FLAME RETARDANCY AND ULTRAVIOLET RESISTANCE OF SILK

FABRIC COATED BY GRAPHENE OXIDE

by

Yi-min JIa, Ying-ying CAOa, Guo-qiang CHENa and Tie-ling XINGa,b*

a
National Engineering Laboratory for Modern Silk, College of Textile and Clothing Engineering,
Soochow University,199 Ren-Ai Road, Suzhou, China
b
Jiangsu HuaJia Group, Suzhou, China

Silk fabrics were coated by graphene oxide(GO) hydrosol in order to

improve its flame retardancy and ultraviolet resistance. In addition,
montmorillonoid (MMT) was doped into the GO hydrosol to further improve
the flame retardancy of silk fabrics. The flame retardancy and ultraviolet
resistance were mainly characterized by limiting oxygen index, vertical
flame test，smoke density test and ultraviolet protection factor (UPF). The
synergistic effect of GO and MMT on the thermal stabilization property of
the treated silk fabrics was also investigated. The results show that the
treated silk fabrics have excellent flame retardancy, thermal stability, smoke
suppression and ultraviolet resistance simultaneously.

Key words: Silk fabric, flame retardancy, graphene oxide, ultraviolet

resistance, smoke density

Introduction

Silk, as a natural cellulose fiber with good air permeability, hygroscopicity and superb
wearing comfortableness, has been extensively applied in clothes and household textiles, and it is
considered as an ideal material for making wearable electronics and flexible sensor[1,2]. However, silk
belongs to flammable fabric, and it can be easily ignited by flame, which confines its further
application. Furthermore, this shortcoming of silk may induce fire disaster and cause huge losses to
people[3]. Meanwhile, the human’s skin exposure to the ultraviolet of sun radiation may cause some
serious consequences like melanin deposition, skin drying, pain and wrinkle. However, ultraviolet
resistance of natural silk fabric is too low to meet the anti-UV standard protecting people’s skin[4].
Therefore, it is significant to improve the flame retardancy and ultraviolet resistance of silk fabric in
some specific application fields.
Graphene, as a new two-dimensional laminar carbon material, has attracted a great deal of
attention recently for its’ excellent electric conductivity, thermal stability and ultraviolet resistance
properties[5-7]. Furthermore, graphene oxide(GO) is a derivative of graphene, which has varieties of
functional groups on the basal planes like hydroxyl, epoxide functional groups and carboxyl. GO, as a
novel environmental friendly flame retardant, has no toxicity and zero halogen, and has been used in

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some flame retardant fields[8]. At present, there are two reported methods of applying the flame
retardancy of graphene to textiles finish: one is layer-by-layer assembly technology, through which the
GO and other flame retardants could be finished onto the fabric surface[9]; the other method is doping
method, that is to say, GO doped with flame retardant nanoparticles to finish textiles[10]. But those
two methods both cannot make the flame retardancy of graphene work most effectively.
In this work, a facile coating method was used to treat silk fabrics with flame retardant
GO hydrosol. Moreover, in order to further improve the flame retardancy of silk fabric, different
quantity of montmorillonoid (MMT) was added into the GO hydrosol. The flame retardancy and
ultraviolet resistance property of the treated silk fabrics were investigated, the synergistic effect
between GO and MMT on the thermal stabilization property of the treated silk fabrics were also
investigated.

Experimental
Synthesis of GO hydrosol

GO was synthesized from graphite powder by the improved Hummer’s method[11]. A 9:1
mixture of concentrated H2SO4/H3PO4(135:15 ml) was added into a 1000 mL of flask containing 3g of
graphite powder, then 21g KMnO4 was added into the mixture with quickly stirring. The reaction
system was maintained at 0℃ in the ice water bath for 30min. The reaction was then heated to 50℃
and stirred for 10h. Finally, the reaction was cooled to room temperature and 450ml deionized water
with 6ml H2O2( 30%) was added to stop the oxidation process. The product was then washed in
succession with 200 mL of water, 200 mL of 30% HCl, and 200 mL of ethanol, for each wash, then the
product was centrifuged at 10000 rpm for 10 min. The remained product was then added with enough
deionized water and dialyzed for 3 days. The final product, GO hydrosol, was obtained.

Preparation of GO coated silk fabrics

Different quantity of montmorillonoid (MMT) was added into the GO hydrosol,

polyvinyl alcohol (PVA) was also added into the GO hydrosol as thickener. Then five different mass
ratios of the GO-PVA-MMT (90:10:0, 85:10:5, 80:10:10, 75:10:15, 70:10:20) flame retardant coatings
were prepared to coat five silk fabrics using a sample coating machine. The prepared silk fabrics with
different flame retardant coatings were designated as silk-1, silk-2, silk-3, silk-4, silk-5 respectively.

Measurements

The flammability of the samples was determined by limiting oxygen index (LOI)
according to ASTM D2863 on a FTT 0002 oxygen index instrument (FTT, UK). The LOI index refers
to the minimum concentration of oxygen in a mixture of oxygen and nitrogen which will just support
flaming combustion over a length of 40 mm at 23 ±2 °C.
The thermal stability of the samples was carried out with YG8158 fabric flame-retardance
tester (Ningbo Textile Instrument Factory, China) according to the ISO 6941:2003 testing standard.
The samples were vertical suspended in the chamber, with 3 cm high flame burning it for 12 s, the
damage length of the samples was measured by a ruler.
The smoke suppression of the samples was carried out with FTT 0064NBS smoke density

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test chamber (FTT, UK) according to the ISO 5659-2 testing standard in terms of flameless
combustion mode at 560℃ for 500s, with the maximum radiant heat of 50kW/m2 and one sample
layer of 80×80mm2.
The morphology of the samples was observed by a Hitachi TM3030 Desktop Scanning
Electron Microscope (SEM) at an acceleration voltage of 3 kV under vacuum condition. The samples
were mounted on a conductive adhesive tape and coated with gold before testing.
The ultraviolet (UV) resistance property of the samples was characterized by Ultraviolet
Protection Factor (UPF) according to UV standard 801 on a UV-1000F UV transmittance analyzer
(Labsphere Inc. , USA). The samples were transmitted by UVA and UVB.

Results and Discussions

Limiting oxygen index analysis

The flame retardancy of the treated and untreated silk fabrics was evaluated by limiting
oxygen index (LOI) test. It can be seen from Figure 1 that the LOI value of the untreated silk fabric is
just 24.5%. With the increasing of the MMT dosage, the LOI value of the treated silk fabrics became
higher. Moreover, the LOI reached 38.5% when the silk fabric coated by GO hydrosol (silk-1), and the
LOI reached up to the highest 44.6% when the silk fabric coated by GO hydrosol with MMT
doped(silk-5). The results proved that the prepared silk fabrics have fabulous flame retardancy
property. Moreover, GO hydrosol with MMT doped can further improve the LOI value of the treated
silk fabrics, MMT and GO has a good synergistic effect on promoting flame retardancy of the
prepared silk fabrics.

45

40
LOI(%)

35

30

25

silk-control silk-1 silk-2 silk-3 silk-4 silk-5

Figure 1. LOI value curve of the treated and untreated samples

Vertical flame test and thermal stability analysis

In order to investigate the thermal stability of the prepared silk fabrics, the vertical flame
test was conducted. The result is showed in Table 1 and Figure 2. It can be seen that there is a serious
damage appeared in the sample silk-control with 22.0 cm of damaged length. In contrast, a slight
damage appeared in the sample silk-1 with 11.5 cm of damaged length. Furthermore, sample silk-5
kept its shape as before and its damaged length is only 9.5cm. The results indicated that GO coating
had an effective protection to silk fabric because the GO films deposited on the silk fabric surface can
protect the fabric from damaging by the flame, and GO coating can also greatly improve the thermal

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stability of the silk fabric. In addition, MMT doped in GO hydrosol appropriately could further
improve the thermal stability and flame retardancy of silk fabric. When the dosage of the MMT doped
in the composite hydrosol reached 20%, the synergistic effect between GO and MMT on promoting
thermal stability and flame retardancy was the best, which was also consistent with the LOI value of
the treated samples.

Table 1. Damaged length of silk samples

Sample silk-control silk-1 silk-2 silk-3 silk-4 silk-5

Damaged length
22.0 11.5 11.0 10.4 10.0 9.5
[cm]

(a) (b) (c)

Figure 2. Vertical flame test images of silk-control (a), silk-1 (b) and silk-5 (c)

Smoke density test

Smoke density refers to the amount of smoke produced by the material under test
conditions. If the material generates great amount of smoke in the fire disaster, evacuating personnel
and extinguishing the fire would be more difficult.
The smoke suppression situation of treated and untreated silk fabrics is depicted in Figure
3. It can be seen that the silk-control kept the smoke density value of 8.20 (/g) after 150 s, in contrast,
the sample silk-1 shows fabulous smoke suppression ability. The maximum smoke density value of
silk-1 was only 3.09 (/g), which appeared at the time of 154s. Furthermore, the smoke density curve of
the sample silk-5 shows that its’ smoke suppression ability is stronger than sample silk-1, and its
maximum smoke density value is 2.72 (/g). These results indicated that GO hydrosol could efficiently
suppress the smoke release of silk fabric under flame burning condition, and the GO films deposited
on the silk surface endowed the silk fabric with excellent smoke suppression ability. In addition, the
synergistic effect between GO and MMT could further decrease the smoke density value of the silk
fabrics. From Figure 3, it also can be seen that curves of the sample silk-1 and silk-5 appear a
downward trend obviously after the maximum smoke density peak, and the final smoke density value
of the sample silk-5 is only about 1.60 (/g). This result might be attributed to the honeycomb structure
consisted of combusted GO films carbon layer upon the silk fabric surface. As a result, the structure

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could absorb a large amount of smoke and reduce the smoke density value of the treated samples.

10
silk-control

per unit of fabric weight ( /g)

8

Smoke density 6

4
silk-1
2

silk-5
0
0 100 200 300 400 500
Time(s)

Figure 3. Smoke density curves of silk-control , silk-1 and silk-5

SEM

The surface morphology of silk samples observed by scanning electron microscope(SEM)

are showed in Figure 4. Compared (b) with (a), it can be seen that the GO films successfully deposited
on the silk fabric surface. These films made silk fabric separate from oxygen just like fire prevention
net. Meanwhile, as a carbon material, GO has higher ignition point than silk fabric and its combustion
would produce a large amount of carbon dioxide. As we know, the carbon dioxide can prevent burning
efficiently. Besides, compared(c) with(b), it can be seen that there were so many MMT particles in the
GO films deposited on the silk fabric surface, indicating that the flame retardant elements Si and Al
have been attached to the surface successfully. The two elements would improve the thermal stability
of the silk fabrics treated by MMT doped GO hydrosol.

(a) (b) (c)

Figure4. SEM images of silk-control(a), silk-1(b) and silk-5(c)

Ultraviolet resistance analysis

In order to investigate the ultraviolet resistance property of the silk fabrics, three
ultraviolet resistance factors were taken into consideration to measure it, i.e. the UPF values,
transmittance of UVA and UVB. The measurement results of three silk fabric samples are showed in
Figure 5. It can be seen that the UPF value of sample silk-control is 7, but the UPF value of all the

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other treated samples reached striking 500. In addition, 28% of UVA and 9% of UVB could transmit
the controlled silk fabric, however, the silk coated by GO can block more than 99.9% of UVA&UVB.
The results indicated that GO films deposited on the surface provide the silk fabric with excellent
ultraviolet shielding effect.

UPF
UVA
UVB
500 30

25
400

UVA&UVB(%)
20
300
UPF

15
200
10

100
5

0 0

silk-control silk-1 silk-2 silk-3 silk-4 silk-5

Figure 5. The UPF value and UVA&UVB transmittance of silk samples

Conclusions

In conclusion, silk fabric coated by graphene oxide has superb flame retardancy, thermal
stability, smoke suppression and ultraviolet resistance properties simultaneously. The graphene oxide
hydrosol doped with montmorillonoid presented a good synergy effect on promoting flame retardancy
and thermal stability of silk fabric. This multifunctional silk fabric would have a promising application
in the future.

Acknowledgements

The work is supported by Natural Science Foundation of Jiangsu Province (BK20151242),

the Six Talent Peaks Project of Jiangsu Province (JNHB-066), China Postdoctoral Science Foundation
(2016M600437),Jiangsu Planned Projects for Postdoctoral Research Funds (1601025B), Priority
Academic Program Development of Jiangsu Higher Education Institutions (PAPD) and Qing Lan
Project.

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Paper submitted: June 15, 2016

Paper revised: August 4, 2016
Paper accepted: Sept. 4, 2016

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