
America, America, America,
The storage modulus, loss modulus, and loss factor (tan
Inc. Inc. Inc.
Particle Size (lm) 12.5 4.8 2.2 delta) of the composite specimen were measured as a func-
Density (lbs/ft3) 50 28 20 tion of temperature (20 to 100 °C for PLA based compos-
Surface area (m2/g) 10.5 12 11 ites and 50 to 150 °C for PP-based composites) using a
Crystalline character Micro- Micro- Micro- TA 2980 DMA equipped with a dual-cantilever bending
crystalline crystalline crystalline
fixture at a frequency of 1 Hz and a heating constant rate
talc talc talc
Chemically pre-treated No No Silane of 5 °C/min.
with surface modifier
Moisture content (%) 0.15 0.1 0.06 2.3.3. Differential scanning calorimeter (DSC)
The melting and crystallization behavior of the matrix
polymer and the composites were studied using a TA
2.2. Fabrication of the composites Instruments 2920 Modulated Differential Scanning Calo-
rimeter (DSC) equipped with a cooling attachment, under
Fig. 1 shows a schematic representation for fabricating a nitrogen atmosphere. The data were collected by heating
hybrid composite. The RNCF and PLA were both dried the composite specimen from 25 to 200 °C at a constant
at 80 °C for 24 h under vacuum (Lab-line, Squaroid-Duo- heating rate of 5 °C/min. A sample weight of approxi-
Vac-Oven, Melrose Park, IL) at 80 kPa and then stored mately 10 mg was used. The samples were sealed in alumi-
over desiccant in sealed containers prior to processing. num pans and the sealed samples were placed on a heating
By vacuum drying, moisture content of RNCF drops down surface in the furnace along with an empty reference alumi-
to 1–2%. The PP matrix, however, was not dried. The poly- num pan. The heat flow and energy changes in and out of
mer, RNCF and/or talc were extruded at 100 rpm with the samples in the sealed aluminum pans were recorded
a Micro 15 cc compounding system (DSM Research, with reference to an empty aluminum pan. The melting
Geleen, The Netherlands) at 183 °C for 10 min [17]. The temperature was obtained from the peak in the heating
extruder has a screw length 150 mm, a L/D of 18, and a curve. The determination of melting temperature of the
net capacity of 15 cm3. In order to obtain the desired spec- PLA-RNCF system helped to evaluate the processing tem-
imen samples for various measurements and analysis, the peratures that were needed on the extruder when natural
molten composite samples were transferred after extrusion fiber was added to the system to fabricate the composite.
through a preheated cylinder to a mini-injection molder,
which was pre-set with the desired temperature (injection 2.3.4. Scanning electron microscopy (SEM)
temperature at 183 °C) and cooling system (mold tempera- The morphology of impact fracture surfaces of the com-
ture at 40 °C). The injection-molded samples were placed in posites was observed by scanning electron microscope
sealed polyethylene bags in order to prevent moisture (SEM) at room temperature. A JEOL (model JSM-
absorption. 6300F) SEM with field emission gun and accelerating volt-
age of 10 kV was used to collect SEM images for the
2.3. Measurements composite specimen. A gold coating of a few nanometers
in thickness was coated on impact fracture surfaces. The
2.3.1. Mechanical properties samples were viewed perpendicular to the fractured
The notched Izod impact strength was measured with a surface.
Testing Machines Inc. (TMI) 43-02-01 Monitor/Impact
machine according to ASTM D256. All results presented 2.3.5. Rheological studies
are the average values of five measurements. A mechanical Dynamic measurements were carried out on Advanced
testing machine, United Calibration Corp., SFM 20, was Rheometric Expansion System (ARES) in the parallel-plate

Newspaper fibers Talc Hybrid composite

Fig. 1. Schematic representation for fabricating the hybrid composite: newspaper fibers and talc in polymer matrix.
370 M.S. Huda et al. / Composites: Part B 38 (2007) 367–379

arrangement with 25 mm plate. The sample used in this Table 3

study was fabricated in a disk with 2 mm in thickness. Flexural properties of the composites
Polymer/fiber or filler Flexural Flexural Improvement
(wt%) strength modulus (modulus)
3. Results and discussions (MPa) (GPa) (%)
Neat PLA 98.8 ± 1.0 3.3 ± 0.1 –
3.1. Mechanical properties PLA/Newspaper 77.7 ± 4.6 6.7 ± 0.1 103
(70/30)
3.1.1. Notched Izod impact resistance of the composites PLA/Newspaper/ 116.0 ± 0.9 12.3 ± 0.2 273
Talc 1 (60/30/10)
The notched Izod impact strength results for the tested
PLA/Newspaper/ 113.3 ± 3.2 12.5 ± 0.5 278
materials are shown in Table 2. The impact properties of Talc 2 (60/30/10)
both PLA- and PP-based composites improved in the pres- PLA/Newspaper/ 132.6 ± 2.1 15.3 ± 0.3 363
ence of talc and RNCF (as seen in Table 2), where an inter- Talc 3
esting development is seen in the relation between stiffness Neat PP 32.9 ± 1.8 1.5 ± 0.2 –
PP/Newspaper 39.8 ± 0.7 2.1 ± 0.2 46
and impact strength. The general trend towards an increase
(70/30)
in impact strength with the incorporation of talc is in agree- PP/Newspaper/Talc 1 57.7 ± 0.4 4.7 ± 0.3 213
ment with the report made by Velasco et al. [4]. Silane trea- (60/30/10)
ted talc showed greater improvement compared to those of PP/Newspaper/Talc 2 51.6 ± 2.4 4.0 ± 0.9 166
untreated talc in the case of PLA-based composites. It (60/30/10)
PP/Newspaper/Talc 3 59.2 ± 1.9 5.1 ± 0.5 233
appears that improved filler-matrix adhesion favored the
(60/30/10)
impact property of the RNCF reinforced talc filled both
PLA- and PP-based composites. Since the impact strength
of the composites tends to increase with the decrease of notably higher due to the effects of ‘hybridization’. This
average particle size and uniform dispersion in matrix, ‘hybridization’ effect could not have happened in single-
silane treated talc might help to increase the impact filler composites [21]. Both PLA- and PP-based hybrid
strength of the hybrid composite. Toughness is the major composites seemed to have better flexural properties com-
factor that controls the impact strength. Generally, the pared to the single-filler composites and even neat PLA
toughness of short fiber reinforced composites can be influ- or PP [21,22]. It seems that talc would act as the main rein-
enced by a number of factors such as the matrix intrinsic forcing filler in the composite [3,4,11]. For the presence of
properties, fiber volume fraction and interfacial bond silane treated talc, the flexural modulus of the composite
strength [9,11,20]. Sahu and Broutman suggested that high increased significantly, which indicates material stiffness
filler/matrix interfacial adhesion provides effective resis- increases for all the PLA- and PP-based hybrid composites.
tance to crack propagation during impact test [20]. The flexural modulus of the hybrid composite containing
Talc 3 (i.e., the silane treated talc) was significantly higher
3.1.2. Flexural properties of the composites than those containing either Talc 1 or Talc 2. Generally,
The flexural properties of the exposed samples are organosilane coupling agents can minimize the incompati-
shown in Table 3. The both flexural strength and flexural bility between the polymer matrix and the filler by improv-
modulus of all PLA- and PP-based hybrid composites were ing interaction at the polymer/mineral interface. Based on
these results, it is apparent that the addition of silane trea-
ted talc to the RNCF reinforced PLA- or PP-composites
Table 2
Notched Izod impact properties of the composites improves the interaction at the polymer/talc interphase,
and thus improve the mechanical properties of the compos-
Polymer/fiber or filler Notched Izod impact Improvement
(wt%) strength (J/m) (%) ites [5,7,8].
Neat PLA 25.7 ± 1.3 –
PLA/Newspaper (70/30) 13.1 ± 1.1 No 3.2. Thermo-mechanical properties
PLA/Newspaper/Talc 1 24.6 ± 2.6 No
(60/30/10)
3.2.1. Cystallization and melting behavior of the composites
PLA/Newspaper/Talc 26.1 ± 3.8 1.6
2 (60/30/10) The thermal properties of neat polymer and polymer/
PLA/Newspaper/Talc 26.3 ± 1.1 2.3 fiber or filler composites were investigated via DSC (in
3 (60/30/10) Fig. 2). The glass transition temperature (Tg), crystalliza-
Neat PP 29.7 ± 3.1 – tion temperature (Tc), melting temperature (Tm), crystalli-
PP/Newspaper (70/30) 31.2 ± 1.4 5
zation enthalpy (DHc) and melting enthalpy (DHm)
PP/Newspaper/Talc 1 35.0 ± 1.8 17
(60/30/10) obtained from the DSC studies are summarized in Table
PP/Newspaper/Talc 2 34.9 ± 2.6 17 4. Using literature reference values for the PLA and PP
(60/30/10) melting enthalpies, under the assumption that the polymer
PP/Newspaper/Talc 3 33.8 ± 0.9 13 is purely crystalline, it was possible to obtain the degree of
(60/30/10)
crystallinity (v%) in the composite, v ¼ DH m =DH 0m  100;
 M.S. Huda et al. / Composites: Part B 38 (2007) 367–379 371

(iv) properties to hard and tough properties [25]. The melting

enthalpy, crystallization enthalpy, and crystallization tem-
perature of the PLA/RNCF composites decreased in the
(iii) presence of RNCF. In this study, the crystallization tem-
perature of the RNCF-reinforced composite decreases by
(ii) up to 6 °C, which signifies that the fibers hinder the migra-
tion and diffusion of PLA molecular chains to the surface
(i)

0 50 100 150 200 18000

Temperature (ºC) (e)
16000

Storage Modulus (MPa)

14000
(iv) 12000 (d)
(iii)
10000 (c))
8000
(b))
(ii) 6000
4000
(i)
2000 (a)
0
10 20 30 40 50 60 70 80 90
-70 -20 30 80 130 180 230
Temperature (ºC) Temperature (ºC)

Fig. 2. DSC thermograms: (A) PLA and PLA-based composites: (i) neat 3500
PLA, (ii) PLA/Talc (70/30), (iii) PLA/Newspaper (70/30), (iv) PLA/
Newspaper/Talc 1 (60/30/10), and (B) PP and PP-based composites: 3000
(e)
(i) neat PP, (ii) PP/Newspaper (70/30), (iii) PP/Talc (70/30), (iv) PP/
Loss Modulus (MPa)

Newspaper/Talc 1 (60/30/10). 2500 (c)

2000 (d)
Table 4 1500 (b)
Thermal properties of neat polymer and polymer/fiber or filler composites
Polymer/fiber or filler Tg Tc DHc DHm v Tm 1000
(wt%) (°C) (°C) (J/g) (J/g) (%) (°C)
(a)
500
Neat PLA 54 96 27.8 47.9 51.1 172
PLA/Newspaper 55 90 23.6 41.2 44.0 172 0
(70/30) 0 10
0 2
20 30 40
0 50
5 60 70
0 80
8 90
0
PLA/Talc 1 (70/30) 56 82 19.7 45.5 48.5 169
Temperature (ºC)
PLA/Newspaper/Talc 1 58 82 16.3 32.6 34.8 169
(60/30/10)
2.5
PLA/Talc 3 (70/30) 57 84 16.6 38.3 40.8 170
PLA/Newspaper/Talc 3 57 81 14.1 30.3 32.3 170
(60/30/10) 2.0 (a)
Neat PP 10 115 84.1 77.7 51.8 153
PP/Newspaper (70/30) 1.8 126 59.6 47.5 31.6 167 1.5
(b)
Tan Delta

PP/Talc 1 (70/30) 9.9 129 57.9 47.6 31.7 167

PP/Newspaper/Talc 1 2.1 126 57.8 45.5 30.4 167 (c)
1.0
(60/30/10)
(e)
0.5

where: DHm = experimental melting enthalpy (J/g) and (d)

0.0
DH 0m ¼ melting enthalpy of a pure crystalline matrix,
PLA (93.7 J/g) [23] and PP (137.9 J/g) [24]. 10 20 30 40 50 60 70 80 90 100
From Table 4, it can be seen that the Tg and Tm of the Temperature (ºC)
composites do not change significantly with the addition of
Fig. 3. Temperature dependence of (A) storage modulus, (B) loss
RNCF fibers to the PLA matrix. Talc filled PLA hybrid
modulus, and (C) Tan delta of PLA and PLA based composites: (a) neat
composite, however, do exhibit an increase in Tg compared PLA (—), (b) PLA/Newspaper (70/30) ðOÞ, (c) PLA/Newspaper/Talc 1
to neat PLA. These observations indicate that a higher Tg (60/30/10) ( ), (d) PLA/Newspaper/Talc 2 (60/30/10) (n), and (e) PLA/
consequently promotes a change from soft and flexible Newspaper/Talc 3 (60/30/10) (s).
372 M.S. Huda et al. / Composites: Part B 38 (2007) 367–379
Table 5
The dynamic mechanical properties of the PLA and PLA-based composites
Polymer/fiber or Tg (°C) (obtained from Storage modulus
filler (wt%) loss modulus curves) (GPa) at 25 °C
Neat PLA 63 3.2
PLA/Newspaper 66 8.9
(70/30)
PLA/Newspaper/ 69 14.0
Talc 1 (60/30/10)
PLA/Newspaper/ 70 13.9
Talc 2 (60/30/10)
PLA/Newspaper/ 68 15.9
Talc 3 (60/30/10)
of the nucleus in the composite. Similar results were
obtained in the case of PLA/Talc (70/30) composite. The
crystallinity was found to decrease as a result of the addi-
tion of talc. The presence of talc resulted in an approxi-
mately 14 °C decrease the value of Tc [25–27]. Similar
results were obtained in the case of talc filled PLA hybrid
composite. It is obvious that the decrease of crystallinity
helps to increase the impact strength of the hybrid compos-
ite, since the flexibility of molecular chains declines for
increasing the crystallinity [25,26].
The effect of the RNCF on the thermal properties of PP
has also been analyzed in DSC experiments. The results are
reported in Table 4. The dynamic crystallization behavior
shows a positive effect from the RNCF on the crystalliza-
tion behavior of PP. A marked increase of the crystalliza-
tion temperature can be observed when the RNCF are
incorporated in the homopolymer matrix. The melting
enthalpy and crystallization enthalpy decreased with the
addition of RNCF when compare with neat PP. Similar
results were obtained in the case of PP/Talc 1 (70/30) com-
posite, though Tg remains consistent with neat PP. In the
presence of RNCF, the Tg, Tm, and Tc did not remain con-
sistent with neat PP. These results suggest that the RNCF
significantly affects the crystallization kinetics of the PP
matrix. The data obtained are in agreement with the results
of Joseph et al. [24], where the nucleating effect of cellulose
fibers on the crystallization rate of PP was demonstrated.
Moreover, these observations indicate that a higher Tg con-
sequently promotes a change from soft and flexible proper-
ties to hard and tough [4].
3.2.2. Dynamic mechanical properties
Fig. 3 shows the temperature dependence of dynamic
storage modulus, loss modulus, and tan delta of the PLA
and PLA-based composites. As seen in Fig. 3A, the storage
modulus of PLA based composites is higher than that of
the unfilled PLA matrix; which indicates that stress transfer
from the matrix to the fiber [28]. Since the talc is a stiffer
material than the PLA, the storage moduli are always
higher when talc is incorporated, and this trend is observed
for all the hybrid composites (Table 5). Furthermore, the
presence of talc produces a more rigid interface in the
PLA matrix. The interface will be even stiffer if the talc is
Storage modulus Storage modulus Reinforcement imparted by the
(GPa) at 40 °C (GPa) at 60 °C fibers at 25 °C (modulus) (%)
3.1 1.8 –
8.6 6.7 178
13.6 12.2 337
13.6 12.8 334
15.4 13.7 396
a treated one [3,4]. So, the silane-treated talc-filled RNCF
reinforced composites have a higher modulus than the
other composites.
Loss modulus for the talc-filled RNCF reinforced PLA
hybrid composites and the neat PLA have been plotted
as a function of temperature (see Fig. 3B and Table 5).
The maximum heat dissipation occurs at the temperature
where loss modulus is maximum, indicating the glass tran-
sition temperature (Tg) of the system [29]. The glass transi-
tion is assigned to the energy dissipation possibilities across
the free amorphous phase [29], and the lower Tg values
would mean an easier mobility of the free amorphous
phase in the composites. The Tg of all the composites
shifted to higher temperatures when the fiber was present
in the PLA matrix. This trend is associated with the
decreased mobility of the matrix chains, due to the pres-
ence of the fibers. Furthermore, the stress field surrounding
the particles induces the shift in Tg. It can be also seen from
Fig. 3B that the most pronounced effect of the fiber has
been the broadening of the transition region of the PLA
composites that contain 30 wt% fiber along with 10 wt%
talc, specifically in the case of silane treated talc.
Fig. 3C shows that the height of the tan delta peak of the
PLA based composites containing talc were all lower than
that of the PLA composite without talc, and much lower
than that of neat PLA. One possible explanation is that
there is no restriction to the chain motion in the case of
neat PLA matrix, while the presence of the cellulose fibers
hinders the chain mobility, resulting in the reduction of
sharpness and height of the tan delta peak [30]. Moreover,
the damping in the transition region measures the imper-
fection in the elasticity and that much of the energy used
to deform a material during DMA testing is dissipated
directly into heat [31]. Hence, the molecular mobility of
the composites decreased and the mechanical loss to over-
come intermolecular chain friction was reduced after add-
ing the RNCF fibers and talc.
The effects of temperature on the thermo-mechanical
properties of talc-filled RNCF-reinforced PP hybrid com-
posites were also studied by DMA (Table 5). In Fig. 4A
and Table 6, the storage modulus of the PP matrix
decreased with increasing temperature due to an increase
in the segmental mobility. Both PP/RNCF composite
 M.S. Huda et al. / Composites: Part B 38 (2007) 367–379 373

16000 [32]. Fig. 4A shows that the storage modulus of all compos-
(e)
14000
ites decreased with increasing temperature. The reduction
Storage Modulus (MPa)

(d) of modulus is associated with softening of the matrix at

12000 (c)
higher temperatures [33]. It is evident from Fig. 4B that
10000 (b) after the addition of newspaper fibers to the PP matrix,
8000 the loss modulus increases with fiber loading, and then
decreasing. It can be also seen from Fig. 4B that the silane
6000 (a) treated talc filled PP/RNCF hybrid composite showed
4000 most pronounced effect of the fiber and talc, where the
2000 broadening of the transition region of the PP/RNCF
hybrid was observed.
0
Fig. 4C shows that the tan delta values of the PP/RNCF
-80 -60 -40 -20 0 20 40 60 80 100 120 140 160 composites are slightly lower than those for the PP matrix
Temperature (ºC) at low temperatures. As reported by Murayama [34],
damping is affected through the incorporation of fibers in
800 (e) a composite system due to shear stress concentrations at
700 (c) the fiber ends in association with the additional viscoelastic
(d) energy dissipation in the matrix material. Here, the tan
Loss Modulus (MPa)

600
delta peak can be related to the impact resistance of a
500 (b) material. As seen in Fig. 4C, incorporation of fibers as well
as talc reduces the tan delta peak height by restricting the
400
movement of the PP polymer molecules. Since the filler sur-
300 face interacts with the polymer through catalytic activity
200 (a) and orientation of molecular segments, any modification
of the filler surface may lead to a change of the nucleation
100
kinetics of PP [35]. Therefore, one important function of
0 filler treatments by silane is to promote alignment of
-60 -40 -20 0 20 40 60 80 100
molecular segments of thermoplastic polymers.
Temperature (ºC)
3.2.3. Dynamic rheology of the composites
0.18 Fig. 5(A) shows the complex viscosity of the PLA based
0.16 composites. Here, dynamic frequency sweep experiments
0.14 (where strain is controlled and stress is measured) were
(e)
done for comparison purpose for PLA based composites.
0.12
The complex viscosity decreases as frequency increases in
Tan Delta

0.10 (a)
both PLA-based composites. The low viscosity of PLA
0.08 may be the reason for the polymer aggregation at the inter-
(b)
0.06 face. Generally, during the fiber–fiber interaction, the vis-
(c)
0.04
cosity are lower, thus the viscous heat generation is also
lower, giving rise to lower melt temperature.
0.02 (d) Fig. 5(B) shows the complex viscosity of the PP-based
0.00 composites, where dynamic frequency sweep experiments
-80 -40 0 40 80 120 160
Temperature (ºC)
(where strain is controlled and stress is measured) were
done for comparison purpose for PP-based composites.
Fig. 4. Temperature dependence of (A) storage modulus, (B) loss The viscosity is increased for the presence of fibers and Talc
modulus, and (C) Tan delta of PP and PP-based composites: (a) neat and decreased with increasing frequency. The additions of
PP (—), (b) PP/Newspaper (70/30) (,), (c) PP/Newspaper/Talc 1 (60/30/
10) ( ), (d) PP/Newspaper/Talc 2 (60/30/10) (n), and (e) PP/Newspaper/
fibers to a polymer melt acts in its influence on viscosity
Talc 3 (60/30/10) (s). like a reduction in temperature in the melt. This supports
the idea that the enhanced viscosity is due to increased vis-
cous dissipation in the matrix.
and talc-filled RNCF-reinforced PP hybrid composites Fig. 6 shows the storage modulus, loss modulus and tan
showed a greater storage modulus than neat PP, due to (delta) with frequency for comparison purpose for PLA
the reinforcement imparted by the cellulose fibers, which based composites. At low frequencies, the qualitative
allowed stress transfer from the matrix to the cellulose fiber behavior of storage modulus increase for the presence of
[28]. Storage modulus values of PP matrix and its compos- fibers and talc, whereas at high frequencies, the qualitative
ite are not the same at low temperature, because the fibers behavior of storage modulus decrease when compare with
impart stiffness to the composite in this temperature region neat PLA. It can be seen that tan (delta) decreased for
374 M.S. Huda et al. / Composites: Part B 38 (2007) 367–379

Table 6
The dynamic mechanical properties of the PP and PP-based composites
Polymer/fiber or filler Tg (°C) (obtained from Storage modulus Storage modulus Storage modulus Reinforcement imparted by the
(wt%) loss modulus curves) (GPa) at 25 °C (GPa) at 40 °C (GPa) at 60 °C fibers at 25 °C (modulus) (%)
Neat PP 13 3.3 2.4 1.4 –
PP/Newspaper (70/30) 7 5.6 4.4 3.1 69
PP/Newspaper/Talc 1 14 7.5 6.0 4.3 127
(60/30/10)
PP/Newspaper/Talc 2 15 7.7 6.2 4.4 133
(60/30/10)
PP/Newspaper/Talc 3 16 7.9 5.9 3.8 139
(60/30/10)

5 frequencies. Here, tan (delta) represents higher melt elastic-

10 60% PLA / 30% Newspaper /
10% Talc (iii)
ity. It can be seen that tan (delta) decreased for the pres-
100% PLA (i) ence of fiber, indicating an increase in melt elasticity.
Complex Viscosity (Pa.s))

70% PLA / 30% Newspaper fiber (iii)

4
10 3.2.4. Thermogravimetrical studies of the composites
The thermal stability of talc filled RNCF reinforced
(i)
PLA hybrid composites were investigated with thermo-
(ii) gravimetric analysis. In Table 7, the 5, 25, 50, and 75%
3
10 (iii) weight-loss temperatures (T5, T25, T50, and T75, respec-
tively) are listed for all specimens shown in Fig. 8. The
TGA curves given in Fig. 8 show the thermal stability of
2
the hybrid composites. As seen in Fig. 8 and Table 7,
10 approximately 0.7% and 0.5% weight-loss were observed
0 1 2 3
10 10 10 10
Frequency (rad/sec) at 150 °C for the composites of PLA/Newspaper/Talc 1
and PLA/Newspaper/Talc 3, respectively. In addition,
6
10 60% PP / 30% Newspaper / 2.6% and 2% weight-loss were observed at 300 °C for the
10% Talc (iii) composites of PLA/Newspaper/Talc 1 and PLA/Newspa-
100% PP (i) per/Talc 3, respectively. TGA was performed on the neat
Complex Viscosity (Pa.s)

70% PP / 30% Newspaper (ii) RNCF and the RNCF degraded in three stages. The first
5
10 stage at from 40 to 130 °C was due to the release of
absorbed moisture in the fibers, even after the 24 h of dry-
ing was conducted to eliminate moisture. The second tran-
4
sition (the temperature range of the decomposition was
10
(iii)
from 195 to 360 °C) was related to the degradation of cel-
lulosic substances such as hemicellulose and cellulose. The
(ii)
third stage (360 to 469 °C) of the decomposition was due to
(i)
3 the degradation of non-cellulosic materials in the fibers.
10
10
0
10
1
10
2
10
3 The thermal stabilities of composites with the same RNCF
Frequency (rad/sec) content is in the order PLA/Newspaper (70/30) > PLA/
Newspaper/Talc 1 (60/30/10) > PLA/Newspaper/Talc 3
Fig. 5. Comparison of complex viscosities for (A) PLA- and (B) PP-based
(60/30/10). Generally, most of the cellulose fiber decom-
composites.
poses at a temperature of 350 °C, and the thermal stability
of the composite materials increases with fiber content [36].
the presence of fiber and talc, indicating an increase in melt
elasticity. Usually, high viscosity resins may have a prob- 3.3. Morphology of the composites
lem wetting out completely for composite with heavy fiber
reinforcement. The viscosity controls the speed of wet-out Fig. 9 shows the morphology of the talc investigated by
(saturation) of the fibers. Since the viscosity varies inversely SEM. Talc 1 and Talc 2 showed that many small talc plates
with the fiber length, in each subsequent extrusion, the vis- are clustered together. In Talc 3, there are platy microcrys-
cosity of the medium decreases. talline talc surface that treated with silane coupling agent.
Fig. 7 shows the storage modulus, loss modulus and tan SEM micrographs of the impact fracture surfaces of the
(delta) with frequency for comparison purpose for PP- PLA/Newspaper/Talc 1 composite are represented in
based composites. The moduli of the fiber reinforced com- Fig. 10. These micrographs illustrate the well dispersion
posites increases for the presence of fibers and talc at all of fibers in the PLA matrix. Fig. 10 also indicates that
 M.S. Huda et al. / Composites: Part B 38 (2007) 367–379 375

7 7
Storage (Elastic) Modulus (dyn/cm2) 10 100% PLA (i) 10
70% PLA / 30% Newspaper Fibers (ii)

Storage (Elastic) Modulus (dyn/cm )

2
10
6 60% PLA / 30% Newspaper Fibers /
10% Talc (iii) (i) 10
6

5 (ii)
10
(iii)
4 5
10 10
(iii)
10
3
(ii)
4
60% PP / 30% Newspaper/
10 (i) 10% Talc (iii)
2
10 100% PP (i)
70% PP / 30% Newspaper (ii)
3
10
0
10
1
10
2
10
3 10
0 1 2 3
10 10 10 10
Frequency (rad/sec)
Frequency (rad/sec)
7
10 7
10
Loss (Viscous) Modulus (dyn/cm2)

Loss (Viscous) Modulus (dyn/cm )

10 (i)

2
(ii) 6
5 (iii) 10
10

10
4
5
(iii)
10 (ii)
3
10 100% PLA (i) (i)
70% PLA / 30% Newspaper Fibers (ii) 4
60% PP / 30% Newspaper /
2
60% PLA / 30% Newspaper Fibers / 10 10% Talc (iii)
10
10% Talc (iii) 100% PP (i)
70% PP / 30% Newspaper (ii)
0 1 2 3
10 10 10 10 10
3
0 1 2 3
Frequency (rad/sec) 10 10 10 10

3
Frequency (rad/sec)
10 1
10
100% PLA (i)
70% PLA / 30% Newspaper Fibers (ii)
2
10 60% PLA / 30% Newspaper Fibers /
10% Talc (iii)
Tan (delta)

Tan (delta)

1
10 0
(iii) 10 (iii)
(ii) (i)
(i) (ii)
0
10 60% PP / 30% Newspaper /
10% Talc (iii)
100% PP (i)
0 1 2 3
70% PP / 30% Newspaper (ii)
10 10 10 10 -1
10
-1 0 1 2 3
Frequency (rad/sec) 10 10 10 10 10
Frequency (rad/sec)
Fig. 6. Temperature dependence of (A) storage modulus, (B) loss
modulus, and (C) Tan delta of PLA and PLA based composites: neat Fig. 7. Temperature dependence of (A) storage modulus, (B) loss
PLA (—), PLA/Newspaper (70/30) (- - -), and PLA/Newspaper/Talc 1 (60/ modulus, and (C) Tan delta of PP and PP-based composites: neat
30/10) (- Æ -). PP (—), PP/Newspaper (70/30) (- - -), and PP/Newspaper/Talc 1 (60/30/
10) (- Æ -).

the fibers have been separated during the extrusion process,

and closer observation of the micrograph (in Fig. 10B) this organization is thought to induce a preferential orien-
shows good fiber-matrix adhesion. Fig. 11 shows the exis- tation in the morphology of PP-based hybrid composite.
tence of the aggregation of the cellulose fiber like materials SEM micrographs of the impact fracture surfaces of the
in the PP/Newspaper/Talc 1 composite sample surface. silane treated talc-reinforced composites are represented in
Some fibers are tightly connected with the matrix, whilst Figs. 12 and 13. Fig. 12 shows that the surfaces of the fibers
other fibers are fractured and/or broken. In Fig. 11, the are covered with layers of the matrix and talc, which effec-
plates of talc particles are dispersed over the surface, and tively link the fiber and matrix together, leading to good
376 M.S. Huda et al. / Composites: Part B 38 (2007) 367–379

Table 7
TGA characterization of the composites
Polymer/fiber and/or T5 (°C) T25 (°C) T50 (°C) T75 (°C)
filler (wt%)
Neat PLA 356 385 401 414
PLA/Newspaper (70/30) 308 336 349 356
PLA/Newspaper/Talc 1 325 355 368 380
(60/30/10)
PLA/Newspaper/Talc 3 337 370 387 425
(60/30/10)
Newspaper fiber (100%) 177 305 330 348

100

80
Weight (%)

(a )
60
(b)
(d)
40

(e )
20
(c )

0
0 100 200 300 400 500 600
Temperature (ºC)

Fig. 8. Thermogravimetric curves of the PLA and PLA-based composites:

(a) neat PLA (- Æ Æ), (b) neat Newspaper (—), (c) PLA/Newspaper (70/30)
(– – –), and (d) PLA/Newspaper/Talc 1 (60/30/10) (  ), and (e) PLA/
Newspaper/Talc 3 (60/30/10) (- - -).

interfacial adhesion between the two. In Fig. 13B, closer

observation of the fiber in the micrograph shows no indica-
tion of matrix materials on the fiber surface. However, it is
noted that some fibers are tightly connected with the
matrix. In the cases of silane treated talc-filled RNCF rein-
forced hybrid composites, fibers have tight contact with
matrix by increasing the effect between the surface treat-
ment of talc and matrix, that resulting in the regularity
of fiber dispersion in the matrix and less large size
aggregate.

4. Conclusions

This paper successfully presents the results of a study of

processing and properties of the environmentally friendly
talc filled RNCF-reinforced PLA hybrid composites that
were processed by using a micro-compounding and mold-
ing system. The mechanical and thermo-mechanical
properties of talc filled RNCF-reinforced PLA hybrid
composites and talc filled RNCF-reinforced PP hybrid
composites have been investigated. The mechanical and
thermo-mechanical properties of the RNCF-reinforced
PLA composites were found to compare favorably with
the corresponding counterparts of PP composites. Com-
pared with neat PLA or PP, the mechanical properties of
Fig. 9. SEM micrographs of (A) Talc 1 (5 lm), (B) Talc 2 (5 lm), and
(C) Talc 3 (10 lm).
the composites were enhanced when PLA or PP was filled
with RNCF and talc, in particular, flexural modulus due to
the stiffening effect of the talc. In the case of hybrid com-
posites, the modulus increases with the addition of talc
because of the greater stiffness of the talc, which generates
a stiffer interface in the polymer matrix. From the DMA
 M.S. Huda et al. / Composites: Part B 38 (2007) 367–379 377

Fig. 10. SEM micrographs of the fracture surface of Notched Izod impact specimens of PLA/Newspaper/Talc 1 (60 wt%/30 wt%/10 wt%) composite:
(A) 50 lm, and (B) 5 lm.

Fig. 11. SEM micrographs of the fracture surface of Notched Izod impact specimens of PP/Newspaper/Talc 1 (60 wt%/30 wt%/10 wt%) composite:
(A) 50 lm, and (B) 5 lm.

Fig. 12. SEM micrographs of the fracture surface of Notched Izod impact specimens of PLA/Newspaper/Talc 3 (60 wt%/30 wt%/10 wt%) composite:
(A) 10 lm, and (B) 5 lm.

results it is revealed that incorporation of the fibers and/or
talc gives rise to a considerable increase of the storage mod-
ulus (stiffness) and a decrease in the tan delta values. Both
treated and untreated talc act as stiffing agents for the poly-
mer matrix, the effect of the silane-treated talc is more
intense. The study performed by DSC revealed that the
PLA crystallinity was found to decrease as a result of the
addition of talc. The crystallization temperature of the talc
filled RNCF-reinforced PLA hybrid composites decreased
as compared to neat PLA, which signifies that the cellulose
fibers and talc hinder the migration and diffusion of PLA
molecular chains to the surface of the nucleus in the com-
posites. This decrease of crystallinity helps to increase the
impact strength of the hybrid composite, since the flexibil-
ity of molecular chains declines for increasing the crystal-
linity. Comparing samples with and without silane
treatment, it can be seen in the scanning electron micro-
graphs of the fracture surface of impact specimen that
378 M.S. Huda et al. / Composites: Part B 38 (2007) 367–379
Fig. 13. SEM micrographs of the fracture surface of Notched Izod impact specimens of PP/Newspaper/Talc 3 (60 wt%/30 wt%/10 wt%) composite:
(A) 50 lm, and (B) 10 lm.
the silane treated talc-filled RNCF reinforced hybrid com-
posite samples show better adhesion between the polymer
and the filler than the untreated talc-filled RNCF rein-
forced hybrid composite samples. Therefore, it is sensible
to modify the surface of the fillers in order to improve ease
of adhesion with and dispersion within the matrix in order
to realize the great potential of natural fiber/biodegradable
thermoplastic matrix composites.
Acknowledgements
Financial supports from USDA-MBI Award Number
2002-34189-12748-S4057 for the project ‘‘Bioprocessing
for Utilization of Agricultural Resources’’, NSF 2002
Award # DMR-0216865, under ‘‘Instrumentation for
Materials Research (IMR) Program’’ and NSF Award
DMI-0400296 ‘‘PREMISE-II: Design and engineering of
‘green’ composites from biofibers and bioplastics’’ are all
gratefully acknowledged. The authors also wish to express
their appreciation to Luzenac America, Inc. (CO, USA), to
CreaFill Fibers Corp. (Chestertown, MD, USA), to Basell
Polyolefins (Elkton, MD, USA), and to Biomer (Krailling,
Germany) for graciously supplying the talc, recycled news-
paper cellulose fibers, polypropylene, and poly(lactic acid),
respectively.
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