Heliyon 8 (2022) e12175

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Heliyon
journal homepage: www.cell.com/heliyon

Research article

Properties of flame-retardant leaf fiber cement-based composites at

high temperatures
Demin Jiang a, *, Haodong Xu a, Shuchen Lv a, Di Jiang c, Suping Cui b, Shiguo Sun a,
Xiaoruan Song a, Shiqin He a, Jingzong Zhang a
a
College of Civil Engineering, North China University of Technology, Beijing 100144, PR China
b
College of Materials Science & Engineering, Beijing University of Technology, Beijing 100124, PR China
c
College of Architecture and Art, North China University of Technology, Beijing 100144, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Flame retardant modification of leaf fibers was carried out to solve the technical problem of poor fire resistance of
Leaf fiber plant fibers and improve the utilization rate of urban fallen leaves in building materials. The modification scheme
Flame retardant modification adopts three flame retardants, i.e., ammonium polyphosphate (APP), magnesium hydroxide (MH), and aluminum
Cement-based composites
hydroxide (ATH), and two covering layers, i.e., pure acrylic polymer lotion and water glass (Na2O ⋅ nSiO2) so-
High temperatures
lution. The modified leaf fiber's combustion behavior and pyrolysis properties were tested and analyzed. The
Properties
physical and mechanical characteristics, as well as the thermal insulation qualities, of leaf fiber cement-based
composites (LFCC) were studied at high temperatures. The findings revealed that the three flame retardants
had an effect on the chemical structure of leaf fibers. In comparison to leaf fibers without flame-retardant
modification, flame-retardant-modified leaf fibers have a much greater thermal stability. and its LOI is greater
than 27.0%, which is a fire-retardant material. Except for the sample with water glass as the modified cover layer,
at high temperatures, the composite flame-retardant fiber LFCC's mass-loss rate is lower compared with fibers
without flame-retardant modification or fibers modified with only one kind of flame-retardant. In the composite
flame-retardant modified fiber LFCC, the samples with better strength at high temperature are those with ATH
replacing 30% and 50% MH. The thermal conductivity of LFCC is negatively correlated with the range of tem-
perature change.

1. Introduction According to statistics, the number of fallen leaves in the cities in-
creases yearly in autumn. The weight of fallen leaves from Beijing and its
Currently, the research on improving the flame retardancy of fiber surrounding areas alone is more than 100 tons per day. Such a spectac-
composites through the modification of plant fibers worldwide mainly ular scene lasts about a month, while the number of leaves falling at the
focuses on papermaking materials, fiber resin matrix composites, wood peak is about 3,000 tons per day in downtown Beijing [4]. The primary
plastic composites, and so on. Faseha Shukor et al. [1] studied the effect research and applications of leaves have focused on producing fertilizer,
of ammonium polyphosphate on flame retardancy, thermal stability, and feed, and medicine in China. However, few research and applications
mechanical properties in alkali-treated kenaf fiber/polylactic acid (PLA) have used leaves as a building material. Most cities and regions do not
biological composites. K. Ramanaiah et al. [2] studied the mechanical have adequate conditions to turn leaves into fertilizers, so most fallen
properties, thermophysical properties, and flammability of sargassum leaves are transported to garbage dumps to be burnt or buried. The
fiber/polyester composites. Nannan Li et al. [3] studied the flame burning debris will produce many floating dust and carcinogenic sub-
retardant and reinforcement modification of ramie/polyethylene com- stances, such as tribenzopyrene and tetrabenzopyrene, increasing par-
posites through surface treatment of ramie fabrics. However, in most ticulates in the air [5], and severe air pollution, severely impacting
literature, the flame-retardant modification of plant fibers is limited to people's health. Nearly 30%–40% of the fallen leaves cannot be recycled,
wood flour fiber, flax fiber, sisal fiber, etc. No reports on the flame causing environmental pollution. Therefore, it is a new subject for sci-
retardancy of leaf fiber cement-based composites. entific research workers to turn their attention to fallen leaves in the

* Corresponding author.
E-mail address: [email protected] (D. Jiang).

https://doi.org/10.1016/j.heliyon.2022.e12175
Received 4 January 2022; Received in revised form 7 May 2022; Accepted 29 November 2022
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D. Jiang et al. Heliyon 8 (2022) e12175

cities and find ways of turning them into treasures to reduce urban smog to increase the comparability. The screened leaf fibers were
weather and beautify the urban environment. combined according to the mass ratio of 0.3 mm: 0.6 mm: 1.18
Plant fiber cement-based composites are a kind of green environment- mm ¼ 1:1:1. Figure 1 depicts the appearance and morphology of
friendly building material made of cement as the cementation material poplar leaves and fibers, while Table 2 depicts the chemical
and plant fibers as reinforcing material through a series of technological components of leaf fibers. Table 3 displays the bulk density and
processes and cement hydration and hardening [6, 7]. apparent density of leaf fibers with varying particle sizes.
If the fallen leaf fibers are applied to cement-based composite mate- (4) Polycarboxylic acid superplasticizer (PC): Purchased from Beijing
rials, and the composite materials are widely used in construction, it Muhu Admixture Co. Ltd., China, PH ¼ 8.5–9.5, solid content
would be a powerful way to solve recycling fallen leaf fibers [8, 9]. In 97%, density 498.0 kg/m3, water reduction rate >35%, and
thermal insulation building materials, we can fully use the light, porous dosage 0.6%–1.3%.
and thermal insulation characteristics of fallen leaf fibers to make ther- (5) Calcium chloride (CaCl2): Produced by Beijing Chemical Plant,
mal insulation materials alone or combined with other materials [10]. China, density 2150 kg/m3 and melting Point 782  C.
As a natural high molecular polymer, plant fibers will degrade ther- (6) Triethanolamine (N(CH2CH2OH)3): Produced by Beijing Chemi-
mally at a certain temperature. Thermal degradation first destroys fibers' cal Plant, China, boiling point 360.0  C, and melting point 21.2  C.
structure and then affects the strength and other properties of the com- (7) Water: Drinking water complied with China's national standards,
posite material. Additionally, plant fibers prone to igniting fiercely in pH ¼ 6.91 at 25  C.
flame because its combustible properties, creating a large amount of (8) Pure acrylic polymer emulsion: PRIMAL MAC-261P acrylic poly-
smoke and hazardous fumes [11] and cause inflicting injuries and mer emulsion by Rohm and Haas, USA, density 1.04 g/ml, total
financial damage. Plant fibers' poor fire resistance performance is one of solid content 50.0%.
the most significant shortcomings limiting their application in con- (9) Water glass solution (Na2O⋅nSiO2): Produced by Beijing Yongfei
struction. To reduce the hazards and losses of fire and prevent cata- Adhesive Factory, China, modulus 3.1, Baum
e scale 40 , density
strophic fires, countries worldwide are generally concerned about 1.38 g/ml, total solid content 36.20%.
developing and producing flame retardants and flame-retardant plant (10) Flame retardant: Procured from Taixing Fine Chemical Co., Ltd.,
fibers. Plant fiber composite wall materials' flame retardancy has Jinan, Shandong Province, China. ①Ammonium polyphosphate
attracted more attention [12]. In plant fiber cement-based composite (APP): The model is HT-208, P2O5 content 57.0%, and N content
materials, plant fibers are encased in cement substrate, this situation will 12.0%, easily soluble in water, pH value 4.5–6.5. ②Magnesium
adjourn or greatly reduces the fibers' flammability. There is still more hydroxide (MH): The model is HT-206, Mg(OH)2 content 91.5%,
research that needs to be done on the mechanical and physical properties molecular weight 58.3 and density 2.36 g/cm3, loss of ignition
of plant fiber cement-based composite materials at high temps. 28%, pH value 9–11. ③Aluminum hydroxide (ATH): The model
To boost the usage rate of fiber plants in buildings, the technical issue is HT-205, Al2O3 content 64.0%, molecular weight 78, and
of their low flame-proof performance must be addressed. Modifying fiber density 2.42 g/cm3, loss of ignition 34.0%–35.0%, and pH
plants and treating flame retardants are critical to resolving this issue 8.5–10.5.
[13].
In this paper, the raw material was the fallen leaves in the cities with 2.2. Methods
enormous output in China. The research object, fibers made from poplar
leaves, and we modify the fibers using a variety of flame retardants. The (1) Determination of the maximum solubility of flame retardants
combustion behavior and pyrolysis performance of leaf fiber and leaf
fiber cement-based composites (LFCC) were tested and analyzed. It was Three flame retardants, APP, MH, and ATH, were used to test the
investigated how modified leaf fiber affected the properties of LFCC at three flame retardants' maximum solubility at different water tempera-
high temps. The changes to the modified leaf fiber's chemical compo- tures (the suspension that can be sprayed is enough) to facilitate the
nents, chemical structure, and thermal stability as well as the micro- spray modification of leaf fibers. The results are shown in Table 4.
morphology of the LFCC hydration products at high temps were analyzed
from the micro point of view. Then, the modified leaf fiber's influence (2) Modification methods of leaf fibers
mechanism on the characteristics of LFCC at high temps was investigated.
The fibers were pretreated with physical processes. First, the leaf
2. Materials and methods surfaces were sprayed with a flame-retardant solution. When dried, we
apply another flame-retardant solution, spraying it over the surface.
2.1. Materials Finally, in order to cover the fiber surfaces in a thin layer, acrylic polymer
emulsion or sodium silicate solution was sprayed onto them. During the
(1) Cement: 42.5R “Diamond” Brand ordinary Portland cement pro- concrete mixing and molding procedure, flame retardants wrapped on
duced by Yanjiao New Building Materials Co., Ltd., Sanhe City, the fiber can easily be lost into the cement, affecting the fibers' flame-
Hebei Province, China. The chemical composition of cement and retardant effect. The covering layer could prevent that by encasing and
mineral admixtures is shown in Table 1. shielding the flame retardant. The modification method of leaf fiber is
(2) Fly ash: II fly ash from Beijing Shijingshan Power Plant, China. shown in Figure 2. The specific way is to smoothly spray the flame-
The chemical composition of the fly ash is shown in Table 1. retardant solution from the sprayer nozzle in a foggy form and achieve
(3) Leaf fibers: The leaves are poplar leaves (from now on referred to a uniform coating. The flame retardant to water dilution ratio was 1:1
as leaves) collected from Beijing's downtown areas in November. (mass ratio). Before dilution, the following is the ratio of flame retardant
The collected leaves were dried, crushed, screened, and processed to the mass of plant fibers: APP, MH, and ATH APP accounted for 60% of
into fibers (granules). The fiber size range was set to 0.3–1.18mm fiber mass, and before dilution, sodium silicate solution and acrylic

Table 1. Chemical composition of cement and mineral admixtures (wt.%).

Type of materials CaO SiO2 Al2O3 Fe2O3 TiO2 MgO SO3 Na2O Ignition loss
Cement 62. 38 25. 52 6. 15 3. 27 0. 57 1. 54 1. 65 0. 21 2. 87
Fly ash 1. 93 54. 88 32. 12 4. 28 — 1. 45 1. 46 — 3. 82

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D. Jiang et al. Heliyon 8 (2022) e12175

Figure 1. Appearance of poplar leaves and their fibers: (a) Poplar leaves; (b) Poplar leaves fibers.

Table 2. Chemical composition of leaf fibers (wt.%).

Item Moisture content Ash content Holo-cellulose Cellulose Pentosan Lignin Pectin Extracts of different solutions

Hot water Cold water Alcohol benzene 1% NaOH

Leaf fibers 5.15 13.15 50.78 25.48 10.44 23.00 — 33.51 28.31 21.44 38.54

Note: It is determined following China's national standard GB/T 2677 the Testing Methods of Relevant Components of Paper-making Materials. Holocellulose is the sum
of cellulose and hemicellulose in raw materials of plant fibers, also known as full-cellulose.

Table 5 displays the LFCC mix proportion. In order to properly mix,

Table 3. Bulk density and apparent density of leaf fibers with different particle the mixture's consistency should be regulated at 303mm, and the ad-
sizes (kg/m3). justments to water consumption should be made accordingly [14].
Particle size (mm) 4.75 2.36 1.18 0.6 0.3 0.15 & below
(4) Fabrication of LFCC mechanical property specimens
Bulk density 97.2 176.1 234.4 280.3 282.1 302.2
Apparent density 224.6 306.7 336.8 357.1 295.4 297.5
Related work was carried out according to GB/T17671-1999 [15].
Note: The sieving of leaf fibers with different particle sizes and the bulk density The size of samples was 40 mm  40 mm  160mm, and standard curing
tests were carried out in accordance with China's national standard GB/T14684- was 28d. From each group, we selected three specimens, dried,
2001 (Building sand). numbered, and weighed them; their mean strength was used to deter-
mine the test result for this group.

(5) Test of LFCC insulation performance

Table 4. Maximum solubility of flame retardants (g/100g water).

Type 20  0.5 ( C) 40  0.5 ( C) 60  0.5 ( C) Relevant tests are carried out as described in GB/T10294-2008 [16].
APP 40 50 60 SSX-DR300 intelligent Double Plate Thermal Conductivity Tester (by
MH 30 40 50 Shaoxing City, China) was used to measure thermal conductivity. The
ATH 30 40 50 hot-plate temperature was set to 50  C and the cold-plate temperature at
30  C. The mix proportion of the specimens was the same as that of the
mechanical property test specimens. The size of the samples was 300 mm
polymer emulsion accounted for 42% of the fiber mass. The sprayed fi-  300 mm  30mm. At a temperature of 85  C, we dried the samples for
bers were placed into an electric blast and dried at 85  1  C for 24–30 h. 24–30h before the test after 28 days of conventional curing. Two plate
They were cooled at room temperature and put in sealed plastic bags for specimens from each group were tested for their thermal conductivity.
future use when reaching the dried state. LCFF's eventual assessment of their thermal insulation performance
depended on the mean of the test results of two specimens.
(3) Mixing ratio of LFCC
(6) Performance test of LFCC at high temperatures

We conduct LFCC high-temperature heating experiments using a box-

type resistance furnace. The specimens in the furnace are shown in
Figure 3. Set the heating rate to 10  C/min, and set the test temperature
to 25  C, 150  C, 250  C, 350  C, 500  C, and 650  C. The furnace will

Table 5. Mix ratio of LFCC (kg/m3).

Cement Fly Leaf Total water PC CaCl2 N(CH2CH2OH)3

ash fibers consumption
668.25 74.25 111.28 360 5.94 14.85 0.74
Figure 2. Sketch map of modification method of leaf fibers.

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4000-400 cm-1, scanning times 32 times, and resolution 4cm1. The

sample was made by mixing KBr and test materials into a semi-
transparent ingot tablet. Way to prepare samples: 3.5mg test materials
and a homogeneous transparent ingot tablet was obtained by pouring
300 mg of the 350 mg of KBr that had been added to the agate mortar,
mingled, and ground into a pressing die pressed for 1–2 min, under
pressure of around 10 MPa.

(10) Analysis of micro-morphology of leaf fibers and their LFCC

The micro-morphology of leaf fibers and their LFCC were examined

using a Carl Zeiss NTS, Germany, SIGMA Thermal Field Emission Scan-
ning Electron Microscope (SEM). In addition, the chemical composition
of the leaf fiber microzones was examined using an X-MAX-20 X-ray
Figure 3. LFCC specimens in furnace. Energy Dispersive Spectrometer (EDS) by Oxford, the UK, linked to a
scanning electron microscope. We set the test voltage to 2 kV when we
continue to heat until it reaches the previously set temperature; it will observe the leaf fiber. First, we dry the samples at 75  1  C and then
keep heating at the constant temperature for an hour; and then the sparge gold onto them for 30 s before testing. When watching LFCC, the
furnace door will be opened to allow the specimens to cool. The samples test voltage was 10Kv. The same 28-day-old specimens used in the me-
were cooled to room temperature for other performance tests. chanical properties test were dried at 85  1  C, broken into 2mm-square
pieces, and then sprayed with gold for half a minute.
(7) Thermal stability analysis of leaf fibers and flame retardants
(11) Modification scheme of leaf fibers
Hitachi STA7300 Thermogravimetric Analyzer analyzed the thermal
stability of the samples. Weigh 5–10 mg of the samples and put them into Table 6 displays the modification scheme for the leaf fibers. Corre-
the crucible. With the protection of nitrogen, we set the heating rate to 10 sponding to the serial numbers of each project in Table 6, in the

C/min, and the heating range was set to 30 C–1000  C The weight loss/ following, the specimen marks of the leaf fiber performance test are
weight loss rate (TG/DTG) curve was chosen as the test mode. Y0~Y7, and the specimen marks of the LFCC performance test are YC-
1~YC-7.
(8) Analysis of the flammability of leaf fibers
3. Results and discussion
The Limiting Oxygen Index (LOI) is used to evaluate materials' com-
bustion properties [17]. The flammability of modified leaf fibers was 3.1. Chemical structure of flame retardants and leaf fibers
evaluated using the JF-3 oxygen index tester. The determination method
was carried out regarding GB/T2406.2–2009 [18] and GB/T 5454–1997 The chemical structure and functional groups of flame retardants and
[19]. Sample preparation: The leaf fibers were inserted into a Φ10 mm  leaf fibers can alter, and this can be detected using Fourier Infrared
120 mm paper tube, and the sample's fibers were made homogeneous Spectroscopy (FTIR). The FTIR spectra of flame retardants and leaf fibers
and solid by compacting it with a thin wooden rod. For each modification are shown in Figures 5 and 6, respectively.
scheme, five samples were chosen, and the average LOI of the five pieces As shown in Figure 5, APP has an antisymmetric stretching vibration
was used as the outcome. Figure 4 shows the LOI test specimens and peak of NH4þ at 3431 cm-1, N–H stretching vibration peak of ammo-
instruments. nium polyphosphate at 3242 cm-1, and N–H bending vibration peak at
1668 cm-1, P¼O stretching vibration peak at 1290 cm-1. 1115cm-1 is the
(9) Chemical structure analysis of flame retardant and leaf fibers asymmetric stretching peak of the P–O bond, and 916cm-1 is the sym-
metric stretching peak of the P–O bond of ammonium polyphosphate
A Tensor 27 Fourier Transform Infrared Spectrometer (FTIR) by [20, 21]. The stretching vibration peak of Mg–OH is denoted as MH. at
Bruker, Germany, was used to analyze the chemical structure of the flame 3705 cm-1 and O–H and Mg–OH bending vibration peaks at 1634 cm-1
retardants and the leaf fibers. The scanning wavenumber range was set to and 1437 cm-1, respectively [22, 23, 24]. Adsorbed water and the –OH

Figure 4. LOI test specimens and instruments: (a) specimens; (b) instruments.

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D. Jiang et al. Heliyon 8 (2022) e12175

results show that the sodium silicate coating was successful in acting on
Table 6. Modification scheme of leaf fibers. the exterior of leaf fibers [30, 31].
No. Scheme As shown in Figure 6, the flame-retardant modifiers and the exterior
0 No treatment coating have an impact on chemical groups of leaf fibers. Thus, the
1 Non-flame retardant →Pure acrylic
change in chemical structure is bound to influence leaf fibers' thermal
2 APP→ Pure acrylic
stability, flammability, and physical and mechanical properties.
3 APP þ MH→ Pure acrylic
3.2. Thermal stability of flame retardants and leaf fibers
4 APP þ MH þ ATH→ Pure acrylic
5 APP þ MH0.7 þ ATH (replacing 30%MH)→Pure acrylic
3.2.1. Thermal stability of flame retardants
6 APP þ MH0.5 þ ATH (replacing 50%MH)→Pure acrylic
The TG/DTG analysis results of APP, MH, and ATH [32, 33, 34, 35]
7 APP þ MH0.5 þ ATH (replacing 50%HM)→Water glass
are shown in Figure 7. As shown in Figure 7(a), the thermal decompo-
sition of APP can be roughly divided into three stages. The volatilization
group's stretching vibration may be superimposed at the absorption of a minor quantity of adsorbed water was mostly responsible for the first
peaks at 3622 cm-1 and 3549 cm-1 in ATH, The CO2 deformation vi- stage, which ranged from 30  C to 182.6  C. The second stage, from 182.6

bration has an absorption peak at 2361 cm1. The absorption peak at C to 542.9  C, primarily generated ammonia and water vapor, and the
1628 cm-1 is the deformation vibration of adsorbed water. At 1396 cm-1, product was polyphosphoric acid. In the third stage, from 542.9  C to
the absorption peak corresponds to the OH group's in-plane bending vi- 1000  C, the weight loss was mostly brought on by the generation of
bration, at 1020 cm-1, 968 cm-1, and 914 c cm-1, and at 667 cm-1, the phosphorus oxides produced by the continued oxidation of poly-
absorption peak corresponds to the stretching vibration of the Al–O phosphoric acid (To create P–O molecules, polyphosphate consumed
group [25]. H2O).
In Figure 6(a), comparing Y1 with Y0, the pure acrylic emulsion film As shown in Figure 7(b), the thermal decomposition of MH can be
acts on the surface of the leaf fibers through a blue shift at 3447 cm1, the roughly divided into two stages: the first stage was 30–428.1  C, mostly
appearance of the absorption peak at 2957 cm1, and the enhancement brought on by the absorbed water's release and the majority of the bru-
of the peak value at 1743 cm1, and the like. APP in Y2 increases the cite's. Brucite was transformed into periclase. The second stage was
absorption peak of hydroxyl stretching vibration by NHþ 4 at 3443 cm
1 428.1–701.5  C, mainly caused by escaping residual crystal water from
and increases the absorption peak value of hydroxyl stretching vibration brucite and the transformation into magnesium oxide.
by 1269 and 1269 in Y2. Moreover, the P¼O stretching vibration peak of The thermal degradation of MH could be generally separated into two
ammonium polyphosphate at 3699 cm1 acts on the surface of leaf fibers; phases, as illustrated in Figure 7(b). The first stage was from 30  C to
MH in Y3 is successfully adsorbed on leaf fibers' surface with the 274.9  C, mainly the adsorption of water volatilization and partial
appearance of free OH stretching vibration characteristic band at 3699 dropout of OH from the gibbsite. The second stage was from 274.9  C to
cm1 to modify them [26, 27, 28, 29]. 314.6  C, Al (OH)3 was severely dehydrated at this stage, and most of the
In Figure 6(b), it can be seen that ATH in Y4 acts on the surface of leaf OH was dropped out from the gibbsite and converted into diaspore
fibers through the superposition effect of the characteristic bands of AlO(OH). The third stage was from 314.6  C to 558.3  C, mainly the
stretching vibration of free –OH in ATH at 3524 cm-1 and the stretching dropout of gibbsite OH, transforming into Al2O3.
vibration at 667 cm-1 of Al–O in ATH. In comparison to Y3, in Y5 and y6,
the stretching vibration peak of the free –OH group of MH at 3699 cm-1 3.2.2. Thermal stability of leaf fibers
gets blurrier as the rate at which ATH replaces MH increases, and the Figure 8 displays the results of the TG/DTG analysis of leaf fibers [36,
corresponding deformation vibration peak of –OH at 1024 cm-1 and 37, 38, 39], and Figure 9 displays the residual weight rate of Y0–Y7 after
Al–O corresponding stretching vibration peak at 667 cm-1 becomes more pyrolysis at 1000 degree centigrade.
evident, indicating that the substitution of MH by ATH affects the Figure 8(a), the pyrolysis process of Y0 leaf fibers can be broadly
chemical structure. When Y7 was compared to Y6, the C¼O bond separated into three phases three stages: the first stage was from 30.0  C
stretching vibration absorption peak of ethyl acrylate (EA) molecules at to about 131.91  C. Free water evaporation and the combined water's
1743 cm-1 vanished, and characteristic Si–O–Si stretching vibration dehydration reaction in the leaf fiber caused this stage, which belongs to
peaks in sodium silicate appeared at 1090 cm-1 and 469 cm-1. These the stage of dehydration and drying. The second stage, from 131.91  C to
471.14  C, was the pyrolyzation stage of holocellulose. The spot at
268.75  C should be where maximum pyrolyzation of hemicelluloses
occurs. Because of the irregular amorphous structure of hemicelluloses,
they have low thermal stability. At 331.45  C, The maximum weight loss
rate peak appeared, which, being cellulose pyrolysis, released much heat.
D-glucose linked to a glycoside bond forms a macromolecular structure
known as cellulose. It has no branches and is challenging to decompose;
the weight loss rate at this stage was 54.63%. In the third stage, from
471.14  C to 1000  C, there are two prominent weight loss rate peaks at
484.34  C and 656.51  C, respectively. Because lignin's primary con-
stituent, a polysaccharide made of phenylpropane joined by an ether and
carbon bond, has a high degree of stability and is challenging to break
down. This stage should be the pyrolysis of lignin.
Comparing Figure 8(b) with Figure 8(a), the DTG curve shows a sharp
peak in the weight loss rate of Y1 at 386.44  C, that was because in pure
acrylic polymer emulsions, the macromolecular polymer could decom-
pose at such a temperature [40].
Comparing Figure 8(c) with Figure 8(b), the DTG curve had two more
weight loss rate peaks at 202.30  C and 899.47  C, which were caused by
the thermal decomposition of APP on the surface of leaf fibers. APP
Figure 5. FTIR spectra of three flame retardants. produced ammonia and water vapor at 202.30  C, the product being

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Figure 6. FTIR spectra of leaf fibers: (a) Y0~Y3; (b) Y4~Y7.

Figure 7. TG/DTG analysis of three flame retardants: (a) APP; (b) MH; (c) ATH.

polyphosphoric acid. The polyphosphoric acid underwent additional maximum rate of weight loss rate at this drying stage is significantly
oxidation at 899.47  C to produce phosphorus oxide. The TG curves show higher than that of Y2 and is 54.65  C later than Y2. At 286.57  C and
that, because of APP's flame retardancy, the total weight loss of Y2 de- 331.84  C, the maximum weight loss rate peaks of hemicellulose and
creases in the temperature range from 30  C to 1000  C, demonstrating a cellulose were observed. The temperature of the two peaks was later
significant improvement in Y2's thermal stability. compared to Y2 due to the synergistic effect of MH. The maximum rate of
Comparing Figure 8(d) with Figure 8(c), the peak maximum weight weight loss peak appeared at 395.29  C, resulting from the breakdown of
loss rate in Figure 8(d) appeared at 111.65  C, which was caused by free macromolecular polymer in pure acrylic polymer emulsion. Under
water volatilization and combined hydrolysis adsorption dehydration of the co-action of APP and MH, the temperature was delayed by 4.10  C
leaf fiber and flame retardants. Due to MH flame retardant addition, the than Y2.

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Figure 8. TG/DTG analysis results of leaf fibers: (a)~(h) correspond to samples Y0~Y7 respectively; (i) TG curves of samples Y0~Y7.

Comparing Figure 8(e) with Figure 8(d), it can be seen on the DTG thermal stability of Y2 at medium and low temperatures is satisfactory,
curve that most peaks appeared at 236.87  C, which was caused by however the weight loss rate decreased distinctly when the temperature
partial loss of OH out of ATH. was above 800  C. The mass-loss rate of Y3 and Y4 modified with com-
Comparing Fig. (f) with Figure 8(e), it is clear that, because of the posite flame retardant is less after 800  C, and the residual weight rates of
decreased ATH content, in Figure 8(f), there is no weight loss rate peak the two at 1000  C are 43.91% and 42.27%, respectively, and the thermal
on the DTG curve. stability of the two is excellent. The thermal stability of Y6 is better than
Under the combined action of MH and ATH, APP produced a portion that of Y5. After 315  C, the thermal stability of Y5 and Y6 is worse than
of water vapor and ammonia, as shown by the DTG curve in Figure 8(g) at that of Y3 and Y4. Y7 exhibited the largest residual weight rate, the less
182.67  C, and the end product was polyphosphoric acid. At238.16  C, mass loss rate, and the best thermal stability when the temperature
the partial loss of OH out of ATH was the reason. exceeded 400  C. The presence of the water-glass layer increases the
Comparing Figure 8(h) with Figure 8(g), because Y7 used sodium retention rate of flame retardants in the fibers, and the thermal stability
silicate as its fiber coating, it has no peak of the macromolecular poly- as well as their flame retardancy are also improved. The sodium silicate
mer's decomposition weight loss rate in the pure acrylic polymer emul- inorganic has good high-temperature stability before 1200  C [42].
sion. Y7 leaf fibers' pyrolysis could be generally separated into three
stages: the first stage is from 30  C to 165.42  C, and the weightless rate
peaks appeared at 65.44  C and 100.46  C, due to free water evaporation
and bound water desorption of leaf fiber, and the application of flame
retardants. belonging to the drying stage. The second stage is from
165.42  C to 352.15  C, and the weight loss rate peak at 243.67  C, which
was caused by partial OH removal from ATH. At 278.47  C and 293.30

C, the peaks are of hemicelluloses and celluloses' maximum weight loss
rate peaks. The third stage is from 352.15  C to 996.37  C, the peak of the
weight loss rate at 397.65  C, which was caused by the partial water loss
of MH. The decomposition caused by high temperatures of some lignin
and complex polymer compounds led to the weight loss rate peaks at
431.52  C and 628.06  C.
Generally, the higher the high-temperature residual weight rate of the
material, the better its thermal stability [41]. Fibers that have not had
flame retardant treated Y0 & Y1 are demonstrated in Figures 8 and 9 to
be relatively constant at the low-temperature stage. nonetheless, the
mass loss decreased significantly after 300  C. Because Y1 is covered in a
pure acrylic emulsion organic coating layer, its fibers have increased
flammability, making its fiber thermal stability worse than Y0. The Figure 9. Pyrolysis residual weight rate of leaf fibers.

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D. Jiang et al. Heliyon 8 (2022) e12175

In short, the ones with satisfactory thermal stability are Y7, Y3, Y4, of fibers by filling holes and fissures on their surface. The existence of
Y2, Y6, and Y5, and the ones with poor thermal stability are Y1 and Y0. polymer film improved the water resistance and alkali corrosion resis-
tance of fibers, reduced the effect of the extracts in fibers on the anti-
coagulation of cement hydration, and improved the interface effect
3.3. Flammability of leaf fibers
between the fiber surfaces and the cement-base materials, thus increasing
the bond between them. However, because the Y2 fibers were modified
If a material is non-flammable, that means its LOI is high. In contrast,
with APP flame retardant, they had to undergo spraying and dry pro-
If a material is combustible, that means its LOI is low [43]. The material
cesses that Y1 did not need, making them suffer more serious surface
with less than 22.0% LOI is generally considered flammable, the material
damage than Y1 fibers and reducing the coating uniformity of polymer
with LOI between 22.0% and 27.0% is flammable, and the material with
film. Similarly, in Y3–Y7, adopting inorganic flame retardants MH and
an LOI greater than 27.0% is considered nonflammable [44, 45]. The LOI
ATH required additional processes, making different sizes of fiber chips
results of leaf fibers are shown in Figure 10.
and flame-retardant agglomerated particles bonded on the surface,
As shown in Figure 10, the LOI of Y0 is 23.0%, meaning a flammable
resulting in increased fiber surface defects and the deterioration of
material. The LOI of Y1 coated with pure acrylic emulsion is 2.0% lower
coating uniformity. As a result, the flame retardant is somewhat lost, and
than Y0, indicating that leaf fibers' flammability is increased by pure
the binding strength among leaf fibers and cement mortar is affected.
acrylic emulsion organic compound. When Y2–Y7 was treated with a
Comparing Y7 with Y6, the particles bonded on Y7 surfaces appeared
flame retardant, the LOI was greater compared to when it wasn't. Because
loose and brittle. In contrast, the particles bonded on Y6 surfaces are
of App, In Y2–Y6, the LOI of Y2 was higher,a flame retardant with good
increasingly hardened and flexible. That is because of the different
properties, is water soluble. Spray modification APP has good retention
characteristics of two organic and inorganic coatings made of pure
in fibers due to its ease of penetration and equal distribution. However,
acrylic emulsion and sodium silicate solution.
the composite flame-retardant modified fibers, resulting from a process
Elements C, O, and Si are mostly present on the exterior of untreated
of stirring and drying, suffered inevitable damage and uneven distribu-
leaf fibers Y0, as illustrated in Figure 12 (The energy spectrum cannot be
tion of inorganic flame-retardant agents on the fiber surfaces, and the
used to detect the single electron that exists outside of the nucleus of
flame-retardant effect was affected. The LOI of Y5 and Y6 dropped by
hydrogen). So, the majority of the leaf fibers are made of organic mate-
2.2% and 2.5%, respectively, as compared to Y3, showing that the flame
rials like C, H, and O, with a trace quantity of ash like SiO2 on the exterior
retardancy of leaf fibers was not enhanced when 30% and 50% of MH
cuticle. On the surface of Y1, there are mainly C and O elements, but no
fibers were substituted by ATH. Compared to Y6, LOI for Y7 is 11.5%
apparent Si elements were found caused by the effect of pure acrylic
greater. The sodium silicate coating has a flawless flame-retardant impact
emulsion coating. The fact that P is present in Y2 shows that the APP
on the leaf fibers due to its good thermal stability and adhesion, which
flame retardant has well attached to the exterior of fibers. Since MH
helps sustain flame retardant retention on the fibers' surface.
flame retardant was effectively deposited on the exterior of fibers, Y3
contains more Mg elements than Y2. Y4 has more Al than Y3, indicating
3.4. Micro-morphology and chemical composition of leaf fibers that the ATH flame retardant has successfully adsorbed on the surface of
fibers. Three flame retardants, P, Mg, and Al, were found in Y5–Y7. Using
Figure 11 depicts the EDS test region and the micro-morphology of sodium silicate as a coating layer, Y7 mainly contains Na2O⋅nSiO2. As a
leaf fibers, and Figure 12 displays the test findings for the chemical result, Si and Na elements were discovered in the fibers, and the peak
composition of the test area. Interpretation of spectrum test processing: strength of the Si element was higher than that in Y0.
The K-line system has been used to normalize all of the evaluated items.
As shown in Figure 11, there are raised pores and granular debris on
the surface of Y0, which, being prone to peel-off, will make fibers more 3.5. Performance of LFCC at high temperatures
permeable to water, which will alter how well fibers adhere to cement-
based surfaces. There is also a smooth wax layer and cuticle layer on 3.5.1. The mass-loss rate of LFCC at high temperatures
the surface of Y0, which is disadvantageous to the wetting, diffusion, and Figure 13 displays the mass-loss rate of LFCC at high temperatures. As
permeation of cement slurry and various additive solutions on the surface shown in Figure 13, YC-7 has the highest mass loss rate of LFCC at high
of fibers affecting the bonding between fibers and cement-based mate- temperatures, of which mass-loss rates are 18.89% at 650  C, followed by
rials [2]. The pure acrylic emulsion film on the surface of Y1 fiber YC-1 and YC-2, of which mass-loss rates are 16.09% and 13.68%,
covered the detritus. It reduced surface flaws and improved the integrity respectively, at 650  C. YC-4 has the lowest mass-loss rate, followed by
YC-3, of which mass-loss rates are 10.26% and 10.93%, respectively, at
650  C. The mass-loss rate is correlated with water volatilization in
concrete, fiber plants', and flame retardants' heat release of water, gas,
etc. The thermal stability of composite flame-retardant treated fibers
LFCC (except YC-7) is higher than that of fibers treated with no flame
retardant and sole component flame-retardant treated fibers LFCC.
Hence, their LFCC mass-loss rate is relatively low. Since the YC-7's
inorganic coating of sodium silicate is brittle and hard, it will inevitably
crack in the LFCC mixing process (see Figure 17). The LFCC will expe-
rience high heat mass loss as a result of loss of flame retardants or the
uneven distribution, which causes poor flame retardancy of fibers.

3.5.2. Strength of LFCC at high temperatures

3.5.2.1. Compression strength of LFCC at high temperatures. The

compressive strength and loss rate of LFCC at high temperatures are
shown in Figure 14.
As shown in Figure 14(a), the compression strength of LFCC
decreased with the increase in temperature, especially from 500  C to
Figure 10. LOI of leaf fibers. 650  C. LFCC suffered significant strength attenuation. At 650  C, YC-7

8
D. Jiang et al. Heliyon 8 (2022) e12175

Figure 11. Micro-morphology and test area of leaf fibers (1000 times): Y0~Y7 correspond to the serial numbers in Table 6.

had the highest compression strength (5.13 MPa), followed by YC-6 (3.60 pyrolysis, and the incomplete pyrolysis of plant fibers could provide
MPa) and YC-5 (3.10 MPa). At 650  C, YC-1 had the lowest compression certain tensile strength for cement matrix. There are the main reasons for
strength (0.33 MPa), followed by YC-2 (0.62 MP A). The strength of YC-2 the decrease in LFCC compression strength at high temperatures: Firstly,
to YC-5 samples increased during the heating process, which is related to the temperature stress will cause the occurrence and expansion of micro-
the rate of hydrate formation being more significant than that of hydrate cracks in the cement matrix. Secondly, the dehydration and

9
D. Jiang et al. Heliyon 8 (2022) e12175

Figure 12. Chemical composition of leaf fibers in EDS test area.

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D. Jiang et al. Heliyon 8 (2022) e12175

and YC-6 have high flexural strength, 0.90MPa, and 0.79MPa, respec-
tively, while YC-3 has low flexural strength, 0.20MPa. The same factor
that causes LFCC's flexural strength to drop at high temperatures also
accounts for its compression strength.
It can be seen from Figure 15(b) that, on the whole, the flexural
strength loss rate of LFCC increases with the increase in temperature. The
flexural strength loss rate of LFCC increases slowly in the range of
25 C–150  C and even increases in YC-3. This is because the damage
made by temperature to the sample's structure is less than the repair
degree made by hydrate growth to the structure [47]. At 650  C, YC-6 has
a small flexural strength loss rate, 74.74%, followed by YC-2 and YC-8,
75.22% and 75.54%, respectively. YC-1 has the largest flexural
strength loss rate, 88.73%, followed by YC-3 and YC-9, of which loss rates
are 85.80% and 85.78%, respectively.
In short, based on the examination of mass loss rate and mechanical
properties presented above, the LFCC with better fiber modification ef-
fect is YC-5 and YC-6, followed by YC-4, YC-3, and YC-7, and the LFCC
with poor fiber modification effect is YC-1 and YC-2. It shows an optimal
match issue between LFCC's mechanical and physical properties at high
Figure 13. Mass-loss rate of LFCC at high temperatures. temps and procedures used to modify leaf fibers for flame retardancy.
The thermal stability of leaf fibers and the bonding strength between
decomposition of hydration products, e.g., hydrated calcium sulphoalu- flame-retardant fibers and cement-base materials are both factors that
minate (Aft), will thermally decompose at 200  C, Ca(OH)2 begins to affect LFCC strength at high temperatures. Among the fiber modifiers YC-
dehydrate at 400  C, while C–S–H gel and CaCO3 start to decompose at 5 and YC-6, the substitution of MH by ATH is 30% and 50%, respectively.
over 600  C [46]. And thirdly, the enhanced crack resistance provided for The three composite flame retardants work well together to improve the
cement matrix by thermal decomposition of fiber plants will reduce to thermal stability of the fibers while also preventing cement matrix from
some extent. containing excessive amounts of MH and ATH filler, which has little
Figure 14(b) shows that at 650  C, YC-1 and YC-2 have the most impact on the processing and mechanical characteristics of the cement-
significant loss rates of LFCC compression strength, which are 95.15% base materials [48]. As a result, the strength loss and mass loss of LFCC
and 83.56%, respectively. YC-3 and YC-4 have the lowest loss rates of are relatively minor.
compression strength, which are 38.27% and 54.01%, respectively.
While YC-5, YC-6, and YC-7 have an approximately similar loss rate of 3.5.3. Thermal insulation performance of LFCC at high temperatures
compression strength. According to the results, composite flame- Figure 16 displays the LFCC's thermal conductivity and mass loss rate
retardant fibers improve the thermal stability of LFCC more than non- under high temperatures. As shown in Figure 16(a), the thermal con-
flame-retardant fibers or single flame-retardant fibers. Hence the loss ductivity of LFCC decreases with the increase in temperature overall.
rate of LFCC compression strength is relatively low. However, in the middle stage, the thermal conductivity of some speci-
mens first increases and then falls, such as YC-3, YC-4, YC-5, and YC-2.
3.5.2.2. Flexural strength of LFCC at high temperatures. Figure 15 displays The main reason is that in the low-temperature stage of 25 C–150  C,
the flexural strength and loss rate of LFCC at high temperatures. as temperature rises, the hydration products of cement increase,
As shown in Figure 15(a), as the temperature rises, the flexural enhancing specimens' compactness and thermal conductivity. In the
strength of LFCC typically declines, which could be generally split into middle and high-temperature stage of 150 C–650  C, the fibers dehy-
three stages: 25 C–150  C, the strength decrease amplitude is relatively drate to shrink, and the cement matrix water evaporates. The cracks and
small, and some even increase; the second stage: 150 C–350  C, the pores increase in the specimens, reducing the thermal conductivity of the
strength decrease amplitude is relatively large, especially at 150 C–250 specimens. Some specimens, such as YC-1, YC-2, YC-5, and YC-6, in-

C, the strength will decrease sharply; the third stage: 350 C–650  C, the crease their thermal conductivity when the temperature exceeds 500  C.
strength decrease amplitude is relatively small but stable. At 650  C, YC-5 It is as a result of the cement matrix cracking, the severe cracking of leaf

Figure 14. Compression strength and its loss rate of LFCC at high temperatures:(a) Compression strength; (b) Compression strength loss rate.

11
D. Jiang et al. Heliyon 8 (2022) e12175

Figure 15. Flexural strength and its loss rate of LFCC at high temperatures:(a) Flexural strength; (b) Flexural strength loss rate.

Figure 16. Thermal conductivity and its loss rate of LFCC at high temperatures:(a) Thermal conductivity; (b) Thermal conductivity loss rate.

fibers at high temps, and the increase of connecting pores, thus increasing temperatures. At the same time, APP with higher solubility is easier to
specimens' thermal conductivity. At 650  C, YC-3 and YC-4 have low penetrate the fiber when modifying leaf fiber, which has little impact on
thermal conductivity, which is 0.12881 (W/m.K) and 0.13073 (W/m.K), the hydration products of cement material. The internal pores of LFCC do
respectively, while YC-5, YC-7, and YC-6 have high thermal conductivity, not increase much under high temperatures.
which is 0.17330 (W/m.K), 0.17291 (W/m.K), and 0.16866 (W/m.K),
respectively. It is because the thermal conductivity of LFCC is related to 3.5.4. Micro-morphology of LFCC at high temperatures
the thermal stability of fibers and the porosity and pore characteristics of The micro-morphology of LFCC was examined using a scanning
the cement matrix [49]. When leaf fibers are modified with flame re- electron microscope (SEM) at 25  C (a normal temperature) and 650  C
tardants, their surface porosity decreases, increasing the thermal con- (a hot temperature), as illustrated in Figures 17 and 18, accordingly.
ductivity of LFCC. Inevitably, during the LFCC molding process, some of As shown in Figure 17, the leaf fibers in specimens have cement hy-
the flame retardants MH and ATH are permeate into the cement-base dration products on their surfaces, which are mainly hydrated calcium
materials, making the cement hydration products crisp and loose to a silicate gel (C–S–H), in addition to two crystals of dicalcium silicate
certain extent, and the porosity of cement matrix increases, thus reducing (2CaOSiO2, C2S), tricalcium silicate (3CaOSiO2, C3S), calcite
the thermal conductivity of composite material. Moreover, the latter (CaCO3), feldspar (Ca54MgAl2Si16O90), and the like [1, 2]. These hy-
played a more prominent role. dration products are flocculent, massive, and granular forms and form a
Figure 16(b) shows that, despite some specimens' loss rates of thermal whole with fibers through adhesion and mechanical bite force. As a result
conductivity decreasing at the middle and low temperatures stages, in of the fiber modification and LFCC molding process, fibers inevitably
general, the loss rate of thermal conductivity of the LFCC increases with sustain damage and cracks, causing more pores to LFCC. There is a
the increase of temperature. This shows that the internal cracks and pores certain gap between fibers and cement-base materials caused by fibers'
of LFCC specimen increase at high temperatures, and the thermal con- volume deformation during shrinkage. These pores will affect the
ductivity of the specimen decreases. At 650  C, YC-3 and YC-4 have the strength and thermal insulation performance of LFCC. Generally
largest loss rate of thermal conductivity, 54.22% and 53.87%, respec- speaking, the structure of YC-3 and YC-2 hydration products is loose.
tively, while YC-2 has the smallest loss rate, 5.47%. This further shows There are many pores and cracks in the hydration products, of which
that MH and ATH with low solubility retain more on the fiber's surface overall strength should not be high. The structure of hydration products
when they modify the leaf fiber, which is easy to drain into the cement in other groups is relatively dense, making the fibers and matrix well
base material, increasing the number of interior pores of LFCC and bonded. Since YC-7 is covered with sodium silicate, the amorphous silica
affecting the hydration of the cement-based material at high gel becomes brittle and hard after hardening. Some cracks appear on the

12
D. Jiang et al. Heliyon 8 (2022) e12175

Figure 17. Micro-morphology of LFCC at 25  C (1000 times): YC-1~YC-7 correspond to the serial numbers in Table 6.

surface of fibers, which will affect the bond strength between the fibers fiber surface. However, more needle-like particles are among the hy-
and the cement matrix to a certain extent. It can be seen from Figure 18 dration products than at 25  C, which is ettringite crystal (AFt) produced
that after 650  C, the leaf fibers in YC-1 and YC-2 are seriously carbon- by cement hydration [50, 51]. Large fractures and pores on the outside
ized. Other composite flame-retardant fiber samples are not entirely and interior of the leaf fibers indicate that they have undergone thermal
carbonized. Many cement hydration products have still adhered to the degradation and damage at high temperatures, fibers' ability to supply

13
D. Jiang et al. Heliyon 8 (2022) e12175

Figure 18. Micro-morphology of LFCC at 650  C (1000 times): YC-1~YC-7 correspond to the serial numbers in Table 6.

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D. Jiang et al. Heliyon 8 (2022) e12175

the cement matrix with reinforcing and fracture resistance will inevitably (PO3)n→P2O5 or P4O10 (3)
decline. Cracks and defects that appear in the cement matrix under
high-temperature stress will also reduce the strength of LFCC. YC-1, H3PO4→HPO2þ5OH (4)
YC-2, and YC-3 hydration products have a crisp and loose structure. A
poor bond between fibers and cement matrix results in low overall PO⋅þH⋅→HPO (5)
strength. The structure of hydration products in other groups is relatively
HPO⋅þH⋅→H2þPO (6)
dense, resulting in a tight bond between fibers and cement matrix.
PO⋅þOH⋅→HPO.þO. (7)
3.5.5. Discussion
Leaf fibers mainly comprise cellulose, hemicellulose, and lignin 2Al(OH)3→Al2O3þ3H2O (8)
polymer compounds. When leaf fibers are heated, they undergo the first Mg(OH)2→MgO þ H2O (9)
stage of moisture content separation. With the increase in temperature,
hemicellulose and cellulose decompose to produce volatile products. Although APP has a good flame-retardant effect, it will produce
Hemicellulose has a lower degree of polymerization than cellulose, an certain smoke (such as carbon monoxide) when the flame-retardant leaf
indefinite structure, and more inadequate thermal stability than cellu- fibers are burned. MH and ATH have the advantages of good flame-
lose, so it is relatively easy to be pyrolyzed. Lignin is an aromatic com- retardant effect, non-toxic and smoke reduction, with good thermal sta-
pound with insufficient chemical activity and relatively high bility, helping them form, together with APP, a composite flame retar-
decomposition temperature, most of which are decomposed into carbon dant. Multicomponent composite flame retardants have a co-action due
[52]. to different flame-retardant mechanisms and decomposition temperature
The combustion of leaf fibers is a complex physicochemical process. of each component, which is usually better than single component flame
The microscopic perspective is a free radical reaction process, including retardants (see 3.2.1 and 3.3).
chain initiation, chain growth, and chain termination reaction. From the
macroscopic point of view, the process results from the interaction of 4. Conclusions
cellulose matrix, oxygen, and heat. Heat is the physical factor in realizing
combustion, and oxygen is the chemical factor of combustion. The cel- We analyzed the thermal stability and flammability of leaf fibers in
lulose matrix is the material basis of combustion [53]. Therefore, the this paper, examined the mechanical and physical properties of LFCC at
combustion process of leaf fibers is a free radical chain reaction process. high temperatures, explored the fiber modification mechanisms with
The three factors work together, and this process is affected by many FTIR, TG/DTG, and SEM methods, and expounded the effects of modified
internal and external factors. leaf fibers on the properties of LFCC at high temperatures, and, on this
The combustion of leaf fibers can be divided into three stages [54]: ① basis, has drawn the following conclusions:
thermal decomposition of cellulose matrix produces combustible gas; ②
combustible gas burns in the air; ③ part of the heat generated by com- (1) The chemical functional groups of leaf fibers have been affected
bustion causes the remaining cellulose matrix or molten material to by the actions of three different types of flame-retardant modifiers
continue to decompose, making the combustion continue. Therefore, to and two different types of exterior coating layers, changing their
make the leaf fibers flame retardant is to terminate one or several stages chemical structure.
of the combustion process. This process can usually be realized by the (2) Flame-retardant modified leaf fibers' thermal stability, with LOI
mechanism of condensed phase flame retardancy, gas-phase flame larger than 27.0%, belongs to refractory materials, is much higher
retardancy, and interruption of heat exchange [55, 56, 57]. than that of the non-flame-retardant modified leaf fibers. The
Gas-phase flame retardant mechanism: when APP is decomposed by flame-retardant fibers Y7, Y3, and Y4 have good thermal stability
heating, it will produce ammonia, polyphosphate, and phosphorus ox- with flame retardancy.
ides, as shown in the reaction Eqs. (1), (2), and (3). Ammonia will dilute
(3) The flame retardants components P, Mg, and Al are well deposited
oxygen, reduce the temperature of combustible gas, and inhibit the
on the exterior of flame-retardant fibers, according to SEM and
occurrence of flame combustion. When MH and ATH are decomposed by
EDS examination. Agglomerated and debris flame retardants
heating, it will produce a large amount of water vapor, as shown in re-
particles are also visible on the exterior of modified leaf fibers.
action Eqs. (8) and (9), diluting the oxygen concentration on the leaf
(4) At high temperatures, composite flame-retardant fiber LFCC has a
fibers' surface and slowing down or stopping the combustion reaction.
lower mass-loss rate than non-flame-retardant or single-
Condensed phase flame retardant mechanism: phosphorus oxide and
component flame-retardant fiber LFCC, in addition to YC-7.
polyphosphoric acid in APP cover the surface of leaf fibers to inhibit the
escape of combustible volatiles. As a strong dehydrating agent, poly- (5) In general, at high temps, with temperature rises, the strength of
phosphoric acid will dehydrate and carbonize leaf fibers to form a LFCC decreases, the rate of strength loss is increases with the rise
carbonization layer with oxygen isolation and heat insulation to play the of temperature. At high temperatures, composite flame-retardant
role of flame retardant. After heating and dehydration, MH and ATH will leaf fibers LFCC have an increased compression strength than fi-
form a metal oxide layer with a great specific surface area. The oxide bers without flame-retardant modification or fibers modified with
layer will absorb smoke and combustible volatiles and cover the surface only one kind of flame-retardant, and their compression strength
of leaf fibers to prevent oxygen and heat, stop the combustion chain re- is lost at a slower pace. YC-5 and YC-6 have better strength at high
action, and play the flame-retardant role. Interruption of heat exchange temperatures among the composite flame-retardant leaf fibers
mechanism: in the decomposition of APP into phosphoric acid, the LFCC.
following reactions Eqs. (4), (5), (6), and (7) will happen to free radicals, (6) In general, the thermal conductivity of LFCC decreases with the
which will capture O⋅ radicals and prevent combustion. When the fiber is increase in temperature, and its loss rate increases with the tem-
heated and burned, MH and ATH are heated to release crystal water, as perature rise. At 650  C, YC-3 and YC-4 have low thermal con-
shown in reaction Eqs. (8) and (9), which will absorb much heat to ductivity, 0.12881 (W/m.K) and 0.13073 (W/m.K), respectively.
decompose and reduce the flame temperature. (7) At 650  C, the leaf fibers in LFCC sustain thermal damage and
thermal degradation at high temperatures. Many cement hydra-
(NH4)nþ2PnO3nþ1→H3nPnO3nþ1 þ NH3↑ (1)
tion products still adhere to the fiber surfaces, and the hydration
H3nPnO3nþ1→(HPO3)n þ nH2O (2) products have more AFt crystals at 25  C.

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D. Jiang et al. Heliyon 8 (2022) e12175

Declarations [12] Y. Xu, W. Li, M. Zhu, X. Yue, M. Wang, Novel porous fiber-based composites with
excellent sound-absorbing and flame-retardant properties, J. Wood Chem. Technol.
40 (2020) 285–293.
Author contribution statement [13] Z. Zhang, Z. Ma, Q. Leng, Y. Wang, Eco-friendly flame retardant coating deposited
on cotton fabrics from bio-based chitosan, phytic acid and divalent metal ions, Int.
Demin Jiang: Conceived and designed the experiments; Contributed J. Biol. Macromol. 140 (2019) 303–310.
[14] D. Jiang, S. Lv, S. Cui, S. Sun, X. Song, S. He, J. Zhang, P. An, Effect of thermal
reagents, materials, analysis tools or data; Wrote the paper. insulation components on physical and mechanical properties of plant fibre
Haodong Xu, Shuchen Lv, Di Jiang: Performed the experiments. composite thermal insulation mortar, J. Mater. Res. Technol. 9 (6) (2020)
Suping Cui: Analyzed and interpreted the data. 12996–13013.
[15] GB/T17671-1999, Method of testing cement—Determination of strength (ISO
Shiguo Sun, Xiaoruan Song: Contributed reagents, materials, analysis method), Chinese National Standard, 1999.
tools or data. [16] GB/T10294-2008, Determination of Steady State Thermal Resistance and Related
Shiqin He, Jingzong Zhang: Conceived and designed the experiments. Properties of Insulation Materials—Protective Plate Method, Chinese National
Standard, 2008.
[17] P. Acu~ na, J. Zhang, G.-Z. Yin, X.-Q. Liu, D.-Y. Wang, Bio-based rigid
polyurethane foam from castor oil with excellent flame retardancy and high
Funding statement
insulation capacity via cooperation with carbon-based materials, J. Mater. Sci.
56 (2021) 2684–2701.
Dr Jiang De-min was supported by Beijing Natural Science Founda- [18] GB/T2406.2-2009, Plastics, Determination of Burning Behaviour by Oxygen index.
tion of China [2172021]. Xiaoruan Song was supported by North China Part 2: Ambient-Temperature Test, Chinese National Standard, 2009.
[19] GB/T 5454-1997, Textiles—Burning Behaviour—Oxygen index Method, Chinese
University of Technology Yuyou Team Training Project [110052972027/ National Standard, 1997.
027]. Shiguo Sun was supported by National Natural Science Foundation [20] G. Tang, H. Jiang, Y. Yang, D. Chen, et al., Preparation of
of China [41772335], 13th Five-Year National Key R&D Program melamine–formaldehyde resin–microencapsulated ammonium polyphosphate
and its application in flame retardant rigid polyurethane foam composites,
“Research on Facilities Hazard Monitoring and Landslide Early Warning J. Polym. Res. 27 (2020) 375.
Standards” [2018YFF0213304], National Key R&D Program [21] E. Asimakopoulou, J. Zhang, M. Mckee, K. Wieczorek, et al., Effect of layered
[2016YFC0701810], Innovative Engineering-Integration and Demon- double hydroxide, expanded graphite and ammonium polyphosphate additives on
thermal stability and flame performance of polyisocyanurate insulation foam,
stration: Key Technology R&D Projects for Improving the Resilience Thermochim. Acta 693 (2020), 178724.
Capability of Urban Rail Transit Infrastructure Disasters [2018–1]. [22] X. Cao, H. Zhao, X. Liu, H. Luo, R. Liu, Preparation of petal-like magnesium
hydroxide particles by adding sulfate ions, J. Cryst. Growth 550 (2020), 125841.
[23] T. Liu, F. Wang, G. Li, P. Liu, C. Gao, Y. Ding, S. Zhang, X. Kong, M. Yang,
Data availability statement Magnesium hydroxide nanoparticles grafted by DOPO and its flame retardancy in
ethylene-vinyl acetate copolymers, J. Appl. Polym. Sci. 138 (2021), 49607.
[24] S. Lan, L. Li, D. Xu, D. Zhu, Z. Liu, F. Nie, Surface modification of magnesium
Data included in article/supplementary material/referenced in hydroxide using vinyltriethoxysilane by dry process, Appl. Surf. Sci. 382 (2016)
article. 56–62.
[25] S. Gypser, F. Hirsch, A.M. Schleicher, D. Freese, Impact of crystalline and
amorphous iron- and aluminum hydroxides on mechanisms of phosphate
Declaration of interests statement adsorption and desorption, J. Environ. Sci. 70 (2018) 175–189.
[26] F.Z. Arrakhiz, M. El Achaby, K. Benmoussa, et al., Evaluation of mechanical and
thermal properties of Pine cone fibers reinforced compatibilized polypropylene,
The authors declare no conflict of interest. Mater. Des. 40 (2012) 528–535.
[27] T. Lu, S. Liu, M. Jiang, et al., Effects of modifications of bamboo cellulose fibers on
the improved mechanical properties of cellulose reinforced poly (lactic acid)
Additional information composites, Composites Part B 62 (2014) 191–197.
[28] K.Z.M. Abdul Motaleb, R. Al Mizan, R. Milasius, Development and characterization
of eco-sustainable banana fiber nonwoven material: surface treatment, water
No additional information is available for this paper.
absorbency and mechanical properties, Cellulose 27 (2020) 7889–7900.
[29] S.P. Kundu, S. Chakraborty, A. Roy, et al., Chemically modified jute fibre reinforced
References non-pressure (NP) concrete pipes with improved mechanical properties, Construct.
Build. Mater. 37 (2012) 841–850.
[30] M.M. Kabir, H. Wang, K.T. Lau, F. Cardona, T. Aravinthan, Mechanical properties of
[1] F. Shukor, A. Hassan, M.S. Islam, M. Mokhtar, M. Hasan, Effect of ammonium
chemically-treated hemp fibre reinforced sandwich composites, Composites Part B
polyphosphate on flame retardancy, thermal stability and mechanical properties of
43 (2012) 159–169.
alkali treated kenaf fiber filled PLA biocomposites, Mater. Des. 54 (2014) 425–429.
[31] Y. Seki, M. Sarikanat, K. Sever, C. Durmuskahya, Extraction and properties of Ferula
[2] K. Ramanaiah, A.V. Ratna Prasad, K. Hema Chandra Reddy, Mechanical,
communis (chakshir) fibers as novel reinforcement for composites materials,
thermophysical and flame properties of sansevieria fiber-reinforced polyester
Composites Part B 44 (2013) 517–523.
composites, Mater. Des. 49 (2013) 986–991.
[32] K.V. Chalapathi, M.N. Prabhakar, J. Song, Impact of surface treatments and hybrid
[3] N. Li, H. Yan, L. Xia, L. Mao, Z. Fang, Y. Song, H. Wang, Flame retarding and
flame retardants on flammability, and thermal performance of bamboo paper
reinforcing modification of ramie/polybenzoxazine composites by surface
composites, J. Nat. Fibers 10 (2020) 1–11.
treatment of ramie fabric, Compos. Sci. Technol. 121 (2015) 82–88.
[33] Y. Liu, H. Li, Q. Chen, F. Luo, C. Cao, Effect of bamboo flour on flame retardancy
[4] D. Jiang, S. Cui, X. Song, J. Zhang, Analysis of micro-morphology and heat-
and smoke suppression of polypropylene/ammonium polyphosphate composites,
insulating property of leaf concrete, Construct. Build. Mater. 49 (2013) 663–671.
Front. Mater. 9 (2020), 574924.
[5] D. Jiang, P. An, S. Cui, F. Xu, T. Tuo, J. Zhang, H. Jiang, Effect of leaf fibers
[34] S.P. Jozi
c, D. Jozi
c, J. Jaki
c, B. Andrici
c, Preparation and characterization of PLA
modification methods on mechanical and heat-insulating properties of leaf fibers
composites with modified magnesium hydroxide obtained from seawater, J. Therm.
cement-based composite materials, J. Build. Eng. 19 (2018) 573–583.
Anal. Calorim. 142 (5) (2020) 1877–1889.
[6] L. Zhang, Z. Jiang, W. Zhang, S. Peng, P. Chen, Flexural properties and
[35] N.H. Thi, T.N. Nguyen, H.T. Oanh, et al., Synergistic effects of aluminum hydroxide,
microstructure mechanisms of renewable coir-fiber-reinforced magnesium
red phosphorus, and expandable graphite on the flame retardancy and thermal
phosphate cement-based composite considering curing ages, Polymer 12 (2020)
stability of polyethylene, J. Appl. Polym. Sci. 11 (2020), 50317.
2556.
[36] C.H.S. Souza Rosa, M.G. Moth
e, M.F.V. Marques, C.G. Moth
e, S.N. Monteiro,
[7] M.M. Camargo, E.A. Taye, J.A. Roether, D.T. Redda, A.R. Boccaccini, A review on
Steam-exploded fibers of almond tree leaves as reinforcement of novel recycled
natural fiber-reinforced geopolymer and cement-based composites, Materials 13
polypropylene composites, J. Mater. Res. Technol. 9 (5) (2020) 11791–11800.
(2020) 4603.
[37] R.F.P. Junio, L.F.C. Nascimento, L.M. Neuba, et al., Copernicia prunifera leaf fibers:
[8] S. Jr Holmer, A. Vahan, Transition zone studies of vegetable fibre-cement paste
a promising new reinforcement for epoxy composites, Polymer 12 (9) (2020) 2090.
composites, Cem. Concr. Compos. 21 (1999) 49–57.
[38] W. Zhang, C. He, Z. Wei, K. Shi, Impact of hot water treated Lotus leaves on
[9] N. Padkho, A new design recycle agricultural waste materials for profitable use rice
interfacial and physico-mechanical of gelatin/Lotus leaf composites, J. Polym.
straw and maize husk in wall, Procedia Eng. 32 (2012) 1113–1118.
Environ. 28 (12) (2020) 3270–3278.
[10] D. Jiang, S. Cui, F. Xu, T. Tuo, Impact of leaf fibre modification methods on
[39] T.M. Loganathan, M.T.H. Sultan, Q. Ahsan, M. Jawaid, J. Naveen, A.U.M. Shah,
compatibility between leaf fibres and cement-based materials, Construct. Build.
L.S. Hu, Characterization of alkali treated new cellulosic fibre from Cyrtostachys
Mater. 94 (2015) 502–512.
renda, J. Mater. Res. Technol. 9 (3) (2020) 3537–3546.
[11] M. Ferrandez-Villena, C.E. Ferrandez-Garcia, T. Garcia-Ortu~no, A. Ferrandez-Garcia,
[40] A.A. Silva, K. Dahmouche, B.G. Soares, The effect of addition of acrylic acid and
M.T. Ferrandez-Garcia, Analysis of the thermal insulation and flame-resistance
thioglycolic acid on the nanostructure and thermal stability of
capacity of particleboards made from vine (Vitis vinifera L.), Prunings. Polym. 12
PMMA–montmorillonite nanocomposites, Appl. Clay Sci. 47 (2010) 414–420.
(2020) 1147.

16
D. Jiang et al. Heliyon 8 (2022) e12175

[41] L. Yan, Z. Xu, N. Deng, Effects of polyethylene glycol borate on the flame retardancy [49] J.C. Mendes, R.R. Barreto, A.C.B. Paula, et al., On the relationship between
and smoke suppression properties of transparent flame-retardant coatings applied morphology and thermal conductivity of cement-based composites, Cem. Concr.
on wood substrates, Prog. Org. Coating 135 (2019) 123–334. Compos. 104 (2019), 103365.
[42] L. Song, W. Liu, F. Xin, Y. Li, Materials studio” simulation study of the adsorption [50] M. Garg, A. Pundir, Investigation of properties of fluorogypsum-slag composite
and polymerization mechanism of sodium silicate on active silica surface at binders – hydration, strength and microstructure, Cem. Concr. Compos. 45 (2014)
different temperatures, Int. J. Metalcast. 11 (2020). 227–233.
[43] Q. Zhang, W. Lu, L. Zhou, D. Zhang, H. Cai, X. Lin, Tensile and flammability [51] H. El-Didamony, M. Heikal, K.A. Khalil, Characteristics of cement pastes containing
characterizations of corn straw slagging/high-density polyethylene composites, sulphoaluminate and belite prepared from nano-materials, Construct. Build. Mater.
J. Thermoplast. Compos. Mater. 33 (11) (2020) 1466–1477. 38 (2013) 14–21.
[44] H. Chai, X. Tang, M. Ni, F. Chen, Y. Zhang, D. Chen, Y. Qiu, Preparation and [52] P. Manimaran, G.P. Pillai, V. Vignesh, M. Prithiviraj, Characterization of natural
properties of flexible flame-retardant neutron shielding material based on methyl cellulosic fibers from Nendran Banana Peduncle plants, Int. J. Biol. Macromol. 162
vinyl silicone rubber, J. Nucl. Mater. 464 (2015) 210–215. (2020) 1807–1815.
[45] L. Gu, Q. Yu, L. Zhang, Preparation and characterization of the halogen-free, smoke [53] T. Lee, Z.A. Zubir, F.M. Jamil, A. Matsumoto, F.-Y. Yeoh, Combustion and pyrolysis
suppression, organic–inorganic hybrid flame-retardant expandable polystyrene of activated carbon fibre from oil palm empty fruit bunch fibre assisted through
materials, J. Appl. Polym. Sci. 137 (45) (2020), 49391. chemical activation with acid treatment, J. Anal. Appl. Pyrolysis 110 (2014)
[46] J. Tang, P. Li, X. Chen, Y. Bai, Experimental study of strength, pore structure and 408–418.
phase evolution characteristics of iron tailings cemented paste backfill under high- [54] Y. Zhang, L. Wang, Y. Wu, Y. Chen, et al., Pyrolysis characteristics, kinetics, and its
temperature, Cem, Wapno Beton 25 (2) (2020) 78–94. product characteristics of grape stem, Bioresources (4) (2019) 7901–7919.

[47] R. Stefan, M. Foglar, J. Fl
adr, K. Horníkov
a, J. Holan, Thermal, spalling, and [55] F.-Q. Zhang, B. Wang, Y.-J. Xu, P. Li, Y. Liu, P. Zhu, Convenient blending of alginate
mechanical behaviour of various types of cementitious composites exposed to fibers with polyamide fibers for flame-retardant non-woven fabrics, Cellulose 27
flame: experimental and numerical analysis, Construct. Build. Mater. 262 (2020), (2020) 8341–8349.
119676. [56] A. Thomas, M. Arun, K. Moinuddin, P. Joseph, Mechanistic aspects of condensed-
[48] S. Zhang, X. Bu, X. Gu, J. Sun, H. Li, W. Tang, Improving the mechanical properties and gaseous-phase activities of some phosphorus-containing flame retardants,
and flame retardancy of ethylene-vinyl acetate copolymer by introducing bis[3- Polymer 12 (2020) 1801.
(triethoxysilyl) propyl] tetrasulfide modified magnesium hydroxide, Surf. Interface [57] T. Ning, J. Zhang, L. Fu, Research advances of flame retardant polymer materials in
Anal. 49 (7) (2017) 607–614. the Field of electrical packaging, China Plast. Ind. 47 (10) (2019) 1–6, 147.

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