Journal of Cleaner Production 243 (2020) 118641

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Flame retardant cellulosic fabrics via layer-by-layer self-assembly

double coating with egg white protein and phytic acid
Xiaohui Liu a, *, Qiuyan Zhang a, Bo Peng a, Yuanlin Ren b, **, Bowen Cheng a, b, Chen Ding a,
Xiaowei Su a, Ju He a, Shenggen Lin a
a
School of Materials Science and Engineering, Tiangong University, Tianjin, 300387, China
b
School of Textiles, Tiangong University, Tianjin, 300387, China

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

Article history: In this work, facile and inexpensive egg white protein with numerous amino acids, calcium, ferric, sulfur,
Received 17 April 2019 and phosphorus was firstly explored to flame retard cellulosic fabrics. This was achieved by generated
Received in revised form phosphorus-nitrogen flame retardant system formed by intense electrostatic attraction of egg white
26 September 2019
protein and phytic acid (PA) with special hexaphosphate-substituted cyclic structure. As expected, the
Accepted 27 September 2019
cotton fabrics treated by protein and PA in sequence exhibit high residue and time to ignition as well as
low values for peak of heat release rate and total heat release after burning than those of control fabrics
Handling editor: M.T. Moreira evaluated by thermogravimetric and cone calorimeter analyses, which is comparable or prior to other
biomaterials. The results suggest that the treated fabrics displayed excellent flame retardancy properties,
Keywords: which is ascribed to synergistic effect of phosphorus and nitrogen granted by the double-coating system
Egg white protein of PA and egg white protein.
Phytic acid © 2019 Elsevier Ltd. All rights reserved.
Cellulosic fabrics
Synergistic effect

1. Introduction et al., 2013). Alternatively, high efficient and environmental-

Cotton, one of the most popular natural cellulosic resources,
possesses excellent advantages, such as softness, breathability,
superior water absorbance, and etc (Ganner T. et al., 2014; Xie et al.,
2013). Therefore, cotton fabrics are usually used for clothing, house
furnishing, and military goods. Unfortunately, the inflammability of
cotton often induces fire hazards, leading to heavy loss of lives and
properties (Shariatinia et al., 2015). Thus, enhancing fire resistance
of cotton fabrics has become an essential and challenging issue in
textile industry.
In the last few decades, the halogen-containing compounds are
the most efficient and widely used flame retardant (FR) for cotton
fabrics (Kemmlein et al., 2009; Qi et al., 2014). However, toxic gases
(e.g., dioxin) are mostly released during the combusting process.
Considering that the toxic gases may successively accumulate in
human bodies or organisms and also pollute environment (Carosio
et al., 2015), the application of this type of flame retardant has been
banned in European countries and USA in recent years (Abou-Okeil
* Corresponding author.
** Corresponding author.
E-mail addresses: liuxiaohui@tjpu.edu.cn (X. Liu), yuanlinr@163.com (Y. Ren).
friendly flame retardant, for example, phosphorus-based com-
pound has been successfully applied for cotton textiles (Basak et al.,
2015, 2016a; Alongi et al., 2012). To date, the representatively and
commercially available phosphorus-based FRs for cotton textiles
include hydroxymethylphosphonium salts (Proban) (Zhang and
Horrocks, 2003) and N-methylol phosphonopropionamide de-
rivatives (Pyrovatex_CP) (Yang et al., 2005; Horrocks, 2011), and etc.
Though their limited quantities are still used, some phosphorus-
based FRs bearing hydroxymethyl group would emit formalde-
hyde during finishing and using process. Generally, formaldehyde is
now regard as a carcinogenic source by World Health Organization
(Nielsen and Wolkoff, 2010). With this regard, it is necessary to
exploit novel, efficient, nontoxic (i.e., halogen-free, and
formaldehyde-free release), and environmentally friendly flame
retardant system.
Biomacromolecules (e.g., DNA, proteins, phytic acid (PA), chi-
tosan, starch, cyclodextrin, and sodium alginatec), one kind of
green, renewable, sustainable natural resources, seem to be ideal
substitutes for flame retardants (Idumah and Hassan, 2016; Basak
and Ali, 2016b; Sharma et al., 2015). Alongi and his co-workers
firstly employed DNA to treat cotton fabrics (Alongi et al., 2013;
Alongi et al., 2014a). The thermal stability and flame retardancy of

https://doi.org/10.1016/j.jclepro.2019.118641
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
2 X. Liu et al. / Journal of Cleaner Production 243 (2020) 118641
treated fabrics were all enhanced. Furthermore, the effect of various
deposited proteins on the surface of fabrics on flame retardancy
properties were examined, including caseins, hydrophobins, whey
proteins, and etc (Alongi et al., 2014b; Costes et al., 2017; Bosco
et al., 2013; Wang et al., 2014; Carosio et al., 2014). Generally, all
of these bio-based compounds are derived from natural resources.
For example, DNA extracts from herring sperm, and protein extracts
from animal or microbial source. However, the extractions work is
complex, tedious, and tremendous, which leads to high production
costs. It undoubtedly limits the exploiting of a wide variety of
expensive proteins on a large scale.
There is few report on flame retardant with the help of natural
additives. The ancient Romans tried to reduce flammability of the
materials of their house and war vessels by dipping into bath of
 et al. measured the efficacy of two
vinegar and clay. Recently, de Sa
vegetable compounds (ginger powder and coffee husk) as a carbon
source in the intumescent flame retardant system (de Sa a et al.,
2017). Qian et al. investigated the synergistic effect of natural-
based tea saponin in intumescent flame retardant coatings (Qian
et al., 2019). However, the applications of these nature additives
to the materials were not reported. Egg white protein is known as
one of the most common and inexpensive proteins in daily life but
it contains numerous amino acids as well as calcium, ferric, and
phosphorus (Zhu et al., 2018). Moreover, intense electrostatic
attraction may occur between egg white protein containing varied
amino acids and the other eco-friendly bio-based compound, e.g.,
phytic acid (PA) with a special cyclic compound containing six
phosphate groups, thus forming a green phosphorus-nitrogen
flame retardant system (Scheme 1). Consequently, this protein is
a promising alternative to expensive ones for flame retardant.
The aim of the present contribution is to explore a novel double-
coating flame retardant system for cotton fabrics via a combination
of egg white protein and phytic acid with peculiar hex-
aphosphonate structure. The structure and morphology as well as
thermal stability and flammability of modified cotton fabrics were
detailedly investigated by various techniques.
2. Material and methods
2.1. Materials
Cotton fabrics were friendly supplied by Dahutong market
(Tianjin, China). Eggs were purchased from supermarket. Egg white
protein was separated from yolk and then dissolved in distilled
water under magnetic stirring (200 rpm) for 2 h at room tempera-
ture (pH ¼ 8.5). Phytic acid (PA, 70 wt% aqueous solution) was
purchased from Nanjing Xiezun Chemical Co. LTD (Nanjing, China)
(pH ¼ 1.5).
2.2. Layer-by-layer self-assembly double coating cotton fabrics with
egg white protein and PA
Firstly, cotton fabrics were immersed in distilled water at 50  C
and then dried in vacuum at 30  C. The dried fabrics were
immersed in the egg white protein solution, and then the excess of
egg white protein solution was removed by gently pressing with a
rotary drum. Cotton fabrics was then immersed in diluted PA
aqueous solution, and the excess of PA solution was extruded by
pressing with a rotary drum. The treated cotton fabrics were dried
to a constant weight at 80  C. Then, the above process was repeated
once again, and the double coated cotton fabrics was obtained, as
shown in Scheme 1. The control cotton fabrics was coined as COT.
Treated fabrics were coined as COT-PA, COT-Pro, COT_PAþPro, and COT-
ProþPA, which refer to cotton fabrics treated with phytic acid, egg
white protein (Pro), phytic acid combined with egg white protein in
sequence (PAþPro), and egg white protein combined with phytic
acid in sequence (ProþPA), respectively.
2.3. Characterization
Fourier transform infrared spectroscopy (FTIR) was used to
detect the structures of COT, COT-PA, COT-Pro, COT_PAþPro, and COT-
ProþPA, and were recorded with KBr powder using a Nicolet iS50
FTIR infrared spectrophotometer. The resolution factor of FTIR
spectrometer was 0.09 cm1, and the spectral range was
400e4000 cm1.
The surface morphologies of all samples and their char residues
after burning were measured by a scanning electron microscope
(SEM). Elemental dispersive X-ray analysis (EDX) of cotton fabrics
treated by egg white protein and phytic acid was carried out using a
cold field emission gun scanning electron microscope (FEG-SEM) to
determine the distribution of various elements and quantity of
chemicals coating on the surface of cotton fabrics.
The thermal stabilities of all samples were evaluated by ther-
mogravimetric analysis (TG), using STA449F3 thermogravimetric
analyzer from 40  C to 800  C with a heating rate of 10  C/min in air.
The vertical flammability of control and treated fabrics was
examined according to ASTM D6413-99 standard test method on a
YG815B vertical fabric FR tester (Nantong Sansi electromechanical
Science & Technology Co., Ltd.,China).
The combustion performances of the control and treated cottons
were measured by a cone calorimeter (FTT, East Grinstead,UK) ac-
cording to ISO 5660-1 under an irradiative heat flux of 35 kW/m2 in
horizontal configuration. All samples with the dimension of
100 mm  100 mm were placed in aluminum foil to protect the
edges and back of the sample and maintained in the correct
configuration by a metallic grid welded at intersections. The tests
were repeated five times for each sample to ensure reproducible
data. All samples were conditioned at 23 ± 1  C for 48 h under the
condition of 50% relative humidity in a climatic chamber before
combustion tests. Time to ignite (TTI), heat release rate (HRR) and
corresponding peak (PHRR), and total heat release (THR) were all
evaluated. The residues after testing were photographed by a dig-
ital camera (Power-Shot A2000 IS, Canon Inc., Tokyo, Japan).
Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS)
system was conducted to detect the pyrolysis volatiles by using a
gas chromatography/mass spectrometry (SHIMADZU GCMS-
QP5050A, Agilent) with a Frontier PYR-4A type pyrolyser. The py-
rolysis was proceeded at 600  C for 30 s. The capillary column
(0.25 mm) of GC was hold at 40  Ce300  C at a heating rate of 10  C/
min.
3. Results and discussion
3.1. Dependence of increased weight of treated cotton fabrics on
different coating agent
As noted elsewhere (Carosio et al., 2014), the flame retardancy of
the coated cellulosic fibers or fabrics show a strongly positive
dependence on the increased weight of the treated sample
compared with the control one. Preliminarily, the influences of the
varied flame retardant combination on the increased weight of the
treated samples were investigated. The weight gain rate values of
treated fabrics (A%) were calculated according to the following
equation:
Wf  Wi
A% ¼  100%
Wi
where Wi and after Wf represent the weight of control and coated
 X. Liu et al. / Journal of Cleaner Production 243 (2020) 118641 3

O O
HO P OH HO P OH
H
OH HO O O HO
O O O O O
P P P P
O O O O
HO OH HO OH
HO OH HO OH
O O O O
P P P P
O OH O OH O O
O O O HO
HO P OH HO P
H OH
O O
H O H O
H R
N C C N C
C C N C C N
R H
R H
O H O H

H O H O
R H R H
N C C N C C
C N C C N
H R
O H O H

H H
O OH O OH
O O O O
O O O
HO HO HO HO
HO HO HO HO

Scheme 1. A general process for layer-by-layer self-assembly double-coating cellulosic fabrics with egg white proteins and phytic acid.

samples, respectively.
As illustrated in Fig. 1, the Awt.% values of all samples increased
after treated with flame retardants. Clearly, the Awt.% value of COT-
Pro (43.2 wt%) is ca. 25% which is higher than that of COT_PA (19.5 wt
%). Moreover, different coating sequences considerably influenced
the Awt.% value of fabrics. When phytic acid was served as the first
coating layer and egg white protein as the second coating layer, the
Awt.% value of the treated sample (COT_ PAþPro) is the highest
(44.3 wt%) among all samples. Contrarily, when egg white protein
was severed as the first coating layer and phytic acid as the second
one, the Awt.% value of the treated sample (COT_ ProþPA) slightly
decreased (39.1 wt%). However, phytic acid (PA) contains six
phosphoric acid members and its aqueous solution shows the
strongly acid of PA (pH ¼ 1.5), which greatly decreases mechanical
properties and handing softness of treated fabrics COT_PAþPro.
Therefore, based on these factors, egg white protein is more suit-
able for using as the inner layer to coat the sample, which also
favors to increase the weight of coated cotton fabrics. It suggests
that though egg white protein separated from yolk contains amino
acids, it belongs to alkaline compounds (pH ¼ 8.5) and will pref-
erably deposit on the surface of the sample.
3.2. Structure characterization
FTIR technique was employed to analyze the structures of con-
trol cotton fabrics, and treated samples with phytic acid (COT_ PA),
protein (COT_Pro), and protein and phytic acid in sequence (COT_-
ProþPA), and the corresponding spectra are shown in Fig. 2. For the
control sample, the characteristic peaks of cellulose units are well
detectable, such as n(OH) at 3300 cm1, n(CH2) at 2900 cm1, d(OH)
at 1640 cm1, d(CH2) at 1425 cm1, d(CH) at 1370 cm1, d(OH) at
1310 cm1, n(C]C) at 1020 cm1, and n(OH) at 894 cm1 (Sahito
et al., 2015). For COT_PA, the new appeared characteristic peak at
980 cm1 assigning to the P]O vibration from phytic acid is clearly
observed (Gospodinova et al., 2002). Similarly, for COT_Pro, there are
new characteristic peaks at 1630 cm1 and 1525 cm1 attributed to
amide I and II vibrations from egg white protein (Liu et al., 2015).
Based on FTIR spectra of treated sample with phytic acid or protein,
4 X. Liu et al. / Journal of Cleaner Production 243 (2020) 118641

43.2 44.3

40 39.1

30
A (%)

19.5
20 COT COT-PA

10

0
PA Pro PA+Pro Pro+PA
Sample
Fig. 1. The weight gain rate values of treated fabrics (A%) by phytic acid (COT_PA), egg
white protein(COT_Pro), phytic acid combined with egg white protein in sequence COT-Pro COT-Pro+PA
(COT_PAþPro), and egg white protein combined with phytic acid in sequence
(COT_ProþPA). Fig. 3. SEM micrographs of control (COT) and treated fabrics with phytic acid (COT_PA),
egg white protein (COT_Pro), and egg white protein combined with phytic acid in
sequence (COT_ProþPA). The scale bar in the right corner is 50 mm for all micrographs.
The magnification is 600 for COT, COT_PA, and COT_Pro, and 700 for COT_ProþPA.

COT
In contrarily, for cotton fabrics treated by phytic acid (COT_PA), its
surface becomes rough and some small holes appear on the surface.
The results indicate that strong acidity of phytic acid has destroyed
Transmittnce (a.u)

COT_PA
the structure of cellulose units of fabrics to some extent. For cotton
fabrics treated by egg white protein (COT_Pro), its surface displays
thickness coating layer compared with the smooth surface of
COT_Pro control sample. The thickness coating layer can protect the struc-
ture of cellulose from heat and oxygen during burning. However,
there are some small cracks on the surface of coating layer.
In order to obtain integrated protective coating layer, phytic acid
COT_Pro+PA
as the out layer was necessarily used to coordinate with egg white
protein as the inner layer, and the treated sample (COT_ProþPA)
would effectively form firming binding through intense electro-
static attraction of phosphoric acid from PA and amino acid from
4000 3500 3000 2500 2000 1500 1000 500 egg white protein. As expected, the surface of sample is composed
of continuous and smooth coating layer with few defects. It
Wavenumber (cm-1) demonstrate that as phytic acid did not directly contact with cel-
lulose units but connect with egg white protein, protein inner layer
Fig. 2. FTIR spectra of control cotton fabrics (COT), and treated fabrics by phytic acid
(COT_PA), egg white protein (COT_Pro), and egg white protein combined with phytic
can effectively protect the structure of cellulose from acid corrosion
acid in sequence (COT_ProþPA). from phytic acid.

3.4. Surface elements composition and distribution

three characteristic peaks at 980, 1525, and 1630 cm1 do also
appear in the spectrum of the cotton fabrics treated with the
combination of protein and phytic acid in sequence (COT_ProþPA),
corresponding to stretching vibration of P]O unit originated from
phytic acid as well as amide I and amide II vibrations originated
from egg white protein. Consequently, the results demonstrate that
egg white protein can efficiently bond phytic acid through elec-
trostatic attraction, and two combined layers were preferably
deposited on the surface of cotton fabrics, which is optimal to
improve the flame retardancy of treated cotton fabrics.
3.3. Surface morphology
The changes of surface morphology of control and treated cotton
fabrics were analyzed by SEM technique (Fig. 3). The surface of
control cotton fabrics (COT) is very smooth without obvious defects.
Elemental dispersive X-ray analysis (EDS) coupled with SEM
was employed to measure the surface element composition and
element distribution. Their images and detailed surface chemical
compositions (Wt % and At%) for cotton fabrics treated with egg
white protein combined with phytic acid in sequence (COT_ProþPA)
are shown in Fig. 4 and Table 1. Obviously, besides carbon and
oxygen elements, nitrogen (N), phosphorus (P), and sulfur (S) ele-
ments consist of the main constituents of the coatings. The contents
of N, P, and S elements reach 5.9%, 6.5%, and 0.43%, respectively,
suggesting the formation of firm bonding on the surface of cotton
fabrics through intense electrostatic attraction between amino
acids from egg white protein and phosphoric acid from PA.
Importantly, three elements possess flame retardant features.
Moreover, as shown in Fig. 4, N and P elements are uniformly
distributed on the surface of treated cotton fabrics.
 X. Liu et al. / Journal of Cleaner Production 243 (2020) 118641 5

100
COT
COT-Pro
80 COT-PA
COT-Pro+PA

Weight loss (%)

COT-PA+Pro
60

40

20

0
100 200 300 400 500 600 700 800
o
Temperature ( C)
Fig. 4. EDS images of cotton fabrics treated by phytic acid and protein in sequence
(COT_ProþPA).
-25
COT
Table 1 COT-Pro

Weight loss rate (dw/dt)

-20
Surface element composition of cotton fabrics treated with egg white protein COT-PA
combined with phytic acid in sequence (COT_ProþPA). COT-Pro+PA
Element Wt % At % COT-PA+Pro
-15
C 42.30 50.53
O 44.87 40.23
N 5.90 6.04 -10
P 6.50 3.01
S 0.43 0.19
-5

3.5. Thermogravimetric analyses

Generally, the thermal stability of textiles materials was mainly
evaluated by thermogravimetric (TG) and derivative thermogravi-
metric (DTG) analysis technique. TG and DTG curves in air as well as
the corresponding data of control cotton fabrics (COT), samples
treated by phytic acid (COT_PA), egg white protein (COT_Pro), phytic
acid combined with egg white protein in sequence (COT_PAþPro),
and egg white protein combined with phytic acid in sequence
(COT_ProþPA) are shown in Fig. 5 and Table 2. Obviously, all samples
possess similar decomposition process, i.e., one main decomposi-
tion stage. Their decomposition temperatures range from 200  C to
600  C. For cotton fabrics coated with egg white protein (COT_Pro),
its initial decomposition temperature (260  C) is close to that of
control sample. In contrast, after 300  C, its decomposition rate is
slower than that of control sample, e.g., the residue at 500  C for
COT_Pro is 16%, whereas the residue at 500  C for COT is ca. 4%. The
results indicate that egg white protein operates effectively in
decreasing decomposition rate. For the sample coated with phytic
acid (COT_PA), it exhibits lower initial decomposition temperature
(169  C), and decomposed much slowly than COT and the COT_Pro
after 318  C. It is ascribed to the fact that phosphorus acid derived
from phytic acid during decomposition process would inhibit
depolymerization of cellulose units and thus promote dehydration
to form char (Cheema et al., 2013). Furthermore, for fabrics treated
with double coating of egg white protein and phytic acid in
sequence (COT_PAþPro), its initial decomposition temperature
(183  C) was little higher than that of COT_PA (169  C), while its
residue at 800  C increase to a higher level (7 wt%), increasing 112%
relative to control sample. It must be pointed out that as noted
previously, phytic acid is not suitable for directly coating and flame
retarding cellulosic fibers or fabrics because of strong acidic me-
dium and greatly lowered mechanical properties and handing
0
100 200 300 400 500 600 700 800
o
Temperature ( C)
Fig. 5. TG and DTG curves in air for control cotton fabrics (COT), sample treated by
phytic acid (COT_PA), egg white protein (COT_Pro), phytic acid combined with egg white
protein in sequence (COT_PAþPro), and egg white protein combined with phytic acid in
sequence (COT_ProþPA).
softness of modified samples. Alternatively, the egg white protein
was coated firstly and then phytic acid in sequence, the obtained
sample COT_ProþPA) decomposed initially at 211  C, and decom-
posed most slowly among the four samples after 316  C, producing
the highest residue at 600 and 800  C (32.9% and 12%, respectively),
increasing 723% and 264% relative to the results of control sample.
Therefore, the double coating of egg white protein and phytic acid
in sequence is the optimal flame retardant system for fabrics.
Alongi et al. investigated caseins and hydrophobins as green flame
retardants to treat cotton fabrics, and the residues of the treated
fabrics in air at 600  C were limited to 2% and 4 wt% (Alongi et al.,
2014a, 2014b). Contrarily, the residues increased up to 8%, 13%,
and 19% when 5%, 10%, and 15% DNA powder from herring sperm
was applied, respectively (Alongi et al., 2013). Bosco et al. obtained
the treated cotton fabrics with char residues of 1.5% and 2.5% by
respectively using folded and unfolded whey proteins (Bosco et al.,
2013). In this work, facile and inexpensive egg white protein
combined with phytic acid in sequence (COT_ProþPA) was success-
fully used to treat cotton fabrics. The residue results with 32.9% and
12% values respectively corresponded to 600 and 800  C is superior
or comparable to literature reports. Thus the intumescent flame
retardant system comprised of egg white protein and phytic acid
6 X. Liu et al. / Journal of Cleaner Production 243 (2020) 118641

Table 2
Thermogravimetric analysis data in air for control cotton fabrics (COT), sample treated by phytic acid (COT_PA), egg white protein (COT_Pro), phytic acid combined with egg
white protein in sequence (COT_PAþPro), and egg white protein combined with phytic acid in sequence (COT_ProþPA).

Sample T10% ( C) Tmax ( C) Residue at 600  C (wt%) Residue at 800  C (wt%) Ref.

COT 290 358 4 3.3 this work

COT_Pro 275 317 4 3.3 this work
COT_PA 208 242 18.5 3.3 this work
COT_PAþPro 245 289 16.8 7 this work
COT_ProþPA 207 249 32.9 12 this work
COT_5 wt% DNA powder from herring sperm 8 Alongi et al. (2013)
COT_10 wt% DNA powder from herring sperm 13 Alongi et al. (2013)
COT_15 wt% DNA powder from herring sperm 19 Alongi et al. (2013)
COT_Caseins 2 Alongi et al. (2013)
COT_Caseins 2 Alongi et al. (2014b)
COT_hydrophobins 4 Alongi et al. (2014b)
COT-Folded whey proteins 1.5 Bosco et al. (2013)
COT-unfolded whey proteins 2.5 Bosco et al. (2013)
COT_Caseins <1 Carosio et al. (2014)

displays remarkable synergistic effect on enhancing the amount of

residue chars of fabrics.
16

Total Heat Release( MJ/m2)

COT
3.6. Flame retardant performance COT-Pro
12 COT-PA
COT-PA+Pro
A new and quantitative analysis technique - cone calorimetry
COT-Pro+PA
was used to evaluate the flame retardant properties of control and
treated cotton fabrics. The obtained curves and detailed data are 8
presented in Figs. 6e7 and Table 3, including time to ignition (TTI),
peak of heat release rate (PHRR), and total heat release (THR), and
the residue after the combustion tests. In case of the PHRR values,
the samples COT and COT_Pro shows higher PHRR values (135.7 and 4
143.0 kW/m2), but the results of COT_PA (54.3 kW/m2), COT_PAþPro
(107.3 kW/m2)), and COT_ProþPA (105.0 kW/m2) decreases sharply.
The THR values of COT_PA (4.9 MJ/m2) and COT_ProþPA (5.6 MJ/m2) 0
are also the lowest among all samples. The TTI values of COT_PA 0 100 200 300 400
(81 s) and COT_ProþPA (80 s) enhance dramatically compared with Time(s)
that of the control cotton fabrics (18 s), showing 350% and 344%
increase. Likewise, the final residues of COT_PA (61.6%) and COT_- Fig. 7. Total heat release profiles of control cotton fabrics (COT), sample treated by
phytic acid (COT_PA), egg white protein (COT_Pro), phytic acid combined with egg white
ProþPA (52.2%) are much higher than that of COT (4.7%), respectively protein in sequence (COT_PAþPro), and egg white protein combined with phytic acid in
showing 1200% and 1011% increase. The improving effect for PHRR sequence (COT_ProþPA). Data in the graph corresponds to PHRR, THR, and TMAX,
and the final reside after the combustion of the coated cotton respectively.

160 fabrics by PA (COT_PA) or egg white protein combined with phytic

COT acid in sequence (COT_ProþPA) is comparable to or superior to the
Heat Release Rate( kW/m )

COT-Pro
2

results by other expensive proteins such as caseins and DNA. Alongi

COT-PA et al. ultilized 19 wt% DNA powder from herring sperm to treat
120 COT-PA+Pro
cotton fabrics. The treated fabrics shows a residue of 24% and
COT-Pro+PA
cannot be ignited (Alongi et al., 2013). The PHRR of treated cotton
fabrics decreased by 27% or 19% when caseins was used (Alongi
80 et al., 2014b; Carosio et al., 2014). Bosco et al. employed DNA
from herring sperm to treat cotton fabrics, showing a PHRR with a
decrease of 22% and a residue of 7% (Bosco et al., 2015). Therefore,
compared the literature reports, the results suggest that the cotton
40 treated by phytic acid or egg white protein combined with phytic
acid in sequence boosted flame retardancy properties obviously.
However, considering that phytic acid cannot directly treat the
cotton due to the strong acidity, the strategy by egg white protein
0
combined with phytic acid in sequence is a better alternative for
0 100 200 300 400
treating the cotton, which supports the formation of effective
Time(s) protective layer (Liu et al., 2018a) through electrostatic interaction
Fig. 6. Heat release rate profiles of control cotton fabrics (COT), sample treated by between phytic acid and egg white protein.
phytic acid (COT_PA), egg white protein (COT_Pro), phytic acid combined with egg white Fig. 8 illustrates vertical flammability tests of fabrics before
protein in sequence (COT_PAþPro), and egg white protein combined with phytic acid in (COT) and after being treated with egg white protein combined
sequence (COT_ProþPA). Data in the graph corresponds to PHRR, THR, and TMAX, with phytic acid in sequence (COT_ProþPA). Obviously, the results of
respectively.
 X. Liu et al. / Journal of Cleaner Production 243 (2020) 118641 7

Table 3
Combustion data obtained by cone calorimetry for control cotton fabrics (COT), sample treated by phytic acid (COT_PA), egg white protein (COT_Pro), phytic acid combined with
egg white protein in sequence (COT_PAþPro), and egg white protein combined with phytic acid in sequence (COT_ProþPA).

Sample TTI(s)(increase, %) PkHRR(kW/m2)(reduction, %) THR(MJ/m2)(reduction, %) Residue(%)(increase, %) Ref.

COT 18 135.7 16.9 4.7 this work

COT_Pro 19 (6) 143.0 (5) 16.4 (3) 3.9 (17) this work
COT_PA 81 (350) 54.3 (60) 4.9 (71) 61.6 (1200) this work
COT_PAþPro 15 (17) 107.3 (21) 12.2 (28) 14.9 (202) this work
COT_ProþPA 80 (344) 105.0 (23) 5.6 (67) 52.2 (1011) this work
COT_DNA_19% No ignition 24 Alongi et al. (2013)
COT_Caseins (-27) e Alongi et al. (2014b)
COT_Caseins (-19) 3 Carosio et al., 2014
COT_FHT DNA (-22) 7 Bosco et al. (2015)

excellent flame retardancy.

The surface morphology of char residues of cotton fabrics
treated with egg white protein combined with phytic acid in
sequence (COT_ProþPA) after combustion was measured by SEM
technique (Fig. 9). The control cotton fabrics burned into ash, and
didn’t produce residual char. Compared with control fabrics,
COT_ProþPA provide compact and continuous char layers. The
carbonaceous residues were generated by dehydration of cellulose
units catalyzed by phosphorus acid originated from flame retardant
phytic acid. Interestingly, numerous bubbles resulted from volatile
gases on the surface were visibly observed, forming special swollen
fibrous char structure. The carbonaceous layers is favorable for
serving as physical barrier and shielding combustible products
from oxygen and heat, efficiently protecting the matrix of treated
cotton fabrics during burning (Liu et al., 2018b; Wang et al., 2016).
Based on the above results, the formation of char network is
attributed to synergistic effect between nitrogen (egg white pro-
tein) and phosphorus (phytic acid).
Py-GC/MS technique was employed to measure the structures of
degraded products of control (COT) and treated fabrics by egg white
protein and PA in sequence (COT_ProþPA). The graphs and the py-
rolyzed volatile products were presented in Fig. 10. The main
thermal degradation products of cellulosic fibers or fabrics includes
alcohols, phenols, aldehydes, ketones, esters, ethers, aromatic rings
and other substances, most of which are flammable. Compared
with COT, COT_ProþPA clearly show lower peak strength and fewer
peaks. Moreover, the non-combustion pyrolysis products were
produced during pyrolysis, e.g., CO2, H2O, and NH3.
Based on the above results, the possible flame retardant
mechanism of fabrics coated with egg white protein and PA in
sequence during burning is proposed. On one hand, under the ac-
tion of heat source, PA first contacts with heat source to decompose
small molecular substances such as phosphoric acid. With the in-
crease of total heat quantity, proteins begin to decompose and
release large amounts of small less flammable molecules, such as
CO2, H2O, and NH3. At the same time, the generated phosphoric
acid also acts on the structural units of protein and cellulose units to

Fig. 8. Digital photographs of control (COT, top) and treated (COT_ProþPA, bottom)
cellulosic fabrics with a combination of egg white protein and phytic acid in sequence
after burning at different time.

two samples exposed to flame after 60 s show a great contrast. The

untreated fabrics burned fast, intensely, and completely, leaving a
very low amount of ash after ca. 20 s burning. Contrarily, the treated
fabrics did not burn obviously even exposed to flame after 60 s.
Thus, the results implies that the modified cellulosic fabrics possess
Fig. 9. SEM magnifications of the residues char of cotton fabrics treated by egg white
protein combined with phytic acid in sequence (COT_ProþPA) after flammability tests.
The scale bar in the right corner is 20 mm and 50 mm for the left and right micrographs,
respectively. The magnification is 2000 and 600 for the left and right micrographs,
respectively.
8 X. Liu et al. / Journal of Cleaner Production 243 (2020) 118641
6
5 possess excellent flame retardant performances, as evidence by
Abundance (×10 )
6
4
O
HO O O
3 O
O OH
2
OH
1
0
2 4 6 8 10
Retention time (min)
Fig. 10. Py-GC/MS curves of control (COT, top) and treated cotton fabrics by egg white
protein combined with phytic acid in sequence (COT_ProþPA, bottom).
promote their dehydration and charring, thus forming more and
larger bubbly carbon layers. The expanded char layer can be
effectively used as a physical barrier to avoid the contact of heat and
oxygen with matrix materials. Therefore, flame retardants play a
role in both gas and solid phases during combustion of treated
fabrics by egg white protein and PA in sequence.
4. Conclusions
The double coatings (i.e., layer-by-layer self-assembly) by varied
combinations of egg white protein and phytic acid (PA) were
explored to flame retard cotton fabrics. The treatment of protein
and PA in sequence (COT_ProþPA) was demonstrated to show an
optimal flame retardancy efficiency and remarkable synergistic
effect of phosphorus and nitrogen. This system reached a high level
of weight gain rate value of ca. 40%. The intense electrostatic
attraction was confirmed from the appearances of stretching vi-
brations of P]O and amide I and amide II, and corresponding el-
ements by FTIR and surface element composition analyses. SEM
analyses prove that the particular coating with protein in the inner
layer and PA in the outer layer didn’t destroy the surface structure
of fabrics, and more carbonaceous residues were preferably pro-
duced during burning. Furthermore, TG analyses in air show that
the char residues increases up to 32.9 wt% at 600  C and 12 wt% at
COT 800  C, which is obviously superior to the results of literature re-
ports with other proteins. Likewise, the modified cellulosic fabrics
lower values for peak of heat release rate and total heat release as
well as higher time to ignition and residues after burning than
OH
those of control fabrics evaluated by cone calorimeter analyses and
vertical flammability tests. Finally, Py-GC/MS analyses suggest that
nonflammable pyrolysis products including CO2, H2O, and NH3
were produced during the pyrolysis. The results are indicative of
flame retardant role in gas and solid phases during combustion of
treated fabrics.
Acknowledgments
12 The authors are very thankful for the financial support provided
by the National Key Research and Development Program of China
(No. 2017YFB0309000).
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