Composites Science and Technology 63 (2003) 18651875

www.elsevier.com/locate/compscitech

Optimization of a ame-retarded polypropylene composite

H. Dvira, M. Gottlieba,*, S. Darenb, E. Tartakovskyb
a

Chemical Engineering Department and Stadler Minerva Center for Mesoscopic Macromolecular Engineering,
Ben Gurion University, Beer Sheva 84105, Israel
b
Dead-Sea Bromine Group Ltd, POB 180 Beer Sheva, Israel
Received 25 April 2002; received in revised form 3 March 2003; accepted 11 March 2003

Abstract
Composite materials demand constant improvements in mechanical and ame retardant (FR) properties. The goal of this project
is to study the eect of additives on these properties in polypropylene composites containing glass bers, pentabromobenzyl acrylate (PBBMA) as a primary FR and magnesium hydroxide as a secondary FR. Optimal composition is reached by means of statistical design of experiments (DOE) rather than by trial and error approach. The DOE approach allows minimization of the
number of experiments, investigation of the inuence of each additive and the mutual interactions between additives. It also allows
here, prediction of optimal sample properties better than 8% from experimental values. The optimal composition exhibits improved
mechanical and FR properties. Both FRs reduce the impact strength while enhancing ame retardancy. Glass bers increase the
modulus, but have only a moderate eect on the impact strength due to poor adhesion with PP. The interpretation of the eect of
glass bers on the ammability is inconclusive.
# 2003 Elsevier Ltd. All rights reserved.
Keywords: A. Glass bers; A. Polymer-matrix composites; B. Mechanical properties; C. Statistics; Flame retardancy

1. Introduction
Polypropylene (PP) is a polymer of great importance
in the industrial sector due to its low density, high water
and chemical resistance, ease of processability and being
one of the most cost-eective polymers available today.
It is employed in numerous applications from nonwoven bers to the automotive industry. Its relatively
low price is the driving force to improve its performance, to broaden its versatility and to enable it to
compete with other polymers used nowadays for more
demanding applications. PP as the polymer host
requires the incorporation of additives and reinforcement in order to enhance its mechanical properties. One
of the most commonly used reinforcement agents are
chopped strand silane surface treated glass bers. The
glass bers are surface modied since PP has a nonpolar nature, which hinders its interaction and adhesion
to polar llers such as glass bers. The surface treatment improves the compatibility of the glass with the PP
* Corresponding author. Tel.: +972-8-646-1486; fax: +972-86472916.
E-mail address: moshe@inca.bgu.ac.il (M. Gottlieb).
0266-3538/03/$ - see front matter # 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0266-3538(03)00170-2

and hence improves the mechanical properties of the

composite [1]. PP, in common with most synthetic
polymers, is ammable and may therefore be hazardous
near an open ame. It may also enhance re propagation due to its tendency to drip when hot. Therefore, the
addition of a ame retardant is an essential requirement
if we wish to achieve a PP based composite with good
ame resistance. Pentabromobenzylacrylate (PBBMA),
used as a ame retardant in PP composites, is a crystalline monomer with a chemical structure shown in
Fig. 1a. PBBMA may polymerize by free radical polymerization of the unsaturated acrylic bond initiated
thermally during reactive extrusion to produce
poly(pentabromobenzylacrylate) (PBBPA) [2] whose
structure is shown in Fig. 1b. The re retardancy
mechanism of this FR and its suitability for use with PP
has been discussed previously [35].
A fraction of PBBMA reacts to a variable degree [3]
with PP to form either a graft (PP-g-PBBPA), or it may
attach to low molecular weight PP chains as an endgroup. The grafting of PBBMA onto PP may increase
the polarity of the PP and thus enhance its adhesion to
polar llers, a role that is presently performed by modiers such as maleic anhydride. More details can be

1866

H. Dvir et al. / Composites Science and Technology 63 (2003) 18651875

Fig. 1. Chemical structure of the FR: (a) monomer (PBBMA), (b)

polymer (PBBPA).

found in our previous work [35] which dealt with the

extent of thermal polymerization, grafting of the FR
onto PP, and the amount of residual monomers left in
the system. The inuence of other additives on the
reaction and resulting morphology was also reported in
these references.
The addition of PBBMA imparts ame retardant
properties to the PP composite and possibly improves
its ller compatibility, as previously discussed. Yet, it
also has adverse eects on the mechanical properties of
the composite. Glass bers may balance these antagonistic eects. Although added as reinforcement agent,
glass bers are also expected to improve ame retardant
properties by diluting the host polymer. The addition of
secondary additives may further improve or deteriorate
the mechanical and ammability properties of the composite. Application requirements, which often demand
dierent combinations of properties, may dictate the use
of a specic composite material whose constituents will
act synergistically to meet the needs of the application.
The eect of each individual additive is easily determined by means of several simple experiments. How-

ever, synergistic/antagonistic interactions between the

dierent additives are not obvious and require in-depth
investigations. Usually, in designing a polymer possessing a specic set of properties, it is necessary to balance
between the product costs and its properties, which
should be at least equivalent if not better than those of
the polymer host. There can never be a single ideal
composite, since each additive contributes its own
particular attributes. Thus, it is of practical importance
rst of all, to understand better the eect of dierent
additives and the interactions between them in the most
ecient way and secondly, to be able to forecast composite properties based on the knowledge acquired.
In this paper, we describe a method for the determination of the contribution of each of the additives (formulation variables) by means of the experimental design
followed by statistical analysis of mechanical and ame
retardant properties (responses). In this approach, the
system is considered as a black box that is aected by a
number of independent controllable input variables
whose actions are transformed to the changes in the
system responses. The variation of the measured
response caused by the modication of controllable
input variables can be translated to a predictive mathematical model. The model developed can then be used
to predict response within the operating range of controllable variables.
In the next section the details of the experimental
methods are described. The statistical methods used to
design the experiments and analyze the data are
detailed in Section 3. The eect of the dierent variables on the tested properties, their statistical signicance, interactions between variables and the
optimization of composite formulation are discussed in
Section 4.

2. Experimental
2.1. Materials
The materials are all technical grade, commercially
available and were used as received. A typical formulation
was prepared by compounding the following materials:
Polymer matrix:
Polypropylene (3120MN1, Appryl, France) d=0.9 g/
cm3, fusion temp=163
C.
Additives:
1. A. PBBMA (FR1025M, DSBG, Israel) primary
FR;
B. Antimony trioxide (ATO). A masterbatch of
80% Sb2O3 and 20% Low Density Poly(ethylene), characteristic diameter 1.5 mm
(L0112 Kafrit, Israel) is added as FR synergist. For optimal FR activity, it is added in
1:3 ratio of ATO:PBBMA.

H. Dvir et al. / Composites Science and Technology 63 (2003) 18651875

2. Irganox B225, a blend of Irganox 1010-hindered

phenol type and Irgafos 168-phosphate type
(Ciba Giegy, Germany). It is an antioxidant,
which is added in order to prevent PP oxidation
during compounding (the commercial PP above
contains  800 ppm of this antioxidant).
3. Magnesium Hydroxide, coated with 2% stearic
acid (FR20, DSBG, Israel). It is used as multifunctional ller with intrinsic ame retardant
properties. It serves as a secondary FR.
4. Chopped Glass Fibers with characteristic length
4.5 mm and characteristic diameter  10 mm,
d=2.6 g/cm3 (P968, Vetrotex, France). Serves as
the primary ller added in order to improve
mechanical properties. The ber surface is treated by the manufacturer with a silane-based
coupling agent for better compatibility with PP.
5. Maleic Anhydride modied PP (PP-g-MAH).
(Exxelor VM42E, Exxon Mobile, USA)
d=0.9g/cm3, used as a compatibilizer, gives the
PP a somewhat polar nature. Only the grafted
polymer is used, no free MAH is added to the
composite.
In addition small amounts (0.2 wt.%) of
Poly(ethylene) wax (AC-6A, Allied, USA) were added
in order to reduce shear stresses developed during
extrusion.
2.2. Compounding of composites
The ve components listed above have been selected
as controllable input variables for the optimization of the
composite. The relative amounts of these additives and
the way these amounts were selected will be described in
the section dealing with the experimental statistical
design. Once the amounts to be used had been determined, the composite was compounded as follows:
All formulations were compounded in a twin screw
extruder (Berstor ZE25 co-rotating, open vent, extruder
L/D=32) at 250
C, and 350 rad/min angular velocity of
the screws rotation, and subsequently pelletized. The
pellets were dried overnight, then injected by means of
an Arburg Allrounder 320S injection molding machine
into molds of the required specimen shape for the
appropriate tests (e.g. dog-bone shape for tensile test,
rods for UL94V ammability test etc.). A nozzle temperature of 240
C and an injection pressure of 1300 bar
were employed.
2.3. Flame retardancy tests
2.3.1. Vertical UL94 (UL94V)
Rectangular rod shaped samples with dimensions of
12712.73.2 (or 1.6) mm are exposed vertically to a
methane gas burner ame for 10 s, as required by

1867

UL94V. The sample is ignited at the bottom and burns

upward. The time required for the ame to self extinguish after burner removal is measured and the occurrence of dripping onto a piece of cotton placed
underneath the sample is recorded. The test is repeated
for ve dierent samples. If none of the samples
burns for more then 10 s and the drips do not ignite
the cotton, the material is classied as V-0. If none
burns for more then 30 s and the drips do not ignite
the cotton, the material is classied as V-1, but if the
cotton is ignited the material classied as V-2. If any
of the samples burns for more than 30 s or if the
entire sample is consumed, the material is classied
as non-rated (NR).
2.3.2. LOI (limiting oxygen index)
Samples shaped as rods or strips with dimensions
756.53 mm were enclosed in an open-vent chamber
in a mixed oxygen/nitrogen environment. The sample is
ignited at its upper end with a hydrogen ame. The
sample burns from the top downwards. The atmosphere
composition that permits steady burning is determined.
The limiting oxygen index is the minimum fraction of
oxygen in the gas mixture that will sustain burning for 3
min or 2 inches, (whichever comes rst). The system was
calibrated using a standard sample with a dened LOI
value (ASTM D-2863-77). It should be reminded that it
is incorrect to assume that material with an oxygen
index over 21% can not burn in practice despite the fact
air contains only 21% oxygen. Such an assumption disregards the fact that burning proceeds upward causing
preheating so that materials with oxygen index over
21% will burn in air.
2.4. Mechanical tests
2.4.1. Izod impact reversed notched
The sample used here is the same as in UL94V test
above. A standard notch (2.5 mm long and 0.25 mm
notch tip radius) is applied to the specimen. For the
reversed Izod, the notch is in the opposite direction to
the striking hammer. The samples were examined in a
Zwick apparatus. The striking energy of the pendulum
was 1 J (ASTM D-256-81).
2.4.2. Tensile strength
The sample used in the tensile test has a dog-bone
shape in order for either necking or failure to occur in
the center of the specimen and not near the clamps. The
sample is loaded at a constant rate and the stress
applied is recorded. The samples were tested in a Zwick
1435 apparatus. Measurement procedure and calibration was performed according to ASTM D-638-95.
Before experiments were carried out optimal testing
conditions were determined. It was determined that the
tensile modulus for our samples should be obtained by

1868

H. Dvir et al. / Composites Science and Technology 63 (2003) 18651875

tests carried out in the range of extension forces

between 200 and 600 N.

Table 2
Initial formulations
Component

Formulation No.
Units

3. Statistical experimental design

3.1. Choice of the operating ranges for the controllable
variables
The amounts of ve additives were chosen as controllable input variables for the experimental design:
glass bers, PBBMA/ATO, PP-g-MAH, Irganox and
Mg(OH)2. The range of concentrations of each variable
is shown in Table 1. The two FRs: PBBMA as a primary FR and Mg(OH)2 as a secondary one, were selected for the following reasons. A ame-retarded PP
composite based on Magnesium Hydroxide alone
requires extreme FR loading up to 65% by weight, in
order to achieve acceptable ame retardancy (V-0 classication). Such loading will result in a composite with
very poor mechanical properties. The same is true for
PBBMA, which requires a loading of approximately
30% if used alone [6]. The incorporation of both FRs in
PP allows the use of lower amounts of FRs with better
mechanical properties and at reduced cost, with identical ame retardancy properties.
The percentage of the PP itself has been set to a constant level of 38.5% in all formulations. Higher concentrations of PP in the composites result in
unacceptable ame retardancy as can be seen in Table 2.
These data show the narrow window available for PP
concentration to obtain a formulation with acceptable
ame retardant properties. For example, the sample
containing 38.5% PP is classied as V-0. Increasing the
PP concentration at the expense of Mg(OH)2, by a mere
1.5% would result in improved mechanical properties
but causes total ammability failure. The high sensitivity
of ame retardancy to small changes in the matrix composition makes the use of statistical design an invaluable
methodological approach. The best composition
obtained prior to the application of the statistical analysis serves as the starting point for the statistical analysis
and will be referred to as the best initial formulation.
On the basis of this narrow window, we attempt to
optimize other components in the composite such that
Table 1
Constrains for controllable variables in DOE
Variable

Upper limit
[+] (% w/w)

Lower limit
[] (% w/w)

Glass bers
PBBMA+ATO (3:1)
MAH
Irganox
Mg(OH)2

25
20
2
0.3
25

15
13.3
1
0
14.15

PP
Glass bers
PBBMA
ATO
MAH
PE Wax
Irganox
Mg(OH)2

%
%
%
%
%
%
%
%

UL-94 Rating (3.2 mm)

Max. aming time
s
Total aming time
s
Cotton ignition
LOI
%
a

A1
38.5
20.0
14.0
4.6
1.0
0.2
0.3
21.4

A2

A3

A4

40.0
20.0
14.0
4.6
1.0
0.2
0.3
19.9

42.0
20.0
14.0
4.6
1.0
0.2
0.3
17.9

44.0
20.0
14.0
4.6
1.0
0.2
0.3
15.9

V0
NRa
10
19
49
86
No
No
25.025.5 25.025.5

NRa
55
178
No
25.025.5

NRa
50
242
No
24.024.5

NR, Non Rated in UL94 classication.

best possible mechanical and ame retardant properties

are obtained. This implies that the amounts of these
components in the composite are varied in a regular
manner between maximum and minimum values based
on prior knowledge.
1. The concentration of glass bers was varied
between 15 and 25% due to the superior
mechanical properties achieved within these
limits.
2. The primary FR PBBMA was used in combination with ATO as an FR synergist at an optimal constant ratio of 3:1 [7]. The selected upper
limit for this FR (15%) is the value in the V-0
formulation in Table 2. Economical arguments
set this as an upper bound for the FR. The lower
limit (10%) is believed to be the lowest value that
can still achieve V-0 ame retardancy in this
system and even that only in the presence of
other components.
3. The amount of PP-g-MAH is varied within the
range from 1 to 2%. It is customary to add 2% of
maleic anhydride to PP. The decision to use a
smaller amount of PP-g-MAH as the lower limit
was based on the assumption that PBBMA may
also graft onto PP and play the same surfacemodifying role as maleic anhydride.
4. The fourth variable is the antioxidant Irganox
B225, which is a radical scavenger and may
interfere with the polymerization of the
PBBMA in the composite. Therefore the lower
limit was set to zero and the upper limit was
based on the amount customarily used in PP
composites.
5. The amount of the last variablethe secondary
FR (Mg(OH)2), was set by the overall amount of
the other components to add up to 100%.

H. Dvir et al. / Composites Science and Technology 63 (2003) 18651875

3.2. Statistical methods

The optimization of the formulation compositions
with respect to their desirable characteristics (called
responses) is performed using the technique of mixture
design. The outcome of the experimental design is a
mathematical expression for the value of the responses
as a function of the dierent ingredients in the composite (named factors). The total number of experimental
points is the smallest number of experiments that still
enable the formulation of this mathematical expression
which is termed the response surface and can be represented by the following quadratic regression formula [8]:
R

q
q
X
X
bi xi  bij xi xj
i1

i<j

where R, the experimentally measured response; xi,

concentration of the ith ingredient (the values of xi are
prescribed by the statistical design and are known for
each experimental plan); bi, the regression coecients,
values of which are chosen to achieve the best tting of
the model to the given experimental data; and q, the
number of ingredients in the mixture.
The terms of the type bixi express the direct inuence
of the ith ingredient on a certain response R (main
eects of factors): the higher the value of bi, the greater
the inuence of the ingredient on the response. The
terms of the type bijxIxj express the so-called interactions
between factors. These interaction terms reect the nonadditivity in the inuence of pairs of factors on a given
response: the higher the value of bij, the higher the
degree of non-additivity in the combined inuence of
the ith and jth factors on the response.
The statistical signicance of the factor eects is
obtained by comparison of the bi values with the estimate of the random noise in the system. This estimate is
obtained as the standard deviation in a series of repeated experiments built into the experimental plan. The
main eects are estimated by the approximate t-test in
the framework of the mixture linear model. The second
order interactions between variables are estimated by a ttest in the framework of a mixture quadratic model. The
level of signicance for all statistical tests, both for the
main eects and second order interactions, was chosen
to be =0.05. In other words, if a p-value in a test for
the signicance of a certain factor is smaller than 0.05,
this factor is considered statistically signicant at
=0.05 level of signicance. One should remember, that
the p-value represents the smallest level of signicance
that would lead to rejection of the null-hypothesis (i.e.
there is no eect of the controllable factor on the
response under investigation) while this hypothesis is
true. The smaller the p-value obtained in the analysis of
the inuence of a certain factor on the response under
investigation, the higher the probability that this factor

1869

does inuence the response. Factor interactions of third

or higher orders are assumed to be negligible, as is routinely practiced in the DOE process.
The design of experiments of choice was a two-level
plan, i.e. the concentration of each factor (ingredient)
was examined at two levels, the high and the low levels
of concentration. Specically, the experimental plan was
a D-optimal two-level mixture design for ve variables.
The statistical analysis of the chosen D-optimal mixture
design was performed by Design Expert software
[Design-Expert1 V 5.0.8, Stat-Ease-Corp., Minneapolis
MN 55413-9827 USA].
The control factors (i.e. concentrations of the additives) and their experimental constraints (high [+] and
low [] levels) are presented in Table 1.
The experimental matrix included 20 runs: 15 runs for
the quadratic model, 2 runs for the curvature estimation
and 3 replicate runs for the estimation of the random
noise [9]. The experimental plan was created and analyzed by the Design Expert software. The full experimental matrix is presented in Table 3. The experiments
were performed in a completely randomized sequence as
set by the software. The nal outcome of the analysis is
an optimal composition with its associated desirability
value (1.0highly desirable, 0highly undesirable) and
predicted properties.

4. Results and discussion

The results of all the mechanical and ame retardancy
tests performed are listed in Tables 4 and 5.
4.1. Statistical analysis of the factors and the interactions on the mechanical properties
In general, the statistical analysis demonstrates the
existence of statistically signicant eects, both main
eects and interactions. The following paragraphs
present the results of the statistical analysis of the chosen D-optimal mixture design and the discussion of
inuence of main eects and of interactions on the
composite properties.
4.1.1. Modulus
Only PP-g-MAH has a statistically signicant inuence (p-value=0.01) on the composite modulus at the
main-eect level of analysis. Maleic anhydride is primarily used as a modier in order to improve the adhesion between the polymer host and the glass bers by
facilitating the interaction between the non-polar PP
and polar ller. Such interactions are known to increase
the modulus of PP composite [10]. On the other hand,
PP-g-MAH is known to adversely aect the modulus of
bulk PP by hindering PP crystallization [11]. Under normal circumstances the improved adhesion overcomes the

1870

H. Dvir et al. / Composites Science and Technology 63 (2003) 18651875

Table 3
Experimental matrix for the mixture design
Component

Formulation No.
Units

PP
Fibers
PBBMA
ATO
MAH
PE Wax
Irganox
Mg(OH)2

%
%
%
%
%
%
%
%
Units

PP
Fibers
PBBMA
ATO
MAH
PE Wax
Irganox
Mg(OH)2

%
%
%
%
%
%
%
%

10

38.50
25.00
10.00
3.30
1.50
0.20
0
21.50

38.50
21.68
12.50
4.15
1.00
0.20
0.30
21.67

38.50
25.00
12.50
4.15
1.00
0.20
0.15
18.50

38.50
17.78
13.90
4.64
1.77
0.20
0.22
22.98

38.50
15.00
14.63
4.87
2.00
0.20
0.30
24.50

38.50
25.00
15.00
5.00
1.50
0.20
0
14.80

38.50
15.00
14.74
4.91
2.00
0.20
0
24.65

38.50
23.35
10.00
3.30
1.00
0.20
0.30
23.35

38.50
15.00
14.74
4.91
2.00
0.20
0
24.65

38.50
22.85
10.00
3.30
2.00
0.20
0.30
22.85

11

12

13

14

15

16

17

18

19

20

38.50
20.00
15.00
5.00
1.00
0.20
0.30
20.00

38.50
20.85
10.00
3.30
2.00
0.20
0.15
25.00

38.50
25.00
12.50
4.15
2.00
0.20
0
17.65

38.50
18.65
12.50
4.15
1.00
0.20
0
25.00

38.50
25.00
15.00
5.00
1.50
0.20
0.30
14.50

38.50
18.10
12.30
4.10
1.50
0.20
0.30
25.00

38.50
25.00
15.00
5.00
1.50
0.20
0.30
14.50

38.50
15.15
15.00
5.00
1.00
0.20
0.15
25.00

38.50
20.00
15.00
5.00
2.00
0.20
0.15
19.15

38.50
22.85
10.00
3.30
2.00
0.20
0.30
22.85

Table 4
Flame retardancy results of the mixture design matrix
Formulation No.
Units
UL-94 Rating (3.2 mm)
Max. aming time
Total aming time
Cotton ignition
UL-94 Rating (1.6 mm)
Max. aming time
Total aming time
Cotton ignition
LOI

V1
s 26
s 143
No
NRa
s 32
s 227
Yes
% 24.024.5
Units

UL-94 Rating (3.2mm)

Max. aming time
Total aming time
Cotton ignition
UL-94 Rating (1.6mm)
Max. aming time
Total aming time
Cotton ignition
LOI
a

10

V0
9
27
No
V1
19
71
No
25.526.0

V1
19
83
No
NRa
40
142
Yes
25.025.5

V0
6
9
No
V0
5
25
No
26.026.5

V1
23
64
No
V2
26
85
Yes
26.527.0

V0
2
4
No
V0
4
12
No
25.025.5

V0
0
0
No
V0
5
13
No
26.026.5

NRa
48
182
Yes
NRa
55
266
Yes
24.525.0

V0
0
0
No
V0
5
15
No
25.025.5

NRa
32
120
No
NRa
39
161
Yes
24.525.0

12

13

14

15

16

17

18

19

20

NRa
40
134
No
NRa
53
241
Yes
24.024.5

V1
13
41
No
V2
20
100
Yes
24.024.5

V0
1
1
No
V0
2
5
No
25.526.0

V1
13
44
No
V1
19
102
No
25.025.5

V1
12
42
No
NRa
47
128
No
25.025.5

V1
24
65
No
NRa
31
86
No
25.526.0

V0
4
6
No
V0
3
8
No
26.026.5

V0
10
45
No
V1
10
54
No
26.026.5

NRa
60
257
Yes
NRa
45
222
Yes
24.024.5

11

V0
7
30
No
V0
s
9
s 48
No
% 25.526.0
s
s

NR, Non Rated in UL94 classication.

negative eect on crystallization resulting in overall

increase in modulus. Contrary to our expectations, a
higher maleic anhydride concentration resulted here in a
lower composite modulus. A possible interpretation is
as follows: the FR replaces PP-g-MAH at the ber surface hence reducing the eectiveness of PP-ber interaction. As a result, we hypothesize that in the present
formulation the maleic anhydride favors the PP bulk on

the PP-glass bers interface. In the PP bulk the grafted

MAH groups of the PP-g-MAH interfere with PP crystallization. This interpretation is not supported by any
direct experimental observation but is indirectly inferred
from DSC measurements, which show that maleic
anhydride lowers the amount of crystalline PP [3]. The
heat of fusion measured by DSC reects the degree of
crystallinity of a composite. When the heats of fusion

1871

H. Dvir et al. / Composites Science and Technology 63 (2003) 18651875

Table 5
Mechanical properties results of the mixture design matrix
Formulation No.

Modulus
Max. strength
Impact


Modulus
Max. Strength
Impact


Units

10

MPa
MPa
J/m
J/m

6297
39.2
78.7
2.4

6288
40.9
87.8
5.4

6488
41.7
101.5
2.5

4777
37.6
100.0
8.9

4874
37.9
103.4
2.8

6521
42.3
98.7
4.2

4508
36.4
90.6
9.1

6396
41.5
97.5
8.4

4245
36.2
89.4
2.8

5690
39.6
90.3
6.8

Units

11

12

13

14

15

16

17

18

19

20

MPa
MPa
J/m
J/m

5683
40.4
95.0
7.2

5373
37.6
92.5
10.2

5803
39.7
82.2
5.9

5082
36.6
83.7
5.6

6032
40.4
101.2
10.0

4890
36.7
93.1
4.6

6021
40.3
93.1
4.6

4354
36.7
95.6
6.5

5047
38.2
85.6
5.2

5444
39.1
96.9
4.4

and crystallization were analyzed as responses in the

framework of DOE, an increase in maleic anhydride
concentration was shown to decrease the heat of fusion
and even more signicantly, the heat of crystallization
(p-value=0.06).
4.1.2. Maximal strength
At the main-eect level of analysis we nd again that the
addition of maleic anhydride (in the form of PP-g-MAH)
lowers the mechanical properties of the composite, in this
case the maximal strength (p-value=0.02). This is ascribed, as before, to the lowering of PP crystallinity.
In addition to the main-eect we also nd here substantial negative interactions of second order:
1. Glass bers enhance maximal strength at low
concentrations of maleic anhydride in a more
pronounced way than at high concentrations
(p-value=0.05).
2. The addition of large amounts of PBBMA over
the entire range of PP-g-MAH concentrations
results in decreased values of maximal strength
relative to those observed with low amounts of
PBBMA (p-value=0.06).
3. The addition of PP-g-MAH in presence of
Mg(OH)2 results in lower maximal strength
(p-value=0.08).
All of the above indicate a poor modifying eect of
maleic anhydride in the presence of the FR apparently
due to its reduced role in adhesion at the polymerller
interface. Maleic anhydride may interact with ller surfaces via a reaction between its functional group and
OH groups on Mg(OH)2 or glass bers [10]. PBBMA
may also react with the llers via a radical mechanism
and hence compete with the maleic anhydride for sites
on the surface of those llers. This may force the maleic
anhydride away from the ller surface and into the
bulk of the PP matrix. It may be concluded that since
both the glass bers and the Mg(OH)2 are surface
modied to render them less polar, the addition of the

maleic anhydride (PP-g-MAH) as compatibilizer was

unnecessary in this case and had negative eects as
result of rejection by the other additives.
4.1.3. Izod impact
Statistical analysis of factor-inuences on impact
strength, as determined by the notched Izod Impact test,
failed to reveal any signicant eects. This was due to,
the large scatter in the data (the range of measured
values was 15 (a.u.) with an absolute standard deviation
of  8) that may have masked any eects present.
Statistical analysis of the reversed notched Izod
Impact test results showed that all of the factors under
investigation had signicant inuence as main eects on
this response. There were no statistically signicant
interactions.
Increasing the PBBMA concentration causes a reduction in impact strength (p-value=0.04). We have determined [3,4] that in its monomeric form the FR is
insoluble in the matrix, while in its polymeric form it
modies the morphology of PP. It is dicult at this
point to determine the exact mechanism by which the
FR reduces the impact strength of the composite. Yet, it
may be attributed either to the change in morphology,
to a plasticizing eect of the monomeric FR, to a
change in interaction between adjacent PP chains due to
FR grafting, or to a combination of these eects.
Increasing the concentration of Mg(OH)2 particles
also aects adversely (p-value=0.02) the impact
strength. The presence of high loading of solid particles
embedded in the polymer matrix results in reduced
ability to absorb impact energy. This is due to the ller
eect, which damages matrix continuity, and each particle is a site of stress concentration, which can act as a
microcrack initiator [12]. Mg(OH)2 is sized with stearic
acid, which comprises a long carbon chain that adheres
to the polymer matrix. It may be argued that these
chains reduce stress concentration in the particle vicinity, but apparently its eect is insucient to overcome
the negative eect of the high loading of particles. Thus,
the net result is a decrease in impact strength.

1872

H. Dvir et al. / Composites Science and Technology 63 (2003) 18651875

The addition of maleated PP also reduces composite

impact strength (p-value=0.07). This may be attributed, as before, to its eect on the morphology and
chain conformation in the PP matrix.
Glass bers have the most unexpected eect observed
in the reduction of impact strength within the 1525%
loading range (p-value=0.02). The increase of glass
ber concentration from low level to high level causes a
small, but statistically signicant decrease (i.e. gentle
negative slope) in impact strength. This is in contrast to
the large expected increase in impact strength and the
increase observed in PP composite, which contain only
glass bers. Glass bers are presumed to disperse the
impact energy over a large volume, especially when the
bers are surface treated with silane coupling agents to
improve direct interaction with the PP matrix. In addition, glass bers have the role of fracture propagation
inhibitors [13]. We have shown [4] that in this composite, despite the sizing, there is poor adhesion and
therefore the glass bers act as an additional solid ller
with a detrimental eect on composite impact resistance, as discussed above.
Increasing the Irganox B225 concentration increases
the impact strength (p-value=0.02). This may be
attributed to the prevention of PP oxidation. PP oxidation gives rise to end products such as ketones, which in
turn may lead to chain degradation and reduction in
molecular weight resulting in loss of mechanical properties. In addition, Irganox, as a radical scavenger, should
inhibit secondary undesirable reactions of free radicals
formed during a mechanical fracture of the chains.
4.2. Statistical analysis of the factors and the interactions on the ame retardant properties
Prior to the discussion of ame retardant properties, we
will briey review the ammability tests carried out.
For a given product, the re hazards in dierent areas
of application (e.g. building, transportation, electrical
consumer products, textile etc.) are so dierent that
ammability information from one category, does not
apply to another. Even within one category there is
large variability between specic applications. Standard
laboratory tests try to remove unimportant parameters
in a certain situation and focus on the relatively important ones. However, these tests do not predict material
behavior in actual re, because they are limited to small
laboratory scale re simulations. These tests are intended only to compare between ammability properties of
dierent materials under similar re conditions. One
cannot compare results obtained by dierent tests
because of lack of correlation due to the dierent purpose and the dierent re situation partially reproduced
in each test. These ammability tests also dier in dierent countries based on local regulations and standards. In
our particular case, the two tests employed are classied

as combustibility tests. The LOI test which is common

for materials used in coverings and linings, and in cables
and wires for the construction industry, expresses
ammability performance by a numerical valuethe
oxygen index (cf. Section 2). UL94V is commonly used
in applications other than building materials, especially
in the electrical consumer products industry (plastic
parts in devices and appliances). UL94V classies a
product by its ammability based on a qualitative
scale [14]. PP the polymer used here, is classied as
NR in UL94V and has a LOI value of 1717.5.
In the evaluation of UL94V results, only the total
aming time was subjected to statistical analysis. As
explained in the Experimental section above, each test is
repeated for ve dierent samples of the same composition. The aming time results for V-0 class samples are
relatively reproducible with low dispersion (for example
in case of a 3.2 mm thick sample the typical aming
time is   1 s with standard deviation of   1.6 s). As
classication deteriorates the results are prone to be
more erratic with higher dispersion of aming times
(V-1:   10 s,   4.5, s; NR:   26 s,   14 s). Therefore, in order to reduce variability and scatter in the
results, we have chosen the total aming time which is
considerably more reproducible, as the response for the
statistical analysis rather than other measures such as
the maximal aming time.
The UL94V measurement was performed on samples
of 3.2 and 1.6 mm thickness. Although test results may
dier between samples of dierent thickness, the results
of the statistical analyses yield identical eect of all
input variables on the ammability irrespective of
thickness.
Statistical analysis of LOI indicates that variations of
PBBMA and Mg(OH)2 concentrations within the selected ranges have no statistically signicant eect. This is
most surprising. In contrast, UL94V statistical evaluation of the FRs shows that increasing the PBBMA
concentration has the most signicant eect in lowering
the total aming time (p-value=0.003). This implies a
superior ame retardant property, as expected. Increasing the Mg(OH)2 concentration also reduces the total
aming time, as would be expected from a secondary
ame retardant (p-value=0.05). The expected eect of
both FRs on the ammability of the samples as determined by the UL94V test is in contradiction to the lack
of any signicant eect measured by the LOI test. It
implies that the LOI test is not sensitive enough to differentiate between the ammability levels of the compositions tested here.
Statistical evaluation of the LOI shows that increasing
Irganox B225 concentration increases slightly the LOI
(p-value=0.09). Whereas, UL94V evaluation shows
that increasing Irganox concentration results in higher
total aming time (p-value=0.04). The higher aming
time may be attributed to the role of Irganox as an

H. Dvir et al. / Composites Science and Technology 63 (2003) 18651875

inhibitor of the PBBMA radical polymerization.

PBBPA, which is formed in situ during extrusion, is well
dispersed in the PP matrix whereas the PBBMA is
undissolved in the PP matrix [4]. The homogeneous
dispersion of the PBBPA in the matrix allows for better
Br release and therefore better ame retardancy. Irganox may inhibit the PBBMA radical polymerization
and hence increase total aming time. In addition, the
high extent of polymerization caused by the low concentration of Irganox, may increase the viscosity of the
composite and subsequently, decrease the owability
during UL94V test. In view of the larger p-value
obtained in the LOI statistical analysis, the conicting
result from the UL94V experiment and the smaller sensitivity of LOI test we consider the increased FR property obtained by the latter as questionable.
Increasing the PP-g-maleic anhydride concentration
results in a lower LOI (p-value=0.03). No statistically
signicant eect was found in UL94V. This eect is due
to the higher chemical activity of PP-g-MAH and lower
molecular weight PP-g-MAH chains, which have high
decomposition rate.
Increasing the glass bers concentration lowers to
some extent the total aming time (p-value=0.1). In
contrast, increasing the glass ber concentration lowers
the LOI (p-value=0.08). Decreased total aming time is
attributed to a straightforward dilution eect of the
polymer matrix by the glass bers. By the same reasoning, we would also expect an increase in LOI, contrary
to our experimental ndings. In the following we shall
try to explain this surprising eect. One possible
mechanism for enhanced ammability is based on the
substantially dierent thermal expansion coecients of
glass-bers and the PP matrix. Upon cooling of the
composite after the compounding, unequal contraction
leads to a tunnel eect that may cause the formation
of air pockets around the glass bers. The air trapped
between the glass bers and the polymer matrix will not
only enhance the burning, but also contribute to the
poor adhesion between the glass and the PP implied in
the discussion of mechanical properties above. The
proposed mechanism does not address the question of
polymer creep into the air pockets eliminating eventually their existence. Further experimentation is
required to test this hypothesis.
It is observed that the two ammability tests (LOI
and UL94V) result in a contradiction as to the eects of
glass bers. This contradiction may be ascribed to the
dierent nature of these tests [15]. Brominated ame
retardants work by releasing HBr gas into the ame
where it acts as a free radical scavenger. In order to
quench the free radical chain reactions that constitute
the burning process, the HBr has to achieve critical
minimum concentration. The chimney-like construction
of the LOI apparatus and the continual gas ow prevent
the HBr from reaching this critical concentration. On

1873

the other hand, the relatively static atmosphere around

the burning UL94V sample allows this critical HBr
concentration to be achieved. This is the source of difference between the two test methods.
The other possible explanation for increased ammability in LOI and decreased ammability in UL94V
is based on the order of magnitude higher thermal
conductivity and thermal diusivity of the glass bers
relative to the PP matrix. Using this argument, the
glass-bers play the role of heat conductors. They conduct the heat faster into the composite and thereby
contributing to further PP decomposition and release of
combustible gases. This progressive breakdown also
results in bromine release. Since as explained earlier, the
LOI is performed in a continuously rejuvenated environment due to oxygen ow, the bromine atoms in the gas
phase are being continually withdrawn from the aming
area, thus preventing them from reaching that critical
concentration, which would quench the free radical reactions. The UL94V is performed in a stagnant environment
where the bromine atoms are able to perform their function, and the opposite statistical inuence is observed.
Finally, glass bers have a large eect on UL94V test
results by the imparted increase in the viscosity of the
heated composite. By reducing the owability of the
composite, an anti-dripping eect is achieved, which
leads to better UL94V evaluation. Dripping and owability are also aected by the thickness of the sample.
There was no indication of second order interactions
in the LOI statistical analysis. The UL94V statistical
analysis revealed several mutual interactions. The interaction between PBBMA and glass bers is signicant
(p-value=0.04): the combination of a high level concentration of PBBMA with a low level concentration of
glass bers causes a signicant decrease in total aming
time. The interaction between PBBMA and Mg(OH)2 is
also signicant (p-value=0.05): again the combination
of high concentration of PBBMA with low concentration of Mg(OH)2 causes a signicant decrease in total
aming time. This is a somewhat puzzling result since
one would expect that the higher the total amount of
FRs (primary and secondary) the lower would be the
aming time since there is no evidence for adverse eect
of one FR on the other. Thus, the results from the statistical analysis may hint at an indirect eect (e.g.
increased melt viscosity, reduced polymerization of
PBBMA etc.), which is responsible for the negative
interaction parameter obtained from the statistical analysis. We are unable to oer an explanation for this
result at this point.
4.2.1. Search for optimal composition
On the basis of the statistical analysis presented above,
we tried to construct the optimal composition of the PP
formulation. The most crucial step in the optimization
process is the ranking of the composite properties by

1874

H. Dvir et al. / Composites Science and Technology 63 (2003) 18651875

their importance. The basic concept of optimization

means compromise in some values in order to reach
higher values in others. The properties with respect to
which this optimization was performed were chosen as
maximal reversed notched impact strength (representative mechanical property) and minimal total aming
time, which provides V-0 in UL94V test (representative
ame retardant property).
After conducting all 20 experiments of the D-optimal mixture design, the software constructs an algebraic equation (statistical model), which connects the
measured responses with the values of factors under
investigation. This statistical model can be employed for
searching the optimal conditions, once the most important responses are specied. The optimization procedure
performed by the software yielded three formulations,
which were expected to meet the optimization requirements. The predicted optimal formulations are presented in Table 6, together with the experimentally
measured responses for these optimal formulations.
The main feature of these results is the similarity of these
proposed compositions as well as the measured characteristics of these formulations. To appreciate the predictive power of the statistical model, we have compared
the predicted characteristics of the best-proposed formulation (desireability=0.995; Table 6 sample B1) with
experimentally obtained characteristics. The results of
this comparison are presented in Table 7. All predicted
responses, with the exception of the modulus, are in
Table 6
Optimal formulations and test results
Component

PP
Fibers
PBBMA
ATO
MAH
PE Wax
Irganox
Mg(OH)2
UL-94 Rating (3.2mm)
Max. aming time
Total aming time
Cotton ignition
UL-94 Rating (1.6mm)
Max. aming time
Total aming time
Cotton ignition
LOI
Modulus
Max. strength
Impact


Units

B1

B2

B3

%
%
%
%
%
%
%
%

38.50
22.31
15.00
5.00
1.00
0.20
0
17.99

38.50
24.10
15.00
5.00
1.30
0.20
0
15.90

38.50
24.77
15.00
5.00
1.41
0.20
0
15.12

s
s
%

V0
0
0
No

V0
1
1
No

V0
1
2
No

V0
1
6
No
25.526.0

V0
2
4
No
25.526.0

V0
2
3
No
25.025.5

MPa 6953
MPa
41.8
J/m
90.6
J/m
3.8

Table 7
Comparison between model prediction and experimental results of
formulation B1
Response

Modulus

Predicted results

Experimental results

Mean

A 95%
condence
interval

Experimental
value

A 95%
condence
interval

5908

55786237

6953 (av.)

64707436

Impact

90.0

82.797.2

90.6 (av.)

8794.2

Max. strength

42.3

40.344.4

41.8 (av.)

40.942.8

(48) 55

(68)a25

24.925.9

25.5 - 26

Total aming
time (1.6 mm)

Formulation No.

s
s

extremely good agreement with the experimentally

obtained values. The condence limits of the predicted
values for the responses do not exceed 8% (see Table 7).
Specically, the condence limits for the impact, maximal strength and LOI are equal to  8,  4.8 and
 2%, respectively. In contrast, the experimental modulus was markedly higher than that predicted by the
model. We are unable to explain this discrepancy.
Table 8 presents the characteristics of four formulations: the best initial formulation (A1), the best predicted formulation by the DOE model (B1) and
additional two formulations found in the course of DOE
study which seem to have highly desirable properties.
The two latter samples have been added to ascertain that
the formulation chosen by the statistical procedure as
optimal formulation is indeed the best available. One may
observe that the best formulation predicted by the statistical model is a desirable compromise between
mechanical and ammability characteristics: relatively

6834
42.1
91.9
4.7

7203
41.6
89.4
5.7

Total aming
time (3.2 mm)

7
(22)a

LOI
a

25.4

Physically equivalent to value of zero.

Table 8
Properties of the optimal formulations
Initial
formulation
A1

The DOE optimal formulations

The best
predicted

The best formulations in the

DOE experimental matrix

B1

1033

90 4

99 4

1009

Modulus

6333

6953

6521

4777

UL94
(1.6 mm)

T=109 V1

T=6 V0

T=12 V0

T=25 V0

UL94
(3.2 mm)

T=49 V0

T=0 V0

T=4 V0

T=9 V0

LOI (%)

25.025.5

25.526.0

25.025.5

26.026.5

Impact

H. Dvir et al. / Composites Science and Technology 63 (2003) 18651875

high impact and V-0 rating (i.e. low total aming time).
The comparison of the latter formulation with the initial
formulation demonstrates the compromise character of
the process optimization: by accepting a slight decrease
in impact value a dramatic improvement in ame retardancy is obtained. It is instructive to examine in detail the
two additional compositions selected as superior formulations. Both of them are found to be inferior to (B1)
the best predicted formulation. Total aming time (1.6
mm) in these formulations is 12 and 25 s, respectively, as
opposed to 6 s for the optimal formulation. However, if
we take into account the high value of the standard error
of the predicted mean for this response (22 s), we are
obliged to reject these formulations, since the total aming
time in UL94V=(V-0) is not allowed to exceed 50 s.
Indeed, these two formulations fail the UL94V test
regarding V-0 at the =0.05 condence level, if we take
the total aming time as a sum of the predicted mean (12
or 25 s) and twice the standard error (222=44 s).

5. Conclusions
The technique of statistical experimental design has
been employed to obtain an optimal formulation of
high loading polypropylene composite with suitable
mechanical and ame retardancy properties. The DOE
technique helps optimize a set of ame retardant additives, which guarantee acceptable ame retardant properties with minimal negative eect on mechanical
properties. Moreover, it allows the study of the inuence of individual additives and the mutual interactions
in the composite within the chosen concentration
working range. DOE provides a route to obtain the
optimal formulations, and to get the abovementioned
information with the minimum number of experiments.
An optimization of dierent additive loads was performed and the nal polypropylene composite exhibited
improved mechanical and ame retardant properties. The
DOE scheme allows a prediction of most sample properties within 8% from the actual experimental values. In a
typical PP composite under investigation, we observed
that maleic anhydride lowers the modulus and impact
strength. This was attributed to the failure of maleic
anhydride to enhance adhesion at the interface between
PP and the dierent llers and its eect was reduced to a
plastizing eect in the bulk. As expected, PBBMA and
Mg(OH)2 decrease the composite impact strength and
enhance ame retardant properties. Glass bers increase
the modulus as a reinforcing agent, but have only a
moderate eect on impact strength within the investigated range, probably due to poor adhesion with PP.
Contradictory results have been obtained for the eect of
glass bers on ame retardant properties. Dierent
explanations for these results have been suggested, but
no denitive conclusion is possible at this point.

1875

Acknowledgements
The Ariel program for French-Israeli cooperation has
nancially supported this work. MG acknowledges the
nancial support of the German-Israel Foundation and
the Israel Basic Science Foundation. We are grateful to
the sta of the Plastics Application Laboratory at
DSBG for their help in carrying out the mechanical and
ammability tests.

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