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High Stiffness Natural Fiber‐Reinforced Hybrid

Polypropylene Composites
a a
Haijun Li & Dr. Mohini M. Sain
a
Natural Composite Group, Forestry/Earth Sciences Center , University of Toronto ,
Toronto, ON, Canada , M5S 3B3
Published online: 14 Feb 2007.

To cite this article: Haijun Li & Dr. Mohini M. Sain (2003) High Stiffness Natural Fiber‐Reinforced Hybrid Polypropylene
Composites, Polymer-Plastics Technology and Engineering, 42:5, 853-862, DOI: 10.1081/PPT-120024999

To link to this article: http://dx.doi.org/10.1081/PPT-120024999

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 POLYMER–PLASTICS TECHNOLOGY AND ENGINEERING
Vol. 42, No. 5, pp. 853–862, 2003

High Stiffness Natural Fiber-Reinforced

Hybrid Polypropylene Composites
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Haijun Li and Mohini M. Sain*

Natural Composite Group, Forestry=Earth Sciences Center,

University of Toronto, Toronto, Canada

ABSTRACT

Natural fibers are potentially a high-performance non-abrasive reinforcing

fiber source. In this study, pulp fibers [including bleached Kraft pulp
(BKP) and thermomechanical pulp (TMP)], hemp, flax, and wood flour
were used for reinforcing in polypropylene (PP) composite. The results
show that pulp fibers, in particular, TMP-reinforced PP has the highest
tensile strength, possibly because pulp fibers were subjected to less severe
shortening during compounding, compared to hemp and flax fiber
bundles. Maleic-anhydride grafted PP (MAPP) with high maleic anhy-
dride groups and high molecular weight was more effective in improving
strength properties of PP composite as a compatiblizer. Coupled with 10%
glass fiber, 40% TMP reinforced PP had a tensile strength of 70 MPa and
a specific tensile strength comparable to glass fiber reinforced PP.
Thermomechanical pulp was more effective in reinforcing than BKP.

*Correspondence: Dr. Mohini M. Sain, Natural Composite Group, Forestry=Earth

Sciences Center, University of Toronto, Toronto, ON, Canada M5S 3B3; Fax: 416-978-
3834; E-mail: m.sain@utoronto.ca.

853

DOI: 10.1081=PPT-120024999 0360-2559 (Print); 1525-6111 (Online)

Copyright # 2003 by Marcel Dekker, Inc. www.dekker.com
 854 Li and Sain

X-ray photoelectron spectroscopy (XPS) and scanning electron micro-

scope (SEM) were used to aid in the analysis. Polypropylene with high
impact strength was also used in compounding to improve the low-impact
strength prevalent in natural fiber-reinforced PP from injection molding.

Key Words: Natural fiber; BKP; TMP; Glass fiber; Polypropylene;

Reinforcing; Composite; Strength properties.

INTRODUCTION
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Natural fibers have recently attracted the attention of researchers because of

the advantages these fibers provide over conventional reinforcement materials,
such as low cost, renewability, biodegradability, low specific gravity, abundancy,
high specific strength, and non-abrasiveness.[1,2] Thus, natural fiber-reinforced
composites seem to be an alternative material to glass fiber-reinforced plastics in
some technical applications. Significant research has been done to achieve high-
performance natural fiber-reinforced thermoplastics, although the problem of
phase incompatibility during compounding of the hydrophilic fibers into non-
polar resin matrix [e.g., polypropylene (PP)] has not been solved.[3–6] In
particular, for the injection-molding process, uniform dispersion of natural
fibers in the resin matrix is a precondition for high-strength properties.
Natural fibers are grouped into three types: seed hair, bast fibers, and leaf
fibers, depending on the source. Of these fibers, jute, ramie, flax, and sisal are
the most commonly used fibers for polymer composites. Natural fibers in the
form of wood flour have also often been used for preparation of natural fiber
composites. In this investigation, an effort has been made to use wood pulp as a
source as reinforcing filler for PP composites. Canada is the largest exporter of
commercial pulp and has the highest production of mechanical pulp in the
world. Wood fibers have specific strength comparable to jute and hemp
although the length of the former is usually shorter.[7] Therefore, it is interesting
to study the behavior of wood fibers in injection molding of polymer
composites, in comparison with natural fiber sources with longer length, such
as flax and hemp. Two typical wood fiber sources, bleached Kraft pulp (BKP)
and thermomechanical pulp (TMP) are used in this study. Bleached Kraft pulp
is well-known reinforcing fiber source in the paper industry, whereas TMP is
a low cost and environment-friendly fibers with more hydrophobic surface.
To overcome the problem of poor compatibility between the polar hydro-
philic natural fiber and the non-polar hydrophobic PP, researchers have used
various kinds of methods, such as physical activations, coupling, or compati-
bility agent.[8–10] Among them, maleated polypropylene (MAPP) as a com-
patibilizer has received attention because of its effectiveness in improving the
 Natural Fiber-Reinforced Hybrid PP Composites 855

mechanical properties (tensile and flexural strength) of the composites.[3–5,10]

The efficiency of MAPP in improving strength properties depends on its
physicochemical composition. Although a lot of research has been done in
the field of natural fiber-reinforced PP composites, the strength properties of the
composites (e.g., tensile strength are still too low compared to that of glass
fiber-reinforced PP. So the objective of this article is to obtain natural fiber (in
particular wood fiber)-reinforced PP composites with high tensile strength.

EXPERIMENTAL
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Material

Polypropylene (PP3632 homopolymer from Atofina and SV440 from

Himont) was used as the polymer matrix. The density of PP was 0.96 g=m3,
and the melt flow index was 12 dg=min. Bleached Kraft pulp, unbleached TMP,
flax, hemp, core hemp, and wood flour were used as reinforcing filler. The pulps
were obtained from Abitibi-Price Inc. (Ontario, Canada). Bleached Kraft pulp
was defiberized in a Wiley Mill (Thomas-Wiley Laboratory Mill Model 4) into
small uniform floc and sieved to 250 mm. Flax, hemp, and core hemp were
supplied by Hempline (Ontario, Canada), wood flour by Northern Fiber
(Ontario, Canada), short glass fiber of 1=2 inch by Vetrotex America. Two
different types of MAPP were used as compatibilizer: Oramac 100 and
MAPP880. These two maleated polyolefines have different content of maleic
anhydride groups and molecular weight. The details are summarized in Table 1.

Methods

Natural fiber, PP, and MAPP were compounded in a high-intensity kinetic

mixer (Werner and Pfleiderer Gelimat model 456441G1). Two methods of
mixing were used in our experiments.

1. Single-stage method: natural fiber, MAPP, and PP were blended in the

K-mixer at 4600 rpm and discharged at 190
C. The total residence
time of the mixing operation was about 120 sec.

Table 1. Typical properties of two MAPP.

Properties Oramac 100 MAPP880

Mw 9,000 60,000
Mn 3,800 20,000
Maleic anhydride units 1.6 10.7
 856 Li and Sain

2. Two-stage method: first, BKP or TMP were defiberized in the K-mixer

at 4600 rpm for 45 sec; then MAPP and PP were added and mixed for
another 30 sec; finally, glass fiber (if required) was added. The mixture
was automatically discharged at 190
C. The total residence time was
about 90 sec. After that, 65 g of K-mixer-treated material was mixed in
a C. W. Brabender Mixer at 200
C and 80 rpm for 5 min.

After compounding, the melted compounds were allowed to cool to room

temperature and then granulated in a Brabender granulator (model S-10-9).
The resulting compounds were preheated at 70
C for 1 hr and injection
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molded by using an Engel ES-28 machine equipped with a standard ASTM

test specimen mold (ASTM 638). The injection molding conditions were as
follows: injection temperature 204
C, injection pressure 4.8 MPa, clamp
pressure 11.7 MPa, injection time 9.5 sec, cooling time 25 sec, and mold
opening time 2 sec.
The tensile, flexural, and Izod impact tests were conducted according to
ASTM D-638, ASTM D-790, and ASTM D 256-90, respectively. Six speci-
mens were tested to obtain an average value. Scanning electron microscopy
(JEOL 840) was used to observe the fiber surface of BKP and TMP.

X-Ray Photoelectron Spectroscopy Analysis

X-ray photoelectron spectroscopy was used to characterize the surface

chemical composition of TMP and BKP fiber. Atomic percentages of the
elements present were derived from spectra run in a low-resolution mode (pass
energy ¼ 192 ev). For the information of C associated functional groups, the
spectra regions of interest were also run in a high-resolution mode (pass
energy ¼ 48 ev).

RESULTS AND DISCUSSION

Effect of Natural Fiber Types on Strength Properties

Table 2 includes the results of the effect of MAPP-treated BKP, flax,

hemp, core hemp, and wood flour on the mechanical properties of injection-
molded composites. Clearly, the BKP-PP composites have the highest tensile
and flexural strength and unnotched impact strength. Flax and hemp-filled PP
composites have similar strength properties. In comparison, wood flour-filled
PP composites have the lowest mechanical strength. Such a trend can be
attributed to the actual fiber length in the composites. It has been observed that
 Natural Fiber-Reinforced Hybrid PP Composites 857

Table 2. Effect of natural fiber type on mechanical strength performance of filled

PP composites (40% filler, 2% Oramac 100).

Milled Core Wood

Fiber type BKP Flax hemp hemp flour
Tensile (MPa) 50 42 42 29 35
Tensile modulus (GPa) 3.0 3.2 3.0 2.3 2.9
Flexural (MPa) 78 67 70 52 59
Flexural modulus (GPa) 3.3 3.4 3.5 2.6 3.0
Notched Izod (J=m) 40 44 42 20 28
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U-notched Izod (J=m) 205 150 145 100 105

after compounding, the fiber length of flax and hemp decrease significantly,
whereas that of BKP fibers dose not change much. This is possibly due to the
fact that the flax and hemp bundles are prone to being torn down to very small
size by the high-shear force from the melted PP. To preserve the fiber length,
less severe treatment is necessary but at the cost of poor dispersion of fibers in
the resin matrix. The poor strength of wood flour reinforced composites is
because of the low aspect ratio of wood flour particles, which is far below the
critical fiber length required for reinforcement.
Thus, the above results indicate that the preservation of fiber length in the
compounding process for composite is critical. On the other hand, it is also
important to disperse the hydrophilic fiber uniformly into the hydrophobic
matrix. So a careful balance between dispersion and preservation of the natural
fibers in the polymer matrix must be attained to achieve high mechanical
strength.

Effect of Maleic-Anhydride Grafted Polypropylene Type on

Strength Properties

The effect of different types of MAPP on the strength performance of

40% BKP and 10% glass fiber-reinforced hybrid composites was examined.
The results are included in Table 3. It shows that MAPP880 is more effective
in improving the mechanical strength of hybrid composites, compared to
Oramac 100. This is possibly because MAPP880 has a higher content of
maleic anhydride groups and higher molecular weight, namely, a longer
molecular chain. The fiber treated with high molecular weight MAPP can
induce greater interdiffusion and interchain entanglements of PP molecules at
the interface.[5,10] The high amount of anhydride groups in MAPP880 can help
 858 Li and Sain

Table 3. Effect of MAPP type on the strength performance of BKP-filled PP

composites (5% MAPP).

40% Kraft fiber þ 10% 40% Kraft þ 10%

Fiber type glass fiber glass fiber
MAPP Oramac 100 MAPP880
Tensile (MPa) 61 65
Tensile modulus (GPa) 4.2 4.1
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to adhere to the hydrophilic fibers through acid-base interaction, thus coating

the fiber surface more uniformly with MAPP. Consequently, the dispersion of
BKP fiber treated with MAPP880 is better in the PP matrix.

Comparison of Thermomechanical Pulp and Bleached Kraft

Pulp in Reinforcing Polypropylene

The comparison of strength performance between TMP- and BKP-

reinforced glass fiber hybrid composites is shown in Fig. 1. Clearly, the
TMP-reinforced hybrid composites have higher tensile strength than that of
BKP-reinforced one. In fact, the 40% TMP-reinforced hybrid composites has a
comparable high specific tensile strength to that of 40% glass fiber-reinforced
composites. Thermomechanical pulp is derived from heat treatment of wood
chips and mechanical separation of wood fibers without any chemical
treatment. Thus, TMP is a much cheaper but more environment-friendly
fiber source, in comparison with BKP. Also interesting to note, it is easier

Figure 1. Comparison of tensile strength of composites prepared from different fiber

types (5% MAPP880).
 Natural Fiber-Reinforced Hybrid PP Composites 859

to compound TMP-PP dry blend than BKP-PP. Thus, TMP is a promising

natural fiber-resource for injection-molded PP composites. However, the
impact strength of all natural fiber-reinforced PP composites in this study is
significantly lower, compared to that of glass fiber-reinforced composites.

Characteristic of Thermomechanical Pulp and

Bleached Kraft Pulp Fiber
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Compared to that of BKP-reinforced PP, the better strength of TMP-

reinforced PP composites are rather surprising, because it is well known that
BKP is a preferred reinforcing fiber source for paper products prepared from
TMP in paper industry. However, the function of reinforcement in polymer
composite is different from that in the paper industry. Thermomechanical pulp
is more effective possibly due to the difference in surface chemical composi-
tion and morphology, in comparison with BKP. Table 4 shows the chemical
composition of two pulps fiber surface using XPS measurement. As expected,
TMP fibers are more hydrophobic than BKP fibers, as indicated by the lower
O=C ratio of the former. The results of C 1-sec high-resolution spectra in
Table 4 also indicate that BKP fibers have a higher C O and low CC=CH
ratio than TMP fibers. Such results are in agreement with the fact that BKP
fibers are fully bleached fiber and almost contains only cellulose, thus having
high content of hydroxyl groups on the surface (C OH).
The scanning electron microscope (SEM) pictures of BKP and TMP
fibers are shown in Fig. 2. Obviously, BKP fibers have a lot of fibrils on the
surface, whereas the surface of TMP fibers are rather ‘‘smooth.’’ It is also well
known that BKP fibers are more flexible than TMP fibers, because the latter
contain a high amount of lignin that makes TMP fibers rigid. Thus, BKP fibers
tend to bond to and entangle with each other strongly through a large amount
of hydrogen bonds because of the rich amount of hydroxyl groups and fibrils
available on the fiber surface, and the flexibility of fibers. Correspondently, the
hydrophilic BKP flocs are much more difficult to disperse and orient in the

Table 4. Surface chemical composition of TMP and BKP fibers.

C associated bonds (total 100%)

Fiber O=C
type ratio C
C=CH C
O C¼
¼O=OCO O
C¼¼O
TMP 0.33 53 35 10 2
BKP 0.56 47 36 17 —
 860 Li and Sain
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Figure 2. (a) SEM of BKP fiber; (b) SEM of TMP fiber.

hydrophilic PP matrix than the more hydrophobic and rigid TMP fibes. It has
also been observed by other researchers.[5]

Impact Strength Properties

To improve the impact strength of natural fiber-reinforced injection-molded

PP composites, PP with high-impact strength was used. The results are
summarized in Table 5. It shows that the impact strength (notched) is improved
by 40%, but the tensile strength of the composites drops by 17%. Even the

Table 5. Impact strength with two different types of PP (5% MAPP880 for PP
composites).

40% TMP= 40% TMP=

Strength 10% GFPP High-impact 10% GFH-PPa
properties PP3622 composite PP composite
Tensile 32 70 26 58
strength (MPa)
Tensile 1.2 4.6 1 4
modulus (GPa)
Impact strength, 21 28 75 40
notched (J=m)
Impact strength, 690 210 1250 265
unotched (J=m )
a
High-impact PP.
 Natural Fiber-Reinforced Hybrid PP Composites 861

impact strength of composites prepared from PP with high-impact strength is

still lower, compared to the value of 110 J=m of glass fiber-reinforced PP
composites. One possible factor here is the length of natural fibers used in this
study: the majority of natural fibers length is shorter than 2 mm after com-
pounding, which is much shorter than that of 12 mm of glass fibers usually used
in composites. Thus, the fiber length of natural fibers is a critical issue for
injection molding. Future work needs to be done to improve the impact strength
of composites reinforced by natural fibers in injection molding.
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CONCLUSIONS

Bleached Kraft pulp fiber is better in reinforcing PP in comparison with

flax, hemp, core hemp, and wood flour, possibly due to the less shortening of
pulp fibers in high-energy compounding. Maleic anhydride PP with a
high content of maleic anhydride groups and high molecular weight is a
more effective compatibilizer for natural fiber-reinforced PP composite.
Thermomechanical pulp, as a low-cost and environment-friendly fiber,
shows better reinforcing function than BKP in PP composite; 40% TMP
and 10% glass fiber-reinforced PP has a tensile strength of 70 MPa and a
specific tensile strength comparable to glass fiber-reinforced PP. The superior
behavior of TMP is possibly due to its better dispersion and orientation in non-
polar PP matrix. In comparison, BKP fibers are more hydrophilic (rich in
hydroxyl groups) and contain a lot of fibrils, which make BKP fibers tend to
bond to and entangle with each other via hydrogen bonds. Consequently, BKP
fiber floc is very difficult to disperse in PP.
Natural fiber-reinforced PP composites have low-impact strength. To
improve that, PP with high-impact strength was used. Although the impact
strength is improved, it is still low. Future work needs to be done.

ACKNOWLEDGMENT

The authors sincerely thank NCE-Auto-21, Canada, and Industry partners

(Atofina) for financing this project.

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 862 Li and Sain

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