Composites: Part B 57 (2014) 126–135

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Composites: Part B
journal homepage: www.elsevier.com/locate/compositesb

Effect of coupling agent on natural fibre in natural fibre/polypropylene

composites on mechanical and thermal behaviour
A. El-Sabbagh ⇑
Institute of Polymer Materials and Plastics Engineering, Clausthal University of Technology, Agricola Str. 6, Clausthal-Zellerfeld D-38678, Germany
Design and Production Engineering Department, Ain Shams University, Cairo, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: To enhance the adhesion between the natural fibre and the thermoplastic matrix, a coupling agent of
Received 29 January 2013 maleic anhydride grafted polypropylene MAPP is applied. In literature, there are different guidelines of
Received in revised form 19 September 2013 the optimum percentage required of MAPP. Therefore, a systematic work is carried out to optimise the
Accepted 23 September 2013
MAPP percent with respect to the type of the natural fibre. Different parameters are investigated namely;
Available online 1 October 2013
Coupling agent ratio to the fibre (0%, 6.67%, 10%, 13.3%, 16.67%), coupling agent source, fibre type (flax,
hemp, sisal), and fibre content (30%, 50%). Composite is produced using a kneader and the resulting mate-
Keywords:
rial is assessed mechanically, thermally, microscopically and for water absorption. For different MAPP
A. Fibres
A. Polymer-matrix composites (PMCs)
source and the natural fibre type, optimum MAPP to fibre ratio is found in average to range between
B. Adhesion 10% and 13.3% according to the investigated property (stiffness, strength and impact). Increase of MAPP
B. Mechanical properties is found to decrease the melting temperature. The thermal behaviour is also linked to the copolymer
E. Thermoplastic resin molecular weight.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Natural fibres polymer composites occupy a significant position
in the engineering market. A lot of automobile interior parts are al-
ready manufactured using these natural fibre composites in order
to replace as much as possible the synthetic fibre products. It is al-
ready known that natural fibre benefits are attractive [1–7]: their
light weight, high mechanical properties, drop of environmental
problems concerning manufacturing, and recycling and longer life
for tooling specially with high shear rate processes. Thermoplastic
composites are earning a lot of attention to have both the functions
of natural fibres and the production easiness of thermoplastics.
However, NFTC still suffer from many problems that hinder the
growth of their markets. Namely, processing problems like the fi-
bres’ limited processing temperature range [3,4], fibre hydrophilic
nature [4–7], bacterial degradation [8], dimensional instability be-
cause of the water absorption [8–10], inconsistent mechanical
properties [3,8], and processing difficulties [11]. The main problem
which arises during the manufacturing phase is the hydrophobic
nature of the polymer and the hydrophilic nature of the thermo-
plastic polymer [12–14].
Lots of methods are adopted to treat either the surface of the fi-
bre or the polymeric matrix in order to enhance the adhesion and
ensure an acceptable load transfer [12,15,16]. Physical treatment
⇑ Tel.: +49 5323722487; fax: +49 5323722324.
E-mail address: ahmed.sabbagh@tu-clausthal.de
includes treatments by heat [6], plasma [17], corona [18], and sur-
face fibrillation [6]. Chemical treatment includes different meth-
ods. Alkalinisation for example depends on the breaking of the
hydrogen bond in cellulose and removes some of the lignin and
wax covering the natural fibres [19]. Free radical formation in cel-
lulose accompanied by graft copolymerisation is another route as
in acrylation, acetylation [20], silanisation [21] and maleic anhy-
dride MA treatment [13].
Of the previous methods, Alkalisation and chemical grafting
using MA treatment are most popular. Alkalisation is even consid-
ered a standard step to increase the efficiency of any further treat-
ment. MA grafting is not only used to modify fibre surface but also
the thermoplastic matrix to achieve better interfacial bonding and
mechanical properties in composites. It exploits the hydroxyl
groups which are abundantly available in the cellulosic natural fi-
bre from one side and grafts to the matrix polymer from the second
side. Additionally, unlike acrylic acid, MA does not react with itself
under typical industrial grafting conditions. MA grafting improves
the mechanical properties, water absorption resistance and dimen-
sional stability of the composites. Besides, it is suitable to be used
cost-wise. Also, grafted MA, like maleic anhydride grafted polypro-
pylene MAPP, can be used directly with the available compounding
machine without inserting a new processing step to the production
cycle.
An issue, however, arises during the use of the MA copolymers
like MAPP. It is the presence of many rules to follow to get best re-
sults of grafting. Table 1 illustrates some of the common practices

1359-8368/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.compositesb.2013.09.047
 A. El-Sabbagh / Composites: Part B 57 (2014) 126–135
Table 1
Plan of investigated parameters.
# Parameter Variation
1 Fibre type Flax, Hemp, Sisal
2 MAPP: NF 0%, 6.7%, 10.0%, 13.3%, 16.7%*
3 NaOh conc. 0%, 5%, 10%
pretreatment
4 Fibre content % 30%, 50%
5 MAPP source Type A from Sigma Aldrich Type B from
Kometra
*
MAPP% in 30% fibre loading is [0%, 6.7%, 10%, 13.3%, 16.7%]⁄30% = 0%, 2%, 3%, 4%,
5%, while in 50% fibre loading the MAPP% is [0%, 6.7%, 10%, 13.3%, 16.7%]⁄50% = 0%,
3.3%, 5.0%, 6.7%, 8.3%.
followed. Bos [8] reported that 3.5% of MAPP powder (Hostaprime
HC5) is optimum in kneaded PP/Flax. Keener et al. [13] similarly
said that 3% is optimum with MAPP Epolene for extruded PP/Agro-
fibre. Sain et al. [22] found that 2.5% of E43 MAPP is the optimum
percent in kneading PP/Wood fibre. Arbelaiz [14] stated that E43
MAPP should be dependent on the retted flax fibre amount in
1:20 ratio. Zampaloni et al. [23] used compression moulding for
PP/Kenaf fibres and reported that 3% MAPP Epolene wax G-3015
is optimum. Bos [24] again in 2006 reported that 1:10 of MAPP
(Epolene TM G-3015) to flax is optimum by kneading with PP.
Pimenta et al. [25] found that 6% of MAPP G-3015 is needed in
the extrusion of PP/Sisal. As seen, the amount of MAPP changes
from 2.5% to 6.0% regardless the natural fibre content. The fibre
type may have an effect on the optimum MAPP% due to the cellu-
lose content. The ratio of the copolymer to natural fibre is another
suggested method to define the amount of the required copolymer
[14,24] regardless of the fibre type or the MAPP properties. A study
is required to see the effect of different parameters and find out the
range of optimality for using the coupling agent. MAPP is taken as
the studied copolymer for different natural fibres with polypropyl-
ene PP matrix. To compare with the literature results regarding the
effect of MAPP effect, weight ratios are used because MAPP is not
evaluated in volume fraction.
2. Experimental work
The objective of this work is to investigate the optimum MAPP
content at different parameters. Table 1 illustrates the factors
investigated in this study. These factors are the copolymer to nat-
ural fibre weight ratio, hereafter called MAPP:NF, the copolymer
molecular weight or graft%, natural fibre type and content. As pre-
viously mentioned, pretreatment with alkalinisation is essential.
Therefore a set of preliminary experiments is added to the plan
of tests in order to find out the optimum NaOH concentration.
Three types of fibres are selected due to their common use. Bast fi-
bres represented in flax and hemp. Leaf fibres which are character-
ised with its coarseness and relatively high stiffness are also
represented in sisal. Fibres were supplied by Sachsenleinen-Ger-
many. Flax, hemp and sisal constitute respectively of 63%, 65%,
63% cellulose, 16%, 16%, 12% hemicellulose, 4%, 4%, 11% pectin/lig-
nin, 1%, 1%, 1% fats/waxes, 4%, 2%, 1% proteins/ashs and 12%, 12%,
12% water. Cellulose and moisture content of the fibres’ three types
are almost the same. This means that the numbers of OH groups
able to react are almost equal. Hemicellulose of the leaf sisal fibres
is 4% less than flax and hemp whereas the pectin/lignin is 10%
more. Lignin has a positive effect on the adhesion behaviour be-
tween the natural fibres and the thermoplastic polymer as re-
ported [26]. Percentages of proteins and ashes are insignificant in
sisal compared to the flax and hemp bast fibres. Homopolymer
PP developed for thin wall high speed injection moulding is used
127
as the host matrix, and is supplied by DOW GmbH (MFR = 52 at
230 °C/2.16 kg and specific density of 0.9).
Fibres are washed with different concentrations of sodium
hydroxide solution for different times at room temperature to re-
move possible surface impurities. The fibres are washed with
water then with acetone to reach neutralisation. Fibres are then
left to dry at 90 °C for 24 h then left in open air for 3–4 days. Before
compounding these alkalinised fibres with PP, they are re-dried
again at 90 °C. Two levels only of fibre contents are selected for this
plan, due to their wide market application, namely 30% and 50%.
The source and the form of the coupling agent are also consid-
ered due to the effect of molecular weight, acid number, outer
surface area and the probable sites of reaction and grafting [13].
Kim [27] reported that neither low nor high molecular weight
copolymers help in the proper entanglement between MAPP
and PP matrix. Also neither low nor high MA grafting provide bal-
anced interaction with PP and the fibres. Molecular weight affects
the resulting composite’s mechanical properties in a direct pro-
portion way [27]. Two types are studied. Type A is the granulate
form MAPP from Sigma Aldrich with molecular weight of 9100
GPC and thermosel viscosity 4000 poise (190 °C). Type B is pow-
der form MAPP supplied by Kometra (SCONA TPPP 8112) with
molecular weight of 119850 g/mol. Grafting increases with MA
content [28]. From another side; higher molecular weight MAPP
has normally lower acid number and hence lower MA content.
This results in higher melt flow index MFI, better mixing, and bet-
ter diffusion [28]. Therefore, both types of MAPP are studied to
see the effect of different shapes and molecular weights of the
coupling agent.
Compounding mechanism is carried out in the batch kneader
Haake with roller type. High speed is used firstly when PP and
MAPP are added. Torque is observed to ensure total melting of
PP and MAPP. Then when the natural fibres are inserted, the
speed is lessened to help in smoothing the acquisition of fibres
for 5 min. This time has allowed also good impregnation. After
the end of fibres insertion, speed is increased again for a while.
Speed is then lessened again to 50 rpm and again increased to
100 rpm for 5 min each. This cycle is not the optimum for fibres’
length but it helps to reach homogeneous well impregnated fibres
using these rollers from one and relatively short rotation cycle.
The kneaded material is then shredded. The granulates are injec-
tion-moulded at a temperature pattern of 185–190–195–200 °C
using Allrounder 220C 600–250, Arburg, Lossburg, Germany.
Samples of mechanical testing are conditioned at 23 °C/50%
relative humidity for at least 88 h according to ISO 291 for test
room conditions. Tension tests were made using Zwick 0.25 ton
tensile machine according to DIN EN ISO 527-1. Test sample is
injection-moulded according to ISO 527-2. Test is conducted
and evaluated according to ISO 527-1. Water absorption test is
conducted also according to DIN 53495-method 3 where the
weight of the sample is observed after 30 min at 100 °C distilled
water followed by 15 min at 23 °C in distilled water and finally
drying of the sample.
[1] Thermal gravimetric analysis TGA is also conducted on the
50% flax PP composites to cover the MAPP:NF spectrum for
both types of the studied MAPP. TGA is conducted using
Q5000 IR from TA instruments in nitrogen atmosphere with
10 k/min rate.
[2] Differential scanning calorimetry DSC test is applied using
DSC Q2000 by cycle heating from 100 to 250 °C then re-
cooling to 100 °C with 2 k/min to observe the melting tem-
perature, recrystallization temperature, melting enthalpy
and recrystallization energy of the composites of different
MAPP:NF ratios and MAPP types.
128 A. El-Sabbagh / Composites: Part B 57 (2014) 126–135

Effect of time Effect of concentration

8 8

Loss in weight [%]

6 6

Loss in weight [%]

4 4

2 2

(a) 0
(b)
0
0 5 10 15 20 25 0 2 4 6 8 10
Time [hr] Concentration [%]

Fig. 1. Effect of (a) Time (b) NaOH Concentration on natural fibre weight loss after alkalinisation.

3. Results Table 2 presents the effect of fibre pre-treatment (alkalinisa-

tion) on the mechanical properties of the manufactured compos-
3.1. Effect of pretreatment course ites. Fibre content is kept at 30 wt%. The ratio of MAPP:NF is kept
constant at 1:10 in the test samples of NaOH effect. The used MAPP
Fig. 1 shows the effect of alkalinisation time and concentration was that of the granulate form out of Sigma Aldrich. Stiffness im-
of NaOH on the natural fibre weight. Loss in weight is taken as an proves with 6–9% for the three types of fibres. Only sisal shows a
indication for the removal of impurities, waxes, hemicelluloses and decrease at 10% NaOH treatment. This may be contributed to the
delignification. Logarithmic plateau form can be depicted from excess removal not only of surface impurities but also of lignin
both curves. 24 h treatment is taken as an appropriate treatment [30]. Therefore sisal, which has already higher content of lignin
period. Actually starting from 5 h, the weight loss in Fig. 2a seems playing a positive coupling rule, was the most influenced one.
to be enough and the increase in loss is not so significant. The Excessive NaOH in a way or another decreases the binding be-
weight loss in Fig. 2b points out that 2% is significant in comparison tween the fibrils and make them move more freely and hence de-
with no treatment. This result matches previous work [29]. How- creases the overall stiffness. Another tentative explanation is due
ever, 5% treatment shows a good improvement even in comparison to the excessive loss of weight of fibres after alkalinisation which
with 2%. The change from 5% to 10% cannot be considered insignif- in turn lessens the load transfer efficiency. This suggests that there
icant. Therefore fibres’ treatments with 0%, 5% and 10% concentra- are two influencing factors on the mechanical effect. First is the
tion values are carried out and then compounded into composites increasing number of sites ready for coupling and adhesion with
to investigate the final mechanical properties. the natural fibres with the increase of NaOH concentration%.

10000 60
9000 (a) (b)
50
8000
Stiffness [MPa]

7000
Strength [MPa]

40
6000
5000 30
4000
20
3000
2000
10
1000
0 0
30 50 30 50
[Wt. %] [Wt. %]
Flax Hemp Sisal Flax Hemp Sisal

6 9
(c) 8 (d)
5
7
Elongation [%]

Impact [kJ/m²]

4 6

5
3
4

2 3

2
1
1

0 0
30 50 30 50
[Wt. %] [Wt. %]
Flax Hemp Sisal Flax Hemp Sisal

Fig. 2. Effect of fibre type and content at 5% NaOH on (a) Stiffness (b) Strength (c) Elongation % (d) Impact.
 A. El-Sabbagh / Composites: Part B 57 (2014) 126–135 129

Table 2
Effect of NaOH concentration on the mechanical properties of PP/30% flax/3% MAPP (Type A).

Fibre Fibre [wt%] NaOH [%] Stiffness [MPa] Dev. [MPa] UTS [MPa] Dev. [MPa] Elongation [%] Dev. [%] Impact [kJ/m2] Dev. [kJ/m2]
Flax 30.0 0.0 5178.0 344.4 40.1 1.3 3.6 1.1 7.1 0.9
Flax 30.0 5.0 5631.4 502.8 43.1 0.9 4.3 0.7 7.4 0.6
Flax 30.0 10.0 5701.4 304.1 44.1 0.4 2.8 0.5 8.1 0.9
Hemp 30.0 0.0 5231.7 203.5 41.1 0.9 4.7 0.7 6.9 0.7
Hemp 30.0 5.0 5608.7 180.1 42.9 1.1 3.1 0.3 7.0 0.6
Hemp 30.0 10.0 5702.7 158.8 46.0 1.0 3.2 0.2 6.9 0.8
Sisal 30.0 0.0 4928.4 417.7 38.0 0.5 4.3 0.4 5.6 1.0
Sisal 30.0 5.0 5205.9 247.6 38.9 1.4 3.5 0.6 6.0 0.7
Sisal 30.0 10.0 4794.9 147.3 40.8 1.0 4.5 1.0 7.3 0.4

Natural Fibres 30% Natural Fibres 50%

6500
10000
6000
9000
(a)
Stiffness [MPa]

5500

Stiffness [MPa]
8000
5000
7000
4500
6000
4000
5000
3500
(a) 4000
3000
0 2 4 6 8 10 12 14 16 18 3000
0 2 4 6 8 10 12 14 16 18
MAPP/Fibre [%]
MAPP/Fibre [%]
Flax Hemp Sisal
Flax Hemp Sisal

Natural Fibres 30%

50 Natural Fibres 50%
60

45 55 (b)
Strength [MPa]

Strength [MPa]

50
40
45
35
40

30 35

(b) 30
25
0 2 4 6 8 10 12 14 16 18 25
0 2 4 6 8 10 12 14 16 18
MAPP/Fibre [%]
MAPP/Fibre [%]
Flax Hemp Sisal
Flax Hemp Sisal
Natural Fibres 30%
9 Natural Fibres 50%
9
8
7
8 (c)
Impact [kJ/m²]

7
6
impact [kJ/m²]

6
5
5
4
4
3
3
2
2
1
(c) 1
0
0 2 4 6 8 10 12 14 16 18 0
0 2 4 6 8 10 12 14 16 18
MAPP/Fibre [%]
MAPP/Fibre [%]
Flax Hemp Sisal
Flax Hemp Sisal
Fig. 3. Effect of MAPP:NF ratio on (a) Stiffness (b) Strength (c) Impact 30% NF.
Fig. 4. Effect of MAPP:NF ratio on (a) Stiffness (b) Strength (c) Impact for 50% NF
composite.

Second is the negative effect of delignification caused by alkalinisa-

tion. Both factors act against each other. Therefore plateau form is sisal strength improves 8% at 10% NaOH treatment whereas sisal
found for both flax and hemp while sisal reaches its saturation le- stiffness decreases 8% between 5% and 10% NaOH treatment. Flax
vel of NaOH treatment at 5% concentration. 5% NaOH pre-treat- and hemp still show an obvious enhancement in strength. Hemp
ment seems to be sufficient for the three types of fibres. has a linear trend increase while flax shows a plateau form. Stiff-
On the other side, strength behaviour is still positively affected ness behaviour reaches its optimum before that of the strength.
with NaOH% compared to the stiffness behaviour. As mentioned, This difference in the optimum values between strength and
130 A. El-Sabbagh / Composites: Part B 57 (2014) 126–135

Table 3
Optimum MAPP:NF ratios (Improvement %) for 30% and 50% NF.

30 wt% 50 wt%
Flax Hemp Sisal Flax Hemp Sisal
Stiffness 10 (3.7) 6.7 (11.7) 6.7 (11.5) 13.3 (20.6) 10 (17.0) 16.7 (6.3)
Strength 6.7 (19.1) 6.7 (13.5) 6.7 (8.4) 6.7 (66.1) 13.3 (28.5) 6.7 (12.8)
Impact 6.7 (23.8) 10 (12.9) 6.7 (34.1) 6.7 (60.1) 6.7 (39.5) 6.7 (19.2)

30 wt%
18 30 wt%
(a) 70
16 (a)
60
14

Improvement [%]
50
12
MAPP:NF [%]

10 40

8 30

6 20

4
10

2
0
Flax Hemp Sisal
0
Flax Hemp Sisal E-modulus Strength Impact
E-modulus Strength Impact
50 wt%
70
50 wt%
18 (b)
60
16
(b)
Improvement [%]

50
14

12 40
MAPP:NF [%]

10
30
8
20
6

4 10

2
0
Flax Hemp
E-modulus Strength
Fig. 5. Optimum MAPP:NF ratios on stiffness, strength and impact for (a) 30 wt% (b)
50 wt%.
stiffness can be related to the nature of fibres’ orientation at the
injection-moulded samples’ surfaces [30]. The fibres are better ori-
ented and shows almost no sign of fibres agglomeration. Thus the
strength values compared to those of stiffness are already way be-
hind and hence NaOH or similar treatments affect the strength
more positively.
The impact values of the un-notched specimens. As expected
from the stiffness and strength results; the impact values show
also an improvement of 13% and 28% for flax and sisal. Hemp fi-
bres, however, has no change. This can be attributed to the differ-
ence in the fibrils orientation. Flax fibrils are almost 10° to the axis
[31]. This gives flax some sort of elasticity compared to hemp. Sisal
has no orientation angle. However it has a little bit elongation be-
cause of the increased quotient of strength to the stiffness.
From the results presented in Table 2, a concentration of 5–10%
NaOH is selected as an almost optimum range to be adopted. How-
ever, the improvement attained by the increase of NaOH concen-
tration from 5% to 10% is not significant especially in stiffness
0
Flax Hemp Sisal
Sisal E-modulus Strength Impact
Impact
Fig. 6. Maximum mechanical properties at optimum MAPP:NF ratios for (a) 30 wt%
(b) 50 wt%.
results for all types of fibres or strength results for flax. The
improvement of strength in flax at 10% is not accompanied with
an improvement in impact. Therefore 10% pretreatment is not so
attractive and 5% is enough to be selected as a constant NaOH con-
centration pretreatment. Also from Table 2, it can be inferred that
sisal out of the three fibre types is the least sensitive fibre to the
alkalinisation treatment in comparison to the flax and hemp fibres.
The significance of the results listed in Table 2 was tested by two
tailed t-test with 95% confidence. T-test proved the significance
for the pairs (0% vs 5%), (5% vs 10%) and (0% vs 10%). Only the im-
pact results of hemp seem totally insignificant.
3.2. Effect of fibre type and content
Fig. 2 presents the mechanical properties spectrum of the 30%
and 50% natural fibre polypropylene composites with the use of
type (A) granulated form MAPP of 1:10 ratio pre-treated with 5%
NaOH. Fig. 2a presents the stiffness results. Addition of fibres en-
hanced the stiffness from almost 1.5 GPa to 5.2–5.6 GPa for the
 A. El-Sabbagh / Composites: Part B 57 (2014) 126–135 131

Fig. 7. Effect of MAPP:NF ratio on impact surface (a) 0.0%; (b) 6.7%; (c) 16.7%.

30% natural fibre loading and 7.6–8.5 GPa for the 50% loading. Flax
and hemp have close stiffness results for both fibre loadings 30%
and 50% with a slight superiority of 7–12% in comparison to the si-
sal behaviour. Fibre content has obviously a positive effect where
the 50% loading has stiffness 42%, 53% and 46% more than those
of the 30% loading for flax, hemp and sisal respectively. Flax has
relatively lower stiffness than hemp because of the 10° inclination
of the fibrils to the stem axis [31].
Fig. 2b shows the strength results. Again the coarser sisal fibres
shows the least strength compared to the bast fibres flax and
hemp. However sisal has the largest jump in strength, where
strength of the 50% group is 18%, 19% and 25% more than the
30% group for flax, hemp and sisal respectively. Close strength re-
the MAPP as a coupling agent in the natural fibre thermoplastic
composites. Figs. 3 and 4 present the effect of different MAPP:NF
ratio on the mechanical properties of natural fibre composites at
30% and 50% fibre content respectively. Maximum value of the
curve plateau is considered the optimum value.
For 30% natural fibre as shown in Fig. 3a, MAPP imparts almost
8%, 10% and 12% improvement in stiffness for flax, hemp and sisal
respectively. Regarding strength improvement after the addition of
MAPP shown in Fig. 3b; 15%, 20% and 4% are attained for the flax,
hemp and sisal. Sisal shows the least improvement with the use of
the MAPP copolymer. This can be attributed to the less number of
120

sults for flax and hemp because both fibres’ constituents and size
(a) 0% 6,7% 10,0% 13,3% 16,7%

100
are similar. This significant increase of strength specially with
the 50% flax can be contributed to the surface matrix adhesion effi- 80
Weight [%]

MAPP:NF increases in
ciency and its impact on the load transfer mechanism [32–34]. 60
the arrow direction

Similar strength and different stiffness values between flax and

40
hemp results, as expected, in lower elongation for hemp. Flax fi-
brils have the chance to elongate along the stem axis. Thus results 20
in the composite elongation shown in Fig. 2c. The elongation of the
50% composites decreased to almost half of the values attained by 0
100 150 200 250 300 350 400 450 500 550 600
30% composites. This results in the non-consistent behaviour of the Temperature [°C]
impact results shown in Fig. 2d. The difference between the aver-
ages of both the 30% and the 50% is insignificant compared to the 1,6
Derivative Weight [%/°C]

inner deviation in each group. 0.4 kJ/m2 difference exists between 1,4 (b) 0% 6,7% 10,0% 13,3% 16,7%

average values of 6.8 and 6.4 kJ/m2 for the 30% and 50% respec- 1,2
tively. While the ranges of the impact results are 1.1 and 1.4 kJ/ 1
m2 for both fibre contents.
0,8
The significance of the results shown in Fig. 2 was also tested by
0,6
two tailed t-test with 95% confidence. T-test proved the signifi-
0,4
cance for the pairs (flax vs hemp), (hemp vs sisal) and (flax vs sisal).
0,2
Two thirds of the results proved significance at 95%.
0
250 300 350 400 450 500 550
3.3. Effect of copolymer to fibre ratio
Temperature [°C]

This section deals with the main problem claimed in this work Fig. 8. Effect of MAPP:NF ratio for 50% Flax PP composites coupled with MAPP
which is the diversity in the optimisation rules for implementing (Type A) on (a) TGA; (b) DTG.
132 A. El-Sabbagh / Composites: Part B 57 (2014) 126–135
Table 4
Effect of MAPP:NF% and type on melt temperature and enthalpy of 50% flax PP composites.
MAPP type MAPP:NF [%] Melt temperature [°C]
Type A 0 167.31
6.7 167.00
10 166.86
13.3 166.28
16.7 166.62
Type B 0 167.81
6.7 166.42
10 164.51
13.3 165.69
16.7 164.29
available sites for copolymerisation on the fibre’s surface due to
their relative bigger size. Impact results shown in Fig. 3c ensures
the efficiency of MAPP copolymerisation compared to the non
MAPP composites. Flax has its optimum results at 10%, 6.7%, 6.7%
for stiffness, strength and impact respectively. Hemp optimum val-
ues are at 6.7%, 6.7% and 10% while sisal values are 6.7%, 6.7%, 6.7%.
Table 3 lists the aforementioned values. Flax has almost 7%
improvement for stiffness at its optimum values while hemp and
sisal have 11% improvement. For strength, sisal has the least
improvement of 5.4% while flax has the best value of 19% and
hemp has 16% increase. Finally for impact, the sisal has the best
improvement more than the other fibres. It is also noted that high-
er MAPP:NF ratio than the optimum induces slightly a negative ef-
fect on the corresponding property.
For 50% natural fibre, flax has optimum values of 13.3%, 6.7%
and 6.7% for stiffness, strength and impact respectively. Hemp val-
ues are 10%, 13.3% and 6.7% while sisal values are 16.7%, 6.7% and
6.7%. Fig. 4a illustrates the stiffness results. Flax stiffness improves
from 6.8 GPa to 8.3 GPa at MAPP:NF = 13.3%. Hemp, similar to its
behaviour at 30% loading, improves from 7.3 GPa to 8.5 GPa at low-
er MAPP:NF = 10%. Sisal slightly improves from 7.6 GPa to 7.6 GPa.
Fig. 4b shows the strength development with the increase of
MAPP:NF ratio. 50% Flax PP composites without coupling agent
show a poor strength of 30.7 MPa which is only 10% more than
the pure PP. However implementing MAPP enhances it immedi-
ately. Therefore at the first investigated point, namely
MAPP:NF = 10%, strength increases of the flax PP composite to
49.6 MPa. Then more MAPP does not result in an improvement
rather a slight strength reduction to 48.6 MPa. Hemp PP composite
without MAPP has a higher strength from the beginning of
41.6 MPa and then improves to 50.8 MPa at 6.7% MAPP:NF. The
same goes for sisal which improves from 43.9 MPa to 51.4 MPa
at 6.7% MAPP:NF. The same behaviour of slight strength reduction
at higher MAPP is observed for the three types of fibres. Finally the
impact behaviour is shown in Fig. 4c. The ratio of 6.7% is enough for
all fibre types to reach the maximum values. Statistical t-test anal-
ysis is applied and confidence of more than 95% is found for the re-
sults of stiffness, strength and elongation.
Fig. 5 summarises the previous section for the 30% and 50% fibre
loadings. It is obvious that 6.7% of MAPP:NF is a suitable solution.
This 6.7% ratio is more consistent with the 30% fibre loading. In
case of 50% fibre loading, the hemp strength is the only deviation
where its optimum at 13.3%. However, the difference in hemp
strength between 6.7% and 13.3% is less than 3 MPa. Only stiffness
which requires 10% for 30% flax and 10–16.7% for all fibres in case
of the 50%. But how much is needed to increase the MAPP: NF ra-
tio? Fig. 6 shows the improvement percentage at the optimum
MAPP:NF. Improvement% is calculated according to Eq. (1).
Improvement% ¼ ½ðP optimum MAPP : NF  PMAPP : NF ¼ 0Þ=
P MAPP : NF ¼ 0 100
where P is the property (stiffness, strength, impact).
Melt enthalpy [j/g] Recrystallisation temp. [°C] Recrystallisation enthalpy [j/g]
51.46 132.26 67.36
54.55 128.87 70.94
58.66 129.18 75.65
56.00 128.99 69.36
44.97 128.19 61.01
51.46
48.75
58.87
50.48
50.84
In general, Stiffness improvement has the least significance
compared to the strength and impact improvements. In other
words; Stiffness shows improvement at higher MAPP:NF where
the tensile and impact strengths are getting maximised at lower
MAPP:NF ratios. This remark can be explained in terms of the more
coupling sites which are reflected in better fibre/matrix adhesion
and hence higher stiffness. On the other side, the tensile and im-
pact strengths are properties related to post-elastic zone range
where the failure either by pull-out or debonding or even fibre fail-
ure promotes the failure regardless how stiff is the composite. An-
other interesting notice is noticed in Fig. 6a where the
improvement of the three fibres at 30% lies in a close range rela-
tively when compared to the deviation between flax and sisal at
50%, Fig. 6b.This is an evidence that natural fibre type and shape
play an important role in the composite behaviour and cannot be
considered as fillers.
Fig. 7 shows SEM fracture surfaces at different MAPP:NF ratios.
Composite free from MAPP copolymer shows long pulled out fi-
bres. At 6.7% MAPP:NF for the 30% flax, the fracture shows less
pulled out fibre length and some fibre debonding sites of transver-
sal fibres. At more MAPP:NF ratio of 16.7%, the fibres are well ad-
hered to the PP matrix and the polymer remnants are present on
the broken pulled fibre surface.
Fig. 8 shows the TGA and the differential thermal gravimetric
DTG of the flax PP composites copolymerised with granulate MAPP
of Type A. Decomposition proceeds by losing the absorbed water
then hemicelluloses followed by alpha cellulose and finally by lig-
nin [35]. The DTG curve in Fig. 8 shows no charring evidence
around 500 °C. This matches the finding of Doan [36] and against
what reported by Bhaduri [37].
Composites show two peaks’ with maxima ranging in 369.4–
374.8 °C and 432.4–481 °C corresponding to the decomposition
ð1Þ
Fig. 9. DSC results of MAPP:NF ratio for 30% Flax PP composites coupled with MAPP
(Type A).
 A. El-Sabbagh / Composites: Part B 57 (2014) 126–135 133

of flax and PP respectively. The recorded decomposition behaviour effect on the fibre matrix interface as reported by [38]. This also
is similar to that of Doan [36]. The temperatures at the peaks’ max- may explain why the wetting seems better although the mechan-
ima are decreasing slightly as the MAPP:NF ratio increases. This ical properties are decreasing when the MAPP:NF ratio is more
note is valid for 0%, 6.7% and 10% of MAPP:NF ratios. For higher ra- than optimum.
tios of MAPP:NF with 13.3% and 16.7%; the decomposition takes DSC results are given in Table 4. Results show similar behaviour
place at significant lower temperatures. This is an evidence that reported by Lee [39]. The melting temperature decrease with the
the excess MAPP induces a dispersion effect rather than a coupling increase of MAPP:NF ratio. The reduction in temperature is too

Flax 30% Flax 50%

7000 10000
6500 (a) 9000 (b)
6000

Stiffness [MPa]
Stiffness [MPa]

8000
5500
7000
5000
6000
4500
5000
4000
3500 4000

3000 3000
0 5 10 15 20 0 5 10 15 20
MAPP/Fibre [%] MAPP/Fibre [%]
Type (A) Type (B) Type (A) Type (B)

Flax 30% Flax 50%

60
49
(c) 55
(d)
47
Strength [MPa]

Strength [MPa]

45 50

43 45
41
40
39
35
37

35 30
0 5 10 15 20 0 5 10 15 20
MAPP/Fibre [%] MAPP/Fibre [%]
Type (A) Type (B) Type (A) Type (B)

Flax 30% Flax 50%

10 4
9 (e) 3,5 (f)
8
Elongation [%]

3
Elongation [%]

7
6 2,5
5 2
4 1,5
3
1
2
1 0,5
0 0
0 5 10 15 20 0 5 10 15 20
MAPP/Fibre [%] MAPP/Fibre [%]
Type (A) Type (B) Type (A) Type (B)

Flax 30% Flax 50%

10 10
9 (g) 9 (h)
8 8
Impact [kJ/m²]

Impact [kJ/m²]

7 7
6 6
5 5
4 4
3 3
2 2
1 1
0 0
0 5 10 15 20 0 5 10 15 20
MAPP/Fibre [%] MAPP/Fibre [%]
Type (A) Type (B) Type (A) Type (B)

Fig. 10. Effect of MAPP:NF on (a,b) Stiffness (c,d) Strength (e,f) Elongation (g,h) Impact.
134 A. El-Sabbagh / Composites: Part B 57 (2014) 126–135

small to be felt as it is almost 0.5%. While in Fig. 9, the melt enthal- 120
py shows an increasing trend or even a plateau effect and a maxi- (a) 0% 6,7% 10,0% 13,3% 16,7%

100
mum value at 10% MAPP:NF then with a steeper trend goes down.
The reduction in enthalpy is greater as it drops to 25% for the MAPP 80

Weight [%]
of Type A and 14% for MAPP of type B. This assures the TGA result
60
of the dispersion phenomenon above 10% MAPP:NF. Interesting is
also the similarity in behaviour of recrystallization where 10% 40
MAPP:NF has the maximum recrystallization energy. This can be
correlated to the maximum efficiency of coupling between the fi- 20

bre and the polymer. Higher MAPP:NF decreases the recrystalliza- 0

tion because the excess MAPP does not react with itself when do 100 150 200 250 300 350 400 450 500 550 600
not undergo grafting [13]. Temperature [°C]

1,8
3.4. Effect of copolymer type
(b)

Derivative Weight [%/°C]

1,6 0% 6,7% 10,0% 13,3% 16,7%

For the sake of comparison between MAPP types A and B, Fig. 10 1,4

shows the mechanical properties corresponding to both 30% and 1,2

50% flax with the different forms of the MAPP. Granulate MAPP, 1

Type A, always shows near parabolic forms with optimum values 0,8

while the powder MAPP, Type B, shows that even after reaching 0,6
the optimum value, constant or slightly increasing trend is still 0,4
going on. Fig. 10a and b show the stiffness behaviour for both fibre 0,2
loadings of 30% and 50%. Type B does not impart improvement for 0
250 300 350 400 450 500 550
the 30% composite stiffness whereas Type A imparts almost 7%
Temperature [°C]
improvement at the 6.7% MAPP:NF ratio. For the 50% fibre loading,
both types A and B result in an improvement namely 20% and 15%. Fig. 11. Effect of MAPP:NF ratio for 50% Flax PP composites coupled with MAPP
It is important to note that the optimum MAPP:NF ratio is the same (Type B) on (a) TGA (b) DTG.
for the 30% and 50% fibre loadings. Fig. 10c and d show the strength
behaviour. Type B has a better effect than Type A on the composite
strength. Type A has a faster strengthening effect than Type B. Type and impact. It is also noted that the change in the first peak around
A has its optimum MAPP:NF ratio of 6.7% in the 30% composite the 370 °C is more affected in case of Type B. This is also matching
whereas Type B has a slower response and reached its maximum with the results of Lee [25] who worked with bamboo fibre PP
at 13.3%. In case of 50% composite, Type A again has a maximum composites.
point at 6.7% of MAPP:NF. The Type B shows an increasing linear DSC results are given in Table 4. Results show similar behaviour
trend of composite strength in the range of 6.7–16.7% without reported by Lee [38]. The decrease in melting temperature and en-
reaching an optimality point. thalpy is slightly larger in MAPP of Type B compared to Type A. This
Fig. 10e shows an interesting observation. Type A composite has is attributed to the more reaction and higher diffusivity of Type B
a decreasing elongation with more MAPP:NF whereas the Type B [31].
has a softer effect where the elongation slightly changes in the Finally the effect of copolymer type on the water absorption le-
30% and 50% fibre loading composites. The same behaviour for vel by natural fibre thermoplastic composite. Fig. 12 shows better
Type A and B is observed in Fig. 10f with lower elongation values. behaviour for the granulated Type A MAPP where the water
Fig. 10g shows the impact results of the un-notched specimens absorption of Type B composites is about 16% more than those of
for the composites filled with 30% flax. Both types A and B are coin- Type A composites. A decreasing trend is noticed with the increase
cident in the 0–6.7% range then Type B continues positively in of MAPP:NF ratio. This points out to sufficient interface reaction
comparison to Type A. Again the same behaviour is repeated in due the Type A copolymer compared to the Type B. This is attrib-
Fig. 10h for the 50% filled composites. However, the change is less uted to the high MA grafting of Type A [27].
positively for Type B and negatively for Type A.
The better behaviour of Type B in general can be attributed to
the better thermal stability of the composites with higher molecu-
lar weight of the powder form MAPP. As mentioned earlier; Type B
has normally lower acid number and hence higher melt flow index
MFI, better mixing, and better diffusion [28]. This explains the
good impregnation of the coupling inside the fibres. Type A shows
a drop in strength after reaching the maximum value because ex-
cess MAPP does not result in more coupling with fibres but results
in self reaction leading to a weak layers instead. Type A has faster
thermal degradation as shown in Fig. 8. This is due to more MAPP:
NF compared to the more thermal stability of MAPP Type B, as
shown in Fig. 11. The DTG curve, shown in Fig. 11b, shows two
peaks with ranges of 357.3–374.8 °C and 480–486 °C. The increase
of MAPP:NF ratio to 16.7% leads to 48 °C degradation of the ther-
mal stability which is less than 6 °C degradation for the Type A
composites. The result, that Type B has more thermal stability,
matches the results of Kim [27] where the lower molecular weight
copolymer has lower thermal stability behaviour. excessive
MAPP:NF does not impart enhancement of composite strength Fig. 12. Effect of MAPP:NF ratio and MAPP type on water absorption.
 A. El-Sabbagh / Composites: Part B 57 (2014) 126–135
4. Conclusions
The behaviour of the NFTC mechanical properties is dependent
on the fibre type. In other words; fibre type plays an important role
in the strengthening and cannot be considered as fillers only. Pre-
treatment of 5% NaOH for 24 days at room temperature is sufficient
to have more efficient fibre surface for coupling with the thermo-
plastic matrix and hence further processing. The optimum
MAPP:NF is searched for and the following points are deduced:
(1) MAPP: NF ratio of 6.7% is enough for having a high improve-
ment in mechanical properties. However for reaching Maxi-
mum value in the studied property (Stiffness, strength,
impact), more MAPP:NF ratio is needed. This result suggests
that lower ratio tan 6.67% can result in an acceptable
improvement in strengthening.
(2) Optimality for each property (stiffness, strength and impact)
are defined for flax, hemp and sisal natural fibres as shown
in Table 3.
(3) In general, it is noticed that the required MAPP:NF ratio for
maximising the Stiffness is less than that needed for maxi-
mising both tensile strength and impact strength properties.
This is explained in terms of the increasing probability that
failure scenarios are most likely to happen in the fibre or
the matrix/fibre interfaces. These failure favourite places
for failure are increasing with the increase of fibres.
(4) Granulated Type A MAPP is better in the range of [0–6.7%]
for stiffness and strength and vice versa. For impact, both
types go on coincidently then type B composites result in
higher impact properties. Composites of high percentage
Type B MAPP has more thermal stability than the Type A
composites. This is related to the more molecular weight
of Type B. Water absorption of the Type A MAPP natural fibre
composites are better than the Type B MAPP composites.
Acknowledgements
Thanks are given to the Fachagentur Nachwachsende Rohstoffe
e.V. (FNR) agency for financing. Also the help of Dr Leif Steuernagel,
Dr Dieter Meiners and Prof Ziegmann through the mutual deep
discussions.
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