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A facile strategy to fabricate intumescent fire-retardant and smoke suppression

protective coatings for natural rubber

Lin Li, Xiaolin Liu, Kai Huang, Yuchao Wang, Xingfu Zheng, Jingchao Wang, Yuqian
Du, Licong Jiang, Shuai Zhao

PII: S0142-9418(20)30966-1
DOI: [Link]
Reference: POTE 106689

To appear in: Polymer Testing

Received Date: 17 April 2020

Revised Date: 4 June 2020
Accepted Date: 10 June 2020

Please cite this article as: L. Li, X. Liu, K. Huang, Y. Wang, X. Zheng, J. Wang, Y. Du, L. Jiang, S. Zhao,
A facile strategy to fabricate intumescent fire-retardant and smoke suppression protective coatings for
natural rubber, Polymer Testing (2020), doi: [Link]

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 A facile strategy to fabricate intumescent fire-retardant and smoke suppression

protective coatings for natural rubber

Lin Li, Xiaolin Liu, Kai Huang, Yuchao Wang, Xingfu Zheng, Jingchao Wang, Yuqian

Du, Licong Jiang, Shuai Zhao*

We develop an highly efficient polyurethane elastomer-based intumescent

fire-retardant and smoke suppression protective coating method. Specially, while

many physically mixed methods are usually seriously detrimental to mechanical

properties of rubber, the influence of coating method on mechanical properties

decreases obviously because fire retardant just directly impact on PU adhesive layer

rather than rubber matrix, moreover, the coating method requires less flame

retardant to achieve high flame retardant effect.

 A facile strategy to fabricate intumescent fire-retardant and smoke suppression

protective coatings for natural rubber

Lin Li, Xiaolin Liu, Kai Huang, Xingfu Zheng, Jingchao Wang, Yuchao Wang, Yuqian

Du, Licong Jiang, Shuai Zhao*

Key Lab of Rubber-plastics, Ministry of Education/Shandong Provincial Key Lab of

Rubber-plastics, School of Polymer Science and Engineering, Qingdao University of

Science and Technology, Qingdao 266042, China

∗Corresponding author E-mail address: lyzhsh@[Link] (S. Zhao).

Abstract

As flammable natural rubber (NR) become becomes more ubiquitous in industrial

field fields, there is a growing need for safe and effective flame retardant treatments

through efficient techniques. Remarkably, our developed highly efficient natural

tannic acid (TA)-based intumescent flame-retardant system (TGA) coated NR through

Polyurethane elastomer (PU) both as adhesive medium and a carbonforming agent

exhibits highly efficient flame retardant performances reflected by a 31.9% reduction

in peak heat release rate and a 27.3% in total heat release and a 26.2% reduction in

total smoke production at 50 wt% TGA loading in an 2 mm thick coating due to

synergistic flame retardant effect. Remarkably, our developed highly efficient natural

tannic acid (TA)-based intumescent flame-retardant system (AGT) has the unique

function in the rubber flame retardant aspect. Meanwhile, the developed coating

method through polyurethane elastomer (PU) both as adhesive medium and a

1
carbonforming agent can not only minimize the influence of flame retardant on the

desirable intrinsic properties of base polymer and also maximize the efficiency of

flame retardant. The flame-retardant coating (AGT/PU) exhibits highly efficient flame

retardant performances reflected by a 31.9% reduction in peak heat release rate and a

27.3% reduction in total heat release and a 26.2% reduction in total smoke production

at 50 wt% AGT loading with 50 wt% loading in 1 mm thick coating due to synergistic

flame retardant effect effects. More importantly, the excellent flame retardancy

performance are obtained by the PU@AGT10, as reflected in flame retardancy index

(FRI) value of 11.88 makes it as excellent flame retardancy performance. While many

physically mixed flame retardants are usually seriously detrimental to mechanical

properties of NR, the influence of TGA coating on mechanical properties decreases

obviously because fire retardant just directly impact on PU adhesive layer rather than

NR matrix, and the reinforcement function of graphene is much significant, moreover,

the coating method requires less flame retardant to achieve high flame retardant effect.

the influence of AGT/PU coating on mechanical properties of NR decreases obviously

because fire retardant just directly impacts on PU adhesive layer rather than NR

matrix, and the reinforcement function of graphene is also much significant. Moreover,

the coating method requires just less flame retardant to achieve high flame retardant

effect for NR. These findings suggest that significant opportunities for flame retardant

polymer materials in industry.

Keywords: intumescent fire-retardant coatings; nanocomposites; NR; PU; natural

tannic acid-based intumescent flame-retardant

2
INTRODUCTION

Surrounded by a variety of rubber materials in daily life, especially natural rubber

(NR) is characterized as both a “commodity polymer” and an “engineering elastomer”

and widely used as an economic industrial raw material in many fields especially as

[1-2]
industrial tires due to its unique combination of physicomechanical properties .

Therefore, the amount of used tires constantly increases worldwide, the recycling of

ground tire rubber have been comprehensively researched in many research works [3-4].

Further, human beings are facing nonnegligible fire security threats everyday

[5]
regarding the inherent ignitability of rubber materials . There, over recent years,

study of flame retardancy of rubbers results in their growing significance.

The most practical approach to enhance fire safety performance is the incorporation of

flame retardant (FR) additives in the polymeric matrix. With the strictness of safety

and environmental protection requirements, halogen-free FRs have attracted a great

deal of attention. However, the flame retardant efficiency of traditional halogen-free

FR consisting of organic components is unsatisfactory for NR because of its high

flammability, whose additive amount usually requires no less than 25 wt% to achieve

a good fire resistance. The high additive amount often leads to unsatisfactory

[4]
processability and deterioration of mechanical properties . More seriously, easy

migration of flame retardants usually results in a substantial discount in flame

retardancy of NR products due to their strong molecular polarity leading to poor

compatibility with nonpolar polyolefin. The intumescent flame retardants (IFRs) not

only have great superiority of halogen-free, low-smoke and low-toxicity, but also has

3
 [5]
higher flame retardance efficiency that become a popular research . In traditional

IFRs, polyammonium phosphate (APP) is superior to other flame retardants due to its

[6]
small load, no additional smoke, low cost and good processing performance .

However, in comparison with halogen-based retardant, the traditional APP-based IFR

suffers from the drawbacks of weak moisture resistance and low flame retardant

[7-10]
efficiency . Therefore, high efficiency IFRs and effective simple processing

technology have become the difficulties in the field of flame retardant rubber

materials.

Nowdays, layer-by-layer assembly has emerged as a promising technique for

depositing environmentally-benign flame retardants on a variety of polymeric

[11-13]
substrates . This technology has allowed nanometer-scale coatings act as a

defensive barrier to hinder heat propagation when the substrates are exposed to the

fire. However, interface between flame retardant and solid polymer is usually very

poor due to the difference in polarity between them. The interface plays an important

role in the mechanical and other related properties of substrates. Another of the

greatest hurdles facing LbL deposition is processing time and the number of the

deposition layers required to achieve a homogeneous and efficient flame retardant

nanocoating. This method requires complicated procedures with deposition of each

[14-16]
layer (sometimes up to 30 layers) and thus may be difficult to scale up .

Targeting thin coatings can not only minimize the influence of coatings on the

desirable intrinsic properties of base polymer and also maximize the efficiency of

flame retardant through a simple and fast coating method. Recently, even the

4
intumescent flame retardants (IFRs) have great superiority of halogen-free,

low-smoke and low-toxicity, large additive amount is also necessary for flame

[6-7]
retardancy of NR . The high additive amount often leads to unsatisfactory

[8]
processability and deterioration of mechanical properties . More seriously, easy

migration of flame retardants usually results in a substantial discount in flame

retardancy of NR products due to their strong molecular polarity leading to poor

compatibility with nonpolar polyolefin. Further, in comparison with halogen-based

retardant, IFR the traditional IFR suffers from the drawbacks of weak moisture

[9-12]
resistance and low flame retardant efficiency . Therefore, high efficiency IFRs

and effectively practical approach have become the difficulties in the field of flame

retardant rubber materials.

Nowdays, coating has emerged as a promising technique for depositing

environmentally-benign flame retardants on a variety of polymeric substrates.

Targeting thin coatings can not only minimize the influence of coatings on the

desirable intrinsic properties of base polymer and also maximize the efficiency of

flame retardant through a simple and fast coating method. Recently, layer-by-layer

[13-15]
assembly (LbL) is a widely used flame retardant technology . This technology

has allowed nanometer-scale coatings act as a defensive barrier to hinder heat

propagation when the substrates are exposed to the fire. However, the greatest hurdles

facing LbL deposition are processing time and the number of the deposition layers

required to achieve a homogeneous and efficient flame retardant nanocoating. This

method requires complicated procedures with deposition of each layer (sometimes up

5
to 30 layers) and thus may be difficult to scale up [16-18]. Nevertheless, Flame retardant

coating constructed with polymer and flame retardants only meet the requirements of

flame retardant efficiently, but also hardly interfere with the processing technology of

rubber products [19]. In case of fire, the coating on polymer substrate can form a thick

carbon protective layer and play a role in delaying the heat into the internal matrix,

[20-25]
buying more time to put out fires and evacuate people . Thus, a simple one-step

coating method are considered attractive if they could provide effective flame

retardancy without concerns of easy migration/absorption into humans while also

[26]
retaining the intrinsic mechanical properties of NR. In our previous work , an

efficient natural tannic acid (TA)-based intumescent flame-retardant system (TGA)

(AGT) has been designed by applying TA functionalized graphene combined with

APP. Inspired by such a strategy, a surface coating of polyurethane elastomer (PU)

and AGT was constructed on the surface of NR via simple surface coating process via

a simple surface coating process. PU as the binder between AGT and NR

simultaneously exhibits a role of carbonization agents for AGT in case of fire [27], and

has little effect on performance of NR matrix during use because of its rubbery

properties. and also endows NR with some excellent properties, such as abrasive

resistance and tear resistance. The combustion performance for NR surface coated

with AGT/PU is evaluated, the morphology of combusted residues and the flame

retardant mechanism are also characterized and analyzed.

2. EXPERIMENTAL DETAILS

2.1 Materials

6
Ammonium polyphosphate (type is TF-201, the degree of polymerization is 1500)

was generously supplied by Shandong Taifeng New Flame Retardant Co., Ltd, China.

Graphene (GE) was supplied by the sixth element (Changzhou) material technology

Co. Ltd. (China). Tannic acid (TA) was purchased from Aladdin Technology Co., LTD

(China). Polyether polyol prepolymer (NCO content: 3%) and 3,3 '-dichloro-4,

4-diamino-diphenylmethane(MOCA) were supplied by Shangdong INOV new

material company Co., LTD (China). NR (SCR20) was provided by Hainan rubber

Co., Ltd. (China). Other reagents, including sulfur,

N-cyclohexyl-2-benzothiazolesulfenamide (CZ), dibenzyldithiocarbamic acid, zinc

salt (ZBEC), N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), zinc

oxide, and N98 (98% SiO2, average diameter: 200 nm) were all industrial grade and

kindly supplied by Qingdao Topsen Chemical co. LTD (China).

2.2 Characterization

Raman spectra were recorded using a high-resolution FRS-100S (Bruker) machine

with a CCD detector. The spectral purity is quoted to be < 700 at wavelength > 2,100

cm-1 from a set wavelength. The morphologies of the residual carbon layer were

observed using JSM-6700F SEM (Japan Electronics Corp.). The SEM samples were

coated with gold for 60 s. TGA measurement was carried out using a TGA-7 type

thermo-analysis instrument (Perkine Elmer Company, USA) from room temperature

to 800 °C at a heating rate of 10 °C /min under air atmosphere. Limited Oxygen Index

(LOI) was measured using a HC-2 oxygen index meter (Jiangning Analysis

Instrument Company, China) according to the standard oxygen index test ASTM

7
D2863. The specimen dimension were 130*6.5*3.2 mm3. UL-94 Vertical Burning

Test was performed using a vertical burning instrument (CFZ-1 type, Jiangning

Analysis Instrument Co., China) according to UL-94 test ASTM D3801-2010. The

dimensions of samples were 130*13*3.2 mm3. The Cone Calorimeter Test (CCT)

was performed on the cone calorimeter (Fire Testing Technology, U.K.) according to

ASTM E1354/ISO 5660. The dimensions of samples were 100*100*3.2 mm3. Each

specimen was wrapped in an aluminum foil and exposed horizontally to 35 kW/m2

external heat flux. The thermal conductivity was measured by a laser flash system

(LFA 447 NanoFlash). Tensile and tear testing were carried out using an AI-7000S

Universal Material Tester, with a dumbbell specimen at a tensile speed of 500 mm

min-1 according to ISO 528:2009. The abrasion test was carried out with the DIN

abrader according to ISO-4649. The abrasion was designed as a volumetric loss of a

strip sample. Flex fatigue property was stretched on a De Mattia Rubber Flexometer

(MZ-4003C, Mingzhu, China).The optimum curing time of NR and its composites

was determined at 150 °C by an ALPHA MDR2000 UCAN rheometer.

2.3 Preparation of TGE

Variable graphene was added into a vial containing 30 ml TA aqueous solution which

the concentration of TA is variable according to the batch compositions. The mixture

was then sonicated for 30 min in a 30-35°C water bath using a bath sonicator

(Elmasonic E30H, 40 W, 37 kHz) to prepare TGE [28].

2.4 Preparation of the NR batches

Mixing was performed in a 200 ml Banbury mixer at a rotor speed of 60 rpm for the

8
 mixing stage at a temperature of 120°C. The NR was fed into the mixer and premixed

for 2 min. This was followed by the sequential addition of zinc oxide (5 phr), SA (1

phr), HD-Silica (60 phr) and Si69 (10.6 phr) and mixing mixed the compounding

ingredients for another 5 min. Next, CZ (2 phr) and ZBEC (0.2) were added followed

by the addition of N98 into the rubber for 2.5 min followed by 6PPD (2 phr), mixed

for 1 min and then the mixture was discharged onto a two roll mill at 80 °C, where the

sulfur (1 phr) was added. Immediately after each mixing, the composition was

removed from the roll, and while still in a hot condition, passed once through a cold

two-roll mill to achieve a sheet of about 2 mm thickness. The batch compositions are

shown in Table 1. The process is shown in Scheme 1 and the batch compositions are

shown in Table 1.

Table 1 NR batch compositions

Samples NR HD-Silica Si69 N98 ZnO SA S CZ 6PPD ZBEC

Amount(g) 100 60 10.6 5 5 1 1 2 2 0.2

2.5 The preparation of AGT/PU flame retardant

A given mass of polyether polyol prepolymer and a given mass of APP were mixed

with A a given mass of TGE under stirring. Then, a certain amount of MOCA (the

mass ratio of polyether polyol prepolymer to MOCA is 10:1) was added to the

mixture with stirring. A stable and compatible inorganic-organic compound flame

retardant (AGT/PU) was prepared followed by these steps. The formulation is

summarized in Table 2.

2.6 Preparation of PU@AGT

9
The process to produce PU@AGT is illustrated in Scheme 1, and the formulation is

summarized in Table 2. NR was surface coated with AGT/PU flame retardant until a

homogeneous physical blocking layer was formed after coating 2 times. Finally, the

PU@AGT composites with a thin physical barrier layer were post cured at 120 °C for

2 h.

Scheme 1 The preparation process for PU@AGT foam plates.

Table 2 Formulations of PU@APP and PU@AGT composites

Samples PU (g) APP (g) TA (g) GE (g)

PU@NR 10 -- -- --

PU@APP6 10 6.0 -- --
PU@AGT6 10 4.4 0.55 1.05

PU@APP8 10 8.0 -- --

PU@AGT8 10 5.8 0.73 1.47

PU@APP10 10 10 -- --

PU@AGT10 10 7.2 0.91 1.89

3．
． RESULTS AND DISCUSSION

10
3.1 Thermal behavior of PU@APP and PU@AGT composites

Fig.1 TGA (a) and DTA thermograms (b) of PU@APP and PU@AGT in N2

atmosphere.

TGA and DTA curves represented in Fig. 1 were used to investigate the

thermos-oxidative degradation behaviour of PU@APP and PU@AGT, the resulted

data are summarized in Table 3. The controlled sample (PU@NR) exhibits sharp and

rapid pyrolysis under N2 atmosphere. The PU@NR remains only 28.5 wt% char

residues when heated to when is heated to 700 °C under N2 atmosphere. After NR

coated with APP/PU (PU@APP), the initial decomposition temperature (T5%) of

PU@APP composites remains nearly constant, however, the thermal degradation

process is moderated to some extent which is ascribed to the flame retardant of APP.

Compared with PU@APP composites, the initial decomposition temperature (T5%) of

PU@AGT composites shifts to a higher temperature owing to barrier effects of

graphene. Besides, the final char residue of PU@AGT generated after the pyrolysis

process is much higher.

11
 Table 3 The LOI values and UL-94 rating are experimentally and theoretically

investigated to figure out the thermal combustion properties of PU@APP and

PU@AGT.

T5% Tmax (°C) Residue at

Samples
(°C) T1max (°C) T2max (°C) T3max (°C) 700 °C (%)

PU@NR 306.15 387.5 393.3 637.4 28.43

PU@APP6 310.73 387.9 394.7 654.2 30.78
PU@AGT6 290.14 363.1 388.3 -- 35.71
PU@APP8 305.04 388.2 395.4 615.7 33.15
PU@AGT8 305.71 358.4 387.9 -- 38.47
PU@APP10 313.07 389.1 402.6 639.3 34.87
PU@AGT10 341.29 391.4 -- -- 40.65

3.2 Combustion behavior of PU@APP and PU@AGT composites

Table 4 LOI and UL-94 tests experimental data for various samples.

LOI
Samples UL-94 Dripping
(%)
PU@NR 19 NC Yes
PU@APP6 26 V-2 Yes
PU@AGT6 27 V-2 Yes
PU@APP8 29 V-1 No
PU@AGT8 30 V-0 No
PU@APP10 31 V-0 No
PU@AGT10 32 V-0 No

The PU@NR burns fiercely after ignited and accompanies with dripping. As shown in

Table 4, the PU@NR can not pass UL-94 test. Remarkably, in comparison with V-1

rating of the PU@APP8, the PU@AGT8 exhibite exhibit highly higher effcient flame

retardant performance performances reflected by V-0 rating with a LOI value of 30%

12
due to synergistic flame retardant synergistic flame retardant effects of AGT. in

comparison with V-1 rating of PU@APP8.

Fig. 2 The digital photos of char residues for PU@APP and PU@AGT

composites after CCT test.

Photographs of char residues of PU@APP and PU@AGT composites from the

cone-calorimetry test are shown in Fig. 2. Compared with PU@APP composites

which the formed char residue layer was discontinuous and bumpy, PU@AGT

composites formed a continuous, denser, smooth and intumescent residual char layer

which look looks like a “hill”. In addition, the char yield has been significantly

increased duo to the synergistic AGT/PU architecture the synergistic flame retardant

13
architecture of AGT/PU, and the formed high strength char residue layer can

effectively improve its fracture strength. and the formed char residue layer is

substantially reinforced by graphene and can efficiently protect the inner matrix

because of its improved fracture strength. For TGA/PU system, superimposed effect

mainly attributed to dual function from each component and intumescent flame

retardant mechanism. For intumescent flame retardant AGT/PU, superimposed effect

mainly attributed to dual function from each component (PU with adhesive and

carbonizing agent functions, APP both acting as acid source and gas source, TA both

acting as acid source and carbonization agent, and graphene with carbonization agent

and carbon layer reinforcing agent functions).

14
 Fig. 3 CCT results of PU@APP and PU@AGT composites under an external heat

flux of 35 kWm−2: (a) HRR, (b) THR, (c) TSP, (d) MASS, (e) CO production rate and

(f) CO2 production rate.

In order to further investigate the flame retardancy of PU@APP and PU@AGT

composites, more scientific cone calorimeter test is also employed to evaluate the

combustion performance, parameters such as time to ignition (TTI), peak heat release

rate (PHRR), total heat release (THR), total smoke production (TSP) and mass residue

after combustion as shown in Fig. 3, and the corresponding data are displayed in

15
Table 5. Peak value of HRR (PHRR), and total heat release (THR) values have been

proved to be the critical parameters in characterizing fire safety of polymers.

Compared with PU@APP, PU@AGT composites brings bring about a satisfactory

improvement of fire retardancy. As shown in Fig. 3(a) and Fig. 3(b), PU@AGT

composites show a steep descent in HRR and THR compared with PU@APP

composites at the same ratio of flame retardant with loading the same content of flame

retardant. Especially for the PU@AGT10 give gives rather low peaks of HRR and

THR (171.9 kWm-2 and 83.5 MJm-2) under heat flux of 35 kWm-2 compared to the

PU@APP10 with value of (252.4 kWm-2 and 114.8 MJm-2), and with a reduction of

31.9% and 27.3% respectively. The gap in PHRR between APP and AGT systems is

also pretty obvious. The PU@AGT10 with 171.9 kWm-2 has a reduction of 20.1%

compared to that of the PU@APP10 (215.1kWm-2) which the PU@AGT10 with 171.9

kWm-2 has a reduction of 20.1% compared to that of the PU@APP10 (215.1kWm-2).

This means that thermal factors necessary for a material materials to continue burning

are significantly reduced, thus significantly increasing the flame resistance of the

protected objects. During a fire, It it is of significant importance to reduce smoke

release during combustion since the smoke toxicity of organic materials causes the

vast majority of fire deaths and injuries. The dynamic smoke production behaviors of

PU@APP and PU@AGT composites are characterized by total smoke production

(TSP), as shown in Fig. 3(c), and the datas data are summarized in Table 5. As shown

in Fig. 3c, TSP of PU@AGT composites remarkably decrease compared with those of

PU@APP at equivalent loading of fire retardant at an equivalent loading of fire

16
retardants. Which TSP of the PU@AGT10 is reduced from 22.1 m-2 of the

PU@APP10 to 16.3 m-2 with a decrement of 26.2%. The reduction in smoke indicates

that TGA AGT flame retardant system can act as the smoke suppression agent, and

increase the chances of survival. the increase in residue mass is also larger and

simultaneously TA and graphene in TGA effectively work to accelerate the strong

char formation acting as a protective layer for matrix. It is mainly because that TA and

graphene in AGT effectively work to accelerate the formation of strong char acting as

a protective layer for matrix, further graphene in AGT also acts as a physical barrier to

limit generated soot transfer. Usually, the surface of formed char layer can be further

oxidized and CO2 and CO, and CO2 and CO is are generated and released out, as a

result, the carbon content in residues immensely decreased. Compared with PU@APP

composites, the reduction in the release of CO and CO2 (Fig. 3e and f) for PU@TGA

composites directly prove the higher stable due to the special structure of the

expanded char layer plusing the barrier effect of graphene. Compared with PU@APP

composites, the reduction in the release of CO and CO2 (Fig. 3e and f) for PU@AGT

composites directly proves that the formed residue layer is higher stable. The

measured average effective heat comb. (EHC) (Table 5) can further provide a better

understanding of the reduced flammability resulting from char formation a better

understanding about the reduced flammability resulting from char formation. The

synergistic improvements of thermal stability and flame retardancy are proven by the

thermal combustion properties of PU@AGT composites.

In order to understand the fire hazard of several studied materials more clearly, the

17
 [29] [30]
fire performance index (FPI) and the fire growth index (FIGRA) are selected.

FPI is defined as the proportion of TTI and PHRR. It has been reported that there is a

certain correlation between the FPI value of material materials and the time to

flashover. When the value of FPI reduces, the time to flashover will be advanced.

Therefore, it can be accepted that when the FPI value of a material materials is

smaller, the fire risk is higher. FIGRA is defined as the proportion of PHRR and the

time to peak HRR. According to the previous report, the larger the FIGRA value is,

the shorter time it takes to arrive at a high peak HRR, and the more fire hazard the

materials have. The comparison between the The values of FPI and FIGRA of these

composites has been are shown in Table 5. Compared with those of PU@APP

composites, the FPI and FIGRA of PU@AGT composites, at an equivalent loading,

are respectively much higher and much lower which indicates more effective at

reducing flammability of NR. The FPI value of the PU@AGT10 is highest (29.66

10-2m2s/ kW), meanwhile, the FIGRA value of that is the lowest (0.5692 kW/(m2/s))

among samples, with an increase of 35.7% in FPI and a reduction of 42.3% in FIGRA

compared to with that of the PU@APP10. These mean that fire risk of the

PU@AGT10 is the smallest. Further, flame retardancy index (FRI), is defined as a

simple yet universal dimensionless criterion born out of cone calorimetry data on

thermoplastic composites and then put into practice for quantifying the flame

retardancy performance of different polymer composites on a set of reliable data [31-33].

The FRI is defined as Equation 1 [31].

18
Based on FRI values shown in Table 5, the excellent flame retardancy performance is

obtained by the PU@AGT10, as reflected in FRI value of 11.88, other samples can be

observed that FRI values up to 101 (1<FRI<10) makes samples as good flame

retardancy performance. This is due to the high efficiency and synergistic flame

retardant behavior of TGA/PU system which can realize the condensed phase and gas

phase dual flame retardation. This is because that the AGT/PU system can realize the

condensed phase and gas phase dual flame retardation due to the high efficiency and

synergistic flame retardant behavior. Among them, TGE plays an important role in

flame retarding for NR because TA can efficiently reduce oxidants and radicals to

[34]
maximize the unburned solid and charred remain, aiding mankind survival , and

graphene has the function functions of gas barrier and char layer reinforcement [35].

Table 5 Cone calorimetry experimental datas for various samples.

19
3.3 The microstructure of char residues for PU@APP and PU@AGT composites

The morphology of char residues and their chemical compositions were studied with

SEM equipped with energy dispersive X-ray (EDX) and the results are presented in

Fig. 4 and Fig. 5. PU@APP composites, especially in the case of low addition

additions of APP shows large cracks (Fig.3a-1), multi-porous and asperous char

morphology with large char particles show up fully with increasing the loading of

APP (see Fig. 4b-2 and c-2), which is attributed to the premature and rapid

degradation derived from PU@APP composites proven by TGA ( Fig.1a) and the low

strength of the resulting char layer which is unable to withstand the impact of volatile

products. and multi-porous and asperous char morphology with large char particles

with increasing the loading of APP (see Fig. 4b-2 and c-2). It is attributed to the

premature and rapid degradation derived from PU@APP composites proven by TGA

( Fig.1a), and the low strength char layer which is unable to withstand the impact of

volatile products. However, PU@AGT composites have relatively continuous,

intumescent, compact and strong char structure with thin char particles, even

flocculent char particles for the PU@AGT10 ( Fig. 5c-3). This is due to This is

ascribed to the high efficiency and synergistic flame retardant behavior of AGT/PU.

20
In the event of a fire, during the earlier degradation, thermally stable graphene sheets

act as a mass barrier to restrain the permeation of flammable gases [36-37]. Meanwhile,

the catalytic charring effect of metaphosphoric acid (HPO4) decomposed from APP

and the absorbed TA structure TA absorbed on the surface of graphene results in the

generation of much phosphor carbonaceous char residue in carbon source (graphene

and PU), meanwhile, ammonia gas released from APP can promote the expansion of

char layer and effectively dilute volatile products during the combustion process. It is

their friendly cooperation that makes them highly flame retardant. In this sense, to

confirm the conjecture, the structural composition of char residues was investigated

by SEM-EDX analysis. In Fig. 4 and Fig. 5, compared with the elemental mappings

of PU@APP, those of PU@AGT composites reveal the better uniform distribution of

C, N, O and P atoms on the char surface. The increase of C atom and the decrease of

O atom (Table 6) for PU@AGT composites further verify the high carbon production

capacity of AGT.

21
Fig. 4 SEM-EDX spectrum of (a) PU@APP6, (b) PU@APP8 and (c) PU@APP10.

22
 Fig. 5 SEM-EDX spectrum of (a) PU@AGT6, (b) PU@AGT8 and (c) PU@AGT10

Table 6 EDX results of surface char residue from different composites.

Weight(%)

Element PU@AAP6 PU@APP8 PU@APP10 PU@AGT6 PU@AGT8 PU@AGT10

C 22.66 28.26 39.56 24.42 31.96 49.11

N 3.30 2.48 4.65 3.26 4.18 4.28
O 65.03 58.04 48.16 60.95 58.82 40.43
P 9.01 11.22 7.63 11.37 5.04 6.18

23
 Fig. 6 Raman peak fitting curves of char residues of composites.

Raman spectra have been importantly used to characterize the structure of

carbonaceous materials. The results of Raman spectroscopy (Fig. 6) can also further

confirm the previously speculated flame retardant mechanism. As shown in Fig. 6,

two characteristic bands are mainly observed, D and G band appearing at

24
approximately 1340 and 1588 cm-1, respectively [38]
. The D band appeared by the

disorder of the sp2 structure of GE sheets. The G band appeared by the in-plane

tangential stretches of C-C bonds in the sp2 structure of GE sheets [40]

. Typically, the

integrated intensities of D to G bands (ID/IG) embody is used to estimate the

graphitization degree of the residual char, and a lower ID/IG value suggests better char

[39]
structures . Notably, the ID/IG ratio always follows the sequence of PU@AGT <

PU@APP with the same loading, demonstrating that AGT system can facilitate the

formation of highly graphitized and thermally insulated char layers, then the formed

char layer is inflated by ammonia gas released from APP, which is primarily

responsible for the suppressed flammability. Moreover, the high-aspect-ratio graphene

can hold the intumescent char particles together to generate a high-strength

adiathermic char shield on the inner materials and act as micro-char to make a great

contribution to graphitized char.

3.4 Physicomechanical behaviors of PU@APP and PU@AGT composites

25
 Fig.7 (a) abrasion loss, (b) tear strength and (c) tensile strength of PU@APP and

PU@AGT composites.

In various applications, the mechanical properties of NR should be considered with

great emphasis. Unfortunately, their additional features such as their fire retardant

action are usually associated with some ineluctably negative effects, such as

contamination of mechanical properties. In this regard, poor particle dispersion and

interface interaction are presumably responsible for the negative effects due to

polarity differences between polar fire retardant and nonpolar NR. In our work,

although adding AGT would also has a negative effect on the mechanical properties

of NR, it the negative effect could be weakened because fire retardant just directly

impact on PU adhesive layer rather than NR matrix. In addition, the reinforcement of

26
graphene is possitive for the mechanical properties of NR. Therefore, in comparison

with PU@APP composites, PU@AGT composites demonstrate a noticeable increase

in wear resistance, tensile strength and tear strength (Fig. 7) with the same addition of

flame retardant. When the quality ratio of PU and flame retardant is 10:6, 10:8 and

10:10 respectively, wear resistence resistance of PU@AGT respective respectively

has an increase of 22.7%, 24.2% and 23.9%, the tensile strength of PU@AGT

composites is respectively 11.4%, 6.6% and 5.5% higher than that of PU@APP

composites, and the tear strength is respectively 11.3%, 6.3% and 3.4% higher than

that of PU@APP composites. The significant improvement benefits from the

reinforcement function of graphene which has strong physical interfacial adhesion

with matrix NR through interfacial regulator regulation of TA [41-44].

The interaction between TA and GE was confirmed by UV-vis and Raman

spectroscopy. As shown in UV-vis spectra (Fig. 8a), TA exhibits two absorption peaks

at 212 and 276 nm, which are separately ascribed to the π-π* transitions of aromatic

C=C bonds (aromatic E bond) and n-π* transitions of C=O bonds (R bond) in TA 26.

When TA absorbs on GE, both absorption peaks blueshift blue shift to 210 and 270

nm, respectively. When GE is modified with TA, Raman spectra (Fig. 8c and d) also

show both main absorption peaks blueshift blue shift from 1345 and 1587 cm−1 for

of GE to 1342 and 1585 cm−1 for of TGE, respectively. This proves the strong π-π

interaction between TA and GE which indicating no performance contamination for

TA and GE. The deprotonation of TA at alkaline condition will be is convenient for

removing TA from TGE to get the pristine GE. Furthermore, the noncovalent π-π

27
interaction between TA and GE is confirmed by Raman spectroscopy of TGE before

and after deprotonization deprotonation of TA. The Raman intensity ratio of D-band

(∼1340 cm−1) to G-band (∼1580 cm−1), denoted ID/IG which has been widely used to

[38]
evaluate the defect content of graphene . As shown in Fig. 8 (c-e), each spectrum

was subjected to peak fitting using the curve fitting software Originpro 2017/Peak

Fitting Module to resolve the curve into 2 Gian bands. The Raman spectra in Fig.

8(c-e) show ID/IG just slightly increases from 1.74 for GE to 1.79 for TGE without

washing with NaOH, and to 1.66 for TGE washing with NaOH, indicating no obvious

defects are introduced to the GE. The Raman spectra in Fig. 8(c-e) show ID/IG just

slightly increases from 1.74 of GE without modified with TA to 1.79 of TGE without

washing with NaOH, and to 1.66 of TGE with washing with NaOH, indicating no

obvious defects are introduced to GE after modified with TA. Raman spectra for TGE

with washing with NaOH almost overlaps with GE, the positions of its characteristic

absorption peaks are almost exactly corresponding to those of GE. In a word, through

the above experimental facts, the π-π interaction between TA and GE is verified.

Physical interactions between them are beneficial for their flame retardant functions

in AGT/PU system.

28
Fig.8 (a) UV-vis and Raman spectra of TA (b), GE (c), TGE without washing (d) and

TGE washing with NaOH (e).

Conclusions

The simple coating method is developed to provide effective flame retardancy while

also retaining the intrinsic mechanical properties of NR. There PU@AGT composites

show a steep descent in all combustion parameters compared with PU@APP

composites at the same ratio of flame retardant at an equivalent loading of fire

retardants. Especially for the PU@AGT10 give gives rather low peaks of HRR and

THR (171.9 kWm-2 and 83.5 MJm-2) under a heat flux of 35 kWm-2 compared to with

29
the PU@APP10 (252.4 kWm-2 and 114.8 MJm-2) with a reduction of 31.9% and

27.3% respectively. TSP of the PU@AGT10 is reduced from 22.1 m-2 of the

PU@APP10 to 16.3 m-2 with a decrement of 26.2%. The FPI value of the

PU@AGT10 is highest (29.66 10-2m2s/ kW) and the FIGRA value of that is the

lowest (0.5692 kW/(m2/s)), with an increase of 35.7% and a reduction of 42.3%

compared to that those of the PU@APP10 respectively. The universal dimensionless

FRI nicely reflects the excellent flame retardancy performance for AGT system,

significantly the FRI of the PU@AGT10 is up to 11.88.

Acknowledgements

The authors gratefully acknowledge support from National Natural Science

Foundation of China [grant numbers 51703111 and 51603111] and Shandong

Provincial Natural Science Foundation, China [grant numbers 2018GGX102015 and

ZR2017BEM011] and China Postdoctoral Science Foundation [grant number

2018M642626 ].

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 Table 5 Cone calorimetry experimental data for various samples.

TTI PHRR THR TSP MASS FPI FIGRA EHC

Samples FRI
(s) (kW/m2) (MJ/m2) (m2) (g) (10-2m2s/kW) (kW/(m2/s)) (MJ/kg)
PU@APP6 38 366.7 116.3 26.37 56 10.36 1.1367 65.35 3.28

PU@AGT6 44 316.3 110.7 19.46 57.3 13.91 1.1058 54.51 4.63

PU@APP8 42 258.9 96 25.91 60.4 16.22 1.0622 47.21 6.23

PU@AGT8 43 222 93 17.46 62.9 19.36 1.0236 45.46 7.67

PU@APP10 47 215.1 93.6 23.73 70 21.85 0.9868 33.63 8.60

PU@AGT10 51 171.9 92 16.28 71.9 29.66 0.5692 30.98 11.88

 Highlights

1. An highly efficient polyurethane elastomer-based intumescent fire-retardant and

smoke suppression protective coating method is studied.

2. Remarkably, the developed highly efficient natural tannic acid (TA)-based

intumescent flame-retardant system (TGA) coated NR through Polyurethane

elastomer (PU) both as adhesive medium and a carbonforming agent exhibits

highly efficient flame retardant performances

3. Specially, the influence of coating method on mechanical properties decreases

obviously because fire retardant just directly impact on PU adhesive layer rather

than rubber matrix.

 Author Statement

We confirm that the manuscript has been revised carefully according to

the comments of editors and reviewers and approved by all named

authors. We declare that we have no conflict of interest.

Sincerely,

Shuai Zhao
 Authors Declaration

We confirm that the manuscript has been read and approved by all named

authors. We declare that we have no conflict of interest.

Sincerely,

Shuai Zhao