Received: 1 November 2019 Revised: 2 June 2020 Accepted: 8 June 2020

DOI: 10.1002/fam.2883

RESEARCH ARTICLE

Preparation, thermal properties and permeabilities of

aluminum-coated fabrics destined for thermal radiation
protective clothing

FL Zhu | QQ Feng

Department of Clothing, Huizhou University,

Huizhou, China Summary
In this study, radiant reflective, flame retardant and water vapor permeable coatings
Correspondence
FL Zhu, Department of Clothing, Huizhou were fabricated on aramid fabric (AF) for thermal radiation protective clothing by
University, Huizhou, CN, China. using a simple cost-effective coating method, which included an aluminum paste,
Email: flzhu_123@163.com
APP-PER-MEL and a silk fibroin powder in the TPU solution system. The permeabil-
Funding information ity, flame retardancy, thermal stability, radiative spectral reflectance, as well as RPP
National Key Research and Development
Program of China, Grant/Award Number: of these prepared fabrics were characterized and compared with the pure AF and
2017YFB0309001 aluminum-foiled AF (AF-AF). Results show that the newly developed aluminized AF
had rather high permeability, and the permeable capability would be further
enhanced with the additive of silk fibroin powder. The flame retardancy (FR) of the
coated fabric sample was also achieved by introducing an intumescent FR system. In
contrast to the pure AF, the aluminum-coated AF provided higher levels of radiation
protection in RPP testing. This was further confirmed by the fact that aluminum-
coated AF exhibited comparative high average reflectivities (more than 0.7) in the
radiant spectral range of 1547 nm to 2500 nm. Thus, the aluminum-coated AF pre-
pared by functional coating method exhibit great and competitive practicability in
thermal protective clothing due to their excellent moisture comfort and radiant ther-
mal protection.

KEYWORDS

aluminum paste, firefighter protective clothing, flame retardancy, permeability, thermal

reflection

1 | I N T RO DU CT I O N important role in promoting flame retardancy and thermal protection.

Firefighters near the fire zone will be exposed to strong thermal radia-
tion, which will cause burn injuries to exposed skin and also result in
charring or ignition of textiles when firefighting or carrying out of a
1,2
rescue. Therefore, they need to wear thermal radiative protective
clothing (TRPC) with a high thermal radiation reflective capacity to
ensure the safety and enhance operational efficiency during fire or
thermal exposures. TRPC is a typical multi-layered personal protective
clothing system, which is composed of an outer shell fabric, a mois-
ture barrier, and a thermal liner.3The outer material layer plays an
In addition, the required thickness for thermal liner is closely related
to the selection of the outer material. To some extent, the overall
practicability, comfort and protection of protective clothing are also
dependent on the outer material.4
The outer layer provides both fire resistance and prevention to
penetration of thermal radiation in such a way that the high heat flux
from the thermal source can be reflected by the outer thermal reflec-
tive surface. Much work has been done to provide aluminized fabrics
with high reflectivity. In general, aluminized or metallic technology
used to generate thermal reflection property for fabrics can be treated

Fire and Materials. 2020;1–10. wileyonlinelibrary.com/journal/fam © 2020 John Wiley & Sons Ltd 1
2 ZHU AND FENG
as: traditional metallic treating method or the magnetron sputter coat-
ing approach.5 The former method produces metallic fabric through a
6
printing or laminating process. Hrynyk et al characterized finished
basalt fabrics with aluminized modifications for application in personal
protective equipment (PPE).Their work indicated that the application
of aluminized basalt fabrics in PPE, for example, protective gloves or
clothing, could give promising results. Aluminum foil which has excel-
lent reflective property was glued onto the surface of AFs using a high
temperature resistant inorganic adhesive. As a result of aluminizing
the fabric with aluminum foil, the reflectance of the AF increased from
63.6% to 92.3% and the thermal resistance was enhanced by almost
45%.7 At the same time, investigations on aluminized basalt and glass
fabrics using aluminum foil were presented by Hao and Yu.8 Their
results showed that the spectral reflectance of aluminized fabrics
exhibit differences over a wide range of wavelengths due to different
yarn parameters and weave structures. The thermal protective perfor-
mance of aluminized fabrics is better than those of the substrate fab-
rics. Jin et al9 examined the effect of aluminum foil on the radiant
protective performance (RPP) and flame protective performance (FPP)
of fire proximity suit materials and found that the RPP of aluminized
fabrics was affected by both the protective film and the structure of
the laminate fabric. Aluminized multi-layered protective fabrics con-
sisting of a layer of aluminum foil, one of glass fabric, and a layer of
cotton fabric were also studied by Ghane and Sarlak.10 They found
that the reflectivity of the aluminum layer had no influence on the
relationship between the radiation heat flux and material thickness
due to utilization of the same aluminum foil for all samples in the
experiments.
Magnetron Sputtering is a Plasma Vapor Deposition (PVD) pro-
cess in which energized gas ions accelerated by an electrical field
strike the “target” and ejects atoms from the target to form a func-
tional coating on the substrate.11 The technology has been widely
used to accumulate very thin films on fiber or fabric substrates for
optical control, and electromagnetic shielding in clothing. Miao et al
deposited Ag and AZO/Ag/AZO ceramic films on cotton fabrics by
radio frequency (RF) magnetron sputtering. They found that Ag
coated cotton fabrics showed an infrared reflection rate of 16% and
an ultraviolet protection factor (UPF) values of 11.096.12 Yuan et al13
prepared Ag/TiO2 composite films by magnetron sputtering method
and further characterized the composite films through photocatalytic
experiments. Their results showed that photocatalytic activities of
fabrics coated with Ag/TiO2 composite films were higher than the
fabric coated with TiO2 films, due to the effect of the underlying Ag
film. Xia et al14 employed the technique of vacuum-assisted resin
transfer molding (VARTM) and Cu film magnetron sputtering to
deposit Cu onto the kenaf fiber composites with electromagnetic
interference (EMI) shielding function. They obtained the results that
after being Cu-sputter coated for 3 hour, the EMI shielding effective-
ness values was increased to be 48.3 dB, which indicated that 99.99%
incident signal was blocked.
The thermal reflective layer are almost always prepared by lami-
nating an aluminum foil or through magnetron sputtering a thin film
onto the substrate fabric to obtain high levels of radiant protection.
However, the aforementioned aluminized fabrics suffer from some
drawbacks, such as flammability, oxidation, poor moisture permeabil-
ity and delamination.15,16 The firefighters' thermoregulatory system
was severely challenged by wearing aluminized protective clothing
during exercise in strong radiant heat environments.17 In this study,
aluminized aramid composite fabrics with reflective function were
fabricated using convenient coating techniques, which included alumi-
num paste, flame retardants and silk fibroin powder. Flame ret-
ardancy, water vapor/air permeability, radiant spectral reflectance, as
well as radiant protective performance were explored. In contrast to
the traditional aluminized fabric, the air and water vapor permeabil-
ities of composite fabrics prepared in this study were significantly
improved.
2 | M A T E R I A L S A N D M ET H O D S
2.1 | Materials
A pure aramid fabric (AF) in griege color with an area density of
210 g/m2 (provided by Baoding Sanyuan Textile Technology Co., Ltd)
was used as substrate matrix. As a contrast, a commercial aluminum-
foiled aramid fabric (AF-AF), which was supplied by Jiangsu Tiandizao
New material technology Co., Ltd, was selected. Their structural
parameters were tabulated in Table 1. Thermoplastic polyurethane
(TPU) particles in coated grade were obtained from Zhonggang Plastic
Materials Co. Ltd, Dongguan, China. N, N-dimethylformamide (DMF)
and ammonium polyphosphate (APP) were obtained from Jinan
Taixing Fine Chemical Co., Ltd (China). Pentaerythrotol (PER), Mela-
mine (MEL) and methylethylketone (MEK) were purchased from Tian-
jin Kermel Chemical Reagant Co., Ltd (China). T8 aluminum pastes
(8 μm) and super fine silk fibroin power (2 μm) were supplied by
Shenzhen Andron Technology Co., Ltd (China) and Huzhou Xintianshi
Biotechnology Co., Ltd. (China), respectively. The thickness of the fab-
ric sample was measured by a fabric thickness digital tester (model
YG141D) with a pressure weight of 25cN. Air permeability was deter-
mined by a digital fabric air permeability tester (YG461E-III) in a pres-
sure difference of 100Mpa.
2.2 | Preparation of TPU solution
Preparation of the coated adhesive was carried out in a three-step
process. Firstly, flame resistant thermoplastic polyurethane (TPU)
solution was prepared by adding TPU into solvent with magnetic stir-
ring at room temperature for 90 minutes. APP, PER and MEL (intu-
mescent FR system) were consecutively added into the prepared TPU
solution, and then the TPU-FR solution was mixed with high-speed
stirring at room temperature for 90 minutes. In order to dissolve the
APP better, the TPU-FR mixed solution was heated at 85
C for two
minutes. At the second stage, MEK was added into the aluminum pas-
tes (AP) with magnetic stirring for 20 minutes and the AP solution in
silvery gray color was obtained. It should be noted that both the
ZHU AND FENG 3

TABLE 1 Descriptions of fabric samples and their permeabilities

Thickness Area density Air permeability WVTR

Sample No. Description (mm) (g/m2) (mm/s)/SD (g/m2 24 h)/SD
AF Aramid fabric 0.412 210.00 145.13 /8.36 2810.45/208.24
AF-AF Aluminum-foiled Aramid fabric 0.425 270.00 1.42 /0.13 24.13/2.55
TPU-AP-AF TPU + aluminum paste 0.454 231.59 3.68/0.46 1179.57/64.41
TPU-AP-SF-AF TPU + aluminum paste+10%Silk 0.506 237.92 11.19/1.28 2258.11/103.87
fibroin powder
TPU-AP-SF-FR-AF TPU + aluminum paste+5%Silk fibroin 0.532 270.50 4.65 /0.68 2361.25/112.38
powder+10%Flame retardant

F I G U R E 1 Photo images of
pure and aluminized aramid
fabrics. (From left to right: A,
AF; B, AF-AF; C, TPU-AP-AF; D,
TPU-AP-SF-AF; E, TPU-AP-SF-
FR-AF)

stirring speed and stirring time at this stage should be low to avoid
destroying the surface coating membrane (SiO2) covering the alumi-
num paste and to prevent rapid oxidation of the aluminum paste coat-
ing. Finally, the FR-TPU solution was added to AP solution. When
stirring, the superfine silk fibroin (SF) powder was added into the FR-
TPU/AP mixed solution. The viscosity of the solution was adjusted
from 3000 to 6000 cP by adding N, N-dimethylformamide and MEK.
After preparation, the TPU-AP-SF-FR solution was allowed to rest for
30 minutes or vacuumed.
remove the DMF and then cured at 140
C for 5 minutes. The thickness
of the TPU coated layer was about 110 ± 5 μm when measured using
the fabric thickness digital tester. The coated and uncoated fabrics are
coded and listed in Table 1. The photo images of surface appearance of
all fabric samples are depicted in Figure 1.
2.4 | Characterization methods
2.4.1 | Scanning electron microscopy (SEM)

2.3 | Coating of fabrics
The aramid fabric (AF) was coated using a knife over roller machine
(MU572C) with different solutions including TPU-AP (TPU + aluminum
paste), TPU-AP-SF (TPU + aluminum paste+silk fibroin) and TPU-AP-SF-
FR (TPU + aluminum paste+silk fibroin+Flame retardants) solutions,
which are listed in Table 1(Descriptions). Before coating, the aramid fab-
ric samples were washed using a 0.5 wt% NaOH solution, and dried in
an oven at 90
C for 10 minutes. The coated fabrics were first pre-dried
at 120
C in an electric thermostatic drying oven for 2 minutes to
Scanning electron microscopy (SEM) images were obtained on a field
emission scanning electron microscope (FEI Quanta 250FEG) oper-
ated at an acceleration different voltage of 5, 10 and 15 kV. Samples
were sputter-coated with gold prior to examination.
2.4.2 | Water vapor transmission rate (WVTR)
The water vapor permeability of a textile material is a key property of
its thermal comfort performance, which can be evaluated by Water
4 ZHU AND FENG
vapor transmission rates (WVTRs). In this work, WVTRs were mea-
sured using an upright-dish tester (W3/301, Labthink Instruments
Co., Ltd. Jinan, China) according to ASTM E96-80B. Three circular
stainless steel dishes, 8 cm in diameter and 2.5 cm in height, were
filled with deionized water. The volume of water in the dish was
adjusted to allow an air gap between the water and the inner face of
the fabric. The fabric samples were placed over the dishes, and sealed
by a fixed gasket. The coated or laminated side was facing the water
in the dish. Water vapor on the outer surface of the fabric was carried
away by pure nitrogen stream. Three replications of the test were run
and an average value of WVTR was obtained. After 12 hour, the
WVTRs could be calculated from a slope between water vapor trans-
fer and time, and expressed in units of g/(m2 24 h).
2.4.3 | Flame resistant performance
Limit oxygen index (LOI) tests of fabric (120 mm × 60 mm) were car-
ried out on a COI oxygen index tester (Motis technology Co., LTD,
China) according to an international standard ASTM 2863. A scale
mark was drawn on each specimen at 50 mm on the ignition side
beforehand. Each test was repeated five times as required, and the
mean value was obtained. The Vertical Burning Test (VBT) was con-
ducted on a LFY-601 type instrument (Shandong Textile Science
Research Institute, China), according to GB/T 5455-1997 (China).
The test method evaluates the vertical burning behavior of the fab-
rics, including after-flame time (the length of time the material con-
tinues to burn after removal of the burner after 12-second ignition
time), after-glow time (the length of time for the material glows
after the flame is extinguished), damaged length, and the char resi-
due length. Eight specimens (300 mm × 80 mm) of each fabric were
required in this test, five specimens for the warp direction test and
the other three for the weft direction test. The average values for
these VBT tested results in the warp and weft directions were
recorded.
2.4.4 | Thermogravimetric analysis and MCC
measurement
The STA449 F3 (Netzsch, Germany) thermogravimetric analyzer was
used to investigate the thermal degradation of the uncoated and
coated fabrics. Thermogravimetric analyzes (TGA) were carried out at
a heating rate of 10
C/min from 35
C to 800
C in a nitrogen
atmosphere.
The flammability of the sample was evaluated using Micro-scale
Combustion Calorimetric (MCC) test, which was conducted on a
FTT0001 micro-calorimeter combustion instrument (FTT, UK)
according to standard ASTM D7309. The sample, which was grinded
approximately 5 mg (fiber powder), was tested on a 40 μL alumina
crucible, and heated from 75
C to 750
C using a linear heating rate
(1
C/s) in a mixture stream by using a flow rate 80 cm3/min for the
nitrogen and a flow rate of 20 cm3/min for the oxygen.
2.4.5 | Spectral reflectance
Radiant heat occupies most of the total heat transportation in
firefighting and radiation heat transfer is the dominant mode of heat
transfer at temperatures higher than 400 K.7 Thus, the study on
thermal protective clothing with prominent radiant protection
capacity, has been of great interest to researcher in the past two
decades.18The spectral reflectance of the specimen was measured
using a UV-Vis-NIR spectrophotometer (Agilent Cary 5000,
Australia) with a scan speed of 10 nm/s over the wavelengths from
0.76 to 2.5 μm. The testing principle is shown in Figure 2. The
selected spectral region was determined by Wien's displacement
law derived from Planck law.
2.4.6 | Radiant protective performance (RPP)
The Radiant Protective Performance (RPP) of the fabric samples
was measured in a modified bench-top RPP tester provided by
Motis Technology Co., Ltd (China), as shown in Figure 3. Thirteen
500-watt quartz tubes were used to deliver the required radiant
heat energy (heat flux level of 21 ± 0.5 kW/m2) to one surface of a
specimen as specified in ASTM F 1939. The required times to first
and second skin burn can be determined by overlaying the curve of
the thermal response of the copper calorimeter with the first and
second burn curves calculated by the embedded software (also pro-
vided by Motis Technology Co., Ltd., China). Exposure time was
30 seconds for all tests. Prior to testing, the fabrics were condi-
tioned for at least 24 h in a standard atmosphere of 65 ± 5%RH and
20
C ± 2
C.
3 | RESULTS AND DISCUSSION
3.1 | Morphology of fabrics
SEM was utilized to characterize the morphology of the surfaces of
the uncoated Aramid 1313 fabric and the coated fabrics. It was found
that the uncoated Aramid fiber showed a smooth surface (Figure 4A).
The coated fibers were fully covered after treatment, and exhibited a
F I G U R E 2 Testing principle of radiative properties: A, reference
measurement; B, directional-hemispherical reflectance
ZHU AND FENG 5

rough surface. A dense membrane coating structure of TPU-AP-AF
can been seen from Figure 4B, while micro- or nano-voids were
formed when silk fibroins were coated onto the fabric samples
(Figure 4C,D. The hierarchical micro- or nano structures can be found
from Figure 5. This is believed to be the key factor in obtaining the
permeability properties for the coated fabric with silk fibroins. Larger
micro-sheets (red circle) formed in the fabrics coated with APP flame
retardants.
Heat insulated board
Fabric sample
Thermal calorimeter
Quartz tubes
Thermocouple
3.2 | Permeability tests
The basic permeability (including air permeability and WVTR) test
results for the pure aramid fabric, aluminum-foiled aramid fabric and
the three coated aramid fabrics, which incorporated the aluminum
paste, are tabulated in Table 1. WVTR is a measure of the amount of
water vapor passing through unit area of material per unit time. The
SD values are listed in Table 1. It can be seen that the air permeability
and water vapor permeability of TPU-SP coated fabrics were
improved by adding superfine silk fibroin powder. Compared with
aluminum-foiled aramid fabric (AF-AF), the air permeability and WVTR
of TPU-AP-SF-FR-AF sample were increased by 2.3 times and about
2300 times, respectively. Figure 6 indicates that AF-AF sample had
the lowest WVTR value (only 24.13 g/[m2 24h]) resulting from imped-
iment to water vapor, through the dense, impermeable aluminum foil.
A significant increase in WVTR is attributed to the voids formed by
the super fine silk fibroin powders, which provide continuous water
vapor channels allowing for moisture transfer. In addition, the silk
fibroin power will absorb moisture due to its biopolymer molecular
structure with hydrophilic material and hygroscopic groups ( COOH,
OH, NH) in its molecular structure.19,20 Improved air and water

Specimen vapor permeability of the aluminum coated fabrics due to addition of

super fine silk fibroin powder will make the wearer comfortable even
FIGURE 3 Schematic diagram of RPP tester if in the hot environment.

FIGURE 4 SEM images of A, uncoated AF; B, TPU-AP-AF; C, TPU-AP-SF-AF; D, TPU-AP-SF-FR-AF, in magnification of 10 000X
6 ZHU AND FENG

FIGURE 5 SEM images of A, neat AF; B, TPU-AP-AF; C, TPU-AP-SF-AF; D, TPU-AP-SF-FR-AF, in magnification of 2000X

3500 fighters' thermal insulation protective clothing. However, it is obvious

30
24.14
that the flame retardancy of the TPU-SPS coated fabric was improved
2810.45
3000 relative to the coated samples without flame retardants (TPU-AP-AF
W T R V /[g /(m 2 2 4 h )]

20

2361.25 and TPU-AP-SF-AF). This can be seen in the damaged length and char
2500 10 2258.11
residue length (Figure 7D-F). Comparisons between the AF-AF and
WTRV/[g/(m224h)]

2000 the TPU-AP-SF-FR-AF samples indicate that the AF-AF samples had
0
AF-AF
longer after-flame time and longer char lengths while the TPU-AP-SF-
1500 FR-AF samples had lower LOI values. The presence of aluminum oxide
1179.57
film in the surface of aluminum foil increases the LOI value since the
1000
aluminum oxide film acted as a physical barrier against the flame.
500 However, once flame combustion occurred, the flammability of alumi-
num foil would accelerate burning of the fabric sample. TPU-AP-AF
24.14
0 had longer damage length than AF/AF. TPU-AP-SF-AF had longer
AF AF-AF TPU-AP-AF TPU-AP-SF-AF TPU-AP-SF-FR-AF
char length than AF-AF and TPU-AP-AF. At the same time, no fabric
FIGURE 6 WVTR values of fabric samples (Error bar) samples exhibited dripping during the testing.
The MCC is an effective micro scale testing method for evaluating
the combustion properties and the fire hazard of a polymer material.
3.3 | Flame retardant properties and burning These parameters are used to characterize the flammability properties
performance such as the peak heat release rate (pHRR), total heat release (THR),
temperature at pHRR (Tmax) and heat release capacity (HRC). All these
Table 2 gives the basic data for LOI values and VBT properties of all data are listed in Table 3. The heat release rate (HRR) curves of all fab-
the tested fabrics. The AF-AF sample had the highest LOI value of ric samples are also shown in Figure 8. The coated fabrics with intu-
32.6, which is 4.5 higher than that of the pure aramid fabric (28.1). mescent flame retardants (TPU-AP-SF-FR-AF) showed decreased
Except for the TPU-AP-SF-AF sample, the VBT values of other four pHRR values relative to the coated fabric without flame retardants
fabrics meet the standard requirements of GA634-2015 (China) fire- (TPU-AP-AF and TPU-AP-SF-AF) and the aluminum foiled aramid
ZHU AND FENG 7

TABLE 2 Flame retardant performance treated and untreated aramid fabrics

Vertical burning

After flame After glow Damage Char residue Surgical cotton

Sample No. LOI/% time/s time/s length/mm length/mm burning status
AF 28.1 1.52 0.9 25 34 Not ignited
AF-AF 32.6 1.23 0 73 72 Not ignited
TPU-AP-AF 26.2 0.98 0.23 81 72 Not ignited
TPU-AP-SF-AF 26.4 1.12 0.38 105 98 Not ignited
TPU-AP-SF-FR-AF 30.2 0.87 0.26 46 46 Not ignited
GA634-2015(China) - ≤2 ≤2 ≤100 - Not ignited
ISO 15538:2001 - ≤2 ≤2 - - Not ignited

F I G U R E 7 The images of the fabric samples after ignition in VBTs. (A, AF; B, the back side of AF-AF; C, the front side of AF-AF; D, TPU-AP-
AF; E, TPU-AP-SF-AF; F, TPU-AP-SF-FR-AF)

T A B L E 3 The MCC data of the pure

Sample No. HRC/[J(g K)−1] pHRR/(W g−1) THR/(kJ g−1) Tmax/
C
and treated samples
AF 68 65.76 11.4 465.9
AF-AF 89 86.03 12.9 436.0
TPU-AP-AF 54 45.75 13.2 372.3
TPU-AP-SF-AF 95 90.34 14.7 399.5
TPU-AP-SF-FR-AF 45 33.09 9.0 373.7

fabric (AF-AF). The total heat release from the TPU-AP-SF-FR-AF
sample was 38.8% less than that of TPU-AP-SF-AF sample. The pHRR
and THR values were important parameters as characterizing the
flammability of materials. The results indicate that the addition of the
intumescent flame retardant improved the flame retardancy of the
material. The HRR curve of the pure aramid fabric (AF), shared an analo-
gous shape with the AF-AF over the temperature range of 400
C to
750
C, and the major heat release happened between 410
C and
520
C (Figure 8). By contrast, the AF sample showed no heat release
rate peaks below 400
C (Figure 8). This was attributed to the thermal
8 ZHU AND FENG

decomposition of the aluminum elements within these aluminized fab-
rics at the early stage. It can be also found that silk fibroin exerted an
influence on the flammability performance. For example, the pHRR and
THR values of TPU-AP-SF-AF sample increased to 90.34w/g and
14.7 kJ/g and were increased by about 100% and 11% in contrast with
those of the treated fabric without silk fibroin (TPU-AP-AF), respec-
tively. The antagonistic effect of silk fibroin on flame retardancy demon-
strates that it is necessary to add more FR compounds into the
composite coating to weaken the effect. Simultaneously, it can be
observed from Table 3 that the AF and AF-AF samples reached higher
Tmax, which indicated the coating provided better thermal protection.
3.4 | Thermal stability
The thermal stability of the uncoated and coated aramid fabrics was
evaluated by using a heating rate of 10
C/min under nitrogen
100
Heatrelease rate (W • g−1)
atmosphere in a TGA (Thermogravimetric analysis), as shown in
Figure 9. The weight loss for all fabric samples was around 3 wt%
below 100
C, which was caused by evaporating adsorbed water from
the fabrics. The process of mass loss in the degradation of uncoated
aramid fabric was divided into three steps.21 It indicated that the ini-
tial degradation temperature of the uncoated aramid fabric was the
highest. More specially, the initial decomposition temperature of the
uncoated AF sample was about 425
C. This temperature was lower
temperature for the TPU-AP-AF samples, the TPU-AP-SF-AF samples
and TPU-AP-SF-FR-AF samples, 290
C, 210
C and 220
C, respec-
tively. The degradation of silk fibroin (SF) occurred at a lower temper-
ature which resulted in a lower onset temperature of the thermal
decomposition.22 The first decomposition peak temperature was
about 210
C for the coated samples doped with silk fibroin powder
(dash line a). The weight loss in the range of 230 to 280
C (Figure 9B,
region b) for the TPU-AP-SF-FR-AF sample was mostly due to the
decomposition of APP and the elimination of phosphoric acid, ammo-
nia and moisture content. Another peak at 360
C for the TPU-AP-AF
sample, and 380
C for the TPU-AP-SF-AF sample and 365
C for the
TPU-AP-SF-FR-AF sample was believed to be the decomposition of
TPU. At 800
C, the char residue indicated that the addition of
APP/MEL/PER intumescent system into the coated fabric enhanced

AF
80 AF-AF
TPU-AP-AF
the flame retarded performance of aluminized aramid fabric.
TPU-AP-SF-AF
TPU-AP-SF-AF

60
3.5 | Spectral radiative reflectance

40
The Wien's displacement law can be obtained from Planck's law,
which can be expressed as follows

20
λm  T = b ð1Þ

0 The Wien's displacement law can tell where the peak of the radia-
0 100 200 300 400 500 600 700 800 900
Temperature/°C tion curve falls and the peak wavelength λm at which the maximum
emittance occurs in terms of the absolute temperature T. In the for-
FIGURE 8 The HRR curves of pure and treated fabrics mula, b is a Wien's displacement constant, equal to 2.898 x 103K μm.

FIGURE 9 TG A, and DTG B, curves of uncoated and coated fabrics under nitrogen atmosphere
ZHU AND FENG 9

Therefore, knowing the temperature of the radiant source allows the
selection of the most suitable spectral region for analysis.
Common aluminum foil thermal insulation clothes have high tem-
perature resistance as high as 886-1600
C. According to Wien's law
of displacement (Equation (1)), the corresponding wavelength range of
thermal radiation in this temperature environment is about 1574 to
2500 nm. We know that the central temperature of some large-scale
thermal disaster environments is higher than 1600
C. Therefore, as a
whole, the thermal protection of flame-retardant and heat-insulating
fabrics for the thermal environment is mainly aimed at the protection
of near infrared radiation (1547-2500 nm) from heat sources at higher
temperature.
The spectral reflectance curves of all fabrics are shown in
Figure 10 for the temperature range of 886-1600
C (1547-2500 nm)
which is common in high temperature thermal environment. From
Figure 10, it can be seen that the spectral reflectance curves of
aluminum-coated AF and aluminum-foiled AF sample followed a simi-
lar trend. The reflectivity of aluminum-coated AFs (TPU-AP-AF, TPU-
AP-SF-AF, and TPU-AP-SF-FR-AF) were much higher than that of
pure AF and were slightly lower than that of AF-AF in the evaluated
spectral range. The surface of aluminum foil was compact and smooth,
and provided high levels of reflectance to radiant heat flux (Figure 10).
The addition of silk fibroin and flame retardant in the coating solution
can reduce the reflectivity of the coated fabrics to a certain extent.
This may be due to the insufficient dissolution or uneven distribution
of silk fibroin and flame retardant particles during the preparation of
the solution. But as a whole, the reflectivity of the coated fabrics was
above 70% in the spectral range of 1547 to 2500 nm, which meant a
large amount of radiation heat was reflected ultimately, protecting
against thermal radiation under high heat flux exposures.
In addition, combined with the equilibrium Equation (2) on radia-
tive heat transfer, Equations (3) and (4) can be gradually derived
Q = Qr + Qα + Qd ð2Þ
Qr Qα Qd
1= + + ð3Þ
Q Q Q
1=r+α+τ ð4Þ
Where r-reflectivity; α-absorptivity; τ-transmittance.
The reflectivities of the coated AF fabrics were higher than those
of pure AF sample. The combinations of transmittance and absorptiv-
ity of coated AF samples were lower than those of AF fabrics. There-
fore, the application of flame retardant aluminum coated fabrics as
the outer layer of a fire proximity suit can effectively reflect the radi-

100
ant heat to the environment. This would reduce the external heat
AF
AF-AF transmitted to the skin, and decrease the probability of heat stress.
TPU-AP-AF
90 TPU-AP-SF-AF
TPU-AP-SF-FR-AF

80 3.6 | Radiant protective performance (RPP)

Reflectance%

70
The RPP test uses a bank of quartz lamps as the thermal radiation
source with different levels of heat flux. Therefore, the RPP tester can
60
provide a more realistic test environment when compared with UV-

50
Vis-NIR spectrophotometer. In the absence of an air layer, the test
results from radiant protective performance test for all fabric samples
40 used in the TRPC outer material are listed in Table 4. It can be seen
1547-2500nm that the thermal protection coefficient of the coated aramid fabrics
30 (TPU-AP-AF, TPU-AP-SF-AF and TPU-AP-SF-FR-AF) were higher
800 1000 1200 1400 1600 1800 2000 2200 2400
than that of the pure AF sample. The measured protection level char-
Wavelength (nm)
acterized by the thermal protection coefficient varied from
FIGURE 10 The comparison of spectral reflectance for tested 32.03 kW s m−2 to 52.34 kW s m−2 for these fabrics. No prediction
samples of a second damage burn on the skin underneath these fabric samples

TABLE 4 Testing results in RPP approach

Thermal protection Temperature rise of Time to first Time to second Variation of burn
Sample No. coefficient/(kwsm−2) Calorimeter(
C) skin burn (s) skin bun(s) temperature, 4T
AF 32.03 3.7 16.75 - 7.2
AF-AF - 0 - - 1.4
TPU-AP-AF 49.66 4.3 29.75 - 4.3
TPU-AP-SF-AF 51.05 4.3 29.65 - 4.3
TPU-AP-SF-FR-AF 52.34 3.3 - - 3.3

Note: “-”denotes no prediction of skin burn or thermal protection coefficient within 30 s.

10
can be detected in thermal exposures of 30s. In the heat flux, expo-
sure of 21 kW/m2, degradation or damage was observed for all fabrics
tested. Sample AF-AF, presented the best thermal insulated perfor-
mance. No first and second skin burn predictions were reported for
sample AF within 30s. Even so, it is worth bearing in mind that the
TPU-AP series samples (TPU-AP-AF, TPU-AP-SF-AF and TPU-AP-SF-
FR-AF) presented excellent thermal protection capacity. For example,
as compared to the pure aramid fabric, the thermal protection coeffi-
cient of TPU-AP-SF-FR-AF sample increased by 63.40%, and the vari-
ation of burn temperature was 3.9
C lower at 30 seconds (ending of
the test).
4 | C O N CL U S I O N S
In conclusion, we have reported the first fabrication of aluminized ara-
mid fabric through wet-coating an aluminum paste onto the fabric sur-
face to protect against high levels of radiant heat. Three coating
recipes were created and aluminum-coated samples were flame-
resistant and water vapor-permeable. The addition of APP-PER-MEL
into the coating system imparted an intumescent effect for flame ret-
ardancy observed in VBT, LOI, TG and MCC tests. Silk fibroin
enhanced the moisture transfer capacity in terms of not only the polar
group hydrophilicity but also by providing porous surface passage
structure which allowed water molecules, as seen in SEM analyzes.
However, the silk fibroin had a negative impact on the flame retardant
properties of the composite aramid fabric based on the VBT and MCC
data for TPU-AP-SF-AF sample. Compared with the pure aramid fab-
ric, the increased weight, lower WVTR and air permeability rates of
treated fabrics can slightly weaken the the comfort and performance
of the wearers. But, the aluminized AF sample with intumescent flame
retardants (TPU-AP-SF-FR-AF) meets the thermal comfort, flame
retardant and heat insulating standard requirements for the outer fab-
ric used in TRPC and other fire protective clothing. The integration of
hydrophilicity with flame retardancy in FR-aluminized fabric provides
a practical application in radiant thermal protection.
AKNOWLEDGEMENTS
This study was financially supported by the National Key Research
and Development Program of China (2017YFB0309001).
ORCID
FL Zhu https://orcid.org/0000-0002-6299-6005
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How to cite this article: Zhu F, Feng Q. Preparation, thermal
properties and permeabilities of aluminum-coated fabrics
destined for thermal radiation protective clothing. Fire and
Materials. 2020;1–10. https://doi.org/10.1002/fam.2883