Composite Structures 183 (2018) 381–388

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Composite Structures
journal homepage: www.elsevier.com/locate/compstruct

Effect of halogen-free nanoparticles on the mechanical, structural,

thermal and flame retardant properties of polymer matrix composite
Metin Yurddaskal a,b,⇑, Erdal Celik a,c,d
a
Center for Fabrication and Application of Electronic Materials (EMUM), Dokuz Eylul University, 35390 Izmir, Turkey
b
The Graduate School of Natural and Applied Sciences, Dokuz Eylul University, 35390 Izmir, Turkey
c
Department of Metallurgical and Materials Engineering, Dokuz Eylul University, 35390 Izmir, Turkey
d
Department of Nanoscience and Nanoengineering, Dokuz Eylul University, 35390 Izmir, Turkey

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

Article history: In this work, polypropylene (PP) nanocomposites were reinforced with 30 wt% of halogen-free flame
Received 24 January 2017 retardants, which were prepared by melt compounding in a twin-screw extruder followed by injection
Revised 22 March 2017 molding technique. It was aimed to produce flame retardant nanocomposites by reinforcing different
Accepted 27 March 2017
halogen-free nanoparticles with various compositions and to investigate the usability of the nanocom-
Available online 29 March 2017
posites in industrial applications. Within this scope, halogen-free nano sized huntite/hydromagnesite,
antimony trioxide, bentonite and zinc borate particles were reinforced to polypropylene matrix. The
Keywords:
influence of different mineral type/content was investigated for polypropylene nanocomposites contain-
Flame retardancy
Polymer nanocomposite
ing halogen-free flame retardants on the structural, thermal, mechanical and flame retardant properties.
Polypropylene The nanocomposites were analyzed with X-ray diffraction (XRD), scanning electron microscopy (SEM),
Thermal stability thermo-gravimetric analysis (TGA), tensile and UL94 flame retardancy tests to characterize the structural,
Mechanical properties thermal, mechanical and flame retardant behaviour of the PP composites. TGA and flame retardant tests
showed that the decomposition temperature was increased in the presence of huntite/hydromagnesite in
comparison to neat PP and PP composites comprising other mineral types. It was concluded that the
flame retardancy behaviour of PP composites was improved within creasing mineral content, indicating
that the UL94 rating reached V-0 via a good compatibility between huntite/hydromagnesite and PP.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction to say, it can be achieved by adding halogen based additives or

Polypropylene (PP) is one of the most important widely used in
various fields, such as electronics, automobiles, interior decora-
tions, architectural materials and other areas for its superior
mechanical properties, low cost, easy processing and chemical sta-
bility [1–4]. Nevertheless, its severely flammability due to its ali-
phatic hydrocarbon structure restricts its further applications.
Therefore, many researchers have carried out intensive investiga-
tions in order to improve the flame retardant properties of PP
[5–9]. The most widely used approach to enhance mechanical,
thermal properties and flame retardancy is addition of reinforcing
materials into PP matrix which result in high strength, high mod-
ulus and high flame retardant performance [10].
Several flame retardant compounds have been used to enhance
the flame retardancy properties of polymeric materials [11]. That is
⇑ Corresponding author at: Center for Fabrication and Application of Electronic
Materials (EMUM), Dokuz Eylul University, 35390 Izmir, Turkey.
E-mail address: metin.yurddaskal@deu.edu.tr (M. Yurddaskal).
halogen-free hydrated inorganic fillers [12]. Nonetheless, the
potential applications of halogen based flame retardants are lim-
ited owing to their hazardous effect on health and environments
[13–15]. Therefore, several studies have been performed on non-
halogen additives such as metal hydroxides, phosphorus, boron
containing compounds and inorganic clay fillers [16–20]. There
are also numerous research articles illustrating effectiveness of
non-halogenated additives to improve mechanical strength and
thermal stability as well as flame retardancy [21–23].
One of the common flame retardant reinforcing material is hun-
tite (Mg3Ca(CO3)4) which is mostly used together with hydromag-
nesite (Mg5(CO3)4(OH)2
4H2O) [24]. The attractive properties of
these minerals are low smoke generation, environmentally safe,
noncorrosive, and low combustion [25]. Besides, there are many
studies have been reported using huntite and hydromagnesite
as flame retardant additives due to their extraction from Greek
and Turkish mines in large quantities with relatively low cost
[25–28]. In spite of the fact that there are several mechanisms to
explain flame retardancy in polymer/clay nanocomposites, the

http://dx.doi.org/10.1016/j.compstruct.2017.03.093
0263-8223/Ó 2017 Elsevier Ltd. All rights reserved.
382 M. Yurddaskal, E. Celik / Composite Structures 183 (2018) 381–388

protective barrier effect of char [29] and the migration of clay min-
eral layers [30] have been confirmed by many researchers [31–33].
Thus, organo-bentonite has been studied in terms of the effects of
inorganic additives on mechanical, thermal stability and flame
retardancy mechanism by Du et al. [9].
In this study, four different types of flame retardant additives,
namely, huntite/hydromagnesite, bentonite, antimony trioxide
and zinc borate were used in PP. Effect of these additives type/
amount on flame retardancy, thermal and mechanical properties
of PP based composites have not been previously investigated, to
the best of our knowledge, in the same study. The objective of this
work is to evaluate the effects of halogen free flame retardant addi-
tives on flame retardancy as well as mechanical, structural and
thermal properties of PP based composites. The effects of filler con-
tent on the flame retardancy, thermal and mechanical properties of
the PP composites have also been studied in detail.
2. Experimental studies
2.1. Materials
Polypropylene (PP) pellets were used as a polymer matrix to
produce huntite/hydromagnesite, bentonite, antimony trioxide
and zinc borate reinforced nanocomposites. A mineral filler with
40% of hydromagnesite and 60% of huntite by weight was used
as a flame retardant additive. PP with a melt flow index (MFI,
230 °C, ASTM D 1238) of 7–8 g/10 min and melting point of
168 °C was supplied by Petkim Petrochemical Co. (Izmir, Turkey).
Physical densities of huntite (Mg3Ca(CO3)4), hydromagnesite
(4MgCO3.Mg(OH)2
4H2O), antimony trioxide (Sb2O3), bentonite
((Na, Ca)(Al, Mg)6(Si4O10)3(OH)6
nH2O) and zinc borate (2ZnO.3B2-
O3
3.5H2O) minerals are 2.70, 2.24, 5.2, 1.65 and 3.64 g/cm3,
respectively [34–37].
2.2. Nano grinding process and particle size distribution
The huntite/hydromagnesite, antimony trioxide, bentonite and
zinc borate powders were separately milled to obtain nano-scale
particles using a high energy ball milling machine (Fritsch, Pul-
verisette 7) at the rate of 700 rpm at room temperature for
20 min in air. In this process, a powder mixture placed in the ball
mill was subjected to high-energy collision from the balls. This
method could successfully produce fine and uniform dispersions
of oxides. To understand the effect of grinding process, a particle
size analysis was carried out using a particle size measurement
machine (Malvern, Zetasizer Nano ZS).
2.3. Production of composites
In the production of polymeric composite materials, extrusion
and injection molding techniques were used for flame retardant
applications. A co-rotating twin screw extruder (Thermo-Fisher,
Eurolab 16) with screw diameter of 16 mm and L/D ratio of 40
was utilized for production of the composites by adjusting 70%
by weight of PP (pellets form) and 30% by weight of halogen-free
inorganic nanoparticles. We also produced 40 and 50 wt% hun-
tite/hydromagnesite reinforced PP composites in order to investi-
gate the effects of filler content on the flame retardancy, thermal
degradation behaviour and mechanical properties of the PP com-
posites. The screw speed was set at 300 rpm and the barrel temper-
atures of the zones were 160, 170, 180, 190, 200 and 180 °C, from
the feeding zone to the die zone. An injection molding machine
(Permak Co.) equipped with a self-designed mold was used to pre-
pare specimens. Injection process was carried out at a melting tem-
perature of 185 °C, a molding temperature of 25 °C and an injection
pressure of 960 kg/cm2. Sample code and composition of PP and PP
composites were listed in Table 1.
2.4. Characterization of composites
The crystallinity of huntite/hydromagnesite, antimony trioxide,
bentonite and zinc borate reinforced composites was characterized
by X-ray Diffraction (XRD) analysis using Thermo-Scientific, ARL Ka
diffractometer with Cu Ka as a radiation source. Diffraction patterns
were collected in the range of 8°–60° with a scanning rate of 2°/min
and X-ray radiation of Cu-Ka was set at 45 kV and 44 mA. Fourier
transform infrared spectroscopy (FTIR) (Thermo-Scientific, iS10)
absorption spectra of the PP and PP composites were measured
between the range of 4000–650 cm 1 at room temperature. FTIR
spectra of the samples were recorded to determine the organic
components in the samples. The surface morphology and
microstructure of the powders and PP composites were character-
ized by a scanning electron microscope (SEM, COXEM EM 30 Plus).
Thermo-gravimetric analysis (TGA) was performed for the all
samples in order to determine the effective content of inorganic
phase and the degradation behaviour by using a TGA analyzer (Per-
kin Elmer, STA 6000). The TGA curves were recorded from 25 °C to
600 °C at a heating rate of 10 °C/min under a nitrogen flow (flow
rate = 20 ml/min).
Tensile properties of PP and PP composites were tested using a
universal testing machine (Shimadzu, AG-50kNG) with a crosshead
speed of 5 mm/min according to ASTM D638. Tensile strength and
Young’s modulus of PP and PP composites were measured to use in
industrial applications.
Flammability of PP and PP composites were studied by a verti-
cal burning test with the sample dimensions of 125  13 
3.2 mm3, angular radius 1.3 mm, in accordance with the American
National Standard UL-94 standard. Limiting oxygen index (LOI)
tests were performed according to ASTM D2863.
3. Results and discussion
3.1. Measurement of particle size distribution
Particle size distribution of all fillers was shown in Fig. 1. As cal-
culated from Fig. 1, the mean particle size of huntite/hydromagne-
site, antimony trioxide, bentonite and zinc borate powders were
121, 141, 380 and 426 nm respectively, which are reasonable

Table 1
Designation and composition of PP and PP composites.

Sample code PP Antimony trioxide Bentonite Zinc borate Huntite/Hydromagnesite

(wt%/vol%) (wt%/vol%) (wt%/vol%) (wt%/vol%) (wt%/vol%)
PP 100/100 – – – –
PP/30A 70/93.06 30/6.94 – – –
PP/30B 70/80.97 – 30/19.03 – –
PP/30Z 70/90.37 – – 30/9.63 –
PP/30H 70/86.43 – – – 30/13.57
PP/40H 60/80.37 – – – 40/19.63
PP/50H 50/73.19 – – – 50/26.81
 M. Yurddaskal, E. Celik / Composite Structures 183 (2018) 381–388 383

40 20
Antimony trioxide Bentonite
35

30 15

Percent of total particles

Percent of total particles

25

20 10

15

10 5

0
0
10 100 1000
10 100 1000
Particle diameter (nm) Particle diameter (nm)

(a) (b)
30
Zinc borate Huntite/Hydromagnesite
20
25

Percent of total particles

Percent of total particles

15 20

15
10

10

5
5

0 0
10 100 1000 10 100 1000

Particle diameter (nm) Particle diameter (nm)

(c) (d)
Fig. 1. Particle size distribution of (a) antimony trioxide, (b) bentonite, (c) zinc borate and (d) huntite/hydromagnesite.

results for flame retardant reinforcements in composite materials. 2965, 2924, 2865, 2834 cm 1 were ascribed to the asymmetric
Decreasing the particle size above micron to the nano scale indi- and symmetric vibration of C–H in CH2 and CH3 [40]. Furthermore,
cates that the grinding process is successful. The particle size dis- the peaks at 650–750 cm 1 can be assigned to oxygen stretching
tribution was also supported by SEM images given in Fig. 4. vibration in oxides.

3.2. Phase analysis 3.4. Morphological properties

Fig. 2 depicts the XRD patterns of pure PP and huntite/hydro-
magnesite, antimony trioxide, bentonite and zinc borate reinforced
PP composites. The XRD pattern of PP showed the typical a-form
PP crystals, which exhibited four strong peaks at 14.12°, 16.91°,
18,61° and 21.38° [38]. Three pronounced peaks were observed
at 31.4°, 31.6° and 37.3° for PP/30H, corresponding to huntite,
hydromagnesite and magnesium hydroxide, respectively. The
XRD investigations demonstrated the presence of antimony triox-
ide phase in PP. Thus, it can be seen that the maximum intensity
diffraction peak appears at 2h = 28.3°. It can be also revealed the
presence of bentonite and zinc borate phases in composite exists
27.8° and 36.3°, respectively. PP peaks can be seen in all compos-
ites except for PP/30A due to extreme crystallinity of antimony
trioxide.
3.3. FTIR analysis
Fig. 3 denotes the FTIR analysis of pure PP and PP based com-
posite materials. The main difference in the spectra was deter-
mined in the IR band at 1445 cm 1 attributed to the O–H
stretching mode or @CH3 structure [39]. The bands at about
Fig. 4 shows the SEM images of the reinforcing materials. The
SEM images also demonstrated the degree of agglomeration of
the all nanoparticles. As expected, the particle size of the additives
is in accordance with the particle size distribution according to
SEM images given inset of the Fig. 4. The morphology of the PP
composites was also investigated using SEM magnified by 20,000
times. Fig. 5 represents the SEM photographs of the PP based
nanocomposites. It is generally believed that the properties of
polymer nanocomposites depend upon the dispersion or distribu-
tion of the reinforcing materials in the polymer matrix [41]. As
shown in Fig. 5, it can be observed that the distribution of the all
additives in PP matrix is uniform. It should be attributed to the
good compatibility between the halogen-free inorganic nanoparti-
cles and PP. It is known that this phenomenon contributed to the
flame retarding mechanism [42].
3.5. Thermal analysis
TGA was used to investigate the thermal degradation behaviour
of pure PP and PP composites. TGA curves of the samples are
shown in Fig. 6. In addition, DTG curves of PP and flame retardant
384 M. Yurddaskal, E. Celik / Composite Structures 183 (2018) 381–388

10 20 30 40 50 60 PP composites at 600 °C are listed in Table 2. Thermal decomposi-

tion temperatures of PP at T5% and T50% are 276 and 356, respec-
PP/30H
tively with no char residue. However, the presence of flame
retardant nanoparticles increased T50% of the pure PP. The temper-
ature corresponding to 5% mass loss (T5%) is considered to be the
initial temperature of the sample’s decomposition process. The
PP/30Z temperature of 50% mass loss (T50%) corresponds to the tempera-
ture range of the decomposition of soft segments, and determines
thermal stability of tested materials. T50% and char residue
observed at 600 °C of the PP composites significantly increased
Intensity (a.u.)

with addition of flame retardants, which indicates that antimony

PP/30B trioxide, bentonite, zinc borate and huntite/hydromagnesite addi-
tives remarkable improved thermal stability of PP composites.
T50% of the PP composites including flame retardant nanoparticles
shift to higher temperature compared with pure PP, mainly
PP/30A because flame retardants form a char layer, which protects the
PP matrix from heat and combustion [43]. As compared to PP com-
posites containing the same amount (30 wt%) of additives, PP/30A
and PP/30H composites have higher char residue and thermal sta-
bility, respectively. We also produced 40 and 50 wt% huntite/
PP hydromagnesite reinforced PP composites in order to investigate
the effects of filler amount on the flame retardancy, thermal degra-
dation behaviour and mechanical properties of the PP composites.
The remarkable increase in the formation of residue was achieved
in PP composites containing higher flame retardant nanoparticles
10 20 30 40 50 60
than PP/30H composite. The results above show that the increases
(2 Theta) of huntite/hydromagnesite concentration in PP composites
enhance the thermal stability of the materials.
Fig. 2. XRD patterns of pure PP and PP/30A, PP/30B, PP/30Z and PP/30H composites.

3.6. Mechanical tests

4000 3500 3000 2500 2000 1500 1000
0.114
Tensile tests were conducted to determine how mechanical
PP/30H properties were influenced by the presence of different fillers and
0.076
filler concentration. Fig. 8 presents the tensile strength and Young’s
0.038 modulus of PP and PP composites and their values are listed in
0.000 Table 3. When PP composites reinforced with 30 wt% of huntite/
hydromagnesite, antimony trioxide, bentonite and zinc borate
0.069 PP/30Z
were investigated, PP/30H composite provides an enhancement
0.046 of Young’s modulus approximately 68% from pure PP. It is signifi-
0.023 cantly evolved by adding different flame retardant nanoparticles
0.000 into polymer matrix since inorganic fillers have much higher stiff-
Absorbance

0.15 PP/30B ness values than the polymer matrix in good agreement with liter-
ature [44]. Although it is generally considered that the addition of
0.10
flame retardants into polymers can cause a reduction of tensile
0.05 properties [44,45], the drops in tensile strength should not be con-
0.00 sidered as negative because they are acceptable levels for indus-
0.69 PP/30A trial applications.
Mechanical properties of PP composites containing 40 and
0.46
50 wt% huntite/hydromagnesite were also demonstrated in Fig. 8.
0.23
From the results, the PP/40H and PP/50H composites exhibited
0.00 higher modulus and lower tensile strength if compared to
0.069 PP PP/30H composite. The incorporation of flame retardants into poly-
0.046 mer decreased the tensile strength of PP by 28%. As expected, the
addition of ceramic based flame retardant reinforcing materials
0.023
into PP tended to improve the stiffness but weaken tensile
0.000 strength. This could be attributed to the poor interaction between
4000 3500 3000 2500 2000 1500 1000 the reinforcing materials and PP which may acted as a formation of
Wavenumber (cm ) -1 crack initiator [46].

Fig. 3. FTIR analysis of (a) PP, (b) PP/30A, (c) PP/30B, (d) PP/30Z and (e) PP/30H
nanocomposite materials.
PP composites are shown in Fig. 7. The initial degradation temper-
ature (T5%), the 50 wt% loss temperature (T50%), the maximum
decomposition temperature (Tmax) and the char residue of PP and
3.7. Flame retardant tests
Table 4 presents the UL94-V testing results of PP and PP com-
posites. Naturally, in the absence of flame retardants, the pure PP
burned easily with allowing melt dripping. Considering different
types of additives reinforced with 30 wt%, while the results of
the PP/30A, PP/30Z and PP/30H correspond to a UL 94 rating of
 M. Yurddaskal, E. Celik / Composite Structures 183 (2018) 381–388 385

Fig. 4. SEM micrographs of (a) antimony trioxide, (b) bentonite, (c) zinc borate and (d) huntite/hydromagnesite.

Fig. 5. SEM micrographs of (a) PP/30A, (b) PP/30B, (c) PP/30Z and (d) PP/30H composites.
386 M. Yurddaskal, E. Celik / Composite Structures 183 (2018) 381–388

100 PP
PP/30A
PP/30B
80 PP/30Z
PP/30H
PP/40H
60 PP/50H
Weight (%)
40

20

0 100 200 300 400 500 600

Temperature (oC)

Fig. 6. TGA curves of PP and PP/30A, PP/30B, PP/30Z, PP/30H, PP/40H and PP/50H composites.

Fig. 7. DTG curves of PP/30A, PP/30B, PP/30Z, PP/30H, PP/40H and PP/50H composites.

Table 2 26 1.8
Tensile strength (MPa)
Thermal properties of PP and PP composites. Young's modulus (GPa)
1.7
Sample code T5% (°C) T50% (°C) Tmax(°C) Char yields at 600 °C (%) 24 1.6

Young's modulus (GPa)

Tensile strength (MPa)

PP 276 356 358 0 1.5

PP/30A 263 389 393 28.2
22 1.4
PP/30B 255 368 371 15.1
PP/30Z 279 376 394 19.9 1.3
PP/30H 250 388 401 8.1 1.2
20
PP/40H 273 371 389 8.5
1.1
PP/50H 256 366 387 15.8
1.0
18
0.9

V-1, the PP/30Z composite is V-2, indicating that the addition of 0.8
16
bentonite into PP did not improve the flame retardant properties
0A

0B
PP

0H
0Z

0H

0H

sufficiently as much as others. With further increased of huntite/

/3

/3

/3
/3

/4

/5
PP

PP

PP
PP

PP

PP

hydromagnesite amount up to 50 wt%, the UL-94 rating could

reach V-0. It is noteworthy that in spite of the leading role of addi-
tive type in thermal stability, the composites with same or higher
huntite/hydromagnesite content performed better in LOI and UL
94 tests compared with the thermally most stable PP/30A sample.
On basis of the above discussions, it was concluded that hun-
tite/hydromagnesite reinforced composite exhibited better flame
retardant performance than other additive reinforced composites
with the same contribution rate. When the effect of the additive
ratio was examined, it is seen that the PP/50H composite has supe-
rior flame retardant property which is dramatically enhanced with
the amount of additive increased by 50 wt%. It is evident that there
was a good compatibility between huntite/hydromagnesite and PP
Fig. 8. Tensile strength and elastic modulus of PP and PP/30A, PP/30B, PP/30Z, PP/
30H, PP/40H and PP/50H composites.
at high contribution rates when the LOI and UL94 performances
considered. Moreover, some interesting events were occurred dur-
ing LOI tests. When the samples were tested with a low oxygen
ratio, the intensity of flame diminished and finally disappeared.
It was understood from this phenomenon, free radicals produced
with quenching effect by the matrix material were adequate to
compress the combustion which result in the formation of char
barrier that protects the sample from further degradation. If the
 M. Yurddaskal, E. Celik / Composite Structures 183 (2018) 381–388 387

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