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Materials Chemistry
Cite this: J. Mater. Chem., 2012, 22, 23057 PAPER
Functionalized graphene oxide for fire safety applications of polymers: a
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combination of condensed phase flame retardant strategies†

Chenlu Bao, Yuqiang Guo, Bihe Yuan, Yuan Hu* and Lei Song*
Received 27th July 2012, Accepted 12th September 2012
DOI: 10.1039/c2jm35001g

Graphene is promising for the fire safety applications of polymers, but the ease of burn out limits
further developments. A novel strategy based on functionalized graphene oxide (FGO) is developed to
overcome this challenge. Graphene oxide is functionalized with char-catalyzing agents and reactive
compounds and incorporated into polystyrene. When FGO–polystyrene composites are degraded or
burned, FGO catalyzes the char formation from polystyrene (Char A). Char A protects FGO from
burning out and then FGO acts as a graphitic char (Char B). Because of the combination of Char
A, Char B, the physical barrier effects of FGO, and the strong interfacial interactions of FGO
and polymers, the fire safety properties of the FGO–polystyrene composites are improved,
including decreased peak CO release rate (66% decrease), decreased peak CO2 release rate (54%
decrease), decreased peak heat release rate (53% decrease), decreased thermal degradation rate (30%
decrease), decreased total heat release (38% decrease), and increased char formation (7 times), etc. This
strategy combines several condensed phase flame retardant strategies such as the nanocomposite
technique, intumescent flame retardant systems and phosphorus–nitrogen synergism systems, and
hence results in more significant improvements as compared with prior work.

1. Introduction when GPCs are burned (see the ESI†).9,10 Therefore, further
improvements are inhibited.
Graphene, a one-atom-thick monolayer of sp2-hybridised The fire safety properties of polymers can be improved by
carbon, has gained increasing interest since it was reported by flame retardants mainly by three strategies: (1) vapor phase
Geim et al. in 2004.1 Graphene has many unique properties such strategies where flame retardants stop or reduce the combustion
as quantum effects, high electron mobility, superior mechanical reaction in the vapor phase; (2) condensed phase strategies where
properties, and large specific area, etc., and is promising in flame retardants inhibit the degradation of the polymer and the
many applications including energy and electronic devices, diffusion of heat, degradation products and gases; and (3) flame
transparent conductive materials, sensors, catalysts, quantum retardants reduce the heat fed back to the polymers from
dots, and high-performance graphene–polymer composites combustion zones or remove heat from the polymers.18–23 There
(GPCs), etc.2–8 has been great interest in condensed phase strategies because of
Recently graphene has shown great potential for fire safety the high efficiency and environmental friendliness, and layered-
applications of polymers.9–16 Polymers are usually easily ignited nanofiller–polymer (nano)composites (LNPCs) and intumescent
and burned, so improved fire safety properties are highly desir- flame retardants (IFRs) are the most promising ones in this
able due to the expanding applications of polymers. With a small family. In LNPCs, layered-nanofillers, e.g. clays, act as physical
additive amount of graphene (usually <2%), the thermal stability barriers in the polymeric matrix to inhibit the diffusion of heat,
of GPCs is improved, and the release of heat and toxic gases gases and thermal degradation products at low loading levels
during the combustion of GPCs is reduced.9–11,14,15 The physical (usually <5% by weight).24–26 In IFR systems, char, a mixture of
barrier effect of graphene which slows down the diffusion of amorphous and graphitic carbon, is formed on the surface of the
gases and degradation products, and the interfacial interactions polymers during combustion, which inhibits the exchange of
among graphene and polymers, are the main reasons for the heat, combustible gases and oxygen between the polymers and
improvements.9,10,17 However, graphene is usually burned out combustion zone.19,27
As a 2-dimensional layered nano-material with high thermal
State Key Laboratory of Fire Science, University of Science and stability and large specific area, graphene is appropriate for the
Technology of China, Hefei, Anhui 230026, P. R. China. E-mail: LNPCs technique; and as a graphitic carbon, graphene may act; Fax: +86-551-3601664; Tel: +86-551-3601664;; +86-551-3601642; +86-551-3601642
as a graphitic char just like the char in IFR systems. Therefore,
† Electronic supplementary information (ESI) available: See DOI: graphene is likely to combine the LNPCs technique and IFR
10.1039/c2jm35001g systems together. However, the ease of burn out of graphene

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makes the combination unavailable. As is well known, graphene  molecular sieves before use. HCCP was
China and dried over 4 A
is more stable in an anoxic atmosphere than in an oxygen-rich obtained from Zibo Lanyin Chemical Co. Ltd (China).
atmosphere. Graphene is degraded in air below 600  C28 but is
highly stable in a nitrogen atmosphere up to 800  C.12 Thus, if an 2.2 Preparation of GO and FGO
anoxic environment is formed around graphene when the GPCs
are burned, there is a strong possibility to prevent graphene from GO was prepared by a modified Hummers’ method and washed
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burning out, and then the graphene may act as a graphitic char to with THF to remove water.17 GO (about 2 g) was dispersed in
protect the underlying polymers. To achieve this objective, THF (400 mL) in a 1000 mL three-necked flask equipped with a
herein, a novel strategy based on functionalized graphene oxide mechanical stirrer and nitrogen inlet. HCCP (36 g) and TEA
(FGO) was developed. Graphene oxide (GO) was functionalized (60 g) were dispersed in THF (100 mL), respectively. The HCCP–
with hexachlorocyclotriphosphazene (HCCP, molecular THF and TEA–THF mixtures were dripped into the GO–THF
formula: P3N3Cl6) and hydroxyethyl acrylate (HEA). As a blend with stirring. The reaction was carried out at 15–20  C for
phosphorus–nitrogen compound, HCCP efficiently catalyzes the 12 h. HEA (70 g) was dispersed in THF (100 mL) and then
char formation from polymers (defined as Char A).29–32 FGO is dripped into the mixture. After 24 h of reaction, the obtained
protected from oxygen by Char A, so it does not burn out and FGO was washed with deionized water and THF. A small
can then act as a graphitic char (defined as Char B). HEA portion of GO and FGO was dried at 80  C for 24 h for
introduces C]C groups to FGO which can be polymerized with characterization.
monomers, so strong covalent interfacial interactions are avail-
able among the FGO and polymers. As a result, several plus 2.3 Preparation of FGO–PS composites
factors are combined in this strategy: (1) Char A protects the
underlying polymers; (2) FGO, which is protected by Char A, FGO–PS composites were prepared by in situ polymerization.
protects the underlying polymers; (3) FGO acts as a physical FGO was dispersed in styrene (total amount: 25 g) in a three-
barrier in the polymeric matrix, which is beneficial to improving necked flask by magnetic stirring. The flask was heated at 70  C
the fire safety properties;9,10 and (4) the strong interfacial inter- in an oil bath. After 30 min of stirring, BPO (1 wt% compared to
actions among the FGO and the polymers may also improve the styrene) was added to the mixture and further stirred until the
fire safety properties.9 mixture turned highly viscous. The blend was poured into a mold
Polystyrene (PS) was chosen as the polymeric matrix. Neat (basal dimension 100  100 cm2) and heated at 80  C for 24 h.
PS forms little char during combustion, and the new strategy Samples are entitled PS/x% FGO, where x (1, 2 and 3) is the mass
may pioneer a route to solve this problem. GO was covalently ratio of the FGO in the composites.
functionalized with HCCP and HEA. FGO–PS composites
were prepared by in situ polymerization (Fig. 1). The compo- 2.4 Characterization
nent, structure and fire safety properties of the FGO and
FGO–PS composites were investigated and compared with Atomic force microscopy (AFM, Veeco DI Multimode V) was
prior work. employed to investigate the morphology of the GO. Samples
were dispersed in water with 20 min of ultrasonication and dip-
coated onto freshly cleaved mica surfaces before observation.
2. Experimental Transmission electron microscopy (TEM, JEM-2011, Japan
Electron Optics Laboratory) was employed to investigate the
2.1 Raw materials
morphology of GO and FGO and the dispersion of FGO in
Expandible graphite was supplied by Qingdao Tianhe Graphite FGO–PS composites. GO and FGO were dispersed in water with
Co., Ltd., China (purity >98%). Sulfuric acid (H2SO4, 98%), 20 min of ultrasonication and dripped onto copper grids; FGO–
sodium nitrate (NaNO3, AP), potassium permanganate PS composites were microtomed to ultrathin sections for obser-
(KMnO4, AP), hydrazine hydrate (85% aq.), hydrochloric acid vation, using a Du Pont MT-6000 Ultratome.
(HCl, 37% aq.), styrene, benzoyl peroxide (BPO, AP), and X-Ray photoelectron spectroscopy (XPS, VG ESCALB MK-
tetrahydrofuran (THF, AP) were obtained from Sinopharm II electron spectrometer) was employed to investigate the
Chemical Reagent Co., Ltd., China. Triethylamine (TEA, AP) elemental composition of GO and FGO. The excitation source
was obtained from Shanghai Chemical Reagents Company of was an Al Ka line at 1486.6 eV.

Fig. 1 Preparation and characterization of FGO: (a) preparation routes of FGO and FGO–PS composites; (b) AFM profiles of GO; (c) TEM
photograph of GO; (d) TEM photograph of FGO.

23058 | J. Mater. Chem., 2012, 22, 23057–23063 This journal is ª The Royal Society of Chemistry 2012
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Fourier-transform infrared (FTIR) spectra of GO and FGO

were obtained on a Nicolet 6700 FTIR instrument. Samples were
mixed with KBr powder and pressed into tablets.
X-Ray diffraction (XRD) of GO and FGO were performed
with a Rigaku D ¼ Max-Ra rotating anode X-ray diffractometer
equipped with a Cu-Ka tube and a Ni filter (l ¼ 0.1542 nm).
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The thermal properties of the GO, FGO and PS–FGO

composites were investigated by a TA Q5000 thermo-analyzer.
Samples were heated at a linear rate of 20  C min1 from room
temperature to 700  C in a nitrogen atmosphere.
The fire safety properties of the FGO–PS composites were
investigated on a Stanton Redcroft cone calorimeter according
to ISO 5660-1 standard, with a heat flux of 35 kW m2. The
dimensions of the samples were 100  100  2 mm3.
The char obtained in the cone test was studied by scanning
electron microscopy (SEM, AMRAY 1000B, Beijing R&D
center of the Chinese Academy of Sciences, China).

3. Results and discussion

The morphology of the GO and FGO was studied by AFM
(Fig. 1b) and TEM (Fig. 1c and d). The thickness of the GO was
1.0 nm, which is typical for single-layer GO.33 The GO presented
a clean morphology (Fig. 1c) but the FGO was a little fuzzy
(Fig. 1d) due to the bonding of functionalization agents.
The chemical components of the GO and FGO were studied
by XPS and FTIR, as shown in Fig. 2. The XPS curves (Fig. 2a)
indicate the presence of three kinds of carbon in the GO and
FGO: C]O, C–O and C]C in the graphitic domain, and a peak
of C–O–P appears in the curve of the FGO. In the FTIR spectra
(Fig. 2b), GO presents the typical spectra of oxygen-based
functional groups: –OH at 3420 cm1, C]O at 1728 cm1, C]C
and the hydroxyl in the adsorbed water at 1625 cm1, and C–O at Fig. 2 XPS (a) and FTIR (b) curves.
1000–1300 cm1.34–38 Several new peaks are observed in the curve
of FGO due to the bonding of HCCP and HEA, and the peak at
about 980 cm1 is attributed to C–O–P.39–41 circumstantial evidence. PS/1% FGO and PS/3% FGO were cut
In the XRD curves (Fig. 8), a typical (001) diffraction of GO is in ultrathin sections and investigated by TEM (Fig. 3b and c).
located at 2q ¼ 11.4 and it is shifted to 2q ¼ 8.9 in FGO, FGO layers are well dispersed in the composites due to the good
implying that the d-spacing is increased from 0.77 nm (GO) to compatibility of FGO and the strong covalent interaction
1.00 nm (FGO) due to the binding of HCCP and HEA. between FGO and PS. In earlier work, the ultrathin sections of
Based on the information above, it is reasonable that GO has GPCs were usually smooth,9,43–51 but the ultrathin sections in
been modified by HCCP and HEA. Fig. 3 are obviously rougher, especially around the FGO layers,
The dispersion of graphene-based nanofillers and the interfa- implying that FGO has formed strong interfacial interactions
cial interactions between graphene-based nanofillers and the with PS due to the functionalization.
polymeric matrix are two key factors for GPCs.42 The dispersion Thermogravimetric analysis (TGA) was employed to evaluate
is influenced by the compatibility of the nanofillers as well as the the thermal stability of the GO, FGO and FGO–PS composites
interfacial interactions between the nanofillers and polymers. (Fig. 4). The mass loss occurring below 100  C is attributed to the
The compatibility of FGO in styrene was compared with that of adsorbed water in GO and FGO. The main mass loss in GO
GO and graphene (Fig. 3a). Graphene (10% oxygen and 90% occurs at about 200  C, due to the decomposition of oxygen-
carbon) was prepared by an ammonia–hydrazine multiplex containing groups.52,53 FGO is more stable than GO because
reduction.10 GO, graphene and FGO were washed with THF to FGO is partially reduced by amines.54,55 The degradation of PS
remove water, dispersed in styrene, sonicated for 10 min, and occurs at 400–450  C. FGO–PS composites have two mass loss
then kept standing for 2 h. As shown in Fig. 3a, GO and gra- stages. The first stage is at 180–400  C, probably due to the
phene precipitate while FGO remains well-dispersed in styrene, release of monomers and oligomers. The second stage, which is
so the compatibility of FGO is improved as compared with GO the main mass-loss stage, occurs between 400 and 470  C. FGO–
and graphene. The interfacial interactions between FGO and PS PS composites present higher thermal stability than neat PS in
not only affect the dispersion of FGO but also influence the the second stage because of the good physical barrier effect of the
properties of the composites. The direct measurement of inter- FGO layers and the strong interfacial interactions between FGO
facial interactions is not easy. Herein, TEM studies offer and PS.9 The char formed during thermal degradation and

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Fig. 3 Dispersion of FGO: (a) photograph of GO, graphene and FGO in styrene after standing for 2 h; and (b) and (c) TEM photographs of the
ultrathin section of PS/1% FGO and PS/3% FGO, respectively.

was actually entirely from the incorporated graphene and no

char was formed from the PS in the composite. From these
comparisons, it is clear that FGO catalyzes the char formation of
PS due to HCCP. Because of the physical barrier effect of FGO
and improved char, differential thermogravimetric (DTG) peaks
of the FGO–PS composites, which indicate thermal degradation
rates, are visibly decreased (Fig. 4b). The maximum decrease is
about 30% (PS/2% FGO and PS/3% FGO), which is also a better
improvement as compared with prior work.9,48,56
The char formation and fire safety properties of FGO–PS
composites were investigated by cone calorimetry. Samples were
heated and ignited under a strong heat flux (35 kW m2). After
burning, neat PS does not form char while the FGO–PS
composites form visible char, and the char is increased when the
FGO level is increased (Fig. 5a). The morphology of the char is
studied by SEM, as shown in Fig. 5b. When the level of FGO
increases, the char surface becomes more compact and tight.
The char of PS/1% FGO is bumpy and porous; the char of
PS/2% FGO is more compact; and the char of PS/3% FGO is
continuous and highly compact (Fig. 5b). The inner structure
of the char of PS/3% FGO is bumpy and porous, and many
layers are observed, implying that FGO is not burned out. The
char contains at least two portions: Char A (from PS) and Char
B (FGO layers). In our prior work, no char was formed in
graphene–PS and GO–PS composites, because GO and gra-
phene burn out in air (Fig. 10, see the ESI†).9 In FGO–PS
composites, Char A is formed around FGO and hence protects
FGO from burning out. As shown in Fig. 5b, many layered
structures are visible which could be attributed to the protec-
Fig. 4 TGA (a) and DTG (b) curves. tive FGO layers. When the FGO level is 3%, so much Char A is
formed that it not only protects the FGO but also constructs a
continuous and compact char surface, and the protected FGO
combustion is important for fire safety applications. The char layers construct a porous framework under the surface
yield of PS is 0.6% at 700  C, and the char yield of the FGO–PS (Fig. 5b). The FGO layers and the continuous and compact
composites is increased, e.g. 6.2% in PS/3% FGO. The residue char surface are good barriers to protect the underlying poly-
amount of FGO is about 54.1%. So in the char of PS/3% FGO mers and inhibit the exchange of degradation products,
(6.2%), 1.6% (3%  54.1%) is from FGO and the rest, 4.6%, is combustible gases and oxygen.
from PS. Therefore, the true char yield of the PS in PS/3% FGO Fire safety properties, including heat release rate (HRR), total
is about 4.7% (4.6%/97%), which is a 7 times increase (4.7%/ heat release (THR), CO2 yield and CO yield, are shown in Fig. 6
0.6%) as compared with neat PS. In earlier work, the char yield of and Table 1. The HRR, THR, peak heat release rate (PHRR),
graphene–PS composites was very little, and the presence of CO2 yield and CO yield are all decreased. The maximum
graphene did not improve the char formation. For example, the decreases are 53% in PHRR (PS/3% FGO), 38% in THR (PS/1%
residue yield of PS–graphene-2 (2 wt% graphene) was 1.7%, and FGO), 54% in CO2 (PS/3% FGO), and 66% in CO yield (PS/3%
the residual weight of graphene was about 87%,9 so the char yield FGO). As compared to graphene, GO and metal-loaded

23060 | J. Mater. Chem., 2012, 22, 23057–23063 This journal is ª The Royal Society of Chemistry 2012
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Fig. 5 Observations of char: (a) digital photographs; and (b) SEM profiles.

graphene,9 FGO performs much better in improving the fire in Fig. 7, the SEA curves fluctuated, so direct comparison among
safety properties of PS. It is attributed to the combination of the different curves is unavailable, and the average SEA is
Char A, Char B, the physical barrier effect of FGO and the employed as shown in Table 1 and Fig. 8. The average SEA
strong interfacial interactions between FGO and PS. values are increased when the FGO loading level is increased,
The specific extinction area (SEA) is employed to evaluate the indicating that FGO increases the smoke yield during combus-
smoke yield during the combustion of the composites. As shown tion. It is probably because of two reasons. First, FGO catalyzes

Fig. 6 Cone calorimeter test results: (a) HRR curves; (b) THR curves; (c) CO2 yield; and (d) CO yield.

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Table 1 Data collected from the cone test

Samples ITT (s) (kW m2) THR (MJ m2) P-COa (g s1) P-CO2a (g s1) Av-SEAb (m2 kg1)

PS 50 1703 139 0.021 0.552 887

PS/0.5% FGO 30 1127 96 0.012 0.391 888
PS/1% FGO 25 1058 86 0.010 0.338 894
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PS/2% FGO 20 908 92 0.008 0.287 1000

PS/3% FGO 20 805 93 0.007 0.226 1086
The peak values of the CO release rate and CO2 release rate, respectively. b The average values the SEA.

speed up the diffusion of heat from the surface into the body of
GPCs. When samples are heated in a cone calorimeter, GPCs are
more easily able to increase their temperature as compared with
neat polymer samples because of the high thermal conductivity
of graphene-based materials, and thus, the ignition of GPCs is
facilitated. Such facilitation is still a challenge to be overcome
because it makes burning easy.
Table 1 and Fig. 8 show the data obtained from the cone test.
Most of the data are decreased when increasing the loading level
of FGO, and the average SEA is increased, indicating increased
smoke yield. This strategy combines several condensed phase
strategies such as the intumescent flame retardant system,
phosphorus-nitrogen synergism system and polymer nano-
composite technique, and causes further improvements in the fire
safety properties of PS as compared with GO or graphene.9 The
Fig. 7 SEA curves. functionalization of char-catalyzing agents, which protect gra-
phene from oxygen when burned, is the key factor for the
combination. This strategy can also be applied in other polymers,
and the results here indicate a promising future of functionalized
graphene in fire safety applications of polymers.

4. Conclusions
GO is functionalized with HCCP and HEA and incorporated
into polystyrene by in situ polymerization. The functionaliza-
tion improves the formation of Char A. Char A protected FGO
from oxygen, so FGO does not burn out and then acts as Char
B. The combination of Char A and Char B resulted in
continuous and compact char on the surface of the composites
to protect the underlying polymers. Due to the improved char,
the physical barrier effect of the FGO, and the strong interfa-
cial interactions among FGO and the polymeric matrix, the fire
safety properties of the composites are improved, including the
Fig. 8 Trends of the data obtained in the cone test. peak CO release rate (66% decrease), peak CO2 release rate
(54% decrease), peak heat release rate (53% decrease), thermal
degradation rate (30% decrease) and total heat release (38%
the char formation of FGO–PS composites; and second, FGO
decrease), etc.
itself is a part of smoke since it is a graphite-based compound.
When FGO–PS composites are burned, the char and FGO are
both released in air, and, as a result, increase the smoke yield as
compared with neat PS.
As reported in our earlier works, graphene-based materials The authors acknowledge the supported from the National Basic
usually facilitate the ignition of GPCs.9,10 Fig. 6 indicates that the Research Program of China (973 Program, no. 2012CB719701),
ignition time (ITT) is decreased when increasing the FGO the joint fund of the National Natural Science Foundation of
loading level, and Fig. 7 indicates that the onset time of smoke China and Guangdong Province (no. U1074001), and the joint
release is also decreased. Such a decrease is attributed to the high fund of the National Natural Science Foundation of China and
thermal conductivity of graphene-based materials, 60–63 which Civil Aviation Administration of China (no. 61079015).

23062 | J. Mater. Chem., 2012, 22, 23057–23063 This journal is ª The Royal Society of Chemistry 2012
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