Polymer Testing 75 (2019) 12–25

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Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Composites of rigid polyurethane foams and silica powder filler enhanced T

with ionic liquid
Sylwia Członkaa,*, Anna Strąkowskaa, Krzysztof Strzeleca, Agnė Kairytėb, Saulius Vaitkusb
a
Institute of Polymer & Dye Technology, Lodz University of Technology, Lodz, Poland
b
Vilnius Gediminas Technical University, Faculty of Civil Engineering, Institute of Building Materials, Laboratory of Thermal Insulating Materials and Acoustics, Linkmenu
st. 28, LT-08217, Vilnius, Lithuania

A B S T R A C T

Rigid polyurethane foams (RPUFs) were successfully modified with different weight ratios (0.5 wt%, 1 wt%, 2 wt%) of nanosilica and nanosilica suspension (na-
nosilica-enhanced with ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF6]). The resulting foams were evaluated by their processing
parameters, chemical structure (Fourier Transform Infrared Spectroscopy Analysis, FTIR), morphology (Scanning Electron Microscopy Analysis, SEM), mechanical
properties (compressive test, three-point bending test), viscoelastic behavior (Dynamic Mechanical Analysis, DMA), thermal property (Thermogravimetric Analysis,
TGA, thermal conductivity) and application properties (water absorption, dimensional stability). The results showed that the morphology of modified foams is
significantly affected by the type of the filler and filler content, which resulted in inhomogeneous, irregular, large cell shapes and further affected the physical and
mechanical properties of resulting materials. RPUFs modified with nanosilica suspension represent better mechanical and thermal properties comparing to the RPUFs
modified with pure nanosilica. The results showed that the best results were obtained for RPUFs modified with 1 wt% of nanosilica suspension. In comparison with
unfilled foam, compositions modified with 1 wt% of nanosilica suspension provide higher density (44 kg/m3), greater compression strength (258 kPa measured
parallel and 162 kPa measured perpendicular), and lower thermal conductivity (0.026 W/m·K). The results obtained in this study suggest that the introduction of
nanosilica and nanosilica suspension over a certain optimal level (such as 2 wt%) has a negative effect on the cell morphology, which leads to deterioration of
physico-mechanical properties of the modified foams.

1. Introduction montmorillonite to enhance several properties of RPUFs. The presence

Rigid polyurethane foams (RPUFs) are highly cross-linked, three-
dimensional polymers with closed-cell structure that account for about
23% of all polyurethane (PU) production [1]. Due to their good thermal
insulating properties, high resistance to weather conditions, good me-
chanical properties and low apparent density [1] they are commonly
used in industries such as construction, fridges, furniture or in the
production of thermal insulation materials [1–4]. RPUFs have become
one of the most diverse and widely used plastics with a continuously
increasing global market. The total value of the global RPUF market
amounts to 401 billion dollars and is expected to grow by 7% from 2018
to 2025 [5–7].
Beside the favorable properties of resulting materials, improving the
mechanical properties of RPUFs is the foundation for their further po-
tential applications. To successfully employ them in building applica-
tion, it is critical that foams be combined with other materials or ele-
ments that provide mechanical strength and low thermal conductivity.
A review of the related literature indicates that applying nanomaterials
contributes a better improvement to mechanical properties and heat
resistance [8–20]. Cao et al. [18] used an organically-modified
of nanoclay resulted in a reduction in cell size compared to a pristine
RPUF sample. In the nanocomposites RPUF which used high molecular
weight polyols, compressive strength was dropped by 650%, but Tg
increased by 6 °C. Widya and Macasko [9] incorporated montmor-
illonite-based organonanoclay into RPUFs at a clay loading of 1 wt %.
They observed a reduction of mean cell size and a decrease in the dif-
fusion of blowing agent. Dolomanova et al. [21] investigated PU foam
reinforced by single-walled carbon nanotube (SWNT) and multiwalled
carbon nanotube (MWNT). The observation showed that both nano-
tubes improved compressive strength and compressive modulus, but,
compared to SWNTs, MWNTs had a more remarkable improvement in
the morphology and mechanical properties of the nanocomposite RPUF.
This was because of the fact that MWNTs can interact with the matrix
material and be better dispersed, which in turn affects the nucleation
process and leads to a finer cell structure.
A good distribution of the filler in the polymer matrix increases the
interfacial interaction between the filler and polymer matrix leading to
an increase of the polymer composites properties [2,6]. However, lit-
erature review has shown that filler particles tend to agglomerate and
as a result, highly filled polymeric systems are characterized by high

*
Corresponding author.
E-mail address: sylwia.czlonka@edu.p.lodz.pl (S. Członka).

https://doi.org/10.1016/j.polymertesting.2019.01.021
Received 5 November 2018; Received in revised form 11 January 2019; Accepted 26 January 2019
Available online 28 January 2019
0142-9418/ © 2019 Published by Elsevier Ltd.
S. Członka et al. Polymer Testing 75 (2019) 12–25

Fig. 1. NS and NS suspension observed in magnification of 50.

viscosity, poor distribution of particles and nonuniformity of properties 2. Experimental

[22–25]. It was previously reported that the addition of ionic liquids
(ILs) into polymeric matrix improved mechanical, electrical property
and thermal stability of the polymer composite through superior dis-
persion of the filler phase inside the polymer matrix [26–29].
Ionic liquids are generally defined as salts with melting points below
100 °C [30,31]. The definition of ILs clearly distinguishes them from
other molten salts. Research on ILs has been one of the most rapidly
growing fields in chemistry and industry in recent years. This rapid
growth is mainly due to the many unique properties of ionic liquids
[32]. Their chemical and physical properties can be tuned for a wide
range of potential applications by varying the cations and anions. The
antielectrostatic properties of ILs have also been recognized [32].
Owing to their unique chemical structure, ILs have been used to im-
prove the dispersion of nanoparticles in polymers matrix [33,34].
Besides the use of ILs in different kind of polymeric matrix, up to
date, there have been no publications with researches carried out to
verify the improvement of physical and mechanical properties of RPUFs
with addition of nanosilica (NS) filler and ILs. Due to the unusual
characteristics, the ILs can act as a template for enhancing the NS or-
dering from the molecular stage through the hydrogen bonding of the
ILs anions with the hydroxyl groups on the NS surface and lead to
improved distribution of the filler in the polymer matrix. Therefore, the
aim of this research is to develop and test PU foams modified with NS
powder filler enhanced with ionic liquid. The influence of different
amount of NS and NS-enhanced with ionic liquid on chemical structure
(Fourier Transform Infrared Spectroscopy, FTIR), thermal properties
(Thermogravimetric Analysis, TGA), dynamic mechanical properties
(Dynamic Mechanical Analysis, DMA), physico-mechanical properties
(compression strength, three-point bending test, apparent density,
thermal conductivity, water absorption) and morphology of obtained
PU composites was examined in current work. The results obtained in
present work, indicate that the addition of NS enhanced with ILs in the
range of 0.5–2 wt% influences the morphology of analyzed foams and
consequently their further mechanical and thermal properties.
2.1. Materials and manufacturing
All RPUFs were synthesized from the same polyurethane-modified
polyisocyanurate rigid foam formulation based on petrochemical
components provided by Purinova Sp. z o.o. (IZOPIANOL 30/10/C and
PUROCYN B). This formulation was selected because its industrial re-
levance for the production of PU insulation ensures that the raw ma-
terials are available from a range of manufacturers at a competitive
cost.
• Izopianol 30/10/C (Purinova Sp. z o.o.) used in the reaction is a
fully formulated mixture containing a mixture of polyester polyol
(hydroxyl number ca. 230–250 mgKOH/g, functionality of 2), cat-
alyst (N,N-Dimethylcyclohexylamine), flame retardant (Tris(2-
chloro-1-methylethyl)phosphate) and chain extender (1,2-propane-
diol) [35].
• Purocyn B (Purinova Sp. z o. o.) used in the synthesis is a polymeric
diphenylmethane 4, 4’-diisocyanate (pMDI) containing 31 wt% of
free isocyanate groups [35].
• Nanosilica with a specific surface area of 380 m2/g (Aerosil 380,
Evonic Industries)
• Ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate,
[bmim][PF6] (Sigma Aldrich)
RPUFs were obtained with the free rise method at room temperature
from a two-component system by chemical foaming with CO2 as the
foaming agent produced by exothermic reaction of water and iso-
cyanate. Two series of modified RPUFs were prepared. One series of
RPUFs was reinforced with 0.5, 1 and 2 wt% of NS (Fig. 1a), while the
second series of RPUFs was reinforced with suspension of NS and ionic
liquid (NS suspension) (Fig. 1b). Unmodified RPUF, without filler, was
used as a reference foam. The foams were marked as F-0.5_NS, F-1_NS,
F-2_NS and F-0.5_NS + IL, F-1_NS + IL, F-2_NS + IL depending on the
presence of ionic liquid and NS content. The formulations of the RPUFs
are shown in Table 1.

Table 1
Foam formulations.
Sample codes Comments Mass content [by weight]

Izopianol 30/10/C Purocyn B NS NS enhanced with [bmim][PF6]

F-0 Reference foam (unfilled) 100 160 – –

F-0.5_NS Foam reinforced with 0.5 wt% of NS 100 160 0.5 –
F-1_NS Foam reinforced with 1 wt% of NS 100 160 1 –
F-2_NS Foam reinforced with 2 wt% of NS 100 160 2 –
F-0.5_NS + IL Foam reinforced with 0.5 wt% of NS suspension 100 160 – 0.5
F-1_NS + IL Foam reinforced with 1 wt% of NS suspension 100 160 – 1
F-2_NS + IL Foam reinforced with 2 wt% of NS suspension 100 160 – 2

13
S. Członka et al.
Fig. 2. Schematic procedure of synthesis of RPUFs.
RPUFs were synthesized as follow. NS was modified with 1-butyl-3-
methylimidazolium hexafluorophosphate [bmim][PF6] by mixing the
suspension in constant ratio (1:3) by weight of NS to [bmim][PF6] till a
white paste was obtained. The adequate amount of pure NS or NS
suspension was added to the Izopianol 30/10/C and the mixture
(component A) was homogenized with overhead stirrer at 600 RPM
under ambient conditions for approximately 60 s. Purocyn B (compo-
nent B) was added to the component A and the mixture was stirred for
10 s at a speed rate of 1800 RPM. Following the information provided
by the supplier the ingredients were mixed in the ratio of 100:160 (ratio
of component A to component B). Such prepared system was poured
into an open mould and allowed to expand freely in the vertical di-
rection. RPUFs were conditioned at room temperature for 24 h. After
this time, samples were cut with a band saw into appropriate shapes
(determined by obligatory standards) and their physico-mechanical
properties were investigated. A schematic figure of synthesis of RPUFs
is presented in Fig. 2.
2.2. Characterization techniques
The absolute viscosities of polyol and isocyanate were determined
corresponding to ASTM D2930 [36] (equivalent to ISO 2555 [37])
using a rotary Viscometer DVII+ (Brookfield, Germany). The torque of
samples was measured as a range of shear rate from 0.5 to 100 s−1 in
ambient temperature.
The chemical structure of RPUFs was determined by Fourier trans-
form infrared spectroscopy (FTIR). FTIR spectra were collected for the
wavelength range of 3500–400 cm−1 at a resolution of 4 cm−1 using a
Nicolet 6700 FTIR Spectrometer (Thermo Fisher Scientific, Germany).
FTIR was performed with a DGTS/KBr detector. Data processing was
performed using OMNIC 3.2 software developed by Thermo Scientific
Products (Thermo Fisher Scientific, Germany). The average of 64 in-
dividual scans were obtained and the average spectrum was presented.
The morphology and cell size distribution of foams were examined
from the cellular structure images of foam which were taken using
JEOL JSM-5500 LV scanning electron microscopy (JEOL Ltd., USA). All
microscopic observations were made in the high-vacuum mode and at
the accelerating voltage of 10 kV. The samples were scanned in the free
rising direction. The average pore diameters, walls thickness and pore
size distribution were calculated using ImageJ software (Media
Cybernetics Inc.).
The apparent density of foams was determined accordingly to ASTM
D1622 [38] (equivalent to ISO 845 [39]). The densities of 5 specimens
per sample were measured and averaged.
The compressive strength (σ10%) of foams was determined accord-
ingly to the ASTM D1621 [40] (equivalent to ISO 844) [41] using Zwick
Z100 Testing Machine (Zwick/Roell Group, Germany) with a load cell
of 2 kN and the speed of 2 mm min−1. Samples of the specified sizes
were cut with a band saw in direction perpendicular to the foam growth
direction. Then, the analyzed sample was placed between two plates
and the compression strength was measured as a ratio of load causing
10% deformation of sample cross-section in the parallel and perpen-
dicular direction to the square surface. The result was averaged of 5
measurements per each sample.
Three point bending test was carried out using Zwick Z100 Testing
Machine (Zwick/Roell Group, Germany) at room temperature,
14
Polymer Testing 75 (2019) 12–25
according to ASTM D7264 [42] (equivalent to ISO 178 [43]). The tested
samples were bent with testing speed 2 mm min−1. Obtained flexural
stress at break (εf) results for each sample were expressed as a mean
value. The average of 5 measurements per each type of composition was
accepted.
Dynamic mechanical analysis (DMA) was determined using ARES
Rheometer (TA Instruments, USA). Torsion geometry was used with
samples of thickness 2 mm. Measurements were examined in tempera-
ture range 20–250 °C at a heating rate of 10 °C min−1, using frequency
of 1 Hz and applied deformation at 0.1%.
The thermal properties of the synthesized composites were eval-
uated by TGA measurements performed using the STA 449 F1 Jupiter
Analyzer (Netzsch Group, Germany). About 10 mg of the sample was
placed in the TG pan and heated in argon atmosphere at a rate of 10 °C
min−1 up to 600 °C with the sample mass about 10 mg. The initial
decomposition temperatures, T10%, T50% and T80% of mass loss were
determined.
LaserComp 50 heat flow meter apparatus (HFMA, LaserComp Inc.,
USA) with a 2.5 cm × 2.5 cm size heat flow transducer was used to
measure the thermal conductivity of the samples. Both surfaces of the
samples were lightly sanded using a belt sander to create uniform
thickness specimens. The upper and lower plates of the HFMA instru-
ment were set at 12.5 °C and 37.5 °C, respectively, with a mean tem-
perature of 25 °C. Prior to testing the sample specimens, the instrument
was calibrated using a similar thermal conductivity reference sample to
improve the accuracy of the measurement.
Changes in the linear dimensions were looked into with accordance
to the ASTM D2126 [44] (equivalent to ISO 2796 [45]). The samples
were conditioned at the temperature of 70 °C and humidity of 70% for
14 days. Change in linear dimensions was calculated in % from equa-
tion (1).
Δl=((l-lo)/lo)∙100 (1)
where lo is length of sample before thermostating and l is length of
sample after thermostating. The average of 5 measurements per each
type of composition was reported.
Water absorption of the RPUFs was measured according to ASTM
D2842 [46], equivalent to ISO 2896 [47]. Samples were dried for 1 h at
80 °C and then weighed. The samples were immersed in distilled water
to a depth of 1 cm for 24 h. Afterwards, the samples were removed from
the water, held vertically for 10 s, the pendant drop was removed and
then blotted between dry filter paper (Fisher Scientific, USA) at 10 s and
weighed again. The average of 5 specimens was used.
3. Results and discussion
3.1. Impact of NS and NS suspension on PU mixture viscosity
The viscosity of the reactive mixture was measured first, since it is a
critical parameter affecting the foaming process [48]. Increased visc-
osity hinders bubble growth, yielding foams with lower cell size.
Table 2 shows the viscosity of the polyol mixture plus the additives and
fillers used in each formulation. The polyol premixes that contained NS
and NS suspension are characterized by an increase in their viscosity
with an increasing fillers content, as a result of the presence of NS
particles interacting with the polyether polyol through hydrogen
S. Członka et al. Polymer Testing 75 (2019) 12–25

Table 2
Dynamic viscosity and logarithmic plot of the fitting equations for polyol premixes.
Sample codes Dynamic viscosity η [mPa·s] Fitting equation Power law index (n) R2

0.5 RPM 5 RPM 10 RPM

[bmim][PF6] 710 328 316 y = −0.061 + 0.325 0.325 0.974

F-0 1000 592 586 y = −0.060 + 0.345 0.345 0.968
F-0.5_NS 2642 1229 1072 y = −0.060 + 0.320 0.32 0.978
F-1_NS 4256 1657 804 y = −0.058 + 0.312 0.312 0.969
F-2_NS 12500 3200 1214 y = −0.059 + 0.302 0.302 0.970
F-0.5_NS + IL 3980 1679 1072 y = −0.059 + 0.302 0.309 0.974
F-1_NS + IL 5769 2234 1254 y = −0.057 + 0.284 0.284 0.977
F-2_NS + IL 17900 3587 1755 y = −0.052 + 0.250 0.25 0.969

Fig. 3. a) Viscosity as a function of shear rate and b) log-log plot of the viscosity vs. the shear rate for the IL and selected polyol premixes.

bonding and van der Wall's interaction [49]. The effect of this higher-
viscosity formulation is increased by the addition of IL. The viscosity of
the polyol premixes containing IL is slightly higher than their NS-
modified RPUFs counterparts.
The rheological properties of the IL and representative polyol pre-
mixes are shown as the viscosity versus shear rate in Fig. 3a. In all
systems, the viscosity is generally reduced at increased shear rates. The
viscosity of the samples initially decreases sharply and then sig-
nificantly slower to reach a relatively stable value, due to the fact that
particles of liquids reach the best possible arrangement. Such phe-
nomenon is typical for non-Newtonian fluids with a pseudoplastic
nature and is quite often found in many previous works [50,51]. To
further analyse the data, graph of viscosity versus shear rate is con-
verted to log viscosity versus log shear rate form as shown in Fig. 3b.
From this graph, it can be seen that the curvatures of viscosity versus
shear rate can be made close to linear using this log-log format with
regression of 0.969–0.978. The power law index (n) was calculated
from the slopes. All results are presented in Table 2. For the systems
containing NS suspension, the power law index is lower than that of
their NS-modified system counterparts. It indicates that the effect of the
filler on the pseudoplasticity behavior becomes more significant for
systems modified with NS suspension, leading to the highly non-New-
tonian behavior.
3.2. The influence of NS and NS suspension on the maximum temperature
(Tmax) of the reaction mixture during the foaming process
As it is known, the reaction of synthesis of RPUFs is highly exo-
thermic. Large amount of heat is released in a short period of time
during the gelling and blowing reaction when most reactions occur
[52,53]. The rate of increase in temperature determines the activity of
reaction mixture, what is associated with the reactivity of the compo-
nents of the mixture. As shown in Table 3, the introduction of NS and
NS suspension into the PU system increases the activity of reaction
mixture which is confirmed by an increase in the Tmax during the
foaming process. The presence of the additional groups as a result of the
incorporation of the filler can lead to the exothermic reaction providing
more heat evaporated to the system, and consequently higher tem-
perature of the modified system compared to the F-0 foam. This effect is
most pronounced in the case of PU composites modified with NS sus-
pension. As compared to the F-0, the Tmax increases by about 30 °C with
the addition of 0.5 wt% of NS suspension. With further increase of the
concentration of the fillers, the Tmax during the foaming process de-
creases. It has been shown that during the synthesis of the foams the
viscosity of the system increased with addition of the fillers, thus a
reduction in the efficiency of the reaction may have occur. Basically,
analogue tendency has been observed by other authors in previous
works [54–56].
3.3. Foaming kinetics
The foaming process was determined by measuring the character-
istic processing times, such as cream, extension and tack-free time. The
results presented in Table 3 indicate a slight increase in cream and
extension time for the RPUFs containing NS and NS suspension in each
amount. This dependence is mostly related to the fact that well-dis-
persed filler in the reaction mixture acts as a nucleating agent in the
nucleation process and higher viscosity of the modified systems is ob-
served. It has been reported in previous works that higher viscosity has
a major impact on the growth of RPUFs and causes an increase in re-
action time by a few minutes [39]. Also, an increase of filler content
affects the kinetics of reaction and the phase separation. The rate of PU
polymerization during foaming and morphology development is slowed
down [40]. The addition of the filler into the system decreases the rate
of isocyanate conversion during the early stage reaction. Also, due to
the presence of the filler, a reduction of the mobility of the molecules
takes place [40], leading to prolonged cream and extension time
[57,58]. Compared to the F-0, composites modified with the addition of
the fillers are also characterized by a shorter tack-free time, indicating
that filler particles act as a curing accelerator. Among studied fillers the
highest values of extension time and tack-free time are determined for
NS suspension-modified composites. This suggests that chemical

15
S. Członka et al. Polymer Testing 75 (2019) 12–25

Table 3
Selected properties of RPUFs.
Sample codes Temperature [oC] Cream time [s] Extension time [s] Tack-free time [s] Cell size [μm] Wall thickness [μm] Apparent density [kg m−3]

F-0 109 43 ± 4 277 ± 10 341 ± 14 472 ± 10 62 ± 4 38 ± 1

F-0.5_NS 130 41 ± 2 312 ± 11 320 ± 12 390 ± 8 66 ± 2 40 ± 2
F-1_NS 127 46 ± 1 358 ± 12 265 ± 10 274 ± 7 68 ± 3 41 ± 1
F-2_NS 120 48 ± 2 370 ± 10 260 ± 12 209 ± 8 70 ± 2 43 ± 1
F-0.5_NS + IL 139 50 ± 2 332 ± 12 335 ± 15 364 ± 9 68 ± 5 42 ± 2
F-1_NS + IL 133 57 ± 4 360 ± 12 277 ± 14 320 ± 8 69 ± 4 44 ± 2
F-2_NS + IL 123 69 ± 3 384 ± 18 270 ± 16 184 ± 10 74 ± 4 40 ± 3

interactions between NS suspension and isocyanate proceed in different Table 4

manner comparing to pure NS filler, which is related to different che- Functional groups of RPUFs.
mical composition and particles size distribution of used fillers. Wavenumber [cm−1] Functional groups
The obtained results are in a good agreement with the processing
times of isocyanate functionalized kraft lignin-based PU foams reported 3200–3600 NeH
by Gómez-Fernández et al. [59], which foaming times prove that the 2268 N=C]O
1700–1750 C=O
use of particles in PU foam mixtures extends the reaction start time and 1590 NeH
slows formation of cellular structures. The same tendency was observed 1513 CH2
by Lee et al. [60]. It has been found that addition of carbon nanotubes 1408 C=C
(CNTs) up to 0.3 wt% into the water-blown PU system has a major 1303 NeC]NeN
1214 CeN
impact on the growth of foam and causes an increase in reaction time
1060 C=C, C]N
by a few minutes. 1015 BeF
1000 OeSieO
880 SieO
3.4. FTIR analysis 809 CeH
749 CeCeO

The FTIR spectra of RPUFs modified with NS and NS suspension are

shown in Fig. 4a and b, respectively. The characteristic bands of PU
Because of this, a decreased number of urethane links in the modified
foams are summarized in Table 4. The urethane moieties of RPUFs are
RPUFs can be observed. Moreover, the band of the carbonyl stretching
confirmed by the presence of the main characteristic absorption bands.
vibration shifted from 1700 to 1710 cm−1 gradually. The shift to a
They are well represented by the characteristic ν(C]O) vibration re-
higher wavenumber suggests that the incorporation of the fillers dis-
gion (1700–1770 cm−1) [61,62], ν(NeH) stretching vibration region
turbs the hydrogen bonding between NH and C]O. In addition, the
(3200–3600 cm−1) [63,64] and δ(NeH) bending vibration absorption
band intensity of residual isocyanate groups v(-N]C]O) at wave-
band at 1590 cm−1 [65]. The relative position of the main character-
number of 1720 cm−1 is increased by increasing the fillers content. This
istic bands for various functional groups in the modified foams is si-
increase may be attributed to the hydroxyl groups of NS which can alter
milar to that of the reference foams outcome. This indicates that the
the isocyanate index (RNCO/OH) defined as the number of moles of NCO
chemical structure of modified RPUFs stayed unchanged in the presence
groups of the isocyanate per OH mole of the polyol thus affecting the
of NS and NS suspension. By comparing the spectra, some changes are
consumption of NCO groups. In the case of RPUFs modified with NS and
observed only in the intensity of the characteristic bands, which were
NS suspension, OeSieO and SieO stretching vibrations appear at 1000
appointed from FTIR spectra of all tested materials.
and 880 cm−1, respectively, however the difference in the intensity of
In both cases, the band intensity of the carbonyl group v(C]O) from
the bands is not observed [66]. Moreover, in the composites spectra for
free urethane at wavenumber of 1720 cm−1 is reduced by increasing
the RPUFs modified with NS suspension it is possible to observe a signal
the content of NS and NS suspension. A possible explanation may be
at 1015 cm−1 corresponding to BeF stretching vibrations of [BF4]-
related to the fact that both fillers can induce a decrease in the re-
anions [9,30,31]. A wide band located at 1060 cm−1 has been assigned
activity of the components of their RPUFs since the OH groups of NS
to the overlapping of the imidazole ring C]C and C]N stretching vi-
chemically reacted with the part of the isocyanate, leaving less iso-
bration [9,30,31].
cyanate groups available for the reaction with the polyol component.

Fig. 4. FTIR spectra of RPUFs modified with a) NS and b) NS suspension.

16
S. Członka et al.
Table 5
Hydrogen bonding index (R) and phase separation degree (DPS) of RPUFs.
Sample codes
F-0 F-0.5_NS F-1_NS
R 1.57 1.61 1.58
DSP [%] 61 62 61
The hydrogen bonding index (R) and the content of rigid poly-
urethane segments may be used to calculate phase separation degree
(DSP) from the FTIR results [67]. The indicator (R) is analyzed based on
the intensity of the characteristic bands derived from the carbonyl
groups present in the urethane and urea formations. For this purpose, a
baseline for carbonyl vibration (1770–1630 cm−1) was determined.
The hydrogen bond ratio was calculated using equation (2).
R = (A1+A2)/(A3+A4)
where A1 and A2 are a range of bands corresponding to hydrogen
bonded carbonyl bonding in urea groups (1640-1686 cm−1) and ur-
ethane groups (1705-1724 cm−1), while A3 and A4 are a range of bands
corresponding to carbonyl not bound by hydrogen in urea groups
(1690-1702 cm−1) and urethane groups (1732-1760 cm−1). Based on
the hydrogen bonding index (R) value the phase separation degree
(DSP) parameter has been calculated from equation (3).
DSP = R/(R+1)
The data presented in Table 5 indicate that the introduction of NS
suspension resulted in the formation of more hydrogen bonds compared
to the RPUFs containing NS, while the phase separation degree remains
almost unchanged.
3.5. Morphology of RPUFs
The morphologies of the RPUFs are shown in Fig. 5, showing
polygon closed-cell structures with many windows. The values of the
cell size of the foams were statistically analyzed by means of ImageJ
software from SEM images and the median values are summarized in
Table 3.
As observed from the micrograph of the reference foam (Fig. 5a),
the cell size and cell distribution are nearly uniform and the foam
consists of closed cells with a negligible amount of cells with broken
walls.
Micrographs of the NS-modified RPUFs are shown in Fig. 5b–d. With
the addition of NS, the overall cell structure becomes more uniform, the
Fig. 5. Morphology of a) F-0, b) F-0.5_NS, c) F-1_NS, d) F-2_NS, e) F-0.5_NS + IL, f) F-1_NS + IL, g) F-2_NS + IL observed at the same magnification.
Polymer Testing 75 (2019) 12–25
F-2_NS F-0.5_NS + IL F-1_NS + IL F-2_NS + IL
1.56 1.64 1.65 1.62
61 62 62 62
cell walls become thinner and the number of broken cells is increased.
Higher content of open cells in the case of RPUFs modified with the
highest amount of NS can be connected with poor interfacial adhesion
between the filler surface and the polymer matrix, which promotes
earlier cell collapsing phenomena and increases a high possibility of
generating open pores [68]. Moreover, the possible interphase inter-
actions between NS and PU in cell struts disturbed formulation of stable
foam structure [69] which results in coalescence of crowded cells. A
(2)
similar trend is observed in the case of RPUFs modified with NS sus-
pension, as shown in Fig. 5e–g. In the case of Fig. 5e, the closed-cell
structure is well preserved, and the cell size is uniform. When the
contents of NS suspension exceed 1 wt%, damaged cells become visible.
The highest number of damaged cells is shown in Fig. 5g, which cor-
responds to the highest amount of NS suspension content. It could be
observed that the addition of NS suspension to PU matrix resulted in the
cells having more regular and less defective shapes and surfaces com-
paring to the RPUFs modified with pure NS. On the other hand, the
(3) microstructure of NS suspension-modified samples is similar to re-
ference sample which indicates that application of NS suspension en-
hances formulation of smaller and more regular PU cells. The disper-
sions of the particles of used fillers in RPUFs are presented in Fig. 6. It is
clearly visible that for both series of modified foams, NS particles are
attached to the cell wall. Some dots and projections also become de-
tectable in the cell void and a coarse surface can be seen in the cell
struts.
In comparison to the F-0, the modified RPUFs are characterized by a
wider cell size range and higher cell distribution frequency (Fig. 7). It is
also observed that the pore size decreases with increasing filler content
(Table 3), so it can be concluded that both NS and NS suspension have
an effect on reducing the cell size. This may be due to the increased
viscosity of the system after the fillers addition which restrains the
expansion of the cells. Moreover, the addition of the fillers can change
the nucleation mode from homogenous to heterogeneous and reduce
the nucleation energy, which in turn promotes the formation of large
numbers of small cells [68]. Comparing Fig. 7a with Fig. 7b, it is ob-
vious that incorporation of NS suspension resulted in smaller cells and
17
S. Członka et al. Polymer Testing 75 (2019) 12–25

Fig. 6. Morphology of a) F-0, b) F-2_NS and c) F-2_NS + IL observed at the same magnification.

more homogenous structure as compared to their NS-modified RPUFs Table 6

counterparts. In case of NS-modified RPUFs two populations of pores Thermal and mechanical properties of RPUFs.
can be distinguished: large ones with a diameter of about 800 nm and Sample codes Compressive Compressive Flexural strength Elongation
small ones which size is about 300 nm. In case of RPUFs modified with strength strength σf [MPa] εf [%]
NS suspension most pores are located in the range of 200–300 nm. Si- (parallel) (perpendicular)
milar observations were described by Zhang et al. [70], who in- σ10% [MPa] σ10% [MPa]
vestigated the impact of soy protein filler on PU foam morphology. F-0 160 ± 4 136 ± 6 0.87 ± 0.08 6.2 ± 2.0
Composite foams with 5, 10, 15 wt% filler had a cell size of 274, 239 F-0.5_NS 170 ± 2 142 ± 5 1.16 ± 0.05 6.1 ± 1.1
and 202 μm, respectively compared with 391 μm of unmodified foam. A F-1_NS 172 ± 4 130 ± 6 1.2 ± 0.05 6.2 ± 1.2
similar trend was also observed in the case of RPUFs, modified with F-2_NS 158 ± 3 110 ± 4 0.71 ± 0.04 6.5 ± 0.8
F-0.5_NS + IL 246 ± 5 158 ± 5 1.32 ± 0.06 5.8 ± 2.0
inorganic filler [71,72].
F-1_NS + IL 258 ± 8 162 ± 8 1.38 ± 0.06 5.6 ± 1.2
F-2_NS + IL 210 ± 7 128 ± 7 0.72 ± 0.05 7.2 ± 1.1
3.6. Apparent density

The apparent density values of all RPUFs are summarized in Table 3.
The apparent density of RPUFs is slightly increased by increasing the
content of NS and NS suspension. The apparent density is generally set
in the range of 40–44 kg m−3 in both cases. The increase of the ap-
parent density of RPUFs can be affected by at least two factors As
presented above, increasing content of the fillers in composites changed
the polymerization kinetics during foaming (see Table 3) and conse-
quently final volume of RPUFs. The viscosity of the mixture containing
used fillers is higher than the viscosity of the mixture for the F-0. As the
content of the fillers is increased, the viscosity of the mixtures con-
taining fillers is increased and the volume expansion is reduced during
the polymerization of reaction mixture. Moreover, it should be pointed
out that another factor affecting the density of RPUFs is higher density
of NS and NS suspension comparing to PU foam matrix. This resulted in
the increase of the apparent density of studied composites, what is also
in agreement with the results reported in the literature [73].
3.7. Compressive test
To examine the reinforcement effect of NS and NS suspension, the
compressive mechanical properties of RPUFs were measured in both the
parallel and perpendicular directions of the foam-rise (Table 6).
Typical stress-strain curves for RPUFs are shown in Fig. 8. It can be
seen that all of the RPUFs exhibit three stages of deformation in com-
pression (the linear elastic region on the stress-strain curve, the plateau
region and the densification region). The increase in brittleness caused
by the reinforcements determines a more abrupt transition from the
elastic region to the plateau, in contrast to the smooth transition ob-
served in the case of the unreinforced material. This is because of
stiffness effect of the used fillers. It can be thought that as a non-de-
formable filler embedded into the foam structure NS would act as a
defect, leading to the embrittlement of the cell walls [26].
In comparison to F-0, all samples exhibit a slight improvement in
the direction of foam-rise and significant improvement in the parallel
direction to the foam-rise, for compressive strength. The significant
improvement of compressive strength parallel to foam rise for the re-
inforced samples could be attributed to arise due to the possible
alignment of the NS particles with the foam-rise (in the direction of
shear forces). Given that the axial surface area of the reinforcing filler is
smaller than the longitudinal surface area, it is not surprising that the

Fig. 7. Cell size distributions of RPUFs modified with a) NS and b) NS suspension.

18
S. Członka et al.
Fig. 8. Compression behaviors of RPUFs modified with a) NS and b) NS suspension.
compressive strength parallel to foam rise was greater than perpendi-
cular to foam rise, simply due to this anisotropy and the more efficient
transfer of stress from matrix to filler.
RPUFs modified with NS suspension show better mechanical prop-
erties as compared to their NS counterparts, suggests that not only
apparent density but also chemical structure and foam morphology
have an effect on compressive strength. Such changes in the mechanical
properties of composite samples can be explained in terms of char-
acteristic features of their structure. The mechanical properties of the
foams depend on the overall porosity, the pore size and size distribu-
tion, as well as the properties of the material itself. As presented in
Fig. 5e–g, samples modified with NS suspension exhibit more homo-
genous structure and the pore size distribution is narrower and shifted
to lower sizes comparing to the RPUFs modified with pure NS.
The general trend for compressive strength of modified RPUFs is to
decrease with filler concentration. With increasing NS content, the
compressive strength of RPUFs in parallel to the foam rising decreases
from 172 to 158 MPa, whereas the compression strength of samples
modified with NS suspension decreases from 258 to 210 MPa. In both
cases, with increased filler content it could be observed that foam cell
structure is more distorted and distribution is less uniform. At this time
if there is an application of loading, bending and shrinkage of cell walls
occur and results in the development of micro cracks. Therefore, foam
strength extremely depends on the initiation of micro cracks and forces
on their growth [27]. So it can be explained with the decreasing of foam
compressive strength with crack initiation and growth.
Finally, the reason for the decreasing mechanical strength might be
that at high filling rate, it is difficult to gain uniform dispersion of
particles and polyol mixture. High tendency to aggregate filler particles,
noticeable in the structure, leads to a weakened interfacial adhesion
between the filler and effective active surface. In consequence, RPUFs
are characterized by microphase separation of the structure, which
leads to the failure of samples in an unexpected manner at random
locations in the samples [74]. Non-uniform concentration of the filler in
some regions is contributed to embrittlement effect of polymer struc-
tures, inhibiting the enhancement of mechanical properties of obtained
foams [75]. The same tendency, i.e. an increase in compressive strength
till 1 wt% of the nanofiller, was observed for multiwall carbon nano-
tubes composite foams, while with the further increase in the filler
amount, the value starts to decrease [76]. Verdejo et al. [77] confirmed
that the negative impact of the addition of carbon nanotubes (CNTs) on
the foam compressive mechanical properties was due to the changes in
foam microstructure which dominate over the reinforcing effect of the
CNTs at the very low loading fractions involved in their work (up to
0.2 wt%). Nazeran et al. [78] concluded that by increasing the content
of added silica aerogel to 5 wt%, the negative effects of silica aerogel
such as disruption of the formation of hydrogen bonds, disruption of the
reaction stoichiometry, probability of the agglomeration of
19
Polymer Testing 75 (2019) 12–25
nanoparticles due to the increase of viscosity and inappropriate dis-
tribution of nanoparticles were increased. Therefore, the nanoparticles
interaction with polyurethane macromolecules was decreased and the
mechanical properties were weakened.
Nevertheless, the NS suspension-modified foams obtained in this
study show apparent density values of 40–44 kg m−3 and compressive
strengths of 210–258 kPa, which are well in the range exhibited by
conventional commercial foams that present densities in the
15–130 kg m−3 range and compressive strength values in the range
200–220 kPa (RPUFs at a density of 40 kg m−3) [79,80]. Based on these
results, the foams modified with silica can potentially be used on an
industrial scale in the construction and packaging industries.
3.8. Three-point bending test
As presented in Table 6, incorporation of NS and NS suspension
affects the flexural strength (σf) of modified foams. Compared to the F-0
and RPUFs modified with pure NS, composites containing NS suspen-
sion exhibit a slight improvement of the σf. The value of σf for samples
F-0.5_NS + IL and F-1_NS + IL increases by 34% and 38% as compared
to the F-0 foam, however, the incorporation of NS suspension in the
amount of 2 wt% leads to a deterioration of σf. The value of σf decreases
by 20%, as a result of a greater elasticity, connected with the cellular
morphology of PU foams (see Fig. 5). Due to an uneven distribution of
the filler in the matrix and many clusters present in the structure of
modified materials, the mechanical properties of the resulting compo-
site are reduced.
As compared to the F-0, the incorporation of NS and NS suspension
reduces the elongation at break (εf) of RPUFs in all cases. The reason is
due to the presence of NS aggregates within the PU matrix, which may
act as defects during the tensile testing process and decrease εf of foam
composites. However, it should be pointed out that with increasing
content of the fillers, RPUFs exhibit extended range of εf as a result of
higher content of open cells and greater flexibility of the PU matrix. The
lack of reinforcing effect with incorporation of the filler was also ob-
served in previous studies [81,82].
3.9. Dynamic Mechanical Analysis
The dynamic mechanical behavior of RPUFs as a function of the
temperature is shown in Fig. 9. The results presented in Fig. 9a and b
and Table 7, indicate that the incorporation of the NS and NS suspen-
sion to the PU matrix affects the value of Tg, which corresponds to the
maximum value of the curve loss tangent (tanδ) versus temperature.
Compared to the RPUFs modified with NS, RPUFs containing NS sus-
pension are characterized by higher Tg, however, with increasing con-
tent of the filler, Tg value of modified RPUFs decreases from 161 to
155 °C. Wu et al. [83] have shown that the Tg of RPUFs reflects the
S. Członka et al. Polymer Testing 75 (2019) 12–25

Fig. 9. a), b) Tanδ and c), d) storage modulus as a function of temperature plotted for RPUFs modified with NS and NS suspension.

Table 7 compared to RPUFs modified with pure NS. It can be concluded that the
The results of thermogravimetric analysis of RPUFs. addition of NS suspension has significantly increased the E′ of PU and
Sample codes Tg [oC] T10 [oC] T50 [oC] T80 [oC]
consequently the stiffness of studied composites is also enhanced. This
is due to the presence of filler in PU matrix as well as higher viscosity of
F-0 143 255 345 488 the modified systems, which imposes serious limits on the mobility of
F-0.5_NS 141 243 332 508 polymer chains, affecting their higher stiffness. In both cases, with in-
F-1_NS 142 241 359 494
F-2_NS 129 240 321 468
creasing content of the fillers in PU matrix the value of E′ slightly de-
F-0.5_NS + IL 160 267 344 500 creases. This decrement in E′ is attributed to the beginning of a thermal
F-1_NS + IL 161 266 349 523 transition, which is associated with hard segments phase. The changes
F-2_NS + IL 155 261 344 475 observed around 100 °C are attributable to the presence of a high
concentration of hydrogen-bonded aromatic urethane groups in the
poly(ether-urethane) phase and hard-segment domains which act as
rigidity of the polymer matrix which is a function of the isocyanate
macroscopic cross links. The higher E’ for PU-0.5_NS and PU-
index, cross-link density and aromaticity level of the RPUF. Given that
0.5_NS + IL indicates more restricted mobility compared to the RPUFs
the isocyanate index has been held constant in this study, the decrease
with higher content of the fillers, thus, the introduction of the fillers
in the Tg must be a reflection of the decreased aromaticity and cross-link
over a certain optimal level, in this kind of RPUFs produces more
density due to the presence of the silica [84]. Silva et al. [85] stated that
flexible materials. Deterioration of dynamic-mechanical properties as a
the larger the concentration of the filler in polyurethane system, the
result of incorporation of the filler was also observed in previous works.
lower is the Tg, indicating that the presence of rice ask hush increases
Mosiewicki et al. [86] reported that the incorporation of the micro/
the chain mobility of the high cross-linked zones of the polymeric
nanocellulose (MNC) particles increased the storage modulus of PU
matrix, which is associated with larger fraction of free volume in the
foams for very small added percentages of MNC. Samples modified with
network due to lower interaction between the polymer chains. A similar
higher content of MNC (3 wt%) presented a lower tanδ peak than the
effect was noticed by Silva et al. [57] in the case of foams modified with
other samples what could be related to a more heterogeneous network
cellulose fibers. They stated that the cellulose fibers could induce a
that started to be revealed at this percentage. Silva et al. [87] reported
decrease in the reactivity of the components of their rigid polyurethane
that the addition of rice husk ash leads to samples with reduced storage
foams since the OH groups of cellulose chemically reacted with part of
modulus respect to the unfilled foam, mainly due to the relaxation of
the isocyanate, leaving less isocyanate groups available for the reaction
zones of higher cross-link density, but also to the decreasing level of
with the polyol component.
physical filler-matrix interactions developed in the system, as the result
In Fig. 9c and d, it is also notable that RPUFs modified with NS
of the increased viscosity of the reactive liquid mixture due to in-
suspension are characterized by higher storage modulus (E′) as
creasing additions of ash.

20
S. Członka et al.
Fig. 10. TGA curves for RPUFs modified with a) NS, b) NS suspension and DTG curves for RPUFs modified with c) NS, d) NS suspension.
3.10. Thermogravimetric Analysis
Thermogravimetric analysis was performed to investigate the effect
of the NS and NS suspension on the thermal behaviors of the RPUFs. As
shown from the degradation TGA curves in Fig. 10a–d, all of the sam-
ples have a narrow degradable temperature range around 300–400 °C.
The decomposition of all modified RPUFs consists of three stages.
The first step of decomposition is connected with dissociation of ur-
ethane bond at a temperature between 150 and 330 °C (corresponding
to the temperature at 10% of total weight losses) [88,89]. The second
step of the degradation of RPUFs occurs in the temperature between
330 and 400 °C and is ascribed to the decomposition of soft polyol
segments (corresponding to the temperature at 50% of total weight
losses) [90]. The third step of degradation, ascribed to the degradation
of the fragments generated during the second step, which corresponds
to loss of weight by about 80%, occurs at the temperature of 500 °C
[88,91].
It is possible to observe that the addition of the fillers influences the
thermal stability of the RPUFs (Table 7). Compared to the foams
modified with NS, the composites containing NS suspension are rela-
tively more thermally stable. The degradation stage of the RPUFs
modified with NS starts at 240–243 °C, while the composite foams
modified with NS suspension start to degrade at slightly higher tem-
peratures (261–267 °C). Furthermore, the temperature at which the rate
of degradation is the highest is increased for these composites, which
could indicate that the incorporation of NS suspension enhances the
thermal properties of the composites. In both cases, for the highest filler
content of 2 wt% one may observe deterioration of thermal properties.
The decrease can be ascribed to the poor dispersion of the filler and
nonhomogeneous microstructure of the sample with higher content of
open cells (see Fig. 5).
3.11. Thermal conductivity of RPUFs
One of the most important parameters of RPUFs is thermal con-
ductivity, which decides of their potential applicability as insulating
21
Polymer Testing 75 (2019) 12–25
materials [92]. Thermal conductivity of foams is governed by several
important factors, like walls thickness and apparent density, together
[53,93]. Total λ value consists of a radiative (λr), a gaseous (λg) and a
solid (λs) contribution. At room temperature, the radiative and gaseous
thermal conductivities could be negligible, thus the density dependence
of solid conductivity contributes to the total λ.
To investigate the effect of NS and NS suspension on RPUFs, thermal
conductivity was measured at ambient temperature. Fig. 11 displays the
variation in the thermal conductivities of NS and NS suspension mod-
ified RPUFs with different amounts of used fillers. In case of NS-mod-
ified RPUFs, the thermal conductivity slightly decreased with NS ad-
dition up to 1 wt% (approximately 3% reduction) but increased with
increasing amount of NS up to 2 wt%. In case of RPUFs modified with
NS suspension, the decrease in thermal conductivity for specific
amounts of NS suspension is similar to that observed for pure NS-
modified RPUFs, however, the amount of the decrease is different. The
thermal conductivity reduced approximately by 6% and 10% with the
addition of 0.5 wt% and 1 wt% of NS suspension, respectively. Thus, the
reduction in the thermal conductivity of RPUFs with 1 wt% of NS sus-
pension addition is significant as compared to F-0 and NS-modified
RPUFs.
The reduction in thermal conductivity of RPUFs is justified by the
influence of the filler on cell morphology of foam and the unique
properties of NS low thermal conductivity. As it was seen in mor-
phology images in previous sections (see Fig. 5), adding NS and NS
suspension in amount of 0.5 wt% to RPUFs led to the decrease of the
cell size and obtained more uniform cell structures. Since the radiant
heat transfer takes place through cell walls, a smaller cell size, reduces
heat transfer by radiation mechanism and therefore thermal con-
ductivity of RPUFs is reduced. Also, the particles of NS dispersed in cell
walls of PU matrix can act as a barrier to heat transfer and decrease the
thermal conductivity of RPUFs through the mechanism of conduction in
the solid phase since they have low thermal conductivity. Increasing the
content of the fillers in PU mixture up to 2 wt% resulted in increased
thermal conductivity. Higher λ can be ascribed to the decreased content
of closed-cells resulting in a higher gas phase conductivity. In addition,
S. Członka et al.
Fig. 11. Thermal conductivity as a function of the filler content measured for RPUFs modified with a) NS and b) NS suspension.
open cells allow air to enter the foam which has higher conductivity
(0.025 W m−1K−1)) than CO2 (0.015 W m−1K−1). The same tendency
has already been reported by Mosiwiecki et al. [93]. The authors
showed that the thermal conductivity of RPUFs based on the castor oil
increases as the wood flour concentration increases and explained that
behavior considering the relative increase of small and/or clustered-
small cells of the reinforced foams. Badri et al. [94] reported a com-
parable behavior in RPUFs reinforced with empty fruit bunch fibers.
Inclusion of untreated fibers ruptured the cellular structure, leading to a
higher rate of diffusion of CO2 and increased the conductivity.
3.12. Water absorption of RPUFs
To widen the characterization of application properties, the water
adsorption of RPUFs was measured. Water uptake depends mainly on
the cellular structure of foams as well as the hydrophobic nature of the
used fillers [95–97]. The presented water absorption kinetic curves of
RPUFs (Fig. 12) indicate that each series of modified foams exhibit si-
milar characteristic of water uptake. It should be pointed out that in the
first hours, the foams absorb the most water, while after 8 h the water
uptake rate is reduced in each case. The results presented in Fig. 12b
indicate that the RPUFs modified with NS suspension are characterized
by a lower water absorption as compared with F-0 and foams con-
taining pure NS (Fig. 12a). In both cases, with increasing content of NS
and NS suspension, foams absorbed more water, as a result of more
open structure. In this case, the cells are broken and are interconnected
to accommodate more amount of water. Thus, it can be concluded that
in this case the cellular morphology of RPUFs is the dominating factor
affecting water sorption of analyzed materials. Beside this dependence,
it should be pointed out that water absorption for all modified materials
Fig. 12. Water absorption curves of RPUFs modified with a) NS and b) NS suspension.
22
Polymer Testing 75 (2019) 12–25
is decreased in comparison with the reference foam what can be at-
tributed to the hydrophobic character of NS and ionic liquid [98] as
well as to the fact that the filler particles can act as a barrier, preventing
the penetration by water and leading to a limited water uptake by
modified foams. A similar trend of fillers, preventing the penetration by
water can be also found in previous works [54,56]. In this case, water
absorption is slightly higher, however, this result is still considered
satisfactory for the use of RPUFs as insulating materials and construc-
tion components [99].
3.13. Dimensional stability of RPUFs
The % linear changes in length, width and thickness after exposure
at 70 °C and 70% of humidity for up to 14 days for samples modified
with NS and NS suspension are presented in Fig. 13. The dimensional
stability of RPUFs indicates that the addition of both fillers resulted in
negligible changes of dimensional stability of the modified foams in
relation to the F-0. In all cases the variations in the sample's dimensions
after the special treatment are random and thus they can be attributed
mostly to experimental errors while measuring. According to industrial
standard, PU panels tested at 70 °C should have less than 3% of linear
change [100]. In each case, the dimensional stability of RPUFs is thus
still considered to be mild and within commercially acceptable limits
[100].
4. Conclusion
RPUFs were successfully reinforced using nanosilica (NS) and na-
nosilica enhanced with ionic liquid (NS suspension). The impact of NS
and NS suspension on chemical structure, thermal properties, dynamic
S. Członka et al.
Fig. 13. Dimensional stability of RPUFs modified with NS (a,b) and NS suspension (c,d) after exposure at 70 °C and 70% of humidity.
mechanical properties, physico-mechanical properties (compressive
strength, three-point bending test, apparent density), foaming para-
meters and morphology of RPUFs was examined. The presented results
indicate that the addition of NS and NS suspension in the range of
0.5–2 wt% influences the morphology of analyzed foams and conse-
quently their further mechanical and thermal properties. It was noticed
that RPUFs modified with NS suspension are characterized by smaller
and more regular polyurethane cells. This suggests better compatibility
between PU foam matrix and NS suspension, comparing to pure NS
filler. This results in significant improvement of physico-mechanical
properties and thermal stability of composites with NS suspension. For
example, compared to the NS-modified RPUFs, composition with 1 wt%
of the NS suspension showed greater compressive strength (258 kPa),
higher flexural strength (1.38 MPa), less water uptake (10.4% after
24 h) as well as lower thermal conductivity (0.026 W/m · K). The results
obtained in this study confirm that the addition of NS and NS suspen-
sion over a certain optimal level has a negative effect on the cell
morphology. The addition of both fillers in amount of 2 wt% led to
samples with reduced compression modulus, compressive strength,
thermal transitions and storage modulus respect to the RPUFs con-
taining 0.5 and 1 wt% of the fillers, mainly due to detrimental changes
induced by the fillers.
References
[1] S. Tan, T. Abraham, D. Ference, C.W. MacOsko, Rigid polyurethane foams from a
soybean oil-based Polyol, Polymer (Guildf) 52 (2011) 2840–2846, https://doi.org/
10.1016/j.polymer.2011.04.040.
[2] M.M.A. Nikje, M. Noruzian, S.T. Moghaddam, Investigation of Fe3O4/AEAP su-
permagnetic nanoparticles on the morphological, thermal and magnetite behavior
of polyurethane rigid foam nanocomposites, Polimery/Polymers 60 (2015) 26–32,
https://doi.org/10.14314/polimery.2015.026.
[3] H. Xie, W. Yang, A.C.Y. Yuen, C. Xie, J. Xie, H. Lu, et al., Study on flame retarded
flexible polyurethane foam/alumina aerogel composites with improved fire safety,
Chem. Eng. J. 311 (2017) 310–317, https://doi.org/10.1016/j.cej.2016.11.110.
[4] C. Yang, L. Fischer, S. Maranda, J. Worlitschek, Rigid polyurethane foams in-
corporated with phase change materials: a state-of-the-art review and future re-
search pathways, Energy Build. 87 (2015) 25–36, https://doi.org/10.1016/j.
23
Polymer Testing 75 (2019) 12–25
enbuild.2014.10.075.
[5] Polyurethane (PU) Market Analysis by Product (Rigid Foam, Flexible Foam,
Coatings, Adhesives & Sealants, Elastomers), by End-Use (Furniture & Interiors,
Construction, Electronics & Appliances, Automotive, Footwear, Packaging), &
Segment Forecasts, (2018) n.d. https://www.grandviewresearch.com/industry-
analysis/polyurethane-pu-market/request.
[6] Rigid Polyurethane Foam Market - Global Industry Analysis, Size, Share, Growth
Trends & Forecasts 2017 - 2025, PR Newswire, New York, 2017https://search.
proquest.com/docview/1966284809?rfr_id=info%3Axri%2Fsid%3Aprimo ,
Accessed date: 27 May 2018.
[7] Global Polyurethane (PU), Foam Market Trends, Analysis & Forecasts 2016-2024,
NASDAQ OMX’s News Release Distrib Channel, New York, 2016https://search.
proquest.com/docview/1793434616?rfr_id=info%3Axri%2Fsid%3Aprimo ,
Accessed date: 27 May 2018.
[8] D. Yan, L. Xu, C. Chen, J. Tang, X. Ji, Z. Li, Enhanced mechanical and thermal
properties of rigid polyurethane foam composites containing graphene nanosheets
and carbon nanotubes, Polym. Int. 61 (2012) 1107–1114, https://doi.org/10.1002/
pi.4188.
[9] T. Widya, C. Macosko, Nanoclay–modified rigid polyurethane foam, J. Macromol.
Sci. Part B Phys. 44 (2005) 897–908, https://doi.org/10.1080/
00222340500364809.
[10] M. Thirumal, D. Khastgir, N.K. Singha, B.S. Manjunath, Y.P. Naik, Effect of a na-
noclay on the mechanical, thermal and flame retardant properties of rigid poly-
urethane foam, J. Macromol. Sci. Part A Pure Appl. Chem. 46 (2009) 704–712,
https://doi.org/10.1080/10601320902939101.
[11] E. Ciecierska, M. Jurczyk-Kowalska, P. Bazarnik, M. Gloc, M. Kulesza, M. Kowalski,
et al., Flammability, mechanical properties and structure of rigid polyurethane
foams with different types of carbon reinforcing materials, Compos. Struct. 140
(2016) 67–76, https://doi.org/10.1016/j.compstruct.2015.12.022.
[12] N. Uthaman, A. Majeed, Pandurangan, Impact modification of polyoxymethylene
(POM), E-Polymers (2006) 1–9, https://doi.org/10.1002/pen.
[13] L. Madaleno, R. Pyrz, A. Crosky, L.R. Jensen, J.C.M. Rauhe, V. Dolomanova, et al.,
Processing and characterization of polyurethane nanocomposite foam reinforced
with montmorillonite–carbon nanotube hybrids, Compos. Part A Appl. Sci. Manuf.
44 (2013) 1–7, https://doi.org/10.1016/J.COMPOSITESA.2012.08.015.
[14] M. Thirumal, D. Khastgir, N.K. Singha, B.S. Manjunath, Y.P. Naik, Effect of a na-
noclay on the mechanical, thermal and flame retardant properties of rigid poly-
urethane foam, J. Macromol. Sci. Part A 46 (2009) 704–712, https://doi.org/10.
1080/10601320902939101.
[15] M. Modesti, A. Lorenzetti, S. Besco, Influence of nanofillers on thermal insulating
properties of polyurethane nanocomposites foams, Polym. Eng. Sci. 47 (2007)
1351–1358, https://doi.org/10.1002/pen.20819.
[16] V. Dolomanova, C.M.R. Jens, L.R. Jensen, R. Pyrz, A.B. Timmons, Mechanical
properties and morphology of nano-reinforced rigid PU foam, J. Cell. Plast. 47
(2011) 81–93, https://doi.org/10.1177/0021955X10392200.
[17] L. Zhang, M. Zhang, Y. Zhou, L. Hu, The study of mechanical behavior and flame
S. Członka et al.
retardancy of castor oil phosphate-based rigid polyurethane foam composites con-
taining expanded graphite and triethyl phosphate, Polym. Degrad. Stabil. 98 (2013)
2784–2794, https://doi.org/10.1016/J.POLYMDEGRADSTAB.2013.10.015.
[18] X. Cao, L. James Lee, T. Widya, C. Macosko, Polyurethane/clay nanocomposites
foams: processing, structure and properties, Polymer (Guildf) 46 (2005) 775–783,
https://doi.org/10.1016/J.POLYMER.2004.11.028.
[19] D. Cai, J. Jin, K. Yusoh, R. Rafiq, M. Song, High performance polyurethane/func-
tionalized graphene nanocomposites with improved mechanical and thermal
properties, Compos. Sci. Technol. 72 (2012) 702–707, https://doi.org/10.1016/J.
COMPSCITECH.2012.01.020.
[20] A. Nik Pauzi NNP, R. Majid, M.H. Dzulkifli, M.Y. Yahya, Development of rigid bio-
based polyurethane foam reinforced with nanoclay, Compos. B Eng. 67 (2014)
521–526, https://doi.org/10.1016/j.compositesb.2014.08.004.
[21] V. Dolomanova, J.C.M. Rauhe, L.R. Jensen, R. Pyrz, A.B. Timmons, Mechanical
properties and morphology of nano-reinforced rigid PU foam, J. Cell. Plast. 47
(2011) 81–93, https://doi.org/10.1177/0021955X10392200.
[22] R. Soltani, M. Dinari, G. Mohammadnezhad, Ultrasonic-assisted synthesis of novel
nanocomposite of poly(vinyl alcohol) and amino-modified MCM-41: a green ad-
sorbent for Cd(II) removal, Ultrason. Sonochem. 40 (2018) 533–542, https://doi.
org/10.1016/j.ultsonch.2017.07.045.
[23] G. Mohammadnezhad, M. Dinari, R. Soltani, Z. Bozorgmehr, Thermal and me-
chanical properties of novel nanocomposites from modified ordered mesoporous
carbon FDU-15 and poly(methyl methacrylate), Appl. Surf. Sci. 346 (2015)
182–188, https://doi.org/10.1016/J.APSUSC.2015.04.005.
[24] G. Mohammadnezhad, M. Dinari, R. Soltani, The preparation of modified boeh-
mite/PMMA nanocomposites by in situ polymerization and the assessment of their
capability for Cu2+ ion removal, New J. Chem. 40 (2016) 3612–3621, https://doi.
org/10.1039/C5NJ03109E.
[25] M. Dinari, G. Mohammadnezhad, R. Soltani, Fabrication of poly(methyl metha-
crylate)/silica KIT-6 nanocomposites via in situ polymerization approach and their
application for removal of Cu2+ from aqueous solution, RSC Adv. 6 (2016)
11419–11429, https://doi.org/10.1039/C5RA23500F.
[26] H.H. Le, A. Das, S. Basak, M. Tahir, S. Wießner, D. Fischer, et al., Effect of different
ionic liquids on the dispersion and phase selective wetting of carbon nanotubes in
rubber blends, Polymer (Guildf) 105 (2016) 284–297, https://doi.org/10.1016/J.
POLYMER.2016.10.045.
[27] K. Subramaniam, A. Das, F. Simon, G. Heinrich, Macromolecular nanotechnology
networking of ionic liquid modified CNTs in SSBR, Eur. Polym. J. 49 (2013)
345–352, https://doi.org/10.1016/j.eurpolymj.2012.10.023.
[28] K. Subramaniam, A. Das, D. Steinhauser, M. Klüppel, G. Heinrich, Macromolecular
Nanotechnology Effect of ionic liquid on dielectric, mechanical and dynamic me-
chanical properties of multi-walled carbon nanotubes/polychloroprene rubber
composites, Eur. Polym. J. 47 (2011) 2234–2243, https://doi.org/10.1016/j.
eurpolymj.2011.09.021.
[29] H.H. Le, A. Das, S. Basak, M. Tahir, S. Wießner, D. Fischer, et al., Effect of different
ionic liquids on the dispersion and phase selective wetting of carbon nanotubes in
rubber blends, Polymer (Guildf) 105 (2016) 284–297, https://doi.org/10.1016/j.
polymer.2016.10.045.
[30] P. Wasserscheid, T (Thomas) Welton, Wiley InterScience (Online Service). Ionic
Liquids in Synthesis, Wiley-VCH, 2008.
[31] R.D. Rogers, K.R. Seddon, Ionic liquids—solvents of the future? Science (80-) 302
(2003) 792–793.
[32] J. Pernak, A. Czepukowicz, R. Poźniak, New Ionic Liquids and Their
Antielectrostatic Properties, (2001), https://doi.org/10.1021/IE000689G.
[33] E. Marwanta, T. Mizumo, N. Nakamura, H. Ohno, Improved ionic conductivity of
nitrile rubber/ionic liquid composites, Polymer (Guildf) 46 (2005) 3795–3800,
https://doi.org/10.1016/J.POLYMER.2005.02.113.
[34] H. Kreyenschulte, S. Richter, T. Götze, D. Fischer, D. Steinhauser, M. Klüppel, et al.,
Interaction of 1-allyl-3-methyl-imidazolium chloride and carbon black and its in-
fluence on carbon black filled rubbers, Carbon N. Y. 50 (2012) 3649–3658, https://
doi.org/10.1016/J.CARBON.2012.03.037.
[35] Purinova, Producer Information n.d.:http://www.purinova.com/product_group,69,
Polyureth.
[36] ASTM D2930 - Standard Test Method for Low-Temperature Viscosity of Automatic
Transmission Fluids, Hydraulic Fluids, and Lubricants Using a Rotational
Viscometer n.d.
[37] ISO 2555 - Plastics - Resins in the Liquid State or as Emulsions or Dispersions -
Determination of Apparent Viscosity by the Brookfield Test Method n.d.
[38] ASTM D1622 - Standard Test Method for Apparent Density of Rigid Cellular Plastics
n.d.
[39] ISO 845 - Cellular Plastics and Rubbers - Determination of Apparent Density n.d.
[40] ASTM D1621 - Standard Test Method for Compressive Properties of Rigid Cellular
Plastics n.d.
[41] ISO 844 - Preview Rigid Cellular Plastics - Determination of Compression Properties
n.d.
[42] ASTM D7264 - Standard Test Method for Flexural Properties of Polymer Matrix
Composite Materials n.d.
[43] ISO 178 - Plastics - Determination of Flexural Properties n.d.
[44] ASTM D2126 - Standard Test Method for Response of Rigid Cellular Plastics to
Thermal and Humid Aging n.d.
[45] ISO 2796 - Cellular Plastics, Rigid - Test for Dimensional Stability n.d.
[46] ASTM D2842 - Standard Test Method for Water Absorption of Rigid Cellular Plastics
n.d.
[47] ISO 2896 - Rigid Cellular Plastics - Determination of Water Absorption n.d.
[48] A. Kairytė, S. Vaitkus, S. Vėjelis, G. Girskas, G. Balčiūnas, Rapeseed-based polyols
and paper production waste sludge in polyurethane foam: physical properties and
24
Polymer Testing 75 (2019) 12–25
their prediction models, Ind. Crop. Prod. 112 (2018) 119–129, https://doi.org/10.
1016/j.indcrop.2017.11.027.
[49] Najwa K, Amin M. Cellulose Nanocrystals Reinforced Thermoplastic Polyurethane
Nanocomposites n.d.
[50] M. Kuranska, A. Prociak, S. Michalowski, U. Cabulis, M. Kirpluks, Microcellulose as
a natural filler in polyurethane foams based on the biopolyol from rapeseed oil,
Polimery/Polymers 61 (2016) 625–632, https://doi.org/10.14314/polimery.2016.
625.
[51] D. Yan, L. Xu, C. Chen, J. Tang, X. Ji, Z. Li, Enhanced mechanical and thermal
properties of rigid polyurethane foam composites containing graphene nanosheets
and carbon nanotubes, Polym. Int. 61 (2012) 1107–1114, https://doi.org/10.1002/
pi.4188.
[52] H. Al-Moameri, Y. Zhao, R. Ghoreishi, G.J. Suppes, Simulation blowing agent per-
formance, cell morphology, and cell pressure in rigid polyurethane foams, Ind. Eng.
Chem. Res. 55 (2016) 2336–2344, https://doi.org/10.1021/acs.iecr.5b04711.
[53] H. Fan, A. Tekeei, G.J. Suppes, F.-H. Hsieh, Rigid polyurethane foams made from
high viscosity soy-polyols, J. Appl. Polym. Sci. 127 (2013) 1623–1629, https://doi.
org/10.1002/app.37508.
[54] S. Członka, M.F. Bertino, K. Strzelec, Rigid polyurethane foams reinforced with
industrial potato protein, Polym. Test. 68 (2018) 135–145, https://doi.org/10.
1016/j.polymertesting.2018.04.006.
[55] S. Członka, N. Sienkiewicz, A. Strąkowska, K. Strzelec, Keratin feathers as a filler for
rigid polyurethane foams on the basis of soybean oil polyol, Polym. Test. 72 (2018)
32–45, https://doi.org/10.1016/j.polymertesting.2018.09.032.
[56] S. Członka, M.F. Bertino, K. Strzelec, A. Strąkowska, M. Masłowski, Rigid poly-
urethane foams reinforced with solid waste generated in leather industry, Polym.
Test. 69 (2018), https://doi.org/10.1016/j.polymertesting.2018.05.013.
[57] M.C. Silva, J.A. Takahashi, D. Chaussy, M.N. Belgacem, G.G. Silva, Composites of
rigid polyurethane foam and cellulose fiber residue, J. Appl. Polym. Sci. 117 (2010)
3665–3672, https://doi.org/10.1002/app.32281.
[58] Z.L. Song, L.Q. Ma, Z.J. Wu, D.P. He, Effects of viscosity on cellular structure of
foamed aluminum in foaming process, J. Mater. Sci. 35 (2000) 15–20, https://doi.
org/10.1023/A:1004715926692.
[59] S. Gómez-Fernández, L. Ugarte, T. Calvo-Correas, C. Peña-Rodríguez,
M.A. Corcuera, A. Eceiza, Properties of flexible polyurethane foams containing
isocyanate functionalized kraft lignin, Ind. Crop. Prod. 100 (2017) 51–64, https://
doi.org/10.1016/J.INDCROP.2017.02.005.
[60] L.J. Lee, C. Zeng, X. Cao, X. Han, J. Shen, G. Xu, Polymer nanocomposite foams,
Compos. Sci. Technol. 65 (2005) 2344–2363, https://doi.org/10.1016/j.
compscitech.2005.06.016.
[61] S. Matsumura, A.R. Hlil, C. Lepiller, J. Gaudet, D. Guay, Z. Shi, et al., Ionomers for
proton exchange membrane fuel cells with sulfonic acid groups on the end-groups:
novel branched poly(ether-ketone)s, Am. Chem. Soc. Polym. Prepr. Div. Polym.
Chem. 49 (2008) 511–512, https://doi.org/10.1002/pola.
[62] D.W. Hatchett, G. Kodippili, J.M. Kinyanjui, F. Benincasa, L. Sapochak, FTIR ana-
lysis of thermally processed PU foam, Polym. Degrad. Stabil. 87 (2005) 555–561,
https://doi.org/10.1016/j.polymdegradstab.2004.10.012.
[63] S. Chuayjuljit, T. Sangpakdee, Processing and properties of palm oil-based rigid
polyurethane foam, J. Met. Mater. Miner. 17 (2007) 17–23.
[64] Y.H. Hu, Y. Gao, N. De Wang, C.P. Hu, S. Zu, L. Vanoverloop, et al., Rigid poly-
urethane foam prepared from a rape seed oil based polyol, J. Appl. Polym. Sci. 84
(2002) 591–597, https://doi.org/10.1002/app.10311.
[65] U. Stirna, I. Beverte, V. Yakushin, U. Cabulis, Mechanical properties of rigid poly-
urethane foams at room and cryogenic temperatures, J. Cell. Plast. 47 (2011)
337–355, https://doi.org/10.1177/0021955X11398381.
[66] G. Mohammadnezhad, R. Soltani, S. Abad, M. Dinari, A novel porous nano-
composite of aminated silica MCM-41 and nylon-6: isotherm, kinetic, and ther-
modynamic studies on adsorption of Cu(II) and Cd(II), J. Appl. Polym. Sci. 134
(2017) 45383, https://doi.org/10.1002/app.45383.
[67] T. Pretsch, I. Jakob, W. Müller, Hydrolytic degradation and functional stability of a
segmented shape memory poly(ester urethane), Polym. Degrad. Stabil. 94 (2009)
61–73, https://doi.org/10.1016/J.POLYMDEGRADSTAB.2008.10.012.
[68] G. Sung, J.H. Kim, Influence of filler surface characteristics on morphological,
physical, acoustic properties of polyurethane composite foams filled with inorganic
fillers, Compos. Sci. Technol. 146 (2017) 147–154, https://doi.org/10.1016/j.
compscitech.2017.04.029.
[69] R. Gu, M. Khazabi, M. Sain, Fiber reinforced soy-based polyurethane spray foam
insulation. Part 2: thermal and mechanical properties, BioResources 6 (2011)
3775–3790.
[70] S. Zhang, A. Xiang, H. Tian, A.V. Rajulu, Water-blown Castor oil-based poly-
urethane foams with soy protein as a reactive reinforcing filler, J. Polym. Environ.
26 (2018) 15–22, https://doi.org/10.1007/s10924-016-0914-0.
[71] A. Wolska, M. Goździkiewicz, J. Ryszkowska, Thermal and mechanical behaviour of
flexible polyurethane foams modified with graphite and phosphorous fillers, J.
Mater. Sci. 47 (2012) 5627–5634, https://doi.org/10.1007/s10853-012-6433-z.
[72] K. Formela, A. Hejna, Ł. Zedler, M. Przybysz, J. Ryl, M.R. Saeb, et al., Structural,
thermal and physico-mechanical properties of polyurethane/brewers' spent grain
composite foams modified with ground tire rubber, Ind. Crop. Prod. 108 (2017)
844–852, https://doi.org/10.1016/j.indcrop.2017.07.047.
[73] M. Kurańska, A. Prociak, U. Cabulis, M. Kirpluks, J. Ryszkowska, M. Auguścik,
Innovative porous polyurethane-polyisocyanurate foams based on rapeseed oil and
modified with expandable graphite, Ind. Crop. Prod. 95 (2017) 316–323, https://
doi.org/10.1016/j.indcrop.2016.10.039.
[74] R.R. Maharsia, H.D. Jerro, Enhancing tensile strength and toughness in syntactic
foams through nanoclay reinforcement, Mater. Sci. Eng., A 454–455 (2007)
416–422, https://doi.org/10.1016/j.msea.2006.11.121.
S. Członka et al.
[75] F. Saint-Michel, L. Chazeau, J.-Y. Cavaillé, E. Chabert, Mechanical properties of
high density polyurethane foams: I. Effect of the density, Compos. Sci. Technol. 66
(2006) 2700–2708, https://doi.org/10.1016/j.compscitech.2006.03.009.
[76] Q. Lin, L. Qu, B. Luo, C. Fang, K. Luo, Preparation and properties of multiwall
carbon nanotubes/carbon foam composites, J. Anal. Appl. Pyrolysis 105 (2014)
177–182, https://doi.org/10.1016/j.jaap.2013.11.002.
[77] R. Verdejo, R. Stämpfli, M. Alvarez-Lainez, S. Mourad, M.A. Rodriguez-Perez,
P.A. Brühwiler, et al., Enhanced acoustic damping in flexible polyurethane foams
filled with carbon nanotubes, Compos. Sci. Technol. 69 (2009) 1564–1569, https://
doi.org/10.1016/j.compscitech.2008.07.003.
[78] N. Nazeran, J. Moghaddas, Synthesis and characterization of silica aerogel re-
inforced rigid polyurethane foam for thermal insulation application, J. Non-Cryst.
Solids 461 (2017) 1–11, https://doi.org/10.1016/J.JNONCRYSOL.2017.01.037.
[79] M. Kuranska, A. Prociak, Porous polyurethane composites with natural fibres,
Compos. Sci. Technol. 72 (2012) 299–304, https://doi.org/10.1016/j.compscitech.
2011.11.016.
[80] N.E. Marcovich, M. Kurańska, A. Prociak, E. Malewska, K. Kulpa, Open cell semi-
rigid polyurethane foams synthesized using palm oil-based bio-polyol, Ind. Crop.
Prod. 102 (2017) 88–96, https://doi.org/10.1016/j.indcrop.2017.03.025.
[81] E. Ciecierska, M. Jurczyk-Kowalska, P. Bazarnik, M. Gloc, M. Kulesza, M. Kowalski,
et al., Flammability, mechanical properties and structure of rigid polyurethane
foams with different types of carbon reinforcing materials, Compos. Struct. 140
(2016) 67–76, https://doi.org/10.1016/j.compstruct.2015.12.022.
[82] R. Gu, S. Konar, M. Sain, Preparation and characterization of sustainable poly-
urethane foams from soybean oils, JAOCS, J Am Oil Chem Soc 89 (2012)
2103–2111, https://doi.org/10.1007/s11746-012-2109-8.
[83] L. Wu, J.V. Gemert, R.E. Camargo, Rheology Study in Polyurethane Rigid Foams.
Auburn Hills, USA, (2008).
[84] H. Hatakeyama, R. Kosugi, T. Hatakeyama, Thermal properties of lignin-and mo-
lasses-based polyurethane foams, J. Therm. Anal. Calorim. 92 (2008) 419–424,
https://doi.org/10.1007/s10973-007-8963-1.
[85] V. Ribeiro Da Silva, M.A. Mosiewicki, M.I. Yoshida, M. Coelho Da Silva,
P.M. Stefani, N.E. Marcovich, Polyurethane foams based on modified tung oil and
reinforced with rice husk ash II: mechanical characterization, Polym. Test. 32
(2013) 665–672, https://doi.org/10.1016/j.polymertesting.2013.03.010.
[86] M.A. Mosiewicki, P. Rojek, S. Michałowski, M.I. Aranguren, A. Prociak, Rapeseed
oil-based polyurethane foams modified with glycerol and cellulose micro/nano-
crystals, J. Appl. Polym. Sci. 132 (2015) 9–12, https://doi.org/10.1002/app.41602.
[87] V. Ribeiro Da Silva, M.A. Mosiewicki, M.I. Yoshida, M. Coelho Da Silva,
P.M. Stefani, N.E. Marcovich, Polyurethane foams based on modified tung oil and
reinforced with rice husk ash I: synthesis and physical chemical characterization,
Polym. Test. 32 (2013) 438–445, https://doi.org/10.1016/j.polymertesting.2013.
01.002.
25
Polymer Testing 75 (2019) 12–25
[88] L. Jiao, H. Xiao, Q. Wang, J. Sun, Thermal degradation characteristics of rigid
polyurethane foam and the volatile products analysis with TG-FTIR-MS, Polym.
Degrad. Stabil. 98 (2013) 2687–2696, https://doi.org/10.1016/j.polymdegradstab.
2013.09.032.
[89] S.V. Levchik, E.D. Weil, Thermal decomposition, combustion and fire-retardancy of
polyurethanes - a review of the recent literature, Polym. Int. 53 (2004) 1585–1610,
https://doi.org/10.1002/pi.1314.
[90] A.A. Septevani, D.A.C. Evans, C. Chaleat, D.J. Martin, P.K. Annamalai, A systematic
study substituting polyether polyol with palm kernel oil based polyester polyol in
rigid polyurethane foam, Ind. Crop. Prod. 66 (2015) 16–26, https://doi.org/10.
1016/j.indcrop.2014.11.053.
[91] D.K. Chattopadhyay, D.C. Webster, Thermal stability and flame retardancy of
polyurethanes, Prog. Polym. Sci. 34 (2009) 1068–1133, https://doi.org/10.1016/j.
progpolymsci.2009.06.002.
[92] S. Estravís, J. Tirado-Mediavilla, M. Santiago-Calvo, J.L. Ruiz-Herrero, F. Villafañe,
M.Á. Rodríguez-Pérez, Rigid polyurethane foams with infused nanoclays: relation-
ship between cellular structure and thermal conductivity, Eur. Polym. J. 80 (2016)
1–15, https://doi.org/10.1016/j.eurpolymj.2016.04.026.
[93] M.A. Mosiewicki, G.A. Dell'Arciprete, M.I. Aranguren, N.E. Marcovich,
Polyurethane foams obtained from castor oil-based polyol and filled with wood
flour, J. Compos. Mater. 43 (2009) 3057–3072, https://doi.org/10.1177/
0021998309345342.
[94] K.H. Badri, Z. Othman, S.H. Ahmad, Rigid polyurethane foams from oil palm re-
sources, J. Mater. Sci. 39 (2004) 5541–5542, https://doi.org/10.1023/B:JMSC.
0000039282.86374.fc.
[95] A.M. Atta, W. Brostow, T. Datashvili, R.A. El-Ghazawy, H.E.H. Lobland,
A.R.M. Hasan, et al., Porous polyurethane foams based on recycled poly(ethylene
terephthalate) for oil sorption, Polym. Int. 62 (2013) 116–126, https://doi.org/10.
1002/pi.4325.
[96] A. Kairyte, S. Vejelis, Evaluation of forming mixture composition impact on prop-
erties of water blown rigid polyurethane (PUR) foam from rapeseed oil polyol, Ind.
Crop. Prod. 66 (2015) 210–215, https://doi.org/10.1016/j.indcrop.2014.12.032.
[97] M. Thirumal, D. Khastgir, N.K. Singha, B.S. Manjunath, Y.P. Naik, Mechanical,
morphological and thermal properties of rigid polyurethane foam: effect of the
fillers, Cell. Polym. 26 (2007) 245–259.
[98] G.C. Basak, L. Goswami, B. Chattopadhyay, A. Bandyopadhyay, Plasticizing poly-
styrene with waste leather buffing dust: a drive towards waste-polymer composite
synthesis, Polym. Polym. Compos. 20 (2012) 279–288.
[99] ENERLAB, Polyisocyanurate Foam Boards, (2012) Retrieved September 2013 from,
n.d http://www.enerlab.ca/vw/fd/CartierECOANG.pdf/$fil.
[100] K.H. Badri, S.H. Ahmad, S. Zakaria, Production of a high-functionality RBD palm
kernel oil-based polyester polyol, J. Appl. Polym. Sci. 81 (2001) 384–389, https://
doi.org/10.1002/app.1449.