Journal of Thermal Analysis and Calorimetry

https://doi.org/10.1007/s10973-018-7331-7(0123456789().,-volV)(0123456789().,-volV)

In situ synthesis of layered double hydroxides-silicon dioxide hybrids

and its flame retardancy in EVA composites
Shaojie Zhou1 • Yi Qian1 • Xilei Chen1 • Long Li1

Received: 30 August 2017 / Accepted: 24 April 2018

 Akadémiai Kiadó, Budapest, Hungary 2018

Abstract
Layered double hydroxides-silicon dioxide hybrids (LDH-Si) were in situ synthesized by a co-precipitation method. Flame-
retardant, smoke suppression and thermal degradation properties of the LDH-Si in ethylene-vinyl acetate (EVA) com-
posites were studied using cone calorimeter test (CCT), limiting oxygen index (LOI), smoke density test (SDT), and
thermogravimetry–Fourier transform infrared spectrometry. The CCT results indicated that the peak heat release rate and
peak smoke production rate of the EVA/LDH-Si composite with 2.5 mass% SiO2 were decreased by 28.5 and 21.9%
compared to EVA/LDH composite, respectively. The LOI results showed that a suitable addition of SiO2 can significantly
enhance the LOI values of the EVA composites. It was obtained from SDT that SiO2 could help smoke suppression. The
EVA/LDH-Si composites possessed a higher thermal stability than the EVA/LDH composites at high temperatures.

Keywords Layered double hydroxide
Silicon dioxide
Ethylene-vinyl acetate
Flame retardant
Thermal degradation

Introduction a very high loading in polymer composites is required to

Recently, a great deal of attention has been focused on the
application of flame-retardant polymeric materials with
non-halogen flame-retardant additives, for example, metal
hydroxides, layered double hydroxides (LDHs), red phos-
phorus, and organophosphorus compounds, as these mate-
rials do not cause environmental pollution [1–6]. LDHs, as
a class of eco-friendly additives, have been widely used in
the flame retardation of polymer-insulated wires and cables
due to their unique chemical composition and layered
structure [4, 7]. Their advantages include low smoke, non-
toxic, and no corrosive gas generation [8]. To compare, the
burning of halogen-containing polymer materials usually
releases large amounts of smoke and toxic gas, which pose
a great threat to the environment and human safety [4].
Thus, the use of halogen-containing flame retardants has
been gradually reduced or even banned in some jurisdic-
tions [7]. LDHs, however, have a critical disadvantage that
& Yi Qian
qianyi1962@126.com
1
College of Environment and Safety Engineering, Qingdao
University of Science and Technology, Qingdao 266042,
Shandong, People’s Republic of China
obtain an adequate level of flame-retardant performance
[7, 9]. This significantly restricts their applications in many
areas. Therefore, it is very necessary to enhance the flame-
retardant efficiency of LDHs. Many works indicated that
some halogen-free synergistic additives, such as expand-
able graphite [10], zinc borate [11, 12], red phosphorus
[4, 13] and ammonium polyphosphate [14, 15], can
improve the flame retardancy and thus reduce usage
amount of LDHs.
Silicon dioxide (SiO2), combining high toughness, high
strength and abrasion, is one of reinforced filling materials
that are extensively used [16]. It is usually used as a syn-
ergist agent in thermoplastic polymers to improve the
flame-retardant properties [17]. Fu and Qu [18] investi-
gated the synergistic flame-retardant mechanism of fumed
silica in ethylene-vinyl acetate (EVA)/magnesium
hydroxide composites. Results showed that the addition of
a given amount of fumed silica apparently enhanced the
flame-retardant property of the EVA composites and
decreased the loading of magnesium hydroxide in EVA
composites. The synergistic flame-retardant mechanism of
fumed silica in the EVA composites is mainly due to the
physical process of fumed silica acting as enhanced char/
silica layers in the condensed phase which prevents the

123

heat and mass transfer in the fire. Jiao and co-workers [17]
studied the influence of fumed silica on the flame-retardant
properties of EVA/aluminum hydroxide composites. The
results showed that fumed silica greatly reduced the heat
release rate of EVA composites, and its synergistic
mechanism in flame-retardant EVA/aluminum hydroxide is
also mainly due to the physical process. Pan et al. [19]
reported the synergistic effect of nano-SiO2 and ammo-
nium polyphosphate on flame retardancy of wood fiber–
polyethylene composites. Results indicated that ammonium
polyphosphate/nano-SiO2 has significant improvements on
flame retardancy of the wood fiber–polyethylene compos-
ites. The presence of nano-SiO2 can further form an
intercalated network in char structure, enhancing the
physical integrity. This char layer with higher thermal
stability and physical integrity results in an effectively
synergistic effect on flame retardancy of wood fiber–
polyethylene composites. Although the synergistic effects
of SiO2 on the flame-retardant properties of polymers have
been studied extensively, there is little information on the
effect of layered double hydroxides-silicon dioxide hybrids
(LDH-Si) on flame-retardant EVA system.
EVA with different vinyl acetate (VA) contents is
extensively used in many fields, especially in the cable
industry as excellent insulating materials with good phys-
ical and chemical properties [20]. However, EVA resins
are easily flammable and emit a large amount of smoke
during burning [4]. Therefore, it is very important to
enhance the flame retardancy of EVA materials. In this
present work, LDH-Si was in situ synthesized and char-
acterized by X-ray diffraction (XRD), scanning electron
microscopy (SEM) and energy-dispersive spectrometer
(EDS) analysis. The flame retardancy, smoke suppression
and thermal degradation behavior of EVA/LDH-Si com-
posites were studied using cone calorimeter test (CCT),
limiting oxygen index (LOI), smoke density test (SDT) and
thermogravimetry–Fourier transform infrared spectrometry
(TG-FTIR).
Experimental
Materials
EVA containing 18 mass% VA was bought from Beijing
Eastern Petrochemical Company (China). SiO2 (30 nm)
was purchased from Aladdin Industrial Corporation
(China). Other reagents were the analytical reagent and
used for the synthesis of LDHs. All of these materials were
used as received without any further purification.
123
S. Zhou et al.
Sample preparation
In situ synthesis of layered double hydroxides-silicon
dioxide hybrids
LDH-Si was in situ synthesized using a co-precipitation
method. Firstly, salt solution (with Mg/(Al ? Fe) molar
ratio of 3:1) was prepared by dissolving the required
amount of MgCl2
6H2O, FeCl3
6H2O and AlCl3
6H2O in
200 mL of deionized water at room temperature. Mean-
while, the required amount of SiO2 was added into the salt
solution, maintaining electric stirring during the synthesis.
Alkali solution was also prepared by dissolving the
required amount of NaOH and Na2CO3 in 200 mL of
deionized water at room temperature. Then, the above
solutions were simultaneously added dropwise into the
stirred deionized water at 80 C, maintaining the pH at
8–9. After salt solution was added, the resulting slurry
mixture was aged for 0.5 h at 80 C. Finally, the suspen-
sion was filtered, thoroughly washed and dried at 80 C for
24 h. The resulting product was grinded into - 200 mesh
particles (with a particle size of about 74 lm) using a ball
mill and characterized by XRD, SEM and EDS.
Preparation of the EVA composites
All compositions were melt-compounded with a mixer at
130 C for 10 min. And, the mixing was carried out at
30 rpm. Then, the resulting EVA composites were hot-
pressed at 130 C for 10 min under a pressure of 10 Mpa
into sheets of suitable thickness (3 mm). Finally, the
compressed sheets were cut into suitable size for fire test-
ing according to the standards mentioned in the following
part. The formulations of the EVA composites are listed in
Table 1.
Table 1 Formulations of the flame-retardant EVA composites
Sample code EVA/mass% LDH-Si/mass%
EVA 100 0
ELS0 50 50 LDH-0 Si
ELS1 50 49.5 LDH-0.5 Si
ELS2 50 49 LDH-1 Si
ELS3 50 48.5 LDH-1.5 Si
ELS4 50 48 LDH-2 Si
ELS5 50 47.5 LDH-2.5 Si
where 50 LDH-0 Si is the LDH; 49.5 LDH-0.5 Si was obtained by
adding 0.5 mass% SiO2 into 49.5 mass% LDH during the in situ
synthesis
In situ synthesis of layered double hydroxides-silicon dioxide hybrids and its flame…

Measurements 30 mL min-1 at a linear heating rate of 10 C min-1. The

mass of sample EVA, ELS0 and ELS5 is 3.511 mg,
XRD analysis 6.047 mg and 5.806 mg, respectively.

The XRD pattern of LDH-Si was recorded on a Rigaku

D/MAX/2500PC system using Cu-Ka radiation Results and discussion
(k = 1.5418 Å) with scan rate of 8 min-1 at 2h values
ranging from 5 to 65. The test was carried out under the Characterization of LDH-Si
tube voltage of 40 kV, current of 150 mA and scanning
mode of 2h/h. XRD characterization

SEM and EDS analysis Figure 1 presents the XRD pattern of LDH and LDH-Si
(obtained by adding 5% SiO2 into 95% LDH during the
The surface morphology of the samples was investigated in situ synthesis). As shown in Fig. 1, the (003), (006),
using a JSM-6700F scanning electron microscopy (SEM; (009), (015), (018), (110) and (113) diffraction peaks of
JEOL, Japan), combined with an Oxford MAX-80 energy- LDH and LDH-Si are in good agreement with hydrotalcite
dispersive X-ray spectroscopy (EDS) for the determination lattice structure [21, 22]. The diffraction peaks of the
of elemental composition. sample are sharp and the baselines are low, indicating a
relatively well-formed crystalline-layered structure. At the
Cone calorimetry test low-angle region, 2h values of (003), (006), and (009)
crystal planes have a good multiple relationship, confirm-
The CCT (Stanton Redcroft, UK) was performed under a ing well crystalline-layered structures; near 60, diffraction
heat flux of 50 kW m-2 according to ISO 5660-1-2002 peaks of (110) and (113) crystal planes are obviously
standard procedures. Each specimen of dimensions separated, indicating that negative ions among layers have
100 9 100 9 3 mm3 was wrapped in aluminum foil. high degree of regularity, and the LDH and LDH-Si syn-
thesized have good symmetry [23]. After adding SiO2, the
Limiting oxygen index interlayer spacing of LDH-Si increases from 0.779 nm
(LDH) to 0.794, which is helpful for improving the barrier
LOI measurements were taken using an HC-2 oxygen effect of the flame-retardant additives during combustion
index meter (Jiangning Analysis Instrument Company, process.
China) according to ASTM D 2863-2013. The samples
used for the test were with dimensions SEM and EDS characterization
100 9 6.5 9 3 mm3.
The SEM coupled with EDS of the LDH and LDH-Si
Smoke density test (obtained by adding 5% SiO2 into 95% LDH during the

The SDT machine (QMY-2, Jianqiao Co., China) was used

to measure the smoke characteristics according to ISO d(003)= 0.779 nm
(003)
5659-2-2006. Each specimen with dimensions of
75 9 75 9 2.5 mm3 was wrapped in aluminum foil and
exposed horizontally to an external heat flux of d(003)= 0.794 nm
25 kW m-2 with or without the application of a pilot (006)
Intensity/a.u.

flame. (009)

(015) (018) (110)(113)

TG-FTIR analysis

TG-FTIR instrument consists of a thermogravimeter LDH

(TG209 F1, Netzsch Instruments, Germany), a Fourier
transform infrared spectrometer (Vertex70, Bruker Optics, LDH-Si
Germany), and a transfer tube with an inner diameter of
0 10 20 30 40 50 60 70
1 mm connected the TG and the infrared cell. The test was 2θ /°
performed from 30 to 800 C under a nitrogen flow of
Fig. 1 XRD pattern of LDH and LDH-Si

123
 S. Zhou et al.

in situ synthesis) is shown in Fig. 2. As shown in Fig. 2a, 350

EVA
the synthesized LDH shows characteristic of plate-like 1510.1 kW m–2 ELS0
300
morphology, which correlates well with hydrotalcite lattice ELS1

Heat release rate/kW m–2

ELS2
structure. After adding SiO2, remarkable changes are 250 272.9 kW m–2 ELS3
observed for LDH-Si in Fig. 2b. It shows the characteristic ELS4
ELS5
of agglomeration or flocculation morphology. The EDS 200
analysis of the LDH-Si (Fig. 2c) shows the presence of 195.0 kW m–2
large amount of Mg, Al and Fe. This is in good agreement 150
with the elemental composition of LDH-Si. At the same 100
time, the diffraction peak of silicon is high and sharp,
indicating that SiO2 was successfully added into LDH. 50
Therefore, LDH-Si was successfully synthesized by adding
SiO2 into LDH using a co-precipitation method. 0
0 100 200 300 400 500 600 700 800
Time/s
Cone calorimeter test
Fig. 3 Heat release rate curves of the EVA/LDH-Si composites
Cone calorimeter is a well-known bench scale instrument
for testing of flammability properties [24], and the obtained of ELS0 obviously declines, and the combustion tended to
results are found to correlate well with those obtained from be mild after the addition of LDH. Its maximal pHRR
a large-scale fire test and can be used to predict the com- (272.9 kW m-2) has an about 82% reduction in compar-
bustion behavior of materials in a real fire [25, 26]. CCT ison with that of pure EVA. This is due to fire retardation
provides a wealth of information on the combustion of LDH in the EVA composite. H2O and CO2 released
behavior based on the oxygen consumption principle from the decomposition of LDH decrease the temperature
including peak heat release rate (pHRR), heat release rate of the substrate, as well as the density of oxygen and
(HRR), total heat release (THR), mass loss, time to ignition flammable gases. The carbonization of the materials can be
(tign), smoke production rate (SPR), total smoke release promoted by the metal oxides from LDH. A protective
(TSR), smoke factor (SF), fire performance index(FPI) carbon layer, covering on the surface of the substrate, can
[24, 27, 28]. act as a physical/thermal barrier. It can prevent heat
transfer and transportation of oxygen and flammable gases
Heat release rate on burning, thus reducing the HRR and related parameters
[7].
Heat release rate measured by CCT is a very important After adding SiO2, the HRR curves of the EVA/LDH-Si
parameter in controlling fire hazards [24]. The HRR of composites (ELS1-ELS5) further decrease, and the com-
EVA and its composites as a function of burning time are bustion time is prolonged compared with ELS0. The phe-
shown in Fig. 3, and the detailed data from CCT are listed nomena can be illustrated by the synergistic effect of SiO2
in Table 2. As shown in Fig. 3 and Table 2, the HRR curve and LDH in the EVA composites. ELS5 (2.5 mass% SiO2)
of pure EVA is very narrow and sharp with a pHRR as high possessed the lowest HRR among all the samples. Its
as 1510.1 kW m-2, indicating that pure EVA is easily maximal pHRR (195 kW m-2) is reduced by 28.5%
flammable polymeric material. To compare, the HRR curve compared with ELS0. Further, the tign for ELS5 is

Fe Ng Spectrum 2

Si

Al
C

C
Fe

Cl
Fe

0 1 2 3 4 5 6 7 8 9
Full scale 7355 cts cursor: – 0.020 (2084 cts) keV

Fig. 2 a SEM image of LDH. b SEM image of LDH-Si. c EDS pattern of LDH-Si

123
In situ synthesis of layered double hydroxides-silicon dioxide hybrids and its flame…

Table 2 Correlated data from cone calorimeter test

Sample tign/s pHRR1/kW m-2 pHRR2/kW m-2 Char THR/MJ m-2 Time to flame pSPR/ TSR/m2
code residue/mass% out/s m2 s-1 m-2

EVA 34 1510.1 – 11.2 120.7 296 0.0633 454.3

ELS0 41 272.9 249.8 30.7 115.1 677 0.0242 743.7
ELS1 47 235.4 267.4 32.1 105.3 603 0.0233 691.8
ELS2 44 202.2 203.6 33.9 102.2 698 0.0197 734.8
ELS3 50 192.2 212.0 35.8 104.2 745 0.0205 740.3
ELS4 49 227.8 186.9 36.6 105.1 728 0.0175 741.5
ELS5 43 159.2 195.0 37.3 99.8 811 0.0189 737.0

prolonged by SiO2. It indicated that an appropriate addition 140

of SiO2 could improve the flame retardancy of the EVA EVA
120 ELS0 120.7 MJ m–2
composites. It acts as a synergistic flame retardant of LDH

Total heat release/MJ m–2

ELS1
to retard the burning of the material. SiO2 has a large 100
ELS2
ELS3
surface area and low density, tending to accumulate near
ELS4
the regressing sample surface without sinking through the 80 ELS5 99.8 MJ m–2
polymer melt layer during the gasification/burning process.
The accumulated SiO2 consequently formed a protective 60
carbon layer by collaborating with metal oxides from the
40
decomposition of LDH, as a heat insulation barrier
[18, 29]. 20
From Fig. 3, it can be seen the HRR curve of pure EVA
has one peak, while the HRR curves of ELS1-ELS5 have 0
0 100 200 300 400 500 600 700 800
two peaks. It reflects that a gradual burning of the specimen
Time/s
through the thickness occurred after the initial char layers
formed [18]. The first peak of HRR curves (pHRR1) is due Fig. 4 Total heat release curves of the EVA/LDH-Si composites
to the development of the protective char. After the first
peak, the HRR curve forms a plateau because HRR is
100
suppressed by the protective carbon layer. The second peak EVA
ELS0
of HRR curves (pHRR2) may be caused by cracking char or
ELS1
increase in the effective pyrolysis [20, 30]. 80 ELS2
ELS3
ELS4
Total heat release 60 ELS5
Mass/%

Figure 4 shows the total heat release curves of the flame-

40
retardant EVA/LDH-Si composites. Slope of THR curves
can be assumed as representative of fire spread rate
[30, 31]. In Fig. 4, slope of THR curves of the EVA 20
composites significantly decreases compared to that of
EVA, indicating that LDH-Si could decrease fire spread 0
rate of EVA. Among all samples, the fire spread rate of 0 100 200 300 400 500 600 700 800
ELS5 is the lowest. Also, its THR value declines rapidly Time/s
from 120.7 MJ m-2 (pure EVA) to 99.8 MJ m-2. These
Fig. 5 Mass-loss curves of the EVA/LDH-Si composites
phenomena indicate that an appropriate amount of SiO2 is
needed to improve the flame retardancy of EVA
Mass loss
composites.
Figure 5 shows the mass-loss curve of the char residues of
the EVA/LDH-Si composites. All composites containing

123
 S. Zhou et al.

LDH-Si have a higher mass of char residues than that of 800

pure EVA. For ELS0, the mass of the char residue clearly EVA
700 686.1 MW m–2 ELS0
increases compared with that of pure EVA. This is due to

Smoke factor/MW m–2

ELS5
that a compact char may generate on the surface of mate- 600
rial, creating a physical protective barrier. The char can 500
also prevent the heat mass transfer between the flame zone
and the burning substrate and thus protect the underlying 400
materials from further burning and retard the pyrolysis of 300
polymers. After the addition of SiO2, the mass of the char 202.8 MW m–2
residue for samples (ELS1 to ELS5) visibly increases, 200
especially for ELS5 containing 2.5 mass% SiO2, the mass 100 143.7 MW m–2
of the char residue can reach up to 37.3% at 800 s. The
reason is that SiO2 can promote char formation during 0
0 100 200 300 400 500 600 700 800 900
combustion, thus enhancing the mass of the char residue. Time/s

Smoke production rate Fig. 7 Smoke factor curves of the EVA/LDH-Si composites

Smoke performance of flame-retardant materials is a sig- Smoke factor

nificant parameter in fire safety fields [32, 33]. The SPR of
EVA and its composites as a function of burning time are
shown in Fig. 6. It is clearly seen that the SPR curve of
pure EVA is very narrow and sharp with a peak SPR
(pSPR) as high as 0.0633 m2 s-1 at 155 s. It indicates that
pure EVA released a large amount of smoke during burn-
ing. Compared to EVA, the SPR curve of ELS0 greatly
decreases with a pSPR value of 0.0242 m2 s-1. And, the
time to pSPR for ELS0 is prolonged due to the addition of
LDH. After adding 2.5 mass% SiO2, the SPR curve for
ELS5 further decreases. And, the pSPR of ELS5
(0.0189 m2 s-1) is reduced by 21.9% compared to ELS0.
This phenomenon can be illustrated by the synergistic
effect of LDH and SiO2 in smoke suppression.
0.07
0.0633 m2 s–1
Smoke production rate/m2 s–1
Smoke factor is the product of peak heat release rate and
total smoke release [31, 34]. Figure 7 gives the smoke
factor as a function of time for EVA and its composites. As
shown in Fig. 7, the SF value of EVA reaches up to
686.1 MW m-2. After adding LDH-Si, the SF curves for
EVA composites clearly decline. The SF values of ELS0
and ELS5 are 202.8 MW m-2, 143.7 MW m-2, respec-
tively. The data show that SiO2 is helpful for the flame
retardancy and smoke suppression of EVA composites.
Fire performance index
FPI is the ratio of tign and pHRR [35]. The index is posi-
tively correlated with the flashover time [36]. The bigger
the FPI is, the higher the safety rank for flame-retardant
materials is [37]. Figure 8 shows the FPI of all samples. As
shown in Fig. 8, the FPI of EVA is 0.023, indicating that
pure EVA poses a great threat to human safety. Compared
to EVA, the FPI of ELS0 increases rapidly from 0.023
EVA (EVA) to 0.150. This demonstrates that LDH can clearly
ELS0

0.06
ELS5
0.30
0.05
0.246
0.236
0.25 0.216 0.215
0.04
0.20 0.176
0.03 0.150
FPI

0.0242 m2 s–1
0.15
0.02 0.0189 m2 s–1
0.10
0.01 0.05 0.023

0.00 0.00
0 200 400 600 800 EVA ELS0 ELS1 ELS2 ELS3 ELS4 ELS5
Time/s Sample code

Fig. 6 Smoke production rate curves of the EVA/LDH-Si composites Fig. 8 Fire performance index of the EVA/LDH-Si composites

123
In situ synthesis of layered double hydroxides-silicon dioxide hybrids and its flame…
enhance the flame retardancy of polymers. After the adding
of SiO2, the FPI of EVA/LDH-Si composites (ELS1 to
ELS5) further increases compared to that of ELS0. This
demonstrates the synergistic effect of SiO2 and LDH on
flame-retardant EVA system. SiO2 with metal oxides from
LDH can promote char formation and improve the struc-
ture of char residue during combustion, thus enhancing the
flame-retardant properties of EVA composites.
Appearance analysis of the char residues
The appearance of char residues for EVA and EVA com-
posites after CCT is shown in Fig. 9. No char is left for
pure EVA after CCT because of its inherent flammability
with whole aliphatic hydrocarbon structure. The other
flame-retardant EVA composites remain as residues. The
char residue of ELS0 has many cracks and holes, which
lower the flame retardancy and smoke suppression on
EVA. With the adding of SiO2, a better carbonaceous
protective layer was formed (Fig. 9g), which is compact,
smoother and integrated on the surface of the char residue.
It indicates that SiO2 can improve the structure of char
residue during burning, and the synergistic mechanism by
SiO2 is mainly the condensed phase process. A protective
char residue can act as not only a heat insulation layer, but
also as a barrier that reduces smoke generation and emis-
sion. In Fig. 9, the morphology of EVA and its composites
after CCT correspond to the results of HRR, mass loss,
SPR and SF.
Fig. 9 Morphology of the charred residues after CCT. a EVA, b ELS0, c ELS1, d ELS2, e ELS3, f ELS4, g ELS5
Scanning electron microscopy
SEM can be used to investigate the relationship between
microstructure of char layer and flame-retardant perfor-
mance. Figure 10 presents the morphologies of char resi-
dues left after CCT. As seen in Fig. 10, many loose and
irregular particles are dispersed on the rough surface of the
residues of ELS0. For ELS5, the particles on the smooth
surface of the char residue are regular and compact. The
formation of the effective protective char layer could pre-
vent the heat transfer between the flame zone and the
burning substrate and thus protect the underlying materials
from further burning and retard the pyrolysis of polymers
during combustion [20]. Moreover, this protective char
layer could also prevent smoke release. The microscopic
observations confirmed that the addition of SiO2 can
improve the char structure and flame retardancy. This
evidence can explain why the HRR and SPR of ELS5
declined.
Limiting oxygen index
Except for CCT, the LOI is also widely used to evaluate
flame-retardant properties of materials [7]. The higher the
LOI value is, the more difficult it is for combustion to
occur. Figure 11 presents the LOI values of EVA and
EVA/LDH-Si composites. It can be seen from Fig. 11 that
the LOI value of ELS0 increases rapidly from 19.2 (pure
EVA) to 28.3%. It can be attributed to the degradation of
123
 S. Zhou et al.

Fig. 10 SEM images of the surface of the charred residues obtained from ELS0 and ELS5

32 30.3
30.8 (a)
30.2 29.8 29.6 with the application of a pilot flame
28.3 100
29
EVA
26
LOI/%

80 ELS0

Luminous flux/%
ELS1
23 ELS2
60 ELS3
ELS4
20 19.2
ELS5
40
17
EVA ELS0 ELS1 ELS2 ELS3 ELS4 ELS5
Sample code 20

Fig. 11 LOI of the EVA/LDH-Si composites 0

0 200 400 600 800 1000 1200
LDH. When the flame-retardant sample was heated, LDH Time/s
decomposed and generated H2O and CO2. It would dilute
the flammable gases and oxygen and lower the tempera- (b)
without the application of a pilot flame
ture, helpful to the LOI test. After the adding of SiO2, the 100
LOI values of the EVA/LDH-Si composites (ELS1 to EVA
ELS5) further increase compared to ELS0, with the highest 80 ELS0
ELS1
Luminous flux/%

value as 30.8%. It indicates that SiO2 can improve flame ELS2

retardancy of the materials because of the synergistic ELS3
60
ELS4
effects between SiO2 and LDH. ELS5
40
Smoke density test
20
While the CCT results reflect the combustion behavior of
the samples, the SDT gives detailed information about 0
smoke generation. It can be used to evaluate the smoke 0 200 400 600 800 1000 1200
suppression performance of the samples [30]. Time/s
Figure 12 shows the luminous flux (LF) curves of the
Fig. 12 Luminous flux curves of the EVA/LDH-Si composites:
EVA/LDH-Si composites with or without the application a with or b without the application of a pilot flame
of a pilot flame. It can be seen from Fig. 12a that the LF
curves of the EVA composites are higher than pure EVA, phenomenon can be illustrated that the carbon layer is not
indicating that LDH-Si can improve the smoke-suppressing formed at the beginning of the combustion. When the time
properties of EVA composites with the application of a exceeds 600 s, it produces less smoke compared to pure
pilot flame. Unfortunately, ELS0 produces more smoke EVA, which is due to the formation of a protective char
than pure EVA at the range of 300-600 s. This layer. The char layer can cover on the surface of the matrix,

123
In situ synthesis of layered double hydroxides-silicon dioxide hybrids and its flame…

(a)
100 347.2 °C 0.20
EVA
EVA

Y [Absorbance units]
90 ELS0
ELS5 0.15
80 188.7 °C 205.7 °C
70 0.10
Mass/%

60 469.7 °C
460.9 °C 0.05
50 34%
0.00 1000
40 463.0 °C 2000
1000
30 X [Wavenumber cm–1]
2000
3000
20 29.6% Z [S] 3000
4000
10
0
0 100 200 300 400 500 600 700 800 900 0.15 ELS0
Temperature/°C

Y [Absorbance units]
(b) 0.10
0.0
EVA
0.05
–0.5 ELS0
Derive mass/% °C–1

ELS5
1000
0.00
–1.0 2000
1000 –1
(469.7 °C, –1.19 % °C–1) 2000 3000 X [Wavenumber cm ]
(467.7 °C, –1.28 % °C–1) Z [S] 3000
–1.5 4000

–2.0 0.10
ELS5
Y [Absorbance units]

(469.7 °C, –2.39 % °C–1) 0.08

–2.5
0 100 200 300 400 500 600 700 800 900
0.06
Temperature/°C
0.04
Fig. 13 TG-DTG curves of EVA, ELS0 and ELS5: a TG; b DTG
0.02
decreasing the production and release of smoke. After 4000
0.00
adding SiO2, the LF curves of samples (ELS1 to ELS5) are 3000
1000
higher than ELS0 on burning. And, the LF value of ELS3 2000 Z [S]
2000
maintains above 88% during combustion. This phe- X [Wavenumber cm–1] 3000 1000

nomenon indicates that an appropriate addition of SiO2

could improve the smoke-suppressing properties of the Fig. 14 3D TG-FTIR spectra of pyrolysis products of EVA, ELS0
and ELS5 during the degradation
EVA composites. SiO2 can work together with LDH to
form a protective char layer, as a barrier that can reduce
LDH-Si composites is mainly due to the formation of a
smoke generation and emission.
protective barrier. When a compact protective char layer is
In Fig. 12b, the smoke suppression character of the
formed by SiO2 and LDH, combustion products such as tar
EVA flame-retardant composites significantly decreases
and soot particles are limited in transportation to the gas
compared to EVA, without the application of a pilot flame.
phase, and thus the smoke suppression can be effectively
Moreover, the amount of smoke production for the EVA/
improved.
LDH-Si composites was reduced by the pilot flame. The
solid particles discharged from the depolymerization of the
TG-FTIR analysis
polymers were mostly burned out to generate gases [8].
They did not directly migrate into the gas phase to increase
TG behavior
the amount of the smoke.
It can be concluded from the aforementioned description
TG-FTIR is usually used to study the thermal degradation
that SiO2 is helpful in smoke suppression with the appli-
behavior of flame-retardant materials and analyze the
cation of a pilot flame. The good performance of the EVA/

123
 S. Zhou et al.

EVA Thermal stability of a polymeric material is extremely

2927
important when it comes to a flame retardant, which is
mainly concerned about the release of decomposition
2354 products and the formation of char [15]. Figure 13 presents
2855
the TG and DTG curves of the EVA, ELS0, and ELS5. In
Absorbance

667 Fig. 13, EVA undergoes two degradation steps. The first
633 °C
510 °C
decomposition step is the loss of acetic acid, and the sec-
ond involves the degradation of the resulting unsaturated
1177 1459 1792 475 °C material [43]. ELS0 and ELS5 show three mass-loss steps.
1000 The first step of the EVA composites is attributed to the
3585
367 °C loss of loosely bound water in the interlayer space of LDH
357 °C
280 °C in the composites [4]. The second and the third steps
230 °C belong to the simultaneous dehydroxylation and decar-
500 1000 1500 2000 2500 3000 3500 4000 4500 bonization of the lattice of LDH, which overlap with the
Wavenumber/cm–1 decomposition of the acetate groups in EVA side chains
and the scission of the main chains of EVA [14, 43].
ELS0 It should be noticed that the EVA composites show
higher decomposition rate in the first step, but lower
2927
2354 decomposition rate in the third step than pure EVA. The
667 incorporation of LDH-Si lowered the decomposition rate of
700 °C
the third step, thus enhancing the thermal stability of EVA
Absorbance

638 °C composites. Above 700 C, EVA leaves no residue, while

2856
ELS0 and ELS5 leave 29.6 and 34%, separately. ELS5,
505 °C
with both SiO2 and LDH, shows higher thermal stability in
1450
470 °C all the degradation process than ELS0. It is also the main
3743
1784 357 °C reason why the EVA/LDH-Si composites assume a better
331 °C flame retardancy than that of the EVA/LDH composite.
230 °C This result confirms the synergistic effects between SiO2
174 °C
and LDH.
500 1000 1500 2000 2500 3000 3500 4000 4500
Wavenumber/cm–1 FTIR characterization

ELS5 Figure 14 shows the 3D TG-FTIR spectra of pyrolysis

2927
products of EVA and its composites during the thermal
degradation process. It can be seen from Fig. 13 that the
730 °C evolved gas products of EVA, ELS0 and ELS5 exhibit
Absorbance

648 °C characteristic bands of 950–1150, 1250–1500, 1700–1850,

2856
540 °C 2250–2400, 2800–3150 and 3400–4000 cm-1. The spectra
1459 fit well the reported FTIR features of gas products such as
3857
475 °C carboxylic acid (1700–1850 cm-1), CO
1731 -1 -1
3743
383 °C
(2250–2300 cm ), CO2 (2300–2400 cm ), H2O
667 2354 363 °C
(3400–4000 cm-1), and aliphatic hydrocarbons
235 °C
(950–1150 cm-1, 1250–1500 and 2800–3150) [8, 14]. It is
220 °C well known that depolymerization is a main process asso-
ciated with the thermal degradation of polymers. In this
500 1000 1500 2000 2500 3000 3500 4000 4500
Wavenumber/cm–1 work, the main decomposition products of EVA, ELS0 and
ELS5 are H2O, CO, CO2, carboxylic acid and aliphatic
Fig. 15 FTIR spectra of pyrolysis products of EVA, ELS0 and ELS5 hydrocarbons.
at different temperatures In Fig. 14, the thermal degradation process of the EVA
and its composites is significantly different. EVA under-
gaseous products at different temperatures during the goes two degradation steps, while ELS0 and ELS5 show
thermal degradation process [38–42]. three degradation steps. It is in good agreement with TG
results. The heated pure EVA decomposed dramatically

123
In situ synthesis of layered double hydroxides-silicon dioxide hybrids and its flame…
since it was without any flame-retardant additive. The
products include large amounts of carboxylic acid and
aliphatic hydrocarbons in the process of decarboxylation
and break of the main chains. As for ELS0, the infrared
signal of aliphatic hydrocarbons is significantly reduced by
LDH at about 2900 cm-1, compared to EVA. It indicates
that the decomposition rate of ELS0 can be effectively cut
down by LDH. After adding SiO2, the degradation rate of
ELS5 further reduces, indicating that SiO2 can enhance the
thermal stability of polymer materials.
Figure 15 shows the FTIR spectra of pyrolysis products
of EVA, ELS0 and ELS5 at different temperatures. For
EVA, there is almost no infrared signal of carboxylic acid
and aliphatic hydrocarbons below 230 C, indicating no
decomposition under this temperature. For ELS0 and
ELS5, the infrared signal of H2O is detected at
3400–4000 cm-1 below 230 C. It is due to the loss of
interlayer water in the interlayer space of LDH in the EVA
composites. With increasing temperature, the signal
intensity of pyrolysis products of EVA, ELS0 and ELS5
gradually increases. When the temperature reaches 357 C
(363 C for ELS5), a maximum signal intensity at
1700–1850 cm-1 is observed, reflecting the evolution of
carboxylic acid. With the further increase in temperature, a
maximum signal at 2800–3150 cm-1 (aliphatic hydrocar-
bons) is observed at about 475 C (470 C for ELS0).
Afterward, the signal intensity of the pyrolysis products
gradually declines. It implies that the decomposition rate of
the mixture is decelerated. It should be noticed from
Fig. 15 that the signal intensity of aliphatic hydrocarbons
(2927 cm-1) of ELS0 and ELS5 is markedly reduced
compared to pure EVA, indicating that thermal degradation
rate of ELS0 and ELS5 is decreased by LDH-Si. This fits
well the TG results.
Conclusions
LDH-Si was in situ synthesized by a co-precipitation
method. The flame retardancy, smoke suppression and
thermal degradation properties of LDH-Si in EVA com-
posites were compared with those of EVA and EVA/LDH
composites utilizing CCT, LOI, SDT and TG-FTIR anal-
ysis. Results confirmed the synergistic effect between LDH
and SiO2 on the flame-retardant EVA composites. The
HRR, THR, mass loss, SPR and SF of the EVA composites
were significantly reduced by LDH-Si compared to EVA/
LDH composites. When adding 2.5 mass% SiO2, HRR of
the ELS5 was the lowest among all samples. A suit-
able addition of SiO2 can apparently enhance the LOI
values of EVA composites. The composites containing
LDH-Si produced less smoke than pure EVA and EVA/
LDH composites with the application of a pilot flame. The
thermal stability of EVA/LDH-Si composites was greatly
improved by SiO2. As a result, the introduction of the
LDH-Si into EVA composites led to higher flame-retardant
efficiency, smoke suppression and thermal stability.
Acknowledgements The authors sincerely acknowledge the financial
supports by the National Natural Science Foundation of China (Nos.
51372129 and 51572138) and the Project of People’s Livelihood
Science and Technology of Qingdao City (No. 16-6-2-54-nsh).
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