Advanced Powder Technology xxx (xxxx) xxx

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Advanced Powder Technology

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

Original Research Paper

Phosphorus-containing silane modified steel slag waste to reduce fire

hazards of rigid polyurethane foams
Gang Tang a,b,⇑, Xinliang Liu a, Yadong Yang a, Depeng Chen a, Hao Zhang a, Lin Zhou b, Ping Zhang b,⇑,
Haohao Jiang a, Dan Deng c
a
School of Architecture and Civil Engineering, Anhui University of Technology, 59 Hudong Road, Ma’anshan 243002, Anhui, China
b
State Key Laboratory of Environment-friendly Energy Materials & School of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang 621010,
Sichuan, China
c
Department of Polymer Science and Engineering, Jiaxing University, Jiaxing 314001, Zhejiang, China

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

Article history: Steel slag (SS) waste was microencapsulated by a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-ox

Received 11 November 2019 ide (DOPO)-derived silane via sol–gel reaction to improve its compatibility with polymer as well as to
Received in revised form 5 January 2020 enhance flame retardant efficiency. The modified steel slag (mSS) was combined with expanded graphite
Accepted 14 January 2020
(EG) as flame retardant system for rigid polyurethane foams (RPUFs). The RPUF-3 sample with 10 wt%
Available online xxxx
mSS and 10 wt% EG showed an optimal comprehensive performance including a compressive strength
of 206.9 kPa, a thermal conductivity of 0.0304 W/(m
K), a limiting oxygen index (LOI) value of 24.0%
Keywords:
and UL-94 V-0 classification. The peak heat release rate (pHRR) and total heat release (THR) of the
Surface Modification
Steel slag
RPUF-3 dropped by 55% and 47%, respectively. By comparison, the RPUF-6 sample with 10 wt% SS and
Waste reutilization 10 wt% EG exhibited poorer flame-retardant behaviors. The superior flame retardancy of RPUF-3 over
Rigid polyurethane foams RPUF-6 could be ascribed to phosphorus-silicon complex in mSS promoted charring that provided better
Flame retardancy barrier effect during combustion.
Ó 2020 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Technology Japan. All rights reserved. All rights reserved.

1. Introduction inorganic oxides have been utilized as flame retardant fillers for
a wide variety of polymers [8–12]. Particularly, ferric oxide
Steel slag (SS) is a by-product of the steelmaking industries, (Fe2O3) is reported to promote charring ability through catalyze
which is estimated to be about 10–15 million tons annually gener- the crosslinking reactions during polymer degradation process
ated in the US [1]. Such a large amount of SS is considered as indus- [13]. As a mixture of these inorganic oxides, SS is anticipated to
trial waste and sent to landfill site eventually, which cause be a potential alternative to traditional flame-retardant fillers.
negative effect on the ecological environment. In order to explore However, the utilization of SS in flame retardant polymer applica-
the practical application of this industrial waste, tremendous effort tions is seldom reported until now.
has been made in various fields including ultra-high performance Rigid polyurethane foam (RPUF) is one kind of polymeric
concrete in construction industry [2–4] and absorbents in wastew- foamy material that combines low density, high specific strength,
ater treatment [5,6]. However, approximately 15 to 40% of the SS superior dimensional stability and low thermal conductivity [14–
output is still stockpiled [1]. It is thereby imperative to find new 16]. Given that RPUF possesses so many advantages, it has been
potential applications for SS, which could relieve the disposal of applied in a wide variety fields, especially used as thermal insu-
such huge amount of this industrial waste. lation materials in building energy conservation industry. RPUF
The main chemical components of SS are silica, calcium oxide, has a fatal disadvantage of high fire risk, however, which restricts
ferric oxide, aluminum oxide and manganese oxide [7]. These its applications. Owing to its organic and porous structure, RPUF
is easy to ignite with a very rapid flame spread rate, accompany-
ing with a large amount of toxic gases release (like hydrogen cya-
⇑ Corresponding authors at: School of Architecture and Civil Engineering, Anhui nide, nitric oxides, carbon monoxide, etc.) during combustion
University of Technology, 59 Hudong Road, Ma’anshan 243002, Anhui, China
[17]. This high fire risk of RPUF potentially threatens people’s
(G. Tang).
E-mail addresses: tanggang@ahut.edu.cn (G. Tang), pingzhang@swust.edu.cn
lives and properties when utilization, so it is essential to endow
(P. Zhang). RPUF with flame retardancy for fire safety applications. Until

https://doi.org/10.1016/j.apt.2020.01.019
0921-8831/Ó 2020 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved. All rights reserved.

Please cite this article as: G. Tang, X. Liu, Y. Yang et al., Phosphorus-containing silane modified steel slag waste to reduce fire hazards of rigid polyurethane
foams, Advanced Powder Technology, https://doi.org/10.1016/j.apt.2020.01.019
2 G. Tang et al. / Advanced Powder Technology xxx (xxxx) xxx

now, there are two major strategies to develop flame retardant 2.2. Synthesis of phosphorus-containing silane modified steel slag
RPUF: reactive-type and additive-type methods. The reactive- (mSS)
type method primarily represents preparation of RPUFs from
flame retardant precursor like phosphorus- and/or nitrogen- The phosphorus-containing silane (DOPO-VTES) was synthe-
containing polyols [17–19]. Although this method has advantages sized through the addition reaction between DOPO and VTES, as
of non-migration and high flame-retardant efficiency, it usually described elsewhere [35]. Typically, VTES (19.0 g, 0.1 mol) and
results in shrinkage during foaming process [20]. The additive- DOPO (21.6 g, 0.1 mol) were introduced into a 250 ml three-
type approach mainly involves physical mixing of various necked flask equipped with a magnetic stirrer and a reflux con-
flame-retardant fillers into RPUFs during foaming process. These denser and a nitrogen inlet. The mixture was heated to 80 °C until
flame-retardant fillers include expandable graphite (EG) [21], DOPO was completely dissolved. Then, AIBN (0.2 g) solution in
melamine polyphosphate [22], melamine cyanurate [22], and toluene (15 ml) was added dropwise during a period of 1 h. The
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)- reaction system was maintained at 80 °C for another 12 h, and
based derivative [23]. In addition, various combined additive- the solvent was subsequently removed by a rotary evaporator. A
type flame retardant systems including pentaerythritol phosphate light-yellow liquid product was obtained and dried in a vacuum
and EG [24], EG@aluminum hydroxide [25], phosphate esters and oven at 80 °C overnight.
EG [26], ammonium polyphosphate (APP) and EG [27], titanium Steel slag was modified by DOPO-VTES through a sol-gel reac-
dioxide modified EG and APP [28], montmorillonite, APP and tion. In detailed, ethanol (150 ml) and deionized water (50 ml)
triphenyl phosphate (TPP) [29], have also been developed for were charged into a 500 ml three-necked flask equipped with a
RPUFs with improved flame retardancy. However, high loading mechanical stirrer and condenser. The mixture was stirred for
of additive-type flame retardants is usually required to obtain sat- 10 min at 40 °C to obtain a uniform solution. Then, steel slag
isfactory flame retardant RPUF materials, which results in deteri- (50 g) and ammonia (25 wt%, 17 g) were added and stirred for
oration of physical–mechanical behaviors. It is thereby necessary another 15 min. DOPO-VTES (20 g) was subsequently added drop-
to explore new additive-type flame retardant systems for RPUFs wise to the mixture within 1 h. The mixture was kept at 40 °C for
with high efficiency. 6 h. After that, the mixture was cooled to room temperature, fil-
In our previous study [30], the co-addition of melamine tered, washed with water, and dried at 80 °C until constant weight.
pyrophosphate (MPP) and steel slag into RPUF showed higher The synthetic route of phosphorus-containing silane modified steel
limiting oxygen index (LOI) values and lower peak heat release slag is illustrated in Fig. 1. The amount of DOPO-VTES on steel slag
rate (pHRR) than the samples with single MPP or steel slag, but particles was calculated by (WmSS  WSS)/WmSS  100%, where WSS
they cannot meet the industrial flame-retardant standard such and WmSS is the weight of steel slag powder before and after mod-
as UL-94 burning tests. The objective of this work is to broaden ification, respectively. The amount of DOPO-VTES on steel slag par-
the application of steel slag wastes in the field of flame- ticles was determined to be approximately 14.7 wt%.
retardant polymeric materials. In order to improve the compati-
bility and flame-retardant efficiency, steel slag powder was mod-
2.3. Preparation of RPUF samples
ified with a phosphorus-containing silane. The phosphorus-
containing silane was selected for two reasons: (1) combination
The RPUF samples were fabricated by a free-rise approach fol-
of phosphorus and silicon could create flame-retardant synergism
lowed the receipt in Table 1. Taking RPUF-2 for example, LY-
[31,32]; (2) hydrolysis of silane has been widely applied for sur-
4110, TED, DBTDL, deionized water, silicone, TEOA, mSS powder
face modification of inorganic fillers [33,34]. The modified steel
and EG were vigorously stirred at 3000 rpm at room temperature
slag (mSS) powder was subsequently mixed with polyol, iso-
for 10 min to obtain a uniform mixture. PM-200 was then added
cyanate and/or EG to produce a series of flame retardant RPUF
into the mixture followed by vigorous mechanical stirring at
samples. The influence of mSS and EG loadings on the compres-
3000 rpm at room temperature for 15 s. The mixture was immedi-
sion strength, thermal stability and flame retardancy of RPUFs,
ately poured into an open mould and placed at 80 °C for 12 h to
especially the role of mSS in the flame-retardant mechanism,
complete the polymerization process. The proper size of the sam-
was studied.
ples was cut to meet various measurements. Other samples were
fabricated by a similar procedure just through changing the mSS
and/or EG contents.
2. Experimental

2.1. Materials 2.4. Characterization

Steel slag with specific surface area of 499.3 m2/kg and average Proton nuclear magnetic resonance (1H NMR) spectrum of
particle size of 6.73 lm was provided by Masteel Group Co., Ltd. DOPO-VTES was collected by a Bruker AV-III 400 spectrometer
(Maanshan, China) and its main components were summarized (Switzerland) at ambient temperature to characterize the chemical
in Table S1 (see supporting information). Azobisisobutyronitrile structure.
(AIBN, 99%), vinyltriethoxysilane (VTES, 97%), and DOPO (97%) Fourier transform infrared (FTIR) spectra of the un-modified
were provided by Aladdin Industrial Corporation (Shanghai, and modified SS powder were recorded by a ThermoFisher Nicolet
China). Toluene was purchased from Sinopharm Chemical Reagent 6700 FTIR spectrometer (USA) using KBr disc method to demon-
Co. Ltd. (Shanghai, China). Polyaryl polymethylene isocyanate strate the successful surface modification of SS. The scan range
(PM-200, NCO content: 30.2–32.0%, average functionality: 2.7), was set from 400 to 4000 cm1 and the scan number was 32 times.
polyether polyol (LY-4110, OH content: 430 mg KOH/g), Density of the RPUF samples was measured following the stan-
triethylene diamine (TED), dibutyltin dilaurate (DBTDL), silicone dard procedure of ASTM D 1622-2008. The average value from at
surfactant (dimethylsilicone oil, viscosity: 100 ± 8 mPa
s), and tri- least five tests was reported.
ethanolamine (TEOA) were industrial grade and supplied from The morphology of the un-modified and modified SS as well as
Lvyuan New Material Company (Nantong, China). Expanded gra- the RPUF samples was observed by a Hitachi SU8220 scanning
phite (EG) was purchased from Xingyuan Colloidal Graphite Co., electron microscope (SEM) (Japan), and the samples were pre-
Ltd. (Qingdao, China). coated with a conductive gold layer. The elemental mapping was

Please cite this article as: G. Tang, X. Liu, Y. Yang et al., Phosphorus-containing silane modified steel slag waste to reduce fire hazards of rigid polyurethane
foams, Advanced Powder Technology, https://doi.org/10.1016/j.apt.2020.01.019
 G. Tang et al. / Advanced Powder Technology xxx (xxxx) xxx 3

Fig. 1. Synthetic route of microencapsulated steel slag by phosphorus-containing silane modifier.

Table 1
Formulations of RPUF samples.

Samples RPUF RPUF-1 RPUF-2 RPUF-3 RPUF-4 RPUF-5 RPUF-6

LY-4110 (g) 100 100 100 100 100 100 100
A33 (g) 1 1 1 1 1 1 1
LC (g) 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Water (g) 2 2 2 2 2 2 2
Silicone (g) 2 2 2 2 2 2 2
TEOA (g) 3 3 3 3 3 3 3
PAPI (g) 135 135 135 135 135 135 135
EG (g) 0 60.9 40.6 30.5 20.3 0 30.5
mSS (g) 0 0 20.3 30.5 40.6 60.9 0
SS (g) 0 0 0 0 0 0 30.5

obtained from an Oxford Aztec X-Max 80 Energy dispersive X-ray SS were determined by BT-2001 laser diffraction particle size ana-
spectroscopy (EDS) (UK). lyzers (China).
The wetting property of the un-modified and modified SS was A XIATECH TC3000E thermal conductivity tester (China) was
assessed by a Solon SL200B Contact Angle System (China) at room employed to study the influence of mSS on the thermal conductiv-
temperature, and the volume of the water drop was 4 lL. For each ity of the RPUF composites following the standard procedure of
sample, at least six points were measured to obtain the average ASTM C1113-09. The size of the RPUF samples used was
value. The un-modified and modified SS powder were pressed into 100 mm  100 mm  10 mm. The average value from at least five
tablets before water contact angle test. specimens was reported.
In order to assess the feature of the powders, the average parti- In order to obtain the mechanical strength, compression prop-
cle size and specific surface area of the un-modified and modified erty of the RPUF samples was measured by an MTS CMT6104 elec-

Please cite this article as: G. Tang, X. Liu, Y. Yang et al., Phosphorus-containing silane modified steel slag waste to reduce fire hazards of rigid polyurethane
foams, Advanced Powder Technology, https://doi.org/10.1016/j.apt.2020.01.019
4 G. Tang et al. / Advanced Powder Technology xxx (xxxx) xxx

tromechanical universal testing machine (China) following the the band at 1633 cm1 is characteristic of portlandite [38]. The
standard procedure of GB/T 8813-2008. The sample dimension characteristic absorption bands at 1434, 873 and 708 cm1 are
used was 100 mm  100 mm  30 mm and the compression rate ascribed to the asymmetric stretching mode and bending mode
was 5 mm/min. The average value from at least five specimens was of carbonate group, respectively [39]. The bands at 1112 and
reported. 986 cm1 are attributable to the stretching vibrations of Si-O
Thermal degradation process of the RPUF samples was recorded [39]. Besides these characteristic bands, there are several new
by a TA Q5000 thermal analyzer (USA) under air atmosphere to bands that are observed in the mSS. These new absorption bands
investigate the influence of mSS on the thermal stability of the at 2930 and 2860 cm1 (stretching vibration of ACH2A),
RPUF composites. Approximately 5.0 mg of the sample was heated 1270 cm1 (P@O), 1130 (SiAOASi in ‘‘cage” siloxane) and
from ambient temperature to 750 °C with a linear heating rate of 1025 cm1 (SiAOASi in ‘‘branching” siloxane) indicate the success-
20 °C/min. ful modification of steel slag by DOPO-VTES.
The LOI measurement is regarded as one of the most popular SEM micrographs of the steel slag before and after DOPO-VTES
screening strategies in research and development of flame- modification are shown in Fig. 4a–d. The original steel slag displays
retardant polymer realm. The LOI value of the RPUF samples was aggregated particles with average diameter of several microns
measured on a JIANGNING HC-2 oxygen index meter (China) fol- (Fig. 4a), while these particles shows irregular shape with a rela-
lowing the standard procedure of ASTM D2863-2017a. The sample tively rough surface under higher magnification (Fig. 4b). By con-
dimension used was 100 mm  100 mm  10 mm. The average trast, the steel slag after DOPO-VTES modification exhibits
value from at least five specimens was reported. In detailed, the aggregated particles with lower average diameter (Fig. 4c), and
sample was vertically placed in a glass column with an oxygen/ni- the surface of the particles becomes smoother (Fig. 4d) owing to
trogen mixture flow. The LOI value is determined as the minimum the presence of the coating induced by the sol-gel reaction
oxygen concentration in the oxygen/nitrogen mixture when either between SS and DOPO-VTES. The average particle size and specific
the burning of material maintains for 3 min or the length of 5 cm of surface area of the SS and mSS (Table S3) also demonstrate that the
sample is consumed. The LOI value is calculated by Eq. (1): DOPO-VTES modification results in lower average diameter and
higher specific surface area of mSS powder. The wetting property
CO 2 of the steel slag before and after DOPO-VTES modification was also
LOI ¼  100% ð1Þ
CN2 þ CO2 evaluated by measuring the water contact angle (WCA). The origi-
The UL-94 measurement proposed by Underwriters Laborato- nal steel slag is highly hydrophilic, showing a WCA of 0° (inset in
ries has been widely applied to assess flame-retardant property Fig. 4a), whereas the modified steel slag exhibits a WCA of 96° (in-
of polymers. The vertical burning tests of the RPUF samples were set in Fig. 4c), indicating the formation of the hydrophobic surface.
performed on a JIANGNING CZF-4 chamber (China) following the This wetting property transformation is attributed to the formation
UL-94 standard procedure. The sample dimension used was of the coating which is composed of abundant hydrophobic struc-
150 mm  100 mm  13 mm. The average value from at least five tures like aromatic and polysiloxane groups after the sol-gel reac-
tion between SS and DOPO-VTES. The improved hydrophobic
specimens was reported. The sample is rated as V-0, V-1 or V-2
classification according to the criteria summarized in Table S2. property is favorable to enhance the affinity between the fillers
and the polymer matrix.
In order to determine the heat and smoke release behaviors
during burning of the RPUF samples, cone calorimeter tests were The influence of EG and mSS on the morphology of the resultant
RPUF was investigated by SEM. Fig. 5 gives the SEM micrographs of
performed on a MOTIS CCT cone calorimeter (China) following
the standard procedure of ISO 5660-1. The sample dimension used the RPUF samples. It can be found that the control RPUF exhibits a
closed cellular micro-structure with an average cell size of about
was 100 mm  100 mm  20 mm. Each specimen was wrapped in
an aluminum foil and exposed horizontally to an external heat flux 200 lm (Fig. 5a). When incorporating EG, the shape of the cell does
not change significantly, but the cell size of RPUF-1 decreases to
of 50 kW/m2. The average value from at least three specimens was
reported. about 150 lm (Fig. 5b). With increasing the addition of mSS, the
reduced trend in the cell size becomes more obviously (Fig. 5c–f).
Raman spectra of the char residues of the RPUF samples after
cone calorimeter measurement were recorded by a LABRAM-HR The powdery flame retardant could serve as nuclei, hence, the cell
size of RPUF/mSS decreases dramatically [40]. The reduced cell size
confocal Raman microscope (France) with a laser at 514.5 nm to
investigate the graphitization degree of carbonaceous materials. means the increased cells that squeeze each other during foaming
process, resulting in some collapse of the cell walls for the RPUF
composite foams. When SS is combined with EG to replace mSS,
3. Results and discussion the RPUF-6 sample shows similar morphological feature to the
RPUF-3 sample (Fig. 5g). The elemental mapping was determined
The 1H NMR spectrum of DOPO-VTES is shown in Fig. 2. The sig- by the energy Dispersive X-ray analysis (EDX) spectra. The virgin
nals at 7.2–7.9 ppm (peak a) are assigned to the aromatic protons RPUF shows carbon, oxygen and nitrogen distributions within the
originated from DOPO species. The signals observed at 0.9 and selected region (Fig. S1). With incorporating EG, the RPUF-1 exhi-
2.1 ppm (peaks b and c) for the DOPO-VTES are attributed to the bits similar elements to the virgin RPUF (Fig. S2). In addition to car-
protons in Si-CH2 and P-CH2, respectively, indicating the successful bon, oxygen and nitrogen elements, the RPUF-3 also shows
addition reaction between DOPO and VTES. The signals at 3.7 and calcium, silicon, ferric, aluminum and phosphorus within the
1.2 ppm (peaks d and e) are ascribed to methylene and methyl selected region (Fig. S3). The calcium, silicon, ferric and aluminum
groups originated from VTES species. The proton signals corre- originate from the steel slag, whereas the phosphorus derives from
spond well with the previously reported values of the DOPO- the DOPO-VTES modifier. All these elements are distributed uni-
VTES [36,37], implying the successful synthesis of DOPO-VTES. formly throughout the cell walls indicating the mSS powder is well
FTIR spectra of the steel slag before and after DOPO-VTES mod- dispersed within the RPUFs.
ification are displayed in Fig. 3. The original steel slag shows the Physical-mechanical behaviors including density, compressive
characteristic absorption bands at 3432, 1633, 1434, 1112, 986, strength and thermal conductivity are crucial parameters for
873 and 708 cm1. The band at 3432 cm1 is assigned to the foamy polymeric materials. The corresponding data are listed in
stretching vibration of the hydroxyl group originated from Table 2. The apparent density of the virgin RPUF is measured to
the weakly absorbed water molecules on the slag surface, while be approximately 60.4 kg/m3. When adding 20 wt% EG, the density

Please cite this article as: G. Tang, X. Liu, Y. Yang et al., Phosphorus-containing silane modified steel slag waste to reduce fire hazards of rigid polyurethane
foams, Advanced Powder Technology, https://doi.org/10.1016/j.apt.2020.01.019
 G. Tang et al. / Advanced Powder Technology xxx (xxxx) xxx 5

Fig. 2. The 1H NMR spectrum of DOPO-VTES.

As seen from Table 2, the compressive stress at 10% strain of the

virgin RPUF is about 247.5 kPa, while the addition of 20 wt% EG sig-
nificantly increases the compressive stress at 10% strain of the
RPUF-1 to 630.6 kPa. Subsequently, the compressive stress at 10%
strain decreases gradually with increasing the mSS loading.
According to the Power law, the compressive strength is propor-
tional to the density of RPUFs [42]. The specific compressive
strength, derived from the ratio of compressive strength and den-
sity, is also used to assess the compression property. The specific
compressive strength of the virgin RPUF is 4.1 kN
m/kg. The addi-
tion of EG increases the specific compressive strength, while the
introduction of mSS decreases it as compared to that of the virgin
RPUF. This result could be attributed to the reduced cell size so that
the cells squeeze each other resulting in the cell collapse as
observed by SEM aforementioned. Furthermore, the specific com-
pressive strength of RPUF-3 is higher than that of RPUF-6, which
is attributable to the DOPO-VTES modification improves the com-
patibility between steel slag powder and RPUF matrix.
Thermal conductivity is one key factor for RPUF samples when
Fig. 3. FTIR spectra of the steel slag before and after DOPO-VTES modification.
applied as thermal insulation materials. As listed in Table 2, the
thermal conductivity value of the original RPUF is about
of the RPUF-1 obviously increases to be 95.6 kg/m3. Because the 0.0335 W/(m
K), which implied a good thermal insulation. The
apparent density of EG (approximately 200 kg/m3) is higher than thermal conductivity value of RPUF-1 is increased to be
that of the virgin RPUF, the incorporation of EG results in the 0.0367 W/(m
K), because its density is much higher than that of
increased density. Furthermore, partial substitution of EG by mSS the original RPUF. Generally, thermal conductivity of RPUFs is
decreases the apparent density of the resultant RPUF samples. It affected by foaming agent, foam density, cell size, and ratio of close
is found that the presence of mSS increases the expand ratio of to open cell [40]. With the addition of mSS, the density as well as
the RPUF samples during foaming process (Fig. S4), leading to a the cell size of RPUF-2, RPUF-3, RPUF-4 and RPUF-5 decreases grad-
decreased trend in the apparent density. With introducing ually, which is good for thermal insulation. That is why the thermal
20 wt% mSS, the density of the RPUF-5 greatly decreases to conductivity of RPUF-2, RPUF-3, RPUF-4 and RPUF-5 are lower than
be 37.5 kg/m3. For comparison, the density of the RPUF-6 is the unmodified RPUF. However, the density of RPUF-6 increases
50.5 kg/m3. This is because the DOPO-VTES modification induces when adding 20 wt% SS. Therefore, the thermal conductivity of
lower particle size of mSS compared to SS (Table S3), which func- RPUF-6 increases to be 0.0322 W/(m
K). The DOPO-VTES modifica-
tions more obvious ‘‘nucleating” effect, and thus causes much tion causes decreasing trend in density of the RPUF samples, which
lower density [41]. thereby accounts for the decreased thermal conductivity. Basically,

Please cite this article as: G. Tang, X. Liu, Y. Yang et al., Phosphorus-containing silane modified steel slag waste to reduce fire hazards of rigid polyurethane
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6 G. Tang et al. / Advanced Powder Technology xxx (xxxx) xxx

Fig. 4. SEM micrographs of (a, b) SS and (c, d) mSS under different magnifications, and the water contact angle images of SS (inset in Fig. 4a) and mSS (inset in Fig. 4c).

the optimal addition of EG and mSS does not deteriorate and even the unmodified RPUF shows a single and intense HRR peak with
exhibits better physical-mechanical property of RPUF. the value of 458 kW/m2. With addition of 20 wt% EG, the pHRR
The flame-retardant property of the RPUF samples was evalu- value of the RPUF-1 significantly decreases to 144 kW/m2, which
ated by the LOI and UL-94 results, as summarized in Table 3. Orig- is ascribed to that the barrier effect created by EG diminishes the
inal RPUF has a relatively low LOI value of 17.5%, indicating a combustion intensity of the matrix [27]. This result could be also
highly flammable material, which is also evidenced by no classifi- evidenced by the obviously prolonged burning time for the
cation in the UL-94 vertical burning test. This high flammability is RPUF-1. Furthermore, when the EG was partially replaced by the
attributable to the porous structure of RPUF which has larger con- mSS, the pHRR value increases gradually with increasing the mSS
tact surface to air when burning. The addition of 20 wt% EG into loading, suggesting the partial substitution of EG by mSS weakens
RPUF-1 increases the LOI value to 31.0% accompanying with a V- the barrier effect. By comparing the pHRR values between RPUF-6
0 classification in the UL-94 vertical burning test. The enhanced and RPUF-3, it can be found that mSS shows superior flame-
flame-retardant property of the RPUF-1 could be attributed to retardant efficiency over SS at the equivalent loading. This result
the expansion of the RPUF/EG formulation generates, on the sur- confirms that the phosphorus-based modifier in mSS could pro-
face, a protective layer which inhibit the flame spread effectively mote the charring ability of the matrix which strengthens the bar-
[43]. Partial replacement of EG by mSS leads to a decreased trend rier effect during combustion.
in the LOI value, and the LOI value of the RPUF-5 containing only Fig. 7 gives the THR as a function of burning time curves of the
20 wt% mSS is reduced to 20.0%. The RPUF-2 and RPUF-3 could still RPUF samples. The unmodified RPUF shows a THR value of
pass the UL-94V-0 classification, but the burnt length increases 39.5 MJ/m2, whereas this value of the RPUF-1 decreases to
(Fig. S5). With further increasing the mSS content, the RPUF-4 32.1 MJ/m2. When the EG was partially replaced by the mSS, the
and the RPUF-5 cannot pass the UL-94V-0 classification, and the THR value further decreases. Since THR represents the accumu-
flame burnt to the top of the samples (Fig. S5). By comparing lated amount of heat release during the whole burning process,
RPUF-6 with RPUF-3, it can be found that the mSS shows better the significantly prolonged burning time of RPUF-1 contributes to
flame-retardant effect in combination with EG than the un- higher THR compared to other flame retardant RPUF samples.
modified SS. Specifically, the THR value of RPUF-3 drops to 21.0 MJ/m2, nearly
In order to explore the influence of EG and mSS on the flame- a 47% reduction compared to that of the unmodified RPUF.
retardant property, cone calorimeter was utilized to investigate Smoke is another important parameter regarding the fire risk
combustion behaviors of the RPUF samples. Cone calorimeter could of polymeric materials which is major reason for casualties in
provide heat-related and smoke emission parameters including fire accidents [47,49,50]. The unmodified RPUF exhibits a TSP
time to ignition (tig), peak of heat release rate (pHRR), total heat value of 9.90 m2, while this value of the RPUF-1 dramatically
release (THR), total smoke production (TSP), time to pHRR (tPHRR), decreases to 2.25 m2, demonstrating good smoke suppression
etc [44–48]. Table 3 summarizes the detailed information about effect of EG. When EG and mSS are jointly added into RPUF,
these parameters. Fig. 6 gives the heat release rate (HRR) as a func- the TSP value begins to increase. This result could be attributed
tion of burning time curves of the RPUF samples. It can be seen that to that the addition of mSS or SS results in incomplete combus-
all the samples show a very low tig value (about 2 s), indicating the tion with the release of a large number of volatiles. Although the
easy ignition of the RPUF samples. The RPUF samples have porous presence of mSS or SS increases the TSP of RPUF samples, their
structure that is filled with air inside, so the samples have rela- TSP values are still lower than that of the unmodified RPUF.
tively high contact surface with air when burning. That is why The lower smoke emission is desirable as thermal insulating
the tig value for all the RPUF samples is very low. After ignition, materials.

Please cite this article as: G. Tang, X. Liu, Y. Yang et al., Phosphorus-containing silane modified steel slag waste to reduce fire hazards of rigid polyurethane
foams, Advanced Powder Technology, https://doi.org/10.1016/j.apt.2020.01.019
 G. Tang et al. / Advanced Powder Technology xxx (xxxx) xxx 7

Fig. 5. SEM micrographs of the fractured surfaces of (a) RPUF, (b) RPUF-1, (c) RPUF-2, (d) RPUF-3, (e) RPUF-4, (f) RPUF-5 and (g) RPUF-6.

Table 2
Density, compressive strength and thermal conductivity of control RPUF and flame-retardant RPUF samples.

Samples Density (kg/m3) Compressive strength (kPa) Specific compressive strength (kN
m/kg) Thermal conductivity (W/(m
K))
RPUF 60.4 247.5 4.1 0.0335
RPUF-1 95.6 630.6 6.6 0.0367
RPUF-2 57.0 269.9 4.7 0.0318
RPUF-3 45.0 206.9 4.6 0.0304
RPUF-4 43.5 167.6 3.9 0.0301
RPUF-5 37.5 145.1 3.9 0.0298
RPUF-6 50.5 192.2 3.8 0.0322

Please cite this article as: G. Tang, X. Liu, Y. Yang et al., Phosphorus-containing silane modified steel slag waste to reduce fire hazards of rigid polyurethane
foams, Advanced Powder Technology, https://doi.org/10.1016/j.apt.2020.01.019
8 G. Tang et al. / Advanced Powder Technology xxx (xxxx) xxx

Table 3
LOI values, UL-94 vertical burning behaviors and cone calorimeter data of control RPUF and flame-retardant RPUF samples.

Samples LOI (%) UL-94 tig (s) pHRR (kW/m2) THR (MJ/m2) TSP (m2) tPHRR (s) FIGRA
(kW/m2
s)
RPUF 17.5 NC* 2 458 39.5 9.90 11 41.6
RPUF-1 31.0 V-0 2 144 32.1 2.25 6 24.0
RPUF-2 26.5 V-0 2 175 25.2 2.84 5 35.0
RPUF-3 24.0 V-0 2 206 21.0 3.46 6 34.3
RPUF-4 23.0 NC 2 245 23.5 5.71 6 40.8
RPUF-5 20.0 NC 2 411 22.7 6.77 10 41.1
RPUF-6 23.0 NC 2 325 21.3 6.97 8 40.6

Note: NC: No Classification.

ing shape, and a lot of holes are dispersed on the surface that can-
not block the escape of flammable volatiles to feed flame
effectively. That is why the unmodified RPUF has so high pHRR
and THR values. From Fig. 8b, it can be seen that the RPUF-1 con-
taining 20 wt% EG presents a loose and worm-like expanded gra-
phite char residue. The residual char of the RPUF-2 in Fig. 8c
becomes intact and maintains the original dimensions of the
matrix owing to combination of EG and mSS, which facilitates to
retard the mass and the heat transfer between matrix and flame.
Such a residual char with similar structure is observed in the case
of the RPUF-3 (Fig. 8d). With further increasing the mSS loading,
the residual char of the RPUF-4 (Fig. 8e) shows a shrinking shape.
The residue of the RPUF-5 (Fig. 8f) is not very much, revealing that
the RPUF-5 burnt more completely. Such a char residue provides
poor barrier effect on fire, which accounts for higher pHRR value
during combustion.
TGA and differential TGA (DTG) thermograms of the RPUF sam-
ples are illustrated in Fig. 9 and the corresponding data are sum-
marized in Table 4. The thermal degradation process of the
Fig. 6. HRR as a function of burning time curves of the RPUF samples. unmodified RPUF is composed of two distinct stages: the first stage
in the temperature range from around 200 to 365 °C (correspond-
ing to about 50% mass loss) is assigned to the de-polymerization of
polyurethanes to generate polyols and isocyanates [53], while sec-
ond one in the temperature range from around 450 to 700 °C (cor-
responding to about 44% mass loss) is ascribed to further
degradation of polyols and isocyanates to form various low-
molecular compounds such as carbon oxides, alcohols, amines,
aldehydes [53]. At the end of the investigated temperature
(750 °C), only 0.8% residue remains, suggesting the poor thermal
oxidative resistance of the unmodified RPUF under air atmosphere.
With the addition of EG and/or mSS, the T-10% of the flame-
retardant RPUF composites is shifted to a lower temperature, and
the T-10% further decreases with increasing mSS loading. This phe-
nomenon is probably caused by the early degradation of EG and/or
mSS. However, the T-50% for the flame retardant RPUF composites
increases compared to that of the unmodified RPUF, meaning the
presence of EG and/or mSS could serve as barrier to delay the sec-
ond decomposition stage. For the flame retardant RPUF composites
containing EG, the third decomposition stage is observed which is
attributed to thermal oxidative degradation of the char residues.
Fig. 7. THR as a function of burning time curves of the RPUF samples. By contrast, there is no the third decomposition stage for the
RPUF-5 and RPUF-6, indicating good charring ability of EG. All
The fire growth rate (FIGRA) is a derivative parameter obtained the flame-retardant RPUF samples exhibit an increased residue
from the ratio between pHRR and tpHRR, which is generally used to yield at 750 °C in comparison to the original RPUF owing to good
quantitatively evaluate the building products reaction to fire prop- charring ability of EG and thermally stable inorganic metal oxides
erties [45,51,52]. The unmodified RPUF shows a high FIGRA value from steel slag. Additionally, from the TGA/DTG curves of the
of 41.6 kW/m2
s, as an indicative of high fire spread rate. As RPUF-3 and RPUF-6 (Fig. S6), it can be seen that both the T-10%
expected, all the flame retardant RPUF samples exhibit lower FIGRA and T-50% of the RPUF-3 decrease compared to those of the RPUF-
value than the unmodified RPUF. Specifically, the FIGRA value of 6, which is ascribed to the earlier degradation of phosphorus-
RPUF-3 drops to 34.3 kW/m2
s, suggesting much lower fire risk. containing modifier in mSS. Generally, the earlier degradation of
The digital photographs of the char residues of the RPUF sam- phosphorus-containing compounds triggers the charring process
ples after cone calorimeter measurements are shown in Fig. 8. immediately [52,54]. That is why the RPUF-3 can pass UL-94V-0
The char residue of the unmodified RPUF (Fig. 8a) shows a shrink- whereas the RPUF-6 cannot.

Please cite this article as: G. Tang, X. Liu, Y. Yang et al., Phosphorus-containing silane modified steel slag waste to reduce fire hazards of rigid polyurethane
foams, Advanced Powder Technology, https://doi.org/10.1016/j.apt.2020.01.019
 G. Tang et al. / Advanced Powder Technology xxx (xxxx) xxx 9

Fig. 8. The digital photographs of the char residues of (a) RPUF, (b) RPUF-1, (c) RPUF-2, (d) RPUF-3, (e) RPUF-4, and (d) RPUF-5.

The char quality is a crucial factor that affects the flame-

retardant property in the condensed phase. Raman spectrum is a
popular tool to investigate the structure of carbonaceous materials.
Fig. 10 gives the Raman spectra of the char residues of all the sam-
ples. It can be found that two predominant bands are observed for
all the samples in the investigated wavenumber range. The band
located at around 1590 cm1 is called G band, while the one
located at around 1360 cm1 is called D band. The G band is related
to the crystalline phase consisted of graphited carbon atoms, and
the D band is associated with the amorphous phase consisted of
disordered carbon atoms [49,55]. In general, the area ratio between
G band and D band (IG/ID) is employed to assess the graphitization
degree of carbonaceous materials. The IG/ID ratio follows the order
of RPUF-1 (0.334)  RPUF-3 (0.333) > RPUF (0.305) > RPUF-5
(0.246). Higher IG/ID ratio means better thermal resistance of the
char residues. The absence of EG in RPUF-5 causes poor char for-
mation ability that could be observed from the less amount of resi-
due (Fig. 8f), and most of the residue is inorganic species from steel
slag, which accounts for the lowest IG/ID ratio. By comparison, the
RPUF-1 and the RPUF-3 show higher IG/ID ratio than the RPUF,
implying higher content of graphitized carbons in the residues that
is beneficial to thermal oxidative resistance. That is why the RPUF-
1 and the RPUF-3 possess better fame retardancy in the LOI, UL-94
and cone calorimeter tests.

4. Conclusion

In this work, steel slag (SS) waste was microencapsulated by a

phosphorus-containing silane via sol-gel reaction to improve com-
patibility between steel slag and polymer matrix. The modified
steel slag (mSS) powder was subsequently mixed with polyol, iso-
cyanate and/or expanded graphite (EG) to produce a series of
flame-retardant rigid polyurethane foam (RPUF) samples. SEM
micrographs showed that the addition of mSS and/or EG decreased
the cell size of RPUF, owing to the nucleating effect of the powdery
flame-retardant additives. The influence of mSS and EG loadings on
the physical-mechanical behaviors of RPUFs was studied to explore
Fig. 9. (a) TGA and (b) DTG thermograms of the RPUF samples under air the optimal formulation. It was found that the RPUF-3 sample with
atmosphere. 10 wt% mSS and 10 wt% EG showed a density of 45.0 kg/m3, a com-

Please cite this article as: G. Tang, X. Liu, Y. Yang et al., Phosphorus-containing silane modified steel slag waste to reduce fire hazards of rigid polyurethane
foams, Advanced Powder Technology, https://doi.org/10.1016/j.apt.2020.01.019
10 G. Tang et al. / Advanced Powder Technology xxx (xxxx) xxx

Table 4
TGA and DTG data of original RPUF and flame-retardant RPUF samples.

Samples T-10% (oC) T-50% (oC) Tmax,1 (oC) Tmax,2 (oC) Tmax,3 (oC) Residues (%) at 750 °C
RPUF 271 369 326 566 / 0.8
RPUF-1 258 454 285 540 732 9.6
RPUF-2 248 445 397 543 719 10.5
RPUF-3 245 427 301 538 718 10.8
RPUF-4 241 448 291 534 696 11.6
RPUF-5 232 377 308 549 / 15.7
RPUF-6 270 429 307 560 / 6.5

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Please cite this article as: G. Tang, X. Liu, Y. Yang et al., Phosphorus-containing silane modified steel slag waste to reduce fire hazards of rigid polyurethane
foams, Advanced Powder Technology, https://doi.org/10.1016/j.apt.2020.01.019